THE EFFECTS ON WATER CONTENT THAT INFLUENCE THE

PERFORMANCE OF PLASTIC OIL EMULSION VIA ULTRASONICATION

NUR ADRIANA AMIRAH BINTI NOOR ROZAIMAN

UNIVERSITY KUALA LUMPUR

MALAYSIAN INSTITUTE OF CHEMICAL AND BIO-ENGINEERING
TECHNOLOGY
JANUARY 2023
 THE EFFECTS ON WATER CONTENT THAT INFLUENCE THE
PERFORMANCE OF PLASTIC OIL EMULSION VIA ULTRASONICATION

NUR ADRIANA AMIRAH BINTI NOOR ROZAIMAN

55221119125

Report Submitted to Fulfill the Partial Requirements

For the Bachelor of Chemical Engineering with Honours
Universiti Kuala Lumpur

JANUARY 2023
 TABLE OF CONTENTS

LIST OF TABLES ........................................................................................... v

LIST OF FIGURES ..........................................................................................vi

CHAPTER 1: INTRODUCTION....................................................................... 1

1.1 Background of Study ....................................................................... 1

1.2 Problem of Statement ...................................................................... 3

1.3 Objectives ......................................................................................... 4

1.4 Research Scope ............................................................................... 4

1.5 Significance of Study ....................................................................... 5

CHAPTER 2: LITERATURE REVIEW ............................................................ 6

2.1 Waste Plastic Oil .............................................................................. 6

2.1.1 Polyethylene terephthalate ....................................................... 6

2.1.2 High-density polyethylene ........................................................ 7

2.1.3 Polyvinyl chloride ...................................................................... 7

2.1.4 Low-density polyethylene ......................................................... 8

2.1.5 Polypropylene ............................................................................ 8

2.1.6 Polystyrene ................................................................................ 9

2.2 Emulsions ......................................................................................... 9

2.2.1 Definitions of emulsions ........................................................... 9

2.2.2 Types of emulsions ................................................................. 10

2.2.3 Emulsion Instability ................................................................. 11

2.3 Processes To Emulsify the Emulsions ......................................... 16

2.3.1 Mechanical agitation................................................................ 16

2.3.2 Ultrasonication technique ....................................................... 16

2.4 Performance of Waste Plastic Oil Emulsion ................................ 18

2.4.1 Viscosity ................................................................................... 18

iii
 2.4.2 Exhaust emission .................................................................... 19

2.4.3 Flash point ................................................................................ 20

2.4.4 Waste plastic oil emulsion as a lubricant .............................. 21

CHAPTER 3: METHODOLOGY.................................................................... 23

3.1 Introduction .................................................................................... 23

3.2 Materials and Apparatus ................................................................ 24

3.3 Addition Of Deionized Water to The Crude WPO......................... 25

3.4 Emulsification of W/O Using Ultrasonication Technology ......... 26

3.5 Properties of Emulsified Fuel ........................................................ 27

3.6 Expected Results ........................................................................... 28

3.7 Cost Estimation .............................................................................. 28

3.8 Gantt Chart ...................................................................................... 29

REFERENCES .............................................................................................. 30

iv
 LIST OF TABLES

Table 3.1 Materials and Apparatus that will be used in methodology............ 24

Table 3.2 Amount of Samples that need to be prepared ............................... 25

Table 3.3 Estimated cost to carry out this methodology ................................ 28

v
 LIST OF FIGURES

Figure 1.1 Plastic Waste to Fuel (Lavina, 2020) ............................................. 1

Figure 1.2 Water-in-Oil and Oil-in-Water Emulsion (Andrews, 2021) .............. 2

Figure 2.1 Mechanism of Emulsion Destabilization (McClements, 2004) ..... 11

Figure 2.2 Types of Floc Produced by Droplets and Characterized by An

Increase in Effective Size (Romero-peña, 2021) ........................................... 14

Figure 2.3 Ostwald Ripening......................................................................... 15

Figure 2.4 Cavitation Process (Xu et al., 2015) ............................................ 17

Figure 3.1 Ultrasound equipment used to emulsify W/O emulsions.............. 26

Figure 3.2 Droplet breakup during ultrasonic emulsification (Sarkar,2023) .. 26

Figure 3.3 The four-ball machine T-02U used to determine the lubricity tests (A
Jaworski et al., 2021)..................................................................................... 27

vi
 CHAPTER 1: INTRODUCTION

1.1 Background of Study

For more than a century, external combustion engines have traditionally used
fossil diesel fuel as their major source of fuel for their diesel engines and other
burners. Sectors that use this form of fossil fuel include transportation,
agriculture, and industry. Due to the finite supply of natural fossil fuel supplies,
scientists and engineers have focused more on looking for alternative fuels
that are accessible and practical to utilize. They can be converted quickly into
different organic compounds and are ready for use as industrial or automotive
fuels (Arjharn et al., 2022).

A potentially useful alternative fuel is Waste Plastic Oil (WPO), which is

produced from municipal solid waste (MSW), any type of plastics and medical
waste. Any type of plastics usually includes High Density Polyethylene
(HDPE), Low Density Polyethylene (LDPE), and Polystyrene (PS). Recently,
Clariant Catalysts collaborated with the Slovakian chemical company Duslo's
VUCHT Research Institute of Chemical Technology, which used the pyrolysis
process to turn plastic waste into diesel fuel as shown in the Figure 1.1 (Lavina,
2020).

Figure 1.1 Plastic Waste to Fuel (Lavina, 2020)

1
Emulsions have become quite important in a variety of sectors, including those
that deal with food, medicine, cosmetics, health care formulations, paints,
polymer blends, and oils. Emulsions are heterogeneous systems made
consisting of at least two immiscible liquids, such as water and oil, with one of
the immiscible liquids usually be uniformly disseminated as tiny droplets
throughout the other liquid phase through mechanical agitation. Emulsions are
defined as a category of liquid-liquid colloid. The surrounding liquid is referred
to as the continuous phase, while the phase that is composed of tiny droplets
is referred to as the dispersed phase. Depending on whether the continuous
phase is made up of water or oil, emulsions are normally classified as either
oil-in-water (O/W) or water-in-oil (W/O) (Lu & Gao, 2010).

Figure 1.2 Water-in-Oil and Oil-in-Water Emulsion (Andrews, 2021)

Performance of the waste plastic oil (WPO) can be analyzed by evaluating its
properties and compared the properties with the commercial diesel. Although
WPO's density was relatively similar to that of kerosene and diesel, it had a
viscosity that was higher than kerosene and lower than diesel. It was clear
from this that WPO might replace petroleum-based goods (Padmanabhan et
al., 2021). Thus, WPO has a similar flash point to other petroleum products at
approximately 41°C. This proves how safe WPO is for engine operations.
However, handling and shipment must be done with greater care (Chandran
et al., 2018). Also, density, vapour pressure, vapour diffusivity, surface tension,
and viscosity were parameters that had a bigger impact on the composition of
the fuel spray, combustion, and emission characteristics.

2
Moreover, to emulsify the fuel with different percentage of water,
ultrasonication technology is used in this research. Ultrasound is distinctive
homogenization method used in a wide range of applications. It is a process
that breaks down large particles into smaller fragments or more uniformly sized
particles in the base fluid (Karami et al., 2019). Also, ultrasonication is a
homogenization procedure that uses ultrasonic rates or frequencies above 20
kHz. The type of sonicators that are frequently used such as probe-type and
bath-type. High intensity probe type sonicators have been found to be more
effective than bath type (Sandhya et al., 2021). The advantages of using
ultrasonic techniques included its low power requirements, in-line
measurement, long-term stability, non-invasiveness, high resolution and
accuracy, and high sensitivity. (Raigan, 2020).

1.2 Problem of Statement

These days, enormous expansion in the production of plastic is produced due

to the significant amount of this type of waste. Plastic waste has cumulative
and long-term environmental effects due to its long lifespan, even though it is
not considered hazardous waste (Fulgencio-medrano et al., 2022). Also, the
world has been experienced energy crisis due to the depleting of the fossil fuel
and the recent case of the war between Ukraine and Russia had caused the
increasing price of the fuel across the world. Due to these problems, making
diesel from plastic waste is one of the techniques to lessen the massive
amount of plastic waste that exists, and waste plastic oil (WPO) is another
renewable energy that can be used to replace fuel.

Then, diesel engine emissions led to the formation of ground-level ozone,

which harms plants such as trees and crops. As a result of the greater levels
of carbon dioxide (CO2) and carbon monoxide (CO) in diesel exhaust,
exposure can cause major health disorders like asthma and respiratory
ailments (EPA, 2022). Recent studies reveal that WPO contains lower content
of CO2 and CO compared to commercial diesel and emit lower greenhouse
gases.

3
1.3 Objectives

• To investigate the viscosity of emulsified fuel with different percentage of

water content.
• To analyze the performance of the emulsified waste plastic oil (WPO) by
evaluating its properties.
• To compare the properties of the emulsified WPO with the crude WPO.

1.4 Research Scope

In this study, raw crude oil will be given by Syngas Sdn. Bhd. which is WPO
that was produced from medical waste. However, the company produced
WPO by using depolymerization process while other company used pyrolysis
process as their main process. Then, a different percentage of water that is
10%, 20%, 30%, 40%, and 50% will be added to the fuel before the mixed
samples are emulsified using ultrasonic technology. Next, the viscosity of the
emulsified fuels will be investigate using a machine named Brookfield
viscometer model LVDV2T with spindle number 40Z and 52Z.

Therefore, the performance of the emulsified fuel will be analyzed by

evaluating its properties which are the emission of CO and CO2, flash point,
the viscosity, and the lubricity of the emulsified fuel. The emission of the CO
and the CO2 can be observed with a gas analyzer. Moreover, the equipment
that will be used to determine the flash point of the samples is Pensky-Martens
and lubricating properties of the crude WPO and emulsified fuel samples will
be tested by using industry standard high frequency reciprocating rig (HFRR)
method. Also, the analyzed properties of the emulsified fuel with different
amount of percentage of water must be compared with the crude WPO to know
which emulsified fuel gives the best performance.

4
1.5 Significance of Study

This study’s finding will redound to society’s benefit, considering waste plastic
oil (WPO) emits lower CO and CO2 compared to commercial diesel. Thus,
WPO can reduced the enormous amount of plastic waste in the landfill since
mostly people in Malaysia use non-degradable plastic bag. Moreover, WPO
can be alternative source of energy. The technology can lessen the demand
for extracting, transporting, and burning fossil fuels while enhancing the energy
security of a community. Keep in mind that the upstream, middle, and
downstream activities of the petroleum business are energy intensive.

Besides, the mixture of water and WPO can provide low cost, low viscosity,
and low pollution. Moreover, this study will supply a water-in-oil emulsion fuel
that can reduce the emissions of pollutants into the exhaust of big combustion
engines, including those used in vehicles, and is stable for a long time.
Therefore, this study proposes a method for preparing a water-in-oil emulsion
fuel product where the water is dispersed in dispersed phases that are
effectively distributed uniformly throughout the oil dispersion medium.

5
 CHAPTER 2: LITERATURE REVIEW

2.1 Waste Plastic Oil

Waste Plastic Oil (WPO) is a different source of renewable energy that can be
used in place of fuel in diesel engine, boilers, cement factory, and steel mill
since WPO has physical properties and a carbon chain characteristic that is
similar to diesel fuel (Arjharn et al., 2022). WPO is well-known for its low cost
and low emissions of carbon compared to fossil fuels (Pahl, 2020). Also,
considering plastic waste is not biodegradable, producing WPO can reduce
the amount of plastic waste in landfill.

Therefore, six different types of plastics, including Polyethylene Terephthalate

(PET), High-Density Polyethylene (HDPE), Polyvinyl Chloride (PVC), Low-
Density Polyethylene (LDPE), Polypropylene (PP), and Polystyrene (PS), are
the most commonly used in the production of WPO.

2.1.1 Polyethylene terephthalate

PET plastics are mostly used for food product packaging, including bottles for
fruit juice, mineral water, soft drink, and other beverages. PET plastics are
used to make electrical insulation, printing sheets, magnetic tapes, X-ray films,
and various photographic films, among other things (Fakhrhoseini &
Dastanian, 2013). Due to their difficult disposal, the applications of PET
polymers result in a significant amount of plastic trash that threatens the
environment. The most effective way to cut down on PET plastic waste right
now is recycling. The rapid accumulation of PET plastics due to massive
container use requires repeated collection schedules, which raises the cost of
transportation (Vijayakumar & Sebastian, 2018). In previous research, the
gaseous product obtained from the production of liquid oil from PET was 76.9
wt.% and the liquid oil was 23.1 wt.% (Çepelioǧullar & Pütün, 2013). The
pyrolysis process was used to produce the liquid oil. The pyrolysis oil has an
6
acidic feature that makes it unfavourable to use in combustion engines since
it reduces the quality of the fuel (Wan Ho, 2015).

2.1.2 High-density polyethylene

HDPE is a lengthy linear polymer chain with excellent strength characteristics.

High degree of crystallinity and limited branching are characteristics that
contribute to the strength. HDPE is used in a wide variety of applications. It is
frequently used to make toys, milk bottles, detergent bottles, oil containers,
and a variety of other products. It is the third-largest form of plastic found in
Municipal Solid Waste (MSW) (Muller-Hagedorn H., 2005). Data from the
pyrolysis process in (Ahmad et al., 2015) shows 80.88 weight percent liquid,
with the whole conversion occurring at a temperature of 350°C. At 300°C, a
large amount of solid residue (33.05 wt.%) was produced. However, in the
pyrolysis of HDPE at 550ºC, the yield of liquid oil was 84.7 weight percent,
while the yield of gaseous product was determined to be 16.3 weight percent
(Marcilla et al., 2009). These results demonstrated that HDPE could produce
more liquid oil at higher temperatures. Unfortunately, a process that reaches a
temperature above HDPE's maximum thermal degradation point will likely yield
less liquid oil and more gaseous products. This conclusion was supported by
an experiment on the pyrolysis of HDPE at 650°C conducted by (Mastral et al.,
2002).

2.1.3 Polyvinyl chloride

PVC, which is made from a mixture of chlorine (57%) and carbon (43%) and
is unusual from other thermoplastics such as polyethylene, polystyrene, and
polypropylene (Federation, 2015). PVC has a high fire resistance and is suited
for electrical insulation since of its chlorine content. Due to the hydrogen
chloride (HCl) fumes that are generated when heated at high temperatures,
almost no work is done on PVC pyrolysis (Vijayakumar & Sebastian, 2018). By
pyrolyzing PVC at temperatures between 220 and 520°C, (Miranda et al.,
2001) produced liquid oil with a range of 0.45 weight percent to 12.79 weight
percent. Thus, the experiment also produced 58.2 wt.% of HCl.

7
2.1.4 Low-density polyethylene

LDPE has enough hardness and tensile strength. This occurs as a result of
LDPE's weaker intermolecular force. LDPE has more branching compared to
HDPE. The second-largest plastic waste in MSW is LDPE, following PP (López
et al., 2011). 95 wt.% of liquid oil was produced from the pyrolysis of LDPE at
550ºC in (Bagri & Williams, 2002), compared to 93.1 wt.% of liquid oil produced
from the identical experiment at 500ºC conducted in (López et al., 2011). The
data resulted from these two experiments show that higher temperature will
yield higher amount of liquid oil.

2.1.5 Polypropylene

PP has high chemical and heat resistant qualities. It is a linear hydrocarbon

chain-containing saturated polymer. Thus, it does not melt at the temperature
lower than 160ºC. PP is preferred by the plastics sector because of its high
rigidity and hardness. PP's density is lower than that of HDPE's. It contributes
the highest amount of plastics in MSW (Federation, 2015). The diverse
applications of PP include the manufacture of flowerpots, office folders,
automobile bumpers, buckets, carpets, various pieces of furniture, storage
boxes, etc. In order to optimize the yield of liquid oil, many researchers have
examined the pyrolysis of PP by varying the parameters (Vijayakumar &
Sebastian, 2018). At a temperature between 250 and 400°C, an experiment
on PP pyrolysis was carried out in (Ahmad et al., 2015). According to the
results of the research, 300°C was the temperature at which 69.82 weight
percent of liquid oil was produced. Therefore, PP was conducted to pyrolysis
in a research by (Fakhrhoseini & Dastanian, 2013) at 500 °C, yielding 82.12
wt.% of liquid. These two experiments shown an increase in the liquid yield
with the increasing of the temperature.

8
2.1.6 Polystyrene

PS is a polymer made of styrene monomers and is produced from a liquid

petrochemical. It contains compounds with lengthy hydrocarbon chains in
which each carbon atom has a phenyl group. Although it is a colourless
substance, it can be coloured using the right colourants. PS is used in many
different industries, including food packaging, electronics, construction,
medical, appliances, toys, and many more thanks to its reasonable durability,
strength, and lightness. Large amounts of waste are accumulating due to the
wider range of applications. Since only glasses, papers, cans, and other light
plastics are accepted in the recycling bins, PS cannot be included in the
roadside recycling programme. People will throw away the foam food
packaging in the regular trash rather than the plastics recycling bin. Therefore,
recycling PS presents a challenge. Pyrolysis is the only technique that can
recover PS waste and turn it into high-quality liquid oil. There are several
researchers who have studied into PS pyrolysis (Vijayakumar & Sebastian,
2018). In the experiment by (Onwudili et al., 2009), the oil yield produced was
around 97.0 wt.% at a temperature of 425°C. In the next experiment of the
pyrolysis of PS that was conducted in (Liu et al., 2000), 98.7 wt.% of liquid oil
was achieved at a temperature of 600°C, and the liquid oil production was
similarly high at lower temperatures of about 450°C.

2.2 Emulsions

2.2.1 Definitions of emulsions

An emulsion is a mixture of two or more liquids that are normally incompatible

but adopt on a macroscopic homogenous and microscopic heterogeneous
appearance under certain transformation processes. One liquid is mixed with
another to form an emulsion (Filippini et al., 2022). Also, emulsions are
colloidal dispersions that contain dispersed droplets with a mean diameter
typically within 0.1 and 100 µm (Ho et al., 2022). Three different classifications
of emulsions that can be identified are oil-in-water (O/W), water-in-oil (W/O),
and oil-in-oil (O/O) (Hayn et al., 2009).

9
2.2.2 Types of emulsions

2.2.2.1 O/W emulsions

O/W emulsions consists of oil droplets in a continuous aqueous phase as a

dispersion phase such as milk, mayonnaise, and vinaigrette. Thus, O/W
emulsions that also known as a direct emulsion are typically thought of as
thermodynamically unstable systems since the mixing of the aqueous and oil
phases produces interfacial tension and new surfaces, which increases the
energy of the system and lipophilic actives are delivered via these emulsions
(Li & Xiang, 2019).

2.2.2.2 W/O emulsions

Then, W/O emulsions are made up of an aqueous phase that is dispersed into
a continuous oil phase in the form of tiny droplets. Studying the stability of W/O
emulsions is important for production, control, and the invention of new
products. These emulsions are used in a variety of goods, such as butter,
margarine, and crude petroleum oil. They are also hugely beneficial in
products meant for those with dry or sensitive skin (Shechter, 2018).

2.2.2.3 O/O emulsions

Therefore, O/O emulsion is used when two organic liquids are emulsified within
one another and O/O emulsions in which both phases are completely non-
polar are rather extremely rare (Min et al., 2017). Three-phase aqueous
emulsions made from stabilised O/O emulsions in which one of the two oil
phases is silicone oil and the other is an organic oil like mineral oil or castor oil
are also used in products for personal care (I. Z. Lin et al., 2001).

10
2.2.3 Emulsion Instability

Emulsion stability refers to an emulsion's ability to endure changes in its

properties over time; the more stable an emulsion is, the more slowly its
properties change. Numerous different kinds of physical and chemical
processes can cause an emulsion to become unstable. In contrast to chemical
instability, which affects the type of molecules present, physical instability
causes changes to the spatial distribution or structural organisation of the
molecules (McClements, 2008). The examples of physical instabilities are:

• Creaming
• Flocculation
• Sedimentation
• Coalescence
• Phase inversion
• Ostwald ripening

Figure 2.1 Mechanism of Emulsion Destabilization (McClements, 2004)

11
2.2.3.1 Creaming and sedimentation

Gravitational separation is the term used to describe processes like

sedimentation and creaming that occur as a result of gravity. These unstable
emulsion forms are frequently encountered. Creaming or sedimentation may
take place, depending on the relative densities of the scattered and continuous
phases. If the dispersed phase's density is lower than the continuous phase's,
the dispersed phase's droplets will rise upward and separate from the
continuous phase, forming a new layer on top of the continuous phase.
Creaming is the phrase used to describe this phenomenon. However, when
the density of the dispersed phase is greater than that of the continuous phase,
droplets are forced to travel downward and form a layer at the bottom of the
continuous phase, which results in sedimentation. As a result, creaming
occurs more frequently in O/W emulsions (Pathak, 2017).

Both creaming and sedimentation follow Stokes' law, and their rates are stated
in terms of velocity:

2𝑔𝑟 2 (𝜌𝑤 − 𝜌𝑜 )
𝑣=
9𝜂𝑤

Where:

𝑣 = Velocity of droplet

𝜌𝑤 = Density of water phase

𝜌𝑜 = Density of oil phase

𝑟 = Radius of the droplet

𝜂𝑤 = Viscosity of water phase

𝑔 = Acceleration due to gravity

According to Stokes' law, the density difference between the two phases,
droplet size, and continuous phase viscosity can all be reduced to decrease
creaming or sedimentation. In general, an emulsion can be considered stable
at low creaming velocities which at the value of 0.1 m/s (Gad, 2010). Therefore,
the gravitational separation between tiny droplets in emulsions can be
reduced. Due to the dominance of Brownian motion, colloidal dispersion to

12
creaming and sedimentation increases dramatically for particles smaller than
90 nm (McClements, 2012).

2.2.3.2 Flocculation and coalescence

Coalescence is the process through which smaller droplets collide and

combine to form larger droplets. This causes the average droplet size to
decrease with time, which in turn causes the stability of the emulsion to
decrease (Maphosa & Jideani, 2018).

Then, flocculation is the separation of colloids or droplets into floc or flakes,

either naturally or as a result of the addition of a reactive agent. Agglomeration
or aggregation are other terms for it (Pathak, 2017). Emulsion flocculation is
caused by van der Waals attraction, which occurs in all dispersion systems. In
fact, the distance between droplets at which Van der Waals force exists is
inversely proportional to the distance (Tweeten & Molloy, 1982). Depending on
the use and functionality of the final product, droplet flocculation in emulsions
can be either beneficial or undesirable. Flocculation is necessary to produce
the desired rheological behaviour, appearance, and texture (Walstra, 2002).

Furthermore, flocs in higher volume fractions can restrict separation by

creating a three-dimensional (3D) network. In diluted emulsions, flocculation
can generate creaming due to the increased droplet effective diameter. Fast
flocculation is connected to stronger attractive forces and a low volume fraction
of the dispersed phase, resulted in an open packing of flocs such as a branch
network that trap a significant amount of the continuous phase. Slow
flocculation, on the other hand, has weaker attractive forces and forms
compact flocs that do not completely enclose continuous phase due to their
compact packing (Romero-peña, 2021).

13
 Figure 2.2 Types of Floc Produced by Droplets and Characterized by An
Increase in Effective Size (Romero-peña, 2021)

2.2.3.3 Phase inversion

Phase inversion is a term used to describe a phenomenon in which an agitated

oil in water emulsion transforms into a water in oil and vice versa. Production
of cosmetics, pharmaceuticals such as vesicles for drug delivery, food, and
detergents all use phase inversion emulsification extensively (Preziosi et al.,
2013).

The phase inversion pathways have been classified as catastrophic or

transitional. The former is a phrase (Salager et al., 1979) used to refer to
emulsion inversion achieved by varying the water/oil ratio. This is also referred
to as phase inversion composition (PIC) and emulsion inversion point (EIP).
(Dickinson, 1982) used the term catastrophic after making assumptions that
the emulsion phase inversion may be described by catastrophe theory.
Despite all efforts, catastrophe theory is unable to serve as a predictive model
and can only accurately predict certain qualitative characteristics of
catastrophic phase inversion. This is because there is not a kinetics coupled
thermodynamic approach, only a thermodynamic approach. According to
transitional phase inversion, the inversion is caused by a change in the
surfactant affinity between the two phases, such as non-ionic surfactants
becoming more lipophilic when heated (Dickinson, 1982).

14
However, considering phase inversion's wide applications and in-depth study,
uncertainty remains about how it operates. The three primary areas of phase
behaviour, interfacial characteristics, and flow-induced morphological
changes, such as droplet breakup and coalescence, can be related to the main
techniques for modelling phase inversion in the literature. Most research
focuses on one of these categories at a time, and it is currently unclear how
these two factors interact (Perazzo et al., 2015).

2.2.3.4 Ostwald ripening

Ostwald Ripening (OR) is the degradation and deposition of smaller particles

or droplets onto larger particles or droplets to get to a state where the surface-
to-area ratio is reduced, which is more thermodynamically stable. The
differential in solubility between small and large particles functions as the
driving force for Ostwald ripening (Tadros, 2013). OR happens because
molecules on a particle's surface are less stable energetically than those
inside. As a result, the unstable surface molecules often dissolve, slowly
reducing the particle and increasing the amount of free molecules in solution.
These free molecules will redeposit on the larger particles when the fluid is
supersaturated with the molecules of the shrinking particles. Thus, while large
particles continue to grow in size, small particles shrink in size until they are
completely gone. The mean diameter of a particle size distribution (PSD) will
be greater as a result of these particles' shrinking and growing. Thus, OR is an
irreversible destabilisation mechanism and frequently occurring in water-in-oil
emulsions where oil molecules will diffuse through the aqueous phase and join
larger oil droplets (Entegris, 2022).

Figure 2.3 Ostwald Ripening

15
2.3 Processes To Emulsify the Emulsions

Emulsification can be done using a variety of agitation techniques, such as

mechanical agitation and ultrasound agitation (Jafari et al., 2008). Mechanical
emulsification is widely used in both laboratory and industrial applications,
while ultrasound emulsification systems are mostly used in laboratories (C. Y.
Lin & Chen, 2008).

2.3.1 Mechanical agitation

Agitation is the mechanical action of causing a fluid to circulate or flow in

another pattern inside a container. Based on the experiment that conducted
by (Shekar et al., 2011), the composite solution was then mechanically
agitated by placing the agitator in the centre of the water-oil interface. Then, A
good, white emulsion is produced by properly mixing the phases. Therefore,
the research reported that compared to mechanical agitation, the ultrasound
technique produces emulsions that are more stable.

2.3.2 Ultrasonication technique

Emulsion preparation by ultrasonic irradiations is an efficient method for

reducing the mean droplet diameter size (MDDS) and is suitable for tiny test
benches. The most essential parameters for ultrasonication emulsification are
frequency, ultrasonication time, and radiation power (Maali & Mosavian, 2013).
Microbubbles contract and expand as a result of the compressive and tensile
stress that ultrasonic waves in the liquid medium produce. Acoustic cavitation,
or sudden bubble collapse, causes an increase in the power intensity of the
waves (Kwan et al., 2015). Following previous research, the beginning of a
breakup is at the cavitation position on an oil droplet, where there is a reported
3000 K temperature rise and 6 GPa impact wave occurrence at a moment with
a period of microseconds (Kanthale et al., 2013). The cavitation process is as
shown as in the figure below.

16
 Figure 2.4 Cavitation Process (Xu et al., 2015)

Ultrasonic waves have varied effects in various media (Gallego-Juarez, 2010).

In solid materials, such as metals, ultrasonic irradiation creates severe
phenomena include acoustic softening, heat generation, and a reduction in
contact friction, either at the nanoscale between two tiny metal grains or at the
macroscale when two surfaces rub against one another (Sarvi Hampa et al.,
2015). However, in liquids, ultrasonic irradiation produces a variety of crucial
phenomena, including cavitation, which is a cloud of high-pressure, high-
temperature bubbles (Abdullah et al., 2012). During ultrasonication, the liquid
medium underneath the oscillating probe is subjected to abrupt variations in
pressure and force, causing the liquid to rupture and form cavities or bubbles.
Thus, the cavitation bubbles grow during the low-pressure expansion half-
cycles of ultrasonic waves after the nucleation (Ashokkumar, 2011).

17
2.4 Performance of Waste Plastic Oil Emulsion

2.4.1 Viscosity

An emulsion's viscosity, which is determined by the correlation between stress

and shear rate, is directly proportional to the continuous phase's viscosity.
Typically, highly viscous oils produce more stable emulsions. These oils make
treating emulsions challenging because they reduced the movement of the
droplets and slowdown coalescence. The most important factor that influences
an emulsion's viscosity is its volume percent of the dispersed phase. The
internal circulation is decreased, and emulsion viscosity increases with an
increase in the volume fraction of the dispersed phase (Goual, 2012). This
research focused on a water-in-oil emulsion, where water is the dispersed
phase that is distribute into the continuous phase, which is oil.

Emulsions only have shear rate effects on viscosity when they have non-
Newtonian fluid characteristics. As a result, the shear rate has no effect on the
emulsion's viscosity when the concentration of the dispersed phase is low, and
the emulsion shows the characteristics of a Newtonian fluid. When the
dispersed phase concentration is high, the emulsions have pseudoplastic fluid
properties that are non-Newtonian, and the apparent viscosity decreases
dramatically as the shear rates increase (Kokal, 2005).

As the amount of water in a solution increases, so do the droplet-droplet

interactions and water-oil interfacial areas. Thus, the viscosity of the emulsion
also increases. Therefore, the impact of this phenomena influences the
amount that the interfacial viscosity has increased (Juntarasakul & Maneeintr,
2018).

18
2.4.2 Exhaust emission

The following observations are a detailed description of how directly emulsion

fuel affects pollutant formation.

2.4.2.1 Nitrogen oxide (NOX)

High latent heat absorption by water particles during combustion will lower the
local high temperature, resulting in a decrease in NOx. The reduction of NOx
will be caused by the high latent heat absorption of water particles during
combustion, which will lower the local high temperature. According to every
research, fuel with a water-in-oil emulsion greatly reduces the emission of NOx
(Vellaiyan & Amirthagadeswaran, 2016a). In comparison to (Attia &
Kulchitskiy, 2014) and (Park et al., 2012), who observed 25% and 20%
reductions in NOx in their investigations, (Vellaiyan & Amirthagadeswaran,
2016b) recorded a 35% reduction in NOx. Low levels of NOx were produced
due to the heat sink effect of emulsion fuel, which also decreased the
combustion temperature. The addition of water in emulsion fuel causes an
increase in hydroxyl (OH) content, which reduces NOx (Farfaletti et al., 2005).
Therefore, with 10% water content in the emulsion, NOx emissions are
reduced by 20%. The lower peak flame temperature during combustion when
using W/D emulsion fuel causes a decrease of NOx (Samec et al., 2002).

2.4.2.2 Soot and particulate matter (PM)

A more efficient combustion is shown by less soot and PM production. The

majority of research found that as water concentrations increase, soot and PM
levels decrease (Vellaiyan & Amirthagadeswaran, 2016a). (Ochoterena et al.,
2010) observed that using W/O emulsion fuel resulted in an 81% reduction in
soot emission. (Fu et al., 2002) discovered a decrease in soot and PM because
of improved mixing and increased atomization caused by the emulsion fuel's
micro-explosion behaviour. It is noted that there is a tendency for PM reduction
in emulsion fuel based on the production behaviour of light hydrocarbons
(LHCs) and polycyclic aromatic hydrocarbons (PAHs). The sulphur level of the
emulsion fuel has a profound impact on the development of PM emission,

19
according to (Noge et al., 2015). The other factors that lead to a low amount
of soot and PM in emulsion fuel are a lower flame temperature, quick water
evaporation, a decrease in the pyrolysis reaction, and increased oxidation.

2.4.2.3 Carbon monoxide (CO), carbon dioxide (CO2) and un-burnt

hydrocarbon

The main factors that lead to CO and unburnt HC in diesel engines include
incomplete combustion, a lack of homogeneity, and slow soot burning. Various
research noted an increase in CO and HC emissions while using W/D emulsion
fuel because of the lower combustion temperature required to completely
convert CO into CO2 (Subramanian, 2011). Then, the higher amount of OH
contribution in emulsion fuel improves the oxidation of carbon to CO, which
leads to an increase in CO and HC levels. Higher levels of CO and HC
emission from diesel engines are also a result of ignition delay extending and
low flame temperature of emulsion fuel (Koc & Abdullah, 2013). Moreover,
another study recorded that the CO2 emissions from emulsion fuel increased
as water concentrations increased (Hasannuddin et al., 2016). However, (Attia
& Kulchitskiy, 2014) stated that complete combustion can result from the
reduction of these emissions brought on by micro-explosion occurrences.

The findings demonstrated that due to the complexity of combustion analysis,

there is inconsistency in the W/O emulsion fuel domain in terms of specific fuel
consumption (SFC), brake power (BP), hydrocarbon (HC), and carbon
monoxide (CO) emissions (Vellaiyan & Amirthagadeswaran, 2016a).

2.4.3 Flash point

Flash point is the lowest temperature at which a liquid (often a petroleum

product) will produce a vapour in the air at its surface that will "flash," or rapidly
ignite, when in exposure with an open flame. Thus, the flash point value is a
crucial property for figuring out a fuel's flammability as well as critical
characteristics as a safety indication for storage and transportation of a fuel. A
liquid's flammability or combustibility can generally be determined by the flash
point. There is not enough vapour present below the flash point to support

20
combustion. The liquid will generate enough vapour to enable combustion at
a temperature that is slightly over the flash point (Curley, 2022).

In addition, the flash point of emulsion W/O increases as the percentage of

water in the WPO increases. The data obtained from a previous study
conducted by (Rosid et al., 2020) can be used as support for this claim.
According to the study, the flash point is 70 °C when there is 50% water in the
WPO.

2.4.4 Waste plastic oil emulsion as a lubricant

Lubricity is the ability of a lubricant to reduce friction on surfaces that are

moved in relation to one another under load. Typically, boundary lubrication
conditions are attempted to be created during experiments to assess the
lubricity of diesel fuel (Jaaskelainen, 2008). Next, the lubrication oil's quality
must remain high because it ensures safe operation of diesel engines,
provides mechanical strength, maintains engine cleanliness, and minimizes
friction. Water-in-oil emulsion lubricants are stable, non-corrosive, and wear-
resistant fluids with good lubricating qualities that are particularly helpful for
fast diesel engines and as fire-resistant hydraulic fluids (Kingsland, 1948).

An important parameter needed to determine a lubricant's internal flow

resistance is its viscosity. It represents the thickness or thinness of a lubricant,
to put it simply (Jaaskelainen, 2008). Thus, a liquid's thickness and resistance
to flow increase with increasing viscosity (Smooth-On, 2023).

The main objective of lubricants is to reduce friction; therefore, viscosity has a

major impact on performance. The strength and durability of the protective
coating formed between moving parts is based on the lubricant's thickness. In
the conclusion, this is what keeps metal from touching metal and reduces
friction. Gears, cylinders, bearings, and other moving parts frequently use
lubricants to decrease heat generation. Then, the ability of a lubricant to reduce
heat and maintain a desirable operating temperature can be influenced by its
viscosity. Also, the effectiveness of a machine can be impacted by the
lubricant's thickness and internal flow resistance. For instance, an emulsion
that is too thin might not be able to provide a barrier that can reduce friction

21
between moving parts. This could speed up wear, raise the machine's
operating temperature, and let contaminated particles into the system.
Similarly, if the emulsion is unusually thick, it could produce unneeded
resistance and make the machine work harder. This might lead to a rise in
energy use and the production of excessive heat (Jaaskelainen, 2008). In
general, the water content must be kept between 35 and 45 percent since
above that point, the fluids start to lose their ability to resist fire. The anti-wear
properties of the fluid will be decreased if the water content is increased above
45% (Corporation, 2023).

22
 CHAPTER 3: METHODOLOGY

3.1 Introduction

The primary goal of this research is to evaluate the performance of waste

plastic oil (WPO) by evaluating its properties and compare the properties of
the emulsified WPO with the crude WPO. WPO that will be used in this
research was produced from the plastic waste that known as low density
polyethylene (LDPE) by using depolymerization process.

Moreover, the properties of the emulsified WPO can be analyzed by using gas
analyzer, Brookfield viscometer model LVDV2T, Pensky-Martens, and high
frequency reciprocating rig (HFRR).

In summary, this methodology is consisting of three major parts:

- Various amounts of water will be added to the crude WPO.

- Emulsification of water-in-oil by using ultrasonication technology.

- Analyzed the properties of emulsified WPO which are the emission of

carbon dioxide and carbon monoxide, viscosity, flash point, and lubricity

and comparing the resulted properties with the crude WPO.

23
3.2 Materials and Apparatus

Materials and apparatus that will be used in this study to carry out the
methodology are as shown in Table 3.1.

Table 3.1 Materials and Apparatus that will be used in methodology

Materials Apparatus

1. Crude WPO from Syngas Sdn. Bhd. 1. Ultrasonicator VCX 750

2. Deionized water 2. 250 mL beaker

3. Gas analyzer

4. Moisture analyzer

5. Measuring cylinder

6. Stopwatch

7. Viscosity model LVDV2T

8. Pensky-Martens

9. HFRR

10. Measuring cylinder

11. Stopwatch

12. Moisture analyzer

24
3.3 Addition Of Deionized Water to The Crude WPO

Experimental procedure for this research begins with checking the moisture
content in the crude waste plastic oil (WPO) that will be given by using moisture
analyzer to make sure there is no water content in the crude oil.

First and foremost, 90% v/v (90 mL) crude WPO and 10% v/v (20 mL)
deionized water must be added in a 250 mL beaker to make water-in-oil (W/O)
emulsions. Before adding them to the 250 mL beaker, the volume of the
deionized water and crude WPO will be measured using a measuring cylinder.
Thus, each sample consists of varying percentage of water, ranging from 10%
v/v to 50% v/v with an additional 10% v/v of deionized water. It will be
necessary to prepare 20 samples of W/O emulsions this methodology. The
amount of samples that need to be prepared in this methodology are according
to Table 3.2 below.

Table 3.2 Amount of Samples that need to be prepared

Amount of Samples Deionized Water to Crude WPO ratio (%)

4 10 : 90

4 20 : 80

4 30 : 70

4 40 : 60

4 50 : 50

25
3.4 Emulsification of W/O Using Ultrasonication Technology

Then, the samples of W/O emulsions must be emulsified by using VCX 750
Sonicator (Newtown, CT, USA) ultrasound equipment as shown in Figure 3.1
below.

Thus, a 13 mm probe with threaded end and replaceable tip must be attached
to the ultrasound equipment. Next, the 250 mL beaker that contains the
emulsions sample must be placed underneath the probe and make sure the
probe is within the sample before starting the emulsification. Moreover, the
ultrasound equipment resonates at the value of frequency of 20 kHz and the
probe will emulsify the W/O sample until the mixture is completely being mixed.
Different time needed to emulsify the W/O for each sample have to be recorded
and measured by using a stopwatch.

Figure 3.1 Ultrasound equipment used to emulsify W/O emulsions

Figure 3.2 Droplet breakup during ultrasonic emulsification (Sarkar,2023)

26
3.5 Properties of Emulsified Fuel

Gas analyzer will be used to determine the amount of emitted carbon

monoxide and carbon dioxide by incinerate the emulsified samples in a
chamber attached to the gas analyzer.

Next, the viscosity of the crude WPO and emulsified samples can be measured
by using Brookfield viscometer model LVDV2T with spindle number 40Z and
52Z. Experimentally, flash points are obtained by heating a liquid in a cup and
then putting a little flame just over the surface of the liquid. The flash point is
the temperature at which a flash or ignition occurs and the equipment that will
be used to determine the flash point of the samples is Pensky-Martens.

Therefore, tests of lubricating properties will be done using crude WPO and
emulsified fuel samples that use the industry standard high frequency
reciprocating rig (HFRR) method. Similar to the previous research, lubrication
experiments were conducted under conditions of continuously increasing load
(A Jaworski et al., 2013). During the test run, the spindle rotated at 500 rpm
while the load build-up speed was 409 N/s. At the start of the test run, the fuel
sample's initial temperature was 64ºC, and it was at this temperature that
HFRR lubricity measurements were taken.

Moreover, the analyzed properties of the emulsified samples must be

compared with the properties of the crude WPO to know which one is the most
compatible with other petroleum products.

Figure 3.3 The four-ball machine T-02U used to determine the lubricity tests
(A Jaworski et al., 2021)

27
3.6 Expected Results

From this study, viscosity of the emulsion fuel will be increased as the amount
of water in the fuel increase (Engineering, 2015). Numerous researchers claim
that adding water tends to lower the cetane number, which ultimately causes
the emulsified fuel's ignition to take longer to ignite (Sadhik Basha & Anand,
2014). Thus, as the water percentage in the emulsion increases, the emission
of carbon monoxide increases. Moreover, the flash point of the emulsified fuels
decreases as the water percentage increases (Kapadia et al., 2019).

3.7 Cost Estimation

For this project, cost for the raw materials which is crude waste plastic oil
(WPO) will not be included in the cost estimation since the WPO will be
provided by Syngas Sdn. Bhd. However, five samples need to be tested at the
outside of the university’s laboratory because the equipment is not available to
use. The price for one emulsified fuel samples that need to be analyzed with
the gas analyzer at University Malaysia Pahang (UMP) is as shown in the table
below:

Table 3.3 Estimated cost to carry out this methodology

COST PER
EQUIPMENT ANALYSIS TOTAL (RM)
SAMPLE (RM)

The amount of carbon

Gas analyzer monoxide and carbon 120.00 600.00
dioxide emitted

28
3.8 Gantt Chart

29
REFERENCES

Abdullah, A., Malaki, M., & Baghizadeh, E. (2012). On the impact of

ultrasonic cavitation bubbles. Proceedings of the Institution of
Mechanical Engineers, Part C: Journal of Mechanical Engineering
Science, 226(3), 681–694. https://doi.org/10.1177/0954406211414769

Ahmad, I., Ismail Khan, M., Khan, H., Ishaq, M., Tariq, R., Gul, K., & Ahmad,
W. (2015). Pyrolysis study of polypropylene and polyethylene into
premium oil products. International Journal of Green Energy, 12(7), 663–
671. https://doi.org/10.1080/15435075.2014.880146

Arjharn, W., Liplap, P., Maithomklang, S., Thammakul, K., Chuepeng, S., &
Sukjit, E. (2022). Distilled Waste Plastic Oil as Fuel for a Diesel Engine:
Fuel Production, Combustion Characteristics, and Exhaust Gas
Emissions. ACS Omega, 7(11), 9720–9729.
https://doi.org/10.1021/acsomega.1c07257

Ashokkumar, M. (2011). The characterization of acoustic cavitation bubbles -

An overview. Ultrasonics Sonochemistry, 18(4), 864–872.
https://doi.org/10.1016/j.ultsonch.2010.11.016

Attia, A. M. A., & Kulchitskiy, A. R. (2014). Influence of the structure of water-

in-fuel emulsion on diesel engine performance. Fuel, 116, 703–708.
https://doi.org/10.1016/j.fuel.2013.08.057

Bagri, R., & Williams, P. T. (2002). Catalytic pyrolysis of polyethylene.

Journal of Analytical and Applied Pyrolysis, 63(1), 29–41.
https://doi.org/10.1016/S0165-2370(01)00139-5

Çepelioǧullar, Ö., & Pütün, A. E. (2013). Thermal and kinetic behaviors of

biomass and plastic wastes in co-pyrolysis. Energy Conversion and
Management, 75, 263–270.
https://doi.org/10.1016/j.enconman.2013.06.036

Chandran, M., Tamilkolundu, S., & Murugesan, C. (2018). Investigation of the

performance, combustion parameters, and emissions analysis on DI
engine using two staged distilled waste plastic Oil-Diesel Blends.

30
 Thermal Science, 22(3), 1469–1480.
https://doi.org/10.2298/tsci170501067c

Corporation, N. (2023). Advice for Using Water-in-Oil Emulsions.

https://www.machinerylubrication.com/Read/29232/water-in-oil

Curley, R. (2022). flash point | physics | Britannica.

https://www.britannica.com/science/flash-point

Dickinson, E. (1982). Thermodynamic aspects of emulsion phase inversion.

Journal of Colloid And Interface Science, 87(2), 416–423.
https://doi.org/10.1016/0021-9797(82)90338-1

Engineering, N. R. (2015). Effect of 20% Water Content on the Properties

(Cetane Number, Rheology and Stability) of Emulsion Fuel in
Comparison To the Commercial Diesel. International Journal of Current
Research.

Entegris. (2022). Unstable - Ostwald Ripening | Entegris.

https://www.entegris.com/en/home/resources/technical-
information/glossary/unstable.html

EPA. (2022). Learn About Impacts of Diesel Exhaust and the Diesel
Emissions Reduction Act (DERA) | US EPA.
https://www.epa.gov/dera/learn-about-impacts-diesel-exhaust-and-
diesel-emissions-reduction-act-dera

Fakhrhoseini, S. M., & Dastanian, M. (2013). Predicting pyrolysis products of

PE, PP, and PET using NRTL activity coefficient model. Journal of
Chemistry, 2013, 7–9. https://doi.org/10.1155/2013/487676

Farfaletti, A., Astorga, C., Martini, G., Manfredi, U., Mueller, A., Rey, M., De
Santi, G., Krasenbrink, A., & Larsen, B. R. (2005). Effect of water/fuel
emulsions and a cerium-based combustion improver additive on HD and
LD diesel exhaust emissions. Environmental Science and Technology,
39(17), 6792–6799. https://doi.org/10.1021/es048345v

Federation, B. P. (2015). Polyvinyl Chloride PVC.

https://www.bpf.co.uk/plastipedia/polymers/PVC.aspx

Filippini, B. B., Mullay, J. J., Sun, Y., & Totten, G. E. (2022). Emulsions.

31
 Handbook of Hydraulic Fluid Technology, Second Edition, 607–662.
https://doi.org/10.1533/9780857097910.175

Fu, W. B., Hou, L. Y., Wang, L., & Ma, F. H. (2002). A unified model for the
micro-explosion of emulsified droplets of oil and water. Fuel Processing
Technology, 79(2), 107–119. https://doi.org/10.1016/S0378-
3820(02)00106-6

Fulgencio-medrano, L., Garc, S., Asueta, A., Lopez-urionabarrenechea, A., &

Perez-martinez, B. B. (2022). Oil Production by Pyrolysis of Real Plastic
Waste.

Gad, S. C. (2010). Introduction: Drug Discovery in the 21 st Century .

Pharmaceutical Sciences Encyclopedia.
https://doi.org/10.1002/9780470571224.pse001

Gallego-Juarez, J. A. (2010). High-power ultrasonic processing: Recent

developments and prospective advances. Physics Procedia, 3(1), 35–
47. https://doi.org/10.1016/j.phpro.2010.01.006

Goual, L. (2012). Petroleum Asphaltenes. In Crude Oil Emulsions-

Composition Stability and Characterization.
https://doi.org/10.5772/35875

Hasannuddin, A. K., Wira, J. Y., Sarah, S., Wan Syaidatul Aqma, W. M. N.,
Abdul Hadi, A. R., Hirofumi, N., Aizam, S. A., Aiman, M. A. B.,
Watanabe, S., Ahmad, M. I., & Azrin, M. A. (2016). Performance,
emissions and lubricant oil analysis of diesel engine running on emulsion
fuel. Energy Conversion and Management, 117, 548–557.
https://doi.org/10.1016/j.enconman.2016.03.057

Hayn, M. H., Averch, T. D., & Jackman, S. V. (2009). Transperitoneal

laparoscopic radical and partial nephrectomy in patients with cirrhosis:
report of three cases. The Canadian Journal of Urology, 16(4), 4770–
4773.

Ho, T. M., Razzaghi, A., Ramachandran, A., & Mikkonen, K. S. (2022).

Emulsion characterization via microfluidic devices: A review on
interfacial tension and stability to coalescence. Advances in Colloid and

32
 Interface Science, 299(October 2021), 102541.
https://doi.org/10.1016/j.cis.2021.102541

Jaaskelainen, H. (2008). Fuel Property Testing: Lubricity.

https://dieselnet.com/tech/fuel_diesel_lubricity.php

Jafari, S. M., Assadpoor, E., He, Y., & Bhandari, B. (2008). Re-coalescence
of emulsion droplets during high-energy emulsification. Food
Hydrocolloids, 22(7), 1191–1202.
https://doi.org/10.1016/j.foodhyd.2007.09.006

Juntarasakul, O., & Maneeintr, K. (2018). Evaluation of stability and viscosity

measurement of emulsion from oil from production in northern oilfield in
Thailand. IOP Conference Series: Earth and Environmental Science,
140(1). https://doi.org/10.1088/1755-1315/140/1/012024

Kanthale, P. M., Brotchie, A., Grieser, F., & Ashokkumar, M. (2013).

Sonoluminescence quenching and cavitation bubble temperature
measurements in an ionic liquid. Ultrasonics Sonochemistry, 20(1), 47–
51. https://doi.org/10.1016/j.ultsonch.2012.05.011

Kapadia, H., Brahmbhatt, H., Dabhi, Y., & Chourasia, S. (2019). Investigation
of emulsion and effect on emission in CI engine by using diesel and bio-
diesel fuel: A review. Egyptian Journal of Petroleum, 28(4), 323–337.
https://doi.org/10.1016/j.ejpe.2019.06.004

Karami, H., Papari-Zare, S., Shanbedi, M., Eshghi, H., Dashtbozorg, A.,
Akbari, A., Mohammadian, E., Heidari, M., Sahin, A. Z., & Teng, C. B.
(2019). The thermophysical properties and the stability of nanofluids
containing carboxyl-functionalized graphene nano-platelets and multi-
walled carbon nanotubes. International Communications in Heat and
Mass Transfer, 108, 104302.
https://doi.org/10.1016/j.icheatmasstransfer.2019.104302

Kingsland, L. C. (1948). The United States Patent Office. Law and

Contemporary Problems, 13(2), 354. https://doi.org/10.2307/1190003

Koc, A. B., & Abdullah, M. (2013). Performance and NOx emissions of a

diesel engine fueled with biodiesel-diesel-water nanoemulsions. Fuel

33
 Processing Technology, 109(x), 70–77.
https://doi.org/10.1016/j.fuproc.2012.09.039

Kokal, S. (2005). Crude-oil emulsions: A state-of-the-art review. SPE

Production and Facilities, 20(1), 5–12. https://doi.org/10.2118/77497-pa

Kwan, J. J., Graham, S., Myers, R., Carlisle, R., Stride, E., & Coussios, C. C.
(2015). Ultrasound-induced inertial cavitation from gas-stabilizing
nanoparticles. Physical Review E - Statistical, Nonlinear, and Soft Matter
Physics, 92(2), 1–5. https://doi.org/10.1103/PhysRevE.92.023019

Lavina, L. (2020). Transforming plastic waste into wealth.

https://www.clariant.com/en/Corporate/Blog/2020-Blog-Posts/10/Plastic-
waste-to-winter-diesel

Li, Y., & Xiang, D. (2019). Stability of oil-in-water emulsions performed by

ultrasound power or high-pressure homogenization. PLoS ONE, 14(3),
1–14. https://doi.org/10.1371/journal.pone.0213189

Lin, C. Y., & Chen, L. W. (2008). Comparison of fuel properties and emission
characteristics of two- and three-phase emulsions prepared by
ultrasonically vibrating and mechanically homogenizing emulsification
methods. Fuel, 87(10–11), 2154–2161.
https://doi.org/10.1016/j.fuel.2007.12.017

Lin, I. Z., Schulz, W. J., City, B., & Us, M. I. (2001). ( 12 ) United States
Patent. 1(12), 1–7.

Liu, Y., Qian, J., & Wang, J. (2000). Pyrolysis of polystyrene waste in a
fluidized-bed reactor to obtain styrene monomer and gasoline fraction.
Fuel Processing Technology, 63(1), 45–55.
https://doi.org/10.1016/S0378-3820(99)00066-1

López, A., De Marco, I., Caballero, B. M., Laresgoiti, M. F., & Adrados, A.
(2011). Dechlorination of fuels in pyrolysis of PVC containing plastic
wastes. Fuel Processing Technology, 92(2), 253–260.
https://doi.org/10.1016/j.fuproc.2010.05.008

Lu, G. W., & Gao, P. (2010). Emulsions and Microemulsions for Topical and
Transdermal Drug Delivery. In Handbook of Non-Invasive Drug Delivery

34
 Systems. https://doi.org/10.1016/b978-0-8155-2025-2.10003-4

Maali, A., & Mosavian, M. T. H. (2013). Preparation and Application of

Nanoemulsions in the Last Decade (2000-2010). Journal of Dispersion
Science and Technology, 34(1), 92–105.
https://doi.org/10.1080/01932691.2011.648498

Maphosa, Y., & Jideani, V. A. (2018). Factors Affecting the Stability of

Emulsions Stabilised by Biopolymers. Science and Technology Behind
Nanoemulsions. https://doi.org/10.5772/intechopen.75308

Marcilla, A., Beltrán, M. I., & Navarro, R. (2009). Thermal and catalytic
pyrolysis of polyethylene over HZSM5 and HUSY zeolites in a batch
reactor under dynamic conditions. Applied Catalysis B: Environmental,
86(1–2), 78–86. https://doi.org/10.1016/j.apcatb.2008.07.026

Mastral, F. J., Esperanza, E., Garciía, P., & Juste, M. (2002). Pyrolysis of
high-density polyethylene in a fluidised bed reactor. Influence of the
temperature and residence time. Journal of Analytical and Applied
Pyrolysis, 63(1), 1–15. https://doi.org/10.1016/S0165-2370(01)00137-1

McClements, D. J. (2008). Stability of Food Emulsions (2). University of

Massachusetts, 1, 1–37.
http://people.umass.edu/mcclemen/FoodEmulsions2008/Presentations(
PDF)/(7)Emulsion_Stability.pdf

McClements, D. J. (2012). Nanoemulsions versus microemulsions:

Terminology, differences, and similarities. Soft Matter, 8(6), 1719–1729.
https://doi.org/10.1039/c2sm06903b

Min, Y., Shin, S., Sun, H., Kim, H. S., Bang, J. S., Cho, G. H., Application, F.,
& Data, P. (2017). Oil-in-Oil Emulsion. 2(12), 1–8.

Miranda, R., Yang, J., Roy, C., & Vasile, C. (2001). Vacuum pyrolysis of
commingled plastics containing PVC. I. Kinetic study. Polymer
Degradation and Stability, 72(3), 469–491.
https://doi.org/10.1016/S0141-3910(01)00048-9

Muller-Hagedorn H., M. &. B. (2005). Feedstock recycling of plastics. In Third

International Symposium on Feedstock Recycling of Plastics and Other

35
 Innovative Plastics Recycling Techniques.

Noge, H., Kidoguchi, Y., Jazair Yahya, W., Imai, Y., & Tajima, K. (2015). An
investigation into the relationship between the formation of thermal
cracked components and PM reduction during diesel combustion using
water emulsified fuel. Journal of Thermal Science and Technology,
10(2), 1–11. https://doi.org/10.1299/jtst.2015jtst0024

Ochoterena, R., Lif, A., Nydén, M., Andersson, S., & Denbratt, I. (2010).
Optical studies of spray development and combustion of water-in-diesel
emulsion and microemulsion fuels. Fuel, 89(1), 122–132.
https://doi.org/10.1016/j.fuel.2009.06.039

Onwudili, J. A., Insura, N., & Williams, P. T. (2009). Composition of products

from the pyrolysis of polyethylene and polystyrene in a closed batch
reactor: Effects of temperature and residence time. Journal of Analytical
and Applied Pyrolysis, 86(2), 293–303.
https://doi.org/10.1016/j.jaap.2009.07.008

Padmanabhan, S., Joel, C., Joel, L., Reddy, O. Y., Harsha, K. G. D. S., &
Ganesan, S. (2021). Evaluation of Waste Plastic Pyrolysis Oil
Performance with Diethyl Ether Additive on Insulated Piston Diesel
Engine. Nature Environment and Pollution Technology, 20(5), 2079–
2086. https://doi.org/10.46488/NEPT.2021.V20I05.025

Pahl, C. (2020). Converting Plastic Waste to Fuel - Plug and Play Tech
Center. https://www.plugandplaytechcenter.com/resources/converting-
plastic-waste-fuel/

Park, J. K., Oh, J. M., Kim, H. I., Lee, C. H., & Lee, K. H. (2012). Combustion
characteristics of MDO and MDO emulsion in automotive diesel engine.
Transactions of the Korean Society of Mechanical Engineers, B, 36(9),
945–951. https://doi.org/10.3795/KSME-B.2012.36.9.945

Pathak, M. (2017). Nanoemulsions and Their Stability for Enhancing

Functional Properties of Food Ingredients. In Nanotechnology
Applications in Food: Flavor, Stability, Nutrition and Safety. Elsevier Inc.
https://doi.org/10.1016/B978-0-12-811942-6.00005-4

36
Perazzo, A., Preziosi, V., & Guido, S. (2015). Phase inversion emulsi fi
cation : Current understanding and applications. Advances in Colloid and
Interface Science, 1–19. https://doi.org/10.1016/j.cis.2015.01.001

Preziosi, V., Perazzo, A., Caserta, S., Tomaiuolo, G., & Guido, S. (2013).
Phase inversion emulsification. Chemical Engineering Transactions, 32,
1585–1590. https://doi.org/10.33032/CET1332265

Raigan, K. (2020). Scholarship @ Western Ultrasonic Techniques for

Characterizations of Oils and Their Emulsions and Monitoring Oil Layer
Depth of Spill.

Romero-peña, M. F. (2021). DEVELOPMENT OF STABLE LIQUID WATER-

IN-OIL EMULSIONS BY MODIFYING EMULSIFIER-AQUEOUS PHASE
INTERACTIONS A Thesis Submitted to the College of By. July.

Rosid, ., Sudarmanta, B., & Atmaja, L. (2020). Stability Behavior of Water-in-

Diesel Fuel Emulsion and Current Trends Engine Performance and
Emission. Senta 2018, 215–220.
https://doi.org/10.5220/0008549302150220

Sadhik Basha, J., & Anand, R. B. (2014). Performance, emission and

combustion characteristics of a diesel engine using Carbon Nanotubes
blended Jatropha Methyl Ester Emulsions. Alexandria Engineering
Journal, 53(2), 259–273. https://doi.org/10.1016/j.aej.2014.04.001

Salager, J. L., Morgan, J. C., Schechter, R. S., Wade, W. H., & Vasquez, E.
(1979). Optimum Formulation of Surfactant/Water/Oil Systems for
Minimum Interfacial Tension or Phase Behavior. Soc Pet Eng AIME J,
19(2), 107–115. https://doi.org/10.2118/7054-pa

Samec, N., Kegl, B., & Dibble, R. W. (2002). Numerical and experimental
study of water/oil emulsified fuel combustion in a diesel engine. Fuel,
81(16), 2035–2044. https://doi.org/10.1016/S0016-2361(02)00135-7

Sandhya, M., Ramasamy, D., Sudhakar, K., Kadirgama, K., & Harun, W. S.
W. (2021). Ultrasonication an intensifying tool for preparation of stable
nanofluids and study the time influence on distinct properties of
graphene nanofluids – A systematic overview. Ultrasonics

37
 Sonochemistry, 73, 105479.
https://doi.org/10.1016/j.ultsonch.2021.105479

Sarvi Hampa, P., Razfar, M. R., Malaki, M., & Maleki, A. (2015). The Role of
Dry Aero-acoustical Lubrication and Material Softening in Ultrasonically
Assisted Milling of Difficult-to-Cut AISI 304 Steels. Transactions of the
Indian Institute of Metals, 68(1), 43–49. https://doi.org/10.1007/s12666-
014-0429-0

Shechter, D. (2018). Oil-in-Water and Water-in-Oil Emulsions: What’s the

Difference? https://www.beei.com/blog/oil-in-water-and-water-in-oil-
emulsions-whats-the-difference-

Shekar, M. C., Chary, B. B., Srinivas, S., Kumar, B. R., Mahendrakar, M. D.,
& Varma, M. V. K. (2011). Effect of ultrasonication on stability of oil in
water emulsions. International Journal of Drug Delivery, 3(1), 133–140.
https://doi.org/10.5138/ijdd.2010.0975.0215.03063

Smooth-On. (2023). Viscosity Scale. https://www.smooth-

on.com/page/viscosity-scale/

Subramanian, K. A. (2011). A comparison of water-diesel emulsion and timed

injection of water into the intake manifold of a diesel engine for
simultaneous control of NO and smoke emissions. Energy Conversion
and Management, 52(2), 849–857.
https://doi.org/10.1016/j.enconman.2010.08.010

Tadros, T. (2013). Oscillatory Marangoni Convection ▶.

https://doi.org/10.1007/978-3-642-20665-8

Tweeten, K. A., & Molloy, G. R. (1982). Inhibition of messenger RNA

synthesis by 5,6-dichloro-1-β-d-ribofuranosylbenzimidazole without its
detectable accumulation in mouse T-lymphoma cells. In Archives of
Biochemistry and Biophysics (Vol. 217, Issue 1).
https://doi.org/10.1016/0003-9861(82)90509-4

Vellaiyan, S., & Amirthagadeswaran, K. S. (2016a). The role of water-in-

diesel emulsion and its additives on diesel engine performance and
emission levels: A retrospective review. Alexandria Engineering Journal,

38
 55(3), 2463–2472. https://doi.org/10.1016/j.aej.2016.07.021

Vellaiyan, S., & Amirthagadeswaran, K. S. (2016b). Zinc oxide incorporated

water-in-diesel emulsion fuel: Formulation, particle size measurement,
and emission characteristics assessment. Petroleum Science and
Technology, 34(2), 114–122.
https://doi.org/10.1080/10916466.2015.1122621

Vijayakumar, A., & Sebastian, J. (2018). Pyrolysis process to produce fuel

from different types of plastic - A review. IOP Conference Series:
Materials Science and Engineering, 396(1). https://doi.org/10.1088/1757-
899X/396/1/012062

Walstra, P. (2002). Physical Chemistry of Foods. In Physical Chemistry of

Foods. https://doi.org/10.1201/9780203910436

Wan Ho, D. M. (2015). Waste Plastics into Fuel Oil? https://www.i-

sis.org.uk/Waste_Plastics_into_Fuel_Oil.php

39