几种硝胺炸药在熔态TNT和DNP中的溶解性及其结晶晶型
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摘要
为研究硝胺类炸药在熔铸载体中的溶解性并分析溶解后硝胺类炸药的相变,采用物理分离的方法分别测出了RDX、HMX和CL-20在90℃的2,4,6-三硝基甲苯(TNT)和3,4-二硝基吡唑(DNP)中的溶解度;通过拉曼光谱对溶解后回收的硝胺类炸药进行了表征。结果表明,90℃下,RDX、HMX和CL-20在TNT中的溶解度分别为3.35、0.24和4.99g/100g,在DNP中的溶解度分别为12.28、2.64和7.03g/100g;RDX在TNT、DNP中溶解冷却后的晶型均为β型,HMX在TNT、DNP中溶解冷却后的晶型均为α型,RDX、HMX在TNT、DNP中溶解前后晶型一致,均未发生变化;CL-20在TNT、DNP中溶解后回收的晶型均由ε型变为β型,说明CL-20在熔铸炸药载体中由于温度与溶剂的作用晶型不稳定,硝胺类炸药在熔铸载体中溶解并发生相变将会严重影响炸药的性能。
To study the solubility of nitramine explosives in melt-casting carriers and to analyze the phase transition of nitramine explosives after dissolving, the solubility of RDX, HMX and CL-20 in 2,4,6-trinitrotoluene(TNT) and 3,4-dinitropyrazole(DNP) at 90℃ was measured by physical separation method, respectively. The nitramine explosives recovered after dissolution were characterized by Raman spectroscopy. The results show that the solubilities of RDX, HMX and CL-20 in TNT at 90℃ are 3.35, 0.24 and 4.99 g/100 g, and the solubilities in DNP are 2.28, 2.64 and 7.03 g/100 g, respectively. The crystal forms of RDX recovered after dissolving and cooling in TNT and DNP are all of α-type and the crystal forms of HMX recovered after dissolving and cooling in TNT and DNP are all of β-type. The crystalline forms of RDX and HMX before and after dissolving in TNT and DNP are the same, and without change. The crystal forms of CL-20 recovered after dissolving in TNT and DNP are all changed from ε-type to β-type, indicating that the crystal form of CL-20 is unstable in melt-casting carrier explosives due to the effect of temperature and solvent. The dissolution and phase transition of nitramine explosives in the melt-casting explosive carrier will seriously affect the performance of the explosives.
To study the solubility of nitramine explosives in melt-casting carriers and to analyze the phase transition of nitramine explosives after dissolving, the solubility of RDX, HMX and CL-20 in 2,4,6-trinitrotoluene(TNT) and 3,4-dinitropyrazole(DNP) at 90℃ was measured by physical separation method, respectively. The nitramine explosives recovered after dissolution were characterized by Raman spectroscopy. The results show that the solubilities of RDX, HMX and CL-20 in TNT at 90℃ are 3.35, 0.24 and 4.99 g/100 g, and the solubilities in DNP are 2.28, 2.64 and 7.03 g/100 g, respectively. The crystal forms of RDX recovered after dissolving and cooling in TNT and DNP are all of α-type and the crystal forms of HMX recovered after dissolving and cooling in TNT and DNP are all of β-type. The crystalline forms of RDX and HMX before and after dissolving in TNT and DNP are the same, and without change. The crystal forms of CL-20 recovered after dissolving in TNT and DNP are all changed from ε-type to β-type, indicating that the crystal form of CL-20 is unstable in melt-casting carrier explosives due to the effect of temperature and solvent. The dissolution and phase transition of nitramine explosives in the melt-casting explosive carrier will seriously affect the performance of the explosives.
引文
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[2] 罗观,黄辉,张帅,等.RDX在2,4-二硝基苯甲醚(DNAN)低共熔体系中的溶解度[J]. 含能材料, 2012, 20(4): 437-440. LUO Guan, HUANG Hui, ZHANG Shuai, et al. Solubility of RDX in melting DNAN / MNA[J]. Chinese Journal of Energetic Materials, 2012, 20(4): 437-440.
[3] 王玮,罗一鸣,王红星,等.HMX在DNTF中的溶解度研究[J]. 火工品, 2017(4): 50-52. WANG Wei, LUO Yi-ming, WANG Hong-xing, et al. Study on the solubility of HMX in DNTF [J]. Initiators & Pyrotechnics, 2017(4): 50-52.
[4] Ghosh M, Banerjee S, Khan M A S, et al. Understanding phase metastable transformation during crystallization of RDX, HMX and CL-20: experimental and DFT studies[J]. Physical Chemistry Chemical Physics, 2016, 18(34): 23554.
[5] Davies P J, Provatas A. Characterisation of 2,4-dinitroanisole: an ingredient for use in low sensitivity melt cast formulations[D]. Australia: Defence Science and Technology Organisation, 2006: 13-14.
[6] Thiboutot S, Brousseau P, Ampleman G, et al. Potential use of CL-20 in TNT/ETPE-based melt cast formulations[J]. Propellants, Explosives, Pyrotechnics, 2008, 33(2): 103-108.
[7] Gao C, Yang L, Zeng Y, et al. Growth and characterization of β-RDX single-crystal particles[J]. Chemical Industry & Engineering Progress, 2007, 26(12): 1761-1766.
[8] 欧育湘,贾会平.六硝基六氮杂异伍兹烷的研究进展(3)[J]. 含能材料, 1999(2): 49-52. OU Yu-xiang, JIA Hui-ping. Research progress of hexanitrohexaazaisowurtzitane(3)[J]. Chinese Journal of Energetic Materials, 1999(2): 49-52.
[9] 徐金江.CL-20重结晶过程中的晶型转变研究[D]. 北京:中国工程物理研究院, 2012. XU Jin-jiang. Polymorphic transformation in CL-20 recrystallization[D]. Beijing: China Academy of Engineering Physics, 2012.
[10] 庞思平,申帆帆,吕芃浩,等.六硝基六氮杂异伍兹烷合成工艺研究进展[J]. 兵工学报, 2014, 35(5): 725-732. PANG Si-ping, SHEN Fan-fan, Lü Peng-hao, et al. Research progress in synthesis of hexanitrohexaazaisowurtzitane[J]. Acta Armamentarii, 2014, 35(5): 725-732.
[11] Goetz F, Brill T B. Laser Raman spectra of alpha- beta-, gamma-, and delta-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine and their temperature dependence[J]. The Journal of Chemical Physics, 1979, 83(3):340-346.