Energetic Materials Frontiers最新文献_第4页

Chemical reaction mechanisms and models of energetic materials: A perspective 高能材料的化学反应机制和模型：透视

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2024.09.003

Li Meng , Qing-guan Song , Chuang Yao , Lei Zhang , Si-ping Pang

Energetic materials (EMs) are a kind of metastable functional materials with certain potential barriers, overcoming which can quickly release the energy stored in EMs. A thorough understanding of reaction mechanisms and accurate quantification of reaction rates are fundamental issues for optimizing energy output, ensuring hazard mitigation, and assessing the safety levels of EMs. This perspective provides an overview of research progress in chemical reaction mechanisms and models, with a particular emphasis on organic EMs and reactive metals. Organic EMs are mainly composed of carbon, hydrogen, nitrogen, and oxygen elements, enabling supersonic and self-sustaining detonation reactions capable of significant energy output. The incorporation of reactive metals like aluminum, magnesium, and boron has been recently found to augment the combustion heat and explosion temperature of EM formulations, sparking heightened research interest. This perspective first presents both EMs’ reaction mechanisms revealed via multiscale simulations and experimental methods, including thermal decomposition, shock initiation, and post combustion. Then, quantitatively characterized expressions of the physical models derived from the revealed mechanisms, including mathematical expressions like elementary and phenomenological reaction kinetic models, and emerging data-driven machine learning models, are reviewed. Finally, the view of the application, existing problems, and further development directions are outlined.

含能材料是一种具有一定势垒的亚稳态功能材料，克服势垒可以使储存在势垒中的能量迅速释放。全面了解反应机制和准确量化反应速率是优化能量输出、确保减轻危害和评估EMs安全水平的基本问题。这一观点概述了化学反应机理和模型的研究进展，特别强调了有机EMs和活性金属。有机电磁主要由碳、氢、氮和氧元素组成，使超音速和自持爆炸反应能够产生大量的能量输出。最近发现，铝、镁和硼等活性金属的掺入可以提高EM配方的燃烧热量和爆炸温度，从而引起了人们对EM配方的高度研究兴趣。这一观点首先通过多尺度模拟和实验方法揭示了EMs的反应机制，包括热分解、激波起始和燃烧后。然后，回顾了从揭示的机制中导出的物理模型的定量表征表达式，包括基本和现象学反应动力学模型等数学表达式，以及新兴的数据驱动机器学习模型。最后，对该技术的应用、存在的问题及进一步发展方向进行了展望。

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引用次数: 0

Synthesis and characterization of amphoteric salts and azo-bridged heat-resistant explosives with a 1,2,4-triazole framework 具有 1,2,4- 三唑框架的两性盐和偶氮桥接耐热炸药的合成与表征

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2024.08.006

En-pei Feng, Jie Tang, Cheng-chuang Li, Teng Zhu, Hong-wei Yang, Guang-bin Cheng

The formation of anions and cations from amphoteric compounds is an effective method to adjust the properties of amphoteric energetic materials, but there are few reports in the field of energetic materials. Based on the excellent properties and modifiability of 1,2,4-triazoles, this work provides a method for the synthesis of novel energetic materials by bridging triazole rings with carboxylic acid, ester and azo groups. Triazole cyclization of carboxylic acids gave the amphoteric compound 6,5-diamino-1′,4′-dihydro-4H,5′H-[3,3′-bis (1,2,4-triazole)]-5′-one (6) and formed the anionic hydroxylamine salt (8), which was not ideal in thermal stability (T_d = 161 °C). In order to further adjust the properties, 6 was reacted with nitric acid to form nitrate 7. Cationic nitrate 7 has good thermal stability (T_d = 334 °C) and high detonation properties (D_v = 8337 m∙s⁻¹) in high-energy nitrates. In addition, azo compound (5-nitro-1H, 2′H-[3,3′-bis (1,2,4-triazole)]-5′-yl) hydrazine (4) has low sensitivity (IS = 20 J, FS = 240 N), good thermal stability (T_d = 287 °C) and detonation characteristics (D_v = 8602 m∙s⁻¹, P = 30.5 GPa) comparable to RDX (D_v = 8795 m∙s⁻¹). Compounds 4 and 7 have good detonation properties and thermal stability, and have broad application prospects as heat-resistant insensitive explosives.

由两性化合物形成阴阳离子是调整两性高能材料性质的有效方法，但在高能材料领域的报道很少。基于 1,2,4-三唑的优异性能和可调控性，本研究提供了一种通过三唑环与羧酸、酯和偶氮基团桥接合成新型高能材料的方法。三唑环化羧酸得到了两性化合物 6,5-二氨基-1′,4′-二氢-4H,5′H-[3,3′-双（1,2,4-三唑）]-5′-酮（），并形成了阴离子羟胺盐（），其热稳定性（= 161 ℃）并不理想。为了进一步调整其性质，将其与硝酸反应生成硝酸盐。阳离子硝酸盐具有良好的热稳定性（= 334 ℃）和高能硝酸盐的高引爆性能（= 8337 m∙s）。此外，偶氮化合物（5-硝基-1H, 2′H-[3,3′-双（1,2,4-三唑）]-5′-基）肼（）灵敏度低（= 20 J，= 240 N），热稳定性好（= 287 ℃），起爆特性（= 8602 m∙s, = 30.5 GPa）与 RDX（= 8795 m∙s）相当。这些化合物具有良好的起爆特性和热稳定性，作为耐热不敏感炸药具有广阔的应用前景。

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引用次数: 0

A low-cost bionic interface modification strategy for enhancing the safety performance of energetic powders using PCPA@MXene double coating 利用PCPA@MXene双涂层提高高能粉末安全性能的低成本仿生界面改性策略

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2025.01.002

Bo-wei Gao , Yan-ze Liu , Xiao-feng Guo , Xu-ran Xu , Hai-feng Yang , Guang-cheng Yang , Jing Lv , Ling-hua Tan

Based on a simple catechol-amine co-precipitation strategy and biomimetic adhesion characteristics, this study prepared a desensitized CL-20@PCPA core-shell energetic powder using the phenolic and amino compound containing low-cost polycatechol/polyamine (PCPA). The results indicate that the CL-20@PCPA composite powder exhibited an elevated characteristic drop height of impact sensitivity (H₅₀) of 34.9 cm and a reduced friction explosion probability of 56 % compared to pure CL-20. PCPA, containing catechol and amine groups, provided a stable platform for secondary modification to enhance the safety of the powder further. Notably, when the CL-20@PCPA@MXene powder was introduced into a propellant system, the resulting propellants displayed a high H₅₀ value of 20.3 cm while its heat of detonation remained unchanged. This study provides a simple and low-cost biomimetic interface modification strategy for preparing desensitized energetic materials.

基于简单的儿茶酚-胺共沉淀策略和仿生粘附特性，本研究采用低成本多儿茶酚/多胺（PCPA）的酚类和氨基化合物制备了脱敏CL-20@PCPA核壳能量粉末。结果表明，与纯CL-20相比，CL-20@PCPA复合粉末的冲击敏感性特征跌落高度（H50）提高了34.9 cm，摩擦爆炸概率降低了56%。PCPA含有儿茶酚和胺基，为二次改性提供了稳定的平台，进一步提高了粉体的安全性。值得注意的是，当CL-20@PCPA@MXene粉末被引入推进剂系统时，所得到的推进剂的H50值高达20.3 cm，而爆轰热保持不变。本研究为制备脱敏含能材料提供了一种简单、低成本的仿生界面修饰策略。

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引用次数: 0

Female power: Contributions to energetic materials science 女性力量：对能量材料科学的贡献

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2025.03.004

Lei Zhang

引用次数: 0

Targeted nano-energetic material exploration through active learning algorithm implementation 通过主动学习算法实现有针对性的纳米高能材料探索

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2024.08.004

Leandro Carreira , Lea Pillemont , Yasser Sami , Nicolas Richard , Alain Esteve , Matthieu Jonckheere , Carole Rossi

This paper presents an active learning-based method designed to guide experiments towards user-defined specific regions, termed ”regions of interest,” within vast and multi-dimensional thermite design spaces. Thermites composed of metallic reactant coupled to an inorganic oxidizer are non-explosive energetic materials which stay inert and stable until subjected to a sufficiently strong thermal stimulus, after which they undergo fast burning with release of high amount of chemical energy (up to 16 kJ⋅cm⁻³). They represent an interesting class of nano-engineered energetic material because of their high adiabatic flame temperature (>2600 °C) and customizable combustion properties. We introduced a new acquisition function combining linearly two factors with the usual standard deviation of a Gaussian Process Regression algorithm. A first factor guides the sampling towards the defined zone of interest, and a second, is an incentive function that encourages the exploration of under-sampled regions of the design space. We found that our algorithm effectively provides up to several tens of nanothermites that achieve specific desired properties well-distributed within the design space, after only 200 samplings, whereas, Latin Hypercube Sampling procedure samples less than 10 points of interest. Our framework is tailored for typical discrete search spaces involving multiple measured physical properties and when only a small dataset is available, as it is the case in thermite materials. But more generally, this research represents a significant advancement for large-scale problems in energetic materials science and engineering, where predicting the effect of feature modification is desired but limited simulations or experiments can be afforded due to their high cost.

本文提出了一种基于主动学习的方法，旨在指导实验朝着用户定义的特定区域，称为“感兴趣的区域”，在广阔和多维铝热剂设计空间。热剂是由金属反应物与无机氧化剂偶联而成的非爆炸性高能材料，在受到足够强的热刺激之前保持惰性和稳定，之后它们经历快速燃烧并释放大量化学能（高达16 kJ·cm−3）。它们代表了一类有趣的纳米工程高能材料，因为它们具有高绝热火焰温度（2600°C）和可定制的燃烧特性。我们引入了一个新的采集函数，将线性两个因素与高斯过程回归算法的标准偏差相结合。第一个因素引导采样到定义的兴趣区域，第二个因素是激励功能，鼓励对设计空间中采样不足的区域进行探索。我们发现，仅在200次采样后，我们的算法就能有效地提供多达数十个纳米热螨，这些纳米热螨可以在设计空间内均匀分布，从而实现特定的所需属性，而拉丁超立方体采样程序的采样次数不到10个。我们的框架是为典型的离散搜索空间量身定制的，涉及多个测量的物理性质，当只有一个小的数据集可用时，就像铝热剂材料的情况一样。但更一般地说，这项研究代表了能量材料科学和工程中大规模问题的重大进步，其中预测特征修改的效果是必要的，但由于其高成本，只能提供有限的模拟或实验。

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引用次数: 0

Tuning thermal stability and mechanical sensitivity of polynitro compounds via integrating energetic ionic salts 通过整合高能离子盐调节多硝基化合物的热稳定性和机械敏感性

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2025.02.003

Mei-Qi Xu, Wen-Shuai Dong, Zu-Jia Lu, Cong Li, Chao Zhang, Bin-Shan Zhao, Deng-Ke Li, Feng-Yuan Tian, Qi-Yao Yu, Jian-Guo Zhang

Polynitro energetic compounds are a class of oxidant-rich energetic materials, playing a significant role in the field of solid propellants. Generally, an increase in the number of nitro groups present in these compounds is associated with a decrease in thermal stability, while simultaneously resulting in an enhancement of mechanical sensitivity. The incorporation of nitrogen-containing organic bases in the synthesis of polynitro energetic ionic salts facilitates a more uniform distribution of charge and promotes the formation of both intramolecular and intermolecular hydrogen bonds. This strategy effectively enhances the thermal stability of HEDMs while decreasing their mechanical sensitivity. In this study, two polynitro nitrogen-containing organic salts based on the triazole framework, namely ammonium salt (4) and hydroxylamine salt (5), were designed and synthesized. Comprehensive characterization revealed that both 4 and 5 exhibited excellent detonation performance (D: 8220–8959 m⋅s⁻¹), good thermal stability (T_d: 154–175°C), and low mechanical sensitivity (IS: 30–32 J; FS: 240–288 N). Therefore, nitrogen-containing organic salts enhance the overall performance of polynitro energetic compounds, offering significant advantages in terms of safety and application potential.

多硝基高能化合物是一类富含氧化剂的高能材料，在固体推进剂领域发挥着重要作用。一般来说，这些化合物中硝基数量的增加会降低热稳定性，同时导致机械灵敏度的提高。在合成多硝基高能离子盐时加入含氮有机碱，可使电荷分布更加均匀，并促进分子内和分子间氢键的形成。这种策略可有效提高 HEDM 的热稳定性，同时降低其机械敏感性。本研究设计并合成了两种基于三唑框架的多硝基含氮有机盐，即铵盐（4）和羟胺盐（5）。综合表征结果表明，4 和 5 均具有优异的起爆性能（D：8220-8959 m-s-1）、良好的热稳定性（Td：154-175°C）和较低的机械敏感性（IS：30-32 J；FS：240-288 N）。因此，含氮有机盐提高了多硝基高能化合物的整体性能，在安全性和应用潜力方面具有显著优势。

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引用次数: 0

A new fluorescent probe based on BODIPY for testing NO2 released from propellants 基于 BODIPY 的新型荧光探针，用于检测推进剂释放的二氧化氮

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2024.11.001

Ying-cui Cui , De-bin Xia , Zhong-yu Cui , Yu-jing Li , Jian Zhang , Ping Wang , Ting Guo , Kai-feng Lin , Yu-lin Yang

After long-term storage, solid propellants often exhibit various aging characteristics. This study presents a strategy for assessing the state of propellants using the Boron-dipyrrole Ni complex (BDP-Ni) as a probe. The thermogravimetric and cyclic voltammetry results indicate that the probe BDP-Ni exhibits excellent thermal stability and electrochemical stability. By utilizing both solution and thin films of BDP-Ni, we successfully detected NO₂ gas and observed a significant fluorescence intensity response to varying concentrations of NO₂. Subsequently, selectivity experiments with other characteristic gases confirmed the high specificity of BDP-Ni for NO₂. Furthermore, accelerated aging experiments of propellants were conducted alongside BDP-Ni films under identical conditions. This method can not only calculate the NO₂ gas concentration released from propellants based on fluorescence changes of BDP-Ni but also infer the state of propellants. The probe can additionally function as an 'alarm' to evaluate the extent of stabilizer consumption in the propellant. This work illustrates the preparation of the fluorescence probe and offers a new approach for detecting characteristic gases released from propellants.

固体推进剂在长期储存后通常会表现出各种老化特征。本研究提出了一种使用硼-二吡咯镍复合物（BDP-Ni）作为探针来评估推进剂状态的策略。热重法和循环伏安法的结果表明，探针 BDP-Ni 具有出色的热稳定性和电化学稳定性。通过利用 BDP-Ni 的溶液和薄膜，我们成功地检测到了二氧化氮气体，并观察到不同浓度的二氧化氮会产生明显的荧光强度反应。随后，其他特征气体的选择性实验证实了 BDP-Ni 对 NO2 的高度特异性。此外，还在相同条件下对推进剂和 BDP-Ni 薄膜进行了加速老化实验。这种方法不仅能根据 BDP-Ni 的荧光变化计算推进剂释放的二氧化氮气体浓度，还能推断推进剂的状态。此外，该探针还可作为 "警报器"，评估推进剂中稳定剂的消耗程度。这项工作展示了荧光探针的制备过程，并为检测推进剂释放的特征气体提供了一种新方法。

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引用次数: 0

Atmosphere effects on 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) nanoparticle pyrolysis: A ReaxFF molecular dynamics study 气氛对1,3,5-三氨基-2,4,6-三硝基苯（TATB）纳米颗粒热解的影响：ReaxFF分子动力学研究

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2025.03.006

Jia-lu Guan , Guan-chen Dong , Yi-dan Tao , Jing Lv , Ling-hua Tan , Xiao-na Huang , Guang-cheng Yang

1,3,5-Triamino-2,4,6-trinitrobenzene (TATB), an insensitive explosive, is exposed to the atmosphere during manufacture, storage and use, which can lead to changes in energy and sensitivity, particularly in nanoparticles. However, the underlying mechanisms of atmosphere effect on TATB pyrolysis remain poorly elucidated due to the limitations of experimental techniques in terms of temporal and spatial scales. This study employs molecular dynamics simulations to explore the impact of common atmospheres, including N₂ atmosphere, H₂O atmosphere, and NH₃ atmosphere, on the pyrolysis of TATB nanoparticles at the atomic level. The results demonstrate that all three atmospheres inhibit TATB pyrolysis, with N₂ atmosphere exhibiting the strongest inhibition, followed by NH₃ atmospheres, and H₂O atmosphere. Regarding the intrinsic mechanism, the inhibitory effects of different atmospheres can be classified into two categories: The influence of N₂ atmosphere and H₂O atmosphere is inert, as they hardly directly react with TATB but instead hinder the initial dehydrogenation reaction, thereby affecting the formation of key intermediates and final products; in contrast, NH₃ atmospheres not only inhibits these reactions but also tends to directly react with TATB to form larger molecules, which remain stable under thermal stimulation and suppress further decomposition of TATB.

1,3,5-三氨基-2,4,6-三硝基苯（TATB）是一种不敏感的炸药，在制造、储存和使用过程中暴露在大气中，这可能导致能量和灵敏度的变化，尤其是纳米颗粒。然而，由于实验技术在时间和空间尺度上的限制，大气对TATB热解影响的潜在机制尚不清楚。本研究采用分子动力学模拟的方法，在原子水平上探讨了常见气氛，包括N2气氛、H2O气氛和NH3气氛对TATB纳米颗粒热解的影响。结果表明：3种气氛对TATB热解均有抑制作用，其中N2气氛抑制作用最强，NH3气氛次之，H2O气氛次之。就其内在机理而言，不同气氛的抑制作用可分为两类：N2气氛和H2O气氛的影响是惰性的，因为它们几乎不直接与TATB反应，而是阻碍了初始脱氢反应，从而影响了关键中间体和最终产物的形成；相反，NH3气氛不仅抑制了这些反应，而且倾向于与TATB直接反应形成大分子，大分子在热刺激下保持稳定，抑制了TATB的进一步分解。

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引用次数: 0

Cover Story 封面故事

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/S2666-6472(25)00018-1

引用次数: 0

Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101 吡唑-四嗪单分子分解机理及取代基效应的量子化学模拟——以BITE-101为例

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY

Energetic Materials Frontiers

Pub Date : 2025-03-01 DOI: 10.1016/j.enmf.2025.01.004

Zi-xuan Yang , Shuang-fei Zhu , Hai Duan , Rui-jun Gou , Yang Liu , Shu-hai Zhang

4-amino-7,8-dinitropyrazolo-[5,1-d][1,2,3,5]-tetrazine 2-oxide (BITE-101) outperforms the benchmark explosive HMX in all aspects, showing application prospects as a new generation of high energy density material. To obtain the thermal decomposition mechanism and key intermediates of BITE-101, the initial decay pathways were studied by using the M062X method for optimization and DLPNO-CCSD(T)/cc-pVTZ methods for energies. The energy barrier results showed that the nitro-nitrite isomerization was the lowest, indicating that this path was the most advantageous in the reaction of BITE-101. In addition, the H transfer reaction has a promoting effect on the ring-opening reaction. Additionally, the influence of functional group position on the initial decomposition mechanism of energetic materials is also discussed. The results show that the most likely first decay paths are all caused by the functional groups on the tetrazine ring, and the position of the amino group had a great influence on the ring-opening reaction. These reactions can be clearly seen from the changes in ELF and Mayer bond order. These results will certainly deepen our understanding of the decay mechanism of pyrazolo-tetrazine.

4-氨基-7,8-二硝基吡唑-[5,1-d][1,2,3,5]-四嗪 2-氧化物（BITE-101）在各方面均优于基准炸药 HMX，显示出作为新一代高能量密度材料的应用前景。为了获得 BITE-101 的热分解机理和关键中间产物，研究人员采用 M062X 方法对其初始衰变途径进行了优化，采用 DLPNO-CCSD(T)/cc-pVTZ 方法对其能量进行了研究。能垒结果表明，亚硝基-亚硝酸异构化的能垒最低，这表明该路径在 BITE-101 的反应中最为有利。此外，H 转移反应对开环反应有促进作用。此外，还讨论了官能团位置对高能材料初始分解机理的影响。结果表明，最可能的第一衰变路径都是由四嗪环上的官能团引起的，而氨基的位置对开环反应有很大影响。从 ELF 和梅耶键顺序的变化可以清楚地看出这些反应。这些结果必将加深我们对吡唑四嗪衰变机理的理解。

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引用次数: 0