RES 701 Research Methodology Assignment 2017

Assignment Submitted by: Jayakaran P., (Reg. No. 16PhD0002)

Under the Guidance of: Dr. G. S. Nirmala, Associate Prof.&Head
Department of Chemical Engineering
School of Civil and Chemical Engineering (SCLAE)
VIT University, Vellore.

SYNTHESIS OF NANOPARTICLES

Introduction

Nanoparticles are particles between 1 and 100 nanometres in size. In nanotechnology, a

particle is defined as a small object that behaves as a whole unit with respect to its transport
and properties. Particles are further classified according to diameter (Al-Amlehet al.,
2010). Ultrafine particles are the same as nanoparticles and between 1 and 100 nanometres
in size, fine particles are sized between 100 and 2,500 nanometres, and coarse particles
cover a range between 2,500 and 10,000 nanometres. Nanoparticle research is currently an
area of intense scientific interest due to a wide variety of potential applications in
biomedical, optical and electronic fields (Al-Amlehet al., 2010; Cales and Stefani, 1994;
Chevalier et al., 2006; Chevalier et al., 2009).

In general, nanoparticles are considered a discovery of modern science; they actually have a
long history. Nanoparticles were used by artisans as far back as the ninth century
in Mesopotamia for generating a glittering effect on the surface of pots (Christel and Peille,
1989).

Even these days, pottery from the middle ages and renaissance often retain a distinct gold-
or copper-colored metallic glitter. This lustre is caused by a metallic film that was applied to
the transparent surface of a glazing. The lustre can still be visible if the film has resisted
atmospheric oxidation and other weathering (Christeland Peille, 1989).

The lustre originated within the film itself, which contained silver and copper nanoparticles
dispersed homogeneously in the glassy matrix of the ceramic glaze. These nanoparticles
were created by the artisans by adding copper and silver salts and oxides together and
with vinegar, ochre, and clay on the surface of previously-glazed pottery. The object was
then placed into a kiln and heated to about 600 C in a reducing atmosphere (Azaet al.,
2002).The reducing atmosphere reduced the ions back to metals, which then came together
forming the nanoparticles that give the colour and optical effect (ChristelandPeille, 1989).
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Zirconium oxide nanoparticles (ZrO2) are available in the form of Nano-dots, Nano-fluids
and Nanocrystals having a white surface area. They are often doped with yttrium oxide,
calcia or magnesia. Zirconium is a Block D, Period 5 element and oxygen is a Block P,
Period 2 element. Zirconium oxide is also known as zirconia, zirconium, zircosol and
zirconic anhydride. The material has a density of 6.49 g/cm2, a melting point of 18520 C and
a boiling point of 35800 C. It has a hexagonal crystal structure and grayish in color. Zr does
not occur in nature in a pure state. It can be found in conjugation with silicate oxide with
mineral name Zircon or as free oxide (ZrO2) with the mineral name Baddeleyite (Dent et al.,
2008). ZrO2 is a polymorphic material and occurs in three forms: monoclinic, tetragonal,
and cubic. The monoclinic phase is stable at room temperature up to 11700 C, the tetragonal
at temperature of 1170-23700 C and the cubic at over 23700 C (Hisbergueset al.,
2009;Hewakuruppu et al., 2013).However, noticeable changes in volume are associated with
these transformation: during the monoclinic to tetragonal transformation a 5% decrease in
volume occurs when zirconium oxide is heated; conversely, a 3-4% increase in volume is
observed during the cooling process (Dent et al., 2008; HjerppeandLassila, 2009).

Several different oxides are added to zirconia to stabilize the tetragonal and cubic phases.
Magnesia (MgO), Yttria (Y2O3), Calcia(CaO), and Ceria (CeO), amongst others, allow the
generation of multiphase materials known as Partially Stabilized Zirconia (PSZ), whose
microstructure at room temperature generally consists of cubic zirconia as the major phase,
with monoclinic and tetragonal zirconia precipitates as the minor phase (Kosmac et al.,
1999; Khan et al., 2012). PSZ materials have been tested for their potential use as ceramic
biomaterials. Mg-PSZ is one of the most commonly used zirconia-based engineering
ceramics (Lange et al., 1986). Residual porosity in the mass of the material, a rather coarse
grain size (30-40 m), and difficulties in obtaining Mg-PSZ precursors free of impurities,
are all factors that have discouraged the interest of ceramic manufacturers in the
development of Mg-PSZ for biomedical applications (Maniconeet al., 2007). It has been
reported that reinforcement by phase transformation toughening is less pronounced in Mg-
PSZ than in Y-TZP (Yttrium-Tetragonal Zirconia Polycrystals, a finding that is discussed
below.

Water and non-aqueous solvents can induce the formation of zirconiahydroxides along a
crack. This process accelerates expansion of the fracture and can result in reduced strength,
toughness, and density, leading to failure of the restoration (Piconi et al.,1995; Reiss and
Andreas, 2010; Suresh et al., 2003). Surface grinding can also reduce strength.
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Kosmac(Kosmacet al., 1999) confirmed this observation and reported reduced mean
strength and reliability of zirconium oxide after grinding. Zirconia is characterized by high
flexural strength and fracture toughness as a result of a physical property known as
transformation toughening (Swab et al., 1991; Saridag et al., 2013). The incidence of
framework fracture was directly related to the design of the FPD, where inlay retained FPDs
(IRFPD) showed the highest failure rate (SaridagandPekkan, 2007; Taylor et al., 2003). The
most common complication observed in zirconia-based restorations was fracture of the
veneering porcelain, manifesting clinically as chiping fractures of the veneering ceramic
with or without exposing the underlying Y-TZP framework (Taylor et al., 2003). Several
factors that may affect the rate of veneering fractures have been investigated. A loss of
veneering material may result from an alteration of the crystal structure of the zirconia
surface during airborne-particle abrasion of the framework before the veneering process.
This may result in a change of the temperature expansion coefficients. Other factors include
the different surface treatments of the frameworks and the bond strength between the
veneering ceramics and zirconia frameworks (Taylor et al., 2012;Evatet al., 2013)

Bansal and co-workers were the first to report a cost-effective, protein- mediated synthesis
method for crystalline zirconia nanoparticles using the fungus, fusariumoxysporum at room
temperatures and natural PH (Chandra et al., 2010).

Fabrication of nanomaterials of various shape, size and controlled dispersity have been the
subject of supreme interest due to their prospective properties such as high surface area and
high fraction of surface atoms.With the development of new and chemical or physical
methods, the concerns for environmental contamination are also heightened and resulted in
generation of large amount of hazardous by-products. Thus there is a need for the
development of green, cost effective and environmentally benign methods and material for
the synthesis of nanoparticles that do not use toxic chemicals in their synthesis protocols.
Though numerous chemical methods are available for the nanoparticle synthesis such as sol-
process, sol-gel, chemical precipitation, pyrolysis, chemical vapour deposition but copious
reactants and starting material external agents and reduction of metal salts involve in these
process are toxic and potentially hazardous. To defeat these problems, a viable alternative
and advanced approach have been raised over chemical methods, of which the biological
synthesis has more environmental concerns such as eco-friendliness and compatibility for
various applications in biomedical and pharmaceutical fields. Many biotechnological
synthesis using micro-organisms, plant extracts or enzymes and templates like DNA,
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membranes, viruses and di-atoms, have been raised (Kroger et al., 2009; Garvey et al.,
1975).ZrO2nanoparticles have received special interest for their attractive scientific and
technological aspects in different fields due to mechanical and electrical properties, high
dielectric constants, and wide band gaps. These mechanical and electronic properties where
were discovered and studies mainly in micro-crystalline zirconia, but recently they have also
been studied in crystalline zirconia. Its attractive properties have extended for many
applications in various fields like gas sensors, solid fuel cells, high durability coating,
catalytic agents, etc. (Somiyaet al., 1988; Duran et al., 2009).Semiconductor nanomaterials
have brought great interest for the photocatalytic degradation of organic dyes because of
their size dependent optical,catalytic, surface to volume ratio and electric properties.

CARBON NANOTUBES

Introduction

The Amazing and Versatile Carbon Chemical basis for life With an atomic number of 6,
Carbon is the 4th most abundant element in the Universe by mass after (Hydrogen Helium
and Oxygen). It forms more compounds that any other element, with almost 10 million pure
organic compounds. Abundance, together with the unique diversity of organic compounds
and their unusual polymer forming ability at the temperatures commonly encountered on
Earth makes the element the chemical basis of all known life.

Carbon Nanotubes

Carbon Nanotubes, long, thin cylinders of carbon, were discovered in 1991 by SumioIijima.
These are large macromolecules that are unique for their size, shape, and remarkable
physical properties. They can be thought of as a sheet of graphite (a hexagonal lattice of
carbon) rolled into a cylinder. These intriguing structures have sparked much excitement in
recent years and a large amount of research has been dedicated to their understanding.
Currently, the physical properties are still being discovered and disputed. Nanotubes have a
very broad range of electronic, thermal, and structural properties that change depending on
the different kinds of nanotube (defined by its diameter, length, and chirality, or twist). To
make things more interesting, besides having a single cylindrical wall (SWNTs), Nanotubes
can have multiple walls (MWNTs)--cylinders inside the other cylinders.

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Key properties of Carbon Nanotubes

Carbon Nanotubes are an example of true nanotechnology: they are less than 100
nanometers in diameter and can be as thin as 1 or 2 nm. They are molecules that can be
manipulated chemically and physically in very useful ways. They open an incredible range
of applications in materials science, electronics, chemical processing, energy management,
and many other fields.

Some properties include

Extraordinary electrical conductivity, heat conductivity, and mechanical properties.

They are probably the best electron field-emitter known, largely due to their high length-
todiameter ratios

As pure carbon polymers, they can be manipulated using the well-known and the
tremendously rich chemistry of that element. Some of the above properties provide
opportunity to modify their structure, and to optimize their solubility and dispersion. These
extraordinary characteristics give CNTs potential in numerous applications.

Key application areas

Field Emitters/Emission: Conductive or reinforced plastics Molecular electronics: CNT

based non volatile RAM CNT based transistors Energy Storage CNT based fibers and
fabrics CNT based ceramics Biomedical applications etc ...

Properties of Carbon Nanotubes

The structure of a carbon nanotube is formed by a layer of carbon atoms that are bonded
together in a hexagonal (honeycomb) mesh. This one-atom thick layer of carbon is called
graphene, and it is wrapped in the shape of a cylinder and bonded together to form a carbon
nanotube. Nanotubes can have a single outer wall of carbon, or they can be made of multiple
walls (cylinders inside other cylinders of carbon). Carbon nanotubes have a range of electric,
thermal, and structural properties that can change based on the physical design of the
nanotube. Single-walled carbon nanotube structure Single-walled carbon nanotubes can be
formed in three different designs: Armchair, Chiral, and Zigzag. The design depends on the
way the graphene is wrapped into a cylinder. For example, imagine rolling a sheet of paper
from its corner, which can be considered one design, and a different design can be formed

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by rolling the paper from its edge. A single-walled nanotubes structure is represented by a
pair of indices (n,m) called the chiral vector. The chiral vector is defined in the image below.

Fig: Structure of Carbon Nanotubes

The structural design has a direct effect on the nanotubes electrical properties. When
n m is a multiple of 3, then the nanotube is described as "metallic" (highly
conducting), otherwise the nanotube is a semiconductor. The Armchair design is
always metallic while other designs can make the nanotube a semiconductor.

Multi-walled carbon nanotube structure

There are two structural models of multi-walled nanotubes. In the Russian Doll
model, a carbon nanotube contains another nanotube inside it (the inner nanotube has
a smaller diameter than the outer nanotube). In the Parchment model, a single
graphene sheet is rolled around itself multiple times, resembling a rolled up scroll of
paper. Multi-walled carbon nanotubes have similar properties to singlewalled
nanotubes, yet the outer walls on multi-walled nanotubes can protect the inner
carbon nanotubes from chemical interactions with outside materials. Multi-walled
nanotubes also have a higher tensile strength than single-walled nanotubes.

Strength

Carbon nanotubes have a higher tensile strength than steel and Kevlar. Their strength
comes from the sp bonds between the individual carbon atoms. This bond is even
stronger than the sp bond found in diamond. Under high pressure, individual

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nanotubes can bond together, trading some sp bonds for sp bonds. This gives the
possibility of producing long nanotube wires. Carbon nanotubes are not only strong,
they are also elastic. You can press on the tip of a nanotube and cause it to bend
without damaging to the nanotube, and the nanotube will return to its original shape
when the force is removed. A nanotube's elasticity does have a limit, and under very
strong forces, it is possible to permanently deform to shape of a nanotube. A
nanotubes strength can be weakened by defects in the structure of the nanotube.
Defects occur from atomic vacancies or a rearrangement of the carbon bonds.
Defects in the structure can cause a small segment of the nanotube to become
weaker, which in turn causes the tensile strength of the entire nanotube to weaken.
The tensile strength of a nanotube depends on the strength of the weakest segment in
the tube similar to the way the strength of a cahin depends on the weakest link in the
chain.

Electrical properties

As mentioned previously, the structure of a carbon nanotube determines how

conductive the nanotube is. When the structure of atoms in a carbon nanotube
minimizes the collisions between conduction electrons and atoms, a carbon nanotube
is highly conductive. The strong bonds between carbon atoms also allow carbon
nanotubes to withstand higher electric currents than copper. Electron transport occurs
only along the axis of the tube. Single walled nanotubes can route electrical signals
at speeds up to 10 GHz when used as interconnects on semi-conducting devices.
Nanotubes also have a constant resistively.

Thermal Properties

The strength of the atomic bonds in carbon nanotubes allows them to withstand high
temperatures. Because of this, carbon nanotubes have been shown to be very good
thermal conductors. When compared to copper wires, which are commonly used as
thermal conductors, the carbon nanotubes can transmit over 15 times the amount of
watts per meter per Kelvin. The thermal conductivity of carbon nanotubes is
dependent on the temperature of the tubes and the outside environment.

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Potential Uses

There are many potential applications for Carbon nanotubes from waterproof and
tear resistant cloth fabrics, concrete and steel like applications (a space elevator has
even been proposed) based on the property of strength, electrical circuits based on
the property of electrical conductivity, sensors based on the property of thermal
conductivity, vacuum proof food packaging, and even as a vessel for delivering
drugs.

Carbon Nanotube technology also holds promise for a wide range of energy-related
applications like Batteries, Solar cells etc.,

Current hurdles

There are several remaining obstacles, technical and non-technical to CNT success.
Covering these in detail is length and probably impossible; flipped on its head, such
a passage would be a path to success with nanotubes. But here are a couple of the
major impediments such as Electronic Heterogeneity, Orientation, Size and Density

Fabrication

The furtherment of fabrication technology will require the ability to target nanotubes
with high yield of specified lengths, diameter, number of walls, and chirality. There
are several procedures that have been developed for fabricating CNT structures. Few
of them are Arc Discharge Method,Laser Ablation Method, Chemical Vapor
Deposition and Pyrolysis.

There is much about carbon nanotubes that is still unknown. More research needs to
be done regarding the environmental and health impacts of producing large
quantities of them. There is also much work to be done towards cheaper mass-
production and incorporation with other materials before many of the current
applications being researched can be commercialized. There is no doubt however
that carbon nanotubes will play a significant role in a wide range of commercial
applications in the very near future. Not only will they help create some very cool
tech gadgets, they may also help solve the world's energy problems.

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 RES 701 Research Methodology Assignment 2017

CHARACTERIZATION OF NANOPARTICLES

UV-Vis Spectroscopy

Ultra-visible spectroscopy or ultraviolet-visible spectrophotometry (UV-Vis) refers

to absorption spectroscopyorreflectance spectroscopy in the ultra-visible-spectral region. It
uses light in the visible and adjacent (near-UV and near infrared regions [NIR]) ranges. The
absorption or reflectance in the visible range directly affects the perceived colour of the
chemical involved. In this region of the electromagnetic spectrummolecules undergo
electronic transitions. This technique is complementary to fluorescence spectroscopy, in that
deals with transitions from the excited state to the ground state, while absorption measures
transitions from the ground state to the excited state. UV/Vis spectroscopy is routinely used
in analytical chemistry for the quantitative determination of different analytes, such
astransition metal ions, highly conjugated organic compounds, and biological
macromolecules. Spectroscopic analysis is commonly carried out in solutions but solids and
gases may also be studied.

The Beer-Lambert law states that the absorbance of a solution is directly proportional to the
concentration of the absorbing species in the solution and the path length.[3] Thus, for a fixed
path length, UV-Vis spectroscopy can be used to determine the concentration of the absorber
in a solution. It is necessary to know how quickly the absorbance changes with
concentration. This can be taken from references (tables of molar extinction coefficients), or
more accurately, determined from a calibration curve.The presence of an analyte gives a
response assumed to be proportional to the concentration. For accurate results, the
instrument's response to the analyte in the unknown should be compared with the response
to a standard; this is very similar to the use of calibration curves. The response (e.g., peak
height) for a particular concentration is known as the response factor.

The wavelengths of absorption peaks can be correlated with the types of bonds in a given
molecule and are valuable in determining the functional groups within a molecule. The
nature of the solvent, the pH of the solution, temperature, high electrolyte concentrations,
and the presence of interfering substances can influence the absorption spectrum.
Experimental variations such as the slit width (effective bandwidth) of the

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spectrophotometer will also alter the spectrum. To apply UV-Vis spectroscopy to analysis,
these variables must be controlled or accounted for in order to identify the substances
present.

X-Ray Diffraction analysis(XRD)

Diffractometer operated at 40 Kv with a current of 30 ma using cu-Ka for the determination

of crystallinity and crystal size of the Nano-particles.X-rays are generated in a cathode ray
tube by heating a filament to produce electrons, accelerating the electrons toward a target by
applying a voltage, and bombarding the target material with electrons. When electrons have
sufficient energy to dislodge inner shell electrons of the target material, characteristic X-ray
spectra are produced. These spectra consist of several components, the most common being
K and K. K consists, in part, of K1 and K2. K1 has a slightly shorter wavelength and
twice the intensity as K2. The specific wavelengths are characteristic of the target material
(Cu, Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, is required to produce
monochromatic X-rays needed for diffraction. K1and K2 is sufficiently close in wavelength
such that a weighted average of the two is used. Copper is the most common target material
for single-crystal diffraction, with CuK radiation = 1.5418. These X-rays are collimated
and directed onto the sample. As the sample and detector are rotated, the intensity of the
reflected X-rays is recorded. When the geometry of the incident X-rays impinging the
sample satisfies the Bragg Equation, constructive interference occurs and a peak in intensity
occurs. A detector records and processes this X-ray signal and converts the signal to a count
rate which is then output to a device such as a printer or computer monitor.

The intensity of diffracted X-rays is continuously recorded as the sample and detector rotate
through their respective angles. A peak in intensity occurs when the mineral contains lattice
planes with d-spacings appropriate to diffract X-rays at that value of . Although each peak
consists of two separate reflections (K1 and K2), at small values of 2 the peak locations
overlap with K2 appearing as a hump on the side of K1. Greater separation occurs at
higher values of . Typically these combined peaks are treated as one. The 2 position of the
diffraction peak is typically measured as the centre of the peak at 80% peak height.

Results are commonly presented as peak positions at 2 and X-ray counts (intensity) in the
form of a table or an x-y plot (shown above). Intensity (I) is either reported as peak height
intensity, that intensity above background, or as integrated intensity, the area under the peak.

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The relative intensity is recorded as the ratio of the peak intensity to that of the most intense
peak (relative intensity = I/I1 x 100).

The d-spacings of each peak is then obtained by solution of the Bragg equation for the
appropriate value of . Once all d-spacings have been determined, automated search/match
routines compare the ds of the unknown to those of known materials. Because each mineral
has a unique set of d-spacings, matching these d-spacings provides an identification of the
unknown sample. A systematic procedure is used by ordering the d-spacings in terms of
their intensity beginning with the most intense peak. Files of d-spacings for hundreds of
thousands of inorganic compounds are available from the International Centre for
Diffraction Data as the Powder Diffraction File (PDF). Many other sites contain d-spacings
of minerals such as the American Mineralogist Crystal Structure Database. Commonly this
information is an integral portion of the software that comes with the instrumentation.

Fourier Transform Infrared Electron Spectroscopy (FTIR)

The Fourier transform infrared spectroscopy (FTIR) analysis was performed by using a
Perkin Elmer make Model Spectrum RX1 (Range 4000/cm-400/cm) to determine the
functional group.Fourier transform infrared spectroscopy (FTIR) is a technique which is
used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. An
FTIR spectrometer simultaneously collects high spectral resolution data over a wide spectral
range. This confers a significant advantage over a dispersive spectrometer which measures
intensity over a narrow range of wavelengths at a time.

The term Fourier transform infrared spectroscopy originates from the fact that a Fourier
transform (a mathematical process) is required to convert the raw data into the actual
spectrum. The goal of any absorption spectroscopy (FTIR, UV-visspectroscopy, etc.) is to
measure how well a sample absorbs light at each wavelength. Fourier transform
spectroscopy is a less intuitive way to obtain the same information. Rather than shining
a monochromatic beam of light at the sample, this technique shines a beam containing many
frequencies of light at once, and measures how much of that beam is absorbed by the
sample. Next, the beam is modified to contain a different combination of frequencies, giving
a second data point. This process is repeated many times. Afterwards, a computer takes all
these data and works backwards to infer what the absorption is at each wavelength.

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The beam described above is generated by starting with a broadband light source one
containing the full spectrum of wavelengths to be measured. The light shines into
a Michelson interferometera certain configuration of mirrors, one of which is moved by a
motor. As this mirror moves, each wavelength of light in the beam is periodically blocked,
transmitted, blocked, transmitted, by the interferometer, due towave. Different wavelengths
are modulated at different rates, so that at each moment, the beam coming out of the
interferometer has a different spectrum.

As mentioned, computer processing is required to turn the raw data (light absorption for
each mirror position) into the desired result (light absorption for each wavelength). The
processing required turns out to be a common algorithm called the Fourier transform . This
instrument covered the wavelength range from 2.5 m to 15 m (wavenumber range
4000 cm1 to 660 cm1). The lower wavelength limit was chosen to encompass the highest
known vibration frequency due to a fundamental molecular vibration. The upper limit was
imposed by the fact that the dispersing element was a prism made from a single crystal of
rock-salt (sodium chloride) which becomes opaque at wavelengths longer than about 15 m;
this spectral region became known as the rock-salt region. Later instruments used potassium
bromide prisms to extend the range to 25 m (400 cm1) and caesium iodide 50 m
(200 cm1). The region beyond 50 m (200 cm1) became known as the far-infrared region;
at very long wavelengths it merges into the microwave region. Measurements in the far
infrared needed the development of accurately ruled diffraction gratings to replace the
prisms. The dispersing elements since salt crystals are opaque in this region. More sensitive
detectors than the bolometer were required because of the low energy of the radiation

FESEM-EDAX

Scanning electron microscope: In an electron microscope electrons emitted from a hot

filament isusually used. However, sometimes cold cathode (a cathode which emits electrons
without heating it) is alsoused. A cold cathode emits electrons under the application of a
very high electric field. It is also known asfield emitter. Such SEMs are known as FE-SEM
and are able to give better images than hot filament SEM.

In scanning electron microscope backscattered electrons or secondary electrons are detected.

Due tointeraction of focused beam with solid, the backscattered electrons are defocused
resulting into loweredresolution than one would expect. In an electron microscope, the

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electron beam can be focused to a verysmall spot size using electrostatic or magnetic lenses.
Usually the electrostatic lenses are used for an SEM.

The fine beam is scanned or rastered on the sample surface using a scan generator and back
scatteredelectrons are collected by an appropriate detector.Signal from scan generator along
with amplified signal from the electron collector generates the image ofsample surface. In
order to avoid the oxidation and contamination of filament as well as reduce the
collisionbetween air molecules and electrons, filament and sample have to be housed in a
vacuum chamber.

Usually vacuum ~10-5 torr is necessary for a normal operation of scanning of electron
microscope.Electrons are accelerated as usual in a vacuum system but they enter the sample
chamber through a thinfoil or aperture so that a large pressure difference can be
maintained.One disadvantage of SEM is that insulating samples cannot be analyzed directly
as they get charged dueto incident electrons and images become blurred/faulty. Therefore,
insulating solids are coated with a verythin metal film like gold or platinum making them
conducting without altering any essential details of thesample. The metal film is usually
sputter coated on the sample to be investigated prior to the introductioninto SEM.

Field emission scanning electron microscopy - Energy dispersive X-ray analysis (FESEM-
EDAX) was performed to check the surface morphology and elemental analysis of
nanoparticles formed. SEM imaging to obtain high magnification images. The samplesand
were placed on carbon tape mounted on an aluminum stub. The EDAX has been carried to
obtain the elemental and/or qualitative composition of the two samples using FESEM,
SUPRA 55-CARL, ZEISS, GERMANY.

Transmission Electron Microscopy (TEM)

Transmission electron microscopy (TEM) is a microscopy technique in which a beam

of electrons is transmitted through an ultra-thin specimen, interacting with the specimen as it
passes through it. An image is formed from the interaction of the electrons transmitted
through the specimen; the image is magnified and focused onto an imaging device, such as
a fluorescent screen, on a layer ofphotographic film, or to be detected by a sensor such as
a CCD camera.

TEMs are capable of imaging at a significantly higher resolution than light microscopes,
owing to the small de Broglie wavelength of electrons. This enables the instrument's user to
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examine fine detail,even as small as a single column of atoms, which is thousands of times
smaller than the smallest resolvable object in a light microscope. TEM forms a major
analysis method in a range of scientific fields, in physical, chemical and biological sciences.
TEMs find application in cancer research, virology, materials science as well
as pollution,nanotechnology, and semiconductor research.

At smaller magnifications,TEM image contrast is due to absorption of electrons in the

material, due to the thickness and composition of the material. At higher magnifications
complex wave interactions modulate the intensity of the image, requiring expert analysis of
observed images. Alternate modes of use allow for the TEM to observe modulations in
chemical identity, crystal orientation, electronic structure and sample induced electron phase
shift as well as the regular absorption based imaging.

High-voltage TEMs require ultra-high vacuums on the range of 107 to 109 Pa to prevent
the generation of an electrical arc, particularly at the TEM cathode. As such for higher
voltage TEMs a third vacuum system may operate, with the gun isolated from the main
chamber either by gate valves ora differential pumping aperture - a small hole that prevents
the diffusion of gas molecules into the higher vacuum gun area faster than they can be
pumped out. For these very low pressures, either an ion pump or a getter material is used.

Poor vacuum in a TEM can cause several problems ranging from the deposition of gas
inside the TEM onto the specimen while viewed in a process known as electron beam
induced deposition to more severe cathode damages caused by electrical discharge. The use
of a cold trap to adsorb sublimated gases in the vicinity of the specimen largely eliminates
vacuum problems that are caused by specimen sublimation.

REFERENCES
1. Ayhan, D. J., Adv. Funct. Mater., 16(2009) 1-9.
2. Banat, I.M., Nigam, P, Singh, D, Marchant, R. (1996). Bioresour. Technol. 58(10)
217227.
3. Bootharaju, M.S., Pradeep, T., Langmuir, 28(2012) 6712679.
4. Bradder, P, Ling, S.K, Wang, S, Liu, S.J.,Chem. Eng. Data.56
(2010) 138141.
5.Cales B., Stefani Y., Mater. Chem., 52 (1994) 376-380.
6. Chandra, V., Park, J., Chun, Y, Lee, J. W, Hwang J., Chem. Commun. , 4(2010)
39793986.

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7. Chandra, V, Kim, K.S., Chem. Commun., 47(2011) 39423946.
8. Chevalier J.,What future for zirconia as a biomaterial, CRC Press. (2006) 535-543.
9.Chevalier J, Gremillard L, Virkar AV, Clarke D., the tetragonal-monoclinic
transformation in zirconia, 28(2009) 1901-1920.
10. Christel P., Meunier A., Heller M., Torre J.P., PeilleC.N.,Mechanical properties
and short-term in-vivo evaluation of yttrium-oxide-partially-stabilized
zirconia,52(1989) 45-61.
11. Demirbas, A. J, Hazard. Mater.,167(2009) 19.
12. Duran, A.,Tuzen, M, Soylak, M. J., Hazard. Mater.,169(2009) 466471.
13. Du Aza A.H., Chevalier J, FantozziG,Schehl M, Torrecillas R., Crack growth
resistance of alumina, zirconia and zirconia toughened alumina ceramics for
joint prostheses, 23(2002)937-945.
14.FirdossAlam khan, Biotechnology Fundamentals, CRC Press. (2011) 328.
15. Fischer J, Stawarczyk B, Hmmerle C.H., Flexural strength of veneering
ceramics for zirconia, J. Dent, 33(2011)316-321.
16. Garvey, R.C., Hannic, R.H., Pascoe, R.T.(2002), Nature, 258 (1975) 703.
17.Gowri, S., Rajiv Gandhi, R., Sundrarajan, M.,J.(2014). Mater. Sci. Technol.,
30(8), 782 790.
18.Gillan, E.G., and Kaner, R.B., J. Mater. Chem., 11(2001) 1951.
19.Hisbergues M, Vendeville S, Vendeville P., Zirconia: Physical and chemical
properties, Am. Chem. Soc., 20(2009) 519-529.
20.Hewakuruppu, Y. L.; Dombrovsky, L. A.; Chen, C.; Timchenko, V.; Jiang, X.;
Baek, S.; Taylor, A., Tex. Res. J, 78(2013) 52-58.
21.Hjerppe J.,Vallittu P.K.,Frberg K, LassilaL.V.,Effect of sintering time on biaxial
strength of zirconium dioxide, Tex. Res. J, 306(2009) 166-171.
22.Kalpana, K.,Selvaraj, V., Synthesis and crystallization of ZrO2nanocrystalline
Powders by Hydrothermal process, Mater Lett, Nature,(2015) 12-22.
23. Kosmac T., Oblak C., Jevnikar P, Funduk N, Marion L., The effect of surface
grinding and sandblasting on flexural strength and reliability of Y-TZP zirconia
ceramic, Nature, (1999) 426-433.
24. Koul, O., Isman, M. B. and Ketkar, C. M., Can. J. Bot., Adv. Funct. Mater,
98(1990) 111.
25. Khan, FirdosAlam ,Biotechnology Fundamentals. CRC Press, (2012)328.
26. Kroger, N., Deutzmann, N., Bersdorf, C., Sumper, M., Proc. Natl. Acad. Sci. U.
S. A., 75 (2000) 14133.

16
 RES 701 Research Methodology Assignment 2017
27. Lange FF, Dunlop GL, Davis BI.,Degradation during aging of transformation-
toughned ZrO2-Y2O3 materials at 2500 C, Am. Chem. Soc., (1986) 237-240.
28. Lovley, R., Stolz, J.F., Nord, Phillips, E.J.F., Nature, 330 (1987) 252.
29.Manicone PF, Rossi Iommetti P, Raffaelli L., An overview of zirconia ceramics:
basic properties and clinical applications, Langmuir, (2007) 819-826.
30. Milligan, N., Morel, F. M. M.,Adv. Funct. Mater, 297(2002) 1848.
31.Mukherjee, P., Senapati, S., Mandal, D., Ahmad, A., Khan, M.I., Kumar R.,
Sastry, M., RSC Adv., 3(2002) 461.
32.Noh, H., Seo, D., Kim H., Lee, J., Mater. Lett., 57(2003) 2425.
33. Omoja, V. U., Anaga, A. O., Obidike, I. R., Ihedioha, T. E., Umeakuana, P. U.,
Mhomga, Chem.C, 4(2011) 337-341.
34. Patwardhan, S.V., Mukherjee, N., Steinitz-Kannan, M., Clarson, S.J., Chem.
Commun., (2003) 1122.
35. Pelez J, Cogolludo PG, Serrano B, Lozano JF, Surez MJ., RSC Adv.,4(2012)
373-379.
36. Philse, P., Maas, D.,Desalination Water, Langmuir, 18 (2002) 9977.
37. Piconi C, Maccauro G., Zirconia as a ceramic biomaterial, Am. Chem. Soc.,
132(1999) 1-25.
38.Raihani, H. A., Durand, B., Chassagneux, B., Kerridge D. and Inman, D., Applied
Catalysis, J. Mater. Sci., 4(1994) 133.
39.Reiss, Gunter; Hutten, Andreas , In Sattler, Klaus D.Handbookof Nanophysics:
Nanoparticles and Quantum Dots, CRC Press,(2010) 53-54
40.Savita Dixit, Huma Ali, J. Chem. &Cheml. Sci. (2010) Vol.1 (1), 79-85.
41.Shevchenko, A.V., Dudnik, E.V., Ruban, A.K., Redko, V.P., Vereschaka, V.M.,
and Lopato, L.M., Adv. Func. Mater, 41(2002) 51.
42. Shimizu, K., Cha, J., Stucky G. D., Morse, D. E., Proc. Natl. Acad. Sci. U. S. A.,
89(1998) 6234.
43.Sleytr, U.B., Messner, P., Pum, D., Sara,M., Angew. Chem., Int. Ed., 38(1999)
1034.
44.Somiya, S., Yamamoto, N., and Yanagina, H., Science and Technology of
Zirconia III, in Advances in Ceramics, American Ceramic Society,
Westerville, J.Mater. Chem, 14(1988) 24-25.
45. Suresh A., Mayo M.J., Porter W.D., RawnCJ.,Crystallite and grain-size-
dependent phase transformations in yttria-doped zirconia, 46(2003) 360-362.
46. Sundh A., SjgrenG.,Fracture resistance of all-ceramic zirconia bridges with
differing phase stabilizers and quality of sintering,8(2006) 778-784.

17
 RES 701 Research Methodology Assignment 2017
47. Swab J.J., Low temperature degradation of Y-TZP materials, 165(1991) 6706-
6714.
48. Saridag S., Sevimay M., PekkanG.,Fracture Resistance of Teeth Restored With
All-ceramic Inlays and Onlays, 24(2013) 12-211.
49. Saridag S., OzyesilA.G,Pekkan G., Fracture strength and bending of all-ceramic
and fiber-reinforced composites in inlay-retained fixed partial dentures,
57(2007) 159-161.
50. Taylor, Robert, Coulombe, Sylvain, Otanicar, Todd, Phelan, Patrick, Gunawan,
Andrey, L.V., Wei, Rosengarten, Gary, Prasher, Ravi,Tyagi, Himanshu, Proc.
Technol. 195(2003)111-113.
51. Taylor, Robert A., Otanicar, Todd P. Herukerrupu, Yasitha, Bremond,
Fabienne, Rosengarten, Gary, Hawkes, Evatt R., Jiang, Xuchuan, Coulombe,
Langmuir 18(2013) 1413-22.
53. VipulBansal, DebabrataRautaray, Absar Ahmad, MuraliSastry, J. Mater. Chem.,
14(2004) 33033305.
54.Xu, H., Quin, D., Yang, D., and Li, H.,, Mater. Chem. Phys., 80 (2003) 509-524.
55. http://en.wikipedia.org/wiki/SWNT#Single-walled

56. CheapTubes.com CNT 101 Presentation (2008, April 24). In

http://www.cheaptubesinc.com/cnt101.htm

57. A 1 GHz Integrated Circuit with Carbon Nanotube Interconnects and Silicon
Transistors - http://nano.stanford.edu/publication.php?id=135

58. Carbon Nanotube Single-Electron Transistors at Room Temperature. By Henk

W. Ch. Postma, TijsTeepen, Zhen Yao,* Milena Grifoni, Cees Dekker
http://www.sciencemag.org/cgi/content/full/293/5527/76

59. Nanotube Field Effect Transistor -

http://www.research.ibm.com/nanoscience/fet.html

60. (Future Of Computing: Carbon Nanotubes And Superconductors To Replace The

Silicon Chip. ScienceDaily.)

61. Carbon nanotube. (2008, April 24). In Wikipedia, The Free Encyclopedia.
Retrieved 03:04, April 28, 2008, from
http://en.wikipedia.org/w/index.php?title=Carbon_nanotube&oldid=207910667

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 RES 701 Research Methodology Assignment 2017
62.Graphene. (2008, April 27). In Wikipedia, The Free Encyclopedia. Retrieved
03:01, April 28, 2008, from
http://en.wikipedia.org/w/index.php?title=Graphene&oldid=208624307

63. Nanotubes pack power.

http://www.trnmag.com/Stories/2002/022702/Nanotubes_pack_power_022702.html

64. Physical properties of carbon nanotubes.

http://www.pa.msu.edu/cmp/csc/ntproperties/

65. Carbon-Nanotube Wiring Gets Real. IEEE - Spectrum

04.08.http://blogs.spectrum.ieee.org/articles/2008/03/carbonnanotube_wiring_gets_rea.html

66. Nanotubes and their implications for computing.

http://www.rpi.edu/dept/phys/ScIT/FutureTechnologies/nano/nanotubes.html [13]
Carbon Nanotube Based NanoComposite Paper Energy Storage May Replace
Batteries - http://www.azonano.com/news.asp?newsID=4710

67. Nano-Manhattan: 3D Solar Cells Boost Efficiency While Reducing Size, Weight
and Complexity of Photovoltaic Arrays - http://www.gtri.gatech.edu/casestudy/3d-
solar-cells-boost-efficiency

68. S. lijima, Nature 354, 56 (1991).

69. Crystalline Ropes of Metallic Carbon Nanotubes. Science, New Series, Vol. 273,
No. 5274 (Jul. 26, 1996), pp. 483-487

70. Large-Scale Synthesis of Aligned Carbon Nanotubes. W. Z. Li, S. S. Xie, * L. X.

Qian, B. H. Chang, B. S. Zou, W. Y. Zhou, R. A. Zhao, G. Wang [18] T. W. Ebbesen
and P. M. Ajayan, Nature 358, 220 (1992); D. T. Colbert etal., Science 266,1218
(1994).

71. Direct Synthesis of Long Single-Walled Carbon Nanotube StrandsDirect

Synthesis of Long SingleWalled Carbon Nanotube Strands. H. W. Zhu, C. L. Xu, D.
H. Wu, B. Q. Wei, R. Vajtai, P. M. Ajayan Retrieved from
http://cubist.cs.washington.edu/wiki/index.php/Csep590a-c

72. BRAZIL: Warning - These Computers Come With Strings Attached

http://www.ipsnews.net/news.asp?idnews=39480

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