Introduction
It is a novel & non destructive method of chemical analysis
and a variety of x –ray techniques are available in practice.
These are : X – Ray Absorption : X-ray diffraction
X-ray Fluorescence
X – ray diffraction
“ Every crystalline substance gives a pattern; the same
substance always gives the same pattern; and in a mixture of
substances each produces its pattern independently of the others”
The X-ray diffraction pattern of a pure substance is, therefore,
like a fingerprint of the substance. It is based on the scattering of
x-rays by crystals.
Definition
The atomic planes of a crystal cause an incident beam of X-
rays to interfere with one another as they leave the crystal. The
phenomenon is called X-ray diffraction.
What is X-ray Diffraction ?
Why XRD?
Measure the average spacing's between layers or rows of atoms
Determine the orientation of a single crystal or grain
Find the crystal structure of an unknown material
Measure the size, shape and internal stress of small crystalline
regions
Basics of Crystallography
The atoms are arranged in a regular pattern, and
there is as smallest volume element that by
repetition in three dimensions describes the
crystal. This smallest volume element is called a
unit cell.
Crystals consist of planes of atoms that are spaced
a distance d apart, but can be resolved into many
atomic planes, each with a different d spacing.
The dimensions of the unit cell is described by
three axes : a, b, c and the angles between them
α, β , and γ are lattice constants which can be
Lattice determined by XRD.
Production of X-rays
X-rays are produced whenever
high-speed electrons collide with
a metal target.
A source of electrons – hot W
filament, a high accelerating
voltage between the cathode (W)
and the anode and a metal target,
Cu, Al, Mo, Mg.
The anode is a water-cooled
block of Cu containing desired
target metal.
Specimen Preparation
Powders:
0.1μm < particle size < 40 μm
Peak broadening less diffraction occurring
Bulks: smooth surface after polishing, specimens should be
thermal annealed to eliminate any surface deformation
induced during polishing.
A Modern Automated X-ray Diffractometer
X-ray
Detector
Tube
θ2
Sample stage
Cost: $560K to 1.6M
Basic components & Features of XRD
Production
Diffraction
Detection
Interpretation
Detection of Diffracted X-rays by a
Diffractometer
Bragg - Brentano Focus Geometry, Cullity
XRD Pattern of NaCl Powder
Miller indices: The peak is due to X-ray
diffraction from the {220} planes.
Diffraction angle 2θ (degrees)
Significance of Peak Shape in XRD
Peak position
Peak width
Peak intensity
Important for
Particle or Can also be fit with Gaussian,
Lerentzian, Gaussian-Lerentzian etc.
grain size
Residual strain
Effect of Lattice Strain on Diffraction
Peak Position and Width
No Strain
Uniform Strain
(d1-do)/do
Peak moves, no shape changes
Shifts to lower angles
Non-uniform Strain
D1 =/constant
Exceeds d0 on top, smaller than d0 on the Peak broadens
bottom
Applications of XRD
XRD is a non destructive technique to identify crystalline phases
and orientation
- Obtain XRD pattern ; Measure d-spacings ; Obtain
integrated intensities ;
- Compare data with known standards in the JCPDS file
To determine structural properties:
- Lattice parameters (10-4Å),, grain size, expitaxy, phase
composition, prefer strained orientation (Laue) order-disorder
transformation, thermal expansion
To measure thickness of thin films and multi-layers*
To determine atomic arrangement
Detection limits: ~3% in a two phase mixture; can be ~0.1% with
synchrotron radiation
Spatial resolution: normally none
Applications of XRD
The electron density and accordingly, the position of the atoms in
complex structures, such as penicillin may be determined from a
comprehensive mathematical study of the x-ray diffraction pattern.
The elucidation of structure of penicillin by xrd paved the way for
the later synthesis of penicillin.
The powder xrd pattern may be thought of as finger print of the
single crystal structure, and it may be used conduct qualitative and
quantitative analysis.
Xrd can also be used to determine whether the compound is solvated
or not
Applications of XRD
Particle size determination by applying the relation.
v= V. δθ. cos θ / 2n
Where v = the volume or size of an individual crystalline
V= the total volume of the specimen irradiated
n = the number of spots in a deffraction ring at a Bragg angle
θ δθ = the divergence of the X –ray beam
Determination of Cis-Trans isomerism
It is used to assess the weathering and degradation of natural and
synthetic , minerals.
Tooth enamel and dentine have been examined by xrd.
State of anneal in metals
Instrumental Sources of Error
Specimen displacement
Instrument misalignment
Error in zero 2 θ position
Peak distortion due to K alfa 2 and K beta wavelengths
Conclusions
Non-destructive, fast, easy sample preparation
High-accuracy for d-spacing calculations
Can be done in-situ
Single crystal, poly, and amorphous materials
Standards are available for thousands of material systems
