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The post-flame oxidation of unburned hydrocarbons released from the ring-pack crevice was investigated for a small, air-cooled, spark-ignition utility engine. Spark timing sweeps were performed at 50, 75 and 100% load and speeds of 1800, 2400 and 3060 RPM while operating at a 12:1 air-fuel ratio, which is typical for these engines. A global HC consumption rate (GCR) was introduced based on the temporal profile of the mass released from the ring pack; the mass release after CA90 and up to the point where the remainder of the ring pack HC mass is equal to the exhaust HC level was taken as the mass oxidized, and a rate was defined based on this mass and the corresponding crank angle period over which this took place. For all conditions tested, the GCR varied with the spark timing; advanced spark timing gave higher GCR.

An investigation of high speed direct injection (DI) compression ignition (CI) engine combustion fueled with gasoline (termed GDICI for Gasoline Direct-Injection Compression Ignition) in the low temperature combustion (LTC) regime is presented. As an aid to plan engine experiments at full load (16 bar IMEP, 2500 rev/min), exploration of operating conditions was first performed numerically employing a multi-dimensional CFD code, KIVA-ERC-Chemkin, that features improved sub-models and the Chemkin library. The oxidation chemistry of the fuel was calculated using a reduced mechanism for primary reference fuel combustion. Operation ranges of a light-duty diesel engine operating with GDICI combustion with constraints of combustion efficiency, noise level (pressure rise rate) and emissions were identified as functions of injection timings, exhaust gas recirculation rate and the fuel split ratio of double-pulse injections.

Several diffusion combustion scaling models were experimentally tested in two geometrically similar single-cylinder diesel engines with a bore diameter ratio of 1.7. Assuming that the engines have the same in-cylinder thermodynamic conditions and equivalence ratio, the combustion models primarily change the fuel injection pressure and engine speed in order to attain similar performance and emissions. The models tested include an extended scaling model, which scales diffusion flame lift-off length and jet spray penetration; a simple scaling model, which only scales spray penetration at equal mean piston speed; and a same speed scaling model, which holds crankshaft rotational velocity constant while also scaling spray penetration. Successfully scaling diffusion combustion proved difficult to accomplish because of apparent differences that remained in the fuel-air mixing and heat transfer processes.

Although the urea-SCR technology exhibits high NO reduction efficiency over a wide range of temperatures among the lean NO reduction technologies, further improvement in low-temperature performance is required to meet the future emission standards and to lower the system cost. In order to improve the catalyst technologies and optimize the system performance, it is critical to understand the reaction mechanisms and catalyst behaviors with respect to operating conditions. Urea-SCR catalysts exhibit poor NO reduction performance at low-temperature operating conditions (T ≺ 150°C). We postulate that the poor performance is either due to NH₃ storage inhibition by species like hydrocarbons or due to competitive adsorption between NH₃ and other adsorbates such as H₂O and hydrocarbons in the exhaust stream. In this paper we attempt to develop one-dimensional models to characterize inhibition and competitive adsorption in Fe-zeolite-based urea-SCR catalysts based on bench reactor experiments.

We describe a study to identify potential biofuels that enable advanced spark ignition (SI) engine efficiency strategies to be pursued more aggressively. A list of potential biomass-derived blendstocks was developed. An online database of properties and characteristics of these bioblendstocks was created and populated. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a bioblendstock met the requirements for advanced SI engines. Criteria included melting point (or cloud point) < -10°C and boiling point (or T90) <165°C. Compounds insoluble or poorly soluble in hydrocarbon were eliminated from consideration, as were those known to cause corrosion (carboxylic acids or high acid number mixtures) and those with hazard classification as known or suspected carcinogens or reproductive toxins.

More stringent emissions regulations are continually being proposed to mitigate adverse human health and environmental impacts of internal combustion engines. With that in mind, it has been proposed that vehicular particulate matter (PM) emissions should be regulated based on particle number in addition to particle mass. One aspect of this project is to study different sample handling methods for number-based aerosol measurements, specifically, two different methods for removing volatile organic compounds (VOCs). One method is a thermodenuder (TD) and the other is an evaporative chamber/diluter (EvCh). These sample-handling methods have been implemented in an engine test cell with a spark-ignited direct injection (SIDI) engine. The engine was designed for stoichiometric, homogeneous combustion.

New techniques have been developed to visualize soot deposition in both traditional and new diesel particulate filter (DPF) substrate materials using a modified cyanoacrylate fuming technique. Loading experiments have been conducted on a variety of single channel DPF substrates to develop a deeper understanding of soot penetration, soot deposition characteristics, and to confirm modeling results. Early results indicate that stabilizing the soot layer using a vaporized adhesive (Cynoacrylate) may allow analysis of the layer with new methods.

This paper describes the application of pore-scale filtration simulations to the advanced ceramic material (ACM) developed for use in advanced diesel particulate filters. The application required the generation of a three-dimensional substrate geometry to provide the boundary conditions for the flow model. An innovative stochastic modeling technique was applied matching chord length distribution and the porosity profile of the material. Additional experimental validation was provided by the single-channel experimental apparatus. Results show that the stochastic reconstruction techniques provide flexibility and appropriate accuracy for the modeling efforts. Early investigation efforts imply that needle length may provide a mechanism for adjusting performance of the ACM for diesel particulate filter (DPF) applications. New techniques have been developed to visualize soot deposition in both traditional and new DPF substrate materials.

Recent work has shown that energy efficiencies as well as yields and selectivities of the NOx reduction reaction can be enhanced by combining a plasma discharge with select catalysts. While analysis of gas phase species with a chemiluminescent NOx meter and mass spectrometer show that significant removal of NOx is achieved, high background concentrations of nitrogen preclude the measurement of nitrogen produced from NOx reduction. Results presented in this paper show that N2 from NOx reduction can be measured if background N2 is replaced with helium. Nitrogen production results are presented for a catalyst system where the catalyst is in the plasma region and where the catalyst is downstream from the plasma. The amount of N2 produced is compared with the amount of NOx removed as measured by the chemiluminescent NOx meter. The measured nitrogen from NOx reduction accounts for at least 40% of the total NOx removed for both reactor configurations.

System-level models containing engine model, emission models, and aftertreatment device models have been developed. All the sub-models have been developed separately and come from a variety of different sources. A new phenomenological CO model recently has been coupled into the previous integrated model. The emission models, including PM (particulate matter), NOx, and CO are also calibrated from experimental data. Some modification has been added to improve the integrated model and accept different aftertreatment device models for future work. The objective of this work is to study the DPF (Diesel Particulate Filter) regeneration during transient operating conditions using the integrated model. The integrated system-level model is used to studying the dynamic performance between engine and aftertreatment system. In this study, the calibrated emission models are validated at transient operating conditions.

This work integrated a CA10 (crank angle at 10% heat release) controller into an integrated engine, emissions and aftertreatment model platform. Two CA10 phasing targets were chosen to analyze how advancing (or retarding) the target combustion phasing (CA10) affect the formation of NO and CO. The effect of intake valve closure (IVC) timing, which is the control mechanism for maintaining the target combustion phasing, on the cylinder trapped mass, and hence the charge temperature after compression is detailed. Finally, the relation between combustion phasing and the blow-down process leading to the exhaust process is discussed. Retarding the target combustion phasing by two degrees saw a 330 K drop in compressed charge temperature and a quadrupled reduction of peak NO emitted. Peak NO₂ emission reduced three times on account of the same. However, an increase in CO emission was observed when the combustion phasing was advanced.

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 Office of Heavy Vehicle Technologies supports research to enable high-efficiency diesel engines to meet future emissions regulations, thus clearing the way for their use in light trucks as well as continuing as the most efficient powerplant for freight-haulers. Compliance with Tier 2 emission regulations for light-duty vehicles will require effective exhaust emission controls (aftertreatment) for diesels in these applications. Diesel-powered heavy trucks face a similar situation for the 2007 regulations announced by EPA in December 2000. DOE laboratories are working with industry to improve emission control technologies in projects ranging from application of new diagnostics for elucidating key mechanisms, to development and evaluation of prototype devices. This paper provides an overview of these R&D efforts, with examples of key findings and developments.

This paper describes two independent studies on γ-alumina as a plasma-activated catalyst. γ-alumina (2.5 - 4.3 wt%) was coated onto the surface of mesoporous silica to determine the importance of aluminum surface coordination on NOx conversion in conjunction with nonthermal plasma. Results indicate that the presence of 5- and 6- fold aluminum coordination sites in γ-alumina could be a significant factor in the NOx reduction process. A second study examined the effect of changing the reducing agent on NOx conversion. Several hydrocarbons were examined including propene, propane, isooctane, methanol, and acetaldehyde. It is demonstrated that methanol was the most effective reducing agent of those tested for a plasma-facilitated reaction over γ-alumina.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

In the discharge-catalyst treatment of diesel exhaust the discharge chemistry is known to oxidize NO to NO2 as well as to produce partially oxidized hydrocarbons for the heterogeneous reduction step. We find NO2 to be much more easily reduced to N2 on our catalysts, as long as there is a sufficient supply of reductant present. Unfortunately we typically find that a fraction of the NO2 is only partially reduced back to NO. Since much of the original hydrocarbon survives both the plasma and our catalyst, a subsequent stage of plasma will oxidize NO back to NO2 while at the same time replenishing the supply of partially oxidized hydrocarbon for another stage of heterogeneous catalysis. We present experimental evidence illustrating the advantages of multi-step discharge-catalyst treatment of NOx in simulated diesel exhaust.

We present here a phenomenological analysis of a cascade of two-step discharge-catalyst reactors. That is, each step of the cascade consists of a discharge reactor in series with a catalyst bed. These reactors are intended for use in the reduction of tailpipe emission of NOx from diesel engines. The discharge oxidizes NO to NO2, and partially oxidizes HC. The NO2 then reacts on the catalyst bed with hydrocarbons and partially oxidized HCs and is reduced to N2. The cascade may be essential because the best catalysts for this purpose that we have also convert significant fractions of the NO2 back to NO. As we show, reprocessing the gas may not only be necessary, but may also result in energy savings and increased device reliability.

The NOx reduction performance under lean conditions over γ-alumina was evaluated using a micro-reactor system and a non-thermal plasma-equipped bench test system. Various alumina samples were obtained from alumina manufacturers to assess commercial alumina materials. In addition, γ-alumina samples were synthesized at Caterpillar with a sol-gel technique in order to control alumina properties. The deNOx performances of the alumina samples were compared. The alumina samples were characterized with analytical techniques such as inductively coupled plasma (ICP) emission spectroscopy, temperature programmed desorption (TPD) and surface area measurements (BET) to understand physical and chemical properties. The information derived from these techniques was correlated with the NOx reduction performance to identify key parameters of γ-alumina for optimizing materials for lean-NOx and plasma assisted catalysis.

A slipstream of exhaust from a Caterpillar 3126B engine was diverted into a plasma-catalytic NOx control system in the space velocity range of 7,000 to 100,000 hr-1. The stream was first fed through a non-thermal plasma that was formed in a coaxial cylinder dielectric barrier discharge reactor. Plasma treated gas was then passed over a catalyst bed held at constant temperature in the range of 573 to 773 K. Catalysts examined consisted of γ-alumina, indium-doped γ-alumina, and silver-doped γ-alumina. Road and rated load conditions resulted in engine out NOx levels of 250 - 600 ppm. The effects of hydrocarbon level, catalyst temperature, and space velocity are discussed where propene and in one case ultra-low sulfur diesel fuel (late cycle injection) were the reducing agents used for NOx reduction. Results showed NOx reduction in the range of 25 - 97% depending on engine operating conditions and management of the catalyst and slipstream conditions.

The hole stretchability of two Aluminum Alloys (AA6111 and AA6022) are studied by using a two stages integrated finite element framework where the edge geometry and edge damages from the hole piercing processes were considered in the subsequent hole expansion processes. Experimentally it has been found that AA6022 has higher hole expansion ratios than those of AA6111. This observation has been nicely captured by finite element simulations. The main cause of differences have been identified to the volume fractions of the random distributed second phase hard particles which play a critical role in determining the fracture strains of the materials.