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An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

A central challenge for efficient auto-ignition controlled low-temperature gasoline combustion (LTGC) engines has been achieving the combustion phasing needed to reach stable performance over a wide operating regime. The negative valve overlap (NVO) strategy has been explored as a way to improve combustion stability through a combination of charge heating and altered reactivity via a recompression stroke with a pilot fuel injection. The study objective was to analyze the thermal and chemical effects on NVO-period energy recovery. The analysis leveraged experimental gas sampling results obtained from a single-cylinder LTGC engine along with cylinder pressure measurements and custom data reduction methods used to estimate period thermodynamic properties. The engine was fueled by either iso-octane or ethanol, and operated under sweeps of NVO-period oxygen concentration, injection timing, and fueling rate.

Development of reliable magnesium (Mg) to steel joining methods is one of the critical issues in broader applications of Mg in automotive body construction. Ultrasonic spot welding (USW) has been demonstrated successfully to join Mg to steel and to achieve strong joints. In this study, corrosion test of ultrasonic spot welds between 1.6 mm thick Mg AZ31B-H24 and 0.8 mm thick galvanized mild steel, without and with adhesive, was conducted. Adhesive used was a one-component, heat-cured epoxy material, and was applied between overlapped sheets before USW. Corrosion test was conducted with an automotive cyclic corrosion test, which includes cyclic exposures of dipping in the 0.5% sodium chloride (NaCl) bath, a constant humidity environment, and a drying period. Lap shear strength of the joints decreased with the cycles of corrosion exposure. Good joint strengths were retained at the end of 30-cycle test.

For renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement.

In this contribution, nuanced changes of a commercial Cu-SSZ-13 catalyst with hydrothermal aging, which have not been previously reported, as well as their corresponding impact on SCR functions, are described. In particular, a sample of Cu-SSZ-13 was progressively aged between 550 to 900°C and the changes of performance in NH3 storage, oxidation functionality and NOx conversion of the catalyst were measured after hydrothermal exposure at each temperature. The catalysts thus aged were further characterized by NH3-TPD, XRD and DRIFTS techniques for structural changes. Based on the corresponding performance and structural characteristics, three different regimes of hydrothermal aging were identified, and tentatively as assigned to “mild”, “severe” and “extreme” aging. Progressive hydrothermal aging up to 750°C decreased NOx conversion to a small degree, as well as NH3 storage and oxidation functions.

The development of new catalytic materials is still dominated by trial and error methods, even though the experimental and theoretical bases for their characterization have improved dramatically in recent years. Although it has been successful, the empirical development of catalytic materials is time consuming and expensive with no guarantee of success. We have been exploring computationally complex but experimentally simple systems to establish a “catalysis by design” protocol that combines the power of theory and experiment. We hope to translate the fundamental insights directly into a complete catalyst system that is technologically relevant. The essential component of this approach is that the catalysts are iteratively examined by both theoretical and experimental methods.

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/γ-AI2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation.

Diesel particulate samples were collected from a light duty engine operated at a single speed-load point with a range of biodiesel and conventional fuel blends. The oxidation reactivity of the samples was characterized in a laboratory reactor, and BET surface area measurements were made at several points during oxidation of the fixed carbon component of both types of particulate. The fixed carbon component of biodiesel particulate has a significantly higher surface area for the initial stages of oxidation, but the surface areas for the two particulates become similar as fixed carbon oxidation proceeds beyond 40%. When fixed carbon oxidation rates are normalized to total surface area, it is possible to describe the oxidation rates of the fixed carbon portion of both types of particulates with a single set of Arrhenius parameters. The measured surface area evolution during particle oxidation was found to be inconsistent with shrinking sphere oxidation.

The friction and wear characteristics of three commercially-available, electrolytic coatings for aluminum engine cylinder bores were compared to those of cast iron liners. A Ni/SiC electrocomposite, a hard anodized treatment, and a Plasma Electrolytic Oxidation (PEO) coating were investigated. ASTM standard test method G133-95, non-firing test method, for linearly reciprocating sliding wear was modified to use segments of piston rings and cylinder liners. Tests were conducted using Mr. Goodwrench™ 5W30 as a lubricant at room temperature. The normal force was 150N, the reciprocating frequency was 15Hz, the stroke length was 8mm, and the test duration was 60 minutes. Kinetic friction coefficients ranged from 0.1 to 0.22, typical of boundary lubrication. The Ni/SiC and cast iron samples exhibited the lowest friction. The wear resistance of the Ni/SiC coating was superior to that of cast iron.

Development of reliable magnesium (Mg) to steel joining methods is one of the critical issues in boarder applications of Mg in automotive body construction. However, due to the large difference of melting temperatures of Mg and steel, fusion welding between two metals is very challenging. Ultrasonic spot welding (USW) has been demonstrated to join Mg to steel without melting and to achieve strong joints. However, galvanic corrosion between Mg and steel is inevitable but not well quantified. In this study, corrosion test of ultrasonic spot welds between 1.6-mm-thick Mg AZ31B-H24 and 0.8-mm-thick galvanized mild steel was conducted. No specific corrosion protection was applied in order to study the worst corrosion behavior. Corrosion test was conducted with an automotive cyclic corrosion test, which includes cyclic exposures of dipping in the salt bath, air drying, then a constant humidity environment. Lap shear strength of the joints decreased linearly with the cycles.

Urea-selective catalytic reduction (SCR) catalysts are the leading aftertreatment technology for diesel engines, but there are major challenges associated with meeting future NOx emission standards, especially under transient drive cycle conditions that include large swings in exhaust temperatures. Here we present a simplified, transient, one-dimensional integral model of NOx reduction by NH₃ on a commercial small-pore Cu-zeolite urea-SCR catalyst for which detailed kinetic parameters have not been published. The model was developed and validated using data acquired from bench reactor experiments on a monolith core, following a transient SCR reactor protocol. The protocol incorporates NH₃ storage, NH₃ oxidation, NO oxidation and three global SCR reactions under isothermal conditions, at three space velocities and at three NH₃/NOx ratios.

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 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.

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.

Phosphorous in diesel exhaust is derived via engine oil consumption from the zinc dialkyldithiophosphate (ZDDP) oil additive used for engine wear control. Phosphorous present in the engine exhaust can react with an exhaust catalyst and cause loss of performance through masking or chemical reaction. The primary effect is loss of light-off or low temperature performance. Although the amount of ZDDP used in lube oil is being reduced, it appears that there may is a minimum level of ZDDP needed for engine durability. One of the ways of reducing the effects of the resulting phosphorous on catalysts might be to alter the chemical state of the phosphorous to a less damaging form or to develop catalysts which are more resistant to phosphorous poisoning. In this study, lube oil containing ZDDP was added at an accelerated rate through a variety of engine pathways to simulate various types of engine wear or oil disposal practices.

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.

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.

An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.

Mixing controlled compression ignition, i.e., diesel engines are efficient and are likely to continue to be the primary means for movement of goods for many years. Low-net-carbon biofuels have the potential to significantly reduce the carbon footprint of diesel combustion and could have advantageous properties for combustion, such as high cetane number and reduced engine-out particle and NOx emissions. We developed a list of over 400 potential biomass-derived diesel blendstocks and populated a database with the properties and characteristics of these materials. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a blendstock met the basic requirements for handling in the diesel distribution system and use as a blend with conventional diesel. Criteria included cetane number ≥40, flashpoint ≥52°C, and boiling point or T90 ≤338°C.