Materials Characterisation

Environmental NanoTechnology
 Analytical Tools

• Powder XRD
• Phase Analysis
• Crystalline structure
• Crystalline size and strain
▪ Single Crystal XRD
▪ Internal lattice of crystalline substances, including unit cell
dimensions, bond-lengths, bond-angles, and details of site-
ordering
▪ Electron Microscopic Technique:
▪ Scanning electron microscopy (SEM), Transmission electron
microscopy (TEM), Scanning transmission electron microscopy
(STEM), Focus ion beam microscopy (FIB), Atomic Force Microscopy
 Analytical Tools

• Energy Dispersive Spectroscopy(EDAX)

• Elemental Composition
• Fourier Transfer Infrared Spectroscopy (FTIR)
• RAMAN Spectroscopy :provides information about
molecular vibrations that can be used for sample
identification and quantitation
• X-ray photoelectron spectroscopy (XPS):
quantitative spectroscopic technique that measures the
elemental composition, empirical formula, chemical state
and electronic state of the elements that exist within a
material.
• Electron paramagnetic resonance (EPR): method for
studying materials with unpaired electrons.
 Analytical Tools

• BET Surface Area Analyser

• Zeta Potential
• UV-Diffuse Reflectance Spectroscopy
• Photoluminance
• Ellipsometry
• TGA/DSC etc
 Power X -ray Diffraction

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Sir William Lawrence Bragg (1890-
1971), the son of Sir William
Maurice Wilkins
Henry Bragg and cowinner of the rosalind franklin
1915 Nobel Prize in Physics
Sir William Henry Bragg (1862-
1942), an English mathematician
and physicist and cowinner of the
1915 Nobel Prize in
Physics

Max von Laue (1879-1960), a

German physicist who won the
1914 Nobel Prize in Physics

Wilhelm Conrad Rontgen (1845-

1923), a German physicist who
won the 1901 Nobel Prize in Physics

Rene-Just Hauy (1743-1822), a

French mathematician and
mineralogist

Auguste Bravais (1811-1863), a

French physicist
Auguste Bravais
• Bravais was responsible for the
revival of interest in the study
of the external forms of
crystals and their internal
structures. After intensive
study of lattice properties, he
derived in 1848 the 14
possible arrangements of
points in space.
 https://www.nobelprize.org/

• A phenomenon known as "diffraction patterns" occurs when

waves pass through small, tightly spaced openings in a screen.
In 1912, Max von Laue came upon the idea that X-rays passing
through crystals might create similar patterns. That is, that a
crystal's structure would correspond to the openings in a
screen. Experiments confirmed Max von Laue's idea. This
demonstrated that X-rays could be described as waves. The
method also made it possible to use diffraction patterns to
determine crystals' structures.
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Work
Max von Laue's discovery that diffraction
patterns occur when X-rays pass through
crystals inspired William and Lawrence Bragg
to conduct their own studies in the area. Their
contributions included establishing the
relationship between the wavelength of the X-
ray, its angle of incidence, and the distance
between the atomic layers inside the crystal.
This provided a powerful tool for studying
crystals' structures. Using diffraction pattern
methods, it now also became possible to
calculate the positions of atoms in crystalline
structures.
Power X -ray Diffraction

Maurice Wilkins
rosalind franklin
Principle
 Principle: Source

• X-rays are electromagnetic radiation with typical photon

energies in the range of 100 eV - 100 keV.
• For diffraction applications, only short wavelength x-rays
(hard x-rays) in the range of a few angstroms to 0.1 Å (1
keV - 120 keV) are used.
• The wavelength of x-rays is comparable to the size of
atoms, they are ideally suited for probing the structural
arrangement of atoms and molecules in a wide range of
materials.
• The energetic x-rays can penetrate deep into the
materials and provide information about the bulk
structure.
 Bremsstrahlung

• X-rays are produced generally by either x-ray tubes or

synchrotron radiation.
• In a x-ray tube, which is the primary x-ray source used in
laboratory x-ray instruments, x-rays are generated when a
focused electron beam accelerated across a high voltage field
bombards a stationary or rotating solid target.
• As electrons collide with atoms in the target and slow down, a
continuous spectrum of x-rays are emitted, which are termed
Bremsstrahlung radiation.
 Bremsstrahlung

• Bremsstrahlung is a German term that means "braking

rays.“
• In the Bremsstrahlung process, a high speed electron
traveling in a material is slowed or completely stopped by
the forces of any atom it encounters.
• As a high speed electron approaches an atom, it will
interact with the negative force from the electrons of the
atom, and it may be slowed or completely stopped.
• If the electron is slowed down, it will exit the material
with less energy.
 Bremsstrahlung
• Electromagnetic radiation produced by the deceleration of a
charged particle when deflected by another charged particle,
typically an electron by an atomic nucleus (as depicted in the
image above).
• The moving particle loses kinetic energy, which is converted
into a photon, thus satisfying the law of conservation of energy.
• The term is also used to refer to the process of producing the
radiation.
• Bremsstrahlung has a continuous spectrum, which becomes
more intense and whose peak intensity shifts toward higher
frequencies as the change of the energy of the decelerated
particles increases.
• The maximum radiation frequency is related to the kinetic
energy of the electrons by the relationship
Principle of Generation Bremsstrahlung
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Case 1
Case 2
Case 3
Bremsstrahlung Radiation
 X-ray Source

• Common targets used in x-ray tubes include Cu and Mo, which

emit 8 keV and 14 keV x-rays with corresponding wavelengths
of 1.54 Å and 0.8 Å, respectively. (Cu-Kα1 parallel beam for
high-resolution diffraction)
• The energy E of a x-ray photon and its wavelength is related by
the equation E = hc/λ
• In recent years synchrotron facilities have become widely used
as preferred sources for x-ray diffraction measurements.
• Synchrotron radiation is emitted by electrons or positrons
travelling at near light speed in a circular storage ring.
• These powerful sources, which are thousands to millions of
times more intense than laboratory x-ray tubes, have become
indispensable tools for a wide range of structural
investigations and brought advances in numerous fields of
science and technology.
Atomic electron transition in Cu with Siegbahn notation

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Generating of X-rays
Powder XRD
Powder XRD
Sample holder
X-Ray Diffraction
Braggs
 Braggs
• When x-rays are scattered from a crystal
lattice, peaks of scattered intensity are
observed which correspond to the
following conditions:
• The angle of incidence = angle of
scattering.
• The path length difference is equal to an
integer number of wavelengths.
Braggs
 BRAGG’s EQUATION

Deviation = 2

Ray 1

Ray 2  

 d

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

▪ For constructive interference: n = 2d Sin
 In plane scattering is in phase
Incident and scattered
waves are in phase if

Scattering from across planes is in phase

 A B

X Y
Atomic Planes

Extra path traveled by incoming waves → AY

These can be in phase if and only if
Extra path traveled by scattered waves → XB → incident = scattered

A B
But this is still reinforced scatterin
and NOT reflection
X Y
In XRD nth order reflection from (h k l) is considered as 1st order reflectio
from (nh nk nl)

n = 2dhkl sin

d hkl
=2 sin 
n

 = 2dnh nk nl sin
 Crystal structure determination

Many s (orientations) POWDER

Monochromatic X-rays Powder specimen METHOD

Single 
LAUE
Panchromatic X-rays
TECHNIQUE

ROTATING
Monochromatic X-rays  Varied by rotation CRYSTAL
METHOD
 THE POWDER METHOD

 = 2dSin
d= a
h +k +l
2 2 2

4a sin 
2 2
 = 2 2 2
2

h +k +l
2
4 a
(h + k + l ) = 2 sin 
2 2 2 2


(h + k + l )  sin 
2 2 2 2
 ▪ Bragg’s equation is a negative law
➢ If Bragg’s eq. is NOT satisfied → NO reflection can occur
➢ If Bragg’s eq. is satisfied → reflection MAY occur
▪ Diffraction = Reinforced Coherent Scattering

Reflection versus Scattering

Reflection Diffraction
Occurs from surface Occurs throughout the bulk
Takes place at any angle Takes place only at Bragg angles
Small fraction of intensity is
~100 % of the intensity may be reflected
diffracted

X-rays can be reflected at very small angles of incidence

 ▪ n = 2d Sin
▪ n is an integer and is the order of the reflection
▪ For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å

n Sin 
First order reflection from
1 0.35 20.7º
(110)
Second order reflection from
2 0.69 43.92º (110)
Also written as (220)
a
d hkl =
a d 220 = d 220 1
8 =
h2 + k 2 + l 2 d110 2
a
d110 =
2
Crystal Systems and elementary cell
Crystal structure and Bravis Lattice
Miller Indices
• The orientation of a surface or a crystal plane may be
defined by considering how the plane (or indeed any
parallel plane) intersects the main crystallographic axes
of the solid.

• The application of a set of rules leads to the assignment

of the Miller Indices , (hkl) ; a set of numbers which
quantify the intercepts and thus may be used to uniquely
identify the plane or surface.
Miller Indices
• Miller indices are defined as the reciprocals of the
fractional intercepts which the plane makes with the
crystallographic axes.
• For example, if a plane is described by the Miller
indices of (h k l), the plane makes fractional intercepts of
1=h, 1=k, and 1=l with the axes a, b, and c, respectively.
• This reciprocal symbolism enables us to give the Miller
indices being zero, when a plane is parallel to an axis.
Example of Miller indices for plane
Miller Indices
Example of some indices for planes and directions in
cubic system
 (100)

(110)

(111)
(200)
(210)
(211)

(220)
(330)(221)
(310)
(311)
(222)
(320)
(321)

(400)
Calculated Patterns for a Cubic Crystal

(410)
 Indexing
Simple Cubic
S1 (mm) () sin2 h2+k2+l2 sin2/ h2+k2+l2
38 19.0 0.11 1 0.11
45 22.5 0.15 2 0.75
66 33.0 0.30 3 0.10
78 39.0 0.40 4 0.10
Not Simple
83 41.5 0.45 5 0.09 Cubic
97 49.5 0.58 6 0.097
113 56.5 0.70 8 0.0925
118 59.0 0.73 9 0.081
139 69.5 0.88 10 0.088
168 84.9 0.99 11 0.09
Not Constant
 Indexing
FCC; wavelength=1.54056Å
S1 () sin2 h2+k2+l2 sin2/ h2+k2+l2 Lattice Parameter, a (Å)
(mm)
38 19.0 0.11 3 0.037 4.023
45 22.5 0.15 4 0.038 3.978
66 33.0 0.30 8 0.038 3.978
78 39.0 0.40 11 0.036 4.039
83 41.5 0.45 12 0.038 3.978
97 49.5 0.58 16 0.036 4.046
113 56.5 0.70 19 0.037 4.023
118 59.0 0.73 20 0.037 4.023
139 69.5 0.88 24 0.037 4.023
168 84.9 0.99 27 0.037 4.023
Constant; so it is FCC
 Indexing
BCC
S1 (mm) () sin2 h2+k2+l2 sin2/ h2+k2+l2
38 19.0 0.11 2 0.055
45 22.5 0.15 4 0.038
66 33.0 0.30 6 0.050
78 39.0 0.40 8 0.050
Not BCC
83 41.5 0.45 10 0.045
97 49.5 0.58 12 0.048
113 56.5 0.70 14 0.050
118 59.0 0.73 16 0.046
139 69.5 0.88 18 0.049
168 84.9 0.99 20 0.050
Not Constant
Diffraction from a variety of materials

(From “Elements of X-ray

Diffraction”, B.D. Cullity,
Addison Wesley)
 Reality

Crystallite size can be

calculated using
Scherrer Formula

0.9
t=
B cos  B

(From “Elements of X-ray Diffraction”, B.D. Cullity, Addison Wesley)

 Intensity of diffracted beam

For most materials the peaks and their intensity are

documented
➢ JCPDS: Joint Committee on Powder Diffraction
Standards
➢ ICDD: International Centre for Diffraction Data
Name and formula
Reference code: 00-001-1260
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (Å): 3.5175
b (Å): 3.5175
c (Å): 3.5175
Alpha (°): 90.0000
Beta (°): 90.0000
Gamma (°): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed.
Stick pattern from JCPDS

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 Actual Pattern

Bulk electrodeposited nanocrystalline nickel

Three Phase of TiO2
Composite