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CHAPTER 2
CHARACTERIZATION TECHNIQUES
2.1 INTRODUCTION
TECHNIQUES APPLICATIONS
1. X-Ray Diffraction (XRD) To study the crystalline properties of solid
substances
microscopy. The first class of microscopy involves a stationary sample in line with a
high - speed electron gun. Both the scanning electron microscope (SEM) and
transmission electron microscope (TEM) are based on this technique. Detailed
information of surface area measurement and pore size measurement of BET
analysis has described in this chapter.
2.2.1 Principle
In this technique, the primary X - rays are made to fall on the sample
substance to be investigated. Because of its wave nature, like light waves, X - ray
gets diffracted to a certain angle. This angle of diffraction, which differs from that of
the incident beam, will give the information regarding the crystal nature of the
substance. The wavelength of the X - rays can be varied for the application by using
a grating plate.
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nλ = AB+BC (1)
Recognizing ‘d’ as the hypotenuse of the right triangle ABZ, we can use
trigonometry to relate ‘d’ and θ to the distance (AB + BC). The distance AB is
opposite θ so,
AB = d sinθ (2)
nλ = 2AB (3)
nλ = 2d⋅sinθ (4)
where,
n - order of diffraction
θ - the angle between the incident ray and the scattering planes.
Note that if only two rows of atoms are involved, the transition from
constructive to destructive interference as θ changes is gradual. However, if
interference from many rows occurs then the constructive interference peaks become
very sharp with mostly destructive interference in between. This sharpening of the
peaks as the number of rows increases that is very similar to the sharpening of the
diffraction peaks from a diffraction grating as the number of slits increases.
2.2.3 Instrumentation
2.2.4 Applications
The X - ray diffraction is a good tool to study the nature of the crystalline
substances. In crystals, the ions or molecules are arranged in well-defined positions
in planes in three dimensions. The impinging X - rays are reflected by each crystal
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plane. So the planes can not be same or identical for any two chemical substances,
this technique provides vital information regarding the arrangement of atoms and the
spacing in between them and also to find out the chemical compositions of
crystalline substances. The sample under study can be of either a thin layer of crystal
or in a powder form. Since, the power of a diffracted beam depends on the quantity
of the corresponding crystalline substance. It is also possible to carry out
quantitative determinations [63].
2.3.1 Principle
Molecules absorb energy and this energy can bring out translational,
rotational or vibrational motion or ionization of the molecules depending upon the
frequency of the electromagnetic radiation. Excited molecules are unstable and
quickly drop down to ground state again giving off the received energy in the form
electromagnetic radiation. The wavelength and intensity of the electromagnetic
radiation absorbed or emitted can be recorded to get a spectrum (Figure 2.4).
Spectral analysis yields qualitative and quantitative information about the materials
under study [64].
2.3.2 Instrumentation
An entrance slit
A collimating lens
A dispersing device
A focusing lens
An exit slit
wavelengths and are temperature insensitive. However, they reflect light in different
orders, which may overlap. As a result, filters must be used to ensure that only the
light from the desired reflection order reaches the detector.
2.3.2.4 Detectors
2.3.2.5 Cells
These are containers for the sample and reference solutions. They must
be transparent to the radiation passing through.
2.3.3 Applications
2.4.1 Principle
2.4.2 Instrumentation
The beam travels through electromagnetic fields and lenses, which focus
the beam down towards the sample. Once the beam hits the sample, electrons and
X - rays are ejected from the sample. Detectors collect these X - rays, backscattered
electrons and secondary electrons and convert them into a signal that is sent to a
screen similar to a television screen. This produces the final image. In this research
work, the powder samples were placed on the carbon tape which is attached to the
sample holder. JEOL JSM 6320F (FESEM), F E I Quanta FEG 200 (HRSEM) are
used to study the surface morphology of the sample.
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2.4.3 Applications
spectrometer. These X - rays are characteristic of the difference in energy between the
two shells, and the atomic structure of the element form which they were emitted.
The excess energy of the electron that migrates to an inner shell (in order
to fill the newly - created hole) can do more than emitting a X - ray. Often, the
excess energy is transferred to a third electron from a further outer shell, prompting
its ejection. This ejected species is called an Auger electron and the method for its
analysis is known as Auger Electron Spectroscopy (AES).
the detector, which creates a pulse of charge that is proportional to the energy of
X - ray. The pulse charge is converted to a pulse voltage (which is proportional to
the energy X - ray) by a charge sensitive preamplifier. The signal is then sent to a
multichannel analyzer where the pulses are sorted by the tension. The energy, as
determined by measuring the voltage per incident X - ray is sent to a computer for
display and further data evaluation. The spectrum of X - ray energy versus counts is
evaluated to determine the elemental composition of the sample volume.
2.6.1 Principle
2.6.2 Instrumentation
lens-systems and especially by the technique with which the preparation has been
made. Modern gadgets have powers of resolution that range from 0.2 - 0.3 nm.
After passing through the object, the scattered electrons are collected by
an objective. Thereby an image is formed, that is subsequently enlarged by an
additional lens - system (called projective with electron microscopes). The formed
image is made visible on a fluorescent screen or it is documented on photographic
material. Photos taken with electron microscopes are always black and white.
The degree of darkness corresponds to the electron density (differences in atom
masses) of the candled preparation.
2.6.3 Applications
2.7.1 Principle
2.7.2 Instrumentation
materials, etc. In this process, the light is dispersed by the monochromator but, this
type of basic design for IR measurements has been outdated. Instead, a newer
technique termed Fourier Transform-Infrared (FT-IR) has been in practice.
This technique utilises a single beam of un-dispersed light has the instrument
components similar to the previous one.
In FT-IR, the un-dispersed light beam is passed through the sample and
the absorbance at all wavelengths is received at the detector simultaneously.
A computerized mathematical manipulation (known as “Fourier Transform”) is
performed on this data to obtain absorption data for each and every wavelength.
To perform this type of calculations interference of light pattern is required for
which the FT-IR instrumentation contains two mirrors; one fixed and one moveable
with a beam splitter in between them. Before scanning the sample, a reference or a
blank scanning is required. The following is the simplified design of the instrument
(Figure 2.9).
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2.7.2 Applications
The surface of a material is the dividing line between a solid and its
surroundings, liquid, gas or another solid. Therefore, the amount of surface or
surface area is an important factor in the behavior of a solid. Surface area has strong
influence on many factors such as dissolution rates of pharmaceuticals, the activity
of industrial catalyst, adsorption capacity of air and water purifiers, and the
processing of most powders and porous materials, etc. Whenever solid matter is
divided into smaller particles, new surfaces are created thereby increasing the
surface area. Similarly, when pores are created within the particle interior
(by dissolution, decomposition or some other physical or chemical means) the
surface area is also increased. There may be more than 2000 m2 of surface area in a
single gram of activated carbon as an example for gas absorption. The true surface
area, including surface irregularities and pore interiors, cannot be calculated from
particle size information but is rather determined at the atomic level by the
adsorption of an unreactive gas or inert gas. The amount adsorbed, let’s call it X, is a
function not only of the total amount of exposed surface but also (i) temperature, (ii)
gas pressure and (iii) the strength of interaction between gas and solid. Because most
gases and solids interact weakly, the surface must be cooled substantially in order to
cause measurable amounts of adsorption - enough to cover the entire surface. Where
the gas pressure increases, more gas is adsorbed on the surface (in a non - linear
way). However, adsorption of a cold gas does not stop when it covers the surface in
a complete layer of one molecule thick (let’s call the theoretical monolayer amount
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of gas Xm)! As the relative pressure is increased, excess gas is adsorbed to form
“multilayers”. [80, 81]
1 1 C 1 P
(5)
x [( P0 P ) 1] X mC X m C P0
where P/P0 is the gas’s relative pressure and constant ‘C’ is related to the strength of
interaction between gas and solid.
The gas most commonly used is nitrogen for a number of reasons. In the
classical manometric technique, relative pressures less than unity are achieved by
creating conditions of partial vacuum (absolute pressures of pure nitrogen below
atmospheric pressure). This method is easily automated and the amount of gas
adsorbed is made at a number different relative pressures. Usually, the analyzer
obtains at least three data points in the relative pressure range between 0.025 and
0.30 Pa. Experimentally measured data are recorded as pairs of values: the amount
of gas adsorbed is expressed as STP volume (VSTP) and the corresponding relative
pressure (P/Po). A plot of these data is called an isotherm.
The Principle of calculation, the computer program takes over and a least
- squares linear regression is used to fit the best straight line through a transformed
data set consisting of the following pairs of values: 1/VSTP (Po/P)-1 and P/Po.
The monolayer capacity, Vm, is calculated from the slope,
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C 1
S (6)
VmC
1
i (7)
VmC
Solving for Vm
1
Vm (8)
si
V m L AV Am
St (9)
M v
where LAV is Avogadro’s number and Am is the cross - sectional area. All surface
area results are finally reported normalized by sample weight, or mass, as square
meters per gram, written m2 /g.
For the DSSC fabrication, ruthenium (II) N - 719 dyes, iodide and
tri - iodide electrolytes and Pt - coated photocathodes were purchased from
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