Propagation and extinction of cyclopentadiene flames

Laminar flame speeds and extinction strain rates of cyclopentadiene/air mixture were determined in the counterflow configuration at atmospheric pressure, unburned mixture temperature of 353 K, and for a wide range of equivalence ratios. The experiments were modeled using recently developed kinetic models. Sensitivity analyses showed that both flame propagation and extinction of cyclopentadiene/air mixtures flames depend notably on the fuel kinetics and subsequent intermediates such as cyclopentadienyl, cyclopentadienone, and cyclopentadienoxy. Analyses of the computed flame structures revealed that the high temperature oxidation of cyclopentadiene depends in general on the kinetics of first few intermediates in the oxidation process following the fuel consumption. The potential reaction pathways of the consumption of cyclopentadienyl radicals were discussed and further investigation and validation is recommended for two relevant reactions that could improve the high temperature oxidation kinetic model of cyclopentadiene. The experimental flame data of this study are the first ones to be reported.     

Reaction propagation modes in millimeter-scale tubes for ethylene/oxygen mixtures

Effects of tube diameter and equivalence ratio on reaction front propagations of ethylene/oxygen mixtures in capillary tubes were experimentally analyzed using high speed cinematography. The inner diameters of the tubes investigated were 0.5, 1, 2 and 3 mm. The flame was ignited at the center of the 1.5 m long smooth tube under ambient pressure and temperature before propagated towards the exits in the opposite directions. A total of five reaction propagation scenarios, including deflagration-to-detonation transition followed by steady detonation wave transmission (DDT/C–J detonation), oscillating flame, steady deflagration, galloping detonation and quenching flame, were identified. DDT/C–J detonation mode was observed for all tubes for equivalence ratios in the vicinity of stoichiometry. The velocity for the steady detonation wave propagation was approximately Chapman–Jouguet velocity for 1, 2, and 3 mm I.D. tubes; however, a velocity deficit of 5% was found for the case in 0.5 mm I.D. tube. For leaner mixtures, an oscillating flame mode was found for tubes with diameters of 1 to 3 mm, and the reaction front travelled in a steady deflagrative flame mode with velocities around 2–3 m/s when the mixture equivalence ratio becomes even leaner. Galloping detonation wave propagation was the dominant mode for the fuel lean regime in the 0.5 mm I.D. tube. For rich mixtures beyond the detonation limits, a fast flame followed by flame quenching was observed.     

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.     

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.     

Ignition of non-premixed counterflow flames of octane and decane isomers

Ignition temperatures of non-premixed flames of octane and decane isomers were determined in the counterflow configuration at atmospheric pressure, a free-stream fuel/N₂ mixture temperature of 401 K, a local strain rate of 130 s^?1, and fuel mole fractions ranging from 1% to 6%. The experiments were modeled using detailed chemical kinetic mechanisms for all isomers that were combined with established H₂, CO, and n-alkane models, and close agreements were found for all flames considered. The results confirmed that increasing the degree of branching lowers the ignition propensity. On the other hand, increasing the straight chain length by two carbons was found to have no measurable effect on flame ignition for symmetric branched fuel structures. Detailed sensitivity analyses showed that flame ignition is sensitive primarily to the H₂/CO and C₁–C₃ hydrocarbon kinetics for low degrees of branching, and to fuel-related reactions for the more branched molecules.     

Reduction of flammability of ultrahigh-molecular-weight polyethylene by using triphenyl phosphate additives

The mechanism of reducing the flammability of ultrahigh-molecular-weight polyethylene (UHMWPE) with triphenyl phosphate (TPP) additives was investigated, using the methods of molecular-beam mass spectrometry (MBMS), differential mass spectrometric thermal analysis (DMSTA), thermocouple, thermogravimetry (TGA), and gas chromatography mass spectrometry (GC/MS). Kinetics of thermal degradation of pure UHMWPE and of that mixed with TPP was studied at high (～150 K/s) and low (0.17 K/s) heating rates at atmospheric pressure. Effective values of the rate constants of the thermal degradation reaction were determined. Times of ignition delay, the limiting oxygen index, the burning rates of UHMWPE and UHMWPE + TPP and their temperature profiles in the flames were measured. The flame structure was investigated and the composition of the combustion products in the flame zone adjacent to the specimen’s combustion surface. TPP vapors in flame were found. Addition of TPP to UHMWPE was found to result in reduction of polymer flammability. TPP was shown to act as flame retardant both in the condensed and gas phases.     

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.     

Critical grain size in the γ→α martensite transformation. Thermodynamic analysis with regard to spatial scales characteristic of martensite nucleation

In the work, it is shown that taking into account the ratio of spatial scales characteristic of martensite crystal nucleation in the elastic field of an individual dislocation localized in a grain of diameter D makes it possible (i) to estimate the critical grain size D_c (～1 μm) characteristic of the γ→α transformation at a martensite starting temperature M_s ～ 100 K from the requirements that threshold strain arises in the elastic region, (ii) to consistently describe the D dependence of M_s with M_s(D_c) = 0 from analysis of the phase free energy difference, (iii) to express D_c through macroparameters and interpret the limiting case M_s∞→0, D_c→∞ (D_c ～ (M_s∞)^?1 with M_s∞ ≡ M_s (∞)), and (iv) to more exactly specify the qualitative dynamic model of the effect of dislocation grain boundaries on the onset of initial excitation.     

Inelastic neutron scattering on iron-based superconductor BaFe2(As,P)2

Inelastic neutron scattering has been performed on powder sample of an iron-based superconductor BaFe₂(As_0.65P_0.35)₂ with superconducting transition temperature (T_c) = 30 K, whose superconducting (SC) order parameter is expected to have line node. In the normal state, constant-E scan of dynamical structure factor, S(Q, E), exhibits a peak structure centered at momentum transfer Q ～ 1.20 Å^?1, corresponding to antiferromagnetic wave vector. Below T_c, the redistribution of the magnetic spectral weight takes place, resulting in the formation of a peak at E ～ 12 meV and a gap below 6 meV. The enhanced magnetic peak structure is ascribed to the spin resonance mode, evidencing sign change in the SC order parameter similar to other iron-based high-T_c superconductors. It suggests that fully-gapped s_± symmetry dominates in this superconductor, which gives rise to high-T_c (=30 K) despite the nodal symmetry.     

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.     

Modeling midwave infrared muzzle flash spectra from unsuppressed and flash-suppressed large caliber munitions

Time-resolved infrared spectra of firings from a 152 mm howitzer were acquired over an 1800–6000 cm^?1 spectral range using a Fourier-transform spectrometer. The instrument collected primarily at 32 cm^?1 spectral and 100 Hz temporal resolutions. Munitions included unsuppressed and chemically flash suppressed propellants. Secondary combustion occurred with unsuppressed propellants resulting in flash emissions lasting ～100 ms and dominated by H₂O and CO₂ spectral structure. Non-combusting plume emissions were one-tenth as intense and approached background levels within 20–40 ms. A low-dimensional phenomenological model was used to reduce the data to temperatures, soot absorbances, and column densities of H₂O, CO₂, CH₄, and CO. The combusting plumes exhibit peak temperatures of ～1400 K, areas of greater than 32 m², low soot emissivity of ～0.04, with nearly all the CO converted to CO₂. The non-combusting plumes exhibit lower temperatures of ～1000 K, areas of ～5 m², soot emissivity of greater than 0.38 and CO as the primary product. Maximum fit residual relative to peak intensity are 14% and 8.9% for combusting and non-combusting plumes, respectively. The model was generalized to account for turbulence-induced variations in the muzzle plumes. Distributions of temperature and concentration in 1–2 spatial regions demonstrate a reduction in maximum residuals by 40%. A two-region model of combusting plumes provides a plausible interpretation as a ～1550 K, optically thick plume core and ～2550 K, thin, surface-layer flame-front. Temperature rate of change was used to characterize timescales and energy release for plume emissions. Heat of combustion was estimated to be ～5 MJ/kg.     

An experimental and numerical investigation of the hetero-/homogeneous combustion of fuel-rich hydrogen/air mixtures over platinum

The hetero-/homogeneous combustion of hydrogen/air mixtures over platinum was investigated experimentally and numerically in a channel-flow configuration at fuel-rich equivalence ratios ranging from 2 to 7, pressures up to 5 bar and wall temperatures 760–1200 K. Experiments involved in situ one-dimensional Raman measurements of major gas-phase species concentrations over the catalyst boundary layer and planar laser induced fluorescence (LIF) of the OH radical, while simulations included an elliptic 2-D model with detailed heterogeneous and homogeneous reaction mechanisms. The employed reaction schemes reproduced the measured catalytic reactant consumption, the onset of homogeneous ignition, and the post-ignition flame shapes at all examined conditions. Although below a critical pressure, which depended on temperature, the intrinsic gas-phase kinetics of hydrogen dictated lower reactivity for the fuel-rich stoichiometries when compared to fuel-lean ones, homogeneous ignition was still more favorable for the rich stoichiometries due to the lower molecular transport of the deficient oxygen reactant that resulted in modest catalytic reactant consumption over the gaseous induction zone. Above the critical pressure, the intrinsic gaseous hydrogen kinetics yielded higher reactivity for the rich stoichiometries, which resulted in vigorous gaseous combustion at pressures up to 5 bar, in contrast to lean stoichiometry studies whereby homogeneous combustion was altogether suppressed above 3 bar. Computations at fuel-rich stoichiometries in practical channel geometries indicated that homogeneous combustion was not of concern for reactor thermal management, since the larger than unity Lewis number of the deficient oxygen reactant confined the flames to the core of the channel, away from the solid walls.     

Critical temperature and reactant mass flux for radiative extinction of ethylene microgravity spherical diffusion flames at 1 bar

In microgravity combustion, where buoyancy is not present to accelerate the flow field and strain the flame, radiative extinction is of fundamental importance, and has implications for spacecraft fire safety. In this work, the critical point for radiative extinction is identified for normal and inverse ethylene spherical diffusion flames via atmospheric pressure experiments conducted aboard the International Space Station, as well as with a transient numerical model. The fuel is ethylene with nitrogen diluent, and the oxidizer is an oxygen/nitrogen mixture. The burner is a porous stainless-steel sphere. All experiments are conducted at constant reactant flow rate. For normal flames, the ambient oxygen mole fraction was varied from 0.2 to 0.38, burner supply fuel mole fraction from 0.13 to 1, total mass flow rate, ṁ_total, from 0.6 to 12.2 mg/s, and adiabatic flame temperature, T_ad, from 2000 to 2800 K. For inverse flames, the ambient fuel mole fraction was varied from 0.08 to 0.12, burner supply oxygen mole fraction from 0.4 to 0.85, ṁ_total from 2.3 to 11.3 mg/s, and T_ad from 2080 to 2590 K. Despite this broad range of conditions, all flames extinguish at a critical extinction temperature of 1130 K, and a fuel-based mass flux of 0.2 g/m²-s for normal flames, and an oxygen-based mass flux of 0.68 g/m²-s for inverse flames. With this information, a simple equation is developed to estimate the flame size (i.e., location of peak temperature) at extinction for any atmospheric-pressure ethylene spherical diffusion flame given only the reactant mass flow rate. Flame growth, which ultimately leads to radiative extinction if the critical extinction point is reached, is attributed to the natural development of the diffusion-limited system as it approaches steady state and the reduction in the transport properties as the flame temperature drops due to increasing flame radiation with time (radiation-induced growth.)     

Effect of pressure on structure and extinction of near-limit hydrogen counterflow diffusion flames

Results of measurements of critical conditions for extinction and of temperature profiles in counterflow diffusion flames are reported. The fuel was a hydrogen–nitrogen mixture with 14 mole percent hydrogen, and the oxidizer was air. Pressures ranged from 0.1 MPa to 1.5 MPa; measurements were made in a facility especially constructed for carrying out counterflow combustion experiments at high pressures. With increasing pressure, the strain rate at extinction first increases and then decreases, in qualitative agreement with predictions, but there are observable quantitative differences. Temperature profiles, obtained employing an R-type thermocouple at a fixed strain rate of 100/s, agree well with predictions, within experimental uncertainty. The results may help to improve knowledge of underlying chemical-kinetic and transport parameters at elevated pressures.     

Influence of radiation losses on the stability of premixed flames on a porous-plug burner

Analysis of the planar premixed flames on a porous plug was performed numerically for finite activation energy within the diffusive-thermal model. The paper is focused on the influence of radiation heat loses on the flame standoff distance and its linear stability. We show that the presence of volumetric heat losses limits the range of the mass flow range as well as it can promote the flame instabilities of different kinds, both oscillatory and cellular. The oscillatory instability, which for freely propagating flames can be usually observed for the Lewis number larger than one, in the porous-plug case occurs also for flames with unity and lower than unity Lewis number. For flames with Le < 1 both cellular and oscillatory instabilities can be observed simultaneously in a certain range of the mass flow rate.     

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.     

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 adsorption and reaction of 2-butanol on clean and oxygen-covered Pd(100)

The surface chemistry of 2-butanol is explored on clean Pd(100), c(2 × 2)-O/Pd(100) and p(2 × 2)-O/Pd(100) surfaces by means of temperature-programmed desorption, reflection–absorption infrared and X-ray photoelectron spectroscopies. 2-Butanol adsorbs molecularly on clean and oxygen-covered Pd(100) below ～ 190 K, but then appears to react to form 2-butoxide species at ～ 200 K. Both 2-butanone and 2-butanol desorb from the clean surface at ～ 226 K, by β-hydride elimination from the 2-butoxide species and rehydrogenation of the 2-butoxide, respectively. In contrast, almost exclusively 2-butanone is formed on oxygen-covered surfaces. Butanone desorbs at ～ 195 K and ～ 260 K from c(2 × 2)-O/Pd(100) with the 195 K peak being the most intense. However, on p(2 × 2)-O/Pd(100), 2-butanone desorbs at ～ 195 K and ～ 295 K, and the latter peak is the most intense. The ～ 195 K, 2-butanone state is proposed to occur due to abstraction by adsorbed atomic oxygen and the change in relative intensity of these features is ascribed to the lower ability of surface hydroxyl groups to facilitate β-hydride elimination on oxygen-covered surfaces. Further heating results in the formation of hydrogen and carbon monoxide and leaves a small amount of carbon deposited on the surface.     

Flame acceleration in long narrow open channels

We study the propagation of premixed flames in long but finite channels, when the mixture is ignited at one end and both ends remain open and exposed to atmospheric pressure. Thermal expansion produces a continuous flow of burned gas directed away from the flame and towards the end of the channel where ignition took place. Owing to viscous drag, the flow is retarded at the walls and accelerated in the center, producing a pressure gradient that pushes the unburned gas ahead of the flame towards the other end of the channel. As a result the flame accelerates when it travels from end to end of the channel. The total travel time depends on the length of the channel and is proportional to γ^?1ln(1 + γ), where γ is the heat release parameter.     

Computational study on lean and rich combustion of flame ball,counterflow flame and planar flame: Their limits and stoichiometries

To investigate (fuel-)lean/rich limits and essential stoichiometries, i.e., the borders of lean/rich combustion, one-dimensional steady computations with detailed chemistry for flame balls, counterflow flames, and stretch-free planar flames were conducted using a CH₄/O₂/Xe mixture that has been used in microgravity experiments. As continuous converged solutions were obtained under lean/rich conditions, it was suggested that the existence of flame ball not only under lean but also under rich condition. Flame radii and temperatures of flame balls decreased and increased toward the lean/rich limits from their maximum and minimum values, respectively. The lean limits were wider in the order of the flame ball, counterflow flame, and stretch-free planar flame. Therefore, the lean flammability limit corresponded to the lean limit of the flame ball in the mixture. Conversely, the rich limits were wider in the order of the counterflow flame, stretch-free planar flame, and flame ball. Thus, the rich flammability limit corresponded to the rich limit of the counterflow flame in the mixture. Essential stoichiometry, which represents the actual stoichiometry depending on the dominant transport in near-flame front, was not uniquely determined as conventional stoichiometry (ϕ = 1); it was located between the equivalence ratio of ϕ = 1 and ϕ_c, where ϕ _c denotes the critical equivalence ratio is evaluated using the fuel and oxidizer Lewis number of a target mixture. The results indicated that the essential stoichiometry of the stretch-free planar flame corresponded to ϕ = 1, that of the flame ball corresponded to ϕ = ϕ _c, and that of the stretched flame was located between ϕ = 1 and ϕ _c depending on the stretch rate.