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X-Ray Diffraction
CONTENTS
INTRODUCTION
BRAGG EQUATION

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INSTRUMENTATION
X-RAY DIFFRACTION METHODS
APPLICATIONS
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ELECTROMAGNETIC
SPECTRUM
 INTRODUCTION
X-Rays :
 X-rays are short wave length electromagnetic radiations
produced by the deceleration of high energy electrons or by

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electronic transitions of electrons in the inner orbital of atoms
 X-ray region 0.1to100 A˚
 Analytical purpose 0.7 to 2 A˚
 More energetic (i.e. can penetrate deeper into a material). 
 Emitted in a continuous band of white radiation as well as a
series of discrete lines that are characteristic of the target
material.
Characteristic Radiation:
 The characteristic lines in an atom's emission spectra are called K, L, M, ... and
correspond to the n = 1, 2, 3, ... quantum levels of the electron energy states,
respectively.
 α lines (n = 2 to n = 1, or n = 3 to n = 2).

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 β lines (n = 3 to n = 1 or n = 4 to n = 2).

Electronic energy levels of an atom

 GENERATION OF X-RAYS

 Generated by bombarding a metal target with an energetic beam of electrons.

 Synchrotrons:
Very expensive to build and maintain.

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 By use of radioactive source like 55Fe.

 A new method of generating X rays that is not yet commercially available

uses an electron-impact beam impinging on a stream of liquid gallium.

 X rays may also be produced while unrolling adhesive tape from a tape
dispenser.
X-RAY TECHNIQUES
X-ray absorption methods
 Fraction of X-ray photons absorbed is considered.
 Used in elemental analysis and thickness measurements.
X-ray fluorescence methods

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 Wavelength and intensity of generated X-rays are measured for
qualitative and quantitative analysis.
 Non-destructive and requires little sample preparation.
X-ray diffraction methods
 Scattering of X-rays by crystals.
 Determines crystalline structure.
X-RAY DIFFRACTOMETER

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The Bruker-D8 diffractometer
 BRAGG’s EQUATION
Constructive interference of the reflected beams emerging from two different planes will
take place if the difference in path lengths of two rays is equal to whole number of
wavelengths.
Deviation = 2

Ray 1

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Ray 2  

 d

dS
in

 The path difference between ray 1 and ray 2 = 2d Sin

 For constructive interference: n = 2d Sin
 INSTRUMENTATION
 X-ray source:1.Crooke’s tube
2.Coolidge tube

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 Collimator

 Monochromator-1.Filter type
2.Crystal type
 Detectors:
a)Photographic methods
b)Counter methods:
1.Geiger-muller counter
2.Proportional counter
3.Scintillation counter
4.Solid-state semi-conductor detector
5.Semi conductor detectors
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INSTRUMENTATION OF XRD
 X-RAY SOURCE
Crookes tube
Called as cold cathode tube.

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Electrons are generated by ionization of
the residual air in the tube, instead of heated
filament.
An aluminum cathode plate at one end of
the tube created a beam of electrons, which
struck a platinum anode target at the center
generating X-rays.
Advantage
Point source X-rays, which resulted in
sharper images.
Disadvantage :Unreliable Crookes tube
Coolidge tube
Called as hot cathode tube.
Works with a very good quality vacuum (about 10-4 Pa,
The electrons are produced by thermionic effect from a tungsten filament heated
by an electric current.
There are two designs:
1.End-window tubes: Have thin "transmission target" to allow X-rays to pass

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through the target
2.side-window tubes:An Electrostatic Lens to focus the beam onto a very small spot
on the anode.
• A window designed for escape of the generated X-ray photons.
• Power 0.1 to 18 kW.
 COLLIMATOR

Inserted in the diffracted-beam to get a

narrow x-ray beam.
It consists two sets of closely

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packed metal plates seperated by a gap.
The left end of the collimator shown is
mounted on the X-ray tube.
 The yellow-colored region at the left
end determines the the size of the beam.
The green region at the right end
removes parasitic radiation.
 MONOCHROMATOR

Filter
MATERIALS USED:NACL,LIF,QUARTZ ETC,.
type
A window that absorbs undesirable radiation and
allows required wavelength to pass.

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Eg:Zr absorbs x-rays emitted by Mo.
Crystal type
Positioned in the x-ray beam so that the angle of
the reflecting planes satisfied the Bragg’s equation
for the required wave length.
Characteristics of a crystal:
Mechanically strong and stable
The mosaicity and resolution of the crystal,
should be small.
 DETECTORS
Photographic methods
Contains photographic plate
Blackening of developed film is expressed in terms of density ,D
D=Log Io/I.

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Photostimulable phosphors
An increasingly common method is the use of photo stimulated luminescence
Photostimulable phosphor plate (PSP plate) is used in place of the photographic plate.
After the plate is X-rayed, excited electrons in the phosphor material remain ‘trapped'
in'colour centres' in the crystal lattice until stimulated by a laser beam passed over the plate
surface.
The light given off during laser stimulation is collected by a photomultiplier tube

ADVANTAGE:The PSP plate can be reused

Counter methods
1.Geiger-muller counter:
Filled with an inert gas like argon.
Measures ionizing radiation. Detect
the emission of nuclear radiation:

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alpha particles, beta particles or
gamma rays
Advantages:
a)Trouble free
b)Inexpensive
Disadvantages:
a)Cannot be used to measure
energy of ionizing radiation.
b)Used for low counting rates
c)Efficiency falls off below 1A
2.Proportional counter:
Filledwith heavier gas like xenon or
krypton as it is easily ionized.
Output pulse is dependent on
intensity of X-rays falling on counter.

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Count the particles of ionizing
radiation and measures their energy.
Advantages:
a)Count high rates with out significant
error.
Disadvantages:
a)Associated electronic circuit is
complex.
b)Expensive.
3.Scintillation counter:
Measures X-rays of shorter
wavelengths.
The sensor, called a scintillator,
consists of a transparent crystal,
usually phosphor, plastic (usually

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containing anthracene), or
organic liquid that fluoresces when
struck by ionizing radiation.
The PMT is attached to an
electronic amplifier to count and
possibly quantify the amplitude of
the signals.
Advantages:
a)Count high rates.
4.Solid state semi-conductor detector:
 The electrons produced by X-ray beam are promoted into conduction
bands and the current which flows is directly proportional to the
incident X-ray energy.
Disadvantage:
 Maintainted at very low Temp to minimise the noise and prevent

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deterioration of the detector.
5.Semi-conductor detectors:
 Silicon-lithium drifted detector.

 The principle is similar to gas

ionization detector.
 Voltage of pulse=Q/C

Application: In neutron activation

Semi-conductor detector
analysis
 X-RAY DIFFRACTION METHODS
1.LAUE PHOTOGRAPHIC METHOD:
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.

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 Back-reflection Laue  Transmission Laue
In the back-reflection method, The film is placed behind the
the film is Placed between X- crystal to record beams which are
transmitted through the crystal.
ray source and crystal.
The beams which are diffracted
in a backward direction are
recorded.

Disadvantage: Big crystals are required

 Back-reflection Laue Transmission Laue

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Crystal orientation and perfection is determined from the position of spots.
 2.BRAGG X-RAY SPECTROMETER METHOD:

Bragg analysed the

structures of Nacl,Kcl and
ZnS.

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Method is based on Bragg’s
law.

The strength of ionisation

current is directly proportional
to intensity of entering
reflected X-rays.

SO2 or CH3I increases

ionisation in the chamber.
3.ROTATING CRYSTAL METHOD:

Shaft is moved to put the

crystal into slow rotation.
This cause sets of planes

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coming successively into their
reflecting position.
Each plane will produce a
spot on the photographic plate.
Can take a photograph of the
diffraction pattern in two ways
1.complete rotation method

2.oscillation method
4.POWDER CRYSTAL METHOD:

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1mg material is sufficient for study.
Applications: useful for
Cubic crystals.
Determining complex structures of metals and alloys.
Making distinction between allotropic modification of the same substance.
APPLICATIONS
Structure of crystals
Polymer characterization
State of anneal in metals
Particle size determination

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Spot counting method
v=V.δθ.cosθ/2n
Broadening of diffraction lines
Low-angle scattering
Applications of diffraction methods to complexes
Determination of cis-trans isomerism
Eg:Bis(pyridine-2-carboxamido)nickel(II) chloride
Determination of linkage isomerism
Eg:Biuret+copper(II)=pottassium bis(biureto)cuprate(II)
tetrahydrate
MISCELLANEOUS APPLICATIONS
 Soil classification based on crystallinity.
 Analysis of industrial dusts.

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 Assessment of weathering & degradation of minerals &
polymers.
 Study of corrosion products.

 Examination of tooth enamel & dentine.

 Examination of bone state & tissue state.

 Structure of DNA&RNA.

 X-ray Diffraction on aerosol drugs -

Measurements on small quantities of pharmaceutical
samples using the X'Celerator detector.
 REFERENCES
1)Instrumental methods of chemical analysis ,B.K.sharma,17 th
edition 1997-1998,GOEL publishing house.page no:329-359

2)Principles of instrumental analysis,5th edition ,by Dougles

a.skoog,f.James holles,Timothy A.Niemen.page no:277-298

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3)Instrumental methods of chemical analysis ,Gurudeep
R.chatwal,sham k.anand,Himalaya publications page no:2.303-
2.332

4) Instrumental Methods Of Chemical Analysis –

H. Kaur pg.no:727-729,737

5) http://www.scienceiscool.org/solids/intro.html

6) http://en.wikipedia.org/wiki/X-ray_crystallography
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