Professional Documents
Culture Documents
The physical and chemical properties of crystals and textured materials often
depend on direction. An understanding of anisotropy requires a mathemat- 1.1 Outline 1
ical description together with atomistic arguments to quantify the property 1.2 Structureproperty
coefficients in various directions. relationships 3
Tensors and matrices are the mathematics of choice and the atomistic 1.3 Symmetry of physical
arguments are partly based on symmetry and partly on the basic physics and properties 4
chemistry of materials. These are subjects of this book: tensors, matrices, 1.4 Atomistic arguments:
symmetry, and structureproperty relationships. Density 5
1.1 Outline
We begin with transformations and tensors and then apply the ideas to the vari-
ous symmetry elements found in crystals and textured polycrystalline materials.
This brings in the 32 crystal classes and the 7 Curie groups. After working out
the tensor and matrix operations used to describe symmetry elements, we then
apply Neumanns Law and the Curie Principle of Symmetry Superposition to
various classes of physical properties.
The first group of properties is the standard topics of classical crystal
physics: pyroelectricity, permittivity, piezoelectricity, elasticity, specific heat,
and thermal expansion. These are the linear relationships between mechanical,
electrical, and thermal variables as laid out in the Heckmann Diagram (Fig. 1.1).
These standard properties are all polar tensors ranging in rank from zero to four.
Axial tensor properties appear when magnetic phenomena are introduced.
Magnetic susceptibility, the relationship between magnetization and magnetic
Electric field
Susceptibility
Polarization
Piezoelectricity Pyroelectricity
Strain Entropy
Magnetization
Magnetoelectricity Piezomagnetism
Pyromagnetism
Electric field Mechanical stress
field, is a polar second rank tensor, but the linear relationships between
magnetization and thermal, electrical, and mechanical variables are all axial
tensors. As shown in Fig. 1.2, magnetization can be added to the Heckmann
Diagram converting it into a tetrahedron of linear relationships. Pyromagnetism,
magnetoelectricity, and piezomagnetism are the linear relationships between
magnetization and temperature change, electric field, and mechanical stress.
Examples of tensors of rank zero through four are given in Table 1.1.
In this book we will also treat many of the nonlinear relationships such as
magnetostriction, electrostriction, and higher order elastic constants.
The third group of properties is transport properties that relate flow to a
gradient. Three common types of transport properties relate to the movement
of charge, heat, and matter. Electrical conductivity, thermal conductivity, and
diffusion are all polar second rank tensor properties. In addition, there are
cross-coupled phenomena such as thermoelectricity, thermal diffusion, and
electrolysis in which two types of gradients are involved. All these properties are
also influenced by magnetic fields and mechanical stress leading to additional
cross-coupled effects such as piezoresistivity and the Hall Effect. The transport
properties analogous to the Heckmann Diagram are shown in Fig. 1.3.
A fourth family of directional properties involves hysteresis and the move-
ment of domain walls. These materials can be classified as primary and
secondary ferroics according to the types of fields and forces required to move
the walls. The primary ferroics include such well-known phenomena as ferro-
magnetism, ferroelectricity, and ferroelasticity (Fig. 1.4). Less well known
are the secondary ferroic effects in materials like quartz which show both
ferrobielasiticity and the ferroelastoelectric effect.
The final portions of the book concern wave phenomena. Crystal optics has
long been an important part of crystal physics with roots in classical optical
1.2 Structureproperty relationships 3
Electric field
Electrical conductivity
Electric current
Electrolysis Thermoelectricity
Ferrobielectric Fer
tric
rom
lec
e
agn
sto
ela
eto
rro
ele
Ferromagnetic Ferroelastic
Fe
ctr
c
eti ic
Fer
agn
rob
Ferroelectric
im
iela
ob
rr
stic
Fe
angles. Unit cell volumes for higher symmetry crystals are easily deduced from
the triclinic formula.
A sample density calculation from quartz is carried out for -quartz (Fig. 1.5).
0.1 5/6 2/3 5/6 0.1 The drawing outlines the structure as viewed along the c-axis. -quartz
1/6
(SiO2 ) belongs to the hexagonal crystal system and has a molecular weight
1/2 1/6 of 60.09 g/mole. Avogadros number N0 is 6.023 1023 molecules/mole. The
1/3 b
1/3 unit cell dimensions are a = b = 4.913 , c = 5.405 . Interaxial angles for
1/6 1/2
1/6
the hexagonal system are = = 90 , = 120 . From this information, the
unit cell volume is
0.1 5/6 2/3 5/6 0.1 V = a2 c( 3/2) = 113 3 = 1.13 1022 cm3 .
a Examining the unit cell drawing, it can be seen that there are eight silicons at
Silicon Oxygen the corners of the unit cell, and four more on the side faces. Since each corner
Fig. 1.5 The unit cell of -quartz viewed belongs to eight cells and each face to two cells, the number of silicons in the
along c. The heights of the oxygen and silicon cell is 8/8 + 4/2 = 3. The number of oxygens can be counted in a similar way.
atoms are expressed in cell fractions.
There are eight O on side faces and two more inside the hexagonal cell. This
adds up to 8/2 + 2 = 6 oxygens. Thus there are three formula units of SiO2
per cell: Z = 3. Collecting all numbers, the density
= MZ/N0 V = 2.65 g/cm3 .
The most important factor affecting density is molecular weight because
atomic weights vary over a wider range than do atomic volumes. Among
difluorides, densities increase with cation atomic weight: BeF2 1.99,
MgF2 3.14, CaF2 3.18, SrF2 4.24, BaF2 4.89, PbF2 8.24. The densities of
MgF2 and CaF2 are nearly the same because the fluorite structure is more open
than the rutile arrangement.
A similar trend is observed in alkali halides when density is plotted as a func-
tion of molecular weight (Fig. 1.6). If all the atoms were similar in size, density
would be linearly proportional to molecular weight. Obviously this is not the
case. Going from LiF to CsI there is an overall increase in density but the rela-
tionship is far from linear. In fact, the fluorides are denser than the chlorides
because of the large increase in ionic radius going from F to Cl . This gives
a dip in the density vs. molecular weight curve that is also observed in some
oxides, semiconductors, and metals.
As a rule, crystals with close-packed atoms have larger densities than those
that do not. Thus the densities of corundum, spinel, chrysoberyl, and olivine
CsI
4.5 LiI CsBr
LiF
KF RbCl
2.5 NaCl KBr
2.0
LiCl KCl
1.5
1.0
0.5
Fig. 1.6 The density of alkali halides with
the rocksalt structure plotted as a function of 0
molecular weight. Density usually increases 100 200 300
with weight but size changes cause anomalies. Molecular weight
1.4 Atomistic arguments: Density 7
Column IV elements
6
Sn
Ge
5
4
Density (g/cm3)
3 Si Ba
Sr
2
Be
Mg Ca
Column II alkaline earth metals
1
Fig. 1.7 Density vs. atomic weight curves for
column IV and column II elements. Note that
0 the densities of column IV elements with four
0 20 40 60 80 100 120 140 bonding electrons per atom are much higher
Atomic weight than the densities of the alkaline earth metals.
24
5d series
20
Density (g/cm3)
16
12
4d series
8
3d series
lie in the range 3.34.0, considerably larger than those of quartz, beryl, and
feldspar that are near 2.7 g/cm3 . The differences in densities of the minerals
are useful in separating them by flotation methods.
Among polymorphs, high-pressure phases are denser than low-pressure
phases because of the importance of the PV term in the free energy when
P is large. Kyanite, the stable high-pressure form of Al2 SiO5 , has a density of
3.63, compared to 3.15 for andalusite. For the same reason, low-temperature
polymorphs are often denser than high-temperature forms. When T is very
small, the PV term dominates the TS term in the free energy function. As an
example, quartz ( = 2.65) is denser than its high-temperature polymorph
cristobalite ( = 2.32).
The density vs. molecular weight curves for semiconductors and metals
resemble those of the alkali halides. Silicon has a lower density than diamond,
and calcium is less dense than beryllium and magnesium (Fig. 1.7). Among
metals the highest densities are found in the 5d transition metal series (Fig. 1.8).
8 Introduction
Note the peaks near the middle of the 4d and 5d series where the d electrons
participate strongly in interatomic bonding. The d electrons in 3d transition
metals are buried further inside the atoms and participate less in bonding, but
give rise to impressive magnetic behavior.
Density is a scalar quantity that does not depend on direction. In the next
chapter, we begin the discussion of anisotropic properties.
Problem 1.1
Sanidine feldspar, KAlSi3 O8 , is monoclinic with lattice parameters a = 8.56,
b = 13.03, c = 7.17 , = 116 . There are four molecular units in the unit
cell. Calculate the density of this common rock-forming mineral.
Problem 1.2
a. Silver and palladium both crystallize with a face-centered cubic crystal
structure. Make a sketch of the structure and count the number of atoms
per unit cell. The cubic cell edges are 3.890 for palladium and 4.086
for silver.
b. Compute the densities of these two metals.
c. AgPd alloys are often used as electrodes. As pointed out in Chapter 17,
they form a complete solid solution with Pd atoms substituting randomly
for Ag. The measured density of a certain AgPd alloy is 11.00 g/cm3 .
Estimate the composition of this Ag1x Pdx alloy in atomic% Pd and
weight% Pd. There are several ways of doing this. One method presumes
Vegards Law, and another is based on Retgers Rule. Vegards Law
states that the lattice parameter of a solid solution changes linearly with
composition, and Retgers Rule states that the unit cell volume changes
linearly with composition. How much difference does it make for the
estimated composition of the AgPd alloy?