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ENHANCEMENT COMBUSTION AND IGNITION CHARACTERISTICS OF BIODIESEL/DIESEL FUEL MIXTURES BY NANO ALUMINIUM (N-AL) AND NANO ALUMINIUM OXIDE (N-AL2O3) ADDITIVES

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International Journal of Civil Engineering and Technology (IJCIET)
Volume 10, Issue 04, April 2019, pp. 114-124, Article ID: IJCIET_10_04_013
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJCIET&VType=10&IType=4
ISSN Print: 0976-6308 and ISSN Online: 0976-6316
© IAEME Publication
Scopus Indexed
ENHANCEMENT COMBUSTION AND
IGNITION CHARACTERISTICS OF
BIODIESEL/DIESEL FUEL MIXTURES BY
NANO ALUMINIUM (N-AL) AND NANO
ALUMINIUM OXIDE (N-AL2O3) ADDITIVES
Jihad.Kadhim.AbdAli
Agriculture College, Al. Qasim Green University, Babil, Iraq
ABSTRACT
The experimental investigation of combustion behavior and ignition process of Al
and Al2O3 nanoparticles which are in stably suspension in mixture of fuel that which
containing from oil fuel such as diesel and biodiesel (jatropha). The problems with
diesel and biodiesel in combustion processes and ignition process are incomplete
combustion, ignition delay and emissions etc. The aluminum (40nm) and aluminum
oxide (30nm) additive nanoparticles size are added to the fuel mixture in order to
enhance combustion and ignition performance. The volume fraction percentage of the
nanoparticles additives are varies from 0.1% to 0.5%. In the current work, we illustrate
the increase in heat of combustion and reduction of ignition delay. This experimental
study shows the characteristics of fuel mixture with nanoparticles for active materials.
The first step of this study is to prepare the fuel mixture from 50%diesel plus 50%
biodiesel , n-Al and n- Al2O3 using the magnetic stirring ceaseless with heating. The
second method is to prepare the fuel mixture by ultrasonic bath. This is used for the
complete mixing of fuel and highly decreases the separation of fuel mixture, Aluminum
and Aluminum oxide. From this investigation, it can be concluded that the aluminum
and aluminum oxide nanoparticles act to increase the energy density and heat of
combustion and reduce evaporation delay. Photographs taken by using scan electron
microscope show the morphology of the state of additives and mixture agglomeration
elements.
Key words: Diesel/biodiesel mixture, stirring process, nano fluid, combustion,
ignition.
Cite this Article: Jihad.Kadhim.AbdAli, Enhancement Combustion and Ignition
Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano Aluminium (N-Al) and
Nano Aluminium Oxide (N-Al2o3) Additives, International Journal of Civil
Engineering and Technology 10(4), 2019, pp. 114-124.
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Enhancement Combustion and Ignition Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano
Aluminium (N-Al) and Nano Aluminium Oxide (N-Al2o3) Additives
1. INTRODUCTION
The current work, investigating nanoscale particle additives, that is not yet complete fully
understood. Recent experimental studies results show that addition of nanoparticles (typically
metal oxides nanoparticles, such as aluminium and alumina) can improve the combustion
process and ignition mechanism of liquid fuels, probably influencing and increasing the thermal
exchange process between the droplets mixture and the surrounding oxidation. The added
nanoscale particles can be little enough to approach dimensions of atoms and molecular
distribution, enhance the physical properties of fuel (such as thermal conductivity, mass
distribution and heat transfer) and increase the surface area to volume ratio of the fuel droplets,
permitting more fuel to be in contact with the oxidant. High energetic metals such as aluminum
have higher combustion energies and have been employed as energetic additives in propellants
and explosives as indicated byYetter.et al. [1].Recent advances in nanoscience and
nanotechnology are in the areas of production, control, and characterization of nanoscale
energetic materials, which have shown substantial merits larger size particles such as micronsized ones. Due to the more specific surface area, particles metallic nanoparticles offer less
ignition delay, reduced burn times, and a more complete combustion than micron-sized particles
.Thus, nanoscale energetic metals as fuel additives to enhance combustion of liquid fuels are an
important concept. The high energy density of energetic materials, especially aluminum, could
significantly enhance the power output of engines and thus decrease fuel consumption and
consequently result in a lower emission of CO, NOx etc. In addition to the higher energy
density, fuel additives have the possibility to shorten the ignition delay time and improve fuel
oxidation by catalytic effect. These investigations are focussed on the analysis of the ignition
probability nanofuel droplets impinging on a hot plate. It has been observed that the ignition
temperature of fuel mixtures containing nanoparticles is lower than that of pure diesel. In fact,
ignition temperature and ignition delay are critical parameters to characterize the rendition of a
fuel mixture, for both emission levels and efficiency of the combustion process. Moreover, it
has been noticed, as indicated by Kuo and Risha [2], that the use of nanoparticles in rocket
propulsion can enhance the engine performance under the point of view of specific thrust.
Previous studies explain the behavior of suspended metallic nanoparticles in liquid fuels and
explored the differences between nano suspensions and micron suspensions. Nanoparticles
have shown such merits as higher reactivity and burning rate over micron-sized particles. More
importantly, nanoparticles are much easier to disperse and suspend in liquid fuels than micro
particles, the latter are inclined to settle quickly as a result of gravity. Nanoparticles have an
extremely high ratio of surface area to space volume; interaction between particle surface and
the surrounding liquid is strong enough to overcome difference in density. Larger surface area
of particle when become nanoscale can be utilized for surface functionalization, making a much
stabilized suspension state possible to maintain for a very long time in practical applications.
In liquid fuel the ionic groups can be absorbed onto particle surfaces to form a charged layer,
which results in repulsive forces. These forces between nanoparticles increase as a result of the
larger specific surface areas of nanoparticles, and this may reduce agglomeration to some
extent.
This study explains effect of nanoenergetic additives on the ignition property of
diesel/biodiesel with a hot-plate requirements setup, and heat of combustion by the static bomb
calorific system to explore the underlying mechanisms of combustion. There are more merits
to adding nanoparticles to liquids and solid fuels, such as shortened evaporation delay, more
energy density, and high burn rates by Galfetti.et al. [3]. The mixture is prepared by the
sonicating process and ultrasonic bath to improve the mixing properties. Recent studies have
also shown that the addition of nanoparticles to a fluid can improve the physical properties such
as thermal conductivity, as outline by Risha and Boyer, Pivkina.et.al and De Luca.et al. [4-6],
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by Prasher.et al. [7-9] mass diffusivity by Krishnamurthy.et al. [10] and radiation heat transfer.
By Prasher and Phelan [11], Pantoya and Granier [12], As a result it is possible in principle to
achieve the desired properties of a fluid by adding some specifically tailored nanoparticles, as
indicated by Gan and Qiao [13].In the current work, aluminium and aluminium oxide are
suspended in mixture fuel , with volume fractions in the range 0.1% to 0.5%. The mixture
droplets are released onto a hot plate at temperatures varying from approximately 700 ºC to 800
ºC .The preparation of the nano fluid is discussed in the Sonication section. The experimental
procedure is discussed in the subsequent section followed by the one on Results and
Discussion.
2. SONICATION
The ultrasonic bath improves the mixing property of nano aluminium and nano aluminium
oxide with fuel mixture .The direct mixing of aluminium or aluminium oxide with
diesel/biodiesel leads to a complete settling down of nanoparticles as shown in Fig.2. Also,
ultrasonic bath leads to improvement of the mixing property of diesel/biodiesel with aluminium
and aluminium oxide by using a sonigator. The properties and characteristics of the nano fluid
depend on the mechanism of mixing and period of time in the bath. Fuel samples were sonicated
in an ultrasonic cleaner for at least 30 minutes at 45 kHz with a power rating of 140 watts.
Ultrasonic-induced cavitation applies mechanical stresses between particles to break them apart
and reduce agglomeration. Two additional approaches to stabilization include electrostatic
stabilization and steric stabilization in the mixing processes. After sonication the mixtures are
permitted to cool down to 25°C for 45 minutes, before starting the experiments. No surfactants
were added to the samples.
Figure 1. Steric stabilization (left) and electrostatic stabilization (right) of additives in a solution
respectively.
3. DIESEL, BIODIESEL ALUMINIUM AND ALUMINIUM OXIDE
PROPERTIES
The properties of diesel/biodiesel are shown in Table 1. A set of tests was performed in order
to observe the solubility of diesel/biodiesel with the help of additives. Diesel/biodiesel is mixed
with n-Al (or n-Al2O3) into a homogenous suspension in a container by stirring it. The mixture
is kept in the container to study the solubility and phase stability. The state of phase separation
takes place soon after stirring.
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Enhancement Combustion and Ignition Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano
Aluminium (N-Al) and Nano Aluminium Oxide (N-Al2o3) Additives
Table 1 Properties of fuel materials
NO
Properties
1
Density
0.86
0.92
Units
Magnitude
g/cc
2
HCV 1008
E-HCV
Krakatau
Flash Point
43.4
63
MJ/kg
40
61
MJ/kg
50
90
Cᵊ
3
4
Diesel
Biodiesel
To surmount this problem, additives are added in equal proportion to diesel. Nanoparticles
are relatively miscible and do not have any clearly visible interface. The mixture is formed after
magnetic stirring. The important parameters in this process are heat, stirring time, time and
frequency for the ultrasonic bath.
Table 2 Properties of nano aluminum and nano aluminum oxide materials
NO
Properties
Aluminum
Aluminum
Oxide
2
1Density
2Manufacturer
Nanoshel LLC
3Oxide phase
4Average particle size
5Specific surface area
6Purity
7Color
Amorphase
40
10.84
99%
Black gray
(a)
3.9
Units
g/cc
Alpha .SRL
Alpha
30
nm
38
m2 /g
99.9%
White
(b)
Figure 2.SEM images of a) N-Al, b) N- AL2O3 at 500 nm magnification.
3. EXPERIMENTALS METHODS
Regarding constant volume calorimeter experiments, the reactants are enclosed in a stainless
steel vessel and ignited in pure O2 to ensure complete combustion. The heat of combustion of
the fuel sample is determined indirectly from the heat transfer to the surrounding distilled water.
In the present study, the combustion experiments were carried out with a modified static bomb
calorimeter .The calorimeter system is well insulated in Fig.3. The hot plate setup is illustrated
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in Fig.4. It can be noticed from the figure that the hot plate is putted directly on the top of a
circular electric heater. The fuel mixture droplets are slowly released onto the hotplate from a
syringe placed on the top. Insulating material is placed around them in order to reducing the
heat losses. The plate is constructed from stainless steel metals, and has a diameter of 60 mm
at the top. It has a small concave portion at the top in order to ensure that the droplet does not
move off the top surface. A plastic pipette was joined to a movable arm such that it could be
positioned directly over the hot plate when desired. In order to reduce the movement of the
droplet, the hot plate was carefully leveled and positioned such that the droplet fell as close as
possible to the center of the plate. Before starting, the plate was carefully polished and cleaned
in order to minimize the effect of the surface or any effects of hot spots remaining.
Figure3. Experimental setup (bomb calorimeter).
Figure4. Schematic of the experimental setup (Hot plate ignition probability).
4. RESULTS AND DISCUSSION
The heat of combustion (HoC) of diesel /biodiesel based fuels is determined for both aluminum
and aluminum oxide, the nanoparticle volume fraction range is from 0.1% to 0.5%. The heat
of combustion values are represented with uncertainty band. From basic energy conservation,
the HoC can be written, as indicated by Jones.et al. [15], as
H = C S T + ngas RT + ngas RT
(1)
Where Δngas is the change in moles of gas between reactants and products, R is the ideal gas
constant (8.3145J mol-1K-1), CS the heat capacity of the system and T the final temperature of
the gases. The first and final terms of RHS of Eq.1 indicate that combustion products with a
higher flame temperature will have a higher heat of combustion. The enhancement in HoC with
n-Al and n-Al2O3 is between 12-41% over pure diesel/biodiesel fuel.
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Enhancement Combustion and Ignition Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano
Aluminium (N-Al) and Nano Aluminium Oxide (N-Al2o3) Additives
Table 3 Symbol and units of quantities for heat of combustion and ignition delay
NO
1
2
3
4
5
6
7
8
9
10
11
12
13
Symbol
HoC
Δngas
H
R
Cs
n-Al
n-l2o3
∆T
t oxide
r
ρAl
ρAl2o3
C
Quantity Magnitude
Heat of combustion
Change in gas moles
Enthalpy
Ideal gas constant
Heat capacity
Nano aluminum
Nano aluminum oxide
Temperature difference
Oxide layer
Outer mean particle radius
Aluminum density
Aluminum oxide density
Pure aluminum and aluminum
Units in SI
MJ/Kg
moles
J
J mol-1K-1
J/Kg.K
Nm
Nm
°C
Nm
Nm
g/cc
g/cc
%volume
fraction
Volumetric HoC(MJ/Kg)
60
50
volumetric HoC
40
30
20
10
Linear (volumetric
HoC)
0
0
0.1
0.2
0.3
0.4
0.5
Fuel mixture+N-Al Volume Fraction (%)
Figure 5. Enhancement ratio of fuel mixture + N-Al.
Volumetric HoC(MJ/Kg)
60
50
40
Volumetric HoC
30
20
10
Linear (Volumetric
HoC)
0
0
0.1
0.2
0.3
0.4
0.5
Fuel mixture +N-Al2O3 volume Fraction (%)
Figure 6. Enhancement ratio of fuel mixture N-Al2O3.
For Al and fuel-oxidizer mixtures with flame temperatures below the aluminum
vaporization temperature, combustion is expected to occur as a heterogeneous surface reflex,
while for mixtures with flame temperatures above the aluminum vaporization temperature,
they typically occur in a diffusive gas-phase, as indicated by Bazyn.et al. [16]. The
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nanoparticles have a dominating component of Al2O3 coating which was found to increase the
stability of the samples. Figures (6, 7) show the enhancement in the HoC for diesel with n-Al
and n-Al2O3 particles. However, as predicted, the n-Al2O3 nanoparticles do not react with the
ambient O2. The increase in HoC is due to the increase in adiabatic flame temperature of
combustion for the mixture, as indicated by Chen .et al. [17]. The oxide layer has a significant
effect on reaction energetic.
Hot plate ignition probability for pure diesel/biodiesel is shown in Fig.7. The
comprehensive results of ignition probability are obtained using the various mixtures of
nanoparticles (Al -40nm and Al2O3 -30 nm) with diesel/biodiesel. Thermally conductive
nanoscale additives in diesel/biodiesel are known to significantly enhance thermal transport
properties in the liquid mixture, leading to reduced ignition delays. The ignition characteristics
may be enhanced due to the reactive nature of the additive material. The (spark) ignition occurs
earlier due to the increased surface area and size-dependent melting point depression due to
additives. The uncertainty in ignition probability is found to be ± 9.8% and the uncertainty in
hot-plate temperature is ±25ºC. This is similar to the procedure adopted by Kim.et al.[18], [19].
The uncertainty in ignition probability is calculated using the Student-t method and assuming a
95% confidence level. The nanoparticles, when added, lead to a decrease in oxide layer
thickness (toxide) because of decreasing particle size and the melting response move toward
lower temperature and heat of fusion decreases. The effect of oxide coating on the particles is
to apply compressive force to the aluminum core, thereby increasing the melting point and
heat of fusion. The size dependent heat of fusion is significantly less than that predicted by the
effect of surface tension, indicating that the solid nanoparticles are at a higher energy than
expected, presumably due to the presence of defects or irregularities in the crystal structure, at
or emanating from the surface, as outlined by Sun and Simon [20]. This is increasing due to
exposure to the atmosphere during storage. The equation for the oxide layer, as given in [20],
is as follows:

 Al2 O3 c
 
= r 1 − 
  + c  Al O −  Al
2 3
  Al
1

3 

toxide
(2)
 
 

Where (ρAl) and (ρAl2O3) are the aluminum and aluminum oxide Al2O3 densities, (r) is the
outer mean particle radius, and (c) is the pure aluminum content by mass. Based on the threshold
of experimental and simulation enhancement (0.5%), the estimated oxide layer thickness from
this calculation is 10nm. A reduction in surface tension and contact angle may facilitate the
occurrence of ignition as indicated by Sanchidrian.et al. [21]. The heterogeneous nucleation has
a vital role in enhancing ignition behavior. A mild disruptive burning phenomenon is observed
for the nano-fuel mixtures, where there is a fragmentation of a parent droplet into smaller ones.
With the vaporization of a volatile liquid, there is a formation of a porous non-volatile shell on
the exterior of the droplet, with subsequent pressure build up and ignition of the interior liquid.
It can be clearly observed From Fig. (8,9) that the mixtures containing n-Al and n-Al2O3 show
significantly higher ignition probability compared to pure diesel. All the mixtures burn 100%
of the time at a temperature of 760ºC.
(
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Enhancement Combustion and Ignition Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano
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Figure7. Ignition probability of pure fuel mixture
The addition of nanoparticles tends to significantly increase the ignition probability of the
fuel, as indicated by Tyagi.et al.[22]. Interestingly, while looking at the corresponding results
of pure diesel/biodiesel (shown in Fig.7), one significant difference can be observed. The
ignition probability of pure diesel at a hot-plate temperature of 760°C is 100%, according to the
data shown in Fig. ( 8,9) however the values of ignition probability of nano mixture are in the
range of temperature ,when take the three points of temperature 720°C ,740°C and 760°C,is
observed the effect of nanoparticles on the ignition temperatures. There are significant
differences in the ignition probabilities of pure diesel depending on whether a particular set of
experiments was performed on an uncontaminated surface which is the case in Fig. 7 or if it
was performed on a surface on which prior experiments had been carried out using any
nanoparticle + diesel/biodiesel mixture, as mentioned by Coops.et al.[23].
Also it can be clearly observed that these increases in ignition probabilities are
comparatively more than the uncertainties associated with measurement of ignition probability
in the current experimental setup. It is suspected that when experiments using fuel mixtures that
contain nanoparticles are performed, some residue is deposited on the hot plate surface. The
presence of any residue on the plate might influence the ignition probabilities of the subsequent
batches of pure diesel droplets which in normal circumstances would have encountered an
uncontaminated surface with no deposited residue.
Figure 8. Ignition probability of fuel mixture+ N-Al.
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Figure 9. Ignition probability of fuel mixture+ N-Al2O3
Figure.10. shows the surface morphology of residual nanoparticles after combustion. In
particular, diesel/biodiesel +0.5%n-Al and 0.5% n-Al2O3 flake into a powdery substance. This
is a characteristic of n-Al and n-Al2O3 combustion products. The probability of ignition to the
nanoparticle fuel mixtures in all cases is observed to be much higher than that of pure
diesel/biodiesel. By adding 0.5% n-Al volume fraction, one observes a 44% increase in ignition
probability at 740ºC. With 0.5% of n-Al2O3, the increase is 35% at the same temperature. This
is due the fact that when the internal heating is increased, the rate of fuel vapor generation is
also increased. At an instantaneous critical point, there is a transition from pure vaporization of
the droplet to active chemical reactions in the surrounding gas-phase, favoring increasing
pressure, temperature, and oxidizer concentration for ignition, as indicated by Law [24].
(b)
(a)
Figure10. SEM images of residual combustion products of (a) fuel mixture + 0.5% n-Al and (b) fuel
mixture + 0.5%n-Al2O3 400 nm magnification.
5. CONCLUSIONS
The effect of n-Al and n-Al2O3 on the fuel mixture has been investigated. The enhancement in
the HoC and ignition probability is determined. It is seen that the HoC increases almost linearly
with the nanoparticle concentration. Metal oxide nanoparticles of aluminium may be not be
stably suspended in oil base fuel up to the concentration of approximately 0.5% volume
fraction, it is recommended in future work that a dispersant be incorporated in the suspension
for higher nanoparticle loadings. It was by experimentally shown that the amount of heat
released from diesel combustion increases almost linearly with n-Al and n-Al2O3
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Enhancement Combustion and Ignition Characteristics of Biodiesel/Diesel Fuel Mixtures by Nano
Aluminium (N-Al) and Nano Aluminium Oxide (N-Al2o3) Additives
concentrations. Hot-plate ignition probability measurements are carried out on various volume
fractions of n-Al and n-Al2O3 mixtures. The measurements are conducted for the temperature
range 700°C - 800°C. Adding nanoparticles to the fuel causes significant enhancements in its
radiative and heat/mass transfer properties and hence the droplets ignited at a much lower
temperature and also more often as compared to pure diesel. Such an increasing heat and mass
transfer properties of fuel has the potential of reducing the evaporation time of droplets in a
compression ignition engine, and hence should favorably influence its ignition delay.
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