Ti/Fe(NCN)新型铝热剂的制备和燃烧性能

doi:10.12382/bgxb.2024.0006

摘要/Abstract

摘要：

铝热剂作为一类高能、钝感、安全性好的含能材料,在固体推进剂、金属焊接、新型材料制造等领域有着广阔的应用前景。近年来,一类金属碳化二亚胺或称金属氰胺化合物M_x(NCN)_y(其中M为碱金属、碱土金属、过渡金属或非金属元素),由于其独特的电子结构和新奇的物化性质,逐渐成为研究热点。借助金属碳化二亚胺化合物的高含氮量和亚稳态特性,以Fe(NCN)为代表,与纳米Ti组装为一种新型铝热剂体系—Ti/Fe(NCN),并对Ti/Fe(NCN)含能材料的组分、结构、形貌、燃烧特性及反应过程进行了探究。研究结果表明:当Ti与Fe(NCN)质量比为5∶1时,燃烧过程剧烈,放热量为605J/g,释放压力319kPa,且反应产物中检测出Fe、TiC_0.2N_0.8及气体产物N₂;Ti/Fe(NCN)新型铝热剂有望丰富含能材料研究体系,同时为新型含能器件的研发提供新思路。

关键词: 铝热剂, Ti/Fe(NCN)含能材料, 燃烧特性, 放热性能, 反应过程

Abstract:

As a type of high-energy, insensitive and safe energetic material, the thermites have been applied in solid propellants, metal welding, new material manufacturing and other fields. In recent years, a type of metal carbodiimide M_x(NCN)_y (where M is an alkali metal, alkali earth metal, transition metal or non-metallic element) has gradually become a research hotspot due to its unique electronic structure and novel physicochemical properties. This study utilizes the high nitrogen content and metastable properties of metal carbodiimides, represented by Fe(NCN), to assemble a new type of thermite system with nano Ti-Ti/Fe(NCN). And the composition, structure, morphology, combustion characteristics and reaction process of Ti/Fe(NCN) are explorated. The results show that the combustion process of Ti/Fe(NCN) is outstanding with a heat release of 605J/g and a pressure release of 319kPa, and Fe, TiC_0.2N_0.8 and gas product N₂ are detected in the reaction products when the mass ratio of Ti-Fe(NCN) is 5∶1. The study of new thermite Ti/Fe(NCN) would enrich the research system of energetic materials and provide new ideas for the development of new energetic devices.

Key words: thermite, Ti/Fe(NCN) energetic material, combustion characteristic, heat release, reaction process

中图分类号:

TQ560.5

万立祥, 朱理想, 李宵鹏, 郎茂运, 蔡昌武, 尹艳君. Ti/Fe(NCN)新型铝热剂的制备和燃烧性能[J]. 兵工学报, 2024, 45(12): 4500-4507.

WAN Lixiang, ZHU Lixiang, LI Xiaopeng, LANG Maoyun, CAI Changwu, YIN Yanjun. Preparation and Combustion Performance of a Ti/Fe(NCN) Thermite[J]. Acta Armamentarii, 2024, 45(12): 4500-4507.

图/表 8

表1 实验中Ti和Fe(NCN)的质量比

Table 1 Mass ratio of Ti and Fe (NCN) for experiment

序号	Ti质量/g	Fe(NCN) 质量/g	Fe(NCN) 质量含量/%
1	0.05	0.01	16.7
2	0.05	0.03	37.5
3	0.05	0.05	50.0
4	0.05	0.1	66.7
5	0.05	0.15	75.0

图1 Fe(NCN)的组分、结构和形貌表征

Fig.1 Composition, structure, and morphology characterization of Fe(NCN)

图2 不同质量比的Ti/Fe(NCN)组分及形貌表征

Fig.2 Characterization of components and their morphologies of Ti/Fe (NCN) with different mass ratios

图3 Ti/Fe(NCN)不同质量比时的燃烧过程记录

Fig.3 Combustion processes of Ti/Fe(NCN) with different mass ratios

图4 Ti/Fe(NCN)不同质量比时的压力-时间

Fig.4 Pressure-time curves of Ti/Fe (NCN) with different mass ratios

表2 不同质量比Ti/Fe(NCN)体系反应时的最大压力及产生时间

Table 2 Maximum pressures and generation times of Ti/Fe (NCN) system under different mass ratios

质量比	压力/kPa	时间/ms
5∶1	319	3.40
5∶3	206	3.38
5∶5	203	3.77
5∶10	123	5.18
5∶15

图5 Ti/Fe(NCN)体系(质量比5∶1)反应放热

Fig.5 Heat releases of Ti/Fe(NCN) with mass ratio of 5∶1

图6 质量比5∶1时Ti/Fe (NCN)的反应过程研究

Fig.6 Study on the reaction process of Ti/Fe (NCN) at the mass ratio of 5∶1

参考文献 21

[1]	李强, 陈令, 甘怀银, 等. 静电喷雾法制备纳米复合含能材料RDX@NGEC及性能[J]. 兵工学报, 2023, 44(7): 1985-1992. doi: 10.12382/bgxb.2022.0228
	LI Q, CHEN L, GAN H Y, et al. Electrostatic spraying preparation and performance of nanocomposite energetic material RDX@NGEC[J]. Acta Armamentarii, 2023, 44(7): 1985-1992. (in Chinese) doi: 10.12382/bgxb.2022.0228
[2]	SULLIVAN K T, ZHU C, DUOSS E B, et al. Controlling material reactivity using architecture[J]. Advanced materials, 2016, 28: 1934-1939. doi: 10.1002/adma.201504286
[3]	刘洁, 李含健, 任慧, 等. 纳米碳材料对含硼铝热剂燃烧性能的影响[J]. 兵工学报, 2019, 40 (1): 42-48. doi: 10.3969/j.issn.1000-1093.2019.01.006
	LIU J, LI H J, REN H, et al. Influences of nano-carbon materials on combustion performance of boron-based thermite[J]. Acta Armamentarii, 2019, 40 (1): 42-48. (in Chinese) doi: 10.3969/j.issn.1000-1093.2019.01.006
[4]	WU T, SINGH V, JULIEN B, et al. Pioneering insights into the superior performance of titanium as a fuel in energetic materials[J]. Chemical Engineering Journal, 2023, 453: 139922.
[5]	COMET M, MARTIN C, SCHNELL F, et al. Nanothermite foams: From nanopowder to object[J]. Chemical Engineering Journal, 2017, 316: 807-812.
[6]	TANG D Y, FAN Z M, YANG G C, et al. Combustion performance of composite propellants containing core-shell Al@M(IO₃)_x metastable composites[J]. Combustion and Flame, 2020, 219: 33-43.
[7]	MA X X, LI Y X, HUSSAIN I, et al. Core-shell structured nanoenergetic materials: preparation and fundamental properties[J]. Advanced Materials, 2020, 32: 2001291.
[8]	WANG Y T, ZHANG X T, XU J B, et al. Fabrication and characterization of Al-CuO nanocomposites prepared by sol-gel method[J]. Defence Technology, 2021, 17(4): 1307-1312.
[9]	薛闯, 高贫, 王桂香, 等. Al/Fe₂O₃纳米铝热剂界面结构和稳定性的周期性密度泛函理论研究[J]. 含能材料, 2022, 30(3): 197-203.
	XUE C, GAO P, WANG G X, et al. Interface structure and stability of Al/Fe₂O₃ nano-thermite: a periodic DFT study[J]. Chinese Journal of Energetic Materials, 2022, 30(3): 197-203. (in Chinese)
[10]	SHI K W, GUO X D, CHEN L, et al. Alcohol-thermal synthesis of approximately core-shell structured Al@CuO nanothermite with improved heat-release and combustion characteristics[J]. Combustion and Flame, 2021, 228: 331-339.
[11]	YIN Y J, LI X M, SHU Y J, et al. Highly-reactive Al/CuO nanoenergetic materials with a tubular structure[J]. Materials and Design, 2017, 117: 104-110.
[12]	XU F Y, BISWAS P, NAVA G, et al. Tuning the reactivity and energy release rate of I₂O₅ based ternary thermite systems[J]. Combustion and Flame, 2021, 228: 210-217.
[13]	JIAN G Q, FENG J Y, JACOB R J, et al. Super-reactive nanoenergetic gas generators based on periodate salts[J]. Angewandte Chemie International Edition, 2013, 52(37): 9743-9746.
[14]	YIN Y J, HU F, CHENG L H, et al. Electrophoretic deposition of hybrid organic-inorganic PTFE/Al/CuO energetic film[J]. Defence Technology, 2023, 22: 112-118.
[15]	张纯, 史凯文, 周翔. 静电纺丝工艺制备Si@PVDF纳米结构含能材料[J]. 火工品, 2020(6): 34-37.
	ZHANG C, SHI K W, ZHOU X. Electrospinning preparation of Si@PVDF nanostructured energetic material[J]. Initiators and Pyrotechnics, 2020(6): 34-37. (in Chinese)
[16]	JABRAOUI H, ESTEVE A, HONG S, et al. Initial stage of titanium oxidation in Ti/CuO thermites: a molecular dynamics study using ReaxFF forcefields[J]. Physical Chemistry Chemical Physics, 2023, 25:11268. doi: 10.1039/d3cp00032j pmid: 37060120
[17]	QIAO X, CHEN K, CORKETT A J, et al. Synthesis, crystal structure, symmetry relationships and electronic structure of bismuth carbodiimide Bi₂(NCN)₃ and its ammonia adduct Bi₂(NCN)₃·NH₃[J]. Inorganic Chemistry, 2021, 60: 12664-12670.
[18]	LIU X H, PUSPITOSARI H, DRONSKOWSKI R. An investigation of the formation mechanism of copper (Ⅱ) carbodiimide[J]. Special Issue: Dedicated to Professor Arndt Simon on the Occasion of His 70th Birthday, 2010, 636(1): 121-125.
[19]	MORITA K, GABRIELA M, KANAME Y, et al. Thermal stability, morphology and electronic band gap of Zn(NCN)[J]. Solid State Sciences, 2013, 23: 50-57.
[20]	GUO P H, CAO L Y, WANG R, et al. In situ construction of “Anchor-Like” structures in Fe(NCN) for long cyclic life in sodium-ion batteries[J]. Advanced Functional Materials, 2020, 30: 2000208.
[21]	HERLITSCHKE M, TCHOUGRE'EFF A L, SOUDACKOV A V, et al. Magnetism and lattice dynamics of Fe(NCN) compared to FeO[J]. New Journal of Chemistry, 2014, 38: 4670.