X-ray Diffraction

Presented by: Mohd. Nasir Mahendra Baingne

Outline
Introduction X-ray diffraction Experimental Method Applications Conclusion

X-rays
X-rays were discovered by the German physicist Roentgen in 1895. It were so named because their nature was unknown at the time. X-ray region lies before the UV region of the electromagnetic spectrum. It covers wavelengths from about 0.1 to 100 .

The spectrum of electromagnetic radiation.

Wavelength Energy
Source: NCERT textbook/Class-11/chemistry-1/page-36

X-rays

Production of X-rays
X-rays are produced whenever high speed electrons collide with a metal target. a). A source of electrons. b). A high accelerating voltage. c). A metal target.

X-rays tube

Crystal Structure

A crystal may be defined as a solid composed of atoms arranged in a periodic pattern in three dimensions.

Lattice
Lattice may be regarded as sort of framework or skeleton on which the actual crystal is built up.

Source: Elements of X-ray diffraction by B.D . Cullity

Unit Cell

a,b, c and , are the lattice parameter.

The fourteen Bravais lattices

Source: Elements of X-ray diffraction by B.D . Cullity

Source: Elements of X-ray diffraction by B.D . Cullity

X-ray Diffraction
When X-rays interact with a solid material the scattered beams can add together in a few directions and reinforce each other to yield diffraction, this is called X-rays diffraction.

This is a tool for the investigation of the fine structure of matter.

Constructive & Destructive Waves

Constructive interference is the result of synchronized light waves that add together to increase the light intensity. Destructive nterference results when two out-ofphase light waves cancel each other out, resulting in darkness.

X-ray diffraction: Braggs Law

2 1 1 2 Rays 1 and 2 interfere constructively if Total Path Difference is integral multiple of the wavelength, Total p.d. = AB + BC OAB and OCB are equivalent. AB=BC=d*sin Diffraction condition is:

O
A C

2 d sin = n

Braggs reflection can only occur for wavelength (<2d). For most of the crystal planes d is of order of 3 A or less, which means can not exceed about 6 A.

Methods of X-ray diffraction

2 d sin =
X-Ray Diffraction Method

Laue

Rotating Crystal

Powder

Orientation Single Crystal Polychromatic Beam Fixed Angle

Lattice constant Single Crystal Monochromatic Beam Variable Angle

Lattice Parameters Polycrystal (powdered) Monochromatic Beam Variable Angle

Methods of powder diffraction

a) Debye Scherrers method b) Focusing method c) Pinhole method Orientation of diffracted beam In these method narrow strip of film is used. Recorded diffraction line consist of short line formed by intersection of cone of radiation and film
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Fundamental of Powder diffraction method

Purpose:- Phase identification and information on unit cell of crystalline material, avg. bulk composition.

Crystalline structure acts as 3D diffraction grating for x rays.

XRD is based on constructive interference of X ray and crystalline sample.

Monochromatic radiation : strong k characteristic component of

general radiation. To expose various planes in the crystal, rather than a rotating a single crystal, powder sample is use. This exposes various crystal planes simultaneously to the X-rays.
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Powder diffraction method

Component of camera

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Bruker D8 Analytical X-ray Systems(source: institute instrumentation centre IIT Roorkee)

Powder diffraction method

Preparation of sample and mounting Film loading Monochromatic X ray production

A the If a sample monochromatic sample ofconsists some x-ray of hundreds some beam tens of is directed of crystals randomly (i.e. at aa single powdered orientated crystal, sample) single then only one crystals, show that the or the two diffracted diffracted diffracted beams beams are may result. seen form continuous to lie on cones. the surface A circle of several film is cones. used The to record cones may the emerge in pattern diffraction all directions, as shown. forwards Each and backwards. cone intersects the film giving diffraction lines. The lines are seen as arcs on the film.

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Intensity measurement
Intensity is measured by electric counter. Electric counter convert x ray into pulse of electronic current in circuit connected to counter. No of pulse is proportional to no of entering electron In diffraction camera intensity is related to amount of blackening produced on photo graphic plate. Amount of blackening is converted in x ray intensity by micro-photometer.
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Determination of Crystal Structure

Step1:Shape and of unit cell are deduced from angular position of diffracted lines. Step2: Number of atoms per unit cell is then computed from shape and of the unit cell, the Chemical composition of the specimen, and its measured density. Step3: finally the position of atoms with in the unit are deduced from the relative intensities of diffracted beams.

Analysis of X-ray film

2 = 0
3 2 1 1 2 3

2 = 180
3 2 1 1 2 3

R d3 d2d1 d1d2 d3 43(rad) = D / R or d3 d2d1 d1d2 d3

D

43(degree) = 57.296 D / R
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Calculating Lattice Constant

4 (degree) = 57.296 D / R
If radius of the camera R = 57.296 mm then, (degree) = D (mm) / 4 For first order diffraction, d can be calculated by : d= 2 sin However, (hkl) assignment is not possible here. Hence
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Lattice Constant Calculation Contd

Now, dhkl =
a

h 2 + k 2 + l 2

d 2hkl = a 2 / N where N = h 2 + k 2 + l 2 2 d sin = 4 a2 4 d 2 sin2 = 2 sin2 2 = Constant = 2 4a

sin2 = 2

Possible values of N can be 1,2,3,4,5,6

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Prepare a Table

10.83

sin
0.1879

sin2
0.0353

sin2 / N

0.0353 0.0177 0.0118

15.39
18.99

0.2654
0.3254

0.0704
0.1059

0.0704 0.0352 0.0235

0.1059 0.0529 0.0353 For = 1.5404 A, a = 4.10 A
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sin2 2 = 0.0353 = N 4 a2

X-Ray Diffraction

X-Ray Tube

Sample Detector

Schematic of difference between the diffraction pattern of various phases

DIFFRACTION PATTERN FOR SINGLE PHASE

Intensity
Source: http://www.spec2000.net/09-xrd.htm

DIFFRACTION PATTERN FOR TWO PHASE

Intensity
Source: http://www.spec2000.net/09-xrd.htm

Chemical Analysis
Qualitative Analysis
diffraction pattern

Quantitative Analysis
Intensities

Pattern of unknown

Source: Elements of X-ray diffraction by B.D . Cullity

Pattern of unknown

Source: Elements of X-ray diffraction by B.D . Cullity

Pattern of copper

Source: Elements of X-ray diffraction by B.D . Cullity

Pattern of copper

Source: Elements of X-ray diffraction by B.D . Cullity

Source: Elements of X-ray diffraction by B.D . Cullity

Why special?
Determines actual compound For example AxBy & AxB2y Other methods only A & B This method- all the chemical compounds in their present states of existence. Plain carbon steel.

 Different allotropes Crystalline modifications in Solid silica . 1 amorphous 6 different crystals Ores, clays, refractories, alloys, corrosion products, wear products, industrial dusts, etc.

Some More Advantages

Much faster. Requires very small sample. Nondestructive. Minimal or no sample preparation requirements. Ambient conditions for all analysis.

Safety Aspects
Electric shock ----high voltage across electrodes Radiation Injury---- tolerance dose. Heat effect Invisible & burns may not be felt immediately. First noticeable effect ---- lowering of WBC.

Conclusion
X-ray diffraction is a tool for the investigation of the fine structure of matter. The relation by which diffraction occurs is known as the Braggs law or equation. Because each crystalline material has a characteristic atomic structure, it will diffract X-rays in a unique characteristic pattern.