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A high density and low sensitivity carrier explosive promising to replace TNT: 3-Bromo-5-fluoro-2,4,6-trinitroanisole 有望取代 TNT 的高密度低灵敏度载体炸药:3-溴-5-氟-2,4,6-三硝基苯甲醚
IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-01 DOI: 10.1016/j.enmf.2024.06.003
Yi Wang , Xiao-lan Song , Zhi-hong Yu , Dan Song , Chong-wei An , Feng-sheng Li

To address the issues of high saturated vapor pressure, high toxicity, and high viscosity of TNT, this article used a chemical method to synthesize a new carrier explosive BFTNAN. The prepared samples were characterized using scanning electron microscope(SEM), energy spectrum(EDS), x-ray diffraction(XRD), infrared spectrum(IR), x-ray photoelectron spectroscopy(XPS), nuclear magnetic resonance, and elemental analysis techniques. The enthalpy of formation of BFTNAN was measured using a specialized calorimeter that is specially used in testing of explosives and powders. The thermal decomposition performance of BFTNAN was tested by DSC technology. Meanwhile, the mechanical sensitivity, thermal sensitivity, and detonation performance of BFTNAN based melt-cast explosive was also tested. The results of characterizations showed that the prepared sample was indeed BFTNAN. The enthalpy of formation of BFTNAN was determined as ΔHf,BFTNAN = −72.6 kJ·mol−1. At a heating rate of 20 °C·min−1, the thermal decomposition peak of BFTNAN is at TP = 250.6 °C, and the activation energy is EK = 80 kJ·mol−1, which is closed to the Tp and EK values of TNT. This indicates that BFTNAN is a relatively easy to decompose explosive, but the decomposition rate is not fast. The critical temperature for thermal explosion of BFTNAN reached Tb = 216 °C, which is also closed to the Tb value of TNT. The impact and friction sensitivity of BFTNAN were lower than those of TNT, which was closed to those of DNAN. The thermal sensitivity of BFTNAN is lower than TNT. The detonation velocity and heat of explosion of BFTNAN based melt-cast explosive were distinctly higher than those of TNT based explosive. Especially, BFTNAN based melt-cast explosive were of the advantages in chemical energy storage, work capacity, brisance, and ability of acceleration metals.

针对TNT饱和蒸气压高、毒性大、粘度高等问题,本文采用化学方法合成了一种新型载体炸药BFTNAN。利用扫描电子显微镜(SEM)、能谱(EDS)、X 射线衍射(XRD)、红外光谱(IR)、X 射线光电子能谱(XPS)、核磁共振和元素分析技术对制备的样品进行了表征。使用专门用于测试炸药和粉末的专用量热仪测量了 BFTNAN 的形成焓。利用 DSC 技术测试了 BFTNAN 的热分解性能。同时,还测试了基于 BFTNAN 的熔铸炸药的机械灵敏度、热灵敏度和起爆性能。表征结果表明,制备的样品确实是 BFTNAN。经测定,BFTNAN 的形成焓为 ΔHf,BFTNAN = -72.6 kJ-mol-1。在加热速率为 20 °C-min-1 时,BFTNAN 的热分解峰值为 TP = 250.6 °C,活化能为 EK = 80 kJ-mol-1,与 TNT 的 Tp 值和 EK 值接近。这表明 BFTNAN 是一种比较容易分解的炸药,但分解速度不快。BFTNAN 的热爆炸临界温度达到 Tb = 216 ℃,也与 TNT 的 Tb 值接近。BFTNAN 的冲击敏感性和摩擦敏感性低于 TNT,与 DNAN 接近。BFTNAN 的热敏性低于 TNT。BFTNAN 基熔铸炸药的爆速和爆热明显高于 TNT 基炸药。特别是,BFTNAN 基熔铸炸药在化学储能、做功能力、刚度和加速金属的能力等方面具有优势。
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引用次数: 0
Advanced Technologies: An efficient toolkit to accelerate the development of novel energetic materials 先进技术:加速新型能源材料开发的高效工具包
IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-01 DOI: 10.1016/j.enmf.2024.06.004
Chunlin He
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引用次数: 0
Enhancing the mechanical properties of TATB-based PBXs through strong hydrogen bonding interactions 通过强氢键相互作用增强基于 TATB 的 PBX 的机械性能
IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-01 DOI: 10.1016/j.enmf.2024.05.002
Xian-zhi Zhou , Cheng-cheng Zeng , Zi-jian Li , Gang Li , Sheng-jun Zheng , Fu-De Nie

Interfacial strength is a key factor affecting the mechanical properties of materials. This study aims to enhance the mechanical properties of energetic polymer bonded explosives (PBXs) by modifying 1,3,5-triamino-2,4,6-trintrobenzene (TATB) crystals—a typical energetic material—using 2-ureido-41H-6-methyl-pyrimidinone (UPy) derivatives with strong hydrogen-bonding interactions. Specifically, strongly adhesive polydopamine (PDA) was employed to graft UPy-functionalized molecules with isocyanate groups (–NCO) and hydroxyl groups (–OH). Scanning electron microscopy (SEM) images indicate that TATB crystals became rougher after being coated with PDA, while the introduction of UPy did not affect the surface morphology. The presence of urethane bond peaks in the samples indicates that UPy-NCO was successfully grafted onto the PDA. UPy is essentially nonpolar and is prone to bind with binders, having the potential to improve the creep resistance of PBXs. Due to the strong interfacial enhancement by UPy and PDA, the tensile strength and compressive strength of the sample grafted with 1 wt% UPy significantly increased by 35.6 % and 26.5 %, respectively. Theoretical calculations indicate interfacial enhancement by UPy introduction, where the strong hydrogen bonding may produce a positive impact. The successful introduction of UPy modified the nature of TATB and improved its interfacial strength, finally enhancing the mechanical properties of the PBXs. The conditions for the grafting reaction in this study are mild and universal and thus can be applied to other compositions.

界面强度是影响材料机械性能的一个关键因素。本研究旨在利用具有强氢键相互作用的 2-ureido-41H-6-methyl-pyrimidinone (UPy) 衍生物改性 1,3,5- 三氨基-2,4,6-三硝基苯(TATB)晶体(一种典型的高能材料),从而提高高能聚合物结合炸药(PBX)的机械性能。具体来说,使用强粘合性的聚多巴胺(PDA)来接枝带有异氰酸酯基团(-NCO)和羟基(-OH)的 UPy 功能化分子。扫描电子显微镜(SEM)图像显示,TATB 晶体在涂覆 PDA 后变得更加粗糙,而 UPy 的引入并未影响其表面形态。样品中出现的聚氨酯键峰表明 UPy-NCO 已成功接枝到 PDA 上。UPy 基本上是非极性的,容易与粘合剂结合,具有改善 PBX 抗蠕变性的潜力。由于 UPy 与 PDA 之间的界面增强作用很强,接枝了 1 wt% UPy 的样品的拉伸强度和压缩强度分别显著提高了 35.6% 和 26.5%。理论计算表明,UPy 的引入会增强界面,其中强氢键可能会产生积极影响。UPy 的成功引入改变了 TATB 的性质,提高了其界面强度,最终增强了 PBX 的机械性能。本研究中的接枝反应条件温和且通用,因此可应用于其他成分。
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引用次数: 0
Real-time X-ray diffraction measurement on laser shock-loaded hexanitrostilbene (HNS) 激光冲击载荷己酮二苯乙烯(HNS)的实时 X 射线衍射测量
Q2 Engineering Pub Date : 2024-05-01 DOI: 10.1016/j.enmf.2024.04.002
Tao Xi, Wei-min Zhou, Jianting Xin, Huan Zhang, Gen-bai Chu, Min Shui, Yong-qiang Zhao, Hao-bin Zhang
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引用次数: 0
Interactions between a neutral polymeric bonding agent and nitramine explosives and their influencing factors 中性聚合粘接剂与硝胺炸药之间的相互作用及其影响因素
Q2 Engineering Pub Date : 2024-03-11 DOI: 10.1016/j.enmf.2024.03.002
Juan Chen, De-qian Meng, Ping-an Zhang, Jian-ru Deng
Neutral polymer bonding agents (NPBAs) have proven highly effective in enhancing the interfacial bonding between the bonding matrix and nitramine explosives such as cyclic trimethylene trinitramine (RDX) and cyclic tetramethylene trinitramine (HMX). However, there is a lack of clear understanding of the mechanisms behind their interactions, and it has been found that NPBAs produce different interfacial bonding effects on RDX and HMX. To gain deeper insights into the molecular-scale interfacial interactions of nitramine explosives/NPBAs, this study investigated the molecular electrostatic potentials, intermolecular interactions, surface structural features, and interfacial adsorption of a NPBA onto nitramine explosives using the density functional theory and molecular dynamics (MD) technique. The results indicate that the N atom on the cyano group of the NPBA molecule can form weak hydrogen bonds C–H⋅⋅⋅N C and C–H⋅⋅⋅O with the H atoms in the RDX and HMX molecules. The strength of such weak hydrogen bonding interactions is affected by the electrostatic potential range of nitramine molecules. Additionally, the surface structure of the nitramine plays a critical role in the NPBA adsorption strength. Compared to HMX, RDX exhibits a narrower surface electrostatic potential range and smoother crystal surface, resulting in weaker intermolecular interactions between the NPBA and the RDX surface.
事实证明,中性聚合物粘接剂(NPBAs)在增强粘接基体与环三亚甲基三硝胺(RDX)和环四亚甲基三硝胺(HMX)等硝胺炸药之间的界面粘接方面非常有效。然而,人们对其相互作用背后的机制还缺乏清晰的认识,而且发现 NPBA 对 RDX 和 HMX 产生不同的界面键合效应。为了深入了解硝胺炸药/NPBA 的分子尺度界面相互作用,本研究利用密度泛函理论和分子动力学(MD)技术研究了 NPBA 在硝胺炸药上的分子静电势、分子间相互作用、表面结构特征以及界面吸附。结果表明,NPBA 分子氰基上的 N 原子可与 RDX 和 HMX 分子中的 H 原子形成 C-H⋅⋅⋅N C 和 C-H⋅⋅⋅O 弱氢键。这种弱氢键相互作用的强度受到硝胺分子静电电位范围的影响。此外,硝胺的表面结构对 NPBA 吸附强度也起着关键作用。与 HMX 相比,RDX 的表面静电势范围更窄,晶面更光滑,因此 NPBA 与 RDX 表面之间的分子间相互作用更弱。
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引用次数: 0
Effects of the crystallinity of fluoropolymer binders components in polymer-bonded explosives on shock Hugoniots: A computational study 聚合物粘结炸药中含氟聚合物粘结剂成分的结晶度对冲击休格诺茨的影响:计算研究
Q2 Engineering Pub Date : 2024-03-08 DOI: 10.1016/j.enmf.2024.03.001
Wen-yu Zhou, Hua-rong Li, Yong Han, Liu Liu, Hong Yang, Yang Zhou
Fluoropolymers play a crucial role as binders in polymer-bonded explosive (PBX) formulations. However, there is a lack of clear understanding of the effects of increased fluoropolymer crystallinity on the shock response of PBXs in the service environment. This study investigated the shock Hugoniots of two widely applied fluoropolymer binders: (1) F2314 from China—a copolymer with a molar ratio of vinylidene fluoride (VDF) to chlorotrifluoroethylene (CTFE) of 1:4 and (2) F2313 from the United States, also known as Kel F-800, with a VDF to CTFE molar ratio of 1:3. The Hugoniot curves of both fluoropolymers were calculated based on equilibrium molecular dynamics (MD) and a mixing rule. Furthermore, the corresponding P–V curves were obtained through fitting using the Tait equation of state (EOS). Their calculated parameters, including zero-pressure bulk modulus () and sound velocity (), agreed well with experimental data. The results reveal that the Hugoniots of amorphous F2314 and F2313 exhibited negligible differences. However, increasing crystallinity significantly impacted the Hugoniot curves of both fluoropolymers, especially for F2314 with high crystallinity. The obtained macroscopic characteristic parameters, namely and , exhibited an exponential dependence on crystallinity. Physically, this phenomenon can be attributed to a reduction in the compressible free volume of the fluoropolymers due to a more orderly chain arrangement. Additionally, under the same compression ratio, the shock temperature of the fluoropolymers increased with the crystallinity, posing potential safety risks to explosives. These findings establish a correlation between the crystallinity of fluoropolymers and the shock properties of PBXs, providing a theoretical reference for the formulation design of fluoropolymer-based PBXs.
含氟聚合物作为粘合剂在聚合物粘合炸药(PBX)配方中发挥着至关重要的作用。然而,人们对增加含氟聚合物结晶度对 PBX 在使用环境中的冲击响应所产生的影响还缺乏清晰的认识。本研究调查了两种广泛应用的含氟聚合物粘合剂的冲击休格尼特曲线:(1) 中国的 F2314(一种共聚物,其偏氟乙烯(VDF)与三氟氯乙烯(CTFE)的摩尔比为 1:4);(2) 美国的 F2313(又称 Kel F-800,其 VDF 与 CTFE 的摩尔比为 1:3)。这两种含氟聚合物的休格诺曲线都是根据平衡分子动力学(MD)和混合规则计算得出的。此外,通过使用 Tait 状态方程(EOS)进行拟合,还得到了相应的 P-V 曲线。其计算参数,包括零压体积模量()和声速(),与实验数据吻合良好。结果表明,无定形 F2314 和 F2313 的休格尼系数差异可以忽略不计。然而,结晶度的增加会对这两种含氟聚合物的休格尼奥特曲线产生重大影响,尤其是结晶度较高的 F2314。所获得的宏观特征参数(即和)与结晶度呈指数关系。从物理学角度看,这一现象可归因于氟聚合物的链排列更有序,从而减少了可压缩自由体积。此外,在相同的压缩比下,氟聚合物的冲击温度随结晶度的增加而升高,这对爆炸物构成了潜在的安全风险。这些发现确立了氟聚合物结晶度与 PBX 冲击特性之间的相关性,为基于氟聚合物的 PBX 配方设计提供了理论参考。
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引用次数: 0
Dual control over the reignition and combustion performance of hydroxylammonium nitrate-based gel propellants 对硝酸羟铵基凝胶推进剂的复燃和燃烧性能进行双重控制
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.03.005
Chun-tian Li, Zi-yang Lu, Zhiwen Wang, Li Lian, Zhi-dong Wang, Yu-cheng Zhang, Rui-qi Shen, Luigi T. De Luca, Wei Zhang
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引用次数: 0
Graphical Abstract 图表摘要
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/S2666-6472(24)00018-6
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引用次数: 0
Azo-linked four-heterocyclic energetic molecule and its complexes: Exploring the important influence of conjugated planar structure on their crystal arrangement and stability 偶氮连接的四杂环高能分子及其配合物:探索共轭平面结构对其晶体排列和稳定性的重要影响
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.01.001
Rui-bing Lv , Jin-yang Zhou , Liu He , Ting-wei Wang , Hong-zhen Li , Qi Zhang

Using two routes, this study designed and synthesized a novel azo-linked four-heterocyclic compound, 1,2-bis(5-(1H-tetrazol-5-yl)-4H-1,2,4-triazol-3-yl) diazene (3, H4BTTD), with high yields. It corroborated that large conjugated planar energetic molecules in energetic compounds, exemplified by H4BTTD, contribute to the formation of layered crystal stacking based on abundant hydrogen bonds and interlayer π-π interactions. This markedly diminishes the mechanical sensitivities of energetic compounds. Single-crystal X-ray diffraction (XRD) experiments revealed the presence of layered structures in H4BTTD hydrate, as well as its magnesium-based complex [Mg2(BTTD)(H2O)8] (4) and calcium salt [Ca(H2O)7] (H3BTTD)2 (5). Based on these structural data, this study analyzed the causes of these layered structures. Furthermore, this study systematically characterized the compounds’ physical and chemical properties, including mechanical sensitivities (IS ≥ 20 J, FS > 360 N), thermal stability (Td = 253.7–287.8 °C), and detonation performance (D = 6808–8253 m⋅s−1), confirming the influence of molecular structures on the macroscopic properties of energetic materials through crystal stacking. Additionally, pyrotechnic formulas based on compounds 3 and 5 exhibited the most intense light emission within a wavelength range of 658.6–689.8 nm, underscoring the potential application of both compounds as promising candidates in preparing high-purity red pyrotechnic formulation.

本研究采用两种路线设计并高产合成了一种新型偶氮连接的四杂环化合物--1,2-双(5-(1H-四唑-5-基)-4H-1,2,4-三唑-3-基)二氮烯(3,H4BTTD)。研究证实,高能化合物中的大共轭平面高能分子(以 H4BTTD 为例)会在大量氢键和层间 π-π 相互作用的基础上形成层状晶体堆积。这明显降低了高能化合物的机械敏感性。单晶 X 射线衍射 (XRD) 实验显示,H4BTTD 水合物及其镁基复合物 [Mg2(BTTD)(H2O)8] (4) 和钙盐 [Ca(H2O)7] (H3BTTD)2 (5) 中存在层状结构。根据这些结构数据,本研究分析了这些层状结构的成因。此外,本研究还系统分析了这些化合物的物理和化学特性,包括机械灵敏度(IS ≥ 20 J,FS > 360 N)、热稳定性(Td = 253.7-287.8 °C )和引爆性能(D = 6808-8253 m s-1),证实了分子结构通过晶体堆叠对高能材料宏观特性的影响。此外,基于化合物 3 和化合物 5 的烟火配方在 658.6-689.8 纳米波长范围内表现出最强烈的光辐射,这突出表明这两种化合物在制备高纯度红色烟火配方方面具有潜在的应用前景。
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引用次数: 0
Stabilizer selection and formulation strategies for enhanced stability of single base nitrocellulose propellants: A review 提高单基硝化纤维推进剂稳定性的稳定剂选择和配方策略:综述
Q2 Engineering Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.007
Siti Nor Ain Rusly , Siti Hasnawati Jamal , Alinda Samsuri , Siti Aminah Mohd Noor , Khoirul Solehah Abdul Rahim

Stabilizers play a crucial role in preventing undesirable decomposition and degradation reactions of propellants, thus ensuring their long-term performance and safe storage. This review highlights recent advancements in stabilizer selection and formulation techniques, aiming to enhance the stability of single base nitrocellulose (SB-NC) propellants. It examines several types of stabilizers for SB-NC propellants, including their reaction mechanisms and effectiveness in preventing degradation reactions of the propellants, as well as the effects of their concentrations, particle sizes, and distributions on the propellants’ stability. Furthermore, it explores innovative approaches such as nano and green stabilizers with improved stability and compatibility. This review also provides insights into methods for evaluating the efficiency and propellant stability of the stabilizers, such as thermal analysis and accelerated aging tests. The findings of this review will assist in developing advanced propellant formulations that meet the growing demand for the applications of NC-based propellants.

稳定剂在防止推进剂发生不良分解和降解反应,从而确保其长期性能和安全储存方面发挥着至关重要的作用。本综述重点介绍了稳定剂选择和配方技术的最新进展,旨在提高单基硝化纤维推进剂(SB-NC)的稳定性。它研究了几种用于 SB-NC 推进剂的稳定剂,包括它们的反应机理和防止推进剂降解反应的效果,以及它们的浓度、粒度和分布对推进剂稳定性的影响。此外,它还探讨了一些创新方法,如具有更高的稳定性和兼容性的纳米和绿色稳定剂。本综述还深入探讨了评估稳定剂效率和推进剂稳定性的方法,例如热分析和加速老化试验。本综述的研究结果将有助于开发先进的推进剂配方,以满足对数控推进剂应用日益增长的需求。
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引用次数: 0
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Energetic Materials Frontiers
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