Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2025.08.005
Parasar Kumar , Ramling S. Mathpati , Vikas D. Ghule , Srinivas Dharavath
Various nitrogen-rich fluorinated energetic materials based on monocyclic triazine, fused triazolo-triazine, and tetrazolo-triazine backbones were synthesized and fully characterized using multinuclear magnetic resonance spectroscopy (1H, 13C, 19F NMR), infrared spectroscopy (IR), high-resolution mass spectrometry (HRMS) and elemental analysis (EA). Additionally, 4-azido-6-(trifluoromethyl)-1,3,5-triazin-2-amine (ATFT, 2) was confirmed using single-crystal X-ray analysis (SC-XRD). All the synthesized compounds possess good density (>1.75 g cm−3), moderate to good thermal decomposition temperature (149–196 °C), good detonation properties (VOD = 6754–8058 m s−1; DP = 12.18–25.90 GPa), and excellent insensitivity (IS = 40 J, FS = 360 N). These findings provide new perspectives for the design of trifluoromethyl-containing energetic materials and also bring a new design of organic explosives with acceptable detonation properties.
{"title":"Nitrogen-rich triazine, triazolo and tetrazolo-triazine-based energetic compounds: A new class of fluorinated organic explosives","authors":"Parasar Kumar , Ramling S. Mathpati , Vikas D. Ghule , Srinivas Dharavath","doi":"10.1016/j.enmf.2025.08.005","DOIUrl":"10.1016/j.enmf.2025.08.005","url":null,"abstract":"<div><div>Various nitrogen-rich fluorinated energetic materials based on monocyclic triazine, fused triazolo-triazine, and tetrazolo-triazine backbones were synthesized and fully characterized using multinuclear magnetic resonance spectroscopy (<sup>1</sup>H, <sup>13</sup>C, <sup>19</sup>F NMR), infrared spectroscopy (IR), high-resolution mass spectrometry (HRMS) and elemental analysis (EA). Additionally, 4-azido-6-(trifluoromethyl)-1,3,5-triazin-2-amine (ATFT, <strong>2</strong>) was confirmed using single-crystal X-ray analysis (SC-XRD). All the synthesized compounds possess good density (>1.75 g cm<sup>−3</sup>), moderate to good thermal decomposition temperature (149–196 °C), good detonation properties (VOD = 6754–8058 m s<sup>−1</sup>; DP = 12.18–25.90 GPa), and excellent insensitivity (<em>IS</em> = 40 J, <em>FS</em> = 360 N). These findings provide new perspectives for the design of trifluoromethyl-containing energetic materials and also bring a new design of organic explosives with acceptable detonation properties.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 326-331"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365961","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2024.08.007
Andrey A. Kulikov , Nikita E. Leonov , Michael S. Klenov , Gennady A. Smirnov , Yurii A. Strelenko , Ivan V. Fedyanin , Tatiana S. Kon'kova , Yurii N. Matyushin , Alla N. Pivkina , Vladimir A. Tartakovsky
This paper provides the first in-depth study of energetic methoxy-NNO-azoxy compounds. 3-Amino-4-(methoxy-NNO-azoxy)furazan (7) is a useful precursor to a number of high-enthalpy substituted (methoxy-NNO-azoxy)furazans enriched with explosophoric functionalities (azofurazan 8, nitrofurazan 9, azoxyfurazan 10 and methylene dinitramine 11). It was shown for the first time that the interaction of nitroso compounds with salts of O-substituted N-nitrohydroxylamines leads to the formation of corresponding azoxy-oxy [N(O)=N–O] compounds, as exemplified by the reaction of 3-amino-4-nitrosofurazan (15) with the ammonium salt of O-methyl-N-nitrohydroxylamine (16) to give 3-amino-4-(methoxy-NNO-azoxy)furazan (7). This novel approach turned out to be the most suitable for the multigram synthesis of aminofurazan 7. The resulting (methoxy-NNO-azoxy)furazans 7–11 have good thermal stability (onset decomposition temperatures 148–238 °C), high experimental enthalpies of formation (1435–2750 kJ⋅kg−1) and acceptable densities (1.57–1.75 g⋅cm−3). In terms of detonation performance, all synthesized compounds (detonation velocities D = 7.9–8.5 km⋅s−1, detonation pressures PC–J = 26–32 GPa) lie between 1,3,5-trinitro-1,3,5-triazinane (RDX) (D = 8.9 km⋅s−1, PC–J = 36 GPa) and N-methyl-N-(2,4,6-trinitrophenyl)nitramide (Tetryl) (D = 7.6 km⋅s−1, PC–J = 26 GPa). The sensitivity study was performed and the results were compared to those for prevalent energetic materials. We have shown the extent to which introduction of the methoxy-NNO-azoxy group into a molecule can be used to tune the crucial properties of energetic materials (enthalpy of formation and thermal stability).
{"title":"First comprehensive study of energetic (methoxy-NNO-azoxy)furazans: Novel synthetic route, characterization, and property analysis","authors":"Andrey A. Kulikov , Nikita E. Leonov , Michael S. Klenov , Gennady A. Smirnov , Yurii A. Strelenko , Ivan V. Fedyanin , Tatiana S. Kon'kova , Yurii N. Matyushin , Alla N. Pivkina , Vladimir A. Tartakovsky","doi":"10.1016/j.enmf.2024.08.007","DOIUrl":"10.1016/j.enmf.2024.08.007","url":null,"abstract":"<div><div>This paper provides the first in-depth study of energetic methoxy-<em>NNO</em>-azoxy compounds. 3-Amino-4-(methoxy-<em>NNO</em>-azoxy)furazan (<strong>7</strong>) is a useful precursor to a number of high-enthalpy substituted (methoxy-<em>NNO</em>-azoxy)furazans enriched with explosophoric functionalities (azofurazan <strong>8</strong>, nitrofurazan <strong>9</strong>, azoxyfurazan <strong>10</strong> and methylene dinitramine <strong>11</strong>). It was shown for the first time that the interaction of nitroso compounds with salts of <em>O</em>-substituted <em>N</em>-nitrohydroxylamines leads to the formation of corresponding azoxy-oxy [N(O)=N–O] compounds, as exemplified by the reaction of 3-amino-4-nitrosofurazan (<strong>15</strong>) with the ammonium salt of <em>O</em>-methyl-<em>N</em>-nitrohydroxylamine (<strong>16</strong>) to give 3-amino-4-(methoxy-<em>NNO</em>-azoxy)furazan (<strong>7</strong>). This novel approach turned out to be the most suitable for the multigram synthesis of aminofurazan <strong>7</strong>. The resulting (methoxy-<em>NNO</em>-azoxy)furazans <strong>7</strong>–<strong>11</strong> have good thermal stability (onset decomposition temperatures 148–238 °C), high experimental enthalpies of formation (1435–2750 kJ⋅kg<sup>−1</sup>) and acceptable densities (1.57–1.75 g⋅cm<sup>−3</sup>). In terms of detonation performance, all synthesized compounds (detonation velocities <em>D</em> = 7.9–8.5 km⋅s<sup>−1</sup>, detonation pressures <em>P</em><sub>C–J</sub> = 26–32 GPa) lie between 1,3,5-trinitro-1,3,5-triazinane (RDX) (<em>D</em> = 8.9 km⋅s<sup>−1</sup>, <em>P</em><sub>C–J</sub> = 36 GPa) and <em>N</em>-methyl-<em>N</em>-(2,4,6-trinitrophenyl)nitramide (Tetryl) (<em>D</em> = 7.6 km⋅s<sup>−1</sup>, <em>P</em><sub>C–J</sub> = 26 GPa). The sensitivity study was performed and the results were compared to those for prevalent energetic materials. We have shown the extent to which introduction of the methoxy-<em>NNO</em>-azoxy group into a molecule can be used to tune the crucial properties of energetic materials (enthalpy of formation and thermal stability).</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 370-382"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365966","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2025.03.008
Qi Zhou, Huan Li, Long Zhu, Bing Li, Yun-zhi Liu, Gui-xiang Wang, Yu Zhang, Jun Luo
Polynitrooxaadamantanes have a broad application prospect in the field of energetic materials. Herein, a novel cage-like energetic compound, 2-oxaadamantane-4,8,9,10-tetrayl tetranitrate, was synthesized from bicyclo[3.3.1]nonane-2,6-dione via six steps. It exhibits high single-crystal density (1.731 g cm−3), good thermal stability (onset decomposition temperature of 177 °C), acceptable detonation performances (theoretical detonation velocity of 7644 m s−1and detonation pressure of 25 GPa). These results imply that the as-prepared compound has the potential to be used as high energy-density energetic compound.
聚硝基恶金刚烷在含能材料领域具有广阔的应用前景。本文以双环[3.3.1]壬烷-2,6-二酮为原料，经6步合成了一种新型笼状含能化合物-2 -草adamantan -4,8,9,10-四硝基四硝酸盐。单晶密度高（1.731 g cm−3），热稳定性好（起始分解温度为177℃），爆轰性能良好（理论爆速为7644 m s−1，爆轰压力为25 GPa）。这些结果表明所制备的化合物具有作为高能量密度含能化合物的潜力。
{"title":"2- Oxaadamantane-4,8,9,10-tetrayl tetranitrate: A novel oxa-type cage-like energetic compound","authors":"Qi Zhou, Huan Li, Long Zhu, Bing Li, Yun-zhi Liu, Gui-xiang Wang, Yu Zhang, Jun Luo","doi":"10.1016/j.enmf.2025.03.008","DOIUrl":"10.1016/j.enmf.2025.03.008","url":null,"abstract":"<div><div>Polynitrooxaadamantanes have a broad application prospect in the field of energetic materials. Herein, a novel cage-like energetic compound, 2-oxaadamantane-4,8,9,10-tetrayl tetranitrate, was synthesized from bicyclo[3.3.1]nonane-2,6-dione via six steps. It exhibits high single-crystal density (1.731 g cm<sup>−3</sup>), good thermal stability (onset decomposition temperature of 177 °C), acceptable detonation performances (theoretical detonation velocity of 7644 m s<sup>−1</sup>and detonation pressure of 25 GPa). These results imply that the as-prepared compound has the potential to be used as high energy-density energetic compound.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 299-304"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365860","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}
The development of energetic compounds with superior comprehensive properties remains a central focus in energetic materials research. By employing positional pyrazole isomerization, we have successfully synthesized 2’-(1H-pyrazol-4-yl)-1H,2’H-5,5’-bistetrazole (2) and its several energetic salts (2a-f). The synthesized compounds were characterized using nuclear magnetic resonance (NMR) and infrared spectroscopy (IR). The structure of compound 2a was further confirmed by single crystal X-ray diffraction analysis. Notably, compound 2, featuring 4-substitution on the pyrazole, demonstrates superior overall properties compared to the previously reported isomer V with 3-substitution. Among the newly synthesized salts, compound 2d exhibits exceptional thermal stability, while compound 2c shows a detonation velocity comparable to RDX. These findings suggest that positional isomerization is a promising approach for enhancing the thermal stability of energetic compounds.
{"title":"Advancing thermal stability through positional pyrazole isomerization: Synthesis and characterization of 2’-(1H-pyrazol-4-yl)-1H,2’H-5,5’-bistetrazole and its energetic derivatives","authors":"Jing Liu, Ya-qun Dong, Miao Li, Yu-ji Liu, Wei Huang, Yong-xing Tang","doi":"10.1016/j.enmf.2024.12.001","DOIUrl":"10.1016/j.enmf.2024.12.001","url":null,"abstract":"<div><div>The development of energetic compounds with superior comprehensive properties remains a central focus in energetic materials research. By employing positional pyrazole isomerization, we have successfully synthesized 2’-(1<em>H</em>-pyrazol-4-yl)-1<em>H</em>,2’<em>H</em>-5,5’-bistetrazole (<strong>2</strong>) and its several energetic salts (<strong>2a-f</strong>). The synthesized compounds were characterized using nuclear magnetic resonance (NMR) and infrared spectroscopy (IR). The structure of compound <strong>2a</strong> was further confirmed by single crystal X-ray diffraction analysis. Notably, compound <strong>2</strong>, featuring 4-substitution on the pyrazole, demonstrates superior overall properties compared to the previously reported isomer <strong>V</strong> with 3-substitution. Among the newly synthesized salts, compound <strong>2d</strong> exhibits exceptional thermal stability, while compound <strong>2c</strong> shows a detonation velocity comparable to RDX. These findings suggest that positional isomerization is a promising approach for enhancing the thermal stability of energetic compounds.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 347-353"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365963","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2024.08.003
Wen-zhe Huang, Lei Liu, Lu Lu, Yu-ji Liu, Wei Huang, Yong-xing Tang
Corrosion between energetic materials and metal containers can accelerate material aging and failure, significantly affecting the safety, reliability, and lifespan of ammunition systems. To address this challenge, we propose the construction of energetic covalent organic frameworks (ECOFs) as a promising solution. We introduce a straightforward method for synthesizing nitrogen-rich ECOFs. The synthesized ECOFs were characterized through powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (ssNMR), and Fourier-transform infrared spectroscopy (FTIR). These frameworks exhibit remarkable thermal stability, with decomposition temperatures above 285 °C. Notably, they display low sensitivity to non-explosive stimuli, as evidenced by impact sensitivity over 60 J and friction sensitivity over 360 N. The anti-rust properties of the ECOFs were further evaluated using Tafel curve analysis, highlighting their exceptional resistance to metal corrosion. Particularly, ECOF-3, synthesized from triaminoguanidine nitrate and 5-nitro-1,3-benzenedicarboxaldehyde, stands out for its superior steel corrosion resistance. These ECOFs have potential applications as high-energy, anti-corrosion coatings materials.
{"title":"Nitrogen-rich skeleton reassembled ECOFs as energetic materials with low sensitivities and good corrosion resistance","authors":"Wen-zhe Huang, Lei Liu, Lu Lu, Yu-ji Liu, Wei Huang, Yong-xing Tang","doi":"10.1016/j.enmf.2024.08.003","DOIUrl":"10.1016/j.enmf.2024.08.003","url":null,"abstract":"<div><div>Corrosion between energetic materials and metal containers can accelerate material aging and failure, significantly affecting the safety, reliability, and lifespan of ammunition systems. To address this challenge, we propose the construction of energetic covalent organic frameworks (ECOFs) as a promising solution. We introduce a straightforward method for synthesizing nitrogen-rich ECOFs. The synthesized ECOFs were characterized through powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (ssNMR), and Fourier-transform infrared spectroscopy (FTIR). These frameworks exhibit remarkable thermal stability, with decomposition temperatures above 285 °C. Notably, they display low sensitivity to non-explosive stimuli, as evidenced by impact sensitivity over 60 J and friction sensitivity over 360 N. The anti-rust properties of the ECOFs were further evaluated using Tafel curve analysis, highlighting their exceptional resistance to metal corrosion. Particularly, ECOF-3, synthesized from triaminoguanidine nitrate and 5-nitro-1,3-benzenedicarboxaldehyde, stands out for its superior steel corrosion resistance. These ECOFs have potential applications as high-energy, anti-corrosion coatings materials.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 291-298"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219645","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2025.09.003
{"title":"Synthesis of energetic materials: from molecular design to performance control","authors":"","doi":"10.1016/j.enmf.2025.09.003","DOIUrl":"10.1016/j.enmf.2025.09.003","url":null,"abstract":"","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 265-266"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365857","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2025.05.004
Yang-rui Cui, Jian-shuo Cheng, Yuan-gang Xu, Ming Lu
Pyrazole derivatives with polynitro groups were extensively researched in energetic material field as they show high energy density and excellent detonation properties, but the specific synthesis process still encounters challenges. In this paper, we firstly combined trinitromethyl, dinitroethyl, oxadiazolyl moieties with pyrazole, successfully designed and synthesized three novel poly-nitro pyrazole energetic compounds by nitration. Their structural features were investigated using single-crystal X-ray diffraction, nuclear magnetic resonance, infrared spectroscopy. 3-(3,5-Dinitro-1H-pyrazol-4-yl)-1,2,4-oxadiazol-5(4H)-one (12) possessed a superior thermal stability (235.1 °C) due to the presence of strong conjugated interaction in this structure. Among all, 3-nitro-1-(trinitromethyl)-1H-pyrazole-5-carboxylic acid (8) exhibited a good thermal stability (163.7 °C), a high density of 1.829 g cm−3 at 298 K in combination with excellent detonation properties (D: 8747 m s−1; P: 33.613 GPa). The results indicate that three compounds have promise to act as novel energetic materials and the synthesis provides a direction for polynitro compounds and oxadiazol based energetic compounds.
多硝基吡唑衍生物具有高能量密度和优异的爆轰性能，在高能材料领域得到了广泛的研究，但具体的合成工艺仍面临挑战。本文首次将三硝基甲基、二硝基乙基、恶二唑基与吡唑结合，通过硝化法成功设计合成了三种新型多硝基吡唑类含能化合物。用单晶x射线衍射、核磁共振、红外光谱等方法研究了它们的结构特征。3-（3,5-二硝基- 1h -吡唑-4-基）-1,2,4-恶二唑-5(4H)- 1（12）由于在该结构中存在强共轭相互作用而具有优异的热稳定性（235.1℃）。其中，3-硝基-1-（三硝基甲基）- 1h -吡唑-5-羧酸(8)表现出良好的热稳定性（163.7℃），298 K时密度高达1.829 g cm−3，爆轰性能优异（D: 8747 m s−1;P: 33.613 GPa）。结果表明，这3种化合物有望作为新型含能材料，为多硝基化合物和恶二唑基含能化合物的合成提供了方向。
{"title":"Nitropyrazole energetic compounds functionalized with dinitroethyl, trinitromethyl, or oxadiazolyl group: Synthesis, structure and energetic performance","authors":"Yang-rui Cui, Jian-shuo Cheng, Yuan-gang Xu, Ming Lu","doi":"10.1016/j.enmf.2025.05.004","DOIUrl":"10.1016/j.enmf.2025.05.004","url":null,"abstract":"<div><div>Pyrazole derivatives with polynitro groups were extensively researched in energetic material field as they show high energy density and excellent detonation properties, but the specific synthesis process still encounters challenges. In this paper, we firstly combined trinitromethyl, dinitroethyl, oxadiazolyl moieties with pyrazole, successfully designed and synthesized three novel poly-nitro pyrazole energetic compounds by nitration. Their structural features were investigated using single-crystal X-ray diffraction, nuclear magnetic resonance, infrared spectroscopy. 3-(3,5-Dinitro-1<em>H</em>-pyrazol-4-yl)-1,2,4-oxadiazol-5(4<em>H</em>)-one (<strong>12</strong>) possessed a superior thermal stability (235.1 °C) due to the presence of strong conjugated interaction in this structure. Among all, 3-nitro-1-(trinitromethyl)-1<em>H</em>-pyrazole-5-carboxylic acid (<strong>8</strong>) exhibited a good thermal stability (163.7 °C), a high density of 1.829 g cm<sup>−3</sup> at 298 K in combination with excellent detonation properties (<em>D</em>: 8747 m s<sup>−1</sup>; <em>P</em>: 33.613 GPa). The results indicate that three compounds have promise to act as novel energetic materials and the synthesis provides a direction for polynitro compounds and oxadiazol based energetic compounds.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 318-325"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365859","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}
Pub Date : 2025-09-01DOI: 10.1016/j.enmf.2024.11.002
Li-nan Zhang, Guang Wu, Ze Xu, Shuai-jie Jiang, Ming Lu, Qiu-han Lin
The pursuit of novel energetic materials with enhanced energy and safety represents an enduring challenge. Towards this goal, we employed the energetic salts to design and synthesize a metal salt (1) as well as three nitrogen-rich energetic salts (2, 3, 4) derived from 1,2-bis(4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazol-2-yl) diazene (NL24). The title compounds were fully characterized using Infrared Spectroscopy (IR), Nuclear Magnetic Resonance Spectroscopy (NMR), and elemental analysis. The structures of the salts 1, 2 and 4 were further confirmed by single crystal X-ray analysis. The results showed that the physiochemical properties of 1 were improved, including thermal stability (Td = 281 °C), and explosive performance (VD = 9200 m s−1). Besides, the physicochemical stability of hydrazine salt (4) reached the optimum level, including thermal stability (Td = 294 °C) and mechanical sensitivity (IS = 25 J, FS = 220 N). In addition, the structure-property relationship was elucidated through investigation of the crystal structure and the noncovalent interactions of 1, 2 and 4.
{"title":"Constructing high-performance and stable energetic salts through enhanced conjugation and increased hydrogen bonds","authors":"Li-nan Zhang, Guang Wu, Ze Xu, Shuai-jie Jiang, Ming Lu, Qiu-han Lin","doi":"10.1016/j.enmf.2024.11.002","DOIUrl":"10.1016/j.enmf.2024.11.002","url":null,"abstract":"<div><div>The pursuit of novel energetic materials with enhanced energy and safety represents an enduring challenge. Towards this goal, we employed the energetic salts to design and synthesize a metal salt (<strong>1</strong>) as well as three nitrogen-rich energetic salts (<strong>2</strong>, <strong>3</strong>, <strong>4</strong>) derived from 1,2-bis(4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazol-2-yl) diazene (<strong>NL24</strong>). The title compounds were fully characterized using Infrared Spectroscopy (IR), Nuclear Magnetic Resonance Spectroscopy (NMR), and elemental analysis. The structures of the salts <strong>1</strong>, <strong>2</strong> and <strong>4</strong> were further confirmed by single crystal X-ray analysis. The results showed that the physiochemical properties of <strong>1</strong> were improved, including thermal stability (<em>T</em><sub>d</sub> = 281 °C), and explosive performance (<em>V</em><sub>D</sub> = 9200 m s<sup>−1</sup>). Besides, the physicochemical stability of hydrazine salt (<strong>4</strong>) reached the optimum level, including thermal stability (<em>T</em><sub>d</sub> = 294 °C) and mechanical sensitivity (IS = 25 J, FS = 220 N). In addition, the structure-property relationship was elucidated through investigation of the crystal structure and the noncovalent interactions of <strong>1</strong>, <strong>2</strong> and <strong>4</strong>.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 3","pages":"Pages 354-361"},"PeriodicalIF":3.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145365964","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}
Pub Date : 2025-06-01DOI: 10.1016/j.enmf.2025.05.003
Chao Zhang , Xue-Xue Zhang , Ha Xiang , Xiao-hong Zhang , Qi-Long Yan
Low temperature sensitivity coefficients are of great significance for improving the combustion stability of modified double-base propellants (MDBPs) under sensitive environmental conditions. In this work, different combined catalyst systems containing Pb-complex, magnesium oxide (MgO), carbon black (CB) and Cu-complex have been employed to tune the combustion behavior of MDBPs. The effects of these catalysts on the combustion properties of MDBP have been comprehensively investigated at the pressure range of 4–15 MPa and different initial temperatures (−40, 20 and 50 °C). The MDBPs with composite catalysts of Pb-complex, MgO, CB and Cu-complex (NRPbMgCBCu) has almost zero temperature sensitivity coefficient. The combined catalyst systems have catalytic effect on thermal decomposition and combustion of MDBPs, which is more likely to cause an intensive combustion especially at lower pressures. The burning rate temperature sensitivity and pressure exponent of NRPbMgCBCu have been largely reduced by adding this combined catalyst systems. The results show that the exothermic peak temperature of NRPbMgCBCu was decreased by 8.2 °C, and its heat release has been increased by 26.4 %, whereas the heat of combustion is 4.1 % higher than that of the blank MDBP. More importantly, the burning rates of MDB propellants with catalysts are notably increased by 86.9 %–169.8 % at 4 MPa. The combination of Pb-complex, MgO, CB and Cu-complex may have the best stabilization effect on the burn rate sensitivity to the initial temperature for MDBPs. The calculated pressure exponent of NRPbMgCBCu at 6–12 MPa was largely reduced to 0.03, whereas the corresponding temperature sensitivity coefficient was only 5.4E-4 %·°C−1.
{"title":"Modified double base propellants containing RDX with zero burning rate temperature coefficient","authors":"Chao Zhang , Xue-Xue Zhang , Ha Xiang , Xiao-hong Zhang , Qi-Long Yan","doi":"10.1016/j.enmf.2025.05.003","DOIUrl":"10.1016/j.enmf.2025.05.003","url":null,"abstract":"<div><div>Low temperature sensitivity coefficients are of great significance for improving the combustion stability of modified double-base propellants (MDBPs) under sensitive environmental conditions. In this work, different combined catalyst systems containing Pb-complex, magnesium oxide (MgO), carbon black (CB) and Cu-complex have been employed to tune the combustion behavior of MDBPs. The effects of these catalysts on the combustion properties of MDBP have been comprehensively investigated at the pressure range of 4–15 MPa and different initial temperatures (−40, 20 and 50 °C). The MDBPs with composite catalysts of Pb-complex, MgO, CB and Cu-complex (NR<sub>PbMgCBCu</sub>) has almost zero temperature sensitivity coefficient. The combined catalyst systems have catalytic effect on thermal decomposition and combustion of MDBPs, which is more likely to cause an intensive combustion especially at lower pressures. The burning rate temperature sensitivity and pressure exponent of NR<sub>PbMgCBCu</sub> have been largely reduced by adding this combined catalyst systems. The results show that the exothermic peak temperature of NR<sub>PbMgCBCu</sub> was decreased by 8.2 °C, and its heat release has been increased by 26.4 %, whereas the heat of combustion is 4.1 % higher than that of the blank MDBP. More importantly, the burning rates of MDB propellants with catalysts are notably increased by 86.9 %–169.8 % at 4 MPa. The combination of Pb-complex, MgO, CB and Cu-complex may have the best stabilization effect on the burn rate sensitivity to the initial temperature for MDBPs. The calculated pressure exponent of NR<sub>PbMgCBCu</sub> at 6–12 MPa was largely reduced to 0.03, whereas the corresponding temperature sensitivity coefficient was only 5.4E-4 %·°C<sup>−1</sup>.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 2","pages":"Pages 202-211"},"PeriodicalIF":3.3,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614291","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}
Pub Date : 2025-06-01DOI: 10.1016/j.enmf.2024.11.005
Jin-ning Hu , Xiao-jing Fan , Jun-feng Wang , Shao-hua Jin , Chang-jun Zhao , Xiu-tian-feng E , Chao-yang Zhang , Liang-liang Niu
3-Nitro-1,2,4-triazole-5-one (NTO) is a promising energetic compound with high energy and low sensitivity. Herein, the elastic properties of three NTO polymorphs are studied using dispersion-corrected density functional theory. The calculation results of three NTO crystal forms show that C11 is 47–64 GPa, and C22 and C33 are 15.8–19 GPa. We show that more than half of the isotropic elasticity of NTO polymorphs arises from the contribution of London dispersion interaction, which is generally considered to be a weak term. Among the polymorphs, β-NTO is demonstrated to be the stiffest and most anisotropic due to the strongest intermolecular electrostatic interactions and hydrogen bonds. Interestingly, the quantification of elasticity anisotropy demonstrates that the London dispersion interactions also contribute to the anisotropy of energetic molecular crystals. These findings facilitate our fundamental understanding of the elastic properties and the structure-property relationships of energetic polymorphs.
{"title":"Quantifying the influence of dispersion interactions on the elastic properties of energetic NTO polymorphs","authors":"Jin-ning Hu , Xiao-jing Fan , Jun-feng Wang , Shao-hua Jin , Chang-jun Zhao , Xiu-tian-feng E , Chao-yang Zhang , Liang-liang Niu","doi":"10.1016/j.enmf.2024.11.005","DOIUrl":"10.1016/j.enmf.2024.11.005","url":null,"abstract":"<div><div>3-Nitro-1,2,4-triazole-5-one (NTO) is a promising energetic compound with high energy and low sensitivity. Herein, the elastic properties of three NTO polymorphs are studied using dispersion-corrected density functional theory. The calculation results of three NTO crystal forms show that <em>C</em><sub>11</sub> is 47–64 GPa, and <em>C</em><sub>22</sub> and <em>C</em><sub>33</sub> are 15.8–19 GPa. We show that more than half of the isotropic elasticity of NTO polymorphs arises from the contribution of London dispersion interaction, which is generally considered to be a weak term. Among the polymorphs, <em>β</em>-NTO is demonstrated to be the stiffest and most anisotropic due to the strongest intermolecular electrostatic interactions and hydrogen bonds. Interestingly, the quantification of elasticity anisotropy demonstrates that the London dispersion interactions also contribute to the anisotropy of energetic molecular crystals. These findings facilitate our fundamental understanding of the elastic properties and the structure-property relationships of energetic polymorphs.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 2","pages":"Pages 156-165"},"PeriodicalIF":3.3,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614863","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}
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