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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.

In Homogeneous Charge Compression Ignition (HCCI) engines, fuel oxidation chemistry determines the auto-ignition timing, the heat release, the reaction intermediates, and the ultimate products of combustion. Therefore a model that correctly simulates fuel oxidation at these conditions would be a useful design tool. Detailed models of hydrocarbon fuel oxidation, consisting of hundreds of chemical species and thousands of reactions, when coupled with engine transport process models, require tremendous computational resources. A way to lessen the burden is to use a “skeletal” reaction model, containing only tens of species and reactions. This paper reports an initial effort to extend our skeletal chemical kinetic model of pre-ignition through the entire HCCI combustion process. The model was developed from our existing preignition model, which has 29 reactions and 20 active species, to yield a new model with 69 reactions and 45 active species.

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.

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.

An inhibitor package which is silicate-, nitrate-, borate- and phosphate-free has been developed as the basis for a world-wide automotive coolant formulation. The formulation contains aliphatic mono- and dicarboxylic acids and tolyltriazole as the sole inhibitors. Formulations containing carboxylic acid inhibitors have been studied in ASTM bench tests and found to sufficiently protect all prevalent cooling system metals. In addition, fleet tests have shown that carboxylic acid inhibitors deplete much more slowly than conventional inhibitors, making possible a much longer life coolant. Results from laboratory tests which simulate extended usage indicated that carboxylic acid-containing coolants have a significantly longer life span for the protection of all cooling system metals. Finally, the carboxylic acid/tolyltriazole inhibitor package is completely adaptable to a propylene glycol base.

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.

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.

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.

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.

Mixtures of a novel corrosion inhibitor, based on the synergistic combination of aliphatic mono- and dibasic acids with a traditional coolant have been evaluated in: a stability test an electrochemical test the ASTM D 1384 Glassware Corrosion Test the ASTM D 4340 Aluminum Heat-Rejection Test a Dynamic Heat-Transfer Test. This paper discusses the results of these tests and the relevance of the tests in assessing the performance of the coolant mixtures. Recommendations are made to the selection of methods that provide significant information on coolant compatibility.

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.

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.

Coolant formulations based on organic acid corrosion inhibitor technology have been tested in over 180 heavy duty engines for a total of more than 50 million kilometers. This testing has been used to document long life coolant performance in various engine types from four major engine manufacturers. Inspections of engines using organic acid based coolant (with no supplemental coolant additive) for up to 610,000 kilometers showed excellent protection of metal engine components. Improved protection was observed against cylinder liner, water pump, and aluminum spacer deck corrosion. In addition, data accumulated from this testing were used to develop depletion rate curves for long life coolant corrosion inhibitors, including tolyltriazole and nitrite. Nitrite was observed to deplete less rapidly in long life coolants than in conventional formulations.

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).

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.

This paper presents a new global reaction model to simulate the Homogeneous Charge Compression Ignition (HCCI) combustion process. The model utilizes seven equations and seven active species. The model includes five reactions that represent degenerate chain branching in the low temperature region, including chain propagation, termination and branching reactions and the reaction of HOOH at the second stage ignition. Two reactions govern the high temperature oxidation, to allow formation and prediction of CO, CO2, and H2O. Thermodynamic parameters were introduced through the enthalpy of formation of each species. We were able to select the rate parameters of the global model to correctly predict the autoignition delay time at constant density for n-heptane and iso-octane, including the effect of equivalence ratio.

The generally accepted explanation of autoignition in engines is that the reactivity is driven by temperature, where autoignition occurs after the mixture has reached some critical temperature (approx. 1000 K) by a combination of self-heating due to preignition reactions and compression heating due to piston motion and flame propagation. During the course of our investigations into autoignition processes and homogeneous charge compression ignition we have observed some ignitions that begin at much lower temperature (< 550 K). In this paper we describe these observations, our attempts to investigate their origins, and an alternative explanation that proposes that traditional models may be missing the chemistry that explains this behavior. Finally, applications of lower temperature chemical reactions are discussed.

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.

Previous studies examined the effect of low levels of silicate (∼<75ppm Si) on hot aluminum corrosion protection. The corrosion protection provided by different coolant technologies was evaluated at different silicate levels. The results indicated that small amounts of silicate have a negative effect on the corrosion protection of aluminum. This work will examine these results and evaluate the effectiveness of different laboratory tests for determining coolant “compatibility.” Results will be examined from several bench and fleet tests showing the effect of coolant mixing on the corrosion rates in various environments. The bench test results will include laboratory glassware and dynamic tests that have been used historically to evaluate coolant compatibility. Differences between the test methods will also be evaluated to determine the relevance of each test procedure in light of the fleet observations.