Effect of Zinc Oxide Nano-Additives and Soybean Biodiesel at Varying Loads and Compression Ratios on VCR Diesel Engine Characteristics

SS symmetry Article Effect of Zinc Oxide Nano-Additives and Soybean Biodiesel at Varying Loads and Compression Ratios on VCR Diesel Engine Characteristics Rakhamaji S. Gavhane 1 , Ajit M. Kate 2 , Abhay Pawar 3 , Mohammad Reza Safaei 4,5,6, * , Manzoore Elahi M. Soudagar 7 , Muhammad Mujtaba Abbas 7 , Hafiz Muhammad Ali 8 , Nagaraj R Banapurmath 9 , Marjan Goodarzi 10 , Irfan Anjum Badruddin 11 , Waqar Ahmed 7 and Kiran Shahapurkar 12 1 2 3 4 5 6 7 8 9 10 11 12 * Department of Mechanical Engineering, Amrutvahini College of Engineering, Sangamner, Ahmednagar 422608, India; rakhmaji.gavhane@avcoe.org Department of Mechanical Engineering, Zeal College of Engineering and Research, Pune 411041, India; ajit.kate@zealeducation.com Department of Mechanical Engineering, D Y Patil College of Engineering, Ambi Talegaon Tal Maval, Pune 410506, India; abhay.pawar@dyptc.edu Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam Faculty of Electrical—Electronic Engineering, Duy Tan University, Da Nang 550000, Vietnam Department of Civil and Environmental Engineering, Florida International University, Miami, FL 33174, USA Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia; manzoor@siswa.um.edu.my (M.E.M.S.); m.mujtaba@uet.edu.pk (M.M.A.); Hva80013@siswa.um.edu.my (W.A.) Mechanical Engineering Department, King Fahd University of Petroleum and Minerals (KFUPM), Dharan 31261, Saudi Arabia; hafiz.ali@kfupm.edu.sa Department of Mechanical Engineering, B.V.B. College of Engineering and Technology, KLE Technological University, Vidyanagar, Hubli 580031, India; nr_banapurmath@kletech.ac.in Sustainable Management of Natural Resources and Environment Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City 700000, Vietnam; marjan.goodarzi@tdtu.edu.vn Research Center for Advanced Materials Science (RCAMS), King Khalid University, P.O. Box 9004, Abha 61413, Kingdom of Saudi Arabia; irfan@kku.edu.sa Department of Mechanical Design and Manufacturing Engineering, School of Mechanical, Chemical and Materials Engineering, Adama Science and Technology University, Adama 1888, Ethiopia; kiranhs1588@astu.edu.et Correspondence: mohammadrezasafaei@duytan.edu.vn; Tel.: (+1)-502-657-9981 Received: 10 May 2020; Accepted: 5 June 2020; Published: 22 June 2020



 Abstract: The present investigation is directed towards synthesis of zinc oxide (ZnO) nanoparticles and steady blending with soybean biodiesel (SBME25) to improve the fuel properties of SBME25 and enhance the overall characteristics of a variable compression ratio diesel engine. The soybean biodiesel (SBME) was prepared using the transesterification reaction. Numerous characterization tests were carried out to ascertain the shape and size of zinc oxide nanoparticles. The synthesized asymmetric ZnO nanoparticles were dispersed in SBME25 at three dosage levels (25, 50, and 75 ppm) with sodium dodecyl benzene sulphonate (SDBS) surfactant using the ultrasonication process. The quantified physicochemical properties of all the fuels blends were in symmetry with the American society for testing and materials (ASTM) standards. Nanofuel blends demonstrated enhanced fuel properties compared with SBME25. The engine was operated at two different compression ratios (18.5 and 21.5) and a comparison was made, and best fuel blend and compression ratio (CR) were selected. Fuel blend SBME25ZnO50 and compression ratio (CR) of 21.5 illustrated an overall enhancement in engine characteristics. For SBME25ZnO50 and CR 21.5 fuel blend, brake thermal efficiency (BTE) increased by 23.2%, brake specific fuel consumption (BSFC) were reduced by 26.66%, and hydrocarbon (HC), Symmetry 2020, 12, 1042; doi:10.3390/sym12061042 www.mdpi.com/journal/symmetry Symmetry 2020, 12, 1042 2 of 31 CO, smoke, and CO2 emissions were reduced by 32.234%, 28.21% 22.55% and 21.66%, respectively; in addition, the heat release rate (HRR) and mean gas temperature (MGT) improved, and ignition delay (ID) was reduced. In contrast, the NOx emissions increased for all the nanofuel blends due to greater supply of oxygen and increase in the temperature of the combustion chamber. At a CR of 18.5, a similar trend was observed, while the values of engine characteristics were lower compared with CR of 21.5. The properties of nanofuel blend SBME25ZnO50 were in symmetry and comparable to the diesel fuel. Keywords: soybean biodiesel; zinc oxide nanoparticles; compression ratio; VCR engine performance; emissions 1. Introduction The global increase in fuel consumption and dependence on petroleum, and the increasing costs due to higher demand, have sparked interest in alternate and sustainable energy sources [1]. Developing nations are highly dependent on fossil fuels, particularly for their industrial and transport sectors [2]. Currently, due to an inadequate supply of fossil fuels, increasing global prices for crude oil and environmental factors have led to renewable energy sources becoming increasingly more important [3,4]. Vegetable oils have certain comparable diesel fuel properties and are known to have several advantages over fossil fuels, such as being environmentally friendly, nontoxic, and biodegradable, and thus help in establishing environmental balance [5,6]. Their cetane number and vaporization pressure is almost equivalent to that of diesel. Biodiesel contains extra oxygen atoms in its molecular structure, which contribute oxygen that assist in enhanced fuel combustion. Nonetheless, despite the numerous advantages of biodiesel, it has certain disadvantages, such as high viscosity, poor cold flow properties and characteristics, and lower heating value [1,7,8]. A recently developed technique to improve combustion characteristics and fuel properties is through the addition of fuel additives. The past decade has witnessed a rise in the utilization of alcohol-based additives in biodiesel fuel blends, such as ethanol, butanol, heptanol, and diethyl ether [9–11]. Alcohol-based additives supply more oxygen in the combustion chamber to reduce emissions, however, due to the formation of a lean mixture it lowers the calorific value, which, combined with higher auto ignition temperatures and lower lubrication properties, results in engine deterioration and reduced performance characteristics. Hence, researchers have explored the potential of micro- and nanoparticle additives. Microparticle additives assisted in improving the engine characteristics, but they tend to agglomerate. Nanotechnology has found a suitable place in many industrial applications, such as engineering, agricultural and medical science, biotechnology, and transport. Nanoparticle additives exhibit higher thermophysical properties and ease of miscibility in any base fluids [12–16]. Previous investigators reported nanoparticle additives to be exceptionally effective in reducing the agglomeration in comparison with microparticles and improve engine characteristics due to the large surface air-to-volume ratio, high thermophysical properties, high combustion velocity, and high thermal conductivity [17–19]. In addition, the addition of nanoparticles to base fluids improves the physiochemical properties, in the form of higher flash point, fire point, cloud point, and calorific value, and lower density and viscosity of the base fluid [1,7,14,20–23]. Table 1 shows the effect of nanoparticles in different fuel blends. Recent studies on the effect of nanoparticles and biodiesel in diesel engines reported an enhancement in combustion characteristics, such as cylinder pressure, heat release rate (HRR), and mean gas temperature (MGT), and reduced the ignition delay (ID) period for metal and carbon-based nano-additives, such as carbon nanotubes, graphene oxide, Cu2 O, FeCl3 , CeO2 , Co3 O4 , Al2 O3 , TiO2 , and ZnO. Symmetry 2020, 12, 1042 3 of 31 Table 1. The effect of nanoparticles in different fuel blends. Biofuel Blends Biodiesel Dosage of NPs Engine Type Application Output D (80%) + BD (20%) Dairy scum oil methyl ester Graphene oxide 20 ppm 40 ppm 60 ppm D (80%) + BD (20%) Pongamia oil methyl ester FeO 30 nm and Ferrofluid 100 nm SC, DI, 4-S, CI engine, 23◦ BTDC, WC, 17.5 CR, 3 FI nozzles D (40%) + BD (30%) + ethanol (30%) Palm oil methyl ester ZnO 250 ppm SC, DI, 4-S, CI engine, 23◦ BTDC, WC, 17.5 CR, 3 FI nozzles D (70%) + BD (20%) + ethanol (10%) Castor oil methyl ester γ-Alumina 10 ppm 20 ppm 30 ppm SC, DI, 4-S, CI Engine, 23◦ BTDC HCC, AC, 17.5 CR 3 FI nozzles, 0.3 mm dia. FI holes, 661 cc BD (91%) + 50 mL DEE Jatropha methyl ester CNT 50 ppm SC, DI, 4-S, CI Engine, 26◦ BTDC HCC, AC, 17.5 CR 3 FI nozzles • • • • • • • • • • Dosage level of 40 ppm of GNPs increased the BTE, HRR and reduced the BSFC, ignition delay. The calorific value increased while the viscosity reduced. The emissions, CO, HC and smoke reduced. The NOx emission slightly increased. Improves the peak HRR, BTE. Reduction in NOx emissions. BSFC reduces for Nanofuel blends. Reduction in CO, HC, PM, smoke. Reduction of BSFC, HRR and cylinder pressure. Decrease in CO, NOx, smoke and BTE. Increases the calorific value. • • Improved BTE, Cylinder pressure and heat release rate. Lower HC, CO emissions, BSEC. • • • • • The CO, HC and NOx reduced in comparison with neat diesel. Enhanced combustion attributes, micro explosion of fuel droplets. Improved BTE and reduced BSFC. Accelerates the burning rate, lowers the ID and HRR. Improves the peak HRR, BTE. Reduces the NOx, smoke and HC. Avoids the accumulation of non-polar complexes on the cylinder wall. Catalytic effect of NPs and micro explosion improved BTE, HRR and cylinder gas pressure. Better atomization and rapid evaporation. NOx was reduced. Supply of excess O leads in lower CO and HC. • • • Improved BTE, Cylinder pressure and heat release rate. Lower HC, CO emissions, BSEC. Lower NOx emissions. • 23◦ BDTC, SC, DI, 4-S, CI engine, 17.5 CR, 3 FI nozzles WC, D (70%) + BD (10%) + ethanol (20%) (Diesterol- E20) Castor oil methyl ester Ceria and CNT 25 ppm 50 ppm 100 ppm CI, WC, DI, 1500 rpm, 19:1, 23◦ BTDC BD + (200 and 500 ppm of Ethanox) Calophyllum Inophyllum Methyl Ester ZnO 50 ppm 100 ppm 2-C, DI, 4-S, CI Engine, 23◦ BTDC, WC, 18.5 CR, 5 FI nozzles, 1670 cc D (70%) + BD (20%) + ethanol (10%) Jatropha methyl ester γ-Alumina 10 ppm 20 ppm 30 ppm SC, DI, 4-S, CI Engine, 23◦ BTDC HCC, AC, 17.5 CR, 3 FI nozzles, 0.3 mm dia. FI holes, 661 cc • • • • • • Ref. [7] [24] [25] [26] [27] [28] [29] [30] D: Diesel; BD: Biodiesel; WC: Water Cooled; SC: Single Cylinder; AC: Air Cooled; 4-S: Four Stroke; DI: Direct Injection; CI: Compression-Ignition; FI: Fuel Injector; CR: Compression ratio; BTDC: Before Top Dead Center. Symmetry 2020, 12, 1042 4 of 31 Özgür et al. [31] investigated the combined effect of the addition of 25 and 50 mg/L of MgO and SiO2 nanoparticles in diesel. The authors observed that the addition of nanoparticles in diesel fuel lowered the NOx and CO, and increased the engine performance marginally. Soudagar et al. [7,32] studied the influence of graphene oxide and Al2 O3 nanoparticles (20, 40, and 60 ppm) in dairy scum methyl ester and honge oil methyl ester. Sodium dodecyl sulfate surfactant was used for nanoparticle stabilization of nanofuel in the base fluid and the ultrasonication process was carried out for proper blending of fuel blends. The authors reported an enhancement in the overall combustion and performance characteristics, and reduction in hydrocarbon (HC), CO, and smoke opacity, of a conventional mechanical fuel injection system diesel engine for the all the nanofuel blends in contrast to B20 fuel. Karthikeyan et al. [33] performed a related study introducing ZnO nanoparticles to canola biodiesel. They observed that for the B20+ZnO fuel blends, the brake thermal efficiency (BTE) increased, and HC and CO decreased, in comparison with neat B20. The influence of alumina (Al2 O3 ) nanoparticles on biodiesel blends was investigated by Venu and Madhavan [34]. The authors reported the Al2 O3 in biodiesel reduced the brake specific fuel consumption (BSFC), NOX , HC, and carbon dioxide despite the increased emission of CO. Sajith et al. [35] studied the influence of CeO2 nanoparticles in biodiesel fuel blends. In order to achieve optimum efficiency, different dosing levels of CeO2 nanoparticles (20, 40, 60, and 80 ppm) were used. The impact of CeO2 nanoparticles on compression-ignition (CI) engine efficiency, thermophysical properties of the fuel, and emissions characteristics were investigated. The authors reported a decline in the NOx and HC emissions and enhancement in the overall engine characteristics. Keskin et al. [36] reported the influence of nanoparticles on specific fuel consumption (SFC) and emission characteristics of diesel engines. The MnO2 and MgO nanoparticles were added to the diesel at concentration levels of 8 and 16 µmol/L. The physiochemical properties of diesel fuel were enhanced due to addition of the nanoparticles. The addition of combined nano-additives reduced CO by 16%, smoke opacity by 29%, and the SFC by 4.16%, whereas a 10% increase in NOx emissions was recorded. Consequently, the previous literature suggests that the addition of nanoparticle additives to biodiesel fuel enhances the overall diesel engine characteristics and the fuel properties. Studies have been carried out using fixed engine variables by numerous investigators. Regarding environmental pollution due to the addition of nanoparticles in fuel, limited research is available concerning the traces of nano-additives in engine exhaust emissions. Deqing Mei et al. [37] reported CeO2 in diesel fuel enhances the combustion process, while a high dosing level of nano-CeO2 can cause early ignition, which can lead to escaping of nanoparticles through the exhaust. However, the authors found only a trace of nanoparticles and an insignificant effect on particulate matter (PM) emission. Qibai et al. [38] investigated the effects of Al and carbon nanoparticles in a diesel-biodiesel blend; the exhaust gases were passed through diesel particulate filters (DPFs), and slight traces of aluminum, oxygen, carbon, and silicon were found. Toxic effects of nanoparticles on animals include crossing cell membranes and inhaled NPs can reach the blood and target sites such as the heart, blood cells, and liver [1]. The information on these pathways is limited, but the actual number of particles that move from one organ to another can be significant, depending on exposure time [39]. Studies on the environmental pollution caused by nanoparticles as fuel additives are limited, hence there is a scope for further study. The objective of the current research is to investigate the combined effect of nanoparticle additives and biodiesel fuel blends at varying compression ratios and loads in a variable compression ratio (VCR) diesel engine. The study delves into the potential of a ZnO nanoparticle and soybean biodiesel blend. The soybean biodiesel (SBME25) is blended with synthesized zinc oxide nanoparticles at varying blending ratios of 25, 50, and 75 ppm. This study facilitates and proposes a direction for future research and commercialization of all aspects of nanotechnology in biodiesel fuels in diesel engine applications. In addition, this study enables the selection of optimal and most suitable compression ratios for enhancement of diesel engine characteristics. Symmetry 2020, 12, 1042 5 of 31 2. Material and Methods 2.1. Production of Soybean Biodiesel A Gas Chromatography Mass Spectrometer (GCMS/MS) Shimadzu, Japan (TQ 8030) was used to analyze the free fatty acid (FFA) percentage in the soybean oil. Table 2 shows the FFA composition of soybean biodiesel. Table 2. Fatty acid composition of soybean oil. Fatty Acid Carbon Chain Composition (wt.%) Palmitic Stearic Oleic Linoleic Linolenic C 16:0 C 18:0 C 18:1 C 18:2 C 18:3 11.24 4.15 23.69 51.66 6.89 The preparation of biodiesel was carried out at Apex innovations laboratory, India. In the esterification method, the soybean oil was heated with sulfuric acid at 70 ◦ C and methanol in an air-oven for about 60 min to eliminate the moisture. In the subsequent step, i.e., the transesterification reaction, the solution was mixed with sodium hydroxide at 6:1 M and heated at 60 ◦ C for about 60 min. The mixing and heating processes were carried out on a magnetic stirrer rotating at a constant speed of 500 rpm. Then, the solution was transferred to a separating funnel and kept steady for 24 h. After 24 h, a clear distinct layer was visible, distinguishing the glycerol and biodiesel. The lower layer containing glycerol was drained and the upper layer was extracted and washed using warm water. The liquid was dried to obtain soybean biodiesel. 2.2. Synthesis and Characterization of Zinc Oxide Nanoparticles The zinc oxide nanoparticles were synthesized using the aqueous precipitation method as previously reported Haniffa et al. [40] and Li Yuan et al. [41]. Initially, 0.5 M zinc nitrate (Zn(NO3 )2 ) was added of drop by drop to 0.5 M of sodium carbonate (Na2 CO3 ) solution under vigorous stirring. Soon after separation from the solution using vacuum filtration technique by washing and rinsing three times with distilled water and then ethanol, the precipitate was dried in an air circulating oven at 80 ◦ C for 2 h. The oven-dried powder was calcined to 500 ◦ C for 3 h to obtain zinc oxide nanopowder. Finally, for a period of 5 h the nano powder was ball-milled at 200 rpm to obtain fine zinc oxide nanoparticles. Figure 1 illustrates a flow chart showing the synthesis of zinc oxide nanoparticles using the aqueous precipitation method. Field emission scanning electron microscope (FESEM) analysis was used to determine chemical composition and visualize the surface morphology of ZnO nanoparticles. The analysis was performed using a Bruker XFlash 6I30, USA. Figure 2 represents the SEM image of ZnO nanoparticles at 25,000× magnification. The synthesized ZnO nanoparticles had Rosette and irregular crystal structures with a wurtzite hexagonal phase, in agreement with previous literature [42,43]. X-ray powder diffraction (XRD) was used to evaluate the crystallinity (phase identification) by comparison with the integrated intensity of a previously reported pattern to that of the observed sharp peaks of the synthesized zinc oxide nanoparticles. The XRD analysis is shown in Figure 3a; the analysis was carried out using a Bruker D8 VENTURE, USA. The calculated hkl values for the peaks observed for ZnO nanoparticles at 2θ = 32.45◦ (100), 34.64◦ (002), 36.57◦ (101), 48.52◦ (102), 56.43◦ (110), 62.66◦ (103), 66.36◦ (200), 68.13◦ (112), 69.44◦ (201), 72.32◦ (004), and 77.73◦ (004). A sharp peak was observed at 36.57◦ (101), which indicates the crystallinity of ZnO nanoparticles; the peaks reported in the current investigation were closer to the characteristic peaks reported by [44,45]. Figure 3b shows the UV-Vis absorption spectra; ultra-violet absorption for ZnO nanoparticles confirms absorbance at a wavelength of 365.47 nm, between the characteristic range of 350 to 380 nm [44]. Symmetry 2020, 12, 1042 6 of 31 Figure 1. A flow chart of the synthesis of zinc oxide nanoparticles through the aqueous precipitation method. μ at 25,000× magnification level. Figure 2. FESEM at 3 µm θ Symmetry 2020, 12, 1042 7 of 31 ZnO nanoparticles Absorbance (a.u.) 365.47 nm 320 340 360 380 400 420 440 460 480 500 520 540 560 Wavelength (nm) (a) (b) (c) Figure 3. Characterization tests: (a) XRD analysis; (b) UV-Vis Absorbance; (c) TEM at 100 nm magnification. The main objective of transmission electron microscopy (TEM) analysis is to produce high magnification images of the internal structure of a sample. Figure 3c illustrates the TEM image at 100 nm and magnification level of 20,000×. The TEM analysis is also used to collect data on crystalline structures, contamination, stress, and internal fractures inside materials [44]. Initially, the ZnO nanoparticles were dispersed in ethanol. The structure of ZnO nanoparticles was found to be hexagonal wurtzite and the size of the nanoparticles was in the range of 15–40 nm. 2.3. Preparation and Physiochemical Properties of Nanofuel Blends A scale was used to measure precise quantities of zinc oxide nanoparticles. The ZnO nanoparticles (25, 50, and 75 mg/L) were mixed with 10 mL of distilled water. Sodium dodecyl sulfate (SDS) surfactant was added for surface modifications and stabilization, to reduce the possibility of coagulation and coalescence, and to reduce the surface tension. Surfactants tend to position themselves at the interface between the nanoparticles and the base fluid, where it establishes a degree of continuity between the Symmetry 2020, 12, 1042 8 of 31 nanoparticles and fluids. The ultrasonication process was carried out for steady blending; initially the ultrasonication bath was used to blend the solution with an agitation time of 60 min. Later, the different nanofluid blends were blended using an ultrasonication probe at a frequency of 15–30 Hz for 20 min. After the zinc oxide nanofluids were prepared they were transferred to the SBME25-diesel fuel blend, and heated and steadily mixed using a magnetic stirrer at 60 ◦ C for 30 min to remove traces of water molecules. Then, the same ultrasonication processes were carried out for a steady dispersion of zinc oxide nanoparticles in SBME25 biodiesel–diesel fuel blend. Figure 4 illustrates the comprehensive steps involved in the preparation of nanofuel. Figure 4. The comprehensive steps involved in the preparation of nanofuel. The experiments were conducted in various lab facilities available in Maharashtra and Karnataka, India. The detailed description of the equipment, procedure, and lab setup was presented in previous articles by Soudagar et al. [7,32] on the addition of graphene oxide and Al2 O3 nanoparticles in dairy scum oil methyl ester and honge oil methyl ester. The physiochemical properties of the test fuel blends are demonstrated in Table 3. The analysis indicates the addition of zinc oxide nanoparticles to soybean biodiesel increases the calorific value and cetane number and demonstrates comparable diesel fuel properties. The fuel blend SBME25ZnO50 demonstrated overall improvement in the physicochemical properties. The analyzed results were within the ASTM D6751 standard for biodiesel. − − − − − − − − Symmetry 2020, 12, 1042 9 of 31 Table 3. Physicochemical properties of fuel blends. Properties Unit ASTM Standards Test Limit ASTM D6751 Diesel SBME25 SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 Density Calorific value Kinematic Viscosity Specific Gravity Cetane Number Flash Point Pour Point Cloud Point Sulphur content Water content kg/m3 at 15 ◦ C kJ/kg cSt at 40 ◦ C gm/cc ◦C ◦C ◦C % w/w % vol D4052 D5865 D445 D891 D613 D93 D97-12 D2500-11 D5453 D2709 860–900 Min. 35,000 1.9–6 0.87–0.90 Min. 40 >130 −15 to 16 −3 to 12 0.05 0.05% vol 810 45,000 2.12 0.811 51 55 −4 −2 0.005 - 845.66 41,684 3.56 0.825 48.66 65.71 −6 4.5 0.012 Trace 845.87 43,400 3.52 0.820 52.55 62.87 −5 3.5 0.0156 Trace 846.22 44,800 3.525 0.821 53.74 60.47 −5.65 3.54 0.0162 Trace 846.84 43,850 3.531 0.824 53.15 61.87 −5.6 3.57 0.0188 Trace Symmetry 2020, 12, 1042 10 of 31 2.4. Uncertainty Analysis of Expected Errors Uncertainty analysis is an organized set of procedures followed for calculation of errors in experimental data. The inaccuracies occur due to the error in electronic and mechanical components, environmental factors, and human miscalculations. The data is gathered in ideal conditions, and specifications and details of all the components are available. Measurement errors from several different sources are classified into bias and precision errors; throughout the experimentation the bias errors remain constant. In this work, the estimation of experimental uncertainty and the evaluation of standard errors in the measurements were derived using the method proposed by Moffat et al. [46]. Table 4 illustrates the uncertainty and accuracy levels of calculated engine parameters. Table 4. Uncertainty and accuracy levels of calculated engine parameters. Parameters Accuracy (±) Uncertainty (%) Brake power (KW) Brake thermal efficiency (%) Brake specific fuel consumption (%) Heat release rate (J/◦ CA) Carbon monoxide emission (%) Nitrogen oxide emission (ppm) Hydrocarbon emission (ppm) Exhaust gas temperature (◦ C) Mean gas temperature (◦ C) Smoke meter (HSU) ±0.01% ±10 ppm ±10 ppm ±1 ±1 ±0.22 ±0.28 ±0.31 ±0.24 ±0.18 ±0.24 ±0.14 ±0.15 ±0.35 ±0.25 In addition, the propagation of errors was studied using standard deviations by plotting error bars, where error bars were derived considering the average of six readings. The propagation of uncertainty for various factors are determined depending on two or more independent parameters is carried out using Equation (1): s Uy y = ux1 x1 !2 +  u 2 x2 x2 + .................. +  u n xn xn (1) where Uy : uncertainty; y: testing value; x1 , x2 ,..., xn : evaluated parameter; and the uncertainty of emissions is Uy = Resolution Range . The overall uncertainty of the engine characteristics is calculated using Equation (2): s Overall uncertainty = ± Uncertainty % o f (BTE2 + BSFC2 + CO2 + NOx2 + HC2 ) +smoke2 + HRR2 + MGT2 + EGT2 = ± 1.82 (2) 2.5. Test Engine Setup The engine used in the current investigation is a variable compression ratio (VCR), Kirloskar make, single cylinder diesel engine. All the experiments were carried-out at Apex innovation laboratory, India. The engine was coupled to a five-gas analyzer and smoke meter. The combustion chamber used in the current investigation was hemispherical; compression ratios were varied without stopping the VCR engine and the readings were derived using enginesoft software. A Data Acquisition System (DAQ) and Labview software was used as an interface between the computer and the engine sensors (air and fuel flow, temperatures, and load measurement sensors). Table 5 illustrates the specification of the VCR test engine used in the current investigation. Figure 5 illustrates the pictorial view of the test engine used in the current investigation. The heat release rate was estimated using the data for 600 crank angle values. The compression ratio was varied by the tilting block arrangement, in which the compression ratio could be varied without stopping the engine. The arrangement consisted of compression ratio indicator and compression ratio adjuster Symmetry 2020, 12, 1042 11 of 31 with a lock nut and six Allen bolts. For varying the compression ratio, the Allen bolts were slightly loosened, and the adjuster lock nut was loosened. Further, the adjuster was rotated to set a desired compression ratio according to the compression ratio indicator, and then locked using a lock nut. The chosen compression ratios in the current investigation were 18.5 and 21.5. Table 5. Test Engine Specifications. Number of Strokes 4 Fuel type Cylinder Rated Power Speed Cylinder diameter Load indicator Fuel tank Exhaust Gas Recirculation Piezo sensor Temperature sensor Load sensor Rotameter Dynamometer Model Make End flanges both sides Air gap Torque Hot coil voltage Continuous current (amp) Cold resistance ohm Diesel, Biodiesel, and Nanofuel Single, Water cooled 3.5 KW 1500 rpm 87.5 mm Digital, Range 0–50 Kg, Supply 230 V air cooled Volume 15 liters with glass fuel metering column Water cooled, Stainless Steel, Range 0–15% Range 5000 PSI, with low noise cable RTD, PT100 and Thermocouple, Type K Load cell, type strain gauge, range 0–50 Kg Engine cooling 40–400 LPH; Cal. 25–250 LPH AG10 Saj test plant rig Cardon shaft model 1260 type 0.77 mm 11.5 Nm 60 V 5 9.8 Figure 5. Variable compression ratio (VCR) test engine setup. Symmetry 2020, 12, 1042 12 of 31 3. Results and Discussions In this section, the combustion, performance, and emission characteristics of the diesel engine are investigated. The effect of nanofuel blends and compression ratios of 18.5 and 21.5 on heat release rate, ignition delay, BTE, BSFC, and mean gas temperature, and CO, NOx, HC, CO2 , and smoke emissions are reported. A constant speed of 1500 rpm, injection timing (IT) of 23.5◦ BTDC (before top dead center), and five loads were maintained. Table 6 illustrates the factors considered and employed in the current investigation. Table 6. Engine parameters. Factors Considered Parameters Employed Engine Combustion Chamber (CC) Injection Pressure (IP) Fuel Injector (FI) holes Injection timing (IT) Speed Compression Ratio (CR) Fuel Variable Compression Ratio (VCR) Hemispherical (HCC) 220 bar 4 holes, 0.25 mm dia. 23◦ BTDC 1500 rpm (constant) 18.5, 21.5 Diesel, SBME25, SBME25ZnO25, SBME25ZnO50, SBME25ZnO75 3.1. The Effect of Zinc Oxide Nano Additives and Soybean Fuel Blend on the Engine Performance 3.1.1. The Effect of SBME25-ZnO Nanofuel Blends on Brake Thermal Efficiency (BTE) at Different Compression Ratios Figure 6 illustrates the variation of BTE at varying loads. The results demonstrate that the BTE of the VCR diesel engine was enhanced at all dosage levels of zinc oxide nanoparticles. The zinc oxide nanoparticles promote complete combustion of the fuel charge when compared with biodiesel fuel blends. Equations (3) and (4) illustrates the estimation of BP and BTE, respectively: BP = 0.785 × N × (W x 9.81) × Arm lenght 2πN (W × R) 2πNT = = kW 60000 60000 60000 BTE = BP × 3600 × 100   % kg Fuel f low hr × Cv (3) (4) Brake thermal efficiency for all tested fuels with different compression ratios at variable load is presented in Figure 7a,b. BTE increased with an increase in load up to 80%, then exhibited a slight reduction at 100% load. At maximum load and CR 21.5, the BTE increased by 11.592% (SBME25ZnO25), 23.2% (SBME25ZnO50), and 19.024% (SBME25ZnO75) compared to SBME25 fuel. Diesel fuel exhibited a BTE value that was 29.64% lower with 18.5 CR at 80% load. All fuel blends showed lower BTE values compared to diesel due to lower calorific value, lower brake power, and higher BSFC. In addition, the BTE value fell with a reduction in compression ratio. All tested fuels showed a reduction in BTE values: 9.88% (diesel), 15.4% (SBME25ZnO25), 6.15% (SBME25ZnO50), 11.1% (SBME25ZnO75), and 20.5% (SBME25) with a compression ratio of 18.5 compared to a CR of 21.5, due to lower compression temperature, which resulted in poor combustion of fuel. BTE is directly proportional to compression ratio [47]. Brake thermal efficiency showed an enhancement with an increase in loads and lower heat losses at higher engine load [48]. The metal zinc oxide nanoparticles improved the combustion process by reducing its duration and ignition delay, and increased in-cylinder temperature and pressure, and high HRR subsequently increased the BTE [49,50]. Zinc oxide nanoparticles act as a potential catalyst due to their high reactive surface area during the combustion process, which leads to a micro explosion of fuel droplets resulting in improved combustion characteristics, such as cylinder pressure and high heat release rate, therefore increasing the BTE. ( × ) . × Symmetry 2020, 12, 1042 40 Compression ratio: 18.5:1 28.547 26.227 27.415 28.478 30.557 25.714 23.63 22.58 20.36 21.87 18.847 16.477 16.79 12.89 14.189 8.63 10 13 of 31 24.412 24.7 18.92 19.786 10.41 11.64 12.884 15 × Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 25 20 × )× . 29.647 30 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 13.57 Brake Thermal Efficiency (%) 35 × ( × 5 0 20% 40% 60% 80% 100% Load (a) 45 Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 27.657 22.71 23.225 25.1 25.923 27.2 28.623 30.498 28.954 30.955 25.894 23.996 20.95 18.56 19.452 12.3 13.479 13.11 14.856 15 21.66 22.677 20 26.784 28.892 30 25 Compression ratio: 21.5:1 31.285 35 15.58 Brake Thermal Efficiency (%) 40 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 10 5 0 20% 40% 60% 80% 100% Load (b) Figure 6. The variation of BTE at compression ratios of (a) 18.5 and (b) 21.5. 14 of 31 0.398 0.41 0.422 0.35 0.295 0.238 0.245 0.242 0.264 0.251 0.256 0.271 0.295 0.289 0.298 0.3 0.315 0.33 0.318 0.315 0.334 0.352 0.378 0.39 0.368 0.4 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical Compression ratio: 18.5:1 0.5 0.415 Brake Specific Fuel Consumption (kg/kWh) Symmetry 2020, 12, 1042 0.2 0.1 0.0 20% 40% 60% 80% 100% Load 0.27 0.234 0.245 0.198 0.221 0.231 0.253 0.278 0.298 0.312 0.232 0.245 0.282 0.2969 0.309 0.315 0.284 0.264 0.3 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 0.248 0.354 0.352 0.4 0.37 0.385 0.415 Compression ratio: 21.5 0.33 Brake Specific Fuel Consumption (kg/kWh) (a) 0.2 0.1 0.0 20% 40% 60% 80% 100% Load (b) Figure 7. The variation of BTE at compression ratios: (a) 18.5 and (b) 21.5. Symmetry 2020, 12, 1042 15 of 31 3.1.2. The Effect of SBME25-ZnO Nanofuel Blends on Brake Specific Fuel Consumption (BSFC) at Different Compression Ratios Figure 7a,b show the variation of BSFC and loads for various fuel blends at different compression ratios. The BSFC is reduced with an increase in engine load. The lowest BSFC value with 21.5 CR 0.198 Kg/kWh for SBME25ZnO50 is obtained at 100% engine load. On average, the BSFC values were 0.258 Kg/kWh (diesel), 0.262 Kg/kWh (SBME25ZnO50), 0.2896 Kg/kWh (SBME25ZnO75), 0.304 Kg/kWh (SBME25ZnO25), and 0.329 Kg/kWh (SBME25) at 21.5 CR. All ternary fuel blends showed reduction in BSFC: 20.37%, 12.18%, and 7.82% for SBME25ZnO50, SBME25ZnO75, and SBME25ZnO25, respectively, compared to SBME25. The minimum BSFC value was recorded with zinc oxide (50 ppm) as a fuel additive. SBME25ZnO50 showed higher BSFC value 0.245 Kg/kWh with 18.5 compression ratio at 100% engine load. The average BSFC values for all tested fuels increased with a decrease in compression ratio. All tested fuels showed a rise in the BSFC for 18.5 compression ratio: 14.47% (diesel), 8.94% (SBME25ZnO25), 15.46% (SBME25ZnO50), 4.48% (SBME25ZnO75), and 13.7% (SBME25), compared to 21.5 compression ratio. At higher load, BSFC values are reduced due to less heat loses and a smaller amount of fuel is required to obtain specific brake power [51,52]. A similar increase in BSFC with an increase in compression ratio has been reported by various researchers [48,53,54]. Biodiesel with fuel additive (ZnO) showed significant reduction in BSFC due to improved combustion characteristics. Nanoparticle enhanced the air–fuel mixing, micro explosion of fuel droplets, and secondary atomization, resulting in lower BSFC. The combustion process is improved with the use of ZnO as a fuel additive (oxidizing agent) due to its high calorific value, shorter ignition delay, and more reactive surface area [49]. Dahad et al. [55] and Deepak et al. [56] reported a similar reduction in BSFC with the use of zinc oxide as a fuel additive in a diesel engine. 3.2. The Effect of Zinc Oxide Nano-Additives and Soybean Fuel Blend on Engine Emissions 3.2.1. The Effect of SBME25-ZnO Nanofuel Blends on Carbon Monoxide (CO) Emissions at Different Compression Ratios The variation in carbon monoxide emissions and loads for all tested fuels at different compression ratio is presented in Figure 8a,b. Carbon monoxide emissions are produced due to incomplete combustion during the combustion process. All tested fuels showed reduction in carbon monoxide emissions, with the exception of diesel, due to the presence of extra oxygen molecules, which results in complete conversion of CO to CO2 [57]. SBME25ZnO50 showed the lowest CO emissions among all tested fuels due to the presence of extra oxygen and reactive surface area (ZnO), which leads to high in-cylinder temperature and pressure resulting in complete combustion. On average, the CO emissions were reduced by 41.08%, 31.44%, and 18.66% for SBME25ZnO50, SBME25ZnO75, and SBME25ZnO25 ternary blends, respectively, compared to SBME25. All tested fuels showed an increase in CO emission values: 20.85% (diesel), 19.87% (SBME25ZnO25), 4.23% (SBME25ZnO50), 6.53% (SBME25ZnO75), and 14.45% (SBME25) with compression ratio of 18.5 compared to a compression ratio of 21.5. This was due to a lower compression temperature, which resulted in poor combustion of fuel. A similar result has been reported by Sharma et al. [58], in which an increase in the compression ratio resulted in an increased air temperature, leading to a reduction in the ignition delay period and CO emissions due to complete combustion. Symmetry 2020, 12, 1042 0.44 16 of 31 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical SBME25 0.22 0.151 0.38 Compression ratio: 18.5:1 0.33 0.161 0.172 0.188 0.396 0.22 0.198 0.0638 0.348 0.0805 0.092 0.105 0.128 SBME25ZnO50 0.261 0.211 0.153 0.174 0.0472 0.48 0.0625 0.0795 0.0838 SBME25ZnO25 0.35 0.36 0.16 0.44 0.115 0.124 0.157 0.189 0.175 0.151 SBME25ZnO75 0.229 0.258 0.17 0.172 0.086 0.0625 0.336 0.309 0.06 0.075 0.088 0.098 0 20% 40% 60% 0.0782 0.0884 0.0921 SBME25ZnO50 0.252 0.201 0.168 0.084 0.144 0.0456 0.300 0.150 0.0608 0.0772 0.0821 SBME25ZnO25 0.225 0.1 0.000 Diesel 0.22 0.00 0.142 0.28 0.2112 0.105 0.24 0.112 0.145 0.178 0.075 0.33 0.11 Carbon monoxide emissions (% vol.) Carbon monoxide emissions (% vol.) 0.174 0.12 0.1365 0.344 0.295 SBME25ZnO75 0.261 0.24 Compression ratio: 21.5:1 0.099 0.348 0.087 SBME25 0.297 0.11 0.087 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 0.21 0.176 0.154 0.088 80% Diesel 0.264 100% 0.000 0.05 0.062 0.074 0.086 0 20% 40% 60% Load Load (a) (b) 0.141 80% 100% Figure 8. The variation of carbon monoxide at compression ratios: (a) 18.5 and (b) 21.5. 3.2.2. The Effect of SBME25-ZnO Nanofuel Blends on Hydrocarbon (HC) Emissions at Different Compression Ratios HC emissions for diesel, SBME25ZnO25, SBME25ZnO50, SBME25ZnO75, and SBME25 at variable load with different compression ratios are shown in Figure 9a,b. HC emissions are mainly affected by fuel characteristics, fuel spray properties, and different engine operating conditions. The average HC emissions at CR 21.5 were 0.131, 0.139, 0.147, 0.1530, and 0.189 g/kWh for SBME25ZnO50, diesel, SBME25ZnO75, SBME25ZnO25, and SBME25, respectively, from minimum to maximum engine loads. All ternary fuel blends showed reduction in HC emissions compared to a neat biodiesel–diesel blend. Overall, significant reductions in HC emissions for a compression ratio of 21.5 of 30.83%, 22.12%, and 18.76% were observed for SBME25ZnO50, SBME25ZnO75, and SBME25ZnO25, respectively, compared to SBME25. The fuel blend SBME25 showed maximum HC emissions due to its viscous attributes, which resulted in poor fuel spray characteristics and led to incomplete combustion. All fuels tested at CR 18.5 showed higher HC emissions compared to CR 21.5. HC emissions are mainly affected by the air–fuel mixture and the air-to-fuel equivalence ratio from rich to lean mixture. A similar increase in HC emissions due to a lower compression ratio was reported by Sharma et al. [58]. All tested fuels showed an increase in CO emission values: 12.58% (diesel), 12.26% (SBME25ZnO25), 14.35% (SBME25ZnO50), 8.27% (SBME25ZnO75), and 20.48% (SBME25) with a compression ratio of 18.5 compared to 21.5 CR. Symmetry 2020, 12, 1042 17 of 31 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical SBME25 0.332 0.166 0.1795 Hydrocarbon Emission (g/kW-h) 0.19 0.2642 0.176 SBME25ZnO75 0.20 0.145 0.05 0.158 0.155 0.148 0.1517 SBME25ZnO50 0.210 0.182 0.138 0.1508 0.14 0.138 0.138 0.126 0.084 SBME25ZnO25 0.25 0.20 0.15 0.21 0.156 0.164 0.1614 0.1709 0.1702 0.126 Compression ratio: 21.5:1 0.179 0.19 0.2 0.21 0.168 SBME25ZnO75 0.135 0.135 0.108 0.145 0.155 0.191 0.1454 0.1472 0.1442 0.1454 0.135 0.145 0.152 0.131 0.128 0.154 0.158 0.165 0.132 0.16 SBME25ZnO50 0.198 0.128 0.132 0.122 0.142 0.099 SBME25ZnO25 0.192 0.168 0.142 0.120 Diesel 0.136 0.151 0.1412 0.165 Diesel 0.170 0.153 0.063 0.000 0.162 0.144 0.10 0.189 0.17 0.189 0.1914 0.10 0.168 0.198 0.154 0.083 0.25 0.15 0.191 0.242 Hydrocarbon Emission (g/kW-h) 0.249 0.254 SBME25 0.220 Compression ratio: 18.5:1 0.1335 0.135 0 20% 0.1264 0.137 0.145 0.152 0.119 0 20% 40% Load (a) 60% 80% 100% 40% 60% 80% 100% Load (b) Figure 9. The variation of hydrocarbon emissions at compression ratios: (a) 18.5 and (b) 21.5. 3.2.3. The Effect of SBME25-ZnO Nanofuel Blends on Nitrogen Oxide (NOx) Emissions at Different Compression Ratios NOx emissions for all tested fuels with variable loads and different compression ratios are presented in Figure 10a,b. NOx emissions increased with increase in engine load. High NOx emissions were generated due to high in-cylinder temperature resulting from complete combustion. Extra oxygen molecules in biodiesel and ternary blends enhanced the combustion process and resulted in the high in-cylinder pressure and temperature that leads to higher NOx emissions. Average NOx emissions at a compression ratio of 21.5 287.73, 290.77, 365.73, 412.51, and 456.14 ppm were obtained for SBME25, diesel, SBME25ZnO25, SBME25ZnO50, and SBME25ZnO75, respectively, between 20% and 100% engine loads. All ternary blends showed a slight increase in NOx emissions compared to diesel and biodiesel–diesel blends due to high in-cylinder temperature and pressure. NOx emissions were increased by 27.10%, 43.36% and 58.52% at 21.5 CR for SBME25ZnO25, SBME25ZnO50, and SBME25ZnO75, respectively, compared to SBME25. Ternary fuel blends improved the combustion process due to high oxygen content in fuel additives as well as in biodiesel, which leads to shorter ignition delay due to high cetane number [57,59]. At a compression ratio of 18.5, NOx emissions were reduced compared to the engine tested at a higher compression ratio of 21.5. The combustion temperature was increased due to a higher compression ratio because of the high oxygen intake that leads to improved combustion phenomena and results in higher NOx emissions. Symmetry 2020, 12, 1042 18 of 31 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical SBME25 Compression ratio: 18.5:1 420 265.84 280 140 62.48 Nitrogen oxide emissions (ppm) 680 640 361.44 300.44 81.74 680 350.45 378.12 457.786 SBME25ZnO25 290.56 340 70.85 600 340.65 370.41 0 SBME25ZnO75 420 210 272.14 75 330.68 365.47 380 264.844 60.89 0 20% 40% Load (a) 60% 80% 100% 251.77 58.25 363.465 455.408 312.671 352.47 442.786 135.65 Diesel 450 0 321.717 SBME25ZnO25 570 150 466.11 142.54 300 158.49 371.786 SBME25ZnO50 570 190 332.109 155.65 380 446.87 430.68 340.85 50.224 6000 271.97 67.54 240.84 300.69 630 190 Diesel 300 445.741 162.65 450 150 468.474 170.84 510 170 387.84 SBME25ZnO50 480 Compression ratio: 21.5:1 125.62 840 180.55 320 SBME25 300 150 310.71 90.55 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 450 SBME25ZnO75 340 160 438.48 140.58 510 170 325.75 357.17 600 Nitrogen oxide emissions (ppm) 560 250.88 310.68 350.66 405.74 135.89 55.67 0 20% 40% 60% 80% 100% Load (b) Figure 10. The variation of nitrogen oxide emissions at compression ratios: (a) 18.5 and (b) 21.5. 3.2.4. The Effect of SBME25-ZnO Nanofuel Blends on Carbon Dioxide (CO2 ) Emissions at Different Compression Ratios The carbon molecules from the fuel combustion combines with the oxygen to produce carbon dioxide emissions. Figure 11a,b show an increasing trend in CO2 emissions with increasing loading conditions. For the compression ratio of 18.5, all the nanofuel blends lowered the carbon dioxide emissions due to complete fuel combustion and lower generation of carbon molecules post combustion process compared to the SBME25 fuel blend. In addition, a similar trend was observed for a compression ratio of 21.5, however, lower carbon dioxide emissions were observed at a higher compression ratio due to rapid combustion and enhanced micro-explosion process. At compression ratio of 21.5, fuel blend SBME25ZnO50 showed lower carbon dioxide emissions compared to all fuel blends at maximum load. The CO2 for 50 ppm of ZnO in SNME25 was lower by 21.66% and 2.36%, respectively, compared to SBME25 and diesel fuel. This was due to the large surface area of ZnO nanoparticles enabling complete combustion of hydrocarbon molecules [59,60]. Symmetry 2020, 12, 1042 SBME25 5.4 3.6 1.8 Carbon dioxide emissions (% vol.) 4.124 4.471 1.211 SBME25ZnO50 3.471 3.712 4.124 2.704 2.6 0.854 0.0 6.0 1.35 SBME25ZnO25 4.5 2.487 3.0 3.312 4.051 4.387 4.714 1.38 0.0 3.22 2.8 0.0 4.2 0.0 4.2 3.56 4.227 40% Load (a) 60% 80% 100% 4.25 3.25 3.45 2.1 SBME25ZnO50 4.003 2.42 0.7 1.11 SBME25ZnO25 4.18 3.75 3.85 3.1 3.4 3.72 40% 60% 80% 4.6 2.28 1.2 Diesel 4.2 0.0 20% 3.85 0.96 2.8 1.4 0.92 0 3.35 2.8 1.98 3.61 SBME25ZnO75 2.8 1.4 5.11 2.85 3.6 1.8 4.82 1.75 0.0 3.914 Compression ratio: 21.5:1 4.52 4.15 5.4 1.4 Diesel 4.2 0.0 0.0 3.854 2.257 0.0 1.4 1.8 3.714 3.9 SBME25 5.4 3.6 SBME25ZnO75 3.2 1.5 5.384 3.174 4.8 1.3 Compression ratio: 18.5:1 5.025 4.641 4.451 1.984 0.0 1.6 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical Carbon dioxide emissions (% vol.) 7.2 19 of 31 4.1 1.75 0.82 0 20% 100% Load (b) Figure 11. The variation of carbon dioxide emissions at compression ratios: (a) 18.5 and (b) 21.5. 3.2.5. The Effect of SBME25-ZnO Nanofuel Blends on Smoke Emissions at Different Compression Ratios The smoke emissions for all tested fuels with variable loads and different compression ratios are illustrated in Figure 12. The smoke emissions are produced due to incomplete combustion of hydrocarbon particles in the combustion chamber, a rich air-to-fuel mixture, and poor fuel vaporization. The SBME25 fuel blend produces higher smoke emissions due to lower calorific value and heat release rate. In contrast, the biodiesel blends with ZnO nanoparticles improved the micro-explosion phenomenon and air-to-fuel mixing, leading to lower smoke emissions. The smoke emissions for compression ratios of 18.5 and 21.5 for SBME25ZnO50 fell by 19.95% and 22.54%, respectively, compared with SBME25 and diesel fuel. The large surface area of the ZnO nanoparticles enhances the combustion process resulting in complete fuel combustion. An increase in the compression ratio leads to better air-to-fuel mixing and increases the temperature during the compression stroke. In addition, an increase in the compression ratio reduces the dilution of the fuel charge by residual gases [61]. Symmetry 2020, 12, 1042 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical SBME25 60 40 20 21.471 64 Compression ratio: 18.5:1 38.94 30.77 Smoke emissions (HSU) 16 SBME25ZnO75 16.67 60 32.971 24.81 15 SBME25ZnO25 18.78 64 27.478 0 43.178 39.471 15.86 0 22.48 20% 18.84 42.714 48.7 51.987 55.741 45.984 50.74 SBME25ZnO75 64 32 16 13.98 (a) 60% 80% 100% 38.9 29.178 45 30 10.556 18.452 13 24.65 41.96 24.71 44.92 49.35 39.667 48.786 45.24 51.644 32.64 15.9 Diesel 64 16 34.548 SBME25ZnO25 52 36.154 32 Load 21.64 58.412 SBME25ZnO50 60 15 55.741 44.6 35.678 48 29.197 40% 27.715 39 Diesel 32 18 52.64 26 48 16 47.48 13.741 35.971 Compression ratio: 21.5:1 54 27.84 21.891 51 17 SBME25 72 48 37.971 68 34 41.77 SBME25ZnO50 45 30 Engine: VCR 4S with EGR , Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm, IP: 240 bar, IT: 23.5°btdc CC: Hemisperical 60.84 36 48 32 47.154 58.741 Smoke emissions (HSU) 80 20 of 31 12.36 0 19.79 20% 42.786 47.92 26.126 40% 60% 80% 100% Load (b) Figure 12. The variation of smoke emissions at compression ratios: (a) 18.5 and (b) 21.5. 3.3. The Effect of Zinc Oxide Nano-Additives and Soybean Fuel Blend on Engine Combustion Characteristics 3.3.1. The Effect of SBME25-ZnO Nanofuel Blends on Ignition Delay at Different Compression Ratios The ignition delay period is a critical phenomenon from the perspectives of preparation of the fuel before being injected into the combustion chamber and selection of ideal injection timings. The ignition delay period of a diesel engine is the time period between the start of injection and start of combustion. The ignition delay period in the context of diesel engines is the period from the first charge of fuel entering the combustion chamber to the period when the first flame propagates [62]. The ignition delay period depends primarily on the ambient temperature. Due to fuel vaporization, the HRR curve shows negative values prior to the start of combustion for diesel engines. As it is evident from Figure 13a,b that the ignition delay period reduces with an increase in the loading conditions due to a rise in the pressure and temperature for all the fuel blends. The rise in pressure results in the mixture of molecules coming closely together, enhancing the chemical reactions due to the active collisions of molecules, and resulting in a shorter ignition delay period. The higher viscosity of soybean biodiesel results in poor atomization of fuel droplets, air-to-fuel mixing, and lower flame cone angle, resulting in an increase in the delay period. The ZnO nanoparticles in SBME25 result in a reduction in the ignition delay period due to enhancement of combustion rate and better premixed combustion phase. At the higher compression ratio of 21.5, due to higher injection air-to-fuel mixture in the combustion chamber, at the same injection timing and injection pressure, the ignition delay period is lowered compared to 18.5 CR. At maximum load and compression ratio of 21.5, the values of ignition delay period for SBME25ZnO concentrations of 50, 75, and 25 ppm, respectively, were 7.21, 8.125 and 8.786 ◦ CA, while at a compression ratio of 18.5 the values were 7.744, 8.125, and 9.174 ◦ CA. At both compression ratios, the ignition delay period observed for SBMEZnO50 was lower than that of all the fuel blends. At a compression ratio of 21.5 for the SBMEZnO50 fuel blend, reductions of Symmetry 2020, 12, 1042 21 of 31 25.02% and 5.38% were observed, and at a compression ratio 18.5, reductions of 23.47% and 2.18% were observed, compared to SBME25 and neat diesel, respectively. This was due to the high catalytic activity of zinc oxide nanoparticles, which enhance the combustion phenomena. However at higher proportions of ZnO in the fuel blends, the ignition delay period slightly increases due to a negligible increase in the viscosity. 11.15 11.52 10.12 10.21 9.174 7.744 8.22 7.917 8.214 8.88 8.57 9.15 9.51 9.25 9.68 10.14 9.94 10 10.842 11.541 11.05 11.514 11.25 Ignition Delay Period (°CA) 12.84 13.157 13.57 15 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical Compression ratio: 18.5:1 5 0 20% 40% 60% 80% 100% Load (a) 10.87 11.421 8.125 7.21 7.62 7.77 8.21 8.786 8.84 9.014 9.64 9.845 9.62 10.021 10.842 9.58 10.04 10.68 11.12 10.82 11.142 11.654 12.51 13.24 12.971 Ignition Delay Period (°CA) 15 10 Fuel Blends Diesel SBME25ZnO25 SBME25ZnO50 SBME25ZnO75 SBME25 Engine: VCR 4S with EGR Injector: 4 holes, 0.25 mm dia. Engine Speed:1500 rpm IP: 240 bar, IT: 23.5°btdc CC: Hemisperical, Compression ratio: 21.5:1 5 0 20% 40% 60% 80% 100% Load (b) Figure 13. Variation of ignition delay period with load at compression ratios: (a) 18.5 and (b) 21.5. Symmetry 2020, 12, 1042 22 of 31 3.3.2. The Effect of SBME25-ZnO Nanofuel Blends on Mean Gas Temperature at Different Compression Ratios The mean value of the cylinder temperature of combusted and unburned gases present in the combustion chamber during a cycle is known as mean gas temperature. Figure 14 illustrates the mean gas temperature of fuel blends at varying crank angles at maximum load and compression ratio of 21.5. The gases present in the cylinder are the blend of combusted and unburned air–fuel mixture. The mean gas temperature ascertains the rate of combustion reaction of the fuel, and the desired value should be nearer to the adiabatic temperature of the flame. The adiabatic flame temperature is achieved when there is no loss in thermal energy and an adiabatic state is reached. At this point, maximum pressure is reached, although the process of combustion is incomplete, and the combustion continues for another few ◦ CA in the boundary of the combustion chamber. Peaks in the mean gas temperature for all the fuel blends are observed from 370 to 385 ◦ CA, and the mean gas temperature for diesel is 1334.29 ◦ C at 380 ◦ CA. The nanofuel blend, SBME25ZnO50, exhibited a mean cylinder temperature of 1329.11 ◦ C at 379 ◦ CA. Slightly lower values of mean gas temperature were observed for SBME25: the peak of 1301.87 ◦ C was seen at 380 ◦ CA due to viscosity and density. @100 Load, 21.5 CR Fuel Blends Diesel SBME25ZnO50 SBME25ZnO75 SBME25ZnO25 SBME25 Mean Gas Temperaure (°C) 1400 1200 1000 800 600 400 200 310 320 330 340 350 360 370 380 Crank Angle (°CA) 390 400 410 420 Figure 14. The mean gas temperature of fuel blends at varying crank angles at maximum load and CR 21.5. Symmetry 2020, 12, 1042 23 of 31 3.3.3. The Effect of SBME25-ZnO Nanofuel Blends on Heat Release Rate at Different Compression Ratios The first law of thermodynamics is used to evaluate the heat release rate (HRR), which is the decrease in heat transfer and mass at cylinder pressure, and effective variations in volume at a closed engine cycle. The contents of the cylinder are considered uniform with modeled properties in the thermodynamic state and characterized by average values. The model is considered as having zero dimension as no spatial variants are considered. In the current investigation, the experimental heat release rate is determined using the first law-single zone model illustrated in Equation (5): γh dp dQn dQw dV 1 = ×p + ×V + dθ γh − 1 dθ γh − 1 dθ dθ (5) where Tm is the mean in-cylinder temperature. γh is the specific heat, shown in Equation (6): γh = 1.35 − 6 × 10−5 × Tm + 10−8 × Tm2 (6) In Figure 15a,b, the heat release rate is averaged over 400 cycles for a smooth curve and to avoid any irregularity in the combustion cycles that may occur in diesel engines fueled with low-ignition biofuels. The HRR is negative during the ignition delay period, due to the cooling effect caused by the vaporization of the fuel and loss of heat at the cylinder walls. Once the auto-ignition starts in the combustion process, the heat release rate becomes positive and a rapid growth in the peak is observed. The increase in the heat release rate for all the nanofuel blends is due to an enhanced cetane number and lower ignition delay period, which assist in increasing the efficiency of the engine. At a compression ratio of 21.5, all the fuel blends illustrated an enhancement in the heat release rate due to higher pressure and combustion rate, leading to complete burning of the fuel charge and resulting in higher energy output compared with the compression ratio of 18.5. The HRR for the SBME25 biodiesel blend was lower than the other fuel blends due to the high molecular weight and low burning velocity. The enhancement in heat release rate for the nanofuel blends is due to improved surface area, volume, high ignition properties, and thermal conductivity. The maximum peaks observed for SBME25 ZnO (25, 50, and 75 mg/L, respectively) at compression ratio 18.5 were 51.31, 58.97, and 62.26 J/◦ CA, while the peaks for diesel and SBME25 were 66.72 and 49.12 J/◦ CA, respectively. The compression ratio of 21.5 illustrated a higher HRR due to higher burning velocity of fuel blends; the HRR values for 25, 50, and 75 ppm of ZnO in SBME25 were 61.844, 70.44, and 65.854 J/◦ CA, respectively. The addition of zinc oxide nanoparticles in the SBME25 biodiesel blend increases the HRR at both compression ratios due to enhancement in oxygen content during combustion and atomization of fuel particles [33,56,60–65]. Table 7 illustrates the final results analysis of SBME25 and nanofuel blends. Symmetry 2020, 12, 1042 24 of 31 @100% load, 18.5 CR 70 Fuel Blends Diesel SBME25ZnO50 SBME25ZnO25 SBME25ZnO75 SBME25 Heat Release Rate (°CA) 60 50 40 30 20 10 0 -10 -20 330 340 350 360 370 Crank Angle (°) 380 (a) 80 @100% load, 21.5 CR Fuel Blends Diesel SBME25ZnO50 SBME25ZnO75 SBME25 SBME25ZnO25 Heat Release Rate (°CA) 70 60 50 40 30 20 10 0 -10 -20 320 330 340 350 360 Crank Angle (°) 370 380 390 (b) Figure 15. The variation of heat release rate with ◦ CA at maximum load and compression ratios: (a) 18.5 and (b) 21.5. Symmetry 2020, 12, 1042 25 of 31 Table 7. The results analysis of SBME25 and nanofuel blends. SBME25 Color Code Description CR 18.5 CR 21.5 Decreases Negative Rise Increases Engine Parameters BSFC (kg/kWh) BTE (%) CO (% vol.) HC (g/kWh) CO2 (% vol.) NOx (ppm) Smoke (HSU) ID (◦ CA) HRR (◦ CA) MGT (◦ K) CR 18.5 0.295 20.36 0.38 0.2642 5.384 438.48 60.84 10.12 49.125 - CR 21.5 0.27 23.23 0.28 0.21 5.11 430.68 58.412 9.64 58.97 1303.36 SBME25ZnO25 CR 18.5 0.264 23.63 0.35 0.21 4.714 445.741 55.741 9.174 51.312 - (%) 10.508 16.56 7.895 20.514 12.44 1.62 8.334 9.347 4.426 - CR 21.5 0.245 25.923 0.24 0.165 4.6 442.786 51.644 8.786 61.844 1311.97 SBME25ZnO50 (%) 9.25 11.592 14.28 21.45 9.98 2.27 11.58 9.72 4.841 0.66 CR 18.5 0.238 28.547 0.211 0.182 4.471 457.786 48.7 7.744 62.26 - (%) 19.322 40.211 44.47 31.112 23.402 4.235 19.954 23.47 26.715 - CR 21.5 0.198 28.62 0.201 0.142 4.003 455.408 45.24 7.21 70.44 1334.72 SBME25ZnO75 CR 18.5 26.66 0.245 23.2 26.277 28.21 0.295 32.234 0.1914 21.66 4.124 5.414 468.474 22.55 52.64 26.2 8.22 19.45 58.97 2.406 (%) (%) 16.94 28.86 22.36 27.55 16.951 6.128 13.477 19.74 20.972 - CR 21.5 0.234 27.65 0.229 0.16 4.25 466.11 49.35 8.125 65.854 1317.22 (%) 13.33 19.024 18.21 23.807 16.82 7.601 15.55 18.64 11.6 1.06 Symmetry 2020, 12, 1042 26 of 31 4. Conclusions The present study focuses on the effects of zinc oxide nanoparticles and soybean biodiesel blends at different loads and varying CRs on a VCR, single cylinder engine with IT of 23◦ BTDC and at a constant speed 1500 rpm. In the investigation, the engine was operated at two compression ratios of 18.5 and 21.5. Three nanofuel blends, SBME25ZnO25, SBME25ZnO50, and SBME25ZnO75, were prepared using the ultrasonication process by varying the dosage levels of ZnO nanoparticles and sodium dodecyl sulfate (SDS) surfactant. The following conclusions are drawn based on the obtained results: 1. 2. 3. 4. The addition of ZnO nanoparticles to SBME25 enhanced the fuel properties, such as the calorific value and cetane number, while the density and viscosity were comparable to SBME25. The performance characteristics of the VCR engine were enhanced for the ternary fuel blends. The dosage level of 50 ppm in SBME25 biodiesel and compression ratio of 21.5 increased the BTE by 20.59% and reduced the BSFC by 20.37% compared with the SBME25 fuel blend due to enhanced catalytic activity of zinc oxide nanoparticles. The heat release rate and mean gas temperature of SBME25ZnO50 were comparable with diesel fuel. The enhancement in the heat release rate is due to the micro-explosion phenomenon occurring in the combustion chamber. Emissions decreased with the addition of ZnO nanoparticles in the fuel blends. HC, CO, smoke, and CO2 emissions were reduced by 30.83%, 41.08%, 22.54%, and 21.66%, respectively. NOx emissions increased slightly due to excess oxygen in the combustion chamber. The results and conclusion validate that ZnO nanoparticles in soybean biodiesel at a CR of 21.5 enhance performance and combustion, and reduce the emissions of a common rail direct injection engine. 5. Recommendations for Future Research Based on a recent comprehensive review of the effect of the addition of nanoparticles to fuel blends on diesel engine characteristics by Soudagar et al. [1], the future research topics are suggested as follows: 1. 2. 3. 4. An extensive investigation of the surface reaction and engine wear on engine parts, such as the combustion chamber, piston and piston rings, cylinder and cylinder linings, fuel injectors and exhaust pipe, is required to confirm the reliability of nano-additives in a diesel engine. The impact of metal-based nanoparticles used as fuel additives in diesel/biodiesel fuel on human health should be examined before commercialization of the technology. There is scope for further research on the effects of nanoparticles in exhaust emissions. This may raise an issue related to environmental pollution caused by the addition of nanoparticles to diesel and bio-diesel fuels. Analysis of the cost and complexity in the preparation of nanoparticles, encompassing public safety and economic feasibility, should be considered in future research. Furthermore, efforts should be made in developing cost-effective and efficient nanoparticles. Author Contributions: R.S.G.: Conceptualization, Methodology, Investigation, Writing-Original Draft; A.M.K.: Supervision and Project administration and Resources; A.P.: Supervision, Project administration; M.R.S.: Project administration, Review & Editing; M.E.M.S.: Design of the study, Conceptualization, Writing Methodology, and Reviewing; M.M.A.: Interpretation of results, and Reviewing; H.M.A.: Formal analyses, Review & Editing; N.R.B.: Review & Editing, Design and Analysis, Interpretation of results; M.G.: Review & Editing, Supervision; I.A.B.: Conceptualization and Reviewing; W.A.: Review & Editing; K.S.: Review & Editing, Formal analysis. All authors have read and agreed to the published version of the manuscript. Funding: This work was funded by King Khalid University under the grant number R.G.P. 2/107/41. Acknowledgments: The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University for funding this work through research groups program under grant number (R.G.P2/107/41). Conflicts of Interest: The authors declare no conflict of interest. Symmetry 2020, 12, 1042 27 of 31 Nomenclature NPs CRDI CI nm g/kWh CC ATDC FFA ASTM ID CO2 NOX BTE SFC IP EGT ◦ CA SBME SBME25 ZnO25 SBME25 ZnO75 ZnO SDS IC ppm m HCC BTDC CR PP HC CO PM BSFC Tw IT HRR D100 SBME25 SBME25 ZnO50 Nanoparticles Common rail direct injection Compression ignition Nanometer Grams per kilowatt hour Combustion chamber After top dead center Free fatty acid American Society for Testing and Materials Injection delay Carbon dioxide Oxides of nitrogen Brake thermal efficiency Specific fuel consumption Injection pressure Exhaust gas temperature Crank angle (degrees) Soybean methyl ester (Soybean biodiesel) SBME25 and 25 ppm ZnO NPs SBME25 and 75 ppm ZnO NPs Zinc oxide Sodium dodecyl sulfate Internal combustion Parts per million Meter Hemispherical combustion chamber Before top dead center Compression ratio Peak pressure Hydrocarbon Carbon monoxide Particulate matter Brake specific fuel consumption Wall temperature Injection timing Heat release rate 100% diesel 25% Soybean methyl ester blended with diesel SBME25 and 50 ppm ZnO NPs References 1. 2. 3. 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