08 Chapter2 PDF

CHAPTER 2
Basic Principle, Working

and Instrumentation of
Experimental Techniques
[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 57

2.1 Introduction
In this chapter, a brief description of basic principle, working and experimental

set up of instrumentation used for studying structural, optical, magnetic and thermal
properties of synthesized undoped and magnetic (Mn, Ni and Co) doped CdS
nanoparticles are described and listed below:
1. Energy Dispersive Analysis of X−rays (EDAX)

2. X−ray Diffraction (XRD)
3. Transmission Electron Microscopy (TEM)
4. UV−Vis−NIR Spectroscopy
5. Spectrofluorometer−PL (Photoluminescence)
6. Fourier Transform Infrared Spectroscopy (FTIR)
7. Raman Spectroscopy
8. Gouy Balance Method
9. Vibrating Sample Magnetometer (VSM)
10. Thermogravimetry Analysis (TGA)
2.2 Characterization Techniques
2.2.1 Energy Dispersive Analysis of X−rays (EDAX)
2.2.1.1 Basic Principle
EDAX is an analytical technique used for elemental analysis or chemical

characterization of a sample. It is based on the investigation of a sample through
interactions between electromagnetic radiation and matter, analyzing X−rays emitted by
the matter in response to being hit with the electromagnetic radiation. Its characterization
capabilities are due in large part to the fundamental principle that each element has a
unique atomic structure allowing X−rays that are characteristic of an element's atomic
structure to be identified uniquely from each other.

To stimulate the emission of characteristic X−rays from a specimen, a high
energy beam of charged particles such as electrons or a beam of X−rays, is focused with
the sample being studied. At rest, an atom within the sample contains ground state (or
unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. The
incident beam may excite an electron in an inner shell, ejecting it from the shell while
creating an electron hole where the electron was. A position vacated by an ejected inner
shell electron is eventually occupied by a higher energy electron from an outer shell and
the difference in energy between the higher energy shell and the lower energy shell may
be released in the form of an X−ray as shown in fig. 2.1. The amount of energy released
by the transferring electron depends on which shell it is transferring from, as well as
which shell it is transferring to. The number and energy of the X−rays emitted from a
specimen can be measured by an energy dispersive spectrometer. As the energy of the
X−ray is characteristic of the difference in energy between the two shells, and of the
atomic structure of the element from which they were emitted, this allows the elemental
composition of the specimen to be measured.
Fig. 2.1 Principle of EDAX.

The position of the peak with appropriate energies gives information about the
qualitative composition of the sample. The number of the X−ray quanta is the measure
for the concentration of the elements (peak height). There is not linear connection
between quantum numbers and concentration portions of the elements. The concentration
calculation needs the net count rates of from it derived measured variables.
2.2.1.2 Experimental Set Up
Fig. 2.2 shows an experimental arrangement of EDAX attached to an SEM. It

consists of four primary components:
1. Beam source
2. X−ray detector
3. Pulse processor
4. Analyzer
EDAX systems are most commonly found on scanning electron microscopes and
electron microprobes. Scanning electron microscopes are equipped with a cathode and
magnetic lenses to create and focus a beam of electrons. The energy of the electron beam
has to be selected to give a compromise between the requirements of resolution and
X−ray production efficiency. The X−radiation excited in the specimen was analyzed in
two fully focusing crystal spectrometers. The EDS X−ray detector measures the relative
abundance of emitted X−rays versus their energy. The detector is typically lithium drifted
silicon, solid state device. When an incident X−ray strikes the detector, it creates a charge
pulse that is proportional to the energy of X−ray. The charge pulse is converted to a
voltage pulse by a charge−sensitive preamplifier. The signal is then sent to a
multichannel analyzer where the pulses are sorted by voltage. The energy, as determined
from the voltage measurement, for each 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.
Elements of low atomic number are difficult to detect by EDAX. The Si (Li)
detector is often protected by a Beryllium (Be) window. The absorption of the soft

X−rays by the Be precludes the detection of elements below an atomic number of 11
(Na). In windowless systems, elements with as low atomic number as 4 (Be) have been
detected, but the problems involved get progressively worse as the atomic number is
reduced [1−2].
Fig. 2.2 Experimental set up of Energy dispersive analysis of X−rays (EDAX).
Specifications:
Model : JOEL JSM−5610
Resolution : With LaB6 filament 2 nm at 30 kV, with W filament 3.5 nm at 30 kV
Accelerating Voltage : 0.2 to 30 kV
Magnification : upto 2,50,000 X
2.2.2 X−ray Diffraction (XRD)
X−ray Powder Diffraction (XRD) is an efficient analytical technique used

determination of grain size, composition of solid solution, lattice constants, and degree of
crystallinity in a mixture of amorphous and crystalline substances [3]. It is a common

technique for the study of crystal structures, atomic spacing, crystallite sizes, stress
analysis, lattice parameters, quantitative phase analysis and can provide information on
unit cell dimensions. This information is important for relating the production of a
material to its structure and hence its properties.
X−ray diffraction is based on constructive interference of monochromatic X−rays

and a crystalline sample. These X−rays are generated by a cathode ray tube, filtered to
produce monochromatic radiation, collimated to concentrate, and directed toward the
sample. The interaction of the incident rays with the sample produces constructive
interference (and a diffracted ray) when conditions satisfy Bragg's Law (nλ = 2d sinθ) as
shown in fig. 2.3. These diffracted X−rays are then detected, processed and counted. By
scanning the sample through a range of 2θ angles, all possible diffraction directions of the
lattice should be attained due to the random orientation of the powdered material.
Conversion of the diffraction peaks to d−spacings allows identification of the mineral
because each mineral has a set of unique d−spacings. Typically, this is achieved by
comparison of d−spacings with standard reference patterns i.e JCPDF files.
Fig. 2.3 A schematic of Bragg’s reflection from a crystal.
X−ray diffractometers consists of three basic elements:
1. X−ray tube

2. Sample holder
3. X−ray detector.
X−rays are generated in a cathode ray tube by heating a filament to produce

electrons, accelerating the electrons toward a target by applying a voltage, and
bombarding the target material with electrons. When electrons have sufficient energy to
dislodge inner shell electrons of the target material, characteristic X−ray spectra are
produced. These spectra consist of several components, the most common being Kα and
Kβ. Kα consists, in part, of Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice
the intensity as Kα2. The specific wavelengths are characteristic of the target material (Cu,
Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, is required to produce
monochromatic X−rays needed for diffraction. Kα1and Kα2 are sufficiently close in
wavelength such that a weighted average of the two is used. Copper is the most common
target material for single−crystal diffraction, with CuKα radiation = 0.5418Å.
These X−rays are collimated and directed onto the sample. As the sample and
detector are rotated, the intensity of the reflected X−rays is recorded. When the geometry
of the incident X−rays impinging the sample satisfies the Bragg Equation, constructive
interference occurs and a peak in intensity occurs. A detector records and processes this
X−ray signal and converts the signal to a count rate which is then output to a device such
as a printer or computer monitor.
The geometry of an X−ray diffractometer is such that the sample rotates in the
path of the collimated X−ray beam at an angle θ while the X−ray detector is mounted on
an arm to collect the diffracted X−rays and rotates at an angle of 2θ as shown in fig. 2.4.
In the experiment goniometer is used to maintain the angle and rotate the sample in the
path of X−ray source.

Fig. 2.4 Schematic representation of sample mounted on a goniometer stage, which can
be rotated about one or more axes, and a detector which travels along the
focusing circle in the Bragg−Brentano geometry.
The complete experimental set−up is shown in fig. 2.5. The intensity of diffracted
X−rays is continuously recorded as the sample and detector rotate through their
respective angles. A peak in intensity occurs when the mineral contains lattice planes
with d−spacings appropriate to diffract X−rays at that value of θ. Although each peak
consists of two separate reflections (Kα1 and Kα2), at small values of 2θ the peak locations
overlap. Greater separation occurs at higher values of θ. Typically, these combined peaks
are treated as one.
Results are commonly presented as peak positions at 2θ and X−ray counts

(intensity) in the form of a table. Intensity is either reported as peak height intensity, that
intensity above background, or as integrated intensity, the area under the peak. The
relative intensity is recorded as the ratio of the peak intensity to that of the most intense
peak For determination of an unknown compound we can follow the below procedure:
The d−spacing of each peak is then obtained by solution of the Bragg equation for the
appropriate value of λ. Once all d−spacings have been determined, compare the d−

spacing of the unknown to those of known materials. Because each mineral has a unique
set of d−spacings, matching these d−spacings provides an identification of the unknown
sample. A systematic procedure is used by ordering the d−spacings in terms of their
intensity beginning with the most intense peak [4−7].
Specification:
Model : Philips Xpert MPD XRD

Source : Cu target X−Ray tube
X−Ray Power : 2 kW
Detector : Xe filled Count rate or Proportional detector
Software : JCPDF database for powder diffractometry
goniometer
Operation Modes : Vertical & Horizontal
Accuracy : ± 0.0025
2θ° Measurement : 3o to 136o
range
Diffractometer radius : 130 to 230 mm
Fig. 2.5 Experimental set up of X−ray diffractometer.

2.2.3 Transmission Electron Microscopy (TEM)
Transmission electron microscopy (TEM) is a technique used for analyzing the

morphology, defects, crystallographic structure, particle size and even composition of a
specimen. In this technique a beam of electrons is transmitted through an ultra thin
specimen, interacting with the specimen as it passes through. An image is formed from
the interaction of the electrons transmitted through the specimen; the image is magnified
and focused onto an imaging device, such as a fluorescent screen, on a layer of
photographic film, or to be detected by a sensor such as a CCD camera. The transmission
electron microscope (TEM) operates on the same basic principles as the light microscope
but uses electrons instead of light. What you can see with a light microscope is limited by
the wavelength of light. TEM use electrons as "light source" and their much lower
wavelength make it possible to get a resolution a thousand times better than with a light
microscope.
TEMs are capable of imaging at a significantly higher resolution than light

microscopes, owing to the small De Broglie wavelength of electrons. This enables the
instrument's user to examine fine detail even as small as a single column of atoms, which
is tens of thousands times smaller than the smallest resolvable object in a light
microscope. TEM forms a major analysis method in a range of scientific fields, in both
physical and biological sciences. TEMs find application in cancer research, virology,
materials science as well as pollution and semiconductor research. At smaller
magnifications TEM image contrast is due to absorption of electrons in the material, due
to the thickness and composition of the material. At higher magnifications complex wave
interactions modulate the intensity of the image, requiring expert analysis of observed
images. Alternate modes of use allow for the TEM to observe modulations in chemical
identity, crystal orientation, electronic structure and sample induced electron phase shift
as well as the regular absorption based imaging.

TEM offers two methods of specimen observation as shown in fig. 2.6.

1. Image mode
2. Diffraction mode
In image mode, the condenser lens and aperture will control electron beam to hit
the specimen, the transmitted beam will be focused and enlarged by objective and
projector lens and form the image in the screen, with recognizable details related to the
sample microstructure. In diffraction mode, an electron diffraction pattern is obtained on
the fluorescent screen, originating from the sample area illuminated by the electron beam.
The diffraction pattern is entirely equivalent to an X−ray diffraction pattern. A single
crystal will produce a spot pattern on the screen and polycrystal will produce a powder or
ring pattern. The microstructure, e.g. the grain size, and lattice defects are studied by use
of the image mode, while the crystalline structure is studied by the diffraction mode.
Fig. 2.6 Shows two different operations of TEM.

Image Modes of TEM
There are two primary image modes in TEM differ in the manner in which way an
objective aperture is used as a filter in electric optics system are
1. Bright field microscopy
2. Dark field microscopy
In bright field imaging, the image of a thin sample is formed by the electrons that
pass the film without diffraction, the diffracted electrons being stopped by a diaphragm.
In the corresponding dark field imaging mode, a diffracted beam is used for imaging. The
technique known as bright Field is particularly sensitive to extended crystal lattice defects
in an otherwise ordered crystal, such as dislocations. The electron rays corresponding to
bright field and dark field imaging are shown in fig. 2.7 respectively and the experimental
set up for transmission electron microscope is shown in fig. 2.8.
Fig. 2.7 Two image modes of TEM.

Fig. 2.8 Experimental set up of Transmission Electron Microscope.
Specifications:
Model : TEM with CCD camera Philips, Tecnai 20
Electron Source : W emitter and LaB6
Accelerating Voltage : 200 kV
Point Resolution : 0.27 nm or better
Line Resolution : 2.0 nm or better
Magnification : 25X to 750000X or higher
2.2.4 UV−Vis−NIR Spectroscopy
The instrument used in ultraviolet−visible spectroscopy is called a UV−Vis−NIR

Spectrophotometer. Spectrophotometer provides a means for analyzing liquids, gases and
solids through the use of radiant energy in the far and near ultraviolet, visible and near
infrared regions of the electromagnetic spectrum. Accordingly, the predetermined
electromagnetic radiation wavelengths for ultra−violet (UV), visible (Vis) and near
infra−red (NIR) radiation are defined as follows:
UV radiation: 300 to 400 nm
Vis radiation: 400 to 765 nm
NIR radiation: 765 to 3200 nm
The instrument operates by passing a beam of light through a sample and
measuring wavelength of light reaching a detector. The wavelength gives valuable
information about the chemical structure and the intensity is related to the number of
molecules, means quantity or concentration. Analytical information can be revealed in
terms of transmittance, absorbance orreflectance of energy in the wavelength range
between 160 and 3500 mill microns [1].
Light is quantized into tiny packets called photons, the energy of which can be
transferred to an electron upon collision. However, transfer occurs only when the energy
level of the photon equals the energy required for the electron to get promoted onto the
next energy state, for example from the ground state to the first excitation state. This
process is the basis for absorption spectroscopy. Generally, light of a certain wavelength
and energy is illuminated on the sample, which absorbs a certain amount of energy from
the incident light. The energy of the light transmitted from the sample afterwards is
measured using a photo detector, which registers the absorbance of the sample. A
spectrum is a graphical representation of the amount of light absorbed or transmitted by
matter as a function of wavelength. A UV−Vis−NIR spectrophotometer measures
absorbance or transmittance from the UV range to which the human eye is not sensitive
to the visible wavelength range to which the human eye is sensitive. Bouguer−Beer law
as shown in fig. 2.9 is a basic principle of quantitative analysis, is also called the
Lambert−Beer rule. The following relationship is established when light with intensity Io
is directed at a material and light with intensity I is transmitted.
Fig. 2.9 Bouguer−Beer Rule.

In this instance the value I/Io is called transmittance (T) and the value I/Io*100 is
called transmission rate (T%). The value log (1/T) = log (Io/I) is called absorbance (Abs).
T = I/Io = 10−kcl
Abs = log (1/T) = log(Io/I) = −kcl
Here k is proportionality constant and & l = length of light path through the cuvette in
cm. As can be seen from the above formulas, transmittance is not proportional to sample
concentration. However, absorbance is proportional to sample concentration (Beer's law)
along with optical path (Bouguer's law). In addition, when the optical path is 1cm and the
concentration of the target component is 1mol/l, the proportionality constant is called the
molar absorption coefficient and expressed using the symbol ε. The molar absorption
coefficient is a characteristic value of a material under certain, specific conditions.
Finally, stray light, generated light, scattered light, and reflected light must not be present
in order for the Bouguer−Beer rule to apply.
Spectrophotometers consist of a number of fundamental components: Light

Sources (UV and VIS), monochromator (wavelength selector), sample holder, a detector,
signal processor and readout. The radiation source used is often a tungsten filament, a
deuterium arc lamp which is continuous over the ultraviolet region, and more recently
light emitting diodes (LED) and xenon arc lamps for the visible wavelengths. The
detector is typically a photodiode or a CCD. Photodiodes are used with monochromators,
which filter the light so that only light of a single wavelength reaches the detector. When
measuring absorbance at the UV spectrum, the other lamp has to be turned off. The same
goes when measuring visible light absorbance. Fig. 2.10 shows schematic diagram of
UV−Vis−NIR Spectrophotometer.

Fig. 2.10 Schematic diagram of UV−Vis−NIR Spectrophotometer.
The light source is a monochromator; the light is split into two equal intensity
beams by a half mirrored device before it reaches the sample. One beam, the sample
beam, passes through a small transparent container (cuvette) containing a solution of the
compound being studied in a transparent solvent. The other beam, the reference, passes
through an identical cuvette containing only the solvent. The containers for the sample
and reference solution must be transparent to the radiation which will pass through them.
Quartz or fused silica cuvettes are required for spectroscopy in the UV−Vis−NIR region.
The light sensitive detector follows the sample chamber and measures the intensity of
light transmitted from the cuvettes and passes the information to a meter that records and
displays the value to the operator on an LCD screen. The intensities of these light beams
are then measured by electronic detectors and compared. Some UV−Vis
spectrophotometry has two detectors the phototube and the photomultiplier tube. The
sample and reference beam are measured at the same time. The intensity of the reference
beam, which should have suffered little or no light absorption, is defined as I0. The
intensity of the sample beam is defined as I. Over a short period of time, the Spectrometer

automatically scans all the component wavelengths in the manner described. The
ultraviolet (UV) region scanned is normally from 200 to 400 nm, and the visible portion
is from 400 to 800 nm. Therefore, this method is excellent to both determine the
concentration and identify the molecular structure or the structural changes.
Spectrophotometer is also useful to study the changes in the vibration and conformation
energy levels after and before an interaction with a substrate, or another molecule [8].
Fig. 2.11 shows experimental set−up of UV−Vis−NIR Spectrophotometer.
Fig. 2.11 Experimental set up of UV−Vis−NIR Spectrophotometer.
Specifications:
Model : UV−Vis−NIR Spectrometer Perkin Elmer Lambda 19
Lamp : Deuterium (UV), Tungsten−Halogen (Vis/NIR)
Detectors : Photomultiplier tube for UV−Vis, Lead−Sulphide cell (PbS) for NIR
Wavelength Range : 185−3200 nm for Absorbance/transmission and 200−2500 nm for
reflectance
Scan Speed : 0.3 to 1200 nm/min
Wavelength accuracy : ± 0.15 nm for UV/Vis & ± 0.6 nm for NIR
Base line flatness : ± 0.001Å, 4 nm slit
Ordinate mode : Scan, time drive, wavelength programming, concentration
Photometric accuracy : ± 0.003 Å or ± 0.08% T

2.2.5 Spectrofluorometer−PL (Photoluminescence)
Photoluminescence spectroscopy is a contactless, versatile, nondestructive,

powerful optical method of probing the electronic structure of materials. Light is directed
onto a sample, where it is absorbed and imparts excess energy into the material in a
process called photo−excitation. One way this excess energy can be dissipated by the
sample is through the emission of light, or luminescence. In the case of photo−excitation,
this luminescence is called photoluminescence. Thus photoluminescence is the
spontaneous emission of light from a material under optical excitation. This light can be
collected and analyzed spectrally, spatially and also temporally. The intensity and
spectral content of this photoluminescence is a direct measure of various important
material properties.
Photo excitation causes electrons within the material to move into permissible
excited states. When these electrons return to their equilibrium states, the excess energy
is released and may include the emission of light (a radiative process) or may not (a non
radiative process) as shown in fig. 2.12. The energy of the emitted light
(photoluminescence) relates to the difference in energy levels between the two electron
states involved in the transition between the excited state and the equilibrium state. The
quantity of the emitted light is related to the relative contribution of the radiative process.
PL spectroscopy gives information only on the low lying energy levels of the investigated
system. In semiconductor systems, the most common radiative transition is between
states in the conduction and valence bands, with the energy difference being known as
the bandgap. During a PL spectroscopy experiment, excitation is provided by laser light
with an energy much larger than the optical band gap. The photo excited carriers consist
of electrons and holes, which relax toward their respective band edges and recombine by
emitting light at the energy of the band gap. Radiative transitions in semiconductors may
also involve localized defects or impurity levels therefore the analysis of the PL spectrum
leads to the identification of specific defects or impurities, and the magnitude of the PL
signal allows determining their concentration. The respective rates of radiative and

nonradiative recombination can be estimated from a careful analysis of the temperature
variation of the PL intensity and PL decay time. At higher temperatures nonradiative
recombination channels are activated and the PL intensity decreases exponentially. Thus
photoluminescence is a process of photon excitation followed by photon emission and
important for determining band gap, purity, crystalline quality and impurity defect levels
of semiconducting material. It also helps to understand the underlying physics of the
recombination mechanism.
PL spectrum is quite different from absorption spectrum in the sense that

absorption spectrum measures transitions from the ground state to excited state, while
photoluminescence deals with transitions from the excited state to the ground state. The
period between absorption and emission is typically extremely short. An excitation
spectrum is a graph of emission intensity versus excitation wavelength which looks very
much like an absorption spectrum. The value of wavelength at which the molecules
absorbs energy can be used as the excitation wavelength which provide a more intense
emission at a red shifted wavelength, with a value usually twice of the excitation
wavelength.
Fig. 2.12 Principle of photoluminescence spectroscopy (PL).

A spectrofluorometer is an analytical instrument used to measure and record the

fluorescence of a sample. While recording the fluorescence, the excitation, emission or
both wavelength may be scanned. With additional accessories, variation of signal with
time, temperature, concentration, polarization, or other variables may be monitored. Fig.
2.13 shows the block diagram of fluorescence spectrometer. Fluorescence spectrometers
use laser sources, which contains wavelength selectors, sample illumination, detectors
and corrected spectra.
Fig. 2.13 Block diagram of fluorescence spectrometer.
Illuminator source:- The continuous light source is 150 W ozone free xenon arc lamp.
Light from the lamp is collected by a diamond turned elliptical mirror, and then focused
on the entrance slit of the excitation monochromator. The lamp housing is separated from
the excitation monochromator by a quartz window. This vents heat out of the instrument,
and protects against the unlikely occurrence of lamp failure. Resolution over the entire
spectral range and minimize spherical aberrations and re diffraction.

Monochromators:- It contains two monochromators : Excitation monochromator and
Emission monochromator. They use all reflective optics to maintain high resolution over
the entire spectral range, and minimize spherical aberrations and re diffraction.
Gratings:- The essential part of a monochromator is a reflection grating. A grating

disperses the incident light by means of its vertical grooves. A spectrum is obtained by
rotating the gratings contain 1200 grooves mm−1, and are blazed at 330 nm (excitation) at
500 nm (emission). Each grating is coated with MgF2 for protection against oxidation.
Slits:- The entrance and exit ports of each monochromator have continuously adjustable
slits. The width of the slits on the excitation monochromator determines the band pass of
light incident on the sample. The emission monochromator’s slits control the intensity of
the fluorescence signal recorder by the signal detector. When setting slit width, the trade
off is intensity of signal versus spectral resolution. The wider the slits are, the more light
falls on the sample and detector, but the resolution decreases. The narrower slits are, the
higher the resolution gets but at the expense of signal.
Shutters:- An excitation shutter is located just after the excitation monochromator’s exit
slit. The shutter protects sample from photo bleaching or photo degradation from
prolonged exposure to the light source. An emission shutter is placed just before the
emission monochromator’s entrance and protects the detector from bright light.
Sample compartment:- The sample compartment accommodates various optional

accessories, as well as fiber optic bundles to take the excitation beam to a remote sample
and return the emission beam to the emission monochromator.
Detectors:- It contains two detectors: Signal detector and reference detector. The signal
detector is a photon conting detector. This detector is an R928P photomultiplier tube,
which sends the signal to a photon counting module. The reference detector monitors the
xenon lamp, in order to correct for wavelength and time dependent output of the lamp.
This detector is a UV enhance silicon photodiode, which is just before the sample
compartment.

Computer Control:- The entire control of the FluoroMax−4 originates in your PC with
our revolutionary new Fluor Essenc software and is transmitted through a serial link. On
start up, the system automatically calibrates and presents itself for new experiments or
stored routines instantly called from memory. Fig. 2.14 shows Experimental set up of
Spectrofluorometer.
Fig. 2.14 Experimental set up of SHIMADZU RF−5301PC Spectrofluorometer.
Specifications:
Light source : 150 W Xenon lamp. Ozone resolving type lamp housing
Excitation and : Concave, blazed holographic grating, F/2.5, 1300
emission grooves/mm
monochromators
Wavelength scale : 220−990 nm
Measuring wavelength : 220−750 nm and 0 order as standard. 220−900 nm with the
range optional R928 photomultiplier
Spectral band with : 6 step selection of 1.5, 3, 5, 10, 15 and 20 nm. (6 nm
bandwidth is available for half sample height on the
excitation side only).

Wavelength accuracy : ±1.5 nm
Light source : Dynode feedback system with monochromatic light
compensation monitoring
Sensitivity : The S/N ratio is 150 or higher for the Raman line of distilled
water (350 nm excitation wavelength, 5 nm spectral
bandwidth, and 2 second response for 98% of the full scale)
Wavelength scanning : 7 step selection of Survey (about 5500 nm/min), Super
(about 3000 nm/min)
Very fast, Fast, Medium, Slow and Very slow
Wavelength slewing : About 20,000 nm/min.
speed
Response : 8 step selection of 0.02, 0.03, 0.1, 0.25, 0.5, 2, 4 and 8
seconds for 98% of the full scale
Sensitivity selection : 2 steps of HIGH and LOW (The sensitivity at HIGH is
about 50 times that of LOW)
2.2.6 Fourier Transform Infrared Spectroscopy (FTIR)
Infrared spectroscopy is an important technique in organic chemistry. It is an

easy way to identify the presence of certain functional groups in a molecule. Also, one
can use the unique collection of absorption bands to confirm the identity of a pure
compound or to detect the presence of specific impurities. Analysis by infrared
spectroscopy is based on the fact that molecules have specific frequencies of internal
vibrations. These frequencies occur in the infrared region of the electromagnetic
spectrum: ~ 4000 cm−1 to ~ 200 cm−1.
When a sample is placed in a beam of infrared radiation, the sample will absorb
radiation at frequencies corresponding to molecular vibrational frequencies, but will
transmit all other frequencies. The frequencies of radiation absorbed are measured by an
infrared spectrometer, and the resulting plot of absorbed energy vs. frequency is called

infrared spectrum of the material. Identification of a substance is possible because
different materials have different vibrations and yield different infrared spectra.
Furthermore, from the frequencies of the absorption it is possible to determine whether
various chemical groups are present or absent in a chemical structure. In addition to the
characteristic nature of the absorption, the magnitude of the absorption due to a given
species is related to the concentration of that species.
Fourier Transform Infrared (FTIR) spectrometry was developed in order to

overcome the limitations encountered with dispersive instruments. The main difficulty
was the slow scanning process. A method for measuring all of the infrared frequencies
simultaneously, rather than individually, was needed. A solution was developed which
employed a very simple optical device called an interferometer. The interferometer
produces a unique type of signal which has all of the infrared frequencies “encoded” into
it. The signal can be measured very quickly, usually on the order of one second or so.
Thus, the time element per sample is reduced to a matter of a few seconds rather than
several minutes. Most interferometers employ a beam splitter which takes the incoming
infrared beam and divides it into two optical beams. One beam reflects off of a flat mirror
which is fixed in place. The other beam reflects off of a flat mirror which is on a
mechanism which allows this mirror to move a very short distance (typically a few
millimeters) away from the beam splitter. The two beams reflect off of their respective
mirrors and are recombined when they meet back at the beam splitter. Because the path
that one beam travels is a fixed length and the other is constantly changing as its mirror
moves, the signal which exits the interferometer is the result of these two beams
“interfering” with each other. The resulting signal is called an interferogram which has
the unique property that every data point (a function of the moving mirror position)
which makes up the signal has information about every infrared frequency which comes
from the source. This means that as the interferogram is measured; all frequencies are
being measured simultaneously. Thus, the use of the interferometer results in extremely
fast measurements. Because the analyst requires a frequency spectrum (a plot of the
intensity at each individual frequency) in order to make identification, the measured
interferogram signal cannot be interpreted directly. A means of “decoding” the individual

frequencies is required. This can be accomplished via a well known mathematical
technique called the Fourier transformation. This transformation is performed by the
computer which then presents the user with the desired spectral information for analysis.
The basic components of an FTIR are shown schematically in fig. 2.15. The
infrared source emits a broad band of different wavelength of infrared radiation. The IR
source used in the Temet GASMET FTIR CR−series is a SiC ceramic at a temperature of
1550 K. The IR radiation goes through an interferometer that modulates the infrared
radiation. The interferometer performs an optical inverse Fourier transform on entering
IR radiation. The modulated IR beam passes through the gas sample where it is absorbed
to various extents at different wavelengths by the various molecules present. Finally, the
intensity of the IR beam is detected by a detector, which is a liquid nitrogen cooled MCT
(Mercury−Cadmium−Telluride) detector in the case of the Temet GASMET FTIR CR
series. The detected signal is digitised and Fourier transformed by the computer to get the
IR spectrum of the sample gas.
Fig. 2.15 Basic components of FTIR.
1. The Source:- Infrared energy is emitted from a glowing black body source. This beam
passes through an aperture which controls the amount of energy presented to the sample
(and, ultimately, to the detector).
2. The Interferometer:- The beam enters the interferometer where the “spectral
encoding” takes place. The resulting interferogram signal then exits the interferometer.
3. The Sample:- The beam enters the sample compartment where it is transmitted
through or reflected off of the surface of the sample, depending on the type of analysis

being accomplished. This is where specific frequencies of energy, which are uniquely
characteristic of the sample, are absorbed.
4. The Detector:- The beam finally passes to the detector for final measurement. The
detectors used are specially designed to measure the special interferogram signal.
5. The Computer:- The measured signal is digitized and sent to the computer where the
Fourier transformation takes place. The final infrared spectrum is then presented to the
user for interpretation and any further manipulation. Fig. 2.16 shows experimental set up
of FTIR spectrometer.
Fig. 2.16 Experimental set up of FTIR spectrometer.
Specifications:
Model : Perkin Elmer Spectrum GX

Sample : Solid, Liquid or Gas
Operating Mode : NIR and MIR
Scan Range : 15600 to 30 cm−1
Optical system : Source NIR: 15,200 – 1,200 cm−1

Beam splitter KBr : 7,800 − 370 cm−1
Detector MIRTGS : 10,000 − 220 cm−1
Beam splitter KBr : 7,800 − 370 cm−1
OPD Velocity : 0.20 cm/s
Inferogram : Bi−Direction
Direction
Scan Time : 20 scan/second
Resolution : 0.15cm−1
Single Beam/Ratio : Single
Detector : MIRTGS
2.2.7 Raman Spectroscopy
Raman spectroscopy is a useful technique for the identification of a wide range of

substances–solids, liquids and gases. It is a straightforward, non destructive technique
requiring no sample preparation. Raman spectroscopy involves illuminating a sample
with monochromatic light and using a spectrometer to examine light scattered by the
sample.
Raman spectroscopy is a spectroscopic technique based on inelastic scattering of

monochromatic light, usually from a laser source. Inelastic scattering means that the
frequency of photons in monochromatic light changes upon interaction with a sample.
Photons of the laser light are absorbed by the sample and then reemitted. Frequency of
the reemitted photons is shifted up or down in comparison with original monochromatic
frequency, which is called the Raman effect. This shift provides information about
vibrational, rotational and other low frequency transitions in molecules. This effect is
based on molecular deformations in electric field E determined by molecular
polarizability (α). The laser beam can be considered as an oscillating electromagnetic
wave with electrical vector E. Upon interaction with the sample it induces electric dipole
moment P = αE which deforms molecules. Because of periodical deformation, molecules
start vibrating with characteristic frequency υm. Monochromatic laser light with
frequency υo excites molecules and transforms them into oscillating dipoles. Such
oscillating dipoles emit light of three different frequencies as shown in fig. 2.17 when:
1. A molecule with no Raman active modes absorbs a photon with the frequency υo. The
excited molecule returns back to the same basic vibrational state and emits light with
the same frequency υo as an excitation source. This type of interaction is called an
elastic Rayleigh scattering.
2. A photon with frequency is absorbed by Raman active molecule which at the time of
interaction is in the basic vibrational state. Part of the photon’s energy is transferred to
the Raman active mode with frequency υm and the resulting frequency of scattered
light is reduced to υo−υm. This Raman frequency is called Stokes frequency or just
“Stokes”.
3. A photon with frequency υo is absorbed by a Raman active molecule, which, at the

time of interaction, is already in the excited vibrational state. Excessive energy of
excited Raman active mode is released, molecule returns to the basic vibrational state
and the resulting frequency of scattered light goes up to υo+υm . This Raman frequency
is called Anti Stokes frequency or just “Anti Stokes’’.
The Raman shift does not depend upon the frequency of the incident light but it is
regarded as a characteristic of the substance causing Raman effect. For Stoke’s lines, ∆υ
is positive and for anti stoke’s lines ∆υ is negative.
From fig. 2.18 we can notice that the stokes and anti stokes lines are equally
displaced from the Rayleigh line. This occurs because in either case one vibrational
quantum of energy is gained or lost. Also, note that the anti stokes line is much less
intense than the stokes line. This occurs because only molecules that are vibrationally
excited prior to irradiation can give rise to the anti stokes line. Hence, in Raman
spectroscopy, only the more intense stokes line is normally measured. Infrared absorption
spectroscopy is another similar vibrational technique used to examine molecular structure
but differs from Raman spectroscopy in the manner in which way the molecular
transitions are taking place. For a transition to be Raman active there must be a change in
the polarizability of the molecule during the vibration. This means that the electron cloud
of the molecule must undergo positional change. On the other hand, for an Infrared
detectable transition, the molecule must undergo dipole moment change during vibration.
Homonuclear diatomic molecules such as H2, N2, O2, etc. which do not show infrared
spectra since they do not possess a permanent dipole moment do show Raman spectra
since their vibration is accompanied by a change in polarizability of the molecule. Thus,
Raman spectroscopy permits us to examine the vibrational spectra of compounds that do
not lend themselves to IR absorption spectroscopy.
Raman spectroscopy can be used on liquids, solids and gases making it very
versatile for studying various materials. Because of the distinct spectra that certain
classes of materials give off, due to their structural arrangement, Raman spectroscopy can
be used to determine the composition of unknown substances. This also makes Raman
spectroscopy ideal for qualitative analysis of materials. In Raman spectroscopy no probe
physically touches the material the laser light is the only thing to disturb the sample, this
means that the material is not disturbed by the probe physically touching it and in some
cases is the only way to accurately study a material.
Fig. 2.17 Shows vibrational levels of the material.

Fig. 2.18 Raman spectrum.
A Raman system typically consists of four major components:
1. Excitation source (Laser).

2. Sample illumination system and light collection optics.
3. Wavelength selector (Filter or Spectrometer).
4. Detector (Photodiode array, CCD or PMT).
Fig. 2.19 Schematic diagram of Raman spectrometer. In Raman instrument a

sample is illuminated with a laser beam. Light from the illuminated spot is collected with
a lens and sent through interference filter or spectrometer to obtain Raman spectrum of a
sample. Wavelengths close to the laser line, due to elastic Rayleigh scattering, are filtered
out while the rest of the collected light is dispersed onto a detector. By changing the laser
light you can confirm if a peak is a true Raman peak and not a peak just associated with
the wavelength of the laser light that was used. Spontaneous Raman scattering signal is
very weak because most of the incident photons undergo elastic Rayleigh scattering.
Therefore special measures should be taken to distinguish it from the predominant
Rayleigh scattering. Instruments such as notch filters, tunable filters, laser stop apertures,
double and triple spectrometric systems are used to reduce Rayleigh scattering and obtain
high quality Raman spectra.

In some instruments, sample is placed into the cryostat chamber where the low
temperature is achieved by the use of liquid helium that cooled the cryostat. The cryostat
is kept in vacuum so that laser light suffer no scattering from the particles of the air in the
chamber. Before every measurement the scattered light would have to be aligned in the
spectrometer so that maximum signal would hit the detector. This can be achieved by
moving the sample to different positions and using lens, mirror system. In earlier times
for taking Raman spectrum single point detectors such as photon counting
Photomultiplier Tubes (PMT) was used. However, due to the consumption of very long
time PMT is not preferred because it slow down any research or industrial activity based
on Raman analytical technique. Nowadays, Raman spectroscopy has become even more
accurate and easier due to advancements in optics, laser and computer technology.
Researchers use multi channel detectors like Photo Diode Arrays (PDA) or, more
commonly, a Charge Coupled Devices (CCD) to detect the Raman scattered light.
Charge Coupled Device (CCD) detectors have enormously helped the use of
Raman spectroscopy by allowing scientist to take data quicker and with more precision
that they were able to with the older photomultiplier tubes. The CCD has an array of
detectors that can look at a range of wavelengths at one time greatly reducing the
collection time. Sensitivity and performance of modern CCD detectors are rapidly
improving. In many cases CCD is becoming the detector of choice for Raman
spectroscopy [9−11].
Raman spectroscopy can be used on liquids, solids and gases making it very
versatile for studying various materials. Because of the distinct spectra that certain
classes of materials give off, due to their structural arrangement, Raman spectroscopy can
be used to determine the composition of unknown substances. This also makes Raman
spectroscopy ideal for qualitative analysis of materials. In Raman spectroscopy no probe
physically touches the material the laser light is the only thing to disturb the sample, this
means that the material is not disturbed by the probe physically touching it and in some
cases is the only way to accurately study a material. Surface Enhanced Raman
Spectroscopy (SERS) and Resonance Raman Effect (RRE) are different types of Raman

spectroscopy. The goal of these two processes is to enhance the weak signal of the
Raman spectra. Micro Raman spectroscopy (MRS) is another type of Raman
spectroscopy and this process reduces the spot size of the light source on the sample,
which is helpful if a small area of the sample is to be observed. It is also used to reduce
damage or heating of the sample by the laser light [9−11]. The experimental set up of
Raman Spectrometer is shown in the fig. 2.20.
Specifications:
Least count : 0.3 cm−1

Range : 50 cm−1 to 4000 cm−1
Detector : Charge Coupled Device (CCD)
Light source : Argon laser (10 mW, λ = 488 nm, color−blue, Eg = 2.53 eV) and He−Ne
(5 mW, λ = 632 nm, color red, Eg = 1.95 eV)
Resolution : Lateral resolution of 1micron, an axial resolution of 2 micron and spectral
resolution of the order of 1 cm−1
Filter : Notch or Plasma filter for intensity variation of incident laser light
Object Lens : Highly stable optics with 10X, 50X, 100X objective lens
Dispersive geometry : 600 and 1800 lines/mm gratings
Temperature range : Low temperature attachment (LN2) upto 85 K
Fig. 2.19 Schematic diagram of Raman spectrometer.

Fig. 2.20 Experimental set up of Raman spectrometer.
2.2.8 Gouy Balance Method
Magnetic susceptibility is measured using very sensitive instrument known as a

magnetic susceptibility balance Gouy balance. The balance contains a pair of magnets
mounted at opposite ends of a beam, initially in equilibrium. When a sample is
introduced into the balance a disruption of the magnetic field results. A current through a
coil located between the poles of a second pair of magnets returns the beam to
equilibrium. The current through the coil is measured and transformed into a numerical
reading. Diamagnetic materials are weakly repelled by an external magnetic field,
resulting in a negative reading. Paramagnetic materials are attracted to an external
magnetic field and give a positive reading.
The Gouy balance measures the apparent change in the mass of the sample as it is
repelled or attracted by the region of high magnetic field between the poles [12]. Some
commercially available balances have a port at their base for this application. In use, a
long, cylindrical sample to be tested is suspended from a balance, partially entering
between the poles of a magnet. The sample can be in solid or liquid form, and is often
placed in a cylindrical container such as a test tube. Solid compounds are generally
ground into a fine powder to allow for uniformity amongst the sample [13]. The sample is
suspended between the magnetic poles through an attached thread or string [12]. The
experimental procedure requires two separate reading to be performed. An initial balance
reading is performed on the sample of interest without a magnetic field (ma). A
subsequent balance reading is taken with an applied magnetic field (mb). The difference
between these two readings relates to the magnetic force on the sample (mb−ma) [12].
The apparent change in mass from the two balance readings is a result of
magnetic force on the sample. The magnetic force is applied across the gradient of a
strong and weak magnetic field. A sample with a paramagnetic compound will be pulled
down towards the magnetic field and provide a positive difference in apparent mass
mb−ma. Diamagentic compounds can either exhibit no apparent change in weight or a
negative change as the sample is slightly repelled by the applied magnetic field [14].
With a paramagnetic sample, the magnetic induction is stronger than the applied field and
magnetic susceptibility is positive. A diamagnetic sample has a magnetic induction much
weaker than the applied field, and a respective negative magnetic susceptibility [15].
In a practical device, the whole assembly of balance and magnet is enclosed in a

glass box to ensure that the weight measurement is not affected by air currents. The
sample can also be enclosed in a thermostat in order to make measurements at different
temperatures [16]. Since it requires a large and powerful electromagnet, the Gouy balance
is a stationary instrument permanently set up on a bench [12]. The apparatus is often
placed on a marble balance table to minimize the vibrations and disruption from the
environment [15]. The stationary magnetic of a Gouy balance is often an electromagnet
connected to a power source, since balance recordings with and without the applied
magnetic field is required of the procedure. Experimental set up shown in fig. 2.21.

Fig. 2.21 Experimental set up Gouy balance method.
Specification:
Magnet : 0.4 Tesla

Balance : Mettler (0.05mg)
2.2.9 Vibrating Sample Magnetometer (VSM)
The vibrating sample magnetometer is a simple yet effective technique for

characterizing properties of magnetic materials. Vibrating sample magnetometry (VSM)
is based on Faraday's law which states that an electromagnetic force is generated in a coil
when there is a change in flux linking the coil [17].
The operation of the VSM is fairly simple: a sample is vibrated between a pair of
pick−up coils and a dc magnetic field is applied to the sample (usually in a direction
perpendicular to the coils). The magnetic field magnetises the sample and so the vibrating
magnetic moment produces a flux that changes with time and, consequently, results in an
ac voltage being induced in the detection coils (From Faraday’s Law). The signal from
the coils is detected with a lock in amplifier because it has both a narrow bandwidth (for
a given relative frequency) and a very high gain. The lock−in amplifier gives a dc voltage
output that is proportional to the magnetic moment of the material; thus one may obtain a
measure of sample magnetisation as a function of magnetic field (magnetisation curve).
Fig. 2.22 shows basic principle of VSM.
Fig. 2.22 Basic principle.
Fig. 2.23 shows Layout of vibrating sample magnetometer. The basic

measurement is accomplished by oscillating the sample near a detection (pickup) coil and
synchronously detecting the voltage induced. By using a compact gradiometer pickup
coil configuration, relatively large oscillation amplitude (1−3 mm peak) and a frequency
of 40 Hz, the system is able to resolve magnetization changes of less than 10−6 emu at a
data rate of 1 Hz. The VSM option for the Physical Property Measurement System
(PPMS) consists primarily of a VSM linear motor transport (head) for vibrating the
sample, a coilset puck for detection, electronics for driving the linear motor transport and
detecting the response from the pickup coils, and a copy of the MultiVu software
application for automation and control.
The sample is attached to the end of a sample rod that is driven sinusoidally. The
center of oscillation is positioned at the vertical center of a gradiometer pickup coil. The

precise position and amplitude of oscillation is controlled from the VSM motor module
using an optical linear encoder signal readback from the VSM linear motor transport. The
voltage induced in the pickup coil is amplified and lock in detected in the VSM detection
module. The VSM detection module uses the position encoder signal as a reference for
the synchronous detection. This encoder signal is obtained from the VSM motor module,
which interprets the raw encoder signals from the VSM linear motor transport. The VSM
detection module detects the in phase and quadrature phase signals from the encoder and
from the amplified voltage from the pickup coil. These signals are averaged and sent over
the CAN bus to the VSM application running on the PC.
The system is designed to be user installable and compatible with existing PPMS
systems. Upgrading your current system will therefore be a simple process. Like the other
PPMS applications, the VSM is used only when required, leaving the PPMS to run other
applications as needed. Since the VSM system is a completely self contained
measurement application, other than one of the PPMS Base Systems, there are no other
PPMS applications or options required for its use. Fig. 2.24 shows experimental set up of
14T PPMS−Vibrating Sample Magnetometer.
Fig. 2.23 Layout of vibrating sample magnetometer.

Fig. 2.24 Experimental set up of 14T PPMS−vibrating sample magnetometer.
Specifications:
Temperature range : 2 to 350 K

Magnetic field : 140 kOe
Sensitivity : 10−5 emu
Temperature stability : ~ 10 mK
2.2.10 Thermogravimetry Analysis (TGA)
It is a simple analytical technique that measures the amount and rate of change in
the weight of a material as a function of temperature or time in a controlled atmosphere.
Measurements are used primarily to determine the composition of materials and to
predict their thermal stability at temperatures up to 1000 °C. It is the most widely used
thermal method as shown in fig. 2.25 which can characterize materials that exhibit weight
loss or gain due to decomposition, oxidation, or dehydration. As materials are heated,
they can lose weight from a simple process such as drying, or from chemical reactions
that liberate gases. Some materials can gain weight by reacting with the atmosphere in
the testing environment. Since weight loss and gain are disruptive processes to the sample
material, knowledge of the magnitude and temperature range of those reactions are
necessary in order to design adequate thermal ramps and holds during those critical
reaction periods. Such analysis relies on a high degree of precision in three
measurements: weight, temperature, and temperature change.
A plot of weight change versus temperature is referred to as the

thermogravimetric curve (TGA curve) which helps in revealing the extent of purity of
analytical samples and determining the mode of their transformations within specified
range of temperature. As many weight loss curves look similar, the weight loss curve
may require transformation before results may be interpreted. A derivative weight loss
curve can be used to tell the point at which weight loss is most apparent.
Therefore, TGA curves can provide information about the composition of multi
component systems, thermal stability, oxidative stability of materials, decomposition
kinetics of materials, the effect of reactive or corrosive atmospheres on materials and
moisture content of materials.
Fig. 2.25 Schematic diagram of thermogravimetric analyzer.
The instrument used in thermogravimetry (TGA) is called a thermobalance. It

consists of a sample pan that is supported by a precision balance. That pan resides in a
furnace and is heated or cooled during the experiment. The mass of the sample is

monitored during the experiment and a purge gas controls the sample environment. This
gas may be inert or a reactive gas that flows over the sample to prevent oxidation or other
undesired reactions and exits through an exhaust. The whole arrangement shown in fig.
2.27 with block diagram in fig. 2.26 provides the flexibility necessary for the production
of useful analytical data in the form of TGA curve. Basic components of a typical
thermobalance are listed below:
1. Balance
2. Furnace: heating device
3. Unit for temperature measurement and control (Programmer)
4. Recorder: automatic recording unit for the mass and temperature changes
The basic requirement of an automatic recording balance are includes accuracy,

sensitivity, reproducibility, and capacity. Recording balances are of two types, null point
and deflection type. The null type balance, which is more widely used, incorporates a
sensing element which detects a deviation of the balance beam from its null position. A
sensor detects the deviation and triggers the restoring force to bring the balance beam to
back to the null position. The restoring force is directly proportional to the mass change.
Deflection balance of the beam type involve the conversion of the balance beam
deflection about the fulcrum into a suitable mass change trace by (a) photographic
recoding i.e. change in path of a reflected beam of light available of photographic
recording, (b) recording electrical signals generated by an appropriate displacement
measurement transducer, and (c) using an electrochemical device. The different balances
used in TGA instruments are having measuring range from 0.0001mg to 1g depending on
sample containers used.
The furnace and control system must be designed to produce linear heating at
over the whole working temperature range of the furnace and provision must be made to
maintain any fixed temperature. A wide temperature range generally 150 °C to 2000 °C
of furnaces is used in different instruments manufacturers depending on the models. The
range of furnace basically depends on the types of heating elements are used. In our
instrument, temperature can vary from 25 °C to 900 °C isothermally and the maximum
temperature range is 1000 °C. Sample weight can range from 1 mg to 150 mg but sample
weights of more than 25 mg are preferred and sometimes excellent results are obtained
with 1mg of material.
Temperature measurement are commonly done using thermocouples,

chromal−alumel thermocouple are often used for temperature up to 1100 °C whereas Pt–
Rh thermocouple is employed for temperature up to 1750 °C. Temperature may be
controlled or varied using a program controller with two thermocouple arrangement, the
signal from one actuates the control system whilst the second thermocouple is used to
record the temperature.
Graphic recorders are preferred to meter type recorders. X−Y recorders are
commonly used as they plot weight directly against temperature. The present instrument
facilitate microprocessor controlled operation and digital data acquisition and processing
using personal computer with different types recorder and plotter for better presentation
of data.
The whole of the balance system is housed in a glass to protect it from dust and
provide inert atmosphere. There is a control mechanism to regulate the flow of inert gas
to provide inert atmosphere and water to cool the furnace. The temperature sensor of
furnace is linked to the programme to control heating rates, etc. The balance output and
thermocouple signal may be fed to recorder to record the TGA Curve [18−26].
Fig. 2.26 Block diagram of thermobalance.

Fig. 2.27 Experimental set up of thermogravimetric analysis.
Specifications:
Temperature Range : Ambient to 1000 ºC
Sensitivity : 0.0001 mg
Atmosphere : N2 or Air
Balance Type : Hangdown Pan
Balance capacity : 1300 mg

2.3 References
[1] J. P. Sibilia
A Guide to Materials Characterization and Chemical Analysis, VCH
Publishers (1998).
[2] D. Brondon, W. D. Kaplan

Microstructural Characterization of Materials, John− Wiley and Sons (1999).
[3] L. F. Vassamillet
J. Appl. Phys. 40 (1969) 1637.
[4] B. E. Warren
X−ray Diffraction, Addison−Wesley (1969).
[5] E. W. Nuffield
X−ray Diffraction Methods, Wiley (1966).
[6] B. D. Cullity
nd
Elements of X−ray Diffraction (2 Ed.), Addison−Wesley (1978).
[7] C. Kittel
th
Introduction to Solid State Physics (7 Ed.), John−Wiley and Sons (1995).
[8] G. R. Chatwal, S. K. Anand

Instrumental methods of chemical analysis, Himalaya Publishing House
(1979).
[9] J. R. Ferraro, K. Nakamoto, C. W. Brown

Introductory Raman spectroscopy, Academic Press (2003).
[10] I. R. Lewis, H. G. M. Edwards

Handbook of Raman Spectroscopy, CRC Press (2001).

[11] E. Smith, G. Dent
Modern Raman Spectroscopy, John Wiley and Sons Ltd. (2005).
[12] A. Saunderson
Physics Education 3 (1968) 272.
[13] F. Brucacher, L. J. Stafford

J. Chem. Educ. 39 (1962) 574.
[14] N. Holzenkaempfer, J. Gipe

Magnetic Properties of Coordination Complexes, UC Davis ChemWiki
[15] S. Liang, B. Harrison, J. Pagotto

Determination of the Impregnant Concentrations on ASC Type Charcoal,
Defence Research Establishment Ottawa (1997).
[16] A. Earnshaw
Introduction to Magnetochemistry. Academic Press. Publisher (1968).
[17] K. H. J. Buschow, F. R. de Boer

Physics of Magnetism and Magnetic Materials. Kluwer Academic/Plenum
Publisher (2003).
[18] T. C. Daniels
Thermal Analysis, John Wiley & Sons, Hanser Publisher, NewYork (1973).
[19] W. W. Wendlandt
Themal Methods of Analysis, Interscience Publishers, New York (1964).
[20] C. Duval
Inorganic Thermogravimetric Analysis, Elsevier Publisher, NewYork (1963).
[21] C. J. Keattc
An Introduction to Thermogravimetry, Dollimore, Heyden & Son Ltd.,
England (1975).
[22] M. E. Brown
Introduction to Thermal Analysis, Kluwer Academic Publisher, London
(2001).
[23] R. A. Meyers
Encyclopedia of Analytical Chemistry, John Wiley & Sons Ltd., Chichester
(2000).
[24] P. J. Haines
Principles of Thermal Analysis & Calorimetry, Royal Society of Chemistry,
Cambridge (2002).
[25] C. M. Earnest
Compostional Analysis by Thermogravimetry, American Society for Testing
and Materials (1988).
[26] P. D. Garn
Thermoanalytical Methods of Investigations, Academic Press Publisher,
NewYork (1965).

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CHAPTER 2

Basic Principle, Working

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 57

In this chapter, a brief description of basic principle, working and experimental

1. Energy Dispersive Analysis of X−rays (EDAX)

2.2 Characterization Techniques

2.2.1 Energy Dispersive Analysis of X−rays (EDAX)

2.2.1.1 Basic Principle

EDAX is an analytical technique used for elemental analysis or chemical

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 58

Fig. 2.1 Principle of EDAX.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 59

2.2.1.2 Experimental Set Up

Fig. 2.2 shows an experimental arrangement of EDAX attached to an SEM. It

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 60

Fig. 2.2 Experimental set up of Energy dispersive analysis of X−rays (EDAX).

2.2.2 X−ray Diffraction (XRD)

2.2.2.1 Basic Principle

X−ray Powder Diffraction (XRD) is an efficient analytical technique used

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 61

X−ray diffraction is based on constructive interference of monochromatic X−rays

Fig. 2.3 A schematic of Bragg’s reflection from a crystal.

2.2.2.2 Experimental Set Up

X−ray diffractometers consists of three basic elements:

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 62

X−rays are generated in a cathode ray tube by heating a filament to produce

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 63

Results are commonly presented as peak positions at 2θ and X−ray counts

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 64

Model : Philips Xpert MPD XRD

Fig. 2.5 Experimental set up of X−ray diffractometer.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 65

2.2.3.1 Basic Principle

Transmission electron microscopy (TEM) is a technique used for analyzing the

TEMs are capable of imaging at a significantly higher resolution than light

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 66

TEM offers two methods of specimen observation as shown in fig. 2.6.

Fig. 2.6 Shows two different operations of TEM.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 67

Fig. 2.7 Two image modes of TEM.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 68

2.2.4 UV−Vis−NIR Spectroscopy

2.2.4.1 Basic Principle

The instrument used in ultraviolet−visible spectroscopy is called a UV−Vis−NIR

Fig. 2.9 Bouguer−Beer Rule.

2.2.4.2 Experimental Set Up

Spectrophotometers consist of a number of fundamental components: Light

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 71

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 72

Fig. 2.11 Experimental set up of UV−Vis−NIR Spectrophotometer.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 73

2.2.5.1 Basic Principle

Photoluminescence spectroscopy is a contactless, versatile, nondestructive,

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 74

PL spectrum is quite different from absorption spectrum in the sense that

Fig. 2.12 Principle of photoluminescence spectroscopy (PL).

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 75

A spectrofluorometer is an analytical instrument used to measure and record the

Fig. 2.13 Block diagram of fluorescence spectrometer.

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 76

Gratings:- The essential part of a monochromator is a reflection grating. A grating

Sample compartment:- The sample compartment accommodates various optional

[Nikita H. Patel / Ph. D. Thesis / Sardar Patel University/ July−2015] Page 77