含能材料燃烧过程中热分解化学的研究进展

从模拟燃烧条件、组分相互作用、组分物理状态、分析测试技术等几方面介绍了含能材料燃烧过程中热分解化学研究近几年来的最新进展。着重介绍燃烧热分解中的基元反应对建立推进剂燃烧新型模型的重要性、氧化剂和黏合剂及催化剂之间的相互作用、氧化剂的黏度和相态变化对燃烧和热分解过程的影响。     

On the nature of the burning rate-controlling reaction of energetic materials for the gas-phase model

For model systems with known kinetics of elementary reactions (CH₃NO₂ and HN₃), temperature ranges are established in which the rate-controlling reactions are the initial endothermic decomposition of the starting material or the subsequent secondary reactions. Heat release in reactions of NO₂, NO, and N₂O with various fuels, such as CH₂O, CO, H₂, and HCN, is modeled to establish the kinetic parameters and nature of the rate-controlling reactions in gas flames of nitro compounds. It is shown that the activation energy of the heat-release reaction due to the interaction of NO₂ with a hydrocarbon fuel (which is characteristic of the first flame of nitro compounds) is in the range of 29–33 kcal/mole, depending on the type of fuel. According to the calculations performed, the activation energy of the rate-controlling heat-releasing process due to the deoxidation of NO and N₂O (which is typical of the second flame of nitro compounds) is 43–58 kcal/mole. In the range of high pressures, where the flames merge, the kinetic parameters of heat release are determined by the reactions of the most reactive nitrogen oxide NO₂. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 3, pp. 59–71, May–June, 2007.     

Thermal Decomposition and Combustion of Ammonium Dinitramide (Review)

A comprehensive review of thermal decomposition and combustion of ammonium dinitramide (ADN) has been conducted. The basic thermal properties, chemical pathways, and reaction products in both the condensed and gas phases are analyzed over a broad range of ambient conditions. Detailed combustion-wave structures and burning-rate characteristics are discussed. Prominent features of ADN combustion are identified and compared with other types of energetic materials. In particular, the influence of various condensed- and gas-phase processes in dictating the pressure and temperature sensitivities of the burning rate is examined. In the condensed phase, decomposition proceeds through the mechanisms ADN → NH₄NO₃ + N₂O and ADN → NH₃ + HNO₃ + N₂O, the former mechanism being the basic one. In the gas phase, the mechanisms ADN → NH₃ + HDN and ADN → NH₃ + HNO₃ + N₂O are prevalent. The gas-phase combustion-wave structure in the range of 5–20 atm consists of a near-surface primary flame followed by a dark-zone temperature plateau at 600–1000°C and a secondary flame followed by another dark-zone temperature plateau at 1000–1400°C. At higher pressures (60 atm and above), a final flame is observed at about 1800°C without the existence of any dark-zone temperature plateau. ADN combustion is stable in the range of 5–20 atm and the pressure sensitivity of the burning rate has the form r _b = 20.72p ^0.604 [mm/sec] (p = 0.5–2.0 MPa). The burning characteristics are controlled by exothermic decomposition in the condensed phase. Above 100 atm, the burning rate is well correlated with pressure as r _b = 8.50p ^0.608 [mm/sec] (p = 10–36 MPa). Combustion is stable, and intensive heat feedback from the gas phase dictates the burning rate. The pressure dependence of the burning rate, however, becomes irregular in the range of 20–100 atm. This phenomenon may be attributed to the competing influence of the condensed-phase and gas-phase exothermic reactions in determining the propellant surface conditions and the associated burning rate. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 54–79, November–December, 2005.     

冷壁效应作用下双基药的燃烧特征

为研究冷壁效应作用下火药燃烧过程及其影响规律,采用常压燃烧实验和定容燃烧实验研究了双基药在壁面基体材料冷壁作用下的燃烧特性。结果表明,常压与定容燃烧条件下冷壁效应作用都会使双基药的燃烧变得不稳定,燃烧速率明显变慢,并在一定条件下燃烧熄灭并形成残药;随着基体材料热传导率的提高,冷壁效应作用效果逐渐增强,导致双基药燃烧时间延长,燃烧最大压力和燃烧速率都逐渐降低。     

Numerical study of coal particle cluster combustion under quiescent conditions

Behavior of ignition and combustion of coal particle cluster under a quiescent condition was numerically simulated by solving balance equations of mass and enthalpy with combustion kinetic models of volatiles and char. Two-flame structure, one flame penetrating into the cluster and the other moving out of the cluster, was predicted during the combustion of coal particle cluster. Effects of radiative heat transfer, group number, ambient temperature, coal particle size, and oxygen concentration on ignition and combustion of coal particle clusters were also analyzed. Simulations indicated that the gas volume fraction of coal particle cluster increases with time after devolatilization. Gas velocity passing through the cluster surface varied significantly at volatile liberation. The ignition time delay was reduced with the increase of ambient temperature. The cluster devolatilization rate and char burning rate increased while the ignition time delay decreased with the increase of ambient oxygen concentration.     

含能黏合剂合成研究新进展

从热塑性含能黏合剂和热固性含能黏合剂两方面综述了国内外含能黏合剂近5年研究的最新进展,重点介绍了叠氮类、硝酸酯类、富氮含能类、聚磷氮烯类、改性端羟基聚丁二烯类热塑性含能黏合剂,GAP基ETPE、BAMO基ETPE、偕二硝基类热塑性含能黏合剂的合成及性能研究情况,对含能黏合剂研究的发展趋势进行了展望,附参考文献25篇.     

Phase,microstructure and sintering of aluminum nitride powder by the carbothermal reduction-nitridation process with Y2O3 addition

Aluminum nitride powders were synthesized by carbothermal reduction-nitridation method using Al(OH)₃, carbon black and Y₂O₃ as raw materials. The change of phase, microstructure and densification during the AlN synthesis and sintering process were investigated and the effects of Y₂O₃ was discussed. The results showed that Y₂O₃ reacted with Al₂O₃ to form yttrium aluminates of YAlO₃ (orthorhombic and hexagonal phases), Y₄Al₂O₉ and Y₃Al₅O₁₂ at the low temperature of 1350 °C. YAlO₃ could firstly be transformed into Y₂O₃ and then completely into YN when the firing temperature and holding time increased. However, YN could be oxidized into Y₂O₃ again after the carbon removal at 700 °C in the air atmosphere. There were two ways generating AlN when adding Y₂O₃ and the possible mechanism was proposed. Y₂O₃ from YN oxidation favored the densification of AlN ceramics because the liquid had better flowability and distribution in the sintering process at 1800 °C.     

Microstructure evolution and simulation of copolymerization reaction using a percolation kinetic gelation model

A new kinetic gelation model that incorporates the kinetics of non-linear free radical copolymerization is presented. Copolymerization of bi- and tetrafunctional monomer mixtures is simulated to characterize kinetic effects on polymerization statistics and microstructures. An algorithm for random next step selection in a self-avoiding random walk and efficient mechanisms of component's mobility are introduced to improve the universality of the predictions by removing commonly occurring simulation deficiencies due to early trapping of radicals. The model has the capability to predict the onset of the sol-gel transition, and the effect of chemical composition on the transition point. It is shown that a better understanding of microstructure evolution during polymerization and chemical gelation is attained. Lastly, one important benefit of the simulation method is the ability to simulate very highly packed random chains or microgels within a polymer network.     

Influence of polymer modulus on the percolation threshold of latex-based composites

Monodispersed copolymer emulsions with different glass transition temperatures were synthesized to investigate the effect of room temperature polymer matrix modulus on the electrical properties of carbon black (CB) filled segregated network composites. The emulsion with the highest modulus at room temperature produced composites with the lowest percolation threshold. The threshold for a composite made from a copolymer latex containing an equal ratio of butyl acrylate and methyl methacrylate (BA5) is 1.5 vol%, while the percolation threshold for the much lower modulus BA7 (7:3 BA/MMA ratio) is 4.93 vol%. The microstructure of each composite shows significant differences in the level of CB dispersion within the polymer matrix. Higher modulus polymer particles push the CB more efficiently into the interstitial space between them, resulting in a lower percolation threshold. This modulus effect was confirmed by increasing the drying temperature, where the moduli of latexes (BA5, BA5.5, and BA6) were more similar and the percolation thresholds for three composites also become closer to one another.     

Dramatically enhanced non-Ohmic properties and maximum stored energy density in ceramic-metal nanocomposites: CaCu3Ti4O12/Au nanoparticles

Non-Ohmic and dielectric properties of a novel CaCu₃Ti₄O₁₂/Au nanocomposite were investigated. Introduction of 2.5 vol.% Au nanoparticles in CaCu₃Ti₄O₁₂ ceramics significantly reduced the loss tangent while its dielectric permittivity remained unchanged. The non-Ohmic properties of CaCu₃Ti₄O₁₂/Au (2.5 vol.%) were dramatically improved. A nonlinear coefficient of ≈ 17.7 and breakdown electric field strength of 1.25 × 10⁴ V/m were observed. The maximum stored energy density was found to be 25.8 kJ/m³, which is higher than that of pure CaCu₃Ti₄O₁₂ by a factor of 8. Au addition at higher concentrations resulted in degradation of dielectric and non-Ohmic properties, which is described well by percolation theory.     

超细含能材料表征技术研究进展

综述了超细含能材料的表征技术研究现状,对超细含能材料的表征技术变化进行了分析,提出了今后的研究方向,即充分发挥多学科优势,进一步开展超细含能材料表征技术及作用机理的研究,以获得具有实际应用价值的超细含能材料的表征技术方法。