含能燃速抑制剂的制备及其对AP分解的负催化效应

doi:10.12382/bgxb.2022.0518

摘要/Abstract

摘要：

燃速抑制剂作为固体推进剂的核心功能组分,在降低固体推进剂高压燃速方面起关键作用。精准设计具有降速效应的季铵与醛基结构,获得高氮三氨基胍乙二醛二维共聚物(Triaminoguaniding Glyoxal two dimensional Copolymer,TAGP)含能配体,并与碱土金属离子K⁺、Ba²⁺和Ca²⁺发生络合反应,制备系列新型含能燃速抑制剂(TAGP-M)。采用粉末衍射、X射线光电子能谱、扫描电镜/能谱和差示扫描量热/热重联用等技术分析其形貌、结构和热稳定性,并研究这些含能燃速抑制剂对高氯酸铵(Ammonium Perchlorate,AP)热分解的负催化作用。研究结果表明:TAGP-K对AP转晶抑制最为显著,使AP的转晶吸热峰温提高5.9℃、低温分解峰峰温升高28.7℃;添加10 wt%的TAGP-K,可使AP的最大热分解速率降低58%;TAGP-Ca燃速抑制剂可使AP的释能效应集中在高温分解过程,AP/TAGP-Ca混合体系的放热量比纯AP提高50%以上;TAGP-Ca和TAGP-Ba燃速抑制剂在抑制含AP分解的同时提高了其释能效率;TAGP-M燃速抑制剂在分解过程中释放NH₃并与AP分解产物HClO₄结合,形成更难分解的$\mathrm{M}\left(\mathrm{ClO}_{4}^{-}\right)_{n}$;通过碱土离子与$\mathrm{ClO}_{4}^{-}$离子强静电作用,抑制后者分解产生氧化性气氛,进而抑制AP高温放热反应过程。

关键词: 含能燃速抑制剂, 原位交联配位, 热稳定性, 结构优选, 降速机理

Abstract:

As the key functional component of solid propellant, the burning rate inhibitor plays an important role in regulating the burning rate of solid propellant. In this paper, the quaternary ammonium and aldehyde-based structures with combustion suppression effect are precisely designed and evaluated. The high nitrogen triaminoguanidine glyoxal two-dimensional copolymer(TAGP) is used as an energetic ligand. It is complexed with alkaline earth metal ions, such as K⁺, Ba²⁺ and Ca²⁺, to prepare a series of novel energetic burning rate inhibitors(so called TAGP-M). The morphologies, structure and thermal stability of the as-prepared compoundsare characterized by X-ray diffraction,X-ray photoelectron spectroscopy, scanning electron microscope/energy dispersive spectrometer, and differential scanning calorimetry and thermogravimetric analysis techniques. The negative catalytic effect of energetic burning rate inhibitor on ammonium perchlorate (AP) decomposition is analyzed. It shows that TAGP-K has obvious inhibitory effect on the crystal transition of AP. In presence of TAGP-K, the endothermic peak temperature of AP crystal transition is increased by 5.9℃, whereas the first peak decomposition temperature is increased by 28.7℃. More importantly, the use of 10 wt% TAGP-K could reduce the maximum thermal decomposition rate of AP by 58%. The corresponding energy release of AP is focused to high-temperature decomposition(HTD) process. The heat release of AP/TAGP-Ca is more than 50% higher than that of pure AP during HTD process. It shows that TAGP-Ca and TAGP-Ba increase the energy release efficiency of AP while inhibitingits decomposition. The TAGP-M burning rate inhibitors release NH₃ during the decomposition process and combine with HClO₄(AP decomposition product) to form $\mathrm{M}\left(\mathrm{ClO}_{4}^{-}\right)_{n}$ which is more difficult to decompose.The HTD process of AP is inhibited by the strong electrostatic interaction between alkaline earth metal ions and $\mathrm{ClO}_{4}^{-}$, which inhibits the decomposition of $\mathrm{ClO}_{4}^{-}$ to generate an oxidizing atmosphere and prevent theoxidative exotherm of the adsorbed NH₃.

Key words: energetic burning rate inhibitor, in-situ cross-linking coordination, thermal stability, structure optimization, burning rate reduction mechanism

中图分类号:

张雪雪, 薛智华, 聂洪奇, 严启龙. 含能燃速抑制剂的制备及其对AP分解的负催化效应[J]. 兵工学报, 2024, 45(1): 15-25.

ZHANG Xuexue, XUE Zhihua, NIE Hongqi, YAN Qilong. Preparation of Energetic Burning Rate Inhibitor and Its Negative Catalytic Effect on AP Decomposition[J]. Acta Armamentarii, 2024, 45(1): 15-25.

图/表 14

表1 优选含能燃速抑制剂和燃速催化剂汇总

Table 1 The summary of preferred energetic burning rate inhibitors and catalyst

样品	差示扫描量热曲线		热重分析曲线			微商热重分析曲线
样品	T_p1	ΔH₁	MS₁	R_s	T_o	T_p3	L_max1
TAGP-Cu	195.2	677.2	27.3	49.7	142.5	184.5	2.2
TAGP-K	201.3	1512.0	24.0	51.8	168.0	229.4	2.7
TAGP-Ba	209.2	427.2	34.3	51.8	187.1	227.7	2.2
TAGP-Ca	206.9	281.4	47.9	41.6	167.1	242.7	3.0

图1 TAGP-Cu、TAGP-K、TAGP-Ba和TAGP-Ca的DSC和TG图

Fig.1 DSC and TG diagrams of TAGP-Cu, TAGP-K, TAGP-Ba and TAGP-Ca

图2 含能燃速催化剂和燃速抑制剂的SEM图和EDS图

Fig.2 SEM and EDS images of energetic burning rate catalysts and inhibitors

图3 燃速抑制剂和燃速催化剂粉末衍射图

Fig.3 The powder diffraction patterns of burning rate inhibitors and catalyst

表2 3种燃速抑制剂和燃速催化剂晶体参数

Table 2 The crystal parameters of three burning rate inhibitors and burning rate catalyst

参数	样品
参数	TAGP-Ba	TAGP-Ca	TAGP-Cu	TAGP-K
晶系	正交	三斜	正交	三斜
空间点阵	Pbca(61)	P1(1)	Pbca(61)	P1(1)
a/Å	13.20	6.77	13.25	6.77
b/Å	11.60	10.67	11.57	10.94
c/Å	10.74	8.43	10.65	8.55
α/(°)	90	47.45	90	45.38
β/(°)	90	54.82	90	54.88
γ/(°)	90	57.59	90	57.02
Vol/Ǎ³	1644.58	355.66	1632.51	359.91

表3 TAGP-M燃速抑制剂性能参数

Table 3 The performances of TAGP-M burning rate inhibitors

样品	计算分子式	分子量	燃烧热/(J·g^-1)	生成焓/(J·g^-1)	密度/(g·cm^-3)
TAGP-Cu	C₃H_5.3O_0.88N₄Cu_0.987·(H₂O)_0.685·(NO₃)_1.16	258.4	6593	-1502.4	2.07
TAGP-K	C₃H_8.4O_0.89N₄K_0.0006·(H₂O)_0.16·(NO₃)_1.556	214.0	10289	1223.8	1.72
TAGP-Ba	C₃H_5.3O_8.94N₄Ba_0.005·(H₂O)_2.247·(NO₃)_1.122	351.0	6047	522.6	1.56
TAGP-Ca	C₃H_7.9O_0.89N_4.64Ca_0.228·(NO₃)_1.598	231.0	9584	1097.8	1.73

图4 含能燃速抑制剂XPS图

Fig.4 XPS images of energetic burning rate inhibitors

图5 TAGP-Ca燃速抑制剂XPS图

Fig.5 XPS diagram of TAGP-Ca

图6 AP和AP/10 wt%燃速抑制剂DSC曲线

Fig.6 DSC curves of AP and AP/10 wt% burning rate inhibitors

图7 AP和AP/10 wt%燃速抑制剂TG/DTG曲线图

Fig.7 TG/DTG curves of AP and AP/10 wt% burning rate inhibitors

表4 工业级AP和AP/10 wt%燃速抑制剂混合体系DSC热分解参数

Table 4 DSC parameters of industrial scale AP and mixtures of AP with 10 wt% of burning rate inhibitors

样品	吸热峰		放热峰
样品	T_p0	ΔH₀	T_p1	T_p2	ΔH₁	ΔH₂
AP	243.0	79.4	283.8	365.7	234.6	866.7
AP/TAGP-Ba	245.1	74.5	300.5	370.7	360.1	779.4
AP/TAGP-Ca	243.9	82.3	273.5	386.3	118.6	1313.0
AP/TAGP-Cu	246.7	8.3	205.4	304.4	150.0	625.4
AP/TAGP-K	248.9	100.3	312.5	382.4	449.0	363.5

表5 工业级AP和AP/10 wt%燃速抑制剂混合体系TG/DTG热分解参数

Table 5 TG/DTG parameters of industrial scale AP and mixtures of AP with 10 wt% of burning rate inhibitors

样品	TG曲线			DTG曲线
样品	T_o/ ℃	MS₁/ %	MS₂/ %	T_p3/ ℃	T_p4/ ℃	L_max1	L_max2
AP	273.6	26.8	67.0	283.4	413.2	8.9	12.1
AP/TAGP-Ba	288.7	26.1	67.9	298.4	371.8	6.0	9.1
AP/TAGP-Ca	263.5	21.5	68.4	276.1	385.1	4.1	16.3
AP/TAGP-Cu	150.2	25.2	17.6	193.8	304.5	1.7	2.8
AP/TAGP-K	292.4	29.7	58.6	313.3	416.1	3.7	7.5

图8 AP和AP/10 wt%燃速抑制剂热分解产物FTIR曲线图

Fig.8 FTIR curves of thermal decomposition products of AP and AP/10 wt% burning rate inhibitor

图9 AP和AP/10 wt%燃速抑制剂热分解产物HCl、HClO4和FTIR曲线图

Fig.9 FTIR curves of thermal decomposition products HCl, HClO4 and NH3 of AP and AP/10 wt% burning rate inhibitors

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