X-ray Powder Diffraction (XRD)

X-ray diffraction (XRD) is a versatile, non-destructive

analytical method to analyze material properties like
phase structure, composition, texture, residual stress and
many more of powder samples, solid samples or even
liquid samples.

The main topics of X-ray diffraction are:

• Qualitative and quantitative phase analysis of pure substances and

mixtures
• Analysis of the influence of temperature and/or other non-ambient variables,
such as humidity or applied pressure
• Analysis of the microstructure of the material, including properties like
crystallite size, preferred orientation effects and residual stress in
polycrystalline engineered materials.
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X-ray powder diffraction is used in a wide variety of research and process
control environments.

For example:

• Characterization of (new) materials at universities and research centers

• Process control in several industries like building materials, chemicals,
pharmaceuticals, for instance phase composition and content
• Determination of polymorphism, API (active pharmaceutical ingredient)
concentration determination, API stability studies in the pharmaceutical
industry
• Phase identification of minerals in geological samples
• Optimization of fabrication parameters for wear-resistant ceramics and
biomaterials
• Determination of the crystallinity of a phase
• Determination of amorphous phase contents in mixtures
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An X-Ray Diffractometer 3
 Advanced analyses
Whole pattern → Phase identification, quantitative analysis

Peak position → Lattice parameters

Peak width → Crystallite size & strain

Diffraction %Crystallinity
Amorphous scattering

Background

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The diffraction pattern of a mixture is a simple sum of the
scattering from each component phase

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Phase identification

Identification of phases is achieved by comparing the

X-ray diffraction pattern obtained from an unknown
sample with patterns of a reference database.

This process is very similar to the identification of

finger prints in crime scene investigations. The
most comprehensive database is maintained by
the ICDD (International Centre of Diffraction Data). 8
Databases such as the Powder Diffraction File (PDF) contain lists
for thousands of crystalline phases.
New Powder Diffraction FileTM (PDF®) contains 1,047,661 unique material
data sets. Each data set contains diffraction, crystallographic and
bibliographic data, as well as experimental, instrument and sampling
conditions, and select physical properties in a common standardized format.

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 PANalytical’s XRD
software suite

Angstrom Advanced Inc.

XRD2DScan software

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The Phase Identification

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 Diffraction
Diffraction is the spreading of waves around obstacles. Diffraction takes place
with sound; with electromagnetic radiation, such as light, X-rays, and gamma
rays; and with very small moving particles such as atoms, neutrons, and
electrons, which show wavelike properties.

Single slit diffraction when a wave

passes through an aperture with width
smaller than the wavelength (d, is less
than, lambda, d<λ).

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Computational model of an interference
pattern from two-slit diffraction.

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 Total Value Total Value of
of amplitude amplitude
and phase at and phase at
A B

Effect of path difference on relative phase.

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If the waves are reinforce one another If the waves are shifted

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Max Von Laue experiment (1912)

"What would happen

if very much shorter
waves travel in the
crystal?" This was the
question posited by Max
von Laue

© WILEY-VCH
X-ray diffraction pattern from a zinc-blende
(ZnS) crystal. Figure reprinted with
permission from W. Friedrich et al. Annalen
der Physik 346, 971–988 (1913).

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 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline a-iron (BCC)

Adapted from Fig. 3.22, Callister 8e.
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 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra l Adapted from Fig. 3.20,
q q
distance
travelled Callister & Rethwisch 8e.
by wave “2” spacing
d between
planes

Measurement of critical X-ray

nl
angle, qc, allows intensity d=
(from 2 sin qc
computation of planar
detector)
spacing, d.
q
qc 22
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 A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.

2q 2q 2q

• For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of27
crystallites, not just one or two.
Fundamentals of X-ray Diffraction

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In physics, attenuation (in some
contexts also called extinction) is the
gradual loss in intensity of any kind 29
of flux through a medium.
X-Ray Scattering

Occurs between X-ray and

loose Valance-e’s

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 Elastic scattering by electron

Interaction of a X-ray front

with an isolated electron,
Incident X-ray which becomes a new
X.ray source, producing
the X-rays waves in a
spherical mode

Although x-rays are scattered in all directions by an electron, the

intensity of the scattered beam depends on the angle of scattering,

An electron will oscillate in-phase with an x-ray

beam according to the following equation (called
the Thompson equation after J.J. Thompson who
demonstrated the relationship in 1906):

where I0 is the intensity of the incident beam; e the charge on the electron; me the mass of
the electron; c the speed of light; and r the distance from the scattering electron to the
detector (with the r2 term in the denominator expressing the inverse square law). 31
 The spherical waves
Incident X-ray produced by two
electrons interact with
each other, producing
positive and negative
interferences.

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 A single atom scatters an
incident beam of x-rays in
«almost» all directions in
space,

(a) Scattering by an atom

But a large number of atoms

arranged in a perfectly
periodic array in three
dimensions to form a crystal
scatters (diffracts) x-rays in
relatively few directions.
(b) Diffraction by a crystal
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n = order of diffraction

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 z
X-Ray Diffraction
z
Pattern
z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline a-iron (BCC)

Adapted from Fig. 3.22, Callister 8e.
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Other Diffraction Methods

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 The Laue method
The first diffraction method ever used.

The Laue method is mainly used to determine the orientation of large single crystals.
White radiation is reflected from, or transmitted through, a fixed crystal.

Back-reflection Laue

In the back-reflection method, the film is

placed between the x-ray source and the
crystal. The beams which are diffracted
in a backward direction are recorded.

One side of the cone of Laue reflections

is defined by the transmitted beam. The
film intersects the cone, with the
diffraction spots generally lying on an
hyperbola.
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Transmission Laue

In the transmission Laue method, the

film is placed behind the crystal to
record beams which are transmitted
through the crystal.

One side of the cone of Laue

reflections is defined by the
transmitted beam. The film intersects
the cone, with the diffraction spots
generally lying on an ellipse.

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Rotating Crystal Method

In the rotating crystal method, a single crystal is

mounted with an axis normal to a monochromatic
x-ray beam. A cylindrical film is placed around it and
the crystal is rotated about the chosen axis.

As the crystal rotates, sets of lattice planes will at

some point make the correct Bragg angle for the
monochromatic incident beam, and at that point a
diffracted beam will be formed.

The reflected beams are located on the surface of

imaginary cones. When the film is laid out flat, the
diffraction spots lie on horizontal lines.

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Debye-Scherrer photographic method

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Diffraction occurs when light is scattered by a periodic array with
long-range order, producing constructive interference at
specific angles.

• The electrons in an atom coherently scatter light.

– We can regard each atom as a coherent point scatterer
– The strength with which an atom scatters light is proportional to the number of electrons
around the atom.
• The atoms in a crystal are arranged in a periodic array and
thus can diffract light.
• The wavelength of X rays are similar to the distance
between atoms.
• The scattering of X-rays from atoms produces a diffraction
pattern, which contains information about the atomic
arrangement within the crystal
• Amorphous materials like glass do not have a periodic array with long-range order, so they do
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not produce a diffraction pattern
 Question

The spacings of planes in a crystal is 1.8 Å and the angle for the first order
Bragg’s reflection is 30. Determine the energy of the X-ray photon in keV.

From Bragg’s law, we have

2𝑑𝑠𝑖𝑛𝜃 2 𝑥 1.8 Å 𝑥 𝑠𝑖𝑛30

λ= = = 1.8 Å
𝑛 1

The energy of the X-ray photon

ℎ𝑐 6.62 𝑥 10−34 𝑥 3 𝑥 108 11.03 x 10−16

E= = J = 11.03 x 10-16 J= eV = 6.90 keV
λ 1.8 x 10−10
1.6 x 10−19

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 Question
The crystal structure of SrTiO3 is cubic, space group Pm3m with a unit cell
edge a= 3.90 Å. Calculate the expected 2θ positions of the the peaks of
100, 110, 111 in the diffraction pattern, if the radiation is Cu Kα (λ = 1.54 Å).

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Search for:

-Texture analysis
-Rieldvelt analysis
-Strain analysis
-Cystallite size
determination via XRD

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