Module – 5

Materials characterization and Instrumentation

Nanomaterials are materials that are characterized by at least one dimension in the
nanometer (1 nm = 10−9m) range. This length scale, which lies within the atomic and the
microscale, brings new physical and chemical properties to a material (i.e., size effects). This
becomes especially apparent when the nanomaterial has at least one dimension between 1 and
100 nm. Thus, it is now widely accepted that this latter specific range covers the term of
nanomaterial. There are several types of nanomaterials classified according to their composition
and shape. A practical way for their classification is according to the structural features of their
elementary units and the number of dimensions, which are outside the nanoscale. Thus, they can
be zero-dimensional (0-D) like nanoparticles, one-dimensional (1-D) like nanorods, and two-
dimensional (2-D) like nanolayers. The various combinations of nanomaterials may configure a
broad spectrum of nanostructures characterized by their discernible form and dimensionality.
Accordingly, for example, a linear or a planar bonding of nanoparticles, of a defined
composition, creates a one- or a two-dimensional nanostructured material, respectively.
Prerequisite for the latter classification in addition is to exhibit size effects. Further, the
construction of ordered arrays of nanostructures can provide strategies for the manufacturing of
nanodevices.

Since nanomaterials possess exceptional properties, they are widely used to mix with the
bulk polymeric material to improve their properties. By definition, nanocomposites are materials
that are reinforced with nanoparticles. Based on the matrix material, nanocomposites are
classified into polymer matrix composites, metal matrix composites, and ceramic matrix
composites. In polymer matrix composites, the most important topic to be considered is the
dispersion of the nanofillers in bulk polymer matrix. Homogeneous distribution of nanomaterials
results in improved properties. But the tendency of particle agglomeration due to the weak van
der Waals forces between the nanomaterials results in deterioration in properties. For example,
homogeneous dispersion of CNTs, graphene, CNFs, and clay in the polymer matrix improved
mechanical, thermal, electrical, optical, gas barrier, and flame retardancy properties of
nanocomposites.

X_ray diffractometer

The powder method of X ray diffraction was devised by Debye & Scherrer in 1916 to determine
the structure of finely powdered polycrystalline materials. X-ray diffraction (XRD) is a powerful
nondestructive technique for characterizing crystalline materials. It provides information on
structures, phases, preferred crystal orientations (texture), and other structural parameters, such
as average grain size, crystallinity, strain, and crystal defects.

Principle:- When x-rays fall on the sample, they interact with atom and changes their direction
causing either constructive or destructive interference. This can be used to gather information
about the sample.

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Construction:

Construction :
1) X-ray tube: X rays are produced from x ray tube by colliding high voltage electrons with
metals. Produced x rays are made monochromatic.
2) Collimator: X-ray beam is made parallel and narrow using collimator.
3) Photographic film: the diffracted beam of x rays are recorded the cylindrical film called
photographic film.

Working:
The powder sample is taken in a glass tube inside the axis of the cylindrical axis of
photographic film. X rays are made to incident on to the powder sample. Different particles of
the powder is having different orientation of plane. X rays are diffracted from the sample when
Bragg’s law is satisfied (nλ = 2d Sinθ) hence a cone of diffracted x rays are formed with same
diffracting angle. Different cones can be observed with different diffracting angle from different
set of planes.

X rays when strikes the photographic film is developed and the pattern is observed as
below. Unscattered x rays will be passing through the exit hole.

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Applications:
1) Used for the identification of unknown material
2) Used for the measurement of samples purity
3) Used for the determination of lattice parameters
4) Used for the determination of crystallite size.
5) Used for the determination of crystalline structure.

Crystal size determination by Scherrer equation:

Scherrer equation in X-ray diffraction is a formula that relates the size of micrometer
crystallites in a solid to the broadening of a peak in diffraction pattern. It is used to find the size
of crystallites in a solid.

Where, L is crystallite size

k is Scherrer constant (0.9 for spherical shape crystallite)
β is Full width at half maxima (FWHM) (in radians)
θ is Bragg’s angle in degrees
λ is wavelength of X-rays 1.54 Ao

Numericals

1) In an X-ray diffraction experiment, peak width at half maxima is 0.60 and its corresponding
bragg angle is 240. Calculate the crystallite size. Given wavelength in X-ray diffraction
experiment is 1.54 Ao. [And: 144.9 Ao]

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Atomic force Microscope

Atomic-force microscope (AFM) is an instrument capable of image and manipulating the

matter at nanoscale.

Principle: AFM microscopes operate on the principle of surface sensing using an extremely
sharp tip on a micromachined silicon probe.

Construction:

It consists of following parts

a) Cantilever: It is the main part having sharp tip at the end.
b) Tip: A very fine tip of the size of the size of the order of nanometer is composed of silicon and
is attached at the end of cantilever.
c) The sample under investigation is place on the platform.
d) Piezoelectric tube: the platform containing sample is mounted on the piezoelectric tube which
can move sample in x, y and z axes.
e) Laser: It helps in cantilever deflection measurement. Laser is deflected from back of cantilever
due to deflection in cantilever while scanning the sample.
f) Photodetector: It consists of several photodiodes which converts laser light into electric current
which helps in imaging of surface sample.

Working:
When the tip is bought close to the sample, force between the tip and sample leads to the
deflection of the cantilever according to the Hook`s law. Instead of using an electrical signal, the
AFM relies on forces between the atom on the tip and in the sample.

The force present in the tip is kept constant and the scanning is done. As the scanning
continues, the tip will have vertical movements depending upon the topography of the sample.

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 A LASER beam is used to have a record of vertical movement of the needle. This
information is later converted into visible from using photo diode. Depending upon the situation,
AFM measures different types of forces like a Vander Waal’s forces, capillary force, mechanical
contact force etc.
Applications:

1. Identifying atoms from samples

2. Evaluating force interactions between atoms
3. Studying the physical changing properties of atoms
4. Studying the structural and mechanical properties of protein complexes and assembly, such
as microtubules.
5. Used to differentiate cancer cells and normal cells.
6. Evaluating and differentiating neighboring cells and their shape and cell wall rigidity.

X ray photoelectron spectroscopy (XPS)

It is is a technique for analyzing a material's surface chemistry. XPS can measure

elemental composition as well as the chemical and electronic state of the atoms within a material.

Principle: When an x-ray (red arrow) bombards a sample (left), some electrons (yellow spheres)
become excited enough to escape the atom.

Construction & Working:

It consists of following parts

a) X-ray source: the simplest x-ray source of x-ray is x-ray tub equipped with magnesium or
aluminum metal target. This provides much smaller spot in the surface to be examined.
b) Sample holder: It is located in between the source and the entrance slit of spectrometer. The
area inside the sample holder is evacuated with 10-5 torr pressure to avoid contamination of the
sample surface. The ejected electrons from the sample is analyzed by electron analyzer.
c) Electron analyser: It has lens system to collect photoelectrons to filter electron energies.

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IT also contains a hemispherical energy analyzer with applied electrostatic field. The pressure
maintained inside the analyser is 10-5 torr.
When an electron enters into the hemispherical analyzer it travels in curved path
d) Detector: The ejected electrons from the hemispherical analyser will be counted and their
kinetic energies are measured using the detector.
Finally energies of all electron are represented in a spectrum. Each electrons energy represents us
the particular element present in the sample.

Applications:

1) Determination of surface contamination on semiconductors

2) Study of oxide layers of metal
3) Analysis of dust on the sample
4) Determination of oxidation state
5) All the elements of periodic table can be identified except hydrogen and helium as they donot
emit inner core electrons.

Scanning electron microscope:

Scanning electron microscope is a type of electron microscope that produces images of a

sample by scanning the surface with a focused beam of electrons.

Principle: The principle used in the working of SEM is the wave nature of electrons. The
electron accelerated under a potential difference of ‘v’ volts behaves like a wave of wavelength.

λ = nm
√ √

Construction:

It consists of highly evacuated chamber inside which there is an electron gun at the top. There
are two magnetic lenses one is condensing lens C and the other is objective lens O, A scan coil is
accompanied with lens O. There is a spray aperture using which spherical aberrations during
focusing will be minimized. A flat surface called stage is provided at the bottom portion of the
apparatus to place the specimen under study.

There are three types of detectors in the apparatus. They are, back scattered electron detector,
secondary emission electron detector and X-ray detector which could be placed selectively
depending upon the particular application.

The electrons incident on the sample are called primary electrons. Out of these, some of them
will be scattered by the sample are called Back scattered electrons and some of them knock out
the electrons from the atoms in the specimen are called secondary electrons. X rays are emitted

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when electrons from a higher shell in the atom transit to a vacant position created in its lower
shell from where, an electron has been knocked off.

Working:

The sample being studied is placed on the specimen stage after which inside of chamber
is evacuated. The accelerated electrons from the electron gun pass through the spray aperture
from where the electron beam emerges. The condensing lens C converges the beam and
eliminates some high angle electrons. The beam then passes through the objective aperture where
then enters into the field of objective lens O. The objective lens focuses the beam onto the
desired part of the specimen.

A set of coils called scan coils place along with the objective lens enable the beam to
scan the specimen due to the impact of the beam. Back scattered electron, secondary electrons
and the X-rays emitted are detected by the respective detectors. Corresponding signals is

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converted into a micro spot of corresponding brightness on a screen. The beam focus is shifted
to the next adjacent spot on order, where it again dwells momentarily and so on. This way image
is built on screen spot by spot by spot.

Applications:

SEM is used to study

1) External morphology of biological organisms in the submicroscope
2) Chemical composition
3) Crystalline structure
4) In Forensic investigation

Transmission electron microscope

Principle: Electrons are 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 that falls on to the
specimen. The specimen is placed in between the condensing lens and the objective lens as
shown.
The magnetic objective lens is used to block the high angle diffracted beam and the
aperture is sued 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 or
(CCD – Charged Coupled device).

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Working:

Stream of electrons are 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. Both these beams are recombined at the E-wald
sphere to form the image. The combined image is called the phase contrast image.
In order to increase the intensity and the contrast of the image, an amplitude contrast has
to be obtained. This can be achieved only by using the transmitting beam and thus the diffracted
beam can be eliminated.
Now in order to eliminate the diffracted beam, the resultant beam is passed through the
magnetic objective lens and the aperture. The aperture is adjusted in such a way that the
diffracted image is eliminated. 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 or CCD. This high contrast image
is called Bright Field Image.

Applications:
TEM is used
1. To visualize and study cell structures of bacteria, viruses, and fungi
2. To view bacteria flagella and plasmids
3. To view the shapes and sizes of microbial cell organelles
4. To study and differentiate between plant and animal cells.
5. Used in nanotechnology to study nanoparticles such as ZnO nanoparticles
6. It is used to detect and identify fractures, damaged microparticles which further enable
repair mechanisms of the particles.

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