CHAPTER 1

INTRODUCTION
The electroplating or metal finishing industry has been playing a momentous role in
the development and growth of numerous metal manufacturing and other engineering
industries since the early part of this century. While electroplating operations have, in
the course of time, become an essential and integral part of many engineering
industries throughout the world, there has also been a steady growth of independent
and small to medium scale electroplating industries, especially in the developing
countries including, India. Electroplating is the electro deposition on metals, alloys
and non-metallic. The electroplating of common metals includes the processes in
which ferrous or non-ferrous base materials is electroplated with nickel, chromium,
copper, zinc, lead, iron, cadmium, aluminum, brass, bronze etc. One of the major
chemical waste producing industries is the electroplating industry generating a
whooping amount of waste which comprises of Nickel, Cadmium, Chromium,
Palladium and several other carcinogenic elements. This waste gets in to the water
cycle and in turn accounts for several diseases in our ecosystem.

1.1 Literature Survey

According to a report about 700,000 electroplating units were working in India, out of
which about 5000 units are in Aligarh. The wastewater generated in Aligarh by lock
industries, specially electroplating industries is around 250 million litres per day.
From all these units a very harmful waste containing carcinogenic elements was found
to be disposed heedlessly in water bodies.
After accessing all these information we came to a conclusion that there is an
immediate need to pacify the adverse impact of these wastes and nevertheless
harnessing the metallic content of these in some lucrative way. With the growth of
industry, environmental pollution is rapidly increasing in our country. The awareness
of environmental pollution control has come much later than the development of
chemical industry in India. The legislation has also come much later than the
industrial growth.

[1]

The successful recovery of this high waste content with development of cleaner
production processes has resulted in huge savings in water, chemicals, degreasing
substances etc. Thus recycling can help in recovery as well as providing better
surroundings. Apart from the above mentioned advantages, some others are:1) Recycling of rinse water and effluent helps in reducing the consumption of costly
bath solution thus reducing the cost of operation.
2) Reduction in the problems and costs associated with the treatment and disposal of
waste.
3) To provide least amount of contaminants and toxic materials so as not to pollute
the environment for better surroundings.
In India though due to lack of awareness and economic reasons these recovery
processes have not been resorted to mainly by the industries in the small scale sector.
Studies are currently in progress to properly define the plating waste market character,
pin point potential clients, and obtain more detailed data on waste volumes,
composition and variability.
Table 1.1 Heavy Metal Concentration in electroplating waste.

Metals

Concentration (in
ppm or mg/L )

Nickel

139

Zinc

27

chromium

17

Cadmium

Lead

Copper

As the table 1.1 suggests that in these wastes, Nickel element is present as a potential
waste. Owing to the characteristics of an element at nano level we inferred that
[2]

synthesising nickel nano particles from waste could pave a way ahead towards a
greener environment.

1.2 Electroplating industry

Electroplating is one of the varieties of several techniques of metal finishing. It is a
technique of deposition of a fine layer of one metal on another through electrolytic
process to impart various properties and attributes, such as corrosion protection,
enhanced surface hardness, lustre, colour, aesthetics, value addition etc. Electroplating
process has applications in large scale manufacturing plants (e.g. automobile, cycle,
engineering and numerous other industries) as well as job-work by small and tiny
units. Though this process has a long history, but it gained momentum after
independence. In 1976, the first semi-automatic plant was set up in Mumbai.
Currently there are more than 600 automatic plants in the county. It is estimated that
electroplating is now worth Rs. 1000 crores and this sector employs 1, 30,000
approximately people in the industry in 12000 organized sectors. However, hardly
any data is available for unorganized sectors and it is difficult to find the distribution
of production in unorganized.

Fig 1.1: An Electroplating unit working in Aligarh.

[3]

The current technology options for recovery which is one of main objectives are given
in brief below:
1) Electro chemical treatment process- This process has been developed to recover
metal from dilute electroplating and rinse water solution. Some of the advantages
are low operating costs that can be applied to all platable materials.
2) By Micro filtration, heavy metals like Nickel, Chromium, Gold, Silver and Copper
can be recovered. The disadvantage of this process is, a filter cake is produced
which is a hazardous waste and thus it is not recommended.

3) Chemelec Cell is one of recommended technologies that has been installed in many
industries abroad giving profitable results. It is an electrolytic recovery process and
is used to recover different precious metals like nickel, cadmium, zinc etc.
Chromium is a metal which cannot be recovered by this process.

1.3 Rationale of study

On one hand, the process has number of applications but, simultaneously it has been
included among 17 major polluting industries in India by Central Pollution and
Control Board, government of India. Electroplating is considered a major polluting
industry because it discharges toxic materials and heavy metals through wastewater
(effluents), air emissions and solid wastes in environment. It was found that a large
amount of metals and chemicals is disposed into main stream without treatment as
they have no effective measures for treatment or recovery of metals in unorganized
sectors. At the same time it is to be kept in mind that majority of units are in tiny and
small scale, which are not able to upgrade the technology immediately to achieve
cleaner production. Thus, it is not possible to protect the environment in a significant
manner, unless cleaner production is achieved. Consequently, there is a need to adopt
a balanced and practical approach so that goal is achieved over a period of time.
Adoption of proper handling and recycling methods will help in the optimization of
the use of various raw materials. The recovered materials can be used again, thus
reducing their consumption in these industries. The recovered materials can also be
used by other industries for their raw materials.
The precious materials, of which most of the requirements are met through imports,
after recovery lead to reduced exploitation of these materials and also reduces the
[4]

burden on imports. The cost benefits due to implementation of pollution control

measures may be long term but they yield better productivity.

1.4 Objective of Our Study

For this project report we met the following objectives:
i)

Preliminary study carried put to confirm the abundance of Nickel in the

waste.

ii)

Collection of detailed information on materials used in electroplating (like

Nickel, Chromium, Silver etc.)

iii)

Different solvent for synthesis and preparation of nano materials.

iv)

Characterisation techniques performed to reveal the properties of

synthesised product.

[5]

CHAPTER 2
NANOTECHNOLOGY: PRINCIPLES AND APPLICATIONS
The term nanotechnology comes from the combination of two words: the Greek
numerical prefix nano referring to a billionth and the word technology. As an
outcome, Nanotechnology or Nano scaled Technology is generally considered to be at
a size below 0.1 m or 100 nm (a manometer is one billionth of a meter, 10-9 m).
Nano scale science (or Nano science) studies the phenomena, properties, and
responses of materials at atomic, molecular, and macromolecular scales, and in
general at sizes between 1 and 100 nm. In this scale, and especially below 5 nm, the
properties of matter differ significantly (i.e., quantum-scale effects play an important
role) from that at a larger particulate scale. Nanotechnology is then the design, the
manipulation, the building, the production and application, by controlling the shape
and size, the properties-responses and functionality of structures, and devices and
systems of the order or less than 100 nm.
Nanotechnology is considered an emerging technology due to the possibility to
advance well-established products and to create new products with totally new
characteristics and functions with enormous potential in a wide range of applications.
In addition to various industrial uses, great innovations are foreseen in information
and communication technology, in biology and biotechnology, in medicine and
medical technology, in metrology, etc. Significant applications of Nano sciences and
Nano engineering lie in the fields of pharmaceutics, cosmetics, processed food,
chemical engineering, high-performance materials, electronics, precision mechanics,
optics, energy production, and environmental sciences.
Nanotechnology is one of the leading scientific fields today since it combines
knowledge from the fields of Physics, Chemistry, Biology, Medicine, Informatics,
and Engineering. It is an emerging technological field with great potential to lead in
great breakthroughs that can be applied in real life. Novel nano and biomaterials, and
nano devices are fabricated and controlled by nanotechnology tools and techniques,
which investigate and tune the properties, responses, and functions of living and nonliving matter, at sizes below100 nm. The application and use of nano materials in
electronic and mechanical devices, in optical and magnetic components, quantum
computing, tissue engineering,

[6]

Fig. 2.1: Nanoscale size comparision

and other biotechnologies, with smallest features, widths well below 100 nm, are the
economically most important parts of the nanotechnology nowadays and presumably
in the near future. The number of nano products is rapidly growing since more and
more
nano engineered materials are reaching the global market The continuous revolution
in nanotechnology will result in the fabrication of nanomaterials with properties and
functionalities which are going to have positive changes in our lives, be it in health,
environment, electronics or any other field. In the energy generation challenge where
the conventional fuel resources cannot remain the dominant energy source, taking into
account the increasing consumption demand and the CO2emissions alternative
renewable energy sources based on new technologies have to be promoted. Innovative
solar cell technologies that utilize nano structured materials and composite systems
such as organic photovoltaics offer great technological potential due to their attractive
properties such as the potential of large-scale and low-cost roll-to-roll manufacturing
processes The advances in nanomaterials necessitate parallel progress of the
nanometrology tools and techniques to characterize and manipulate nanostructures.
[7]

Nanotechnology can help in solving serious humanity problems such as energy

adequacy, climate change or fatal diseases. Nanosciences and nanotechnologies open
up new avenues of research and lead to new, useful, and sometimes unexpected
applications. Novel materials and new-engineered surfaces allow making products
that perform better. New medical treatments are emerging for fatal diseases, such as
brain tumours and Alzheimers disease. Computers are built with nanoscale
components and improving their performance depends upon shrinking these
dimensions yet further.
Nanomaterials with unique properties such as: nanoparticles carbon nanotubes,
fullerenes, quantum dots, quantum wires, nanofibers, and nanocomposites allow
completely new applications to be found. Products containing engineered nano
materials are already in the market. The range of commercial products available today
is very broad, including metals, ceramics, polymers, smart textiles, cosmetics,
sunscreens, electronics, paints and varnishes.
Nanomaterials must be examined for potential effects on health as a matter of

Fig. 2.2: Diverse application of nanotechnology

[8]

precaution, and their possible environmental impacts. However new methodologies

and instrumentation have to be developed in order to increase our knowledge and
information on their properties.
The development of specific guidance documents at a global level for the safety
evaluation of nanotechnology products is strongly recommended. Ethical and moral
concerns also need to be addressed in parallel with the new developments.
Huge aspirations are coupled to nano technological developments in modern
medicine. The potential medical applications are predominantly in diagnostics(disease
diagnosis and imaging), monitoring, the availability of more durable and better
prosthetics, and new drug-delivery systems for potentially harmful drugs.
While products based on nanotechnology are actually reaching the market, sufficient
knowledge on the associated toxicological risks is still lacking. The size reduction of
structures to nano level results in distinctly different properties. As well as the
chemical composition, which largely dictates the intrinsic toxic properties, very small
size appears to be a dominant indicator for drastic or toxic effects of particles.

2.1 What Makes Nanostructures Unique

Nanoscale particles are not new in either nature or science. However, the recent leaps
in areas such as microscopy have given scientists new tools to understand and take
advantage of phenomena that occur naturally when matter is organized at the
nanoscale. In essence, these phenomena are based on quantum effects and other
simple physical effects such as expanded surface area (more on these below). In
addition, the fact that a majority of biological processes occur at the nanoscale gives
scientists models and templates to imagine and construct new processes that can
enhance their work in medicine, imaging, computing, printing, chemical catalysis,
materials synthesis, and many other fields. Nanotechnology is not simply working at
ever smaller dimensions; rather, working at the nanoscale enables scientists to utilize
the unique physical, chemical, mechanical, and optical properties of materials that
naturally occur at that scale.
2.1.1 Scale at which quantum effects dominates the property of materials
When particle sizes of solid matter in the visible scale are compared to what can be seen in a
regular optical microscope, there is little difference in the properties of the particles. But when
[9]

particles are created with dimensions of about 1100 nanometers (where the particles can be
seen only with powerful specialized microscopes), the materials properties change
significantly from those at larger scales. This is the size scale where so-called quantum effects
rule the behavior and properties of particles. Properties of materials are size-dependent in this
scale range. Thus, when particle size is made to be nanoscale, properties such as melting
point, fluorescence, electrical conductivity, magnetic permeability, and chemical reactivity
change as a function of the size of the particle.

Nanoscale gold illustrates the unique properties that occur at the nanoscale. Nanoscale
gold particles are not the yellow color with which we are familiar; nanoscale gold can
appear red or purple. At the nanoscale, the motion of the golds electrons is confined.
Because this movement is restricted, gold nanoparticles react differently with light
compared to larger-scale gold particles. Their size and optical properties can be put to
practical use: nanoscale gold particles selectively accumulate in tumors, where they
can enable both precise imaging and targeted laser destruction of the tumor by means
that avoid harming healthy cells.
A fascinating and powerful result of the quantum effects of the nanoscale is the
concept of tunability of properties. That is, by changing the size of the particle, a
scientist can literally fine-tune a material property of interest (e.g., changing
fluorescence color; in turn, the fluorescence color of a particle can be used to identify
the particle, and various materials can be labeled with fluorescent markers for
various purposes). Another potent quantum effect of the nanoscale is known as
tunneling which is a phenomenon that enables the scanning tunneling microscope and
flash memory for computing.

2.1.2 Scale at which much of biology occurs

Over millennia, nature has perfected the art of biology at the nanoscale. Many of the
inner workings of cells naturally occur at the nanoscale. For example, hemoglobin, the
protein that carries oxygen through the body, is 5.5 nanometers in diameter. A strand
of DNA, one of the building blocks of human life, is only about 2 nanometers in
diameter.
Drawing on the natural nanoscale of biology, many medical researchers are working
on designing tools, treatments, and therapies that are more precise and personalized
than conventional onesand that can be applied earlier in the course of a disease and
[10]

lead to fewer adverse side-effects. One medical example of nanotechnology is the biobarcode assay, a relatively low-cost method of detecting disease-specific biomarkers
in the blood, even when there are very few of them in a sample. The basic process,
which attaches recognition particles and DNA amplifiers to gold nanoparticles,
was originally demonstrated at Northwestern University for a prostate cancer
biomarker following prostatectomy. The bio-barcode assay has proven to be
considerably more sensitive than conventional assays for the same target biomarkers,
and it can be adapted to detect almost any molecular target.
Growing understanding of nanoscale biomolecular structures is impacting other fields
than medicine. Some scientists are looking at ways to use nanoscale biological
principles of molecular self-assembly, self-organization, and quantum mechanics to
create novel computing platforms. Other researchers have discovered that in
photosynthesis, the energy that plants harvest from sunlight is nearly instantly
transferred to plant reaction centers by quantum mechanical processes with nearly
100% efficiency (little energy wasted as heat). They are investigating photosynthesis
as a model for green energy nanosystems for inexpensive production and storage of
nonpolluting solar power.

2.2.3 Large Surface to Volume ratio

Nanoscale materials have far larger surface areas than similar masses of larger-scale
materials. As surface area per mass of a material increases, a greater amount of the
material can come into contact with surrounding materials, thus affecting reactivity.
A simple thought experiment shows why nanoparticles have phenomenally high
surface areas. A solid cube of a material 1 cm on a side has 6 square centimeters of
surface area, about equal to one side of half a stick of gum. But if that volume of 1
cubic centimeter were filled with cubes 1 mm on a side, that would be 1,000
millimeter-sized cubes (10 x 10 x 10), each one of which has a surface area of 6
square millimeters, for a total surface area of 60 square centimeters. When the 1 cubic
centimeter is filled with micrometer-sized cubesa trillion (1012) of them, each with
a surface area of 6 square micrometersthe total surface area amounts to 6 square
meters. And when that single cubic centimeter of volume is filled with 1-nanometersized cubes1021 of them, each with an area of 6 square nanometerstheir total
surface area comes to 6,000 square meters. In other words, a single cubic centimeter
[11]

of cubic nanoparticles has a total surface area 1 million times the total surface area of
1mm cube.

Fig. 2.3: Increasing surface area for the nanoparticles.

One benefit of greater surface areaand improved reactivityin nanostructured

materials is that they have helped create better catalysts. As a result, catalysis by
engineered nanostructured materials already impacts about one-third of the huge
U.S.and globalcatalyst markets, affecting billions of dollars of revenue in the oil
and chemical industries. An everyday example of catalysis is the catalytic converter in
a car, which reduces the toxicity of the engines fumes. Nano engineered batteries,
fuel cells, and catalysts can potentially use enhanced reactivity at the nanoscale to
produce cleaner, safer, and more affordable modes of producing and storing energy.
Large surface area also makes nanostructured membranes and materials ideal
candidates for water treatment and desalination, among other uses. It also helps
support functionalization of nanoscale material surfaces (adding particles for
specific purposes), for applications ranging from drug delivery to clothing insulation.

2.2 CHEMINANOTECHNOLOGY
The term Cheminanotechnology represents the most pervasive nanotechnology which
is applied to chemical processes. Most commentaries on nanotechnology start with
[12]

reference to Eric Drexler, who is credited with coining the term, and then proceed to
discuss physicist Richard Feynmans assertion that there is plenty of room at the
bottom, by which he meant the advances that remain to be made in manipulating and
controlling things on the small scale. Nanotechnology can mean little machines that
will pump miniscule volumes of liquid, or it can refer to some new development in
fabrics that repel water. The term nanotechnology covers a whole range of very
different developments, ranging from nanostructuring of surfaces important to the
semi-conductor industry and biosensors, right up to nanoparticulate systems. The
latter are relevant to the finishing of synthetics or for catalytic processes in
'chemistry'. Because of this wide variety of applications, it is not easy to describe how
we benefit from nanotechnology.

Chemistry can be loosely described as the study of the formation, properties, and
interactions of molecules, while chemical engineering is the control of chemical
processes on a large scale. It has been known since at least the time of Lord Kelvin
and J.Williard Gibbs that the thermodynamic properties of a chemical substance are
not constant but are in fact affected by the size of the piece of the substance being
studied. For example, at 1 atm pressure water boils at 100 C. However, this is true
only of relatively large volumes of water. A droplet of water of 5 nm radius will boil
at 95.9 C. The physics behind this has been understood for over a hundred years.
Similarly, melting points are affected by size; gold, which normally melts at 1064 C,
will melt at temperatures as low as 350 C when it is a 2 nm particle.
At the nanoscale, not only do these physical properties change but enthalpies of
fusion, vaporization, and chemical reaction change. These can affect the equilibrium
of a chemical reaction or can lead to chemical reactions being possible that do not
take place on larger particles. An early example is the observed change in the nickelnickel carbonyl equilibrium. A more recent example is the discovery that small
particles of gold exhibit catalytic behavior. Previous studies on larger particles of gold
showed no catalytic activity, and the change is known to be chemical rather than
depend upon the increase in surface area per mass as a substance is divided up into
smaller pieces. Properties thought to be characteristics of the substance start to
become inconstant at small sizes, and at the nanometer level the effects have dramatic
results.

[13]

It is not only chemical reactions but also fluid flows that change at small size. When
dealing with liquids at small scales, that indispensable engineering concept, the Reynolds number (the dimensionless ratio of viscosity to momentum) is usually less than
unity, and handling fluids becomes quite a different task with the intuitive notions of
the flow and behaviour of a liquid being overturned.
We now have techniques that can look at, or work with, single molecules to establish
the properties of molecules individually rather than as an average of a collection. A
good example here is the scanning probe microscope (SPM) that enables us to
visualize single atoms and even electron waves in a way we may never have thought
possible. Now we can see defects in surfaces at which catalysis may be occurring,
whereas previously we knew that they must exist but could only infer their properties
by other means. We can stretch single molecules and obtain directly physical
properties and thermodynamic data from force measurements on the single molecule
rather than the large numbers of molecules in a calorimeter or a spectrophotometer.
We can look at the effect of possible new drugs on a single live bacterium rather than
on a whole population of bacteria.
Not only do we have new techniques but we have new materials that were not
available previously. Challenges still lie in determining how these new products can
be used, but they are providing opportunities for new and innovative exploration into
fields ranging from medicine to mineral processing. Examples include carbon nanotubes and titanium dioxide nanotubes. We can now use our understanding of the
adhesion forces we observe in nature, such as a gecko clinging to a wall solely by
means of van der Waals forces, and mimic these structures in synthetic adhesive
materials. A further spectroscopic technique of interest to chemists is surfaceenhanced Raman spectroscopy whereby the signals can be enhanced up to 1015 times
for molecules adsorbed onto clusters of small particles of gold or silver. Advances in
technology will therefore be dependent on corresponding progress in application
technology, which will have to supply cost-effective processes in particular, such as
modern

dispersant

technologies,

emulsifying

and

encapsulation

processes,

precipitation, gas-phase reactions and suitable grinding techniques

The blurring of the traditional disciplinary boundaries between chemistry, physics,
and chemical engineering is reflected in the lack of clear distinctions between the
[14]

branches that make up nanotechnology. Nevertheless, cheminanotechnology can be

delineated as a subset of nanotechnology that is focused on understanding the effect
that very small size has on chemical reactions, and the subsequent use of this
understanding in new product and process development.

2.3 Application of Nanoparticles

Fig.2.4: Application of nanotechnology

[15]

CHAPTER 3

SYNTHESIS OF NANOPARTICLES
3.1 Introduction:
Verbally Synthesis refers to the consolidation of ideas into a complex whole one.
Chemical synthesis is a purposeful execution of chemical reactions to obtain a
product, or several products. This happens by physical and chemical manipulations
usually involving one or more reactions. In modern laboratory usage, this tends to
imply that the process is reproducible, reliable, and established to work in multiple
laboratories. A chemical synthesis begins by selection of compounds that are known
as reagents or reactants. Various reaction types can be applied to these to synthesize
the product, or an intermediate product.

3.2 Sample collection

Electroplating waste sludge was collected in the form of liquid from one of the
electroplating industries in Aligarh titled as M/s. Player Locks, Aligarh, in which
Nickel, Chromium, Zinc and Cadmium plating is done, associated mostly of lock and
other allied industries. There are more than 5000 number of big and small plants are
working. These plants generate large quantity of waste. The quantity of articles plated,
depends on shape, property desired for various articles. This industry is having 130
20 75 cm size tanks for collecting wastes of Nickel, Chromium, Zinc and Cadmium
etc. There is no appropriate arrangement for proper disposal of these wastes, generally
these wastes are disposed off directly in the drains without any treatment causing
environmental and ground water pollution in the disposal area.

Fig 3.1: Procured waste samples

[16]

Fig 3.2: Electroplating Unit

Fig 3.3 Tanks Containing Waste

3.3 Methods and Materials:

In our present work Nickel oxide nano particles were successfully synthesised by
chemical route in which sucrose and honey were used as precursor and sodium
hydroxide was required for maintaining the homogeneity and ph value of the solution
and helps to make a stoichiometric solution to get Nickel oxide nanoparticles.

[17]

1) The sample which we procured was first of all subjected to heating up to a

temperature of around 85-90 C. Afterwards heated sample was stirred and during
this continuous stirring 50gm of sodium hydroxide solution was added.

Fig 3.4 Heating and Stirring of Sample.

For the purpose of stirring and heating a magnetic stirrer was used. In magnetic
stirring the given sample is subjected to a rotating magnetic field and a small magnet
is dropped in the sample. As the magnetic field alters in direction in a circular path the
magnet also moves in this direction and we get a continuous stirring. The stand (on
which sample is placed) also serves for the purpose of heating as there are induction
plates on it. By this mechanism both heating and agitation operations are served at the
same place without much hassle.
2) After the addition of NaOH, around 1 hour later, in the state of continuous stirring,
50 gm. sucrose and 10 g honey were added to the sample. After 5 hours of
continuous stirring and heating a thick tar like solution was obtained.

[18]

Fig 3.5 Product after Stirring and Heating

Fig 3.6 Product taken in Petri dish

3) For the further analysis and operation we needed to check its solubility in water
and we came to conclude that our product was water soluble.

[19]

Fig 3.7 Dissolved product in water

Fig 3.8 Comparison of sample and the product obtained from it

4) For getting the nano particles ultimately, we needed the product to be dried up
completely. For this purpose, the product obtained, was transferred in a petri dish
and then placed in a vacuum oven at a temperature of 95 C for 24 hrs. After this
heating operation the product gets dried up and is depicted in figure 3.11 and 3.12

[20]

Fig 3.9 Product kept in vacuum oven for drying

Fig 3.10 Product obtained after drying

5) After this much heating, this dried product was transferred to a muffle furnace
where it was subjected to a high temperature of about 500 C for 2 hours. Heating
in muffle furnace was required because our product vas a very thick fluid rather
than a solid. This would have created glitches in comminution.

[21]

Figure 3.11 Muffle furnace

6) The ultimately dried product obtained after this was grinded to make a fine powder
by using simple pestle and mortar

Fig 3.12 Pestle and mortar

Fig 3.13 Fine powder obtained

The fine powder so obtained is our anticipated product, i.e. Nickel\ Nickel oxide nano
particles. Now to check whether the product thus obtained is the looked-for product or
not, if yes then what is its structure and configuration, we need certain
characterisation techniques to ascertain all these.
In these techniques we are confronted by various methodology of testing like XRD,
SEM, FTIR, and UV Visible. All these are elaborated in the ensuing chapter.

[22]

CHAPTER 4

CHARACTERIZATION TECHNIQUES
There are various techniques for detecting, measuring and characterizing
nanoparticles. There is not a method that can be selected that is the best method but
rather a method is chosen to balance the restriction of the type of sample, the
information required, time constraints and the cost of the analysis. A straight forward
technique may simply detect the presence of nanoparticles, others may give the
quantity, the size distribution or the surface area of the nanoparticles. These
measurement techniques differ from characterization techniques for assessing the
chemical content of a nanoparticle sample, the reactions on the surface of the
nanoparticles or for the interactions with other chemical species present. There is also
a division between techniques that give information on an amount of nanoparticulate
material and those that can look at the individual nanoparticle within the sample.
Sometimes measurement techniques will be combined to provide more information
from one sample.
Generally there are two types of characterization techniques involved in accessing the
information about the desired nano particle sample viz. Analysis by Microscopy and
the other is Analysis by Spectroscopy.
Table 4.1: Different characterization techniques

Structural Analysis

Optical Analysis

Thermal Analysis

1. X-Ray Diffraction

1.UV Visible

1.Thermo Gravimetric

2. Scanning Electron

Spectroscopy

Analysis

2.Fourier Transform

2.Differential Scanning

Infrared Spectroscopy

Calorimetry

Microscopy

3.Energy Dispersive
Spectroscopy

Since different techniques provide different information and accuracy, efforts have
been made to standardize the way nanoparticles are measured to assess particle size,
[23]

heat stability, behaviour towards ultra violet light and etc.. The most common
techniques are shown in the table above.

4.1 Scanning Electron Microscopy

The scanning electron microscope (SEM) uses a focused beam of high-energy
electrons to generate a variety of signals at the surface of solid specimens. The signals
that derive from electron reveal information about the sample including external
morphology (texture), chemical composition, and crystalline structure and orientation
of materials making up the sample. In most applications, data are collected over a
selected area of the surface of the sample, and a 2-dimensional image is generated that
displays spatial variations in these properties. Areas ranging from approximately 1 cm
to 5 microns in width can be imaged in a scanning mode using conventional SEM
techniques (magnification ranging from 20X to approximately 30,000X, spatial
resolution of 50 to 100 nm). The SEM is also capable of performing analyses of
selected point locations on the sample; this approach is especially useful in
qualitatively or semi-quantitatively determining chemical compositions (using EDS),
crystalline structure, and crystal orientations.

Fig 4.1: Scanning Electron Microscope at USIF-AMU

[24]

4.2 Energy Dispersive Spectroscopy

EDS makes use of the X-ray spectrum emitted by a solid sample bombarded with a
focused beam of electrons to obtain a localized chemical analysis. All elements from
atomic number 4 (Be) to 92 (U) can be detected in principle, though not all
instruments are equipped for light elements (Z < 10). Qualitative analysis involves
the identification of the lines in the spectrum and is fairly straightforward owing to the
simplicity of X-ray spectra. Quantitative analysis (determination of the concentrations
of the elements present) entails measuring line intensities for each element in the
sample and for the same elements in calibration Standards of known composition.
Energy-dispersive spectrometers (EDSs) employ pulse height analysis: a detector
giving output pulses proportional in height to the X-ray photon energy is used in
conjunction with a pulse height for analyser (in this case a multichannel type). A solid
state detector is used because of its better energy resolution. Incident X-ray photons
cause ionization in the detector, producing an electrical charge, which is amplified by
a sensitive preamplifier located close to the detector. Both detector and preamplifier
are cooled with liquid nitrogen to minimize electronic noise. Si(Li) or Si drift
detectors (SDD) are commonly in use.

Fig 4.2: EDS Detector.

[25]

4.3 Fourier Transform Infrared Spectroscopy

In the region of longer wavelength or low frequency the identification of different
types of chemicals is possible by this technique of infrared spectroscopy and the
instrument requires for its execution is Fourier transform infrared (FTIR)
spectrometer. The spectroscopy merely based on the fact that molecules absorb
specific frequencies that are characteristic of their structure termed as resonant
frequencies, i.e. the frequency of the absorbed radiation matches the frequency of the
bond or group that vibrates. And the detection of energy is done on the basis of shape
of the molecular potential energy surfaces, the masses of the atoms, and the associated
vibronic coupling. As each different material is a unique combination of atoms, no
two compounds produce the exact same infrared spectrum. Therefore, infrared
spectroscopy can result in a positive identification (qualitative analysis) of every
different kind of material. In addition, the size of the peaks in the spectrum is a direct
indication of the amount of material present. FTIR can be used to analyse a wide
range of materials in bulk or thin films, liquids, solids, pastes, powders, fibers, and
other forms. FTIR analysis can give not only qualitative (identification) analysis of
materials, but with relevant standards, can be used for quantitative (amount) analysis.
FTIR can be used to analyse samples up to ~11 millimetres in diameter, and either
measure in bulk or the top ~1 micrometre layer. FTIR spectra of pure compounds are
generally so unique that they are like a molecular fingerprint.

Fig 4.3: FT-IR Instrument at Department of Applied Physics.

[26]

4.4 Differential Scanning Calorimetry (DSC)

Thermal Analysis (STA) generally refers to the simultaneous application of
Thermogravimetry (TGA) and Differential Scanning Calorimetry (DSC) to one and
the same sample in a single instrument. The test conditions are perfectly identical for
the TGA and DSC signals (same atmosphere, gas flow rate, vapour pressure of the
sample, heating rate, thermal contact to the sample crucible and sensor, radiation
effect, etc.).Thus, Thermal analysis (TA) is a group of techniques in which changes of
physical or chemical properties of the sample are monitored against time or
temperature, while the temperature of the sample is programmed which may involve
heating or cooling at a fixed rate, holding the temperature constant (isothermal), or
any sequence of these.

Fig 4.4: TGA & DSC at Department of Applied Physics

4.4.1 Working of DSC
The sample and reference chambers are heated equally into a temperature regime in
which a transformation takes place within the sample. As the sample temperature
deviates from the reference temperature, the device detects it and reduces the heat
input to one cell while adding heat to the other, so as to maintain a zero temperature
[27]

difference between the sample and reference. The quantity of electrical energy per
unit time which must be supplied to the heating element in order to maintain null
balance is assumed to be proportional to the heat released per unit time by the sample.
4.4.2 Working of TGA
Measurements of changes in sample mass with temperature are made using a thermo
balance. This is a combination of a suitable electronic microbalance with a furnace
and associated temperature programmer. The balance should be in an enclosed system
so that the atmosphere can be controlled. Y axis is %mass loss; X axis is temp (or
time, since usually a linear heating rate). As the specimen changes weight, its
tendency to rise or fall is detected by LVDT. A current through the coil on the
counterbalance side exerts a force on the magnetic core which acts to return the
balance pan to a null position. The current required to maintain this position is
considered proportional to the mass change of the specimen.

4.5 X-Ray Diffraction (XRD)

Till 1895 the study of matter at the atomic level was a difficult task but the discovery
of electromagnetic radiation with 1 (10-10 m) wavelength, appearing at the region
between gamma-rays and ultraviolet, makes it possible. As the atomic distance in
matter is comparable with the wavelength of X-ray, the phenomenon of diffraction
find its way through it and gives many feasible results related to the crystalline
structure. The unit cell and lattices which are distributed in a regular threedimensional way in space forms the base for diffraction pattern to occur. These
lattices form a series of parallel planes with its own specific d-spacing and with
different orientations exist. The reflection of incident monochromatic X-ray from
successive planes of crystal lattices when the difference between the planes is of
complete number n of wavelengths leads to famous Braggs law:
2d Sin = n
Where n is an integer 1, 2, 3.. (Usually equal 1), is wavelength in angstroms, d is
interatomic spacing in angstroms, and is the diffraction angle in degrees. Plotting
the angular positions and intensities of the resultant diffracted peaks of radiation
produces a pattern, which is characteristic of the sample.
[28]

Fig4.5 X-ray Diffraction in accordance with Braggs Law

Fig 4.6: XRD Apparatus at Department of Physics-AMU

Measurement conditions:
X-ray tube
Target

= Cu

Voltage

= 40.0 (kV)

Current

= 30.0 (mA)

Slits
Divergence slit

= 1.00000 (deg)

Scatter slit

= 1.00000 (deg)

Receiving slit

= 0.30000 (mm)
[29]

Scanning
Scan range

= 20.000 - 80.000

Scan mode

= Continuous Scan

Scan speed

= 2.0000 (deg/min)

Sampling pitch

= 0.0200 (deg)

Preset time

= 0.60 (sec)

4.6 UV Visible Spectroscopy

The wavelength of UV is shorter than the visible light. It ranges from 100 to 400 nm.
In a standard UV-V is spectrophotometer, a beam of light is split. one half of the
beam (the sample beam) is directed through a transparent cell containing a solution of
the compound being analysed, and one half (the reference beam) is directed through
an identical cell that does not contain the compound but contains the solvent. The
instrument is designed so that it can make a comparison of the intensities of the two
beams as it scans over the desired region of the wavelengths. If the compound absorbs
light at a particular wavelength, the intensity of the sample beam (IS) will be less than
that of the reference beam. Absorption of radiation by a sample is measured at various
wavelengths and plotted by a recorder to give the spectrum which is a plot of the
wavelength of the entire region versus the absorption (A) of light at each wavelength.
And the band gap of the sample can be obtained by plotting the graph between (h
v/s h) and extrapolating it along x-axis.

Fig 4.7: UV Visible Spectrometer at Centre of Excellence in Nano Materials, Dept. of

Applied Physics-AMU.

[30]

CHAPTER 5

RESULTS AND DICUSSION

5.1 X-Ray Diffraction Analysis
The synthesized nanoparticles were characterized by powder X-ray diffractometer.
Fig.5.1 shows the X-ray diffraction spectrum of NiO sample. This shows crystalline
structure with 7 peaks. The XRD pattern shows a significant amount of line
broadening which is a characteristic of nanoparticles. The XRD pattern exhibits
prominent peaks at 31.4, 43.3, and 63.

Fig. 5.1: X-ray diffraction spectrum of NiO sample

The crystal size can be calculated according to Debye-Scherrer formula.
..... (1)

[31]

Where k=0.9, is the wavelength of the Cu-K radiations, is the full width at half
maximum and is the angle obtained from 2 values corresponding to maximum
intensity peak in XRD pattern. The mean crystal size of NiO nanoparticle is 8.25 nm.
The inter planar distance was calculated using Braggs Law .
2d Sin = n

....... (2)

Where, n was taken as 1. The value of d for the most intense peak was 2.846. The
Diffraction peaks thus obtained from X-ray diffraction data are in good agreement
with the standard pattern of NiO .

5.2 XRD - Crystallinity Index

It is generally agreed that the peak breadth of a specific phase of material is directly
proportional to the mean crystallite size of that material. From our XRD data, a peak
broadening of the nanoparticles is noticed. The average particle size, as determined
using the Scherrer equation, is calculated to be 8.25 nm. Crystallinity is evaluated
through comparison of crystallite size as ascertained by SEM particle size
determination.
Crystallinity index Eq. is presented below:
.... (3)

(Icry 1.00)
Where Icry is the crystallinity index; Dp is the particle size (obtained from either
TEM or SEM morphological analysis); Dcry is the particle size (calculated from the
Scherrer equation).

Table 5.1: The crystallinity index of Nickel Oxide Nanoparticles

Sample

Dp (nm)

Dcry (nm)

Icry

Particle Type

NiO nanoparticles

100

8.25

12.12

Polycrystalline

Table 5.1 displays the crystallinity index of the sample that scored higher than 1.0.
The data indicate that the NiO is highly crystalline. If Icry value is close to 1, then it is
assumed that the crystallite size represents monocrystalline whereas a polycrystalline
have a much larger crystallinity index.

[32]

5.3 XRD - Specific Surface Area

Specific surface area (SSA) is a material property. It is a derived scientific value that
can be used to determine the type and properties of a material. It has a particular
importance in case of adsorption, heterogeneous catalysis and reactions on surfaces.
SSA is the Surface Area (SA) per mass.
. (4)

SSA =

Here, Vpart is particle volume and SApart is particle Surface area

....... (5)

Where S is the specific surface area, Dp is the size of the particles, and is the density
of NiO 6.67 g cm-3. Mathematically, SSA can be calculated using these formulas 4
and 5. Both of these formulas yield same result. Calculated value of (SA = 213 nm 2,
Volume= 295 nm3 and SSA = 109 m2 /g) prepared NiO nanoparticles are presented in
Table 5.2
Table 5.2: Specific Surface Area of Nickel oxide Nanoparticles
Particle

Surface

Volume

Density

SSA

Surface

Size (nm)

Area (nm2)

(nm3)

(g/cm-3)

(m2/g)

area to
volume
ratio

8.25

213

295

6.67

109

0.722

5.4 SEM Analysis

The surface morphological features of synthesized nanoparticles were studied by
scanning electron microscope. Fig 5.2; 5.3; 5.4 shows the SEM image of NiO
nanoparticles with magnification of 1600, 1000 and 2500 respectively. The
instrumental parameters, accelerating voltage, spot size, and magnification and
working distances are indicated on SEM image. The results indicate that monodispersive and highly crystalline NiO nanoparticles are obtained. The appearance of
some particles is in spherical shape and some are in rod shape. We can observe that
the particles are highly agglomerated and they are essentially cluster of nanoparticles.
[33]

The SEM picture indicates the size of polycrystalline particles. The observation of
some larger nanoparticles may be attributed to the fact that NiO nanoparticles have
the tendency to agglomerate due to their high surface energy and high surface tension
of the ultrafine nanoparticles. The fine particle size results in a large surface area that
in turn, enhances the nanoparticles catalytic activity. So we can conclude that the
prepared NiO particles are in nanometre range. The average diameter of the particle
observed from SEM analysis is 100 nm, which is larger than the diameter predicted
from X-Ray broadening.

Fig 5.2: SEM image of nickel oxide nanoparticles at 1600 magnification

[34]

Fig. 5.3: SEM image of nickel oxide nanoparticles at 1000 magnification

Fig. 5.4: SEM image of nickel oxide nanoparticles at 2500 magnification

[35]

5.5 EDS Analysis

Fig 5.5: EDS spectrum for NiO nanoparticle

Fig 5.6: Weight % elemental analysis in NiO nanoparticle sample

[36]

Table 5.3: % analysis of different elements in NiO nanoparticles by EDS

Element

Approx. conc.

Weight %

Atomic %

0.45

14.85

32.69

Na

0.13

10.52

16.12

0.20

7.96

8.74

Cl

0.14

6.22

6.18

Ni

1.81

60.46

36.27

100

Total

Fig 5.7: Position of different elements in the electron image

[37]

5.6 FT-IR Analysis

Fig 5.8 shows Fourier transformed spectrum of NiO nanoparticles at room temp. The
spectrum was recorded in the range of 4000cm-1 400cm-1. The FTIR spectrum
shows the characteristics peaks at 460cm-1, 540 cm-1, 555 cm-1, 560 cm-1, 3250 cm-1,
3310 cm-1 , 3405 cm-1 . The band at 460 cm-1 reveals the presence of NiO. Despite
drying this sample contained traces of water (peaks at 3250 cm-1, 3310 cm-1). The
other peaks indicate the presence of impurities. This shows that the sample contains
some impurity. The same chemical composition is confirmed by the XRD pattern.

Fig 5.8: FT-IR Spectra of NiO nanoparticles.

[38]

5.6 UV-Visible Studies of Nickel oxide nanoparticles

Once nano nickel oxide is confirmed then the optical characterization is important.
The optical absorption spectrum of nickel oxide is shown in Fig 5.9. It can be seen
that the strongest absorption peak of the as-prepared sample appears at around 290
nm, which is fairly blue shifted from the absorption edge of bulk NiO nanoparticle.

Fig 5.9: U V-visible Spectra of NiO Nanoparticles

5.7 DSC Analysis

Several thermo analytical techniques are often used to follow the course of solid state
reactions. Differential Scanning Calorimetry (DSC) is one of the most commonly
used techniques. Inherent in such studies is the assumption that the property measured
is directly related to concentration of the product or reactant (fraction reacted) so that
the rate of the specific chemical reaction is determined versus time (isothermal) or
temperature (dynamic). The sensitivity of the technique depends upon the enthalpy of
the process. DSC measurement would follow the weight sum of the decomposition
and the subsequent amorphous to crystalline transition of intermediate. The weighing
factor would depend on the change in enthalpy for each step.

[39]

As subjected to DSC, a graph is obtained shown in Fig 5.10. A peak is found at 225
C and an upward peak shows the endothermic reaction. This peak is probably due to
dehydration reactions, due to the loss of water. Also the rate of heat flow is increased
exponentially afterwards.

Fig 5.10: DSC spectra of NiO nanoparticles.

[40]

CHAPTER 6

INDUSTRIAL RELEVANCE
Nanoparticles research is growing widely as their properties can be easily altered by
changing their shape, size & chemical properties. Nanoparticles have unexpected
optical properties, and produce quantum effects. The results of characterization
techniques have ascertained that the Nano particles so developed are the quantum dots
of Nickel is more commonly found in ores and sometimes found free in nature. It can
be alloyed with tungsten, molybdenum, chromium, iron and other metals to form
corrosion-resistant alloys. It is electrically --conductive and hence used for several
applications. Nickel nanoparticles are available as Nano fluid and in passivized, ultra
high purity, high purity, coated and dispersed forms. Various uses of NI nanoparticles
are enlisted below:

6.1 Efficient catalyst

Due to its large surface and high activity, nickel nanoparticles are efficient catalysts
for chemical reactions such as hydrogenation and treatment of exhaust to reduce
harmful chemicals. Nickel Nano particle s is also used as catalyst in hydrogen transfer
reduction reaction. In such reaction Ni Nano particles are considered as semi
heterogeneous catalyst.

Fig 6.1 portraying catalysis of Nickel

[41]

6.2 Propellant additive

Adding nickel nanoparticles to solid (rocket fuel) propellant increases combustion
heat, combustion efficiency and combustion stability.

Fig 6.2 Use in rocket propellant

6.3 Conductive paste

Conductive paste is commonly used for wiring and packaging. In the microelectronics
industry, it plays an important role in the miniaturization of electronic devices and
circuits.

6.4 High-performance electrodes

Nickel nanoparticles can be made into electrodes with a large surface area to
considerably improve energy density.

Fig 6.3 Depicting use in High performance electrode

[42]

6.5 Sintering additive

As an additive, Ni nanoparticles can effectively reduce sintering temperatures of
metals and ceramics.

6.6 Conductive coating

A coating of Ni nanoparticles can be prepared in an inert environment and below the
melting point of the bulk metal

Figure 6.4 Conductive coating.

6.7 Synthetic skin

A synthetic skin that may be used in prosthetics has been demonstrated with both selfhealing capability and the ability to sense pressure. The material is a composite
of nickel nanoparticles and a polymer. If the material is held together after a cut it
seals together in about 30 minutes giving it a self-healing ability. Also the electrical
resistance of the material changes with pressure, giving it sense ability like touch.

Fig 6.5 Artificial skin

[43]

CONCLUSION
Nanostructured particles of NiO have been successfully synthesized from the
electroplating industry waste. XRD, SEM, EDS, FT-IR, UV-Visible, DSC
characterizations studies have also been done for the synthesized nanoparticles.
XRD results estimate the average particle size as 8.25 nm and the specific surface area
is 109 m2/g having a surface to volume ratio as 0.722. It also confirms the high degree
crystallinity i.e. polycrystalline nature of the prepared sample.
SEM confirms that the particles are in nano size and the appearance of some particles
is in spherical shape and some are in rod shape. EDS analysis clearly indicates the
presence of Nickel, Oxygen, Sodium, Chlorine and Sulphur with the highest
percentage of Nickel as 60.4%. The FTIR spectrum confirms the presence of NiO
nanoparticles. DSC analysis gives an idea about the heat flow in the sample and its
stability. This simple, novel and cost effective synthesis method with the economical
and environmental handling of the hazardous waste of electroplating industries and
will be useful for industries for the preparation of nickel oxide nano-sized particles.

[44]

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[45]