Chapter 1

GENERAL INTRODUCTION

1.1. Nanotechnology

Nanotechnology (NT) arises from the exploitation of physical, chemical,

and biological proper tit:^ of systems that are intermediate in size between isolated
atoms and bulk materials. It is recognized as an emerging technology of the 21''
century, along with the already established areas of information and
biotechnologies. Nanotechnology is now at a level of development comparable to
that of information technology in the 1950s. New experimental and simulation tools
emerging in the last few years and the discovery of novel phenomena and processes
at the "nano" scale have opened revolutionary opportunities for developments in
nanoparticles, nanostmctured materials, and nanodevice~.'.~
Their properties are
significantly different From those of corresponding bulk materials, and desirable
novel properties may be obtained. Scientific and technological discoveries in
nanotechnology are growing at an unprecedented rate.

Engineered nanostructures include nanostructured materials such as

ceramics, optical materials, polymers, and metals; nanocomponents such as
coatings and connectors; and nanodevices such as sensors, switches, and reactors.
Application areas include the pharmaceutical and chemical industries,
nanoelectronics, space exploration, metallurgy, biotechnology, cosmetics, the food
industry, optics, nanomnedicine, metrology and measurement, and ultraprecision
engineering -- there are practically no unaffected fields. NT implies direct control
of materials and decices on molecular and atomic scales, with engineered
properties. The purpose is to produce materials and devices that take advantage of
physical, chemical, and biological principles whose causes are found in the
nanometer scale. The most revolutionary NT approach is building up from the
molecules and nanoparticles, the so-called "bottom-up" (building blocks) approach
versus the "top-down' (extreme miniaturization) approach. 'Top-down' refers to
making nanoscale structures by milling and etching techniques, whereas 'bottom-
up', or molecular nanotechnology, applies to building structures atom-by-atom, or
Chapter 1 2

molecule-by-molecule. Top-down or bottom-up is a measure of the level of

advancement of nanotechnology. NT, as applied today, is still in the main at what
may be considered the more priinitive 'top-down' stage.

Top-down technology has distinct advantages. First, it provides a massive

parallel assembly of nano-structures with a high production rate, in addition to the
ability to organize the nanostructures into a desired pattern. Second, top-down
technology can integrate heterogeneous nanostructures. Third, it allows precisely
controlling the destiny of the nano-structures, therefore minimizing the generation
of defects commonly found in self-assembly. Finally, it promises a multi-scale
assembly technique by linking the dimensions from nano and micro to macro
world. Therefore, top-down technology has the potential to lead to cost-effective
manufacturing of more complex structures.

1.2. History of the Nanotechnology Idea

The human race is approaching the great historical transition, thorough

inexpensive control of the structure of matter, with all that implies for medicine, the
environment, and our way of life. What happens before and during that transition,
will shape its direction, and with it the future.

The history of nanot~:chnology begins in the 1860s, when the British

scientist Thomas Graham introduced the idea of colloid science, as dispersed
system of particles with sizes in the range 1-100 nrn. Till then, the physists Albert
Einstein, John Tyndall, Ostwald, ~ u b o ' .and
~ a lot of other researchers predicted
that small metal particles should exhibit physical properties quiet different from
those of bulk materials. Nanomatenals have actually been produced and used by
humans for hundreds of years. The ruby red colour of some stained glass is due to
gold nanoparticles trapped in the glass matrix. The decorative glaze known as
lustre, found on some medieval pottery, contains metallic spherical nanoparticles
dispersed in a complex way in the glaze, which gives rise to its special optical
properties. After the advent of atom clusters with selected sizes2 in the 1980%there
has been tremendous improvement in the study of small particles and their
enhanced potentials. Herbert Gleiter first suggested the synthesis of materials by
consolidation of small clusters.
General Introduction 3

Achievements in physics, biology, and chemistry have gathered together

information relevant to the process of understanding nanotechnology and necessary
to pursue the field. Despite the achievements of others, Richard P. Feynman is the
one most credited of starting it all. Prof. Feynman, a Nobel Prize winner in Physics,
gave a dinner talk in 1959, to the American Physical Society that seems to have
utilized or made the idea evident to the people.2 The dinner speech was titled,
"There's Plenty of Room at the Bottom." His speech included the idea that you
could write the whole Encyclopaedia Britannica on the head of a pin, which is
1125000 the normal size. He also spoke about duplicating single atoms, about
shrinking the size of the computers and developing better techniques of viewing and
examining nanotechnology. Richard Feynman was the first scientist to suggest that
devices and materials could someday be fabricated to atomjc specifications.

K. Eric Drexler is the one who is most recognized for driving the
nanotechnology revolution to where it is today. He has written numerous books and
publications about nanotechnology. In 1981 he published a paper, "Molecular
Engineering: An approach to the development of general capabilities for molecular
manipulation",6 about how the use of nanomachines can fabricate products with
atomic accuracy. Another book, "Engines of Creation: The Coming Era of
~ a n o t e c h n o l o ~ printed
~ " ~ , in 1986, and yet another book, "Unbounding the Future:
The Nanotechnology e evolution"^ in 1991.
In 1990, IBM meticulously and carefully positioned 35 xenon atoms to spell
the business' 3-letter name, which made it the world's tiniest company logo. Cornell
University scientists produced a non-visible "nanoguitar," in 1994, which cannot be
seen by the naked eye The strings, only a few atoms across, could be "plucked" by
laser beams to play 17 octaves above those made by a typical guitar. Following this,
in 1999, circuits one nlolecule thick is created, the smallest ever made, by scientists
from the Hewlett-Packard Company in California. The developments of these
circuits were announced in an essay in the magazine "Science" on July 16, 1999.

Over the past decade nanostmctured materials have been the subject of
enormous interest, with the potential for wide-ranging industrial, biomedical: and
electronic applications. This includes metals, ceramics, polymeric materials, and
nanocomposites.

1.3. Synthesis of Nanocrystalline Materials

The synthesis of nanocrystalline materials depend on the control of a variety

of nanoscale attributes desired in the final product. In general, four methods" have
been used to make nanophase materials.

1.The first technique involves the production of isolated, ultrafine crystallites

having uncontaminated free surfaces followed by a consolidation process either at
room temperature or at elevated temperatures. The processes used to isolate the
nanocrystalline materials are, inert-gas condensation, decomposition of the
precursors and precipitation from solutions.

2. Chemical vapour deposition (CVD), Physical vapour deposition (PVD), and

some electrochemical methods have been used to deposit atoms or molecules of
materials on suitable substrates. Depositing chemically different materials
simultaneously or consecuti\'ely can produce nanocomposites.

3. New classes of nanocrystalline materials can be synthesised by introducing

defects in a formerly perfect crystal such as dislocations or grain boundaries.
Subjecting the materials to high energy by ball milling, extrusion, shear, or high-
energy irradiation can bring about such deformations.

4. The final approach used to make nanocrystalline materials is based on

crystallization or precipitation from unstable states of condensed matter such as
crystallization from glasses or precipitation from supersaturated solid or liquid
solutions.

There are basically two broad areas of synthesis for nanocrystalline

materials, namely physical methods and chemical methods.

1.3(i)Physical methods

Several physical methods are currently in use for the synthesis of

nanocrystalline materials. Among them, the most widely used technique involves
the synthesis of single-phase metals and ceramics by inert-gas evaporation
General Introduction 5

technique." Atom clusters are generated by gas phase condensation proceeds .by
evaporating a precursor material in a gas maintained at a low pressure. The
evaporated atoms or molecules undergo a homogeneous condensation to form atom
clusters via collision with gas atoms in the vicinity of a cold - powder collection
surface. The clusters once formed are readily removed from the surface either by
natural convection of the gas or by forced gas flow. Sputtering is another method
used to produce nanocrystalline materials. This technique involves the ejection of
atoms or clusters of designated materials by subjecting them to an accelerated and
highly focussed beam of inert gas such as argon or helium. The third physical
method is through mechanical deformations.12 In this method, nanocrystalline
materials are produced by st~ucturaldegradation of coarser-grained structures
induced by the application of high mechanical energy. The nanometer sized g r a m
nucleate within the shear bands of the deformed materials converting a coarser
grained structure to an ultra fine powder. The heavy deformation of the coarser
material is effected by means of a high-energy ball-mill or a high-energy shear
process. In addition, various other physical methods such as sol-gel method, spray
pyrolysis, microwave decomposition, laser ablation, arc method etc., are also used
for the preparation of nanocrystalline materials.

1.3(ii) Chemical methods

Chemistry has played a major role in developing new materials with novel
and technologically important properties.13 The primary advantage that chemical
processes offer is good chemical homogeneity, as chemical synthesis offers mixing
at the molecular level. A basic understanding of the principles of crystal chemistry,
thermodynamics, phase equilibrium and reaction kinetics is important to take
advantage of the many benefits that chemical processing has to offer.14

Solution chemistry is used to prepare the precursor, which is subsequently

converted to the nanophase particles by nonliquid phase chemical reactions.15
Precipitation of a solid from a solution is a common technique used for the
synthesis of nanocrystalline materials. Nanocrystalline materials are also prepared
by chemical vapour depositic~n or chemical vapour condensation.I6 In these
processes, a chemical precursor is converted to the gas phase and it then undergoes
decomposition at low or atmospheric pressure to generate the nanocrystalline
material.

In general, the particle size and particle size distribution, the physical
properties such as crystal structure and the degree of dispersion can be affected by
the chemical reaction kinetics. The concentration of reactants, the reaction
temperature, the pH and the order of addition of reactants to the solution etc. are
also important. It is reported1 that the average particle size could be easily varied by
variations in the reactant concentrations, the temperature, and the composition of
the polymeric material^.'^'^^
1.4. Characterization Techniques

Success in devising and assembling systems on the scale of nanometers

require a deeper understanding of the basic processes and phenomena involved.
Hence, one of the current key objectives is to adapt and develop a range of
techniques that can characterize the structural, thermal, electronic, magnetic,
electric and optical properties of nanostmctured systems. High-resolution
techniques, that provide local information on the nanometer scale as well as those
provide only ensemble-average measurements, are all important in obtaining a
complete picture of material properties.

One of the most fundamental characteristics of nanometer-sized particles is

their very high surface-to-volume ratio.19 This can lead to novel and unexpected
atomic arrangements, and may also have dramatic effects on other physical or
chemical attributes. Because of this, the precise determination of nanoparticle
structure is a fundamental issue. Methods of structure determination can broadly be
classified in two categories, depending on the use of real or reciprocal space data.
Direct space methods allow the visualization of the atomic arrangement in
nanometer-sized regions; the most vivid examples are: High Resolution
Transmission Electron Microscopy (HRTEM), Scanning Electron Microscopy
(SEM), Atomic Force Microscopy (AFM) etc. Reciprocal space-based methods
exploit interference and diffraction effects of photons and electrons, to provide
sample-averaged information about structure. X-ray diffraction (XRD) ha5 been
recognized as the most important technique for determining the structure of
General Introduction 7

materia~s.'~A powerful technique used to probe the local environment. of a

particular element is Extended X-ray Absorption Fine Structure (EXAFS).~' Small-
angle elastic X-ray scattering (SAXS) can provide direct information about the
external form of nanoparticles or macromolecules, by measuring the typical size of
the electron density variations.

FTIR spectroscopy22is a powerful technique to provide deep insight in the

structural evolution from single atoms to crystalline solids. In vibrational
spectroscopy, the character of chemical bonds determines the spectral features.
Grain boundary interactions and surface amorphousness are prominent in
nanornaterials, which greatly influence their structure. The observed frequency shift
in the FTIR spectra of nanoclystals is due to the additional restoring force created
by surface polarization charges. Observation of the broadening of bands is
explained on the basis of surface phonons, characteristic of small particles. The
quantum confinement effect and small size effect in nanocrystals play important
roles in the lattice vibrations; including the appearance of new IR active modes, the
change in positions of active modes and in the broadening of bands.

Nuclear Magnetic Resonance (NMR) spectroscopy23 is used to study the

structural phase transitions in solids. The analysis of chemical shifts gives a lot of
information about the type of electronic environments present in a molecule. NMR
technique is used to understand the atomic structure, particularly of coordination
numbers of atoms or ions, group distributions, bridging and non-bridging of oxygen
atoms etc. of nanocrystalline materials. At present, two-dimensional (2D) NMR
technique enable more detailed knowledge of the atomic structure.

Transmission Electron Microscopy (TEM) is a unique technique, for it can

provide a real space image on the atom distribution in the nanocrystal and on its
surface.24 Today's TEM is a versatile tool that provides not only atomic resolution
lattice images, but also chemical information at a special resolution of 1 nm or
better, allowing direct identification of the chemistry of a single nanocrystal.
Scanning Electron Microscopy (SEM) instruments are tailor-made to provide
structural, chemical and morphological information about individual nanoparticles
on a nanometer scale. The applications of Atomic Force Microscopy (AFM) are
increased rapidly in the last decade. Since the requirement for a conductive surface
for Scanning Tunneling Microscopy (SlM),is not the necessary condition for
AFM, the objects are extended to insulating materials and cover a wide range of
surfaces such as metals, semiconductors, polymers, biological materials and
ceramics.

Thermal analysis methods f ~ n dwide spread applications for both quality

control and characterization of nanocrystalline materials. These analyses include a
variety of different methods of which Thermogravimetry (TG), Differential
Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC) are widely
employed.

In TG analysis25,a temperature variation must bring about a change in mass

of the analyte. Thus thermogravimetric methods are largely limited to
decomposition and oxidation reactions and to such physical processes as
vaporization, sublimation and desorption. Thennograms provide information about
decomposition mechanisms for various preparation routes. In addition, the
decomposition patterns are characteristic for each kind of reaction and in some
cases, can be used for identification purposes.

Differential thermal .analysis26is a technique in which the difference in

temperature between a substance and a reference material is measured as a function
of temperature while the substance and reference material are subjected to a
controlled temperature programme. DTA finds widespread application in
determining the thermal behaviour and composition of naturally occurring and
manufactured products. DTA measurements have been used for studying the
thermal behaviour of inorganic substances such as ferrites, clays, oxides, ceramics,
catalysts, and glasses. Infor~nationis obtained in the form of fusion desolvation,
dehydration, oxidation, reduction, adsorption and solid state reactions. An
important use of DTA is for the generation of phase diagrams and in the study of
phase transitions. The differential thermal method provides a simple and accurate
way of determining the melting, boiling and decomposition points of organic
compounds.
 General Introduction 9
-
. a thermal technique in which
Differential scanning calorimetry 27 is
differences in heat flow in to a substance and a reference are measured as a function
of sample temperature while the two are subjected to a controlled temperature
programme. Here, the difference in temperature rather than the difference in energy,
are recorded.

Various electrochemical methods have been used successfully to

characterize nanophase materials. In an electrochemical measurement, electrical
potential or current can be readily controlled or measured. Both steady state and
transient techniques2* have been used to determine the electrical and
electrochemical properties of nanophase materials. In a steady-state experiment, a
constant current or potential is applied and the steady-state response of the material
is monitored. In a transient experiment, the system is perturbed from an equilibrium
state and the relaxation of the system, such as current, potential, charge, impedance,
optical reflectance or other measurable properties of the system, is monitored as a
function of time. Impedance spectroscopy IS)'^ has emerged as a powerful
experimental tool in the study of electrical, electrochemical, and catalytic properties
of materials, including transport of ionic and electronic defects, dielectric
polarization, electrode kinetics, and other bulk or interfacial phenomena in various
material systems. As a non-destructive method with high accuracy and
reproducibility, impedance spectroscopy has been widely used as an in-situ
technique to elucidate e:lectrode kinetics and reaction mechanisms and to monitor
the electrical behaviour of various materials.

1.5. Properties of Nanocrystalline Materials

Nanocrystalline Materials are classified as crystalline materials with grain

sizes up to about 100nn1. Properties of nanocrystalline materials include increased
strength, enhanced diffusivity, improved ductility, reduced density, reduced
modulus, higher electrical resistance, increased specific heat, higher thermal
expansion coefficient, lower thermal conductivity, superior soft magnetic properties
etc., in comparison with conventional coarse-grained materials. Nanocrystalline
material^'^, which are expected to play a key role in human civilization, are
assembled with nanometre-sized "building blocks" consisting of the crystalline and
inter-crystalline components. Nanocrystals (NCs) of nanometer size are a new
generation of advanced materials exhibiting both chemical and physical properties,
which are different from those of the bulk materials and the single atoms. Interest in
materials that are an assemblage of nanornetre-sized "building blocks", arises from
the realization that by controlling the sizes of such "building blocks", one begins to
alter a variety of the physical, mechanical, and chemical properties of bulk
materials.31-35 These assembled materials, of single or multi-phase systems, in the
nanometre range are called nanocrystalline or nanophase materials.

Nanoparticles of intermetallic alloys are of particular interest to materials

engineers, because they create low-density, high-strength, high-performance
materials such as corrosion-resxstant coatings and heating elements. New ceramic
materials using the nanoparticles are developed that are stronger, flexible, and
having heat-resistant properties without their characteristic brittleness.
Nanomaterials have numerous commercial and technological applications. It is
often the unique properties of nanomaterials that make them useful for specific
applications.

Materials with nanometer size have unusual electronic, magnetic, optical,

and structural properties. Magnetic colloids and ferrofluids are used to study the
dependence of the fundamental properties of magnetic materials with size. The
desire to identify and understand the size-dependent properties of materials at the
nanometer scale has motivated the preparation of size-tunable monodisperse
nanoparticles with controllable internal structures.36In order to predict the unique
properties of nanocrystalline materials, which are a combination of the properties of
the crystalline and inter-crystalline regions, it is essential to understand precisely
how the structures of crystalline and intercrystalline regions vary with decrease in
crystallite size.

Nanopowders, controlled to nanocrystalline size (under 100 nm), can show

atom like behaviours resulting from higher surface energy due to their large surface
area and wider band gap between valence and conduction band when they are
divided to near atomic sizes?'
General Introduction 11

1.6. Nanocomposites

Nanocomposites offer the possibility of creating materials with superior

properties or improved functionality. The main types of nanocomposites currently
under investigation include polymer nanocomposites, metal matrix nanocomposites
and ceramic matrix nanocomposites. Future research challenges include the use of
biological materials in narlocomposites, synthesis of smart nanocomposites that can
be used in sensors, strengthening of nanocomposites to withstand effects of
explosions e t ~ . ~ '

There are a number of existing and proposed applications of electroceramics

in nanocomposite form, including batteries, fuel cells, gas separation membranes,
solar cells, etc.39,40Nanoceramic composites are utilized as chemical catalysts and
as chemical sensors. Their microcrystalline counterparts are often used as active
electrical devices such as varistors and thermistors. Due to the high surface-to-
volume ratios in nanoceramic composites, grain boundaries are found to exert
greater influence over electiicaVdielectric properties than in conventional
microcrystalline ceramics,.

1.7. Applications of Nanocrystalline Materials

Nanocrystalline materials are widely used in applications such as UV

protection, photocatalysis, field emission displays, varistors, functional devices, and
thermoelectric materials, etc4'"' due to their exceptional physical and chemical
qualities. Henceforth, they can be applied extensively to IT (information
technology), BT (bio technology) and ET (environmental technology) as next
generation technologies.

~anofabrication~"
encornpasses the making of things with dimensions less
than 100 nm. The ability to pattern any structure better than 100 nm provides the
key to top down nanotechnology. Combination of top down and bottom up areas of
nanotechnology and the materials issues associated with this, could have interesting
implications. The nanoelectronics industry4' has pioneered many of the techniques
now being applied more widely.
Chapter 1 12

Allied to nanofabrication, n a n o m e t r o 1 0 ~is~ ~the

~ precise measurement of
structures fabricated with dimensions less than 100 nm, and includes the
development of measurement techniques such as X-ray interferometry. Progress in
materials science is intimately related to achievements in the development of
dedicated analytical techniques that enable us to examine the atomic and electronic
structure of materials at the nano scale.

Nanostructured matenals, where the grain size is less than 100 nm, offer the
potential for stronger, more wear and corrosion resistant materials. This area is
closely linked to extreme nanotechnology. and covers the production of nanocages
used for drug encapsulation, nanotubes for use in displays, and photonic crystal
fibers and grating for use in telecommunications.49The grain size of materials
strongly affects their charactt:ristics. The ability to control the morphology and size
of nanoparticles is of fundamental importance.

The long established field of microelectromechanical systems5' is now being

pushed towards nano-scale precision with the development of nanofabrication
techniques such as focused ion beams. Molecular motors, such as those used in
muscles of bacterial flagellae, may be of use in pumping or controlling fluid flows
systems (NEMS) can be made, they
at this scale. If very fast nan~~electromechanical
could find uses as fast actuators where very small forces are required.

A wide range of advanced nanoceramicssl is being developed for future

applications such as enviror~mentalsensors, electronic components, turbine blades
and fuel cells. Improved processing and quality control will enable structural
nanoceramics to be used in areas such as aeronautics, space flight and power
generation. The distinction between structural and functional ceramics will become
narrow,52 as smart materials, nanoceramics and bioceramics are developed. The
main themes in this area include: integration of nanoceramics with other materials
to form smart composites; development of nanotechnology and miniaturization; and
increasing the functionality of ceramic materials.

Nanomaterials are e:merging as one of the fastest growing segments of the

chemical and materials industries. Nanomaterials show unusual performance
because of size confinement effects. Today, stoichiometric and non-stoichiometric
General Introduction 13

nanomaterials, single and mixed metal based compositions, doped nanomaterial

compositions, same ccmposition with different phases (cubic, monoclinic,
tetragonal, etc), nanoscale materials with non-spherical shapes, nanoparticles with
precision surface compositions etc are available in the market. These are
technology-intensive products in commercial quantities at cost-effective prices. The
processes and know-how to manufacture building blocks of nanotechnology IS

unique and distinctive ]In a number of ways when compared with competitive
technologies.

1.8. Phosphates

For chemists, phosphates are the salts of phosphoric acid. For life,
phosphates are indispensable. Whether for the food and pharmaceutical industries
or for technical applications, highly purified phosphates are working for us
everywhere - by nature. No living being can exist without phosphates.53-60 They are
involved in countless key functions in organisms. They are responsible for
budgeting the energy balance, and are also instrumental in transferring hereditary
information. 53 The skeleton and teeth's of human beings and animals consist of
phosphates to a large extent. Plants depend on phosphates for the photosynthesis.54
The phosphates they extract from the soil have to be replenished and are returned in
the form of fertilizer. Phosphates are also an important element of food. Excretion
as a result of metabolis~nnecessitates their constant fresh supply. Phosphates are
natural partners of our life. Following the example of nature, humans also take
advantage of the positive: properties in phosphates for a wide variety of purposes.

Phosphates form the largest number and greatest variety of phosphorus

based compounds. The basic phosphate nit^^-^^ has the chemical formula ~ 0 4 and
~ -

is known as orthophosphate. The simplest polyphosphates, the diphosphates contain

two units and have the general formula M(4/n)P207where cation(s) M represent a
valency of 4. The triphosphates, contain three units have the formula M ( Y n ) P 3 0 1 ~
Polyphosphates with four or more units are named following the same pattern
although they are usually referred to as "long chain" or "higher" polyphosphates.
Hexametaphosphate is a commonly used tradit~onalname for the longer chains
(usually eight or more units). The general formula is M (n+2)PnO(3n+l).
 Polyphosphates are excellent Sequestrants. They have the ability to form
stable, water-soluble complexes with a variety of cations including calcium,
magnesium, iron and some large proteins, preventing these from precipitating.
Phosphates have the ability to act as buffers5" and stabilise the pH of a system due
to their multi-basic nature. Polyphosphates also have the capacity to act as buffers
although this effect decreases with increasing chain length. As buffering ability
decreases, the sequestering ability increases and so the long chain polyphosphates
have negligible buffering capacity but are excellent sequestrants. Tripolyphosphates
have a degree of both properties and are often used where both processes are
required.

Threshold effect, sequestering ability and dispersant properties all make

phosphates as ideal products to use in the treatment of both potable and industrial
water supplies. The alkaline phosphates are well-established products in many
detergent applications, covering a wide variety of cleaning operations, both
domestic and industrial. Phosphates aid detergency by a combination of properties
of which sequestration, dispersion and buffering ability are the most important. The
polyphosphates have the ability to lower the critical Micelle Concentration of many
surfactants. Polyphosphates can be applied to both the chemical bonding of a
refractory system and the dispersion of its components. Phosphates can also be used
to give improved strength in refractory products.

The versatility of phosphates means they are widely used within the textile
industry. Their sequestering pnsperties were the first to be utilised, leading to their
other abilities for water softening, dispersion, deflocculation, cleansing, buffering
and flame retardancy. The buffering capacity of a phosphate mixture can be used
for many aspects of textile treatment, especially when dyeing. Polyphosphates are
used as dispersants for aqueous based emulsion paints.

Polyphosphates, have the ability to combine with proteins and act as protein
coagulants. Phosphates are water-soluble flame retardant additives, which can be
applied to a wide variety of materials to prevent flame spread and after-glow. They
can be used with textiles, timber, paper, paint and plastics.
 General Introduction 15

The main applications of phosphates67 7' in metal treatment are the

phosphating of ferrous metals and use in electroplating systems. Phosphating of
ferrous metals involves the formation of a strongly adherent iron phosphate film
over the surface of the metal. This forms an ideal pre-coat, preventing corrosion of
the cleaned metal surface prior to application of other surface coatings such as
paints and lacquers. A very low dose is added at the treatment works to prevent
corrosion of lead pipework in distribution systems.

Phosphates are suitable for horticultural use as they can supply three
nutrients; nitrogen, phosphorus and potassium, essential to plants for healthy
growth and rooting. Phosphates are used in many aspects of chemical manufacture,
both as reagents and processing aids. Pyrophosphates are widely used as anti-tartar
agents in toothpastes due to their ability to sequester calcium. Phosphates find
numerous applications in the food industry ranging from acidity regulators to anti-
coagulants. They are considered suitable for human consumption and for inclusion
in pet foods.

1.9. Metal Phosphates

1.9(i) Aluminium phosphnte

Metal phosphates have properties that range from catalysts through nuclear
waste disposal to synthetic: bone application. The aluminophosphate (A1Po4) family
of molecular sieves72-88 has been studied extensively, since their structural and
chemical properties are analogous to zeolites and they find applications in ion
exchange and catalysis. Aluminium phosphate has been used as a catalyst camer
and catalyst for dehydration of 2-propanol, isomerization of n-butene and
decomposition of methanol. Recently, various types of alumino phosphates,
substituted with different divalent ions in their framework have been synthesized.
These materials find different applications such as ion exchanger, adsorbent,
catalyst and so on. The modification of A1PO4 surface with various inorganic and
organic substances is predicted to give novel functions to this material. The
regulation of the surface sites may be expected to give various properties, such as
acidity and basicity, affinity and reactivity to molecules, and catalytic activity.
 Alp04 exists basically in seven polymorphic form^^^-^', which are analogs
of high and low temperature forms of quartz, midymite, and cristobalite. The stable
form below 475 OC is berlinite (isostmctural with quartz), between 475 and 750°C it
is phospho-tridymite, and above 750 O C it is phospho- cristobalite. The structures of
all polymorphic forms of Alp04 contain alternately tetrahedra of [AIPO~]~.
and
[PO~J'. High temperature berlinite crystallizes in the hexagonal group with three
AlPO4molecules per unit cell. Transition to the low temperature form decreases the
symmetry of the system to migonal symmetry group, also with three Alp04
molecules per unit cell. Alp04 tridymite has been studied extensively, 82-88 because
of its potential application as a catalyst support and microwave substrate. AIP04
berlinite, which is isostructural with quartz, undergoes a pressure-induced
amorphization at 20 GPa at ambient temperature. However, unlike quartz, berlinite
is believed to behave as a "memory glass", a term used to characterize a group of
materials which will undergo an amorphous transition when subjected to high
pressure, yet will recrystallize to the original crystallographic orientation on
quenching. This is a new phenomenon, which has been observed in several
materials that are isostmctural with quartz. The enhanced oxygen coordination
around the aluminium atoms in Alp04 at high pressure led to a mechanical
instability that caused the transformation from single crystal to an amorphous solid.
The 0-P-0 bond angle distribution remains close to the original and the PO4
tetrahedra remain four coordinated, even when severely distorted. This gives the
structural memory behaviour observed. The existence of a memory effect was
subsequently observed in molecular dynamics calculations.

Existence of a large and varied range of microporous aluminosilicates,94-102

including zeolites, clays and pillared clays, is well established, but only recently has
it become clear that similar versatility is also exhibited by aluminium phosphates
(AIPOs). The synthesis of 11ovel three-dimensional AlPOs with unique pore and
channel systems is an important goal as such compounds have potential uses as
molecular sieves, ion exchange resins and also, when suitably modified (e.g. by
partial replacement of P by Si, or A1 by a divalent metal), as solid acid catalysts.
General Introduction 17

1.9(ii) Copper phosphate

Copper phosphates103~'16
are a new class of synthetic zeolites. Zeolite
structures 103-1" are of current scientific interest because they are very efficient as
molecular sieves, in gas separation, and catalytic processes. Naturally formed
zeolites are aluminosilicates, and provide beneficial applications in commercial,
agricultural, and environmental areas. Usages range from detergents and water
softeners to petroleum cracking. Copper phosphates are expected to be used for
molecular sieving purposes (means of distillation of unwanted materials), ion
exchange (adsorption of unwanted chemicals from soil, water, and/or air, i.e. air
purification systems), catalysis processes (detergents, petroleum refining, synthetic
fuels production, water softening systems), and adsorption (drying agents,
purification, and separation).

The leaching of copper into plumbing systems can be greatly reduced by

introducing water-soluble orthophosphates into potable water distribution systems.
At low levels, the phosphates react with the copper to form copper orthophosphate
as an insoluble coating on the internal surfaces of the distribution system. Once this
coating is formed, observed copper levels in the drinking water drop rapidly. This
effect can be maintained by continued metering of phosphates into the system.

1.9(iii) Magnesium phosphate

Magnesium phosphates 117-131 have important applications. They are used as

bondings in refractories and mortars and as rapid setting cements. They are an
important ingredient in fertilizers and play a role in medical research. They are
widely used in glass industry, and magnesium phosphate glasses exhibit unusual
behaviour in their physical properties (mass density, refractive index etc.) as a
function of glass composition. Magnesium phosphate cement is a rapid setting,
early strength gain cement. It is usually used for special applications, such as repair
of pavements and concrete structures or for resistance to certain aggressive
chemicals.

Magnesium phosphate is an excellent chemically bonded phosphate ceramic

(CBPC) binder. Investigations of waste stabilization and volume reduction were
Chapter I 18
---
conducted using spiked soil and ;ash wastes coniaitling heafv metals such as Cd, Cr,
Pb, Ni, and Hg. The waste streams were stabiiized and solidified using chemically
bonded phosphate ceramic (CBPC) binder, anti then compacted by either uniaxial
or harmonic press for volume reduction. This method reduces heavy metal mobility
in soil and ash wastes by producing relatively inert waste forms with good
structural properties. In addition, it reduces the final volume of the waste, leading to
reduction in transportation and landfill disposal costs.

1.10. Present Work

The present investigation is concentrated on the synthesis, characterization

and property studies of the nanocrystalline forms of the above mentioned metal
phosphates; namely Aluminiuin phosphate, Copper Pyrophosphate, Magnesium
Pyrophosphate and the Magnesium Pyrophosphate-Iron Phosphate nanocomposite.
Each nanocrystalline sample is synthesised in three different grain sizes by
changing the corresponding reactant concentrations. Each sample is subjected to
undergo different heat treatment conditions depending on the nature of the sample.
Varying the mixing ratios changed the grain size of the nanocomposite. The crystal
size and structure of the nanoparticles were studied using X-ray diffraction, NMR
and TEM analysis. The vibrational properties of nanoparticles were studied using
FTIR spectrometry. The thermal analyses were made using TG and DTA. The
electrical properties of all the samples and their corresponding variations were
systematically investigated by studying the dielectric constant, dielectric loss factor
and the ac electrical conductivity. ?he analysis of impedance spectroscopy gave
valuable information about the grain contribution of the consolidated nanoparticles
and nanocomposites of all the prepared samples.

1.11. Conclusion

Nano-scale research promises to revolutionise the way we live, from

manufacturing and medicine to computing and communications. Many new
combinations of materials, n~olecules,atoms and ions will emerge that display
unusual and unexpected behaviour, allowing the development of new devices and
applications. In the nano world, dimensions and tolerances in the range 1 nm to 100
nm play a critical role. The field of nanotechnology, nanoengineering and
General lntroducrion 19

nanoscience is very broad, and covers everything from electronics, sensors,

healthcare and personal products. The nano scale world is truly interdisciplinary
requiring a mix of skills from mathematics, engineering and the physical, medical,
biological and sociological sciences. This inherent multidisciplinarity brings with i t
the challenges of language, training, and research methodology, all of which require
particular care if this important field is to flourish. There are important applications
of nanotechnology in manufacturing, biotechnologies, medicine, information
technology, electronics, processing technologies and elsewhere. Nanotechnology
produces smaller, cheaper, faster devices, and also systems with new functionality
offered by the quantum effects. Part of the motivation for working at the nano scale
comes from the evolution of microelectronics and the limitations of
microtechology. Almosr: all future materials science will be based on
nanotechnological concepts. Materials will be able to be assembled layer-by- layer
or even atom-by-atom to generate new atomic arrangements with completely new
properties. The interplay of the three main phenomena of confinement, proximity
and organisation creates rich new areas for uncovering novel materials behaviour.
Materials research bridges the atomic/molecular world and the macro world of
engineering. Since this bridge crosses the nanoscience space, it is not surprising that
materials scientists have been pioneers in nanotechnology. In a real sense
nanomaterials research forms an amalgam between the divergent research of
science, and the converge:nt research of engineering.

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