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An experimental study was performed in a firing SI engine at conditions representative of the warmup phase of operation in which liquid gasoline films were established at various locations in the combustion chamber and the resulting impact on hydrocarbon emissions was assessed. Unique about this study was that it combined, in a firing engine environment, direct visual observation of the liquid fuel films, measurements of the temperatures these films were subjected to, and the determination from gas analyzers of burned and unburned fuel quantities exiting the combustion chamber - all with cycle-level resolution or better. A means of deducing the exhaust hydrocarbon emissions that were due to the liquid fuel films in the combustion chamber was developed. An increase in exhaust hydrocarbon emissions was always observed with liquid fuel films present in the combustion chamber.

Comparisons have been made between dual-fuel (80% port-injection gasoline and 20% direct-injection diesel by mass) Highly Premixed Charge Combustion (HPCC) and blended-fuel (80% gasoline and 20% diesel) Low Temperature Combustion (LTC) modes on a 1-L single-cylinder test engine. In the HPCC mode, both early-injection (E-HPCC) and late-injection (L-HPCC) of diesel have been used. The comparisons have been conducted with a fixed fuel injection rate of 50 mg/cycle at 1500 rpm, and with the combustion phasing fixed (by adjusting the injection timing) so that the 50% heat release point (CA50) is at 8° ATDC. The rapid heat release process of LTC leads to the highest maximum pressure rise rate (MPRR). A two-peak heat release process is observed in L-HPCC, resulting in a lower MPRR. The heat release rate and MPRR values for the E-HPCC are comparable to the L-HPCC values. The EHPCC mode provides the lowest NOX emission. The soot emissions for all three modes are low.

Long-haul and other heavy-duty trucks, presently almost entirely powered by diesel fuel, face challenges meeting worldwide needs for greatly reducing nitrogen oxide (NOx) emissions. Dual-fuel gasoline-alcohol engines could potentially provide a means to cost-effectively meet this need at large scale in the relatively near term. They could also provide reductions in greenhouse gas emissions. These spark ignition (SI) flexible fuel engines can provide operation over a wide fuel range from mainly gasoline use to 100% alcohol use. The alcohol can be ethanol or methanol. Use of stoichiometric operation and a three-way catalytic converter can reduce NOx by around 90% relative to emissions from diesel engines with state of the art exhaust treatment.

The quest for higher efficiency and performance of automotive vehicles requires application of materials with high strength, stiffness and lower weight in their construction. Particulate-reinforced aluminum-matrix composites are cost-competitive materials, which can meet these requirements. MMCC, Inc. has been optimizing particulate-reinforced alloy systems and developing the Advanced Pressure Infiltration Casting (APIC™) process for the manufacture of components from these materials. This paper discusses the results of a recent study in which composites reinforced with 55 vol.% alumina were cast using two sizes of alumina particulate and eight different matrix alloys based on Al-4.5 wt.% Cu with varying amounts of silicon and magnesium. Optimum heat treatments for each alloy were determined utilizing microhardness studies. The tensile strength and fracture toughness were evaluated as a function of alloy chemistry, particulate size, and heat treatment.

This paper provides an overview of spark-ignition engine unburned hydrocarbon emissions mechanisms, and then uses this framework to relate measured engine-out hydrocarbon emission levels to the processes within the engine from which they result. Typically, spark-ignition engine-out HC levels are 1.5 to 2 percent of the gasoline fuel flow into the engine; about half this amount is unburned fuel and half is partially reacted fuel components. The different mechanisms by which hydrocarbons in the gasoline escape burning during the normal engine combustion process are described and approximately quantified. The in-cylinder oxidation of these HC during the expansion and exhaust processes, the fraction which exit the cylinder, and the fraction oxidized in the exhaust port and manifold are also estimated.

The chemistry of unburned hydrocarbon oxidation in SI engine exhaust was modeled as a function of temperature and concentration of unburned gas for lean and rich mixtures. Detailed chemical kinetic mechanisms were used to model isothermal reactions of unburned fuel/air mixture in an environment of burned gases at atmospheric pressure. Simulations were performed using five pure fuels (methane, ethane, propane, n-butane and toluene) for which chemical kinetic mechanisms and steady state hydrocarbon (HC) emissions data were available. A correlation is seen between reaction rates and HC emissions for different fuels. Calculated relative amounts of intermediate oxidation products are shown to be consistent with experimental measurements.

To understand the effects of crevices on the engine-out hydrocarbon emissions, a series of engine experiments was carried out with different piston crevice volumes and with simulated head gasket crevices. The engine-out HC level was found to be modestly sensitive to the piston crevice size in both the warmed-up and the cold engines, but more sensitive to the crevice volume in the head gasket region. A substantial decrease in HC in the cold-to-warm-up engine transition was observed and is attributed mostly to the change in port oxidation.

Currently, states that are out of compliance with the National Ambient Air Quality Standards must, according to the Clean Air Act Amendments of 1990 (CAAA), develop and implement control strategies that demonstrate specific degrees of reduction in emissions-with the degree of reduction depending upon the severity of the problem. One tool that has been developed to aid regulators in both deciding an appropriate course of action and to demonstrate the desired reductions in mobile emissions is EPA's Mobile 5a emission estimation model. In our study, Mobile 5a has been used to examine the effects of regulatory strategies, as applied to the Northeast United States, on vehicle emissions under worst-case ozone-forming conditions.

The oxidation chemistry of paraffins, aromatics, olefins and MTBE were examined. Detailed chemical kinetics calculations were carried out for oxidation of these compounds in the engine cycle. The oxidation rates are very sensitive to temperature. At temperatures of over 1400 K (depending on the fuel), all the hydrocarbons are essentially oxidized for typical residence time in the engine. Based on the kinetics calculations, a threshold temperature is defined for the conversion of the fuel species to CO, CO2, H2O and partially oxidized products. The difference in the survival fraction between aromatics and non-aromatics is attributed to the higher threshold temperature of the aromatics.

The engine-out (EO) total and speciated hydrocarbon emissions data from the Auto-Oil Program Phase II Heavy Hydrocarbon Study had been analyzed. The methodology was to first investigate the stabilized EO emissions (Bag 2) of a specific vehicle (Vehicle 04B, a 1989 Model Year Ford Taurus); then the vehicle-to-vehicle differences in Bag2 emissions were considered. Finally, the differences in the Bag2 and the starting/warm-up EO emissions (Bag1) were examined. The speciated emissions may be interpreted as a “feed-through” part due to the unreacted fuel species, and an “offset” part due to the decomposition products. The significant non-fuel emitted species were methane and the olefins. The HC emissions for vehicles with different total emissions were similar in species composition. For both the total and speciated emissions, there was no substantial difference between the Bag1 and Bag2 values for Vehicle 04B.

A technique has been developed to measure the desorption and subsequent oxidation of fuel in the oil layer by spiking the oil with liquid fuel and firing the engine on gaseous fuel or motoring with air. Experiments suggest that fuel desorption is not diffusion limited above 50 °C and indicated that approximately two to four percent of the cylinder oil layer is fresh oil from the sump. The increase in hydrocarbon emissions is of the order of 100 ppmC1 per 1% liquid fuel introduced into the fresh oil in a methane fired engine at mid-speed and light load conditions. Calculations indicate that fuel desorbing from oil is much more likely to produce hydrocarbon emissions than fuel emerging from crevices.

A fuel volatility model based on the major species present in the fuel has been formulated. The model accurately predicts the ASTM distillation curves and Reid Vapor Pressure for hydrocarbon fuels. The model may be used to assess the fuel effects on the extent of evaporation and the vapor composition in the mixture preparation process.

The effect of engine operating parameters (speed, spark timing, and fuel-air equivalence ratio [Φ]) on hydrocarbon (HC) oxidation within the cylinder and exhaust system is examined using propane or isooctane fuel. Quench gas (CO2) is introduced at two locations in the exhaust system (exhaust valve or port exit) to stop the oxidation process. Increasing the speed from 1500 to 2500 RPM at MBT spark timing decreases the total, cylinder-exit HC emissions by ∼50% while oxidation in the exhaust system remains at 40% for both fuels. For propane fuel at 1500 rpm, increasing Φ from 0.9 (fuel lean) to 1.1 (fuel rich) reduces oxidation in the exhaust system from 42% to 26%; at 2500 RPM, exhaust system oxidation decreases from 40% to approximately 0% for Φ = 0.9 and 1.1, respectively. Retarded spark increases oxidation in the cylinder and exhaust system for both fuels. Decreases in total HC emissions are accompanied by increased olefinic content and atmospheric reactivity.

A model has been developed which predicts engine-out hydrocarbon (HC) emissions for spark-ignition engines. The model consists of a set of scaling laws that describe the individual processes that contribute to HC emissions. The model inputs are the critical engine design and operating variables. This set of individual process scaling relations was then calibrated using production spark-ignition engine data at a fixed light-load operating point. The data base consisted of engine-out HC emissions from two-valve and four-valve engine designs with variations in spark timing, valve timing, coolant temperature, crevice volume, and EGR, for five different engines. The model was calibrated separately for the three different engines to accommodate differences in engine design details and to determine the relative magnitudes of each of the major sources. A good fit to this database was obtained.

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke.

The effects of lubrication system parameters on particulate emission rate and composition were studied. Engine load, viscosity and piston-ring gap were varied. Particulate rate and composition were measured for multiple combinations of lubricant and ring-gap configurations at three different engine operating conditions. Particulate rates were higher with the lower viscosity oil and larger with the wider top-ring gap. At high load, the difference in particulate rate was due to changes in the non-soluble portion, while at medium and low loads, the change in particulate rate was due to differences in the lubricant-derived portion of the soluble organic fraction (SOF). Additionally, changes in the fuel-derived portion of the SOF were discovered and attributed to changes in fuel-absorption in the oil film.

In order to understand how unburned hydrocarbons emerge from SI engines and, in particular, how non-fuel hydrocarbons are formed and oxidized, a new gas sampling technique has been developed. A sampling unit, based on a combination of techniques used in the Fast Flame Ionization Detector (FFID) and wall-mounted sampling valves, was designed and built to capture a sample of exhaust gas during a specific period of the exhaust process and from a specific location within the exhaust port. The sampling unit consists of a transfer tube with one end in the exhaust port and the other connected to a three-way valve that leads, on one side, to a FFID and, on the other, to a vacuum chamber with a high-speed solenoid valve. Exhaust gas, drawn by the pressure drop into the vacuum chamber, impinges on the face of the solenoid valve and flows radially outward.

A sampling system was developed to measure the evolution of the speciated hydrocarbon emissions from a single-cylinder SI engine in a simulated starting and warm-up procedure. A sequence of exhaust samples was drawn and stored for gas chromatograph analysis. The individual sampling aperture was set at 0.13 s which corresponds to ∼ 1 cycle at 900 rpm. The positions of the apertures (in time) were controlled by a computer and were spaced appropriately to capture the warm-up process. The time resolution was of the order of 1 to 2 cycles (at 900 rpm). Results for four different fuels are reported: n-pentane/iso-octane mixture at volume ratio of 20/80 to study the effect of a light fuel component in the mixture; n-decane/iso-octane mixture at 10/90 to study the effect of a heavy fuel component in the mixture; m-xylene and iso-octane at 25/75 to study the effect of an aromatics in the mixture; and a calibration gasoline.

A method to collect and speciate the components of gasoline absorbed in the lubricant oil using gas chromatography has been developed. Samples were collected continuously from the piston skirt, baffle and sump in a Saturn engine. A long (18 hours) test was performed to determine the build up of hydrocarbons in the sump, and a shorter (25 min) test was performed to determine the build up of hydrocarbons in the piston skirt and baffle during engine warm-up. The first experiment showed that the total hydrocarbon concentration in the sump oil reached a steady state of about 1.35% mass fraction after 11 hours of engine operation. The relative concentration of individual fuel hydrocarbon species absorbed in the oil increases exponentially with boiling point. Most of the identified species in the oil consist of the heavy end aromatics. Similar compositions but lower concentrations were found for samples collected from the piston skirt during engine warm-up.

About 50-90 percent of the hydrocarbons that escape combustion during flame passage in spark-ignition engine operation are oxidized in the cylinder before leaving the system. The process involves the transport of unreacted fuel from cold walls towards the hotter burned gas regions and subsequent reaction. In order to understand controlling factors in the process, a transient one-dimensional reactive-diffusive model has been formulated for simulating the oxidation processes taking place in the reactive layer between hot burned gases and cold unreacted air/fuel mixture, with initial and boundary conditions provided by the emergence of hydrocarbons from the piston top land crevice. Energy and species conservation equations are solved for the entire process, using a detailed chemical kinetic mechanism for propane.