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This project team conducted a life-cycle-based environmental evaluation of new, lightweight materials (e.g., titanium, magnesium) used in two concept 3XVs -- i.e., automobiles that are three times more fuel efficient than today's automobiles -- that are being designed and developed in support of the Partnership for a New Generation of Vehicles (PNGV) program. The two concept vehicles studied were the DaimlerChrysler ESX2 and the Ford P2000. Data for this research were drawn from a wide range of sources, including: the two automobile manufacturers; automobile industry reports; government and proprietary databases; past life-cycle assessments; interviews with industry experts; and models.

An optical-based sensor for detecting particulate matter (PM) in diesel engine exhaust has been demonstrated. The position of the sensor during the experiments was the exhaust manifold prior to the turbocharger. The sensor is constructed of fiber optics which transmit 532-nm laser light into the exhaust pipe and collect backscattered light in a 180° geometry. Due to the optical nature of the probe, PM sensing can occur at high temporal rates. Experiments conducted by changing the fuel injection properties of one cylinder of a four cylinder engine demonstrated that the sensor can resolve cycle dependent events. The feasibility of the probe for examining PM emissions in the exhaust manifold will be discussed.

As interest has grown in diesel emissions and diesel engine aftertreatment, so has the importance of analyzing all components of the exhaust. One of the more costly and difficult measurements to make is the collection and analysis of semivolatile organic compounds (SOCs) in the exhaust. These compounds include alkane and alkenes from C12-C24, and the 2-5 ring polycyclic aromatic hydrocarbons (PAH). These compounds can be present in both the particulate (i.e. on the filter) and gaseous phase, and cannot be collected with bag samples. Typically, a sorbent is used downstream of the particulate collection filters to collect these compounds. Sorbent phases include polyurethane foam (PUF), Tenax™, XAD-type resins, and activated carbon. The SOCs are removed from the sorbent either by solvent extraction (PUF and XAD) or thermal desorption (Tenax™ and activated carbon). Each of these methods have advantages and disadvantages.

Interest in operational cost reduction is driving engine manufacturers to consider low-cost fuel substitution in heavy-duty diesel engines. These dual-fuel (DF) engines could be operated either in diesel-only mode or operated with premixed natural gas (NG) ignited by a pilot flame of compression-ignited direct-injected diesel fuel. Under certain conditions, dual-fuel operation can result in increased cycle-to-cycle variability (CCV) during combustion. CFD can greatly help in understanding and identifying critical parameters influencing CCV. Innovative modelling techniques and large computing resources are needed to investigate the factors affecting CCV in dual-fuel engines. This paper discusses the use of the High Performance Computing resource Titan, at Oak Ridge National Laboratory, to investigate CCV of a dual-fuel engine.

A high-resolution corrosion probe was placed within the airhorn section of the exhaust gas recirculation (EGR) loop of a heavy-duty diesel engine. The corrosion rate of the mild-steel probe elements was evaluated as a function of fuel sulfur level, EGR fraction, dewpoint margin, and humidity. No significant corrosion was observed while running the engine using a No. 2 grade, < 15ppm sulfur diesel fuel; however, high corrosion rates were observed with No. 2 diesel fuel (∼350 ppm sulfur) while condensing water in the EGR loop. The rate of corrosion on the mild steel elements increased with increasing levels of sulfate in the condensate. However, the engine conditions influencing the sulfate level were not clearly identified in this study.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

Computational approaches have been limited to examining catalytic processes using models that have been greatly simplified in comparison to real catalysts. Experimental studies, especially on emission treatment catalysts, have primarily focused on fully formulated systems. Thus, there remains a knowledge gap between theory and experiments. We combine the power of theory and experiment for atomistic design of catalytically active sites that can translate the fundamental insights gained directly to a catalyst system suitable for technical deployment. In this article, we describe our results on a model platinum-alumina catalyst that is a common constituent of emission treatment catalysts such as three-way, NOx trap, oxidation, and HC-SCR catalysts. We present theoretical and experimental studies of the oxidation and reactivity of Pt catalyst clusters towards O, CO, and NOx.

The low temperature conditions that occur during high efficiency clean combustion (HECC) often lead to the formation of partially oxidized HC species such as aldehydes, ketones and carboxylic acids. Using the diesel fuels specified by the Fuels for Advanced Combustion Engines (FACE) working group, carbonyl species were collected from the exhaust of a light duty diesel engine operating under HECC conditions. High pressure liquid chromatography - mass spectrometry (LC-MS) was used to speciate carbonyls as large as C 9 . A relationship between carbonyl species formed in the exhaust and fuel composition and properties was determined. Data were collected at the optimum fuel efficiency point for a typical road load condition. Results of the carbonyl analysis showed changes in formaldehyde and acetaldehyde formation, formation of higher molecular weight carbonyls and the formation of aromatic carbonyls.

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 effects of cetane number (CN) on homogeneous charge compression ignition (HCCI) performance and emissions were investigated in a single cylinder engine using intake air temperature for control. Blends of the diesel secondary reference fuels for cetane rating were used to obtain a CN range from 19 to 76. Sweeps of intake air temperature at a constant fueling were performed. Low CN fuels needed to be operated at higher intake temperatures than high CN fuels to achieve ignition. As the intake air temperature was reduced for a given fuel, the combustion phasing was retarded, and each fuel passed through a phasing point of maximum indicated mean effective pressure (IMEP). Early combustion phasing was required for the high CN fuels to prevent misfire, whereas the maximum IMEP for the lowest CN fuel occurred at a phasing 10 crank angle degrees (CAD) later.

The focus of the present study was to characterize Reactivity Controlled Compression Ignition (RCCI) using a single-fuel approach of gasoline and gasoline mixed with a commercially available cetane improver on a multi-cylinder engine. RCCI was achieved by port-injecting a certification grade 96 research octane gasoline and direct-injecting the same gasoline mixed with various levels of a cetane improver, 2-ethylhexyl nitrate (EHN). The EHN volume percentages investigated in the direct-injected fuel were 10, 5, and 2.5%. The combustion phasing controllability and emissions of the different fueling combinations were characterized at 2300 rpm and 4.2 bar brake mean effective pressure over a variety of parametric investigations including direct injection timing, premixed gasoline percentage, and intake temperature. Comparisons were made to gasoline/diesel RCCI operation on the same engine platform at nominally the same operating condition.

The CRC Fuels for Advanced Combustion Engines (FACE) Working Group has provided a matrix of experimental diesel fuels for use in studies on the effects of three parameters, Cetane number (CN), aromatics content, and 90 vol% distillation temperature (T90), on combustion and emissions characteristics of advanced combustion strategies. Various types of fuel analyses and engine experiments were performed in well-known research institutes. This paper reviews a collection of research findings obtained with these nine fuels. An extensive collection of analyses were performed by members of the FACE working group on the FACE diesel fuels as a means of aiding in understanding the linkage between fuel properties and combustion and emissions performance. These analyses included non-traditional chemical techniques as well as established ASTM tests. In a few cases, both ASTM tests and advanced analyses agreed that some design variables differed from their target values when the fuels were produced.

The effect of biodiesel content on homogeneous charge compression ignition (HCCI) engine performance has been investigated both experimentally and by computer simulation. Combustion experiments were performed in a single cylinder HCCI engine using blends of soy biodiesel in ultra low sulfur diesel, with concentrations ranging from 0 to 50 vol% and equivalence ratios (Φ) from 0.38 to 0.48. Data from the engine tests included combustion analysis and exhaust composition analysis with standard gaseous emissions equipment. The engine utilized a custom port fuel injection strategy to provide highly premixed charges of fuel and air, making it possible to compare the results with single zone chemical kinetics simulations that were performed using CHEMKIN III, with a reaction set including 670 species and over 3000 reactions.

The compatibility of elastomer materials used in fuel storage and dispensing applications was determined for an off-highway diesel fuel and a blend containing 20% bio-oil (Bio20) derived from a fast pyrolysis process. (This fuel blend is not to be confused with B20, which is a blend of diesel fuel with 20% biodiesel.) The elastomer types evaluated in this study included fluorocarbon, fluorosilicone, acrylonitrile rubber (NBR), styrene butadiene rubber (SBR), polyurethane, neoprene, and silicone. All of these elastomer types are used in sealing applications, but some, like the nitrile rubbers are also common hose materials. The elastomer specimens were exposed to the two fuel types for 4 weeks at 60°C. After measuring the wetted volume and hardness, the specimens were dried for 65 hours at 60°C and then remeasured. A solubility analysis was performed to better understand the performance of plastic materials in fuel blends composed of bio-oil and diesel.

The compatibility of plastic materials used in fuel storage and dispensing applications was determined for an off-highway diesel fuel and a blend containing 20% bio-oil (Bio20) derived from a fast pyrolysis process. Bio20 is not to be confused with B20, which is a diesel blend containing 20% biodiesel. The feedstock, processing, and chemistry of biodiesel are markedly different from bio-oil. Plastic materials included those identified for use as seals, coatings, piping and fiberglass resins, but many are also used in vehicle fueling systems. The plastic specimens were exposed to the two fuel types for 16 weeks at 60°C. After measuring the wetted volume and hardness, the specimens were dried for 65 hours at 60°C and then remeasured to determine extent of property change. A solubility analysis was performed to better understand the performance of plastic materials in fuel blends composed of bio-oil and diesel.

The compatibility of notable infrastructure elastomers and plastics with DME and its blends with diesel fuel were examined using solubility analysis. The elastomer materials were fluorocarbon, acrylonitrile butadiene rubber (NBR), styrene butadiene (SBR), neoprene, polyurethane and silicone. Plastic materials included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), polybutylene terephthalate (PBT), polypropylene (PP), high density polyethylene (HDPE), along with several nylon grades and thermosetting resins. These materials have been rigorously studied with other fuel types, and their volume change results were found to correspond well with their predicted solubility levels. A Hansen solubility analysis was performed for each material with DME, diesel, and blends of both fuel components.

Polyoxymethylene dimethyl ethers (PODEs) have shown promise as candidates for diesel fuel blendstocks due to their low sooting tendency, high cetane number, and diesel-comparable boiling point range. However, there is a lack of literature regarding compatibility of PODEs with common automotive elastomers, which would be a prerequisite to their adoption into the marketplace. To address this need, an exposure study and complementary solubility analysis were undertaken. A commercially available blend of PODEs with polymerization degree ranging from 3 to 6 was blended with diesel certification fuel at 0, 33, 50, 67, at 100% by mass. Elastomer coupons were exposed to the various blends for a period of 4 weeks and evaluated for volume swell.

Reliable means for on-board detection of particulate filter failures or malfunctions are needed to meet diagnostics (OBD) requirements. Detecting these failures, which result in tailpipe particulate matter (PM) emissions exceeding the OBD limit, over all operating conditions is challenging. Current approaches employ differential pressure sensors and downstream PM sensors, in combination with particulate filter and engine-out soot models. These conventional monitors typically operate over narrowly-defined time windows and do not provide a direct measure of the filter’s state of health. In contrast, radio frequency (RF) sensors, which transmit a wireless signal through the filter substrate provide a direct means for interrogating the condition of the filter itself.

A new analytical method to aid in the understanding of the organic carbon (OC) phase of particulate matter (PM) from advanced compression ignition (ACI) operating modes, is presented. The presence of NO2 and unburned fuel aromatics in ACI emissions, and the low exhaust temperatures that result from this low temperature combustion strategy, provide the right conditions for the formation of carboxylic acids and nitroaromatic compounds. These polar compounds contribute to OC in the PM and are not typically measured using nonpolar solvent extraction methods such as the soluble organic fraction (SOF) method. The new extraction and detection method employs capillary electrophoresis with electrospray ionization mass spectrometry (CE-ESI MS) and was specifically developed to determine polar organic compounds in the ACI PM emissions. The new method identified both nitrophenols and aromatic carboxylic acids in the ACI PM.

The accelerated ash loading of diesel particulate filters (DPFs) with diesel oxidation catalysts (DOCs) mounted upstream by lube-oil derived products was investigated using a single cylinder diesel engine and fuel blended with 5% lube oil. An ash loading protocol is developed which combines soot loading, active soot regeneration, and periodic shutdowns for filter weighing. Active regeneration is accomplished by exhaust injection of diesel fuel, initiated by a backpressure criteria and providing DPF temperatures up to 700°C. In developing this protocol, five DPFs of various combinations of substrates (cordierite, silicon carbide, and mullite) and washcoats (none, low PGM, and high PGM) are used and evaluated. The initial backpressure and rate of backpressure increase with ash varied with each of the DPFs and ash was observed to have an effect on the active soot light-off temperature for the catalyzed DPFs.