DETERMINATION OF

CRYSTAL STRUCTURE AND

CRYSTALLITE SIZE USING
X-RAY DIFFRACTION

Presented by
R.Asika
INTRODUCTION
X-rays were discovered by Wilhelm Roentgen who called them X-rays ,so x-rays
are also called as Roentgen rays. X-ray diffraction in crystals was discovered by Max
Von Laue.
X-rays are short wavelength electromagnetic radiations produced by the
deceleration of high energy electrons or by electronic transitions of electrons in the inner
orbital of atoms.
X- ray region 0.1 to 100Å. For analytical purpose X-rays in the range of 0.7 to 2Å
is used.
The penetrating power of X-rays depends on energy also, there are two types of
X-rays.
 Hard X-rays : which have high frequency and have more energy.
 Soft X-rays: which have less penetrating and have low energy
X-RAY DIFFRACTION
X-ray diffraction is based on constructive interference of
monochromatic x-rays and a crystalline sample. These x-rays are
generated by a cathode ray tube filtered to produce monochromatic
radiation collimated to concentrate and directed towards the sample.
The interaction of incident rays with the sample produces constructive
interference when conditions satisfy Bragg’s law.
X-rays are usually used as medium to perform diffraction in crystals.
It helps in
 Identifying the crystal structure
 Calculate lattice parameter
 Measure stresses in the material.
 Measure crystallographic texture.
BRAGG’S LAW
Concept of d spacing (spacing between two parallel planes) was
used to mathematically define diffraction by William L. Bragg and
William H. Bragg in 1913.
“Bragg’s law states that X-rays reflected from different parallel
planes of a crystal interfere constructively when the path difference is
integral multiple of wavelength of X-rays” .
CONT….
Constructive interference occurs only when
nλ= AB+BC
AB=BC
nλ=2AB
Sinθ=AB/d
nλ=2dsinθ
where,
n is an integer(1,2,3,…)
λ is the wavelength of the x-rays
d is the interplanar spacing in the specimen
θ is the diffraction angle

The magnitude of the distance between two adjacent and parallel planes of atoms (i.e. Interplanar spacing) is
given by

where,
a-Lattice parameter
CONSTRUCTIVE AND DESTRUCTIVE
INTERFERENCE
X-rays interact with each other Produces interference.
Light passing through two slit Separated by a distance similar to the
wavelength produces an interference pattern.
DETERMINATION OF CRYSTAL STRUCTURE BY X-RAY DIFFRACTION

• Crystalline solids have long – range order of their atoms or molecules..It act as
scattering center for X-rays.
• When X-rays interact with the crystalline lattice, a diffraction pattern is formed
which reveals the spacing between planes of atom.
• X-ray crystallography is used to determine the structure of simple atomic
lattices and proteins, DNA and other biologically important molecules.
Crystal structure from X-ray diffraction peaks
Diffraction scan gives data in form of 2θ vs Intensity.
d spacing can be calculated from Bragg’s law- if we know angle θ and
wavelength of X-ray used.
CONT….
We need to know that in a particular crystal structure which
particular planes are going to take part in diffraction.

where h,k and l are Miller indices.

• If both h and k are odd or even ,it is said to be unmixed.
• If one of them is even and another one is odd, it is said to be mixed.
Example
• From the diffraction peak of aluminium,

(111) – where h=1,k=1,l=1, these three values are odd and hence it is
unmixed.
(200) - h ,k and l are even –unmixed
• Likewise, (220),(311),(222),(400),(331),(420) are unmixed.
• All the planes that mentioned above satisfies the condition for FCC
structure.
• Thus the crystal structure of aluminium is FCC structure.
DETERMINATION OF CRYSTALLITE SIZE
The crystallite (grain) size can be calculated from XRD data using
Scherrer equation. The Scherrer equation in X-ray diffraction and
crystallography is a formula that relates the size of sub-micrometer
crystallites in a solid to the broadening of a peak in a diffraction pattern.
It is named after Paul Scherrer and it was published in 1918. It is used in
the determination of crystal size in the form of powders. The equation is
D=Kλ/βcosθ
Where,
D= crystallite size (nm)
k=0.9 (scherrer constant)
λ=0.15406 nm (wavelength of the X-ray source)
β=FWHM(radians)
θ=Peak position (radians)
FWHM (Full Width at Half Maximum)
 It is the width of the spectrum curve measured between those points
on the Y-axis which are half the maximum amplitude.
EXAMPLE
Applicability of Scherrer Formula
 Scherrer equation is limited to nano-scale crystallites, or more-strictly the
coherently scattering domain size, which may be smaller than the
crystallite size.
 It is not applicable to grains larger than about 0.1 to 0.2 μm(i.e. The
equation is effective when the crystalline size of the powder is below 100
nm).
 Variety of factors contribute to the width of a diffraction peak besides
instrumental effect and crystallite size; the most important of these are
inhomogeneous strain and crystal lattice imperfections.
 If all of these other contributions to the peak width ,including instrumental
broadening were zero, then the peak width would be determined solely by
crystallite size and scherrer formula would apply.
REFERENCE
https://youtu.be/pRwv3kiAkOQ
https://youtu.be/H8C14RvICNI
https://youtu.be/m8L-B4A75Ec
https://www.slideshare.net/mobile/bharathpharmacis
t/81347482-xraydiffractiontechnique-39635806
https://googleweblight.com/i?u=https://
en.m.wikipedia.org/wiki/Full_width_at_half_maximu
m&hl=hi-IN
https://googleweblight.com/i?u=https://en.m.wikiped
ia.org/wiki/Scherrer_equation&hl=en-IN
THANK YOU