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Technical Paper

Tracer Fuel Injection Studies on Exhaust Port Hydrocarbon Oxidation: Part II

Recently, studies were conducted on a single cylinder, four stroke engine to investigate the effect of temperature and local mixedness on exhaust port hydrocarbon oxidation. To examine the effect of temperature, hydrocarbon tracers (propane, propene, 1-butene, n-butane, and n-pentane) were individually injected into the exhaust port just behind the exhaust valve for operating conditions that provided different exhaust port temperatures. For the local mixedness experiments, tracer mixtures (propane + n-butane, 1-butene + n-butane, propene + n-butane) were injected into the exhaust port just behind either a normal exhaust valve or a shrouded exhaust valve. The concentration of tracers and their reaction products were measured using gas chromatography of samples withdrawn from the exhaust stream. The tracer consumption behavior with changing port temperature confirmed that there is a minimum port temperature for hydrocarbon oxidation.
Technical Paper

Instrument for Field Monitoring of Carboxylate Coolants and Heat-Exchange Fluids

For several years now, organic acid based coolants and heat exchange fluids have been introduced on the automotive and industrial market place. The organic acid based coolants provide improved high temperature aluminum corrosion protection and longer drain intervals when compared to traditional coolants. In order to evaluate the organic acid based coolant quality in the field; the end user needs to be able to check several physico-chemical parameters of the coolant. First of all the amount of carboxylate based inhibitors should be determined because the customers can top the system with water. As a result the carboxylates can drop under the minimum required inhibitor level.
Technical Paper

Prediction of Pre-ignition Reactivity and Ignition Delay for HCCI Using a Reduced Chemical Kinetic Model

Homogeneous Charge Compression Ignition (HCCI) engines have the possibility of low NOx and particulate emissions and high fuel efficiencies. In HCCI the oxidation chemistry determines the auto-ignition timing, the heat release rate, the reaction intermediates, and the ultimate products of combustion. This paper reports an initial effort to apply our reduced chemical kinetic model to HCCI processes. The model was developed to study the pre-ignition characteristics (pre-ignition heat release and start of ignition) of primary reference fuels (PRF) and includes 29 reactions and 20 active species. The only modifications to the model were to make the proscribed adjustments to the fuel specific rate constants, and to enhance the H2O2 decomposition rate to agree with published data.
Technical Paper

The Autoignition of n-Pentane in a Non-Fired Single Cylinder Engine

The detailed chemical reactions leading to autoignition of n-pentane are investigated in this study. A single-cylinder engine operating in a nonfired mode was used. The engine is supercharged and the temperature of the inlet fuel/air mixture is varied. By increasing the inlet manifold temperature, at a given inlet manifold pressure, the fuel/air mixture can be made to undergo autoignition. In-cylinder pressure and temperature profiles were measured. Gas samples from the combustion chamber were extracted and analyzed using gas chromatography techniques. The detailed chemical reaction mechanisms explaining the products from the different stages of the fuel oxidation process are presented. It is speculated that the generation of OH radicals from the peroxide (QOOH) decomposition is responsible for the autoignition of the n-pentane fuel/air mixture.
Technical Paper

A Study on the Application of a Reduced Chemical Reaction Model to Motored Engines for Heat Release Prediction

We investigated the ability of a reduced chemical kinetic model of 18 reactions and 13 active species to predict the heat release for a blend of primary reference fuels with octane rating 63 in a motored research engine. Given the initial fuel-air mixture concentration and temperature, the chemical kinetic model is used to predict temperature, heat release and species concentrations as a function of time or crank angle by integrating the coupled rate and energy equations. For comparison, we independently calculated heat release from measured pressure data using a standard thermodynamic model.
Technical Paper

Predictions of Cyclic Variability in an SI Engine and Comparisons with Experimental Data

An investigation of cyclic variability in a spark ignition engine is reported. Specifically, the predictions of an engine code have been compared with experimental data obtained using a well-characterized SI engine. The engine used for the experimental work and modeled in the code is the single cylinder research engine developed at Sandia National Laboratories and now operating at Drexel University. The data used for comparison were cylinder pressure histories for 110 engine cycles gathered during operation at a single engine operating condition. The code allows the various factors that could influence cyclic variability to be examined independently. Specifically, a model has been used to independently examine the effects of variations in equivalence ratio and of the turbulence intensity on cycle-to-cycle variations in the peak cylinder pressure, the crankangle of occurrence of peak pressure, the flame development angle, and the rapid burning angle.
Technical Paper

Prediction of Preignition Reactivity for n-Butane and iso-Butane Blends Using a Reduced Chemical Kinetic Model

Recently, we reported the development of a new reduced chemical kinetic model for predicting reactivity and autoignition behavior of primary reference fuels in a motored research engine. The predicted oxidation behavior (ignition delay, preignition heat release, and evolution of key chemical species) is in fairly good agreement with experiments. In addition, the model reproduced the experimentally observed dependence of overall reactivity on charge density and manifold inlet conditions. This paper reports our initial effort to apply this new reduced chemical kinetic model to other fuels. Specifically, the model was tested using neat n-butane and n-butane/iso-butane blends (10, 20, and 48 percent by volume iso-butane) under skip fired conditions. The only adjustments made in the model were to the fuel specific rate parameters of the RO2· isomerization reaction, the reaction of aldehydes with OH·, and the reaction forming cyclic ethers.
Technical Paper

Coolant Pump Failure Rates as a Function of Coolant Type and Formulation

Automobile coolant pump failure rates have been observed to be influenced by the coolant inhibitor package. A fleet test consisting of 196 1991 Ford Crown Victoria taxi cabs was utilized to test six coolant formulations. Four of the test formulations were monobasic/dibasic organic acid technology coolants and two were traditional technology coolants containing nitrate, phosphate, and silicate. Coolant pump failure rates were monitored as a function of mileage. Results indicate that the service life of coolant pumps for those systems employing organic acid technology coolants was significantly greater than those systems utilizing traditional inhibitor technology coolants.
Technical Paper

The Effects of Methanol and Ethanol on the Oxidation of a Primary Reference Fuel Blend in a Motored Engine

This experimental study was conducted in a motored research engine to investigate the effect of blending methanol and ethanol on hydrocarbon oxidation and autoignition. An 87 octane mixture of primary reference fuels, 87 PRF, was blended with small percentages of the alcohols to yield a constant gravimetric oxygen percentage in the fuel. The stoichiometric fuel mixtures and neat methanol and ethanol were tested in a modified single-cylinder engine at a compression ratio of 8.2. Supercharging and heating of the intake charge were used to control reactivity. The inlet gas temperature was increased from 325 K to the point of autoignition or the maximum achievable temperature of 500 K. Exhaust carbon monoxide levels and in-cylinder pressure histories were monitored in order to determine and quantify reactivity.
Technical Paper

Comparison of Surface Coatings Formed from Carboxylic Acid-Based and Conventional Coolants in a Field-Test Study

Field-test samples cut from radiator tubes in two 1990 Chevy Luminas (3.1L engine) after 100,000 miles were analyzed to determine corrosion layer differences. One car used a carboxylic acid-based inhibitor technology (C1). The other car used a conventional coolant (C2). X-ray photoelectron spectroscopy (XPS) analysis of the two samples was performed. Results indicate a significant difference between the two samples. The C1 sample had a thin (<60Å) organic coating bound to the aluminum alloy surface, while the C2 sample had a much thicker (>1000 Å) silicate-rich layer. This resulted in the C2 sample exhibiting “surface charging” behavior. These results relate directly to the metal/insulator (conductor/insulator) characteristics of the two samples, and imply that the heat transfer of the protective coating provided by the carboxylate technology (C1) is significantly better than that of traditional inhibitor technology (C2).
Technical Paper

A Reduced Chemical Kinetic Model for Autoignition of the Butanes

A reduced chemical kinetic model by Li et al. [1]* for predicting primary reference fuels' reactivity and autoignition behavior was modified to apply to the butanes, and it was correlated to experimental results from the non-fired engine cycles under skip fired conditions. The fuels examined in this work were neat n-butane and n-butane/iso-butane blends (10, 20, and 48 percent by volume iso-butane). In our initial work using measured pressure data from the first skip cycle, we modified Li et al.'s model by only adjusting the fuel specific rate parameters of the alkylperoxy radical (RO2·) isomerization reaction, the reaction of aldehydes with OH·, and the reaction forming cyclic ethers. In this work, analysis was extended to the second skip cycle and additional oxidation rate parameters with high fuel sensitivity were adjusted. Several reactions, which are not significant in butane oxidation, were temporarily made to be inactive in the model.
Technical Paper

Post Combustion Hydrocarbon Oxidation and Exhaust Emissions - Neat Fuel and Fuel Blend Studies

Inevitably a fraction of the hydrocarbon fuel in spark ignition engines escapes in-cylinder combustion and flows out with the burned products. Post combustion oxidation in the cylinder and exhaust port may consume a part of this fuel and plays an important role in determining exhaust emission levels. This paper presents results from experiments designed to identify the factors that control post-combustion oxidation. Regulated exhaust components and detailed hydrocarbon species were measured using seven neat hydrocarbons and four blends as fuel. The fuels were selected to compare the relative rates of mixing and chemical kinetics. The results indicate that exhaust temperature, diffusion rates and fuel kinetics each play a complicated role in determining emission levels.
Technical Paper

Autoignition Chemistry Studies on Primary Reference Fuels in a Motored Engine

Autoignition chemistry of n-heptane, iso-octane and an 87 octane blend, 87 PRF, was studied in a single-cylinder modified Wisconsin model AENL engine under motored conditions. Use of a fast-acting sampling valve and gas chromatographic analysis allowed measurement of in-cylinder gas composition during the ignition process. Crank angle resolved species evolution profiles were generated for all three fuels at a fixed inlet temperature of 376 K. For n-heptane, the measurements were made during a cyclically repeatable two stage ignition process up to the point of hot ignition (the second stage ignition). These n-heptane experiments were run at ø = 0.3 to avoid excessive pressure rise at hot ignition which might damage our engine. iso-Octane and 87 PRF were run at stoichiometric equivalence ratio which did not have a second stage ignition, and species were measured only during the first stage of ignition.
Technical Paper

The Effects of Octane Enhancing Ethers on the Reactivity of a Primary Reference Fuel Blend in a Motored Engine

This paper presents results of studies investigating the effect of octane enhancing ethers on the reactivity of an 87 octane mixture of primary reference fuels, 87 PRF, in a motored engine. 87 PRF was blended with small percentages of MTBE, ETBE, TAME and DIPE based on a constant gravimetric oxygen percentage in the fuel. The experiments were conducted in a modified single-cylinder Wisconsin AENL engine at compression ratios of 5.2 and 8.2. Supercharging and heating of the intake charge were used to control reactivity. The inlet gas temperature was increased from 320 K, where no reactivity occurred, until either autoignition occurred or the maximum temperature of the facility was reached. Exhaust carbon monoxide levels and in-cylinder pressure histories were monitored in order to determine and quantify reactivity.
Technical Paper

Corrosion Mechanism of High Lead Solder and Correlation to Dissolved Oxygen

High lead solder coupons are frequently tested in ASTM D 1384-87 and D 2570-91 tests to determine the corrosion protection provided by engine coolants. In contrast to 70/30 solder, high lead solder is often observed to show relatively high corrosion rates in D 1384-87 testing. Surprisingly, the high lead solder corrosion rates tend to be lower in the D 2570-91 test, despite the longer duration of this test. The basis of this effect has been investigated in different coolant formulations and in both ethylene glycol and propylene glycol. The corrosion of high lead solder was found to be directly related to the presence of oxygen in the D 1384-87 test. Replacement of the air purge with a nitrogen purge significantly reduced the corrosion rate of high lead solder in inhibited coolants. These results are interpreted in terms of the solder composition.
Technical Paper

The Effect of Silicate Content in Engine Coolants on the Corrosion Protection of Aluminum Heat-Rejecting Surfaces

The effect of small amounts of silicate on coolant performance has been studied. The corrosion protection provided by different coolant technologies was evaluated for different silicate contents. This work includes results from electrochemical tests and static and dynamic heat-rejecting tests on aluminum surfaces. The results indicate that small amounts of silicate have a negative effect on the corrosion protection of aluminum. Depletion of silicates can therefor be expected to affect aluminum heat-rejecting surfaces. The use of carboxylic acid corrosion inhibitors can overcome this problem.
Technical Paper

Effects of DTBP on the HCCI Combustion Characteristics of SI Primary Reference Fuels

One option for ignition control of Homogeneous Charge Compression Ignition (HCCI) engines is to use small amounts of ignition-enhancing additives to alter the ignition properties. Di-tertiary Butyl Peroxide (DTBP) is one such additive and it has been suggested as a cetane improver in diesel engines. In this study, the effects of DTBP on spark ignition (SI) primary reference fuels (PRFs, n-heptane and iso-octane) and their blends (PRF20, PRF50, PRF63, PRF87 and PRF92) were investigated during HCCI engine operation. Experiments were run in a single cylinder CFR research engine for three inlet temperatures (410, 450 and 500 K) and several equivalence ratios (0.28 - 0.57) at a constant speed of 800 rpm and a compression ratio of 16.0. Experimental results show that ignition delay time, cycle to cycle variation, and stable operating range were all improved with the addition of less than 2.5% DTBP by volume.
Technical Paper

A Detailed Kinetic Study on the Effect of DTBP on PRF Combustion in HCCI Engines

The effect of Di-tertiary Butyl Peroxide (DTBP) on Primary Reference Fuels (PRFs) in Homogeneous Charge Compression Ignition (HCCI) engines was investigated numerically and was compared with trends from previous experimental observations. A detailed kinetic mechanism for PRF combustion containing more than a thousand species and four thousand reactions was combined with a twenty one species, sixty-nine reaction mechanism for DTBP decomposition. This mechanism predicted the observed experimental trends reasonably well and was used to examine how DTBP addition acts to advance combustion timing and to induce hot ignition for lean and high octane number mixtures. The study suggests that DTBP's predominant mode of action for low Octane Number (ON) fuels is thermal, while for high ON fuels it is chemical. The extended kinetic model compiled for this study and the results obtained can be used to aid in the understanding and development of tailored additives for HCCI engines.
Technical Paper

Time Resolved Exhaust Port Sampling Studies Related to Hydrocarbon Emissions from SI Engines

The role of post-combustion oxidation in influencing exhaust hydrocarbon emissions from spark ignition engines has been identified as one of the major uncertainties in hydrocarbon emissions research [l]*. While we know that post-combustion oxidation plays a significant role, the factors that control the oxidation are not well known. In order to address some of these issues a research program has been initiated at Drexel University. In preliminary studies, seven gaseous fuels: methane, ethane,ethene,propane,propene, n-butane, 1-butene and their blends were used to examine the effect of fuel structure on exhaust emissions. The results of the studies presented in an earlier paper [2] showed that the effect of fuel structure is manifested through its effect on the post-combustion environment and the associated oxidation process. A combination of factors like temperatures, fuel diffusion and reaction rates were used to examine and explain the exhaust hydrocarbon emission levels.
Technical Paper

Tracer Fuel Injection Studies on Exhaust Port Hydrocarbon Oxidation

Time resolved exhaust port sampling results show that the gas mixture in the port at exhaust valve closing contains high concentrations of hydrocarbons. These hydrocarbons are mixed with hot in-cylinder gases during blowdown and can react either via gas phase kinetics in the exhaust port/runner system or subsequently on the exhaust catalyst before they are emitted. Studies were conducted on a single cylinder, four stroke engine in our laboratory to determine the interaction between the hot blowdown gases and the hydrocarbons which remain in the exhaust port. A preselected concentration and volume of hydrocarbon tracers (propane, propene, n-butane, and 1-butene) in either oxygen/nitrogen mixtures or pure nitrogen were injected into the exhaust port just behind the exhaust valve to control the initial conditions for any potential oxidation in the port.