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X-RAY DIFFRACTION

METHODS

Prepared by:
Ms.M.Shalini
(i) Laue Method
The Laue method is mainly used to
determine the orientation of large
single crystals while radiation is
reflected from, or transmitted
through a fixed crystal
Laue Studied The phenomena of

crystal diffraction by two methods:


(a). Transmission method

(b). Back reflection method


(a). Transmission method
(b). Back reflection method
Back Reflection

Transmission Laue

Laue

• In the transmission Laue • In the back-reflection


method, the film is method, the film is
placed behind the placed between the x-
crystal to record ray source and the
beams which are crystal. The beams
which are diffracted in
transmitted through a backward direction
the crystal. are recorded.
• •
• One side of the cone of • One side of the cone of
Laue reflections is Laue reflections is
defined by the defined by the
transmitted beam. transmitted beam.
The film intersects the The film intersects the
cone, with the cone, with the
diffraction spots
diffraction spots generally lying on an
generally lying on an hyperbola.
ellipse.
Bragg X-ray spectrophotometer
method
vBragg analyzed the structure of crystals of NaCl, KCl, and ZnS
using the Laue’s Photographs.
vHe devised a spectrophotometer to measure the intensity of X-ray
beam.
vThe Bragg’s equation is as follows:
The Bragg Equation

nλ = 2d sinθ
where n is an integer
 is the wavelength of the x-rays
d is the interplanar spacing in the specimen
 is the diffraction angle

The Bragg equation is the fundamental equation,


valid only for monochromatic X-rays, that is used to
calculate interplanar spacings used in XRD analysis
WORKING OF BRAGG
SPECTROPHOTOMETER
• The crystal is mounted in such a position that θ=
0ο and the ionization chamber is adjusted to
receive x-rays.
• The crystal and ionization chamber are moved in
steps so that the angle through which the
chamber is rotated is twice the angle through
which the crystal is rotated.
• The ionization at first fall as θ rises but for certain
values of θ it rises sharply.
• This corresponds to the direction of X-ray
spectrum.
• X-ray spectrum are obtained by plotting a graph
between ionization current and the glancing
angle θ1, θ2 and θ3.
• With known values of d and n and from observed
An X- ray spectrum showing variation
of ionization current as a function of
glancing angle θ
The following figures show experimental x-ray

diffraction patterns of cubic SiC


Measurement of λ
Ø The wavelength of the x-rays can be
determined by employing the eqn:

n λ= 2 d sin Θ
Ø The value of θ for various order
spectra produced by crystal was
measured.
Ø The mean value of λ/d was
calculated. The value of λ/d is
known as lattice constant.
Ø Knowing d, the wavelength is thus
Measurement of d
• d= a(2)0.5 /2 for simple cubic lattice
• d= a/2 for fcc lattice
• d= a(3)0.5 /2 for bcc crystal lattice
• Where a= ( Mol.wtXNo.Of atoms in
unit cell)0.333
 (Avogadro’s NoX
Density)
SIMPLE CUBIC

BODY CENTERED CUBIC

FACE CENTERED CUBIC


Determination of crystal
structure by Bragg’s law
From Bragg’s eqn the ratio of lattice
spacing for various groups of plane is
recorded. This ratio is different for
different crystals.
d100:d110:d111= 1:1/√2: 1/√3 for

simple cubic
d100:d110:d111= 1:1/√2: 1/√3 for fcc

crystal
d100:d110:d111= 1:1/√2: 1/√3 for for

bcc crystal
3. Powder crystal Method
What is X-ray Powder Diffraction (XRD)?

X-ray powder diffraction (XRD) is a rapid analytical technique


primarily used for phase identification of a crystalline material
and can provide information on unit cell dimensions. The analyzed
crystal is finely ground, homogenized, and average bulk composition
is determined.

It was devised independently by Debye and Scherrer in Germany and by


Hull in America at the same time.
The experimental setup was shown in figure below:
Powder Crystal method
THE POWDER METHOD

If a powdered specimen is used,


instead of a single crystal, then there is
no need to rotate the specimen, because
there will always be some crystals at an
orientation for which diffraction is
permitted. Here a monochromatic X-ray beam
is incident on a powdered or
polycrystalline sample.
This method is useful for samples
that are difficult to obtain n single
crystal form.

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The powder method is used to determine the
value of the lattice parameters accurately .
Lattice parameters are the magnitudes of the unit
vectors a, b and c which define the unit cell for
the crystal.

For every set of crystal planes, by
chance, one or more crystals will be in the
correct orientation to give the correct Bragg
angle to satisfy Bragg's equation. Every crystal
plane is thus capable of diffraction. Each
diffraction line is made up of a large number of
small spots, each from a separate crystal. Each
spot is so small as to give the appearance of a
continuous line.
ROTATING CRYSTAL METHOD

Lattice constant of the


crystal can be determined by means of
this method; for a given wavelength if
the angle θat which a
reflection occurs isd hklknown,
can be determined.
a
d =
h2 +
k 2+l 2
The reflected beams are located on the surface of imaginary cones. By
recording the diffraction patterns (both angles and intensities) for
various crystal orientations, one can determine the shape and size of
unit cell as well as arrangement of atoms inside the cell.
Application of XRD
XRD is a nondestructive technique. Some of the uses
of x-ray diffraction are;

1.Differentiation between crystalline and


amorphous materials;
2.Determination of the structure of crystalline
materials;
3.Determination of electron distribution within
the atoms, and throughout the unit cell;
4.Determination of the orientation of single
crystals;
5.Determination of the texture of polygrained
materials;
6.Measurement of strain and small grain
size…..etc
QUERIES???????????