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All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

The carbon dioxide chaperon efficiency for the reaction H + O2 + M yields HO2 + M from ignition delay times behind reflected shock waves

Ignition delay times for stoichiometric hydrogen-oxygen in argon with and without carbon dioxide were measured behind reflected shock waves. A 20-reaction kinetic mechanism models the measured hydrogen-oxygen delay times over the temperature range 950 to 1300 K. The chaperon efficiency for carbon dioxide determined for the hydrogen-oxygen carbon dioxide mixture was 7.0. This value is in agreement with literature values but much less than a recent value obtained from flow tube experiments. Delay times measured behind a reflected shock wave were about 20% longer than those measured behind incident shock waves. The kinetic mechanism successfully modeled the high-pressure data of Skinner and the hydrogen-air data of Stack. It is suggested that the lowest temperature points for the hydrogen-air data of Slack are unreliable and that the 0.27-atm data may illustrate a case where vibrational relaxation of nitrogen is important. The reaction pathway HO2 yields H2O2 yields OH yields H was required to model the high-pressure data of Skinner. The successful modeling of the stoichiometric hydrogen-air data demonstrates the appropriateness of deriving kinetic models from data for gas mixtures highly diluted with argon. The technique of reducing a detailed kinetic mechanism to only the important reactions for a limited range of experimental data may render the mechanism useless for other test conditions.

Brabbs, Theodore A.↗
NASA NTRS1985

Ignition delay times of benzene and toluene with oxygen in argon mixtures

The ignition delay times of benzene and toluene with oxygen diluted in argon were investigated over a wide range of conditions. For benzene the concentration ranges were 0.42 to 1.69 percent fuel and 3.78 to 20.3 percent oxygen. The temperature range was 1212 to 1748 K and the reflected shock pressures were 1.7 to 7.89 atm. Statistical evaluation of the benzene experiments provided an overall equation which is given. For toluene the concentration ranges were 0.5 to 1.5 percent fuel and 4.48 to 13.45 percent oxygen. The temperature range was 1339 to 1797 K and the reflected shock pressures were 1.95 to 8.85 atm. The overall ignition delay equation for toluene after a statistical evaluation is also given. Detailed experimental information is provided.

Burcat, A.↗
NASA NTRS1986

Methane oxidation behind reflected shock waves: Ignition delay times measured by pressure and flame band emission

Ignition delay data were recorded for three methane-oxygen-argon mixtures (phi = 0.5, 1.0, 2.0) for the temperature range 1500 to 1920 K. Quiet pressure trances enabled us to obtain delay times for the start of the experimental pressure rise. These times were in good agreement with those obtained from the flame band emission at 3700 A. The data correlated well with the oxygen and methane dependence of Lifshitz, but showed a much stronger temperature dependence (phi = 0.5 delta E = 51.9, phi = 1.0 delta = 58.8, phi = 2.0 delta E = 58.7 Kcal). The effect of probe location on the delay time measurement was studied. It appears that the probe located 83 mm from the reflecting surface measured delay times which may not be related to the initial temperature and pressure. It was estimated that for a probe located 7 mm from the reflecting surface, the measured delay time would be about 10 microseconds too short, and it was suggested that delay times less than 100 microsecond should not be used. The ignition period was defined as the time interval between start of the experimental pressure rise and 50 percent of the ignition pressure. This time interval was measured for three gas mixtures and found to be similar (40 to 60 micro sec) for phi = 1.0 and 0.5 but much longer (100 to 120) microsecond for phi = 2.0. It was suggested that the ignition period would be very useful to the kinetic modeler in judging the agreement between experimental and calculated delay times.

Brabbs, T. A.↗
NASA NTRS1986

Ignition delay times of cyclopentene oxygen argon mixtures

The oxidation of cyclopentene was studied experimentally to expand the database on pyrolysis and the reaction products of five carbon unsaturated ring compounds. Pyrolysis was carried out in a single-pulse shock tube. Data were gathered on the shock speed, wall pressure, and reflected shock temperatures. Four different mixtures of C5H8, O2 and Ar, ranging from 0.25-1 percent cyclopentene and 1.75-7 percent O2, were examined in 76 different trials. The data showed a shock temperature range of 1323-1816 K and a pressure range of 1.67-7.36 atmospheres. A student-t test analysis of the results led to definition of an ignition delay equation accurate to the 2-sigma level.

Burcat, A.↗
NASA NTRS2009

Ignition Delay of Combustible Materials in Normoxic Equivalent Environments

Material flammability is an important factor in determining the pressure and composition (fraction of oxygen and nitrogen) of the atmosphere in the habitable volume of exploration vehicles and habitats. The method chosen in this work to quantify the flammability of a material is by its ease of ignition. The ignition delay time was defined as the time it takes a combustible material to ignite after it has been exposed to an external heat flux. Previous work in the Forced Ignition and Spread Test (FIST) apparatus has shown that the ignition delay in the currently proposed space exploration atmosphere (approximately 58.6 kPa and32% oxygen concentration) is reduced by 27% compared to the standard atmosphere used in the Space Shuttle and Space Station. In order to determine whether there is a safer environment in terms of material flammability, a series of piloted ignition delay tests using polymethylmethacrylate (PMMA) was conducted in the FIST apparatus to extend the work over a range of possible exploration atmospheres. The exploration atmospheres considered were the normoxic equivalents, i.e. reduced pressure conditions with a constant partial pressure of oxygen. The ignition delay time was seen to decrease as the pressure was reduced along the normoxic curve. The minimum ignition delay observed in the normoxic equivalent environments was nearly 30% lower than in standard atmospheric conditions. The ignition delay in the proposed exploration atmosphere is only slightly larger than this minimum. Interms of material flammability, normoxic environments with a higher pressure relative to the proposed pressure would be desired.

Ignition delay time↗
NASA NTRS1986

Theoretical kinetic computations in complex reacting systems

Nasa Lewis' studies of complex reacting systems at high temperature are discussed. The changes which occur are the result of many different chemical reactions occurring at the same time. Both an experimental and a theoretical approach are needed to fully understand what happens in these systems. The latter approach is discussed. The differential equations which describe the chemical and thermodynamic changes are given. Their solution by numerical techniques using a detailed chemical mechanism is described. Several different comparisons of computed results with experimental measurements are also given. These include the computation of (1) species concentration profiles in batch and flow reactions, (2) rocket performance in nozzle expansions, and (3) pressure versus time profiles in hydrocarbon ignition processes. The examples illustrate the use of detailed kinetic computations to elucidate a chemical mechanism and to compute practical quantities such as rocket performance, ignition delay times, and ignition lengths in flow processes.

Bittker, David A.↗
NASA NTRS1985

Ignition of mixtures of SiH sub 4, CH sub 4, O sub 2, and Ar or N sub 2 behind reflected shock waves

Ignition delay times in mixtures of methane, silane, and oxygen diluted with argon and nitrogen were measured behind reflected shock waves generated in the chemical kinetic shock tube at Langley Research Center. The delay times were inferred from the rapid increase in pressure that occurs at ignition, and the ignition of methane was verified from the emission of infrared radiation from carbon dioxide. Pressures of 1.25 atm and temperatures from 1100 K to 1300 K were generated behind the reflected shocks; these levels are representative of those occurring within a supersonic Ramjet combustor. Expressions for the ignition delay time as a function of temperature were obtained from least squares curve fits to the data for overall equivalence ratios of 0.7 and 1.0. The ignition delay times with argon as the diluent were longer than those with nitrogen as the diluent. The infrared wavelength observations at 4.38 microns for carbon dioxide indicated that silane and methane ignited simultaneously (i.e., within the time resolution of the measurement). A combined chemical kinetic mechanism for mixtures of silane, methane, oxygen, and argon or nitrogen was assembled from one mechanism that accurately predicted the ignition of methane and a second mechanism that accurately predicted silane hydrogen ignition. Comparisons between this combined mechanism and experiment indicated that additional reactions, possibly between silyl and methyl fragments, are needed to develop a good silane methane mechanism.

Mclain, A. G.↗
NASA NTRS1980

Autoignition characteristics of aircraft-type fuels

The ignition delay characteristics of Jet A, JP 4, no. 2 diesel, cetane and an experimental referee broad specification (ERBS) fuel in air at inlet temperatures up to 1000 K, pressures of 10, 15, 20, 25 and 30 atm, and fuel air equivalence ratios of 0.3, 0.5, 0.7 and 1.0 were mapped. Ignition delay times in the range of 1 to 50 msec at freestream flow velocities ranging from 20 to 100 m/sec were obtained using a continuous flow test apparatus which permitted independent variation and evaluation of the effect of temperature, pressure, flow rate, and fuel/air ratio. The ignition delay times for all fuels tested appeared to correlate with the inverse of pressure and the inverse exponent of temperature. With the exception of pure cetane, which had the shortest ignition delay times, the differences between the fuels tested did not appear to be significant. The apparent global activation energies for the typical gas turbine fuels ranged from 38 to 40 kcal/mole, while the activation energy determined for cetane was 50 kcal/mole. In addition, the data indicate that for lean mixtures, ignition delay times decrease with increasing equivalence ratio. It was also noted that physical (apparatus dependent) phenomena, such as mixing (i.e., length and number of injection sites) and airstream cooling (due to fuel heating, vaporization and convective heat loss) can have an important effect on the ignition delay.

Spadaccini, L. J.↗
NASA NTRS1986

Effect of silane concentration on the supersonic combustion of a silane/methane mixture

A series of direct connect combustor tests was conducted to determine the effect of silane concentration on the supersonic combustion characteristics of silane/methane mixtures. Shock tube ignition delay data indicated more than an order of magnitude reduction in ignition delay times for both 10 and 20 percent silane/methane mixtures as compared to methane. The ignition delay time of the 10 percent mixture was only a factor of 2.3 greater than that of the 20 percent mixture. Supersonic combustion tests were conducted with the fuel injected into a model scramjet combustor. The combustor was mounted at the exit of a Mach 2 nozzle and a hydrogen fired heater was used to provide a variation in test gas total temperature. Tests using the 20 percent silane/methane mixture indicated considerable combustion enhancement when compared to methane alone. This mixture had an autoignition total temperature of 1650 R. This autoignition temperature can be contrasted with 2330 R for hydrogen and 1350 R for a 20 percent silane/hydrogen mixture in similar hardware. Methane without the silane additive did not autoignite in this configuration at total temperatures as high as 3900 R, the maximum temperature at which tests were conducted. Supersonic combustion tests with the silane concentration reduced to 10 percent indicated little improvement in combustion performance over pure methane. The addition of 20 percent silane to methane resulted in a pyrophoric fuel with good supersonic combustion performance. Reducing the silane concentration below this level, however, yielded a less pyrophoric fuel that exhibited poor supersonic combustion performance.

Northam, G. B.↗
NASA NTRS2004

A New Test Method for Material Flammability Assessment in Microgravity and Extraterrestrial Environments

The standard oxygen consumption (cone) calorimeter (described in ASTM E 1354 and NASA STD 6001 Test 2) is modified to provide a bench-scale test environment that simulates the low velocity buoyant or ventilation flow generated by or around a burning surface in a spacecraft or extraterrestrial gravity level. The Equivalent Low Stretch Apparatus (ELSA) uses an inverted cone geometry with the sample burning in a ceiling fire (stagnation flow) configuration. For a fixed radiant flux, ignition delay times for characterization material PMMA are shown to decrease by a factor of three at low stretch, demonstrating that ignition delay times determined from normal cone tests significantly underestimate the risk in microgravity. The critical heat flux for ignition is found to be lowered at low stretch as the convective cooling is reduced. At the limit of no stretch, any heat flux that exceeds the surface radiative loss at the surface ignition temperature is sufficient for ignition. Regression rates for PMMA increase with heat flux and stretch rate, but regression rates are much more sensitive to heat flux at the low stretch rates, where a modest increase in heat flux of 25 kW/m2 increases the burning rates by an order of magnitude. The global equivalence ratio of these flames is very fuel rich, and the quantity of CO produced in this configuration is significantly higher than standard cone tests. These results [2] demonstrate the ELSA apparatus allows us to conduct normal gravity experiments that accurately and quantifiably evaluate a material s flammability characteristics in the real-use environment of spacecraft or extra-terrestrial gravitational acceleration. These results also demonstrate that current NASA STD 6001 Test 2 (standard cone) is not conservative since it evaluates materials flammability with a much higher inherent buoyant convective flow.

Olson, S. L.↗
NASA NTRS2019

Two-Stage Autoignition Dynamics of N-Dodecane Droplets Under Normal Gravity at High Pressures

Experimental observations of two-stage, autoignition characteristics of fiber-supported, n-dodecane fuel droplets under normal gravity are reported for a wide range of ambient temperatures, and pressures varying from 1 atm to 25 atm, which encompasses the fuel critical pressure (~ 18 atm). A high-speed camera is used to obtain backlit images of the autoignition process. During two-stage ignition, a cool-flame front forms below the droplet in the natural convective plume of the fuel vapor originating from the vaporizing droplet, and propagates upward, followed by the formation of a hot-flame kernel that expands rapidly and surrounds the droplet, eventually leading to the classical diffusion flame. Experimentally measured cool, and hot flame formation locations and propagation speeds are presented for varying initial temperatures and pressures. Measured first, and second stage ignition delay times are also reported. The influences of negative temperature coefficient (NTC) regime chemistry on flame starting location, propagation speeds, and ignition delay times are described. The first-stage cool flame characteristics are found to be controlled by both the chemistry, and physical aspects such as droplet evaporation and fuel-oxidizer mixing, while the second-stage hot flame ignition is primarily controlled by chemical kinetics. Further work is currently underway to develop models to quantitatively predict the observed behavior.

Rose, Evan↗
NASA NTRS1988

Detailed mechanism of toluene oxidation and comparison with benzene

A detailed mechanism for the oxidation of toluene in both argon and nitrogen dilutents is presented. The mechanism was used to compute experimentally ignition delay times for shock-heated toluene-oxygen-argon mixtures with resonably good success over a wide range of initial temperatures and pressures. Attempts to compute experimentally measured concentration profiles for toluene oxidation in a turbulent reactor were partially successful. An extensive sensitivity analysis was performed to determine the reactions which control the ignition process and the rates of formation and destruction of various species. The most important step was found to be the reaction of toluene with molecular oxygen, followed by the reactions of hydroperoxyl and atomic oxygen with benzyl radicals. These findings contrast with the benzene oxidation, where the benzene-molecular oxygen reaction is quite unimportant and the reaction of phenyl with molecular oxygen dominates. In the toluene mechanism the corresponding reaction of benzyl radicals with oxygen is unimportant. Two reactions which are important in the oxidation of benzene also influence the oxidation of toluene for several conditions. These are the oxidations of phenyl and cyclopentadienyl radicals by molecular oxygen. The mechanism presented successfully computes the decrease of toluene concentration with time in the nitrogen diluted turbulent reactor. This fact, in addition to the good prediction of ignition delay times, shows that this mechanism can be used for modeling the ignition and combustion process in practical, well-mixed combustion systems.

Bittker, David A.↗
NASA NTRS1985

Theoretical studies of the ignition and combustion of silane-hydrogen-air mixtures

A chemical kinetic mechanism is proposed for the combustion of silane-hydrogen-oxygen-nitrogen mixtures in the initial temperature range from 800K to 1250K and pressure range from 0.5 to 1.35 atm. The mechanism yields results which are in agreement with published ignition delay times obtained from shock tube experiments. Comparisons between the results obtained using the proposed mechanism and that of an alternative mechanism reveal that the former predicts appreciably shorter ignition delay times, but a flame blowout envelope which is shifted so as to decrease the stable flame region. Over much of the thermodynamic range examined, the mechanism predicts long reaction times. A three step global mechanism is proposed which closely models the ignition phase of SiH4 - H2 - air combustion; however, the reaction phase is less well reproduced by the global model. The necessity for additional experimental data to further assess the proposed models is stressed.

Chinitz, W.↗
NASA NTRS1981

Autoignition characteristics of no. 2 diesel fuel

Parametric tests to map the ignition delay characteristics were conducted at pressures of 3, 4, and 5 atm, inlet air temperatures up to 1150 K and fuel air equivalence ratios ranging from 0.2 to 1.0. Ignition delay times in the range of 6 msec to 60 msec at freestream flow velocities ranging from 10 m/sec to 40 m/sec were obtained. The ignition delay times appeared to correlate with the inverse of pressure and the inverse exponent of temperature.

Tevelde, J. A.↗
NASA NTRS1992

Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method - Combustion of methane

A method of systematic optimization, solution mapping, as applied to a large-scale dynamic model is presented. The basis of the technique is parameterization of model responses in terms of model parameters by simple algebraic expressions. These expressions are obtained by computer experiments arranged in a factorial design. The developed parameterized responses are then used in a joint multiparameter multidata-set optimization. A brief review of the mathematical background of the technique is given. The concept of active parameters is discussed. The technique is applied to determine an optimum set of parameters for a methane combustion mechanism. Five independent responses - comprising ignition delay times, pre-ignition methyl radical concentration profiles, and laminar premixed flame velocities - were optimized with respect to thirteen reaction rate parameters. The numerical predictions of the optimized model are compared to those computed with several recent literature mechanisms. The utility of the solution mapping technique in situations where the optimum is not unique is also demonstrated.

Frenklach, Michael↗
NASA NTRS2024

Fundamental Experimental Tests and Modeling of LOX/CH4 Engines at High Pressures

In recent years, the space travel industry has grown exponentially, resulting in the need for a low-cost, efficient rocket engine fuel. As such, there has been renewed interest in utilizing liquid natural gas (LNG) as it is less likely to soot than kerosene-based fuels and has widespread availability and low cost of use as compared to the traditional RP-X and even liquid methane (LCH4) fuels due to the reduced need for refinement. However, current literature does not fully cover varying blends of natural gas and the effects that impurities have on natural gas/methane fuels, with most studies being confined to low-pressure applications. Therefore, new experimental ignition delay time measurements at rocket engine relevant pressures are essential to ensure current chemical kinetic models capture the ignition behavior at these elevated conditions and to determine the optimal purity levels for a reliable, cost-efficient, aerospace-grade LCH4/LNG fuel. The current work explores various blends of natural gas/methane fuel with various impurities, including higher hydrocarbons as well as nitrogen-carriers. A shock tube study was carried out to study the ignition delay times and carbon monoxide time histories of these natural gas blends utilizing chemiluminescence and laser absorption spectroscopy at 20, 50 and 100 atm over temperatures ranging from 1400-1700K and at an equivalence ratio of 1. The experimental data was then compared to two different chemical kinetic mechanisms: the industry-standard GRI 3.0 and the in-house UCF 2022. The data is used to improve chemical kinetic mechanisms and modeling of LNG fuels for rocket engine applications.

Methane↗