Effectiveness of flame suppressants on cool flames and hot flames

While the effectiveness of various flame suppressants such as bromotrifluoromethane and trimethylphosphate on hot flames has been relatively well studied over the years, such suppressants have not been examined in the context of low-temperature cool flames. This investigation solves this issue by exploring the extinction limits of six suppressants on both hot flames and cool flames in the counterflow geometry using n-dodecane as the fuel. In contrast to hot flames, it is found both experimentally and numerically that cool flames are relatively impervious to chemically based suppressants such as bromotrifluoromethane; these suppressants are essentially diluents at low temperatures. Detailed examination of the computed flame structure reveals that the reactions composing the catalytic cycles that interfere with hydrogen radical and hydroxyl radical production in hot flames are orders of magnitude lower in cool flames. Furthermore, mildly flammable suppressants such as trimethylphosphate and 2‑bromo-3,3,3-trifluoropropene are observed to ignite under the conditions necessary to initiate cool flames, which limits measurements of the cool flame extinction limits. This premature oxidation is not predicted by kinetic models describing the suppressant chemistry.     

Kinetic effects of NO addition on n-dodecane cool and warm diffusion flames

The kinetic effects of NO addition on the flame dynamics and burning limits of n-dodecane cool and warm diffusion flames are investigated experimentally and computationally using a counterflow system. The results show that NO plays different roles in cool and warm flames due to their different reaction pathway sensitivities to the flame temperature and interactions with NO. We observe that NO addition decreases the cool flame extinction limit, delays the extinction transition from warm flame to cool flame, and promotes the ignition transition from warm flame to hot flame. In addition, jet-stirred reactor (JSR) experiments of n-dodecane oxidation with and without NO addition are also performed to develop and validate a n-dodecane/NO_x kinetic model. Reaction pathway and sensitivity analyses reveal that, for cool flames, NO addition inhibits the low-temperature oxidation of n-dodecane and reduces the flame temperature due to the consumption of RO₂ via NO+RO₂?NO₂+RO, which competes with the isomerization reaction that continues the peroxy radical branching sequence. The model prediction captures well the experimental trend of the inhibiting effect of NO on the cool flame extinction limit. For warm flames, two different kinds of warm flame transitions, the warm flame extinction transition to cool flame and the warm flame reignition transition to hot flame, were observed. The results suggest that warm extinction transition to cool flame is suppressed by NO addition while the warm flame reignition transition to hot flame is promoted. The kinetic model developed captures well the experimentally observed warm flame transitions to cool flame but fails to predict the warm flame reignition to hot flame at similar experimental conditions.     

Studies of autoignition-assisted nonpremixed cool flames

Autoignition-assisted nonpremixed cool flames of diethyl ether (DEE) are investigated in both laminar counterflow and turbulent jet flame configurations. First, the ignition and extinction limits of laminar nonpremixed cool flames of diluted DEE are measured and simulated using detailed kinetic models. The laminar flame measurements are used to validate the kinetic models and guide the turbulent flame measurements. The results show that, below a critical mixture condition, for elevated temperature and dilute mixtures, the cool flame extinction limit and the low-temperature ignition limit merge, leading to autoignition-assisted cool flame stabilization without hysteresis. Based on the findings from the laminar flame experiments, autoignition-assisted turbulent lifted cool flames are established using a Co-flow Axisymmetric Reactor-Assisted Turbulent (CARAT) burner. The lift-off heights of the turbulent cool flames are quantified using formaldehyde planar laser-induced fluorescence. Based on an analogy with autoignition-assisted lifted hot flames, a correlation is proposed such that the autoignition-assisted cool flame lift-off height scales with the product of the flow velocity and the square of the first-stage ignition delay time. Using this scaling, we demonstrate that the kinetic mechanism that most accurately predicts the laminar flame ignition and extinction limits also best predicts the turbulent cool flame lift-off height.     

On the chemical characteristics and dynamics of n-alkane low-temperature multistage diffusion flames

We demonstrate experimentally, perhaps for the first time, the existence of low-temperature multistage diffusion flames of n-alkanes. Multistage diffusion flames of n-heptane, n-decane, and n-dodecane are established in an atmospheric counterflow burner. Planar laser-induced fluorescence, chemiluminescence, and thermometry are used to probe the structures of such flames. In the first flame zone, the majority of the fuel is partially oxidized via low-temperature peroxy chemistry. In the second flame zone, the intermediate species produced are further oxidized via intermediate-temperature chemistry. The two stages of the flame are coupled such that significant fuel and oxidizer leakage occur, respectively, from the first and second reaction zones. The fuel is then further consumed, in the second stage, after the radical pool is replenished by the oxidation of the intermediates. The structure of the n-alkane multistage flame is found to be consistent with that previously observed for acyclic ethers. Owing to the different classes of temperature-dependent chemistries dominating the first and second stages, the reaction zone structure of multistage diffusion flames is dramatically influenced by the reactant concentrations and flame temperatures. The first stage is relatively favored at lower temperatures whereas the second stage is favored at elevated temperatures. Moreover, near extinction where the flame temperature is low, the multistage flame dynamics are controlled by the first oxidation stage, governed by peroxy chemistry, whereas the second oxidation stage, governed by intermediate chemistry, is dominant near high-temperature ignition conditions. Finally, by doping the oxidizer with ozone, we demonstrate the role of ozone doping on the multistage flame structure and the existence of a separate low-temperature ozone-assisted burning mode.     

Dynamics and burning limits of near-limit hot,warm, and cool diffusion flames of dimethyl ether at elevated pressures

The near-limit diffusion flame regimes and extinction limits of dimethyl ether at elevated pressures and temperatures are examined numerically in the counterflow geometry with and without radiation at different oxygen concentrations. It is found that there are three different flame regimes—hot flame, warm flame, and cool flame—which exist, respectively, at high, intermediate, and low temperatures. Furthermore, they are governed by three distinct chain-branching reaction pathways. The results demonstrate that the warm flame has a double reaction zone structure and plays a critical role in the transition between cool and hot flames. It is also shown that the cool flame can be formed in several different ways: by either radiative extinction or stretch extinction of a hot flame or by stretch extinction of a warm flame. A warm flame can also be formed by radiative extinction of a hot flame or ignition of a cool flame. A general €-shaped flammability diagram showing the burning limits of all three flame regimes at different oxygen mole fractions is obtained. The results show that thermal radiation, reactant concentration, temperature, and pressure all have significant impacts on the flammable regions of the three flame regimes. Increases in oxidizer temperature, oxygen concentration, and pressure shift the cool flame regime to higher stretch rates and cause the warm flame to have two extinction limits. At elevated temperatures, it is found that there is a direct transition between the hot flame and warm flame at low stretch rates. The results also show that, unlike the hot flame, the cool flame structure cannot be scaled by using pressure-weighted stretch rates due to the its significant reactant leakage and strong dependence of reactivity on pressure. The present results advance the understanding of near-limit flame dynamics and provide guidance for experimental observation of different flame regimes.     

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.)     

Experimental investigation of partially premixed,highly-diluted dimethyl ether flames at low temperatures

Atmospheric-pressure highly-diluted laminar dimethyl ether (DME)–oxygen flames with temperatures below 1500 K were stabilized for the first time on a specially designed burner which allows preheating of the gas streams of fuel and oxidizer. With regard to the partially premixed structure of these flames which contain up to 90% argon in the unburnt gases, molecular-beam mass spectrometry (MBMS) with electron ionization (EI) was used to investigate chemical species profiles of reactants, intermediates, and products at a series of lateral positions and as function of distance from the burner. The flame structure reveals a near one-dimensional behavior at the flame front and beyond, towards the burnt gas. In a systematic approach, combustion parameters including stoichiometry, dilution, and gas preheating temperature were varied. The partial premixing effects upon the flame were revealed by comparing the distribution of flame species in a full two-dimensional concentration field above the burner, which is a starting point to model such flames in further studies. Formaldehyde and the methyl radical as two prominent species in the combustion process of DME were used to discuss characteristics of both high- and low-temperature kinetics.     

Extinction characteristics of isolated n-alkane fuel droplets during low temperature cool flame burning in air

Large carbon number n-alkanes are a notable component in all real transportation fuels, and their chemical structure fosters substantial low temperature kinetic reactivity. Normal alkanes have been studied in various canonical configurations but rarely in systems with strong coupling between low temperature chemistry and transport for pure as well as for multi-component n-alkane mixtures. The Flame Extinguishment (FLEX) experiments onboard the International Space Station provided a unique platform for investigating low temperature multi-phase n-alkane and iso-alkane combustion. Among the many interesting phenomena experimentally observed, cool flame extinction can occur, accompanied by the concurrent formation of a surrounding cloud of condensed vapor. In this work we conduct numerical simulations of high and low temperature combustion of large, initially single-component n-heptane, n-decane and n-dodecane droplets. The role of initial droplet diameter, operating pressure, and n-alkyl carbon number on the extinction of hot and low temperature flames is investigated and compared against the available experimental data. While all three fuels exhibit similar hot flame behavior, cool flame activity increases with the carbon number, resulting in an increased cool flame temperature and decreased extinction diameter. Multi-cyclic “hot/cool flame transitions” are found in air as pressure is slightly increased above one atmosphere. The cyclic behaviors correspond to continuously varying hot and cool flame transitions across the high, low, and negative temperature coefficient (NTC) kinetic regimes. Further increase in pressure results in a second stage steady “Warm flame” transition. The extinction of hot and cool flame has a strong non-linear dependence on ambient pressure but as the hot flame extinction diameter increases with pressure the extinction diameter of the cool flame decreases. The computational results are compared with a recent asymptotic analysis of FLEX n-alkane cool flames.     

DME/Oxygen wall-stabilized premixed cool flame

Wall-stabilized cool flames have been studied through numerical analysis and a series of experiments. One- and two-dimensional numerical simulations were performed to estimate the characteristics of the wall-stabilized cool flames, such as flammability and temperature/species distributions. Based on the computational results, the ignition condition of the cool flame at a fixed wall temperature has been identified with the strain rate between the van't Hoff point and the cool flame extinction point. In experiments with an impinging jet burner and a heated plate, the spontaneous ignition of the cool flame on the heated wall has been successfully established under the conditions predicted by the present numerical simulations. Spatial distributions of the HCHO concentration and flame temperature were measured through formaldehyde Planar Laser-Induced Fluorescence (HCHO-PLIF) and thermocouple measurements, respectively. It is found that the measurement data show a reasonable accordance with the simulation results with reduced low-temperature reactivity.     

2D computations of FREI with cool flames for n-heptane/air mixture

Two-dimensional axisymmetric numerical simulation reproduced flames with repetitive extinction and ignition (FREI) in a micro flow reactor with a controlled temperature profile with a stoichiometric n-heptane/air mixture, which have been observed in the experiment. The ignition of hot flame occurred from consumption reactions of CO that was remained in the previous cycle of FREI. Between extinction and ignition locations of hot flames, several other heat release rate peaks related to cool and blue flames were observed for the first time. After the extinction of the hot flame, cool flame by the low-temperature oxidation of n-heptane appeared first and was stabilized in a low wall temperature region. In the downstream of the stable cool flame, a blue flame by the consumption reactions of cool flame products of CH₂O and H₂O₂ appeared. After that, the hot flame ignition occurred from the remaining CO in the downstream of the blue flame. Then after the next hot flame ignition, the blue flame was swept away by the propagating hot flame. Soon before the hot flame merged with the stable cool flame, the hot flame propagation was intensified by the cool flame. After the hot flame merged with the stable cool flame, the hot flame reacted with the incoming fresh mixture of n-C₇H₁₆ and O₂.     

Spherical gas-fueled cool diffusion flames

An improved understanding of cool diffusion flames could lead to improved engines. These flames are investigated here using a spherical porous burner with gaseous fuels in the microgravity environment of the International Space Station. Normal and inverse flames burning ethane, propane, and n-butane were explored with various fuel and oxygen concentrations, pressures, and flow rates. The diagnostics included an intensified video camera, radiometers, and thermocouples. Spherical cool diffusion flames burning gases were observed for the first time. However, these cool flames were not readily produced and were only obtained for normal n-butane flames at 2 bar with an ambient oxygen mole fraction of 0.39. The hot flames that spawned the cool flames were 2.6 times as large. An analytical model is presented that combines previous models for steady droplet burning and the partial-burning regime for cool diffusion flames. The results identify the importance of burner temperature on the behavior of these cool flames. They also indicate that the observed cool flames reside in rich regions near a mixture fraction of 0.53.     

Computational and experimental study of JP-8, a surrogate, and its components in counterflow diffusion flames

Non-sooting counterflow diffusion flames have been studied both computationally and experimentally, using either JP-8, or a six-component JP-8 surrogate mixture, or its individual components. The computational study employs a counterflow diffusion flame model, the solution of which is coupled with arc length continuation to examine a wide variety of inlet conditions and to calculate extinction limits. The surrogate model includes a semi-detailed kinetic mechanism composed of 221 gaseous species participating in 5032 reactions. Experimentally, counterflow diffusion flames are established, in which multicomponent fuel vaporization is achieved through the use of an ultrasonic nebulizer that introduces small fuel droplets into a heated nitrogen stream, fostering complete vaporization without fractional distillation. Temperature profiles and extinction limits are measured in all flames and compared with predictions using the semi-detailed mechanism. These measurements show good agreement with predictions in single-component n-dodecane, methylcyclohexane, and iso-octane flames. Good agreement also exists between predicted and measured variables in flames of the surrogate, and the agreement is even better between the experimental JP-8 flames and the surrogate predictions.     

Low- and high-temperature study of n-heptane combustion chemistry

n-Heptane has been used extensively in various fundamental combustion experiments as a prototypical hydrocarbon fuel. While the formation of polycyclic aromatic hydrocarbon (PAH) in n-heptane combustion has been studied preferably in premixed flames, this study aims to investigate the combustion chemistry of n-heptane in less-studied diffusion flame and highly rich high-temperature homogeneous oxidation configurations by using a counterflow burner and a flow reactor, respectively. This work addresses the formation of higher-molecular species in the mass range up to about 160 u in both configurations. Samples are analyzed by time-of-flight (TOF) molecular beam mass spectrometry (MBMS) using electron-impact (EI) and single-photon ionization (PI). Highly resolved speciation data are reported. Laminar flow reactor experiments cover a wide temperature range. Especially the measurements at low temperatures provide speciation data of large oxygenates produced in the low-temperature oxidation of n-heptane, which are scarce in the literature. Important precursor molecules for PAH and soot formation, such as C₉H₈, C₁₀H₈, C₁₁H_10, and C₁₂H₈, are formed during the high-temperature combustion process in the counterflow flame, while oxygenated growth species are observed under low-temperature conditions, even at the fuel-rich equivalence ratio of ?=4.00.Numerical modeling for both conditions is performed by using a newly developed kinetic model of n-heptane, which includes the n-heptane and PAH formation chemistry with state-of-the-art kinetic knowledge. Good agreement between model predictions and experimental data of counterflow flame and flow reactor is observed for the major species and some intermediates of n-heptane oxidation. While the concentrations of benzene and toluene measured in the counterflow burner are well-reproduced, the numerical results for flow reactor data are not satisfactory. Differences are found between the formation pathways of fulvene, from whose isomerization benzene is produced in diffusion flame and flow reactor.     

Experimental low-stretch gaseous diffusion flames in buoyancy-induced flowfields

The present study experimentally investigates the structure and instabilities associated with extremely low-stretch (1 s⁻¹) gaseous diffusion flames. Ultra-low-stretch flames are established in normal gravity by bottom burning of a methane/nitrogen mixture discharged from a porous spherically symmetric burner of large radius of curvature. OH-PLIF and IR imaging techniques are used to characterize the reaction zone and the burner surface temperature, respectively. A flame stability diagram mapping the response of the ultra-low-stretch diffusion flame to varying fuel injection rate and nitrogen dilution is explored. In this diagram, two main boundaries are identified. These boundaries separate the stability diagram into three regions: sooting flame, non-sooting flame, and extinction. Two distinct extinction mechanisms are noted. For low fuel injection rates, flame extinction is caused by heat loss to the burner surface. For relatively high injection rates, at which the heat loss to burner surface is negligible, flame radiative heat loss is the dominant extinction mechanism. There also exists a critical inert dilution level beyond which the flame cannot be sustained. The existence of multi-dimensional flame phenomena near the extinction limits is also identified. Various multi-dimensional flame patterns are observed, and their evolutions are studied using direct chemiluminescence and OH-PLIF imaging. The results demonstrate the usefulness of the present burner configuration for the study of low-stretch gaseous diffusion flames.     

Soot formation and temperature field structure in co-flow laminar methane-air diffusion flames at pressures from 10 to 60 atm

The effects of pressure on soot formation and the structure of the temperature field were studied in co-flow methane-air laminar diffusion flames over a wide pressure range, from 10 to 60 atm in a high-pressure combustion chamber. The selected fuel mass flow rate provided diffusion flames in which the soot was completely oxidized within the visible flame envelope and the flame was stable at all pressures considered. The spatially resolved soot volume fraction and soot temperature were measured by spectral soot emission as a function of pressure. The visible (luminous) flame height remained almost unchanged from 10 to 100 atm. Peak soot concentrations showed a strong dependence on pressure at relatively lower pressures; but this dependence got weaker as the pressure is increased. The maximum conversion of the fuel’s carbon to soot, 12.6%, was observed at 60 atm at approximately the mid-height of the flame. Radial temperature gradients within the flame increased with pressure and decreased with flame height above the burner rim. Higher radial temperature gradients near the burner exit at higher pressures mean that the thermal diffusion from the hot regions of the flame towards the flame centerline is enhanced. This leads to higher fuel pyrolysis rates causing accelerated soot nucleation and growth as the pressure increases.     

The role of DME addition on the evolution of soot and soot precursors in laminar ethylene jet flames

Dimethyl ether (DME) has received considerable attention as a fuel additive to reduce the emission of particulate matter (PM) due to its low-temperature chemistry, molecularly bound oxygen atom and the absence of CC bonds. However, the effect of DME addition on the evolution of soot and particularly soot precursors is not entirely understood. This study aims to shed light on this issue by blending different proportions of DME with diffusion, E60, and partially premixed, PP12, base cases of laminar ethylene flames using the Yale benchmark burner. Laser-induced fluorescence (LIF) intensity and decay time are used to characterize the structure and evolution of soot precursors, while laser-induced incandescence (LII) is utilized to determine the soot volume fraction (SVF) and the effective primary particle diameter (D_p). For the diffusion flames, the addition of 10% DME increases the concentrations of both soot and soot precursors. With the further addition of DME to 20%, the SVF decreases to levels similar to those of E60 and then decreases further with 30% DME addition. All diffusion flames with DME addition exhibit higher concentrations of soot precursors than those of the reference E60 case. For PP12, the addition of 10% DME shows similar concentrations of soot precursors and a slight reduction in the SVF which continues to decrease with further increases in DME additions to the PP12 flame. The addition of DME seems to have little effect on the soot particle diameters for all the studied flames. Overall, the PP flames result in smaller mean particle diameters than the diffusion flame counterparts.     

Stationary combustion regimes and extinction limits of one-dimensional stretched premixed flames in a gap between two heat conducting plates

Stationary combustion regimes, their linear stability and extinction limits of stretched premixed flames in a narrow gap between two heat conducting plates are studied by means of numerical simulations in the framework of one-dimensional thermal-diffusion model with overall one-step reaction. Various stationary combustion modes including normal flame (NF), near-stagnation plane flame (NSF), weak flame (WF) and distant flame (DF) are detected and found to be analogous to the same-named regimes of conventional counterflow flames. For the flames stabilized in the vicinity of stagnation plane at moderate and large stretch rates (which are NF, NSF and WF) the effect of channel walls is basically reduced to additional heat loss. For distant flame characterized by large flame separation distance and small stretch rates intensive interphase heat transfer and heat recirculation are typical. It is shown that in mixture content / stretch rate plane the extinction limit curve has ε-shape, while for conventional counterflow flames it is known to be C-shaped. This result is quite in line with recent experimental findings and is explained by extension of extinction limits at small stretch rates at the expense of heat recirculation. Analysis of the numerical results makes possible to reveal prime mechanisms of flame quenching on different branches of ε-shaped extinction limit curve. Namely, two upper limits are caused by stretch and heat loss. These limits are direct analogs of the upper and lower limits on conventional C-shaped curve. Two other limits are related with weakening of heat recirculation and heat dissipation to the burner. Thus, the present study provides a satisfactory explanation for the recent experimental observations of stretched flames in narrow channel.     

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.     

Effect of addition of a non-equidiffusional reactant to an equidiffusional diffusion flame

A Burke–Schumann (flame-sheet) formulation is developed for diffusion flames between a fuel and oxidiser with Lewis numbers of unity, subject to addition to the fuel and/or oxidiser stream of a different reactant for which the Lewis number differs from unity. This formulation is applied to laminar counterflow diffusion-flame experiments, reported here, in which hydrogen was added to either methane–nitrogen mixtures or oxygen–nitrogen mixtures at normal atmospheric pressure, with both feed streams at normal room temperature. Experimental conditions were adjusted to fix selected values of the stoichiometric mixture fraction and the adiabatic flame temperature, and the strain rate was increased gradually, maintaining the momentum balance of the two streams, until extinction occurred. At the selected sets of values, the strain rate at extinction was measured as a function of the hydrogen concentration in the fuel or oxidiser stream. The ratio of the fraction of the oxidiser flux that consumes hydrogen to the fraction that consumes fuel was calculated from the new Burke–Schumann formulation, and it was found that, within experimental uncertainty, the ratio of the extinction strain rate with hydrogen addition to that without was the same at any given value of this oxygen flux ratio, irrespective of whether the hydrogen was added on the fuel or oxidiser side. This experimental result was also in close agreement with computational predictions employing detailed chemistry. These results imply that differences in detailed hydrogen concentration profiles within the reaction zone have little or no influence on the chemical kinetics of extinction when the stoichiometric mixture fraction, the adiabatic flame temperature, and the proportion of oxygen that consumes the added fuel are fixed. This same correspondence may be expected to apply for other fuels and additives.