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Journal Article

Characterization of Zirconium Oxide-Based Pretreatment Coatings Part 1 - Variability in Coating Deposition on Different Metal Substrates

2009-04-20
2009-01-0890
One of the key coating layers that inhibits corrosion on modern automobiles is the pretreatment film. This layer, which is typically a tri-cationic zinc phosphate material, provides both corrosion protection and enhanced paint adhesion to the base metal. Recent tightening of environmental regulations has made the use of this coating more difficult. In response to these pressures, pretreatment suppliers have been developing a new generation of metal pretreatments based on zirconium oxide. Characterization of these new materials is challenging as the zirconium oxide-based coatings are over ten times thinner than the current zinc phosphate coatings. Methods that are currently employed for studying zinc phosphate films such as coating weight determination by weighing, and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) are not sensitive enough to fully characterize these materials.
Technical Paper

Direct Measurement of EGR Cooler Deposit Thermal Properties for Improved Understanding of Cooler Fouling

2009-04-20
2009-01-1461
Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOx emissions standards. This paper reports results of a study of fundamental aspects of EGR cooler fouling. An apparatus and procedure were developed to allow surrogate EGR cooler tubes to be exposed to diesel engine exhaust under controlled conditions. The resulting fouled tubes were removed and analyzed. Volatile and non-volatile deposit mass was measured for each tube. Thermal diffusivity of the deposited soot cake was measured by milling a window into the tube and using the Xenon flash lamp method. The heat capacity of the deposit was measured at temperatures up to 430°C and was slightly higher than graphite, presumably due to the presence of hydrocarbons. These measurements were combined to allow calculation of the deposit thermal conductivity, which was determined to be 0.041 W/mK, only ∼1.5 times that of air and much lower than the 304 stainless steel tube (14.7 W/mK).
Technical Paper

Numerical Modeling and Experimental Investigations of EGR Cooler Fouling in a Diesel Engine

2009-04-20
2009-01-1506
EGR coolers are mainly used on diesel engines to reduce intake charge temperature and thus reduce emissions of NOx and PM. Soot and hydrocarbon deposition in the EGR cooler reduces heat transfer efficiency of the cooler and increases emissions and pressure drop across the cooler. They may also be acidic and corrosive. Fouling has been always treated as an approximate factor in heat exchanger designs and it has not been modeled in detail. The aim of this paper is to look into fouling formation in an EGR cooler of a diesel engine. A 1-D model is developed to predict and calculate EGR cooler fouling amount and distribution across a concentric tube heat exchanger with a constant wall temperature. The model is compared to an experiment that is designed for correlation of the model. Effectiveness, mass deposition, and pressure drop are the parameters that have been compared. The results of the model are in a good agreement with the experimental data.
Journal Article

Hydrocarbons and Particulate Matter in EGR Cooler Deposits: Effects of Gas Flow Rate, Coolant Temperature, and Oxidation Catalyst

2008-10-06
2008-01-2467
Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.
Journal Article

Diesel EGR Cooler Fouling

2008-10-06
2008-01-2475
The buildup of deposits in EGR coolers causes significant degradation in heat transfer performance, often on the order of 20-30%. Deposits also increase pressure drop across coolers and thus may degrade engine efficiency under some operating conditions. It is unlikely that EGR cooler deposits can be prevented from forming when soot and HC are present. The presence of cooled surfaces will cause thermophoretic soot deposition and condensation of HC and acids. While this can be affected by engine calibration, it probably cannot be eliminated as long as cooled EGR is required for emission control. It is generally felt that “dry fluffy” soot is less likely to cause major fouling than “heavy wet” soot. An oxidation catalyst in the EGR line can remove HC and has been shown to reduce fouling in some applications. The combination of an oxidation catalyst and a wall-flow filter largely eliminates fouling. Various EGR cooler designs affect details of deposit formation.
Technical Paper

Soybean and Coconut Biodiesel Fuel Effects on Combustion Characteristics in a Light-Duty Diesel Engine

2008-10-06
2008-01-2501
This study investigated the effects of soybean- and coconut-derived biodiesel fuels on combustion characteristics in a 1.7-liter direct injection, common rail diesel engine. Five sets of fuels were studied: 2007 ultra low sulfur diesel (ULSD), 5% and 20% volumetric blends of soybean biodiesel with ULSD (soybean B5 and B20), and 5% and 20% volumetric blends of coconut biodiesel with ULSD (coconut B5 and B20). In conventional diesel combustion mode, particulate matter (PM) and nitrogen oxides (NOx) emissions were similar for all fuels studied except soybean B20. Soybean B20 produced the lowest PM but the highest NOx emissions. Compared with conventional diesel combustion mode, high efficiency clean combustion (HECC) mode, achieved by increased EGR and combustion phasing, significantly reduced both PM and NOx emissions for all fuels studied at the expense of higher hydrocarbon (HC) and carbon monoxide (CO) emissions and an increase in fuel consumption (less than 4%).
Technical Paper

EGR Cooler Performance and Degradation: Effects of Biodiesel Blends

2008-10-06
2008-01-2473
Exhaust gas recirculation (EGR) coolers experience degradation of performance as a result of the buildup of material in the gas-side flow paths of the cooler. This material forms a deposit layer that is less thermally conductive than the stainless steel of the tube enclosing the gas, resulting in lower heat exchanger effectiveness. Biodiesel fuel has a fuel chemistry that is much more susceptible to polymerization than that of typical diesel fuels and may exacerbate deposit formation in EGR coolers. A study was undertaken to examine the fundamentals of EGR cooler deposit formation by using surrogate tubes to represent the EGR cooler. These tubes were exposed to engine exhaust in a controlled manner to assess their effectiveness, deposit mass, and deposit hydrocarbon content. The tubes were exposed to exhaust for varying lengths of time and for varying coolant temperatures. The results show that measurable differences in the response variables occur within a few hours.
Journal Article

Mixed-Source EGR for Enabling High Efficiency Clean Combustion Modes in a Light-Duty Diesel Engine

2008-04-14
2008-01-0645
The source of exhaust gas recirculation (EGR), and consequently composition and temperature, has a significant effect on advanced combustion modes including stability, efficiency, and emissions. The effects of high-pressure loop EGR (HPL EGR) and low-pressure loop EGR (LPL EGR) on achieving high efficiency clean combustion (HECC) modes in a light-duty diesel engine were characterized in this study. High dilution operation is complicated in real-world situations due to inadequate control of mixture temperature and the slow response of LPL EGR systems. Mixed-source EGR (combination of HPL EGR and LPL EGR) was investigated as a reasonable approach for controlling mixture temperature. The potential of mixed-source EGR has been explored using LPL EGR as a ‘base’ for dilution rather than as a sole source. HPL EGR provides the ‘trim’ for controlling mixture temperature and has the potential for enabling precise control of dilution targets.
Technical Paper

Low Volatility ZDDP Technology: Part 2 - Exhaust Catalysts Performance in Field Applications

2007-10-29
2007-01-4107
Phosphorus is known to reduce effectiveness of the three-way catalysts (TWC) commonly used by automotive OEMs. This phenomenon is referred to as catalyst deactivation. The process occurs as zinc dialkyldithiophosphate (ZDDP) decomposes in an engine creating many phosphorus species, which eventually interact with the active sites of exhaust catalysts. This phosphorous comes from both oil consumption and volatilization. Novel low-volatility ZDDP is designed in such a way that the amounts of volatile phosphorus species are significantly reduced while their antiwear and antioxidant performances are maintained. A recent field trial conducted in New York City taxi cabs provided two sets of “aged” catalysts that had been exposed to GF-4-type formulations. The trial compared fluids formulated with conventional and low-volatility ZDDPs. Results of field test examination were reported in an earlier paper (1).
Technical Paper

Laboratory Postmortem Analysis of 120k mi Engine Aged Urea SCR Catalyst

2007-04-16
2007-01-1579
Selective Catalytic Reduction (SCR) of NOx with aqueous urea and a Catalyzed Diesel Particulate Filter (CDPF) has been considered as one of the emission control systems for diesel vehicles required to meet Federal Tier 2 and California LEVII emission standards. At Ford Motor Company, a DOC-SCR-CDPF system containing a copper / zeolite SCR catalyst was aged to 120k mi on the engine dynamometer using an aging cycle that mimicked both city and highway driving modes. A total of 643 CDPF regenerations occurred during the aging that raised the SCR catalyst to a temperature of up to 650°C on a regular basis. A series of lab analyses including activity tests, ammonia thermal desorption, BET surface area, XRF, XRD, and EPMA was conducted on cores taken from the 120k mi engine aged SCR catalyst brick. The lab post-mortem characterizations revealed the changes of catalyst properties, and the deterioration profile of the SCR catalyst brick after undergoing real aging conditions.
Technical Paper

An Estimate of Diesel High-Efficiency Clean Combustion Impacts on FTP-75 Aftertreatment Requirements

2006-10-16
2006-01-3311
A modified Mercedes 1.7-liter, direct-injection diesel engine was operated in both normal and high-efficiency clean combustion (HECC) combustion modes. Four steady-state engine operating points that were previously identified by the Ad-hoc fuels working group were used as test points to allow estimation of the hot-start FTP-75 emissions levels in both normal and HECC combustion modes. The results indicate that operation in HECC modes generally produce reductions in NOX and PM emissions at the expense of CO, NMHC, and H2CO emissions. The FTP emissions estimates indicate that aftertreatment requirements for NOX are reduced, while those for PM may not be impacted. Cycle-average aftertreatment requirements for CO, NMHC, and H2CO may be challenging, especially at the lowest temperature conditions.
Technical Paper

Fuel Property Effects on Emissions from High Efficiency Clean Combustion in a Diesel Engine

2006-04-03
2006-01-0080
High-efficiency clean combustion (HECC) modes provide simultaneous reductions in diesel particulate matter and nitrogen-oxides emissions while retaining efficiencies characteristic of normal diesel engines. Fuel parameters may have significant impacts on the ability to operate in HECC modes and on the emissions produced in HECC modes. In this study, 3 diesel-range fuels and 2 oxygenated blends are burned in both normal and HECC modes at 3 different engine conditions. The results show that fuel effects play an important role in the emissions of hydrocarbons, particulate matter, and carbon monoxide but do not significantly impact NOx emissions in HECC modes. HECC modes are achievable with 5% biodiesel blends in addition to petroleum-based and oil-sands derived fuels. Soot precursor and oxygenated compound concentrations in the exhaust were observed to generally increase with the sooting tendency of the fuel in HECC modes.
Technical Paper

Characterization of Phosphates Found in Vehicle-Aged Exhaust Gas Catalysts: A Raman Study

2006-04-03
2006-01-0410
Phosphorus contamination from engine oil additives has been associated with reduced performance of vehicle-aged exhaust gas catalysts. Identifying phosphorus species on aged catalysts is important for understanding the reasons for catalytic performance degradation. However, phosphorus is present only in small quantities, which makes its detection with bulk analytical techniques difficult. Raman microscopy probes small regions (a few microns in diameter) of a sample, and can detect both crystalline and amorphous materials. It is thus ideal for characterizing phosphates that may have limited distribution in a catalyst. However, suitable Raman spectra for mixed-metal phosphates that might be expected to be present in contaminated catalysts are not generally available.
Technical Paper

Implications of Particulate and Precursor Compounds Formed During High-Efficiency Clean Combustion in a Diesel Engine

2005-10-24
2005-01-3844
Advanced diesel combustion modes offer the promise of reduced engine-out particulate and nitrogen oxide emissions, thereby reducing the demand on post-combustion emission control devices. In this activity, a light-duty diesel engine was operated in conventional and advanced combustion modes. The advanced combustion modes investigated correspond to both clean (i.e., low PM and low NOX) and clean efficient combustion. The low-NOX, low-PM mode is considered an intermediate condition and the low-NOX, low-PM efficient mode is referred to as high efficiency clean combustion (HECC). Particulate and gaseous emissions were analyzed during all of these experiments. The detailed exhaust chemistry analysis provided significant new information to improving our understanding of these modes as well as identifying potentially important unregulated emissions.
Technical Paper

Low Temperature Urea Decomposition and SCR Performance

2005-04-11
2005-01-1858
Urea-SCR systems are potentially a highly-effective means of NOX reduction for light-duty diesel vehicles. However, use of urea-SCR technologies at low temperatures presents unique technical challenges. This study was undertaken to provide more knowledge about low temperature urea decomposition and the resulting effects on SCR performance. Data are presented for experiments using two SCR catalysts of differing size with a light-duty diesel engine. Analyses of the NOX reduction efficiency, NH3 storage phenomena, and unregulated emissions are shown. Over production of NO2 by the oxidation catalyst is demonstrated to be problematic at 25,000 hr-1 space velocity for a range of temperatures. This leads to production of N2O by both SCR catalysts that is higher when urea is injected than when NH3 is injected.
Technical Paper

A Thermal Conductivity Approach for Measuring Hydrogen in Engine Exhaust

2004-10-25
2004-01-2908
Thermal conductivity detection has long been used in gas chromatography to detect hydrogen and other diatomic gases in a gas sample. Thermal conductivity instruments that are not coupled to gas chromatographs are useful for detecting hydrogen in binary gas mixtures, but suffer from significant cross-interference from other gas species that are separated when the detector is used with a gas chromatograph. This study reports a method for using a commercially-available thermal conductivity instrument to detect and quantify hydrogen in a diesel exhaust stream. The instrument time response of approximately 40 seconds is sufficient for steady-state applications. Cross-interference from relevant gas species are quantified and discussed. Measurement uncertainty associated with the corrections for the various species is estimated and practical implications for use of the instrument and method are discussed.
Technical Paper

Exhaust Chemistry of Low-NOX, Low-PM Diesel Combustion

2004-03-08
2004-01-0114
The exhaust chemistry of combustion regimes characterized by simultaneous low-NOX and low-PM emissions were investigated on a Mercedes 1.7-L diesel engine. Two approaches for entering low-NOX low-PM regimes were explored using a California specification low aromatic certification diesel fuel. Detailed characterizations of gas-phase hydrocarbons, particulate soluble organics, and aldehydes are presented for both approaches. Results indicate significant formation of partially oxygenated hydrocarbons and fuel reformation products during periods of low-NOX, low-PM combustion.
Technical Paper

Effects of Regeneration Conditions on NOX Adsorber Performance

2002-10-21
2002-01-2876
A 1999 Mercedes A170 CDI has been equipped with prototype NOX adsorber devices in order to study the impacts of regeneration conditions on the emissions reduction performance of the devices. This study consisted of a number of laboratory experiments utilizing a bottled-gas injection system to periodically provide fuel-rich exhaust conditions for device regeneration. The NOX adsorbers were evaluated on the LA4 driving cycle using a fixed regeneration schedule. The rich-pulse duration and minimum air/fuel ratio during the rich pulse were varied and the impacts upon pollutant emission rates measured. Results are presented for 5 prototype NOX adsorbers.
Technical Paper

Performance of a NOX Adsorber and Catalyzed Particle Filter System on a Light-Duty Diesel Vehicle

2001-05-07
2001-01-1933
A prototype emissions control system consisting of a close-coupled lightoff catalyst, catalyzed diesel particle filter (CDPF), and a NOX adsorber was evaluated on a Mercedes A170 CDI. This laboratory experiment aimed to determine whether the benefits of these technologies could be utilized simultaneously to allow a light-duty diesel vehicle to achieve levels called out by U.S. Tier 2 emissions legislation. This research was carried out by driving the A170 through the U.S. Federal Test Procedure (FTP), US06, and highway fuel economy test (HFET) dynamometer driving schedules. The vehicle was fueled with a 3-ppm ultra-low sulfur fuel. Regeneration of the NOX adsorber/CDPF system was accomplished by using a laboratory in-pipe synthesis gas injection system to simulate the capabilities of advanced engine controls to produce suitable exhaust conditions. The results show that these technologies can be combined to provide high pollutant reduction efficiencies in excess of 90% for NOX and PM.
Technical Paper

NOx Adsorber Performance In A Light-Duty Diesel Vehicle

2000-10-16
2000-01-2912
Light-duty chassis dynamometer driving cycle tests were conducted on a Mercedes A170 diesel vehicle with various sulfur-level fuels and exhaust emission control systems. Triplicate runs of a modified light-duty federal test procedure (FTP), US06 cycle, and SCO3 cycle were conducted with each exhaust configuration and fuel. The fuels used in these experiments met the specifications of the fuels from the DECSE (Diesel Emission Control Sulfur Effects) program (1, 2, 3 and 4)1. Ultra-low sulfur (3 ppm) diesel fuel was doped to 30 and 150 ppm sulfur so that all fuel properties except sulfur content would be the same. Although the Mercedes A170 vehicle is not certified for sale in the United States, its particulate matter (PM) and nitrogen oxide (NOx) emissions in the as-tested condition were within the Environmental Protection Agency's Tier 1 full useful life standards with its OEM oxidation catalysts installed. Engine-out tests showed that the OEM catalysts reduce PM by 30-40%.
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