Materials science and Engineering

CHE F243

Karthik Chethan V.
BITS Pilani, Hyderabad Campus
2024

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X-Ray Diffraction (XRD)

The Braggs were awarded the Nobel

Prize in physics in 1915 for their work
in determining crystal structures
beginning with NaCl, ZnS and
diamond.

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• Bragg developed a relationship in 1913 to explain
why the faces of crystals (unit cells) appear to
reflect X-ray beams at certain angles of incidence
(theta, ϴ).
• The variable d is the distance between atomic
layers in a crystal, and the invariable lambda, λ is
the wavelength of the incident X-ray beam; n is
an integer. This observation is an example of X-
ray wave interference.
• 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.
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 XRD
• X-rays are produced whenever high-speed
electrons collide with a metal target.
• A source of electrons – hot tungsten filament, a
high accelerating voltage between the cathode
(tungsten) and the anode will produce high-
speed electrons.
• High-speed electrons collide with metal target,
Cu, Al, Mo and Mg. The anode is a water-cooled
block of Cu containing desired target metal.
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 Why XRD
• Measure the average spacings between layers
or rows of atoms (clathrates).
• Determine the orientation of a single crystal
or grain.
• Find the crystal structure of an unknown
material. The size, geometry and internal
stress of small crystalline regions.

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Interference (scattering or diffraction)

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 Bragg’s Law
• Constructive interference occurs only when n λ = AB + BC
• AB=BC, n λ = 2AB, sinϴ=AB/d, AB=d sinϴ
• n λ =2dsinϴ

X-ray 1

X-ray 2

AB+BC = multiples of nλ

To satisfy Bragg’s Law, ϴ must change as d

changes.

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Method

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 Randomization
• Since the three rotations result in the crystal
being oriented in every possible position in
space, it is equivalent to use powdered
crystals which, because of their random
orientation, are already oriented in every
possible direction.

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 POWDER METHOD
 In the powder sample there are crystallites in different ‘random’ orientations (a polycrystalline
sample too has grains in different orientations)
 The coherent x-ray beam is diffracted by these crystallites at various angles to the incident direction
 All the diffracted beams (called ‘reflections’) from a single plane, but from different crystallites lie
on a cone.
 Depending on the angle there are forward and back reflection cones.
 A diffractometer can record the angle of these reflections along with the intensities of the reflection
 The X-ray source and diffractometer move in arcs of a circle- maintaining the Bragg ‘reflection’
geometry as in the figure (right)

Different cones
for different
reflections
 How to visualize the occurrence of peaks at various angles
It is ‘somewhat difficult’ to actually visualize a random assembly of crystallites giving peaks at various angels in a XRD
scan. The figures below are expected to give a ‘visual feel’ for the same. [Hypothetical crystal with a = 4Å is assumed with
=1.54Å. Only planes of the type xx0 (like (100,110)are considered].

Random assemblage of
crystallites in a material
As the scan takes place at increasing
angles, planes with suitable ‘d’,
which diffract are ‘picked out’ from
favourably oriented crystallites

h2 hkl d Sin(q) q

1 100 4.00 0.19 11.10

2 110 2.83 0.27 15.80
3 111 2.31 0.33 19.48
4 200 2.00 0.39 22.64
5 210 1.79 0.43 25.50
6 211 1.63 0.47 28.13
8 220 1.41 0.54 32.99

9 300 1.33 0.58 35.27

10 310 1.26 0.61 37.50

• A sample of some hundreds of crystals (i.e. a powdered sample)
show that the diffracted beams form continuous cones.
• A circle of film is used to record the diffraction pattern as shown.
Each cone intersects the film giving diffraction lines. The lines are
seen as arcs on the film.

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• The angles at which x-rays are diffracted depends on the distance
between adjacent layers of atoms or ions. X-rays that hit adjacent
layers can add their energies constructively when they are “in
phase”. This produces dark dots on a detector plate.

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Example

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Example

Increasing d

Increasing q

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Model Question and Indexing

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 Applications
• XRD is a nondestructive technique.
• To identify crystalline phases and orientation.
• Lattice parameters (10-4Å), strain, grain size,
phase composition, preferred orientation, order-
disorder transformation and thermal expansion.
• To measure thickness of thin films and multi-
layers.
• To determine atomic arrangement.
• Detection limits: ~3 wt % in a two phase mixture
can be detected.

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 Conclusions
• Non-destructive, fast, easy sample prep.
• 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.

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