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The effects of fuel injection and spark timing on engine-out, regulated (total HC, NOx, and CO) and speciated HC emissions have been investigated for a 0.31L, single-cylinder, direct-injection, spark-ignition (DISI) engine equipped with an air-forced fuel injector. When the timing of the start of the air injection (SOA) is varied during high stratification operation, the mole fractions of all regulated emissions vary sharply over relatively small (20-30 crank angle degrees) changes in SOA. In addition, the distribution of exhaust hydrocarbon species changes significantly. As stratification increases, the contribution of unburned paraffinic fuel components to the HC emissions decreases by a factor of two while the olefinic partial oxidation products increase. When the spark timing is varied during high stratification operation, the HC emissions increase sharply as the spark timing is retarded relative to MBT.

Although the intent of the SHED test (Sealed Housing for Evaporative Determination) is to measure evaporative fuel losses, the SHED sampling methodology in fact measures hydrocarbons from all vehicle and test equipment sources. Leakage of air conditioning (AC) refrigerant is one possible non-fuel source contributing to the SHED hydrocarbon measurement. This report describes a quick and relatively simple method to identify the contribution of AC refrigerant to the SHED analyzer reading. R134A (CH2FCF3), the hydrofluorocarbon refrigerant used in all current automotive AC systems, as well as its predecessor, the chlorofluorocarbon R12, can be detected using the gas chromatography methods currently in place at many emissions labs for the speciation of exhaust and evaporative hydrocarbon emissions.

Development of the Sequence VIB dynamometer engine test procedure for evaluating the fuel efficiency benefits of engine oils has recently been completed. This test was designed as an improvement over its predecessor, the Sequence VIA test. It evaluates fuel economy using a range of boundary/mixed and hydrodynamic lubrication stages selected to better represent a wider range of engines. In addition to determining “fresh oil” fuel economy, the new test determines fuel efficiency retention after a second oil aging stage that corresponds to 6437 - 9674 km (4,000 - 6,000 miles) of pre-certification aging of engine oils in vehicles and is representative of customer use. This paper describes the selection of aging conditions and length.

The newly developed Sequence VIB engine dynamometer test for measuring the ability of engine oils to improve engine fuel efficiency was designed as an improvement on its predecessor, the Sequence VIA test. The Sequence VIB test features an additional, extended oil aging to correspond to aging of engine oils in certification vehicles and in customer use, and a new set of boundary/mixed and hydrodynamic lubrication stages to better represent a wider range of engines. Five fuel economy measurement stages were chosen for the Sequence VIB test from a larger set of prototype stages, based on extensive friction modeling of engines, analysis of Sequence VIA data on reference oils, and operational considerations. Time factors for these stages were derived based on a mini-mapping of engines considering engine operating conditions in the Metro/Highway Federal fuel economy test procedure (FTP M/H) and the estimated market volume of each engine-vehicle.

A single-cylinder, spark-ignited engine was run on a certification test gasoline to saturate the oil in the sump with fuel through exposure to blow-by gas. The sump volume was large relative to production engines making its absorption-desorption time constant long relative to the experimental time. The engine was motored at 1500 RPM, 90° C coolant and oil temperature, and 0.43 bar MAP without fuel flow. Exhaust HC concentrations were measured by on-line FID and GC analysis. The total motoring HC emissions were 150 ppmC1; the HC species distribution was heavily weighted to the low-volatility components in the gasoline. No high volatility components were visible. The engine was then fired on isooctane fuel at the above conditions, producing a total engine-out HC emission of 2300 ppmC1 for Φ = 1.0 and MBT spark timing.

Total and speciated, engine-out, hydrocarbon (HC) emissions have been measured as a function of time after a 23°C cold start of a gasoline-fueled, V-8 engine. Hydrocarbon emissions from two fuel injection systems were compared: a production port-fuel-injection (PFI) system; and a pre-vaporized (heated) central-fuel-injection (PV-CFI) system. The results indicate that, for this particular engine at the chosen operating conditions, the effect of fuel preparation on HC emissions during cold start is minimal at low load (2.57 bar IMEP (gross), MAP = 0.34 bar) but becomes significant at higher load (5.15 bar IMEP, MAP = 0.58 bar) early in the cold start. Comparison of the relative contribution to the exhaust HC of a series of fuel-derived alkanes suggests that fuel absorption in oil films is a minor contributor to HC emissions from this engine during a 23°C cold start.

The main factors influencing the development of engine oils for the future are environmental protection, resource utilization and customer satisfaction. Improving engine oil no longer means just providing adequate durability but also maximizing fuel efficiency, minimizing detrimental effects on emission systems and maximizing useful life. Opportunities for improvements in these areas, discussed in detail in this paper, will be considered by ILSAC (International Lubricant Standardization and Approval Committee formed by the American Automobile Manufacturers Association, AAMA, and Japan Automobile Manufacturers Association, JAMA) in developing the ILSAC GF-3 standard to be introduced around the year 2000.

Although much has been learned in recent years about the atmospheric reactivity of the hydrocarbon (HC) emissions from gasoline-fueled vehicles, there is only a limited database of corresponding information for exhaust emissions from diesel-fueled vehicles. An assessment of exhaust reactivity requires “speciation”, or measurement of the individual species of the HC fraction. The HC exhaust emissions are a complex mixture of unburned and partially burned fuel components. Because diesel fuel contains a much higher molecular weight range (typically C9-C26) than gasoline (typically C5-C12), new methodology was required to accommodate the collection and analysis of the >C12 fraction of the HC exhaust. As part of a study of the effects of fuel and other factors on the chemical nature of diesel emissions, we have developed a method for the collection and analysis of the semivolatile or heavy HC (>C12) fraction of the exhaust.

Obtaining the maximum benefits from advanced fuel efficient engine oils will require that those oils not only provide fuel efficiency when new but also throughout the service interval for the oil. The effects of laboratory and engine aging on the ability of an oil containing a molybdenum dialkyldithiocarbamate (MoDTC) additive to provide reduced friction have been investigated. Results of these studies show that the friction reducing capability of this oil, as measured in a laboratory test, was lost prior to depletion of the MoDTC. Interactions between MoDTC and other additives were found to be important with regard to providing friction reduction. Implications for development of advanced oils that will provide lasting fuel efficiency benefits are discussed.

Modern four-valve engines are running at ever higher compression ratios in order to improve fuel efficiency. Hotter cylinder bores also can produce increased fuel economy by decreasing friction due to less viscous oil layers. In this study changes in compression ratio and coolant temperature were investigated to quantify their effect on exhaust emissions. Tests were run on a single cylinder research engine with a port-deactivated 4-valve combustion chamber. Two compression ratios (9.15:1 and 10.0:1) were studied at three air/fuel ratios (12.5, 14.6 and 16.5) at a part load condition (1500 rpm, 3.8 bar IMEP). The effect of coolant temperature (66 °C and 108°C) was studied at the higher compression ratio. The exhaust was sampled and analyzed for both total and speciated hydrocarbons. The speciation analysis provided concentration data for hydrocarbons present in the exhaust containing twelve or fewer carbon atoms.

As vehicle tailpipe emission levels decrease with improvements in emission control technology and reformulation of gasolines, exhaust hydrocarbon levels begin to approach the levels in ambient air. Hydrocarbon speciation at these low levels requires high sensitivity capillary gas chromatography methods. In this study, a mixture of “synthetic” exhaust was prepared at two concentration levels (approximately 5 ppm C and 10 ppm C), and was analyzed by the widely-used Auto/Oil Air Quality Improvement Research Program (AQIRP) Phase II (gas chromatography) speciation method with a sensitivity of 0.005 ppm C for individual species. The mixture at each concentration level, along with a sample of ambient air, was analyzed a total of 20 times on 10 separate days over a 2½ week period. Concentrations of total hydrocarbons (HCs) and individual species (using the AQIRP library) were measured; averages and standard deviations were calculated.

Recent changes in regulatory practices have brought about a need for speciated analysis of the volatile organic components of vehicle exhaust. The purpose of this study was to allow interested laboratories to participate in a Round Robin so that each could assess its speciation methodologies for hydrocarbons, alcohols, and carbonyls. The results from analysis of the liquid samples (methanol, ethanol, and DNPH-derivatives of carbonyls) were reported in SAE 941944. For gaseous hydrocarbon samples, two gasolines from the Auto/Oil Air Quality Improvement Research Program (AQIRP) were used to prepare compressed gas cylinders of “synthetic exhaust.” These samples were also doped with typical light hydrocarbon combustion components, marker compounds, and MTBE (in one of the two sets of samples). The cylinders were circulated to 16 laboratories, which included automotive and petroleum companies, contract laboratories, and regulatory agencies.

For several years, a single-cylinder, spark-ignited engine without catalyst has been operated at Ford on single-component fuels that are constituents of gasoline as well as on simple fuel mixtures. This paper presents a review of these experiments as well as others pertinent to understanding hydrocarbon emissions. The engine was run at four steady-state conditions which are typical of normal operation. The fuel structure and the engine operating conditions affected both the total HC emissions and the reactivity of these emissions for forming photochemical smog in the atmosphere. These experiments identified major precursor species of the toxic HC emissions benzene and 1,3-butadiene to be alkylated benzenes and either straight chain terminal olefins or cyclic alkanes, respectively. In new data presented, the primary exhaust hydrocarbon species from MTBE combustion is identified as isobutene.

A hydrocarbon trapping system for cold start emissions was constructed and tested using two types of carbonaceous adsorbents provided by Corning, Inc. One was made by combining activated carbon with an organic binder and extruding it into a honeycomb, and the other by depositing a carbon coating on a ceramic monolith. The tests were carried out on an engine in a dynamometer laboratory to characterize the performance of the carbon elements under transient cold start conditions. Performance was evaluated by continuously measuring exhaust gas hydrocarbon concentrations upstream and downstream of the trap, using conventional emissions consoles. Samples were also collected for off-line analysis of individual hydrocarbon species using gas chromatography to examine differences in adsorption of individual species. The speciated hydrocarbon data were used to distinguish between the mass trapping efficiency and a reactivity-based trapping efficiency of the adsorbant traps.

Speciated HC emissions from the exhaust system of a production engine without an active catalyst have been obtained with 3 sec time resolution during a 70°F cold start using two control strategies. For the conventional cold start, the emissions were initially enriched in light fuel alkanes and depleted in heavy aromatic species. The light alkanes fell rapidly while the lower vapor pressure aromatics increased over a period of 50 sec. These results indicate early retention of low vapor pressure fuel components in the intake manifold and exhaust system. Loss of higher molecular weight HC species does occur in the exhaust system as shown by experiments in which the exhaust system was preheated to 100° C. The atmospheric reactivity of the exhaust HC emissions for photochemical smog formation increases as the engine warms.

Analytical procedures for the speciation of hydrocarbons and oxygenates (ethers, aldehydes, ketones and alcohols) in vehicle evaporative and tailpipe exhaust emissions have been improved for Phase II studies of the Auto/Oil Air Quality Improvement Research Program (AQIRP). One gas chromatograph (GC) was used for measurement of C1-C4 species and a second GC for C4-C12 species. Detection limits for this technique are 0.005 ppm C or 0.1 mg/mile exhaust emission level at a chromatographic signal-to-noise ratio of 3/1, a ten-fold improvement over the Phase I technique. The Phase I library was modified to include additional species for a total of 154 species. A 23-component gas standard was used to establish a calibration scale for automated computer identification of species. This method identifies 95±3% of the total hydrocarbon mass measured by GC for a typical exhaust sample. Solid adsorbent cartridges or impingers were used to collect aldehydes and ketones.

An analytical method for the determination of hydrocarbon and ether emissions from gasoline-, methanol-, and flexible-fueled vehicles is described. This method was used in Phase I of the Auto/Oil Air Quality Improvement Research Program to provide emissions data for various vehicles using individual reformulated gasolines and alternate fuels. These data would then be used for air modeling studies. Emission samples for tailpipe, evaporative, and running loss were collected in Tedlar bags. Gas chromatographic analysis of the emissions samples included 140 components (hydrocarbons, ethers, alcohols and aldehydes) between C1 and C12 in a single analysis of 54-minutes duration. Standardization, quality control procedures, and inter-laboratory comparisons developed and completed as part of this program are also described.

A reaction scheme depicting engine oil oxidation chemistry occurring in internal combustion engines is proposed. This scheme reflects the idea that hydroperoxides, which are initial oxidation products, are formed continuously in engine oil, regardless of the presence of radical trapping inhibitors, due to a continuous influx of free radicals from the combustion process. Therefore, the antioxidant behavior of a zinc dialkyldithiophosphate (ZDTP) itself and in combination with an ashless phenolic antioxidant has been investigated using a model hydrocarbon oxidation system in the presence of excess hydroperoxides. In order to approximate temperatures existing in critical engine locations, these studies were carried out at 160°C. Results obtained contribute to a better understanding of the antioxidant mechanisms of ZDTP and also provide basic information needed in development of laboratory test procedures for evaluation of engine oil antioxidant systems under realistic conditions.

Selected engine oils and zinc dialkyldithiophosphate additive concentrates have been added to used oils in various engines and subjected to engine testing. Oil samples obtained as a function of mileage accumulation have been analyzed using the peroxy radical titration method and 31P NMR. The engine studies were supplemented by laboratory investigations of antioxidant behavior of pure neutral and basic zinc dialkyldithiophosphates, dialkyldithiophosphoric acid, tetraalkylthioperoxydiphosphate (disulfide), and of neutral zinc dialkyldithiophosphate in combination with a hindered phenol antioxidant, 4,4′-methylenebis(2,6-di-tert-butylphenol). These investigations included studies of the effects of hydroperoxides and hydrocarbon oxidation products on the radical scavenging activity of the above compounds.