火炸药学报

为了改善HATO炸药晶体的品质,进一步提高其在火炸药中应用的安全性能,利用平衡法测量了HATO在4种纯溶剂及3种混合溶剂中的溶解度,优选HATO重结晶溶剂体系; 采用降温重结晶的方法,通过控制溶剂种类、降温速率、搅拌速率等参数制备得到高品质HATO炸药晶体; 同时利用Materials Studio软件对HATO与几种常用黏结剂材料的结合能力进行仿真计算,优选出与HATO结合能力强的材料进行包覆,并对包覆前后HATO的机械感度进行测试。结果表明,HATO在水-甲酸体系中具有较高的溶解度,但水-乙醇混合溶剂体系更有利于HATO的球形化。经降温重结晶得到的HATO晶体密度达到1.87g/cm3,5s爆发点为286.12℃,爆速为9550m/s,撞击感度和摩擦感度分别为24%和16%,均优于原料HATO。同时发现含氟材料与HATO的内聚能密度大于非含氟材料,对HATO具有更强的黏附效果,包覆后的HATO无晶体裸露,机械感度显著降低。

In order to improve the crystal quality of HATO and promote its safety performance in the application of explosives, the solubilities of HATO in four pure solvents and three mixed solvents were measured by the equilibrium method, and the recrystallization solvent system of HATO was optimized. By using cooling recrystallization method, high-quality HATO crystal was prepared by controlling the type of solvent, cooling rate, and stirring rate. The Materials Studio software was used to simulate the binding ability of HATO with several common adhesive materials, and the materials with strong binding ability with HATO were selected for further coating. The mechanical sensitivities of HATO before and after coating were also tested. The results show that HATO has a higher solubility in the water-formic acid system, but the water-ethanol system is more favorable to the sphericity of HATO. The density of HATO crystal obtained by cooling recrystallization is 1.87g/cm3, the 5s bursting point is 286.12℃, the detonation velocity is 9550m/s, the impact sensitivity and friction sensitivity are 24% and 16%, respectively. The above performances are better than those of raw material HATO. The cohesion energy density of fluorine-containing materials and HATO is higher than that of non-fluorine-containing materials, proved that fluorine-containing materials has a stronger adhesion effect on HATO. The coated HATO has no crystal face exposed, and the mechanical sensitivity is significantly reduced.

引言
1 实验
2 结果与讨论
3 结论

图1 HATO在4种纯溶剂中的溶解度<br/>Fig.1 Solubility of HATO in four pure solvents

图1 HATO在4种纯溶剂中的溶解度
Fig.1 Solubility of HATO in four pure solvents

图2 HATO分别在水-甲酸、水-乙酸和水-乙醇混合体系中的溶解度<br/>Fig.2 Solubility of HATO in ater-formic acid,water-acetic acid and water-ethanol

图2 HATO分别在水-甲酸、水-乙酸和水-乙醇混合体系中的溶解度
Fig.2 Solubility of HATO in ater-formic acid,water-acetic acid and water-ethanol

图3 不同溶剂制得HATO样品照片<br/>Fig.3 Photographs of HATO samples prepared by different solvents

图3 不同溶剂制得HATO样品照片
Fig.3 Photographs of HATO samples prepared by different solvents

图4 不同搅拌速率下HATO样品照片<br/>Fig.4 Photographs of HATO samples at different stirring rates

图4 不同搅拌速率下HATO样品照片
Fig.4 Photographs of HATO samples at different stirring rates

图5 不同降温速率下HATO样品照片<br/>Fig.5 Photographs of HATO samples at different cooling rates

图5 不同降温速率下HATO样品照片
Fig.5 Photographs of HATO samples at different cooling rates

图6 重结晶前后HATO样品红外光谱图<br/>Fig.6 IR spectra of HATO samples before and after recrystallization

图6 重结晶前后HATO样品红外光谱图
Fig.6 IR spectra of HATO samples before and after recrystallization

图7 HATO的核磁谱图<br/>Fig.7 NMR spectra of HATO

图7 HATO的核磁谱图
Fig.7 NMR spectra of HATO

图8 原料HATO与高品质HATO的DSC曲线<br/>Fig.8 DSC curves of raw HATO and high quality HATO

图8 原料HATO与高品质HATO的DSC曲线
Fig.8 DSC curves of raw HATO and high quality HATO

表1 原料HATO的性能参数<br/>Table 1 Performance parameters of raw HATO

表1 原料HATO的性能参数
Table 1 Performance parameters of raw HATO

表2 高品质HATO的性能参数<br/>Table 2 Performance parameters of high quality HATO

表2 高品质HATO的性能参数
Table 2 Performance parameters of high quality HATO

图9 HATO与不同材料平衡结构图<br/>Fig.9 Balance structure diagram of HATO with different materials

图9 HATO与不同材料平衡结构图
Fig.9 Balance structure diagram of HATO with different materials

表3 HATO与不同材料的结合能及内聚能密度<br/>Table 3 Binding energy and cohesive energy density of HATO with different materials

表3 HATO与不同材料的结合能及内聚能密度
Table 3 Binding energy and cohesive energy density of HATO with different materials

图10 不同材料包覆后HATO样品<br/>Fig.10 HATO samples after coating with different materials

图10 不同材料包覆后HATO样品
Fig.10 HATO samples after coating with different materials

表4 不同材料包覆HATO样品感度<br/>Table 4 Mechanical sensitivities of HATO samples after coating with different materials

表4 不同材料包覆HATO样品感度
Table 4 Mechanical sensitivities of HATO samples after coating with different materials

[1] FISCHER N, FISCHER D, KLAPÖTKE T M, et al. Pushing the limits of energetic materials-the synthesis and characterization of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate[J]. Journal of Materials Chemistry, 2012, 22(38): 20418-20422.
[2]张保良,张红,李哲.低易损性炸药的应用研究[J].兵工自动化,2017, 36(7): 9-11.

Ordnance Industry Automation

[3]王昕.美国不敏感混合炸药的发展现状[J].火炸药学报,2007, 30(2): 78-80.

Chinese Journal of Explosives & Propellants(Huozhayao Xuebao)

[4]王苏炜,肖磊,胡玉冰,等.纳米单质含能材料制备及其应用现状[J].火炸药学报,2021, 44(6): 705-734.

Chinese Journal of Explosives & Propellants(Huozhayao Xuebao)

[5]田龙,吴晓青,郑主宜,等. 粒度对炸药感度影响的研究进展[J]. 四川化工, 2013, 16(1): 28-30.

Sichuan Chemical Industry

[6]曹霞,向斌,张朝阳.炸药分子和晶体结构与其感度的关系[J].含能材料,2012,20(5):643-649.

Chinese Journal of Energetic Materials

[7]朱周朔,姜振明,王鹏程,等. 5,5'-联四唑-1,1'-二氧二羟铵的合成及其性能[J].含能材料,2014,22(3): 332-336.

Chinese Journal of Energetic Materials

[8]毕福强,肖川,许城,等.1,1'-二羟基-5,5'-联四唑二羟胺盐的合成与性能[J].含能材料,2014,22(2): 272-273.

Chinese Journal of Energetic Materials

[9]GOLENKO Y D, TOPCHIY M A, ASACHENKO A F,et al. Optimization studies on synthesis of tkx-50[J]. Chinese Journal of Chemistry, 2017, 35(1): 5.
[10]HEMMANN M, FRTER-BARTH U. Thermal behavior and micro structure of TKX-50[J]. Propellants, Explosives, Pyrotechnics, 2021, 46: 262-266.
[11]TALAWAR M B, NANDAGOPAL S, SINGH S, et al. TGA, DSC and DFT studies of TKX, ABTOX and their key precursors[J]. ChemistrySelect, 2018, 3(43): 12175-12182.
[12]MURAVYEV N V, MONOGAROV K A, ASACHENKO A F, et al. Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate(TKX-50)[J]. Physical Chemistry Chemical Physics, 2016, 19: 436-449.
[13]KLAPÖTKE T M, CUDZIO S, TRZCIńSKI WA. An answer to the question about the energetic performance of TKX-50[J]. Propellants, Explosives, Pyrotechnics, 2022(6):47.
[14]KLAPÖTKE T M, WITKOWSKI T G, WILK Z, et al. Determination of the initiating capability of detonators containing TKX-50, MAD-X1, PETNC, DAAF, RDX, HMX or PETN as a base charge, by underwater explosion test[J]. Propellants, Explosives, Pyrotechnics, 2016, 41(1): 92-97.
[15]WANG Shu-Ji, WANG Di, LIU Ping, et al. Enhanced combustion behavior of TKX-50/B/NC composites via electrospray[J]. Journal of Energetic Materials, DOI: 10.1080/07370652.2022.2094034
[16]任晓婷,张国涛,何金选,等. 1,1'-二羟基-5,5'-联四唑二羟胺盐的晶形计算及控制[J].火炸药学报,2016, 39(2):68-71.

Chinese Journal of Explosive & Propellants(Huozhayao Xuebao)

[17]米向超. 新型高能炸药TKX-50的结晶研究[D]. 太原:中北大学, 2015.
[18]米登峰, 张瑞, 张璇,等. 球形化TKX-50的制备及性能表征[J]. 火炸药学报, 2020, 43(1):64-68.

Chinese Journal of Explosive & Propellants(Huozhayao Xuebao)

[19]周畅.TKX-50结晶工艺的研究[D]. 北京:北京理工大学, 2017.
[20]DAN L, DUAN-LIN C, LI-ZHEN C, et al. Solubility of dihydroxylammonium 5,5'-Bistetrazole-1,1'-diolate in(formic acid, water)and their binary solvents from 298.15K to 333.15K at 101.1kPa[J]. The Journal of Chemical Thermodynamics, 2019, 128: 10-18.
[21]XU Xin, CHEN Dong, LI Hong-zhen,et al. Crystal morphology modification of 5,5'-bisthiazole-1,1'-dioxyhydroxyammonium salt[J]. ChemistrySelect, 2020, 5: 1919-1924.
[22]马凤利, 吴晓青, 白宇,等. 5,5-联四唑-1,1-二氧二羟胺(TKX-50)球型化的研究[J]. 精细化工中间体, 2018, 48(5):48-51.

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引言

1 实验

2 结果与讨论

3 结论

期刊信息

备注

引言

1 实 验

2 结果与讨论

3 结 论

期刊信息

1 实验

3 结论