火炸药学报

为了改善高氯酸铵(AP)的热分解性能, 基于聚乙烯亚胺(PEI)本征的正电荷和氨基基团,在与负电荷AP发生静电自组装包覆的同时,吸附铜金属催化剂于AP表面,制备了AP/PEI/Cu(ClO₄)₂包覆样品,并通过DTA和TG-DSC等热分析技术研究了其热分解行为; 通过SEM、XPS、XRD、IR、ICP-OES和Zeta电位等测试手段对AP/PEI/Cu(ClO₄)₂包覆样品的形貌与结构进行了表征。结果表明,与原料AP相比,AP/PEI/Cu(ClO₄)₂包覆样品的高温分解峰温降低了94.2℃,表观放热量增加了512.91J/g,证实PEI/Cu(ClO₄)₂对AP的热分解具有良好的催化效果; PEI的加入能增强金属催化剂和AP的界面作用,使得催化剂更均匀地分布于AP表面,从而促使金属催化剂更好地发挥热分解催化作用。

In order to improve the thermal decomposition performance of AP, based on the intrinsic positive charge and amino group of polyethyleneimine(PEI), the AP/PEI/Cu(ClO₄)₂ coated sample was prepared by adsorbing copper metal catalyst on the surface of AP while electrostatic self-assembly coating with negative charge AP, and its thermal decomposition behavior was studied by thermal analysis technology. The morphology and structure of AP/PEI/Cu(ClO₄)₂ coated samples were characterized by SEM, XPS, XRD, IR, ICP-OES, and Zeta potential. The results show that compared with raw AP, the high temperature decomposition peak temperature of AP/PEI/Cu(ClO₄)₂ coated sample is reduced by 94.2℃, and the apparent heat release is increased by 512.91J/g, which confirmed that PEI/Cu(ClO₄)₂ has a good catalytic effect on the thermal decomposition of AP. The addition of PEI can enhance the interfacial interaction between metal catalyst and AP, making the catalyst more evenly distributed on the surface of AP, promoting the better catalytic effect of metal catalyst on the thermal decomposition.

引言
1 实验
2 结果与讨论
3 结论

图1 升温速率10℃/min下不同金属盐和PEI/金属盐催化AP热分解的DTA曲线<br/>Fig.1 DTA curves of thermal decomposition of AP catalyzed by different metal salts and PEI/metal salts at the heating rate of 10℃/min

图1 升温速率10℃/min下不同金属盐和PEI/金属盐催化AP热分解的DTA曲线
Fig.1 DTA curves of thermal decomposition of AP catalyzed by different metal salts and PEI/metal salts at the heating rate of 10℃/min

图2 升温速率10℃/min下不同铜盐和PEI/铜盐催化AP热分解的DTA曲线<br/>Fig.2 DTA curves of thermal decomposition of AP catalyzed by different copper salts and PEI/copper salts at the heating rate of 10℃/min

图2 升温速率10℃/min下不同铜盐和PEI/铜盐催化AP热分解的DTA曲线
Fig.2 DTA curves of thermal decomposition of AP catalyzed by different copper salts and PEI/copper salts at the heating rate of 10℃/min

图3 升温速率10℃/min下不同含量催化剂包覆AP的DTA曲线<br/>Fig.3 DTA curves of AP coated with different contents of catalyst at the heating rate of 10℃/min

图3 升温速率10℃/min下不同含量催化剂包覆AP的DTA曲线
Fig.3 DTA curves of AP coated with different contents of catalyst at the heating rate of 10℃/min

图4 不同升温速率下AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的DTA曲线<br/>Fig.4 DTA curves of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2 at different heating rates

图4 不同升温速率下AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的DTA曲线
Fig.4 DTA curves of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2 at different heating rates

图5 高温分解阶段AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的KAS方法和FWO方法的拟合结果<br/>Fig.5 The fitting results of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2 by using the KAS method and FWO method in the HTD stage

图5 高温分解阶段AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的KAS方法和FWO方法的拟合结果
Fig.5 The fitting results of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2 by using the KAS method and FWO method in the HTD stage

表1 AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的热分解动力学参数<br/>Table 1 Kinetic parameters of thermal decomposition of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2

表1 AP、AP/Cu(ClO4)2和AP/PEI/Cu(ClO4)2的热分解动力学参数
Table 1 Kinetic parameters of thermal decomposition of AP, AP/Cu(ClO4)2 and AP/PEI/Cu(ClO4)2

图6 升温速率15℃/min下AP和AP/PEI/Cu(ClO4)2的TG-DSC曲线<br/>Fig.6 TG-DSC curves of AP and AP/PEI/Cu(ClO4)2 at the heating rate of 15℃/min

图6 升温速率15℃/min下AP和AP/PEI/Cu(ClO4)2的TG-DSC曲线
Fig.6 TG-DSC curves of AP and AP/PEI/Cu(ClO4)2 at the heating rate of 15℃/min

表2 样品的放热量和失重率<br/>Table 2 The heat release and mass loss rate of samples

表2 样品的放热量和失重率
Table 2 The heat release and mass loss rate of samples

图7 AP、AP/PEI/Cu(ClO4)2的SEM及对应的Cu-Mapping<br/>Fig.7 SEM images of AP, AP/PEI/Cu(ClO4)2 and corresponding Cu-Mapping of AP/PEI/Cu(ClO4)2

图7 AP、AP/PEI/Cu(ClO4)2的SEM及对应的Cu-Mapping
Fig.7 SEM images of AP, AP/PEI/Cu(ClO4)2 and corresponding Cu-Mapping of AP/PEI/Cu(ClO4)2

图8 AP和AP/PEI/Cu(ClO4)2的N1s谱图<br/>Fig.8 N1s spectra of AP andAP/PEI/Cu(ClO4)2

图8 AP和AP/PEI/Cu(ClO4)2的N1s谱图
Fig.8 N1s spectra of AP andAP/PEI/Cu(ClO4)2

图9 AP和AP/PEI/Cu(ClO4)2的粉末XRD图谱<br/>Fig.9 XRD spectra of AP and AP/PEI/Cu(ClO4)2 powder

图9 AP和AP/PEI/Cu(ClO4)2的粉末XRD图谱
Fig.9 XRD spectra of AP and AP/PEI/Cu(ClO4)2 powder

图10 AP和AP/PEI/Cu(ClO4)2的红外光谱图<br/>Fig.10 Infrared spectra of AP and AP/PEI/Cu(ClO4)2

图10 AP和AP/PEI/Cu(ClO4)2的红外光谱图
Fig.10 Infrared spectra of AP and AP/PEI/Cu(ClO4)2

图11 AP/PEI/Cu(ClO4)2的TG-MS图<br/>Fig.11 TG-MS spectrum of AP/PEI/Cu(ClO4)2

图11 AP/PEI/Cu(ClO4)2的TG-MS图
Fig.11 TG-MS spectrum of AP/PEI/Cu(ClO4)2

图12 PEI/Cu(ClO4)2催化AP热分解的示意图<br/>Fig.12 Schematic diagram of PEI/Cu(ClO4)2 catalyzed AP thermal decomposition

图12 PEI/Cu(ClO4)2催化AP热分解的示意图
Fig.12 Schematic diagram of PEI/Cu(ClO4)2 catalyzed AP thermal decomposition

[1] BECKSTEAD M W, PUDUPPAKKAM K, THAKRE P, et al. Modeling of combustion and ignition of solid-propellant ingredients[J]. Progress in Energy and Combustion Science, 2007, 33(6): 497-551.
[2]WENXIAN WEI B X, QINGLI HUANG. Controllable synthesis and catalytic property of novel copper oxides(CuO and Cu2O)Nanostructures[J]. International Journal of Materials Science and Applications, 2016, 5(1):18-22..
[3]YAN N, QIN L, LI J, et al. Atomic layer deposition of iron oxide on reduced graphene oxide and its catalytic activity in the thermal decomposition of ammonium perchlorate[J].Applied Surface Science, 2018, 451: 155-161.
[4]BENHAMMADA A, TRACHE D, CHELOUCHE S, et al. Catalytic effect of green CuO nanoparticles on the thermal decomposition kinetics of ammonium perchlorate[J].Zeitschrift Für Anorganische und Allgemeine Chemie, 2020, 647(4): 312-325.
[5]叶平, 鲁月文, 许鹏飞, 等. 纳米CoFe2O4@C复合催化剂的制备及其对AP的催化性能[J]. 火炸药学报, 2019, 42(4): 358-362.

₂

₄

[6]刘波, 刘少武, 于慧芳, 等. 二硝酰胺铵防吸湿技术研究进展[J]. 化学推进剂与高分子材料, 2011, 9(6): 57-60.
[7]ATHAR J, GHOSH M, DENDAGE P S, et al. Nanocomposites: An ideal coating material to reduce the sensitivity of hydrazinium nitroformate(HNF)[J]. Propellants, Explosives, Pyrotechnics, 2010, 35(2): 153-158.
[8]ZHENG S, LIU J, WANG Y, et al. Effect of aluminum morphology on thermal decomposition of ammonium perchlorate[J].Journal of Thermal Analysis and Calorimetry, 2018, 134(3): 1823-1828.
[9]XU H, ZHAO C, HU T, et al. Electrostatic self-assembly of PEI-imidazole derivative and its application in catalytic thermal decomposition of AP[J].Catalysis Letters, 2024, 154: 206-216.
[10]LI S, NIU Z, JIAO Y, et al. Preparation of different morphology Cu/GO nanocomposites and their catalytic performance for thermal decomposition of ammonium perchlorate[J].RSC Advance, 2022, 35(12): 22806-22814.
[11]JAIN S, VARMA V K, MAHAJAN A K, et al. Thermal decomposition of ammonium perchlorate in the presence of copper tungsten oxide(CuWO4)[J]. Propellants, Explosives, Pyrotechnics, 2021, 46(5): 758-765.
[12]TONDA S, KUMAR S, KANDULA S, et al. Fe-doped and-mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight[J].Journal of Materials Chemistry A, 2014, 19(2): 6772-6780.
[13]YU Z, CHEN L, LU L, et al. DSC/TG-MS Study on in situ catalytic thermal decomposition of ammonium perchlorate over CoC2O4[J].Chinese Journal of Catalysis, 2009, 30(1): 19-23.
[14]BIRCUMSHAW L L, NEWMAN B H. The thermal decomposition of ammonium perchlorate-I. Introduction, experimental, analysis of gaseous products, and thermal decomposition experiments[J].Proceedings of the Royal Society of London(Series A: Mathematical and Physical Sciences), 1997, 227(1168): 115-132.
[15]ZHANG Y, LI K, LIAO J, et al. Microwave-assisted synthesis of graphitic carbon nitride/CuO nanocomposites and the enhancement of catalytic activities in the thermal decomposition of ammonium perchlorate[J].Applied Surface Science, 2020, 499: 143875(1-10).
[16]LI Y, LI J, TANG Q, et al. Catalytic decomposition effect and mechanism of energetic complex Cu(NH3)4(AFT)2 towards fine AP[J]. Catalysis Letters, 2021, 152(9): 2678-2687.
[17]BENHAMMADA A, TRACHE D. Thermal decomposition of energetic materials using TG-FTIR and TG-MS: a state-of-the-art review[J].Applied Spectroscopy Reviews, 2019, 55(8): 724-777.
[18]CHATURVEDI S, DAVE P N, PATEL N N. Nano-alloys: Potential catalyst for thermal decomposition of ammonium perchlorate[J].Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2013, 44(2): 258-262.
[19]LI X, LI S, HU H, et al. Facet effects of α-Fe2O3 with different morphologies on the thermal decomposition of ammonium perchlorate[J]. Catalysis Letters, 2022, 152(11): 3479-3488.
[20]KECHIT H, BELKHIRI S, BHAKTA A K, et al. The effect of iron decorated MWCNTs and iron-ionic liquid decorated MWCNTs onto thermal decomposition of ammonium perchlorate[J].Zeitschrift Für Anorganische und Allgemeine Chemie, 2021, 647(16/17): 1607-1619.
[21]NABID M R, BIDE Y, DASTAR F. One pot synthesis of nickel nanoparticles stabilized on rGO/polyethyleneimine aerogel for the catalytic hydrogen generation[J]. Catalysis Letters, 2015, 145(9): 1798-1807.
[22]ABRISHAMI F, SOUFI A, MAHYARI M. Cu(I)@g-C3N4/PEI: A new heterogeneous catalyst for glaser reaction in deep eutectic solvent[J]. Catalysis Letters, 2023, 153: 2989-3002.
[23]NABID M R, BIDE Y, SHOJAIPOUR M, et al. Yolk/shell AuNPs@polyethyleneimine-derived carbon nanoparticles as nanoreactor for catalytic nitroarenes reduction[J].Catalysis Letters, 2015, 146(1): 229-237.
[24]CHEN Y, PAN B, LI H, et al. Selective removal of Cu(II)Ions by using cation-exchange resin-supported polyethyleneimine(PEI)nanoclusters[J].Environmental Science & Technology, 2010, 44: 3508-3513.
[25]SONG X, HUANG Q, JIN B, et al. Preparation of desensitizing CL-20/rGO composites by in-situ reduction[J].Propellants, Explosives, Pyrotechnics, 2020, 45(8): 1293-1299.
[26]VARA J A, DAVE P N, CHATURVEDI S. The catalytic activity of transition metal oxide nanoparticles on thermal decomposition ofammonium perchlorate[J]. Defence Technology, 2019, 15(4): 629-635.
[27]冯海萌, 赵向华, 罗小凡, 等. 一种三唑类配合物对高氯酸铵的催化性能研究[J]. 石油化工应用, 2021, 40(9): 113-116.
[28]BEARD B C, SANDUSKY H W, GLANCY B C, et al. Quantitative correlation of XPS linewidth with dislocation density in shock-loaded ammonium perchlorate[J]. Surface and Interface Analysis, 1993, 20(2): 140-148.
[29]CHOUDHARY B C, PAUL D, BORSE A U, et al. Surface functionalized biomass for adsorption and recovery of gold from electronic scrap and refinery wastewater[J].Separation and Purification Technology, 2018, 195: 260-270.
[30]BEDIAKO J K, CHOI J W, SONG M H, et al. Self-coagulating polyelectrolyte complexes for target-tunable adsorption and separation of metal ions[J]. Journal of Hazardous Materials, 2021, 401: 123352(1-11).
[31]SONG X, HUANG Q, JIN B, et al. Fabrication and characterization of CL-20/PEI/GO composites with enhanced thermal stability and desensitization via electrostatic self-assembly[J].Applied Surface Science, 2021, 558:149933(1-9).
[32]高小慧, 宋小兰, 张效, 等. 纳米结构高氯酸铵的制备及其性能和防吸湿性研究[J]. 固体火箭技术, 2022, 45(2): 261-268.
[33]YAN J, WANG H, JIN B, et al. Cu-MOF derived Cu/Cu2O/C nanocomposites for the efficient thermal decomposition of ammonium perchlorate[J]. Journal of Solid State Chemistry, 2021, 297:122060(1-10).
[34]LIU L, HAO W, HUANG Q, et al. Three new energetic coordination polymers based on nitrogen-rich heterocyclic ligand for thermal catalysis of ammonium perchlorate[J].Journal of Solid State Chemistry, 2022, 314:123375(1-8).
[35]HANAFI S, TRACHE D, HE W, et al. Thermostable energetic coordination polymers based on functionalized GO and their catalytic effects on the decomposition of AP and RDX[J].The Journal of Physical Chemistry C, 2020, 124(9): 5182-5195.

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