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Ferrocene-fullerene dyad as a novel burn rate modifier for propellants 二茂铁-富勒烯二元化合物作为推进剂的新型燃烧速率调节剂
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.001
Shrutika Sriramrao, Parveen Raman, Akash Dhas, Shaibal Banerjee

The burn rate of composite rocket propellants serves as a critical ballistic parameter in the construction of a rocket engine. Due to their large surface areas, carbon-based materials such as carbon nanotubes, graphene, and fullerene have demonstrated promising results as burn rate modifiers (BRMs) for propellants. Unlike their inorganic counterparts, these materials, being combustible, contribute to energy output besides enhancing the burn rate. This study reported a ferrocene-fullerene dyad as a BRM prepared through the thermal decomposition of ammonium perchlorate (AP) in composite solid propellants. By incorporating 0.6 wt% of the dyad, the burn rate of the prepared propellants increased by 70%, accompanied by a rise in their calorific value.

复合火箭推进剂的燃烧速率是制造火箭发动机的关键弹道参数。由于碳基材料(如碳纳米管、石墨烯和富勒烯)具有较大的表面积,因此作为推进剂的燃烧速率改性剂(BRMs)已显示出良好的效果。与无机材料不同,这些材料具有可燃性,除了提高燃烧速率外,还有助于能量输出。本研究报告了一种二茂铁-fullerene二元化合物,它是通过热分解复合固体推进剂中的高氯酸铵(AP)制备的BRM。通过加入 0.6 wt% 的二茂铁,所制备推进剂的燃烧速率提高了 70%,同时热值也有所提高。
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引用次数: 0
Cover Story 封面故事
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/S2666-6472(24)00017-4
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引用次数: 0
Auto-ignition of ionic liquid fuels with hydrogen peroxide triggered by copper-containing liquid promoter 含铜液体促进剂引发过氧化氢离子液体燃料自燃
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.006
Si-cheng Liao , Tian-lin Liu , Zhi-yu Zhou , Kang-cai Wang , Qing-hua Zhang

Research into next-generation propellants with green fuel–oxidizer pairs to replace the currently used highly toxic hydrazine–N2O4 system has attracted widespread attention. Ionic liquids (ILs) and hydrogen peroxide have demonstrated their feasibility as a green fuel and an oxidizer, respectively. However, the realisation of effective auto-ignition is the key problem. In this study, a new strategy to trigger the auto-ignition of ILs fuels with hydrogen peroxide by using a unique copper-containing liquid as the promoter is developed. The copper-containing promoter is designed such that its cationic structure is similar to that of the ILs fuels. Based on the principle of “like dissolves like,” the fuel and promoter can be miscible at any ratio to eventually form a catalytic fuel. In addition, the physicochemical properties (e.g. density, viscosity and decomposition temperature) and performance parameters (e.g. ignition delay time and specific impulse) of the as-prepared catalytic fuel are completely characterised. Owing to their excellent hypergolic performance with a short ignition delay time of 16 ms, in combination with the advantages of simple preparation, perfect solubility and green characteristics, the catalytic fuel–oxidizer pair demonstrates promise as bipropellants for rocket applications.

为取代目前使用的剧毒肼-N2O4 系统,对具有绿色燃料-氧化剂组合的下一代推进剂的研究引起了广泛关注。离子液体(IL)和过氧化氢已分别证明了其作为绿色燃料和氧化剂的可行性。然而,实现有效的自燃是关键问题。本研究开发了一种新策略,通过使用一种独特的含铜液体作为促进剂来触发离子液体燃料与过氧化氢的自燃。含铜促进剂的阳离子结构与 ILs 燃料的阳离子结构相似。根据 "同类相溶 "的原理,燃料和促进剂可以任意比例混溶,最终形成催化燃料。此外,制备的催化燃料的物理化学特性(如密度、粘度和分解温度)和性能参数(如点火延迟时间和比冲)也得到了完整表征。由于催化燃料-氧化剂组合具有出色的双酚性能,点火延迟时间短至 16 毫秒,同时还具有制备简单、溶解性好和绿色环保等优点,因此有望成为火箭应用的双推进剂。
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引用次数: 0
CL-20 analogues: Structure - Thermal stability/decomposition mechanism relationships CL-20 类似物:结构-热稳定性/分解机理关系
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.008
Valery P. Sinditskii , Nikolai V. Yudin , Valery V. Serushkin , Anna O. Gubina , Anastasia D. Smirnova , Vladimir V. Parakhin , Gennadii A. Smirnov , Kyrill Yu Suponitsky , Aleksei B. Sheremetev

The thermal decomposition of a number of analogues of hexanitrohexaazaisowurtzitan (CL-20), in where one or more N-nitro groups have been replaced by another explosophoric unit (diverse N-alkylnitramine groups or N- trinitroethyl), has been studied by methods of isothermal and non-isothermal kinetics. It was found that replacing the N-nitro group with even a more thermally stable substituent leads to a decrease in the stability of the nitrated hexaazaisowurtzitane framework. It was suggested that the substituent distorts the symmetry of the strained hexaazaisowurtzitane cage, which affects the strength of the N–NO2 bond. When a substituent less stable than the N-nitro group in the parent CL-20 is installed, the initial stage of degradation is determined by the decomposition kinetics of this substituent. One of the objects of this study, 4,10-dinitro-2,6,8,12-tetrakis (2,2,2-trinitroethyl) −2,4,6,8,10,12-hexaazaisowurtzitane (8), was synthesized for the first time; it was fully characterized and also confirmed by X-ray structural data.

通过等温和非等温动力学方法,研究了一些六硝基六氮唑麝香草烷(CL-20)类似物的热分解,其中一个或多个-硝基被另一个爆炸单位(多种多样的-烷基硝胺基团或-三硝基乙基)取代。研究发现,即使用热稳定性更高的取代基取代-硝基,也会导致硝化六氮唑乌齐坦框架的稳定性降低。研究表明,取代基改变了六氮aisowurtzitane 应变笼的对称性,从而影响了 N-NO 键的强度。如果在母体 CL-20 中加入稳定性低于 N-硝基的取代基,降解的初始阶段将由该取代基的分解动力学决定。本研究首次合成了 4,10-二硝基-2,6,8,12-四(2,2,2-三硝基乙基)-2,4,6,8,10,12-六氮唑乌齐坦(),并对其进行了全面表征和 X 射线结构数据确认。
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引用次数: 0
N-Acetonitrile functionalized 3-nitrotriazole: Precursor to nitrogen rich stable and insensitive energetic materials N-乙腈官能化 3-硝基三唑:富氮稳定不敏感高能材料的前体
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.01.003
Prachi Bhatia, Peddapothula Sahithi Priya, Priyanka Das, Dheeraj Kumar

In the field of energetic materials, prime attention has been given to the synthesis of environmentally compatible energetic materials having an adequate balance between energy and stability. For this purpose, nitrogen-rich heterocyclic rings have contributed as pivotal frameworks. Nitro-functionalized 1,2,4-triazoles have been profusely used as a constituent for synthesizing high-performing energetic materials (EMs) due to their high nitrogen content, good thermal stability, and modifiable sites via functionalization. Combination with a different energetic scaffold may provide an opportunity for accessible tailoring. In this work, in an effort to investigate the potential of 3-nitrotriazoles, its N-acetonitrile derivative 2 was synthesized, which was further converted to various explosophores. N-methylene-C bridged asymmetrically connected tetrazole (3) and 1,2,4-oxadiazole (9 and 10) based EMs have been synthesized. Further tuning of energetic properties via salt formation strategy was employed for the synthesis of compounds 47, 11 and 12. 1,2,4-oxadiazole-based compound 9 was also confirmed via X-ray diffraction analysis, and 10 was analyzed with 15N NMR spectroscopy. Compounds 3, 4, 5, 7 and 9 exhibited high thermal stabilities and were found to be insensitive towards impact and friction. Compounds 5, 6, and 10 exhibited detonation performance comparable to the conventional insensitive explosive TATB.

在高能材料领域,人们最关注的是合成与环境相容的高能材料,并在能量和稳定性之间取得适当的平衡。为此,富氮杂环作为关键框架做出了贡献。硝基官能化的 1,2,4- 三唑因其氮含量高、热稳定性好以及可通过官能化修饰位点而被广泛用作合成高性能高能材料(EMs)的成分。与不同的高能支架结合可为无障碍定制提供机会。在这项工作中,为了研究 3-硝基三唑的潜力,我们合成了其 N-乙腈衍生物 2,并进一步将其转化为各种爆炸物。基于 N-亚甲基-C 桥接的不对称连接四氮唑(3)和 1,2,4-恶二唑(9 和 10)的 EM 已被合成。在合成化合物 4-7、11 和 12 时,通过盐形成策略进一步调整了能量特性。基于 1,2,4-噁二唑的化合物 9 还通过 X 射线衍射分析得到了证实,而 10 则通过 15N NMR 光谱进行了分析。化合物 3、4、5、7 和 9 具有很高的热稳定性,并且对冲击和摩擦不敏感。化合物 5、6 和 10 的引爆性能与传统的不敏感炸药 TATB 相当。
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引用次数: 0
3,7-Dinitroimidazo[1,2-b]pyridazine-6,8-diamine: A promising building block for advanced heat-resistant and low-sensitivity energetic materials 3,7-二硝基咪唑并[1,2-b]哒嗪-6,8-二胺:先进耐热和低敏感高能材料的理想构件
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.003
Jing Feng , Jie Sun , Lei Yang , Zhen-qi Zhang , Yang Liu , Qing Ma , Li-shuang Hu

Constructing heat-resistant fused heterocyclic compounds is increasingly fascinating in the field of energetic materials due to their excellent energy, high thermal stability, and low sensitivity, as well as high density in general. This study synthesized a novel heat-resistant explosive based on the imidazo [1,2-b]pyridazine fused ring,3,7-dinitroimidazo [1,2-b]pyridazine-6,8-diamine (5),using a three-step facile method. This compound exhibited a high density (1.856 g cm−3) and low mechanical sensitivities (IS = 40 J, FS = 350 N). Meanwhile, it displayed a higher thermal decomposition temperature of 324 °C compared to conventional heat-resistant explosive HNS (Td = 318 °C). In addition, it demonstrated significantly higher detonation performance (D = 8336 m s−1, p = 27.25 GPa) than both TNT (D = 6881 m s−1, p = 19.5 GPa) and HNS (D = 7612 m s−1, p = 24.3 GPa). Theoretical analysis shows that the intramolecular hydrogen bonding interactions of NH2–NO2–NH2 might be the main reason for the heat resistance of energetic materials based on the imidazo [1,2-b]pyridazine fused ring. The results of this study suggest that compound 5 is a promising building block and a candidate for heat-resistant energetic materials.

由于具有卓越的能量、高热稳定性、低敏感性和高密度等特点,构建耐热的融合杂环化合物在高能材料领域越来越具有吸引力。本研究采用三步法合成了一种基于咪唑并[1,2-]哒嗪融合环的新型耐热炸药,即 3,7-二硝基咪唑并[1,2-]哒嗪-6,8-二胺()。该化合物密度高(1.856 g cm),机械敏感性低(= 40 J,= 350 N)。同时,与传统的耐热炸药 HNS(= 318 ℃)相比,它的热分解温度更高(324 ℃)。此外,它的引爆性能(= 8336 秒,= 27.25 GPa)明显高于 TNT(= 6881 秒,= 19.5 GPa)和 HNS(= 7612 秒,= 24.3 GPa)。理论分析表明,NH-NO-NH 的分子内氢键相互作用可能是基于咪唑[1,2-]哒嗪融合环的高能材料具有耐热性的主要原因。研究结果表明,该化合物是一种很有前景的构筑基块,是耐热高能材料的候选材料。
{"title":"3,7-Dinitroimidazo[1,2-b]pyridazine-6,8-diamine: A promising building block for advanced heat-resistant and low-sensitivity energetic materials","authors":"Jing Feng ,&nbsp;Jie Sun ,&nbsp;Lei Yang ,&nbsp;Zhen-qi Zhang ,&nbsp;Yang Liu ,&nbsp;Qing Ma ,&nbsp;Li-shuang Hu","doi":"10.1016/j.enmf.2024.02.003","DOIUrl":"10.1016/j.enmf.2024.02.003","url":null,"abstract":"<div><p>Constructing heat-resistant fused heterocyclic compounds is increasingly fascinating in the field of energetic materials due to their excellent energy, high thermal stability, and low sensitivity, as well as high density in general. This study synthesized a novel heat-resistant explosive based on the imidazo [1,2-<em>b</em>]pyridazine fused ring,3,7-dinitroimidazo [1,2-<em>b</em>]pyridazine-6,8-diamine (<strong>5</strong>),using a three-step facile method. This compound exhibited a high density (1.856 g cm<sup>−3</sup>) and low mechanical sensitivities (<em>IS</em> = 40 J, <em>FS</em> = 350 N). Meanwhile, it displayed a higher thermal decomposition temperature of 324 °C compared to conventional heat-resistant explosive HNS (<em>T</em><sub>d</sub> = 318 °C). In addition, it demonstrated significantly higher detonation performance (<em>D</em> = 8336 <em>m</em> s<sup>−1</sup>, <em>p</em> = 27.25 GPa) than both TNT (<em>D</em> = 6881 <em>m</em> s<sup>−1</sup>, <em>p</em> = 19.5 GPa) and HNS (<em>D</em> = 7612 <em>m</em> s<sup>−1</sup>, <em>p</em> = 24.3 GPa). Theoretical analysis shows that the intramolecular hydrogen bonding interactions of NH<sub>2</sub>–NO<sub>2</sub>–NH<sub>2</sub> might be the main reason for the heat resistance of energetic materials based on the imidazo [1,2-<em>b</em>]pyridazine fused ring. The results of this study suggest that compound <strong>5</strong> is a promising building block and a candidate for heat-resistant energetic materials.</p></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666647224000046/pdfft?md5=9e766e598dae0d3ef17fcad7727fdaf5&pid=1-s2.0-S2666647224000046-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139926593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A density functional theory investigation of the substituent effect on acyclovir and guanine derivatives for applications on energetic materials 对阿昔洛韦和鸟嘌呤衍生物取代基效应的密度泛函理论研究,以应用于高能材料
Q2 Engineering Pub Date : 2024-02-23 DOI: 10.1016/j.enmf.2024.01.002
Luciana Amorim da Silva, Gabriel Monteiro-de-Castro, Erick Galante, Itamar Borges Jr, Aline Cardoso Anastácio
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引用次数: 0
Tensors of thermal deformation for various polymorphic modifications of 2,4-dinitroanisole 2,4-二硝基苯甲醚各种多晶型修饰的热变形张量
Q2 Engineering Pub Date : 2024-02-05 DOI: 10.1016/j.enmf.2024.02.002
Aleksandr V. Stankevich, Nikolay A. Rasputin, Anisa Kh Rudina, Gennady L. Rusinov, Vera I. Filyakova, Valery N. Charushin

The anisotropic characteristics of thermal deformation of ultrapure 2,4-dinitroanisole (2,4DNAN) crystals were determined by the methods of powder thermorentgenography of the internal standard. The points of structural changes are registered in increments of 10 K, and in the melting region of 2 and 1 K. Calculations of powder X-ray diffraction data are performed by methods of full-profile analysis with a cycle of quantum modeling of the structure of molecules integrated into the algorithm. The Pauli, Le Bail (WPPD), Rietveld (WPPF) and WPPM methods were used as reference methods for full-profile analysis. The main crystallographic axes and characteristic surfaces of the thermal deformation tensor α and β-2,4-DNAN are determined. At atmospheric pressure, the main coefficients of linear (α) and volumetric (β) thermal deformation (expansion) were at 293 K for α-2,4-DNAN with α1(293) = 11,516 × 10−5 K−1, α2(293) = −0,120 × 10−5 K−1, α3(293) = 5,098 × 10−5 K−1, β(293) = 16,333 × 10−5 K−1; at 293 K for β-2,4-DNAN with α1(293) = 13,217 × 10−5 K−1, α2(293) = 0,494 × 10−5 K−1, α3(293) = −8,6504 × 10−5 K−1, β(293) = 6,8191 × 10−5 K−1; at 260 K for β′-2,4-DNAN with α1(260) = 25,214 × 10−5 K−1, α2(260) = −5,823 × 10−5 K−1, α3(260) = 7,741 × 10−5 K−1, β(260) = 27,112 × 10−5 K−1.

超纯 2,4-dinitroanisole (2,4DNAN) 晶体热变形的各向异性特征是通过内标粉末热成像仪方法测定的。结构变化点以 10 K 为增量,在 2 K 和 1 K 的熔化区域进行记录。粉末 X 射线衍射数据的计算是通过全剖面分析方法进行的,算法中集成了分子结构的量子建模循环。保利法、勒贝尔法(WPPD)、里特维尔德法(WPPF)和 WPPM 法被用作全剖面分析的参考方法。确定了热变形张量 α 和 β-2,4-DNAN 的主要晶体学轴线和特征面。在大气压力下,α-2,4-DNAN 的主要线性(α)和体积(β)热变形(膨胀)系数在 293 K 时为 α1(293) = 11,516 × 10-5 K-1,α2(293) = -0,120 × 10-5 K-1,α3(293) = 5,098 × 10-5 K-1,β(293) = 16,333 × 10-5 K-1;293 K 时,β-2,4-DNAN 的 α1(293) = 13,217 × 10-5 K-1,α2(293) = 0,494 × 10-5 K-1,α3(293) = -8,6504 × 10-5 K-1,β(293) = 6,8191 × 10-5 K-1;α1(260) = 25,214 × 10-5 K-1,α2(260) = -5,823 × 10-5 K-1,α3(260) = 7,741 × 10-5 K-1,β(260) = 27,112 × 10-5 K-1。
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引用次数: 0
A new sulfur-containing laser-sensitive primary explosive based on thiazole-4-carbohydrazide 基于噻唑-4-甲酰肼的新型含硫激光敏感原爆物
Q2 Engineering Pub Date : 2024-02-01 DOI: 10.1016/j.enmf.2024.02.005
Chao Zhang, Ting-wei Wang, Zu-jia Lu, Zhen-xin Yi, Meiqi Xu, Yan Li, Qi-yao Yu, Zhi-min Li, Jian-guo Zhang
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引用次数: 0
A new sulfur-containing laser-sensitive primary explosive based on thiazole-4-carbohydrazide 基于噻唑-4-甲酰肼的新型含硫激光敏感原爆物
Q2 Engineering Pub Date : 2024-02-01 DOI: 10.1016/j.enmf.2024.02.005
Chao Zhang, Ting-wei Wang, Zu-jia Lu, Zhen-xin Yi, Meiqi Xu, Yan Li, Qi-yao Yu, Zhi-min Li, Jian-guo Zhang
{"title":"A new sulfur-containing laser-sensitive primary explosive based on thiazole-4-carbohydrazide","authors":"Chao Zhang, Ting-wei Wang, Zu-jia Lu, Zhen-xin Yi, Meiqi Xu, Yan Li, Qi-yao Yu, Zhi-min Li, Jian-guo Zhang","doi":"10.1016/j.enmf.2024.02.005","DOIUrl":"https://doi.org/10.1016/j.enmf.2024.02.005","url":null,"abstract":"","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139886297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Energetic Materials Frontiers
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