CHAPTER 1

NANOTECHNOLOGY AN OVERVIEW

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1.1 Introduction

In 1996,as the scientific and economic potential of nano scale science and technology was beginning to be
recognized,a federal interagency working group formed to consider creation of a National Nanotechnology
Initiative(NNI).Nanotechnology is not confined to any one industry and its applications are found in several
industries including surface chemistry,medical fields,organic chemistry,semiconductor fabrication and micro
fabrication etc.Nanotechnology helped researchers to create new materials with several applications in several
industries and also several devices in ultra-small size.It is an undeniable fact that the future will be of
nanotechnology.This chapter gives an introduction to nanotechnology and areas.

1.2 Nanotechnology

Nanotechnology is the science and technology of small things, in particular things that are less than 100nm
in size.One nanometer is 10-9 meters or about 3 atoms long.For comparison,a human hair is about 60-80000
nanometers wide.Scientists have discovered that materials at small dimensions can have significantly different
properties than the same materials at larger scale.There are thus endless possibilities for improved
devices,structures and materials if we can understand these differences,and learn how to control the assembly of
small structures.There are two types of manufacturing techniques involved in nanotechnology.One is “Bottom-
up”approach the other is “Top-down”approach.In the first approach,by using chemical characteristics of different
components we manipulate the substances at molecular level with molecular recognition technology.In the second
approach nano objects are constructed from large substances with advanced technology available at industries.

Nano word is originated from latin word,which means dwarf.Ideal size range offered by nanotechnology
refers to one thousand millionth of a particular unit thus nanometer is one thousand millionth of a meter.The
branch nanotechnology is the science that particularly deals with the processes that occur at molecular level and of
nano length scale size.

Nanotechnology is now become an allied science which is the most commonly used in other fields of science like
electronic,physics and engineering since many decades.Recent exploration of nanotechnology in biomedical and
pharmaceutical science results in successful improvement of conventional means of drug delivery system.

1.3 Nanoparticles

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 Nanoparticles are the particles (crystalline or amorphous) of organic or inorganic materials having sizes in
the range of 1-100nm.Nanoparticles are classified into nanostructured materials and nanophase/nanoparticle
materials.The former refer to condensed bulk materials that are make-of grains with grain sizes in the nanometer
size range while the latter are usually the dispersive nanoparticles.To distinguish nanomaterials from bulk,it is
vitally important to demonstrate the unique properties of nanoparticles and their prospective impacts in science
and technology.

Technology in the twenty first century requires the miniaturization of devices in to nanometer sizes while
their ultimate performance is drastically enhanced.This raises many issues regarding to new materials for achieving
specific functionality and selectivity.

1.3.1 Classification of nanoparticles

Depending on the dimensions in which Nanoparticles can be classified as

(a) Zero dimensional (Quantum dots) : Nanomaterials in which the movement of electrons is
confined in all three dimensions.Semiconductor nanocrystals are zero dimensional quantum dots,in which the
special distributions of the excited electron-hole pairs are confined within a small volume,resulting in the enhanced
non-linear optical properties.For example : clays,natural colloids such as milk and blood,fog,gelatin,ocean
spray,insect wings,lotus leaf and volcanic ash etc.

(b) One-dimensional (Quantum wires) : Nanomaterials in which the electrons can only move
freely in the X-direction.These include nanowires,nanorods and nanotubes.These materials are long but with
diameter of few nanometer.

(c) Two dimensions (Thin films) : Nanomaterials in which the free electron can move in X-Y
plane.These include different kind of nanofilms such as coatings and thin film –multilayers,nanosheets or
nanowalls.The area of nanofilms can be large (several square micrometer),but the thickness is always in nanoscale
range.

(d) Three dimensional : Nanomaterials in which the free electron can move in the X,Y,Z
directions.Eg:fullerenes : fullerenes are spherical cages containing from 28 to more than 100 carbon

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atoms,contains c60 this is a hollow ball composed of inter connected carbon pentagons and hexagons,resembling a

soccer ball.

Fig 1.1 Different dimensional nanomaterials (a) Zero dimensional clusters , (b) One dimensional
nanotubes,fibers,rods , (c) Two dimensional films,coats (d) Three dimensional poly crystals

1.3.2 Types of nanomaterials

(1) Fractals

Real fractals are self-similar structures that result from physical,chemical or biological growth processes.A
colloidal suspension is a fluid containing small charged particles,monomers,which are kept afloat by Brownian
motion and kept apart by coulomb repulsion.Charging the chemical composition of the solution can induce a
change in the interaction and an aggregation process can be initiated.The universal features have been
demonstrated for colloidal aggregates of gold,silica and polystyrene.

(2) Porous materials

Porous materials are characterized by a solid network having voids throughout the materials and have been
recognized as an important class of materials that can find applications in various fields.The percentage of porosity
varies from – 5% to 25% in nanophase materials.The value is higher for consolidated oxide nanoparticles
compared to metal nanoparticles.The porosity enhances diffusion nanophase ceramics.According to IUPAC
porous materials are characterized by pore size categorized by sorption behavior.Theymicroporous materials with
sizes smaller than 2 nm and 50 nm and macroporous materials with pores larger than 50 nm.

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(3) Zeolites

Zeolites are often referred to as molecular sieves because their physical shapes allow them to sift matereials.In
structure they look like nanoscopic galleries or chambers interconnected by nanoscopic tunnels or pore, all dug out
of a solid oxide.There are hundreds of different zeolites structures.The special nanopore structure of zeolites is the
secrets of their catalytic capabilities,and they represent highly profitable applications of nanotechnology.

(4) Fullerenes

Research in c60 fullerene has sparked a great effort in carbon related nanomaterials.Fullerenes and nanotubes
can be chemically functionalized and they can serve as sites/cells for nanochemical reaction.The ballistic quantum
conductance of carbon nanotube was observed in defect free carbon nanotubes.This effect may have great impact
on molecular electronics in which carbon nanotubes could be used as interconnects for molecular devices with no
heat dissipation,high mechanical strength and flexibility.

(5) Self-assembly passivated nanocrystals super lattices

Self-assembly passivated nanocrystals superlattices involve self-organization in to monolayers,thin films and

super lattices of size selected nanoclusters encapsulated in protective compact organic coating.A key step in this
process is fabrication of size and shape controlled nanocrystals assemblies that have the potential to assemble in to
large super lattice crystals for technological applications.

(6) Micelles

When the surfactant concentration exceeds the critical micelle concentration(cmc) in water, micelles are
formed as aggregates of surfactant molecules.In normal micelles the hydro phopic hydrocarbon chains of the
surfactant are oriented with the surroundings aqueous medium.Above the cmc the physical state of the surfactant
molecules changes dramatically,and an additional surfactant exists aggregates or micelles.The bulk properties of
the surfactant change around the cmc,such as osmotic pressure,turbidity,surface tension,conductivity and self-
diffusion.

(7) Self assembled monolayers

Self-assembled monolayers (SAM) are a prototypical form of nanotechnology:the molecules that form the SAM
carry the instructions required to generate an ordered,nanostructured materials without external invention.SAMs
demonstrate that molecular-scale design,synthesis,and organization can generate macroscopic materials properties
and functions.SAMs are important components of many other forms of nanotechnology.Because SAMs can
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assemble onto surfaces of any geometry or size,they provide a general and highly flexible method to tailor the
interfaces between nanometer-scale structures and their environment with molecular precision.

(8) NC core/shell structures

There are also different cellular organisms creating and using nanoparticles.One can find
Fe3O4,Fe3S4,CdS,La(NO3)2,Ag,Te,Se,Au and Tc nanoparticles in natural systems.The most amazing example is the
creation and use of magnetic nanoparticles enabling the use of biomagnetism.The Fe3O4 crystals exhibit a magnetic
moment and enable the organism to navigate within the magnetic field of earth.Magnetotactic bacteria live in
anaerobic environments and the magnetic sensor enables them to swim downwards,away from the oxygen rich
water-air surface.

1.4 Properties of nanomaterials

Nanomaterials can have significantly different properties when compared to the bulk equivalents.Large surface
area to volume ratio,large surface energies,Plasmon excitation,quantum confinement are some among the key
features of nanomaterials.It is seen that reactivity of nanoparticles increases with decrease in particle size,melting
temperature of nanophase is considerably lower than their bulk material and colour of a nanoparticle changes with
its size .The important properties of nanoparticles are discussed below.

1.4.1 Optical properties

All the nanostructured materials exhibit unique and complex optical properties.Semiconductor and
metallic nanomaterials and nanocomposites possess interesting linear absorption,photoluminescence emission,and
nonlinear optical properties.The most striking phenomenon exhibited by metal nano structures is Surface Plasma
Resonance (SPR).Colloidal solutions of spherical gold nanoparticles exhibit a deep red colour due to the well-
known surface Plasmon absorption.Noble metals such as copper,silver and gold,have strong visible light Plasmon
resonance.Size effects play a crucial role in influencing the magnetic and dielectric characteristics.When the size of
the semiconductor nanoparticles are reduced,the energy gap between the valence and conduction band
increases.Consequently,the optical absorption shows a blue shift.

1.4.2 Magnetic properties

Magnetic materials exhibit size-dependent magnetic properties that range from ferromagnetic to
paramagnetic to super paramagnetic with decreasing size.The magnetic properties of nanoparticles differ from
those of bulk mainly in two points.The large surface-to-volume ratio result in a different local environment for the
surface atoms in their magnetic coupling/interaction with the neighbouring atoms,leading to the mixed volume and
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surface magnetic characteristics.Magnetic nanocrystals have other important applications such as in colour
imaging,bioprocessing,magnetic refrigeration,and ferrofluids.Similarly,the properties (eg.Meissner effect) of the
superconductors also depend on particle size.

1.5 Synthesis route

There are two types of manufacturing techniques involved in nanotechnology .One is “bottom-up” approch the
other is “top-down”approach . in the first approach ,by using

chemical characteristics of different components we manipulate the substances at molecular level with molecular
technology. In the second approach nano objects are constructed from large substances with advanced technology.

(a) (b)

Fig 1.0 Two approaches of nano synthesis (a) top-down (b)bottom up

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 Bottom
up method Top-down
method

Physica Chemic Plasma Sol-gel Soft Self High Lithogra Gas Savere
l al process proces Lithogr Assem energy conden plastic
vapour vapour es sing bly phy
aphy Ball sation deforma
deposit deposit Milling tion
ion ion

Fig 1.2 General nanosynthesis routes

1.5.1Physical routes

Some physical methods are discussed below

(1)Spray pyrolysis : Spray prolysis is a simple ,reducible ,size controllable ,cheap

Method for synthesis some nano metal oxides mixed metal oxide .powders prepared through this method ,when
compared with those from wet chemical ones ,are more crystalline ,less agglomerated with higher purity and
also have large surface areas[29]

(2)Pulse laser ablation/deposition : This technique is carried out in a vaccum chamber and in the presence
of some inert gas .A high power pulsed laser beam is focused inside a vaccum chamber to strike a target in the
material and plasma is created , which is then converted in to a colloidal solution of nanoparticles

(3)Mechanical/ball milling method :In this technique ,row material of micron size is fed to undergo
several changes .these mills are categorized according to their capacities and applications. Mechanical mills which
are commonly used for the synthesis of copper nanoparticles are planetary, vibratory,uniball and attritor . this is
usually viewed as a trivial method forthe preparation of fine nanoparticles , for milling can only facilitate
production of particls nearer to nano size

1.5.2 Chemical routes

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Chemical methods are usually used to synthesize metal nanoparticles and among them, chemical reduction
is the most frequently applied method for the preparation of stable, colloidal dispersions in water or organic
solvents . commonly used chemical methods are listed below

(1)Chemical reduction method : The “bottom up” methods of wet chemical nanoparticles preparation rely
on the chemical reduction of metal salts. The chemical reduction of transision metal salts in the presence of
stabilizing agents to generate field . a large variety of stabilizers,eg.,donor ligands .polymers .and surfactants , are
used to controll the growth of the primarily formed nanoclusters and to prevent them from agglomerating . the
metal salt is reduced to give zero valent metal atoms in the embryonic stage of nucleation . these can colloid in
solution with further metal ions , metal atoms ,or clusters to form an irreversible “seed” of stable metal nucli can .
depending on the difference of the redox potensils between the metal salt and the reducing agent applied ,and the
strenghth of the metal –metal bonds, the diameter of the “seed” nucli can be well below 1nm .the type of reducing
agent employed has been found to greatly affect the resulting particles.

(2)Sol-gel method : Sol –gel method of synthesis consisting in the preparation of a sol and successive gelatin
and solvent removal . the precursors consist of a metal or metalloid element surrounded by various ligands . In
nanotechnology it is used most often to obtain metal oxides but is also applicable to the synthesis of nano sized
metals and fused bimetallic and hetero element particles .

(3)Micro emulsion method : Micro emulsion is a technique for the synthesis of nanoparticals in which two
immiscible fluids such as water in oil or oil in water or water in supercritical carbon dioxide become a
thermodynamically stable dispersion with the aid of surfactsnt . A typical emulsion is a single phase of three
components , water,oil and a surfactant

(4)Co-precipitation method : The inorganic colloidal routes is special case of precipitation with nucleation
and grwoth to amorphous or cristalline particles . If the concentration of feed is low and the PH value of the
solutionis in a range that surface charges are generated particle with diameters in the lower nanometer range are
accessible . In many cases an organic capping agent that is normally used to prevent agglomeration can serve as the
reducing agent

1.5.3 Biological routes

Many chemical and physical methods have been applied for synthesis of metallic nanoparticals. But various
problems are related with these methods which include use of harmful and expesive chemical reagents
,production of hazardous commodities etc .so we need to develop reliable, non-toxic ,clean, eco-friendly and
green experimental protocols for the synthesis of nanoparticals.
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Many biological systems including plants , fungi, actinomycetes ,bacteria , yeast and carbohydrates have the
ability to transform inorganic metal ions in to metal nanoparticals via the capacities of the proteins and
metabolites present in these organisms and sugars . use of plants in synthesis of nanoparticals has drown more
interest of workers as it provides single step process and makes rapid synthesis of nanopartical than chemical
methods . plants tender a superior option for synthesis of nanoparticals , the protocols involving plant
sources are free from toxicants ,morover natural capping agents are readily supplied by plants .

1.6 Importance of Cu nanoparticles

Nonmaterial are being applied in more and more fields in engineering and technology one of the
befits of nanomaterials is that their properties differ from bulk material of the same composition. The
properties of nanoparticles for example can be easily altered by varying their size shape and chemical
environment.Cu is a block D period 4 element it is ductile with very high chemical and electrical
conductivity . the morphology of cu nanoparticles is round ,and they appears as brown black powder.Cu is
found to be too soft for some applications and hence it is often combined with other metals to form
numerous alloys such as brass , which is a cu zinc alloy Cu nanoparticles are graded as highly flammable
solids therefore they most be stored away from sources of ignition . they are also known to be very toxic
to aquatic life.Cu nanoparticle showing catalytic and antifungal antibacterial activities are not observed in
commercial copper which demonstrate a very strong catalytic activity a property that can be attributed to
thier large catalytic surface area . Cu nanoparticles are able to achieve a higher reaction yield and shorter
reaction time when utilised as reagents in organic or organo metallic synthesis.Cu nano particles are used
in a condensation reaction of iodobenzene attained about 88% conversion to biphenyle.Copper nanoparticles
that are extremely small and have high surface to volume ratio can also serve as antifungal agent the
antimicrobial activity is included by their close interaction with microbial membranes and their metal ions
released in solutions.

Copper nanoparticle synthesis is of great research interest due to their optical,catalytic

mechanical and electrical properties.Copper is a good alternative material for noble metals such as Ag and Au as it
is highly conductive and much more economical than them.Copper plays an important role in electronic circuits
because of its excellent electrical conductivity. Copper nanoparticles have been explored as a new class of
heterogeneous catalyst in various chemical transformations. This review surveys the most useful organic
transformations which were carried out in the presence of copper nanoparticles as catalyst .Copper nanoparticles
catalysed reactions are advantageous over the conventional metal catalysed reactions in terms of low catalyst
loading,high atom economy,better yield ,inexpensive ,shorter reaction times and recyclability of the catalyst.

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1.7Applications Of Copper Nanoparticles

Some other applications of Cu nanoparticles are given below:

 Act as an anti-microbial,anti-fungal,anti-biotic added to plastics,coatings and textiles

 Copper diet supplements with efficient delivery characteristics
 High strength metals
 EMI shielding
 Thermal conductive materials
 Capacitor materials
 Conductive inks containing Cu nanoparticles
 Superficial conductive coating
 Microelectronic devices
 Nanometal lubricant additives

1.7.1 Motivation for the present study

The method of chemical synthesis does not require complicated equipment and any significant investment
thus it can be easily incorporated into industrial technology.Moreover,it allows controlling the particle size and
morphology of the products formed via maintaining certain reaction parameters.However,contemporary methods
for copper nanoparticle synthesis require the use of organic solvents as well as strong and toxic reducing agents
which are potentially hazardous to the environment.The attention of researchers is increasingly attracted to
chemical processes those are aimed at avoiding or minimizing any use of hazardous substances.

The present study aims to propose a simple,environmentally safe (green) method for the synthesis copper
nanoparticles.Carbohydrates such as sucrose and Ascorbic acid were used as reducing agents.PVA was used as
capping agent.The synthesized nanocolloids were characterized by various techniques such as UV-Vis absorption
Spectroscopy,X-ray Diffraction(XRD)Spectroscopy etc.

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 CHAPTER 2
EXPERIMENTAL TECHNIQUES

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2.1 Green synthesis
Well-dispersed and ultra-fine metal nanoparticles,especially transition metals,are of great interest due to
their distinctive physicochemical and thermodynamic properties,which have made them suitable for use in various
fields,such as catalysis,optics,and medicine.The development of efficient green chemistry methods for synthesis of
metal nanoparticles has become a major focus of researchers.Chemical reduction method is commonly used to
prepare metal nanoparticles in industrial applications,because of its great advantages in generating high
yields.However,this method is one of the conventional methods that employ many chemical agents hazardous to
the environment.As an alternative,methods based on the principle of green synthesis can be followed.In this
chapter we discuss the green methods used for synthesizing copper nanoparticles.The characterization techniques
to determine the size and morphology of the particles are also discussed.

2.2Copper nanoparticles

Copper nanoparticles are copper based particles 1 to 100 nm in size.Like many other froms of
nanoparticles,copper nanoparticles can be formed by natural processes or through chemical synthesis.These
nanoparticles are of particular interest due to their historical application as colouring agents and their modern days
biomedical ones.Copper nanoparticles display unique characteristics including catalytic and antifungal/antibacterial
activities that are not observed in commercial copper.First of all,copper nanoparticles demonstrate a very strong
catalytic activity,a property that can be attributed to their large catalytic surface area.With the small size and great
porosity,the nanoparticles are able to achieve a higher reaction yield and a shorter reaction time when utilized as
reagents in organic and organometallic synthesis.Copper nanoparticles that are extremely small and have a high
surface to volume ratio can also serve as antifungal/antibacterial agents.

2.3Green synthesis of copper nanoparticles using two reducing agents

Traditionally,in order to obtain copper nanoparticles one carries out a controlled chemical reaction of
producing copper (II) ions in solutions.The method of chemical synthesis does not require complicated equipment
and any significant investment thus it can be easily incorporated into industrial technology.Moreover,it allows
controlling the particle size and morphology of the products formed via maintaining certain reaction
parameters.Owing to a high reactivity of nanosized copper which is oxidized in the presence of even small amount
of oxygen in the solution,the nanoparticles formed should be protected from oxidation.These problems are solved
with the use of special materials,stabilizers.

The following are the key aspects of a synthesis route based on green chemistry principles.

 Selection of a biocompatible and non-toxic solvent medium

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  The selection of environmentally benign reducing agents
 The selection of non-toxic substances for stabilization of the nanoparticles

The field of nanotechnology is the one of the most active areas of research in modern material science.Among
various metal particles,use of copper nanoparticles has been highly considered due to their availability,low cost and
optical,electrical,catalytic,mechanical,magnetical and conductive properties.Copper nanoparticles are less
expensive alternative to highly expensive noble metal nanoparticles.Different chemical and physical method have
been employed for the synthesis of nanoparticles.Ofcourse, green synthesis seem to be the best option.we used two
reducing agents such as Sucrose and Ascorbic acid and employed two methods for the synthesis of copper
nanoparticles.

In various synthesis routes, chemical reduction is the most frequently applied method for the
preparation of metal nano colloids.Among two methods, Copper sulphate and Cupric acetate were chosen as the
precursors.In one method,nanoparticles were synthesized by carbohydrate (Sucrose)reduction of aqueous copper
acetate.In the second method,synthesis was done by reducing aqueous copper sulphate using Ascorbic acid.In both
cases we used deionised water as the solvent.PVA and Sodium hydroxide (NaOH) were added which acted as
capping and accelerating agents respectively.The experiment was done with PVA and Without PVA,and the results
were compared.The reduction of Copper sulphate using Sucrose was also tried with PVA and without PVA.The
reaction seemed to be incomplete with PVA.And the reaction became successful without PVA.

2.4 Materials and methods

2.4.1 Materials

The chemicals and reagents used in our studies is listed in the table given below

Solvent Distilled water

Precursor Cupric
Acetate(CH3COO)2CU.H2O
Copper Sulphate(CUSO4.5H2O)

Reducing agent Sucrose, Ascorbic acid

Stabilizing Agent PVA

Accelerating Agent Sodium Hydroxide(NaOH)

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2.4.2 Method of preparation

1) Ascorbic acid as the reducing agent

Precursor-Copper sulphate

 With PVA

For the synthesis of Cu nanaparticles (0.5g) of PVA was added to 20 ml of deionised water in 100ml flask and
stirred till a clear solution was obtained.10ml salt solution of Copper sulphate (0.01M) and 5ml of NaOH
(0.5M)was added to the above solution drop wise with continuous stirring for 15 minutes to obtain a light blue
colour solution.For the reduction,10 ml of 0.11M solution of Ascorbic acid was added to the above
solution.The resulting solution was continuosly stirred and subjected to temperature 80-850C.The individual
reactions took 30 minutes for completion.Nanoparticle formation was visually confirmed from the colour change
of the solution.

(a) (b) (c)

(a) Solution obtained by stirring for 30 minutes (b) Solution obtained after heating (c)Final solution obtained
by Ascorbic acid with PVA

 Without PVA

In this case,the above procedure was repeated without PVA.The final solution became Orange in colour.Above 850
C no colour change was observed.And colour of the final solution remained unchanged after several days.

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 (a) (b)

(a)Solution obtained by heating at 80-850C (b) Final solution obtained by Ascorbic acid without PVA

2) Sucrose as the reducing agent

Precursor-Cupric acetate

 With PVA

For the synthesis of Cu nanoparticles,(0.5g)of PVA was added to 20 ml of deionised water in 100ml flask and
stirred till a clear solution was obtained.5ml salt solution of cupric acetate(0.05M)and 5ml of NaOH was added to
the above solution drop wise with continuous stirring for 15 minutes to obtain a blue colour solution.For the
reduction,5ml of 1M solution of Sucrose was added to the above solution.The resulting solution was stirred and
subjected to temperature in the range 80-850C.The colour of the solution changed which indicated the formation of
Cu nanoparticles.

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 (a) (b) (c)

(a)Solution obtained by stirring of about 30 minutes (b) Solution obtained after heating at 80-850C (c) Solution
obtained from Sucrose with PVA.

 Without PVA

In this case,the above procedure was repeated without PVA.The final solution became dark green and then brown
in colour.Colour of the final solution remained unchanged even after few days.Hence the reaction became
complete.

(a) (b)

(a)Solution obtained from heating at 80-850C (b)Solution obtained from Sucrose with out PVA

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Precursor Copper Sulphate

Without PVA

We tried the same experiment with PVA but the reaction seemed to be incomplete.

After two weeks we filtered these solutions to obtain the nanoparticles.The obtained nanoparticles were cleaned
with distilled water and dried at room temperature and then taken for characterization.

2.5 Characterization Techniques

The characterization of nanoparticles can be done by using different techniques such as uv-vis spectroscopy
, x-ray diffraction method , scanning electron microscopy (SEM)),fourier transform infrared chararcterization
(FTIR) ,Dynamic Light scattering (DLS), transmission electron Microscopy (TEM) atomic force Microscopy
(afm) etc.

Microscopy based techniqes such as AFM,SEM, and TEM are considered direct methods of obtaining
data from images taken of the nanoparticle. In particular ,both SEM and TEM have been extensively used
to determine size and morphological features of nanoparticles .spectroscopy based techniques such as UV-
VS ,DLS-XRD and FT-IR are considered indirect method of determining data related to composition
,structure ,crystal phase and properties of nanoparticles .XRD examination produces a diffraction pattern
that is subsequqntly compared with the data contained in a standard crystallographic database to determine
structural information. Analysis of XRD data identifies crystallite size , structure , preferred crystal
orientation and phases present in samples. FT-IR spectroscopy can be used to investigate surface chemistry
identify surface residues such as functional groups like carbonyls and hydroxyls moieties that attach to
the surface during nanoparticles synthesis.

In our studies, we used the UV-Vis absorption spectroscopy , transmission electron microscopy
(TEM) and fluorescence spectroscopy for characterizing the synthesized nano colloids.

2.5.1 UV-Vis Absorption spectroscopy

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 Absorption spectroscopy or optical absorption spectroscopy is a very important tool used for the
characterization of nanomaterial[4].the most striking phenomenon encountered in metal nano particles is
the electromagnetic resonances resulting from the collective oscillations of conduction band electrons called
plasmons. Plasmon modes vary doepending on the geometry and are studied especially in noble metals like
silver ,gold and copper. The electrons in these metals originated from particle . the completely filled d
bands,which are relatively close to the fermi enrgy. Since the diameter of the nanoparticles is of the order
of the penetration depth of electromagnetic waves in metals,the excitation light is able to penetrate the
particles . the field inside the particle shifts the conduction electrons collectively with respect to the fixed
positive chrage of the lattice ions . the electrons build up a charge on the surface at one side of the particle.
The attraction of this negative charge and positive charge of the remaining lattice ions on the opposite
side results in a restoring force. If the frequency of the excitation light field is in resonance with with the
eigen frequency of the collective oscillation,even a small exciting field leads to strong oscillation. The
resonance frequency mainly depends on the restoring force this force in turn depends on the separation of
the surface charges ,ie.,the particle size,and the polarizability of the medium between and around the
charges . the alternating surface charges effectively forms an oscillating dipole , which radiates
electromagnetic waves . nanoparticles of noble metals are characterized by surface plasmon resonance(SPR)
which results in strong absorption charateristics in the visible or UV region. The absorption maximum and
the bandwidth are dependent on the size,shape,morphology, composition and dielectric enivronment of the
prepared nanoparticle , in addition to the nature of the metal.

Diagram of UV-Vis Spectrometer

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2.5.2 X-Ray Diffraction spectroscopy(XRD)

X- Ray Diffraction spectroscopy can provide a wealth of information concerning the physical electronic structure
of crystalline and non crystalline meterials in a variety of external conditions and environment.Surface X ray
diffraction allows the determination of atomic structure of ordered crystal surface in an analogous way to x ray
crystallography for the determination of three dimentional crystal structure.

Diffraction effects are observed when electromagnetic radiation impinges on periodic structures with
geometrical variations on the length scale of the wave length of the radiation.the inter atomic distances in crystals
and molecules amount to 0.15-0.4 nm which correspond in the electromagnetic spectrum with the wave length of
x rays having photon energies between 3 and 8 Kev.Accordingly, phenomena like constructive and destructive
interference should become observable when crystalline and molecular structures are exposed to x rays.There are
several special consideration for using XRD to characterize nano particles.First,reflection geometry is used for
these measurements as substrates are generally too thick for transmission. Second,high angular resolution is
required becouse the peaks from semiconductor materials are sharp due to very low defect densities in material.A
simple interpretations of the diffraction pattern was given by W.L.Bragg according to him the spots are produced
due to reflection of some of the incident x rays from the various sets of parallel crystal planes called Bragg’s planes
which contain a large number of atoms .consider the reflection of x ray from lattice in a crystal.Bragg derived the
conditions for constructive interference as

2dsinθ=nλ

Where θ is the angle made by the incident radiation with the lattice plane,d is the inter planar spacing of planes,λ is
the wavelength and n=1,2,3,......stand for first order,second order ,third order.......Maxima respectively.
Equation 1 is known as Bragg’s law.It should be remembered that the intensity that goes on decreasing as the
order of spectrum increases.From the Braggs law,it is clear that to obtain the diffraction effect there should be
matching between d, λ,θ .Therefore Bragg’s diffraction is totally different from ordinary diffraction where there
is no restriction on incident angle θ.For nano particles,the powder techniques in conjunction with diffractometer is
most commonly used.in this technique the diffracted radiation is detected by the counter tube,which moves along
the angular range of reflection.This intensities are recoded on a computer system. The ‘d’ values are calculated
using relation for known values of θ,λ , and n.The x ray diffraction data thus obtained is printed in tabular form on
paper and is compared with joint commitee power diffraction standerds(JCPDS) data to identify the unknown
material . The sample used may be power ,single crystal,or nano particles.Scherrer formula is used to estimate
particle size of very small crystals from the measured width of their diffracted curves.

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Scherrer formula is given as :

Particle size =0.9λ/βcosθ

Where λis the wave length .θ is the Bragg angle and β is the full width at half maximum, measured in
radians.From XRD,used scherrer formula the particle size of the samples were calculated .It can be concluded that
each sample have nano crystalline structure . The strain included in powders due to crystal imperfections and
distortion can be calculated using the formula

ε =βcosθ/4

X-ray, interact with electron cloud of atoms and because of their shorter wavelength.X-rays are scattered by
adjacent atoms in crystals which can interfere and give rise to diffraction effects .When X-rays enter into a
crystal,each as a diffraction centre and a crystal as a whole acts like three dimensional diffraction grating.The
diffraction pattern so produced can tell us much about the internal arrangement of atoms in crystals.The German
physicist M.Von Laue suggested the possibility of diffraction of X-rays by crystals.The reason for this suggestion
was that the wavelength of X-ray was of about the same order as the inter atomic distance in a crystal.In fact
,W.H.Bragg succeeded in diffracting X-rays from sodium chloride crystal.

The Bragg Equation

Bragg pointed out that unlike reflection of ordinary light,the reflection X-rays can take place
only at certain angles which are determined by the wave length of X-rays and the distance between the planes in
the crystal.The fundamental equation which gives a simple relation between the wavelength of X-rays,the
interplanar distance in thecrystal and the angle of reflection is known as the Bragg equation

21
In the above figure horizontal lines represent parallel planes in the crystal structure seperated from one another by
the distance d.Suppose a beam of X-rays falls on the crystal at glancing angleƟ ,some of these rays will be
reflected from the upper plane at the same angle Ɵ while some others will be absorbed and get reflected from the
successive layers.The waves reflected by different planes will be in phase with one another only if the difference in
the path length of the waves reflected from the successive planes is equal to an integral number of wavelength
s.Drawing ACand AD perpendicular to the incident and reflected beams,it will be seen that the difference in the
path lengths (S) of the curves reflected from the two planes is given by,

S-CB+BD

This should be equal to a whole number multiple of wavelength λ i.e.,

CB+BD= nλ, Here, CB=BD

Therefore,2CB=nλ

Or,2dsinθ=nλ

This is the Bragg equation.Knowing θ,λand n,d can be calculated.Generally in experiments on X-ray reflection,n is
set as equal to 1,if λ is known,it is possible to determine the d, the distance between atomic planes in the crystal by
determining θ experimentally.

22
 CHAPTER 3

CHARACTERIZATION OF SYNTHESISED NANOPARTICLES

23
3.1 X-Ray Diffraction Studies

The mean size of nanocrystals was measured from the broadening of the diffraction peaks corresponding to the
most intensive reflections according to the JCPDS (Joint Committee on Powder Diffraction Standards) database.
Scherrer equation was used to determine the crystallite size from XRD diffraction pattern measured for
nanoparticles:
d = Kλ/βcosθ …(3.1)

where K is the Scherrer constant (shape factor, its value is 0.9), λ is the X-ray wavelength ( = 0.154 nm), β is the
line broadening at half the maximum intensity (FWHM) in radians, θ is the Bragg angle, (the position of the
diffraction peak maximum) and d is the averaged dimension of crystallites in nanometers.

3.2 XRD Analysis of samples prepared by chemical reduction of Copper sulphate by

Ascorbic acid

3.2.1 Sample prepared in PVA matrix

The XRD patterns of the nanoparticles synthesized with the stabilizing agent PVA are shown in figure 3.1 .

Fig 3.1 XRD Analysis of of samples prepared with (Copper sulphate+Ascorbic acid+ PVA)

24
These three peaks were quite consistent with those of the standard JCPDS for the standard spectrum of the pure fcc
(face centered cubic) metallic Cu.
Besides the metallic Cu peaks, three more diffraction peaks appeared at 36.6260, 42.5380 and 61.61950
corresponding to (111), (002) and (022), planes of cuprite, respectively, indicate the formation of cubic copper
(I) oxide nanocrystals . The XRD pattern reveals that prepared nanoparticles are a mixture of metallic Cu and
copper (I) oxide (Cu2O).

3.2.2 Sample prepared in the absence of PVA

The XRD patterns of the nanoparticles synthesized without PVA is shown in figure 3.2

Fig 3.2 XRD Analysis of Sample prepared with ( Copper sulphate+Ascorbic acid)

Peaks observed at 2θ values of 43.2770, 50.4050 and 74.0940 correspond to (111), (002) and (022) planes of
metallic Cu. Only these three peaks are present, leading to the conclusion that the nanoparticles contain metallic
copper alone and no oxides of copper.

3.3 XRD Analysis of samples prepared by chemical reduction of Copper sulphate by Sucrose

3.3.1 Sample prepared in the absence of PVA

The XRD pattern obtained in this case showed the peaks corresponding to Cu2O alone and no peaks corresponding
to metallic Cu was present.

25
Fig 3.3 XRD Analysis of Sample prepared by (Copper sulphate+Sucrose)

Peaks observed at 2θ values of 36.4960, 42.4070, 61.57610 and 73.7900 correspond to (111), (002), (022) and (113)
planes of Cu2O.
3.4 XRD Analysis of samples prepared by chemical reduction of Copper Acetate by Sucrose
3.4.1 Sample prepared in PVA matrix

Fig 3.4 XRD Analysis of Samples prepared with (Copper Acetate+Sucrose+PVA)

26
Peaks observed at 2θ values of 36.5830, 42.4940, 61.6190 and 73.7900 respectively correspond to (111), (002),
(022) and (113) planes of Cu2O.
3.4.2 Sample prepared in the absence of PVA

Fig 3.5 XRD Analysis of sample prepared with (Copper acetate+Sucrose)

Peaks observed at 36.2350, 42.1460 and 61.3580 correspond to (111), (002) and (022) planes of Cu2O.
3.5 Size Determination of Cu and Cu2O nanoparticles
The mean size of the crystalline Cu and Cu2O nanoparticles was calculated from the major diffraction peaks using
the Scherrer formula.

Nano 2θ (in
Sample Specification β (in radians) Particle size(in nm)
particle deg.)
Copper Sulphate +
Cu 50.622 5.308 x 10-3 28.88
Ascorbic acid +

PVA
Cu2O 36.626 5.309 x 10-3 27.49

Copper Sulphate +
Cu 50.405 6.065 x 10-3 25.26
Ascorbic Acid

Copper Sulphate +
Sucrose
Cu2O 36.496 4.5 x 10-3 32.45

Copper acetate +
Sucrose + PVA
Cu2O 36.583 3.79 x 10-3 38.52

Copper acetate + Sucrose Cu2O 36.235 4.549 x 10-3 32.06

Table 3.1(Size Determination of Cu and Cu2O nanoparticles)

27
3.6 UV-VISIBLE ABSORPTION SPECTROSCOPY
Sample-A (Copper Sulphate+PVA+Ascorbic Acid)

Sample-B (Copper sulphate+NaOH+Sucrose)

28
Sample-C (Copper Sulphate+NaOH+Ascorbic Acid)

Sample-D (Cupric acetate+NaOH+Sucrose)

29
Sample-E (Cupric acetate+PVA+NaOH+Sucrose)

UV-Vis spectra of SamplesA,B,C,D and E

Formation of copper nanoparticles was conformed by the UV-Visible spectroscopy.Sample prepared with
Ascorbic acid as the reducing agent yield successful result.

30
3.7 Discussions
Metallic Cu and cuprite nanocrystals have been synthesized by facile chemical reduction methods. in an alkaline
medium. Different methods were employed to synthesise the nanoparticles.
In one method, copper sulphate was chosen as the precursor and ascorbic acid, which is an organic-based
reductant , as reducing agent. Copper is easily reduced in solution using this mild reductant. Addition of sodium
hydroxide augmented the rate of reduction. We have observed that pure Cu nano particles are formed by ascorbic
acid reduction of copper sulphate. But in the presence of PVA, a mixture of Cu and Cu2O nanoparticles were
formed as evident from the XRD analysis. The second method was based on a carbohydrate (sucrose) mediated
reduction mechanism of copper acetate and copper sulphate .The XRD pattern revealed the formation of Cu 2O
alone.
The size of the produced nanocrystals is relatively small when the rate of reduction is slow; therefore, less
powerful reducing agents are favorable for generating smaller size nanoparticles Ascorbic acid is a mild reducing
agent when compared to sucrose. This property lead to the formation of well-structured nanoparticles with a
decrease in the mean crystal size with time. The Cu nanoparticles formed had an average size of 25.26 nm. When
reaction was performed in the presence of capping agent PVA, we obtained Cu and Cu2O nanoparticles with
mean size 27.49 and 28.88 nm, respectively. The oxidation of metallic Cu is a key to the production of greater
amount of cuprite instead of metallic Cu. The addition of sodium hydroxide is also expected to form Cu(OH)2
which subsequently produce Cu2O upon reduction. As metal particles are generated in the aqueous phase, they are
unstable by nature, and these metal atoms tend to agglomerate so as to decrease the total surface energy. In
addition, some metals serve as nuclei for others to grow on. The XRD diffraction pattern showed the coexistence
of two crystalline phases, i.e., metallic Cu and Cu2O. This obviously illustrates that the zero-valent copper
nanoparticles formed in the chemical reduction stage go through decomposition due to limited stability of Cu and
Cu2O might be formed by oxidation . All the nanocubes were indeed Cu and Cu2O; no other phase of copper oxide
(CuO) was present. Oxidation of unstable Cu particles obtained via carbohydrate mediated synthesis resulted in the
formation of Cu2O nanoparticles alone. We also recorded the UV-Vis Absorption spectra of the prepared
nanocolloids. The presence of copper oxides in some samples were also evident from the spectra. The present
study demonstrates that ascorbic acid with its anti oxidant properties, serves as an effective reducing agent that
resulted in the fabrication of small-sized Cu nanoparticles. However, the effect of PVA should be investigated in
detail.

31
 CHAPTER 4
SUMMARY AND FUTURE PROSPECTS

32
4.1 General Conclusion

Copper nano particles were synthesized from copper sulphate and cupric acetate through a simple,cost
effective and green method. Various reducing agents like sucrose and ascorbic acid were used. A polymer PVA
was used as the stabilizing agent.The formation of nanoparticles was confirmed by the colour change of the
colloidal solutions and by UV-Vis absorption spectroscopy. X-ray diffraction studies were done to analyse the
structure and size of the chemically synthesized nanoparticles.

Pure Cu nano particles were formed by ascorbic acid reduction of copper sulphate. The Cu nanoparticles
formed had an average size of 25.26 nm. But in the presence of PVA, a mixture of Cu and Cu 2O nanoparticles
were formed as evident from the XRD analysis. The mean size of these particles were found to be 27.49 and 28.88
nm respectively. Another synthesis method was based on a carbohydrate (sucrose) mediated reduction mechanism
of copper acetate and copper sulphate. In this case, we obtained only Cu2O nanoparticles with slightly bigger size.
Oxidation of unstable Cu particles obtained via carbohydrate mediated synthesis resulted in the formation of Cu 2O
nanoparticles alone. From the present study we can conclude that ascorbic acid with its anti oxidant properties,
serves as an effective reducing agent for the fabrication of small-sized stable Cu nanoparticles. However, the
effect of stabilizing agent should be investigated in detail.

4.2 Scope for future work

.Metals and Semiconducting materials in nanostructures form remain an extensively investigated subject in
current Physics (nanoscience,nanotechnology, materials science and solid state physics) and Chemistry. Most of
the promising technological applications deals with size dependent properties. The ability to manipulate matter at
the atomic scale bears promise to produce devices of unprecedented speed and efficiency. The emerging area
called nanoscience and nanotechnology which has seen phenomenal growth in the past decade and is likely to be
the frontal area of research for the next few decades.
Copper nano particles have many applications in biology and medicine,including protein purification,drug
delivery and medical imaging. . Synthesis of Cu nanoparticles is quiet challenging due to its high tendency for
oxidation. It is extremely sensitive to air, and the oxide phases are thermodynamically more stable . Hence,
development of improved methods for the synthesis of copper nanoparticles is of high priority for the advancement
of material science and technology.
Copper nanoparticles prepared under optical experimental conditions can display an intense and narrow
Surface Plasmon resonance peak that is comparable to Silver and Gold. Hence copper may potentially be used to
33
replace the more expensive metals of Ag and Au for certain applications.But,the optical properties of copper
nanoparticles are significantly affected by the presence of copper oxides.This is further dependent on the nature of
the reducing agent. The effect of various other factors such as pH of the solution and concentrations of reducing
agents and precursor are to be studied in detail. The effect of stabilizing agent is yet another factor to be explored.
A detailed investigation is required to set up optimal conditions for obtaining stable copper nanoparticles through
chemical reduction.

34
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