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The use of biodiesel requires the development of proper quantification procedures for biodiesel content in blends and in lubricants (fuel dilution in oil). Although the ester carbonyl stretch at 1746 wavenumbers (cm-1) is the most prominent band in the IR spectrum of biodiesel, it is difficult to use for quantification purposes due to a severe fluctuation of absorption strength from sample to sample, even at the same biodiesel content. We have demonstrated that the ester carbonyl fluctuation is not caused by variation in the ester alkyl chain length; but is most likely caused by the degree of hydrogen bonding of the ester functional group with water in the sample. Water molecules can form complexes with the ester compound affecting the strength of the ester carbonyl band. The impact of water on quantification of the biodiesel content of blends was significant, even for B100 samples that met the proposed ASTM D6751 water limit of 500 ppm by D6304 (Karl Fischer Methdod).

Pure biodiesel fuel (B100) is typically made of fatty acid methyl esters (FAME). FAME has different physical properties as compared to mineral diesel such as higher surface tension, lower volatility and higher specific gravity. These differences lead to a larger droplet size and thus more wall impingement of the fuel during injection in the combustion chamber. This results in higher levels of fuel dilution as the oil is scraped down into the crankcase by the scraper ring. The lower volatility also makes biodiesel more difficult to evaporate once it enters the crankcase. For these reasons, levels of fuel dilution in biodiesel fueled engines are likely to be higher compared to mineral diesel fueled engines. When in-cylinder dosing is applied to raise the exhaust temperature required for the regeneration of Diesel Particulate Filters (DPF's), biodiesel dilution in the engine oil may be elevated to high levels.

In this work fuel dilution of engine oil, and the impact of biodiesel fuel on dilution, were examined. New emissions requirements have driven the adoption of a range of aftertreatment systems for diesel engines. These aftertreatment devices in many cases have specific requirements for exhaust composition and temperature. Meeting these requirements can lead to fuel dilution of the engine oil. Measurement of fuel dilution of engine oil can be challenging, and in this study a new strategy for utilizing Fourier Transform Infrared Spectroscopy (FTIR) was examined. A synthetic component of aviation oil, pentaerythritol ester (PE), was found to be a very useful tracer for measuring dilution with ultra low sulfur diesel (ULSD), but not useful for measuring dilution with B20. Fuel dilution and evaporation rates were measured for both ULSD and for a blend of biodiesel and ULSD (B20).

As the world market develops for biodiesel fuels, it is likely that a wider variety of biodiesels will become available, both locally and globally, and require engines to operate on a wider variety of fuels than experienced today. At the same time, tighter emissions regulations and a drive for improved fuel economy have focused interest on advanced combustion modes such as HCCI or PCCI, which are known to be more sensitive to fuel properties. This research covers two series of biodiesel fuels. In the first, B20 blends of natural methyl esters derived from palm, coconut, rape, soy, and mustard were evaluated at light load in an HCCI research engine to determine combustion and performance characteristics. These fuels showed performance differences between the biodiesels and the base #2 ULSD fuel, but did not allow separation of chemical effects due to the small number of fuels and correlation of various properties.

Nine identical 40-ft. transit buses were operated on B20 and diesel for a period of two years - five of the buses operated exclusively on B20 (20% biodiesel blend) and the other four on petroleum diesel. The buses were model year 2000 Orion V equipped with Cummins ISM engines, and all operated on the same bus route. Each bus accumulated about 100,000 miles over the course of the study. B20 buses were compared to the petroleum diesel buses in terms of fuel economy, vehicle maintenance cost, road calls, and emissions. There was no difference between the on-road average fuel economy of the two groups (4.41 mpg) based on the in-use data, however laboratory testing revealed a nearly 2% reduction in fuel economy for the B20 vehicles. Engine and fuel system related maintenance costs were nearly identical for the two groups until the final month of the study.

Oxidative degradation of biodiesel under accelerated conditions has been examined by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and gravimetric measurement of deposit formation. The formation of gums and deposits caused by oxidation in storage or in an engine fuel system is a significant issue because of the potential for fuel pump and injector fouling. The results of this study indicate several important pathways for degradation and two pathways leading to formation of oligomers and, ultimately, deposits. Peroxides formed in the initial stage of oxidation can decompose to form aldehydes, ketones, and acids. These can react further in aldol condensation to form oligomers. Additionally, peroxides can react with fatty acid chains to form dimers and higher oligomers. Deposits form when the polarity and molecular weight of these oligomers is high enough.

Tests of ultra-low sulfur diesel blended with soy-biodiesel at 5% and 20% were conducted using a 2002 model year Cummins ISB engine (with exhaust gas recirculation) that had been retrofitted with a passively regenerated catalyzed diesel particulate filter (DPF). Results show that on average, the DPF balance point temperature (BPT) is 45°C and 112°C lower for B20 blends and neat biodiesel, respectively, than for 2007 certification diesel fuel. Biodiesel causes a measurable increase in regeneration rate at a fixed steady-state condition, even at the 5% blending level. The data show no significant differences in NOx emissions for these fuels at the steady-state regeneration conditions, suggesting that differences in soot reactivity are responsible for the observed differences in BPT and regeneration rate.