CHAPTER ONE

INTRODUCTION

1.1 Background of Study

Energy is prime mover of any kind of industries. Industrial revolution in Europe

late 18th century to early 19th century was a new mark of new manufacturing processes
industry. This is technology transition from hand production methods to machines
productions methods. Growth of these industries relies on sustenance of long term energy
sources. Attractive factors such as affordable, accessible, and environmentally friendly
must be look upon too. There are lots of sources of energy in this world. Some sources of
energy are renewable energy sources such as hydro, wind, geothermal, solar, and marine
energy. The major source in the world is fossil fuels which is non-renewable energy
sources such as petroleum, natural gases, and coal. Nuclear energy also used by advance
and modern country such as United States of America (USA), Japan, and Russia.
Non-renewable energy sources specifically petroleum is the most important and
the most abundant available energy sources is largely consumed in the world. As seen in
Figure 1.1, US energy consumption by source shows that petroleum is the major source
that had been consumed in 2010 [1]. Even though right now fossil fuels still being
processes in earth crust, the consumption of petroleum is rapidly increasing every year
because it is the most abundant resources available and it is the most reliable resources
among all. Data of petroleum consumption from US Energy Information Administration
recorded that from the past five years since 2010, most of Organisation for Economic Co-
operation and Development (OECD) and non-OECD country shown increasing number
of petroleum consumption especially for the non-OECD country or developing country
(Table 1.1). This will lead to shortage of this resource in the future. Declining supply of
crude oil due to continuous utilization of petroleum will cause petroleum price to
fluctuate.

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 Figure 1.1: USA energy consumption by energy source in 2010. (From US Energy Information
Administration, Monthly Energy Review, Table 10.1 (June 2011)) [1].

Table 1.1: Total petroleum consumption (Thousand Barrels Per Day). (From US Energy
Information Administration, www.eia.gov) [2]
Country 2010 2011 2012 2013 2014
Canada 2283 2310 2351 2431 2412
Mexico 2080 2112 2085 2044 1965
United States 19180 18882 18490 18961 19034
Australia 1005 1048 1073 1082 1082
Japan 4429 4442 4694 4530 4297
Korea, South 2268 2259 2321 2324 2350
New Zealand 152 154 151 152 156

The price of crude oil is driven by world market price and it is not steadfast.
Developing countries consumed around 22 million barrels per day (MBD) on average,
while developed industrialized countries consumed average of 43 MDB daily [3].
Depleting resources increase the price of the crude oil over the globe, thus affecting
world economy. Figure 1.2 shows price trends of crude oil from 2006 to 2013. After
2009, the price of crude oil keeps increasing over 3 USD per gallon. This is due to
continuous consumption of crude oil around the world that will cause depletion on this
particular resource in the future.

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 Figure 1.2: Crude Oil in Dollars per Barrel, Products in Dollars per Gallon from 2006 to 2013.
(Data from US Energy Information Administration, www.eia.gov)[2]

The issue of declining of crude oil supply and fluctuating oil price initiate the
research of alternative fuels [36]. This is to reduce the dependence on crude oil for
energy resource as it is will be facing depletion if it is consumed rapidly. Moreover,
petroleum resources only concentrated within few regions in the world. Country that do
not have this resources will have problem regarding resource exchange when it is limited
[7]. Countries that do not have supply of crude oil resources will depend on import of this
resource which will affect their economic and political factors. In general, entire globe is
too dependable on crude oil for transportation fuel, power generation, and utilization in
industry sectors. The study of alternative fuel goes on every year to find the best and most
reliable solution towards replacing petroleum dependence.
There are several points of view to importance of alternative fuels. First of all,
majority of alternative fuels are produced from domestic resources. This will decrease the
dependence on import energy resources. Most of alternative fuels can be produced from
biomass resources and agricultural wastes while electricity can be generated from
utilization of solar and fuel cells. This phenomenon of using local resources will reduce

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the import resources bill. Secondly, some alternative fuels are cheaper to operate
compared to petroleum products. Currently, most of alternative fuels cost slightly higher
than conventional fuel. But biodiesel and Compressed Natural Gas (CNG) have the most
competitive cost with petroleum cost [3].
Moreover, another factors that brings alternative fuels to attention is alternative
fuels generally reduce the vehicle exhaust emission and hence contributing towards
cleaner emission [2-3, 5]. Alternative fuels consist of simpler molecular structure than
petrol or diesel which has different mixtures of molecules (Figure 1.3). Furthermore, low
C:H ratio of alternative fuels generates less hydrocarbon emission. While the hydrogen
fuel is the clean fuel and generates no hydrocarbon emission. This will reduce global
pollution. Since 2005, Kyoto Protocol 1997 had been enforced in order for the developed
countries to reduce emission of transportation. This is international treaty that had been
signed by 192 parties purposely to reduce global pollution and global warming problems
around the globe. Some major pollutant produced by internal combustion (IC) engine
including carbon monoxide (CO), unburned hydrocarbon (UHC), particulate matter
(PM), NOX, and SO2. These emission leads towards many calamities such as health
problems, acid rain, and global warming.

Figure 1.3: Production of biodiesel. The left side shows the structure of glycerine. The right
structure shows three separate fatty acid chains that are now called biodiesel [9].

Problems of depletion, price increment, and global pollution lead the engineers
and scientists to look upon this solution seriously as it is affecting all industries especially
transportation industries. Therefore a lot of research conducted all over the world to
figure the best alternative fuels option to replaced petrol and diesel. There is a lot
candidate of attractive alternative fuels to replaced petroleum in automotive industry.

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Some if the attractive candidates that are still going through research and development of
many institutions are:
i. Biofuel (biodiesel and vegetable oils)
ii. Alcohols (methanol and ethanol)
iii. Gaseous fuels (natural gas, liquefied petroleum gas, and hydrogen)
iv. Electric vehicles
Current technologies of Compression Ignition (CI) engine contribute global
pollution due to its exhaust emission. At World Exhibition 1900, Rudolph Diesel the CI
engine inventor demonstrated his engine running on peanut oil after tragedy of engine
explosion running with powder coal. This is the beginning of utilization of biofuel
operating on diesel engine which is vegetable oils in that era [4]. There are lots of biofuel
that gone through research and development since the World Exhibition in 1900 such as
bioethanol and biodiesel to replace diesel in compression ignition (CI) engine [2, 3].
Currently, biodiesel is the most competitive and attractive among the other alternative
due to its abundant resources around the world and the feed stocks can be grown
domestically. Besides that, usage of biodiesel in CI engine does not require vast or no
modification at all for engine model 1992 onwards [4]. Although biodiesel have a lot of
benefits, there are some drawbacks of its utilization on diesel engine. Although pure
biodiesel (B100) benefits a lot towards cleaner exhaust emission, it is not suitable for
current CI engine because vast modification will be needed to countermeasure the
problems regarding lubricant performance [8]. Some of biodiesel property that is not
suitable for CI engine also disadvantages usage of pure biodiesel in CI engine. There is
also on-going debate with the issue of food versus fuel, environment issue, and various
economic and social issues regarding production of biodiesel.
To solve disadvantages of biofuel, the properties of particular biofuels is altered
by blending it with some additives in it. There are long list of fuel additives today, but
generally metal based additive and oxygenated additives are two major fuel additives that
being used in industry to compensate weakness of biofuels and improve performance and
emission of the CI engine operated by biodiesel [10]. Generally additive functions are to
act as combustion catalyst in order to promote better combustion and to improve the
property of the biodiesel.

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1.2 Problem Statement

Twin issues of declining crude oil supply and global pollution have raised the
world concern to solve the regarding issues. This is because shortage of crude oil supply
leads to high demand and low supply concept which increases the global price of that
particular resource. Another reason behind this problems is regarding exhaust emission of
CI engine that aggravates air pollution [3, 7, 8]. Rapid growth of society increases the
usage of crude oil by transportation throughout all over the world. Current CI engines
that operating with conventional diesel fuel emitting harmful and poisonous emission.
This is including carbon monoxide (CO), unburned hydrocarbon (UHC), particulate
matter (PM), NOX, and SO2. These emission leads to a lot of complication such as health
problems, global warming, air pollution, and acid rains. Although CI engines produce
better performance than Spark Ignition (SI) engine in term of power output and lower
cost of diesel rather than petrol, problems regarding emissions of CI engine operated with
conventional diesel cannot be avoided [3, 5, 9-8]. These drawbacks initiate vast research
of alternative fuels around the world to find a better substitute of current petroleum
resources.
There is long list of attractive alternative fuel that being researched until today.
Currently the most competitive alternative fuels to replace conventional diesel is
biodiesel [3]. Pure biodiesel promote better emission than conventional diesel engine, but
due to some components that contain elastomer, it is not compatible with higher
concentration ratio blend of biodiesel. Higher concentration ratio blends of biodiesel will
degrade fuel system primarily fuel pump and fuel hoses [3, 5]. Therefore a lower
concentration ratio blend of biodiesel is more suitable to use without modification.
However, there are some major disadvantages of biodiesel such as lower heating
value, higher viscosity, higher density, higher fuel consumption, and higher NO X
emission. These are the drawbacks of using biodiesel in CI engine. The main problems of
this research is how to improve all these drawbacks using fuel additive in order to have a
better result of the performance and emission of CI engine operating with Palm Oil
Methyl Ester (POME) biodiesel and metallic fuel additive. This research focuses on what
are the effects of metallic additive from Group 1A and 2A in POME biodiesel blended

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fuels. Therefore this research conducted for future fuel blends especially for POME
biodiesel.

1.3 Objective of Study

The objectives of this research are as follows;

1. To identify the feasibility of selected metal-based additive used in Palm Oil
Methyl Ester (POME) biodiesel.
2. To analyse the impact of various types of metallic additive towards CI engine
fuelled with POME biodiesel.
3. To compare the performance and emission of each types and ratio between
metallic additives, diesel, and POME biodiesel.

1.3.1 Research Question:

1. What degree of feasibility of selected metal-based additive used in Palm Oil

Methyl Ester (POME) in terms of stability and consistency of the mixture?
2. What are the impacts of various ratios and types of metallic additive towards the
engine performance and emission of CI engine fuelled with POME biodiesel?
3. Which ratio blends of POME biodiesel and metallic additive is the best for
emission and performance of CI engine for future fuel formulation?

1.4 Scope and Limitation of Study

This project focuses on the improvement of engine performance and emission of

each blend by analysing the effect addition of metallic fuel additive. Then characterising
the improvement based on specific parameter which is BSFC, torque, power, and exhaust
gas emission, etc.
1. Properties of POME biodiesel must be determined for each blend ratio
used such as B5, B10, B15, and B20. Property that will be taken into
consideration including viscosity, density, cetane number (heating value),
flash point, and pour point and cloud point.

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2. Metallic additive will be added into each blend to improve the weakness
of that particular blend ratio of POME biodiesel. Metallic additive that
will be used including magnesium, manganese, cerium, calcium, iron,
copper, barium and platinum. This metallic additive mainly from Group
1A and 2A of periodic table namely alkali metals and alkaline earth
metals.
3. All test sample or test fuel will be mixed and used instantly in order to
avoid phase separation of the sample. This project focuses only during the
combustion process of the fuel to analyse the effect of the additive towards
engine performance and exhaust emission.
4. The whole steady-state engine testing was done using engine
dynamometer but, exhaust gas emissions data was obtained by utilizing
the gas analyser.
5. Speed range during the testing of the engine using engine dynamometer is
between 1000 to 3000 RPM.
6. There will be no specific simulation done because the main focus of this
research is the impact of metallic additive towards performance and
emission of CI engine fuelled with different blend ratio of POME
biodiesel.

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1.5 Significance of Study

This study will be beneficial to students in Mechanical Engineering as well as to

practicing engineers, particularly in automotive field and fuel formulation scientists. This
study will affect economic sector, academic sector, and environment sector. With success
of this study, a fundamental toward solving global fuel price will be funnel towards a
better solution. This will be a benchmark of producing new fuel formula for the next
generation. In academic sector, this study will give a new fundamental of fuel additive in
fuel formulation specifically for chemical engineering students and effect of fuel additive
towards CI engine for mechanical engineering student. In environment sector, this study
will provide a better fundamentals and idea towards environmentally friendly of CI
engine with the new fuel formulation. All the data and findings will be published to be
guidance for future researcher that prone into this area of study which is metallic fuel
additive in POME biodiesel.
Moreover, the proposed research will benefit biofuel and automotive industry to
produce better fuel formulation. Biodiesel will be a suitable and relevant substitute of
conventional diesel. POME biodiesel that enhance with metallic fuel additive will be the
solution towards weaknesses of nowadays biodiesel and it will be one of the main fuel
formulations in the near future to cope with twin problems of fuel price and global
pollution.

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 CHAPTER II
LITERATURE REVIEW

2.1 Introduction

In automotive industry, engine performance is an important criterion. With a good

engine performance, fuel consumption can be optimized. Non-renewable resources such
as petroleum are important for automotive industry and it is facing depletion. Declining
of crude oil supply and fluctuating oil price initiate the research to use biofuel [4].
Moreover, petroleum resources only concentrated within few regions in the world.
Country that do not have this resources will have some problem regarding resource
exchange when it is limited [7]. Engineers and researchers are researches to improve
biofuel technology in automotive industry. There are a lot of biofuel that gone through
research and development such as bioethanol and biodiesel to replace diesel in
compression ignition(CI) engine [2, 4]. Usage of biodiesel in CI engine does not require
vast or no modification at all for engine model 1992 onwards [4].

2.2 Emissions Characteristics

Carbon dioxide (CO2) which is product from burning of hydrocarbon is

accumulated in the atmosphere. Since Industrial revolution in Europe late 18 th century to
early 19th century, greenhouse gases had been increasing until today in the atmosphere.
Greenhouse gases that produced by exhaust emission is nitrous oxide and carbon dioxide.
Greenhouse gases will increase temperature of the planet. This will cause ice melting in
north and South Pole. Besides that, CI engine fuelled with conventional diesel emitting
harmful and poisonous emission poisonous air pollutant. Main pollutants of CI engine
include carbon monoxide (CO), unburned hydrocarbon (UHC), particulate matter (PM),
NOX, and SO2 [3]. These emissions have serious effects on human health and some of it is
carcinogenic [14]. Concentration of NOx which is consists of nitric oxide (NO) and

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nitrogen dioxide (NO2) is greatest in urban areas with heavy traffic. Exposure of NO x will
leads to many problems such as respiratory infection, lung infection, and allergies [3].
NO combined with H2O vapour to form nitric acid and are removed from atmosphere by
direct deposition to the ground or transferred as rain water. NO x formed at higher
temperature in combustion chamber usually between (2500-3000 K). Other gases such as
oxygen and water vapour also contribute to formation of NO x at higher temperature in
combustion chamber [11-12]. Factors that affect formation of NOx includes fuel/air
equivalence ratio, burned gas fraction (EGR and residual gas fraction), and combustion
duration within the cylinder. Increasing of fuel-air equivalence ratio will cause the
emission of NOx to be higher (Figure 2.1(a)). Combustion timing also play important role
in formation of NOx. Advanced combustion time will increase flame temperature inside
combustion cylinder and cause the NOx formation to increase (Figure 2.1(b)). By
lowering the compression ratio also reduces NOx emissions due to decreasing maximum
cycle temperature. Reaction of NOx and atmosphere in the ozone will form
photochemical smog (smoke + fog).

(b)
(a)
Figure 2.1: (a) Fuel-air equivalence ratio for CI engine and (b) Combustion timing with
generation of NOx [15].

CI engine produces one-fifth Hydrocarbon (HC) emission than SI engine. This

partially or unburned hydrocarbon consist of two types of HC which is volatile organic
compounds (VOs) and polycyclic aromatic hydrocarbons (PAHs). VOC emits by exhaust
either as unburned fuels or as combustion products [3]. Due to combustion of CI engine
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that is efficient as much as 98%, only 2% of HC being emitted by CI engine[15]. This is
because molecular weight of diesel fuels is higher than gasoline fuels which will cause it
to boil and condense at higher temperature. This causes surface of solid carbon soot that
being generated during combustion mixed with HC and while the combustion take place
some of the UHC exhausted out of the cylinder. Secondly, HC formed due to incomplete
combustion caused by overmixing or undermixing. Undermixing caused by some fuel
particles does not have enough oxygen to react with and there are some spots that is to
lean in the fuel-lean zone for the combustion to take place. While overmixing causes by
some of the fuel particles mixed with burned products and causes incomplete combustion
happen. Next, HC formed due to small volume of fuel trapped on the tip of injector which
evaporates into exhaust slowly [16].
Particulate matter (PM) also known as soot concentration that increases rapidly
over recent years also brought into attention all over the world [3]. Particulate formed in
fuel-rich zones in the cylinder during combustion and it consists of solid carbon soot
particles[11-12]. PM formation is due to incomplete combustion of hydrocarbon. Engine
lubricating oil also contributes to formation of particulate. The emissions of particulate
will be high during high load condition of the engine. During this moment, to produce
maximum power output the amount of fuel injected also will be increased which will
result rich mixture that leads to incomplete combustion.
Carbon monoxide (CO) which is poisonous, odourless and colourless gas formed
because of incomplete combustion of hydrocarbon fuels [2, 11-12]. Moreover, poor
mixing and increasing fuel-rich equivalent ratio also produces CO as there is not enough
oxygen to convert all carbon to carbon dioxides. While fuel-lean mixtures produce lower
CO emission.

2.3 Combustion Behaviour

CI engine is different compared with SI engine in term of combustion mechanism.

In CI engine, air is highly compressed with high compression ratio (16:1 or 10:1) to raise
the temperature and pressure inside combustion chamber [15]. Fuel that is injected into
combustion chamber will mix with high temperature and pressure of air inside the

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combustion chamber. Then when it achieves auto-ignition temperature provided with
correct air-fuel ratio, combustion will take place. Ignition delay period is a preparatory
phase where fuel already injected but not yet ignited.

Figure 2.2: Stages of combustion in CI engine [15].

2.4 Biodiesel:

Biodiesel mostly is derived from vegetable oil or animal fats. The vegetable oil
gone through transesterification process which is has become common process nowadays
[3]. The reaction with alcohol usually methanol, removed the glycerine from the raw
material and produced alkyl ester product also known as biodiesel. There is some popular
feedstock used to produce biodiesel. Soybean oil biodiesel mostly produced in United
States of America (USA) while Europeans prefer to produced biodiesel from rapeseed
[12]. Most of tropical climate countries produce biodiesel from coconut oil or palm oil
[12]. Malaysia and Indonesia is the major palm oil producer in the world. Therefore palm
oil biodiesel is the best candidates of feedstock to use as alternative fuel to replace diesel
fuel in diesel engine also known as Compression Ignition (CI) engine in tropical climate
country [17]. Palm oil gone through process if esterification to produce Palm Oil Methyl
Ester (POME). The main problem of biodiesel application is common CI engine can only
operating with biodiesel blend B20 and below only. Otherwise additional modification
must be done to the engine [1, 4, 6-7]. Most of the research paper agreed that blend of
biodiesel with higher concentration will increase the fuel consumption. Brake specific

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fuel consumption (BSFC) increase when high concentration of biodiesel used. Blends of
20% above may require minor modification in order to decrease the fuel consumption
otherwise lower blend such as B10 or B15 can be used without modification [12]. The
reason behind this is because of low heating value and high density and viscosity of
biodiesel [18]. Therefore lower concentration of biodiesel used to attain lower
consumption [12]. Use of biodiesel also caused reduction of power due to the lower
heating value of the biodiesel [4, 8]. Biodiesel application however, showed a promising
result on exhaust emission to reduce pollution [7, 1820]. Most of research paper agreed
that high concentration of biodiesel blends reduce all the dangerous gas and PM emission
except for the NOx [1, 3-4, 7-8]. Vast reduction attained when using biodiesel as
alternative fuel as reduction of carbon monoxide (CO) and particulate matter (PM) is
50% and 30% respectively lower than petrodiesel [12]. Reduction of polycyclic aromatic
hydrocarbons (PAH) also advantage of using biodiesel in CI engine because PAH is
carcinogenic [12].

2.5 Fuel Additives:

To compensate with disadvantages of using biodiesel compared with neat diesel,

various fuel additive added into the biodiesel. Pure biodiesel is not used in diesel engine
due to higher viscosity and higher density [9-11]. Fuel additives used purposely to
improve the properties and characteristics of biodiesel fuel [10]. This is done to improve
performance and emission of CI engine operating with biodiesel and fuel additives blends
better than CI engine operating with neat biodiesel. There is some additives being
researched and developed such as metal based additives.

2.5.1 Effects of Fuel Additive to Engine Performance

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2.5.1.1 Power and Torque

Ali Keskin et al [23] found that power and torque values of single cylinder direct
injection diesel engine were increased slightly by addition of Manganese, Mn in diesel
fuel at some engine speeds between 18003200 rpm. This is due to the catalyst effect
which leads to shorter ignition delay period and slightly high heat release rates which
increase the temperature and cylinder pressure. This will result in increase of force
applied to the piston and give more power to the engine. However, in earlier research, Ali
Keskin et al [24] found that engine torque and power output values for B60 tall oil
biodiesel blends with Mg and Mo did not change significantly.

2.5.1.2 Brake Specific Fuel Consumption (BSFC)

Review by Ayhan Demirbas [12] state that brake specific fuel consumption
(BSFC) increase as concentration of biodiesel increase. Therefore, metal additives used to
enhance the combustion properties of the biodiesel. Specific fuel consumption values are
slightly decreased as a result of catalyst effect of metallic-based additives in diesel fuel
lead to shorter ignition delay period and greater heat release rates [23]. Reduction in
specific fuel consumption is 2.16% with D-8Mn, 3.12% with D-16Mn, 1.02% with D-
8Mg, and 2.01% with D-16Mg. Addition of homogeneous combustion catalysts
(FTC/FPC) in diesel fuels led to decreases in brake specific fuel consumptions under all
test conditions due to the improved fuel efficiency under the tested conditions between
2800 rpm (low) and 3200 rpm (medium) using single cylinder, naturally-aspirated, four-
stroke, air-cooled, direct-injection YANMAR L48AE diesel engine, which means less
fuel was burned to produce the same amount of work at higher loads. A maximum of
3.7% fuel saving was observed at 3200 rpm engine speed and 0.14 MPa BMEP [25].
Research by S. Karthikeyan et al. [26] found that addition of zinc oxide nanoparticles in
Pomolion Stearin Wax oil biodiesel blends reduced the brake specific fuel consumption
of single cylinder, four strokes, and vertical air cooled diesel engine. BSFC decrease as
dosing level of nanoparticle increases. The reason behind this improvement is because of
the delay of ignition time which leads to better combustion. Ali Keskin et al. [24] found

15
that higher specific fuel consumption values were measured with B60 tall oil biodiesel
fuels. This is more likely because of lower calorific value of tall oil biodiesel fuels. But
addition of metal additives which is Mo, decrease specific fuel consumption as much as
2.43% compared to B60 fuels. This is due to catalyst effect of metal based additives that
provide better thermal efficiency of the engine. Another research publish recently found
that for the case of influence of alumina nanoparticles, ethanol and isopropanol blend
with B20 soybeans biodiesel, brake specific energy consumption is higher for the B20
and D80SBD15E4S1+ alumina fuel blends compared to neat diesel at 25% and 50% load.
This is due to low calorific value of the fuel. Therefore more fuel needed to be injected to
gain the same amount of power output [27]. But for the same case of alumina
nanoparticles, ethanol and isopropanol blend with B20 soybeans biodiesel, at higher
loads of 75% and full load, the BSEC is minimum compared to the neat diesel. High
viscosity in the case of the B20 and D80SBD15E4S1+ alumina fuel blends at lower load
is overcome by a decrease in the viscosity at higher temperature (full load condition).
Presence of the alumina nanoparticle enhances the atomization rate that facilitates
complete combustion, and also increases the heat transfer from the products of
combustion. Thereby it reduces the sink temperature, which improves the engine
performance. Besides that, in another paper, slight improvement of BSFC was observed
with FBC added waste cooking palm oil (WCO) biodiesel with reduction of 8.6%. This is
due to catalyst effect of ferric chloride (FeCl3) that improves the oxidation of
hydrocarbons [28]. Research by V. Arul Mozhi Selvan et al. [29] using single cylinder,
four strokes, naturally aspirated, water-cooled, constant speed direct injection diesel
engine found that the addition of Cerium Oxides Nanoparticles (CERIA) and Carbon
Nanotube (CNT) in castor oil biodiesel decreases the specific fuel consumption compared
to E20 blend as CERIA and CNT enhance the combustion. Lowest specific fuel
consumption is 0.36 kg/kWh for E20 + CERIA 100 + CNT 100, whereas for the E20
blend it is 0.39 kg/kWh at the same bmep of 0.44 MPa. The reason behind this result is
because of CERIA acts as a catalyst and provides oxygen for the combustion, while the
Carbon Nanotubes accelerates the combustion and the combination effect of these
nanoparticles additive cause for the improvement in fuel consumption and thereby
increase in the brake thermal efficiency.

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2.5.1.3 Brake Thermal Efficiency (BTE)

Brake thermal efficiency increases with the addition of CERIA and CNT in
Diesterol blend to 7.5% when comparing with the Diesterol (castor oil biodiesel) blend
(E20) [29]. Reduction of BTE with biodiesel blends was caused by poor spray properties,
poor fuel air mixture, higher volatility, higher viscosity and lower calorific value, shorter
ignition delay time and heat loss. Cerium and platinum additives improved BTE
compared biodiesel without additives [30]. At full load, BTE of CNT blended JME
emulsion fuels are enhanced due to its improved combustion characteristics [31]. JME
fuel shows 24.8% BTE, while it is 28.45% and 26.34 % for JME2S5W and
JME2S5W100CNT respectively. BTE increase due to addition of cerium oxide
nanoparticles in the jathropa biodiesel [7, 26]. Cerium oxide nanoparticles promote
longer and complete combustion and acting as oxygen buffer which increase the
efficiency. There is maximum increase of 1.5% with dosing level of 20 ppm to 80 ppm of
cerium oxide nanoparticles.

2.5.2 Effects of Fuel Additive to Exhaust Emission

2.5.2.1 Carbon Monoxide (CO)

Biodiesel emission is cleaner than neat diesel emission. Therefore, to achieve

better emission, metal based additive is a good option to blend with biodiesel. Carbon
monoxide, CO which is carcinogenic is the biggest pollutant emits by CI engine that
operated by neat diesel. Therefore, CO emissions with Mn and Mg based additives blend
into neat diesel are decreased by 16.35% and by 13.43%, respectively which is effective
in decreasing CO emissions. Reduction of CO emission achieved due to reduced ignition
temperature during combustion process [23]. Another finding by Yu Ma et al. [25]
maximum reduction ratios for CO and UHC emissions of ferrous picrate-based catalyst in
diesel fuel was 21.1% and 13.1%, respectively. Reduction of CO and UHC is due to

17
improved brake specific fuel efficiency and increased combustion temperature at higher
loads. While in the case of Pomolion stearin wax biodiesel and zinc oxide nanoparticles
blends, CO emission are lower than B20 Pomolion stearin wax biodiesel due to short
ignition delay and improved ignition characteristic that provide better combustion process
[26]. Ali Keskin et al. [24] proves that CO emissions of B60 tall oil biodiesel with Mg
and Mo metallic additive decreased by 56.42% in single cylinder, four stroke direct
injection diesel engine Lombardini 6LD 400. Reduction of CO compared to B60 fuels
was 36.21% with B60 12Mg at 2600 rpm. While for B6012Mo at 2400 rpm was
24.12%. This is due to high oxygen content, low sulphur content, high cetane number,
and catalyst effect that reduced CO emission. For the case of influence of alumina
nanoparticles, ethanol and isopropanol blend with B20 soybeans biodiesel, the CO
emission is higher 66 % at 25% load compared to neat diesel and B20. But at full load
condition it reduces as much as 40% compared to neat diesel and B20 fuel. This is due to
inherent oxygen present in the soybean biodiesel with utilization of alumina nanoparticle
that enhance atomization which leads to complete combustion of the fuel [27]. Carbon
monoxide (CO) emission of FBC added waste cooking palm oil (WCO) biodiesel
decreased by 52.6%. Lowest CO emission of 1.9 g/kWh was obtained with FBC added
biodiesel due to improves oxidation of CO into CO2 [28]. This is further improved by
influence of increasing injection pressure and advancing injection timing that resulted in
better combustion [28]. Recent study of Nano technology additives shows that additives
of CNT and CERIUM in castor oil biodiesel operated by single cylinder, four strokes,
naturally aspirated, water-cooled, constant speed direct injection diesel engine increases
the carbon monoxide emission to 22.2% compared to E20 blend. This is due to not
enough oxygen to convert all carbon into CO2, some fuels do not get burned and some
carbon ends up as carbon monoxide. A thick quench layer created by the cooling effect of
vaporizing alcohol also play a major role on CO emission at part loads [29].

2.5.2.2 Oxides of Nitrogen (NOx)

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 S. Karthikeyan et al. [26] found that there is no significant differences were
observed on NOx emissions of all zinc oxide nano-additives with Pomolion Stearin Wax
Biodiesel blended fuels. However, addition of alumina nanoparticle in diesel-soybean
biodiesel blends enhances the NOx emission, due to the maximum cylinder pressure and
higher heat release achieved. Beyond 50% of the load, the NOx emission is high for B20
diesel-soybean biodiesel and D80SBD15E4S1 + alumina fuel blend when compared to
neat diesel. However at full load NO x emission is 1792 ppm for neat diesel, whereas it is
1921 ppm, 1971 ppm for B20 and D80SBD15E4S1 + alumina fuel blend respectively. An
increased emission of 7.2% and 9.9% was observed for B20 and D80SBD15E4S1 +
alumina fuel. This is due to higher heat release for the case of D80SBD15E4S1 + alumina
fuel compared to neat diesel. Therefore this result in higher temperature which produce
more NOx emission [27]. Ferric chloride (FeCl3) which is acting as Fuel Borne Catalyst
(FBC) in waste cooking palm oil biodiesel shows an increment of NOx emission
compared to biodiesel without FBC. This is due to presence of FBC which oxidizes the
nitrogen into nitric oxide during combustion process [28]. It is observed that the lower
concentrations of CERIA and CNT in the fuel castor oil biodiesel blend increase the
nitrogen oxide emissions and the higher concentrations decrease the nitrogen oxide
emission. Lowest nitrogen oxide emission is observed as 283 ppm for the E20 + CERIA
50 + CNT 50 blend and it is 308 ppm for the E20 + CERIA 25 + CNT 25 blend under the
BMEP of 0.44 MPa. The nitrogen oxide emission increases with increase in loads due to
the increase in cylinder gas temperature. While the addition of CERIA and CNT enhances
the combustion and causes an increase in the cylinder gas pressure and the corresponding
temperature which subsequently increases the nitrogen oxide emission [29]. J. Sadhik
Basha et al. [31] found that NOx emission reduced with the CNT addition into the fuel
samples of Jathropa Methyl Ester biodiesel blends. This is due to significant heat sink
effect during the combustion in the diesel engine. The heat absorbed rapidly thus
decreasing the burning gas temperature in the combustion chamber. At full load, NOx
emission for JME fuel is 1282 ppm, while it is 1001, 961 and 910 ppm for JME2S5W,
JME2S5W50CNT and JME2S5W100CNT fuels respectively. Another research using
Jathropa biodiesel show that NOx emission also reduced with increasing dosing level of

19
cerium oxides nanoparticles [32]. This is maybe due to catalyst effect of the additive
which reduced the nitrogen oxides.

2.5.2.3 Smoke and Particulate Matter (PM)

Smoke opacity of tall oil biodiesel and metal based additives of Mg and Mo
decreased smoke opacity by 30.43%. High oxygen content and catalyst effect reduced the
smoke opacity [24]. Additives of CNT and CERIUM in castor oil biodiesel enhances the
combustion and reduces the hydrocarbon and smoke emission to 7.2% and 47.6%
respectively when comparing with the E20 blend. This is due to function of CERIA that
enhances the combustion and CNT that suppress the soot [29]. Smoke opacity shows
significant reduction with addition of CNT in the JME emulsion fuels [31]. This is due to
reduced soot formation and improved rapid secondary atomization effects. At the full
load, the magnitude of smoke opacity observed for the JME fuel was 69%, whereas it
was 60%, 57%, 52% and 49% for the JME2S5W, JME2S5W25CNT, JME2S5W50CNT
and JME2S5W100CNT fuels respectively.

2.5.2.4 Hydrocarbon (HC)

HC emission slightly increased compared to neat Jathropa Methyl Ester (JME)

due to water content in the emulsion fuels that lowered the temperature in combustion
chamber and enhanced the unburned HC. But, there is reduction in HC emission for the
CNT and JME emulsion fuels. This is due to intensive secondary atomization in the
combustion chamber which causes HC to oxidize [31]. At full load, JME fuel produce 59
ppm of HC, while it is 60 and 57 ppm for JME2S5W50CNT and JME2S5W100CNT
respectively. HC emission decrease as much as 25% to 40% with increasing dosing level
of cerium oxide additive in Jathropa biodiesel [32]. This is because of the catalyst effect
by cerium oxide which lowers the carbon combustion activation temperature and thus
enhances the HC oxidation. This resulting in complete combustion and reduce the HC.

20
 CHAPTER THREE
METHODOLOGY

3.1 Introduction

This chapter will be describes the research methodology of this research. To

achieve the objective of this project, suitable and appropriate procedures will be applied.
The procedures start with fuel sampling process, engine baseline data collection, sample
fuel testing and data collection, and data analysis for each fuel sample. The detail process
of the characterization will be discussed in this chapter.

21
 3.2 Flow Chart

Engine Baseline Data Collection

(Diesel Fossil Fuels)

Engine Baseline Data Collection

(POME Biodiesel)
B5, B10, B15, B20

ADDITION:
METALLIC ADDITIVES
- Alkali Metals (Group 1A)
-Alkali Earth Metals (Group 2A)

ELECTRIC DYNAMOMETER
AND
Alkali
Alkali Metals (Group 1A) Earth(B5,
+ POME Metals (Group
B10, 2A) + POME (B5,GAS
B15, B20) B10,ANALYZER
B15, B20)

STEADY STATE PERFORMANCE ANALYSIS

THESIS DOCUMENTATION

22
3.3 Equipment and Materials

3.3.1 Palm Oil Methyl Ester (POME) Biodiesel Blend Ratio

This research will be using Palm Oil Methyl Ester (POME) biodiesel as
experiment fuel. POME biodiesel with different blend ratio of Palm Oil and petroleum
diesel will be used to operate CI engine. Fuel standard will follow standard specification
by European standard EN 14214 and ASTM International D6751. All fuel samples will
be stored in glass container to avoid unnecessary reaction of POME biodiesel. There are
four POME blends ratio that will be used in this research:
i. B5 (5% Palm Oil : 95% Diesel)
ii. B10 (10% Palm Oil : 90% Diesel)
iii. B15 (15% Palm Oil : 85% Diesel)
iv. B20 (20% Palm Oil : 80% Diesel)
Properties of each fuel sample will be determined and act as a benchmark or baseline.
This is to compare the properties before and after addition of metallic additives.
Properties that will be focused on are:
i. Flash point.
ii. Density.
iii. Viscosity.
iv. Calorific value or heating value.

Figure 3.1: POME biodiesel sampling in glass container.

3.3.2 Metallic Fuel Additives:

23
 POME biodiesel will be blends with metallic additives. Metal additives used will
be in the powder form to ensure it will mix well heterogeneously. Metal additives used
will be from Group 1A (Alkali Metals) and Group 2A (Alkali Earth Metals) of the
periodic table.
a) Alkali Metals (Group 1A):
i. Lithium, Li.
b) Alkali Earth Metals (Group 2A):
i. Beryllium, Be.

(b)
(a)
Figure 3.2: (a) Beryllium, Be in powder form; (b) Lithium, Li in powder form.

24
3.3.3 Engine Specification:

Engine that will be used for this research will be Yanmar Air Cooling LN Series
Diesel Engine.

. (b)
(a)

Figure 3.3: (a) and (b) Yanmar Air Cooling LN Series Diesel Engine that will be used. (From
www.yanmaritaly.it) [33]

Table 3.1: Yanmar Air Cooling LN series engine specification. (From www.yanmaritaly.it) [33]
Engine model L70N
4 stroke, vertical cylinder, air cooled
Type
diesel engine
No. of Cylinders 1
Bore x Stroke mm 78 x 67
Displacement liter 0.320
Maximum Engine Speed rpm(min-1) 3600
Rated Output / Engine
kW 4.9
Output Speed
High Idling rpm(min-1) 3800 30

25
3.4 Testing Plan/Matrix

Initially, baseline data of the engine will be taken for both performance and
emission. Baseline data will be fuelled by petroleum diesel. Then data of each POME
blends ratio (B5-B20) will be taken. Finally, each POME blends ratio will be added with
each metal additive and performance and emissions data will be collected. The testing
matrix is listed in Table 3.2.

Table 3.2: Testing matrix for all types of POME blends ratio and metal additives. Performance
and emission data will be collected for each fuel sample.

1 = Present 0 = Absent
Test Mode Diesel B5 B10 B15 B20 Li Be
Baseline 1 0 0 0 0 0 0
T1 0 1 0 0 0 0 0
T2 0 0 1 0 0 0 0
T3 0 0 0 1 0 0 0
T4 0 0 0 0 1 0 0
T5 0 1 0 0 0 1 0
T6 0 1 0 0 0 0 1
T7 0 0 1 0 0 1 0
T8 0 0 1 0 0 0
T9 0 0 1 0 0 0 1
T10 0 0 0 1 0 1 0
T11 0 0 0 1 0 0 0
T12 0 0 0 1 0 0 1
T13 0 0 0 0 1 1 0
T14 0 0 0 0 1 0 0
T15 0 0 0 0 1 0 1

26
3.5 Data Collection Method

The engine will be run at full load condition between 1000 RPM to 2000 RPM
with data steps of 200 RPM for all tests. Each test will be run three times and the average
will be calculated to be analysed. Data that will be collected for every fuel samples are:

Engine Performance Exhaust Emission

i. Torque i. Carbon Monoxide, CO
ii. Power ii. Oxides of nitrogen, NOx
iii. Brake Specific Fuel Consumption iii. Carbon Dioxide, CO2
iv. Brake Thermal Efficiency iv. Particulate matter/soot.

3.5.1 Exhaust Emission Data

Desired emission data will be collected by using gas analyser. Figure 3.4 is the
MRU gas analyser that will be used to collect exhaust emission data except particulate
matter/soot. The probe of the gas analyser will be located at the exhaust tail and the gas
analyser will display the data on the monitor on the gas analyser. For particulate
matter/soot, filter paper will located at the tip of the tail pipe the difference between
weight before and after will be observed.

(a) (b)
Figure 3.4: (a) MRU gas analyser that will be used to collect exhaust emission data [34]; (b)
Monitor of MRU gas analyser that show the data collected .

27
3.5.2 Engine Performance Data

Electric dynamometer also called electric dyno will be used in this research. All
the performance data will be collected using electric dyno. Yanmar diesel engine will be
mounted to the electric dyno and external fuel tank will be mounted to collect fuel
consumption data. The others data will be collected manually from test bench controller.

(a)

(c)
(b)

(d)
Figure 3.3: (a) Electric dyno model; (b) engine mounted to dyno; (c) Test bench control
hub; and (d) external fuel tank.

3.6 Research Planning

28
 I. Please refer to Appendix I for Gantt chart planning of research activities.
II. Please refer to Appendix II for Milestone Chart planning of research activities

29
 REFERENCES:

[1] US Energy Consumption by Source , 2010. [Online]. Available: www.eia.gov.

[2] US Energy Consumption by Source , 2010, US Energy Information

Administration, 2011. .

[3] A.Ramadhas, Alternative fuels for transportation, 1st ed., Boca Raton, FL: CRC
Press, 2011, pp. 4180.

[4] U. Department of Energy, Freedom CAR & Vehicle Technologies Program Just
the Basics, Energy, 2003.

[5] S. A. Basher, A. a. Haug, and P. Sadorsky, Oil prices, exchange rates and
emerging stock markets, Energy Econ., vol. 34, no. 1, pp. 227240, 2012.

[6] S. miech and M. Papie, Fossil fuel prices, exchange rate, stock market: A
dynamic causality analysis on the European market, Econ. Lett., vol. 118, no. 1,
pp. 199202, 2012.

[7] A. K. Agarwal, Biofuels (alcohols and biodiesel) applications as fuels for internal
combustion engines, Prog. Energy Combust. Sci., vol. 33, no. 3, pp. 233271,
Jun. 2007.

[8] P. D. Hill, Biodiesel Basics, Department of Energy, US, vol. 4, no. 2, pp. 113,
2011.

[9] J. Hafalia, A Chemistry Perspective: Gasoline or Biodiesel?, Yale National

Initiative, Yale University, 2015. [Online]. Available: teachers.yale.edu.

[10] S. Dinesh, L. Kumar, R. P. P, P. Patel, and K. Nikul, Performance and Emission

By Effect of Fuel Additives for Ci Engine Fuelled With Blend of Biodiesel and
Diesel - a Review Study, J. Eng. Res. Stud., vol. III, no. IV, pp. 58, 2000.

30
[11] V. I. . Ajiwe, V. . Ajibola, and C. M. A. O. Martins, Biodiesel Fuels From Palm
Oil Methylester And Ester-Diesel Blends, vol. 17, no. 1, pp. 1926, 2003.

[12] A. Demirbas, Importance of biodiesel as transportation fuel, Energy Policy, vol.

35, no. 9, pp. 46614670, Sep. 2007.

[13] Y. A. Cengel and M. A. Boles, Thermodynamics: An Engineering Approach, SI

Version. McGraw-Hill Education, 2014.

[14] M. C. Turner, D. Krewski, C. A. Pope, Y. Chen, S. M. Gapstur, and M. J. Thun,

Long-term Ambient Fine Particulate Matter Air Pollution and Lung Cancer in a
Large Cohort of Never-Smokers, Am. J. Respir. Crit. Care Med., vol. 184, no. 12,
pp. 13741381, Dec. 2011.

[15] V. Ganesan, Internal Combustion Engines. McGraw-Hill Education, 2012.

[16] H. N. Gupta, Fundamentals of Internal Combustion Engines. Prentice-Hall Of

India Pvt. Limited, 2006.

[17] A. Rahmadi and L. Aye, Biodiesel from Palm Oil as an Alternative fuel for
Indonesia: Opportunities and Challenges, pp. 322328, 2003.

[18] J. Xue, T. E. Grift, and A. C. Hansen, Effect of biodiesel on engine performances

and emissions, Renew. Sustain. Energy Rev., vol. 15, no. 2, pp. 10981116, Feb.
2011.

[19] M. Shahabuddin, A. M. Liaquat, H. H. Masjuki, M. A. Kalam, and M. Mofijur,

Ignition delay, combustion and emission characteristics of diesel engine fueled
with biodiesel, Renew. Sustain. Energy Rev., vol. 21, pp. 623632, May 2013.

[20] M. . Kalam and H. . Masjuki, Biodiesel from palmoilan analysis of its

properties and potential, Biomass and Bioenergy, vol. 23, no. 6, pp. 471479,
Dec. 2002.

31
[21] Y. Lin, Y. G. Wu, and C.-T. Chang, Combustion characteristics of waste-oil
produced biodiesel/diesel fuel blends, Fuel, vol. 86, no. 1213, pp. 17721780,
Aug. 2007.

[22] M. H. Mat Yasin, T. Yusaf, R. Mamat, and a. Fitri Yusop, Characterization of a

diesel engine operating with a small proportion of methanol as a fuel additive in
biodiesel blend, Appl. Energy, vol. 114, pp. 865873, 2014.

[23] A. Keskin, M. Gr, and D. Altparmak, Influence of metallic based fuel

additives on performance and exhaust emissions of diesel engine, Energy
Convers. Manag., vol. 52, no. 1, pp. 6065, 2011.

[24] A. Keskin, M. Gr, and D. Altiparmak, Influence of tall oil biodiesel with Mg
and Mo based fuel additives on diesel engine performance and emission,
Bioresour. Technol., vol. 99, no. 14, pp. 64346438, 2008.

[25] Y. Ma, M. Zhu, and D. Zhang, The effect of a homogeneous combustion catalyst
on exhaust emissions from a single cylinder diesel engine, Appl. Energy, vol. 102,
pp. 556562, Feb. 2013.

[26] S. Karthikeyan, A. Elango, and A. Prathima, Performance and Emission Study on

Zinc Oxide Nano Particles Addition with Pomolion Stearin Wax Biodiesel of CI
Engine, vol. 73, no. March, pp. 187190, 2014.

[27] T. Shaafi and R. Velraj, Influence of alumina nanoparticles, ethanol and

isopropanol blend as additive with dieselsoybean biodiesel blend fuel:
Combustion, engine performance and emissions, Renew. Energy, vol. 80, pp.
655663, 2015.

[28] G. R. Kannan, R. Karvembu, and R. Anand, Effect of metal based additive on

performance emission and combustion characteristics of diesel engine fuelled with
biodiesel, Appl. Energy, vol. 88, no. 11, pp. 36943703, 2011.

32
[29] V. Arul Mozhi Selvan, R. B. Anand, and M. Udayakumar, Effect of cerium oxide
nanoparticles and carbon nanotubes as fuel-borne additives in diesterol blends on
the performance, combustion and emission characteristics of a variable
compression ratio engine, Fuel, vol. 130, pp. 160167, 2014.

[30] H. K. Rashedul, H. H. Masjuki, M. a. Kalam, a. M. Ashraful, S. M. Ashrafur

Rahman, and S. a. Shahir, The effect of additives on properties, performance and
emission of biodiesel fuelled compression ignition engine, Energy Convers.
Manag., vol. 88, pp. 348364, 2014.

[31] J. Sadhik Basha and R. B. Anand, Performance, emission and combustion

characteristics of a diesel engine using Carbon Nanotubes blended Jatropha Methyl
Ester Emulsions, Alexandria Eng. J., vol. 53, no. 2, pp. 259273, 2014.

[32] V. Sajith, C. B. Sobhan, and G. P. Peterson, Experimental investigations on the

effects of cerium oxide nanoparticle fuel additives on biodiesel, Adv. Mech. Eng.,
vol. 2010, 2010.

[33] Yanmar Air Cooling LN Series Diesel Engine, Yanmar Italy S.p.A., 2015.
[Online]. Available: www.yanmaritaly.it/.

[34] Portable Gas Monitoring System MRU Vario Plus, MRU Measuring instruments
for flue gases and environmental protection GmbH, 2015. [Online]. Available:
en.mru.eu/.

33
APPENDICES
 APPENDIX I
Research Gantt chart

YEAR 1 (2014/2015) SESSION 2 YEAR 1 (2015/2016) SESSION 1 YEAR 2 (2015/2016) SESSION 2 YEAR 2 (2016/2017) SESSION 1
Project Activities FIRST SEMESTER SECOND SEMESTER THIRD SEMESTER FOURTH SEMESTER
MA AP JU JU AU OC NO DE JA FE MA AP JU JU AU SE OC NO DE JA
MAY SEP MAY FEB
R R N L G T V C N B R R N L G P T V C N
Identification of Project
Titles
Gathering of References
Proposal Writing
Proposal Submission
Defence Research Proposal
Experimental Set up
Prelimenary Results

Minimal Modification on
Exprerimental Set Up

Collect, Analyse and data

Validation

Publication

Thesis Writing and

Submission
Viva and Final Correction
 APPENDIX II
Research Milestone Chart

YEAR 1 (2014/2015) SESSION 2 YEAR 1 (2015/2016) SESSION 1 YEAR 2 (2015/2016) SESSION 2 YEAR 2 (2016/2017) SESSION 1
Project Activities FIRST SEMESTER SECOND SEMESTER THIRD SEMESTER FOURTH SEMESTER
MA AP JU JU AU OC NO DE JA FE MA AP JU JU AU SE OC NO DE JA
MAY SEP MAY FEB
R R N L G T V C N B R R N L G P T V C N
Identification of Project
Titles
Gathering of References
Proposal Writing
Proposal Submission
Defence Research Proposal
Experimental Set up
Prelimenary Results

Minimal Modification on
Exprerimental Set Up

Collect, Analyse and data

Validation

Publication

Thesis Writing and

Submission
Viva and Final Correction