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This paper examines the issues concerning particulate matter (PM) emissions measurement at the 3 mg/mi level proposed as the future LEV III standard. These issues are general in nature, but are exacerbated at the low levels contemplated for upcoming emissions standards. They are discussed in the context of gasoline direct injection (GDI) engines, where they can have an important impact on the continued development of this technology for improved fuel economy. GDI particulate emissions, just as engine-out diesel PM, contain a high fraction of soot. But the total PM mass is significantly lower than from diesel engines, and there can be significant variations in emissions rate and apparent PM composition between cold-start and running emissions. PM emissions levels depend on sampling method and location. As a result, there can be substantial differences in PM sampled and diluted directly at the exhaust pipe, as opposed to measurements from a dilution tunnel.

The characteristics of the early development of fuel sprays from pressure swirl atomizer injectors of the type used in direct injection gasoline engines is investigated. Planar laser-induced fluorescence (PLIF) was used to visualize the fuel distribution inside a firing optical engine. The early spray development of three different injectors at three different fuel pressures (3, 5, and 7 MPa) was followed as a function of time in 30 μsec intervals. Four phases could be identified: 1) A delay phase between the rising edge of the injection pulse and the first occurrence of fuel in the combustion chamber, 2) A solid jet or pre-spray phase, in which a poorly atomized stream of liquid fuel during the first 150 μsec of the injection. 3) A wide hollow cone phase, separation of the liquid jet into a hollow cone spray once sufficient tangential velocity has been established and 4) A fully developed spray, in which the spray cone angle is narrowed due to a low pressure zone at the center.

FTP emissions tests on a passenger vehicle equipped with a 1.8 L IDI turbo-charged diesel engine show that the mass emissions of particles decrease by (36±8)% when 16.6% dimethoxymethane (DMM) by volume is added to a diesel fuel. Particle size measurements reveal log-normal accumulation mode distributions with number weighted geometric mean diameters in the 80 - 100 nm range. The number density is comparable for both base fuel and the DMM/diesel blend; however, the distributions shift to smaller particle diameter for the blend. This shift to smaller size is consistent with the observed reduction in particulate mass. No change is observed in NOx emissions. Formaldehyde emissions increase by (50±25)%, while emissions of other hydrocarbons are unchanged to within the estimated experimental error.

The presence of liquid fuel inside the engine cylinder is believed to be a strong contributor to the high levels of hydrocarbon emissions from spark ignition (SI) engines during the warm-up period. Quantifying and determining the fate of the liquid fuel that enters the cylinder is the first step in understanding the process of emissions formation. This work uses planar laser induced fluorescence (PLIF) to visualize the liquid fuel present in the cylinder. The fluorescing compounds in indolene, and mixtures of iso-octane with dopants of different boiling points (acetone and 3-pentanone) were used to trace the behavior of different volatility components. Images were taken of three different planes through the engine intersecting the intake valve region. A closed valve fuel injection strategy was used, as this is the strategy most commonly used in practice. Background subtraction and masking were both performed to reduce the effect of any spurious fluorescence.

Measurements of particulate matter (PM) from spark ignition (SI) engine exhaust using dilution tunnels will become more prevalent as emission standards are tightened. Hence, a study of the dilution process was undertaken in order to understand how various dilution related parameters affect the accuracy with which PM sizes and concentrations can be determined. A SI and a compression ignition (CI) engine were separately used to examine parameters of the dilution process; the present work discusses the results in the context of SI exhaust dilution. A Scanning Mobility Particle Sizer (SMPS) was used to measure the size distribution, number density, and volume fraction of PM. Temperature measurements in the exhaust pipe and dilution tunnel reveal the degree of mixing between exhaust and dilution air, the effect of flowrate on heat transfer from undiluted and diluted exhaust to the environment, and the minimum permissible dilution ratio for a maximum sample temperature of 52°C.

PM (Particulate Matter) emitted by vehicles and engines is most often measured quantitatively by collecting diluted exhaust samples on filters that are weighed pre-and post-test. The filter media used have high efficiency for small particles found in vehicle exhaust, but they also collect organic matter from the vapor phase with a lower, but nonzero, efficiency. In the past, organic vapor adsorption was usually negligible compared with PM levels from untreated diesel engine exhaust. For vehicles employing a DPF (Diesel Particulate Filter) and emitting very low PM, that is no longer the case. This paper reports measurements of the organic vapor deposition artifact for different filter media, including the two types (TX40 and Teflo) called for by the 2007 regulations for heavy duty diesel engines. The vapor artifact represents a substantial fraction of the 2007 regulatory standard of 10 mg/mi for light duty vehicles.

The autoignition characteristics of methanol, ethanol and MTBE (methyl tert-butyl ether) have been investigated in a rapid compression machine at pressures in the range 20-40 atm and temperatures within 750-1000 K. All three oxygenated fuels tested show higher autoignition temperatures than paraffins, a trend consistent with the high octane number of these fuels. The autoignition delay time for methanol was slightly lower than predicted values using reported reaction mechanisms. However, the experimental and measured values for the activation energy are in very good agreement around 44 kcal/mol. The measured activation energy for ethanol autoignition is in good agreement with previous shock tube results (31 kcal/mol), although ignition times predicted by the shock tube correlation are a factor of three lower than the measured values. The measured activation energy for MTBE, 41.4 kcal/mol, was significantly higher than the value previously observed in shock tubes (28.1 kcal/mol).

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.

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.

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.

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.

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.

Concentrations of individual species in the engine-out exhaust gas from a gasoline-fueled (101.5 or 91.5 RON), direct-injection, compression-ignition (HCCI) engine have been measured by gas chromatography over the A/F range 50 to 230 for both stratified and nearly homogeneous fuel-air mixtures. The species identified include hydrocarbons, oxygenated organic species, CO, and CO2. A single-cylinder HCCI engine (CR = 15.5) with heated intake charge was used. Measurements of the mass and size distribution of particulate emissions were also performed. The 101.5 RON fuel consisted primarily of five species, simplifying interpretation of the exhaust species data: iso-pentane (24%), iso-octane (22%), toluene (17%), xylenes (10%), and trimethylbenzenes (9%).

Previous research into Particulate Matter (PM) emissions from a spark-ignition engine has shown that the main factor determining the how PM emissions respond to transient engine operating conditions is the effect of those conditions on intake port processes such as fuel evaporation. The current research extends the PM emissions data base by examining the effect of transient load and speed operating conditions, as well as engine start-up and shut-down. In addition, PM emissions are examined during “real-world” driving conditions - specifically, the Federal Test Procedure. Unlike the previous work, which was performed on an engine test stand with no exhaust gas recirculation and with a non-production engine controller, the current tests are performed on a fully-functional, production vehicle operated on a chassis dynamometer to better examine real world emissions.

A one-dimensional model has been developed for the species and energy transfer over a thin (0.1-0.5 mm) layer of liquid fuel present on the wall of a spark-ignition engine. Time-varying boundary conditions during compression and flame passage were used to determine the rate of methanol vaporization and oxidation over a mid-speed, mid-load cycle, as a function of wall temperature. The heat of vaporization and the boiling point of the fuel were varied about a baseline to determine the effect of these characteristics, at a fixed operating point and lean conditions (ϕ = 0.9). The calculations show that the evaporation of fuels from layers on cold walls starts during flame passage, peaking a few milliseconds later, and continuing through the exhaust phase.

Numerical calculations of the fuel spray structure from a high-pressure swirl injector were used to enable the interpretation of experimental observations obtained in hot, hollow-cone fuel sprays issued into sub-atmospheric-pressure environments. The experiments show that the spray becomes narrower, more compact, but with a relatively long penetration depth. Model input parameters, including the droplet size distribution, early vapor production, and initial cone angle, were modified to determine which spray characteristics are important in recreating observed spray structures. A very small mean droplet diameter is needed to recreate the experimentally observed structure of the high-temperature, low-pressure sprays. Vapor addition to the emerging spray is then required to increase the axial penetration and provide the observed vapor core.

A one-dimensional model for crevice HC post-flame oxidation is used to calculate and understand the effect of operating parameters and fuel type (propane and isooctane) on the extent of crevice hydrocarbon and the product distribution in the post flame environment. The calculations show that the main parameters controlling oxidation are: bulk burned gas temperatures, wall temperatures, turbulent diffusivity, and fuel oxidation rates. Calculated extents of oxidation agree well with experimental values, and the sensitivities to operating conditions (wall temperatures, equivalence ratio, fuel type) are reasonably well captured. Whereas the bulk gas temperatures largely determine the extent of oxidation, the hydrocarbon product distribution is not very much affected by the burned gas temperatures, but mostly by diffusion rates. Uncertainties in both turbulent diffusion rates as well as in mechanisms are an important factor limiting the predictive capabilities of the model.