Energy Conversion and Management 178 (2018) 146–177

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

The effect of nano-additives in diesel-biodiesel fuel blends: A comprehensive T

review on stability, engine performance and emission characteristics
Manzoore Elahi M. Soudagara, , Nik-Nazri Nik-Ghazalia, , Md. Abul Kalama, I.A. Badruddinb,
⁎ ⁎

N.R. Banapurmathc, Naveed Akrama

a
Faculty of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Mechanical Engineering, King Khalid University, Abha 62529, Saudi Arabia
c
Department of Mechanical Engineering, B.V.B. College of Engineering and Technology, Vidyanagar, Hubli 580031, India

ARTICLE INFO ABSTRACT

Keywords: Biodiesel is an unsurpassed alternative fuel source intended to extend the value to fossil fuels, and the longevity
Diesel and cleanliness of diesel engines. It reduces the dependence on the foreign fuels and reduces the greenhouse gas
Biodiesel emissions due to its closed carbon cycle. The plentiful advantages of biodiesel are overcome by few drawbacks
Nanoparticles such as the increase in the nitrogen oxide emission, its incompatibility with cold weather conditions, and the
Stability
regular intervals of engine parts replacement such as fuel filters, fuel tanks and fuel lines due to clogging. There
Performance
is a further scope for enhancement in fuel properties and to overcome the drawbacks by addition of nano-
Emission
particles as fuel additives. Recent researches on fuel additives indicated the inclusion of nano-sized particles
(metallic, non-metallic, oxygenated, organic and combination) with diesel-biodiesel fuel emulsion. The results
achieved demonstrated an improvement in the thermophysical properties, enhancement in the heat transfer rate,
and stabilization of the fuel mixtures. Also, there was an increase in the engine performance parameters and
reduction in the exhaust emissions depending on the dosage of nanofluid additives. This review paper includes
the methods for preparation of nanofluids, the stability enhancement of nanofluids by various technique, several
characterization methods to find the chemical bonding, nanoparticle shape, and size, dispersion of nano-ad-
ditives in liquid fuel, the health effects, and applications of nanoparticles in the automotive industry.
The numerous literature reviewed had some degree of indistinct and inconsistent outcomes. The experimental
results from the various researchers were not generalized to reach a general accord regarding this innovative
approach of fuel adulteration. The present work summarizes the literature from most recent articles on nano-
particles as a liquid fuel additive. The effect of dispersion of several nanoparticles on the enhancement in the
performance characteristics and reduction in emission of a CI engine fuelled with diesel-biodiesel blends are
discussed. The further scope suggests the development of an economically sustainable and feasible nanoparticle
additive for diesel and biodiesel fuel. Nevertheless, few obstacles and challenges which have been recognized in
this review must be addressed before they can be fully put into practice in the industrial applications.

1. Introduction
The decline in the fuel reserves, population growth and high living
standards of the urban class have led to an energy crisis and an en-
ormous increase in the demand and cost of the fossil fuels. The US
Energy Information Administration (EIA) has predicted that the global
fuel consumption mainly liquid fuel, will rise from 86.1 million bbl/day
to 110.6 million bbl/day by the year 2035 and the global sales of pas-
senger cars are forecasted to hit 78.6 million vehicles in 2017 [1]. The
consumption of petroleum products can carry the key environmental
impact that may be regional or global in scale, including air pollution,
climate change, and oil spills [2,3]. The dependency of world energy on
conventional fuels such as petroleum-based products, coal, and natural
gas has elevated to two-thirds of the global energy demand. The fuel-
importing developing Asian countries are in a severe economic dis-
parity due to unequal distribution of fuel prices [4]. Engine exhaust
comprises of volatile organic compounds (VOCs), which represent un-
burned fuel emissions and other VOCs produced as by-products of in-
complete combustion. Few VOCs described as being of health concern
are acetaldehyde, acrolein, benzene, 1,3-butadiene, formaldehyde, and
naphthalene. Petrol and diesel-powered automobiles are the major
sources of VOCs in urban areas. A severe problem related to diesel

⁎
Corresponding authors.
E-mail addresses: me.soudagar@gmail.com (M.E.M. Soudagar), nik_nazri@um.edu.my (N.-N. Nik-Ghazali).

https://doi.org/10.1016/j.enconman.2018.10.019
Received 7 June 2018; Received in revised form 21 September 2018; Accepted 8 October 2018
0196-8904/ © 2018 Elsevier Ltd. All rights reserved.
M.E.M. Soudagar et al. Energy Conversion and Management 178 (2018) 146–177

Nomenclature CIME Calophyllum inophyllum methyl ester

Si silicon
IC internal combustion engine Ti titanium
NPs nanoparticles Al aluminium
B100 pure biodiesel TiO2 titanium dioxide
BSFC brake specific fuel consumption Co3O4 cobalt oxide
BTE brake thermal efficiency Ni nickel
BSEC brake specific energy consumption Fe3O4 iron oxide
BP brake power CNTs carbon nano-tubes
CI compression ignition ASTM D6751-01 American Society for Testing and Materials
CO2 carbon dioxide MWCNTs multi-walled carbon nano-tubes
NOx oxide of nitrogen CuO copper oxide
NO2 nitrogen dioxide MnO manganese oxide
HC hydrocarbon CoCl2 cobalt chloride
PM particulate matter Al2O3 aluminium oxide
CO carbon monoxide CuSO4 copper sulfate
WC water cooled Al-Mg magnalium
NA naturally aspirated CeO cerium oxide
AC air cooled CuCl2 copper chloride
IL in-line GNPs graphene nanoparticles
DI direct injection FeCl3 ferric chloride
TC turbo charged EGR exhaust gas recirculation
Zr zirconium ppm parts per million
Mg magnesium bbl barrel
POME palm oil methyl ester nm nanometer
HOME honge oil methyl ester ID ignition delay

emissions is the presence of polycyclic aromatic hydrocarbons (PAHs).
Numerous PAHs are known to be mutagenic and/or highly carcinogenic
towards humans [3].
The diesel engines are widely used to power vehicles, trains, ships,
airplanes, irrigation pumps and also extended to produce electric
power. The emissions produced by the combustion of fossil fuels have a
severe effect on the ecosystem and the human health. To overcome
these drawbacks, it has become a global agenda to develop clean sub-
stitute fuels that are easily available, globally acceptable, and techni-
cally feasible. Owing to the consciousness of energy concerns and en-
vironmental glitches related through the burning of petroleum-based
fuels have fortified numerous researchers to examine the opportunity of
utilizing non-conventional energy sources, as an alternate fuel source to
fossil fuels and its derivatives [5,6]. The renewable energy sources have
a very high potential and enormous availability, which makes them
meet numerous times the earth’s energy demand. The biodiesel has
emerged as the most popular alternative fuel source to diesel [7].
Biodiesel is a non-conventional fuel source and can be made directly
from edible and non-edible oils, waste cooked oils, and animal fats like
tallow and lard [8]. The use of biodiesel in CI engine has some lim-
itations such as a minor reduction in fuel economy on an energy basis
(about 10%), marginally higher density, poor fuel atomization, lower
cloud and pour points, piston ring sticking, high NOX emission and cold
starting problems [8–10]. These disadvantages can be overcome by
applying few relatively new approaches such as addition of fuel ad-
ditives and using hybrid fuel, which results in the enhancement of en-
gine performance and reduction in exhaust emissions [11].
Among the recent additives used in diesel and biodiesel fuels, the
nanoparticles have emerged as a novel and promising additive which
results in the reduction of exhaust emissions and enhancement in en-
gine performance. Many researchers have focused their attention on
fuel modification methods by using the nano-additives for achieving
improved performance and emission characteristics [12–20]. A strict
emission regulation has been globally enforced on the emissions re-
leased from CI engines. The use of fuel additives in the fuel can modify
numerous fuel properties such as the density, sulfur content, and vo-
latility, which affects the fuel emissions. The potential of adding the
nanoparticle additive with liquid fuels as a secondary energy carrier has
improved combustion characteristics, the investigators have tried to
find the feasibility of these modified fuels with diesel engines. The
metal oxides of Cu, Fe, Ce, Pt, B, Al, and Co have been widely used as
additives in diesel and biodiesel fuel blends [15–19,21–32]. Skillas
et al. [33] studied the size distribution effect and composition of PM
using cerium as nano-additives, and reported an increase in ultrafine
but reduction in the accumulation mode. An increase in efficiency re-
sulted from the influence of nano-additives, likewise, it affects the
physicochemical properties and emission of the fuel. Sajith et al. [34]
reported that the CeO2 NPs exhibit a high catalytic activity due to their
enormous surface area per unit volume, which leads to enhancement in
the fuel efficiency and decrease the emissions. Iranmanesh et al. [35]
reported that, the fuel properties and combustion characteristics of
Karanja biodiesel in diesel engine with addition of 5%, 10%, 15% and
20% by volume of DEE, exhibited enhancement in the physicochemical
properties such as the specific gravity, calorific value, viscosity, and
liquidity with respect to the ASTM standards with improvement in
combustion and cold starting problems.
The matter of concern with the addition of nanoparticles as fuel-
additive is their stability aspects. The nanoparticles tend to aggregate
due to their large surface area and surface activity. Few studies revealed
that the clogging of the fuel injection system is caused due to the
coagulation of nanoparticles. The proper quantity of surfactant added
reduces the agitation and coagulation of nanoparticles in the base fluid
[36–42]. This review proposes the selection of best-suited surfactant for
nanoparticles based on several criteria discussed. Even though there are
several growing numbers of researches relating to biodiesel feedstocks,
engine performance, and emissions by utilizing biodiesel and nano-
technology. However, very limited articles are reviewed on the stabi-
lity, performance and emission characteristics of diesel and biodiesel
fuel blends by inclusion of various nanoparticles in the diesel and
biodiesel fuel.
In this review article, the literature is derived from research journals
and environmental magazines in scientific indices up to the year 2018,
which comprises the recent trends in nano-additive technology used in
diesel and biodiesel. Recently, few review articles are published in the

147
M.E.M. Soudagar et al.
field of nanoparticles inclusion as an additive in diesel and biodiesel
fuels, which focussed their literature on the performance, emission and
stability aspects [2,43–45]. Nevertheless, this review concentrates on
all the aspects of nano-additive technology in liquid fuels. The aim of
this paper is to comprehensively distribute information in the area of
nano-additives fueled with diesel and biodiesel fuels. It is helpful (1) to
recognize the integrated overview of using nano-additives in diesel and
biodiesel fuel blends, techniques for preparation of nanofluids, ambi-
guities in nanofluids, stability enhancement methods, stability inspec-
tion instruments, and thermophysical properties, combustion and eva-
poration characteristics of nanofluids; (2) to select the best suited nano-
additives for diesel and biodiesel based on the CI engine performance
parameters and emission characteristics; (3) to comprehend the noxious
effects of nano-additives on human health, the applications of nano-
additives, the outcome of nano-additives during combustion and in
exhaust, engine corrosion and limitations of nano-additives.
2. Nano-additives: the quality enhancers in diesel-biodiesel fuel
blends
The fuel enrichment method by addition of nano-additives is widely
accepted by numerous researchers. The nano-additives are used to
achieve specific fuel properties and to improve the performance char-
acteristics and to attain a good emission control of the CI engine
without any modification. Nubia et al. [2] summarized the basic ne-
cessities of fuel additives added to commercially available diesel fuels
in varying quantities to perform specific functions: (1) the additives
should reduce the exhaust emissions, (2) increase the oxygen con-
centration in the engine and in the particulates filter, (3) improve the
fluid stability over a wide-ranging conditions, (4) increase the viscosity
index, (5) reduction in ignition delay time, and flash point, (6) the
chemical-to-chemical contact should be improved rather than the
metal-to-metal contact under high-load conditions to reduce the wear
agents that adsorb onto the metal planes.
The advancement in nanotechnology, nanoscience and material
technology, has led to expansion of nano-scale particulate matters
whose physicochemical properties are relatively diverse with respect to
the micron scale elements of the same source material such as larger
contact surface area, better stability, fast oxidation, lower melting
point, enormous heat of combustion, reduced heat of fusion rate and
large heat and mass transfer rates [7,43]. The fuel modification and
Fig. 1. The comprehensive steps involved in the study of nanoparticle-diesel-biodiesel emulsion fuel.
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Energy Conversion and Management 178 (2018) 146–177
revision techniques are extensively known by many investigators to
make the specific fuel properties. The effect of the addition of nano-
particles to fluids is investigated in many studies. The high thermal
conductivity fluid in engine cooling systems, higher density fuels in
propulsion systems, and due to the favorable heat release rate they are
used as additives for improvement of the combustion rate of fuels and
that adding nanoparticles to a fluid can improve its physical properties,
such as thermal conductivity, evaporation rate, shortened delay period
and stimulates secondary atomization [29]. The catalytic performance
is increased because of the large surface area (high surface: volume)
and high energy level [45]. Nano-Al particles are more conducive to the
creation of micro-explosions during combustion, leading to the A-F
mixing and resulting in a complete combustion. Cobalt nano-additives
reduces NOx production, magnalium particles act as a heat sink inside
the combustion chamber by decreasing the overall temperature, and it
avoids hotspots and reducing NOX production [19,20,30,46–48], Mn-
based nanoparticle additives reduces emissions such as polycyclic aro-
matic hydrocarbons (PAHs) [49]. Ichikawa et al. [50] reported that the
hydrogen from water is generated by using TiO2 nano-additive due to
its photoelectric catalytic effect and its capability to activate the mo-
lecular bond in the water-diesel emulsion.
The literature is derived from the studies on the fuels with nano-
additives, the nano-additives were derived from various sources such as
ferro material, polymeric materials, ceramics, non-organic materials,
metal oxides such as aluminium, carbon, titanium, iron, and CNTs.
With the constant development in blending capabilities of nanoparticle
with biodiesel and ease of preparation, the method has created nu-
merous opportunities in the manufacturing of several nano-fuels from
diverse nanoparticles. The fuel-additives are used to enhance the
quality of the fuel, nano-additives also acts as a catalyst to increase the
rate of a chemical reaction, supply more oxygen for complete com-
bustion of fuel thereby enhancing the engine characteristics. Likewise,
the effect of nano-additives can be considered as catalytic effects. Fig. 1
illustrates the steps involved in the preparation of nanoparticle-diesel-
biodiesel emulsion fuel and analysis of performance and emission
characteristics of dairy scum oil biodiesel (DSOME) and graphene na-
noparticles (GNPs).
Many researchers reported that biodiesel leads to the increased
emission of GHG gases, HC and PM. However, the technological ad-
vancement of nano-additives and their use in biodiesel reduced the
emissions, which proved to be a potential fuel additive. Various
M.E.M. Soudagar et al.
investigations have been conducted to find the magnitude of heat rea-
lized by using nanoparticles, to enhance expiry time during storage,
stability, minimize the undesirable health impact and in some studies
the nanofluids were used directly in the engine reducing the emissions
and an attempt was made to utilize the combination of different na-
noparticles such as, TiO2/PrSO3H, MWCNT, Graphistrenght C100, and
Zn/CaO. There is a broad gap in the studies relating to cost feasibility,
solubility in liquid fuels, high energy density, heterogeneous combus-
tion kinetics, the formation of unstable nanoparticles, fuel suspension,
the introduction of water in nanoparticles and blends of fuels to en-
hance the engine characteristics [12,20,44,51–58]. Thus, the in-
vestigators have tried to recognize the feasibility of these modified fuels
with actual diesel engines. Some of the noticeable results are discussed
in the literature, such as a considerable development in the combustion
feature of spray flame was observed with a reduction in CO emissions
using Al2O3 nanoparticle inclusion with diesel fuel [59]. Keskin, Ali
et al. [29] reported the outcome of the metallic nanoparticles on per-
formance characteristics of CI engine with TOME. Metal fuel additives
enhanced the physiochemical properties of biodiesel fuels, such as the
viscosity values and pour point.
The inclusion of organic-based manganese additives to diesel con-
tributed to a maximum reduction in the freezing point and likewise,
many researchers concluded that the organic-based manganese lowers
the flash point, and viscosity [60]. Combustion is a complex progression
in the engine and therefore numerous parameters could hypothetically
affect the amount of engine emissions [61]. One of the chief sources
originates from incomplete combustion of fuels in the engine initiated
due to shortage of supply of oxygen [62]. This can be overcome by
increasing the volume of oxygen in the cylinder, or by increasing the
A:F ratio. Hence the addition of oxygenated nano compounds can solve
this problem [63,64]. The main oxygenated compounds presently uti-
lized with the diesel-biodiesel fuel are n-butanol, polyethoxy-ester,
methanol, glycerine tri-acetate, triacetin, dimethyl carbonate (DMC),
di-n-pentyl ether (DNPE), ethyl tert-butyl ether (ETBE) [61,64–67]. The
particulate matter emissions are reduced due to complete and cleaner
combustion of fuels due to oxygenated additives [68]. The alcohols
such as ethanol/methanol and diesel blends are the most used oxyge-
nated additives. In few investigations, the blends with methanol re-
sulted in higher bsfc values compared with ethanol blends, the dilution
of oxygenated additives in the diesel blends results in a reduction of the
calorific value of the base fluid [69].
Fig. 2 illustrates the behavior of cerium oxide at high concentra-
tions, the nanoparticle species accumulate the peroxide radicals to
overcome the steric hindrance. Subsequently, the peroxides are sur-
rounded by nanoparticles in the propagation step of biodiesel oxidation
chain reactions and avoid their contact with the new biodiesel
Fig. 2. Nano cerium oxide oxidative-reductive acting mechanism on biodiesel molecules (Adapted from [70] with permission).
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Energy Conversion and Management 178 (2018) 146–177
molecules. Thus, additional degradation of biodiesel molecules is sup-
pressed by converting the free radicals to the previous biodiesel mole-
cules [70]. The nanoparticles are broadly classified based on the ma-
terial, shape, size, origin, and occurrence. Metal oxide additives of
aluminium (Al), manganese (Mn), titanium (Ti), zirconium (Zr), cerium
(Ce), copper (Cu) and zinc (Zn) generally act as the catalysts for com-
plete combustion of fuel, in addition to minimize fuel consumed and
reduction in the emissions. Metallic additives were used since the year
2000 as diesel fuel additives, but the progress weakened through pas-
sing years, however recently the interest in the metallic based nano-
particles has renewed [71]. The NPs decrease the C.I engine flue gas
discharge by two ways: the metals/non-metals react with water to
generate HO radicals, the ash oxidation is enhanced, and the nano-
metal additives react straight-away with the carbon (C) molecules in
the ash (soot), thus temperature for oxidation is reduced [2].
3. Preparation of nanofluids
The primary stage in experimental studies of the nanofluids is their
preparation, the necessities of a specific application requires numerous
mixtures of NPs and fluids. For instance, NPs of metals, nitrides, metal
carbides, oxides, and non-metals with/without surfactant can be dis-
persed in the fluids such as oils (diesel, biodiesel, vegetable oils, mi-
neral oils and so on and so forth), water, and ethylene glycol. The ad-
vancement and interest in NPs have resulted in the innovation in the
nanoparticle production and dispersion in the fluids [72]. Nanofluids
can be prepared using two techniques known as one-step and two-step
approaches. The prerequisite of nanofluid preparation includes an even
and stable suspension of NPs with the base fluid, low agglomeration of
NPs, and low chemical variation of the liquid [73]. The liquid route for
the preparation of NPs involves the sol–gel and wet chemical methods,
which normally involves chemical reactions of a few substances with
one anticipated product while normally generating other impurities
that are challenging to control. The growth and nucleation in a vapor-
phase route producing a reactive phase take place through combustion,
laser ablation pyrolysis, laser pyrolysis plasmas, or chemical vapor
deposition. Owing to strong Van der Waals attractive force and due to
the economical and quality considerations which results in selecting the
gas phase route to be the most favorable technique for vast production
of NPs [74].
3.1. One-step preparation method
One step approach which was developed by Akoh et al. [75], also
known as Vacuum Evaporation onto a Running Oil Substrate (VEROS)
technique, it associates the preparation and dispersion of NPs with the
M.E.M. Soudagar et al.
base fluid in a single step. One of the commonly used technique in the
one-step method also known as a direct evaporation method. In this, the
nanofluids are synthesized by solidification of the NPs, which are in-
itially in a gaseous state. Other methods in one-step approach include
the production of alumina nanofluids by laser ablation method [76],
preparation of copper NPs dispersed in ethylene glycol using chemical
synthesis of nanofluids [77]. Few limitations include the separation of
the particles from the fluids to yield dry NPs, it is a very complex
process by utilizing the one-step approach, due to incomplete reaction
or stabilization the residual reactants are left in the nanofluids, difficult
to measure the quantity for large industrial applications, relevant for
only low vapor pressure fluids [78–80]. Lo et al. [81] initiated a new
system to prepare nanofluid using SANSS (Submerged Arc Nanoparticle
Synthesis System) method in which submerged arc is used to heat a
pure metal rod. SANSS is an effective way to avoid NPs agglomeration
and helps in to produce uniformity in the dispersion of NPs in deionized
water. Chang and Kao [82] enhanced the SANSS method. It helped in
improving the quality of NPs when compared with the previous SANSS
technique. The major advantage of this method is a low agglomeration
of NPs which leads to a better stability of nanofluids. The cost of drying
and dispersion can be minimized using this method.
3.2. Two-step preparation method
In the two-step method, is the widely utilized method for the
synthesis of nanofluids. The NPs are first manufactured and then dis-
seminated in the base fluids. The nano-powders are commercially
supplied by the NPs producing industries and produce good results with
the oxide nanoparticles because of their chemical stability and with the
particle concentrations larger than 20 vol%. The NPs can be synthesized
in a wide-ranging methods, the mechanical process of synthesizing in-
volves milling and grinding, which is exhaustive and energy intensive
[80,83]. The ultrasonic agitation techniques are used to agitate sur-
factants to the fluids and to reduce the particle aggregation and en-
hance dispersion response. Lee et al. [83] prepared the nanofluid by
dissolving a measured amount of NPs deionized water and sodium
lauryl sulfate (SLS) as a dispersant in an ultrasonic vibrator. The lim-
itations of the two-step method is their agglomeration (found usually in
metallic NPs), due to poor dispersion with the base fluids, hence a large
quantity of NPs are required and cost incurred for loading in high
[80,84].
Praveen et al. [85] prepared the TiO2 nanoparticles by sol-gel
method. The titanium tetra-isopropoxide was blended with ethanol and
deionized water in the proportion of 1:3 and the mixture was constantly
stirred on a magnetic stirrer for a time duration of 1 h. The following
step involves the addition of, Nitric acid (HNO3) with the blended so-
lution to obtain the sol-gel. The completed sol-gel was heated at 250 °C
for 2 h in a furnace to vaporize the water and to escalate the viscosity of
the blend. The drying process was carried out and the deposits of TiO2
crystals were obtained as nano-powder having nano-size crystals. Sa-
jeevan et al. [58] used the co-precipitation method for the synthesis of
cerium-zirconium mixed oxide NPs. In the desired weight ratios of 6:4,
8:2 and 9:1 the ammonium ceric nitrate and zirconium oxychloride
aqueous solution were mixed with distilled water and magnetic stirrer
was used to stir the mixture for 15 min at room temperature. A pH value
of 10 was achieved by the addition of aqueous ammonia and the so-
lution turns yellow in colour. Furthermore, the mixture was stirred for
2 h and the precipitate collected was washed with acetone and water
repeatedly to remove excess ammonia, for a time interval of 8 h the
sample was dried at 60 °C to get a porous yellow powder. The powder
was further grounded to get a fine powder calcinated at 500 °C tem-
perature for 1 h. Zafarani-Moattar and Majdan-Cegincara [86] used the
electrical oven to dry ZnO nanoparticles at a temperature of about
110 °C for a time interval of 24 h to remove the adsorbed water
moisture from the ZnO NPs surface. Ultrasonication process was carried
out for the dispersion of NPs in the aqueous solution of polyethylene
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Energy Conversion and Management 178 (2018) 146–177
glycol. The authors measured the particle size of nanofluids and found
the size to be larger than that of the average particle size. An excellent
stability was observed for ZnO–PEG nanofluid for a time of 140 min.
Furthermore, a long-term stability was seen when the bath was soni-
cated for 10 min and using acac. Kumar et al. [87] used ferric nitrate
salt of concentration 1 mol was dissolved in 40 ml concentration of
distilled water and 2 mol concentration of NaOH was dissolved in 50 ml
of distilled water. The two solutions were mixed, and the sonication
process was carried out for 1 h at 20 kHz for uniform distribution and
finally the homogenous product is calcined up to 350 °C.
The first investigators to disperse AIN nanoparticles were Peng et al.
[88], the AIN was produced by plasma arc in the gas phase mixed with
an ethanol blend, the dispersant used was castor oil as it improved the
suspension stability. The emulsion with the suspension was stirred
using a magnetic stirrer rotating at high-speed. The ultrasonic homo-
genizer was used in this process, and then the suspension was in-
troduced into the ultrasonic homogenizer for 10 min. The authors re-
vealed that the sample remained stable for a time duration of more than
2 weeks without settling. Tamjid and Guenther [89] used a colloid of Ag
NPs formed by the vacuum evaporation on running liquids (VERL) at
the volumetric solids concentration of 4.37%. The ultrasonic agitator
for diethylene glycol agitation and it was stirred continuously for 5 min
to ensure a uniform dispersion of the Ag NPs in diethylene glycol.
3.3. Stability aspects of nanoparticles
Many researchers conducted the various experiments to improve the
stability of nanofluids through, the ultrasonic vibration, addition of
surfactants and controlling the pH to get a proper blending of the na-
noparticles with the liquid fuel. The fluid dispersion technology consists
of three methods: mechanical control, medium control, and agent
control. The mechanical control uses a disintegrator, ultrasonic oscil-
lator, and an electromagnetic stirring for particle dispersion. The
medium control uses different media for different particles in terms of
surface properties such as polarity to attain an improved dispersion
effect. The agent control applies to the various dispersants to various
particles in terms of the physical and chemical state of the medium to
improve the rejection amongst the particles [90]. Aggregation leads to
the formation of an assembly of a large network of fractal aggregates.
This process is called gelation. The gravitational sedimentation is en-
hanced through gelation by chain-like aggregates which forms a fractal
network [91]. The rheological properties of the dispersion such as
viscosity, which is affected by the gelation process, that can limit their
mobility, it can also lead to pore plugging which limits the transport
[92]. Thermodynamically, the emulsion fuels are unstable, and hence
they are gradually separated into two immiscible phases. The most
frequent processes of emulsion fuel destabilization are droplet-droplet
coalescence, flocculation, and creaming [93].
Coalescence is the vanishing of the boundary in between two par-
ticles (generally droplets or bubbles) in contact, or between one of these
and a bulk phase followed by changes of shape resulting in a decrease of
the total surface area. The flocculation of an emulsion, viz. the devel-
opment of aggregates is followed by coalescence. If coalescence is ex-
tensive then it may lead to the formation of a macrophase and the
emulsion is said to break [94,95]. Creaming is the macroscopic se-
paration of a dilute emulsion into an extremely concentrated emulsion,
in which inter-globular contact is vital, and a continuous phase under
the act of gravity or a centrifugal field. This separation generally takes
place upward, but the term may still be used if the relative densities of
the isolated and continuous phases are such that the concentrated
emulsion settles downward [96,97]. Sedimentation is the settling of the
suspended NPs under the influence of gravity or a centrifugal field. If
there is a high concentration of NPs and the inter-particle forces are
strong, then the process of sedimentation, explained as the compaction
of the NPs structure with pressing-out of the liquid, this settling is also
called subsidence [13,98].
M.E.M. Soudagar et al.
A few investigational and theoretical studies have been carried-out
by researchers to know the characteristics of nanofluids such as ag-
gregation and sedimentation. Tiny particle size and high surface en-
ergies makes the nanofluids more susceptible to agglomerations and
particle size is responsible for high electrolyte concentration which
causes a decrease in zeta potential, thus producing an unstable nano-
suspension [43]. Nevertheless, a few models have been presented to
know the mechanism of aggregation and sedimentation of nano-sus-
pensions which comprises, Brownian dynamics sedimentation model
[99], Fractal models [100], Diffusion-limited aggregation model [101].
Nanoparticles aggregate with the time, due to their high surface ac-
tivity. The agglomeration of NPs results not only in the settlement and
clogging of microchannels but also the reduction of thermal con-
ductivity of nanofluids. Dispersion and stability are the essential char-
acteristics for improving the thermal conductivity of nanofluids. Uni-
formity in the dispersion and stability of suspended NPs in liquids
foremost important applications of nanofluids since their absolute
properties are determined by the superiority of dispersed state of the
suspension [83]. Eastman et al. [102] investigated the effect of ethylene
glycol-based nanofluids containing copper NPs, the thermal con-
ductivity of ethylene glycol-based nanofluids containing 0.3% copper
NPs is reduced with time. In the experimentation, the thermal con-
ductivity of nanofluids was measured twice: the first was within 2 days
and second was 2 months. The authors concluded that the fresh nano-
fluids demonstrated slightly higher thermal conductivity than the na-
nofluids that were stored for 2 months. The reason might be due to the
reduced dispersion stability of NPs with respect to the time. NPs may
tend to agglomerate when kept for a longer period.
Colloidal stability is the ability of particle dispersion to oppose ag-
gregation for a specified time. Colloidal stability promoted by the
presence of an energy barrier in the inter-particle interaction potential.
The DLVO theory elucidates the aggregation of aqueous dispersions
quantitatively and explains the force between the charged surfaces in-
teracting through a liquid medium. It is the combination of the Van der
Waals attraction effect and the electrostatic repulsion due to the double
layer of counter ions. The electrostatic part of the DLVO interaction is
calculated as the mean field approximation in the limit of low surface
potentials i.e. when the potential energy of an elementary charge on the
surface is much smaller than the thermal energy scale [103]. The fre-
quency of collision is formed due to the Brownian motion and the
probability of cohesion during collision is used to find the rate of ag-
gregation of NPs. The agglomeration of NPs in nanofluids can block the
parts and, the instability of the nanofluid can change its thermophysical
properties like thermal conductivity, viscosity, density, etc. with time.
The nanofluid stability determined by the sum of van der Waals at-
tractive forces and electrostatic repulsive forces that exist between NPs
dispersed in the nanofluids. The higher electrostatic repulsive force
leads to a better stability [104]. The repulsive forces between NPs en-
hanced by using two mechanisms: Steric mechanism and Electrostatic
mechanism.
3.3.1. Steric mechanism
Certain additives like surfactants/dispersants possess the ability to
prevent the aggregation of NPs dispersed in nanofluids. The aggrega-
tion of NPs dispersed in the nanofluids is prevented by addition of the
surfactants/dispersants. These surfactants cover the surface of NPs with
a long loop and tail, which extends out into the nanofluids. The NPs
surface is covered with a long loop and tail which stretches out into the
nanofluids [104]. The stability of graphite based nanofluid increased
with the addition of polyvinylpyrrolidone (PVP) which formed a pro-
tective layer around the graphite NPs and avoided the formation of
agglomerates because the nanofluid was sterically stabilized [105].
3.3.2. Electrostatic mechanism
The adsorption of ions creates a charge in the NPs present in na-
nofluids which results in the Electrostatic stabilization. The adsorption
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Energy Conversion and Management 178 (2018) 146–177
of ions generates an electrical double layer around the NPs, which
produces repulsive forces between NPs. The use is limited and it is
considered a pH-sensitive mechanism [104].
3.4. Techniques for nanofluid stability
The literature suggests that there are three operational strategies
used to achieve stability of suspension against sedimentation of NPs.
Few of the investigators applied all of these methods to gain better
stability [106,107] but others applied only one [108] or two techniques
[109,110] with gratification. There is no standard to identify the su-
perlative mix up of coalescing methods. This area requires more ex-
perimentations to be clarified. The techniques are summarized below:
3.4.1. Ultrasonic vibration
The ultrasonication is an established physical technique to disperse
agglomerated NPs in the base fluid. An extended sonication is also li-
able to damage the surfactants present inside the nanofluids. There
must be an optimum sonication time to obtain a stable nanofluid irre-
spective of the concentration of the stabilizer used [111]. To disperse
the aggregates of NPs, ultrasonication bath or probe-based ultrasonic
devices are generally used. The probe-based ultrasonic device functions
at the very high frequency. Therefore, there may be the possibility of
contamination of nanofluids due to the disconnection of very minute
metal particles from the surface of the metal probe. This might ad-
versely affect the stability of nanofluids. Such loose metal particles,
which are present in nanofluids, may erode the heat transfer apparatus
surface during its use. An attention should be paid for the detection and
removal of such particles from nanofluids [112]. El-Seesy et al. [113]
investigated the stability of the Alumina (Al2O3) NPs, the Al2O3 nano-
particle concentrations of 10–50 mg/l were mixed in JB20D fuel blend
using ultrasonic stabilization. A sample containing 50 mg/l Al2O3 and
JB20D fuel emulsion were kept in an elongated tube in static conditions
to notice blend stability. The author observed the mixture for one week
and there was no NPs settlement. The SiO2 nanoparticles were dis-
persed in distilled water, and an ultrasonic bath was used for sonication
for 90 min. The silica nanofluids continued to remain stable for a period
of 72 h without any noticeable settlement [114]. An ultrasonic vibra-
tion for 2 h was used to break down the agglomeration of mixed NPs of
Al2O3 and SiO2 of pure methanol based nanofluids. Furthermore, the
authors calibrated the zeta potential with respect to the pH of the
suspension and found the zeta potential of Al2O3, and SiO2 nanofluids
to be 60 mV and 30 mV respectively, which specified that the Al2O3
nanofluids and SiO2 nanofluids were stable with the base fluid [31].
In the synthesis of water-soluble ZnO NPs, initially the water-so-
luble ZnO NPs was sonicated for 1 h and a measured quantity of acet-
ylacetone (acac) was added as a dispersant to the solution and sonicated
over again for 10 min. The investigators found that the NPs were stable
for over 9 months to 1 year, and there was a reduction in the size of ZnO
NPs from 150 nm to 80 nm due to the chemical reaction [115]. Lamas
et al. [116] investigated the effect of MWCNTs NPs, the MWCNTs NPs
were prepared by the chemical vapor deposition technique. The neat
MWCNTs were refluxed at 413 K in HNO3 and H2SO4 at 1:3 volume
ratio for half an hour, subsequently with washing with distilled water
(DW) till no signs of acidity remained and parched in an oven for 72 h
at a temperature of 373 K, to eliminate the humidity. Furthermore, the
ultrasonication was carried out for one hour for an amalgamation of
functionalized MWCNTs (50 ml) and base fluid with a magnetic stirrer.
The authors observed that after 24 h, the sedimentation rate became
constant and slower. Aimed at determining the of separation of emul-
sion layer and sedimentation formation, the investigators reserved a
sample of Aluminium hydroxide oxide AlO(OH) NPs amalgamated with
water and biodiesel emulsion in a few clean and transparent test tubes
at steady condition, it was found that the fuels persisted to be stable for
more than one week [117].
The copper NPs were prepared by Kathiravan et al. [118] by the
M.E.M. Soudagar et al.
sputtering method. The NPs were dispersed in a water bath with 9.0%
of sodium dodecyl sulfate (SDS) which acts as an anionic surfactant
using an ultrasonication process. After 10 h it was observed that the NPs
were dispersed in water evenly even with some agglomerates. Longo
and Zilio [119] dispersed the mixed NPs of Al2O3–water (15 wt%) and
TiO2–water (25 wt%) in a nanofluid. A two-step process was carried
out, in the initial step, the NPs were mechanically stirred, and in the
next step, they were sonicated at 25 kHz for 48 h. The authors con-
cluded that the ultrasound treatment demonstrates an improved dis-
persion efficiency than simple mechanical stirring, and the stability of
both the nanofluids was found to be for more than one month. Sundar
et al. [120] used a small quantity of sulfuric acid (H2SO4) in the Fe3O4
and water nanofluid, the pH value was found to be 3. The approximate
sonication time of the emulsion fluid was 2 h. The author reported to
have found a uniform dispersion of NPs without any settlement, the
density of the nanofluids was measured at different locations in the
container. Parametthanuwat et al. [121] prepared Ag nanofluids by
means of an ultrasonic bath at 43 kHz for 3 h. The authors found the
NPs were stable up to a time period of 48 h. Harikrishnan and Kalai-
selvam [122] used precipitation method to synthesize the CuO NPs and
the ultrasonic vibrator was utilized for the preparation of CuO and oleic
acid nanofluids blends at a frequency of 40 kHz. Furthermore, the time
intervals of 30, 35, 40 and 45 min in the vibrator were changed for
various mass fractions of 0.5, 1.0, 1.5 and 2.0 wt%, respectively. The
authors reported that the dispersion of the NPs in the base fluid was
uniform with an excellent stability. It was also found that the CuO NPs
did not dissolve in the oleic acid; however, it was assumed that dis-
sociative adsorption might exist between oleic acid and CuO NPs.
3.4.2. Addition of surfactant/activator
This is a widely used method to control the NPs sedimentation. The
surfactant addition can the enhance the stability of NPs in aqueous
suspensions because it carries the characteristics to convert the surfaces
of NPs from hydrophobic to hydrophilic and conversely for non-aqu-
eous liquids. The addition of surfactants reduces the possibility of
coagulation, coalescence, and the surface tension. Surfactants have a
tendency to position themselves at the interface between the NPs and
the base fluid, where it set up a degree of continuity between the NPs
and fluids [123]. The magnetic NPs are generally coated with, surfac-
tants in order to avoid the agglomeration and oxidation from the at-
mospheric oxygen [124]. The various surfactants used in nanoparticles
are shown in Table 1.
The zeta potential causes a repulsive force between the suspended
particles in the base fluid, it can be avoided by the addition of enough
surfactant to sufficient coating, which avoids the electrostatic repulsion
and compensates the Van der Waals attractions [125–127]. To prepare
paramagnetic NPs stable, an appropriate surfactant should be chosen
during synthesis. The strong bonding between the functional group of
surfactants and the surface of NPs can make them stable. For magnetic
NPs, the distinctive surfactant includes trioctylphosphine oxides, oleic
acid, dioctylamine, and tryoctylamine [128]. However, at high tem-
peratures above 60 °C, the bonding between the surfactant and NPs is
broken, hence leading to the sedimentations [78]. The surfactant con-
verts the available surface energy of the particles so that the surface
Table 1
Various surfactants used in nanoparticles [36,37,41].
Type of surfactant Examples
Anionic Sodium dodecylbenzene sulfonate (SDBS), Sodium dodecyl sulfate (SDS), Magnesium laureth sulfate, Ammonium lauryl sulfate, Potassium lauryl sulfate,
Sodium stearate, Sodium pareth sulfate etc.
Cationic Cetyl trimethyl ammonium bromide (CTAB), Benzalkonium chloride, Cetrimonium chloride, Distearyl dimethylammonium chloride, etc.
Non-ionic Oleic acid, Poly vinyl pyrrolidone (PVP), Tween 80, Gum arabic (GA), Polyoxyethylene (10) nonylphenyl ether, Tween X-100, Stearyl Alcohol, Oleyl alcohol,
Rokanol K7, Rokacet O7, etc.
Amphoteric Lauryl betaine, Betaine Citrate, Lecithin, Sodium lauroamphoacetate, Hydroxysultaine, Cocamidopropyl betaine, etc.
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Energy Conversion and Management 178 (2018) 146–177
tension is lowered, and the Kelvin barrier shifts, allowing more particles
to escape the aggregation process and reducing the mean particle size.
Surfactants act as a link between NPs and base fluids which creates
continuity between NPs and base fluids. A variety of surfactants are
available depending on the charge on the head group of surfactants.
Therefore, the surfactants can be anionic (negatively charged) like alkyl
benzene sulfonate and cationic (positively charged) like quaternary
ammonium chloride, non-ionic (neutral, having strong affinity for polar
groups) like polyethylenated alcohols or amphoteric (both positively
and negatively charge) like sulfobetaine [112].
Addition of stabilizers can overcome the stability problem. During
the formulation process, the stabilizers are introduced. Fig. 3 elucidates
the nanofluid formulation process in three steps (a) The pure liquid is
prepared, (b) The base liquid is mixed with appropriate stabilizers (c)
dispersion of NPs into the base liquid. In the nanofluid research field, a
comparison is carried out between the heat transfer capability of na-
nofluids and the pure liquid, which is rather deceptive and responsible
for the perceived large data scattering. The loose stabilizers are shown
in Fig. 3(c) can change the values of viscosity, surface tension, and
wettability alone. The behavior of the nanofluids with respect to the
factors like flow and heat transfer are discussed below. The NPs and the
stabilizers are mixed together, and a proper comparison must be carried
out to differentiate the effect of stabilizer and NPs. A proper dispersion
process and strong bonding of stabilizer and NPs may eradicate the
loose stabilizers in the liquid phase, care should be taken so that there is
no breakage of the bonding. The other key issue includes the tem-
perature effect of the functionalized NPs. Many researchers have con-
firmed, a breakage of the bond will occur at elevated temperatures
affecting the stability however the bonding is strong at room tem-
peratures [74]. The negative aspect of using surfactants is that it may
generate fumes while heating. Also, the addition of an excess surfactant
may raise the thermal resistance, which may limit the development of
the effective thermal conductivity [129]. The factors for selection of
surfactants are elucidated in Table 2.
3.4.3. pH control (surface chemical effect)
The Nano-powder suspension stabilities in aqueous solution are
associated with their electro-kinetic properties. The strong repulsive
forces can be generated through the high surface charge density by
utilizing the finely dispersed suspension. The dispersion behavior NPs
can be well defined by the study of electrophoretic behavior with re-
spect to the measurement of the zeta potential and particle size. The
increase in zeta potential leads to a reduced particle size and stable
suspension [137,138]. A simple acid treatment of CNT suspension in-
creased stability in water. This was formed by a hydrophobic to the
hydrophilic conversion of the surface nature owing to the generation of
a hydroxyl (HO) group [139]. The factor in which the zeta potential is
zero due to the concentration of potential controlling ions is known as
isoelectric point (IEP). Thus, at the isoelectric point (IEP) the surface
charge density equals the charge density in the layer which is equal to
zero. Considering the nucleation and stabilization of NPs in the solu-
tion, for smaller particle size the repulsive energy decreases, hence the
zeta potential for the suspension stability will increase [140]. Lee et al.
[141] investigated the nanofluids with different pH levels using Al2O3
M.E.M. Soudagar et al. Energy Conversion and Management 178 (2018) 146–177

Fig. 3. Two-step method for nanofluid formulation (a) pure liquid, (b) pure liquid and stabilizer, and (c) nanofluids with loose stabilizers in the liquid (Adapted from
[74] with permission).

as NPs, the authors experimental data proposes that, at pH of 1.7 of the
nanofluid due to reduction in electric repulsion force, the agglomerated
particle size decreases by 18% and at a pH of 7.66 of the nanofluid was
observed, and the agglomeration size rose by 51%. The hydroxyl group
ions are produced at the surface of the Alumina when it is immersed in
water. The pH results in the relevant reactions to occur. At lower pH
value, the hydroxyl groups react with the positively charged H+ from
the water.
3.5. Stability inspection instruments
The stability inspection of nanofluids in biodiesel assesses the sig-
nificant data such as the chemical bonding, nanoparticle shape, and
size, dispersion and stability. However, various researchers have con-
ducted the characterization studies using different techniques explained
in this section and there is no absolute standard rule to use a particular
characterization technique. The characterization test for nanofluids is

Table 2
The factors for selection of surfactants and results.

Ref. Surfactant Nanoparticles Factors for selection and Results

[130] Sodium dodecyl sulfate (SDS) MWCNTs and fullerene (a) Aqueous solution of SDS is accepted universally for dispersing or suspending carbon
nanotubes, (b) The SDS hydrophilically modify the hydrophobic surfaces of MWCNTs
and fullerene and the repulsion forces between the suspended particles increase due to
increase of zeta potentials which is the surface charge of particles in fluid, (c) The
stability of the aqueous solution is observed for 800 h.
[40] Sodium dodecylbenzenesulfonate (SDBS) Graphene (a) SDBS acts as an anti-hygroscopic and anticaking additive, (b) The increase in the
concentration of surfactants, enhances the value of absorbance, above the critical
surfactant concentration, it was found that the dispersed state becomes increasingly
stabilized, and the growing kinetic barrier prevents the aggregation for a longer period,
(c) The surface electric charges of the surfactant are the major source of kinetic stability
of dispersion, (d) The stability of the aqueous solution was observed for a period of
8 weeks
[131] Cetyl Trimethyl Ammonium Bromide (CTAB) Magnalium and cobalt (a) CTAB acts as a cationic surfactant, (b) It forms an envelope on the surface of the
oxide particle and makes the surface as a negative charge, the particle sedimentation was
controlled.
[132] Sodium dodecyl sulfate (SDS) Cobalt ferrite (a) SDS surfactant significantly limits the agglomeration because of its high dielectric
constant with CoFe2O4 NPs, (b) The Magnetic measurement illustrated an enhanced
saturation magnetization coercivity and retentivity for SDS added to CoFe2O4 NPs
[133] Tetramethylammonium hydroxide (TMAOH) Magnetite It surrounds the magnetite particles with hydroxide anions and tetramethylammonium
cations to create electrostatic interparticle repulsion in an aqueous environment to
stabilize and avoid agglomeration of TMAOH in diesel
[134] Sorbitan Olieate Nano-Al (a) It reduces the coagulation and enhances the stability of metal n-Al NPs in n-alkane
and reduce the agglomeration, (b) The stable state observed for more than 24 h.
[98] Sorbitan monooleate Silver (a) it acts as A high suspension stability, good oil-soluble emulsifying agents, (b) A high
(hydrophilic–lyophobic balance) HLB value of the surfactant prevents agglomeration of
Ag NPs in diesel
[135] Dodecenyl succinic anhydride (DDSA) Cerium oxide (a) DDSA acts as a stable compound with adhesive property, slight odor and is totally
soluble in diesel, (b) The TEM images and the broader peaks indicated the reduction in
particle size with the addition of DDSA, the smaller particle size helps to reduce the
chance of aggregation of NPs, (c) Zeta potential of nanofluids can be improved by the
addition of surfactant and a higher zeta potential indicates a better stable dispersion, (d)
Reduction in HC was observed with higher concentration of DDSA.
[22] Oleic acid Zirconium-Cerium (a) The stability of modified diesel nano-suspension was found to be maximum at a
oxide particle loading of 10 ppm of oleic acid as surfactant with minimum settling effect, as the
concentration of oleic acid increases the agglomeration is reduced, (b) The stability of
zirconium-cerium oxide NPs and diesel fuel with oleic acid as surfactant was observed
for 1344 h
[136] Sorbitan monostearate (Span80) and Polyethylene Aluminium oxide (a) The Span80 is insoluble in water and soluble in organic solvents, (b) It acts as water/
sorbitol ester (Tween80) oil type emulsifier, (c) stability was observed for more than one year.
[39] Sodium dodecyl sulfate (SDS) Titanium dioxide (a) Nanofluids with surfactant would have a rising rate of precipitation, homogenized
suspension, enhancement in the absorbance of UV, less clustering and agglomeration, (b)
Stable suspension with the maximum thermal conductivity for further applications
within 1 month.

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M.E.M. Soudagar et al.
accomplished by the methods such as UV–Vis spectroscopy, SEM, XRD,
TEM, zeta potential analysis, TGA and DLS.
3.5.1. UV–Vis spectroscopy
The absorption spectroscopy in the ultraviolet–visible spectral re-
gion is investigated by using the ultraviolet (UV)-visible spectroscopy
(vis) or ultraviolet–visible spectrophotometry (UV–Vis), usually with a
wavelength ranging between 200 and 900 nm. The method uses the
visible light and the light in the adjoining edges (near UV and near IR)
ranges. The visible range directly affects the perceived colours of the
chemicals used during the absorption. The molecules experience elec-
tronic transitions in the region of the electromagnetic spectrum. The
instrument used for characterization of colloidal stability of the dis-
persions is known as the Ultra Violet–Visible spectrophotometer, where
the most prominent features of this device are its suitability for all base
fluids. Normally, the suspension stability is determined by evaluating
the sediment volume vs. the sediment time. However, this technique is
incompatible for nanofluid dispersions with high concentrations and
specifically for carbon nanotubes (CNT) solutions, these dispersions are
obscured to distinguish the sediment visibility [141]. The following
steps are used in the characterization process: The first step is to obtain
the peak absorbance of the dispersed NPs at a highly diluted suspension
by scanning. The second step is to prepare a standard to suit the linear
relation to various diluted concentrations usually (0.01–0.03%), be-
cause of the linear relationship absorbance and concentration of the
suspension. The desired concentration of nanofluid is prepared fol-
lowed by relative stability measurement and kept for few of days.
Whenever required, the relative stability of supernatant concentration
will be determined by using a UV–Vis spectrophotometer [142–144].
However, this method is not helpful for highly concentrated nanofluids
or dark in colour, because the high concentration of nanofluids results
in high absorbance of incident light and reduce the intensity of scat-
tered light which decreases the superiority of data [145].
3.5.2. Zeta potential analysis
The electric potential in the interfacial double layer at the position
of the slipping plane, which is relative to a point in the large quantity of
fluid apart from the interface, known as zeta potential. It is the potential
CeO2-MWCNTs [57] Cerium Oxide [152]
CaO eggshell [18] Ti(SO4)O nano-catalyst [26]
Fig. 4. SEM Images nanofluid blends (Adapted from [57,152,20,18,26], and [153] with permission).
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Energy Conversion and Management 178 (2018) 146–177
difference between the static layers of fluid coupled to the dispersed
particle and the dispersion medium [77]. The colloidal dispersed par-
ticles stability is influenced by zeta potential or their surface charge. If
the suspensions have a zeta potential of more than 60 mV, this shows
excellent stability, above 30 mV they are physically stable whereas the
suspension below 20 mV, this shows constrained stability, and a pro-
nounced agglomeration is undergone by the particles below 5 mV
[83,146]. Many researchers studied the zeta potential of nanofluids to
find their stability. Singh et al. [147] dispersed Al2O3 NPs produced by
vapor condensation method in ethylene glycol and water. The Al2O3
and water nanofluids were stabilized through the electrostatic process,
a few drops of hydrochloric acid were mixed to sustain the zeta po-
tential, the value was found to be 58.7 mV. They concluded that the
nanofluids were stable for a long period. Suganthi and Rajan [148]
produced ZnO NPs by chemical precipitation process using zinc nitrate
hexahydrate as a precursor. Ultrasonication (750 W and 20 kHz) pro-
cess was used to prepare the zinc oxide and water nanofluid for 3 h and
sodium hexametaphosphate (SHMP) was used as a dispersant for sta-
bilization. A measured quantity of ZnO in the ratio of five was added to
the surfactant solution in a ratio of one and homogenized for 20 min at
7000 rpm. The authors observed, a higher zeta potential and a higher
colloidal stability of nanofluid dispersions.
Few limitations of zeta potential include the electrode polarization
and degradation which is caused due to the movement of highly con-
ductive ions, hence it results in the inability of the zeta potential in the
analysis of highly conductive nanofluids, enough light scattering ele-
ments are required to find the zeta potential of nanofluids of very low
concentrations. Likewise, it is not suitable for high concentration as NPs
since it absorbs a maximum of the incident light and weakens the in-
tensity of scattered light. Furthermore, for precise zeta potential cal-
culations, the properties of the nanofluids must be known to avoid
multiple scattering [149,150].
3.5.3. Transmission Electron Microscopy (TEM) and Scanning Electron
Microscope (SEM)
Scanning Electron Microscope (SEM) is a category of the electron
microscope in which images of the substances are formed by scanning
the surface with the aid of a focused beam of electrons. The data about
Graphene nanoplatelets [20]
Calcined seashell [153]
M.E.M. Soudagar et al. Energy Conversion and Management 178 (2018) 146–177

MgO nanoparticle [154] Pristine C60 GNPs [155] Aluminium Oxide [156]
Fig. 5. TEM Images of Nanoparticles (Adapted from [154,155], and [156] with permission).

the substance surface topography and composition is produced by the
interaction of electrons with the atoms present in the sample and TEM
is recognized as the most important tool to determine the size dis-
tribution and the morphology of the synthesized NPs. TEM and SEM are
highly advantageous tools to find the shape, distribution, and size of the
NPs. Min-Sheng Liu et al. [151] used a method to attribute the standard
SEM/TEM micrographs of Cu NPs. Firstly, the stable solution form of Cu
nanofluid is prepared. Secondly, a droplet of the prepared solution was
dropped on to the surface of sticky tape of the SEM specimen holder and
finally, for the solution to adhere to the sticky tape, it is heated in a
vacuum oven or dried in natural air. Hence, the solid Cu particles were
obtained and finally, the Cu NPs are coated with Au and Pd and the
mixture was sent to the SEM chamber for a picture. Fig. 4 illustrates the
characterization test of various nanoparticles blended with the diesel-
biodiesel emulsion, where the Scanning Electron Microscope (SEM)
images of CeO2-MWCNTs blended with waste cooking oil biodiesel, Ti
(SO4)O nano-catalyst with used cooking oil (UCO) to produce biodiesel,
GNPs blended into jatropha biodiesel, waste mussel used as catalyst in
synthesis of sunflower oil biodiesel, CeO2 used as additives in Jatropha
biodiesel, and hydrated calcined Cyrtopleura-costata seashells used as
catalyst for synthesis of palm oil biodiesel. Fig. 5 shows the Transmis-
sion Electron Microscopy (TEM) images of the magnesium oxide NPs,
pristine C60 graphene oxide NPs and aluminium oxide NPs.
of nanofluids depends on the following parameters: (1) the particle size
is one of the most significant parameters which affects the thermal
conductivity of nanofluids. The NPs can be synthesized a in many sizes,
from the range of 5 and 100 nm, (2) the particle shape consists of cy-
lindrical and spherical particles. For vast length to diameter ratio, the
cylindrical shapes are used, (3) the particle material and base fluid play
vital roles in the thermal conductivity of nanofluids. The oxides of NPs
such as SiO2, CuO, TiO2, Al2O3, Fe2O3, etc., CNTs and metals such as
Cu, Ag, Au, etc. mixed in base fluids such as engine oil, ethylene glycol,
propylene glycol, water, etc. resulted in the increase in thermal con-
ductivity of the blend, and (4) the thermal conductivity of the base fluid
and particle depends on the temperature. Fig. 6 illustrates the above-
discussed factors that affect the thermal conductivity.
The two significant mechanisms in the improvement of thermal
conductivity of nanofluids are the liquid layering around NPs and the
Brownian motion of NPs. The two mechanisms work perfectly when the
particle size is reduced and enhances the thermal conductivity. The
clustering of NPs is useful in enhancing the thermal conductivity.
However, the excessive clustering creates a reverse effect on the
thermal conductivity due to related sedimentation [162]. Karthikeyan
et al. [163] used simple precipitation technique to study the synthesis
of copper oxide NPs with an average diameter of 8 nm, as well as
thermal properties of the suspensions in water and ethylene glycol as

3.5.4. Infrared spectroscopy

The infrared spectroscopy (IR-Spectra) method is commonly used
for the characterization of a diversity of NPs that includes metallic NPs,
CNTs, and some organic NPs such as core-shells and hybrid NPs. The
Fourier transform infrared spectroscopy (FTIR) is used for assessing the
functional groups existing inside a colloidal suspension of NPs. The
vibrational signatures of the elements present in the neighboring media
of the NPs are found out by IR-spectra. For instance, the metallic NPs
production revealed a complex medium of biological extracts such as
proteins and metabolites via functional groups of carboxylic acids, al-
cohols, aldehydes, ketones, and amines [157,158]. Additionally, the IR
spectra also provide information on the size of the NPs. The IR spectra is
also suitable for characterizing carbon nanomaterials like CNTs, carbon
dots (CDs), graphene quantum dots (GQDs), nano-diamonds [159]. The
characterization molecular nature of a substance is analyzed using IR
spectroscopy for the core-shell NPs such as Au@TiO2, Ag@ZrO2,
Ag@TiO2, Au@ZrO2, and Ru-Pt through investigating the features as-
cribed to Ti-O-Ti and Zr-O-Zr stretching modes [160].

3.6. Thermophysical properties, combustion and evaporation characteristics

of nanofluids

3.6.1. Thermal conductivity of nanofluids

The investigators provided an extra contemplation towards the Fig. 6. Factor affecting the thermal conductivity of nanofluids the (Adapted
thermal conductivity of nanofluids. The effects on thermal conductivity from [161] with permission).

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M.E.M. Soudagar et al.
base fluids. The 1% volume concentration of CuO NPs were dispersed in
the base fluid. The authors stated that with the increase in the particle
size and monodispersity of nanoparticles, the thermal conductivity in-
creases. Furthermore, a study of the influences of NPs and cluster size, a
polydispersity of NPs on thermal conductivity of the base fluid was
conducted. Minakov et al. [164] investigated the dependencies of the
viscosity of nanofluids of liquid Ar with Al and Li NPs for the NPs size
ranging from 1 to 4 nm and 1–12% of concentration volume. The au-
thors observed that, when there was a decrease in the NPs size, the
viscosity of nanofluids increases and the viscosity increase depends on
materials of the NPs. Farboda et al. [165] studied the thermal con-
ductivity of effect of three water-based nanofluids containing a high
aspect ratio fillers of CNTs, Ag nanowires, Cu nanowires which were
measured by transient hot-wire technique. The CNT nanofluid becomes
more stable when they are functionalized where the enhancement of
thermal conductivity of the nanofluids depends on the length of CNTs.
Hwang et al. [166] reported that in a circular tube with constant
heat flux, the convective heat transfer coefficient and pumping power
in terms of pressure fall is enhanced due to the addition of Al2O3 NPs in
water. The authors proposed Darcy's equation to be the most suitable
for finding the pressure drop initiated by the nanofluid and it could be
avoided by treating the nanofluid as a homogenous liquid. For a volume
concentration of 0.3% of NPs, the improvement in the convective heat
transfer coefficient was 8%. Besides that, they also investigated the
Brownian diffusion, thermophoresis, and non-uniform shear rate and
studied the energy transfer by the NPs dispersion, the thermal con-
ductivity in heat transfer and the movement of NPs due to the different
viscosity. Mintsa et al. [167] studied the effects of particle volume
fraction and size, the temperature on the thermal conductivity of Al2O3-
water and CuO-water nanofluids. The researcher concluded that the
when the volume concentration of the particle increase and when the
particle size decreases, the effective thermal conductivity increases.
Then at high temperatures, there was a relative increase observed in the
thermal conductivity. Moosavi et al. [168] investigated the effects of
zinc oxide NPs blend in ethylene glycol and glycerol as base fluids. The
dispersion of the nanofluids were improved by adding the ammonium
citrate dispersant. The volume fraction and temperature were used to
find the thermal conductivity of ZnO nano-fluids. It was observed that,
with the addition of 3% by vol. of ZnO NPs increased the thermal
conductivity of ZnO-ethylene glycol by 10.5% and ZnO-glycerol by
7.2%. Yu et al. [169] used the graphene nanosheets to produce ethylene
glycol nanofluids developing a simplistic technique. The thermal con-
ductivity of the base fluid increased by dissolving graphene nanosheets
in it and the thermal conductivity enhanced by 86% for 5.0 vol% gra-
phene NPs dispersion. The authors concluded that due to the graphene
and graphene oxide's two-dimensional geometry, stiffness and high
aspect ratio helped to increase the thermal conductivity and thermal
transport property of the base nanofluid. Cuenca et al. [170] studied the
thermal conductivity on the effect of ammonia and water (ammonia
mass fractions from 0.10 to 0.50) at temperatures between 293.15 K
and 313.15 K respectively. The authors concluded that the thermal
conductivity of ammonia and water mixtures decreased with the am-
monia mass fraction and increased with the rise in the temperature.
Hajjar et al. [171] used the modified Hummers method to synthesize
graphene oxide (GO) nanosheets which resulted in the formation of
homogeneous and stable graphene oxide-water nanofluids. The study
also investigated the temperature and effects of NPs concentration on
the thermal conductivity. The authors concluded that the enhancement
ratio is 33.9% at a temperature of 20 °C and 47.5% at a temperature of
40 °C with the loading of 0.25 wt% of GO nanosheets. Hence, the de-
pendence of temperature in the measured range is evident. Megatif
et al. [172] used TiO2–CNT hybrid nanofluids under the laminar flow to
investigate the effect of convective heat transfer coefficient of the shell
and tube heat exchanger (HE). The effects of mass fraction and the
temperature on the convective heat transfer were studied. The thermal
conductivity of the hybrid nanofluid was found to be 21.5%, which was
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Energy Conversion and Management 178 (2018) 146–177
higher than the base fluids.
3.6.2. Evaporation rate
Evaporation rate is the rate at which the material will vaporize
(evaporate, change from liquid to vapor) when compared to the rate of
vaporization of a specific known material. The factors affecting the rate
of evaporation are temperature, surface area, and humidity. Gan et al.
[173] studied the evaporation characteristics of ethanol and n-decane
nanofluids under natural and forced convection, the NPs aggregation
effect on evaporation rate of droplets were investigated using numerical
modeling and ethanol and n-decane are considered as base fuels at
different concentrations of n-Al. The authors found that the droplets of
pure fuel follow D2 Law using free and weak forced convection while
the evaporation process by n-Al particles suspended in ethanol droplet,
follows the D2 law with only natural convection. Also, it is reported
that at 300 K, there was a reduction of 30% to 50% in the droplet
evaporation rate. Mehta et al. [174] found an enhanced evaporation
rates and an improved flame sustainability of Al and Fe in comparison
with boron laden diesel fuel which resulted in the agglomeration of
unburnt NPs of Al and Fe in a diesel. The diesel droplet with NPs of Al
and Fe ignited for an extended time which delivered longer flame
sustainability. Javed et al. [175] studied the evaporation rates of hep-
tane droplets containing n-Al particles hanging at silicon carbide fiber
at a temperature range of 100–600 °C. An analysis was carried out to
investigate the shell formation during evaporation and its effects on
evaporation rate. The authors revealed that the bubble formation of
heptane droplets was reduced by adding n-Al, and with the addition of
n-Al, there is the formation of highly porous structure up to a tem-
perature of 100–300 °C due to small agglomerates which are re-
sponsible for the improvement in evaporation rates of n-Al heptane
droplets.
3.6.3. Ignition delay (ID)
The time period between the beginning of fuel injection to the be-
ginning of combustion inside the combustion chamber is known as ig-
nition delay and is found out by pressure crank angle diagram [176].
Ignition-delay (ID) is one of the important combustion characteristics in
determining engine efficiency, diesel emissions, and smoothness of
engine operation. It is influenced by the physical processes (e.g., fuel
droplet breakup rate, vaporization rate, spray penetration, and fuel-air
mixing) and chemical processes (e.g., the precombustion reaction of the
fuel, air, and residual gases). Many investigators from their experi-
mental work observed that nano-additives mixed with fuel run engine
have a short ignition delay in comparison to that of neat diesel thus
providing an improvement in combustion efficiencies [128,177,178].
Tyagi et al. [179] conducted a hot-plate ignition probability test and
witnessed that, by adding aluminium/alumina NPs to the diesel fuel
results in a significant enhancement in the ignition temperature and
shorter ignition delay. Kannan et al. [128] investigated the combustion
characteristics of CI engine, they revealed that the FeCl3 NPs mixed
with waste cooking palm oil biodiesel shortens the ignition delay as a
result of better atomization of fuel and proper A-F mixture. Wickham
et al. [180] investigated the effect of NPs addition with fuels on ignition
delay (ID) and found the reduction in ID of JP-10 and JP-5. Allen et al.
[181] and Jackson et al. [182] found similar results when n-dodecane
and ethanol are used with aluminium NPs. Lenin et al. [183] in-
vestigated the effect of manganese oxide (MnO) and copper oxide
(CuO) NPs with diesel fuel. The inclusion of diesel with NPs causes a
substantial reduction in ignition delay which was largely responsible
for providing enhancement in combustion efficiencies. Jong Boon et al.
[184] defined ID of a droplet in their perspective as the time interval
between the start of heating and the start of ignition. The start of ig-
nition was determined when the lowest value of droplet gradient
temperature (i.e., dT/dt ≥ 0) and the first successive point of inflection
for second derivative of droplet gradient temperature (i.e., d2T/
dt2 = 0) are reached. The results revealed with the inclusion of CeO2,
M.E.M. Soudagar et al.
the ID of the diesel fuel is shortened by up to 48.4% when the fuel is
dosed with nanoparticles at 0.01% and 0.1%, while graphene oxide
reduced ID by 38.2% and 0.1% aluminium oxide reduced ID by 35.1%.
The reason is that the evaporation rate increases, because of additional
heat being absorbed through radiation by the NPs that are distributed
within the liquid droplet and additional oxygen is readily available to
form higher concentrations of combustible blends due to fuel-borne
oxygen content provided by mixing of the NPs oxides. The authors
concluded that a significant reduction in the ID seen for all the dosed
fuel droplets when compared with undosed diesel fuel droplets.
3.6.4. Secondary atomization and micro-explosion
The method of splitting larger fuel droplets into smaller and finer
droplets of fuel is known as secondary atomization, due to the micro-
explosion and secondary atomization phenomenon, the condensed NPs
in the water droplet fragment along with the fuel and reacts with the air
efficiently, due to their high surface area to volume ratio [185]. Micro-
explosion is caused by heterogeneous nucleation, where nucleation
occurs at the droplet surface [184]. The secondary atomization study on
the role of nano-CeO2 fuel mixtures promotes enough mixing of fuel
with air and thus can effectively decrease fuel-rich zones, reducing the
generation of ethane, the precursor of PM generated during combus-
tion. Moreover, due to the exceptional oxygen storing capacity of CeO2,
it can allow oxygen to enable the additional oxidation of soot. This
micro-explosion encourages the secondary atomization of fuel droplets
towards ultrafine granularities and thus reduces the physical prepara-
tion period before ignition [186].
Sadhik Basha et al. [187] explained the microexplosion phenom-
enon in the water-biodiesel emulsion fuel using alumina NPs in Fig. 7.
The phenomenon occurs due to the volatility difference between water
and biodiesel. Once the alumina NPs encased in water droplet biodiesel
emulsion are fuel exposed to high pressure and high-temperature en-
vironment in the engine cylinder, the water droplets will absorb the
heat rapidly due to the lower boiling point of water in comparison to
the biodiesel. This effect leads to the explosion of water droplets
through the surrounding oil layers called microexplosion. Conse-
quently, a number of secondary fuel droplets of very fine size are
formed, which, in turn, evaporates quickly. Therefore, the formation of
secondary droplets in the combustion chamber enhances the fuel-air
mixing in the presence of potential NPs. Sadhik et al. [188] revealed
that due to the collective effects of micro-explosion and secondary
atomization phenomenon related with the CNT-JME emulsion fuels, the
level of toxic pollutants in the exhaust gases were significantly reduced
and combustion rate was improved in comparison with the neat JME
[188]. Jong Boon et al. [184] observed the micro-explosion for GNPs,
Al2O3, and CeO2. The authors observed that the GNPs demonstrated a
better micro-explosion compared to Al2O3, and CeO2, the reason is due
to the GNPs exhibited a weaker van der Waals forces bonding, whereas
Al2O3 and CeO2 are held together by the stronger ionic bonds, giving
the latter two higher resistance to thermal decomposition. The in-
creased micro-explosion frequency of GNPs can speed up the combus-
tion process in diesel engine. The addition of CNTs in water and diesel
Fig. 7. Schematic of microexplosion and secondary atomization effect of the biodiesel emulsion fuel (Adapted from [187] with permission).
157
Energy Conversion and Management 178 (2018) 146–177
emulsion fuels increases the micro-explosion phenomenon. Enhance-
ment in BTE was observed for LGO nano-emulsion test fuel when
compared to neat LGO due to better atomization and rapid evaporation
rate of fuel due to the large surface area to volume ratio of CeO2 NPs
[189].
3.6.5. Pressure rise and peak pressure
The combustion process of a distinctive diesel engine is partly pre-
mixed combustion and partially diffusive. These phenomena are com-
plex mechanisms to recognize and they essentially depend on the fuel,
fuel injection timing, compression ratio, engine load, temperature and
intake boosting the pressure. The cylinder pressure is a function of the
crank angle during the end of the compression stroke and throughout
the initial part of the expansion stroke. The peak pressure rise rate is a
vital design parameter that reflects the dynamic limits to be resisted by
various engines components. Sivakumar et al. [190] investigated Al2O3
NPs and pongamia methyl ester (PME). The author reported that the
Al2O3 blends increase the cylinder pressure compared to DF and bio-
diesel. The Al2O3 large surface area to volume ratio and abundant
oxygen content improves cylinder pressure. Shaafi et al. [191] reported
that the addition of alumina NPs to diesel and soyabean biodiesel
blends resulted in an appreciable increase in cylinder pressure from 7°
to 8° after TDC when compared with diesel and soyabean biodiesel
blends. The authors stated that the improvement in cylinder pressure
was attributed to higher exposure of a surface area of NPs and rich
inherent oxygen content of soyabean biodiesel. In addition, better air
and fuel mixing further promotes the rapid burning of fuel inside the
cylinder. El-Seesy et al. [113] reported the peak pressure reduced at
high engine load and speed, which could be due to the increase in
friction losses resulting in reduced heat release rate. The addition of
Al2O3 additives into JB20D blended fuel leads to an advanced position
of Pmax. This was accredited to enhanced evaporation rate and im-
proved A-F mixture resulting in shortened ignition delay. The maximum
advance in the position of peak pressure occurs at Al2O3 additives dose
level of 20–30 mg/l. Furthermore, the maximum value of the percen-
tage increase of the cylinder pressure is about 4.5% at Al2O3 additives
concentration of 30–40 mg/l as compared to JB20D mixture fuel. Basha
and Anand [23] carried out experimental studies on the performance
and combustion characteristics of a diesel engine, using carbon nano-
tubes blended water-diesel emulsion fuels. The authors stated that the
cylinder peak pressure is lower for the CNT blended water-diesel
emulsion fuels, due to the reduced ignition delay when compared to
that of the water-diesel emulsion fuel. At full load, the cylinder peak
pressure for the D2S5W and D2S5W50CNT is observed to be 75.4 and
71.2 bar, respectively. Chen et al. [192] varied the cylinder pressure of
nanoparticle-diesel fuel blends at 50% and 100% engine loads from 10°
bTDC to 10° aTDC. All the NPs-diesel fuel blends illustrated significant
improvement in the cylinder pressure and ignition delay. The peak
combustion pressure explains an inverse relation with compression
pressure and thermal conductivity. The highest pressure achieved by
CNT was DC25 at 6.1 bar and 7.2 bar for engine loads 50% and 100%,
respectively. Al2O3 has higher thermal conductivity of 30 W/m∙K
M.E.M. Soudagar et al.
showing highest pressure observed by DA100 resulting in pressure of
6.4 bar at 50% engine load and 6.8 bar at 100% engine load. Ramesh
et al. [193] investigated the effect of peak pressure by using Poultry
litter biodiesel (PLOME) and alumina NPs. The B20PLOME and
B20PLOME30A showed a higher peak pressure than diesel. At full load
condition the B20PLOME blend showed an increase in peak pressure
due to higher ignition delay which arises due to premixed combustion.
4. Nano-additives in the diesel-biodiesel fuel blend
The literature review of the effect of various biodiesel and diesel
fuel blends, with nano-additives on engine performance and emissions
(metal-based, organic, originated, antioxidizing, non-metallic, carbon
nanotubes, water emulsion fuels) are discussed in this section.
Yuvarajan et al. [194] investigated the effects of titanium-oxide (TiO2)
NPs and mustard oil methyl ester (MOME). TiO2 NPs of the average size
of 50 nm was characterized by X-ray diffraction technique, 100 and
200 ppm of titanium oxide (TiO2) blended with different conc. of
MOME, the results revealed that due to the oxygen content in MOME,
MOMET100 and MOMET200 the HC, CO was reduced, the longer delay
period of biodiesel resulted in higher fuel ignition temperature, hence
NOX emissions were higher than diesel at all loads. Ramesh et al. [193]
conducted an investigational work on a CI engine using poultry litter oil
(B20) biodiesel blend and alumina (Al2O3) nanoparticles as an additive,
with 30 mg/l as the dosage value. The test results revealed that the
combustion and performance characteristics were improved with B-20
biodiesel blend (in comparison with and without nanoparticles). The
substantial reduction in CO, UHC and an increase in NOX emissions
were attained while using the B20 biodiesel blend in comparison with
the diesel. Nevertheless, there was a remarkable reduction in CO, UBHC
and NOX emissions for the B20 and nanoparticles additives in com-
parison with the B20 biodiesel blend and diesel [193]. The combination
of zinc and calcium oxide metal additives (zinc doped calcium oxide)
was studied by Kataria et al. [195] on waste cooking oil (WCO) bio-
diesel. The ideal condition for base-catalyzed transesterification of
WCO was found to be 12:1. Tests were conducted on CI engine running
at a constant speed of 1500 rpm, an injection pressure of 200 bar,
compression ratio 15:1 and 17.5, and varying engine load. B40 amongst
all the fuels tested having C.R 17.5:1 exhibited maximum thermal ef-
ficiency at full load. The cleaner and complete combustion of the fuel
resulted in a decrease in the emission of HC and CO due to the in-
creasing concentration nano-additives in the blends. Sajith et al. [34]
conducted experimental studies on Jatropha and commercially avail-
able cerium oxide (CeO2) nanoparticles additives (10–20 nm size). The
flash point of biodiesel increased with the presence of the CeO2 NPs.
The viscosity of biodiesel was found to increase with the addition of
cerium oxide nanoparticles and the BTE increased with the dosing level
of nanoparticles.
Some authors investigated the addition of carbon nanotubes (CNTs)
in dosages of 100–300 ppm into diesel-biodiesel fuel emulsion and
achieved reductions in BSFC [15]. Praveen et al. [85] investigated the
performance and emission characteristics of a single cylinder diesel
engine by using blends of Calophyllum Inophyllum biodiesel and TiO2
nano-additives and exhaust gas recirculation (EGR). The Calophyllum
Inophyllum (B20) + 40 ppm of TiO2 NPs were dispersed into a B20 fuel
to prepare the B2040TiO2 fuel sample. The experiments were con-
ducted on diesel engine by using B20, B2040TiO2, B20 + 20% EGR,
B2040TiO2 + 20% EGR fuel samples at various load conditions. The
authors concluded that when Calophyllum Inophyllum biodiesel blend
(B20) is added with the of TiO2 nanoparticles and EGR, the engine
performance is enhanced and reduction in emissions is observed as
compared to other fuels. Sabet Sarvestany et al. [196] reported that the
nanoparticle additives, even at low concentrations have significant in-
fluence in diesel engine characteristics. Fe3O4 nanoparticles in the
concentrations of 0.4 and 0.8 vol% were dispersed in the diesel fuel.
NOX and SO2 emissions reduced, while CO emissions and smoke opacity
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Energy Conversion and Management 178 (2018) 146–177
strikingly increased with increase in the dosing level of nanoparticles.
The effects of magnetite ferrofluid + methyl esters of mustard oil
(MEMO) were investigated to evaluate the influence on performance
and emission characteristics. Magnetite ferrofluid can be removed from
exhaust gas unlike any other additives and releases a large quantity of
heat at higher combustion temperature, which decreases the ignition
delay and NOX emissions. The experiments carried out suggests that, by
addition of (1% by volume) of magnetite ferrofluid to MEMO, 5.122%
increase in BTE and 4.72% reduction in BSFC were observed. Further,
7.74, 5.8, and 2.66% and reductions in NOX, HC, and CO emissions
were also observed [197]. Caulerpa Racemosa oil methyl ester
(CROME) blended with ferrofluid. Reacting Iron III (FeCl3) and Iron II
(FeCl2) in aqueous ammonia (H5NO) solution to synthesize nano-fluid,
magnetite ferrofluid (Fe3O4) is formed. CROME (98.7%) + Fe3O4
(1%) + (CH3)3NOH (0.3%) by volume were tested on CI engine. The
engine performance revealed an increase in BTE, and reduction HC, CO,
NOX, SO2, and smoke [198].
Harish Venu et al. [42] studied the effect of biodiesel-ethanol (BE)
blends in a CI engine using TiO2 (Titanium oxide) nanoparticle, ZrO2
(Zirconium oxide) nanoparticle and DEE (Diethyl ether) additives.
Biodiesel (80%) + ethanol (20%), a blend of BE with 25 ppm of tita-
nium oxide nanoparticle (BE-Ti), a blend of BE with 25 ppm ZrO2 na-
noparticle (BE-Zr) and a blend of BE with 50 ml DEE (BE-DEE). With the
addition of titanium nanoparticles, NOX, HC and smoke were increased,
whereas BSFC and CO decreased. As for the addition of ZrO2 nano-
particle increased the BSFC and HC emissions and lowered CO, CO2 and
smoke emissions in comparison with BE blends. The heat release rate
improved using DEE and increased HC and CO emissions, while the
BSFC, NOX, and smoke reduced. Srinivasa Rao et al. [117] studied the
performance and emission characteristics of Aluminium oxide hydro-
xide (AlO(OH)) nanoparticles as a fuel additive in Jatropha oil tested on
Direct Injection Compression Ignition (DICI) engine. The biodiesel
emulsion fuels, BD5W: Blend of 93% biodiesel + 1% Span80 + 1%
Tween80 + 5% water, and BD10W: Blend of 88% biodiesel + 1%
Span80 + 1% Tween80 + 10% water were dispersed in 25, 50 and
100 ppm dosage of nanoparticles. The authors revealed that the BTE
decreases and NOX emissions increased. However, the performance and
emission characteristic were improved by adding water and nano-
particles. Vinukumar et al. [199] investigated the engine performance
by addition of coconut shell (CS) nanoparticles which were prepared
using mechanical ball milling process. The average particle size of co-
conut shell nanoparticles was 20 nm in diameter and Pungamia pinnata
was used as base fuel. Without modification in the engine design, the
performance and emission test were conducted in single cylinder diesel
engine with fuel ratio of 100%DF, 20%BD80%DF, and 20%BD80%DF.
The NOX, HC and CO emissions reduced and the BTE improved. The
authors concluded that the coconut shell (CS) can be used as nano-
additive in diesel. Yang et al. [200] introduced a novel emulsion with
nano-organic fuel additives. The glycerine was used as the organic
nano-additive with 10–15% water content, which was transparent and
light green with a high stability. The results were compared to neat
diesel and the diesel-emulsion fuel. The results revealed that the phe-
nomenon of micro-explosion of the nanosized water drops in the
emulsion fuel can accelerate fuel evaporation and the mixing process
with air, decreasing the total combustion duration. When 10% emulsion
fuel was used, the BTE of the engine was enhanced considerably by
14.2% compared to pure diesel, and there was a reduction in NOX
emissions by 30.6%.
4.1. Physicochemical properties of nano-additives in diesel-biodiesel fuel
blend
Numerous investigators studied the properties of nano-additive fuel
blend and its effect on various properties such as calorific value, flash
point, density, viscosity, cetane number, etc. The motive behind the
addition of metal based nano-additives to the diesel/biodiesel is to
M.E.M. Soudagar et al. Energy Conversion and Management 178 (2018) 146–177

improve the performance of the engine by enhancing the properties of
fuel. The addition of NPs to diesel/biodiesel blends improved the ca-
lorific value and cetane number and it reduced the sulfur content in the
fuel. Table 3 illustrates the summary of properties of nanofluids used in
the CI engine by most recent studies. The inclusion of Al2O3, CNT,
CeO2, Al, Ag and graphene NPs with neat biodiesel lowered the flash
point values while they increased the viscosity and density values
[14,24,128]. There was an increase in the calorific value of neat bio-
diesel with addition of CNT, graphene and Al NPs [128]. Addition of
ZnO NPs increased the flash point, viscosity, density and calorific value
of the fuel. Whereas, the addition of Mn, Mg, Al NPs in diesel-biodiesel
blends reduced the flash point values [13,29,60]. Gumus, Soner, et al.
[55] investigated the physicochemical properties of diesel-biodiesel-
NPs emulsion. The authors revealed that, the pH of the nano-diesel
greatly influences the dispensability of Al2O3 and CuO nanoparticles in
the diesel. The suspension for pH 7.7 of both Al2O3/diesel and CuO/
diesel produces good stability. The nanoparticles of mass concentration
25 ppm to 100 ppm in diesel, results in no significant change in the
kinematic viscosity, CFFP, sulfur, density, and distillation character-
istics. An increase in flash point and cetane index was observed with the
addition of 50 ppm of NPs, EN 590 diesel fuel standards were com-
parable with the results from using the Al2O3/diesel and CuO/diesel
nano-diesel blends. Zilch ignition is observed for standard diesel, at
temperatures lower than 475 °C, and 100% ignition above 515 °C. The
AITs of CuO/diesel nano-diesels are remarkably higher than the Al2O3/
diesel nano-diesel. The maximum AITs for Al2O3-nano-diesel were
505 °C at 100% ignition, while CuO/diesel nano-diesels exhibits 510 °C
at 100% ignition. The author concluded that Al2O3 and CuO nano-
particle additives have better characteristics to enhance fuel properties
like flashpoint, cetane number, and ignition. Tan et al. [201] conducted
the physiochemical fuel analysis on the emulsion fuels to find the
emission and their effect on the performance of a diesel engine. The
parameters such as density, total heating value, specific gravity, kine-
matic viscosity, API gravity, cloud point, cetane number, flash point,
and pour point were investigated. The water content in bioethanol (5%)
affected the physiochemical properties of the diesel-biodiesel-bioe-
thanol emulsions, 44 MJ/kg of heat was released by burning the diesel-
biodiesel-bioethanol emulsions, and it was 21% higher than the pure
biodiesel heating value and 2% less than the diesel fuel. Hence, the
above-mentioned physiochemical properties of diesel-biodiesel-bioe-
thanol emulsions were lower than the diesel and biodiesel. Sajeevan
et al. [135] investigated the physicochemical properties of base fuel and
nanoparticle added modified fuel with respect to standards provided by
ASTM under identical laboratory conditions. For 80 ppm of nano-
particle added, the flashpoint was tested, it was found to be higher with
the presence of nano-additives. The surfactant DDSA was used to obtain

Table 3
Properties of nano additives fuel blend used in diesel engine applications.

Ref. Fuel Kin. viscosity Density Sp. gravity Flash Fire Cetane Calorific Cloud Pour Total acidity
(cst) (kg/m3) point point number value (kJ/kg) point (°C) point (mg of KOH/
(°C) (°C) (°C) g)

[202] B100 4.1 873 – 85 94 – 39,500 – 1 0.46

B20 2.58 843 – 55 63 – 41,700 – −6 0.4
B100A30C30 4.1 874 – 83 93 – 40,200 – 1 0.47
B20A30C30 2.59 844 – 52 61 – 42,200 – −5 0.4
[38] UCO 32. 91 921 at – 289 – – – – – 4.04
15 °C
Synthesised 4.8 898.1 – 171 – – – – – 0.41
biodiesel + TiO2/PrSO3H
[203] BCO 34.87 at 894 – 195 – – 38,480 10 2 –
40 °C
BCME 4.78 875 – 155 – 40,320 3 −4 –
Diesel 2.63 840 – 60 – 42,500 −5 −12 –
[194] MOME 4.3 at 35 °C 864 at – – – 52 38,108 – – –
18 °C
MOMET100 4.34 884 – – – 54 37,854 – – –
MOMET200 4.38 891 – – – 57 37,652 – – –
[20] JB20 3.33 at 40 °C – 849.3 at 51.6 41,142 – – –
15.56 °C
JB2025GNPs 4.05 – 850.1 – 52.3 41,160 – – –
JB20100GNP 4.22 – 850.4 – 57.4 41,230 – – –
[113] JME (B100) 11.72 – 864.5 at – – 44,866 – – –
15.56 °C
JB20D 4.06 – 847.1 – – 52 45,432 – – –
JB20D10A 4.12 – 847.1 – – 53.1 45,439 – – –
JB20D20A 4.28 – 847.1 – – 54.4 45,445 – – –
JB20D30A 4.29 – 847.1 – – 55.2 45,453 – – –
JB20D50A 4.38 – 847.1 – – 57 45,467 – – –
[24] JBD 5.25 895 – 85 – 53 38,880 – – –
JBD50CNT 5.33 897.9 – 81 – 57 39,780 – – –
JBD25AO25CNT 5.36 895.2 – 81 – 57 39,990 – – –
[56] Diesel 2 830 – 50 56 46 42,300 – – –
D70C10E20 2.35 820 – 11 14 44.6 39,000 – – –
[25] Diesel 2.1 830 – 50 – 46 42,500 – – –
D2S15W100AO 5.01 859.6 – 66 – 50 39,900 – – –
[200] Diesel 2.8 850 – – – – 45,000 – – –
E10 8.8 880 – – – – 38,250 – – –
E15 11.4 890 – – – – 36,160 – – –
[204] WD 2.85 832 – – – 50.83 42,930 – – –
WDA 2.53 834 – – – 49.6 42,920 – – –
WDSi 2.55 832 – – – 51.37 42,940 – – –
[205] HOME 5.6 880 – 170 – – 36,016 – – –
HOME25CNT 5.7 898 – 166 – – 34,560 – – –
HOME50CNT 5.8 900 – 164 – – 34,560 – – –

159
M.E.M. Soudagar et al.
a stable suspension of the diesel-nanoparticle blend. The viscosity also
decreased with the addition of DDSA surfactant.
4.2. Performance analysis of nano-additives with diesel-biodiesel fuel blend
Biodiesel fuels are the most promising alternate fuel source and
unmatched replacement for diesel fuels in the near future, which have
comparable properties of diesel. However, due to few drawbacks like
lower oxidation stability, lower engine speed and power, excessive
carbon deposition and gum formation, biodiesel is not brought to full
use in the engine. Many researchers are developing new technologies
and methods to overcome these problems. One such novel method of
enhancing the properties of biodiesel is by addition of nano-additives.
In this section, the performance parameters of C.I engine such as brake
thermal efficiency (BTE), brake specific fuel consumption (BSFC),
power output (BP) of different diesel-biodiesels emulsions with the
addition of various nanoparticles like metallic, non-metallic, combina-
tion, and organic have been reviewed.
4.2.1. The effect of nano-additives on brake thermal efficiency
The relationship between the actual BP generated by the engine and
the energy transferred to the engine is known as brake thermal effi-
ciency (BTE). The effects of several fuels and fuel blends on the engine
performance can be investigated by using BTE. The addition of nano-
particles with diesel-biodiesel fuel emulsions, encourages fast and
comprehensive combustion process owing to better radiative and heat-
mass transport properties, which leads to a substantial improvement in
combustion efficiency. Nanthagopal et al. [206] investigated the var-
iation of BTE with BMEP for neat CIME, CIME emulsions with ZnO and
TiO2 at dosage levels of 50 and 100 ppm and diesel. The BTE increased
with engine load, the improvement was due to higher BP with an in-
crease in fuel rate. A maximum BTE for diesel was 3%, 31% for CIME-
T100, 30% for CIME-T50, 27% for CIME-Z100, 28% for CIME-Z50 and
26% for CIME biodiesel at the maximum BMEP. The authors observed
that the CIME nano-emulsions blends tend to show a higher BTE with
respect to neat CIME at higher loads, this may be because of the micro-
explosion of water molecules in the fuel and catalytic effect of metallic
oxides. The water particle helps in the better mixing of fuel atoms with
air and a fast evaporation. The nanoparticle in the emulsion has a large
surface to volume ratio it leads to rapid evaporation and better ato-
mization [207]. Furthermore, the nanoparticle may help to split the
hydrogen atom from water and that could involve the combustion. The
author concluded that the BTE of CIME–Z100 was lesser than the CIME-
T100, hence titanium dioxide was found to have higher oxidizing
characteristics as compared to zinc oxide. Ranjan, Alok, et al. [32] re-
ported that the BTE of all test fuels improved with the increase in en-
gine load. A maximum BTE was observed for engine load of 18.11 kg.
Various emulsions were tested, B100 showed an average BTE of 27.4%.
The maximum BTE for a load of 13.41 kg was 34.3% for PBD fuel, the
PBD fuel has a lower density, viscosity, and high calorific value. The
lower viscosity and density levels of PBD fuel resulted in an increase of
combustion, fuel atomization, and evaporation, thus increasing the BTE
[208]. For the BTE of fuels blended with nanoparticles, the BTE in-
creased by 4.01%, 4.91% and 4.8% for B100W30A, B20W30A, and
B10W30A respectively which were higher than the B100, B20, and B10
fuel. Furthermore, the nanoparticles in general, hold an improved
surface area and responsive surfaces which lead to developed chemical
reactivity to perform as a catalyst [187]. The addition of graphene
nanoparticles GNPs at 25–50 mg/L dosage level to the diesel-biodiesel
blend, increases the brake thermal efficiency by 25% [20]. In Simar-
ouba biodiesel and diesel blends, GNPs enhanced brake thermal effi-
ciency by 9.14% [142]. By adding 150 ppm carbon nanotubes (CNT)
blended with water-diesel emulsion, a maximum of 30.5% BTE was
achieved, due to the characteristics of CNT to exhibit a high surface
area/volume ratio and contribute more efficiently in the combustion. It
is because of the reactive surfaces of CNT which acts as a potential
160
Energy Conversion and Management 178 (2018) 146–177
catalyst in the combustion process [209]. The addition of 25 ppm silver
nanoparticles to the biodiesel blend increases the BTE by 51.44%, the
increase is due to the action of Ag as an oxidative catalyst which results
in increased combustion [143]. Some investigational studies were car-
ried on diesel engine performance to investigate the BTE using ferro-
fluid with diesel, biodiesel fuel mixtures. Ferrofluid emulsion fuels
deliver fast flame propagation in the combustion chamber, which re-
sults in an improved heat release patterns and complete combustions.
Yuvarajan et al. [197] observed that at all loads, the thermal effi-
ciencies of MOME and MOMEF were lower than the diesel due to the
existence of moisture in biofuels, the moisture varied from 0.09 to
0.12% in the biofuels in comparison to zero content of moisture in
diesel. Due to the combustion of biofuels, a higher moisture content was
produced in the engine. Hence, for generating the similar power as
compared diesel the energy required was higher, consequently causing
lower efficiencies and heat losses, owing to higher moisture in the en-
gine the BTE for MOMEF was increased by 2.27% for MOMEF. Fur-
thermore, due to the addition of ferrofluid, the temperature is increased
which results in longer and complete combustion, hence the efficiency
is enhanced [133]. The magnetic field changes the hydrogen in the fuel
into para-H that reacts with existing oxygen in the chamber through the
combustion that results in enhanced combustion and higher BTE [210].
The BTE at full load was found to be 28.54% for MOMEF, while it was
25.25% and 29.01% for MOME and diesel respectively. Hence, the
ferrofluid inclusion showed an increase in the BTE. The effect of Fe
nanoparticles additives with respect to the biodiesel blend and diesel
fuels in terms of BTE was experimentally investigated in a stationary
diesel engine. In palm biodiesel (PB20) and neat diesel (D) and fuel
additive were mixed through the ultrasonication process. For the
modified fuels D + 50Fe and PB20 + 50Fe, the BTE is improved by
2.06% for PB20 + 50Fe and 0.36% for D + 50Fe with respect to BTE of
PB20 and D [19].
There are limited studies were conducted on the organic and non-
organic additives with diesel and biodiesel blends. Yang et al. [200]
analyzed the effect of organic material on the engine characteristics,
glycerine was used as nano-additive. The glycerine was blended with
diesel-water blended fuel and was tested on a CI engine. The BTE sig-
nificantly enhanced for the blend of diesel-glycerine with an increase in
engine speed in comparison with that of neat diesel. The BTE increased
by 7.8% and 14.2% for E10 (10% water conc.) and E15 (15% water
conc.) at constant speed condition and at full load. This improvement
was attributed to micro-explosion phenomenon, in which the tiny
droplets fragment from the larger fuel droplets. This tiny droplet pro-
vides a larger active surface and contact areas, and the particles hasten
the vaporization process with an increase in A-F ratio resulting in
complete enhancement in the combustion process which result in an
increase in the ηth of the engine.
4.2.2. The effect of nano-additives on brake specific fuel consumption
BSFC is the ratio of the fuel expended by the engine to the engine
power generated with respect to a time a given frame. It is anticipated
to achieve a lesser value of BSFC because the engine consumes more
fuel for an equivalent performance. BSFC generally reduces with in-
crease in the load, therefore the comparison with engine load is an
important parameter. The performance characteristics that govern the
BSFC, is the viscosity, density, volumetric fuel injection and calorific
value [211]. In this section, the investigations on various nano-ad-
ditives are studied.
Ranjan et al. [32] investigated the effect of MgO NPs on WCO
biodiesel. The authors reported that the fuel sample B100W30A pro-
duced the maximum amount of BSFC 0.49 kg/kW while petroleum-
based diesel (PBD) produced least BSFC 0.35 kg/kW-h both at a con-
stant load of 4.73 kg in comparison to the other test fuels. The increase
in engine load from 4.73 kg to 18.11 kg for all test fuels reduces the
BSFC. Hence, when the A-F mixture is improved and the loads are in-
creased, there was a reduction in the BSFC. The average BSFC of PBD
M.E.M. Soudagar et al.
was 10.37%, 9.43%, 7.54%, 41.5%, 9.81% and 10.18% less than the
B100, B20, B10, B100W30A, B20W30A and B10W30A respectively,
because of less denser fuel blend. Kumar et al. [87] reported that with
the addition of ferrofluid in pongamia biodiesel leads to a reduction in
the specific fuel consumption in comparison with the neat biodiesel.
The inclusion of ferrofluid resulted in a reduced ignition delay and the
fuel properties were transformed which leads to a comprehensive
combustion of fuel. Furthermore, the momentum of fuel and the pro-
pagation is changed which may have improved combustion effect and a
cloud-like atomization of the emulsified moisture during injection is
promoted due to the improved combustion efficiency, water content
and higher viscosity of the fuel. There was a maximum reduction of
11.1% in BSFC for B20-1F at full load condition when compared with
the neat B20 fuel blend because of the addition of ferrofluid additive.
B20-1.5F and B20-0.5F showed 6.7% and 4.8% reduction in BSFC at full
load condition as compared to B20. Moreover, with the increase in the
dosage of nanoparticle in biodiesel, BSFC augmented due to inadequate
mixing of fuel. Ganesh et al. [131] investigated the effect of a mixture
of Magnalium and Cobalt oxide nanoparticles in Jatropha biodiesel, the
nanoparticles of dosage level 100 mg/l were distributed in the fuel by
using an ultrasonicator with an optimized surfactant to hold the na-
noparticles in the fuel. The investigators revealed that by the addition
of nanoparticles of cobalt oxide the BSFC was reduced at all load con-
ditions and also with the addition of Magnalium nanoparticles the en-
ergy consumption decreases and increases the thermal efficiency.
Khalife et al. [212] reported that as the water content of biodiesel is
higher, hence with the addition of nanoparticles in the biodiesel the
bsfc increases. Therefore water addition in B5 increases the bsfc, further
the addition of cerium oxide in B5 comprising water, bsfc values were
enhanced. For instance, the bsfc of B5W3m was 5% and 16% inferior to
those of neat B5 and neat B5W3, respectively. The metal-based NPs are
generally decomposed before vaporization of fuel and water, dischar-
ging active metal atoms (cerium) which could thus reduce the devel-
opment of unburned carbon deposits on cylinder interior surface which
could lead to friction reduction in the engine, i.e., parts like the piston
and the cylinder resulting in abridged bsfc [213,214]. The water in
diesel-biodiesel blends could possibly cause an upsurge in specific fuel
consumption and emissions such as CO. But the WDE fuels have a de-
cent NOX reducing capability, hence some authors have suggested a
novel method of combining metallic-based additive with WDE has been
set forth as an effective approach to concurrently overcome the draw-
backs of using water in CI engines and to covering its advantages [212].
Addition of TiO2 nanoparticles to Calophyllum Inophyllum biodiesel
blends and increasing the load results in the decreases the bsfc values as
compared with the B20 fuel due to a reduction in the ignition delay
period. Additionally, the collective effect of EGR and TiO2 nano-ad-
ditives in the biodiesel mixtures increases the bsfc slightly [85]. The
cobalt oxide (Co3O4) NPs with biodiesel emulsion resulted in a 4%
decrease in bsfc due to the catalytic oxidation of the fuel. The addition
of TiO2 in biodiesel blends caused by a 2% decrease in bsfc. The na-
noparticles perform as an oxygen buffer so that complete combustion
ensues. Hence the fuel consumption decreases compared to neat bio-
diesel [215].
4.2.3. The effect of nano-additives on brake power
The output of power of a drive shaft of an engine lacking any power
loss instigated by the gear, transition friction, etc. is known as brake
power. Ranjan, Alok, et al. [32] reported that, with the increase in
loads, the BP for all fuels increased gradually. The maximum power
output for PBD measured at 5.75 kW for a load of 18.11 kg. The BP for
PBD were 11.69%, 9.26%, 11.35%, 11.08%, 8.92%, and 9.12% higher
than B100, B20, B10, B100W30A, B20W30A and B10W30A respec-
tively. The increase in the BP value of PBD fuel was due to its high
calorific value and low viscosity. Hence, combustion occurs more effi-
ciently, leading to rising in BP, due to the larger surface area and en-
ough fuel built up in the combustion chamber leading to air-fuel
161
Energy Conversion and Management 178 (2018) 146–177
mixture formation. Furthermore, due to the high density and viscosity
of blended nanoparticles fuel, this reduces the pump leakage and thus
reduces the BP [216,217]. Gumus, Soner, et al. [55] reported that by
adding Al2O3 and CuO to the neat diesel there was a slight gain in the
BP and torque of the calibrated engine. The addition 50 ppm dosage of
CuO and Al2O3 to the neat diesel, increases the torque by a maximum
value of 1.0% and power by 3.28% for nano-diesel fuels. Kumar et al.
[87] used compression ignition (CI) for the experiential studies of CeO2
nanoparticles emulsion fuel, where the loading condition was from 2.1
to 15.9 kg. The author reported that when the load is increased at
constant engine speed, there was an increase in brake power. The
metallic nano-additives can react with the water at advanced tem-
peratures throughout the combustion process which promotes the
combustion in the engine cylinder and results in hydrogen generation.
Khalife et al. [212] reported that there was a slight reduction in BP for
B5 with the addition of water in comparison with the neat diesel fuel.
The addition of WBDE fuel blends decreased the BP due to the property
of WDE to lower the temperature of the engine. Furthermore, the au-
thor added 90 ppm of CeO2 to B5W3 and B5W5 blend, which enhanced
the BP as compared to the B5. Furthermore, when the CeO2 was added
to B5W7 fuel blend, the BP reduced due to enhanced cooling impact
which suppresses the micro-explosion phenomenon which is produced
by the compressed water in the blend. Mirzajanzadeh et al. [57] used a
combination of nanoparticles, the multiwall carbon nanotubes
(MWCNT) and cerium oxide, blended in proportions of B5 and B20
diesel-biodiesel blend. They were analyzed on a 6-cylinder, heavy duty
C.I engine. At 1500 rpm of engine speed and full load, the author re-
vealed that there was a relationship among the doping levels and the
engine power output of diesel-biodiesel fuel blends. Results revealed
that, at B5 blend with dosing of 30, 60, and 90 ppm of the nanoparticle,
there was the rise of 0.58%, 1.79% and 3.52% in engine power, while
for B20 blend with a dosage level of 30, 60, and 90 ppm resulted in an
increase in 2.28%. 5.72% and 7.81% respectively. The inclusion of
nanoparticles in diesel-biodiesel blend resulted in an increase in BP
compared with the neat diesel without any nano-additives.
4.3. Engine emission characteristics of diesel-biodiesel fuel blends with
nano-additives
The diesel engine produces a very low amount of HC and CO as
compared to petrol engines, however, the emission of PM and soot is
higher because of a high oxide of nitrogen. Even though the advances in
the current diesel engines design and combustion conditions have led to
substantial reductions in both NOX and PM emissions, these reductions
have not been adequate to meet the new standards without supple-
mentary control measures. In the following section, the literature
survey of the emission characteristics of various nanoparticles additives
in diesel and biodiesel fuels are investigated from most recent work.
Table 4 shows the literature derived from various research papers and
their findings.
4.3.1. The effect of nano-additives on carbon monoxide emission
Many authors concluded in their research that, as the proportion of
biodiesel is increased, the emission of CO was lowered drastically. The
addition of nano-additives in the biodiesel blends reduced the CO
emission. The higher the amount of oxygen and advanced cetane
number will result in comprehensive combustion. Due to the high
temperature in the engine, lack of oxygen, and dwell time for oxidation,
results in incomplete combustion of the fuel and hence emit CO
[177,183,226–228]. The overall trend noticed in most of the literature
review was a reduction in CO emissions when replacing diesel fuel with
nano-biodiesel blends. However, a few researchers didn't find much
difference between biodiesel with nanoparticles additives and biodiesel
without nanoparticles. A majority of the papers reviewed were inclined
towards the reduction of CO as the percentage of nanoparticles in the
biodiesel increased. The significant findings of the addition of various
 Table 4
The engine performance and emissions using various nano-additives in diesel and biodiesel blend.
Ref. Engine Specification
[190] AV1-Kirloskar, 4
-Stroke, single cylinder,
230 BTDC, 210 bar
[32] Kirloskar TV1, vertical,
single cylinder, constant
speed, WC, 3710C,
ATDC
[218] Urea-SCR equipped DI,
Inline, 4-cylinder, 4-
stroke, WC, 23°BTDC,
210 bar
[113] DEUTZ F1L511, 1-
cylinder, 4-stroke, DI,
AC, 24 °C.A, BTDC;
175 bar
[219] Lombardini Diesel
3LD510, Single cylinder,
4-stroke, DI
[87] Kirloskar TV1, single
cylinder, 4-stroke, DI,
WC, 23°BTDC, 210 bar
[220] Simpson - S217, 2-
cylinder, 4- stroke diesel
162
engine, DI, Vertical, IL,
23°BTDC, 200 bar
[20] HATZ-1B30-2, single
cylinder,4- stroke diesel
engine
[202] Kirloskar, Single
cylinder, 4-stroke, AC,
D.I, 23°BTDC, 220 bar
[221] Kirloskar TAF1, Single
cylinder, 4-stroke,
vertical, AC, constant
speed, DI, 23°BTDC,
220 bar
[30] Kirloskar oil engines,
single cylinder, 240 four
stroke, 220 bar
[27] Lombardini Model
3LD510, four-stroke,
single-cylinder, AC
diesel engine, 200 bar
[199] Single cylinder, (DI), 4-
stroke, Constant Speed,
Water Cooled, 23°BTDC,
210 bar
[222] Cummins diesel engine
4-cylinder, 4-stroke
diesel engine, TC, Euro 5
[223] Kirloskar (TV1), 4-
Stroke, single cylinder
Engine Speed & C.R
1500, 16.5:1
1500 rpm; 17:1
17.9:1; 10–99,999 rpm
1500 rpm; 17.5:1
1500 rpm, 18:1
1500 rpm; 17.5:1
2000 rpm; 1 8.5:1
1500 rpm; 21.5:1
1500 rpm; 17.5:1
1500 rpm; 17.5:1
1500 rpm; 16:1
1800 rpm; 17.5:1
1500 rpm; 17.5:1
2500 rpm
1500 rpm; 17:1
Loading and swept Vol. Bio-diesel Blend NPs and part. size NPs dosage and
surfactant
M.E.M. Soudagar et al.
553 cc POME Aluminium oxide; 50–100 ppm;
100 nm Cetyltrimethylammoniu-
m bromide
4.73 kg to 18.11 kg WCO MgO; 20.76 nm 30 ppm MgO;
ClC6H4COCl
(10–25 mol)
Electrical generator 20% waste frying oil Mn2O3 and Co3O4; 50 ppm (Mn2O3) and
30 nm and 10–30 nm 50 ppm (Co3O4)
DC generator 10.5 kW Egyptian Jojoba oil Al2O3, 50–100 nm 20–30 mg/L
510 cm3 Ailanthus altissima Graphene oxide; 150 nm B10 and B20 - 30, 60,
and 90 ppm
– POME (B20) Ferrous oxide, 30 nm 0.5%, 1% and 1.5% in
and ferrofluid (FF) B20; 2 mol of NaOH
100 nm
Eddy current CIME Zinc oxide (ZnO) and ZnO, 50 and 100 ppm;
dynamometer; 1670 cc Ethanox; 20 and 40 nm Ethanox- 200 and
500 ppm.
– JME (B20) Graphene nano-platelets 6–8 nm thick, 5 nm
wide; 50 mg/L
661 cm3 JME Al2O3; CeO2 Al2O3, 51 nm and CeO2,
32 nm; Al2O3 + CeO2,
30 ppm,
661 cm3 CIME 1-pentanol and 1- 40%, 50% and 60% of
butanol each alcohol in varying
% of CIME.
Dynamometer load Canola Oil methyl ester Acetylferrocene, 25 ppm
4–16 N-m; 661 cm3 AcCp2Fe and palladium
(II), PdL
Eddy current WCO CNT's, dia, 10 to 20 nm 30, 60, and 90 ppm in
dynamometer & length, 5 to 15 mm. each fuel blend
661.45 cm3 20% HOME Coconut shell nano –
additives;20 nm
– POME carbon coated 30 ppm; 4% ethanol
aluminium (Al@C)
Eddy current Dyn. CIME Cerium oxide; 25 nm 40 ppm
661 cc
Energy Conversion and Management 178 (2018) 146–177
(continued on next page)
 Table 4 (continued)

Ref. Engine Specification Engine Speed & C.R Loading and swept Vol. Bio-diesel Blend NPs and part. size NPs dosage and
surfactant
M.E.M. Soudagar et al.

WC, DI, 23°BTDC,

250 bar (modified)
[85] Kirloskar, Single 1500 rpm; 17:1 Electrical dynamometer CIME TiO2; 30–40 nm 40 ppm TiO2; Cetyl
cylinder, 4- stroke, DI bromide (CH3)3. NH4
engine, 23°BTDC,
220 bar
[224] Kirloskar, 4- stroke, 1500 rpm; 17:1 661 cc JME B20 and ethanol Alumina (Al2O3) 25 ppm Al2O3 in BDE
single cylinder, AC, DI 10%-BDE nanoparticle; 28–30 nm
diesel engine, 23, 27,
and 19°BTDC
[193] Single cylinder, 4-stroke 1500 rpm; 17:1 – Poultry litter oil Gamma alumina; 30 mg/l Al2O3 in B20;
diesel engine, DI, B20PLOME 20–50 nm 0.24 g of KOH, 15 ml
23°BTDC, 180 bar methanol
[55] Lombardini,15LD 350, 3600 rpm; 20.3:1 Water-brake JME CuO-30 to 50 nm; Al2O3- 50 ppm CuO and Al2O3;
single cylinder4-stroke, dynamometer 27 to 43 nm Na2O7Si3
WC
[142] Single-cylinder, 4- 1500 rpm; 17:1 Eddy current Dyn; Simarouba methyl ester Graphene Oxide; 20–60 ppm GO; SDS
stroke, WC, 661 cc (SME) 22.5 nm - 26 nm
computerized diesel
engine, 23°BTDC,
205 bar
[225] Single-cylinder, 4- 1500 rpm; 17:1 Electrical generator CIME MWCNT 40 ppm in B20
stroke, DI, 23°BTDC

163
Ref. N fluid Prep. Performance and Emission characteristics Increase(s) (↑) and Decrease(s) (↓)

BTE BSFC CO HC PM NOx

[190] 2-Step For B25A10029, 7%↑ (at ↓Using B25A100(0.3 kg/ ↓Using B25A50 and ↓Using B25A50 and - ↑For 0–5000 (ppm)
maximum load) kW-hr), B25A50,↓ B25A100 (acts as B25A100 (acts as (elevated cylinder
50 ppm, for all loads, catalyst and lowers ID) catalyst) peak temperatures,
oxidizes more N2)
[32] 2-Step For B20W30A, 4.57%↑ B100W30A, 28.2% For, B100W30A ↓B100W30A, B20W30A, ↓B100W30A, B20W30A, For PBD
(for max. power 5.75 kW higher than the B100, 15.71%↓; For, PBD 0.0182 g/kWh (22.27%) 4.68% compared with (1 ppm ± 15 ppm),
and engine load- The mean BSFC of PBD 52.77% and 38.88% in. compared with B100, B100, B20 by 14.09%↑
18.11 kg) was 10.37% compared with B100, B20
B20.
[218] 2-Step For B20 + 50 ppm ↓B20 + 50 ppm (Co3O4) B20 + 50 ppm (Co3O4) – – ↓B20 + 50 ppm
(Mn2O3) 1.2%↑; 4% ↓B20 + 50 ppm 450 ppm ↓; (Co3O4)-40%;
B20 + 50 ppm (Co3O4) (Mn2O3) 2% B20 + 50 ppm (Mn2O3) ↓B20 + 50 ppm f
2.7%↑ 500 ppm ↓ (Mn2O3)-14%
[113] 2-Step 15%↑for 40 mg/l, for 40 mg/l, 12%↓ for 20 mg/l, 80%↓ for 20 mg/l, 60%↓ for 20 mg/l 35%↓ For 20 mg/l, 70%↓.
[219] 2-Step – B10G0- 1.9%↑; B20G0- For B10G30, 4.84%↓; For B10G0, 10.28%↓; – For B10G0- 1.9%↑;
5.1%↑ For B10G60, 10.4%↓; For B20G0, 25.27% ↓ B20G0- 11.65%↑ than
For B10G90, 18.55%↓ than (B0G0) diesel (B0G0)
[87] 2-Step For B20-1F16.6% ↑; For B20-1F, 11.1%↓; For For FF0.5%, 1% and For FF 0.5%, 10.4%↓;FF For FF 0.5%, 19%↓, FF 0.5%, 5 to 50 ppm↓
B20-0.5F, 5.5%↑; B20- B20-1.5F, 6.7%↓; For 1.5%. CO↓by 5%, 35.8% 0.5%, 14.5%↓ 37%↓;FF 1.5%, 24.4%↓ ; FF 1%, 80 to
1.5F, 11.1%↑than B20 at B20-0.5F 4.8%↓ and 16% 100 ppm↓; FF 1.5%,
full load 60–75 ppm↓.
[220] 2-Step For ZnO (50 and For CIME (100 ZnO50, For, CIME ZnO50, 15%↓ For ZnO (100 ppm), Ethanox (500 ppm),
100 ppm), 29.5% and ZnO100, ETH200 and and For CIME ZnO100, 13%↓; For ZnO 17.8%↓; ZnO
30.7% (↑); ETH200 and ETH500), 0.241, 0.298, 18.4%↓; For CIME (50 ppm), 6.7%↓. (100 ppm), 12.6%↓
ETH500, 26.8% and 0.266, 0.248, 0.287 and ETH200, 7.5%↓ and For
Energy Conversion and Management 178 (2018) 146–177

27.1% (↑) 0.273 kg/kWh (↑) CIME ETH500, 20.7%↓

 Table 4 (continued)

Ref. N fluid Prep. Performance and Emission characteristics Increase(s) (↑) and Decrease(s) (↓)

BTE BSFC CO HC PM NOx

M.E.M. Soudagar et al.

[20] 2-Step ↑25% ↑20% ↓65% (0–4000 ppm) ↓65% ↓55% –

[202] 2-Step For B20A30C30, 12%↑ – 60%↓ 44%↓ 38% reduction in smoke –
emission
[221] 2-Step ↑For higher 1-pentanol ↑For higher 1-pentanol ↑For higher 1-pentanol ↑For higher 1-pentanol For high, 1B50-CB50, NOx↓ from 10% to
and 1-butanol + CIME and 1-butanol + CIME and 1-butanol + CIME and 1-butanol + CIME 49.5%↑ 23%
compared to pure CIME
fuel.
[30] 2-Step – – 60.07%↓ 0–20,000 ppm↓ 0–1000 ppm 51.33% ↓ ↑For higher loads
[27] 2-Step For B5C90, 3.67%↑ – 65.70%↓ 44.98%↓ 29.41%↓ 27.49↑(For higher
loads)
[199] 2-Step – – 0.01% vol.↓ 20%BD80%DF↓ – 18.56% ↓
[222] 2-Step – 6% ↓ B10E4N30 (Al@C)- B10E4 (Al@C)- 14.5% ↓. – For B10E4N30
19%↓ (Al@C), 6%–22%↓.;
For B10E4N30,
3.45 g/kWh↓
[223] 2-Step For higher CeO2, BTE↑ ↑At NH3, due to higher ↓at full load, due to the ↓with increase in the ↓using CeO2& with an
viscosity and lower addition of CeO2 at concentration of increase in no. of
calorific value NH5and better CeO2from 20 ppm to nozzle holes from 3 to
atomization 60 ppm 5
[85] 2-Step For ↓For B2040TiO2 ↓23% for B2040TiO2 ↓12% for the B2040TiO2 – For B2040TiO2,
B2040TiO2 + 20%EGR (reduced ignition delay fuel fuel 63 ppm↑
fuel 3.1%↑ period)
[224] 2-Step – At ADV IT, 4.5%↓; At At 19 deg bTDC + Al2O3 For ORG IT- In. by 8.8% For ORIG IT 54.36%↓ at ↓23 to 27 deg bTDC
ORG IT, 9.37%↓at 33.33%↓ and For RET IT- 6.06%↓ engine loads of 25% ↓At 19 deg bTDC

164
engine loading of 25% at 100% load.
[193] 2-Step ↑For B20PLOME30A – ↓B20PLOME and ↓B20PLOME and ↑ (due to higher ↓for B20PLOME30A;
B20PLOME30A B20PLOME30 viscosity and poor for B20PLOME
volatility)
[55] 2-Step – Add CuO, 0.5%↓and Add Using Al2O3, 11%↓; Using Al2O3, 13%↓; – Using Al2O3, 6%↓;
Al2O3, 1.2%↓ Using CuO, CO, 5%↓ Using CuO, 8%↓ Using CuO, 2%↓
[142] 2-Step For SME2040BTE – For SME2040, 42.85%↓ For SME2040, 15.38%↓ – For SME2040,
9.14%↑ 12.71%↓
[225] 2-Step For B20MWCNT40- – ↓Using ↓Using ↓Using B20MWCNT40 For B20 + 20%EGR,
7.6%↑ and B20MWCNT40 + 20% B20MWCNT40 + 20% 25.6%↓; For
B20MWCNT40 + 20% EGR EGR B20MWCNT40+ 20%
EGR, fuel 2.26%↑ EGR fuel 29.7%‘↓
Energy Conversion and Management 178 (2018) 146–177
M.E.M. Soudagar et al.
nanoparticles as biodiesel fuel additives are explained in this section.
The Manganese oxide (MgO) and cobalt oxide (CO) nanoparticles
were added to B20 blended biodiesel (20% WVO and 80% diesel fuel)
in fractions of 25 and 50 ppm, the result suggested that there were
considerable reduction the CO emission, MgO and CO metal oxide na-
noparticles accelerated the combustion rate and behave as an oxidation
catalyst, leading to reduced ignition delay. Hence it resulted in a degree
of mixing between fuel emitted lower CO emissions due to complete
combustion [218]. The Fe NPs additive with Palm Oil biodiesel (PB20)
reduces CO emissions by 6–12% [19]. Addition of TiO2 nanoparticle
(200 ppm) to mahua biodiesel reduced carbon monoxide by 9.3% when
compared to neat mahua biodiesel [229]. Jatropha oil + 33% Al-Mg
and Co3O4 additive resulted in 66% reduction in CO emission [131].
Mg-based additive, DEE 15%, and chicken fat biodiesel resulted in re-
duced carbon-monoxide emission by 67% [60]. Additives of Mg and Mn
metal-based additives caused to reduce carbon-monoxide emissions by
13.43 and 16.35 percentage [230]. Keskin et al. [29] studied Magne-
sium oxide, Magnesium dioxide, CuO, and CaO additives and observed
that the CO was decreased when the Mn additive was dosed with the
diesel fuel. The CO emission of biodiesel fuel reduced with Mn and Ni-
based additives. When relating to Ni to Mn-based additive, Ni relatively
resulted in a lower CO emission.
MgO nanoparticles mixed with waste cooking oil biodiesel
B100W30A, B20W30A and B10W30A produced less CO than B100,
B20, B10 and PBD [32]. Increasing the percentage of Graphene Oxide
(GO) nanoparticles in Ailanthus altissima biodiesel B10G30, B10G60,
and B10G90 resulted in reduced CO emissions 4.84, 10.48, and 18.55%
respectively, less than net-diesel (B0G0) [219]. In Simarouba biodiesel
and Graphene oxide (GO), nanoparticles reduce carbon monoxide (CO)
by 42.855% [142]. Addition of 25–50 mg/L dose levels of graphene
nanoplatelet (GNP’s) to jatropha biodiesel–diesel mixture reduced the
CO emission to 65% [20]. At the full load, CO decreases to 26% and
48% of the cases of MME20 + ANP50 and MME20 + ANP100 fuels,
respectively, compared with neat diesel fuel [13].
Mirzajanzadeh et al. [57] presented an equation to oxidize CO or
CnHn by utilizing cerium oxide as an additive, the Eq. (1) for oxidation
of CeO2 is shown below,
2CeO2 + CO → Ce2O3 + CO2 (1)
The addition of carbon nanotubes and nano silver particles de-
creases the CO emission in comparison with neat diesel. The CO
emission of CNT120-diesel-biodiesel was least amongst all the fuel
mixtures. The minimum CO emission was observed at 25.17% for
CNT120-D80-B20 blend and it was 22.48% for CNT120-D100 com-
pared with the neat diesel fuel. Prabu et al. [152] demonstrated the
effects of carbon monoxide emissions by adding alumina and cerium
oxide nanoparticle to Jatropha biodiesel. The experimental results re-
vealed that the CO emission for JBD5A5C, JBD15A15C and JBD30A30C
test fuels were 0.03% vol., 0.03% vol. and 0.02% vol. respectively, in
comparison with the neat biodiesel of 0.05% vol. and with neat diesel of
0.09% vol. These reductions of CO emission for the test fuels are due to
the capability of nanoparticles to convert CO to CO2 by its persuasive
redox-active property. Basha, Sadhik [16] investigated the effect of
CNT, DEE in JME biodiesel, Jatropha biodiesel 91% quantity, 5% of
water and 4% of emulsifiers, 50 ppm of CNT, and 50 ml of DEE and
combined mixture of CNT + DEE (50 ppm CNT + 50 ml DEE) resulted
in complete combustion of the fuels JME5W50CNT,
JME5W50CNT50DEE, and JME5W50DEE. The percentage of CO was
observed to be 0.48 (% by vol.) for JME5W50CNT50DEE, whereas it
was 0.55, 0.57, 0.66, 0.61 and 0.53 (% by vol.) for the pure diesel, JME,
JME5W, JME5W50CNT and JME5W50DEE at the full load respectively.
The addition of zinc oxide (ZnO) nanoparticles as a fuel additive to
Mahua Methyl Ester (MME), B20 with 50 ppm ZnO, resulted in reduced
CO emissions [231]. When W/D is used in all load conditions, higher
CO was formed than D2. The CO emissions using W/D are maximum for
165
Energy Conversion and Management 178 (2018) 146–177
the no-load condition, specifically for E20 [232]. Rubber seed oil (B20)
blended with pure diesel fuel along with Aluminium oxide (Al2O3) was
used in the proportions of 10 ppm, 20 ppm and 30 ppm reduces CO by
44.8% [46]. Aluminium oxide nanoparticles at high temperatures dis-
sociate into Al2O and oxygen as shown in Eq. (2) [13].
Al2O3 → Al2O + 2O (2)
Al2O3 is unstable at high temperatures during combustion in the
combustion chamber, so it decomposes as shown in Eq. (3),
Al2O → 2Al + O (3)
Canola oil biodiesel and the additives dosage of 25 ppm of Bis-pal-
ladium (II), PdL2 were prepared as a palladium-based additive, the
result revealed a reduction in CO emissions up to 60.07% [30]. CO
emissions were reduced by 31% using Fe2O3-WO3 particles and mixture
of 6 biodiesels: sunflower methyl ester (SuME), soybean methyl ester
(SME), grape seed methyl ester (GME), corn methyl ester (CME), olive
methyl ester (OME) [21] and rapeseed methyl ester (RME) [17]. Ad-
dition of 200 ppm of TiO2 nanofluid to MOME results in 8% and 13%
reduction in CO emissions [194].
4.3.2. The effect of nano-additives on carbon dioxide emission
Many researchers reported a slight reduction in CO2 at a different
speed and load conditions due to the addition of metal additives
[13,16,230,233]. The amount of oxygen present in biodiesel and less
amount of carbon causes higher carbon dioxide emission. The cotton-
seed + 0.01% L-ascorbic acid, nano-biodiesel reduces CO2 by 1% [21].
The fish oil biodiesel and 2% DEE resulted in a reduction of CO2
emission [234]. Ghanbari et al. [235] revealed that the CO2 emission
increased because of the lean burning related to increasing nano-
particles and due to the improved combustion. Karavalakis et al. found
that increasing the bioethanol quantity in the diesel-biodiesel-bioe-
thanol blends, results in a decrease in the CO2 emission by 57% as
compared to the diesel fuels. This is due to the low carbon-to-hydrogen
ratio in the bioethanol molecule that stimulates the oxidation of CO
molecule to CO2. Therefore, there was an increase in the quantity of
water and less CO2 was emitted [28]. The increase in the proportions of
graphene oxide (GO) nanoparticles in the biodiesel blend, in the blends
B10G30, B10G60, and B10G90 the CO2 reduced to 4.15, 5.34, and
7.12% respectively, less than that of neat-diesel (B0G0) [219]. Nan-
thagopal et al. [206] The existence of TiO2 and ZnO nanoparticles in the
CIME nanoparticle emulsion behaves as an oxygen buffer and thus
delivers combustion. Furthermore, the carbon dioxide emission was
high for CIMET100 nanoparticle emulsion in comparison with diesel,
neat CIME and other CIME nano emulsions. Diesel resulted in a lower
carbon dioxide emission as compared with other fuels because of the
HC-chain constitution of diesel. Ranjan et al. [32] reported the reduc-
tion in CO2 emissions by 1.12%, 1.7% and 0.71% for B100W30A,
B20W30A, and B10W30A the nano-biodiesel blends respectively. They
emitted less CO2 (1.2% on average) as compared to B100, B20, and
B10. Ithnin et al. [236] used TiO2 and ZnO in the CIME nano-emulsion
performs as an oxygen buffer and thus provides complete combustion.
Furthermore, for CIME-T100 nano emulsion the CO2 emissions were
higher, as compared with pure CIME and other CIME nano emulsions.
Kumar et al. [87] reported that, due to a higher load, the level of CO2
emission increases for all fuel blends at a constant speed. In addition,
there was an increase in the carbon dioxide contents due to the inherent
property of biodiesel to contain oxygen. The authors revealed in their
test that the addition of ferrofluid nanoparticles to the biodiesel-diesel
blend further increases the CO2 emissions. The addition of 0.5% of
ferrofluid exhibited an increase of 10.1% carbon dioxide and 1% ad-
dition of ferrofluid showed 23% increase in carbon dioxide and 18.5%
increase in carbon dioxide emissions with the addition of 1.5%, the
results were compared with neat B20 fuel at full load condition.
M.E.M. Soudagar et al.
4.3.3. The effect of nano-additives on hydrocarbon emission
Hydrocarbon emissions are fragments of partially burned fuel mo-
lecules. Many researchers have found that the blending of biodiesel
with diesel fuel leads to complete combustion due to the amount of the
oxygen present in the biodiesel. The addition of nanoparticles can sig-
nificantly reduce HC emissions. The quantity of a relative air-fuel
mixture and higher cetane number reduces the ignition delay, hence the
concentration of HC emission decreases [4,237–240]. Due to carbon in
their structure, the CNT particles increases the HC emission, while the
oxygenated additives encourage complete combustion and the nano-
silver particles decrease hydrocarbon emission in comparison with neat
diesel [56]. Addition of TiO2 nanoparticle (200 ppm) to mahua bio-
diesel, reduced hydrocarbon emission by 6.6% when compared with
neat mahua biodiesel [229]. There was a maximum HC increase of
14.21% for CNT120-BD and a maximum reduction of 28.56% was ob-
served for Ag120-BD [235]. Jatropha biodiesel (B100) with a dispersion
of Cobalt oxide (Co3O4) and magnalium (Al-Mg) nanoparticles of do-
sage level of 100 mg/l, resulted in 70% reduction in HC emission at
75% load [131]. Zinc nanoparticles in mass fractions of 50 ppm and
100 ppm in blends of diesel–pomoplion stearin wax biodiesel resulted
in the higher reduction of HC emission as compared to biodiesel-diesel
blends without additives due to improved ignition characteristics
[241].
A reduction of 26.04% in hydrocarbon emission was observed for
Mahua biodiesel MME20 + ANP100 aluminium oxide nanoparticles
(ANPs) [13]. There was a reduction in unburnt hydrocarbon (HC) by
15.38% using graphene oxide nanoparticles [142]. The mechanism of
oxygen supply by cerium oxide which leads to reduced emissions of
unburned hydrocarbons (UHC), soot and carbon monoxide (CO) re-
spectively [34], as shown in Eq. (4).
1 x y with D2. E20 is reported to be the best in reducing PM with an average
(2 x+ y)CeO2 + C x Hy (2x + y ) Ce2 O3 + CO2 + H2 O
2 2 2 (4)
The emissions of HC for Iron oxide nanoparticles blended with
POME biodiesel is lower in comparison with B20. The HC emissions are
significantly reduced by adding the iron oxide nanoparticles
B20Fe3O4100 (80% Diesel + 20% POME + 100 ppm Fe3O4) with
varying loads [233]. By using waste cooking oil (WCO) and 5 wt% of
zinc doped calcium oxide, there were reductions in the UHC emissions
[195]. Raju et al. [236] studied the emission characteristics of tamarind
seed methyl ester (TSME) blended with 60 ppm of alumina oxide. The
TSME20Al2O3 in the entire loading operation showed a 24–68% re-
duction in unburned hydrocarbon emissions. Hosseini et al. [17] in-
vestigated waste cooking oil (WCO) as bio-fuel and Multi-walled
Carbon Nanotubes (MWNTs) as an additive. They were mixed in with
concentrations of B5 and B10 WCO biodiesel, CNTs with the con-
centrations of 30, 60, and 90 ppm were used for each fuel blend, B10
fuel blends with 90 ppm of CNT showed 44.98% reduction of UHC
emissions. Ghanbari et al. [235] added CNT (40, 80 and 120 ppm) and
nanosilver particles (40, 80 and 120 ppm) as an additive to the bio-
diesel-diesel blended fuel, UHC emission with silver nanoparticles-
diesel-biodiesel blended fuel decreased by 28.56%. Devarajan et al.
[242] added Mahua Oil Methyl Ester with ferrofluid (MOMEF) resulting
in an average reduction of 16.72%. The difference of HC emissions of
MOMEF and MOME varied from 0.033 g/kWh at lower loads to
0.073 g/kWh at higher loads. Mirzajanzadeh et al. [57] investigated the
overall effect of the nano-additives with the addition of 30, 60 and
90 ppm concentrations of CeO2 and MWCNT in B5 and B20 biodiesel
blend The investigation resulted in a substantial decline in all emissions
with the inclusion of nano-additives. The maximum reduction in the
volume of pollutants was recorded at 90 ppm concentration of nano-
additives.
4.3.4. The effect of nano-additives on particulate matter emissions
Particulate matter contains soot and various liquid or solid particles
[174,243,244]. Smoke is mainly formed in the region of rich fuel
166
Energy Conversion and Management 178 (2018) 146–177
mixture zone and hence it will be more advanced at the full load con-
dition for all tested fuels. The catalytic effect of the nanoparticle and
higher surface to volume ratio results, in an improved combustion, to
minimize the smoke formation [236]. The increase in the oxygen con-
tent in the fuel blend means there is a reduction in the emitted PM. This
is possible by using the oxygenated NPs which influences the properties
of the fuel. In numerous studies, the high level of oxygen has been
emphasized as the reason behind the substantial reductions attained in
PM emissions.
The TPR analysis conducted by Sajeevan et al. [58] reported that
the temperature at tailpipe was 300–400 °C and ceria-zirconium nano-
particle releases enough oxygen to neutralize the high-temperature soot
particles, the soot particles decreased by 3.5–26.3% for nanocatalyst-
containing fuel samples. Sajeevan et al. [135] and Mirzajanzadeh et al.
[57] presented the Eq. (5) for oxidation of the soot particles using CeO2
NPs.
4CeO2 + Csoot → 2Ce2O3 + CO2 (5)
The smoke emission increases with the load for all the fuel blends,
with the addition of ferrofluid, exhibited a reduction in emission
compared to the neat fuel. Kumar et al. [87] investigated the variation
in smoke emission with respect to the load. The reduction in smoke
emission is due to the oxygen content in blended fuel and nanoparticle
additive. Addition of 0.5% ferrofluid exhibited a reduction of 19%, 1%
addition showed 37% reduction and 1.5% ferrofluid additive showed
24.4% decrease in smoke emission in comparison with neat B20 fuel at
full load condition.
The MgO nanoparticles and blended biodiesel for B100W30A,
B20W30A and B10W30A smokes remained 1.59%, 8.94% and 3.5% less
opaque (on average 4.68%) [32]. For every type of W/D associated
decrease of 35% for each load condition [232]. AcCp2Fe behaved as an
effective additive in reducing PM than PdCl2 additive, due to the re-
action of metals with water vapors to yield hydroxyl radicals which act
as oxidation rich catalyst, which further decreases the PM emission due
to a reduction in oxidation temperature [30]. The addition of ferrofluid
demonstrated a reduction in emission compared to the non-additive
fuels, 0.5% ferrofluid resulted in a decrease of 24.4% in smoke emission
when compared to emission characteristics of neat B20 fuel at full load
condition [240]. Smoke opacity is strongly dependent on the amount of
air in the cylinder and oxygen in fuel. The addition of ferrofluid to
MOME has resulted in shortened ignition delay, better evaporation, and
better ignition characteristics. An average of 14.28% reduction in
smoke emission was observed by appending ferrofluid to MOME [242].
The smoke concentration for TSME20, TSME20ANP30, TSME20ANP60,
TSME20CNT30 and TSME20 CNT60 is found to be 1.79%, 44.35%,
46.6%, 41.41% and 41.92% lower than diesel fuel at full load condition
[236]. The addition of Manganese (Mn) based NPs in diesel fuel re-
duced the polycyclic aromatic hydrocarbons (PAHs) emission sig-
nificantly [245]. The other purpose of utilizing the metal oxides such as
TiO2 is to stimulate the molecular bonding between the water and
diesel emulsion and to yield benefit from the photoelectrocatalytic ef-
fect of these metal oxides to generate hydrogen from water.
4.3.5. The effect of nano-additives on nitrogen oxide emissions
Nitrogen oxide (NOX) is the emissions of oxides of nitrogen, NOX in
the exhaust consists of nitric oxide (NO) and nitrogen dioxide (NO2).
Many researchers blended additives with biodiesel to decrease the NOX,
by adding an oxygenated additive, metal-based additives, and cetane
improver [55,57,58,235,246]. The investigations revealed that the
emission of biodiesel-nanoparticles blends increased the NOX emissions
when the nanoparticles concentration increases. When the combustion
flame temperature increases and the process is closer to stoichiometric,
the NOX emission increases, largely due to the increase of thermal NOX.
NOX emissions were reduced for JME5W50CNT fuel, compared to pure
M.E.M. Soudagar et al.
diesel and JME5W fuel. A comparable effect was also seen with regards
to DEE blended biodiesel emulsion fuel due to the secondary atomiza-
tion and micro-explosion. However, the CNT + DEE blended biodiesel
fuel, induced a reduced level of NO emissions amongst the tested fuels.
The NO emission at the full load was 895 ppm for
JME5W50CNT50DEE, while it was 1340 ppm, 1292 ppm, 948 ppm,
930 ppm and 920 ppm for the pure diesel, JME, JME5W,
JME5W50CNT, and JME5W50DEE respectively [16]. Tan et al. [201]
reported that at 1600–2100 rpm, the development of NOX was gradu-
ally reduced, yet it progressively increased at high engine speed. At a
speed range of 1600–2100 rpm, around 30–54% reduction in NOX
emissions were observed for diesel-biodiesel-bioethanol fuel mixtures
than diesel.
Aluminium oxide nanoparticle additives increased NOX emission
noticeably, with an average increment of around 4.8% and 7.95% for
MME20 + ANP50 and MME20 + ANP100 fuels, respectively [13]. NOX
emissions from the B0G0 fuel were slightly lower than those from
B10G0 and B20G0. Also, the NOX levels from B10G0 and B20G0 were
1.9% and 11.65% higher than that of neat-diesel (B0G0), respectively
[219]. El-Seesy et al. [20] reported that due to the decrease in com-
bustion duration, it was found that the NOX emissions for GNP-JB20
blended fuel at different engine speeds and torques were considerably
lower than those recorded for JB20, irrespective of the engine load. The
result is attributed to the fact that the at an engine speed of 2000 rpm,
superior engine performances were obtained at the GNP additive level
of 25–50 mg/L, and the NOX reduced by 55%. Furthermore, it was
observed for an engine speed of 2500 rpm and 25–50 mg/L GNP’s
concentration the NOX reduced by 40%. Sajith et al. [34] reported that
the CeO2 with dosing level of 80 ppm has been emphasized for its af-
firmative effect when mixed with biodiesel, resulting in a 30% reduc-
tion of NOX reduction. Keskin et al. [29] used an air-cooled, DI diesel
engine with a single cylinder to investigate the effect of 8 mmol/L of
MnO2 and 12 mmol/L of NiO. The authors concluded that the com-
bustion of biodiesel blends of B60-Mn and B60-Ni reduced the NOX as
compared with the neat diesel, whereas, Mn reduced the effluents more
readily than the Ni additives due to its advanced catalytic effect. Eq. (6)
and Fig. 8 illustrates the mechanism of oxygen adsorption by cerium
oxide (Ce2O3) which breaks NOx into simple nitrogen.
Ce2O3 + NO → 2CeO2 + N2 (6)
In contrary to the many investigations, most of the researchers re-
ported a positive impact of NOx reduction by utilizing metal additives.
However, few reported increased emission of NOx by use of metal ad-
ditives. For example, Ma et al. [213] reported an increase in NOx by
6.8% and 6.3% for FTC-Diesel (1:3200) and FPC-Diesel (1:10,000) in
comparison with the neat diesel at 2800 rpm and 0.21 MPa BMEP.
Keskin et al. [230] reported that inclusion of 8 and 16 mmol/L MnO2
and MgO nano-catalysts led to an increased NOx emission. Some in-
vestigators stated that ethanol-biodiesel-diesel combustion with high
EGR, in comparison with the above results, showed NOX rises at low
loads and NOX reduces at high loads [247,248]. Wang et al. [249]
Fig. 8. Cerium oxide role in the combustion process (Adapted from [58] with
permission).
167
Energy Conversion and Management 178 (2018) 146–177
studied the effect of oxygenated nano-additives with ultra-low sulfur
diesel (ULSD). The results showed that with the increase in the ethanol-
ULSD blends which contains more oxygen, the NOX emission increased.
However, with the increase in the oxygen content in DGM-ULSD blends,
the NOX reduced. The authors also concluded that the DGM reduced the
quantity of fuel combusted in the pre-mixed combustion phase due to
the characteristics such as the low heating value (24.5 MJ/kg) and a
higher cetane number of 126.
The addition of Co3O4 nano-additives exemplifies an improved re-
duction in the NOx emission at all loads in comparison with Mn2O3
nano-additives. With the addition of 50 ppm of Co3O4 and at maximum
load, there is almost 40% decrease in NOx emission, whereas for Mn2O3
for the same concentration the reduction in NOx emission is about 14%
[218].
5. Nano-additives: combustion and exhaust emissions, toxicity
effects on humans, corrosion in the engine, applications, and
limitations
5.1. Nano-additives during combustion and exhaust emissions
Several researchers, such as [13–16,19,29,32,38,42,43,45–47,
55,57,60,61,86,113,128,143,144,152,185,188,190,194,197,199,201,
205,209,215,218,220,221,223–225,229,233,241,250–253], etc. have
effectively investigated and reported the effects of nano-additives and
fuel blends on stability, combustion characteristics, engine performance
and emission. However, a major question arises in the inclusion of
nano-additives in fuel, which has not been addressed by a majority of
researchers “What happens to nanoparticles during the engine exhaust
emission?” A very scarce literature is available concerning the traces of
nano-additives in engine exhaust emissions. The authors have at-
tempted to collect information from a few available literatures, which
are summarized in this section.
Even as the nano-additives have established the potential to im-
prove fuel efficiency and the eminence of exhaust emissions, they may
also cause environmental concerns if they are carried by the exhaust
gases. The metal particle size, morphology, oxide layer thickness, am-
bient pressure, and temperature are the key controlling parameters for
controlled ignition and combustion. The microexplosion promotes the
secondary atomization of fuel droplets towards ultrafine granularities.
Deqing Mei et al. [186] reported in their study that the nano-CeO2 acts
as a smoke suppression additive, CeO2 is an efficient nano-additive in
diesel. During the combustion process, CeO2 releases oxygen and pro-
mote dehydrogenation on the particle surface to form active radicals
such as OH−, which can facilitate the spontaneous and complete
combustion of diesel fuel. A diesel fuel blend with a high dosing level of
nano-CeO2 can cause an early ignition, which can lead to escaping of
nanoparticles through the exhaust. The authors concluded that a trace
amount of CeO2 has little effect on PM emissions. Qibai et al. [222]
investigated the effects of Al@C nanoparticles in the diesel-biodiesel
blend. The Al@C provides excess oxygen in the fuel blend. The exhaust
gas is passed through four multiple filter papers, the particulates, in-
cluding combustion residues and other particles were adhering to filter
paper in different scales are investigated. The EDX spectrum displays
the microstructure of nanoparticles embedded in the collected com-
bustion residues on filter papers. The residues contain aluminium,
oxygen, carbon, and silicon in the exhaust. High-resolution TEM images
revealed that the NPs were crystalline, and having calculated lattice
spacing of 0.212 nm and 0.258 nm. The results revealed that Al@C
nanoparticles have been transformed into alumina particles during the
combustion process in an engine, which leads to a reduction NOX
emission, performance enhancement. However, the PN emission in-
creased, which may result in more ash accumulation in Diesel Parti-
culate Filters (DPF) and affect the performance of the after-treatment
system and the engine itself. It may hence be essential to clean or
change the after-treatment system more often. According to Karmakar
M.E.M. Soudagar et al.
et al. [254] and Karmakar et al. [255], the combustion of boron NPs
consists of a complex process of removal of the oxide layer, followed by
the combustion of bare boron. The presence of an oxide layer on boron
NPs not only covers the large fraction of its volume, but also limits the
combustion process which could probably confine the complete com-
bustion of boron particles. The incomplete combustion causes a sig-
nificant reduction in total energy available in the particles and escaping
of boron particles through the exhaust.
Jong Boon, et al. [184] investigated the combustion progression of
graphite oxide NPs in diesel fuel, initially, all the test fuel droplets
experience preheating for a brief period before ignition. Through this
period, the diesel and the dosed diesel at 0.01% and 0.1% dosing begins
to vaporize and expand progressively. The observed trend can be
credited to thermal expansion and cavitation build-up in the fuel dro-
plet during pre-heating. The subsequent period of heating (i.e., ignition
delay), the droplets of all the fuels eventually ignite at various time
intervals. A shortened ID for the dosed fuels was observed from single
droplet test, less amount of fuel was burned in the pre-mixed combus-
tion, resulting in lower flame temperature, hence resulting in less NOx
emission. The additional heat absorbed by the NPs is transported away
from the droplet to the fuel vapor-air mixing region by diffusion, hence
the diffusion rate was reduced with larger and heavier GNPs from the
droplet surface. This caused most GNPs to be trapped inside the droplet
and absorb heat, thus resulting in a higher temperature at the point of
ignition. After ignition, steady burning was observed for all fuel dro-
plets. In the second stage, the burn-rate constant of the dosed diesel
fuels increased up to 29% compared to the neat diesel. Primarily, this
can be attributed to the presence of oxygen content in the NPs, resulting
in more rapid combustion within the flame front. A better heat scat-
tering by the NPs was observed due to their improved radiative heat
absorbance thus causing the higher vaporization rate of the fuel droplet
for more rapid burning. The high-intensity radiation released by the
flame at 1500 K to 3000 K is absorbed by GNPs ensuing higher vapor-
ization rate of the fuel droplet and hence the combustion takes place
more rapidly. The higher burn-rate constant indicates complete com-
bustion due to the additional oxygen and high heating values supplied
during the breakdown of the NPs. During the fuel injection, micro-ex-
plosions from GNP droplets further extend the air-fuel vapor region.
The coalescence decreases due to the expansion of the spray and frag-
mentation stop due to the reduced relative velocity between the dro-
plets and entrained air. At fuel injection, micro-explosions from GDD
droplets discharge smaller droplets and spread the air-fuel vapor region
to achieve more rapid burning. Thus, increasing the fuel conversion
efficiency and work output in diesel engines. The peak temperature of
all the dosed diesel reduced and can reach up to 13.8% reduction
compared to the neat diesel. A deposition of unburned GNPs was ob-
served on the thermocouple wire.
Studies have shown that the addition of CeO2 NPs to fuel as an
additive has resulted in the emission of a small amount of the NPs.
These particles are expected to accumulate in the environment, parti-
cularly on the roadside [131,250,256]. Kim et al. [257] who reported
that the silver NPs are transformed to silver sulfide when the Ag NPs are
emitted into the atmosphere and combine with the water in canals,
ponds, or rivers. The Aluminium NPs after combustion are exposed to
air and reacts with oxygen to form a passivation layer of aluminium
oxide (4 nm in thickness) and since Al2O3 is insoluble in water, they
either float on the surface of water or settle on the ground. The piston of
aircraft operating on leaded aviation fuel results in the production of
lead, which is the major source of lead in the air [258]. As with many
NPs, the main concern which will have to be dealt with before is the full
commercial use of nano-additives are their environmental impact.
Paramashivaiah et al. [142] investigated the effect of graphene NPs
with different dosage levels on Simarouba biodiesel. It was observed
that there was an increase in the smoke level with the increase in the
load. PM emission was higher for SME fuel, which indicates incomplete
combustion of the fuel at all the loads. The authors observed that at all
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Energy Conversion and Management 178 (2018) 146–177
loads the smoke emission reduces with the increase in the dosage level
of graphene, however, the emission test for highest graphene dose re-
vealed unburnt graphene NPs with the exhaust emissions.
Cerium oxide has the capability to go through a conversion from the
stoichiometric CeO2 (+4) valence state to the Ce2O3 (+3) state
through a moderately low energy reaction. Cerium oxide supplies the
oxygen for the reduction of the HC as well as the soot and gets con-
verted to cerous oxide (Ce2O3). Cerium oxide lowers the carbon com-
bustion temperature and thus improves HC oxidation, promoting
complete combustion of fuel [34]. Due to its high thermal stability,
Ce2O3 formed from the oxidation of HC and soot remains active after
enhancing the initial combustion cycle and gets reoxidised to CeO2
through the reduction of nitrogen oxide, considering the reactions of
CeO2 with biodiesel, the authors informed the presence of infinitesimal
amount of CeO2 NPs [34,44]. Lee et al. [95] tested ferrocene as a fuel-
borne catalyst, the ferrocene additive was introduced into the fuel by
suspending ferrocene powder in a small volume of diesel and then
blending with the bulk fuel to the required concentrations. Ferrocene
doping was found to generate Fe-rich NPs, whose size and concentra-
tion increased with the doping level. The soot production was reduced,
but included the Fe metal oxide particles. The authors reported that the
Fe oxide molecules being bulkier settled in the exhaust manifold and
few the escaped particles were collected as ash in a filter attached to the
exhaust. Gantt et al. [259] used electron microscopy to characterize
cerium emissions from a small engine utilizing EnviroxTM. They found
that around 40% of the cerium particles were linked with micron-sized
soot particles, the remainder of which were emitted as individual par-
ticles into the air. Some Ce escaping in the emissions could accumulate
in soils [260,261]. When the magnetic materials are used as fuel ad-
ditives, they have a marked advantage: they can be collected at the
exhaust and therefore will not escape into the atmosphere. This drags
more consideration to use of ferro-based nano-additives in diesel and
biodiesel engines [251]. The literature presented on nano-additives in
diesel-biodiesel fuel blends is lagging the consequence of nanoparticles
after combustion. Hence, there is a future scope of study in the field of
nanoparticles in exhaust gases.
5.2. Toxicity effects of nanoparticles on humans
The interaction of NPs with living structures includes their dose and
solubility, and the ability of NPs to spread within the human body.
Some NPs dissolve easily and their effects on humans are the same as
the effects of the chemicals from which they are manufactured.
However, NPs do not degrade or dissolve readily instead, they may
accumulate in biological systems and persist for a long time, which
makes them a matter of concern. But the interaction with living systems
is also affected by the dimensions of the NPs. For instance, NPs not
bigger than a few nm may reach well inside biomolecules, which is
probably low for larger NPs. The NPs may cross the cell membranes and
the inhaled NPs can reach the blood and target sites such as the heart,
blood cells, and liver [262]. Polycyclic aromatic hydrocarbons (PAHs)
are identified as mutagenic and/or potentially carcinogenic for humans.
Manganese-based additives were used to investigate the effects of PAH
emissions. Mn-based additives reduced the emission of regulated and
unregulated pollutants [245].
A fundamental fraction of inhaled NPs can deposit in the lungs. NPs
can potentially move from the lungs to other organs such as the brain,
the liver, the spleen and probably the fetus of pregnant women. The
information on these pathways is limited, but the actual number of
particles that move from one organ to another can be significant, de-
pending on exposure time [262,263]. A majority of people are regularly
exposed to metallic NPs in ambient air, mainly from diesel fumes,
combustion of fuels with additives produces a vast number of NPs
which are primarily only about 10 nm in size, but rapidly link together
to form larger groups of up to 100 nm that may linger in the air for days
or weeks. Researchers have proposed that NPs of size less than 10 nm
M.E.M. Soudagar et al.
acts comparable to a gas and can enter human tissues easily and may
disturb the cell’s normal biochemical environment. To clear these NPs
from the body, the mechanisms of the immune system are activated.
The estimated half-life of NPs in human lungs is around 700 days posing
a consistent threat to the respiratory system. During metabolism, some
of the NPs are congregated in the liver tissues [264]. The exposure of
CeO2 particles is through inhalation, CeO2 is poorly-soluble and thus
deposit within the respiratory tract based on aerodynamic properties
associated with its size division and aggregation state [264]. Gatti
[265] found that few NPs and microparticles were found in the in-
testinal walls and appeared to be related with inflammatory intestine
illnesses and intestinal cancer. The air in a normal room can contain
10,000–20,000 NPs/cm3 while concentration in urban streets can be
1,00,000 NPs/cm3 [264,266]. The effect of the use of various NPs on
human health is explained briefly in the following section.
A study on the oral toxicity of ZnO NPs in humans revealed that a
significant accumulation of NPs in the liver leads to cellular injury and
oxidative stress-mediated DNA damage and apoptosis after sub-acute
oral exposure of ZnO NPs for 14 consecutive days. In addition, the
genotoxic properties and the proinflammatory potential of ZnO NPs
affected the nasal mucosa cells [267]. Brunner et al. [268] found the
exposure of ZnO NPs with a high concentration (49 mg/mL) on human
mesothelioma cells resulting in almost a complete cell death in the cell
culture. ZnO NPs have resulted in a change in the cell morphology, DNA
damage, alteration in mitochondrial activity in human hepatocytes, and
embryonic kidney cells.
Gui et al. [309] found TiO2 NPs inhibited proliferation and induced
morphological changes that were related with a decline in im-
munolocation of F-actin fibers. TiO2 NPs could move among organs and
pass through the blood-brain and the blood–heart barrier after long-
lasting exposure and accumulate and get dispersed in liver, heart, and
brain. TiO2 NPs collect in the kidney, resulting in nephric inflammation,
cell necrosis, and dysfunction [267]. The SiO2 NPs causes pulmonary
damage when inhaled, nano-SiO2 are easily transported into the blood
and settle in target organs such as kidney where they exert a possible
toxic effect [269]. A study utilizing a cerium additive has revealed that
cerium can notably change the physical and chemical properties of
diesel exhaust emissions, resulting in higher levels of toxic air, chemi-
cals such as benzene, 1,3-butadiene, and acetaldehyde. According to
Poland et al. [270], the multi-walled CNTs produce carcinogenic effects
comparable to asbestos after introducing into the peritoneal cavity, as
compared to single-walled CNTs, which were readily absorbed by
macrophages.
The copper nano-materials have been recognized to possess toxic
effects on the liver and kidney. Lei et al. [271] reported the use of nano-
copper caused severe damage in liver, kidney, and spleen in experi-
mental animals. After oral administration and interacting with gastric
juice, highly reactive ionic copper is formed, which then accumulates in
the kidney of exposed animals. Chen et al. [272] reported that Al2O3
NPs disturb the cell viability, modify the mitochondrial function, in-
crease the oxidative stress, and change tight junction protein expression
of the blood-brain barrier.
5.3. Corrosion in engine and engine parts
The corrosive wear results from the chemical action of diesel and
additives. The corrosive action is more deceptive than abrasive action.
Corrosion quietly destroys the engine as acid products collect in the oil.
During the combustion, sulfur in diesel fuel and additives forms sulfur
oxides, which then combines, with moisture in the intake air and fuel to
produce sulfuric and sulphurous acids. These acids affect the cylinder
walls, piston rings, damages the exhaust valve guides and engine
bearings [252,273,274]. The copper strip corrosion test plays an im-
portant role in the selection of dosage limit of the metal-based additive
for biodiesel. Kannan et al. [128] used ferric chloride (FeCl3) of dosage
level between 5 and 20 lmol/L in biodiesel in accordance with the
169
Energy Conversion and Management 178 (2018) 146–177
ASTM limit of class 1b. Beyond the acceptable level, it deteriorates the
engine parts.
The nano-additives in fuels are also used as corrosion inhibitors. The
corrosion inhibitors are additives that prevent chemical attack on a
metal surface. Anti-corrosion additive are more effective in enhancing
the engine performance as such, timely ignition for complete combus-
tion. This group of additives repels water and neutralizers the acidic
reaction byproducts of corrosion formed at the lubricant surface. Some
of the corrosion inhibitors are hexamine, phenylenediamine, and di-
methyl ethanolamine, and their derivatives sometimes sulfite and as-
corbic acid are also used [274,275]. The water-based additives sus-
pended in diesel-water emulsion fuel to result in corrosion and
malfunction of precision engine parts such as fuel injectors. Water in
the additives is the main perpetrator that spurs the growth of fungi and
bacteria beneath the fuel tank. Some of the bacteria in the tank release
acidic by-products as part of their life cycle. This acid causes corrosion
within the fuel system [276]. Biodiesel can cause fuel filter blocking,
increased fuel system corrosion and microbial contamination, the pre-
sence of multifunctional diesel fuel additive provides excellent emul-
sion control. IRGALUBE 349 additive helps in improving the corrosion
control in the engine. When it is added to diesel and biodiesel, the metal
limits the formation of ions, which catalyze oxidation processes to gum
formation [252]. De Caro et al. reported that the use of steel and copper
cylinders immersed in the ternary blends were not corroded, even when
the 1-octylamino-3-octyloxy-2-propanol additive exist. The blends were
mixed with hexadecane as HC base to prevent the need for antic-
orrosion additives in commercial diesel fuel. The authors reported,
though there is no real threat of corrosion from the 1-octylamino-3-
octyloxy-2-propanol, however the metallic parts needs to be protected
from any traces of water existing in the fuel. The diesel fuel leads to the
formation of sulfur and asphaltenes during the combustion process,
high asphaltene concentrations in fuel require more time, energy and
higher temperatures to combust. The asphaltene jams the cylinder,
valves, and filters, thus corroding the engine parts in a long run, the
corrosion can be avoided by using antioxidant additives and ultra-low
sulfur diesel [276].
5.4. Applications of nano-additives
The nanofluids are used in the transportation sector to improve the
thermal efficiency, mass diffusivity, reduction of the vehicle weight by
redesigning a compact and lighter radiators and aerodynamic chassis,
making the thermal management systems simpler, reduction of friction
and wear, improved radiative heat transfer, increase in the fuel
economy and enhanced cooling rates especially in high-performance
engines. In the engine coolant system, ethylene glycol is mixed with
water in the ratio of 50:50, which is very commonly used motorized
coolant, because of the higher boiling point, the nanofluid can absorb
more heat [277,278]. The Al2O3 nanofluid was used as a car coolant to
investigate the thermal conductivity and viscosity of the coolant. The
addition of 3.5% volume fraction of Al2O3 resulted in a 10.41% increase
in the thermal conductivity as compared with the base fluid [279]. Lv
et al. [280] investigated the effects of Cu–water and Cu–oil in the en-
gine parameters, with the addition of 5.0 vol% NPs concentration the
heat transfer coefficient enhanced by 46% and heat dissipating capacity
of the engine increased by 43.9% as compared with pure water. Ali
et al. [281] reported that, with the addition of 1 vol% concentration of
Al2O3 NPs in water, the engine attained a maximum heat transfer
coefficient of 14.72%. Furthermore, the Nusselt number increased by
9.51%, an enhanced coolant heat transfer rate of 14.79% was observed.
Tzeng et al. [310] used CuO and Al2O3 nanoparticles dispersed in
engine transmission oil for cooling of automatic transmissions. The
author found out the temperatures at high and low rotating speeds were
reduced. Fan et al. [282] reported that TiO2 NPs dispersed in ethylene
glycol used in an integrated reactor heat exchanger. In steady state
continuous experiments, there was an increase of 35% in the overall
M.E.M. Soudagar et al. Energy Conversion and Management 178 (2018) 146–177

heat transfer coefficient. Table 5 illustrates the NPs synthesis method

Catalytic converter, solar cells, gas sensors, metallurgical

Electrodes, hydrogen storage media, sensors and probes,

Electrodes, hydrogen storage media, sensors and probes,

Anticorrosion agent; electronic devices; electrodes and

and applications.

Paints, fabric coatings, catalysis, cosmetics, papers.

A study on US industry for generating electric power suggested that

Biomedical; gas sensors, solar energy conversion,

Surgical equipment, contraceptive devices, water
Sensors, cosmetics, photovoltaic cells, catalysts.
10–30 trillion btu/year can be saved by utilizing the nanofluids in
closed loop cooling cycles which is equal to approximately about the

MRI, DDS, catalysts, spintronics devices.

consumption of energy for 50,000–150,000 households. Furthermore,
the reductions in emissions were approximated to 5.6 million metric
tons of CO2, 21,000 metric tons of SO2 and 8600 metric tons of NOX
[283]. NPs in nanofluids exhibit exceptional lubricating properties be-
cause of the formation of a shielding film with lower hardness and

field emission devices.

field emission devices.

elastic modulus on the worn-out surface. Zhou et al. [284] estimated Cu

sensors, Li-batteries.
NPs tribological behavior with oil on a four-ball machine. The Cu NPs
as an oil additive reduced friction drastically and improved antiwear

applications.
Application

purificants.

electrodes.
properties compared with zinc dithiophosphate, specifically at high
functional load. Furthermore, the author reported it also increase the
load carrying capacity of the base oil.
The distinct types of nanofluids are the ferromagnets. They com-

Carbon arc discharge, laser ablation, CVD, electrolysis, pyrolysis over

Thermal and sonochemical reduction; sol-gel reaction; hydrothermal

Sol-gel method, inverse micelle method, chemical vapor deposition
prise of small magnetic particles of magnetite and are known as stable

Electric arc technique, carbon arc discharge, laser ablation, CVD,

Chemical reduction, electrochemical techniques, photochemical
colloidal suspensions. In order to obtain the colloidal stability, the
magnetic nanofluids size can be varied and they are capable of adapting
the surface coating [297]. It can be used as an alternative to the me-
chanical sealing, the magnetic sealing results in an economical solution
to the hazardous gas sealing and offers an eco-friendly alternative. It is

Hydrothermal, solvothermal, electrodeposition

extensively used in engineering rotation equipment which offers a high-
speed competence, lower friction power losses, extended life and high

Hydrothermal, reverse micellar synthesis

reliability [298]. In building heating systems, the nanofluids are used as

Electro-deposition, micro emulsion

a favorable alternative. A proportion of 60:40 ethylene glycol and water

electrolysis, pyrolysis over metal

(by weight) were used as a base fluid. There was a reduction of volu-
metric and mass flow rates in heat exchangers by using the nanofluids,
resulting in the power savings. Nanofluids reduces the initial equipment
cost, delivers the same amount of thermal energy as compared to the
Synthesis method

CVD, electrolysis
other larger heating appliances, hence the heating system size is opti-
mized [299]. The brake fluid used in the hydraulic braking unit assists

reduction
in dispersing the heat produced during the braking process which dis-
metal

perses the automobile’s kinetic energy. The CO and Al2O3 nanofluids

were used in the braking system, they were prepared by means of
submerged-arc synthesis and plasma-charging arc system respectively.
Particle size (nm)

The CO and Al2O3 nanofluids improved the mechanical and thermal

0.4–3.0 and

properties such as increase in the boiling point, viscosity, thermal 100–300

0.5–3.25

1.4–100

conductivity resulting in reduced occurrence of vapor-lock and im-

10–120
10–20

10–34
5–40

2–30

3–20
proved safety, in comparison with the commonly used brake fluid
[300].
Other applications include electrical power transformers, cooling,
AgNO3, Au, citrate, tannic acid, EDTA, graphene
Oleic acid, oleyl amine, triethanolamine, Pt, Au,
Zn acetate, polysaccharides, 2-mercaptoethanol,
Ce(NO3)3·6H2O, citrate, trioctylphosphine oxide

and heating in buildings, solar water heating, coolant in machining,

Graphite, hydrocarbons, Si, TiO2, methane

domestic refrigerators and chillers; cameras, micro-devices, and dis-

CuCl2·2H2O, NaOH, tetraoctyl ammonium
The nanoparticles synthesis method, applications and toxicity effect.

plays; cooling of electrical appliances and transformers; space, defense

and ships, nuclear reactor, and medical applications.
Graphite, Si or SiO2, Cu, and Al

5.5. Limitations of nano-additives

Precursor/surface coating

Several motivating properties of nano-additives have been de-

scribed in the review. In the previous literature, thermal conductivity
Fe3O4; Au, SiO2
and oleic acid

had gained the maximum consideration, however many investigators

TEA, Li-OH

have recently introduced studies on other heat transfer properties as

Graphite

bromide

well. The use of nano-additives in a wide-ranging variety of engine

Ag

applications appears encouraging. According to Saidur et al. [301], the

development in this field is hindered by (i) reduced characterization of
Graphene nano-foils
CNTs and MCNTs

suspensions; (ii) dearth of agreement of results achieved by different

researchers; (iii) lack of theoretical understanding of the mechanisms
responsible for changes in properties. Namburu et al. [302] reported
DCNTs

that CuO/ethylene glycol nanofluids, SiO2/ethylene glycol nanofluids,

Cu2O
CeO2
Type

TiO2
ZnO

FeO

and Al2O3/ethylene glycol nanofluids exhibits a lower specific heat

Ag

compared to the base fluids in engine applications. According to Lee

[285,286]

[287,288]

[290,291]

[295,296]

et al. [303] and Pantzali et al. [107], the main hindrance to the ap-
Table 5

[289]

[292]

[289]

[293]

[294]

plication of nanofluids in industries is its higher production cost. Na-

Ref.

nofluids are produced by either one-step or two-steps methods.

170
M.E.M. Soudagar et al.
However, both methods require advanced and sophisticated equipment.
The NPs propensity to agglomerate into larger particles, which limits
the advantage of the high surface area NPs. To avoid this tendency, the
particle dispersion additives are regularly added to the base fluid with
the NPs. Regrettably, this preparation can change the surface properties
of the particles, and nanofluids prepared in this way may comprise
undesirable levels of impurities. There is a lot of chemistry involved in
most of the oils that are used in engines. The oils are complex combi-
nations of chemicals that are in balance with one another and need to
be valued. It is for these reasons that the mixing of different oils and
adding more than one additives should be evaded. Young [304] re-
ported that the aluminium or boron NPs have an oxide layer. Although
the oxide layer is usually only a few nm, as the particles size reduces,
the oxide layer starts to occupy a higher fraction of the volume of the
particle. This in effect confiscates some of the accessible energy from
the particle. Qibai Wu et al. [222] concluded that the use of carbon-
coated aluminium may result in more ash accumulation in Diesel Par-
ticulate Filters (DPF) and affect the performance of the aftertreatment
system and the engine itself. It may, therefore, be necessary to clean or
change the after treatment system more frequently. Some of the
drawbacks from various literatures described: decreased cooling effect
inside the cylinder leading to increased HC emissions [305]; increase in
NOx emission probably owing to the catalytic effect of metallic ad-
ditives on combustion process [306]; dissolution in fuels at ultra-low
rates [230]; reduced combustion temperatures which could possibly
lead to weakened rate of biodiesel oxidation reaction in the chamber
and subsequently, depreciated combustion efficiency [307]; reduction
in ignition temperatures and calorific values [69]; low stability and
emulsifiers/surfactants need to be added and to avoid phase separation
[249]; there is a need for enhanced antioxidant additives that provide a
better balance between cost and performance [308].
6. Summary and conclusion
A comprehensive review on nano-additives preparation to their
application in diesel and biodiesel fuels has been presented in preceding
sections. The inclusion of nanoparticles in liquid fuel can offer many
advantages, such as the enhancement in performance and reduction in
exhaust emission. The following section summarizes the findings from
the exhaustive literature survey and a proposition is presented for the
study of nanoparticles as an additive for diesel and biodiesel fuel.
1. Around 90% of the literatures reviewed have shown a reduction in
exhaust emissions such as unburned hydrocarbons (UBHC), carbon
monoxide (CO) and particulate matters (PM) with the inclusion of
metallic and oxygenated additives in the diesel-biodiesel blends due
to enhanced ignition characteristics, higher oxygen content and
presence of lower aromatic compounds in biodiesel fuel and NPs
additives, that resulted in complete combustion. However, few in-
vestigators reported an increase in the concentration of CO emis-
sions due to the addition of magnetic NPs (FeCl3) in the fuel blend.
The addition of oxygenated additives leads to the formation of NOX
due to the excess amount of oxygen supply to the fuel and likewise
with the addition of Al-Mg and Co3O4 to jatropha biodiesel (JOME)
increase the NOX emission.
2. The addition of metal-based (Mn, Ni, Mg, Co) additives and few
oxygenated additives to the biodiesel blend decreases the viscosity,
density and flash point, though, the oxygen content of the blend is
increased. Although, few antioxidant additives increased the cetane
number and the flash point. In most of the recent studies, the oxy-
genated additives are used due to their low cost and the availability
of synthesis devices. At higher engine loads, the oxygenated ad-
ditives reduce the CO emission due to rise in temperature of the
combustion chamber. Furthermore, the oxygenated additives have
an inherent property of cooling, resulting in the reduction of cy-
linder temperature, and hence there is a negative impact on the
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Energy Conversion and Management 178 (2018) 146–177
engine performance parameters (BTE is reduced, BSFC is increased).
Generally, this is caused due to fumigation of oxygenated additives,
however, fumigation results in a reduction of the emissions, due to a
lower cylinder temperature.
3. A lower BSFC is preferred for the higher engine efficiency but, most
of the studies reported an increase in BSFC with the inclusion of
biodiesel due to the lower heating competence and lower calorific
value, hence the amount of the biodiesel emulsion fuel required to
reduce BSFC and increasing the efficiency will be higher. However,
the presence of metallic additives and oxygenated additives (diethyl
ether, isobutanol, ethanol) results in reduced BSFC due to higher
calorific value, catalytic oxidation enhancement and complete
combustion of the blended fuel.
4. There is a large literature gap in the investigational studies in the
addition of various types of NPs in various biodiesel feedstocks. The
combination of metallic NPs is investigated in many studies, how-
ever, the combination of organic NPs with metallic and/or CNT NPs
in diesel/biodiesel fuel is yet to be investigated, and a comparative
performance analysis on NPs and fuel blends and optimization of
dosage rate of NPs is needed.
5. The stability of the nanoparticles plays a vital role in the study of
performance enhancement and emission reduction of diesel-bio-
diesel fuel blend with NPs additives. The stability of the sonicated
nanofluids were studied only during the period of the experi-
mentation, the long-term stability of nanoparticles were not en-
compassed which, hinders the future use of nanoparticles for com-
mercialization. It is essential to conduct investigational studies on
the selection of an effective surfactant to avoid the agglomeration
and precipitation of nanoparticles.
6. The nanofluids should be improved and optimized with respect to
the properties such as stability, particle size distribution, material,
temperature, and shape. The knowledge of nanofluids is in devel-
oping phase and the results from the literature are insufficient to
conclude a complete enhancement in heat transfer characteristic by
using nanoparticles. In addition, there is a necessity in preparation
of low viscosity and high thermal conductivity nanofluids to meet
the broad heat transfer applications.
7. The metallic and CNTs nano-additives were found favorable with
respect to their effects on emission reduction and engine perfor-
mance enhancement. TiO2 additives were more effective in enhan-
cing the engine power. Addition of metallic NPs resulted in reduced
ignition delay period, enhanced the calorific value and oxidation
rates leading to a complete and cleaner combustion.
These are some of the probable facts through which the study on the
inclusion of nanoparticles in the diesel-biodiesel blends can be ac-
complished by the researchers. Also, there is a necessity in the in-
vestigation of the dosage value and the long-term stability of the na-
noparticles with the fuel blend. Furthermore, a cost-effective method
for developing nanoparticles, and the environmental damages and
health risk on exposure of nanoparticles on humans, should be in-
vestigated.
7. Future recommendation
1. An extensive investigation of the surface reactive NPs on engine
wear and engine parts (piston and piston rings, cylinder and cy-
linder linings, and fuel injectors) and exhaust pipe corrosion is re-
quired to confirm the reliability of nano-additives in a diesel engine.
2. There is a need of the exhaustive study on the stability, thermal
conductivity, durability tests, unconventional models, and shelf life
of NPs with respect to liquid fuels. The automobiles should be de-
signed and modified with respect to the parameters like the swirl
ratio, pilot injection and nozzle geometry modification (enhances
the spray patterns and reduces the droplet size). Improvising the
engine compatibility with nano-additives and diesel/biodiesel fuels
M.E.M. Soudagar et al.
and making it feasible for commercialization.
3. The research on the use of organic NPs as nano-additives with
diesel/biodiesel fuels is lagging in comparison with the metallic,
non-metallic and CNT NPs.
4. The impact of metallic-based and carbon-based NPs used in diesel/
biodiesel on human health should be obligated before introducing
the technology in the market.
5. The cost analysis and the complexity in preparation of NPs, public
safety, and economic feasibility should be considered in the future
researches. Furthermore, efforts should be made in developing cost-
effective and efficient NPs.
6. A further scope of research is needed in the superficial and inter-
facial effects, the nanoparticle motion, and the interactions between
the static and flow conditions.
7. There is a further scope in the study on the effects of nanoparticles
in the exhaust emission. It raises an issue on the environmental
pollution caused due inclusion of nanoparticles in diesel and bio-
diesel fuels.
Acknowledgment
The authors would like to acknowledge the Ministry of Higher
Education of Malaysia and University of Malaya, Kuala Lumpur,
Malaysia for their financial support under the BKP Special Grant
(BKS060-2017) and UMRG Grant (RP046C-17AET).
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