Advanced Mineralogy, Vol.1

To Be Published in This Series
Volume 1
Composition, Structure, and Properties

of Mineral Matter: Concepts, Results, and Problems
Volume 2
Methods and Instrumentations:

Results and Recent Developments
Volume 3
Mineral Matter in Space, Mantle, Ocean Floor,

Biosphere, Environmental Management, Jewelry
Volume 4
Processes of Mineral Formation:

Frontiers in Experiment and Evolution in
Geological History
Volume 5
Minerals as a Source of Metals, Energy, and Materials
A.S. Marfunin
(Ed.)
Advanced
Mineralogy
Volume 1
Composition, Structure, and Properties
of Mineral Matter:
Concepts, Results, and Problems
With 133 Figures and 40 Tables
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona
Budapest
Prof. Dr.
A.S.
MARFUNIN
Geological Faculty
University of Moscow
119899
Moscow
Russia
ISBN-13 :978-3-642-78525-2
e-ISBN-13 :978-3-642-78523-8
DOl: 10.1007978-3-642-78523-8
CIP data applied for
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Springer Verlag Berlin Heidelberg 1994

Softcover reprint of the hardcover 1st edition 1994
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5 4 3 2 10
Printed on acidfree paper
Preface
All existing introductory reviews of mineralogy are written according to the same algorithm, sometimes called the "Dana System of
Mineralogy". Even modern advanced handbooks, which are certainly necessary, include basic data on minerals and are essentially
descriptive. When basic information on the chemistry, structure,
optical and physical properties, distinguished features and paragenesis of 200-400 minerals is presented, then there is practically no
further space available to include new ideas and concepts based on
recent mineral studies.
A possible solution to this dilemma would be to present a book
beginning where introductory textbooks end for those already familiar with the elementary concepts. Such a volume would be tailored to
specialists in all fields of science and industry, interested in the most
recent results in mineralogy.
This approach may be called Advanced Mineralogy. Here, an
attempt has been made to survey the current possibilities and aims in
mineral matter investigations, including the main characteristics of
all the methods, the most important problems and topics of mineralogy, and related studies.
The individual volumes are composed of short, condensed chapters. Each chapter presents in a complete, albeit condensed, form
specific problems, methods, theories, and directions of investigations,
and estimates their importance and strategic position in science and
industry.
The following fields will be covered in the individual volumes:
Vol. 1 Composition, Structure, and Properties of Mineral Matter:
Concepts, Results, and Problems
Vol. 2 Methods and Instrumentations: Results and Recent Developments
Vol. 3 Mineral Matter in Space, Mantle, Ocean Floor, Biosphere,
Environmental Management, Jewelry
Vol. 4 Processes of Mineral Formation: Frontiers in Experiment
and Evolution in Geological History
Vol. 5 Minerals as a Source of Metals, Energy, and Materials
VI
Preface
The book thus attempts to present a universal (or perhaps a

wholistic) approach to the nature and role of mineral matter, by
presenting frontier facts and hypotheses in as many fields of the
mineral science as possible.
A complex set of volumes like this could never have been written
by just one author. I am therefore happy that top specialists from all
over the world and from different disciplines agreed to contribute. I
have had the priviledge of discussing the topics through extensive
communication with the authors, orally and in writing, and I wish to
thank them for their support and collaboration.
I am also grateful for the discussions of the different aspects of the
book with R.1. Kirkpatrick (Urbana), G. Rossman (Pasadena), Chr.
Amstutz (Heidelberg), W. Baur (Frankfurt), G. Amthauer (Salzburg),
A. Beran (Vienna), S. Hafner (Marburg), Ch. Prewitt (Washington),
Xie Xiande (Guangzhou), Y. Dusausoy (Nancy), W. Engel (Heidelberg, Springer-Verlag), L. V. Bershov and N. F. Chelishchev (Moscow).
Moscow, May 1994
A.S. Marfunin
Contents
Introduction . . . . . . . . . . . . . . . . . . . .
XXIII
Chapter I The Chemical Nature of Minerals . . . . . . . . . .
1.1
Chemical Composition of Minerals. Crystallochemical

Constraints and the Nature of Impurities
R.H. MITCHELL, M.I. NOVGORODOVA, and E.!. SEMENOV.
1.2 Treatment of Chemical Composition Data for Minerals

1.2.1 Structural Formulae
A.G. BULACH and J. ZUSSMAN . . . . . . . . . . .
1.2.2 Multivariate Statistical Analysis for Processing
Chemical Data of Minerals
C. JOHN MANN and V.M. RYAKHOVSKY . . . . . .
1.3
The Mineral Composition of the Earth's Crust,

Mantle, Meteorites, Moon and Planets
A.A. YAROSHEVSKY and A.G. BULAKH . . . . . .
Chapter 2 Crystal Structures of Minerals . . . . . . . .
2.1
2.1.1
2.1.2
2.1.3
2.1.4
2.1.5
General Results of Crystal Structure Analysis of

Minerals . . . . . . . . . . . . . . . . . . . . . . . .
Stages of Scientific and Technical Development
V.A. DRITs, F. LIEBAU, and Ch. PREWITT. . . . . .
Symmetry Bases. The Contemporary Symmetry
Theory in Solids
V.A. KOPTSIK . . . . . . . . . . . . . . . . . . . . .
Empirical Relationships in Structural Geometry
W.H. BAUR. . . . . . . . . . . . . . . . . . . . . .
Systems of Empirical Radii of Atoms and Ions;
Orbital and Pseudopotential Radii
W.H. BAUR. . . . . . . . . . . . . . . . . . . . . .
Representation of Crystal Structures as Packings
of Spheres, Coordination Polyhedra, or Nets of Bonds
W.H. BAUR and D. KASSNER. . . . . . . . . . . . . . . ..
2
12
12
18
27
37
38
38
50
55
61
64
VIII
Contents
2.1.6 Computer Simulation of Crystal Structures

G.D. PRICE and V.S. URUSOV . . . . . . . . .
2.1.7 Precision Electron Density Calculations:
Relation to Chemical Bonding and to Localization
of Impurities in Crystal Structures
V.G. TSIRELSON and O.V. FRANK-KAMENETSKAYA.
2.1.8 High-Temperature and High-Pressure Crystal
Chemistry
S.K. FILATovand RM. HAZEN. . . . . . . . .
2.2 Types of Structural Relations in Minerals . .
2.2.1 Modulated and Incommensurate Structures;
Spinodal Unmixing
N.I. ORGANOVA . . . . . . . . . . . . . . . . . .
2.2.2 Hybrid Layer Structures, Commensurate and
Incommensurate
R. ALLMANN . . . . . . . . . . . . . . . . . . . .
2.2.3 Tunnel-Structure Oxide Minerals
S.R. TURNER, A.1. GORSHKOV, and P.R BUSECK
2.2.4 Polytypism in Minerals
A.G. CHRISTY and B.B. ZVYAGIN
2.2.5 Mixed-Layer Minerals
V.A. DRITS and RC. REYNOLDS .
2.2.6 Structural and Magnetic Phase Transitions
S. GHOSE . . . . . . . . . . . .
2.2.7 Poorly Crystallized Minerals
G. BESSON and V.A. DRITS. .
2.2.8 The Metamict State
RC. EWING and J. AKIMOTO .
2.3
2.3.1
2.3.2
2.3.3
2.3.4
2.3.5
2.3.6
Systematics of Crystal Structures and

Crystallochemical Classifications of Minerals .
Prolegomenon
P.B. MOORE . . . . . . . . . . . . . . . . .
Contemporary Aspects of Classifications
G.B. BOKIY. . . . . . . . . . . . . . . . . .
Two Approaches Toward Crystallochemical
Classification of Minerals and Inorganic Crystals
G.B. BOKIY. . . . . . . . . . . . . . . . . . . . .
Crystallochemical Classifications of Minerals
G.B. BOKIY. . . . . . . . . . . . . . . . . . .
The Structural Classification of Minerals
J.M. LIMA-DE-FARIA. . . . . . . . . . . . . .
Counting Theory and Classification of Crystal
Structures
P.B. MOORE . . . . . . . . . . . . . . . . . . . . . . . . . .
69
72
76
90
90
95
101
106
124
133
138
140
147
147
152
154
155
159
164
Contents
Chapter 3 Real Structures of Minerals

3.1
3.2
3.3
3.4
3.5
IX
169
Point Defects in Minerals

A. DUBA and R. SCHOCK ..
170
Direct Imaging of Point Defects by HRTEM

D.R. VEBLEN and J.M. COWLEY . . . . . .
172
Point Defects and Diffusion in Minerals

FJ. RYERSON and R.H. CONDIT . . . . . .
175
Point Defects as Precursors for Electron-Hole Centers:

Systematics and Theories of Radiation Centers
in Minerals
Y. DUSAUSOY and J.A. WElL. . . . . . . . . . . .
180
Structural Types of NonStoichiometry in Minerals

D.R. VEBLEN. . . . . . . . . . . . . . . . . . . . . .
197
3.6
X-Ray Topographic Study of the Real Structure

of Minerals
A. AUTHIER and A. ZARKA . . . . . . . . . .
. ... 221
3.7
Twinning Due to Phase Transformations

and Plastic Deformation
A.c. McLAREN. . . . . . . . . . . . . . . . .
Chapter 4 Natural Glasses.

4.1
233
237
Structure and Properties of Silicate Glasses and

Melts; Theories and Experiment
B.O. MYSEN and D. VIRGO. . . . . . . . . . . . . .
238
4.2
X-Ray Studies of Glass Structure

D.A. McKEOWN and N. ZOTOV. .
254
4.3
Terrestrial and Lunar, Volcanic and Impact Glasses,

Tektites, and Fulgurites
V. BOUSKA and V.I. FELDMAN . . . . . . . . . . . .
4.4
. 258
Nuclear Waste Glasses: Recent Advances in the

Spectroscopic Investigation of Their Structure
D. PETIT-MAIRE, J. PETIAU, and G. CALAS .
266
Chapter 5 Chemical Bonding in Minerals . . . . . . . . . .
271
5.1
Survey of Quantum Chemistry and Methods Used

to Calculate the Electronic Structures of Minerals
S.P. DOLIN and D.M. SHERMAN. . . . . . . . . . . . . . . 272
x
5.2
5.3
5.4
5.5
5.6
Contents
Chemical Bonding in Silicates

S. DUBROVINSKyand D.M. SHERMAN.
296
Chemical Bonding in Sulfide Minerals

D.W. BULLETT . . . . . . . . . . . . . . .
310
Bonding in Oxides, Oxyanions, and Halides

D.S. URCH . . . . . . . . . . . . . . . . . . . . .
319
Electronic Structures of Iron Oxides and Silicates

D.M. SHERMAN . . . . . . . . . . .
327
Hydrogen Bonding in Minerals

F.e. HAWTHORNE and W.H. BAUR
340
Chapter 6 Properties of Minerals . . . . . . . . . . . . . . . . . 349

6.1
Elastic Properties of Minerals

V.M. AGOSHKOV and V.L. PANKOV .
350
6.2
Hardness of Minerals . . . . . . . . .
6.2.1 Hardness, Compressibility, Cohesive Energy
S.V. TITKOV . . . . . . . . . . . . . .
6.2.2 Problems of Extra Hard Materials
e.A. BROOKES . . . . . . . . . . . . .
358
6.3
Deformations in Minerals . . . . . .
6.3.1 Mechanisms of Plastic Deformation in Minerals;
Role of Dislocations
e. WILLAIME and M. GANDAIS. . . . . . . . . .. . . . .
6.3.2 Fracture Mechanics and Fracture Mechanisms
in Minerals
...
G.E. LLOYD and e.e. FERGUSON . . . . . . . . .
6.3.3 High Resolution Electron Microscopic Techniques
in the Study of Defects
S. AMELINCKX . . . . . . . . . . . .
6.3.4 Hydrolytic Weakening of Quartz
J.e. DOUKHAN and P. CORDIER . .
6.3.5 High Temperature Flow in Minerals and Ceramics
and Its Bearing on the Creep Behavior
of the Earth's Silicate Mantle
M.R. DRURY . . . . . . . . . . . . . . . . .
366
358
361
366
370
377
383
390
395
6.4
Electrical Properties of Minerals. . . . . . . . . . . ..
6.4.1 Electrical Conductivity in Iron-Bearing Minerals and
Materials
T.O. MASON . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Contents
6.4.2 Superionic Conductors

B.A. MAXIMOV. . . . . .
6.4.3 Electrical Properties of Ore Minerals
G.A. GORBATOV . . . . . . . . . . . . .
6.4.4 Dielectric Properties of Minerals and Rocks:
Applications to Microwave Remote Sensing
B. CERVELLE and XIAO lIN-KAI . . . . . .
XI
399
402
. . . . . . 405
Lattice Dynamics, Vibrational Spectra,

Thermodynamic and Heat Properties of Minerals.
6.5.1 Lattice Dynamics and Force Fields in Crystals
P.F. McMILLAN, A.N. LAzAREv, and S.W. KIEFFER
6.5.2 Lattice Dynamics and Thermodynamic Properties
of Minerals
V.M. AGOSHKOV, S.W. KIEFFER, and
P.F. McMILLAN. . . . . . . . . . . . .
6.5.3 Heat Flow in the Earth's Crust and Mantle
G. BUNTEBARTH and A. GLIKO. . .
6.5
412
412
419
430
6.6
Magnetic Properties of Minerals .
6.6.1 Magnetic Minerals
W. O'REILLY . . . . . . . . . . . . .
6.6.2 Self-Reversal of Natural Remanent Magnetization
and Magneto Mineralogical Processes.
Magnetic Properties and Geothermometry
V.1. TRUKHIN and F. HELLER . . . . . . . . . . . . . . . . .
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor,
and Plate Tectonics
H.e. SOFFEL and D.l. DUNLOP . . . . .
6.6.4 Aeromagnetic Exploration Mineralogy
St.E. HAGGERTY . . . . . . . . . . . . . .
6.6.5 Magnetic Separation; High Magnetic Fields
P.A. CHEREMNYKH. . . . . . . . . . . . . . . . .
436
6.7
Optical Properties of Minerals . . . . . . . .
6.7.1 General Review of Optical Mineralogy and
Phenomenological Crystal Optics
W.D. NEsSE and Y.O. PUNIN . . . . . . .
6.7.2 Theoretical Interpretation of Refraction
1. ARNDT . . . . . . . . . . . . . . . . . . .
6.7.3 Reflectance Spectra: Their Interpretation Using
Band Theory and Application in Mineral
Identification
A.l. CRIDDLE and E.G. RYABEVA . . . . . .
6.7.4 Ellipsometry and Modulation Spectroscopy
R.M.A. AZZAM and lA. BRYZGALOV . . . . .
472
436
450
457
464
470
472
477
487
492
XII
Contents
6.7.5 Nonlinear Optical Characteristics of Minerals

L.B. MEISNER . . . . . . . . . . . . . . . . . ..
6.8
6.9
. . . . . 495
Technological Mineralogy and Technological

Properties of Minerals
O.V. KONoNovand W. PETRUK . . . . . . . .
497
Mineral Properties in Engineering Geology

J.E. GILLOTT and V.1. OSIPOV . . . . . . . . .
504
Chapter 7 Mineralogical Material Science . . . . . . . . . . . . 511
7.1
Concept of Materials as a New Approach to Solids

and Minerals; Natural Minerals, and Their Synthetic
Analogs as Materials
A.S. MARFUNIN . . . . . . . . . . . . . . . . . . .
. 512
7.2
An Overview of Materials for Electronics and

Optics
R.E. NEWNHAM and M.1. SAMOILOVICH.
Piezoelectric Materials. . . . . . . . . .
Materials for Acoustoelectronics . . . .
Materials for Optics, Electro-optics and
Acousto-optics. . . . . . . . . . . . . . . .
Laser Materials . . . . . . . . . . . . . . .
Cathodochromic Screens and Scintillation Counters
Nonlinear Optic Materials . . . . . . . . . . . .
7.2.1
7.2.2
7.2.3
7.2.4
7.2.5
7.2.6
514
514
515
516
519
520
520
7.3 Multifunctional Minerals . . . . . . . . . . . . .

7.3.1 Diamond: the Mineral-Absolute. Applications
in Electronics
A.S. MARFUNIN . . . . . . . . . . . . . .
7.3.2 Quartz Crystals in Devices
M.1. SAMOlLOVICH and R.E. NEWNHAM.
7.3.3 Corundum-Ruby-Sapphire
R.E. NEWNHAM and M.1. SAMOILOVICH .
7.3.4 Natural and Synthetic Zeolites. Applications
in Radioactivity, Ecology, Petroleum Chemistry,
and Agrotechnology
N.F. CHELISHCHEV and LV. MISHIN .
521
528
Mineral Index
541
Subject Index .
545
521
526
527
List of Contributors
AFONIN, V.P., Institute of Geochemistry, Favorky Str. la,

Irkutsk 664033, Russia
AoosHKov, V.M., Vernadsky Institute of Geochemistry,
Kosygina 19, Moscow 117975, Russia
AKIMOTO, I., Department of Chemistry, The University of
Tsukuba, Sakura-mura, Ibaraki, 305 Japan
ALEINIKOFF, 1., US Geological Survey, Denver Federal Center,
PO Box 25046, Denver, CO 80225, USA
ALLMANN, R., Institut fUr Mineralogie und Kristallographie,
Universitiit Marburg, D-35037 Marburg/Lahn, Germany
ALTANER, S., Department of Geology, University of Illinois,
Urbana, IL 61801, USA
AMELINCKX, S., University of Antwerp, Groenenbergelaan 171,
B-2020 Antwerp, Belgium
AMTHAUER, G., Institut fiir Mineralogie, Universitiit Salzburg,
Hellbrunnerstrasse 34, A-5020 Salzburg, Austria
ANDERSON, T., Department of Geology, University of Illinois,
ARNDT, J., Freie Universitiit Berlin, Institut fUr Mineralogie,
Takustrasse 6, D-14195 Berlin, Germany
AUTHIER, A., Laboratoire de Mineralogie-Cristallographie,
Universites Paris VI et VII, Tour 16, 4 Place Jussieu,
F-75252 Paris Cedex 05, France
AzzAM, R.M.A., Department of Electrical Engineering, University
of New Orleans, Lakefront, New Orleans, LA 70148, USA
BAUR, W.H., Institut fiir Kristallographie der Universitiit
Frankfurt, Senckenberganlage 30, D-60325 Frankfurt/Main,
Germany
BELLER, u., Fachgebiet Qualitiitkontrolle, Universitiit Dortmund,
Emil-Figge-Strasse 74, D-44227 Dortmund, Germany
BERAN, A., Institut fUr Mineralogie and Kristallographie der
Universitiit Wien, Dr-Karl-Liiger-Ring 1, A-I0tO Wien, Austria
BESSON, G., Laboratoire de Cristallographie, Universite d'Orleans,
B.P. 6759, F-45067 Orleans Cedex 2, France
BIBIKOVA, E.V., Vernadsky Institute of Geochemistry,
XIV
BOKIY, G.B., IGEM Academy of Sciences, Staromonetniy 35,

Moscow 109017, Russia
BOUSKA, V., Prirodovedecka Fakulta UK, Praha 2 - Albertov 6,
12843, Czech Republic
BRICK, A., Institute of Geochemistry and Physics of Minerals,
Palladina 34, 252680 Kiev 142, Ukraina
BRIGGS, P.H., uS Geological Survey, Denver Federal Center,
Denver, CO 80225, USA
BRINKMANN, D., Physik-Institut der Universitiit Zurich,
Schonberggasse 9, CH-8001 Zurich, Switzerland
BROOKES, CA., Department of Engineering Design and
Manufacture, University of Hull, Hull HU6 7RX, England
BRYZGALOV, 1.A., Geological Faculty, Moscow University,
BULAKH, A.G., Chair of Mineralogy, St. Petersburg University,
St. Petersburg 199034, Russia
BULLETT, D.W., School of Physics, University of Bath,
Claverton Down, Bath BA2 7AY, England
BUNTEBARTH, G., Institut fur Geophysik, Technische Universitiit,
Postfach 1253, D-38678 Clausthal-Zellerfeld, Germany
BUSECK, P.R., Department of Geology, Arizona State University,
Tempe, AZ 85287, USA
BYKOV, A.V., Physical Faculty, Moscow University,
CALAS, G., Laboratoire de Mineralogie-Cristallographie,
Universites Paris VI et VII, Tour 16,4 Place lussieu,
F -75252 Paris Cedex 05, France
CERVELLE, B., Laboratoire de Mineralogie-Cristallographie,
Universite Pierre et Marie Curie Paris VI-VII, Tour 16,
4 Place lussieu, F-75252 Paris Cedex 05, France
CHELISHCHEV, N.F., Institute of Mineralogy, Geochemistry and
Crystal Chemistry of Rare Metals, Sadovnicheskaya 71,
CHEREMNYKH, P.A., Kurchatov Institute of Atomic Energy,
Kurchatov Place, Moscow 123098, Russia
CHERNYSHEV, J.V., IGEM Academy of Sciences, Staromonetny 35,
CHRISTY, A.G., Department of Earth Sciences, University of
Cambridge, Downing Street, Cambridge CB2 3EQ, England
CONDIT, R.H., Lawrence Livermore National Laboratory,
Livermore, CA 94550, USA
CORDIER, P., Laboratoire de Structure et Proprietes de l'Etat
Solid, Universite de Lille-Flandres-Artois, F-59665 Villeneuve
d' Ascq Cedex, France
COWLEY, 1.M., Department of Physics, Arizona State University,
Tempe, AZ 85287, USA
xv
CRIDDLE, AJ., Department of Mineralogy, British Museum

(Natural History), Cromwell Road, London SW7 5BD,
England
CROCK, J.G., US Geological Survey, Branch of Geochemistry,
Mail Stop 973, Denver Federal Center, Denver, CO 80225,
USA
DELYAGIN, N.N., Physical Faculty, Moscow University,
DE PAOLO, D.I., Department of Earth and Space Sciences, UCLA,
Los Angeles, CA 90024, USA
DOLIN, S.P., IGEM Academy of Sciences, Staromonetny 35,
DOUKHAN J.-c., Laboratoire de Structure et Proprietes de I'Etat
Solid, Universite de Lille-Flandres-Artois, F-59655 Villeneuve
d'Ascq Cedex, France
DRITS, V.A., Geological Institute, Academy of Sciences,
Pyzhevsky 7, Moscow 109017, Russia
DRURY, M.R., Research School of Earth Sciences, The Australian
National University, Canberra, ACT 2601, Australia
DUBA, A., Earth Sciences Department and Energy Program,
Lawrence Livermore National Laboratory, University of
California, Livermore, CA 94550, USA
DUBESSY, J., CREGU, 3, rue de Champelle, F-54501 Vandoeuvre
les Nancy Cedex, France
DUBROVINSKY, L.S., IGEM Academy of Sciences, Staromonetny 35,
DUNLOP, D.1., Erindale College, University of Toronto,
3359 Mississauga, Ontario, L5L 106, Canada
DUSAUSOY Y., Laboratoire de Mineralogie-Cristallographie,
Universite de Nancy, F-54037 Nancy Cedex, France
ERMAKOV, A.V., Institute of Physics, St. Petersburg University,
Ulyanovskaya 1, St. Petersburg-Petrodvorets 198904, Russia
EWING, R.c., Department of Geology, University of New Mexico,
Albuquerque, NM 87131, USA
FELDMAN, V.I., Geological Faculty, Moscow University,
FERGUSON, C.c., A.G. Weeks and Partners Ltd., Maidstone,
Kent ME14 5LH, England
FILATOV, S.K., Chair of Crystallography, St. Petersburg
University, St. Petersburg 199034, Russia
FRANK-KAMENETSKAYA, O.V., Chair of Crystallography,
Leningrad University, Leningrad 199034, Russia
FUESS, H., Technische Hochschule, Karolinenplatz 5,
D-64289 Darmstadt, Germany
GALIMOV, E.M., Vernadsky Institute of Geochemistry,
XVI
GANDAIS, M., Laboratoire de Mineralogie-Cristallographie

Universites Pierre et Marie Curie Paris VI et VII, Tour 26,
4 Place Jussieu, F-75252 Paris Cedex 05, France
GHOSE, S., Mineral Physics Group, Department of Geological
Sciences, University of Washington, Seattle, WA 98195, USA
GILLOTT, J.E., Department of Civil Engineering University of
Calgary, 2500 University Drive, N.W. Calgary, Alberta,
T2 Nl N4 Canada
GLlKO, A.O., Institute of Physics of the Earth, Bolshaya
Grusinskaya 10, Moscow 123810, Russia
GORBATOV, G.A., Institute of Mineral Resources (VIMS),
Staromonetny 33, Moscow 109017, Russia
GOROBETS, B.S., Institute of Mineral Resources (VIMS),
GORSHKOV, A.I., IGEM, Academy of Sciences, Staromonetny 35,
GUINIER, A., Laboratoire de Physique des Solides, Universite
Paris-Sud, F-91405 Orsay Cedex, France
GULSOl\, B.L., Division of Mineral Physics and Mineralogy,
CSIRO, Institute of Energy and Earth Resources, North Ryde,
N.S.W. 2113, Australia
HAENDEL, D., Central Institute of Isotope and Radiation Research,
Permoserstrasse 15, D-04318 Leipzig, Germany
HAGGERTY, St.E., Morrill Science Center, Geological Department,
University of Massachusetts, Amherst, MA 01003, USA
HAHN, T., Institut fur Kristallographie, RWTH, Templergraben 55,
D-52062 Aachen, Germany
HAWTHORNE, F.e., Department of Geological Sciences, University
of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
HAZEN, R.M., Geophysical Laboratory, 5241 Broad Branch Rd.,
Washington, DC 20015, USA
HELLER, F., Institut fUr Geophysik, ETH, Hunggerberg,
CH-8093 Zurich, Switzerland
HOEFS, I., Geochemisches Institut, Universitiit G6ttingen,
Goldschmidtstrasse 1, D-37077 G6ttingen, Germany
HOFMEISTER, A.M., Department of Geology, 175 Physics/Geology
University of California, Davis, CA 95616, USA
ILlEV, M., Faculty of Physics, University of Sofia, 1126 Sofia,
Bulgaria
JARVIS, K., Geology Department, Royal Holloway and Bedford New
College, University of London, London TW20 OEX, England
KAMENTSEV, I.E., Chair of Crystallography, St. Petersburg University,
St. Petersburg 199034, Russia
KARPENKO, S.F., IGEM, Academy of Sciences, Staromonetny 35,
XVII
KASSNER, D., Institut fUr Kristallographie der Universitat

Frankfurt, Senckenberganlage 30, D-60325 Frankfurt/Main,
Germany
KIEFFER, S.W., Geology Department, Arizona State University,
Tempe, AZ 85287-1404, USA
KIRKPATRICK, R.J., Department of Geology, University of Illinois,
KOEBERL Chr., Institute of Geochemistry, University of Vienna,
A-lOlO Vienna, Austria
KONONOV, O.V., Geological Faculty, Moscow University,
KOPTSIK, V.A., Physical Faculty, Moscow University,
KORTOV, V.S., Department of Experimental Physics,
Ural Poly technical Institute, Ekaterinburg 62002, Russia
KULIKOV, O.A., Geographical Faculty, Moscow University,
LANGER, K., Institut fur Mineralogie und Kristallographie,
Technische Universitat Berlin, Ernst-Reuter-Platz 1,
D-I0587 Berlin, Germany
LAZAREV A.N., Institute of Silicate Chemistry, Makarov Quay 2,
Leningrad 199034, Russia
LEBEDEV Ya.S., Institute of Chemical Physics, Kosygina 4,
LIEBAU, F., Mineralogisch-Petrographisches Institut, Universitat
Kiel, Olshausenstrasse 40-60, D-24118 Kiel, Germany
LIMA-DE-FARIA, J., Instituto Nacional de Investigacao Cientifica
Tropical, AI. Alfonso Henriques, 41-4E, 1000 Lisboa,
Portugal
LIPPOLT, H.I., Laboratorium fUr Geochronologie, Universitat
Heidelberg, D-69121 Heidelberg, Germany
LLOYD, G.E., Department of Earth Sciences, The University,
Leeds LS2 9JT, England
MANCEAU, A., Laboratoire de Mineralogie-Cristallographie,
Universite Paris VI-VII, Tour 16, 4, Place Jussieu, F-75252 Paris
Cedex 05, France
MANN, J., Department of Geology, University of Illinois, Urbana,
IL 61801, USA
MARFUNIN, A.S., Department of Mineralogy, Geological Faculty,
Moscow University, Moscow 119899, Russia
MASON, T.O., Department of Material Sciences and Engineering,
The Technological Institute, Northwestern University,
Evanston, IL 60201, USA
MAXIMOV, B.A., Institute of Crystallography, Leninsky Prospect 59,
Moscow 117333. Russia
XVIII
McDERMOTT, P.F., Department of Earth Sciences, The Open

University, Walton Hall, Milton Keynes MK7 6AA, England
McKEEVER, S.W.S., Department of Physics, State University of
Oklahoma, Stillwater, OK 74078, USA
McKEOWN, D.A., Chemistry Department, Haward University,
525 College Street N.W., Washington, DC 20059, USA
McLAREN, A.C., Research School of Earth Sciences, The
Australian National University, Canberra A.C.T. 2601,
Australia
McMILLAN, P.F., Department of Chemistry, Arizona State
University, Tempe, AZ 85287, USA
MEISNER, L.B., Institute of Mineral Resources (VIMS),
MISHIN, LV., Institute of Organic Chemistry, Academy of Sciences,
Leninsky Prospect 47, Moscow 117913, Russia
MITCHELL, R.H., Department of Geology, Lakehead University,
Thunderbay, Ontario P7B 5El, Canada
MOORE, P.B., Department of Geophysical Sciences, University of
Chicago, 5734 South Ellis Avenue Chicago, IL 60637, USA
MYSEN, B.O., Geophysical Laboratory, 5251 Broad Branch Road,
Washington, DC 20015-1305, USA
NAMBI, K.S.V., Environmental Assessment Section,
Bhabha Atomic Research Center, Trombay, Bombay 85, India
NESSE, W.D., Department of Earth Sciences, University of
Northern Colorado, Greeley, CO 80639, USA
NEWNHAM, R.E., Material Science Center, Pennsylvania State
University, University Park, PA 16802, USA
NIKLAS, LR., Experimentalphysik, UniversiHit-Gesamthochschule
Paderborn, Warburgerstrasse l00A, D-33098 Paderborn,
Germany
NIKOLAEV, V.I., Physical Faculty, Moscow University,
Moscow, 119899, Russia
NOVGORODOVA, M.L, IGEM, Academy of Sciences,
O'NEIL, LR., Department of Geological Sciences, The University
of Michigan, 1006 c.c. Little Building, Ann Arbor,
MI 48109-1063, USA
O'REILLY, W., Department of Geophysics, University Newcastle
on Tyne, Newcastle on Tyne NEI 7RU, England
ORGANOVA, N.L, IGEM, Academy of Sciences, Staromonetny 35,
ORLOV, R.lu., Geological Faculty, Moscow University,
OSIPOV, V.I., Geological Faculty, Moscow University,
Moscow 119899. Russia
XIX
OZIMA, M., Geophysical Institute, University of Tokyo,

Tokyo 113, Japan
PANKOV, V.L., Institute of Physics of the Earth, B. Gruzinskaya 10,
PARRY, SJ., Imperial College Reactor Centre, Silwood Park,
Buckhurst Road, Ascot, Berks. SL5 7TE, England
PENKOV, I.N., Geological Faculty, Kazan University, Lenina 4/5,
Kazan 420111, Russia
PENNOCK, G., Research School of Earth Sciences,
The Australian National University, Canberra, A.C.T. 2601,
Australia
PETIAU, J., Laboratoire de Mineralogie-Cristallographie,
Universite de Paris VI et VII, 4 Place Jussieu, F-75252 Paris
Cedex 05, France
PETIT-MAIRE, D., Saint Gobain Recherche, F-93304 Aubervilliers
Cedex, France
PETRUK, W., CANMET, 555 Booth St., Ottawa,
Ontario KIA OGl, Canada
PLATONOV, A.N., Institute of Geochemistry and Physics of
Minerals, Palladina 34, Kiev 252680, Ukraina
POKROVSKIY B.G., Geological Institute, Academy of Sciences,
POLSHIN, E.M., Institute of Geochemistry and Physics of Minerals,
Palladina 34, Kiev 252680, Ukraina
POTTS, P.J., Department of Earth Sciences, The Open University,
Walton Hall. Milton Keynes MK7 6AA, England
PREWITT, Ch., Geophysical Laboratory, 5251 Broad Branch Road,
PRICE, G.D., Department of Geological Sciences, University
College London, Gower Street, London WClE 6BT, England
PUNIN Yu.O., Chair of Mineralogy and Petrology, St. Petersburg
University, St. Petersburg 199034, Russia
REED, S.J., Department of Earth Sciences, University of
Cambridge, Cambridge CB2 3EQ, England
REYNOLDS, R.C., Department of Earth Sciences, Dartmouth
College, Hanover, NH 03755, USA
ROMANENKO, I.M., Institute of Experimental Mineralogy,
Academy of Sciences, Chernogolovka 124432, Moscow Region,
Russia
ROSSMAN, G.R., Division of Geological and Planetary Sciences,
California Institute of Technology, Pasadena, CA 91125, USA
RUMBLE, D., Geophysical Laboratory, 5241 Broad Branch Road,
RYABEVA, E.G., Institute of Mineral Resources (VIMS),
Staromonetny 33, Moscow 109017. Russia
xx
RYAKHOVSKY, V.M., Aerogeology, Krzhyzhanovsky 5,

RYERSON, F.J., Lawrence Livermore National Laboratory,
University California, Livermore, CA 94550, USA
SAMOILOVICH, M.I., Institute of Synthesis of Minerals,
Alexandrov 601600, Russia
SCHOCK, R.N., Earth Science Department, Lawrence Livermore
National Laboratory, University of California, P.O. Box 808,
Livermore, CA 94550, USA
SEMENOV, E.I., Institute of Mineralogy, Geochemistry and Crystal
Chemistry of Rare Metals, Sadovnicheskaya 71,
SENDOVi\-VASSILIEVA, M. Faculty of Physics, Sofia University,
Sofia BG-1l26, Bulgaria
SHERMAN, D.M., Molecular Science Research Center, Pacific
Northwest Laboratory, K-195, P.O. Box 999, Richland,
W A 99352, USA
SHUKOLYUKOV, Ju.A., Vernadsky Institute of Geochemistry,
SIMONOV, V.I., Institute of Crystallography, Leninsky Prospect 59,
SMITH, D.G.W., Department of Geology, University of Alberta,
Edmonton, Alta, T6G 2E3, Canada
SOFFEL, H.C., Institute fUr Allgemeine und Angewandte
Geophysik, Theresienstrasse 41, D-80333 Munchen, Germany
SPAETH, I.M., Experimentalphysik, Universitat-Gesamthochschule
Paderborn, Warburgerstrasse l00A, D-33098 Paderborn,
Germany
SUTTER, J.F., US Geological Survey, Reston, Virginia 22092, USA
T ARASHCHAN, A.N., Institute of Geochemistry and Physics of
Minerals, Palladina 34, Kiev 252142, Ukraina
TITKOV, S.V., IGEM, Academy of Sciences, Staromonetny 35,
TROCELLIER, P., Laboratoire Pierre Sue, Direction des Sciences de
la Matiere, Departement de Physique General, CEA/CEN
Saclay, F-91191 Gif sur Yvette, France
TRUKHIN, V.I., Physical Faculty, Moscow University,
TSIRELSON, V.G., Mendeleev Institute of Chemical Technology,
Miusskaya Place 9, Moscow 125190, Russia
TURNER, S., Center for Analytical Chemistry, National Institute of
Standards and Technology, Gaitherburg, MD 20899, USA
URCH, D.S., Department of Chemistry, Queen Mary College,
Mile End Road, London El 4NS, England
XXI
URUSOV, V.S., Department of Crystallography, Geological Faculty,

Moscow University, Moscow 119899, Russia
VEBLEN, D.R., Department of Earth and Planetary Sciences,
John Hopkins University, Baltimore, MD 21218, USA
VINOGRADOV, V.I., Geological Institute, Academy of Sciences,
VIRGO, D., Geophysical Laboratory, 5251 Broad Branch Road,
Washington, DC 20015-1305, USA
VOTYAKOV, S.L., Institute of Geology and Geochemistry,
Pochtovy 7, Ekaterinburg 620644, Russia
WALKER, G., Department of Pure and Applied Physics, University
of Manchester, Institute of Science and Technology,
Manchester M60 lQD, England
W AYCHUNAS, G.A., Center for Materials Research,
351 McCullough Bldg, Stanford University, Stanford,
CA 94305, USA
WElL, J.A., Department of Chemistry, University of Saskatchewan,
Saskatoon, Saskatchewan S7N OWO, Canada
WENK, H.R., Department of Geology and Geophysics,
University of California, Berkeley, CA 94720, USA
WETZEL, K., Central Institute of Isotope and Radiation Research,
Permoserstrasse 15, D-04318 Leipzig, Germany
WHITE, W., Material Research Laboratory, Pennsylvania State
University, University Park, PA 16802, USA
WILLAIME Chr., Laboratoire de Mineralogie Physique,
CAESS-CNRS, Universite de Rennes I, F-35042 Rennes Cede x,
France
WOOLUM, D.S., Physics Department, California State University,
Fullerton, CA 92634, USA
XIAO JIN-KAI, Academia Sinica, Institute of Geochemistry,
Guiyang, Gizhou, China
Y AROSHEVSKY, A.A., Geological Faculty, Moscow University,
ZARKA, A., Laboratoire de Mineralogie-Cristallographie,
Universites Paris VI et VII, Tour 16, 4 Place Jussieu,
F-75252 Paris Cede x OS, France
ZOTOV, N.S., Institute of Applied Mineralogy, Bulgarian Academy
of Sciences, Rakovski Street 92, Sofia 1000, Bulgaria
ZUSSMANN, J., Department of Geology, The University of
Manchester, Oxford Road, Manchester M 13 9PL, England
ZVYAGIN, B.B., IGEM, Academy of Sciences, Staromonetny 35,
Introduction
Important progress has been made in numerous fields of mineralogy over the
last decades and even in the most recent years. The time has now come to
summarize these new results on structural crystallography.
After more than half a century of determination and precision refinement of
crystal structures (which still continues for new mineral species) scientists are
now facing new problems and purposes.
Based on the enormous amount of data on the atomic arrangement in
minerals various new insights in the structure of minerals have been achieved,
including
- a polyhedral vision of inorganic mineralogy;
- a symmetry approach to solids (based on the concepts of colored symmetry,
the symmetry of multidimensional space, and anti symmetry);
- computer models of crystal structures for structural drawings and projections,
bond lengths and angles;
- quantum mechanical interpretations of the empirical relation in structure
geometries;
- high-pressure and high-temperature crystal chemistry;
- computer simulation and prediction of crystal structure with special reference
to mineral phases in the Earth's mantle.
Two important systems are derived from these results: the crystallographic
classfication of minerals and the systematics of structural geometry existing in
minerals and crystalline matter. Sophisticated data bases for crystal structures
and powder diffraction patterns are now available.
This amount of data on crystal structures and solid-state spectroscopy
parameters has led to a breakthrough in studies of chemical bonds in minerals
and crystalline materials.
The quantum mechanical formalisms, computations and concepts introduced to mineralogy by the outstanding works of several groups of chemists and
mineralogists in the 1980s have transformed the mostly qualitative patterns of
chemical bonding in minerals into calculations of their characteristics. Numerous methods of calculation have been brought together and presented in a
systematic way, composing a system of contemporary approaches to chemical
bonding, including first-principle approximations ("molecules as models of
XXIV
Introduction
bonding" or "molecular mimicry"), ab initio Hartree-Fock computations, band

theory and ionic lattice simulations.
These formalized descriptions, the energy levels and bands, their populations, quantum mechanical characteristics and spectroscopic parameters build a
framework for the fundamental understanding of the inorganic mineral world as
well as a base for nonempirical interpretations of bond length and bond angle
variations, solid state spectra, properties of solids as applied in material science
and technology, properties of minerals found in the Earth's interior, kinetic
mechanisms, equations of state, and electron and oscillation spectroscopy.
Multilateral manifestations of the real structure of minerals have been
revealed as a result of several new approaches:
- direct imaging of point defects by high-resolution transmission electron
microscopy;
- X-ray topography of dislocations;
- electron paramagnetic resonance of radiation electron-hole centers as a unique
method to describe in detail the models of the point defects as precursors of the
centers;
- quantum mechanical calculations for defect structures;
- studies of the role of point defects in mechanisms of diffusion, electrical
conductivity, and plastic deformation in relation to processes in the Earth's
interior;
- effects of point defects on semicondution and quantum electronics used in
material science and technology;
- several structural types of nonstoichiometry in minerals.
Vast and new developments in surface science over the last decade stimulated studies of mineral surfaces: e.g. STM, ESCA, LEED, among other methods, theoretical calculations of surface electronic structure and properties,
electron spectroscopy for surface analysis, consequences of the role of surfaces in
catalysis, chemisorption, solubility, sorption reactions at the aqueous solutionmineral interfaces.
Two different fields revolutionized the concept of mineral properties:
1. Mineral Physics. The necessity of using the most elaborate theoretical
approaches and experimental studies under extreme pressure and temperature
conditions, corresponding to the Earth's mantle and the Earth's core, attaches a
new quality to the understanding of mineral properties in general and to studies
of elastic and anelastic properties, inelastic deformation and solid mantle flows,
transport processes and point defects, thermal and electrical conductivity,
diffusivity, creep deformation, mineral magnetism, phase transformation, the
nature and movement of melts, high-pressure crystal chemistry and computer
simulations of crystal structures.
These theoretical and experimental data of mineral physics present an
objective basis and constraints for all geophysical interpretations and for
understanding the solid Earth and planets.
Introduction
xxv
2. Mineralogical Material Science. Further enhancement and enrichment of the

concept of mineral properties can be linked with studies and uses of natural
minerals and their synthetic analogues as modern components of various
techniques, especially semiconduction and quantum electronics. The use of
minerals in most complicated electronic devices reveals new and sophisticated
understanding of the properties of solids.
Some minerals are used for nonlinear optics, acoustics, radiation dosimetry,
semiconduction, superionic conduction, piezoelectricity, quantum electronics,
heat sinkers, etc.; others are multifunctional minerals, e.g. diamond, quartz,
ruby, zeolite, etc.
New diamond investigations have revealed for the first time that their
properties are extraordinary regarding not only the maximum value of hardness, but functionally related characteristics of elastic, heat, and electrical
parameters, including light velocity or absolute zero of temperature. Diamond is
the ultimate mineral.
Zeolites can be regarded as the minerals of the century because of their
unique applications in ecology, radioactivity, oil production, and agriculture.
With regard to a sophisticated, modern approach to solids, more detailed
studies of minerals are required. Hence, some special studies focus on geological
and planetary materials or on materials from the Earth's interior.
Using all the complex data obtained by modern methods and theories shows
that the study of numerous minerals may contribute to the understanding of
processes going on in the Earth, in Space and in crystalline matter. This can be
demonstrated by listing, for instance, the current topics of interest in studies of
olivine:
1. Dislocation mechanisms, TEM investigation of dislocation substructure
density, configuration in experimentally and naturally deformed olivines and
their relationship to solid-state flow and creep in the upper mantle and to the
velocity of plate movements.
2. High-pressure and high-temperature investigations of olivines up to the
melting point and pressures corresponding to depths of 100 km; in situ
observation of the olivine-spinel transition using laser heating and synchrotron
radiation; computer simulation of olivine structure for mantle parameters;
equation of state at high P and T; interpretations from interaction of interatomic
forces, electron density distribution; point defects; changes in ion sizes and
compressibility; bond calculations by CNDO/MO and ab initio methods;
nonhydrostatic thermodynamics, mechanism and kinetics of the olivine-spinel
transition and its implications for deep-focus earthquake genesis and consequences on the dynamics of the subsiding lithosphere; transformations to
perovskite-bearing assemblages at ultra-high pressures of the lower mantle and
to the major seismic discontinuity at 670 km which defines the boundary
between the transition zone and the lower mantle.
3. Determinations of the Ni, Co, Cr impurities (EPR, ENDOR of Cr 3 + in
forsterite); incompatibles Na, K, P, Ti; ion microprobe determination of U, rare
XXVI
Introduction
earth elements; distribution coefficient of impurities between olivine and melts,

olivine and sulphides; Mossbauer measurements of intracrystalline distribution
and order-disorder; enrichment by Ca; possibility of carbon solid solutions in
olivine at high pressures.
4. Color, optical absorption and chromatic coordinates for olivines of different
origin.
5. Dating of xenocrysts and phenocrysts by K-Ar, 87Sr_86Sr, excess of 129Xe,
relation of 3He-4He in connection with crustal spreading; diffusion coefficient
calculations and growth of olivine in magma; theoretical morphology, formation of large crystals of olivine in komatiite; CO 2 inclusions in olivines;
geothermometry by coexistence with olivine minerals.
6. Registration of traces (channels and "capillarity") of heavy cosmic nuclei;
observation of fission tracks from iron group element nuclei from cosmic rays.
7. Determination of cooling rate, physicochemical fractionation, pre-solar
matter accumulation, radiogenic ages.
Important for various fields in geosciences and in several cases for material
science are studies of garnets, enstatite, perovskite, zeolites, sodalite, clay
minerals, zircon, quartz, corrundum, uraninite, wiistite, manganese oxides,
spinels-chromites-magnetites, hematites, apatites, diamonds, fluorites, pyrrhotites, etc. The data of several groups of minerals (pyroxenes, amphiboles, mica,
serpentine) and even classes of minerals (native elements, sulphosalts, borates,
phosphate) have been considerably revised.
The number of known mineral species has increased twofold over the last
three decades: In the future research will focus on the question which role each
of the ca. 3500 minerals are playing in the geological evolution and in the
formation of minerals resources.
Radiation mineralogy has emerged as a special field of science, resulting
from the important impact radiation has on any crystalline matter.
Like temperature or chemical composition radiation is an intrinsic characteristic of Nature. The natural, generally weak radiation influences the structure
of minerals (with point defects as precursors of radiation centers) and leads over
geological time scales to the formation and broad distribution of radiation
electron-hole centers in minerals, thus influencing the general properties of
geological materials.
Artificially created, radiation can be very strong. Here, the boundary is
crossed from the harmonic existence of weak, natural radiation to high concentrations of radioactivity in more than 400 nuclear power reactions. Moreover,
even if the fabrication and processsing of uranium-plutonium fuel were stopped
now, the disposal of radioactive wastes and the conservation of disused atomic
electric power stations would still represent the sword of Damocles for a very
long period of time. Hence, mineralogists and geologists are asked to perform
long-term studies on the influence radioactivity has on both artificial (glass) or
natural (clay, salt) barriers for radioactive waste.
For the first time in the history of the Earth the largest ore deposits, ore
regions and oil and gas provinces have been nearly discovered. Thus, the
Introduction
XXVII
available sources for metals, energy and solid matter are fairly well known. As a
consequence, technological mineralogy (so called process mineralogy) has to
seek new ways to improve their effectiveness. These include: a concentration on
low-grade, difficult to process ores from giant mineral deposits; mineralogicaltechnological mapping; purposive induced changes in mineral properties for ore
separation and processing; complex and less waste producing ore and metal
production; enormous accumulations of billions of tons of anthropogenic waste
still containing unextracted metals, suitable for conversion into industrial and
other materials.
The biggest industrial enterprises are involved with the extraction, processing and consumption of mineral resources. However, they are also, at all
stages of their activity, the main cause of ecological disasters. Mineralogical and
geochemical aspects compose an essential part of environmental studies.
The most striking changes in several branches of the mineral industry over
the last decades are related to studies of mineral matter, including the mineralogy of gold, mineralogy of platinum group metals, mineralogy of uranium, rare
metals and rare earth minerals, mineralogy of diamond, mineralogy of phosphates, borates, nonmetallic resources etc. These results represent extremely
important aspects of mineralogical studies.
There are now more than 100 known varieties of natural minerals occurring
in gem-quality crystals. Jewelry can be regarded as an aesthetic aspect of
mineralogy. On the other hand, physico-mineralogical methods and theories
present scientific bases for the identification, synthesis, improvement, and the
technology of grading and faceting of precious stones.
The aesthetic properties of gems in combination with their physical properties can find impartial expression through measured spectroscopic parameters
and details of their chemical composition. The development of synthetic analogues resembling natural minerals in detail and the increasing number of
shrewd methods of identification of natural, synthetic, treated stones and
imitations give rise to the speculation whether precious stones will remain
precious.
The breakthroughs regarding the mineral composition of the mantle, moon,
and ocean floor, and the earliest stages of the earth's evolution as well as the
advancements in the measurement and analysis of mineral matter have contributed to the creation of modern geology. The two final aims of geology are: the
understanding of the global evolution of the Earth and its units, and the global
mineral and energetic potential of the planet.
CHAPTER 1
The Chemical Nature of Minerals
Chapter 1. The Chemical Nature of Minerals
1.1 Chemical Composition of Minerals, Crystallochemical

Constraints and the Nature of Impurities
R.H. MITCHELL, M.1. NOVGORODOVA, and E.1. SEMENOV
Minerals are defined as any naturally occurring crystalline substance. While over
1 million compounds have been synthesized in the laboratory, only about 3500
minerals have been recognized. Geochemical factors, e.g. element abundance,
solid solution limits, mineral stability, place a limit on the composition and
stability of naturally occurring compounds, hence, the relatively small. number of
minerals. Minerals and synthetic compounds may have identical structures.
However, they differ in that minerals are rarely pure substances and typically
show wide compositional variations. Minerals range in terms of their composition from pure elements (Fe,Au,Ag) through relatively simple compounds (PbSgalena, KCI - sylvite) to very complex compounds, e.g. steenstrupine Na14Ce6Mn2+Mn3+Fe~+(Zr,Th)(S018h(P04h 3H zO. Chemically simple
minerals (Si0 2 ) do not necessarily have simple structures, e.g., alpha quartz.
Minerals are usually named after scientists (kullerudite, gagarinite, ringwoodite)
or the place of first recognition (isokaite, bytownite, atacamite). This practice
leads to the introduction of names that provide no information concerning the
composition or structure of the mineral.
Chemical classifications of minerals are based on the predominant anion
or anionic group. The following classes are recognized: (1) native elements;
(2) sulphide, telluride, arsenide and selenide minerals including sulphosalts of
antimony and bismuth; (3) halides; (4) oxides; (5) hydroxides; (6) carbonates; (7)
nitrates; (8) borates; (9) chromates; (10) tungstates; (11) molybdates; (12) phosphates; (13) arsenates; (14) vanadates; (15) silicates and aluminosilicates. Because
of the dominance of oxygen, silicon and aluminum in the earth, silicates and
aluminosilicates are quantitatively the most important class of minerals. Minerals of mixed anion composition, e.g. F in topaz or apatite, S in helvite-danalite,
OH in phyllosilicates, CI in rasvumite, are usually classified according to the
nature of the dominant anion. Hybrid minerals, such as valleriite and tochilinite,
which are sulphides containing layers of hydroxides, are not common.
Each major compositional class of minerals is subdivided into groups of
minerals having similar crystal structures. Thus, the silicate and alumino silicate
class comprises orthosilicates, sorosilicates, inosilicates, phyllosilicates and
tectosilicates. Each of these divisions is further subdivided into mineral groups of
different structure, e.g. the cyclosilicates into, among others, the beryl, tourmaline and axinite groups.
The divisions arise because atoms of similar size and bonding character
adopt similar structures with a particular anion or anionic group. Hence,
minerals of very different composition possess the same crystal structure.
Structurally identical, but compositionally dissimilar, compounds are referred to
as isomorphs. Isomorphic compounds typically exhibit extensive solid solution
1.1 Chemical Composition of Minerals
between pure compounds, termed end member components or molecules. Solid

solution refers to the ability of cations of similar size and charge to substitute for
one another at lattice sites in a particular crystal structure. Thus, the olivine
group of the silicate class has the structural formula M 2Si0 4 (where
M = Mg,Fe,Mn,Ni) and consists of a family of isomorphs, i.e., forsterite (Mg),
fayalite (Fe), tephroite (Mn), liebenbergite (Ni). Naturally occurring olivines do
not correspond in composition to pure end member components and have the
composition (Ni,Mn,Fe,Mg)2Si04. In such formulae, cations are listed in order
of increasing atomic abundance. Individual olivines are named on the basis of
the dominant cation.
Similar principles are applicable to other mineral classes, thus the sulphate
class contains the barite group AS0 4, where A = Ba,Pb,Sr, and the structurally
dissimilar rozenite group AS0 44H 20. Typically, solid solution is extensive
within a mineral group, but limited between groups having different structures,
even though they may be based upon similar cations. Thus, solid solution
between orthosilicate olivines (Mg,FehSi0 4 and inosilicate pyroxenes
(Mg,Fe)Si0 3 does not occur.
In dominantly ionic minerals, cation substitution may be simple homo valent
between cations of similar size and charge (Table 1) or heterovalent between
several cations of dissimilar charge and size (Tables 2, 3). Substitutions of the
latter variety are termed coupled substitutions. The principal requirement of this
type of substitution is that the electrical neutrality of the crystal structure be
maintained. Cation substitutions which would disrupt the structure with respect
to charge or size are not permitted. Thus, K cannot substitute for Mg at lattice
sites in an olivine and there are no K-olivines.
Table 1. Homovalent substitutions in minerals
M1+
Lithiophosphate
Zirsinali te
Albite
Analcite
Teepleite
Jarosite
Li
[N'
Na
Na
Na
Na
Na
H
K
Cs
Cu
Ag
Lovoserite
Microc1ine
Pollucite
Bandylite
Lepidolite
Avogadrite
Murunskite
Alum
[i
Rb
Cs
Tl
NH4
Astrophyllite
[Rb
Rb
Cs
Tl
Galkhaite
Cs
Tl
Marshite
Copper
[cu
Cu
Ag
Au
Myersite
Gold
Silver
Rayite
[Ag
Ag
Au
Tl
Gold
Tha1cusite
Tschermigite
Pollucite
Table 1. (Continued)
M 2 -'
Phenakit.e
Musgravite
~Be
Be
Zn
Mg
Willemite
Taalfeite
Magnesite
Chondrodite
Forsterite
Bobierrit.e
Bobierrite
Hoernesite
Mg
Mg
Mg
Mg
Mg
Mg
Ca
Mn
Fe
Co
Ni
Zn
Calcite
Alleghanyite
Fayalite
Erythrite
Annabergite
Koettigite
Aragonite
Calcite
Ca
Ca
Sr
Ba
Strontianite
Benstonite
Pectolite
Wollastonite
Calcite
Apatite
Ca
Ca
Ca
Ca
Mn
Fe
Cd
Pb
Serandite
Bustamite
Otavite
Pyromorphite
[sr
Sr
Ba
Eu
Witherite
Ba
Ra
Ilmenite
Mn
Mn
Mn
[M"
Fe
Co
Ni
Zn
Ilmenite
Aplowite
Morenosite
Genthelvite
Fe
Fe
Co
Ni
Gaspeite
Iron
Siderotil
[Fe
Fe
Pt
Cu
Platinum
Chalcantite
Erythrite
Devillite
Co
Cu
Ni
Zn
Annabergite
Ktenasite
Zn
Zn
lZ"
Cd
Hg
Fe
Otavite
Metacinnabar
Siderite
Cd
Sn
Hg
Pb
Saukovite
Teallite
Al
Al
Al
Al
Al
Al
Al
Sc
Ti
V
Cr
Mn
Fe
Ga
Eggonite
Sc
Y
Y
Ce
Y
Ln(Yb)
(Ce)
Bi
La
Strontianite
Strontianite
Barite
Pyrophanite
Ilesite
Fauserite
Helvite
Siderite
Siderite
Smithsonite
Sphalerite
Smithsonite
Hawleyit.e
Herzenbergite
M3 Variscite
Hibonite
Corundum
Spinel
Andalusite
Zoisite
Tugtupite
Thortveitite
Thortveitite
Abukumalite
Gadolinite
Monazite
Karelianite
Chromite
Kanonaite
Epidote
Keivyite
Britholite
Minasgeraisite
Table l. (Continued)
Gadolinite
Monazite
[La
Ln
Lu
Ac
Sohngeite
Karelianite
Karelianite
Ga
In
Cr
Fe
Brownite
[~
Escolaite
Hematite
Fe
GMn
Mn
TI
Avicennite
Rh
Ga
As
Sb
Ir
In
Sb
Bi
Kashinite
lalindite
Senarmontite
Bismuthinite
[Si
Si
Ti
Ge
Rutile
Argutite
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Argutite
Zircophyllite
Malayaite
Paramontroseite
Pyrolusite
Ti
Ge
Zr
Sn
V
Mn
Re
Pt
Pb
Te
[:Ge
Ge
Ge
Sn
Pb
Mn
Cassiterite
Plattnerite
Oespujolsite
Zr
Zr
Zr
Hf
Th
U
Sn
Hafnon
Thorite
Coffinite
Sn
Pb
Plattnerite
Hafnon
Hafnon
[Hf
Hf
Th
U
Thorite
Coffinite
Cerianite
[ce
Ce
Th
U
Thorianite
Uraninite
Th
S
Se
Mo
U
Se
Te
Uraninite
Molybdomenite
Teineite
V
As
Vanadinite
Mimetite
V
Sb
Nb
As
As
Mimetite
~b
Nb
Sb
Ta
Romeite
Microlite
Boweite
Sohngeite
Arsenolite
Stibnite
M4 +
Stishovite
Stishovite
Rutile
Astrophyllite
Titanite
Rutile
Rutile
Senaite
Ulvite
Rutile
Rutile
Argutite
Argutite
Schaurteite
Zircon
Terskite
Cassiterite
Thorianite
Scotlandite
Chalcomenite
Tugarinovite
Ti
['
-
~~~
Plattnerite
Paratellurite
M5 +
Pyromorphite
Pyromorphite
Rhabdophanite
Vanadinite
Stibiconite
Pyrochlore
Pyrochlore
M6 +
Arcanite
Anglesite
Olascherite
Fornacite
Powellite
Powellite
[~
Cr
Se
Se
Cr
Te
Mo
[MO
Mo
W
U
[f
CI
OH
Br
I
Tarapakaite
Olsacherite
Scheelite
X1-
Apatite
Apatite
Chlorargyrite
Nantokite
Bromargyrite
[9
CI
Br
Bromargyrite
Marshite
Iodargyrite
X2 -
Cancrinite
Galena
Galena
Clausthalite
Bystrite
[~
Se
Te
Clausthalite
Altaite
Te
Altaite
Se
In covalent minerals, elements which have similar bonding characteristics

may replace each other either at cation or anion sites (Table 1). Thus, the pyrite
group contains the isomorphs pyrite (FeS 2 ), cattierite (CoS 2 ) and vaesite (NiS 2 ).
There is continuous solid solution between PbS (galena) and PbSe (dausthalite)
or vaesite (NiS 2 ) and melonite (NiTe 2 ). Elements of unlike bonding character will
not form extensive solid solutions, e.g. ZnS (sphalerite) and pyrite (FeS 2 ).
The compositions of minerals are expressed in terms of major ( > 1 wt%);
minor (0.1-1.0wt%); or trace 0.1 wt% or < 1000 ppm or < lOOOj.tg/g)
element abundances. Major elements are those cations and anions which determine the crystal structure of the mineral. All major and most minor element
cations in compositionally complex minerals are present at lattice sites. Analysis
of any mineral will reveal the presence of a significant number of trace elements
whose abundance may range from the ppm (j.tg/g) to the ppb (ng/g) level. Some of
these trace elements may be present at lattice sites, but a substantial proportion
may be located elsewhere (see below) and are regarded as impurities.
Deviations from the rules which govern solid solution in crustal minerals
occur only in high-pressure environments such as are found in the deeper parts
( > 150 km) of the Earth's mantle. An example is the substitution ofK ( + AI) in
a coupled substitution for Ca in pyroxenes. Typically, in this environment, a
different assemblage of minerals is stable. These may represent high-pressure
polymorphs of compositions stable at low pressure (e.g. coesite instead of
quartz), or may be new phases stable only at high pressure, e.g. yimengite.
The composition of the Earth's crust is dominated by eight major elements:
0, Si, AI, Fe, Mg, Ca, Na, K and four minor elements: Ti, Mn, P, H. All other
Table 2. Heterovalent substitutions in minerals

1.
Lil +Ba2+
Mg2+Kl+
2.
Li 1+AI3+
Be 2+Be 2+
Beryl
[NaAI
NaAI
MgMg
CaMg
Neighborite
Diopside
NaFe
NaCe
KFe
AgBi
Agln
TlBi
CaFe
CaCa
PbCu
PbPb
PbPb
PbPb
Hedenbergite
Perovskite
Beaverite
Galena
Galena
Galena
Lil +Si 4 +
LiZr
Mg2+ AI3+
FeFe
Phlogopite
Tuhualite
aSi
NaSi
CaAI
SrAI
Anorthite
~NaTi
CaFe
Augite
NaTi
NaZr
KSi
SrFe
CaY
BaAl
Lamprophyllite
Donneyite
Hyalophane
Mg2+Ti 4 +
Taeniolite
Perovskite
Eudialyte
Cryolite
Jadeite
Aegirine
Loparite
Jarosite
Schapbachite
Potosite
Po to site
3. Taeniolite
Zektzerite
Albite
Chabazite
Weloganite
Orthoclase
Li1+Nb s +
4.
Lueshite
~NaNb
Phlogopite
NaNb
NaP
NaAs
KNb
CaTi
CaZr
CaSi
CaSi
BaTi
Li1+Nb s +
AI3+ AI3+
Polylithionite
NaS
KS
Ca 2+ps+
CaAs
SrP
Apatite
Tirolite
Svanbergite
7.
Nat +W 6 +
Ce 3 +Ti 4 +
Marignacite
8. Gadolinite
Be2+y3+
MnY
FeY
FeCe
FeSb
Ca 2+C 4 +
BeSi
B3 +Ca 2+
AICa
FeCa
AICa
AICa
Datolite
Grossular
Steenstrupite
Berzeliite
5.
6.
Cesanite
Alunite
Chevkinite
Allanite
9.
Vaterite
Tugtupite
Melilite
Enstatite
Grossular
Brownite
Katoptrite
Pseudo brookite
Tadjikite
Perovskite
~Nal +S6+
Ce 3 +B 3 +
AlAI
~MgS;
AlAI
ScAI
CrAI
~caSi
CaSi
CaSi
CeB
YAI
MnMn
ZnSi
MgTi
AlAI
Fe Fe
caTi
GCaTi
YAI
CeFe
MgSi
MgSi
Labuntsovite
Epidote
Vesuvianite
Sodalite
Stilwellite
Bixbyite
Hellandite
Shorlomite
Schoenfliesite
Eudialyte
Cheralite
Kusuite
lO. Zirkelite
11.
Apatite
Pyrochlore
Columbite
Welshite
12. Gypsum
Svanbergite
Powellite
Wulfenite
S(:heelite
13.
14.
Aeschynite
Kimzeyite
15.
Melanocerite
FeTi
MgSn
CaZr
CaTh
PbPb
FeAI
Inln
CeY
CeCe
CeY
--
Ca2+Ti +
Th 4
Ca2+p5+
Ce3+Si 4 +
CeTi
FeTi
AITi
y3+p5+
CeP
-YNb
YV
YNb
U 4 +U 4 +
CaNb
FeNb
BeSb
Ca2+S6+
SrS
CaMo
PbMo
CaW
Pb2+U 6 +
Ce3+Ti 4 +
FeZr
B3+P5+
Andradite
Xenotime
+Fe2+
Britholite
Rhoenite
Churchite
Florensite
Uraninite
Th 4 +Fe3+
SiAl
Si 4 +Si 4 +
[YbP
CeP
--
ZrSi
ThSi
Zircon
Thorite
FeP
ThSi
Thorite
CeNb
CeNb
YNb
ZrTi
-ThTh
ThTi
UTi
Zirkelite
Thorite
BTa
FeTa
FeSb
SiZr
TiSn
TiTi
Zircon
16.
Fe3+W 6 +
Ti 4 +Ta5+
Samarskite
17.
Ti 4 +W 6 +
Nb5+Nb 5 +
Pyrochlore
Aeschynite
Behierite
Samarskite
Melanostibite
Brannerite
Cluster isomorphism
3Ti4 +
18.
Ilmenorutile
Fe2+Nb~+
19.
Florencite
Ce3+p~+
Kl+S~+
Jarosite
elements are present only in trace quantities. The mineralogy of the crust is
therefore dominated by minerals based upon these major and minor elements.
The composition of individual minerals reflects the local geochemical environment in which the mineral formed. Compositional ranges are restricted by the
possible simple and coupled substitutions permissible for a given crystal
structure. Elements which have low natural abundances will typically substitute
for major elements at lattice sites as trace components, e.g. Sr for Ca in diopside,
Pb for K in potassium feldspar, Re for Mo in molybdenite. This dispersion of
Table 3. Complex cation-anion substitutions

l.
Taeniolite
Mosandrite
Phlogopite
2.
Phlogopite
Fluorite
Astrophyllite
Matlockite
Dadsonite
3.
Mullite
Li1+FlNaF
KCl
Mg2+F 1 CaF
FeF
PbF
PbCl
Phlogopite
Gotzenite
Anandite
[AI3+ F lAlF
Mg2+02CaO
BaS
AI3+02YO
FeO
Bi
BiS
Si 4 +0 2TiO
TiO
Nb5+02-
Narsarsukite
W6 +0 2-
4.
Rinkite
FeF
Ti4 +F 1 -
5.
Pyrochlore
Nb5+F 1 -
Muscovite
Bismodite
Titanite
Cluster isomorphism
6.
7.
Clinohumite
Cuspidine
Mg2+F~-
Ti4+0~-
CaF2
Zr0 2
Lepidolite
AI3+F~ -
NbS+O~-
Baghdadite
trace elements within other minerals is the principal reason for the limited
number of naturally occurring minerals.
Trace elements in the earth's crust may be concentrated by geochemical
processes which cause them to reach, locally, major element status, e.g. the
minerals of ore deposits, evaporites, sublimates etc. The rare earth elements
(REE) exemplify these processes. In many common minerals REE may be found
dispersed throughout the crystal lattice where they typically replace Ca, Sr, Ba,
Zr or Th. Only in low-temperature hydrothermal/carbothermal environments
do they become sufficiently concentrated to form REE-based minerals. Although
the REE typically behave as a chemically coherent group, selective concentration of individual elements is possible, e.g. La in davidite, Ce in fluocerite, Gd in
samarskite.
Many elements are found in minerals which do not occur in structural lattice
sites yet are an integral part of the mineral. In these cases the mineral has a
relatively open structure and contains channels which accommodate large
cations. Two examples of this phenomenon are the presence oflarge cations (Cs)
located within the silicate rings of the cyclosilicates beryl and kupletskiite; and
the presence ofBa and K within the tunnels formed by chains of Ti0 6 octahedra
in the hollandite group of oxides. Further examples are found in the zeolite
group of tectosilicates. The open framework structure of these minerals permits
the entry of cations into the large spaces within the structure. Because the size of
the pore spaces is determined by the composition of the zeolite, individual
minerals exhibit selectivity as to the nature of interlattice cations. Thus,
mordenite, clinoptylolite and erionite may contain Cs, Rb, and Ba, whereas
zeolites with smaller pore spaces, such as analcime and natrolite, cannot
accommodate these elements.
10
In some minerals not all lattice sites are occupied by cations (or anions). Such
lattices are known as defect lattices and the vacant sites are represented by holes
which may act as electronic color centers. Minerals possessing defect lattices are
non-stoichiometric compounds. Common examples include wustite (Fe1-xO)
and pyrrhotite (Fe1-xS). In the structural formula, x represents the atomic
fraction of vacant lattice sites and typically ranges up to 0.2. Lattice vacancies are
also commonly developed in many minerals as a consequence of complex,
coupled substitutions, e.g. the substitution of one Ba atom for two K atoms in
phyllosilicates results in the creation of a lattice vacancy (Table 4).
Many of the elements reported in bulk analyses of minerals reflect the
presence of microinclusions of other phases. These elements are impurities and
not integral parts of the minerals. Microinclusions may be easily recognized by
electron microbeam and X-ray investigations of minerals. The inclusions may be
solid or fluid and originate during growth of a mineral from a liquid or in the
solid state. Such inclusions were never structurally or chemically part of the host
mineral. Important in this category are fluid inclusions representing samples of
the fluids from which the host mineral grew. The inclusion may consist of COz,
CH 4 , and H 2 0 in various combinations with dissolved salts (Na,K,CI,SO~-).
Physically, the inclusion may consist of supercritical fluid, fluid + liquid (brine)
or fluid + liquid + solid. In the latter, minerals differing in composition from the
host crystal are precipitated from the trapped fluids upon cooling, e.g. halite in
calcite host crystal.
Other microinclusions result from ex solution; in this case, solid solutions,
which are complete at high-temperature, breakdown upon the cooling of a
previously crystallized mineral. Physically, the exsolution process is manifested
by the formation of microinclusions of the ex solved phase in the host mineral.
Commonly, ex solution is confined to particular crystallographic planes of the
host. Examples include the ex solution of rutile (Ti0 2 ) from quartz (Si0 2 ); the
breakdown of continuous alkali feldspar solid solutions into albite and orthoclase; the ex solution of dolomite from calcite.
Some minerals contain occluded gases which may be trapped in structural
voids, or adsorbed onto crystal surfaces during growth of the host. For example,
the cyclosilicates beryl and cordierite commonly contain trapped argon. Natural
diamonds may contain substantial amounts of N (up to 0.5 wt%) together with
occluded He, Ar, Kr and Xe. The N commonly occurs in discrete aggregates
termed platelets. These may have formed by aggregation of substitutional
nitrogen atoms subsequent to the growth of the diamond. Occluded gases
(N 2 ,C0 2 ,CH 4 ) in graphite may form clathrate impurities in the interlayer spaces.
Other impurities in minerals arise from the adsorption or precipitation of
finely dispersed, commonly colloidal compounds, on crystal faces during growth.
This material may recrystallize into aggregates of microinclusions. Common
examples are the hydroxides of Fe and Mn included in the citrine and rose
varieties of hydrothermal quartz. Included material may be expelled from a
crystal during prolonged recrystallization, e.g. the expulsion of graphite from the
chiastolite variety of andalusite.

Table 4. Defect isomorphism
I.
~Be2+
Na l +Li1+
CsLi
Beryl
Beryl
Ca
Lca
HNa
KNa
Gismondine
Ekanite
Ba
Fe
Mg
Pb
KK
NaLi
KNa
KK
Labuntsovite
Zertzerite
Zippeite
Beaverite
Al
Al
Lil +Ba 2 +
NaBe
NaMg
Carpholite
Beryl
Hastingsite
TR
NaCa
Eudialyte
Wn
Mn
NaMn
LiMn
Eudialyte
Lithiophyllite
~e
Fe
KFe
NaFe
Astrophyllite
Hastingsite
~Bi
Bi
CuPb
AgPb
Aikinite
Benjaminite
HBa
HCa
loakinite
Churchite
Si
Si
Si
H 1 +B 3 +
LiAI
NaAI
KAI
Datolite
Virgilite
Heulandite
Heulandite
Ti
Zr
NaFe
NaFe
Titanite
Zektzerite
KCI
HY
Na l +Si 4 +
Ekanite
Zircon
Be
2.
[AI"
r
[~e
3.
4.
[Th
Th
p5+
5.
S6+
HI+ps+
Kemmlizite
6.
U6 +
H1 +U 4 +
Coffinite
7.
2AI3+
2Bi
2Y
2Fe
3Mg2+
3Pb
3Ca
3Fe
Sap phi rite

Galena
Fluorite
Spinel
8.
Ti 4 +
Sn
2Fe 2 +
2Pb
Ellenbergite
Franckeite
9.
3Th 4 +
4TR 3 +
Thorite
10.
2Si 4 +
2Ti
Latiumite
Pride rite
II.
Mn 4 +
Ti
12.
Ca2+
Ca2+ Aq+
BaFe 2
Ba 2 +Mn 2 +
MgMg
y2+F 1 -
Shallerite
Coronadite
Hoegbomite
Fluorite
11
12
Minerals rich in the radioactive elements U and Th are typically poorly

crystalline due to the destruction of their crystal structure by alpha particles
emitted from these elements. Alpha particle damage is also evident where
radioactive minerals, such as zircon and monazite, are included in other
minerals. Typically, aureoles of radiation damage are formed around the
inclusion. In micas these damaged regions are known as pleochroic haloes and
their size is proportional to the age of the host mineral. Radioactive decay
products, such as Pb, are partially retained with the parent mineral.
Ore deposits, which are assemblages of minerals, may be considered as being
either simple or complex. Simple ores are exploited principally for one to three
elements with other elements being obtained as by-products from the extraction
process. The latter are typically present in solid solution or as minor phases
included in the major ore-forming minerals. Examples include: Pb and Zn with
by-product Ag, Ga and In from galena-sphalerite ores; or Ni and Cu with byproduct Ir, Pd, Rh etc., from copper nickel sulphide ores. Complex ores contain
several multicomponent minerals. Their benefication is complex and they may
only be viable ore deposits if many elements can be simultaneously recovered. An
example is the Nb-Ta-Y- Th-Zr-REE mineralization associated with
an orogenic granites. World resources of particular elements depend upon the
type of ore deposit with which they are associated and whether or not it is
technologically, and economically, feasible to extract them.
New minerals are constantly being discovered. The rate of discovery has
increased in the past decade due to technological advances such as the coupling
of scanning electron microscopy with energy dispersive X-ray spectrometry.
Commonly, many new minerals are represented only by micron-sized grains
which previously would not have been observed by simple petrographic or X-ray
methods. Despite these advances the nomenclature of minerals has not been
rationalized and new names perpetuate the traditional schemes. Advances in
analytical techniques have substantially increased the number of analyses of
minerals. The exponentially increasing amount of compositional data has not
yet been incorporated into data bases and unfortunately remains either unpublished or widely scattered in the scientific literature. Compilation of data bases
for specific mineral groups in a universally applicable, computerized format
should be undertaken as soon as possible.
1.2 Treatment of Chemical Composition Data for Minerals

A.G. BULAKH and J. ZUSSMAN
Structure-chemical formulae not only show the relative proportions of the
various atoms in the composition of a mineral but also give information
13
concerning its crystal structure. Many systems of notation have been devised,
giving greater or lesser structural detail, including those by Hey (1950), Povarennykh (1972), Strunz (1982), and more recently Lima-de-Faria et al. (1990), the
latter being recommended by a subcommittee of the International Union of
Crystallography. The notation recommended would give for example, for pyrite:
Fe[601{g} [SP;llt], indicating Fe in sixfold octahedral coordination by sulfur
and S tetrahedrally coordinated by 3 Fe and 1S, and for Mg, Al spinel:
[Mg[4tlAI2[60104[1,3;12C01], indicating Mg in fourfold tetrahedral and Al in
with one Mg and 3AI neighbors and selfsixfold octahedral coordination,
coordinated by a cubo-octahedron of oxygens. Lima-de-Faria et al. also give
the so-called Bauverband description indicating structure types by a latticecomplex notation.
The full notation gives information about structural units (chains, ~ layers, ~
etc.) and the packing of structural units, as well as the coordination of atoms and
the presence of interstitial atoms. Use ofthe full notation is suitable for relatively
simple inorganic compounds, but is impractical for many minerals which have
complex chemistry and structure, and for these a system like that of Strunz
(1982), giving less complete structural information, is more appropriate. Thus
alternatives for the formula for muscovite would be:
K 6+ 6{:}[ A1 2[6 Ol{:}(AISi3)[4t][1;310s }(OH)2

K[61 AI~~ [Al'Si~010](OH)2
K AI2 [(OH}z IAISi 30 10]'
For silicates, Deer et al. (1962) gave greater prominence to the scheme of
(Si,Al)-O tetrahedral linkage as, for example: tremolite Ca 2Mg s[Si s0 22 ] (OH)z,
muscovite KAI 2[AISi 30 lO ] (OH)z, emphasizing in parentheses the characteristic
(Si,AI):O ratio for the double chain and sheet-like structure respectively.
When solid solution occurs, e.g., Mg and Fe distributed over similar sites in
the structure of olivine, this is denoted by the use of parentheses and commas
thus, for example (Mg1.S1FeO.19}z.00Si04, or (Mg,Fe}zSi0 4 if the proportions of
Mg and Fe are unknown. If there are distinguishable sites, subscripts are used
to indicate the proportions of atoms in each site, e.g., (MgO.S6Feo.14)
(Feo.6sMgo.32)Si206' showing the contents of the Ml and M2 sites in an
orthopyroxene.
In many minerals a particular structural site may be filled, partially filled, or
empty, as, for example, in the calcic amphiboles, where we may have for an
edenite NaCa zMg s[Si 7AI0 22 ](OH)z or for another edenite Do.zNao.sCazMg5
[Si7.2Alo.s022](OH)z, with the vacancies indicated D, or for tremolite
CazMg s [Si s0 22 ](OH)z when the vacancy is usually not depicted. Other
examples involving vacancies are those sometimes called solid solutions
of the "second" type, or omission solid solutions, e.g., cryptomelanes
Ro _ z(Mn2+,Mn3+MO,OH)16' ferric molybdenites MOS2-Mol-xDxFexSz,
pyrrhotites Fe 1-x D xS, and "stuffed derivatives" of silica R~ + [Si 1- xR; +Oz]
(x = 0, tridymite; x = 1/2 nepheline).
14
Chapter l. The Chemical Nature of Minerals
Nonstoichiometric chemical formulae can result from mixed-layer structures, e.g., montmorillonite/mica with different proportions of the two components. Similar nonstoichiometry can occur, for example, in manganese oxides and
hydroxides with mixed-tunnel structures.
Nonstoichiometric chemical composition can also occur for minerals with
"recombinations structures" (a term recommended by the nomenclature commission of the International Union of Crystallography). These structures are
formed when topologically simple parent structures are periodically divided into
blocks, rods or slabs, which in turn are recombined into derivative structures by
means of one or more structure-building operations (unit-cell twinning, crystallographic shear planes, intergrowth of blocks, periodic out-of-phase or antiphase
boundaries, rotation of rods and blocks, vernier principle). Some further
examples of nonstoichiometry are: the homologous series galena PbS-lillianite
Pb 3Bi 2S6 (through compounds Pb n_ 1Bi 2Sn+ 2), homologous series of sulfosalts,
and biopyriboles, e.g., Mg 3n + 1Si4n010n+ 2(OH}zn- 2. The latter are in effect chain
silicates with chain-width variations; pyroxene, n = 1; amphibole n = 2, etc.).
Minals. It is often useful in the case of solid solutions to express the composition
as percentages of end-member "molecules" sometimes called minals since the
structures do not really contain molecules. Thus, as examples, an olivine
Mgo.64Fe1.36Si04 may be expressed as Mg 2Si0 4 (forsterite) 32%, Fe 2Si0 4
(fayalite) 68% or F0 32 Fa 6S ' a sphalerite (Zno.slFeo.10Mno.09)S may be plotted
on a triangular diagram as 81 % ZnS, 10% FeS and 9% MnS, and a garnet
Ca3(Alo.s6Feo.lOCro.o4}z(Si04h as grossular 86%, andradite 10%, uvarovite
4%.
Calculation of Mineral Formulae
The classical methods of gravimetric chemical analysis involved converting each

constituent element to its oxide and presenting each as a percentage of the total.
Even when nongravimetric methods are used (e.g., atomic absorption, electron
probe), it has remained conventional to express the results in terms of oxide
percentages. When the cell volume and density are both known with sufficient
accuracy, the mineral formula can be calculated directly as follows: if there is P
wt. % of an oxide RmOn the number of R atoms per formula unit is given by
NR
0.6023. d. Vo. P. m
=-------
Z. S. M.
where Vo = unit cell volume (A 3), d = mineral density (g/cm 3), Z = no. of
formula units in the unit cell. S = total of oxide percentages, M = mol. wt. of
RmOn
If an analysis is presented as weight percentages of atoms R instead of oxides
(e.g., for sulfides), m/M in the above formula is replaced by I/A, where
A = atomic wt. of R.
15
The direct method can be used for partial as well as full analyses, and the
errors and assumptions involved have been discussed, e.g., by Hey (1939, 1954),
Nicholls and Zussman (1954), Bulakh (1969, 1970, 1984), and Dollase and
Newman (1984).
When the cell volume and density are not known, the chemical analysis still
provides the relative proportions of the various atoms, and these can be
converted to absolute numbers of atoms in a formula in relation to an assumed
number for anyone of them, usually an anion (most commonly oxygen) or an
anion group, most commonly E"(O,OH,F,Cl), or a cation group, e.g., E"R
octahedral; the number assumed has to be based on sound crystal-chemical
principles.
Thus, it would be unwise to use cation groups that include sites that may
have vacancies, e.g., the A sites of amphiboles, or the octahedral sites in micas,
which may be intermediate between di- and tri-octahedral in character. In
practice, scaling of atom proportions should be to as large a number of ions as
can be assumed with confidence, e.g., E" (oxygen, etc.), or E" (all cations), since
scaling to small groups will propagate greater errors.
When normalizing to a number of cations N c , the number of R atoms NR is
given by NR/Nc = PR/Pc . P R and Pc are the atomic proportions of Rand C
respectively.
When normalizing to total oxygen (N EO ) the required expression is
NR/N"o = PR/P"o'
The methods of calculation are best illustrated by examples as in Table 5, a
sphalerite, Table 6, an ilmenite, and Table 7, a clinohumite.
The third example (Table 7) is instructive as to the method of dealing with a
mineral that contains structural (OH), wholly or partially replaced by (F, CI). In
Table 7 it is seen that the wt. % of the oxygen equivalent of F present must be
subtracted in column 1 (2.74 x 16/38 = 1.15) and the atomic equivalent of F
present subtracted in column 3.
In many published analyses values for H 2 0 + and for F are lacking or may
be suspect. In Table 7, for example, H 2 0 and F can be ignored and anion
Table 5. Sphalerite. (Berry et al. 1983)
Weight
Atomic
weight
Atomic
proportions
Fe
Mn
Cd
Zn
S
18.25
2.66
0.28
44.67
33.57
55.85
54.94
112.41
65.38
32.07
0.327
0.048
0.002
0.683
1.047
Total
99.43
L(Fe
+ Mn + Cd + Zn) =
1.060
a) To make L Fe, etc. = 1, multiply all by 1/1.060, i.e., 0.9434

b) To make S = 1, multiply all by 1/1.047, i.e., 0.9551
Formula a) (Zn O.61 Fe o.31 Mn O. 1s lt.ooSO.99
Forumla b) (Zno.6sFeo.31 MnO.Oslt.o1 S1.00
16
Table 6. Ilmenite (formula on the basis of three oxygens)

Weight
%
Ti0 2
MgO
FeO
MnO
H2O
53.80
2.72
38.70
4.77
0.13
Molecular
weight
79.90
40.32
71.85
70.93
Atomic proportions
Molecular
proportions
0.6733
0.0675
0.5386
0.0672
Numbers
of cations
Cations
Anions
Oxygen
atoms
0.6733
0.0675
0.5386
0.0672
1.3466
0.0675
0.5386
0.0672
2.000
0.100
0.800
0.100
1.000
0.100
0.800
0.100
2:0
= 2.0199 3.000
100.12
To make 2:0 = 3 mUltiply by 3/2.0199, i.e., by 1.4852
Formula: Feo.soMgo.lOMno.lOTi03.oo
Table 7. Clinohumite analysis. (Deer et al. 1992)

Wt.% of
oxides
Mol. prop.
of oxides
Atom. props.
of oxygen
from each
mol.
No. of ions
in formula
No. of anions
on basis of 18
(0, OH, F),
i.e., col. (3) x
6.3943
Si0 2
Ti0 2
Al I 0 3
36.53
0.26
0.22
0.6080
0.0033
0.0022
1.2160
0.0066
0.0066
7.775
0.042
0.042
Si
Ti
Al
3.888}
0.021 3.94
0.028
Fe 2 0 3
FeO
MnO
MgO
0.56
5.04
0.34
54.16
0.0035
0.0701
0.0048
1.3439
0.Q105
0.0701
0.0048
1.3439
0.067
0.448
0.031
8.593
Fe+ 3
Fe+ 2
Mn
Mg
n~5}
H 2 O+
H 2 OF
1.52
0.04
2.74
0.0844
0.0844
0.540
OH
0.1442
0.1442
0.922
1.080}
2.00
0.922
101.41
-O=F
Total
0.448
0.031
8.593
912
.
2.8871
1.15
- 0.0721 (
100.26
=! xO.1442)
2.8150
18
--= 6.3943
2.8150
proportions can be scaled, making the total 0 atom proportions equal 17, i.e.,
18-1- (OH,F,CI). [This procedure makes the assumption of 2(OH,F,CI) and is
also equivalent to re-calculating cations to balance 34 negative charges.] The
result in Table 7 is: l: 0 props. = 2.6577, giving 17/2.6577 = 6.3965 as the
scaling factor, which in this case is very close to the 6.3961 previously used, and
almost identical cation numbers will result.
17
For an amphibole, the formula involving (Si,AI)s022(OH,F)2 would be

derived normally on the basis of 24(0, OH, F) but if(OH,F) is uncertain, the basis
would be 23(0). This procedure would not, however, be safe for an oxidized
amphibole, in which some OH is replaced by 0; the correct basis would then be
between 23 and 24(0).
Electron probe analyses do not differentiate between Fe 2+ and Fe 3 + and the
total iron present is usually given as an Fe 2+ equivalent. Various ways of gaining
an approximate estimate of Fe 3 + and Fez + have been suggested, e.g., Robinson
et al. (1982), and are reviewed by Droop (1987). Some assign Fe so that trivalent
ions in octahedral balance Al in tetrahedral sites. Some methods distribute iron
between Fe z0 3 and FeO so as to give the ideal total for all cations, or for a
particular cation group. Here again, difficulties can occur where cation totals are
uncertain, through vacancies or unanalyzed elements, and also in cases where
there is more than one element with variable oxidation state (e.g., Fe
and Mn).
Many computer programs have been designed for the calculation of mineral
formulae and minal percentages from analyses (see for example, Rock and Carroll
1990).
References
Bulakh AG (1969) Calculation of mineral formulas 2nd edn. Nedra, Leningrad (In Russian).
Bulakh AG (1970) Berechnung von Mineralformeln. VEB Deutscher Verlag fUr Grundstoffindustrie, Leipzig
Bulakh AG (1984) On errors in formulas of minerals recalculated from inaccurate chemical
data. Mineral J (Kiev) 4: 87-92 (In Russian)
Deer WA, Howie RA, Zussman J (1962,1963) Rock-forming minerals, vols 1-5. Longman
Deer WA, Howie RA, Zussman J (1992) An introduction to rock-forming minerals, 2nd edn.
Longman
Dollase WA, Newman WI (1984) Statistically most probable stoichiometric formulae. Am
Mineral 69: 553-556
Droop GTR (1987) A general equation for estimating Fe3+ concentrations in ferromagnesian
silicates and oxides from microprobe analyses using stoichiometric criteria. Mineral Mag 51:
431-435
Hey MH (1939) On the presentation of chemical analyses of minerals. Mineral Mag 25:
402-412
Hey MH (1950) An index of mineral species and varieties arranged chemically. London, British
Museum
Hey MH (1954) A further note on the presentation of chemical analyses of minerals. Mineral
Mag 30: 481-497
Lima-de-Faria J, Hellner E, Liebau F, Makovicky E, Part he E (1990) Nomenclature of
inorganic structure types. Report of the International Union of Crystallography Commission on Crystallographic Nomenclature Subcommittee on the Nomenclature of Inorganic Structure Type, Acta Crystallogr A46: 1-11
Nicholls GD, Zussman J (1954) The structural formula of a hydrous amphibole. Mineral Mag
30: 717-722
Povarennykh AS (1972) Crystal chemical classification of minerals, vols 1 and 2. Plenum Press,
New York
Robinson P, Spear FS, Schumacker JC, Laird J, Klein C, Evans BW, Doolan BL (1982) Phase
18
relations of metamorphic amphiboles; natural occurrence and theory. In: Veblen DR, Ribbe
PH (eds) Reviews in Mineralogy, 9B, pp 1-227, Min. Soc. America
Rock NMS, Carroll GW (1990) MINTAB: A general-purpose mineral recalculation and
tabulation program for Macintosh microcomputers. Am Mineral 75: 424-430
Strunz H (1982) Mineralogische Tabellen, 8 Auff. Akad Verlag, Leipzig
1.2.2 Multivariate Statistical Analysis for Processing

Chemical Data of Minerals
C. JOHN MANN and V.M. RYAKHOVSKY
When studying mineral associations and paragenesis, the necessity to classify

mineralogical objects and processes is constantly present. The best solution is
determined by a number of successive operations which lead to a grouping of
the objects or processes by their similarities in an objective manner. The results
will closely resemble an a priori classification, if that existing classification is
good, or a new classification will be revealed based solely upon the empirical
data available. The term classification usually means dividing a population of
things, samples, or objects into different subgroups (classes, clusters, units, taxa,
etc.) on the basis of various attributes identifiable in the population. Each group
or subdivision will be characterized by the values or features of attributes
recognized for individuals in that group.
Quantitative or objective classification is based on probability theory.
Boundaries for subgroups in a classification may range from a prior specification that is completely arbitrary or based on arbitrary facts, which may be
construed to reflect a "natural" or "real" subdivision, to a completely objective
basis, such as maximum similarity, minimum dissimilarity, or minimum distance
in multidimensional space. In any case, individuals will be placed objectively in
subgroups according to whatever rules are defined.
Discussion here is directed primarily toward only those classification methods that are used most widely in mineralogy, but brief consideration is given also
to expert systems, sensitivity analysis, and image analysis. All multivariate
classification methods use probability theory to geometrically group an empirical data set of n objects from a specified population in multi-dimensional
Euclidean space.
Classification by Multivariate Methods

Classification by statistical methods consists of a variety of mathematical
techniques for grouping objects numerically in some optimum manner or
ordering of objects on the basis of their similarities or dissimilarities (van Ryzin
1977; James 1985). Because classification is common to all sciences, it has been
1.2.2 Multivariate Statistical Analysis for Processing Chemical Data
19
reinvented numerous times in different sciences and many names thus are
associated with mathematical methods of classification. Some of these are
cluster analysis, discriminant analysis, multidimensional graphical procedures,
pattern recognition, decision theory, image analysis, assignment analysis, homogeneity analysis, and various other multivariate statistical methods.
Three major aspects commonly are revealed by these multivariate statistical
techniques. They provide a classification of objects in a population, they provide
a determination of informative combinations of characteristics associated with
each object, and they provide an estimation of relations between random
variables.
Classification methods can be considered easily to be primarily of two types.
"Assignment" classification is interested mainly in classifying new observations
as belonging to one of a finite number of known, already established subpopulations, or groups. "Identification" classification, on the contrary, is dividing a population into an unknown number of subpopulations or groups, so that
similarity within each group is greater than similarity across groups. The
resulting groups were not known a priori but are determined by data of the
population being classified. Discriminant analysis (Eisenbeis and Avery 1972;
Hand 1981) is an example of a multivariate method originating primarily for
assignment classification, whereas cluster analysis (Romesburg 1984) is designed
for identification classification.
Many of these employ procedures that are based commonly on Euclidian
distances in multidimensional space, in which dimension is determined by the
number of attributes (m) recognized or utilized for each object being classified.
Normally those classifications having the smallest intra-group distances and the
largest intergroup distances are considered optimum.
Although these methods provide an objective classification based on data
available or utilized, empirical data do not necessarily provide clearly defined, or
"natural" groups. Often boundaries will be gradational and some arbitrary and
subjective judgements must be imposed upon the methodology; the result is an
arbitrary classification.
Alternately, the formalized procedures of an expert system (James 1985;
Negoita 1985; Haux 1986; Lausen and Vach 1986) may be substituted for
statistical methods. Here, an expert system is a computer program designed to
act like a human, mineralogical expert who will place objects in an ideal
classification. The system is based on present mineralogical concepts, knowledge, and experience of the designer. The resulting classification will not be
dependent solely upon the empirical data, as in mathematical classifications,
although an expert system can be designed to change in some specified ways as a
result of new empirical data; that is, the expert system can learn as new data are
acquired and the computer program will change automatically to reflect this
new knowledge.
The objects may be individual rock samples collected in some specified
space, perhaps a geographical area or a lithostratigraphic unit. Each object is
described in some fashion mineralogically, commonly by chemical analyses.
20
Each measured chemical variable (e.g., a chemical element, an oxide, a compound) represents an attribute of each object. Thus, if 15 attributes are measured, each object or rock sample can be represented by a single point in
IS-dimensional Euclidean space; each coordinate corresponds to one measured
value or attribute.
Although a human may find it impossible to visualize, 15 orthogonal axes
and coordinates for a point are no more difficult to compute mathematically
than a point in three- or four-dimensional space; distances between pairs of
points and other statistical summary values are equally easy to calculate.
Because space here is inadequate to fully develop sufficient details of each
statistical technique so as to be comprehensive, accurate, and useful to the
mineralogist, the reader is referred to one or more references provided for each
method. These references do provide adequate and rigorous mathematical
treatment for each method. Furthermore, a researcher should be fully aware of
all mathematical assumptions that are inherent in methods being used because
they impose limitations both on the data that can be used safely and the validity
of results obtained by the analysis.
Cluster Analysis
Cluster analysis (Romesburg 1984) can be divided conveniently into two

categories:
1. Classification of relatively small sets of observations (n is small).
2. Classification of large sets of observations that number in the hundreds or
even thousands (n is large).
The former case often is simpler but less satisfactory, whereas the latter case may
be more difficult because an abundance of data may deny sharp boundaries
between groupings, forcing more subjective judgements to be imposed but
nonetheless resulting in more rigorous classification.
Similarly, classifications also can be divided into three categories according
to the type of prior information available:
1. The number of classes is known.
2. The number of classes is not known and must be determined.
3. The number of classes is not known, but its determination is not required.
When the number of clusters (g) is unknown, hierarchical trees, or dendrograms,

are helpful. Clustering may be either agglomerative or devisive (Good 1977). An
agglomerative clustering begins with every object being a cluster in itself (g = n);
or number of clusters equals number of objects to be classified. Successively,
clusters are combined so that each contains more objects and the total number
of clusters diminishes. Conversely, a devisive clustering begins with all objects in
a single cluster (g = 1) and successively the number of clusters increases by
subdivision so that initial clusters gradually contain fewer objects.
21
The manner in which cluster analysis is applied will not necessarily be the
same in different situations. For example, different types of distance measures or
relatedness may be used other than a Euclidian measure, and in fact many of
these are more widely used because they are superior in various ways. Certainly,
identical rules can be established for clustering in different situations but this
will not always guarantee optimum clusters. An objective criterion for comparing clusters based on different sets of data is difficult to construct. Estimation
indices which have been deduced from criteria for internal (intracluster) and
external (intercluster) values and from measures of regeneration (Kleijnen 1987)
can be used. Alternately, correspondence analysis (Bezdek 1981; Greenacre
1984) can be substituted.
The most widely used cluster analysis methods used in mineralogical
research are based on agglomerative hierarchical procedures (Romesburg 1984).
Distance between all pairs of objects in m-dimensional space, where m equals
number of attributes given for each object, is calculated and tabulated. Sequentially, clusters are aggregated by combining those two clusters that are nearest.
Merging may continue until some specified criterion is met; this might be a
specified number of clusters, a minimum distance between clusters, a maximum
distance between any points in a cluster, or many other possible criteria.
Similarly, mean distances and/or maximum distances can be computed for
all objects in each cluster and compared to mean and/or minimum distance
between all clusters to establish some stopping point in the classification.
Optimum clustering normally is considered to occur when a minimum number
of clusters are found which neither overlap nor are so close together to make
addition of new objects to clusters difficult. Another way to think about a good
classification is that it minimizes the probability of misclassification when new
objects are assigned.
The process can be carried to extreme so that all objects fall into a single
cluster, g = 1, but then no classification of the population is made. Just where
the process terminates is a matter of individual judgement, experience, and
knowledge; in some cases, the purpose of the classification may playa part in
this decision.
This approach is based on the heirarchical principles;
1. Agglomeration into clusters is governed by
min
Lpk
where
> min
L pq ,
Lpk is a distance measure of inclusion of point P in cluster K, Lpq is a

distance measure of inclusion of point P in cluster Q, Q is the
complement of K in a sample space of size N.
2. The following inequalities are assumed to be true in each step of agglomeration for all points Pn that have entered a group,
22
where
Lpk is mean distance of points P k to the center of mass in cluster K for

step Z of agglomeration, Lkr is mean distance of points P k + 1 to the
center of mass in cluster K for step Z + 1 of agglomeration.
The manhattan norm may be taken as a measure of distance between two points
of M -dimensional space (P l' P 2):
Lpl -p2 = (XPl - Xp2 ),
where X is location specified by m coordinates on m orthogonal axes.

Principal Components Analysis
Principal components analysis (Anderson 1984; Jolliffe 1986) is a classificationrelated method which is valuable for mineralogical study when the characteristics, features, or variables (m) are large in number. It attempts to reduce the
dimensionality ofthe original data set into a simpler set which retains most of the
original information but which will be easier to understand. The reduction is
performed by linear transformations.
This statistical method attempts to combine those variables that are most
similar statistically by relating them to a few orthogonal axes which can be
interpreted, hopefully, in physical terms. That is, each simplifying axis, or
principal component, can be interpreted to represent one important physical
factor or process which controls or significantly affects observed variables,
features, or characteristics. This method is an attempt to compress information
into a more manageable mass that can be understood more easily in the major
aspects and, in doing so, will reveal information about the structure of the data.
The first principal component, which accounts for the largest amount of total
variance in the data, will be associated with the most important natural or
physical factor. The second principal component will account for the next largest
amount of variance and represents the second most important physical factor,
and so forth for subsequent components.
The common difficulty in using principal components scientifically lies in
assigning meaningful or accurate interpretations of physical meaning to the most
important orthogonal axes or principal components.
For example, chemical reactions that are affected by the composition of
reagents and physical environment (temperature, pressure, etc.) might appear as
factors (principal components) in hydrothermal solutions. These circumstances
might lead to a decrease in number of variables that need to be considered in
detail, which in turn facilities comprehension of cause and consequence relationships. The interpretation of multidimensional observations is reduced to determining role factors in the origin of the mineralogical phenomena observed and to
a removal of possible nonlinear dependencies between variables. In the study
that would then follow, models of specific correlations of natural processes can
be developed by considering typical changes that would occur spatially and
temporally due to effects of individual factors and their combinations.
23
Principal components have been used widely in studying origins of structures

in hydrothermal formations and in analysis of paragenetical associations. This
methodology also is useful in verifying clusters or classifications and helping to
understand or interpret those clusters formed by other multivariate methods.
Image Analysis
A growing method of classification is image analysis or image understanding

(Serra 1982, 1988), which mathematically is more complex but also theoretically
more general. Images are viewed as domains in multidimensional space. The
classification procedure is reduced to choosing different fixed sets of characteristics and assigning them to the same image. Description of an image is made by a
sample and a separate point in the domain is a realization of this image. Image
analysis can be used both for digital data, as can all multivariate statistical
methods, and, more importantly, for optic or photographic images.
Image analysis usually is reduced to comparing an image with samples of
other images and then attributing it to a specific image on the basis of earlier
chosen criteria of similarity. The process of understanding is preceded by the
process oflearning, when a set of relatively simple rules are compiled. These rules
make a consistent result possible and determine what the criteria of similarity
will be. Image analysis thus is more suitable for making the transition from
classical scientific methods for classification to using expert systems and artificial
intelligence for classification.
Sensitivity Analysis
Sensitivity analysis (Hendrickson 1984) may be used to estimate the influence of

various factors that simultaneously are affecting a value which is a random
variable. It examines the magnitude of change occurring in a dependent variable
for specific changes in each independent variable successively as all other
independent variables are held constant. The methodology normally employs
stepwise multilinear regression to determine the degree of influence each factor
has on the total variance of the system. However, a great variety of other
methods are available for sensitivity analysis depending upon the nature of the
functional relationships.
Application of sensitivity analysis in mineralogical research can be illustrated
by an example. Suppose a clear zoning has been observed in an ore body. A
selection of some mineral, say arsenopyrite, and chemical analyses are made. A
question now arises whether average values of chemical composition of arsenopyrite are different in each zone. The answer will permit a definite composition to
be associated with a specific zone or zones in the arsenopyrite ore body; in
addition, the influence of zonation on chemical composition will be revealed.
24
Here, zones of the ore body are considered fixed; they are not arbitrary.
However, results of the chemical analyses show all the properties of a random
variable.
Next, a large number of ore bodies are now included in the study. If the
domains are tested in such a way that chemical compositions of arsenopyrite are
determined only within individual zones, results of these tests can be regarded as
a random sampling of all possible alternatives. Dividing this random sampling
into three groups, each corresponding to a specific zone in the ore body, the
influence of zonation on chemical composition can be estimated.
The parameters involved in sensitivity analysis above are different in each
case but the same goal is achieved. In the first case, expected values of average
sample values for concentration of chemical elements in arsenopyrite are treated
as an unknown constant; whereas, in the second case, expected values of the same
geochemical variables are treated as a realization of random variables.
This example illustrates that care must be exercised when choosing criteria
for statistical testing and verification of hypotheses and when using multivariate
analyses.
Cautions
Although simple in concept, classification and related mathematical methods

must be used with caution. All of the methods have assumptions or limitations
that a user must recognize. If these mathematical assumptions are not fulfilled,
results obtained by an analysis may have little or no meaning and may be
extremely misleading. For example, most of the methods are based on Gaussian
or normally distributed variables. If the attribute or variable being used does not
have a multivariate Gaussian distribution, the results technically are incorrect.
How serious or inconsequential this may be commonly will be a function of how
much the true distribution deviates from a Gaussian distribution. If the distribution of each variable is not known to be Gaussian, a user should either
(1) examine the distribution of each variable to determine how significantly it
departs from Gaussian or (2) use nonparametric statistical methods (Conover
1980; Gibbons 1985).
In cluster analysis, points that are among extreme values for each cluster may
strongly distort the systematics. To prevent this, a small "correction" may be
added. For example, average values of the attributes for each cluster may be
calculated at each step and a measure of dispersion, an average distance between
all points in the cluster, might be used for comparison of clusters at each level
with those for the following level. If certain criteria are not met in each
comparison, a correction will be made. If these failures to meet the established
criteria are due to normal, natural variation in a population that really is
Gaussian, the corrections will have little affect on the classification and will be
acceptable. However, if the failure to meet the criteria is due to a population that
really has, say, a lognormal distribution rather than the assumed Gaussian
25
distribution required by clustering theory, the classification will not be valid and
any corrections will further distort the reality of the data.
Mineralogists must also be concerned about using data that represent a
closed data set (Aitchison 1986, 1990). Because mineralogical data and analyses
normally sum to one, or 100%, or can be represented in a ternary, or tetrahedral
diagram, they are constrained in some manner. Care thus must be exercised in a
statistical analysis because constraints will yield false correlations and covariances for the variables in the analysis. Adverse effects due to closed number systems
will diminish as the number of variables increases (m becomes larger).
Users of multivariate statistical methods must be familiar with all mathematical assumptions and limitations inherent in each method and determine if their
data meet these criteria. If they do not satisfy the assumptions, an analysis must
be made as to what the effect has been for their data. Many times the resulting
consequence is small and not significant; but nevertheless, failure to note the
violations is dangerous and can be extremely misleading.
Mineralogical Aspects
Because these statistical methods of clustering or classification result in each
group or cluster of points having objects with the maximum similarity of
attributes (characteristics or features), some homogeneity will exist in the
classification. Thus, all mineral samples in an individual cluster can be assumed
to have a common geochemical nature and hence belong to a specific mineralogical type.
However, different norms may be used for calculation of a measure of
distance between objects for cluster analysis; thus, results may vary depending
upon which measure is used. From the mineralogical viewpoint, the choice of
norm which will define the similarity or differences of mineral features in a
classification should depend upon the mineralogical-geochemical state of the
samples being studied (solid state, heterogeneous mixtures, etc.). In order to
choose the norm, the concept of symmetry can be used because the structure of
symmetry has been a significant factor in constructing natural classifications
(U rmantsev 1986) classically.
Alternately, newer methods of cluster analysis utilizing fuzzy set theory
(Zadeh 1977; Yager et al. 1987; van Rijckevorsel 1987) can be used which will
provide a more objective mathematical basis for interpreting natural data and
systems (Bezdek 1981; Bezdek et al. 1981a, b). These methods have been
successful in solving other geological problems (Granath 1984, 1988; Kacewicz
1989).
Summary
Multivariate or multidimensional statistical methods provide a powerful and
useful tool for mineralogists. Classifications of chemical data can reveal natural
26
groups and paragenetic information about the rocks. Statistical classifications

are extremely versatile, accepting either a priori criteria specified by the user or
being governed completely by the natural data being used. Addition of new or
different data can either follow the groupings already established by earlier
classifications or provide a completely new classification.
Classifications can be based on a great variety of measures of similarity,
dissimilarity, distance, and other criteria. In addition, the various statistical
methods for classifying objects are all slightly different mathematically. Thus,
one can learn different things by using different methods on the same set of
mineralogical data. A classification by one method can be compared to another
by a different method to see which may establish the better classification in each
situation.
Even though these methods are widely used in mineralogy, they must be used
with intelligence and caution. Each data set and application must be examined
by the user to determine if the mathematical assumptions inherent in the
methodology are being met by their data. A mineralogist should not idly
presume that the method works correctly and gives meaningful results every
time. Rather, results obtained directly reflect the data used and the validity of the
application being made by the mineralogist.
References
Aitchison 1 (1986) The statistical analysis of compositional data. Methuen, New York, 405 pp
Aitchison 1 (1990) Relative variation diagrams for describing patterns of compositional
variability. Math geol 22(4): 487-511
Anderson TW (1984) An introduction to multivariate statistical analysis, 2nd edn. Wiley and
Sons, New York, 665 pp
Bezdek lC (1981) Pattern recognition with fuzzy objective functions. Plenum Press, New York,
256 pp
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cluster substructure. I. Linear structure: fuzzy c-lines. SIAM 1. Appl Math 40: 339--357
Bezdek lC, Co ray C, Gunderson R, Watson 1 (1981b) Detection and characterization of
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Conover Wl (1980) Practical nonparametric statistics. 2d edn. Wiley and Sons, New York,
485 pp
Eisenbeis RA, Avery RB (1972) Discriminant analysis and classification procedures: theory
and applications. Lexington Books, Lexington, Massachusetts, 250 pp
2d Ed., Marcel Dekker, Inc., 398 p.
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Greenacre Ml (1984) Theory and applications of correspondence analysis. Academic Press,
London, 357 pp
Hand Dl (1981) Discrimination and classification. Wiley and Sons, Chichester, Great Britain,
209 pp
1.3 The Mineral Composition of the Earth's Crust
27
Haux R (ed) (1986) Expert systems in statistics. Gustav Fischer, Stuttgart, 190 pp
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Kleijnen JPC (1987) Statistical tools for simulation practitioners. Marcel Dekker, New York,
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Negoita CV (1985) Expert systems and fuzzy systems. Benjamin/Cummings, Menlo Park,
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van Rijckevorsel (1987) The application of fuzzy coding and horseshoes in multiple correspondence analysis. DSWO Press, Leiden, 271 pp
van Ryzin J (ed) (1977) Classification and clustering. Academic Press, London, 458 pp
Yager RR, Ovchinnikov S, Tong RM, Nguyen HT (1987) Fuzzy sets and applications: selected
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Zadeh LA (1977) Fuzzy sets and their applications to pattern classification and clustering
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1.3 The Mineral Composition of the Earth's Crust,

Mantle, Meteorites, Moon, and Planets 2
A.A. YAROSHEVSKY and A.G.
BULAKH
Total Number of Minerals
Up to 1990 about 3500 mineral species have been found. The latest Glossary of
Mineral Species by Fleischer (1987, 1989) contains 3430 mineral species and
varieties. At present, about 60-70 new minerals are described every year (one or
two new minerals every week).
Nearly all the minerals were discovered in the Earth's rocks and ores, while
only 17 were first found in meteorites (some specific sulfides, phosphates,
2 This is a preliminary overview. Mineralogy of the mantle, meteorites, and Moon is considered
in special Chapters of Vol. 3.
28
silicates, carbides, and nitrides) and only two (armalcolite and tranquilitite) on
the Moon.
The increase in the total number of minerals has depended on several factors:
introduction in mineralogy of the new methods (after optics and wet chemistry,
X-ray diffraction, instrumental analytical methods, and especially microprobes),
the industrial use of new types of mineral resources (uranium, thorium, rare
metals, rate earths, borates) and new geological types of ore deposits, the
enormous development of prospecting and mapping, detailed mineralogical
studies of large ore deposits and the largest intrusive massifs, especially such
unique massifs as the Khibin massif in the Kola peninsula (where more than 500
minerals were described), Green River, Tsumeb, Franklin, and other mineral
deposits.
By the mid-1960s about 1700 mineral species had been established (in 1966
A.S. Povarennykh listed 1692 minerals). Now, about 25 years later, this number
has increased twofold.
The causes of the limited total number of minerals in comparison with the
number of chemical compounds included the following aspects. (1) The composition of the Earth's crust (and mantle) is dominated by eight major elements
(O,Si,AI,Fe,Mg,Ca,Na,K) and four minor elements (Ti,Mn,P,H), while all other
elements are present only in trace quantities. This element distribution depends,
in turn, on the chemical composition of the protoplanetary nebula. (2) Extensive
solid solutions are formed in most groups of minerals and especially minor and
trace elements occur as disperse impurities in the crystal structure of minerals
(see Chap. 1.1). (3) There are some crystallochemical constraints. (4) Thermodynamic factors, as well as the narrow ranges of acid-alkaline and redox conditions
III
Cii
.c
Ca Fe Si
3
Te
Ag
Pd
Pto AJj 0
Sb
0
o S
.2
Re
o
Bi
u0
.Ge
S
Nb .Ba TI
e Hg
n Be.N V Tr
00
Ta..
..U Sr
TI~oWTh. Ca CrZr
C>
Pb~U
Fl Mn M9.NIfAI
0
CI'
C
Boo Ni~n F , . K
Cd
In
:l
As
**
* *
O~TnMTnnTnnTrnTnMTnnTnMTnnTnnTrnTnnTnnTnnTrnTn
-6
-4
-2
log Element abundances in upper part

of continental crust, ppm
Fig. 1. Number of mineral species for the chemical elements vs. element abundances in the
Earth's crust
29
Table 8. The numbers of minerals for the chemical elements
> 1000
300-1000
0(2709), H (1921)
Si (906), Fe (883), Ca (867), S (761), Al (714), Na (560), Mg (555), Cu (437),
Mn (416), P (398), As (387), Pb (371)
100-300
K (288), C (272), F (221), Cl (220), U (199), Ti (196), Sb (195), Zn (193),

B (179), Y + TR (160), Bi (148), Ba (142), Ni (142), V (133), Ag (126),
Te (117), Nb (104)
30-100
Se (82), Sn (78), Sr (74), Be (71), N (70), Ta (69), Cr (69), Hg (68), Zr (65),

Li (65), Co (56), Pd (47), Pt (37), Th (37), Tl (34), Mo (33)
< 30
W (28), Au (28), Ir (17), Ge (16), I (16), Rh (13), Ru (12), Br (12), Cs (10),

Os (9), Sc (8), In (7), Ga (2), Hf (2), Re (2), Rb (0)
Compiled from M. Fleischer's Glossary (1987, 1989) with additions by V.A. Frank-Kamenetsky to the Russian edition (1990).
Table 9. The numbers of the minerals of different chemical classes in the Earth's crust, Moon,
and meteorites
Classes of minerals
Simple materials, intermetallides
Sulfides, selenides, tellurides
Sulfosalts
Arsenides, antimonides, bismutides
Oxides
Hydroxides
Silicates
Carbonates
Sulfates
Phosphates
Arsenates
Vanadates
Molibdates, wolframates
Chromates
Borates
Nitrates
Tellurites, selenites,
tellurates, selenates
Iodates
Fluorides
Chlorides, oxychlorides
Bromides, iodides
Carbides, phosphides, nitrides
Silicides
Organic compounds
Total number of mineral species
Earth's crust
82
245
256
62
212
180
883
165
293
352
198
64
25
6
128
15
57
8
42
82
6
17
5
30
3413
Moon
Meteorites
7
9
13
21
20
1
37
1
26
2
73
7
3
13
2
3
1
85
11
1
1
175
Based on M. Fleischer's Glossary (1987, 1989) with additions by V.A. Frank-Kamenetsky to

the Russian edition (1990).
30
and water and carbon dioxide activities are typical for the geological conditions
of mineral formation.
A correlation exists between the number of minerals containing an element
and the abundance ofthe 52 elements in the Earth's crust (Fig. 1). However, there
are several exceptions which include (1) the elements which are primarily
dispersed in natural matter (Rb,Ga,Hf,Sc,Cs,Br), and (2) the elements which have
some crystallochemical constraints for their scattered insertion in crystal
structures of the rock-forming minerals and which form their own mineral
phases (H,S,P,B,Se,Te,As,Sb,Bi,Cu,Ag,Au,Pb,Hg,Pt, and Pt-group metals).
The number of minerals containing an element, and the distribution of
minerals and classes of minerals in the Earth's crust, meteorites, and Moon are
shown in Tables 8 and 9.
The mineral composition of the Earth's crust is presented in Table 10 for the
sedimentary, granite-metamorphic, and ocean basaltic shells.
These data are based (1) on the estimations of the relative volumes of the
principal rock types in these shells (Table 11) and (2) the modal compositions of
the rocks, taken from their average mineral compositions (Bogatikov 1983, for
magmatic rocks; F. Clarke, F. Pettijohn, M.S. Shvetsov for sedimentary and
metamorphic rocks).
Other minerals and the less common rocks as well as ores compose in total
no more than 0.1 % of the Earth's crust.
W uile the estimates should not be taken as absolutely accurate, they show a
strong predominance offeldspars, quartz, and groups offemic minerals (olivines,
Table 10. Mineral compositions of the shells of the Earth's crust
Minerals
Sedimentary
shell
Granitemetamorphic
shell
Basaltic
shell
of the ocean
Feldspars
Olivine
Pyroxenes
Amphiboles
Micas
Chlorites-serpentines
Other silicates
Clay minerals
Quartz
Carbonates
Sulfates
Chlorides
Fe hydroxides
Ore minerals
(ilmenite, chromite, sulfides etc.)
Phosphates
Other minerals
Organic material
Volcanic glass
17.3
52.2
0.40
3.40
9.8
34.3
7.6
28.5
0.5
4.8
0.02
0.03
5.60
0.8
2.9
32.8
18.4
19.2
0.5
22.5
1.50
0.5
2.0
0.6
0.20
0.45
0.40
2.3
0.7
0.2
3.0
26.6
31
Table 11. Abundances of the main rock types in the Earth's crust.
(Ronov et al. 1990)
Shell and rock type
Sedimentary shell
Sands and sandstones
Clays and shales
Carbonates (limestones, dolomites)
Evaporites (gypses, halite etc.)
Volcanics
- Basalts
- Andesites
- Dacites
- Rhiolites
Granite-metamorphic shell
Granites, granodiorites, granito-gneisses
Gabbros and related rocks
Syenites and nepheline syenites
Ultramafic rocks
Meta-arkoses and metagraywackes
Paragneisses and schists
Metacarbonates
Silica-iron formations
Amphibolites and related basic rocks
Metamorphosed silicic volcanics
Basaltic shell of the ocean
Olivine tho lei tic basalts and related
metamorphosed rocks
S ubalkalic basalts
Abundance,
% of shell
volume
21.8
44.6
17.8
2.0
7.5
4.0
0.6
0.6
46.5
1.9
< 0.1
< 0.1
4.0
39.1
1.6
0.4
4.1
2.3
99.4
0.6
pyroxenes, amphiboles, and mica), as well as clays and carbonates (calcite and
dolomite). The mineral composition of these upper shells ofthe continental crust
is much more diverse than that of deeper geospheres, meteorites, or the Moon.
The mineral composition of the deeper zones of the continental crust (its
granulite-basi tic shell) is considered to be similar to the mafic magmatic rocks
(plagioclase, pyroxenes, olivine, ore minerals, garnets).
The mineral composition of the Earth's mantle (from the Mohorovicic
discontinuity down to 2900 km) has to be considered separately for the upper
mantle (down to 350 km), the middle or transition zone (350-900 km), and the
lower mantle (deeper 900 km).
Estimations of the composition of the upper mantle are based mostly on
geophysical data (velocity of longitudinal seismic waves 8.2 0.2 km/s; density
3.3-3.1 g/cm 3 ) and the mineral composition of xenoliths:
- spinel peridotites (up to 80% of xenoliths), pyroxenites, and other ultramafic
rocks, and small quantities (2-5%) of eclogites, brought by alkali basaltoids
from depths of about 80 km,
32
- spinel and garnet peridotites and eclogites brought by kimberlites from about
130 km depth.
The mineral composition of these rocks includes olivine, orthopyroxene
(enstatite-hypersthene), clinopyroxene (chromdiopside, omphacite, augite),
pyrope, spinel, chromite, amphiboles, phlogopite, plagioclase, apatite, and
diamond.
These petrological, geophysical, and geochemical studies suggest that the
essentially peridotite composition of the upper mantle (Ringwood 1975) with
some heterogeneous lateral and vertical changes is due to mantle metasomatism.
The rapid increases in the velocity of longitudinal seismic waves and in the
density of the rocks in the middle zone are related to the phase transitions which
lead to changes in the mineral composition. According to experimental data,
olivine (Mg 2 Si0 4 ) transforms at these pressures into the phase with a spinel
structure (SiMg 2 0 4 ) and pyroxene transforms into the granate structure phase:
2Mg 2 Si 2 0 6 -+Mg 3 (MgSi)Si 3 0 12 . At a depth ofabout 650 km, spinel transforms
into the assemblages MgO (periclase structure) and MgSi0 3 (perovskite structure).
The main minerals of the lower mantle are magnesto-wiistite (Mg,Fe)O and
silicate-perovskite MgSi0 3 .
The Earth's core is composed, according to recent models, of Fe-Na alloy
similar to the iron meteorites.
Lunar Mineralogy
About 90 minerals were discovered on the lunar surface, and most are of
magmatic origin; however, under the influence of meteorite impacts, processes of
impact metamorphism (crushing, thermal action, caking) occurred. There are
three groups of minerals formations (rocks) on the Moon:
1. Basalts of lunar mares (about 3.9-3.1 billion years old). They are formed due
to the near-surface crystallization of basaltic lavas. The main minerals are
pyroxenes, plagioclase, olivine, and ilmenite.
2. ANT rocks (anorthosite-norite-troctolite) comprising the predominant part
of the lunar highland material and consisting of plagioclase, pyroxene, and
olivine. Their ages are 4.6-4.1 billion years. They are breccias of various rocks
which were reworked by meteoritic impacts.
3. KREEP rocks. These are impact, metamorphosed breccias often containing a
glass. Their name is an acronym formed from the chemical elements which
enrich these rocks: K, rare earth elements, P. They correspond to the basalts
and are composed of plagioclase, pyroxene, and glass.
Thus, the main minerals of the lunar surface are plagioclases, clinopyroxenes
(augite and pigeonite), orthopyroxenes, olivine; in several types of rocks ilmenite
and armalcolite are found. The minor minerals are represented by chromecontaining spinel and silica minerals. Together there are only nine minerals.
33
There are another 80 minerals (zircon, some sulfides, and some phosphates)
which play the role of accessory minerals or rarities.
In the form of films on the surfaces of grains in lunar regolite, as microinclusions, and in small voids there are rare occurrences of the Moon minerals in
the form of native metals (Fe,Ti,AI) and water-containing minerals (amphiboles),
halite.
The mineral composition of the interior zones of the Moon is hypothetical. A
survey of this problem is given by Ringwood (1979), who suggests that the
average composition of the interior layer down to hundreds of kilometers [the
lunar mantle and core (?)] is similar to the pyrolite of the Earth's upper mantle.
The normative mineralogy of the Moon was calculated by Wanke and Dreibus
(1988); Dreibus and Wanke (1990); plagioclase (12.7%), pyroxenes 34.6%, olivine
51.7%, chromite 0.6%, other minerals 0.4%.
Mineral Composition of Meteorites

About 100 minerals were discovered in meteorites, more than 20 of them are
minerals specific to meteorites and have not as yet been found on Earth.
Meteorites vary considerably in their composition, texture, and structure. They
can be divided into three classes; stony (95.5%), iron-stony (1.3%), and iron
(3.2%); these classes can be divided into 20 chemical groups. The most
widespread and typical minerals of meteorites are olivines, pyroxenes, plagioclases, taenite, kamacite, troilite, and schreibersite.
The average mineral composition of the most widespread meteorite types ordinary chondrites which may be generally considered as a good representative
of known meteorite matter - can be calculated from data on the average
chemical composition of H- and L-chondrites (Table 12). For the characterization of meteoritic matter, carbonaceous chondrites are of particular significance. The chemical composition of carbonaceous chondrites is considered to be
Table 12. Mineral composition of high-iron low-iron chondrites.

(Dodd 1981)
Minerals
H-chondrites
L-chondrites
Olivine
Hypersthene
Diopside
Plagioclase
Apatite
Chromite
Ilmenite
Troilite
Fe-Ni metal
(kamacite + taenite)
36.2
24.5
47.0
4.0
10.0
0.6
0.6
0.2
5.3
4.6
10.7
0.6
0.6
0.2
6.1
18.6
7.5
22.7
34
representative for the composition of the nonvolatile fraction of matter from the
Solar System. Their most important peculiarity is the presence of hydrated
phases (montmorillonite, serpentine, chlorites, hydrocarbonates, hydrophosphates), magnetite, and carbonaceous material containing various organic compounds (including amino acids). Hydrosilicates, magnetite, and carbonaceous
particles have also been found in the composition of cosmic dust distributed
along the Solar System.
Another peculiarity of some carbonaceous chondrites is the presence of
inclusions consisting of high-temperature minerals assemblages (spinel, anorthite, melilite, perovskite, hybonite, as well as rate and extremely rare minerals
such as hedenbergite, andradite, sodalite, unusual metallic alloys, and some
others, which are unusual for meteorites).
From specific minerals, known only for meteorites, it is necessary to mention
nitrides (carlsbergite CrN, os bornite TiN, sinoite Si 2 N 2 0), sulfides of lithophile
elements [niningerite MgS, oldhamite CaS, brezinaite Cr 3 S4, caswellsilverite
NaCrS 2 , heideite (Fe,Cr)l +x(Ti,FehS4]' and minerals such as lawrensite FeCI 2 ,
kosmochlor NaCrSi 2 0 6 . Most of these minerals were formed in a unique
environment of very low oxygen fugacity (in enstatite chondrites).
Minerals of Inner and Outer Planets
Information about minerals of the planets is based only on some indirect

astronomical and cosmochemical data. V. Smith (1979) analyzed the structure of
Table 13. Probable rocks and minerals of Mercury, Venus, and Mars
Planets
Rocks and minerals
Spheres
Notes
Mercury
Fe,Ti-rich anorthosites
(plagioclae, pyroxenes,
ore minerals)
Crust
From reflection
spectra
Venus
K-rich basalts (plagioclase, pyroxenes)

Tholeiitic basalts
(plagioclase, pyroxenes)
Olivine gabbro-norite
(plagioclase, pyroxenes, olivine)
Surface
Venera -8,13
(X-ray fluorescence data)
Venera-9,1O,14
(XRF data)
Vega-l,2
(XRF data)
H 2 O-ice
CO 2 -ice
Titanomagnetite, magghemite,
pyrrhotite, nontronite
Montmorillonite and nontronite (80%), ferroxides
(5%), Mg sulfates and carbonates
(15%)
Fe,Ti-rich basalts
Polar caps
Mars
Surface
Surface
Soil on
basalts
From reflection
spectra
Viking lander
imaging data
imaging data
imaging data
Surface
imaging data
Airsols
35
Table 14. Probable rocks and minerals of outer planets and some satellites
Planets,
satellites
Rocks and minerals
Spheres
Notes
Surface
Europa
S
S03-ice
H 2 O-ice
Surface
Ganymeda
H 2 O-ice
Surface
Callisto
H 2 O-ice
Surface
Voyager and
Pioneer spectral
Voyager and
Pioneer spectral
Voyager and
Pioneer spectral
Voyager and
Pioneer spectral
Satellites and
rings of Saturn
Rings
Some satellites
H 2 O-ice
H 2 O-ice
Grain surfaces
Surfaces
Voyager spectral data

Satellites of
Uran
Ariel
Titania
H 2 O-ice
H 2 O-ice
Surface
Surface

Pluto
CH 4 -ice
Surface
Asteroids
Olivine, pyroxene,
hydrosilicates,
metal (Fe-Ni)
Surfaces
Spectral data
Satellites of
Jupiter
10
data
data
data
data
the planets and suggested models of their mineral composition. The normative
mineral composition of the inner planets was calculated by Morgan and Anders
(1978). Other methods still give limited results, but they are based on studies of
planets with data obtained by devices installed on space vehicles. These types of
data are summarized in Tables 13 and 14 using different sources.
This information indicates the common mineral nature of the matter of inner
planets (terrestrial planets) and the predominance of ices (carbon dioxide,
methane) in the composition of solid satellites of giant planets. Ices and silicates
with a significant admixture of carbonaceous material compose also the main
mass of comets.
References
Bogatikov OA (1983) Magmatic rocks, parts 1 and 2. Nauka, Moscow 766 p (in Russian)
Dodd RT (1981) Meteorites. A petrologic-chemical synthesis. Univ Press, Cambridge
Dreibus G, Wanke H (1990) Comparison of chemistry of Moon and Mars. Adv Space Res
10(3-4): 7-16
Fleischer M (1987) Glossary of mineral species. Mineral Record Inc Tucson, 227 pp
Fleischer M (1989) Additions and corrections to the glossary of mineral species. Mineral
Record Inc. Tucson, 30 pp
36
Florensky CP, Bazilevsky AT, Burba GA et al. (1981) Essays of comparative planetology.
Nauka, Moscow, 326 p (in Russian)
Frondel JV (1975) Lunar mineralogy. Wiley and Sons, New York
Phillips RI, Hartman WK, Taylor GI (eds) Origin of the Moon (1986) Lunar Planet Inst,
Houston
Mason B (1979) Meteorites. US Geol Surv Prof Pap 440-B-l
Morgan JM, Anders E (1978) Moon and Planets 18: 465-478
Petaev MI (1988) List of meteoritic minerals. Meteoritika Nauka, Moscow 47: 156-166
(in Russian)
Povarennyk AS (1972) Crystal chemical classification of minerals. Plenum Press, New York
(translated from Russian edition, 1966, Naukova Dumka, Kiev)
Ringwood AE (1975) Composition and pet~ology of the Earth's mantle. McGraw-Hili,
New York
Ringwood AE (1979) Origin of the Earth and Moon. Springer, Berlin Heidelberg New York
Ronov AB, Yaroshevsky AA, Migdisov AA (1990) Chemical structure of the Earth's crust and
major element geochemical balance. Nauka, Moscow, 180 pp
Sidorov YuI, Zolotov MYu (1989) Rocks and soils of the Martian surface. Nauka, Moscow,
224 pp (in Russian)
Smith JV (1979) Mineralogy of planets: a voyage in space and time. Mineral Mag 43 (325): 1-89
Taylor SR, McLennan SM (1985) The continental crust: its composition and evolution.
Blackwell, Oxford, 349 pp
Wanke H, Dreibus G (1988) Chemical composition and accretion history of terrestrial planets.
Philos Trans R Soc Lond Ser A 325: 545-557
CHAPTER 2
Crystal Structures of Minerals
38
Chapter 2. Crystal Structures of Minerals
2.1 General Results of Crystal Structure Analysis

of Minerals
2.1.1 Stages of Scientific and Technical Development
V.A. DRITS, F. LIEBAU, and Ch. PREWITT
The discovery of X-ray diffraction (XRD) in 1912 (Friedrich et al. 1912) marked
the beginning of a new era in the study of the atomic structure of crystals, as it
became possible to "visualize" the arrangement of atoms in the unit cell repeated
periodically over all the crystal volume. From then on, numerous structure
studies have ensured deep insight into the complex and versatile world of
minerals. These studies are of tremendous scientific and practical significance, as
the knowledge of crystal structure is indispensable for reliable interpretation of
data on chemical composition and physicochemical properties of minerals, for
predicting and synthesizing crystals having specific properties, and for analyzing
the formation and transformation conditions of minerals in various environments.
Methods of Crystal Structure Determination
In the first two decades of X-ray diffraction, beginning with the first crystal
structure determinations by Bragg (1913), hundreds of mineral structures were
deciphered including numerous halides, oxides, sulfides, carbonates, and the
main rock-forming silicates with different types of tetrahedral radicals. Structures were determined using the trial-and-error method where the correspondence of a model to the actual structure was tested by comparing calculated with
experimental X-ray ciffraction intensities. This method required rich imagination, intuition, and the ability to guess a model near enough to the actual
structure. In addition, it stimulated the analysis of general rules governing crystal
structures. This promoted elucidation of relationships between structure, composition, and properties of minerals and, eventually, effective interpretation of
new and more complicated structures. A new scientific domain, crystal chemistry
of minerals, as part of a more general crystal chemistry, was thus created, and its
progress was accompanied by the revelation of still finer details of the mineral
structure. It was during the early period of the development of crystal chemistry
that the ionic model was elaborated, a system of ionic radii was proposed, and
the additivity rule of such radii as well as the rules governing essentially ionic
crystals was formulated. The concepts of the valence state of atoms, hybridization of orbitals with overlap of electron density, electronegativity, and polarizability of atoms formed the basis for the modern theory of chemical bonding.
Analysis of a great deal of experimental data provided new insights into the
39
concepts of solid solubility, polymorphism, and morphotropy. In geometric

crystal chemistry, the theory of close packing was developed, the notions of the
structure type, stoichiometry, coordination numbers, and coordination polyhedra were introduced, and methods were elaborated for polyhedral representation of structures.
The limitations in the trial-and-error method were overcome when it was
found that the interatomic-vector function - the Patterson function - which is
constructed by using diffraction intensities, contains, in principle, enough
information to solve most crystal structures (Patterson 1934). With the use of
Patterson syntheses it became possible to determine more and more complicated structures. However, this method proved to be effective only for structures
containing relatively small numbers of heavy atoms in the asymmetric unit.
Direct determination of a crystal structure from its diffraction pattern was
long believed not feasible. However, analytical methods to determine the phases
of structure amplitudes directly from the diffraction intensities (now called direct
methods) were found eventually (Sayre 1952; Karle and Hauptman 1953;
Hauptman and Karle 1953; Woolfson 1987), and the basic problem in structure
analysis was thus solved. Effective application of theoretical and methodological
innovations was for a long time hampered by photographic registration of
intensities which limited the accuracy of structure determinations. The situation
was much improved with the development offour- and five-circle diffractometers
using electronic photon detectors. In these, high precision in intensity measurements is combined with completely automatic data collection and treatment,
leading to accurately refined atomic coordinates and other structure parameters.
Theory as well as the technique of single crystal X-ray diffraction structure
analysis have thus reached such a high level that routine structure determinations no longer require serious intellectual efforts. Even rather complicated
structures containing up to 200 atoms per asymmetric unit can be deciphered,
provided a high quality single crystal of suitable dimensions is available.
Although structure studies of newly discovered or relatively rare minerals
continued, "geometric" analysis of mineral crystal structures was, to a first
approximation, completed during the 1960s. The main attention was then
focused on high-precision determination of atomic positions and occupancies,
with subsequent derivation of correlations between mean and individual bond
lengths and angles in polyhedra, as well as the nature of chemical bonding,
polyhedron linkage, relative electro negativity of atoms surrounding the polyhedron involved, the degree of polyhedral distortion, metal-metal bonding
through shared polyhedral elements, etc. New structure data were used to obtain
a revised system of effective radii of ions for different charges and coordination
numbers (Shannon and Prewitt 1969, 1970; Shannon 1976). These new values are
now widely applied to various crystal-chemical problems associated with
isotypism, prediction of bond length, construction of structure models, etc. An
alternative system of non bonded radii (Glidewell 1975), however, made investigators aware that the ionic radii are not reality but just a very effective system of
quantities to be used for measuring the sizes of atoms in crystal structures.
40
The advent of modern sources of neutron radiation promoted rapid development of neutron-diffraction structure analysis which proved extremely fruitful in
precise structure determinations of minerals containing light elements (H, He, B,
etc.) and, in particular, of magnetic structures (Fuess 1979; White 1987).
Substantial amounts of new data on chemical bonding, valence state of
atoms, their effective charges and intercrystalline distribution, the nature of
defects including color centers, the contents of minute impurities, and other
subtle structure peculiarities have been obtained with the help of various
spectroscopic methods. These methods are based on the interaction of different
types of radiation, from y to radio waves, with matter and include Mossbauer
(y-resonance), X-ray absorption (XAS) and X-ray photo-electron spectroscopy
(XPS), optical absorption and reflection spectroscopy, luminescence, infrared
(IR) and Raman spectroscopy, electron paramagnetic resonance (EPR), nuclear
magnetic resonance (NMR), and nuclear quadrupole resonance (NQR).
Recently, solid state NMR has proved to be a very powerful method (Fyfe
1983; Engelhardt and Michel 1987). Since diffraction is based on the interference
of rays scattered by all atoms of a sample, long-range order of the atoms in a
crystal of suitable size is required to determine the structure with diffraction
methods. In contrast, since a measurable influence on the magnetic field at an
atomic position is only exerted by atoms within less than ca. 5 A distance, only
short range order is required for NMR methods so that poorly crystallized and
even amorphous and vitreous samples can be studied. Consequently, diffraction
and NMR methods complement each other ideally to determine the atomic
structure of minerals.
Application of synchrotron radiation (SR) offers new prospects for diffraction and spectroscopic methods. SR is characterized by exceptionally high
intensity, wide wavelength range, small incident-beam divergence, and high
polarizability, and is widely used in crystallography. SR is applied to structure
determination of single crystals as small as 1 to 5 J1m (Bachman et al. 1985); it
allows extremely rapid registration of diffraction patterns (Helliwell et al. 1989),
which ensures a qualitatively new level in studying the kinetics and mechanisms
of various processes, such as crystal growth, and phase transformations resulting from external effects (changes of pressure, temperature, and different
physical fields). Effective use of SR in real-time crystallography is promoted by
the advent oflinear and area detectors, which greatly increase the speed of XRD
work owing to simultaneous recording of diffraction patterns within a large
solid angle (Lehmann et al. 1988). The advent of SR marked the "second birth"
for X-ray absorption spectroscopy (XAS) and made feasible, in particular, great
progress in extended X-ray absorption fine structure (EXAFS) (Lytle 1989;
Greaves 1990; Lengeler 1990). These methods are effective tools for analyzing
the electronic structure of mineral components (oxidation state, site symmetry,
covalency, electronic transitions) and the local structural environment of a given
type of atom (number and types of the surrounding atoms, their distances from
the absorber, etc.), for revealing short-range ordering in the distribution of
41
diadochic atoms and studying crystal chemistry of minor elements in minerals,

etc.
Powder XRD was for a long time confined to qualitative and quantitative
phase analysis and to compiling computerized databanks and catalogs for
identification of minerals and mineral mixtures. However, because numerous
natural and synthetic compounds are formed in the microcrystalline state with
their crystals being too small for single-crystal structure determination, it was
urgent to develop diffraction methods for deciphering crystal structures of such
substances. This was complicated by low resolution resulting from the available
instruments, overlapping of diffraction peaks, "weak" reflections disappearing in
noise, etc. These difficulties have been overcome more recently as a result of
sophistication of the XRD experiments (Finger 1989) and computer methods for
data processing. The first method developed was that of profile analysis (the
Rietveld method - Rietveld 1969; Post and Bish 1989) for refining crystal
structures with known structural models. The method is based on the comparison of experimental and calculated XRD curves without separating individual reflections. The efficiency of the Rietveld method is, however, limited by
the need to take into account various instrumental effects arising in conventional
XRD powder diffractometers. The use ofSR makes it possible to apply a parallel
beam of high intensity that allows description of the peak form with high
precision as well as to determine the peak positions with a resolution of 0.02 in
2(}. This resolution level allows the separation of a number of reflections
sufficiently large for an ab initio structure determination using either Patterson
syntheses or direct methods (McCusker 1988), with subsequent refinement of
structural parameters by the Rietveld method. Such problems were not even
considered 10 years ago. The accuracy level achieved with SR provides results
that may compete with single crystal refinements.
Further realization of the potential of SR in powder XRD is associated with
application of anomalous scattering effects for a wide range of elements, with the
recording of XRD patterns in milliseconds or even shorter times, with simultaneous registration of several XRD patterns from the same sample with
different wavelengths, etc. In the near future, it is expected that increasing
attention will be given to structure determinations of mineral powders with 100
to 200 refined parameters, to studies of the kinetics of transformations of
minerals exposed to various external factors (e.g., pressure, temperature, electric
and magnetic fields, radiation, etc.), to unstable phases, to the analysis of
electron density distribution, and to investigations of powdered superconducting materials.
A substantial contribution to structure studies of microcrystalline minerals
was made by electron diffraction methods (e.g., Cowley 1953; Vainshtein 1964).
Oblique-texture electron diffraction is effective in structure analysis of finely
dispersed phyllosilicates and other minerals consisting of platy particles
(Zvyagin 1967; Drits 1987). Selected-area electron diffraction in combination
with X-ray energy-dispersive analysis has been used in the recent decade, not
42
only to identify phases but, under favorable conditions, also to determine

structures of microdivided, poorly crystallized minerals (Drits 1987). Convergentbeam electron diffraction is mostly used for unambiguous determination
of the space group symmetry. At present, the results of application of a wealth
of modern solid-state physical methods are used effectively in the domains
of structural mineralogy and crystal chemistry described below.
General Results of Crystal Structure Determination

Crystal-Chemical Classification of Minerals. The development of more and more
sophisticated experimental techniques is accompanied by an increasing accumulation of complicated structures of oxides, sulfides, carbonates, silicates, phosphates, arsenates, and other types of compounds. To handle such a vast number
of structures, suitable classifications for each class of compound have to be
elaborated. The best classification that can be chosen is the one that is best able
to serve a specific purpose. Since there are different purposes, different classifications have to be considered.
Because of the close interdependence between chemical composition, atomic
structure, thermodynamic stability, and chemical reactivity, a classification
based on crystal-chemical principles is probably the most widely applicable one.
However, the seardi for composition-structure-properties interrelations is based
on empirical generalizations and, therefore, allows alternative classifications.
Since silicates are by far the largest group of minerals and since phosphates,
germanates, and borates follow very similar crystal-chemical principles, several
slightly different classifications suggested for silicates shall be mentioned here.
Most silicates contain [Si0 4 ] tetrahedra as basic building units. Since the
Si-O bond is the strongest bond within most silicate structures, the various
crystal-chemical classifications of silicates are based on the way the [Si0 4 ]
tetrahedra are linked to form SimOn, anions which have the shape of groups,
rings, chains, layers, and three-dimensional frameworks.
One approach is based on the concept of tetrahedral radical polymorphism.
Here the minerals are classified into groups with geometrically distinct tetrahedral radicals of identical composition. The number of new radicals was shown
to be associated not with radicals having "new" stoichiometry but with new
"polymorphs" corresponding to simple Si: ratios.
Other approaches take, in addition, into account the influence of the cations
on the structure of the SimOn anions. Considering the size of the cations, the
principle of adjustability of tetrahedral anions to cation-oxygen polyhedral
motifs explains why a [Si0 4 ] tetrahedron is the basic building unit in silicates
containing small cations (Mg2 + ,A1 3 + ,Fe 2 + ,Fe 3 +, etc.) while in those with larger
ones (K + ,Na + ,Ca2+), the basic structural units are diorthogroups, [Si z07],
and triorthogroups, [Si 3 0 10 ]. Singling out these groups that are condensed
into more complicated tetrahedral anions consisting of chains, layers, and
rings constitutes one of the approaches to the classification of silicates (Belov
1961).
43
Another approach (Liebau 1985) to crystal-chemical classification of silicates

takes into account, in addition to the size of the cations, their electro negativity
and valence and the presence or absence of additional non silicate anions and/or
water molecules. This leads to further subdivision of silicates according to,
among other parameters, the number of bridging apices of the [Si0 4 ] tetrahedra, branching of silicate anions, and the periodicity of fundamental chains
and rings from which a silicate anion can be constructed.
Among the recent achievements in crystal chemistry, one of the most
significant is the derivation of an integral system of structure vs. composition
relationships for sulfosalts, a family of extremely complicated, nonstoichiometric
compounds (Kostov and Minceva-Stefanova 1982). Mineralogical crystal-chemistry of elements, another domain in classification studies, is aimed at revealing
the principles in distribution of a certain element over different minerals.
Classification of structural motifs consisting of [CaO n ] polyhedra in calcium
containing minerals is one example (Chiari 1990), that of structures built by
linking [CuO n ] groups with n = 2, 4, 5, and 6 is another (Ferey 1990). Such
studies are of practical significance, since the crystal chemistry of these elements
as well as of uranium, lithium, beryllium, boron, and others that occur in various
minerals is associated with problems of raw materials and of technical products
used in the building industry, energy production and storage, and many other
modern industries.
Real Structure of Minerals. The atomic structure determined by diffraction
methods is, in fact, the result of averaging over many thousands of unit cells in
the crystal volume. However, actual crystals may contain a variety of derivations from the periodic arrangement of atoms. These include, in the order of
increasing spatial extension, radiation centers, impurity atoms, vacancies, dislocations, twin planes, stacking faults, intergrowth effects, incommensurate structure modulations, commensurate and incommensurate interstratifications, etc.
Because various properties of a crystalline material are dramatically modified by
kind and density of such defects, while at the same time, details of kind and
distribution of such faults contain valuable information on the conditions which
existed when the mineral formed, it is of great importance to study the real
structure of a mineral.
In order to study the nature of defects in crystals, a number of specific
methods have been elaborated. An enormous contribution to the analysis of the
structure of a crystal is made by high-resolution transmission electron microscopy (HRTEM) (Veblen 1981; Downing et al. 1990). Owing to HRTEM, the old
dream of crystallographers to observe direct images of atoms in a crystal has
come true. The main advantage of HRTEM is the opportunity to observe
aperiodic, structural details of defects with a resolution between 2 and 5 A.
Among other methods, one should mention X-ray topography (Klapper 1991)
that reveals, in particular, dislocation structures, as well as methods for
simulating diffraction effects from structure models containing various defect
types (e.g., Veblen and Burnham 1977; Czank and Liebau 1980; Veblen 1981;
Drits and Tchoubar 1990).
44
Impurity atoms, radiation centers, vacancies, and other point defects affecting numerous physical properties (e.g., coloration, conduction etc.) are effectively detected by a number of modern spectroscopic methods.
Deformation Electron Density. Modern methods of high-precision XRD analysis
provide unique information on deformation density distribution, bp , i.e., the
distribution of valence electrons which remains after subtracting from the
experimental electron density the contribution of the spherical electron-density
component of each atom (Coppens 1982). The significance of such data is hard to
overestimate, as it is the valence bonds that determine to a large extent many
physical and chemical properties of crystals. A fairly large number of papers in
the field having appeared to date have demonstrated actual differences in bp
distribution for crystals with ionic, covalent, and metallic bonding. For example,
residual bp peaks are observed around Si atoms in some silicates, coinciding with
predictions of molecular-orbital calculations, thus indicating the covalent
component contributing to the Si-O bond (e.g., Wal et al. 1987). Further
sophistication in theoretical and experimental methods is required, however, in
order to ensure such a precision in evaluating electron density that would allow
quantitative interpretation of the nature of the chemical bond.
Analysis of valence-electron density distribution allows, in principle, estimation of the dimensions and shape of atoms (effective ionic radii in the case of
essentially ionic crystals), as well as the numbers of electrons ascribed to them.
Effective atomic charges and the degree of bond ionicity may be thus determined,
and the results obtained may be compared with the data of X-ray emission
spectroscopy and the molecular orbital method. Studies in this domain are of
great promise, although there are at present no unambiguous criteria for the
adequacy of corresponding results obtained by different methods.
Diadochy, Solid Solubility, and Nonstoichiometry. The main directions in the
study of structure-composition relationships concern the study of the nature and

limits of isomorphous substitutions, i.e., diadochy of atoms, in solid solutions
(mixed crystals), the determination of short-range and long-range ordering in
cation distribution (cluster formation), analysis of the role of various crystalchemical, and physico-chemical factors in differentiation of rare earth elements,
insight into physico-chemical and thermodynamic aspects of the theory of solid
solubility, better understanding of nonstoichiometry, analysis of the role of
micro impurities in stabilizing mineral structures, etc. High-precision determination of bond lengths between and scattering powers of atoms occupying
crystallographic positions allow quantitative evaluation of cationic composition
for each site (Alberti and Gottardi 1988) and can be used to either determine or
revise a mineral's crystal-chemical formula. These data form the necessary basis
for interpreting the results obtained by spectroscopic methods. When studying
the nature of diadochy, it is most important to apply the combination of
diffraction and spectroscopic methods to the same sample, in order to obtain
compatible results. Correct interpretation of the data of chemical analysis and,
45
specifically, analysis of non-stoichiometry requires information on compositional variations due to defects in the mineral structure.
Structure Modeling. One of the fundamental crystal-chemical problems is

prediction of structure and properties for given compositions and physicochemical parameters of the material from which the crystals are formed. It is obvious
that among all possible arrangements of atoms, the one actually realized at
equilibrium is that corresponding to the minimum of free energy. At present the
general solution of this problem is hampered by the unrealizably long computing
times. Therefore, various approximations are being developed. The quantumchemical approximations are based on the search for the minimum interaction
energy of all atoms and nuclei. The need to allow for interatomic interactions
that have a minor effect on the arrangement of atoms is, in itself, a complicated
problem and, therefore, a serious limitation for this method. Another approach is
based on the minimization of the interaction energy of atoms that are a priori
provided with assigned dimensions and other properties and arranged in a
regular fashion in accordance with space-symmetry rules. Although this method
has no strict physical foundation, the account of empirical short-range repulsive
potentials, along with the Coulomb energy, has ensured effective prediction of
the basic structural features and properties for a number of minerals including
complex oxides and silicates (Gibbs 1982). An approximation that uses empirical
potentials for the atoms is known as the molecular dynamics method. In addition
to predicting structures, it is also suitable to predict atomic mechanisms of
diffusion and rheological processes, phase transformations, and solid state
reactions (Angell et al. 1981; Soules 1990).
Another structure-simulation method is based on least-squares refinement of
roughly assigned atomic coordinates so as to minimize the discrepancies either
between the calculated and predicted interatomic distances (distance leastsquare method, DLS (Biirlocher et al. 1977) or between bond-valence sums
received by ions and their formal charges (valence least-squares, VLS, (Brown
1977), or by a combination of these two methods (Kroll et al. (1992)). Such
techniques are most suited for inorganic compounds containing no isomorphous cation substitutions and for simple ionic crystals with minor structural
distortions.
If minor distortions in structures of well-known topology depend on diverse
composition variations, then another approach is preferred. It is based on direct
calculations of unit-cell parameters using relevant geometric constructions and a
set of empirical formulas relating parameters that describe fine structural details
as well as composition and cell constants (Smoliar and Drits 1991).
Polymorphism, Phase Transformation Under High P and T. The problem of
mineral associations at large depths in the Earth's mantle has long been stirring
the imagination of the researchers. Moreover, modern technologies require
materials that can endure high temperature and pressure. One of the most
important crystal-chemical problems is, therefore, the study of structure trans-
46
formations with changes of temperature and pressure. Experimental methods to

solve this problem have now reached very high standards. A combination of
synchrotron radiation and area detectors supplied with high-temperature diamond-anvil cells is used to study both powder samples and single crystals under
simultaneous effect of pressure (greater than 50 GPa) and temperature (up to
1200 K). The most powerful devices supplied with laser heaters generate
pressures up to ca. 250 G Pa and temperatures of several thousand degrees. Highprecision structure determinations are performed with diffraction intensities
collected in situ in reasonably short time. In the nearest future similar progress
may be achieved in powder and single-crystal neutron-diffraction structure
analysis by using powerful pulsed neutron sources (Clearfield and Rudolf 1987;
Schultz 1987). At present, however, this method can be used to study structure
transformations under pressures up to only 3-5 GPa, a serious limitation of
information on the behavior of magnetic structures and light atoms under higher
pressure.
The very powerful experimental techniques available allow the synthesis of
many phases having new physicochemical properties. This provides a deeper
insight into mineral crystal chemistry, including that of mantle materials which
cannot be studied using any other method.
The abundant experimental data accumulated to date have served as a basis
for a classification of the basic types of structural mechanisms for polymorphic
transitions depending on the degree and nature of structural changes during the
transitions (Buerger 1971; Liebau 1983) and to formulate general rules that
control phase transitions. These data can also be used as a guide to synthesize
phases with new properties, to reveal sequences of phase transitions and stability
fields for minerals, and to construct constitution diagrams describing polymorphic interrelations (Biirnighausen 1980). With regard to symmetry changes with
increasing temperature T and/or pressure P the following general conclusions
can be drawn.
1. An increase in T is, in general, accompanied by an increase of symmetry.
2. A moderate increase in P is, in general, accompanied by a decrease of
symmetry as long as no reconstructive phase transformation takes place.
3. Reconstructive phase transformations by further increase of P are, in general,
accompanied by an increase of the ionic character of the chemical bonds.
Since the Coulomb field is spherical the higher ionicity of high pressure phases
causes an increase of symmetry. This is particularly true if the basic phase
transformation is accompanied by an increase of coordination number. As a
consequence, the transition from metamorphic rocks to upper mantle material should be accompanied by the transformation of low-symmetry minerals
of the Earth's crust, such as olivines, pyroxenes, and feldspars, into more
symmetric and closer-packed spinels, garnets, ilmenite, stishovite, etc. of the
mantle.
Another peculiarity of polymorphic transformations is that under high

pressure many of the crystal-chemical rules valid for ambient P and/or Tare
preserved. For example, since the radius ratio reation/ranion ofGe and 0 is near to
47
the lower limit for octahedral coordination, many germanates contain both
[Ge0 6 ] octahedra and [Ge0 4 ] tetrahedra under ambient P and T conditions.
For comparison, silicates with their lower radius ratio rsi: ro transform into
similar phases containing [Si0 4 ] and [Si0 6 ] polyhedra simultaneously under
the higher PIT conditions of the Earth's upper mantle. Germanates are,
therefore, suitable high-pressure models for silicates (Ringwood 1975).
The purpose of future studies should be, in addition to accumulating new
data and searching for empirical rules, to correlate structural transformations of
minerals under high P and T with their thermodynamical, physical, and chemical
properties. Very promising results in this field have, for example, been obtained
by developing the Landau theory further to a time-dependent order parameter
theory (Carpenter and Salje 1989) and measuring the order parameters through
various physical properties such as lattice parameters, intensities and broadening of superlattice reflections, birefringence, frequencies and line widths of
selected modes in IR and Raman spectra, NMR spectral peak intensities, etc. (e.g.
Palmer and Salje 1990; Palmer et al. 1990; Winkler and Buehrer 1990).
Polytypism, OD Structures, Polysomatic Series. Crystal structures in many
mineral families may be described in terms of rather large basic structural units
or modules. In this case, many very complicated structures can be analyzed
readily in terms of a series of different packings of elementary modules that
are infinite in one or two directions, and described in a simple analytical way
(Guinier et al. 1984; Zvyagin 1993). Various packing patterns of structurally
compatible, isochemical two-dimensional modules lead to poly type families
(phyllo-silicates, pyroxenes, etc.) (Baronnet 1980; Cameron and Papike 1980).
OD structures require, in addition, that layer pairs be symmetrically equivalent (e.g., wollastonites) (Dornberger-Schiff 1964). In the general case, structurally
compatible modules may differ in structure and composition. Combination of
such modules, in different proportions and with different patterns of alternation,
within one structure leads to polysomatic series (biopyriboles, the humite group,
pyroxenoids, neophites, Ti-silicate analogues of micas, etc.). (Takeuchi and Koto
1977; Thompson 1981; Veblen 1991; Mellini et al. 1985).
Melts and Glasses. Melts and glasses of diverse compositions are studied both to
determine their structural state and to analyze structural mechanisms of mineral
melting, differentiation, and crystallization of melts under various physicochemical conditions (e.g., Taylor and Brown 1979; Mysen et al. 1982). A model for the
melt structure should explain and predict various thermodynamic and rheological properties, such as viscosity, liquation, etc. Glasses that may be treated as
undercooled melts having similar structures are widely used. In particular,
special glasses are suitable to store or dispose radioactive waste.
The absence oflong-range order has for a long time been a serious hindrance
to unambiguous reconstruction of the three-dimensional structure of a polycomponent glass, even when a combination of diffraction, spectroscopic, and
electron microscopic methods were applied. Therefore, despite certain progress
in determining the main factors governing the glass structure and inter-
48
relationships between glass composition and properties, many of the present

concepts of glass structural features are hypothetical and sometimes conflicting.
Discussions on the local environment of Fe cations in silicate glasses and melts of
basic and ultra basic composition may serve as an example (My sen and Virgo
1989). Only recently substantial progress is being made with the aid of NMR
spectroscopy (Murdoch et al. 1985; Oestrike and Kirkpatrick 1988; Stallworth
and Bray 1990). See references in the following sections of this chapter and in the
chapters on real structures, chemical bonding, natural glasses, diffraction
methods, solid state spectroscopy and databases.
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Stallworth PE, Bray PJ (1990) In: (Uhlmann DR, Kreidl NJ, eds) Glass - science and
technology. Vol. 4B Chapter 2
Takeuchi Y, Koto K (1977) Miner J 8: 272-285
Taylor M, Brown GE (1979) Geochim Cosmochim Acta 43: 61-75,1467-1473
Thompson Jr, 18 (1981) Reviews Miner 9A: 141-188
Vainshtein BK (1964) Structure analysis by electron diffraction. Pergamon Press, Oxford
Veblen DR (1981) Reviews Miner 9A: 189-236
Veblen DR (1991) Amer Miner 76: 801-~826
Veblen DR, Burnham CW (1977) Science 198: 359-365
Wal Rl van der, Vos A, Kirfel A (1987) Acta Cryst B43: 132-143
White JW (1987) Trans Amer Cryst Assoc 23: 1-17
Winkler B, Buehrer W (1990) Phys Chern Minerals 17: 453-461
Woolfson MM (1987) Acta Cryst A43: 593-612
Zvyagin BB (1967) Electron-diffraction analysis of clay mineral structures. Plenum Press,
New York
Zvyagin BB (1993) Crystallogr Report 38: 54-60
50
2.1.2 Symmetry Bases. The Contemporary Symmetry

Theory in Solids
v.A.
KOPTSIK
In the second part of the 20th century, the classical theory of symmetry has been
enriched by many new fields, e.g., antisymmetry, colored symmetry, the symmetry of multidimensional spaces, etc. The use of symmetry theory in the natural
sciences - physics, chemistry, and biology - in their many ramifications has
become broader and deeper. The methods of symmetry have acquired a
philosophical significance: they have become some of the most general and
effective methods of theoretical investigation in contemporary natural philosophy as a whole. The fundamental significance of this method arises from its
capacity to reveal the invariants of transformations and to describe the inner
structure of material and ideal systems - the objects of scientific and artistic
research.
The concept of symmetry has two opposing aspects: transformation (change)
and conservation (in variance}. That which is conserved during a change is an
invariant; the set of transformations which keeps something invariant is its
symmetry group or semigroup.
Different ways of distinguishing the structural sublevels associated with one
particular object lead to different definitions of its symmetry groups. We
therefore define symmetry as the law governing the constitution of structural
objects or, more precisely, as the highest group of automorphisms conserving the
qualitative completeness of the systems under consideration. In a single real
object we could see a whole hierarchy of symmetries, which are active at different
structure levels.
Growing in the soil of structural biology (and its precursor, structural
crystallography), structure-system methods of investigation have gradually
spread to other fields of modern natural science and art. The great generality of
these methods follows from the fact that structure is a common form of the
existence and development of matter.
The theory of symmetry took its modern scientific form, however, only after
the development of the concept of groups (Calois 1830) and then its generalization. At the beginning of the twentieth century the theory of crystal
symmetry was the most highly developed, taking the form of the classical space
group of rigid transformation (Fedorov and Schonflies 1891). After the development of crystallography and crystal physics, group-theoretical methods were
applied in physics and other natural sciences, the method of symmetry has
become a powerful and effective instrument of theoretical research in modern
science. The problem of classification is a primary one for every science, so that
symmetry, which establishes structural invariants, constitutes an essential
technique for all of them.
2.1.2 Symmetry Bases. The Contemporary Symmetry Theory in Solids
51
It may be shown that classical three-dimensional space groups 1> are the
invariant extensions of the translation groups T by means of the crystallographic
points groups G or the groups by modulus G T isomorph with the group G,
1> = TIXG or 1> = TIXG T , for the groups ofsymmorphic and non-symmorphic
types correspondingly, IX being the symbol of the semi direct products of both
group.
In the same way one may consider all the generalized symmetry groups as
extensions of the corresponding classical groups by the use of certain groups of a
new kind. The latter include the antisymmetry (two-color) and poly-colored
point and space group in three- and n-dimensional spaces (n > 3).
The idea of anti symmetry was put forward independently by Heesch (1929)
and Shubnikov (1945). There exist 58 two-colored point groups G' isomorphic
with G. The classical operators g E G' constitute the subgroups He G' of index
two, the other operators g' E G' are combined with the antisymmetry operator I',
g' = gl' = l'g,
g = 1,2, 3,4,6,
I, 2 = m, 3, 4, 6.
In the same way, among 1651 anti symmetry space groups there are 230 1>-groups
of classical type, 230 (1) x 1')-neutral groups (direct product 1> with 1') and 11911>'
two-colored groups of the types TIXG' and T'IXG being in number 674 and 517
correspondingly.
We note that the antisymmetry groups describe the symmetry properties of
material two-colored figures (or the three-dimensional two-colored spaces
enveloping them). The nongeometric quality ascribed to the points of these
spaces is abstractly modeled by color or by any function that can take on two
values, for instance the function of atom magnetic moments ill (f) describing the
distribution of the moments ill(f) in ferromagnetic and antiferromagnetic
colinear crystalline structures. In another interpretation the anti symmetry
groups may be treated as the symmetry groups G(4) or 1>(4) of four-dimensional
spaces in which the nongeometric coordinate takes only two fixed values x4 .
For homogeneous four-dimensional spaces the number of point symmetry
groups increases from 58G'(3) to 227G(4) and of space symmetry groups from
11911>'(3) to 47831>(4).
If instead of antisymmetry operator I' = 1(2) the operators 1(p) which map
onto themselve p orientational states of magnetic moments ill(f) are introduced,
one receives the 256 (G x I(P) neutral and 81G (p) p-colored point groups with
the crystallographic number of colors or 134G(P)+-+32G(3), p = 3,4, 6, 8, 12, 16,
24, 48. Point groups with cyclic color permutations were first obtained by Niggli
(1959) and Indenbom et al. (1960). The theory of derivation of color groups was
developed by Van der Waerden and Burckhardt (1961).
The derivation of the true colored-symmetry groups, i.e., those not containing 1(p) subgroups, was started in 1969 by Zamorzaev, who calculated the
number of three-, four-, and six-colored space groups and obtained the corresponding colored lattices.
In 1945 Shubnikov suggested the idea of many-fold anti symmetry and in
1960 the idea of similarity symmetry. Both ideas received ample development
52
and were further extended by Zamorsaev and collaborators. The idea of colored
symmetry received further development in the works of Niggli, Wondratschek,
Wittke, Van der Waerden, Burckhard, Pawley, Mascay, and Zamorzaev
(1959-1971). A number of works have indicated ways of obtained colored
symmetry groups containing classical subgroups which are not normal divisor.
Among them, Van der Waerden and Burkhardt groups are defined by a threetermed symbol G jH' jH in which the classical group G is isomorphic to G(p), the
subgroup H' c G of index p corresponds by isomorphism to the subgroup
H!P)cG(Pi), which preserves the quality (color) i, and the normal divisor
H = G n G' is defined by the intersection of all the conjugate subgroups
H= ngH'g-l,gEG.
gEG
The development of questions relating to the symmetry of multidimensional

geometric spaces has continued to move forward vigorously. Four-dimensional
space groups <P(4) were derived in number 4783 by H. Brown, R. Biilov,
1. Neubiiser, H. Wonderatschek and H. Zassenhaus (1978), their predecessors
being C. Hermann (1949), A. Hurley (1951), H. Wondratschek (1967), A. Mackay
and G. Pawley (1963), A. Zamorzaev and B. Tsekinovskii (1968), N. Belov and
T. Kuntsevich (1971).
In a series of papers by B.N. Delone (1959-1961), the construction of the
general theory of stereohedra (the theory of the regular division of space into
convex polyhedra) was essentially perfected. B.N. Delone proved the theorem:
the number of topologically different regular divisions of n-dimensional Euclidean space into convex polyhedra contiguous along whole faces is finite for
any n. The local theorem of regularity of (R, r)-point system are also proved.
The axiom of equivalence, according to which two objects equivalent to a
third object are equivalent to one another, forms the basis for the fact that the set
of transformations which keeps some particular object invariant constitute its
symmetry groups; but automorphic transformations by no means exhaust every
aspect of relations between objects. The very discovery of new equivalence
relationships and new automorphisms in known objects signifies a penetration
into a deeper structural level of research. For instance, we can study not only
metric properties of finite figures which are preserved under rigid motions, but
also their affine, conformal, projective, and topological properties. In physical
applications of the group theory not only discrete groups are important but also
the groups of continuous transformations.
The idea of deriving groups of affine deformations earlier noted by Viola
(1904) and Wulff (1909) underwent further development in papers by Mikheev
(1961), Nalivkin (1951), Dubov (1970) and Zabolotnii (1973) in the form of socalled groups of homology and groups of curvilinear symmetry which are the
other concrete interpretation of the color symmetry groups.
It is known that the main channel connecting symmetry with physics is the
channel of irreducible, vector and tensor representation of symmetry groups.
In monographs by Faddeev (1961) and Kovalev (1961, 1988), Miller and Love
(1967), Zak et al. (1969), Bradley and Gracknell (1971), the development of the
2.1.2 Symmetry Bases. The Contemporary Symmetry Theory in Solids
53
theory of irreducible representations and corepresentations of Fedorov-Shoenflies and Shubnikov space groups has been essentially completed, and the results
have been expressed in term of tables of characters of the corresponding matrix
groups.
The laws of conservation of symmetry play an important part in thermodynamics of equilibrium states and in the theory of phase transitions for isolated
system. In order to study quasi-invariant objects (for example, irreversible
physical processes) or aspects of the nonconservation of invariance in partly
ordered sets, in addition to group methods we may also require more general
methods allowing for the irreversibility, nonassociativity, or ambiguity of the
transformations, the absence of the identify operation from the set of transformations etc. For such cases we have the mathematical apparatus of the socalled semigroups, gruppoids, quasi-groups, and structures.
The importance of symmetry methods for investigations of physical processes is connected also with the symmetrical aspects of the causality principle
(the generalized principle of Curie-Shubnikov). It may be formulated as follows:
GconseqUencesi;:2
or ;:!,
Gsystem of reasons
(n
i
Gparticular
reason
i)
Gsymmetrizer,
which means that symmetry groups ofi-th system consequence must include the
symmetry group of systems of reason, the latter being defined through the
intersection (the common part) of symmetry group of particular reason multiplied by some symmetrizer. For example, the symmetry group of system of two
equal cubes with common face is 4/mmm = 4mm x 4m.L' where 4mm = m3m(1)
nm3m(2) is the intersection and symmetry plane m.L is the symmetrizer. If the
system consists of an object (crystal) and some external action, then according to
the Curie principle, it may manifest only such physical properties whose
symmetry is
GphYSical propertYi;;;2
or .;::!,
Gsystem = GObject (crystal)nGexternal action
During the last two decades the symmetry theory of imperfect, magnetic,
nonrigid crystals with internal degrees of freedom, and also the incommensurable space-modulated crystal phases p(f) was developed. The theory is based on
the abstract symmetry conversation (or extension) law and on the construction
of wreath products of two groups, one of them being symmetry group of some
average basic structure Po(f) and the other being symmetry group of perturbation function pp(f) which describes the distortion of the ideal average structure.
According to the Curie-Shubnicov principle, the symmetry group of composite
system is.
p(f) = Po(f)
+ bp(f) will
be
G p = (G pO nG bp ). Gsymmetrizer .
A good approximation to G p is the subgroup of the wreath product G bP wrG bp

isomorphic to G bp (the abstract symmetry conversation law!)
GpcGbpwrGpO
= (G~~xG~~x ...
G~~)t><Gpo, Gp+->G po .
54
The main feature of generalized (color) group G p is the positional dependence of

its combined symmetry elements (pf'pf2 ... pfnlgk), EGpo , {gl"'" gn}
= H c: Gpo, Pj E G~p. This dependence allows one to describe the generalized
space symmetry of such a complicated object as recently discovered quasicrystals with the icosahedron point symmetry and quasi-lattice (positional color
translation group). The positional color symmetry groups, the highest achievements of contemporary theory, are the concrete interpretation of n-dimensional
space groups, which serves as the other approach to the symmetry of imperfect
and partly perfect crystals.
In the course of this review we have tried to reveal both the fundamental and
applied aspects of the symmetry theory in solids. Let us summarize its meaning
for structural and genetic mineralogy.
All the physical and chemical methods of investigation may be applied to the
mineral, which is considered as a physical or chemical object; Among these are
the symmetry methods, which are connected with physics and chemistry of solids
through the properly determined representations of their symmetry groups; the
conservation laws and subordination principles between symmetries of the
composite material systems and their properties.
The symmetry considerations - the appropriate representations of the
appropriate symmetry groups - determine the selection and prohibition rules of
the physical properties of the material systems - crystals, minerals, rocks etc. At
the macroscopic level they determine the specific thermodynamics and mechanics of the material bodies and media, their thermal, electrical, magnetic, and
mechanical properties, which are described by vectors and tensors. At the
microscopic level they describe the electronic and vibrational structure of the
bodies, their vibrational dynamics and phase transitions, the optical, electronic
and phonon spectra, etc. The quantum-chemistry principles of the conservation
of orbital symmetry determine the possibility of the realization of chemical
reactions at laboratories and plants, and the geochemical evolution of minerals
at the Earth's crust. The quantum-field symmetry conservation principles
determine the nuclear reaction processes in the nuclear reactors of atomic power
stations, in the Earth's crust, in the cosmos, and so forth.
In the literature, one can find the necessary information about the practical
applications ofthe symmetry methods to different fields of investigations of ideal
and imperfect solids as well as additional references.
References
Brown H, Bulov R, Neubuser J, Wondratschek H, Zassenhaus H (1978) Crystallography
groups of four-dimensional space. Wiley and Sons, New York
Grebille D, Weigel D, Veysseyre R, Phan T (1990) Crystallography, geometry and physics in
higher dimensions. VII. The different types of symbols of the 371 mono-incommensurate
superspace groups. Acta Cryst A 46: 234-240
Hahn T (ed) (1983, 1987) International tables for crystallography, vol 1. Space-group
symmetry. Birmingham, Kinoch Press
2.1.3 Empirical Relationships in Structural Geometry
55
Hargittai I, Hargittai M (1986) Symmetry through the eyes of a chemist. VCH Verlagsgesellschaft, Weinheim
Hargittai I, Vainshtein BK, Udalova VV (eds) (1988) Crystal symmetries. Shubnikov centennial
papers. Comput Math App116: 351-669
Janssen T (1988) Aperiodic crystals: a contradicto in terminis. Phys Rep Rev Sect Phys Lett
168: 55-113
Koptsik VA (1966) Shubnikov groups. The reference book on symmetry and physical
properties of crystal structures. Moscow Univ Publ House (in Russian)
Koptsik VA (1975) Advances in the theoretical crystallography. Colour symmetry of defect
crystals. Kristall Technik 10: 231-245
Koptsik VA (1980) The symmetry of imperfect crystals. On the theory of structure phase
transition in crystals with internal degress of freedom: MATCH, Informal Commun Math
Chern 8: 3-20; 21-35
Koptsik VA (1983) New group theoretical methods in physics of imperfect crystals and the
theory of structure phase transitions. Symmetry principles in physics: J Phys C Sol State
Phys 16: 1-22; 23-35
Koptsik VA (1988) Generalized symmetry in crystal physics. Comput Math App116: 407-424
KoptsikVA (1991) Crystallography of quasicrystals: The problem of restoration of broken
symmetry. In: Manko V and Dodonov (eds) Lecture notes in physics. Springer, Berlin
Heidelberg New York, No 382: 588-600
Kotzev JN, Alexandrova DA (1988) Full tables of colour space groups with colour-preserving
translations. Acta Cryst A 44: 1082-1096
Kovalev OV (1987) Irreducible representations of the space groups. Gordon and Breach, New
York (1964); Irreducible representations, co-representations and induced representations of
the space groups. Nauka, Moscow (in Russian)
Shubnikov AV, Koptsik VA (1974) Symmetry in science and art. Plenum Press, New York
(translated from Russian edn. Nauka, Moscow 1972)
Smirnov VP, Evarestov RA (1988) Quantum chemistry of solids. The applications of symmetry
methods. Vysshaiya Schkola, Moscow (in Russian)
Talis AL, Koptsik VA (1990) Wreath algorithms for constructing of modular crystal structures.
SOy Cryst 35: 1347-1353
Vainstein BK (1979) Contemporary crystallography, vol 1. Symmetry and structures of
crystals. Nauka, Moscow (in Russian)
Wolff PM de, Janssen T, Janner A (1981) The superspace groups for incommensurate crystal
structures with one-dimensional modulation: Acta Cryst A 37: 625-636
Zamorzaev AM, Galarsky EI, Palistrant APh (1978) Colour symmetry: its generalizations and
applications. Shtiinza, Kishinev

W.H.
BAUR
High-quality modern refinements of crystals structures using X-ray or neutron

diffractiol. data collected on single crystals of minerals allow the determination
of atomic positions within 0.001 A or less. Rietveld-type refinements (i.e.,
analyses of the full profile of the powder pattern) of powder diffraction data, may
give estimatt:d standard deviations which are about one order of magnitude
larger, but still define the details of the structures well. The main limitations of
the results are inherent in the diffraction method itself: we obtain an averaging of
the locations of multitudinous atoms in all the unit cells of a macroscopic piece of
56
a crystal. This obscures two separate effects, namely the thermal motion of the
atoms and the random occupancy of sites where atoms are replacing each other.
Thus we see only a static picture of a crystal structure in which all atoms are
actually thermally vibrating, and we see only a superposition of statistical
occupancies of crystallographically equivalent sites by chemically different
atoms. The details of local, nonperiodic atomic environments get lost in the
process of a crystal structure determination. Nevertheless, the results of
thousands of precise crystal structure determinations have allowed us to
correlate observed interatomic distances and angles and structural geometries
with a number of empirical factors, thus giving us the possibility to make certain
predictions about details of crystal structures.
Polyhedral Distortions
When we describe coordinations of atoms around each other we speak of

tetrahedral, octahedral, trigonally prismatic coordinations, etc.; however, usually these coordination polyhedra are far from being regular. In a few simple
crystal structures coordination polyhedra of maximum symmetry and regularity
can be found. However, most central atoms in coordination polyhedra are
located in sites oflow symmetry and the distances to surrounding atoms can vary
from their means easily by 10% or more. Distortions of coordination polyhedra
can affect either the central atom to ligand distance, or the angles subtended by
the ligands at the central atoms, or the edges of the coordination polyhedra, that
is the contact distances between the ligands. Thus, it is not sufficient to say that a
coordination polyhedron is distorted, it has to be specified as well what it is that
is distorted in that polyhedron. Within an AX n polyhedron the A-X distances
can be changed without affecting the X-X edge lengths by changing the X-A-X
angles, the A-X bond length can be changed without affecting the angles
X-A-X, by disturbing the edge lengths X-X, and finally the angles X-A-X can
be distorted without involving the A-X distances by changing in the process the
lengths of the edges X-X. When distortions are discussed it is useful to have
available a quantitative measure. A simple way to express them is as mean
deviations from the mean. Even a group as strongly bound as the phosphate
tetrahedron can have distortion indices of the bond lengths of about 5%. Silicate
tetrahedra are slightly more regular, the distortion index of the bond lengths is
usually less than 3%.
Some transition metal ions exhibit the static Jahn-Teller effect when their eg
orbitals are only partly filled. Well known examples are ions with d 4 electronic
configuration such as Cr2 + or Mn 3 +, or with d 9 configuration such as Cu 2+.
Another common example of distorted coordination polyhedra is given by
atoms with nonbonding (lone) electronic pairs (valence shell electron pair
repulsion = VSEPR), compare SnS0 4 with BaS0 4 The Sn atom forms with
three near ligands a pyramid with angles O-S-O of 78, while the Ba ion is
surrounded by 12 oxygen atoms in a reasonably regular way. In terms ofVSEPR
57
we can say that Sn2+ engages in covalent bonds with the three oxygen atoms.
The fourth orbital (pointing away from the pyramid) is occupied by the lone
electron pair which acts as an additional ligand and prevent a close approach by
other oxygen atoms. Such asymmetric coordination environments are displayed
not only by Sn2+, but also by Ge 2 +, Pb 2 +, As3+, Sb3+, Bj3+, Se4 +, Te 4 +, Br 5 +,
15 +, and Xe 6 +.
Another example, where the geometry of the coordination polyhedra is
greatly distorted is provided by linear uranyl groups O-U-O and by vanadyl
groups Y-0. In both cases the bond lengths within these groups are much
shorter (1.6 to 1.8 A) than the remaining bond lengths (usually longer than 2.0 A)
within the coordination polyhedra around the y5 +- or U 6 +-ions. Obviously the
bonding (possibly multiple) within the UO~ + or Y03 + groups is stronger than to
further neighbors. One can assign to each of the different observed bond lengths
a corresponding bond strength, s, so that the sum of these s received by each
oxygen atom is 2.0 by constructing an empirical bond strength vs bond length
curve based on the available crystal structure data of the uranyl compounds.
These empirical bond strengths are not identical to the Pauling (formally
electrostatic) bond strengths obtained by dividing the formal charge of a cation
by its coordination number. However, they preserve, with a twist, Pauling's
postulate according to which the sum of the bond strengths received by the anion
should equal (with opposite sign) the formal charge of this anion. Alternately,
one can relate the observed bond lengths to bond orders using Pauling's
logarithmic formula
Dn - Dl
= 2klogn.
(1)
Assuming the single bond length Dl to be 1.81 A and a value of k of 0.39 one
obtains for vanadates bond orders which within reasonable limits add up to the
formal charges of 5 + for vanadium and of2 - for oxygen. By defining the bond
orders in this way Pauling's postulate is satisfied.
Distortions Due to Differences in the Environment of Individual Atoms
However, there are other distortions in crystalline solids which are not related to
electronic asymmetries or to preferential strong bonding between selected atoms.
This can be observed in a large number of individual crystal structures and their
interpretation shows that in cases in which Pauling's postulate is not obeyed an
effective charge balance is achieved by adjustments in the cation-anion distances. For instance, for a series of precisely determined borate structures this
was described by empirically derived bond strength vs bond length curves for the
B-O and O-H---O distances (analogously to the treatment of the uranyl
compounds). The difference lies in the fact that the short U-O bonds are inherent
to the uranyl groups, while in the borates (and the other structures mentioned in
this section) the short and long cation-anion distances are externally imposed on
the atoms by their "underbonding" or "overbonding" (Zachariasen).
58
In the early 1970s, a number of papers were published in which various

attempts were made to put the relationships between bond lengths and bond
strengths on a quantitative basis. Two different approaches were followed, both
related to Pauling's electrostatic valence rule. In one the deviations from
Pauling's postulate are used as a measure for bond length changes, thus allowing
the prediction of bond lengths for given bond strength deviations (extended
electrostatic valence rule). In the other approach the bond strengths are
redefined in such a way that their sums yield the proper formal charges at the
sites of the different ions, thus preserving the validity of Pauling's postulate
(valence balancing). Both these approaches are like different sides of the same
coin and both have their advantages and their drawbacks.
Extended Electrostatic Valence Rule and the Prediction of Bond Lengths
Pauling postulated that his second rule shall be satisfied within rather narrow
limits. Accordingly deviations by as much as 1/6 valence units (v.u.) should be
rare in silicate minerals. Meanwhile it is obvious that even in stable rock-forming
silicate structures variations in the sum of the Pauling bond strengths received by
the oxygen atoms can range from 1.67 to 2.33 v.u. In less stable structures the
deviations can be even larger. Therefore, Pauling's postulate has to be modified
somewhat.
The value of Px received by the anions in a crystal structure is on the average
equal, with changed sign, to the valences of the anions. For any individual anion,
however, Px can deviate from this value up to about 50%.
The bond lengths to an anion vary proportionally to the Pauling bond
strengths received by this anion as the average bond strength received by all
anions in a coordination polyhedron is close to the ideal value (the charge of the
anion with reversed sign). If all anions in a polyhedron are over- or undersaturated, the mean value ofthe cation-anion distance is not affected. This can be
summarized (Baur) by:
The average value of the distance d(A-X) within a coordination polyhedron
is approximately constant and independent of the sum of the Px values received
by all the anions in the polyhedron. Therefore, the deviation of an individual
bond length d(A-X) from d(A-X)mean is proportional to Apx and the bond
lengths d(A-X) can be predicted to a second approximation from equations of
the form
d(A-X)
= (d(A-X)mean + bApx) A,
(2)
where d(A-X)mean and b are empirically derived constants for given pairs of A
and X in a given coordination, and where Apx is the difference between the
individual Px and the mean Px for the coordination polyhedron:
Apx = Px - Px(mean)'
(3)
This relationship can be called the extended electrostatic valence rule because it
59
extends Pauling's original valence rule by accounting for bond lengths as well as
for bond strengths.
The agreement between predicted and observed interatomic distances has
been compared for several thousand examples. On the average, the predicted
distances based on this relationship agree within 0.01 Awith the experimentally
determined values for tetrahedrally coordinated ions of high formal charge (Si 4+,
p 5 +, S4+). For distances involving ions of smaller charge and/or higher
coordination number the average difference between prediction and observation
can be several hundredths of an A, reaching up to 0.1 A.
The possibility of predicting individual interatomic distances based on such
an empirical approach becomes useful when we predict distances serving as input
to the computer simulation of crystal structures, or when we use predicted
distances as a criterion whether or not a particular structure has been correctly
determined, or when we compare observed and predicted distances to establish
the correct crystal chemistry of a mineral. Above a linear relationship between
bond strength and observed bond length is assumed. The scatter in the
experimental data and the limited range of bond lengths investigated do not
allow to ascertain the existence of a nonlinear relationship.
Valence Balancing
Pauling's logarithmic formula (1) is the basis of the reverse procedure in which
the bond strengths are redefined in such a way that their sum yields the proper
valence at all the ions. This way nonlinear relationships can be represented. One
can employ nonanalytical bond strength versus bond length curves, or use
logarithmic forms, simple inverse relations, fit curves by third degree polynomials, or balance the valences by assuming that the bond strengths are
proportional to the inverse n-th powers of the bond length. The approach most
used is the one favored by Brown and Shannon. It has been recently extended to
allow the prediction of bond valences and thus of bond lengths as well.
Si-O and AI-O Bonds
Of particular importance for many common minerals are the bond lengths in
silicates. It was realized a long time ago that experimentally determined bond
lengths can be used for estimating the AI-content of (Si,AI)O 4 tetrahedra and this
concept was subsequently refined. Since the mean Si-O distance depends on the
Si-O-T angle (where T is a tetrahedrally coordinated cation), on the mean
coordination number of the oxygen atoms and on the connectivity of the silicate
tetrahedron with other coordination tetrahedra, the relationship between mean
(Si,AI)-O distance and AI-content is actually more complex than originally
thought. Recently a computer program was written, which calculates the Si/ Al
ratio deduced for an (Si,AI)04 tetrahedron of known dimensions. Such empirical
60
relationships allow the prediction of individual Si-O distances within average

deviations of 0.010 A from the experimental values and of mean Si-O distances
within 0.007 A of experimental values. The average AI-content of (Si,AI)04
tetrahedra in framework silicates can be estimated within about 1%, when
compared with chemical analyses of some feldspars and zeolites, and within 1 or
2% when compared with MASNMR data on zeolite rho.
Computer Simulation of Crystal Structures
While we cannot predict crystal structures from first principles, we can, for a
known or assumed topology, simulate the details of a crystal structure by a
distance least squares procedure (DLS). Empirical relationships of the kind
presented above are necessary to provide observations in terms of input of bond
distances and bond angles, and of weights for these observations. In fact, a
properly weighted DLS calculation is analogous to a force model, where the
predicted bond lengths correspond to the unstressed lengths of the springs, while
the squares of the weights correspond to the force constants (strengths) of the
springs. The Pauling bond strengths proved in this context to be excellent, when
used as weights in the DLS simulations.
Empirical Models and Quantum Chemistry
Many of the empirical relationships discussed above are derived from, or
extensions of Pauling's rules governing the geometries of essentially ionic
crystals. Inasmuch as we are certain today that purely ionic structures are rather
uncommon, this seems surprising. However, it has been shown recently that an
orbital interpretation of Pauling's rules leads to similar predictions as the
original electrostatic picture. On the other hand, Cruickshank emphasized that
empirical correlations have played a role as stimulus for theoretical approaches.
References
Alberti A, Gottardi G (1988) The determination of the AI-content in the tetrahedra of
framework silicates. Z Krist 184: 49-61
Baur WH (1970) Bond length variation and distorted coordination polyhedra in inorganic
crystals. Trans Am Cryst Assoc 6: 129-155
Baur WH (1978) Variation of mean Si-O bond lengths in silicon-oxygen tetrahedra. Acta Cryst
B34: 1751-1756
Baur WH (1981) Interatomic distance predictions for computer simulation of crystal structures. In: O'Keeffe M, Navrotsky A (eds) Structure and bonding in crystals, vol 2. Academic
Press, New York, pp 31-52
Baur WH, Fischer RX, Shannon RD, Staley RH, Vega AJ, Abrams L, Corbin DR, Jorgensen
JD (1987) Neutron powder diffraction study and physical characterization of zeolite
D-RHO shallow-bed calcined at 773 K and 873 K. Z Krist 179: 281-304
2.1.4 Systems of Empirical Radii of Atoms and Ions
61
Bersuker IB (1984) The Jahn-Teller effect and vibronic interactions in modem chemistry.
Plenum, New York
Bish DL, Post JE (eds) (1989) Modem powder diffraction. Reviews in mineralogy, vol 20,
Mineralogical Society of America, Washington, DC
Brown ID (1987) Recent developments in the bond valence model of inorganic bonding. Phys
Chern Mineral 15: 30-34
Brown ID, Shannon RD (1973) Empirical bond-strength-bond-Iength curves for oxides. Acta
Cryst A29: 266-282
Burdett JK (1980) Molecular shapes. Wiley, New York
Burdett JK, McLarnan TJ (1984) An orbital interpretation of Pauling's rules. Am Mineral 69:
601-621
Cruickshank DWJ (1985) A reassessment of dn-pn bonding in the tetrahedral oxyanions of
second-row atoms. J Mol Struct 130: 177-191
Liebau F (1985) Structual chemistry of silicates. Springer, Berlin Heidelberg New York
Meier MW, Villiger H (1971) Die Methode der Abstandsverfeinerung zur Bestimmung der
Atomkoordinaten idealisierter Geriiststrukturen. Z Krist 129: 411-423
O'Keeffe M (1989) The prediction and interpretation of bond lengths in crystals. Struct Bond
71: 161-190
Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell Univ Press, Ithaca
Smith JV, Bailey SW (1963) Second review of AI-O and Si-O tetrahedral distances. Acta Cryst
16: 801-811
Stout GH, Jensen LH (1989) X-ray structure determination, 2nd edn. Wiley, New York
Wells AF (1984) Structural inorganic chemistry, 5th edn. Clarendon, Oxford
Zachariasen WH, Penneman RA (1980) Application of bond length-bond strength analysis to
5f element fluorides. J Less-Comm Met 69: 369-377
2.1.4 Systems of Empirical Radii of Atoms and Ions;

Orbital and Pseudopotential Radii
W.H.
BAUR
Interatomic distances in crystal structures cannot be calculated from first

principles. Nevertheless, they can be predicted fairly accurately by using the
empirical knowledge accumulated in almost 80 years of diffraction studies of
crystals. A rigorous, widely acceptable, physically meaningful definition of
atomic or ionic radii is not available. If it were, this would imply that atoms or
ions can be treated as hard spheres. However, the current systems of empirical
radii are extremely useful in guiding and interpreting experiments in crystal
chemistry (in its widest sense).
Distances between any two neighboring atoms, A and X, in crystals depend
on their atomic sizes (numbers of electrons) and on the forces exerted between
them. The distance between A and X can be thought of as being determined by an
equilibrium between the attractive and the repulsive forces acting between the
two atoms. Different environments around the atoms can influence their
equilibrium distances. Therefore, it should not be expected that a given
interatomic distance A-X will always be of identical length when observed in
different crystal structures. Individual distances A-X can vary greatly even
within one coordination polyhedron AX n However, mean distances A-X for a
62
given type of polyhedron are fairly constant when values from different
structures are compared. The following treatment deals only with a discussion of
mean distances within coordination polyhedra.
Empirical Atomic Radii

The distance A-X (usually measured in Angstroms, A), between two atoms can
be expressed as
(1)
where rA and rx are the radii of atoms A and X. The radii are additive in the sense
that the interatomic distance is obtained as a sum of the radii. One can deduce
from a series of experimentally determined interatomic distances in metallic,
covalent, and ionic compounds a set of atomic radii for all elements. The mean
deviation between observed interatomic distances and those calculated from the
sum of such atomic radii is about 0.12 A. This agreement between observed
interatomic distances and the sums of the atomic radii is remarkable if one
considers the wide range of bond types covered by them. The atomic radii
correspond to the radii of maximum charge density of the outermost shells of the
atoms as shown by a comparison of these empirical radii with the radii of
maximum radial charge density of the largest shells of atoms calculated using the
self-consistent-field method. An approach oftwo atoms to a distance equal to the
sum of their atomic radii means that their outermost electron shells overlap, i.e.,
a covalent bond is formed between them. Therefore, atomic radii are particularly useful when we wish to test whether or not an experimentally determined
interatomic distance corresponds to a bond. The additivity of atomic radii only
works well within given classes of compounds and when the numbers and
arrangements of atoms around each other are similar. Consequently sets of
radii, which apply only to certain classes of compounds (ionic, covalent, or
metallic) were developed. Such more specialized sets of radii allowed for
corrections for valence state and coordination number.
Empirical Ionic Radii

Most important for mineralogical applications are sets of effective ionic radii
(Shannon-radii). These traditional ionic radii are approximately 0.8 A larger
than atomic radii for the anions and by the same amount smaller for the cations.
As long as only cation-anion distances are considered, any set of radii will of
course remain self-consistent when a constant amount is subtracted from all
cation radii and the same amount is added to all anion radii (and vice versa). This
is evident from Eq (1). Only the interatomic distance d(A-X) can be determined
experimentally. The apportionment of d(A-X) between rA and rx has to be based
on additional assumptions. Therefore we do not have an unambiguous method
2.1.4 Systems of Empirical Radii of Atoms and Ions
63
of assigning physically meaningful absolute values to ionic radii. The usually

assumed ionic radius for oxygen is about 1.4 A, implying that oxygen ions should
not approach each other closer than 2.8 A. However, non-bonding oxygenoxygen distances as short as 2.15 Ahave been observed in a variety of crystalline
environments. Insofar as atomic radii allow such close approaches of oxygen
ions, they seem to be physically more reasonable than ionic radii. It is recognized
that the apparent ionic radii vary not only with the formal oxidation states of the
ions, but also with the coordination numbers ofthe ions around each other. Thus
even ions cannot be pictured as hard spheres of a certain size.
The following assumptions were made when deriving effective ionic radii:
1. The radii are addictive [see Eq. (1)] provided effects of coordination number,
electronic spin, covalency, and repulsive forces are accounted for.
2. The effects of covalency in shortening the A-X bonds are similar in all A-F or
in all A-0 bonds.
3. Radii are independent of structure type except for the effects mentioned under
point (1).
4. The variation of radii with coordination number effects both the cations and
the anions, however, anions are more effected.
5. The mean cation-anion distances remain constant in similar polyhedra in one
crystal structure, while the individual cation-anion distance may vary.
6. For a constant anion (or cation), the volume of the unit cells within an
isostructural series is proportional to the third power of the radius of the
cation (or anion).
It has been established empirically which factors contribute to variations in
bond lengths. With increasing accuracy in the measurement of interatomic
distances, ever smaller effects could be identified. Important are: the variation
with spin state, the dependence on covalency, and the relationship with the
distortion of coordination polyhedra.
Shannon's radii are based mostly on oxides and the fit for fluorides is not as
good as for oxides, and it is even worse for sulfides or nitrides. Discrepancies such
as this were the starting point for the introduction of a covalency contraction
parameter. Sets of empirical self-consistent effective ionic radii have been
derived, which are useful for cations bonded to sulfide ions and for nitride ions.
Individual cation radii can assume rather different values, depending on whether
they are bonded to oxide, sulfide, or nitride ions. All these sets of radii are
empirically useful, but it would be dangerous to attach too much physical reality
to them.
Orbital Radii and Structure Maps

Possibly the calculated orbital radii of the valence electrons (i.e., pseudopotential
or nodal radii) are physically more significant. When linear combinations of such
radii are used as sorting parameters, one can construct structural maps in which
64
chemical compounds of the same crystal structure type are classified correctly in
the same areas of such maps. This approach is useful even for molecules.
References
Baur WH (1987) Effective ionic radii in nitrides. Cryst Rev 1: 59-83
Burdett JK, Price GD, Price SL (1981) Factors influencing solid state structure - an analysis
using pseudo potential radii structural maps. Phys Rev B24: 2903-2912
Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances
in halogenides and chalcogenides. Acta Cryst A32: 751-767
Shannon RD (1981) Bond distances in sulfides and a preliminary table of sulfide crystal radii.
In: Q'Keeffe M, Navrotsky A (eds) Structure and bonding in crystals, vol 2. Academic Press,
New York, pp 53-70
Shannon RD, Prewitt CT (1969) Effective ionic radii in oxides and fluorides. Acta Cryst B25:
925-945
Slater JC (1964) Atomic radii in crystals. J Chern Phys 41: 3199-3204
Waber JT, Cromer DT (1965) Orbital radii of atoms and ions. J Chern Phys 42: 4116-4123
2.1.5 Representation of Crystal Structures as Packings of

Spheres, Coordination Polyhedra, or Nets of Bonds
W.H.
BAUR
and D.
KASSNER
Physical models of inorganic crystal structures can be divided into three kinds:
those made of spheres in contact with each other, those made of coordination
polyhedra, and finally the ball and spoke models produced out of small wooden
balls and hard wire. The illustrations of these models projected into the plane of
the paper fill our scientific papers and monographs dealing with crystal structures of minerals and inorganic compounds. These three manners of depicting
inorganic crystal structures correspond to the various mental pictures we make
for ourselves of the arrangement of atoms and their groupings in these structures. Each of these modes of visualizing crystal structures is useful for understanding the topology and geometry of a given crystal structure, for classification purposes, as a help in solving unknown crystal structures and finally for the
generation of as yet unobserved, but hypothetically possible structures. The
various kinds of structural representation should be seen as complementary to
each other, because each stresses a different aspect of what we perceive as a
crystal chemical reality. Physical models of crystal structures are laborius and
expensive. Projected images of these models, however, can today be relatively
easily prepared with the help of numerous computer programs which are now
available.
Sphere Models
Representing individual atoms within a crystal structure as an arrangement of
rigid spheres in contact with each other is a gross oversimplification, but a very
2.1.5 Representation of Crystal Structures as Packings of Spheres
65
useful one, see Bragg. Viewing crystal structures as sphere packings makes the
implicit assumption that the forces between the atoms are radially symmetric.
Nevertheless, it is the basis of various systems of effective atomic, covalent, van
der Waals, metallic, orbital and ionic radii (see Chap 2.1.4) which have proved
their worth as empirical guideposts in crystal chemistry again and again. When
viewing a crystal structure as a packing of spheres, we are considering its
smallest possible building unit~, the atoms, and do not immediately perceive the
complete architectural complexity of the arrangement. Sphere packings can be
powerful classification devices, however, when we describe the various closest
packings of spheres and consider the possible stuffings of their interstitial spaces
by smaller atoms. In practical terms, both physical models constructed of
touching spheres and drawings of such models tend to obscure the insides of the
structure to be viewed. This can be avoided by making the spheres relatively
smaller (see below).
Polyhedral Models
Coordination polyhedra (sometimes referred to as Pauling polyhedra) combine
several atoms within a group and thus allow us to see the architecture of atoms
around each other and furthermore the condensation of these polyhedra into
larger units, such as chains, sheets, or frameworks. Since the centers of the
coordination polyhedra represent the central atoms, while the vertices stand for
the ligands, this approach emphasizes the covalent, directional nature of
bonding. We can picture more easily in our minds, or in models or figures what
the overall arrangement of the constituent parts of a given crystal structure is.
This can be used as a practical device, when solving the crystal structure of a
compound with known or assumed coordination of atoms around each other
(compare, for instance, the solution of the crystal structure of brookite; later
literature provides many additional examples). It can also be used as the basis of
classifications of groups of compounds, as has been done from several possible
viewpoints for the silicates and also for other mineral groups. When visualizing
crystal structures as assemblages of coordination polyhedra one abstracts from
the individual atoms. One can carry the abstraction one step further and
construct certain crystal structures not from individual coordination polyhedra,
but instead from groups of them; thus, for example, zeolites can be seen as
composed of secondary building units, each of which may consist of several
silicate tetrahedra, or micas can be seen as made up of sheets consisting of
coordination tetrahedra and octahedra. In practice, the polyhedral representation displays structural relationships very clearly, both in drawings and in
physical models.
Nets of Bonds
An alternate viewpoint has been proposed and advocated by Wells. He represents structures as three-dimensional systems of linked points. In these nets, or
66

Fig.2a-c. Perspective view of
the crystal structure of natrolite along the c-axis, using
STR UPLO'90, in all three
diagrams the small circles represent water molecules, the
medium circles the alkali cations. a The large spheres represent the oxygen atoms of the
framework, small spheres
standing for the silicon and
aluminum atoms in the centers of the tetrahedra are
hardly visible. b Polyhedral
view of the aluminosilicate
framework, the Si coordination tetrahedra are lightly shaded, the AI-tetrahedra densely,
c the Si- Si and Si- AI vectors
are shown as straight lines
connecting the centers of the
coordination tetrahedra. All
three diagrams are oriented
the same way, the origin is in
the lower left corner, the a-axis
runs from left to right, the baxis from top to bottom
skeletons, the atoms are the nodes, and the connections between them correspond to the bonds between the atoms. This emphasizes both the topology of the
links between the atoms, and the directional nature of the bonding arrangements. On the other hand, the restrictions on the geometry of certain bonds may
impose limits on the topology of periodic systems of such bonding arrangements. Nets are a particularly powerful way of depicting structures when dealing
with three-dimensional frameworks. A consideration of the connectivities of
2.1.5 Representation of Crystal Structures as Packings of Spheres
67
Fig. 2. Conld.
bonds provides sometimes startling relationships between structural types

which otherwise might seem to be unrelated. The net representation also lends
itself as a starting point for the simulation of crystal structures by methods such
as the distance least squares procedure, which is of considerable importance
given the absence of any practical way of calculating details of crystal structures
from first principles. Practically, two-coordinated atoms are not represented in
such nets separately, but instead the two bonds to them are treated as one. This
applies especially to bridging oxygen atoms in tetrahedral frameworks as in
Figs. 2 and 3. Drawings of nets are, of course, very transparent, but may be
confusing, unless they are rendered stereoscopically. One can imagine all
intermediate stages of models between the spherical and the net representation
by making the spheres relative to the bond distance smaller and smaller and
increasing the lengths of the links standing for the bonds. The ball and spoke
model is thus a physical realization of this compromise between the two modes
of representing crystal structures.
Computer Programs
Most packaged systems of crystallographic computer programs, such as XT AL,
provide today one or more of the currently available crystal structure plotting
programs. In addition, there are several stand-alone graphics programs available for crystallographic purposes. ORTEP was the first computer program
which allowed a semi-automatic production of structural drawings and is still
very much in use. It can be used to prepare all but polyhedral drawings of crystal
structures. STRUPLO is written primarily to provide just what ORTEP could
not give, namely polyhedral plots, but it can be used for skeletal drawings just as
much as for the representation of structures as assemblages of spheres. More
and more crystallographic programs are available on personal computers; an
example of a program written specifically for crystal structure plotting is
68
oo
oo
oo
oo
CD
o o
Fig.3a- b. View of the fibrou chain of natrolite parallel to
the 0- 0 vector of the outer oxygen atom of oppositely

located AI-coordination tetrahedra. The c-axis i pointing
IOwords the LOp. Same conventions as in Fig. I
69
ATOMS. An attempt to be exhaustive would be very lengthy, therefore the

reader is referred to a recent compilation by DK Smith. As an illustration of the
capabilities of a modern computer program views in two different directions of
the crystal structure of natrolite are presented in Figs. 2 and 3, in turn in terms of
packing of spheres, as coordination tetrahedra and finally represented as a net.
References
Baur WH (1977) Computer simulation of crystal structures. Phys Chern Mineral 2: 3-20
Baur WH, Kassner D, Kim CH, Sieber NHW (1990) Flexibility and distortion of the
framework of natrolite: crystal structures of ion-exchanged natrolites. Eur J Mineral 2:
761-769
Bragg WL (1920) The arrangement of atoms in crystals. Philos Mag [6] 40: 169-189
Dowty E (1990) ATOMS, atomic structure display software. Shape Software, Kingsport
Fischer RX (1985) STRUPL084, a FORTRAN program for crystal structure illustrations in
polyhedral representation. J Appl Cryst 18: 258-262
Fischer RX, Ie Lirzin A, Kassner D, Riidinger B (1991) STRUPLO'90, eine neue Version des
Fortran Plotprogramms zur Darstellung von Kristallstrukturen. Z Krist Suppl 3: 75
Hawthorne FC, Smith JV (1988) Enumeration of four-connected three-dimensional nets and
classification of framework silicates. Combination of zigzag chains with 63 , 3.12 2 , 4.8 2 ,
4.6.12, and (5 2 .8lz(5.8 2)! nets. Z Krist 183: 213-231
Johnson CK (1970) ORTEP: a FORTRAN thermal-ellipsoid plot program for crystal
structure illustrations. ORNL-3794, Oak Ridge National Laboratory, Oak Ridge
Liebau F (1985) Structural Chemistry of Silicates. Springer, Berlin Heidelberg New York
Meier WM, Olson DH (1987) Atlas of zeolite structure types, 2nd edn. Butterworths, London
Pauling L, Sturdivant JH (1928) The crystal structure of brookite. Z Krist 68: 239-256
Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell Univ Press, Ithaca
Smith DK (1989) Computer analysis of diffraction data. In: Bish DL, Post JE (eds) Modern
powder diffraction. Reviews in mineralogy, vol 20, Mineralogical Society of America,
Washington, DC, pp 183-216
Stewart JM, Hall SR (eds) (1990) XTAL System of crystallographic programs, release 3.0.
Universities of Maryland and Western Australia, Perth
Tillmanns E, Hofmeister W, Baur WH (1985) Variations on the theme of closest packing: the
structural chemistry of barium titanate compounds. J Sol State Chern 58: 14-28
Wells AF (1977) Three-dimensional nets and polyhedra. Wiley, New York
Wells AF (1984) Structural inorganic chemistry, 5th edn. ciarendon, Oxford

G.D.
PRICE
and V.S.
URUSOV
Significant progress has been made in the past 10-15 years in the application of
computer modeling to the prediction of crystal structures and their spectroscopic, thermodynamic, and defect properties. The approaches used range from
simple static energy minimization codes, through more sophisticated free-energy
minimization methods based on the calculation of lattice dynamical properties
within the quasi-harmonic approximation, to molecular dynamics, and most
70
recently full periodic boundary conditions quantum mechanical calculations

based upon both Hartree Fock and Local Density Approximation methods.
Central to simulation (as opposed to the quantum mechanical) methods is
the use of interatomic potentials to describe the energy of interaction between
pairs or groups of atoms or ions. These potentials contain parameters which can
be obtained either by fitting to quantum mechanically derived energy surfaces,
or empirically by fitting to experimentally determined crystal properties, such as
cell parameters, atomic coordinates, elastic constants, dielectric constants, etc.
Having defined a potential and a given crystal structure, it is possible to evaluate
the lattice energy of the structure and the forces acting on the atoms in the
lattice. It is generally desirable to allow the atomic coordinates and cell
geometry to be varied, so as to minimize the interaction energy, and reduce the
forces acting on the ions to zero.
There are many codes now available that can produce energy minimized
crystal structures, and which can then go on to calculate the accessible physical
properties predicted for a given structure by the chosen potential. These codes
include WMIN, METAPOCS, PARAPOCS, SIMPLEX, PLUTO, ELEN,
LEMINPI, and others. They all tend to have some features in common, and
particularly, most of them use the Ewald method to evaluate the electrostatic or
Madelung energy. This method transforms the slowly convergent l/r ij term into
two rapidly convergent series, one of which is calculated in real space and the
other in reciprocal space. Short-range potential terms (such as repulsion,
covalent, van der Waals, etc. contributions) are summed directly in real space,
within some user defined cutoff (typically between 10 and 20 A).
If the cohesion energy of a crystal is defined as a sum of interatomic
potentials, then one is in a position to calculate the optimum structure,
corresponding to an energy minimum, by varying the structural parameters.
Thus in the widely used code WMIN, the following functional is minimized:
(1)
where Wand Wi ar(; weight factors, U is the lattice energy, and Pi are the
parameters associated with atomic coordinates and cell geometry.
The codes available differ in the way in which they establish the minimization of the energy of a structure; some use the steepest descent method, which
requires the evaluation of the first derivatives of the potential in order to solve
the system, while others use the more efficient Newton-Raphson method, which
requires the calculation of a second derivatives matrix. The relative speed of
these methods depends upon the number of atoms in the crystal, but simulations
can now routinely be carried out with up to 500 species in the unit cell. Other
fast optimization methods can be established by using penalty functions or by
constraining the limits of variable searches.
All codes require as input a trial structure, which is subsequently refined.
Ideally, no symmetry constraints are placed on the refinement, so that subtle
displace transformations can be investigated. By their nature, these static
minimizations cannot guarantee finding a global minimum, but relax into the
71
nearest local minimum. Care must be taken therefore if an "idealized" structure

is taken as a starting point. Techniques, such as molecular dynamics or Monte
Carlo methods, may be needed if the system under investigation has many local
minima. Having established a relaxed structure, some codes (e.g., PARAPOCS)
can subsequently calculate the elastic constants, lattice vibrational modes, heat
capacity, entropy, etc. predicted by the potential for the relaxed structure. It is
then possible to minimize not the lattice energy of a structure, but its free energy
(within the quasi-harmonic approximation) to predict its thermal expansion,
Gruneisen parameters, etc.
Successful models now exist that will describe virtually all anhydrous
silicates, be they framework species, such as zeolites, or close-packed, high
density structures, such as MgSi0 3 -perovskite. Indeed, much recent effort has
gone into the simulation of the physical properties of the high pressure
polymorphs of magnesium silicate, as these phases determine the properties of
the Earth's mantle. Experimental studies under mantle pressure and temperature conditions are very difficult, and computer simulations are now being
successfully used to predict the properties of mantle phases at high P and T. In
addition to silicates, oxides and halogenides are routinely studied, and progress
is being made in the study of hydrous phases and those containing molecular
ions.
Modeling has been used to predict the relative stability of polytypes, and to
calculate the phase diagrams of some silicate phases. Defect properties are now
also being modeled, with specific emphasis on trying to establish the atomistic
processes that occur during diffusion in complex silicates. In the future, the
scope of static simulations will be widened still further, and when combined with
molecular dynamic simulations and quantum mechanical methods, will provide
us with a full methodology to establish the microscopic processes which
determine and underpin the macroscopic properties of minerals and inorganic
materials.
References
Burnham CW (1985) Mineral structure energetics and modelling using the ionic approximation. Reviews in Mineralogy 14, Springer, Berlin Heidelberg New York, pp 347-388
Catlow CRA, Mackrodt WC (1982) Computer simulation of solids. Lecture Notes in Physics,
166, Springer, Berlin Heidelberg New York
Catlow CRA, Price GD (1990) Computer modelling of solid-state inorganic materials. Nature
347: 243-248
Catti M (1986) Theoretical computation of the physical properties of mantle minerals. In:
Saxena S (ed) Advances in physical geochemistry 6. Springer, Berlin Heidelberg New York
Matsui M (1986) Computer simulations of structures and elastic constants of minerals.
J Mineral Soc Jpn 17: 169-179
Parker SC, Price GD (1989) Computer modelling of phase transitions in minerals. In: Catlow
CRA (ed) Advances in solid state chemistry, London, AI Press 1, pp 295-327
Urusov VS, Dubrovinsky LS (1989) Computer modelling of crystal structures and properties
of minerals. Moscow Univ Press, Moscow (in Russian)
72
2.1.7 Precision Electron Density Calculations: Relation to

Chemical Bonding and to Localization of Impurities in
Crystal Structures
V.G. TSIRELsoN and O.V. FRANK-KAMENETSKAYA
There are two ways to obtain the electron density of minerals. The first is to
calculate electron density by quantum chemistry methods, the second is by
X-ray diffraction measurement. In the latter case, a special experimental
procedure is needed and the accurate single-crystal X-ray diffraction analysis is
used for this purpose. The total X-ray intensities are measured with an accuracy
of about I % and secondary diffraction effects such as absorption, extinction,
thermal diffuse scattering, and anomalous dispersion are appropriately corrected. As a result, moduli of structure amplitudes are obtained. For the extraction
of crystal chemical information from X-ray data, the values of structure
amplitudes are approximated by their theoretical analogs, calculated from the
model of a given mineral. The refined parameters of the model are atomic
coordinates, harmonic and anharmonic characteristics of atomic thermal vibrations, and populations of valence electron shells of atoms. In this way the atomic
charges in many minerals have been determined.
The electron density in the unit cell can be mapped by Fourier series using
structure amplitudes as coefficients (Fig. 4). The phases of structure amplitudes
are calculated by means of a crystal model. The "experimental" electron density
maps have a resolution of 0.2 A and they are the basis for studying chemical
bonding in minerals. The deformation electron density (OED) is usually
calculated, in order to obtain characteristics of a chemical bond. OED is the
Fig. 4. Electron density distribution

in fluorite CaF 2 as observed by xray diffraction. Positions of maxima
are atom sites
73
2.1.7 Precision Electron Density Calculations
difference between crystal electron density restored from the X-ray diffraction
data and electron density of the ensemble of spherically symmetric atoms
calculated by quantum chemistry methods. DED describes the redistribution of
electrons during crystal formation from atoms.
There are general principles for the interpretation of DED maps. The excess
of DED appears as peaks on these maps in regions of bonding overlap of the
atomic orbitals and in the regions of the orbitals of electron lone pairs location.
Negative DED is connected with anti-bonding orbital overlap regions, and with
the regions where bonding overlap of atomic orbitals are subjected to weaker
changes than mutual penetration of atomic clouds. The DED peaks connected
with n-bonds are elongated in the internuclei space perpendicular to the line
linking the interaction atoms. In ionic bonds, DED peaks are displaced along the
bond line to more electronegative atoms and in strained bonds these peaks are
shifted from bond line.
An example of the significance of electron density studies for minerals is the
rutile-type high pressure porymorph of silica stishovite SiOz' In this mineral,
Si is coordinated by six oxygen atoms in an octahedral configuration. The
structure contains two nonequivalent Si- O bonds: the longer (equatorial) bonds
are 1.757 A. and are about 3% shorter than axial bonds; but the ionic model
predicts that ratio between Si- Oe and Si- O. bond length should be more than
unity. Furthermore, non bonding 0 - 0 edges of Si- octahedra (2.29 A.) are
Fig. Sa, h. Experimental deformation electron density (the difference between measured electron density for crystal and sum of calculated atomic electron densities) for stishovite Si0 2 . a
Map of the octahedron axial/equatorial bond plane. b Map of the coordination plane of the
oxygen atom. The contour interval is 0.05 eA - 3. Excess of electron density (dark lines) on the
bond lines is responsible for chemical bond forming: electron density peaks are shifted to more
electronegative oxygen atoms and elongated perpendicular to the bond line (n-character of the
bond). Negative electron density (dashed lines) characterizes the region from which the electron
is removed when the crystal is formed from atoms
74
shorter than the double oxygen radii (2.54-2.80 A). Thus, the real structure
contradicts the Pauling rule of shortening the shared edges of the polyhedra in an
ionic model. The DED maps (Fig. 5) reveal the bonding peaks with a height of
0.47 eA -3 on the Si-O. bonds and of 0.29 eA -3 on the Si-O. bonds. These
peaks are shifted toward oxygen atoms (partly ionic covalent u-bond) and shifted
from the bond line (some strain in the four-membered ring). The maxima in the
equatorial plane are linked by "bridges" of electron density. These bridges have a
shielding effect on the cation interaction across the shared edge, and reduce the
repulsive forces between Si atoms. Thus, electron density study explains the
origin of the Pauling rule violation. Note that the average distance between the
Si atom and the nearest DED peak is 1.10 A, which is close to the Slater atomic Si
radii of 1.15 A..
The observation of splitting of 3d-element electron energy levels in a crystal
field via electron density maps can be demonstrated for high-pressure phase
y-M 2 Si0 4, where M = Fe, Co, and Ni. These minerals belong to normal spinels
in which transition-metal atoms are situated in the centers of oxygen octahedra
(B-position) with symmetry position D 3d Eight positive peaks 0.9-1.0 eA -3 in
height located at the corners of a cube have been revealed on the DED map for yNi 2Si0 4 near a B-position (Fig. 6). The octahedral crystal field symmetry in the
position of a Co atom is more trigonally distorted, and peaks ofDED lying along
the threefold axis of the octahedron are higher. A further trigonal distortion of
the Fe-octahedron leads to the presence of excess DED peaks only along the
threefold axis. These DED maps may be interpreted in terms of the crystal field
theory as follows. The trigonal distortion of octahedron in this spinels is its
compression along the threefold axis [111]. This compression leads to the
splitting the 3d-electron energy levels of B-cations into a singlet ag with
corresponding orbital lies along the threefold axis, and two doublets: eg and e~
(the latter are described by n-orbitals lying in the plane perpendicular of the
threefold axis). The level a g is the lower in energy than e~. In the near perfect
octahedral environment, six of the eight 3d-electrons of the NF + must be
occupied ag and e~ orbitals and the remaining two must be occupied eg-orbitals.
Thus, Ni 2 + electronic configuration (ag)2(e~)4(eg)2 may be expected. Excess and
deficit of the electrons on corresponding orbitals as compared to the spherical
atom average orbital populations, equal to 8/5 electrons, are reflected in the
formation of positive and negative regions around Ni atoms on the DED map.
The position ofDED minima and maxima correspond to the crystal field theory
picture. As the number of 3d-electrons of the B-cation in a series Ni-Co-Fe
decreases, geometrical distortions in the structure increase, and the electron
density around the B-cation is changed: the ag-orbital electron population grows,
and the electron density of the e~-level decreases. This picture agrees well with the
simple qualitative predictions of the crystal field theory.
The results of experimental electron density analysis can be summarized as
follows. In all minerals (from halite-type to silicates, spinels, garnets, etc.) atomic
charges are smaller than the formal atomic oxidation numbers. The difference is
greater when a real chemical bond is distinguished from an idealized ionic bond
2.1.7 Precision Electron Density Calculations
75
[100]
- - -....-[110]
a
[100]
-b--"--
[110]
[100]
- - - t....
[110]
Fig. 6a-c. Experimental deformation electron

density for y-Ni 2 Si0 4 (a) (Marumo et al. 1974),
y-Co 2 Si0 4 (b), and y-Fe 2 Si0 4 (c) (Marumo et
al. 1977). The contour intervals are 0.2 eA -3 (a),
0.4 eA - 3 (b and c). Arrows show the threefold
axis in trigonal distorted oxygen octahedron.
The d.-orbitals (e~-levels) are perpendicular to
this axis, and their electron populations decreases in the series Ni-Co-Fe when the octahedron is compressed
picture. The chemical bond in Si-tetrahedrons of silicates have a predominant

covalent character with some n-components. In ring, chain, and framework
silicates, condensation of Si-tetrahedra results in the accumulation of electron density on the bridging oxygen atoms. Multicenter partially covalent
cation-anion chemical bonds are in corundum-type minerals (space group R3c).
An additional metal-metal bond can be formed in the basal plane (karelianite
V203) or perpendicular to this plane (hematite a-Fe 20 3) if the cation is at 3delement. The chemical bond nature in garnet oxygen polyhedrons is remarkable
for central atoms. Nontransition elements form ionic bonds with environment,
and transition and rare-earth elements form multicenter covalent bonds having
(J- and n-components.
The characteristics of fine crystal structure of minerals (real composition,
impurity distribution) can be studied by the X-ray diffraction method. They are
included into the crystallographic model by placing different atoms in the same
structure positions or by removing the atoms from others. Such a complication
76
of the crystal model results in correlations between refined structural parameters.

In order to weaken the correlation influence, one may either put restrictions on
the bulk chemical composition, optimize the model by a step-by-step fixation of
the population parameters, or refine the population parameters only with low
angle reflections, which are not affected by uncertainties in the other structural
parameters. The obtained parameters are model-dependent due to the approximate nature of the crystal model, and complication of the extinction effects
considerations, so additional criteria are needed. A criterion which is used to
estimate the reliability of results is a good agreement between the results of
chemical analyses and the chemical composition obtained from X-ray data
without restrictions on the chemical composition during the process of model
optimization. When the element composition of the minerals mark ably varies,
the chemical analysis has to be obtained from the sample used in the diffraction
experiment.
References
Gibbs (1982) Molecules as models for bonding in silicates. Am Mineral 67: 421-450
Kirfel A, Eichorn k (1990) Accurate structure analysis with synchrotron radiation. Acta Cryst
46: 271-284
Lewis J, Schwarzenbach D, Flack HD (1982) Electric field gradients and charge density in
corundum, IX-Al z0 3 Acta Cryst A38: 733-739
Marumo F, Isobe M, Saito Y et al (1974) Electron-density distributions in crystals of Ni zSi0 4
Acta Cryst B30: 1904-1906
Marumo F, Isobe M, Akimoto S (1977) Electron-density distributions in crystals of y-Fe zSi0 4
and y-Co zSi0 4 . Acta Cryst B30: 713-716
Sasaki S, Takeuchi Y, Fujino K, Akimoto S (1982) Electron-density distribution of three
orthopyroxenes, Mg zSi z0 6 , Co zSi z0 6 and Fe zSi z0 6 . Z Krist 158: 279-297
Spackman MA, Hill RJ, Gibbs GV (1987) Exploration of structure and bonding in stishovite
with Fourier and pseudoatom refinement methods using single-crystal and powder X-ray
diffraction data. Phys Chern Mineral 142: 139-150
Tsirelson VG, Ozerov RP (1994) Electron density and bonding in crystals. Adam Hilger,
Bristol
Tsirelson VG, Evdokimova OA, Belokoneva EL, Urusov VS (1990) Electron density distribution and bonding in silicates. Phys Chern Mineral 17: 275-292
2.1.8 High-Temperature and High-Pressure Crystal Chemistry

S.K. FILATOV and R.M. HAZEN
High-temperature, high-pressure, and compositional crystal chemistry are crystallographic subdisciplines devoted to studying the nature and causes of crystal
structure variations with changes in temperature (T), pressure (P), or composition (X). These studies, collectively called "comparative crystal chemistry", have
been conducted by materials scientists for more than 65 years, since the pioneer-
77
ing high-temperature X-ray diffraction studies of Wyckoff (1925), although the

past two decades have seen especially intensive research.
This review considers structural deformations which are common to all
crystals with changes in T, P, or X. We consider both continuous changes and
discontinuities (phase transitions) in lattice parameters and atomic coordinates.
Experimental studies of comparative crystal chemistry focus both on lattice
deformation, the external manifestation of changes, and at the atomic level
through studies of atomic coordinates, coordination polyhedral distortions, and
changes in interatomic distances and angles.
Powder and single-crystal X-ray diffraction are widely used to characterize
structural deformations and phase transitions of crystalline materials. Several
authors have summarized work at high T or P (Clark 1966; Buerger 1971;
Krishnan et al. 1979; Hazen and Finger 1982, 1985; Urusov and Pushcharovsky
1984; Taylor 1984-1988; Filatov 1990).
High-Temperature Crystal Chemistry
Three simple rules describe the basic features of thermal deformation of crystals.
Rule 1. The effect of temperature is scalar; therefore, thermal deformation of
a crystal is controlled by a structure and is described by a second rank tensor.
Rule 2. Anharmonicity of thermal oscillations of atoms results in an increase
in interatomic distances, i.e., in thermal expansion. More anharmonic oscillations with higher amplitudes, i.e., weaker bonds, result in more pronounced
thermal expansion.
Rule 3. An increase in crystal temperature is equivalent to an increase in the
intensity of thermal motion (vibrations, rotations, and jumps) of atoms and
molecules and gives rise to a chain of transformations whose tendency is toward
rising crystal symmetry: rising vibrational symmetry of atoms and molecules -+ deformation-structural rearrangement in the direction of rising symmetry -+ transformation into more symmetrical high-temperature modification.
The following regularities were obtained from a generalization of experimental data. They follow from the principles given above.
Deformations of Coordination Polyhedra. The mean linear coefficient of thermal
expansion, ci( ci = rty /3, where rty is the coefficient of volumetric expansion), of
a coordination polyhedron formed by essentially ionic bonds has simple reversible relations to Pauling bond strength (Fig. 7):
-
rt1000
1 ad
= ~ aT ~ 4.0(4)
(n) _
S2 ZcZa x 10
C,
(1)
where d is the cation-anion separation, n is the coordination number of the

cation, Zc and Za are cation and anion charges, respectively and S2 is the ionic
bond coefficient which is equal to ~ 0.5 for oxygen compounds. Thus, all types
of polyhedra with a definite cation and anion have the same parameter ci, which
78
t(S
points)
x
30
\\
II>
2S
c:
0
~\1+
\\ :
)(
20
4;~ 0
"0
l!,,~
IS
'" X
>- 0
'11
.J:.
Cl.
~
'"
0
0
la- 10
c:
+"
.-I
c:
0
'"
:::;;
.J:.'
~ ~
- co
e l
a Oxides 8. Silicates
x Halides
0
Carbides 8. Nitrides
Sulfides, Selenides, 8.
Tellurides
\ \
Co
(a)(S2ZxZa) = 4.0(4) X 10- 6
\~\ \
c:
..,"
.....
.......
-....;
.......
.......
-- ---.:::~
-0
0
0
0.2
0.4
0.6
f 1i
0.8
1.0
1.2
S2 ze Zo
n
Pauling Bond Strength
Fig. 7. The inverse relationship between polyhedral thermal expansion and Pauling bond
strength. (Hazen and Finger 1982)
can be used for predicting the effect of temperature on the polyhedron; fi. does
not depend on the structural bonds in the polyhedron. Furthermore, all coordination polyhedra with similar values of Pauling bond strength have a similar
coefficient IX. For example, in octahedra with divalent Ni,Mg,Co,Fe,Cd,Mn,
Ca,Ba, and Sr fi. 1000 = 14 1 x 1O- 6 C- 1 .
In a structure with more than one type of cation polyhedron, the effect of
temperature is proportional to a polyhedral size. However, thermal expansion of
a crystal is usually not just the simple sum of changes in the cation-anion
separation; changes in angles between polyhedra must be also considered.
The Intensity of Thermal Expansion of Oxygen Compounds with Oxyanion
Radicals. Strengths of crystals are limited by their weakest bonds. In oxygen
compounds with triangular and tetrahedral radicals, which compose nearly all
the Earth's crust, the bonds out of radicals are the weakest. Therefore, such
compounds are characterized by an increase in the thermal expansion coefficient, ex, and by a decrease in melting point, T m' with decreasing value of
79
a residual charge of one radical participating in bond formation in one space

dimension, Z. In general, this relationship is illustrated by Table 15; Z = Z/N,
where N is the number of space dimensions to form bonds out of polyions. For
example, N = 3 in silicates with isolated tetrahedra, 2 in chain and doublechain silicates, 1 in layer silicates; in frame silicates Z and N toward 0 but
Z moves toward 1.
The Character of Thermal Deformations. This is controlled by crystal symmetry
and crystal structure; thus, deformations of isostructural compounds and members of homological series are similar (for example, Fig. 8a-b, c-f). Cubic
crystals deform isotropically, while anisotropy of deformations of noncubic
crystals is determined by anisotropy of bond strength and by structural rearrangements, especially shearing of the structure.
Shears. The cell angles of triclinic and monoclinic crystals are not fixed by
symmetry; with changing temperature crystal structures are subjected to shears,

which are by nature highly anisotropic. Many oblique-angle crystals reveal
anisotropic thermal deformations, including a negative thermal expansion in
some directions.
Crystals with negative linear thermal expansion are uncommon in hexagonal,
trigonal, tetragonal, and orthorhombic materials, but in monoclinic and triclinic
crystals such an expansion is common. Note, however, that negative volumetric
thermal expansion is observed in few materials, except at temperatures near
absolute zero.
Oblique-angle crystals such as feldspars, amphiboles, many pyroxenes, and
micas, due to highly anisotropic deformations, are responsible for the decompression of the rocks which they make up, as well as for increases in rock
permeability by fluids and in some cases for the accumulation of ores under
metamorphic conditions. Higher thermal deformation anisotropy, for instance,
the anisotropy of calcic pyroxenes (Fig. 8a-b) relative to alkaline (Fig. 8c-f) is
suggestive of a higher capacity for thermal decompression of the rocks.
Similarly, highly anisotropic thermal expansion of calcite is responsible for
the thermal decompression of marbles; the anisotropy of feldspars, specially of
high albite, for the decompression of rocks bearing them; and a sudden change
in volume for 0.6% during rx-fJ transformation in quartz at the temperature of
573C is responsible in part for the decompression of granites, etc.
High-Pressure Crystal Chemistry

Three rules describe continuous structural variations with changing pressure for
most oxide and silicate minerals.
Rule 1. Changes in lattice parameters and atomic coordinates may be
characterized by second rank tensors. Lattice volume change with pressure is
constrained to be negative, and crystal axes almost always compress. (In
80
Table 15. Composition, structure, and thermal properties of oxygen compounds

Triangular radicals
Valency of the central atom
2+
4+
3+
(borates)
Tm
(carbonates)
!~
[T0 3 ]3-
[T0 3 ]2-
[T02.5r
[T0 2 ]2-
6+
[T0 3 r
[T0 3 ]0
[T0 3 ]+
Isolated
triangles
[T0 3 ]
[T02.5]O
[T02.5] +
[TO Z 5 ]2+
Double
triangles
[T Z 0 5 ]
[TO z ]+
[TO z ]2+
[TO z ]3+
Rings
[TO z ],
chains
[TO z ]",
[TO Z 5 ]2-
[T02.5r-
5+
(nitrates)
:x _ _
~,
[T0 3 ]4-
7+
Examples
of geometry
of polyions
[TOz]O
[T0 2 r
/
I
I
I
I
[ TO 1.75 ]1.5- [TO 1.75 ]0.5I [TO 1.75 ]0.5+ [TO 1.75 ]1.5+ [TO 1.75 ]Z.5+ [TO 1.75 ]3.5+ Double
I
chains
/
[T4 0 7 ]",
/
[T01.5]O
/
[TOx]Z is the formula of the radical on a one-central-atom basis; X is the extent of polymerization of
triangles or tetrahedra through common tops (X = O:T): Z is the radical charge available for bonds
out of the polyion; =0>, -+ are the basic tendencies of variations in strength of the compounds; ex is the
coefficient of thermal expansion; Tm is the melting point.
81
Tetrahedral radicals
Examples
of geometry
of poly ions
Valency of the central atom
2+
(beryllates)
4+
3+
(borates)
6+
5+
(silicates,
germanates)
(phosphates,
vanadates)
7+
(sulphates,
chromates)
(permanganates,
perchlorates,
perioates)
[T0 3 . 5 ]0
[TO;]O
/
I
I
I
I
Isolated
tetrahedra
[T0 4 ]
Double
tetrahedra
[T 207]
Rings
[T0 2 ],
'pyroxene'
chains
[T0 3 1o
[ TO 2.75 ]3.5- [TO 2.75 ]2.5- [TO 2.75 ]1.5- [TO 2.75 ]0.5I [TO 2.75 ]0.5+ [TO 2.75 ]1.5+ 'Amphibole'
I
double
chains
/'
/'
[TO u/' ]
/'
[T0 2]O
/'
/'
/'
/'
/'
/'
[T 4 0
11
J"
'Mica' layers
[T 2 0 5 ]oooo
'Silic'
frames
[T0 2 ]oooooo
LiALH
;;;"
0<./1
\
\
""-------~
,4
':i1
\_200
~.
ctJ.3
II,
.....
CaMg
\ ______?poC
a~"
-k
J+
-Y .
Nare
ex,,,
NaAL J +
,=-==
CY-"
~.--=-;;J!!!!! -~,
otJ3
Fig. 8a-f. The figures for the coefficients of thermal expansion of the ac plane in diopside (a), hedenbergite (b), spodumene (c),
ureyite (d), acmite (e), and jadeite (f). (After Filatov 1990). Each radius-vector represents the value of the coefficient of thermal
expansion in a given direction. Shaded areas correspond to negative thermal expansion
600-fOOO ...---',
400
p:
...,
~
~.
a:::
o....,
en
(1)
rl
'...,2"
~
...,
n
...,
t'"
<t
...,
'1:l
n
po
00
IV
83
LaNb0 4 one axis becomes slightly longer with pressure, but this expansion is
coupled to greater compression of a pseudo-orthogonal cell axis).
Rule 2. Cation-oxygen bond distances, d, show an average compressibility,
if (Fig. 9):
P- =
3) -6 bar -1 ,
ad ~ 0.044 (d
d1ap
S2ZcZa
10
(2)
where Sand Z are defined as above. Thus a given type of cation coordination
polyhedra (e.g., Mg0 6 ) displays similar compression in different structures.
Rule 3. Total volume compression of Il}ost rock-forming minerals is the sum
of polyhedral compressibilities, plus interpolyhedral compression related to
changes in cation-oxygen-cation angles. Polyhedral distortion (as characterized
by changes in oxygen-cation-oxygen angles) plays a minor role in mineral
compression below 100 kbar.
The driving force behind structural changes with pressure is volume reduction. Discontinuous structural changes involving increase in cation coordination are of special importance in understanding the Earth's deep interior.
Transformations, such as those of MgSi0 3 from pyroxene to garnet to perovskite, result in large density increases because of increased atom packing efficiency. Surprisingly, however, cation-oxygen distance generally increases across
such transitions (cation-anion distance increases with coordination number), so
high-pressure phases are often more compressible than their low-pressure polymorphs.
.......'... 2
III
.c
ICC
10
20
30
40
d3
50
60
70
Fig. 9. The bulk modulus-volume relationship for polyhedra in

a variety of materials. (Hazen
and Finger 1979)
84
Comparative Crystal Chemistry

The Analogy of the Variation of Volume with Temperature, Pressure, and Composition. Variation of coordination polyhedral volume can be predicted on the
basis of simple bond parameters: cation- anion separation (d), coordination
number of the cation (n), cation radius (r), cation and anion formal charges
(Zc and Za , respectively) and ionization (S2) :
I
IXv=-y
(av)
aT
(n)
~12.0 S2ZcZa xlO
-6 0
-1
(3)
(4)
(5)
where X is the atomic fraction of the larger cation.

All crystalline substances can be represented in T - P- X space by surfaces of
a constant molar volume (isochoric surfaces) (see, for example, Fig. 10). One of
the consequences of a structural analogy between T, P, and X is the fact that
isochoric surfaces for many substances are at the same time isostructural
surfaces in T - P- X space.
800
MgO
0.2
0.4
Fe/( Mg
0.6
+ Fe)
0.8
FeO
Fig. 10. Isostructural surfaces for (Mg,Fe)O in T- P- X space. (Hazen and Finger 1982)
85
Equations (3) and (4) lead to an important relationship of

a polyhedron (Hazen and Finger 1982):
0(//3 ~ 90 n/d 3 barre.
0(
to
/3
for
(6)
Deformations caused by T or P or X may reveal similar features. In

compounds with essentially ionic bonds, an increase in temperature causes
structural deformation similar to the effect of a decrease in hydrostatic pressure
(inverse relationships), or to the effect of isomorphic substitutions of smaller
structural elements for larger ones. Substitutions in highly anisometric positions
or occurring together with other disturbances in the quasi-scalar effect can result
in moderation of such a similarity or even in its absence.
Figure 11 shows examples of the similarity of thermal (b) and pressure (c) as
well as thermal (d) and chemical (e) deformations of clinopyroxene structures
caused by the transformations of the most "soft" (large and irregular) M2
polyhedron (a).
Fig. lla-e. Examples of the similarity of crystal deformations of various nature. (Filatov
1990). Compound~ with the clinopyroxene structure. a Coordination polyhedron M2 controlling the deformation of the crystal lattice. b Thermal-induced deformations of diopside.
c Pressure-induced deformations of diopside. d Thermal-induced deformations of vanadate
Li2 V206' e Chemical deformations of Li2 V206 (substitution Li-Na in M2). Arrows indicate
an increase in bond lengths, LlI, in M2 multiplied by 10 for thermal-induced and pressureinduced deformations and by 5 for chemical deformations. Figures of deformations are given
for the crystal lattice
86
The inverse relationship between thermal-induced and pressure-induced

deformations occurs if the ratio n/d 3 is similar for all cation polyhedra in the
crystal structure (Hazen and Prewitt 1977a) or if one of the polyhedra in the
structure is more rigid (for example, in silicates) compared to other polyhedra
with similar alP. Many cation polyhedra in rock-forming minerals have similar
alP ratios; all Mg, Fe2+, AI, and Fe3+ octahedra have alP ~ 65 barre. Therefore, many silicate minerals reveal inverse relationships, such as low albite
(Fig. 12b), diopside, and pyroxmangite. Rutile, on the other hand, being a compound with essentially covalent bonds, demonstrates the absence of inverse
relationships (Fig. 12c).
The Relationship Between Thermal Expansion and Lithostatic Compression of the
Earth's Shells. During subsidence into the depths from the earth's surface, the
rocks, being subjected to the contrary influences of pressure and temperature,

expand and compress simultaneously. The relationship between these two
components is controlled by the equivalents alP for minerals and by temperature and pressure gradients which are different at different depths.
The minerals of a single zone of the Earth have similar deformation equivalents alP. The average value of the equivalent alP for atmospheric conditions
through a zone (Fig. 13), increases with increase in (1) depth of the zone, h,
(b) rock density, p, (3) p-wave velocities within the zone, Vp , and (4) the mean
symmetry of the minerals of the zone, (T. It is apparent that the higher coordination numbers (n) of the atoms in the deep-seated phases [or shorter bonds
(d) with constant n numbers] determine their greater values of density and
deformation equivalent alP [see Eq. (6)].
There is experimental and theoretical evidence that the deformation equivalent alP increases with rise in pressure and increase in the depth of rocks in the
Earth. However, experimental data on the coefficients a and Punder conditions
of high temperature and pressure are insufficient at present to calculate the
values of alP for the minerals in abyssal zones.
IDEAL CASE
Structural Parameter
~creaSing
Pressure
Fig. 12a-c. To the problem of the "inverse" relationship between thermal- and pressureinduced deformations of crystals. a Ideal case, after Hazen and Finger 1982. b Example of the
inverse relationship in low albite (Hazen and Prewitt 1977b). c Example of the absence of the
inverse relationship in rutile, after Hazen and Finger 1981
87

LOW ALBITE NaAISi 30 S
111.0
Ul
Ql
Cl
Ql
116.6
Qi
-,
co
CD
116.2
::J
7.18
7.16
7.14
7.12
\jlYo
1.02
/lncreaSing Temperature
1.01
cIa
0.99
,/
./"
0.646
Y...
Vo 1.00
/
.
, Cryogenic
0.647
Temperatures
'ncreasing Pressure
"'-
'~
l(
~
III
::J
::J
(')
"C
0.98
Fig. 12. Contd.
Ul
88

50
'0
;(3
'>0
0
.t::
40
(J
.....
(/)
0
~
~
:l
c:
c:0
Q)
.!!!
"0
30
.0
I~
20
10
2900 km
40km
4km
10
h. km
60
1000
100
/(
40
20
3
p. g/cm 3
10
12
12
24
36
48
(f
Fig. 13a-d. Pressure equivalent of thermal deformation (rxIP), averaged on a mineral basis for
different zones of the Earth, as a function of depth to zone h (a), mean rock density under
atmospheric conditions p (b), P-wave velocities Vp within zone (c) and mean symmetry of
minerals in zone (J (d). (Filatov 1988). AI granite-metamorphic layer of continental crust;
A2 granulite-basite layer of crust; B upper mantle; C I transitional zone of mantle; C2 mantle at
depths of 600-800 km
In the deep-seated zones such a comparison can be made with the use of
approximate values a./p. With depth, expansion is slowed down as a consequence of a decrease in the temperature gradient with depth, the proportion of
compression increases.
Beneath the stable continental regions, the top of the upper mantle separates
a near-surface shell of intense cooling of the planet (we may assume that the
mean value of the temperature gradient with depth is approximately 20 DCjkm
near the surface and 10 DC/km at a depth of 40 km) from the quite thermostable
upper mantle, in which the temperature gradient may be taken as constant and
equal to 1.3 DC/km. The pressure gradient is also constant to a first approximation and may be estimated at 1/3 kbar/km. As a result, during the subsidence of
rocks in the upper mantle, a temperature increase of 1 DC appears to correspond
89
to a pressure increment of 1/4 kbar. This is 20 times greater than near the
surface, and an order of magnitude greater than at the Moho discontinuity.
Thus, the rates of pressure and temperature change with depth vary, and
their ratio may be estimated at 12 barre near the surface, 25 barre at a depth
of 40 km, and 250 barre in the upper mantle. The ratio of velocities equal to the
deformation equivalent for rocks of the upper mantle, a/f3 = 40-50 barre, is
reached between the Moho discontinuity and the stable portion of the upper
mantle, that is, in the top the upper mantle. This means that compensation for
thermal expansion by the lithostatic compression of the rocks is achieved at the
top of the upper mantle. During subsidence to greater depths, the rocks of the
upper mantle are subjected to a strongly rising pressure and are therefore
compressed. The effect of the slowly rising temperature may be neglected in
making approximate estimates.
Experimental data (e.g. f3 = 0.8 '10- 6 bar- i for diopside in the 0-53 kbar
range) have enabled us to estimate the average value of the coefficient of
lithostatic compression in the depth interval of 40 km (approximate pressure
10 kbar) to 320 km (110 kbar) for minerals of the upper mantle, at f3 = 0.5-0.7
(10- 6) bar-i. From this it follows that under conditions of relative constancy of
chemical and phase compositions, the density of the pyroxenes, olivines, and
garnets that make up the upper mantle increases monotonically during subsidence from 40 to 320 km by 5-7%.
In the transitional zone (320-400 km), compressibility as a result of PT
deformations turns out to be a minor factor compared to the effect of phase
transitions (apparently, pyroxene-garnet and 0Iivine-spinel-f3-Mg 2 Si0 4 (Ringwood 1975)), each of which is accompanied by a density increase of approximately 10%, and creates an important seismic discontinuity.
In the lower mantle, the pressure gradient increases to 1/2 kbar/km, and the
temperature gradient apparently does not exceed 1 e, and so the change in
parameters with depth exceeds 1/2 kbar per e (Ringwood 1975). This means
that compressibility in the lower mantle predominates over thermal expansion;
but compression as a result of phase transformations predominates.
Thus, volume and density of rocks change during vertical displacements in
the Earth, primarily as a result of phase transformations and to a lesser degree
owing to PT-induced deformation. During subsidence from the Earth's surface,
rocks subjected to the contrary influences of pressure and temperature expand
as a result of PT-induced deformation. With depth, expansion is slowed down as
a consequence of a decrease in the temperature gradient with depth and the
proportion of compression increases until compensation is reached at the top of
upper mantle. At greater depths, compression predominates. These volume
effects of deformation cause a monotonic change in the rock density with depth,
and although minor in magnitude compared to the effects ofthe numerous deepseated phase transitions, they make a substantial contribution to the change in
rock density in the absence of significant volume effects of phase transitions, for
instance in the stable inner portion of the upper mantle.
90
References
Buerger MJ (1971) Phase transitions. Kristallografiya 16: 1084-1096
Clark SP Jr (ed) (1966) Handbook of physical constants of rocks. Geol Soc Am, vol 97
Filatov SK (1990) High-temperature crystal chemistry. Nedra, Leningrad (in Russian)
Hazen RM (1977) Temperature, pressure and composition: structurally analogous variables.
Phys Chern Mineral 1: 83-94
Hazen RM, Finger LW (1979) Bulk modulus-volume relationship for cation-anion polyhedra.
J Geophys Res 84: 6723-6728
Hazen RM, Finger L W (1981) Bulk moduli and high-pressure crystal structures of rutile-type
compounds. J Phys Chern Sol 42: 143-151
Hazen RM, Finger LW (1982) Comparative crystal chemistry. London
Hazen RM, Finger LW (1985) Crystals at high pressure. Sci Am 252: 110-117
Hazen RM, Prewitt ChT (1977a) Effects of temperature and pressure on interatomic distances
in oxygen-based minerals. Am Mineral 62: 309-315
Hazen RM, Prewitt ChT (1977) Linear compressibilities of low albite: high pressure structural
implications. Am Mineral 62: 554-558
Krishnan RS, Srinivasan R, Devanarayanan S (1979) Thermal expansion of crystals.
Pergamon Press, Oxford
Mariathasan JWE, Finger LW, Hazen RM (1985) High-pressure behavior of LaNb0 4 Acta
Cryst B41: 179-184
Ringwood AE (1975) Composition and petrology of the Earth's mantle. McGraw-Hili, New
York (Russian translation, 1987, Nedra, Moscow)
Taylor D (1984-) Thermal expansion data. Br Ceram Trans J (1984) 83, 5-9, 32-37, 92-98,
129-133; (1985) 84, 9-14,121-127,149-153,181-188; (1986) 85,111-114,147-155; (1987)
86, 1-6; (1988) 87, 39-45, 88-95
Urusov VS, Pushcharovsky DYu (1984) The principles of high-pressure crystal chemistry.
Mineral Zh 6: 23-36 (in Russian)
Wyckoff RGJ (1925) The crystal structure of a high-temperature form of cristobalite (Si0 2 ).
Am J Sci 9: 448-459
2.2 Types of Structural Relations in Minerals

2.2.1 Modulated and Incommensurate Structures;
Spinodal U nmixing
N.!.
ORGAN OVA
The crystalline state of matter is realized by a perfectly periodic atom distribution in space and, as a rule, is thermodynamically stable. Natural and artificial
crystals, however, contain defects. Modulated structures can be regarded as a
variety of defect structures. The term modulated structure is used to describe any
periodic or partly periodic perturbation of a crystal structure with a repetition
distance greater than basic cell dimensions. The number and variety of the
known structural modulations is large. They can be commensurate or incommensurate depending on a multiple or nonmultiple relation between basic and
perturbated unit cell dimensions. A modulation can be longitudinal or trans-
2.2.1 Modulated and Incommensurate Structures
tttJj
91
tttjj~
~E
Fig. 14a, b. Two types of modulated structures. a Longitudinal modulation of one-dimensional lattice. I undisturbed unit cell; II modulated structure; III commensurate wave of
displacement. b Commensurate transverse wave of displacement. Above real; below reciprocal
space; M number of cells, multiple to large unit cell
versal, of a displacement or substitution, sinusoidal or triangular, or presented

by their combination (Fig. 14a, b). One can see in the reciprocal space (in X-ray
or electron diffraction patterns) strong spots from the starting structures
satellites (Fig. 14b, bottom). Distances between main (strong) reflections and
satellites are multiple for a commensurate case and irrational for an incommensurate one.
Intensities, number, and positions of satellites depend on the modulation law.
Only the first satellite order appears for a small sinusoidal perturbation; a larger
amplitude causes its number to increase. An evaluation of the intensity distribution in a reciprocal space permits determination of the modulation law.
Spinodal Decomposition
A long period modulation arises at the first stages of atom clustering which is
followed by phase unmixing with a spinodal mechanism. Indeed, the sinusoidal
compositional changes during ex solution spread as a rule along one crystallographic direction perpendicular to a constant composition plane which can be
considered as a one-dimensional substitutional longitudinal modulation. Electron diffraction patterns from such a crystal volume have satellites.
Thermodynamics Aspects
Theoretical consideration of a modulation for the incommensurated onedimensional conductors has shown an energy reduction of the electron system as
92
a result of the introduction of the displacement wave with energies near the
Fermi level. A universal phenomenological second-order phase transformation
theory explains the appearance of incommensurate and modulated structures.
Its initiation has been caused by the reduction of the free energy of a crystal close
to the transition temperature using an order parameter and group theoretical
approach.
Time-dependent order parameter theory allows the description by one
equation of both spinodal decomposition and order-disorder transition with
modulation.
A modulation state is as a rule transitional and nonequilibrium, and is an
object of nonequilibrium thermodynamics.
Methods of Study
Single crystal X-ray measurements are fruitful. Sometimes, however, electron
beam diffraction has been more effective. The immediate picture of the modulation can be provided by high-resolution transmission of electron microscopy
(HRTEM). Another technique include IR, NMR, and calorimetry. It is very
useful to accompany such measurements by changing temperature to find time
dependences.
It is possible to determine the kinetic laws of such processes. Modulated
structures have been determined and refined until now with usual crystallographic programs - separately for main and satellite reflections. A new approach
began by using four-dimensional (4-0) space by the introduction of the fourth
coordinate axis along the modulation direction. Programs for modulated 4-0
structures have been worked out. They can be used not only for modulated
structures but also for quasi-crystals and polytypes.
Examples of Crystals with Modulated Structures
There are many such structures among minerals (Table 16).
The diffraction patterns of intermediate plagioclase-An2s-An7s have satellites. Their arrangement changes depending on their composition. Comparison
between diffraction characteristics, composition, and high resolution electron
micrographs permits the connection of satellite appearance with different
Ca-Na distribution including their segregation. It can be considered as the first
stage of phase unmixing. An intermediate incommensurate phase of quartz
exists in the temperature interval of 1.3 K between p- and a-phases. Each of its
Bragg peaks is surrounded by six satellites. The modulation vector (0.033-0.029)
decreases with decreasing temperature and vanishes with transition to a-quartz.
The mechanism of such transformation has not yet been explained. According to
elastic neutron scattering data, the modulation has a wavelength of 125 A. At
847 K a first-order transition occurs, at 845.7 K a second-order transition.
2.2.1 Modulated and Incommensurate Structures
93
Table 16. Incommensurately modulated structures in minerals

Name and formula
of mineral
Modulation characteristics
Intermediate
plagioclase
(Ca,Na)(Si,AlhOB
Arrangement of satellites depends on composition and is connected

with different Ca-Na distribution
Nepheline
KNa3AI4Si4016
Intensities of reflections change upon temperature according to

vacances and K, Na, Si, AI-atoms ordering
Quartz
Si0 2
Intensities and coordinates of satellites change with temperature at

transition
Tridimite
Si0 2
Satellites at 150-190C depending on atoms displacements for

forming ditrigonal ring
Mullites
AI 2 SiO s
Iron akermanite
(Ca,FehMgSi 2 0 7
Satellite disposition is connected with ordering of AI, Si atoms, and

vacancies
There are three sorts of satellites changing intensities and disposition with temperature and composition and being connected with
ordering Ca and Fe
Hollandites
AB B(O,OH)16
Pyrrhotite
Fe1_xS
Irrational satellite disposition depends on large cations position in

cannals structure forming their own periodicity
Digenite-bornite
Cii9SS-CusFe-S4
Incommensuration arises from two types of clusters (with vacancies

or without them)
Proustite
Ag 3AsS 3
Incommensuration at temperature interval 45-210 K
Satellites are characterized by different laws in l.:stribution of Fevacancies
Kimrite, a Ba-alumosilicate with feldspar-like formula, contains double

hexagonal Si-AI-O- tetrahedral nets. Initial refinement was carried out with
ordinary programs and the modulation with period B = 4b was explained by
substitution of Si by Al in every fourth tetrahedron along the corresponding
direction. Ba atoms have transversal displacement along axis X. Repeated
refinement using the 4-D program has resulted in another model: every second
hexagonal net consists of Si- and AI-layers only. R- and temperature factors are
better for the second model. Only high-resolution electron microscopy can give a
final conclusion as to which version will be right. Electron diffraction patterns of
one pyrrhotite Fe 1 _ x S contain satellites situated with nonintegral spacing (1/5, 1Co)
along z*. High-resolution imaging of minerals has displayed a mixture of two
different domains - with C = 5C o and C = 6C o according to different vacancies
ordering. The diffraction pattern is the result of electron scattering from different
sorts of domains.
The layer structure of 2HTaSe 2 has been investigated with an electron
microscope. Its first-order phase transition during cooling was found at 124 K.
Satellites appear in the diffraction pattern. The second-order transition was
94

Fig. 15a, b. High-resolution
electron micrographs of
Bi- Sr- Cu- O ceramics with
incident electron beam
parallel to a the [100] and
b [010] directions. One can
see in a modulation wave
along y, of displacement
and substitution
found at 90 K. Within the temperature range 123- 90 K there are two stripe
systems. These stripes can be interpreted as different phases.
Examples of great theoretical and applied interest have been the hightemperature superconductor ceramics. All of them are layer structures with
interchanging layers of two types - perovscite- and rock-salt-like ones. For the
Bi- Sr- Ca- Cu- O system the crystal structure was investigated by both highresolution electron microscopy and diffraction (X-ray and synchrotron).
In Fig. 15 electron images of the structure of 2212 along two different
directions are shown. One can see modulation along axis Y - displacive and
substitution. Diffraction data have permitted the quantitative evaluation of
incommensurate modulation for every sort of atom. Four cations and one anion
have displacements with the different amplitudes and the same wavelength.
Hybrid mixed-layer structures are examples of incommensurate or commensurately modulated ones (see Chap. 2.2.2).
Conclusion
Modulated commensurate or incommensurate structures are important because
they usually represent an intermediate stage between two stable structures with
2.2.2 Hybrid Layer Structures, Commensurate and Incommensurate
95
either a periodic modulation of atoms and their ordering or their clustering

during unmixing. Their study will not only help to understand fundamental laws
of mineral building, but also to reveal a connection between structure and
microstructure peculiarities and geological conditions of their formation.
References
Buseck PR, Cowley JM (1983) Modulated and intergrowth structures in minerals and electron
microscope methods for their study. Am Mineral 68: 18-41
Carpenter MA, Salje E (1983) Time-dependent Landau theory for order-disorder processes in
minerals. Mineral Mag 53: 483-504
Cowley JM, Cohen ID, Salomon MV (eds.) (1979) Modulated structures. Proc Int Conf Am
Inst of Physics, New York, p 430
Dolino J, Becheimer JP, Berge CM, Zeyen E (1984) Incommensurate phase of quartz: I Elastic
neutron scattering. J Phys 45: 361-371
Makovicky E, Hyde BG (1981) Non-commensurate (misfit) layer structures. Struct Bond 46:
101-170
Morimoto N (1978) Incommensurate superstructures in transformation of minerals. Recent
Prog Nat Sci Jpn 3: 183-203
Organova NI (1989) Crystallochemistry of incommensurate and modulated mixed layer
minerals. Nauka, Moscow, pp 144 (in Russian)
Seifert F, Zank MC, Simons B, Sahmahl W (1987) A commensurate-incommensurate phase
transition in iron-bearing akermanites. Phys Chern Mineral 14: 26-35
Yamamoto A (1986) Refinement of polytype, modulated and quasi-crystal structures - higher
dimensional approach. Int Conf Poly type Modul Str Abstr, Wroc1aw, pp 16-17
2.2.2 Hybrid Layer Structures, Commensurate and

Incommensurate
R.
ALLMANN
Hybrid layer structures are composed of two kinds of differently charged layers,
which because of charge compensation exactly alternate in stacking direction.
The single layer ions may be silicates, hydroxides, sulfides, or chlorides with a
hexagonal or tetragonal (sub)structure. One of the two layers may even be
composed of isolated ions and water molecules only. Here we will confine
ourselves mainly to such compounds with hexagonal brucite-like layer cations
[Me(II)l-x Me(III)iOHhY+ (the main layers).
The most frequently occurring but negatively charged layers occur in
the well-known phyllosilicates and clay minerals, [A12 -xMgiSi4-yAlyOlo/
(OHh]<x+ y)- for instance, but these compounds are not called hybrid layer
structures, even though they obey the above definition.
In nature these two kinds of layer ions are counterparts in their ability to
absorb charged radicals at their surfaces and within the interlayers: the phyllosilicate layers bind cations (like K +), whereas the brucite-like layers bind anions
(e.g., CO~-). This capacity may even have triggered the polymerization of amino
96
and nucleic acids during the prebiotic evolution of life. As both layer types have
similar dimensions and opposite charges, they can even be combined to form
minerals of the chlorite group.
The most simple hybrid layer structures belong to the hydrotalcite (or
pyroaurite/sjogrenite) group. Hydrotalcite itself has the approximate formula
[Mg 6AI 2(OH)16]2+. [C0 3 4H 20]2-, but the amount x of the Al contents may
at least vary from 0.2-0.33. As Mg and Al are distributed statistically within the
octahedral sites of the main layer (avoiding direct AI-AI contact) and as the
interlayer is completely disordered (i.e., liquid-like), the lattice constants reflect
only the size of the octahedral site (ao '" 3.1 A) and the thickness of the double
layer package (c' '" 7.7 = 4.8 + 2.9 A) with c = 3c' because of the rhombohedral
stacking sequence ... BC. .. CA ... AB. .. BC ... of the OH-groups. In nature the
hexagonal sequence ... BC. .. CB. .. BC. .. is also found (mineral manasseite), but in
all laboratory syntheses until now only the rhombohedral. Another reason for
reflection broadening is turbostratic disorder, i.e. individual layer packets are
twisted against each other. Stacking was found with more or less disorder, i.e.,
the reflections 012, 015, and 018 are mostly broader than reflections independent
of the stacking mode (e.g., 003, 006, 110, and 113). In extreme cases, the stacking
sensitive reflections vanish completely.
The a o value varies with the AI-contents (for x = 0.25 ao = 3.07 A, for
x = 0.33 ao = 3.05 A). Mostly, x = 0.33 is the upper limit of the AI-contents, but
when using a pressure of 1 kbar during synthesis, x could be increased to at least
0.44. However because Al octahedra must then be directly connected, the
repulsion AI-AI will counteract the shrinking of the Me(OH)6 octahedra,
i.e., above x = 0.33 a o is about constant at 3.04 A.
As an OH-group connected to 1 Me(III) and 2 Me(II) has to balance a
charge of 13/6 + 22/6 = 7/6, the OH bond strength must be reduced from 1 to
5/6, i.e., these OH-groups must be involved as donors in hydrogen bonds
between main and interlayer with OH .... O '" 2.9 A. This is reflected in a
decrease ofthe wave number of v(OH) to about 3450 cm -1 and in a shrinking of
c' ( = 7.71 for x = 0.25, 7.60 for x = 0.33, and about 7.40 for x = 0.44). The
thickness c' can also be decreased by heating, as the interlayer water is zeolitic
and can be removed by heating up to 180C without destroying the structure.
The [Mg 1- xAl x(OHhY+ layer cation is remarkably stable in chemical
reactions. The AI-contents prevent solution in acids for PH > 4.5 and even for
smaller PH - values in a first step the CO~ - of the interlayer will be replaced by
the acid anion (e.g., CI-) before the solution of the main layer starts. This is the
reason why hydrotalcite is a much better antacid than magnesia (or brucite)
alone. Nevertheless, the carbonate forms are the most stable (and less reactive)
compounds of the hydrotalcite family.
Even oxidation and reduction of, for instance, Fe(II,III) in the main layer
may occur without destroying the layer. Thus, an iron brucite (Mg,Fe)(OH)2
with x = 0.19 Fe(II) changed in open air within 1 year to coalingite, in which
two slightly charged brucite layers alternate with one interlayer [C0 3 nH 20]
(c' = 12.6 A). The final product of this spontaneous oxidation and CO 2 uptake
will be pyroaurite, the iron analogon of hydrotalcite.
97
Recently hydrotalcite found much attention and application in industry,

besides as an antacid, mainly as catalyst (e.g., for aldol synthesis) and as fire
retardant additive to plastics (about 12 + 24 wt.% H 20 from H 20 and OH are
released up to 180 and 380C respectively together with 7 wt. % CO 2).
The variability of Me(II) and Me(III) in the main layer is rather great, with
Me(II) = Mg, Fe, Mn, Co, Ni, Zn, Cd, Cu, and Me(III) = AI, Cr, Mn, Fe, Co, Ni,
Ga. [AI 2Li(OH)6] + forms similar but ordered layer cations with a o = )33.1
= 5.2 A. If Me (II) = Ca, Sr or Ba, the size difference will be too great for
statistical distribution of Ca and AI, resulting in ordered main layers
[Ca 2AI(OH 6]+2H 20 with a = )33.32 = 5.72 A. The two water molecules
increase the coordination number of Ca to 7, as the Ca are shifted by about
0.57 A out of the center of their (OH)6 octahedron in direction to a water
molecule of the interlayer, which is bound somewhat more tightly than the
remaining water molecules. These Ca-aluminate layers are common constituents of hydrated Portland cements (e.g., [Ca4Alz(OH)12l [S04 (4 + 2)H 20]
with c' = 8.94 A, called C 3 A CaS0 4 aq in the short notation of cement nomenclature).
As interlayer cation nearly every cation may be incorporated, even large
organic anions like amino acids or naphtol-yellow-S, but the most stable
interlayer cation between Mg, Al main layers is CO; 2. The interlayer water may
be removed reversibly by heating to about 180C. Above this temperature,
dehydroxylation starts and is finished at about 380C, with an amorphous
phase as calcination product, which, at about 800 DC, turns to spinel.
Only if the interlayer is one atom thick, are the OH-groups of adjacent layers
opposite (e.g., .. BC .. CA .. AB .. BC .. ) and form nearly linear O-H .. O .. H-O
hydrogen bond systems. In wermlandite, [Mg 7 (AI,Fe)z(OH)18] [Ca(H 20)6
2S0 4 6H 20], the interlayers contain some supplementary cations and are
completely ordered (c' = 11.2 A) (see Fig. 16). With respect to the subcell with
a' = a/3 = 3.1 A, the OH sequence is .. BC .. BC .. Be. ... The (AI, Fe) are also
ordered at the threefold axes in 1/3, 2/3 and 2/3, 1/3 of the main layer. A similar
stacking is to be expected for the water-rich sulfate-hydrotalcite with
c' = 11.1 A. At lower room humidity this changes into a water-poor phase with
a' = 8.5 A. In contrast to wermlandite the sulfate-hydrotalcite seems to contain
no cations within the interlayer. Supplementary interlayer cations prevent
shrinking from 11.1 to 8.5 A.
Hydrotalcite was found as a first weathering product of basaltic glasses in
seawater, from which after half a year alumo-serpentine starts to form. When
hydrotalcite is treated with silica solutions at about 100C, alumo-serpentine is
only the first step in a reaction series, later yielding mordenite and as final stable
phases saponite and analcite. In soil formation also phases like hydrotalcite,
pyroaurite, and green rust (the Mg,AI, Mg,Fe, and Fe,Fe phases) play an
important role, but are often overlooked because of their small grain size (down
to some tOO A).
Probably the first polymerization of amino and nuclei acids occurred at the
surface of hydrotalcite-like phases. Even L- and D-forms seem to differ in their
resorption activity, as was found for histidine.
98
,
.1
c'
[o,l-fg
o--d
'
);).
AUe
o
I1g
Fig. 16. Structure of wermlandite. The OH(I) groups are bound to 3 Mg and form no
hydrogen bonds, whereas OH(2) and OH(3) are bound to 2 Mg + I(AI,Fe) and form hydrogen
bonds of OH ... 0 = 2.92 and 2.91 A respectively
In the above compounds the interlayers consist of individual ions and water
molecules and may be disordered, more liquid like as in hydrotalcite, or ordered
as in wermlandite. The interlayers, however, may be two-dimensional layer
cations by themselves, as the mica layer in chlorite. Both layers must have
numerically the same, but opposite charges per unit area; but it is not necessary
that they fit together geometrically. If they do not, incommensurate hybrid layer
structures are formed, Their diffraction patterns look like a superposition oftwo
independent patterns with only the 001 reflections in common, to which both
substructures contribute coherently,
As a commensurate layer anion the mica layer of chlorites was already
mentioned. Another kind of silicate layer was found in vertumnite,
~ [Ca 2 AI(OH)6J +. [Si30sH3' 2H 2 0 r (c' = 12.56 A.), with Si 4 0 s double
layers as in HT-Celsian, in which about 25 to 33% of the tetrahedral sites
remain empty (Si + 4 -> 3H +). Similar interlayers were also found with Mg,AImain layers (c' ~ 11.94 A.).
More interesting are the incommensurate hybrid layer structures with
chloride or sulfide interlayers, such as koeneite, valleriite, and tochilinite.
Koenenite occurs in salt deposits and has the approximate formula
[Mg 7 AI 4 (OHbl [Ca 2 Na 4 Cl 12 J. The lattice constants are a OH = 3,05, aCt
= 4,07, c' = 10.88 A with C OH = 3c' and C CL = c', The angle between a OH and aCt
is 28.3 (Fig. 17). No superstructure reflections common to both lattices could be
99
{13,5.0j
{13,5,O}
.{too],.
Fig. 17. Possible but not proven supercell for koenenite. Left for chloride partial structure;
right for hydroxide partial structure
detected. The ratio OH:Ci is fixed by aEl:a~)H = 1.78 and may vary only slightly
with changing composition of the chloride layer: some Ca can be replaced by
Mg and 2Na + by Ca 2 + + D, yielding an end member [Ca 4D 2CI12]. Such Na-free
koenenites could be synthesized at 200-400C. The chloride layer is very
sensitive to humidity and mechanical stress. Even short grinding yields separate
NaCI, and by humidity the chloride layer will be destroyed, leaving only 4 CI in
the interlayer, which are needed for charge compensation of the stable hydroxide layer. Only storage in concentrated MgCl 2 or CaCl 2 solution will prevent
koenenite from decomposition.
Valleriite is a graphite-like bronze-colored sulfide-hydroxide mineral,
~ [Mg2AI(OH)6l(Fe,Cu)4S4J, with a OH = 3.07, as = 3.79, c' = 11.37 A. Here
aOH and as have the same direction. The ratio OH: S equals a~ : a~)H = 1.52 and
may vary from 1.47 to 1.71. Within the sulfide layers (Fe,Cu) occupies all
possible tetrahedral sites.
Even more exciting is the structure of tochilinite, ~ [Mg 3 . sFe1.5(OH)lOl
[FeS.4Do.6S6J, which was found as a main constituent of corbonaceous chondrites. Here the pseudo-trigonal hydroxide layers are interleaved by pseudotetragonal mackinawite-like sulfide layers with c' = 10.68, a'OH = 3.11 and a's
= 3.75 A. For tochilinite I a common supercell was reported with a = 5.37
= J3'a OH = J2'a s , b = 15.65 = 5'a OH = 3J2as , c = 10.72 A, a = y = 90,
fJ = 95, space group Cl. But for tochilinite II (with about 4.8 instead of 5.4 Fe at
the six tetrahedral sites of the sulfide layer), both layers are incommensurate
(OH: S in both cases about 1.67, but values from 1.61 to 1.75 were found also for
other tochilinites) (Fig. 18).
This alternation of hexagonal and tetragonal layers was also found for
several pure sulfide structures. Both layer types can be deduced from the PbS
structure (a = 5.94 A), cutting this parallel 111 to obtain a hexagonal layer H
with formula Me n- 1 Sn (thickness about n' 3.2 A) and parallel 100 to obtain a
tetragonal one (T, formula MeS, thickness per atom about 2.9 A). Both layers
have the direction [O-11J (d(110) = 4.20 A) in common, but the perpendicular
directions [ - 211J and [OllJ resp. have an incommensurate ratio of
1
J3:
100
5 (Fe, Mg) (OH)2
o
10.8 A
6 (Fe, NI, Cu) 5
5 (Fe, Mg) (OH)2
(A)
Fig. 18. Structure of tochilinite
[Mg 3.s Fe1.5[OH] [Fe s .4 S6 ]
ox+
8000 2
Fig. 19. Ideal scheme of H- and T-Iayers in cannizzarite. Only one T-Iayer is shown above.
I metal atoms; 2 sulfur atoms (different symbols correspond to different heights)
= 1.732 ,...., 3: 5 or 4: 7 (Fig. 19). A good example is cannizzarite, ,...., Pb 3 Bi 4

(S,Se)9 = MeS0.587Me 2 S3 , with the following lattice constants: T: a = 15.48,
b = 4.09, c = 4.13 A, f3 = 98.56, and H: a = 15.46, b = 4.09, c = 7.03
= )3'4.06 A, f3 = 98.0, layer thickness a' = 15.31 ,...., 2,2.9 + 3,3.2 A, Ch:CT
= 1.70,...., )3. The misfit of both layer types may lead to bent layers as for
cylindrite, ,...., FePb 3 Sn4 Sb 2 S14 = 2MeS' 1.45MeS 2 , with a' = 11.71 ,...., 2 2.9
+ 2 3.2 A. Other minerals of this kind are inkaite, potosite, and frankeite.
References
AHmann R (1970) Doppelschichtstrukturen mit brucitiihnlichen Schichtionen [Me(II)l-x
Me(lII)x(OH)],+. Chimia 24: 99-108
Aslani-Samim S, Lohse H-H, AHmann R, Schiirmann K (1985) Koenenite synthesis within the
system MgO-AI203-NaCI-MgCI2-CaCI2-H20. Neues Jahrbuch Mineral, Mh 497-507
101
Barber DH (1985) Phyllosilicates and other layer-structured materials in stony meteorites.

Clay Mineral 20: 415-454
Ikeda T, Amoh H, Yasunaga T (1984) Stereoselective exchange kinetics of L- and D-histidines
for Cl- in the interlayer of a hydrotalcite-like compound by the chemical relaxation method.
J Am Chem Soc 106: 5772-5775
Kuma K, Paplawsky W, Gedulin B, Arrhenius G (1989) Mixed-valence hydroxides as bioorganic host minerals. Origin, Life Evol Biosphere 19: 573-602
Miyata S (1983) Anion-exchange properties of hydrotalcite-like compounds. Clays Clay
Mineral 31: 305-311
Organova NI, Drits VA, Dmitrik AL (1973) Structural study of tochilinite, part I Sov Phys
Cryst 17: 667-671; part II (1974) ibid 18: 606-609
Rius J, Allmann R (1984) The superstructure of the double layer mineral wermlandite. Z Krist
168: 133-144

S. TURNER, A.1. GORSHKOV, and P.R. BUSECK
Among the many diverse structural arrangements that occur in minerals, there is
a large group of structures containing tunnels or channels. These tunnels are in
some cases vacant and in other cases occupied by molecular ionic species, large
cations, or water molecules. The tunnel-structure minerals include, for example,
silicates with broad channels that are rectangular in cross section (sepiolite and
palygorskite) and silicates with channels with more equidimensional cross
sections (zeolites). The oxides of AI, Fe, Mn, Ti and some other elements
encompass a wide variety of tunnel structures. Study of some of these oxides by
high-resolution transmission electron microscopy (HRTEM) has revealed a
variety of new structural types and has shown the occurrence of coherent
intergrowths between related structures.
Much attention has been given to the study of the tunnel-structure oxides,
not only as a result of their abundance in nature but also because of their present
and potential practical applications. Among the more significant applications
are their use as the cathodic material in dry-cell batteries, and their potential
uses as (1) ionic conductors, (2) as material for disposal ofradioactive waste, and
(3) as sources of transition metals in manganese nodules. For many of these
applications, detailed knowledge of the structures of the materials is important.
The basic structural unit of the tunnel oxides is an oxygen octahedron with a
cation in the center (the octahedral site). An octahedron can be linked to another
octahedron by sharing a common edge formed by two adjacent oxygens. Many
octahedra can be linked together in this manner to form a larger unit termed a
chain of octahedra. A chain has a width of one octahedron and a length that,
unless interrupted by defects, is limited only by the dimensions of the crystal in
which it occurs. These chains can, in turn, be linked to one another to form
larger units by sharing edges. These multichain units will here be termed
"ribbons".
lO2
Ribbons are connected to one another through shared apical oxygens to

form three-dimensional frameworks that have tunnels that are parallel to the
lengths of the octahedral chains. The various tunnel-structure oxides differ in
tunnel cross-sectional dimensions (as a result of differences in octahedral ribbon
width), in the arrangement of tunnels, in their compositions as well as in the
composition and ordering of the tunnel contents.
For a large subset of tunnel-structure oxides, octahedral ribbons are linked
to form square or rectangular tunnels. This linkage leads to the formation of two
distinct channels in the structure as can be observed in the sketches of Fig. 20.
The structures can be described by the number of octahedral chains defining the
cross-sectional dimensions of the two tunnels. The structures can be represented
by the notation [ml x n l ; m z x n z], where m and n are the dimensions of the
tunnels expressed in units corresponding to the number of octahedral chains in
the ribbons. The subscripts 1 and 2 denote the larger and smaller tunnels,
respectively. For many structures, the second tunnel has dimensions that
correspond to one octahedron (or a 1 x 1 cross section). For these cases, it is
necessary to report only the dimensions of the first tunnel.
The tunnel structure type designated by [1 x 1] contains only one type of
tunnel (Fig. 20a) and includes the rutile-group minerals - rutile (TiO z), pyrolusite (p-MnO z), stishovite (SiO z), cassiterite (SnO z), paratellurite (TeO z ), and
plattnerite (PbO z). These structures consist of single octahedral chains oriented
along the c axis. The adjacent chains are linked to one another so that vacant
tunnels are formed along [001]. The unit cell is tetragonal.
Another type of tunnel structure type containing only one type of tunnel is
denoted [1 x 2; 1 x 2] (Fig. 20b). The basic structural unit is a ribbon consisting
of two octahedral chains. The ribbons are linked together by octahedral apices
to form 1 x 2 tunnels. The ribbons are nearly parallel to one another. The
structure is characteristic of diaspore (AIOOH), montroseite (VOOH), goethite
(()(-FeOOH), groutite (()(-MnOOH), and ramsdellite (MnO z).
Structures denoted as [2 x 2] are characteristic for isostructural hollandite,
cryptomelane, and coronadite, having the common formula Az-yBSX16 (A
= Ba, K, Pb: B = Mn4+, Mn3+; X = 0, OH) as well as for priderite [(K,Ba)
(Ti,Fe)s016] and akaganeite [p-FeO(OH,CI)]. For this case, double-chain
octahedral ribbons are linked to from narrow 1 x 1 tunnels as in rutile and larger
tunnels with dimensions twice those of rutile (Fig. 20c). The larger tunnels
contain Ba, K, Pb, or Cl ions or HzO molecules. The symmetry of hollandite
type structures may be either tetragonal or monoclinic depending on their
compositions.
The [2 x 3] structure, consisting of double- and triple-chain octahedral
ribbons (Fig.20c), is observed in the case of romanechite (Ba,HzO)zMns0 10
(Ba: HzO = 1: 2). Its tunnels are wider than those in hollandite and are occupied
by two strings of Ba cations and HzO molecules.
The four structures discussed above were determined by use of single-crystal
X-ray diffraction (XRD). Application of HRTEM to some manganese oxides has
revealed a variety of new structural types for the tunnel-structure oxides and has
103
Cl[JI
e
Fig. 20a-h. Examples of octahedral-tunnel structures: a Rutile. b Ramsdellite. c Hollandite.

d Romanechite and e-h Various todorokite structures
shown the occurrence of coherent intergrowth between similar structures. The

new structural types are closely related to the four structures of Fig. 20a-d. For
example, the mineral todorokite contains structures denoted as [3 x 3J, [3 x 4J,
[3 x 5J, etc. These structures consist of manganese oxide octahedral frameworks
that form large tunnels with triple-chain ribbons for one dimension. Several of
the structures are illustrated in Fig. 20e-h in which a triple-chain (Fig. 20e),
quadruple-chain (Fig.20f), quintuple-chain (Fig.20g) or septuple-chain
104
(Fig. 20h) ribbon forms the second dimension of the tunnel. The tunnels can
contain Na, Ca, and K cations and H 20 molecules.
Coherent intergrowth between related structures is possible if a common
dimension or structural unit is present. Use of HRTEM has provided confirmation of the suspected coherent intergrowth of pyrolusite and ramsdellite type
structures to form an intergrowth material termed nsutite (y-Mn02)' New
I
......1;;;.:0
2242222224 2322
3223232222322
533
1 1
.1
~"'IIlJ~L~:I1~ ....~[fI~,~",l't'. . .ali'i8~I ~ i
t t.: I. I
(~ .... :J. [ [ I. I. 1
4323233343333
Fig. 21a-c. HRTEM images of manganese oxide intergrowth structures (scale bar = 2 nm for
all images) a Hollandite-romanechite intergrowth viewed down the tunnel direction. b
Hollandite-romanechite intergrowth with included [2 x 4] structures viewed perpendicular to
the tunnels. c Todorokite intergrowth viewed down the tunnel direction. (Turner and Buseck
1979, 1981)
105
structural types occurring in small domains or defects have been observed in

nsutite including those designated [1 x 2], and [1 x 3; 1 x 2]. Additionally, use of
HRTEM has demonstrated the coherent intergrowth of hollandite and romanechite structures as shown by the image of Fig. 21a. New structural types noted in
this intergrowth material include [2x 4] (Fig. 21b) and [2x 7] structures.
Finally, the structural types of todorokite have been found to occur exclusively
as intergrowths in which the triple-chain ribbon of the tunnel structures are
shared (Fig. 21c).
The variety of structural types that have been found for the manganese
tunnel oxides can be classified into three families based on the common tunnel
dimension formed by either single-chain, double-chain, or triple-chain ribbons.
The single-chain family includes structures that can be represented as [1 x n;
1 x n] such as pyrolusite and ramsdellite. The double-chain family consists of
[2 x n] structures such as hollandite and romanechite. The third family consists
of todorokite or [3 x n] structures. This classification system encompasses the
known manganese-oxide tunnel structures and suggests the possibility of a series
of related structures. For example, a recently described synthetic manganese
oxide, Rbo.27 Mn0 2 , falls into the hollandite-romanechite group and has a [2 x 5]
structure.
All of the previously discussed structures occur in the manganese oxides. The
number of tunnel oxides known thus far for materials with AI, Fe, Pb, Sn, Te, Ti,
or V in the octahedral site is limited. Continued application of both XRD and
HRTEM techniques should more fully delineate the range of structural possibilities of the tunnel-structure oxide minerals.
References
Burns RG, Burns VM, Stockman HW (1983) A review of the todorokite-buserite problem:
implications to the mineralogy of marine manganese nodules. Am Mineral 68: 972-980
Chukhrov FV, Gorshkov AI, Drits VA (1989) Hypergene manganese oxides. Moscow, Nayka
Liebau FL (1985) Structural chemistry of silicates. Berlin, Springer
Post JE, Von Dreele RB, Buseck PR (1982) Symmetry and cation displacements in hollandites:
structure refinements of hollandite, crystomelane and pride rite. Acta Crystallographica B38:
1056-1065
Tamada 0, Yamamoto N (1986) The crystal structure of a new manganese dioxide
(Rb o.27 Mn0 2 ) with a giant tunnel. Mineral J 13: no 3, 130-140
Turner S, Buseck PR (1979) Manganese oxide tunnel structures and their intergrowths.
Science 203: 456-458
Turner S, Buseck PR (1981) Todorokites: a new family of naturally occurring manganese
oxides. Science 212: 1024-1027
Turner S, Post JE (1988) Refinement of the substructure and superstructure of romanechite.
Am Mineral 73: 1155-1161
106

A.G. CHRISTY and B.B. ZVYAGIN
The term polytypy (Polytypie) was coined by Baumhauer (1915) to describe a
special type of polymorphism found in silicon carbide. The SiC polymorphs are
unusual in that all of them can be described as stackings of topologically similar
SiC layers. The nearest neighbor coordination is tetrahedral about both Si and
C in all structures. There is little difference in enthalpy, entropy, or molar
volume between the polytypes. Concomitant with this fact, a large number of
different regular stacking patterns are known. Some of them have extremely
large lattice repeats ( > 1500.4.) along the stacking axis. Parallel intergrowth of
different polytypes and stacking disorder are also well known.
Similar behavior was soon discovered in a variety of other materials. These
"classical polytypes" are stoichiometrically simple compounds: elements (graphite), AB binaries such as ZnS, and AB2 compounds such as MoS 2, CdI 2, and
PhI 2. Around 200 different regular structures are now known for each of ZnS
and CdI 2.
Hendricks and Jefferson (1934) noted that a similar style of polymorphism
also occurred in the micas (although they credit Linus Pauling with having
anticipated this possibility). Although the layered nature of the mica structures
is still very apparent, they are structurally and chemically far more complex than
the classical polytypes. A few more examples of polytypy in minerals are cited in
the monograph by Verma and Krishna (1966).
In the last 25 years, it has become apparent that many mineral structures
can be regarded as stackings of layer modules, or indeed as two-dimensional
stackings of prismatic modules. A given pair of such modules can often stack
together in more than one way whilst still satisfying local bonding requirements
at the module interfaces. The description of a structure in terms of module
stackings can therefore be important in the understanding of both polymorphic
variation and structure defect behavior.
Several different degrees of structural freedom can be involved in modular
stacking variation. This has led to proliferation of the terminology used to
describe modular structures, but has also inspired attempts to classify them
hierarchically. At present, polytypism has not been rigorously defined. There is a
continuum between the simple stacking behavior of the classical polytypes and
a variety of types of structural variation which are not usually described in
polytypic terms.
The Scope of Polytypism
Because different polytypes of a substance are very similar in their local

topology, their relative stability can be extremely sensitive to small variations in
107
chemistry. Nonstoichiometry and impurities are now known to have a significant effect on the occurrence of SiC polytypes at even the parts-per-million level.
In view of this fact, an IMA/IUCr joint committee on nomenclature distinguished polytypism from polymorphism on the grounds that specific structural modules are present and small chemical differences were permitted
between polytypes. The term polytypoid was to be used for materials differing
in composition by more than 0.25 atoms per formula unit in any element.
Angel makes the point that any such distinction is arbitrary, and may prove
inconvenient when discussing the extensive solid solutions characteristic of
mineral systems. He recommends that polytypism be seen as a geometrical
relationship between structures that are composed of topologically similar
modules, irrespective of chemistry.
Thompson (1981) defines polytypes as isochemical stackings of "structurally
compatible" modules, and gives the relationship between chlorite and serpentine
structures as an example. However, these structures have different building
modules 2: 1 : 1 and 1 : 1 (more correctly, 2: 1 + 0: 1), and should be considered as
polymorphs although they are similar in energy and physical properties, and
natural examples of intermediate stackings are known.
Stacking change which preserves composition and stoichiometry is seen as a
special case of a wider class of structural variation, termed polysomatism by
Thompson, in which modules of distinctively different chemistry stack together
in different proportions. Thompson's (1978) terminology is retained here, although Angel (1986) advocates that "polytypism" be extended to embrace
polysomes as well.
Another type of stacking variation occurs when different modular structures
have at least one atom in a different nearest-neighbor coordination. This is the
case for TaSe 2, in which a given layer may have Ta in octahedral coordination
(as in the CdI 2 polytypes) or in trigonal prismatic coordination, as in molybdenite. The spinelloids have structures derived from that of spinel by 1/2 [001]
translation on (110). This causes condensation of the isolated tetrahedra found
in spinel to produce pairs or longer chains, for instance:
2 [Si0 4 ]
--+
[Si 20
7]
[0]
y-Mg 2Si0 4 P-Mg 2Si0 4

This condensation can also occur on two {11 O} planes related by a tetrad. This
gives rise to cyclic Li 4 0 12 tetramers in Li2 W0 4 -II. However, such an extension
is unjustified. The extended "polytypism" would cover a number of other terms
already introduced for different kinds of modular structures (MS), making them
redundant. The different kinds of MS are distinguished from one another by the
distribution of and stacking rules for the building modules (BM). "Topological
similarity" of BMs is defined by topological features of coordination polyhedra
and their recurring combinations, while size and shape variations may depend
on compositional differences. The composition may be fairly constant as in ZnSand kaolinite modifications, or variable as in mica- and serpentine modifications
Table 17
Layers
Blocks
Succession of adjacent
modules
Module sequence order
Module proportions
Different:
Polysomes
Modules
Ambiguous
Periodic
Variable:
Mixed-layer structures
("Polytypes III")
Modules: fragments of one

or different structures
Rods
~----~----~I
Dimensionality of modules (2-, 1-,0-)
Single module str1uctures ("Polytypes - Type I")
I
I
Rods
saje
--- ------
Constant:
("Polytypes II")
I
Unambiguous:
Hyt dS
Aperiodic
One:
Monosomes
Different
Blocks
Mixed modile structures
-----~
I
Layers
Modular structures ("Polytypes")
::r
en
~.
o
-,
en
(")
...,~
'<
en
(j
...,
!'"'
...,
"Sa
<>
I>'
(j
00
,-
Homogen.:
simple
polytypes
Periodic
Inhomogen.:
complex
polytypes
Aperiodic
-,
Homogen.:
MDO ODstructures
Periodic
Inhomogen.
Aperiodic
Sequence of
stacking
variants
Stacking variants
succession
Symmetry equivalence of pairs

of adjacent modules
~---'I
Equivalent:
OD-structurr
Unambiguous:
inhomogeneous
module sequences
Crystallochemical equivalence
of module stacking variants
mod"'"
Stacking of adjacent
Nonequivalent
Unambiguous
Nonequivalent
Equivalent:
Polytypes
Ambiguous
Aperiodic
Homogen.:
MDO ODstructures
Inhomogen.
,----1
Periodic
I . -
Nonequivalent
I I
Periodic
Inhomogen.:
complex
poly types
Aperiodic
Nonequivalent
~
Homogen.:
siinple
polytypes
Equivalent:
Polytypes
I
module sequ~
-
Ambiguous
homogeneo~:nces
Unambiguous:
Equivalent:
OD-structures
Ambiguous
tv
en
5'
...,'"
5'
~.
"0
-<
-<
'"0
:.,.
110
serving then as a factor for realization of a definite modification. Hypothetical

structural modifications of a given composition are readily constructed, and
may subsequently be found to exist.
The relationship between different kinds of MS is shown in a scheme
constructed according to principles similar to those used by Angel (Table t 7).
This scheme defines the special position of polytypes and illustrates the vague
sense of different "types of polytypes" introduced by Angel (the corresponding
terms are given in quotation marks).
Some branches of this scheme will not be discussed because their continuation is beyond the scope of this text. In particular, the unambiguous homogeneous module sequences and homogeneous polytypes may be further divided
into categories which were introduced by Dornberger-Schiff for MDO ODstructures. Several members of the scheme need comments. Thus, mono somes
exist among hexagonal Ba-ferrites which contain spinel-magnetite slices of
different thicknesses. An unambiguous stacking of adjacent modules is a feature of high-Tc superconductors and layer sulfide semiconductors (A, B)mSm+ 1
(A, B = In, Ga, Zn ... m ~ 3).
According to the determinative features indicated, there is a hierarchic
sequence of notions: modular structures - polysomes, mono somes - hybrids polytypes - OD-structures. In particular, chlorites, consisting of alternating 2: 1
and 0: 1 layers (i.e., mica-pyrophyllite and brucite-gibbsite layers, respectively)
belong simultaneously to mixed-layer polysomes .and hybrids, and may form
polytype and OD-families. It is seen that OD-structures are at the same time
polytypes, but not all polytypes have OD-structures.
Dornberger-Schiff, Durovic, and Weiss have shown in a number of publications that many apparent "pure" polytypes may be considered as ODstructures with another choice of building layers, usually by increasing the
number of the layer kinds (e.g., three OD-layers instead of one "polytype" 1: 1
layer of the kaoline minerals).
Although much of the stacking variation which occurs in different structure
types can be described in OD terms, many cases are known in which this cannot
be done. Molybdenite is the simplest example. Its building layers MoS z are
composed of trigonal prisms MoS 6 sharing lateral edges. The layers are closepacked, may have two opposite orientations, and form layer pairs that are
symmetrically nonequivalent in different polytypes (Fig. 21). Hence the molybdenite structures are polytypes but not OD-structures.
The aluminum hydroxides are another example of a non-OD polytypic
system. The AI(OHh polymorphs are all constituted from the same type of MX 3
layer, in which one third of the octahedral cation sites are vacant. In bayerite
and doyleite the anions form a hexagonal close-packed array. The two phases
are distinguished by their different distributions of vacant cation sites. However,
gibbsite and nordstrandite have the anion layer packings AABBAABB
and AABBCC respectively, indicative of strongly directed interlayer hydrogen
bonding which is not present in the other two phases.
The term poly tropism was recommended by Ghose for a special type of
polytypism found in the hilgardite (CazBsOgCl) family of borates. Chiral
111
Fig. 21. Two molybdenite polytype structures (both 2H) composed of prismatic building
layers divided by octahedral interlayers
[B 5 0 12 J mOIetIes are cross-linked into a [B509J framework in which the

component borate chains have distinct polarities along x and y. The naturally
occurring phases have different sequences of dextro and laevo sheets parallel to
(100). Stacking operations which mayor may not invert the polarity of a module
along the stacking axis are not permitted by the 00 vicinity conditions.
Polytropic systems such as the hilgardites fall therefore outside OD-structures.
Polytype Nomenclature
The profusion of possible structures in poly typic systems renders it pointless

to apply trivial names or simple numbering schemes to different phases. Two
IMAj IUCr committees have provided guidelines for nomenclature. Their recommended system is consistent, compatible with those used by many early
workers, and with the symbology of 00 theory.
There are two distinct styles of polytype symbol. Indicative symbols are a
concise (but not necessarily unambiguous) label for a structure. Descriptive
symbols explicitly define the stacking relationships between modules, and are
simple and powerful means for operations with polytypes and their derivation.
The indicative symbology recommended by Guinier (1984) is based on those
of Ramsdell and Gard, and conveys both periodicity and crystal system or
lattice type. For example, wurtzite is ZnS-2H, and sphalerite is ZnS-3C. Changes
112
in axial setting, or stacking variation or disorder in more than one direction can
be shown by using a more extended form of the symbol, as in xonotlite-Ma d 2bc.
The "ABC" notation for close packings is a simple example of descriptive
terminology. It is in fact somewhat redundant for close-packed structures and
their simple derivates (e.g., SiC, ZnS) since these structures have only two
distinguishable stacking vectors. Hiigg represented these as " + " and" - ", so
that the 2H structure is represented [+ - J and the 3C structure, [+ + + J
or [- - -]. Zhdanov (1945) condensed this notation by replacing strings of
one sign with the length of the string. 2H and 3C are then [1J2 and [00 J
respectively. A complementary notation developed independently by Ewald and
Hermann, Pauling and Belov uses hand k (or c) to denote layers which lie
between different and similar Hiigg signs (similar or different letters A, B, C)
respectively, indicating the local analogy to hexagonal and cubic close packings.
The micas, with six possible stacking vectors in each layer, require more
complex symbology. Zvyagin indicates absolute orientation of successive layers
enumerated from 1 to 6 (Fig. 22). Ross et al. use 0, 1, 2, 3 to indicate the
relative rotation between layers. The 2M! polytype of Smith and Yoder (1956) is
then (2 2), whereas 2M2 becomes (1 1). Thompson (1981) replaces these integers
by symbols emphasizing the local symmetry operators.
The 1: 1 phyllosilicates, the 2: 1 talc/pyrophyllite and the (2: 1 + 0: 1)chlorite minerals, are structurally more complex than the micas in that the
Fig. 22a, b. Scheme of two adjacent sheets (T- and 0-) in the normal projection on the plane,
ab, displaying six choices of axes a i which being parallel to a common axis, a, define possible
azimuthal orientations of phyllosilicate layers
113
30
1:[
2T
20,toH
2 M J+ (3M 2 +)
30H
0:1_
Fig. 23. Scheme of phyllosilicate layers 1: 1,2: 1 and of the combination 2: 1 + 0: 1
Fig.24. Vectors of intra- and interlayer displacements of consecutive

sheets (T-O- and O-T-)
positions of adjacent layers (Fig. 23) are determined by H-bonding (between 1: 1

layers, as well as between 2: 1 and 0: 1 layers) or Si-Si repulsion (2: 1) rather than
by the presence of a large interlayer cation. This allows displacements between
successive layers as well as relative rotation of layers. Zvyagin uses notations in
which successive symbols show of intra- and interlayer displacements of consecutive tetrahedral (T) and octahedral (0) sheets, Sj and tk respectively (Fig. 24).
These symbols describe both single layers and their stacking for all phyllosilicates. The indices i, k = 1 ... 6 correspond to displacements a/3 in six different
directions related by angles that are multiples of 2n/6 (cL Figs. 22 and 24). Two
consecutive displacements SjSj denote a 2: 1 mica layer. If i = j the layer is
114
centro symmetric and corresponds to the i-th orientation, if i =f. j, it is noncentro symmetric, and orientational symbols are not applicable. For 1: 1 and 2: 1
+ 0: I phyllosilicates there are three additional displacements: equal or translationally equivalent to b/3 and zero (t+, L and to, respectively, Fig. 24). This
alternation of orientation and displacement symbols where both are necessary is
incorporated into the system advocated by Guinier (1984).
The much more complex notations devised to describe the chlorites concern
cases which require symbols not only describing the module stacking (positions,
orientations, operations of displacement, rotation, reflection and inversion) but
also designating (specifying) modules of different kind (e.g., T- and O-sheets).
Dornberger-Schiff and Grell (1982) have proposed general notation principles
for OD-structures which, however, may be extended for all layered structures.
They applied different symbols for polar and nonpolar layers and have distinguished r- and p-operations which retain and invert the polarity of polar
layers. Depending on the distribution of polar and nonpolar layers, the structures are classified into three and four categories with layers of the same or
different kind, respectively.
Guinier (1984) suggests that currently there is no consistent descriptive
notation for polytypic or polysomatic variation in two dimensions - the "rod"
and "block" structures. However, it is often possible to reduce them to the case
of a one-dimensional alternation of two-dimensional modules - "layers".
The Identification of Polytypes
Originally, polytypes were generally identified by diffraction methods.

The finite number of possible positions for each component module of
a polytypic structure implies that it is often possible to regard polytypes as
atomically ordered superstructures of a hypothetical superposition structure.
This aspect of polytypism is emphasized in 00 theory, and leads to distinctive
diffraction behavior. The true periodicity of the structure is often only apparent
from the reflections of particular rows in reciprocal space, whereas only the
superposition structure contributes significantly to others. In simple cases it is
straightforward to identify the stacking direction(s) and the particular poly type
by inspection of diffraction patterns alone. The number of polytypes with a
given periodicity increases dramatically with the periodicity, so simulation of
X-ray intensities may become necessary to characterize the stacking arrangement (provided two or more poly types are not intergrown).
Different electron microscopic techniques, such as high-resolution (HREM)
and selected area diffraction (SAED), provide essential advantages for the
polytype analysis. Oblique-texture ED patterns have proved to be especially
effective. Features of similarity (common building modules) and difference (in
the stacking of these modules) are separately displayed there in a definite set of
ellipses and by reflection positions and intensities along the ellipses. In most
cases, visual inspection of these patterns is sufficient for poly type identification.
SAED patterns are very sensitive to fine structural variations and may reveal
115
small admixtures of different polytypes present in one and the same or different
particles. This is indispensable in studying of such complicated mineral systems
as serpentines (polytypes with cylindrical lattices, superperiods ranging between
20 and 100 A).
Mardix (1986) stresses the utility of additional techniques such as birefringence measurement to identify specific stacking sequences. Many of the shorterperiod polytypes of Sb s0 7 I could be identified from their optical extinction
angle and ferroic transition temperatures.
Since intergrowth and stacking disorder are common in poly typic systems,
the combination of diffraction and direct imaging facilities provided by highresolution transmission electron microscopy (HRTEM) has proved invaluable
for precise identification of different stackings. Two-dimensional images may be
interpreted directly, or compared with calculated images. Even the contrast
variations in one-dimensional images may be correlated with ED and X-ray
intensities or simulations to characterize structures successfully.
HRTEM samples a very small specimen volume, and hence may not provide
representative data. However, it is a particularly good technique for the study of
intergrowths of different polytypes or polysomes, and isolated structure defects.
Many studies have discovered fine lamellae of new ordered structures which are
not known as macroscopic phases, e.g., Ca-Ce f1uocarbonates, biopyriboles, the
humite-olivine-leucophoenicite series. Veblen and Buseck devised a simple
statistical test to calculate the probability of such sequences occurring through
random stacking. In general, the new lamellar phases have low probabilities of
occurring through chance alone; hence their structures are probably determined
by local energetic considerations. It should be noted, however, that local
stacking variations could be considered as belonging to a definite poly type if
there were sufficient repeats in the corresponding stacking for distinctive
polytype reflections to appear. Combination of HREM with SAED thus permits
obtaining complete information on the distribution of polytypes and their
defects.
Natural Examples of Polytypes and Polysomes
Space constraints make it impossible to catalog comprehensively the natural
occurrences of modular stacking variation. Structural details for many examples
were described by Zvyagin (1988) and Hyde and Andersson (1989). The layer
silicates, in which polytypism is particularly prevalent, are reviewed by Bailey
(1984, 1988) and Guggenheim and Eggleton (1988).
The list of polytypes includes close packings of identical and different atoms,
stackings of tetrahedral, octahedral, and prismatic sheets, phyllosilicates and
complex silicates having a variety of relative positions and/or orientations of
their building modules, numerous inorganic and organic structures (e.g., borates
and amino-complexes) for which operations of partial symmetry playa significant role, combinations of building modules periodic in two and one dimensions
or having finite dimensions (e.g., palygorskites, Fig. 25), as well as purely chain-
116

Fig. 25. Scheme of condensation of 2: 1 TOT rods into a
ribbon-layer structure of palygorskite
ribbon structures (e.g., biopyriboles). Here it suffices to illustrate certain notable

forms of polytypism, the diversity of polytypic behavior in two simple systems,
and of both polytypism and polysomatism in interrelating a very large class of
rock-forming minerals.
rt is commonly accepted that polytype layers should have equal translations
forming the basis of all polytype cells. This is not the case even for di"
trioctahedral chlorites consisting of dioctahedral 2: 1 layers and trioctahedral
0: 1 layers. Other polytype structures for which the unit cell basis is a multiply
primitive supercell of the unit mesh of at least one component building layer are
exemplified by modulated layer silicates such as astrophyllite, pyrosmalite
(Fig. 26), zussmanite, and stilpnomelane. In these structures, topologically
complex silicate layers coordinate to simple octahedral sheets which are relatively 7-, 13- 16-, and 48-fold primitive, respectively, when idealized.
The astrophyllite structure presents a possibility of a supercell basis relative
to both kinds of layers alternating in it. The reason for this is difference in
rotational symmetry of the two-layer two-dimensional lattices. If the orthogonal
cell of consecutive T-layers has different azimuthal orientations permitted by the
hexagonal lattice of the intermediate octahedral sheets, the hexagonal supercell
basis will contain seven primitive cells of the T-layer and 49 of the O-sheet
(Fig. 27).
The various polymorphs of elemental carbon can be classified according to
the dimensionality of bonding in their structures. Diamond, in which the
bonding is tetrahedrally directed throughout the structure, is polytypically
related to the hexagonallonsdaleite, known from shocked environments. These
are respectively analogs of the 3C and 2H forms of ZnS or SiC. The twodimensional graphite structure is also polytypic. One-dimensional carbon polymorphs (carbynes, or chaoite) are known from interstellar space and terrestrially
from shocked graphite, and exhibit chain kinks with variable periodicity,
117
Fig. 26. The T- and O-Iayers of pyrosmalite
00
0
0
00
O . 0
0 0
00
00
O 0
0
0
0
0
0
0
0
BoO
00
00
,.
00
00
00
00
0
0
00
00
0-0
0
C
00
O 0
0
00
0-0
0
0
0
0
Fig. 27. The la yer cells and supercell in the superposition of astrophyllite T-Ia yers which differ
in azimuthal orientations
118
whereas finite C 60 -C 70 molecules (fullerenes) are a component of soot. Fullerenes have recently been obtained as macroscopic crystals displaying stacking
disorder.
The structure of rutile, Ti0 2 , is related to the corundum structure of Ti 2 0 3
and a large series of intermediate phases by crystallographic shear. The same 1/2
[011] displacement does not affect the stoichiometry when it takes place on
(OIl) planes: this relationship is polytypic. The new structure is that of the highpressure phase Ti0 2 -II (isostructural with a-Pb0 2 ). The straight chains of edgesharing Ti0 6 octahedra in rutile are converted into zig-zag chains, whilst
preserving the approximate hexagonal close-packing of the oxygen sublattice.
The other two polymorphs ofTi0 2 have the same zig-zag chains as Ti0 2 -II, and
may be derived from it by displacements on {lOO)ruo converting the ABAB
oxygen stacking into ABAC (brookite) or ABCABC (anatase). This system
therefore exhibits two-dimensional polytypism in which the two stacking axes
are symmetrically unrelated.
The structural relationship between zoisite and clinozoisite, Ca 2 Al 3
(Si0 4 ){Si 2 0 7 )00H, was originally described in terms of "unit cell twinning". It
has since been shown that their relationship is poly typic, successive (OlO)
structural layers being shifted 3c/8, with the sense of displacement constant
for the 1M structure, alternating for the 20 structure. Interestingly, the closely
related pUmpellyite-sursassite minerals show stacking variation on (OOI) rather
than (OlO), suggesting that two-dimensional variation is feasible.
The known structures of Mg 2 Si 2 0 6 pyroxenes are polytypic, being distinguished by the orientations of the Mg octahedra along x: [+ +] or
[- -] for clinoenstatite, [+ -] for protoenstatite, and [+ + - -] for
orthoenstatite. Very similar behavior is seen in the amphiboles and higher
pyriboles. This is not surprising, since all these phases are simply related by
polysomatic chain condensation along y, which would ultimately lead to the
formation of a mica structure. Pyroxene-like modules may stack with wollastonite units on (Ill) to produce pyroxenoid polysomes with longer chain periodicities. Wollastonite itself (Ca 3 Si 3 0 9 ) shows polytypism by chain slip on (lOO),
whereas slip on (OOI) produces the bustamite structure. The high-temperature
polymorph, pseudo wollastonite, is itself polytypic, but the structural topology is
very different. Continuous edge-sharing sheets of Ca octahedra are linked by
finite Si 3 0 9 rings in a manner reminiscent of the phyllosilicates.
Pyroxene-like modules may also interleave with spinel modules on (OlO) to
produce the structures of sapphirine and surinamite. Additionally, polytypism in
sapphirine arises because a c/2 pseudoperiodicity in the pyroxene units allows a
choice of two positions for each spinel module.
Factors Affecting Polytype Occurrence

Empirically, the shorter-period members of a polytype family are usually found
to be the most common. In particular, "homogeneous" stacking sequences, in
119
which all modules are crystallographically related, are very frequent. This is
understandable since less regular structures can be described as interlayerings of
different homogeneous structures, and will tend to be intermediate in energy
between the extreme stacking configurations represented by the homogeneous
phases.
The pressure, temperature, and compositional controls on the relative
stability of some silicate polytypes are fairly well known (zoisite, sapphirine, Mgrich pyroxenes). It is clear that the simple phases in these systems have stability
fields that are well-defined in P-T space, but are very sensitive to composition.
Although temperature plays some role in determining structure in the
classical polytypes, it has often been assumed that the known structures do not
in general correspond to equilibrium phases in one-component systems. The
only reversed equilibrium observed appears to be the 2H-12R transition in PbI 2 .
There are factors which appear to determine polytypic diversity in MX and
MX 2 compounds. Trace impurities, nonstoichiometry, and the concentration of
structure defects all have a significant effect on poly type stability, which is
presumably thermodynamic in nature. Thompson (1981) points out that the
incidence of stacking disorder in phyllosilicates should decrease as the crystal
size increases. For small grains, the configurational entropy associated with
stacking disorder provides a free energy which may compensate for the stacking
fault energy.
Kinetic factors such as crystal growth rate may also be important. Fast
crystallization of SiC favors metastable formation of the high-temperature 3C
structure, which has been observed to transform to other structures subsequently. A specific growth mechanism is invoked to explain polytypic variation in the screw dislocation theory of Frank (1951). Most of the long-period
structures observed in polytypic systems can be derived by insertion of periodic
stacking faults into a simpler structure. According to Frank's theory, the
complex structure is, in fact, generated by propagation of a stacking fault by
growth around a giant screw dislocation. Subsequent developments of this
model hypothesise that stacking fault propagation relieves thermal stresses
during cooling (in vapor-grown ZnS whiskers), and that the faults initiate in
highly disordered nuclei before being propagated during a subsequent phase of
more orderely growth as in micas. Rai et al. (1986) show electron micrographs of
a spectacular long-period silicon carbide sample with a 1734R structure (c/3
= 1455 A). The repeat unit can be subdivided into four subunits of width 137,
131, 137, and 173 layers respectively. This correlates with the observation offour
interacting growth spirals on the surface of the crystal, but other studies on
various systems have failed to find quantitative correlation between growth
spiral step heights and the observed structure. In any case, the screw dislocation
model does not apply when layer-by-Iayer crystal growth occurs, and it cannot
account for the irregularly placed stacking defects so common in polytypic
systems.
Recently, models have been proposed which account for long-period structures as equilibrium phases. The axial Ising models map a suitable structural
120
parameter for each module onto a pseudo spin variable, and then generate phase
diagrams for a small number of different interactions between neighboring spins.
At low temperature, only a few simple phases are stable, but entropic contributions associated with spin flips stabilize longer-period phases as T increases. A
well-defined suite of polytypes emerges, in which the more complex structures
have progressively smaller stability fields. Distinctive poly type suites occur,
depending on which short-range interactions are most significant.
Pseudo potential calculations on systems such as SiC and ZnS have provided
quantitative estimates of the relevant interaction energies. The additional
entropy associated with long-period structures arises from a combination of
electronic and elastic interactions associated with small static relaxations in
interlayer spacing (0.0685% difference between the 2H and 12R polytypes
of PbI 2 ). Lattice vibrations also effect variation in the interlayer spacing
dynamically which is capable of stabilizing long-period structures provide
experimental evidence that Raman-active lattice modes are softer in the hightemperature 12R phase of PbI 2 than in the 2H form.
Salje et al. (1987) give an alternative phenomenological treatment of PbI 2
polytypism in terms of Landau theory. The "ferro" (2H) and "antiferro" (12R)
phases are derived from a hypothetical "para" phase, which may be equated
with the disordered superposition structure of OD theory. Longer-period
phases can be stabilized by Umklapp terms in the Landau potential.
Polytype Transformation Mechanisms

In many layered modular structures, the two-dimensional lattices of all layers
possess the same rotational symmetry along the stacking axis. In general,
therefore, it is possible to tranform between these structures by relative translation of component layers, that is, by the propagation of stacking faults, which
are bounded by partial dislocations. Transformational faults are similar in
geometry to those of deformational origin, but can be distinguished from many
faults arising during crystal growth. Local diffusion may be associated with
dislocation movement. Similar solid-state mechanisms involving considerable subsequent lattice relaxation effect poly somatic transformations in the
pyroxenoids.
Intermediate stacking configurations generated during such a transformation can significantly affect local stacking fault energies, and direct the
placement of the next fault. This can impede the transformation kinetically, and
provides another mechanism for generating long-period structures metastably.
Clearly, applied nonhydrostatic stresses can also generate metastable phases. A
good example of this is the production of clinoenstatite lamellae in sheared
orthoenstatite.
It has been found that the 3C-2H transformation in ZnS is athermal, and
appears to nucleate on preexisting defects. The transformation in PbI 2 is also
strongly defect-controlled. It occurs stepwise over a finite temperature range.
The transformation front advances supersonically, indicating that it is diffu-
121
sionless and solitonic in nature. The transformation has a large activation

energy (3.8 eV) but a very small latent heat (276 J/mol), as might be expected.
The situation is much more complicated when the rotational symmetries of
layers and their two-dimensional lattices do not coincide. This is the case with
almost all phyllosilicates and even with close packed structures where layers
have threefold axes while their lattices have sixfold axes. In such structures the
layers may have different azimuthal orientations (six at most and two opposed
ones at least). In such cases, physically implausible rigid layers rotations would
be needed for solid state transitions from one polytype to another (e.g., between
dioctahedral micas 1M and 2M!, kaolinite lTC and dickite 2M, bayerite and
gibbsite, molybdenites 2H and 3R). Polytypes often observed in close mixtures
and intergrowth may be formed simultaneously under specific crystallization
conditions. Polytype transitions may result from diffusion of atoms leading to
redistribution of their positions and change of layer azimuthal orientations.
Otherwise it requires complete or partial destruction of one polytype lattice and
nucleation of the other. Substance reconstruction with partial retainment of
some layer fragments is supposed to occur in transitions between different
phyllosilicates: kaolinite-mica, kaolinite-pyrophyllite, pyrophyllite-chlorite, etc.
Such transitions were realized experimentally and an inheritance effect has been
observed, displayed by preservation of layer orientations of initial and resulting
phyllosilicates.
Applications of Polytypism
We conclude with a few examples that illustrate the practical applications of
polytypism, and its relationship to other physical and chemical properties.
The sensitivity of polytype structures to small chemical variations makes
them useful indicator species in petrology. Clay mineral polytypes and their
defects are especially useful as indicators of environment and formation conditions as well as of the quality of raw materials.
Sapphirine structure is determined by mean iron oxidation state. The 3R
structure of molybdenite correlates strongly with an elevated Re content.
Molybdenite is the principal economic source of this rare metal.
The pyrochlore-zirke1ite-zirconolite A2 B2 0 7 phases are important constituents of "SYNROC", used for containment of nuclear waste. Their utility
derives from the polytypic relationship between their structures.
Layers of octahedral cations stack so as to provide a variety of five to eight
coordinated interlayer sites, which can firmly incorporate both actinides and a
wide range of fission products.
Polytypism in zeolites affects the distribution of cage and channel sizes, and
thus their efficacy as molecular sieves and catalysts. Intergrowths of the sodalitecancrinite-gmelinite-chabazite zeolites are known.
There is a strong correlation between periodicity and band gap in semiconducting polytypes. For SnS 2 , the band gap falls from 2.18 eV in the 2H phase
to 0.81 eV in 50H. Rao et al. (1986) discuss the possibility of constructing ultra-
122
high efficiency photovoltaic cells from lattice-matched multilayers of such

materials. They also point out that both the REE-Ni alloys used for solid-state
hydrogen storage and TiS 2 :Li, used in solid-state battery electrodes, are polytypic. Understanding the stacking behavior of these materials is likely to be
important in optimizing their technical performance.
The high-Tc oxide superconductors have structures which are polysomatic
stackings of perovskite- and rock salt-like units. Their periodicities and stacking
patterns have a marked effect on their critical temperatures, which has been
important in directing the search for new superconductors.
Polytypism is an important conceptual tool which facilitates the description
and rationalization of many mineral structures. The chemistry, stability, and
transformation mechanisms of many phases are readily understood in the
context of their polytypic and polysomatic relationships. The appreciation of
modular structure can also be used to predict hitherto unobserved phases,
syntactic intergrowths, and solid-state transformation mechanisms.
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V.A.
DRITS
and
R.C. REYNOLDS
Mixed-layer minerals (MLM), or interstratified minerals, are remarkable natural examples of one-dimensional order-disorder in crystals. They are composed
of layers of differing structures and/or compositions that alternate in variable
proportions and in different stacking patterns that may be random, partially
ordered, or fully ordered with short or long range ordering patterns.
Interstratification effects have been found in structures of various natural
and synthetic compounds such as layer silicates, phyllo-manganates, carbonates, oxides, and hydroxides, including high-temperature superconductors, intercalated graphites, and other lamellar compounds. Interstratification effects in
natural crystals are especially widespread amid clay minerals which differ in
types of layers (micaceous, chlorite, smectite, kaolinite, etc.) as well as in their
alternation patterns.
There are several reasons for special interest in the mixed-layer minerals. In
the field X-ray diffractometry, they have given impetus to new theoretical and
methodological developments because their unusual diffraction effects cannot
be interpreted using conventional X-ray diffraction structural-analysis techniques.
125
Studies of mixed-layer minerals with modern physical and physicochemical

methods have shown that there are different ways in which a transformation of
one mineral into another may proceed. The understanding of such transformations has made significant contributions to our understanding of the
structural mechanisms of phase transitions.
Interstratification effects have posed new problems for the thermodynamicist, who must answer questions concerning whether mixed-layer minerals are
always metastable, and whether they are mono-phase or poly-phase, etc.
Mixed-layered clays are exceptionally abundant in the various geological
settings of continental and oceanic environments at the Earth's surface. This,
coupled with observations that some of the minerals are restricted to certain
geological environments, and that the minerals display a high sensitivity to
changing physicochemical environments and many other factors, has made this
group of minerals an important source of geological information.
Types of Mixed-Layer Structures
Mixed-layered clays can be either two- or multi-component. The structure of the

layer types in these minerals is to a large extent similar to that of a given layer
type in the pure mineral that exemplifies the layer type. For example, mixedlayer illite-smectite (I/S) is composed of mineral crystallites that contain alternating illite and smectite layers, if the boundaries between the layers pass through
the planes of 2: 1 layer octahedral cations.
Two categories may be singled out, depending on the type of alternation of
layer types: (1) ordered structures where different layer types alternate along axis
"z" in a periodic fashion, i.e., layers A and B, for example, alternate as ABAB or
as AAABAAB. Such minerals usually have names of their own (chlorite,
corrensite, tosudite, rectorite, cylindrite, tochilinite, etc.), (2) irregular mixedlayer minerals where different layer types may either alternate at random, or
only tend to some sort of ordering or segregation.
MLM can be grouped in three categories, depending on the dimensions and
shapes of the unit cells of the different layer types. First are the MLM with
identical two-dimensional unit cells (in the x-y plane) for each of the different
layer types. Identical two-dimensional periodicity, combined with a similar
anionic structure of basal surfaces in different layer types ensures stable interlayer bonds in these minerals (illite-smectite, kaolinite-smectite) etc. Then there
are commensurable ML structures, or structures with commensurable layers of
different types. In such structures, the unit cell of the one of the layer types is a
subcell of the other type, or otherwise, a supercell exists for the whole structure
although the periodicity of each layer can be described in terms of smaller unit
cells. The examples include structures of chlorite, tochilinite, intercalated graphites, etc. Finally, there are incommensurable ML structures, or structures whose
layer types have their own two-dimensional periodicity without any rational
relations between the cell parameters in alternating layers.
126
Incommensurability may be caused by other factors. For example, the

alternating layers may differ either in structure, or having a similar structure,
they may differ in the cation/or anion composition. In the structure of asbolanes,
e.g., the incommensurability is due to the different ionic radii of Mn4+ and Ni
cations in the alternating layers. In the structure of valleriite, it results from
differences in the radii of sulfur and oxygen anions that form layers of a different
nature. Incommensurable structures may have either ordered or disordered
alternation of different layer types. The former, in addition to valleriite, tochilinite, kennenite, asbolanes, and some sulfosalts (cylindrites), include trioctahedral
chlorite-dioctahedral smectite. The latter include, for example, asbolane-buserites, and chlorite-swelling chlorite. What distinguishes these minerals is that their
description requires not one, but two or even three incommensurable lattices. A
unique feature of the crystals of irregular incommensurable mixed-layer minerals is that they have no common periodicity either along the normal to the layer
or in the basal plane.
Identification of Irregular Mixed-Layer Minerals

The basic technique for the identification of irregular mixed-layer minerals is
X-ray powder diffraction analysis of oriented samples. Irregular alternation of
layers differing in thickness leads to XRD patterns that have an irrational series
of basal reflections, that is, their spacings do not follow the Bragg law. The
d-spacing values measured from basal reflection positions are only apparent as
they do not correspond to real inter-layer distances in mixed-layer minerals.
Figure 28 shows an XRD curve of ML mica-smectite. Irregular mixed-layering
is also manifested by non-systematic broadening of the peaks that comprise the
basal diffraction series. If the peak breadths increase systematically with respect
to diffraction angle, then the broadening is caused by particle-size effects, strain,
crystal defects along the z-direction, or crystal bending. But if, for example, the
9.78
G
Fig. 28. Comparison between experimental (circles) and calculated (full line) XRD curves for
an interstratified leucophyllite-montmorillonite (I-m) solvated by ethylene glycol. The parameters of the model used for the calculations were WI: Wm = 0.89: 0.11; P mm = P mlm = O. P mUm
= 0.15; R = 3 d 1 = 9.88 A, d m = 16.6 A,s,,; N ,,; 10
127
003 reflection is broad and the 005 is sharp, then the cause can only be some sort
of irregular interstratification.
In some MLM structures, the thicknesses of alternating layers are related as
d 1 = nd 2 (n is an integer), and then the diffraction pattern is not irrational and
the line-broadening pattern will cycle with respect to diffraction angle in some
fashion such as broad-sharp-broad-sharp for the 001, 002, 003, and 004 reflections in, for example, diffraction patterns from mixed-layered chlorite that
contains some serpentine layers. But for all such structures, a detailed analysis of
basal reflection intensities and line breadths, or the application of high-resolution electron microscopy is required.
Interpretation ofXRD patterns of all types of MLM requires development of
special techniques. Identification of incommensurable MLM is most effectively
accomplished with selected-area electron diffraction.
Models of Irregular Mixed-Layer Structures

Qualitative description of the alternation pattern in irregular mixed-layer
crystals or their coherent-scattering (CSD) domains is usually based on
Markovian statistics. Its main assumption is that the occurrence probability for
a layer of the given type depends only on the closest preceding neighbors. An
important parameter in this model is the short-range order factor, R, which is
equal to the number of preceding layers that influence the occurrence probability of a final layer of the given type. The case of R = 0 corresponds to
random layer alternation, while with R = 2, the probability of occurrence of the
given layer type depends on the nature of the two nearest predecessors. A
definite set of conjunction probability parameters corresponds to each R. If, for
example, two types oflayers, A and B, alternate in the crystal with R = 1, then to
characterize the structure, six probability parameters will be needed: WA, WB,
P AA, P AB, P BA , and P BB . Here Wi is concentration of layers of type i, Pij is the
conjunction probability of layer type j following layer type i (i, j = A,B). The
higher the R value the greater the tendency towards long-range regular alternation of different layer types and the larger the number of parameters required
for a description of the structure. For example, if R = 2, eight more conjunction
probabilities P ijk define the probability of layer type k following a pair of layers
of the sequence ij. Using the set of probability parameters for the given R value,
the probability of occurrence of any layer subsequence in a mixed-layer crystal
can be readily calculated. The probability of occurrence, for example the
subsequence ABAAB, is equal to WA P AB P BA P AA P AB for R = 1; WA P AB PABA
P BAA P AAB for R = 2, WA P AB PABA PABAA P BAAB for R = 3, etc. The probability
parameters are interrelated and the number of independent parameters for each
given R is therefore relatively small. For a two-component system with R = 1,
there are two, and for R = 2, there are four independent parameters.
Structures with the maximum possible degree of ordering in the alternation
of different-type layers for a given R (MPDO structures) are common in nature.
128
Such cases are realized, e.g., when R = 1 and WA = WB and P BB = 0; if R = 2,

W A = 2/3 and P BB = P BAB = 0; and if R = 3, WA = 3/4 and P BB = P BAB
= PBAAB = O. Description of two-component MPDO structures requires only
the values for Rand WA
Many natural mixed-layer minerals consist of extremely thin microcrystals.
The total number of layers in coherent domains in such mixed-layer minerals
rarely exceeds a few dozens. In Markovian statistics, such a MLM, from the
point of view of X-ray diffraction, is a statistically weighted assemblage of
microcrystals that differ from one another not only by the alternation patterns
of different layer types but also by the proportions of these layer types. The
heterogeneity of the microcrystal is a function of the total number of layers N in
it, the average content of different layer types Wi in the powder, and the pattern
of their alternation. For example, for N = 10, R = 1, WB = 40% and P BB = 0,
the powder will contain microcrystals of the compositions 8A2B (12%), 7A3B
(26%), 6A4B (46%), and SASB (16%), where concentrations are in brackets.
Thus, in terms of this model, the XRD pattern of a powder MLM is a
statistically weighted sum of XRD patterns from many microcrystals, each of
which has a given proportion of layer types and a unique but statistically
allowable (for Rand WA) arrangement in the distribution of the different layer
types.
For the particular case of mixed-layer illite-smectites, Nadeau et al. (1984)
suggested a model of fundamental particles. It is based on the assumption that,
actually, there exist only illite particles whose outer basal surfaces expand with
solvation like smectite. Face-to-face stacking along the (001) plane of the
fundamental particles leads, as the authors believe, to interstratification, since
the properties between the outer surfaces of each pair of particles are the same as
those of smectites. This model has the advantage that it explains the presence of
different values for R for different occurrences of illite/smectite. For example, for
R = 1, WA = 0.5, the MLM contains fundamental particles that consist of only
two 2: 1 silicate skeletons centered on a potassium ion. For R = 2, the fundamental particles consist of three 2: 1 skeletons with two internal potassium ions,
etc. The transformation of smectite to illite is thus visualized as the progressive
growth of thicker and thicker fundamental particles. The present authors
disagree on the validity of this concept, as indeed do many other workers in the
field. More work is required to validate or deny it, and in this regard, modern
studies using high-resolution electron microscopy (HRTEM) will be important.
It may be that there is only an apparent difference between the concept of
fundamental particles and the statistical model described above.
Methods for the Study of MLM Structures and Their Crystal Chemistry
A wide range of methods are used for studying MLM structures and crystal
chemistry that include X-ray powder diffraction, selected-area electron diffraction, microanalytical techniques for chemical composition, NMR, and IR
spectroscopy.
129
The XRD powder method is the main method for determining structural
characteristics of mixed-layer minerals. At present, there are two approaches to
the interpretation of experimental diffraction patterns. One is based on direct
methods of Fourier transformation which provide structural parameters for the
sample (values of Wi' W ik , Wikl' etc.) using the measured values of d-spacings and
basal-reflection intensities. These methods, however, have certain serious theoretical and practical limitations and are rarely used.
The most widely used approach is based on the simulation of diffraction
effects from mixed-layer structural models and their comparison with experimental diffraction patterns. The basic advantage pf indirect methods is that they
may be used to predict diffraction effects from all theoretically possible structural models. This method makes it possible to analyze the effect of various
chemical and structural parameters for a MLM. The calculations can deal with
proportions of the different layer types, their chemical compositions, the
thicknesses of alternating layers, their alternation patterns, microcrystal thickness, and the distribution of thicknesses. The effects of all of these on the
positions, intensities and profiles of basal reflections can be determined. A
systematic and purposeful analysis of the data obtained using the approach
described has led to a set of diffraction criteria widely used for the identification
and quantification of the most abundant MLM.
Effective application of indirect methods requires that the initial structural
models be as close to the actual structures as possible. This requirement may be
a rather difficult task to cope with in the general case, since even if the choice of
the model is correct (i.e., with very good values of S, Wi' P ik ), its refinement will
require a great number of various parameters (composition, z-coordinates of
atoms, layer thicknesses, microcrystallite dimensions, instrumental factors)
many of which can be determined only by the trial-and-error method.
The most widely and successfully used recently developed procedures for
MLM studies are high-resolution transmission electron microscopy (HRTEM)
combined with energy-dispersive X-ray analysis (EDX). Their combination
provides information on the structure and composition of the objects from tens
to hundreds of Angstrom units in diameter. The HRTEM and EDX reveal data
on the specific distribution of sheets and layers with a resolution of structural
components of the order of 3 A. In particular, this technique was used to
visualize particles with alternating 14 A chlorites layers and 7 A berthierine
layers. Such mixed-layer structures are difficult to identify using XRD, and can
be dealt with only by very careful studies of line-broadening of basal reflections.
HRTEM and EDX can potentially provide an altogether new level of
knowledge of MLM structures which can be vital in revealing the mechanisms
of formation and transformation of MLM.
Practical Techniques for Analyzing Structural Parameters of MLM
Structural parameters for which the best possible agreement is achieved between
the X-ray diffraction intensity distributions of the simulated and experimental
130
XRD curves can be considered as those that adequately describe the MLM
structure (Fig. 28). Reliability of structural determinations substantially increases if, with the same probability parameters, the same agreement between
observed and calculated patterns is obtained for two different states of a given
sample (e.g., saturated with ethylene glycol and glycerol) that produce different
positions and intensities of reflections (Fig. 29). This method is very timeconsuming, so researchers often confine themselves to semi-quantitative fitting
of experimental and simulated XRD curves (Fig. 30).
lB.~
4.53
3.526
3.366
3.56
3.56
1.80
3.48
3.34
Fig. 29a, b. Comparison between

experimental (circles) and calculated (full line) XRD curves obtained from ML celadonite-nontronite mineral saturated with glycerol (a) and ethylene glycol (b).
The parameters of the model used
for calculation were We: Wn = 0.4:
0.6; Po, = 0.55, R = 1, d, = 10 A,
d n = 16.90 A or 17.78 A; the distribution of thicknesses of coherence domains ranged from N = 2
to 8
7.80
1.65
7.60
d
3.48
Fig. 30a, b. Comparison between experimental (a) and calculated (b)

XRD patterns for an interstratified
kaolinite-montmorillonite (k-m) solvated by ethylene glycol (a) and after
dehydration at 350C (b). The parameters of the model used for calculations were W k : Wm = 0.75: 0.25; R
=0,
d k =7.15A,
dl"=17.78A
(curve c) and d m = 9.6 A (curve d),
10:::; N:::; 20
131
X-ray diffraction approaches require relevant computer programs that are

somewhat difficult to produce, and a more widely used technique is employed in
MLM structure determinations. It is based on the systematic calculations made
by some authors for XRD curves of the most common MLM (e.g., illite-smectite,
glauconite-nontronite, chlorite-saponite) with varying values of S, Wj, P jk and
other chemical and structural parameters. Using these data, some researchers
have suggested different graphic methods for determining the concentrations of
different layer types and their alternation patterns.
Geological Significance of MLM
The common interest from MLM stems from their wide abundance in diverse
geological environments - weathering crusts, contemporary sediments, hydrothermally altered rocks, and rocks having undergone postsedimentary transformations. They are found in oceanic sedimentary rocks, nonmarine sediments,
and altered oceanic basalts. The important point is that various types of MLM,
especially mixed-layer clays, are associated with definite geological environments, and their identification and description is essential for determining the
genesis of the enclosing rocks.
Mixed-layer illite-smectite, for example, is one of the most common clay
components in sedimentary rocks that have been subjected to diagenesis and
low-grade metamorphism. Such MLM are also widespread among the hydrothermally altered rocks of subsurface mineral ore deposits. Illite-smectites with
R> 1 make up the bulk of the K-bentonites of Silurian and Mid-Ordovician
deposits of the Baltic region, Sweden and North America. Peculiar interstratified leucophyllite-smectite minerals have been found in ash strata of a
number of salt-bearing deposits.
Ordered or almost ordered chlorite-saponites (corrensites) can be grouped
into five major genetic categories based on composition and paragenetic
associations.
(1) Mg-rich diagenetic corrensites of evaporitic terrigenous chemogenic and
carbonate formations, and of hydrothermally altered dolomite-gypsum rocks.
(2) Mg-Fe corrensites of thick clastic volcano-sedimentary and sedimentary
rocks transformed under regional epigenesis. (3) Fe-rich corrensites formed in
the course of postsedimentary transformation of terrigenous rocks. (4) Corrensite with variable compositions resulting from post-magmatic alterations of
basic and intermediate rocks on land and under water. (5) Corrensites as
weathering products and soil components. Depending on the exact geologic
setting, corrensites may form distinct paragenetic associations with Fe-illite,
laumontite, and analcime.
MLM are widely studied because their structural and compositional peculiarities sometimes reflect the dynamics of physicochemical changes in the
course of a geological process. Thus MLM are often an intermediate link in the
series of stage-by-stage transformations of layer silicates. Such transformations
132
are possible largely because it is the phyllosilicate interlayers that are most
sensitive to environmental changes, so that a change from one structural type to
another can proceed without radical restructuring of the silicate layers. Clay
mineral reactions take place at relatively low temperatures, so the possibility
must always be considered that the reaction progress is kinetically controlled
and does not necessarily represent equilibrium conditions with respect to any
specific chemical environment.
Despite the complexity of possible kinetic constraints, revealing relationships between physicochemical conditions of the environment, and structural
and crystal-chemical peculiarities of the mixed-layer phases favor the use of
MLM as indicators of various stages of regional epigenesis and of the degree of
hydrothermal alteration of rocks.
A transition from one mineral to another via a series of mixed-layer phases is
not necessarily the result of a solid-phase transformation. MLM may form as a
result of synthesis from a solution, or through dissolution-reprecipitation or
metasomatic reactions. Therefore, in an analysis of the alteration of MLM at
any stage of their existence, much attention is paid to determining the structural
mechanism for MLM formation. These data, together with detailed tectonic,
lithological, and petrographical studies of enclosing rocks can provide a basis
for the solution of various geological problems. As an example, interstratified
illite-smectites are being used to unravel the thermal history of sedimentary
rocks, processes of sandstone cementation, dynamics of oil migration, and the
origin of hydrothermal solutions.
Despite intense and comprehensive research on MLM that involves considerable intellectual efforts throughout the world, there still are a lot of spots in
our knowledge of these minerals. Development of new methods and improvement of existing ones should help to determine unambiguously the status of
MLM, their fine structural and crystal-chemical features, the rules that govern
the patterns of alternation of different layer types, and analyses at the atomic
level. Synthesis of such information should lead to a good understanding of the
formation mechanisms as well as the transformation dynamics. The sophistication of emerging methods should add considerably to the range of examples in
which an irregular alternation of two-dimensional structural fragments takes
place. There is still much to be done to elucidate the effect of various factors
(e.g., temperature, presssure, porosity, rock type and age, composition of
solutions, kinetics of the processes) that are responsible for the detailed morphological, structural, crystal-chemical and, finally, indicator characteristics of
various mixed-layer minerals.
References
Drits VA, Tchoubar C (1990) X-ray diffractIOn by disordered lamellar structures. Springer,
Berlin Heidelberg, New York, 370 pp
Drits VA (1987) Electron diffraction and high resolution electron microscopy of mineral
structures. Springer, Berlin Heidelberg New York, 304 pp
133
Nadeau PH, Tait JM, McHardy WJ, Wilson MJ (1984) Interstratified X-ray diffraction
characteristics of physical mixtures of elementary clay particles. Clay Mineral 19: 67-76
Reynolds RC (1988) Mixed-layer chlorite minerals. In: Bailey SW (ed) Hydrous phyllosilicates
(exclusive of mica). Reviews in Mineralogy. Mineral Soc Am, pp 601-629
Reynolds RC (1980) Interstratified clay minerals. In: Brindley GW, Brown G (eds) Crystal
structures of clay minerals and their X-ray identification. Mineral Soc, London, pp 249-303
Srodon J (1980) Precise identification of illite/smectite interstratification by X-ray powder
diffraction. Clays Clay Mineral 28: 401-413

S.
GHOSE
Two types of phase transitions in minerals, structural and magnetic, which are
continuous or nearly continuous (second- or nearly second-order) have been
extensively investigated in the last few years. These transitions are characterized
by a change in symmetry (structural or magnetic) as a function of an external
variable (temperature T, pressure P, chemical composition, X, etc.) such that the
symmetries are related by a supergroup-subgroup relationship. Familiar examples are pI-II transition in anorthite, CaAl 2Si 20 g at 514 K; P2t/c-+C2/c
transition in clinohypersthene (Fe, Mg)2Si206' at '" 1000 K, the IX-P quartz
transition at 846 K, etc. For continuous structural transitions, an order parameter, '1, is defined which describes the pattern of atomic displacements, which is
responsible for the lowering of symmetry; '1 decreases continuously as T
approaches the critical transition temperature, Te. The order parameter is
usually described by a particular wavevector within the Brillouin zone and may
be written as '1j (q), where q is the wave vector of j'th phonon branch. During the
paraelectric (cubic) to ferroelectric (tetragonal) transition of BaTi0 3 with the
perovskite structure, the Ti-ions are displaced away from the center of the
oxygen octahedra, causing thereby an electric polarization. This distortion
corresponds to a transverse optic mode (TO), whose phonon frequency dependence on temperature is given by w 2 TO = C(T - T c), which has been experimentally observed by inelastic neutron scattering. Such a phonon mode, whose
frequency approaches zero as T -+ Tc is known as a soft mode. In BaTi0 3 , the
wavevector q of this mode is zero which lies at the zone-center, and two unit cells
have nearly the same volume. In SrTi0 3 on the other hand, the cubic to
tetragonal transition requires alternate clockwise and anticlockwise rotation of
the [Ti0 6] octahedra, resulting in a cell doubling below Te ( '" 105 K); here the
q is at the zone boundary point, R [111]. The index (1 ~ j ~ n) describes the
number of components of the order parameter. In cubic ferroelectrics such as
BaTi0 3 n = 3, corresponding to polarization along x, y, or z crystal axes.
Following Landau theory, for the simplest possible case of the single
component order parameter (n = 1), the free energy of the crystal through the
134
transition can be expanded in a power series in the order parameter,

F ==
AI]2
1];
+ BI]3 + DI]4 + ....
(2)
From symmetry considerations it can be shown that A can be written as

A == a(T - TJ,
(3)
and B = 0 for a continuous phase transition.

For T > T e, the average of the order parameter <IJ) = 0 and the undistorted
phase is stable. For T < T e, the free energy minimum corresponds to
<1J>2 = (a/2D)(T e - T),

and the (less symmetric) distorted phase is stable and I] ex (Te - T)1/2. The
critical exponent 1/2 predicted by Landau theory, however, is rarely observed,
indicating that Landau theory is at best an approximation, which breaks down
within the critical region around Te. The primary order parameter, IJ always
couples with other secondary order parameters such as spontaneous strain, [;ij
which arises due to the atomic displacements from the more symmetric phase.
The nature of the coupling between IJ and [; depends on the irreducible
representations according to which they transform. Usually the coupling between IJ and [; are linear-linear or linear-quadratic.
The soft phonon mode referred to above arises from the similarity of the
leading term in the Landau free energy expression a(T - T c) with the free energy
of a harmonic crystal. We obtain
[W(q)]2 = K(T - T e),
where w (q) is the frequency of one of the modes of vibration of the crystal with
the wavevector corresponding to the distortion of the low temperature phase.
According to this view (Cochran 1960) the structural phase transition results
from the instability of the crystal with respect to a particular mode of vibration.
In the low temperature phase, the crystal increasingly distorts below Teas the
temperature is lowered in order to stabilize this normal mode. Interestingly
enough the soft mode idea was already suggested by Raman and Nedungadi
(1940) for the rx-fJ quartz transition from Raman spectroscopic measurements.
The soft modes in the low temperature phase are always Raman and IR active;
however, they may be inactive in the high temperature phase if the unstable (soft)
phonon mode lies at a point other than the center of the Brillouin zone (e.g.,
SrTi0 3 ). In such a case, the soft mode can be measured by inelastic neutron
scattering.
As mentioned earlier, spontaneous strain always arises as a result of the
increasing distortion below Te. The coupling of the spontaneous strain with the
primary order parameter implied either a jump or a softening of one or more
elastic constants at Te. The coupling of the optical soft mode with an acoustic
mode near Te results in the onset of critical fluctuations. Near T e, these long
wavelength fluctuations have a hydrodynamic character with a frequency in the
acoustic range or below and can be directly imaged by transmission electron
135
microscopy (e.g., a-[3 quartz transition: Van Tendeloo et al. 1976; pI-IIanorthite transition: Van Tendeloo et al. 1989). Further above T e, both the
increasing fluctuation frequency and decreasing correlation length (cluster size)
with increasing temperature can be measured by inelastic neutron- and Raman
scattering. In most cases, the phase transition is initiated by a soft mode
(displacive) mechanisms in the low temperature phase, but finally driven by
critical fluctuations near T e, where an order-disorder mechanism predominates.
In such a case, the average order parameter may have a small nonzero value
above T e because of the persistence of small clusters of the low temperature
phase within the stability field of the high temperature phase. Immediately
above T e, the high temperature phase is a statistical dynamical average of
domains of the low temperature phase. Again, a-[3 quartz and pI-II anorthite
transitions serve as good examples.
Structural Phase Transitions
We will now illustrate several structural phase transitions in minerals, which

have been studied by a variety of experimental and theoretical techniques. The
a-[3 quartz transition is a nearly second order transition (but first order near T e),
which is characterized by a sharp lambda peak in the specific heat curve. An
incommensurate phase spanning a temperature range of 1.4 K exists between
the a and [3 phases (Dolino 1988). The tilt angle of the [Si0 4 J tetrahedra is taken
as the primary order parameter, which decreases continuously as T -+ Te; but
close to T C' critical fluctuations cause a change in the domain configuration
from a 1 to (12' which are related by the Dauphine twin law. The soft mode in the
(1 phase corresponds to the mode with a frequency of ~ 107 cm - 1. The high
temperature [3-phase is a dynamic average of a-type domains above Te. These
dynamic phenomena including the formation of the incommensurate phase have
been observed directly by high temperature electron microscopy. During the pIII phase transition in anorthite, CaAI 2 Si 2 0 s, the alumino silicate framework
and the Ca-coordination polyhedra approach the II symmetry as T-+Te; close
to T e, the aluminosilicate framework attains virtually the II symmetry, whereas
the Ca configurations related by R = 1/2 [l11J which should attain identical
configurations at Te are still distinct and retain their pI character. Near T e,
breathing motion type fluctuations of the aluminosilicate framework cause the
Ca configurations related by 1/2[111J to dynamically interchange, thereby
causing the boundaries of the c-type antiphase domains to be mobile and
dynamic. The size of the dynamic domains decreases and the fluctuation
frequency increases with increasing temperature above Te. Similar dynamic
phenomena have been observed during the P2da-+A2/a transition in titanite,
CaTiSiO s, where the order parameter is taken as the Ti displacements parallel
and anti parallel to a from the centers of the [Ti0 6 J octahedra (Ghose et al.
1991). The Ti displacement continuously decreases as T -+ T C' but close to Te it
still retains a small but non-zero value; near T e, the critical fluctuations then
136
cause the Ti displacements to change dynamically from + a to - a configuration and vice versa, thereby causing mobility of the antiphase domain walls. In
ilvaite Ca(Fe z +Fe3+)Fe2+Si0 7 0(OH), the phase transition from P2da--+Pnam
is driven by electron delocalization between Fe z + and Fe3+ ions in adjacent
octahedral A sites, reminiscent of the Verwey transition in magnetite, Fe 3 0 4 at
120 K (Ghose et al. 1989). The order parameter is the degree of electron order
at the Am and Ao sites in the monoclinic phase. Valence fluctuations near Te
finally drive the phase transition. Here also dynamic precursor clusters are
present above Te. Leucite, KA1Si z0 6 shows two phase transitions: cubic
(Ia:3d).... tetragonal{I4dacd) --+ tetragonal (I4da) at ~ 950 and ~ 920 K respectively as determined by crystallographic and differential scanning calorimetry measurements resulting in pseudomerohedric {I1O} twins and merohedric
twins with {II O} as the twin plane, respectively. The first transition shows
hysteresis effects and is first order (nearly second order), whereas the second one
may be second order. Partial AljSi order in the low temperature (P4da) has
been confirmed by MAS NMR and neutron diffraction on powder samples,
whereas the high temperature cubic phase must have complete AljSi disorder.
From neutron (elastic) diffuse scattering near T e , it appears that the cubic phase
is a dynamic average of fluctuating {I1O} twin domains of the tetragonal phase
(P4dacd) showing partial AljSi order (Boysen 1990). The primary order parameter is the degree of Al/Si order at the tetrahedral site, which is coupled to K +ion displacements and spontaneous strain. A similar situation also exists in the
case of rx-fJ transition in cristobalite, SiOz at ~ 493 K (Hatch and Ghose 1991).
The fJ-cristobalite (cubic, Fd:3m) phase appears to be a dynamic average of 12rxcristobalite domains (tetragonal P4 3 2 1 2 or P4 1 2 1 2); these fluctuating domains
are of three types: {II O} twin domains resulting from a loss of the :3 axes,
enantiomorphous domains resulting from a loss of the inversion center, and
antiphase domains resulting from the loss of the translation vector (F --+ P). The
dynamically averaged fJ-phase explains the anomalous situation in fJ-cristobalite found by X-ray and neutron diffraction, namely, sixfold disorder of the
oxygen ion in small rings round the Si-Si axes (Peacor 1973).
Magnetic Phase Transitions

Except a few iron oxides and sulfides, such as hematite, Fe Z 0 3 , magnetite,
Fe 3 0 4, and greigite, Fe 3 S4, which are antiferro- or ferri-magnetic, all iron
silicate minerals are paramagnetic under ambient conditions and show transitions to the anti ferromagnetic state at temperatures ranging from 120-4 K. Thus,
the Neel points for fayalite, Fe zSi0 4, ferrosilite, Fe zSi z0 6 , and grunerite,
Fe 2 Si s Ozz{OH}z, are 65, 40, and 47 K respectively (Coey and Ghose 1988). The
magnetic structures of a number of iron silicate minerals (both ferrous and ferric,
also mixed-valence) have been recently determined by neutron diffraction. The
evolution of the magnetic moment as a function of temperature below Te serves
as the primary order parameter. In the chain silicates (hedenbergite,
137
CaFe2+ Si 2 0 6 , acmite, NaFe H Si 2 0 6 , ferrosilite, Fe~ + Si 2 0 6 , and grunerite,

Fe~ + Si 8 0 22 (OHh), the spins are coupled ferromagnetically within one octahedral chain which are antiferromagnetically coupled to neighboring chains. In
ferrosilite and grunerite, the spins are parallel and anti parallel to b below the
Neel points 40 and 47 K respectively. In both cases, there is a spin-canting
transition at 7-10 K, below which some of the spins are canted away from the b
axis. In hedenbergite (TN = 38 K), the spins are in the ac plane (132 from c) and
in acmite (TN = 8 K) nearly parallel to c (Ghose et al. 1988; Ballet et al. 1989).
Fayalite, Fe~+Si04 where Fe 2 + ions occur on two types of octahedral sites M1
and M2, shows a more complex behaviour. Below TN (65 K), the spins on two
M2 sites (with M1 in the middle) are parallel and anti parallel to b, whereas the
spin on M 1 is canted away from b and still fluctuating. With decreasing
temperature, the M 1 spins rotate and finally order below about 23 K (Fuess et
al. 1988). The complex spin ordering processes result in a sharp lambda peak in
the specific heat at 65 K followed by a broad shoulder around 30 K (Robie et al.
1982). Quite a different magnetic ordering behavior is shown by the mixedvalence iron silicate, ilvaite, (CaFe 2 +Fe H )Fe 2 +Si 2 0 40(OH), where Fe 2 + and
Fe 3 + ions occur in double octahedral chains (A sites), above the below which
occur larger Fe 2 + octahedra (B sites). Below TN (120 K), within one octahedral
chain, the alternating Fe 2 + and Fe 3 + ions are ferromagenetically coupled,
which are antiferromagnetically coupled to the edge-sharing adjacent
Fe2+ -Fe H chain; the Fe2+ spins (B site) are still fluctuating and order at a
much slower rate from below TN to about 50 K, at which point they order
rapidly. This behaviour stems from spin frustration; the B site spin, which occurs
at the apex of a slightly distorted square pyramid, senses parallel A site spins on
one side and anti parallel spins on the other. It finally adopts a parallel
configuration to the nearer set of A site spins. This effect is shown also by the
magnetic susceptibility measurements and specific heat. The evolution of the
magnetic moments and the internal magnetic fields as a function of temperature
has been measured by neutron diffraction and M6ssbauer spectroscopy, respectively (Ghose et al. 1990).
0
References
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acmite, NaFeSi 2 0 6 Phys Chern Mineral 16: 672-677
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transitions in ferroelastic and coelastic crystals. Cambridge Univ Press, Cambridge, U.K.,
pp 334-349
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Coey JMD, Ghose S (1988) Magnetic phase transitions in silicate minerals. In: Ghose S, Coey
JMS, Salje E (eds) Structural and magnetic phase transitions in minerals. Springer, Berlin
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Dolino G (1988) Incommensurate phase transitions in quartz and berlinite. In: Ghose S, Coey
JMD, Salje E (eds) Structural and magnetic phase transitions in minerals. Springer, Berlin
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Fuess F. Ballet 0, Lottermoser W (1988) Magnetic phase transitions in olivines, M 2 Si0 4

(M = Mn,Fe,Co,FexMn l _ x)' In: Ghose S, Coey JMD, Salje E (eds) Structural and magnetic
phase transitions in minerals. Springer, Berlin Heidelberg New York, pp 185-207
Ghose S, Hewat AW, Van Dang N, Weidner JR (1988) Magnetic phase transitions in quasione dimensional antiferromagnets: ferrosilite, Fe 2 Si 2 0 6 and hedenbergite, CaFeSi 2 0 6 .
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Ghose S, Tsukimura K, Hatch DM (1989) Phase transitions in ilvaite, a mixed-valence iron
silicate. II. A high temperature single crystal X-ray diffraction study and Landau theory of
the monoclinic to orthorhombic phase transition induced by electron delocalization. Phys
Ghose S, Hewat AW, Pinkney M (1990) A powder neutron diffraction study of magnetic phase
transitions and spin frustration in ilvaite, a mixed-valence iron silicate showing a semiconductor-insulator transition. Sol State Commun 74: 413-418
Ghose S, Ito Y, Hatch DM (1991) Paraelectric-antiferroelectric phase transition in titanite,
CaTiSiO s. I. A high temperature X-ray diffraction study of the order parameter and
transition mechanism. Phys Chern Mineral 17: 591-602
Hatch DM, Ghose S (1991) The rx-fJ phase transition in cristobalite, Si0 2 . I. Symmetry
analysis, domain structure and the dynamical nature of the fJ-phase. Phys Chern Mineral 17:
554-562
Peacor DR (1973) High temperature single crystal study of the cristobalite inversion. Z Krist
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Raman CV, Nedungadi TMK (1940) The rx-fJ transformation in quartz. Nature 145: 147
Robie RA, Finch CB, Hemingway BS (1982) Heat capacity and entropy offayalite (Fe 2 Si0 4 )
between 5.1 and 383 K. Am Mineral 67: 463-469
Van Tendeloo G, Van Landuyt J, Amelinckx S (1976) The phase transition in quartz and
AIP0 4 as studied by electron microscopy and diffraction. Phys State Sol A33: 723-735
Van Tendeloo G, Ghose S, Amelinckx (1989) A dynamical model for the pI-IT phase
transition in anorthite, CaA1 2 Si zO g I. Evidence from electron microscopy. Phys Chern
Mineral 16: 311-319

G.
BESSON
and V.A.
DRITS
Poorly crystallized substances occupy a special place among natural and

synthetic compounds. They are characterized by very small particle size, high
contents of various defects, metastability and, consequently, low stability with
respect to external action.
The conventional notion of a crystal structure viewed as an arrangement of
atoms repeated all over the three-dimensional crystal volume has practically no
physical meaning in such conditions. This, however, does not preclude the
existence of one- or two-dimensional periodic structural units within such
compounds.
Poorly crystallized minerals (PCM) are abundant is weathering crusts, soils,
products of volcanic, hydrothermal, and magmatic activities; they are contained
in marine and river sediments. They result form bacterial activity and are
formed at initial stages of crystallization of gels, colloids, and glasses. PCM
include various oxyhydroxides and, primarily, oxyhydroxides of Fe, i.e., limonites, ferroxyhites, ferrihydrites, and of Mn, i.e., vernadites, achtenskites, many
139
clay minerals (smectites, metahalloysites, greenalites, hysingerites, minessotaites), carbonates, and carbon of different degrees of graphitization.
The nature of defects in PCM structures is extremely diverse. Very small
coherent scattering domains, stacking faults of different types, and compositional heterogeneity are typical of PCM. Failures of periodicity are often due to
intergrowth effects. In this case, structurally compatible one- or two-dimensional modules of distinct structure and composition are combined within the
crystal, with varying degree of order/disorder and in different proportions. As a
result, irregular mixed-layer (e.g., illite-smectite, asbolane-buserite), mixed-channel (e.g., nsutite), and mixed-chain (e.g., some biopyriboles) structures are
formed, that are characterized by nonstoichiometric compositions. The conventional definition of "phase" is, in fact, unsuited for such formations. Among
microdivided PCM, compounds occur with either commensurate or incommensurate modulated structures, such as minessotaite, greenalite, antigorite,
valleriite, and tochilinite.
The basic hindrance to the analysis of structural and crystal-chemical
features of PCM is that most solid-state physical methods are indirect ones.
Interpretation of experimental spectra and diffraction patterns is therefore a
complicated problem, and an unambiguous solution requires a special methodological approach. The essence of this approach, valid for various specific
methods, consists in elaborating theoretical and methodological developments.
For various structural models these would allow a simulation of spectra and
diffraction patterns identical to experimental ones.
The main methods for investigating PCM structures are those based on
X-ray, electron, and neutron diffraction. The presence of defects substantially
modifies the intensity distribution in a diffraction pattern. The problem is to
determine the nature of defects, their contents and distribution pattern from
diffraction data. Conventional methods of diffraction structure analysis are
obviously fruitless in this case. One of the effective methods is simulation of
diffraction patterns from structural models containing various defect types and
their comparison with the experimental ones. This approach is being effectively
developed at present and has been used for revealing the basic structural
peculiarities of many PCM such as defective kaolinites, smectites, mixed-layer
minerals, and various Fe- and Mn-oxyhydroxides.
An extraordinary contribution to the analysis of PCM real structure has
been made by high-resolution and analytical electron microscopies. These
methods are especially effective for revealing dislocations, stacking faults,
commensurate and incommensurate modulated structures, intergrowth, and
nonstoichiometry. The significance of these techniques is that they yield structural and chemical information obtained from mineral particles in mixtures with
crystallites of other minerals. Combination of HRTEM with simulation of
diffraction effects is a promising way for an unambiguous determination of
PCM real structures.
Application of modern spectroscopic methods is indispensable for PCM
studies. High sensitivity to short-range order and electronic state of atoms
140
enables the analysis of the local structure around atoms of interest, oxidation
state, and the pattern in the cation distribution.
Methodologically, it is most important that the results obtained by spectroscopic methods be always treated in the light of diffraction data on the structural
peculiarities of the sample involved. For example, EXAFS and XANES spectra
of todorockite and vernadite are practically identical; they indicate similar
short-range order in these Mn-oxides. Diffraction data, however, show that their
three-dimensional structures differ substantially.
At present, comprehensive studies of PCM real structure are being intensively developed. The appropriate approach to such studies is to apply a
representative panel of modern solid-state physical and chemical methods to the
same sample (not just to the same mineral!) and to obtain compatible results.
References
Buscek P, Cowley J, Ewing L (eds) (1989) High resolution electron microscopy. Univ Press,
Oxford 645 p
Drits VA (1987) Electron diffraction and high resolution electron microscopy of mineral
structures. Springer, Berlin Heidelberg New York
Drits VA, Tchoubar C (1990) X-ray diffraction from disordered microdivided lammelar
structLires. Theory and application to silicates and carbons. Collaboration with Besson G,
Bookin A and et al. Springer, Berlin Heidelberg New York
Hawthorne FC (ed) (1988) Spectroscopic methods in mineralogy and geology (1988) In:
Hawthorne FC (ed) Reviews in mineralogy, vol 18. Mineral Soc, Washington, DC
Zvyagin BB (1967) Electron diffraction analysis of clay mineral structures. Plenum, New York

R.C. EWING and J. AKIMOTO
Metamict minerals are a special class of naturally occurring amorphous materials. The radiation-induced, periodic-to-aperiodic phase transition (metamictization) is caused by alpha-decay of constituent radionuclides of the uranium and
thorium decay series. The damage is caused by two, separate, simultaneous
processes associated with the alpha-decay event. (1) An alpha particle
( '" 4.5 MeV) with a range of 10 000 nm. (2) The alpha-recoil atom
( '" 0.07 MeV) with a range of 10 nm. The transition from a periodic to an
aperiodic structure occurs over a rather narrow range of dose (10 25 to 10 26
alpha-decay events/m 3 ) and can be studied in natural materials (e.g., zircon and
microlite) which contain significant quantities of U and Th which in combination with their age (10 6 to 10 9 years) results in alpha-decay doses up to 10 27
alpha-decay events/m 3 . A succession of techniques - X-ray diffraction, high
resolution transmission electron microscopy, extended X-ray absorption, fine
141
structure spectroscopy, and X-ray absorption near edge structure spectroscopy

have been used to follow the radiation-induced transition. The transition progresses through three stages.
1. Accumulation of Frenkel defect pairs which causes a shift in the position of
diffraction maxima to lower values of two theta (unit cell expansion) and
diffraction maxima broadening (an increase in strain and decrease in crystallite
size).
2. Significant in-growth of aperiodic areas with alpha-recoil track overlap
which causes a decrease in diffraction maxima intensity and a decrease in the
strain of the remaining aperiodic areas. Vacancies may migrate to aperiodic
regions.
3. Complete overlap of alpha-recoil "tracks" resulting in an aperiodic structure
that is electron diffraction amorphous. Individual network-forming coordination polyhedra may have decreased coordination numbers, shortened M-O
bond lengths, and slightly increased and a wider range of second nearest
neighbor (e.g., M-O-M) bond lengths.
Of the naturally occurring phases which become metamict, zircon, ZrSi0 4 , is

perhaps the most important and the most studied. Zircon occurs with total
uranium and thorium concentrations up to 3000 ppm. Alpha-decay doses, over
periods of hundreds of millions of years, may reach values as high as 10 26 alphadecay eventsjm3, equivalent to one displacement per atom (dpa). Over the
narrow range of dose from 10 25 to 10 26 alpha-decay eventsjm\ crystalline
zircon is converted to an X-ray and electron diffraction amorphous material
(Fig. 31). The transition is marked by a pronounced change in properties: (1)
decrease in density (17%); (2) decrease in refractive indices and birefringence
until isotropic; (3) darkening of color; (4) decrease in intensity and broadening of
optical and infrared absorption bands with loss of polarized spectra; (5)
increasing thermoluminescence; (6) broadening, decrease in intensity, and shift
in the position of diffraction maxima to lower values to 2(} which corresponds to
an increase in unit cell volume (5%); (7) decrease in elastic modulus (70%); (8)
decrease in hardness (40%); (9) decrease in Poisson's ratio (7%); (10) decrease in
thermal conductivity; (11) increase in absorbed water; (12) increased susceptibility to dissolution (13) increased chemical diffusion. Pu-doped synthetic zircons,
show approximately the same density change (16%) at doses of 10 26 alphadecay eventsjm 3 . Individual, zoned (with respect to U and Th concentrations)
zircons (Fig. 31) and a suite of micro lites from a single locality (Fig. 32), spanning
the range of doses over which metamictization occurs, have been studied by
transmission electron microscopy.
The most recent focus of research on the metamict state has been on the
explicit determination ofthe damage in-growth process and the final structure of
the metamict state. Damage in-growth experiments have been completed on a
number of phases (e.g., zircon, zirconolite, and apatite) which have been doped
with highly-active P U 238 or Cm 244, causing the doped phases to reach saturation doses of alpha-decay events in 2 to 4 years. These studies provide an
142
143
accelerated view of the metamictization process. Zircon became fully amorphous at a dose of 14 x 10 25 alpha-decay events/m 3 ; apatite, 11.7 x 10 24 alphadecay events/m 3 . Volume expansions were 16.6 and 8%, respectively. Ion
implantation experiments have been completed on zircon using Ar and Kr at 1
to 3.5 MeV up to 10 15 ions/cm 2 , Pb at 40 to 240 keV up to 10 13 Pb/cm 2 , Pb at
approximately 230 keV up to 10 15 Pb/cm 2 , Pb at 540 keV up to 10 15 ions/cm 2 ,
and fast neutron irradiations up to 3.6 X 10 20 neutrons/cm 2 . In addition, single
types of irradiation (1.5 MeV Kr+) have been used to irradiate a wide variety of
structure types (e.g., neptunite, titanite, gadolinite, zircon, and olivine). In all
cases, it was demonstrated that crystalline phases undergo the radiationinduced transformation to the aperiodic state. Principal conclusions from these
experimental studies include: (1) The initial expansion of the unit cell may be
anisotropic with the greatest expansion occurring between well-bonded structural units (e.g., perpendicular to sheets or chains). (2) At higher doses, the
volume change is associated with radiation-induced amorphization as the
fraction of amorphous material increases (e.g., overlap of alpha-recoil tracks). (3)
The amorphization process is consistent with a model of multiple overlap of
displacement cascades, suggesting amorphization is the result of defect accumulation rather than simply amorphization in the collision cascades created by the
alpha-recoil nucleus. This model requires further refinement and confirmation.
(4) In the case of zircon, simple defects are annealed over geologic time, and this
suppresses the initial swelling and delays the onset of amorphization. (5) Still, as
far as alpha-decay event damage is concerned, dose rate effects (the difference
between experimentally damaged zircons and natural zircons is on the order of
10 8 ) appear to be minimal. (6) Structure and bonding affect the damage ingrowth process. For a range of structure types implanted by 1.5 Me V K + ions,
the range of critical dose required for amorphization is from 1.7 to 6
x 10 14 ions/cm 2 . There is a correlation between the critical dose required for
amorphization and structural complexity (lower for more complex structures)
and melting temperatures (higher for higher melting points) of the structure
types examined .
..
Fig. 31a-c. High-resolution transmission electron micrographs and electron diffraction patterns of zircon. a The least-damaged area displays mottled diffraction contrast in the (101)
plane. Two-dimensional lattice fringes are evident and a unit cell (a = 0.66 nm and c
= 0.60 nm) is outlined. Some lattice fringes are bent and discontinuous. Examples of aperiodic
domains (I to 5 nm) in which lattice fringes are almost absent, possibly because of alpha-recoil
tracks, are indicated by arrows. In spite of these bright-field features, the electron diffraction
spots are sharp and clear. b The intermediately damaged area. The bright-field image is
paralled to (Ill). The spots in the diffraction pattern are broad and diffuse, which corresponds
to increased structural distortion. Although the aperiodic domains are as abundant as the
domains of distinct lattice fringes, the distorted crystalline domains have the same orientation.
Lattice dimensions are given for the [110] (1.01 nm) and [OIl] (0.97 nm) directions. c The most
damaged area. The bright-field image shows no evidence for long-range periodicity. In
addition to diffuse rings, the electron diffraction pattern has powder rings that result from
misoriented microcrystallites. The arrow points to a micro crystallite displaying [100]
(0.66 nm) lattice fringes. (Chakoumakos et a!. 1987)
144
Fig.32a-j. HRTEM images showing progressive structural damage to microlite as a function

of increasing alpha-decay event dose (IX-decay events/mg, uncorrected for annealing): a
< I015. b3 X1016. C 3 X1016. e 9 XI01 6.fI017.g4 xI0 17 .hEnlargementofareaoutlineding.
i and j are SAD patterns corresponding to HRTEM images in a and h. (Ewing et al. 1988)
X-ray absorption spectroscopy has been the most commonly applied technique for the determination of the structure of the metamict state, as it can
provide information on coordination number and bond-lengths in the first and
second coordination spheres. However, because the compositions of most
metamict minerals are so complex, it has not been possible to construct a unique
model for the aperiodic arrangement that is consistent with bulk properties such
as density. Still, principal conclusions from XAS studies include: (1) For most
phases, nearest-neighbor coordination geometries (eN and M-O distances)
remain nearly constant with the possibility of limited distortion of the coordination polyhedron. Major changes in the coordination geometry are a result of the
stereochemistry of the cations involved. (2) The loss of long-range periodicity is
Fig. 32. Contd.
145
146
associated with changes in the metal-oxygen-metal bond angles caused by tilting

of joined coordination polyhedra across shared corners and edges. (3) For
certain cations (i.e., Zr and Th) the nearest-neighbor structure is different that
found in quenched glasses.
The study ofmetamict minerals remains an active area ofresearch because of
its application to the evaluation of the long-term durability of ceramic nuclear
waste forms which serve as actinide hosts. In addition, the radiation-induced
changes in the properties of ceramics have many technological applications
(e.g., improved tribological properties of ceramic-made prosthetic devices, e.g.,
artificial hips).
References
Akimoto J, Imafuku M, Sugitani Y, Nakai I (\988) Fe K-Edge Xanes and Mossbauer study of
the amorphous state in metamict gadolinite and samarskite. In: Synchrotron radiation
applications to mineralogy and petrology. Theophrastus, Athens, Greece, pp 141-171
Chakoumakos BC, Murakami T, Lumpkin GR, Ewing RC (1987) Alpha-decay induced
fracturing in zircon: the transition from the crystalline to the metamict state. Science 236:
1556--1559
Clinard FW, Jr (1986) Review of self-irradiation effects in Pu-substituted zirconolite. Ceram
Bull 65: 1181-1187
Ewing RC (1975) The crystal chemistry of complex niobium and tantalum oxides. IV. The
metamict state: discussion. Am Mineral 60: 633-728
Ewing RC, Chakoumakos BC, Lumpkin GR, Murakami T (1987) The metamict state. Mater
Res Soc Bull 3: 58-66
Ewing RC, Chakoumakos BC, Lumpkin GR, Murakami T, Greegor RB, Lytle FW (1988)
Metamict minerals: Natural analogues for radiation damage effects in ceramic nuclear waste
forms. Nucl Instr Meth Phys Res B32: 487-497
Farges F, Calas G (1991) Structural analysis of radiation damage in zircon and thorite: an
X-ray absorption spectroscopic study. Am Mineral 76: 60-73
Farges F, Ewing RC, Brown GE (1993) The structure of aperiodic, metamict,
(Ca,Th)2Zr2Ti4014: an EXAFS study of the Zr, Th, and U sites. J Mater Res 8: 1983-1995
Greegor RB, Lytle FW, Chakoumakos BC, Lumpkin GR, Ewing RC, Spiro CL, Wong J
(1987) An investigation of the Ta site in radiation damaged natural pyrochlores by X-ray
absorption spectroscopy. In: Bates JK, Seefeldt (eds) Scientific basis for nuclear waste
management. Mater Res Soc Proc 84: 645-658
Hawthorne FC, Groat LA, Raudsepp M, Ball NA, et al. (1991) Alpha-decay damage in titanite
Holland HD, Gottfried D (1955) The effect of nuclear radiation on the structure of zircon. Acta
Cryst 8: 291-300
Lumpkin GR, Ewing RC (\988) Alpha-decay damage in minerals of the pyrochlore group.
Lumpkin GR, Chakoumakos BC, Ewing RC (1986) Mineralogy and radiation effects of
microlite from the Harding Pegmatite, Taos County, New Mexico. Am Mineral 71: 569-588
Lumpkin GR, Eby RK, Ewing RC (1991) Alpha-recoil damage in titanite (CaTiSi05): Direct
observation and annealing study using high resolution transmission electron microscopy.
J Mater Res 6: 560-564
Murakami T, Chakoumakos BC, Ewing RC, Lumpkin GR, Weber WJ (1991) Alpha-decay
event damage in zircon. Am Mineral 76: 1510-1532
Nakai J, Akimoto J, Imafuku M, Miyawaki R, Sugitani Y, Koto K (1987) Characterization of
the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses.
Phys Chern Minera115: 113-124
2.3 Systematics of Crystal Structures and Crystallochemical Classifications
147
Wang LM, Eby RK, Janeczek J, Ewing RC (1991) In situ study of ion-beam-induced
amorphization of complex silicate structures. Nuc1 Instr Meth Phys Res Beam interactions
with materials and atoms. B59/60: 395-400
Weber WJ (1983) Radiation-induced swelling and amorphization in Ca2Nd8(Si04)602.
Radiat Elf 77: 295-308
Weber WJ (1990) Radiation-induced defects and amorphization in zircon. J Mater Res 5:
2687-2697
Weber WJ, Eby RK, Ewing RC (1991) Accumulation of structural defects in ion-irradiated
Ca2Nd8(Si04)602. J Mater Res 6: 1334-1345
2.3 Systematics of Crystal Structures and Crystallochemical

Classifications of Minerals
Taxonomies and classifications always turn into ogres and monsters.
P.B. Moore (from a letter to the editor)
2.3.1 Prolegomenon
P.B.
MOORE
What is the goal of crystal structure analysis? What purpose does contemporary
crystal structure analysis and refinement serve? The goal is to provide a correct
structure solution and a high level of precision for the refined data. Modern
technology can allow very precise data, indeed. Much of the quality of the data
hinges on the quality of the crystal. A small, ground sphere has many advantages, as correction for absorption anisotropy is usually the most critical aspect
in preparing good observed structure factors. Film data should always be
collected in advance, and careful check for twinning, spot shape, and possible
weak superstructure reflections can be more easily facilitated. The range in the
final discrepancy index (R) should be below R = 0.06, and superior cases will
provide R = 0.01 -0.03.
Many structure refinements are hampered by lack of elemental analysis of
the sample. For minerals, where solid solution and mixed valences abound, lack
of assayed cation and anion content could be disastrous. A good electron probe
analysis should accompany the structure study. Unfortunately, many mineral
crystals are not simple parsimonious things but can be very complex, and a few
contain over 20 different ionic components in amounts greater than 0.5 wt. %
each. Clearly, not much of their crystal chemistry can be known with any degree
of precision, let alone confidence, in the absence of some preliminary analytical
study. In crystals with more than one structure domain or with an extensively
disordered region such as a sheet component, even R < 0.10 may be hard to
achieve. Such structure solutions and refinements are called "averaged structures".
The purpose of crystal structure analysis is quite another matter. In the past,
structure work often accompanied more general studies by a mineralogist or a
petrologist. (Naturally, a firm background in inorganic chemistry is implied in
148
these disciplines). It is a sad but ineluctable modern fact that many crystallographers who study mineral structures are neither mineralogists nor petrologists at
all, but treat the structure investigation as an end in itself. Alas, all the time and
effort is put into the problem which often becomes an "abandoned orphan of
science". But the superior refinement can provide a check on the indexed powder
data files; an explanation of hardness and cleavage; a check on specific gravity
by density calculation; a suggestion toward explaining color, pleochroism, and
reflectance; a possible calculation of the optical characters including indices of
refraction; bond distances, bond angles, coordination polyhedra, solid solutions,
bond strength, and bond valence sums - all these characters which make up so
much of mineralogy from one crucial study! For this reason, crystal structure
analysis should be in the armamentarium of every good mineralogist.
Beyond the physical characters, resides the classification of the mineral. And
here, the most essential experimental tool is crystal structure analysis. At the
most rudimentary level, classification serves as a "pigeonholing" of the structure
in the large class of known mineral structures. In principle, there are infinitely
many classifications but we are only interested in those which possess a
hierarchy. Mineral classification today is largely chemical-crystallographic,
where the connectedness of the hierarchical tree is based on some rules which
define structure similarity. A paragenetic classification of minerals is commendable and is based on associations in the field (the "sociology" of crystal
phases), P-T -X conditions and Eh-pH diagrams in the laboratory. The
wedding of mineral paragenesis to structure type would be a fruitful albeit
difficult task, say toward unravelling the geochemistry of some complex ore
deposit such as at Franklin, New Jersey, USA.
Recently, evidence has been accumulating concerning the uncanny frequency of close eutactic arrangement of cations in an oxysalt mineral to the
elements in some intermetallic phase. The path-breaking paper by O'Keeffe and
Hyde (1985) is one such example. This relationship, the observations of which
can no longer be denied, languishes for want of some underlying theoretical
basis. It seems, however, that many such cases involve oxysalts/intermetallics
which are based on the close-packing of cations/elements rather than the
classical model of anion close-packing which, by the way, does not have a strong
theoretical basis either. At best, we can declare that a troubling array of
structure/anti structure pairs exists, e.g., CaF 2/0Li2'
Unfortunately, a disturbing number of reported crystal structures of minerals
are wanting an appropriate representation (the "abandoned orphan" idea looms
forth again!). Appropriate representation is how we relate structures to each
other. About the highest structural character in any good structural hierarchy is
the fundamental idea of close-packed spheres of anions or of cations (or in
mixed-layer structures as in perovskite, Ti[03Ca]"). Once the stacking sequence
of close-packed layers is known, the refined structure can be directly compared
with the ideal calculable geometrical model. Yet ironically, but few investigators
go through the trouble to demonstrate this comparison. Close-packed structures open up a whole new world in combinatory theory, order-disorder,
2.3.1 Prolegomenon
149
group-subgroup relationships. Just why are these structures arranged and

populated that way? And some of these sequences can be very complex, indeed,
such as the electronically important magnetoplumbite structure type,
2Felz[019Pb]" x = 'chhhcchhhc', a ten-layer sequence. It appears that a
significant number of mineral structures belonging to the monoclinic or triclinic
systems are based on the principles of close-packing. The principle was often
missed by the earlier investigators. Common examples include a stacking vector
along the [100]*-, [001]*-, or general [hkl]*-direction in the monoclinic system,
or a stacking vector along the [100]*-, [010]*-, [001]*-, or general [hkl]*direction in the triclinic system. There is no physical reason why the stacking
vector should coincide with an axis of symmetry. Such a list of candidates is
probably large, and the study requires an intimate association with group
theory, set theory, and the manipulation of matrices. Because so many more
fundamental principles have been overlooked in existing structure representation, the classification of mineral structures still has a long path to face in its
evolution toward a closed, countable set of objects.
Which classification do we desire? Because a good scientific model is based
on its ability to predict, we would desire a natural scheme which embraces all
objects in the set of mineral structures. It should be logical and inclusive, that is
a slot must be available for a newly solved mineral structure. It must be based on
the most fundamental principles of bonding. The chemical classification as we
practice it probably began with Berzelius. He considered minerals as salts of
anions and anionic radicals. Familiar examples are Fl - , Cl l - , Brl - , 11 - , OZ -,
SZ-, Se Z-, Te z -; NOj-, CO~-, BO~-, CIO!-, SOi-, POl-, SiO!-, BO~-.
Berzelius presaged the concept of electronegativity and the formation of Lewis
octets. The anion is the most electronegative element in the mineral's formula
and it completes its octet (inert gas configuration) with the addition of electrons
in its valence shell. An anionic radical is created by the inert gas anion
coordinating to a small cation usually stripped of its valence electrons. This
small cation, usually with high charge, is often the next most electronegative
element in the mineral's formula.
It appears that two criteria are sufficient to uniquely define mineral species:
end-member formula and structure type, that is a necessary chemical-crystallographic duality. The Berzelius criterion is merely broadened to include solid
solutions. Thus, any sensible system would classify a mineral structure according to (1) anionic group and (2) structure. It would be natural to commence with
the simplest formulae (cell contents) and work up to increasing complexity. The
structure classification adopts the classical convention of some hierarchy based
on the polymerization of the anionic radical. Consider T -0-T, two tetrahedrally coordinated cations bonded to one central oxide anion. If Po, the sum of
Pauling (1960) bond strengths of cations to that oxide anion is > 2.0, the oxide
will rarely be coordinated by 2T (e.g., SOi - , POl- , etc.). If Po ::; 2.0, then the
anionic radical will easily form polymers (e.g., BzO~ -, SizO~ - , etc.). Further
condensation, as in the silicates, occurs. Thus, we have nesosilicates, oligosilicates, inosilicates, phyllosilicates, tektosilicates.
150
This classification scheme is being exploited effectively by H. Strunz in his

new crystal-chemical tabulation of the mineral species. It is a logical system and
is based on running indices which ease retrieval and which are based on the
anionic group and the structure type. Strunz has the foresight to exploit a unit
(usually cluster, chain, or sheet) of structure which tends to repeat itself over one
or many different structure types. The term fundamental building block (f.b.b.) has
become entrenched in the literature. This f.b.b. tends to be that part of the
structure which possesses the greatest bond strengths. It is often written in
brackets. A good example is laueite:
H18Mn2+Fd+P~+018
empirical formula
(element ratios)
Mnz+Fe~ + (OH}z
(P0 4}z' 8H zO
"hydrated" formula
(vogue)
Mnz+(H zO)4 [Fe~ + (H zO)z(OH}z(P0 4)zJ' 2H zO
structural formula
The first formula is perfectly reasonable: it gives the ratios of ions present.
Unfortunately, it says nothing about chemical bonding. The second is, ironically, the one most frequently used to this day but is delusive in misleading the
reader about bonding. The third, still somewhat incomplete, strives to emphasize bonding. The f.b.b., a sheet, is in brackets. There are four kinds of protons:
those bonded as hydrate water after the period, those bonded as hydroxyl, those
bonded as aqua ligated to Fe3+ and those bonded as aqua ligated to Mn2+.
Experimentally, the hydrate water is easily lost below ca. 120C; only above ca.
180C is the remaining water lost and with the destruction of the structure.
Clearly, this formula makes more sense that the second "hydrated" formula so
much in vogue. Water plays an important and variegated role in mineral
structures. This is why it is incumbent upon mineral chemists to state water's
role(s) whenever a structure is known. Such distinction among hydroxyl,
hydrated, and aquated is important, if not necessary, in some mineral groups
such as the H-bearing borate minerals.
The classifications proposed in the literature are vast, most apply to
restricted families of structures and all are wanting in details. In close-packing,
for example, the perfect geometrical model is already known once the structure
cell contents and stacking sequence are known. In principle, all possible
arrangements could be worked out for some given cell, then one could step back
and speculate why one arrangement has been selected by Nature over all the
others. Yet combinatorial problems usually tend to be rather difficult to solve.
Besides, the representation of real structures among all hypothetical possibilities
tends to comprise only a tiny fraction of all possible arrangements. (See
McLarnan and Moore 1981 for a review on this problem, the central vehicle
being the famous P6lya enumeration theorem.) Classifications also tend to be
highly subjective, and they rarely have any predictive value. Predictions, when
they do pan out, usually exploit some other truncating vehicle, such as the
Pauling (1960) electrostatic valence rules. So, enumeration may be a vehicle, but
151
2.3.1 Prolegomenon
the number of elements (called "animals") in the set is usually so large that the
framework eventually collapses.
Another famous problem involves the populations of valence electrons
remaining for a cation. An element can be considered in a mineral crystal as (1) a
metal (as in native elements and intermetallics), (2) an anion (closed Lewis octet),
(3) a Jahn-Teller cation (polyhedral distortion for certain d; -y2, d; populations), (4) a lone pair cation (ns 2 valence electrons remaining, n = row of
Periodic System), and (5) a naked cation (an element stripped of all valence
electrons to form a closed core). Categories (2) and (5) are the classic examples
which Pauling used to obtain his electrostatic valence rules. These rules are not
very helpful for categories (1), (3), and (4). However, the eutactic relation of
atoms in metal phases in category (1) to cations in oxysalts in (2), (3), (4), and
(5) is intriguing. Some examples are presented where the relation is calculated as
(d), the atom coordinate difference between oxysalt and metal, scaled to the
larger oxysalt cell:
4Pb2Mn~ + 0z(Si 20
7)
kentrolite (5 unique cations)
3Mni+ Mn~+Sb5+Si2024
hlngbanite (13 unique cations)
4Mg 3 Ti0 2(B 20 6 D)
warwickite
(3 unique cations)
SURe 2(' ch .), d = 0.00-0.34 A

a Laves phase, e.g., MgZn2
4SLa (. ch .), d
4Na 2CaZrF 2(Si 20 7 )

wohlerite
(14 unique cations)
= 0.00-0.32 A
SC0 2Si, d = 0.00-0.62 A

synthetic
These are but few of many such relationships. Note the diversity covered in
the third line. For some structures, it seems our notions of mineral atomic
arrangements are turned on their heads, as if the cation packaging provides the
interstices for the anions!
Jahn-Teller ion and lone pair ions invariably induce a distortion in the
coordination polyhedron. Distortions can be severe. For example, [9] Pb 2+_0 2= 2.2-3.2 A range is a consequence of lone pair-bond pair interactions. In
naked [6] Pb4 +-0 2- = 2.16-2.20 A, the range for the highly charged cation
is small and its oxide coordination octahedron is fairly regular. In fact, the
Pb 4 +_0 2- = 2.IS A average is roughly the lower limit found for Pb2+ _0 2-.
The lone pair distortion is fairly well understood only recently with the advent of
precise structure refinements. It appears to be an electrostatic phenomenon.
Thus, the short Pb 2+_0 2- = 2.2 A values are not indicative of covalent
bonding, but are bonded on that side of Pb 2+ (the "naked side") opposite the
centroid of the lone pair. Jahn-Teller ions such as 4d 4Mn3+ and 4d 9 Cu2+ can
be similarly treated: the distortion is a more symmetrical version of the lone pair
distortion. For example, four long equatorial (dx 2_y2 electron population) and
two short apical octahedral bonds for Mn3+ _0 2- create an oblate ellipsoid and
the more frequent four short equatorial and two long apical (dz 2 electron
population) octahedral bonds create a prolate ellipsoid. In turn, these ellipsoids
provide directed bond strengths whose Pauling sums to anions are more nearly
152
neutral. Similar reasoning has been applied to the distorted polyhedra enveloping a lone pair cation, but here the displacement of the central cation toward the
lone pair centroid can be predicted by use of the Pauling electrostatic valence
rules.
These are but a few of the examples which face the chemical crystallographer
of minerals. Electronic distortions result from a wide variety of origins, but all
seem to manifest themselves in well-refined crystal structures. For this reason,
the crystal and chemical aspects of structure are inseparable and both require
equal attention. Let us remark finally that nearly every topic in this book
ultimately touches upon some aspect of chemical crystallography.
2.3.2 Contemporary Aspects of Classifications

G.B.
BOKIY
A classification is a system whose property embraces a countable arrangement

of some set of objects. It is based on the established limits and relations between
the properties of these objects. It is one of the fundamental processes in science.
Facts and phenomena must be ordered before they can be understood through
working out the common principles which demonstrate their existence and
apparent order. Hopefully, classification also has some predicitive power.
Classification (or taxonomy) became a scientific discipline which corresponds to all categories that define an independent subject. In 1984 the International Classification Federation was founded. In the same year the international
Journal of Classification appeared. Classification is connected with many sciences, in particular with information and computer sciences.
Contemporary banks of data are created as storage for retrieving data
amidst large bodies of information, in which mechanical methods are broadly
implemented. If the classification is unsatisfactory these methods cannot be
efficiently applied. Beyond the time-consuming process of information recovery,
classification consolidates the general knowledge earlier obtained, eases and
intensifies the work of an investigator, and helps find the path to the discovery of
the regularities and laws of Nature.
The set of the objects of the investigation and practical activity is presently
so large and the objects themselves so complex that the usual human intuitive
approach is not enough to classify, in order to satisfactorily organize this set. No
languages, no effective information searching systems are possible without good
classifications. It is impossible to find analogs, to diagnose, and to predict
unknown things and their properties. It is difficult to predict reliably and to
chart the development of a given scientific branch.
The classification systems allow the construction of predictive models. These
logical models afford the opportunity without experiment to predict the possibilities of retrieving the novel objects and processes, to find "white spots" in
2.3.2 Contemporary Aspects of Classifications
153
the functional systems. The predictive models are intended for enumerating the
taxa, i.e., they fulfil the same functions which lead to the descriptors in the
classification of biological objects.
In the descriptor automatic information systems where there is a set of the
physical objects and documents of the information, the automation of the classification methods is necessary for the creation of the data banks of the "expert"
system for general use.
The mathematical methods: cluster analysis and the methods of grouping
are used simultaneously with the intuitive methods for the construction of the
classifications. Counting theory plays a role here. The purpose of the cluster
analysis is a choice of the groups of the synonymous objects, the various groups
differing greatly between each other. In general, it is clear that when using
the whole system of attributes, a full correspondence can be made between "the
space of the attributes" and the "space of the objects".
It is absolutely clear that the task of the recognition of the images and the
tasks of the classification have the same purposes, and it is impossible to solve
these without use of the modern developments of applied mathematics and the
computer technology.
All classifications according to their internal structure are divided into
hierarchical and combinatorial ones. On the other hand, it is possible to
subdivide all classifications into two groups: the Natural classifications and the
Artificial classifications, the former reflecting the laws of Nature.
The artificial classifications are created for a variety of purposes. For
example, the purpose of the artificial classification can be simply the creation of
the searching system. The Natural classifications are equal to the laws of Nature,
i.e., it is unreasonable to put the question: "What are they for?"
There are a plethora of artificial classifications, much more than natural
ones, as they are used in all spheres of human activity. For natural classifications, which relate mainly to the exact and usually fundamental sciences, their
number is much less.
These types of classification are discriminated also by the character of the
attributes they use. The use of many attributes is typical for the Artificial
classifications. The special divisions of mathematics (statistical methods, cluster
analysis, and so on) are often used for investigations with these attributes. The
attributes become synonymous for this purpose. They are often contrived, i.e.,
the subjective aspect is brought into the classification. In the Natural classifications very few attributes are used, ideally only one. This attribute must be the
essential one. The change of one essential attribute by another one is always "an
event". Recalling that in evolving the Periodic System of the chemical elements,
more than 50 years were needed to effect the change of "an atomic weight" into
"an atomic number". One (essential) attribute among the set of the properties
existing for every chemical element was given, which was the basis of the
classification.
In another instance, the classification attribute "crystal form" was replaced
by "symmetry". The choice of the essential attribute and its replacement by
another more essential one bears an objective character.
154
It is important to fulfil the rule that every division gives approximately an

equal quantity of objects (a coefficient of information). The selectivity is met
rather often in the Natural classifications. The natural classifications always
"act" (see, for example, the Periodic System of the chemical elements and the
symmetry of crystals). Of course, some error may occasionally exist. As a result
of more detailed investigation, some elements can change their places, but it is
the result of the inadequate investigation of the elements classified. This is why
the Natural classifications playa fundamental role in science. The Artificial
classifications often can be temporary, single-time events. Sometimes they play
an auxiliary role.
2.3.3 Two Approaches Toward Crystallochemical Classification

of Minerals and Inorganic Crystals
G.B.
BOKIY
These two approaches depend on what is taken for the first basis of a
classification: (1) chemical composition of minerals or (2) crystal structure.
In the first case it is division of minerals (chemical compounds) into chemical
types, subtypes, classes, and the structural classifications are applied to these
classes of minerals. This is a classification of minerals which are fundamentally
chemical compounds, each possessing a crystal structure.
In this manner, structural classifications have been elaborated for several
classes of minerals: silicates, sulfates, arsenates, vanadates, sulfosalts. Povarennykh (1972) applied this principle to the whole domain of minerals, systematically presenting chemical-structural distributions of all minerals known at
that time.
This approach permits more detail and versatile consideration of each class
of mineral structures which differ radically from crystal structures of other
classes of minerals. An attempt to summarize the principles for this chemicalplus-structural, i.e., crystallochemical, systematics is portrayed in Chapter 2.3.4.
In the second case, a rather new and quite special approach was developed
for classification, which takes structural criteria as a basis. It is a systematics of
structure types independent in principle of their chemical composition. Thus
NaCI-MgO-PbS present one structure type which finds its place in the classification.
.
This is a logically natural stage in the evolution of crystal structure analysis.
It could be useful from the point of view of contemporary materials science
which considers, for example, garnets as composed of rare-earth oxides, Y-AI,
Y-Fe, and silicate garnets all having the same crystal structure; but this is just a
geometrical systematics of crystal structures, not only of minerals. Attempts to
find general principles which can include all different classes of compounds of
extreme diversity can lead to artificial and complicated schemes.
2.3.4 Crystallochemical Classifications of Minerals
155
In principle, the systematics of crystal structure types could be independent

of chemical composition but: (1) in elaborating their bases the chemical bonding
between structural units has to be taken into consideration, and (2) compounds
belonging to the same structure type are then ordered chemically, the chemical
criteria being the same as that normally used for the classical taxonomy. In the
case of the NaCI-MgO-Pbs structure type the halogenides are considered first,
followed by the oxides, and then by sulfides, tellurides, nitrides, roughly in the
order of decreasing electronegativities. The systematics is not purely structural,
but structural-chemical. The principles of this approach to the mineral classification have been considered by Lima-de-Faria (1983, 1986), Hawthorne (1985,
1990).
Lima-de-Faria and Figueiredo (1978) applied these principles to inorganic
structures in general and systematically to about 3000 crystal structures (see
Chap. 2.3.5).
2.3.4 Crystallochemical Classifications of Minerals

G.B.
BOKIY
Principal criteria of the crystallochemical-mineralogical classification can be

stated as follows:
1. The minerals are natural chemical compounds, and for this reason they
should be classified as chemical compounds with the Periodic Law of the
chemical elements as the basis of the classification.
2. The division of the chemical elements into metals and nonmetals assumed
by Berzelius in the first part of the 19th century is to this day a basis of every
chemical classification. Using the long form of the Periodic Table, it is easy to
fulfil these divisions. The metals are spread to the left from the Z-shaped
boundary and to its right are the nonmetals.
3. In the process of the division of "a set" of minerals, the first taxa must be
based on the pure chemical attributes. The structural characters are applied to
the taxa lying lower in the hierarchy.
4. The terminology of the taxa is accepted as the same as in biology:
kingdom - phylum - type - class - order - family - tribe - genus - species. More
fractional subdivisions are supplied by the prefixes sub- and super-.
It is necessary to establish all these taxa as "a set", whose properties allow
classification. Thesauri are usually composed to define elements in the set. [See
the Bokiy et al. (1976-1983) Thesaurus on 2760 minerals in five volumes,
published in Russian and German, in 1976-1983 by VINITI].
The first action in the division of the kingdom of the chemical compounds:
1. Simple metals and intermetallics.
2. Elementary substances of the nonmetallic elements and their compounds
156
Table 18. Division of the sections of the chemical compounds into

types
11.
12.
21.
22.
(31.
41.
42.
(43.
(44.
51.
52.
53.
54.
55.
61.
62.
63.
64.
Pure metals (native metals)

Intermetallic compounds
Pure nonmetals (native nonmetals)
Compounds of nonmetals with nonmetals
Borides)
(65. Polonides)
Carbides
(71. Hydrides)
Silicides
72. Fluorides
Germanides)
73. Chlorides
Stannides)
74. Bromides
Nitrides
75. Iodides
Phosphides
(76. Astatides)
Arsenides
(81. Compounds of helium)
Stibides
(82. Compounds of neon)
Bismuthides
(83. Compounds of argon)
Oxides
(84. Compounds of krypton)
Sulfides
(85. Compounds of xenon)
Selenides
(86. Compounds of radon)
Tellu rides
Note: Parenthesis indicate compounds which do not exist as minerals.
Table 19. Division of the type of the oxides (61) into classes
Subtypes
Me [yIlI_O]
613
Me [B-O]
6132
borates
Me [ylv_O]
614
Me[Yv-O]
615
Me [yVI_O]
616
Me [yvlI_O]
617
Me [yVIII_O]
618
Me [H-O]
6171
Me [He-O]
6181
Me [C-O]
6142
carbonates
Me[N-O]
6152
nitrates
Me [0-0]
6162
peroxides
Me [F-O]
6172
fiuorates
Me [Ne-O]
6182
Me [Si-O]
6143
silicates
Me [P-O]
6153
phosphates
Me [S-O]
6163
sulfates
Me [Cl-O]
6173
chlorates
Me [Ar-O]
6183
Me [Ge-O]
6144
germanates
Me [As-O]
6154
arsenates
Me [Se-O]
6164
selenates
Me [Br-O]
6174
bromates
Me [Kr-O]
6184
Me[Sn-O]
6145
stannates
Me [Sb--O]
6155
stibates
Me [Te-O]
6165
tellurates
Me [J-O]
6175
iodates
Me [Xe-O]
6185
Me [Bi-O]
6156
bismuthates
Me [Po-O]
6166
pollonates
Me [At-O]
6176
astatates
Me [Rn-O]
6186
L,
Lz
L3
Fz
3 Chain
4 Band
5 Tube
6 One
store
layer
7 Twostore
layer
8 Threestore
layer
9 Framework
10 Zeolite
Si:O and O:Si ratios
a numerator, 0: Si
=
a denominator)
10
2
3
4.00 3.50 3.33 3.25 3.20 3.17 3.00 2.86 2.83 2.80 2.75 2.71
T
3n
In
In
2.70 2.66 2.63 2.60
In
2.51
In
In
---------
2.50 2.40 2.37 2.33 2.30 2.25 2.20 2.17 2.05 2.00
1:4 2:7 3:10 4:13 5:166:19 1:3 7:206:175:144:11 7:19 10:27 3:8 8:21 5:13 12:31 2:5 5:128:19 3:7 10:23 4:9 5:11 6:13 20.41 1:2
Numbers in the table show the number of the varieties in the subclass.
n = nonmineral
I,
2 Island
ring
Island
noming In
N Name
and
symbol
of the
subclass
Table 20. Subclasses in the class of the silicates and the corresponding silicon-oxygen radicals. (Si: 0
-.I
.....
VI
a
'"
~.
'"o
-.
3::
o
el
e?
g>
'"
f!l.
f.
.:!
(')
Ms and
their
names
Cations
in the
positions
Genders structural
types
M2
M1
Ca
Ti'
:I:
>.
-5'"
'"c
Fe 2
Mg
C2/c
'"t:
"-'"
3
'"6
.~
Fe 2
Fe 2
15
:~Ci
16
00
Ca
Fe 2
~'Oh
c~
17
18
~'5
.., '" X]
c '"
0:
Ca
Mn
1111
Ca
Mg
~c
.~
Mg
Mg
Cations
in the
positions
MS and
their names
P2,cn
(pbcn)
00
Ca
Al
~..r::
'08... >.
Fe 2
Fe 2
o
Fe
Mg
as
0
.;:J
Mg
Mg
P2,ca
00
Na
Fe 2
Na
Fe'
00
Na
Mg
'E
S'"
Na
Al
Na
Sc 3
~
.;;;
P2/n = P2/c
Vl
0.
"0
0
'"c
'";;l
S
000
Na
Mg
11
Li
Al
19
20
21
22
23
24
25
26
I I I I I I I I
00
Ca
Fe'
'"
'"
oI~
...
Fe 2
Mg
.=~
e~
~ iJ
Mg
Mg
m n
Pbca
Genders structural
types
M2
Ml
Table 21. Family of pyroxenes M 2 M, T 206
-as
'g
Ca
Mg
10
Na
V3
27
00
Ca
Al
11
~0
:2
u
...0
Na
Cr
C2/c
28
Q~
.~
c ..
0-
Mg
Mg
P2,/c
12
00
Na
Fe 2
29
.g~
Mn
Mg
'"
-<:
13
'"
SO
c
.;:::
Na
Fe'
30
Mn
Fe 2
31
32
~..c:-= ~~;;j
tU
Fe 2
Fe 2
,
]~~;~.~
o''''
~
Fe2+
Mg
14
..,
"0
.iii
Na
Al
go
'"
s::~.
S,
2
~
['"
...,~
(')
!'-'
...,0'
'0
(')
00
.....
Vl
2.3.5 The Structural Classification of Minerals
159
with each other (these substances do not contain the metallic elements in their
composition).
3. * Metals with the nonmetallic elements of subgroup IIIB (borides).
4. Metals with the nonmetallic elements of subgroup IVB.
5. Metals with the nonmetallic elements of subgroup VB.
6. Metals with the nonmetallic elements of subgroup VIB.
7. Metals with the nonmetallic elements of subgroup VIIB.
8. * Metals with the nonmetallic elements of subgroup VIIIB.
The empty sections for mineralogy are marked by an asterisk. The second set
of subdivision gives 31 types (for minerals, 20) (see Table 18). Two figures in the
decimal system correspond to this action.
Under a type of the oxides (61) including the chemical compounds and the
minerals, oxygen predominates in the anionic composition. The number of such
minerals (in percent) exceeds the number in other types. As oxides, in the narrow
sense of this term, so the silicates and other salts of the oxygen acids relate to this
type. This type is divided into six subtypes (Table 19).
These chemical divisions are followed by structural classifications for classes
and orders of minerals.
Principles of the classification of silicate minerals are presented in Table 20.
As an example, the structural classification of the pyroxene family is given in
Table 21. See also classifications of silicates by Zoltai (1960) and by Liebau
(1985).
The crystal structure classifications have been presented for several classes of
minerals:
- borates (based on the polymerizations of the B0 3 and B0 4 anionic groups) by
Christ and Clark (1977).
- phosphates, sulfates, arsenates, vanadates (based on the polymerization of
M2+ and M3+ cation octahedra) by Moore (1980).
- aluminum hexafluorides by Pabst (1950).
- sulfosalts by Makovicky.

J. LIMA-de-F ARIA
When extensive data are accumulated in a certain domain of science there is
a need for systematization in order to relate the new information, retrieve it and
hopefully to make predictions. The systematization will enable a natural
relationship among the different kinds of materials to be studied, and it will also
help uncover the rules governing their constitution and properties.
The structural relationship among minerals has been hampered by the
emphasis given to their chemical composition, which is clearly expressed by the
160
use of a chemical classification of minerals for more than 100 years, and of
chemical formulae to characterize the mineral species. Substantial structural
data have been accumulated since the discovery of X-ray diffraction by crystals,
in 1912, and it is convenient to take advantage ofthese data by clarifying certain
structural mineralogical concepts, and by developing a new crystal-chemical
classification, a structural classification of minerals, where structures are
brought together not by their chemical similarity but the resemblance of their
atomic structural arrangements, and consequently bringing together minerals
that belong to the same structure type.
The Concept of Structure Type
There are several ways to establish structural relationships among crystal

structures, to which correspond different degrees of similarity.
Crystal structures are similar when a correspondence exists between
structural arrangements of the atoms. For example, thorianite, Th0 2, has
a structure similar to that of fluorite, CaF 2, these two structures having the same
cubic symmetry, the same corresponding occupied equivalent positions,
differing by the size of their unit cells. In such cases the compounds are called
isotypic, that is, they belong to the same structure type.
However, when the equivalent positions are not invariant and the radius
ratio between corresponding atoms changes, the relationship becomes more
complicate. These and other crystal-chemical considerations, such as the bond
strength distribution, bond character, electronegativities assigned to the atoms,
and electronic states, may still complicate the definition of isotypy. In a report of
a Subcommittee of the Crystallographic Commission on Crystallographic
Nomenclature of the International Union of Crystallography (Lima-de-Faria
et al. 1990), three main degrees of similarity between crystal structures have been
defined:
- Two structures are isopointal if they have the same space group or belong to a
pair of enantiomorphous space groups, and the corresponding atoms occupy the
same equivalent positions, either fully or partially at random (FeS2 and CO 2).
- Two structures are isoconfigurational if they are isopointal, and their
geometrical properties are similar, such as axial ratios and interaxial angles
(CaF 2 and OLi 2, in the strict geometrical sense; Ca3Al2Si3 0 12 and Y3FeSOd.
- Two structures are crystal-chemically isotypic, or belong to the same structure
type if they are isoconfigurational and the corresponding atoms have similar
physical/chemical characteristics (CaF 2 and Th0 2; NaCI and MgO; Mg 2Si0 4,
olivine, and A12Be04, chrysoberyl).
Other close relations between relative structures may be considered, which
are called homeotypic. Two structures are homeotypic if one or more of the
conditions required for isotypism are relaxed, such as identity or enan-
161
tiomorphism of the space group, similarity of axial ratios and interaxial angles,
values of the adjustable positional parameters, coordinations of atoms, same site
occupancy allowing given sites to be occupied by different atomic species.
Some of the important homeotypic structures are the so-called distortion
and substitution derivatives. In the case of distortion derivatives, the atomic
arrangement suffers a slight distortion. Examples are NaCI (halite) and FeSi
(fersilicite) or TiCa03 (ideal perovskite) and CuKF 3, with subgroup symmetry.
Other relative structures may be considered such as; polytypic structures (SiC
polytypes), "interstitial" or "stuffed" derivatives (AuCu3 and TiCa03), and
recombination structures (olivine-norbergite homologous series).
General Classification of Inorganic Structures. The Concept of

Structural Units
Attempts to replace the chemical by structural criteria in the classification of
inorganic structures were made by Machatschki (1928), WL. Bragg (1930) and
Niray-SzabO (1930), but these were limited to the silicates. The structural
classification of the silicates based on the bond strength distribution probably
led to the concept of structural units (Laves, 1930), which correspond to the
assemblage of atoms more tightly linked together, a kind of skeleton of the
structure. This classification of silicates considered five kinds of structural units
based on Si0 4 tetrahedra: isolated tetrahedra, finite groups, infinite chains,
infinite sheets and frameworks. Extensions of this classification to the whole
domain of crystal structures were proposed by Laves (1930), Niggli (1945),
Garrido and Orland (1946), Bokii (1954), De Jong (1959), Lima-de-Faria and
Figueiredo (1976), and Hawthorne (1983).
As already pointed out, the crystal-chemical isotypy may be defined in
different ways, according to the choice of physical/chemical characteristics
considered as more important. The concept of structure type adopted by
Lima-de-Faria and Figueiredo (1976) is based on the strength distribution and
directional character of the bonds among the atoms, and it is also in agreement
with the one adopted in the Report 1990.
In inorganic structures there is a tendency to close packing (first Laves
principle). When the bonds are predominantly non directional, the bond
strength distribution is homogeneous in most cases. However, if the character of
certain bonds is directional a deviation from the close packing takes place, that
is, the structures tend to form less dense atomic arrays, and certain atoms are
more tightly linked together than others, forming finite groups, or assemblages
that are infinite in one, two or three dimensions. These assemblages are called
structural units and the remaining atoms are the interstitial atoms.
There are five categories of structural units, in a broader sense, distributed
among the four dimension ali ties:
162
Dimensionality of
structural unit
O-dimensional
I-dimensional
2-dimensional
3-dimensional
Category of structural unit

individual atoms
groups (i.e. rings, chain fragments, cages)
chains
sheets
frameworks
{
The corresponding kind of structures are designated by: atomic, group, chain,
sheet, and framework structures.
While most of the structural classifications are restricted basically by
consideration of the principles formulated, Lima-de-Faria and Figueiredo (1976,
1978) systematically applied these concepts and presented a general table of
inorganic structure types including 782 structure types to which correspond
approximately 5200 structures, and a chart containing the 174 structural units
which form these types.
The Structural Classification of Minerals

The classification of minerals has changed throughout the ages, the criterion of
classification following the development of the mineralogical sciences.
A sketch of the evolution of the basic criteria of the mineralogical
classification has been already presented by Lima-de-Faria (1983). It is apparent
from this sketch that the classification of minerals went through different stages:
from practical, to physical, to physical-plus-chemical, to chemical, to chemical-pIus-structural. Although the chemical classification of minerals seems to be
well established, some dissatisfaction has become apparent particularly during
the last decades, and other criteria have been proposed for the classification of
minerals. Some criteria are related to particular domains of application, such as
geological (Lapparent 1884) or geochemical (Uklonskii 1940; Kostov 1954);
others, to more theoretical purposes, such as the one proposed by Machatschki
(1953), which was based on crystallochemical grounds and on the hierarchy of
the complexity of their formulae. It seems that it is now time to attribute the
primary role to the structural criterion and to propose a structural classification
of minerals. Such classification has been proposed (Lima-de-Faria 1983, 1988),
and is in a certain wayan extension of the structural classification of silicates to
the whole domain of minerals, and also the result of the application of the
general structural classification of inorganic structures to mineral structures.
Minerals belonging to the same structure type are placed together, and
within each category, they are ordered chemically. As an example, the halite
structure type includes the halogenides, followed by the oxides, sulfides,
tellurides, and nitrides, belonging to the halite structure type. This clearly shows
that the classification is not purely structural, but a structural-chemical
classification of minerals. Part of this synthesis is shown in Table 22 to give an
idea of its construction.
163
Table 22. First part of the outline of a structural classification of minerals. (Lima-de-Faria 1983)
ATOMIC
(Fe,Sn)OTaO[04]h Ixiolite Pbcn
Homogeneous
Layered
Closest-packed
Non-interstitial
[CuJ Copper
[PtJ Platinum
[Pd]' Palladium
[Ir]' Iridium
[Ni]' Nickel
FeOWO[04]h Wolframite P2/c

ZnOWO[04]h Sanmartinite
Nb~Feo[06]h Columbite Pbcn
Ta~FeO[06]h Tantalite Nb~MgO[06]h Magnocolumbite
Fm3m
[Ag]' Silver
[Au]' Gold
[(Ag,Au)]' Electrum
[(Ag,Hg)]' Kongsbergite
[Pb]' Lead
[Hg)' Mercury R3m

[In]' Indium
I4/mmm
[AuCu]' Cuproaurite P4/mmm
[FePt)' Ferroplatinum [PdHg)' Potarite
[AUCU3]' Tricuproaurite Pm3m
[PbPd3]' Zvyagintsevite
[(Os,lr)]h Iridosmine P6 3/mmc
[ZnI2]h Zinc P6 3/mmc
Interstitial
Octahedral
NaO[CI]' Halite Fm3m
NaO[F]'
Viliaumite
CaO[O]' Lime
KO[CI]'
Sylvine
CdO[O]' Monteponite
AgO[(Br,CI)]' Cerargyrite
CaO[S]' Oldhamite
MgO[O]'
Periclase
Mno[S), Alabandite
Nio[O]'
Bunsenite
PbO[S), Galena
Pb[Te]' Altaite
FeO[O),
Wiistite
MnO[O]'
Manganosite Tio[N]' Osbornite
Fe 7 [Si]' Fersilicite
CoO [AS]h Langisite
NiO[Sb]h Breithauptite
FbO[Sblh Palstibite
pta [Sb] Platstibite
FeO[S]h TroiIite
(Fell,FellI)O[S]h Pyrrhotine
COO [S]h Jaipurite
COO[AS]h Modderite
P2 1 3
FeO[Se]h Achavalite
CoO[Se]h Freboldite
(Nill,NillI)O[Se]h Sederholmite
Nio[Te]h Imgreite
PdO[Te]h Kotulskite
PtO[Sn]h Niggliite
Pbnm
MgO[Ch]' Chloromagnesite R3m

MnO[Ch]' Scacchite
FeO[Ch]' Lawrencite
NiO[Te2]h Melonite P3ml
SnO[S2]h Berndtite
PtO[Te2]h Moncheite
NiO[Se2]h Nidiselite
Pdo[Te2]h Merenskyite
NiO[SeTe]h Kitkaite
CaO[Cb]h Hydrophilite Pnnm

FeO[AsS]h Arsenopyrite P2t/c
MnO[02]h Ramsdellite
VO[02]h Paramontroseite
Pbnm
Aln03]h Corundum R3c

Hematite
Vn03]h Karelianite
Eskolaite
FeOTiO[03]h Ilmenite R3
MnoTiO[03]h Pyrophanite MnO(Fe,Sb)0[03]h
Melanostibite
Fe~[03]h
Cr~[03]h
Tellurobismuthite R3m
BinTe 2S]Chh Tetradymite R3m
Bi~[Te2Se]'hh Kawazulite
Bi~[Te3]'hh
TiO[Ca03]' Perovskite Pm3m (ideal)

TiO[(Na,Ce)OJ]' Loparite Nbo[NaOJ]' Igdloite
(Ti,Nb)0[(Na,Ca)03]' Latrappite Pcmn
NbO[Na03]' Lueshite P222 1
TiO[Pb0 3), Makedonite P4/mmm
NaOAI0[K 2F 6)' Elpasolite Pa3
Tetrahedral
2n' [S)' Sphalerite F43m
Cu'[CI]' Nantokite
Hg'[S]' Metacinnabarite
Cu'[I]' Marshite
Zn' [Se]' Stilleite
Ag' [I]' Miersite
Hg'[Te]' Coloradoite
Cd' [S]' Hawleyite
Cu'Fe'[S2]' Chalcopyrite 142d
Cu'Ga'[S2)' Gallite TI'Fe'[S2]' Raguinite
Cu'ln'[S2)' Roquesite
Cu~Sb'[S4)' Famatinite 142m
Cu~ Fe'Sn' [S4]' Stannite 142m
CuHFe,Zn)'Ge'[S4]' Briartite Cu~Zn'Sn'[S4]' Kosterite
Cu~Zn'ln'[S4]' Sakuraiite Ag~Fe'Sn'[S4]' Hocartite
164
In order to emphasize the important aspects of a structure, in an abbreviated

manner, one should use an appropriate notation: the structural formulae. These
are based on the chemical formulae with the addition of subscripts, superscripts
and parenthesis, which indicate the structural characteristics of the crystal
structure.
Other Recent Approaches to the Systematics of Minerals
Bokii (1982) and Hawthorne (1984,1985) have also suggested new classifications
of minerals based on their general classifications. A structural classification of
minerals, restricted to those that contain octahedral cations, has been suggested
by Moore (1974).
Hawthorne (1984, 1985) has suggested a general structural classification of
mineral structures based on the polymerization of coordination polyhedra (not
necessarily of the same type) with the higher bond valence, as a consequence of
the application of bond-valence theory to inorganic structures. The structures
are organized by families based on different arrangements of fundamental
building blocks or modules. The possible modules are the tightly bound units
within the structure, and correspond to clusters of polyhedra that are most
strongly bonded. One of the differences of this classification concept from that
proposed by Lima-de-Faria is based on the fact that for Hawthorne the
"modules" (or structural units) are only polyhedra, and never individual atoms,
as admitted by Lima-de-Faria. For instance, olivine, Mg 2 Si0 4, would be
classified according to the Hawthorne model in the category of unconnected
polyhedra, the Si0 4 tetrahedra being the structural units; for Lima-de-Faria,
Olivine is an atomic (or close-packed) structure, where the oxygens (individual
atoms) are the structural units forming an hexagonal close-packing, with
magnesium and silicon located in the interstices (octahedral and tetrahedral,
respectively); the corresponding structural formula is therefore Mg~SjI[04]h.
2.3.6 Counting Theory and Classification of Crystal Structures

P.B.
MOORE
A subject of wide ramification and bearing to the systematics of structure

classification appears in counting theory. Most classifications of mineral structures begin with the set of known crystal structures and proceed to evolve a
hierarchy of structures according to geometrical/topological properties of subsets or families of these structures. For example, silicate radicals are based on
condensations of the fundamental Si0 4 tetrahedra and the hierarchy proceeds
according to the successive condensations of these radicals; but this is like saying
2.3.6 Counting Theory and Classifications of Crystal Structures
165
the oceans have water in them. Tetrahedral chain periodicity, loops (rings), open
wings, closed cages, etc. all bear upon the classificatory scheme of Liebau (1985),
which results in a magnificent edifice. One is struck, as with any structure
classification, that the number of arrangements increases exponentially as the
number of participating fundamental units. The problem in classification is not
one of pigeonholing but one of taxonomic gigantism. As more and more useful
distinguishing characters appear, so do the labels until the edifice collapses by
sheer weight. This will always remain a problem for classifications based on
structure, perhaps less so for classification based on paragenesis or even anion
packing efficiency.
It is reasonable to assume that the known mineral structures which are based
on some bonding principle number far fewer than all the structures which could
possibly exist according to the same bonding principle, for example the silicates.
Counting theory helps guide the investigator in ascertaining how many structures could theoretically exist under an appropriate principle, and may even
contribute to an understanding why certain arrangements frequently appear in
crystals while others are singular in their very absence of any known crystalline
representative.
McLarnan and Moore (1981) is a brief introduction to counting problems
applied to mineral structures; it has references to some of the key literature in
this rapidly growing field. Solutions from counting (or graphical enumeration)
problems tend to exponentially increase as the elements in a domain increase.
For example, four kaolinite polytypes occur among one-layer structures but
ca. 10 17 arrangements occur among 12-layer structures! Investigators in
counting theory get used to these large numbers. The underlying principle
is the famous Polya's Theorem, PET. More recently, more powerful generalizations of PET have appeared. All consist of several sets of objects, briefly written
M, H, G and Z{G}. The number of elements in a set S will be designated lSI.
The set to be colored is M. For an octahedron, it could represent the domain
of vertices (IMI = 6), edges, (IMI = 12), or faces (IMI = 8). Such domains are
appropriate for convex polyhedra, in particular the tetrahedron, octahedron,
cube, icosahedron, and pentagonal dodecahedron. In these cases of the regular
polyhedra, a domain of elements (such as the labeled edges) are equivalent to
each other, which one quickly notices by some reorientation either of the labels
or of the polyhedron itself.
H are the colors to be applied to the domain. The order, lSI or number of
elements in the set, is usually written in magnitude notation I I. For example in
the octahedron, IMI = 12 for the edges. Typical colorings of octahedral edges
may involve IHI = 1 (one color) to 12 (12 colors) where 1 and 12 are obviously
trivial. Most commonly IHI = 2 (occupied/empty, on/off, yes/no, black/white,
shared/unshared, etc.). This approach is especially convenient in retrieving
clusters, such as occupied/empty for octahedral edges: (12/0, 11/1, 10/2,9/3,8/4,
7/5,6/6 ...). Note distributions are symmetrical about (6/6) merely by switching
the two colors. Colorings may also be distributed over lattices. Here, clever
algorithms may be devised based on a generalization of PET, such as for the
166
domain of dense sphere packings or of sheets with ever increasing orders, IM I, of

spheres or of layers.
G is the permutation group which is applied to (acted upon) the domain. It
lists the number of equivalences (group operations) associated with the domain.
For the octahedron, IG{4/m:3 2/m}1 = 48, the number of equivalences in the
cubic holosymmetric crystal class. The elements of symmetry (equivalence
operations) are listed, then their corresponding permutation notation, then
their cycle notation, and finally their pattern inventory, Z{ G}. What about
G{432} cG{4/m:3 2/m}? The enantiomorphic group is contained within the
holosymmetric group, viz. {i} G{432} = G{4/m:3 2/m}, has IG{432}1 = 24
elements and distinguishes an enantiomorphic cluster from its chiral mate,
but G {4/m :3 2/m} does not, since the inversion operation is included. Therefore,
G{ 432} must contain more clusters - conveniently called animals - than
G{4/m:3 2/m}. These group-subgroup relationships are also convenient devices
for extracting information.
Z{ G} is the pattern inventory. This equation is a polynomial in cycle
structure notation which provides an immediate determination of the number of
patterns. As expected, if the order of the domain, M, increases or the order of the
colorings, H, increases, the number of animals retrieved by the pattern inventory
also increases. Many scaffoldings or hierarchies of the result can be immediately
conceived, for example, the cascade of arrangements under one symmetry group,
the cascade under one coloring occupied/empty, or the cascade of the group G
itself. Polya's theorem conveniently gives the number of animals under G acting
on M, but it does not conveniently provide us with the arrangements or the
point symmetries of the animals. For example, Moore (1974) listed 144 animals
representing the geometrically distinct adjacent octahedral edge-sharings about
a central octahedron. Actually, 74 of these had chiral mates, so there were 144
+ 74 = 218 unique arrangements. These were accumulated by "brute force"
from computer iteration. From PET, IZ{4/m:3 2/m}1 = 144 and IZ{432}1 = 218,
a result later achieved on the back of an envelope! Of course, once the numbers
of animals are known, retrieving the animals and their symmetries as polyhedral
clusters becomes tractable and certain.
For the chemical crystallographer and mineral taxonomist, it is a powerful
and straightforward technique for enumeration. It is doubted that PET will
provide the foundation for mineral classification because, as we have stated, the
solutions for most problems give a large number of animals where only a
handful of natural objects may be represented; in other words, the classification
is rather thin or sparse. However, it is of great importance in questions related to
chemical bonding such as why some domains are richly represented by natural
objects, yet others are practically empty. PET provides a way of counting and
listing, and may temper the vehicles for classification, for there are infinitely
many ways of classifying things, most of them rather thin and inefficient. Several
good introductions, with references and examples, exist for PET and its
application to mineral structures: McLarnan and Moore (1981), Liu (1968), and
Harary and Palmer (1973) are examples.
2.3.6 Counting Theory and Classifications of Crystal Structures
167
References
Bokiy GB (1989) Classifications and systematic approaches in mineralogy. In: Classifications
in contemporary science. Novosibirsk, pp 89-95 (in Russian)
Bokiy GB, Kochanova NN et al. (1976, 1977, 1979, 1981, 1983) Thesaurus on minerals.
VINITI, Moscow (in Russian and in German)
Christ CL, Clark JR (1977) A crystal-chemical classification of borate structures with emphasis
on hydrated borates. Phys Chern Mineral 2: 59-87
Frevel LK (1985) A systematic classification of crystal structures. Acta Cryst B41: 304-310
Harary F, Palmer EM (1973) Graphical enumeration. Academic Press, New York
Hawthorne FC (1983) Graphical enumeration of polyhedral clusters. Acta cryst A39: 724-736
Hawthorne FC (1985) Towards a structural classification of minerals: V1M1vT 200 minerals.
Hawthorne FC (1986) Structural hierarchy in VIMxlllTy02 minerals. Can Mineral 24: 625-642
Hawthorne FC (1990) Structural hierarchy in [6[M[4[T0 2 minerals. Z Krist 192: 1-52
Hellner E (1965) Descriptive symbols for crystal-structure types and homeotypes based on
lattice complexes. Acta Cryst 19: 703-712
Hellner E (1984) Frameworks and a classification scheme for inorganic and intermetallic
structure types. Acta Cryst A40 (suppl): 214 (Abstr)
Hellner E (1986) Einfiihrung in eine anorganische Strukturchemie. Z Krist 175: 227-248
Liebau F (1985) Structural chemistry of the silicates: structure, bonding and classification.
Springer, Berlin Heidelberg New York
Lima-de-Faria J (1983) A proposal for a structural classification of minerals. Garcia de, Ser
Geol6: 1-14
Lima-de-Faria J (1988) The need for a structural classification of minerals. Rend Soc Ital
Mineral Petrol 41: 157-179
Lima-de-Faria J, Figueiredo MO (1978) Classification, notation, and ordering on a table of
inorganic structure types. J Sol State Chern 16: 7-20
Lima-de-Faria J, Hellner E, Liebau F, Makovicky E, Parthe E (1990) Nomenclature of
inorganic structure types. Report of the International Union of Crystallography Commission on Crystallographic Nomenclature Subcommittee on the Nomenclature of Inorganic Structure Types. Acta Cryst A46: 1-11
Liu CL (1968) Introduction to combinatorial mathematics. McGraw-Hill, New York
McLarnan TJ, Moore PB (1981) Graph-theoretic enumeration of structure types: a review. In:
Navrotsky A, O'Keeffe M (eds) Structure and bonding in crystals. II. Academic Press,
New York, pp 133-165
Moore PB (1974) Structural hierarchies among minerals containing octahedrally coordinating
oxygen. II. Systematic retrieval and classification of octahedral edge-sharing clusters: an
epistemological approach. Neues Jahrb Mineral Abh 120: 205-227
Moore PB (1980) The natural phosphate minerals: crystal chemistry. Second International
Congress. International Mondial du Phosphate, pp 105-130
O'Keeffe M, Hyde BG (1985) An alternative approach to molecular crystal structures, with
emphasis on the arrangement of cations. Struct Bond 61: 149-165
Pabst A (1950) A structural classification of fluoaluminates. Am Mineral 35: 149-165
Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell Univ Press, Ithaca,
New York
Pearson WB (1967) A handbook of lattice spacings and structures of metals and alloys.
Pergamon Press, Oxford
Povarennykh AS (1972) Crystal chemical classification of minerals. Plenum Press, New York
Zoltai T (1960) Classification of silicates and other minerals with tetrahedral structures.
CHAPTER 3
Real Structures of Minerals
Chapter 3. Real Structures of Minerals
170
3.1 Point Defects in Minerals

A.
DURA
and R. SCHOCK
All crystals have point defects that are formed as the consequence of both
thermal activation and aliovalent impurities. Properties such as diffusion, creep,
and electrical conductivity have been shown to depend on point defects in all
types of crystals. This has been demonstrated well for olivine, for example [Jaoul
et al. 1980; Ryerson et al. 1987; Kohlstedt and Hornack 1981; Hermeling and
Schmalzried 1984; Schock et al. 1989; Bai et al. 1991 J. The minerals pyroxene
[Duba et al. 1973; Huebner et al. 1979J and spinel, as well as polymorphs of
these minerals and olivine [Hirsch & Shankland 1991J, which are stable at
higher temperatures and pressures, are also likely to have their, physical
properties determined by point defects [Paterson and Kekulawala 1979; Linker
et al. 1984]. The mechanical properties of quartz, the dominant constituent of
the crust, are also related to point defect concentrations.
An impetus for ascertaining the role of point defects in determining physical
properties of earth materials is to obtain a means of predicting physical
properties of these materials at conditions not attainable in the laboratory but
which can prevail in the Earth's interior. A good case in point is the recent
theoretical prediction of point defects in the high-pressure perovskite phase of
pyroxene [Hirsch and Shankland 1991J based on earlier work done on magnesiowiistite, olivine, and pyroxene. Critical to development of these predictions are
experimental data under known thermodynamic conditions of pressure, temperature, and component activities. The experimental data usually
comprise determination of the effect of variation of the oxygen fugacity on a
transport property while pressure, temperature, and the activity of other
components is held constant. These data together with other relevant data are
then used in conjunction with models of defect behavior to determine the
particular defect mechanism that prevails.
Olivine is the most studied mineral in these terms because it is a major
constituent of Earth's upper mantle and provides a good example of the
development of our understanding. Schock et al. (1989) conclude that the low
activation energies for electrical conduction in olivine compared to those
relative to the band gap make it unlikely that intrinsic electronic conduction is
occurring in olivine during laboratory measurements. Since some of these
measurements have been made at pressures and temperatures equivalent to
about 150 km in the Earth's interior, Schock et al. conclude that point defects
playa key role in determining the electrical properties of olivine to at least this
depth in the Earth.
Defect models for conduction in olivine have been generated by Stocker
(1978) from theory and by Schock et al. using data available from the
measurement of electrical conductivity as a function of oxygen fugacity, the
directional dependence of conductivity in olivine's orthorhombic structure, and
the sign of the dominant change carriers as determined from measurement of the
3.1 Point Defects in Minerals
171
thermoelectric coefficient in olivine. The notation of Kroger and Vink (1956) is

used here ... X~ is an atom (X) or vacancy (V) that occupies a site, y is the species
normally occupying the site and z is the effective charge associated with that site.
Prime indicates negative charge, superscript dot indicates positive charge,
x indicates neutral. An interstitial is Xi.
There is a wealth of possible defect mechanisms which can give rise to
conduction in olivine. [Stocker 1978; Smyth and Stocker 1975; Schock et al.
1989; Hirsch and Shankland 1991]. In order to differentiate among them, the
sign of the charge carrier determined from thermoelectric measurements on San
Carlos olivine and the slope of the conductivity/oxygen-fugacity relationship
has been used. Combining this information with the oxygen-partial-pressuredependence of defect reactions and the sign of the charge carrier produced, one
is able to determine the defect reactions which govern conduction in olivine. For
olivine with about 10% iron, the typical olivine derived from mantle nodules,
the analysis of Schock et al. indicates that mixed conduction is occurring over
the temperature range 1200-1500 C with electron hole conduction dominating
below 1390C and magnesium vacancies dominating above that temperature.
The defect reactions describing these processes are reactions (1) and (2) below.
For electron hole conduction the defect reaction is
8FeMg
+ 20 2 -40~ + 2V~g + V~;' + 8FeMg .
(1)
Similarly, for magnesium vacancies the defect reaction is

MgMg
+ 2FeMg -+ 2FeMg + V~g + Mg!.
(2)
This model is consistent with the interpretation of Sato (1986) of measurements

of the frequency variation of the dielectric constant in olivine in terms of partial
blocking of magnesium vacancies at the electrodes while electronic carriers are
not blocked by the metal electrode. There is a great deal of work left to be
accomplished in understanding the role of defects in olivine as well as other
important earth-forming minerals, as shown by many of the contributions in
this volume.
References
Bai Q, Mackwell SJ, Kohlstedt DL (1991) High-temperature creep of olivine single crystals:
I. mechanical results for buffered samples. J Geophys Res 96: 2441-2464
Duba AG, Boland IN, Ringwood AE (1973) Electrical conductivity of pyroxene. J Geol 81:
727-735 .
Hermeling J, Schmalzried H (1984) Tracer diffusion of the Fe-cation in olivine
(Fe xMg ' - xhSi04 (III). Phys Chern Mineral ll: 161-166
Hirsch LM, Shankland TJ (1992) Olivine point defect chemical model and the role of Feimpurities: insights on electrical conduction, diffusion, and creep. J Geophys Int 144: 21-35
Hirsch LM, Shankland TJ (1991) Point defects in (Mg,Fe)Si0 3 perovskite. LA-UR 90-3736
Geophys Res Lett 18: 1305-1308
Huebner JS, Duba A, Wiggins LB (1979) Electrical conductivity of pyroxene which contains
trivalent cations: laboratory measurements and the lunar temperature profile. J Geophys
Res 84: 4652-4656
Jaoul 0, Froidevaux C, Durham WB, Michaut M (1980) Oxygen self-diffusion in forsterite:
implications for the high temperature creep mechanism. Earth Planet Sci Lett 47: 391-397
172
Kohlstedt DL, Hornack P (1981) Effect of oxygen partial pressure on the creep of olivine. In:
Stacey FD, Paterson MS, Nicholas A (eds) Anelasticity in the Earth. Geodyn Ser, vol 4.
AGlJ, Washington, DC, pp 101-107
Kroger FA, Vink Hl (1956) In: Seitz F, Turnball D (eds) Solid state physics, Advances in
Research and Application, Academic Press New York, pp 307-435
Linker MF, Kirby SH, Ord A, Christie 1M (1984) Effects of compression direction on the
plasticity and rheology of hydrolytically weakened synthetic quartz crystals at atmospheric
pressure. 1 Geophys Res 89: 4241-4255
Paterson MS, Kekulawala KRSS (1979) The role of water in quartz deformation. Bull Mineral
102: 92-98
Ryerson Fl, Durham WB, Cherniak D, Lanford WA (1987) Oxygen diffusion in olivine. EOS
Trans AGU 68: 417
Sato H (1986) High temperature a.c. electrical properties of olivine single crystal with varying
oxygen partial pressure: implications for the point defect chemistry. Phys Earth Planet Int
41: 269-282
Schock RN, Duba A, Shankland TJ (1989) Electrical conduction in olivine. 1 Geophys Res 94:
5829 -5839
Smyth DM, Stocker RL (1978) Point defects and non-stoichiometry in forsterite. Phys Earth
Planet Int 17: 118-129
Stocker RL (1978) Influence of oxygen pressure on defect concentrations in olivine with a fixed
cationic ratio. Phys Earth Planet Int 17: 118-129
3.2 Direct Imaging of Point Defects by HRTEM

D.R.
VEBLEN
and 1.M.
COWLEY
Most mineralogical applications of transmission electron microscopy (TEM)

and high-resolution TEM (HRTEM) have involved the imaging of extended
defects, such as dislocations, stacking faults, Wadsley defects, and antiphase
boundaries. Modern electron microscopes, however, are capable of imaging
individual, isolated atoms (e.g., Isaacson et al. 1979), raising the question of
whether individual or clustered point defects can be resolved within mineral
crystals.
Point defects of interest to the mineralogist include vacancies or substitutional atoms on cation or anion sites, interstitial atoms occupying otherwise
vacant sites, and more complex localized defects that can, in some cases, be
described as clusters of simpler point defects. In addition, there is interest in the
variations in the electrical potential of a crystal due to the nonrandom distribution of different atomic species on a specific crystallographic site in a solid
solution.
In some cases, interactions between defects in a crystal can cause them to
order into a periodic array, producing an ordered superstructure. Alternatively,
point defects can occur in random positions. Intermediate between these two
cases is short-range ordering (SRO) in which the distribution of defects is not
random, but the range of correlation in their ordering pattern (or the size of the
ordered domains) is small. These different types of point-defect distributions
present different problems for electron microscopic imaging experiments.
173
3.2 Direct Imaging of Point Defects by HRTEM
Imaging Ordered Point Defects

In some mineral structures, point defects can cluster into linear or planar arrays,
producing systematic variations in the projected atomic density. These variations can be imaged using normal bright-field, multiple-beam HRTEM experiments, in which the image is formed from the central electron beam plus
some of the surrounding diffracted beams. In addition, the superperiodicities
produced by the ordering are manifested by additional, superstructure spots in
electron diffraction patterns.
Examples of ordered defect distributions include the various pyrrhotite
structures, Fe1-XS, which contain substantial numbers of metal vacancies. At
high temperatures, the vacancies are disordered, but at lower temperatures they
order into various patterns, producing a variety of commensurate and incommensurate superstructures that are a function of composition and annealing
temperature. Columns of Fe atoms containing appreciable numbers of the
vacancies are readily imaged with HRTEM (Pierce and Buseck 1974; Nakazawa
et al. 1975). The Cu-Fe sulfides of the bornite-digenite series also show ordering
of defects into vacancy clusters, which have been imaged using both bright-field
and dark-field HRTEM methods (Pierce and Buseck 1978).
The ordering of vacancies and metal atoms in silicates and oxides also can
produce superstructures that are observable with electron diffraction and direct
HRTEM imaging. For example, oxidation of Fe 2 + to Fe 3+ in olivine minerals
can proceed by reactions of the type
Fe 2 Si0 4 + 0.44 O 2 --+ DO.67Fe1.33Si04
+ 0.22Fe 30 4,
in which the iron component of the olivine reacts with oxygen to form a
vacancy-rich olivine component plus an oxide such as magnetite. This vacancyrich olivine-type structure is called laihunite and is produced during the
oxidation of fayalite. It occurs as several structural variants in which the
vacancies are ordered onto specific planes of Fe atoms, and the resulting
superstructures can be observed with electron diffraction or imaged with TEM
(Kitamura et al. 1984). In the oxidation of more magnesian olivine, ordered
intergrowths of Mg-rich and Fe/vacancy-rich structure form, and the vacancyrich regions can be imaged directly with HRTEM (Banfield et al. 1990).
Furthermore, the ordering of vacancies and metal ions in some silicates can
result in the formation of an antiphase or twin domain structure that can be
imaged with either amplitude-contrast or phase-contrast TEM experiments, as
in the case of vesuvianite (Veblen and Wiechmann 1991).
Imaging Disordered and Short-Range-Ordered Point Defects

Imaging point defects in crystals is not nearly so straightforward when their
spatial distribution is random, or disordered. It is observed in some HRTEM
images that nominally equivalent crystallographic sites exhibit differences in
174
contrast. Iijima et al. (1973) interpreted this effect in tourmaline as resulting from
variations in the cations occupying these sites. However, the quantitative
interpretation of such subtle variations in image contrast in terms of the precise
occupancy of individual sites has not been explored.
The theoretical feasibility of imaging individual vacancies and interstitial
defects in minerals has been explored by Bursill (1985). Using computer image
simulation methods, it can be shown that individual point defects should be
observable in bright-field images formed from the central beam and the diffuse
scattering that lies inside the first set of Bragg diffracted beams (i.e., no diffracted
beams contribute to the image). Furthermore, different types of defects should
produce different types of contrast in such images, and hence it should be
possible to differentiate different defect types. Point defects also may produce
interpretable contrast in lattice images, although the strong contrast arising
from the basic crystal structure may overwhelm the defect contrast, unless the
defects are clustered.
Although it is theoretically possible to image the original distribution of
point defects in a mineral, it is essential for such studies to eliminate a variety of
artifacts that can result from specimen preparation and interaction with the
electron beam, as well as to differentiate between surface and bulk defects.
Nonetheless, Bursill (1985) and his coworkers have produced high-resolution
images showing defect clusters in slightly reduced synthetic rutile and chromium-doped rutile, as well as in several nonmineral structures, including
(Sr,Ba)Nb4 0 12 and (W,Nb)02.93. Bursill and Glaisher (1985) used computer
simulations to interpret images of defects in natural gem-quality diamonds
corresponding to clusters of four missing carbon atoms.
Intermediate between the cases of disordered point defects and ordered
arrays of such defects is the situation known as short-range order, or SRO. In
this case, the defects are ordered, but the size of the ordered domains is too small
(e.g., 10 nm or smaller) to give rise to the diffraction effects generally associated
with ordered structures, such as superstructure spots. Instead, organized diffuse
intensity appears between the Bragg beams in diffraction patterns (Cowley
1950; Clapp and Moss 1968), and dark-field TEM images formed from the
diffuse scattering show a characteristic speckling related to the SRO domain
structure (Howie 1988). However, as shown by Cowley (1973), this speckling
generally cannot be interpreted directly as the SRO domains themselves, due to
electron optical effects such as dynamical diffraction and overlapping of domains in the specimen. An evaluation of the effects of dynamical diffraction on
HRTEM images of thin alloy films with SRO (Tanaka and Cowley 1987)
suggests that at least semi-quantitative interpretations of image intensities are
feasible for this imaging mode. Although most studies of SRO have been
confined to alloys, another example of these diffraction and imaging effects
occurs in the high-pressure hydrous magnesium silicate known as Phase E
(Kudoh et al. 1990). This material contains partially occupied octahedral and
tetrahedral sites, the occupancy of which is correlated over short distances.
Whereas there have been numerous TEM studies of minerals exhibiting
ordered point defects, relatively few systematic studies have explored randomly
3.3 Point Defects and Diffusion in Minerals
175
distributed point defects or SRO of defects in minerals. Now that studies on

nonmineral systems have shown the feasibility of imaging point defects with
HRTEM, applications to minerals will no doubt expand in the coming years.
References
Banfield JF, Veblen DR, Jones BF (1990) Transmission electron microscopy of subsolidus
oxidation and weathering of olivine. Contrib Mineral Petrol 106: 110-123
Bursill LA (1985) The interpretation of HRTEM images of crystals. Ultramicroscopy 18: 1-10
Bursill LA, Glaisher RW (1985) Aggregation and dissolution of small and extended defect
structues in Type Ia diamond. Am Mineral 70: 608-618
Clapp PC, Moss SC (1968) Correlation functions of disordered binary alloys, II. Phys Rev 171:
754-763
Cowley JM (1950) X-ray measurement of order in single crystals of Cu 3 Au. J Appl Phys
21: 24-30
Cowley JM (1973) High resolution dark-field electron microscopy. II. Short-range order in
crystals. Acta Cryst A29: 537-540
Howie A (1988) Highly disordered materials. In: Buseck PR, Cowley JM, Eyring L (eds) Highresolution transmission electron microscopy and associated techniques. Oxford University
Press, Oxford, pp 607-632
Iijima S, Cowley JM, Donnay G (1973) High resolution electron microscopy of tourmaline
crystals. Tschermaks Mineral Petrogr Mitt 20: 216-224
Isaacson M, Ohtsuki M, Utlaut M (1979) Electron microscopy of individual atoms. In: Hren
JJ, Goldstein JI, Joy DC (eds) Introduction to analytical electron microscopy. Plenum Press,
Kitamura M, Shen B, Banno S, Morimoto N (1984) Fine textures of laihunite, a nonstoichiometric olivine-type mineral. Am Mineral 69: 154-160
Kudoh Y, Finger LA, Hazen RM, Prewitt CT, Kanzaki M, Veblen DR (1990) Phase E: a highpressure silicate with unique crystal chemistry. Trans Am Geophys Union 71: 528
Nakazawa H, Morimoto N, Watanabe E (1975) Direct observation of metal vacancies by
high-resolution electron microscopy: 4C type pyrrhotite. Am Mineral 60: 359-366
Pierce LP, Buseck PR (1974) Electron imaging of pyrrhotite superstructures. Science 186:
1209-1212
Pierce LP, Buseck PR (1978) Superstructuring in the bornite-digenite series: a high-resolution
electron microscopy study. Am Mineral 63: 1-16
Tanaka N, Cowley JM (1987) Electron-microscope imaging of short-image order in disordered alloys. Acta Cryst A43: 337-346
Veblen DR, Wiechmann MJ (1991) Domain structure of low-symmetry vesuvianite from
Crestmore, California. Am Mineral 76: 397-404

F.l.
RYERSON
and
R.H. CONDIT
Defects in minerals playa central role in the mechanics of many geochemical

and geophysical phenomena. Prominent among these phenomena are processes
whose rates are controlled by bulk diffusion or the coupling of bulk diffusion
and other mechanisms. Among these are (1) the homogenization of zoned
crystals, (2) alteration of the compositions of minerals, (3) order-disorder
176
reaction, (4) resetting of radiometric ages and the formulation of closure

temperatures, (5) isotopic equilibration, (6) plastic deformation of minerals,
(7) formation of exsolution lamellae, and (8) growth and dissolution of minerals
and related processes such as sintering. Largely due to the compositional
complexity of geologic materials, progress in understanding the relationship
between mineral point defect chemistry and diffusion in geologic materials has
been rather limited. In fact, entitling this chapter "Point Defects and Diffusion in
Olivine" would have required the omission of surprisingly little data. Before
continuing, we refer the reader the texts of Lasaga and Kirkpatrick (1981) and
Schmalzried (1981), and the references therein, for more detailed descriptions of
point defect chemistry.
Point Defects and Diffusion
Point defects may be vacancies, created when a regular lattice site is left
unoccupied, or interstitials, if the normally unoccupied interstices between
regular lattice sites are occupied. These intrinsic defects are present in all crystals
in equilibrium at temperatures above 0 K. Point defects are also required to
accommodate deviations from ideal atomic ratios in nonstoichiometric crystals.
Substitutional disorder is produced by the insertion of an impurity atom/ion
into a normal lattice site. Substitutional disorder can be coupled to the
production of vacancies or interstitials by the insertion of aliovalent cations or
anions. In order to maintain electrical neutrality, this excess charge localized
at the aliovalent ion site must be compensated by an opposing charge at a
neighboring site. Such extrinsic defects are primarily a function of crystal
composition.
A type of substitutional disorder that is particularly important in rockforming minerals is the substitution of iron for magnesium in phases such as
olivine and pyroxene. If the oxidation state of the iron is trivalent, a net + 1
charged is localized on that site is produced requiring charge compensation on a
neighboring site; the concentration of point defects is, therefore, dependent upon
the fugacity of oxygen.
The relationship between diffusion and point defects is immediately apparent when one considers the steric complications associated with the alternative,
diffusive transport in a perfect crystal. Diffusion of ions in densely packed
lattices by mechanisms such as direct exchange or cyclical exchange of two or
more ions is highly unlikely, due to the large lattice distortions required
(cf. Schmalzried 1981). As such, the elementary steps in the transport of ions
(and, hence, charge) within a lattice are coupled to the complementary flux of
point defects. The description of diffusion and point defect chemistry are, thus,
inseparable.
Variations in point defect concentrations are a function of the independent
thermodynamic variables and can be formulated using the law of mass action
for the various defect-forming reactions coupled with assumptions of conserva-
177
tion of mass, charge and structure. Experimental validation of these models

(vs. conductivity, diffusivity, thermogravimetry) must use data acquired under
the same experimental constraints; this, in part, explains the overwhelming
emphasis on the relatively simple and geophysically important olivine structure/composition. A number of treatments of olivine defect chemistry have
yielded qualitative evaluations of the variation in point defect concentrations as
a function of external variables. Constraints such as constant Mg/Si ratio, and
buffering of enstatite activity have been imposed (cf. Stocker and Smyth 1978).
General, quantitative models of defect concentration have recently been formulated which do not require such simplification (Hirsch and Shankland 1991).
Such models require estimates of the energetics of defect-forming reactions, are
capable of evaluating both extrinsic and intrinsic defect populations, and are
worthy of further emphasis. One attempt to describe the specific atomic jump
mechanisms involving point defects in olivine has been reported (Condit, 1981).
The diffusion coefficient of an atomic species is dependent upon the energetics of defect formation and migration. As an example, the diffusion coefficient
for a vacancy is given as:
D = d2 vX e _ [AhmJ
v
3 v
RT'
(1)
where d is the interatomic jump distance, v is a vibrational frequency, and A hm is

the energy barrier between a filled site and an adjacent vacancy site. The site
fraction of vacancies, Xv, is also dependent upon temperature,
Xv
= e-[~J
2RT '
(2)
where A he is the enthalpy of formation for the vacancy (see Lasaga and
Kirkpatrick 1981, for a more detailed derivation of this relationship). Equation
(2) illustrates the concentration of intrinsic vacancy drops exponentially with
temperature; this is in contrast to the relatively constant concentration of
extrinsic defects due to impurity atoms. Hence, at high temperatures, intrinsic
defects dominate the point defect concentrations, but at lower temperatures
extrinsic defects predominate. Comparison of Eqs. (2) and (3) with the Arrhenius
relationship,
D = Do
e-[~J
RT'
(3)
indicates that the activation energy, Q, in the intrinsic region is equal to:
Ahe
Q =T+Ahm.
(4)
Equation (4) predicts that the activation energy should undergo an abrupt
decrease at the transition temperature between intrinsic and extrinsic behavior
as the concentration of defects is no longer related to temperature in the
178
extrinsic region. Such "kinks" or changes in diffusion mechanisms have been

observed in Arrhenius plots of a number of minerals (cf. Mg-Fe interdiffusion in
olivine: Buening and Buseck 1973).
Diffusion Measurements in Olivine

The relationship between the point defect chemistry of olivine and diffusion of
Fe/Mg, 0 and Si in both Fe-bearing olivine and forsterite has been the subject of
a number of investigations. Such investigations are intimately related to studies
of electrical conductivity, plastic deformation, and thermogravimetry. In many
of these investigations, attempts have been made to constrain the thermodynamic state of the sample during the measurement through the imposition of solid
buffers and f0 2 -controlling gas environments. To date, the thermodynamic
variable of prime interest has been f0 2 , since it can be easily varied over a wide
range of values, and the results can be directly related to the defect models.
Both Fe/Mg interdiffusion (Buening and Buseck 1973; Nakamura and
Schmalzried 1984) and Fe tracer diffusion (Hermeling and Schamlzried, 1984)
have been measured in Fe-bearing olivine (F0 9o). The f0 2 exponent for these
experiments lies between + 1/5 and + 1/6. Based upon thermogravimetric data
from unbuffered olivine, Nakamura and Schmalzried (1983) concluded that the
majority defects are a magnesium vacancy, V~g, a trivalent iron ion on a Mgsite, FeMg , and the associate [Fe~i Fe Mg ] and that the f0 2 dependence is for V~g is
+ 1/5. For a similar charge neutrality condition, 2[V~g] = [FeMg ], Stocker and
Smyth (1978) found an f0 2 -dependence of + 1/6 for [V~g]. Hence, measured
diffusion of these cations (via a vacancy mechanism) is in good agreement with
predictions based solely upon defect thermodynamics, as well as those based
upon related experimental data.
Silicon has been shown to be the slowest diffusing major species in both Febearing olivine (Houlier et al. 1988, 1990) and forsterite (Jaoul et al. 1981). Jaoul
et al. (1981) demonstrated f0 2 -independent Si diffusion over nine orders of
magnitude variation in f0 2 for MgO-buffered forsterite. This observation is in
agreement with Smyth and Stocker (1975), who concluded that the concentration of silicon interstitials, was independent of f0 2 Houlier et al. (1990) obtained
a - 1/3 fOrdependence for silicon diffusion in Fe-bearing olivine buffered with
orthopyroxene. This is in agreement with the calculations of Stocker and Smyth
(1978), which predicted such a dependence for the concentration of silicon
in tersti tials.
Oxygen diffusion has been measured in both Fe-bearing olivine (Ryerson
et al. 1989; Gerard and Jaou11989) and in forsterite (Jaoul et al. 1980,1983). The
studies agree to the extent that both experiments determined a positive fOr
dependence for oxygen diffusion. However, quantitatively, they are in disagreement. Ryerson et al. (1989) observe a f0 2 -dependence of approximately + 1/5
(Ryerson et al. 1989) while Gerard and Jaoul (1989) observe a f0 2 -dependence of
+ 1/3. In both cases the positive fOrdependence rules out the participation of
179
oxygen vacancies since Stocker and Smyth (1978) have shown that doubly
ionized, V and singly ionized, V oxygen vacancies have f0 2-dependencies of
- 1/6 and - 1/3, respectively. Based on comparison with the Stocker and
Smyth (1978) calculations, Ryerson et al. (1989) suggested that oxygen diffusion
takes place by transport of a doubly ionized oxygen interstitial, 0;'. Gerard and
Jaoul (1989) reformulated the calculations of Stocker and Smyth (1978) to
account for the role of singly charged oxygen interstitials, 0;, and found a + 1/3
dependence comparable to that observed in their experiments. Both studies
alluded to the steric difficulties produced by the presence of oxygen interstitials
in a closely packed oxygen lattice.
There is no straightforward or unequivocal manner with which to reconcile
the differences in the two sets of oxygen diffusion data. Gerard and Jaoul (1989)
used a hydrous carrier gas (Ar/H2 + H 2 18 0) while Ryerson et al. (1989)
employed a nominally anhydrous mixture OfCI80/CI802' It is possible that the
presence and transport of 18 0 as hydrous species coupled with differences in
buffer assemblages could be responsible for the differences observed. Zhang
et al. (1990) have suggested that diffusion of 18 0 as hydrous species may be
important in silicates and help in reconciling the differences in diffusion
coefficients measured under dry and wet conditions. Little quantitative information ofthe concentration of water in olivine as a function offO 2 and temperature
exists. It is conceivable that such a dependence could influence the diffusivity of
oxygen and its f02-depend~nce. In this regard, Mackwell and Kohlstedt (1990)
have demonstrated relatively rapid hydrogen diffusion in San Carlos olivine.
A number of investigations should be undertaken in order to improve the
data for oxygen diffusion in Fe-bearing olivine. Specific investigations should be
undertaken to determine the effects of hydrous multi-species diffusion on oxygen
diffusion as well as the solubility and homogeneous equilibria of hydrous
species. As part of such an effort, methods for using C180/C180Z without
restriction to solid buffers should be developed to improve the data coverage for
the anhydrous case. Finally, experiments should be conducted imposing variable activities of orthopyroxene. Stocker and Smyth (1978) demonstrate that the
concentrations of defects should vary with silica activity, as well as fO z , and
such measurements would provide an additional means of validating defect
models.
o,
o,
References
Buening DK, Buseck PR (1973) Fe-Mg lattice diffusion in olivine. Geophys Res 78: 6852-6862
Condit RH (1981) An approach to analyzing diffusion in olivine. In: (Schock RN, ed) Point
Defects in Minerals. Geophys Monogr Ser vol 31, pp 106-115, AGU, Washington, DC
Gerard 0, Jaoul 0 (1989) Oxygen diffusion in San Carlos olivine. J Geophys Res 94:
4119--4128
Hermeling J, Schmalzried H (1984) Tracer diffusion of Fe-cations in olivine, (Fe x Mg 1 - x)zSi0 4
(III). Phys Chern Minerals 11: 161-166
Hirsch LM, Shankland TJ (1991) Determination of defect equilibria in minerals. Geophys Res
(in press)
180
Houlier B, Jaoul 0, Abel F, Liebermann RC (1988) Oxygen and silicon self-diffusion in natural
olivine at T = 1300C. Phys Earth Planet Inter 50: 240-250
(1990) Silicon diffusion in San Carlos olivine. Phys
Houlier B, Cheraghmakani M, Jaoul
Earth Planet Int 62: 329-340
Jaoul 0, Froidevaux C, Durham WB, Michaut M (1980) Oxygen self-diffusion in forsterite:
implications for high-temperature creep mechanism. Earth Planet Sci Lett 47: 391-397
Jaoul 0, Poumellac M, Froidevaux C, Havette A (1981) Silicon diffusion in forsterite: A new
constraint for understanding mantle deformation. In: (Stacey FD, Paterson MS, Nicolas A,
eds) Anaelasticity in the Earth. Geodyn Ser vol 4, pp 95-100, AGU, Washington, DC
Jaoul 0, Houlier B, Abel F (1983) Study of 180 diffusion in magnesium orthosilicate by
nuclear microanalysis. J Geophys Res 88: 613-624
Lasaga AC, Kirkpatrick RJ (1981) Kinetics of geochemical processes. Mineralogical Society of
America, Washington, DC, pp 398
Mackwell SJ, Kohlstedt DL, Paterson MS (1985) The role of water in the deformation of
olivine single crystals. J Geophys Res 90: 11,319-11,333
Nakamura A, Schmalzried H (1983) On the nonstoichiometry and point defects of olivine.
Phys Chern Minerals 10: 27-37
Nakamura A, Schmalzried H (1984) On the Fe2+ _Mg2+ interdiffusion in olivine (II). Ber
Bunsenges Phys Chern 88: 140-145, 1984
RicouIt DL, Kohlstedt DL (1985) Experimental evidence for the effect of chemical environment upon the creep rate of olivine. In: (Schock RN, ed) Point defects in minerals. Geophys
Monogr Ser vol 31, pp 171-184, AGU, Washington, DC
Ryerson FJ, Durham WB, Cherniak DJ, Lanford W A (1989) Oxygen diffusion in olivine: effect
of oxygen fugacity and implications for creep. J Geophys Res 94: 4105-4118
Schmalzried H (1981) Solid state reactions. Verlag Chemie, Weinheim, pp 254
Smyth DM, Stocker RL (1975) Point defects and non-stoichiometry in forsterite. Phys Earth
Planet Inter 10: 183-192
Stocker RL, Smyth DM (1978) Effect of enstatite activity and oxygen partial pressure on the
defect chemistry of olivine. Phys Earth Planet Inter 16: 145-156
Zhang Y, Stolper EM, Wasserburg GJ (1990) Role of water during hydrothermal oxygen
diffusion in minerals. Trans Am Geophys Un 71: 650
3.4 Point Defects as Precursors of Electron-Hole Centers:

Systematics and Theories of Radiation Centers in
Minerals
Y. DusAusoyand l.A.
WElL
Many of the local (point) defects in solids are paramagnetic or can be made so,
and hence are amenable to study by electronic paramagnetic resonance (EPR) as
well as by optical spectroscopy. In many cases, it is convenient to classify these
into two general types: missing-electron species and excess-electron species, as
compared to some diamagnetic precursor. The concept of holes is useful when
the number of electrons is insufficient to fill a given atomic or molecular orbital.
Typically, when one more electron is required for this completion, i.e., one
negative charge is missing (this is theoretically equivalent to the presence of a
hypothetical positive charge), then one can speak of the existence of a hole in the
orbital, and treat this as a physically meaningful entity. It is fruitful to speak of
the paramagnetism and EPR spectrum of such a hole. However, the concept is
3.4 Point Defects as Precursors of Electron-Hole Centers
181
not universally valuable, e.g., for species HO and Fe 3 + which have half-filled
shells.
Electron and hole centers occur ubiquitously, in solids found in nature as
well as in those prepared by man. They can be important in various areas of the
Earth Sciences: dating rocks by determination of the concentration of such
centers accumulated over geological time; describing the thermal history of
rocks by the use of the thermal stability of such centers; discerning genetic types
of ore deposits, their zonality, and the stages of mineralization. Moreover, the
knowledge of the structural and chemical nature of such centers in minerals and
also in glasses (Griscom 1990), is fundamental in the comprehension of the
physical properties such as electric conductivity and color. The presence of such
defect centers often results in a loss of quality and reliability for using the
crystals, for instance in high-technology applications that depend on their
piezoelectric and nonlinear optical properties (e.g., frequency doubling oflight).
Various different types of electron/hole centers have been observed in
silicates, carbonates, and other minerals. They display a wide variety of structures and properties, as compared to the traditional atom-vacancy defects
(e.g., the so-called f centers in alkali halides). The former centers appear mostly
in connection with impurities and other nonthermal defects, in crystal structures
greatly different from that of the simple binary halides. Moreover, the centers in
noncubic minerals were observed to be similar to those found in chemistry and
biology representing fragments of molecular radicals, especially ions formed by
trapping or losing an electron. A listing of relevant species and their magnetic
properties has been prepared. (Morton and Preston 1977, 1987; von Zelewsky
et al. ibid). The interpretation of such free radicals in irradiated inorganic
crystals (Atkins and Symons 1967) has given the foundation to the mineralogists
for identifying these centers in natural minerals.
Studies of the electron/hole centers in minerals often are based on the
observation of EPR spectra. The subsequent interpretation of the measured
parameters is based on the molecular orbital pattern of the center, on the crystal
structure, relative covalency, and ionicity of the structure, as well as on the
impurity composition of the mineral. To access a substantial relevant bibliography focused on the field of mineralogy, the reader may refer to two reviews
(Marfunin 1979; Vassilikou-Dova and Lehmann 1987).
Electron and Hole Center Types and Crystal Defects

Paramagnetic electron/hole centers are connected generally with local defects in
the crystal. Often, to attain local electroneutrality of the crystal, a surplus (or
deficit) electron is introduced into the defect, resulting in the creation of an
electron-type (or hole-type) paramagnetic center. The defect can be an anion or
cation vacancy, an interstitial atom or molecule, or an isomorphous (or
interstitial) impurity ion. Mobility of a hole, of course, actually implies electron
hopping. Vacancies are generally labeled using the notation Vx, where X
182
symbolizes the missing atom. Every defect is a potential precursor for various
centers.
Anion and Cation Defects
In ionic crystals, the presence of an anion vacancy implies the lack of negative
charge. The charge-compensation requirement often results in formation of an
electron center (f center). By contrast, a cation vacancy, or the presence of a
structural cation impurity with a too-small positive charge, implies a local
deficit of positive charge. Such a negatively charged structure can act as an
effective trap for a hole. For instance, in the case of a Na + vacancy in NaCl,
electroneutrality can be achieved via loss of an electron from the outer shell of a
neighboring chloride ion. This (p-orbital) hole is in fact found to be delocalized
over two chloride atoms, forming the "molecular" center el;.
Another kind of electron center is due to substitutional cations with
inappropriate charge states:
X+
IM 2 +
substitution
irradiation
IM 2 + +e-
electron trapping
IM+.
Here X is a structural atom and for example could be Na, while its replacement
M could be Mg. The electron source is not specified.
In more covalent materials, similar electron transfers can occur (say, via
irradiation), leading to ions with unusual oxidation states. For example, in
oxides with tetrahedrally coordinated cations, one has:
[X0 4 ]O--+ [X0 4 ] +
[Y0 4 ]O
+ e-
+ e- --+ [Y04 r.
The total charge of the local cluster is indicated as a superscript. For instance,
X could be AI, Ga ... , and Y could be Ge, Fe, P, Ti .... The bracket notation
denotes that the cluster is embedded in the crystal structure.
In crystalline quartz, when AI3+ replaces Si 4 +, an electron is easily removable from a neighboring oxygen ion to form what is effectively a hole center, 0In such cases, the unpaired electron density is not located at the primary defect
(AI) but is on a structural neighboring site (O). In this sense the trapping process
is not generally symmetric for a hole center as compared to an electron center. In
all cases, the surplus electron or hole is distributed to some extent throughout
a group of atoms and its behavior must be interpreted in terms of molecular
orbitals.
Radicals in Crystals
While electron configurations of single-ion centers are well described by atomic
orbitals, those of complex ions are described by molecular orbitals: bonding,
anti bonding, or non bonding. The electrons taken into account in populating the
relevant molecular orbitals are the n outer (valence) electrons of all atoms in the
183
species. Consider the relatively simple ions denoted by AWn), AB~n), AB~n), and
AB~) (Atkins and Symons 1967). Atoms A and B often encountered include: B,
Al (n = 3); C, Ge (4); N, P, As (5); 0, S, Se (6). Some corresponding diamagnetic
complex ions are BO~ - (n = (1 x 3) + (3 x 6) + 3 = 24), CO~ - (24), POl- (32),
SO~ - (32). Here the charge number q indicated (as an unparenthesized superindex) is a formal one, that of the sum of all electrons and nuclei in the cluster of
interest, no account being taken of covalency when the ion is imbedded in a
crystal. If the latter situation is to be emphasized, then the notation [AWn)]q may
be used.
By trapping an electron, each of the complex ions listed above can become
an electron center (e.g., PO!- (33), with formal valency p 4 +). The unpaired
electron is found in a molecular orbital derived mainly from the sand p orbitals
of the central cation.
By losing an electron, the diamagnetic complex ions become hole centers
[e.g., PO~ - (31)J; the remaining unpaired electron occurs in a molecular orbital
consisting predominantly of oxygen nonbonding orbitals.
These processes can be written as reactions:
+ M2+ -CO~- + M3+ electron center (e.c.)

CO~- + M2+ -CO;- + M+ hole center (h.c.)
SO~- + M2+ -SO~- + M3+ + e- -SOl- + M3+ (e.c.)
POl- + M3+ _ POl- + M2+ + e+ _ PO~- + M2+. (h. c.)
CO~-
Here ions M represent electron donors/acceptors present somewhere in the

crystal.
Radicals sometimes can be found in nonisostructural substitutions: species
SO;, SSO-, SO;-, SSO; have all been observed. For example, in sulfates,
radicals SO;- can result from the presence of oxygen vacancies.
Identification of Electron and Hole Centers from EPR Spectra

For more information regarding the EPR technique and relevant notation,
the reader is asked to refer to Chapter 10.8, this volume. The identification of
electron/hole centers from EPR spectra generally occurs in two stages:
1. Observation ofthe EPR spectrum. Relevant information includes the number
of absorption lines, their intensities, the line splittings, and the behavior of the
spectrum on rotation ofthe crystal relative to the applied static magnetic field
(flux density) B. The field magnitude, B, is measured in units of Teslas or
Gauss (1 mT = 10 Gauss).
2. Interpretation of the measured parameters based on the molecular orbital
pattern of the centers, as well as on the crystal structure and impurity
composition of the mineral.
These two stages of the study generally allow identification and site assignment
of the paramagnetic center in the crystal. Let us turn to details of these stages:
184
Observation of the EPR Spectrum
1. The Number of Lines. In most cases, a single fine-structure line occurs and is
due to an electron or hole center with an electronic spin S = 1/2. In the presence
of nuclear spins I on the central and neighboring atoms, the electronic-nuclear
spin coupling(s) leads to splitting, i.e., hyperfine structure (HFS) in the spectrum.
In the presence of a Zeeman interaction, the relevant energy operator (spin
Hamiltonian) is
N
JI'=PBgS+SA
e
0 1+ "SA.-f.
~
1
P
i-I
where Pe = lelh/2me is the Bohr magneton, Ao is the primary hyperfine matrix,

and Ai the superhyperfine matrices describing hyperfine splittings from relatively distant nuclei. This operator is used to compute the spin energy levels, and
subsequently the EPR line positions and relative intensities. Note that, for
S = 1/2, the line is not split by the crystal electric field, and that higher-order
parameters B::' are not included in JI'; the situation is more complex when
S> 1/2.
In noncubic materials, the detail of the EPR spectrum generally changes
rapidly with orientation of the crystal relative to the magnetic field. To
understand the spectra, it is necessary to take into account the crystal pointgroup symmetry controlling the number of geometrically different but chemically equivalent centers in the structure.
In the case of N identical nuclei of nuclear spin I, the EPR spectrum of the
centers generally consists of 2NI + 1 equally spaced lines (for sufficiently great
excitation frequencies v and fields B). For instance, the center AI3+ -0- -Si 4 +
7 Al 100% abundance, I = 5/2) in quartz shows six anisotropic lines with equal
intensities, whereas the AI3+ -0- -AI3+ center in alkali feldspars shows 11 lines
with unequal intensities (Fig. 33). Here the notation -0- - denotes the absence
of the non bonding electron from the oxygen ion, i.e., presence of a hole.
If there are several isotopes with applicable abundance (some with nonzero
nuclear spin), then the spectrum is more complex, and the intensity of the lines
arising from the hyperfine couplings is a function of the natural abundances of
the isotopes (e.g., boron: lOB 18.83% I = 3, and liB 81.17%, I = 3/2; evenSi
95.33%, I = 0; and 29Si 4.67%, I = 1/2). The hyperfine splitting patterns provide
valuable clues for the interpretation of EPR spectra. Furthermore, the hyperfine
splitting values L1A often allow identification of the different paramagnetic
centers. Thus, for phosphorus: 31 P 100% I = 1/2, the L1A values occur in the
ranges: PO!- (110-120mT), POI- (2-5), PO~- (45-70), and PO~- (4-9).
2. Theg Values. Thegfactorg = hv/veB at any crystal orientation is obtainable

experimentally. Such data can be summarized by means of the 3 x 3 parameter
matrix g. Thus, by changing the orientation of the crystal relative to magnetic
field B, it is possible, with rotations (sometimes about several perpendicular
axes), to determine the three field positions of the absorption line corresponding
AI-O--AI
185
Fig. 33. EPR spectrum of a natural alkali feldspar (80 K;

9.24 GHz) shows two types of centers: 27AI_O- _27AI with
11 equidistant lines (relative intensities 1:2:3:4:5:6:5:4:
3: 2: 1), and unstable Si-O - _27 Al with six equidistant lines
7 AI, 100% abundance, 1= 5/2) (Petrov et al. 1989). Spectra
at two orientations of the crystal relative to field Bare
shown, and illustrate anisotropy
AI-O--Si
AI-O--AI
314
324
334
344
MAGNETIC FIELD B(mT)
to the principal values of gx gy gz and in the same way the three values (for each
nucleus) of the principal hyperfine parameters Ax Ay Az, which often but not
always occur at nearly the same crystal positions as those for g. The values and
the corresponding orientations of the g principal axes and HFS axes (of A)
relative to the crystal-axis system generally allows one to locate the center and
to suggest a possible model for it. Moreover, the form of the g and A matrices is
connected with the symmetry (e.g., group C 3v for CO~ -) of the paramagnetic
species.
3. The HFS Components. The principal values Ax, Ay, and Az give details of the
hyperfine coupling, and thus an idea of the highest occupied molecular orbital
involved in the paramagnetic center. The isotropic component Aiso = (Ax + Ay
+ Az}/3 of A is related to the magnetic interaction of the unpaired electron (in
186
the s-electron orbital portion of its wavefunction) with the nucleus; the anisotropic part Aaniso is related to interaction of the unpaired p (also d and f, if any)
electron(s) with the nucleus. Thus the relation between those two parts yields the
degree of sp hybridation of the unpaired-electron wavefunction.
Interpretation on the Basis of the Molecular Orbital Scheme
If the unpaired electron resides in a molecular orbital formed chiefly from the
central-atom orbitals, then the magnitude of the hyperfine interaction with the
nucleus of the central cation is strong and consequently a substantial splitting
----
,*
5 01
----20~*
2pC
V--'
h'--ft
2pO
#=fF
10 2
Ie"
A
I
2e'
I02II
HH
Ie'
tf
25C
/,
3e
2e
I
I
ENERGY
40 1
. 5 , 52 5 3
As,(2"? (0,,)
##
#=4f
50 1
Ie
##
40 1
5 15 2 5 3
AS,(2'C,,)
Fig. 34. Qualitative molecular-orbital schemes for radicals ABj23) (planar: CO.l. PO~) and
AB~25) (pyramidal: CO~ -, PO~ -, S0.l). The energy levels are labeled with group-theoretical
symbols. The 23rd electron (ABj23/) is in the non bonding molecular orbital la~ formed
primarily from atomic 2p orbitals of the three oxygens; thus the interaction of the 23rd electron
with the central nucleus is weak, and the hyperfine structure very small. The 25th electron
(AB~25) lies in the molecular orbital 6aj formed mainly from sand p orbitals of the central
atom; thus large hyperfine structure occurs in the EPR spectrum. (Marfunin 1979, p. 250)
187
is visible in the EPR spectra (when I > 0). If the molecular orbital is based
primarily on nearest-neighbor atoms, say it is formed from oxygen orbitals, then
there is a weaker interaction of the electron with the cation nucleus, as evidenced
by a much smaller (superhyperfine) splitting in the EPR spectra. The molecularorbital situation for two such situations is depicted in Fig. 34.
The sign of the shift Ag = g - ge (where ge = 2.00232 is the free-electron
value) of the g-factor measured is determined by the relative ordering and
energies of various outer-electron molecular orbitals. The analysis is complicated. The Ag value tends to be negative for electron centers and positive for hole
centers, but depends also on covalency effects.
Let us turn to some examples. In irradiated calcite, the 13C (1.11 % abundance, I = 1/2) hyperfine structure visible in the EPR spectra of C0 3 center
AB~23) is relatively small (ca. 10 G, nearly isotropic) due to very weak interaction
between the 23rd electron and the central nucleus (Serway and Marshall 1967).
In the case of the CO~- radical AB~25), interaction with the central atom
is strong and hence the hyperfine structure in large (Ax = Ay = 111 G and
Az = 171 G). These species are, respectively, isoelectronic with (for instance)
N0 3 and NO~ -, and thus are similar in their EPR characteristics.
Electron paramagnetic resonance of a natural barite crystal (Ryabov et al.
1983) has revealed the presence of several distinct electron centers (Fig. 35). Ions
S03 and PO~ - both belong to the radical type AB~25), with the 25th (unpaired)
even
80 3- ~
even
802-
10- 2
\1\
~+
+---i
Fig. 35. EPR spectra of oxygenic phosphorus and sulfur radicals in barite (290 K; X band;
Bllb), exhibiting site splittings and showing central-nucleus hyperfine multiplets. (Ryabov et al.
1983)
188
electron in the molecular orbital 6at. The two centers evenS03" and evenso; do
not show hyperfine structure (S33 = 1/2 and 1 = 0 for all nuclei), i.e., show only
one line. The 33S03" center (S = 1/2,1 = 3/2) shows 21 + 1 = 4 lines with a large
hyperfine splitting. The two different 31PO~- centers (S = 1/2, 1 = 1/2) show
two lines with a very large hyperfine splitting. The ions SO; belong to the
ABi19 ) radical type with the 19th electron in the antibonding molecular orbital
2bt formed mainly from a p orbital of the central atom.
Varieties of Electron and Hole Centers

A systematic survey of the electron/hole centers in minerals and inorganic
compounds are shown in Table 23 (Marfunin 1979, p. 255). The electron/hole
cations are presented in the table in such a way that they are grouped according
to their basic (over-simplified) outer-electron configuration types. All valenceisoelectronic radicals are describable by the same molecular-orbital scheme,
whatever the studied mineral.
Table 23. Systematic survey of the electron/hole centers in inorganic compounds and minerals
Anion vacancies, with ne trapped
electrons
ne
Cations with trapped electron or hole
HO Lio Mg+ Ca+ Be2+ Ge3+ p 4+
F center
F+ =
()(-center
F-
F(2) =
M-center
F(~)
F(l)
pI
Tl o Pb+
F(3) =
R-center
F(;)
F(3)
dl
F(4) =
N-center
d10S l
Ti3+ V4+(*) Cr 5+ Mn 6 yZ+ Zn3+ ...

* often occurring as VOZ +
Fe+ ~ Fe z + ~ Fe3+ ~ Fe 4 + Ni+
~ Ni2+ ~ Ni3+ ...
Cu o AgO Zn +
fn
RE+
Anions, with trapped hole

p5 0- S- Se- Te- FO (FClo (Cl;) Bro (Br;l 1
Sl
Pb 3 +
dn
+ FO =
F;)
RE2+
RE3+
RE 4+
0- centers in polymeric structures

Si-O- -AI Al-O- -AI
B-O- -Ii
Inorganic radicals, with trapped electron or hole

AB(n) n = 11/13/15: BO z - CO- SiO- NO PO ... /0; SO- /O~- F; Cl; ...
AB~n) n = 17/19: BO~- CO; SiO; NO z POz SO; .. /NO~- PO~- AsO~- SO; 0; ..
AB)n) n = 23/25/27: BO~ - CO; SiO; .../CO~ - SiO~ - SO; .../O! - ...
AB~) n = 31/33: B01- SiO!- POi- .. ./SiO~- P01- SO!- .. .
MB4 V01- CrO!- MnOi- WOl- ...
189
The center characteristics as obtained by means of EPR do not vary much

from one mineral to another, in contrast to the changes observed in thermoluminescence peaks. Thus the centers are generally identifiable unambiguously,
together with their concentrations and structural and chemical nature. Furthermore, information often can be deduced about center precursors: substitutional
impurities, vacancies, and interstitial ions.
Electron and Hole Centers in Minerals

Because of the selected bibliography, all the results presented in this chapter are
not referenced. For more information the reader may write to the authors. Most
electron/hole centers are formed by natural or artificial irradiation (IX-, X-, y-rays,
electrons, neutrons). Numerous studies on electron-hole centers in major rockforming minerals (such as quartz, feldspars, calcite, anhydrite, and accessory
minerals such as zircon and apatite) have been carried out (e.g., see the two
reviews cited in the introduction). The technique provides an excellent means for
characterizing these minerals and the rocks enclosing them. We turn now to
some specific systems:
Quartz. Crystalline silicon dioxide is the most studied mineral, not only on
natural specimens because of its geological importance, but also on synthetic
crystals on account of the fundamental interest in it and its technological
applications (e.g., electronic oscillators and laser modulators). Quartz can be
called the "hydrogen atom" of minerals. The EPR characteristics of the different
center types have been reviewed (WeilI984) with 230 references. In IX-quartz, the
space group is P3 1 21 or P3 2 21 (left or right quartz), each with two sets of crystal
twofold rotational axes (the first set bears silicon atoms; the second, at 30 to set
1, carry no atoms) which are electrically polar. The local symmetry at each Si0 4
tetrahedron is only the twofold axis, consistent with the presence of two Si-O
bond types with lengths: "short" 1.610 and "long" 1.645 A at 94 K (Fig. 36a, b).
Perfect (ground-state) quartz would not contain unpaired electrons and hence
would yield no EPR spectrum. In practice, numerous paramagnetic centers arise
from impurity ions (Ag, AI, Cu, Fe, Ge, H, P, Ti) as well as from centers (E')
associated with oxygen vacancies in the quartz structure. The kind of chargecompensator ions M+ (H+, Li+, Na+, Ag+) present in the structural channels,
as well as the exact positions of the compensators, cause occurrence of many
varieties of the centers.
Centers Having Impurities as Precursors. The replacement Si --+ Al leads to
various types of paramagnetic centers. The initial species [AI0 4 /M]O, diamagnetic unless the interstitial ion M + is paramagnetic (e.g., Agi), is a precursor to a
paramagnetic (S = 1/2) center [AI0 4 /M] + created by X-irradiation at low
temperature ( < 77 K). This cation has a hole on a (short-band) oxygen ion
nearest-neighbor to AI, i.e., AI-O- -Si in the previously used notation. For
190
/\
o SILICON
OXYGEN
/\
~~~~--~~~------~~---+
""
I,
If"
1\
"
""
"
/I
""'6il- .
~--"':'~~if.{}-=':'::'-~. ::.:---.
>r
/1/
,I
Lx
I"
"
/I
,I ""
b
Fig. 36a, b. a-Quartz structure (a) projection onto the plane perpendicular to the c axis
(b) Si0 4 tetrahedron showing two non-equivalent Si-O bonds and two possible sites for
interstitial ions in the middle of the large c-axis channels. (Weil 1984)
M = H, the superhyperfine structure in the EPR spectrum allows one to

visualize the proton in the adjacent large c-axis channel as being hydrogenbonded to an oxygen ion on the long-bond side of the Al0 4 tetrahedron. With
Li +, the ion also occurs in the channel and (unlike H +) is on the twofold axis.
On warming (or directly by irradiation at room temperature), diffusion away of
M+ leads to formation of a new center, [Al0 4]O (Fig. 37). Here a hole, on a
(long-bond) neighbor oxygen ion at 77 K, on heating becomes thermally
activated, eventually to reside in turn equally on each of the four oxygen ions,
191
Fig. 37a-e. EPR transitions for
[AI0 4]O in IX-quartz. (a Experimental spectrum (35 K; 9.98 GHz;
Bile) calculated spectrum and b, e
energy level diagram. (Wei! 1984).
Here, rather than the simple firstorder spectrum consisting of six
hyperfine lines from 27 AI, a more
complex spectrum is observed, at
v = 10GHz
b
B
1.0 mT
'1
ENERGY
causing broadening of the EPR spectrum. The hole transfer also can be induced
by absorption of light (smoky quartz color), and this has been studied (Meyer
et al. 1984) by optically detected magnetic resonance (ODMR). In addition, by
irradiation below 77 K without subsequent warmup, an unstable center
[AI0 4]+ forms and can be observed by EPR. This species contains two holes,
on nearest-neighbor (short-bond) oxygen ions related by the structural twofold
symmetry axis, in a triplet state. Similarly, a center in which four protons appear
to have replaced a Si 4+ ion leads on irradiation to an oxygen hole center
[(OH)4] + which transforms to [O(OHh]O by proton loss, both observable
by EPR.
The [Ge0 4 center (formally Ge3+) is obtained in the same way, by
electron trapping at the diamagnetic precursor [Ge0 4]o. EPR spectra from the
ground-state species as well as from a thermally accessible excited-state species,
[Ge04]~' are observed. However, above 100 K, charge compensation occurs,
via migration to the anions of Li + ions along the c-axis channels. Thus the two
best-known centers are [Ge04/Li]O with Li+ in either of two different sites.
With Na + as compensator ion, only one such center is stable at 300 K, and none
occurs with H + or K + ions. Other Ge 3 + centers have been observed, including
[Ge04/H-Li+Li+]O and [Ge04/H-H+H+]o.
With phosphorus as an impurity, X-irradiation creates p 4 + centers. Here as
with germanium, two EPR spectra, from [P0 4]O and [P04]~S' are observed. In
192
another a-quartz species, the EPR hyperfine structure has been attributed to the
cluster [03AI-0- -P0 3]+ (Maschmeyer and Lehmann 1983).
In natural rose quartz, the diamagnetic species [Ti0 4]0, as a result of
X-irradiation below tOO K, accepts an electron to yield the 3d 1 center [Ti0 4
which is unstable at room temperature. On warming, diffusion of an M + cation
leads to formation of centers [Ti0 4 /Li]O, [Ti0 4 /Na]O and/or [Ti0 4 /H]o. The
latter is formed from [Ti0 4 ]O by accepting a hydrogen atom. Various iron (III)
centers have been characterized, corresponding to substitutional sites, including
[Fe0 4
[Fe0 4 /H]o. [Fe0 4 /Li]O, [Fe04 /Na]O and [Fe0 4 ]o. The EPR spectra
of [FeO 4] - have been used to investigate the a-fJ phase transition of crystalline
quartz (847 K) and of berlinite (Lang et al. 1977).
r,
r,
Centers Due to Oxygen Vacancies. The best-known such center, E'l' (Fig. 38a, b)
results from a missing bridging oxygen ion between two silicon ions and can be
depicted as [03Si Si0 3] +. The unpaired electron is predominantly located on
one silicon ion, Si(1). The presence of E'l centers is applicable in mine prospecting (Chatagnon 1986). A similar center, E~, is found in irradiated quartz and
exhibits EPR hyperfine structure attributed to a remote hydrogen ion, with the
unpaired electron density appearing to be greatest on Si(2) (Fig. 39). The E~
center simultaneously present contains a proton bonded as a hydride ion:
[03Si' H: Si0 3]O; this increasingly hops between the Si ions as the temperature
is increased.
Various discussions on the origins of quartz coloration have been published,
as well as investigations of defects in shock-loaded quartz, connected with
metamorphism.
Ice. Irradiation of frozen water leads to various defect species. Prominent
unpaired-electron centers include the radicals 0 -, OH and OOH, as well as

atomic hydrogen.
Feldspars. The distribution of centers varies in the many feldspar types. Microcline presents the greatest number of centers, followed by orthoclase, sanidine,
plagioclases, and their end members albite and anorthite. Irradiation develops
oxygenic hole centers 0 - in all feldspars.
The replacement Si --. Al here too is the principal cause for various paramagnetic centers to be observable. In feldspars, each structural alumina tetrahedron normally is surrounded by four silica tetrahedra. The replacement of a
silicon by an aluminium ion produces a local structure Al (structural) -0 - -AI
(impurity) with loss of an electron from the bonding oxygen between the two
tetrahedra. The number of lines in the EPR spectrum of such a center is
2 (2 x 5/2) + 1 = 11. The number of nonequivalent centers observed in the feldspar depends on the symmetry (triclinic or monoclinic) and on the twinning
(cross-hatched in microcline) present. Other centers occur as clusters containing
at least three aluminium ions. They are not detectable by EPR except at low
temperatures, indicating that here too the hole is rapidly transferred between
nearly equivalent oxygens. The probability for having such a cluster increases
193
+
Magnetic field (G)
a
1\
f------'.,. 1\
Fig. 38a, b. E'l center in IX-quartz. a EPR

spectrum (297 K; 9.33 GHz; Bile) exhibiting
a single intense line flanked by two nearby
pairs of weak hyperfine lines 9 Si, abundance 4.67%, 1= 1/2; splittings 8.02 and
9.12 Gauss) and a pair of remote hyperfine
lines 9 Si; splitting 403.6 G). (Jani et al.
1983). b Model of the E'l center showing the
missing bridging oxygen ion between Sill)
and Si(2) as a dotted circle. The unpaired
electron is predominantly located on Sill)
which yields the major hyperfine doublet
(Isoya et al. 1981)
OSi
b
00
markedly as the Al/Si ratio approaches the value 2. It seems that the Si-O - -AI
center, only observed after low-temperature ( < 77 K) irradiation, is unstable,
relative to the AI-O- -AI center at higher temperatures.
In amazonite, a pale-green variant of microcline (KAISi 3 0 s), the Pb impurity center is converted to Pb-O- -x by X-irradiation and the color thereby
194
...
~~
O.2SmT
I
f
E4 'L
__________ I ___________ IL __________ .JI

~
Fig. 39. EPR spectra of centers E~ and E~ in a-quartz (300 K; 9.8 GHz; Bile) normal hyperfine
I H doublet of E~ and unusual 1 H quartet of E~, with 29Si superhyperfine structure on both.
([soya et al. 1981)
attains a brownish tint. A [Ti04]O center is reported in some feldspar types - its
principal EPR values are similar to those observed in quartz. The formation of
NHj and N 2 - centers from NHt ions is connected with the presence of M +
vacancies. The NHj EPR spectrum disappears after heating the specimen to
temperatures higher than ca. 470 K, whereas the N 2 - center is stable up to
ca. 820 K. Also observed were the formation of atomic hydrogen from an
OH- group, and the E'l center (similar to the E~ center in quartz) stable up to
ca. 420 K.
The study of irradiation defects in 15 feldspars of various compositions
(utilizing EPR, optical absorption, and thermoluminescence emission bands)
shows that these are remarkably independent of the mineral specimen, composition, and AI/Si structural disorder.
Zircon. Numerous investigations have been carried out to characterize the
various types oflocal structural defects in ZrSi0 4 . The spectroscopic character-
195
istics of natural zircons can be used as indications of the genesis of different

rocks: granitoids, pegmatites, kimberiites, and sedimentary specimens.
Aluminosilicates with Channels or Voids in the Framework. Additional anions
such as Cl-, CO~-, SO~- (coordinated with Na+ orCa2+ cations) can befound
in the channels or voids of the alumino silicate skeletons of minerals such as
cancrinite, sodalite, and lazurite, and cause colors to be generated on irradiation. In these materials, the blue color comes from SOi or S03". The pink
variety of sodalite contains the hole center S02' due to the loss of an electron
from the precursor SO~ -. In scapolites, the centers S03" , S02, C03" and CO 2
have been found. In topaz, tourmaline, and phenakite (Nassau and Prescott
1975), the same type of studies related the color origin to specific centers, mostly
paramagnetic, some of them induced by irradiation.
Carbonates - Sulfates - Phosphates - Tungstates. Various center types have
been observed in the minerals: calcite, anhydrite, barite, celestine, apatite,
scheelite. These include:
- numerous impurities substituting for the cation: e.g., Ca2+ -+ Mn 2+, Fe 2+ ,

Ni 2+, ... , Fe3+, Gd3+, y3+ and other rare earths. These replacements do
not all lead directly to paramagnetic center formation;
- numerous anionic substitutions: CO~ - in calcite-+ PO~-, pog, PO~-, PO~,
AsO~-, S03", BO~-, SO~- in anhydrite-+PO~-, BO~; PO~- in apatite-+CO~-, C03", SiO~-; WO~- in scheelite-+SO~-;
- interstitial ions: 03", O 2 , S2 in anhydrite.
The existence of varieties of substitutions (particularly rare earths), vacancies
and interstitial ions allows nominally identical minerals coming from different
types of deposits to be distinguished.
Cubic Ionic Crystals. Many detailed studies of the defects in alkali halides,
alkaline oxides and chalconides have been published. Commonly, sites where
atoms (ions) are missing from the regular structure lead to paramagnetic species
amenable to EPR investigation.
The first color-center studies were performed on the F centers in alkali
halides. The understanding of their properties has been arrived at with the use of
polarized absorption, luminescence, and (above all) with EPR and electronicnuclear double-resonance (ENDOR) spectroscopy. These methods have confirmed that the F center is an electron trapped at an anion vacancy, and that the
electron interacts equally with the six nearest-neighbor cations.
EPR spectroscopy shows that the F-center electron interacts not only with
the six nearest cations but also with anions and cations in further coordination
spheres, up to the 16th. The EPR spectrum shows an unusually broad band,
from 58 Gauss in KCl to 800 G in CsC!. The broadending is due to the resolved hyperfine structure arising from interaction of the F-center electron
with neighboring nuclei such as 6.7Li, 23Na, 39.41 K, 85. 87Rb, 133CS or
196
19F, 35, 37 Cl, 79,81 Br, all with nonzero nuclear spins and appreciable natural
abundances. The densities of the spin states determine the relative intensities of
the hyperfine-structure lines. In some alkali halides (LiF, NaF, RbCl, CsCI),
partially resolved hyperfine structure has been observed. The use of ENDOR
substantially improves the resolution, making it possible to measure transitions
between nuclear spin levels and enabling measurement of the isotropic and
anisotropic parts of the electron-nuclei hyperfine interactions.
The F centers give intense bands (e.g., at energy 2.6 eV) in optical absorption
spectra, corresponding to electronic transitions. The F-center concentration can
be determined by measuring the optical absorption coefficient, by chemical
analysis, magnetic susceptibility measurements and by EPR intensity measurements. In addition, aggregate F centers called f(2) ... f(4) form in alkali halides,
corresponding to clusters of two, three, and four F centers.
The F center also occurs in other crystalline compounds in which halogen,
oxygen, sulfur vacancies trap electrons, e.g., in compounds with the fluorite
structure (CaF 2, SrF 2' BaF 2) or with the rutile structure (MgF 2)' In apatite and
fluorite, one finds F centers each consisting of a fluorine vacancy containing a
trapped electron, and 0 2- centers formed due to the substitution 0 2- ~ F - .
The centers in fluorite allow its use as a radiation dosimeter. In these, the gfactor values exhibit a greater shift ~g than in the case of the alkali halides. The
features of the hyperfine structure of EPR spectra are dominated by the isotope
compositions of the nearest cations. Nonmagnetic nuclei prevail in the alkalineearth compounds. In alkaline-earth oxides, the F center contains two electrons
in an anion (X2 -) vacancy, and thus is neutral. Because of spin pairing, it is
diamagnetic and EPR-mute. Optical excitation can unpair the electrons, yielding a triplet state accessible to EPR, as is the ionized center F (Henderson and
Wertz 1977). The F center is also thought to be present in silicates such as
sodalite and zeolite (but not in quartz).
References
Atkins PW, Symons MCR (1967) The structure of inorganic radicals. An application of
electron spin resonance to the study of molecular structure. Elsevier, Amsterdam
Bershov LV, Marfunin AS (1967) Paramagnetic resonance of electron-hole centers in minerals.
Dokl Akad Nauk 173: 410-412
Bershov LV, Martirosyan VO, Marfunin AS, Speranski AV (1975) EPR and structure models
for radical ions in anhydrite crystals. Fortschr Mineral 52: 591-604
Bill H, Calas G (1978) Color centers associated rare-earth ions and the origin of coloration in
natural fluorites. Phys Chern Mineral 8: 161-166
Chatagnon B (1986) La resonance paramagnetique electronique du center E'l dans Ie quartz.
Aspect fondamental et interet en geologie et en prospection miniere. These d'Etat INPL
Nancy
Edgar A, Vance ER (1977) Electron paramagnetic resonance, optical absorption and magnetic
circular dichroism of the CO; molecular ion in irradiated natural beryl. Phys Chern
Mineral 1: 165-177
Griscom DL (1990) Electron spin resonance. Glass Sci Technol 48: 151-251
Henderson H, Wertz JE (1977) Defects in alkaline earth oxides. Wiley, New York
3.5 Structural Types of NonStoichiometry in Minerals
197
Hofmeister AM, Rossman GR (1985a) A spectroscopic study of irradiation coloring of

amazonite: structurally hydrous, lead-bearing feldspar. Am Mineral 70: 794-804
Hofmeister AM, Rossman GR (1985b) A model for the irradiative coloration of smoky
feldspar and the inhibitive influence of water. Phys Chern Mineral 12: 324-332
Isoya J, Weil JA, Halliburton LE (1981) EPR and ab initio SCF-MO studies of the Si.H-Si
system in the E~ center of alpha-quartz. J Chern Phys 74: 5436-5448
Jani MG, Bossoli RB, Halliburton LE (1983) Further characterization of the E'l center in
crystalline Si0 2 . Phys Rev B27: 2285-2293
Krasnobaev AA, Votyakov SL, Krokhalev VYa (1988) Spectroscopy of zircons: properties and
geological applications. Nauka, Moscow, 150 pp
Lang R, Calvo C, Datars WR (1977) Phase transformation in AIP0 4 and quartz studied by
electron paramagnetic resonance of Fe 3 +. Can J Phys 55: 1613-1620
Lehmann G, Bambauer HU (1973) Quartz crystals and their colors. Angew Chern 85: 281-289
Marfunin AS (1979) Spectroscopy, luminescence and radiation centers in mInerals. Springer,
Marfunin AS, Bershov LV (1970) Electron/hole centers in feldspars and their possible crystal
chemical and petrological significance. Dokl Akad Nauk 193: 412-424
Marshall SA, McMillan JA (1968) Electron spin resonance absorption spectrum of CO 2
molecule ions associated with F- ions in single-crystal calcite. J Chern Phys 1: 4887-4890
Maschmeyer D, Lehmann G (1983) A trapped-hole center causing rose coloration of natural
quartz. Z Krist 163: 181-196
Morton JR, Preston KF (1987) Magnetic properties of free radicals. In: Fischer H (ed)
Landolt-Bornstein numerical data and functional relationships in science and technology,
New Ser, Group II, 17a. Springer, Berlin Heidelberg New York, pp 5-198. Also: Von
Zelewsky A, Daul C, Schliipfer CW (1987) Table 2, pp 199-205
Nassau K, Prescott BE (1975) Blue and brown topaz produced by gamma irradiation. Am
Mineral 60: 705-709
Petrov I, Agel A, Hafner SS (1989) Distinct defect centers at oxygen positions in albite. Am
Mineral 74: 1130-1141
Ryabov ID, Bershov LV, Speransky AV, Ganeev IG (1983) Electron paramagnetic resonance
of PO~ - and SO; radicals in anhydrite, celestite and barite: the hyperfine structure and
dynamics. Phys Chern Mineral 10: 21-26
Schulman JH, Compton WD (1963) Color centers in solids. Pergamon Press, New York
Seitz F (1954) Color centers in alkali halides crystals. Rev Mod Phys 26: 7-94
Serebrennikov AI, Valter AA, Mashkostsev RI, Scherbakova MYa (1982) The investigation of
defects in shock-metamorphosed quartz. Phys Chern Mineral 8: 153-157
Solnstev VP, Scherbakova MYa (1973) EPR study of structure defects of CaW0 4 . Zh Strukt
Chim 14: 222-229
Speit B, Lehmann G (1982) Radiation defects in feldspars. Phys Clem Mineral 8: 77-82
Vassilikou-Dova AB, Lehmann G (1987) Investigations of minerals by electron paramagnetic
resonance. Fortschr Mineral 65: 173-202
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paramagnetic defects in crystalline quartz. Phys Chern Mineral 10: 149-165

D.R.
VEBLEN
Some minerals possess virtually fixed stoichiometry, with the coefficients in the
structural formula all being integers. Naturally occurring quartz, for example,
does not deviate far from pure Si0 2 Many other minerals, however, can exhibit
198
marked nonstoichiometry, with nonintegral formulae, although their nonstoichiometry is sometimes masked by presenting their compositions in terms of
idealized, nominally stoichiometric end members. Some of the most important
rock-forming silicates, oxides, and sulfides, as well as minerals of geophysical
interest, exhibit major deviations from stoichiometry, and hence it is essential to
recognize when a mineral is non stoichiometric and to understand the structural
basis for the nonstoichiometry. Furthermore, the degree of nonstoichiometry
affects thermodynamic, physical, and transport properties in minerals, such as
magnetic properties, deformation properties, electrical conductivity, and diffusion rates.
Nonstoichiometry commonly arises in structures where cations of different
valences can occupy the same crystallographic site (e.g., Fe 2 + and Fe 3 + in iron
oxides, or AI3+ and Si 4 + in silicates), and the phenomenon can be understood
structurally by considering crystal defects of various sorts. Although some types
of defects do not appreciably alter the chemical composition or ratios of various
crystallographic sites, other types do, most notably point defects and some types
of planar defects. Crystal defects and their effects on mineral stoichiometry and
other properties have been reviewed by Wadsley (1964), Greenwood (1970),
Hannay (1973), Kroger (1974), Lasaga (1980), Schmalzried (1981), Tilley (1987),
Serenson (1981), Schock (t 985), and Veblen (1991). The structures of defects and
methods of observing them are also described in Chapter 3.7, this Volume.
The structural classification of non stoichiometry varies somewhat from
author to author, but most classification schemes follow that of Wads ley (1964),
who noted five major categories. Substitution involves the replacement of a
nonmetal atom by a metal atom or vice versa, leading to a structural formula
such as B(BxX 1 - x), where B = metal, X = nonmetal. This mechanism is not to
be confused with substitution of one cation for another (or an anion for an
anion) within the same crystallographic site, which gives chemical formulae of
the type (AxBl-x)X, The latter means of incorporating "impurity" atoms is the
basis for normal solid solution in minerals and will not be considered further
here. Interpolation imolves the incorporation of interstitial atoms in normally
vacant sites, and Wadsley noted that it can take place in sites arranged in
isolated cages, linear tunnels, or sheets. Subtraction entails the omission of atoms
from normally occupied sites, thus forming vacancies. Subtraction can involve
metal atoms, nonmetal atoms, or both. Crystallographic shear involves collapse
or dilation of the structure across a planar boundary, relative to the ideal,
stoichiometric crystal. The chemistry in the region of the shear plane differs from
that of the ideal structure, thus causing nonstoichiometry when a nonperiodic
array of shear planes is present. Intergrowth nonstoichiometry occurs when
slabs with different structures and compositions intergrow with each other in
a disordered sequence. It is now known that other types of planar defects
(chemical twins) and unusual planar intergrowths known as vernier structures
also can accommodate nonstoichiometry.
The above types of nonstoichiometry can be separated into two broad
categories: (1) nonstoichiometry resulting from point defects, and (2) non-
199
stoichiometry resulting from planar defects. In the present treatment, we will

explore these two classes through a series of mineralogical examples that
illustrate the various subcategories. Note, however, that non stoichiometry in a
given compound can result from a combination of several different types of
point defects (Tilley 1987), or even from a combination of point and planar
defects. Indeed, the same basic structure type can exhibit substantially different
defect structures in different portions of its compositional range. Thus, classification of a mineral in a specific category should not be construed to mean that its
nonstoichiometry is related to only one type of defect. The degree of nonstoichiometry also depends on the history of the sample: temperature of
equilibration, oxygen fugacity, and cooling rate, for example.
A final complication results from ordering of the defects that cause nonstoichiometry. Either point or planar defects can interact and organize themselves into periodic arrays. If the resulting structure is truly ordered, then it must
be considered as a distinct, stoichiometric compound. Thus, it is possible for a
disordered, nonstoichiometric compound at high temperatures to be replaced
by a series of stoichiometric derivative structures at lower temperatures.
Experimental Methods for Investigating Nonstoichiometry

In some cases, nonstoichiometry in mineral systems has been examined in
natural samples. It is more common, however, to use synthetic materials, in order
to determine how sample chemistry, pressure, temperature, and the activities of
components such as oxygen influence the nonstoichiometry. In the discussions
that follow, therefore, reference will be made not only to work with natural
minerals, but also to studies of synthetic minerals and analog systems.
A wide array of experimental approaches has been used to elucidate the
limits of nonstoichiometry in minerals, the defects that lead to the compositional
deviations, and the effects of nonstoichiometry on mineral properties. Refinement of X-ray and neutron diffraction data provides average structural data,
and other methods, such as Patterson synthesis (Angel and Prewitt 1987), can be
used to characterize modulated structures that can result from nonrandom
distributions of defects. Diffuse scattering of X-rays, neutrons, or electrons
provides information on distributions of point defects and the structures of
defect clusters, especially when coupled with simulations and optical diffraction
studies of alternative defect structures (WeI berry and Withers 1990). Highresolution transmission electron microscopy (HRTEM) has been used to image
modulations resulting from ordering of point defects (see Chap. 3.2). Transmission electron microscopy also provides the primary means for studying the
arrangements and structures of planar defects that result in non stoichiometry.
A variety of spectroscopic methods have been employed to study structures
of point defects and to quantify the effects of defects on optical and other
properties. M6ssbauer spectroscopy has played a role in unraveling the defect
200
chemistry of nonstoichiometric oxides of iron and other metals, and IR spectroscopy has revealed the extent and structural nature of nonstoichiometric
hydrogen incorporation in a wide range of nominally anhydrous minerals
(Rossman 1988; Skogby et al. 1990). Similarly, the interest in Fe oxides for
recording and memory media and paleomagnetic studies has led to numerous
investigations relating nonstoichiometry to magnetic properties.
The transport properties of many minerals depend critically on the degree
of nonstoichiometry, particularly when it results from point defects. There have
therefore been numerous studies that relate nonstoichiometry to electrical
conductivity, ionic conductivity, chemical diffusion rates, and other properties.
In turn, diffusion and other transport properties can, in some cases, be used to
understand aspects of the defect structure, for example, whether or not different
types of point defects are bound to each other in the crystal or are dissociated
(Schmalzried 1981).
The most common analytical method employed by petrologists is electron
microprobe analysis, and assuming that adequate standards and correction
procedures are used, microprobe analyses can be used to detect major deviations from stoichiometry. However, accurate analysis for oxygen and lighter
elements was not possible until recently and is still a specialized procedure.
Coupled with the inability to determine valence, this lack of an oxygen analysis
makes it impossible to determine the degree of nonstoichiometry or a reliable
structural formula for many minerals containing elements with mixed valence
states, such as Fe. Furthermore, many minerals can contain substantial amounts
of elements such as Li, Be, B, C, and N. Failure to use analytical methods that
can measure all possible elements thus can result in an incorrect assessment of
the degree of nonstoichiometry. In the ideal case, oxidation states will also be
determined directly, in order to obtain an accurate structural formula.
Nonstoichiometry Resulting from Point Defects

The simplest types of point defects that cause variations in mineral stoichiometry are vacancies (missing atoms in normally occupied crystallographic sites)
and interstitials ("extra" atoms that occur at normally vacant positions in the
structure). Vacancies and interstitials can involve either cations or anions.
Cation Vacancies
Some of most commonly recognized nonstoichiometric minerals owe their
deviations from stoichiometry to high concentrations of cation vacancies, as
illustrated by the following examples. Several of these examples also demonstrate that a simple classification scheme for nonstoichiometry can be somewhat misleading, because many non stoichiometric compounds contain several
types of defects, including both vacancies and interstitial atoms. Furthermore,
201
the defects on a given site may be vacancies for one structure but interstitials
relative to another, closely related structure (as in the case of the amphibole
A-site).
Pyrrhotite. The chemical formula commonly given for pyrrhotite, Fe 1 - x S,
reveals this common sulfide mineral to be nonstoichiometric. In fact, the name

pyrrhotite encompasses a relatively large number of stoichiometric, ordered
structures between FeS and Fe 7 Ss , as well as truly nonstoichiometric and
disordered or incommensurate structures. At high temperatures, pyrrhotites
possess the NiAs structure, and the nonstoichiometry is accommodated by Fe
vacancies that are disordered over all the Fe sites of the structure (Kissin and
Scott, 1982). At lower temperatures, the vacancies order. The equilibrium
polymorph of Fe 7 Ss , for example, is based on the NiAs structure but contains
layers with 1/4 of the Fe positions vacant, alternating with completely filled Fe
layers (Bertaut 1953; Fleet 1971). As shown in Fig. 40, the Fe vacancies also are
ordered within the layers. Other compositions of pyrrhotite possess related
structures exhibiting a variety of sequences of vacancy-rich and filled layers and
different ordering patterns of the vacancies within the layers, leading to a series
of superstructures in both the a and c directions and a variety of symmetries
(Morimoto et al. 1975a, b).
HRTEM investigations of pyrrhotite (Pierce and Buseck 1974; Nakazawa
et al. 1975; D6dony and P6sfai 1990) have revealed the importance of extended
Fig. 40. The arrangement of metal vacancies

(squares) and filled Fe sites (filled circles) in 4C
pyrrhotite. Only the Fe layers are shown for
simplicity. Layers with vacant sites alternate with
filled layers. (Nakazawa et al. 1975, after Bertaut,
1953)
202
defects, such as twinning and antiphase boundaries. Pyrrhotites with integral

superstructures may be described as having regular arrays of such defects,
whereas incommensurate pyrrhotites have disordered arrays of antiphase
boundaries. Mossbauer spectroscopy also has been used to examine the local
structure and environment of Fe sites in pyrrhotite (Kruse 1990). Although
pyrrhotites have generally been assumed to be binary phases in the system Fe-S,
there are indications that oxygen may also play an important structural role,
possibly displacing phase boundaries for natural pyrrhotites from their ideal
positions (Graham 1987).
Spinel Structures and Hematite. Numerous materials that crystallize with the
spinel structure exhibit deviations from the ideal stoichiometry A2+ B ~ + 4,
yielding formulae of the type DX/3Ai~xB~~2x/304' where A and B refer to
tetrahedral and octahedral sites respectively. Here we consider two important
cases, spinel proper (Mg-Al) and defect Fe-rich spinels, which have been studied
extensively as ceramic and magnetic materials and are important for rock
magnetism. In the Mg-AI-O system, Viertel and Seifert (1979) synthesized and
characterized physical properties of a large number of spinels ranging from
stoichiometric MgAl204 to the defect spinel y-AI 20 3, or AI 2.67 0 4, which is an
important catalyst support material. This alumina material, which is commonly
synthesized by dehydroxylation of Al hydroxides, can occur with either disordered or ordered vacancies. The structural chemistry of intermediate compositions is very complex, with cation vacancies potentially occurring on both
types of sites, variations in Mg and Al occupancies, and, in some cases,
interstitial cations as well; the exact defect structure depends not only on
composition, but also on the precise synthesis route and conditions of equilibration (Moroz et al. 1987). The details of the non stoichiometry are important,
because they can influence the mechanical properties of Mg-AI-O ceramics
(Chiang and Kingery 1989).
Because of their importance as carriers of rock magnetism and in magnetic
recording media, the defect structures of magnetite, Fe 30 4, the defect spinel
maghemite, y-Fe203' their compositional intermediates, and titanium-substituted variants have been examined extensively by X-ray, electron, and neutron
diffraction (Fleet 1982; Greaves 1983; Boudeulle et al. 1983), as well as by
Mossbauer spectroscopy (Weber and Hafner 1971; Collyer et al. 1988) and by
measurement of electrical and magnetic properties (O'Reilly 1983; Wu and
Mason 1981). The defect structures and their relationship to physical properties
are reviewed by Gleitzer and Goodenough (1985), and Lindsley (1976) reviewed
the departures from stoichiometry that occur in the magnetite-ulvospinel series
(ideally Fe30cFe2 Ti0 4).
Fe-rich spinels, like their Mg-AI-O counterparts, possess a range of defect
structures involving both vacancies and interstitial atoms. Even nominally
stoichiometric magnetite at room temperature has interstitial Fe atoms that
form defect clusters with surrounding vacancies. The interstitials and vacancies
can occur in both octahedral and tetrahedral sites; octahedral vacancies as high
203
as 7% have been reported (Fleet 1982). The defect structure is annealed out at
high temperatures, where stoichiometric magnetite approaches the ideal inverse
spinel structure (Fleet 1984). In maghemite, the vacancies appear to be predominantly on the octahedral sites and can order, leading to a reduction from cubic
to tetragonal symmetry (Smith 1979; Greaves 1983). Collyer et al. (1988) showed
that the vacancies in titanomaghemite also occur on the octahedral sites
and discussed the structural formula of this nonstoichiometric oxide. As in
Mg-AI-O spinels, the exact defect structure of Fe 3- x0 4 and titanomaghemites
that accommodates the non stoichiometry is strongly dependent on the conditions and mechanisms by which the material formed (O'Reilly 1983). Most, ifnot
all, maghemites also contain hydrogen, but its precise structural role and
whether H is an essential component have not been resolved.
The iron hydroxide goethite, nominally IX-FeOOH, always contains excess
water, presumably in the form of interstitial H 20 molecules. During dehydroxylation, the goethite framework collapses to a nonstoichiometric hematitelike structure, Fe2-x/3(OH)x03-x, with x approximately equal to 1 (Wolska and
Schwertmann 1989). Upon further dehydroxylation, another transitional, hematite-like phase appears at x ~ 0.5, before finally being replaced by a true
hematite structure that is still hydrogen-bearing and non stoichiometric.
Wustite and M agnesiowustite. Wiistite is important both for materials science (it
is a major component of the oxide scale that forms on iron alloys) and earth
science (magnesiowiistite is thought to be an important lower-mantle phase).
The defect chemistry of wiistite is very complex and has been covered by several
reviews (Hazen and leanloz 1984; Gleitzer and Goodenough 1985; Mrowec and
Podg6recka 1987). Although wiistite is here classified in the section on cation
vacancies, interstitial defects play an equally essential role in the defect chemistry and nonstoichiometry. The chemical formula is commonly written Fe1-xO,
but it should more properly be given as VI[Fei '::3xFe~:_t D x+t] IVFe~ +0, where
VI and IV indicate octahedral and tetrahedral coordination, to emphasize the
nature of the defect chemistry (Hazen and leanloz 1984). Ideal, stoichiometric
FeO possesses the NaCI structure, and since the early work of Roth (1960),
numerous diffraction and spectroscopic studies have confirmed that the primary
cause of nonstoichiometry in wiistites is a defect cluster in which a Fe 3+ ion
occupies a normally vacant tetrahedral site in the FCC oxygen framework. The
occupied tetrahedral site is surrounded by four vacant octahedral sites in a
tetrahedral arrangement. These 4/1 clusters can order to form larger clusters,
as shown in Fig. 41. The magnetite structure contains 4/1 clusters that share
corners, but the predominant defect types in wiistite involve 4/1 clusters that
share faces and edges.
In addition to diffraction studies, there have been numerous investigations of
the physical properties of wiistite and magnesiowiistite. The precise defect
structure and physical properties strongly depend on the method of synthesis
and history of the sample (Hazen and leanloz 1984). It is not yet clear whether
diffusion in wiistite occurs by the movement of nondissociated defect clusters or
204
14/11 =
Type 1
Type 2
17/21
116/51
~17/21
Type 3
@16/21
.
fHj

19141
~113/81
@ """ ti1Y
Fig.41. Defect clusters in wiistite. At the top right is shown an isolated cluster, which consists
of an interstitial Fe 3 + atom (triangle) surrounded by a tetrahedron of octahedral vacancies. In
the remaining diagrams, these clusters are represented by cubes in which the interstitial atom is
shown as afWed circle. The clusters may be linked by corners (Type 1), as in magnetite, but
face-sharing (Type 3) clusters apparently are the most common, followed by edge-sharing
clusters (Type 2). The symbols are derived from the ratios of vacancies to interstitials in the
cluster. (Hazen and leanloz 1984)
by the migration of free vacancies dissociated from the clusters (Mrowec and
Podg6recka 1987).
Chain Silicates. Pyroxenes (single-chain silicates) commonly possess the ideal
stoichiometry (M2)(Ml)T 2 0 6 , but some synthetic high-pressure pyroxenes
deviate substantially from this formula, with up to 10% octahedral vacancies
apparently occurring on the M2 site (Wood and Henderson 1978). Large
octahedral vacancy components are also reported for mantle omphacites from
kimberlites. Crystal structure refinement and chemical analyses suggest that
the nonstoichiometry results from incorporation of a Ca-Eskola component,
Ca o.s D o.s AlSi 2 0 6 , and confirm that the vacancies are on M2 (McCormick
1986).
Although the nonstoichiometry is commonly masked by writing their
formulae as end members, natural amphiboles are almost invariably nonstoichiometric with respect to their A-site occupancies (Robinson et al. 1982;
Hawthorne 1983). The occupancy of the A-site can vary from 0 to 1, but it is
generally between these values. Hornblendes, for example, exhibit a wide range
of occupancies. Nominally A-site-empty amphiboles such as anthophyllite and
205
actinolite commonly show at least small A-site occupancies, whereas nominally

A-site full species seldom attain occupancies of exactly 1. This amphibole
non stoichiometry is implicitly recognized in the approved nomenclature (Leake
1978), which allows individual amphibole names to correspond to wide variations in A-site occupancy. Combined with the other chemical degrees of
freedom inherent in the amphibole structures, the A-site nonstoichiometry
makes it very difficult to obtain a unique and reliable structural formula from
chemical analyses, leading to numerous schemes for recalculating amphibole
analytical data (Robinson et al. 1982; Hawthorne 1983). Relative to an A-sitefull end member, the nonstoichiometry can be considered to result from cation
vacancies. (Of course, relative to an A-si~e-empty end member, the A-site
occupants would be considered as interstitial atoms.) The nonstoichiometry of
amphiboles, like many other silicates, is related to often complex coupled
substitutions involving several crystallographic sites. As a historical note, the
importance of large numbers of vacancies in a crystal structure was probably
first demonstrated for the case of amphiboles by Warren (1930).
Sheet Silicates. Like the rock-forming amphiboles, many sheet silicates are
almost invariably nonstoichiometric, but with both partially filled interlayer
sites (analogous to the amphibole A-site) and nonintegrally filled octahedral
sites. In addition, many sheet silicates are prone to non stoichiometry resulting
from mixed-layering defects, as discussed below. Most 2: 1 sheet silicates
(e.g., micas, illite, smectites, talc) are apparently seldom, if ever, truly stoichiometric, although it is extremely difficult to determine accurately the degree of
nonstoichiometry, due to the problems of renormalizing analyses and in finding
suitable crystals for single-crystal diffraction studies. Due to chemical substitutions that commonly involve all of the metal sites, the interlayer sites are almost
invariably only partially occupied (Foster 1960; Guidotti 1984). Based on
hundreds of analyses from the literature, Guidotti (1984) indicated that interlayer occupancies are generally 0.90 to 0.96 in muscovite and also deviate from 1
in biotite, although analytical ambiguities prohibit accurate determinations of
vacancy concentrations and H 30 + may occupy some of the apparent vacancies.
The nonstoichiometry varies with rock type and conditions of equilibration
(Wang and Banno 1987). Muscovite, which is nominally dioctahedral, typically
shows octahedral occupancies ranging from 2.01 to 2.05, rather than the
stoichiometric ideal of 2; there are thus 1 to 5% interstitial cations in the
nominally vacant octahedral sites. Similarly, octahedral occupancies in biotites
(nominally trioctahedral) generally range from 2.80 to 2.95, indicating approximately 2 to 7% vacancies. The sodium trioctahedral mica wonesite is highly
nonstoichiometric, with interlayer occupancy close to 0.5 (Spear et al. 1981;
Veblen 1983a). Pyrophyllite octahedral occupancies vary between 1.95 and 2.05,
and those of talc can show minor deviations from the ideal occupancy of 3.0.
Na, K, and Ca in talc and pyrophyllite may be accommodated as interlayer interstitials, or as planar defects (Evans and Guggenheim 1988, and see
below).
206
Illites and smectites, which are important 2: 1 clay minerals, are by definition
nonstoichiometric, with much larger proportions of vacancies in the interlayer
sites. Illites commonly show interlayer occupancies of about 0.75 (Srodon and
Eberl 1984), while smectites exhibit wide variations with interlayer occupancies
as low as about 0.25. The interlayer cations in smectites are exchangeable, and
smectite interlayers can swell, as described in the section on interstitial cations
and molecules.
Framework Silicates and Silica Minerals. Substitutions of the type (K, Na, Li,
1/2Ca, etc.) AI ...... D Si can produce substantial deviations from stoichiometry in

framework silicates and silica minerals (Veblen 1985a). Feldspars can show
substantial deficiencies in alkali cations or Ca, attributable to solid solution
involving a component such as D Si 4 0 8 (Smith and Brown 1988). Anorthite can
form solid solutions with Si0 2 attaining up to 11 % vacancies on the Ca sites
under some conditions (Ito 1976; Longhi and Hays 1979), as can the alkali
feldspars. Diffusion studies suggest that, when small in number, the defects
responsible for feldspar nonstoichiometry are largely dissociated at high temperatures (Behrens et ai. 1990).
The feldspathoid leucite and stuffed derivatives of tridymite and cristobalite,
such as nepheline, can show a marked deficiency ( > 10%) in alkali cations and
excess Si, due to a coupled incorporation of vacancies and Si replacing AI, as in
feldspars (Deer et ai. 1963; Edgar 1984; Rossi et ai. 1989). The reverse substitution (i.e., interstitial alkali cations coupled with substitution of Al for Si) can
occur in the silica minerals with open frameworks, and analyses of naturally
occurring terrestrial tridymite and cristobalite invariably show substantial
alkali ions and AI.
Cation and Molecular Interstitials
In the previous section, it was noted that a number of mineral groups that show
major deviations from stoichiometry due to cation vacancies also exhibit
important deviations due to interstitial defects (e.g., magnetite, wiistite, some
sheet silicates, silica polymorphs). Here we explore additional examples, where
cation or molecular interstitials form the major contribution to the nonstoichiometry.
Manganese Oxides. As described by Wadsley (1964), some of the tunnel manganese oxides and phyllomanganates are interstitial nonstoichiometric compounds based on interpolation of cations in columns and sheets. Structurally,
the best-understood of these minerals belong to the hollandite group, with the
idealized structural formula Ao _ 2(Mn 4 + ,Mn3+ )8016 and tunnel structures
similar to that shown in Fig. 42. If all the Mn were tetravalent, the tunnels would
be vacant, but the natural structures contain substantial interstitial tunnel
cations: ideally A = Ba2+ in hollandite, Pb2+ in coronadite, K + in cryptomel-
<
207
Fig. 42. The hollandite structure viewed

parallel to the tunnels. Double chains of
edge-sharing Mn0 6 octahedra surround
the interstitial tunnel site (large filled circle),
which can be occupied by variable amounts
of cations. The occupancy of the tunnel
sites depends on the Mn oxidation state.
(Post and Bish 1989)
ane, and Na + in manjiroite, although the A site generally contains a mixture of

several different cations. The mineral priderite, (K,Ba)o_2(Ti 4 +,Fe3+)s016, is
isostructural with the hollandite group. Crystal structure refinements (Post et al.
1982; Post and Bish 1989) confirm the partial occupancies of the interstitial sites
and indicate a variety of displacements and large apparent thermal motions for
the tunnel cations, indicative of a high degree of positional disorder. In addition,
diffraction studies suggest that the interstitial tunnel cations and vacant sites are
ordered in individual tunnels, but the occupancy patterns are disordered from
tunnel to tunnel. Other Mn-oxide tunnel structures, such as romanechite and
todorokite, exhibit similar crystal chemical variations. In addition, many tunnel
manganese oxides possess structural disorder based on planar defects (Turner
and Buseck 1979).
The phyllomanganates, such as chalcophanite and birnessite, contain sheets
of edge-sharing Mn0 6 octahedra similar to the Mg hydroxide sheets found in
brucite (Post and Appleman 1988; Post and Veblen 1990). Variable numbers of
interstitial cations such as Zn, Na, Mg, and K can reside in various positions
between the sheets and can, in some cases, exhibit rapid ion exchange at room
temperature. Interstitial water molecules also are found between the sheets,
which collapse in some birnessites when the water is removed under highvacuum conditions.
Smectites and Zeolites. As noted in the section on cation vacancies, clay

minerals of the smectite group consist of 2: 1 silicate layers exhibiting nonstoichiometry with respect to interlayer and octahedral cations. Smectites also
can take up variable amounts of interstitial H 20 and other molecules between
the layers, causing the structure to swell normal to the layers. For example,
under vacuum or very dry conditions, the interlayer spacing is about 1.0 nm, but
at increasing humidities the structure swells to about 1.2 nm with a single layer
of interlayer H 2 0, then 1.4 nm with a double water layer. Interpolation with
various organic molecules can produce other spacings (e.g., 1.7 nm with ethylene
glycol). Similarly, vermiculites can have highly variable amounts of water and
various cations between their 2: 1 layers.
208
Zeolites possess very open alumino silicate frameworks and can possess
cation-vacancy non stoichiometry analogous to that exhibited by feldspars. In
addition, zeolites with interconnected tunnel structures can absorb variable
amounts of interstitial water, commonly referred to as "zeolitic water," and are
hence generally nonstoichiometric with respect to H 20. Similarly, many zeolites
can absorb other molecular species that can fit through the apertures of their
tunnels. This interstitial nonstoichiometric behavior of swelling clays and
zeolites gives them a number of industrially useful chemical properties, such as
catalytic activity (Barrer 1978).
Anion Vacancies
Mullite. Mullite, AI2(AI2+2xSi2-2x)01O-x Ox, is an important nonstoichiometric ceramic material in which the deviation from stoichiometry results
primarily from oxygen vacancies. Crystal structure refinements of the average
structure (Angel and Prewitt 1986; Burnham 1964), which is similar to that of
sillimanite, demonstrate that the oxygen vacancies occur on the Oc sites and that
cations adjacent to the vacancies are displaced, as shown in Fig. 43. Between
about 12.5% and 20% of the Oc sites are vacant, depending on composition.
The oxygen vacancies and related displaced cations order to form an incommensurate modulated structure, which greatly complicates determination of the
detailed structure of mullite.
A variety of experimental methods have been used to understand the
structure ofmullite. Angel and Prewitt (1987) used Patterson functions construc-
Fig. 43. A schematic diagram of the

mullite structure. In sillimanite,
A1 2Si0 5 , all of the Oc oxygen sites
and T tetrahedral sites are filled. In
mullite, AI2(AI2+2xSi2-2x)01o-x DX'
vacancies occur on some of the 0.
sites. The adjacent T site is then also
vacant, the alternative tetrahedral
site T* is instead occupied, and the
occupied Oc site belonging to that
T* site is shifted to the alternative
site 0c* (indicated on the diagram by
c*). (Welberry and Withers 1990)
209
ted from satellite intensities of a mullite with x = 0.40 to show that the
modulation results from two ordering patterns, one of occupied and vacant Oc
sites and the other of tetrahedral Al and Si. Their results are consistent with the
theoretical considerations of McConnell and Heine (1985). The modulated
structure and associated microstructures at different compositions have been
imaged with HRTEM, and computer simulations have been used to interpret
the images (Nakajima and Ribbe 1981; Schryvers et al. 1988; Rahman and
Weichert 1990). Wei berry and Withers (1990) used a novel approach in which
they obtained optical diffraction patterns from masks prepared by Monte Carlo
generation of defect structures. They compared these patterns with X-ray diffuse
scattering observed with a position-sensitive detector system. The diffuse
scattering favors a model in which each Oc atom is bonded to only three, rather
than four, tetrahedral cations. Mullite is thus a good example of how new
diffraction, imaging, and theoretical methods can work together in the development of structural models for incommensurate nonstoichiometric materials.
Perovskite Structures and their Derivatives. Synthetic mixed oxides with the
perovskite structure are commonly nonstoichiometric as a result of planar
defects (discussed below), oxygen point defects, or both; the equilibria of defects
in oxygen-deficient perovskites have been reviewed by Smyth (1989). Depending
on their concentration, oxygen vacancies may be isolated, ordered into linear
arrays, arranged in microdomains of ordered rows, or ordered into defect planes
which can themselves occur in either ordered or disordered sequences (Grenier
et al. 1981; Gonzalez-Calbet et al. 1987). Vacancies in the oxygen sites can result
in unusual four- and five-fold coordination polyhedra for the cations, and there
are numerous structures based on different arrangements of these polyhedra and
the normal perovskite polyhedra (Reller et al. 1984).
The new high-temperature ceramic superconducting materials are nonstoichiometric, perovskite-derivative layer structures, such as YBa Z Cu 3 0 7 - 0 In
some of these structures, the superconducting properties depend critically on the
number of oxygen vacancies (15), which is coupled with the valence of Cu.
Nonstoichiometry in these oxide superconductors is reviewed by Raveau et al.
(1990).
Anion Interstitials
Fluorite Structures. The fluorite structure can be described as a simple-cubic

arrangement of anions, with half the resulting cubic coordination polyhedra
filled with anions. Fluorite structures such as uraninite, DO z , can accommodate large degrees of anion-excess nonstoichiometry based primarily on interstitial anions on the unoccupied cubic sites of the ideal, stoichiometric structure,
whereas other fluorite structures exhibit anion deficits. The relationships between the non stoichiometry and physical and chemical properties have been
investigated in detail for actinide oxides, AcO z .. primarily because of the
210
importance of some of these oxides as nuclear fuels. Pa and U form oxygenexcess structures, whereas the actinide and lanthanide oxides of Pu, Am, Cm,
Bk, Cf, Pr, Ce, and Tb exhibit oxygen deficits. The structural basis for the
nonstoichiometry has been reviewed by Manes and Benedict (1985).
At temperatures above 1100 c, uranium oxide can take on any composition
between UO z and approximately UO Z . Z5 ' and the non stoichiometry is compensated by oxidation of U 4 + to either U 5 + or, less likely, U 6 +. Oxygen interstitial
defects are accompanied by oxygen vacancies to form defect clusters of at least
two types, sometimes called Willis clusters. Recent neutron diffraction results
(M urray and Willis 1990) confirm that the oxygen interstitials are displaced
from the center of the cubic site to two other sites, 0' and 0". Two 0' and two
0" interstitials can combine with two oxygen vacancies to form the so-called
2: 2: 2 cluster, or the more complex U 6 0 37 or cuboctahedral cluster can form, as
shown in Fig. 44. Similar clusters also form in other anion-excess fluorite
structures, such as (Ca 1 - xYx)F2+x'
It is generally agreed that the nonstoichiometry in the ABz-x fluorite
structures results primarily from anion vacancies (Manes and Benedict 1985).
The vacancies apparently cluster, although there have not been direct structural
observations to characterize the cluster structures as well as has been done for
the anion-excess clusters. Some anion-deficient fluorite structures order to form
superstructures (Wallenberg et al. 1989). Some other nonstoichiometric fluorites
form derivative vernier structures (Makovicky and Hyde 1981), which are
discussed below in relation to sulphosalts.
0
0
0
0
0
_Go
0
0
0
Fig. 44. The complex cuboctahedral

defect cluster in V0 2 +x' The symbols are as follows: (0) normal oxygens at z = 1/4; (e) uranium at z
= 0; () oxygen interstitials at z
= 0; (EEl) oxygen interstitials at z
= 1/4. (Murray and Willis 1990)
211
Nonstoichiometry Resulting from Extended Defects

Extended defects include dislocations (linear defects) and two-dimensional
defects (commonly called planar, although they may form surfaces with complex
morphology). Many extended defects, such as dislocations, stacking faults,
antiphase boundaries, and isolated twin boundaries typically do not have major
effects on the crystal stoichiometry.
Other classes of planar defects, however, can alter both the crystal structure
and chemical composition of a mineral drastically. Solid-state chemists recognize several classes of such defects (Hyde et al. 1974; Tilley 1987), including
(1) crystallographic shear planes (or Wadsley defects), which possess fault
vectors that cannot be described as being parallel to the fault plane; (2) chemical
twins, in which the material at the twin plane possesses a different structure and
chemistry from that of the untwinned material; and (3) intergrowth structures,
in which a slab of a new material is introduced into the structure. A series
of structures that form by repeated shearing, twinning, or intergrowth with
different periodicities has been called a homologous series (MagneIi 1953).
All of these defects can be described alternatively with the formalism called
polysomatism (Thompson, 1978; Ferraris et al. 1986; Veblen 1991). Polysomes
are structures that can be sliced into at least two different types of structurally
and chemically distinct slabs, and a polysomatic series is a group of stoichiometrically collinear compounds that can all be constructed from the same slabs.
Deviations from a perfectly periodic sequence of the slabs result in nonstoichiometric members of the series. Although any of the alternative descriptions of poly somatic structures is equally valid, in this section we use this
unifying way of viewing non stoichiometry based on extended defects. Polysomatic disorder in minerals and its compositional effects have been reviewed by
Veblen (1991).
Silicates and Phosphates
Biopyriboles. To mineralogists, the best known polysomatic series is probably

the biopyribole chain and sheet silicate group (Thompson 1978; Veblen 1981),
which can also be represented as a crystallographic shear system (Chisholm
1975). The biopyriboles illustrate many of the principles of other polysomatic
structural series. All the biopyribole structures can be cut parallel to (0 10) into
slabs of pyroxene or mica structure, called P and M slabs. P slabs can be
assembled alone to form the single-chain pyroxene structures (P), and M slabs
will form micas or talc (M), which are sheet silicates. When P and M slabs are
combined so that they alternate in a 1: 1 ratio, the double-chain amphiboles are
formed (MP), whereas a 2: 1 ratio of mica to pyroxene in the sequence (MMP)
produces jimthompsonite or clinojimthompsonite, which have triple silicate chains
(Fig. 45).
212

I
I
I
I
I
I
I
I
I
I
I
I
I
,I
I
I
I
I
I
I
I
B~.B
I
I
I
I
I,
I,
I
,.
I
I
I
I
I
I
I
Pra :
Mica
Pya
Mica
Pya:
I
I
I
Mica
: Pya
Pya
Mica
Mica
Pya
Mica
MiCO
Pya
Mico
Mir.o
Pya:
b
Fig. 45a, b. Clinoamphibole (a) and the triple-chain silicate clinojimthompsonite (b), showing
that these structures are comprised of (010) mica and pyroxene slabs in the sequences (MP)
and (MMP). (Thompson 1978; Veblen 1981)
Because they are constructed from exact ratios of two different components,
pyroxenes, amphiboles, jimthompsonite, and micas are all stoichiometric minerals (assuming the ideal case of no nonstoichiometry resulting from point defects).
It is possible, however, to combine the polysomatic slabs in a disordered fashion,
which produces a nonstoichiometric crystal with a chemical composition that
lies between those of two ordered members of the series. Although poly somatic
disorder of this sort can be difficult to recognize with many experimental
methods, it is readily observed using HRTEM: Fig. 46 shows an example of a
crystal that is predominantly the amphibole anthophyllite (double silicate
chains), but with defects corresponding to triple chains (the isolated sequence
MMP), quadruple chains (a defect with structure MMMP), and sextuple chains
-- --_
......
- ...... ---- .
.:.=
:-=""=
.
:
.
:
.
:
.
:
.
:
-:
-:
...
:
.:
.
:-:.:.:
.':-:"':.:'.:":.:.,
....: ..... : . : . . :-: -:. :.: -:-:-:-:-:.:.: . . :.: ..: ..:.:.:.
........ -
213
:-=. . :. . :.:-: . :. :-:-:-;-:. :-:-:.:-:--:.:-:

. :-:.:-:
......... .
.:, ~
.. :--:-=-: .. :.. :-: . . : . . : .. : .....":.: ... :-:-:.:.:.: ..: ..:-:..:-:.

....=.:-: -: -:- :-:
--: ......
. :-:
-. :-=
.. ....: .. :-:-:-:-:-:.:~:-:-:.:-=-',
-::-=~:~:.:
...=-. =.-.. :-:-:
-:
.
:~::"'::-:::"':...:..:-X-.:.. ~
. . :-:.:
........ :-:.. :.:-:.:.:-:
: ...
"
.... .. :... : ~~
.. .. ..--.
....:.:-......
..........
- ........-.., ....-.. - _.............
--.
..- .....- .. - .....-.-......
-
.. X .
:-:
:-.:.:-:-:-:-:-:
...:;:.:-:-:-.:-:.:-:-:.
..:-:..:-. .
.... ..............
..................
_.......................
-_
.
.
.
.
.
.
.
.
.
.
.
...... -- ....... -.. ~ .~ -...... ~--.~~
.....-,
..
.. ....
...
-..
....
-.. .. . ..... ............ .:
:.:-...::::..:.:-:
...... - -
~--.--.-
~-
-.-- ..:-:...
.. ..:........:-:---.:.....:-::......
. -.--,
:.:.
~
........
. . . . . . . . . . .
:-::~:
:.:.:.:~ ,
--.
..
......
.....
....
~-
...
-~'\'--"
.. -
-~......':"""'-.~'--,
~:
,,~
:.:-:.:.:.:-.
......
.-_~.~~...
:s.~~
... ...a. . . . . . . . _....
131
. . . . . . . . . . . . ...0-. . . . . . .
~:.:.:.:-:.:.:.:.:~~~:~ ~
:-.........
:=: ..: ....-:.:.
_~~~~.. _w.......
.... ....-. ..-.. - ,. .. . ... -_..........
__
. _ ___ ~ . . . ." . - _. . .~,~"
...... - ... .......
~~
Fig. 46. A c-axis HRTEM image of a nonstoichiometric crystal that is predominantly the
amphibole anthophyllite. The defects that cause the nonstoichiometry consist of slabs with
triple chains (3). quadruple chains (4). and sextuple chains (6). (Veblen 1981)
(the defect MMMMMP). These defects make the crystal nonstoichiometric,

displacing its composition off that of ideal anthophyllite and toward talc.
The degree of polysomatic disorder, and hence nonstoichiometry, is highly
variable, depending on both chemistry and geological history. Most, if not all,
amphibole compositions can occur with a high degree of structural order.
However, all amphiboles and wider-chained pyriboles that have been investigated in detail possess major disorder of this type in at least some occurrences.
These include ferromagnesian amphiboles such as anthophyllite and cummingtonite (Veblen and Buseck 1979; Maresch and Czank 1988), calcic amphiboles of the actinolite and hornblende series (Dorling and Zussman 1987; Ahn
et al. 1991), and the sodic amphibole riebeckite (Ala rio Franco et al. 1977). This
type of nonstoichiometry appears to be especially common in asbestiform
amphiboles, and it can occur in both natural occurrences and synthetics. In
addition, pyroxenes, especially those that have experienced hydrothermal alteration or weathering, can exhibit nonstoichiometry based on the polysomatic
intergrowth of double- and wider-chain material (Veblen and Buseck 1981).
Other Chain and Sheet Silicates. Several other polysomatic series occur in the
chain and sheet silicates, and disorder and resulting nonstoichiometry have been
observed in all of them (Veblen 1991). A partial list includes the following
groups. (1) Members of the pyroxenoid series, which can be represented as
intergrowths of pyroxene and wollastonite slabs parallel to {II I} of pyroxene,
commonly intergrow and show polysomatic defects (Czank and Liebau 1980;
Veblen 1985b). (2) The mixed-layer clays are polysomatic structures, and when
disordered they are nonstoichiometric (in addition to point-defect nonstoichiometry discussed above). In more coarsely crystalline sheet silicates, unit-cell-
214
scale intergrowth among the 1: 1,2: 1, and chlorite structures is common and
likewise results in nonstoichiometry (Thompson 1978; Veblen 1983b; Veblen
and Ferry 1983). (3) The antigorite structure can be represented as a polysomatic
series with three types of slabs. Especially in low-temperature occurrences, it
shows major structural disorder and hence nonstoichiometry (Livi and Veblen
1987; Mellini et al. 1987). (4) Carlosturanite is nonstoichiometric due to polysomatic disorder based on intergrowth of lizardite slabs and slabs of a hypothetical chain-silicate structure (Mellini et al. 1985).
Olivine and the Humite Group. Many olivine specimens do not show any planar
defects (White and Hyde 1982), but others can contain planar defects that cause
nonstoichiometry. Olivine and minerals of the humite group form a polysomatic
series, and intergrown slabs with humite structures can perturb the chemical
composition of olivines to less silica-rich compositions and also contain hydrogen (Kitamura et al. 1987). Similar polysomatic disorder leads to nonstoichiometry in the humite-group minerals (White and Hyde 1982). In laihunite, a
Fe H -rich derivative structure of fayalite, vacancies on Fe sites order to form
planar defects that accommodate the nonstoichiometry (Kitamura et al. 1984).
Similar defects also form during the natural oxidation of relatively magnesian
volcanic olivines (Banfield et al. 1990). Olivine also can possess significant
nonstoichiometry based on point defects (Jaoul et al. 1987), but the extent of the
compositional deviations is not well known.
Apatite. Both inorganically and organically precipitated apatites can show
major deficiencies in Ca, compared to the ideal stoichiometry Ca S (P04h(OH,F), with Ca/P molar ratios as low as 1.48 (Nelson and Barry 1989; Zawacki
et al. 1990). It is not known how much of this nonstoichiometry can be
attributed to point defects, but at least part of it results from planar defects.
Some of these defects, as well as the seeds for the growth of apatite crystals in
dental enamel, apparently have the octacalcium phosphate structure,
CaSHZ(P04)65HzO.
Oxides
Rutile. Numerous experimental studies have elucidated the complex structural
basis for the non stoichiometry in reduced, TiH -bearing rutiles, TiOz-X' as well
as in rutiles doped with other trivalent cations (Tilley 1980; Millot et al. 1987). At
high temperatures, the oxygen deficiency in slightly reduced rutile is accommodated by randomly distributed vacancies, but upon cooling the vacancies typically condense to form crystallographic shear planes, which can also be
described as polysomatic defects. These planar defects can take on numerous
structures, orientations, and degrees of ordering into periodic arrays as a
function of different compositions and thermal histories. In some cases (e.g.,
Cr z0 3 -doped rutiles), the shear planes can swing through various orientations,
215
and any composition can be accommodated; the term infinitely adaptive compounds has been used to describe such structures (Anderson 1973). For some
cooling rates, unit-cell scale features called platelet defects develop to accommodate the nonstoichiometry (Bursill et al. 1984). Most metamorphic rutiles
contain some Fe 3 + in solid solution, and upon cooling the nonstoichiometry
results in the formation of analogous Fe-rich platelets (Banfield and Veblen
1991). These platelet defects can be described as having a structure similar to
hematite and are typically only one or two unit cells thick.
Perovskite Structures and Other Derivatives of the Re03 Structure Type. The
concept of homologous series in solids was first developed by MagneIi (1953),
based on observations on W0 3 - x and Mo0 3 - x , which are crystallographic
shear structures derived from the Re0 3 structure type. The shear planes
can occur with different orientations, spacings, and in ordered and disordered
arrays (Tilley 1980). The perovskite structure, which is of critical importance in
geophysics and materials science, is a simple stuffed derivative of the Re0 3
structure. As noted above, perovskites can accommodate deviations from the
ideal AB0 3 stoichiometry with point defects, but many families of perovskite
derivative structures are based on planar defects and can also be described as
polysomatic series. Many of these structures are reviewed by Tilley (1980) and in
Navrotsky and Weidner (1989), and nonstoichiometry based on planar defects
in perovskite-derivative high-Tc superconductors was reviewed by Raveau et al.
(1990).
Sulfosalts
Homologous Series. Makovicky (1989) recognized about 20 different homologous series based on operations such as chemical twinning (Hyde et al. 1979),
antiphase boundary formation, and shear. Many of these structural groups can
also be described as polysomatic series. There is at least the potential for
nonstoichiometry based on planar defects in all of these structures, and such
disorder has been recognized in a number of cases. For example, structures of
the lillianite series contain chemical twin planes separated by slabs of galena
structure, and non stoichiometry can be attributed to defects involving mistakes
in the widths of these slabs (Tilley 1987). Similarly, chemical variations are
related to structural disorder in the bismuthinite-aikinite series (Pring and Hyde
1987).
Vernier Structures. Vernier structures, also called noncommensurate or misfit
layer structures, are based on the intergrowth of two different types oflayers that
have different periodicities. Such structures occur in many chemical systems
and have been reviewed extensively by Makovicky and Hyde (1981). The
"beating" between the two periodicities can result in very long-period superstructures, and variations in the chemical compositions (and exact dimensions)
216
of the two layers lead to variations in stoichiometry. Sulfosalt examples of

vernier structures include cylindrite, frankeite, and cannizzarite. HRTEM
and electron diffraction studies of these structures have helped to show how
structural variations and defects accommodate variable chemical compositions
(Williams and Hyde 1988a, b).
Summary
The above discussion indicates that nonstoichiometry is a very common
phenomenon in minerals, affecting most if not all of the important rock-forming
mineral groups. Substantial deviations from stoichiometry result primarily from
two phenomena: (1) the incorporation oflarge numbers of point defects into one
or more crystallographic sites in the mineral and (2) the presence of planar
defects, especially polysomatic defects, that possess a composition different from
that of the ideal mineral in which they are intergrown.
As more accurate data are complied on the detailed chemistry of rockforming minerals, these deviations from ideal stoichiometry have become more
apparent. Yet, it is commonly difficult to detect departures from ideal chemistry
by using chemical analysis alone, especially in materials with complex structural
formulae and containing multivalent elements such as Fe. For"such structures, it
is commonly possible to normalize an analysis so that the structural formula
appears to be reasonable but is nonetheless incorrect and masks the nonstoichiometric character of the mineral. In other cases, structurally "impossible"
analyses may be interpreted as resulting from analytical error and thus ignored,
when in fact they result from non stoichiometry. It is essential, therefore, that
mineralogists and petrologists who work with mineral chemistry be aware that
non stoichiometry resulting from crystal defects is common in at least some
minerals from virtually every structural group. It is also clear that full structural
understanding of the nonstoichiometry in minerals requires the application of a
wide array of experimental approaches.
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3.6 X-Ray Topographic Study of the Real Structure of Minerals
221
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3.6 X-Ray Topographic Study of the Real Structure

of Minerals
A. AUTHIER and A. ZARKA
Minerals in rocks are usually rather imperfect, but individual minerals which
have been allowed to grow without hindrance and with free surfaces, such as in
pegmatites or druses, may be highly perfect. X-ray topography is an imaging
technique which is very sensitive to local strains and which is therefore applied
to perfect or nearly perfect crystals. It enables one to visualize and to characterize defects such as dislocations, growth bands, growth sector boundaries, low
angle grain boundaries, stacking faults, twin boundaries, etc. It has been used
successfully to assess the crystalline perfection of many types of minerals,
carbonates (calcite, dolomite, magnesite, cerussite), quartz, silicates (beryl, topaz,
spodumene, orthose), diamond, fluorite, phosphates (apatite), etc. The main
motivation for such studies is the determination of the growth history of the
minerals and the understanding of their genesis. But they are also very useful to
determine the characteristics of the defects responsible for the deformation of
minerals.
After pioneer works in 1931 and 1944-1945, the first topographic techniques
enabling the imaging of individual defects such as dislocations were developed in
1957-1959, the method most often used in mineralogy being that due to A.R.
Lang. It enables one to observe the three-dimensional distribution of defects
in large samples up to a few square centimeters and 100 J1.m to 1 mm thick,
depending on how absorbing it is. The radiation used is MoKoc or CuKoc from
conventional tubes, occasionally AgKoc. The width of dislocation images is of the
order of a few microns and the magnification of the image of the crystal on
the photographic plate is of the order of one. The operation conditions of the
technique are therefore widely different from those of electron microscopy and
one understands that, if it is possible to observe large samples, these must be
highly perfect; the density of dislocations which can be separated is of the order
222
of l04jcm2. When it is available, the use of synchrotron radiation as a source is

strongly recommended, not only because of its high intensity, but also because it
is polychromatic and its angular divergence is very small. This increases the
number of possibilities of the technique, enabling photographs to be taken with
very short exposure times and dynamic experiments to be performed under
unusual pressure or temperature conditions, under an applied stress field, or an
applied magnetic or electric field, etc.
A great advantage of the diffraction techniques, such as electron microscopy
and X-ray topography, for the observation of crystal defects is that they provide
not only images, but also the characteristics of the defects, such as the Burgers
vectors of dislocations, the fault vector of a stacking fault, the nature of a twin
boundary.
Principle of X-Ray Topographs

The aim of X-ray topographs is to give a one-to-one correspondence between
images on a photographic plate or a direct viewing system and the distribution
of defects or distorted areas within the crystal. There are many possible setups.
The geometry may be for reflection or transmission. The incident beam may be
monochromatic or white (using synchrotron radiation), pseudo-plane parallel
or divergent. The choice depends on the desired exposure time, spatial and
angular resolutions.
Origin of the Contrast of the Images of Defects on X-Ray Topographs

There are several possible origins for the formation of images on a topograph:
misorientation or variation of lattice spacing between one region and another
one (the so-called orientation contrast), or variation of the diffraction and
propagation properties of X-rays in regions of different degrees of perfection (the
so-called extinction, or diffraction contrast). The latter is the more important
effect to be considered for the interpretation of the contrast of the images of
isolated defects such as dislocations or planar defects.
It is precisely the origin of the contrast of the defect images which explains
why the crystallographic characteristics of the defects can be determined: in the
case of a dislocation, for example, the lattice planes which are parallel to
the Burgers vector are least deformed, in particular, the planes parallel to the
Burgers vector of an edge dislocation and normal to the line are not deformed at
all. The contrast of dislocation images on topographs taken using reflecting
planes parallel to the Burgers vector is therefore very weak; by taking a series of
topographs with various orientations of the reflecting planes, it is thus possible
to find the orientation of the Burgers vector of dislocations.
223
Reflection, or Bragg Case

There are two families of setups. In the first one, due to IB. Newkirk (1959), a
divergent beam falls on the crystal at the Bragg angle at a grazing incidence, and
a photographic plate is placed at an angle as small as possible to the crystal
surface (Fig. 47). If there are large distortions or variations in the degree of
perfection along the surface, a small area A may diffract more, or less, than the
neighboring areas (orientation or extinction contrast, respectively). This will be
recorded on A' on the plate, giving rise to an image.
In the second type of setup, a nearly plane wave coming from a monochromator falls on the crystal at an incidence angle corresponding to a reflected
intensity of about half the maximum value (double crystal topography). Any
small distortion at the surface of the crystal will give rise to a fluctuation of the
reflected intensity which will be recorded as an image on the plate. The observed
images are highly strain sensitive.
Transmission, or Laue Case
Again, the various topographic techniques can be sorted in two classes: those for
which the incident beam is either collimated characteristic radiatic-' or nearly
parallel synchrotron white radiation, and those for which the incident beam is a
nearly plane wave produced with a monochromator using radiation coming
either from a tube or from a synchrotron source.
The former situation is schematically described on Fig. 48 for the case of
collimated characteristic radiation (the method due to A.R. Lang). The angular
and spectral widths of the beam are in general so large that only a small part of
the incident beam is reflected through the crystal. The remaining part, or direct
beam, propagates undergoing only normal photoelectric absorption. The part
which is reflected generates a fan of wavefields which, inside the crystal,
propagate within a triangle, ABC, limited by the incident and reflected directions, called the Borrmann triangle. Its sides make an angle equal to twice the
Bragg angle.
Fig. 47. Principle of reflection

X-ray topography. F X-ray
source; P photographic plate,
() Bragg angle
224
The image of a defect is due in part to the kinematical diffraction of the direct
beam AB by the distorted areas, the so-called direct image, and in part to the
perturbation by even slightly deformed areas of the paths and phases of the
wavefields propagating within the Borrmann triangle ABC. The former is used
to obtain a general picture of the defect distribution in the crystal, while the fine
structure of the latter gives information on the strain field of the defect, usually
through comparisons between experimental images and computer simulations
performed using the dynamical theory of X-ray diffraction.
As an example, Fig. 48 illustrates the image formation in the case of a
dislocation line; the volume around the intersection of the line with the direct
beam AB behaves like a small imperfect crystal and diffracts this direct beam
giving rise to the direct image (D on Fig. 48). At the same time, the dislocation
line perturbs the propagation of wavefields inside the Borrmann triangle and
casts a shadow along its projection AP drawn from the apex, A, of the Borrmann
triangle (Fig. 48). This shadow is called the dynamical image.
There are many variants of the setups used in transmission topography.
Only the principle of the most important ones is given in the following:
Traverse
Fig. 48. Principle of transmission X-ray topography. F X-ray source; D direct image;
P dynamical image. The height of the slit in front of the crystal in the out-of-plane direction
can be up to a few centimeters
225
Section Topographs. By simply putting a photographic plate after the slit shown
on Fig. 48, one can record the various components of the image: D, the direct
image of the intersection of the defect with the direct beam, from the distance of
which to the edge of the topograph one can deduce the depth of the defect, and
P, the dynamical image, respectively.
Projection Topographs. Using collimated characteristic radiation (Fig. 48), one
isolates the reflected beam with a slit and traverses simultaneously the crystal
and the photographic plate in a direction parallel to the crystal surface. The
direct images of the defects are then projected on the photographic plate. All
the topographs shown here (Figs 49 to 53) are examples of images obtained in
that way.
Synchrotron Topographs. Using white synchrotron radiation which has a narrow natural divergence, one simply puts the photographic plate far enough from
the crystal so that the various Laue spots are separated from one another. The
spatial resolution on the topographs is as good as when using monochromatic
radiation. Many reflections are simultaneously present on the Laue diagram
and the properties of the defects can be deduced from the comparison of their
contrast for the various reflecting planes.
In these techniques, the direct images are predominant for crystals with
a small value of }1t (}1, linear absorption coefficient, t, crystal thickness). The
shadows due to the disruption of anomalous transmission along paths ARP are
predominant for high values of }1t (dynamical images).
Nature and Origin of the Defects Present in Minerals

There are many kinds of defects contained in minerals. They may have
originated at various stages in the history of the mineral: during the growth
itself, immediately after growth, during cooling, for instance, or during a
deformation completely independent from the growth period. The main types
are briefly reviewed in the following.
Growth Bands. The inevitable instabilities of the growth front result in variations in the level of impurities of minor elements incorporated in the growing
crystal. When these variations are large, they result in zoning which is visible
optically, but when they are small, they give rise to growth bands which are only
visible by X-ray topography. The correlation of the growth bands observed on
the X-ray topographs with the variation of the impurity content has been
established using many techniques for the detection of impurities, such as
thermoluminescence, cathodoluminescence, and electron microprobe analysis.
These growth bands usually fill up completely a growth sector. They indicate the
successive positions of the growth front and the direction of the growth. They
are very useful to reconstruct the evolution of the habit of the crystal during the
226
growth. This evolution is usually to be correlated to an evolution of the growth

medium which is thus revealed by X-ray topography.
Example. Figure 49a is an X-ray topograph of a thin plate cut normal to the c-axis in a topaz
crystal from Nigeria and Fig. 49b is a drawing of the successive habits of the crystal during its
growth (c. Giacovazzo et a\. 1975). To each face of the crystal corresponds a growth sector
filled with growth striations. Figure 49b has been drawn thanks to the interpretation of
Fig. 49a. It can be observed that the faces {IIO} were the major ones at the beginning while it is
the faces {120} in the later stages. The growth horizons can be followed through the various
growth sectors.
Growth Sector Boundaries. The average lattice parameters usually have slightly
different values in different growth sectors (for instance, lattice parameter a takes
different values in a (100) and a (010) growth sector of a tetragonal crystal. For
this reason, there is always a small strain and a small phase shift associated with
the boundary between two neighboring growth sectors which are revealed by a
characteristic contrast on X-ray topographs.
Example. One can observe contrast at the boundaries between growth sectors on Fig. 49. It
can either be due to a diffraction effect, as between the (120) and (ITO) growth sectors, or to a
decoration by inclusions as between the (023) and (III) growth sectors.
Fig. 49a, b. a X-ray topograph of a (001) slab cut normal to the c-axis of a prismatic topaz
crystal from Nigeria. 120 reflection, MoKIX radiation. Height of the crystal: 13.9 mm. (Giacovazzo et a\. 1975). b Drawing of the successive habits of the crystal during its growth. 1{120} ;
m {IIO}; u {Ill} f {021}; x {023}
227
Inclusions. Liquid or solid inclusions are frequently imbedded in solutiongrown crystals. They can be isolated but they can also decorate growth horizons
or be incorporated at growth sector boundaries. The density of inclusions is
often related to the supersaturation and indicates the direction of the solution
fluxes. During the cooling period after growth, thermal stresses often appear,
due to the differences in the anisotropic thermal expansion coefficients in the
inclusion and in the matrix.
Example. Figure 50 is an X-ray topograph of a thin plate cut normal to the c-axis of a crystal
of beryl from Brazil (Scandale et al. 1979b). The topograph shows that there have been three
main stages in the history of the growth of the crystal. The central part of the crystal grew
during the first stage. It then underwent a stage of dissolution which gave it its round shape. Its
surface was decorated with impurities and growth started again. The lower part of the
boundary between the first and the second stages of growth presents a very strong contrast
associated with liquid inclusions. From the presence of these inclusions, it can be inferred that
the direction of the solution flux came along the opposite direction, indicated by an arrow.
Several dislocation bundles originate from some of the inclusions at the interface. At a later
stage, growth stopped again, as shown by a fine growth horizon decorated by a few inclusions
from which emanate dislocation bundles.
Precipitates. When the mineral is a solid solution of one phase in another one,
and the temperature is decreased below the saturation value, demixion occurs
and that phase precipitates.
Dislocations formed during growth are usually generated because of lattice
misfits around the nucleus or around the inclusions incorporated during the
growth. These dislocations are usually straight, their direction being that which
Fig. 50. X-ray topograph of a beryl thin plate normal to the c-axis.
(Scandale et al. 1979b). 1010 reflection, MoKoc radiation. Height of
the crystal: 8.9 mm. Three stages of
growth, A, B, and C separated by
two growth horizons, F 1 and F 2'
can be observed. The direction of
the solution flux in the last stage of
growth is indicated by an arrow.
Several dislocation bundles originate at inclusions decorating the
two growth horizons
228
minimizes the elastic energy. This direction of minimum energy depends on the
direction of their Burgers vector and on that of the growth, that is on the
orientation of the growth sector within which the dislocation lies. It may happen
that a dislocation crosses a growth sector boundary, going from one growth
sector to the other. As it does so, the direction of the dislocation changes because
the direction of minimum energy is different in both sectors. The dislocation
thus appears to have been refracted when crossing the boundary. As a dislocation cannot terminate inside the crystal unless it is a loop, the dislocations
formed at inclusions constitute bundles which are quite characteristic of solution-growth. If they have a strong screw component, they may play an important role in the growth mechanism and growth kinetics. When such a dislocation
intersects a growth face, it gives rise to a growth spiral.
Example. Figure 51 is the X-ray topograph of a 1.5 mm thick slice cut normal to the c-axis of a
quartz crystal (Ser et al. 1980). The growth sectors are clearly visible, the orientations of which
are given on the figure. So are also dislocations lines. Some are isolated, D, others lie in dense
(1100)
Fig.51. X-ray topograph of a quartz plate, 1.5 mm thick, normal to the c-axis. (Ser et al. 1980).
toTO reflection, MoKa radiation. Height of the crystal: 18.6 mm. The major growth sectors are
indicated on the topograph. They correspond to the {lOTO} prism faces and to the {toTI}
rhombohedral faces. Dislocation bundles, B, originate at the growth sector boundaries
between the (toTO) and (toT I), and (OITO) and (OlIl) growth sectors, respectively. Isolated
dislocations can be seen in the other growth sectors. Brazil twins and stacking faults can also
be observed in the (OlIO) growth sector
229
bundles, B. The latter have originated at inclusions which decorate growth sector boundaries
between growth sectors.
Dislocations formed after growth usually present different characteristics and,

in particular, are not straight. The thermal stresses which are created during
cooling between inclusions or precipitates and the matrix are relaxed by the
formation of prismatic loops.
Channels. If there is a decrease of the supersaturation at a certain time during
growth, or after growth, the crystal may undergo a redissolution episode. This
redissolution may occur not only at the crystal surface, but also along dislocations bundles, creating channels which are visible because they correspond to
natural etch pits at the surface, and also because they present contrast on X-ray
topographs.
Example. Figure 52 is an X-ray topograph of thin plate of a spodumene crystal from Minais
Gerais, Brazil (Authier and Zarka 1977). It shows two growth sectors with growth bands, a
growth sector boundary between them, and, on this boundary, an inclusion from which
originate two channels, T. These channels are empty and terminate at each pits on the surface.
Their diameter is of the order of 15- 30 11m. The one on the right hand side is decorated with
inclusions. A third channel, also marked T, can be seen on the top left hand corner of the
topograph.
Stacking Faults separate parts of the crystals which are shifted with respect to
one another by a translation which is a lattice vector. This shift results in a phase
Fig. 52. X-ray topograph of a spodumene

thin plate from Minais Gerais, Brazil, of the
kunzite variety. (Authier and Zarka 1977).
Reflection 020, MoKIX radiation, orientation
of the plate: normal to the [001] direction.
Height of the crystal: 12.3 mm. Two growth
sectors parallel to (110) and (010) can be
observed. They are separated by a growth
sector boundary. Three channels denoted by
T can be seen. Two originate at an inclusion
decorating the growth sector boundary
230
shift between the structure factors of the two parts which gives rise to a contrast
observable on X-ray topographs. These stacking faults are bordered by partial
dislocations with Burgers vectors which are not translations of the lattice.
Twins and Twin Boundaries. By taking X-ray topographs of a twinned crystal
with a reflecting plane which is not common to the two individuals in the twin,
or which playa different role in the structure, it is possible to image the two
individuals separately, while they can be observed simultaneously with a
reflection which is common to the two individuals and has the same structure
factor.
Example. Figure 53a is a 10To X-ray topograph of a thin plate cut in a quartz crystal twinned
according to the Dauphine law. Figures 53b and 53c are topographs of the two individuals,
Fig. 53a-c. X-ray topographs of

a quartz Dauphine twin. a IOTo
reflection: the two individuals
making up the twin are both visible because they have the same
structure factor. Height of the
crystal: 8.9 mm. b 3031 reflection:
the left hand side individual only
is visible, it presents some growth
bands and a few isolated dislocations. The right hand one has a
very small structure factor and is
not visible. c 3031 reflection: the
situation is opposite to that of b;
the left hand side individual has a
very small structure factor and is
not visible. The right hand one
presents a few dislocation bundles originating at inclusions
231
taken with the 3031 and 3031 reflections, respectively. The former presents growth bands and a
few individual dislocations, while the latter presents a few dislocation bundles originating at
inclusions. The twin boundary is clearly to be seen on Fig. 53a. The reason for the difference in
contrast of the two parts of the twin on the three topographs is the following: they are rotated
with respect to one another by 60 around the c-axis and, while they have the same structure
factor for the 1010 reflection, they have very different structure factors for the 3031 and 3031
reflections. Twins according to the Brazil law can also be seen on Fig. 51.
Twins can be formed during growth, but also through the application of a stress
(mechanical twinning), as in calcite. In the latter case, twinning dislocations are
usually observed in the twin boundary.

Conclusion
X-ray topography is an ideal tool to reveal growth defects in large size nearly
perfect minerals. These growth defects, growth bands, inclusions, dislocations,
can be correlated to variations of the chemical composition of the growth
medium or to accidents which occurred during the growth. They are therefore
very useful to reconstruct the growth history of the minerals. These successive
accidents are usually characteristic of the growth medium and can therefore be
found in different specimens coming from the same source. X-ray topography
is also a very good tool to study the early stages of plastic deformation, but
minerals are less ductile than metals, and these early stages are difficult to
observe by this technique, electron microscopy being much better adapted.
References
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Authier A (1972) X-ray topography as a tool in crystal growth studies. J Cryst Growth 13/14:
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Authier A (1977) X-ray and neutron topography of solution-grown crystals. In: Kaldis E,
Scheel HJ (eds) Crystal Growth and Materials. North Holland, pp 516-548
Authier A (1980) Recent developments in the topographic assessment in crystals. J Cryst
Growth 48: 683-686
Lang AR (1958) Direct observation of individual dislocations by X-ray diffraction. J Appl
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Lang AR (1959a) The projection topograph. A new method in X-ray diffraction micrography.
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Baran Z, Godwod K, Warminski T (1987) X-ray study of Brazil twins in natural amethyst.
Phys Stat Sol (a) 101: 9-24
Lang AR (1965) Mapping Dauphine and Brazil twins in quartz by X-ray topography. Appl
Phys Lett 7: 168-170
Lang AR (1967) Fault surfaces in alpha quartz: their analysis by X-ray diffraction contrast and
their bearing on growth history and impurity distribution. 1 Phys Chern Sol suppl 1:
833-838
McLaren AC, Phakey PP (1969) Diffraction contrast from Dauphine twin boundaries in
quartz. Phys Stat Sol 31: 723-737
McLaren AC, Pitkethly DR (1982) The twinning microstructure and growth of amethyst
quartz. Phys Chern Mineral 8: 128-135
Phakey PP (1969) X-ray topographic study of defects in quartz. I. Brazil twin boundaries. Phys
Stat Sol 34: 105-119
Scan dale E, Stasi F (1985) Growth defects in quartz druses. <a) Pseudo-basal dislocations.
1 Appl Cryst 18: 275-278
Scan dale E, Stasi F, Zarka A (1983) Growth defects in a quartz druse. <a + c) Dislocation.
J Appl Cryst 16: 399-403
Ser A, Bideau IP, Clastre J, Zarka A (1980) Etude des defauts de croissance dans des
monocristaux naturels de quartz. J Appl Cryst 13: 50-57
On X-Ray Topography of Beryl
Graziani G, Scandale E, Zarka A (1981) Growth of a beryl single crystal - history of the
development and the genetic medium. J Appl Cryst 14: 241-246
Graziani G, Lucchesi S, Scandale E (1990) General and specific growth marks in pegmatite
beryls. Phys Chern Mineral 17: 379-384
Herres N, Lang AR (1983) X-ray topography of natural beryl using synchrotron and
conventional sources. 1 Appl Cryst 16: 47-56
Scandale E, Scordari F, Zarka A (1979a) Etude des dCfauts dans des monocristaux de beryl. I.
Observations des dislocations. J Appl Cryst 12: 70-77
Scandale E, Scordari F, Zarka A (1979b) Etude des DCfauts dans des monocristaux de beryl. II.
Etude de croissance. J Appl Cryst 12: 78-83
Scandale E, Lucchesi S, Graziani G (1990) Growth defects and growth marks in pegmatite
beryls. Eur J Mineral 2: 305-31\
On X-Ray Topography of Topaz
Giacovazzo C, Scandale E, Zarka A (1975) Etude des defauts dans des monocristaux naturels
de topaze. II. Etude de gem:se. J Appl Cryst 8: 315-324
lsogami M, Sunagawa I (1975) X-ray topographic study of a topaz crystal. Am Mineral 60:
889-897
Phakey PP, Horney RB (1976) On The nature of grown-in defects in topaz. Acta Cryst A32:
177-182
Zarka A (1974) Etude des dCfauts dans des monocristaux naturels de topaze. I. Observation
des dislocations. J Appl Cryst 7: 453-460
On X-Ray Topography of Spodumene
Authier A, Zarka A (1977) Observation of growth defects in spodumene crystals by X-ray

topography. Phys Chern Mineral I: 15-26
On X-Ray Topography of Diamonds
Lang AR (1974a) Glimpses into the growth history of natural diamonds. J Cryst Growth
24/25: 108-115
3.7 Twinning Due to Phase Transformations and Plastic Deformation
233
Lang AR (1974b) On the growth-sectorial dependence of defects in natural diamonds. Proc R

Soc Lond A 340: 233-248
Lang AR (1977) Defects in natural diamonds: recent observations by new methods. J Cryst
Growth 42: 625-631
Lang AR (1979) Internal structure of diamond. In: Field JE (ed) The properties of diamond.
London, Academic Press, Chap 14
Lang AR, Woods GS (1976) Fingerprinting diamonds by X-ray topography. Indian Diamond
Rev 36: 96-103
Lawn B, Kamiya Y, Lang AR (1965) An X-ray topographic study of planar growth defects in a
natural diamond. Phil os Mag 12: 177-189
Miuscov VF, Orlov YuL (1966) X-ray topographic study of Yakoutia diamonds. Dokl Akad
Nauk SSSR 166: 198-201 (in Russian)
Moore M, Lang AR (1972) On the internal structure of diamonds of cubic habit. Philos Mag
26: 1313-1325
Moore M, Lang AR (1974) On the origin of the rounded dodecahedral habit of natural
diamond. J Cryst Growth 26: 133-139
Orlov YuL, Bulienkov NA, Martovitsky VP (1982) A study of internal structure of variety. III.
Diamonds by X-ray section topography. Phys Chem Mineral 8: 105-111
Suzuki S, Lang AR (1977) X-ray Bragg reflection, "spike" reflection and ultraviolet absorption
topographic studies of internal structures of natural diamonds revealing mixed-habit
growth. J Cryst Soc J pn 19: 207-214
Wild RK, Evans T, Lang AR (1967) Birefringence, X-ray topography and electron microscope
examination of the plastic deformation of diamond. Philos Mag 15: 267-279
On X-Ray Topography of Fluorite
Beswick DM, Lang AR (1972) Some X-ray topographic observations on natural fluorite.
Philos Mag 26: 1057-1070
Calas G, Zarka A (1973) Etude des dHauts de croissance dans des monocristaux de fluorite
naturelle. Bull Soc Fr Mineral Crist 96: 274-277
On X-Ray Topography of Apatite
Phakey PP, Leonard JF (1970) Dislocations and fault surfaces in natural apatite. J Appl Cryst
3: 38,44
3.7 Twinning Due to Phase Transformations and

Plastic Deformation
A.C.
McLAREN
When a crystal transforms (usually on cooling) to a lower symmetry structure in

which there are two or more orientational variants, transformation twinning is
an almost invariable consequence if the new phase is nucleated at more than one
center in the original phase. Two well-studied examples will now be considered
briefly.
When the hexagonal, high-temperature form of quartz (space group C6 z2 or
C6 4 2) is cooled below 573C, the a-axes become polar and the symmetry is
lowered to trigonal (space group P3 121 or P3 2 21). Since there are two choices
for the polarity of the a-axes, domains in which the a-axes are anti parallel are to
be expected. Such domains are related by a rotation of 180 about the unique
0
234
c-axis and are called Dauphine twins. These twins are not observed when
normal petrological thin sections are viewed between cross-polarizers because
the axes are parallel in the twins. For the same reason, Dauphine twins are not
readily detected in normal X-ray and electron diffraction patterns. However,
because the modulii of the structure factors F(hkil) and F(hkil) of the original
and twin orientation are significantly different for some reflections (e.g., 0111
and OlIl), Dauphine twins can be observed by X-ray topography and by
transmission electron microscopy.
In sanidine (monoclinic; space group C2/m) the Si and Al atoms are
disordered among the tetrahedral T sites. Over geological time, ordering takes
place and in maximum microcline (triclinic; space group CT) the ordering is
complete. In this structure there are four main orientational variants: two
orientations related by the albite twin law (rotation of 180 about b*) and two
orientations related by the pericline twin law (rotation of 180 about b). The
composition planes are (010) and the rhombic section which is parallel to band
approximately normal to (001), respectively. Thus, the cross-hatched pattern
observed in (001) sections between crossed-polarizers is generally interpreted as
intersecting sets of albite and pericline twin lamellae formed as a consequence
of the transformation from monoclinic to triclinic. However, recent studies of
micro cline using transmission electron microscopy, indicate that this is a
simplistic picture although the observed cross-hatched patterns are based on the
four orientational variants.
Tweed structures due to the intersection of two near-orthogonal sets of
modulations that are qualitatively related to albite and pericline twin lamellae
are often observed by TEM in partially ordered orthoclase and adularia.
Deformation (or mechanical) twinning is an important mode of plastic
deformation in some common rock-forming minerals, such as calcite, for
example. In most cases, the twinned orientation is produced from the host lattice
orientation by a simple shear parallel to the composition or twinning plane K j
and in the twinning direction M l ' as shown in Fig. 54. A large shear (S = tan!{!,
where !{! is the angle of external rotation) may be achieved by small local
rearrangements of the atoms.
0
--+
Fig. 54. Geometry of twinning by shear
3.7 Twinning Due to Phase Transformations and Plastic Deformation
235
Twinning on e = {I012} planes is readily induced in calcite at room

temperature by compression normal to [0001]. S = 0.694 and corresponds to a
maximum possible strain of 29%. The c-axis rotates through 52S. TEM
observations have shown that single crystals deformed in compression with a
confining pressure of 1 GPa develop a high density of e-twins in suitably
oriented specimens. At strains of about 2%, the twin lamellae are usually planar
and parallel, their thickness being about 111m, which is similar to that of the
un twinned lamellae. Commonly, the twin boundaries contain loosely spaced
arrays of twinning dislocations and the sheared lamellae usually contain glide
dislocations generated by the twinning. Dislocations are generated in both the
sheared lamellae and the matrix by the need to relax the intense stresses
produced by the shape change at the surfaces near the tip of a moving twin
lamella. At high temperatures twinning on more than one plane is common and
high densities of tangled dislocations are generated when one twin lamella
passes through another.
References
Barber OJ, Wenk H-R (1979) Deformation twinning in calcite, dolomite, and other rhombohedral carbonates. Phys Chern Mineral 5: 141-165
Fitz Gerald JD, McLaren AC (1982) The microstructures of microcline from some granitic
rocks and pegmatites. Contrib Mineral Petrol 80: 219-229
Frondel C (1962) Dana's system of mineralogy, vol III. Wiley and Sons, New York, pp 76-87
McLaren AC, Fitz Gerald JD (1987) CBED and ALCHEMI investigation oflocal symmetry
and AI, Si ordering in K-feldspars. Phys Chern Mineral 14: 281-292
McLaren AC, Phakey PP (1969) Diffraction contrast from Dauphine twin boundaries in
quartz. Phys Stat Sol 31: 723-737
Nicolas A, Poirier JP (1976) Crystalline plasticity and solid state flow in metamorphic rocks.
Wiley and Sons, London, pp 45-46; 218-219
Putnis A, McConnell JDC (1980) Principles of mineral behaviour. Blackwell, Oxford,
pp 119-121
CHAPTER 4
Natural Glasses
238
Chapter 4. Natural Glasses
4.1 Structure and Properties of Silicate Glasses and Melts;

Theories and Experiment
B.o. MYSEN and D.
VIRGO
The structure of silicate liquids provides a basis for characterization of the

physical and chemical properties needed to describe igneous processes. With a
sufficient data base of melt structure in binary, ternary and quaternary systems,
the principal structural features likely to exist in silicate melts in the bulk
compositional range of natural igneous rocks can be identified.
Silica
The three principal groups of structure models are the random network
structure, pseudocrystalline structure, and coexisting discrete structure. The
individual groups of structural models are not distinctive in the sense that
aspects of one cannot be incorporated into another.
The random network structure model rests on the premise that in a glass
such as that of Si0 2, all oxygen and all silicon structural positions are
energetically equivalent. In this model there is no ordering except for the
existence of individual SiO!- tetrahedra where the oxygen corners are shared
between neighboring tetrahedra. Experimental support for the random network
model has been found in spectroscopic analysis of Si0 2 glass. The neutron,
Raman, and infrared spectra of vitreous Si0 2 and related compounds can be
reproduced theoretically from the random network model, although there are
some important discrepancies between calculated and measured spectra.
Discrepancies between theoretical and observed spectra point to the fact that
some ordering must exist. In early attempts to deduce the structure of vitreous
Si0 2 from X-ray data, local structural similarity between vitreous silica and
cristobalite was suggested. More recent interpretations of the X-ray data
(Fig. 55) indicate that the greatest similarity is between the structure of tridymite
and that of vitreous Si0 2 and that this similarity persisted to distances of
15-20 A. X-ray data can displayed in terms of pair function distributions
(Fig. 55). The first three peaks, at 1.62, 2.65, and 3.12 A (Fig. 55A) are the
contributions from the nearest neighbor Si-O, 0-0, and Si-Si in the sample.
The Si-O distance to the second nearest oxygen neighbor appears near 4.15 A.
It can be seen from the difference curve (C) between the observed curve (A) and
the sum of the contributions from the Si-O, Si-Si, Si-2nd 0, and Si-2nd Si
(curve B), that the observed spectrum is quite well matched through the nearest
neighbor pairs (1.62, 2.65, and 3.12 A), but the difference between the observed
and calculated curves increases rapidly at greater distances.
Structural studies of vitreous and molten Si0 2 have also utilized vibrational
spectroscopy and to a lesser extent 29Si NMR. A principal aim of these studies
4.1 Structure and Properties of Silicate Glasses and Melts
4000
.Q
239
3000
/--------./
t5
c
.2
'co 2000
0...
~
'C
1000
Radial distance,
c
.Q
40
t5
c
.2
c
"-5
30
140
160
~20
.0
.;::
W
10
ti
'6
Q)
c;,
0...
<l:
Si-O-Si angle, degree
120
180
Si-O-Si angle, degree
Fig. 55A-C. A Pair function distribution curve for vitreous Si0 2 . B Angle distribution
function (intertetrahedral angle, Si-O-Si) versus intertetrahedral angle for vitreous Si0 2 .
e Intertetrahedral angle (Si-O-Si) distribution in vitreous Si0 2 from molecular dynamics
calculations
has been to obtain better characterization of the Si-O-Si angles and their
distribution (120-180; see also Fig. 55B, C). From the discrepancies in the
spectral interpretations on the basis of a single structure it has been suggested
that the vibrational spectra are better interpreted on the basis of two or more
three-dimensionally interconnected structures. The differences between the
structures might be different intertetrahedral angles and angle distributions
and, perhaps, different Si-O bond lengths. Raman spectra of vitreous SiOz are
consistent with the coexistence of at least two coexisting, three-dimensionally
interconnected structures with different average intertetrahedral angles (5-10).
The exact nature of the rings (in particular the number of Si per ring) remains
under debate.
240
Metal Oxide-Silica
A variety of structural models has been proposed. These are the polymer
model, the multicomponent mixing model, and the pseudocrystalline model.
The principal structural premise of the polymer model is that silicate melts
and glasses can be viewed as continuously evolving polymers containing
bridging (0), nonbridging (0-) and free (0 2-) oxygen. An equilibrium of the
form:
0
+ 0 2-
>20-,
(1)
can be written. The equilibrium constant for reaction (1) is:

K1
(ao _)2 .
a o Oa o 2-
(2)
In the simplest case, the mixing is considered ideal and activities can be
substituted with mol fractions. The abundance of oxygen species can then be
calculated from the bulk composition of the melt. Three examples with K1 = 0,
K 1 = oc, and K1 at an intermediate value are considered. With K = 0 only free
and bridging oxygens exist in the melt. With K = oc, either only free and
nonbridging oxygens coexist or bridging and non bridging oxygens coexist. At
exactly 33 1 / 3 mol %, only nonbridging oxygens exist. This composition corresponds to that of orthosilicate stoichiometry. Thus orthosilicate melts would
consist only of SiO:- tetrahedra in association with metal cations. For any
intermediate value of K 1, all three oxygen species coexist in the melt.
In developing a thermodynamic basis for a multicomponent mixing model, it
is assumed that the structural units present in a multicomponent melt system are
those that are produced by melting of the known crystalline materials in the
system. This assumption is also made in the polycrystalline model. For example,
in the system MgO-Si0 2, liquidus phases are periclase (MgO), forsterite
(Mg 2Si04 ), clinoenstatite (MgSi0 3 ), and silica polymorphs (Si0 2). The species
assumed to exist in the liquid were MgsOs, Mg 4 Si 20 s, Mg2.67Si2.670s, and
Si 4 0 s. The model reproduces the liquidus phase diagram in the system
MgO-Si0 2. Thus, provided that sufficient thermodynamic data are available,
the model of multicomponent mixing can be used to calculate liquidus phase
equilibria.
In Raman spectroscopic studies involving a variety of metal oxide silicate
glasses and melts in the compositional range from near that of orthosilicate
(NBO/Si 3 = 4) to fully polymerized melts (NBO/Si = 0), it has been found that
the compositional ranges within which vibrations from Si-O - in the structural
units (SiO:-, Si20~-, SiO~- and Si20~-) could be identified, varied as a
function of the type of metal cation (Table 24). As the M/Si was varied within a
3 NBO/Si: Nonbridging oxygen per silicon. A more general form by which to describe degree
of polymerization is NBO/T; nonbridging oxygen per tetrahedrally coordinated cations.
241
Table 24. Compositional ranges (expressed as bulk melt NBO/Si)

of coexisting structural units (within analytical uncertainty) for
melts on metal oxide-silica joins
NBO/Si range
Coexisting anionic structural units

NazO-SiO z
SiOz, SizO~SiOz, SizO~ -, SiO~
SizO~-, SiO~-, SiO!-
> 0-0.05
0.05-1.0
1.0-1.4
1.4-2.0
SizO~-, SiO~-, SizO~-,
SiO!-
BaO-SiO z
SiOz, SizO~SiOz, SizO~ -, SiO~SiO z, SizO~ -, SiO~ -, SiO!SizO; -, SiO~ -, SizO~ -, SiO!SiO~-, SizO~-, SiO!-
> 0-0.2
0.2-1.0
1.0-1.1
1.1-2.4
> 2.4
CaO-SiOz
SiOz, SizO;SiOz, SizO; -, SiO~SizO; -, SiO~ -, SiO!SiO~-, SizO~-, SiO!SiO~-, SizO~-, SiO!-,
> 0-0.3
0.3-1.0
1.0-2.2
2.2-3.0
> 3.0
oz-
(Cao.sMgo.s)O-SiOz
SiOz, SizO; -, SiO~SiOz, SizO~ -, SiO~ -, SiO!-
> 0-1.2
1.2-2.0
2.0-2.4
2.4-3.0
> 3.0
SizO;-,
SiO~-,
SiO~-, SizO~-,
SiO~-, SizO~-,
SiO!SiO!SiO!-, 0
2-
given system, the degree of polymerization of the individual structural units does
not change as a function of bulk melt polymerization. Only their relative
abundance changes.
With this information in hand, a set of equations that describe the anionic
equilibria in the bulk melt compositional range between ortho- and tecto silicate
can be written;
+ 0 2-,
3Si20~- <o:>2SiO~- + 2SiO!-,
6SiO~- <0:> 2Si 20;- + 2SiO!- ,
2SiO~- <o:>Si0 2 + SiO!-,
2SiO!-
<o:>Si20~-
(3)
(4)
(5)
(6)
and
(7)
Silicon-29 NMR spectroscopy can be used to shed further light on the

anionic structure of metal oxide-silica melts. As a structural unit becomes
242
increasingly polymerized, there is a systematic decrease in the 29Si chemical

shift. These relationships can be used to deduce the presence or absence of
specific structural units in melts and glasses. For example, in 29Si NMR spectra
of disilicate glasses, in addition to the main peak near - 91 ppm, there is a peak
near - 77 and one near - 105 ppm, respectively. The - 77 ppm peak can be
assigned to a Q2 unit (NBO/Si = 2; equivalent to an SiO~ - unit), the - 91 ppm
peak to a Q3 unit (NBO/Si = 1; Si20~-), and the - 105 ppm peak to a Q4 unit
(NBO/Si = 0; Si0 2). Similar interpretations have been offered for spectra of
other compositions. The 29Si NMR spectral interpretation thus supports the
interpretation of the Raman spectroscopic data. Additional experimental support is found in X-ray data. The structural interpretation is also consistent with
results from computer simulation of metal oxide-silica melts. The spectroscopic
and simulation structural data are totally inconsistent with the polymer model
which requires a continuous evolution in melt polymerization when, in fact, a
relatively small number of discrete structural units of fixed degree of polymerization exists in the melts and glasses. The experimental and simulation data do
not explicitly support the assumed structural units employed in the multicomponent mixing or the pseudocrystalline model wherein the liquid in a given
system contains species defined by the liquidus phases in the system. However,
not uncommonly many of the structural elements of common liquidus phases do
seem to exist in the melts.
Both Raman and 29Si NMR spectroscopy can be used to deduce abundance
of the various structural units (Fig. 55). These data show several important
features. (1) There are maxima in the molar abundance patterns of individual
units. The maximum abundance of SiO~ - units is at bulk melt NBO/Si slightly
less than 2.0 and the maximum of Si20~ - slightly less than 1.0. (2) As the
ionization potential of the metal cation(s) increases, a given equilibrium shifts in
the direction of the least polymerized unit. For example, equilibria (6) and (7)
would shift to the right.
Aluminum in Silicate Melts and Glasses

A substantial body of information on the structure of alumino silicate glasses
and melts has been acquired from X-ray diffraction, nuclear magnetic resonance,
and from Raman spectroscopy. These data are consistent with aluminum in
tetrahedral coordination under most conditions relevant to igneous rockforming processes, at least at 1 bar pressure. Aluminum differs, however, from
silicon, in that it is a trivalent cation and, therefore, electrical charge-balance of
tetrahedrally coordinated AP + is necessary in order to attain an effective
electrical charge of 4 + . This charge-balance can be obtained with alkali metals
or alkaline earths.
The 29Si chemical shift in the NMR spectra of alumino silicate melts along
aluminate-silica joins exhibit a systematic decrease with increasing Alj(AI + Si)
regardless of the type of charge-balancing metal cation. This shift is a result of
243

1.0
1.0
0.8
0.8
0.6
0.6
0.4
0.4
.... 0.2
0.2
_::J 0.0
0
c:
U
nl
'-
0.6
~~ao-sio21
T02
"0 0.5
:2:
2 0 .0
NBO/Si
0.4
T20 S
0.3
.'
,,
0.2
0.5
TO..
,~
0.4
0.3
~
/+
0.1
0.0
0
NBO/Si
NBO/Si
0.6
T03
0.2
0.1
0.0
3
NBO/Si
Fig. 56. Molar abundance of structural units in quenched melts on metal oxide-silica joins as
indicated as a function of bulk melt NBO/Si. Shaded symbols represent data obtained with
29Si NMR
decreasing shielding of the 29Si nucleus as AI3+ is substituted for Si4 + in the
tetrahedral network. The line width, however, does increase with increasing
polarizing power of the charge-balancing cation. Similar behavior has been
observed in the 29Si NMR spectra of metal oxide-silica melts. This linebroadening may possibly be ascribed to a wider range of T -0-T angles in the
network as the polarizing power of the metal cation(s) increases.
Systematic studies of melt and glass structure on aluminate-silica joins as a
function of AI/(AI + Si) and electronic properties of the charge-balancing metal
cation have relied primarily on Raman spectroscopy as the structural probe.
The variations in spectral topology of Si0 2-NaAI0 2 glasses with AI/(AI + Si)
might be viewed as reflecting a gradual decrease in the Raman frequencies of
(Si,AI)-OO (0; bridging oxygen) stretch bands as a function of bulk Alj(AI
+ Silo This decrease might result from increasing substitution of AI3+ for Si4 +
in the network. In contrast, in the spectra of alkaline earth aluminosilicate glass
the Raman frequencies of individual stretch bands did not shift with changes in
bulk melt AI/(AI + Silo Only the intensities of particular bands and, therefore,
the proportions of the structural units in the melts varied. The spectra are
consistent with two or three different coexisting three-dimensional interconnected structural units in fully polymerized alkaline earth aluminosilicate
244
glasses. One was the A12Si20~ - unit (this unit could be viewed as the equivalent
of the "anorthite" entity suggested for CaAl 2Si 20 s composition glass from xray data). A second unit may be a six-membered, three-dimensionally interconnected ring similar to that of molten Si0 2. Finally, there are indications of AIOi
units in very aluminous melts [Alj(AI + Si) > 0.5]. The abundance of these
units in CaAI 20 4-Si0 2 quenched melts follows a pattern as a function of the
Alj(AI + Si) of the melt such as that shown in Fig. 57, with a gradual increase in
abundance of A12Si20~ - units with increasing Alj(AI + Si) to a maximum at
Alj(AI + Si) slightly greater than 0.5, followed by an abundance decrease as the
aluminum content is increased further. In the same concentration range, the
coexisting Si0 2 units decreased in abundance. A similar abundance behavior
was suggested for MgAl 20 c Si0 2 composition melts (Fig. 57).
In depolymerized alumino silicate melts and glasses, the structural complexity is increased because AI3+ may be partitioned between coexisting structural units of varying degree of polymerization. In melts with three or more
coexisting units of differing degree of polymerization, the preference is for the
most polymerized unit followed by the unit of intermediate degree of polymerization [i.e, Alj(AI + SW0 2 > Alj(AI + SW205 > Alj(AI + SW03]' Raman and
29Si NMR spectra of quenched melts in the system Li 20-Na 20-K 20CaO-AI 20 3 -Si0 2 show that in depolymerized melts [where structural units
with different degree of polymerization coexist, i.e., Eqs. (3)-(7)] Al 3 + exhibits a
strong preference for the most polymerized of these coexisting structural units.
This conclusion is also consistent with observations of the crystal chemical
behavior of AI3+ in aluminosilicate crystals wherein AI3+ tends to associate
with a tetrahedral site nearest the smallest available intertetrahedral angle. In
de polymerized silicate melts with coexisting structural units, the structural unit
with the smallest intertetrahedral angle is the three-dimensional network unit.
The structural behavior of AP+ under these circumstances can be illustrated
by substitution of charge-balanced (MAI)4+ (M = 0.5 Ca, Mg, M = K, Na and
100
(5
"::'
0 !.
80
E
ai
0
60
c:::
C\l
"0
c:::
:::::I
.0
40
..
c:t:
20
0.2
0.4
0.6
AI/(AI+Si)
0.8
1:0
Fig. 57. Molar abundance of three-dimensionally interconnected structural units in

CaAI 2 0 c Si0 2 and MgAI 2 0 4 -Si0 2 quenched melts as a function of bulk melt All
(AI + Si)
'::l
c
0.6
0.5
0.4
iii
0.3
U5
0.2
::l
245
:ii:
0.1
0.2
0.3
AI/(AI+Si)
0.5
0.1
PTPs+T03
0.2
0.3
0.4
0.5
AI/(AI+Si), bulk melt
Fig. 58A, B. A Abundance of coexisting structural units in quenched melts along tetrasilicatetetra-aluminate joins (M2Si409-M6AI409 joins with results from the Na2Si409-Na6A1409
join as examples). B Aluminum content of individual structural units in quenched (from
1400 C and 1 bar) melts
Li) for Si 4 + (Fig. 58A) where there is a systematic increase in the abundance of
T0 2 units (or Q4) and a concomitant decrease in the abundance of T 20S units
(Q3). This trend is accompanied by an increase in abundance ofT0 3 units (Q2).
An equilibrium of the form;
(8)
might explain the observations. The equilibrium shifts to the right thus forming
T0 2 and T0 3 units as Alj(AI + Si) of the system increases. The Alj(AI + Si) of
the T0 3 unit is significantly less than in T 20S units and that in T 20S units less
than in T0 2 units (Fig. 58B). The extent of this aluminum preference diminishes
in a systematic manner as a function of increasing Zjr2 of the metal cation.
Iron-Bearing Systems
Iron is the only major element that occurs in more than one oxidation state in
natural magmatic liquids under terrestrial rock-forming conditions. The local
structural environments in Fe-bearing silicate melts have been studied by
Mossbauer, luminescence, absorption, EPR spectroscopy, and by Raman,
NMR, and X-ray absorption K-edge spectroscopy.
On the basis of several hundred M6ssbauer spectra of iron-bearing glasses,
by using structural inferences from other spectroscopic techniques (luminescence, optical absorption, EPR, EXAFS), and by comparison with M6ssbauer
spectra of ferri-silicate minerals with well characterized ferric iron-oxygen
polyhedra, it is generally concluded that with the isomer shift of ferric iron
(IS Fe 3 + ) less than about 0.3 mmjs (relative to metallic iron) for spectra recorded
at 298 K, this ferric iron is in tetrahedral coordination. From 298 K spectra of
crystalline material, IS Fe 3 + > 0.4 mmjs is diagnostic of octahedrally coordinated
ferric iron. From spectra of glassy materials, this latter value appears greater
246
than about 0.5 mm/s. The isomer shifts of ferric iron vary with Fe3+ / EFe. With
up to about 10 wt. % iron oxide added as Fe 2 0 3 , the IS Fe 3 + remains nearly
constant (between 0.25 and 0.35 mm/s for 298 K spectra) in the Fe 3 + I EFe range
0.5- 1.0. In the Fe 3 + I EFe range 0.5- 0.3, the IS Fe 3' increases to above 0.50 mm/s
with decreasing Fe 3 + I EFe and remains constant for Fe3+ I EFe values lower
than about 0.3. These observations indicate that for oxidized, iron-bearing
silicate melts (Fe3+ I EFe > 0.5), ferric iron is principally in tetrahedral coordination, whereas for reduced (Fe 3 + I EFe < 0.3) melts, ferric iron is in
octahedral coordination. In the intermediate Fe 3 + / EFe range (0.5- 0.3), these
Mossbauer data are consistent with coexisting tetrahedrally and octahedrally
coordinated ferric iron.
Ferric iron occurs in clusters in silicate melts and glasses. From the Raman
spectroscopic data either these clusters have invariant Fe/ Si or Si 4 + is absent. A
structural model with FeOi complexes (or units) and units stoichiometrically
resembling Fe 3 0 4 in highly oxidized melts, and Fe3+ as a network modifier
(octahedral coordination) in very reduced compositions has been suggested
from spectroscopic observations (Fig. 59). The proportions of these structural
units vary with Fe3+ / EFe.
Optical absorption spectra of quenched melts in Fe-bearing alkali silicate
melt systems may indicate the presence of two ferrous iron-oxygen polyhedra
(near 5000 and 10000 em - 1) with Fe 2 + in octahedral coordination. Whereas in
Fe3+ -free, iron-bearing samples, from Mossbauer spectroscopy the IS Fe 2+ values of both doublets accord with those found for octahedrally-coordinated
ferrous iron ( '" 1.1 mm/s), with increasing Fe 3+ / EFe, the average IS Fe 2+ values
tend to decrease below 1 mm/s (relative to Fe metal). The decrease in IS Fe 2 +
might be due to different number of oxygens in the Fe 2 + -polyhedra (e.g., four
rather than six). Four-coordinated Fe2+ has also recently been suggested for
melts on the basis of EXAFS and Raman spectroscopic data although this
conclusion differs from that based on optical and luminescence spectroscopy. It
is also difficult to rationalize why Fe 2 + should prefer tetrahedral coordination
0.12,....---- - - - - - - --------,
.;, 0.08
u.
Fe(IV)o;~ Fe3+(VI) + 20 2","",c---.",,-c,IV)02~ 4FEf++ 6d- + 02
0.04
0.00
!~""':"~~~~- 4Fe 3"'(VI) + 2cJ-~ 4Fe 2\ 0 2
0.7
0.6
0.5 0.4 0.3 0.20.1 0.0

Fe3+ILFe
Fig. 59. Proportions of four- and six-coordinated ferric iron in Na-silicate melts as a function
of Fe 3+ /1:Fe of the melt
247
whereas cations such as Mg2 +, Ca 2+, are octahedrally coordinated. Furthermore, tetrahedrally coordinated ferrous iron is extremely rare in crystalline
silicates. Thus, there is little crystallographic precedent for such a structural
position of Fe 2+ in iron-bearing glasses.
Other Cations
Among the major element oxides in igneous rocks, titanium, and phosphorus
generally are the least abundant. Nevertheless, these two oxides have attracted
considerable attention because even in their natural abundance ranges melt
properties are profoundly affected.
Titanium. The coordination number ofTi 4 + has been defined with XANES and
EXAFS data, which indicate that there are two different Ti-O polyhedra in
Si0 2- Ti0 2 glass. One has a Ti-O distance of 1.80 0.02 A, and the other 1.92
0.02 A. The shorter distance is characteristic of Ti + in fourfold coordination,
whereas the latter is consistent with Ti 4+ in six-fold coordination. Four-fold
coordinated Ti 4 + occurs in all concentration ranges and nearly 100% of the
Ti 4 + is in tetrahedral coordination in the concentration range between about 1
and 7 wt. % Ti0 2. This concentration range is that most relevant to natural
magmatic liquids. Six-coordinated titanium becomes rapidly important as the
Ti0 2 content decreases below 1 wt. %. As the Ti0 2 content increases above
about 7 wt. %, the proportion of octahedral Ti 4 + increases concomitantly with a
reduction in abundance of tetrahedrally coordinated Ti4 +. The general conclusions from X-ray absorption studies accord with the interpretations of the
vibrational spectra of Si0 2- Ti0 2. Less is known about the structural role of
Ti 4+ in depolymerized melts and glasses. The existing structural data are
derived principally from Raman spectroscopy. Most of this information is
consistent with Ti 4+ in tetrahedral coordination, but the data do not conclusively rule out other interpretations.
Phosphorus. The structural role of phosphorus in silicate melts has been
investigated principally with vibrational spectroscopy. Details of the interaction
between pH and the silicate melt structure have also been studied with
31PNMR.
In the Si02-P20s glass system the Raman spectra are consistent with the
existence of p=o bonds and P-O-Si bridges in vitreous Si0 2-P 20 s. With
increasing phosphorus concentration, there is an abundance increase of both
these types of bonds in the glass.
In depolymerized melts and glasses, Raman and 31 P NMR spectroscopic
results are consistent with phosphate complexing as the principal solution
mechanism. Most of the Raman data suggest that this phosphate is of orthophosphate type. The 31p NMR chemical shifts for amorphous P-bearing metasilicate glasses are in the range 1.5 to 3.9 ppm, in accord with that of crystalline
248
orthophosphates. Phosphorus in meta silicate melts therefore most likely exists

in separate orthophosphate tetrahedra (POl-) consistent with Raman spectra
of Na 20-CaO-Si0 2-P 20 s glasses with up to 15 wt. % P 20 S. Thus, it would
appear that the polymerization of phosphate complex(es) does not change as the
concentration of phosphorous is varied in simple metal silicate glasses. This
behavior differs, however, somewhat from that found in the system
CaSiOl-CaAI2Si20s-P20s (2wt.% P20S)' where the 31p chemical shift
became increasingly negative with increasing abundance of the CaAlzSi 20 s
component (ranging up to - 7.5 ppm). This change is consistent with increasing
polymerization of the phosphate complex(es), but may be insufficiently negative
to be consistent with aluminophosphate complexing (about - 32 ppm). Details
of the solution mechanisms in these complex alumino silicate glasses remain to
be identified.
Implications for Properties Synthetic and Natural Glasses and Melts
Perhaps the most important conclusion to be drawn from the rather extensive
experimental and simulation studies of silicate melts and glasses is that these
materials cannot be viewed as continuous polymers that evolve continuously as
a function of changes in melt polymerization. Instead, it has been found that a
small number of comparatively simple tetrahedral complexes (units) coexist.
Their proportions (and activities) are bulk compositionally dependent. It is also
notable that cations other than Si 4 + in tetrahedral coordination do not always
substitute randomly for Si 4 +. Instead clusters or units with local order are
found. Further, tetrahedrally coordinated cations other than Si 4 + tend to favor
particular structural units in the melts and glasses.
These structural features appear reflected in a variety of melt and glass
properties. The activity coefficient of Si0 2 in metal oxide-silica melts with the
same overall degree of polymerization (NBO/Si) is a positive function of the
ionization potential of the metal cation. The relative abundance of Si0 2
structural units is also positively correlated with the ionization potential, thus
suggesting that at least some of this increase in activity coefficients is directly
related to the anionic structure of the melt as controlled by the properties of the
metal cation.
Rheological properties of silicate melts can be characterized in part via an
understanding of the properties of bonds that need to be broken and recreated
during flow, and activation energies of viscosity, diffusivity and conductivity
may respond to the bond energies. In simple metal oxide-silica melts, the
activation energy of viscous flow exhibit discontinues functional relations to the
degree of polymerization of the melts (Fig. 60). The melt compositions at which
these discontinuities are observed correspond to those where the anionic
equilibria [Eqs. (3)-(7), see also Table 24] change. Molar volume versus composition functions also display discontinuities at these compositions (Fig. 60).
Further, the compositions at which the discontinuities are observed are sys-
ns
Jot
Q
en
CD
Fig. 60A-C. Activation energy of viscous flow

as a function of NBOjSi (A), molar volume as a
function of mol percent metal oxide (B), and
viscosity of alkali aluminodisilicate melts (C)
80
60
40
c:
.Q
iii
.<!:
20
Li~O
O'---'-___'---'-----I'--...L---1----.J
o
20
40
60
mol % metal oxide
C')-
t
~
29
r-----.---..-----~
27
25.0 36.3
I
25
249
23L-_ _...L~_~_ _~
o
60
20
40
mol % metal oxide
20
mol %
40
N~AI4,\
250
tematic functions of the electronic properties of the metal cation. Similar

functional relations can be observed in the compositional ranges of a specific
system over which a particular anionic equilibrium describe the melt structure.
The role of aluminum in silicate melts is particularly interesting in that
although AI3+ substitutes nearly randomly for Si 4 + in alkali alumino silicate
melts the relationships between a physical property such as an activation energy
of a transport property (and, therefore, the property itself), is not always a
simple function of bulk melt Alj(AI + Si). Substitution of AI3+ by itself weakens
the (Si,AI)-O bond as reflected in lowered force constants and lowered viscosity
and activation energy of viscous flow in fully polymerized melts. In such melts,
all oxygens are bridging, and only. bridging oxygen bonds are involved in the
transport process. In depolymerized melts, on the other hand, AI3+ substitutes
principally for Si 4+ in fully polymerized units thus driving a reaction such as Eq.
(8) to the right. That is, the abundance of fully polymerized units increases with
Alj(AI + Si). In metal oxide-silica melts, the abundance of such structural units
is positively correlated with the degree of melt polymerization. In depolymerized
alumino silicate melts, we have, therefore, two competing mechanisms that affect
the melt viscosity. The viscosity decreases as the melt becomes more aluminous,
but increasing Alj(AI + Si) also causes an increase in abundance of fully
polymerized units, which would tend to cause an increase in viscosity. These two
competing mechanisms can be used to rationalize the minima in melt viscosity
as a function of Alj(AI + Si) along silicate aluminate joins such as those shown
in Fig.60C.
Less experimental data are available for transport properties other than
viscosity. However, it has been demonstrated that viscosity can be related to
diffusion. Experimentally, the Eyring equation;
D = kTjA.'1,
(9)
is a good approximation. In this expression, D is diffusion coefficient, k is

Planck's constant, T is absolute temperature, '1 is viscosity, and A. is translation
distance. Thus, the diffusivity is inversely related to viscosity. One would predict,
therefore, that any intensive or extensive variable that is positively correlated
with viscosity is negatively correlated with diffusivity. For example, the more
fluid a melt (fluidity = 1 j'1), the larger is the diffusion coefficients.
The structure of natural magmatic liquids, and, therefore, our ability to
characterize relationships between their structure and petrologically important
properties, can be inferred from data in simple binary, ternary and quaternary
systems. For example, the abundance of individual structural units in a complex
natural melt can be described with an expression of the form;
Xi = a
+ b(NBOjT) + c(NBOjTf + d(NBOjT)3 + e(NBOjT)4,
(10)
where Xi is the abundance of a unit i associated with a particular metal, and a, b,

c, d, and e are coefficients that have been determined experimentally from
structural data in binary metal oxide-silica melt systems. The degree of polymerization, NBOjT, of the melt can be calculated from the composition of the
251
magmatic liquids on the basis of simple system data:

(11)
where n is the electric charge of the network -modifying metal cation, Mi'
Similar expressions have been derived empirically for the abundance of
AI-bearing structural units;
Xi
= a + b [Alj(AI + Si)] + c [Alj(AI + Si)]2
+ d [Alj(AI + Si)]3 + e [Alj(AI + Si)]4,
(12)
where Xi is the abundance of the particular unit, the Alj(AI + Si) is the bulk
melt Alj(AI + Si). From considerations such as this, it has been found that the
two most important structural units in natural magmatic liquids are the fully
polymerized units (T0 2), and units with two nonbridging oxygens per tetrahedrally coordinated cations (T0 3). Orthosilicate units (T0 4) are also important
in particular for systems where alkaline earth contents are high. In an analysis of
a wide variety of extrusive igneous rocks ranging from rhyolite to picrite, it has
been found that in 90~95% of the cases, at least 50% of the structure consists
of T0 2 units.
From results of structural calculations as illustrated with Eqs. (10)~(12), it
has been found that molar volumes of natural magmatic liquids are linearly and
positively correlated with the concentration of T0 2 units in the melts and
linearly and negatively correlated with the abundance of T0 3 and T0 4 structural units. Similar numerical experiments have been conducted for viscosity. A
bimodal distribution in isothermal viscosities and activation energies of viscous
flow of natural liquids has been observed. Rhyolite and dacite comprise the
high-viscosity maximum, and the remaining, less polymerized melts define the
other maximum. Exponential functions describe the relationships between
structural unit abundance, melt viscosity and their activation energies of viscous
flow. In light of the Eyring relation [Eq. (9)], similar relations are likely for
diffusivity (and conductivity) of natural magmatic liquids.
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4.2 X-Ray Studies of Glass Structure

D.A. McKEOWN and N. ZOTOV
The development of new and traditional methods for atomic structure determination led to direct structural investigations of natural and synthetic
noncrystalline materials. More recently, computer programs modeling glass
structure, as well as modeling the effects of glass structure on scattering and
spectroscopic experiments, have been used to complement, and at times, unravel
ambiguities in experimental results. In earth sciences, most research done on
amorphous materials concentrates on silicate glasses, and this will be emphasized here.
255
Techniques: Experimental and Theoretical
Monochromatic and energy dispersive X-ray scattering experiments yield the

radial distribution function (RDF) of a glass. The methodology of X-ray
scattering experiments, data correction, calculation of the RDF, and limitations
of the Fourier method are well established. The range of the data in q-space
[q = (4nsinO)/A] determines the resolution and the quality of the structural
information which can be extracted from the experiment. By using energy
dispersive X-ray scattering, one can collect data over a larger q-space range than
the range available for conventional monochromatic X-ray scattering. The
new pulsed neutron sources can extend q-space to qmax = 100 A-1. These new
developments can improve the RDFs of complex multicomponent oxide glasses,
such as most natural glasses. However, due to ambiguities from overlapping pair
correlations, there are no easy ways for direct assignment of the peaks in the
RDF of an amorphous material with three or more atom types. The quasicrystalline model approach is still the most popular and acceptable model, since
an RDF of a quasi-crystalline model can be generated and compared with
experiment.
In recent years, EXAFS (extended X-ray absorption fine structure) has
become a complementary tool for the determination of nearest neighbor atoms
around a particular atomic species. EXAFS has been used to determine the
coordination environments of minor and major elements, as well as networkmodifiers and network-formers of glasses.
Computer-based energy minimization models of glass structure, such as
molecular dynamics and Monte Carlo simulations, are dependent on the choice
of interatomic potentials. Most of these studies have not simulated glass
structures more complicated than sodium-silicate glass. The implementation of
new three-body potentials may produce models with more realistic bond angle
distributions. An alternative approach is the Reverse Monte Carlo method,
which has been introduced recently.
Natural Glasses
Natural glasses are a variety of materials that include volcanic glasses, tektites,
impactites, fulgurite glasses, glasses from the lunar regolith, natural gels, microcrystalline precipitates, and metamict minerals. Problems of nomenclature are
compounded by the complexity of the phase composition and microstructure of
natural glasses. These materials consist of a glassy matrix and distinct crystalline
phases (phenocrysts). The glassy matrix usually contains microcrystals of these
minerals. This necessitates the combination of several diffraction and spectroscopic techniques for understanding the structure and composition of natural
glasses and the implications to earth sciences.
256
The investigation of inhomogeneities and microcrystals in the glassy matrix

by high resolution electron microscopy, transmission electron microscopy
(TEM), and small-angle X-ray scattering (SAXS), can give valuable information
about the genesis and thermal history of natural glasses. The short-range order
of the glassy matrix itself can be determined from conventional X-ray or neutron
scattering.
However, only a few papers devoted to natural glasses have appeared. The
first paper, as far as we know, is on the structure of tektites. An X-ray scattering
study of diaplectic labradorite glass concludes that this material is made up of
randomly oriented feldspar-like structural units. The RDFs of synthetic anhydrous glass of rhyolitic composition and natural acidic volcanic glasses have
been recently published.
Synthetic Glasses
Much greater attention has been drawn to the investigation of synthetic glasses
of geologically relevant compositions. In a series of fundamental papers, it has
been proposed that structural models of feldspar and feldspathoid composition
glasses can be based on quasi-crystalline structures. Albite (NaAISi 3 0 s) and
orthoclase (KAISi 3 0 s) glass structures, in contrast with anorthite (CaAI 2 Si 2 0 s)
glass structure, are better explained by a stuffed tridymite quasi-crystalline
model, that is made up of six-membered rings and is similar to the nepheline
(Na 2 AI 2 Si 2 0 s ) structure. The anorthite glass structure can be modeled as a
feldspar-like quasi-crystalline structure that is based on four-membered rings.
These findings indicate that monovalent network-modifying Na + and K + have
a very different effect on glass structure compared with the divalent networkmodifier Ca2+.
EXAFS results have been presented on the network-modifying Na +, K +,
and Ca2+ environments in aluminosilicate glasses. However, due to the disordered nature of these sites, EXAFS is probably sensitive only to the nearest
oxygens surrounding the network-modifiers; and the results of the analysis are
probably taking into account only part of the network-modifying coordination
environment. The structural role of Al as a network-former in sodium-aluminosilicate glasses was clearly determined qualitatively by XANES (X-ray absorption near-edge structure) and quantitatively by EXAFS.
Future Trends and Conclusions

To learn more about glass structure, improvements need to be made to the
experimental and theoretical methods available today. A major unknown aspect
of silicate glasses is the middle-range structure, or ring statistics. Here we are
considering combinations of three-, four-, six-, and other-membered rings in a
257
glass structure. Another important problem is determining the long-range order

of a glass, which has been hypothesized as either a continuous random network,
or a random packing of strained crystalline spheres approximately 20 to 30 Ain
diameter (strained cluster model). To date, there is no atomic structural evidence
to support the strained cluster model. X-ray experiments alone will probably not
be effective in unraveling these middle- and long-range order problems. Other
techniques will be needed to determine the longer-range nature of glass structure, which has important effects on the macroscopic physical properties of a
glass. Some of these techniques may include spectroscopies sensitive to vibrational modes of clusters of atoms, scanning tunneling microscopy, and electron
microdiffraction.
Raman spectroscopy, which is sensitive to the middle-range order of a solid,
may be a way of determining ring statistics of a glass. Calculations have been
made to determine vibrational modes for three-membered silicate rings; comparisons have been made between the calculations and the Raman spectrum of
Si0 2 glass. Raman spectra gathered on single-crystal cyclosilicates, which have
isolated silicate rings, may be useful in determining ring vibrational modes. As
far as we know, only powder Raman has been done on some cyclosilicates. As
a future step, Raman spectra gathered on single crystal phyllosilicates and
tecto silicates may provide information on vibrational modes of rings that are
linked together to form two- and three-dimensional networks. Vibrational
modes of the linked rings in the crystal structures may more realistically model
the ring vibrational modes of a silicate glass. Ring mode assignments from the
single crystal silicates may be used to model the 50 to 700 cm - 1 range of the
Raman spectrum of a glass, where most ring modes probably exist.
References
Brown GE, Waychunas GA, Ponader CW, Jackson WE, McKeown DA (1986) EXAFS and
NEXAFS studies of cation environments in oxide glasses. J Phys Paris 47 Coli C8: 661
Diemann MD, Arndt J (1984) Diaplectic labradorite glass from the Manicouagan impact
crater II. X-ray diffraction studies and structural model. Phys Chern Mineral 11: 278
Dorfman MD, Sokolov AI, Podleskaya AV (1976) About the question of the X-ray structure of
tektites, Meteoritika 35: 87 (in Russian)
Galeener FL, Bario RA, Martinez E, Elliott RJ (1984) Vibrational decoupling of rings in
amorphous solids. Phys Rev Lett 53: 2429
Goodman CHL (1983) The strained mixed-cluster model of the glassy state. Standard
Telecommunications Laboratories, Harlow, Essex, England. Publ AW6564-4
Greaves GN, Fontaine A, Lagarde P, Gurman SJ (1981) Local structure of silicate glasses.
Nature 293: 611
Griffith WP (1969) Raman studies on rock-forming minerals. Part I. Orthosilicates and
cyclosilicates. J Chern Soc AI: 372
Hansma PK, Tersoff J (1987) J Appl Phys 61: 15
Hochella MF, Brown GE Jr (1984) Structure and viscosity of rhyolitic composition melts.
Geochim Cosmochim Acta 48: 2631
Inoue H, Yasui I (1987) A molecular dynamic simulation of the structure of silicate glasses.
Phys Chern Glass 28: 63
258
Jackson WE, Brown GE Jr, Ponader CW (1987) X-ray absorption study of the K coordination
environment in glasses from the NaAISi 30 s-KAISi 30 s binary. Structural implications for
the mixed-alkaline effect. J Non-Cryst Sol 93: 311
Karlsson KH, Froberg K (1987) Structural units in silicate glasses. Chern Geol 62: 1
Konnert J, d' Antonio P (1986) Ultramicroscopy 19: 267
Leadbetter AJ, Wright AC (1972) Diffraction studies of glass structure I., J Non-Cryst Solids
7: 23
McGreevy RL, Pusztai L (1987) Mol Simul 1: 359
McKeown DA (1987) Radial distribution analysis of a series of silica rich sodium aluminosilicate glasses using energy dispersive X-ray diffraction. Phys Chern Glass 28: 156
McKeown DA, Waychunas GA, Brown GE Jr (1985) EXAFS study of the coordination
environment of aluminum in a series of silica-rich glasses and selected minerals within the
NazO-Alz03-SiOz system, J Non-Cryst Sol 74: 349
Murray RA, Song LW, Ching WY (1987) Structural models for (Na zO),(SiO zl 1 - , glasses with
periodic boundaries. J Non-Cryst Sol 94: 133
Sharma SK, Philpotts JA, Matson DW (1985) Ring distribution in alkali- and alkaline-earth
aluminosilicate framework glasses - a Raman spectroscopy study. J Non-Cryst Sol 71: 403
Taylor M (1979) A quasi-crystalline model for interpretation of radial distribution functions:
theory and experimental confirmation. J Appl Cryst 12: 442
Taylor M. Brown GE Jr (1979) Structure of mineral glasses I. The feldspar glasses NaAISi 30 s,
KAISi 30 s, CaAlzSizOs. Geochim Cosmochim Acta 43: 61 and 1467
Teo BK, Joy DC (1981) EXAFS spectroscopy, technique and applications. Plenum Press,
New York
Vessal B, Amini M, Leslie M, Catlow CRA (1990) Potentials for molecular dynamics
simulations of silicate glasses. Mol Simul 5: 1
Wright AC (1985) Scientific opportunities for the study of amorphous solids using pulsed
neutron sources. J Non-Cryst Sol 76: 187
Wright AC, Leadbetter AJ (1976) Diffraction studies of glass structure. Phys Chern Glass
17: 122
Zachariasen WH (1932) The atomic arrangement in glass. J Am Chern Soc 54: 3841
Zemann J (1988) What is glass? In: Konta J (ed) Proc 2nd Int Conf Natural Glasses, 21-25
Sept 1987, Prague, Czechoslovakia. Prague, Univ Karlova, p 35
Zotov N, Dimitrov V, Yanev Y (1989) X-ray radial distribution function analysis of acid
volcanic glasses from the Eastern Rhodopes, Bulgaria. Phys Chern Mineral 16: 774
4.3 Terrestrial and Lunar, Volcanic and Impact Glasses,

Tektites, and Fulgurites
V.
BOUSKA
and V.1.
FELDMAN
Like minerals and rocks, natural glasses, can provide important information on
the history of the Earth, the Moon, and the planets. However, they are much
rarer on the surface of the Earth than crystalline rocks and minerals (mineralogists have described about 3450 minerals). The reason for this difference can be
found in the contents of water and other volatiles in the parental melt. These
components reduce the viscosity of terrestrial magmas and increase the diffusion
rate of dissolved oxides, with consequent crystal growth. It is unusual to find
lava on the surface of the Earth that has solidified sufficiently fast to be
preserved as glass. Conditions on the Moon are different. The lunar surface has
4.3 Terrestrial and Lunar, Volcanic and Impact Glasses, Tektites, and Fulgurites
259
been found to contain a wide variety of different kinds of glass, but only about
90 minerals have been identified. A similar, though less pronounced, phenomenon can be observed for the meteorites except for "wet" carbonaceous
chondrites.
Natural glasses are formed from a liquid state by supercooling, as condensates from a rapidly cooled sublimate or by pressure destruction of the crystal
structures of substances.
Natural glasses can be classified as: (1) terrestrial, lunar and planetary
volcanic glass, (2) impact glass formed by thermal fusion ofthe original minerals
and rocks during impact on the Earth, Moon, planets, and meteorites, including
tektites, (3) diaplectic glass formed during impact by a pressure shock wave,
(4) fulgurite glass formed after lightning shock. There are also glasses formed
during the combustion of coal seams and oil, and also during tectonic processes
(frictionites). Glassy meteorites from the Moon have been described by Fudali
et al. (1984).
All natural glasses are thermodynamically unstable under conditions on the
Earth's surface and have a tendency to chemically weather or recrystallize
(devitrification). These processes lead to glass destruction. Volcanic glasses of the
Earth are rarely older than 65 Ma, but silicate glass may exist over geological
ages in other environments, e.g., the age of lunar glasses is hundreds of million
and billion years. Older impact glasses have undergone alteration and the oldest
North American tektites have been dated at 35 Ma.
Terrestrial and Lunar Volcanic Glasses

Volcanic glasses are produced by rapid cooling oflava. Their chemical composition is as differentiated as that of any volcanic rock (basaltic, intermediate, and
acid volcanic glasses). Moreover, the glasses are more enriched in silica and
alkalies than the corresponding volcanic rocks. Basaltic opaque glass packed
with fine particles of ore minerals is sometimes called tachylite; transparent
basaltic glass is known as sideromelane. Fibrous basaltic glass in the Hawaiian
Islands is named Peleine's hair and the lapilli of this glass are called Peleine's
tears.
The chemical composition of basaltic volcanic glasses varies within the
following ranges (wt.%): Si0 2 (49-54), Ti0 2 (0.5-1.0), Al 2 0 3 (15-17), Fe 2 0 3
(3-5), FeO (4-6), MnO (0.1-0.2), MgO (9-10), CaO (8-10), Na 2 0 (2.5-3.5), K 2 0
(0.5-2), H 2 0 (0.1-1.0); F, CI, S, CO 2 -tenths of a percent (Nasedkin 1985). The
values n ~ 1.6, p ~ 2.8-2.9 gcm- 3
Acid volcanic glasses are usually designated according to their water content
and structural and textural properties. Their composition ranges (wt. %): Si0 2
(71-77), Al 2 0 3 (12-14), FeO + Fe 2 0 3 (1), CaO + MgO (0.5-2), Na 2 0 (3-5),
K 2 0 (3-5).The values n ~ 1.480-1.493, p = 2.27-2.40 gcm- 3
Obsidian is a compact black, grey, purple, or reddish glass with a water
content of up to 1%.
260
Some glasses possess a high water content (perlite 1.5-6 wt. %; pitchstone
6-16 wt. %). Pumice is usually considered to be foamed obsidian, but often has a
water content similar to that of perlite. It is light and floats on water.
Experimental data (IR, PMR) and geological observations reveal that the
high water content (up to 16 wt. %) of some volcanic glasses is due to the reserve
of endogenic water under instant isobaric chilling. During this process the
greater part of it remains in molecular form. As the pressure decreased while
the glass was being formed, the water content in the melt also diminished
(Marakushev et aI., 1988). Consequently, a small quantity (less than 1%) of it can
be found in obsidians in a dissociated form. Study of the isotope ratios (15 18 0,
15 D) indicates that all water in pitchstone is meteoritic in origin. The water was
absorbed by the glass at low temperature.
Lunar volcanic glasses differ radically from terrestrial ones by the absence or
very low content of water and other volatiles (carbonaceous compounds, sulfur
etc.). Volcanic origin was first assigned to the green glass from the regolith
collected by Apollo 15 and the orange glass collected by Apollo 11, and
especially Apollo 17. Lunar volcanic glasses are of basaltic composition and
originated in the period 3.7 x 109 to 3.3 X 109 years ago. Lunar basaltic glasses
are rich in Fe and Ti (1.5 times more than terrestrial ones) and depleted in
alkalies (3-7 times less than terrestrial analogs). Concerning trace elements, a
lack of volatile chalcophiles (Ag, Zn, Cd, Au, Te, Bi) is characteristic (two orders
of magnitude less), but an abundance of refractory elements such as Zr, Hf. High
reduction conditions (partial pressure of oxygen is only 10- 13 in contrast to
10- 8 in terrestrial basalts) are also typical, which is why there is virtually only
Fe 2 + present, and no Fe 3+ . (Here also, Ti3+, Cr2+, Eu 2 + can be found).
Impact Glasses
Impact glasses originated in meteorite craters through thermal fusion of the
target rock, and are more or less affected by evaporization of the parental
material (impact glass proper and tektites) or during impact by a pressure shock
wave (diaplectic glass). Geological data and explosion experiments showed that
the glasses were formed at a striking rate: 17-20 orders more for shock
deformation and 9-11 orders more for thermal process than for magmatic
processes.
Impact glass proper is formed by the rapid melting of the target rocks and
minerals at a high temperature (about 2000C or more) during a short time
period with subsequent solidification of the melt to glass. The melting of
minerals proceeds along fractures, planar elements, and the fault margins of
mineral grains, where the shock pressure and consequently the post-shock
temperature exceeds 1.5-2 times these values in the undisturbed parts of the
grains.
Fusion starts at a shock pressure of 30 GPa (in biotite), but at a pressure of
45-70 GPa practically all rock-forming minerals are melted. Impact glass is
261
either monomineral or polymineral, depending on the number of original

components melted and mixed. The most common representative of the monomineral glasses is quartz glass (lechatelierite; unique pieces of it have been found
in the Zhamanshin crater, Kazakhstan). Other glasses are formed from feldspar,
hornblende and pyroxene.
Polymineral glasses are more typical for astroblemes. They originate from
either one rock or mixed rocks. The former are known to be found in the crater
ejecta (forming at the first stage of impact event) and in suevites of Popigai, Ries,
etc. The glasses formed from mixed melts constitute the layers or deposits in the
bottom facies of the craters. In general, the composition of glasses is rather
similar to the average composition of the surrounding target rocks; but there are
some cases when the composition differs due to the selective volatilization of the
elements (AI, Ti, Mg, Ca, and sometimes K contents increased, while Si and Na
decreased) and also because of the contamination of meteorite matter (the excess
of Ni, Co, Cr, Ir, Os, and other elements).
In contrast to volcanic glass, impact glass is heterogeneous with frequent
inclusions of shock metamorphosed minerals and rocks and a lack of phenocrysts. Impact glass contains grains of fused quartz, baddeleyite, magnetite, and
rutile. Impact glasses sometimes contain tiny beads of metallic iron or gas-liquid
inclusions in which free oxygen is absent and the CO/C0 2 ratio is usually higher
than 1. These factors indicate that the glass was formed under reducing
conditions. Judging from X-ray diagrams, IR-spectra, EPR-spectra, electron
spectroscopy data, low-angle diffraction method and the study of the structure
and sizes of diffusion halos in the glasses around xenoliths, the impact glasses are
recognized to be related to high temperature ( ~ 2000~ 3000 DC) overheated
melts (above liquidus temperature). Accordingly, they are characterized by a
high degree of depolymerization in comparison with the volcanic melts which
originated near the liquidus temperature (700~ 1200 QC). Together with Si0 4 tetrahedrons and their groups, there may be found AI0 4 - and Fe0 4 tetrahedrons as well as less frequent cells with P and Sn. Microheterogeneity in
impact glasses conforms to the groups of only a few tetrahedrons (1.3~2 nm),
contrasting to obsidians, where they are an order of magnitude larger
(14.2~34.5 nm). The differences in the structure of impact and volcanic glasses
remain preserved due to the high rate of impact cooling rising to 1OO~ 200 DC S - 1
as compared with the few degrees per second for volcanic glasses. For impact
glasses this cooling rate gives rise to a divergence between the index of refraction
as measured in immersion and calculated from their chemical composition. The
difference may reach 0.030, and increases in proportion to the temperature of
melt. For volcanic glasses both indexes of refraction are equal.
Diaplectic glasses represent the highest degree of isotropization of crystalline
substances in solid state caused by the shock wave. The shape of the original
crystal or grain boundaries or twin lamellas and cleavage is retained. The shock
wave destroys the mineral structure, but the temperature is lower than the
melting point of the given compound. The crystal matter is transformed by
crushing in blocks of not more than 1000 nm of size. These blocks bear the
262
crystallo-chemical peculiarities of the primary matter, e.g., a diaplectic quartz

glass contains "quartz block crystallites". This is in contrast to quartz glass
formed by thermal fusion consisting of "tridymite crystallites".
Isotropization of quartz occurs in a shock wave of 26-30 GPa (n decreases
from 1.5487 to 1.470) and quartz is converted at a pressure of 35-50 GPa to
diaplectic quartz glass with n = 1.458-1.463. The index of refraction is lower
as compared to the mineral, but higher than that of impact glass of equal
composition formed by thermal melting. Diaplectic glasses develop within the
range of a shock pressure of 15 to 60 GPa. With increasing pressure the glasses
show signs of melting, so that shocked rocks may exhibit evidence of flow at a
pressure of about 45-55 GPa, with nonhomogeneous glasses corresponding to
mixed mineral composition.
Lunar impact glasses are more common on the surface of the Moon and
differ from volcanic ones by certain criteria, e.g., chemical homogeneity within
spherules of volcanic glasses and heterogeneity of impact glasses; the lunar
volcanic glasses have high Mg/AI ratios (more than 1.5; e.g., mafic composition)
and have Mg-correlated abundances of Ni. In contrast to lunar impact glasses,
this latter criterion indicates that these volcanic glasses are free of any meteoritic
contamination. Other criteria also exist, but all are still insufficient to distinguish
between the two types unambiguously.
Tektites
Tektites (Greek tektos = molten) are usually small (their size varying from
microscopic grains - microtektites to 12.8 kg - the Muong Nong type from
Thailand, usually only a few cm long) rounded, natural acidic silicate glasses,
black, brown or green in color, with a high melting point (1320-1640 K). They
are scattered in a number of regions on the surface of the Earth, which are called
strewn fields:
1. North American tektites and microtektites (bediasites, georgianites from
2.
3.
4.
5.
6.
Texas, Georgia, Martha's Vineyard, Barbados, Cuba). Radiometric age

(K;'Ar, Ar/Ar, fission track methods): 35 Ma. Estimated amount: 1010 tons.
Urengoites from Novyi Urengoi, West Siberia, CIS. Radiometric age: 24 Ma.
Amount: (to date only three specimens).
Moldavites from Czech Republic (Radessen and Altenburg, Austria; around
Dresden in Germany). Radiometric age: 14.7 Ma. Estimated total amount:
3000 tons.
Tektites and microtektites from the Ivory Coast (ivorites). Radiometric age:
1.1 Ma. Estimated amount: 10 7 tons.
Irghizites and microirghizites from the Zhamanshin crater, Kazakhstan.
Radiometric age: 0.8 to 1.1 Ma. Estimated amount: dozens of tons.
Australasian tektites and microtektites (australites, indochinites, billitonites,
thailandites, javanites, phillippinites, malaysianites, Muong Nong type).
263
Radiometric age 0.7 Ma. (Asian tektite field) and 0.83 Ma. (Australian tektite
field). Estimated total amount: 108 tons.
Tektites are not known in older geological formations. If older tektites
existed, they were probably destroyed by transport or completely dissolved.
Tektite glass can be divided into four major types: (1) layered Muong Nong type,
(2) frozen droplets from splashed melt, which include spherical and teardrop
shapes, so called shaped tektites, (3) ablation types, mainly in Australia, and
(4) microtektites.
Muong Nong tektites are very similar to normal tektites except for high
intrasample variation, corresponding to chemical layering. Shaped tektites
obtained their shape (sphere, ellipsoid, disc, lens, teardrop, etc.) through rotation
ofthe viscous melt - the splash form. These tektites are usually characteristically
sculptured. The sculpture is a result of chemical corrosion.
Tektites with ablation phenomena (button-shaped) are modified by atmospheric ablation at their rims during remelting as they re-entered the Earth's
atmosphere. The button shape of tektites has also been formed artificially in
aerodynamic tunnels. Microtektites are shaped identically to other shaped
tektites, but are defined as bodies less than 1 mm in diameter. Microtektites are
found in deep ocean sediments (Australasian, North American, and Ivory Coast
microtektites).
The Australasian microtektite layer is associated with the BrunhesMatuyama reversal of the Earth's geomagnetic field, while the Ivory Coast
microtektites are associated with the Jaramillo event. The North American
microtektite layer is probably connected with the Eocene-Oligocene boundary.
Tektite glasses have a fluidal texture and commonly contain particles of pure
quartz glass (lechatelierite) which was formed by fusion of quartz grain. This
substance is absent in all volcanic glasses. The fluidal texture of tektites is
marked by schlieren. Commonly bubbles of different sizes are present. The gas
pressure in tektite bubbles is very low and corresponds to one thousandth to one
twentieth of the pressure of the Earth's atmosphere at sea level. Rare inclusions
(from tens to a few hundred microns in size) usually are formed by quartz,
coesite, baddeleyite (a decomposition product of zircon), zircon, corundum
(probably a decomposition product of AI 2 SiO s), rutile, chromite, and monazite;
occasionally, Ni-Fe spherules containing schreibersite and troilite have been
described as well as an magnetic spherules. These mineral inclusions lie in a
similar size fraction (silt to fine sand) and their original presence in graded very
fine well separated sediments would thus seem possible. Finally such associations as quartz, chromite, and zircon are not found together in any type of
igneous rock. Some of these relict minerals are cracked and show signs of shock
metamorphism. The average values of the density and refractive index of tektites
vary: n = 1.485-1.518, p = 2.335-2.502 g cm - 3.
The chemical composition of tektites manifests a close similarity with the
sedimentary rocks of the Earth's surface. The silica content in tektites is greater
than would be expected on the basis of the mafic oxide content, and thus
264
corresponds more closely to sediments as the source material than to any

igneous rock. They have an excess of Al 20 3 compared to igneous rocks and low
content of alkalies, usually with the predomination of K 20 over Na 20 (ivorites
constitute an exception). Iron is reduced more in tektites (by three to five times)
and thus the (FeO + MgO)/(Na 20 + K 20) ratio is higher compared to granite
or obsidian with the same silica content. The average chemical composition of
tektites and microtektites (n = 458): Si0 2 75.56 wt. %, Ti0 2 0.60 (n = 455),
Al 20 3 12.67, FeO total 4.06 (n = 284), MnO 0.08 (n = 245), MgO 3.18, CaO
2.64, Na 20 1.13, K 20 2.47, P 20 S 0.05 (n = 102). The average chemical composition of tektites is most similar to that of terrestrial surface rocks-clay sediments,
graywackes, sandstones, soil, loess and (or) mixtures of them. The distribution of
trace elements, Ni/Co, Fe/Ni ratios, and especially the isotope characteristics
(0, Pb, Rb, Sr, Sm, Nd, Mg) support this phenomenon. Tektites differ from
obsidians also by being "drier" (H 20 < 0.02 wt. %).
The relation (geochemical, e.g., main elements content, REE elements and
other trace elements distribution, isotopes, petrological and age data) of tektites
with astroblemes (most completely shown for moldavites and the meteorite
crater Ries, ivorites and the meteorite crater Bosumtwi, and irghizites and the
meteorite crater Zhamanshin), the presence of inclusions with signs of shockwave influence, the presence of coesite, a very high melting temperature (up to
2500-3000 0c) and a very rapid rate of cooling - all these factors evidence the
impact origin of tektites from the uppermost layers of the Earth's crust (residual
rocks, sediments, soil), which are always affected by the weathering processes
that had modified the composition of the parental material prior to impact.
Modeling of large impact structures has demonstrated that a rising column
of hot air could carry tektite melt to the upper atmosphere with a very great
velocity. This mechanism can also explain the wide geographical distribution
of tektites in a single strewn field. Nonetheless, it must be admitted that the
mechanism of tektite formation is not yet completely understood because there
is limited knowledge of the environment in which the rocks were exposed to the
high pressure of the shock waves and also of the processes that occurred at high
temperatures in a very short period.
Fulgurites
Fulgurites originate when lightning strikes soil, sand, or rocks, causing melting
of these materials and glass formation when all the material in the immediate
vicinity of the strike site vaporizes. Fulgurites (Latin fulgur = lightning) form
glassy tubes in soil and sands and glassy crusts (1-3 mm thick) in crystalline
rocks. They are exceptionally found up to 20 m long and 20-30 em wide in
sandy deserts. The glass of fulgurite is heterogeneous, with abundant inclusions
and fragments of target minerals bearing marks of shock metamorphism (planar
elements, lower values of birefringence and refractive indices of the shocked
265
minerals, the appearance of coesite). Also identified were native iron, carbon
(chaoite), gold, silicon, aluminum, phosphides, sulfides and silicides of iron, and
other reduced phases (log f02 = - 20 to - 10) which had developed under high
temperature. The structure, temperature, and cooling rate of fulgurite glass are
similar to those of impact glass originated by thermal fusion. The changes in
chemical composition appear on a micrometer scale. Usually the fulgurite glass
is enriched in Si0 2, and K prevails over Na compared to the target rock,
resulting from selective volatilization of the elements, melting at high temperature (up to 3000C and shock pressure of 20-25 GPa) and the short duration
of the whole process. Fulgurites have been produced artificially in sand by an
electric discharge or have been found in nature where high tension electricity
wires have fallen to the ground, i.e., pseudofulgurites.
At the strike of an electric charge of lightning (temperature up to 30000 K
and shock pressure about 0.05 GPa) while traveling from the atmosphere (gas)
to the ground (solid phase) there occurs a decrease in temperature of one order
and an increase of pressure of two to three orders accompanied by melting and
selective vaporization of the target rocks.
References
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Bouska V, Borovec Z, Cimbalnikova A, Kraus I, Lajcakova A, Pacesova M (1993) Natural
glasses. Academia Praha, Horwood Chichester, pp 1-354
Delano JW, Livi K (1981) Lunar volcanic glasses and their constraints on mare petrogenesis.
Geochim Cosmochim Acta 45(11): 2137-2149
Feldman V (1988) Comparative characteristics of impactite, tektite and fulgurite glasses. In:
Konta J (ed) 2nd Int Conf Nat Glasses, Prague 1987, pp 215-220
Fudali RF, Kreutzberger M, Kurat G, Brandstiitter F (1984) Aspects of a glassy meteorite
from the Moon bearing of some problems in extraterrestrial glass-making. J Non-Cryst Sol
67: 383-396
Glass BP (1978) Australasian microtektites and the stratigraphic age of the australites. Geol
Soc Am Bull 89: 1455-1458
Glass BP (1984) Tektites. In: Pye LD, O'Keefe JA, Frechette VD (eds) Natural glasses. NorthHolland, Amsterdam, pp 333-344
Grothues J, Hornemann U, SHiffler D (1989) Mineralogical shock wave barometry: (I)
calibration of refractive index data of experimentally shocked a-quartz. Lunar and Planetary Conf (Abstr) Houston, NASA, pp 365-366
Grieve RAF (1975) Petrology and chemistry of the impact melt at Mistastin Lake crater,
Labrador. Bull Geol Soc Am 86(12): 1617-1629
Marakushev AA, Persikov ES, Bukhtiyarov PG (1988) Endogenic nature ofperlites. In: Konta
J (ed) 2nd Int Conf Nat Glasses, Prague 1987, pp 89-96
Nasedkin VV (1985) Volcanic glasses, their properties and deposits. XVII session ofInt Geol
Congr, Sec 15, Dokl 15, Moscow 1984 Izd Akad Nauk, pp 15-24
O'Keefe JA (ed) (1976) Tektites and their origin. Elsevier, Amsterdam, pp 1-254
Schneider H (1978) Infrared spectroscopic studies of experimentally shock-loaded quartz.
Meteoritics 13(2): 227-234
Taylor HP Jr (1968) The oxygen isotope geochemistry of igneous rocks. Contrib Mineral
Petrol 19: 1-71
266
4.4 Nuclear Waste Glasses: Recent Advances in the

Spectroscopic Investigation of Their Structure
D. PETIT-MAIRE. J. PETIAU. and G. CALAS
High- and intermediate level, long-lived wastes (class I and II wastes: IAEA
1981) result from the irradiation of the nuclear fuel within a reactor and its
subsequent reprocessing. They include the fission products, actinides, and heavy
elements formed in the fuel by neutron capture and radioactive decay reactions.
The largest volumes are produced during spent fuel reprocessing and contain
only about 0.1 % of the uranium and 1% of the plutonium (Roxburgh 1987) and
are referred to as high-level wastes (HL W). HL W need to be contained in an
environment providing an efficient shielding and isolation from biosphere as
well as an efficient dissipation of the heat generated by the radioactive decay of
the waste. At present, most HLW are stored in liquid cooling tanks, though they
are not thought to provide a long-term solution to the disposal of high-level
nuclear waste. The long term disposal option remains deep geological burial,
isolating the waste from the biosphere for the requisite periods of time, mostly
by preventing from transportation by groundwater. Among the main technical
requirements of solidified HL Ware low leachability, high chemical, thermal,
and mechanical stability as well as industrial feasability. A large number of solid
waste forms meet these criteria, and they include glasses, cements, and synthetic
rocks. Nuclear waste glasses of borosilicate composition are now developed at
an industrial scale (Sombret 1985) and we will survey below some recent findings
concerning their structure. Attention has also focused on the use of an artificial
rock, known as SYNROC (Ringwood et al. 1979; Ringwood and Kelly 1986).
SYNROC contains various crystalline phases able to fix some radionuclides: for
example actinides, Cs/Ba and Sr are incorporated into zirconolite, hollandite,
and perovskite phases, respectively.
On account of the high activity and the chemical complexity of glasses
containing HL W products, most studies of the glasses including structure and
leaching rates have been conducted on analogs which are less active and
chemically simpler. Two typical compositions are reported in Table 25. These
Table 25. Composition of borosilicate glasses used for radwaste
Glass
Waste
load'
Si0 2 B2 0
AI 2 0
Li 2 0 Na 2 0 K 2 0
MgO CaO
BaO
Fe 2 0
R7T7 b
14.3
UK-209 c 9.8
45.5
50.9
14
11.1
4.9
5.1
2
4.
9.9
8.3
6.3
, The various waste elements, including fission products and actinides.

b After Godon et al. (1988).
C After Milnes (1985).
0.6
0.4
Others
FeO
2.9
2.7
2.2
1.4
4.4 Nuclear Waste Glasses: Recent Advances in the Spectroscopic Investigation
267
model glasses have been extensively investigated, concerning their physicochemical properties (see, e.g., Sombret 1985). For instance, on account of the
preferential trapping of the heavy elements within the altered layers resulting
from glass leaching, the mechanisms of element retention has received much
attention (God on et al. 1988; Petit et al. 1989; Abrajano et al. 1990). The
dissolution and long-term immobilization of HLW in silicate glasses has given
an impetus for detailed studies of actinide-bearing silicate glasses. Indeed, the
physicochemical behavior of most elements which represent fission products is
known in glasses quite extensively, because they are classical components:
alkalis, alkaline earths, transition elements, lanthanides. On the contrary, the
specific physicochemical behavior of actinide elements has been elucidated only
a few years ago (Veal et al. 1987).
Because the solubility of actinides is strongly dependent upon the oxidation state, quantitative determinations of the redox states occurring in the
borosilicate glasses have been performed, mostly on the inactive U-bearing
glasses (Schreiber and Balazs 1982; see also the extensive bibliography of
Schreiber et al. 1985). Under oxidizing conditions, up to 20 mol% U 308 may be
dissolved in the borosilicate matrix. A major finding concerning the chemistry of
uranium in silicate glasses has been the discovery of the pentavalent state (Calas
1979), which explains the behavior of uranium under intermediate redox
conditions. Actually, the best knowledge on the speciation of uranium in silicate
glasses has been obtained by using synchrotron radiation-based X-ray absorption spectroscopy (XAS) at ULm edge, with complementary data from optical
absorption spectroscopy. XAS encompasses two complementary methods,
namely X-ray Absorption Near Edge Structure (XANES) and Extended X-ray
Absorption Fine structure (EXAFS), which give access to the oxidation state
and site geometry and to the interatomic distances around the selected element,
respectively (see, e.g., Brown et al. 1988, and more specifically in glasses: Calas
et al. 1987, 1988, and 1990). In glasses synthesized under oxidizing conditions,
uranium occurs as uranyl groups UO~ +, with two oxygens at short distances
( ~ 1.8 A) and four to five oxygen equatorial ligands at significantly larger
distances ( ~ 2.2 A) (Petiau et al. 1984; Petit-Maire et al. 1986; Veal et al. 1987).
The geometry of the uranyl group is different from that known in aqueous
solutions and most uranyl minerals, in which the equatorial oxygens are at
larger distance from uranium (generally ~ 2.4-2.5 A). This explains the differences observed in the XANES spectra ofU-bearing glasses and solutions (Petiau
et al. 1986). Using glancing angle XAS, it has been possible to take advantage of
this difference to investigate in situ the leaching of U-bearing borosilicate glasses
(Greaves 1989). Pentavalent uranium occurs in octahedral coordination with
various degrees of axial distortion (Calas 1979, Petit-Maire 1988). Under
reducing conditions, tetravalent uranium is encountered but some disagreement
exists concerning its coordination number: six fold coordination according to
EXAFS (Veal et al. 1987), eight fold coordination according to optical absorption spectra (Calas 1979) or the coexistence of both kinds of sites (Petit-Maire
1988). In nonactive borosilicate glasses, the redox state of uranium in the glass
268
has been shown to have a negligible influence on the leaching rate of this element
(Schreiber et al. 1985).
The local surrounding of the other actinides is only partly known owing to
the diflkulty of investigating highly radioactive glasses. Neptunium is probably
the transuranic element which has received the greatest attention. 237Np
Mossbauer spectroscopy provides an unambiguous way to determine the
oxidation state of neptunium, together with optical absorption spectroscopy
(Veal et al. 1987; Boge et al. 1986; Eller et al. 1985; Karraker 1982). Neptunium is
present under the tetravalent state in glasses equilibrated in air, but may exist in
the pentavalent state as neptunyl groups (NpOi) ou Np3+ions under oxidizing
or reducing conditions, respectively. A comparative EXAFS study (Petit-Maire
1988) of tetravalent actinides (Th, V, Np) has shown that a coordination 6 is
favored as Z increases, in accordance with the decrease of the ionic radius
("actinide contraction"). This systematics is obeyed for Pu 4 + -containing glasses
(Knapp et al. 1984). In the case of the Np3+ ions, EXAFS data are difficult to
analyze on account of an important radial disorder (distance distribution
between 2.4 and 2.8 A). Finally the geometry of the neptunyl group is similar to
that of uranyl groups, with Np-O distances slightly larger than the V-O
distances: the cation-oxygen distance relaxation, despite the similarity of the
ionic radii of V 6 + and Np 5 + is accounted for by the smaller oxidation number
of Np (Petit-Maire et al. 1989).
The spectroscopic investigation of actinides in multicomponent borosilicate
glasses of industrial interest show the importance of the chemical selectivity of
these methods to obtain quantitative information on elements which are
only minor components of these glasses. One of the major conclusion is that
these elements are located in fairly well-defined environments, whatever their
oxidation state. Spectroscopic methods have provided structural models to
explain actinide solubility in borosilicate matrices molten under various redox
conditions (Veal et al. 1987) as well as they have given a coherent model
concerning the processes monitoring glass leaching at low temperature (Greaves
1989). However, the coexistence of various oxidation states makes it difficult to
use model glasses to investigate the actual surrounding of actinides in industrial
glasses used for HLW storage.
References
Abrajano TA, Bates lK, Woodland AB, Bradley IP, Bourcier WL (1990) Secondary phase
formation during nuclear waste-glass dissolution. Clays Clay Mineral 38: 537-548
Boge M, Blaise A, Bonnisseau D, Fournier 1M, Therond PG, Poi rot I, Beauvy M (1986) 237Np
Mossbauer spectroscopy on neptunium doped borosilicate glasses. Hyperfine Interactions
28: 765-767
Brown GE, Calas G, Waychunas GA, Petiau J (1988) X-ray absorption spectroscopy:
applications in mineralogy and geochemistry. Rev Mineral 18: 431-512
Calas G (1979) Etude experimentale du comportement de l'uranium dans les magmas: etats
d'oxydation et coordinance. Geochim Cosmochim Acta 43: 1521-1531
4.4 Nuclear Waste Glasses: Recent Advances in the Spectroscopic Investigation
269
Calas G, Brown GE, Waychunas GA, Petiau J (1987) X-ray absorption spectroscopic studies
in minerals and glasses. Phys Chern Mineral 15: 19-29
Calas G, Manceau A, Petiau J (1988) Crystal chemistry of transition elements in minerals
through X-ray absorption spectroscopy. In: Synchrotron radiation applications in mineralogy and petrology. 77-95, Teophrastus Sub., Athens
Calas G, Manceau A, Combes JM, Farges F (1990) Applications of EXAFS in Mineralogy. In:
Mottana A, Burragato A (eds) Absorption spectroscopy in mineralogy. Elsevier, New York,
pp 171-204
Eller PG, Jarvinen GD, Purson JD, Penneman RA, Ryan RR, Lytle FW, Greegor RB (1985)
Actinide valences in borosilicate glasses. Radiochim Acta 39: 17-22
Godon N, Thomassin J, Touray J, Vernaz E (1988) Experimental alteration of R7T7 nuclear
model glass in solutions with different salinities (90C, 1 bar): implications for the selection
of geological repositories. J Mater Sci 23: 126-132
Greaves GN (1989) EXAFS, glass structure and diffusion. Philos Mag B60: 793-800
IAEA (1981) Underground disposal of radioactive wastes, Basic Guidance. IAEA Safety
Series, No 54, Vienna
Karraker DG (1982) Actinide valences in borosilicate glass. J Am Ceram Soc 65: 53
Knapp GS, Veal BW, Paulikas AP, Mitchell AN, Lam DJ, Klippert TE (1984) EXAFS study
of sodium silicate glasses containing dissolved actinides. In: Hogdson KO, Hesnner Band
Penner-Hahn JE (eds) EXAFS and near edge structure. Springer Proc Physics 2: 305-308
Milnes AG (1985) Geology and radwaste. Academic Press, London
Petiau J, Calas G, Dumas T, Heron AM (1984) EXAFS and edge studies of transition elements
in silicate glasses. Springer Proc Phys 2: 291-296
Petiau J, Calas G, Petitmaire D, Bianconi A, Benfatto M, Marcelli A (1986) Delocalized versus
localized unoccupied 5f states and the uranium site structure in uranium oxides and glasses
probed by X-ray absorption near edge structure. Phys Rev B34: 7350-7361
Petit JC, Dran JC, Trotignon L, Casabonne JM, Paccagnella A, Della Mea G (1989)
Mechanism of heavy element retention in hydrated layers formed on leached silicate glasses.
In: Lytze W (ed) Scientific Basis for Nuclear waste management XII, Mater Res Soc Symp
Proc 127: 33-40
Petit-Maire D (1988) Structure locale autour d'actinides et d'eU:ments nucleants dans les verres
borosilicates d'internh nucleaire: resultats de spectroscopie d'absorption x. Thesis, Universite Pierre et Marie Curie, Paris 6
Petit-Maire D, Petiau J, Calas G, Jaquet-Francillon N (1986) Local structures around
actinides in borosilicate glasses. J Phys 47-C8: 849-852
Petit-Maire D, Petiau J, Calas G, Jaquet-Francillon N (1989) Insertion of neptunium in
borosilicate glasses. Physica B158: 56-57
Roxburgh IS (1987) High level nuclear waste disposal. An introduction. Chapman and Hall,
London
Ringwood AE, Kelly PM (1986) Immobilization of high-level waste in ceramic waste forms.
Philos Trans R Soc Lond Ser A 319: 63-82
Ringwood AE, Kesson SE, Ware NG, Hibberson W, Major A (1979) Immobilization of highlevel nuclear wastes in SYNROC. Nature 278: 219
Schreiber HD, Balazs GB (1982) The chemistry of uranium in borosilicate glasses. Part 1.
Simple base compositions relevant to nuclear waste immobilization. Phys Chern Glass 23:
139-146
Schreiber HD, Balazs GB, Solberg TN (1985) The chemistry of uranium in borosilicate glasses,
part 6. The leaching of uranium from glass. Phys Chern Glass 26: 35-45
Sombret CG (1985) The vitrification of high-level radioactive wastes in France. Nucl Energy
24: 85-98
Veal BW, Mundy IN, Lam DJ (1987) Actinides in silicate glasses. In: Freeman AJ, Lander GH
(eds) Handbook Phys Chern Actinides, Elsevier, Amsterdam, pp 271-309
CHAPTER 5
Chemical Bonding in Minerals
Chapter 5. Chemical Bonding in Minerals
272
5.1 Survey of Quantum Chemistry and Methods Used to

Calculate the Electronic Structures of Minerals
S.P. DOLIN and D.M. SHERMAN
In recent years there has been a rapid growth in the applications of computational quantum chemistry to mineralogy. Band structure and molecular orbital
calculations are being used to understand mineral spectra, equations of state,
and crystal structures. In this survey various computational methods used to
study the electronic structures of molecules and solids are briefly reviewed.
The electronic structure of an atom, molecule, or solid is given by the
solutions to the time-independent (stationary) Schrodinger equation
Ap = EP,
(1)
where A is the Hamiltonian operator, P is the wavefunction of the system and

E is the total energy. First, we will assume that it is sufficient to use the
nonrelativistic approximation, so that the total Hamiltonian A tot in Eq. (1)
comprises the kinetic energy T of nuclei (n) and electrons (e) as well as their
potential energy V, and only the Coulomb interaction between charged particles
is taken into account
(2)
Second, we will assume that the electron motion may be considered separately
from the nuclear motion (Born-Oppenheimer approximation). Our electronic
Hamiltonian will then be A(e) = A tot - Tn. An eigenfunction of this operator
[the total electronic wavefunction, p(e)] describes electron motion in the field of
the motionless nuclei, while the eigenvalue, E(e) is the total energy of the system
with a particular nuclear configuration or adiabatic potential. It is the electronic
Schrodinger equation f!<e)p(e) = E(e)p(e) in the simple adiabatic approximation
that is solved in the methods reviewed here.
Hartree-Fock Formalism
The Independent Electron Approximation. We are still faced with the dilemma
that our electronic SE is a many-body problem. When solving a differential
equation for a function of several variables, it is a common strategy to try and
express the solution in terms of the product of functions of only one variable.
For the multielectronic Schrodinger equation, this approach was used by
Hartree, who expressed the multielectronic wavefunction in terms of the product
of one-electron wavefunctio!ls:
(3)
where ri is the coordinate of electron i. Hartree's trial wavefunction, however,
5.1 Survey of Quantum Chemistry and Methods
273
violates the Pauli exclusion principle which requires that the wavefunction must
be anti symmetric under electron exchange (that is, the wavefunction must
change sign when any two electrons are interchanged). Algebraically, we can do
this if the wavefunction takes on the form of a linear combination of determinents over the one-electron orbitals. In the case of an N-electron closed shell
system (Na = Np = N/2 where ()( and f3 refer to spin-up and spin-down), P (index
"e" omitted) is a single determinant of one-electron orbitals, each of which must
not be occupied by more than two electrons (the certain occupation of these
levels defines the electronic configuration)
(4)
The Variational Principle and the Fock Equations. If Ptrial is any antisymmetric
trial wavefunction, then one can evaluate an expectation value for the total
energy associated with that wavefunction
Etrial = < Ptriad B I Ptrial) == JP*B P dr,

where dr means we integrate over all space. If P is the correct wavefunction,
then Etrial = E. However, if P is any other normalized, anti symmetric wavefunction, the variational principle states that Etrial > E. Hence, we can improve our
trial wavefunction by minimizing the total energy. If we take the single determinental wave function and substitute it for P(rl' r2, ... , rN) in the electronic
Schrodinger equation, we generate an expression for the total energy
E = <PIBI P) =
L>d cPr(1)h1cPi(1)drl
+ Li<j nind cPr(1)cPj(2)r~2[cPi(1)cPj(2)
- cPj(1)cPi(2)] dr l dr2.
(5)
Now, we use the variational principle to minimize the total energy with respect
to each one-electron orbital subject to the constraint that the orbitals are
orthonormal. Doing this yields a set of simultaneous equations for the oneelectron orbitals known as the Hartree-Fock equations:
(6)
In Eq. (6) F is the Fock operator defined through the MOs; Gi is the one-electron
energy level, h = Te + Vne ; the Coulomb Jj and exchange Kj operators are
related to the operator Vee = Li> jriJ 1 and define the contributions to the
effective SCF potential from the electron-electron interaction.
The Linear Combination of Atomic Orbital (LCAO) Approximation. For an
atom, we can solve the Hartree-Fock equations and obtain numerical atomic
274
orbitals. These can then be fit to some analytic form (such as Slater or Gaussian
orbitals discussed below). For a molecule or crystal, a natural way to construct
the one-electron molecular or crystal orbitals is to express them as a finite linear
combination of atomic orbitals (LCAO):
(/l
1, 2, . . . , L).
(7)
Each of Xli is an atomic orbital centered on one of the nuclei of the molecule. The
one-electron orbital formalism has dominated the theoretical study of the
electronic structure of atoms, molecules, and solids. Not only is it used in
calculations of physical observables but it also provides the "language" to
describe electronic structures and chemical bonding.
We can use the variational principle again to solve for the coefficients C ili of
the atomic orbitals. This gives the set of SCF LCAO MO equations
L
L(F liv - EiSliv)Civ
0,
(8)
Ii
where the elements of the Fockian F and overlap S matrices are defined in terms
of the LCAO basis {Xli}
Fliv = Hliv + GliV ;

SliV = <X~l) IX~l),
(9)
(to)
where
(11 )
(12)
(13)
The large number of two-electron integrals [/lV IAt5] limits the size of practicable
calculations. The summation in Eq. (8), which is limited by occupied MOs only,
yields the density matrix: PA~ = 2L~ccCiACi~' Equation (8) is solved iteratively
since the matrix F itself depends upon unknown MOs (or upon unknown C ili in
the LCAO approximation). The MOs obtained from the solution of Eq. (6) are
called canonical. The restricted HF method (RHF) described above is usually
employed in such form for closed-shell systems, when the nuclear configuration
does not strongly differ from that at equilibrium.
Open-Shelled Systems: Restricted Hartree Fock (RHF). The many-electron
wavefunction P can be written in a single-determinant form not only in the case

of a closed shell but also in the case of a half-filled shell (when the microstate is
that which has the maximum magnetic spin quantum number; the energy of this
microstate will be the same as that of the term with maximum multiplicity
275
arising from the configuration). For such configurations one can make use of
RHF algorithm for open-shell systems developed by Roothaan. Here eigenfunctions and eigenvalues for closed- (<Pd, Bd) and open- (<p .. lOs) shells are found from
the system of coupled SCF equations:
Fd<Pd = Bd<Pd;
(14)
Fs<Ps = Bs<P ..
(15)
where the operators Fd and Fs depend not only on the open-shell type but on the
off-diagonal Lagrange multipliers as well. The MOs obtained through Eq. (14)
are not generally orthonormal and cannot, therefore, be used in CI refinement
(vide infra).
There are several modifications of the open-shell RHF method. In the
partitive HF (PH F) scheme the eigenvector spectrum can be produced from
three coupled equations:
+ I~ (2Jd - K d) +
~
L
( JS - -1 KS ) (d + v)
(16)
d= 1
s=N,+ 1
2
N,
N.
(P - KS)(s + v)
F'v = h +
(2Jd - K d) +
(17)
d=l
s=N,+ 1
N,
N.
Fdv = h +
(2Jd - K d) +
(18)
J'(d + s),
d=l
s=N,+l
which are obtained using the energy stationary criterion found with variation
mixing of the double (d) and single (s) occupied and virtual (v) MO subspaces.
These operators are not diagonal in the complete space dis/v, but each operator
is diagonal in own subspace. The effectiveness of the PHF appreciably increases
if instead of Eq. (12) one makes use of the single FPHF where
Fdv = h
F PHF = Hllv
+ I PH {[,uv lAb] AO
P H ~ P10 + P~o.
~ [,uA IVb]};
2
(19)
(20)
This substitution is not justified in every case. Predominantly in cases such as

nondegenerate radicals and certain biradicals, the FR and F PHF solutions are
quite close to each other and the differences can be considered as a result of
interaction between "halfs" of electron with (J. and f3 spins on <Ps (of the radical).
Using this method one can make correct estimates of the vertical ionization
potentials (IP) evaluated as a difference between the ionized and initial total
energies corrected by suitable manner. Other generalizations and simplifications
of the open-shell RHF have not been widely used in systematic calculations.
They are usually employed only for probing of a trial algorithm on certain
molecular systems.
Open-Shell Systems: The Unrestricted Hartree-Fock (UHF) Method. The electronic structures of open-shell molecules and ions can be treated in the
276
framework of the unrestricted HF approximation as well, where the Slater

determinant's more general form is used for the total wavefunction:
tp(1,2, ... , N)
dl)a
N(1)a
1 (1){J
N(1){J
1 (2)a
N(2)a
1 (2){J
N(2){J
dN){J
N(N){J
..
1(N)a
N(N)a
(21)
Here the spatial parts of any electron "pair" with opposite spins are generally
different (hence the understanding of "different orbitals for different spins"). As
before, we substitute this determinental wavefunction into the Schrodinger
equation and use the variational principle to minimize the total energy with
respect to the one-electron orbitals. Here, however, we obtain two sets of
coupled equations:
t (1j + 1; - Kj) ] i = ii
~ = [ h + t + 1f - Kf) ] ~ ~ ~
Pi = [ h +
FP
(Jj
(22)
(23)
or in the LCAO approximation

L
L (F~v -
iSllv)Civ =
L (F~v -
~SIlJC~v
= 0,
(24)
(25)
where if No #- N p, then i #- ~ and 1 #- ~. Although the MOs from Eqs 22

and 23 are the eigenvectors of different operators, they do form an entirely
orthonormal set.
The tpUHF from Eq. (21) is an eigenfunction only for the Sz operator, but not
for S2, because it contains an "admixture" of components of higher multiplets
(e.g., quartet etc. for doublet term) and therefore cannot be used (strictly
speaking) to describe real spectroscopic states. This drawback can be removed
by projection operator technique allowing us to eliminate these components
from the tpUHF and to produce "projected" tp~UHF with corresponding given
S-value:
(26)
where the projection operator
P_
S2 - L(L + 1)
- L"SS(S+ l)-L(L+ 1)
(27)
In most cases the elimination of the component with maximum magnetic
277
spin quantum number is a fairly reliable approximation. This method of obtaining the projected function is referred to UHF with annihilation of (S + 1)
component.
Although the p~UHF is an eigenfunction of the 8 2 operator, it is not necessarily an eigenfunction of the symmetry operators of the system (that is,
p~UHF does not transform as an irreducible representation of the symmetry
group of a molecule). There is as yet no general method for simultaneous spatial
and spin projection. Moreover, the p~UHF (as the p~UHF) produced by the
projection procedure does not correspond to minimum of energy. The correction of this shortcoming by using a variational energy minimization with
a many-determinant p~UHF results in the wave function of the extended HF
method. However, because of its cumbersome nature, the extended HF method
is not generally used.
As mentioned above the p~UHF (pAUHF) is a many-determinant function and
certain parts of correlation energy are accounted for by these methods (as in the
UHF). It should be noted, that the lowering of a total energy in passage from the
pUHF to the pEHF is accompanied by more accurate consideration of molecular
symmetry, i.e., symmetry properties of total wavefunction (Fig. 61).
Correlation Methods. In the unrestricted Hartree-Fock theory, we are including
correlation between electrons with the same spin (the correlation described as
a Fermi hole). What we are not including is the correlation between electrons
with opposite spins (the so-called Coulomb hole). It is this correlation that one
attempts to account for in the methods reviewed below. Moreover, the "correlation energy" will be taken to mean the energy gained by inclusion of the
Coulomb hole. Neglecting this correlation is what gives the wrong behavior
when molecules are disassociated. Figure 61 shows the different components of
the electronic correlation.
There are two aspects of the correlation problem. The first is a qualitative
one, when one may account for effects that cannot be described using an
independent particle models (Van der Waals interaction, exciton states in solids,
etc.). The second is a quantitative one, when the correlated wave function results
in more accurate properties under consideration (bond and ionization energies,
barriers, etc.), that sometimes leads to unexpected qualitative conclusions.
The configuration interaction (CI) approach is one of the most wide-spread
correlation methods. Here the multielectronic wavefunction is described in the
form of a linear combination of determinants:
pCI
CocP o + L CkcPk[P(j)],
k
(28)
where each of the determinants corresponds to a certain electronic configuration

and has the right symmetry. Excited configurations are usually composed of
virtual MOs obtained from the calculation of the ground state (cPo), whereas the
coefficients C k are determined from the secular equation:
detlH kl - ESkl1
0;
(29)
278

E
EH
Fig. 61. Energies of different

methods of Hartree-Fock theory
(arbitrary scale). EH the Hartree
method energy; Enonr the nonrelativistic energy; Eexp the experimental value; E~on the Fermi
correlation energy; E~orr the
Coulomb correlation energy.
Ecorr
E~orr
- - - -
(30)
It is particularly important to take CI into account when considering open-shell
systems or excited states, because in such cases there are configurations with
nearly the same energies that mix together.
The CI procedure involves several stages, among which the stage of configuration selection (usually in basis of canonical, rarely of localized MOs) is
particularly important. Because of great computational difficulties, which occurs even in the case of small molecules, different ways to the number of terms in
Eq. (28) are used instead of the CI with complete (valence) active space of
orbitals. The iterative procedure with the pseudo natural orbitals, as well as
using the multi-reference configurations resulting in correct disassociation
limits, are probably preferable in practical calculations. Different selection
279
criteria (based on energetics or excitation multiplicity) are used. Usually the

single and double, rarely the triple and quadruple (the latter by means of
Davidson's formula) excitations are included in the expansion (28). Some extrapolation procedures are very useful in the correlation calculations, which allow
the limited values of the correlation energy to be estimated with all configurations of given type relative to selected reference configurations is taken into
account) using several basic calculations with restricted configurational set. The
problem of the configuration selection is at present far from being solved. The
available experience of the CI calculations shows that the use of a great number
of configurations (10 6 ) instead of the careful selection of the most important of
them ( ~ 10 3 - 104 ) is not always justified.
Another widely applied correlation method is the multi-configurational SCF
technique (MC SCF). In this method, in contrast to CI, the variational principle
is used to simultaneously optimize the coefficients of Eq. (28) as well as the
LCAO ones of Eq. (7). The quadratic Newton-Raphson optimization procedure
is generally used and the fulfillment of the orbital orthogonality conditions
during optimization process is provided with exponential transformations.
When the number of members in Eq. (28) is sufficiently large, the MC SCF can
be considered as a direct way of solution of the correlation problem. However,
we are still faced with the great computational problem of configuration selection. This has led to several schemes: for diatomics with simple bonds the
double-configuration scheme is used and for these with multiple bonds one
needs the optimized valence configurations scheme. There are several other
schemes in the frame of the MC SCF (e.g., complete active orbital space). This
method has been applied in practical calculations not only for diatomics.
Generally it provides the balanced description various electronic states and
physical properties (ionization and excitation energies, disassociation limits,
dipole moments, etc.).
The Moller-Plessett perturbation theory is one of the simple ways to obtain
an approximate solution of the correlation problem. In this method the multielectronic wavefunction takes the form
pMP
= Co tPbUHF)
+ L Ci tPi +
i,a
L Cit tPi + ... ,

jb
(31 )
i<j;a<b
Where the tPo is defined by Eq. (21) and the tPk are obtained from the tPo via
substitutions i --+ ., j --+ b etc. The use of perturbation theory (to second
order) results in the MP2 expansion of the total energy:
E=(tPoIHltPo >+
L (tPo IHltPi >2 + ... ,

i<j;.<b ei + ej - e. - eb
j
(32)
where the terms beginning from the second relate to the correlation energy. The
results of calculations depend on the order of the perturbation theory, the kinds
of electron excitations and the chosen active orbital space. Usually for mediumsized molecules the MP2 with single and double excitations and valence active
orbital space yields more than 50% of the correlation energy.
280
The search for effective correlation methods is one of the most intense
activities in the development of quantum chemistry. Additional correlation
methods being used include:
Group orbital method, particularly, geminal models, based on dividing of
the N-electron system onto weakly interacting groups of electrons.
Coupled pair and coupled cluster approximations (CPA, L-CPMET, CEPA,
MR CC, etc.), based on dividing of the N-electron system onto subsystems of
less sizes, but without dividing onto weakly interacting subsystems.
Methods based on the valence bond theory taking into account many
"resonant" structures.
Many-body perturbation theory (MBPT) or diagrammatic perturbation
theory (DPT). This approach is the basis for effective analysis of various
correlation methods for atoms and molecules. Moreover, it is used to develop
working schemes of calculations.
The DPT gives the clear ordering parameter for expansions of wavefunction
and corresponding eigenvalues, providing with the least biased estimate of
relative importance of different components and unambiguous criteria of limited
expansions.
Basis Set Functions. The accuracy of the nonempirical (ab initio) calculations
mentioned above depends not only on the specific method applied but also on
the "completeness" of the AO basis set. Basis sets may be "minimal" (i.e.,
includes only AOs occupied in ground states of atoms) or extended (i.e., includes
additionally external AOs). Atomic orbitals can take two analytical forms in
routine calculations: the Slater-type orbitals (STO) with the radial parts
R~~P '" ro-Ie-~r (and angular parts in a form of spherical harmonics, Y1m(lj, )
are used in studies of atoms, diatomic molecules, and linear polyatomic molecules. In the general case of polyatomic molecules, however, Gaussian-type
functions are used: R~Y '" ro-Ie-ar2. The form of the Gaussian-type orbitals
simplifies the computation of molecular integrals; in particular, evaluating the
many-center integrals becomes much easier.
A major drawback of the GTFs is their wrong behavior at r -+ 0 and
r -+ 00. Instead of replacing the Slater-type orbitals with a single Gaussian,
therefore, one typically replaces the STO by a finite expansion of Gaussians
xSTO(r,O =
L CkxrTF(r,
(Xk),
(33)
where the numerical parameters C k and (Xk are determined by, e.g., least-square
fitting the STO. It is desirable, or course, to use wide expansions, particularly,
when the double or polyexponential STO sets as well as the HF AO bases are
approximated. Expansions that are too elaborate, however, will make the
calculation impracticable. It is very common to see STO's expanded in terms of
three gaussians (the STO-3G scheme). However, this basis set is too simple to be
very reliable. We can greatly improve the flexiblity of the valence electron
orbitals by using a "split valence shell". This represents the outer valence shell by
281
two (or more) independent gaussian expansions. Consider, for example, an

oxygen atom with configuration 1s2 2s 2 2p4. We could represent the Is orbital by
a single function made up of 6 Gaussians. The 2s and 2p orbitals might each be
made up of two functions, say one of 3 Gaussians and the second of only
1 Gaussian. In the nomenclature used, this would be called a 6-31G basis set.
Many variations on this approach are possible and one will see 4-21G, 3-21G
etc. basis sets used. Variational flexibility of any basis set can be improved by
adding to it polarization functions (corresponding to AOs unoccupied in ground
states of atoms, such as d-orbitals for silicon, p-orbitals for hydrogen) and
diffuse functions [usually s- and p-types, rarely d- and f(g)-types].
It can be expected that the total wavefunction and energy obtained will be
close to HF limit, when the basis set is sufficiently complete (Fig. 62). The basis
set "completeness" is an important consideration in correlation calculations as
well. Moreover, the error due to basis set "incompleteness" is generally greater
than that due to limited expansion of the total wavefunction or energy and
cannot be compensated by summation of higher order perturbation terms.
Experience with molecular calculations suggests that the error due to basis set
incompleteness is more important for the calculation of physical properties
(e.g., dipole moments) rather than for the total energy.
The problem of basis set completeness is complex. It would be helpful to
have a systematic understanding of how a property converges with the chosen
HF with 'minimal' basis set
HF with 'extended' basis set

HF limit
Correlation calculation with limited basis set
_____
Eexp
Fig. 62. Effects of basis set in the

Hartree-Fock and correlation
calculations (arbitrary scale).
(Wilson, Electron Correlation in
Molecules, Clarendon Press,
Oxford 1984)
282
basis set. At present, the choice of basis set is largely up to the art and intuition
of the investigator and the amount of computer memory and time available.
Density Functional Theory
Density functional theory underlies most currently used methods applied to the
electronic structures of solids. The formalism is based on a theorem by Hohenberg and Kohn (1964), which states that the total energy of a many particle
system can be expressed in terms of the ground state single-particle charge
density, p(r). Hohenberg and Kohn (1964) also showed that the total energy
assumes its minimum value (the ground state) for the correct charge density.
Consider the Hamiltonian for an n-electron system in some external potential V:
(34)
H =T+ U + V,
where T is the kinetic energy, U is the interelectronic potential. For an atom, the
external potential V would be the potential due to the electron-nucleus interaction. In terms of the charge density, p(r), we can write the total energy as
E[p(r)]
= T[p(r)] + U[p(r)] + fV(r)p(r)dr.
(35)
T[p(r)] is the kinetic energy of a set of interacting electrons. Consider now a set
of noninteracting electrons with kinetic energy To[p(r)] in some external
potential V(r)
E[p(r)] = To [p(r)]
+ fV(r)p(r) dr.
(36)
If we minimize the total energy with respect to the charge density p(r) subject to
the constraint that the total number of electrons is constant, we obtain a set of
one-electron Schrodinger equations:
[ - V 2 + V(r)]cl>i(r)
= Bjcl>i(r).
(37)
The charge density in this case is then given in terms of the one-electron orbitals
p(r) =
L nd (/>;(rW,
(38)
where nj is the occupancy of orbital i. What is significant is that this can be done
for a noninteracting set of electrons in any external potential V (r). This led Kohn
and Sham (1965) to express the total energy of the interacting system in terms of
the kinetic energy of a fictitious non interacting set of electrons and an "exchange-correlation" energy
E[p(r)]
= To[p(r)] + (1/2) If 2p(r)p(r')/ Ir - r'l drdr'

+ Exc[p(r)] + fV(r)p(r)dr
= To + fVext(r)p(r) dr.
(39)
The second term is the classical Hartree contribution to the interelectronic
283
potential. The third term is the "exchange-correlation" energy and includes the
difference between T and To together with the nonclassical (exchange) part ofU.
If we use the variational principle and minimize the total energy with respect to
the charge density, we obtain the Kohn-Sham equations
{ - V2
+ S2p(r)/ Ir -
r' Idr'
+ v(r) + vxc(r) }(r) = ei ;,
(40)
where Vxc is the exchange-correlation potential defined as

d Exc [p(r) ]/dp.
(41)
If we knew Exc[p(r)] or vxc(r), we could express the exact solution for any
system in terms of single-particle (one-electron) functions i. Note that the

"one-electron" functions i do not really correspond to the electrons in the
system, but instead to fictitious quasielectrons that do not interact with one
another. The orbital energies actually correspond to the chemical potentials of
these quasielectrons. In practice, the distinction between the real electrons and
the fictitious quasi electrons is ignored.
The Local Density Approximation. Thus far, everything we have done is "exact".
Unfortunately, Exc is unknown and it contains the whole complexity of the
many-body problem. On the other hand, Exc is much smaller than either the
kinetic energy or the Coulomb energies. A reasonable approximation to
Exc might allow one to do accurate electronic structure calculations. A common,
and practical, approach to evaluating the exchange-correlation potential is to
start with the local density approximation
(42)
where exc is the exchange-correlation energy density. In the local density approximation, we assume that the inhomogenous charge density of the interacting
system can be broken up into infinitesimal regions of constant (homogenous)
charge density. This is exact in the regime of slowly varying charge densities. The
reason why this approximation is useful is that there are stochastic models for
the behavior of a homogenous gas of electrons and these can be used to derive
analytic expressions for the exchange-correlation energy density. Below, we will
derive the simplest form of the local density exchange-correlation potential.
However, a number of other analytic forms for the exchange-correlation potential have been proposed, the most commonly used being that of Hedin and
Lundquist (1971). In passing, note that we can extend the density functional
formalism to a spin unrestricted one by defining separate charge densities for
spin-up and spin-down electrons. In conjunction with the local density approximation, the resulting theory is often referred to as the local spin density (LSD)
formalism.
The XCI. Approximation: Relation Between Hartree-Fock and Density Functional

Formalisms. The simplist local density exchange-correlation potential, is the XCI.
potential. This was originally derived by Slater as a statistical approximation to
284
the Hartree-Fock exchange term. We can show, however, how the XIX potential
and the local density approximation relate to the Hartree-Fock formalism in
a more general sense. We will do this in the spin-unrestricted formalism.
Let us start with spin-up and spin-down charge densities
p"(r)
= L nf4>f(l)4>i(l)
i
pP(r)
(43)
= L nf4>f(l)4>i(l).
i
We can write the Hartree-Fock total energy in terms of the charge density
(44)
where
(45)
The exchange potential can be expressed in terms of an "exchange charge

density"
p~(l, 2)
= -
L n~nj4>t(1)4>j(2)4>i(2)4>j(1)/p"(1),
ij
(46)
so that
(47)
The exchange charge density has several properties that help clarify its physical
meaning: First,
(48)
The exchange potential U XHF , therefore, serves to correct the coulomb potential
for an electron's interaction with itself. If we integrate the exchange charge
density over all of the coordinates of electron 2, we find
Jp~(l, 2)dr2 =
- 1
(49)
This means that the exchange charge represents an electron hole of charge + 1
that follows the electron and defines a region of space where electrons of the
same spin are excluded. This electron hole is often called a Fermi hole.
The local density approximation is that we can express our exchange charge
density in terms of the charge density of a single electron and a function which
describes the shape of the Fermi hole:
(50)
285
For the case of a free-electron gas, we can calculate U~HF(l) exactly and hence
we can calculate p~(1, 2) and the shape function exactly. We then find that
U~HF(1 )(free
- electron)
3
J1 /3
6 [ 4n pa(l)
(51 )
Although this is for a free-electron gas, we can also apply it to atoms if we

introduce a scaling factor a:
(52)
The a parameter is chosen so that the total energy of the free atom is the same as
the Hartree-Fock value. This approximation of the exchange potential results in
the Hartree-Fock-Slater (HFS) equations [cf. Eq. (4)]:
(53)
where VXa = (2/3)U xa . We can solve the HFS equations for a molecule or solid
using the LCAO approach as before. However, now that we have expressed
everything in terms of the charge density, we are liberated from using an
analytical expansion of the one-electron orbitals. Moreover, we can simplify the
geometry of the crystal or molecular potential to a "muffin-tin" form.
The Muffin-Tin Approximation and the Multiple-Scattered Wave Method. The
Multiple Scattered Wave (or SCF-Xa-SW) method of Johnson (1973) arose out
of the tradition of solid state physics and is basically the same as the Green
Function or KKR method of band theory (Korringa 1947; Kohn and Rostoker
1954) but without the periodic boundary conditions. It differs, therefore, from
other molecular orbital methods in using the scattered wave formalism instead
of the linear combination of atomic orbitals (LCAO) approach. However, the
conceptual utility of the LCAO formalism is retained in the scattered wave
method since each molecular orbital is an expansion of partial waves hl(K I rj)
with definite angular momemta I centered on specific atoms j. The SCF -Xa-SW
method is orders-of-magnitude faster than the Hartree-Fock LCAO approach.
Consequently, the very large systems of interest in mineralogy (such as
transition-metal oxide and sulfide clusters) can be investigated. A number of
applications of the SCF-Xa-SW method to minerals are reviewed later in this
chapter. Because of its practical and conceptual importance, it is worthwhile to
give a brief outline of the Scattered Wave formalism and the muffin tin potential.
Here, the space within a molecule or solid is divided into atomic spheres
centered about each atom. Within each atomic sphere, we set-up an initial radial
potential for the region from the charge densities of the free ion or atom. The
Coulomb potential is evaluated by solving Poisson's equation to give
- 2Z
Vc(r) = - - + (l/r) S~ 4nr,2 p (r') dr' +
r
S;' 4nr'p(r') dr',
(54)
286
where Z is the nuclear charge and r is the electron-nuclear distance. The

exchange potential is expressed in terms of the charge density using the XC( or
other local density approximation. The potentials from the different atoms are
then superimposed to give an initial molecular (or crystal) potential. The
potential (coulomb or exchange) within each atomic sphere j is then
Y(rj) = yj(rj) +
in
(55)
yi(lri-Rijl),
where Rij is the i-j internuclear distance. Within each atomic sphere, the
potential resulting from the superpositioning is spherically averaged. The general solutions to the SE within each atomic sphere j is then
1m
(56)
'Pj(r) = I e!mR!(K; r)Ylm(rj),
where R!(K: r) is the solution to the the radial Schrodinger equation within the
atomic sphere
~~I'z dr
~ + 1(1 r2+ 1) + yj(r)
+ yj(r)
c
x
[ -- r2 dr
KZJRj(K' r) = 0
I
(57)
and Y1m(r) is the spherical harmonic with angular quantum number I and
magnetic quantum number m (where m takes the values - 1, ... , + I).
In the region between the spheres, the superimposed atomic potentials are
averaged over the interatomic volume to give a constant potential. For a negative constant potential, we can express the solution in the interatomic region as
a linear combination of spherical Hankel functions:
'Pint =
jim
A!mh,(Klrjl)Y'm(rj),
(58)
where j denotes the jth atom and h,(K I rj I) is a spherical Hankel function
centered at atomic site j. To obtain the molecular (or crystal) orbitals, we require
that the atomic and interatomic solutions and their first derivatives be continuous at the sphere boundaries. This is done by setting the "Wronskian" to zero
at each sphere boundary j:
(59)
This generates a set of simultaneous equations for the coefficients elm and A!m.
Finding the zeros of the corresponding determinent gives the molecular orbitals
and their energies. However, to set up the equations, we need to express the
partial waves h,Krj in terms of a single atomic center i. This is done using the
expansion theorems in Johnson (1973).
Non-Muffin-Tin-Based Density-Functional Methods. One apparent drawback of
the muffin tin potential, at least for small clusters, is the poor prediction of total
287
energy as a function of geometry. Several methods, therefore have returned to

the atomic orbital basis set approach but have retained the useful XOC or other
local-density exchange potential. In the Discrete-Variational XOC method, the
matrix elements F /lV and S/lV are evaluated numerically over a representative
point network (using a positive weight function). This enables one to use any
basis sets, in particular, that of the numerical HF AO. Chosen basis set can be
expanded by any number of polarization and diffuse functions.
In the LeAO Xoc approach, one uses a series expansions of the numerical
electron density and exchange potential in analytical fitting functions
p(r) =
L aj fj(r)
j
Vxa(r)
= L bjgj(r),
(60)
where the coefficients aj and b i are found by least-squares fitting on each step of
the iterative procedure.
Orbital Energies in the Local-Density Approximation. A comment should be
made about the meaning of the one-electron orbital energies. In the HartreeFock approximation, the one-electron orbital energies obey Koopman's
theorem which states that
(61)
so that orbital energies correspond to ionization energies. In the local density

approximation, orbital energies have a somewhat different meaning:
(62)
where nj is the occupancy of orbital i (fractional occupancies are allowed in the

local density approach). Slater showed that we can calculate electronic
transition energies using the transition state formalism. For a transition between
two electronic configurations A and B,
(63)
e:
where s is the energy of orbital i in the configuration halfway between that of

A and B. The transition state procedure allows us to account for orbital
relaxation during the electronic transition.
Semi-Empirical Methods
The computational difficulties involved in calculations of complex molecular
systems have resulted in various approximations to reduce the number of
required integrals and facilitate their determination.
288
The spatial and energetical separation of core and valence electrons, taking
place for any molecule, leads to the valence approximation and makes it
possible to solve the SCF equations only for valence electrons, which determine
the major physical and chemical properties. This approximation does not
impair the results appreciable if the valance AOs are orthogonalized to the core
ones of all the atoms of system and if the potential set up by atomic cores are
correctly allowed for.
The valence approximation is used in all semiempirical methods, particularly in zero differential overlap (ZDO) techniques, based on the neglect of
terms of the type in molecular integrals [except for H, Eq. (7)] and results in
a large reducing of the number of them. The available ZDO methods in
accordance with their formal schemes can be conventionally divided into three
groups.
In the simplest scheme CNDO (complete neglect of differential overlap) all
integrals with above-mentioned distributions are neglected. Moreover, appreciable simplifications are accepted to retain the invariance of the SCF equations
with respect to orthogonal transformations.
There is intermediate scheme INDO (intermediate neglect of differential
overlap) that is more rigorous than previous, where all of one-center integrals
and averaged (interatomic) values of the two-center Coulomb integrals are
accounted for. In this scheme the SCF equations are solved with additional
limitation that they are invariant under any local orthogonal transformations.
In the most rigorous NDDO scheme (neglect of diatomic differential overlap) all the one-center and two-center Coulomb integrals are retained.
Along with above mentioned ZDO methods, developed by Pople and
coworkers, many other ZDO algorithms were introduced, which differ from
each other in concrete ways of estimation of the diagonal and off-diagonal
H matirix elements and electronic interaction integrals as well as in schemes
of parametrization, basis sets and invariance criteria used. Various CNDO
methods, such as CNDO/2, CNDO/K, CNDO/S, CNDO/R, CNDO/SW,
CNDO/BW, differ from each other mainly the parametrization schemes. The
projection technique of diatomic differential overlap in all of two-center electronic interaction integrals is used in the PDDO and LEDO (here and further
the author's abbreviations of methods are retained). In the PRDDO (as in the
AAMOM) the diatomic differential overlap is retained only partly and accordingly all the two-center integrals are taken into account. In the latter much more
"physically justified" assumptions are made, that results in appreciable simplification of calculation procedure. In the various ZDO schemes (e.g., SESMO,
MINDO/I) some integrals or whole matrix elements are considered as parameters and are estimated from experimental data for isolated atoms and ions
(usually spectroscopic) and for molecules (heats of formations and geometrical
parameters). In the SESMO, besides, the MOs are constructed from STOs
having own scale factors. The major peculiarity of MNDO and MINDOs is the
use of a number of fitting functions, that allow simply evaluate all required
integrals. In the "combined" IRDO method, the NDDO rules of matrix element
289
calculations is used for the "classical" chemically bonded atoms and CNDO/2
rules for unbonded atoms. Various multiple expansions of charge distribution
potential (as i/rij) in series of spherical harmonics are used in the DRINDO,
which is an intermediate scheme between the NDDO and INDO ones. Directed
character of chemical bonds is taken into account in MCZDO and CNDO/R. It
should be pointed out different schemes, formulated in the frame of the hybrid
orbital method, where "chemical MOs" in systems are constructed from approximately orthogonalized hybrid AOs. There are several working schemes,
accounting for configuration interaction (CI) and thereby being suitable for
computing excited state properties (MNDOC/CI, MINDO/CI, PCILO, etc.).
There are some ZDO schemes, which are especially oriented to calculation of
spectral data (SPINDO, CNDO/S), magnetic properties (CNDO/SP, DEPAC),
thermochemical and other energy parameters (CNDO/SW, CNDO/BW,
MINDOs, MNDO, AMi).
It has been shown that with certain approximations ZDO calculations (as
correct to the terms of the S2 order in matrix elements ofSCF equations) may be
considered as imitation of SCF ones (without the ZDO) carried out in a symmetrically-orthogonalized basis set related to initial basis as. The analysis of this
problem in the framework of more general theory leads to still less conforming
conclusions. Therefore, one should attach with care to the results of this
semiempirical method. Nevertheless, it should not be forgotten, that the ZDO
methods (and Pariser-Parr-Pople as the first ZDO method) have played exceptionally important roles in quantum chemical studies in 60th-80th years and
many obtained results are valuable up to date. At present, when nonempirical
methods become much more accessible, the application of ZDO-based methods
sharply decreased even for medium size systems. The extended Huckel method
(EHT) that combines various versions of simple MO theory, provides the
roughest approximation since it does not account for electronic interaction
even for valence electrons. Today these methods even in the most sophisticated iterative versions (SCEHT, IEHT, etc.) are practically not applied at all.
Table 26 shows the main available methods of quantum chemistry.
Electronic States in Crystalline Solids
Everything we have described about molecules and clusters is also true for the
electronic structures of solids. The electronic states of a molecule must be
invariant under the rotations of the point group. The electronic states of
a crystalline solid, however, must also be invariant under the translational
periodicity of the space group. Hence,
(r
+ R) = (r),
(64)
where R is a translation vector of the lattice. To account for this periodicity,

Bloch showed that our crystalline orbitals must have the form
(k; r
+ R) =
(k; r)e ikR .
(65)
Restricted
(RHF)
Local exchange
density
SW XC(
DV XC(, LCAO XC(
Partitioned
(PHF)
Multiconfiguration
SCF
Extended Huckel theory (EHT)

Wolfsberg-Helmholz, Hoffmann, IEHT, SCEHT, etc.
Configuration
interaction
M611er- Plessett
perturbation
theory
Projected
(PUHF)
Coupled Cluster
coupled pair
approximations
Zero Differential overlap (ZDO)

NDDO type: PRDDO, MNDO, AM 1, MNDOCjCI, etc.
INDO type: MCZDO, IRDO, MINDOs, etc.
CNDO type: CNDO/2, CNDO/BW, PCILO, etc.
Semi-Empirical Methods
Unrestricted
(UHF)
Annihilated
(AUHF)
Valence bond
theory ("multistructure")
SCF MO (Hartree-Fock type)
Group Orbital
method
("geminals")
Correlation methods
Nonempirical methods
Table 26. Different methods of quantum chemistry in molecules
Extended
(EHF)
Many-body
perturbation
theory
tv
'-D
en
'"
a
OQ
5.
I;tl
e:.
'"('i'3
::r
'"
...,'"
::r
291
Here, we introduce the wavevector, k which provides a convenient index to

enumerate the one-electron states in solids. We can still express our crystal
orbitals in terms of linear combinations of atomic orbitals. Recently, in fact,
a Hartree-Fock LCAO program for crystalline solids has been developed
(Pisani et al. 1988) and coded as the CRYSTAL program (Dovesi et al. 1988). As
of this writing, the CRYSTAL program is starting to be applied to a number of
mineralogical problems. One advantage of the LCAO method for solids is that
we can analyze the bonding in terms of atomic properties and interactions. In
particular it allows the Mulliken population analysis (early developed for
molecules) to be transferred to solids with its generalization by virtue of
introducing the "differential" characteristics, such as the AO population densities and overlap population densities (along with the integral ones - atomic
charges, AO populations and overlap populations).
Traditionally, however, crystalline orbitals have been expressed in terms of
plane- or spherical-waves. These functions are used in four wide-spread band
structure calculation methods: APW (augmented plane waves method), GFM
(Green function method or Korringa-Kohn-Rostoker (KKR-method), OPW
(orthogonalized plane waves method), PPM (pseudopotential method).
The APW and Green's Function (or KKR) methods use both the local
density approximation to the exchange potential and the muffin tin approximation to the crystalline potential. Both methods are very similar to the MS-Xa (or
SCF-Xa-SW) molecular orbital method. The latter, in fact, is an adaptation of
the KKR method to finite clusters. Each atom is surrounded by a sphere in
which the potential is spherically averaged. In the interatomic regions, the
potential is constant. Within each atomic sphere, the solution to the Schrodinger
equation is expressed as an expansion of spherical waves while in the interatomic region the solution is a plane wave. The crystal orbitals are obtained by
matching the solutions at the sphere boundaries. This generates a secular
determinant or matrix that gives the wavefunctions and energies as a function
of k.
Recently, linear modifications of the APW and GFM (LAPW and LMTO
respectively) have been developed which greatly increase with computational
speed with only a small loss in accuracy. These have been reviewed in Anderson
(1983). A detailed account of the LMTO method is given by Skriver (1984). In
the "conventional" APW and GFM the matrix elements depend on energies
being evaluated because of the energy dependence of the radial wave functions
within the MT -spheres. This energy dependence can be eliminated if the If we
expand the radial wave functions polynomials in energy and retain only the
terms linear in energy, we can remove the energy dependence of the matrix
elements in the secular equation. Consequently, the (effective one-electron)
Hamiltonian and overlap matrices become independent of energy. The error
resulting from this procedure is less than that resulting from the muffin-tin
potential. The method of linear combinations of the MT orbitals (LCMTO) is
a "linear" one too. Its secular equation is similar to that of the LCAO but matrix
elements of secular determinant (due to energy dependence of radial functions)
292
depend on energy as well. The linearity of functions does sufficiently simplify the
computational problems.
In the OPW method all electronic states in crystals are divided onto core
and valence ones. Core states are defined by the Bloch sums in the LCAO form
and OPW functions are found in a form of plane waves and the linear combinations of core functions with the coefficients that are determined from the
orthogonality conditions of the OPW functions to the Bloch sums of core
electrons. Resulted OPW functions are used then as basic ones, over which the
unknown valence Bloch functions are expanded.
In the PP method the idea that the orthogonality of valence wave functions
to core ones is an equivalent of effective repulsion is realized. The latter partly
compensates the attractive potential, acting on valence electrons. Thus the
Schrodinger equation for these electrons can be substituted by equation
"pseudo-potentials", which is affected by the weak pseudopotential instead of
real one. This potential is often designed in model forms using simple analytical
functions with fitting parameters (model PP method). In another version of the
PP (so-called empirical PP method) crystalline pseudopotential is expanded in
Fourier series with coefficients that are regarded as fitting parameters (usually
it's needed a great number of such coefficients).
There are nonrelativistic as well as relativistic forms of the band theory
methods mentioned above. The latter is preferable in the case of heavy element
compounds. However, this approach may be used for other purposes, e.g., for
detail description of level splittings due to spin-orbital coupling.
Quantum chemical models and methods, which are used in cluster and solidstate approaches to the crystal structure, are summarized in Table 27.
Information from Electronic Structure Calculations

It should be briefly outlined what information can be derived from electronic
structure calculations (close to HF limit) and what experimental data can be
compared with this information.
The Nature of Chemical Bonds. From the one-electron orbitals, we can investigate the nature of bonding in a molecule or solid. This can be done according to
the Mulliken population analysis via AO populations P~ which is the total
number of electrons on X~ in all filled molecular (or crystal) orbitals. For
a closed-shell system:
occ
P~ = 2
L (CC)2 + k L P~VB,
(66)
where CC is the coefficient of the AO Xm uA of the atom A in the i = th (double)

occupied MO, and P/,'vB is the overlap population corresponding to X~
and Xn uB
LCAO X
DV Xa
SW Xa
Nonmuffin-ti n
Muffin-tin
EHT
ZDO
Semiempirical
Hartree-F ock
Local density
(the ories)
Shell
model
MP
CI
MBPT
SCF
Minimal
(Basis
Nonempirical
Electron
correlation
HF
Limit
Modified
electron gas
Ionic model
Extended
set)
H'l' = E'l'
Table 27. Methods for electronic structure calculations of molecules and solids. (Tossell)
Band theory
APW
GFM
LAPW
LMTO
Local density
(muffin-tin)
EHT
ZDO
Semiempirical
Hartree-Fock
(periodic)
SCF
Nonempirical
::l
v:>
en
0-
So
."
0-
Pol
::l
~
...,
'<
2.
::r
."
(j
a-
<=
Pol
10
o
-.
<:
."
'<
...,<=
en
y.
294
The total overlap population

occ
PAD ==
L P~P~ = 4 L L CCC~VSIlAvD'
Il. v
(67)
/J. v
is usually regarded as a measure of A-B bond strength. To get an approximate

estimate of the electron density distribution in a system, effective charges on
atoms are usually introduced
Z~f
= ZA -
PvA.
(68)
vA
Serious limitations of the Mulliken scheme (k = 1/2) should be noted. In any

case the overlap population is partitioned equally between the atoms A and
B (other schemes, e.g., k "# 1/2, are available, but the above scheme is commonly
accepted). It fails to account for real spatial distribution of the Xil radial part. The
latter circumstance is of particular importance for outer diffuse and polarization
AOs because a considerable portion of the density of such AOs lies in the
adjacent atom regions. All the above shows that one should not attach too much
importance to the absolute values of effective charges and populations. However, these values are very useful when comparing data obtained for related
compounds by identical procedures and with similar basis sets.
MO calculations make it also possible to give (on the basis of molecular
wave function) a descriptive spatial picture of bonding by way of electron
density maps (total or difference, i.e., with subtracted atomic contributions).
Of particular interest is the possibility of transforming conventional MOs
into localized ones, using for this purpose one of the available localization
procedures.
For so-called "first-order properties" (dipole and higher moments, charge
and spin densities, field gradients, etc.) theoretical values are obtained as the
expectation values of the single operators. The accuracy of calculations depends
on the type of property under consideration. Usually for expectation values of
the one-electron operators theoretical data are quite well at the Hartree-Fock
level. For expectation values of the two-electron operators correlation wave
functions are needed. An interesting example is the calculation of dipole moments, where the Hartree-Fock level sometimes exhibits appreciable differences
with experiment. The dipole moment is a small difference between two large
quantities of opposite sign; hence, wave functions of high accuracy are needed to
reproduce experimental values.
For the second- and higher-order properties (electric polarizabilities, chemical shifts, magnetic susceptibilities, etc.) only calculations which include electron correlation have quantitative meaning.
Force Constants, Elastic Properties and Equilibrium Geometries. The calculation
of the total energy and its derivative with respect to atomic position or unit cell
volume allows one to determine interatomic force constants and elastic properties. This information can, in turn, be used to calculate equations of state of
295
solids, vibrational spectra and thermodynamic quantities. Force constants also

can be used to determine equilibrium structures and predict phase transitions.
There are, of course, many potential applications of such first-principles calculations to problems in geophysics and geochemistry. The calculation of elastic
properties (i.e., bulk modulus and its pressure derivative) of solids is a recent
application of Hartree-Fock LCAO methods. At present, it is not clear what
kind of basis set expansion is required for reliable predictions that can be
extrapolated to the Earth's interior. This will probably be an active area of
research in the next few years.
For properties derived from the total energy, the Hartree-Fock level is
usually sufficient for geometric parameters (such as equilibrium geometry and
force constants). Correlation calculations (using Moller-Plesset perturbation
theory or at least limited CI wave functions), however, are needed for energetic
parameters (such as the dissociation energy).
Electronic Transition Energies: Spectroscopy and Semiconducting Bandgaps. The

energy differences between one-electron orbitals in both the Hartree-Fock and
Density functional theories cannot be related to electronic transition energies
and band gaps because of orbital relaxation. To evaluate electronic transition
energies, one must calculate the total energy difference between the ground and
excited state configurations. In the local density approximation, however, one
can use the Slater transition state formalism. Calculations of electronic
transition energies using density functional methods (i.e., the Xrx scattered-wave
method) give results that are within 20% of experiment (and often much better)
provided the transition state formalism (or other correction for orbital energy
relaxation) is used. However, in their simplest form, such calculations only give
the one-electron energies. In systems where the states can be described by
a single Slater determinent (or a linear combination of degenerate Slater determinants) the one-electron transition energies can be equated to spectroscopic
transition energies. The projection techniques discussed above are sometimes
used to determine spectroscopic multiplet energies. More generally, to evaluate
the energies of spectroscopic multiplets, it is necessary to calculate the coulomb
and exchange integrals from the one-electron orbitals. Little work in this area
has been done. Some bandgaps cannot be described at all without accounting
for electronic correlation. Perhaps the most important example is the MottHubbard gap that is used to explain the insulating nature of some transition
metal oxides.
References
Anderson OK (1975) Linear methods in band theory. Phys Rev B12: 3060-3083
Binkley IS, Pople lA, Hehre WI (1980) Self-consistent molecular orbital methods 21. Small
split-valence basis sets for first row elements. I Am Chern Soc 102: 939-946
Dovesi R, Pisani C, Roetti C, Silvi B (1988) CRYSTAL88. An ab initio all-electron LCAOHartree-Fock program for periodic systems. QCPE Program 577. Quantum Chemistry
Program Exchange, Indiana University, Bloomington, Indiana, USA
296
Gordon MS, Binkley JS, Pople JA, Pietro WJ, Hehre WJ (1982) Self-consistent molecular
orbital methods, 22. Small split-valence basis set for second row elements. J Am Chern Soc
104: 2997-2803
Hedin L, Lundquist BI (1971) Explicit local exchange-correlation potentials. J Phys C (Solid
State) 4: 2064-2083
Hehre WJ, Radom L, Schleyer VvR, Pople JA (1986) Ab initio molecular orbital theory.
Wiley-Interscience, New York, pp 1-548
Herman F, Skillman S (1963) Atomic structure calculations. Prentice-Hall, New Jersey
Hohenberg P, Kohn W (1964) Inhomogenous electron gas. Physical Rev B 136: 864-871
Johnson KH (1973) Scattered wave theory of the chemical bond. Adv Quant Chern 7: 143-145
boundary: Geophys Res Lett 16: 515-518 (1989)
Kohn W, Rostoker J (1954) Solution of the Schrodinger equation in a periodic lattice with
applications to metallic lithium. Phys Rev 94: 1112
Kohn W, Sham LJ (1965) Self-consistent equations including exchange and correlation effects.
Physical Rev 140A: 1133-1140
Korringa J (1947) On the calculation of the energy of a Bloch wave in a metal. Physica 13: 392
Muhlhausen C, Gordon RG (1982) Density-functional theory for the energy of ionic crystals:
test of the ionic model. Phys Rev B 24: 2147-2160
Pisani C, Dovesi R, Roetti C (1988) Hartree-Fock ab initio treatment of crystalline systems.
Lecture Notes in Chemistry, 48. Springer, Berlin Heidelberg New York, 193 pp
Schwarz K (1972) Optimization of the statistical exchange parameter IX for the free atoms
H through Nb. Phys Rev B 5: 2466--2468
Skriver HL (1984) The LMTO method. Springer Ser in Solid State Sciences, 41. Springer,
Slater .IC (1974) The self-consistent field for molecules and solids, vol 4. Quantum theory of
Molecules and solids. McGraw-Hill, New York, 583 pp
Wilson S (1984) Electron Correlation in molecules. Clarendon Press, Oxford
5.2 Chemical Bonding in Silicates

S. DUBROVINSKY and D.M. SHERMAN
How the nature of chemical bonds in silicates governs their structural and
physical properties has long been of interest. Experimentally, the bonding in
silicates can be investigated using spectroscopy and by mapping electron density
distributions with X-ray and neutron diffraction. Since the 1970s, there has also
been much effort directed towards the study of bonding from first-principles
electronic structure calculations using molecular orbital and band theory. This
chapter will review the experimental and theoretical investigations on the nature
of the Si-O bond.
Chemical Bonding in Silicates According to the Data of X-Ray Spectroscopy
X-ray spectroscopy studies the interaction offree electrons or photons with fixed
electrons and measures the energies of core electron states of atoms in solids.
From the core-state energies, one may determine the site symmetry and
coordination of an atom and the atom's effective charge. X-ray spectra also are
used to study the nature of chemical bonds and the energy level schemes of
electronic states in the valence and conduction bands.
297
The redistribution of the electron density during the formation of a chemical

bond will induce a change in the screening of the core electrons by the valence
electrons; this, in turn, should lead to a displacement (chemical shift) of an X-ray
line relative to its energy in the pure element. Although the chemical shifts,
measured relative to the pure elements, are small (for Si: 0.49-0.61 eV,
A1: 0.11-0.50 eV), it is still possible to relate them to crystal-chemical trends.
From the chemical shift, one can judge the change of the effective charge. For
example, changes in chemical shift for Si (and an increase in the effective charge)
can be seen on going from island silicates (e.g., olivine) to framework silicates
(e.g., quartz). At the same time, however, the variation of the Si effective charge
within a given class may be greater than that between classes. Thus the shifts of
the main levels connected with screening effects are not always useful. The most
dramatic changes in effective charge are associated with changes in coordination
number. For example, the effective charge on Si for quartz is 1.03 e, whereas in
stishovite it is 1.48 e). A direct relationship between K1X 1 ,2 shifts on Al and
average AI-O distances in silicates has also been found.
Aside from oxygen, the main silicate-forming elements fall in the third period
(e.g., Mg, AI, Si). Their spectra reflect the distribution ofthe 3s, 3p and vacant 3d
states. Examples of the spectra are exhibited in Fig. 63. Naturally, both the
emission part and the quantum emission spectra depend on the coordination
number, symmetry, and bond length of silicate-forming atoms. However, most
intriguing is the fact established in comparing the emission part of Si LUIII
spectra of various silicates and that of quartz. It turned out that all the spectra
may be divided into those similar to the Ln,1II band in quartz (Fig. 64) (A and B
maxima are predominantly developed, the intensity of A prevailing over the
intensity of B) and into spectra characterized by reduced maximum A and
strongly developed intermediate B' maximum. The analysis of spectra shows
that the first variant is specific of minerals with a compositionally homogeneous
radical, and the second variant is peculiar of minerals which contain Si0 4
tetrahedra linked with tetrahedral groups of a different composition (Be,B,AI).
4a,3t 2
S;L".",
~
80
120
E, eV
1820
Fig, 63, Si Lu,m-spectra and

Si KfJ-spectra of quartz
298
MO
AOSi
eV
0
10
20
30
40
3d
_~ 3p~~
--
~"'-
Si spectra
in Si0 2
-+ t2 e
~- 3,~a,
-
SiOa-
3t ~2
1e
-'2
2a,
1a
....
'0
L(B)
50
ID_
2S -+ t2 a,(u)
--~--...
_
L(C)
-en
en
_t2:(~~I':(')=:
1t2
...J
0 spectra
in Si0 2
-ID
"'-
AO
"
L( A)
SiL
~ ---- =
>0
en
g.--=
~
11.111 - - - - - -
Q)
lU
2s
Kx(C)
510
~p,
X(B)
Kx(A)
520
530
Kp
1S
1S
- - - - - - OK
1820
1830
1840
SiK
~---
Fig. 64. Molecular orbital diagram for the SiO!- group with X-ray spectra (Marfunin 1979, p. 278)
In this fashion, the effect of the trans-influence upon the structure of the valence
band of atoms from various tetrahedra is displayed.
Investigations of X-ray photoelectron spectra reveal that the range of the
shifts of the main electronic levels of Si, AI, 0 does not exceed 1.5 eV. There is a
tendency for the Is level of 0 and the 2p level of Si to be displaced to greater
binding energies as the condensation of silicon oxygen radicals increases and
Si-O bond length decreases (i.e., upon going from neso silicates to framework
silicates).
Description of the Chemical Bond in the Silicates
Using Molecular Orbital Theory
X-ray spectra are usually interpreted in terms of the molecular orbitals of a finite
cluster of atoms. For example, the X-ray spectra of many silicates might be
299
interpreted (to first order) in terms of the molecular orbitals of a (SiO)! - cluster.
It is found that irrespective of the calculation method and basis set of atomic
orbitals (AOs), an identical sequence oflevels for a tetrahedral complex of SiO!has been obtained: inner ones (purely atomic)-Ia 1 , 2a 2, H 2, 3a 1 , 2t 2, and valent
levels-4a l , 3t 2, 5a l , 4t 2, Ie, 5t, HI (Fig. 65).
The qualitative interpretation of X-ray emission spectra, absorption spectra
and X-ray photoelectron spectra is essentially the estimation of the degree of
participation of different AOs in occupied and free molecular orbitals (MOs).
Low-lying valence levels 4a and 3t are loosely binding and consist essentially of
oxygen 2s AOs with admixture of silicon 3s (for 4a 1 MO) or 3p (for 3t 2 MO)
AOs. The 5a l and 4t2 orbitals are multicenter MOs responsible for the
formation of a-bonds and formed as a result of the interaction between 3s and
3p silicon AOs and 2p oxygen AOs. The composition of the next MO group Ie,
5t 2 and 1tl is governed to a considerable degree by 2p oxygen AOs. Also, under
the conditions of symmetry vacant 3d silicon AOs may take part in the
formation of MO e and t 2 . Early molecular orbital calculations suggested that
Si20~
(r------------~A~
E, eV
30
'Y. =
2s0
+ 3sSi
2s0
+ 3pSi
312 -
180'
'Y.
= 164
'Y.
___________ ,
= 147
'Y.
= 132'
c _____
---~
2s0 + 3sSL::::--_
~2s0 ~
=::=---==:!I ~~ ~
"
18
16
Fig. 65. Molecular orbital diagram for the
Si20~ -
group
300
the Si d-orbitals playa substantial role in forming the Si-O bond. However, as
the reliability of spectroscopic measurements and quantum mechanical calculations has increased, it has become apparent that the degree of the participation
of 3d-orbitals of Si is only a few percent for ordinary silicates.
Although the (Si0 4 )4- cluster provides a useful starting point, it still gives
an incomplete description of the band structures of even simple silicates. For
example, the electron density distribution in a (Si0 4)4- cluster cannot account
for the high-energy part of the intensity distribution in the L",III Si emission
spectrum ofSi0 2 . A more complex ditetrahedral cluster, (Si 2 0 7 )6- resolves this
problem since the intercluster interaction generates additional levels occupied
by 3s states of silicon at the top of the valence band (Fig. 66). The results of the
calculations of (Si 2 0 7 )6- cluster reveal that changes of the angles of Si-O-Si
from 180 to 147 induce slight alterations in MO, and only subsequent decrease
of the intertetrahedral angle leads to a marked splitting of most of the MOs.
Studies of tetrahedral T04n- (T = B,Be,AI,Ge etc.) and octahedral M06m(M = Fe,Mn,Ti,Cr,V etc.) clusters by MO method revealed that irrespective of
the nature of the central atom, molecular levels may be divided into the same
basic groups which have already been described when discussing the MO
scheme of SiO!- complex. The first group comprises MO determined by AOs
initial atoms. The second group of MO is most significantly contributed by 2s
oxygen AOs; however, s, p and d AOs ofthe central atom also participates in the
formation of these MO. The third group ofMO includes bonds originating due
to valence AO orbitals of the central atom and 2p oxygen AOs. Next follow MO
containing prevailing amounts of 2p oxygen AOs and loosening MO not
occupied in main states.
The MO method has also been employed for the interpretation of silicate
NMR spectra. Correlation was found between the value of Do slot, between the
upper occupied and lower vacant MO and the paramagnetic constituent p
which determines the value of the constant of magnetic screening 9 Si). This
result enables us to explain the chemical shifts occurring in direction of low
0
-2
:;.!!!.
>-
Ol
Gic:
-4
-6
-8
-10
L
Arb.
XZW
1:
Fig. 66. The energy bands for cristobalite (bond orbital approximation)
301
fields during the transition from polymorphic modifications of Si0 2 to feldspars,

as well as the shifts taking place in direction of high fields during the transition
from orthosilicates to framework silicates. Calculations by SCF MO method for
a series of Si(O,F)-bearing molecules (SiF 4,SiO!- ,(H 3Si}zo) permitted in a
reasonable correlation with experimental data to reproduce an electric field
gradient upon oxygen nuclei in silicon tetrafluoride, olivine and polymorphic
modifications of Si0 2 It is established that screening constants upon the nuclei
increase with increase of the coordination number of Si. In this case the
anisotropy of magnetic screening increases upon oxygen nuclei, whereas upon
silicon nuclei it decreases. According to calculations, shortening of the length of
Si-O bonds in SiO!- and (H3Si}zO leads only to the decrease of the electric field
gradient on the oxygen, whereas in the screening constants do not change
practically. Deformation of Si0 4 tetrahedron results in the strengthening of the
oxygen electric field gradient. This correlates with the results of olivine NMR
spectra studies.
Chemical Bonding in Silicates According to Experimental Electron
Density Distributions
During recent years an intensive study of the distribution of valent electrons in
silicates was made on the the basis of precision diffraction experiments using
X-ray beams and neutrons. This work has enabled us to present graphically the
characteristics of the chemical bonding and valent states of atoms. The analysis
of experimental data using VB and MO methods reveals that in typical silicates
(in forsterite, for instance) there occurs a strong hybridization of silicon 3s and
3p-orbitals resulting in the formation of four hybrid Sp3 -orbitals. Each branch of
the hybrid orbital overlaps with an oxygen atom 2p-orbital to form O"-bonds.
Overlap of the remaining oxygen atom 2p-orbitals with silicon 3d-orbitals may
also take place to form n-bonds. In M lSimO n silicates containing electropositive
M cations, the extent of participation of 3d x 2 _y2 and 3d z 2 silicon orbitals in the
formation of the Si-O bond is less than that of 3d xy -, 3d xz - and 3dyz -orbitals. As
the electronegativity of the M atom increases, the contribution of n-bonding to
the Si-O bond becomes greater.
The analysis of the electron density distribution in crystals of several siliconoxygen compounds using quantum-chemical calculations enabled us to reveal
the dependence of the lengths of Si-O bonding and the effective charge on Si
atom upon the silicon coordination number. It is interesting to note that the
latter dependence has a nonlinear character. The nature of the Si-O bond and
the effective charge on the Si atom depends not only on the bond length and
coordination number but also on the effect of next-nearnest-neighbors. Consider the bonding in a structural fragment Si-O(br)-Si-O(ap)-M (where O(br)
is a bridging oxygen atom, O(ap) is an apical oxygen atom and M is a cation
such as Mg) From the results of deformation electron density study in orthoenstatite, it is found that the apical oxygens have a higher charge density than the
302
bridging oxygens. This is expected insofar as the M-O(ap) bond is much more
ionic than the Si-O bond. The larger charge density of the apical oxygens allows
the Si-O(ap) bond to be more covalent than the Si-O(br) bond.
Electron density distribution studies in olivines and orthopyroxenes have
shown that the effective charges of ions in the M2 sites of forsterite and fayalite
are higher than those of ions in the Ml sites. In enstatite and hyperstene,
however, the situation is reverse. To explain this phenomenon calculations were
performed using CNDO/2 method for large clusters comprising, along with the
central polyhedron, all the edge-sharing polyhedra. Hydrogen atoms were
added to exterior atoms of oxygen in clusters to assure electro neutrality. As a
result, values of 0.68 and 0.80 e in forsterite and 0.73 and 0.69 e in enstatite were
obtained for cations in Ml and M2 positions respectively, which qualitatively
correlates with X-ray study data.
A final example worth mentioning are the electron density distributions in
beryllium silicates. Because Be is a strong Lewis acid and forms covalent bonds
with oxygen, its presence may affect the nature of the Si-O bond. The electron
distribution in beryl shows that Si-O bonds have predominantly covalent
character and peaks of deformation electron density are shifted to oxygen atoms
and directed to peaks of Si0 4 -tetrahedron according to sp3-hybridization. At
the same time there are no localized directed covalent bonds in silicon oxygen
tetrahedra in phenakite, and one can observe a shift of electron density in
direction of the edge of tetrahedron parallel to the channels in the structure. The
explanation of subtle characteristic properties of electron density distribution in
these phases requires detailed quantum-chemical analysis.
Band Structures of Silicates
Cluster calculations using the methods of molecular quantum chemistry enable

us to gain valuable information concerning the character of chemical bonding in
silicates. However, in crystals the chemical bonding is described more completely in the framework of the band structure. The band structure of polymorphic modifications of Si0 2 (p-quartz, cristobalite) has been most thoroughly
studied (Fig. 66). Calculations with the Hartree-Fock method show that the low
narrow valent band is formed due to 2s oxygen AOs. The middle and upper
valent bands located above are formed of 2p oxygen AOs and sp3-hybridized
silicon orbitals. Major contribution to the middle band is made by 2p oxygen
AOs directed along the line of Si-O-Si bonding, and by the two remaining 2p
oxygen AOs to the upper band. The conductivity band is formed as a result of
the combination of antibonding AOs of sp3-silicon and 2p of oxygen.
One can also describe the band structure of polymorphic modifications of
Si0 2 in terms of three-center bonding orbitals (TBO). The three-center functions
Si(sp3)-O(2p)-Si(sp3) also include 2p oxygen AOs and sp3-hybridized silicon
orbitals: bonding (I/Ib)' anti bonding (I/Ia) and non bonding (I/In) ones of (J"-TBO
and two 2p(n) of the oxygen bridge atom AOs. Each fragment of Si-O-Si, in
303
addition to the 2s-electrons ofthe oxygen bridge atom, has six valence electrons.
They are located upon bonding (J- TBO t/lb' as well as upon n-orbitals. Thus the
occupied valence band, for instance, in a-cristobalite (where the Si-O-Si angle
equals 180) contains two bands, one being formed predominantly by TBO t/lb,
the other by Sp3 -orbitals of Si and n-orbitals of the bridging oxygen. Due to the
stronger interaction between Sp3 AO's of silicon and (J-bonding 0(2p) orbitals,
the t/lb band lies significantly lower than the n-band. These bands do not cross
and are separated by a moderately wide gap. Vacant TBO t/ln and t/la generate an
unoccupied conduction band. This conduction band is separated from the
valence band by a gap whose width determines optical and electro physical
properties of the crystal.
If the Si-O-Si angle is less than 180 (as, for instance, in a-quartz), then one
of 2p oxygen AOs can interact with sp3-hybrid orbitals of the silicon forming a
new band. With small deviations of the Si-O-Si angle from 180 0 this band may
be overlapped with band, and with big deviations with t/lb-zone. Hence, though
qualitatively the band structure of different modifications of Si0 2 is similar, the
width of band and densities of states are different. On the whole the TBO model
ensures good reproduction of the band structure and of the photoelectronic and
vibrational characteristics of polymorphic modifications of Si0 2
The band structure of amorphous Si0 2 and silicate systems shows that most
sensitive to local disordering are bands located near the forbidden band and that
the change of the angle of Si-O-Si from 90 to 180 is accompanied by the
increase of the effective charge on oxygen atoms by 0.2-0.4 e.
Interesting results have been obtained during the study of the band structure
of two-dimensional layers of silicon-oxygen tetrahedra ~ (Si 2 0 5 )2- by the
methods of perturbation theory and the extended Huckel molecular orbital
approach (Fig. 67). It turned out that the results of the MO-derived of clusters,
band structure of polymorphic modifications of Si0 2 and layers ~ (Si 2 0 5 )2- of
different symmetry are qualitatively similar - it is possible to distinguish MO
and band formed mainly due to the interaction of these or other AOs of silicon
and oxygen (Fig. 67). Reciprocal turns of Si0 2 -tetrahedra slightly effect the
band structure within ~ (Si 2 0 5 )2- layer and manifest themselves only in the
interaction of the nearest oxygens. Correlation of the results of the calculations
of the band structure of isolated layers and those found in kaolinite, lizardite,
pyrophyllite, and talc ~ (Si 2 0 5 )2 - shows that the interaction of apical oxygens
with octahedrally coordinated atoms of Al and Mg results in the perturbation of
the band structure within the layers of silicon-oxygen tetrahedra. The latter is
manifested by the formation of chemical bonds by those orbitals which are
nonbonding in isolated layers (Fig. 68).
Charges on Si and O(br) calculated from the data on the population of
different states do not change significantly during the transition from isolated
layers to mineral structures. However, the charge on O(ap) during such a
transition decreases from - 1.62 e to - 1.46 e (for Mg-bearing lizardite and
talc) and even to - 1.39 e (for AI-bearing kaolinite and pyrophyllite). The
analysis of band and crystal-orbital-overlap-populations demonstrates that the
0
304
r 2P6mm (1b 2)
r 4P6mm (2a)1
r 3P31m (1a2)
r 2P31m (2a)1
(1b)
r P6mm
13
1
(4a)
r P31m
11
1
Fig. 67. Selected states ofp6mm and p31m2 [Si 2 05]2- tetrahedral sheets at the center of the
Brillouin zone (Bleam and Hoffmann 1988)
coordination of O(ap) in minerals by octahedral cations reduces the charge on

apical oxygens but effects slightly the bonding force of Si-O(ap).
Chemical Bonding and Distinctive Features of Silicate Crystallic Structure
Understanding silicate structures is one of the most important problems in the
quantum-chemical study of silicates. For this purpose numerous ab initio
investigations have been performed using different basis sets and various
molecular clusters found in crystalline silicates.
Even using qualitative MO arguments (Fig. 69), it is possible to explain the
observed decrease (B-A-B (B-atom or a group of atoms) with the decrease of
305
-14
-16
-18L---~~------~
- 31
4a,/r 7
-33~==========~
- 35
-37L---------____~
Fig. 68. Brillouin zone for single-layer lizardite (Bleam and Hoffmann 1988)
the electronegativity of the central atom (for instance, according to calculations,

(Si-O-Si is 125 (SiH3-0-SiH3) and (Si-S-Si is 100 (SiH3-S-SiH3)' with
increase of electronegativity of B (during the transition from Si-O-Si to C-O-C
the decrease of valence angle is 20-30), as well as with increase of the distance
R(A-B). However, such a simple model cannot be employed for the analysis of
the change of the bonding lengths and angles on bridge and apical atoms of
oxygen in silicates. The latter may be done with the help of electron vibrational
theory of the heteroligand systems. The direct application of this theory to
quasitetrahedral heterosystems TLn-kXk [T -Si, L-O(br), X-O(ap)] enables us
to prove that bridging bonding in heterosystems should be longer than that in
SiO(br)4 and far more longer than the end bonding; in this case Si-O(ap) in
heterosystems should be shorter than similar bonding in the SiO(ap)4 homosystern. The angles between bridging bonding of O(br)-Si-O(br) should be smaller
306
Fig. 69. MO correlation diagrams
li near
D",
C2v
bent
and ( O(ap)- Si-O(br) may be both smaller and greater as compared to the
tetrahedral angle, the difference being insignificant in this case (the conclusions
are true for the coordination number equal to two).
These qualitative results are confirmed by the calculations of clusters H6 T zO
(T - C,Si,Ge,Sn) and Hn T Z07 (T - Si,P,S). Electron density concentration on C- O
bonding is observed in H 6 C ZO cluster having an acute angle, whereas a more
uniform distribution of electron density occurs on H 6 Si zO, H 6 Ge ZO, H 6 Sn ZO
clusters (T - 0 - T angle is obtuse). The analysis of theoretically plotted maps of
deformation electron density shows that a systematic decrease of T -0- Tangle
in the clusters H 6 Si z0 7, H 4 P Z0 7, H ZSZ0 7 also correlates with the decrease of
the charge density within the T -0- T triangle. All this enables us to consider the
increase of the T -0- T valence angle to be induced by electron repulsion at T - 0
bonding and in the inner region of TOT. On the whole, the calculations give a
reasonable explanation of the observed decrease of angles in the series
Si- O(br)-Si, P-O(br)- P, S- O(br)- S upon bridging atoms of oxygen in crystal~
of the respective compounds.
Quantum-chemical study of clusters of a mixed composition TSi0 7(T = B,Al,P) revealed that addition of a group with a more electronegative or
equal atom to silicon-oxygen tetrahedron leads to the loosening of Si- O(br)
bonding as compared to Si- O(ap) bonding with the respective redistribution of
silicon atomic orbitals from the levels of intra tetrahedral interaction. On the
contrary, when tetrahedron with a central atom, more electropositive than
silicon, becomes adjacent with silicon-oxygen tetrahedron, there occurs a sharp
strengthening of intratetrahedral interactions due to levelling of population of
307
overlapping silicon and oxygen bonding. Thus depending on the composition of

the second coordination sphere, silicon-oxygen tetrahedra in silicates may turn
out to be energetically nonequivalent. It is interesting to compare this conclusion with the above-described difference in emission parts of X-ray spectra Ln .m
Si in various silicates.
Particularly interesting information concerning the regularities of the structure of silicates and related compounds is obtained through quantum- chemical
calculations of clusters containing several silicon-oxygen tetrahedra. Thus, for
instance, CNDO/2 method has been employed for the theoretical study of
polymorphic modifications of Si0 2 - quartz, crystabolite, and coesite. The
model object chosen was Si50~~ - cluster neutralized by hydrogen atoms which
were located at a distance of 1 A from each non bridging atom of so that the
Si-O-H angle was rectangular. The initial angles of O-Si-O equalled 109.47.
The symmetry of the initial cluster was T d - 43 m R(Si-O) distances and
Si-O-Si angles varied during modeling the structures of polymorphic modifications of Si0 2. In this case the cluster symmetry was fixed in the framework of
point groups D 2d and C v whereas the changing of R(Si-O) distances and
Si-O-Si angles was made in such a way as to escape the alternation of the
number of degrees of atom freedom in the cluster. In the first model (symmetry
D 2d ) interatomic distances Si-O were fixed at the value 1.611 A, whereas
Si-O-Si angles were changed in the range of 140-180 and the change of the
total energy Et of cluster depending on the Si-O-Si angle. Energy minimum
was found from the condition of equality of zero of Et derivative with respect to
the Si-O-Si angle; it corresponds to the value of 146. This result is in good
agreement with the observed Si-O-Si angles in the studied polymorphic
modifications of Si0 2.
Calculations based on the second model having Cv symmetry, concerned
three clusters H12S15016. All the Si l -0 2-Si 2 angles in each cluster was fixed at
the value of 180, and all the Si 2-0 2 distances were equal to 1.611 A. Study was
made of the change of the energy of the interatomic interaction E(Si-O),
E(Si-Si) and the energy of Et cluster as a function of the Sil-Ol-Si l angle. The
investigations reveal that there is a relationship between R(Si-O) and values of
the minimum of interatomic interaction energy in each cluster. The theoretical
dependence of R(Si-O) from sec Si-O-Si) reproduces fairly well the experimental data for polymorphic modifications of Si0 2.
Use of Chemical Bonding Information for Modeling the Structure and

Properties of Silicates
The results of quantum-chemical calculations of molecular clusters can be used
to model structure and properties of mineral crystals. To do this, one starts with
the description of the potential surface obtained for clusters of H 6Si 20 7
composition as a result of calculations in basis STO-3G and 6-31G* (see Sect.
308
5.1). The potential surface can be fit to a model potential such as the 1-3
covalent potential
Vij = KjiRjj - R?/
+ (qjqiRjj)
(1)
or the Morse potential

Vjj
= Dij{exp[ -
2lXjj(R jj - R;j)] - 2exp[ - lXij(Rij - R;)]}
+ (zjzj/Rjj),
(2)
where kjj , Rij, R;j, D jj , IXjj are the potential parameters and qj, Zj are the effective
changes.
Good agreement between the data calculated with the use of potentials
(1) and (2) and the experimental data on the structure and the elastic properties
of quartz and forsterite indicates that the described methods of extending the
results of quantum-chemical investigations of clusters of crystals have broad
opportunities. The success of this approach is determined by the dominant
contribution of short-range interactions of modeled properties of crystals.
Since 1972, the so-called electron gas approximation for the nonempirical
evaluation of the interionic repulsion in crystals has been developed. Various
contributions made to such a repulsion are calculated by methods of quantum
mechanics from the electron density of the interacting ionic pair which is formed
by the superposition of electron densities of individual ions. Later, to this
approach were added corrections for the compression of the electron shell of
anions in the electrostatic field of surrounding cations (enlargement of the
electron shell of cations is less significant). The crystal field is modeled by the
charged spheric shell around the anion; the radius r of this shell is determined
from the condition of equality of potential within sphere Vj = qJr j (qj-the anion
charge) to the electrostatic potential in the position of anion in the crystal
[approximation of the modified electron gas (MEG)]. Calculations of the
structure and properties of polymorphic modifications of Si0 2 , Mg 2 Si04 ,
diopside, and a number of silicates in MEG approximation are known.
The structure of the low-temperature IX-quartz, for example, was calculated
with the radius of the shell 0 2 - equal to 0.93 A. The calculated parameters of
the cell and the volume turned out to be more alike the structure of the hightemperature IX-quartz, but the Si-O distance is considerably shorter (by
0.03-0.04 A) than the observed one. Generally speaking, the increase of the
radius of the shell 0 2 - improves the agreement of calculated distances with
experimental values, but the volume of the elementary cell in this case becomes
substantially larger (by 5-10%) than the observed one and the structure stability
increases.
Particularly unsuccessful is the modeling of the configuration of bonding
among tetrahedra: the calculated (Si-O-Si is significantly greater than the
observed one, though there is a considerable improvement as compared with the
earlier calculations which yielded (Si-O-Si 180. The energy of the lattice is
nearly 6% less than the experimental value which may be attributed to the
neglect of considerable covalence of Si-O bonding. It should be particularly
noted that the improvement of MEG model for quartz is achieved by the
309
introduction of the approximation ofthe anisotropic polarization ofthe electron

shell of ion 0 2 -, which is in agreement with the results of the electron density
distribution study.
References
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tetrahedral oxyanions in crystals. Phys Chern Mineral 14: 373-376
Bleam WF, Hoffmann R (1988) Orbital interactions in phyllosilicates: pertrubations of an
idealized two-dimensional, infinite silicate frame. Phys Chern Mineral 15: 398-408
Burdett JK (1982) Predictions of structure of complex solids. Adv Chern Phys 49: 47-112
Coppens EP, Hall MB (eds) (1982) Electron distributions and the chemical bond. Plenum
Press, New York
Dikov YuP. Rekharsky VI, Gutzev GI, Dolin SP, Levin AA (1986) Model investigation of
electronic structure of some silicate clusters by DVM-XIX. Phys Chern Mineral 13: 48-60
Dovesi R, Pisani C, Roetti C (1987) The electronic structure of IX-quartz. A periodic HartreeFock calculation. J Chern Phys 86: 6967-6971
Downs JW, Gibbs GV (1981) The role of the BeOSi bond in the structures of beryllosilicate
minerals. Am Mineral 66: 819-826
Downs JW, Gibbs GV (1987) An exploratory examination of the electron density and
electrostatic potential of phenakite. Am Mineral 72: 769-777
Fisher B, Pollak RA, Distefano TH, Grobman WD (1977) ELectronic structure of Si0 2 ,
Si xGe 1 - x0 2 and Ge0 2 from photoemission spectroscopy. Phys Rev B 15: 3193-3199
Geisinger KL, Gibbs GV, Navrotsky A (1985) A molecular orbital study of bond length and
angle variations in framework structures. Phys Chern Mineral 11: 266-283
Gibbs GV (1982) Molecules as models for bonding in silicates. Am Mineral 67: 421-450
Gibbs GV, Boisen MB Jr (1986) Molecular mimicry of structure and electron density
distributions in minerals. Mat Res Soc Symp Proc 73: 515-527
Hargittai M, Hargittai I (1987) Gas-solid molecular structure differences. Phys Chern Mineral
14: 413-425
Harrison WA (1980) Electronic structure and the properties of solids. Freeman, San Francisco
Hoffmann R (1988) Soilds and surfaces: a chemist's view of bonding in extended structures.
VCH, New York
Jackson MD, Hem RJ, Gordon RG (1985) Recent advances in electron gas theory for
minerals. Trans Am Geophys Union 66: 357
Jackson MD, Gordon RG (1985) MEG investigation of low pressure silica-shell model for
polarization. Phys Chern Mineral 16: 212-220
Lasaga AC, Gibbs GV (1988) Quantum mechanical potential surfaces and calculations on
minerals and molecular clusters. Phys Chern Mineral 16: 29-41
Liebman JF, Greenberg A (eds) (1987) Molecular structure and energetics. Deerfield Beach
(FL), New York
McMillan PF, Hess AC (1990) Ab initio valence force field calculations for quartz. Phys Chern
Mineral 17: 97-107
Newton MD, Gibbs GV (1980) Ab initio calculated geometries and charge distributions for
H 4 Si0 4 and H 6 Si 2 0 7 compared with experimental values for silicates and siloxanes. Phys
O'Keeffe M, Navrotsky A (eds) (1981) Structure and bonding in crystals. Academic Press,
New York
O'Keeffe M, Domenges B, Gibbs GV (1985) Ab initio molecular orbital calculations on
phosphates: comparison with silicates. J Phys Chern 89: 2304-2309
Pantelides ST (1977) Recent advances in the theory of electronic structure of Si0 2 Comm Sol
State Phys 8: 55-60
Post J, Burnham CW (1986) Ionic models of mineral structures and energies in the electron gas
approxmation: Ti0 2 polymorphs, quartz, forsterite, diopside. Am Mineral 71: 142-150
310
Tamada 0, Tanaka K (1988) Molecular orbital study (CNDO/2) of cation charge in forsterite
(IX-Mg 2Si0 4 ). Mineral J 14: 12-20
Tossell JA (1984) A qualitative MO model for bridging bond angle variations in minerals.
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silicon sulfides. Acta Cryst A34: 463-472
TossellJA, Lazzeretti P (1986) Ab initio calculations of 29Si NMR chemical shifts for some gas
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Paris
5.3 Chemical Bonding in Sulfide Minerals

D.W.
BULLETT
Our knowledge and understanding of the electronic structure, chemical bonding, and physical properties of the chalcogenides of transition metals have
advanced enormously over the last two decades. From the viewpoint of the
theoretical solid-state physicist or chemist these advances were driven by the
orders of magnitude increases in computer power that have made quantitatively
accurate calculations of electron band structure a routine possibility. Within this
chapter we highlight a few such applications, concentrating on two groups of
mineral sulfides: the transition-metal dichalcogenides (including both the layerstructure family and the pyrite/marcasite structures) and the tetrahedrite and
related family of minerals. While the chapter focusses on the results provided by
band-structure calculations, it is recognised that these can only be convincing
given the experimental back up provided by techniques such as ultraviolet or
X-ray photoemission and Auger electron studies (Vaughan and Tossell 1986).
Traditionally the various techniques for solving the electron band-structure
problem have been described as empirical, semi-empirical, or ab initio, according to the ratio of intuitive chemical concepts to numerical rigour involved. For
many years the linear-combination-of-atomic-orbitals (LCAO) method sat
firmly at the empirical end of the spectrum; the LCAO integrals were regarded
as free interpolation parameters in some, largely unspecified, basis. Fully ab
initio calculations often involved large-scale pseudopotential computations, and
interpretative chemical concepts could be obscured by the very large sets of
plane-wave basis functions required to represent the rather localised shape of
the electron d-wave in the vicinity of a transition-metal atom. More recently
LCAO has become important as an essentially non-empirical tool, at least as far
as the one-electron properties of complex solids are concerned, since it now
seems that all the significant two-centre interatomic matrix elements needed to
set up a one-particle band structure calculation for transition-metal compounds
can be computed quite accurately from the wave functions and potentials of the
311
isolated atoms. This approach then bridges the gap between the mathematically
elegant localized-orbital transformations arising out of the linear muffin-tinorbital method (Andersen and Jepsen 1984), and the semi-empirical Huckel-type
parameterisations that have also seen remarkable success in solid-state applications to complex structures by Hoffmann and coworkers.
Transition-Metal Dichalcogenides
Layer Compounds. The layer dichalcogenides of the transition elements form a

fairly coherent family of quasi-two-dimensional materials. In these compounds
metal (M) atoms occupy a two-dimensional hexagonal lattice of sites, each
surrounded by six chalcogens (X) in adjacent close-packed layers, positioned to
give either trigonal prismatic or near octahedral coordination around the metal.
Successive XMX sandwiches are separated by a van der Waals' gap, and the
sandwiches stack in a variety of different relative orientations in the various
compounds. The pioneering interpretations of the optical properties of these
compounds in terms of chemical bonding ideas and energy band schemes were
made by Wilson and Yoffe (1969). Since then the most sophisticated band
structure techniques have been used to elucidate fine details of the electronic
structure and associated properties such as charge density waves, phonon
properties and incipient metal-metal bonding, and the properties associated
with atoms and molecules intercalated between the layers.
Group IVa dichalcogenides all occur in the 1T layer structure, with metal
atoms in a near octahedral coordination and successive layers of metal sites
directly above the neighboring layers, giving one formula unit per unit cell.
Group VI dichalcogenides (apart from the ditellurides, in which metal atoms are
displaced from the centres of the coordinating units) occur in a trigonal
prismatic coordination within the individual stacking sandwiches. The reasons
for this difference are clear from the results of electronic structure calculations
such as those shown for TiS z and MoS z in Fig. 70. For TiS z, as might be
anticipated, a semiconducting p-d gap separates the six "sulfur p bands" from
the five "metal d bands", which themselves split in the octahedral field into t Zg
and eg sub-bands. Formally it is convenient to view this compound in terms of
the ionic configuration Ti 4 + (SZ -b and the semiconducting properties can then
be seen as a natural consequence of the filled-shell configuration; in a population
analysis of the occupied molecular orbitals the actual charge occupation is much
closer to Ti2+ (Sl-)Z. Coulombic repulsion between the anions provides one of
the factors favoring the octahedral coordination about the metal sites over a
trigonal prismatic geometry. In related compounds such as TiTe z, TiSe z, and
HfTe z the semiconducting gap disappears; p-d band overlap arises from the
slightly less ionic nature of the constituents.
A trigonal prismatic environment splits the t Zg triplet of states further into a
lower singlet, sometimes called the d z 2 band, and upper doublet. Complete filling
of the "d z 2 band" stabilizes the trigonal prismatic coordination in group VI
312
-.,......
~
... . -..
.....
:
: "'~
I
I
c/2
. - - - - n(E)
Fig. 70. The octahedral and trigonal prismatic coordination of metal atoms in the layer
dichalcogenides TiS 2 and MoS 2 , and the calculated electron energy bands and densities of
states for these semiconductors. Symmetry points in the irreducible Brillouin zone have been
given their conventional labeling. (Bullett 1989)
dichalcogenides such as molybdenite and tungstenite. A resulting electron band

structure for MoS 2 is depicted in Fig. 70. Molybdenite was calculated to be a
semiconductor, with an indirect gap of about 0.7 eV separating the occupied
from the unoccupied bands of d states; the smallest direct gap (at the zone center
r) is 1.4 eV. The occupied d z 2 band is 1.3 eV wide and overlaps the sulfur p band
by about 0.4 eV. While calculations such as this tend to underestimate energy
gaps, because of the errors involved in approximating the exchange and
correlation aspects of the potential, the overall picture of the chemical bonding
and physical properties in these materials does appear to be correct.
313
Pyrite- and Marcasite-Structure Compounds. Qualitative energy-level schemes

have been developed over the last two decades to explain the physical properties
of pyrite-type transition metal dichalcogenides MX z (Hulliger and Mooser
1965; Bither et al. 1968; Goodenough 1971, 1972). Applications to the series of
3d disulfides FeS z, CoS z, NiS z, CuS z, and ZnS z have since provided a coherent
account of the bonding in these materials (Bullett 1987, 1989).
In the pyrite and marcasite MX z crystal types (Fig. 71) each metal atom is
surrounded by six nearest-neighbor anions in a distorted octahedral environment, while each anion bonds to one anion and three cations in a distorted
tetrahedron. x-x pairs are a characteristic feature of both structures. The cubic
pyrite structure may be loosely thought of as a rock salt type of face centered
array in which the anions are x-x pairs with their diatomic axes oriented
equally along the four <Ill> cube directions. Cation octahedra share common
corners. In the orthorhombic marcasite structure edge-sharing of cation octahedra also occurs, in linear chains parallel to the orthorhombic c-axis.
Formally the chalcogen pairs may be considered divalent anions (Xz)Z-, in
which the anti-bonding pa* molecular orbital is unoccupied. For the series
FeS 2 , CoS 2, NiS 2, CuS 2, ZnS 2 the transition-metal ions thus take up formal
valence configurations increasing from d 6 to d io respectively. The quasioctahedral environment splits the d-band manifold into t 2g and eg sub-bands.
Provided that ligand-field energies are much greater than Hund's rule couplings,
we may anticipate that FeS z will be semiconducting (with the Fermi level falling
in the gap between t 2g and eg manifolds), but that the following members will be
paramagnetic metals until we reach the d io filled band configuration ofZnS2' In
fact CoS 2 (cattierite) is a ferromagnetic metal, and the anti ferromagnet NiS 2
(vaesite) occurs on the insulating side of the Mott transition (except at pressures
exceeding 46 kbar) whereas NiSe z does show metallic band-like behavior
(Wilson 1972).
---0,Fig. 71. The cubic pyrite and orthorhombic marcasite structures of FeS 2
314
IE,
. F
- 20
_. 16
-12
-8
-4
(eV)
- 20
-16
-12
-8
-4
Fig. 72. Calculated densities of electron sta-
- 20
-16
- 12
-8
-4
Binding energy (eV)
tes in the series of pyrite structures FeS 2

CoS 2 NiS 2 CuS 2 ZnS 2 (Bullett 1982). together with some X-ray photoelectron spectra
for the S 3s and valence-band electrons. (After
van der Heide et al. 1980)
315
Calculated density-of-states spectra for the pyrite series of sulfides are shown
in Fig. 72 (Bullett 1982). The main features are confirmed by experimental
photoelectron distributions (Li et al. 1974; Yamamoto et al. 1977; van der Heide
et al. 1980). Figure 73 displays a more schematic block representation of the
individual band limits as a function of energy below the highest occupied state in
each material, to emphasize the general trends associated with the stronger
binding of the metal d-state as we traverse the series.
At strong binding energies 10-19 eV below the Fermi level lie the two
discrete bands originating from bonding and antibonding s-states between S2
pairs. The next higher group of bands may be loosely labeled as the 5 S p-states
for each S2 pair in the unit cell (although of course they do also contain a
substantial proportion of metal d-orbitals). The sixth p-band, associated with
S2PU* anti bonding pair orbitals, lies several volts higher in energy. For FeS 2
FeS 2
(OS2
NiS 2
( US 2
~~U________LJ~J=kIJ
-5
-10
-15
~~~
~ f[][[a-~
Fig. 73. Schematic block diagram of the valence and conduction bands in the pyrite series
FeS z to ZnS z. In this figure the zero of energy corresponds to the highest filled state
316
these occupied S p-states extend from 1.6 to 8.5 eV below the valence band
maximum; in ZnS z the top of the S p-band forms the valence band maximum
and the calculated bandwidth is 6.6 eV.
Metal d-states descend towards and through the main S p-block as we cross
the series. In the calculated results for FeS z a clear gap of 0.7 eV separates the
occupied t 2g d-manifold from the unoccupied eg d-states; there is no complete
distinction between e g and SzPO"* bands, although the latter orbitals contribute
principally at the top of the first conduction band, 2.2-2.7 eV above the valence
band maximum. The size of the experimental band gap in pyrite, as determined
from optical and photoelectrochemical measurements, has been the subject of
much investigation, recently reviewed by Ferrer et al. (1990); estimates range
from 0.7 to 1.2 e V depending whether results are analyzed in terms of an indirect
or direct transition model. In CoS z the e g sub-band is 25% filled, and in this
calculation for assumed paramagnetic material the t Zg sub-band is about 0.9 eV
lower than in FeS z. At NiS z the Fermi level falls in the middle of the eg states
(and the occurrence of antiferromagnetism is not altogether surprising for a halffilled band) while the t Zg sub-band just touches the top of the S p-band. For the
copper compound the d-states lie entirely within the S p-band and contribute
the sharp peak 3 eV below E F . Finally at ZnS z the d-states sink below the
p-band and a semiconducting gap ~ 2 eV separates the latter from the lowest
conduction band states.
While states within the "metal d-band" energy range, ~ 1.5 eV in CuS z
and ~ 3 eV in FeS z, are overwhelmingly metal d-states, the metal d-orbitals do
also make a substantial contribution throughout the sulfur p-bands. The
calculated ionicity increases steadily through the series, from FeO. 6 + (SO.3 -}z to
Zn1.4+ (SO.7-}z.
The essential modification in the electronic structure of the marcasite phase
is the extra splitting of the t Zg orbitals in the more distorted quasi-octahedral
environment. Increased metal-metal interactions can be seen in the reduction of
dynamical effective ionicities in the a and c directions, relative to pyrite (Lutz
and Wiischenbach 1985). Atomic-orbital-based calculations (Bullett 1982) predict some overlap of the lowest metal d-band with the S p valence bands and a
slight decrease to 0.4 eV in the FeS z (marcasite) semiconducting indirect gap
between filled t Zg and empty e g bands. Other density-of-states features are
broadly similar to those of FeS z (pyrite).
Tetrahedrite and Related Structures
Tetrahedrite is a common mineral that occurs in most sulfide ore deposits. Early
studies proposed the chemical formula Cu 12 Sb 4 S 13 and a crystallographic unit
cell that can be derived by imposing ordered sulfur vacancies on a sphaleritetype (ZnS) super-structure (Pauling and Neumann 1934), a structure subsequently confirmed by Wuensch (1964, Wuensch et al. 1966). However, natural
317
tetrahedrite and tennantite/binnite (the corresponding mineral with As in place

of Sb) contain substantial amounts of other elements. A more general formula
has been proposed as (Cu,Ag) 1o(Fe,Zn)z(Sb,As)4S13, with a complete solid
solution existing between the Sb rich and As rich minerals. Problems of
non stoichiometry complicate studies of even the pure synthetic compound of
formula Cu 12 Sb4S13 : Makovicky and Skinner (1979) have shown this to contain
coexisting copper-rich and copper-poor exsolved phases of approximate compositions CU12.3Sb4S13 and CU13.sSb4S13, with cubic lattice constants a
= 1.0323 and 1.0448 nm respectively. The unsubstituted tetrahedrite, particularly the copper-rich phase, behaves as a room-temperature solid electrolyte.
The unit cell contains two types of Cu site and two types of S site, and some
of the coordination polyhedra depart substantially from any underlying tetrahedral structure. Twelve sulfur sites S(I) are each surrounded in a distorted
tetrahedron by two Cu(l) at 0.2342 nm, one Cu(2) at 0.2272 nm, and one Sb at
0.2446 nm. Each of the six Cu(l) sites is coordinated by four S(I) atoms in an
almost regular tetrahedron, while Sb atoms have three S(I) neighbors in a
trigonal pyramidal coordination: the fourth tetrahedral direction around Sh
corresponds to a sulfur vacancy of the sphalerite lattice. The remaining six
copper sites Cu(2) form a regular octahedron about a central S(2) atom at
distances of 0.2234 nm, with each Cu(2) threefold coordinated by two S(l) and
one S(2) almost within the same plane. Diffuse peaks of electron density at sites
adjacent to the base of SbS 3 pyramids have been attributed by Makovicky and
Skinner (1979) to mobile copper ions diffusing through these Cu(3) sites. Their
refined structure has only a 67% occupation ofCu(l) sites and 28% ofthe total
copper as the mobile portion; in their copper-poor phase 7% of the copper
would be mobile. Further information concerning the local environment of Cu +
in these minerals might be provided by nuclear quadrupole resonance studies
such as those performed by Abdullin et al. (1987) on a range of oxides, sulfides,
and sulfosalts.
Calculations of electronic structure confirm the intrinsic electron-deficient
character of the Cu 12 Sb4S13 structure (Bullett and Dawson 1986). A gap of
1.2 eV occurs in the energy distribution of electron states (Fig. 74) after doubly
occupying 116 valence states per unit cell, one more than the available 115 pairs
of valence electrons. Thus natural tetrahedrite can contain substituted Zn atoms
up to the composition limit CU10Zn2Sb4S13, and at this composition the
compound behaves as a diamagnetic semiconductor. Given this picture of the
electron spectrum, it is hardly surprising that there exists a copper-rich phase of
tetrahedrite containing almost exactly two additional Cu ions per formula unit.
Two of the Cu(l) atoms are displaced in order to accommodate these extra ions,
so that the copper-rich phase ends up with approximately four mobile Cu ions
per formula unit. Band-structure calculations for such a copper-rich arrangement generate a filled-valence-band structure with an energy gap of 0.9 eV
between highest filled and lowest empty sites, even before any allowance for
relaxation of the atoms about these interstitial sites. Experimental optical
318
undisplaced Cu
displaced Cu
-20-18 -16-14 -12-10 -8 -6 -4 -2 eV
-20-18-16-14 -12 -10 -8 -6 -4 -2 eV
Fig. 74. Calculated densities of electron states and its projection on individual sites in the
tetrahedrite structures Cu 12 Sb 4S 13 and CU14Sb4S13' Results for the copper-rich phase
demonstrate the similarity of contributions from the displaced and undisplaced copper sites.
(Bullett 1987)
absorption spectra for a range of tetrahedrites indicate a gap between valence

and conduction bands of about 1.7 eV in the semiconducting tetrahedrites
(Jeanloz and Johnson 1984).
This bonding picture suggests there is no difficulty in absorbing up to two
Cu atoms per Cu 12 Sb 4S13, and at the copper-rich limit at least four out of every
14 copper atoms are present as highly mobile ions. The easy diffusion of these
ions from one Cu(3) site to another gives the Cu-rich (and to a lesser extent the
Cu-poor) unsubstituted tetrahedrites solid-electrolyte properties at room temperature. Formally one can think of the energy gap as arising either from the
ionic extreme (CU+)14(S3+)4(S2-)13' or from a more covalent picture (which is
probably nearer the truth) with each neutral Sb atom making covalent bonds to
three S- ions in the electron configuration (Cu+)14(SbS 3)l-(S2-).
References
Abdullin RS, Kal'chev YP, Pen'kov IN (1987) Investigation of copper minerals by NQR:
crystallochemistry, electronic structure, lattice dynamics. Phys Chern Mineral 14: 258-63
Andersen OK, Jepsen 0 (1984) Explicit first-principles tight-binding theory. Phys Rev Lett 53:
2571--74
Bither TA, Bouchard RJ, Cloud WH, Donchue PC, Siemons WJ (1968) Transition metal
pyrite dicha!cogenides. High pressure synthesis and correlation of properties. Inorgan Chern
7: 2208-20
5.4 Bonding in Oxides, Oxyanions, and Halides
319
Bullett DW (1982) Electronic structure of 3d pyrite and marcasite-type sulfides. J Phys C 15:
6163-74
Bullett DW (1987) Applications of atomic-orbital methods to the structure and properties of
complex transition-metal compounds. Phys Chern Mineral 14: 485-91
Bullett (1989) Structure and bonding in the chalcogenides of the early transition metals.
Polyhedron 8: 1619-24
Bullett DW, Dawson WG (1986) Bonding relationships in some ternary and quaternary
phosphide and tetrahedrite structures. J Phys C 19: 5837-47
Ferrer IJ, Nevskaia DM, de las Heras C, Sanchez C (1990) About the band gap nature ofFeS z
as determined from optical and photoelectro-chemical measurements. Sol State Commun
74: 913-6
Goodenough 18 (1971) Conceptual phase diagram and its application to the spontaneous
magnetism of several pyrites. J Sol State Chern 3: 26-38
Goodenough 18 (1972) Energy bands in TX z compounds with pyrite, marcasite, and
arsenopyrite structures. J Sol State Chern 5: 144-152
Hulliger F, Mooser E (1965) Semiconductivity in pyrite, marcasite and arsenopyrite phases. J
Phys Chern Sol 26: 429-33
Jeanloz R, Johnson ML (1984) A note on the bonding, optical spectrum and compositions of
tetrahedrite. Phys Chern Mineral II: 52-54
Li EK, Johnson KH, Eastman DE, Freeouf lL (1974) Localised and bandlike valence electron
states in FeS z and NiS 2 . Phys Rev Lett 32: 470-2
Lutz HD, Wiischenbach G (1985) Infrared reflection spectra, directional dispersion of the
phonon modes and dynamical effective charges of FeS 2-marcasite. Phys Chern Mineral 12:
155-60
Makovicky E, Skinner BJ (1979) Studies of the sulfosalts of copper. ':::an Mineral 17: 619-34
Pauling L, Neumann EW (1934) The crystal structure of binnite, (Cu,Fe)12As4S13' and the
chemical composition and structure of minerals in the tetrahedrite group. Z Krist 88:
544-62
van der Heide H, Hemmel R, van Bruggen CF, Haas C (1980) X-ray photoelectron spectra of
3d transition metal pyrites. J Sol State Chern 33: 17-25
Vaughan DJ, Tossell JA (1986) Interpretation of the auger electron spectra (AES) of sulfide
minerals. Phys Chern Mineral 13: 347-50
Wilson JA (1972) Systematics of the breakdown of Mott insulation in binary transition metal
compounds. Adv Phys 21: 143-198
Wilson lA, Yoffe AD (1969) The transition metal dichalcogenides. Discussion and interpretation of the observed optical, electrical and structure properties. Adv Phys 18: 193-335
Wuensch Bl (1964) The crystal structure of tetrahedrite CU 12 Sb 4S 13 . Z Krist 119: 437-54
Wuensch Bl, Tajeuchi Y, Nowacki W (1966) Refinement of the crystal structure of binnite
CU12As4S13' Z Krist 123: 1-20
Yamamoto H, Nakagawa T, Odonera H, Watanabe H (1977) X-ray photoelectron spectra of
valence electron in CU,Ni l -,S2 and ZnS 2 . 1 Phys Soc Jpn 43: 1095-6

D.S.
URCH
The most direct way to investigate the electronic structure of minerals is by PAX
(photoelectron and X-ray emission) spectroscopy. X-rays which are generated
by electron transitions from the valence band to a core hole (valence X-rays,
VXR) exhibit fine structure which is determined by the energies of the molecular
orbitals (MOs) and by the atomic orbital (AO) composition of those orbitals.
320
Photoelectron (PE) spectroscopy enables the VXR spectra to be aligned on a

common energy scale so that the structure of the molecular orbitals can be
observed.
When chemical bonds are formed between atoms (or ions), individual atomic
orbitals are perturbed and character associated with anyone atomic orbital will
be found, in varying amounts, in many molecular orbitals, each with a different
energy. Relaxation processes from these MOs (or bands in a solid) will give rise
to a set of X-rays spread over an energy range determined by the energy range of
the molecular orbitals. Furthermore, as the X-ray emission process can be
shown to be a localized, essentially atomic phenomenon, even when the atom is
engaged in chemical bonding, the relative intensity of peaks in a VXR spectrum
will be a direct reflection of the amount of a specific type of atomic orbital from
the emitting atom present in different molecular orbitals (or a direct reflection of
a partial density of states at the emitting atom). The type of AO will be
determined by the electric dipole selection rule, Lli = 1, just as for an isolated
atom. This selection rule is well obeyed for X-rays with wavelengths in excess of,
say, about 5 A. Thus a VXR spectrum that arises, for example, from relaxation
to an s orbital vacancy on atom M is a direct representation, on an energy scale,
of the extent to which valence shell p character from M participates in each of
the individual molecular orbitals of the compound. Similarly, if the relaxation is
to a p vacancy on M, then the corresponding VXR spectrum maps out the
amount of Ms and Md character present in the different molecular orbitals.
A peak in a VXR spectrum measures the energy difference between an initial
core hole state and a final state with a vacancy in a specific MO. If the ionization
energy of the core hole state is measured by XP spectroscopy, then the
ionization energy of the molecular orbital can be calculated. If this is done for a
series of VXR spectra from a mineral then they can all be aligned on a common
energy scale, that of the molecular orbitals. Thi6 alignment allows the composition of each molecular orbital to be observed in terms of its constituent atomic
orbitals and thus the electronic structure of the chemical bonds in the mineral to
be established.
This approach to the study of the chemical bond is particularly fruitful where
partial covalency is suspected. Examples will be given in the sections below in
which PAX spectroscopy has been used to investigate the bonding in oxides,
hydroxides, and oxyanions. Investigations of halide minerals have been less
interesting because of the highly ionic nature of most bonds to halides.
Bonding in Oxide Minerals
One of the first oxide minerals to be studied by PAX spectroscopy was periciase.
It was thought that its simple cubic structure would be reflected in simple VXR
spectra from both magnesium and oxygen. However, as can be seen from
Fig. 75, this is not so. The main peak in both the 0 and the Mg spectra is split,
indicating the presence of two bands of orbitals. Furthermore, the observation
321
i.1\.\
l.J
.
-.-.-.-_..-1'
'-
"
"
1280
30
Fig. 75. PAX spectra for periclase. Top (dot-dashed line) oxygen KIX VXR spectrum; center
magnesium VXR spectra, Mg
KP (solid line upper energy
scale) and Mg L2 3 M (dashed
line lower energy scale); bottom
valence band X-ray PE spectrum. All spectra aligned to the
lower, molecular orbital energy
scale
,-v
1290
20
10
of a Mg KP spectrum shows that occupied orbitals with Mg 3p character exist

and so a simple ionic model for the bonding in MgO must be wrong. A detailed
model to describe the extent and type of covalent bonding between magnesium
and oxygen has been proposed based on the Mg 4 0 4 cube. This model has been
extended to Mg 32 0 32 to show how the bonding in a localized unit can be
extended to build up a band structure. An alternative bonding model based on
[Mg06r 10 and [OMg 6J + 10 has also been described.
Whilst the VXR spectra of a few other oxide minerals have been reported,
only a superficial correlation with bonding has been attempted.
Spinel is not strictly an "oxide" mineral but it can be regarded as a mixed
oxide and so bonding in spinel will be considered here. The PAX spectra for
both magnesium and aluminum as well as for oxygen, together with the valence
band PE spectrum have all been reported. When aligned on a common energy
scale the spectra show that two main bands of orbitals exist in the structure. The
least tightly bound band has considerable oxygen 2p character together with
some participation from magnesium and aluminum orbitals. In the more tightly
bound band, where there is less oxygen character, the magnesium contribution
is also reduced but there is a slight increase in the amount of Al 2p character. It
322
is interesting to note that hexacoordinate aluminum in spinel gives rise to a

VXR spectrum that is very similar to that from magnesium in periclase. This
suggests that it may well be possible to use VXR spectra peak shapes to
determine the coordination number of a metal in an oxide lattice.
Bonding in Hydroxide Minerals
The PAX spectra of brucite [Mg(OHh] have been reported. As with periclase,
the presence of a Mg Kf3 spectrum indicates that the bonding between magnesium and hydroxide must have some covalent character. A detailed investigation of the PE and VXR spectra shows, however, that the most important
covalent bond exists between the oxygen and hydrogen of the hydroxyl group.
The orbitals about oxygen can then be described as, two 0 2p lone pairs (A), an
o 2s orbital (B) and a O-H (J bond with considerable 0 2p character (C). The
disposition of 0 2p character can be determined directly from the 0 Ka VXR
spectrum which shows an intense peak at 526 eV (A) and a peak with about 25%
intensity at 521 eV (C). The Mg Kf3 spectrum, which follows the 0 Ka spectrum
closely, can be rationalized as due to weak covalent bonding between magnesium and oxygen. Magnesium interacts with both A and C orbitals but causes
only a minor perturbation. Relative peak intensities in the valence band PE
spectrum provide evidence for the presence of a little 0 2s character in the O-H
(J bond.
Similar PAX spectra are observed from gibbsite [AI(OHh] from which it
may be concluded that the nature of the bonding is similar to that in brucite. The
Al Kf3 VXR spectra have been reported for the oxy-hydroxides diaspore [a-AIO
(OH)] and boehmite [y-AIO(OH)]. In these minerals the changes in the peak
profile can be directly related to the structural changes in the chemical environment of the aluminum.
Bonding in Oxyanions
After silicates, carbonates form the largest group of minerals which contain oxyanions. Other oxy-anions of mineralogical importance include borates, sulfates
and phosphates. In this section the bonding in these latter, tetrahedral anions
will be considered first as their high symmetry makes the classification of
molecular orbitals easier.
Tetrahedral Anions. A qualitative molecular orbital energy level diagram for the
tetrahedral unit M0 4 is shown in Fig. 76. It has been assumed that M is a maingroup atom like sulfur, phosphorus, or boron. The same figure can therefore be
used to discuss the bonding in SO~ -, PO~ - and B01-. The diagram indicates
that the B Ka and S or P Kf3 spectra could have three peaks, reflecting valence
shell p character in 1t 2 , 2t 2 , and 3t 2 orbitals. This can be seen in the S Kf3 VXR
323
en
3d
ooo3p
xxx 35 - 2 p
~a1-1i0J]2t-T3t2
I 2 I
=25
n~a L_~1t2
Ii
II
il
It
-2p
-25
-15
-15
II
i:
II
II
II
II
II
II
II
II
Ii
II
II
II
II
II
I
I
I
I
-1t1
I 1e
I
I
i
o Ka
--------ij~-------------Kf3
Fig. 76. Molecular orbital energy level diagram for a tetrahedral unit, M0 4 . Vertical
scale is energy (logarithmic).
Left hand column atomic orbitals for M (assuming M to be
a 2nd row element - if M were
from the 1st row then 3s becomes 2s, 3p becomes 2p and
3d is absent). The orbitals are
coded as follows: 3s (or 2s)
cross; 3p (or 2p) open circle; 3d
solid dot. Next column, atomic
orbitals for oxygen: 2s open; 2p
solid. To the right of the verticai
line the molecular orbitals that
arise from the interaction of
the M and oxygen valence orbitals are grouped according
to the irreducible representations of the tetrahedral point
group. Relative contributions
of different AOs to the MOs
are indicated, in a qualitative
way, by area. The VXR spectra
are shown as follows: 0 Ka
solid lines; M Kf3 dashed lines;
M L 2 3 M dot-dashed (3s --> 2p),
dot-dot-dashed (3d --> 2p)
spectrum for sulfate in Fig. 77. The Kf3' satellite peak at 2453 eV shows the
presence of some S 3p character in the 1t2 orbitals which are mostly 0 2s. The
Kf3-Kf3' separation is determined by the difference between 2s and 2p ionization
energies on the ligand atom. The energy of this separation can therefore be used
to identify the ligand (see below "Halides").
The main peak at 2467 eV shows the presence of much more S 3p character
in the 2t2 orbitals. This peak aligns with the 0 Koc peak at 521 eV showing that
2t2 orbitals have both S 3p and 0 2p character and are therefore strongly
(J bonding. The very weak feature at 2471 eV aligns with the main 0 Koc peak
and locates the 3t 2 orbitals. From the intensity of the 0 Koc peak these orbitals
are almost exclusively 0 2p lone pair in character. The sulfur L2,3M spectrum is
especially interesting. The tetrahedral symmetry of the anion restricts 3s character to the la l and 2a l orbitals which can be ascribed to peaks at 140 eV and
155 eV. As there are no other occupied orbitals of a l symmetry, the only
reasonable explanation for the peak at 162 eV is that it is due to MOs with 3d
character. The peak aligns with a shoulder on the low energy side of the main
o Koc peak as would be expected if empty 3d orbitals were to interact with the
o 2p "lone pair" orbitals, Ie and 3t 2 . The observation of this peak in the PAX
spectra for phosphate and sulfate (also silicate) thus provides direct evidence for
the use, by second row elements, of their 3d orbitals in chemical bond formation.
324
----------' "
510
500
...--
,..-.--
520
'--.-.,/
,/
530'
.r'\
'-
150
2450
2460
2470
30
20
10
Fig. 77. PAX spectra for the sulfate anion. Top oxygen Ko: (dashed line is solid line x 10);
center sulfur VXR spectra, S Kf3 solid line (lower energy scale) and S LZ,3M dot-dashed line
(upper energy scale); bottom, valence band X-ray PE spectrum. All spectra are aligned to the
lower, molecular orbital, energy scale
Whilst the L2,3M spectra provide convincing proof of the role played by 3d
orbitals, the presence of a weak "high energy" satellite peak in the K{J spectrum
is also of significance in understanding the nature of the bonding in tetrahedral
anions. This peak shows that 3p character is present in the 3t 2 orbitals that are
mostly oxygen "lone pair". This in turn implies the existence of (J-rr; mixing,
i.e., an interaction between the 2t2 (J bonds and oxygen lone-pair orbitals.
PAX spectra from borates in which the boron enjoys tetrahedral coordination by oxygen are restricted to boron and oxygen VXR spectra and the PE
valence band spectrum. An examination of such spectra, from minerals such as
pinnolite and danburite reveals a very similar basic picture to that found in
sulfate and phosphate. 1t2 is mostly 0 2s in character, but there is evidence for
some participation by B 2p in the presence of the B KIX' peak at 167 eY. The
325
main boron KO( peak, at 182 eV, aligns with the shoulder in the 0 KO( indicating
the presence of both B 2p and 0 2p in the B-O (1 bonds. There is no X-ray
emission spectrum that involves B 2s orbitals and so no direct evidence of the
role played by these orbitals in bonding.
Trigonal Anions. Carbonate and borate are iso-electronic, which is reflected in
the similarities in their PAX spectra. For carbonate the oxygen KO( spectrum
shows two principal features (521 and 526 eV) which can be correlated with
non bonding orbitals (either lone-pairs or n-orbitals) and bonding orbitals. The
C KO( peak (279 eV) is remarkably sharp. This indicates that the MOs in which
carbon 2p character is concentrated have similar ionization energies. Whilst the
non bonding n orbitals will be located wholly on the oxygen atoms the bonding
n orbital, a~, has both C 2p and 0 2p character. The PAX spectra show that this
bonding n orbital has just about the same ionization energy as the (1 orbitals.
Evidence for carbon 2p participation in the e' orbitals which are mostly 0 2s, is
provided by a satellite peak at about 260 eV, comparable to the KP' peak for
sulfate and phosphate.
When VXR spectra are measured from a single crystal of calcite it is possible,
by taking advantage of the anisotropic emission of X-radiation, to distinguish
between (1 and n bonds.
Boron KO( spectra from mineral in which it is trigonally coordinated show
a remarkable "high-energy" satellite at about 192 eV. This is very near the
energy of the boron X-ray absorption edge and is absent (or of very low
intensity) when boron is tetrahedrally coordinated. This feature is therefore a
most useful indicator of the coordination environment of boron. Its origin
would appear to be due to the excitation to, and subsequent relaxation from, the
n* orbital. It is reasonable to suppose that this orbital will be more tightly
bound than the (1* orbital which would be present in tetrahedral borates. If,
furthermore, n* is a bound orbital but (1* lies in the continuum (i.e., it has an
energy greater than the B Is ionization energy), then an electron excited to the
former will be localized on the boron atom with the Is -1 vacancy, whilst
excitation to the (1* will allow the electron to escape. Resonance relaxation,
giving the high energy satellite, will therefore only be observed for boron in
trigonal coordination.
Bonding in Halide Minerals

The bonding in halide minerals (e.g., halite, fluorspar) is mainly ionic and VXR
spectra (e.g., F KO( from CaF 2) show only small perturbations which can be
ascribed to partial covalency. A different situation exists for the one halide
mineral for which PAX spectra have been measured - cryolite (Na 3 [AIF6]). In
this mineral the aluminum atom is surrounded by six fluorine atoms ranged at
the apices of an octahedron. The molecular orbital energy level diagram (based
on Oh point group symmetry) has many similarities with that for the tetrahedral
326
oxy-anions (Fig. 76). The Al L 2 . 3 M spectrum shows Al 3s character to be

present in 2a 1g and an additional, higher energy, peak in this spectrum shows
that Al3d orbitals are also used in bonding in this complex. The Al Kf3 spectrum
aligns with a shoulder on the low energy side of the F KO( peak - direct evidence
for the formation of a bond with covalent character between aluminum and
fluorine.
The presence of a Kf3' satellite with an energy some 20 eV less than that of
Kf3 is indicative of some Al 3p character in 1t 1 u' orbitals that are mostly F 2s.
The Kf3-Kf3' of 20 eV is characteristic of bonds to fluorine. The use of this
separation to establish the presence of specific bonds in a mineral is nicely
demonstrated by the Al Kf3, f3' spectrum from topaz where two Kf3' satellites are
observed, one at about 20 eV from the main Kf3 peak, the other at about 15 eY.
The presence of the former indicates AI-F bonds, the latter AI-O bonds, as
should be expected for this mineral in which the aluminum is surrounded by two
fluorine and four oxygen atoms.
As in the case of the tetrahedral oxyanions in which the central atom Kf3
spectrum shows a weak high energy satellite, so too the Al Kf3 exhibits a
corresponding feature due to Al 3p character in the 3t 1u orbitals that are mostly
F 2p. This indicates some slight interaction between the 2t 1u (J bonds and
fluorine lone-pairs.
Conclusion
Whilst, in isolation, PAX or even VXR spectra can give valuable, qualitative
indications as to the nature of chemical bonds in minerals, their greatest value is
when used in combination with theoretical calculations. PAX spectra are unique
in giving data (energy levels, AO coefficients) that can be compared directly with
theoretical predictions. When good accord is achieved, it is then reasonable to
assume that the theoretical model provides an accurate picture of the electronic
structure of the mineral.
References
Haycock DE, Kasrai M, Nicholls CJ, Urch DS (1979), The electronic structure of magnesium
hydroxide (brucite) using X-ray emission, X-ray photoelectron and Auger spectroscopy.
J Chern Soc Dalton Trans: 17911796
Hessabi R, Urch DS (1990) J Chern Soc Faraday Trans 86: 247-252
Nefedov VI, Buslaev Yu A, Sergushin NP, Kokunov Yu V, Kovalev VV, Bayer I (1975)
J Electron Spec Rei Phenom 6: 221-229
Kosuch N, Wiech G, Faessler A (1980) J Electron Spec Rei Phenom 20: 11-23
Urch DS (1985) X-ray spectroscopy and chemical bonding in minerals. In: Berry FJ, Vaughan
DJ (eds) Chemical bonding and spectroscopy in mineral chemistry. Chapman and Hall,
London, pp 31-36
Urch DS (1988) PAX (Photoelectron and X-ray emission) spectroscopy: Basic principles and
chemical effects. In: Gomes Ferreira J, Teresa Ramos M (eds) X-ray spectroscopy in atomic
and solid state physics. NATO Sci Affairs Div, Plenum Press, New York, pp 155-200
5.5 Electronic Structures of Iron Oxides and Silicates
327

D.M.
SHERMAN
Most applications of electronic structure calculations are concerned with

understanding chemical bonds and predicting geometrical properties and force
constants. Transition metal oxides and silicates, however, provide an additional
set of problems, since much of their physics and chemistry is associated with
electronic transitions involving the partially occupied d-orbitals. The past few
years have seen a renewed interest in transition metal oxides. The current
picture regarding some aspects of their electronic structures, moreover, is
rapidly evolving and controversial. Many of the fundamental questions being
debated, however, have important consequences for problems in the Earth and
planetary sciences.
Electronic transitions of iron oxides and silicates give rise to absorption
bands in the visible and near-infrared reflectance spectra of planetary surfaces.
These absorption bands are used to map the surface mineralogy of the Earth,
Moon, and Mars. Iron oxides and silicates may participate in photochemical
processes on planetary surfaces. In the precambrium, photochemical processes
involving iron oxides and silicates may have played a significant role in prebiotic
chemistry. Even on the present-day Earth's surface, photochemically induced
electron transfer between organic molecules and colloidal iron oxides is
a significant process in lakes and rivers.
In the Earth's interior, electronic transitions of iron oxides and silicates may
playa fundamental role in the electrical and thermal conductivity of the mantle.
It is often assumed, for example, that the d-d or ligand field transitions of Fe 2 +
in the near-infrared would block heat flow by radiative conduction in the
Earth's interior. The apparent semiconducting behavior of the lower mantle
may reflect small polaron conductivity or thermally induced intervalence charge
transfer Fe 2 + + Fe3+ ~ Fe3+ + Fe2+. In the lower mantle, Fe2+ cations may
undergo a spin-pairing transition at high pressure. Spin-pairing of Fe 2 + may
increase the density of (Fe,Mg)O and should be considered in arguments about
convective mixing between the upper and lower mantle. Finally, electronic
transitions may change the nature of the Fe-O chemical bond. It is currently
being proposed that iron oxides transform from simple ionic compounds to
metallic alloys at high pressure and that such changes allow FeO to be
incorporated into the outer core.
Electronic Structures of Fe Sites in Silicates and Oxides
Insofar as iron oxides and silicates are crystalline solids, one would expect that
their electronic structures should be given in terms of Bloch wavefunctions.
However, the orbitals of interest in silicates and oxides, namely those in the
328
Fe(3d) orbitals, are quite localized. (This reflects the partial ionic character of
the bonding in these minerals.) Bloch wavefunctions are awkward to use when
attempting to describe electronic transitions between localized states. A different
approach would be to look at the electronic structure of a small cluster of atoms
representing some structural unit in the crystal by using molecular orbital
theory. With increasing cluster size, the molecular orbital description will
converge to the band structure of the crystal. The molecular orbital view can
account for both localized (ionic) electrons and (if the cluster is sufficiently large)
delocalized (metallic) electrons. We should, at least to a first approximation, be
able to describe the Fe(3d) electronic states in terms of the molecular orbitals of
simple Fe06, and Fe04 clusters. This approach has its precedent in ligand field
theory and should be useful to the extent that the Fe(3d) electrons are localized.
As will be discussed below, this approximation might completely break down in
the Earth's interior where FeO may undergo a Mott transition. Even in the
Earth's crust, there are some electronic states (in particular, those involved in
Fe 2+ --> Fe 3 + charge transfer) in which the Fe(3d) electrons are de localized over
more than one Fe06 coordination polyhedron. To understand such delocalized
states, we will have to use larger clusters or approach iron oxides and silicates in
terms of band theory. Calculations on (Fe2010)15- dimers have been done to
describe intervalence charge transfer and will be described here. As computers
become faster, sophisticated calculations on even larger clusters will become
practicable.
Accurate molecular orbital calculations on transition metal oxide clusters
cannot be easily done using current Hartree-Fock type ab initio methods based
on the linear combination of atomic orbital (LCAO) formalism. A very
successful approach, however, is the XIX-scattered wave method discussed earlier
in this volume.
Electronic Structure of Fe3+ in Octahedral Coordination. Figure 78 shows the
molecular orbital diagram for an (Fe06)9 - cluster with an Fe-O bond length of
200 pm. The electronic structure of the same cluster with a somewhat longer
Fe-O bond length is discussed in Sherman (1985). The O(2p)-like molecular
orbitals are Fe-O bonding while the Fe(3d) like molecular orbitals are Fe-O
anti bonding. Some of the orbitals are labeled according to their associated
irreducible representation of the Oh point group. The orbitals of eg symmetry are
a-bonding (3e g ) or a-anti bonding (4e g ). The orbitals with t 2g symmetry are
n-bonding (lt 2g ) or n-antibonding (2t 2g ). The calculation was done using
a spin-unrestricted exchange potential. This gives separate exchange potential
for spin-up (IX-spin) and spin-down (fJ-spin) electrons and is essential for
describing the electronic structures of open-shell configurations. Note that the
spin-unrestricted molecular orbital results correctly show that Fe 3 + will be in
the high spin configuration in its ground state. Low spin Fe3+ or Fe2+ has not
been observed in any silicate or oxide mineral. Presumably, one must attain
pressures comparable to those in the lower mantle for the spin pairing transition
to occur.

IFeOa)9- RIFe-O)=200 pm
Spin Up
Spin Down
Fe(4s)
-7
329
Fig. 78. Electronic structure of
(Fe06)9- cluster. The orbitals
are labeled according to their
associated
irreducible
representation of the Oh point group.
Orbitals indicated by dashed lines
are unoccupied
-9
>
.!
4e g
-15
>-
} Fe(3d)
Cl
iiic:
--- 2t 29
~
:0
-20
-25
3eg
O(2pl
1t2g
It is important to note that the orbital energy differences in the ground state
electronic structure do not correspond to electronic transition energies. The
latter are calculated using the transition state formalism (Slater 1974) which
accounts for the orbital relaxation about the excited state electronic
configuration. Two kinds of electronic transitions can be described using this
simple cluster: d-d or "ligand field" transitions and ligand-to-metal charge
transfer (LMCT) transitions. As discussed below, the one-electron orbitals give
only a partial description of the different ligand field states of the Fe 3 + cation.
The ligand to metal charge transfer transitions, however, seem to be well
described in terms of the one-electron orbitals of the (Fe06)9- cluster. The
lowest energy LMCT transition, from the O(2p) band to the 2t 2g (P) orbital, is
calculated to have an energy near 38000 cm -1. This energy agrees well with that
found in the spectra of iron(III)-bearing oxides, silicates and oxo complexes
(e.g., Tippins, 1970). The energies of the states arising from the different
330
40
ElkKI
30
4Tl
Fig.79. Multiplet states arising

from the d-orbital configurations
of Fe 3+ . The energy scale is in
cm - 1/1000. The energies of the
multiplet states and the calculated
one-electron configuration energies are from Sherman (1985)
It2ile~)2It~g )1
4E
It2lle~)1 te~)l
4T2
4E,4Al
20
It29)3Ie~)1Ittg)1
10
-L'T'
4Tl
o
configurations over the Fe(3d) one-electron orbitals (4eg and 2t zg ) cannot be
calculated directly from the molecular orbital diagram. This is because a given
one-electron orbital configuration corresponds to several multielectronic
states, as shown in Fig. 79. For example, the one-electron orbital transition
4eg(o:) -+ 2tzg(O:) corresponds to both the 6A 1g -+ 4T 1g and 6A 1g -+ 4T zg
spectroscopic transitions that are observed in the visible and near infrared
spectra of iron (III) silicates. We can, however, understand the states arising from
the d-orbital electronic configurations using ligand field theory. Ligand field
theory expresses the state energies in terms of the three parameters lODq, Band
C. lODq is a measure of the splitting between the 4eg and 2t zg orbitals; Band
C are related to the coulomb and exchange integrals. In principle, we can
calculate these parameters from the one-electron orbitals. However they are
usually determined from optical spectra.
The Fe 3 + ligand field transitions are spin-forbidden since the ground state
has spin quantum number S = 5/2 while the excited states have S = 3/2 or 1/2.
One would expect the ligand field bands in Fe 3 + minerals to be very weak.
However, the spin-selection rule can be effectively relaxed when next-nearest
neighbor Fe3+ cations are magnetically coupled to each other (Krebs and
Maisch 1971; Lohr 1972; Rossman 1975; 1976; Sherman and Waite 1985). The
331
extent to which the spin selection rule is relaxed depends on the strength of the
magnetic coupling between Fe 3 + cations. A pair of Fe 3 + cations are coupled
antiferromagnetically by superexchange. The superexchange interaction
depends on the nature of the bridging ligand L and on the Fe-L-Fe bond angle.
There is a great deal of theoretical work that can be done to understand
the quantum mechanical nature of superexchange and its dependence on the
mode of Fe-Fe bridging. Superexchange is a direct consequence of the
spin-dependency of the chemical bond (e.g., Goodenough 1972). We expect that
coupling due to superexchange will increase as the covalency of the Fe-L
bond increases. Superexchange coupling via Fe-O-Fe bridging is relatively
strong. However, if the bridging oxygen is also bonded to a strong
electron-withdrawing center (Lewis acid) such as H + or Si 4 +, then we would
expect the superexchange coupling to be weaker. This effect is seen in minerals:
strong superexchange due to Fe-O-Fe bridging in iron oxides results in strong
intensification of the Fe 3 + ligand field transitions and gives these minerals their
red to orange color. Weaker superexchange via Fe-OH-Fe and Fe-O(Si)-Fe
coupling in iron silicates (e.g., nontronite) results in a weaker intensification of
the Fe 3 + ligand field bands and gives nontronite a green to pale yellow color.
These effects in the spectra of iron sulphate minerals have been described by
Rossman (1974; 1975).
The strong magnetic coupling, and the consequent intensification of the
Fe 3 + ligand field bands, results in an absorption edge in the visible region
spectra of iron oxides. This edge is often mistaken for the optically induced band
gap transition. Since band gaps in semiconductors are often obtained from
optical measurements, one may see erroneously low values for the band gaps
energies of iron oxides in the literature. The band gap in iron (III) oxides and
silicates corresponds to the 0 2 - ---+ Fe 3 + charge transfer transition (i.e., the
0(2p) to Fe(3d) band gap). As discussed above, the lowest energy 0 2 - ---+ Fe3+
charge transfer transition in the (Fe06)9- cluster has an energy near
38000 cm -lor 4.7 eV; this is well into the near-ultraviolet.
Electronic Structure of Fe3+ in Tetrahedral Coordination. There are several
minerals in which Fe 3 + may be in tetrahedral coordination (e.g., micas, cronstedite, spinels). In the electronic structure of an (Fe04)5 - cluster the Fe(3d)
orbitals are Fe-O antibonding while the 0(2p) orbitals are Fe-O bonding and
o nonbonding. The lowest energy LMCT transition is calculated to occur at
40400 cm - 1 when the Fe-O bond length is 186.5 pm.
The ligand field transitions of tetrahedrally coordinated Fe 3 + are Laporteallowed. Consequently, small amounts of tetrahedrally coordinated Fe 3 + may
have a large effect on the spectra of iron-bearing silicates. The band assignments
are often difficult to make, however, since bands due to tetrahedral Fe 3 + overlap
other electronic transitions of Fe.
Electronic Structure of Fe2+ in Octahedral Coordination. The electronic structures of(Fe06)IO- clusters have been calculated by Tossell et al. (1974). Tossell
332
-8
Spin Up
Fig. 80. Electronic structure of

(Fe06)10- cluster
Spin Down
Fe(4s)
-10
--_ 4eg
:>
} Fe,"d)
-15
2t 2g
.!
>-
OJ
CD
c:
w
:e
0
-20
===----
3eg
} 0(2pJ
1t2g
(1976) determined the pressure dependence of the electronic transition energies.

Recent calculations (Sherman 1991) improved on the earlier results by using the
overlapping sphere approach to the muffin-tin potential. Figure 80 gives a molecular orbital diagram for an (Fe06)10- cluster with R(Fe-O) = 216 pm. The
overall topology of the orbitals is the same as in the analogous Fe3+ cluster. The
one-electron orbital transition 2t 2g (p) ~ 4e g (fJ) corresponds to the 5T 2g ~ 5Eg
absorption band observed in the optical spectra of Fe 2 + oxides and silicates
near 10 000 cm -1 (e.g., Blazey 1977). The calculated energy for this transition is
11 600 cm - 1. The lowest energy ligand-to-metal charge transfer transition in the
Fe 2 + cluster is calculated to be 6.6 eV or 53200 cm - 1. Optical spectra of iron
silicates (Nitsan and Shankland 1976) in, fact, show an intense absorption band
at this energy. As expected from the decreased electronegativity of Fe 2 + over
Fe 3+ , 0 2 - ~ Fe2+ charge transfer is at much higher energy than 0 2 - ~ Fe3+
charge transfer.
Fe2+
Fe3+ Charge Transfer
Many silicate and oxide minerals contain Fe 2 + and Fe 3 + cations occupying

edge-sharing Fe06 coordination polyhedra. Such a condition allows for
333
optically (and perhaps thermally) induced intervalence charge transfer (IVCT)

transitions:
Fe1+
+ Fd+
Fel+
+ Fd+,
where A and B refer to two different sites (which may be crystallographically

equivalent). Optically induced IVCT gives rise to an absorption band near
13000 cm -1 in the optical spectra of silicates and have been the subject of much
interest.
Thermally induced IVCT is a potential mechanism for semiconduction
in the Earth's mantle. Thermally induced IVCT is readily observed in the
Mossbauer effect since (in paramagnetic minerals) it results in a quadrupole
doublet with an isomer shift midway between that expected for Fe 2+ and Fe 3 +.
Phases in which thermally induced IVCT is observed at 298 K include ilvaite,
cronstedite, laihunite, and magnetite. It would be very interesting if high
temperatures could induce IVCT in more common rock-forming minerals.
Minerals in which thermally induced IVCT occurs are characteristically black
owing to a very intense optical IVCT band.
Understanding the nature of IVCT (and the orbitals pathways involved) in
minerals is of great fundamental interest insofar as it relates to electron transfer
and redox mechanisms. The basic model for ICVT is given in the potential
surfaces for an (Fe2010 )15 - dimer shown in Fig. 81. This dimer consists of Fe2+
and Fe 3 + cations occupying octahedral coordination sites sharing a common
q=A
>-
e>
OJ
c::
-\.
q= -A
Configurational coordinate Iq)
Fig.81. Potential energy surfaces describing Fe 2 + [2 t 2 .(#)] ---> Fe 3 + [2 t 2 .(#)] charge transfer.
The solid curves correspond to the potential for the "ionic" states 1/1 1 and 1/1 2' The dashed curves
correspond to the potential energy surfaces for the states '1'+ and '1'_ that result from coupling
1/11 and 1/12' The curves a-a' correspond to the case of weak coupling and give an activation
barrier for thermally induced rVCT. The curves b-b' correspond to strong coupling which
completely delocalizes the Fe2 + [2td 2.(#)] electron over the two Fe sites
334
edge. The dimer has C l v symmetry (Fe sites inequivalent). If we consider the two
sites A and B, we can consider two zeroth-order states corresponding to the two
possible charge configurations:
1/11
Fe1+ Fd+
1/11 = Fel+ Fe~+.

We are interested in the energies of these states along a configurational
coordinate q which traps the electron to a given site. Here, q is a normal of Al
symmetry along which the Fe-O bond length of one site expands while that for
the other site contracts. Let us designate the equilibrium Fe2+ -0 and Fe 3 +-0
bond lengths by RI and R z , respectively. (In oxides and silicates, RI is about
216 pm and R z is about 200 pm.) We are interested in the electronic structure of
the dimer at several points along the configurational coordinate q: At q = - A,
we have R(FeA-O) = RI and R(FeB-O) = R z . At q = )~, we have FeA = Rl and
FeB = R I . At q = 0, R(FeA-O) = R(FeB-O) = (RI + R 2)/2. At q = - )~,
the lowest energy configuration is Fe1 + Fe~ +. At q = )~, the lowest energy
configuration is Fel+ Fe~+. If there is a weak coupling between the Fe atoms at
sites A and B (the nature of which will be described below), the states 1/1 I and 1/1 2
will mix to form the new states
P+
= (X 1/1 I + (1
- (Xl)+ 1/12
P _ = (1 - (Xl)1: 1/1 I
(X 1/1 2,
where (X is the delocalization coefficient and describes the degree to which the
Fe2+ [tlg(P)] electron is delocalized over the two sites. From simple perturbation theory,
(xz
1/2 _
LIE
2(LlEZ + 4J2)+
Here, LIE is the energy difference between 1/11 and 1/12; J is the "resonance
integral" which describes the degree of coupling between the states 1/1 I and 1/11.
At equilibrium, the Fe-Fe pair is at the point q = - Ie: The optical IVCT
transition is then P + ~ P _. The energy for this is indicated by Eop in Fig. 81.
Since (X is small, this effectively corresponds to an electron transfer from site A to
B. The thermally induced IVCT process is for the dimer to stay in the ground P+
state but to move along the q coordinate from q = -)~ to q = )~. If the coupling
between the ionic configurations 1/1 I and 1/1 z is weak (J = J I in Fig. 81), there will
be an activation barrier.
Molecular orbital calculations can give us some insight into the physical
nature of the coupling integral J. Coupling can occur either by direct Fe-Fe
bonding or through "superexchange" via the bridging oxygens. A simple
molecular orbital approach to the problem is to look at the electronic structure
of an (Fe20IO)15- cluster. The electronic structure of this cluster has been
calculated using the SCF-X(X-SW method. Fe2+ ~ Fe3+ charge transfer
is allowed through weak Fe 2+ - Fe 3 + d-orbital overlap across the shared
polyhedral edge. The J parameter is simply a description of the Fe l +- Fe 3 +
Spin Down
-15
Spin Up
Fe 3 +(egl
Fe 2 +(eg)
Fa3+(t 2g1
>OJ
Fe(3d)
335
Fig. 82. Molecular orbital
diagram
for
the
(FezO 10)15 - cluster used
to understand the orbitals
involved in charge transfer.
The
absorption
band
observed near 13 000 cm- I
in
the
spectra
of
mixed-valence silicates is
due to the transItion
Fe2+ [2t Zg (f3)] --+ Fe3+ [2t Zg
(f3)] A transition state
calculation for that energy
in the cluster presented
here gives 10 570 cm - I in
fair
agreement
with
experiment
O(2pl
-25
bonding interaction through such d-orbital overlap. A simplified MO diagram

for the cluster is shown in Fig. 82. Using the transition state formalism, it is
found that the optically induced intervalence charge transfer band results from
the transition
Fe2+ [2t 2g (fJ)]
->
Fe3+ [2t 2g (P)].
In the context of the (Fe2010)15- cluster, the Fe2+ [2t 2g (P)] orbitals are
Fe 2+ -Fe3+ bonding while the Fe3+ [2t2g(P)] orbitals are Fe 2+ -Fe3+ antibonding [all of the Fe(3d)-like molecular orbitals are Fe-O antibonding, of
course]. To determine the activation energies associated with thermally induced
IVCT would require that we calculate the total energy of the (Fe2010)15cluster along the q coordinate. Such calculations cannot be accurately done
using the muffin-tin potential of the SCF-XIX-SW method. Similar calculations
to those described here have also been done to understand Fe 2+ -> Ti 4 + charge
transfer and Fe- Mn charge transfer.
Pressure-Induced Electronic Transitions
High-Spin to Low-Spin Transition. The suggestion that Fe2+ cations may
undergo a high-spin to low-spin transition in the Earth's mantle was first given
336
by Fyfe (1960). The idea has since been elaborated upon and refined by several
investigators (Strens 1969; Gaffney and Anderson 1973; Tossell 1976; Ohnishi
1976; Sherman 1988). The high-spin to low spin transition is geophysically
important, since it should give a significant volume decrease for FeO and greatly
affect the electronic properties of FeO.
The exchange splitting of the electronic orbitals serves to stabilize electronic
configurations which maximize the number of unpaired electrons. At zero
pressure, the high-spin configuration of octahedrally coordinated Fe 2+,
(2t2g)4(4eg)2 is stable relative to the low spin configuration (2t 2g )6 because the
crystal field splitting, 10 Dq, is smaller than the exchange splitting U ex (the
exchange splitting is that between the spin-up and spin-down Fe(3d) orbitals).
With increasing pressure, the crystal field splitting increases; eventually,
10 Dq > U ex and the low-spin configuration will be stable.
A number of attempts have been made to calculate the free energy of the
HS ~ LS transition of FeO as a function of pressure and temperature (e.g.,
Strens 1969; Gaffney and Anderson 1973; Tossell 1976; Ohnishi 1978; Jackson
and Ringwood 1981; Sherman 1988). Both the volume change, L1V, and the
entropy change, L1S can be estimated from first principles while the internal
energy change, L1U, can be approximated by the spin-pairing energy in
a (Fe06)10- or larger cluster. (This can be estimated from ligand field theory
or molecular orbital calculations.) However, estimating these quantities, in
particular, L1V, is subject to considerable uncertainty. Because the ionic radius
for low-spin Fe 2+ is 17 pm smaller than that for high-spin Fe 2+ (Shannon and
Prewitt 1969), the high-spin to low-spin transition of FeO is predicted to have
a volume decrease (at 0 GPa) near 2.50 cm 3 /mole. However, this is a crude
approximation; a first principles calculation of the equation of state of low-spin
FeO is needed. Nevertheless, it appears that a HS ~ LS transition of FeO
is a physically reasonable possibility within the range of pressures and
temperatures of the Earth's lower mantle.
Semiconductor to Metal Transitions. At high pressures and temperatures, FeO
appears to go to a metallic state (Knittle et al. 1986). This transition has been
invoked to allow oxygen into the Earth's core (Knittle and Jeanloz 1986; Jeanloz
1990). This is a significant hypothesis insofar as the nature ofthe light element in
the core may be a fundamental constraint on theories of the Earth's formation
and differentiation. If stoichiometric FeO were stable at zero pressure, it would
be an insulator (or, more precisely, a semiconductor with a larger band gap). The
origin of the insulating nature of FeO (i.e., the nature of the band gap) is
controversial. For many years, FeO was regarded as a prototypical Mott
insulator (discussed below). In the past few years, however, it has been proposed
that FeO is a charge-transfer insulator (e.g., Fujimori et al. 1987; Lad and
Henrich 1989). In the charge-transfer picture, the lowest energy band gap would
correspond to the O(2p)-Fe(3d) separation. Tossell (1976) showed that the
O(2p)-Fe(3d) separation increases with pressure. Hence, semiconduction by
thermally exciting electrons across the O(2p)-Fe(3d) gap is not significant for
337
planetary interiors. Several investigators (e.g., Strens 1976) have proposed that,
at high pressures, FeO might adopt an electronic structure corresponding to the
formal charge configuration Fe +0 -. The Fe +0 - -configuration requires an
O(2p) electron to be excited to the Fe(3d) band. It is clear, however, that the
internal energy of such a charge-transfer state is much too high to have any
geophysical significance.
One possible explanation (Sherman 1989) for the high-pressure metallization
of FeO is a breakdown of the Mott insulting condition (Mott 1961). This
illustrates an important case where the one-electron picture of electronic structure fails; hence, it is worthwhile to outline the essential idea. In FeO, the
minority spin t 2g Fe(3d) band is partially occupied. In the early Bloch-Wilson
view of electronic structure, this would imply that FeO should be metallic.
However, the t 2g Fe(3d) electrons are localized to their parent Fe atoms by the
interelectronic repulsion or correlation energy (Mott 1961). The correlation
energy might be thought of as that required for the charge transfer transition
Fe2+
+ Fe 2 + --+ Fe 3 + + Fe+.
This energy is often referred to as the Hubbard gap and results, in part, from the
increased interelectronic repulsion that must be overcome to form an Fe +
cation. Phases which have localized electrons due to the correlation energy are
referred to as Mott insulators. The inclusion of this correlation energy is
a fundamental problem for electronic structure calculations and requires us to
go beyond the one-electron orbital formalism. The Hubbard gap for FeO is
presumably on the order of several electron volts so that the charge transfer
transition as given above is not possible under geophysically significant temperatures. Mott insulators can become metals if the 3d electrons have enough
kinetic energy to overcome the correlation energy. This is expected to occur at
high pressure and temperature: The kinetic energy increases with the width of
the Fe(3d) band which, in turn, increases with (nominally weak) metal-metal
bonding interactions between next-nearest neighbor Fe atoms. Fe- Fe bonding,
of course, increases with decreasing Fe- Fe separation. This mechanism for an
insulator (or semiconductor) to metal transition is known as a Mott transition.
Although FeO may become metallic at high pressures, we might expect it to
ultimately return to an insulating state if it undergoes a high-spin to low-spin
transition. Of course, if, with increasing pressure, FeO undergoes a high-spin to
low-spin transition before it undergoes a Mott transition, we would never see
metallic behavior in FeO. Since we do not know the equation of state for
low-spin FeO and the critical Fe-Fe separation needed to induce a Mott
transition, it is not clear which electronic phase transition FeO might undergo
first at high pressure.
The apparent metallization of FeO implies that FeO remains high-spin at
least to 70 GPa. Low-spin FeO could not be metallic because the t 2g band
would be full. This would imply that the volume change for the spin-pairing
transition is much smaller than that expected from ionic radii considerations.
An interesting possiblity is that FeO has adopted the CsCI structure at high
338
pressure (Jeanloz and Ahrens 1980). The eightfold coordination of Fe would

preclude spin-pairing (Sherman 1988). On the other hand, in the CsCI structure,
FeOs polyhedra share faces allowing for Fe(3d)-Fe(3d) overlap and, perhaps,
metallic conductivity.
Our present understanding of the high-pressure electronic structures of iron
oxides is poor and the ideas outlined here are speculative. An important point
to note, however, is that the Earth's interior is defining a paradigm for many
fundamental problems in solid state physics. This will, undoubtably, stimulate
new work in the future. First-principles band structure calculations, together
with more experimental work using the diamond anvil cell, will give a much
better understanding of the high pressure electronic structures of iron oxides
and their effects on the physics and chemistry of the Earth's lower mantle.
References
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Mineral 11: 37-51
Banks RJ (1972) The overall electrical conductivity distribution of the Earth. J Geomagn
Geoelect 24: 337-351
Biazey KW (1977) Optical absorption of MgO:Fe. J Phys Chern Sol 38: 671-675
Burns RG (1981) Intervalence transitions in mixed valence minerals of iron and titanium.
Annu Rev Earth Planet Sci 9: 345-383
Burns RG, Nolet DA, Parkin KM, McCammon CA, Schwartz KB (1979) Mixed valence
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Cheng JC, Kemp JC (1971) Magneto-optical study of the spin-lattice relaxation of Fe3+ in
MgO. Phys Rev B Condens Matter 4: 2841-2846
Ducruix J, Courtillot V, Mouel JL (1980) The late 1960s secular variation impulse, the eleven
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Fujimori A, Kimizuka N, Taniguchi M, Suga S (1987) Electronic structure of Fe,O. Phys Rev
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Fyfe WS (1960) The possibility of d-electron coupling in olivine at high pressures. Geochim
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Gaffney ES, Anderson DL (1973) Effect of low-spin Fe2+ on the composition of the lower
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Goodenough JB (1980) The Verwey transition revisited. In: Brown DB (ed) Mixed-valence
compounds. Reidel, Dordrecht, Netherlands, pp 413-415
Goodenough JB (1972) Metallic oxides. Prog Sol State Chern 5: 1-399
Jackson I, Ringwood AE (1981) High-pressure polymorphism of the iron oxides. Geophys JR
Astr Soc 64: 767-783
Jeanloz R (1989) High-pressure chemistry and physics of the Earth's mantle and core, chap 4,
In: Peltier WD (ed) Mantle convection, pp 203-259
Jeanloz R (1990) The nature of the Earth's core. Annu Rev Earth Planet Sci 18: 357-86
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505-528
Johnson KH (1973) Scattered wave theory of the chemical bond. Adv Quant Chern 7: 143-145
Knittle E, Jeanloz R (1986) High-pressure metallization of FeO and implications for the
Earth's core. Geophys Res Lett 13: 1541-1544
339
Krebs JJ, Maisch WG (1971) Exchange effects in the optical absorption spectra of Fe3+ in
A1 20 3. Phys Rev B4: 757-769
Lad RJ, Henrich VE (1989) Photoemission study of the valence-band electronic structure in
Fe,O, Fe304 and IX-Fe203 single crystals. Phys Rev B 39: 13,478-13,485
Lohr LL (1972) Spin-forbidden electronic excitations in transition metal complexes.
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340
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5.6 Hydrogen Bonding in Minerals

F.C HAWTHORNE and W.H. BAUR
Hydrogen Bonds
Hydrogen is quite electropositive and can be represented as a cation, H +, which

usually has a coordination number of [2]. This arrangement generally undergoes a spontaneous distortion with the hydrogen moving off-centre towards one
of the two coordinating anions. Hydrogen forms a strong covalent bond with
the closer anion, and has a weak interaction with the more distant anion. Such
an arrangement can be represented as D-H. .. A, where D is the strongly bonded
donor anion and A is the weakly bonded acceptor anion; the H. .. A bond is
referred to as a hydrogen bond. When the coordination number of hydrogen is
greater than [2], there is one short D-H bond and two or more H ... A hydrogen
bonds; the latter are called bifurcated (or trifurcated) bonds. The geometry of
this arrangement has been well-characterized by neutron diffraction, and is
conveniently interpreted using bond-valence theory.
Hydrogen-Bearing Groups
There are five different hydrogen-bearing groups in minerals: (OH)-, (H 20)O,

(HJO)t-, (H S 0 2 )+, and (NH4)+; sketches of local geometry and bond-valence
distributions in these species are shown in Fig. 83. The positively charged
groups act as complex cations and are extremely uncommon, although they
have been identified in such minerals as hydronium jarosite {(H30)
[Fe~ +(S04}z(OH)6]}' rhomboclase {(H S 0 2 )Fe3+ (S04}z(H 2 0)2]} and tobelite
{(NH 4)[AI 2(Si 3AI)01o(OHh]}. On the other hand, (OH)- and (H 2 0)O groups
play very important roles in the structures of oxysalt minerals. The reason for
this stems from the extremely directional nature of the bonding associated with
these two groups; on the oxygen side of each group, they function as an anion,
whereas on the hydrogen side of each group, they function as a cation, giving
these two groups some very unique structural properties and allowing them to
play four structurally different roles in minerals.
(0 H rand (H 2 0) in the Structural Unit. The structural unit of a mineral is

that part of the structure that is strongly bonded together (e.g., a feldspar
framework, a mica sheet). For both (OH)- and (H 20)O, the bonding on the
anionic side of the group is fairly strong [ '" 1.2 v.u. for (OH) - and '" 0.4 v.u.
341
~
OH
(a)
.:0.33
0.2 !
0.33:
I
I
(c)
i
:0.33
(b)
(e)
(d)
If
,"0.25
......
0.25
0.25
......
0.25,
}I'
... 0.25
"
Fig. 83a-e. Hydrogenbearing groups in minerals, showing geometry and bond-valence

distributions. a (OH)-. b (H 2 0)o. c (H30)+. d (H S 02)+' e (NH4)+
for (H 2 0)D] whereas the bonding on the cationic side of the group is much
weaker ( '" 0.2 v.u. for both groups). Thus on the anionic side of the group, the
strong bonding constitutes part of the bond network of the structural unit;
conversely, on the cationic side of the group, the hydrogen bond is too weak to
form part ofthe bond network ofthe structural unit. The role of both (OH)- and
(H 2 0)o is thus to "tie off" the polymerization of the structural unit in specific
directions. This is illustrated for artinite (Mg 2 (C0 3 )(OH}z(H 2 0h) in Fig. 84; the
occurrence of both (OH)- and (H 2 0)0 as anions bonded to octahedrally
coordinated Mg prevents further structural polymerization in any direction
except along the length of the ribbon. Thus the dimensionality of the structural
unit of a mineral is primarily controlled by the amount and role of hydrogen in the
structure. As the character of the structural unit is the primary factor affecting
the physical properties and stability of a mineral, it follows that hydrogen is

perhaps the most significant element in controlling the properties and behaviour
of minerals.
(H 2 0)0 Bonded Only to Interstitial Cations. Cations whose bonding is too weak
to be considered as part of the bonding network of the structural unit are called
interstitial cations; these are generally alkalis and alkaline earths. (H 2 0)0 can act
342
OH
Fig. 84. The structural unit in artinite, a ribbon of (Mg06) octahedra and (C0 3 ) triangles; all
anions not bonded to carbon are either (OH) - or (H 2 0)O
as a ligand for these cations, and often does for one or more of the following
reasons:
1. to satisfy bond-valence requirements around the interstitial cation in cases
where there are insufficient anions available from adjacent structural units;
2. to transfer bond-valence from the interstitial cation to a distant unsatisfied
anion of an adjacent structural unit;
3. to act as a bond-valence transformer between the interstitial cation and the
anions of the structural unit.
The structure ofstringhamite {Ca[Cu(Si0 4 )](H 2 0)} is a good example (Fig. 85).
The structural unit is a sheet of corner-sharing (Si0 4 ) tetrahedra and squareplanar (Cu0 4 ) groups arranged parallel to (010). These sheets are linked
together by interstitial Ca atoms, each Ca linking to 4 anions of one sheet and 1
anion of the adjacent sheet. The coordination number of [5], rarely observed for
Ca, is not adequate with regard to the satisfaction of local bond-valence
requirements at the Ca, and 2 (H 2 0)0 complete the Ca coordination; in addition,
these (H 2 0)0 groups carry the bond-valence (via hydrogen bonding) from Ca to
anions too far away to bond directly to Ca. Thus the structural role of such
(H 2 0)0 groups is very different from when (H 2 0)0 is part of the structural unit.
Hydrogen-Bonded Interstitial ( H 2 0 ) 0 Groups. In some structures, (H 2 0)0

groups occur as interstitial species without bonding to an interstitial cation, but
still participate in a well-defined hydrogen-bonding network. (H 2 0)0 groups of
this sort act both as hydrogen-bond donors and as hydrogen-bond acceptors.
Minerals with such hydrogen-bonded networks can be envisaged as intermediate between anhydrous minerals and clathrate structures. An example is
343
f
a
~I
Fig. 85. The crystal structure of stringhamite, showing the structural units linked by Ca that
also bonds to two interstitital (H 2 0)O groups
mandarinoite {[Fe~+(Se03h(HzOh](HzOh} (Fig. 86). The structural unit is a

heteropolyhedral framework of corner-linking (Se0 3) triangular pyramids and
(Fe0 6 ) octahedra, with large cavities that are occupied by hydrogen-bonded
(HzO)O groups in well-defined positions. Thus of the 6 (HzO)O groups in this
mineral, three are part of the structural unit and 3 are hydrogen-bonded
interstitial (HzO)o.
Occluded (H zO)O Groups. In some structures, interstitial (HzO)O is not involved

in any static hydrogen bonding arrangement. Normally, such (HzO)O groups are
located in large holes or cavities within the structure, and their interaction with
the rest of the structure is through a Van der Waals effect. Such groups are found
in beryl, cordierite and the large-pore zeolites such as faujasite. Such (HzO)O
does not playa significant structural role, but can have important effects on such
physical properties as specific gravity, refractive index and dielectric behavior.
Experimental Determination of H-Stereochemistry
There are three principal methods by which presence and stereochemical details
of hydrogen-bearing groups can be detected: (1) neutron diffraction; (2) X-ray
diffraction; (3) infrared spectroscopy.
344
.. , /
-1';:'' \
r" ~
/
,,
T
b
i . '
------,I-~" "' - """"'"
-....,(
\
+!,
I~
\
~I
Fig. 86. The crystal structure of mandarinoite; note the two types of (H 2 0)O groups, one
bonded to cations of the structural unit, and the other held only by a network of hydrogen
bonds
Neutron Diffraction. Hydrogen has a reasonably large negative neutron

scattering length, and thus hydrogen can be accurately located in most minerals
by crystal structure solution and refinement, the most direct and reliable way of
deriving this information. Often, the available material is not suited to this
experiment and other methods must be used.
X-Ray Diffraction. Hydrogen scatters X-rays very weakly, and the location of
hydrogen atoms directly by crystal structure refinement of X-ray data can be

difficult or unreliable. However, bond-valence and stereochemical arguments
involving the rest of the structure are generally sufficient to derive accurate
(although not very precise) hydrogen locations and/or details of hydrogenbearing groups present.
Infrared Spectroscopy. Both (OH) - and (H 2 0)O groups have fundamental
vibrational motions that absorb radiation in the infrared region. The (OH) group shows a single stretch usually around 3600 cm - 1, but varying between
3700 and 2000 cm -1 depending on the strength of the associated hydrogen
345
o+
(a) /
/'
o+
vI
3652cm- 1
(c) /
---....
....
v2
1595cm-1
(b)
Fig_ 87. The three normal modes of vibration for the H 2 0 group. a Symmetric stretch.
b Asymmetric stretch. c Symmetric bend
Table 28. (OH)- and (HzO)O principal absorption bands in
minerals
Wavenumber
Group
1630cm- 1
3400
3500
Motion
H-O-H bend
O-H stretch
O-H stretch
bonding; weak hydrogen bonds have absorption frequencies around 3600 em -1,
the frequency decreasing with increasing hydrogen-bond strength. The (HzO)O
group is a little more complicated. There are two fundamental stretching
motions and one bending motion (Fig. 87), and these give rise to a set of
characteristic absorptions in the infrared (Table 28), the exact energies of which
are affected by details of local stereochemistry. Thus polarized infrared spectroscopy is a powerful method for detecting the presence of hydrogen in a mineral,
and for determining its speciation. In turn, the method can also be used as a
probe of local structure (particularly order jdisorder) when details of the hydrogen speciation are known. This method has been particularly important in
detecting the presence of minor to trace amounts of hydrogen in minerals
previously thought to be anhydrous (e.g., olivine, feldspar, garnet).
Geometry of Hydrogen Bonds

Reliable local geometries for ordered hydrogen-bonded systems can be derived
from neutron diffraction experiments. Statistical analysis of a large amount
of such data gives the local geometries of Table 29. The value
D-H ... O for (HzO)O shows a wide variation (range ~ 100-180), but most
values lie within 10 of the mean. The data of Table 29 are very useful for
assigning hydrogen-bond arrangements in X-ray structural studies.
346
Table 29. Local geometries of hydrogen bonds involving

(OH)- and (H 2 0)O
O-H
O-A
H-O-H
0.96 A
2.81
108
H... A
H-H
O-H ... A
1.88 A
1.56
170
Solid Solution in Minerals

The (OH)- group is a common major constituent of many minerals, the
amphiboles and the micas being of particular petrological significance. There
are other (fairly) common monovalent anions (e.g., F - ,Cl-) present in many
geological environments, and there is the possibility of extensive monovalent
anion solid solution. However, there are significant structural constraints on
such substitutions. The most significant is the fact that the (OH)- is involved in
hydrogen bonding, unlike the simple monovalent anions which are anionic in all
directions. Thus F- and Cl- will generally substitute for (OH)- only when the
(OH)- group is involved with weak hydrogen bonding and the local structure is
able to adjust to the absence of hydrogen bonding around the substituent F- or
CI-. In common rock-forming minerals with such weak hydrogen bonding,
both silicates (e.g., amphiboles, micas) and nonsilicates [e.g., amblygonitemontebrasite, LiAI(P0 4 )(OH,F)] commonly show partial to complete solid
solution of this sort, and it should be noted that the (OH) = F substitution is an
important factor affecting the stability of such minerals.
Hydrogen Bonding and Complexity in Minerals

There are approximately 3500 known minerals, and the maJonty of these
contain hydrogen as a major constituent. As noted above, both (OH)- and
(H 2 0)0 exert a dominant control on the dimensionality of the structural unit. It
is apparent that it is the availability of hydrogen, together with the weak and
anharmonic nature of the hydrogen bond, that accounts for the gradual increase
in number and complexity of minerals from the core through the mantle and
crust to the surficial environment.
References
Baur WH (1965) On hydrogen bonds in crystalline hydrates. Acta Cryst 19: 909-916
Baur WH (1972) Prediction of hydrogen bonds and hydrogen atom positions in crystalline
solids. Acta Cryst B 28: 1456-1465
Brown ID (1976) On the geometry of O-H ... O hydrogen bonds. Acta Cryst A 32: 24-31
Emsely J, Jones DJ, Lucas J (1981) Detecting and measuring strong hydrogen bonds: recent
developments. Rev Inorg Chern 3: 104-140
347
Ferraris G, Franchini-Angela M (1972) Survey of the geometry and environment of water

molecules in crystalline hydrates studied by neutron diffraction. Act Cryst B 28: 3572-3583
Ferraris G, Ivaldi G (1984) X-OH and OH ... O bond lengths in protonated oxoanions. Acta
Cryst B 40: 1-6
Kvick A (1986) Hydrogen bonding in zeolites. Trans Am Cryst Assoc 22: 97-106
Newton MD (1986) Current views of hydrogen bonding from theory and experiment structure, energetics, and control of chemical behaviour. Trans Am Cryst Assoc 22: 1-17
CHAPTER 6
Properties of Minerals
Chapter 6. Properties of Minerals
350
6.1 Elastic Properties of Minerals

Y.M. AGosHKovand V.L. PANKOV
Elasticity of solids is the property that restores their form after deformation. The
elastic properties of minerals and rocks are widely utilized in geophysics and
geochemistry to interpret information on the interior of the Earth and other
planets; these properties are indispensable in solid state physics for constructing
the acoustic branch of vibrational spectra and equation of state, and also in
geotectonics for characterizing the rheology of the Earth's crust and mantle.
To describe deformation of a single crystal, the continuous medium model
is generally used. In this model a material point represents a volume element
consisting of a great number of lattice cells. For a perfectly elastic material Hooke's law establishes a linear relation between the stresses O"j and the
strains Gj:
O"j ==
L C j/ j
j = I
or
Gj
L1 SjPj,
j=
where C jj are the elastic constants (the stiffness constants or elastic moduli), Sjj
are the elastic compliance coefficients, the indices 1,2,3 refer to the normal stressstrain values, and 4,5,6 to similar shear characteristics.
The anisotropy of a crystal lattice leads to the anisotropy of elastic properties characterized by a set of elastic constants Cjj or Sjj. The number of
independent moduli corresponding to the crystal symmetry varies from 21 for
triclinic crystals to 3 for cubic crystals.
By using special combinations of the Cjj in an averaging procedure, we may
define two independent elastic moduli that completely describe the elasticity of
homogeneous, isotropic mineral aggregates. In practice, however, it is more
convenient to use a set of interrelated elastic characteristics such as Young's
modulus E, shear modulus 11, and bulk modulus K = - VL1P/L1V, where Pis
pressure and V is volume, Poisson's ratio 0", etc. All these values depend on the
thermodynamic P-T conditions of the deformation process. Therefore we
distinguish the isothermal and adiabatic constants KT and Ks as well as the
elastic constants
or C~j. In particular for isotropic material we have:
Cr;
Ils
= IlT'
Ks
p(ap/ap)s
KT(l
+ ayT),
Ks/KT
Cp/C v ,
where p is density, a = V-I (aV/aT)p is the volume coefficient of thermal

expansion, y = aKs/ pCp the thermal Griineisen parameter, and Cp and C v are
heat capacities at constant pressure and volume, respectively.
There are numerous possible schemes for averaging Cij over all of the lattice
orientations that give isotropic mineral properties. The most widely utilized
scheme for practical reasons is the method of Voigt-Reuss-Hill (VRH), which
averages Ks and 11. In the case of strongly anisotropic crystals with low
symmetry, the accuracy of VRH averaging is not sufficient, and the more
complicated Hashin-Strickman method is recommended as physically valid.
351
The elastic moduli, K s , 11, and the density, p, determine one longitudinal
or compressional Vp and the two shear or transversal wave velocities Vs in
isotropic aggregate:
V~ = Ks + 4/3 11 , V~ = ~.
p
The elasticity of heterogeneous polyphase mineral aggregates such as rock

can be characterized by a set of polycrystalline elastic moduli or constants Cij.
These values are related to the preferred orientation of constituent mineral
components. It should be mentioned that available seismic data for the Earth's
upper mantle suggests rather essential elastic anisotropy that could be interpreted in terms of the texture of anisotropic grains of olivine and the stress
fields in the mantle.
For a statistically isotropic, single-phase polycrystal which consists of a
compact mixture of chaotically oriented, small crystallites, the elastic constants
are naturally averaged values and consequently, measured velocities of Vp and
Vs in such a material should be close to the averaged properties of the
monocrystal. Experiments on natural and synthetic isotropic samples, however,
show different and not always understandable occurrences of their texture,
porosity, and other microstructural features which can plausibly account for the
observed discrepancies in elasticity of poly- and monocrystals. Thus in geophysical applications, preference is given to monocrystal elastic data.
The macroscopic elastic properties of minerals are directly related to forces
acting between microscopic structural units of the mineral: atoms, ions, ion
clusters, and electrons. These forces are integral weighted characteristics of
interatomic interactions. For example, the elastic constants Cij can be expressed
in terms of the lattice-summarized force constants which represent the second
derivatives of the monocrystal potential energy on atomic displacements from
their equilibrium positions. The influence of temperature atomic vibrations on
elasticity is taken into account by the expansion of potential energy in a series of
atomic displacements. The truncation of the second order terms leads to a
quasi harmonic approximation but only the fourth order terms give complete
anharmonic approximation.
In a crystal lattice containing N atoms, the vibrational spectrum consists of
3N different types of oscillations or modes. The three elastic modes form the
acoustic branch and the remaining 3N - 3 oscillations form the optical branch of
the spectrum. In some circumstances, as proposed by Debye, the vibrational
spectrum can be entirely approximated by the acoustic branch. In this case, the
solid is considered as an isotropic elastic continuum, and the number of all the
elastic modes is assumed to be equal to 3N. In such a case, the vibrational
spectrum is limited by the highest cutoff frequency, Wm' which corresponds to a
Debye temperature eo : eo = wmfl/k, where fl is Planck's constant, and k is the
Boltzmann constant. In the Debye model, eo is expressed in terms of velocities of
the longitudinal Vp and the transversal Vs acoustic waves. In a low temperature
region when T ~ eo, almost all the optic lattice modes are "frozen" and the rest
of spectrum consists of only elastic vibrations which are correctly described
352
by Debye theory. In contrast, at high temperatures (T ~ (JD) all vibrating modes

are excited and according to that theory molar specific heat has the limit,
C y ~ 3RN (where R is a gas constant).
Elasticity of Minerals
Experimental Methods of Investigations. Experimental methods for determining
elasticity are subdivided into static and dynamic. The experimental methods are
used for the investigation of strains, deformations, and strength under tension,
bending, and the torsion of metals, polymers, and ceramics. Dynamic methods
are widely used to measure the elastic properties of rocks and minerals.
1. Ultrasonic methods which are based on the determination of the velocities of the polarized elastic waves, Vp and Vs, along various directions over a
wide range of frequencies (USV). Different modifications of the ultrasonic
method, for example, pulse echo, pulse transmission, modified pulse, or pulse
repetition permit investigation of elastic moduli of mono- and polycrystal in the
range of pressures up to 80 kbar and temperature ::; 1000 K. Because of the
accuracy and broad intervals of P and T experimental data, it is possible to
calculate the first and second derivatives of elastic moduli.
2. Resonance methods in which free vibrations of rectangular parallelepiped
samples are utilized (RPR). The measured set of such vibrations of a sample is
compared with the theoretical one, depending on sample dimensions, density,
and elastic constants C jj The principal advantage of RPR is the ability to
measure the elastic characteristics of monocrystals up to extreme temperatures
of 1800-2000 K under ambient pressure because of strong attenuation of free
oscillations at elevated P.
3. Brillouin scattering of optic vibrations (BS), whose essence consists in the
unelastic scattering of light on acoustic phonons and changing the frequency of
optic oscillations. The Doppler shift of frequency is applied to the optic
properties of crystal and the velocities of acoustic vibrations. BS measurements
of mineral elastic properties carried out during the last decade, allow the
investigation of small crystals in diamond anvils under high pressure (up to
100 kbar). Brillouin scattering is possibly a unique way to obtain information on
the elasticity of mineral polymorphs synthesized at high pressure and temperatures.
The X-ray static method should be mentioned for determining bulk moduli
of minerals under pressure of up to - 1 mbar by fitting the relevant type of
equation of state to experimental volume-pressure values; but this method is not
highly accurate for pressure derivatives of bulk modulus K' = oK/oP.
Furthermore, the shockwave data of elastic properties are reliable, and are
widely used for geophysical purposes in the very high pressure range.
The most complete recent summary on mineral elastic properties determined
by various generally ultrasonic methods was published in 1984 by Sumino and
Anderson. This compilation, based on single-crystal data for 164 minerals, their
353
6.l Elastic Properties of Minerals
polymorphs, and solid solutions gives information on isotropic elastic characteristics such as K s , K T, Vp , Vs , j1., (1, e, and P- T derivatives as well as
thermodynamic values: Griineisen constants, Anderson-Griineisen parameters,
and some critical gradients considered in geophysical applications.
Oxides
RPR data which had been obtained before 1983 for different simple oxides were
repeated for periclase and corundum over a temperature range up to 1300 K,
and showed that in general the values of Cij diminished linearly with temperature. This fact leads to the approximately linear decrease of values Ks and j1. at
elevated temperatures. These results, combined with additional independent
data on volume thermal expansion, a:(T), and heat capacity, C p , have given other
elastic and thermodynamic characteristics for oxides. Thermal Griineisen
gamma Ylh is influenced insignificantly on T at P = const, but at V = const for
all considered minerals Ylh essentially decreases with T up to 30%, which
suggests some serious deviations from the Mie-Griineisen approximation
Y = y(V). At high temperatures, anharmonic parameters J T and J s tend
to constant values which satisfy a condition J T - J s ~ y. This corresponds to
(aKT/aT)v ~ 0, or with a good approximation J T ~ K~ and a:*K T ~ const.
These high-temperature elastic properties have been for the most part
confirmed by further RPR measurements on synthetic samples of periclase and
corundum over a temperature range of 1800 K (e/T = 1.8-2.2). Some weak
deviations from the usual linearity Cij(T) have been demonstrated at the highest
temperatures. It was especially pointed out that at extremely high T, distinctions
and scattering data of thermal expansion volume coefficient a:(T) strongly
influenced anharmonic properties, but calculated values of moduli Cij were
practically independent of a:(T) data.
Ultrasonic measurements (USV) of elasticity on MgO have been extended
to 78 kbar under quasi-hydrostatic conditions. The Birch-Murnaghan theory,
applied for extrapolation with experimental C jj , predicted elastic softening of
modulus C 44 at - 1 Mbar, but a hardemng of shear constant C s =
Cll -C 12
2
that led to lattice instability and phase transition in the vicinity of 1 Mbar. The
next unusual result of extrapolation was a negative mean a:(T) at pressures
> 500 kbar, which could not be explained without the assumption on phase
transition.
Elastic moduli of spinel, MgAI 2 0 4 , up to 60 kbar showed agreement in
moduli with previous measurements, hence P derivatives received at high
pressure had marked difference from those at lower pressures. Extrapolation to
higher pressures according to the Birch-Murnaghan equation leads to softening
of the elastic moduli - all Cij < 0 and Ks < 0 at P > 200 kbar. This latter
confirms the supposed mechanical instability in spinels and testifies in favor of a
similar explanation of seismic anomalies in the transition zone of the mantle.
354
Silicates
The elastic properties of olivine have been studied in greater detail than any
other silicate material. High temperature RPR data on C ij of forsterite up to
1700 K (TIf) = 2.3) reveal the same regularities as in oxides: an almost linear
decrease of Vp and Vs with rising temperatures, a decrease of isothermal bulk
modulus with temperature being more essential than that of adiabatic value, K s ,
the difference reaching 10% at high T. From linear temperature dependence of
Vs and Vp, an important parameter v = (aln VslaIn Vp) ~ 1-1.4 has been found.
However, recent values for the lower mantle are v = 2 -:- 3.
Elastic moduli C ll-C 66 of forsterite, investigated up to 40 kbar in a
diamond anvil cell by BS, are almost the same as those measured by ultrasonic
methods. The pressure derivatives C'1l-C~3 are 7-22% higher than those
determined by USV, but C~4' C~5' and C~6 are lower. Negative values of second
P derivatives C~4' C~5' C~6 confirm Pourier's proposed mechanism for the
transformation from olivine to spinel structure by gliding of oxygen closepacked layers.
A complete set of elastic moduli and their P-T derivatives have been
measured by USV for fayalite. These data are in excellent agreement with the
static X-ray measurements up to 70 kbar, but they differ significantly from high
temperature RPR results, which give values of Ks 8% higher.
The elastic properties of olivines - forsterite-fayalite solid solutions - have
an almost linear correlation with end members, as was established by ultrasonic
measurements of 12 intermediate compositions. The results of the investigation
are inconsistent with the systematic decrease in bulk modulus with increasing
molar volume found in olivine-structured silicates. For all silicate olivines the
longitudinal moduli decrease in the order C II > C 22 > C 33 , regardless of
composition.
Single crystal elastic moduli or y- and fJ-spinel phases of Mg 2 Si0 4 have been
determined by Brillouin scattering at ambient conditions. Values of the bulk
moduli of both of these phases are lower than previous measurements. Elastic
properties of y- and fJ-spinels Mg 2 Si0 4 are quite similar, with the greatest
differences related to the C axes of the beta, which is relatively softer under
compression. The polycrystalline acoustic velocities differ by only 1% for these
two phases. Thus there should be no seismic discontinuity associated with a beta
to gamma phase transitions. The derivatives of elastic moduli with respect to
iron content are very similar to those observed in olivine phases. The most
striking similarity of elastic moduli between IX-olivine and y-spinel is C II of
olivine and C~ I of spinel, which represent the stiffness along the close-packed
directions of each polymorph.
In silicate, as in other spinels, elastic anisotropy increases rapidly if the
crystallographic parameter, U, approaches a limiting value near 0.27, which may
be related to the mechanical stability of the spinel structure. Therefore, germanium spinels which have U ~ 0.3-0.32 are inappropriate analogies of elastic
properties for silicate spinels. Polycrystalline y-Mg 2 Ge0 4 has pressure deriva-
355
tives, especially /l', essentially lower than the values for spinel, MgA1204' and
y-Mg zSi0 4
The bulk moduli of orthopyroxenes measured by different methods are
essentially constant for all compositions, but shear modulus, /l, decreases
linearly with increasing iron content. A striking feature in the ultrasonic data for
monocrystal bronzite, Enso and MgSi0 3 , is a high mean for the first (and/or
second) pressure derivative, K' = 10-11, that is much greater than the usual
range for many minerals K' = 4-6.
The same insignificant variations of moduli among Mg-Fe-Ca-bearing
monoclinic pyroxenes was demonstrated by BS measurements of hedenbergite
at P = 0. The dependence of the elastic properties on the composition of the
Ml site is affected by the composition of the M2 site. The substitution of AI3+
for Fe3+ on the Ml site has a great effect on those moduli when Na 1 + occupies
the M2 site instead of Ca Z +.
The high pressure phase of pyroxenes which constitutes the lower mantle of
the Earth is cubic or orthorhombic perovskite-like polymorph. Elastic properties of orthorhomobic MgSi0 3 were investigated by BS. Measured moduli are
10% lower than previously determined in diamond anvil cells, but the agreement is reasonable when uncertainties of the compression studies are taken into
account. A MgSi0 3 is considered to be a ferroelastic phase. A great number of
single-crystal elastic moduli reflect the rigidity of the Si0 6 octahedron under
compression and shear. In particular the ratio of the shear modulus to bulk
modulus MgSi0 3 is larger than has been reported for any other compounds in
the structure of perovskite. This behavior is consistent with earlier observations
on the elastic properties of stishovite and MgSi0 3 ilmenite; but P and T
derivatives of bulk and shear moduli for the perovskite phase are not yet known
in detail.
The elastic moduli of garnet solid solutions have been measured by various
methods including RPR, USV, and BS, and they are safely described by the
linear relationship between the properties of end members. However, data on
the elasticity of majorite are inconsistent. According to ultrasonic measurements, the elastic moduli of solid solution 70% of pyrope-30% of majorite are
almost the same as for pyrope, but X-ray data on the elasticity of solid solution
42% Py-58% Mj reveal a marked decrease in majorite bulk moduli in comparison with those for pyrope. There is the same tendency towards a decrease in
bulk modulus for almandine-ferrous majorite solid solution with increasing iron
content.
Elasticity and Equations of State
Investigations of the elastic properties of minerals are used to construct

equations of state which establish the relations between pressure, density, and
temperature. Further progress on composition and properties of mantle is made
356
by means of these equations and the seismic characteristics of minerals and

rocks.
Semi-empirical equations of state including material parameters are widely
used. These parameters are expressed by means of "hydrostatic" elastic constants Ko, K~, K~ - compressional bulk modulus and its pressure derivatives,
i.e., moduli 2nd, 3rd and 4th orders; the subscript "0" means that the pressure is
equal to zero. The kind of functions P(p,T) in finite strain theory is determined
phenomenologically. The Birch-Murnaghan equation of the 3rd order which is
often used in geophysics is concerned with a similar function, though different
types of equations could be applied.
In another approach, the so-called method of potentials, the simple exponential dependence potential of volume is assumed, but thermal vibrations can
be taken into account in quasiharmonic or unharmonic approximations. Truncation by quasiharmonic terms leads to the Mie-Griineisen equation of state. In
this equation the most complicated circumstance is the evaluation of the
Griineisen parameter averaged according to the vibrational modes. To avoid
such a procedure, it is supposed that a high temperatures, i.e., T> 0D, IXKT
= const, KT = KT(P), and IX '" P -b T The value <>T is the Anderson-Griineisen
parameter, and it could be expressed by the formula: <>T = (clM/clnp) =
- (IXK T)-l*(cKT/cT)p. These expressions introduce the proper correlations
between the compressional modulus and the thermal expansion of crystal.
In semi-empirical equations of state, parameters Ko, K~, K~ are determined
from precise ultrasonic or Brillouin measurements, and also by means of fitting
P-p- T dependencies from shock-waves or X-ray experimental data to a chosen
type of equation of state.
Another way to construct equations of state which has been intensively
developed within the last 6-8 years consists in solving the problem ab initio,
from first principles. Some numerical experimental or empirical parameters are
introduced into a given type of interatomic potential for computer simulating
the model of vibrational spectrum, lattice parameters, and different properties of
the mineral, including elastic constants. In this case, the equation of state is
derived from this model spectrum as a function of volume. Such a computer
simulation was provided for forsterite, [3- and y-spinels, and the results were in
excellent agreement with the equation of state calculated according to ultrasonic
data.
The main feature of almost all minerals is polymorphism under high
pressure. Some of these phases formed at high pressure: coesite, stishovite, [3and y-spinels, ilmenite and perovskite phases of pyroxenes, majorite, and others
can be quenched and studied in metastable conditions. The construction of
pressure-temperature phase diagrams of multicomponent systems with the help
of concordant equations of state or thermodynamic potentials is one of the aims
in investigations in geochemistry and geophysics, where simultaneous utilization of thermodynamic and elastic properties is required.
Relations between thermodynamic and elastic properties of minerals are
illustrated by the known paradox of the Anderson-Griineisen parameter, <>T' for
357
the lower mantle. According to seismic tomogrpahy, the mean c5 T ~ 2-3, but for
many substances, experimental data and equations of state showed that c5 T ~
4-6. It is supposed that the differences in c5 T are caused by variations in the
composition or the viscous peculiarities of the mantle.
The equation of state is directly connected with bulk moduli Ks or K T
Another principal parameter of isotropic minerals is the shear modulus, j1.,
which enters the equation of state in a nonevident way. Shear modulus is more
sensitive to the crystal structure of mineral than bulk modulus, but there are no
reliable methods to measure j1. at a pressure of more than 100 kbar. Hence the
study of this parameter influenced by T and P is of great interest, as it offers the
possibility of appreciating the rheological properties mantle of the Earth and
associating them with tectonic movements and continental drift.
References
Anderson OL, Goto T (1989) Measurements of elastic constants of mantle-related minerals at
temperatures up to 1800 K. Phys Earth Planet Int 55: 241-253
Bass JD (1986) Elasticity of uvarovite and andradite garnets. J Geophys Res 91: 7505-7516
Bass JD (1989) Elasticity of grossular and spessartite garnets by Brillouin sepctroscopy.
Bass JD, Weidner DJ, Hamaya N, Ozima M, Akimoto S (1984) Elasticity of the olivine and
spinel polymorphs of Ni zSi04 Phys Chern Minerals 10: 261-272
Basset WA, Shimizu H, Brody EM (1982) Pressure dependence of elastic moduli of forsterite
by Brillouin scattering in a diamond anvil cell. In: Akimoto S, Manghnani MH (eds)
High pressure research in geophysics. Centre for Academic Publication Japan, Tokyo,
pp 115-124
Duffy TS, Anderson D L (1989) Seismic velocities in mantle minerals and the mineralogy of the
upper mantle. J. Geophys Res 94: 1895-1912
Duffy TS, Vaughan MT (1988) Elasticity of enstatite and its relationship to crystal structure.
Goto T, Yamamoto S, Ohno I, Anderson OL (1989) Elastic constants of corundum up to
1825 K. J Geophys Res 94: 7588-7602
Graham EK, Schwab JA, Sopkin SM, Takei H (1988) The pressure and temperature
dependence of the elastic properties of single-crystal fayalite Fe zSi 0 4 Phys Chern Minerals
16: 186-198
Isaak DG, Anderson OL, Goto T (1989a) Elasticity of single-crystal forsterite measured to
1700 K. J Geophys Res 94: 5895-5906
Isaak DG, Anderson OL, Goto T (1989b) Measured elastic moduli of single-crystal MgO
up to 1800 K. Phys Chern Minerals 16: 704-713
Jeanloz R, Thompsen AB (1983) Phase transitions and mantle discontinuities. Rev Geophys
21:51-74
Kandelin J, Weidner DJ (1988a) The single-crystal elastic properties of jadeite. Phys Earth
Planet Int 50: 251-260
Kandelin J, Weidner DJ (1988b) Elastic properties of hedenbergite. J Geophys Res 93:
1063-1072
Knitte E, Jeanloz R (1987) Synthesis and equation of state of (Mg,Fe)Si0 3 perovskite to over
100 gigapascals. Science 235: 668-670
Peercy MS, Bass JD (1990) Elasticity of monticellite. Phys Chern Minerals 17: 431-437
Sawamoto H, Weidner DJ, Sasaki S, Kumazawa M (1984) Single-crystal elastic properties of
the modified spinel (beta) phase of magnesium orthosilicate. Science 224: 749-751
Sumino Y, Anderson OL (1984) Elastic constants of minerals. In: Carmichael RS (ed)
Handbook of physcial properties ofrocks, V. III. CRC Press, Boca Raton, FL, pp 39-138
358
Sumino Y, Anderson OL, Suzuki I (1983) Temperature coefficients of elastic constants of

single crystal MgO between 80 and 1300 K. Phys Chern Minerals 9: 38-47
Suzuki I, Anderson OL, Sumino Y (1983) Elastic properties of a single-crystal forsterite
Mg 2 Si0 4 up to 1200 K. Phys Chern Minerals 10: 38-46
Watt JP (1988) Elastic properties of polycrystalline minerals: comparison of theory and
experiment. Phys Chern Minerals 15: 579-587
Webb SL (1989) The elasticity of the upper mantle orthosilicates olivine and garnet to 3 GPa.
Phys Chern Minerals 16: 684-692
Weidner DJ, Hamaya N (1983) Elastic properties of the olivine and spinel polymorphs of
Mg 2 Ge0 4 and evaluation of elastic analogues. Phys Earth Planet Int 33: 275-283
Weidner DJ, Ito E (1985) Elasticity of MgSi0 3 in the ilmenite phase. Phys Earth Planet Int
40:65-70
Weidner DJ, Sawamoto H, Sasaki S (1984) Single-crystal elastic properties ofthe spinel phase
of Mg 2 Si0 4 . J Geophys Res 89: 7852-7859
Yagi T, Akaogi A, Shimomura 0, Tarnai H, Akimoto S (1987) High pressure and high
temperature equations of state of majorite. In: Manghnani MH, Syono Y (eds) Highpressure research in mineral physics. The Akimoto volume. TERRAPUB Tokyo & American Geophyscial Union, Washington, pp 141-148
Yamomoto S, Anderson OL (1987) Elasticity and anharmonicity of potassium chloride at high
temperature. Phys Chern Minerals 14: 332-340
Yamomoto S, Ohno I, Anderson OL (1987) High temperature elasticity of sodium chloride.
J Phys Chern Solids 48: 143-161
Yeganeh-Haeri A, Weidner DJ, Ito E (1989) Elasticity of MgSi0 3 in the perovskite structure.
Science 243: 787-789
Yoneda A (1990) Pressure derivatives of elastic constants of single crystal MgO and MgAI 2 0 4
J Phys Earth 38: 19-55
6.2 Hardness of Minerals

S.V.
TITKOV
Hardness of minerals is usually defined as their resistance to mechanical

destruction. Hardness is an integral characteristic of the mechanical properties
of minerals and it is determined by mineral elasticity, strength, ductility, and
brittleness. Hardness is not a physical constant and its value is dependent not
only on the material under investigation, but also on the chosen method of
measurement.
In physics there are a variety of methods to measure material hardness.
These include static and dynamic indentation, scratching, grinding, drilling, and
the measurement of the recoil height of an impinging hammer. The influence of
any mechanical characteristic on the results of the hardness measurement varies
with the method being used. Hardness is determined primarily by ductility when
the indentation test is applied, by brittleness when scratching and grinding tests
are used, and by elasticity in the case of the hammer recoil test.
359
The scratching and indentation methods are most widely used in mineralogy.
The Mohs' scratch hardness is defined as the ability of one mineral to be
scratched by another, harder mineral. Suggested in the early 19th century by
F. Mohs, the hardness scale of ten standard minerals has been applied up until
now. This scale is not linear, the difference in hardness between the first standard
minerals being much less than that between the last ones. Modern handbooks
give the optimal test planes of the standard minerals to eliminate the hardness
anisotropy effect.
The Vickers hardness, measured by indenting a diamond pyramid into
the mineral being tested, is determined as the ratio of the indentor load to
the indentation lateral area. After the removal of the load, the diagonal of the
pyramid indentation base is measured, and the indentation apex angle is taken
by convention to equal the indentor apex angle. Besides the Vickers square
pyramid, the Berkovitch triangular pyramid and Knoop rhombic pyramid are
used.
The indentation hardness is sometimes referred to as micro hardness, since
the measurements are performed in a limited region.
Many hardness data are express\!d as either Mohs or Vickers hardness, so
that conversion from one scale to the other is necessary. A comparison between
the Mohs and Vickers hardness reveals a nearly parabolic dependence. Numerical correlations between Mohs and Vickers hardness for index minerals
were proposed by Reckmann: Hv = 86.3 - 90.9Hm + 34.6H~, and by Westbrook and Conrad: Hv = 5.25H!" 73.
Hardness of minerals is determined first and foremost by crystallochemical
factors. The hardness value varies in inverse proportion to the crystal interatomic spacing (isodesmic compounds are characterized by an inverse quadratic
dependence). The hardness increases as the cation valence increases, which is
revealed even more strongly with the simultaneous increase in the anion valence.
The hardness increases discontinuously with the increase in the coordination
number. An increase in hardness is also observed at a higher density of atomic
packing. Other conditions being equal, mineral hardness increases at the
transition from the ionic to the covalent bond. The influence of the electron shell
structure is revealed particularly by the fact that the presence of the electron gas
shell reduces the hardness. The presence of hydroxyl or water molecules in the
mineral structure always reduces the hardness.
Proceeding from the main crystallochemical parameters, different formulae
for the calculation of mineral hardness have been suggested. However, the
theoretical results and the experimental data disagree appreciably. This is
related to the fact that being a strength characteristic, mineral hardness is also
determined by the peculiarities of the crystal internal structure and depends on
the presence of various types of dislocations, disoriented blocks, microinclusions, and other defects. For example, the hardness of halite is 18-22 kg/mm2 for
ordinary cubic crystals and can be as high as 90 kg/mm2 for threadlike
dislocation-free crystals. Therefore, both the crystallochemical factors and the
360
crystal internal structure should be taken into account in the estimation of the
mineral hardness.
Compressibility of minerals is the isothermal change in volume of a crystal
with pressure, fJ = -
(~)
(:;)T.
This property depends upon the same factors
that determine hardness. Compressibility can be measured directly from the

change in volume with confining pressure or can be computed from elastic
constants. The bulk modulus of minerals is the reciprocal of the compressibility,
and is more useful. Plendl et al. (1965) expressed the empirical correlation
between hardness and compressibility as:
l/fJ = --/-, where Z is the maximum
Zm q
valence, m the number of components, and q the number of atoms per molecule.
It should be noted that in chemistry hardness is defined as the resistance of
the chemical potential to change with regard to the number of electrons
assumed for the classification of reactivity of molecular species. However, two
very distinct concepts of hardness, one for the microscopic chemical reactivity,
the other for microscopic mechanical resistance to destruction of minerals, have
a common ground in thermodynamics: they are both measures of N(Ofl/oN) or
its multicomponent generalization, where N is number of electrons, fl the
chemical potential. On the basis of this analogy, a theoretical relation between
mineral hardness (H) and compressibility (fJ) was proposed by Yang et al. (1987):
H
where M is the molecular weight, P the density, and q the number of

PqfJ
atoms in a formula unit.
The cohesive energy of solid state materials is defined as the work required
to dissociate 1 mol of the substance into its free constituents. It characterizes the
bond strength of the crystal and determines all its mechanical properties.
Cohesive energy U of an ionic crystal may be calculated using the equation:
U = - (ZaZce2NA/Z)(1 - l/n), where Za is the anionic valence, Zc the cationic
valence, e the electronic charge, n the repulsive force parameter, r the mean
atomic radius, Na Avogadro's number. Goble and Scott (1985) showed that the
Mohs hardness is proportional to the second derivative of the volumetric
cohesive (lattice) energy with a change in the interatomic distance (d 2U/dr2)ro.
= --,
References
Anderson OL (1972) Patterns in elastic constants of minerals important to geophysics. In:
Robinson E (ed) Nature of the solid earth. McGraw-Hill, New York
Beckmann G (1971) Uber den Zusammenhang zwischen Kompressibilitiit und Hiirte von
Mineralen und nichtmetallischen kristallinen Substanzen. Kristall und Technik 6: 109-117
Birch F (1966) Compressibility: elastic constants. In: Clarke SP Jr (ed) Handbook of physical
constants. Geol Soc Am Mem 97: 97 173
Cisenstadt MM (1971) Introduction to mechanical properties of materials. Macmillan,
New York
Goble RJ, Scott SD (1985) The relationship between mineral hardness and compressibility (or
bulk modulus). Can Mineral 23: 273-285
361
Ivan'ko AA (1971) Handbook of hardness data. Israel Program for Scientific Translations,
Keter Press, Jerusalem
Plendl IN, Mitra SS, Gielisse PJ (1965) Compressibility, cohesive energy, and hardness of
nonmetallic solids. Phys Stat Sol 12: 367-374
Povarennykh AS (1964) A calculation of the hardness of minerals on the basis of crystallochemical data. In: Battey MH, Tomkieft' SI (eds) Aspects of theoretical mineralogy in the
USSR. Macmillan, London
Simmons G, Wang H (1971) Single crystal elastic constants and calculated aggregate
properties: a handbook. The Mass Inst Technol Press, Cambridge, Mass
Urysovskaya AA (1981) Mechanical properties of crystals. In: Modern crystallography, vol 4.
Vainstein BK, Chernov AA, Shuvalov ZA (eds) Physical properties of crystals. Science,
Moscow (in Russian)
Wang HF (1978) Elastic constant systematics. Phys Chern Minerals 3: 251-261
Westbrook JH, Conrad H (1973) The science of hardness testing and its research applications.
Am Soc Metals, Columbus, Ohio
Yang W, Parr RG, Uytterhoeven L (1987) New relation between hardness and compressibility
of minerals. Phys Chern Minerals 15: 191-195
Yushkin NN (1971) Mechanical properties of minerals. Science, Leningrad (in Russian)

CA.
BROOKES
The reader is referred elsewhere for a more general treatment of the hardness of
minerals (Bowie and Simpson 1977) but here we shall address the problems of
such measurements in very hard materials by summarizing work on diamond.
Not only is this the hardest material, but it is also the one where the phenomena
described below are most marked and therefore where control of the experimental conditions will be critical in obtaining reproducible and accurate results.
The original Mohs hardness scale, which was based simply on the ability of
one mineral to make a visible scratch on the surface of another, represents a
remarkably diligent piece of research on many more materials than the ten listed
in the scale. However, a scratch can sometimes be produced on one material by
another whose Mohs number may be lower by up to two increments and the
introduction of indentation techniques enabled more quantitative measurements to be made. The first method of measuring indentation hardness (Brinell)
was based on the use of a steel sphere to obtain a hardness number after dividing
the applied normal load by the curved surface area of the indentation. Such
indenters develop tensile stresses just outside the area of contact which encourage brittle fracture, rather than plastic flow, with a consequent lack of accuracy
in measurement of the permanent indentation. The pyramidal indenters Vickers, Berkovich, and Knoop - have all been used to indent the hardest solids
(Brookes and Moxley 1975) but there is little doubt that the shape of the Knoop
indenter is best suited for accuracy; minimizing cracking in the specimen; and
maintaining its own shape. This indenter has a rhombohedral base and produces an indentation in which, with the normal load still applied, the long
diagonal is seven times the length of the short diagonal. On removal of the load,
362
the long diagonal does not change, but elastic recovery of the short diagonal
occurs -- for diamond this recovery results in a ratio of about 14 rather than
seven. The projected area ofthe unrecovered indentation is determined using the
long diagonal length only, i.e., assuming the short diagonal to be about seven,
and dividing this area into the applied normal load yields the Knoop hardness
value in terms of a mean pressure. There is a direct linear relationship between
the relevant Mohs number and indentation hardness values for all minerals except for diamond (Tabor 1970). In this case, the extrapolation of the straight
line relationship for Mohs numbers 1 (talc) to 9 (corundum) would correspond
to a value of 15 and not 10. However, here we shall be concerned principally
with the Knoop indenter and we may note that 0.5-100 Gpa (50 to
10 000 kg/mm2) covers the range of hardness values for most materials. A more
detailed account of the important experimental variables which influence
hardness measurements has been published previously (Brookes 1984) but these
will be summarized.
Indentation Size Effects

The first consideration of the size of the indentation is with regard to the volume
of material which is being deformed by the indentation process. In the case of
metals, grain boundaries cause an increase in the measured hardness if that
volume extends beyond one grain. Hence, single crystals are significantly softer
than polycrystalline specimens of the same metal and the hardness value
increases with decreasing grain size. In minerals, grain boundaries are generally
much less important in hardness measurements - other than when associated
with impurities and/or environmental reactions. The hardest materials also have
a tendency to fracture and, since this is exacerbated with increasing normal
loads, most definitive measurements have been carried out at low loads within
individual crystals, i.e., micro-indentation hardness.
The law of geometrical similarity implies that, for pyramidal indenters, the
hardness of a crystal should be independent of the normal load. However, it is
now well established that, for measurements using normal loads of less than
20 N, the indentation hardness tends to increase with decreasing load (P) for all
crystalline solids, such that:
P = Ad n ,
where d is the diagonal length of the indentation, A is a constant and n < 2.
When the hardness is load independent n = 2, and therefore the magnitude of
the effect is increased as the value of the exponent decreases [i.e., H = f(d)-n].
This indentation size effect is such as to become more pronounced as the
intrinsic hardness ofthe specimen material increases. Thus, the lowest value of n
reported is that of about 1.5 for diamond whilst sapphire is 1.8 and most metals
are around 1.95. No entirely satisfactory explanation of the mechanism responsible for this effect has yet been developed, but it does explain the apparent
363
discrepancy in hardness values quoted over the range of 80 Gpa to 180 Gpa for
diamond. This particular experimental variable has very important implications
for the measurement of the hardness of diamond and diamond-like coatings. In
those particular applications, the coating is generally a few micrometers thick
and light loads are necessary in order to keep the deformation within the
coating. Consequently, we should anticipate values of hardness towards the top
of this range.
Crystallographic Orientation and Anisotropy

The mechanical properties of crystalline solids are intrinsically anisotropic and
therefore indentation hardness measurements, using pyramidal indenters, reflect
this property to a greater or lesser degree. Again, the evidence shows that this
effect is most pronounced in the hardest solids. For example, consider Knoop
hardness measurements in which the orientation of the long diagonal with
respect to the crystallographic direction on a given plane is a convenient way of
studying anisotropy. Typical results show that, on a (001) plane of a type Ia
diamond, the Knoop hardness with the long diagonal parallel to the [110]
direction is about 81.34 GPa compared with 96.04 GPa in the [100] direction.
Whilst different types of diamond vary in hardness, the nature of this anisotropy
is always the same, i.e., (100) are always harder than (110). Indeed, the
consistency of the nature of anisotropy in a wide range of crystals is such that
Knoop indentation hardness measurements have been used to identify the active
slip systems in a number of materials.
In the most commonly used model for explaining anisotropy in indentation
hardness, the resolved shear stresses developed in the bulk of the crystal are
determined. The magnitude of these stresses is dependent on the orientation of
the indenter facets with respect to the operative slip systems, i.e., {Ill} <11 0) in
diamond. Thus:
Te
(J
cos () COsA. 0.5(cos sin<5),
where Te is the mean effective resolved shear stress developed by the four facets;
is the stress applied by the indenter which need not be specified for considerations of the nature of anisotropy; cos () cos A. is the Schmid Boas factor; O.5(cosq,
+ sin <5) is a rotational constraint factor reflecting the ease of displacement of
material on the surface and from beneath the indenter. Then, the higher the
mean effective resolved shear stress for a given normal load and indenter
orientation, the greater the amount of plastic deformation and the lower the
hardness. Whilst the extent of plastic deformation of diamond at room temperature must be very limited, dislocations beneath Knoop indentations have been
observed by TEM (Humble and Hannink 1978).
This earlier work on anisotropy resulted in the introduction of a pyramidal
indenter with a pentagonal base whose fivefold symmetry negates that of cubic
and hexagonal crystals and gives results which are essentially independent
(J
364
Table 30. Hardness values of minerals (GPa)

Specimen
Plane
Pentagonal
CaF2
Quartz
Al 2 0 3
Diamond
(001)
(0001)
(0001)
(111)
1.87
10.06
21.09
88.29
a 1000 g,
0.06
0.29
0.98
9.813
Knoop
Vickers
Berkovich
1.76/1.57
6.87 0.15
12.75/13.73
73.58/81.42 3
1.89 0.05
10.71 0.24
19.88 0.49
105.95 b
1.81 0.Q7
9.61 0.78
16.19/19.62
98.10 9.81a
200 g, otherwise 500 g load used.
of orientation. For example, Table 30 summarizes hardness values for a few

minerals, using various indenters, and demonstrates that the pentagonal indenter can be used to rank materials. In Table 30, the range of anisotropic
values is given, e.g., Hk 73.58/81.42 for diamond.
Other Experimental Variables

As a general rule, Knoop indentations in the hardest crystallographic direction
are the least likely to be affected by cracking and therefore give greater reliability
and accuracy than those in softer directions. In diamond at room temperature,
such cracks tend to radiate from the indentation ~ in particular from the short
diagonal. [In other hard minerals, e.g., quartz and corundum, cracks initiated
roughly parallel to the indented surface (lateral venting) may propagate up to
that surface and completely distort or remove the indentation.] These cracks are
thought to be due to a combination of plastic and elastic recovery within the
deformed volume and may develop some minutes after the load has been
removed. These effects may well be attributable to a form of stress corrosion/
embrittlement and therefore could be exacerbated in certain environments.
Finally, the effect of relatively modestly elevated temperatures, e.g., about
one third of the melting point, should be noted. In recent work on diamond, it
has been shown that dislocations become very much more mobile at temperatures in the region of 1000C and that significant creep is obtained by
increasing the time over which the normal load is maintained. (Brookes et al.
1990).
Diamond - the Ultimate in Hardness?

The intrinsic rigidity and strength of diamond is due to the fact that every
carbon atom shares an electron with each offour nearest neighbors, i.e., covalent
bonds with tetrahedral coordination, representing the strongest possible type of
interatomic binding in crystals. Consequently, diamond has the highest theoretical values of cleavage fracture stress and shear stress of any solid, i.e., 205 GPa
and 121 GPa respectively (Kelly 1966). In fact, these theoretical values are
365
reduced by stress concentrators on one hand and dislocations on the other but it
is unlikely that the hardness of diamond will be surpassed when measured with
due regard to the experimental variables identified earlier.
Nevertheless, the recent development of the so-called soft indenter technique
demonstrates vividly that hard materials can be plastically deformed, work
hardened, and worn by softer ones (Brookes et al. 1987). Thus, the clearest
demonstration of the difference in mechanical properties of various types of
diamond has been achieved through pressing a cone of cubic boron nitride onto
(001) surfaces at elevated temperatures. Whilst the cone blunts under the applied
normal load, the mean contact pressure is sufficient to initiate bulk plastic flow
and creep in the diamond. On the basis of this work, it has been shown that the
threshold temperature marking the onset of plastic flow is about 750 DC for
synthetic type Ib crystals, 950 DC for natural type la, 1000 DC for type lIb and
1100 DC for type IIa diamonds. In addition, whilst dislocation-induced cracking
on {1l0} planes is observed in both type I diamonds, fracture does not develop
around the impressions in type II. It is considered likely that the presence of
nitrogen in type la and Ib plays an important role in determining this mode of
behavior but, clearly, more research with this technique will provide valuable
information concerning the conditions which encourage plasticity in all hard
crystalline materials. Already we are able to confirm that the indentation
hardness of such materials is about 30 times the relevant critical resolved shear
stress - thus indicating that even the hardest of solids can be mechanically worn
by significantly softer ones.
References
Bowie SHU, Simpson PR (1977) Microscopy: refllight. In: Zussman J (ed) Physical methods in
determinative minerology, Chapter 3, Academic Press, London, 720, 2nd edn, pp 109-165
Brookes CA (1979) In: Field J (ed) The properties of diamond. Academic Press, London,
pp 383-402
Brookes CA (1986) Hardness measurements in the evalution of hard materials. Proc ICSHM2.
In: Almond EA, Brookes CA, Warren R (eds) Inst of Physics Publication CS 75, Adam
Hilger Press, pp 207-220
Brookes CA, Shaw MP, Tanner PE (1987) Non-metallic crystals undergoing cumulative workhardening and wear due to softer lubricated metal sliding surfaces. Proc R Soc Lond A409:
141-159
Brookes CA, Brookes EJ, Howes VR, Roberts SG, Waddington CP (1990) A comparison of
the plastic deformation and creep of type I, type II and synthetic diamonds at 1100 C under
conditions of point loading. J Hard Mater 1(1): 3-24
Brookes CA, Moxley B (1975) A pentagonal indenter for hardness measurements. J Physics E
8: 456-460
Humble P, Hannink RHJ (1978) Plastic deformation of diamond at room temperature. Nature
273: 37-39
Kelly A (1966) Strong solids. Clarendon Press, Oxford, pp 12-28
Tabor D (1970) The hardness of solids. Rev Phys Sci Technol 1: 145-156
366
6.3 Deformations in Minerals

6.3.1 Mechanisms of Plastic Deformation in Minerals;
Role of Dislocations
C. WILLAIME and M. GANDAIS
Minerals submitted to tectonic stresses may deform plastically, i.e., continuously

at the lattice scale. Various mechanisms of plastic deformation may be involved,
depending on several parameters, e.g., temperature T, pressure P, applied stress
a, strain rate i;, chemical composition of the mineral, presence of fluids. Values of
these parameters are different for different tectonic events; in crustal deformation, pressure and temperature may be 0.5 Gpa and 500C, whereas in the upper
mantle, they are 10 Gpa and 1500C. Deformation occurs at the time scale of
geological events, i.e., with strain rates as low as 10- 12 S - 1. The first important
results on the mechanisms of plastic deformation were obtained from transmission electron microscope studies of naturally deformed samples (Christie and
Ardelll976). Nevertheless, precise determination of these mechanisms needed to
know exactly the deformation conditions and therefore implied the study of
laboratory deformed samples (i.e., with strain rates ca. 10- 4 _10- 6 S-I).
Slips Systems
Macroscopic deformation of crystals results from the motion of dislocations in
the lattice. Dislocations may glide; the glide plane (hkl) and the Burgers vector
b define the slip system (hkl) [b]. Dislocations may climb out of the glide plane;
this motion implies atomic diffusion and is therefore thermal-activated. At high
enough temperature, both glide and climb occur and cooperate in the dislocation movement. Nonetheless, the most important contribution to the bulk strain
of the crystal is that of dislocation glide. The gliding of dislocations needs to
break atomic bonds within the structure and therefore is very dependent on the
nature of the bonds and their orientations; e.g., ionic bonds are easier to break
than covalent bonds.
In ionic minerals with a high symmetry such as halite, dislocation glide is
easy to describe; it occurs along {1l0} dense planes with 1/2 <011) as Burgers
vectors (Amelinckx 1972). In minerals such as silicates, the situation is more
complex. There are usually several types of bonds, with different characters
ranging from highly ionic to highly covalent, and the crystal often has a low
symmetry. Therefore, dislocation glide is strongly dependent on the mineral
structure; if it is possible, it should avoid the breaking of strong bonds such as
Si-O bonds in the Si0 4 tetrahedra. In olivine, Si0 4 tetrahedra are isolated and
dislocation glide may occur on several planes which never cut Si-O bonds: (100),
6.3.1 Mechanisms of Plastic Deformation in Minerals
367
(010), {Okl}. The stress necessary for breaking bonds is very similar for all these
planes. The preference for one or the other glide plane is therefore dependent on
small variations of the bond strength such as those induced by temperature
variation. Indeed, the dominant slip systems in olivine depend upon the
deformation temperature. At low temperature, the dominant slip system is
(100) [001] whereas at high temperature it is (010) [100] (Goetze 1978). In
pyroxenes, Si0 4 tetrahedra are linked along [001]. The glide planes are parallel
to this direction: (100), (010). The dominant slip system depends on the
deformation temperature as well. In orthopyroxenes, (100) [001] is dominant at
low temperature and (010) [001] becomes important at high temperature. In
tecto silicates (quartz, feldspars), any plane direction intersects strong Si~O~Si
bonds. Similarly, in the pyrite structure any plane intersects strong bonds
connecting S~S atoms or Fe~S atoms. Gliding of dislocations is therefore more
difficult; the easiest glide planes are assumed to be those cutting the smallest
number of strong bonds (McLaren et al. 1967). In pyrite, glide planes are {100}
that intersect only a few Fe~S and no S~S bonds (Levade et al. 1979). Besides
temperature, other parameters may modify this strength and therefore the
gliding of dislocations; e.g. a small amount of water within the quartz structure
weakens the Si~O bonds (see Chap. 6.3.5).
Role of Dislocation Dissociation in the Deformation Process
Possible bulk deformation of a mineral may be predicted from the knowledge

of the orientation of glide planes, as described in the previous section. But
deformation will be effective only if dislocations can be created and if they are
easily mobile, i.e., if they have a low energy. Around a dislocation, the crystal
lattice is elastically strained, with a stored elastic energy proportional to b2 .
Furthermore, there is a core energy related to the disturbance of bonds along the
defect. The occurrence and behavior of dislocations are controlled by the whole
value of stored energy. Evaluation of dislocation energy and its minimization
implies a careful examination of the mineral structure and of the dislocationcore configuration. In minerals, lattice translations are usually large: 0.5 to more
than 1 nm. Both the elastic energy and the core energy are reduced by
decreasing the Burgers vector length. Therefore, dislocations in minerals tend to
dissociate into partial dislocations separated by stacking faults. This occurs if
the crystal structure allows low energy stacking faults. Dissociation of dislocations in minerals has been firstly evidenced and extensively studied in phyllosilicates: symmetrical arrangement of oxygen atoms in the glide plane allows
easy dissociation and creation of multiple stacking-fault ribbons (Amelinckx
1972). Dislocations may dissociate as well in minerals with more complex
structures. The dissociation may be explained through two approaches depending on the kind of atomic bonds: mainly ionic or mainly covalent.
If ionic bonds are involved, models of hard spheres generally account for
dislocation substructures. In the example of pyroxene (Fig. 88), the easy slip
368
Fig. 88. (100) [001] dislocations in orthopyroxenes. Weak beam electron micrograph. Dislocations in the foil plane.
Dissociation into four partials bounding
three stacking faults. The external ribbons
are 10 nm wide approximately and the
median fault is 50 nm wide approximately
0.1
I
tJrn
I
system (100) [001] involves dislocations which are dissociated into four partials
separated by a triplet of stacking fault ribbons, the wider lying between the other
two. These observations are explained by considering dislocations gliding and
dissociating between compact planes of the oxygen sublattice. Dissociation
occurs in two steps (Van Duysen et al. 1985): (1) [001] -> 1/6 [013] + 1/6 [013]
which creates a low-energy stacking-fault because it does not affect the oxygen
stacking; the corresponding stacking-fault ribbon is the wide one; (2) 1/6
[013] -> 1/6 [011] + 1/3 [001] and 1/6 [013] -> 1/6 [011] + 1/3 [001] which
modify the oxygen stacking and thereafter the shape of the interstitial cavities,
giving rise to cation displacement by a synchroshear mechanism; thus-created
stacking faults have a higher energy and correspond to the narrow ribbons. In
the uneasy slip system (l00) [010] of the pyroxene structure, dislocations are not
dissociated. Indeed, any dissociation would lead cations in forbidden octahedral
sites. In covalent bounded crystals, dislocation dissociation may be predicted
from the value of the energy as estimated from the deformation of atomic bonds
in modelized planar defects and dislocation cores. The efficiency of such
modeling is shown in feldspars (Fig. 89). In the feldspar structure, two glide
planes situated between the double-crankshaft chain involve the breaking of a
minimum of bonds: (001) and (010) (Tullis 1982; Gandais and Willaime 1984).
However the dislocation mobility along (010) is higher than along (001) due to a
dissociation giving rise to a stacking fault (010) 1/2 [001]. Examination of the
feldspar structure shows that such a fault is lying within the double crankshaft
chain. A dislocation gliding along this plane requires twice more broken bonds
than if it was gliding between the double chains, but the total energy involved is
lowered by the dissociation. Indeed, the core energy is reduced by the reconstruction of atomic bonds in the core; this is made possible by the high
369
6.3.1 Mechanisms of Plastic Deformation in Minerals
II
6.5A
1 1
Fig. 893, b. (010) [001] dislocat ion in sanidine. 3 High resolution electron micrograph.
b Filtered image showing (001) planes. The dislocation is perpendicular to the foil plane. The
arrows indicate the partial dislocations bounding the (010) 1/2 [001] stacking fault
atomic density within the double chain, and the short Burgers vector of
dissociated dislocations (Zheng et al. 1988).
Dissociation of dislocations may hinder the gliding process and harden the
mineral. This occurs when the dislocation dissociates out of its glide plane, as it
has been shown in spinel: 1/2 [110] dislocations gliding in (nO) plane dissociate
into 1/4 [110] + 1/4 [110] in (110) plane (Doukhan et al. 1982). Other
deformation mechanisms involving the gliding of partial dislocations may occur
in peculiar mineral structure. Mechanical twinning is produced by the gliding of
a twin dislocation; in calcite partial dislocations with a Burgers vector parallel to
[010] (with respect to the cleavage cell) and only 0.13 nm long are responsible
for the mechanical twinning of the crystal (Sauvage and Authier 1965; Wenk
et al. 1990). M artensitic phase transformation is also the result of partialdislocation gliding under an applied stress. For instance, orthopyroxene crystals
may transform into clinopyroxene by gliding of dislocations (100) 0.83 [001]
(Kirby 1976). In both cases, the mineral is plastically deformed through a shear
of the structure, and the maximum strain has a finite value.
Conclusion
Valuable data on mechanical properties of the main mineral species have been
obtained by different means, including experimental deformation, transmission
370
electron microscope studies and structure modelling. Nevertheless, mineral

structure is often complicated (e.g., low-symmetry, nonstoichiometry) and the
deformation mechanisms may change with the deformation conditions. Therefore, more sophisticated experiments - with precise controls of stress, temperature, presence of a fluid phase, etc. - should be performed for a better
knowledge of the deformation mechanisms. Furthermore, extrapolation of the
obtained experimental data to geological deformation conditions (i.e., low
strain rate) needs careful TEM examination of the microstructure of naturally
deformed minerals. It should be recalled that the observed microstructure is
characteristic of the last tectonic event: any heating of the rock induces a
recovery process which hides the previous deformation stages.
References
Amelinckx S (1972) Dislocations in particular structures. In: Nabarro FRN (ed) Dislocations
in solids. North Holland Publishing Company, Amsterdam, pp 67-460
Christie JM, Ardell AJ (1976) Deformation structures in minerals. In: Wenk HR (ed) Electron
microscopy in mineralogy. Springer, Berlin Heidelberg New York, pp 374-403
Doukhan N, Duclos R, Escaig B (1982) Climb dissociation in {U3} planes in Al-Mg spinels.
J Physique 43: 1149-1157
Gandais M, Willaime C (1984) Mechanical properties of feldspars. In: Brown WL (ed)
Feldspars and feldspathoids. NATO ASI series C137, DReidel Publ Comp, Dortrecht,
pp 207-246
Goetze C (1978) The mechanisms of creep in olivine. Philos Trans R Soc Lond A 288: 99-119
Kirby SH (1976) The role of crystal defects in the shear-induced transformation of orthoenstatite to clinoenstatite. In: Wenk HR (ed) Electron microscopy in mineralogy. Springer, Berlin
Levade C, Couderc JJ, Bras J, Fagot M (1979) Etude par microscopie electronique en
transmission des dislocations dans la pyrite FeS 2 Phil os Mag A 40: 111-120
McLaren AC, Retchford JA, Griggs DT, Christie JM (1967) Transmission electron microscopy
study of Brazil twins and dislocations experimentally produced in natural quartz. Phys Stat
Sol 19: 631-644
Sauvage M, Authier A (1965) Etude des bandes de croissance et des dislocations de macle. Bull
Soc Fr Mineral Cristallogr 88: 379-388
Tullis J (1982) Deformation offeldspars, In: Ribbe PH (ed) Feldspar mineralogy. Reviews in
mineralogy 2, 2nd edn. Chelsea, Michigan, Mineralogical Society of America, pp 297-323
Van Duysen JC, Doukhan N, Doukhan JC (1985) Transmission electron microscope study of
dislocations in orthopyroxene (Mg,FehSi 2 0 6 Phys Chern Minerals 12: 39-44
Wenk HR, Barber DJ, Reeder RJ (1990) Microstructures in carbonates. In: Reeder RJ (ed)
Carbonates: mineralogy and chemistry. Reviews in Mineralogy 11, 2nd printing, Chelsea,
Michigan, Mineralogical Society of America, pp 301-394
Zheng Y, Gandais M, Heggie M (1988) Study of (010) [101] and (001) [110]/2 dislocations in
K-feldpsars by HRTEM and Modelling. Phys Chern Minerals 15: 349-354
6.3.2 Fracture Mechanics and Fracture Mechanisms in Minerals

G.E.
LLOYD
and C.C. FERGUSON
Crystalline materials fail by several alternative mechanisms ranging from purely

brittle fracture to purely ductile creep rupture. There is very little experimental
371
data on mineral failure under various environmental conditions and few

minerals are well characterized. An alternative approach, fracture mechanics,
does not depend explicitly on identifying microstructural processes. The literature here is larger but the need for fairly large and carefully machined specimens
means that rather little experimental work has been done on single crystals and
even less under environmental conditions relevant to natural failure. This review
addresses both approaches and emphasizes the links between "brittle" and other
processes. The bibliography highlights landmark papers and works containing
data on particular minerals.
Response of Minerals to Applied Stress
Minerals respond to applied stress by elastic deformation, fracture or flow,

depending on material strengths (the maximum differential stress supported).
This influences time and strain to fracture, the most efficient deformation
mechanisms up to fracture, and the fracture mechanism, and varies for each
available fracture or deformation mechanism. The lowest value determines
which mechanism occurs. Thus, strength is not a material constant, its value
depending on confining pressure, temperature, strain, strain-rate, stresses, fluid
pressure, structure and microstructure, and system chemistry.
Low temperatures and confining pressures but high strain-rates promote
brittle deformations dominated by fracturing at all scales. High temperatures
and confining pressures but low strain-rates promote ductile deformations
dominated by crystal plasticity and/or diffusion. This suggests that the upper
crust is dominated by brittle (seismic) deformation mechanisms which tend to
produce random structures and fabrics (e.g., breccia, gouge, cataclasites etc.).
Lower crustal environments should be dominated by ductile (aseismic) deformation mechanisms which tend to produce nonrandom structures and fabrics. The
transition from brittle to ductile behavior is neither instantaneous nor reliably
depth-dependent. Fractures may contribute to a macroscopically ductile
response, and ductile processes often contribute to macroscopic fracture
evolution.
Fracture Mechanics
Fracture mechanics is based on the pioneer work of Griffith (1920) and Irwin
(1957). It attempts to define material parameters which predict fracture response; e.g., the critical stress intensity factor, K e , characterizes resistance to
fracture propagation at an existing crack-tip (i.e., fracture toughness). Experimental determination of mineral fracture mechanics parameters is difficult
because most methods are unsuitable for individual minerals, or for studying
how variations in mineralogy and microstructure affect crack propagation.
Nevertheless, several fracture mechanics criteria can be defined depending on
scale, as follows.
372
Atomistic. Compression causes the average atomic spacing to be less than the
equilibrium spacing (a o), resulting in repulsive forces. Extension causes the
spacing to be greater than ao, resulting in attractive forces. Compression is
effectively stable, but tension eventually breaks atomic bonds resulting in
catastrophic failure at the theoretical strength (oth). However, this is rarely if
ever reached due to the presence of flaws in the crystal structure.
Microstructural. This scale ranges from dislocations and intracrystalline plasticity to microcracks. Cracks form in a variety of ways; e.g., motion of dislocations and glide planes, the presence of inclusions and voids, or by stress
corrosion (see below). Material flaws act locally to raise applied stress such that
a eone = a(1 + c/r), where c is the flaw or microcrack half-length and r is the
crack-tip radius. Since clr can be of order 103 , stress concentrations can be large
and can exceed the theoretical fracture strength. However, propagation causes
crack area to increase and hence so must the surface energy necessary for
fracture. To continue propagation, more energy (increased applied stress) is
required. If this is provided by increase in clr, the fracture can become unstable.
But, if a eone ~ a y , local crack-tip plasticity develops, absorbing energy and
arresting crack propagation. Crack-tip stress concentrations can be either
symmetric or asymmetric depending on crack orientation relative to the applied
stress field. They can also develop remote from crack-tips, leading to new
microcracks; tensile stress is released oblique to the parent crack and a "shear
zone" develops consisting of regularly spaced tension gashes.
Macroscopic. Several different theories exist at this scale. (1) Energy balance
theories are based on identifying a dominant flaw which initiates fracture.
Parameters include flaw size distribution, applied stress and the energy required
to create new fracture surface (i.e., fracture energy). (2) Linear elastic fracture
mechanics (LEFM) relates all contributing parameters to a stress intensity
factor, K, which describes the total stress field around a crack or flaw and
therefore takes account of local inelastic deformations. Cracks propagate at a
value, K e, which is a function of crack opening mode (i.e., mode I, tensile
opening; mode II, shear opening; and mode III, tearing opening). Mode I is
commonest, possibly because all materials are weakest in extension; critical
stress intensity factor is defined by K'e = YaJ(2c) where Y is a function of crack
size, shape, and position. (3) Plastic instability occurs if crack-tip stresses exceed
the plastic yield stress over an area considerably greater than the crack size;
plastic yield occurs and fracture toughness increases due to crack-tip blunting.
Crack-tip plasticity is characterized by the stretch, d, in the plane ahead of a
propagating crack, fracture resistance being defined by the critical opening
displacement, de. The crack-tip plasticity consumes energy and results in
fracture arrest. Successive stages of crack development may be analogous to the
"crack-seal" process recognized in many vein array systems.
373
Fracture Mechanisms
There are several mechanisms by which cleavable crystalline materials such as
minerals can fracture.
1. Fracture at the ideal strength theoretically occurs at the stress (typically
E/10) required to break atomic bonds, but is unlikely due to inherent flaws.
2. Dynamic fracture occurs at large applied stresses and is driven by
propagation of elastic waves. It may be pertinent to major seismic activity in
continental scale fault zones.
3. Cleavage fracture occurs if resistance to plastic shear exceeds the cohesive
strength of cleavage planes. Of three possible mechanisms, two are grain sizedependent. Initial flaws cause stress concentrations; when the fracture stress is
exceeded, flaws propagate at stresses less than the yield stress so that no general
plasticity occurs (cleavage I). Where initial flaws are extremely small, stress
concentrations can exceed the yield stress for slip/twinning leading to ::;; 1%
bulk plastic strain. This may induce other internal stresses which can nucleate
cracks, e.g., at dislocation pile-ups (cleavage II). If the yield stress exceeds the
fracture stress, a crack nucleated by plasticity will propagate, but if the fracture
stress exceeds the yield stress propagation is arrested until the stress is raised
further. With suitably high temperatures and small grain sizes up to 10%,
general plasticity may be accommodated by crystal plasticity and/or grain
boundary sliding. As the general plasticity increases large grain boundary cracks
can develop until their increased length and higher stresses (due to plastic workhardening) cause unstable propagation (cleavage III).
4. Brittle intergranular fractures (BIF I, II, III) can develop because of the
delicate balance between the stress required for cleavage fracture and that
necessary to cause fracturing along grain boundaries. Whichever has the lowest
fracture stress will develop, and this depends on impurity content, composition,
grain-boundary cement, rock texture, and temperature.
5. Low temperature ductile fracture (LTDF) occurs when > 10% general
plasticity is possible without cleavage fracture. Voids nucleate and grow
(possibly by diffusion) and eventually coalesce to form either transgranular
or intergranular cracks.
6. Transgranular creep fracture involves dislocation creep processes at
0.3-0.5 T m temperatures. The yield stress is much less than the fracture stress
and large strains (and considerable work hardening) may occur before fracture.
7. Intergranular creep fracture occurs at temperatures > 0.5 Tm and low
applied stress. Creep rates are low but voids and/or wedge-shaped cracks may
still nucleate and grow slowly (particularly at grain and phase boundaries) and
eventually coalesce. Nucleation and growth probably depend on local diffusion
rates. Coalescence occurs at small ductile deformations but may allow seismic
activity in otherwise stable fault zones.
8. Creep rupture occurs if no other fracture deformation mechanism is
possible; ductile deformation becomes localised and the cross-sectional area
374
reduces to zero. Such extreme ductility is enhanced by recrystallization and

occurs in mylonitic shear zones, particularly where superplastic processes
dominate.
Fracture Deformation Mechanism Maps. The fracture mechanisms described
above can be combined into "maps", plotted as normalized stress (o/E) against
homologous temperature (TIT m), showing the conditions under which different
mechanisms dominate (provide the shortest time to failure). The maps are only
guides and many boundaries are determined by observation rather than theory.
Each map is unique for a given boundary type, composition, grain-size, porosity,
and mechanism. They do not consider subcritical crack propagation (see below).
Fracture and deformation mechanism maps for quartz suggest that the
upper 20 km of the Earth's crust is dominated by cleavage and BIF mechanisms,
although dynamic fracture is also possible. However, significant crack growth
can occur far below the critical values of fracture mechanics parameters and is
known as subcritical crack propagation.
Subcritical Crack Propagation. This type of behavior is not predicted by
classical Griffith-type fracture mechanics. For example, corrosion due to enhanced chemical activity caused by crack-tip stress concentrations can promote
crack propagation. Other mechanisms include: diffusion (particularly at high
TIT m); dissolution (provided products are removed rather than precipitated at
crack-tips); ion exchange (resulting in lattice strains due to mismatch in ionic
sizes); and microplasticity (involving episodic crack extension into a damage or
process zone ahead of a crack-tip). Subcritical crack propagation also allows for
crack-healing and, since healed fractures are common, it is an important mineral
fracture mechanics concept.
Linked Fracture and Deformation Mechanism Processes

Fracture is the logical termination of many deformations irrespective of temperature, provided strain, strain-rate andlor time are sufficient. This suggests a
relationship between eventual fracture mechanism and the preceding ductile
mechanism(s). Structures which indicate such intimate relationships abound in
tectonites. Linked processes probably represent the norm in geology and the
assumption of a single mechanism, and its use to constrain deformation
conditions, paths and histories, is an unwarranted simplification responsible for
many erroneous conclusions.
For example, low temperature ductile fracture (LTDF) can involve up to
100% bulk plasticity prior to failure and we suggest this is a significant but
hitherto unappreciated geological deformation process. The plasticity involves
localized work-hardening due to transient dislocation glide and raises the yield
stress above the fracture stress, causing crack-like flaws to develop. These
coalesce and concentrate stresses allowing further dislocation glide, but eventually the fracture stress is exceeded, leading to microfracturing. A crys-
375
tallographic control on the relative development of plastic and fracture

microstructures is also likely, since it is well known that Kc depends on
crystallographic orientation (for quartz the variation in Kc with crystal direction
is: r{1011} 1.74, m{1010} 2.14, and c{OOOl} 2.40 MNm- 3 / 2 , this increase being
exactly that predicted from the areal density of Si-O bonds in the quartz
structure). Thus, we expect LTDF to produce a narrow "process or wake zone"
of slightly misoriented fragments separated along microcrack boundaries, which
obviously differs from intragranular micro crack microstructures.
Another linked deformation process is suggested by the common association
of diffusion mass transfer (DMT) features and fractures filled with material
precipitated from solution. Dilation at fracture sites may be sufficient to induce
thermodynamic instability, local solution, and mass transfer. Conversely, solution and hence the need for migration from source to sink may promote fracture.
Effective tensile stresses at depth require fluid pressure to exceed confining
pressure plus local tensile strength. Many extension fractures are filled by
minerals crystallized from aqueous fluids, but the low solubility of minerals such
as quartz suggests that many thousands of crack volumes of water must pass
through a crack for it to be filled. This suggests either an external water reservoir
(almost certainly required to produce most vein deposits of ore minerals) or that
crack-filling material is derived via local DMT.
Conclusions
Recent research shows that fracture processes in minerals are much more
complex than was hitherto assumed, and are often intimately linked to nonfracture deformation mechanisms. There is an extensive body of fracture
mechanics theory but little of it is directly relevant to natural fracturing in the
Earth's crust. The experimental and theoretical foundations for understanding
fracture mechanisms in minerals and rocks are in their infancy.
References
Ague DM (1988) Universal stage measurements and transmiSSIOn electron microscope
observations of fractured plagioclase. J Struct Geol 10: 701-706
Ashby MF, Verrall RA (1977) Micromechanisms of flow and fracture, and their relevance to
the rheology of the upper mantle. Philos Trans R Soc Lond A 288: 59-95
Atkinson BK (1987) Fracture mechanics of rock. London, Academic Press, 534 pp
Barber DJ, Meredith PG (1990) Deformation of materials. Mineral Soc Spec Publ 1, London,
Unwin Hyman
Brown WL, Macaudiere J (1984) Microfracturing in relation to atomic structure of plagioclase
from a deformed meta-anorthosite. J Struct Geol 6: 579-586
Carrio-Schaffilauser E, Gaviglio P (1990) Pressure solution and cementation stimulated by
faulting in limestones. J Struct Geol 12: 987-994
Carter NL, Friedman M, Logan JM, Stearns DW (1981) Mechanical behaviour of crustal
rocks. Am Geophys Union Monograph 24, Washington, USA
376
Chell GG (1979) Developments in fracture mechanics. Barking, Essex, Applied Science

Publishers
Davidge RW (1980) Mechanical behaviour of ceramics. Cambridge University Press
Evans AG (1980) Fatigue in ceramics. Int J Fract 16: 485-498
Ferguson CC, Lloyd GE, Knipe RJ (1987) Fracture mechanics and deformation processes in
natural quartz: a combined Vickers indentation, SEM and TEM study. Can J Earth Sci 24:
544-555
Fredrich JT, Evans B, Wong TF (1989) Micromechanics of the brittle of plastic transition in
Carrera marble. J Geophys Res 94: 4129-4145
Griffith AA (1920) The phenomena of rupture and flow in solids. Philos Trans R Soc Lond A
221: 163-178
Groshong R (1988) Low-temperature deformation mechanisms and their interpretation. Geol

Soc Am Bull 100: 1329-1360
Hirth G. Tullis J (1989) The effects of pressure and porosity on the micromechanics of the
brittle-ductile transition in quartzite. J Geophys Res 94: 17825-17838
Irwin GR (1957) Analysis of stresses and strains near the end of a crack traversing a plate.
J Appl Mechanics 24: 361-364
Katz 11 (1986) A model of propagating brittle failure in heterogeneous media. J Geophys Res
91: 10412-10420
Kirby SH (1984) Introduction and special digest to the special issue on chemical effects of
water on the deformation and strength of rocks. J Geophys Res 89: 3991-3995
Knipe RJ (1989) Deformation mechanisms - recognition from natural tectonites. J Struct Geol
11: 127-146
Knipe RJ, Rutter EH (1990) Deformation mechanisms, rheology and tectonics. Geol Soc Lond
Spec Publ 54, 535 pp
Latzko DGH (1979) Post-yield fracture mechanics. Barking, Essex, Applied Science Publishers
Lawn BR (1983) Physics of fracture. J Am Ceram Soc 66: 83-91
Lawn BR, Wilshaw TR (1975) Fracture of brittle solids. Cambridge University Press
Lin J, Parmentier EM (1988) Quasistatic propagation of a normal fault: a fracture mechanics
model. J Struct Geol 10: 249-262
Lloyd GE, Knipe RJ (1992) Deformation mechanisms accommodating faulting of quartzite
under upper crustal conditions. J Struct Geol 14: 127-143
Nishiyama T (1989) Kinetics of hydrofracturing and metamorphic veining. Geology 17:
1068-1071
Paterson MS (1978) Experimental rock deformation - the brittle field. Springer, Berlin
Heidelberg New York
Petit J-P, Barquin M (1988) Can natural faults propagate under mode II conditions? Tectonics
7: 1243-1256
Pollard DD, Aydin A (1988) Progress in the understanding of jointing over the past century.
Geol Soc Am Bull 100: 1181-1204
Power WL, Tullis TE, Weeks JD (1988) Roughness and wear during brittle faulting.
J Geophys Res 93: 15268-15278
Pure and Applied Geophysics (1989) Special issue: fractals in geophysics. Pure Appl Geophys 131
Rutter EH (1986) On the nomenclature of mode of failure transitions in rocks. Tectonophysics
122: 381-387
Scholz CH (1988) The brittle-plastic transition and the depth of seismic faulting. Geol
Rundsch 77: 319-328
Scholz CH (1989) Mechanics of faulting. Annu Rev Earth Planet Sci 17: 309-334
Sih GC, Chow CL (1977) Fracture mechanics and technology. Sijthoff & Noordhoff
Tullis TE (1986) Special issue: friction and faulting. Pure Appl Geophys 124: 375-608
Tullis TE, Tullis J (1986) Experimental rock deformation techniques. Geophys Monograph
Am Geophys Union 36: 297-324
Wang c-y (1986) Special issue: internal structure of fault zones. Pure Appl Geophys 124
373 pp
Zhang J, Wong TF, Davis DM (1990) Micromechanics of pressure-induced grain crushing in
porous rocks. J Geophys Res 95: 341-352
6.3.3 High Resolution Electron Microscopic Techniques in the Study of Defects
377
6.3.3 High Resolution Electron Microscopic Techniques in

the Study of Defects
S.
AMELINCKX
Dislocations and other structural defects in minerals, or in crystals in general,

can be studied by a variety of transmission electron microscopic techniques
combined with electron diffraction.
Diffraction Contrast (foil thickness 1000-3000 A, resolution <20 A)
Diffraction contr.ast images are in fact formed by a single magnified electron
diffraction spot either produced by the direct beam (bright field image) or by
a well-defined intense diffracted beam (dark field image). In this technique the
"image" is the intensity distribution in a single diffraction spot, mapped after
magnification. The dislocations produce contrast as a result of the sensitive
dependence of the diffracted intensity on the local lattice orientation.
High resolution diffraction contrast images can be obtained when making an
image in a weakly excited beam, the deviation from the Bragg condition being
large, e.g., image made in g when the Bragg condition is satisfied for - 2g in the
perfect part of the foil. The dislocations are then imaged as very fine bright lines
on a darker background. This technique called weak-beam method, is mainly
useful for the study of the fine structure of dislocations, i.e., their dissociation
in two or more partial dislocations, coupled by faults, for instance in view of
determining stacking fault energies.
Planar interfaces in inclined planes with respect to the foil plane are imaged
as fringe patterns, the fringes being parallel to the intersection lines of the fault
plane with the foil surfaces, the depth period being equal to the extinction
distance. Stacking faults parallel to the foil plane are imaged as areas with a
different brightness (lighter or darker), limited by partial dislocation lines. In
weak beam images the spacing of the fringes becomes small since the effective
extinction distance becomes smaller as the deviation parameter increases.
Domain structures can be imaged as areas of different brightness because of the
sensitive dependence of the scattered intensity on the lattice orientation.
High Resolution Images (foil thickness < 100 A, resolution < 2.6 A)
With the improvements in the instrumental resolution of electron microscopes
(in 1988 ~ 1.6 A) it has become feasible to image individual atom columns when
viewing a crystal along a zone axis parallel to such columns. As many beams as
are compatible with the instrumental resolution, are then allowed to pass
through the electron optical system and made to interfere so as to form the
378
image. Unfortunately, the relative phases of the contributing beams are changed
in passing through the electron optical system due to lens aberrations and
defocusing. Computer simulation of images is therefore important for a correct
interpretation. However, in the very thin parts, close to the edge of the foil,
where the thickness is only a few unit cells ( < 100 A) the heavy atom columns
are imaged as dark dots whereas the light atoms and the inter-column channels
appear as bright spaces, and a directly interpretable image of the structure can
be obtained under suitable focussing conditions (Scherzer focus). In the thicker
parts heavy atom columns are imaged as bright dots. These phenomena are
explained by the strong forward scattering of electrons, the smallness of the
Bragg angles, and by noting that the electrostatic potential associated with an
atom column acts as an axially symmetric lens which periodically, along the
Fig. 9Oa-f. Diffraction contrast image of anti-phase boundaries in Anorthite. In-situ heating
cycle through the I -+ P -+ I phase transitions. The same area is imaged throughout from a to f.
In c the specimen is in the P-phase (high temperature phase). Note the pronounced "memory
effect", i.e., the same configuration of anti-phase boundaries as in a is re-established in f
379
column, makes the electrons converge and diverge. Electron transmission

through a foil is thus largely a "local" phenomenon and a periodic structure is
not required to obtain an image of an arrangement of columns. As a consequence also deviations from a periodic structure, such as dislocations,
anti-phase boundaries and stacking faults, can be imaged provided the configurations are formed by straight atomic columns parallel to the incident beam.
High resolution electron microscopy is especially powerful in revealing
planar defects such as stacking faults, out-of-phase boundaries, crystallographic
shear planes, etc. as well as the regular sequences of these such as they occur in
polytypes, mixed layer compounds, shear structures, etc. by viewing them along
a zone axis parallel to the plane of the defects and with the close packed atom
Fig. 91. High resolution

image across an anti-phase
boundary in anorthite. Note
the shift of the atom rows
Fig. 92. High resolution image of stacking fault in the

wurtzite structure (ZnS). The
letters symbolize the stacking
of the layers
380
rows. In pure edge dislocations the atomic configuration is essentially twodimensional; it can therefore be revealed when viewed along the dislocation line.
In particular, the supplementary halfplane and the displacement field can be
visualized directly. Screw dislocations do not allow a similar meaningful projection. Examples of observations are shown in Figs. 90 - 99. Thanks are due to
Prof. G. Van Tendeloo, J. Van Landuyt, D. Van Dyck, 1. Van Hellemont,
H. Bender, C. Van Heurck, for the use of photographs from joint papers.
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...
-:"
..
__
w "
'.I .... .. &
It
.....
til
....
t .~.~.-~
~_
t1
fit'"
~
:t
C""
k~~~
e ~
!' ;a J
...
'
...
-'
A
B (' .'
,#'
C3 -I
.......-..... - -
10.
" fI
'- s #-.,. ,"
_&
"
, A
j.
..
..-. ,.
'-
~-
II ... ,. - ........_ .... ., . . . . . . . . 10 ..
'1* ......
. . .
.....
..... ......
....' .. ..
"
10 ..
...
#' ~ .j ti
.....
."-
~.~
-~\
__ . .
... ..
. . . . . . . .- . . . .
~~
'"
~I
s .... '"
.. '
...............
, .....
~.~_.~~~K.'.~
~~~&~~~~...~
w~~-~~
~-~~.~,.~4~~~~~~~~~4~
10, ... ,,--.~ ... "" .... -..",....... 4i "fIo," "'.--'" .............. ,..-'.,.
...... .~ ...........'". +
,,~
ill ..,. . . . . . . . . . . *'';'''~
.fIt
-"IC.." ""
.........
Fig. 93. High resolution image

of "micro twin" in the sphalerite
~~+, ...... -* ,If,..~,.... 4~~~~'ir!
structure (ZnS)
t ...
i>c(ot,..... .....,"" ......... ,. ....
3"0 .......... .\, ....
~. . . . It .. ~- ;. .
Fig. 948, b. Periodic anti-phase

boundaries in the modulated
structure of sylvanite (Au,Ag)
Te z. Arrows indicate the antiphase boundaries. 8 Low magnification, high resolution. b
High magnification, high resolution
381
, 100 nm
Fig. 95. Diffraction contrast image of incommensurately modulated structure, occurring in a

narrow temperature interval between 0( and {3 quartz. The triangular regions image 0( and 0(2
(Dauphine twins). The domain size decreases with increasing temperature (from top to bottom)
Fig. 96. Multiple twinning in

krennerite (AuAg)Te 2 The unit
cell is outlined
382
Fig. 97. Intergrowth of different members of the synchisite-bastnaesite family of mixed layer
compounds. One-dimensional lattice fringes. (S synchisite layer; B bastnaesite layer)
Fig. 98. Anti-ferroelectric domain walls in titanite (diffraction contrast). The temperature (T)
of the specimen is indicated relative to the critical temperature (Te)
383
Fig. 99. Fringe patterns due to outof-phase boundaries in pyrhotite
J.c.
DOUKHAN and P. CORDIER
Historical Overview
The phenomenon of hydrolytic weakening in quartz was discovered by Griggs

and Blacic in 1965 (Griggs and Blacic 1965; Griggs 1967, 1974). This solved the
apparent paradox with which the mineral physicist's community was faced for
more than a decade. Indeed, in laboratory experiments, natural (dry) quartz
crystals exhibited a very high strength, even at high temperature and confining
pressure l (Carter et al. 1964; Christie et al. 1964; see also a review in Blacic and
Christie 1984). By contrast, in quartz-bearing rocks there is abundant microscopic evidence that quartz has flowed extensively and is weaker than other
minerals such as feldspars, under most conditions occurring in the Earth's crust
(i.e., moderate temperature and stress level).
1 Quartz is so strong that Bridgmann considered at one time its use for fabricating pistons for
his high pressure apparatus but in fact this application was not pursued because of the
brittleness of the material (after Blacic and Christie 1984).
384
a(MPa)
4000
dry
2000
Fig. 100a, b. a Stress-strain curves

for dry (natural) and wet (synthetic)
quartz. b Griggs model of hydrolytic weakening: the open circles
represent the Si atoms while the
bars represent the strong Si-O-Si
bonds. The broken line is a hydrolyzed bond (Si-OH ... HO-Si)
wet
b
5
10
15
Griggs and Blacic showed in 1965 that synthetic wet 2 quartz is ductile under
moderate stress while natural (dry) quartz becomes ductile in the presence of
water. The strengths of such crystals are at least one order of magnitude lower
than those of natural crystals deformed in a dry assembly (Fig. 100). Water
contents as low as 0.005 wt. % (HjSi :::; 300 at. ppm) induce the weakening effect,
even without confining pressure (see for instance Baeta and Ashbee 1970;
Kekulawala et al. 1981; Linker and Kirby 1981; Doukhan and Trepied 1985).
Griggs and Blacic (1965) postulated that the weakening effect stems from the
hydrolysis of the strong Si-O bonds by the water molecules contained in the
crystal; an enhanced glide mobility of the dislocations would thus result. They
2 The concentration of water in quartz is measured by infrared spectroscopy (Paterson 1982;
Aines and Rossman 1984).
385
also suggested that other nominally anhydrous silicate minerals should similarly
be weakened by very small water contents. Although less marked than in quartz,
this effect has been detected in a number of minerals like olivine (Karato et al.
1986) and clinopyroxenes (Ross and Nielsen 1978); however, this effect seems
more marked in berlinite AIP0 4 , a structural analog of quartz (Boulogne et al.
1988). This probably means that the structure of the crystal is also a relevant
parameter of the weakening phenomenon.
Along the same lines McLaren and Retchford (1969) suggested that water
assists dislocation climb rather than glide. Both models are localized ones, i.e.,
only the water defects lying in the immediate vicinity of the dislocation core
enhance its mobility; hydrolytic weakening thus requires (is governed by?)
diffusion of the water defects towards the dislocation cores. In contrast, Hirsch
(1981) and Hobbs (1981, 1985) have proposed independently a delocalized
model. In strong analogy with the case of covalent semiconductors (Alexander
and Hasen 1968), they assume that dislocations in quartz are terminated by
unsaturated (dangling) bonds and that water (the dopant) induces shallow levels
in the band gap. Kinks and/or jogs, which form localized levels in the gap, can
thus trap the carriers of the shallow level and form new (charged) kinks and/or
jogs; the total density of kinks and/or jogs increases and an enhanced glide
and/or climb mobility of the dislocations results. Heggie and Nylen (1984,1985)
have performed computer simulations of dislocation cores in CL quartz and
shown that the cores should be reconstructed, i.e., the orbitals along the
dislocation core should rotate in such a way that they would overlap, forming
weak bonds. As a result no unsaturated (dangling) bonds are expected, i.e., no
extra kinks and/or jogs should form. It can thus be said that actually, the
mechanism(s) of hydrolytic weakening in quartz is not yet fully elucidated.
The Present State of the Art
Clearly, a number of problems are still to be solved: what is the nature of the
water associated point defects? What is their solubility as a function of standard
thermodynamic parameters like T, P, P 02 ' etc.? What is their diffusivity? By
which mechanism do they enhance the glide and/or the climb mobility of the
dislocations? Is this mechanism identical for the various glide systems which can
be activated in quartz: glide directions (Burgers vectors) a, C and c + a in various
glide planes? What happens in other nominally anhydrous silicates?
A number of investigations by transmission electron microscopy (TEM)
have shown that in most wet synthetic quartzes, water is not truly dissolved; it
occurs under the form of tiny water bubbles 100 to 1000 A in diameter. During
high temperature deformation the state of dispersion of this water changes
continuously; the bigger bubbles grow at the expense of the smaller ones; this
requires some material to be removed from the bigger bubbles (to relax their
inner pressure) and diffused towards the cores of the mobile dislocations, thus
inducing their climb motion. Superimposed to the applied stress, the driving
386
force associated to this Oswald rippening phenomenon seems to govern the

plasticity of wet quartz. This is the first important aspect of the hydrolytic
weakening phenomenon in quartz. It affects all types of dislocations (Burgers
vectors a, c and a + c).
There exists however some wet synthetic quartzes containing a significant
and homogeneous (supersaturated) concentration of water point defects of the
order of H/Si ~ 100 at. ppm but no fluid inclusions. These crystals have been
plastically deformed in thermodynamic conditions T, P, P 02 such that the water
defects remain soluble. They exhibit a ductile behavior at moderate stress and
temperature. Furthermore only a glide can be activated, in various {1 0 In}
planes. A similar situation occurs in dry quartz; only a glide can be activated, but
at stresses markedly higher. In berlitine too, only a glide can be activated in dry
material while, when the crystals contain numerous tiny water bubbles, all types
of dislocations are nucleated, even the ones with unexpectedly large Burgers
vectors like a + c ( ~ 13 A); all these dislocations are found in climb configuration, even after deformation at moderate temperature. Therefore in quartz as
well as in berlinite, water point defects assist a dislocation glide only, probably in
facilitating the nucleation (and the propagation?) of elementary double kinks
along the mobile dislocations. This is the second important aspect of the
hydrolytic weakening phenomenon.
Oxygen fugacity also affects the ductility of quartz probably because it affects
the solubility and/or the activity of the water defects; this is the third important
aspect of the hydrolytic weakening phenomenon.
The possibility of introducing water point defects in initially dry quartz
(diffusional uptake) has been carefully tested at high temperature and high
pressure. No significant increase of OHs was detected, which means that either
their solubility or their diffusivity is very low. It is thus at present supposed that
in the original weakening experiments of Griggs, water was introduced in the
samples along their numerous fractures due to the large confining pressure (Fitz
Gerlad et al. 1991), while the wet synthetic quartz with only water point defects
have been grown in conditions such that water point defects have a supersaturated concentration. Their nature is not yet fully elucidated. In strong
analogy with the case of hydrogarnets, the substitutional defect (4H)Si has been
deduced by Wei I (1984) from electron spin resonance (ESR) experiments (one Si
is substituted by four Hs or equivalently one Si0 2 group by two H 20). The
equilibrium concentration of such defects must thus depend on the partial
pressure of H2 (or H 20 or 02)' Another model deduced from computer
simulations (Haggon et al. 1987a, b) rather suggests that water enters and
diffuses in the c channels in the form of interstitial molecules. Whatever their
exact nature, the solubility and the diffusivity of the water point defects has been
tentatively estimated experimentally and theoretically. Depending upon the
models, this solubility varies from H/Si ~ 10 to a few hundreds at. ppm. The
diffusion coefficient of water is found to follow the law
D = Doexp( - E/RT) with Do = (10 2) 10- 11 m 2 s- 1
E = (95 10) kJoulemol- 1 .
and
387
Fig. lOla-c. TEM micrographs showing

typical dislocation microstructures in experimentally deformed quartz. All the samples have been compressed along the same
0 + orientation which promotes at a time c
glide in {I 1 :2 O} and a glide in basal or
rhombohedral planes; the bar stands for
1 j.lm. a dry quartz deformed at T
= 1300 C, P = 300 MPa, constant strain
rate e = 10 - 5 S - I; total strain G ~ 5%
(Doukhan and Trepied, 1985). The deformation is heterogeneous, concentrated in
narrow bands with a large density of a
dislocations; no c dislocations are detected.
The a dislocations exhibit marked crystallographic orientations parallel to low index
directions. Such a microstructure is consistent with a deformation regime controlled by a strong Peierls friction. b Synthetic quartz with a homogeneous
concentration of water point defects
HjSi ~ 100 at. ppm
deformed
at
T
= 700 C, P = 1000 MPA (water point defects remain dissolved), constant strain rate
e = 10- 6 S-I, total strain G = '.5% (Cordier and Doukhall 1989). The deformation
microstructure is similar to the previous
case. It is heterogeneous, concentrated in
narrow bands with a large density of a
dislocations (no c dislocations detected);
these a dislocations exhibit crystallographic
orientations parallel to low index directions. This microstructure is also consistent
with a Peierls regime but the deformation
temperature and the applied stress are
markedly lower than in case a. Glide was
assisted by hydrolytic weakening. c Synthetic quartz with a homogeneous concentration of water point defects HjSi
= 180 at. ppm larger than the solubility at
T = 700 C, P = 1000 MPa. Constant
strain rate e = 10- 6 S - I, total strain G
= 1.5% (Cordier and Doukhan 1989). The
dislocation microstructure is homogeneous.
Dislocations are in climb configuration and
form rough subgrain boundaries. Water
has precipitated in tiny bubbles; c dislocations have been activated. The flow stress
is lower than in b. This deformation is
assisted by water precipitation and Oswald
ripening of the precipitates; it corresponds
to what has often been called hydrolytic
weakening in wet synthetic quartz
388
Conclusion
A number of problems dealing with hydrolytic weakening still are to be solved.
What is the nature of the water point defects and what is their equilibrium
solubility? However since the discovery of the phenomenon of hydrolytic
weakening of quartz our knowledge of its micromechanisms has considerably
progressed. This is illustrated in Fig. 101, which summarizes some typical
dislocation microstructures resulting from experimentally deformed quartz with
various water contents. These micrographs illustrate the various processes by
which what is called by the unique name of "hydrolytic weakening" operates. It
should also be mentioned that until now, there is no reliable creep law of wet
quartz which would take into account the parameter "water content" and which
could be extrapolated to the very low strain rates and low stresses of natural
deformation in the earth's crust. Indeed in almost all the published deformation
experiments, the state of dispersion of water is not controlled like the more usual
parameters T and P. This is probably an important experimental work to
do now. In other silicate minerals, the understanding of the micromechanisms
associated to hydrolytic weakening is just beginning.
References
Aines RD, Rossman GR (1984) Water in minerals? a peak in the infrared. J Geophys Res 89:
4059-4071
Aines RD, Kirby SH, Rossman GR (1984) Hydrogen speciation in synthetic quartz. Phys
Chern Minerals 11: 204-212
Alexander H, Hasen P (1968) Dislocations and plastic flow in the diamond structure. Sol State
Phys 22: 27-158
Baeta RD, Ashbee KHG (1970) Mechanical deformation of quartz. I Constant strain rate
compression experiments. Philos Mag 22: 601-624
Blacic JD, Christie JM (1984) Plasticity and hydrolytic weakening of quartz single crystals.
Boulogne B, Francois P, Cordier P, Doukhan JC, Philippot E, Jumas JC (1988) Plastic
deformation of wet synthetic IX berlinite AIP0 4 Philos Mag A 57: 411-430
Carter NL, Christie JM, Griggs DT (1964) Experimental deformation and recrystallization of
quartz. J Geol 72: 687-733
Christie JM, Griggs DT, Carter NL (1964) Experimental evidence of basal slip in quartz.
J Geol 72: 734-756
Cordier P, Doukhan JC (1989) Water in quartz, solubility and influence on ductility. Eur J
Mineral 1: 221-237
Cordier P, Doukhan JC (1991) Water speciation in quartz; a near infrared study. Am Mineral
76: 361-369
Cordier P, Boulogne B, Doukhan JC (1988) Water precipitation and diffusion in wet quartz
and wet berlinite AIP0 4 Bull Mineral 111: 113-137
Doukhan JC, Trepied L (1985) Plastic deformation of quartz single crystals. Bull Mineral 108:
97-123
FitzGerald JD, Boland IN, McLaren AC, Ord A, Hobbs BE (1991) Microstructures in waterweakened single crystals of quartz. J Geophys Res 96: 2139-2155
Gerretsen J, Paterson MS, McLaren AC (1989) The uptake and solubility of water in quartz at
elevated pressure and temperature. Phys Chern Minerals 16: 334-342
389
Griggs DT (1967) Hydrolytic weakening of quartz and other silicates. Geophys J R Astr Soc
14: 19-31
Griggs DT (1974) A model of hydrolytic weakening in quartz. J Geophys Res 79: 1653-1661
Griggs DT, Blacic IN (1965) Quartz: anomalous weakness of synthetic crystals. Science 147:
292-295
Haggon JP, Stoneham AM, Jaros M (1987a) Transport processes in silicon oxidation. I Dry
oxidation. Phil os Mag 55(2): 211-224
Haggon JP, Stoneham AM, Jaros M (1987b) Transport processes in silicon oxidation. II wet
oxidation. Phil os Mag B 55(2): 225-235
Heggie M, Nylen M (1984) Dislocations core structures in ex quartz derived from a valence
force potential. Phil os Mag 51: L69-L72
Heggie M, Nylen M (1985) Dislocations without deep states in ex quartz. Philos Mag 51:
L69-L72
Hirsch PB (1981) Plastic deformation and electronic mechanisms in semiconductors and
insulators. J Phys C: 3149-160
Hobbs BE (1981) The influence of metamorphic environment upon the deformation of
minerals. Tectonophysics 78: 335-383
Hobbs BE (1985) The hydrolytic weakening effect in quartz. In. Schock RN (ed) Point defects
in minerals. Geophys Monogr 31. Am Geophys Union, Washington, pp 151-170
Karato S, Paterson MS, Fitzgerald JD (1986) Rheology of synthetic olivine aggregates:
influence of grain size and water. J Geophys Res 91: 8151-8176
Kekulawala KRSS, Paterson MS, Boland IN (1981) An experimental study of the role of water
in quartz deformation. In: Carter NL, Friedman M, Logan JM, Stearns DW (eds)
Mechanical behaviour of crustal rocks. Geophys Monograph 24 Am Geophys Union,
pp 49-60
Kronenberg AK, Kirby SH, Aines RD, Rossman GR (1986) Solubility and diffusional uptake
of hydrogen in quartz at high water pressures: implications for hydrolytic weakening.
J Geophys Res 91: 12723-12744
Linker MF, Kirby SH (1981) Anisotropy in the rheology of hydrolytically weakened synthetic
quartz crystals. In: Carter NL, Friedman M, Logan JM, Stearns DW (eds) Mechanical
behaviour of crustal rocks. Geophys Monograph 24 Am Geophys Union Washington,
pp 29-48
McLaren AC, Retchford JA (1969) TEM study of the dislocations in plastically deformed
synthetic quartz. Phys Stat Sol 33: 657-668
McLaren AC, Retchford JA, Griggs DT, Christie JM (1967) TEM study of Brazil twins and
dislocations experimentally produced in natural quartz. Phys Stat Sol 19: 631-644
McLaren AC, Cook RF, Hyde ST, Tobin RC (1983) The mechanisms of the formation and
growth of water bubbles and associated dislocation loops in synthetic quartz. Phys Chern
Minerals 9: 79-94
McLaren AC, FitzGerald JD, Gerretsen J (1989) Dislocation nucleation and multiplication in
synthetic quartz: relevance to water weakening. Phys Chern Minerals 16: 465-482
Ord A, Hobbs BE (1986) Experimental control of the water-weakening effect in quartz. In:
Hobbs BE, Heard HE (eds) Mineral and rock deformation: laboratory studies. Geophys
Monogr 36 Am Geophys Union Washington, pp 51-72
Paterson MS (1982) The determination of hydroxyl by infrared absorption in quartz, silicate
glasses and similar materials. Bull Mineral 105: 20-29
Paterson MS (1986) The thermodynamics of water in quartz. Phys Chern Minerals 13:
245-255
Ross JV, Nielsen KC (1978) High temperature flow of wet polycrystalline enstatite. Tectonophysics 44: 233-261
Rovetta MR (1989) Experimental and spectroscopic constraints on the solubility of hydroxyl
in quartz. Phys Earth Plan Int 55: 326-334
Rovetta MR, Holloway JR, Blacic JD (1986) Solubility of hydroxyl in natural quartz annealed
in water at 900 C and 1.5 GPa. Geophys Res Lett 13: 145-148
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390
6.3.5 High Temperature Flow in Minerals and Ceramics and Its

Bearing on the Creep Behavior of the Earth's Silicate Mantle
M.R.
DRURY
Flow in Crystalline Materials

All crystalline materials when subjected to stress at elevated temperatures
exhibit creep which is the slow accumulation of time-dependent permanent
strain. Experimental deformation and electron microscopy studies have demonstrated that, in general, high temperature flow phenomena and basic deformation mechanisms are the same in all types of crystalline material from metals,
semiconductors, simple oxides, and silicate minerals. The basic deformation
mechanisms involved in creep are motion of defects such as point defects and
dislocations in crystalline grains and sliding along the boundaries between
crystalline grains. The basic processes involved in grain sliding are also motion
of point defects and interfacial dislocations.
Many materials when deformed at constant stress exhibit conventional creep
behaviour which can be divided into three distinct stages. In the primary stage
the strain-rate decreases with time; in the secondary stage the strain-rate
approaches a steady state value and in the tertiary stage the strain-rate increases
with time. In general, the steady-state creep strain-rate is a function of the stress
magnitude, homologous temperature and microstructural state of the material.
Equations (1) and (2) are commonly used constitutive laws which describe the
creep behaviour in the secondary stage;
t = Aand-mexp[ -(E
+ PV)/RT]
t = Band-mexp( - gTm/T)
(1)
(2)
where t is the steady state strain-rate, a the stress, T the temperature, Tm the
melting temperature, P the confining pressure, E the activation energy, V the
activation volume and A, d the grain size, B, m, n, and g constants. When creep
occurs by dislocation processes the constants commonly have values in the
range of n = 3-5, m = 0-1, E = 1.5-0.6 ESD (where ESD is the activation energy
for self diffusion). For creep by diffusion processes or by grain boundary sliding
n = 1-2, m = 1-3, and E = 0.6-1.0 ESD '
The occurrence of steady state creep in crystalline materials enables the flow
of the material to be described in terms of a stress-dependent viscosity '1 = a/3t.
Most theoretical continuum models of flow in the Earth's mantle assume that
the creep in the mantle is a linear viscous process with the stress exponent n in
Eqs. (1) and (2) equal to one. In this simple case the solid state viscosity can then
be simply expressed as a function of temperature and pressure.
Recent experiments on olivine (Borch and Green 1987) suggest that the effect
of pressure is described best by a dependence of creep-rate on the homologous
391
temperature, e.g., Eq. (2). Borch and Green (1987), however, used the solidus of
the mineral assemblage to normalize their data. It is probably physically more
realistic to use the melting temperature of olivine.
The traditional interpretation of conventional creep curves has recently been
questioned. Evans and Wilshire (1985) suggest that a true steady state is never
attained. In their model the shape of the creep curve is related to the superposition of primary creep produced by work hardening processes and tertiary creep
produced by recovery processes. If this model is correct there are major
implications for the nature of large-strain creep processes in the mantle. In
particular it would no longer be possible to define a strain-independent solid
state viscosity. For a large-strain flow as encountered in the convecting mantle
the creep-rate could be cyclic with each cycle terminated by a creep instability.
Special Aspects of Creep in Minerals and Ceramics

The complex nature of minerals and ceramics is responsible for some complications in creep behavior. Some of the more important effects are outlined
below.
1. Climb dissociation of dislocations is common in minerals and can result
in anomalous creep behavior where the viscosity increases with increasing
temperature (Doukhan and Paquet 1982). Climb dissociation is important
in spinels and perovskites (Poirier 1985; Poirier et al. 1989) and in olivine
segregation of hydrogen to dislocation cores can induce climb dissociation of
dislocations with Burgers vector b = [001] (Drury 1991).
2. Some ceramics and minerals exhibit inverse primary creep (Evans and
Langdon 1976; McLaren et al. 1989) with increasing strain-rate with time. This
behavior is observed in materials which have a low initial content of mobile
dislocations. The creep rate in this case is not controlled by hardening interactions of dislocations but by the nucleation and multiplication kinetics of
mobile dislocations. Work on synthetic quartz (McLaren et al. 1989; Fitz Gerald
et al. 1991) suggests that the so-called hydrolytic weakening effect may be largely
related to the difficulty of dislocation nucleation and multiplication in dry
quartz crystals.
3. Grain boundary structures in rocks can have a range of structures from
narrow semicoherent structures with structural widths comparable to those in
metals (Hay and Evans 1988, Bons et al. 1990) and in simple oxides (Ruhle 1985)
to interfaces defined by thin films of a segregated second phase. The second
phase film can be crystalline (Bons et al. 1990) or a fluid or melt film. Differences
in grain boundary structure can lead to large differences in diffusion creep
kinetics. Semi-coherent grain boundary structures are likely to be more important in the transition zone and lower mantle owing to the predominance of cubic
and distorted cubic phases.
4. The polyphase nature of most rocks can lead to complicated rheological
behaviour. It is usually assumed that the predominant mineral in the assemblage
392
will provide a stress supporting framework and control the behavior of the rock.
During large-strain deformation, mechanical or chemically induced segregation
of a weak minor phase along the foliation can result in deformation being
concentrated in the weak phase. In many cases these weak bands can be
produced in rocks by the transformation of hard phases to fine-grained polyphase reaction products which deform by the Grain-Size Sensitive (GSS) creep
or dislocation creep of weak minerals. GSS creep in polyphase multi-component
materials can occur with faster kinetics than in single phase materials.
5. Minerals show a rich diversity of transformations which may have a
considerable influence on the high temperature flow behavior in some critical
regions of the Earth. The fundamental physical basis for transformation enhanced plasticity is poorly established at present. Traditional models derived
from studies on metals have considered the role of stresses induced by the
volume changes associated with transformation. Current research suggests that
other aspects of the transformation may also be important (McLaren and
Meike, in progess).
Application to Flow Phenomena in the Mantle

It should be noted that the constitution of the mantle is still a subject of
controversy. The most simple model that appears to be consistent with current
seismological, geochemical, and mineral physics constraints is a homogeneous
mantle in terms of bulk composition. In this pyrolite model (Ringwood 1975)
the upper mantle consists of peridotite dominated by olivine and pyroxene, the
transition zone consists mainly of(Mg,Fe)2Si04 spinel and M3 (MSi,AI 2 ) Si 30 12
garnet (where M = Mg, Fe, Ca) and the lower mantle an assemblage of
(Mg,Fe)Si03 peroskvite and (Mg,Fe)O. Other models propose that the transition zone and lower mantle have a more silica-rich composition.
Upper mantle minerals have been studied extensively. It is commonly
assumed that olivine will control the rheology of the upper mantle. In the
dislocation creep regime flow-laws have been established for dry single crystals
and wet and dry polycrystals. In the grain size-sensitive creep regime flow-laws
have been established for fine-grained wet and dry polycrystals. Extrapolations
of the experimental data on olivine to conditions in the convecting upper mantle
indicates that dislocation creep will be the dominant process if the olivine grain
size is controlled by dynamic recrystallisation. GSS creep may occur locally if
a small grain size is maintained with grain growth limited by the presence of
a high second phase content.
Experimental data and observations on naturally deformed upper mantle
peridotites show that GSS deformation mechanisms are important in lithosphere shear zones. The rheology of the lithosphere is often modeled with a
power law rheology. This can be a considerable over-simplification owing to the
influence of localized shear zones which will result in a complex strain and timedependent rheological evolution during large strain deformation.
393
Experimental creep data on phases from the transition zone and lower
mantle are non-existent, although there is some information on the relative yield
strengths and hardness of the phases at room temperature and information
on the creep properties of structural analogs. Attempts have been made to use
generalized creep-systematics for crystalline materials to predict transition zone
and lower mantle rheology. These models predict viscosity structures which are
compatable with other geophysical contraints, which indicate that the lower
mantle has similar or higher viscosity than the upper mantle. The assumption of
whole mantle or layered convection has an important influence on the predicted
viscosity profiles (Ranalli 1987).
Using the approach of defining iso-mechanical groups of crystalline materials, it can be shown that garnets and spinels generally have very high normalized (dislocation) creep resistance, higher than both upper and lower mantle
phases. If the rheology of the transition zone is controlled by these phases, then
the transition zone may conceivably be a zone of relatively high viscosity. The
occurrence of pyroxene in the uppermost part of the Transition Zone may lead
to the occurrence of weak zones developed by local segregation of the weak
phase. In addition, the possible effects of transformation-enhanced-creep may
possibly counter balance any intrinsically high viscosity of the predominant
phases. The high viscosity model for the Transition Zone assumes that dislocation creep is the predominant creep mechanism. If GSS creep is predominant,
the Transition Zone will not necessarily be a zone of high viscosity. For
example, rheological data on MgGe0 4 (an analog for olivine) shows that finegrained y spinel has a viscosity about one or two orders of magnitude lower than
the coarse-grained olivine phase.
For the case of the lower mantle, the rheology will be sensitive to the bulk
composition which will control the amount of magnesiowiistite present. Microstructural observations (Poirier et al. 1986) suggest that perovskite has a higher
creep resistance than magnesiowiistite as is also suggested by normalized creep
data for structural analogs of these phases (Karato 1989). Normalized data
suggest that on average perovskites are weaker than olivine phases; however,
some perovskites have higher creep resistance than some olivine phases. Current
data on perovskite indicate that they do not form a well-defined iso-mechanical
group, so it may be difficult to infer the properties of MgSi0 3 perovskite from
studies of analogs. The results on yield strength experiments indicate that
MgSi0 3 perovskite has a higher creep resistance than olivine at room temperature; however, extrapolation of these data to mantle conditions is extremely
hazardous until there are constraints on the temperature dependence of creep
in MgSi0 3 perovskite. Under most situations perovskite should control the
rheology of the lower mantle, but local segregation of magnesiowiistite in highstrain zones could result in local rheology being controlled by magnesiowiistite.
In addition, a high magnesiowiistite content should inhibit grain growth of the
perovskite, thus favoring GSS creep processes over dislocation creep.
Owing to the difficulty of performing creep measurements on transition zone
and lower mantle phases, the rheology of these phases may not be understood
394
until further advances are made in the theoretical understanding of creep

processes and the influence of crystal structure, bonding, composition, and
transformations. Such progress may well depend on the characterization of isomechanical groups or finding suitable individual analogs for the mantle phases.
There are also important aspects of upper mantle rheology that are poorly
contrained. The most important of these is the effect of various second phases
such as pyroxenes, melts and (in the case of the lithospheric mantle) the effects of
hydration reactions during fluid infiltration in shear zones. These problems can
be addressed partly by experimental studies on synthetic polyphase upper
mantle aggregates.
References
Anderson DL (1989) Theory of the Earth. Blackwell Scientific, Boston
Beauchesne S, Poirier JP (1990) In search of systematics for the viscosity of perovskites: creep
of potassium tantalate and niobate. Phys Earth Planet Int 61: 182-198
Bons AJ, Drury MR, Schryvers D, Zwart HJ (1990) The nature of grain boundaries in slates.
Implications for mass transport processes during low temperature metamorphism. Phys
Borch RS, Green HW II (1987) Dependence of creep in olivine on homologous temperature
and its implications for flow in the mantle. Nature 330: 345-348
Cannon WR, Langdon TG (1988) Creep of ceramics, J Mater Sci 23: 1-20
Chen I-W (1983) Effects of grain boundary mobility and phase equilibrium on kinetic
processes of multi-component polyphase ceramics. In: Yan MF and Heuer AH (eds)
Advances in ceramics. Vol. 6, Character of grain boundaries. Am Ceramics Soc Inc,
Columbus, Ohio, pp 224-235
Doukhan JC, Paquet J (1982) Plastic deformation of andalusite single crystals AI 2 SiO s. Bull
Mineral 105: 170-175
Drury MR (1991) Hydration induced climb dissociation of dislocations in naturally deformed
olivine. Phys Chern Mineral 18: 106-116
Drury MR, Hoogerduijn Strating EH, Vissers RLM (1990) Shear zone structures and
microstructures in mantle peridotites from the Voltri massif, Ligurian Alps, N.W.ltaly. Geol
Mijnbouw 69: 3-17
Evans AG, Langdon TG (1976) Structural ceramics. Prog Mater Sci 21: 171-441
Evans RW, Wilshire B (1985) Creep of metals and alloys, Institute of Metals, London
Fitz Gerald JD, Boland IN, McLaren AC, Ord A, Hobbs BE (1991) Microstructures in waterweakened single crystals of quartz. J Geophys Res 96: 2139-2155
Frost HJ, Ashby MF (1982) Deformation mechanism maps. Pergamon, Oxford
Gwanmesia GD, Rigden SM, Jackson I, Liebermann RC (1990) Pressure dependence of elastic
wave velocity for b Mg 2 Si0 4 and the composition of the Earth's mantle. Science 250:
794-797
Handy MR (1989) Deformation regimes and the rheological evolution of fault zones in the
lithosphere: the effects of pressure, temperature, grain size and time. Tectonophysics 163 :
119-152
Hay RS, Evans B (1988) Intergranular distribution of pore fluid and the nature of high-angle
grain boundaries in limestone and marble. J Geophys Res 93: 8959-8974
Karato S-I (1989) Plasticity-crystal structure systematics in dense oxides and its implications
for the creep strength of the Earth's deep interior: a preliminary result. Phys Earth Planet Int
55: 234-240
Karato S-I, Paterson MS, Fitz Gerald JD (1986) Rheology of synthetic olivine grain
aggregates: influence of grain size and water. J Geophys Res 91: 8151-8176
Karato S-I, Fujino K, Ito E (1990) Plasticity of MgSi0 3 perovskite: the results of microhardness tests on single crystals. Geophys Res Lett 17: 13-16
6.4 Electrical Properties of Minerals
395
Mackwell SJ, Bai Q, Kohlstedt DL (1990) Rheology of olivine and the strength of the
lithosphere, Geophys Res Lett 17: 9-12
McLaren AC (1991) Transmission electron microscopy of minerals and rocks, Cambridge
University Press, New York
McLaren AC, FitzGerald JD, Gerretsen J (1989) Dislocation nucleation and multiplication in
synthetic quartz: relevance to water weakening. Phys Chem Mineral 16: 465-482
Meade C, Jeanloz R (1990) The strength of mantle silicates at high pressures and room
temperature: implications for the viscosity of the mantle. Nature 348: 533-535
Poirier JP (1985) Creep of crystals. Cambridge University Press, Cambridge
Poirier JP, Peyronneau J, Madon M, Guyot F, Revcoleshi A (1986) Eutectoid phase
transformation of olivine and spinel into perovskite and rock salt structures. Nature 321:
603-605
Poirier JP, Beauchesne S, Guyot F (1989) Deformation mechanisms of crystals with perovskite
structure, In: Navrotsyy A, Weidner DJ (eds) Perovskite: a structure of great interest to
geophysics and materials science. Geophys Monograph 45, Am Geophys Union, Washington DC, pp 119-124
Ranalli G (1987) Rheology of the Earth, Allen and Unwin, Boston
Ringwood AE (1975) Composition and petrology of the Earth's mantle, McGraw-Hill,
New York
Ruhle M (1985) Comparisons between observed and computed grain boundary structures and
energies in ceramics. J Phys Coli: C4- 281-292
Rutter EH, Brodie KH (1988a) Experimental "syntectonic" dehydration of serpentinite under
conditions of controlled pore water pressure. J Geophys Res 93: 4907-4932
Rutter EH, Brodie KH (1988b) The role of grainsize reduction in the rheological stratification
of the lithosphere. Geol Rundsch 77: 295-308
Vaughan PJ, Coe RS (1981) Creep mechanism in Mg 2 Ge0 4 : effects of a phase transition.
6.4 Electrical Properties of Minerals

6.4.1 Electrical Conductivity in Iron-Bearing Minerals and
Materials
T.O.
MASON
Many transition metal oxides possess intermediate values of electrical conductivity (l0-2-10 2 (Q-cm)-1) which exhibit Arrhenius behavior with small
(::;; 0.5 eV) activation energies. It can be demonstrated that the mobility in such
materials is often activated, e.g., conduction is via small polaron hopping
(Mason 1988). Among these are the simple oxides of iron and various ironcontaining complex oxides, e.g., spinels, olivines, etc. Such materials have both
geological and technological importance. The electrical properties are closely
related to defect phenomena in these materials, e.g., point defect formation,
multi-site exchange reactions, solid solution, etc. The equations below are
completely general for all the materials and phenomena considered. A more
thorough treatment is given in (Mason 1987).
Assuming that ionic conductivity is negligible (usually valid in the conductivity range given above) and that small polaron hopping is the dominant
396
electronic conduction process, the conductivity is given by:

a == gNc(1 - c)eZaZv exp ( _ EH)
kT
kT '
(1)
where g is a geometric factor on the order of unity, N is the density of iron ions
involved in conduction (cm - 3), c is the fraction of these which are small
polarons, (I - c) is the fraction of iron ions which are of the opposing valence
and therefore available for hopping, e is the unit of electronic charge, a is the
jump distance (cm), v is the lattice vibrational frequency responsible for hopping,
k is Boltzmann's constant, and EH is the hopping energy. In Fez + jFe 3 + systems
the Fez + species are the small polarons, i.e., an electron plus the associated
lattice distortion. For such materials the Seebeck coefficient is given by:
(X
== _
~ln2(1
e
- c)
c
~ln2([Fe3+]),
e
[Fe z +]
(2)
where the parameters have been defined above. [A "transport term" often
appears in expressions for Seebeck coefficient; this is usually negligible in the
case of small polaron conduction, so has been omitted from Eq. (2)]. Given the
unique relationships between the electrical properties and the concentrations of
iron species involved in small polaron conduction, a powerful capability exists
to study defect phenomena in iron-based minerals and materials.
It is important to first establish whether or not small polaron conduction is
dominant in a given system. A number of techniques, based upon manipulations
of Eqs. (1) and (2) can be applied. The most basic, "isothermoelectric conductivity analysis" (Chen et al. 1982), involves demonstrating the existence of an
activated mobility by plotting the electrical conductivity at fixed Seebeck
coefficient vs. inverse temperature. This is tantamount to analyzing the conductivity at fixed carrier content; Arrhenius behavior is clear evidence of an activated
mobility. A second procedure involves isothermal plots of Seebeck coefficient vs.
the logarithm of electrical conductivity, so-called lonker plots, after Jonker
(1968). As opposed to conventional semiconductors, which exhibit a marked
discontinuity at the intersection of p-type and n-type legs at high carrier
contents, small polaron materials exhibit a smoothly varying "knee" at the
highest value of c(1 - c) = 0.25 for c = 0.5 in Eqs. (1) and (2). In addition, n-type
small polaron behavior is symmetric about a value of (X = - kje In 2 [see
Eq. (2)], whereas p-type small polaron behavior is symmetric about a value of
(X = kje In 2 [see Nell et al. 1989a for the p-type small polaron equation
analogous to Eq. (2)]. Thus, the sign of the small polaron can be determined.
Finally, in systems where there is a large and previously determined variation in
Fez + and Fe 3 + contents with composition, adherence to Eq. (2) can be taken as
confirmation that small polaron conduction is present (Wu et al. 1981).
Given the relationships between the electrical properties and the Fez + jFe 3 +
concentrations, Eqs. (I) and (2) have been used to study a variety of point defect
phenomena in iron-containing minerals and materials. A high temperature
6.4.1 Electrical Conductivity in Iron-Bearing Minerals and Materials
397
combined conductivity/Seebeck coefficient apparatus is described in TrestmanMatts et al. (1983a). Conductivity has been employed to study the cation
vacancy formation in fayalite (Sockel 1974), for example. An extensive study of
cation vacancy formation in magnetite was carried out via conductivity and
Seebeck measurements (Dieckmann et al. 1983). Point defect formation in
wiistite and the clustering of cation vacancies and interstitials into defect
aggregates was studied by analysis and modeling of high temperature electrical
properties (Gartstein and Mason 1982; Gartstein et al. 1986).
Cation site exchange in crystal structures with two or more inequivalent
cation sites can also be studied via electrical property variations, if small polaron
conduction predominates. For example, the exchange of Fe 2 + and Fe3+
between tetrahedral and octahedral sites in magnetite has been studied thermoelectrically (Wu and Mason 1981). Because the density of conducting iron ions
(N) is equal to the octahedral site density (tetrahedral iron does not participate
in conduction) and does not change with temperature, the cation distribution in
magnetite can be uniquely determined from Eq. (2). A similar argument should
extend to the situation in fayalite, where two distinct octahedral sites exist, but
this has yet to be confirmed (see Mason (1987) for a discussion of fayalite).
Cation mixing and ordering phenomena can be investigated in solid solutions if small polaron conduction predominates. It should be pointed out that
the overall iron concentration must be kept above a percolation threshold,
e.g., ~ 10% of the total cation sites, for this to hold. Spinel solid solutions of
magnetite with a foreign cation prefering only tetrahedral or octahedral sites
have been analyzed thermoelectrically, e.g., Zn 2 + (tetrahedral site) (Wu et al.
1981), Cr3+ (octahedral site) (Wu et al. 1981), and Ti 4 + (octahedral site)
(Trestman-Matts et al. 1983b). This follows because the density of iron ions
involved in conduction (N) is either invariant (for a tetrahedral substituent) or is
merely the total number of octahedral sites minus the substituent concentration
(for an octahedral substituent). By combining the electro neutrality condition
and Eq. (2), the overall cation distribution can be determined. Although there
have not been published examples to date, ordering of cations should have a
profound and measurable effect on the high temperature electrical properties.
In many instances, solid solutions involve foreign cations which can also
exchange between cation sublattices. In such cases it is still possible to solve for
the overall cation distribution by carefully combining data for both Seebeck
coefficient and electrical conductivity (Mason 1987). The procedure involves
normalizing the electrical conductivity of a given composition to that in the pure
iron oxide end member, correcting for the composition dependence of the
hopping energy [Eq. (1)] and of the product c(l - c) on the basis of the Seebeck
data [Eq. (2)]. The resulting ratio is equal to the ratio of octahedral iron (Fe 2 +
and Fe 3 +) in the given composition to that in magnetite, which is known. This
procedure has been used to establish the overall cation distribution of magnetite
solid solutions involving C0 2 + (Erickson 1985) and AI3+ (Mason 1985 as
described in Mason 1987). The procedure was recently employed to study the
cation distribution in the extremely complex multicomponent system:
398
Fe30cMgA120cMgFe20cFeAl204 (Nell et al. 1989b,c). Application of the

procedure to existing data for (Fe,Mg)2Si04 indicates that either iron or
magnesium are randomly distributed between the octahedral sites, or that the
two sites are electrically equivalent, to a good approximation (Mason 1987).
An even more complex situation involves a variable valence substituent;
oxidation-reduction reactions need to be considered. The Fe304-Mn304 solid
solution was studied by Dorris (Dorris 1988). Equations (1) and (2) were still
employed to solve for the overall cation distribution, but additional information, in this case Mossbauer spectroscopic data on quenched specimens, had to
be supplied. Furthermore, a second competing p-type mechanism in Mn-rich
compositions had to be taken into account (see below). Nevertheless, a more or
less complete picture of the overall cation distribution could be obtained.
To this point, we have intentionally limited discussion to iron-based systems.
Additional valence/defect phenomena occur in other small polaron systems and
are amenable to study. For example, it was shown that disproportionation of
octahedral Mn3+ to Mn2+ and Mn 4+ takes place in Mn 30 4, leading to the
formation of p-type Mn 4 + small polarons (Nell et al. 1989a; Dorris 1988).
Disproportionation plays an important role in determining the cation distribution in Mn 30 4 (Dorris and Mason 1988) and its solid solutions, e.g.,
Mn30cFe304' described above (Dorris 1988). (There is some evidence that
disproportionation and site exchange play an important role in YBa 2Cu 30 6 + y ,
also believed to exhibit small polaron conduction at high temperature (Su et al.
1988; Mason 1991).
Finally, changes in defect structure or cation distribution can be monitored
by transient electrical property changes. Sujata constructed a low thermal mass
furnace and determined the kinetics of site redistribution reactions in previously
quenched spinel ferrites (Sujata 1989). There are important technological and
geological ramifications for such a capability.
References
Chen HC, Gartstein E, Mason TO (1982) Conduction mechanism analysis for Fel_~O and
CO l _6 J Phys Chern Sol 43: 991-995
Dieckmann R, Witt CA, Mason TO (1983) Defects and cation diffusion in magnetite (V):
Electrical conduction, cation distribution and point defects in Fe 3- 6 0 4 Ber Bunsen-Ges
Phys Chern 7: 495-503
Dorris SE (1988) The electrical properties and cation distributions of the Fe30cMn304
solidsolution. PhD Thesis, Northwestern University, Evanston, IL
Dorris SE, Mason TO (1988) The electrical properties and cation valencies in Mn 30 4 J Am
Ceram Soc 71: 379-385
Erickson DS, Mason TO (1985) Nonstoichiometry, cation distribution, and electrical properties in Fe30CCoFe204 at High Temperature. Sol State Chern 59: 42-53
Gartstein E, Mason TO (1982) Reanalysis ofwiistite electrical properties. J Am Ceram Soc 65:
C-24-C-26
Gartstein E, Cohen JB, Mason TO (1986) Defect agglomeration in wustite at high temperatures - II. An electrical conduction model. J Phys Chern Sol 47: 775-781
JonkerGH (1968) The application of combined conductivity and Seebeck-effect plots for the
analysis of semiconductor properties. Philos Res Rep 23: 131-138
399
Mason-TO (1985) High-temperature cation distributions in Fe30cFeA1204' J Am Ceram

Soc 68: C-74-C-75
Mason TO (1987) Cation intersite distributions in iron-bearing minerals via electrical
conductivity/seebeck effect. Phys Chern Mineral 14: 156-162
Mason TO (1988) Electronic behavior and cationic defects in cubic transition metal oxides.
Physica B 150: 37-43
Mason TO (1991) Defect chemistry of high Tc superconducting cuprates. In: Nowotny J (ed)
Electronic ceramic materials. Trans Technol Publ, Zurich, pp 503-536
Nell J, Wood BH, Dorris SE, Mason TO (1989a) Jonker-type analysis of small polaron
conductors. J Sol State Chern 82: 247-254
Nell J, Wood BJ, Mason TO (1989b) Cation distributions in Fe30 4-MgAI 20 4 from thermopower/conductivity measurements. J Phys Chern Mineral 74: 339
Nell J, Wood BJ, Mason TO (1989c) High-temperature cation distributions in Fe30c
MgAI 20 c MgFe 20 4 spinels from thermopower and conductivity measurements. Am
Mineral 74: 339-351
Sockel HG (1974) Defect structure and electrical conductivity of crystalline ferrous silicate. In:
Seltzer MS, Martin S, Jaffee RI (eds) Defects and transport in oxides. Battelle Inst Mat Sci
Coil 8: 341
Su MY, Dorris SE, Mason TO (1988) Defect model and transport at high temperature in
YBa2Cu306+y' J Sol State Chern 75: 381-389
Sujata K (1989) Kinetics of cation distribution in ferrospinels. PhD Thesis, Northwestern
University, Evanston, IL
Trestman-Matts A, Dorris SE, Mason TO (1983a) Measurement and interpretation of
thermopower in oxides. J Am Ceram Soc 66: 589-592
Trestman-Matts A, Dorris SE, Kumarakrishnan S, Mason TO (1983b) Thermoelectric
determination of cation distributions in Fe 3 0 4-Fe 2Ti0 4. J Am Ceram Soc 66: 829-834
Wu CC, Mason TO (1981) Thermopower measurement of cation distribution in magnetite.
JAm Ceram Soc 64: 520-522
Wu CC, Kumarakrishnan S, Mason TO (1981) Thermopower composition dependence in
ferrospinels. J Sol State 37: 144-150

B.A.
MAXIMOV
Ionic conductivity in crystals can be described by charge transfer within a

crystal, which takes place under the influence of an electrical field. Conductivity
can be due to various sorts of ions, such as cations of silver, copper, potassium,
sodium, lithium, divalent cations of zinc, magnesium, barium, as well as fluorine
or oxygen anions or complex large molecules. There are compounds with a high
ionic conductivity due to vacancies or point defects.
At present, many solid materials (both natural and synthesized) possessing
ionic conductivity, called ionic conductors, are known. These are various oxide
compounds belonging to the class of phosphate and silicate materials, and
halogenides, stoichiometric and non stoichiometric compounds, solid solutions,
composite materials, amorphous substances, glasses, and polymeric materials.
Ionic conductors comprise crystals of the structure-families of fluorite, tysonite,
feldspar, perovskite, pyroxene, hollandite, pyrochlore, and carnegieite.
400
A specific feature of ionic conductors is a combination of hardness and

elasticity of the solid with ionic conductivity that can take place sometimes only
in liquid ionic conductors - melts and concentrated electrolytes. If the ionic
conductivity in such materials exceeds 5 x 10 - 2 Ohm - 1 cm -1, and the electronic conductivity is smaller by at least one order of magnitude, these materials
are usually called superionic conductors.
The first report on conductivity in solids was made by Faraday in the first
half of the last century. In 1884, Warburg discovered ionic conductivity in glasslike solid phases; later, in 1888, Nernst measured high values of ionic conductivity at high temperatures in mixed oxide systems. In 1914 Tuband and Lorentz
discovered high values of ionic conductivity in AgI attaining 0.26 Ohm - 1cm - 1
in the temperature range 147-550C.
Despite the fact that ionic conductivity in solids had been known for a long
time, its mechanism remained unclear. First, suppositions were made that this
phenomenon was due to dielectric charge shifts in the crystal lattice. The first
explanations of the nature of ionic conductivity were given by Frenkel. He
pointed out the inevitable structural disorder in crystals at temperatures other
than zero. Frenkel's ideas were later developed in works by Schottky and
Wagner, who created the foundation of modern concepts about the nature of
ionic conductivity in crystals.
For a long time interest in solid electrolytes was modest, but starting from
the late 1960s, investigations of solid electrolytes rose to a new height. This was
stimulated mainly by synthesis of Ag 4RbI s and its application as a solid
electrolyte in electric sources intended for work in space. This compound
undergoes a superionic phase transition at a very low temperature of - 151C,
having the lowest conductivity, close to 0.3 Ohm - 1cm - 1 at room temperature.
At present, the atomic structures and structural phase transitions in many
superionic conductors based on silver-containing compounds, such as IX-AgI,
Ag4Rbl s, IX-Ag 3SI, silicate, and phosphate materials Na3Sc2(P04h, Li 3M 2(P04h where M = Sc, Fe, Cr, Na sRESI 40 12 where RE = Sm - Lu, Y, Sc,
NASICON- Na1+xZr2SixP3-x012 have been studied.
The structural investigations of superionic conductors have demonstrated
once again that the main criterion for the presence of ionic transfer in crystals is
the structural disorder of some sorts or groups of atoms in a crystal. That is,
crystals with high ionic conductivity contain conducting ions that are randomly
distributed over energetically equal or almost equal sites. In this case the ionic
transport pathway in a crystal depends mostly on the distribution of atoms not
involved in the ionic transport. Depending on the mutual orientation of
conductivity channels, the conductors can be divided into one-dimensional,
two-dimensional, and three-dimensional.
The first example of a one-dimensional ionic conductor was fJ-eucriptite,
LiAISi0 4.lts structure is similar to that of quartz; the main channels containing
Li + ions are positioned parallel to the z axis. Conductivity in fJ-eukripite in the
[001] direction at 300C is higher by three orders of magnitude than that in the
directions perpendicular to this axis, i.e., it is the main channels that are the
conducting pathways for the ions within the structure. Crystals of fJ-eukriptite
401
become superionic conductors as a result of a temperature phase transition.

During the phase transition the ordered distribution of Li + ions in a crystal of
p-eukripite is replaced by a statistical one. When ordered, Li + ions occupy
tetrahedral sites so that, if one site is occupied, the next one is vacant, the next
one is occupied again, etc. The occupied and vacant sites are not completely
equivalent in terms of energy; but in a case of statistical disorder I ions are
distributed over all the tetrahedral sites. This is an example of an ionic
conductor in which the conducting ions move over a set of sites that are not
completely equivalent in their energy.
p-Alumina, Na 2 0 nAl 2 0 3 is an example of a superionic conductor with Na
ion two-dimensional conductivity. Its structure consists of spinel blocks located
perpendicular to the z-axis. Oxygen atoms and mobile Na + ions are a located
between the blocks. Occupancy coefficients for Na + are function of temperature.
Electrochemical and electro physical characteristics can be varied upon partial
replacement of Na + ions by Li + , K +, Rb + , Ag +, Ti + ions. Ionic conductivity in
crystals of p-alumina at room temperature is 10- 1 Ohm -1 cm -1.
Three-dimensional superionic conductors are widely represented by a family
with crystal-chemical frameworks M 2[X0 4]3 of the rhombohedral and
langbeynite types. The three-dimensional frameworks of these structures are
built of M-octahedra and X-tetrahedra. In such frameworks the conductivity
channels exist in several noncoplanar directions. Various Li +, Na +, K + ions
located in such channels ensure high values of ionic conductivity.
As for ionic conductivities, ionic conductors cover a wide range of the values,
from 10- 14 _10- 12 Ohm -1 cm -1, typical of weak ionic conductors like NaCI
at room temperatures, to the so-called superionic crystals Ag4Rbls and Na 2 0
nAl 2 0 3 (p-alumina).
The wide range of ionic conductivities and current carriers in these crystals,
as well as remarkable differences in their physical and electrochemical properties
extend the limits of the area of their practical application. Solids possessing ionic
conductivity are used as current sources and capacitors, time-delay relays,
various sensors, thermocouple sensors, strain gauges, electrochemical energy or
information con vergers, etc.
References
Bykov AB, Chirkin AP, Demyanets LN et al (1990) "Superionic conductors Li 3 M 2 (P0 4 h,
(M = Fe, Sc, Cr): synthesis, structure and electrophysical properties. Sol State Ion 38: 31-52
Chebotin VN, Perphiljev MV (1978) Electrochemistry of solid electrolytes. NAUKA (RUSS)
Moscow
Collongues R, Khan A, Michel D (1979) Superionic conducting oxides. Annii Rev Mater Sci 9:
123-150
Goodenough IB, Hong HY-P, Kafalas JA (1976) Fast Na + -ion transport in skeleton
structures. Mat Res Bull, vol 11, pp 203-220
Hagenmuller P, Gool van W (eds) (1978) Solid electrolytes, Academic Press, New York
Schulz H (1980) Crystal structure and ionic conductivity. Rev Chern Miner 17: 229-242
Subbarao EC (ed) (1980) Solid electrolytes and their applications, Plenum Press, New York
402

G.A. GORBATOV
All minerals, except native metals, are classified according to electrical properties as semiconductors (specific conductance u = 10- 7 _10 6 cm/m; the band gap
0< Eg < 4.5 eV for pyrite, galenite.) or dielectrics (u < 10- 8 cm/m, Eg > 4.5 eV
for quartz, feldspar).
In semiconductors directed mobility appears in two charge carriers; electrons, in a normally unfilled conduction band, and holes in a normally filled
valence band, under the action of external electric and magnetic fields and
temperature gradients. The concept of a hole possessing a positive charge and
positive mass has been introduced to avoid the difficulties in describing this
mobility. The sources of charge carriers are the deviations from the stoichiometric compositions, the electroactive impurities of substitutional and interstitial types (the impurities giving off the electrons into the conduction band are
known as donors, and the impurities taking up the electrons from the valence
band are referred to as acceptors) as well as the transfer of electrons through the
energy gap as a result of thermal excitation. If the latter is predominant, with
the densities of electrons and holes being equal, the conductance is called the
intrinsic conductance. Since the transfer of electrons and holes is proportional to
the acting force, the quantitative analysis of this transfer allows the experimental
determination of semiconducting characteristics of minerals, which are closely
connected with the band structure, chemical composition, and crystal structure.
The most widely used characteristics are the forbidden band width Eg , the
ionization energy of impurities E j , the chemical potential J.l*, the effective mass
m:,p, the concentration of n, p electrons and holes, the mobilities Un,p' the
scattering mechanisms of charge carriers, and the type of conductance. To
determine these characteristics the following values are measured: the specific
conductance u, the Hall effect RH , the thermoelectromotive force coefficient oc,
and the temperature dependences of the above values. Optical and other
methods to determine Eg , E j , and m:,p are also applied.
The semiconductor-specific conductance (J is usually measured by the DC
four-probe method. The value of specific conductance is expressed by the
relations (J = enU n, and (J = epU p for unipolar conductance; (J = en Un + epU p
for mixed conductance, where e is the electron charge, mobility U cm 2 /(V.s)
is the average velocity of charge carriers in a field of 1 B/cm. There is little
information to be obtained from measurements of (J at room temperature. Much
more information is provided by combined measurement of the Hall effect and
conduction, the analysis of the temperature dependence of conduction, the Hall
effect, the thermo-EMF coefficient; all of them give enough data to determine
the relevant characteristics of semiconductors.
The measurement of the Hall effect involves the passage of electric current Ix
through a sample in the form of a rectangular plate, the application of a normal
403
magnetic field Bz , and the measurement of the potential gradient Ey in the third
perpendicular direction. When the charge carriers are electrons, RH = - 1/2n;
in the case of holes, RH = l/ep. Simultaneous measurement of specific conductance allows the Hall mobility of charge carriers n = RH. (J' to be determined.
The peculiarities of natural minerals are responsible for difficulties in
measuring (J' (T), R H, RH+ (J', RH(T). Quite often the smallness of mineral grains
and their inhomogeneity, which may be accompanied by alternating charge
carriers, make it difficult (if not impossible) to prepare samples of the required
sizes and shape, i.e., plates and prisms with the minimal dimensions 1 x 2
x6mm.
The method of measuring the thermo-EMF coefficient is most widely used in
practice. The (X-probe method of measurement (two copper or tungsten thermoelectrodes are attached to the surface of a mineral sample) makes it possible to
study minerals of various sizes and shapes, such as samples of ore, manufactured
pellets, agglomerations of grains and crystals as well as powdered mineral grains
of 0.1 mm. There are several modifications of this method: (1) measurements of
(X using manual probes or those unattached to a microscope; (2) scanning the
metallographic specimen surface using an automated system; (3) measurement
of the temperature dependence of the integral thermo-EMF using a computerized, automated system; (4) "field" measurement of the sign and amplitude
of thermo-EMF without heating one of the probes (heating being substituted by
inelastic collision of the probe with the mineral surface). In the Zabaikal
Geological Institute (USSR), the specialized thermo-EMF meters (Znak-3,
ITRM-3, and others) are commercially manufactured as well as the KOD-1O
automated system supplied with PASCAL software for the evaluation of ore
deposits.
Pyrite FeS z, arsenopyrite FeAsS, chalcopyrite CuFeS z, galenite, PbS, molybdenite MoS z, and some other minerals belong to a well-conducting group of
semiconductors. Characteristically, within a certain temperature interval and
with certain "critical" concentrations of impurities, the electrical properties of
these semiconductors turn out to be similar to those of metals, although in a less
pronounced form. The transition from purely semiconducting properties to
degenerate ones can be observed quite often in the same mineral with changing
concentrations of donors and acceptors, temperature, and other parameters.
Pyrite is found in modifications ofn-, pn-, np-, and p-types, Eg '" 0.9 eY. The
mobility of the electrons is nearly by two orders greater than that of holes. Co,
Ni, Cu impurities, and S-vacancies represent donors, As, impurities and Fevacancies are acceptors. The dependence of pyrite semi-conducting properties
upon the relative temperature of mineral formation has been established
(Fig. 102).
Arsenopyrite is found in modifications of n-, pn-, np-, and p-types.
Eg '" 0.34 eV. The mobility of electrons and holes is low, Un,p'" 0.1-1 cm z
V - 1 S - 1. Arsenopyrite with a nearly stoichiometric composition is an intrinsic
semiconductor at room temperature. S (substituting As), Co, and Ni are donors,
As (substituting S) is an acceptor. The dependence of arsenopyrite semi-
404
II _10 18
1017 1016 1015
10 18
10 19
-TI
, )Ira
600
Fig. 102. Dependence of semiconducting properties of pyrite

on the relative temperature of
mineral formation. p Number
of charge carriers, cm- 3 ; IX
thermo-EMF coefficient in
MkVjdegree
400
200
0
- 200
- 400
- 600
20!l
3!l0
400
500
t:C
conducting properties upon the relative temperature of mineral formation has

been established.
Chalcopyrite is characterized by the n-type of conductance due to an excess
of metal atoms. Eg '" 0.6 eV. The mobility of electrons is less than that of holes,
which is very unusual. The samples of iron-rich ores have a much higher electric
conductivity than those of copper-rich ores.
Galenite refers largely to the n-type, although modifications of pn- and
p-types are also found, Eg '" 0.37 eV. The charge carriers have a small effective
mass, m:,p '" 0.11 mo' Bi, Sb, Cu (in interstitials), and S-vacancies are donors,
Ag, Cu (substitutional impurity), and Pb-vacancies are acceptors.
Molybdenite is found in modifications ofn-, pn-, np-, and p-types, Eg '" 1 eV.
(J < 10 3 cm/m. Molybdenite is a relatively poor conductor with a high anisotropy of electrical properties. The conduction within S-Mo-S atomic layers is
much greater than in the direction parallel to the c-axis. The reduced effective
mass is m;.L = 0.65 mo, m;1I = 0.46 mo' The mobility of charge carriers in the
basal plane is high, Un,p '" 100-200 cm 2 V-I S -1, the holes jump between the
layers with Up'" 0.1 cm 2 V-I S - 1. The nature of the donors and acceptors is
unknown.
For the above-mentioned and some other semiconducting minerals, the
regular variability of electrical properties has been established (both for mineral
samples taken from deposits of different genetic types and those taken from
different zones of the deposits). As a result, the measurements of the electrical
parameters of the commonest minerals, particularly pyrite and arsenopyrite, can
be used to evaluate the productive mineralization and development of mineral
deposits. For example, the change in thermoelectrical properties of pyrite can be
6.4.4 Dielectric Properties of Minerals and Rocks
405
considered as a function of gold-bearing ore in some of the veins of the Darasun

gold-ore regions (sulfide formation at medium depth). Here, pyrite with the p-n
type of conductance (more seldom with the p-type of conductance) is a major
concentrator of gold. Fine pieces of gold are concentrated at- the p-n transition
or in the regions ofp-crystals with a discontinuous change in thermo-EMF. The
upper limit of mineralization corresponds to the zone of p-type pyrite, the lower
one - to that of n-type pryite. The optimal productive mineralization region is
attended by pyrite with 0 < Dn < 75%. Dn denotes the fraction of thermoEMF changes attributed to n-type pyrite as compared to the total amount of
changes. This regularity is typical only of medium depth deposits.
It has been found that the semiconducting properties of pyrite, arsenopyrite,
galenite, ilmenite, columbite, tantalite, rutile, and some other minerals significantly affect their flotation, especially at low concentrations of a collector, while
the semiconducting properties of cassiterite and scheelite affect electric separation. Mineral properties change, depending on their genetic features and under
external action (such as heating, oxidation, grinding, X-ray and radioactive
irradiation). By taking these factors into account, it is possible to make
technological maps of deposits according to the conductance of minerals and to
choose optimal concentration regimes; by directly influencing the properties
of minerals, it is possible to improve the efficiency of collective and selective
flotation and electrical separation.
References
Ginsburg AI (ed) (1985) Methods of mineralogical research. A reference book. Nedra,
Moscow, pp 140-177 (in Russian)
Krasmikov VT (ed) (1981) Electrical properties of ore minerals in exploration of endogenic
deposits. A handbook. Zabaikal Research Institute, Nedra, Leningrad, 91 p (in Russian)
Shuey RT (1975) Semiconducting ore minerals. Elsevier, Amsterdam
6.4.4 Dielectric Properties of Minerals and Rocks:

B.
CERVELLE
and XIAO JIN-KAI
Microwave (radar) remote sensing, for example with the satellite Seasat, the US
shuttle instruments SIR-A and SIR-B, and with the European ERS-l and the
future Radarsat, has the great advantage of being an all-weather technique, with
a certain power of ground penetration. Radar images are function not only
of the technical parameters of the sensor, for example the wavelength - centimetric - or the polarization state of the incident beam, but also of the terrain
topography and of the dielectric constants c; of the ground materials, particularly
the minerals and the rocks.
406
Dielectric Constants of Rocks and Minerals
Some dielectric constants e (e' being the real part and elf the imaginary part)
measured for more than 100 pure minerals, using the resonant cavity perturbation method, are given in Table 31a. It shows that at the wavelength A = 3.2 em,
e' and elf of the minerals vary by two to four orders of magnitude. Sulfides and
oxides have the largest range of variation, the sulfides having larger ranges than
oxides containing the same cation. Dielectric constants are generally low for
silicates and for complex oxides, except a few phyllosilicates, Pb-bearing and
mafic minerals.
Therefore, radar imagery of the ground is controlled by the dielectric
constants of the rocks, i.e., mixtures of minerals. Measurements have shown that
e' and elf of magmatic rocks decrease following the series ultra basicbasic-intermediate-acidic. This correlation is consistent with the variation of
dielectric constants against the chemical compositions: e' and elf decrease with
increasing Si-, K- and Na-contents, and decreasing, Fe, Mg, Mn, Ti, and Ca
contents in the rocks. Dielectric constants of sedimentary and metamorphic
Table 31a. Dielectric constants of minerals

f= 9370 MHz
Mineral
Sulfides
Oxides
Hydrides
Silicates
Complex oxides
e'
e'
e"
6.00-450
4.50-173
4.39-12.3
4.30-25.4
4.90-26.8
4.44-600
4.17-150
5.37-18.0
3.58-24.8
3.84-44.0
0.020-900
0.020-4.04
0.020-0.110
0.020-0.901
0.020-0.368
Table 31b. Microwave dielectric constants of some rocks

Rock type
Ultrabasic-basic rock
Intermediate rock
Acidic rock
Alkaline rock
Shale and mudstone
Sandstone
Limestone
Gneiss
Skarn
Marble
Slate
e'
e"
Range
Average
Range
Average
3.76-7.99
3.58-7.46
3.45-5.97
3.96-5.08
3.90-6.92
3.94-7.01
6.02-8.53
4.30-5.89
5.68-8.62
5.22-8.15
4.34-5.92
5.65
5.27
4.64
4.46
5.38
5.22
6.91
5.50
7.18
6.52
5.39
0.024-0.534
0.020-0.387
0.020-0.322
0.020-0.141
0.058-0.452
0.020-0.328
0.020-0.148
0.020-0.185
0.023-0.488
0.020-0.163
0.026-0.286
0.142
0.109
0.050
0.103
0.253
0.109
0.032
0.073
0.117
0.041
0.111
407
rocks vary similarly to those of igneous rocks, but in a more complex way,
following the chemical composition, metamorphic conditions and sedimentary
environment. The dielectric constants of some rocks are listed in Table 31 b.
Factors Influencing the Dielectric Properties of Minerals

Among the parameters which influence the microwave dielectric properties of
the minerals, some are important for the purposes of geological remote sensing:
the frequency of the incident beam, the water content of the minerals and the
soils, the chemical composition and the density of the rock.
Effect afthe Frequency afthe Radar Beam. For a perfect dielectric mineral, the
dielectric constants can be expressed as a function ofthe frequency (Xiao lin-Kai
1990), but departure from the perfect dielectric is usually observed because of
impurities and defects in natural minerals and rocks. Dielectric dispersion
200
100
90
80
70
'",
60
50
40
-g
30
U;
20
'",
U;
c 10
0
9
8
7
6
u
-;:
tl
Q)
.
\
cca
tl
Q)
.8
Q)
.~~
+"-...
~ ___
20
~P--:- ~----~. 2
~~~:
.
...
-----
116
7
103 104 105 106 107 108 109 10 10

Frequency (Hz)
10
9
8
7
6
5L-~~--~~--~~--~~---
103 104 105 106 107 108 109 1010

Frequency (Hz)
Fig. l03A, B. Dispersion of the dielectric constant (e) of some minerals against frequency.
f(Hz). e': real part. A 1 augite; 2 olivine; 3 witherite; 4 albite; 5 sodalite; 6 amethyst; 7 white
quartz. B 8 montmorillonite; 9 kaolinite; 10 opal; 11 hornblende; 12 glauconite; 13 orthoclase;
14 microcline
408
20
18
Fig. 104. Dispersion of the dielectric constant (E) of some rocks

against frequency f (Hz). E' real part
BASALT 41
ANDESITE )( 2
SLATE 3
GRANITE + 4
16
C 14
til
iii
c
o
() 12
SHALE 85
')
\
Q)
Ci
QUARTZITE
6.
.....
~.
" ......
",':>..:. "t,.".e.......
........... e. . . .
....... .
\ \..
10
Ii
DOLOMITE. 7
"GD
\
<.>
.;:
t5Q)
LIMESTONE
........
.~
~"-'"
+,
..........
""""""
103
.... '::t:
".
-~-~--~...
+.................
-......:::.....
-~:::.."
..............
4L-~
...........
.. ~--- ...
.f="",_
--_
-...............
_..
__ -..;:
(;'""-...o-_ ... ...._

---- ---.. ,;5
... _ _~.-:-:..:.::::~
__
104
__L-__
105
~~L-~
106
107
__~__- L _
108
109
10 10
Frequency (Hz)
curves are given for some minerals in Fig. 103, and for rocks in Fig. 104.
Generally, hydrothermal minerals are characterized by strong dispersion curves,
and minerals with relatively stable crystallographic structure and chemical
composition display lower dispersion.
Effect of the Soil Moisture. Water is a dipolar liquid with a high dielectric
constant. At 23C and for ). = 3.2 cm, s' = 61.5 and s" = 31.4. Since s for
minerals and rocks is much lower, the dielectric properties of the ground can
vary to a great extent if water is present. Nevertheless, experiments have shown
that structural water has little effect compared with that of water adsorbed in the
porosity of the rock. Experiments indicate that for moistened minerals and
rocks, the relation between s' and volumic percentage of adsorbed water Sw can
be expressed as:
s'
= s~ p s~
Sw,
where p is the porosity of the material, s~ the dielectric constant (real part) of
the material under water-free conditions, and s~ the real part of the complex
dielectric constant of water. Likewise, s" increases exponentially with the
adsorbed water content.
Effect of Chemical Substitutions. The types of cations and anions, the ionic radii
and the ionic polarizability determine directly the polarization intensity, then
409
Table 32. Microwave dielectric constants of some homeomorphous minerals

Mineral
Molecular
formula
E'
En
Magnesite
Calcite
Smithsonite
Siderite
Otavite
Rhodochrosite
MgC0 3
CaC0 3
ZnC0 3
FeC0 3
CdC0 3
MnC0 3
6.65
7.90
10.40
9.97
0.030
0.030
0.030
0.043
n.d.
n.d.
13.80
0.050
Aragonite
Witherite
Cerussite
CaC0 3
BaC0 3
PbC0 3
8.31
8.95
21.1
0.036
0.040
0.030
Sylvite
Halite
Galena
KCI
NaCI
PbS
5.73
6.33
71.6
0.046
0.033
0.43
the dielectric constant of a mineral material. Experimental data show that 6' and
6" vary with the isomorphic substitution of cations. Table 32 gives the microwave dielectric constants of some isomorphous mineral species.
Effect of Density. According to Olhoeft (1981), a linear relation between 6' and
the density d of Hawaii basalts has been established: In 6' = 0.839 + 0.524d.
Microwave remote sensing images represent the brightness temperatures T B of

the objects outcropping at the surface, They are determined by the microwave
emissivity e and the temperature T of each object: T B = eT.
The microwave emissivities e(h,v) can be calculated from the reflectivities
R(h, v) = 1 - e(h,v) of a nonmagnetic homogeneous insulated smooth and flat
object, illuminated by a vertically (v) or horizontally (h) polarized centimetric
wave:
R(h) = Icose cose +
J6 - sin 2 e 12
J6 - sin 2 e
R(v) = 16cose 6cos e +
J6 - sin 2 e 12
J 6 - sin 2 e
where e is the incident angle. Figure 105 shows, for some geological objects, the
microwave emissivity e curves against the incident angle e. They have been
calculated from the experimental dielectric constants for perfect reflectors,
i.e., flat and smooth surfaces. Results obtained on rough surfaces would be
somewhat different. Nevertheless, the brightness temperatures can be estimated
by the dielectric properties of the objects, which allows interpretation of the radar
images and prediction of the capability of the microwave radiation in prospecting and discriminating between lithological facies. For example, the tectonic
410
e
1.0
0.5
0
Q)
1.0
Z'
.:;
iii
E'"
0.5
w
Q)
>
<IS
~
.~
~
5
30
60
900
30
gO 60 900
30 860
90
1.0
Incident Angle (0)
Fig. 105. Microwave emissivity (e) curves of some geological samples H and V horizontal and
vertical polarization; 0 incident angle; J basalt; 2 limestone; 3 granite-gneiss; 4 iron ore; 5
desert sand; 6 violet organic soil; 7 lateritic soil; 8 water surface; 9 asphalt surface
belts, fractured and highly impregnated with water, can be mapped by microwave remote sensing. Water prospecting is greatly facilitated by use of this
technology.
On the other hand, very dry grounds with a smooth surface (versus the
centimetric wavelength), for example a sandy desert, can be penetrated to a
certain extent by the microwave beam. This phenomenon allows the subsurface
mapping of arid regions up to a few meters, leading to many applications in
Earth Sciences. This ability to penetrate dry surface and vegetation layers makes
the radar imaging data particularly useful in structural geology. Linear features
such as faults, folds, and fractures can be detected remarkably well by microwave remote sensing.
411
Conclusion
Microwave remote sensing gives unique information for Earth Sciences. On the
one hand, visible and infrared imagery, using the reflected radiation of the sun,
provides information about the surface of the Earth. Geological imagery, in this
part of the electromagnetic range, is impossible when clouds, vegetation, snow,
or alteration cover mask the lithological features. On the other hand, radar
imagery, using a centimetric wavelength beam emitted from the satellite and
then completely independent of weather and illumination, allows probing a
few meters under the surface. It gives volumetric information, depending on the
dielectric constant and the 3D-heterogeneities of the near-surface layer.
Therefore, the registration of radar imagery with other types of remotely
sensed data, with different spectral and spatial resolution, is particularly profitable, for example with data acquired in the visible-infrared range (Spot 2 and 3,
Landsat 4 and 5, Cosmos 1870). The two technologies are not competing, but
complementary, especially for Earth Science purposes.
References
Blom R, Elachi C (1981) Spaceborne and airborne imaging radar observation of sand dunes.
J Geophys Res 86: 3061
Blom RG, Crippen RJ, Elachi C (1984) Detection of subsurface features in Seasat radar images
of Means Valley, Mojave Desert, California. Geology 12: 346-349
Carver KR, Elachi C, Ulaby FT (1985) Microwave remote sensing from space. Proc IEEE 73:
970-996
Cervelle B (1991) Application of mineralogical constraints to remote sensing. Eur J Mineral 3:
677-688
Cervelle B, Moelo Y (1990) Reflected light optics. In: Jambor JL, Vaughan DJ (eds) Advanced
microscopic studies of ore minerals. Mineralogical Assoc Canada, Ottawa, pp 87-108
Elachi C, Brown WE, Cimino JB et al. (1982) Shuttle imaging radar experiment. Science 218:
996-1003
Liu JY, Teng XY, Xiao J-K (1985) Application of the shuttle imaging radar image to land use
investigation. Kexue Tongbao 30: 1241-1246
McCauley J, S-.:haber GG, Breed CS et al. (1982) Subsurface valleys and geoarcheology of the
eastern Sahara revealed by Shuttle Radar. Science 218: 1004-1020
Olhoeft GR (1981) Electrical properties of rocks. In: Toiiloiikian YS (ed) Physical properties of
rocks and minerals. McGraw-Hili, New York, pp 257-330
Sabins FF (1983) Geologic interpretation of space shuttle radar images of Indonesia.
Am Assoc Petrol Geol Bull 67: 2076-2099
Teng XY, Shi CQ, Peng HX, Xiao J-K, Lai ZS, Yang BL (1984) Passive microwave radiometry
in the Gobi Desert region. Remote Sens Environ 15: 37-46
Wang JR (1980) The dielectric properties of soil-water mixtures at microwave frequencies.
Radiol Sci 15: 977-985
Xiao J-K (1985a) Microwave dielectric properties of minerals and rocks. In: ESA SP-247 (ed)
Proc 3rd Int Colloquium on Spectral Signatures of Objects in Remote Sensing, Les Arcs,
France, 16-20 Dec. 1985, pp 293-296
Xiao J-K (1985b) A study on microwave dielectric properties of solid bitumen. Geochem 4:
67-76
Xiao J-K (1990) Dielectric properties of minerals and their applications in microwave remote
sensing. Chin J Geochem 9: 169-177
412
6.S Lattice Dynamics, Vibrational Spectra, Thermodynamic

and Heat Properties of Minerals
P.F.
McMILLAN,
A.N.
LAZAREV,
and S.W.
KIEFFER
The crystal structure of a mineral is determined by its interatomic potential

energy function, which also determines the atomic motions and vibrational
frequency spectrum. The relation between the potential energy function, atomic
motions, and frequency spectrum is the subject of lattice dynamics. Lattice
dynamics also provides a link between the microscopic vibrational properties
and macroscopic elastic and thermodynamic parameters as discussed in the next
chapters.
The potential energy function Y(r) represents the potential energy as a
function of the relative positions of different atoms within the crystal. The first
derivatives of the potential energy with respect to the atomic positions, dY /dr,
are identically zero for a stable crystal at equilibrium. This represents one set of
stability criteria for the crystal lattice. The second derivatives d 2 y /dr 2 are
commonly termed the harmonic force constants, and are the dominant terms
determining the crystal lattice dynamics. Higher derivatives, ignored in harmonic treatments of the lattice vibrations, are denoted "anharmonic" terms, and
are responsible for the phenomenon of thermal expansion.
At the most fundamental level, the potential energy function is determined
by the various internuclear and electronic interactions. In principle, Y (r) can be
obtained from solution of the complete electronic wave equation, within the
Born-Oppenheimer approximation. Although recent advances in theoretical
methods and computational techniques have made this possible for many
molecules and solids, in practice, the lattice dynamics of complex minerals are
usually treated using a simple ionic model for the crystal potential, or an
empirical force constant model for its second derivatives.
In general, if the Cartesian atomic position coordinates are given by a matrix
X, and the matrix of second derivatives of the potential energy function with
respect to Cartesian atomic displacements U j and u j (d 2 Y/du j du j ) is 0, the
vibrational frequencies ware given by solution of the determinantal secular
equation, det 10 - Mw 2 I1 = O. In the secular equation, M is the matrix of
nuclear masses, and I is the identity matrix. If the system contains N atoms,
there are 3N solutions (eigenvalues Wf and corresponding eigenvectors QJ,
because each atom has 3 degrees of freedom. Six of these correspond to
translations and rotations of the entire crystal, and have W = O. The remaining
3N-6 solutions correspond to the vibrational normal modes of the crystal.
A typical crystal contains on the order of 10 23 atoms, and it is not useful to
attempt to describe each of the very large number of lattice vibrations independ-
413
ently. Instead, use is made of the translational symmetry of the crystal lattice.
Each primitive unit cell contains n atoms. The lattice vibrations take the form of
vibrational waves propagating through the crystal with the periodicity of the
underlying crystal lattice, and can be grouped into 3n branches. Within each
branch, the relative atomic displacements within each unit cell are similar, but
the phase of the displacements in adjacent unit cells varies to give a lattice
vibrational wave propagating through the crystal. This lattice wave is described
by the inverse of its wavelength, the wavevector q, in the direction of propagation. Within this model, each lattice vibrational mode Qi(W, q) is described by its
characteristic frequency wand wavevector q. Plots of the mode frequencies
against wavevector are known as the dispersion curves for the crystal lattice
vibrations. The minimum wavelength is fixed by the dimensions of the primitive
unit cell, and defines the boundaries of the first Brillouin zone in reciprocal
space. For very long wavelength modes, the magnitude of the wavevector q
tends to zero, which defines the center of the Brillouin zone.
The three solutions to the secular equation which correspond to translation
of the entire crystal involve all atoms in all unit cells being displaced in the t>ame
direction at the same time. This motion has no restoring force, so has zero
frequency. Shorter wavelength lattice modes of this type, with atoms in each unit
cell moving in the same direction, but adjacent unit cells moving out of phase, do
have finite frequencies. These displacements generate local density fluctuations
within the crystal, providing a mechanism for sound transport and the three
branches are known as acoustic branches. The remaining 3n-3 branches involve
relative atomic displacements of atoms within the unit cell which can generate
fluctuating electric dipole moment contributions. These modes can interact with
light, giving rise to infrared and Raman spectra, and these branches are referred
to as optical branches. The lattice modes are further classified as transverse or
longitudinal, depending on whether the atomic displacements within the unit
cell (and hence the direction of the dielectric polarization vector) are perpendicular or parallel to the propagation direction of the lattice vibrational wave.
The normal vibrational modes or lattice vibrations of the crystal have been
described above via solution of the classical equations of motion for the atomic
or ionic displacements within the harmonic approximation. These can also be
obtained from a quantum mechanical treatment, solving the vibrational Schrodinger equation HA> = Ev<p, in which <p represents the vibrational wave function. If the vibrational Hamiltonian Hv is written in terms of the normal mode
coordinates Q(w,q), the vibrational energy levels Ev are given by (Vi + 1/2)hwi'
where Vi is a vibrational quantum number (Vi = 0,1,2, ... ), and Wi is the
classical vibrational frequency obtained above. Excitation of a vibrational mode
occurs via absorption of a quantum of energy hWi to change the vibrational
quantum number by one unit. This quantum mechanical model leads to a useful
descriptive terminology, in which each unit of vibrational excitation is termed a
phonon. These phonons can be treated as particles carrying the equivalent of
momentum (although no actual mass transport is involved) through their
wavevector q. Absorption or emission of one quantum of vibrational energy (in
414
classical terminology, excitation of a fundamental vibrational mode) is described

as creation or annihilation of one phonon. Usually this occurs with no change in
wavevector, but because of the lattice translational symmetry, the magnitude of
q can change by one reciprocal lattice unit. Such Umklapp processes are
responsible for transport of heat through the crystal. Multiphonon events
involve simultaneous excitation or relaxation of two or more lattice vibrations,
with a total vibrational energy change hw = h(wl ( 2 ) (sum or difference
processes), and the total wavevector q is conserved (Aq = 0).
Crystal lattice vibrations are most commonly studied via infrared and
Raman spectroscopy. In an infrared experiment, infrared light is passed through
the sample or reflected off a crystal face, and absorption maxima or reflectance
minima mark the frequencies of transverse and longitudinal vibrational modes.
Because the wavelength of infrared light is so much larger than typical crystal
lattice dimensions, the lattice waves probed via infrared spectroscopy have very
long wavelength, so that infrared measurements give information on vibrational
modes close to the centre of the Brillouin zone with Iql = O. In Raman
(combination) spectroscopy, monochromatic light from a visible or near-IR
laser is passed through a sample. Most of the scattered radiation is unshifted in
frequency, but a small proportion of the scattered photons have their frequency
shifted by small amounts through inelastic interaction with the lattice vibrations, or phonons. The phonon wave vectors probed by Raman scattering are
small, on the order of 0.001-0.01 Iqmaxl. Because of these restrictions on the
maximum wave vector set by the wavelength of light in the visible or infrared
region, infrared and Raman spectroscopy can only give information on vibrational modes close to Iql. = 0, and dispersion relations of crystal lattice vibrations cannot be studied. One experimental technique which does permit lattice
vibrations to be studied over the entire range of q is inelastic neutron scattering
(INS) spectroscopy. In this technique, a beam of thermal neutrons is allowed to
interact with the sample. The neutrons exchange both energy and momentum
with the vibrational modes of the crystal, and neutron velocities can be chosen
so that the energy and momentum transfers cover the entire wand q range of
crystal lattice vibrations.
There are two major families of empirical methods for calculating crystal
lattice vibrations, which differ essentially in the coordinate systems used for the
calculation, and in the form of the model for the interatomic potential energy
function or force field. The first type of calculation is carried out within a
Cartesian coordinate system, and involves modeling the interatomic potential
using an ionic pair potential. The simplest models consider the ions to be rigid,
with long range Coulombic attractive and repulsive forces acting between them
as well as short range repulsive interactions, usually between the anions. More
sophisticated models (shell models) allow for some polarization of the ions
during the vibrational motion. Within these empirical models, partial charges
and repulsive parameters are initially set from chemical intuition, and refined
against experimentally determined properties of the static or dynamic lattice.
These models have been used with great success in interpolating and extrapol-
415
ating dispersion curves obtained from inelastic neutron scattering experiments,

and give a useful description of the form of the atomic vibrations for each mode
as a function of q. Vibrational calculations of molecular crystals are commonly
carried out in an internal coordinate system, in which the coordinates are
defined in terms of bond stretching and angle bending. The dynamical matrix is
formulated in terms of a set of internal valence force constants, which are usually
refined against experimental data. As for the empirical ionic models, the initial
values for these force constants are determined intuitively or are transferred
from the results of prior calculations on related molecular systems. Finally, some
types of empirical model combine these two approaches, and contain both long
range Coulombic terms and short range valence force constants.
Lattice dynamic calculations are usually carried out for one of a number of
reasons. Once a potential energy function or set of valence force constants has
been chosen, the vibrational calculation gives vibrational mode frequencies w as
a function of q, and the atomic displacement pattern associated with each of
these vibrations. The frequency calculations can be used for interpolation or
extrapolation of phonon dispersion curves, when these have been measured over
some region of q-space via inelastic neutron scattering. The calculations also
give vibrational frequencies for modes inactive in infrared or Raman spectra, at
the Brillouin zone center. Such frequency calculations can be highly reliable,
especially when the potential or force field model is flexible, and well constrained
by existing data. This type of calculation is extremely useful for obtaining the
total vibrational density of states [i.e., the vibrational spectrum summed over all
modes at all points in the Brillouin zone, g(w)], for use in calculation of heat
capacities and other thermodynamic properties. This application is described in
a later section.
The calculated atomic displacement patterns for the vibrational modes are
essential for using vibrational spectroscopy as a structural tool, because they
allow a relationship to be made between peaks measured in the experimental
vibrational spectrum and structural features of the mineral. Unfortunately, the
calculated eigenvectors can be highly dependent on the assumed crystal potential function or force field, and a good fit between calculated and experimentally
measured mode frequencies is no guarantee that the calculated mode displacements are correct. This is because the vibrational problem is highly underdetermined. In general, for a system containing N atoms, there are 3N-6
vibrational degrees offreedom and 1/2(3N-6)(3N-5) independent harmonic force
constant terms. This number can usually be reduced by symmetry, and many of
the second derivative terms are often negligible. However, it is almost always
true that the number of terms needed to fully describe the force field is much
larger than the number of vibrational mode frequencies. The consequences of
this underdetermination are that the experimental vibrational mode frequencies
do not provide sufficient constraints to fully determine the major parameters of
the force field, and for this reason, the calculated mode eigenvectors in an
empirical vibrational calculation may not correspond to the true atomic
displacements.
416
In an effort to remove the ambiguity associated with empirical vibrational

calculations, several ab initio approaches have recently been applied to calculation of the lattice dynamics of minerals, using a variety of methods. One type
of calculation involves deriving sets of valence force constants from ab initio
calculations on molecules or molecular fragments, designed to model portions of
mineral structures. These force constants are then transferred into the solid, and
a lattice dynamic calculation is carried out. This approach has been applied to
diamond, using qCH 3)4 as a structural model, and vibrational and elastic
properties were calculated, in good agreement with experiment. Calculations of
this type have also been carried out for the infrared and Raman active vibrations
of quartz. The calculated zone center frequencies, 28SiroSi and 160j180 isotope
shifts, and mode Gruneisen parameters were in reasonable agreement with
experiment. In these studies, the ab initio calculations on the molecular fragments resulted in systematic 5-10% errors due to finite basis set size and neglect
of electron correlation. These can be scaled by comparison with vibrational data
for gas phase molecules, before transferring the force constants into the solid.
This can pose a problem which data for appropriate molecular species are not
available. A more serious problem is that this technique does not account for
long range electrostatic forces in the crystal, which affect the frequencies of
longitudinal lattice vibrations. Some attempts have been made to incorporate
these into valence force field calculations, by adding a Coulombic part to the
crystal potential, using partial charges derived from the ab initio calculation.
With this type of approach, it can be difficult to avoid introducing redundancies
into the potential energy function. One major drawback to the ab initio-derived
valence force field approach to calculation of vibrational properties of minerals
will probably remain the problem of including long range electrostatic terms in
the crystal potential. A second problem is the design of suitable molecular
clusters to adequately model the structural units of the crystal. However, a
major advantage of the local force field approach is that it is easily applicable to
complex mineral structures with many atoms in the unit cell. Because longrange Coulombic terms do not contribute to the frequencies of transverse optic
vibrations - which are observed in Raman and infrared absorption - the local
force constant models provide a useful method of calculating atomic displacements for use in interpretation of Raman and infrared absorption spectra.
Several ab initio methods have been developed which allow direct calculation of the crystal lattice dynamics, in which long range electrostatic contributions to the crystal potential are evaluated implicitly. In the modified electron
gas (MEG) theory, the crystal potential is written as a sum of contributions from
the Coulombic interaction of closed shell ions (although calculations with open
shell systems are possible), a short range contribution from overlapping regions
of the ionic electron density, and the intrinsic self-energies of the ions. The short
range interaction energies are calculated as functionals of the ionic electron
densities, usually obtained in a prior step from ab initio calculations of the free
or stabilized ions, and contain terms for the electronic kinetic, exchange, and
correlation energies. Once the crystal potential is obtained in terms of these
417
contributions, the full lattice dynamics are easily calculated via diagonalization
of the dynamical matrix. Recent improvements on the original MEG model
include the potential-induced breathing (PIB) model, in which the anion charge
density is allowed to relax during vibrational displacements, and the variationally stabilized MEG (VSMEG), in which the crystal free energy is minimized
during vibrational (or static) distortions. These methods have been applied with
considerable success not only to the vibrational properties, but also in calculating elastic and thermodynamic properties, of a range of important minerals,
especially MgO and related oxides and halides, rutile, corundum, and MgSi0 3
and CaSi0 3 perovskites. As might be expected, this approach works best for
more "ionic" structures with high symmetry. In general, calculated zone center
vibrational mode frequencies are in excellent agreement with available experimental data, although LO mode frequencies are overestimated, due to the
assumption of spherical charge densities. Calculations on more "covalent"
minerals such as quartz have been less successful, and have required the
inclusion of additional, empirical, parameters to account for nonspherical
polarization of the electron density.
Very recently, more intrinsically ab initio approaches have been applied to
the static and dynamic lattice properties of minerals and related complex
crystals, in which an approximate electronic wave equation for the crystal is
solved directly, providing a potential energy function for obtaining the classical
vibrational modes of the crystal. Several approaches have been used. In tightbinding methods, the total electronic wavefunction is modeled as a linear
combination of overlapping atomic orbital wavefunctions. These methods are
most applicable to insulators, but fail badly for metallic solids. In plane wave
methods, the wavefunction for the crystal is expanded in a series of plane waves,
which works well for metallic systems. Augmented plane wave techniques, which
combine a plane wave expansion with more rapidly varying basis functions in
the core region, were developed to account for the rapid oscillations in charge
density in the vicinity of the cores. Pseudopotential methods provide a convenient way of modeling the local potential in the core region seen by valence
electrons, without including a large number of basis set terms to model the core.
Once the model wave function has been constructed, the electronic energy
(including exchange and correlation energies, depending on the method of
solution) can be obtained and combined with core-core repulsion terms to
provide an ab initio crystal potential V. At this point, the atoms can be moved
along coordinates corresponding to vibrational mode displacements Qj, and the
total energy re-evaluated at each step. Differentiation of the function V(Qj)
determines the stability of the crystal against that type of atomic displacement,
which can be extremely useful in studying displacive phase transitions associated with soft mode behavior, and allows calculation of the vibrational mode
frequency from the ab initio potential energy surface. This type of dynamical
calculation is known as a "frozen phonon" approach, and has been applied
successfully to graphite and diamond, and very recently to stishovite and
lanthanum copper oxide superconductors. In Hartree-Fock-Slater self-con-
418
sistent field theory applied to molecular systems, methods have been developed
to directly obtain the first, second, and higher derivatives of the total energy with
respect to atomic displacement coordinates. These calculations are particularly
useful, in that they provide information on all of the vibrational modes of the
molecule, in a single calculation step. Hartree-Fock calculations are now being
carried out for minerals, including forsterite, corundum, spinel, quartz, and clay
minerals, and derivative Hartree-Fock methods are being developed and coded
for these complex crystalline systems. These ab initio techniques will revolutionize the study of the vibrational, thermodynamic, and elastic properties of
minerals, especially when used in a complementary fashion with experimental
data.
References
Bilz H, Kress W (1979) Phonon dispersion relations in insulators. Springer, Berlin Heidelberg
New York, 241 pp
Born M, Huang K (1954) Dynamical theory of crystal lattices. Oxford, University Press,
Oxford, 420 pp
Burnham CW (1990) The ionic model: perceptions and realities in mineralogy. Am Mineral 75:
443-463
Chelikowsky JR, Chou MY (1987) Pseudopotential approaches to the structural energies of
crystalline solids and solid surfaces. Phys Chern Mineral 14: 308-314
Cohen RE, Boyer LL, Mehl MJ (1987) Theoretical studies of charge relaxation effects on the
statics and dynamics of oxides. Phys Chern Mineral 14: 294-302
Cohen RE, Pickett WE, Krakauer H (1989) First-principles phonon calculations for
La 2 Cu0 4 . Phys Rev Lett 62: 831-834
Ghose S, Hastings JM, Corliss LM, Rao KR, Chaplot SL, Choudhury N (1987) Study of
phonon dispersion relations in forsterite, Mg 2 Si0 4 by inelastic neutron scattering. Sol State
Comm 63: 1045-1050
Guth JR, Hess AC, McMillan PF, Petuskey WT (1990) A valence force field for diamond from
ab initio molecular orbital calculations. J Phys C: Sol State Phys 2: 8007-8014
Hemley RJ, Jackson MD, Gordon RG (1987) Theoretical study of structure, lattice dynamics,
and equation of state of perovskite-type MgSi0 3 and CaTi0 3 . Phys Chern Mineral 14: 2-12
Hemley RJ, Chen RE, Yeganeh-Haeri A, Mao HK, Weidner DJ, Ito E (1989) Raman
spectroscopy and lattice dynamics of MgSi0 3 , perovskite at high pressure. In: Navrotsky A,
Weidner DJ (eds) Perovskite: a structure of great interest to geophysics and material science.
Am Geophys Union, Washington DC, pp 35-53
Jackson MD, Gordon RG (1988) MEG investigation of low pressure silica-shell model for
polarization. Phys Chern Mineral 16: 212-220
Lazarev AN (1988) Vibrational spectra, lattice dynamics and chemical constitution of oxides.
Lazarev AN, Shchegolev BF, Smirnov MB, Dolin SP (1988) Quantum chemistry of molecular
systems and the crystal chemistry of silicates (in Russian). Nauka, Leningrad
Louie SG (1985) Pseudopotential and total energy calculations: applications to crystal
stability, vibrational properties, phase transformations, and surface structures. In: De Vreese
JT, Camp P van (eds) Electronic structure, dynamics, and quantum structural properties of
condensed matter. New York, Plenum, pp 350-396
McMillan PF (1985) Vibrational spectroscopy in the mineral sciences. In: Kieffer SW,
Navrotsky A (eds) Microscopic to macroscopic: atomic environments to mineral theromodynamics, reviews in mineralogy, vol 14. Mineral Soc Am, pp 9-63
Mineral 17: 97-107
6.5.2 Lattice Dynamics and Thermodynamic Properties of Minerals
419
Mehl MJ, Hemley RJ, Boyer LL (1986) Potential-induced breathing model for the elastic
moduli and high-pressure behavior of the cubic alkaline-earth oxides. Phys Rev B 33:
8685-8696
Pisani C, Dovesi R, Roetti C (1988) Hartree-Fock ab initio treatment of crystalline systems.

Lecture Notes in Chemistry 48. Springer, Berlin Heidelberg New York, 193 pp
Price DL (1988) Lattice dynamics and inelastic neutron scattering from forsterite: phonon
dispersion relation, density of states and specific heat. Phys Chern Mineral 16: 83-97
Price GD, Parker SC, Leslie M (1987) The lattice dynamics and thermodynamics of Mg 2 Si0 4
polymorphs. Phys Chern Mineral 15: 181-190
Reissland JA (1973) The physics of phonons. John Wiley, New York, 319 pp
Wolf GH, Bukowinski MST (1987) Theoretical study of the structural properties and
equations of state of MgSi0 3 and CaSi0 3 perovskites: implications for lower mantle
composition. In: Manghnani MH, Syono Y (eds) High pressure research in mineral physics.
Terra Scientific Pub/Am Geophys Union, pp 313-331
Wolf GH, Bukowinski MST (1988) Variational stabilization of the ionic charge densities in the
electron-gas theory of crystals: applications to MgO and CaO. Phys Chern Mineral 15:
209-220
6.5.2 Lattice Dynamics and Thermodynamic Properties

of Minerals
V.M.
AGOSHKOV,
S.W.
KIEFFER,
and P.F. McMILLAN
The physical macroscopic properties of minerals are determined by the lattice

dynamics of the microscopic atomic state. The elastic and shear moduli, free
energies, specific heat, entropy, thermal coefficients of linear and volumetric
expansion, and other thermodynamic properties represent the result of averages
over the interatomic forces or the atomic vibrations that depend on them. The
range of frequencies and their distribution are the spectrum of oscillations, that
is, the phonon spectrum g(w). The phonon spectrum is determined by the interatomic potential energy function.
If the displacements of the atoms from their equilibrium positions are
assumed to be small, the potential energy V(r) can be expanded as a power series
in the atomic displacements. In the so-called harmonic approximation, the
power series includes only two-body interactions between pairs of atoms or ions,
and the interaction potentials are parabolic. Real interatomic potentials are not
parabolic, and the thermodynamic properties of minerals show anharmonic
behavior. If lattice-vibrational behavior were strictly harmonic, there would be
no thermal expansion, the heat capacity would become constant (equal to the
Dulong-Petit limit) at high temperature, and the specific heats at constant
pressure (C p ) and constant volume (C y ) would be equal. The force constants
(and, hence, the elastic moduli) would be independent of temperature and
pressure, and line-widths of infrared absorption peaks, and of Raman, Brillouin,
and inelastic neutron scattering peaks would have zero width. The thermal
conductivity of a perfectly harmonic crystal would be zero because there are no
collisions between phonons and their mean free paths are infinite.
420
More realistic model potentials for anharmonic crystals include higher order
terms in the power series expansion for V(r) and are used to model thermal
expansion and thermal conductivity. In the so-called quasiharmonic approximation, the temperature dependence of the force constants and phonon vibrational frequencies is assumed to be due only to the effects of thermal expansion.
That is, the normal vibrations are still assumed to be uncoupled, but the force
constants and, therefore, the vibrational frequencies of the crystal change with
pressure and temperature because the equilibrium positions and distances
change.
More complicated models attempt to account fully for anharmonic effects by
including many-body interactions as well as effects thermal of expansion and the
coupled effects of phonon-phonon interactions.
The thermodynamic properties are given by integrals of energy functions
over the vibrational spectrum. For example, the heat capacity, C v , is given by
Cy
Jg(w) E (hw/kT) dw.
In this equation, E represents the Einstein heat capacity function, h is the Planck
constant divided by 2n, k is the Boltzman constant, and T is absolute temperature.
Data from elastic, infrared, Raman, and inelastic neutron scattering experiments can now be used, in conjunction with theoretical models of lattice
vibrations, to construct approximations to the total vibrational spectra, g(w).
Information from individual experiments is typically limited, e.g., optical spectroscopic methods give information primarily about the behavior of the modes
at the center of the Brillouin zone, whereas elastic measurements give information only about long wave-length behavior. However, enough information can
be extracted from lattice dynamics and crystal structure systematics to allow
useful thermodynamic calculations to be made.
The practical and applied significance of lattice dynamics investigations is in
the establishment of quantitative ties between the microscopic and macroscopic
properties of crystals. If these ties are well established, then properties can be
predicted from statistical thermodynamics. This is particularly valuable in the
case of metastable minerals that are only formed at high pressures and temperatures since the amounts of sample that would be required for calorimetry or
ultrasonic experiments may not be available. Calculation of the thermodynamic
properties by statistical mechanics methods is also of use when reaction kinetics
inhibit laboratory measurements, viz., isotopic fractionation at low temperatures.
Vibrational Spectra and Thermodynamics
Until a decade ago, it was common to use the Debye approximation based
on acoustic properties (elastic constants) to calculate mineral thermodynamic
421
properties. However, this approximation is not good for many minerals of

common geologic interest. The Debye theory assumes that minerals are monatomic and isotropic, and that acoustic waves in the minerals are dispersionless
(that is, the wave velocity depends linearly on the wave length). Furthermore, the
Debye theory specifies that the thermal properties are given by a single
parameter - the Debye temperature (or, equivalently, frequency) - that is determined by the elastic constants of the crystal.
Most minerals are not this simple. The Debye model fails over nearly the
entire temperature range from 0 to 1000 K for most minerals. Although it
remains useful for many high-temperature approximations (T > 1000 K) and for
relatively simple oxides, the Debye model does not provide a sensitive enough
estimate of the thermodynamic functions that phase equilibria or isotopic
fractionation can be calculated for most minerals. Furthermore, even when the
mineral thermodynamic properties can be described by a Debye-like spectrum,
the Debye temperature that best characterizes the behavior is often substantially
different than the elastic Debye temperature; this "effective Debye temperature"
is called the thermal or calorimetric Debye temperature.
The deviation of thermodynamic behavior from Debye-like behavior increases as the minerals become structurally more complicated and atomically
more heterogeneous. The deviations are largest for the framework silicates, and
systematically tend toward Debye-like behavior in the sequence through chain
and orthosilicates to oxides. Even though a more accurate model than the
Debye model is required for complex minerals, extreme detail is generally not
required in the mode representation because the thermodynamic properties of
minerals represent averages over the entire vibrational spectrum.
Of the phenomena that cause deviation from Debye-like behavior, the
existence, nature, and distribution of optic modes is the most significant.
Methods of accounting for optic modes range from a relatively simple modification of a Debye spectrum by addition of optic modes as Einstein oscillators to
complex models of g(w) from spectral data and theoretical calculations.
The Debye model, a Debye model modified by a single Einstein oscillator,
and more complex schematic vibrational spectrum are shown in Figs. 106 and
107. The simplest modification of a Debye model incorporates any enumerable
vibrations into one or more Einstein oscillators. These typically would represent
molecular-like internal vibrational modes of clusters, such as Si0 4 , C0 3 , or
O-H. Typical internal vibrations that can be identified and enumerated in
silicates are the (Si,AI)-O antisymmetric stretching modes. The acoustic and
low-frequency part ofthe optic spectrum can be represented together by either a
dispersionless Debye approximation, or one that includes dispersion (Fig. 106).
In this approximation, a reduced characteristic temperature, e R , is used, and
anisotropy is ignored, that is, the three acoustic modes are represented by a
single mode with an average wave velocity, and the low-frequency optic modes
are assumed to represent an extrapolation of the acoustic modes. e R is
determined from the elastic Debye temperature eD' the total number of lattice
422
: ,f
~/
.
;
1
1
/::
1
1
1
1.
v.::
/1 .. :
/: / f :
..... ....:..r:.- .... ,

/
1
....:
..
....~
....
Fig. 106. Schematic diagram

of lattice vibrational spectrum
according to a Debye model for
an isotropic mineral (dashedsolid curve extending to frequency WD and temperature
eD. The dotted curve shows a
Debye spectrum for an isotropic material for which there are
three branches - two transverse
and one longitudinal. The
dashed curve shows a truncated
Debye spectrum having a reduced Debye temperature QR
and reduced Debye frequency
e R, and two Einstein oscillators, WEI and W E2
Einstein
oscillators
optic
continua
Fig. 107. Schematic diagram of

a spectrum that allows for separate representation of three
acoustic modes, three different
types of optic modes grouped
into optic continuua, and four
Einstein oscillators
co
vibrational modes (n), and the number (m) of high frequency Einstein modes that
have been represented separately:
BR = BD*(l - m/n)1/3.
Over the temperature range from 200 to 1500 K, this kind of model can give
values of C p and S that agree with measured values within 2.5 to 3%.
For the more complex silicates, this simple modification of the Debye
spectrum may not be adequate to predict thermodynamic properties for which
a high degree of accuracy is required (e.g., phase equilibria for which the free
energy differences are small; low-temperature isotopic fractionation). A generalized spectrum that has been applied to a number of minerals over the past
decade is shown in Fig. 107. In this representation (referred to below as the
Kieffer model), acoustic and optic modes are properly enumerated according to
mineral structure (viz., considerations given in the previous chapter). Anisotropy
and dispersion in acoustic modes are modeled semi quantitatively by incorporation of a spectral form based on that appropriate to a diatomic solid. Optic
423
modes can be conveniently modeled in two ways: (a) as "optic continuua":

blocks of modes in frequency space which represent modes with high dispersion,
typically in the low- to mid-frequency range, and (b) as Einstein oscillators:
isolated modes with little dispersion. Modes that are grouped into optic
continuua are typically Si-O deformations, cation-O deformations, (Si,Al)-O
bending, polyhedral deformations, or (Si,Al)-)-Si symmetric stretching modes.
The Einstein oscillators usually correspond to internal vibrations of molecular
units within the crystal structure, a typical example being the (Si,AI)-O antisymmetric stretching modes.
The parameters required for models that approximate the spectral density of
states are obtained from crystallographic, elastic, and spectroscopic data. The
models can be independent of any calorimetric data; alternatively, calorimetric
data - if available - can be used to constrain the model density of state. A model
that used the spectral form shown in Fig. 107 was tested against accurate
calorimetric data for 31 minerals of relatively complex structure: halite, periclase, brucite, corundum, spinel, a-quartz, a-cristobalite, coesite, silica glass,
stishovite, rutile, albite, microcline, anorthite, talc, muscovite, tremolite, enstatite, jadeite, diopside, forsterite, zircon, pyrope, grossular, spessartine, almandine, andradite, kyanite, andalusite, sillimanite, and calcite. For these minerals,
there were good results over the range 298-1000 K. Entropy at 298 K matched
calorimetrically determined values to 1.5%. Applications (summarized below) to other minerals have developed over the past decade with similar results.
Differences between calculated and measured properties (the specific heat,
C p , and the entropy, S;n are most marked below 100 K (because the thermodynamic properties are sensitive to the shape of the phonon spectrum at lower
temperatures), and above 1000 K (because anharmonic effects are important).
Applications
MgO Periclase. Periclase is of major interest to Earth scientists because it is

a likely major constituent within the Earth's mantle. The specific dynamics of
Mg-O bonds are also of importance because of their ubiquitous presence in
crystal and mantle minerals.
Periclase has the crystal symmetry Fm3m with two atoms per unit cell. There
are therefore three acoustic and three optic branches in the phonon dispersion
curves. The optic modes are triply degenerate (split by TO-LO splitting) at the
zone center. The infrared absorption spectrum shows one peak, and there are no
first-order Raman active modes. The phonon spectrum g(w) is well known from
inelastic neutron scattering experiments, and the positions of critical points
(zone center and zone edge frequencies along special symmetry directions) have
been fixed accurately by second order Raman spectroscopy.
The harmonic component of the periclase thermodynamic properties may
be the most Debye-like of all minerals of general interest to Earth scientists,
particularly at the high pressures and temperatures of interest in the Earth's
424
mantle. However, even though the thermodynamic properties through

the temperature range 298-1000 K are well approximated by a Debye model,
the Debye temperature that gives the best calorimetric results (762 K) is not
the elastic Debye temperature derived from first principles (942 K). More accurate models using spectra derived from the inelastic neutron scattering data
have permitted detailed examination of the MgO heat capacity, and the harmonic and anharmonic effects at I atm are quite well understood.
Critical point frequencies can also be examined by measuring the vibronic
spectrum of MgO doped with low concentrations ( < 0.2%) of a fluorescing
transition metal ion (e.g., Cr 3 +). This technique has been particularly useful
for examination of spectra while a mineral is confined at high pressures in a
diamond cell. From the measurement of the bands (6 in the case of periclase),
mode Gruneisen parameters and thermal expansion can be calculated.
Measurement of the dependence of mode frequency on pressure, in turn,
allows an approximation to the vibrational spectrum g(w) as a function of
pressure to be made. C v can then be calculated as a function of pressure, and
from C v and other macroscopic parameters, the dependence of thermal expansion with pressure (or, equivalently, volume) can be estimated. For periclase,
the conclusion was reached that the thermal expansion of MgO at the bottom of
the lower mantle could be an order of magnitude less than at surface pressure.
SiO z , GeO z , and TiO z Polymorphs. Knowledge of the phase boundaries in the
Si0 2 system is important because of the ubiquitous occurrence of the minerals
on the surface of the Earth (quartz, glass, cristobalite, tridymite), and in the
interior (coesite, stishovite). Determination of the phase boundaries, particularly
of the high-pressure polymorphs, has proved difficult because ofthe sluggishness
of the reactions under laboratory conditions. There has also been some question
about the meaning of the thermochemical data on coesite and stishovite because
the data were obtained on natural samples from Meteor Crater, and the purity
and grain size in the samples were not ideal for calorimetric samples. Theoretical
calculation of the heat capacities from spectra has addressed the problems in
the calorimetric data and calculation of the free energies has contributed to
narrowing the range of plausible the phase boundaries.
Considerable work has been devoted to obtaining and interpreting vibrational spectra of different polymorphic modifications of silica (SiO z), particularly the high-pressure polymorphs coesite (monoclinic) and stishovite
(tetragonal). GeO z provides a good structural analog for Si0 2 because it has
isomorphous forms with quartz and stishovite, and the rutile-structured GeO z
and Ti0 2 polymorphs are stable at room pressure, and can be more easily
studied than stishovite. Although infrared and Raman data are available for all
of these oxides, inelastic neutron scattering data are available only for a-quartz
and rutile.
The heat capacity at 1 atm pressure has been calculated for quartz with a
number of different models, each accounting for the optic modes in slightly
different ways. It is possible to enumerate the zone-center mode frequencies
425
for all optic modes, and the various models that have been presented in the
literature differ only in the way in which the dispersion in the modes is treated to
obtain an assumed g(ro). Most models give heat capacities that are within 1-2%
of calorimetric values at temperatures above 298 K.
Measurements of the infrared and/or Raman spectra as a function of
pressure have allowed a number of new kinds of thermodynamic calculations
based on vibrational spectroscopy to be introduced. Measurement of the shift of
spectral lines as function of pressure allows calculation of the mode Gruneisen
parameters. Variations in the spectra with temperature allow modeling of
anharmonic contributions to the thermodynamic functions. Models that take
account of the anharmonicity (both the pure-volume contribution that arises
from the change in bond length with pressure and temperature and the volumeindependent contribution arising from the higher-order anharmonic terms in
the potential energy function) reproduce the calorimetric results for Cp very well.
Comparison of the thermodynamic properties obtained from high-pressure and
high-temperature spectroscopy with range of experimentally measured phase
boundaries for the coesite-stishovite transition suggests that the most current
"best guess" for the phase boundary is 8 0.3 Gpa at 300 K and that the
boundary has a slope of 2 x 10- 3 Gpa K - 1.
Measurement of the change of vibrational band frequency upon isotopic
substitution allows calculation of isotopic fractionation. Oxygen fractionation
has been calculated for at least a dozen minerals - including calcite - in this way
and the results agree with experimentally determined values to within a few
parts per million. Such calculations have not yet been carried out for silicon
fractionation, although 28Si/30Si vibrational data are now available.
In quartz, the 207 cm - 1 mode broadens and shifts rapidly to lower frequency with increasing temperature. This is known as soft mode behavior. The
atomic displacements of this mode mimic those of the 1Y.-f3 phase change, and
thermal excitation of the anharmonic mode is responsible for the displacive 1Y.-f3
phase transition in quartz. The mode at 517 cm - 1 in Ge0 2 shows a lesser, but
still appreciable, degree of anharmonicity. The vibrational spectra of stishovite,
tetragonal Ge0 2 , and Ti0 2 rutile all show interesting and significant mode
anharmonicity. Studies of the so-called soft-modes in these minerals, as well as
in cassiterite (Sn0 2, rutile structure) have led to increased understanding of the
mechanisms of phase transitions.
Large mode Gruneisen parameters represent a challenge in attempts to
relate mode Gruneisen parameters (Yi) to thermal Gruneisen parameters (Yth).
Mg2 Si04 Forsterite and its High-Pressure Spinel and Spinelloid Polymorphs. A
particularly well-examined problem has been that of the thermochemical properties and phase relations of forsterite [1Y.-Mg 2 Si0 4 ] and its high-pressure
polymorphic modifications [f3- and y-Mg 2Si0 4 ], from a combination of thermodynamic calculations, calorimetry, and high pressure synthesis and phase
equilibrium experiments. The results of these experimental and theoretical
studies have been combined with work on MgO and Si0 2 and MgSi0 3
426
polymorphs (described below) to constrain phase boundaries in the geophysically important system MgO-SiO z '
The vibrational properties of forsterite have been studied extensively via
infrared, Raman, and inelastic neutron scattering spectroscopy, for polycrystalline and single crystalline samples. In addition, several lattice dynamic calculations have been carried out for this phase, so that the phonon frequency
spectrum g(w) is well constrained for oc-Mg zSi0 4 Quasiharmonic calculations
of specific heat, and entropy from 0 to 1000 K are in highly satisfactory
agreement with calorimetric measurements. The thermal coefficient of volume
expansion (oc), as well as Cp , and S for oc-Mg zSi0 4 was calculated in the range
50-1200 K and for pressures up to 180 kbar. The derivative of thermal expansion with respect to volume was found to be 6.1 to values up to 10% volume
compression.
Infrared and Raman-active frequencies of forsterite have been measured
at pressures up to 180 kbar in diamond anvil cells. The pressure-dependence of
the phonon density of state g( w) can be modeled from these measurements, with
the additional knowledge of the equation of state of the mineral (specifically,
the isothermal bulk modulus, K T ), with the mode Gruneisen parameters defined as:
All the mode Gruneisen parameters were found to be positive and to lie
between 0.382 and 2.09. The averaged mode Gruneisen parameters give a mean
of 1.09, in reasonably good agreement with the macroscopic thermal Gruneisen
parameter Ylh of 1.17.
The phonon density of states functions for the high-pressure Mg zSi0 4
phases (p and y) are less well constrained from experimental data, although zone
center (infrared and Raman) data and elasticity measurements are available, and
rigid ion model lattice dynamic calculations have been carried out. The entropy
and heat capacity for these phases have been calculated using vibrational
models like that shown in Fig. 107, constrained by the experimental vibrational
spectra and elastic constants. The calculations support experimental results that
P-Mg zSi0 4 is intermediate in lattice entropy and energy to the oc and Y forms.
The calculated entropies were combined with calorimetric measurements of
enthalpies to examine the stability fields of the three polymorphs. The entropy
differences among the phases allows determination of the oc-P, p-y, and oc-y
phase changes. These were compared with AS,,_p and AS p _ y as determined from
the slopes of monovariant equilibria lines on the Mg zSi04 phase diagram:
AS = AV*(ap/aT).
The differences in slopes were about 30% and the differences in positions
of curves, about 2.5 Gpa (25 kbar) [at approximately 17 Gpa (170 kbar)], but
such differences are plausible when limits of experimental and model errors are
considered. Phase relations to 30 Gpa (300 kbar) and to melting temperatures
have been reproduced.
427
In a different treatment, the lattice dynamics of IX-, f3- and y-Mg 2 Si0 4 were
calculated using an empirical rigid ion treatment, which was used to construct
theoretical g( w) curves for the three polymorphs. The density-of-state spectrum
for forsterite was very close to those obtained by optic and inelastic neutron
methods. The elastic and shear moduli as well as Cp , S~, IX, and Ylh were
calculated. The calculations of the harmonic properties of specific heat and
entropy were in excellent agreement with corresponding calometric data, but the
anharmonic parameters IX and Ylh were approximately 30% lower than measured values. An attempt was carried out to compute the mono variant equilibria
for the 1X-f3-y phases of Mg 2 Si0 4 using this Born ion model. The P-T slopes for
the 1X-f3 and f3-y transitions corresponded to the experimental slopes; however,
the curve positions differed from the experimental phase equilibrium data:
- 15 kbar for 1X-f3 and + 40 kbar for the f3-y transitions. Thus, the error using
g(w) functions determined from empirical lattice dynamical calculations within
the ionic model is comparable to that using the Kieffer model.
XY0 3 Garnets, Iimenites, and Perovskites. This class of minerals, especially
the high pressure garnet, ilmenite, and pervoskite polymorphs of MgSi0 3 , are
extremely important for understanding the mineralogy and thermoelastic properties of the Earth's mantle. Partial infrared and Raman data and elastic
constants are available for these phases, and these have been used to construct
g(w) models like those in Fig. 107 for calculation of heat capacities and
entropies. As for the Mg 2 Si0 4 polymorphs, the calculated thermochemical
properties have been combined with data from calorimetric and high pressure
synthesis and phase equilibrium experiments to construct a self-consistent phase
equilibrium diagram for the MgSi0 3 system at high pressure and temperature.
These attempts to integrate spectral, thermodynamic, and phase-equilibria data
have been particularly useful in pointing out existing inconsistencies and
suggesting needed measurements, e.g., there is a need for thermal expansion data
on ilmenite at high temperature; there is an inconsistency between spinel
= perovskite + MgO and ilmenite = perovskite phase boundaries; thermodynamic data on garnet MgSi0 3 are lacking; and there is a need for in situ
measurements of volume in the IX-, f3-, y-Mg 2 Si0 4 system.
Similar thermochemical calculations using g( w) functions determined from
experimental spectroscopic data have been carried out for several germanate
systems, including CaGe0 3 , CdGe0 3 , and MnGe0 3 . Study of minerals with
cation substitution in this group has been particularly useful in vibrational/
thermodynamic modeling because spectra often change in a systematic way
upon cation substitution. For example, the pyroxenoid (or pyroxene, either
denoted by py) to garnet (g) phase relations have been examined for CaGe0 3 ,
CdGe0 3 , MnSi0 3 , and MgSi0 3 . Calculation of the entropies of the phases by
combining calorimetric, phase-equilibria, and lattice-vibrational modeling confirmed shallow positive slopes for the phase boundaries in P-T space. The
studies suggest that perovskite forming transitions [from either ilmenite (il) or g]
have negative P-T slopes (g = pv for CaGe0 3 ; il = pv for CdTi0 3 , CdGe0 3 ,
and MgSiOh.
428
Al2 Si0 5 Polymorphs. Calculation of the phase boundaries between the polymorphs of Al 2 Si0 5 provides a sensitive test of the vibrational approach to
thermodynamic calculations. The computed and calorimetric C p and S agreed
at the level of 1% at 298 K because the spectral assignments can be made
quite accurately. Modeling of the phase boundaries requires calculation of
differences in the free energy AG p T at the phase boundaries, and also requires
incorporation of the thermochemical heat of solution calorimetry data. The
different calculations done constraint the triple non-variant point of kyanite- and
alusite-sillimanite at 477-557C and 3-4.6 kbar (compare with 430 10 K, 3
0.1 kbar originally in Salje and Werneke 1982b). Although this may seem like
a large range, it should be remembered that the free-energy surfaces intersect at a
very shallow angle and that experimentally determined values span a similar
range.
The System BeO-AI 2 0 3 -Si02 -HzO. The vibrational/thermodynamic approach
has been applied to several minerals in the system BeO-Alz03SiO z--H 2 0, including bromellite (BeO), chrysoberyl (Al zBe0 4 ), phenakite
(Be 2 Si0 4 ), bertrandite [Be 4 Si 2 0 7 (OH}z], beryl (Be3AlzSi601s), and euclase
[BeAISi0 4 (OH)]. Experimental infrared and Raman spectra have been measured, and used to construct g( w) models for thermochemical calculations. If the
Be-O, Si-O, and OH stretching modes are correctly enumerated and assigned,
heat capacities can be predicted to within 5% at T < 500 K. The comparison of
models with different interpretations of the Be-O and Si-O band assignments
with calorimetric data demonstrates that even with incomplete, but reasonable,
band assignments, good thermodynamic results can be obtained.
Summary
Models of thermodynamic behavior based on vibrational spectra cannot be
constrained uniquely. Rather, a family of models can be examined, each
consistent with vibrational and structural data. When combined with experimental calorimetric work, the models are allowing many new insights both into
microscopic lattice properties and into macroscopic harmonic and anharmonic
properties of minerals.
References
Agoshkov VM (1985) Calculating mineral thermodynamic parameters from a lattice vibrational-spectrum model for silicates and oxides, Geokhymia N 10: 1441-1454 (in Russian);
also in English (1986) in Geochemistry International 23 (1-4): 154-167
Akaogi M, Ross NL, McMillan P, Novrotsky A (1984) The Mg 2 Si0 4 polymorphs (olivine,
modified spinel and spinel) - thermodynamic properties from oxide melt solution calorimetry, phase relations and models of lattice vibrations. Am Mineral 69: 499-512
Brehat F, Wyncke B, Leonard JM, Dusausoy Y (1990) Infrared reflectivity spectra of single
crystal cassiterites. Phys Chern Mineral 17: 191-196
429
Chopelas A (1990a) Thermal expansion, heat capacity, and entropy of MgO at mantle
pressure. Phys Chern Mineral 17: 142-148
Chopelas A (1990b) Thermal properties of forsterite at mantle pressures derived from
vibrational spectroscopy. Phys Chern Mineral 17: 149-156
Clayton RN, Kieffer SW (1991) Oxygen isotopic thermometer calibrations. In Taylor HP,
O'neil JR, and Kaplan IR (eds) Stable Isotope Geochemistry: a tribute to Sam Epsten.
Geochemical Society spec. Publ. No.3, Sanantonis, Texas, pp 3-10
Fei Y, Saxena SK, Navrotsky A (1990) Internally consistent thermodynamic data and
equilibrium phase relations for compounds in the system MgO-Si0 2 at high pressure and
high temperature. J Geophys Res 95: 6915-6928
Ghose S, Hastings JM, Corliss LM, Rao KR, Chaplot SL, Choudhury N (1987) Study of
phonon dispersion relations in forsterite MgSi0 4 by inelastic neutron scattering. Sol State
Commun 63: 1045-1050
Gillet PH, Guyot F, Malezieux JM (1989) High pressure and high temperature Raman
spectroscopy of Ca 2 Ge0 4 : some insights on anharmonicity. Phys Earth Planet Int 58:
141-154
Gillet PH, Le Cleac'h A, Madon M (1990) High temperature Raman spectroscopy ofSi0 2 and
Ge0 2 polymorphs: anharmonicity, thermodynamic properties and phase relations among
the Si0 2 polymorphs at high temperatures. J Geophys Res 95: NB13 21, 635-21, 655
Hemley RJ, Chen RE, Yeganeh-Haeri A, Mao HK, Weidner DJ, Ito E (1989) Raman
spectroscopy and lattice dynamics of MgSi0 3 -perovskite at high pressure. In: Navrotsky A,
Weidner DJ (eds) Perovskite: a structure of great interest to geophysics and material science.
Geophys Union, Washington DC, pp 35-53
Hemly RJ, Jackson MD, Gordon RG (1987) Theoretical study of structure, lattice dynamics,
and equation of state of perovskite-type MgSi0 3 and CaTi0 3 . Phys Chern Mineral 14: 2-12
Hofmeister AM, Hoering TC, Virgo D (1987) Virbrational spectroscopy of beryllium aluminosilicates: heat capacity calculations from band assignments. Phys Chern Mineral 14:
205-224
Ito E, Navrotsky A (1985) MgSi0 3 ilmenite: calorimetry, phase equilibria, and decomposition
at atmospheric pressure. Am Mineral 70: 1020-1026
Kieffer SW (1979a) Thermodynamics and lattice vibrations of minerals: 1. Mineral heat
capacities and their relationships to simple lattice vibrational modes. Rev Geophys Space
Phys 17: 1-19
Kieffer SW (1979b) Thermodynamics and lattice vibrations of minerals: 2. Vibrational
characteristics of silicates. Rev Geophys Space Phys 17: 20-34
Kieffer SW (1979c) Thermodynamics and lattice vibrations of minerals: 3. Lattice dynamics
and an approximation for minerals with application to simple substances and framework
silicates. Rev Geophys Space Phys 17: 35-59
Kieffer SW (1980) Thermodynamics and lattice vibrations of minerals: 4. Applications to
chain and sheet silicates and orthosilicates. Rev Geophys Space Phys 18: 862-886
Kieffer SW (1982) Thermodynamics and lattice vibrations of minerals: 5. Application to phase
equilibria, isotopic fractionation, and high-pressure thermodynamic properties. Rev Geophys Space Phys 20: 827-849
Kieffer SW, Navrotsky A (eds) (1985) Microscopic to macroscopic: atomic environments to
mineral thermodynamics. Reviews in Mineralogy, vol 14, Mineral Soc Am 428 pp
Lazarev AN (1988) Vibrational spectra, lattice dynamics and chemical constitution of oxides.
Lazarev AN, Shchegolev BF, Smirnov MB, Dolin SP (1988) Quantum chemistry of molecular
systems and the crystal chemistry of silicates. Nauka, Leningrad (in Russian)
Mineral 17: 97-107
McMillan PF, Ross NL (1987) Heat capacity calculations for AI 2 0 3 corundum and MgSi0 3
ilmenite. Phys Chern Mineral 14: 225-234
Navrotsky A (1987) Silicate and germanate garnets, i1menites and perovskites: thermochemistry, lattice vibrations, and spectroscopy. In: Manghnani MH, Syono Y (eds) Highpressure research in mineral physics, pp 261-268
Navrotsky A (1989) Thermochemistry of perovskites. In: Navrotsky A, Weidner DJ (eds)
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Perovskite: a structure of great interest to geophysics and materials science. Geophys

Monograph 45, Am Geophys Union, Washington, DC, pp 67-80
Price DL (1988) Lattice dynamics and inelastic neutron scattering from forsterite: phonon
dispersion relation, density of states and specific heat. Phys Chern Mineral 16: 83-97
Price GD, Parker SC, Leslie M (1987) The lattice dynamics and thermodynamics of Mg 2 Si0 4
polymorphs. Phys Chern Mineral 15: 181-190
Ross NL, Akaogi M, Navrotsky A, Susuki n, McMillan P (1986) Phase transitions among the
CaGe0 3 polymorphs (wollastonite, garnet and perovskite structures): studies by high
pressure synthesis, high temperature calorimetry and vibrational spectroscopic techniques.
Salje E, Werneke Chr (1982a) How to determine phase stabilities from lattice vibrations. In:
Schreyer W (ed) High pressure researches in geosciences. Schweizbart'sche Verlagsbuchhandlung, Stuttgart, pp 321-348
Salje E, Werneke Chr (1982b) The phase equilibrium between sillimanite and andalusite as
determined from lattice vibrations. Contrib Mineral Petrol 79: 56-67
Sangster MJL, Peckham G, Saunderson DH (1970) Lattice dynamics of magnesium oxide.
J Phys C 3 : 1026-1036
Valley JW, Taylor HP, Jr, O'Neil JR (eds) (1986) Stable isotopes in high temperature
geological processes. Reviews in Mineralogy, vol 16. Mineral Soc of Am, Washington, DC,
570 pp
Weidner DJ, Savamoto H, Sasaki S, Kumazava M (1984) Single crystal elastic properties of
spinel phase of Mg 2 Si0 4 1 Geophys Res 89: 7852-7860
Williams Q, leanloz R, Akaogi M (1986) Infrared vibrational spectra of beta-phase Mg 2 Si0 4
and Co 2 Si0 4 to pressures of 27 GPa. Phys Chern Mineral 13: 141-145
Williams W, leanloz R, McMillan P (1987) The vibrational spectrum of Mg 2 Si0 3 -perovskite:
zero pressure Raman and mid-infrared spectra to 27 GPa. 1 Geophys Res 92: 8116-8121

G.
BUNTEBARTH
and A. GUKO
The temperature to which a rock and ultimately each of its constituents is

exposed at a given depth of the Earth's interior is dependent on the amount of
heat flow density passing through the rocks. This amount is the result of the
contributions of three main mechanisms of heat transfer in the earth, i.e., lattice
(or phonon) conduction, convection, and radiation. The contribution of each
mechanism depends strongly on the prevailing physical conditions.
The conductive and also radiative heat flows are proportional to the thermal
properties of the rocks and their mineral constituents, whereas the convective
heat flow is dominated by the mechanical properties, if an overall mass
transport of the rock occurs, or by the properties of the pore space between the
mineral grains, if a fluid flow occurs.
Within the crust, the radiative heat transport can be neglected, so that the
heat conduction can be described by the equation:
Aa div(grad T) - div(Prcrvr T)
+ H = PaCa {)T,
{)t
assuming a homogeneous isotropic space with fluid flow, where T = temperature, t = time, H = heat generation, A = thermal conductivity, = porosity,
P = density, c = specific heat capacity, Yr
+ </1 Ar , P.C. =
(1 - </1) PrCr
+ </1 Pr cr , r =
431
= filtration velocity, A. = (1 - </1) Ar

refers to rock, and f = to fluid within
the pore space.

A change in temperature (right hand side) is a result of the source terms (left
hand side), i.e., a spatial variation in the temperature gradient (1st term), in the
fluid flow through the pore space (2nd term) or a constant heat generation rate
(3rd term). The last term is a result of the radiogenic heat generation of U, Th,
and K40. This term can also have a negative value, reflecting a heat sink, as, for
example, during dehydration of pelites.
In the continental lithosphere heat is transferred mainly by conduction,
except in the uppermost layers, where the migration of pore fluid may contribute
substantially to the heat flow. In the oceanic lithosphere, these processes only
dominate at distances far away from the mid-ocean ridges. Near the ridges, the
migration of water percolating the bottom sediments and the uppermost layers
of rocks seriously disturbs the conductive temperature distribution. Within the
asthenosphere, heat is transported mainly by convection, and the radiative heat
transfer also increases in importance.
Thermal Conductivity and Dilfusivity
The lattice thermal conductivity is defined as the ratio of heat flow density to
temperature gradient. Since it is related to lattice properties, the thermal
conductivity is sensitive to variations in temperature and pressures, as are the
lattice properties. At temperatures above the Debye temperature, a relationship
for isotropic single crystals has been deduced as:
A = ~ cyvaO
3 oeyvT'
where Cy = specific heat capacity at constant volume, v = mean sound velocity,

a o = lattice constant, oey = volumetric thermal expansion coefficient, v = Griineisen parameter, T = temperature.
If the equation of heat conduction is divided by the thermal capacity (pc), the
thermal diffusivity a further thermal property is defined as:
A
a=-.
pc
During a nonsteady state, the process of temperature equalization is regulated by this property; but when the stationary state is approached, the thermal
conductivity A regulates the heat transfer.
Methods to Measure the Thermal Conductivity and Dilfusivity

The commonly used methods may be divided into two classes, i.e., steady state
and transient techniques. The steady state methods are usually comparative
432
techniques where the one dimensional heat flows along the unknown specimen
and a reference disc. The heat flow density Q is determined at the reference
probe and with the measured temperature gradient across the specimen, the
thermal conductivity of the specimen is determined. Using different fluids or
diamond powder and an uniaxial pressure in addition, the contact resistances
are small enough to be negligible, so that
A. s
= Q/(dT/dx}s where Q = ).r(dT/dx}r'
sand r refer to specimen and reference probe, respectively.

An absolute method is the cylindrical heat flow technique. A long heating
wire supplies thermal energy radial-symmetrically into the specimen whereby
the temperatures are monitored at two points, r 1 and r 2' When the stationary
state is reached, the thermal conductivity can be determined by:
A.
= Q In(r 2/r 1}
2n T1 - T 2 '
where Q is the energy per unit time and unit length and T 1 - T 2 is the
temperature difference between the radii r 1 and r 2' The transient state can be
used to determine the thermal diffusivity. The previously described heat flow
Table 33. Thermal conductivity of some minerals at room temperature.

(Roy et al. 1981; Buntebarth 1994)
a) Polycrystalline
Flourite (CaF 2)
Quartz (Si0 2)
Dolomite (CaMg(C0 3}z)
Grossularite (Ca3AI2Si3012)
Forsterite (Fo 9S Fa 2)
Diopside (CaMgSi 20 6)
Enstatite (En 9s Fs 2)
Calcite (CaC0 3)
Pyrope (Mg 3AI 2Si 30 12 )
Muscovite (K3AI4Si6AI2020(OH)4)
Orthoclase (KAlSi 30 s )
Albite (Ab 99 An l )
Anorthite (Ab 4An 96 )
b) Single crystals
Corundum (AI 20 3)
Diamond (C)
Graphite (C), parallel (001)
Graphite (C), perpendicular (001)
Quartz, direction of optical axis c
Quartz, perpendicular of optical axis c
Muscovite, parallel (001)
Muscovite, perpendicular (001)
9.5
7.7
5.5
5.5
5.1
5.1
4.3
3.6
3.2
2.3
2.3
2.3
l.7
27
120-160
355
89
12.0
6.0
0.8
5.0
433
meter method is also applicable for determining the thermal diffusivity, if the
temperature is varied at one face of the bar.
A rapid method to determine the thermal diffusivity is the "flash" method
where heat pulses, usually from a laser or a xenon lamp, are absorbed at one face
of a thin specimen, and the temperature rise is measured at the other face as a
function of time. This method is applied up to 1800C.
The values of the thermal conductivity of most common crustal rocks at near
surface conditions vary between 2 and 5 W jmK. The range is due to the thermal
conductivity of the poor heat conducting but very abundant feldspars and
to the, in general, better conducting chain silicates (Table 33). An exception
is quartz, whose content in crustal rocks determines its total conductivity.
Forsterite, which is abundant in the upper mantle, also conducts heat well.
From the viewpoint of mineralogy, an attractive way to determine the
distribution of thermal parameters for different mineralogical mantle models is
10
~_~1
___
600
1200
1800
T, K
Fig. 108. Temperature dependence

of thermal conductivity for some
minerals (average values). 1 pyrophillite; 2 fused quartz; 3 forsterite;
4 quartz (010); 5 quartz (001); 6
MgO; 7 AI 2 0 3
434
to use the methods of estimating thermal properties from mineral content. The
theories which may be used are based on a statistical approach or on the
consideration of specific simple structural models of rocks. The experimental
data on the thermal conductivity of some minerals (the average values) at
elevated temperatures are shown in Fig. 108. The influence of pressure can be
taken into account by the use of empirical linear or quadratic relationships
between the thermal conductivity and pressure. There are minerals with very
unusual, extremely high, thermal conductivities such as diamond (120
- 160 W m - 1 K - 1 at 0 0c) and, in particular, sapphirine, whose conductivity at
very low temperatures is comparable with the conductivity of metallic materials.
These features find applications in material science.
Influence of Mineral Reactions on the Thermal State
During the devolatilization of rocks, H 20 and CO 2 are released from those

rocks containing, e.g., chlorite, muskovite, and other minerals which become
unstable with increasing temperature. These reactions absorb energy ranging
between 60 kJ and more than 100 kJ according to the type of devolatilization
reaction. The total amount of heat needed for dehydration has to be supplied by
a heat source which can be a magma body or, on a more regional scale, the heat
flow from the deeper interior of the Earth. During the time at which such
reactions are not completed, the temperature cannot increase. The strength of
the heat sink H which can exceed that of heat sources like radiogenic heat
generation by several orders can be estimated by:
H
= Ep/t,
where E = energy for dehydration of each kg rock, p = rock density, and

t = reaction time.
Similar estimations are yielded with other mineral reactions which consume
or supply heat in the Earth's interior.
Heat Flow Density Data (HFD) and Mantle Heat Flows
The average HFD is equal to 57 mW/m2 for continents and 99 mW/m2 for
oceans. There are differences in the average HFD for different continents, i.e., the
lowest value is reported for Africa, 49.8 mW/m2, and the highest for Australia,
63.6 m W /m 2. The continental crust contains a significant amount of radioactive
heat sources the most important being U 235 , U 238 , Th 232 , and K 40 , which are
associated mainly with acidic rocks. They contribute for different tectonic
structures from 1/3 to 1/2 of the observed HFD. The rest is due to the heat
supplied to the base of the lithosphere. At oceans almost the total HFD is
related to the convective processes in the mantle and the cooling of the
lithospheric plates spreading from the mid-ocean ridges.
435
Heat Transfer in the Sublithosphere Mantle

The thermal structure of the mantle is defined gradually by a high temperature
gradient at the base of the lithosphere and at the boundary between the mantle
and the Earth's core. Estimates for Rayleigh number which controls the state of
a convective system show that a well-developed convection should occur in the
mantle. Two alternative models are being discussed by geophysicists and
geochemisists: in the model of the whole mantle convection, the temperature
distribution is nearly adiabatic throughout the mantle and in the alternative
two-stage model, the upper and lower mantles are separated by a thermal
boundary layer.
Thermal Events and Problem of Paleo thermal Reconstructions

One of the actual problems lying at the boundary between geophysics and
geochemistry is to find a way to reconstruct the thermal evolution of the
lithosphere. There are a number of methods for paleotemperature estimations
for sedimentary basins, based on the data on the maturation of organic
materials.
Several attempts have been made to reconstruct the evolution of mantle heat
flow during continental rifting based on petrochemical data and on the solution
of the nonsteady state boundary value problem.
References
Buntebarth G (1991) Thermal models of cooling. In: Voll G, Topel J, Pattison D, Seifert F (eds)
Equilibrium and kinetics in contact-metamorphism: the Ballachulish igneous complex and
its aureole. Springer, Berlin Heidelberg New York, pp 379-402
Buntebarth G (1994) Thermal properties of some sedimentary rocks. (in prep)
Buntebarth G, Stegena L (1986) Methods in paleogeothermics. In: Buntebarth G, Stegena L
_ (eds) Paleogeothermics. Springer, Berlin Heidelberg New York, pp 5-39
Cermak V, Rybach L (1982) Thermal properties. In: Angenheister G (ed) Physical properties of
rocks. Landolt-Bornstein, New ser, group V, voila. Springer, Berlin Heidelberg, New York,
pp 305-343
Gliko A, Grachev AF, Magnitsky VA (1985) Thermal model for lithospheric thinning,
associated uplift in the neotectonic phase of intraplate activity and continental rifts.
J Geodyn 3: 137-153
Haenel R, Rybach L, Stegena L (eds) (1988) Handbook of terrestrial heat-flow density
determination. Kluwer Acad Publ, Amsterdam
Roy RF, Beck AE, Touloukian YS (1981) Thermophysical properties of rocks. In: Touloukian
YS, Judd WR, Roy RF (eds) Physical properties of rocks and minerals. McGraw-Hill,
Sclater JG, Jaupart C, Galson DA (1980) The heat flow through oceanic and continental crust
and the heat loss of the earth. Rev Geophys Space Phys 18: 269-311
Turcotte DL, Schubert G (1982) Geodynamics, vol 2. J Wiley & Sons, New York
Wendlandt RF, Morgan P (1982) Lithospheric thinning associated with rifting in East Africa.
Nature 298: 734-736
436
6.6 Magnetic Properties of Minerals

W.O'REILLY
All materials respond in some way to a magnetic field so that all minerals have
magnetic properties. Minerals which contain no ions with uncompensated spins
(e.g., an absence of, notably, the transition series elements) are diamagnetic.
Those containing transition elements in low concentrations are paramagnetic.
The ratio of the magnetic susceptibilities of these two categories of mineral can
be high enough ( ~ 10 2 ) that magnetic methods can be employed to physically
separate, e.g., the desirable (diamagnetic) fraction from the undesirable (paramagnetic) fraction of the raw material used for porcelain manufacture. Thus
even diamagnetism can be usefully exploited.
Minerals with high concentrations of transition elements may be ferrimagnetic, antiferromagnetic, or ferromagnetic at ambient temperatures. Sometimes
the magnetic properties of these minerals are directly useful in, for example,
refining ores, including the separation of coal from stone. Sometimes the
magnetic properties are used less directly; for example, a magnetic survey reveals
magnetic ore which in turn indicates the probable presence of more valuable
minerals, such as gold.
Ferrimagnetic minerals are widely dispersed in the rocks of the Earth's crust
in concentrations rarely exceeding 10%. Just as is the case with the more
abundant rock-forming minerals, the state of the magnetic minerals reflects the
physical and chemical history of the host rock. The state of the minerals can be
inferred from the magnetic properties of the bulk rock, and magnetic measurements can therefore reveal information about the state or history of the rock.
Thus anisotropy of magnetic susceptibility is used to determine rock fabric; or
Curie point temperature measurements indicate the degree of oxidation of a
submarine basalt. Although an indirect method compared to optical study, the
magnetic method does have the advantage of sampling vast numbers of mineral
grains.
The presence of ferrimagnetic minerals in crustal rocks has had monumental
importance in leading to the study of paleomagnetism, by which the history of
the geomagnetic field and motions of the crust can be traced over geological
time. This is possible because the ferrimagnetic mineral fraction can acquire a
record of the direction of the geomagnetic field at more or less the time of
formation of the rock. The consequent study of the relationship between the
magnetism of minerals and their chemical composition, crystal structure, microstructure, the effect of transformations (e.g., oxidation), and of elevated temperatures and pressures, and the mechanisms (thermoremanence, chemical
remanence, depositional remanence, piezoremanence) by which they may acquire
437
a magnetic record which can survive more or less intact over geological time, has
evolved into the field of study known as rock and mineral magnetism. One goal is
to provide theory and practice which underpins the paleomagnetic method, and
which may lead to an understanding of the magnetism of the Earth's crust at a
profound level. The theoretical and experimental work that is inspired by
observations of the magnetism of rocks, also leads to new science by attacking
problems which otherwise might not have been recognized. Nature's recording
medium is imperfect and problems of unsuitable compositions, nonideal particle
size and shape, and complex recording processes, which can be avoided by the
designers of man-made recording media, must be confronted by rock magnetism
researchers, and science (and technology) profits. Thermoremanence, the mechanism hypothesized and studied to explain the stable remanent magnetization of
igneous rocks, now finds application in the replication of prerecorded video
tapes.
Magnetic minerals also figure in the human and animal worlds. A record of
human activity (e.g., the Industrial Revolution) is found in the magnetic
properties of soils, sediments, and peats; and the magnetic properties of artefacts
may allow events in antiquity to be dated, or provide details of human practices
(e.g., how the pots in a kiln were stacked during firing). Magnetite occurs as
a biomineral in many species, from bacteria to whales, where it appears to
provide a means of navigation.
The Titanomagnetites
The composition of most magnetic minerals can be closely approximated by
points in the FeO-TiO z-Fe z0 3 ternary diagram (Fig. 109). The titanomagnetites Fe 3 _ xTixO 4 (0 < X < 1) have the spinel structure like many ferrite oxides. Of
particular interest is the strongly magnetic magnetite, Fe 3 0 4, (x = 0) and the
less strongly magnetic composition Fe Z .4 Tio.6 0 4 (x = 0.6, often referred to as
TM60) which approximates to the magnetic mineral in the newly constructed
crust at the spreading centers. The intrinsic magnetic properties, such as
spontaneous magnetization (Ms), magnetocrystalline anisotropy constants
(K l , K z), magnetostriction coefficients (Aloo' Al1l etc.), and Curie point temperature (Te), depend, for a given composition, on the distribution of the constituent
cations - FeZ + , Fe 3 + and Ti4 + - between the tetrahedral and octahedral sites of
the structure. As the compositional parameter x increases through the solid
solution series, the increasing concentrations of FeZ + and diamagnetic Ti4 + ,
and reducing concentration of Fe3+ lead to a decrease in Ms and a fall in Te.
Variations in Ms and Te for nominally the same x values have been the subject of
some investigation. For x = 0.6, Ms values (at low temperature) range from
30-40 A m Z kg-l, and Te from 150-220 0c. Ms, being the difference between the
magnetization of the two crystallographic (and magnetic) sublattices, is sensitive
to cation distribution, whereas Te, being more like a product, is relatively
insensitive. The variations in Ms have been ascribed to variations in the cation
438
FeO
1/3 Fe304
magnetite
112 Fe20~
maghemlte
haematite
Fig. 109. The FeO-Ti0 2 -Fe 2 0 3 ternary diagram on which many of the more abundant
magnetic minerals can be located (species other than Fe and Ti generally occur in small
concentrations only). Primary magnetic minerals in igneous rocks can be modeled by
Fe2.4TiO.604 (TM60) or Fe 3 0 4 (magnetite). Oxidation of primary minerals is common and
results in movement to the right in the diagram. Hematite (IXFe 2 0 3 ) is the ultimately stable
oxidized magnetic mineral (see also Fig. 125)
distribution due to the thermal history of the investigated samples. The Ms of a

particular titanomagnetite sample would reflect the last elevated temperature at
which there was time for the equilibrium cation distribution to be reached.
The time (r) required for the di~tribution to have moved a significant
distance towards equilibrium at temperature T is r oc exp (LljkT), where Ll is
related to the energy barriers which oppose the interchange of ions between the
two crystal sublattices. A value of Ll of about 0.1-0.2 eV has been inferred from
experiments on simple 2-3 spinel oxides such as Mg2+Fe~+04' for which
variations in cation distribution can readily be induced in practicable laboratory
times. If Ll is much larger than 0.2 eV, or is itself temperature-dependent, so that
Ll grows as T falls, r becomes a much stronger function of temperature. It may
become impossible to demonstrate the temperature dependence of the distribution in the laboratory, although the wide range in cooling rate possible in nature
could produce variations in cation distribution in naturally occurring materials.
In laboratory studies, the cation distribution, and observed M s , at room
temperature will correspond to only a narrow temperature range for which the
439
experimental time is of the same order as T. This may explain why direct attempts
to observe the temperature-dependent cation distribution in titanomagnetites
have failed. If reliable values for the potentials of Fe 2 + , Fe 3 +, and Ti4 + in oxides
are available, a computational approach might be fruitful and illuminating.
The observed variation in Ms of the synthetic titanomagnetites must still be
explained, and one possibility may be in a variable concentration of vacant
lattice sites ("high temperature nonstoichiometry"). High temperature nonstoichiometry certainly appears to have a strong (but unexplained) influence on
T c such that Tc(x,z) = T c(x,o) + 700 z, where z is an oxidation parameter. The
limiting value for z is temperature-dependent, but can be as large as ~ 0.1. Thus
Tc may vary by about 70C for a given x.
The spin structure-dependent properties (Ms' K 1 , A) depend on temperature
and vanish at the Curie point. The temperature variation of K1 and A can be
quite complex. The variation of K1 with temperature for some titanomagnetite
compositions is shown in Fig. 110. The zero point in K1 indicates a switch in the
preferred direction of spontaneous magnetization from [100] (K1 > 0) to [111]
(K1 < 0). K1 results from the individual, "single-ion", contributions of Fe 2 + and
Fe 3 + in the octahedral and tetrahedral sites. The temperature dependence of the
Fe2+ contribution (in octahedral sites in near-Fe 3 0 4 compositions) is the most
Normalised temperature (T ITc )
,.,
-...
....,
0.4
0.6
c
0
iii
c:
0
>Go
0III
c:
<{
2
xl0 4
Fig. 110. The temperature dependence of the first magnetocrystalline

anisotropy constant Kl of Fe-rich
titanomagnetites. The zero points in
Kl may be due to the complex behavior of Fe 2 + in the octahedral
sites of the spinel structure
440
complex and may be directly responsible for the zero point in K t . Magnetocrystalline anisotropy and magnetostriction are related, and the increasing concentration of highly anisotropic Fe2+ in higher x-value compositions (say, TM60)
is believed to be responsible for the "giant magnetostriction" found at low
tern perature.
The room temperature values of the composition-related intrinsic magnetic
properties result from an interplay between the changing composition (increasing Fe2+, decreasing Fe3+), and the consequences of the changing composition
on Curie point temperature. Thus the introduction of Fe 2 +, which being an
anisotropic ion is expected to increase the anisotropy of the material, may bring
about a decrease in anisotropy at some specific temperature (say room temperature), because the exchange interaction has also been weakened and the Curie
point temperature lowered (to, say, even below room temperature). The systematic variation of the intrinsic properties with temperature and composition is
often best revealed by replacing temperature, T, by the dimensionless magnetic
temperature, T/Tc.
The magnetization process parameters - susceptibility (X), remanence, etc. are extrinsic, depending on microstructure, in addition to their dependence on
the intrinsic properties. Their connection to the intrinsic properties takes the
5
x 10-2
X I Ms
I K11 1Ms
I K11
Ms
3
2
I
,,
,;
.,- ...
.,-
x 10-10
X
Ms
6
A
.,- ...
"d
tf'
0
10
,,:.1>----0-- _--000-- --- __

.AI
0.4
Composition, x
---0...
-----0
0.6
Fig. 111. The room temperature values of the ratios

IKII/Ms and IAI/Ms of titanomagnetites as a function of
composition. These ratios indicate the compositional influences on the magnetization
process parameters. The potential via IAI/Ms for high
magnetic "hardness" due to
stress in x = 0.6 (TM60) is
evident
441
form ofa dependence on the ratios IK11/Ms or IAI/M s. A high Ms means that even
a small applied field will couple strongly with the magnetization and make the
material "soft" (e.g., a high X). On the other hand, a high IK11 or IAI indicates a
strong coupling of the magnetization to the crystal axes or a strain direction,
making the material "hard" (low X). The room temperature values for the
hardness parameters of the titanomagnetites is shown in Fig 111. The variation
of IAI/Ms with composition is striking. The value achieved for TM60, when
combined with the stress which may be incorporated into the crystal structure by laboratory pulverization, say, or by compositional gradients in naturally
occuring crystals - results in the highest magnetic hardness (highest coercive
force, most stable remanence etc.), so for observed, for any mineral at room
temperature.
The Titanomaghemites
The titanomaghemites are non stoichiometric spinel oxidation products of the
titanomagnetites produced by adding oxygen to the structure or removing iron
from it. The titanomaghemite field is the quadrilateral Fe 30 4-Fe 2 TiOc(near)
Fe 2 TiOs-Fe 2 0 3 of the ternary diagram (Fig. 109). One well-known member of
the tianomaghemite family is maghemite (y-Fe 2 0 3, or as a spinel, Fe s/3D 1/304'
where D represents vacant cation sites). On raising the temperature or pressure,
y-Fe 2 0 3 "inverts" to hematite (a-Fe 2 0 3); the titanomaghemites are structurally
metastable.
The intrinsic magnetic properties of the titanomaghemites depend on composition and cation distribution. The cation distribution is believed to depend
on the distribution in the initial titanomagnetite and the mechanism, at the
atomic level, by which oxidation - "maghemitization" - takes place. In the
laboratory, maghemitization is induced by heating in air or water at low
temperatures (100-350 Qq. Models for the maghemitization mechanism involve
the relative availabilities for oxidation of Fe 2 + in the octahedral and tetrahedral
sites of the structure, and the location of the consequent vacancies. Laboratory
maghemitization usually requires fine particle sizes, which can lead to difficulties
in interpreting Ms in terms of cation distribution; nor do M. measurements
alone produce a unique solution for cation distribution. Nevertheless, there is
good broad agreement between experiment and model predictions. At room
temperature, Ms falls as degree of maghemitization increases for TM60 and
compounds close to TM60 in composition (often Mg, AI, and other cations are
included to more closely simulate natural materials). The fall in spontaneous
magnetization alone is not enough to explain the fall, with increasing degree of
maghemitization, in remanence intensity of the titanomaghemite bearing rocks
of the submarine crust (see below). Curie point temperature rises steadily as
degree of maghemitization increases, indicating that the effect of the dilution by
the growing vacancy concentration is offset by the increase in concentration of
the strongly exchange-coupled Fe3+ ions. When a titanomagnetite with Tc
442

Fig. 112. The fall in unit cell parameter with
increasing degree of oxidation (z,O < z < 1) of
maghemitized titanomagnetites. This fall has
implications for the mechanical and micromagnetic state of the heterogeneously maghemitized
particles in submarine basalts
x=
1.0
6 52
0<t
Q/
1/1
Q; 6.40
6.36
6 32 L-_--'-_-1.._----l_ _.L..-_....I
o 0.2 0.4 0.6 0.6 1.0
Oxidation paramE'tE'r,
initially below room temperature achieves a Tc above room temperature by

undergoing maghemitization at near-ambient temperature in the presence of a
field, the product acquires a species of chemical remanent magnetization.
The products of maghemitization are metastable and invert without change
in bulk composition to a more stable configuration. Incompletely maghemitized
compositions will include a component near Fe 3 0 4 in composition in their
inversion products, and the question of the relationship between the magnetic
remanence direction of the product to that of the starting compound has both
intrinsic interest and relevance to paleomagnetism. The processes of maghemitization and inversion figure prominently in attempts to understand the magnetism of the submarine crust. The cell edge parameter of titanomaghemites is
reduced as maghemitization proceeds (Fig. 112), and it seems likely that the
microstructural consequences of this lattice shrinkage is a major influence on
the magnetism of the heterogeneously maghemitized particles produced at
ambient temperatures over long times in the submarine crust.
Hematite and the Hematite-Ilmenite Solid Solution Series
Hematite (a-Fe 2 0 3 ) has the corundum structure which leads to (an imperfect)
antiferromagnetism. The ilmenite structure is essentially similar to the
443
corundum structure, but has basal plane cation layers occupied alternately by
Fe2+ and by Ti4+. The hematite-ilmenite solid solution Fez _yTiy03 (0 < Y < 1)
(Fig. 109) may have ordered or disordered distributions of FeZ +, Fe 3+, and Ti 4 +
between the cation layers. An ordered distribution could have layers with
(1-y)Fe3+ and yTi4 + alternating with layers containing (l-y)Fe3+ and yFe2+. If
the layers are oppositely coupled by exchange interactions, the spontaneous
magnetization would be 4y Bohr magnetons per formula unit at low temperature. Moments approaching these values have been found for slow cooled
samples of composition y = 0.6-0.8. These strong magnetizations cannot persist
up to y = 1, regardless of the degree of order produced by slow cooling. One
sublattice becomes totally populated by nonmagnetic Ti 4 + ions, and the spin
structure must be organized by the separated Fe2+ -rich layers. This results
in antiferromagnetism and the low Neel point temperature (TN = 55 K) of
ilmenite.
At the other end of the series, the abundant mineral hematite is an
antiferromagnet, at least in mm-size crystals and at low temperature, when the
moments of the Fe 3+ ions lie perpendicular to the basal planes and the
magnetization of alternate layers is precisely antiparallel. The orientation of the
spin structure is governed by the sign of the anisotropy constant Ku' This
consists of two terms due to the competing single-ion and dipolar contributions
to the anisotropy, which may cancel at a Ku = 0 point (the Morin transition).
The dipolar term falls less quickly as T rises and dictates the sign ofK u above the
compensation point. Thus above about - 10 e, the spin structure switches to
lie within the basal planes of the crystal structure (Fig. 113). The two magnetic
sublattices of the antiferromagnetic structure no longer lie closely antiparallel.
This is accounted for by a antisymmetric exchange interaction described by a
term - D Ml X M z in the expression for the free energy. The vector D, lying
along the trigonal axis of the structure, represents the exchange energy constant
(in appropriate units) and Ml and M z are the sublattice magnetizations. The
combination of this antisymmetric exchange interaction with the interaction
Fig. 113. The corundum structure of

hematite and the antiferromagnetic
spin structure above the Morin transition. The canting of the spin structure, which cannot be shown on the
scale of the diagram, leads to the weak
ferromagnetic moment at right angles
to the antiferromagnetic spin axis and
within the basal plane.
444
represented by IJIM 1 . M 2 , and the sign of the anisotropy constant corresponding to the spins lying in the basal plane, results in a coexistence of antiferromagnetism and a kind of ferromagnetism (i.e., the presence of a spontaneous
magnetization). The basic antiferromagnetism comes from alternately magnetized basal planes (Fig. 113) and has an anti ferromagnetic perpendicular susceptibility, when H is within the basal plane, of 110/J (J in appropriate units). The
"weak ferromagnetism" of about 0.4 A m 2 kg -1 arises because the two antiferromagnetic sublattices are not perfectly anti parallel for the minimum free
energy, but are canted by a small angle. The net spontaneous magnetization is
then DMo/J and lies in the basal plane (Mo = IMII = 1M2!)' No spontaneous
magnetization can exist outside of the basal plane. The Morin transition
temperature is depressed in fine enough particles, thus extending the temperature range for ferromagnetism. A change in composition (e.g., Ti substitution)
naturally affects both terms and usually depresses the transition temperature.
Because the spontaneous magnetization is small, the ratio AIMs is large, and
hematite has the potential to be magnetically hard when suitable internal stress
is present.
The Pyrrhotites
Troilite, FeS, which crystallizes in the NiAs structure has, like hematite above
the Morin transition temperature, magnetized layers lying in the basal planes
with alternating orientation. The spin structure is colinear and has only
antiferromagnetic susceptibility. Monoclinic pyrrhotite (Fe 7 SS ) is cation-deficient and, below the f3 transition, the vacancies are located in layers which
alternate with completely filled layers. This gives rise to a strong ferrimagnetism
of about 30 A m 2 kg-I confined to lie in the basal plane by a strong crystal
anisotropy (Ku '" 10 5 J m - 3).
The hexagonal pyrrhotites (Fe 9 S IO ' FelOS ll and Fe ll S 12 ) have fewer vacancies. Ordered arrangements, which may consist of layers which contain 25%
vacancies (like Fe 7 SS ) separated by different numbers of filled layers, as appropriate to the compositional formula, are ferrimagnetic. The ferrimagnetic ordered arrangement is stable between about 200C (T y) and the T c of about
250C. The ferrimagnetism of about 10 A m 2 kg-I can be preserved at room
temperature by quenching from above Ty- The anisotropy within the basal plane
of Fe 7 SS seems to be triaxial with magnitude 3 x 10 3 J m - 3.
The iron sulfide Greigite, Fe 3 S4 , which is ferrimagnetic with spontaneous
magnetization of 20-30Am2 kg- 1 and a Tc of about 300-340C is probably
structurally metastable but may be widespread in low-temperature environments like lake sediments.
The Magnetic State of Mineral Grains
When magnetic particles are small enough ( < 111m or thereabouts), they are
monodomain; each particle has a magnetization equal to the spontaneous
445
magnetization and cannot be demagnetized. This is the state of the particles

developed for man-made recording media. The direction of the magnetic
moment within the particle is stable (in the absence of a remagnetizing field) for
a time which is of the order of the relaxation time fo 1exp (Ku vjkT) where
f-01 '" 10- 10 _10- 9 s, Kuv is the barrier which the magnetic moment in the grain
of volume v must overcome to reverse its magnetization, and kT is average
thermal energy. Thus, as v decreases the magnetization may not be stable over
the time of interest and the particle becomes superparamagnetic. The variations
of the relaxation time with a time-varying T, v and Ku are central to mechanisms
for the acquisition of weak-field remanence in nature. An applied field also alters
the barriers to magnetization change and hence alters the relaxation time, and
accounts for the imprintation of recording in man-made media under conditions
which, in contrast to nature, correspond to constant T, constant microstructure,
and constant composition (hence constant Ku). The magnetization process in
particles which are too large to be mono domain is also governed by barriers to
magnetization change. These barriers oppose the motion of domain walls,
oppose the nucleation of domain walls at the surfaces of particles, and generally
oppose the transformation of one style of spin structure to another. Fine
particles, large enough to contain spin structures which are incoherent, have
smaller moments than the smaller monodomain particles. They are thus less
suitable for magnetic recording. The spin structures in such particles have been
studied intensively by rock magnetism researchers, because magnetic minerals
in the relevant particle size are abundant in rocks, and because it came to be
generally believed that the fraction of mineral particles in the stable monodomain state was too small to account for the intensity of the stable remanent
magnetization in rocks. It was felt that particles above and near the monodomain size must be able to carry remanent moments comparable in intensity
and stability to the mono domain state.
The study of the magnetism of rocks and minerals has inspired research into
many aspects of materials and physical processes. Prominent among these is the
spin structure and magnetization of fine particles above the mono domain size;
indeed the interest in this topic remains as intense now as it was 35 years ago
when the term pseudo-single-domain was coined. Among the many topics
competing for a place in this chapter, some aspects of the work involving the
spin structure in fine particles have been chosen to give the flavor of current rock
magnetism research.
Theoretical Work. Micromagnetic calculations are concerned with finding the
spin structures which correspond to minima in the free energy of a magnetic
particle. Contributions to the free energy come from the exchange energy, Eox,
the magnetocrystalline anisotropy energy, E anis , and the magnetostatic selfenergy E solf . In the presence of a magnetic field the magneto static energy due to
the field, Ems, must also be included. A coherent spin structure is favored in
minimizing Eex and E anis , and an incoherent structure reduces E self . A starting
point to micromagnetics calculations can be made by assuming a combination
446
of coherent and incoherent regions, in the simplest form an array of lamellar

domains, with direction of magnetization alternating by 180, separated by
lamellar domain walls with moments in the planes of the lamellae and at right
angles to the domain moments. The number and thickness of the walls can be
varied to minimize the total energy for a given particle size and shape. For cubes
of Fe 3 0 4 the calculated size above which the energy of the monodomain state
exceeds that of two-domain (2D) state is 0.08 11m. The 2D-3D and 3D-4D
transitions occur at 0.15 11m and 0.3 11m. Within the size zone for a given domain
multiplicity (say 2D), the relative volumes occupied by the walls and the
domains vary, so that thick walls and thin domains at the lower end of the zone
give way to thin walls and thick domains at the upper end of the zone. The thick
walls will have moments comparable to the domains. For small odd numbers of
domains or walls, the net moment of domains or walls be significant; as the
multiplicities of domains and walls increases, the resultant moment from either
source is reduced.
Calculations can be made by methods which do not require the assumption
that the lamellar structure is composed of 180 domains with wall moments at
right angles. Such calculations again show that a particle of nominally 2D size
could be largely filled by an incoherent spin structure (a "wall"), and in addition
have the angles by which the spins rotate with increasing distance coordinate
going beyond 180 in one "domain" and below 0 in the other. These "overshoots" reduce the domain wall moment. A further result of such calculations is
that, although a given multiplicity of domains may represent the lowest possible
energy for the particle, the particle may be in different stable state (say with fewer
domains) with higher energy. The particle cannot achieve the lower energy
minimum because a potential barrier (the work done to construct a domain wall
at the surface) must first be overcome (Fig. 114). After the nucleated wall has
0
Outside
Wall
Inside
position
Fig. 114. The calculated work done to

build a sixth domain wall (in a particle
which contains five domains) is offset by a
reduction in the magnetostatic self-energy
once the wall migrates into the body of the
particle. The height of the barrier is much
greater than average thermal energy and
the nucleation of walls in real particles is
believed to be sanctioned by surface defects. (After Moon and Merrill 1985)
447
propagated into the interior, the reduction in Eself brings about a net saving in
energy. Thus a particle of a given size may be found in one of several energy
minima, each corresponding to a certain number of domains, separated by
potential barriers from each other and from the lowest energy state.
Finally, using supercomputers, it is possible to carry out unconstrained
calculations of the free energy of small crystals. These calculations produce a
variety of different nonuniform structures with energies and magnetic moments
much less than lamellar structures.
Experimental Studies. The intersection of an inhomogeneous spin structure with
the (polished) surface of a particle can be studied by the interaction of the
nonuniform leakage field and the fine magnetic particles suspended in a
ferrofluid ("Bitter patterns"). Figure 115 shows the observation of the stable
monodomain state, induced by the application of a saturating field, in a
pyrrhotite particle which is also stable in the 2D state. The difficulty the particle
has in nucleating a domain wall, and the consequent stability of the me . :stable
monodomain state, is indicated by the high back-field (43 kA m -1) necessary to
nucleate a domain wall. The nucleation field is great enough to drive the
nucleated wall past the internal domain wall barriers to reverse the magnetization in a single Barkhausen jump. On reduction of the back field to 40 kA m - 1 a
wall nucleates and migrates back into the particle.
The potential barrier which prevents domain wall nucleation (Fig. 114) may
be reduced locally by surface defects. The probability of occurrence of such
defects can be described by Poisson statistics. It has been observed that the
number of particles f(n) containing (n - 1) successfully nucleated walls, and
hence n domains, in a population of small pyrrhotite particles in a state of
saturation remanence, is well described by f(n) = (fi - It -1' exp(1 - fi)/(n - 1)!,
where fi is the mean number of domains per particle in the population. If the
mean number of domains is given by n = (L/LJ1 /2, where L is the particle size
NRM
Mrs
H = -43 kAm-1
H = -40 kAm-1
Fig. lIS. Observations of domain structure is a small pyrrhotite particle. a In the state of
natural remanent magnetization (NRM) the particle accommodates a domain wall presumably nucleated at high temperature. b After application and removal of a saturating field,
the particle is unable to nucleate domain walls and is left in the monodomain state. c A back
field of - 43 kA m - 1 causes a domain wall to nucleate and cross the particle in a single jump
to produce a reversed magnetization. d Relaxation of the back field to a value of - 40 kA m - J
allows a domain wall to nucleate and migrate into the particle. (After Halgedhal and Fuller
1983)
448

Fig. 116. Variation of the
log of coercive force with
the square root of particle
size for monoclinic pyrrhotite. This linear relationship
may be suggestive that domain wall nucleation plays
a dominant role in the magnetization process in this
mineral
60
50
'E
40
""
<II
2
<II
>
'0
30
20
3
Root mean grain size
L1/2 (~m 1/2 )
and Lc is the critical size for the monodomain/multidomain transition, then the
number of particles in the monodomain state, in a saturated assemblage of
particles, is proportional to exp{ - (L/Lc)1/2}. The form of the grain size
dependence of magnetization process parameters in pyrrhotite fine particles
(Fig. 116) may, therefore, be suggestive of the importance of domain wall
nucleation in the magnetization process of this mineral.
Application to the Magnetism of the Earth's Crust. The submarine crust reveals
an interesting and fruitful convergence of geomagnetism and tectonics. One
aspect which has intrigued rock magnetists is the decay in amplitude of the
magnetic stripe anomalies, and the directly observed fall in remanence intensity
of recovered basalts, with increasing age. The source of the decay is believed to
be submarine weathering (maghemitization), but the precise connection between
the course of alteration and the decrease in magnetization is uncertain. The
effect of compositional change on the intrinsic properties (principally Ms) seems
unable to account for the 90% fall in remanence intensity. The effect of the
microstructural consequences of maghemitization on the spin structure within
the particles must therefore be invoked as the cause of the fall in remanence
intensity. Maghemitization results in a decrease in lattice parameter (Fig. 112)
and overall shrinkage of the crystal lattice. A heterogeneously maghemitized
titanomagnetite, therefore, acquires an outer oxidized mantle stretched over an
un oxidized core. The mechanical failure of the mantle results in the shrinkage
cracks observed in the larger ( > 5.um) titanomagnetite grains of submarine
449
ttttttttt
t t t t t 1t t t t t t t
t t t 1 t 11t 1 t 1 t t 11
11111 t t t 1 t 1 t 11t
tttt1ttt111t1t1
11t11t1ttt1tt
t1tttttt11
Fig. 117a, b. Postulated spin structure in a model titanomagnetite grain which has undergone
partial maghemitization to produce a strained outer mantle. The incoherent spin structure (a)
may have a reduced energy compared to the coherent monodomain structure (b) especially in
grains which lie just below the monodomain/multidomain transition before the growth of the
strained mantle
basalts. Smaller grains, which include the most potent carriers of the paleomagnetic record, accommodate the shrinkage-induced strain without cracking.
The strained mantle of the grain now carries induced magnetic anisotropy strain anisotropy - and a homogeneously magnetized monodomain grain now
has increased magnetic energy. Other, incoherent, spin structures with symmetry in harmony with the mechanical state of the strained grain may now have
lower energy than the monodomain structure. Figure 117 shows a hypothesized
spin structure for a model, heterogeneously maghemitized, grain. Calculations
show that this structure will have lower energy than the coherent spin structure,
especially for large monodomain particles. The falling magnetic moment of the
progressively smaller coherently magnetized core provides a plausible explanation for the fall in intensity of submarine basalts with increasing age and degree
of maghemitization.
References
Dunlop OJ (1990) Developments in rock magnetism. Rep Prog Phys 53: 707-792
Halgedahl S, Fuller M (1983) The dependence of magnetic domain structure upon magnetization
state with emphasis upon nucleation as a mechanism for pseudo-single-domain behavior.
Moon TS, Merrill RT (1985) Nucleation theory and domain states in muItidomain magnetic
material. Phys Earth Planet Int 37: 214-222
O'Reilly W (1984) Rock and mineral magnetism. Blackie, Glasgow (Chapman & Hall/Methuen,
New York), 220 pp
450

and Magnetomineralogical Processes.
Magnetic Properties and Geothermometry.
Y.. I. TRUKHIN and F. HELLER
The formation of rocks proceeds in the presence of the geomagnetic field (He)
that permeates through the Earth, ocean, and atmosphere and affects animate
and inanimate nature. In ferromagnetic minerals included in rocks, the natural
remanent magnetization (NRM) is formed under the action of He' these
minerals becoming the source of an anomalous geomagnetic field. The NRM is
carried commonly by Fe-Ti oxides such a magnetite (Fe 30 4 ) with a Curie
temperature Tc = 575C and a spontaneous magnetization Ms = 92 Amz/kg
at room temperature, maghemite (y-Fe Z 0 3) which is unstable above 350 C, with
an extrapolated Tc ~ 700C and Ms = 85 A m Z/kg, minerals of the two solid
solution series: magnetite-ulvospinel (Fe 3 _ xTi x 0 4 with 0 ~ x:-:::; 1; titanomagnetite series) and hematite-ilmenite (Fez _ y TiP3 with 0 :-:::; y :-:::; 1; hemoilmenite series) whose ferrimagnetic properties are suppressed with increasing
content of titanium. Specific properties are found in anti ferromagnetic hematite (IX-Fe 2 0 3) exhibiting weak ferromagnetism due to noncollinear or canted
spin arrangement in the antiferromagnetic sublattices, its Tc = 675C, Ms ~
0.04 A m 2 /kg.
According to the basic hypothesis of paleomagnetism, the NRM of rocks
reflects the geomagnetic field polarity state at the time of the formation of a rock.
Therefore, in general, normally and reversely magnetized rocks are due to the
numerous geomagnetic field inversions which occurred during the geological
history.
Unmixing, oxidation, and ex solution complicate composition and structure
of the rock forming Fe-Ti oxides thereby changing their magnetic properties,
too. These processes take place in the ambient geomagnetic field and are called
magnetomineralogical processes. They initiate evolution of microstructures in
the Fe-Ti oxides which in turn affect the NRM formation and hence that of
anomalous geomagnetic fields. One of the possible consequences of magnetomineralogical processes is an anomalous magnetization of rocks which is
imprinted antiparallel with regard to He and is referred to as self-reversal of
NRM. The presence of rocks with self-reversed NRM changes the morphology
of geomagnetic anomalies and may provoke erroneous paleomagnetic interpretations. In addition to the Fe-Ti oxides, Fe sulfides like greigite, smythite, or
pyrrhotite are potential candidates for self-reversing mineral properties.
It has been shown theoretically that magnetization self-reversal can occur
both in one-phase and two-phase (multi-phase) ferromagnets. The one-phase
self-reversal is realized only in ferromagnetic material with an anomalous
temperature dependence of spontaneous magnetization (N-type dependence).
When such a ferromagnetic mineral is cooled from T;:::.: T c' its Ms direction
451
changes by 180 at a certain temperature T k, the compensation temperature. As

a result, the thermoremanent magnetization (TRM) of the ferromagnet will be
antiparallel to H when it is cooled to room temperature in a moderate external
magnetic field H (H < He' where He is the coercive force).
Self-reversal due to anomalous N-type Ms(T) dependence was observed
in one-phase chrome-lithium and other synthetic ferrites. In nature, however, it
is unlikely to occur, since no N-type minerals have been found so far with
Tk > 20e. In natural one-phase ferromagnetics of this type, the self-reversal is
supposed to take place due to low-temperature ionic re-ordering of cations in
magnetic sublattices which leads to a sign change of the resulting Ms below T k'
In two-phase ferromagnets, the magnetization self-reversal occurs as a result
of a negative (exchange or magneto static) interaction between the phases, the
exchange interaction being several orders stronger than the magnetostatic one.
In the magnetization sequence of such a two-phase ferromagnet, phase 1
acquires a magnetization M 1 in the direction of H whereas phase 2 acquires a
magnetization M2 which is antiparallel to H, due to negative interaction with
phase 1. IfM2 > Ml at room temperature, the resulting magnetization M = Ml
- M2 will be reversed with respect to H. This self-reversal is referred to as a
complete reversal (Fig. 118). The self-reversal is partial (Fig. 119), ifMl > M 2; in
this case M = Ml - M2 will be parallel to H, but its value will be less than that
of M = Ml + M2 that would occur, if the negative interaction were absent.
Self-reversals ofNRM observed in rocks are connected mainly with two- and
multi-phase structures of ferromagnetic minerals. Most volcanic rocks have an
NRM of thermomagnetic origin whereas in some cases the NRM ;s due to
partial or complete crystallization remanent magnetization (CRM). A TRM selfreversal may proceed during thermomagnetization of rocks, if the interacting
phases have been created at higher temperatures, i.e., prior to the formation of
the TRM. Upon cooling, the phase with higher Te is the first to be magnetized.
Self-reversal can also occur after the formation of TRM as a result of lowtemperature growth of a new phase with ferromagnetic properties. In this case it
is not a self-reversal of TRM but that of crystallization magnetization formed
during growth of the new phase. Here Te of the new phase may be either higher
or less than Te of the primary phase. After self-reversal the total NRM will
consist of two components: TRM + CRM.
Partial self-reversal ofTRM due to the interaction of two phases is observed
in natural titanomagnetites with signs of a spinodal decomposition of the solid
solution. The effect takes place either during thermo magnetization of the
samples in the natural state or after previous laboratory treatment at temperatures between 600 and 700e. Titanomagnetites which are stable at high
temperatures decompose at T :::;; 500 C into phases near the end members,
magnetite and ulvospinel, of the solid solution series. Spinodal decomposition is
the alternative process as compared to discontinuous exsolution due to nucleation in a homogeneous matrix. Regardless of its mechanism, the unmixing
process goes towards a reduction of the total free energy of a mineral. The
ex solution mechanism determines its kinetics only. During spinodal decomposi-
452
-0.6
__- L_ _ _ _ _ _L -_ _ _ _ _ _
Heating
_ _ _ _~_ _ _ _L -_ _~
Heating
Cooling
90,---------------------------------------.
~ 360
.~
~~
270
~
180-
90~--~------~--------~--~----~----~
100 165 100
11
100
200
300
400
Temperature (DC)
90
E:l
45
::J
QI
.E:l
.:::
\J
.::
0
-45
-90
Fig. 118. Intensity, inclination, and declination of NRM during thermal cycling in air and zero
magnetic field of an andesitic sample from the Nevado del Ruiz (Colombia) eruption in 1985
showing complete self-reversal. Heating and cooling cycles indicated
4.0
~
~
~
2.0
200
400
T(ee)
600
Fig. 119. Partial self-reversal of TRM in a Siberian

trapp sample. Continuous thermal demagnetization of
TRM during repeated (1-4) heating cycles. Applied
field H = 80Am- '
453
Fig. 120. Solvus (1) for the system Fe30cFezTi04 after

Kawai (1956) and coherent spinodal temperature (2)
600
400
200
60
40
20
Fe 2Ti04 (mole %)
tion, slight fluctuations of the composition appear at first. They are associated
with much less activation energy as compared to that of nucleation. The
sinusoidal waves of fluctuations simultaneously propagate through the whole
structure. With time the composition fluctuations are intensified in wavelength
and amplitude, until eventually the crests and nodes of the waves become two
separate phases. Spinodal decomposition is most likely to occur in solid
solutions with similar structures of end members, magnetite, and ulvospinel
being such members in the case of titanomagnetite exsolution. Coherent stresses
that appear during unmixing, due to the emergence of regions with slightly
different chemical composition and lattice parameters, limit the amplitude of the
composition fluctuations. In the composition-temperature diagram (Fig. 120)
the region of spinodal decomposition is to be found within the coherent spinodal
temperature range. The spinodal decomposition temperature is referred to as
the spinodal temperature Tsp"
Electron microscope studies have shown that the exsolution structures in
titanomagnetites are 3D lattices in regions (enriched or depleted in titanium) of
alternating directions [100]. The dimensions of these regions range from 10 to
1000 nm or more. There are structures of secondary finer exsolution in the
ulvospinel regions. At the early stages of unmixing, shorter periods of recurrence
and "magnetite" regions of cubic shape are observed, the latter becoming
stratified at the late coarsening stages and arranging themselves parallel to the
(100) planes.
Since spinodal decomposition proceeds very slowly, it cannot be completed
in quickly cooled geological bodies. In very slowly cooled bodies the process
goes practically to completion forming a ferromagnetic phase that is close to
magnetite and a non-ferromagnetic phase that is close to ulvospinel. In order to
promote the formation of magnetically interacting phases, the exsolved solution
should be partially homogenized. In the laboratory this homogenization is
facilitated by heating to 600 C-700 0c. During thermomagnetization of partially homogenized titanomagnetite in H ::;; 80 A m -1 a weak, probably magnetostatic interaction appears between the Ti poorer and Ti richer phases. The Ti
454
poorer phase with a higher T ep than T er of the Ti richer phase is the first to
become magnetized.
At T < T er the Ti richer phase is magnetized in the effective field H - Hp
which acts anti parallel to H under the condition that the field of the Ti poorer
phase is Hp > H. In titanomagnetites, Ms decreases with increasing Ti content.
Therefore during the spinodal decomposition of titanomagnetite a partial selfreversal of TRM may be observed which in turn indicates the spinodal
decomposition. When heating to 600-700 C is repeated many times, the selfreversal properties disappear. This can be accounted for by the fact that the solid
solution becomes a one-phase solution as a result of homogenization. A similar
partial self-reversal was observed during spinodal decomposition of titanomagnetites containing magnesium and chromium. The spinodal decomposition
affects the magnetic properties resulting in self-reversal and increasing stability
ofTRM due to separation of unmixing phases. Also there is an opposite effect of
ferrimagnetism of titanomagnetites on the spinodal decomposition of the latter.
This is associated with the fact that a decrease in free energy kT sp during
ex solution is comparable to the energy of magnetic ordering k Te. This effect is
revealed in the violation of the spinodal symmetry.
Complete and partial self-reversal of NRM has been observed in titanomagnetites contained in continental and oceanic basalts and affected by lowtemperature oxidation. In fields H.::; 800 Am - 1, oxidized cation-deficient
titanomagnetite (titanomaghemite) with an oxidation degree z ranging from 0.52
to 0.66 (Te ~ 400C) may acquire a CRM that is antiparallel to H due to
magnetic interaction with the primary titanomagnetite with Te around 180C.
There may be either complete or partial self-reversal of NRM in consequence of
the ratio of the components: normal TRM and reversed CRM. When reaching a
high oxidation degree (z > 0.6), exsolution of titanomagnetite continues and
may also be accompanied by self-reversal. The transformation of titanomagnetite into hemoilmenite, which is found in oceanic basalts, may lead to a complete
self-reversal.
The most recent observations ofNRM self-reversal come from magnetomineralogical studies of kimberlites and associated trapps of the Siberian platform
and andesitic to dacitic rocks of different provenance. In kimberlites and trapps
the NRM is carried by a variety of different minerals such as picroilmenite,
a member of the solid solution series FeTi0 3 -MgTi0 3 -Fe z0 3 with small
amounts of Cr Z 0 3 and Al z0 3 , magnetite, maghemite, titanomagnetite, chromium-bearing titanomagnetite and other ferrispinellides, as well as iron hydroxides (mainly goethite) and iron sulfides (pyrrhotite).
During thermal treatment in the laboratory, various transformations of the
ferromagnetic minerals contained in kimberlite and trapp samples were observed: maghemite into hematite, titanomaghemite into magnetite with ilmenite
lamellae, pyrite into pyrrhotite, pyrrhotite into magnetite and partial homogenization of unmixed members of the titanomagnetite series. The initial composition of the ferromagnetic minerals in kimberlites and trapps and their transformation during and after rock formation can be determined by the analysis of
455
high-temperature magnetomineralogical processes. The presence of minerals of

the maghemite-magnetite series indicates that the oxidation took place at high
temperatures and proceeded during rapid cooling. A high content of isomorphous impurities in ferrispinellides as well as the fringing of ilmenite grains which
contain ex solved lamellae of ilmenohematite, indicates slow cooling from high
tern pera tures.
Complete self-reversal of TRM was found first in the hemoilmenites of the
Haruna dacite (Japan) and later in the NRM of thermal origin of other rocks
such as andesitic pyroclastics of the Nevado del Ruiz (Colombia) 1985 eruption
(Fig. 118). In the laboratory, the maximum fields in which the effect can be
measured in hemoilmenites, do not exceed 1000 Am -1. With further increasing
applied field or upon annealing at 700C, the effect is suppressed or disappears.
An analogous complete self-reversal ofTRM in observed in kimberlites containing picroilmenites that are stable when heated to 350C. The reversed TRM
appears upon cooling from 350 to 20C in magnetic fields up to 320 Am - 1.
Depending on composition, the Curie points of the hemoilmenites and picroilmenites vary between 150 and 250-300 0C. The TRM self-reversal in hemo- and
picroilmenites has been argued to be due to both exchange interaction of
magnetostatic interaction of a grain matrix with hematite-like micro inclusions
whose Curie point is higher than that of the matrix. Negative magnetostatic
interaction is compatible with the small fields needed to suppress the selfreversal, but works under very restricted geometrical conditions only. On the
other hand, the strong negative exchange coupling between two phases is not
influenced by small applied fields. Therefore domain wall nucleation and
subsequent wall movement in the matrix as a function of the effective field have
been introduced recently to explain the low suppressing fields.
The ferromagnetism of the Siberian trapps is determined by minerals of the
solid solution Fe304-(Fe,Mg)2 Ti0 4, this series being at different stages of
exsolution. Some trapps contain low-temperature oxidized titanomagnetites.
Partial self-reversal of TRM is observed in trapp samples which contain the
products of spinodal decomposition after thermal treatment at T = 700C in
fields H S 80 Am -1 (Fig. 119).
Although NRM self-reversal has been found only in a small fraction of the
rock samples examined, the possibility of remagnetization of rocks as a result
of magneto mineralogical self-reversal processes is of principal importance for
magnetic prospecting, paleomagnetism and those branches of geology and
geophysics where paleomagnetic interpretations are widely used. The presence
of self-reversed NRM in rocks may lead to ambiguous conclusions, since it may
result in a change of the sign of geomagnetic anomalies or in a wrong estimate of
the actual number of geomagnetic polarity inversions. It is interesting and
paradoxical to note that self-reversal is as a rule observed in reversed rocks,
although it should be exhibited with equal probability in rocks of both normal
and reversed polarity. Moreover, reversed rocks are characterized statistically
by a higher oxidation degree of titanomagnetites and a higher stability of
NRM.
456
Composition and structure of ferromagnetic minerals and their magnetic

properties strongly depend on temperature. There is a possibility to use
magnetomineralogical data to determine the temperature of certain geological
processes. Geothermometers have been suggested that are based on the temperature and oxygen fugacity dependence of the equilibrium of ulvospinel-magnetite and ilmenite-haematite solid solutions. Due to the complexity and
ambiguity of oxidation exsolution processes in titanomagnetites, however,
the application of such geothermometers does not always give satisfactory
results.
The TRM of igneous rocks itself, however, may serve as a reliable geothermometer. The TRM follows the law of additivity of partial thermomagnetizations
(PTRM), i.e., TRM is the sum of PTRMs formed in consecutive temperature
intervals upon cooling from T c to room temperature To. As a first approximation, each PTRM is destroyed upon heating to the highest temperature of the
interval it was formed in. Making use of this TRM property, the temperatures of
secondary heating events in the history of a rock can be estimated under the
conditions that the heating temperature did not exceed the maximum blocking
temperatures of the TRM carrier and that the paleomagnetic field had changed
direction since the primary magnetization had been induced. In this case, the
measured NRM will be the vectorial sum of two PTRMs with different
directions. Subsequent thermal demagnetization of the rock changes simultaneously intensity and direction of the NRM until a temperature is reached, above
which no variation of the magnetization direction takes place. This temperature
can be related to the temperature of the secondary heating event if corrections
for laboratory and geologic heating times are taken into account. As an
example, the temperatures of secondary metamorphism in the Yakutia kimberlites of Siberia were calculated in this way.
References
Buddington AF, Lindsley DH (1964) Iron-titanium oxide minerals and synthetic equivalents.
J Petrol 5: 310-357
Haag M, Heller F, Carracedo JC, Soler V (1990) Remanent magnetization of andesitic and
dacitic pumice from the 1985 eruption of Nevado del Ruiz (Colombia) reversed due to selfreversal. J Volcan Geothermal Res 41: 369-377
Haggerty SE (1975) The chemistry and genesis of opaque minerals in kimberlites. Phys Chern
Earth 9: 295-308
Heller F, Petersen N (1982) Self-reversal explanation for the Laschamp/Olby geomagnetic
field excursion. Phys Earth Planet Int 30: 358-372
Hoffman KA (1975) Cation diffusion processes and self-reversal of thermoremanent
magnetization in the ilmenite-hematite solid solution series. Geophys JR Astr Soc 41: 65-80
Kawai N (1956) Subsolidus phase relation in titanomagnetite and its significance to rockmagnetism. Proc 20th Int Geol Congr 11 A: 103-120
Khisina NR (1987) Subsolidus transformations of solid solutions of rock-forming minerals.
Nauka, 207 pp
Lawson CA, Nord GL, Champion DE (1987) Fe-Ti oxide mineralogy and the origin of
normal and reverse remanent magnetization in dacitic pumice blocks from Mt. Shasta,
California. Phys Earth Planet Int 46: 270-288
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor, and Plate Tectonics
457
Pullaiah G, Irving E, Buchan KL, Dunlop OJ (1975) Magnetization changes caused by burial
and uplift. Earth Planet Sci Lett 28: 133-143
Readman PW, O'Reilly W (1971) Oxidation processes in titanomagnetites. Z Geophys 37:
329-338
Ryall PJC, Hall JM (1979) Laboratory alteration of titanomagnetites in submarine pillow

lavas. Can J Earth Sci 16: 496-504
Scherbakov YP (1988) The influence of magnetic transformations upon unmixing of titano
magnetites. Izv AN SSSR Fiz Zem 10: 50-53
Smith PPK (1980) Spinodal decomposition in a titanomagnetite. Am Mineral 65: 1038-1043
Trukhin VI, Zhil'ajeva VA, Zinchuk NN, Romanov NN (1989) Magnetism of kimberlites and
trapps. Moscow University Press, 165 pp
Uyeda S (1958) Thermo-remanent magnetism as a medium of palaeomagnetism, with special
reference to reverse thermo-remanent magnetism. Jpn J Geophys 2: 1-123
6.6.3 Paleomagnetism, Magnetic Fields of the Ocean Floor,

and Plate Tectonics
H.C.
SOFFEL
and
D.l. DUNLOP
Paleomagnetism
Almost all rock types possess a natural remanent magnetization (NRM) carried
by natural ferrimagnetic minerals, the most important of which are magnetite,
titanomagnetite, hematite, and pyrrhotite. With the help of field tests and
laboratory cleaning procedures (Collinson 1983), the primary part of the NRM
can be isolated from secondary NRM overprints. The direction of the primary
NRM vector (described by its inclination or dip I and its declination D with
respect to present north) records the local geomagnetic field at the time and
place the rock formed (or was metamorphosed, in the case of high-grade
metamorphic rocks) in the geological past.
Early work in paleomagnetism investigating the geometry of the ancient
geomagnetic field showed that the field, when averaged over several tens of
thousands of years, approximated that of a geocentric dipole aligned with the
Earth's rotation axis. In this case, the geomagnetic and geographic poles
coincide and D = 0 everywhere on the Earth's surface. Field inclination I is
related to latitude A. by A. = tan - l(! tan I), allowing the paleolatitude of a site
to be calculated from the NRM inclination. Rotations of a geological unit, a
tectonic block, or even a continent are recorded by nonzero NRM declinations.
A common way of storing the NRM paleodirectional information embodied
in (D,I) is to report the computed paleomagnetic pole, which is the position, in
present geographic coordinates, of the ancient north pole or spin axis. Time
sequences of paleomagnetic poles, or simply paleopoles, form apparent polar
wander paths (APWPs), which record the drift history of rigid lithospheric
blocks relative to the spin axis. APWPs commence at the present geographic
north pole and radiate away from it along different paths. Figure 121 shows
458

Fig. 121. Simplified apparent
polar wander paths of the major
continental plates for the last
300 Ma, based on a compilation
by Irving and Irving (1982).
Conventional abbreviations are
used for geological periods.
simplified APWPs of the major continental blocks of the last 300 Ma, based on
the data compiled by Irving and Irving (1982).
By rotating continental blocks so as to bring the pre-180 Ma parts of their
APWPs into coincidence, one can deduce the relative positions of the different
blocks in the supercontinent Pangea, which existed until the opening of the
Atlantic Ocean. For times earlier than 300 Ma, the APWPs are more complicated and are also different for subunits of the present continents, showing that
Pangea assembled from a different set of continental blocks than those we
see at present. Paleocontinental maps based on paleomagnetic data are given by
Smith et al. (1981), Irving (1981,1983), and Van der Voo (1988). The pre-300-Ma
reconstructions are tentative and uncertain.
Another important feature of the geomagnetic field is its frequent reversal of
polarity. The reversal process is brief (4-10 ka) compared to the duration of a
polarity epoch or time between major reversals ( ~ 1 Ma). The geometry of the
geomagnetic field during a reversal (switching of the dipole, growth and decay of
axial and equatorial multipoles) is still controversial (Hoffman 1988). The field
intensity during a reversal seems to decrease to 10-20% of its usual intensity;
such a reduction in geomagnetic shielding would allow an increased penetration
of solar radiation to the Earth's surface, although atmospheric shielding is more
important.
The geomagnetic polarity time scale is known with high precision for the last
5 Ma. The principal polarity epochs (or chrons), named after prominent geomagnetists, are interrupted by short reversal events (subchrons, named after type
localities). The most recent major reversal, about 0.7 Ma ago, marks the
transition from the Matuyama reversed chron to the (present) Brunhes normal
chrvn (Fig. 122). There are fragmentary indications of several short reversal
events and excursions (incomplete reversals) during the Brunhes. Evidence of
Age [106 0J Events
0_
-laschomp
0.70
0.87
0.92
Jaramillo
1.58
1.71
Gilsa
1.86
Olduvei
2.02
Reunion
2.17
2.41
2.84
2.92
2.99
3.09
Keena
Mammoth
3.l2
3.72
3.82
3.97
4.14
U3
4.45
Cochiti
Nunivak
Sidufjall
4.60
lhvera
4.81
5.30
459
Fig. 122. Geomagnetic polarity time scale for the last 5 Ma.
(After Hailwood, 1989)
460
global synchroneity in these events is lacking, however. They could be manifestations of reversed magnetic flux in local regions of the Earth's outer core, rather
than reversals of the entire core dynamo which is believed to generate the
geomagnetic field.
The polarity time scale for the last 160 Ma has been established mainly from
the sequence oflinear magnetic anomalies over actively spreading oceans, as will
be discussed in the next section. Polarity time scales for earlier times (before the
birth of the present oceans) are based on reversal sequences in radiometrically
dated lava flows and sedimetary successions on land. Reversal records become
less continuous and less accurately dated with increasing age (see Hailwood
1989 and Harland et al. 1982 for compilations). Polarity reversals are also
recorded by Precambrian rocks, suggesting that geodynamo action in the
earth's liquid core was already active early in geological history.
Magnetic Fields of the Ocean Floor
During the 1950s and early 1960s, oceanographic research expanded dramatically, in part at least because of improved instruments for geophysical remote
sensing and for positioning of research ships and aircraft. Measurement of the
geomagnetic field over the oceans with high precision and spatial resolution by
shipboard and airborne magnetometers revealed strikingly linear magnetic
anomaly patterns, particularly near mid-ocean ridges. The interpretation of
these magnetic lineations or stripes is based on the model of seafloor spreading
(Vine and Matthews 1963). Rigid seafloor plates, created at the ridge when
intrusive and extrusive magmas cool and acquire NRM in the geomagnetic field
direction, subsequently spread laterally at constant velocity (the plate velocity:
see following section), symmetrically about the ridge. Reversals of NRM due to
reversals of the field result in bands of alternately magnetized seafloor paralleling the ridge. The fields created by these normal and reverse bands produce
corresponding anomalies in the total field, which are linea ted parallel to the
ridge. Vine and Matthews' interpretation, which ushered in the era of plate
tectonics and was a milestone in the history of Earth Sciences, was made
possible by the developing knowledge of geomagnetic reversals, based at that
time on Kj Ar-dated lava sequences on land.
Figure 123 shows a profile oflinear magnetic anomalies across the Southeast
Indian Ridge between Australia and Antarctica, combining the observed profile
(the anomaly in the total intensity of the local geomagnetic field measured at the
sea surface), a model anomaly profile assuming a constant spreading rate of
68 mm/a, the block model for magnetization of the underlying seafloor (black:
normal polarity; white: reversed polarity), the polarity time scale (cf. Fig. 122),
and the age of seafloor and distance from the ridge. The striking coincidence
between the mostly land-based polarity time scale for this age interval (Fig. 122)
and the time scale developed from marine magnetic anomalies and their
461
OBSERVED
PROFILE
SYNTHETIC
PROFILE
(assuming
68 mm/year
spreading)
MARINE MAGNETIC
ANOMAL Y NUMBER
llT.......h_-.-.rn..-~...
SEAFLOOR
.. MAGNETIC POLARITY
REVERSAL TIME SCALE
5.4 5.0
I
3.0
I
100
2.0
1.0
1.0
2.0
3.0
I
100
4.0
II
5.05.4
I I
AGE (Me)
DISTANCE (Km)
Fig. 123. Seafloor spreading model for a magnetic anomaly profile from the southeastern
Indian Ocean. (After Gordon and Acton 1989)
interpretation in terms of seafloor spreading led Heirtzler et al. (1968), among

others, to expand the polarity time scale beyond 5 Ma, using the magnetic
stripes over older seafloor.
Deep-sea drilling projects (DSDP, ODP) began in the 1970s and yielded
further support for the idea of seafloor spreading, for example from the regular
increase in ages of crystalline basement and overlying sediments with distance
from mid-ocean ridges. However, the magnetization of the seafloor turned out
to be less simple as model calculations had assumed. The most important
ferrimagnetic mineral in ocean floor basalts (which carry most of the NRM that
produces magnetic lineations) proved to be a titanomagnetite with mean
composition
It corresponds to an Al-, Mg- and Mn-substituted titanomagnetite of roughly

the composition 60 mol% ulvospinei and 40 mol% magnetite (TM60). Its Curie
temperature Tc ranges from 125C in the un oxidized state to as high as 400C
when highly oxidized. Oxidation increases with distance from a spreading ridge
(i.e., with age), so that the lowest Tc values are found close to the ridge axis while
high Tc values are typical for distances of 100 km or more (Bleil and Petersen
1983).
60'
lO'
50'
2.3
00~3
'5.9 I]
'54
"'-...
~7
00
-,~
#u
...
PAC
""
"8
0
"'"
~82~
00
~gg"
Q
Dr
60'
""
~~
33
~
'" 6
41.7
3.5
10
jf#f'6 1.6
-;i9
-rg
37 ~
o~~
0.2
~OC.6 A'zrt-"~
":25
_2.5
':"'27
2J
60
0~1
-.;
d>
'1.6
dg
'Y25
IND
17
67
7.2
ANT
tl6
7.5
oj.
0~
\1
~)if
""1.6
F5
EUR
~.
oj:.
t;;"
...'"
5-
'"0-,
(j)-
'"
::l.
'0
..."d
?'
;;
...
'0
::r
(j
0'\
N
463
Plate Tectonics
During the 1960s, a combination of seismic data (global distribution of earthquakes and the determination of focal mechanisms of suboceanic earthquakes)
with paleomagnetic data (APWPs of continents and spreading of seafloor
derived from linear magnetic anomalies) made a strong case in support of
Wegener's hypothesis of drifting continents. The hypothesis was further supported, although not so directly, by geological evidence and the model calculations showing that convection of the Earth's mantle is possible and should
have rates comparable with drift rates of the overlying lithosphere, as deduced
from seafloor spreading. The subdivision of the lithosphere (the Earth's crust
and uppermost mantle) into rigid plates with little or no internal deformation
is now undisputed among Earth Scientists (Fig. 124). Current plate motions
have been summarized by De Mets et al. (1990), Jacoby (1985), and Minster
and Jordan (1978). The highest present plate velocities are about 150 mm/a
(150 km/Ma); average plate velocities are 20-40 mm/a (Fig. 124). Precambrian
APWPs indicate similar drift rates, so that plate velocities have been of the same
order of magnitude for about the last 2500 Ma and the rheology and temperature distribution in the mantle cannot have changed greatly since quite early in
the Earth's history.
Colliding lithospheric plates are now considered to be the main mechanism
for earthquakes and orogenic belts. Higher-density oceanic plates can be
subducted below lower-density continental plates, resulting in oceanic trenches,
Andean-type mountains, and earthquakes at depths up to 700 km. A classical
collision zone of this type is the subduction of the Nazca plate (NAZ in Fig. 124)
under the South American plate (SAM), forming a long, deep offshore trench,
deep earthquakes extending hundreds of km into and beneath South America,
and spectacular volcanism and mountain building in the Andes. Collisions of
two continental plates, neither of which can readily subduct beneath the other
[e.g., the Indian plate (IND) and the Eurasian plate (EUR)J result in Himalayan-type mountain belts of enormous scale.
The concepts of continental drift, seafloor spreading, and plate tectonics,
whose most direct basis and proof is in paleomagnetism, have revolutionized
thinking in the Earth Sciences in the past 25 years. Along with this new picture
of how the surface of our planet has evolved and is presently developing have
come new strategies for averting the consequences of natural disasters like
earthquakes and volcanic eruptions and for tapping new mineral and energy
resources .
Fig. 124. Mercator projection of major lithospheric plates. EUR Eurasian; IND Indian; PAC
Pacific; NAM North American; COC Cocos; NAZ Nazca; CAR Caribbean; SAM South
American; AFR African; ARA Arabian; ANT Antarctic. Open circles, triangles, diamonds
represent earthquake epicentres with increasing focal depths. Arrows with numbers are plate
velocities in em/a. (After Jacoby 1985, adapted and modified from Minster and Jordan 1978)
464
References
Bleil U, Petersen N (1983) Variations in magnetization intensity and low-temperature
titanomagnetite oxidation of ocean floor basalts. Nature 301: 384-388
Collinson DW (1983) Methods in rock magnetism and palaeomagnetism. Chapman and Hall,
London, 503 pp
De Mets C, Gordon RG, Argus DF, Stein S (1990) Current plate motions. Geophys J Int 101:
425-478
Gordon RG, Acton G (1989) Paleomagnetism and plate tectonics. In: James DE (ed)
Encyclopedia of solid earth geophysics. Van Nostrand Reinhold, New York, pp 909-923
Hailwood EA (1989) Magnetostratigraphy. Geol Soc Lond Spec Rep 19, Blackwell, London
Harland WB, Cox AV, Llewellyn PG, Pickton CAG, Smith AG, Walters R (1982) A geologic
time scale. Cambridge Univ Press, Cambridge, 131 pp
Heirtzler JR, Dickson GO, Herron EM, Pitman WC, Le Pichon X (1968) Marine magnetic
anomalies, geomagnetic field reversals, and motions of the ocean floor and continents.
Hoffman KA (1988) Ancient magnetic reversals: clues to the geodynamo. Sci Am 256: 76-83
Irving E (1981) Phanerozoic continental drift. Phys Earth Planet Int 24: 197-204
Irving E (1983) Fragmentation and assembly of the continents, mid-Carboniferous to present.
Geophys Surv 5: 299-333
Irving E, Irving GA (1982) Apparent polar wander paths, Carboniferous through Cenozoic,
and the assembly of Gondwana. Geophys Surv 5: 141-188
Jacoby W (1985) Theories and hypothesis of global tectonics. In: Fuchs K, Soffel H (eds)
Geophysics of the solid Earth, the Moon and the Planets. Landolt-Bornstein, New ser, vol V
2b, pp 298-369
Minster JB, Jordan TH (1978) Present-day plate motions. J Geophys Res 83: 5331-5354
Smith AG, Hurley AM, Briden JC (1981) Phanerozoic paleocontinental world maps.
Cambridge Univ Press, Cambridge, 102 pp
Van der Voo R (1988) Paleozoic paleogeography of North America, Gondwana, and
intervening displaced terranes: comparisons of paleomagnetism with paleoclimatology and
biogeographical patterns. Geol Soc Am Bull 100: 311-324
Vine FJ, Matthews DH (1963) Magnetic anomalies over ocean ridges. Nature 199: 947-949

St.E.
HAGGERTY
The magnetic signatures of igneous rocks are resident in mineral solid solutions
that are defined by the end members magnetite-ulvQspinel (Fe 3 0 4 -Fe 2 Ti0 4 )
and hematite-ilmenite (aFe 2 0 3 -FeTi0 3 ). Compositional variations along these
solid solution joins, in Fe 2 +, Fe 3 + and Ti, control the physical response patterns
which emerge in magnetic property measurements. Temperature, oxygen fugacity, and bulk rock chemistry are the intrinsic parameters which define modal
abundances, the compositions of coequilibrated magnetic oxides, subsolidus
reequilibration paths, and ultimately the magnetic character of the rock.
The magnetic mineralogy of igneous rocks may be broadly defined within
three chemical systems: (1) the oxide system FeO-Fe 2 0 3 - Ti0 2 (Fig. 125); (2) the
sulfide system Fe-Ni-S; and (3) the metal alloy system Fe-Ni-Co. Solid
solutions are present among the mineral end members in each system and
465
magnetic properties vary as a function of the degree of solid solubility

(Table 34). The compositions of individual minerals are controlled by their
initial temperatures of formation, by the presence of solvi along solid solution
joins, by bulk rock chemistry, and by the magnitudes of oxygen and sulfur
fugacities, f0 2 and fS 2 respectively.
Members of the magnetite-ulvospinel (Mt-UsPsJ solid solution series are
the dominant magnetic carriers in igneous and metamorphic rocks. This series
varies in oxidation state (Fe 2+ + Ti ~ 2Fe 3+) and in magnetic structural behavior from ferrimagnetic magnetite to antiferromagnetic ulvospinel (Table 34,
Fig. 125). Mineral compositions, along the join Mt-Usps", vary between felsic
and mafic suites and between extrusive and intrusive units. Cooling rates, bulk
rock chemistry, and the oxidation state of the rock define the magnitude of the
antiferromagnetic or ferrimagnetic component of the unit, and this in turn
determines the quality of the enhancement or the suppression of a magnetic
response signature. The redox state of this solid solution series is the important
chemical variable that influences the magnetophysical character of the rock.
Members of the ilmenite-hematite (Ilm-Hem ss ) series are equally responsive
to redox, bulk rock chemistry, and cooling rate. The series is magnetically
complex with antiferromagnetic ilmenite, an intermediate compositional range
between 0.5 < x < 0.8 along the join xFeTi03-(1 - x)Fe203 which is ferrimagnetic (21 emu/g maximum), and hematite which displays both antiferromagnetism and weak parasitic ferrimagnetism (0.5 emu/g). Hematite-rich constituents
are widespread in felsic suites but decrease in rocks having more mafic affinities.
Minerals within the sulfide system Fe-Ni-S have intrinsically weak magnetic moments. Pyrrhotite, pyrite, or pentlandite, which are the most common
igneous-forming sulfides, therefore, do not make a significant contribution to
the overall magnetic properties of a rock. However, the presence of mineral
sulfides is significant from the standpoint that Fe-Ni-S members may decompose to form metallic alloys by processes of desulfurization (e.g., Fe 7 SS --+ 7Fe
+ 8S; FeNiS (pentlandite) --+ FeNi + S). Although these metal alloy systems,
and those in association with Cu or Co have a restricted distribution, in
ophiolite complexes and in partially serpentinized ultramafic rocks, there is
evidence to suggest that these minerals are major contributors to sources of deep
crustal magnetic anomalies. The high values of saturation magnetization should
be noted (Table 34).
In reversing the application of data obtained from oxide geothermometryoxygen geobarometry determinations, an important first order approximation
in unraveling the source rocks responsible for aeromagnetic anomalies has been
established. These data show conclusively that granitic and rhyolitic suites are
more highly oxidized than those of gabbroic and basaltic suites, and hence the
former are characterized by ferrimagnetic magnetite solid solutions, whereas
the latter are dominated by antiferromagnetic ulvospinel. However, the complexities of solubility and immiscibility in magnetic oxide solid solutions
(Fig. 125), and the contrasts in cooling rates between intrusive and extrusive
suites are compounding factors in magnetic anomaly interpretations. Prolonged
20
FeO
Usp
200
400
600
40
/ '"
60
/--.
\
\
80
"-
Mt
. r ' constont
, \ ), I
'
I to
Fe304
t.:5
roc
I I( I( I (
f (
40
\
60
~-('('
'I'((~
~ft
200
I' (
r:1I~-'----
400
600
I
ox;dot;~ ~ :;;;...---
;:;...--
.j:>.
()
en
...,
s
ro
o
.....,
::l
,,''"
-g
."
"...,
'"...,
'0
::r
~
0\
0\
467

Table 34. Magnetic properties of minerals
Mineral
Composition
Magnetic structure
Ulvospinel
Magnetite
Ilmenite
Hematite
Fe 2Ti0 4
Fe 30 4
FeTi0 3
IlFe 20 3
Maghemite
Pyrrhotite
Iron
Cobalt
Nickel
Awaruite
Wairauite
'l'Fe 20 3
Fe 7 SS
Fe
Co
Ni
Ni3Fe
CoFe
Antiferromagnetic
Ferrimagnetic
Antiferromagnetic
Antiferromagnetic
Parasitic ferromagnetism
Ferrimagnetic
Ferrimagnetic
Ferromagnetic
Ferromagnetic
Ferromagnetic
Ferromagnetic
Ferromagnetic
J,
92
0.5
85
20
220
162
57
110
232
Tc or Tn (0C)
- 153
580
- 190
680
400-500
305
770
1123
358
620
986
J, = saturation magnetization emu/g. Tc and Tn are Curie temperatures and Neel temperatures respectively.
cooling induces mineral ex solution (Fig. 125), and this results in increases in
saturation magnetization, Curie temperature and magnetic stability. Partial
high temperature ( '" 600 0c) oxidation of ulvospinel-rich solid solutions, to
magnetite-rich solid solutions and ilmenite, yields a similar increase in magnetic
properties (Fig. 125). Advanced oxidation, on the other hand, is a magnetically
destructive mineral transformation process which activates the inversion of
ferrimagnetic minerals into minerals having antiferromagnetic and paramagnetic properties (Fig. 126). Exsolution is characteristic of all intrusive suites; partial
oxidation is prevalent in mafic suites (extrusive and intrusive) and less common
in felsic suites (extrusive and intrusive). Although advanced oxidation is typical
of subaerial basalts, high deuteric temperatures ( > 600 0c) are attained and
olivine and pyroxenes are oxidized to form single domain sized particles of
magnetite. Silicate decomposition is prevalent in medium to high grade metamorphic rocks and aeromagnetic signatures may be due entirely to secondary
rather than primary magnetite.
High magnetic susceptibilities and large concentrations of iron oxides are
present in Kiruna-type ore deposits, banded iron formations, and ore deposits
..
Fig. 125. Phase relationships in the system FeO-Fe 20 3- Ti0 2. Tie lines between ulvospinel
(Fe 2Ti0 4 )-magnetite (Fe 30 4 ), ilmenite (FeTi0 3)-hematite (IlFe 20 3), and ferropseudobrookite
(FeTi205)-pseudobrookite (Fe 2Ti0 5) are solid solution joins. The solvi, which define regions
of immiscibility for the spinel and ilmenite joins, are schematically shown as a function of
temperature and composition. The photomicrograph to the left illustrates the fine scale
exsolution of magnetite from ulvospinel, and oxidation to ilmenite lamellae; the photomicrograph to the right shows hematite (white) exsolved from ilmenite (gray), and ilmenite from
hematite; both assemblages are typical of plutonic rocks and some high grade metamorphic
assemblages. The contours are Curie temperatures. The shaded region represents the field of
titanomaghemite ('l'Fe 20 3). A typical oxidation trend is illustrated by the dashed line from
Fe 2Ti0 4 to Fe 2Ti0 5; the phases produced by oxidation are a function of temperature and
examples of these assemblages are shown in Fig. 126
..
-.,
R3
,/
-:-::-.: 0"',
-~
:3'~~;'~:
.
...... -
C4
MOLE PERCENT
TiOZ
\:.
..
R4
R5
. ".",;,.,.:
.;..-, '. ......
~
, '~~,'
, .~c ,t
\
..... ~.a1
~~-:+~
':i-~~,~.,~,
.~~,':.~
'i~t~~~
.::.:...,~
Fig. 126. This composite illustrates the complexities in oxide minerals and oxide mineral textures as a function of redox state,
Two series are illustrated: Cl to C7 represents the progressive decomposition in magnetite (cubic) series minerals; and Rl to R7
the corresponding trend in ilmenite solid solutions, The sequence of assemblages that form on oxidation may be traced along an
oxidation-reduction tie line (e.g" Fig. 125) of constant Fe: Ti ratio from the FeO- TiO z sideline to the Fe Z0 3 - TiO z sideline. For
a complete discussion see Haggerty (1976a, b, 1991)
C2
'
,-
f~'r_"
'. '.. ' ............"'.
;t:'?:"
;~"""'" ... .....
,.,'.:"'..:"".....:','
- '.~~"":~
,
"
~>' ~<,:~.~.',::(-..::,;~
~
0"-
c;>
S'
<P
....
~
o
....,
;;;'
en
~
::l
"0
?'
'0
:T
(J
00
469
associated with mafic and ultramafic rocks; these are all readily detected by
aeromagnetic surveys. Important advances, however, have been made in the
magnetic recognition of felsic rocks, ore mineralization, and redox states.
Granites, for example, are classified as I (igneous), S (meta-sedimentary), and A
(anorogenic) types, but are also distinguished as magnetite-series and ilmeniteseries granites. I-type granites are typically in the magnetite-series, are more
highly oxidized than S-type granites, and are hosts to Mo, scheelite, and Au
deposits. Ilmenite-series granites are more reduced, are typically graphitebearing, but are not necessarily of meta-sedimentary (S-type) origin; ilmeniteseries granites may host Sn and wolframite deposits. From the presence of
magnetite, the magmatic I-type granites are more responsive to aeromagnetic
detection. This response, however, as is the case for all magnetic surveys, is
directly related to magnetic contrasts between mineralized targets and barren
country rocks.
Of equal significance in the correlation of magnetic signatures and ore
deposits are those associations in which magnetite is closely linked to a central
ore-depositional process. The most prominent of these ancillary associations
are: banded iron formations with some stratiform Pb-Zn deposits; Kuroko-type
ores of volcanoclastic origin and the association of ferruginous cherts; laminated
jaspilites in some Au districts; aureole magnetite in the cores of porphyry eu
deposits, and in the outermost margins of skarn deposits. Unequivocal interpretation of these associations is rarely possible but district-wide magnetic
signatures in known ore deposits have been shown to be useful.
There are at present no simple (or even complex) algorithms relating
igneous, metamorphic, and sedimentary rocks to specific types of mineralization, redox state, magnetic mineralogy, and aeromagnetic response. Advances have been, and will continue to be made, but the qualitative and comparative
approach, regretably, remains in vogue.
References
Grant FS (1984a) Aeromagnetics, geology, and ore environments. I Magnetite in igneous,
sedimentary and metamorphic rocks: An overview. Geoexploration 23: 303-333
Grant FS (1984b) Aeromagnetics, geology and ore environments. II Magnetite and ore
environments. Geoexploration 23: 335-362
Haggerty SE (1976a) Oxidation of opaque mineral oxides in igneous rocks. In: Rumble D (ed)
Reviews in mineralogy. Mineral Soc Am, chapter 4, pp 1-100
Haggerty SE (1976b) Opaque mineral oxides in igneous rocks. In: Rumble D (ed) Reviews in
mineralogy. Mineral Soc Am, chapter 8, pp 101-300
Haggerty SE (1991) Oxide minerals: a mini-atlas. In: Lindsley DH (ed) Reviews in mineralogy.
Mineral Soc Am, chapter 5, pp 129-219
Ishihara S (1981) The granitoid series and mineralization. Econ Geol 75th Anniv vol: 458-484
470

P.A.
CHEREMNYKH
Magnetic separation (m.s.) as a technological method to concentrate ore and to

purify feed has been in use for 100 years. Recently, there has been important
progress in its development due to the exhaustion of ore sources and the
appearance of new methods involving highly intensive magnetic field generation.
M.s. is based on the fundamental principle of magnetism: any particle of
volume V has a dipole magnetic moment 11m = M V in the magnetic field B. The
moment is oriented along the field. The force is the gradient of magnetic
potential energy: F m = - VU and magnetization is M = KB. Therefore, the
magnetic force is Fm = 0.5KVVB 2 1110' where K is the volume of magnetic
susceptibility, 110 = 4nlO- 7 Hn/m. The forces, F c ' which compete with the
magnetic force, are hydrodynamic drag, friction, inertia, and gravity. The
gravitation force, F g = V(pp - Pr)g, is significant for large particles, the hydrodynamic drag force, F d = 3nDI]vp, is important for small particles in wet m.s., Pp
and Pr are the densities of the particle and fluid medium used in the separator,
respectively, g is the gravitation constant, I] is the kinematic viscosity of the fluid
medium, D is the particle diameter, and vp is the velocity of the particle relative
to the stream. The competition between F m and F c determines the probability
that the particle will be trapped in the separator. The interparticle forces,
depending on the magnetic interaction and electrostatic interaction (Coulomb,
van der Waals, and double-layer forces), determine the quality of the m.s.
The m.s. falls into two general categories: (1) isodynamic and (2) catodynamic. The force F mis constant over the working zone in category (1) ofm.s, thus
allowing separation based only on the magnetic susceptibility K. The m.s. (2)
depends on K and D, but is widely used for wet and dry separation because of its
simplicity.
Most minerals are weakly magnetic with K = 10- 6 -10- 3 SI units. The
magnetic force, fm ~ 10 5 N/m 3 , is enough to concentrate ferrous ores, but
weakly magnetic particles can be trapped by the separator with
fm ~ 108 _10 11 N/m 3 At present, there are two types of magnetic separators,
based on the two categories of m.s.
The first type is a high-gradient magnetic separator (HGMS). The working
zone of HGMS is packed with a ferromagnetic matrix (grooved plates, steel
wool, and grids) in the background magnetic field. Usually, the saturation value
offerromagnetics Bs is about 1.5-2 T and VB ~ Bs/s ~ (0.3-1.5) X 104 Tim in the
matrix surface, the radius of matrix wire is s = 0.1-1.5 mm. The matrix volume is
equal to 5-8% of the working zone volume. The force fm increases up to
1011 N/m 3 , fm amounts to loll N/m 3 Therefore, the device effectively traps
particles with K ~ 10- 6 and D~2 x 10- 5 m, but the available trapping surface
471
is very limited. HGMS of Jones, Sala Magnetics, Eries Magnetics are well
known.
The second type is a volume-gradient magnetic separator (VGMS). The m.s.
in this separator is based on field distributions which produce high-gradient and
large magnetic forces over the whole working zone. It may be explained as
follows. If the conductor current is I, one can thus express the values on
the conductor surface: B = I/(2nr), VB = I/(2nr2), and Fm = I/(4n 2r 3), where r
is the conductor coil radius. These coils are placed (with period T) on
the plane or the cylinder surface of the working zones. The currents of
neighboring coils are directed in the opposite direction (line multipoles). In this
open system F m decreases with distance z from coils F mexp( - 4nz/T). The
VGMS can use either electromagnets or permanent magnets (BaFeO, SrFeO,
Fe-Ni-AI-Co, Nb-Fe-Br, and others).
Superconductors most effectively generate the VGMS magnetic field: B ::;:; 5
- 6T in the working zone volume 0.5 m 3 and fm ::;:; 108 N/m 3 without a matrix.
The particles are deflected from the main stream and trapped by the separator.
The deflection depends on B2. The separation in VGMS is close to isodynamic
m.s., therefore this device improves ore fractionation with high selectivity.
The ideal result of any m.s. is the fractionation of ore into all components. As
most components are small, there is the problem of colloidal medium separation. This process obeys the law of statistic fluctuation.
All theoretical models of m.s. based on competition between forces described
this process with fair accuracy but with some uncertainties in some parameters.
A more precise solution can be obtained with methods from nonlinear dynamic
systems. Magnetic separation is the most promising technique of ore concentration and purification. M.s. can coordinate current and future interests of
mankind in the areas of minerals, energy consumption, and environment
protection.
References
Cheremnykh P, Dmitrievskaya T, Piskunov A, Fedorov V (1985) Optimal plane VGMS with a
linear-conductor based magnetic system. In: Magnetic technology. Proc Int Conf IEEE
Ziirich, p 777
Gerber R, Watmough M (1990) Superconductive and conventional VGMS; comparative
study. J Magnet Magn Mat 83: 490-492
Svoboda J (1987) Magnetic methods for the treatment of minerals. Elsevier, Amsterdam
Watson JH (1975) Theory of capture of particles in magnetic high-intensity filters. IEEE Trans
Mag 11: 1597
472
6.7 Optical Properties of Minerals

6.7.1 General Review of Optical Mineralogy and
Phenomenological Crystal Optics
W.D.
NESSE
and Y.O.
PUNIN
The study of minerals using optical techniques, principally employing a petrographic microscope, is most commonly undertaken to obtain information such
as mineral identity, chemical composition and structural state, and growth and
strain history. While this information often can be obtained by other more
sophisticated techniques such as X-ray diffraction, X-ray fluorescence, and
electron microscopy, the methods of optical mineralogy have the advantage that
they are simple, inexpensive, reliable, reasonably accurate, and require small
samples. In addition, optical examination of mineral samples is typically
required before the more sophisticated techniques are employed, and optical
identification of minerals is routinely done in the study of rocks and mineral
deposits.
Optical Theory
Optical mineralogy theory is based on consideration of the index of refraction
n = vo/v (where v is the velocity of a light wave in the mineral and Vo is the
velocity of light in vacuum) of light which passes through the mineral. All
minerals except those in the isometric system are optically anisotropic: index of
refraction varies as a function of direction, and the light following most paths is
birefringent or doubly refracted; it is split into two rays which vibrate at right
angles and which have different indices of refraction. Optical anisotropy is a
consequence of anisotropy of the dielectric property of tetragonal, hexagonal,
orthorhombic, monoclinic, and triclinic minerals. In order to geometrically
illustrate these properties, the optical indicatrix is used. The optical indicatrix is
a geometric figure in which indices of refraction are plotted as vectors from the
origin whose length is equal to the index of refraction and whose orientation is
parallel to the electric optical indicatrix and the details of measurement of
optical properties can be found in any textbook on optical mineralogy. The
shape and symmetry of the indicatrix is controlled by the symmetry of the
mineral.
For isometric minerals which have a single unit cell dimension and a high
degree of symmetry, the velocity of a given wavelength of light is the same
regardless of direction; hence the indicatrix is a sphere whose radius equals the
index of refraction. Isometric minerals are optically isotropic.
6.7.1 General Review of Optical Mineralogy
473
For tetragonal and hexagonal minerals which have two unit cell dimensions
(a and c) and a high degree of symmetry about the c crystal axis, two indices of
refraction (nro and n.) are required to define the indicatrix whose form is an
ellipsoid of revolution whose axis is the c crystal axis. The radius along the c axis
is n. and the radius at right angles to the c axis is nro' Light propagating in a
random direction is doubly refracted. The two rays vibrate parallel to and have
indices of refraction equal in magnitude to the lengths of the semiaxes of the
elliptical section through the indicatrix which is parallel to the wave front of
the light. In hexagonal and tetragonal minerals there is one direction, along the
c crystal axis, in which the light is not doubly refracted. The section through the
indicatrix parallel to the wave front is a circle with radius nro' This direction
along the c axis is called an optic axis, and because hexagonal and tetragonal
minerals have only one optic axis, they are optically uniaxial. If n. > n ro , the
mineral is optically positive, and if n. < n ro , negative. The birefringence
(n. - nro) is a useful diagnostic value.
Orthorhombic, monoclinic, and triclinic minerals require three unit cell
dimensions to describe their crystallography and require three indices of
refraction (n" < np < ny) to describe their optical properties. The optical indicatrix is a triaxial ellipsoid defined by plotting the three principal indices of
refraction (n", np, ny) along orthogonal X, Y, and Z axes, respectively. The
geometry of a triaxial ellipsoid requires that there are two circular sections
which intersect in the Y axis. Directions perpendicular to the two circular
sections are the two optic axes along which light is not doubly refracted; these
minerals are optically biaxial. The size of the 2V or optic angle between the optic
axes is a useful diagnostic property as is the birefringence (ny - nIX)' If the X
indicatrix axis bisects the acute angle between the optic axes, the mineral is
optically negative, and if Z is the bisectrix, positive. As with the uniaxial case,
light entering a biaxial mineral in a random direction is doubly refracted and the
indices of refractions and vibration directions of the two rays (usually termed r:t.'
and y') are found as described above.
The orientation of the biaxial indicatrix within a mineral is constrained by
the mineral symmetry. For orthorhombic minerals, the indicatrix axes coincide
with crystal axes. For monoclinic minerals, one indicatrix axis coincides with the
b crystal axis. For triclinic minerals, indicatrix axes and crystal axes do not
coincide except by chance.
For all three optical classes (isotropic, uniaxial, and biaxial) dispersion, i.e.,
variation of index of refraction and hence dimensions and/or orientation of the
indicatrix as a function of wavelength, may also be a useful diagnostic property.
Methods
The petrographic microscope differs from a conventional transmitted light
microscope in that it is equipped with a rotating stage on which the sample is
placed, the light source provides plane polarized light, and a polarizing filter and
474
other optical elements are placed above the sample to analyze the light after it
passes through the sample. The upper polarizing filter is typically oriented so its
vibration direction is at right angles to the lower polarizer. The microscope may
be configured either for orthoscopic or conoscopic illumination.
With orthoscopic illumination, weakly converging light is used, allowing the
mineral sample to be examined directly with the upper polarizing filter either in
(crossed polars) or out (plane light) of the optical path. Isotropic minerals do not
influence the polarization of the incident light; in plane light the mineral color
will be observed, with crossed polars the mineral will appear black because the
plane polarized light passing through the mineral is entirely absorbed by the
upper polarizing filter. Light entering anisotropic minerals in most orientations
is doubly refracted. In plane light colored minerals will typically be pleochroic,
they change color as the microscope stage is rotated and the two vibration
directions are brought parallel to the vibration direction of the lower polarizer.
Between crossed polars anisotropic minerals display interference colors because
the two rays have different velocities; when they are resolved into the vibration
direction of the upper polarizing filter some wavelengths of light constructively
interfere and others destructively interfere. The complement of wavelengths that
pass is perceived as an interference color, and the mineral appears illuminated.
As the stage is rotated, the mineral will go dark, or extinct, every 90 degrees as
the mineral vibration directions are brought into coincidence with the vibration
directions of the lower and upper polarizing filters. Orientation of extinction
positions relative to cleavages and crystal outlines provides information about
the indicatrix orientation in the mineral.
Conoscopic illumination uses strongly converging light to produce optical
phenomena called interference figures which are observed at the upper focal
plane of the objective lens. The interference figure allows determination of
optical class, optic sign, dispersion characteristics, 2V angle, and indicatrix
orientation. Consult an optical mineralogy text for details of procedures.
The measurement of refractive indices is most commonly accomplished by
comparing the index of refraction of an unknown mineral with that of a known
immersion liquid. With the spindle stage method, a grain of the unknown is
mounted on a fine wire that can be rotated about a horizontal axis while holding
the unknown in a cell of immersion liquid. This allows each of the indicatrix axes
in the mineral to be placed horizontal and parallel to the lower polarizing filter
vibration direction so that the index of refraction associated with that axis can
be compared with that of the immersion oil. With the grain mount method,
loose grains of the unknown are placed in an immersion liquid on a glass
microscope slide. Grains which by chance happen to be oriented with one of the
indicatrix axes horizontal are selected based on the properties displayed in both
orthoscopic and conoscopic illumination, and the mineral index of refraction for
light vibrating parallel to that axis is then compared with that of the immersion
oil. A universal stage, which allows the microscope slide to be rotated in a wide
range of orientations, may be employed with grain mounts to allow selected
6.7.1 General Review of Optical Mineralogy
475
grains to be precisely oriented, but it is much more cumbersome than the spindle
stage. With routine work accuracy of 0.001 index of refraction units is
attainable. With thin sections, which are typically 0.03 mm-thick slices of
rock/mineral permanently mounted on glass microscope slides and used to
study rock mineralogy, texture, and structure, only rough estimates of index of
refraction are possible.
Other optical properties (optical class, optical sign, 2V angle, dispersion
properties, mineral color, birefringence) may also be determined with grain
mounts and the spindle stage and are the primary diagnostic properties
observed with thin sections. A universal stage may be employed to rotate a thin
section to place a selected grain in a desired orientation.
Mineral Identification
In many cases the identity of an unknown mineral may be quickly determined
on the basis of its optical properties. The most complete tabulation of mineral
optical data is that of Fleischer et al. (1984), which presents data for about 2400
minerals. The Russian translation of this work contains 99 additional minerals.
The tabulations of Trager (1982), Phillips and Griffin (1981), and Deer et aJ.
(1962-1986) also are recommended.
Composition Determination
It has long been recognized that optical properties of minerals vary as a function
of composition. In general, compositions with higher average electron density
have higher indices of refraction, so substitution of a higher Z element typically
results in an increase in index of refraction as, for example, the substitution of
Fe or Mn for Mg. In many cases, reasonable estimates of average index of
refraction can be obtained from knowledge of mineral composition and structure. Similarly, diagrams and equations have been developed for many minerals
and mineral groups which allow composition to be estimated based on optical
properties. While optical methods are quick and inexpensive, they have significant limitations and are most reliable in binary systems, i.e., minerals which have
substitution of two elements in a single structural site (e.g., Fe and Mg in olivine
or orthopyroxene). In minerals which have substitutions in several structural
sites, or numerous elements in a single site, it is generally found that there are
too few optical variables to uniquely identify the composition. In an attempt to
overcome this limitation, data from X-ray diffraction has been combined with
the optical data with some success. Despite the limitations, optical estimates of
composition are quite useful and can be valuable guides in planning more
sophisticated chemical analyses.
476
Other Applications
Many minerals display a range of ordering of selected cations in certain

structural sites. In some minerals, such as the alkali feldspars, the degree of
cation ordering influences both the symmetry and the mineral's optical properties so that it is possible to provide an excellent estimate of cation ordering based
on the optical properties.
Growth-related structures which may be studied with the techniques of
optical mineralogy include textural intergrowths with associated minerals,
twinning, chemical zoning, and a process which has been termed "dissymetrization".Twins will be visible provided that the twin operation results in
different twin segments having different optical indicatrix orientations. Chemical zoning present in many minerals may be recognized because of variation in
color, indicatrix orientation, and/or birefringence. Growth structures related to
dissymetrization appear to be metastably produced because segments of crystals
growing on different crystal faces acquire different symmetry. The lamellar
structures that result may be recognized optically.
Twins, deformation bands, and other microstructures may be developed
if minerals are strained. The study of these features is referred to as microstructural analysis, and may provide information about the orientation and
magnitude of the applied stresses.
References
Bloss FD (1981) The spindle stage: principles and practice: Cambridge Univ Press, Cambridge,
340 pp
Bulka GR, Vinokurov VM, Nizamutdinov NM, Hasanova NH (1980) Dissymetrisation of
crystals: theory and experiment. Physics and chemistry of minerals, vol 6, pp 283-293
Deer WA, Howie RA, Zussman J (1962-1986) Rock-forming minerals, 8 vols, J Wiley & Sons,
New York
Fleischer M, Wilcox RE, Matzko JJ (1984) Microscopic determination of the nonopaque
minerals. US Geol Surv Bull 1627: 453
Hauser J, Wenk NR (1976) Optical properties of composite crystals. Z Kristallogr 143:
188-219
Jaffe HW (1988) Crystal chemistry and refractivity. Cambridge Univ Press, 335 pp
MacKenzie WS, Guildord C (1980) Atlas of rock-forming minerals in thin section. John Wiley
& Sons, New York, 98 pp
Nesse WD (1991) Introduction to optical mineralogy, 2nd edn. Oxford Univ Press, New York,
335 pp
Phillips WR, Griffin DT (1981) Optical mineralogy, the nonopaque minerals. WH Freeman
and Co, San Francisco, 677 pp
Punin YuO (1989) Anomal optics of layer heterogeneous crystals. Zhapisky Vres Mineral Ob
1I8: 76-90
Su SC, Bloss FD, Ribbe PH, Stewart DB (1984) Optic axial angle, a precise measure of AI, Si
ordering in T 1 tetrahedral sites of K-rich alkali feldspars. Am Mineral 69: 440-448
Troger WE (1982) Optische Bestimmung der gesteinbildenden Minerale, Teill, Bestimmungstabellen (5th ed). Schweizerbart'sche Veriagsbuchhandlung, Stuttgart, 188 pp (English
translation of 4th edn available)
477

1.
ARNDT
The refractive index is a fundamental macroscopic property of matter. According to the theory of refraction in dielectric materials, the dielectric constant and
th us the refractive index arise in the range of optical frequencies (4 x 10 14 -7.5
X 10 14 Hz) solely from the electronic polarizabilities of the atoms or ions. The
electronic polarizability is therefore the fundamental optical property. Any
theoretical interpretation of refractive index data must inevitably address
considerations about the electronic polarizabilities and their dependence on
changes in the state of material due to temperature, pressure, and structural
changes.
The Classical Theory of Refraction of Light

The starting point in the theory of refraction of light in dielectric materials is the
equation of electrostatics
eE
= E + 4nP,
(1)
where e is the dielectric constant and E and P are the applied electric field and
the polarization, respectively. These macroscopic quantities are related with
microscopic atomic parameters. The polarization is interpreted as the total
dipole moment per unit volume, given by the number N j of oscillators of type i
with induced dipole moment f1.i and polarizability ai per unit volume, i.e.,
(2)
~oc is the local electric field that is effective in polarizing each individual atom. It
includes in general a contribution from the polarization due to mutual interactions between the induced dipoles, i.e.
E 10c
= E + bP,
(3)
where b is the Lorentz factor.

Combining Eqs. (1), (2), and (3) together with the Maxwc:;11 identity which
relates the dielectric constant e and the refractive index n at optical frequencies by
(4)
one obtains a general refractivity formula
where NA is Avogadro's number (6.022045 x 1023 mol-I), M is the molecular
478
weight, p is the density (g x cm - 3), Xi is the number of atoms of type i per

formula unit and oc is the molar polarizability.
Electric field, polarization, and induced dipole moment are vector quantities,
while polarizability and dielectric constant are second rank tensor properties.
The refractive index itself is not a tensor, although its variation with direction is
determined by the dielectric constant tensor.
In the refraction theory of Lorentz and Lorenz, the Lorentz factor is
b = 4n/3. By inserting this value into Eq. (5) one obtains the Lorentz-Lorenz
refractivity formula
[(n 2
1)/(n 2
+ 2)](M/p) = (4n/3) oc.
(6)
The Lorentz-Lorenz theory applies to ideal dipoles arranged in a cubic lattice or

in a random distribution. Hence there is no overlap of the electronic charge
distributions of nearest neighbors and the effective field polarizing each atom is
taken as the sum ofthe macroscopic field and the distant neighbor Lorentz field.
In reality, however, the charge distributions of nearest neighbors overlap, giving
rise to an overlap field which counteracts the Lorentz field and thus reduces the
effective field. As a result, the Lorentz factor becomes smaller than the value 4n/3
characteristic of ideal point dipoles. When the overlap field exactly cancels
the Lorentz field, Eloc = E and b = O. Inserting this value into Eq. (5) yields
formally the Newton-Drude refractivity formula
(n 2
1)M/p
= (4n) oc.
(7)
However, it must be emphasized that this formula is based on the assumption

that the local field is represented simply by the macroscopic electric field.
The left-hand sides of Eqs. (6) and (7) are called the Lorentz-Lorenz and
Newton-Drude refractivities, respectively. Both refractivity formulae are often
used in the interpretation of experimentally observed relationships between the
refractive index n and density p. In addition, a number of "empirical" refractivity
formulae are in use, the most common of which are listed in Table 35. These may
be obtained from the general refractivity formula [Eq. (5)] by choosing arbitrary
values for b, as is also shown in Table 35.
In deriving the Lorentz-Lorenz and the Newton-Drude refractivity formulae, the electronic polarizabilities are assumed to be constant and independent of density. This assumption applies also to the "empirical" refractivity
formulae. The increase in refractive index with increasing density of a material
calculated by each of these refractivity formulae is thus solely the result of the
increasing number of oscillators per unit volume. Figure 127 shows the experimentally determined n-p relationship for Si0 2 -glass and quartz, the structures
and hence the densities of which had been altered by various processes. As is
seen, the Lorentz-Lorenz formula overestimates and the Newton-Drude formula underestimates the experimentally measured increase in refractive index
with density. This observation has been made also for experimental n-p
relationships of other materials. In addition, it has been observed on glasses that
elastic compression and permanent densification yield different n-p relationships for the same material. In the case of permanently densified and sub-
479

Table 35. Empirical refractivity formulae
Refractivity formula
Gladstone-Dale
Values of b for refractive index values of

n = 1.7
n = 1.5
n = 1.3
1
(n - 1)- = KG
P
2.4
2.0
1.7
5.2
4.6
4.1
Eykman
3.4
2.8
2.4
Johst
3.7
3.2
2.8
8.6
8.0
7.6
11.5
2.0
0.1
Lichtenecker
Edwards
Allen
(log n)P
(~)~n
p
-
(n3)~ =
P
KL
KED
KA
Some of the constants K have been given names such as:

KG: specific refractivity,
K L : Lichtenecker constant,
K A : specific refractive capacity.
sequently annealed Si0 2 -glass, different refractive index values are obtained for
the same density value, depending on the initial density of the densified glass.
This indicates that the refractive index may even be not a single-valued function
of the density. Moreover, in contrast to all other crystalline materials, it is
observed for crystalline MgO and diamond that the refractive index decreases
on elastic compression and increases on thermal expansion. Similar behavior
has been found for silica glass and other glasses.
These examples clearly indicate that the Lorentz-Lorenz and Newton-Drude
formulae are based on inappropriate assumptions and that both changes in the
polarizabilities and overlap of the charge distributions of the atoms must be
accounted for. However, both effects cannot be separated from each other and
no unambiguous conclusions can be drawn about the extent of the overlap field
and the constancy or alteration of the atomic polarizabilities. Therefore, in
analyzing an experimentally determined n-p relationship, one must assume that
one of the two factors remains constant during the density change. Therefore,
two different methods of analysis have been developed. These will be outlined in
the following.
Analysis Based on the Ideal Dipole Theory of Lorentz and Lorenz
Change of the Refractive Index by Hydrostatic Pressures at Constant Temperature. In his theory of the photo elastic effect of cubic crystals and amorphous
480
1.60
1.58
1.56
Q)
"0
1.54
Q)
>
c.l
CO
....
I'""~"
1.52
'-
Q)
a:
1.50
;' Coesite
Keatite / ~uartz.
SiO glass,' Crlstoballte
',
1.48
1.46
...
/:
: Porosils
'/
1.44
2.2
2.4
2.6
2.8
If [g/c",3j
3.0
Density [g/cm 3 ]
Fig. 127. Plots of data of refractive index versus density of the SiOz polymorphs and the
structurally altered SiOz glass and quartz.
Large diagram: Upper and lower solid lines calculated with the Lorentz-Lorenz and NewtonDrude formulae, respectively; middle solid line calculated with the general refractivity formula
with b ,= 1.3.
For uniaxial and biaxial mineral the refractive index is represented by arithmetic mean, i.e., by
(2nD + l1e)/3 and (n. + np + n y)/3, respectively . SiOz polymorphs (L: lechatelierite; T: lowtridymite; CR: low-crystobalite; K: keatite; Q: low-quartz; C: coesite; + SiOz glass, densified
by static pressure; SiOz glass, densified by dynamic pressures; 0 SiOz glass, densified by
neutron irradiation; ... quartz, neutron irradiated; quartz, shock-loaded. (Large diagram
from Arndt and Hummel 1988; inset from Marler 1988)
solids, Mueller assumed that the Lorentz-Lorenz theory is valid but, in addition,
he assumed that the molar polarizability changes linearly with strain in isothermal elastic compression under hydrostatic pressures. Mueller's reasoning was
later extended to the Newton-Drude formula. Accordingly, the experimentally
observed change in refractive index with strain is the result of the change which
arises from the increase in the number of oscillators per unit volume due to the
increase in density and in addition of a change in the polarizabilities of the
atoms due to the decrease in the interatomic distances. The change in molar
polarizability due to strain S = dV/V = - dp/p is given by
I'/.
I'/.o(l
+ LS),
(8)
where 1'/.0 and I'/. are the molar polarizabilities of the undeformed and deformed
crystal, respectively and L is the macroscopic strain polarizability parameter
481
defined by Mueller by
L = -- (d(J./(J./dp/p) = (d(J./(J./dVIV).
(9)
The total change in refractive index with density, i.e.,

dn/dp
= (on/op)~ + (on/o(J.)pd(J./dp
(10)
is given according to Mueller by

dn/dp = (on/opla(1 - L).
(11)
If polarizability does not change with changing density, then

dn/dp = (on/op)~
and
L= 0
(12)
The theoretical value p(on/op)~ can be calculated from the partial derivatives
of the Lorentz-Lorenz or Newton-Drude formula, which are given under the
assumption that the polarizability is constant and independent of strain by
p(on/op)~ = (n 2
+ 2)/6n
1)(n 2
1)/2n.
(13)
and
p(on/op)~ = (n 2
(14)
The proportional change in refractive index with density, p(dn/dp), can be

obtained from the slope of the curve of the experimentally observed change in
refractive index An versus the volume strain, since
p(dn/dp)
=-
An/(AV/V o).
(15)
Values of p(dn/dp) can also be obtained from experimentally determined

elasto-optic coefficients Pij' For amorphous materials such as glasses as well as
crystals of the cubic classes with tetrads as the cube axes, i.e., the classes m3m,
43m and 432, the change in refractive index produced by a hydrostatic pressure
is given by
(16)
In Table 36 are given data of experimental p(dn/dp), of p(on/op)rz calculated
from the Lorentz-Lorenz and Newton-Drude relations and the resulting values
of the macroscopic strain polarizability parameter LLL and L D, respectively. As
is seen, the experimental values of p(dn/dp) are in general smaller than the values
calculated from the Lorentz-Lorenz formula and the Newton-Drude formula.
Mueller has related macroscopic and microscopic strain polarizability parameters by assuming that for a small change AV of the atomic volume the molar
polarizabilities of the atoms change also linearly with strain S = dVIV =
- dp/p, i.e.,
(17)
where (J. and (J.i are the molar polarizabilities of atoms of type i in the strained
2.417
1.736
1.544
1.392
1.559
1.458
1.447
Diamond
MgO
NaCI
LiF
KBr
Si0 2 -glass
B2 0 3 -glass
2.202
1.833
3.51
3.58
2.16
2.60
2.75
(g/cm
3)
0.32
0.41
- 0.28
- 0.40
0.24
0.1
0.35
p(:~)exp
0.53
0.51
2.62
0.97
0.66
0.44
0.68
p Cn)
-=- ex LL
cp
0.40
0.24
1.11
1.41
0.58
1.00
0.48
LLL
All data, except those for B2 0 3 -glass, from Waxler and Weir (1965).
Data for B2 0 3 -glass from K. Vedam and W.e. Schneider (1972).
nD
Material
0.39
0.38
1.00
0.58
0.45
0.34
0.46
p -;::- ex D
. Cn)
cp
0.17
- 0.08
1.28
1.68
0.38
1.00
0.24
LD
-1.3
0.92
-1.3
- 3.6
1.0
1.6
- 3.8
0.15
4.56
0.31
3.9
12.0
10.2
12.0
r
(x lO- S(C)
dn/dT
(xlO- S(C)
Table 36. Analysis of changes in refractive index and polarizability for some cubic crystals and glasses
2.6
0.6
1.0
- 0.7
- 3.9
0.9
(x lO- StC)
::;;
;;l
5'
o
-,
en
;::l.
,,'
'"d
o
'"...,
;;
....
'0
(")
;:,-
tv
.j:>.
00
483
and unstrained crystal, respectively, and Ii are their strain polarizability parameters.
If all atomic volumes change by an amount proportional to the total volume
change, this change is given by Eq. (11) where
(18)
It is plausible to assume that a decrease in volume, i.e., an increase in density,
decreases the polarizabilities of the atoms. Each Ii is thus a measure of the
decrease of the polarizability of an atom of type i when its volume is decreased
by hydrostatic pressure. If the material is compressed to a strain of 1%, the
polarizability of the atoms is reduced by Ii %. In oxide materials, such as the
silicates, the polarizability changes are for the same compression much larger for
the oxygen atoms than for the cations, i.e., L is practically identical wi"th I for
oxygen.
According to the above considerations, the change of the refractive index on
elastic hydrostatic compression is the result of two opposite effects. The increase
of the number of oscillators per unit volume leads to an increase, the concomitant decrease of polarizability leads to a decrease of the refractive index. Up to
now, it has been found that the first effect dominates in all materials except of
MgO and diamond the refractive index of which decreases on compression,
apparently as a result of the dominating decrease of the polarizability. These two
materials also show the largest values of the macroscopic strain polarizability
parameter of all materials listed in Table 36. This parameter has been regarded
as a measure of ionic overlap and the degree of homopolar bonding, but this
physical interpretation is questionable.
Mueller has pointed out that his theory of photoelasticity applies to small
deformations only for which Hooke's law holds. Analysis of relationships of
concomitant changes in refractive index and density resulting from structural
changes which are produced, for example, in glasses by permanent densification
or by annealing in the glass transition range is not accounted for by this theory.
Change of the Refractive Index with Temperature at Constant Pressure. In

extending the theory of photoelasticity, Ramaseshan et al. (1958) showed that
the temperature change of the refractive index of amorphous materials and
cubic crystals can be expressed by the temperature-polarizability coefficient
(19)
With rising temperature at constant pressure, the change in polarizability is
given by
oc
= oco(1 + LrT + rT),
(20)
which to a first approximation gives the change in refractive index with

temperature by
dn/dT = p(i'Jn/op)a( -
r + Lr + r),
(21)
484
where
r
= - (l/p)(dp/dT) = (l/V)(dV/dT) and L = (v/rx)(arx/avh.
(22)
r is the coefficient of thermal volume expansion and L is the macroscopic strain
polarizability parameter.
For the interpretation of the thermal behavior of the refractive index of
different materials one has to consider therefore the relative magnitudes of L, r,
and r. The first term in Eq. (21) represents the pure density contribution. It is
always negative. The product Lr is in general positive and r can be positive
or negative. It must be pointed out that dn/dT itself is also a function of
temperature.
Values of experimentally observed changes of the refractive index with
temperature and of the temperature-polarizability coefficient r are also given in
Table 36. As is seen, dn/dT is negative for KBr, NaCl, LiF and B2 0 3 -glass and is
positive for MgO, diamond, and silica glass. These results may be explained in
that the volume expansion leads to a decrease in the number of oscillators per
unit volume resulting in a decrease in the refractive index and, on the other
hand, it leads to an increase of the polarizabilities, resulting in an increase in
refractive index with rising temperature. The net result then depends on the
predominance of either of these effects. For example, in silica glass the thermal
expansion and thus the increase in specific volume with increasing temperature
is extraordinarily small and therefore the increase in polarizability dominates,
resulting in the observed increase in refractive index with temperature. In
contrast, the refractive index of B2 0 3 -glass decreases appreciably with rising
temperature due to its rather large thermal expansion resulting in a strong
increase in specific volume which dominates over the increase in polarizability.
Change of Refractive Index with Pressure and Temperature. According to the
extended theory of photoelasticity, a general expression for the change in
refractive index during a change in the material state is given by
dn =
p(an/ap)~[(I/rx)(arx/aT)vdT
+ ((V/rx)(drx/dVh - l)dVjV].
(23)
Inserting the various coefficients given above into Eq. (23) yields
dn =
p(an/ap)~[(l
- L)dp/p
+ rdT].
(24)
This expression may be applied, for example, for the calculation of the
change in refractive index during shock compression of materials (Setchell1979).
For this case, Eq. (24) is written
p(dn/dp) =
p(an/ap)~[1
- L
+ pr(dT/dP)a],
(25)
where (dT/dP)a corresponds to an adiabatic change in state which can be

evaluated for weak shocks with the isentropic relation
(26)
where 'Yo is the Griineisenparameter evaluated at standard conditions.
485
'"
6
'D
00
6
~
'D
;:
I
'"
6
\
'-
..".
.:!:!
U
;;:
"ua
:c
E'"
0'"
"-
'"
102 xc.n
\
\
(Experimental)
L'
c:
<J
::"
N
..".
'"
'" u,.
e
'e
Fig. 128. Calculated shock

polarizability coefficient L'
and change in refractive index LIn for shock-compressed SiOl-glass. Calculations are based on the
Lorentz-Lorenz formula,
(Setchell 1979)
."
-0
.S
."
102xt.n
(Linear photoelasticity theory)
.9
"c:
-=U'"
Of)
00
Shock pressure (GPa)
Substituting this relation into Eq. (25) yields

p(dn/dp)
= p(on/op)a[1 - L']
(27)
where the shock polarizability coefficient L', which gives the relative magnitude
of refractive index changes due to changes in polarizability during shock
compression, is given by
L'=L-yorT.
(28)
Results of calculations of the coefficient L' and the change in the refractive
index are shown in Fig. 128 for the case of shock compression of silica glass and
using the Lorentz-Lorenz formula.
Analysis Based on the Assumption of Constant Polarizability

Change in Refractive Index and Density by Structural Changes
It has been emphasized above that concomitant changes in density and refractive index resulting from structural differences or alterations in structure may
not be analyzed with the aid of the theory of photoelasticity. Rather, such an
analysis may be performed on the basis of the general refractivity formula
[Eq. (5)], i.e., on the assumption that the polarizabilities remain constant during
the structural changes.
Mineralogical and Geophysical Aspects of Refraction. The Si0 2 system is an
example of considerable mineralogical interest for the study of the effects of
486
structural differences on the relationship between refractive index and density

within an isochemical series. The Si0 2 polymorphs cover large ranges of
refractive index and density and exhibit appreciable differences between their
structures. As is seen from the inset in Fig. 127, all polymorphs in which the Si0 4
tetrahedron is the basic structural unit plot in very good approximation on a
common linear n-p relationship. This gives evidence that differences in the
topological arrangements of the interconnected Si0 4 tetrahedra have no significant influence on the polarizability of the oxygen ions. The refractive index is
therefore essentially a function of the density, which is equivalent with the
number of tetrahedra per unit volume. In addition, the fact that Si0 2 glass plots
equally well on this relationship indicates that the amorphous structure does not
differ significantly from the crystalline structures as regards polarizability. Using
the general refractivity formula [Eq. (5)], a value ofb = 1.2 is obtained from this
relationship. This value implies considerable overlap of the electronic charge
distributions in the Si0 2 structures.
The n-p relationship for structurally altered Si0 2 glass and quartz and for
the Si0 2 polymorphs (Fig. 127) yields a value b = 1.3. A statistical constrained
refinement analysis of all Si0 2 data as well as of data obtained on densified
glasses of the systems Ti0 2-Si0 2, Na 20-Si0 2 and NaAISi30s-CaAI2Si20s
converged at the same value of b. This fact gives evidence that a common,
constant value of the oxygen polarizability may be assumed for all these
materials in which the cations are tetrahedrally coordinated by the oxygen ions.
The refractive index thus depends only on density and is independent of
composition and structure. However, as is seen from the inset in Fig. 127, the
n-p data of the silica polymorph stishovite do not fit in the common Si0 2 n-p
relationship. Since stishovite is built up of Si0 6 octahedra, it appears that the
change in the first coordination number of silicon with regard to oxygen from
four to six has a profound influence on the oxygen polarizability.
Many years ago, Anderson and Schreiber found for a large number of rockforming silicates and oxide minerals that these fit in good approximation the
n-p relationship ofth~ Si0 2 polymorphs. All these minerals have a mean atomic
weight of about 21 g-atom/mol and therefore obey Birch's law, i.e., they exhibit
an approximately linear dependence of the velocity of elastic waves on density,
irrespective of structure and composition. This analogy between the linear
dependencies of refractive index and sound velocity on density may be helpful in
studies of the elasticity and constitution of the Earth's interior which is
predominantly composed of oxide minerals. However, both relationships refer
to ambient conditions. It is apparent now that Birch's systematic law does not
adequately account for the effects of temperature, pressure, and phase transformations on the wave velocity-density behaviour observed experimentally in
specific oxide materials. The same restriction applies equally to the systematic
refractive index-density relationship which does not account for the effects of
temperature and pressure on the pol ariz abilities and hence on the refractive
index. These effects can, however, be accounted for by the extended theory of
photoelasticity. It appears that at present no theory exists that describes the
6.7.3 Reflectance Spectra: Their Interpretation Using Band Theory
487
transformations on refraction, although refractive index measurements are a

common method for monitoring polymorphic phase transitions.
Additivity of Polarizabilities. The analysis of n-O" relations of densified glasses of

different compositions with the general refractivity formula and the common
factor b = 1.3 provides a possibility of calculating individual polarizabilities of
atoms and oxide components. It has been demonstrated that the assumption of
the additivity of individual polarizabilities of oxide components is valid and may
be applied, for example, for calculating the polarizabilities of glasses of any
intermediate composition in complex silicate systems from the polarizabilities of
the end-members.
References
Anderson OL, Schreiber E (1965) The relation between refractive index and density of
minerals related to the Earth's mantle. J Geophys Res 70: 1463-1471
Arndt J, Hummel W (1988) The general refractivity formula applied to densified silicate
glasses. Phys Chern Mineral 15: 363-369
Ramaseshan S, Vedam K, Krishnan RS (1958) Chap V in Progress in crystal physics Vol I:
Thermal elastic and optical properties, Krsihnan RS (ed) New York, Interscience, p 139
Marler B (1988) On the relationship between refractive index and density for SiO zpolymorphs. Phys Chern Mineral 16: 286-290
Mueller H (1935) Theory of the photoelastic effect of cubic crystals. Phys Rev 47: 947-957
Setchell RE (1979) Index of refraction of shock-compressed fused silica and sapphire. J Appl
Phys 50: 8166-8192
Vedam K, Schneider WC (1972) Variation of the refractive index of boric oxide glass with
hydrostatic pressure to 7 kbar J Appl Phys 43: 3623-3627
Waxler RM, Weir CE (1965) Effect of hydrostatic pressure on the refractive indices of some
solids. J Res Natl Bur Standards 69A: 325-333
6.7.3 Reflectance Spectra: Their Interpretation Using Band Theory,

and Application in Mineral Identification
A.J.
CRIDDLE
and E.G.
RVABEVA
In recent years the interpretation of the optical and physical behavior of

minerals has been transformed through the application of crystal field, ligand
field, molecular orbital, and band theories. The first two theories, dealing with
intra-electronic transitions in the transition metals, will not be examined here;
instead, the charge transfer transitions - electronic transitions between atomsof band theory will be briefly considered.
From the 1960s, onwards, band models, based on the interpretation of
specular reflection spectra, and sometimes supported by information from
transmission, diffuse reflectance, Mossbauer, X-ray emission, and X-ray photoelectron (or ESCA) spectra, have been developed for numerous opaque minerals.
488
Some have benefited from data obtained from 0-20 eV, e.g., galena, clausthalite,
altaite, molybenite, the Ag-Au alloys, sulfotellurides of Bi, etc., but for most,
measured data are available for a very much more restricted energy or wavelength range. Many texts provide summary interpretations (with copious references) for a wide range of metal sulfides and oxides; here we will restrict
ourselves to a single example, that of the much discussed group of semiconducting lead minerals: galena (S), clausthalite (Se), and altaite (Te).
In the reflectance spectra (Fig. 129) of these minerals, peaks E 1 , E z and
E3 have been interpreted as corresponding to electronic transitions from the
p-valence band of the sulfur (Se,Te) nonbonding molecular orbitals into the
p-conduction band of lead, and E 4 , and Es and E6 from lead 6s/sulfur 3p
bonding, and sulfur 3s non bonding orbitals. Such interpretations have a degree
of uncertainty even where, as in this instance, R spectra, measured and extrapolated to 25 eV, permit the application of the Kramers-Kronig relations, and are
supported by ESCA spectra. These uncertainties are related primarily to the
large spin-orbit-coupling of Pb, but also to the possibility that a single peak may
disguise the presence of two or more transitions of similar energy, and that some
transitions will belong to different points within the Brillouin zone. Nevertheless, there is a good correlation between the transition energies, cell dimensions,
. p - Te -
s - Pb -p - Pb
p - Pb
Ii
Inn
r
N.%(PbS)
60
60
Pble
o
20
PbSe
PbS
o ,
fj
Fig. 129. Reflectance spectra of PbS, PbSe, and PbTe, and their interpretation. (Marfunin
1979)
489
and interatomic distances for these minerals. At the absorption edge (Fig. 130),
at the top of the valence and bottom of the conduction bands, the reflectance
increases dramatically. For this reason, and because, in the self-conduction
band, the reflectance is independent of admixture concentration, this region of
the spectrum is characteristic for a given species. In galena, the onset of the
absorption edge is in the far infrared at 0.37 eV (3351 nm). In general, the
position of the absorption edge determines, through its effect on the dispersion
of the reflectance, the color of the mineral: where it is in the IR, the mineral
appears white or gray, and where in the UV, the mineral is yellow, pink, or red.
Some workers describe such curves as normal and anomalous, respectively.
Although less significant than the absorption edge in determining the physical
cause of color, high energy electronic transitions, predominantly between the 3p
non bonding band and the conduction band, are marked in the spectrum of
galena at 350 nm and 670 nm. Of course, reflectance spectra in the visible region
for most ore minerals are monotonous, and without peaks, e.g., as in the shaded
region of Fig. 129, and specifically for galena in Fig. 131. Reflectance spectra
measured in the visible region are of limited use in the interpretation of
electronic structure; however, they are characteristic in themselves, and, from
data obtained by microscope-spectrophotometry, form the basis of many ore
mineral identification schemes.
The examples selected to illustrate the interpretation of electronic structure
from band theory were of isotropic minerals. In some anisotropic minerals, and
particularly in those of lower symmetry, the reflection spectra for the principal
vibration directions cross (as do those of the refractive indices and absorption
coefficients, though not usually at the same wavelength). The spectral position of
this change in optical sign is distinctive and even diagnostic for a given species:
within the visible region, the ratio R ~ 1: Eg (Eg = the width of the energy gap)
has been established for more than 70 minerals.
Recently, automated, computer-controlled, microscope-spectrophotometers
(MSP) have been introduced which are capable of measuring from 230 nm
(5.4 eV) to 2,100 nm (0.59 eV) relative to one or more of the internationally
Gr.cm-I
R.%
70
5QfI(J()
1IJfI(J()
IOfl(J()
60
IfI(J()
40
I()(J
02
O.
06
01
lO,V
Fig. 130. Spectra at the absorption edge

(in the infrared) of PbS, PbSe, and PbTe.
(Marfunin 1979)
7()(J
600
SIJ(J
4i.I1nm
I
Fig. 131. Visible spectrum specular reflectance spectra for Pbs. (Marfunin 1979)
490
approved and directly calibrated reflectance standards: WC, (W,Ti)C, Si, and
SiC. Instruments such as the Zeiss (Oberkochen Ltd) MPM 400/800, and those
produced by Leitz, Polyspec, Nanospec, MSFU-L-312, etc. are capable of a
relative accuracy of 1% down to beam spots of 0.5 j1.m. Refractive indices and
absorption coefficients may be calculated, using the Koenigsberger equations,
from reflectances measured in two media (usually air and oil, nD = 1.515, but
glycerine/glycol for UV measurement), and these are physically significant for
isotropic and crystallographically orientated sections of uniaxial, orthorhombic,
and for the unique twofold axis of monoclinic crystals. Alternative approaches
require a much wider spectral range for measurement, e.g., Kramers Kronig, and
Fourier transform analysis, which can be used to derive near-approximations
for the optical constants from randomly orientated sections of a mineral. In
addition to specular reflectance, modern MSP can be used to measure diffuse
reflectance and transmission/absorption spectra for transparent or especially
thinned absorbing minerals. For isotropic minerals of sufficiently large grain size
and homogeneity, wavelength scanning ellipsometers, including the Laser ellipsometers Ll16-B-85B, Ll26B, Ll06B, are an alternative to MSP. Measuring
phase and amplitude, they directly provide the dielectric constants 8 1 and 8 2 , n
and k, from which the intensity R is derived. Other, recently developed
instrumentation, including IR-microscopes, scanning-tunnelling microscopes,
ultrasound- and laser-scanning microscopes, provides additional information
on the surface or body properties of a material.
With a new stimulus being provided by the need for noninvasive measurement techniques in the electronics and materials sciences industries, it can be
anticipated that further advances will be made in the spectral range and
sensitivity ofMSP. Already, curve-fitting algorithms have been developed which
enable the structure and composition of complex rn,ulti-Iayer structures, e.g.,
SIMOX, AIGaAs and other III-V compounds, to be reliably determined from
R spectra. With the continuing development of the theoretical basis of polarized
specular reflectance at near-normal incidence, we can expect to better understand the electronic properties and their structural significance for a wide variety
of minerals and synthetic materials.
F or now, and to return to the limited spectral range required for ore mineral
identification - the visible spectrum - we note the application of the Commission Internationale de I'Eclairage (CIE) system for the quantification of
color, widely applied in identification schemes and recommended by the Commission on Ore Mineralogy of the International Mineralogical Association
(COM-IMA). The CIE system, based on RGB (red, green and blue) primaries
transformed to trichromatic coefficients x, y, and z, and the reflected intensity, or
luminance, Y%, also contains information which can be computed (e.g., using
affine geometry), or graphically plotted on a chromaticity diagram to provide
quantitative equivalents for the subjective phenomena of color saturation
(excitation purity) and hue (dominant wavelength). Color values have a role to
play in identification schemes based on R spectra, particularly those using
computerized databases. In addition, the color of anisotropic minerals between
491
crossed polars (anisotropic rotation tints) have recently been investigated and a
unifying theory, bringing together these colors and those perceived in planepolarized light, based on dielectric tensors, and consistent with the electronic
properties of a mineral, has been developed to account for the physical causes of
color phenomena arising from specular reflectance.
Many "stand-alone" ore mineral identification schemes now exist using
reflectance data as the primary parameter. These are often supplemented by
color values and micro-indentation hardness data. The most effective are those
for which the optical data correspond to minerals of known (pre- or postdetermined) chemical composition and crystallographic symmetry. At present
there are few inter-active identification schemes: a good example is that of the
MSFU-L-312, in which the measured values are automatically compared with
those from a pre-established database containing R data for more than 800
minerals. More, and more complete schemes are being developed.
References
Atkin BP, Harvey PK (1979) The use of quantitative color values for opaque mineral
identification. Can Mineral 17: 639-647
Chvileva TN, Bessmertnaya MS, Spiridonov EM (1988) Ore mineral identification in reflected
light. Kedra, Moscow
Criddle AJ, Stanley CJ (eds) (1986) The quantitative data file for ore minerals. 2nd issue,
IMA/COM. British Museum (Natural History), London
Gerlitz CN, Leonard BF, Criddle AJ (1989) QDF Database System. Reflectance of ore
minerals - a search-and-match identification system for IBM compatible microcomputers
using the IMAICOM Quantitative Data File for ore minerals, 2nd issue. US Geol Surv
Open-File Rep 89-0306A-89-0306E
Jambor JL, Vaughan DJ (eds) (1990) Advanced microscopic studies of ore minerals. MAC;
Commission on Ore Mineralogy Short Course Handbook, 17. Mineralogical Association of
Canada, Nepean, Canada
Marfunin AS (1979) Physics of minerals and inorganic materials. Springer, Berlin Heidelberg
New York
Peckett A (1992) The colors of opaque minerals. John Wiley & Sons, Chichester, England
Phillips JC (1966) The fundamental optical spectra of solids. Sol State Phys 18: 55-164
Reeson KJ, Criddle AJ, Pearson P, Chater RJ, Chrisstensen K, Alderman J, Booker GR,
Kilner JA (1991) Microscope-spectrophotometric analysis to determine the origins of the
color variations on SIMOX wafers. Nucl Instr Meth 55: 718-724
Criddle AJ, Pearson PJ, Reeson KJ, Robinson AK, Hemment PLF, Marsh CD, Booker CG
(1992) Non-destructive characterization of thin film SIMOX structures using microscope
spectrophotometry. Materials Sci Eng B12: 185-190
Shuey RT (1975) Semiconducting ore minerals, Developments in Economic Geology 4.
Elsevier, Amsterdam
Strens RGJ (1979) Determining the optical constants of opaque minerals. Bull Mineral 102:
308-313
Strens RGJ, Freer R (1978) The physical basis of mineral optics. Mineral Mag 42: 19-30
Tossell JA, Vaughan DJ (1991) Theoretical geochemistry: applications of quantum mechanics
in the Earth and mineral Sciences. Oxford Univ Press, England
Vaughan DJ, Craig JR (1978) Mineral chemistry of metal sulfides. Cambridge Univ Press,
England
492

R.M.A. AzzAM and LA. BRYZGALOV
Some new aspects of optical spectroscopy as a vehicle of investigating absorbing
minerals have emerged in recent years. In the past the main problem was the
diagnostics of minerals, which was successfully solved by direct measurements of
reflection. At present the urgent problems involve the investigation of the fine
band structure of minerals, the quantitative estimate of the state of their
surfaces, as well as the study of their interaction with reagents and of the
consequences of their exposure to some active factors with the purpose of
optimizing their properties to solve problems of technology and materials
science. The intense continuous background in the spectral reflectance curves
which results from the normal incidence of light on the specimen is an obstacle
to revealing the specificity of the material band structure.
The sensitivity and accuracy of measurements of reflection spectra can be
improved by several orders of magnitude if use is made of modulation spectroscopy. In this technique the derivative of reflectance L1RjR with respect to some
parameter which can influence the optical transitions is measured. What can be
modulated is the wavelength of light interacting with the crystal (external
modulation) or some field (e.g., temperature, electric, or elastic fields) to which
the crystal is exposed (internal modulation). The general principles of modulation spectroscopy, detailed descriptions of its techniques, and a review of its
results can be found in the monograph of Cardona (1969) and in conference
proceedings. Of particular interest are the results for gold and silver, lead
chaicogenides, and zinc sulfide, whose optical modulation spectra clearly exhibit
the features connected with bandgap and inner transitions, spin-orbit splitting,
and with the exciton interaction. The technique of modulation spectroscopy
imposes strict requirements on the state of aggregation (homogeneity) of the
material under study and on its crystallographic orientation. For this reason
modulation spectroscopy is impossible to apply to all minerals. There are also
additional limitations with respect to the accuracy and information yield of the
technique when processing the results with the Kramers-Kronig integral relations. Unfortunately, at present, there are no commercial modulation spectrophotometers.
Neither direct measurements of reflectance nor modulation spectroscopy
allow dependable quantitative estimate of the surface state of the material.
Ellipsometry is free from the afore-mentioned limitations and has a variety
of advantages over other optical techniques. The term ellipsometry, introduced
nearly 50 years ago, exactly expresses the essence of the technique of investigating variations in the elliptic polarization parameters caused by the lightmaterial interaction.
When the incident light is linearly polarized at 45 azimuth with respect to
the plane of incidence, the main parameters of the polarization ellipse of the
reflected wave are the angles L1 and '1' which characterize, respectively, the phase
493
difference between two components (p and s) of the electric vector of the

reflected light and the ratio of their amplitudes. The relationship between the
experimentally determinable L1 and If' and the optical characteristics of
a particular optical system is expressed by the fundamental equation of ellipsometry, p = tg If' eiLl , where p = Rp/Rs is the complex relative reflection coefficient. The angles L1 and If' are related to the refractive index (n) and extinction
coefficient (k) of the substrate material. In investigating complex optical systems
(anisotropic, multilayered, absorbing) p becomes a complicated function of the
parameters of the reflecting structure which requires a specific body of mathematics and computational techniques to interpret.
Elliptical polarization is analyzed with special instruments called ellipsometers. The classical ellipsometer comprises a light source, monochromator,
collimator, linear polarizer and analyzer, and a detector. The specimen is placed
between the polarizer and analyzer, and a phase shifter (compensator) is
installed either before or after the specimen. All of the polarizing optical
elements of the ellipsometer are housed in rotatable precision mounts and can
be adjusted to make any angle with the plane of light incidence. The parameters
L1 and If' of the polarization ellipse depend not only on the properties of the test
object and the azimuth of the linear polarization of incident light, but also on the
angle of incidence. That is why the specimen surface should be accurately
positioned and oriented and the angle of incidence <p must be chosen for
maximum possible accuracy (usually near the so-called principal angle). The
angles L1 and If' can be determined in different ways. Accordingly, we can
distinguish null, photometric, and interferometric ellipsometers. Of wide current
usage are photometric ellipsometers, in particular those that employ a rotating
analyzer or a photoelastic polarization modulator.
An analysis of the advantages and drawbacks of different ellipsometers
shows that automated modulation null ellipsometry is characterized by a higher
accuracy of measuring L1 and If' and by a speed of response of several
milliseconds, which enables one to observe the kinetics of such processes as
deposition, implantation, epitaxy, or desorption of a substance. On the other
hand, ellipsometers with a rotating analyzer or polarizer (or those with modulation of the angle of incidence) are preferable in spectral measurements because
they allow one to abandon the compensator.
Commercial ellipsometers are manufactured by Gaertner Scientific Corporation, Rudolph Research Corporation, and John Woollam Company in the
USA. In France, Jobin-Yvon produces spectroellipsometers based on the
photo-elastic modulator for 230-930 nm, and Sopra makes spectroellipsometers
with a rotating polarizer. The USSR has mastered the manufacture of
ellipsometers of series LEF and LEM. The most promising (for mineralogical
investigations) are automatic computer-controlled modulation spectroellipsometers which enable the study of micro-objects in different media and in a
wide temperature range.
Because of its numerous valuable attributes, and first of all its unique
sensitivity, ellipsometry has found widespread applications in optics for studying the properties of absorbing materials, and in the physics of solids in
494
ascertaining the peculiarities of the band structure of metals and semiconductors. In the physical chemistry of surfaces, ellipsometry has become a major
method of investigation, for it provides information about:
1. surface roughness;
2. thickness, composition, and structure (crystalline or amorphous) of a natural
or deposited layer;
3. composition and thickness of each layer of a multi-layered system resolvable
to 1--3 A.
Ellipsometry has played an important role in microelectronics and materials

technology for the rapid quality control of various films and coatings and for the
determination of their parameters. It is an efficient technique for studying
different processes occurring at interfaces. Because it is a noncontacting and
nondisturbing method, ellipsometry is also widely employed in the study of
living matter.
In mineralogy, ellipsometry is mainly used for studying the optical properties of minerals and for establishing the composition-dependent properties of
isomorphous minerals (chromospinellides, lead sulfoantimonides, fahlores, iron
mono sulfides, garnets). However, no account has yet been taken in such studies
of the effect of surface layers, oxide films, and roughness on the optical
characteristics of the examined materials.
Further application of ellipsometry to anisotropic absorbing objects will
obviously lead to novel diagnostics of minerals based on the determination of
the fundamental optical and energy constants of specimens. This will allow the
refinement of optical mineralogy of known substances and the determination of
new composition-dependent properties for isomorphous and variable-composition minerals. Ellipsometry also enables: (1) the study of the relation between the
characteristic band structure and the variability in the physical properties of
a mineral formed under certain physicochemical conditions; (2) the study of
phase transitions of minerals at low temperature; (3) the investigation of the
physics and chemistry of surfaces of minerals and the nature and parameters of
mineral surface films for technological mineralogy and materials science; and
(4) the investigation of the interaction between living and inanimate matter in
bacterial ore leaching.
It should also be noted that ellipsometry is especially effective whenever it
can be used in combination with Auger electron spectroscopy.
References
Azzam RMA, Bashara NM (1977) Ellipsometry and polarized light. North-Holland Publ Co
Amsterdam
Cardona M (1969) Modulation spectroscopy. Academic Press, New York
Proc 2nd, 3rd, and 4th Int Conf on Ellipsometry (1969, 1976, 1980) Surf Sci vols 16, 56,96,
North-Holland, Amsterdam
Pollak FH, Cardona M, Aspnes DE (eds) Proc Int Conf on Modulation spectroscopy. SPIE
Proc, 1990, vol 1286. SPIE, Bellingham, Washington
495
Proc Int Con on Ellipsometry and other optical methods for surface and thin film analysis
(1983) ] Phys vol 44, Colloq CIO, Les Editions de Physique Les Ulis, France
Proc 1st Int Conf on Spectroscopic ellipsometry (1993) Thin Solid Films, vols 233 and 234.
Elsevier, Amsterdam
Proc 1st Int Conf on Modulation spectroscopy (1973) Surf Sci vol 37 North-Holland,
Amsterdam

L.B.
MEISNER
The study of nonlinear optical characteristics began in 1961 when Franken and
his collaborators in the USA first observed how the red beam of the ruby laser
with the frequency w (Al = 694 nm) partly transformed to ultraviolet with the
frequency 2w and A2 = Al/2 after its passage through quartz crystal. Such an
effect, known as the second-harmonic generation (SHG), represents a nonlinear
optical effect, since the optical polarization of the medium depends on the
square of the optical electric field. The lack of an inversion center which permits
second-harmonic production is just that condition which permits piezoelectricity.
After the first SHG observation, a number of other nonlinear optical effects
were discovered: third-harmonic generation, forced Raman scattering, and selffocusing and defocusing of the laser light. The appearance of tunable lasers led
to the original revolution in the spectroscopy of liquids, gases, and condensed
media: the methods of saturation, absorption, and two-photon excitation, free of
Doppler broading, the spectroscopy of the coherent anti-stokes, Raman light
scattering, and other methods appeared.
The physical reasons for the appearance of nonlinear optical phenomena are
sufficiently obvious and allow the application of a classical treatment. In the
intense light fields (which have the magnitude of intra-atomic fields), outer
electrons of highly polarizable atoms behave as anharmonic oscillators (dipoles),
and the field of light reradiated by them differs in frequency from incident light.
The optical polarization is a nonlinear function of the applied optical electric
field. Therefore, the optics of high intensity light is called nonlinear optics. The
optics of weak light flows, when the outer electrons behave as harmonic
oscillators and the optic polarization of the medium is a linear function of the
applied optical electric field, is called linear or common (pre-laser) optics.
Studies of the nonlinear optical characteristics of minerals also consider the
SHG effect, since most minerals are available as small grains. For such materials
to determine the noncentrosymmetric structure, based on the coherence of the
second-harmonic electromagnetic wave, coherent microscopy is used. The
essence of this method is as follows: a single grain of the mineral or
a powder specimen is placed in front of the objective of the microscope and
496
irradiated by the focused beam of a Nd 3 + laser (AI = 1064 nm). If the laser
induces SHG in the grain, in the field of vision in the eyepiece of the microscope,
a speckled (interference) image is formed, consisting of green (SH wavelength
A2 = 532 nm) and black spots; if the mineral has a centro symmetric structure,
the speckled image is absent.
In applied nonlinear optics a method for estimating the value of the
quadratic nonlinearity of powder materials (method of Kurtz) and a device for
its realization were developed.
The combined application of coherent microscopy and the method of Kurtz
eliminates many difficulties and makes it possible to identify noncentrosymmetric structures, which are characterized by the extremely low integral level of
the SH signal, and to estimate the nonlinearity. At present the space symmetry
groups for 50 mineral species, have been refined; it was established that for
samples of micas (for example, lepidolite) the same polytype may double the
frequency of the laser beam (the absence of an invasion center) or may not. The
quadratic nonlinearity of 27 mineral species was determined. It was shown that
its variation in the samples of different genesis reaches a factor of 100-150 (for
example, nepheline); the prospective mineral for quantum electronics, shortite,
was also revealed. A laser method for the rapid determination of the concentration of a quartz and other noncentrosymmetric mineral phases in (1) powder
samples and (2) thin sections was developed. Based on the integral principle, the
first method involves the measurement two parameters: the relative intensity of
the SH radiation of the sample and the relative transparency at the SH
wavelength. Using these parameters, the concentration of the noncentrosymmetric phase in the sample is calculated. The second method is based on a
differential principle and requires the determination of the relative number of
video impulses at a frequency different from the laser radiation frequency (for
example, SH impulses, photoluminescence impulses) on the condition that the
mean differential amplitude of the impulses reaches a predetermined level. This
method has no sensitivity restrictions and allows the analysis of any form of
sample (luminescence mineral phases are used).
New possibilities have appeared in the area of mineral separation. For
example, minerals of the feldspar group do not double the frequency of the laser
radiation, but quartz does. It should thus be possible to use this principle to
remove feldspar from quartz-feldspar raw material. Quartz which contains gasliquid inclusions and quartz which does not differ both in the intensity of the SH
and in the angular distribution of this intensity. This phenomenon can be used
in quartz separation. Certain perspectives are gained for the gold-containing
ores i.e., those in which gold associates with quartz.
The study of SHG effects in minerals provides new information and allows
one to choose new methods for a number of traditional mineralogical and
technological tasks. Although the investigation of the frequency dispersion of
cubic nonlinearity is very difficult, it actually opens boundless possibilities for
obtaining spectroscopic information on minerals.
6.8 Technological Mineralogy and Technological Properties of Minerals
497
References
Guggenheim S, Schulze WA, Harris YA, Jiunn-Chorng L (1983) Noncentric layer silicates:
an optical second harmonic generation, chemical, and X-ray study. Clays Clay Miner 31(4):
251-260
Meysner LB, Golubnichiy VV (1988) Theoretical principles of laser optics - geometrical
method of mineralogical analysis. Miner J 10(6): 90-96 (in Russian)
Meysner LB, Kuzmin VI (1986) Theoretical aspects of nonlinear optical methods of separation. Obogashenie rud 5: 22-25 (in Russian)
Zernike F, Midwinter JE (1973) Applied nonlinear optics. John Wiley and Sons, New York
6.8 Technological Mineralogy and Technological Properties

of Minerals
O.V. KONoNovand W.
PETRUK
The constantly rising demand for mineral-bearing materials has led to the
exhaustion of rich, accessible, and easily processable ore reserves. The demand is
currently satisfied by open-pit mining and large scale processing of low-grade
finely disseminated, complex-composition, and difficult-to-enrich ores. The ore
volume processed has doubled in the last 10 to 15 years, with the current
amount being tens of billions tonnes per year. Similarly, the amount of mining
wastes increases by more than 5000 tonnes per minute in the USSR and
probably tenfold in the world. The mining wastes contain deleterious elements
and pose a threat to the environment because processing low grade mineralbearing materials entails enormous losses of major and minor valuable components.
The extensive development using traditional technological principles has
probably exhausted most possibilities for improving recoveries from low grade
ores. Consequently there is a need for new technological approaches and
processes which will improve recoveries of metal and nonmetal constituents
from mineral-bearing raw material. The need for technological approaches can
be met by technological mineralogy.
Technological Mineralogy
Technological mineralogy is a methodological and scientific basis for minerallurgy, i.e., the technology of primary processing of mineral-bearing raw material
for the metallurgical and chemical industry, for nuclear engineering, and for
making materials with valuable technological properties. The methodological
aspect of technological mineralogy is a complex of traditional and modern
techniques for investigating ores and processing products. The complex comprises:
498
1. geological and mineralogical mapping;

2. a study of spatial distributions and compositional variations of ore types;
3. a study of dependence of final compositions of ore deposits on enrichment
indices, and effect of enrichment indices on mineral behaviors during processing;
4. a study of the correlation between ore genesis and chemical, physical, and
physicochemical properties of minerals and mineral aggregates in ores;
5. a study of the relationship between mineral behaviors during processing
and the chemical, physical, and physicochemical properties of minerals and
mineral aggregates in ores;
6. development of processing requirements which must be met to achieve
optimum recoveries;
7. providing guidance for designing flow-charts of circuits in mills, concentrators, smelters, and refineries.
Technological mineralogy methods of studying ores employ theoretical
advances and analytical techniques which are used for genesis mineralogy,
crystal chemistry, physics, and physical chemistry of minerals. The analytical
tools include the electron microprobe, which is used for in-situ quantitative
analysis of major and minor elements in minerals; the PIXE, secondary ion mass
spectrometer (SIMS), laser ion microprobe (LIMS), laser ablation microprobe
(LAM), and other instruments, which are used for quantitative analysis of trace
elements (0.1 to several hundred ppm) in minerals; LIMS and auger microprobe
are used to determine elemental concentrations on particle surfaces; the scanning electron microscope (SEM), which is used for identifying minerals and
for observing mineral textures; and an SEM-EDX-image analysis unit, which
provides quantitative data on mineral characteristics with respect to processing.
The mineralogical characteristics obtained by SEM/image analysis are
mineral quantities, liberations of mineral grains, indices of intergrowths of
ore minerals with other minerals, distributions of grain sizes and shapes, and
relative and absolute areas of intergrain boundaries. Data collected by SEMI
image analyzers are evaluated by materials balancing techniques to determine
recoveries of liberated and partly liberated grains within each size range
throughout processing circuits. The results provide metallurgical engineers with
information about particles which tend to be recovered by each circuit and form
a basis for modifying circuits for maximum recoveries at optimum grades.
A chemical-mineralogical balance of mineral quantities and mineral compositions define the distribution of elements among minerals and is another
reliable mineralogical technique. The chemical-mineralogical balance combined
with materials balancing of liberated and unliberated grains determines the
distributions of valuable constituents in ores and in comminution and enrichment products. These data are necessary for calculating the theoretical
(limiting) recovery of the valuable ore constituents and for estimating the quality
of the final products. The evaluation of image analysis data by materials
499
balancing techniques provides the basis for predicting the feasibility and
economic practicality of ore enrichment while conducting geological prospecting; for defining comminution requirements and ore enrichment potential
while performing laboratory testing; and for improving comminution and
enrichment operations at mining and concentrating plants.
Mineralogical Characteristics that Affect Comminution
The response of minerals to comminution depends on such properties as

hardness, brittleness, elasticity, malleability, cleavage, chemical composition,
imperfection and deformation of crystal structure, inclusions of other minerals,
bond strength between minerals, degree of recrystallization, and tectonic disintegration. In addition, comminution is influenced by morphogranulometric
characteristics of mineral aggregates, and the proportion of different hardness
minerals in the aggregates.
When ores composed of different hardness minerals are ground, the hard
minerals are broken into coarse-grained particles, whereas soft and brittle
minerals are broken into fine-grained particles. For example, comminution of
the Akchatau ore (USSR) produces coarse-grained fractions enriched in quartz
and pyrite, medium-grained fractions enriched in tungstate, scheelite and fluorite, and fine-grained fractions enriched in bismutinite and mica. Similarly,
crushing and grinding the volcanogenic base metal ores from New Brunswick,
Canada, produces coarse-grained fractions enriched in pyrite and quartz,
medium-grained fractions enriched in sphalerite, pyrite and galena, and finegrained fractions enriched in galena, sphalerite, chalcopyrite, and chlorite.
The power consumption required for the ore comminution process, which
accounts for 80% of the total power consumption for ore processing, increases
considerably with the gradual comminution of ores. In particular, a study on
breakage of a volcanogenic ore composed of massive pyrite and sphalerite
showed that initial breakage occurred by splitting along cracks in massive pyrite
and along cleavage planes in massive sphalerite and galena, and produced a
large particle size reduction; secondary breakage occurred by separating weakly
bonded pyrite grains along grain boundaries, and produced a moderate particle
size reduction; tertiary breakage, which took three times the power consumption
and occurred by separating moderately bonded pyrite grains along grain
boundaries, produced a much smaller particle size reduction; and a final
breakage of fine-grained material, which required an additional threefold power
consumption and occurred by random breakage across grain boundaries,
produced very little particle size reduction.
Mineral grains exposed to the mechanical actions of comminution may
experience elastic and plastic deformations, lead to twinning, and polymorphic
conversions. For instance, gold leafs may be rolled into ellipsoidal balls, and
calcite can be displaced on the surface by aragonite. The mechanical actions can
also cause an increase in the dislocation density and may lead to surface
500
amorphism. In other instances the actions stimulate oxidation and dissociation

processes, and may lead to changes in the chemical composition, structure, and
physicochemical properties of the surface.
Mineralogical Characteristics Which Affect Enrichment

The differences in chemical, physical, and physicochemical properties of minerals are used to separate valuable minerals from gangue, and to concentrate the
valuable minerals. The technological mineral properties include radioactivity,
luminescence, gravitational, magnetic, flotation, induced radiation, heat treatment, electromagnetic, electrostatic, and chemical action. Some of the properties
are used for ore sorting, some for bulk separations, and some for both.
Ore Sorting
Radioactivity and Radiation-Absorbing/Reflecting Properties
Ore sorting based on radioactivity and radiation-absorbing/reflecting properties of minerals is dependent on the chemical compositions of the minerals.
These are:
- natural radioactivity which is characteristic of uraninite, thorite, uraniumbearing micas, as well as of phosphorites and combustible shale owing to
traces of U and Th;
- radioactivity induced by C(-, /3-, Y-, and neutron (n) radiation of different
energles;
- characteristic X-ray radiation induced by C(-, /3-, Y-, and n-radiation of ores of
rare-earth and nonferrous metals (Cu, Pb, Zn, Sb, W, Mo, Ta, Nb, Sn, Bi, etc.);
- different degrees of absorption and reflection of radioactive radiation and
X-rays by different minerals.
Luminescence Properties
The luminescence properties of minerals are employed in the lump separation

of scheelite ores, fluorites, and diamond kimberlites. Luminescence is excited
by ultraviolet radiation or X-rays. The difference in the kinetic parameters of
luminescence (build-up and quench rates) is effective for the X-ray luminescence
separation of scheelite and diamond ores. In this case it becomes possible to
separate scheelite from calcite, fluorite from wollastonite, and diamond from
calcite, apatite, and zircon.
The luminescence separation of cassiterite with the use of an UV laser as
the exciter has been established. Novel nonlinear optical technique has been
developed for separating nepheline-feldspar from a quartz-feldspar raw material. These techniques are based on the ability of crystalline structures of minerals
without the inversion centers to generate the second harmonic on their exposure
to laser radiation.
501
Photometric Properties
The color contrast of the minerals to be separated is used in the photometric
separation of gold-bearing white quartz from enclosing black shales, and white
magnesite from green serpentinite.
Bulk Separations
Gravitational Methods
The density of minerals is employed as a separation technique during beneficiation and during concentrate enriching operations with ores of noble (Au,Pt),
rare (W,Mo,Sn,Zr,Ti,Ta,Nb), nonferrous (Pb,Zn,Cu) metals, and diamonds.
Techniques using density of minerals include mechanical methods such as
tabling, jigging, spirals, cones, hydrocyclones, and heavy media suspension
(mainly magnetic fluids).
Skarn-carbonate W-Mo ores of the Tyrnyauz deposit (USSR) have been
enriched in heavy media suspensions by separating heavier skarn pieces with
scheelite from light marble calcite. The Altai disseminated polymetallic ores in
the USSR are separated from metamorphosed enclosing rock by the difference
in density between the ore minerals and rock. The magnetite and hematite
in iron ores in Canada are separated from silicate and carbonate gangue with
large scale spirals in concentrators that process over 100 000 tonnes of iron ore
per day.
The efficiency of gravitational enrichment is influenced by the mass, size, and
morphology of mineral particles to be separated, and by the change in the
density of variable-composition minerals as well as intergrowths containing
mineral inclusions. Process Mineralogy investigations may define the optimum
degree of comminution for maximum possible yield of liberated and unliberated
mineral grains.
Magnetic Properties
The magnetic properties of magnetite and maghemite are employed for dry
lump separation of iron ores in weak magnetic fields. Wet electromagnetic
separation in fields of up to 1000 oersteds is used to separate magnetite from
quartz and other minerals in finely disseminated ores. Process mineralogy
investigations have shown a relationship between the quality of ore concentrates
and the amount of intergrowths of quartz with magnetite, as well as the presence
of isomorphous impurities of magnesium, titanium, and other elements. The
recovery of iron is also influenced by the natural magnetization of magnetite and
the decreasing amount of isomorphous impurities as well as oxidation and
pseudomorphous substitution by maghemite and hematite. Recent developments on high intensity magnetic separation (over 10000 oersteds) have made it
possible to recover hematite from iron ores.
The differences in magnetic properties are also useful in enriching tungstate
from tantalite--columbite ores, and in separating pyrrhotite from copper-nickel
and polymetallic ores.
502
Flotation
The flotation properties of minerals are used for enriching almost 80% of rare
minerals, nonferrous metal-bearing minerals, and finely disseminated ores.
Flotation is based on the differences in the surface properties of minerals, their
hydrophobicity or water receptivity, as well as on their different abilities of
reacting with flotation agents. Apolar and polar organic molecules play the role
of collectors, and salts of inorganic acids represent depressors. The flotation
properties of minerals are determined by the chemical bond type and by the
degree of compensation of comminuted particles on the surface. They also
depend on the crystallographic orientation of cleavage splitting, isomorphous
impurity content, and on the presence of structural imperfections and mineral
inclusions.
The natural floatability in water and oil-receptivity are exhibited by native
metals with metallic bonds, nonmetals with covalent and molecular bonds,
sulfides and oxides with donor-acceptor, covalent and molecular bonds, and
layered silicates such as talc and pyrophyllite with Van-der-Waals bonds on the
surfaces of cleavage flakes. Most oxides, oxygeneous salts, and silicates with
prevailing ionic bonds are hydrophillic and therefore unfloatable. If polar
molecule collectors are adsorbed on the surfaces of such minerals, the latter
manifest floatability. The induced flotation properties of minerals depend on the
degree of attachment of flotation agents on their surfaces. Their adsorption may
be prevented by surface pretreatment with depressors. The process mineralogical study of ores from various deposits has shown a strong variability of the
flotation properties of many minerals.
The natural floatability of the minerals of the scheelite-molybdoscheelitepowellite series is proportional to the amount of isomorphous molybdenum
which increases the degree of covalence of the chemical bond. The induced
floatability due to formation of hydrophobic calcium oleate on the surfaces of
cleavage splitting along a dipyramid and a prism is inversely proportional to the
molybdenum content. This may be accounted for by the processes of concentration ordering and decomposition of the solid solution with the formation of
oriented powellite micro-inclusions. Variations of the floatabilities of fluorite
modifications differing in the color and luminescence are caused by different
concentrations of structural-chemical defects on the particle surfaces. These
defects are mainly represented by anion vacancies and rare-earth ions with
locally uncompensated excessive positive charges which provide the stable bond
with the oleinic acid molecules.
The variability of the flotation properties of minerals is also dependent on
the flotation agent conditions and the salt composition of the flotation pulp. In
real flotation conditions the salt composition is determined by the presence in
ores of readily oxidizable, easily solvable minerals, as well as minerals with
a high specific surface area and a crystalline structure which ensures a high
adsorptivity and the ion-exchange properties. The dissolution of the products of
oxidation of pyrrhotite and chalcopyrite, i.e., melanterite, chalcanthite, gypsum,
and calcite, leads to the continuous presence of ions of calcium, iron, copper,
503
sulfate and bicarbonate in the pulp. It is known that the adsorption of copper
ions on the surface of sphalerite intensifies its flotation by xanthogenate, but the
effect can be reduced or eliminited by conditioning with Na cyanide. The joint
flotation of fluorine-containing biotite with scheelite, fluorite, and calcite, which
worsens the quality of the scheelite concentrate, is explained by the activation of
the cleavage plane of this mineral by calcium ions with which the hydrophobic
molecules of oleinic acid form stable bonds.
Induced Properties
An intentional change in the technological properties of minerals, aimed at
intensification of ore processing, may be achieved by radiation, thermal, chemical and mechanical actions on minerals. A study is also being carried out on the
influence of the laser, electron beam, plasma, ultrasonics, electric pulses, and
other techniques on the technological properties of minerals.
Radiation. Exposure of minerals to radiation induces radioactivity and characteristic X-ray radiation which enable enrichment separations of ores that could
not otherwise be enriched. The radiation displaces atoms from their equilibrium
positions and produces thermally unstable defects which play the role of optical
centers and centers of adsorption of flotation agents due to the excessive charges
of atoms.
The radiation also ionizes and distributes charges and thereby localizes the
trapping levels and the formation of thermally unstable color centers with their
corresponding neutral adsorption centers on the surface. This process prepares
an ore for flotation.
The irradiation of scheelite with high-energy particles causes its long-time
afterglow due to an emission shift towards the long-wave region by 100 nm. This
induced property can be used to improve X-ray luminescence separation;
Heat Treatment causes the following:
1. Complete or partial decomposition of minerals, as occurs, in magnetic
calcination of oxidized iron ores and in sintering and agglomeration of their

enriched products.
2. Partial thermal dissociation of minerals. For example, water-soluble nonstoichiometric calcium tung states, such as Ca 2 WO s and Ca 3 W0 6 , are
formed by heat treatment of a scheelite concentrate.
3. Polymorphic conversions and the production of new technological properties. For example, the calcination of spodumene ores up to 950C leads to the
cubic modification (LiAISi 2 0 6 ) which is easily powdered. Screening into
a fine fraction enables separation of the cubic LiAISi 2 0 6 from quartz and
feldspar.
4. Structural ordering and homogenization of heterogeneous mineral systems
which are the products of decomposition of solid solutions. In this case the
representatives of the isomorphous series of ferrispinelides experience a
504
considerable change in their magnetic properties, whereas those of the

scheelite-molybdoscheelite-powellite series demonstrate changes in their
floatability and luminescence properties.
5. Formation of equilibrium point defects and decomposition of associative
defects, as well as delocalization of charge carriers from trapping levels. This
is accompanied by a change in the spectroscopic kinetic parameters of
luminescence directly related to X-ray luminescent and photometric separations.
6. Temperature quenching of the luminescence of some minerals, thermal
magnetic disordering of others with a decrease in magnetization, and diffusion of atoms with a rise in the ionic conductivity.
The Chemical Action on minerals leads to a change in the chemical composition

of mineral surfaces and to formation of new phases in the form of thin
enveloping films. For example, the sulfidization of oxidized copper ores coats
the surfaces of mineral particles with copper sulfides and causes the particles to
be readily floatable in the presence of xanthogenate.
References
Barskii LA, Kononov OV, Ratmirova LI (1979) Selective flotation of calcium-containing
minerals. Nedra, Moscow, 232 pp
Barskii LA (1984) Fundamentals ofminerallurgy. Theory and minerals separation technique.
Nedra, Moscow, 270 pp
Ginzburg AI, Kuzmin VI, Sidorenko GA (1981) Mineralogical investigations in geological
prospecting. Nedra, Moscow, 237 pp
Laguiton D (1985) The SPOC manual, CAN MET Report SP 35-1/3. 2E, CAN MET,
Department of Energy, Mines and Resources, Ottawa, Canada
Petruk W (1988) Ore characteristics that affect breakage during grinding. In: Carson DJT,
Vassiliou AH (eds) Process Mineralogy VIII. (Warrendale, PA; AIME/TMS), pp 181-193
Petruk W (1988) Capabilities of the microprobe Kontron image analysis system: application to
mineral beneficiation, Scanning microscopy, 2(3), pp 1247-1256
Pirogov BI, Porotov GS, Kholoshin IV, Tarasenko VN (1988) Process mineralogy of iron
ores. Nauka, Leningrad, 304 pp
6.9 Mineral Properties in Engineering Geology

J.E.
GILLOTT
and V.I.
OSIPOV
The study of minerals in engineering geology is focused mainly on their physical,

physicochemical, and mechanical properties. These properties depend in turn on
the chemical composition of the minerals, their structure, and the energy and
direction of the interatomic bonds.
505
Physical Properties
The physical properties of minerals of greatest importance to the engineering
geologist are density, specific surface area and electrical and thermal properties.
Minerals may be subdivided on the basis of density into light
(Pm < 2.5 g/cm 3 ), medium (2.5-3.3), heavy (3.4-6.0) and very heavy (Pm>
6.2 g/cm 3 ).
Specific surface area refers to the surface area per unit weight or volume of
the sample. It may be expressed as m 2 of surface per g of solid. Specific surface
area is important to adsorption processes. For most minerals (primary silicates,
simple salts, etc.) the specific surface is not large ( < 1 m2/g) and depends on the
crystal dimensions. Some minerals such as the clay minerals, however, have
large specific surface areas reaching 600-800 m 2/g in smectites.
Minerals are subdivided in terms of electrical resistivity into dielectrics
(quartz, mica, feldspars P ~ 10 12 _10 16 Q mm), and semiconductors (carbonates, sulfates, halogens) (10 4 -10 8 ), clay minerals 104 ), ore minerals
(p < 1 Qmm).
The specific heat of most minerals varies from 0.50 to 1.0 kJ /kg K, organic
substances - 0.8-2.10, and ice 2.09 kJ/kg K.
Thermal conductivity of common minerals varies from 0.40 to 7.00 W/m K;
thermal conductivity of water is equal to 0.63, and ice (0 dc) 2.20.
The electrical resistivity, thermal heat capacity, and thermal conductivity of
minerals depend on their composition, structure, and the type of chemical
bonding; properties vary anisotropically in crystals of lower symmetry.
Physicochemical Properties
Among physicochemical properties, those of most importance are affinity for
water, solubility, and resistance to weathering.
It is customary to express hydrophilicity in terms of the angle of wetting (8 0 )
or heat of wetting. The surface of a mineral is considered to be hydrophilic if
8 < 90 or when f3 = HB/HM > 1, where HB and HM refer to the heat of wetting
of the mineral with water and hydrocarbons. Hydrophilicity depends on the
chemical composition and structure of the surface of the mineral. Most minerals
are hydrophilic. Clay minerals and organic substances possess the largest
hydrophilicity.
Solubility depends on the size of the minerals, the temperature, pressure,
pH, and chemical composition of the natural waters. Minerals show considerable variation in solubility in water (e.g., halite, NaCl, 6.1 mol/I; dolomite,
CaMg(C0 3 b 0.35 x 10- 4 mol/I), those in which bonding is mainly ionic (simple
salts) generally being the most soluble. Silicates, including both primary and
secondary minerals and organic materials, generally have low solubilities in
water.
0
506
Resistance to weathering depends on the composition, crystal chemistry, and

the presence of large cations in the structure. Silicate minerals with the lowest
stability to weathering appear to be those containing heavy metals and large
cations (amphiboles, pyroxenes, feldspars). Minerals without large cations are
the most stable to weathering (quartz). The resistance to weathering of clay
minerals in ordinary conditions is rather high; however, it may significantly
decrease with change of pH in the environment.
Mechanical Properties
Important mechanical properties of minerals include their compressibility,
hardness, and strength.
Load induces strain, which in general is partly elastic and reversible and
partly irrecoverable due to plastic deformation and viscous flow. Stress, which is
load per unit area, occurs as three main types which are compressive, tensile, and
shear. [mportant elastic constants are the modulus of elasticity (Young's
modulus) (GPa), the modulus of rigidity (shear modulus) (GPa), the modulus
of volume compressibility (bulk modulus) (GPa) and Poisson's ratio (dimensionless quantity).
Hardness of minerals is often described in terms of resistance to scratching
by reference to Mohs scale of ten minerals. Hard minerals are as hard or harder
than quartz (7 on Mohs scale) and soft minerals fall below 7. A modified scale of
15 minerals is used for technical purposes. Microindentation hardness may be
determined by application of a controlled load to a pyramid-shaped (Vickers) or
rhombus-shaped (Knoop) diamond indentor. Vickers or Knoop hardness number may be calculated from a simple formula. The Vickers hardness is proportional to the ratio of the load to the square of the average length ofthe diagonals
of the indent. Hardness is also measured in the study of metals and in other
related fields where Brinnell and Rockwell hardness tests are performed together
with other techniques. In a comparable series of ionic compounds hardness
decreases with increase in inter-ionic distance. Hardness has been related to
strength.
Strength is the ability of a material when loaded to resist deformation and
fracture. The strength, stiffness, and strain capacity of the component minerals
and the cohesion and frictional resistance between them determines the mechanical properties of rocks and soils though porosity, discontinuities, mineral
orientation, pore water pressure, etc., have an important influence on behavior.
Compressive, tensile, and shear forces develop under load and lead to plastic
yielding or brittle fracture. Mechanical properties of rocks and minerals are
often determined from a stress-strain curve and materials are tested in compression, tension, direct shear, and torsion.
The mechanical properties of minerals depend on the mineral's structure,
types of interatomic bonding, presence of cleavage and crystal imperfections, as
well as on the conditions under which the tests are carried out.
507
Applications
Knowledge of the fundamental properties of minerals holds the key to modeling
the engineering-geological behavior of rocks and soils as foundation materials
and materials of construction.
As an example we may consider the hydration of clay minerals which may
involve formation of several layers of oriented water molecules at the surface,
ion hydration, development of a hydrous double layer, and intra-crystalline
expansion. Water uptake may form films with a thickness of several tens of
Angstrom units. Water uptake generates swelling pressure and expansion
(swelling), decreases soil strength, increases compressibility, and leads to plastic
deformation.
Swelling is one of the most destructive processes encountered in clay soils.
Swelling develops as a result of the disjoining action of hydrate films formed of
linked water molecules at the contacts of clay particles. Pressure of the order of
10 MPa may develop and result in reconstruction of the whole clay fabric. As
a result, the volume of the soil increases and the thickness of a clay soil may
increase by some tens of centimeters. Engineering structures (buildings, roads,
canals, pipes, etc.) built on such soils may be so damaged as to become
completely unserviceable. The total cost of repair to structures built on swelling
clay terrains requires large sums of money. Thus, in the USA the annual
expenditures connected with this process are about 6 billion dollars.
Deformation of foundations results not only from heave due to the swelling
of clay soils on moisture uptake or the growth of ice lenses but also from
settlement. This commonly results from shrinkage on moisture loss, but soils
which show a decrease in bulk volume on moisture uptake are relatively
common. Such soils include loess, some residual and alluvial deposits, and fill
materials. The effect is known as soil collapse, subsidence, and hydroconsolidation. Soils of this type generally have a low density, a high porosity, a void
ratio greater than 1, and significant differences in mechanical properties before
and after collapse; in loess there is also a relatively high vertical permeability
associated with pores formed from root casts. Potential for collapse of low bulk
density loess has been found to be considerable when the moisture content
exceeds the liquid limit and various procedures including consolidation tests
have been used to obtain a measure of collapse potential. Loess consists of
calcareous silt with smaller amounts of fine sand and clay; the principal
constituents are quartz, feldspars, clay minerals (kaolinite, hydromica), goethite,
and salts (carbonates and sulfates). Loess is widely distributed around the
margins of the Pleistocene glaciation in Asia, Europe, and North America. The
silt particles are thought to have been formed by glacial grinding or by
weathering under cold conditions. Most workers have concluded that loess was
transported by wind from arid regions, alluvial valleys, outwash surfaces, and
unconsolidated glacial and fluvioglacial deposits. Loess is also associated with
problems caused by slope instability, silting of canals and reservoirs, and soil
erosion. Special techniques have been developed to improve stability but
building costs on loess often increase by 10 to 20%.
508
Hydration of clay minerals is also accompanied by a significant decrease in

soil strength and, even more importantly, by a reduction in resistance to shear
stress. This is one of the main reasons for the loss of stability of soils and rocks
on slopes with the development oflandslides, debris flows, and mudflows. Slides
and flows are often associated with the development of excess pore water
pressure. Extra water may become available due to heavy rain, melting snow, a
rise in the groundwater table, or flooding caused by natural or human agencies.
The excess pore pressure is also associated with a change in the arrangement of
the fabric elements in a soil. Contractive or dilative processes may occur. In
quick clays the soil fabric is thought to change from a relatively open to a more
close-packed arrangement. The open fabric was stable on deposition but
environmental changes caused the loose packing to become metastable. Disturbance results in a change to a more close packed configuration and the
deposit becomes oversaturated so that shear resistance decreases drastically and
the soil flows like a viscous liquid. Quick clays are common in eastern Canada,
Alaska, and parts of Scandinavia. The volume of the largest landslides reaches
several hundred millions of cubic meters. Damage from landslides in such
countries as the USA, Japan, and China reaches 1-2 millions of dollars
annually. Many landslides cause not only financial loss but also loss of life, and
sometimes become national disasters. Thus, for example, the landslides in the
province of Cansu (China) in 1920 caused the death of about 100000 people. At
present about 600 people die annually worldwide because of landslides.
Another example of the importance of the fundamental properties of minerals in engineering relates to their solubility. Problems arise in soils and rocks due
to the solubility of gypsum, anhydrite, calcite, dolomite, and others. Sulfate and
carbonate rocks formed from these minerals under specific hydrodynamic
conditions may experience chemical dissolution with the development of karst
terrane. In cases when karst cavities are located at a small depth from the
surface, the roof rocks may collapse with the development of sinkholes with
a diameter of up to several tens of meters and depths of up to 10 meters. The
development of such failures creates serious difficulties during construction and
increases the risk ofloss oflife. Thus, for example, in Russia, near Ufa for the last
65 years more than 80 karst failures have been reported and similar problems
have been described elsewhere. We know examples of modifying the properties
of the rocks in foundations of engineering structures by adding to them mineral
formulations. For example, the addition of an organic formulation based on
peat, in a proportion of 1% by weight, to asandy soil decreased the permeability
to water by a factor of several hundreds. Addition of soluble sodium salts to
carbonate-containing clay soils (clay, loess) decreased their permeability to
water by about 50 times. Both these effects are used in engineering practice
during the construction of canals, dams, and containers for industrial and
domestic waste.
During recent years it has become common to mix clay minerals with
polymers for injection grouting into rock fractures, thereby decreasing their
permeability to water, creating barrier zones with a low permeability and high
509
absorption capacity surrounding containers of toxic chemical agents and radioactive wastes.
References
Bates RL, Jackson JA (eds) (1979) Glossary of geology. Am Geol Inst, Falls Church, Virginia,
751 pp
Beck BF (ed) (1989) Engineering and environmental impacts of sinkholes and karst, AA
Balkema, Rotterdam, 384 pp
Clark SP (ed) (1966) Handbook of physical constants. Geol Soc Am Mem 97, 587 pp
Fleming RW, Ellen SD, Algus MA (1989) Transformation of dilative and contractive landslide
debris into debris flows - an example from Marin County, California. Eng Geo127: 201-223
Gillott JE (1987) Clay in engineering geology. Elsevier, Amsterdam, 468 pp
Grabowska-Olszewska B (1988) Engineering-geological problems of loess in Poland. Eng
Geol 25: 177-199
Gray DE (ed) (1972) American Institute of Physics Handbook. McGraw-Hill, i~ew York,
3rd edn. vii + 2442 pp
Handy RL (1973) Collapsible loess in Iowa. Soil Sci Am Proc 37: 281-284
Knight K (1963) The origin and occurrence of collapsing soils. Proc 3rd Regional Conf for
Africa on Soil Mech Found Eng 1: 127-130
Kutepov VM, Kodgevnikova VN (1989) Stability of karst territories. Science, Moscow, 150 pp
(in Russian)
Landolt-Bornstein (1950) Euken A, Hellwege KH (eds) Landolt, Hans Heinrich, Zahlenwerte
und Functionen aus Physik, Chemie, Astronomie, Geophysik und Technik, Sechste Auflage.
Springer, Berlin Heidelberg, New York
Lutenegger AL, Hallberg GR (1988) Stability of loess. Eng Geol 25: 247-261
Lynch CT (ed) (1974) Practical Handbook of materials science. CRC Press, Boca Raton,
Florida. 1989, 636 pp
Osipov VI, Babak VG (1987) Nature and mechanism of clay swelling. Eng Geol 5: 18-27
(in Russian)
Povarennih AS (1963) Strength of minerals. Academy of Sciences of the Ukrainian SSR, Kiev,
304 pp
National Research Council Advisory Board on the Built Environment Reducing losses from
land sliding in the United States. National Academy Press, Washington, D.C. 1985,41 pp
Sergeev EM, Golodkovskaya GA, Ziangirov RS, Osipov VI, Trophimov VT (1983) Terrain
science. Moscow State Univ, 388 pp (in Russian)
Smalley IJ (1966) The properties of glacial loess and the formation ofloess deposits. J Sediment
Petrol 36: 669-676
CHAPTER 7
Mineralogical Material Science
512
Chapter 7. Mineralogical Material Science
7.1 Concept of Materials as a New Approach to Solids and

Minerals, Natural Minerals, and Their Synthetic Analogs
as Materials
A.S. MARFUNIN
The next step in developing an understanding of solids is connected with the use
of extremely diverse, special manifestations of the properties of materials, with
their innumerable applications in many completely different fields. Moreover,
a transition from general theories to the most detailed elaborations of particular
theories regarding structural types families of materials has taken place.
Technical parameters describing the properties of modern materials reflect
the much more complicated characteristics of solids used as materials. This
applies not only to the use of materials in electronics, but also the consideration
of many kinds of mechanical, thermal, optical, and magnetic properties in
various technical devices.
All the properties of materials are electronic properties. Consequently,
calculations of chemical bonding (or electronic structure) in solids are necessary
to understand the theories of particular parameters describing the action of
materials in devices.
In the interrelations: crystal structure-electronic structure-solid state spectroscopy-electronic properties, these properties have provoked radical changes
in the approach to solids and consideration of them as material.
It is in this area that the most sophisticated understanding of matter and its
most intricate applications in new branches of technical methods and electronics
are being developed.
A general overview of solids as possible materials can be represented by
structure types (as in Chap. 2.3) or (taking chemical substitutions into account)
by families of materials. Many of the materials and families of materials are
designated by title compounds represented by minerals, e.g.:
garnets M3M2 T 3012 (silicate garnets, rare earth garnets, Y-AI garnets, etc.),
tourmalines MM3M6 T 601SB03X3+ 1, zeolites (M +, 1/2M2+)TxSi 1_x 0iH 20)n,
sodalite Na sCI 2AISi0 4, petalite LiAISi0 4, spodumene LiAISi 20 6, wollastonite
CaSi0 3, beryl Be3A12Si601s,
quartz SiOrberlinite AIP0 4, corundum-ruby-sapphire A1 20 3, chrisoberyl
A1 2Be0 4, rutile Ti0 2, wiistite Fe 1- xO, ferrites-spinels MM 20 4, hematite
Fe 20 3, ilmenite FeTi0 3, perovskites CaTi0 3, paratellurite Te0 2, sillenite
Bi 20 3, apatites Ms[T04]3X, alunites M+M~+[T04]2X6' boracites
M3B7013X, calcite CaC0 3, scheelites CaW0 4, powellites PbMo0 4, anhydrite
CaS04,
pyrites, marcasites MS 2, arsenopyrites FeAsS, nickeline NiAs, pyrrhotite Fe 7SS,
molybdenite MoS 2, cinnabar HgS, sphalerite ZnS, galena PbS, proustite
Ag 3AsS 3, pyrargyrite Ag 3SbS 3, stanosulites (berndtite) SnS 2-SnSe2' stibnite
7.1 Concept of Materials as a New Approach to Solids and Minerals
513
(antimonite) Sb 2 S3 , sulvanites CU 3 VsS4 ,

fluorite CaF 2, sellaite MgF2' calomel Hg 2Cl 2, and diamond.
Some of these are represented by a single material (e.g., diamond), while
others comprise dozens of compounds: 60 pyrites and similar types, about
100 nickelines-pyrrhotites, 120 zeolites, several dozens of apatites, alunites and
boracites.
However, there are many important materials which do not have analogs
among the minerals: silicon, germanium, GaAs, LiNb0 3 , Bi12Ge02, KH 2P0 4 ,
etc.
Besides the conventional uses of minerals as refractory, abrasive, ceramics,
binders, and other materials (see Szymanski 1988)1 their most interesting
applications now exist in extremely important new fields such as solid-state
electronics, space techniques, communications, energetics, nuclear technology,
instrumentation, new generations of construction materials, new engineering
ceramics, and composites. It is exactly these fields which characterize modern
material science and technology.
What is the common feature for all these applications and what sharply
separates them from conventional uses? The common denominator here is that
all these materials are functional materials: working crystals, active glasses,
films, and ceramics, whereby, their use is determined by processes, at the
electronic atomic, and molecular levels.
These are the materials which generate, modulate, transform, and absorb
radiation; count photons, electrons, and nuclear particles; register ionizing
radiation; change polarization and magnetization; and react to electrical, magnetic, and mechanical forces.
Other types of crystals separate and absorb molecules, split them, and
control the direction of their reactions. Still other materials resist extreme
working conditions e.g., in heat-resistant satellite shields, in nuclear reactors, in
radioactive waste containers. Thus, the diversity and depth of understanding of
material properties were revealed through the use of devices which have brought
corresponding phenomena of nature to their ultimate possibilities. Technical
characteristics which control the action of the devices are at the same time
experimental parameters describing the properties and relating them to the
electronic structure of solids.
One of the most striking features of some unique materials is their multifunctional applications: for instance, diamond is used not only due to its hardness
but also due to its heat conductivity, its semiconducting, counting, spectroscopic
surface, and many other properties and their combinations in extremely diverse
types of devices.
Another feature of materials is the complex set of properties which characterize them as real and concrete crystals with individual behavior at high or low
1 Szymanski A (1988) Technical mineralogy and petrography, An introduction to materials
technology. PWN-Elsevier, Amsterdam
514
temperatures, under different working conditions, with characteristic impurities

which determine semiconducting and spectroscopic properties, with specific
interactions with radiation.
In most cases minerals serve as search systems for new materials. Natural
minerals used as materials in electron techniques are represented by diamonds,
quartz, zeolites, but even here their synthetic analogs are most suitable. Many
other minerals are used in technical applications.
This concept of materials now concentrates the most sophisticated results
of studies and the application of solids It casts its gleam on minerals used as
materials and opens a window inside this world of modern technology. It
presents possibilities with respect to studies at the boundary between materials
science and mineralogy.
Materials now include working crystals, films, glasses, synrocks, ceramics,
and composites.
When natural minerals are considered in connection with the extreme
conditions of their existence, which need the most complicated interpretations
and calculations, one often prefers to write about geological and planetary
materials, or about materials from the Earth's interior.
In the following sections of this chapter the materials for semiconducting
and quantum electronics and optics as well as the most important multifunctional minerals-materials are considered. In other chapters many other problems related to minerals-materials are discussed: poly types of layered minerals
(similar to stanosulite) as possible materials for energy conversion, glasses and
synrocks for radioactive wastes, extra hard materials, plastic deformation in the
production of construction materials, superionic conductivity, microwave
dielectric properties, nonlinear optics, thermal, electrical, magnetic, technological, and radiation properties, and remote sensing methods.
7.2 An Overview of Materials for Electronics and Optics

R.E. NEWNHAM and M.1. SAMOILOVICH
7.2.1 Piezoelectric Materials

A vast class of piezoelectric materials find their main application in devices
transforming mechanical energy into electrical energy. These materials are used
in instrumentation for metrology, radio and television, and communication.
Various sensors are used to determine temperature, humidity, stresses and
strains, as well as piezoresonators, piezotransformers, and piezomotors. Piezocrystals are used also in devices for frequency filtration.
Piezoelectric materials are characterized by the tensors of dielectric permittivity, elasticity (compliance) and piezoelectric modulus. Practically, for the
characterization of these materials the values of electro-mechanical coupling
coefficient (F, changing in the range of 0.01 % to 99%), temperature frequency
515
7.2.1 Piezoelectric Materials
coefficient (TFC, the best value is zero), and indices offrequency stability (10- 5
to 10- 12 , from some milliseconds to several years) are used in the needed ranges
of frequencies and temperatures. In some particular devices the combinations of
the nonoptimal values ofk 2 and TFC are necessary (for example, in devices with
broad frequency bands).
Piezoelectric devices with frequencies of some kHz to hundreds of MHz are
made of single crystals with low k 2 < 2% ("weak" piezoelectric materials) as
well as of piezoceramics. The single crystals are quartz ((X-Si0 2), tourmaline,
XY 3Z 6 (B0 3hSi 6 0dOH,F)4' where X stands for Na+, Ca2+, K +, Mg2+; V-for
Mg2+, Fe2+, Fe3+, Li +, AP + and Z-for AP +, Fe 3+. An example of the
"strong" piezoelectric material for this frequency range is Rochelle salt,
KNaC 40 6 H 4 '4H 20 with k 2 = 65%. The popular and inexpensive PZT
ceramics (PZT = PbZr 1 _ xTix 03) have a basic working range of 1 kHz to
1 MHz and k 2 values up to 50%. Piezoelectric ceramic materials must be
carefully poled to align the ferroelectric domains.
Both "weak" and "strong" materials (k 2 > 2 %) are used in the manufacture
of devices for the MHz range. Single crystals of quartz, LiNb0 3, LiTa0 3,
berlinite (AIP0 4), and lithium tetraborate (Li 2B40 7 ) are utilized by the electronics industry. Similar characteristics are shown by perovskite ceramics
(AB0 3) and most especially by modified lead zirconate-titanate compositions.
Melt grown LiTa0 3 is a reasonably strong piezoelectric material with k 2
values up to 4% and special orientations with resonant frequencies that are
temperature-insensitive. LiNb0 3 has larger values of the piezoelectric coefficients but the thermal instability of resonant frequency is troublesome.
Phosphates and borates have lower k 2 though the frequencies are stable over
broad temperature ranges. Berlinite (AIP0 4) is representative of phosphate
materials of the type MeP0 4 (Me = AI, Ga, Mn, Fe) and is a promising material
for the electronics industry. It is a structural analog of quartz with a temperature
coefficient near zero (10- 9 C), and it surpasses (X-Si0 2 with k 2 = 2.3%. Uses of
berlinite are restricted because of hydroxyl groups incorporated in crystals
during hydrothermal growth.
Lithium tetraborate also surpasses quartz in some piezoelectric properties.
Cuts of 0, 78, 90 with temperature coefficients approaching zero have k33 four
times greater than kll of quartz. Crystals are grown by the Czochralski method.
This material would be used more widely were it not so hard to cut and polish
because of its solubility in acids.
In microwave piezodevices for GHz frequencies, the materials with high k 2
values are mainly piezoceramic materials and thin film piezoelectric structures.
Thin films of zincite (ZnO) deposited on insulating substrates such as glass,
sapphire, and silicon are good piezoelectric materials.
7.2.2 Materials for Acoustoelectronics

Acoustoelectric materials are used to generate, transform, and transmit radio
signals. Operating mechanisms are based on a number of phenomena related to
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the intrinsic interaction of different types of acoustic waves with the electronphonon system of the material. Acoustoelectric materials are used in communication and information systems, instrumentation engineering, and in
various other systems for generating and filtering signals and controlling their
frequencies.
Requirements for material properties depend on the type of wave propagation: bulk acoustic waves (BA W), surface acoustic waves (SAW), magnetostriction waves (MSW) and subsurface acoustic waves (SSA W).
For signals generated in piezoelectric materials, the basic parameters include
elastic wave velocity, intrinsic loss, insertion loss, thermal variations in velocity,
and time delay. Important characteristics of acoustoelectric materials are
flatness, cleanliness, and cost.
The acoustic velocity is very slow in acoustoelectric devices used for low
frequencies such as bismuth germanate (v = 1680 m/s) and very fast in crystals
used at high frequencies, such as diamond with its record v = 12100 m/s.
The group of "slow" materials includes bismuth germanate and silicate
(Bi 1z GeO zo , Bi 12 Si0 2o ) and thallium sulvanite (TI3BX4)' These materials are
used for broad band filters with low frequencies and for delay lines because of
their low acoustic wave velocity and high k 2 values. The drawback of these
crystals is the large temperature dependence of SAW propagation and time
delay. Thallium sulvanites are not widely used because of ecological problems
encountered during production.
The "slow" crystals, ceramics and quartz glass, are used mainly as low
frequency acoustoelectrics. Devices working at 150 MHz are manufactured
from crystalline quartz, lithium tetraborate, berlinite, and piezoelectric ceramics
of lead zirconate-titanate, LiNb0 3 is superior to quartz in some applications
because of its high k 2 (6%), easy production and rapid wave propagation up to
3488 m/s in YZ-cuts.
Ruby and rare earth-doped garnets are used as substrates. Sound waves
travel in yttrium aluminum garnet (YAG) at 8563 mls in the [001] direction and
at 5029 m/s along [110]. Control of the acoustic velocities and insertion losses is
achieved by means of different rare-earth dopants. Lutetium doped garnet has
much lower damping than ruby. Current industrial practice utilizes piezoelectric
semiconductors such as GaAs on glass or sapphire substrates for devices in the
high frequency range. They are manufactured in the form of laminar or layered
systems. Materials with high k 2 and high propagation velocities are used in the
form of thin films (ZnO, AIN, Li 2 B40 7 , Ta 2 0 s, Ba 2 Si 2 TiO s).
7.2.3 Materials for Optics, Electro-optics, and Acousto-optics

A great number of synthetic analogs to minerals are used as optical materials.
These components are employed for transmitting, converting, and storing light
energy, and consequently information. They are used in communication lines,
7.2.3 Materials for Optics, Electro-optics, and Acousto-optics
517
in signal processing devices, various types of sensors, as well as in medical

instruments.
Among optical materials there are several special groups, but some general
characteristics apply to all: transparency over certain frequency ranges, indices
of absorption or attenuation within this range, optical homogeneity, and the
absence of bubbles and inclusions.
Traditional applications are as optical components for light transmission in
the infrared, ultraviolent and visible spectrum, although only a few materials are
transparent in sufficiently broad range (0.1 to 0.8 }Lm). Optical crystals are used
for manufacturing lenses, windows, and prisms where low refractive index and
minimum absorption are required. Quartz leads this group along with lithium
niobate (LiNb0 3), fluorite (CaF 2), corundum (AI 20 3), and the alkali halides
(NaCl, CsI, KBr, etc.).
Synthetic LiNb0 3 is transparent in the range of 0.35-4.5 }Lm, its absorption
coefficient being of the order of 10- 2-10- 3 cm- I . This material is optically
homogeneous and can withstand powerful pulses with duration up to several
picoseconds, though high energy fields alter its refractive index.
Natural fluorites are seldom used, not because of the lack of transparency,
but rather because of small size of usable crystals and because of phosphorescence and thermoluminescence. The crystals are also fragile and easily
scratched. In optical instruments synthetic fluorites are preferable.
Optical materials for the infrared spectrum (3 to 5}Lm in particular) are
required to have high strength and thermal stability up to 1300 K. Useful
materials for this IR range include sapphire (AI 20 3), spinel (MgAI 20 4 ), yttrium
oxide (Y 203)' magnesium oxide (MgO) and transparent mullite ceramics
(3AI 20 3 2Si0 2). Knoop hardnesses for these are 2200, 1300, 1950, 660, and
640 kg/mm 2, respectively. The corresponding absorption coefficients at 5}Lm
are 0.92, 0.5,1.5,0.1, and < 0.1 cm- I .
Another class of optical materials are the polarizer and analyzer crystals that
polarize light beams in various directions. These crystals are used to control the
propagation of electromagnetic radiation in microscopes, polarimeters, and in
integrated optic devices.
The basic parameter of these is birefringence (LIn). The value of birefringence
should be large in optically homogeneous crystals without structural defects.
In natural minerals LIn is the greatest in rutile (Ti0 2, LIn ~ 0.287), calomel
(Hg 2CI 2, LIn ~ 0.683), soda niter (NaN0 3, LIn ~ - 0.251), and calcite (CaC0 3,
LIn ~ - 0.172).
Somewhat smaller LIn values are found in lithium niobate (LiNb0 3,
LIn ~ 0.09), potassium dihydrogen phosphate (KH 2P0 4 , LIn ~ 0.041), ammonium dihydrogen phosphate (NH 4 H 2P0 4 , LIn ~ 0.045), natural quartz (Si0 2,
LIn ~ 0.009), and in sellaite (MgF 2, LIn ~ 0.01). Materials with low LIn are usable
when their lower limit of transparency extends far into the vacuum region of the
ultraviolet. In CaC0 3 this absorption limit is about 200 nm, whereas in Si0 2 it
is 160 nm, and in MgF 2 it is 110 nm. It should be noted, however that the
518
minerals and their synthetic analogs (CaC0 3, NaN0 3) having the best polarizing properties are not very hard, making it difficult to obtain polished surfaces.
Yet another group of optical crystals is composed of materials capable of
rotating the plane of polarization under an applied magnetic field (Faraday
Effect). These materials are used in fast-latching optical switches, modulators,
and as optical isolators in communication lines. They are characterized by an
angle of rotation per unit path length. Included in this group are garnets
(Me 3AI s0 12 -type), fluorides (CeF 3, LaF 2' EuF 2, LiTbF 4), and selenides (ZnSe).
Y3FeSOlZ: Bi-substituted garnets produces 45 rotation for 2 mm microwaves.
Electro-optic crystals change their refractive index under applied electric
fields. Materials which change their optical activity under field (electro gyration)
also are part of this group. It is necessary to distinguish between linear changes
in the refractive indices in noncentrosymmetric crystals (Pockels effect) and
quadratic changes (Kerr effect). The electro-optic materials find applications in
the modulation and control of laser beams in signal processing devices and in
the holographic storage of information. Electro-optic materials are characterized by a half-wave voltage, (V;'/2 - the lower, the better) or by an electro-optic
efficiency factor (I:V . . /2)-1. The possibility of optically induced changes of
refraction must be also taken into account.
Representative electro-optic materials are synthetic lithium tantalate,
lithium niobate, potassium dihydrogen phosphate, potassium titanyl phosphate,
bismuth silicate, bismuth germanate, bismuth titanate, and zinc telluride.
LiTa0 3, LiNb0 3 and KTiOP0 4 have V;'/2 values of 2.5 kV, 3.5 kV, and 2.0 kV
in the range of 0.35-4.5 !lm. The best electro-optic properties are those of
(Ba,Sr)Nb 20 6 (BSN) and K(Ta,Nb)03 (KTN). Although difficult to obtain,
large BSN crystals have VAj2 as low as 0.45 kV in the range 0.4 to 4.5 !lm.
In acousto-optic materials, acoustic waves produce a diffraction grating for
incident light, causing changes in frequency, amplitude, and direction ofthe light
beams. These materials are used in high resolution processors of optical
information, principally in communication optoelectronics as well as in microscopes. Selection of acoustic materials is not an easy problem because high
acousto-optic efficiency must be accompanied by low acoustic losses.
In the visible spectrum proustite (Ag 3AsS 3), lithium niobate (LiNb0 3), paratellurite (Te0 2), lead molybdate (PbMo0 4 ), germanosillenite (Bi 12 Ge0 2o), and
lithium iodate (a-LiJ0 3) are used. The synthetic materials have somewhat better
properties compared to natural crystals and are more reproducible technologically.
Devices for the infrared range incorporate complex halides, chalcohalides,
and chalcogenides that have high indices of refraction. Materials in this
group include cinnabar (a-HgS), calomel (Hg 2 CI 2), thallium phosphoselenide
(Ti 3PSe4)' and thallium arsenoselenide (TI3AsSe3)' Cinnabar has a damping
coefficient of 7dB/(s MHz2) for }, = 1.153!lm along [001]. Its transparency
range is from 0.62 to 16!lm and n = 2.705. TIAsS 4 has n = 2.626 and is
transparent from 2 to 35!lm with a damping coefficient of 6.2 dB/s'MHz 2 at
Ii = 1.153 !lm along [001].
7.2.4 Laser Materials
519
Optical fibers transmit great volumes of information in a broad band of

frequencies without electromagnetic interference. Communication lines and
devices with integrated optical systems utilize optical fiber networks. Up to now
manufacturers have used silica fibers, and many countries have developed their
own production of this material. However, a need for higher working wave
lengths has stimulated research on other materials, especially on alkaline earth
fluorides and various chalcogenides. The useful range of Si0 2 fibers extends
from 0.4 to 2.4 fJm, the fluoride fibers (ZrFcBaF 2-CdF 3-AIF 3) from 0.4 to
4.3 fJm, and chalcogenide fibers (As3SGeSSeS7) offer a wide band from 1.6 to
10 fJm. The fibers used in communication systems are characterized by optical
loss factors which must be kept very low for long range transmission lines. The
loss factor depends on impurities (Fe,Ni,Co,OH-,H+) in the material. These
may be eliminated in the preparation cycles if optimum conditions of growth are
created. It should be noted that the losses in silica fibers at 1.55 fJm amount to
0.1 dB/km, whereas those in fluoride materials are far smaller. The fluoride
fibers have found only limited application since they are chemically unstable in
aggressive media and tend to recrystallize. Silica glass fibers have no rivals at the
present time.
7.2.4 Laser Materials

Quantum electronic materials are used in the generation and modulation
of electromagnetic radiation by induced emission monochromatic radiation.
Microwave amplifiers or masers are employed in radio telescopes, radar units,
and communication lines because of their low noise levels.
Optical range oscillators (lasers) are noted for their highly monochromatic
coherent radiation and have found application in LASER technology extending
from space technology to medical instrumentation. A solid state quantum
generator consists of a host crystal with a number of active centers (activators).
The matrix material must be highly transparent ( ~ 80%), optically homogeneous, mechanically strong, and thermally conducting to remove heat.
The first laser matrix was made of ruby, then came the garnet group
materials along with scheelite, spinel, alex and rite, andalusite, fluorite, and
complex borates. The basic requirements for activator ions are a good crystallochemical match to the matrix material, a high distribution factor and a broad
absorption band. Ions of Cr3+, Ti3+, Nd3+, rare earths, and those of the Fe
group are used as activators. The main laser properties, the wavelength of the
emitted radiation, and the lifetime of the excited state depend on the activator.
Ruby lasers work at 0.694 fJm, while for longer waves in fiber optics
(A > 1.06 fJm) YAG (Y 3AIsOd doped with Nd3+ and Cr3+ is used. The lasers
active at A = 3.0 fJm are made from Y3Als012 heavily doped with Er3+, Cr3+ or
Tm3+ activators. Semiconductor lasers made from Ga1-xAlxAs are in widespread use.
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7.2.5 Cathodochromic Screens and Scintillation Counters

Materials which generate or modify their luminescence when exposed to
electrons, ions, ionizing radiation, or mechanical stress are classified as phosphors. Cathodoluminescent materials generate or change their glow under
radiation by fast electrons or ions. They are used as screens in cathode ray tubes
or television sets. Their principal properties are color, spectral range, inertia,
light intensity, secondary emission coefficient, and chemical and thermal
stability. Willemite (Zn 2Si0 4 :Mn), scheelite (CaW0 4 ), a series of garnets
(Re 3Me sOd, sodalite (Na3AI3Si3012: Ce), and sphalerite (ZnS) are important
crystalline phosphors. Zinc and cadmium sulfides have the best glow and afterglow times (10- 3-10 s) and the best color range (ZnS: Ag-various shades of blue;
ZnS-CdS:Ag(Ni)-yellow; ZnS(Se):Ag-white). They have rather poor thermal
and chemical stability.
Silicate phosphors (ZnSi0 4 : Mn) have a lower luminous efficiency in the
green and greenish yellow spectra and smaller afterglow (10- 4 to 10- 9 s) but are
far more resistant to changes in temperature and radiation damage.
Vanadates (YV0 4 :Eu) and wolframites (CaW0 4 ) are used in narrow spectral ranges (red and green) and are thermally and chemically stable, but
somewhat inferior to the sulfides in luminous efficiency.
Among commercialized single crystals and epitaxial films, yttrium aluminum
garnet (Y AG) and gadolinium gallium garnet (GGG) doped with Ge3+, Eu3+,
Tb 3+ have high luminosity, high heat conductivity, and are radiation-resistant.
Scintillation materials used for transformating 0(-, /3-, y- and X-ray radiation
into visible light find applications in high energy physics, well logging, geophysical prospecting, and in medicine.
7.2.6 Nonlinear Optic Materials

Nonlinear optic devices are used to generate second harmonic waves, and to add
and substract the frequencies of two optical fields. These devices place strict
requirements on crystals with quadratic nonlinearity: they must be transparent
for all of the interesting frequencies, as well as highly nonlinear and mechanically strong.
Among the nonlinear materials are the synthetic analogs of the minerals
proustite, pyrargyrite, cinnabar, and quartz. The first three are used to transform infrared laser radiation, while quartz being a universal material of excellent
optical quality is used as a standard for the relative assessment of nonlinear
susceptibility. Many other minerals analogs have been tested including bromellite, sphalerite, and zinc tellurite, but the properties are not strong enough for
applications in quantum electronics. The only exception may be shortite
(Na 2Ca 2C 30 9 ), which has shown a high quadratic nonlinearity coefficient when
exposed to a Nd laser beam.
7.3 Multifunctional Minerals
521
Lithium niobate, potassium dihydrogen phosphate and gallium arsenide

semiconductor are widely used in nonlinear integrated optic systems.
7.3 Multifunctional Minerals

7.3.1 Diamond: the Mineral-Absolute. Applications in Electronics
A.S.
MARFUNIN
Diamond's exceptional esthetic qualities, its position in the jewelry hierarchy as

the highest material concentration of value, are merely the consequences and
continuation of its more general characteristic as the ultimate matter of nature.
Its hardness has to be considered not just as a record measured number but
as the ultimate attainable value, as a law of nature, as a Kelvin zero or velocity of
light. This is, however, only one of the manifestations of its special quality, all of
which can be deduced from the single origin.
A full understanding of this exceptional status of diamond could not be
revealed until its newest applications in electronics demonstrated the extreme
range of its possibilities.
The list ofthe properties of diamond which, like its hardness, are not only the
highest but the ultimate ones, shows its new status. Diamond's thermal conductivity (related through lattice dynamics and force fields to hardness and compressibility etc.) of 2000 w/mK (several times higher than the next best value in
copper) led to a radical change in the technology of heat sinks for semiconductor
and laser devices. Its highest electric and optical strength, electron-hole mobility, and its properties in fast-latching devices of picosecond (10- 12 s) optoelectronics determine the future possibilities of diamond in electronic techniques. In the series of semi-conducting materiah Si-Ge-SiC-GaAsInP-AIP, diamond is the latest and with ultimate possibilities. The large
variation of electrical resistance from nearly ideal insulator (less than
10 ohm cm) to a semi-conductor (lla type up to 106 ohm cm, la
104 -10 16 0hmcm).
Unique surface property: Negative electron affinity (which has to be created
by complicated technology on other semiconductor materials). The highest
radiation resistance and radiation sensitivity. Heat-resistance, cold-resistance,
water-resistance, very low porosity, high effective density. Transparence in the
ultra-violet, infrared, and X-ray regions. Retention of its work properties under
conditions of extreme radiation and temperature, even in aggressive media.
Counting properties, thermoluminescent tissue-equivalent dosimeter properties.
Acoustic properties: very high sound velocity (18 km/s).
Maximum attainable density of integrating diamond nanometer elements
as small as necessary. A unique capacity for obtaining extremely dense micro-
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electronic structures by high-energy ion implantation in diamond. which is

capable of withstanding local pressures up to 0.5 GPa.
Quasi-point semiconductors in devices can use diamond heat sinks of
0.3-1 mm in size which could be considered as semi-infinite. (In jewelry - e.g.,
the Drukker company - the smallest brilliant can be as small as 0.22 mm or
0.0001 carats, but still have all 57 facets of perfect brilliant cut).
The unique combination of all these characteristics has led to widespread,
extremely versatile, and unsurpassed applications.
The origin of these exceptional characteristics of diamond is determined by a
combination of the properties of the carbon atom (its position in the Periodic
Table of Elements) and the type of crystal structure.
Strongest bonding can be realized only in simple structures and with
equivalent bonds (since cohesion forces in complex, layer, molecular structures
are determined by the weakest bonds), with highest atomic charge, shortest
bond distances, the smallest number of bonds (tetrahedral coordination), and
covalent bonding.
Diamond as a material exists in several forms:
- Natural diamonds exhibit an extremely large variety of crystals with variations in nitrogen impurity content (and rare boron) and high diversity of
properties and qualities extremely sensitive to the nitrogen content, a matter
of crucial importance for electronics, jewelry, technique. A special group is
presented by microdiamonds (micron sizes) from meteorite crater and metamorphic deposits.
- Brilliant cut of diamond.
- Natural diamonds subjected to high-energy ion implantation (used as a
method for creating all necessary types of semiconducting structures): Li, B, C,
N, He, H, AI, Si, P, Ne, Ti, Cr, Ni, As, Ag, Sb, Xe, and Tl. Implantation of
boron at energies of 100-200 keY to attain a content of 1021 at. cm - 3
(0.5 at.%) (simulating rare natural lIb type diamond) is most important for
diode and transistor construction.
- Treated natural diamonds: plastic deformation, heating, radiation.
- Synthetic diamonds:
* grown from graphite in the presence of solvent-catalyst metals (Fe,Co,Ni);
most commercially produced synthetic diamonds (up to 1 mm in size) are
obtained in this way.
* grown using a reconstitution technique with dissolved diamond as a source of
carbon; large diamonds (from 0.1 carats up to 11 carats in weight or 17 mm in
size) synthesized with low nitrogen content (less than 0.001 at.%) and borondoped are used for direct reading, pulse counting, radiation detector, for
thermoluminescent dosimetry, semiconductor devices (as well as standard
cutting tools, special microtome and fibre optic cleaving knives. diamond
anvils, ultra sharp surgical blades. wire drawing dies, etc.).
Synthetic diamonds with ion implantation.
523
- Diamond films: mono crystalline, poiycrystalline, microcrystalline diamond

films, and diamond-like amorphous carbon films; obtained by low-pressure
synthesis by plasma-enhanced chemical vapor deposition (CVD) technique from
hydrocarbon gases (methane, acetylene, etc.) at 600-1600 K or from accelerated
atoms, ions, hydrocarbon plasma at 100-600 K on diamond substrate (epitaxial
films) or on Si, silica glass, quartz, refractory metals, etc. Boron-doped diamond
films can be grown.
(These results are compared with the observation of nanometer sized
diamond-like particles in meteoritic residues).
- Diamond ceramics and diamond-bearing composites.
- Diamond coatings (less than 50 nm thick) for optical components, magnetic
discs, electrical insulators, etc., and for gem coating.
A further special feature of diamond is a peculiarity in its real chemical
composition. Always existing in minerals, in diamond impurities are reduced to
a minimum, even if trace elements within the limit of their detection are taken
into account.
Diamond is the most simple and most pure system in regard to a number of
isomorphic elements. Diamond lattice expels even negligible amounts of impurities except those of its neighbors in the Periodic Table of Elements: nitrogen
and boron (rare Ni).
On the other hand, however, nitrogen (1) is always present as an impurity in
natural diamonds (albeit in some types in minimal quantities), (2) occurs in
extremely diverse forms, (3) has a definite effect on all its properties: electronic,
industrial, and gemological.
The second impurity, boron, is present in even smaller quantities and only in
rare types of natural diamonds, where they are, in jewelry, exceptional blue
diamonds and the largest crystals, and in electronics, the most valuable semiconducting diamonds.
More than 50 elements have been detected in natural colorless diamonds without visible mineral inclusions - in quantities 10- 5 _10- 8 gig by neutron
activation, gas chromatography, and other specialized techniques.
However, (1) there exists a correlation between the contents of these elements and that of the usual mineral micro inclusions in diamonds: olivine,
garnet, enstatite, diopside, chrom-spinelides, magnetite, rutile, pirite, pyrrhotite,
pentlandite, etc.; (2) no other elements were detected by even the most sensitive
direct solid state spectroscopy methods; (3) crystallochemically these elements
are not compatible with diamond structure; (4) they do not manifest themselves
in any of the extremely sensitive (till 10 16 at.cm -3, i.e., 0.000005%) electronic
characteristics and in photoelectric spectra.
Hydrogen impurities occur in micropores and in fluid hydrocarbon inclusions as C 2 H 2 , H 2 , CH 4 , C 2 H 4 , C 3 H 6 , CH 3 0H, and CH 3 CH 2 0H.
Oxygen impurities are adsorbed by surfaces of crystals.
The types of diamonds are distinguished by their nitrogen (and rare boron)
content (and by their impurity-dependent properties):
524
Type I: nitrogen-containing diamonds: 2 x 10 18 to 1020 at.em -3, i.e.,

0.001 at. %-0.28 at. % (1.76 x 10 23 at.em - 3 in diamond cell);
Type II: "nitrogen-free" diamonds: containing less than 2 x 10 18 at.cm- 3
(0.001 %) nitrogen, but in all natural crystals not less than
10 17 at.em- 3 (0.00005%).
Type I accounts for about 95-98% of all natural diamonds, while only 2-3%
belong to type II.
The next step in distinguishing diamonds of type I is related to the structural
position of the nitrogen impurities:
la: nitrogen is predominantly not in the form of isolated substitutional atoms
(paramagnetic) but in the form of aggregation, and extended defect structures; most (98%) natural diamonds (including gem quality diamond) are of
this type, la.
Ib: single dispersed nitrogen atoms substituting for carbon sites (paramagnetic
N defect); all synthetic diamonds are of this type, Ib; a small number of N
defects can exist in natural diamonds.
Type II is subdivided into two types:
IIa: nominally "nitrogen-free' diamonds, containing less than 0.001 % nitrogen
(and any other impurity); very rare (1-2%) natural diamonds.
lIb: "nitrogen-free", boron-containing diamonds (up to 10 21 at.em - 3 or 0.5%
but mostly 10 18 _10 19 at.cm -3); very rare natural diamonds among the very
rare diamonds of Type II; synthetic lIb boron-containing diamonds are
grown or obtained by boron implantation; this type has the most important semiconducting properties; although the lIb type is extremely rare in
natural diamonds, most of the largest gems (Cullinan, Excelsior, Lesotho
Brown, etc.) are of this lIb type.
The following relationships hold with respect to the forms of nitrogen in
diamonds (in diamonds of the la type, in Ib there is only one nitrogen form
N~C):
N~C
(nitrogen atoms substituting for carbon atoms);

N-center (defect) (or C-center);
(pairs of nitrogen atoms): A-center;
(three nitrogens with a vacancy); N3-center;
(four-six-eight nitrogen atoms segregations Ns: in (111) planes
= Bl-center or in (100) planes = B2-center; more extended nitrogen segregations ( '" 100 nm), called platelets.
Of all these types of centers, only Nand N3 are paramagnetic, and can be
observed directly by optical and luminescence spectra, while the A and B centers
(most usual in natural diamonds) are non-paramagnetic and optically nonactive. However, the contents of A and B centers correlate with conjugated
525
centers which enable their determination:

A=N 2
Bl = N s(l1l)
B2 = Ns(100)
C=N
N3=NV
H3 (520nm) = N 2 V2
H4 (520nm) = N 2 V2 and S2 (550nm) = NoV
N3 (450 nm) = N3 V
Sl (610) = NV
Natural diamonds contain mostly A = N 2, B1 = Ns (111), and B2 = Ns (100)

centers and N-platelets. The type containing all these centers la(A,Bl,B2) can be
distinguished from laA, laBl, IaB2 containing mostly one type of center.
Type Ie represents diamonds containing a higher density of dislocation (Ie D).
Each crystal of naturally produced diamonds has to pass through special
laboratories for sorting and grading to determine not only the gem qualities but
dozens of factors of significance to different branches of electronics and other
techniques, each imposing particular constraints and demands.
Specialized methods have been elaborated to satisfy particularly sensitive
conditions. Each method has to be nondestructive, and (without affecting the
sample) be able to determine nitrogen contents as small as 0.0005-0.3% and its
distribution in different types of centers (since each of them has its own system of
analytical special lines). The bulk of the nitrogen (mostly in A, B1, and B2
centers) can be determined by the displacement of the absorption edge in UV
from 220 nm (in nitrogen-free diamonds) to 330 nm and further up to the visible
region.
Each type of center has its own system of IR lines from 7.3 to 20.8 mu.
Luminescence spectra and photoelectric spectra are extremely sensitive to
the smallest nitrogen contents and permit determination of the individual forms
of nitrogen impurities in diamonds.
"Nitrogen-free" diamonds do not exhibit photoluminescence; but in all types
of diamonds, X-ray luminescence and catodoluminescence can be observed as
broad bands with superimposed systems of sharp lines.
Electron Paramagnetic Resonance spectra are unique for unambiguous
deciphering of the models for the paramagnetic types of centers: NV, N 2 V, N 3V,
NCN, B(boron), implanted Ni, Co, surface centers, and several radiation
centers.
Specific features are characteristic for nitrogen manifestation in optical
absorption spectra in the visible region and hence in the related color of a
diamond.
The most widely distributed A(N 2)- and B(Ns)-forms of nitrogen in natural
diamonds do not absorb visible light. Hence the main body of natural diamonds, even containing significant amounts of nitrogen impurities, are colorless,
and can be graded as highest quality gems.
Yellow coloration is, however, still related to nitrogen in the form mostly of
N3 and the consequent lines 4153, 4520, 4650, 4780 A ("Cape series" lines) which
impart "Cape yellow color" to most natural diamonds or "fancy yellow" when
there is more nitrogen (and, combined with isolated N atoms, "canary" color).
526
Yellowish tints can be observed even at nitrogen contents of about

2 x 10 18 at.cm- 3 (0.001 %) and at 5 x 10 19 (0.03%).
Boron impurities in nitrogen-free diamonds are responsible for the color of
the rarest blue diamonds. (The Cullinan is rare not only because of its enormous
size, but also as belonging to this rare lIb type of blue semiconducting
diamonds).
Yellow-brown color can also be connected with dislocations. Enhancement
of color for this type of diamonds can be obtained by treating them at high
pressures and temperatures to eliminate the dislocation traces of plastic deformation or transform the N3-centers into optically nonactive forms of nitrogen
References
Bachman PK, Collins AT, Seal M (eds) (1993) Diamond 1992. Elsevier Sequoia, Lausanne
Davies G (1984) Diamond. A Hilger, London
Diamond Films-90 (1990) First Eur Conf on Diamond- and Diamond-like Carbon Coatings.
Crans-Mon
Field J (ed) (1979) Properties of diamond. Acad Press, New York
Kvaskov VB (ed) (1990) Diamond in electronics. Energoatom, Moscow
New Diamond (1988) First lnt Conf on the New Diamond Science and Technology, Tokyo
7.3.2 Quartz Crystals in Devices

M.I SAMOILOVICH and R.E. NEWNHAM
Quartz (ex-Si0 2 ) occupies a special position among the minerals because of its
wide geological distribution and its numerous applications.
Single crystals and polycrystalline quartz are used as a final product and also
as a raw material in the production of silicates, glass, porcelain, ceramics,
gaseous silanes, and in the growth of high quality single crystals. Quartz is a
useful material for many technical applications because of its excellent technological properties: hard but brittle, insoluble in acids (except in hydrofluoric
acid) and its availability and relative cheapness. The world output of quartz
exceeds 10000 tons yearly. Since natural high quality crystals are scarce and
their characteristics variable, and demand is rising, industries of a number of
countries have begun synthetic production. During the 1950s, the USA, Germany, the USSR, Japan, and Great Britain began to develop synthetic quartz
crystals by hydrothermal processes. Technologies differed in vessel design,
solution compositions, as well as in temperature, pressure, and kinetic factors.
Modern-day synthetic quartz production satisfies 95 to 98% of the industrial
demand for electronic grade material.
In addition to technical quartz, a number of colored varieties with excellent
gem qualities have been obtained: amethyst, citrine, and blue quartz, a Co-
7.3.3 Corundum - Ruby -Sapphire
527
doped variety. Compared to tens or hundreds of kilograms of the mined gem

material, synthetic colored quartz is produced in volumes measured in tons.
Piezoelectric quartz crystals are used as resonators and filters in radio
devices and in computers for frequency selection and stabilization. Stable and
temperature-compensated cuts of quartz crystals (zero value of the temperaturedependent frequency factor) and the low value of internal friction [reciprocal of
Q (quality)] outweigh in importance the small value of electromechanical
coupling factor. There are many quartz devices employing frequencies of kHz
to GHz with Q values of thousands to tens of millions and with frequencies
stabilized to ppm fractions (10- 6 _10- 12 ).
Quartz glass is widely used in optics because of its transparency over a wide
range of frequencies and its excellent homogeneity. The absorption edge of silica
is in the vacuum UV at 151 nm, making it useful as windows and prisms.
Quartz glass obtained from natural vein and granular quartz, as well as from
low quality crystals, is used to manufacture mask substrates, chemical utensils,
crucibles, and forms for semiconductor devices.
Quartz fibers obtained from high quality starting materials are used in
optical communication systems, where they occupy a leading position. Si0 1 based fibers are used for a frequency range of 0.4 to 2.4 ,urn, with optical losses
less than 0.2 dB/km, close to the theoretical values. Since the losses depend
entirely on the purity of the raw material and on the techniques of production, it
is important that the starting materials be extremely transparent. Iron and water
content must be carefully controlled.
7.3.3 Corundum - Ruby - Sapphire

R.E. NEWNHAM and M.1. SAMOILOVICH
Corundum is a multifunctional material like diamond, quartz, and fluorite. Its

colored varieties (ruby, sapphire) are highly prized gem stones, while colorless
corundum (leucosapphire) has a great number of technical applications.
The high mechanical strength and hardness (Knoop 2200 kg/mml) and
the high specific gravity (3.92 to 4.08) of ruby and leucosapphire make them
indispensable for load-bearing devices in watches and for dies and spinnerets in
drawing machines. High strength, together with chemical and thermal stability,
are qualities needed for the abrasive ceramics used in the manufacture of high
speed drills and machine tools.
A broad range of transparency (0.15 to 6.5 ,urn) and high thermal conductivity are important for windows, lenses, and optical filters. Compared to yttrium
oxide and spinel, sapphire is somewhat inferior in this application because its
strength degrades notably with temperature.
Ruby is an excellent laser host because of its heat conductivity
(0.42 W/cm K), the long lifetime of excited state (3000,us) and relatively high
528
damage threshold. Corundum is doped usually with Cr or Ti ions when used as

a tunable laser.
Ruby crystals are also used in delay lines and as substrates for various
electronic devices. Surface acoustic wave (SAW) transducers made of leucosapphire coated with CdS, ZnO, or AIN films have good electromechanical
coupling coefficients and excellent frequency stability.
Alumina ceramics are used for strong refractory elements resistant at high
temperatures (up to 1900 0c) and in aggressive environments. They are also used
for thick film substrates and as multilayer packaging materials for integrated
circuits.
References
Genmuller P (ed) (1985) Inorganic solid fluorides: chemistry and physics. Academic Press,
Orlando
Jaffe B, Cook W, Jaffe H (1971) Piezoelectric ceramics. Academic Press, New York
Japan Electronics Industry Development Association (JEIDA) (ed) (1985) Future of electronic
parts and materials. Tokyo, pp 231~255
Kamada N, Gomi T, Shindo M (eds) New materials developed in Japan 1987. Toray Research
Center, Tokyo
Kaminskii AA (1980) Laser crystals, Springer ser in optical sciences 14. Springer, Berlin
Heidelberg New York
Lemanov VV (1988) Acousto-optic devices and materials for IR. In: Acoustic devices of
radioelectronic systems. Nauka, Leningrad (in Russian)
Macleod HA (1985) Thin film optical filters. Adam Hilger, Boston, Matthews H (1977) Surface
wave filters: design, construction and use. Wiley and Sons, New York
Moulson AJ, Herbert JM, Electroceramics. Chapman and Hall, London
Musikant S (ed) (1990) Optical materials: a series of advances vol I. Marcel Dekker, New York
Oliner AA (1978) Acoustic surface waves. Springer, Berlin Heidelberg New York
Salt D (1987) Hy-D handbook of quartz crystal devices. Van Nostrand Reinhold (UK),
Wok ingham, Berkshire (England)
Savage JA (1985) Infrared optical materials and their antireflection coatings. Adam Hilger,
Bristol
Stwalley WC, Marshall Lapp (cds) (1986) Advances in laser science. Proceedings of the First
Intern Conference, Dallas, Texas
Suprigo D (1986) Surface acoustic wave devices. Prentice-Hall, Englewood Cliffs
Synthesis of minerals (1987) Vol 1, 2. Nedra, Moscow (in Russian)
Zelenka J (1986) Piezoelectric resonators and their applications. Academia, Elsevier, Prague
7.3.4 Natural and Synthetic Zeolites: Applications in Radioactivity,

Ecology, Petroleum Chemistry, and Agrotechnology
N.F.
CHELISCHEV
and LV.
MISHIN
The first zeolite mineral was discovered in 1756 and over the next two centuries
zeolites remained the subject of intensive field and laboratory investigations.
Ion-exchange properties of zeolites were recognized in 1858 and adsorption of
7.3.4 Natural and Synthetic Zeolites
529
gases by dehydrated chabazite was observed in 1909, but the first industrial
application commenced as late as 1954 with the production of oxygen-enriched
air by the selective adsorption of nitrogen and the purification of the gasoline
fraction from normal paraffins on CaA zeolite.
Since then, these microporous solids have been developed into key materials
in oil processing and in the petrochemical and chemical industries. Only a few
hundred tons of zeolites were produced in the late 1950s, about 60000 t in 1975
and in 1987 the production of zeolites had increased to 460000 t worldwide.
Hundreds of thousand tons of natural zeolites are mined as components of
volcanic tuffs, sedimentary and low-grade metamorphic rocks. Workable deposits of zeolite-containing rocks were discovered in the USA, Japan, Cuba, Russia,
Italy, Hungary, Bulgaria, and in other countries, where zeolite minerals often
occur in megaton quantities at high purities.
Increasing production of zeolites was a response to the growing need of these
solids as ion exchangers, adsorbents, and catalysts. Following their rapid
introduction as commercial, molecular sieve adsorbents, zeolites came to dominate the petroleum refining industry. In the United States, approximately onethird of all processed crude oil is catalytically converted over zeolite-containing
catalysts. Over 500 t of catalyst are required daily. In future years the worldwide
sales of zeolite catalysts to the petroleum, petrochemical, and chemical industries are expected to exceed 5 billion dollars.
The estimated annual use of A zeolites as builders of detergent comes close
to 400 000 t. Natural high silica zeolites were recognized as unique materials
for removing 137CS, 90Sr, and 90y from liquid nuclear effluents, for soil
enrichment, and even for preparing animal feed supplements. The advent of
zeolites as commercial inorganic materials helps to solve three major problems
encountered in our century: the development of effective industrial technologies,
the improvement of agricultural productivity, and the reduction of environmental damage created by industrial and municipal effluents.
Comprehensive information on the industrial application of zeolites can
be found in excellent books compiled by Breck (1974) and Rabo (1976). Here,
we give only some typical examples of the uses of zeolites as ion exchangers,
sorbents, and catalysts.
Zeolites display outstanding properties in separation, purification, and
molecular rearrangements, which can be attributed to a unique combination of
strong active sites and spatial selectivity. The reasons for this behavior lie in the
topologies of the anionic frameworks of zeolites.
As in other tecto silicates, the main building unit in zeolites is the T0 4
tetrahedron, where T may be Si, AI, or some other element capable of forming a
tetrahedral coordination with oxygen. The T0 4 units are linked with other T0 4
tetrahedra through shared oxygens. In contrast to other tecto silicates, the
zeolites have, however, a well-developed intracrystalline channel system. At
present, 39 naturally occurring zeolite minerals and more than 100 synthetic
species are available, among which about 40 different topologies can be
identified.
530
a

Fig. 132a, b. The arrangement of tetrahedra in the secondary building units of zeolites. a for 4-ring, b for 6-ring
The number of TO 4 tetrahedra in the unit cell varies from 24 as in A zeolite

to 672 as in paulingite. For a simplified description of zeolite structures, it is best
to consider the simplest structural features rather than the topology of the unit
cell. The most common way of formulating the zeolite framework topology is
to join the centers of adjacent tetrahedra. The zeolite framework is then
represented by a four-connected, three-dimensional network, where polygons
and polyhedra as subunits can be readily recognized (Fig. 132). These subunits
or secondary building units (single four-ring, single six-ring, single eight-ring,
cube, h~xagonal prism, and more complex combinations) can serve to construct
zeolite frameworks. In addition to the single four rings, single six rings, single
eight rings, larger rings, containing 10 or 12 oxygen atoms can be identified in
the framework of zeolites. These rings are produced by joining the subunits, and
they control the accessibility of the intracrystalline pores for the guest molecules
and ions. The free dimensions of the windows made by rings of linked tetrahedra
are very important in determining the molecular-sieving properties of the
zeolite. The pore openings vary in size from 3 to 12 A and govern the passage of
molecules and ions in ion exchange, adsorption, and catalysis (Table 37).
Under normal conditions zeolite intracrystalline voids are filled with water.
Intracrystalline pores are joined in an open system and water molecules can be
mobile. After dehydration by heat and evacuation, water or some other guest
molecules can penetrate the channels and cavities of zeolites. Such a process is
known as adsorption. Cations which are distributed within the zeolite pore
system show a certain mobility. The number of cations present in a zeolite
structure is determined by the number of [AI0 4 ] 5 - tetrahedra included in the
framework. This arises from the isomorphous substitution of AI3+ for Si 4 +,
causing a residual negative charge on the oxygen framework. Due to the
531
Table 37. Molecular sieve pore structures

Zeolite
Ring
opening
Free
aperture
(Angstrom)
Pore"
structure
Faujastite
Mordenite
12
8
12
7.4
2.9 x 5.7
6.7 x 7.0
3D
lD
lD
0.53
0.26
L
ZSM-5
12
10
10
7.1
5.4 x 5.6
5.1 x 5.6
lD
lD
lD
0.28
0.32
Erionite
8
8
8
6
3.6 x 5.2
4.2
3.7 x 4.2
2.6
2D
3D
lD
lD
0.36
0.47
0.48
8
10
8
4.0 x 5.5
4.4 x 7.7
4.1 x 4.7
lD
lD
lD
Offretite
6
6
3.6 x 5.2
6.4
lD
lD
0.34
Ferrierte
10
8
4.3 x 5.5
lD
lD
0.24
Chabazite
Clinoptilolite
Pore volume,
cm 3 jcm 3
0.34
aiD = one-dimensional channels.

2D = two-dimensional channels.
3D = three-dimensional channels.
mobility of cations, they can participate in the ion-exchange reactions. Due to

their favorable ion-exchange and adsorption properties, zeolites are among the
most important ion exchangers and sorbents.
The sizes of the molecules and hydrated ions that can traverse the oxygen
windows of zeolites range from 3 to 12 A. By the proper choice of molecular
sieve, selectivity between the molecules and ions of different size and shape can
be achieved. By comparing the free aperture of the windows, one can select the
most appropriate sieve for each process. This form of selectivity is known as ion
sieve, and molecular sieve effects help to explain why some ions and molecules
readily penetrate zeolites, whereas more bulky species are excluded as potential
ingoing ions, sorbed molecules, and reactants. A number of new industrial
processes currently take advantage of these unique zeolite properties.
In addition to the lock and key relations, the mobility of the guest species in
zeolites may be influenced by the interaction with cations and zeolite frameworks. The variation in sorption site energies can arise from the different shapes
and sizes of channels and cavities where guest species are accommodated to the
energetic heterogeneity of active sites. As a result, molecules of comparable size
and shape but with different electronic structures will be consumed at different
rates and thus properly separated in the presence of appropriate zeolites.
532
Finally, very high silica zeolites can now be readily synthesized, whereby the
content of Al and cations is so low, that they have lost much of their polar
character and show the properties of hydrophobic rather than hydrophilic
sorbents. These solids retain the full power of molecular sieving, but cannot sorb
small polar molecules such as water at low and moderate external pressure.
In summary, the separation of the complex mixtures in the presence of
zeolites can be due to many factors. The most important factors governing the
selective behavior of zeolites in separating the different substances can be
described as follows:
1. Molecular sieving with the adequate shape and size differences between the
molecules to be separated based on the different accessibility of the intracrystalline pores.

2. Interaction of the adsorbed molecules with the electrostatic fields of the
cations.
3. Unequal distribution of the negative charge among the framework oxygen
and the energetic heterogeneity of the ion-exchange and adsorption sites.
4. Hydrophobization of the zeolite surfaces.
The versatility of these general principles is used in the application of zeolite as
ion exchangers, sorbents, and catalysts.
Zeolites as Ion Exchangers

The ion-exchange capacity and selectivity to the given ion characterize the
replacement of the zeolite cations by the ions present in the external solution.
The exchange capacity of a zeolite depends on the chemical composition and
increases with the decreasing Si/Al ratio. The selectivity is estimated by the
distribution of the exchange cation between the exchanger and the external
solution.
Zeolite A (Si/ Al = 1) has the highest exchange capacity among the known
zeolites. In a typical sample all divalent cations can be favorably accommodated
near the centers of the six rings. For divalent ions in zeolite A the order of
decreasing selectivity is:
Zn > Sr > Ba > Ca > Co > Ni > Cd > Hg > Mg.
This zeolite is very selective toward Ca2+ in comparison to Na + and to a
lesser extent to Mg2 +. Small crystallites of synthetic zeolite A (2-10 jlm), which
have no natural counterpart, ensure the high rate of exchange. They form
a stable suspension in water and have proven to be an ideal scavenger of Ca 2+
in hard water. Zeolite is used as a builder in detergent powders to replace
phosphates, which are banned in many countries throughout the world. The
large role played by phosphates in the autrophication of stagnant or slowly
flowing surface waters led to extensive research into the problem of finding
suitable substitutes for phosphates in detergents. When combined with small
533
amounts of water-soluble substances, such as polycarboxylates and sodium

carbonate, zeolite A provides an attractive alternative to phosphates.
The small additives of NaX zeolites enhance the selectivity of nonphosphate
detergent toward Mg2+ ions. It is expected that more than 500 000 t of NaA
zeolite will be manufactured in the next years to cover the needs for the builder
components in detergents.
Zeolite A is the only aluminous molecular sieve used commercially as an ion
exchanger. All other instances of the use of crystalline aluminosilicates in ionexchange processes are related to high silica natural zeolites, such as clinoptilolite, mordenite, erionite, and chabazite. These acid-resistant materials are widely
applied in the treatment ofliquid effluents. The density of electrostatic charges in
zeolites with a reduced aluminum content is much lower than in aluminous
solids, thus explaining the high preference of clinoptilolite, mordenite, and
erionite for bulky, univalent cations. The selectivity series for univalent cations
was observed, in terms of decreasing selectivity, to be:
Cs > Rb > K > NH4 > Na.
This series corresponds to the decreasing cation size. The same trend can be seen
in the divalent cations: Ba > Sr > Ca. A similar sequence was observed for the
rates of ion exchange.
Table 38. Zeolites used as ion-exchangers
1. Manufacturing of detergents
Zeolites
NaA;NaX
Effective removal of Ca2+ - and Mg2+ -ions
Advantage in using zeolite based materials
Zeolites
2. Treatment of nuclear waste

Natural clinoptilolite, mordenite, chabazite
Advantage in using zeolite sorbents

Zeolites
3. Treatment of waste waters

Natural mordenite, clinoptilolite, phillipsite,
chabazite, and zeolite-containing tuffs
Advantage in using zeolite sorbents
Zeolites
Removal of NH 4 + -ions, traces of Fe, Zn, Cu,

caprolactam, and lubricants
4. Soil benefication
Synthetic A zeolite, natural clinoptilolite, and
mordenite
Advantage in using zeolites
Zeolites
Selective removal of 137CS and 90Sr
Stabilization of soil pH, moisture contents and

manure malodour
5. Animal feed supplementation
Synthetic A zeolite, natural clinoptilolite and
mordenite
Advantage in using zeolite-containing diets
Beneficial weight gain, control of ammonium

level, regulation of blood protein levels
534
The selective and rapid uptake of the bulky, monovalent cations from
aqueous solutions by clinoptilolite and mordenite was used for the decontamination of radioactive effluents (Table 38) and the treatment of wastewaters. The
use of these minerals for soil improvement is related to the ability of these
zeolites to improve nitrogen retention in the soil. Zeolite addition to the growing
media has a beneficial effect on the production of vegetables. The beneficial
effects of 5-6% supplementation to the diet of animals is also attributed to the
ion-exchange control of ammonium levels.
Zeolites as Adsorbents
In contrast to other adsorbents, zeolites offer increased possibilities for exploiting molecular level differences among adsorbates. They separate molecules
based on the accessibility of the main apertures of the zeolite structure for
molecules with different sizes and configurations. Moreover, they show an
affinity to the polar sorbents and interact with these molecules with exceptional
selectivity (Table 39).
Strong interaction with water molecules makes zeolites most useful as
practical drying agents. The most important application of zeolites as a desiccant remains the drying of natural gas, halocarbons, and liquid hydrocarbons,
especially liquid propane gas. Zeolite A in Na-form with 4 A windows is used in
the purification of natural gas, since it excludes hydrocarbon molecules and
removes H 20, CO 2, and H 2S. In large-scale operations the columns are loaded
with hundreds of tons of NaA zeolites and operate for 2-4 years without
regeneration. Attempts to utilize natural clinoptilolite and mordenite for purification of natural gas have been successful. Potassium A (3 A windows) is the
preferred zeolite for the dehydration of unsaturated hydrocarbon streams, such
as cracked gas, as well as ethylene, propylene, and methanol. Clinoptilolite and
3 and 4 A zeolites are used to dry halocarbon refrigerants, in vehicle braking
and air conditioning systems, and in heavy duty transformers filled with
hydrocarbon liquids. More recently, KA, NaA, and NaX zeolites were found to
be uniquely suited for removing traces of water from sealed glazing units
containing gases (Ar, SF 6, halocarbon), to improve heat and sound insulation.
The best-known separation based upon a molecular sieving action is the
separation of high purity n-paraffins from i-paraffins. The larger molecules of
paraffin isomers and the cyclic hydrocarbons, which are present in the feed, are
excluded, whereas n-paraffins are admitted into the cavities of A zeolite and
exchanged with Ca 2+ and Mg2 + ions. Commercial processes for this separation
to provide feedstocks for the detergent and chemical industry have been
developed by Union Carbide (Isosiv), BP, Shell, Texaco, Exxon, and Leuna
Werke (Germany). More recently, UOP has licensed Sorbex processes for
separation of p-xylene from C s aromatics, olefins from paraffins, p- or
m-cymene from other cymene isomers, p- or m-cresol from cresol isomers, and
fructose from dextrose and polysaccharides. The total product capacity of the
535
Table 39. Zeolites used as adsorbents

1. Drying gases and solvents
Zeolites
Synthetic Na., K. and NaX zeolites, natural

clinoptilolite, and mordenite
Advantage in using zeolite dessicants
Efficiency for water scavenging at low partial

pressures of water vapors and elevated temperatures, removal of CO 2 and H 2 S in addition to
H 2 0, simple regeneration
2. Removal of carbon dioxide, hydrogen sulfide, ammonia, and organic sulfides from natural
gas and industrial gas streams
Zeolites
Synthetic CaA zeolite, dealuminized varieties
of high silica natural and synthetic zeolites
such as mordenite and clinoptilolite
Advantage in using zeolite adsorbents
Combined drying and purification due to the

strong adsorption of both CO 2 and H 2 0, the
use of evacuation to regenerate adsorbent, reo
duced operational costs
3. Envirnomental protection of the atmosphere

Zeolites
Synthetic and natural mordenite and clinoptilolite
Compact equipment, the replacement of the

spent adsorbent every 1-2 years without regeneration
4. Purification of motor fuels from paraffins to reduce environmental damage from vehicle
emissions
Zeolites
Synthetic CaA zeolite
Low cost for increase in octane number

5. Commercial processes for bulk separation of linear branched paraffins to provide feedstocks for proteins and detergents
Zeolites
Synthetic CaA, CaMgA, and NaX zeolites
6. Liquid phase separation

Zeolites
Production of pure long-chain normal paraffins (99.5%) without traces of aromatic hydrocarbons
Synthetic CaA, NaX, and BaX zeolites
Complete separation of chemically similar
components such as xylenes, ethylbenzenes,
and saccharides unattainable by traditional
separation techniques
7. Enrichment of air by oxygen, nitrogen, or inert gases

Zeolites
Synthetic NaA zeolite
Production of high purity gases avoiding

cryogenical technique, use of portable pressure
swing oxygen generators in hospitals or as
home oxygen supplies for patients with respiratory problems
536
Sorbex processes exceeds 8 million t year. All these processes are based on the
sieving properties of large and small port zeolites.
Finally, another large-scale sieving operation, involving zeolite adsorbents,
is the production of oxygen-enriched air by selective adsorption of nitrogen on
various zeolites. This process uses the selective uptake of nitrogen, due to
quadrupole interaction.
Zeolites as Catalysts
Catalysts for modern chemical processes (Table 40) have to show excellent
activity and selectivity and also have to satisfy purely practical considerations in
their use and performance, such as thermostability and resistance to attrition.
Most of the synthetic zeolites meet all these requirements. These crystalline
aluminosilicates in appropriate ion-exchanged forms can offer sizeable activity
Table 40. Zeolites used as catalysts
I. Catalytic cracking oflarge petroleum molecules into smaller hydrocarbons, primarily in the
gasoline range to produce gasoline
Rare-earth, ammonium, magnesium, exZeolites
changed Y zeolites or mixed REHY and
MgHY zeolites embedded in a matrix of dense,
amorphous silica-alumina
Advantage in using zeolite catalysts
Increased gasoline yield, enhanced gasoline

octane number, stable performance in the hydrothermal stability of the catalysts in the regenerators
2. Hydrocracking of heavy gasoils to producce gasoline, central heating oil, jet diesel fuels,
and petrochemical feedstocks
Zeolites
Faujastite, mordenite or HZSM-5 loaded with
transition metals ions
Resistance to metals (like N;, Y, Cu, and Fe)

contaminants in the feed, versatility in processing crude oils of different nature, favorable
time on stream behavior
3. Selectoforming of reformer product streams to produce low paraffin gasolines

Zeolites
Synthetic or natural erionites and c1inoptilolites containing N;
Selective uptake of the unbranched paraffins

from the feed eliminating low octane rating
fractions can be achieved only by zeolites with
narrow channels ( < 5 A)
4. Paraffin isomerization to produce components of higher octane numbers

Zeolites
Synthetic mordenite, containing noble metals
Conversion of low octane pentane and hexane

feeds to higher octane yields
537

5. Isomerization of aromatic hydrocarbons to produce feedstocks for polyester manufacture
Zeolites
HZSM-5
Increase in selectivity to p-isomers, low yields

of by-products
6. Catalytic dewaxing of heavier oils to produce diesel fuels with lower pour points
Zeolites
Synthetic mordenite, HZSM-5, ferrierite, offretite, L, and mazzite
Removal of long-chain paraffins from heavier

oils, improvement of viscosity, production of
arctic diesel fuels without the need to incorporate a noble metal in the catalyst
7. Alcylation of benzene by olefines to produce ethyl benzene, alkyl benzenes with long alkyl
substituents and other intermediates in the manufacture of styrene, phenole, and detergents
Zeolites
HZSM-5
8. Methanol to gasoline conversion
Zeolites
9. Catalytic reduction of nitrogen oxides

Zeolites
Replacement of the corrosive aluminum chloride, which contaminates plant waste waters
ZSM-5
A promising way to produce high quality octane fuels from different carbon sources, such
as coal, methanol, biomass etc.
Mordenite
Removal of NO x from industrial gas streams in
nitric acid and nuclear processing plants
enhancement and selectivity alterations for certain reactions when compared

with amorphous silica-alumina. Due to the porosity and crystallinity, the active
sites are regularly distributed in three-dimensional crystallites. The activity of
zeolites in acid-catalyzed reactions is associated with "protonated" forms which
can be made either by direct exchange with mineral acids or by calcination of
zeolites containing ammonium or polyvalent cations. The protonated forms
contain Bronsted or Lewis acid sites which are related to the activity in acidcatalyzed transformations:
Bnmsted site
Lewis site
The activities of a series of zeolite catalysts are reported to be more than

10 000 times the activity of amorphous silica-alumina for n-hexane cracking.
538
The site densities of zeolites are 10 to 100 times greater than those of silicaalumina. Such effects are explained by the following factors:
1. Greater concentration of active sites;
2. Greater effective concentration of hydrocarbons in the vicinity of a site,
resulting from strong adsorption in the fine micropore structure;
3. Electric fields in the zeolite pores may enhance the formation and reactions of
carbonium ions through polarization of C-H bonds.
Cracking, i.e., the conversion of large petroleum molecules into smaller

hydrocarbons, primarily in the gasoline range, is one of the largest scale catalytic
processes. The most important advance in cracking technology in the last three
decades has been the development of zeolite catalysts. The most significant
improvement offered by zeolites over silica-alumina is better selectivity. Zeolitecontaining catalysts provide more products in the CS-C 10 range and fewer in
the C 3 -C 4 range. The yields of gasoline are thus improved and the formation of
light gases reduced. In the United States more than 250000 t of crude oil is
processed every day over zeolite-containing cracking catalysts.
Selectoforming is another industrial use of shape selectivity, involving the
selective uptake of C S-C 9 n-paraffins from the crude oil distillates. The selectoforming catalyst selectively cracks these n-paraffins to liquid propane gas. In this
way the selectoforming increases the octane number of gasoline (Fig. 133).
Benzene alkylation and xylene isomerization were traditionally performed
with aluminum chloride and BF-HF catalysts, which are corrosive and produce
product contamination. New zeolite-based processes help to avoid the problems
of corrosion and improve the selectivity for cumene, styrene, and p-xylene,
which are valuable chemicals for polystyrene, phenol, acetone, and polyester
production.
Molecular sieving can be observed in the catalytic transformation of methanol to gasoline. This new industrial process uses high silica ZSM-5 type
zeolites. Among the products formed from methanol only those with proper
dimensions can diffuse out and appear as gasoline hydrocarbons. Bulky products are then retained in the pores until converted to less bulky molecules.
Methanol to gasoline conversion is a promising way to produce fuel from coal
and natural gas.
~----1"-
Fig. 133. Representation of reactant shape selectivity in zeolite channels. Rejection of

branched chain hydrocarbons
539
References
Barrer RM (1982) Hydrothermal chemistry of zeolites. Academic Press, London
Breck DW (1974) Zeolite molecular sieves. John Wiley and Sons, New York
Dyer A (1988) An introduction to zeolite molecular sieves. John Wiley and Sons, Chichester
Occelli (1988) Recent trends in fluid catalytic cracking technology. In: Fluid catalytic cracking.
ACS Symp Ser, ACS, Washington, DC, vol 375, P 1
Rabo JA (1976) Zeolite chemistry and catalysis. ACS Monogr Ser, Washington, DC, vol 171
Roland E (1989) Studies in surface science and catalysts, vol 46. In: Jacobs PA, Van Santen RA
(eds) Zeolites as catalysts, sorbents and detergents builders. Applications and innovations.
Elsevier, Amsterdam, p 645
Mineral Index
achtenskite 138
actinolite 205, 213
albite 79, 86, 256, 407, 432
alexandri te 519
amazonite 193
ambligonite-montebrasite 346
amethyst 467
amphiboles 13, 14, 30, 79, 204, 211, 346
analcime 131
anatase 118
andalusite 10, 428
anhydrite 195
anorthite 133, 135, 206, 256, 378~379, 432
antophyllite 204, 212, 213
apatite 33, 141, 196,221,233,512
aragonite 409
arsenopyrite 403, 512
asbolane-buserite 139
astrophyllite 116, 117
baddeleyite 261
barite 187, 195
bayerite 121
beriinite 385,512,515,516
berthierite 129
bertrandite 428
beryl 9, 221, 227, 228, 232, 428, 515
birnessite 207
boehmite 322
borates 29, 57, 110, 159, 325
brezianite 34
bromellite 428
brucite 96, 322
calcite 187, 195,235,409,425,432,512
calomel 518
cancrinite 195
cannizzarite 100, 216
carbon polymorphs 117
carbonates 29, 30, 124, 139, 195, 231, 325,
505
carisbergite 34
carnegieite 399
cassiterite 102, 425
caswellsilverite 34
cathierite 313
celadonite-nontronite 130
cerussi te 409
chalcophanite 207
chalcopyrite 403, 404
chlorites 30, 98, 115, 124, 125, 129
chrysoberyl 160,428
cinnabar 512, 518
clay minerals 93, 139, 213, 505
c1inohumite 16
c1inojimthomsonite 211~212
clinoptilolite 9
coesite 307, 424, 480
coronadite 102, 206
corrensite 125, 131
corundum 118, 353, 364, 433, 512, 517,
526,527
cristobalite 136, 206, 300, 302, 307, 480
cronstedtite 333
cryolite 325
cryptomelane 102, 207
cylindrite 125, 216
danburite 324
davidite 9
diamond 10, 116, 174, 221, 232, 364~365,
432, 434, 482, 500, 512, 521~526
diaspore 102, 322
digenite 93
diopside 8, 33, 82, 86, 89, 432
euclase 428
eucriptite 400~401
fayalite 136, 354, 397
feldspars 8, 30, 79, 185, 189, 192~ 194, 206,
261, 367, 399, 496, 500, 505
ferrosilite 136, 137
fluorite 72, 160, 196, 209, 210, 233, 364,
432, 512, 517~519
frankeite 100, 216
gadolinite
143
542
Mineral Index
galena 403,404,488, 512

garnets 14, 89, 355, 427, 512, 516
gibbsite 110, 121
glauconite 131,407
goethite 102, 203, 507
graphite 10, 124, 432
greenalite 139
greigite 136
groutite 102
halides 78, 195,409
heideite 34
hematite 75, 136, 202, 438, 442-444, 450,
457, 467, 501, 512
hilgardite 110
histidine 97
hollandite 93, 102-105, 206, 207, 266, 399
hornblende 204, 407
humite 115, 214
hydrotalcite 96, 97
hydroxides 29, 95, 124, 322
hysingerite 139
illite 131,206
illite-smectite 125, 128, 131, 139
ilmenite 16, 355, 427, 438, 450, 467, 512
ilvaite 136, 137, 333
inkaite 100
jarosite 340
jimthomsonite
211-212
kamacite-taenite 33
kaolinite 107, 121, 124, 303, 407
kaolinite-smectite 125, 130
karelianite 75
keatite 480
kentrolite 151
kimrite 93
koeninite 98, 99
kosmochlor 34
krennerite 381
kupletskite 9
kyanite 428
laihunite 333
langbanite 151,401
laueite 150
laumontite 131
lawrensite 34
lazurite 195
lechatelierite 480
leucite 136
leucophoenicite 115
lilliani te 14
limonite 138
lizardite 303, 305
lonsdaleite 116
mackinawite 99
maghemite 202,438,441,450,467, 501
magnesiowiistite 170, 203, 393
magnesite 409
magnetite 136, 202, 203, 261, 333, 397,
437, 450, 457, 461, 467, 501
manasseite 96
mandarinoite 343-344
manjiroite 102, 207
marcasite 313
metahalloysite 139
micas 30, 79, 107, 112, 113, 121, 212, 346,
496, 505
microlite 144-145
minessotaite 139
molybdenite 8, 13, 111, 121,312,403,404,
512
montmorillonite 407
montroseite 102
mordenite 9
mullite 93, 208, 209
muscovite 205, 432
natrolite 66-68
nepheline 13, 93, 256, 496, 500
neptunite 143
niningerite 34
norbergite 161
nordstrandite 110
nsutite 104, 139
oldhamite 34
olivines 13, 30, 32, 89, 115, 143, 161, 170,
171, 173,214,354,366,385,392,407
olivine-spinel 89, 354, 425-427
opal 407
orthoclase 256,407,432
osbornite 34
otavite 409
palygorskite 101, 115, 116
paratellurite 102, 512, 518
pentIandite 465
periclase 353, 423, 512
perovskite 71, 83, 122, 161, 170, 209, 215,
266,355,393,399,427,512
phenacite 195
phosphates 29, 30
phyllomanganates 207
phyllosilicates 112, 113, 132
picroilmenite 455
pinnolite 324
plagioclase 32, 33, 93
plattnerite 102
potosite 100
priderite 102, 207
protoenstatite 118
proustite 93, 512, 518, 520
543
Mineral Index
pseudowollastonite 118
pumpellyite 118
pyrargirite 520
pyrite 13,313-315,367,403-405,512
pyroaurite 96
pyrochlore 121, 399
pyrolusite 102, 105
pyrope 432
pyrophyllite 112, 205, 303, 433
pyrosmalite 116, 117
pyroxenes 14, 30, 32, 79, 83, 89, 118, 119,
158, 159, 170, 204, 211, 261, 355, 367,
368, 385, 399
pyroxmangite 86
pyrrhotite 13, 93, 173, 201, 202, 383, 444,
447, 457, 465, 467, 512
quartz 79,93, 133, 135, 189-192,221,
228-230, 232, 233, 261, 297, 302, 307,
364,367,375,381-388,407,424,428,
432,433,480,496,505,512,515,517,
520, 526, 527
ramsdellite 102, 103
rectorite 125
rhodochrosite 409
rhomboclase 340
romanechite 102, 103, 104
ruby 519, 527
rutile 86, 102, 103, 118, 174, 214, 215, 261,
424, 425, 512
samarskite 9
sanidine 234, 369
sapphire 517, 527
sapphirine 119, 121,434
scapolite 195
scheelite 195,500,502,503,512,520
shortite 496, 520
selenides 29, 78
sellaite 517
sepiolite 101
serpentine 30, 97, 107, 115
silica polymorphs 206
silicates 29,30, 71, 78, 95, 124, 157,307,
308,406
silicon carbide 106, 119, 120
sillenite 512
sinoite 34
sjogrenite 96
smectites 124, 139, 206, 207
sodalite 195,407,512,520
sphalerite 14, 15, 111, 380, 512
spinel 13,32,202,353,397,512,517
spodumene 221, 229, 230, 232, 503, 512

stanosulite 121, 512, 515
steenstrupine 2
stilpnomelane 116
stishovite 73, 102, 424
stringhamite 342, 343
sulfates 29, 30, 159, 195, 324, 505
sulfides 29, 78, 95, 136, 156,406
sulfosalts 14, 29, 159, 215, 216
sulvanite 516
sursassi te 118
sylvanite 380
synchisite-bastnaesite 382
talc 112, 205, 303
tantalite-columbite 501
tellurides 29, 78
tetrahedrite 316-318
titanite 135, 143, 382
titanomaghemite 203,441
titanomagnetite 438,449, 457, 461
tobelite 340
tochilinite 98, 99, 105, 125, 139
topaz 221, 226, 227, 232
tosudite 125
tourmaline 195, 515
tridimite 13,93, 206, 262, 480
troilite 33
tysonite 399
ulvospinel 438, 450, 461, 465, 467
uraninite 209-210
vaesite 313
valleriite 98, 99, 139
vermiculite 207
vernadite 138
warwickite 151
wermlandite 97, 98
willemite 520
witherite 407, 409
wohlerite 151
wollastonite 118
wonesite 205
wiistite 203, 204, 206, 512
wurtzite 111, 379
zeolites 9, 71, 101, 121, 207, 208, 512,
528-538
zirkelite 121
zircon 33, 141-143, 194
zirconolite 121, 141, 266
zoisite 118, 119
zussmanite 116
Subject Index
actinides in silicate glasses

Np-237 M6ssbauer spectroscopy
neptunyl groups 268
Pu 4 + 268
267
band structure
crystobalite 300
pyrite series 315
silicates 302-304
single-layer Iizardite 305
biominerals 437
biopyriboles 14, 115, 139, 211-213
bond lengths
computer program 59
electrostatic valence rule 58
in borates 57
in silicates 59
relation to bond strength 58
bond strength 57, 58
by-product elements 12
in complex ores 12
multicomponent minerals 12
charge transfer
Fe 3 +-Fe 2 + 332-334,337
chemical bond calculations
in molecules 290
in solids 293
chemical bonding
band structure in silicates 300, 302
dichalcogenides 312-314
electron density 301-302
halides 325-326
Hartree-Fock formalism 272-287
hydrogen bonding 340
hydroxide minerals 322
marcasite-pyrite structures 313-315
methods for molecules 290
methods for solids 293-294
modelling structure and properties
307-308
molecular orbital theory 298-300, 306
molybdenite and tungstenite 312
oxide minerals 320-321
oxyanions 322-324
semi-empirical methods 287-288
silicates 297
sulfides 310
tetrahedrite structure 316-318
classification
combinatorial 153
concept of structural units 161
counting theory 164-166
hierarchy 148-153
multivariate methods 18
natural and artificial 153
classification of inorganic structures
160-163
structure types 160
structure units 161
classification of minerals
chemical compounds 156
crystal-chemical 2, 42, 148, 149, 154
oxides 156
polymerization of coordination
polyhedra 164
principal criteria 154-155
pyroxenes 158
silicon-oxygen radicals 157
structural 160,162-163
cluster analysis 19, 20-22, 24, 25
classification of minerals 153
dendrograms 20
fuzzy set theory 25
comparative crystal chemistry 76
analogy of variation of volume 84
isostructural surfaces for (Mg,Fe)O 84
similarity of deformations 85, 86
composition of the Earth's crust 6
computer programs
bond lengths in silicates 59
calculation of structural formulae 17
image simulation for point defects 174
modelling glass structure 254
ORTEP, STRUPLO, XTAL, ATOMS
67-69
semi-automatic production of structural
drawings 67
546
computer programs (Contd.)
SIMPLEX, PLUTO, ELEN, LEMINPI
70-72
simulation of crystal structures 69-71,
356
WMIN, METAPOCS, PARAPOCS
70-72
XRD data processing 41
counting theory 153, 164-166
crystal structure analysis
general results 38, 42-48
purposes 147-148
technical developments 38-42
crystal structure representation
computer programs 67
coordination polyhedra 64
natrolite structure 68
semi-automatic production 67
sphere models 64
topology and geometry 64, 66
visualizing 64
data banks 41, 152
powder XRD 41
reflectance spectra 491
diadochy and solid solutions 44
dislocations 43, 22i, 227-228, 372
dissociation 367, 369
halite, pyrite, olivine, pyroxenes,
feldspars 366-367
HRTEM 369, 377
role in plastic deformation 366-368
slip systems 366-367
distance least-square method 45
elastic properties of minerals
Brillouin scattering 352
equation of state 356
forsterite-fayalit 354
garnets 355
Hartee-Fock calculations 294 295
mantle 350
perovskites 355
pyroxenes 355
rheology of mantle 350, 357
shockwave data 352
seismic tomography 357
spinel Mg 2 Si0 4 354
summary of properties 352
ultrasonic methods 352
vibrational spectrum 351
X-ray static method 352
electrical conductivity of minerals
fayalite, magnetite, wiistite 397
transition metal oxides 395, 398
electrical properties of minerals
band gap 402
Subject Index
dielectric constants 406
galena, molybdenite 403-404
Hall effect 402
microwave dielectric constants 406, 409
pyrite, arsenopyrite, chalcopyrite 403
thermo-EMF 403
electron density
chemical bonding in silicates 301-302
deformation of electron density 72
fluorite 72
high-pressure M 2 Si0 4 74-75
mapping by Fourier series 72
quantum chemical calculation 72
stishovite 72
electron diffraction
oblique-texture 114
selected area 114
electron-hole centers 43, 180-196
amazonite 193
carbonates 195
EPR spectra 183-188
feldspars 192-194
fluorite 196
molecular orbitals 186
quartz 189-192
radicals in crystals 182 -183
systematics 188
zircon 194
Electron Paramagnetic Resonance 40,
183-188,525
electronic transitions
high-spin to low-spin 335
pressure induced 335-336
semiconductor-metal 335
engineering geology
calcite 508
hydration of clay minerals 508
loess 507
mineral properties 505-508
radioactive wastes 509
swelling in clay soils 507
EXAFS 40
poorly crystallized minerals 140
extra hard materials 361-365
flow in crystalline materials
creep in minerals and ceramics 392
models of flow in mantle 390, 392-394
olivines 391
perovskite 393
force constants calculations 294-295
fracture mechanisms in minerals
dislocations and plasticity 372
theories 370-372
glasses
computer modeling glass structure 254
Subject Index
diaplectic 259,261
dispersive X-ray scattering 255-256
electron-hole centers 181
EXAFS and XANES 256
fulgurites 259, 264-265
glassy meteorites 259
impact 259-260,262
lunar volcanic 259-262
nuclear waste glasses 266-268
obsidian 259
Raman spectra 242
ringe statistics 257 - 258
silicon-29 NMR 238
strained cluster model 257
structure of magmatic liquids 250
synthetic glasses 256
tectites 262-264
vitreous Si0 2 239
hardness of minerals
Calculation 359
Correlation Mohs-Vickers 359
crystallographic orientation 363
crystallochemical factors 359
hardness-compressibility 360
indentation size effects 362
relation to chemical reactivity 360
heat flow
mechanisms 430-431
paleo thermal reconstruction 435
radioactive heat sources 434
in sublithosphere mantle 430, 435
thermal conductivity 431-432
thermal structure of mantle 435
high-pressure and high-temperature phase
transformations
general rules 45, 46
structural mechanisms 46
high-temperature crystal chemistry 76
HRTEM 43, 115
anti-ferroelectric domain walls 382
anti-phase boundary 379, 380
dislocations in silicates 368-369
hydrolytic weakening in quartz 387
mixed-layer minerals 129
nonstoichiometry in minerals 199
out-of-phase boundaries in pyrrhotite
383
poorly crystallized minerals 139
in study of defects 377-379
homologous series 14
hybrid layer structure 95
cannizzarite 100
commensurate and incommensurate 98
hydrotalcite 96
koeninite 99
in prebiotic evolution of Life 96
547
tochilinite 97,98
wermlandite 98
hydrogen-bearing groups 340-342
geometry of bonds 345
infrared spectra 344
mandarinoite structure 344
neutron diffraction 344
hydrolytic weakening
olivine pyroxene, berlinite 385
quartz 384, 387
image analysis 23
incommensurate structures 43
infrared spectroscopy 40
hydrogen bonding 343-344,414
interstratification in minerals 43, 124
lattice dynamics
Al 2 SiO s polymorphs 428
Be minerals 428
forsterite and spinel Mg 2 Si0 4 425
garnets, ilmenites, perovskites 427
lattice vibrational spectr"'m 422
periclase 423
Si0 2 , Ge0 2 , Ti0 2 polymorphs 424
luminescence 40
magnetic phase transitions
iron silicates 137
neutron diffraction 136
magnetic properties
domain structure 446-447
Fe-Ni-S system 464-465
FeO-Ti0 2 -Fe 2 0 3 diagram 438, 453,
464
geothermometry 450, 456, 465
hematite-ilmenite 442-444,450,465
high magnetic fields 470
list of properties 467
magnetic separation 470
natural remanent magnetization 450,
452
pyrrhotites 444, 465
superparamagnetism 445
titanomaghemites 441-442,450
titanomagnetites 437-441,449,450,
461,464,468
magneto-mineralogical processes
aeromagnetic exploration
mineralogy 464-467
magnetic fields of the Ocean floor 457,
459
paleomagnetism 257
plate tectonics 458-460, 463
unmixing, oxidation, exsolution 450,
453-455
548
material science
families of materials 512-513
mineralogical aspects 512
materials
acoustoelectronics 516
cathodochromic 520
diamond in electronics 521-524
electro-optics, acousto-optics 517
laser 519
multifunctional 521
nonlinear 520
mathematical methods of classification 19
melts
mechanisms of melting 47
structural state 47
metamict minerals 140
ceramic nuclear waste forms 146
HRTEM 142-145
microlite 144
stages of transition 141
X-ray spectroscopy 144
zircon 141-143
methods of crystal structure determination
direct analysis 39
high precision 39
Patterson function 39
microinclusions in minerals 10, 227
microwave dielectric constants 406, 409
mixed-layer minerals
HRTEM 129
indirect methods 129
ordered and irregular 125
special techniques for
identification 126-127
stage-by-stage transformations 131
modeling crystal structures 69-71
modeling properties 69-71
modulated structures
anti-phase boundary 380
HRTEM in quartz 381
list of minerals 93
two types 91
Mi:issbauer spectroscopy 40
Np-237 in glasses 268
molecular orbitals
Fe0 6 clusters 329, 332
FeO lo clusters 335
Si0 4 group 298
SilO o group 299
tetrahedral M0 4 323
neutron diffraction
hydrogen bonding 340-344
magnetic transitions 136
non-stoichiometric compounds 10, 14, 44,
197
extended defects 211-216
Subject Index
HRTEM 199
manganese oxides 206-207
mullite 209
perovskite 209, 215
point defects 200-202
pyrrhotite 201
rutile 214
spinel and hematite 202-203
structural classification 198
sulfosalts 215-216
uraninite 210
wiistite and magnesiowiistite 203-204
nuclear magnetic resonance 40, 48
silicon-29 NMR 239-242
nuclear quadrupole resonance 40
chemical bonding in sulfides 317
nuclear waste glasses 266-268
number of minerals 27-35
occluded gases 11, 343
OD structures 47, 110
optical absorption spectroscopy 40
optical mineralogy
dissimetrization 476
non-linear optics of minerals 495
summary of crystal optics 472-475
theory of refraction 477
phase analysis 41
plastic deformation 233-234
point defects
diffusion 170, 175-176
direct imaging 172-175
electrical conductivity 170
magnesiowiistite 170
non-stoichiometry 200-202
olivine 170-171, 176, 178-179
perovskite 170
pyrrhotite 173
polyhedral distortions 56, 77, 82, 83,
151-152
polysomatic series 47,107,211
polysomatism 118, 211
polytypism 47, 106
astrophyllite 117
modular structures 108-109
molybdenite 111
nomenclature 111
notation for chlorites 114
perovskite 122
photovoltaic cells SnS l 121-122
symbology for micas 112
transformation mechanisms 120
polytypoid 107
poly tropism 110
poorly crystallized minerals 42, 139, 140
principal components analysis 22
549
Subject Index
pyriboles
118
quasicrystals
54
radar images in remote sensing 405, 411

radiation centers 43
radii of ions
orbital radii 63
pseudopotential 62
structure maps 63
systems of empirical radii 62-63
radioactive decay products 12
Raman spectroscopy 40
lattice dynamics 414
real structures of minerals 43
real-time crystallography 40
reflectance spectra of minerals
band theory 487
PbS-PbSe-PbTe 488-489
computer-controlled
micro spectrophotometer 489
data bases 491
ellipsometry 492
mineral identification 491
modulation spectroscopy 492
quantification of color
refraction of minerals
classical theory 477
empirical refraction formulae 479
geophysical and mineralogical
aspects 485
rafraction index versus density 480
shock-compressed Si0 2 -glass 485
Si0 2 polymorphs 480
Rietveld-type refinements 41, 55
second-harmonic generation
mica polytypes 496
noncentrosymmetric minerals 496
nonlinear optics 495
quartz, shortite, nepheline 496
sensitivity analysis 23
separation of minerals
feldspar from quartz 496
magnetic separation 470, 501
nonlinear optics 496
spinodal decomposition 91
stacking faults 43, 221, 229
HRTEM 377
wurtzite structure 379
stereohedra, symmetry theory 52
structural formulae 12, 150
Bauverband description 13
computer programs 17
electron probe data 17
nonstoichiometric 14
recombination structures 14
systems of notations 13
structural phase transitions
anorthite 135
crystobalite, leucite 136
quartz 135
Vervey transition in magnetite 136
structure modeling 45
structure-simulation methods 45, 60
substitutions in minerals
cations in channels 9
defect isomorphism 11
heterovalent, list of minerals 7-8
homo valent, list of minerals 3-6
trace elements 9
supergroup-subgroup relationships 133
magnetic phase transitions 137
structural phase transitions 135
superionic conductivity of minerals
eucriptite 400
langbeynite 401
materials and minerals 399
symmetry theory
anti symmetry 51
generalized symmetry groups 51
groups of curvilinear symmetry 52
groups of homology 52
multidimensional geometric spaces 52
poly-colored point and space groups 51
synchrotron radiation 40
X-ray topography 225
SYNROCK
polytypic relationships 121
pyrochlore-zirkelite-zirconolite 121, 266
taxonomy 152
technological properties of minerals
density 501
enrichment 500
flotation 502
induced properties 503
luminescence 500
magnetic 501
radioactivity in ore sorting 500
tectites 262-264
thermal conductivity of minerals
diamond 434
list of minerals 432
methods of measurements 431-432
sapphirine 434
thermal expansion 78
coefficients 82
relation to lithostatic compression 86
tunnel-structure minerals
disposal of radioactive wastes 101
HRTEM 101
ionic conductors 101
manganese oxides 104
Subject Index
550
tunnel-structure minerals (C ontd.)
ribbons 101
sepiolites, palygorskites, zeolites
twin planes 43, 221, 230, 234
uranium in silicate glasses
uranyl group 57, 267
101
267
valence least-squares 45
vanadyle group 57
Vernier structures 215
vibrational spectra calculation
X-ray absorption spectroscopy
296-298
412-418
40,
X-ray energy dispersive method 41

X-ray photoelectron spectroscopy 40
bonding in oxides 320-321
carbonates, borates, sulfates 324-325
electron states in pyrite series 315
X-ray topography 43, 221
apatite 233
beryl 227, 232
diamond 232-233
images of defects 222
quartz 228-230, 232
spodumene 229, 232
synchrotron topographs 225
topaz 226-227

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To Be Published in This Series

Composition, Structure, and Properties

Methods and Instrumentations:

Mineral Matter in Space, Mantle, Ocean Floor,

Processes of Mineral Formation:

Minerals as a Source of Metals, Energy, and Materials

With 133 Figures and 40 Tables

Springer Verlag Berlin Heidelberg 1994

Printed on acidfree paper

The book thus attempts to present a universal (or perhaps a

Moscow, May 1994

Chapter I The Chemical Nature of Minerals . . . . . . . . . .

Chemical Composition of Minerals. Crystallochemical

1.2 Treatment of Chemical Composition Data for Minerals

The Mineral Composition of the Earth's Crust,

Chapter 2 Crystal Structures of Minerals . . . . . . . .

General Results of Crystal Structure Analysis of

2.1.6 Computer Simulation of Crystal Structures

Systematics of Crystal Structures and

Chapter 3 Real Structures of Minerals

Point Defects in Minerals

Direct Imaging of Point Defects by HRTEM

Point Defects and Diffusion in Minerals

Point Defects as Precursors for Electron-Hole Centers:

Structural Types of NonStoichiometry in Minerals

X-Ray Topographic Study of the Real Structure

Twinning Due to Phase Transformations

Chapter 4 Natural Glasses.

Structure and Properties of Silicate Glasses and

X-Ray Studies of Glass Structure

Terrestrial and Lunar, Volcanic and Impact Glasses,

Nuclear Waste Glasses: Recent Advances in the

Chapter 5 Chemical Bonding in Minerals . . . . . . . . . .

Survey of Quantum Chemistry and Methods Used

Chemical Bonding in Silicates

Chemical Bonding in Sulfide Minerals

Bonding in Oxides, Oxyanions, and Halides

Electronic Structures of Iron Oxides and Silicates

Hydrogen Bonding in Minerals

Chapter 6 Properties of Minerals . . . . . . . . . . . . . . . . . 349

Elastic Properties of Minerals

6.4.2 Superionic Conductors

Lattice Dynamics, Vibrational Spectra,

6.7.5 Nonlinear Optical Characteristics of Minerals

Technological Mineralogy and Technological

Mineral Properties in Engineering Geology

Chapter 7 Mineralogical Material Science . . . . . . . . . . . . 511

Concept of Materials as a New Approach to Solids

An Overview of Materials for Electronics and

7.3 Multifunctional Minerals . . . . . . . . . . . . .

AFONIN, V.P., Institute of Geochemistry, Favorky Str. la,

BOKIY, G.B., IGEM Academy of Sciences, Staromonetniy 35,

CRIDDLE, AJ., Department of Mineralogy, British Museum

GANDAIS, M., Laboratoire de Mineralogie-Cristallographie

KASSNER, D., Institut fUr Kristallographie der Universitat

McDERMOTT, P.F., Department of Earth Sciences, The Open

OZIMA, M., Geophysical Institute, University of Tokyo,

RYAKHOVSKY, V.M., Aerogeology, Krzhyzhanovsky 5,

URUSOV, V.S., Department of Crystallography, Geological Faculty,

bonding" or "molecular mimicry"), ab initio Hartree-Fock computations, band

2. Mineralogical Material Science. Further enhancement and enrichment of the

earth elements; distribution coefficient of impurities between olivine and melts,

The Chemical Nature of Minerals

Chapter 1. The Chemical Nature of Minerals