Title Science and Technology Indonesia e-ISSN:2580-4391 p-ISSN:2580-4405 Vol. 7, No. 4, October 2022 Research Paper Investigation of the Physical Properties and Droplet Combustion Analysis of Biofuel from Mixed Vegetable Oil and Clove Oil Adhes Gamayel1*, Mohamad Zaenudin1, M. N. Mohammed2, Eddy Yusuf3 1Department of Mechanical Engineering, Faculty of Engineering and Computer Science, Jakarta Global University, Depok, West Java, 16412, Indonesia2Mechanical Engineering Department, College of Engineering, Gulf University, Sanad, 26489, The Kingdom of Bahrain3Department of Pharmacy, Faculty of Pharmacy, Jakarta Global University, Depok, West Java, 16412, Indonesia *Corresponding author: adhes@jgu.ac.id AbstractThe study of vegetable oil used as fuel in conventional engines leads to problems like the low volatility and high viscosity. Thisresearch aims to evaluate the droplet combustion characteristics that correlated with the density, viscosity, and the flash point of thebiofuel from mixed vegetable oil with clove oil. Biofuels used in research are Jatropha Oil (CJO), Kapok Oil (KSO), Coconut oil (CCO),and all biofuel mixed with clove oil in 5% basis volume. Fuel properties that tested both biofuel and fuel mixture using the ASTMmethod are density (ASTM D1298), viscosity (ASTM D445), The flash point (ASTM D93). The droplet combustion experiment usedsuspended droplets placed in the junction of the K-type thermocouple and the Ni-Cr wire (as the coil heater) to heat the droplet untilthe combustion occurred. The result indicates that adding 5% clove oil in biofuel creates higher density, the viscosity decreasesuntil 10%, and the flash point decrease to 30%. Droplet combustion results that adding 5% clove oil creating a more completecombustion process in CCO than KSO and CJO. Higher viscosity in KSO and CJO leads to eugenol and terpene (clove oil compound)trapping in the fuel droplet. Due to eugenol and terpene having great volatility, they are evaporating rapidly leading to secondaryatomization and micro-explosion phenomena. KeywordsBiofuel, Vegetable Oil, Clove Oil, Micro-Explosion, Combustion Received: 21 July 2022, Accepted: 12 October 2022 https://doi.org/10.26554/sti.2022.7.4.500-507 1. INTRODUCTION The issue of global warming and climate change continues to strengthen cause the demand for substitute fuel has increased. Many researchers have been conducted studies to substitute diesel fuel with vegetable oils because of their advantages such as non-toxic and biodegradable (Che Hamzah et al., 2020). However, the demerit of vegetable oils for feasibility as diesel fuels are high viscosity and low volatility. High viscosity leads to poor fuel atomization and has a signicant eect on spray characteristics. Subsequently, the rate of evaporation of fuel has been decreased and creates inecient mixing of oil with air that contributes to incomplete combustion and leads to car- bon deposit formation on the crown piston, ring, and injector. Misre, ignition delay, and poor cold engine start-up are the eect of a combination of high viscosity and low volatility of vegetable oils. To reduce the demerit of vegetable oil, they can be mixed with oil that has low viscosity and high volatility (Al-Abdullah et al., 2015). Essential oil is a natural volatile oil that renewable resource and it is mostly used as additives in the pharmaceutical and cosmetic industries. It can be extracted from leaves, roots, buds, and petals using distillation (Gad et al., 2021). The main compound of essential oil is aromatics which involves single or multiple rings which are planar and have a periodic order of a p orbitals having 4n+2𝜋 electrons, and each atom involved in the fragrant ring includes a p orbital (Fu and Turn, 2018). Nowadays, the researcher is studying essential oil as blended fuel due to the equivalences in properties to conventional fuel. Pine oil has some prominent fuel-related properties, such as lower viscosity, ash point, and boiling point than those of pure diesel (Huang et al., 2019; Vallinayagam et al., 2013). Another essential oil, turpentine oil, could be implemented as additional fuel for implementation in diesel engine refers at many studies haveresulted inmuch-improvedperformancewhenturpentine oil has been used for up to 30% (Jeevanantham et al., 2020). Eucalyptus, tea tree oil, and orange have comparable values in basic fuel properties and higher surface tension than diesel fuel (Rahman et al., 2019). The addition of clove oil which acts as an antioxidant to B20 has decreased viscosity, density, ash https://crossmark.crossref.org/dialog/?doi=10.26554/sti.2022.7.4.500-507&domain=pdf https://doi.org/10.26554/sti.2022.7.4.500-507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 point, and caloric value and meet the ASTM standard for cold ow properties (Jeyakumar and Narayanasamy, 2019). To analyze combustion characteristics based on fuel com- ponents and properties, droplet combustion is a simple method thathavemodestutilization,andanattractiveanalysis (Gamayel et al., 2020). The disruptive burn in multicomponent fuel droplets has been compared with the steady burn in mono- component fuel (Hoxie et al., 2014). Many researchers have studied the single droplet combustion of vegetable oil in re- cent years. The Jatropha oil change at various diameters of droplet, but it does not change the ignition temperature at vari- ous oil temperatures (Wardana, 2010). Ignition characteristics and burning behaviors from butanol in the range of 25-75% mixed with soybean oil were analyzed as a result of the micro- explosion case in most violent at mixed butanol in 40% (Hoxie et al., 2014). In an extended experiment, butanol, pentanol, and soybean oil were blended in the binary-ternary form and then examined as single droplet combustion (Coughlin and Hoxie, 2017). Based on the previous study, a single droplet experiment and multicomponent analysis using essential oil as an addition to vegetable oil are rare. The correlation of molecule geometry and the motion of the molecule with prop- erties and the combustion need to be observed. Subsequently, an explanation of the ame geometry during micro-explosion needs to be studied. Hence, this experiment aims to study the performance of mixed vegetable oil with clove oil in terms of basic fuel properties and single droplet combustion. 2. EXPERIMENTAL SECTION 2.1 Materials Vegetable oil used in this experiment was crude oil, namely Jatropha Oil (CJO), Kapok Seed Oil (KSO), and Coconut Oil (CCO). Clove oil was mixed with each vegetable oil in 5% basis volume with initial namely, CJO95C5, KSO95C5, and CCO95C5. The observation in basic fuel properties and droplet combustion between vegetable oil and its blend. They were prepared using the splash blending method and kept at room temperature for several days to observe any phase sepa- ration in the fuel blend. Table 1. The Chemical Compound of Clove Oil Compound % Eugenol 63.74 cis-Caryophyllene (C15H24) 26.32 Caryophyllene 6.31 a-Humulene 3.53 The chemical compound of clove oil taken from our pre- vious study Gamayel et al. (2020), shown in Table 1 eugenol has the biggest compound with 63.74% in clove oil. Eugenol has a structure consisting of aromatics and hydroxyl groups (-OH). Phenol is one classication of eugenol where the pri- maryantioxidant which has a function to convert radical energy to become stable. An aromatics structure is a bulky structure composed of ring benzene. It leads to the density of aromatic compounds higher than diesel fuel and biofuel. Aromatic pro- motes the adiabatic ame temperature (Han, 2013). Hydroxyl groups are atoms with electronegative and donors in hydrogen bond (Lapuerta et al., 2015). a-Humulene, cis-Caryophyllene, and Caryophyllene are classied as sesquiterpenes with volatile compounds, a strong odor, and an antioxidant. Thevegetableoilcompositionfromtheliteratureandshown in Table 2. According to fatty acid composition, both CJO and KSO are unsaturated fatty acids, due to the high percentage of oleic acid and linoleic acid which have double carbon chains and bulky structures of the molecule. Meanwhile, CCO is a saturated fatty acid due to the highest compound is lauric acid which builds with 12-carbon atom a single chain. 2.2 Methods 2.2.1 Fuel Physical Properties Density is an important quality indicator for automotive, ma- rine, and aviation fuels. This number aects handling, storage, and combustion. Density is expressed in units of grams per liter, dene as the relationship between the mass and volume of a liquid (Atabani et al., 2013). It was found to relatively increase in density with the increase of unsaturation degree of vegetable oil (Altaie et al., 2015). Viscosity is an indication of a uid ability to owand it’s related to the cohesion forces among the molecule (Conceição et al., 2005). It has a signicant eect on spray characteristics and takes a long time to mix with air. The measurement used Leybold Didactic viscometerapparatus with the standard of ASTM D445. This method determines of kinematic viscosity of a liquid both transparent or opaque. The ash point indicates the presence of a highly volatile and ammabilityproperties of fuel (Atabani et al., 2013). The ash point also denes as a temperature that shows the rst ignition above the liquid of fuel (Keshavarz and Ghanbarzadeh, 2011). The measurement method used ASTM D93 with the closed cup ash point tester from Leybold Didactic. These test meth- ods cover the determination of the ash point of petroleum products, but this standard also can use for vegetable oil in similar diesel engine implementation 2.2.2 Droplet Combustion The experimental setup was similar to the previous study by Gamayel et al. (2020) were used the transformer, Ni-Cr wire, K-type thermocouple, syringe, data acquisition system, and camera. The Hamilton microliter syringe was used to create a droplet in the volume range 0.5∼1 microliter. The use of syringes is dierent from the previous studydue to the dierent syringe materials leading to an easier practical handling of the droplet in junction thermocouple. Digital single-lens reex camera at 25 fps (Canon EOS 4000D) used to record the ame evolution. The disruptive light has created the capture of ame shape and the color degradation of ame is unclear. Besides that, the micro-explosion phenomena that describe in ’ame in ame’ can’t be captured. The disruptive light in ame © 2022 The Authors. Page 501 of 507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 Table 2. Fatty Acid Percentage Fatty Acid Composition Number of C CCO (Nakpong and Wootthikanokkhan, 2010) KSO (Wirawan et al., 2014) CJO (Meher et al., 2013) Caprylic Acid (C8:0) 3.35 0.009 - Capric Acid (C10:0) 3.21 0.072 - Lauric Acid (C12:0) 32.72 0.071 - Myristic Acid (C14:0) 18.38 1.22 0-0.1 Palmitic Acid (C16:0) 13.13 2.4 14.1-15.3 Stearic Acid (C18:0) 3.6 - 3.7-9.8 Oleic Acid (C18:1) 12.88 20.15 34.3-45.8 Linoleic Acid (C18:2) 4.35 53.78 29-44.2 Linolenic Acid (C18:3) n.d 1.30 0-0.03 % Unsaturation 17.23 73.93 63.3-90 duringtherecordwouldbeminimizedwithsetuptheExposure Value (EV) in 1600. The result of the video recording is to be converted to image in JPEG format using "Free Video to JPG Converter" to know the detail of the evolution of ame. The thermocouple was plugged into the DATAQ acquisition system to measure the droplet combustion temperature. This installation was connected to the computer to display the result in excel form. The experiments were performed in normal gravity and shown schematically in Figure 1. A microliter syringe creates a droplet and takes it to suspend in the junction of the thermocouple. Thus, the nickel coil heater and video recording are turned on together to ensure data take at the same time with the thermocouple. When ame-o occurs, all measurement takes a stop. Figure 1. Droplet Combustion Experimental Set-up 3. RESULT AND DISCUSSSION 3.1 Fuel Physical Properties The result of density according to Figure 2; for CJO, KSO, CCO, namely 0.921 gr/mL, 0.917 gr/mL, 0.913 gr/mL, then add clove oil become slightlyhigh at 0.93 gr/mL, 0.926 gr/mL, 0.923 gr/mL. The previous experiments result the density of CJO, KSO, CCO, namely 0.901-0.940 gr/mL (No, 2011), 0.923 gr/mL (Vedharaj et al., 2013), 0.920 gr/mL (Chin- nammaetal.,2015). Thefuel injectionprocessdependsonthe densitydue to the estimation in its volume (Sajjadi et al., 2016). CCO has a lowerdensity than CJO and KSO. Molecularweight and structure are the factors that aect density. Vegetable oil has a molecular weight of 600-900 g/mol (Misra and Murthy, 2010) due to triglycerides and their fatty acid. Based on Ta- ble 2, fatty acids with double bonds in each vegetable oil are CJO±80%, KSO±70%, and CCO±18%. It can be stated that density increases in vegetable oil with a high percentage of unsaturated fatty acid. The aromatic structure that compounds clove oil consists of one aromatic ring and a few sides of the alkyl chain. The aromatic ring that arranged in a dense and rigid was inuenced a high density of clove oil. The result shows that blending with clove oil at 5% makes all the density of vegetable oil increase. CJO95C5 is the highest density due to the unsaturated fatty acid percentage until 80%. Since the density of vegetable oil and its blend higher than diesel fuel (0.840 gr/mL), the use of fuel blends in diesel fueling systems would require modication of the equipment designed to work with a lighter fuel (Laza and Bereczky, 2011). Figure 2. The Density of Vegetable Oil and Their Mixture Figure3 illustrates theeectsofmixedcloveoil at5%onthe viscosity of vegetable oil. CJO and KSO are a higher viscosity than CCO due to the percentage of oleic acid in CJO and KSO higher than in CCO. Oleic acid is an unsaturated fatty acid with a single double bond. The presence of a single double © 2022 The Authors. Page 502 of 507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 Figure 3. The Viscosity of Vegetable Oil and Their Mixture bond leads to increase viscosity, whereas two or three double bonds caused a decrease in viscosity (Demirbas, 2008). It gave rise to stronger intermolecular interaction between the 𝜋 electron of the double bond because a spatial geometry of the cis conguration of the one double bond of oleic still allowed a close packing between a molecule (Romuli et al., 2019). The stronger intermolecular interaction causes the motion of the molecule to become inactive and viscosity is become increase. In this experiment, CCO is the most viscous oil due to more percentage of lauric acid, which has a weak van der Waals interactions and does not have strong orbital. BasedonFigure3,viscositydecreasedto10%whenblended with clove oil 5%. Viscosity in 24.33 mm2/s2 reached by CCO mixed with clove oil 5% marked as lower viscosity than KSO and CJO. Meanwhile, the viscosity of clove oil is 4.1 mm2/s (Mbarawa,2010) betweentherangeofdiesel fuelviscosity(2.2- 5.3 mm2/s). It can be stated that all of these vegetable oils and their blend can’t directly use in the engine due to the viscosity number not being in the range of diesel fuel. It requires fuel modication like preheating or transesterication to biodiesel. Figure 4. The Illustration Motion of Molecule (a) Vegetable Oil, (b) add Clove Oil Vegetable oils are non-polar molecules with a low degree of electronegativity. The intermolecular bond in vegetable oils is the London dispersion force with the instantaneous dipole and the aected dipole. The London dispersion force causes the molecule to move even if only for a moment. Adding clove oil makes the motion of the triglycerides becomes active. Clove oil is moderately polar due to eugenol and terpene be- ing a major compound that has a hydroxyl group (-OH) and aromatic structure. The dipole generated by eugenol that its polarity induced by the hydroxyl group (-OH). The electron has active motion around the aromatic ring which is called de- localized. The repulsive and attractive force created byelectron motion between aromatics and triglyceride. The force leads to molecule oscillation between them. A detailed illustration of the molecule’s motion can be seen in Figure 4. With more oscillation of molecules on the fuel blend, viscosity would be lower or the fuel mixture more viscous. The ash point of vegetable oil depends on molecular weight, long-chainhydrocarbon, andthedegreeofdoublebond fatty acid (Carareto et al., 2012; Keshavarz and Ghanbarzadeh, 2011). The previous paper reported that the molecular weight of vegetable oil is 20% higher than diesel fuel and causes low volatility (Misra and Murthy, 2010; No, 2011). Vegetable oil has a strong London dispersion force caused by its large molec- ular weight and bulky structure. That makes vegetable oil need more energy to vaporize and dicult to ignite when exposed to a ame. Figure 5. The Flash Point of Vegetable Oil and its Blend Figure 5 shows that the ash point of KSO is the highest. Other literature Blin et al. (2013) was stated that the higher percentage of the single double bond composition in the veg- etable oil led to a higher ash point. More energy is needed to break this interaction and release the molecule which is in the liquid to vapor phase to form a combustible mixture in air. It produces higher temperature in the liquid where the tempera- ture is the main factoron the ash observed. The mixture at 5% clove oil on vegetable oil can depress the ash point until 30%. All vegetable oils that add 5% clove oil has the ash point in the range of 182-188◦C. It means that the blended fuel with clove oil increases the volatility and consumes lower energy than usual to obtain the same evaporation amount. The aromatic structure and hydroxyl group in clove oil are the main factor to depress the ash point in vegetable oil. The presence of aromatic structure and hydroxyl group makes molecular inter- action of triglyceride weaker than usual and causes oscillation of triglyceride more active. As a result, the fuel blend needs lower energies to be vaporized into the vapor phase. At the © 2022 The Authors. Page 503 of 507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 ash point, the concentration of vapor on a fuel surface is equal to the lower explosive limit (LEL) of the vegetable oil-clove oil, vapor-air mixture. 3.1.1 Droplet Combustion Figure 6. The Sequence of Droplet Combustion in Vegetable Oil and its Blend Figure 6 exhibit the ame evolution with the sequence in each frame is 0.04 second with the result that CCO and CCO95C5 get a more complete combustion process than KSO and CJO. The ovoid ame denes as a ame with the similar shape of an egg and has around in tip ame. It explains perfect combustion in the sequence of ame. It’s exhibits that the ovoid ame occurs more frequently in CCO than in KSO and CJO. The ovoid ame that occurs in CCO was captured in 10 frames, CCO95C5 in 11 frames, KSO and CJO in the range of a 6-8 frame. Generally, the geometry of ame gets dierences from the rst ignition, micro-explosion, and ame extinction in CCO, KSO, CJO, and its blend. The bulge geometry of ame and rapid change becomes like a spike is the mark of the initial micro-explosion (Wardana, 2010). In CCO, the geometry of ame is like an ovoid from the start ignition until 0.4 seconds and then the bulge geometry and spike ame height take place. The Ovoid ame geometry takes place in CCO95C5 more than in CCO. It takes time in 0.48 second before the bulge geometry and spike ame starts. The ovoid ame geometry in CCO and its blend has a long duration time due to the presence of lauric acid which contain up to 30% in triglyceride that led to stable combustion. In CCO, the change of oil in liquid phase to vapor phase, namely lauric acid, unsaturated fatty acid, and glycerol. Lauric acid is a carbon chain without a double bond with the advantages such as creating a combustion process perfectly and being easier to evaporate than fatty acid with a double bond. In CCO95C5, the fuel component that has been evapo- rated namely eugenol, terpene lauric acid, unsaturated fatty acid, and glycerol. Figure 6 exhibits the micro-explosion in CJO, KSO, and its blend occur earlier than CCO. The unsat- urated fatty acid contains in CJO and KSO until 70% leads to viscosity higher than CCO and its blend. Vegetable oil with high viscosity causes eugenol and terpene trapping in the droplet. The rapid evaporation of eugenol and terpene lead to micro-explosion inside the droplet and form secondary atom- ization outside the droplet. The presence of eugenol, terpene, and the double bond in KSO and CJO aect the geometry of ame. Micro-explosion in KSO and CJO take place due to the saturated and unsaturated fatty acid having dierences in volatility. Figure 7. Flame Geometry at Micro-Explosion (a) CCO, (b) CCO95C5, (c) KSO, (d) KSO95C5, (e) CJO, (f) CJO95C5 Figure 7 exhibit the ame geometry at micro-explosion phenomenaineachvegetableoilanditsblend. Micro-explosion exhibits the ame geometry of KSO95C5 and CJO95C5 have disruptive burning due to trapped molecules in droplets like eugenol and terpene. They have great volatility that creates them to come out of the droplet and initiate more micro- explosion. Theevaporationphasecreates thegrowthofbubbles inside the droplet. It leads to an internal pressure increase and the droplet sheet becomes thinner (Rao et al., 2017). Due to the pressure, the bubble comes out from the droplet and form secondary atomization, resulting in a substantial decrease in droplet size and an increase in burning rates (Coughlin and Hoxie, 2017). The small size of the bubble that ejected outside thedropletwaseasier toburnthanthemaindropletandformed a spherical ame. At that moment occur the ame-in-ame phenomena, which was illustrated in Figure 8. Figure 8. The Sequence of Coming Out Bubbles Creates Micro-Explosion and Flame-in-Flame The thermocouple signal is given from the droplet that was ignited on the K-type thermocouple shown in Figures 9 and 10. Heating, evaporation, and burning are the step of the droplet combustion process. When the coil heater ignited, heat transfer takes place from coil to droplet until reached around 400◦C to 500◦C. At this temperature, evaporation and droplet © 2022 The Authors. Page 504 of 507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 Figure 9. The Droplet Combustion Result of Vegetable Oil ignition occurs at the same time. The dierences in volatility at each compound led to evaporation occurring in more than one step. The burning process is identied as increasing steeper temperature from ignition temperature until peak temperature, then continuing to burn out temperature. Based on Figure 9, CCO has a lower ignition delay than CJO and KSO due to their chemical composition such as lauric acid in apercentage of 47%. CCOisalsocalledsaturatedoilbecauseof thepresenceof lauric acid and stearic acid. More sequential CH2 (methylene) groups in the fatty compound cause the ignition delay to become short and the cetane number becomes high. On the opposite, long ignition delay times with low Cetane Numbers and subsequent poorer combustion have been associated with more highly unsaturated components. The peak temperature in Figure 10 shows that KSO and CJO are higher than CCO. The presence of a double bond in their composition caused more energy to abstract hydrogen bonds until complete combustion. More energy is identied as more combustion temperature in the droplet. KSO and CJO are bulkier than CCO because they have rigid molecules. This rigid molecule led to evaporation and burning diculties at low temperature. CJO has the highest peak temperatures due to its density of CJO is the highest. Besides that, CJO has unsaturated fatty acid composition more than CCO. In the range of temperature 400-500◦C, evaporation and droplet ignition occurat the same time. Figure 11 describes the presence of clove oil that aects droplet ignition temperature. The ignition delay time of dierent fuels varied greatly, which was mainly related to the ash point of the fuel (Meng et al., 2020). The volatility of clove oil created evaporation time to become concise and ignition occurred at a lower temperature. The previous study mixed the coconut oil with clove oil in 10% basis volume and have the lowest ignition temperature if com- pare with the present study. It means that more percentage of clove oil in the fuel blend can decrease the ignition temperature and get a lower ignition delay time. Figure 10. The Droplet Combustion Result of Vegetable Oil Blended with Clove Oil 5% Figure 11. The Ignition Temperature of Vegetable Oil and its Blend 4. CONCLUSION The density of vegetable oil mixed with clove oil is slightly higherthanpurevegetableoil. CJO,KSO,CCO,namely0.921 gr/mL, 0.917 gr/mL, 0.913 gr/mL, then add clove oils be- come slightly high at 0.93 gr/mL, 0.926 gr/mL, 0.923 gr/mL. It’s due to the cumulative large molecular weight and the bulk structure of vegetable oil with the dense and rigid molecules of clove oil. As the density of the fuel blend is higher, fuel con- sumption will increase. The viscosity of vegetable oil mixed with clove oil is lower than pure vegetable oil. Viscosity CJO, KSO, and CCO namely decrease from 37.17 to 33 mm2/s, 37.83 to 35.24 mm2/s, 30.1 to 24.43 mm2/s. The energy input in the molecule creates rotation and vibration movement that causes the viscosity to decrease. The ash point of veg- etable oil mixed with clove oil lower than pure vegetable oil. Their mixture can decrease the ash point to 35%. It’s due to the volatility of clove oil creating short evaporation time in the fuel blend. Droplet combustion of vegetable oil blended with clove oil gets a shorter ignition delay time than pure vegetable oil. The presence of clove oil can reduce the ignition delay time by 5%. It’s due to the volatility of clove oil that can reduce the evaporation time and trigger the ignition. In vegetable oil © 2022 The Authors. Page 505 of 507 Gamayel et. al. Science and Technology Indonesia, 7 (2022) 500-507 mixed with clove oil, more ovoid ame occurs at the begin- ning of combustion. Non-ovoid ame marked as incomplete combustion with bulge or spike ame geometry. 5. 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