X – RAY DIFFRACTION (XRD)

Introduction

 It is a novel & non destructive method of chemical analysis

and a variety of x –ray techniques are available in practice.
 These are : X – Ray Absorption : X-ray diffraction
X-ray Fluorescence
 X – ray diffraction
“ Every crystalline substance gives a pattern; the same substance
always gives the same pattern; and in a mixture of substances
each produces its pattern independently of the others”
 The X-ray diffraction pattern of a pure substance is, therefore,
like a fingerprint of the substance. It is based on the scattering of
x-rays by crystals.
 Definition
The atomic planes of a crystal cause an incident beam of X- rays to
interfere with one another as they leave the crystal. The
phenomenon is called X-ray diffraction.
What is X-ray Diffraction ?
Why XRD?

 Measure the average spacing's between layers or rows of atoms

 Determine the orientation of a single crystal or grain

 Find the crystal structure of an unknown material

 Measure the size, shape and internal stress of small

crystalline regions
Effect of sample thickness on the
absorption of X-rays

incident beam

diffracted beam
crystal

film
 Detection of Diffracted X-rays by
Photographic film

 A sample of some hundreds of

crystals (i.e. a powdered
sample) show that the
diffracted beams form
continuous cones. A circle of
sample film is used to record the
diffraction pattern as shown.
Each cone intersects the film
X-ray giving diffraction lines. The
film lines are seen as arcs on the
film.
Bragg’s Law and Diffraction

 How waves reveal the atomic

structure of crystals
N ƛ = 2d sinθ N = integer
 Diffraction occurs only when
Bragg’s Law is satisfied
Condition for constructive
Atomic interference (X-rays 1 & 2)
plane from planes with spacing d
 Deriving Bragg’s Law: n ƛ = 2d sin θ

X-ray 2
 Constructive
interference
AB+BC = multiples of n ƛ
X-ray 2 occurs only
when
n ƛ= AB + BC AB=BC
n ƛ = 2AB Sin θ =AB/d
AB=d sin θ
n ƛ =2d sin θ
ƛ = 2 d hkl sin θ hkl
Planes in Crystals-2 dimension

 Different planes have different

spacing

 To satisfy Bragg’s Law, q must

change as d changes e.g., q
decreases as d increases.
 Basics of Crystallography

 The atoms are arranged in a regular pattern, and

there is as smallest volume element that by
repetition in three dimensions describes the
crystal. This smallest volume element is called a
unit cell.

 Crystals consist of planes of atoms that are spaced

a distance d apart, but can be resolved into many
atomic planes, each with a different d spacing.

 The dimensions of the unit cell is described by

three axes : a, b, c and the angles between them
Lattice
α, β , and γ are lattice constants which can be
determined by XRD.
Miller Indices: hkl

 Miller indices-the reciprocals

of the fractional intercepts
which the plane makes with
crystallographic axe
 Axial length 4Å 8Å 3Å
 Intercept lengths 1Å 4Å 3Å
 Fractional intercepts ¼ ½ 1
 Miller indices 421
hkl
Production of X-rays

 X-rays are produced whenever

high-speed electrons collide with
a metal target.
 A source of electrons – hot W
filament, a high accelerating
voltage between the cathode (W)
and the anode and a metal
target, Cu, Al, Mo, Mg.
 The anode is a water-cooled
block of Cu containing desired
target metal.
Specimen Preparation

 Powders:
0.1μm < particle size < 40 μm
Peak broadening less diffraction
occurring

 Bulks: smooth surface after polishing, specimens should be

thermal annealed to eliminate any surface deformation
induced during polishing.
 A Modern Automated X-ray
Diffractometer

X-ray
Detector
Tube
θ2

Sample stage

Cost: $560K to
 Basic components & Features of
XRD

 Production

 Diffraction

 Detection

 Interpretation
Detection of Diffracted X-rays by a
Diffractometer

Bragg - Brentano Focus Geometry, Cullity

XRD Pattern of NaCl Powder

Miller indices: The peak is due to X-ray

diffraction from the {220} planes.

Diffraction angle 2θ (degrees)

 Significance of Peak Shape in XRD

 Peak position
 Peak width
 Peak intensity

Important for
 Particle or Can also be fit with Gaussian,
Lerentzian, Gaussian-Lerentzian etc.
 grain size
 Residual strain
 Effect of Lattice Strain on
Diffraction Peak Position and Width

No Strain

Uniform Strain (d1-do)/do

Peak moves, no shape changes

Shifts to lower angles

Non-uniform Strain
D1 =/constant
Exceeds d0 on top, smaller than d0 on the Peak broadens
bottom
Applications of XRD

 XRD is a non destructive technique to identify crystalline phases

and orientation
-Obtain XRD pattern ; Measure d-spacings ; Obtain
integrated intensities ;
-Compare data with known standards in the JCPDS file
 To determine structural properties:
-Lattice parameters (10-4Å),, grain size, expitaxy, phase
composition, prefer strained orientation (Laue) order-disorder
transformation, thermal expansion
 To measure thickness of thin films and multi-layers*
 To determine atomic arrangement
 Detection limits: ~3% in a two phase mixture; can be ~0.1% with
synchrotron radiation
Spatial resolution: normally none
Applications of XRD

 The electron density and accordingly, the position of the atoms in

complex structures, such as penicillin may be determined from a
comprehensive mathematical study of the x-ray diffraction pattern.

 The elucidation of structure of penicillin by xrd paved the way for

the later synthesis of penicillin.

 The powder xrd pattern may be thought of as finger print of the

single crystal structure, and it may be used conduct
qualitative and quantitative analysis.

 Xrd can also be used to determine whether the compound is solvated

or not
Applications of XRD

 Particle size determination by applying the relation.

v= V. δθ. cos θ / 2n
Where v = the volume or size of an individual crystalline V=
the total volume of the specimen irradiated
n = the number of spots in a deffraction ring at a Bragg angle θ
δθ = the divergence of the X –ray beam
 Determination of Cis-Trans isomerism
 It is used to assess the weathering and degradation of natural and
synthetic , minerals.
 Tooth enamel and dentine have been examined by xrd.
 State of anneal in metals
Synchrotron

 A synchrotron is a
particle
acceleration
device which,
through the use of
bending magnets,
causes a charged
particle beam to
travel in a circular
pattern.
 Advantages of using synchrotron
radiation
 Detecting the presence and quantity of trace elements

 Providing images that show the structure of materials

 Producing X-rays with 108 more brightness than those from

normal X-ray tube (tiny area of sample)

 Having the right energies to interact with elements in light

atoms such as carbon and oxygen

 Producing X-rays with wavelengths (tunable) about the size

of atom, molecule and chemical bonds
Instrumental Sources of Error

 Specimen displacement

 Instrument misalignment

 Error in zero 2 θ position

 Peak distortion due to K alfa 2 and K beta wavelengths

Conclusions

 Non-destructive, fast, easy sample preparation

 High-accuracy for d-spacing calculations

 Can be done in-situ

 Single crystal, poly, and amorphous materials

 Standards are available for thousands of material systems