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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.

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.

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).

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.