Tribology of lubricated nitrocarburised and titanium carbonitride surfaces

In the current work, two different coatings, nitrocarburised (CN) and titanium carbonitride (TiCN) on M2 grade high speed tool steel, were prepared by commercial diffusion and physical vapour deposition (PVD) techniques, respectively. Properties of the coating were characterised using a variety of techniques such as Glow-Discharge Optical Emission Spectrometry (GD-OES) and Scanning Electron Microscopy (SEM). Three non-commercial, oil-based lubricants with simplified formulations were used for this study. A tribological test was developed in which two nominally geometrically-identical crossed cylinders slide over each other under selected test conditions. This test was used to evaluate the effectiveness of a pre-applied lubricant film and a surface coating for various conditions of sliding wear. Engineered surface coatings can significantly improve wear resistance of the tool surface but their sliding wear performances strongly depend on the type of coating and lubricant combination used. These coating-lubricant interactions can also have a very strong effect on the useful life of the lubricant in a tribological system. Better performance of lubricants during the sliding wear testing was achieved hen used with the nitrocarburised (CN) coating. To understand the nature of the interactions and their possible effects on the coating-lubricant system, several surface analysis techniques were used. The molecular level investigation of Fourier Transform Infrared Spectroscopy (FTIR) revealed that oxidative degradation occurred in all used oil-based lubricants during the sliding wear test but the degradation behaviour of oil-based lubricants varied with the coating-lubricant system and the wear conditions. The main differences in the carbonyl oxidation region of the FTIR spectra (1900-1600 cm-1) between different coating-lubricant systems may relate to the effective lifetime of the lubricant during the sliding wear test. Secondary Ion Mass Spectrometry (SIMS) depth profiling shows that the CN coating has the highest lubricant absorbability among the tested tool surfaces. Diffusion of chlorine (C1), hydrogen (H) and oxygen (O) into the surface of subsurface of the tool suggested that strong interactions occurred between lubricant and tool surface during the sliding wear test. The possible effects of the interactions on the performance of whole tribological system are also discussed. The study of Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) indicated that the envelope of hydrocarbons (CmHn) of oil lubricant in the positive TOF-SIMS spectra shifted to lower mass fragment after the sliding wear testing due to the breakage of long-chain hydrocarbons to short-chain ones during the degradation of lubricant. The shift of the mass fragment range of the hydrocarbon (CmHn) envelope caries with the type of both tool surface and lubricant, again confirming that variation in the performance of the tool-lubricant system relates to the changes in surface chemistry due to tribochemical interactions at the tool-lubricant interface under sliding wear conditions. The sliding wear conditions resulted in changes not only in topography of the tool surface due to mechanical interactions, as outlined in Chapter 5, but also in surface chemistry due to tribochemical interactions, as discussed in Chapters 6 and 7.

Improved efficiency and stability of flexible dye sensitized solar cells on ITO/PEN substrates using an ionic liquid electrolyte

Flexible dye-sensitized solar cells (DSSCs) built on plastic substrates have attracted great interest as they are lightweight and can be roll-to-roll printed to accelerate production and reduce cost. However, plastic substrates such as PEN and PET are permeable to water, oxygen and volatile electrolyte solvents, which is detrimental to the cell stability. Therefore, to address this problem, in this work, an ionic liquid (IL) electrolyte is used to replace the volatile solvent electrolyte. The initial IL-based devices only achieved around 50% of the photovoltaic conversion efficiency of the cells using the solvent electrolyte. Current-voltage and electrochemical impedance spectroscopy (EIS) analysis of the cells in the dark indicated that this lower efficiency mainly originated from (i) a lack of blocking layer to reduce recombination, and (ii) a lower charge collection efficiency. To combat these problems, cells were developed using a 12 nm thick blocking layer, produced by atomic layer deposition, and 1 μm thick P25 TiO2 film sensitized with the hydrophobic MK-2 dye. These flexible DSSCs utilizing an IL electrolyte exhibit significantly improved efficiencies and a <10% drop in performance after 1000 h aging at 60°C under continuous light illumination.

Characterising vehicle emissions from the burning of biodiesel made from vegetable oil

Biodiesel manufactured from canola oil was blended with diesel and used as fuel in two diesel vehicles. This study aimed to test the emissions of diesel engines using blends of 100%, 80%, 60%, 40% , 20% biodiesel and 100% petroleum diesel, and characterise the particulate matter and gaseous emissions, with particular attention to levels of polycyclic aromatic hydrocarbons (PAHs) which are harmful to humans. A real time dust monitor was also used to monitor the continuous dust emissions during the entire testing cycle. The ECE(Euro 2) drive cycle was used for all emission tests. It was found that the particle concentration was up to 33% less when the engine burnt 100% biodiesel, compared to 100% diesel. Particle emission reduced with increased percentages of biodiesel in the fuel blends. Reductions of NOx, HC and CO were limited to about 10% when biodiesel was burned. Levels of CO2 emissions from the use of biodiesel and diesel were similar. Eighteen EPA priority PAHs were targeted, with only 6 species detected in the gaseous phase from the samples . 9 PAHs were detected in particulate phases at much lower levels than gaseous PAHs. Some marked reductions were observed for less toxic gaseous PAHs such as naphthalene when burning 100% biodiesel, but the particulate PAH emissions, which have more implications to adverse health effects, were virtually unchanged and did not show a statistically significant reduction. These findings are useful to gain an understanding of the emissions and environmental impacts of biodiesel.

A new method to warm up lubricating oil to improve the fuel efficiency during cold start

Cold start driving cycles exhibit an increase in friction losses due to the low temperatures of metal and media compared to normal operating engine conditions. These friction losses are responsible for up to 10% penalty in fuel economy over the official drive cycles like the New European Drive Cycle (NEDC), where the temperature of the oil even at the end of the 1180 s of the drive cycle is below the fully warmed up values of between 100°C and 120°C. At engine oil temperatures below 100°C the water from the blow by condensates and dilutes the engine oil in the oil pan which negatively affects engine wear. Therefore engine oil temperatures above 100°C are desirable to minimize engine wear through blow by condensate. The paper presents a new technique to warm up the engine oil that significantly reduces the friction losses and therefore also reduces the fuel economy penalty during a 22°C cold start NEDC. Chassis dynamometer experiments demonstrated fuel economy improvements of over 7% as well as significant emission reductions by rapidly increasing the oil temperature. Oil temperatures were increased by up to 60°C during certain parts of the NEDC. It is shown how a very simple sensitivity analysis can be used to assess the relative size or efficiency of different heat transfer passes and the resulting fuel economy improvement potential of different heat recovery systems system. Due to its simplicity the method is very fast to use and therefore also very cost effective. The method demonstrated a very good correlation for the fuel consumption within ±1% compared to measurements on a vehicle chassis roll.

Oxidation and stability of food grade fish oil : role of antioxidants

Oxidation of lipids containing unsaturated fatty acids is a common and complicated phenomenon. Volatile compounds generated during the oxidation of fish oil contribute to the unfavourable flavours and odours of the oil and the food products containing them. Although the initial mechanism of the oxidation seems simple, the mechanism and product mix become much more complicated and unpredictable during its progress, depending upon factors including the nature of the substrate and its environment. Oxidation of unsaturated fatty acids such as oleic, linoleic, and α-linolenic, predominantly from vegetable oils, and eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) from fish or microbial oil, produce several types of flavour volatiles that affect the sensory properties of these oils. Antioxidants are commonly used to retard the oxidation and improve the quality of food-grade oils. This chapter will discuss mechanisms of lipid oxidation and methods to control lipid oxidation, including the use of antioxidants.

Diesel engine performance and emission study using soybean biodiesel blends with fossil diesel

Biodiesel is an ecofriendly and renewable source of energy which can be used as a sustainable alternative fuel fordiesel engine. The study investigated engine performance and emission using soybean biodiesel blends with fossildiesel. The physio-chemical fuel properties of the biodiesel were determined using ASTM and EN standards. Thebiodiesel was blended in different proportions like 5% biodiesel and 95% diesel (by volume) denoted as B5, similarlyB10, B20 and B50. The biodiesel blends were tested in a multicylinder, diesel engine coupled with electromagneticdynamometer, under ISO 8178-4 test procedure. The study found that the biodiesel blends produces less brakepower, brake torque and relatively higher brake specific fuel consumption compared with diesel fuel. However, thesefules significantly reduces exhaust gases namely, CO, CO2 and HC but emits a bit more NOx compared with diesel.The reduction in emissions were different for each biodiesel blends. The study concluded that both B5 and B10blends are the optimum blends that produce more consistant and expected results compared with other blends.

The effect of triacetin as a fuel additive to waste cooking biodiesel on engine performance and exhaust emissions

This study investigates the effect of oxygenated fuels on engine performance and exhaust emission under a custom cycle using a fully instrumented 6-cylinder turbocharged diesel engine with a common railinjection system. A range of oxygenated fuels based on waste cooking biodiesel with triacetin as an oxygenated additive were studied. The oxygen ratio was used instead of the equivalence ratio, or air to fuelratio, to better explain the phenomena observed during combustion. It was found that the increased oxygen ratio was associated with an increase in the friction mean effective pressure, brake specific fuel consumption, CO, HC and PN. On the other hand, mechanical efficiency, brake thermal efficiency, CO2, NOx and PM decreased with oxygen ratio. Increasing the oxygen content of the fuel was associated with a decrease in indicated power, brake power, indicated mean effective pressure, brake mean effective pressure, friction power, blow-by, CO2, CO (at higher loads), HC, PM and PN. On the other hand, the brakespecific fuel consumption, brake thermal efficiency and NOx increased by using the oxygenated fuels. Also, by increasing the oxygen content, the accumulation mode count median diameter moved toward the smaller particle sizes. In addition to the oxygen content of fuel, the other physical and chemical properties of the fuels were used to interpret the behavior of the engine.

Performance and gaseous and particle emissions from a liquefied petroleum gas (LPG) fumigated compression ignition engine

In this study, an LPG fumigation system was fitted to a Euro III compression ignition (CI) engine to explore its impact on performance, and gaseous and particulate emissions. LPG was introduced to the intake air stream (as a secondary fuel) by using a low pressure fuel injector situated upstream of the turbocharger. LPG substitutions were test mode dependent, but varied in the range of 14-29% by energy. The engine was tested over a 5 point test cycle using ultra low sulphur diesel (ULSD), and a low and high LPG substitution at each test mode. The results show that LPG fumigation coerces the combustion into pre-mixed mode, as increases in the peak combustion pressure (and the rate of pressure rise) were observed in most tests. The emissions results show decreases in nitric oxide (NO) and particulate matter (PM2.5) emissions; however, very significant increases in carbon monoxide (CO) and hydrocarbon (HC) emissions were observed. A more detailed investigation of the particulate emissions showed that the number of particles emitted was reduced with LPG fumigation at all test settings – apart from mode 6 of the ECE R49 test cycle. Furthermore, the particles emitted generally had a slightly larger median diameter with LPG fumigation, and had a smaller semi-volatile fraction relative to ULSD. Overall, the results show that with some modifications, LPG fumigation systems could be used to extend ULSD supplies without adversely impacting on engine performance and emissions.

Experimental study of the degradation of volatile organic compounds by photocatalytic oxidation using TiO2 pellets

A fixed bed photocatalytic reactor has been designed and built with a UV
radiation source. Ti02 pellets were placed on the three fixed beds within the
reactor. Acetone was used as an indicator of volatile organic compounds (VOCs) during the experiment. Under the flow rate of 12.75 l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranged from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency; the obtained oxidation efficiency was in the range of 40-70% for various concentrations of untreated gases.

Effects of dietary oil source on growth and fillet fatty Acid composition of Murray cod, Maccullochella peelii peelii

The Murray cod, an Australian native freshwater fish, supports a relatively small but increasing aquaculture industry in Australia. Presently, there are no dedicated commercial diets available for Murray cod; instead, nutritionally sub-standard feeds formulated for other species are commonly used. The aim of the present investigation was to assess the suitability of two plant based lipid sources, canola oil (CO) and linseed oil (LO), as alternatives to fish oil for juvenile Murray cod. Five iso-nitrogenous, iso-calorific, iso-lipidic semi-purified experimental diets were formulated with 17% lipid originating from 100% cod liver oil (FO), 100% canola oil, 100% linseed oil and 1 : 1 blends of canola and cod liver oil (CFO) and 1 : 1 blends of linseed and cod liver oil (LFO). Each of the diets was fed to apparent satiation twice daily to triplicate groups of 50 Murray cod with initial mean weights of 6.45 ± 1.59 g for 84 days at 22 °C. Final mean weight, specific growth rate and daily feed consumption were significantly higher for the FO and LFO treatments compared to the LO treatment. Feed conversion and protein efficiency ratios were not significantly different amongst treatments. Experimental diets containing vegetable oil and vegetable oil blend(s) had significantly higher concentrations of n-6 fatty acids, predominantly in the form of linoleic acid (LA), while n-3 fatty acids were present in significantly higher concentrations in LO and LFO treatments. The fatty acid composition of Murray cod fillet was reflective of the dietary lipid source. Fillet of fish fed the FO was highest in EPA (20:5n-3), ArA (20:4n-6) and DHA (22:6n-3). Fish fed the CO diet had high concentrations of oleic acid (OlA) (192.2 ± 10.5 mg g lipid− 1), while the fillet of Murray cod fed the LO diet was high in α-linolenic acid (LnA) (107.1 ± 6.7 mg g lipid− 1). The present study suggests that fish oil can be replaced by up to 100% with canola oil and by up to 50% with linseed oil in Murray cod diets with no significant effect on growth.

Effects of dietary lipid sources on flavour volatile compounds of brown trout (Salmo trutta L.) fillet

The high cost and unpredictable availability of fish meal and fish oil (FO) forced feed mill companies to look for alternative ingredients for aquafeeds. In this study, the effects of alternative dietary lipid sources [FO as control, canola oil (CO), oleine oil (OO), poultry fat (PF) and pork lard (PL)] in trout feed on flavour volatile compounds occurring in brown trout (Salmo trutta L.) fillet were evaluated after 70 days of feeding (rearing temperature 14.6°C). Total amounts of volatile compounds identified were higher for fillets of fish fed diets containing only FO as lipid sources. Total amount of alcohols and aldehydes of the fillets were linearly directly related to the percentage content of polyunsaturated fatty acids (PUFA) n-3 of brown trout flesh. The use of alternative dietary lipid sources, modifying the fillet fatty acids composition, affect the total amount of volatile compounds and, changing the relative amount of each volatile compound, affect the flavour of the fish flesh.

Effect of crude oil extracts from trout offal as a replacement for fish oil in the diets of the Australian native fish Murray cod Maccullochella peelii peelii

The efficacy of trout oil (TO), extracted from trout offal from the aquaculture industry, was evaluated in juvenile Murray cod Maccullochella peelii peelii (25.4-0.81 g) diets in an experiment conducted over 60 days at 23.7-0.8 °C. Five isonitrogenous (48% protein), isolipidic (16%) and isoenergetic (21.8 kJ gm1) diets, in which the fish oil fraction was replaced in increments of 25% (0-100%), were used. The best growth and feed efficiency was observed in fish fed diets containing 50-75% TO. The relationship of specific growth rate (SGR), food conversion ratio (FCR) and protein efficiency ratio (PER) to the amount of TO in the diets was described in each case by second-order polynomial equations (P<0.05), which were: SGR=-0.44TO2+0.52TO+1.23 (r2=0.90, P<0.05); FCR=0.53TO2-0.64TO+1.21 (r2=0.95, P<0.05); and PER=-0.73TO2+0.90TO+1.54 (r2=0.90, P<0.05). Significant differences in carcass and muscle proximate compositions were noted among the different dietary treatments. Less lipid was found in muscle than in carcass. The fatty acids found in highest amounts in Murray cod, irrespective of the dietary treatment, were palmitic acid (16:0), oleic acid (18:1n-9), linoleic acid (18:2n-6) and eicosapentaenoic acid (20:5n-3). The fatty acid composition of the muscle reflected that of the diets. Both the n-6 fatty acid content and the n-3 to n-6 ratio were significantly (P<0.05) related to growth parameters, the relationships being as follows. Percentage of n-6 in diet (X) to SGR and FCR: SGR=-0.12X2+3.96X-32.51 (r2=0.96) and FCR=0.13X2-4.47X+39.39 (r2=0.98); and n-3:n-6 ratio (Z) to SGR, FCR, PER: SGR=-2.02Z2+5.01Z-1.74 (r2=0.88), FCR=2.31Z2-5.70Z+4.54 (r2=0.93) and PER=-3.12Z2-7.56Z+2.80 (r2=0.88) respectively. It is evident from this study that TO could be used effectively in Murray cod diets, and that an n-3:n-6 ratio of 1.2 results in the best growth performance in Murray cod.

Effects of dietary lipid source on fillet chemical composition, flavour volatile compounds and sensory characteristics in the freshwater fish tench (Tinca tinca L.)

In this study the effects of soybean and linseed oils on chemical and sensory characteristics of fillets were evaluated in the freshwater fish tench (Tinca tinca L.). Five experimental diets, differing only in the relative amount of soybean and linseed oil, were formulated and the experiment was conducted on 360 sub-adult tench for 12 weeks. The fatty acid composition of muscle reflected that of the diets and significant correlations were observed. Diets containing higher amounts of n − 6 fatty acids were responsible for an increased level of n − 6 fatty acids in the fish flesh. Consequently, an increase in the relative amount of n − 6-derived volatile aldehydes was also observed. These latter compounds are generally reported to contribute negatively to the general aroma of fish muscle and, consistently, the results of the sensory analysis showed a high value for the “off-flavour” attribute for fish fed the diet containing only n − 6-rich soybean oil.

Flavour as an analytical tool : an anti-inflammatory compound in olive oil

The chemical senses have been underutilised as analytical instruments, although as detectors of chemicals our senses are highly specialised biological machines. This paper reviews the current state of knowledge of the chemical senses. A novel technique was used to isolate and identify a flavour-active non-steroidal antiinflammatory compound in virgin olive oil.