X-Ray Diffraction (XRD)

 Theory and Analytical Technique

X-Ray Analysis

 X-rays discovered in 1895

 Fundamental to understanding of crystal
structure and symmetry
 Powder diffraction analyses are a simple and
inexpensive method for identifying minerals,
especially fine-grained minerals
 X-ray Crystallography

X-ray wavelengths are on the same order of

magnitude as atomic spacings.
Crystals thus make excellent diffraction
gratings
Can use the geometry of the x-ray spots to
determine geometry of grating (i.e. the
crystal)
nλ = 2d sin θ
 Bragg Diffraction
 Diffraction from a three dimensional periodic
structure such as atoms in a crystal is called
Bragg Diffraction.
 Similar to diffraction though grating.
 Consequence of interference between waves
reflecting from different crystal planes.
 Constructive interference is given by Bragg's
law: nλ = 2d sin θ
 Where λ is the wavelength, d is the distance
between crystal planes, θ is the angle of the
diffracted wave. and n is an integer known as
the order of the diffracted beam.
Following Bragg's law, each dot (or reflection), in this
diffraction pattern forms from the constructive interference of
X-rays passing through a crystal. The data can be used to
determine the crystal's atomic structure.
 X-ray Generation
X-rays – High energy*, highly penetrative
electromagnetic radiation

*E = hc/λ λ(X-rays) = 0.02-100Å (avg. ~1 Å)

λ(visible light) = 4000-7200Å

X-ray Vacuum Tube

Cathode (W)– electron

generator

Anode (Mo, Cu, Fe, Co, Cr) –

electron target,
X-ray generator
Our instrument uses a copper target
 When light hits an electron, the
X-ray Spectra electron jumps to a higher energy
level, then drops back to its original,
shell, emitting light

 Continuous spectra (white

radiation)– range of X-ray
wavelengths generated by the
absorption (stopping) of
electrons by the target
 Characteristic X-rays –
particular wavelengths created
by dislodgement of inner shell
electrons of the target metal;
x-rays generated when outer
shell electrons collapse into
vacant inner shells
 K peaks created by collapse
from L to K shell;
K K peaks created by collapse
K from M to K shell
X
X-ray Crystallography Methods
Single-Crystal: Laue Method

Several directions simultaneously fulfill Bragg equations

Good for symmetry, but poor for analysis because distorted

Fig 7.39 of Klein (2002) Manual of Mineral

Science, John Wiley and Sons
X-ray Diffraction (Bragg’s Law)
nλ = 2d sinθ
Defines the spacing (d) of atomic planes and incident
angle (θ) at which X-rays of a particular wavelength
will reflect in phase (i.e., diffract)

GE+EH = nλ

θ’

≠ nλ
GE + EH is the path difference, waves add if equal to nλ
 X-ray Crystallography Methods:
Single-Crystal: Precession

Use motors to move crystal & sensor to satisfy

Bragg equations for different planes without
distortions

Fig 7.40 of Klein (2002)

Manual of Mineral Science,
John Wiley and Sons
 X-ray Crystallography Methods

Powder

Easiest
Infinite orientations at once, so only need to vary q ,
the angle of the incident beam of x-ray light.
Powder Diffraction Method
 Requires random
orientation of very fine
crystals
 Incident beam of a certain
X-ray wavelength will
diffract from atomic
planes oriented at the
appropriate θ angles for
the characteristic d
spacing
 Random orientation of
crystals will produce more
intense diffraction peaks
for particular angles that
correspond to
characteristic atomic
planes
Powder Diffraction Plots
θ = arcsin (nλ / 2d)

λ(Cu) = 1.54Å
d - Qtz [101] = 3.342
θ = 13.32° ; 2θ = 26.64°

Quartz
 Interpreting X-ray data
 We will use the data obtained to
 identify the mineral
 determine the dimensions of the unit
cell.