STKK 6014

X-RAY DIFFRACTION

Group Presentation

WHAT IS X-RAY DIFFRACTION ?

XRD WORKING CONCEPT

When a monochromatic x-ray beam with wavelength is incident on

the lattice planes in a crystal planes in a crystal at an angle ,
diffraction occurs only when the distance traveled by the rays reflected
from successive planes differs by a complete number n of
wavelengths. By varying the angle , the Braggs Law conditions are
satisfied by different d-spacing in polycrystalline materials. Plotting the
angular positions and intensities of the resultant diffraction peaks
produces a pattern which is characterised of the sample. Where a
mixture of different phases is present, the diffractogram is formed by
addition of the individual patterns.

WHERE DO XRAYS COME FROM?

Two principal methods for Xray
generation:
1) Fire beam of electrons at metal target.
Ionization of inner shell electrons results in
formation of an electron hole.
Relaxation of electrons from upper shells.
The energy difference E (1010 m) is
released in the form of Xrays of specific
wavelengths.
Commonly used metals are Cu K (=
1.5418 ) and Mo K ( = 0.71073 ).
Very Inefficient. Most energy dissipated at
heat (requires permanent cooling).

2)Accelerate electrons in a particle

accelerator
(synchrotron
source).
Electrons accelerated at relativistic
velocities in circular orbits. As velocities
approach the speed of light they emit
electromagnetic radiation in the Xray
region.

The Xrays produced have a range of

wavelengths (white radiation or
Bremsstrahlung).
Results in high flux of Xrays.
Laue experiment

BRAGGS LAW
n = 2d sin
The Braggs were awarded the
Nobel Prize in physics in 1915 for
their work in determining crystal
structures beginning with NaCl, ZnS
and diamond.
Although Bragg's law was used to
explain the interference pattern of
X-rays
scattered
by
crystals,
diffraction has been developed to
study the structure of all states of
matter with any beam, e.g., ions,
electrons, neutrons, and protons,
with a wavelength similar to the
distance between the atomic or
molecular structures of interest.

Braggs Law and Diffraction:

How waves reveal the atomic structure of crystals
n = 2d sin
= xray wavelength, d = distance between lattice planes, = angle of
incidence with lattice plane, n = integern-integer
Diffraction occurs only when Braggs Law is satisfied
Condition for constructive interference (x-rays 1 & 2) from planes with
spacing d

XRD INSTRUMENT

Detector

Electron gun

Known as
goniometer
Sample holder

goniometer

GONIOMETER
Theta : 2-Theta
(1:2)

SAMPLE PREPARATION
The single most important determinate of the quality of XRD

data obtained from a powder sample.

To be able to see all of the diffraction peaks, the specimens

powder must present a large number of crystallites in a

random orientation to the incident beam.
There is no standard way to prepare a specimen for

powder diffraction, and the most important consideration is

the objective of the experiment.

 Step 1 : Sample Preparation Methods

The sample size should be reduced from a fist-sized hand
specimen to a powder suitable for XRD analysis.

Step 2 : Sample Mount Methods

There are many different ways of mounting specimens for
analysis:
For rapid determination of accurate peak positions, a thin
sample with as much area as possible presented to the
beam is generally best.
For accurate intensities, you will want a thick sample of
randomly oriented crystallites.
Important note: Run an empty sample holder as a blank:
Although most materials used as sample holders are
ostensibly amorphous and do not yield a diffraction pattern,
in practice this is rarely the case

 Specimens and Experimental Errors

Several factors that contributed to diffraction errors are as
follows :
Flat Specimen Error - Occurs - surface of the specimen is flat, and
does not conform to the curvature of the focusing circle.
Compositional Variations between Sample and Specimen - related to
grinding, environmental interaction or irradiation effects.
Specimen Displacement - geometry of the sample mount - causes
positional deviation on the focusing circle.
Specimen Transparency - Penetration of the beam into a thick
specimen changes the location in which diffraction occurs.
Specimen Thickness - Thin specimens - produce accurate peak
positions; thicker specimens - produce more accurate peak
intensities.
Particle Inhomogeneity - Inhomogenities can significantly alter
diffraction intensities and peaks seen.
Preferred Orientation - Non-random orientation of crystallites can
produce large variations in intensity and limit the peaks seen.

APPLICATIONS OF XRD

 Powder (polycrystalline) diffraction - commonly used

for chemical analysis

Identification Phase identification (search/match)

Investigation of high/low temperature phases
Solid solutions
Determinations of unit cell parameters of new materials

crystallinity parts give sharp narrow diffraction peaks

amorphous region - a very broad peak (halo)

ratio between the intensity of crystallinity and

amorphous part can be used to calculate the amount of

Polymer
crystallinity

crystallinity in the material.

Notes :
A polymer can be considered as partly crystalline and
partly amorphous. The crystalline domain act as a
reinforcing grid, improves the performance over a wide
range of temperature. However, too much crystallinity
causes brittleness.

 The principles of stress analysis by X-ray diffraction is

based on measuring angular lattice strain distributions.
A reflection at high 2 is chosen and the change in the
d-spacing is measured with different orientations of the
sample.
The stress can be calculated from the strain distribution
by using Hookes law.

Residual
stress

Notes :
Residual stress is the stress remains in the material
after the external force that caused the stress have been
removed. Stress is defined as force per unit area.
Positive values indicate tensile (expansion) stress, while
negative values indicate a compressive state.
The deformation per unit length is called strain.
The residual stress can be introduced by any chemical,
mechanical or thermal process; such as machining,
plating and welding.

Texture
analysis

determination of the preferred orientation of the

crystallites in polycrystalline aggregates.
Texture - synonym to preferred crystallographic
orientation in the polycrystalline material, normally single
phase.
preferred orientation -described in terms of polefigures.
A polefigure - scanned by measuring the diffraction
intensity of a given reflection (2 is constant) at a large
number of different angular orientation of the specimen.
polefigures represent sterographic or equal area
projection.
The intensity of a given reflection (h, k, l) is proportional
to the number of h, k, l planes in reflecting condition
(Braggs law).
The polefigure gives the probability of finding a given
crystal-plane-normal as function of the specimen
orientation. If the crystallites in the sample have a
random orientation, the recorded intensity will be
uniform.

APPLICATIONS OF POWDER
DIFFRACTION
Diffraction line parameter

Applications

Peak position

Unit-cell parameter refinement

Pattern indexing
Space group determination
Anisotropic thermal expansion
Macrostress: sin2 method
Phase identification

Intensity

Phase abundance
Reaction kinetics
Crystal structure analysis
Rietveld refinement
Search/match, phase identification
Preferred orientation, texture analysis

Diffraction line parameter

Applications

Width/breadth and shape

Instrumental resolution function

Microstructure: line profile analysis
Microstructure (crystallite size, size
distribution, lattice distortion, structure
mistakes, dislocations, composition
gradient), crystallite growth kinetics
Three dimensional microstructure

Non-ambient and dynamic

diffraction

In situ diffraction under external constraints

Reaction kinetics

SUMMARY
X-ray diffraction provides a powerful
tool to study the structure and
composition of the materials which is a
key requirement for understanding
materials properties