1

CHAPTER 1

INTRODUCTION

1.1 AUTOMOBILE POLLUTION

Pollution is defined as the introduction of chemicals, particulate matter, or

biological materials to the atmosphere that cause harm or discomfort to the living
organisms.

Due to the advancement in science and technology there is an drastic

improvement in automobile production which results in more amount of harmful gas is
let into the atmosphere. Thus these gases react with the atmosphere and pollute it.

Generally, automobile plays an important role in contribution to the pollution.

Various exhaust product and its characteristics were listed below.

Table 1.1 Pollutants and its characteristics

Pollutant Characteristics
Nitrogen oxides It is an reddish-brown toxic gas emitted
from high temperature combustion
Carbon monoxide Colourless, odorless, non-irritating but
very poisonous gas.
Particulate matter These are tiny particles of solid or liquid
suspended in a gas which cause health
hazards such as heart disease, altered lung
function
Sulfur oxides Generally SO2 reacts with atmosphere to
form H2SO4, and thus acid rain

Thus it is really necessary to incorporate a device which reduces the exhaust

pollution.
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1.2 NANOTECHNOLOGY

Nanotechnology refers to a field of applied science and technology whose

theme is the control of matter on the atomic and molecular scale, generally 100
nanometers or smaller, and the fabrication of devices or materials that lie within that size
range.

As far as nanotechnology is concern, Nanoparticles may be defined as those

particles have dimensions in the range 1 to 100 nm. Nanoparticles possess unique hybrid
properties of neither the molecular nor the bulk solid-state limits. Materials reduced to the
nanoscale can suddenly show very different properties compared to what they exhibit on
a macroscale, enabling unique applications. For instance copper nanoparticles smaller
than 50 nm are considered super hard materials that do not exhibit the same malleability
and ductility such a huge improvement in properties is observed in case of nano
materials. Generally nanoparticles are classified as nanotubes, nanowire, nano crystals
etc. Table 1.2 summarizes the main categories of nanoparticle according to their
morphologies, material from which they may be composed and the type of application in
which they may be used.

Table 1.2 Nanoparticles-Categories and Applications

Nanostructure Example Material or Application

Nanotubes Carbon, (fullerenes)

Nanowires Metals, semiconductors, oxides

Nanocrystals, quantum dots Insulators, semiconductors, metals,

1.3 NANOMATERIALS

Nano materials widely used are metallic nanoparticle, germanium, ceramic

and aluminium oxide nanowires, carbon, silicon and germanium nanotubes, zinc oxide
nanocrystals, gold nanowafers and copper oxide nanotubes which can be synthesized by
 3

various processes such as laser ablation, condensation from vapour, thermal

decomposition etc.

1.4 CATALYTIC CONVERTER

A catalytic converter is most effective after treatment process used to reduce

the toxicity of emissions from an internal combustion engine. A catalytic converter is a
device that converts the harmful toxic combustion products and its by-products into less-
toxic substances. Catalyst is not consumed during the reaction hence it is non-degradable.
Catalytic converter is generally used for reduction of HC, CO and NOx. It consists of
steel container of honeycomb structure through which the gas flows. It consists of small
embedded particles of catalytic materials such as platinum, palladium, rhodium that
promotes oxidation reaction in exhaust gas. Catalytic converter uses alumina as base
material because it can withstand high temperature, low thermal expansion etc.

Reaction that take place inside the catalytic converter as shown

2CO + O2 → 2CO2
2NOx → xO2 + N2
2CxHy + (2x+y/2)O2 → 2xCO2 + yH2O

1.5 APPLICATIONS OF CATALYTIC CONVERTER

Catalytic converter is widely used in various sectors such as

Petrol engine emission control

Diesel engine emission control

Food processing industries.

Chemical manufacturing industries

Gas turbines

1.6 PRESENT WORK

Recent year’s catalytic converter has becoming an important device for

reducing the exhaust emission. Due to the advancement in technology there is a drastic
 4

improvement in automobile production which results in more amount of pollution is fed

into the atmosphere. Thus focus should be made in the field of catalytic converter for the
reduction of exhaust emission must be done.

Thus this project deals with design and fabrication of catalytic converter by
replacing the expensive metals such as platinum, palladium etc with the nano iron oxide
powder which results in reduction of the exhaust pollution. Further the characterization of
nano iron oxide powder is made through scanning electron microscope, X-ray diffraction,
transmission electron microscope.
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CHAPTER 2

LITERATURE SURVEY

Flytzani-Stephanopoulos et al (2008) have studied that SO2-introduction

increases stability of Ag-alumina catalysts for the selective catalytic reduction of NO
with methane. The reaction generally taken place above the temperature of 600oC at those
temperatures catalytic deactivate is more and measurable. By using Time-resolved TEM
analyses it is studied that deactivation is due to sintering of silver at that temperature
range. Thus presence of SO2 dramatically suppresses the sintering of silver. Further
structural stabilization is achieved by using SO2 thus accompanies stable catalyst activity
for reducing NO.

Shanks et al (2008) have illustrated that Potassium promoted iron oxide

catalysts are primarily used for producing styrene. In this process, a large amount of
steam is used and for economic reasons it is desirable to be able to operate at lower
steam/ethylbenzene molar ratios without creating severe short term deactivation. Thus in
this study, the stabilities of Fe2O3, K Fe2O3 (10 wt% K+), KFeO2 (30 wt% K+), and a
potassium polyferrite mixed phase (K2Fe10O16/K2Fe22O34) were investigated in different
gas phases including H2, CO2, and ethyl benzene. The effect of simultaneous steam
addition was also considered. Thermo gravimetric analysis and x-ray powder diffraction
were used to monitor sample weight variation and phase change, respectively. Fe2O3 and
K2Fe10O16/ K2Fe22O34 were stable in CO2 but not stable in H2KFeO2 was resistant to
H2but easily decomposed by CO2. K-Fe2O3 was adversely impacted by both H2and CO2
the results suggest that the reduction of the iron oxide in this system was mainly caused
by surface deposited carbon instead of H2. A transformation diagram is proposed for the
phase changes of potassium promoted iron oxide materials in the reaction-relevant gas
phase conditions
 6

Koganei-shi et al (2006) have studied that anodic alumina supported silver

catalyst with a low Ag loading of about 1.68 wt.%is used to measure NOx adsorption and
NOx-temperature programmed decomposition (TPD)/temperature programmed surface-
reaction (TPSR) measurements in different gas streams (He, C3H6/He, C3H6//O2/He) for
investigating the formation, consumption and reactivity of surface adsorbed NOx species.
During NO adsorption, no noticeable uptake of NO was detected. Introducing oxygen
greatly improved adsoption of NOx species.Thus the result of TPSR indicates that the
surface nitrate species can be effectively reduced by propene when oxygen is introduces
into it. Thus selective reduction of NOx in the presence of excess oxygen is proposed to
pass through the selective reduction of the adsorbed nitrate species with the activated
propene.

Sipho C. Ndlela et al (2006) have illustrated that Potassium-promoted iron

oxide catalysts are used in large volume for the commercial ethylbenzene
dehydrogenation to styrene process. Short-term deactivation of these catalysts, which is
addressed by operating in excess steam, is thought to be caused due to reactive site loss
through coking and/or reduction. Further the relative importance of the two mechanisms
is not known. Thermo gravimetric experiments and X-ray diffraction analysis were used
to examine the reduction behavior of potassium-promoted iron oxide materials. The
reduction behavior was then compared with results from isothermal ethylbenzene
dehydrogenation reactor studies under low steam-to-ethylbenzene operation. Potassium
incorporation was found to stabilize the iron oxide against reduction apparently through
the formation of KFeO2. Chromium addition improved the reduction resistance has stated
in this paper.

Apostolescu et al (2005) has stated that new Fe2O3 based materials are
developed for the selective catalytic reduction (SCR) of NOx by NH3 in diesel exhaust.
As a result of the catalyst screening, ZrO2 is considered to be the most effective carrier
for Fe2O3. The modification of the Fe2O3ZrO2 system with tungsten leads to drastic
increase of SCR performance as well as pronounced thermal stability. These results show
that tungsten acts as bifunctional component. The highest catalytic activity is observed
 7

for ZrO2 that is coated with 1.4 mol% Fe2O3 and 7.0 mol% WO3 (1.4Fe/7.0W/Zr) also
discussed in this paper.

Hizbullah et al (2004)have illustrated that with the preparation and

modification of iron oxide with different alkali metals which can be used as catalysts for
exhaust reduction. Among the prepared catalysts, Fe1.9K0.1O3 proved to be the most
promising catalyst which is suitable for the simultaneous removal of NOx and soot from
diesel engines exhaust. The study has shown that long-time treatment leads to a decline in
the activity, and remains constant after at least 20 sample experiments. This shows that
the catalysts can be used for particular long time. On the other hand long-time treatment
causes a significant enhancement of N2 selectivity, and the formation of by-product N2O
was not observed. This alteration of catalytic performance is likely due to addition of the
potassium as the promoter. This study confirms that Fe1.9K0.1O3 is a suitable catalyst for
simultaneous removal of soot and NOx between 350 and 480 ◦C.

Jan Kaspar et al (2003) have illustrated technology for importance of exhaust

emissions by analyzing the current understanding of three way catalytic converter, the
specific role of the various components, the achievements and the limitations. The
challenges in the development of new automotive catalysts, and the future pollution
nomes are also discussed.

Guido Ketteler et al (2002) have stated the details of the surface structure and
composition of potassium promoted iron oxide model catalyst films prepared on Ru are
investigated by scanning tunneling microscopy (STM), low energy electron diffraction
(LEED), and Auger electron spectroscopy (AES). At 700 K, polycrystalline KFeO2 films
are formed.On annealing, the potassium content in KFeO2 films decreases and a mixed
phase which consists of polycrystalline KFeO2 on top of partially uncovered
K2Fe22O34forms. At 970 K, the whole film transforms to K2Fe22O34
 8

Kureti et al (2002) stated that simultaneous catalytic conversion of NOx and

soot into N2 and CO2 in diesel exhaust gas. Several iron containing oxide catalysts were
partially modified by the alkali metal potassium and were used for NOx–soot reaction in
a model exhaust gas. Fe1.9K.1O3 has shown highest catalytic performance for N2
formation in the so far investigated catalysts. Further studies have shown that Fe1.9K.1O3
was deactivated due to the agglomeration of the promoter potassium. Experiments carried
out over the aged Fe1.9K.1O3 catalyst have shown that NOx–soot reaction was suppressed
at higher O2 concentration. In contrast to that, the catalytic activity was increased in
presence of NO2 and H2O also explained in this paper.

Joseph et al (2001) have stated that Potassium promoted iron oxide model
catalyst films were prepared by deposition of potassium onto epitaxial Fe2O3 at 200 K,
followed by annealing in the range 200 to 970 K. Their formation and composition were
investigated by X-ray photoelectron spectroscopy (XPS) in combination with thermal
desorption spectroscopy (TDS) Already at 300 K a solid-state reaction occurred and the
iron oxide was partly reduced. For certain potassium content, this surface develops a well
ordered phase with a superstructure. The potassium containing phases are not stable in
water atmosphere:

Keshavaraja et al (1999) have studied that Silver-alumina catalysts prepared

by a single-step co-gelation technique is used for the selective catalytic reduction of NO
with methane. This type catalyst is active over a temperature range from 450 to 650oC,
and for a relatively wide range of Ag loading (1–7 wt.%) is used. Excess O2 in is fed for
better SCR reaction. This Catalysts having high conversions efficiency of NOx by CH4.
The structural stability of Ag was studied in by using UV–VIS diffuse reflectance
spectroscopy.
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CHAPTER 3

NANOTECHNOLOGY

3.1 INTRODUCTION

Nanotechnology refers to a field of applied science and technology whose

theme is the control of matter on the atomic and molecular scale, generally 100
nanometers or smaller, and the fabrication of devices or materials that lie within that size
range.

Nanotechnology is a highly multidisciplinary field, drawing from fields such

as applied physics, materials science, interface and colloid science, device physics,
supramolecular chemistry( which refers to the area of chemistry that focuses on the non
covalent bonding interactions of molecules), self replicating machines and robotics,
chemical engineering, mechanical engineering, biological engineering and electrical
engineering. Grouping of the sciences under the umbrella of “nanotechnology” has been
questioned on the basis that there is little actual boundary-crossing between the sciences
that operate on the nanoscale. Instrumentation is the only area of technology common to
all disciplines; on the contrary, for example pharmaceutical and semiconductor industries
do not “talk with each other”.

Examples of nanotechnology are the manufacture of polymers based on

molecular structure, and the design of computer chip layouts based on surface science.
Despite the promise of nanotechnologies such as quantum dots and nanotubes, real
commercial application have mainly used the advantages of colloidal nanoparticle in bulk
form, such as suntan lotion, protective coatings, drug delivery and stain resistant clothing.

3.2 NANO PARTICLES

Nanoparticles possess unique hybrid properties of neither the molecular nor

the bulk solid-state limits. Nanoparticles processing offers a practical way to tailor the
 10

properties at the atomic or molecular level, producing novel materials with a unique size-
dependent behavior such as quantum size effect and greater micro-structural uniformity.
The advancement of technology at different levels has improved the manufacturing of
materials with improved and definite characteristics. Hence the traditional materials are
facing high competition with the advanced materials. Ceramics, composites and
polymeric materials claim to provide lighter weight, greater strength and overall better
electrical, thermal and optical properties than the conventional materials. The recent
technology focuses mainly on the size of the particles in the order of nano meters.
Nanoparticles may be defined as those particles have dimensions in the range 1 to 100
nm.

It is realized that the nano particles have high surface to volume ratio, the
basic factor that has improved the material performance in general. The volume of an
object decreases as the third power of its linear dimensions, but the surface area only
decreases as its second power. This somewhat subtle and unavoidable principle has huge
ramifications. Materials scientist are challenged to identify, build, control and test the
structures whose dimensions are in the nanometer scale and to demonstrate the potentials
of these nanostructures in scientific, industrial or medical applications while keeping in
mind their potential impact on the society. In general, the nanoparticles are larger than
individual atoms and molecules but are smaller than bulk solid. Hence they obey neither
absolute quantum chemistry nor laws of classical physics and have properties that differ
markedly from those expected.

Nanoclusters have at least one dimension between 1 and 10 nanometers and a

narrow size distribution. Nanopowders are agglomerates of ultrafine particles,
nanoparticles, or nanoclusters. Nanometer sized single crystals, or single-domain
ultrafine particles, are often referred to as nanocrystals.

Nanoparticle research is currently an area of intense scientific research, due to

a wide variety of potential applications in biomedical, optical, and electronic fields.
 11

3.3 PROPERTIES OF NANOPARTICLES

The properties of materials change as their size approaches the nano scale and
as the percentage of atoms at the surface of a material becomes significant. For bulk
materials larger than one micro meter the percentage of atoms at the surface is minuscule
relative to the total number of atoms of the material. The interesting and sometimes
unexpected properties of nanoparticles are not partly due to the aspects of the surface of
the material dominating the properties in lieu of the bulk properties

Materials reduced to the nanoscale can suddenly show very different

properties compared to what they exhibit on a macroscale, enabling unique applications.
For instance, opaque substances become transparent (copper); inert materials become
catalysts (platinum); stable materials turn combustible (aluminum); solids turn into
liquids at room temperature (gold); insulators become conductors (silicon). Materials
such as gold, which is chemically inert at normal scales, can serve as a potent chemical
catalyst at nanoscales the bending of bulk copper occurs with movement of copper
atoms/clusters at about the 50 nm scale. Copper nanoparticles smaller than 50 nm are
considered super hard materials that do not exhibit the same malleability and ductility as
bulk copper.

The change in properties is not always desirable. Ferroelectric materials

smaller than 10 nm can switch their magnetization direction using room temperature
thermal energy, thus making them useless for memory storage. Suspensions of nano
particles are possible because the interaction of the particle surface with the solvent is
strong enough to overcome differences in density, which usually result in a material
either sinking or floating in a liquid. Nanoparticles often have unexpected visible
properties because they are small enough to confine their electrons and produce quantum
effects. For example gold nanoparticles appear deep red to black in solution. Much of the
fascination with nanotechnology stems from these unique quantum and surface
phenomena that matter exhibits at the nanoscale. Generally nano particles are classified
as nano tubes, nano wires, nano crystals which are discussed below.
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3.3.1 Nanotubes

Nanotubes are a particularly novel form of nanoparticles about which there is

great interest and excitement. Carbon Nanotubes (CNT) were first discovered by Iijima
(1991), and are a new form of carbon molecule. They are similar in structure to the
spherical molecule C60 (buckminsterfullerene or bucky balls) discovered in the 1980s
but are elongated to form tubular structures 1-2 nm in diameter. They can be produced
with very large aspect ratios and can be more than 1 mm in length. In their simplest form,
nanotubes comprise a single layer of carbon atoms arranged in a cylinder. These are
known as single-wall carbon nanotubes (SWCNTs). They can also be formed as multiple
concentric tubes (multi-wall carbon nanotubes, MWNTs) having diameters significantly
greater, up to 20 nm, and length greater than 1 mm.

CNTs have great tensile strength and are considered to be 100 times stronger
than steel whilst being only one sixth of its weight thus making them potentially the
strongest, smallest fibre known. They also exhibit high conductivity, high surface area,
unique electronic properties, and potentially high molecular adsorption capacity.
Applications which are currently being investigated include; polymer composites
(conductive and structural filler), electromagnetic shielding, electron field emitter, super
capacitors, batteries, hydrogen storage and structural composites.

Synthesis methods

• Laser ablation
• Arc discharge
• Chemical Vapour Deposition (CVD)
• Plasma-enhanced CVD
• Chemical precipitation

One major focus of current research on nanotubes is on scaling-up of

production rates to kilogram quantities. Nanotubes have also been produced from other
 13

materials including silicon and germanium but the development of various forms and
applications for CNTs remains the main focus of activity.

3.3.2 Nanowires

Nanowires are small conducting or semi-conducting nanoparticles with a

single crystal structure and a typical diameter of a few 10s of nanometres and a large
aspect ratio. Various metals have been used to fabricate nanowires including cobalt, gold
and copper. Silicon nanowires have also been produced.

Most approaches to the fabrication of nanowires are derived from methods

currently used in the semi-conductor industry for the fabrication of microchips. Typically
they involve the manufacture of a template followed by the deposition of a vapour to fill
the template and grow the nanowire. Deposition processes include Electrochemical
Deposition and CVD. The template may be formed by various processes including
etching, or the use of other nanoparticles, in particular, nanotubes.

3.3.3 Quantum dots

Quantum dots of semiconductors, metals and metal oxides have been at the
forefront of research for the last five years due to their novel electronic, optical, magnetic
and catalytic properties. The number of atoms in a quantum dot, which range from 1000
to 100,000, makes it neither an extended solid structure nor a single molecular entity.
This has led to various names being attributed to such materials including nanocrystals
and artificial atoms. To date, chemistry, physics and material science have provided
methods for the production of quantum dots and allow tighter control of factors affecting,
for example, particle growth and size, solubility and emission properties.

The main objective of the present work is to produce nano iron oxide (Fe2O3)
powder by using the special technique and to characterize them to confirm the formation
of nanosized powder. Further introduction of nano iron particles into the catalytic
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converter, comparison is made based on their properties To understand the basic

property of the produced nano iron powder, certain physico chemical diagnostic studies
were carried out using high resolution powder X-ray Diffraction (PXRD), The size and
shape of the powder were analyzed by carrying out through scanning electron microscope
(SCM) and Transmission Electron Microscope (TEM) studies.
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CHAPTER 4

CHARACTERIZATION OF NANOCOMPOSITES

4.1 SCANNING ELECTRON MICROSCOPE (SEM)

4.1.1 Introduction

The scanning electron microscope (SEM) is a type of electron microscope

that images the sample surface by scanning it with a high-energy beam of electrons in a
raster scan pattern. The electrons interact with the atoms that make up the sample
producing signals that contain information about the sample's surface topography,
composition etc.

4.1.2 Principles of Operation

SEM operates by scanning an electron beam over the sample and measuring
the electrical interactions with the surface. When the electrons hit the surface, weakly
bound electrons will be ejected to produce secondary electrons. These secondary
electrons can then be measured by a detector, and used to calculate the color for each
pixel of an SEM image. Since these secondary electrons are of low energy their
trajectories can be easily influenced by electromagnetic fields. In order to avoid a charge
build-up on the surface of the sample must be conducting. However, by using shadowing
methods non-conductive samples is coated with conductive material with a thin layer of
metal so that SEM measurements can be done easily.

4.1.3 Sample preparation

The types of signals produced by an SEM include secondary electrons, back

scattered electrons (BSE), characteristic x-rays, transmitted electrons. These types of
 16

signal require specialized detectors for their detection. SEM can produce very high-
resolution images of a sample surface, 1 to 5 nm in size.

For conventional imaging in the SEM, specimens must be electrically

conductive, at least at the surface, and electrically grounded to prevent the accumulation
of electrostatic charge at the surface. Metal objects require little special preparation for
SEM except for cleaning and mounting on a specimen stub. Nonconductive specimens
tend to charge when scanned by the electron beam, and especially in secondary electron
imaging mode, this causes scanning faults and other image artifacts. They are therefore
usually coated with an ultra thin coating of electrically-conducting material, commonly
gold, deposited on the sample either by low vacuum sputter coating or by high vacuum
evaporation. Conductive materials in current use for specimen coating include gold,
gold/palladium alloy, platinum etc. Two important reasons for coating, even when there
is more than enough specimen conductivity to prevent charging, are to maximize signal
and improve spatial resolution, especially with samples of low atomic number (Z).
Broadly, signal increases with atomic number, especially for backscattered electron
imaging. The improvement in resolution arises because in low-Z materials such as
carbon, the electron beam can penetrate several micrometres below the surface,
generating signals from an interaction volume much larger than the beam diameter and
reducing spatial resolution. Coating with a high-Z material such as gold maximises
secondary electron yield from within a surface layer a few nm thick, and suppresses
secondary electrons generated at greater depths, so that the signal is predominantly
derived from locations closer to the beam and closer to the specimen surface than would
be the case in an uncoated, low-Z material. These effects are particularly, but not
exclusively, relevant to biological samples.

4.1.4 Detection of secondary electrons

The most common imaging mode collects low-energy (<50 eV) secondary
electrons that are ejected from the k-orbital of the specimen atoms by inelastic scattering
interactions with beam electrons. Due to their low energy, these electrons originate within
 17

a few nanometers from the sample surface. The electrons are detected by an Everhart-
Thornley detector which is a type of photo multiplier system. The secondary electrons are
first collected by attracting them towards an electrically-biased grid at about +400V, and
then further accelerated towards a phosphor or positively biased to about +2000V. The
accelerated secondary electrons are now sufficiently energetic to cause the scintillator to
emit flashes of light which are conducted to a photomultiplier outside the SEM column
via a light pipe and a window in the wall of the specimen chamber. The amplified
electrical signal output by the photomultiplier is displayed as a two-dimensional intensity
distribution that can be viewed and photographed on an analogue video display. Thus
image is obtained

Figure 4.1 Electron Beam Scanning

4.1.5 Detection of backscattered electrons

Backscattered electrons (BSE) consist of high-energy electrons originating in

the electron beam that are reflected or back-scattered out of the specimen interaction
volume by elastic scattering interactions with specimen atoms. Since heavy elements
 18

backscatter electrons more strongly than light elements and thus appear brighter in the
image, BSE are used to detect contrast between areas with different chemical
compositions

The Everhart-Thornley detector, which is normally positioned to one side of the

specimen, is inefficient for the detection of backscattered electrons because few such
electrons are emitted in the solid angle subtended by the detector, and because the
positively biased detection grid has little ability to attract the higher energy BSE
electrons. Dedicated backscattered electron detectors are positioned above the sample in a
"doughnut" type arrangement, concentric with the electron beam, maximizing the solid
angle of collection. BSE detectors are usually either of when all parts of the detector are
used to collect electrons symmetrically about the beam, atomic number contrast is
produced. Thus advantages of scanning electron microscope are higher resolution, Faster
Scanning, provides surface image. .

4.2 TRANSMISSION ELECTRON MICROSCOPY (TEM)

4.2.1 Introduction

Transmission electron microscopy (TEM) is a microscopy technique whereby

a beam of electrons is transmitted through an ultra thin specimen, interacting with the
specimen as they pass through. Thus the image is formed from the interaction of the
electrons transmitted through the specimen, which is magnified and focused by an
objective lens and onto an imaging device, such as a fluorescent screen, thus the image of
the specimen is produced.

4.2.2 Sample preparation

The TEM is generally used in material science, metallurgy and the biological
sciences. In each case the specimens must be very thin and able to withstand the high
vacuum present inside the instrument.
 19

Sample preparation in TEM can be a complex procedure. TEM specimens are

typically hundreds of nanometres thick, as the electron beam interacts readily with the
sample, High quality samples will have a thickness that is comparable to the mean free
path of the electrons that travel through the samples, which may be only a few tens of
nanometres. Preparation of TEM specimens is specific to the material under analysis and
the desired information to obtain from the specimen. As such, many generic techniques
have been used for the preparation of the required thin sections.

To withstand the instrument vacuum, biological specimens are typically held

at liquid nitrogen .Generally samples are prepared as a thin foil, or etched so some
portion of the specimen is thin enough for the beam to penetrate.

4.2.3 General properties of TEM

The transmission electron microscope (TEM) operation has same optical

principle as that of light microscope. The TEM has the added advantage of greater
resolution. This increased resolution allows us to study ultrastucture of viruses and
macromolecules etc. Specially prepared materials samples may also be viewed in the
TEM. The light microscope and TEM are commonly used in conjunction with each other
to complement a research project.

Since electrons are very small and easily deflected by hydrocarbons or gas
molecules, it is necessary to use the electron beam in a vacuum environment. A series of
pumps are used to accomplish an adequate vacuum for this purpose. Rotary Pumps are
the first in the series. They are also called the “roughing pumps” as they are used to
initially lower the pressure within the column through which the electron must travel to
10 -3 mm of Hg range. Diffusion Pumps is used to achieve higher vacuums of about 10-5
mm Hg range but must be backed by the rotary pump.
 20

4.2.4 Working of TEM

The electron gun which is at top, producing a stream of monochromatic electrons.

This stream is focused to a small, thin, coherent beam by the use of condenser
lenses. The first lens largely determines the "spot size”. The second lens usually
controls the intensity or brightness of the image.

The beam is restricted by the condenser aperture, knocking out high angle
electrons

The beam strikes the specimen and parts of it are transmitted

This transmitted portion is focused by the objective lens into an image

The image is passed down the column through the intermediate and projector
lenses, being enlarged all the way

The image strikes the phosphor image screen and light is generated, allowing the
user to see the image. The darker areas of the image represent those areas of the
sample that fewer electrons were transmitted and the lighter areas of the image
represent those areas of the sample that more electrons were transmitted through
the space which is useful to represent the size of the sample. Schematic diagram
of TEM as shown in Figure 3.2 and Figure 3.3

Figure 4.2 Transmission Electron Microscope (TEM) apparatus

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Figure 4.3 Transmission Electron Microscope (TEM) setup

4.3 X-RAY DIFFRACTION

4.3.1 Introduction

X-rays are electromagnetic radiation of wavelength about 1 Å (10-10 m),

which is has the same size as an atom. They occur in that portion of the electromagnetic
spectrum between gamma-rays and the ultraviolet. Each crystalline solid has its unique
characteristic. Once the material has been identified, X-ray crystallography may be used
to determine its structure, i.e. how the atomic packing in the crystalline state and to find
the inter atomic distance and angle are etc. X-ray diffraction is one of the most important
characterization tools used in solid state chemistry and materials science
for determine the size and the shape of the unit cell for any compound
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Figure 4.4 X-ray diffraction

4.3.2 Working principle

The X-ray radiation most commonly used is that emitted by copper, whose
characteristic wavelength for the K radiation is =1.5418Å. When the incident beam
strikes a powder sample, diffraction occurs in every possible orientation of 2θ. The
diffracted beam may be detected by using a moveable detector such as a Geiger counter,
which is connected to a chart recorder.

Figure 4.5 Schematic diagram of X-ray powder diffractometer

 23

In normal use, the counter is set to scan over a range of 2θ values at a constant
angular velocity. Routinely, a 2 θ range of 5 to 70 degrees is sufficient to cover the most
useful part of the powder pattern. Minimum time of about 30 minutes is needed to obtain
a trace. Schematic diagram for X ray diffraction as shown in Figure 3.5

1. Place the sample onto the double-side tape which is then placed on an aluminum
sample holder.
2. Switch on the start knob and chart recorder (slow) simultaneously, run your
sample on constant speed.
3. Draw the graph by taking intensity on y axis and diffraction angle 2θ on X axis.
4. Locate all peaks on the chart and corresponding 2θ values and write their values
into the data chart below

4.4 FOURIER TRANSFORM INFRARED (FT-IR) SPECTROMETRY

4.4.1 Introduction

FT-IR stands for Fourier Transform Infrared, the preferred method of infrared
spectroscopy. In this process IR radiation is passed through a sample. Some of the
infrared radiation is absorbed by the sample and some of radiation transmitted through
the sample. Thus by analyzing the resulting spectrum molecular representation of
particular specimen can be found out.

Information obtained from FT-IR:

• It can be used to identify the unknown materials
• It can be used to determine the quality or consistency of a sample
• It can also determine the amount of components present in the mixture

4.4.2 Working Principle

Infrared spectroscopy is an unique technique for analysis the material in the

laboratory . In this method, absorption peaks represents the frequencies of vibrations
between the bonds of the atoms of the material. Since different material is a unique
combination of atoms, no two compounds produce the exact same infrared spectrum.
 24

Therefore, infrared spectroscopy can be used for positive identification of every different
kind of material. Further the size of the peaks in the spectrum is a direct indication of the
amount of material present in the sample. Fourier Transform Infrared (FT-IR)
spectrometry was developed in order to overcome the limitations encountered in ordinary
infra red spectrometer. The main difficulty was the slow scanning process. FT-IR is the
method for measuring all the infrared frequencies simultaneously, rather than
individually. In this process a very simple optical device called an interferometer is
employed which produces unique type of signal which has all infrared frequencies
encoded into it. Thus the resultant signal can be measured easily and quickly. At the next
process the encoded frequency are decoded into indugual frequency through the process
Fourier transformation. This transformation is performed by means of computer represent
the desired spectral information for analysis.

4.4.3 Sample preparation

Gaseous samples require little preparation beyond purification, but a sample

cell with a long path length (typically 5-10 cm) is normally needed, as gases show
relatively weak absorbance.

Liquid samples can be sandwiched between two plates of a high purity salt.
The plates are transparent to the infrared light and will not introduce any lines onto the
spectra. Some salt plates are highly soluble in water, so the sample and washing reagents
must be without water

Solid samples can be prepared in three major ways. The first method is to
grind a quantity of the sample with a specially purified salt (usually potassium bromide) .
This powder mixture is then crushed in a mechanical die press to form a pellet through
which the beam of the infra red rays can travel through. The second technique is the Cast
Film technique, which is mainly used for polymeric materials. The sample is first
dissolved in a suitable, non hygroscopic solvent. A drop of this solution is deposited on
surface of KBr or NaCl cell. The solution is then evaporated to dryness and the film
formed on the cell and it is analyzed directly. Care is important to ensure that the film is
 25

not too thick otherwise light cannot pass through. This technique is suitable for
qualitative analysis.

The final method is to obtain a thin (20-100 micrometer) film from a solid
sample. This is one of the most important ways of analyzing plastic products because the
integrity of the solid is preserved.

4.4.4 Experimental procedure

Infrared energy is emitted from a glowing black-body act as the source for
infrared spectrometer. This beam passes through an aperture which is used to controls the
amount of energy presented to the sample. Then the beam enters the interferometer where
the “spectral encoding” takes place. The resulting interferogram signal then exits the
interferometer. At next stage the beam enters the sample compartment where it is
transmitted through or reflected off of the surface of the sample, depending on the type of
analysis being accomplished. This is the region where adsorption of energy takes place.
Then the beam finally passes to the detector for final measurement. The detectors used
are specially designed to measure the special interferogram signal. Finally the measured
signal is digitized and sent to the computer where the Fourier transformation takes place.
The final infrared spectrum is then presented to the user for interpretation and
manipulation.

Figure4.6 Schematic Diagram of Infrared Spectroscopy

 26

4.4.5 Advantages of FT-IR

• Speed
Since all of the frequencies are measured simultaneously, most of the
measurements made by FT-IR are made in a matter of seconds rather than several
minutes. This is called as the Felgett Advantage.

• Sensitivity
Sensitivity is dramatically improved by employing FT-IR . The detectors
employed are much more sensitive which results in reduction of the noise to any desired
level

• Mechanical Simplicity
The simple moving mirror is employed on to the interferometer for the
continuous monitoring of part in the instrument. Thus, there is very little possibility of
mechanical breakdown.

• Internally Calibrated
These instruments employs HeNe laser for internal wavelength calibration
standard. These instruments are self-calibrating and never need to be calibrated by the
user.

4.4.6 Application Of FT-IR

• Infrared spectroscopy is widely used in both research and industry as it is simple

and reliable technique for measurement, quality control and dynamic measurement.
It is of especial use in forensic analysis in both criminal and civil cases, enabling
identification of polymer degradation
• By measuring at a specific frequency over time, change in the character of a
particular bond can be measured. This is especially useful in measuring the degree
of polymerization in polymer manufacture.
 27

• Techniques have been developed to assess the quality of tea-leaves using infrared
spectroscopy. This will mean that highly trained experts (also called 'noses') can be
used more sparingly, at a significant cost saving.
• Infrared spectroscopy has been highly successful for applications in both organic
and inorganic chemistry. Infrared spectroscopy has also been successfully utilized
in the field of semiconductor microelectronics for example, infrared spectroscopy
can be applied to semiconductors like silicon, gallium arsenide, gallium nitride,
amorphous silicon, silicon nitride, etc.

4.5 ENERGY DISPERSIVE X-RAY ANALYSIS

4.5.1 Introduction

Energy dispersive X-ray Analysis (EXDA) is an analytical technique used

predominantly for the elemental analysis or chemical characterization of a specimen.
Being a type of spectroscopy, it relies on the investigation of a sample through
interactions between electromagnetic radiation and matter, analyzing X-rays emitted by
the matter in this particular case. Its characterization capabilities are due in large part to
the fundamental principle that each element of the periodic table has a unique atomic
structure allowing x-rays that are characteristic of an element’s atomic structure to be
uniquely distinguished from each other.

This technique is used in conjunction with SEM and is not a surface science
technique. An electron beam strikes the surface as a conducting sample. The energy of
the beam is typically in the range 10-20Ke. This causes X-rays to be emitted from the
point of material. The energy of the X-rays emitted depends on the material under
examination. The X-rays are generated in a region about 2 microns in depth, and thus
EDX is not a surface science technique. By moving the electron beam across the material
an image of each element in the sample can be acquired in a manner similar to SAM. Due
to low X-ray intensity, images usually take a number of hours to acquire. Elements of
low atomic number are difficult to detect by EDX. The SiLi detector is often protected by
a Beryllium window. The absorption of the X-rays by the Be precludes the detection of
elements below n atomic number of 11 (Na). In windowless systems, elements with as
 28

low atomic number 4 (Be) have been detected, but the problems involved get
progressively worse as the atomic number is reduced. Spectroscopy data is often
portrayed as a graph plotting x-ray energy vs. count rate. The peaks correspond to
characteristic elemental emissions.

To stimulate the emission of characteristic x-rays from a specimen, a high

energy beam of charged particles such as electrons or protons, or a beam of x-rays, is
focused in to the sample to be characterized. At rest, an atom within the sample contains
ground state (or unexcited) electrons situated in discrete energy levels or electron shells
bound to the nucleus. The incident beam may excite an electron in an inner shell,
prompting its ejection and resulting in the formation of an electron hole within the atom’s
electronic structure. An electron from an outer, higher-energy shell then fills the hole, and
the difference in energy between the higher-energy shell and the lower energy shell is
released in the form of an X-ray. The x-ray released by the electron is then detected and
analyzed by the energy between the two shells, and of the atomic structure of the element
from which they are emitted.

4.6 THERMO GRAVIMETRIC ANALYSIS

4.6.1 Introduction

Thermo gravimetric Analysis or TGA is a type of testing that is performed on

samples to determine changes in weight in relation to change in temperature. Such
analysis relies on a high degree of precision. A derivative weight loss curve can be used
to tell the point at which weight loss is most apparent. TGA is commonly employed in
research and testing to determine characteristics of materials such as polymers, to
determine degradation temperatures, absorbed moisture content of materials, the level of
inorganic and organic components in materials, decomposition points of explosives, and
solvent residues. It is also often used to estimate the corrosion kinetics in high
temperature oxidation.
 29

4.6.2 Working principle

DTA involves heating or cooling a test sample and an inert reference under
identical conditions, while recording any temperature difference between the sample and
reference. This differential temperature is then plotted against time, or against
temperature. Changes in the sample which lead to the absorption or evolution of heat can
be detected relative to the inert reference.

Differential temperatures can also arise between two inert samples when
response to the applied heat {treatment is not identical. DTA can therefore be used to
stuffy thermal properties and phase changes which do not lead to change in enthalpy. The
baseline of the DTA curve should then exhibit discontinues at the transition temperatures
and the slope of the curve at any point will depend on the micro structural constitution at
that temperature. A DTA curve can be used as a finger print for identification purposes,
for example, in the study of clays where the structural similarity of different forms
renders diffraction experiments difficult to interpret.

The area under a DTA peak can be the enthalpy change and is not affected by
the heat capacity of the sample. DTA may be defined formally as a technique for
recording the difference in temperature between a substance under reference material
against either time or temperature as two specimens are subjected to identical temperature
regimes in an environmental heated or cooled at a controlled rate.

4.6.3 Apparatus required

• Sample holder comprising thermocouples, sample containers and a

ceramic or metallic block.
• Furnace
• Temperature programmer
• Recording system.
 30

The last three items come in a variety of commercially available forms are not
being discussed in any detail. A temperature programmer is essential in order to obtain
constant heating rates. The recording system must have a low inertia to faithfully
reproduce variations in the experimental set-up.

Figure 4.7 Schematic Diagram of TG-DAT

The sample holder assembly consists of a thermocouple each for the sample and
reference, surrounded by a block to ensure an even heat distribution. The sample is
contained in a small crucible designed with an indentation on the base to ensure a snug fit
over the thermocouple bead. The crucible may be made of materials such as Pyrex, silica,
nickel or platinum, depending on the temperature and the nature of the tees involved. The
thermocouples should not be placed in direct contact with the sample to avoid
contamination and degradation, although sensitivity may be compromised. On the other
hand, the high thermal conductivity leads to smaller DTA peaks. The sample assembly is
isolated against electrical interference from the furnace wiring with an earthed sheath,
often made of platinum coated ceramic material. The sheath can also be used to contain
the sample region with in a controlled atmosphere or a vacuum. During experiments a
temperature in the range of -200 to 500oC, problems are encountered in transferring heat
uniformly away from this spectrum. This may be migrated by using thermocouples in the
form of (degree) at discs to ensure optimum thermal contact with the flat bottomed
sample container, made of aluminum or platinum foil. To ensure reproducibility, it is then
necessary to ensure that the thermocouple and a container are consistently located with
respect to each other.
 31

CHAPTER 5

CATALYTIC CONVERTER

5.1 INTRODUCTION

A catalytic converter is a device used to reduce the toxicity of emissions from

an internal combustion engine. A catalytic converter converts the harmful toxic
combustion products and its by-products into less-toxic substances.

• It is the most effective after treatment process for reducing engine emission.
• Catalyst do not consume during the reaction hence it is non-degradable.
• Catalytic converter is generally called as three way catalytic converter
because it promotes in reduction of HC, CO and NOx.
• It consists of steel container of honeycomb structure inside which contains
porous ceramic structure through which the gas flows.
• It consists of small embedded partials of catalytic materials that promotes
oxidation reaction in exhaust gas.
• Catalytic converter uses alumina as base material because it can withstand
high temperature, low thermal expansion etc.
• Catalyst generally used are platinum, palladium and rhodium.
• Materials such as platinum, palladium promotes oxidation of HC&CO while
rhodium promotes reaction of NOx
Reaction as shown below
2CO + O2 → 2CO2
2NOx → xO2 + N2
2CxHy + (2x+y/2)O2 → 2xCO2 + yH2O
 32

5.2 CATALYSIS

Catalysis is the process in which the rate of a chemical reaction is increased by

means of a chemical substance known as a catalyst. Unlike other reagents a catalyst is not
consumed during the chemical reaction. Thus, the catalyst may participate in multiple
chemical transformations, although in practice catalysts are secondary processes

5.2.1 General principles of catalysis

Catalysts generally react with one or more reactants to form intermediate

substances that subsequently give the final reaction product, in the process regenerating
the catalyst. The following is a typical reaction, where C represents the catalyst, X and Y
are reactants, and Z is the product of the reaction of X and Y:

X + C → XC......................... (1)
Y + XC → XYC ...................(2)
XYC → CZ ...........................(3)
CZ → C + Z ..........................(4)

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction

4, thus the overall reaction is listed below:

X+Y→Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase
the rate of the reaction. In practice, however, catalysts are sometimes consumed in
secondary processes.
 33

5.2.2 Catalysis and reaction energetic

Catalyst is used serves for two purpose

1. Enhances the reaction rate
2. Direct the reactants to specified product.

General potential energy diagram showing the effect of a catalyst in the

chemical reaction of X + Y to give Z. Due to presence of the catalyst reaction occurs
in different pathway which results in lower activation energy. The final result and the
overall thermodynamics are the same. Potential energy diagram as shown in Figure 4.1

Fig 5.1 Potential Energy Diagram

Rate of reaction(R) is inversely proportional to exponential of the activation

energy. Let k be the reaction rate constant, Ca, Cb be the concentration at point of time
of reactant molecules and x, y be the reaction order. Thus rate of reaction is represented
as

Rate of reaction R =kCaxCby

 34

Catalysts work by providing an (alternative) mechanism involving a different

transition state and lower activation energy. The effect is due to the molecular collisions
have the energy needed to reach the transition state. Catalysts do not change the
favorableness of a reaction: they have no effect on the chemical equilibrium of a reaction
because the rate of both the forward and the reverse reaction are both affected.

5.2.3 Mechanism of catalytic reaction

Mechanism of catalyst by chemisorption. Chemisorption is the type of

adsorption where the molecules adhere to the surface of catalyst through the formation of
chemical bond.
Strength of the adsorption in the order of O2>C2H2>CO>H2>CO>N2
variation of chemisorption among metals is represented as follows. Based on this it is
clearly represented that Au can readily react with metal and can act as efficient catalyst
for most of the reaction. At the same time Ti has low chemisorption thus it cannot be
used as catalyst.
Au>Cu>Pd>Pt>Rh>Co>Ni>Ag>Mn>Fe>Mo>W>Nb>Ta>Ti

5.2.4 Catalytic materials

Many types of material often used as catalyst in the recent years. Proton acids
are probably the most widely used catalysts, especially for the many reactions involving
water, including hydrolyses and its reverse. Multifunctional solids often are catalytically
active, e.g. zeolites, alumina, certain forms of graphitic carbon etc. Transition metals
such as platinum,paladium, rhodium, iron, silver are often used to catalyses redox
reactions

5.2.5 Types of catalyst

Generally catalyst can be classified into two types

1. Homogeneous catalyst
 35

2. Heterogeneous catalyst
3. Electrocatalyst
Homogeneous catalyst
Homogeneous catalysts are those in which reactant and product are of same
phase. One example of homogeneous catalysis involves the influence of H+ on the
etherification of esters, e.g. methyl acetate from acetic acid and methanol.
Heterogeneous catalysts

Heterogeneous catalysts are those in which reactants and product are of

different phase. For example, in the Haber process, finely divided iron serves as a catalyst
for the synthesis of ammonia from nitrogen and hydrogen.

Electrocatalyst

In the context of electrochemistry, specifically in fuel cell engineering,

various metal-containing catalysts are used to enhance the rates of the half reactions that
comprise the fuel cell. One common type of fuel cell electrocatalyst is based upon
nanoparticles of platinum that are supported on slightly larger carbon particles. When this
platinum electrocatalyst is in contact with one of the electrodes in a fuel cell, it increases
the rate of oxygen reduction to water (or hydroxide or hydrogen peroxide).

5.2.6 Significance of catalyst

• Estimates are that 90% of all commercially produced chemical

products involve catalysts at some stage in the process of their
manufacture.
• Increases the reaction rate
 36

5.2.7 Application of catalyst in various fields

Petroleum refining

Petroleum refining makes intensive use of catalysis for alkylation, catalytic

cracking naphtha reforming, steam reforming

Exhaust gas treatment

Exhaust gas which is obtained by burning the fossil fuels are treated through
Catalytic converters, typically composed of platinum and rhodium, break down some of
the more harmful byproducts of automobile exhaust.
2 CO + 2 NO → 2 CO2 + N2

Chemical manufacturing

Many other chemical products are generated by large-scale reduction, often

via hydrogenation. The largest-scale example is ammonia, which is prepared via the
Haber process from nitrogen. Methanol is prepared from carbon monoxide. Bulk
polymers derived from ethylene and propylene are often prepared via Ziegler-Natta
catalysis. Polyesters, polyamides, and isocyanates by acid-base catalysis. Many fine
chemicals are prepared by catalysis; methods include those of heavy industry as well as
more specialized processes that would be prohibitively expensive on a large scale.

Biology and biotechnology

In nature, enzymes are catalysts in metabolism and catabolism. Most

biocatalysts are protein-based, i.e. enzymes, but other classes of bimolecular also exhibit
catalytic properties including enzymes, ribozymes, and synthetic deoxyribozymes.
 37

5.3 DISPERSED CATALYTIC CONVERTER MODEL

• Number of reacting molecules to product is directly proportional to

the number of catalytic sites available
• For increasing number of catalytic sites catalytic component are
dispersed on to the surface of the substrate.
• In normal practice dispersing the catalyst such as Pt, Rh, Pd, Fe, Ag in
powder form into the high surface charge carriers such as Al2O3, SiO2,
TiO2 etc
• Carriers are themselves catalytically active but pay a major role in
overall stability and durability.
• In general practice Pt,Pd,Rh practical are deposited by solution
impregnation.
• Alumina Al2O3 is bonded to monolithic honeycomb structure.
• The internal structure of Al2O3 is rich with OH-groups. These OH-
covers entire surface and parts of wall of each pores represents site on
which catalytic substances can bond physically or chemically.
• Thus physical surface of Al2O3 is the sum of internal areas of oxides
from all wall of the pores.
• Catalytic surface is the sum of all areas of the catalytic compounds
• Thus small size of the pores result in more catalytic reaction of the
species.
• Thus tiny catalytic particles are dispersed through porous Al2O3 thus
generate high Pt surface area.

5.4 GENERAL TYPES OF CATALYTIC CONVERTER

Catalytic converters are also used on generator sets, forklifts, mining

equipment, trucks, buses, trains, and other engine-equipped machines.
Generally there are two types of catalytic converter widely used. They are
 38

1. Three-way catalytic converters

2. Two-way catalytic converters

5.4.1 Three-way catalytic converter

Three-way catalytic converter is widely used in the automobile

industries. The three-way catalytic converter is scheduled to perform three simultaneous
tasks
• Reduction of nitrogen oxides to nitrogen and oxygen
2NOx → xO2 + N2
• Oxidation of carbon monoxide to carbon dioxide
2CO + O2 → 2CO2
• Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water:
CxH2x + 2xO2 → xCO2 + 2xH2O
These three reactions occur most efficiently when the catalytic converter receives exhaust
from an engine running slightly above the stoichiometric point. This is between 14.6 and
14.8 parts air to 1 part fuel, by weight, for gasoline.

5.4.2 Two-way catalytic converters

These types of catalytic converter not widely used in the automobile sector. A
two-way catalytic converter is scheduled to perform two simultaneous tasks:
• Oxidation of carbon monoxide to carbon dioxide:
2CO + O2 → 2CO2
• Oxidation of unburnt hydrocarbons (unburnt and partially-burnt fuel)
to carbon dioxide and water:
CxH4x + 2xO2 → xCO2 + 2xH2O

This type of catalytic converter is widely used on diesel engines to reduce hydrocarbon
and carbon monoxide emissions.
 39

5.4.3 Catalyst poisoning and deactivation

Catalytic poisons are the substances which retards the catalytic activity of the
other substances. Catalyst poisoning occurs when the catalytic converter is exposed to
exhaust containing substances that coat the working surfaces, encapsulating the catalyst
so that it cannot contact and treat the exhaust. Some of the catalytic poison that occurs in
exhaust system is listed below.
Lead, manganese silicon, phosphorus, zinc etc

5.5 PROPERTIES OF CATALYST

Surface area and pore size

High surface area results in maximum dispersion of catalytic compound.
Smaller pores size result in increase in catalytic activity.

Particle size distribution

Thus more number of particles dispersed result in increase in catalytic
activity. Thus huge number of particle distribution obviously increases the catalytic
action.

Wash coat thickness

Optical microscope study is often used to obtain washcoat thickness directly.
The space between washcoat and monolith gives the washcoat thickness measurement.
Thus wash coat formed must be as small as possible.

Adhesion
Common method for the measure of the adhesion between washcoat
monotyth is passing jet of air that simulates velocity used to measure adhesion between
substrate and catalyst. There must be sufficient adhesion between molecules for higher
catalytic activity.
 40

5.6 STEPS FOR DISPERSION OF PARTICLES ON TO THE CATALYTIC

CONVERTER

Capillary Impregnation
It is the process by which adsorption of nano particles on to the surface of
catalyst converter when the particles are dispersed in the liquid medium. The
adsorption of particles on to catalytic converter takes place unto saturation limit.
Further drying and calcinations at high temperature results in fixing of particles on to
catalytic converter.

Drying
Drying process take place at 110oc for the matter of one hour in the closed
furnace.

Calcinations
Calcinations process take place at 550oc for the matter of five hour in the
closed furnace. Thus results in fixing of particles on to the catalytic converter.

5.7 INTRODUCTION TO 4 STROKE DIESEL ENGINE

Intake Stroke

The piston is at top dead center at the beginning of the intake stroke, and, as the piston
moves downward, the intake valve opens. The downward movement of the piston draws
air into the cylinder, and, as the piston reaches bottom dead center, the intake valve
closes.
 41

Compression Stroke

The piston is at bottom dead center at the beginning of the compression

stroke, and, as the piston moves upward, the air compresses. As the piston reaches top
dead center, the compression stroke ends.

Power Stroke

The piston begins the power stroke at top dead center. The air is compressed
to as much as 25 bar and at a compressed temperature of approximately 1400°C. At this
point, fuel is injected into the combustion chamber and is ignited by the heat of the
compression. This begins the power stroke. The expanding force of the burning gases
pushes the piston downward, providing power to the crankshaft. The diesel fuel will
continue to bum through the entire power stroke (a more complete burning of the fuel).
The gasoline engine has a power stroke with rapid combustion in the beginning, but little
to no combustion at the end.

Exhaust Stroke
As the piston reaches bottom dead center on the power stroke, the power
stroke ends and the exhaust stroke begins. The exhaust valve opens, and, as the piston
rises towards top dead center, the burnt gases are pushed out through the exhaust port. As
the piston reaches top dead center, the exhaust valve closes and the intake valve opens.
The engine is now ready to begin another operating cycle.
 42

CHAPTER 6

PROCESS COMPARISON AND MATERIAL SELECTION

6.1 NANOPARTICLES PREPARATION METHODS AND ITS

CHARACTERISTICS

Various physical and chemical methods, their advantages and limitations are
tabulated in tables 3.1 and 3.2

Table 6.1 Physical methods for preparation of nanoparticles

Method Advantages Limitations

Evaporation condensation High purity powder The limitation
method of mass
production

Plasma heating method High melting point and low vapour Very expensive
pressure materials (W, Al2O3, SiO2, C) equipment
CO2 laser method Low vapor pressure materials Difficult for the
application of
Metal nano
powder

Mechanical alloy method Nano powder of metal alloy Agglomeration

& introduction
of impurity

Pulsed wire evaporation wire Metal wire source Low energy

consumption &
friendly
environment
 43

Table 6.2 Chemical method for preparation of nanoparticles

Method Advantages Limitations

Chemical Vapor Deposition Mass production facility Impurity
(CVD) contamination
Liquid phase reduction method & the danger
of chemical
Hydro-thermal synthesis materials
Sol-gel method

6.2 METALS AND ITS PROPERTIES

Generally material selection for catalytic activity is done through by

chemisorptions. Chemisorptions is the type of adsorption where the molecules adhere to
the surface of catalyst through the formation of chemical bond. Generally transition
metals have high catalytic activity.

Strength of the adsorption in case of gases is of order

O2>C2H2>CO>H2>CO>N2

Generally transition metals have high catalytic activity. variation of

chemisorption among metals were listed below

Au>Pd>Pt>Rh>Co>Ni>Ag>Mn>Fe>Mo>W>Nb>Ta>Ti

Thus finally five materials are selected and their properties are compared. The
materials are Pt,Pd,Rh,Ag,Fe. There properties are shown below.
 44

Table 6.3 Properties of the metals based on its catalytic activity

Properties Platinum Palladium Rhodium Nano Silver Nano iron

Pore size Max 106 A Max 106 A Max 106 A 200-300nm 200-300nm

Specific 10-20m2/g 10-20m2/g 10-20m2/g 10-20m2/g 10-20m2/g

surface area

Particle 6% 6% 6% 6% 6%
distribution

Bulk density 1-1.5 g/cm3 1-1.5 g/cm3 1-1.5 g/cm3 0.3-0.6 g/cm3 0.1-
0.25g/cm3

chemisorption Pt>Pd>Rh>Ag>Fe

6.3 MATERIAL SELECTION

From the material comparison and material study it is noted that iron oxide
supported by potassium can be effectively used in catalytic converter for the removal of
exhaust gas. Potassium being highly reactive metal it generally acts the promoter which
initiates the catalytic activity of iron oxide powder.

6.3.1 SAMPLE PREPARATION

General step for preparation of potassium supported ferric oxide powder involves
various processes such as mixing, drying, calcinations etc. First step of sample
preparation is to mix 17.7 wt% K2CO3 and 82.3 wt% Fe2O3 in the ball mill. At next step
the sample is allowed to dry in the oven at 90-105oC for the time duration of 1 hour.
Finally dried mixture was re-ground and followed by calcinations in air at 1100oC for the
 45

time duration of about 7 hours. Thus EDX pattern of the sample clearly indicated a
mixture has potassium polyferrite phases.
Next step of preparation of nano composites through planetary ball milling
process. Ball mill is an efficient tool for grinding many materials into fine powder. A ball
mill is an cylindrical device used for grinding (or mixing) materials like ores, chemicals,
ceramic raw materials and paints. Ball mills rotate around a horizontal axis, partially
filled with the material to be ground plus the grinding medium. Different materials are
used as media, including ceramic balls, stainless steel balls. It is noted that loading the
ferric oxide composites on to the ball mill results in gradual reduction in size of the
particles which is represented through Figure-6.1

250
Particle size (nm)

200
150
100
50
0
0 8 16 24
Milling time (hours)

Figure-6.1 Particle size reduction chart

 46

CHAPTER 7

RESULT AND DISCUSSION

7.1 SCANNING ELECTRON MIROSCOPE

Powder morphology and its composition were observed with

SEM(JEOL(Japan)) model JSM-840A combined with energy dispersed analysis through
X-ray spectroscopy(EDAX).The scanning electron microscope (SEM) is a type of
electron microscope that images the sample surface by scanning it with a high-energy
beam of electrons in a raster scan pattern. The electrons interact with the atoms that make
up the sample producing signals that contain information about the sample's surface
topography, composition etc. SEM image of the ferric oxide nano composites as shown
in Figure-7.1 which indicates the microstructure of the sample and its size.

Figure-7.1 SEM image of nano-ferric oxide composites (a)Before milling (b) 8 hrs
image (c) 16 hrs image (d) 24 hrs image
 47

Ferric oxide composites of size 225 nm are taken as the sample. Figure-7.1(a)
shows the size and structural orientation of ferric oxide composites which has been taken
for milling
The periodical analysis of ferric oxide nano composites is done by collecting
the samples after milling at an regular intervals of 8,16,24 hours.
Figure-7.1(b) illustrates the SEM image of samples after 8 hours of milling. It
is observed that the particles size varies from 163nm to 180 nm. The kinetic energy
transferred during the milling process leads to the production of array of dislocation. This
is accompanied by atomic level straining. At certain strain level, these dislocations
annihilate and recombine to form small angle grain boundaries separating the individual
grains. Thus sub grains are formed with reduced grain size. The stage conversion
efficiency was found to be 23%.
Figure-7.1(c) illustrates the SEM image of samples after 16 hours of milling.
After 16 hours there is some kind of agglomeration.The particles size varies from 106nm
to 124 nm. This is due to the delayed process and environmental factors. This revels that
the time period after each milling must be uniform and the temperature change have a
impact in the process.
Figure-7.1(d) illustrates the SEM image of samples after 24 hours of milling.
It is observed that the particles size varies from 80 nm to 104nm. During further milling,
the particles experience very high stress and the particle size decreases and reach
nanosize.

7.2 ENERGY DISPERSIVE X-RAY DIFFRACTION

Energy dispersive X-ray spectroscope is an analytical technique used for the

elemental analysis or chemical characterization of a sample. A high energy beam of
charged particles such as X-rays, is focused into the sample. The energy of the X-rays
emitted from a specimen indicates the elemental composition of the specimen. EDX
image of the ferric oxide composites as shown in the Figure-7.2.Further the composition
of various elements present in the sample are listed in Table-7.1. The EDAX pattern
 48

clearly indicates that the composite contains 61.75wt% of iron, 18.26wt% of oxygen and
2.21wt% of potassium which together acts used for the production of nano ferric oxide
composites. Ferric oxide present in the composites acts as a base material and the
Potassium added in this process acts as a re-enforcement material. Oxygen present in the
significant amount (18.26 wt%) indicates the presence of oxide particles in the
composites.

Figure-7.2 EDAX pattern for nano-ferric oxide composites

Table-7.1 Composition of elements present in nano-Ferric oxide composites

Elements Net count Weight% Atom%

C 1076 6.69 18.92
O 11105 18.26 38.77
Fe 5248 61.75 37.57
K 1740 2.78 2.42
Al 556 .46 .58
Au 5768 10.06 1.74
Total 100 100
 49

7.3 X- RAY DIFFRACTION

XRD measurement is done on nano ferric oxide composites with the scan rate
of 28/min at 2000 cycle using CuK radiation of wavelength 1.54 Ao was applied.
Figure7.3 shows the XRD spectrum of ferric oxide nano composites obtained using
planetary ball milling process. Thus by calculating using sheer formula the crystalline
size of the particles was found to be 90 nm. Further intense peak were observed below 20
degree. This is due to the presence of nano sized particles. The morphology of the
spectrum clearly indicates that the nano composites are amorphorous in nature. The small
peak observed during 21, 25, 31 degree indicates the presence of potassium crystal.

Figure-7.3 XRD pattern for nano-ferric oxide composites

 50

7.4 TEM IMAGE

The TEM study was carried out on Phillips transmission electron microscope.
Fig7.4 shows the TEM structure of nano ferric oxide composites obtained by planetary
ball milling process. From the figure the particle size were found to be varying from 80
nm to 106 nm. Further it is observed that the particle sizes are found to be non-uniform
over the surface. Thus is due to the amorphorous nature of the particles.

Figure-7.4 TEM image for nano-ferric oxide composites

 51

7.5 FOURIER TRANSFORM- INFRARED SPECTROSCOPY

Fourier transform infrared spectrum of potassium doped ferric oxide nano
composites as shown in figure 7.5. The intense band was found at 3444 cm inwards is
due to the overstretching vibration of water. The presence of water is once again
confirmed at bending vibration at 1630 inwards. The peek at 2853cm, 2923cm inwards
are due to the symmetric and asymmetric vibration of arsenic group(potassium). The
corresponding bending of arsenic group was found to be occurring at 1283 cm inwards.
The ferric oxide vibration was produced at the intense broad band between 720 cm and
500 cm inwards.
From this analysis it is concluded that ferric oxide nano composites are
prepared by doped potassium molecules with ferric oxide particles in the presence of
water molecules.

100.0 Fe2O3
95
791
90
774
85
857
80
2853
1021
75

70

65 2923 1384
1558
60 481

55 1630
1119
50
%T
45

40

35

30

25
693
20 3433

15

10
587
5

0.0 634 618

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1

Figure7.5 FT-IR Spectrum

 52

7.6 THERMO GRAVIMETRIC-DIFFERENTIAL THERMAL ANALYSIS

The TGA-DTA study was carried out with netzch STA 409PC equipment.
The experiment was performed in a nitrogen atmosphere in the range 25oC to 1400oC, at
a heating rate of 27oC/min, alumina is used as the standard catalyst.
In TG curve, an gradual reduction in weight loss of about 4.0-6.0% is
observed between 1000-1400oC. This is due to the phenomenon by which degradation of
arsenic and ferric oxide takes place at that temperature with the release of oxygen.
Figure 7.6 shows differential thermal analysis curve of nano- ferric oxide
composites prepared by planetary ball milling process. It has been seen from the
figure7.6 that sharp endothermic peak is observed at 316oC. This is due to the fact that
evaporation of water molecules which results in change of chemical composition. A
small endothermic peak is observed at 1271oC. This is due to the degradation of arsenic
and oxide particles. Finally at 1333oC an endothermic peak is observed due to the phase
change. No other exothermic peak is observed below this temperature.

Figure7.6 TG-DTA pattern

 53

7.7 ENGINE ANALYSIS-PERFORMANCE PARAMETER

7.7.1 Specific Fuel Consumption

The variation of specific fuel consumption with different brake power value
and at different conditions as shown in the figure 7.7. The specific fuel consumption
value is found to be increasing on introduction of catalytic converter and finally reaches
the maximum value on using coated catalytic converter. Thus at no load condition there
is about 5 %increase in SFC value and at peak load condition there is about 5.56
%increase in SFC value. This is due to the fact that back pressure at the engine exhaust
increased on introduction of catalytic converter. Thus more fuel is consumed to overcome
the back pressure. Thus the SFC value steadily increases with the introduction of coated

catalytic converter.

0.8

0.7
WITHOUT
0.6 CATALYTIC
CONVERTER
0.5
SFC(kG/kW-hr)

WITH UNCOATED
0.4 CATALYTIC
CONVERTER
0.3 WITH COATED
CATALYTIC
0.2 CONVETRE
0.1

0
0 1.0697 2.1395 3.2093 4.279
bp(Kw)

Figure-7.7 Variation Of Specific Fuel Consumption With Brake Power

 54

7.7.2 Brake Power Efficiency

The variation of brake power efficiency with brake power value and at
different conditions as shown in the figure 7.8. The brake efficiency percentage keeps on
decreasing on introduction of catalytic converter and finally reaches the minimum value
on using coated catalytic converter. Thus at no load condition there is about 5.7 %
decrease in BP value and at peak load condition there is about 8.2 % decrease in BP
value. This is due to the fact that more fuel is consumed on using coated catalytic
converter which results in decrease in brake power efficiency. Thus the brake power

efficiency steadily decreases with the introduction of the coated catalytic converter.

30
Brake thermal efficiency(%)

25
WITHOUT
CATALYTIC
20 CONVERTER
WITH UNCOATED
15 CATALYTIC
CONVERTER
10 WITH COATED
CATALYTIC
CONVETRE
5

0
0 1.0697 2.1395 3.2093 4.28
BP(kW)

Figure-7.8 Variation of brake efficiency with brake power

 55

7.7.3 Nox Reduction

The variation of NOx value with brake power value and at different
conditions as shown in the figure 7.9. The NOx value keeps on decreasing on
introduction of catalytic converter and finally reaches the minimum value on using coated
catalytic converter. Thus at no load condition there is about 33.33% decrease in NOx
value and at peak load condition there is about 54.3 % decrease in NOx value. This is due
to the fact that NOx undergoes catalytic reaction with catalytic particles such as platinum,
palladium, rhodium, nano ferric oxide composites results in the production nitrogen and
oxygen as the end product. Thus there is steady decrease in NOx value with the

introduction of the coated catalytic converter.

800

700
WITHOUT
600 CATALYTIC
NOx Value(ppm)

CONVERTER
500
WITH UNCOATED
400 CATALYTIC
CONVERTER
300
WITH COATED
200 CATALYTIC
CONVETRE
100

0
0 1.0697 2.1395 3.2093 0.48
BP(kW)

Figure-7.9 Variation of NOX value with brake power

 56

7.7.4 HC Reduction

The variation of HC value with brake power value and at different conditions
as shown in the figure 7.10. The HC value keeps on decreasing on introduction of
catalytic converter and finally reaches the minimum value on using coated catalytic
converter. Thus at no load condition there is about 72.1% decrease in HC value and at
peak load condition there is about 68.8 % decrease in HC value. This is due to the fact
that HC undergoes catalytic reaction with catalytic particles such as platinum, palladium,
rhodium, nano ferric oxide composites results in the production water and oxygen as the
end product. Thus there is steady decrease in HC value with the introduction of the

coated catalytic converter.

100
90
80 WITHOUT
70 CATALYTIC
HC value(ppm)

CONVERTER
60
WITH UNCOATED
50 CATALYTIC
CONVERTER
40
WITH COATED
30 CATALYTIC
20 CONVETRE

10
0
0 1.0697 3.2093 0.48
BP(kW)

Figure-7.10 Variation of HC value with brake power

 57

7.7.5 CO Reduction

The variation of CO value with brake power value and at different conditions
as shown in the figure 7.11. The CO value keeps on decreasing on introduction of
catalytic converter and finally reaches the minimum value on using coated catalytic
converter. Thus at no load condition there is about 60% decrease in CO value and at peak
load condition there is about 40 % decrease in CO value. This is due to the fact that CO
undergoes catalytic reaction with catalytic particles such as platinum, palladium,
rhodium, nano ferric oxide composites results in the production carbon di oxide and
oxygen as the end product. Thus there is steady decrease in CO value with the

introduction of the coated catalytic converter.

0.035

0.03
WITHOUT
0.025 CATALYTIC
CONVERTER
CO value(%)

0.02 WITH UNCOATED

CATALYTIC
0.015 CONVERTER
WITH COATED
0.01 CATALYTIC
CONVETRE
0.005

0
0 1.0697 2.1395 3.2093 0.48
BP(kW)

Figure-7.11 Variation of co emission value with brake power

 58

CHAPTER 8

CONCLUSION

A detailed work has been done on synthesis and characterization of nano

ferric oxide composites by using planetary ball mill. Preparation of ferric oxide nano
composite is found to be feasible.

It is concluded that the conversion efficiency of the particles is found to be

about 26% during 8 hrs and 16 hrs samples. Thus there is a great reduction in size of the
particles during 8 hrs and 16 hrs sample. The conversion efficiency of the particles is
found to be 16% during 24 hrs sample. Thus there is less reduction in size of the particles
observed during 24 hrs sample. The particles are found to be in dispersed state with the
particle size ranging from 90-95 nm. Further EDAX pattern obtained for ferric oxide
nano- composites shows the composite contains 61.75wt% of iron which acts as a base
metal and 2.21wt% of potassium which acts as a re-enforcement material. Presence of
oxygen in significant amount (18.16 wt %) indicates that there is an presence of oxide
particles in the composites. The XRD pattern shows the intense peak below 20 degree.
This confirms the presence of nano sized particles and by using sheer formula the
crystalline size of the particles was found to be 90 nm. The morphology of the spectrum
clearly indicates that the nano composites are amorphorous in nature. TEM image clearly
identifies that the particle size were found to be varying from 80 nm to 106 nm. Further
the particle is found to be non-uniform over the surface. The Fourier transform infrared
spectroscopy shows the intense band at 3444 cm inwards due to the overstretching
vibration of water. The presence of water is once again confirmed at bending vibration at
1630 inwards. The peek at 2853cm, 2923cm inwards are due to the symmetric and
asymmetric vibration of arsenic group (potassium). The corresponding bending of arsenic
group was found to be occurring at 1283 cm inwards. Finally the intense broad band
between 720 cm and 500 cm inwards are due to the vibration was produced by the ferric
oxide molecules.
 59

The engine exhaust test has been carried out by using nano composites coated
catalytic converter Thus by using nano composite coated catalytic converter there is
about 33.33% decrease in NOx value at no load condition and about 54.3 % decrease in
NOx value at peak load condition. HC value is found to be decreasing 72.1% at no load
condition and at peak load condition. Finally at no load condition there is about 60%
decrease in CO value and at peak load condition there is about 40 % decrease in CO
value.
 60

REFERENCES

1. Apostolescu , B. Geiger , K. Hizbullahb, M.T. Jan , S. Kureti , D. Reichert, F.

Schott , W. Weisweiler, (2005),’ Selective catalytic reduction of nitrogen oxides
by ammonia on iron oxide catalysts’, vol 62 pp 104–114

2. Guido Ketteler, Wolfgang Ranke, and Robert Schl, (2002), ‘Potassium-Promoted

Iron Oxide Model Catalyst Filmsfor the Dehydrogenation of ethylbenzene: An
Example for Complex Model Systems’, vol 212, pp104–111

3. Hizbullah , S. Kureti , W. Weisweiler, (2004), ‘Potassium promoted iron oxide

catalysts for simultaneous catalytic removal of nitrogen oxides and soot from
diesel exhaust gas’, vol93–95 pp-839–843

4. Joseph, G. Ketteler, C. Kuhrs, W. Ranke, W. Weiss and R. Schlo, (2005),

‘Preparation and composition of potassium promoted iron oxide model catalyst
films’.

5. Kureti , W. Weisweiler , K. Hizbullah, (2003), ‘Simultaneous conversion of

nitrogen oxides and soot into nitrogen and carbon dioxide over iron containing
oxide catalysts in diesel exhaust gas’, vol-43 pp 281–291

6. Li, B.H. Shanks, Stability, (2006), ‘Phase Transitions of Potassium Promoted Iron
Oxide in Various Gas Phase Environments’, APCATA 11768

7. Ronald M.Heck and Robert J.Farrauto, (1997),‘Catalytic Air Pollution Control’,

by Tata Mcgraw-Hill publication limited, New Delhi

8. She, M. Flytzani-Stephanopoulos, C. Wang, Y. Wang, C.H.F. Peden, (2008),

‘SO2-induced stability of Ag-alumina catalysts in the SCR of NO with methane’,
APCATB-10478

9. Sipho C. Ndlela and Brent H. Shanks, (2006), ‘Reduction Behavior of Potassium-

Promoted Iron Oxide under Mixed Steam/ Hydrogen Atmospheres, vol-45 pp 22.

10. Yu Guo , Makoto Sakurai, Hideo Kameyama, (2008), ‘Temperature programmed

desorption/surface-reaction study of an anodic alumina supported Ag catalyst for
selective catalytic reduction of nitric oxide with propene’, vol-79 pp382–393.
 61

PUBLICATION

National Conference

1. N.Harshavardhana, G.Sakthinathan (2009) ‘Synthesis and Characterization of

Ferric oxide nano composites’ RTMT conference 2009, Department of
Manufacturing Engineering, Anna University Chennai.
 62

ANNEXURE-I

ENGINE SPECIFICATION

NAME Kirloskar
Bore 87.5mm
Stoke 110mm
CC 662 CC
No. of cylinders 1- vertical
Compression ratio 17.5:1
Cooling system Air
Peek pressure 76 bar
Rated speed 1500 rpm
Weight 163 Kgs
Specific fuel consumption 251 g/kW-hr
Injection pressure 200 bar
Brake power 4.4 kW