X-ray Diffraction Analysis

Principle, Instrument and Method

M.S.Pandian
Dept of Earth Sciences
Pondicherry University

X-ray Diffraction Analysis

Principle, Instrument and Method

M.S.Pandian
Dept of Earth Sciences
Pondicherry University

Lecture Topics
X-ray Diffraction
Powder X-ray Diffractometer
Applications of Powder XRD
(continued in next part)

 X-ray Diffraction
Powder X-ray Diffractometer

Electromagnetic Spectrum

Interaction of X-ray with

Matter

Fluorescence
Ionisation
Diffraction

Fluorescence

Ionisation

Ionisation
Ionizing radiations carry enough energy to
break chemical bonds and separate
electrons from the parent atoms and
molecules, thereby creating ions in the
irradiated material.

Diffraction
Coherent scattering of X-ray by
crystalline substance

Matter
Chemical composition
Physical property
Crystal structure
Crystalline
Amorphous

Diamond and Graphite

Crystalline Substances (inorganic)

Crystalline Substances
Ordered arrangement of atoms
Atom positions are regularly repeated in space
following a pattern defined by crystal lattice
Distribution of atoms in crystal structure
follows one of 14 Bravais Lattices derived from
6 Crystal System.

The 14 Bravais Lattices

Bravais Lattices

Molecules, Unit Cell & Crystal

Every crystal structure has a unit cell

Smallest unit into which a crystal structure
can be broken down that sill retains the
properties of the whole structure

Crystal System
Each crystal system has a different axis
length and angles that separate the
atoms
lengths of the axes are a, b, and c
angles between the atom planes are , and
Crystal
Cubic

Axis Length
a=b=c

Angles
= = = 90

Rhombohedral

a=b=c

= = 90

Tetragonal

a=bc

= = = 90

Orthorhombic

a=bc

= = = 90

Hexagonal

a=bc

= = 90, = 120

Monoclinic

abc

= = 90, 90

Triclinic

abc

90

c
b
y

Crystal System

Lattice Planes

Miller Index
(William Hallowes Miller 1839)
Defining particular plane of the atom with Miller Index
3 steps to determine the Miller Index
Find the intercepts x = 2, y = 3, and z = 2 from figure
Take the reciprocal of the axis length, 1/2, 1/3, and 1/2
Find LCM and then multiply
the reciprocal
z
Then, the Miler Index is (3, 2, 3) 6*1/2, 6*1/3, 6*1/2..
Example,
c=2
a=2
b=3
y

X-ray Diffraction
The spacing of atoms in crystal lattices
is of the same order as the wavelength
of X-radiation (0.1 to 100 Angstrm ). Von
Laue discovered (1912) that a crystal could
be used as a diffraction grating for X-rays.

William Lawrence Bragg discovered

(1912) law relating the spacing between
atoms in a crystal to the angle at which
X-rays are scattered when they strike
the crystal.
n = 2d Sin

In-phase scattering of 2 rays depends on the distance

d and the wavelength () of the incident radiation.
The distance l is equal to d sin. For the 2 rays to
scatter in phase, = 2d sin. This is Braggs lawin its
simplest form.

X-Ray Diffraction
Bragg equation relates the spacing between
adjacent crystal planes and the angle of
diffraction.

= 2d sin
d spacing between crystal planes
angle of scattering
wavelength of x-ray beam
2 diffraction angle.

Diffraction of X-ray by Lattice Planes

X-ray Diffraction
in Crystalline Materials
Every crystalline substance produces a unique
diffraction pattern, which is a fingerprint of the
material
In polycrystalline materials each phase produces
its pattern independently of the others.
X-ray diffraction analysis is thus ideally suited for
characterization and identification of phases.

 X-ray Diffraction

X-ray Diffractometer
Powder
Single Crystal

X-ray Powder Diffractometer

X-ray tube
Goniometer and optical path
Sample holder
Detector

X-ray Powder Diffractometer

X-ray tube
Goniometer and optical path
Sample holder
Detector

Generation of X-rays

When an atom is bombarded with sufficiently high energy

electrons, electrons of the atom are knocked out from their
shell (excited state, unstable). Leads to transition of
electrons to fill up the vacancy (ground state, stable). Each
electron transition generates X-rays of a specific energy
(with wave length in the range from 0.1 to 100)
equivalent to that shell.

CuK1
CuK2
K1/K2
CuK

=
=
=
=

1.540598
1.544426
2
1.392250

X-ray Tube

X-ray Tube

Goniometer: 2 Theta - Theta

Goniometer: Theta - Theta

Goniometer in Theta-Theta Geometry

Optical Path
Soller slits
Divergence slit
Beam Mask
Sample
Anti-Scatter slit
Receiving slit
Monochromator or Beta filter

Basic Geometry of a diffractometer

without monochromator

Geometry of a diffractometer
with monochromator
Detector
Soller slits
Receiving slit

X-ray tube
(line focus)

Soller slits

Beam mask
Divergence slit

Curved crystal
monochromator
(Graphite)

Anti scatter slit

Polycrystalline sample

Sample Preparation

Powder Sample Preparation

on a Aluminium Holder

Detector: Scintillation Counter

Scintillation detectors work by transferring the X-ray photon into light

by Tl activated NaI crystal.
This in turn will release electrons which fall sequentially on 10 dynodes
which multiplies the electrons 2 exp10 causing a negative pulse

Detector: Proportional Counter

Gas filled (Ar-Methane) counter. X-rays cause ionization of the gas.

Ions are drawn to wire at high tension.
At the wire they cause a dip in the high voltage which is counted as a
pulse.

General Scan Condition

Generator Settings:
Step Size [2Th.]:
Scan Step Time [s]:
Scan range [2Th.]:

25 mA, 40 kV
0.0200
1.0000
15-75

Amorphous Patterns

Counts

150

Metal Tape 5991

100

50

0
20

30

40

50
Position [2Theta]

60

70

80

XRD Pattern of a Mineral

Peak Parameters: 2, d spacing, I/Io, FWHM

( = 2d Sin )

Peak Broadening due to

Instrument:
optics, convolution of beam
Sample:
Particle size, Crystal defects (lattice
strain, vacancy, substitution, interstitial)

Instrumental broadening in silicon standard

Peak Broadening due to Crystallite Size

Peak Broadening due to Lattice Strain

 X-ray Diffraction
Powder X-ray Diffractometer

Applications of Powder
XRDcontinued in next part