Physics for Mechanical Engineering Stream 22PHYM12/22

Module -5
Material Characterization and Instrumentation
Techniques
SYLLABUS:
Introduction to nano materials: Nanomaterial and nanocomposites. Principle, construction and
working of X-ray Diffractometer, Crystallite size determination by Scherrer equation, Atomic
Force Microscopy (AFM): Principle, construction, working and applications, X-ray
photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), Transmission
electron microscopy (TEM), Numerical Problems.

Nano materials
Nanomaterials can be defined as materials possessing, at least, one external dimension
measuring 1-100 nm. The properties exhibited by nanomaterials strikingly different from those
of bulk materials due to the surface effects and size effects. Nanotechnology is the design and
fabrication of devices using such nanostructures.

Nanoparticles have a high surface to volume ratio. As a result, they can display physical
and chemical properties significantly different from the bulk material. Because at this level
quantum effects are significant. At nano level, the mechanical, electrical, optical, electronic,
catalytic, magnetic, etc. properties of solids are significantly altered with reduction in particle
size.

For example:

 Nano scale copper is five times stronger than ordinary copper.

 Silver foil does not react with dilute HCl but silver nanoparticles rapidly react with dilute
HCl.

 Gold and silver both are chemically inert but their nanoparticles show catalytic property.

 Gold nanoparticles are deep red but its bulk material (gold pieces) is gold coloured.

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CLASSIFICATION OF NANOMATERIALS:

Nanomaterials are classified based on the number of dimensions at nano-scale as follows.

a. Zero-dimensional (0D) nanomaterials or quantum dots:

Here, all dimensions (x, y, z) are at nanoscale, i.e., no dimensions are greater than 100 nm.

Eg: nanospheres and nano-clusters.

b. One-dimensional nanomaterials (1D) or Quantum wires:

Here, two dimensions (x, y) are at nanoscale and the other is outside the nanoscale. This leads
to needle shaped nanomaterials.

Eg: nano-fibres, nano-tubes, nano-rods, and nano-wires.

c. Two-dimensional nanomaterials (2D) or Quantum wells:

Here, one dimension (x) is at nanoscale and the other two are outside the nanoscale. The 2D
nanomaterials exhibit plate like shapes.

Eg; nano-films/thin-films nano-layers and nano-coatings.

Properties of nanomaterials:

Due to large fraction of surface atoms, large surface energy, spatial confinement, and reduced

imperfections the nanomaterials exhibit

 Enhanced mechanical properties

 Different optical properties
 Higher or lower electrical conductivity
 Altered magnetic properties
 Enhanced chemical reactivity

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Applications:

Nanomaterials find wide range of applications in various fields. They are used in
1. targeted, controlled drug delivery in cancer therapy
2. CNTs attached to the tips of the scanning probe, microscopes are used to identify and
characterize biological specimens. Lung cancer cells etc.
3. contact lenses, Dental implants and artificial heart valves
4. Integrated memory circuits in electronic gadgets.
5. CNTs act as EM shield for costly electronic materials as they are poor transmitters of Electro-
magnetic radiations
6. fuel cells - hydrogen storage is made easy with CNT
7. Transistors with p-n junctions can be made by nano wires.
8. Ag nanomaterials are used as anti-bacterial agent in air-conditions and refrigerators.
9. Nano ATO (Antimony-Tin-Oxide) is used in car windows to reduce solar heat radiation.
10. Nano fibre is used to produce wrinkle free, stain resistance fabrics in textile industry.

NANOCOMPOSITES:
Nano composites are materials that incorporate Nano-sized particles into a matrix of standard
material. The idea behind Nano composite is to use building blocks with dimensions in nano-
meter range to design and create new materials with improved physical properties. A very small
quantity of nano scale materials added to the bulk matter results in drastic improvement in their
mechanical strength, toughness and electrical or thermal conductivity. Nanoparticles have an
extremely high surface to volume ratio which dramatically changes their properties when
compared with their bulk sized equivalents. It also changes the way in which the nanoparticles
bond with the bulk material.

Nano composites can dramatically improve properties like :

1. Mechanical properties including strength, modulus and dimensional stability
2. Electrical conductivity
3. Decreased gas, water and hydrocarbon permeability
4. Flame retardancy
5. Thermal stability
6. Chemical resistance

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7. Surface appearance
8. Optical clarity
Applications Nano-composites being used in a number of fields and new applications are being
continuously developed.
Applications for nanocomposites include:
1. Thin-film capacitors for computer chips
2. Solid polymer electrolytes for batteries.
3. Automotive engine parts and fuel tanks
4. Impellers and blades
5. Oxygen and gas barriers
6. Food packaging materials

X-ray Diffraction
The basic principle of an X-ray diffractometer is the Bragg’s law which is the fundamental
equation relating the wavelength (λ) of X-rays, the inter planar distance (d) in crystalline
materials, and the glancing angle (𝜃) or angle of diffraction.

Consider a set of parallel atomic planes of the Crystal such that the distance between the two
successive planes is d. Let a beam of monochromatic X-rays fall on a crystal plane at a glancing
angle of 𝜽. Let AB and DE be the two parallel rays of the incident beam get reflected by the
atoms B and E. In a crystal, each of the atoms scatters the incident ray in all directions. For
constructive interference and hence maximum to observe, the path difference between the rays
ABC and DEF must be an integral multiple of wavelength, (𝒏𝝀), given by

𝒏𝝀 = 𝟐𝒅 𝒔𝒊𝒏 𝜃

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X-ray Diffractometer
Principle:

X-ray diffractometer works on the principle of constructive interference of x-rays diffracted

from different atomic planes in crystals satisfying the Bragg’s law given by

𝒏𝝀 = 𝟐𝒅 𝒔𝒊𝒏 𝜽; n = 1, 2, 3….

Where λ - wavelength of X-rays; 𝜽 - glancing angle; d - the inter planar distance,

Construction:

Three (3) basic components of an x-ray diffractometer are:

 X-ray source
 Specimen/sample
 X-ray detector

X rays produced from X ray tube are passed through two slits S 1 and S2 to obtain a fine
collimated X-ray beam. This beam is made to fall on the crystal/sample C fixed on the top of
a thin wire mounted exactly at the centre of a turn table. The position of the turn table can be
read by means of a vernier V1. The reflected X ray beam is made to enter an ionization chamber
D filled with a gas. The ionization chamber is mounted on a mechanical arm which can rotate
coaxially with the turn table. When the turn table rotates by an angle θ, the mechanical arm
rotates by 2θ. The position of the arm can be read by means of vernier V 2. The X rays in the

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arm are made to pass through the slits S3 and S4. The ionization current is measured by the
electrometer E. Working: The X -ray beam is made to fall on the sample mounted on the turn
table. The sample and the detector are rotated and the intensity of the diffracted/reflected X-
rays is recorded in the form of ionization current. When the geometry of the reflected X-rays
satisfies the Bragg’s equation, the constructive interference occurs and the intensity of the X-
rays will become maximum. The detector detects these X-rays and converts into pulses of
electric current. The number of current pulses per unit of time is counted which is directly
proportional to the intensity of the X-ray beam entering the detector. A typical x-ray diffraction
pattern is a plot of peak intensity against the measured diffraction angle 2θ as shown. The
positions of the peaks in an x-ray diffraction pattern depend on the crystal structure (shape and
size of the unit cell) of the materials.

Application:
XRD is used in
1. Phase identification
2. Identification unknown crystalline materials
3. Determination of crystal size
4. Identifying crystal quality
5. Determination of crystal structure, unit cell dimensions.

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Crystal size determination by Scherer equation

The Scherer equation, in X-ray diffraction and crystallography, is an equation that relates the
size of tiny crystallites (Particle size) in a solid to the broadening of a peak in a diffraction
pattern.
It is given by
𝑘𝜆
𝐷=
𝛽𝑐𝑜𝑠𝛳
Where D – particle size,
K is a constant, called shape factor with a value close to unity depending on the

crystallite shape
λ − Wavelength of the X-ray used for the diffraction
β − Full width at half maximum (FWHM). It is the width of a line shape at half of its
maximum amplitude.
θ − Peak position Bragg angle.
FWHM can be determined as the distance between the curve points at the peak half maximum
level. On a data graph, draw a vertical line from the peak maximum to the baseline. Measure
the length of this line and divide it by 2 to find the center of the line. Draw a line passing
through the line center and parallel to the baseline, the length of this line is the FWHM.

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Atomic Force Microscope (AFM)

Atomic Force Microscope or AFM is a high-resolution form of scanning probe microscope that
employs a sharp tip in a raster motion to measure and visualize materials at the atomic and
nano scales

Principle:

The basic principle of AFM is measuring the intermolecular forces. It is based on the
cantilever/tip assembly known as probe that interacts with the sample. A laser beam is focused
on the back of the cantilever that moves up and down as it scans the surface of a sample and
the deflections are captured by photo detector.

Construction & working:

An AFM consists of a cantilever with a sharp tip at one end, a laser source, a photo detector
(photodiode), detection and feedback system and piezoelectric sensor. The working of the
AFM involves surface sensing, detection and imaging. The cantilever is typically silicon or
silicon nitride with a tip radius of curvature of the order of nanometers. The surface of a sample
is scanned in raster motion with a very sharp tip attached to the cantilever. As the tip approaches
the surface, the forces such as Vander Waal’s forces, electrostatic forces, magnetic forces cause
the cantilever to deflect depending on the topography of the sample. A laser beam is focused
to the back of the cantilever to detect its deflections. The cantilever deflections will cause slight
changes in the direction of the reflected beam. A position sensitive photo diode (PSPD) is used

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to track these changes. This information is processed and converted in to a 3D image of the
sample surface using the electronic processing unit.

Applications of AFM:
AFM is used in wide range of disciplines which include
1. Identifying atoms from samples
2. Evaluating force of interactions between atoms

3. Studying the physically changing properties of atoms

4. Thin film and coatings
5. Tribology (surface and friction interactions)
6. Cell biology-to differentiate normal cells and cancer cells.
7. Energy storage (batteries) and energy generation (photovoltaic) materials
8. Piezoelectric and ferroelectric materials

Scanning Electron Microscope

Microscope is an instrument which provides a magnified image of an object. Scanning Electron
Microscope is the kind of microscope that creates a magnified image of the specimen by
scanning it with a high-energy beam of electrons.

Principle:

The principle used in the working of an SEM is the wave nature of electrons. Electrons
accelerated under a potential difference of V volts behave like a wave of wavelength.

When an object is illuminated by this electron wave, it results in an increase in the resolving
power by a factor of 105.

Construction:

 The apparatus consists of a highly evacuated chamber inside which there is an electron gun
at the top which comprises of the filament and anode.

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 There are two magnetic condenser lenses, used to obtain a fine beam of electron by
controlling the beam diameter.

 The number of electrons reaching the sample can be controlled by the objective apertures.

 A flat surface called stage is provided to place the specimen.

 The apparatus has 3 types of detectors namely back scattered electron detector, secondary
emission electron detector and X-ray detector.

Working:

 The sample is placed on the specimen stage.

 Electrons are emitted by the filament by thermionic emission and are accelerated by a
suitable positive potential.

 The electron beam falling on the condensing lens is converged. The high angle electrons
are eliminated.

 The objective lens focuses the thin electron beam on to the desired part of the specimen.

 The scan coils enable the beam to scan the specimen in a particular way called raster (in
rectangular fashion).

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 Upon incidence, three signals are obtained in the form of Backscattered electrons,
secondary electrons and X-rays.

 The emitted signals are detected by the detector and signals are produced. These signals are
processed to get the desired information about the sample/specimen.

Applications:
SEM is used in
 Forensic investigations
 Visualizing the virus, bacteria, DNA and other microorganisms.
 Filament bulb investigations at traffic accidents
 High resolution surface imaging
 To study Crystalline structure
 Chemical composition studies
 Study of colloids

Transmission electron microscope (TEM)

A Transmission Electron Microscope (TEM) utilizes energetic electrons to provide

morphologic, compositional and crystallographic information of samples. At a maximum
potential magnification of 1 nanometer, TEMs produce high-resolution, two-dimensional
images, allowing for a wide range of educational, science and industry applications.

Principle:

In this microscope, an accelerated beam of electrons is made to pass through the specimen and
the image is formed on the fluorescent screen, either by using the transmitted beam or by using
the diffracted beam.

Construction:

It consists of an electron gun to produce electrons. Magnetic condensing lens is used to

condense the electrons and is also used to adjust the size of the electron beam that falls on to
the specimen. The specimen is placed in between the condensing lens and the objective lens as
shown.

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The magnetic objective lens is used to block the high angle diffracted beam and the aperture is
used to eliminate the diffracted beam (if any) and in turn increases the contrast of the image.
The magnetic projector lens is placed above the fluorescent screen in order to achieve higher
magnification. The image can be recorded by using a fluorescent (Phosphor) screen

Working:
Stream of electrons is produced by the electron gun and is made to fall over the specimen using
the magnetic condensing lens.

Based on the angle of incidence the beam is partially transmitted and partially diffracted. The
high intensity and high contrast image can be obtained only by using the transmitting beam and
thus the diffracted beam need to be eliminated.

To eliminate the diffracted beam, the resultant beam is passed through the magnetic objective
lens and the aperture. The aperture is adjusted to eliminate diffracted beam. Thus, the final
image obtained due to transmitted beam alone is passed through the projector lens for further
magnification.

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The magnified image is recorded in fluorescent screen. This high contrast image is called
Bright Field Image and is purely due to the elastic scattering (no energy change) or due to
transmitted beam.

TEM is used

 to study topographical, morphological composition

 in studying structure of complex materials and atomic structure defects.
 nanotechnology.
 Medical field.
 in determining the phase transformations
 Forensic analysis.
 gemology and metallurgy.
 Industry and education.


X-ray photoelectron spectroscopy (XPS)

X-ray photoelectron spectroscopy (XPS) is a surface characterization technique based on the
photo electric effect that can analyse a sample to a depth of 2 to 10 nanometers (nm). XPS
reveals which chemical elements are present at the surface and the nature of the chemical bond
that exists between these elements. It can detect all of the elements except hydrogen and
helium.

Principle:
The working principle of XPS is the study of kinetic energy of the photoelectrons ejected from
the surface of a sample when it is exposed to x-rays (photoelectric effect). When X-ray photon
of energy ′𝒉𝝂′ is incident on surface, the ejected electron has the kinetic energy (𝐸𝐾) given by

𝐸𝐾 = ℎ𝜈 − 𝐸𝐵 − 𝜑𝑠

Where 𝐸𝐵 = 𝑏𝑖𝑛𝑑𝑖𝑛𝑔 𝑒𝑛𝑒𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛

𝜑𝑠 = work function [The work function is a correction factor for the instrument and correlates
to the minimum energy required to eject an electron from an atom] The XPS spectrum

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displayed as a plot of the binding energy as function of electron counting rate. Binding energy
is a unique character of each element.

Construction:
An XPS instrument contains an x-ray source, sample holder, electron lenses, electron energy
analyzer, and detector housed in an ultra-high vacuum environment. A schematic diagram of
an XPS system is shown below.

The x-ray source is designed to provide a high intensity x-ray beam, as the number of electrons
emitted is proportional to the x-ray source intensity. A common source is an X-ray tube with
both Al or Mg target and a suitable filter. Samples are placed in ultra-high vacuum (10 −9 torr)
to avoid any contamination by Air (Oxygen) and water vapours.

Extraction lenses placed between the sample and the analyzer forms the electron optics which
defines the acceptance angle for collecting electrons emitted from the sample. Electrons of
different energies are identified by hemispheric analyzer. Voltages are applied to the
hemispheres, with the outer hemisphere being more negative than the inner hemisphere. As a
result, only electrons with a specified energy will be able to travel through the analyzer.

A solid-state detector is used to detect the electrons escaping from the sample and a signal
processor is used to determine the electron count and the energy.

Working:
When X-rays shot on the sample, the electrons absorb the incident photon energy and get
ejected with certain kinetic energy given by

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𝐸𝐾 = ℎ𝜈 − 𝐸𝐵 − 𝜑𝑠

The work function and photon energy are known and the kinetic energy is measured by the
detector. Thus, binding energy of the electrons can be determined. The binding energy of the
ejected electrons is analyzed by a detector and a plot of these energies and relative numbers of
electrons is produced.

As electrons are in orbitals farther from the nucleus, less energy is required to eject them, so
the binding energy is lower for higher orbitals. Electrons contained in different sub shells (s,p,d,
etc.) have different energies as well. Electrons of different energies follow different paths
through the detector which allows the computer to differentiate the electrons. By showing the
energy of electrons emitted from a material, the composition of a material can be determined.

Applications of XPS:

It can be used to

 Determine elemental composition of the surface (top 2 – 10 nm usually)

 determine elements that contaminate a surface

 determine thickness of thin films

 identify the type of chemical bonds (Si-O or Si-C)

 determine Oxidation states of elements (𝑇𝑖3+)

 determine Chemical or electronic state of each element on the surface

 determine uniformity of elemental composition across the top surface

Important Questions:
1. Define nano-material and classify the nano-materials based on the dimensional constraints.
2. With neat diagram, explain the principle, construction and working of Atomic Force
Microscope

3. Explain in brief how crystal size is determined by Scherrer’s equation

4. Explain the construction and working of X-Ray diffractometer
5. With neat diagram, explain the principle, construction and working of X-ray photoelectron
spectroscope

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6. Describe the construction and working of Scanning Electron Microscope with the help of a
neat diagram.
7. Mention the principle and applications of X-ray photoelectron spectroscope.
8. Illustrate the working of Transmission Electron Microscope

Numerical:
1. Determine the wave length of X-rays for crystal size of 1.188×10 -6 m, peak width is 0.5O
and peak position 30O, for a cubic crystal. Given Scherrer’s constant k= 0.92.
Solution: D = 1.188×10-6 m, β = 0.5O(peak width should be in radians), β = 8.276 x 10-3 rad
2ϴ = 30O, ϴ = 15O k = 0.92.
𝑘𝜆
𝐷=
𝛽𝑐𝑜𝑠𝛳
. ×
1.188×10-6 =
.

λ = 10.87 n m
2. Determine the crystallite size given the Wavelength of X-Rays 10 nm, the Peak Width
0.5° and peak position 25 ° for a cubic crystal given K = 0.94.
Solution: λ = 10 nm = 10 x 10-9 m, β = 0.5° (peak width should be in radians),
β = 8.276 x 10-3 rad,
2ϴ = 25 °, K = 0.94
𝑘𝜆
𝐷=
𝛽𝑐𝑜𝑠𝛳
D = 1.103 x 10-6 m

3. The first order Bragg reflection occurs when a monochromatic beam of X-rays of
wavelength 0.675Ao is incident on a crystal at a glancing angle of 4o. What is the
glancing angle for third order Bragg’s reflection to occur?
Solution: n =1, λ = 0.675Ao = 0.675 x 10-10m
Glancing angle ϴ = 4o
d =?
2𝑑 sin 𝛳 = n λ
d = 3.6 x10 -10 m.

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4. X-rays are diffracted in the first order from a crystal with d spacing 2.8 × 10 −10 m at a
glancing angle 60°. Calculate the wavelength of X-rays.
Solution: n =1, d = 2.8 × 10−10 m , Glancing angle ϴ = 60°
λ=?
2𝑑 sin 𝛳 = n λ
λ = 4.84 x 10-10 m

5. In a x-ray diffraction experiment, the glancing angle for the first order spectrum was
found to be 6o. Find the wavelength of the x-rays if inter planar distance is 28.2 nm.

Hint: n = 1, ϴ = 6o, λ = ?, d= 28.2 nm

2𝑑 sin 𝛳 = n λ

6. First order spectrum is formed when the x-rays of wavelength 1.5 A o is incident on a
crystal at 12o. Calculate the inter planar spacing in the crystal. (3.6 Ao )

Hint: n =1, λ = 1.5 Ao, ϴ = 12o, d = ?

2𝑑 sin 𝛳 = n λ

7. In a calcite crystal, second order Bragg’s reflection occur from the planes with d-spacing
3Ao, at a glancing angle of 24O. Calculate the path difference between X-rays reflected
from the two planes. Also calculate the wavelength of the X-rays.

Hint : n= 2, d= 3Ao = 3 x 10-10 m, ϴ = 240,

Path difference 2𝑑 sin 𝛳 = ?

wavelength of the X-rays λ = ? 2𝑑 sin 𝛳 = n λ

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