Modeling of HMX combustion

A mechanism of HMX combustion was proposed and the corresponding model was developed under the assumption that the combustion wave consists of two zones, with consideration given to the reaction of decomposition and vaporization of the initial energetic material in the condensed phase and the subsequent decomposition of its vapor in the gas phase. An analysis of the results showed that, at low pressures, the burning rate is largely determined by the exothermic decomposition of the material in the condensed phase, but at pressure above ∼20 atm, the processes in the gas phase begin to play an increasingly important role, where the limiting process is the bimolecular activation reaction with the subsequent dissociation of HMX accompanied by the secondary reactions between the products. A comparison of the calculation results with experimental data showed that the model adequately describes a number of characteristics of the combustion wave and ballistic properties, such as the burning rate and its sensitivity to pressure and initial temperature.     

Effects of Explosive Particle Microstructure Parameters on NQR Parameters in RDX

The effects of the particle size, density and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) content on 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) nuclear quadrupole resonance (NQR) line have been studied at 5, 10, 15 and 20?°C. The RDX line at 3.41?MHz has been measured in 17 different quality lots. The RDX line was not modified in this temperature range but was strongly altered in some lots. No significant correlation was found between line characteristics and particle sizes or particle bulk densities. Correlation coefficients were computed between the HMX content measured using high-performance liquid chromatography and the NQR line intensity and NQR line width. Significant correlations were found. They were based on the study of 11 RDX lots which exhibited 4 different HMX contents from 0 to about 9 percent in weight. Further studies are needed to precise the HMX effect in relation with the HMX location. HMX can be located inside or outside the RDX crystal. Further studies are also needed to determine the line broadening mechanism.     

Unreacted equation of states of typical energetic materials under static compression:A review

The unreacted equation of state(EOS) of energetic materials is an important thermodynamic relationship to characterize their high pressure behaviors and has practical importance. The previous experimental and theoretical works on the equation of state of several energetic materials including nitromethane, 1,3,5-trinitrohexahydro-1,3,5-triazine(RDX),1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane(HMX), hexanitrostilbene(HNS), hexanitrohexaazaisowurtzitane(HNIW or CL-20), pentaerythritol tetranitrate(PETN), 2,6-diamino-3,5-dinitropyrazine-1-oxide(LLM-105), triamino-trinitrobenzene(TATB), 1,1-diamino-2,2-dinitroethene(DADNE or FOX-7), and trinitrotoluene(TNT) are reviewed in this paper. The EOS determined from hydrostatic and non-hydrostatic compressions are discussed and compared. The theoretical results based on ab initio calculations are summarized and compared with the experimental data.     

Flame structure of HMX/GAP propellant at high pressure

The chemical and thermal structure of a HMX/GAP propellant flame was investigated at a pressure of 0.5 MPa using molecular beam mass spectrometry and a microthermocouple technique. The pressure dependence of the burning rate was measured in the pressure range of 0.5–2 MPa. The mass spectrometric probing technique developed for flames of energetic materials was updated to study the chemical structure of HMX/GAP flames at high pressures. Eleven species, including HMX vapor, were identified, and their concentrations were measured in a zone adjacent to the burning surface at pressures of 0.5 and 1 MPa. Temperature profiles in the propellant combustion wave were measured at pressures of 0.5 and 1 MPa. Species concentration profiles were measured at 0.5 MPa. Two main zones of chemical reactions in the flame were found. The data obtained can be used to develop and validate combustion models for HMX/GAP propellants.     

Factors affecting the NQR line width in nitramine explosives

A number of factors associated with crystal quality contribute to the nuclear quadrupole resonance (NQR) line width. Imperfections such as dislocations, voids, strain and impurities can be electrical sources that distort the electric field gradient at nearby quadrupolar nuclei and broaden the observed NQR line. We measured the¹⁴N NQR line widths in powdered samples of the nitramine explosives hexahydro-1,3,5-trinitro-s-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and show correlations with sample purity, particle size distribution and density. Cast plastic-bonded explosives containing either RDX or HMX were also studied and their line widths compared with those of the powdered samples.     

A method to calculate the thermal conductivity of HMX under high pressure

A method based on Debye theory is developed to calculate the thermal conductivity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The phonon–phonon interaction model is built up for solid HMX. The phonon lifetime formula is derived by the phonon–phonon scattering mechanism, and the thermal conductivity tensor is derived by the phonon dispersion model. The thermal conductivities of α/β/δ-HMX are calculated in the temperature range 0–700?K and pressure range of 0–10?GPa. The phonon softening process of HMX is investigated. We have proven that the Debye frequency and thermal conductivity tend to 0 at the phonon softening point. A physical picture of the phonon–phonon interaction, phonon lifetime and phonon softening is built up.     

The pressure-induced phase transition of the solid β–HMX

The structural, vibrational and thermodynamic properties of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (β–HMX) crystal have been studied using the isothermal-isobaric molecular dynamics (NPT-MD) simulations. The variations of cell volume, lattice constants and molecular geometry of solid β–HMX are presented and discussed at different pressure and temperature. It was found that the N–N bond is significantly lengthened with increasing temperature, which suggests that it is relevant to the initial decomposition. An abrupt change at 27 Gpa for the volume and internal geometrical parameters was observed. This is in good accord with the experimental observation that there is a phase transition at 27 GPa, which is clearly due to conformational change, not chemical reaction. The vibrational frequencies at ambient conditions agree well with experimental results, and the pressure/temperature-induced frequency shifts of these modes are discussed. Frequency discontinuity was also observed at pressure when the phase transition occurred. The Grüneisen parameter was obtained using the vibrational frequency.     

环五甲撑五硝胺(CRX)结构和性质的DFT预示

用密度泛函理论 (DFT)B3LYP方法 ,在 6 31G 基组水平下 ,全优化计算了环五甲撑五硝胺 (CRX)的分子几何和优化构型下的电子结构 .环C -N键长为 0 .144～ 0 .148nm ,N -NO2 键长为 0 .139～ 0 .142nm ;CRX的最高占有MO(HOMO)能级和最低未占MO(LUMO)能级之间的差值ΔEg(5 .2 0 5 4eV)较大 ,预示CRX较稳定 .基于简谐振动分析求得IR谱频率和强度 .运用统计热力学方法 ,求得在 2 0 0～ 12 0 0K的热力学性质C0p ,m、S0 m 和H0 m.还运用Kamlet公式预示了它的爆速和爆压分别为 916 9m/s和 37.88GPa .     

Role of gas- and condensed-phase kinetics in burning rate control of energetic solids

A simplified two-step kinetics model for the combustion of energetic solids has been used to investigate the effect of gas-phase activation energy on flame structure and burning rate and the role of gas- versus condensed-phase kinetics in determining burning rate. The following assumptions are made: a single-step, unimolecular, high activation energy decomposition process which is overall relatively energetically neutral, is followed by a highly exothermic single-step, bimolecular, gas-phase reaction with arbitrary activation energy, E? _g. The results show that at extremely low (<10⁴ Pa) or high (>10¹² Pa) pressures the burning rate is controlled by the condensed-phase reaction kinetics for any E?_g. At intermediate pressures (10⁵-10¹⁰ Pa) gas reaction kinetics contribute strongly to the burning rate. In this pressure range the value of E?_g plays an important function in determining the role of gas- and condensed-phase reactions: for high E?_g a gas-phase kinetically controlled regime exists; for low E?_g both condensed and gas-phase kinetics are important. The limiting behaviour of asymptotically large E?_g (gas kinetically controlled burning rate) occurs at about E?_g=20 kcal mol^?1 for parameters representative of HMX, while the vanishingly small E?_g behaviour occurs near E?_g. Previous comparison with burning rate and temperature profile data has suggested that the small-E?_g limit is the more accurate of the two extremes. This may imply that the important (burning rate influencing) primary gas reaction zone near the surface has more the character of a chain reaction mechanism than the classical high activation energy thermal decomposition mechanism. To the degree that the low-E?_g chain reaction model is a better approximation than the high-E?_g thermal decomposition model, the possibility exists that the chemistry of either reaction zone, including the molecular structure of the material, might be exploited for favourable tailoring of burning rate. The low-E?_g model also provides a rational mechanistic explanation of observed trends in burning rate temperature sensitivity with pressure and temperature for materials like HMX in terms of a gradual transition from mixed gas- and condensed-phase kinetic control to condensed-phase only kinetic control as the pressure decreases.     

DFT studies on a high-energy density cage compound 1, 3, 5, 7, 9, 11-hexo(N(CH3)NO2)-2, 4, 6, 8, 10, 12-hexaazatetracyclo[5, 5, 0, 0, 0] dodecane

The infrared and Raman spectra, heat of formation (HOF) and thermodynamic properties were investigated by B3LYP/6-31G^** method for a new designed polynitro cage compound 1,3,5,7,9,11-hexo(N(CH₃)NO₂)-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0,0]dodecane. The detonation velocity (D) and pressure (P) were predicted by the Kamlet–Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analysed to investigate the thermal stability of the title compound. The computational result shows that the detonation velocity and pressure of the title compound are superior to those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), but inferior to those of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and hexanitrohexaazaisowurtzitane (HNIW). And the analysis of thermal stability shows that the first step of pyrolysis is the rupture of the N₇–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to the P2₁ space group, with the lattice parameters Z = 2, a = 11.8246 Å, b = 10.4632 Å, c = 15.9713 Å, ρ = 1.98 g cm^?3.     

Optimization of global kinetics parameters for heterogeneous propellant combustion using a genetic algorithm

We examine the combustion of heterogeneous propellants for which, necessarily, the chemical kinetics is modelled using simple global schemes. Choosing the parameters for such schemes is a significant challenge, one that, in the past, has usually been met using hand-fitting of experimental data (target data) for global burning properties such as steady burning rates, burn-rate temperature sensitivity, and the like. This is an unsatisfactory strategy in many ways. It is not optimal; and if the target set is large and includes such things as stability criteria, or bounds, difficult to implement. Here we discuss the use of a general optimization strategy which can handle large data sets of a general nature. The key numerical tool is a genetic algorithm that uses MPI on a parallel platform. We use this strategy to determine parameters for HMX/HTPB propellants and AP/HTPB propellants. Only one-dimensional target data are used, corresponding to the burning of pure HMX (AP) or a homogenized blend of fine HMX (AP) and HTPB. The goal is to generate kinetics models that can be used in the numerical simulation of three-dimensional heterogeneous propellant combustion. The results of such simulations will be reported in a sequel.     

Theoretical studies on the structure,sensitivity, density,thermodynamic properties and detonation performance of dinitrobitriazoles

Azodinitro- and dinitroethylene-bridged bitriazoles are of interest in the contest of high explosives, and were found to have true local energy minima at the B3LYP/aug-cc-pVDZ level of theory. The optimised structures, vibrational frequencies and thermodynamic quantities for bitriazoles were obtained in the ground state. Kamlet–Jacobs equations were used to evaluate the performance of bitriazoles based on the predicted density and the calculated heat of explosion. Detonation properties (D = 8.12 to 9.23 km s^?1 and P = 28.0 to 39.83 GPa) of bitriazoles were found to be promising compared with those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, D = 8.75 km s^?1 and P = 34.7 GPa) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, D = 8.96 km s^?1 and P = 35.96 GPa). The fusion of azoles particularly appears to be a promising area for investigation, since it may lead to the desirable consequences of higher heat of explosion, higher density and thus improved detonation performance.     

Modified double-base propellants: Combustion wave parameters and burning rate response functions

The burning rates of modified double-base propellant at various pressures and initial temperatures were determined. The sensitivities of the combustion wave characteristics to the pressure and initial temperature were obtained. The functions of response of the burning rate to oscillatory pressure were calculated. Three types of response functions were identified. The errors in determination of these functions were estimated.     

A detailed chemical kinetic model for gas phase combustion of TNT

A detailed chemical kinetic mechanism for gas phase combustion of 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and of soot formation during the destruction of munitions. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reactions for the decomposition and oxidation of TNT and its intermediate products are assembled, based on information from the literature and from analogous reactions where the rate constants are available. The resulting detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons which can be produced from TNT and RDX. Properties of the reaction mechanism are demonstrated by examining problems of soot formation during open burning of TNT and mixtures of TNT and RDX. Computed results show how addition of oxygen to TNT can reduce the amounts of soot formed in its combustion and why RDX and most mixtures of RDX and TNT do not produce soot during their combustion or incineration.     

Three stage cool flame droplet burning behavior of n-alkane droplets at elevated pressure conditions: Hot,warm and cool flame

Transient, isolated n-alkane droplet combustion is simulated at elevated pressure for helium-diluent substituted-air mixtures. We report the presence of unique quasi-steady, three-stage burning behavior of large sphero-symmetric n-alkane droplets at these elevated pressures and helium substituted ambient fractions. Upon initiation of reaction, hot-flame diffusive burning of large droplets is initiated that radiatively extinguishes to establish cool flame burning conditions in nitrogen/oxygen “air” at atmospheric and elevated pressures. However, at elevated pressure and moderate helium substitution for nitrogen (X_He?>?20%), the initiated cool flame burning proceeds through two distinct, quasi-steady-state, cool flame burning conditions. The classical “Hot flame” (～1500?K) radiatively extinguishes into a “Warm flame” burning mode at a moderate maximum reaction zone temperature (～ 970?K), followed by a transition to a lower temperature (～765?K), quasi-steady “Cool flame” burning condition. The reaction zone (“flame”) temperatures are associated with distinctly different yields in intermediate reaction products within the reaction zones and surrounding near-field, and the flame-standoff ratios characterizing each burning mode progressively decrease. The presence of all three stages first appears with helium substitution near 20%, and the duration of each stage is observed to be strongly dependent on helium substitutions level between 20–60%. For helium substitution greater than 60%, the hot flame extinction is followed by only the lower temperature cool flame burning mode. In addition to the strong coupling between the diffusive loss of both energy and species and the slowly evolving degenerate branching in the low and negative temperature coefficient (NTC) kinetic regimes, the competition between the low-temperature chain branching and intermediate-temperature chain termination reactions control the “Warm” and “Cool” flame quasi-steady conditions and transitioning dynamics. Experiments onboard the International Space Station with n-dodecane droplets confirm the existence of these combustion characteristics and predictions agree favorably with these observations.     

Flame structure of composite pseudo-propellants based on nitramines and azide polymers at high pressure

The chemical and thermal structures of flame of composite pseudo-propellants based on cyclic nitramines (HMX, RDX) and azide polymers (GAP and BAMO–AMMO copolymer) were investigated at a pressure of 1.0 MPa by molecular beam mass spectrometry and a microthermocouple technique. Eleven species H₂, H₂O, HCN, CO, CO₂, N₂, N₂O, CH₂O, NO, NO₂, and nitramine vapor (RDX_v or HMX_v), were identified, and their concentration profiles were measured in HMX/GAP and RDX/GAP pseudo-propellant flames at a pressure of 1 MPa. Two main zones of chemical reactions in the flame of nitramine/GAP pseudo-propellants were found. In the first, narrow, zone 0.1 mm wide (adjacent to the burning surface), complete consumption of nitramine vapor and NO₂ with the formation of NO, HCN, CO, H₂, and N₂ occurs. In the second, wider high-temperature zone, oxidation of HCN and CH₂O by NO and N₂O with the subsequent formation of CO, H₂, and N₂ takes place. The leading reactions in the high-temperature zone of flame of nitramine/GAP pseudo-propellants are the same as in the case of pure nitramines. In the case of nitramine/BAMO–AMMO pseudo-propellants a presence of carbonaceous particles on the burning surface did not allow us to analyze the zone adjacent to the burning surface, therefore only one flame zone was found. Temperature profiles in the combustion wave of nitramine/azide polymer pseudo-propellants were measured at 1 MPa. The data obtained can be used to develop and validate a self-sustain combustion model for pseudo-propellants based on nitramines and azide polymers.     

天然气在不同初始温度和压力下的燃烧特性研究

利用定容燃烧弹研究了不同初始温度和初始压力下的天然气燃烧特性,分析了初始温度、初始压力和当量比对其燃烧过程的影响.研究结果表明:随着初始温度的升高(300～450 K),天然气质量燃烧速率明显增加,燃烧持续期和火焰发展期显著缩短.随着初始压力的升高(0.1～0.75 MPa),天然气质量燃烧速率明显减慢,燃烧持续期和火焰发展期显著增长.且稀混合气和浓混合气条件下初始温度和初始压力的变化对燃烧持续期和火焰发展期的影响更明显.     

Calculation of the unsteady burning velocity according to a known law of pressure variation during transient processes in a solid-propellant rocket engine

The burning velocity during pressure decay in a model solid-propellant engine caused by the opening of an additional nozzle concurrently with the operation of the main nozzle is calculated; i.e., the inverse problem of internal ballistics is solved. The calculations are performed using experimental pressure versus time dependences and the laws of conservation of mass and energy in the thermodynamic and isothermal approximations. The problem is solved in two formulations: using the basic parameters of the combustion chamber before depressurization and in a formulation based on using initial conditions for pressure decay. In the latter case, the unsteady burning velocities are smaller than the corresponding steady-state velocities at the same pressures and close to the calculated velocities obtained for the same pressure decays by solving the direct problem.     

弱点火条件下炸药燃烧转爆轰的数值模拟

考察颗粒炸药从传导燃烧到对流燃烧再到爆轰的过程.对装填密度为85%的HMX颗粒炸药的燃烧转爆轰过程进行数值模拟,分析传导燃烧、对流燃烧和爆轰的发展过程.点火早期燃烧速度很低,火焰面在8.16 ms之内只前进了不到0.2 mm;形成对流燃烧之后燃烧速度快速增加,只用了0.1 ms就形成了速度为8 165 m·s^-1的稳定爆轰.当炸药颗粒直径或点火压力减小时,形成稳定爆轰所需的时间增加.     

Generalized analytical expressions for the burning velocity in a combustion model with non-constant transport coefficients and several specific heats

We derive new expressions to estimate the burning velocity of a laminar gas flame in a simplified combustion model based on a one-step single reaction with transport coefficients (mass and heat) depending on temperature, and species with different specific heats. These new expressions generalize the bounds and approximations previously derived by Williams, von Karman, Zeldovich and Frank-Kamenetskii, Benguria and Depassier, and the matching asymptotic expansion method in a two zone model. The comparison of the flame speed predicted by these new analytical expressions with that numerically simulated by the full combustion model for a large variety of cases allows us to determine their range of validity. The upper bound based on the Benguria and Depassier method provides very good approximations for the actual propagation speed of combustion flames, being substantially better than the asymptotic method used in the recent papers.