XRD 1

9/25/2020
Dr. Santanu Das
MCR 501: Advanced Technique For Materials Characterizations

Department of Ceramic Engineering
Indian Institute of Technology (BHU)
Course Structure:
Technique for Materials Characterizations

1. X-ray Diffraction (XRD)
2. Thermal Analysis (Differential Thermal
Analysis/ Thermogravimetric Analysis)
1. Microscopic Techniques
a. Optical Microscopy
b. Electron Microscopy
i. Scanning Electron Microscopy
ii. Transmission Electron Microscopy
c. Probe Microscopy
i. Scanning Tunneling
ii. Atomic Force Microscopy
5. Spectroscopic Techniques
a. UV-VIS
b. Fourier Transform Infra-Red Spectrosocpy
c. X-ray Photoelectron Spectroscopy
Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)
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BASIC SCIENTIFIC GRAMMAR
Microscopy - Technique
Microscope- Instrument
Micrograph – Results/Data/Image/Pictures
Micro-structure
Spectroscopy- Technique
Spectrometer/spectroscope- Instrument
Spectrograph- Results/Data
Books
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CHARACTERIZATIONS
Why Characterizations are essential part of Materials Development?
What Kind of Characterizations are primarily important in Ceramic Science?
To Identify the
Ceramic Materials Structure-Properties
Correlations of a
Ceramic System
Processing
Structure-Properties Phase Microstructure

Correlations
A different chemical Structure at

Various New Applications or states of a solid with micron-level
Improvement in Conventional various
Applications compositions/structure
/bonding
Dr. Santanu Das
MCR 501: Advanced Technique For Materials Characterizations

Department of Ceramic Engineering
Indian Institute of Technology (BHU)
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Books: XRD
 Theory and Analytical Technique
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A Schematic representation of the

techniques
Why XRD?
• Measure the average spacings 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
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c
c c
v c c
c v c v c c v c
c c v c vv
v v cv v c v
v v v vv
v v v v v vv v
v c c v v
v v c
v v
cv
v v
v
v
v
Basic Crystal Systems
Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU) Book: Materials Science and Engineering, V. Raghavan
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Miller Indices: hkl
Simple Cubic
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Planes and spacings
Indexing: planes and Directions
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XRD is a nondestructive technique
• To identify crystalline phases and orientation

• To determine structural properties: Lattice parameters (10-
4Å), strain, grain size, epitaxy, phase composition, preferred
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
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PROGRESS OF STRUCTURE
DETERMINATION USING X-RAY
PROGRESS OF STRUCTURE
DETERMINATION USING X-RAY
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 X-rays discovered in 1895

 Fundamental to understanding of crystal
structure and symmetry
 Powder diffraction analyses are a simple and
inexpensive method for identifying minerals,
especially fine-grained minerals
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 X-rays with energies ranging from about 100 eV to 10MeV are

classified as electromagnetic waves
 Different from the radio waves, light, and gamma rays in wavelength
and energy on the basis of their wave length
 X-rays show wave nature with wavelength ranging from about 10 to 10-3
nm
 As per the quantum mechanics theory, the electromagnetic wave can

be treated as particles called photons or light quanta
 The essential characteristics of photons such as energy, momentum are

given as follows:
 The propagation velocity c of electromagnetic wave (velocity of

photon) with frequency  and wavelength  is given by the relation
c =  (1)
The velocity of light in the vacuum is a universal constant given as c =

299792458m/s (2.998x 108 m/s).
Each photon has an energy E, which is proportional to its frequency
(2)
(3)
The momentum p is given by mv, the product of the mass m, and its velocity v.
The de Broglie relation for material wave relates wavelength to momentum
 = h/p = h/mv (4)
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Now, the velocity of light can be reduced when traveling through a material
medium, but it does not become zero. Therefore, a photon is never at rest and
so has no rest mass me. However, it can be calculated using Einstein’s mass-
energy equivalence relation E = mc2.
(5)
This is a relation derived from Lorentz transformation in the case where the
photon velocity can be equally set either from a stationary coordinate
or from a coordinate moving at velocity of v
The increase in mass of a photon with velocity may be estimated in the

following equation using the rest mass me:
(6)
For example, an electron increases its mass when the accelerating voltage
exceeds 100kV, so that the common formula of 1/2mv2
for kinetic energy
cannot be used. In such case, the velocity of electron should be treated
relativistically as follows:
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When light hits an electron, the

electron jumps to a higher energy
level, then drops back to its original,
shell, emitting light
 Continuous spectra (white
radiation)– range of X-ray
wavelengths generated by the
absorption (stopping) of electrons
by the target
 Characteristic X-rays – particular
wavelengths created by
dislodgement of inner shell
electrons of the target metal; x-
rays generated when outer shell
electrons collapse into vacant
inner shells
 K peaks created by collapse from
K L to K shell;
K
X K peaks created by collapse from
M to K shell
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X-rays – High energy*, highly penetrative

electromagnetic radiation
*E = hc/λ λ(X-rays) = 0.02-100Å (avg. ~1 Å)

λ(visible light) = 4000-7200Å
X-ray Vacuum Tube
Cathode (W)– electron

generator
Anode (Mo, Cu, Fe, Co, Cr) –

electron target,
X-ray generator
Our instrument uses a copper target
 Electrostatic potential 20
to 60 kV
 Anode current 10 to 50
mA
 Input power ~ 0.5 to 3 kW
 Only 0.1% transforms
into X-ray beam
 The wavelengths, most

commonly used in
crystallography: 0.5-2.5 Å
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When a high voltage with several tens of kV is applied between two

electrodes, the high-speed electrons with sufficient kinetic energy, drawn out
from the cathode, collide with the anode (metallic target)
Since the slowing down patterns (method of loosing kinetic energy) vary with
electrons, continuous X-rays with various wavelengths are generated.
When an electron loses all its energy in a single collision, the generated X-ray
has the maximum energy (or the shortest wavelength SWL).
The total X-ray intensity released in a fixed time interval is equivalent to the
area under the curve in Fig below:
It is related to the atomic number of the anode

target Z and the tube current i
Icont = AiZV2
Where, A is a constant
In general, most of the kinetic energy of

the electrons striking the anode (target
metal) is converted into heat and less
than 1% is transformed into X-rays.
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 If the electron has sufficient

kinetic energy to eject an inner-
shell electron, for example, a K
shell electron, the atom will
become excited with a hole in
the electron shell.
 When such hole is filled by an

outer shell electron, the atom
regains its stable state.
 This process also includes

production of an X-ray photon
with energy equal to the
difference in the electron energy
levels.
As the energy released in this process is a value specific to the target metal
and related electron shell, it is called characteristic X-ray
A linear relation between the square root of frequency of the

characteristic X-ray and the atomic number Z of the target
material is given by:
Moseley’s law:
BM and σM are constants.
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This Moseley’s law can also be given in terms of wavelength of emitted

characteristic X-ray:
Where, “R” is the Rydberg constant (1:0973 x 107 m-1), SM is a screening

constant, and usually zero for K line and one for K line.
n1 and n2 represent the principal quantum number of the inner shell and
outer shell, respectively, involved in the generation of characteristic X-
rays.
For example, n1 = 1 for K shell,

n2 = 2 for L shell,
and
n3 = 3 for M shell.
As characteristic X-rays are generated when the applied voltage exceeds the
so-called excitation voltage, corresponding to the potential required to eject
an electron from the K shell
For Example, The potential required for

Cu: 8.86 keV,
Mo: 20.0 keV
Then, the intensity of the K radiation, IK can be
represented as:
Where, the “i” is tube current, “V” the applied voltage, and “VK” is the
excitation voltage
BS is a constant and the value of BS = 4.25x108
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Therefore, this phenomenon occurs with a specific energy (wavelength) and

is called “photoelectric absorption.”
The energy, Eej, of the photoelectron emitted may be described in the
following form as a difference of the binding energy (EB) for electrons of
the corresponding shell with which the photoelectron belongs and the
energy of incidence X-rays (h)
 The recoil of atom is necessarily produced in the photoelectric absorption

process, but its energy variation is known to be negligibly small.
 The above equation is based on such condition. Moreover, the value of

binding energy (EB) is also called absorption edge of the related shell.
 X-rays which enter a sample are scattered by electrons around the nucleus
of atoms in the sample.
 The scattering usually occurs in various different directions other than the
direction of the incident X-rays, even if photoelectric absorption does not
occur.
 As a result, the reduction in intensity of X-rays, which penetrate the

substance is necessarily detected.
 When X-rays with intensity I0 penetrate a uniform substance, the intensity I

after transmission through distance x is given by
The proportional factor 

is called linear absorption coefficient, which is
dependent on the wavelength of X-rays
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Since the linear absorption coefficient “” is proportional

to density ,(/) becomes unique value of the substance,
independent upon the state of the substance.
The quantity of (/) is called the mass absorption

coefficient
Equation can then be re-written as in terms of
the mass absorption coefficient.
Mass absorption coefficient of the sample of interest containing two or more

elements can be estimated from the equation below:
using the bulk density, , and weight ratio of wj for each element j.
Wavelength dependences of mass absorption coefficient of X-ray using

the La as an example
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 An X-ray beam is an electromagnetic wave characterized by an electric

field vibrating at constant frequency, perpendicular to the direction of
movement.
 This variation of the electric field gives electrons (charged particles) a

sinusoidal change with time at the same frequency.
 As a result of periodic acceleration and deceleration of the electron, a new

electromagnetic wave, i.e., X-rays are generated
 In this sense, X-rays are scattered by electrons.
 This phenomenon is called Thomson scattering.

“Diffraction as a function of atomic position” is also found when an X-
ray beam encounters a crystal whose atomic arrangement shows the long
range periodicity
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Thomson scattering is the elastic scattering of electromagnetic

radiation by a free charged particle, as described by classical electromagnetism.
It is the low-energy limit of Compton scattering: the particle's kinetic energy and
photon frequency do not change as a result of the scattering.
 The intensity of diffracted X-rays depends on not only the

atomic arrangement but also the atomic species
 Atomic Scattering Factors: A measure of the scattering

ability of X-rays/atom.
 Since the nucleus of an atom is relatively heavy compared

with an X-ray photon, it does not scatter X-rays. The
scattering ability of an atom depends only on electrons,
their number, and distribution.
X-ray scattering by electrons, the scattered X-rays have the

same frequency (wavelength) as the incident beam and is
“coherent” with the incident X-rays
If the incident X-ray beam traveling

along the X-axis meets a single
electron with mass m (kg) and
charge e coulombs (C) located at
the origin O, the intensity I of the
scattered X-rays at position P in the
X-Z plane at a distance r (m) from
the origin may be expressed by the
“Thomson equation”
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Where I0 is the intensity of incident X-rays, 0 = 4 x 10-7 (mkgC2), and  is

the angle between the scattering direction and that of the acceleration of
electron.
On the other hand, 2 is the angle between the line of OP connecting from
the origin O to the point of measurement P, and the X-axis, the direction of the
incident X-ray beam.
The constant K = (2.8179 x10-15)2 (m2) is equivalent to the square of the

electron radius re in classical electromagnetic theory
polarization factor
Thomson equation:
 X-rays are scattered by an electron in all directions
 The intensity of scattered X-rays decreases as the inverse

square of the distance from the electron at origin, as well as
a function of the scattering angle.
 The intensity of scattered X-rays is larger both in forward

and backward directions compared to the direction at right
angle to the incident X-ray beam.
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There is another way for X-ray scattering by an electron and it is

characterized by a quite different mechanism
Compton scattering occurs when X-rays

encounter a loosely bound or free electrons
If a photon collides with a loosely bound electron

and the collision between photon and electron is
considered an elastic one
The electron is knocked aside at an angle  and the direction of the incident
X-ray photon is altered by an angle 2
In this collision process, a part of the energy h0 of the incident X-ray photon
is converted to kinetic energy of the electron
The energy of the incident X-ray photon after collision becomes h,
which is smaller than h0
The wavelength  after collision becomes slightly longer

than the wavelength of the incident X-ray beam 0
The term of (h/mc) = 0.002426 nm is called the “Compton wavelength.”
The increase in wavelength due to the Compton scattering depends only

on the scattering angle 2
The values are estimated to be 0 at 2=0 and
0.005 nm at 2 =180o,
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Characteristics:
The phase of X-rays produced by Compton scattering is not the same as

that of the incident X-ray beam, because of the change in wavelength
The Compton modified radiation cannot take part in diffraction

because it has no specific phase relation with the incident X-ray beam
and therefore cannot produce any interference effect.
For this reason, Compton scattering is often Known as

“incoherent scattering.”
Problem: From high-precision scattering experiments, 0.002426 nm is obtained

as the wavelength of Compton scattering. Calculate the effective mass of
photon me using the so-called Einstein relation E = mc2 showing relationship
between the mass of photon m and its energy E.
 = 0.002426 nm
= 0.002426 nm x 10-9 m
c =h E = h = hc/
To calculate the effective mass of photon me
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9/25/2020

Dr. Santanu Das

MCR 501: Advanced Technique For Materials Characterizations

Technique for Materials Characterizations

BASIC SCIENTIFIC GRAMMAR

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Why Characterizations are essential part of Materials Development?

What Kind of Characterizations are primarily important in Ceramic Science?

Structure-Properties Phase Microstructure

A different chemical Structure at

Dr. Santanu Das

MCR 501: Advanced Technique For Materials Characterizations

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

 Theory and Analytical Technique

A Schematic representation of the

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Basic Crystal Systems

Miller Indices: hkl

Planes and spacings

Indexing: planes and Directions

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

XRD is a nondestructive technique

• To identify crystalline phases and orientation

Spatial resolution: normally none

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

 X-rays discovered in 1895

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

 X-rays with energies ranging from about 100 eV to 10MeV are

 As per the quantum mechanics theory, the electromagnetic wave can

 The essential characteristics of photons such as energy, momentum are

 The propagation velocity c of electromagnetic wave (velocity of

The velocity of light in the vacuum is a universal constant given as c =

Each photon has an energy E, which is proportional to its frequency

 = h/p = h/mv (4)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

The increase in mass of a photon with velocity may be estimated in the

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

When light hits an electron, the

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

X-rays – High energy*, highly penetrative

*E = hc/λ λ(X-rays) = 0.02-100Å (avg. ~1 Å)

Cathode (W)– electron

Anode (Mo, Cu, Fe, Co, Cr) –

 The wavelengths, most

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

When a high voltage with several tens of kV is applied between two

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

It is related to the atomic number of the anode

In general, most of the kinetic energy of

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

 If the electron has sufficient

 When such hole is filled by an

 This process also includes

Dr. Santanu Das, Department of Ceramic Engineering, IIT (BHU)

A linear relation between the square root of frequency of the