Fuel 257 (2019) 115944

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Microemulsion fuels for compression ignition engines: A review on engine T

performance and emission characteristics
Iyman Abrar, Ashok N. Bhaskarwar⁎
Department of Chemical Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India

ARTICLE INFO ABSTRACT

Keywords: Fossil fuels are currently the world’s primary source of energy. Their limited reserves and increasing emissions
Diesel have, however, generated an interest in the development of renewable and cleaner alternative sources of energy.
Microemulsions Compression ignition (CI) engine is an extensively used internal combustion engine, with a better fuel economy
Vegetable oils and efficiency as compared to spark ignition (SI) engine. Particulate matter (PM) and NOx emissions generated
Alcohols
from diesel fuel are serious environmental and health concerns, which also have led to an interest in the diesel
CI engine
alternatives. Most commonly used diesel alternatives are either uneconomical or require modifications in current
Emissions
engine and infrastructure. Microemulsification is a developing technique, which is economical and does not
require any changes in the current systems. In this review, we have focused our attention on diesel, vegetable oil,
and alcohol based microemulsion fuels as an alternative to diesel for the CI engines. While most of the micro-
emulsions have lower calorific values and higher fuel consumptions, the thermal efficiency is improved due to
the presence of water. Moreover, it helps in the simultaneous reduction of PM and NOx emissions. Considering
the trends in the costs of fossil fuels in recent past and present, microemulsions seem to be most promising,
cleaner, and powerful alternative to fossil fuels, such as gasoline, diesel and aviation fuels.

1. Introduction well [3]. Stringent environmental regulations are being enforced to

The compression ignition (CI) engines are more popular than spark
ignition (SI) engines due to their better fuel economy and efficiency. CI
engines run on diesel fuel, which is obtained from the distillation of
crude oil, in the temperature range of 180–360 °C. It consists of ap-
proximately 75% of saturated hydrocarbons, mainly paraffins, naph-
thenes, and 25% of aromatic hydrocarbons [1]. Various properties of
diesel as per ASTM D975 are given in Table 1, for No. 1 and No. 2
diesel. No. 1 diesel is less viscous and has a better temperature oper-
ability, with properties similar to those of kerosene, while No. 2 diesel
has lower volatility and better fuel economy, and is therefore used more
extensively in CI engines than the No. 1 diesel. CI engines are used in a
wide range of operations, such as transportation (road, rail, and
marine), agriculture, and construction.
The limited reserves and increasing prices of diesel have raised
concerns over energy security and economy, while the emissions are
leading to the environmental degradation and healthcare concerns as
limit the emissions, such as of particulate matter, nitrogen oxides,
carbon monoxide, unburnt hydrocarbons, and smoke [4]. The emissions
from CI engines are lower than from the SI engines, except for those of
PM and NOx. PM poses serious environmental and health concerns,
while NOx emissions are responsible for acid rain, smog and ozone
formation [5]. Thus, there is a need for renewable and cleaner sources
of energy.
1.1. Alternative fuels for CI engines
1.1.1. Vegetable oils
Rudolf Diesel ran diesel-car first on peanut oil in the year 1909.
Thus, vegetable oils, which primarily consist of triglycerides of fatty
acids, could be potentially used as an alternative fuel. They are en-
vironmentally carbon neutral, apart from being renewable and non-
toxic [6]. Carbon dioxide is consumed by plants to produce biomass,
which can be processed to form vegetable oils, within a life cycle of a

Abbreviations: ASTM, American society for testing and materials; BSEC, Brake specific energy consumption; BSFC, Brake specific fuel consumption; BTE, Brake
thermal efficiency; CI, Compression ignition; CPP, Critical packing parameter; CTAB, Cetyl trimethyl ammonium bromide; DTBP, Di-tert-butyl peroxide; EGBE,
Ethylene glycol butyl ether; EGT, Exhaust gas temperature; FT, Fischer-Tropsch; HC, Hydrocarbon(s); PIT, Phase inversion temperature; PM, Particulate matter;
ULSD, Ultra low sulfur diesel
⁎
Corresponding author.
E-mail address: ashoknb@chemical.iitd.ac.in (A.N. Bhaskarwar).

https://doi.org/10.1016/j.fuel.2019.115944
Received 30 May 2019; Received in revised form 30 July 2019; Accepted 1 August 2019
Available online 31 August 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
I. Abrar and A.N. Bhaskarwar
Notations
ao effective area of head group, m2
I intercept of equation, dimensionless
K solubility constant of alcohol to oil at given temperature,
dimensionless
Kd distribution coefficient, dimensionless
lc maximum effective length of hydrocarbon chain, m
MH molecular mass of hydrophilic head group of the surfac-
tant molecule, kg/mol
ML molecular mass of lipophilic tail of the surfactant mole-
cule, kg/mol
na total number of moles of alcohol in microemulsion system,
mol
nia number of moles of alcohol at interface in the micro-
emulsion system, mol
noa number of moles of alcohol in oil phase in the micro-
emulsion system, mol
few years. When the vegetable oils are burned, they liberate carbon
dioxide back to the environment. The net emissions of carbon dioxide
into the atmosphere are potentially zero, at least theoretically. Vege-
table oils have a high viscosity and a low volatility, and therefore they
have lower droplet evaporation rates and do not form homogenous air-
fuel mixtures, which leads to increased CO, HC, and smoke emissions.
Moreover, when burnt in the CI engines, they stick to piston rings and
cause coking of injector nozzles. They have a lower oxygen stability as
well. The viscosity of vegetable oils can be reduced by various methods,
such as transesterification, catalytic cracking, blending, emulsification,
microemulsification, Fischer-Tropsch process, and preheating.
Transesterification of vegetable oils with alcohols leads to the for-
mation of biodiesel and glycerol, as shown in equation (1). Apart from
vegetable oils, biodiesel can also be obtained from animal fat. It is an
oxygenated fuel, having an improved combustion efficiency and re-
duced exhaust gas emissions. It is biodegradable and non-toxic. How-
ever, it is more viscous than diesel, has a higher pour point, lower
oxidation stability, and the transesterification process is uneconomical.
The saturated compounds in the biodiesel crystallize at low tempera-
ture, clogging the fuel filter and fuel lines, which causes incomplete
combustion and thus creating cold-start problems in the engine [7].
Moreover, it has higher NOx emissions. Thus, biodiesel is blended with
diesel instead of using it directly in compression ignition engines.
The thermally cracking of vegetable oils is done in the presence of
hydrogen, to obtain diesel-like hydrocarbons known as hydrotreated
vegetable oil. But, the quality control of products is challenging as the
reaction takes place at a high-pressure (6–20 MPa) and an elevated
temperature (300–400 °C), under conditions which increase the oper-
ating cost of the fuel production [8]. The reactions are also sensitive to
2
Fuel 257 (2019) 115944
naw number of moles of alcohol in water phase in the micro-
emulsion system, mol
no total number of moles of oil in the microemulsion system,
mol
ns total number of moles of surfactant in the microemulsion
system, mol
R universal gas constant, J.mol−1.K−1
S slope of equation, dimensionless
T temperature, K
v volume of hydrocarbon chain, m3
x ia mole fraction of alcohol in the interfacial composition,
dimensionless
mole fraction of alcohol in the bulk oil phase, di-
mensionless
x1 volume percentage of n-hexadecane, %
x2 volume percentage of heptamethylnonane, %
Got standard Gibbs free energy, J.mol−1
the various process parameters, for example, the high temperature
causing cracking of products to gasoline; whereas pressure controls the
isomerization of carbon chains, and the catalyst can get deactivated due
to impurities present in the vegetable oil.
Bio-oils, produced by the liquefaction or pyrolysis of biomass, are
being used as an alternative fuel for combustion. However, those cannot
be directly used in engines as they have high water and oxygen con-
tents, and are therefore corrosive in nature [9]. This problem could
possibly be overcome by using bio-oil-in-diesel microemulsions.
The blending of diesel and vegetable oil is economical, but the re-
sultant viscosity is still higher than that of neat diesel. Moreover, the
fuel consumption is increased, along with an increase in the smoke and
HC emissions [10]. Besides, the direct blending of vegetable oils with
diesel does not reduce coking or cause a reduction in the cloud point.
1.1.2. Alcohols
Addition of oxygenates into the fuel leads to a more complete
combustion of the fuel, thus reducing the emissions of particulate
matter and unburnt hydrocarbons. Oxygenating fuels, such as alcohols,
esters, and ethers, reduce the PM by 15–20% for an oxygen content of
2–3% [11]. Bioethanol, having 2–10% water content, is used as an al-
ternative renewable fuel [12]. Ethanol is a highly volatile alcohol with
a low production cost. It can be used in the CI engines by either fu-
(1)
migation and dual-fuel which require engine modifications, or in the
form of blends, emulsions, or microemulsions which require fuel
modification.
Ethanol is fumigated into the combustion chamber of the CI engine
by using a carburettor. It helps to improve the thermal efficiency and
reduce the EGT; however, the ignition delay is increased. Moreover,
NOx emissions decrease significantly with the aqueous ethanol, but
I. Abrar and A.N. Bhaskarwar Fuel 257 (2019) 115944

Table 1 at specific compositions, known as microemulsions. Various dispersions

Properties of diesel fuel oil [2]. of emulsions and microemulsions for the alcohol-diesel-water system
S. No. Property No. 1 Diesel No. 2 Diesel are given in Fig. 1. Microemulsification improves the water tolerance and
stability of ethanol-in-diesel. Moreover, the addition of a small amount
of water improves the efficiency of combustion, and reduces NOx, PM,
2
1 Kinematic viscosity @ 40 °C (mm /s) 1.3–2.4 1.9–4.1
2 Cetane number, minimum 40 40
CO, and smoke emissions [19].
3 Flash point, minimum (°C) 38 52
4 Sulfur, maximum (ppm) 15 15
5 Ash, maximum (% mass) 0.01 0.01 1.2. Microemulsions
6 Ramsbottom carbon residue, maximum (% 0.15 0.35
mass)
The term microemulsion was coined by Schulman for an optically
7 Conductivity, minimum (pS/m) 25 25
8 Lubricity, maximum (micron) 520 520 isotropic dispersion of oil and water [20]. Later on, the thermodynamic
stability of microemulsions was studied [21]. The microemulsions are
defined as transparent and thermodynamically stable colloidal disper-
increase if anhydrous ethanol is used instead [13]. The fuel consump- sions of polar phase and non-polar phase, stabilized by a surfactant,
tion is also increased, along with an increase in emissions of CO and with the particle size smaller than one-fourth of the wavelength of
unburnt HC. visible light [22].
Dual-fuel is another technique in which the engine runs on two fuels, The structure of formed microemulsions depends on the ratio of oil
such as diesel and alcohol. The fuels are stored in different tanks, and to water, and the nature of surfactant used [23]. Spontaneous emulsi-
the engine can run either on one fuel at a time or both the fuels si- fication was classified by Winsor into four systems, namely, Winsor I
multaneously. It improves the BTE, and reduces NOx and PM emissions. (oil-in-water in contact with excess oil phase), Winsor II (water-in-oil in
However, CO, unburnt HC, and aldehydes emission are increased, contact with excess water phase), Winsor III (middle layer of bi-
especially at lower loads. The temperature and pressure of the com- continuous microemulsions in contact with excess oil and water
bustion chamber are lower at low loads, and hence significantly af- phases), and Winsor IV (single phase bicontinuous microemulsions)
fected by the latent heat of ethanol [14]. Moreover, the dual-fuel [24]. This system has usually been used for classification of micro-
technique requires separate injection systems and leads to a lower emulsions by subsequent researchers. The arrangement of micelles and
power at higher loads. bilayers of a hydrocarbon-based surfactant is governed by the critical
The blending of alcohol and diesel significantly reduces carbon packing parameter (CPP) which depends on the maximum effective
monoxide, unburnt hydrocarbons, and smoke emissions, and improves length of the hydrocarbon chain, lc, the volume of hydrocarbon chain,
the combustion efficiency [15]. The limited miscibility of alcohol in v, and effective area of head group, ao, as given by the equation (2)
diesel restricts the percentage of blending, and additives or emulsifiers [25]. CPP is equal to one-third for the formation of spherical micelles
are required to enhance the stability of blends. The lower cetane (Fig. 2), half for cylinder micelles, and one for planer bilayers. It is
number and higher oxygen content increase the combustion tempera- further suggested that the increase in the value of CPP through and
ture, while higher latent heat decreases the same. It has, however, been beyond one leads to the formation of bicontinuous (Fig. 4) and reverse
found that there is a slight increase in NOx emissions for alcohol-diesel aggregate structures (Fig. 3), respectively [26]. The value of CPP can be
blends as compared to those for neat diesel [16]. changed various methods, such as changing the concentration of sur-
Emulsions are formed by mixing two immiscible fluids, such as diesel factant, adding another surfactant or co-surfactant, changing tempera-
and water, by mechanical agitation with the help of a homogenizer or ture and pH, and adding salt [27]. Hence, the transitions of micro-
by ultrasonication [17]. The water content of as low as 0.05% v/v emulsions through various Winsor types can be affected by such
becomes critical for diesel-ethanol blends, as it can cause the phase parameters. For example, a change in salinity, at constant temperature
separation at 0 °C [18]. This is attributed to the higher polarity of and pressure, modified oil-in-water microemulsions into water-in-oil
ethanol, and its affinity with water. The emulsions thus need a con- microemulsions [28].
tinuous agitation to be sustained for a longer time. Surfactants can be v
added to the emulsions to increase the miscibility of ethanol and diesel CPP =
a ol c (2)
forming thermodynamically stable and optically isotropic dispersions,
The formulation of stable microemulsions is dependent on the HLB

Fig. 1. Alcohol-diesel-water system: (a) turbid emulsion with dispersed water droplets, (b) milky-white emulsion with a high percentage of water, (c) emulsion
separated into two layers of oil and water when kept undisturbed over a period of time, (d) clear microemulsion.

3
I. Abrar and A.N. Bhaskarwar
Fig. 2. Formation of oil-in-water microemulsions.
(hydrophilic-lipophilic balance) of surfactant used. HLB of a surfactant
was introduced by Griffin in 1949, with HLB range from one to forty,
where low HLBs are assigned to lipophilic surfactants and high HLBs to
hydrophilic surfactants [29]. Equation (3) gives the formula for calcu-
lation of HLBs of non-ionic surfactants [30].
20MH
HLB =
(MH + ML ) (3)
where MH and ML are the molecular masses of hydrophilic head groups
and lipophilic tails of the surfactant molecule. Later on, the scale of HLB
was changed from (1–40) to (0–20), where zero and twenty represent
extreme cases of entirely lipophilic and hydrophilic surfactant mole-
cules, respectively. Strong oleophilic surfactants have a lower HLB
number, such as oleic acid which has a HLB number of 1, and cannot
form stable microemulsions [31]. In such cases, they are neutralized by
hydrophilic surfactants with a higher HLB number in order to have the
maximum amount of water in the microemulsions. The generalized
empirical equation for the HLB was given later by Davies in 1957, i.e.
equation (4) [32].
HLB = Sum of hydrophilic group numbers
+ (Number of CH2 groups in surfactant molecule)
× (Group number per CH2 group) + 7 (4)
Microemulsions are sensitive to temperature since the curvature of
the film changes at a critical point known as phase inversion tem-
perature, or PIT [33]. Oil-in-water microemulsions are formed below
phase inversion temperature, whereas water-in-oil microemulsions are
formed above it. Bicontinuous microemulsions form when the tem-
perature is equal to PIT. The asymmetric distribution of oil and water in
Fig. 3. Formation of water-in-oil microemulsions.
4
Fuel 257 (2019) 115944
microemulsions using a non-ionic surfactant, such as Tween-80, causes
aggregation of the surfactant molecules used. The literature suggests
dehydration of these aggregates happening as the temperature is in-
creased, causing clouding of the microemulsions. The two phases thus
formed have been identified with dye-probing method [34]. The upper
region is oil-rich while the lower region is water-rich. The surfactant is
partitioned in both the phases depending on the hydrophobic chain
length. Moreover, the turbid emulsion can also be separated into oil-
rich, water-rich, and bicontinuous zones in microemulsions with the
incremental adjustments in temperature.
Surfactants help achieve the droplet size range of 10–100 nm by
reducing the interfacial tension [35]. Non-ionic surfactants have a
higher hydrophobicity than of ionic surfactants and lower down the
interfacial tension and also increase the solubility, and hence reduce the
droplet sizes more as compared to the ionic surfactants [36,37]. The
microemulsion region based on hydrophobic surfactant can be in-
creased by introducing hydrophilic surfactant; for example, Brij 35 and
Tween-80, where, Brij 35 is required in lesser quantity than Tween-80,
as it is linear and more hydrophilic [35].
Surfactivity is the adsorption ability of a surfactant onto the surface
of a solution, which results in the reduction of surface free energy.
Addition of a small amount of a cationic surfactant into an anionic
surfactant and vice-versa increases the surfactivity, thereby increasing
the quantity of solubilized water [31]. The interfacial tensions are
further reduced by using mixed co-surfactants over mixed non-ionic
surfactants or a single co-surfactant due to better synergetic effects
[38]. Biosurfactants, such as ramnolipid, are biodegradable, efficient,
and sustainable in comparison to the synthetic surfactants. Ramnolipid
has ten times the solubilization capacity for glycerol with respect to
Span-80/Tween-80 mixtures, due to its molecular structure [39].
I. Abrar and A.N. Bhaskarwar
1.2.1. Oil-in-water microemulsion
A small quantity of oil dispersed in a large amount of water, and
stabilized by a surfactant leads to the formation of oil-in-water micro-
emulsions. The surfactant molecules have CPP of 1/3, leading to the
formation of spherical micelles, which trap the oil droplets inside them
and are dispersed in a continuous water phase, as shown in Fig. 2. The
temperature should remain below PIT, as discussed earlier. These mi-
croemulsions find a wide range of applications in various fields [40].
They increase the uptake of cosmetic products into the skin. Some
microemulsions are used for controlled release of drugs in organisms, as
well as of agrochemicals into the soil. They are also widely used in the
food industry for various purposes, such as glyceride production and for
forming coatings on citrus fruits.
1.2.2. Water-in-oil microemulsion
Water droplets dispersed in oil, and stabilized by a surfactant leads
to the formation of water-in-oil microemulsions. The surfactant mole-
cules having CPP of 3, and temperature above PIT, lead to the forma-
tion of reversed micelles, which trap water droplets inside them, and
disperse in the continuous oil phase, as shown in Fig. 3. This class of
microemulsions have been used as lubricants, corrosion inhibitors, and
as cutting oils, owing to their high heat capacity [41]. Further, they
improve the fuel atomization, and reduces the combustion temperature
and soot formation, hence used as a fuel replacement.
1.2.3. Bicontinuous microemulsion
Bicontinuous microemulsions are formed by surfactant molecules
having CPP of 1, at a temperature near PIT, as shown in Fig. 4. The
surfactant molecules arrange themselves in a lamellar structure leading
to the formation of bicontinuous microemulsions, which is achieved by
bicontinuous partitioning of the volume into mutually connected in-
terpenetrating sub-volumes [42]. They have been used as detergents
due to their ability to solubilize both polar and non-polar phases. They
have also been used for environmental remediations, such as removal of
polyaromatic hydrocarbons, polychlorinated biphenyls, and other or-
ganic compounds from the soil [41].
2. Microemulsion fuels for CI engine
Microemulsions are preferred over other alternative fuels, such as
biodiesel, hydrotreated vegetable oil and Fischer-Tropsch diesel, as
they do not involve any reactions. This fuel modification is simple,
having a low production cost, and does not require any changes in the
existing engine or infrastructure. The source of diesel has a high impact
on the microemulsion formation; for example, Fisher-Tropsch (FT)
diesel prepared from synthetic gas has a higher lower emissions than
petro-diesel [43].
Fig. 4. Formation of bicontinuous microemulsions.
5
Fuel 257 (2019) 115944
The water droplets are dispersed in a continuous phase of diesel in
cases of both emulsions and microemulsions. As the temperature inside
the combustion chamber increases, the water droplets evaporate ra-
pidly as the boiling point of water is much lower than that of diesel.
These microexplosions of water droplets result in breaking up of diesel
films into finer droplets, leading to secondary atomization of the fuel
inside the combustion chamber, as shown in Fig. 5 [34]. These fine
droplets of diesel have an increased specific surface area, and hence are
readily combustible. The microexplosions also increase the turbulence
which improves the air-fuel mixing and further enhances the combus-
tion. The water droplets do not have any direct contact with engine
cylinder, as they are tightly bound inside diesel droplet, thus it does not
impose any issue on engine wear or lubrication oil contamination [44].
Microexplosions in water-in-diesel microemulsions have been ex-
perimentally confirmed by the presence of glow spots, which are
otherwise absent in case of the neat diesel [46]. Microemulsion fuels
have a higher droplet penetration as compared to the emulsions and
neat diesel due to the lower volatility of water. Microexplosions have
also been observed in water-in-diesel emulsions during the Leidenfrost
effect, using a high-speed camera [47]. The microexplosions were
present in all the cases of mechanically stirred emulsions, and were
absent for homogenized emulsions. Khan et al. have captured the mi-
croexplosions in mechanically stirred emulsions with 5%, 10% and 20%
water, as shown in Fig. 6. The emulsion droplets are initially opaque
due to the presence of water. As the temperature is increased, ag-
gregation and coalescence occur, followed by boiling of water, and fi-
nally microexplosion.
The surfactant used for formulating microemulsions should be free
from nitrogen and sulfur, and should be readily combustible [48].
Moreover, branched-chain surfactants within their loose aggregation
have easier penetrability, thereby increasing the solubilization of oil as
compared to linear surfactants [49]. Cationic surfactants have nitrogen,
which increases the NOx emissions, while anionic surfactants usually
contain sulfur which causes poisoning of exhaust catalyst, and phos-
phorous which decreases the activity of the catalyst [23]. Non-ionic
surfactants have an aliphatic hydrocarbon tail, such as fatty acid
ethoxylates and alcohol ethoxylates, with C, H and O atoms. They are
mostly biodegradable and non-toxic, and are thus preferred over ionic
surfactants. The phase interaction is enhanced in extended surfactants
due to the presence of intermediate polar groups such as ethylene and
propylene oxide groups, between the polar and the non-polar groups.
Alcohol ethoxylates are considered renewable and low-sulfur co-sur-
factant alternatives, which increase the microemulsification because of
the improved solubilization of water in oil [12].
Co-surfactant reduces the intermolecular stress between heads and
tails at the interface by packing themselves between the surfactant
molecules. The ratio of the surfactant to co-surfactant has a high impact
I. Abrar and A.N. Bhaskarwar Fuel 257 (2019) 115944

Fig. 5. Secondary atomization of water droplets present in the continuous oil phase, due to the microexplosions [45]. Note: Figure reprinted from https://www.
sciencedirect.com/science/article/pii/B9780128151624000197, further permissions related to the material excerpted should be directed to Elsevier.

Fig. 6. Microexplosion in water-in-diesel emulsions with different percentages of water [47]. Note: Figure reprinted from https://pubs.acs.org/doi/10.1021/
ef501588z, further permissions related to the material excerpted should be directed to the ACS.

on the microemulsion region, as seen in the case of quaternary micro-
emulsion system, consisting of Tween-80, n-butanol, diesel and water
[34]. The microemulsion region reduces with the increase in co-sur-
factant percentage. A lower surfactant to co-surfactant ratio minimizes
the solubilization of water in the reverse microemulsions, thereby de-
creasing the microemulsion region [6]. Moreover, at lower tempera-
tures, water, and hydrophilic co-surfactants tend to separate out from
the microemulsions as they have a higher tendency for hydrogen
bonding. Thus, to solubilize the same quantity of ethanol and water, a
higher amount of surfactant is required. However, in the case of water-
in-diesel microemulsions with Triton X-100 as a surfactant, the micro-
emulsion region decreased with a decrease in co-surfactant percentage
[50]. Pseudo-ternary phase diagrams have been used to plot micro-
emulsions with more than three components, wherein surfactant and
co-surfactant have generally been clubbed together as an emulsifier.
Alcohols are usually used as co-surfactants to form uniform micro-
emulsions, as they decrease the interfacial tension and rigidity of the
interface, and adjust the HLB of the microemulsion system [31]. The
solubilization capacity of an alcohol increases upon increasing its chain
length up to n-pentanol, and thereafter it decreases, modifying the
microemulsion domains accordingly [51]. The droplet size of water-in-
diesel microemulsions decreases with an increasing chain length of the
alcohol [35]. Branched chain alcohols are required in higher quantities
as compared to linear chain alcohols of the same chain length, and also
need a higher surfactant concentration since they have a higher water
solubility [52]. Alcohols also help in the reduction of the viscosity of
microemulsions, and the viscosity decreases with the decrease in chain
length from C8 to C4. Apart from alcohols, ethers, acetals, and esters
also help reduce the electrostatic repulsion between surfactants, thus
acting as a co-surfactant.
The concentration of an electrolyte affects the quantities of surfac-
tant and co-surfactant required for microemulsion formation. Water
solubilization of hydrophilic surfactants is reduced by the addition of
electrolyte as it minimizes the dissociation of their hydrophilic groups,
and enhances the molecular packing, thereby decreasing the interfacial
fluidity [37]. Moreover, at lower electrolyte concentrations, a higher
ratio of surfactant to co-surfactant concentrations is required to form
stable microemulsions [52]. In case of CTAB-based diesel

6
I. Abrar and A.N. Bhaskarwar
microemulsions, at a lower concentration of sodium nitrate, butanol
aids in solubilizing CTAB in water, thereby reducing the concentration
of CTAB at the interface. This necessitates CTAB to be used in a higher
quantity to form stable microemulsions. At higher salt concentrations,
butanol solubility is reduced, and hence a lesser amount is available to
solubilize CTAB. Sodium chloride has been found to destabilize the
microemulsion at higher co-surfactant concentrations. The extent of
destabilization decreases with a decrease in the co-surfactant con-
centration [34].
Glycerol, which is used as an anti-freeze additive in microemulsion
fuels, does not burn entirely due to its high auto-ignition temperature,
high viscosity, and low energy density, and also emits carcinogens and
higher amount of ash. The cloud and pour points of glycerol-in-diesel
microemulsions are lower as compared to those of neat diesel, along
with a reduction in the calorific value of the fuel [39]. Crude glycerol
with impurities like alcohol, water, and sodium chloride, could also be
utilized to formulate microemulsions; however, the impurities have a
negative effect on glycerol solubilization.
2.1. Diesel microemulsions
Both water-in-diesel and bicontinuous microemulsions can be for-
mulated using alkyl polyglycol ethers as surfactants, in combination
with alcohol ethoxylates as cosurfactants [48]. Diesel microemulsions
have been formulated using ethoxylated nonylphenol as a surfactant
with its concentration kept constant at 15% w/w, and the water per-
centage varied from 0 to 14% w/w. Density and viscosity of micro-
emulsions were found to be higher than those of neat diesel, while there
were negligible differences in their cloud points and corrosivities [53].
The presence of water in the microemulsions resulted in an increase in
the flash point. The performance and emission characteristics of the
microemulsion fuels are discussed separately in later sections (Sections
4 and 5) of the present review.
Smaller surfactant molecules have a higher diffusion coefficient,
and leads to lower droplet sizes as compared to the larger molecules.
They have therefore been used to formulate FT-diesel microemulsions
with 9–13% (w/w) water [43]. NMR studies also revealed that the
system with smaller surfactant molecules had higher diffusion coeffi-
cients, and thus were more dynamic than the traditional surfactants.
Bio-oil, which is ordinarily immiscible in diesel, can form homo-
genous microemulsions with diesel using rhamnolipid biosurfactants
[54]. The microemulsion fuel had lesser calorific value and higher
viscosity with respect to neat diesel. Similarly, bio-oil obtained from
sewage sludge at liquefaction temperature of 260–370 °C has been used
to formulate water-in-diesel microemulsions with Span-80 as a surfac-
tant [9]. In another study, bio-oil produced from methanol, castor oil,
and sewage sludge was used to formulate diesel microemulsions with
the help of Span-80 and Tween-80 as a surfactant, and n-hexanol as co-
surfactant [55]. These microemulsions showed a slight reduction in
calorific values, and higher viscosities than those of diesel. Synthetic
bio-oil has been upgraded to a microemulsion fuel using Span-80,
wherein the non-polar compounds were dissolved in diesel, while the
polar compounds in water. The viscosity, cloud point, and pour point of
these microemulsions were comparable to those of neat diesel [56]. A
reduction in the calorific value and a higher amount of water present
had been reported for microemulsions, when compared to the neat
diesel, but the calorific value improved with respect to bio-oil.
2.2. Alcohol-diesel microemulsions
Diesel microemulsions prepared using aqueous ethanol (95%),
Emersol 315, and n,n-dimethylethanolamine as surfactants do not un-
dergo phase separation upon centrifugation. However, they cannot
work on full load, when used as a fuel in CI engines, due to the va-
porization of ethanol [18]. Moreover, the peak power is 7% lesser as
compared to that with neat diesel, and the injector pump also required
7
Fuel 257 (2019) 115944
a readjustment to overcome such power loss. In another experimental
investigation, ethanol–diesel microemulsions, (with 100% and 95%
ethanol) were stabilized by ethyl acetate. These microemulsions re-
placed upto 49% (v/v) diesel, with density, viscosity, cloud and pour
points close to those of neat diesel [11]. In an extension of the above
work, microemulsions with a wide range of concentrations of the
aqueous ethanol (95% v/v, 90% v/v and 85% v/v) have been studied
[57]. The densities of ethanol-(ethyl acetate)-diesel microemulsions
were found to be close to neat diesel, while those with anhydrous
ethanol had lower densities. The cloud and pour points increased with
an increase percentage of water and ethyl acetate in the microemul-
sions, while the flash and fire points were reduced due to the presence
of a higher percentage of ethyl acetate, when compared to neat diesel.
Ethanol-diesel microemulsions have been formulated using single
non-ionic surfactant Alfonic 1214 GC-3, tri(ethylene glycol) mono tetra
decyl ether (C14E3), which solubilized up to 37 water % (w/w) with
reduced emissions of CO2, NOx, and soot [58]. Ethanol-diesel micro-
emulsions have also been formulated using synthetic diesel having 73%
(w/w) tetradecane, 15% (w/w) cyclohexane, 7% (w/w) nujol, and 5%
(w/w) p-xylene in its composition [59]. The light-scattering measure-
ments indicated that the microemulsions of synthetic diesel with 20%
(v/v) ethanol and 2% (w/w) dodecylamine had an average droplet
radius of 1.5 ± 0.1 nm while those with 20% (v/v) ethanol, 2% w/w
dodecylamine and 2% (w/w) oleic acid had an average droplet radius
of 1.4 ± 0.2 nm. Furthermore, an increase in the percentage of ethanol
in microemulsions, or a decrease in temperature led to an increase in
the droplet radius.
Some alcohols can act both as a surfactant and a co-surfactant, for
the formulation of alcohol-diesel-water microemulsions, without the
need of additional surfactant [60]. Alcohol-diesel-water microemul-
sions reported recently are found to have a slight reduction in the ca-
lorific value, while the densities, viscosities, sulfur content, Rams-
bottom carbon residue, and copper strip corrosion rating are as per
ASTM standards [61]. There is a slight reduction in the flash point,
which would require a careful handling of the fuel. Effect of different
types of surfactant on the microemulsion region have also been studied,
and it is observed that Triton X-100 (hydrophilic non-ionic surfactant)
expands the microemulsion region while Span-80 (hydrophobic non-
ionic surfactant) narrows it [62].
In a similar study, surfactant-free alcohol-diesel-water microemul-
sions had shown higher calorific values as compared to the volume-
fraction weighted averages of the calorific values of the pure compo-
nents [63]. These microemulsions had viscosities, cloud points, and
sulfur contents within the ASTM D975 permissible limits. The cetane
number, however, was significantly lower for higher volume-percen-
tages of replacement of diesel. In extension of the above work, micro-
emulsions were reported with 42.2% (v/v) diesel successfully replaced
with alcohol and water [64]. These microemulsions were economical,
with fuel consumption and thermal efficiencies comparable to those of
diesel, and further had lower emissions of HC and NOx at all loads.
2.3. (Vegetable oil)-diesel microemulsions
The vegetable oils have limited solubility in conventional surfac-
tants, therefore, vegetable-oil microemulsions are difficult to formulate.
They have highly hydrophobic alkyl chains, and hence required addi-
tional extended surfactants, co-surfactants, and linkers [37]. Biodiesel-
water microemulsions prepared using Span-80 as a surfactant, and
ethanol as a co-surfactant could result in lower energy consumption,
reduced smoke, and slightly lower NOx emissions [65]. However, the
ignition delay for biodiesel-water microemulsions was higher than that
for neat diesel, which led to a lower cylinder pressure at low engine
loads. Similarly, water in (colza-oil)-diesel microemulsions were for-
mulated using Brij-30 and Tween-80 as surfactants, and n-butanol as
co-surfactant [66]. The higher amount of co-surfactant was required to
solubilize more water in the microemulsions. In an extension of same
I. Abrar and A.N. Bhaskarwar
work, it was observed that the water droplets were uniformly dispersed
upto 1000 rpm, but the size increased at 1500 rpm, possibly due to the
dispersion of oil droplets inside the water droplets [67].
Diesel with up to 25% of soybean-oil as oil phase had been used for
formulating microemulsions with water, and with fatty acid diethano-
lamine as a surfactant, and isoamyl alcohol as a co-surfactant, keeping
the surfactant to co-surfactant ratio at 0.5 [36]. These microemulsions
were claimed to have properties close to those of diesel, but the engine
studies had not been carried out. Moreover, microemulsions of B5 and
B20 methyl esters derived from refined soybean-oil reduced CO, NOx,
and smoke emissions, but increased the hydrocarbon emissions [68].
The density, viscosity, and the flash point of microemulsions were
higher due to the presence of biodiesel with a flash point of 172 °C.
Similarly, microemulsions based on palm-oil methyl ester had very high
viscosities and lower calorific values when diesel was replaced with
higher percentages of water, mixed surfactants, and co-surfactants [38].
The flash point was also reduced due to the presence of alcohols, but it
did not affect the engine performance. Microemulsification has also
been used found to improve cold flow properties, and reduce ignition
delay in case of waste cooking oil derived water-in-biodiesel micro-
emulsions [69].
2.4. (Vegetable oil)-alcohol microemulsions
Limited work has been done on (vegetable oil)-alcohol microemul-
sions due to their limited stability and lower cetane number.
Microemulsions of waste cooking oil with ethanol and butanol have
been formulated, which resulted in higher viscosity and lower calorific
value of the fuel, when compared to neat diesel [70]. Ionic micro-
emulsions of soybean-ethanol have been studied, using linoleic acid and
triethylamine as the surfactants and butanol as a co-surfactant. Even
though the microemulsion fuel produced 5% less power than neat
diesel, BTE was higher as the fuel was burnt in a leaner mixture, due to
the presence of oxygenates [22]. BSFC was, however, 16% higher than
that for neat diesel. Moreover, the microemulsion separated into two
layers at 0 °C, and hence would lead to cold-start issues. Cetane number
of 29.8 for microemulsion was also much lower than the prescribed
limit of 40 for neat diesel. Thus, a cetane improver, i.e. primary alkyl
nitrate, had been added to the microemulsions. But, the nitrates could
possibly increase the NOx emissions in the exhaust.
2.5. (Vegetable oil)-alcohol-diesel microemulsions
Studies on soyabean-oil based biodiesel as a surfactant had been
carried out, for the formation of ethanol-diesel microemulsions,
wherein gasoline was added as a denaturant for ethanol [71]. The
microemulsions formulated as such lead to 34% reduction in sulfur
content with respect to neat diesel. That, however, increased from 1.2
to 18 ppm in case of ULSD, due to the presence of gasoline. The mi-
croemulsion fuels, however, showed a two-fold and four-fold increase
in lubricity as compared to diesel and ULSD, respectively.
In another study, ethanol was used as a polar phase to formulate
microemulsions with canola-oil and diesel (in the ratio of 1:1) as oil
phase, using various surfactants, such as oleyl alcohol, Surfonic L24-1,
Span-80, and Alfoterra 168-42C [12]. The microemulsion formation
was confirmed using a red laser beam, which transmitted the beam
without diffusing it. Microemulsions formulated with Span-80 required
the least amount of surfactant, as the other surfactants were more
bulky, and thus had lower solubilization. All microemulsions for-
mulated as such were unstable below 0 °C, and hence required addi-
tional co-surfactants to avoid phase separation. The studies had also
been carried out with surfactants mixed in different ratios, and it was
observed that the concentration of surfactant required was reduced
when lower molecular weight surfactants were used. Oleyl alcohol and
Surfonic L24-1 were required in the least amounts to formulate the
microemulsions.
8
Fuel 257 (2019) 115944
Non-edible oils, such as castor and algal oils were also studied.
Ethanol was miscible in (castor oil)-diesel blend, while (castor oil)-
(algal oil) blends required a surfactant to formulate the microemulsion
[12]. Algal oil has a higher degree of polyunsaturated fatty acids, and
thus is more hydrophobic. Moreover, di-tert-butyl-peroxide was used as
the cetane enhancer, and ethylene glycol butyl ether as an anti-freezing
agent. All the above-mentioned microemulsions had higher viscosities
and lower calorific values (35–38 MJ/kg) compared to those of neat
diesel. 2-ethylhexylnitrate was used as cetane improver in case of
(sunflower oil)-butanol-diesel and (sunflower oil)-pentanol-diesel mi-
croemulsions [72]. The addition of nitrates in the fuel was expected to
increase the NOx emissions; however, it was found that the NOx emis-
sions actually decreased by 0.26–5.26%. The combustion chamber
temperature is reduced due to a shorter ignition delay caused by the
improved cetane number, thereby decreasing the NOx emissions.
Waste cooking oil based fuels can be used as a potential alternative
fuel. (Waste cooking oil)-ethanol-diesel microemulsions with Dehydol
LS1 and Span-80 as surfactants were found to have droplet sizes smaller
than 200 nm [73]. The viscosities of the microemulsions increased with
an increase in their percentage content of waste cooking oil. It was also
observed that the flash points had significantly reduced to 11 °C for
microemulsions, in comparison to 69 °C for diesel, which could possibly
lead to some handling and storage issues.
Linear and branched alkyl propoxylated ethoxylated carboxylate
surfactants were studied for the formation of reverse microemulsions
with ethanol as a polar phase, canola oil as a non-polar phase, n-octanol
and iso-octanol as co-surfactants, ethylene glycol butyl ether as an anti-
freezing agent, and di-tert-butyl-peroxide as a cetane enhancer [74]. It
was observed that branching increased the water solubility of the sur-
factants. Anhydrous ethanol was completely miscible with diesel at
25 °C, and did not require any surfactant. However, with an increase in
the percentage of canola oil in diesel, a higher amount of surfactant was
required to achieve the miscibility. The viscosity of microemulsions
with fifty and lower percentages of canola oil in diesel met the ASTM
requirements of diesel oil. Moreover, when the temperature was in-
creased from 0 °C to 40 °C, ethylene oxide groups in the surfactant were
dehydrated, resulting in a more hydrophobic surfactant. Ethanol also
became less hydrophilic at a higher temperature, and thus less surfac-
tant was needed to formulate the microemulsion at higher tempera-
tures.
3. Thermodynamics of microemulsions
The initial studies on thermodynamics of microemulsions have been
done by calculating the effect of free energy of mixing on interfacial
free energy change, the energy of interaction among droplets, entropy
effect, and stable radius of droplet [21]. The first two effects have ne-
gative free energy change, while the latter two have positive free en-
ergy change. Hence, thermodynamically stable microemulsions are
formed when the interfacial tension is decreased to a very low value,
and its small positive value is overcome by negative free energy change
due to the entropy of dispersion and dilution effect [75].
A simplified form of the thermodynamics of microemulsion systems,
wherein higher alcohols, immiscible with water, were used, appeared in
the literature [76,77]. The number of moles of alcohol in microemul-
sion system is given by
na = nai + naw + nao (5)
where na represents the number of moles of alcohol; the superscripts i,
w and o indicate interface, water, and an oil phase, respectively. At a
given temperature, the solubility constant of alcohol to oil is constant,
say K. Then, the equation (5) reduces to
na = nai + naw + Kno (6)
where no is the number of moles of oil in the microemulsion system. The
I. Abrar and A.N. Bhaskarwar
ratio of the total number of moles of alcohol (na ) to those of the sur-
factant (ns ) is given by
na n i + naw n
= a +K o
ns ns ns (7)
The solubility of higher alcohols (C > 4) in water could be neglected
[77], reducing the equation to
na ni n expected value for the microemulsion having 4% water. It is also ob-
= a +K o
ns ns ns (8)
Using this equation to plot na /ns versus no /ns , slope S = K and in-
tercept I = nai / ns are obtained. These relations were further used to
calculate nao by using K = nao /no and nai from I. The partitioning of al-
cohol in oil phase and the interface was then given by distribution
coefficient K d , where
xai n i /(n i + ns ) I (S + 1)
Kd = = ao ao =
xao na /(na + no) S (I + 1) (9)
where xai is the mole fraction of alcohol in the interfacial composi-
tion, and xao is the mole fraction of alcohol in the bulk oil phase. The
standard Gibbs free energy, Gto , would then be determined from
I (S + 1)
Gto = RT lnK d = RTln
S (I + 1) (10)
4. Performance characteristics of microemulsion fuels
4.1. Calorific value
Calorific value or the heating value gives the amount of heat re-
leased per unit mass during complete combustion of the fuel in the
presence of oxygen at standard conditions. The microemulsions have
lower calorific values as compared to neat diesel. Ethanol is used to
reduce the viscosity of vegetable-oils based microemulsion fuels, which
also leads to a reduction in the calorific value of these fuels [6]. In one
of the studies, the calorific value of ethanol-(ethyl acetate)-diesel mi-
croemulsions reduced from 46.85 MJ/kg for neat diesel to
30.47–45.7 MJ/kg for the microemulsions [57]. The calorific value for
these microemulsions reduced more with an increase in the percentage
of water in ethanol (5% v/v, 10% v/v, and 15% v/v) when compared to
the anhydrous ethanol. In another study, the calorific value of alcohol-
diesel-water microemulsion fuels was observed to be higher than the
weighted mass basis at 60% and 70% diesel concentrations [78]. These
microemulsions were reported to modify reaction pathways due to the
presence of alcohol and water, leading to more complete combustion.
4.2. Viscosity
Viscosity is a measure of the resistance offered by a fluid to flow.
The viscosity of diesel should be from (1.9–4.1) × 10−6 m2/s as per
ASTM D975 [2]. The viscosity of a microemulsion fuel depends on its
composition. Ethanol has a lower viscosity than diesel, and is thus used
as a viscosity modifier in “vegetable oils and diesel” blends. In order to
reduce the viscosity of canola and palm oil based microemulsions,
having 50% (v/v) of respective vegetable oils, 24% (v/v) ethanol is
required [6]. Similarly, the viscosities of ethanol-(ethyl acetate)-diesel
microemulsions reduces from 33.4 Redwood seconds for neat diesel to
25.9–30.1 Redwood seconds for the microemulsions of different com-
positions [57]. Ethanol has also been used both as a polar phase, and as
a viscosity modifier to formulate (palm oil)-diesel microemulsions,
using methyl oleate as a surfactant [79].
Researchers have used various viscosity-prediction models, among
which the Chevron model is used most commonly [80]. The interaction
of dispersed phase droplets with the continuous phase leads to an in-
crease in the viscosity of microemulsions. Ethanol-based
9
Fuel 257 (2019) 115944
microemulsions with 1:1 volumetric ratio of diesel and vegetable oil
(where the vegetable oil is canola, algae or palm oil) have been for-
mulated, using oleylamine as a surfactant and octyl alcohol as a co-
surfactant in the molar ratio of 1:4 [80]. Viscosities of the micro-
emulsions are correctly predicted by the model, a finding which in-
dicates that the dispersed phase has the minimum effect on the visc-
osities. Moreover, the viscosity is accurately predicted for the
microemulsion having 2% water, but the value is much higher than the
served that the viscosity increases with an increase in surfactant con-
centration and with a decrease in temperature.
4.3. Ignition delay and cetane number
Cetane number gives the measure of the ignition delay of the fuel,
i.e. the time lag from the start of injection of fuel to the start of com-
bustion is termed as an ignition delay, and is an essential property of
the fuel [81]. It has more influence on crank angle degrees as compared
to the time scale of combustion. Longer ignition delays cause in-
complete combustion of the fuel, leading to knocking and an increase in
the amount of pollutants, such as unburnt HC gases and CO. Ignition
delay increases at lower engine loads as the charge temperature is
lower, and decreases at higher engine loads. The highest cetane number
of 100 is assigned to n-hexadecane (cetane), while heptamethylnonane
(isocetane) has 15. Initially, 1-methylnaphthalene was used as a lower
reference for cetane number, with a value of zero assigned to it, but was
later replaced by isocetane due to the difficulty in handling and cost. A
fuel with cetane number less than forty will ignite too soon, leading to
knocking which is harmful to the engine. Cetane number is calculated
using equation (11).
Cetane number (CN ) = x1 + 0.15x2 (11)
where x1 and x2 are the volume percentages of n-hexadecane and
heptamethylnonane in the mixture, respectively.
Microemulsions have a higher latent heat of vaporization due to the
presence of water, which reduces the temperature, thereby increasing
the ignition delay. Ethanol has a lower cetane number, and therefore
ethanol-based microemulsion fuels have a much lesser cetane rating
than the neat diesel, which results in a higher ignition delay [18]. The
ignition delay of microemulsions is higher than that of biodiesel, and it
increases with an increase in the percentage of water in the micro-
emulsion [65]. The cetane numbers of ethanol-biodiesel-diesel micro-
emulsions are lower than those of diesel and ULSD [71]. Cetane im-
provers, such as, di-tert-butyl-peroxide and ethyl hexyl nitrate need to
be added to the fuel, if it has the cetane number below forty.
4.4. Brake specific fuel/energy consumption (BSFC/BSEC)
BSFC is dependent on the calorific value of the fuel. The calorific
value of the fuel is decreased due to the presence of water in the mi-
croemulsion fuel. This led to an increase in the fuel consumption [53].
The specific fuel consumption of water-in-diesel microemulsion was
found to be higher than neat diesel due to the reduced calorific value of
the fuel [58]. The BSFC of water in (colza-oil)-diesel microemulsion was
found to be 9.7–17.6% higher than neat diesel at 25–100% load [82].
Similarly, the fuel consumption increased from 0.4 to 1 l/kW-h at 30%
throttle with an increase in the speed of the engine from 1400 to
1900 rpm in case of water-in-diesel microemulsions as compared to the
increase from 0.35 to 0.5 l/kW-h for neat diesel [48]. In another study,
BSFC of (bio-oil)-diesel microemulsions increased upto 12% due to
lower calorific value and higher viscosity of the microemulsions when
compared to neat diesel [55]. In order to compare various fuels with
different calorific values, BSEC is a more appropriate parameter to use.
BSFCs of microemulsion fuels were found to be higher than that of
biodiesel, due to their lower calorific values, but the BSEC reduced
because of the improved vaporization and atomization [65].
I. Abrar and A.N. Bhaskarwar
However, some researchers reported a decrease in fuel consumption
with microemulsions as compared to neat diesel. Jatropha Curcas based
biodiesel used to stabilize ethanol-diesel blends showed 2.7% lesser
BSFC than that of neat diesel [83]. The presence of oxygen in ethanol
and biodiesel perhaps promotes more combustion of the fuel, thus re-
ducing the BSFC. The difference, however, was reduced at the full load
which could be either due to an increased thermal efficiency or due to
the relatively decreased heat losses. Similarly, the BSFC of alcohol-
diesel-water microemulsion fuel run in a constant speed CI engine
showed a 2% reduction compared to that of diesel, due to the more
complete combustion aided by oxygenates[84]. At lower loads, the
BSFC of all the (jatropha oil)-diesel microemulsions with Dehydol LS1
as surfactant and ethanol as co-surfactant was lower than neat diesel
[85]. As the percentage of ethanol is increased in the microemulsions,
the fuel consumption also increases, due to the lower calorific value of
ethanol. The effect of various microemulsion fuels on BSFC has been
compiled in Table 2.
4.5. Brake power and brake thermal efficiency (BTE)
BTE represents the efficiency of the engine to convert chemical
energy to useful work. Usually, the brake power decreases with mi-
croemulsions due to the lower heating values of alcohol and water.
However, in some cases, the brake power was reported to increase, as in
the case of ethanol-(ethyl acetate)-diesel microemulsions, where an
increase of 0.3–2.4% in the brake power was observed as compared to
neat diesel [57].
BTE and BSFC are inversely related to each other. In most of the
literature, the BTE was found to improve upon using the microemul-
sions instead of neat diesel, as can be observed in Table 3, due to en-
hanced pre-mixed combustion caused by microexplosions. BTE of al-
cohol-diesel-water microemulsion fuel increased by 5% for a 2%
decrease in BSFC, with respect to neat diesel [61]. All other tested
microemulsion compositions had a comparable/higher efficiency to/
than that of neat diesel, indicating that the aforementioned micro-
emulsions could be used as diesel replacements. Similarly, ethanol-
based microemulsions using Emersol 315 and n,n-dimethylethanola-
mine as surfactants had 4–5% higher BTE as compared to that for neat
diesel [18]. In another study, the BTE of water in (colza-oil)-diesel
microemulsion was found to be comparable to neat diesel [82].
In some of the literature, reduction in BTE was observed due to a
reduction in calorific value, and increase in BSFC of the fuel. For ex-
ample, BTE of ethanol-(ethyl acetate)-diesel microemulsions was in the
range of 22.8–30.1% in comparison to 25.4% for neat diesel [55]. The
efficiency increased for aqueous ethanol (95%), while it reduced for
anhydrous ethanol (100%) at the full load. Similarly, the BTE of (bio-
oil)-diesel microemulsions was reduced at lower loads due to lower
Table 2
Effect of microemulsion fuels on the fuel consumption in compression ignition engine.
S. No. Reference Microemulsion system
1. [22] soyabean oil, ethanol, butanol, linoleic acid, triethyl amine
2. [48] diesel, water, Berol-533, Berol-535, alkyl ethoxylates
3. [53] diesel, water, NFE-5
4. [55] bio-oil, diesel, Span-80, Tween-80, hexanol
5. [57] ethanol, ethyl acetate, diesel
6. [58] diesel, water, Alfonic 1214 GC-3, tri(ethylene glycol) mono tetra decyl ether,
limonene, ethanol
7. [65] biodiesel from soyabean oil, water, ethanol, Span-80
8. [79] diesel, palm oil, methyl oleate, ethanol, butanol/octanol/decanol
9. [82] diesel, colza oil, water, Tween-80, Brij-30, butanol
10. [85] jatrpha oil, diesel, ethanol, Dehydol LS-1
11. [86] diesel, ethanol, Span-80 or biodiesel from jatropha oil
12. [87] tung oil, diesel, ethanol, oleic oil, butanol
10
Fuel 257 (2019) 115944
heating value, but became comparable to neat diesel as the load was
increased due to more complete combustion caused by microexplo-
sions.
5. Emission characteristics of microemulsion fuels
5.1. Nitrogen oxides (NOx)
As per the Zeldovich mechanism, NOx formation requires a high
temperature. The NOx emissions are expected to be reduced due to the
presence of water in the microemulsion which increases its latent heat,
and thereby the temperature inside the engine is reduced. It was ob-
served that the NOx emissions were significantly reduced for water-in-
diesel microemulsions formulated with ethoxylated nonylphenol sur-
factant. NOx emissions were reduced from 90 to 52 ppm at 0.33 kW and
from 221 to 105 ppm at 2 kW, with an increase in water content from 0
to 14% (w/w) in the microemulsions [53]. Similarly, water-in-diesel
microemulsions formulated using a combination of non-ionic surfac-
tants and alcohol ethoxylates reduced the NOx emissions upto as much
as 71% at higher speeds (2600 rpm) and higher throttle (40%) as
compared to that for neat diesel [48]. Water-in-diesel microemulsions
with C14E3 as surfactant and ethanol as co-surfactant reduced up to
80% NOx emissions at 30% throttle, when compared to neat diesel [58].
The NOx emissions were also found lower in (bio-oil)-diesel micro-
emulsions due to thermal dilution of microemulsion in the presence of
water [55].
The EGTs of ethanol-(ethyl acetate)-diesel microemulsions were
found to be higher than that of petro-diesel, along with higher peak
temperature and pressure, which could be due to an increase in the
ignition delay. The NO emissions, however, were found to be lower
than those with neat diesel, under all load conditions (0–110% load),
when anhydrous and aqueous ethanol (95% v/v) were used for for-
mulating the microemulsions [11]. The NO2 emissions, however, were
lower only for no load to 75% load; and the emissions increased at
100% and 110% load. The increase in NO2 emissions was because of the
increase in peak temperature mentioned earlier. It was also observed
that the emissions were lower for microemulsions with aqueous ethanol
than those with anhydrous ethanol, which indicated that the presence
of water reduced the NO2 emissions. Similarly, the NOx emissions for
canola oil and algal oil based ethanol-in-diesel microemulsion fuels
were found to be almost similar to those of neat diesel, but showed an
increase in case of nitrogen-containing oleyl amine and ethylhexylni-
trate [6].
Thus, the NOx emissions are reduced for microemulsions due to the
presence of the higher latent heats of vaporization of water (~2260 kJ/
kg at 100 °C) and ethanol (~855 kJ/kg at 78 °C) in microemulsions, the
effect of water being greater than that of ethanol. Moreover, the
Effect on engine
16% increase in BSFC w.r.t diesel
fuel consumption is doubled at 1900 rpm when compared to diesel
increased BSFC w.r.t diesel
8–12% increase in BSFC w.r.t diesel
increase in BSFC w.r.t diesel
increase in fuel consumption (upto 31%) when compared to diesel
increase in BSFC w.r.t biodiesel
7–27% increase in BSFC w.r.t diesel
9.7–17.6% increase in BSFC w.r.t diesel
lower BSFC than diesel at lower loads, significant increase at higher loads
2.7% decrease with biodiesel microemulsions; same for Span-80
microemulsions w.r.t diesel
9.2–20.3% increase in BSFC w.r.t diesel
I. Abrar and A.N. Bhaskarwar Fuel 257 (2019) 115944

Table 3
Effect of microemulsion fuels on the thermal efficiency in compression ignition engine.
S. No. Reference Microemulsion system Effect on engine

1. [18] Diesel, 95% ethanol, Emersol 315, n,n-dimethylethanolamine 4–5% increase at higher loads w.r.t diesel
2. [22] soyabean oil, ethanol, butanol, linoleic acid, triethyl amine 6% increase in BTE w.r.t diesel
3. [53] diesel, water, NFE-5 increased BTE w.r.t diesel
4. [55] bio-oil, diesel, Span-80, Tween-80, hexanol 6% decrease to 10% increase w.r.t diesel
5. [57] ethanol, ethyl acetate, diesel 10.2% decrease in BTE for 200 proof ethanol, 18.5% increase for 180 proof ethanol w.r.t
diesel
6. [82] diesel, colza oil, water, Tween-80, Brij-30, butanol 5% decrease to 3% increase w.r.t diesel
7. [86] diesel, ethanol, Span-80 or biodiesel from jatropha oil 10.7% decrease with biodiesel microemulsions, 10.4% increase for Span-80 microemulsions
w.r.t diesel
8. [87] tung oil, diesel, ethanol, oleic oil, butanol upto 15.4% increase w.r.t diesel

addition of nitrate compounds (as cetane improvers) to the fuel leads to
an increase in the NOx emissions. The effect of different microemulsion
fuels on NOx emissions has been represented in Table 4.
5.2. Carbon monoxide (CO)
The presence of water in the microemulsions decreased the tem-
perature inside the combustion chamber, which further reduced the
combustion efficiency and led to an incomplete combustion near the
wall of the combustion chamber [53]. The CO emissions were found to
increase from 430 ppm at 2 kW for neat diesel to 463 ppm at 2 kW for
nonylphenol-based diesel microemulsions having 14% (w/w) water. In
continuation of the above work, when 5% and 20% of diesel was re-
placed with biodiesel, it was observed that the CO emissions increased
for microemulsion with 5% biodiesel, while there was a slight decrease
in CO emissions for microemulsion with 20% biodiesel [68]. It was
concluded that this decrease was due to the presence of more oxygen in
the biodiesel, which led to a more complete combustion.
Other researchers have also reported a reduction in CO emissions.
For example, a higher degree of mixing in ethanol-(ethyl acetate)-diesel
microemulsions due to the micro-explosions resulted in lower CO
emissions at higher loads (75%-110% load) when compared to that for
neat diesel [11]. Similarly, CO emissions were less, at full power, in
ethanol-based microemulsions using Emersol 315 and n,n-dimethy-
lethanolamine as surfactants due to the presence of oxygen in alcohols
[18]. In another study, CO emissions were also reported to be 80%
lesser for canola, palm, and algal oils based microemulsions than that
for neat diesel [6]. The CO emissions of (bio-oil)-diesel microemulsions
showed upto 66.7% reduction when compared to neat diesel, due to the
homogenous distribution of alcohol in the microemulsion [55]. The
effect of microemulsion fuels on the CO emissions has been compiled in
Table 5.
5.3. Unburnt hydrocarbons (HC)
The CO and HC emissions usually have a similar trend.
Microemulsions with a lower combustion temperature result in an in-
complete combustion of the fuel near the engine walls, resulting in an
increase in the HC emissions. However, the presence of oxygenates
leads to a more complete combustion, resulting in a decrease in HC
emissions. The net increase or decrease in the unburnt HC depends on
these above two factors. At lower temperatures, the HC emissions can
also be controlled with the use of grid heaters and glow plugs [88]. The
effect of microemulsion fuels on the HC emissions has been summed up
in Table 6. The unburnt HC emissions were found to be higher in case of
ethanol-diesel microemulsions with Emersol 315 and n,n-dimethy-
lethanolamine as surfactants than those for neat diesel [18]. Similarly,
for ethanol-diesel microemulsions with ethyl acetate as a surfactant, the
emissions were 25–40% higher as compared to those for neat diesel,
except for microemulsion fuel with 75.5% diesel and pure ethanol at
full load, where the HC emissions decreased by 33.4% [11]. The
emissions were even higher for aqueous ethanol (95%) as compared to
anhydrous ethanol (100%), which might be due to the slower vapor-
ization of the formulated aqueous microemulsions.
Biodiesel contains oxygen, leading to a more complete combustion.
The microemulsion formulations using 20% biodiesel reduced the un-
burnt HC emissions with respect to diesel [68]. The emissions, however,
increased with the microemulsions formulated using 5% biodiesel. The
trends are thus similar to those of CO emissions, as discussed earlier.
5.4. Soot and particulate matter
Polyaromatic hydrocarbons, especially pyrene and fluorene, are the
precursors of soot formation. The soot emissions, in turn, lead to the PM
formation [89]. The presence of oxygen in microemulsion fuels, in the

Table 4
Effect of microemulsion fuels on the NOx emissions in compression ignition engine.
S. No. Reference Microemulsion system Effect on engine

1. [6] canola oil/algal oil/palm oil, diesel, oleyl alcohol/amine, isooctanol octanol, canol oil microemulsions showed increase in emissions, while algal and
2ethylhexylnitrate, ethylene glycol butyl ether, ethanol palm oil microemulsions had emissions similar to diesel
2. [11] ethanol, ethyl acetate, diesel NO emissions are reduced, while NO2 emissions are increased w.r.t diesel
3. [46] diesel, water, penta(ethylene glycol) monoundecyl ether, sorbitan monooleate 7.9% average decrease w.r.t diesel
4. [48] diesel, waterBerol-533, Berol-535, alkyl ethoxylates 3% to 71% reduction in w.r.t diesel
5. [53] diesel, water, NFE-5 50% decrease to 46.8% increase w.r.t diesel
6. [55] bio-oil, diesel, Span-80, Tween-80, hexanol decrease in emissions upto 14.7% w.r.t diesel
7. [58] diesel, water, Alfonic 1214 GC-3, tri(ethylene glycol) mono tetra decyl ether, 3% to 80% reduction in w.r.t diesel
limonene, ethanol
8. [65] biodiesel from soyabean oil, water, ethanol, Span-80 decrease at lower loads, and increase at higher loads w.r.t biodiesel
9. [68] biodiesel from soyabean oil, water, NP5EO decrease in NOx emissions w.r.t diesel
10. [79] diesel, palm oil, methyl oleate, ethanol, butanol/octanol/decanol 7–30% decrease w.r.t diesel
11. [82] diesel, colza oil, water, Tween-80, Brij-30, butanol upto 21% reduction in NOx emissions w.r.t diesel
12. [87] tung oil, diesel, ethanol, oleic oil, butanol upto 54% increase w.r.t diesel

11
I. Abrar and A.N. Bhaskarwar Fuel 257 (2019) 115944

Table 5
Effect of microemulsion fuels on the CO emissions in compression ignition engine.
S. No. Reference Microemulsion system Effect on engine

1. [6] canola oil/algal oil/palm oil, diesel, oleyl alcohol/amine, isooctanol, octanol, 80% reduction in CO emissions w.r.t diesel; palm oil
2ethylhexylnitrate, ethylene glycol butyl ether, ethanol microemulsions showed maxium reduction
2. [11] ethanol, ethyl acetate, diesel lower emissions at higher loads when compared to diesel
3. [18] Diesel, 95% ethanol, Emersol 315, n,n-dimethylethanolamine higher at lower loads, and lower at higher loads w.r.t diesel
4. [48] diesel, water, Berol-533, Berol-535, alkyl ethoxylates 18% to 32% reduction w.r.t. diesel
5. [53] diesel, water, NFE-5 3.5% decrease to 98.7% increase w.r.t diesel
6. [55] bio-oil, diesel, Span-80, Tween-80, hexanol 66.7% decrease to 12% increase in emissions w.r.t diesel
7. [57] ethanol, ethyl acetate, diesel 18–44% decrease for 200 proof ethanol, 1.4–37.7% decrease for
180 proof ethanol w.r.t diesel
8. [68] biodiesel from soyabean oil, water, NP5EO Increase in CO emissions for most of microemulsion, slightly lower
for B20 when compared to diesel
9. [79] diesel, palm oil, methyl oleate, ethanol, butanol/octanol/decanol 22–77% increase w.r.t diesel
10. [82] diesel, colza oil, water, Tween-80, Brij-30, butanol upto 23% increase in emissions w.r.t diesel
11. [85] jatrpha oil, diesel, ethanol, Dehydol LS-1 lower emissions at most of loads when compared to diesel
12. [87] tung oil, diesel, ethanol, oleic oil, butanol 300% increase to 33% decrease w.r.t diesel

Table 6
Effect of microemulsion fuels on the HC emissions in compression ignition engine.
S. No. Reference Microemulsion system Effect on engine

1. [11] ethanol, ethyl acetate, diesel increase in emissions at low loads (upto 10 times), slight reduction at higher loads when
compared to diesel
2. [18] diesel, 95% ethanol, Emersol 315, n,n- lower at lower loads, and higher at higher loads w.r.t diesel
dimethylethanolamine
3. [53] diesel, water, NFE-5 67.2% decrease to 77.1% increase w.r.t diesel
4. [57] ethanol, ethyl acetate, diesel marginally higher emissions
5. [68] biodiesel from soyabean oil, water, NP5EO increase for B5 microemulsions, slightly lower for B20 microemulsions when compared to
diesel
6. [82] diesel, colza oil, water, Tween-80, Brij-30, butanol higher HC emissions (upto 34%) w.r.t diesel
7. [87] tung oil, diesel, ethanol, oleic oil, butanol 91% increase to 16% decrease w.r.t diesel

form of water, alcohol or biodiesel, oxidizes the soot, leading to a more
complete combustion, with the consequent reduction in soot formation.
All the literature suggested a decrease in soot emissions of the micro-
emulsion fuels when compared to neat diesel, as observed in Table 7.
The soot and smoke formation thus reduced due to the presence of
water in microemulsions in spite of the decrease in the combustion
temperature [53].
The soot collected from quaternary microemulsions by placing a
pre-weighed cover on the flame was found to be upto 89% lower than
that obtained from diesel, and the microemulsions burned for a longer
period of time without leaving any trace of water, indicating that the
microemulsions were stable during burning [34]. Similarly, soot re-
duced from 6 to 12% for neat diesel to 2–4% for water-in-diesel mi-
croemulsions at 30% throttle and 1400–1900 rpm; as compared to the
reduction from 5 to 9% for neat diesel to 1–8% with microemulsions at
40% throttle and 1800–2600 rpm [48]. In another study, water-in-
diesel microemulsions led to a reduction of up to 74% of soot emissions
at 40% throttle, when compared to neat diesel [58].
In another study, lower flame temperatures and rapid evaporation
of water in microemulsions led to a reduction of upto 89% of soot as
compared to that for neat diesel [46]. Flame intensities produced were
higher in all cases as compared to neat diesel. The oxygen content in
ethanol-in-diesel microemulsions with Emersol 315 and n,n-dimethy-
lethanolamine as surfactants increased the combustion in fuel-rich re-
gions, and thus reduced the exhaust smoke [18]. The smoke and par-
ticulate matter emissions were lower for water-in-diesel
microemulsions, using 5% and 20% biodiesel blended with diesel, and
nonylphenol ethoxylate surfactant [68]. It was observed that the in-
crease in the biodiesel percentage led to a further reduction in the
emissions.

Table 7
Effect of microemulsion fuels on the soot emissions in compression ignition engine.
S. No. Reference Microemulsion system Effect on engine

1. [18] Diesel, 95% ethanol, Emersol 315, n,n-dimethylethanolamine significant decrease at all loads w.r.t diesel
2. [46] diesel, water, penta(ethylene glycol) monoundecyl ether, sorbitan monooleate 89% average decrease w.r.t diesel
3. [48] diesel, water, Berol-533, Berol-535, alkyl ethoxylates 22–86% reduction w.r.t. diesel
4. [53] diesel, water, NFE-5 decrease at all loads w.r.t. diesel
5. [55] bio-oil, diesel, Span-80, Tween-80, hexanol reduction of upto 20% of smoke
6. [58] diesel, water, Alfonic 1214 GC-3, tri(ethylene glycol) mono tetra decyl ether, limonene, 94% decrease to 37% increase in comparison to diesel
ethanol
7. [68] biodiesel from soyabean oil, water, NP5EO decrease at most of the loads w.r.t. diesel
8. [85] jatrpha oil, diesel, ethanol, Dehydol LS-1 lower smoke, especially at lower loads when compared to
diesel

12
I. Abrar and A.N. Bhaskarwar
6. Conclusion
There has been a substantial increase in the cost of fossil fuels due to
limited reserves and increasing demand in recent times, raising con-
cerns over energy security and the associated economy. Diesel is a
widely used fuel, which emits exhaust gases containing nitrogen oxides
(NOx), carbon monoxide (CO), unburnt hydrocarbons (HC), particulate
matter (PM), and smoke. The PM and NOx emissions pose the most
severe environmental and health concerns, and thus there is an urgent
need for sustainable alternative fuels. Diesel alternatives commonly
include vegetable oils and alcohols, which need pre-processing before
combustion in the engine. These techniques, however, have certain
limitations. Biodiesel has a cold-start problem, and also higher NOx
emissions; blends are not stable, and hence separate over a period of
time; and dual-fuel and fumigation techniques require engine mod-
ifications. Microemulsification, on the contrary, helps in the simulta-
neous reduction of PM and NOx emissions, and in addition, does not
require any changes in the current engines and storage-transport-supply
infrastructure.
Diesel-based microemulsion fuels usually have diesel and/or (ve-
getable oil)-diesel blends as a non-polar phase, and water and/or al-
cohol as the polar phase. The calorific value of a microemulsion is lower
than that of neat diesel due to the lower calorific value of the polar
phase in it. Its viscosity depends on the components used; for example,
vegetable oils increase the viscosity, while alcohols decrease the same.
The cetane number is lower due to ignition delay caused by the higher
latent heat of vaporization of the polar phase. However, in the majority
of the literature, it is observed that the BTE is comparable to or higher
than that for neat diesel, along with a reduction in NOx, soot, and in PM
emissions. It is also observed that some researchers have reported an
increase while others a decrease in BSFC, and CO, and HC emissions.
Very accurate comparative analysis of the literature is not possible,
as different researchers have analyzed the emissions under different
conditions, such as of throttle, load or rpm, making it challenging to
conclude the effect of microemulsion compositions on CO emissions
unambiguously. A unifying system is, therefore, a must to study the
impact of different parameters under some standard set of conditions,
as is in the case of measurement of properties as per standards.
7. Future prospect
Relatively limited research has been done on diesel-based micro-
emulsion fuels, and hence, this area needs to be extensively in-
vestigated. The microemulsions could soon be used as an economical
and environment-friendly diesel replacement, as they are comparable
or better than diesel in terms of properties, performance, and emissions,
and besides the process of making microemulsion is facile.
Microemulsions involve simple, gentle mixing, and are compatible with
the existing infrastructure, giving them an edge over other alternatives.
Since the formation of microemulsion requires two immiscible
phases, many alternative fuels could be used in combinations for diesel
replacement. For example, alcohols, both hydrous and anhydrous,
could be used as a polar phase for the formation of microemulsions.
Similarly, bio-oil and biodiesel based microemulsions also have po-
tential as a diesel replacement. Microemulsification could also reduce
the viscosity of vegetable oil with the help of alcohols. Thus, the mi-
croemulsions could plausibly replace diesel completely in the future
with water or/and alcohol as the polar phase, and vegetable oils or/and
its derivatives as the non-polar phase. The microemulsions can corre-
spondingly be used to replace other fossil fuels, such as gasoline and
aviation fuel.
One of the alternative, economical microemulsion fuels could pos-
sibly be achieved by replacing the surfactant by a co-surfactant,
wherein the co-surfactant could help in solubilization of the polar phase
in the non-polar phase. For a 20% (v/v) diesel replacement with al-
cohol, the cost of fuel reduced by 5.57% as per USA pricing, and 5.40%
13
Fuel 257 (2019) 115944
as per Indian pricing of the fuels. Such fuels would also emit lesser
levels of pollutants in the form of exhaust gases, helping the mankind in
protecting the environment for all life forms on our exceptional “blue-
green planet”.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by DST-INSPIRE (IF150907), and SERB
(EMR/2016/004152), Government of India.
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