火炸药学报

为研究TKX-50对GAP基高能固体推进剂性能的影响,采用DSC-TG、50℃恒温贮存、摩擦感度、撞击感度、静电感度等方法研究了TKX-50与GAP基高能固体推进剂组分间安全性和相容性,并制备成TKX-50/GAP基高能固体推进剂药块,研究其密度、力学性能、安全性能、燃烧性能等,采用小型标准发动机研究其能量性能; 通过DSC测试多种升温速率下的热分解性能,并使用Ozawa模型计算得到TKX-50的热分解活化能。结果表明,TKX-50与GAP黏合剂、AP、Al等相容性良好; TKX-50的热分解活化能为143.57kJ/mol; 随着TKX-50含量的增加,25℃时TKX-50/GAP基高能固体推进剂的摩擦感度从100%降至44%,撞击感度从8.1J升至43.3J,静电感度变化不大,为16.0～42.0mJ; 随着TKX-50含量的增加,25℃时TKX-50/GAP基高能固体推进剂的最大应力从0.65MPa降至0.35MPa,最大伸长率从25.5%升至34.33%,断裂伸长率从29.9%升至37.5%,模量从1.59MPa降至0.48MPa; 低压段(3～9MPa)和高压段(12～25MPa)的燃速压强指数均呈现上升趋势,7MPa下静态燃速为17.2～18.0mm/s,低压段燃速压强指数为0.7～0.8,高压段燃速压强指数相对较高,最高达0.98。在6.86MPa下,动态燃速为21.07mm/s,BSFΦ165发动机实测比冲为256.7s。

To study the effects of TKX-50 on the properties of GAP-based high-energy solid propellant, the safety and compatibility between TKX-50 and components from the GAP-based high-energy solid propellant were studied by using DSC-TG, constant temperature storage at 50℃, friction sensitivity, impact sensitivity and electrostatic sensitivity. TKX-50/GAP-based high-energy solid propellant blocks were prepared for studying their densities, mechanical properties, safety and combustion properties. The energy performance of TKX-50/GAP-based propellant was studied by using small standard engines. The thermal decomposition behavior of the propellant was tested by DSC at various heating rates, and the activation energy of TKX-50 was calculated using the Ozawa model. The results show that TKX-50 is well compatible with GAP binder, AP and Al, etc. The activation energy of TKX-50 thermal decomposition is 143.57kJ/mol. With the increase of TKX-50 content, the friction sensitivity of TKX-50/GAP-based propellant at 25℃ decreases from 100% to 44%, the impact sensitivity increases from 8.1J to 43.3J, and the electrostatic sensitivity does not change much, ranging from 16.0 to 42.0mJ. With the increase of TKX-50 content, the maximum stress of TKX-50/GAP-based propellant at 25℃ decreases from 0.65MPa to 0.35MPa, the maximum elongation increases from 25.5% to 34.33%, the elongation at break increases from 29.9% to 37.5%, and the modulus decreases from 1.59MPa to 0.48MPa. The pressure exponents in the low-pressure section(3-9MPa)and high-pressure section(12-25MPa)show an increasing trend, and the static burning rate at 7MPa is 17.2-18.0mm/s, and the pressure exponent in the low-pressure section was in the range of 0.7—0.8, higher than that of the low-pressure, which can reach 0.98. At 6.86MPa, the dynamic burning rate is 21.07mm/s, and the measured specific impulse of the propellants on the BSFΦ165 engine is 256.7s.

引言
1 实验
2 结果与讨论
3 结论

图1 TKX-50、GAP、TK5X-50/GAP的DSC和TG曲线<br/>Fig.1 DSC and TG curves of TKX-50, GAP binder and TKX-50/GAP mixtures

图1 TKX-50、GAP、TK5X-50/GAP的DSC和TG曲线
Fig.1 DSC and TG curves of TKX-50, GAP binder and TKX-50/GAP mixtures

图2 TKX-50/GAP/Al、TKX-50/GAP/AP和TKX-50/GAP/Al/AP的DSC和TG曲线<br/>Fig.2 DSC and TG curves of TKX-50/GAP/Al, TKX-50/GAP/AP and TKX-50/GAP/Al/AP

图2 TKX-50/GAP/Al、TKX-50/GAP/AP和TKX-50/GAP/Al/AP的DSC和TG曲线
Fig.2 DSC and TG curves of TKX-50/GAP/Al, TKX-50/GAP/AP and TKX-50/GAP/Al/AP

表1 混合体系药浆的DSC测试结果<br/>Table 1 DSC results of mixtures

表1 混合体系药浆的DSC测试结果
Table 1 DSC results of mixtures

图3 50℃恒温条件下质量随时间变化曲线<br/>Fig.3 Curves of the mixtures mass change with time under the constant temperature of 50℃

图3 50℃恒温条件下质量随时间变化曲线
Fig.3 Curves of the mixtures mass change with time under the constant temperature of 50℃

表2 混合体系药浆感度测试结果<br/>Table 2 Sensitivity test results of mixtures

表2 混合体系药浆感度测试结果
Table 2 Sensitivity test results of mixtures

表3 不同含量TKX-50推进剂药浆的安全性能测试结果<br/>Table 3 Safety performance of propellant slurry with different TKX-50 contents

表3 不同含量TKX-50推进剂药浆的安全性能测试结果
Table 3 Safety performance of propellant slurry with different TKX-50 contents

表4 25℃时不同TKX-50含量推进剂药条的力学性能<br/>Table 4 Mechanical properties of propellant with different TKX-50 contents at 25℃

表4 25℃时不同TKX-50含量推进剂药条的力学性能
Table 4 Mechanical properties of propellant with different TKX-50 contents at 25℃

表5 TKX-50/GAP基高能固体推进剂的静态燃烧性能 <br/>Table 5 Static combustion performance of TKX-50/GAP-based high-energy solid propellant

表5 TKX-50/GAP基高能固体推进剂的静态燃烧性能
Table 5 Static combustion performance of TKX-50/GAP-based high-energy solid propellant

表6 TKX-50/GAP基高能固体推进剂动态燃速(BSFΦ75发动机)<br/>Table 6 Dynamic burning rate(BSFΦ75 engine)of TKX-50/GAP-based high-energy solid propellant

表6 TKX-50/GAP基高能固体推进剂动态燃速(BSFΦ75发动机)
Table 6 Dynamic burning rate(BSFΦ75 engine)of TKX-50/GAP-based high-energy solid propellant

图4 BSFΦ165发动机试验p—t、F—t曲线<br/>Fig.4 The p—t and F—t curves of BSF Φ165 engine test

图4 BSFΦ165发动机试验p—t、F—t曲线
Fig.4 The p—t and F—t curves of BSF Φ165 engine test

表7 计算得到的标准理论比冲和比冲效率<br/>Table 7 Standard theoretical specific impulse and specific impulse efficiency calculated from different literature reports

表7 计算得到的标准理论比冲和比冲效率
Table 7 Standard theoretical specific impulse and specific impulse efficiency calculated from different literature reports

[1] FISCHER N, FISCHER D, KLAPOTKE T M, et al. Pushing the limits of energetic materials the synthesis and characterization of di-hydroxylammonium 5, 5'-bistetrazole-1, 1'-diolate [J]. Journal of Materials Chemistry, 2012, 22(38): 20418-20422.
[2]KLAPOTKE T M, MAYR N, STIERSTORFE J, et al. Maximum compaction of ionic organic explosives: Bis(hydroxylammonium)5,5'-dinitromethyl-3,3'-bis(1,2,4-oxadiazolate)and its derivatives [J].Chem Eur J, 2014, 20(5): 1410-1417.
[3]TOBIAS S H, KONSTANTIN K, KLAPOTKE T M. Synthesis and characterization of 2,2'-dinitramino-5,5'-bi(1-oxa-3,4- diazole)and derivatives as economic and highly dense energetic materials [J]. Chemistry A European Journal, 2017, 23(50): 12087-12091.
[4]李猛,赵凤起,罗阳,等. 含 5,5'-联四唑-1,1'-二氧二羟铵推进剂的能量特性计算[J]. 含能材料,2014,22(3):286-290.
[5]曹一林,刘建平. 氧化高氮杂环羟胺盐在固体推进剂中的能量性能分析[J]. 含能材料,2015,23(10):919-923.
[6]刘运飞,庞维强,谢五喜,等. TKX-50 对HTPE推进剂能量特性的影响及应用可行性[J],推进技术,2017,38(12):2851-2856.
[7]SINDITSKIIA V P, FILATOV S A, KOLESOV V I, et al. Combustion behavior and physico-chemical properties of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate(TKX-50)[J]. Thermochimica Acta, 2015, 614(1): 85-92.
[8]NICOLICH S, AMUELS P, DAMAVARAPU R, et al. 5,5'-bis-tetrazole-1,1'-diolate(TKX-50)synthesis and lab scale characterization[R].New Jersey: US Army Arments Research, 2015.
[9]AN Qi, LIU Wei-guang, GODDARD W A, et al. Initial steps of thermal decomposition of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate crystals from quantum mechanics [J]. J Phys Chem C, 2014, 118: 27175-27181.
[10]FISCHER Niko, KLAPOTKE Thomas M., MUSANIC Sanja Matei, et al. TKX-50(bishy-droxyl ammonium 5, 5'-bis(tetrazolate-1N-oxide))[C]∥New Trends in Research of Energetic Materials. Czech Republic: [s.n.],2013: 566-577.
[11]HUANG Hai-feng, SHI Ya-meng, YANG Jun, Thermal characterization of the promising energetic material TKX-50 [J]. J Therm Anal Calorim, 2015, 121:705-709.
[12]王俊峰,杨云峰,张春园,等. 5, 5'-联四唑-1,1'-二氧二羟胺的热分解动力学[J]. 火炸药学报,2015,38(2):42-45.
[13]GJB772A-1997 502.1,DTA和DSC测试安定性和相容性[S].1997.
[14]李谨卫,庞爱民,吴京汉. GAP高能低特征信号推进剂的研究[J]. 固体火箭技术,2001,24(3):42-46.
[15]胡润芝,张小平,郑剑,等. 高能推进剂燃烧效率研究和实测比冲预估[J]. 推进技术,2001,22(5):415-417.
[16]王世英,钱勖,高能推进剂主要组分对燃烧效率的影响研究[J].固体火箭技术,2000,23(2):32-35.
[17]ZHANG Jia-heng, MITCHELL L A, PARRISH D A, et al. Enforced layer-by-layer stacking of energetic salts towards high-performance insensitive energetic materials [J]. J Am Chem Soc, 2015, 137: 10532-10535.
[18]RAMESH K, JAWALKAR S N, SACHDEVA S, et al. Development of a composite propellant formulation with a high performance index using a pressure casting technique [J]. Central European Journal of Energetic Materials, 2012, 9(1): 49-58.

备注

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