聚四氟乙烯基铝活性材料的热化学反应特性

doi:10.3969/j.issn.1000-1093.2020.10.005

摘要/Abstract

摘要： 为获得聚四氟乙烯（PTFE）基铝（Al）活性材料的热化学反应性能，开展包含不同Al粒径的PTFE基Al活性材料在不同升温速率下的热化学反应实验。采用湿混工艺制备包含50 nm和10 μm两种Al粒径的PTFE基Al活性材料，并利用差示扫描量热法与热重分析法分析它们在10 ℃/min、 15 ℃/min、20 ℃/min、30 ℃/min升温速率下的热化学反应行为。结果表明：在10~ 30 ℃/min升温速率中，包含纳米Al颗粒的PTFE基Al试样都发生了反应放热，而包含微米Al颗粒的PTFE基Al试样在小于900 ℃时并未与PTFE分解产物发生反应； Al颗粒的加入会对PTFE的热分解起到一定催化作用；对于Al粒径为50 nm的PTFE基Al活性材料，随着升温速率的增大，反应放热峰的峰值温度不断向高温区移动（由10 ℃/min的578.9 ℃移动到30 ℃/min时的608.5 ℃），单位放热量逐渐增多（由10 ℃/min升温速率下的331.6 J/g升高到30 ℃/min升温速率下的641.3 J/g）；研究结果对PTFE基Al活性材料的工程化应用具有参考意义。

关键词: 活性材料, 热化学反应特性, 聚四氟乙烯, 铝粒径

Abstract: In order to obtain the thermochemical reaction properties of PTFE/Al reactive materials, the thermochemical reaction experiments of PTFE/Al reactive materials with different aluminum particle sizes were carried out at different heating rates. The PTFE/Al active materials with 50 nm and 10 μm aluminum particle sizes were prepared by wet mixing process, and their thermochemical reaction behaviors at heating rates of 10 ℃/min, 15 ℃/min, 20 ℃/min and 30 ℃/min were analyzed by differential scanning calorimetry (DSC) and thermogravimetry (TG). The results show that, at the heating rate from 10 ℃/min to 30 ℃/min, all the PTFE/Al samples containing nano Al particles are exothermic, while the PTFE/Al samples containing micro Al particles do not react with the decomposition products of PTFE at a temperature lower than 900 ℃; in addition, the addition of Al particles plays a catalytic role in the thermal decomposition of PTFE. For PTFE/Al active materials with aluminum particle size of 50 nm, the peak temperature of reaction exothermic peak moves to high temperature zone with the increase in heating rate, from 578.2 ℃ to 608.5 ℃. The unit heat release increases from 331.6 J/g to 641.3 J/g. The research results have important reference value for the engineering application of PTFE/Al reactive materials.

Key words: reactivematerial, thermochemicalcharacteristic, polytetrafluoroethylene, Alparticlesize

中图分类号:

TJ410.4

毛亮，叶胜，胡万翔，姜春兰，王在成. 聚四氟乙烯基铝活性材料的热化学反应特性[J]. 兵工学报, 2020, 41(10): 1962-1969.

MAO Liang， YE Sheng， HU Wanxiang， JIANG Chunlan， WANG Zaicheng. Thermochemical Reaction Characteristics of PTFE/Al Reactive Material[J]. Acta Armamentarii, 2020, 41(10): 1962-1969.

参考文献

［1］叶文君, 汪涛, 鱼银虎. 氟聚物基含能反应材料研究进展[J]. 宇航材料工艺, 2012,42(6): 19-23.
YE W J, WANG T, YU Y H. Research progress of fluoropolymer-matrix energetic reactive materials[J]. Aerospace Materials and Technology, 2012,42(6): 19-23.(in Chinese)
[2] 李玲琴. 金属/氟聚物反应材料性能的研究[D]. 太原: 中北大学, 2015.
LI L Q. Research on detonation properties of metal-fluride reactive materials[D]. Taiyuan: North University of China, 2015.(in Chinese)
[3] KOCH E C. Metal-fluorocarbon based energetic materials[M].Weinheim, Germany：Wiley-VCH Gmbh & Co.KGa A, 2012：6-17.
[4] 张先锋, 赵晓宁.多功能含能材料研究进展[J]. 含能材料, 2009, 17(6): 731-739.
ZHANG X F, ZHAO X N. Review on multifunctional energetic structural materials[J]. Chinese Journal of Energetic Materials, 2009, 17(6): 731-739.(in Chinese)
[5] 张昊, 王海福, 余庆波，等. 活性射流侵彻钢筋混凝土靶后效超压特性[J]. 兵工学报, 2019, 40(7): 1365-1372.
ZHANG H, WANG H F, YU Q B, et al. Aftereffect overpressure of reactive jet perforating into reinforced concrete[J]. Acta Armamentarii, 2019, 40(7): 1365-1372.(in Chinese)
[6] 苏成海, 王海福, 谢剑文,等. 活性射流作用混凝土靶侵彻与爆炸效应研究[J]. 兵工学报, 2019, 40(9): 1829-1835.
SU C H, WANG H F, XIE J W, et al. Penetration and damage effects of reactive material jet against concrete target[J]. Acta Armamentarii , 2019, 40(9): 1829-1835. (in Chinese)
[7] 吴家祥, 李裕春, 方向,等. Al粒径对Al-PTFE准静压反应和落锤撞击感度的影响[J]. 含能材料, 2018, 26(6): 524-529.
WU J X, LI Y C, FANG X, et al. Effect of Al particle size on the quasi-compression reaction and drop hammer impact sensitivity of Al-PTFE[J]. Chinese Journal of Energetic Materials, 2018, 26(6): 524-529.(in Chinese)
[8] 吴家祥, 方向, 李裕春，等. Al-Ni-PTFE反应材料的准静压力学响应与毁伤性能研究[J]. 火工品, 2019(1): 34-37.
WU J X, FANG X, LI Y C, et al. Study on quasi-static compression mechanical response and damage performance of Al-Ni-PTFE reactive materials[J]. Initiators & Pyrotechnics, 2009(1) : 34-37.(in Chinese)
[9] 任俊凯, 李裕春, 方向，等. PTFE/Al/MnO₂复合材料制备及性能[J]. 工程塑料应用, 2018, 46(10): 35-38,43.
REN J K, LI Y C, FANG X, et al. Preparation and performance of PTFE/Al/MnO₂ composite[J]. Engineering Plastics Application, 2018, 46(10): 35-38,43.(in Chinese)
[10] 黄骏逸, 方向, 李裕春,等. PTFE/Al/MoO₃复合材料的力学和反应性能[J]. 材料工程, 2019, 47(7): 92-98.
HUANG J Y, FANG X, LI Y C, et al. Mechanical and reactive properties of PTFE/Al/MoO₃ composites[J]. Journal of Materials Engineering, 2019, 47(7): 92-98.(in Chinese)
[11] 曾亮, 焦清介, 任慧,等. 纳米铝粉粒径对活性量及氧化层厚度的影响[J]. 火炸药学报, 2011, 34(4): 26-29.
ZENG L, JIAO Q J, REN H, et al. Effect of particle size of nano-aluminum powder on oxide film thickness and active aluminum content[J]. Chinese Journal of Explosives & Propellants. 2011, 34(4): 26-29.(in Chinese)
[12] HOBOSYAN M A, KIRAKOSYAN K G, KHARATYAN S L, et al. PTFE-Al₂O₃ reactive interaction at high heating rates[J]. Journal of Thermal Analysis and Calorimetry, 2015, 119(1): 245-251.
[13] OSBORNE D T, PANTOYA M L. Effect of al particle size on the thermal degradation of Al/Teflon mixtures[J]. Combustion Science and Technology, 2007, 179(8): 1467-1480.
[14] MULAMBA O, PANTOYA M L. Exothermic surface chemistry on aluminum particles promoting reactivity[J]. Applied Surface Science, 2014, 315: 90-94.
[15] 刘璐, 任慧, 焦清介. 纳米镁粉对聚四氟乙烯热分解规律的影响[C]∥ 2014中国功能材料科技与产业高层论坛. 西安: 中国功能材料学会, 2014.
LIU L, REN H, JIAO Q J. The effect of nanometer magnesium powder on the thermal decomposition of polytetrafluroethylene[C]∥Proceedings of China Functional Materials Technology and Industry Forum. Xi'an: China Instrument Functional Materials Society, 2014.(in Chinese)
[16] 周禹男, 刘建忠, 王家皓,等. 铝颗粒氧化机理与燃烧理论研究进展[J]. 兵器材料科学与工程, 2017, 40(2): 122-128.
ZHOU Y N, LIU J Z, WANG J H, et al. Progress in oxidation mechanism and combustion theory of aluminum particles[J]. Ordnance Material Science and Engineering, 2017, 40(2): 122-128. (in Chinese)
[17] LWVITAS V I, PANTOYA M L, DIKICI B. Melt dispersion versus diffusive oxidation mechanism for aluminum nanoparticles: critical experiments and controlling parameters[J]. Applied Physics Letters, 2008, 92(1): 011921.
[18] PANTOYA M L, DEAN S W. The influence of alumina passivation on nano-Al/Teflon reactions[J]. Thermochimica Acta, 2009, 493(1/2): 109-110.
[19] STARINK M J. The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods[J]. Thermochimica Acta, 2003, 404(1/2): 163-176.
[20] KISSINGER H E. Variation of peak temperature with heating rate in differential thermal analysis[J]. Journal of Research of the National Bureau of Standards, 1956, 57(4): 217-221.
[21] OZAWA T. Estimation of activation energy by isoconversion methods[J]. Thermochimica Acta, 1992, 203: 159-165.
[22] FAN R H, L H L, SUN K N, et al. Kinetics of thermite reaction in Al-Fe₂O₃ system[J]. Thermochimica Acta, 2006, 440(2): 129-131.

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