1

PROJECT REPORT ON

OPTICAL STUDY OF CO-PRECIPITATED

CERIUM MOLYBDO IODATE AND CERIUM
MOLYBDO PHOSPHATE NANOPARTICLES

CHAPTER 1
NANOSTRUCTURED MATERIAL-A
BRIEF INTRODUCTION

1.1. Nanotechnology and Nanomaterials :

An introduction
The roots of Nanotechnology and Nanomaterials can be traced to a lecture
delivered by Richard Feymann(Nobel Laureate) in 1959 in a meeting of
American physical society, when he speculated this future scientists and
engineers would build structures from atoms and molecules(1). He gave a
talk, "There's Plenty of Room at the Bottom," at an American Physical Society
meeting at caltech. Nanotechnology shortened to "nanotech", is the study of
manipulating

matter

on

an

atomic

and

molecular

scale.

Generally,

nanotechnology deals with structures sized between 1 to 100 nanometre in

at least one dimension, and involves developing materials or devices
possessing at least one dimension within that size. Quantum mechanical
effects are very important at this scale, which is in the quantum realm.The

3
Greek word nano refers to a dimension ,one thousand times smaller than a
micron.

Richard Feymann

Although nanotechnology is a relatively recent development in

scientific research, the development of its central concepts happened over a
longer period of time. The emergence of nanotechnology in the 1980s was
caused by the convergence of experimental advances such as the invention
of

the scanning

tunneling

microscope in

1981

and

the

discovery

of fullerenes in 1985, with the elucidation and popularization of a conceptual.

framework for the goals of nanotechnology beginning with the 1986
publication of the book Engines of Creation.

4
The scanning tunneling microscope, an instrument for imaging surfaces at
the atomic level, was developed in 1981 by Gerd Binnig and Heinrich
Rohrer at IBM Zurich Research Laboratory, for which they received the Nobel
Prize in Physics in 1986. Fullerenes were discovered in 1985 by Harry
Kroto, Richard Smalley, and Robert Curl, who together won the 1996 Nobel
Prize in Chemistry.
Around the same time, K. Eric Drexler developed and popularized the
concept

of

nanotechnology

and

founded

the

field

of molecular

nanotechnology. In 1979, Drexler encountered Richard Feynman's 1959 talk

"There's Plenty of Room at the Bottom". The term "nanotechnology",
originally coined by Norio Taniguchiin 1974, was unknowingly appropriated
by Drexler in his 1986 book Engines of Creation:
One of the problems facing nanotechnology is the
confusion about its definition. Most definitions revolve around the study and
control of phenomena and materials at length scales below 100nm and quite
often they make a comparison with a human hair, which is about 80000nm
wide. There has been much debate on the future

implications of

nanotechnology. Nanotechnology has the potential to create many new

materials and devices with a vast range of applications, such as in
medicine,electronics and energy production.
Nanomaterials is a field that takes a materials science-based approach to
nanotechnology. It studies materials with morphological features on the
nanoscale, and especially those that have special properties stemming from
their nanoscale dimensions. Nanoscale is usually defined as smaller than a
one tenth of a micrometer in at least one dimension, [2 ] though this term is
sometimes also used for materials smaller than one micrometer.
Nanomaterials (nanocrystalline materials ) are materials possessing
grain sizes of the order of a billionth of ammeter.A nanocrystalline material

5
has grains of the order of 1-100 nm.The average size of an atom is of the
order of 1 to 2 Angstroms in radius. 1 nanometer comprises 10 Angstroms;
hence in one nm there may be 3 to 5 atoms,depending on their radii.
Nanocrystalline materials are exceptionally strong,hard, and ductile at high
temperatures,wear

resistant,corrosion

resistant,

erosion

resistant

&

chemically very active.

1.2. Classification of nanomaterials.

1.2.1. On the basis of dimension

Nanostructured materials are Classified into four
different

categories depending on their physical dimensions.

They are

a. Nanomaterials in zero dimension(clusters)

This is the recent type of the nanostructured materials. The zero
dimensional clusters are being investigated to tailor optical properties. Solgel
process has been commonly used to generated clusters.The typical method
of synthesis of the recent zero dimensional nanostructured materials are
the solgel process.They are also called quantum dots.
b. Nanomaterials in one dimension:
One dimensional nano structure has been called by a variety of
names

including

whiskers,fibres

or

fibrids,nanowires

or

nanorods.One

6
dimensional nanostructured materials there will be a layered structure or a
lamellar structure.Vapour deposition, sputtering techniques and electro
deposition techniques have been used to synthesize the one dimensional
layered nanostructured materials.The magnitude of length & width are much
greater than the thickness of the layered nanocrystals. Monolayers(layers
that are one atom or molecule) are also routinely mace & used in chemistry.
c. Nanomaterials in two dimension:
In this nanostructured materials synthesized are filamentary in
nature.The length substancially larger than the width or dimeter in
filamentary nanocrystals. Two dimensional nanomaterials includes tubes &
wires.Because of filamentary nature,this type of nanostructured materials is
referred to as two dimensional.The typical method of synthesis of

two

dimensional nanostructured material is chemical vapour deposition.(CVD)

Nanowires
Nanowires are ultrafine wires or linear arrays of dots,formed by self
assembly.They can be made from a wide range of materials.Semiconductor
Nanowires made of silicon,gallium nitride & indium phosphide have
demonstrated remarkable optical,electronic & magnetic characteristics.

d. Nanomaterials in three dimension

7
The nanostructured materials are basically in equiaxed in and are
hence called as nanocrystallites or three dimensional nanostructured.The
methods commonlyemployed to synthesis nanocrystalline phase in a variety
of

materials

are

gas

condensation,mechanical

alloying

&

chemical

precipitation and spray conversion prosessing technjques.

1) Nanoparticles.
Nanoparticles are sized between 1&100nms. Nanoprticles may
or may not exhibit size related properties that differ significantly from those
observed in fine particles or bulk materials.
Nanoclusters have atleast one dimension between 1&10nms and
anarrow size distribution.Nanopowders are agglomerates of ultrafine
Particles, nanoparticles or nanoclusters.Nanometer sized single crystals,or
single domain ultrafine particles are often referred to as nanocrystals .
Nanoparticles research is currently an area of intense scientific interest due
to a wide variety of potential applications in biomedical,optical & electronic
fields.
2) Fullerene
A fullerene is any molecule composed entirely of carbon, in the
form of ahollow sphere ,ellipsed,or tube.Spherical fullerenes are also called
Carbon nanotubes or buckytubes. Fullerenes are similar in structure to
graphite,which is composed of stacked graphine sheets of linked hexagonal
rings .

Fig.1.1

Fullerene

3) Den drimers
Den drimers are spherical polymeric molecules,formed
through a nanoscale ,hierarchial self assembly process.There are many types
of den drimers ; the smallest is several nanometers in size. Den drimers are
used inconventional applications such as coatings & links.
4) Quantum dots.
Nanoparticles of semiconductors(quantum dots) were
theorized in the 1970s and initially created in early 1980s.If semiconductors
particles are made small enough, quantum effects come into play ,which
limit the energies at which electrons & holes can exist in the particles.
Fig 1.2

Fig1.2. represents the schematic representation of the four different types

of nanostructured materials.

1.2.2 Phase composition

According to phase composition nanostructured materials are
classified into 3 groups.They are
Single phase solids

Crystalline ,amorphous particles &

Multi phase solids

Layers etc.
Matrix composites,coated particles

Multi phase systems

etc.
Colloids,aerogels,ferro fluids etc

Table 1.2.2.Classification based on phase composition.

1.2.3 Manufacturing process

Gas phase reaction

Flame

Liquid phase reaction

synthesis,condensation,CVD etc
Solgel,precipitation,hydrothermal

Mechanical procedures

processing etc.
Ball milling,plasyic deformation
etc

10
Table 1.2.3.Classification based on manufacturing process.

1.3. Properties of Nanostructured Materials

Owing to the very fine grain size, nanostructured materials exhibit a
variety of properties that are different and often considerably improved in
comparison with those of conventional coarser grained polycrystalline
materials.

If the size of the atomic ensemble becomes comparable to or

smaller than the typical length scale of a physical phenomenon, then the
spatial confinement can affect any property.

Some of the properties of

nanostructured materials are given below.

(a). Mechanical Properties

Elastic constants of nanocrytstalline materials have been reduced
considerably compared to those of bulk materials.

This is due to the

comparatively higher inter-atomic spacing in the boundary regions. The

strength of nanocrystalline material increases considerably than that of
coarse-grained material. Hardness also increases with decreasing grain size
in conventional coarser grained materials. This relationship is called HallPetch relationship5. For nanocrystalline materials hardness decreases with
decrease in grain size. It is referred to as inverse Hall-Petch effect. In some
grains, direct relationship between Youngs modulus and hardness has been
established. Reducing the grain size can lower the ductile/brittle transition
temperature.

The fracture stress of nanocrystalline material is lower than

that of conventional coarse-grained material.

Grain size and shape, their

11
distribution, pores and their distribution, surface condition, all affect the
mechanical behaviour of nanocrystalline materials.

(b).Thermal Properties
The thermal expansion coefficient of nanocrystalline material is greatly
enhanced due to the presence of large amount of grain boundaries.

The

specific heat of a material is closely related to the vibrational and

configurational entropy of the material, which is directly related to the
nearest neighbour configuration.

The specific heat in nanocrystalline

material is much higher than that in the coarser grained material. The
increase in specific heat in nanocrystalline material is art attributed to the
complicated structure of grain and phase boundaries. The enthalpy and
entropy of nanocrystalline material is very high.

(c). Electrical Properties

The electrical resistivity of nanocrystalline metal is higher than in both
coarse-grained polycrystalline metal and alloys.

The residual resistivity of

nanocrystalline metals of 00K decreases with an increase in grain size. If the

crystal size is smaller than the electron mean free path, grain boundary
scattering dominates and hence electrical resistivity as well as the
temperature coefficient is increased.

It has been shown that the AC

conducting of nanocrystalline TiO2 doped with about 1% Pt is reversible with

temperature.

The magnitude of electrical resistivity and hence the

conductivity in composites can be changed by altering the size of the

electrically conducting component.

(d). Magnetic Properties.

Magnetic Properties of nanocrystalline materials depend on the grain
size.

It was noted that with increasing grain size d, the coercivity H c

increases following d6 power law up to 50nm, runs through maximum of the

12
Hc 30A/cm and then decreases for grain sizes of about 50nm decoding to the
well known 1/d law for polycrystalline magnets.

Nanostructured materials

show a reduction in the saturation magnetization and ferromagnetic

transition temperature, due to the deviations of inter-atomic spacing in the
interfacial region.5
Nanocrystalline

iron

based

alloys

are

used

for

soft

magnetic

applications due to their specific characters like low coercivity, high

permeability, zero magnetostriction, low core losses due to high electrical
receptivity and good thermal stability.

Magnetic calorific effect is another

important magnetic property of nanocomposites 5. The magnetic property of

nanosized particle depends on the large surface to volume ratio. Unlike bulk
materials

consisting

of

multiple

magnetic

domains,

several

small

ferromagnetic particles can form single magnetic domains, giving rise to

supramagnetism. This behaviour opens the possibly for application in
information storage.

(e). Optical Properties

When the diameter of the nanostructured material is decreased,
discrete electronic energy states are formed. The exciton Bohr radius play
the central role in the optical properties of semiconductor nanostructures,
when the size of nanostructure component approaches the Bohr radius
electronic and optical absorption changes and the integrated absorption can
increase.

If the crystallite size of a nanocrystalline material becomes

comparable or smaller than de-Broglie wavelength of the charge carriers

generated by the absorbed light, the confinement increases energy required
for absorption.

This energy increase shifts the absorption/luminescence

spectra towards shorter wavelength (blue). The blue shift is a quantum size

13
effect.

Example: Blue shift is observed in the luminescence spectra of

nanocrystalline ZnO as a function of crystal size.

Controlling particle size can change optical properties of nanostructure
samples.

By controlling the cluster size of CdSe, Steigerwald and Burs

(1989) were able to synthesize clusters of very narrow size distributions and
show that they indicate varying degrees of quantum confinement and
different band gaps. Clusters of 1.2-1.5nm diameter have a band gap of 3eV
and those having diameter of 3.5nm have a band gap of 2.3eV while the bulk
material have a band gap of 1.8eV. Due to three dimensional confinements,
the mechanisms for resonant band edge optical non-linearities in nano
crystallites are different from those in bulk materials. Optical and infrared
absorption measurements have been performed for nano crystalline Si film
at different temperatures.

A pronounced red shift of the absorption was

noticed with increasing temperatures up to 350 0C. If deposition temperature

was increased to 4000C blue shift was observed which shows the relation
between crystal size and deposition temperature

1.4 Characteristic features of nanostructured

materials
In nanostructured materials, two types of atoms can be
distinguished crystal atoms and boundary atoms. Schematic representation
of hard sphere model of an equiaxed nanocrystalline metal is shown in
Figure 1.3. and two types of atoms can be distinguished, of these the first
one

contains

crystal

atoms

with

nearest

neighbor

configuration

corresponding to the lattice and boundary atoms with a variety of inter

14
atomic spacing differing from boundary to boundary. A nanocrystaline metal
contains a large number of interfaces (~6*1025m-3)with random orientation
relationships and consequently a substantial fraction of atoms lie in the
interfaces.

Assuming that grains have the shape of spheres or cubes the

volume fraction of the nanocrystaline materials associated with the boundary

can be calculated as 3 /d, where is the average grain boundary thickness
and d the average grain diameter. Thus the volume fraction of atoms in the
grain boundaries can be as much as 50% for 5nm grains and decrease to
about 30% for 10nm grains and 3% for 100nm grains.

Figure 1.3

1.5 Applications of nanotechnology

With nanotechnology, a large set of materials and improved products
rely on a change in the physical properties when the feature sizes are
shrunk. Nanoparticles, for example, take advantage of their dramatically
increased surface area to volume ratio. Their optical properties, e.g.
fluorescence, become a function of the particle diameter. When brought into
a bulk material, nanoparticles can strongly influence the mechanical
properties of the material, like stiffness or elasticity. For example, traditional
polymers can be reinforced by nanoparticles resulting in novel materials
which can be used as lightweight replacements for metals. Therefore, an
increasing societal benefit of such nanoparticles can be expected. Such

15
nanotechnologically enhanced materials will enable a weight reduction
accompanied by an increase in stability and improved functionality. There
are many applicatons of nanotechnology, few of them are show here.

a Tissue engineering
Nanotechnology can help to reproduce or to repair damaged tissue.
Tissue engineering makes use of artificially stimulated cell proliferation by
using suitable nanomaterial-based scaffolds and growth factors. Tissue
engineering might replace todays conventional treatments like organ
transplants or artificial implants. Advanced forms of tissue engineering may
lead to life extension.

b Chemistry and environment

Chemical catalysis and filtration techniques are two prominent
examples where nanotechnology already plays a role. The synthesis provides
novel materials with tailored features and chemical properties: for example,
nanoparticles with a distinct chemical surrounding (ligands), or specific
optical properties. In this sense, chemistry is indeed a basic nanoscience. In
a short-term perspective, chemistry will provide novel nanomaterials and
in the long run, superior processes such as self-assembly will enable
energy and time preserving strategies. In a sense, all chemical synthesis can
be understood in terms of nanotechnology, because of its ability to
manufacture

certain

molecules.

Thus,

chemistry

forms

base

for

nanotechnology providing tailor-made molecules, polymers, etcetera, as well

as clusters and nanoparticles.

c Catalysis
Chemical catalysis benfits especially from nanoparticles, due to the
extremely large surface to volume ratio.

The application potential of

nanoparticles in catalysis ranges from fuel cell to catalytic converters and

16
photocatalytic devices.

Catalysis is also important for the production of

chemicals.

d Medicine
The biological and medical research communities have exploited the
unique properties of nanomaterials for various applications. Terms such as
biomedical nanotechnology, nanobiotechnology, and nanomedicine are used
to describe this hybrid field. Functionalities can be added to nanomaterials
by interfacing them with biological molecules or structures. The size of
nanomaterials is similar to that of most biological molecules and structures;
therefore, nanomaterials can be useful for both in vivo and in vitro
biomedical

research

and

applications.

Thus

far,

the

integration

of

nanomaterials with biology has led to the development of diagnostic devices,

contrast agents, analytical tools, physical therapy applications, and drug
delivery vehicles.

e Filtration
A strong influence of nanochemistry on waste-water treatment, air
purification and energy storage devices is to be expected. Mechanical or
chemical methods can be used for effective filtration techniques. One class
of filtration techniques is based on the use of membranes with suitable hole
sizes, whereby the liquid is pressed through the membrane. Nanoporous
membranes are suitable for a mechanical filtration with extremely small
pores smaller than 10 nm (nanofiltration) and may be composed of
nanotubes. Nanofiltration is mainly used for the removal of ions or the
separation of different fluids. On a larger scale, the membrane filtration
technique is named ultrafiltration, which works down to between 10 and 100
nm. One important field of application for ultrafiltration is medical purposes
as can be found in renal dialysis. Magnetic nanoparticles offer an effective
and reliable method to remove heavy metal contaminants from waste water
by making use of magnetic separation techniques. Using nanoscale particles

17
increases the efficiency to absorb the contaminants and is comparatively
inexpensive compared to traditional precipitation and filtration methods6

f Information and communication

Current high-technology production processes are based on traditional
top down strategies, where nanotechnology has already been introduced
silently. The critical length scale of integrated circuits is already at the
nanoscale (50 nm and below) regarding the gate length of transistors in
CPUs or DRAM devices.

g Novel semiconductor devices

An example of such novel devices is based on spintronics.The
dependence of the resistance of a material (due to the spin of the electrons)
on an external field is called magnetoresistance. This effect can be
significantly amplified (GMR - Giant Magneto-Resistance) for nanosized
objects, for example when two ferromagnetic layers are separated by a
nonmagnetic layer, which is several nanometers thick (e.g. Co-Cu-Co). The
GMR effect has led to a strong increase in the data storage density of hard
disks and made the gigabyte range possible. The so called tunneling
magnetoresistance (TMR) is very similar to GMR and based on the spin
dependent tunneling of electrons through adjacent ferromagnetic layers.
Both GMR and TMR effects can be used to create a non-volatile main
memory for computers, such as the so called magnetic random access
memory or MRAM.
In 1999, the ultimate CMOS transistor developed at the Laboratory for
Electronics and Information Technology in Grenoble, France, tested the limits
of the principles of the MOSFET transistor with a diameter of 18 nm
(approximately 70 atoms placed side by side). This was almost one tenth the
size of the smallest industrial transistor in 2003 (130 nm in 2003, 90 nm in
2004, 65 nm in 2005 and 45 nm in 2007). It enabled the theoretical

18
integration of seven billion junctions on a 1 coin. However, the CMOS
transistor, which was created in 1999, was not a simple research experiment
to study how CMOS technology functions, but rather a demonstration of how
this technology functions now that we ourselves are getting ever closer to
working on a molecular scale. Today it would be impossible to master the
coordinated assembly of a large number of these transistors on a circuit and
it would also be impossible to create this on an industrial level7.

h Cosmetics
One field of application is in sunscreens. The traditional chemical UV
protection approach suffers from its poor long-term stability. A sunscreen
based on mineral nanoparticles such as titanium dioxide offer several
advantages. Titanium oxide nanoparticles have a comparable UV protection
property as the bulk material, but lose the cosmetically undesirable
whitening as the particle size is decreased.

i Energy
The most advanced nanotechnology projects related to energy are:
storage, conversion, manufacturing improvements by reducing materials and
process rates, energy saving and enhanced renewable energy sources.

j Reduction of energy consumption

A reduction of energy consumption can be reached by better insulation
systems, by the use of more efficient lighting or combustion systems, and by
use of lighter and stronger materials in the transportation sector. Currently
used light bulbs only convert approximately 5% of the electrical energy into
light. Nanotechnological approaches like light-emitting diodes (LEDs) or
quantum caged atoms (QCAs) could lead to a strong reduction of energy
consumption for illumination.

19

1.6 Present Work

Nanomaterials have fascinated scientific community in recent past.
Nanosized materials are those which have particles-organic, inorganic or
combinations that are of nanometer size. These materials exhibit unusual
properties

compared

to

their

bulk

counterparts.

The

synthesis

of

nanomaterials with uniform particle size is a subject of intensive research in

recent times because of their fundamental scientific interest as well as for
technological importance.
Acid salts of metals (TMA salts) are obtained in amorphous and
crystalline form.

These compounds have the general formula M(IV)

(HXO4)2nH2O where, M(IV)=Ce,Zr,Th,Ti etc X=P,Mo,W etc. The properties of

the -OH group of above materials can be exchanged for several cations and
thus these materials are termed inorganic ion exchangers.

A number of

cation can be exchanged with H+ due to which the material possess cation
exchange properties

depending on the stoitiometry of the reagent used,

temperature at which they are mixed, rate of addition, mode of mixing, P H

etc.

The resultant materials vary in water content, compostition and

crystallinity.

Literature shows that these materials are well studied in

crystalline and amorphous forms.

In the present work, nanoparticles of Cerium molybdoiodate and
Cerium molybdophosphate are synthesized by controlled chemical coprecipitation method using EDTA as the organic templating agent. The as
prepared samples are annealed at 5000C for 2 hours. The average crystalline

20
size of both samples are determined from X-ray diffraction line broadening
by using Scherrer equation. The surface morphology and chemical
composition of both samples are obtained from SEM with EDAX techniques.
The FTIR spectrum of both samples are recorded for determining the
different stretching and bending frequencies of molecular groups in the
samples.

1.7 Reference
1. (H Gleiter,prog.Mater.Sci.33(1988)223.)
2.Cristina Buzea, Ivan Pacheco, and Kevin Robbie (2007). Nanomaterials and
Nanoparticles: Sources and Toxicity.
3.N. Taniguchi (1974). On the Basic Concept of Nano-Technology.
Proc. Intl. Conf. Prod. London, Part II British Society of Precision Engineering.
4.Kahn, Jennifer (2006). "Nanotechnology". National Geographic 2006 (June):
98119.
5.Alivasatos A.P.Johnson K.P, Peng X, Wilson T E, Loweth C J, Schultz P G,
Nature, 382

(1996) 609.

6.Sergey P. Gubin (2009). Magnetic nanoparticles. Wiley-VCH.

21

CHAPTER-2
CHARACTERIZATION
TECHNIQUES

22

2.1. Introduction
The nanomaterials can be investigated and characterized using
different techniques like X-ray diffraction (XRD), UV-Visible Spectroscopy(UVVis),Infrared Spectroscopy(IR), Scanning Electron Microscopy(SEM), Tunneling
Electron Microscopy(TEM) etc. This chapter briefly describes the theory and
instrumentation of X-ray diffraction analysis, SEM with EDAX technique and
UV-visible Spectroscopy.

2.2. X-Ray Diffraction

2.2(a).Introduction
X-ray Diffraction (XRD) is one of the most versatile and widely
employed experimental techniques for the structural characterization of
crystalline materials

1-3

. X-ray diffraction pattern of the sample primarily give

information about the different crystalline phases present 4,5 . Therefore, the
first step after synthesizing the crystalline sample is to record its X-ray
diffraction pattern. X-ray diffraction is the most convenient indirect method

23
for the determination of average crystallite size of nanocrystalline samples
7

6-

2.2(b).Theory and Instrumentation

X-ray powder diffraction has been used in two main areas, for the
finger

print

characterization

of

determination of their structure.

crystalline

materials

and

for

the

Each crystalline solid has its unique

characteristic X-ray powder pattern, which may be used as a

finger

print for its identification. X-ray crystallography can also be used to

determine crystal structure. The measurement of crystalline size of a
polycrystalline specimens by means of X-ray is based on the broadening of
diffraction lines when the crystallite size is very fine i.e., less than 10 -7m 4,5 .
The broadening of diffraction peak can be used to determine the size of the
crystalline sample using the Scherrer equation.

t = 0.9*/hkl*Cos hkl

Scherrer equation is,

Braggs law is given by,

2dsin = n .. (1)
For first order diffraction,
2dsin = (2)
Multiplying both sides by an integer m such that md =t, thickness of the
crystal
2tsin =m .......... (3)
Eqn(2), can also be interpreted as the

m th order reflection from a set of

planes with interplanar distancet.

Differentiating both sides of (3), remembering m is a constant.
2tcos +2sin t =0 (4)

24
can be positive or negative. Considering magnitude only (4) leads to
t=tsin/ cos
Since the smallest increment in t is d, using t=d, and substituting /2 for
dsin [from (2)], we get
t= /2cos.. (5)

A
C

C
D

0
1
2

M
N

t=md
L

25
.

Figure :2.1
Let 1 = + , be the highest possible angle that can be got before
complete destructive interference and let 2= be lowest angle that can
be got before complete destructive interference. Now we can interpret 2
as the angular width of the X-ray diffraction line.
In the X-ray diffractometer what is recorded is the variation in
intensity of the diffraction lines with 2, so in the X-ray diffractogram we can
see diffracted X-rays over all scattering angles between 2 1and22.

If we

assume a triangular shape for the peak, the full width at half maximum
(FWHM) will be,

(21 - 22 ) /2

1-2
= ( + ) ( )

2 (6)

Imax
Intensity
Imax/2.

..

26

22

21

Figure:2.2
Diffraction from finite thickness crystal, substituting for 2 on (5), we get
t

/ Cos.. (7)

This is essentially the Scherrer equation.

A more rigorous treatment (using a Gaussian function, rather than a
triangular function) gives,
t

0.9 / Cos (8),

for

spherical

crystal of diameter t.
t

k* /hkl *Coshkl

Here,t is the average crystallite size normal to the reflecting planes ,k is the
shape factor, which lies between 0.95 and 1.15 depending upon the shape of
the grains in the wave length of X-ray used and hkl is the Full Width at Half
Maximum(FWHM) of the diffraction in radians and hkl is the Bragg angle
corresponding to the diffraction line arising from the planes designated by
the Miller indices(hkl)7. Knowing the wave length () of the X-ray and
analyzing the spectrum, the thicknesst of the crystalline sample can be
determined. The instrument for taking X-ray diffraction pattern is shown in
Figure:2.3.

27

Figure:2.3.Experimental set up for XRD

X-Ray diffractometer

28

2.3. Scanning Electron Microscope with EDAX

2.3.1. Introduction
SEM stands for scanning electron microscope.

The SEM is a

microscope that uses electrons instead of light to form an image. Since their
development in the early 1950's, scanning electron microscopes have
developed new areas of study in the medical and physical science
communities. The SEM has allowed researchers to examine a much bigger
variety of specimens.
The

scanning

electron

microscope

has

many

advantages

over

traditional microscopes. The SEM has a large depth of field, which allows
more of a specimen to be in focus at one time. The SEM also has much
higher resolution, so closely spaced specimens can be magnified at much
higher levels. Because the SEM uses electromagnets rather than lenses, the
researcher has much more control in the degree of magnification. All of
these advantages, as well as the actual strikingly clear images, make the
scanning electron microscope one of the most useful instruments in research
today.

29
Figure:2.4
Morphological studies of the samples are done using scanning electron
microscopy. SEM is a very efficient tool to study the surface textures of
materials. Here the surface of the sample is irradiated with a beam of
accelerated electrons. Since electrons have shorter wavelengths compared
to photons, the resolution obtained in SEM is very high compared to that in
conventional optical microscopy. Furthermore, the depth of focus in SEM is
much greater than that achieved in optical microscopy. In addition to the
above two factors, it has the advantage of greater magnifying power and
hence SEM has become a very powerful technique to explore the free
surfaces of materials. The energy dispersive spectrum of the sample are also
shown along with the SEM image.
The SEM is an instrument that produces a largely magnified image by
using electrons instead of light to form an image. A beam of electrons is
produced at the top of the microscope by an electron gun. The electron
beam follows a vertical path through the microscope, which is held within a
vacuum. The beam travels through electromagnetic fields and lenses, which
focus the beam down toward the sample. Once the beam hits the sample,
electrons and X-rays are ejected from the sample.

Figure:2.5

30
Detectors collect these X-rays, backscattered electrons, and secondary
electrons and convert them into a signal that is sent to a screen similar to a
television screen. This produces the final image.

2.3.2.Instrumentation:

Figure:2.6
SEM opened sample chamber
The SEM micrographs of our samples are obtained with a Hitachi Model
S-3000H electron microscope. The electron beam is focused on selected
areas of the samples according to the requirements and at different
magnification. The kinetic energy acquired by electrons in an electron
column, when they are accelerated through an electric field, is transferred to
the sample and its dissipation yields a variety of signals available for analysis
of electron from the highest occupied molecular orbital to the lowest
available unfilled molecular orbital. In most of the cases, several transitions
occur resulting in the formation of several bands.

31
The most important property of a semiconductor nanostructure is its
optical behavior to crystallite size. Optical properties may be absorption, spectral
response,

photoluminescence,

photoluminescence

excitation,

electroluminescence and Raman scattering whose optical properties respond

to crystalline size. As the size is decreased, the electronic states are
discretized and results in widening of the band gap and increases the
oscillator strength. The radiative recombination life time of carrier is lowered
from nanosecond to picoseconds. These features known as quantum size
effect (QSE) are observed in semiconductor nanocrystals.

2.4. Fourier Transform Infrared Spectroscopy

2.4.1. Introduction
Spectroscopy is the study of interaction of electromagnetic radiation
with matter. Infrared Spectroscopy is one of the most powerful analytical
techniques which offer the possibility of chemical identification. One of the
most important advantages of IR spectroscopy over the other usual methods
of structural analysis is that it provides useful information about the structure
of molecule quickly.

This technique is based on the fact that a chemical

substance shows selective absorption in the infrared region. After absorption

of IR radiation, the molecule of a chemical substance vibrate at many rate of
vibration giving rise to packed absorption band, called IR absorption spectra.
Various bands will correspond to the characteristic functional groups and
bond present in a chemical substance. Thus an IR spectrum of a chemical
substance is fingerprint for its identification.
A molecule absorbs radiation only when the natural frequency of
vibration of some part of a molecule is the same as the frequency of the
radiation. The molecules vibrate at increased amplitude. This occurs at the
expense of the energy of IR radiation which has been absorbed. In Infra-red
spectroscopy, the absorbed energy brings about predominant changes in the
vibrational energy which depend upon:

32
(a) Mass of the atom present in the molecule
(b) Strength of the bond
(c) The arrangement of atom within the molecule.
It has been found that no two compounds except the enantiomers can
have similar Infra-red spectra.

When infra-red light is passed through

sample, the vibrational and rotational energies of the molecule are

increased. Two types of fundamental vibrations are stretching and bending.
In stretching vibrations, the distance between the two atoms increases or
decreases but the atom remain in the same bond axis.

But in bending

vibrations the position of atoms changes with respect to the original bond
axis. There are two types of stretching vibrations. Also there are four types
of bending vibrations- scissoring, rocking, wagging and twisting.
Another condition for a molecule to absorb IR radiation is its electric
dipole. A molecule can only absorb IR radiation when its absorption causes a
change in its electric dipole. A molecule is said to have an electric dipole,
when there is a slight positive charge and a slight negative charge on its
component atoms.

2.4.2. Instrumentation
The apparatus for measuring infrared spectra is different from that for
visible and ultraviolet regions because the optical materials like glass and
quartz absorb strongly in the infrared region.

The main parts of an IR

spectrometer are as follows.10

a
b
c
d

The IR radiation source.

The monochromators.
The sample cells and sampling of substances.
Detectors.

33

Figure: 2.7
(a) The IR radiation source
The various popular sources of IR radiations are,
i

Incandescent lamp
In the near infrared instruments an ordinary incandescent lamp is

generally used, which fails in the far infrared.

ii Nernst glower
It consist of a hollow rod which is about 2mm in diameter and 30mm in
length, which is non conducting at room temperature and must be heated by
external means to bring it to a conducting state. The main disadvantage of
Nernst glower is that it emit IR radiation over wide wavelength range, the
intensity of radiation constant over long period of time.
iii Glower source
It is a rod of sintered silicon carbide which is about 50mm in
length and 4mm in diameter.

Unlike the Nernst glower it is self

starting and more satisfactory. The main disadvantage is that it is a

less intense source than the Nernst glower.

34
(iv) Mercury arc
It is used in far infrared instrument.

(b) Monochromator
The radiation source emits radiation of various frequencies as the sampling
electrons absorbs at certain frequency. It is necessary to select desired
frequency from the radiation source.

This selection is advised by

monochromators, which are mainly of two types, prism monochromator and

grating monochromator.

(c) Sample cells and sampling of substances

Sample can be solid, liquid or gas. But it should be contained in a cell
transparent to IR radiation. Sample cells are usually made of alkali metal
halides such as sodium chloride, potassium bromide etc.
Sampling of solids
Four techniques are generally employed for preparing solid samples.
These are:
Solid run in solution
If the solution of solid can be prepared in a suitable solvent then the
solution is run in one of the cells for liquids. But this method cannot be used
for all solids because suitable solvent are limited in number and there is no
single solvent which is transparent throughout the IR region.
(ii) Solid films
If the solid is amorphous in nature, the sample is deposited on the
surface of KBr or NaCl cell by evaporation of a solution of the solid.
iv Mull technique
In this technique, the finely ground solid sample is mixed with nujol
(mineral oil) to make a thick paste which is then made to spread between IR
transmitting windows. When IR spectrum of a solid sample is taken in nujol
mull, absorption bands of the sample that happen to coincide with the
absorption band of the nujol mull will be hidden, but others will be clearly

35
seen in the IR spectrum. This method is good for qualitative analysis but not
for quantitative analysis.
v Pressed Pellet technique
In this technique a small amount of finely ground solid sample is
intimately mixed with about 100 times its weight of powdered potassium
bromide. The finely ground mixture is then passed under very high pressure
in a press to form a small pellet (about 1-2mm thick and 1cm in diameter).
The resulting pellet is transparent to IR radiation and is run as such.
Advantages
1 KBr pellets can be stored for long period of time.
2 As the concentration of the sample can be suitably adjusted in the
pellets, it can be used for quantitative analysis.
3 The resolution of the spectrum in the KBr is superior to that obtained
with mulls.
Disadvantages
1 The high pressure involved during the formation of pellets may bring
about polymorphic

changes in crystallinity in the samples, which may

cause complication in IR spectrum.

2 This method is not successful for some polymers which are difficult to
grind with KBr.
From the above discussion we knows that one may employ the Nujol
method for running crystalline compounds in the solid and may reserve the
KBr pellet method for remaining solid samples.

d Detectors
Two main types are in common use, one sensing the heating effect of
radiation, the other depending up on photoconductivity. In the near infrared
region photoconductivity cell is generally used that is the radiation is
allowed to fall on photo conducting material and conductivity of material
measured continuously by a bridge network.

Usual IR detectors are

thermocouple, thermisters, golay cell, photoconductivity cell, bolo meters

etc.

36

2.5. References
1. J S Blackmore, in Solid state Physics, Second Edition, Cambridge University
Press, Cambridge (1985).
2. J P Srivasthava, in Elements of Solid State physics-Prentice-Hall India, New
Delhi (2001).
3. C.Kittel, Introduction to solid state physics, Seventh Edition, John Wiley &
Sons Inc., Singapore (1995).
4. N F M Henry, H Lipson and W A bWooster, in Interpretation of X-ray
diffraction Photographs, Mac Milan & Co Ltd., London (1961).
5. B D Cullity, in Elements of X-ray diffraction, I Edition, Addison-Wesley
Company, Inc., Massachusetts (1978).
6. Suryanarayana C., Bull.Mat.Sci. 17 (1994) 307.
7. A Cervellnio, C Giannini, A Guagliardi and M Ladisa, Phy.Rev.B.72 (2005)
035412. (Electronic version).
8. R Jamutowski,J.R.Ferraro, and D.C Lanski, Spectroscopy,7(1992) 22;
I.R, Altemose, J.Chem.Educ, 63 (1986) A216, A262.

9. Skoog, Holler and Nieman, in Principles of Instrumental Analysis, Fifth

edition.

37
10. G.Aruldhas, Molecular Structure and Spectroscopy, II (2007)198-200.

CHAPTER-3
SYNTHESIS AND CHARACTERIZATION
OF NANOCRYSTALLINE CERIUM
MOLYBDOIODATE AND CERIUM
MOLYBDOPHOSPHATE SAMPLES

38

3.1. Introduction
Chemistry has played a major role in developing the materials with
new and technologically important properties. The advantage of chemical
synthesis is its versatility in designing and synthesizing new materials that
can be refined into final products. The primary advantage is that chemical
methods offers mixing at molecular level. However the benefits of employing
simple

and

recognized

cost
and

effective
appreciated

chemical
1-5

.The

processing

methods

properties

and

are

widely

application

of

nanoparticles are largely dependent on their size, shape and textures 6.

Considerable attention has been drawn towards the size and shape
controlled synthesis of nanostructured materials

1-3

. Depending upon the

specific requirements such as material to be synthesized, the grain size and

maximum permissible size distribution, purity of sample required, quality of
sample generated etc., different methods are employed for synthesizing
nanophase materials. In the present study, nanocrystalline cerium molybdate
and cerium molybdoiodate were synthesized through controlled chemical
precipitation method.

3.2. Sample preparation and Experimental

Procedure
Nanoparticles of Cerium Molybdoiodate were prepared by controlled coprecipitation method using analytical grade chemicals. Sodium Molybdate,
Pottasium Iodate and Ammonium ceric sulphate were used as the starting
materials. EDTA was used as the stabilizer. Aqueous solutions of Sodium

39
Molybdate (0.1M, 50 ml) Ammonium ceric sulphate (0.1M, 50ml) Pottasium
iodate (0.1M, 50ml) and EDTA(0.0125M, 50 ml) were slowly mixed drop wise
into

a conical flask

and it is stirred well using a magnetic stirrer . This

process is to be done in one hour. The stabilizer EDTA was used to prevent
growth and agglomeration of the particles. In this process the particle size is
governed by the experimental parameters like concentration of the
reactants, rate of mixing, pH, Viscosity of the solutions etc 7. It is important to
note that the stabilizers used for controlling the precipitation reaction should
be easily and completely removable from the sample so as to avoid any
possible contamination of the samples.The metal molybdoiodate precipitate
formed was washed several times in distilled water to free it from ions and
other

impurities.

The

wet

precipitate

obtained

was

dried

at

room

temperature and thoroughly ground using an agate motor to obtain the

Cerium Molybdoiodate precursor in the form of a fine powder. The Cerium
Molybdoiodte precursor material was treated with 1N HCl.The acid treated
Cerium Molybdoiodate precursor was annealed at 500 oC

for 2 hours to

prepare nanoparticles of Cerium Molybdoiodate.

Nanoparticles of Cerium Molybdophosphate were prepared by controlled coprecipitation method using analytical grade chemicals. Sodium Molybdate,
Disodium hydrogen otho phosphate and Ammonium ceric sulphate were
used as the starting materials. EDTA was used as the stabilizer. Aqueous
solutions of Sodium Molybdate (0.1M, 50 ml) Ammonium ceric sulphate
(0.1M, 50ml) , Disodium hydrogen othophosphate (0.1M, 50ml) and
EDTA(0.0125M, 50 ml) were slowly mixed drop wise into a conical flask and
it is stirred well using a magnetic stirrer . This process is to be done in one
hour.The Cerium Molybdophosphate precursor material was treated with 1N
HCl.The acid treated Cerium Molybdophosphate precursor was annealed
500oC for 2 hours to prepare nanoparticles of Cerium Molybdophosphate.
The sample code was assigned to the four samples along with
annealing temperature and duration of annealing is shown in Table.3.1.

40

Table.3.1

3.3.

Sample

Annealing

Duration of

code

Temperature

annealing

CMI

CMI 500

500oC

2hrs

CMP

CMP 500

500oC

2hrs

Recording of X-ray Diffraction pattern

The X-ray diffraction pattern of the samples CMI,CMI 500,CMP and CMP
500

were

recorded

using

XPERT-PRO

powder

diffractometer

analytical, Netherlands) employing Cu- K radiation .

In tensity(Arb.U nits)

Fitted curve

CMI

200

150

100

50

10

20

30

40

50

60

70

80

90

Figure.3. 1 XRD pattern of CMI

Measurement Conditions:
Dataset Name

CMI 500

(PAN

41
File name
C:\X'Pert Data\general\S N College\CMI 500.xrdml
Comment
Configuration=Flat Sample Stage, Owner=User-1,
Creation date=10/9/2008 2:19:33 PM
Goniometer=PW3050/60 (Theta/Theta); Minimum
step size 2Theta:0.001; Minimum step size Omega:0.001
Sample stage=PW3071/xx Bracket
Diffractometer system=XPERT-PRO
Measurement program=General 10-90,
Owner=User-1, Creation date=4/2/2009 12:03:19 PM
Measurement Date / Time
8/17/2011 3:11:11 PM
Operator
NIIST
Raw Data Origin
XRD measurement (*.XRDML)
Scan Axis
Gonio
Start Position [2Th.]
10.0194
End Position [2Th.]
89.9874
Step Size [2Th.]
0.0170
Scan Step Time [s]
10.3371
Scan Type
Continuous
PSD Mode
Scanning
PSD Length [2Th.]
2.12
Offset [2Th.]
0.0000
Divergence Slit Type
Fixed
Divergence Slit Size [] 0.4354
Specimen Length [mm] 10.00
Measurement Temperature [C]
25.00
Anode Material
Cu
K-Alpha1 []
1.54060
Generator Settings
30 mA, 40 kV
Diffractometer Type
0000000011045531
Diffractometer Number 0
Goniometer Radius [mm]
240.00
Dist. Focus-Diverg. Slit [mm] 100.00
Incident Beam Monochromator
No
Spinning
No

42

Counts
CMI 500

80

60

40

20

0
20

30

40

50

60

70

80

Position [2Theta] (Copper (Cu))

Figure.3. 2.XRD pattern of CMI 500

Peak List:
Pos.
[2Th.]
28.2372
56.3435
74.7780

Height
[cts]
47.68
6.66
7.86

FWHM
[2Th.]
0.4080
0.9792
0.2040

d-spacing
[]
3.15787
1.63159
1.26856

Rel. Int.
[%]
100.00
13.97
16.48

43

Experimental data

CMP

14

Intensity(Arb.Units)

12
10
8
6
4
2
0
0

20

40

60

80

100

Figure.3. 3.XRD pattern of CMP

Measurement Conditions:
Dataset Name
CMP 500
File name
C:\X'Pert Data\general\S N College\CMP 500.xrdml
Comment
Configuration=Flat Sample Stage, Owner=User-1,
Creation date=10/9/2008 2:19:33 PM
Goniometer=PW3050/60 (Theta/Theta); Minimum
step size 2Theta:0.001; Minimum step size Omega:0.001
Sample stage=PW3071/xx Bracket
Diffractometer system=XPERT-PRO
Measurement program=General 10-90,
Owner=User-1, Creation date=4/2/2009 12:03:19 PM
Measurement Date / Time
8/17/2011 3:26:46 PM
Operator
NIIST
Raw Data Origin
XRD measurement (*.XRDML)
Scan Axis
Gonio
Start Position [2Th.]
10.0194
End Position [2Th.]
89.9874
Step Size [2Th.]
0.0170
Scan Step Time [s]
10.3371
Scan Type
Continuous
PSD Mode
Scanning

44
PSD Length [2Th.]
2.12
Offset [2Th.]
0.0000
Divergence Slit Type
Fixed
Divergence Slit Size [] 0.4354
Specimen Length [mm] 10.00
Measurement Temperature [C]
25.00
Anode Material
Cu
K-Alpha1 []
1.54060
Generator Settings
30 mA, 40 kV
Diffractometer Type
0000000011045531
Diffractometer Number 0
Goniometer Radius [mm]
240.00
Dist. Focus-Diverg. Slit [mm] 100.00
Incident Beam Monochromator
No
Spinning
No

Counts
CMP 500

60

40

20

20

30

40

50

60

70

80

Position [2Theta] (Copper (Cu))

Figure.3. 4.XRD pattern of CMP 500

Peak List:
Pos.
[2Th.]
25.1729
28.8952
31.3014
41.9456
48.1860

Height
[cts]
9.12
33.49
37.84
17.84
17.00

FWHM
[2Th.]
0.9792
1.1424
0.4896
0.6528
0.6528

d-spacing
[]
3.53490
3.08744
2.85537
2.15213
1.88697

Rel. Int.
[%]
24.10
88.51
100.00
47.14
44.93

45

3.4. DETERMINATION OF AVERAGE

CRYSTALLITE SIZE USING SCHERRER
EQUATION
In this section, the average crystallite size of sample CMI 500
CMP 500 are determined from

and

X-ray diffraction line broadening, without

taking instrumental correction to line broadening. Scherrer equation is the

simplest method of determining the average size of nanocrystalline samples
from X-ray diffraction line broadening.
Scherrer equation8 is,
t = k/ (hkl) measured*cos hkl
Here, t -is the average crystallite size normal to the reflecting planes, k- is
the shape factor which lies between 0.95 and 1.15 depending on the shape
of the grains (k=1 for spherical crystallites), -is the wavelength of X-ray
used and (hkl) measured is the measured FWHM of the diffraction line in radians
and hkl is the Bragg angle corresponding to the diffraction line arising from
the planes designated by Miller indices (hkl).9

Table :3.2. Average crystallite size of CMI 500 determined using Scherrer
equation
2

28.2372

hkl
0.408

14.1186
56.3435

0.9792
28.17175

74.778

0.204
37.389

Crystallite
Size(nm)
2.00773E08
9.20306E09
4.9012E08

Average
Crystallite
Size(nm)

26.0974

46

Table :3.3. Average crystallite size of CMP 500 determined using Scherrer
equation
2

25.1729

hkl
0.9792

12.58645
28.8952

1.1424
14.4476

31.3014

0.4896
15.6507

41.9456

0.6528
20.9728

48.186

0.6528
24.093

Crystallite
Size(nm)
8.3126E09
7.18094E09
1.68504E08
1.30327E08
1.33305E08

Average
Crystallite
Size(nm)

11.7414

RESULTS AND DISCUSSION

The XRD pattern of the samples of both CMI and CMP shows no welldefined peaks, reveals the particles synthesized was amorphous in nature.
The annealed samples of both materials show some well-defined peaks in
the XRD pattern, confirms the crystalline nature of the samples.

The

average crystallite sizes of CMI 500 and CMP 500 were calculated from Xray diffraction line broadening using Scherrer equation. The average
crystallite size obtained for Cerium molybdoiodate heated at 5000C for2
hours(CMI 500) is 26.0974 nm and that for Cerium molybdophosphate
heated at 5000C for 2 hours(CMP 500) is 11.7414 nm.

47

3.5. SEM images with EDAX

The surface morphology of the powder samples was characterized by
scanning electron microscope (SEM) JEOL/EO JSM-6390. The energy
dispersive analysis of X- rays (EDAX) was carried out on the samples to
ascertain the chemical composition.

3.5.1. SEM image of CMI

Figure.3.5

3.5.2.

SEM image of CMP

48
Figure.3.6

3.5.3. EDAX of CMI

Figure.3.7

3.5.3.

EDAX of CMP

49

Figure.3.8
RESULTS AND DISCUSSION
The SEM image of the CMI and CMP are reproduced in Figure: 3.5 &
3.6. The morphology obtained from the SEM image indicates that
nanoparticles are agglomerated to spherical shape. The EDAX spectrum of
the sample CMI and CMP are shown in Figure: 3.7 & 3.8. From the
figure, it is clear that the prepared sample contain no other impurities.
The SEM with EDAX spectrum of CMI contains elements such as Ce, Mo,
I and O but CMP contains elements such as Ce, Mo, O, and P.

3.6.RECORDING OF FTIR SPECTRUM OF THE

SAMPLES
The infrared spectroscopic (IR) studies of the samples

CMI,CMI

500,CMP and CMP 500 were maderecorded using Perkin- Elmer FTIR
Spectro Photo Meter in the wavenumber range 500 and 4000cm-1 by KBr
disc method.

50

100
90

60

99 6. 67

14 46 .0 8

70

14 07 .2 9

80

40 4. 85

-10
4000

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

Figure.3.9.FTIR SPECTRUM OF CMI

100
90

80

1623.19

70

60

%T

50

606. 17

30

1137.38

3402.86

40

20

838. 90

10

0
-10
4000

3500

3000

2500

2000
Wavenumbers (cm-1)

1500

1000

500

41 9. 95

33 98 .0 4

10

54 3. 20
48 2. 15

20

80 9. 61

10 79 .3 5

30

11 81 .0 5

40

13 35 .7 5

16 12 .7 1

%T

50

51

Figure.3.10.FTIR SPECTRUM OF CMI 500

1 00

14 01.76

90

40

Figure.3.11.FTIR SPECTRUM OF CMP

10

100
0

6 1 5 .1 1

10 51.24

20

5 4 0 .4 5

34 27.22

30

7 9 9 .6 3

%T

29 25.76

50

16 25.57

60

4 0 3 .3 1

70

14 52.28

23 62.23

80

90
-1 0
4 000

3 500

3 00 0

2 500

80

2 000

1 500

1 000

W ave num bers (c m -1 )

1626.17

70

60

%T

50

949.49

20

537.95

30

848.42

3407.61

40

614.80

561.83

1047.26

10

-10
4000

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

Figure.3.12.FTIR SPECTRUM OF CMP 500

5 00

52

RESULTS AND DISCUSSION

The FTIR spectrum of samples CMI and CMI 500 was reproduced in
Figures.3.8 & 3.9.
The broad absorption bands in the region 3398cm-1 ,1612 cm-1, 3402cm-1
& 1623 cm-1 is due to the valance vibration of occluded/ entrapped water 10.
The bands around 809 cm-1,543 cm-1,482 cm-1 ,
410 cm-1,838 cm-1 and 606 cm-1 corresponds to the intrinsic stretching
vibration of the metal with oxygen atoms 11.The additional weak bands and
shoulders

inthe spectrum due to the microstructural formation of the

samples.
The FTIR spectrum of samples CMP and CMP 500 was reproduced in
Figures.3.11 & 3.12.
The broad absorption bands in the region 3427cm-1 ,1625cm-1, 3407cm-1 &
1626 cm-1 is due to the valance vibration of occluded/ entrapped water 10.
The bands around 815 cm-1,799cm-1,540 cm-1 ,848 cm-1,614cm-1 , 561cm1

and 537 cm-1 corresponds to the intrinsic stretching vibration of the metal

with oxygen atoms11.The additional weak bands and shoulders

inthe

spectrum due to the microstructural formation of the samples.

3.7.Conclusion
Nanoparticles of Cerium molybdoiodate and Cerium molybdophosphate
were prepared by the chemical co-precipitation method using EDTA as the
organic templating agent. The as prepared samples was annealed at 5000C
for two hours. The XRD pattern of the samples of both CMI and CMP
shows no well-defined peaks, reveals the particles synthesized was
amorphous in nature. The annealed samples of both materials show some
well-defined peaks in the XRD pattern, confirms the crystalline nature of the

53
samples.

The average crystallite sizes of CMI 500 and CMP 500 were

calculated from X-ray diffraction line broadening using Scherrer equation.

The average crystallite size of CMI 500 is 26.0974 nm and that for CMP
500 is 11.7414 nm. The SEM with EDAX spectrum of CMI contains
elements such as Ce, Mo, O and I but , SEM with EDAX spectrum CMP
contains elements such as Ce, Mo, P and O. From the SEM image of both
samples reveals that the particles are agglomerated into spherical shapes
and the as prepared samples of CMand CMI contains no other impurities.
The FTIR Spectrum of CMI,CMI 500,CMP & CMP 500 were recored and
the bands were identified.

3.8.

Reference

1.

H Gleiter, Prog.Mater.Sci.33 (1989)223.

2.

H Gleiter, Adv.Mater (1992)474.

3.

C Suryanarayana, Bull.Mater.17 (1994)307.

4.

M Mofitt, H Vali and A Einsenberg, Che.Mater.10 (1998)1021.

5.
6.

L Brus, J.Phys.Che.Solids.59 (1998) 459.

Ying Zhang, Yu Fang, Shan Wang, Shuya Lin, J.Cis.Elsevier, 272(2004),

321-325.
7.

P.Pramanik, Bull.Mater.Sci.18 (1995)819.

8.
Harol P Klung and Leroy Alexander, X-ray Powder Diffraction Procedure
(John Wiley and
Sons, New York) (1954).
9.
N F M Henry, H Lipson and W A bWooster, in Interpretation of X-ray
diffraction photographs,
Mac Milan & Co Ltd., London (1961).

54
10.

Zawarch M F M and E I Kheshen A A, British Ceramic transitions, 101

(2002) 71.
11.

S.Hafner, Zeit. Kristallogr. 115 (1961) 331.