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。     

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.     

含能材料分子设计与性能预测研究

利用分子设计软件预测含能材料的物化性能及爆炸参数,并与实测值进行了比较。结果表明,TNT分子理论预测值与实测值基本一致;八硝基立方烷的爆炸参数,除爆速相差较大外,其他参数与实测值接近。     

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.     

Thermal decomposition kinetics and compatibility of NH3OHN5

Hydroxylammonium cyclo-pentazolate (NH₃OHN₅), as one of the poly-nitrogen compounds, has a broad prospect in the field of energetic materials, due to its high specific impulse, high detonation velocity, and the pollution-free products. In this paper, the thermal decomposition behavior of NH₃OHN₅ was studied by differential scanning calorimetry (DSC) using four heating rates (2, 5, 8, 10 °C min⁻¹). The apparent activation energy (E_K,O=114.31 kJ mol⁻¹), the pre-exponential factor (A_K=4.78×10¹¹ s⁻¹) and the critical temperature of the thermal explosion (T_b=108.08 °C) of NH₃OHN₅ were calculated by Kissinger and Ozawa method under non-isothermal heating conditions. The compatibility of NH₃OHN₅ with 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaza-isowurtzitane (CL-20), ammonium perchlorate (AP), and hydroxy-terminated polybutadiene (HTPB) were tested and judged based on a standard agreement (STANAG-4147). The DSC results showed that NH₃OHN₅/HMX, NH₃OHN₅/RDX, NH₃OHN₅/CL-20, NH₃OHN₅/AP and NH₃OHN₅/HTPB had good compatibility.     

Highly Thermal Stable TATB‐based Aluminized Explosives Realizing Optimized Balance between Thermal Stability and Detonation Performance

In this work, a series of TATB‐based aluminized explosives were formulated from 1, 3, 5‐triamino‐2, 4, 6‐trinitrobenzene (TATB), aluminum powders and polymeric binders. The thermal stability, heat of detonation, detonation velocity and pressure of the TATB based aluminized (TATB/Al) explosives were systematically investigated by cook‐off, constant temperature calorimeter, electrometric method and manganin piezo resistance gauge, respectively. The selected PBX‐3 (70 wt% TATB/25 wt% Al/5 wt% fluorine resin) achieved optimized balance between thermal stability and detonation performance, with the thermal runaway temperature around 583 K. The thermal ignition of TATB‐based aluminized explosive occurred at the edge of the cylinder according to the experimental and numerical simulations. Moreover, the critical thermal runaway temperature for PBX‐3 was calculated based on the Semenov's thermal explosion theory and the thermal decomposition kinetic parameters of the explosive, which was consistent with the experimental value.     

含能配合物Ni（C5N5O5H-4）2（by）2的晶体结构和热分解性能

培养了含能配合物Ni(C5N5O5H42)(by2)(by=吡啶)晶体,用X射线单晶衍射法测定了其分子结构。其晶体属于单斜晶系,空间群为P21/C,a=9.0070(18)nm,b=10.002(2)nm,c=19.445(4)nm,β=93.69(3),V=1748.1(6)nm3,μ=0.633mm-1,Z=4,S=1.00,最终残差因子[I>2σ(I)]R1=0.0530,WR2=0.1162,对于全部数据R1=0.0965,WR2=0.1358。用DSC、TG-DTG对该配合物的热分解过程进行了研究。结果表明,该配合物的热分解过程仅由1个剧烈的放热峰组成,剩余残渣量约5.508%。用Kissinger法和Ozawa-Doyle法计算出配合物热分解过程中的表观活化能和指前因子分别为224.30kJ/mol和7.32×1019s-1。     

Thermal behavior of gradient charring materials with improved iterative method

The lightweight material of the thermal protection system for a reentry vehicle has become a trend in order to maximize the payload. To explore the effect of gradient density on the thermal behavior of charring materials, a pyrolysis layer model considering of variable density is developed and discretized with the central difference method. An iterative method is improved to look for the locations of the moving interfaces and boundary in each time step. Taken different gradient phenolic impregnated carbon ablator under a return trajectory heat flux for the Orion vehicle as example, their thermal behavior and effective heat capacities are simulated using the code written. Numerical results indicate that the gradient designs can improve the thermal protection performance of charring materials effectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47076.     

腐殖酸热分解动力学

采用热重分析法（DTA-TGA）研究了腐殖酸的热分解过程及其动力学,分析其DTA-TGA曲线可得：热分解反应发生在284.65～417.16℃; 用红外光谱（FT-IR）、核磁氢谱（¹H NMR）、核磁碳谱（¹³C NMR）对腐殖酸结构进行表征,用Flynn-Wall-Ozawa（F-W-O）法、Kissinger法及Šatava-Šesták法计算出腐殖酸热分解反应的表观活化能为210.83 kJ·mol^-1,指前因子对数为17.55;确定了其热分解反应的级数和动力学参数,且热分解反应机理为二级反应;腐殖酸在氮气氛围下维持1min寿命的最高使用温度为278℃;同时,计算出腐殖酸样品热力学参数焓变、熵变及摩尔自由能变分别为67.99 kJ·mol^-1、-164.83 J·（mol·K）^-1 和176.36 kJ·mol^-1。     

苦味酸碳酰肼含能配合物的制备及其对CL-20热分解的影响

用碳酰肼、苦味酸与相应的金属盐在水溶液中反应制备出苦味酸碳酰肼钴、铜、铅含能配合物Co(CHZ)4(PA)2.3H2O、Cu(CHZ)4(PA)2.4H2O和Pb(CHZ)2(PA)2.4H2O(CHZ为碳酰肼,PA为苦味酸),通过元素分析和FT-IR分析对产物进行了分子式推测。用标准方法测定了含能配合物的撞击、摩擦和火焰感度,应用DSC和TG-DTG法测试了含能配合物对CL-20热分解过程的影响。结果表明,含能配合物都能够一定程度降低CL-20的起始分解温度和峰值,用Kissinger法和Ozawa-Doyle法获得了含能配合物/CL-20混合物的第一放热分解过程的活化能Ea和指前因子A,表明含能配合物Cu(CHZ)4(PA)2和Co(CHZ)4(PA)2使CL-20的热分解活化能由原来的222.8kJ/mol降至186.6kJ/mol和183.0kJ/mol。     

可生物降解高分子材料的研究与进展

高分子材料难以自然降解,会造成环境污染。可生物降解高分子材料在其使用寿命后,可以自行降解,是未来高分子材料发展的重要方向之一。简要介绍了生物降解高分子材料及其分类,探讨了可生物降解材料的降解机理、影响材料生物降解的因素和生物降解材料的制备方法、评价方法、研究与应用概况,并指出了可生物降解高分子材料未来发展的方向。     

应力作用下高分子材料的老化行为研究

从微观角度综述了应力影响高分子材料老化性能的现象,提出了应力引发材料老化的特殊性,并分析了其产生的原因,总结了应力引发材料老化的机理,讨论了应力与其他因素相结合对材料老化的影响,展望了其研究方向。     

PC热分解机理及PC、PC/ABS的阻燃机理

综述和讨论了芳香族磷酸酯阻燃聚碳酸酯（PC）／丙烯腈-丁二烯-苯乙烯共聚物、硅化合物和硫化合物阻燃PC的阻燃机理以及PC的热分解机理。涉及的反应有碳酸酯基的重排、羟基化合物与PC的作用、Fries重排、异亚丙基键的断裂及PC的热氧化等。今后的研究重点之一是应取得更多证据支持已提出的机理,使其日趋完善。     

Thermal and Combustion Properties of 3,4‐Bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF)

Thermal decomposition of melted 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF) in isothermal conditions was studied. The burning rates of DNTF were measured in the pressure interval of 0.1–15 MPa. The thermal stability of DNTF was found to be close to the stability of HMX, while the burning rate of DNTF was close to the burning rate of CL‐20. The thermocouple measurements in the combustion wave of DNTF showed that combustion of DNTF was controlled by the gas‐phase mechanism. The DNTF vapor pressure was determined from thermocouple measurements and agreed well with data obtained at low temperatures under isothermal conditions.     

热分析质谱联用技术在催化材料研究中的应用

介绍了热分析质谱联用技术(TG-DSC/DTA-MS)以及近几年来该技术在催化材料研究中的应用进展,包括在金属催化剂、金属氧化物催化剂、沸石分子筛与多孔材料等方面的应用.     

含能材料热安定性及热安全性评价方法研究进展

概述含能材料热安定性及热安全性的 3类评价方法在操作过程及试验结果上的局限性。介绍了一种将基本安定性试验评价法与自加速分解温度 (SADT)评价法相结合 ,从而实现对含能材料热安定性及热安全性进行评价的新方法。对该方法的先进性和应用前景进行了论述。     

Thermal decomposition of potassium permanganate: Thermogravimetry,differential scanning calorimetry and hot-stage microscopy studies

Thermogravimetry (TG), differential scanning calorimetry (d.s.c.), and hot-stage microscopy (HSM) techniques have been applied in a study of the thermal decomposition of potassium permanganate. Single crystals of potassium permanganate and ground samples are studied at heating rates from 0.62 to 10 °C min^?1, and results compared with previous isothermal studies. Comparison of theoretical and experimental weight loss is made, for both forms of potassium permangante, and a possible mechanism based on diffusion chain theory and nucleation suggested.     

2,4-二氯过氧化苯甲酰的热分解及等温动力学模型

引言2,4-二氯过氧化苯甲酰(双-2,4,DCBP)工业上常用作自由基引发剂、高温硅橡胶固化剂和无模硫化剂。因用该物质生产的硅橡胶制品无毒,可用于人工脏器、牙托、奶瓶等,也可用作高功率发电机绝缘用品,尤其适用于导弹、航天器中密封圈及耐热胶管带[1]。有机过氧化物中含有不稳定的"—O—O—"键,导致此类物质易受热分解,并引     

用单一非等温DSC曲线确定双基发射药热分解反应的最可几机理函数和动力学参数

根据CDR-1型差动热分析仪上测得的一条DSC曲线,利用计算非等温动力学的积分方程和微分方程拟合实验数据,逻辑选择确定双基发射药CB0617在分解深度为0.03～0.41范围内的热解反应的微分形式的最可几机理函数为f(α)=(1-α)n.用放热速率方程算得其热解反应的表观活化能、指前因子和微分形式的最可几机理函数分别为145.23kJ/mol、1013.27s-1和f(α)=(1-α)0.90.积分方程逻辑选择求得的表观活化能和指前因子分别为146.31kJ/mol和1013.35s-1.微分方程逻辑选择求得的表观活化能和指前因子相应为148.77kJ/mol和1013.69s-1;三者吻合良好.