Ignition of non-premixed cyclohexane and mono-alkylated cyclohexane flames

Ignition temperatures of non-premixed cyclohexane, methylcyclohexane, ethylcyclohexane, n-propylcyclohexane, and n-butylcyclohexane flames were measured in the counterflow configuration at atmospheric pressure, a free-stream fuel/N₂ mixture temperature of 373 K, a local strain rate of 120 s^?1, and fuel mole fractions ranging from 1% to 10%. Using the recently developed JetSurf 2.0 kinetic model, satisfactory predictions were found for cyclohexane, methyl-, ethyl-, and n-propyl-cyclohexane flames, but the n-butylcyclohexane data were overpredicted by 20 K. The results showed that cyclohexane flames exhibit the highest ignition propensity among all mono-alkylated cyclohexanes and n-hexane due to its higher reactivity and larger diffusivity. The size of mono-alkyl group chain was determined to have no measurable effect on ignition, which is a result of competition between fuel reactivity and diffusivity. Detailed sensitivity analyses showed that flame ignition is sensitive primarily to fuel diffusion and also to H₂/CO and C₁–C₃ hydrocarbon kinetics.     

The effects of water dilution on hydrogen,syngas, and ethylene flames at elevated pressure

This work investigates experimentally and numerically the kinetic effects of water vapor addition on the burning rates of H₂, H₂/CO mixtures, and C₂H₄ from 1 atm to 10 atm at flame temperatures between 1600 K and 1800 K. Burning rates were measured using outwardly propagating spherical flames in a nearly constant pressure chamber. Results show good agreement with newly updated kinetic models for H₂ flames. However, there is considerable disagreement between simulations and measurements for H₂/CO and C₂H₄ flames at high pressure and high water vapor dilution. Both experiments and simulations show that water vapor addition causes a monotonic decrease in mass burning rate and the inhibitory effect increases with pressure. For hydrogen flames, water vapor addition reduces the critical pressure above which a negative pressure dependence of the burning rate is observed. However, for C₂H₄ flames, the burning rate always increases with pressure. The results also show that water vapor addition has the same effect as a pressure increase for H₂ and H₂/CO flames, shifting the reaction zone into a narrower window at higher temperatures. For all fuels, water vapor addition increases OH formation via H₂O + O while reducing the overall active radical pool for hydrogen flames. For C₂H₄, the additional HO₂ production pathway through HCO results in a dramatic difference in pressure dependence of the burning rate from that observed for hydrogen. The present work provides important additions to the experimental database for syngas and C₀–C₂ high pressure kinetic model validations.     

Modeled quenching limits of spherical hydrogen diffusion flames

Hydrogen–air diffusion flames were modeled with an emphasis on kinetic extinction. The flames were one-dimensional spherical laminar diffusion flames supported by adiabatic porous burners of various diameters. Behavior of normal (H₂ flowing into quiescent air) and inverse (air flowing into quiescent H₂) configurations were considered using detailed H₂/O₂ chemistry and transport properties with updated light component diffusivities. For the same heat release rate, inverse flames were found to be smaller and 290 K hotter than normal flames. The weakest normal flame that could be achieved before quenching has an overall heat release rate of 0.25 W, compared to 1.4 W for the weakest inverse flame. There is extensive leakage of the ambient reactant for both normal and inverse flames near extinction, which results in a premixed flame regime for diffusion flames except for the smallest burners with radii on the order of 1 μm. At high flow rates H + OH(+M) → H₂O(+M) contributes nearly 50% of the net heat release. However at flow rates approaching quenching limits, H + O₂(+M) → HO₂(+M) is the elementary reaction with the largest heat release rate.     

Fundamental burning velocities of meso-scale propagating spherical flames with H2, CH4 and C3H8 mixtures

This study is performed to experimentally examine the fundamental burning velocity characteristics of meso-scale outwardly propagating spherical laminar flames in the range of flame radius r_f approximately from 1 to 5 mm for hydrogen, methane and propane mixtures, in order to make clear a method for improving combustion of micro–meso scale flames. Macro-scale laminar flames with r_f > 7 mm are also examined for comparison. The mixtures have nearly the same laminar burning velocity (S_L0 = 25 cm/s) for unstretched flames and different equivalence ratios ?. The radius r_f and the burning velocity S_Ll of meso-scale flames are estimated by using sequential schlieren images recorded under appropriate ignition conditions. It is found that S_Ll of hydrogen and methane premixed meso-scale flames at the same r_f or the Karlovitz number Ka shows a tendency to increase with decreasing ?, whereas S_Ll of propane flames increases with ?. However, S_Ll tends to decrease with the Lewis number Le and the Markstein number Ma, irrespective of the type of fuel and ?. It also becomes clear that the optimum flame size and Ka to improve the burning velocity exist for some mixtures depending on Le and fuel types.     

The structure and extinction of nonpremixed methane/nitrous oxide and ethane/nitrous oxide flames

Knowledge of combustion of hydrocarbon fuels with nitrogen-containing oxidizers is a first step in understanding key aspects of combustion of hypergolic and gun propellants. Here an experimental and kinetic-modeling study is carried out to elucidate aspects of nonpremixed combustion of methane (CH₄) and nitrous oxide (N₂O), and ethane (C₂H₆) and N₂O. Experiments are conducted, at a pressure of 1 atm, on flames stabilized between two opposing streams. One stream is a mixture of oxygen (O₂), nitrogen (N₂), and N₂O, and the other a mixture of CH₄ and N₂ or C₂H₆ and N₂. Critical conditions for extinction are measured. Kinetic-modeling studies are performed with the San Diego Mechanism. Experimental data and results of kinetic-modeling show that N₂O inhibits the flame by promoting extinction. Analysis of the flame structure shows that H radicals are produced in the overall chain-branching step 3H₂ + O₂ ? 2H₂O + 2H, in which molecular hydrogen is consumed. Hydrogen is also consumed in the overall step N₂O + H₂ ? N₂ + H₂O where stable products are formed. Inhibition of the flames by N₂O is attributed to competition between these two overall steps.     

The diffusion flame structure of an ammonium perchlorate based composite propellant at elevated pressures

Examination of the surface behavior and flame structure of a bimodal ammonium perchlorate (AP) composite propellant at elevated pressure was performed using high speed (5 kHz) planar laser-induced fluorescence (PLIF) from 1 to 12 atm and visible surface imaging spanning 1–20 atm. The dynamics of the combustion of single, coarse AP crystals were resolved using these techniques. It was found that the ignition delay time for individual AP crystals contributed significant to the particle lifetime only at pressures below about 6 atm. In situ AP crystal burning rates were found to be higher than rates reported for pure AP deflagration studies. The flame structure was studied by exciting OH molecules in the gas phase. Two types of diffusion flames were observed above the composite propellant: jet-like flames and v-shaped, inverted, overventilated, flames (IOF) lifted off the surface. While jet-like diffusion flames have been imaged at low pressures and simulated by models, the lifted IOFs have not been previously reported or predicted. The causes for the observed flame structures are explained by drawing on an understanding of the surface topography and disparities in the burning rates of the fuel and oxidizer.     

Cup-burner flame structure and extinguishment by CF3Br and C2HF5 in microgravity

The effects of fire-extinguishing agents CF₃Br and C₂HF₅ on the structure and extinguishing processes of microgravity cup-burner flames have been studied numerically. Propane and a propane–ethanol–water fuel mixture, prescribed for a Federal Aviation Administration (FAA) aerosol can explosion simulator test, were used as the fuel. The time-dependent, two-dimensional numerical code, which includes a detailed kinetic model (177 species and 2986 reactions), diffusive transport, and a gray-gas radiation model, revealed unique flame structure and predicted the minimum extinguishing concentration of agent when added to the air stream. The peak reactivity spot (i.e., reaction kernel) at the flame base stabilized a trailing flame. The calculated flame temperature along the trailing flame decreased downstream due to radiative cooling, causing local extinction at <1250 K and flame tip opening. As the mole fraction of agent in the coflow (X_a) was increased gradually: (1) the premixed-like reaction kernel weakened (i.e., lower heat release rate) (but nonetheless formed at higher temperature); (2) the flame base stabilized increasingly higher above the burner rim, parallel to the axis, until finally blowoff-type extinguishment occurred; (3) the calculated maximum flame temperature remained at nearly constant (≈1700 K) or mildly increased; and (4) the total heat release of the entire flame decreased (inhibited) for CF₃Br but increased (enhanced) for C₂HF₅. In the lifted flame base with added C₂HF₅, H₂O (formed from hydrocarbon-O₂ combustion) was converted further to HF and CF₂O through exothermic reactions, thus enhancing the heat-release rate peak. In the trailing flame, “two-zone” flame structure developed: CO₂ and CF₂O were formed primarily in the inner and outer zones, respectively, while HF was formed in both zones. As a result, the unusual (non-chain branching) reactions and the combustion enhancement (increased total heat release) due to the C₂HF₅ addition occurred primarily in the trailing diffusion flame.     

An experimental and modeling study of the autoignition of 3-methylheptane

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C₈ alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.     

An experimental study on the formation of polycyclic aromatic hydrocarbons in laminar coflow non-premixed methane/air flames doped with four isomeric butanols

Experimental measurements were conducted for temperatures and mole fractions of C1–C16 combustion intermediates in laminar coflow non-premixed methane/air flames doped with 3.9% (in volume) 1-butanol, 2-butanol, iso-butanol and tert-butanol, respectively. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) technique was utilized in the measurements of species mole fractions. The results show that the variant molecular structures of butyl alcohols have led to different efficiencies in the formation of polycyclic aromatic hydrocarbons (PAHs) that may cause the variations in sooting tendency. Detailed species information suggests that the presence of allene and propyne promotes benzene formation through the C₃H₃ + C₃H₄ reactions and consequently PAH formation through the additions of C2 and C3 species to benzyl or phenyl radicals. As a matter of fact, PAHs formed from the 1-butanol doped flame are the lowest among the four investigated flames, because 1-butanol mainly decomposes to ethylene and oxygenates rather than C3 hydrocarbon species. Meanwhile, the tert-butanol doped flame generates the largest quantities of allene and propyne among the four flames and therefore is the sootiest one.     

Ignition delay times of methyl oleate and methyl linoleate behind reflected shock waves

Ignition delay times for methyl oleate (C₁₉H₃₆O₂, CAS: 112-62-9) and methyl linoleate (C₁₉H₃₄O₂, CAS: 112-63-0) were measured for the first time behind reflected shock waves, using an aerosol shock tube. The aerosol shock tube enabled study of these very-low-vapor-pressure fuels by introducing a spatially-uniform fuel aerosol/4% oxygen/argon mixture into the shock tube and employing the incident shock wave to produce complete fuel evaporation, diffusion, and mixing. Reflected shock conditions covered temperatures from 1100 to 1400 K, pressures of 3.5 and 7.0 atm, and equivalence ratios from 0.6 to 2.4. Ignition delay times for both fuels were found to be similar over a wide range of conditions. The most notable trend in the observed ignition delay times was that the pressure and equivalence ratio scaling were a strong function of temperature, and exhibited cross-over temperatures at which there was no sensitivity to either parameter. Data were also compared to the biodiesel kinetic mechanism of Westbrook et al. (2011) [10], which underpredicts ignition delay times by about 50%. Differences between experimental and computed ignition delay times were strongly related to existing errors and uncertainties in the thermochemistry of the large methyl ester species, and when these were corrected, the kinetic simulations agreed significantly better with the experimental measurements.     

Tunable fiber laser based photoacoustic gas sensor for early fire detection

A photoacoustic gas sensor using a near-infrared tunable fiber laser and based on wavelength modulation spectroscopy technique is developed. This sensor is capable of quasi-simultaneous quantification of water vapour, acetylene, carbon dioxide, and carbon monoxide (H₂O, C₂H₂, CO and CO₂) concentrations in the fire emulator. The feasibility of using this sensor as an early fire detector was demonstrated. The fire warning gases from smoldering paper were measured. The peak concentrations of gases from smoldering paper were 20,300 ppm H₂O, 2.1 ppm C₂H₂, 756 ppm CO, and 1612 ppm CO₂ after 400 s.     

Direct ignition and S-curve transition by in situ nano-second pulsed discharge in methane/oxygen/helium counterflow flame

A well-defined plasma assisted combustion system with novel in situ discharge in a counterflow diffusion flame was developed to study the direct coupling kinetic effect of non-equilibrium plasma on flame ignition and extinction. A uniform discharge was generated between the burner nozzles by placing porous metal electrodes at the nozzle exits. The ignition and extinction characteristics of CH₄/O₂/He diffusion flames were investigated by measuring excited OH¹ and OH PLIF, at constant strain rates and O₂ mole fraction on the oxidizer side while changing the fuel mole fraction. It was found that ignition and extinction occurred with an abrupt change of OH¹ emission intensity at lower O₂ mole fraction, indicating the existence of the conventional ignition-extinction S-curve. However, at a higher O₂ mole fraction, it was found that the in situ discharge could significantly modify the characteristics of ignition and extinction and create a new monotonic and fully stretched ignition S-curve. The transition from the conventional S-curves to a new stretched ignition curve indicated clearly that the active species generated by the plasma could change the chemical kinetic pathways of fuel oxidation at low temperature, thus resulting in the transition of flame stabilization mechanism from extinction-controlled to ignition-controlled regimes. The temperature and OH radical distributions were measured experimentally by the Rayleigh scattering technique and PLIF technique, respectively, and were compared with modeling. The results showed that the local maximum temperature in the reaction zone, where the ignition occurred, could be as low as 900 K. The chemical kinetic model for the plasma–flame interaction has been developed based on the assumption of constant electric field strength in the bulk plasma region. The reaction pathways analysis further revealed that atomic oxygen generated by the discharge was critical to controlling the radical production and promoting the chain branching effect in the reaction zone for low temperature ignition enhancement.     

Ignition behavior of pure and blended methyl octanoate,n-nonane,and methylcyclohexane

Excited-state species profiles and ignition delay times were obtained under dilute conditions (99% Ar) using a heated shock tube for methyl octanoate (C₉H₁₈O₂), n-nonane (n-C₉H₂₀), and methylcyclohexane (MCH) over a broad range of temperature and equivalence ratio (? = 0.5, 1.0, 2.0) at pressures near 1 and 10 atm. Measurements were then extended to include two ternary blends of the fuels using 5% and 20% (vol.) of the methyl ester under stoichiometric conditions. Using three independently validated chemical kinetics mechanisms, a model was compiled to assess the influence of methyl ester concentration on ignition delay times of the ternary blends. Under near-atmospheric pressure, ignition delay times were of the following order for the pure fuels: methyl octanoate < n-nonane < methylcyclohexane. Experimental results indicate that the ignition behavior of the higher-order methyl ester approaches that of the higher-order linear alkane with increased pressure regardless of equivalence ratio. Methyl octanoate also displayed significantly lower pressure dependence relative to the linear alkane and the cycloalkane species. Both of these results are supported by model calculations. Blending of methyl octanoate with n-nonane and methylcyclohexane impacted ignition delay time results more strongly at 1.5 atm, yet had only a small effect near 10 atm for temperatures above 1400 K. The study provides the first shock-tube data for a ternary blend of a linear alkane, a cycloalkane, and a methyl ester. Ignition delay time measurements for the C₉:0 methyl ester were also measured for the first time.     

Theoretical study of the reaction 2,5-dimethylfuran + H → products

The reaction of 2,5-dimethylfuran (DMF) with H-atoms was studied using a potential energy surface calculated at the CBS-QB3 level of theory and master equation/RRKM modeling. Hydrogen abstraction by H-atom and hydrogen additions on DMF were considered. As the decomposition pathways of the initial adducts were unknown, a large number of decomposition routes was explored for these adducts. An important number of interconnected product channels were found and preliminary master equation calculations were performed to select the crucial wells and exit channels. The ipso substitution DMF + H → methylfuran (MF) + CH₃ and the formation of 1,3-butadiene and acetyl radical (CH₃CO) were found to be the major product channels in the addition process. The total calculated rate constant was found in good agreement with experimental data and is nearly pressure-independent. A small sensitivity to pressure was found for the computed branching ratios. At 1 bar, the yields of the two product channels of the addition process are maximal at 1100 K with computed branching ratios of 39% (MF + CH₃) and 27% (1,3-C₄H₆ + CH₃CO). Above 1300 K, hydrogen abstraction by H-atom becomes dominant and reaches a branching ratio of 56% at 2000 K.     

Stabilized flames in hybrid aluminum-methane-air mixtures

A premixed methane–air bunsen-type flame is seeded with micron-sized (d₃₂ = 5.6 μm) atomized aluminum powder over a wide range of solid fuel concentrations. The burning velocities of the resulting two-phase hybrid flame are determined using the total surface area of the inner flame cone and the known volumetric flow rate, and spatially resolved flame spectra are obtained with a spectral scanning system. Flame temperatures are derived through polychromatic fitting of Planck’s law to the continuous part of the spectrum. It is found that an increase in the solid fuel concentration changes the aluminum combustion regime from low temperature oxidation to full-fledged flame front propagation. For stoichiometric methane–air mixtures, the transition occurs in the aluminum concentration range of 140–220 g/m³ and is manifested by the appearance of AlO sub-oxide bands and an increase in the flame temperature to 2500 K. The flame burning velocity is found to decrease only slightly with an increase in aluminum concentration, in contrast to the rapid decrease in flame speed, followed by quenching, that is observed for flames seeded with inert SiC particles. The observed behavior of the burning velocity and flame temperature leads to the conclusion that intense aluminum combustion in a hybrid flame only occurs when the flame front propagating through the aluminum suspension is coupled to the methane–air flame.     

Kinetics for the reactions of phenyl with methanol and ethanol: Comparison of theory and experiment

The kinetics of the C₆H₅ reactions with CH₃OH and C₂H₅OH has been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 306–771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to improve our low temperature measurements down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH₃OH) = (7.82 ± 0.44) × 10¹¹ exp [?(853 ± 30)/T] and k(C₂H₅OH) = (5.73 ± 0.58) × 10¹¹ exp [?(1103 ± 44)/T] cm³ mol^?1 s^?1 for the temperature range studied. Theoretically, four possible product channels of the C₆H₅ + CH₃OH reaction producing C₆H₆ + CH₃O, C₆H₆ + CH₂OH, C₆H₅OH + CH₃ and C₆H₅OCH₃ + H and five possible product channels of the C₆H₅ + C₂H₅OH reaction producing C₆H₆ + C₂H₅O, C₆H₆ + CH₂CH₂OH, C₆H₆ + CH₃CHOH, C₆H₅OH + CH₃CH₂ and C₆H₅OCH₂CH₃ + H have been computed at the G2M//B3LYP/6?311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers than those for the substitution reactions and their rate constants were calculated by the microcanonical variational transition state theory at 200–3000 K. The predicted rate constants are in good agreement with the experimental values. Significantly, the rate constant for the CH₃OH reaction with C₆H₅ was found to be greater than that for the C₂H₅OH reaction and both reactions were found computationally to be dominated by H-abstraction from the hydroxyl group attributable to the affinity of the phenyl toward the OH group and the predicted lower energy barriers for the OH attack.     

Experimental study of minimum ignition energy of lean H2-N2O mixtures

Ignition energies for short duration (<50 ns) spark discharges were measured for undiluted and nitrogen-diluted H₂-N₂O mixtures of equivalence ratios ? = 0.15 and 0.2, dilution of 0% and 20% N₂, and initial pressures of 15–25 kPa. The ignition events were analyzed using statistical tools and the probability of ignition versus spark energy density (spark energy divided by the spark length) was obtained. The simple cylindrical ignition kernel model was compared against the results from the present study. Initial pressure has a significant effect on the width of the probability distribution, ranging from a broad (P = 15 kPa) to a narrow (P = 25 kPa) probability distribution indicating that the statistical variation of median spark energy density increases as initial pressure of the mixture decreases. A change in the equivalence ratio from 0.15 to 0.2 had a small effect on the median spark energy density. The addition of 20% N₂ dilution caused a significant increase in the median spark energy density when compared to no dilution. The extrapolation of the present results to atmospheric pressure, stoichiometric H₂-N₂O indicates that the electrostatic discharge ignition hazards are comparable to or greater than H₂-O₂ mixtures.     

IR spectral shifts and adsorption potentials of CO and N2 adsorbed on LiF and LiCl

Following our recent work on IR spectra of molecules adsorbed on C₆₀ embedded in LiF and LiCl films, adsorption potentials of CO and N₂ adsorbed on LiF (100) and LiCl (100) were calculated. For CO on LiF, a value of 2.0 kcal mol⁻¹ was obtained, close to that calculated for CO adsorbed on a single C₆₀ molecule. The calculated value for CO on LiCl is much higher, 6.8 kcal mol⁻¹. It is therefore concluded that in the case of CO adsorbed on mixed LiF/C₆₀ films, the adsorbed CO molecules are distributed almost evenly on the LiF and C₆₀ single molecules, whereas in the case of CO adsorbed on mixed LiCl/C₆₀ films the salt is greatly preferred as the adsorption site. Adsorption potential calculations for a similar system, N₂ on LiF and LiCl, gave values of 1.5 and 4.4 kcal mol⁻¹, respectively. In this case, a much too large value was found for the adsorption potential on the LiCl surface. IR spectra of CO on the two substrates showed two strong absorptions for each of them. With N₂ induced spectra were obtained. Spectral shifts have been calculated for the above systems and were all toward higher frequencies, in agreement with experimental findings.     

Experimental investigation of flame spreading over pure methane hydrate in a laminar boundary layer

Flame spreading over pure methane hydrate in a laminar boundary layer is investigated experimentally. The free stream velocity (U_∞) was set constant at 0.4 m/s and the surface temperature of the hydrate at the ignition (T_s) was varied between ?10 and ?80 °C. Hydrate particle sizes were smaller than 0.5 mm. Two types of flame spreading were observed; “low speed flame spreading” and “high speed flame spreading”. The low speed flame spreading was observed at low temperature conditions (T_s = ?80 to ?60 °C) and temperatures in which anomalous self-preservation took place (T_s = ?30 to ?10 °C). In this case, the heat transfer from the leading flame edge to the hydrate surface plays a key role for flame spreading. The high speed flame spreading was observed when T_s = ?50 and ?40 °C. At these temperatures, the dissociation of hydrate took place and the methane gas was released from the hydrate to form a thin mixed layer of methane and air with a high concentration gradient over the hydrate. The leading flame edge spread in this premixed gas at a spread speed much higher than laminar burning velocity, mainly due to the effect of burnt gas expansion.