Model of Cellular Instability of Flames of Ternary Mixtures

A simple phenomenological diffusive-thermal model of cellular instability of premixed flames of ternary mixtures is developed and presented. The model shows that preferential diffusion can alter stoichiometry of the mixture, i.e., the ratio of the fuel and oxidizer concentrations, and also its effective dilution by an inert. Key parameters of the model are estimated using numerical modeling of burning velocities. Laminar burning velocities are calculated for hydrogen-oxygen-nitrogen, methane-oxygen-nitrogen, and propane-oxygen-nitrogen mixtures. Conditions for the appearance of cellular instability in ternary mixtures are determined and compared with experiments. In good agreement with experimental observations, the diffusive-thermal instability is predicted in hydrogen flames with equivalence ratios φ ≲ 1.45, in lean methane flames with φ ≲ 1.02, and in rich propane flames with φ ≳ 1.03. The magnitude of the change in the local flame velocity due to preferential diffusion is evaluated. It is demonstrated that nitrogen diffuses faster than oxygen in hydrogen-air and methane-air flames, while oxygen diffuses faster than nitrogen in flames of propane and other heavier hydrocarbons. In mixtures of air with propane or heavier hydrocarbons, the transition between stable and unstable regimes is predicted in mixtures that are leaner than the mixture corresponding to the peak of the burning velocity curve, in agreement with experimental observations. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 5, pp. 14–22, September–October, 2005.     

Numerical simulation of the effect of the addition of NO and NO<Subscript>2</Subscript> on a rich hydrogen flame using the tracer method

The effect of the addition of nitric oxides (NO and NO₂) on rich hydrogen-air flames was studied using the tracer method in numerical simulation. It is shown that the effects of these additives are not similar. Both oxides promote the formation of OH and H₂O in the low-temperature zone of the front. The addition of NO reduces the first maximum of the OH profile and the burning velocity. The addition of NO₂ increases the first maximum of the OH profile and does not change the burning velocity. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 3, pp. 19–25, May–June, 2009.     

Filtration combustion of hydrogen-air, propane-air, and methane-air mixtures in inert porous media

The filtration combustion characteristics of hydrogen-air, propane-air, and methane-air mixtures in inert porous media have been studied experimentally. It is shown that the dependences of the combustion wave velocity on the fuel-air equivalence ratio are V-shaped. For hydrogen-air mixtures, the velocity minimum is shifted to the rich region, and for propane-air and methane-air mixtures, it is shifted to the lean region. For lean hydrogen-air and rich propane-air mixtures, the measured maximum temperatures in the combustion wave are found to be reduced relative to those calculated theoretically. For methane-air mixtures, a reduction in the measured temperatures is observed over the entire range of the mixture composition. The results are interpreted within the framework of the hypothesis of selective diffusion of gas mixture components. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 8–20, July–August, 2006.     

Effect of trimethylphosphate additives on the flammability concentration limits of premixed methane-air mixtures

The effect of small additives of trimethylphosphate (TMP) on the lean and rich flammability concentration limits of CH₄/air gas mixtures were studied using an opposed-flow burner and numerical modeling based on detailed kinetic mechanisms. TMP was found to narrow the flammability concentration limits of premixed CH₄/air mixtures. Modeling using a previously developed model for flame inhibition by phosphorus compounds showed that the model provides a satisfactory fit to experimental results on the effect of TMP additives on the lean concentration limit. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 1, pp. 12–21, January–February, 2008.     

Inhibition of various hydrogen combustion regimes in air by Propylene and Isopropanol

This paper studies the effects of small additives of propylene and isopropanol on the hydrogen-air flame speed in the predetonation regime, deflagration-to-detonation transition, and burning rate. It is shown that the difference in the effects of these additives on the combustion is determined primarily by their ability to terminate reaction chains. In hydrogen flames, the additives are consumed as a result of their reactions with the active intermediate products of H₂ combustion in which these species are replaced by inactive radicals.Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 1, pp. 3–14, January–February, 2005.     

Modeling combustion of lycopodium particles by considering the temperature difference between the gas and the particles

The effect of the temperature difference between the gas and the particles on propagation of premixed flames in a combustible mixture containing volatile fuel particles uniformly distributed in an oxidizing gas mixture is analyzed in this paper. It is presumed that the fuel particles vaporize first to yield a gaseous fuel, which is oxidized in the gas phase. The analysis is performed in the asymptotic limit, where the value of the characteristic Zel’dovich number is large, which implies that the reaction term in the preheating zone is negligible. Required relations between the gas and the particles are derived from equations for premixed flames of organic dust. Subsequently, the governing equations are solved by an analytical method. Finally, the variation of the dimensionless temperatures of the gas and the particles, the mass fraction of the particles, the equivalence ratio ϕ _g as a function of ϕ _u , the flame temperature, and the burning velocities of the gas and the particles are obtained. The analysis shows that the calculated value of ϕ _g is smaller than unity for certain cases, even though ϕ _u ⩾1. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 3, pp. 49–57, May–June, 2009.     

Measurement of laminar burning velocity of dimethyl ether-air premixed mixtures

Measurement of laminar burning velocity of dimethyl ether-air mixtures was taken under different initial pressures and equivalence ratios using a constant volume bomb and high-speed schlieren photography. The stretched laminar burning velocity increases with the increase of stretch rate. At equivalence ratio of 1.0, low initial pressure gives high stretched flame speed. At initial pressure less than 0.1 MPa, the stoichiometric mixture gives the higher value of stretched flame speed than those at ? = 1.2 and ? = 0.8. The Markstein numbers decrease with the increase of equivalence ratio, and this reveals that lean mixture will maintain higher stability of flame front surface than that of rich mixture in dimethyl ether-air premixed flames.     

Inhibition of Methane–Oxygen Flames by Organophosphorus Compounds

For CH₄/O₂ flames doped with trimethyl phosphate (TMP), the flame structure is examined and the velocity of flame propagation is determined with the aim of studying the mechanism of inhibition of flames doped with organophosphorus compounds. The structure of a methane–oxygen flame doped with TMP stabilized on a flat burner at a pressure of 1 atm was studied. The dependence of flame propagation velocity on the concentration of TMP is measured using a Mache–Hebra burner to determine the effectiveness of a number of MP as a flame inhibitor. The mechanism of destruction of TMP in flames was used to model the flame structure and calculate the velocities of propagation of a methane–air flame as functions of the initial concentration of TMP. Calculation and experimental results are compared.     

Skeletal mechanism of inhibition and suppression of a methane-air flame by addition of trimethyl phosphate

A skeletal mechanism of inhibition and quenching of methane flames by addition of trimethyl phosphate was developed. It includes a mechanism of methane oxidation consisting of 19 elementary steps involving 15 species (including N₂), and four elementary reactions involving three phosphorus-containing species (PO₂, HOPO, and HOPO₂). The developed skeletal mechanism adequately predicts the burning velocity of flames with added inhibitor over a range of equivalence ratio of 0.7–1.4 and can be used to model fire suppression.     

Effect of the addition of ultrafine aluminum powders on the rheological properties and burning rate of energetic condensed systems

The effect of small additives (1.25–5.00%) of ultrafine aluminum powders (UFAP) on the rheology and combustion of model four-component energetic condensed systems is studied. It is found that the addition of UFAP decreases the temperature of HMX decomposition. Small additives of UFAP increase the burning rate of model energetic condensed systems and decrease the exponent ν in the burning rate law without deteriorating the rheological characteristics of the model propellants. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 1, pp. 54–59, January–February, 2007.     

Adiabatic laminar burning velocities of CH4 + H2 + air flames at low pressures

Experimental measurements of the adiabatic burning velocity in methane + hydrogen + air flames using the Heat Flux method are presented. The hydrogen content in the fuel was varied from 0 to 20%. Non-stretched flames were stabilized on a perforated plate burner from 20 to 100 kPa. The equivalence ratio was varied from 0.8 to 1.4. Adiabatic burning velocities of CH₄ + H₂ + air mixtures were found in good agreement with the literature results at atmospheric pressure. Also low-pressure measurements in CH₄ + air flames performed earlier were accurately reproduced. The effects of enrichment by hydrogen on the laminar burning velocity at low pressures have been studied for the first time. Calculated burning velocities using the Konnov mechanism are in satisfactory agreement with the experiments over the entire range of conditions. Pressure dependences of the burning velocities for the three fuels studied could be approximated by an empirical exponential correlation.     

Role of atomic hydrogen diffusion in hydrogen flame inhibition

A laminar flame propagating in a rich homogeneous hydrogen-air mixture with addition of propylene is numerically simulated. Small amounts of propylene are shown to reduce the concentrations of HO₂ and OH in the low-temperature zone of the flame front, which effectively reduces the laminar burning velocity. In the flame front, propylene is consumed completely with formation of CO, CO₂, CH₄, C₂H₂, H₂, and H₂O, whereas hydrogen undergoes little oxidation compared to propylene. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 3–7, July–August, 2006.     

Gas combustion in a narrow channel at high pressure

This paper presents experimental results on the effect of pressure on the flame propagation velocity in a tube with diameter close to the critical diameter. An important feature of the investigated combustion regime is heat transfer along the tube wall from the combustion products to the fresh mixture. Methane-air and hydrogen-air mixtures were used. The experiments show that with increasing pressure, the burning velocity of methane-air flames decreases whereas the burning velocity of hydrogen-air flames is almost unchanged. This behavior is explained by the pressure dependence of the laminar burning velocity.     

Enhancement of combustion of a hydrogen-air mixture by excitation of O<Subscript>2</Subscript> molecules to the <Emphasis Type="Italic">a</Emphasis><Superscript>1</Superscript>Δ<Subscript><Emphasis Type="Italic">g</Emphasis></Subscript> state

The possibility of increasing the laminar flame velocity in a hydrogen-air mixture by excitation of O₂ molecules into the a ¹Δ _g singlet state. The presence of 10% of O₂(a ¹Δ _g ) molecules in oxygen is demonstrated to result in noticeable (up to 50%) enhancement of mixture burning. The temperature of combustion products and also the concentrations of H₂O, NO, and other constituents increase. The greatest effect of O₂(a ¹Δ _g ) molecules is manifested in combustion of lean mixtures; the least pronounced effect is observed in rich mixtures. These effects are caused by intensification of the chain mechanism in the presence of a super-equilibrium amount of excited O₂(a ¹Δ _g ) molecules in a hydrogen-air mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 3–12, July–August, 2008.     

Increasing the burning velocity of a low-pressure hydrogen-oxygen flame by the addition of trimethyl phosphate in terms of Zel’dovich’s chain mechanism of flame propagation

The chain reaction mechanism and theoretical approach proposed by Zel’dovich for hydrogen flame propagation are used to describe the effect of increasing the burning velocity of a low-pressure hydrogen-oxygen flame by the addition of trimethyl phosphate (TMP), which induce a catalytic recombination of hydrogen atoms. The promotion of a stoichiometric hydrogen-oxygen flame at subatmospheric pressure by the addition of TMP at a low concentration (0.1–0.5%) is described using a model of the catalytic recombination of hydrogen atoms. The results of calculation using Zel’dovich’s theory with the proposed simplified kinetic model are in good agreement with simulation results for the complete kinetic mechanism. It is shown that increasing the recombination rate of hydrogen atoms in a catalytic reaction involving phosphorus-containing species increases the heat release rate and, hence, the flame burning velocity. A kinetic analysis was performed of the dependence of the ratio of the recombination and branching rates, the temperature at the maximum reaction rate, and the maximum mole fraction of hydrogen atoms on the pressure and additive concentration. The study confirmed Zel’dovich’s prediction that the recombination not only has the harmful effect of terminating chains, but it also has the beneficial effect of releasing heat.     

Experimental and numerical study of CH4/CH3Cl/O2/N2 premixed flames under oxygen enrichment

A comprehensive experimental and numerical study has been conducted to understand the influence of CH₃Cl addition on CH₄/O₂/N₂ premixed flames under oxygen enrichment. The laminar flame speeds of CH₄/CH₃Cl/O₂/N₂ premixed flames at room temperature and atmospheric pressure are experimentally measured using the Bunsen nozzle flame technique with a variation in the amount of CH₃Cl in the fuel, equivalence ratio of the unburned mixture, and level of oxygen enrichment. The concentrations of major species and NO in the final combustion products are also measured. In order to analyze the flame structure, a detailed chemical kinetic mechanism is employed, the adopted scheme involving 89 gas-phase species and 1017 elementary forward reaction steps. The flame speeds predicted by this mechanism are found to be in good agreement with those deduced from experiments. Chlorine atoms available from methyl chloride inhibit the oxygen-enhanced flames, resulting in lower flame speeds. This effect is more pronounced in rich flames than in lean flames. Although the molar amount of CH₃Cl in the methane flame is increased, the temperature at the post flame is not significantly affected, based on the numerical analysis. However, the measured concentration of NO is reduced by about 35% for the flame burning the same amount of methyl chloride and methane at the oxygen enrichment of 0.3. This effect is due to the reduction of the concentration of free radicals related to NO production within the flame. In the numerical simulation, as CH₃Cl addition is increased, the heat flux is largely decreased for the oxygen-enhanced flame. It appears that the rate of the OH + H₂ → H + H₂O reaction is reduced because of the reduction of OH concentration. However, the function of CH₃Cl as an inhibitor on hydrocarbon flames is weakened as the level of oxygen enrichment is increased from 0.21 to 0.5. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 103–111, November–December, 2006.     

Effect of the addition of triphenylphosphine oxide,hexabromocyclododecane, and ethyl bromide on a CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame at atmospheric pressure

The chemical and thermal structure of a Mache-Hebra burner stabilized premixed rich CH₄/O₂/N₂ flame with additives of vapors of triphenylphosphine oxide [(C₆H₅)₃PO], hexabromocyclododecane (C₁₂H₁₈Br₆), and ethyl bromide (C₂H₅Br) was studied experimentally using molecular beam mass spectrometry (MBMS) and a microthermocouple method. The concentration profiles of stable and active species, including atoms and free radicals, and flame temperature pro.les were determined at a pressure of 1 atm. A comparison of the experimental and modeling results on the flame structure shows that MBMS is a suitable method for studying the structure of flames stabilized on a Mache-Hebra burner under near-adiabatic conditions. The relative flame inhibition effectiveness of the added compounds is estimated from changes in the peak concentrations of H and OH radicals in the flame and from changes in the flame propagation velocity. The results of the investigation suggest that place of action of the examined flame retardants is the gas phase. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 12–20, September–October, 2007.     

Soot formation in laminar diffusion flames of natural gas with hydrocarbon and air additive

It is shown that when acetylene, ethylene, hexane, octane, benzene, and naphthalene are introduced into natural gas, new soot particles are not formed in laminar diffusion flames and the hydrocarbon additives are expended only in particle growth. A similar effect, referred to as the inhibition of soot formation, has been observed previously during isothermal pyrolysis of hydrocarbon mixtures. Introducing air into the gas sharply reduces the yield of soot. Complete cessation of soot production, as observed from the disappearance of the luminous flame tip, corresponds to an air/natural gas ratio of 2.1. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 1, pp. 11–15, January–February 1999     

Molecular-beam mass-spectrometric study of the flame structure of composite propellants based on nitramines and glycidyl azide polymer at a pressure of 1 MPa

A study was performed of the chemical and thermal structure of flames of model composite propellants based on cyclic nitramines (RDX and HMX) and an active binder (glycidyl azide polymer) at a pressure of 1 MPa. Propellant burning rates were measured. The chemical structure of the flame was studied using molecular-beam mass spectrometry, which previously has not been employed at high pressures. Eleven species (H₂, H₂O, HCN, N₂, CO, CH₂O, NO, N₂O, CO₂, NO₂, and nitramine vapor) were identified, and their concentration profiles, including the composition near the burning surface were measured. Two chemical-reaction zones were observed. It was shown that flames of nitramine/glycidyl azide polymer propellants are dominated by the same reactions as in flames of pure nitramines. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 48–57, November–December, 2006.     

Influence of organophosphorus inhibitors on the structure of atmospheric lean and rich methane-oxygen flames

The inhibition of atmospheric laminar methane-oxygen flames of various compositions by trimethyl phosphate was studied experimentally and by numerical modeling using mechanisms based on detailed kinetics. The H and OH concentration profiles in flames with and without the addition of trimethyl phosphate were measured and calculated. It was shown that the addition of the inhibitor reduced the maximum (in the reaction zone) concentrations of H and OH in lean and rich flames. The concentration reduction was higher in rich flames than in lean flames. The concentration profiles of the phosphorus-containing products PO, PO₂, HOPO, HOPO₂, and (HO)₃PO in lean and rich flames stabilized on a flat burner were measured and calculated. Tests of the previously developed model of flame inhibition by phosphorus compounds showed that the model provides adequate predictions of many experimental results. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 2, pp. 23–31, March–April, 2007.