Identify minerals: to know structure and composition

What are these minerals?

A B
Feldspar

Quartz

X-ray Diffraction: a powerful tool for studying minerals and rocks (DGT: Ch 15)

XRD

Electromagnetic Radiation: rays with different wavelengths

The relationship between energy and wavelength (!) is governed by Plancks law: E = hc/! Real number: ! () = 12.398 / E (keV) E: energy of photon h: Plancks constant c: velocity of light ! : wavelength

Generation of X-ray
High energy electrons from tungsten filament hit metal targets (like Cu, Co, Mo) in high vacuum (X-ray tube). White (continuous) X-ray, and characteristic X-ray (sharp peaks with strong intensity, and directly related to atomic structure of metal atoms.
Characteristic X-ray K"

K#

White (continuous) X-ray

Generation of X-ray (continue)

Characteristic X-ray
Knock out electrons in inner shell (like K shell). Electrons from high energy shells (like L shell) fill the empty sites in lower energy shell (like K shell) produces characteristic X-ray radiation, such as Cu K" radiation (! = 1.5418 ). Synchrotron radiation X-ray (white X-ray): extremely strong intensity. You can make very small (micron to nanometer size) beams / probes. (UW has Synchrotron Radiation Center)
Energy

E = 8.046 KeV

X-ray Terminology
Wavelength of X-ray: measured by X unit (Xu), 1 (Angstrom) = 1000 Xu, 1 = 0.1 nm = 10-4 m = 10-10 m Hard X-ray: short wavelength, for medical applications, security checks, and less harmful. Soft X-ray: long wavelength, for diffraction and chemical studies.

Family of (hkl) planes

Interplanar spacing: d-spacing, or d-value: 1/d2hkl = h2/a2 + k2/b2 + l2/c2 (for orthorhombic crystals) 1/d2hkl = (h2+ k2 + l2)/a2 (for cubic crystals)
d120 b/2 1a

Principle: Braggs Law

2dhkl sin$ = !,

2$ A set of (hkl) planes One diffraction peak corresponds one set of (hkl) planes. Theta ($) is called Bragg angle. If there is a diffraction, it must satisfy the Braggs law.

X-ray Diffractometer
in S. W. Bailey XRD Laboratory, Room A 353
XRD with 2-D detector Liquid Nitrogen X-ray tube Specimen Detector

Detector (moving)

X-ray Diffractometer
Crystal (moving) Controller and Data Collection

HV

Fixed X-ray tube

NaCl and KCl: Same structure, different unit cell sizes

Unit Cell of halite (NaCl): a = 5.64 , cubic, (or 4/m 3 2/m) Unit Cell of sylvite (KCl): a = 6.2788 200 220 222 311 400 2dhkl sin$ = !
_

111

200

220 222 331 400

111 2$

311

Peak positions are related to unit cell sizes. Peak intensities are related to atom species (composition) and positions of atoms. Peak width is related to size of crystals.

People laid foundation for XRD of Minerals and Materials

W. C. Rontgen (was awarded the first Nobel prize in 1901) Max von Laue (was awarded the Nobel prize in 1914) W. H., Bragg and W. L. Bragg (father and son were awarded the Nobel prize in 1915) Paul Debye, and Paul Scherrer Linus Pauling (received two Nobel Prizes) And more

W. H., Bragg

W. L., Bragg

Case study I: Silica polymorphs (quartz, cristobalite, tridymite)

quartz

cristobalite

tridymite

X-ray powder diffraction patterns are finger prints of minerals.

Case study II: Olivine

Identify mineral, obtain unit cell parameters, and calculate composition of olivine (Fo89) based on cell parameters in Forsterite -Fayalite solid solution series.
Sample: d020 = 5.1049 , (Fo89Fa11)

Forsterite: d020 = 5.1035 Fayalite: d020 = 5.2355

Applications
Identify minerals based on XRD pattern (values of dspacing, intensity of peaks), like finger prints. By matching patterns in data base (Powder Diffraction Files, or PDF). Quantify concentrations of minerals in a mixture of clays. Identification of fine grain minerals (micron size and submicron sized minerals like clay minerals) relies on XRD. What if it does not match? A possible new mineral species. It is required to have a powder XRD pattern for a new phase or new mineral. Determine crystal sizes and shapes, especially for nanocrystals. Determine crystal structures (unit cell parameters, i.e., shape and size, and positions of atoms inside the unit cell), chemistry, defects, and texture (preferred orientations). And more (You can see lots of invisible things with invisible X-ray.)

PDF of NaCl (Halite) and KCl (Sylvite)

PDF#75-0306: QM=Calculated (C); d=Calculated; I=Calculated Halite: Na Cl Radiation=CuKa1 Lambda=1.54060 Filter= Calibration= 2T=27.366-83.992 I/Ic(RIR)=4.71 Ref: Calculated from ICSD using POWD-12++ (1997) Cubic, Fm3m (225) Z=4 CELL: 5.64 x 5.64 x 5.64 <90.0 x 90.0 x 90.0> P.S=cF8 (?) Density (c)=2.163 Density (m)=2.16A Mwt=58.44 Vol=179.41 Ref: Barrett, W.T., Wallace, W.E. J. Am. Chem. Soc., v76 p366 (1954) Strong Lines: 2.82/G 1.99/G 1.63/G 1.26/G 1.15/X 3.26/9 1.41/6 1.70/2 1.29/1 0.00/1 2-Theta 27.366 31.703 45.448 53.868 56.472 66.227 73.070 75.292 83.992 d() 3.2563 2.8200 1.9940 1.7005 1.6281 1.4100 1.2939 1.2611 1.1513 I(f) 9.4 100.0 57.4 1.7 16.2 6.4 0.7 15.2 10.2 (hkl) ( 1 1 1) ( 2 0 0) ( 2 2 0) ( 3 1 1) ( 2 2 2) ( 4 0 0) ( 3 3 1) ( 4 2 0) ( 4 2 2) PDF#73-0380: QM=Calculated(C); d=Calculated; I=Calculated Sylvite, syn: K Cl Radiation=CuKa1 Lambda=1.54060 Filter= Calibration= 2T=24.536-87.892 I/Ic(RIR)=6.07 Ref: Calculated from ICSD using POWD-12++ (1997) Cubic - Powder Diffraction, Fm3m (225) Z=4 CELL: 6.2788 x 6.2788 x 6.2788 <90.0 x 90.0 x 90.0> P.S=cF8 (?) Density (c)=2.000 Density(m)= 2.23A Mwt=74.55 Vol=247.53 Ref: Ahtee, M. Ann. Acad. Sci. Fenn., Ser. A6, v313 p1 (1969) Strong Lines: 3.14/G 2.22/G 1.81/G 1.40/G 1.28/G 1.57/7 1.11/3 3.63/1 1.89/1 1.44/1 2-Theta 24.536 28.406 40.607 48.018 50.298 58.776 64.653 66.548 73.884 79.205 87.892 d() 3.6251 3.1394 2.2199 1.8931 1.8125 1.5697 1.4405 1.4040 1.2816 1.2084 1.1099 I(f) 0.6 100.0 59.5 0.4 17.5 7.1 0.1 17.1 11.3 0.1 3.1 (hkl) ( 1 1 1) ( 2 0 0) ( 2 2 0) ( 3 1 1) ( 2 2 2) ( 4 0 0) ( 3 3 1) ( 4 2 0) ( 4 2 2) ( 5 1 1) ( 4 4 0)