CHAPTER-3

INSTRUMENTATION
This chapter describes the instruments: TL glow curve recorder, XRD, TGA (Thermal
gravimetric Analysis), FTIR, ICP-AES (Induction Coupled Plasma Atomic Emission
Spectroscopy) and Laser diffraction particle size analyzer used for the characterization
of collected minerals.
3.1 FURNACE
Thermal annealing treatment for the specimen was carried out in the muffle furnace.
The muffle furnace with maximum 1200C heating capacity and control options was
used for Thermal annealing treatment. The temperature was maintained with 1oC
accuracy using a temperature controller. Alumina crucibles were used in the furnace
3.2 THERMOLUMINESCENCE READER
Nucleonix PC Controlled Thermoluminescence Reader [Type: TL1009] was
employed for the thermoluminescence property analysis of the samples [1]. The
heating rate was set as 1C/sec and samples were heated from room temperature to
400C. Before TL procedure, 5mg sample was exposed to radiations at room
temperature for 5 minutes. After 1-minute retention period, sample was put into TLD
reader.
PC Controlled Thermoluminescence Reader [TYPE: TL 1009]
Thermoluminescence Reader Type TL1009 designed and offered by NUCLEONIX
SYSTEMS is a versatile controller based unit, facilitating the user to subject the TL
sample under study to the desired heating profile, to record the digitized TL glow
curve (Figure-3.1). This unit stores both integral value and digitized glow curve into
EEPROM memory. This unit records the data in 200 channels, temp, TL intensity &
Run time values. Entire electronics including PMT, HV bias, Temperature controller
circuit, Heater transformer heater strip, sample drawer assembly, data acquisition
electronics is all integrated into a single enclosure. The user interface to the unit is
through a powerful software GUI, coded in VB which runs on Windows platform.
This system essentially works as a PC controlled TLD reader with command buttons
and dropdown menus defined for various functions. Built-in small keypad and visual
indication through a 20x4 LCD dotmatrix display provide limited functions to the
40

users which essentially serve the purpose of checking the majority of the unit
hardware functionality. Built-in serial port in the unit facilitates the user to connect it
to a PC for GUI and to achieve full functionality [2].

(i) Features

Micro controller based Integral system and works as a PC controlled TL Reader.

Built-in serial port facilitates connection to PC

Heating rates are 10c/sec to 400c/sec

Max. Set temperature 500oC.

Heating profile: Linear, Linear clamped.

Software features include glow curve, acquisition, display, filing, printing, processing
etc.
(ii) Hardware specifications
PMT housing and TL sample heating assembly: This unit has a photomultiplier
Tube generally of Hamamatsu / ET make, is used. However, assembly facilitates one
to go in for other photomultiplier tubes also with appropriate modification in the PMT
socket wiring. The cylindrical shell containing the Photomultiplier is fitted on to a
rectangular base drawer block containing a heater arrangement and thermocouple,
heater rods, connected to a power transformer.
Heating Arrangement: Resistive heating method.
Heating Element (Heater Strip): Kanthal strip (72% Fe, 23% Al and 2% Cr or
Nichrome) is used as a heating element. Kanthal Strip has a circular depression of
14mm to hold discs and powder samples.
Heating Process: Programmed heating can be done in two modes i) "PROG MODE"
of Temperature Controller through personal computer program. ii) "ISO MODE"
(Internal mode) of Temperature Controller, by varying the ten turn dial.
Temperature Sensor: Thermocouple Sensor (Cr-Al spot-welded to heater strip).
PMT Cooling: Thermoelectric cooling arrangement for the PMT is provided.
High voltage to PMT: A continuously adjustable HV (0 to -1500V) @1mA is
generated by HV circuits. User can select desired HV from front panel. There is HV
socket (test) for checking HV presence on rear panel.
Auto -Ranging: Current output from the photomultiplier is taken to I-F converter, to
give frequency output proportional to PMT current. This wide dynamic range is
achieved for plotting TL intensity on Y-axis
41

Fig.3.1 Thermoluminescence Reader Type TL1009

Fig. 3.2 Block Diagram of TL Set-up

42

Temperature range: From room temperature up to 500oC, in linear, linear clamped

mode of heating can be programmed.
Heating Rates: Heater strip can be programmed to heat the sample from 1oC/sec up
to 40oC/sec and a max set temperature (allowed) is 500oC.
Arrangement for Optical Filters: One Heat absorbing glass / filter (IR cutoff filter):
This is essentially an IR cut-off filter which allows only visible light and cuts- off IR
Radiation has been provided just below the PMT window. Additionally filters (Band
pass) if required by the user may be positioned above with IR filter.
Nitrogen Flushing Nozzle: Nitrogen gas flushing (sent through a flexible rubber
pipe), suppresses spurious luminescence from oxidation effects & combustion
phenomena has been provided.
Dimensions of Integral unit: 25.5W X 26ht. X 48D
(iii) Applications
TL Phosphor Characterization, Medical Dosimetry, Personal Monitoring Research,
Archeology dating, Environmental Radiation Monitoring, Medicine, Biology,
Neutron Dosimetry, Reactor Engineering, High Level Photon Dosimetry with TL
materials, standardisation and intercomparison of TL dosimeters used in personnel
monitoring etc.
(iv) Block diagram description
Now this block diagram as in figure-3.2, explains how this PC based digitalized glow
curve recording system has been realized. This system has a PMT housing & drawer
assembly with sample heater strip. This PMT housing with drawer assembly has PMT
arrangement for loading TL phosphor in any form such as powder, discs, micro-rod,
pellet chip etc., which is placed on the circular depression of a kanthal strip. There is a
heater transformer, which is provides current to the heater strip. Heater has
thermocouple spot-welded at the bottom of it. This thermocouple wire leads are taken
to the front side of drawer (just behind front handle), and is again pushed back
through a small hole along the sample drawer assembly.
High voltage unit HV 501(as indicated in the block diagram provides D.C. bias to the
PMT (typically about -700V is applied).Thermocouple output taken from the PMT
housing is connected to temperature controller unit TC575. This Temperature
controller unit amplifies the thermocouple output and temperature indication is
43

provided on the DPM of TC. Also parallel the TC output is sent to TL Acquisition
Module AM 576. Heating is controlled by the TL Acquisition Module as per the
parameter settings. TL Acquisition Module AM 576 reads temperature and TL
intensity (I-F) & displays them on LCD Alphanumeric display. DAC is programmed
to generate different heating profile for heating the sample. The printer attached to a
PC under software control provides plot-out of glow curve & printing of TL intensity,
temperature, glow curve analysis report etc.
3.3 POWDER X-RAY DIFFRACTOMETER
X-ray diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell
dimensions. The analyzed material is finely ground, homogenized, and average bulk
composition is determined [3].
To characterize the crystal structure of synthesized strontium pyrophosphate and the
doped samples, the powder X-ray diffraction (XRD) measurements were established.
For these measurements, Rigaku MiniFlex X-ray Diffractometer with a radiation
source of CuK was used [4,5].
Basics of X-ray Diffraction:
About 95% of all solid materials can be described as crystalline. When X-rays are
incident on a crystalline substance (Phase), one gets a diffraction pattern. In 1919
A.W.Hull gave a paper titled, A New Method of Chemical Analysis. Here he
pointed out that .every crystalline substance gives a pattern; the same substance
always gives the same pattern; and in a mixture of substances each produces its
pattern independently of the others.
The X-ray diffraction pattern of a pure substance is, therefore, like a fingerprint of the
substance. The powder diffraction method is thus ideally suited for characterization
and identification of polycrystalline phases [4,5,6]. The main use of powder
diffraction is to identify components in a sample by a search/match procedure.
Furthermore, the areas under the peak are related to the amount of each phase present
in the sample.
Theoretical Considerations
The atoms are arranged in a regular pattern, and there is a smallest volume element
that by repetition in three dimensions describes the crystal. This smallest volume
element is called a unit cell. The dimensions of the unit cell is described by three axes
a, b, c and the angles between them alpha, beta, gamma.
44

Fig. 3.3 Orientation and interplanar spacings of planes

Fig. 3.4 X Rays diffraction

45

An electron in an alternating electromagnetic field will oscillate with the same

frequency as the field. When an X-ray beam hits an atom, the electrons around the
atom start to oscillate with the same frequency as the incoming beam. In almost all
directions have destructive interference and there is no resultant energy leaving the
solid sample. However the atoms in a crystal are arranged in a regular pattern, and in
a very few directions have constructive interference. The waves will be in phase and
there will be well defined X-ray beams leaving the sample at various directions.
Hence, a diffracted beam may be described as a beam composed of a large number of
scattered rays mutually reinforcing one another.
This model is complex to handle mathematically. The orientation and interplanar
spacings of these planes are defined by the three integers h, k, l called indices. A
given set of planes with indices h, k, and l cut the a-axis of the unit cell in h sections,
the b- axis in k sections and the c- axis in l sections. A zero indicates that the planes
are parallel to the corresponding axis. Fig-3.3 shows planes cut the a- axis and the b
axis in half, but are parallel to the c- axis. If dimensional diffraction grating as a
mathematical model, the three indices h, k, l become the order of diffraction along the
unit cell axes a, b and c respectively. It should now be clear that, depending on what
mathematical model we have in mind, we use the terms X-ray reflection and X-ray
diffraction as synonyms. Let us consider an X-ray beam incident on a pair of parallel
planes P1 and P2, separated by an interplanar spacing d, shown in fig-3.4.
The two parallel incident rays 1 and 2 make an angle with these planes. A reflected
beam of maximum intensity will result if the waves represented by 1 and 2 are in
phase. The difference in path length between 1 to 1 and 2 to 2 must then be an
integral number of wavelengths, . We can express this relationship mathematically in
Braggs law [6,7].
2d sin = n
The process of reflection is described here in terms of incident and reflected (or
diffracted) rays, each making an angle with a fixed crystal plane. Reflections occur
from planes set at angle with respect to the incident beam and generates a reflected
beam at an angle 2 from the incident beam.

46

The possible d-spacing defined by the indices h, k, l are determined by the shape of
the unit cell. Rewriting Braggs law we get:
sin = /2d
Therefore the possible 2 values where we can have reflections are determined by the
unit cell dimensions. However, the intensities of the reflections are determined by the
distribution of the electrons in the unit cell. The highest electron density is found
around atoms. Therefore, the intensities depend on what kind of atoms we have and
where in the unit cell they are located. Planes going through areas with high electron
density will reflect strongly, planes with low electron density will give weak
intensities.
3.4 FOURIER TRANSFORM INFRARED SPECTROMETER
Fourier transform spectroscopy is a measurement technique where by spectra are
collected based on measurements of the coherence of a radiative source, using timedomain or space-domain measurements of the electromagnetic radiation or other type
of radiation[8]. It can be applied to a variety of types of spectroscopy including
optical spectroscopy, infrared spectroscopy (FTIR, FT-NIRS), nuclear magnetic
resonance.Fourier Transform Infrared Spectroscopy (FTIR) identifies chemical bonds
in a molecule by producing an infrared absorption spectrum. Thus, the presence of
specific functional groups can be monitored. The pellet samples for Fourier
Transform Infrared Spectrometer (FTIR) measurements prepared based on 100mg:
2mg sample to KBr ratio [9,10,11]. The produced samples were studied by VARIAN
1000 FTIR spectrometer and the wave numbers were set between 400 and 4000cm-1.
Infrared Spectroscopy: Infrared spectroscopy has been a workhorse technique for
material analysis in the laboratory for over seventy years. An infrared spectrum
represents a fingerprint of a sample with absorption peaks which correspond to the
frequencies of vibrations between the bonds of the atoms making up the material.
Because each different material is a unique combination of atoms, no two compounds
produce the exact same infrared spectrum. Therefore, infrared spectroscopy can result
in a positive identification (qualitative analysis) of every different kind of material. In
addition, the size of the peaks in the spectrum is a direct indication of the amount of
material present. With modern software algorithms, infrared is an excellent tool for
quantitative analysis.
47

Fig: 3.5

Fig: 3.6

48

Fourier Transform Infrared (FT-IR) 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 beamsplitter 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 beamsplitter. The two beams reflect off of their respective mirrors and
are recombined when they meet back at the beamsplitter. 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.

49

The Sample Analysis Process

The normal instrumental process is as follows:
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.
Because there needs to be a relative scale for the absorption intensity, a background
spectrum must also be measured. This is normally a measurement with no sample in
the beam. This can be compared to the measurement with the sample in the beam to
determine the percent transmittance. This technique results in a spectrum which has
all of the instrumental characteristics removed. Thus, all spectral features which are
present are strictly due to the sample. A single background measurement can be used
for many sample measurements because this spectrum is characteristic of the
instrument itself.
Advantages of FT-IR
Some of the major advantages of FT-IR over the dispersive technique include:
Speed: Because all of the frequencies are measured simultaneously, most
measurements by FT-IR are made in a matter of seconds rather than several minutes.
This is sometimes referred to as the Felgett Advantage.
Sensitivity: Sensitivity is dramatically improved with FT-IR for many reasons. The
detectors employed are much more sensitive, the optical throughput is much higher
(referred to as the Jacquinot Advantage) which results in much lower noise levels, and

50

the fast scans enable the coaddition of several scans in order to reduce the random
measurement noise to any desired level (referred to as signal averaging).
Mechanical Simplicity: The moving mirror in the interferometer is the only
continuously moving part in the instrument. Thus, there is very little possibility of
mechanical breakdown.
Internally Calibrated: These instruments employ a He-Ne laser as an internal
wavelength calibration standard (referred to as the Connes Advantage). These
instruments are self-calibrating and never need to be calibrated by the user.
These advantages, along with several others, make measurements made by FT-IR
extremely accurate and reproducible. Thus, it is a very reliable technique for positive
identification of virtually any sample. The sensitivity benefits enable identification of
even the smallest of contaminants. This makes FT-IR an invaluable tool for quality
control or quality assurance applications whether it is batch-to-batch comparisons to
quality standards or analysis of an unknown contaminant. In addition, the sensitivity
and accuracy of FT-IR detectors, along with a wide variety of software algorithms,
have dramatically increased the practical use of infrared for quantitative analysis.
Quantitative methods can be easily developed and calibrated and can be incorporated
into simple procedures for routine analysis. Thus, the Fourier Transform Infrared (FTIR) technique has brought significant practical advantages to infrared spectroscopy. It
has made possible the development of many new sampling techniques which were
designed to tackle challenging problems which were impossible by older technology.
It has made the use of infrared analysis virtually limitless.
3.5 THERMOGRAVIMETRIC ANALYZER (TGA)
Thermogravimetric analysis or thermal gravimetric analysis (TGA) is a type of testing
performed on samples that determines changes in weight in relation to change in
temperature. Such analysis relies on a high degree of precision in three measurements:
weight, temperature, and temperature change [12]. 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 identify the point where weight loss is
most apparent. Again, interpretation is limited without further modifications and
deconvolution of the overlapping peaks may be required.

51

Thermogravimetric curves (thermograms) provide information regarding polymerization reactions, the efficiencies of stabilizers and activators, the thermal stability of
final materials, and direct analysis.
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
identify the point where weight loss is most apparent. Again, interpretation is limited
without further modifications and deconvolution of the overlapping peaks may be
required.
TGA is commonly employed in research and testing to determine characteristics of
materials such as polymers, to determine degradation temperatures, absorbed moisture
content of materials, the level of inorganic and organic components in materials,
decomposition points of explosives, and solvent residues. It is also often used to
estimate the corrosion kinetics in high temperature oxidation.
The analyzer usually consists of a high-precision balance with a pan (generally
platinum) loaded with the sample. A different process using a quartz crystal
microbalance has been devised for measuring smaller samples on the order of a
microgram versus milligram with conventional TGA.The sample is placed in a small
electrically heated oven with a thermocouple to accurately measure the temperature.
The atmosphere may be purged with an inert gas to prevent oxidation or other
undesired reactions. A computer is used to control the instrument.
Analysis is carried out by raising the temperature of the sample gradually and plotting
weight (percentage) against temperature. The temperature in many testing methods
routinely reaches 1000C or greater. After the data are obtained, curve smoothing and
other operations may be done to find the exact points of inflection.
A method known as hi-resolution TGA is often employed to obtain greater accuracy
in areas where the derivative curve peaks. In this method, temperature increase slows
as weight loss increases. This is to more accurately identify the exact temperature
where a peak occurs. Several modern TGA devices can vent burnoff to an infrared
spectrophotometer to analyze composition.
52

THEORY
TGA is used primarily for determining thermal stability of polymers. The most widely
used TGA method is based on continuous measurement of weight on a sensitive
balance (called a thermobalance) as sample temperature is increased in air or in an
inert atmosphere. This is referred to as non-isothermal TGA. Data are recorded as a
thermogram of weight versus temperature. Weight loss may arise from evaporation of
residual moisture or solvent, but at higher temperatures it results from polymer
decomposition. Besides providing information on thermal stability, TGA may be used
to characterize polymers through loss of a known entity, such as HCl from poly (vinyl
chloride). Thus weight loss can be correlated with percent vinyl chloride in a
copolymer. TGA is also useful for determining volatilities of plasticizers and other
additives. Thermal stability studies are the major application of TGA. A variation of
the method is to record weight loss with time at a constant temperature, called
isothermal TGA, this is less commonly used than non-isothermal TGA. Modern TGA
instruments allow thermograms to be recorded on microgram quantities of
material.Some instruments are designed to record and process DSC and TGA data
simultaneously, and may also be adapted for gas chromatographic and/or mass
spectrometric analysis of effluent degradation products.
Advantages of using TGA for Materials Analysis
Thermogravimetric analysis uses heat to force reactions and physical changes in
materials. TGA provides quantitative measurement of mass change in materials
associated with transition and thermal degradation. TGA records change in mass from
dehydration, decomposition, and oxidation of a sample with time and temperature.
Characteristic thermogravimetric curves are given for specific materials and chemical
compounds due to unique sequence from physicochemical reactions occurring over
specific temperature ranges and heating rates. These unique characteristics are related
to the molecular structure of the sample. When used in combination with FTIR,
TGA/FTIR is capable of detailed FTIR analysis of evolved gases produced from the
TGA.

53

Fig; 3.7 a

Fig:3.7 b

Fig:3.7 c

54

TGA 50 Thermogravimetric Analyzer

The low mass balance mechanism, constructed of super light weight components is
engineered to withstand vibrations and to provide high sensitivity and low noise.
Furthermore, integrating this super light weight balance mechanism with the low mass
furnace minimizes the buoyancy, ensuring stable baselines.
Principle and Construction of the TGA-50
In Thermogravimetry (TG), the change in sample weight is measured while the
sample is heated or cooled at a constant rare. This technique is effective for
quantitative analysis of thermal reactions that are accompanied by mass changes, such
as evaporation, decomposition, gas absorption, desorption, and dehydration. The
change in sample mass affects the equilibrium of the balance. This imbalance is
feedback to the force coil, which generates additional electromagnetic force to recover
equilibrium. The amount of additional electromagnetic force is proportional to the
mass change.
3.6 LASER DIFFRACTION PARTICLE SIZE ANALYSER
Laser diffraction is the most widely used technique for particle size analysis.
Instruments employing this technique are considered easy to use and particularly
attractive for their capability to analyse over a broad size range in a variety of
dispersion media.
The Mie solution is named after its developer, German physicist Gustav Mie. Mie
theory, also called LorenzMie theory or LorenzMieDebye theory is an analytical
solution of Maxwell's equations for the scattering of electromagnetic radiation by
spherical particles (also called Mie scattering) [13]. For particles much larger or much
smaller than the wavelength of the scattered light there are simple and excellent
approximations that suffice to describe the behavior of the system. But for objects
whose size is similar to the wavelength (e.g., water droplets in the atmosphere, latex
particles in paint, droplets in emulsions including milk, and biological cells and
cellular components) this more exact approach is necessary.
The formalism allows the calculation of the electric and magnetic fields inside and
outside a spherical object and is generally used to calculate either how much light is
scattered, the total optical cross section, or where it goes, the form factor. The notable
55

features of these results are the Mie resonances, sizes that scatter particularly strongly
or weakly. This is in contrast to Rayleigh scattering for small particles and RayleighGans-Debye scattering for large particles [14]. The existence of resonances and other
features of Mie scattering, make it a particularly useful formalism when using
scattered light to measure particle size.
Using Mie Theory and the Fraunhofer Approximation
When setting up laser diffraction methods, users are faced with the decision as to
whether to use Mie Theory or the Fraunhofer Approximation to calculate the particle
size distribution results.
The Fraunhofer Approximation represents the easiest model to set-up as, in contrast to
Mie Theory, it does not require the user to provide any optical property information.
However, its use can lead to significant errors due to the assumptions it makes
regarding the nature of the materials being measured. As such, users need to consider
the following when selecting the Fraunhofer Model:

Particle Absorption: If the particles show some transparency (absorption < 0.2),
then the Fraunhofer approximation will tend to yield inaccurate results below
50m in size. If the absorption is high (>0.2), good results may be obtained down
to 2m in size, although this does depend on the refractive index.

Particle Refractive Index : If the refractive index different between the particle
and the medium which surrounds it is low, then the Fraunhofer model can shown
errors, even up to very large particle sizes (>200m).

Particle Size: If the particle size distribution contains material less than 2 microns
in size then the Fraunhofer Approximation will lead to an incorrect assessment of
the fine particle fraction.

The nature of the errors observed when using the Fraunhofer Approximation is not
always predictable. In most instances an over-estimation of the fine particle fraction is
observed, as shown here for a pharmaceutical material. However, it is also possible
for the Fraunhofer model to underestimate the fine particle fraction, as is seen for
materials such as calcium carbonate, because it incorrectly predicts the scattering
efficiency of these particles.
56

In the present investigation the Mastersizer Micro system, Version 2.19 was used to
find out the particle size (Figure 3.8). The following are the technical details.
Extensive market research and customer opinion directed the development of the
Mastersizer Micro systems. The result is a small footprint, low cost instrument that
takes laser diffraction out of the specialist laboratory and into the hands of particle
technologists everywhere. The Micro is an instrument system in the clear Malvern
tradition with no compromise on sample handling, Mastersizer Micro performs like a
research machine and yet operates like a cost effective QC tool. The wide measuring
range makes it ideal for application in fundamental studies and quality control of
production lines in diverse industries such as pharmaceuticals, mining, minerals, clays,
food, metal powders, emulsions, ceramics, polymers, pigments, paints and coatings to
name a few. The Block diagram of the detection system is in figure 3.9.
Easy Operation and Maintenance
Single button operation means that inexperienced users can perform repetitive
measurements easily and reproducibly. The stable single lens optics minimizes set up
and routine maintenance.
Rapid data acquisition and analysis allows repeatable measurements to be made in
less than 4 seconds. A unique "dip-in" probe provides sample agitation, sonication
and circulation through the measuring system. By allowing the use of standard
laboratory beakers as the sample tank, variable volumes of material can be analyzed.
Superior Software Complete Control: Malvern software sets an acknowledged
world-wide standard for instrument operation, data acquisition and handling,
reporting and systems integration.
Set up as easy as ABC: A special "ABC" icon guides the user through a set-up
routine ensuring that no parameters are over looked.

57

Fig: 3.8

Laser diffraction particle size analyzer

Fig: 3.9 Block Diagram of the Detection System

58

Mastersizer Micros Technical Specifications

Size Range

: Mastersizer Micro: 0.3um 300um

Mastersizer Microplus: 0.05um 550um

Measurement Principle

: Mie scatteringime

Measurement Time

: < 4 seconds typical user variable

Light Source

: He-Ne laser of wavelength 632.8nm

Accuracy

: 2.0% on Dv50 on Malvern reference standard

Power

: 100-240V, 50/60Hz

External Dimensions

: 500 (w) x 560 (h) x 325 (d) mm

Weight

: 32Kg

Refractive index in the present study is taken as 1.5.

Easy Mode: a "GO" button runs the complete measurement to pre-selected
requirements.
Report Generation: company logos, typestyles and formats can be incorporated into
printouts.
Flexible Data Processing: a range of data processing options are available allowing
the user to specify the graph format and scale.
Statistical Analysis: reproducibility of results and size trends can be reported using
built-in statistical analysis options.
Security Features: four password access levels are available from supervisor down
to a level for the infrequent or unskilled user.
Full Mie theory: full Mie theory matrix generator enables compliance with ISO13320.
Advanced features: Malvern BASIC a powerful set of programming tools enable the
user to customize measurement parameters.
Windows operation: all the benefits of the Windows operating system are available
to the Mastersizer user. A key feature is the ability to integrate particle size data by
"cutting and pasting" into other independent software packages.
Additional features for specific needs: For measurement of solvent based systems,
Malverns QSpec small volume sample dispersion unit can be used, and when only
very small amounts of material are available a direct injection small volume flow cell
is available.
Laser Diffraction: Laser diffraction particle size analysis is based on the
phenomenon that all particles scatter light at a range of angles, which is a
characteristic of their size. Large particles scatter at small angles and vice versa.
59

The Mastersizer Micro comprises a Helium-Neon laser as a light source, which

illuminates the dispersed particles in the measuring zone. This is then focused by a
Fourier lens to a detector, which consists of a large number of photosensitive elements
radiating outward from the centre. A novel property of a Fourier lens is that it collects
the scattered light from an ensemble of particles, and overlays the common angles of
scattering on the detector array. The intensity of the scattered light is measured and
using an optical model (Mie theory) to calculate the scattering

pattern and a

mathematical deconvolution procedure, a volumetric particle size distribution is

calculated that best matches the measured pattern. The Mastersizer Micro produces
volume-based measurements based on the measurement of ensembles of particles
sampled at a rate of 500 snaps per second, simultaneously from all detectors. This
means that the system is exceptionally suitable for the detection of rogue coarse
particles.
3.7INDUCTIONCOUPLEDPLASMAATOMICEMISSIONSPECTROSCOPY
Inductively coupled plasma atomic emission spectroscopy (ICP-AES), also referred to
as inductively coupled plasma optical emission spectrometry (ICP-OES), is an
analytical technique used for the detection of trace metals. It is a type of emission
spectroscopy that uses the inductively coupled plasma to produce excited atoms and
ions that emit electromagnetic radiation at wavelengths characteristic of a particular
element[15]. The intensity of this emission is indicative of the concentration of the
element within the sample.
Mechanism: The ICP-AES is composed of two parts: the ICP and the optical
spectrometer. The ICP torch consists of 3 concentric quartz glass tubes. The output or
"work" coil of the radio frequency (RF) generator surrounds part of this quartz torch.
Argon gas is typically used to create the plasma .When the torch is turned on, an
intense electromagnetic field is created within the coil by the high power radio
frequency signal flowing in the coil. This RF signal is created by the RF generator
which is, effectively, a high power radio transmitter driving the "work coil" the same
way a typical radio transmitter drives a transmitting antenna. The argon gas flowing
through the torch is ignited with a Tesla unit that creates a brief discharge arc through
the argon flow to initiate the ionization process. Once the plasma is "ignited", the
Tesla unit is turned off.
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Fig: 3.10 (a) ICP atomic emission spectrometer

Fig: 3.10 (b) ICP Plasma "torch"

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The argon gas is ionized in the intense electromagnetic field and flows in a particular
rotationally symmetrical pattern towards the magnetic field of the RF coil. A stable,
high temperature plasma of about 7000 K is then generated as the result of the
inelastic collisions created between the neutral argon atoms and the charged particles
[16,17].
Within the optical chamber(s), after the light is separated into its different
wavelengths (colours), the light intensity is measured with a photomultiplier tube or
tubes physically positioned to "view" the specific wavelength(s) for each element line
involved, or, inperistaltic pump delivers an aqueous or organic sample into a nebulizer
where it is atomized and introduced directly inside the plasma flame. The sample
immediately collides with the electrons and other charged ions in the plasma and is
broken down into charged ions. The various molecules break up into their respective
atoms which then lose electrons and recombine repeatedly in the plasma, giving off
radiation at the characteristic wavelengths of the elements involved.
In some designs, a shear gas, typically nitrogen or dry compressed air is used to 'cut'
the plasma flame at a specific spot. One or two transfer lenses are then used to focus
the emitted light on a diffraction grating where it is separated into its component
wavelengths in the optical spectrometer. In other designs, the plasma impinges
directly upon an optical interface which consists of an orifice from which a constant
flow of argon emerges, deflecting the plasma and providing cooling while allowing
the emitted light from the plasma to enter the optical chamber. Still other designs use
optical fibers to convey some of the light to separate optical cha more modern units,
the separated colours fall upon an array of semiconductor photo detectors such as
CCDs charge coupled devices. In units using these detector arrays, the intensities of
all wavelengths (within the system's range) can be measured simultaneously, allowing
the instrument to analyze for every element to which the unit is sensitive all at once.
Thus, samples can be analyzed very quickly. The intensity of each line is then
compared to previously measured intensities of known concentrations of the elements,
and their concentrations are then computed by interpolation along the calibration lines.
In addition, special software generally corrects for interferences caused by the
presence of different elements within a given sample matrix.
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Applications:
Examples of the application of ICP-AES include the determination of metals in wine,
arsenic in food, and trace elements bound to proteins. ICP-OES is widely used in
minerals processing to provide the data on grades of various streams, for the
construction of mass balances.
In 2008, the technique was used at Liverpool University to demonstrate that a ChiRho amulet found in Shepton Mallet and previously believed to be among the earliest
evidence of Christianity in England, only dated to the nineteenth century.
ICP-AES is often used for analysis of trace elements in soil, and it is for that reason it
is often used in forensics to ascertain the origin of soil samples found at crime scenes
or on victims etc. Taking one sample from a control and determining the metal
composition and taking the sample obtained from evidence and determine that metal
composition allows a comparison to be made. While soil evidence may not stand
alone in court it certainly strengthens other evidences.

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