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Advanced Chemistry of Energetic Materials
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Advanced Chemistry of Energetic Materials

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (31 May 2020) | Viewed by 73967

Special Issue Editor

Prof. Dr. Svatopluk Zeman

E-Mail Website
Guest Editor
Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Republic
Interests: chemical physics; initiatory reactivity; energetic materials; organic chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Over the past 30 years, there has been an unprecedented increase of information from chemistry and less so from technology of energetic materials (EMs) in the open literature. However, a large amount of that information here has turned labyrinthine in its form, and the presence of a bigger amount of quantum-chemical studies is leading to a certain “diluting” of the chemical information available. Therefore, it would be useful to draw attention to the methods and findings of major importance for further research and development in this field, even for the mentioned quantum-chemical approaches, which often lack links to real practice, especially with EM testing. Of course, the publication of technological information is bound up with production and other secrets, but it is still possible to find papers pointing to developments in this field—for example, new approaches to prepare of CL-20, HMX, FOX-7, TKX-50, BCHMX and other technically attractive EMs. Crystal engineering, that is to say, the theory, methods, and technologies of co-crystals preparation, which is one of the major and promising sectors of contemporary development of explosives, has experienceed a significant upswing in attempts to use it, as chemical methods have almost reached their maximum usable potential. For this reason, a similar interest also exists in the development of nano-EMs and mixtures containing them, but also mixed explosives of the PBXs type with new binders and plasticizers, in new propellants and, last but not least, in industrial explosives type W/O and others.

Prof. Svatopluk Zeman
Guest Editor

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Energetic heterocyclic compounds
  • Nitramines
  • Polynitroarenes
  • Nitric esters
  • Synthesis
  • Technology
  • Co-crystals
  • Binders
  • Plasticizers
  • Nano-energetic materials
  • Plastic bonded explosives
  • Propellants
  • Industrial explosives
  • Testing
  • Sensitivity
  • Performance

Published Papers (16 papers)

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Research

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13 pages, 1215 KiB  
Article
Structural and Energetic Insights on Two Dye Compounds: 1-Acetyl-2-Naphthol and 2-Acetyl-1-Naphthol
by Vera L. S. Freitas and Maria D. M. C. Ribeiro da Silva
Molecules 2020, 25(17), 3827; https://doi.org/10.3390/molecules25173827 - 22 Aug 2020
Cited by 4 | Viewed by 2389
Abstract
The energy involved in the structural switching of acyl and hydroxyl substituents in the title compounds was evaluated combining experimental and computational studies. Combustion calorimetry and Knudsen effusion techniques were used to determine the enthalpies of formation, in the crystalline state, and of [...] Read more.
The energy involved in the structural switching of acyl and hydroxyl substituents in the title compounds was evaluated combining experimental and computational studies. Combustion calorimetry and Knudsen effusion techniques were used to determine the enthalpies of formation, in the crystalline state, and of sublimation, respectively. The gas-phase enthalpy of formation of both isomers was derived combining these two experimental data. Concerning the computational study, the G3(MP2)//B3LYP composite method was used to optimize and determine the energy of the isomers in the gaseous state. From a set of hypothetical reactions it has been possible to estimate the gas-phase enthalpy of formation of the title compounds. The good agreement between the experimental and computational gas-phase enthalpies of formation of the 1-acetyl-2-naphthol and 2-acetyl-1-naphthol isomers, provided the confidence for extending the computational study to the 2-acetyl-3-naphthol isomer. The structural rearrangement of the substituents in position 1 and 2 in the naphthalene ring and the energy of the intramolecular hydrogen bond are the factors responsible for the energetic differences exhibited by the isomers. The gas phase tautomeric keto ↔ enol equilibria of the o-acetylnaphthol isomers were analyzed using the Boltzmann’s distribution. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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15 pages, 2819 KiB  
Article
Synthesis of 2,4,6-Trinitrotoluene (TNT) Using Flow Chemistry
by Dimitris Kyprianou, Michael Berglund, Giovanni Emma, Grzegorz Rarata, David Anderson, Gabriela Diaconu and Vassiliki Exarchou
Molecules 2020, 25(16), 3586; https://doi.org/10.3390/molecules25163586 - 6 Aug 2020
Cited by 12 | Viewed by 16959
Abstract
This paper describes the nitration of 2,4-dinitrotoluene (DNT) and its conversion to 2,4,6-trinitrotoluene (TNT) at a gram scale with the use of a fully automated flow chemistry system. The conversion of DNT to TNT traditionally requires the use of highly hazardous reagents like [...] Read more.
This paper describes the nitration of 2,4-dinitrotoluene (DNT) and its conversion to 2,4,6-trinitrotoluene (TNT) at a gram scale with the use of a fully automated flow chemistry system. The conversion of DNT to TNT traditionally requires the use of highly hazardous reagents like fuming sulfuric acid (oleum), fuming nitric acid (90–100%), and elevated temperatures. Flow chemistry offers advantages compared to conventional syntheses including a high degree of safety and simpler multistep automation. The configuration and development of this automated process based on a commercially available flow chemistry system is described. A high conversion rate (>99%) was achieved. Unlike established synthetic methods, ordinary nitrating mixture (65% HNO3/98% H2SO4) and shorter reaction times (10–30 min) were applied. The viability of flow nitration as a means of safe and continuous synthesis of TNT was investigated. The method was optimized using an experimental design approach, and the resulting process is safer, faster, and more efficient than previously reported TNT synthesis procedures. We compared the flow chemistry and batch approaches, including a provisional cost calculation for laboratory-scale production (a thorough economic analysis is, however, beyond the scope of this article). The method is considered fit for purpose for the safe production of high-purity explosives standards at a gram scale, which are used to verify that the performance of explosive trace detection equipment complies with EU regulatory requirements. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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14 pages, 8898 KiB  
Article
The Study of HEMs Based on the Mechanically Activated Intermetallic Al12Mg17 Powder
by Sergei Sokolov, Alexander Vorozhtsov, Vladimir Arkhipov and Ilya Zhukov
Molecules 2020, 25(16), 3561; https://doi.org/10.3390/molecules25163561 - 5 Aug 2020
Cited by 4 | Viewed by 2885
Abstract
In this work, Al–Mg intermetallic powders were characterized and obtained by melting, casting into a steel chill and subsequent mechanical activation in a planetary mill. The method for producing Al12Mg17 intermetallic powder is presented. The dispersity, morphology, chemical composition, and [...] Read more.
In this work, Al–Mg intermetallic powders were characterized and obtained by melting, casting into a steel chill and subsequent mechanical activation in a planetary mill. The method for producing Al12Mg17 intermetallic powder is presented. The dispersity, morphology, chemical composition, and phase composition of the obtained powder materials were investigated. Certain thermodynamic properties of high-energy materials containing the Al-Mg powder after mechanical activation of various durations were investigated. The addition of the Al-Mg powders to the high-energy composition (synthetic rubber SKDM-80 + ammonium perchlorate AP + boron B) can significantly increase the burning rate by approximately 47% and the combustion heat by approximately 23% compared with the high-energy compositions without the Al-Mg powder. The addition of the Al12Mg17 powder obtained after 6 h of mechanical activation provides an increase in the burning rate by 8% (2.5 ± 0.1 mm/s for the mechanically activated Al12Mg17 powder and 2.3 ± 0.1 mm/s for the commercially available powder) and an increase in the combustion heat by 3% (7.4 ± 0.2 MJ/kg for the mechanically activated Al-Mg powder and 7.1 ± 0.2 MJ/kg for the commercially available powder). The possibility of using the Al-Mg intermetallic powders as the main component of pyrotechnic and special compositions is shown. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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12 pages, 42025 KiB  
Article
Structure and Stability of Aromatic Nitrogen Heterocycles Used in the Field of Energetic Materials
by He-Hou Zong, Chuang Yao, Chang Q Sun, Jian-Guo Zhang and Lei Zhang
Molecules 2020, 25(14), 3232; https://doi.org/10.3390/molecules25143232 - 15 Jul 2020
Cited by 17 | Viewed by 2984
Abstract
Understanding the stabilization of nitrogen heterocycles is critical in the field of energetic materials and calls for innovative knowledge of nitrogen aromatics. Herewith, we report for the first time that nitrogen lone pair electron (NLPE) delocalization in five-membered nitrogen heterocycles creates a second [...] Read more.
Understanding the stabilization of nitrogen heterocycles is critical in the field of energetic materials and calls for innovative knowledge of nitrogen aromatics. Herewith, we report for the first time that nitrogen lone pair electron (NLPE) delocalization in five-membered nitrogen heterocycles creates a second σ-aromaticity in addition to the prototypical π-aromaticity. The NLPE delocalization and the attendant dual-aromaticity are enhanced as more carbon atoms in the ring are substituted by unsaturated nitrogen atoms. The presence of adjacent nitrogen atoms in the ring can enhance the aromaticity of the nitrogen heterocycles and improve in-crystal intermolecular binding strength but will decrease the firmness of the individual molecular architecture. Notably, such σ-aromaticity is not present in six-membered nitrogen heterocycles, probably due to the longer bonds and broader regions of their rings; therefore, six-membered heterocycles present overall lower aromaticity than five-membered heterocycles. This work brings new knowledge to nitrogen aromatics and is expected to inspire broad interest in the chemistry community. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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17 pages, 4010 KiB  
Article
Experimental Study of Pyrolysis and Laser Ignition of Low-Vulnerability Propellants Based on RDX
by Jordan Ehrhardt, Léo Courty, Philippe Gillard and Barbara Baschung
Molecules 2020, 25(10), 2276; https://doi.org/10.3390/molecules25102276 - 12 May 2020
Cited by 8 | Viewed by 2665
Abstract
Low-vulnerability propellants are propellants designed to resist unintended stimuli to increase safety during transport, storage and handling. The substitution of usual nitrocellulose-based gun propellants with these new materials allows maintaining interior ballistics performances while increasing the safety. In this paper, the pyrolysis, ignition [...] Read more.
Low-vulnerability propellants are propellants designed to resist unintended stimuli to increase safety during transport, storage and handling. The substitution of usual nitrocellulose-based gun propellants with these new materials allows maintaining interior ballistics performances while increasing the safety. In this paper, the pyrolysis, ignition and combustion of such propellants are investigated in order to study conditions leading to a safe and reproducible ignition. Low-vulnerability propellants studied are made of different ratios of hexogen (RDX) and nitrocellulose (NC). Three compositions are studied by varying weight percentages of RDX and NC: 95-5, 90-10 and 85-15 for respective weight percentages of RDX-NC. Pyrolysis of these propellants is studied with two different experimental setups: a flash pyrolysis device linked to a gas chromatograph coupled to a mass spectrometer (Py-GC-MS) and a closed-volume reactor coupled to a mass spectrometer. Different molecules, like NO2, CO, CH3COCH3 or CH2NCH2NCH2, are obtained during the decomposition of these propellants. Laser ignition of these propellants is studied in a cylindrical closed-volume reactor using a laser diode. Several combustion characteristics, such as ignition delays, maximal overpressures and combustion rates are given for the three propellants using the pressure signals. Moreover, ignition energies are also investigated. Obtained results are compared to the few available literature data. A particular behavior is noticed for the 90-10 propellant. The experimental data collected should serve in the future to have a better understanding of the chemical reactions driving the combustion process of these low-vulnerability propellants. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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12 pages, 2578 KiB  
Article
Mechanical and Thermal Properties of Polyether Polytriazole Elastomers Formed by Click-Chemical Reaction Curing Glycidyl Azide Polymer
by Liming He, Jun Zhou, Yutao Wang, Zhongliang Ma and Chunlin Chen
Molecules 2020, 25(8), 1988; https://doi.org/10.3390/molecules25081988 - 23 Apr 2020
Cited by 10 | Viewed by 2699
Abstract
Energetic binders are a research hot-spot, and much emphasis has been placed on their mechanical properties. In this study, propargyl-terminated ethylene oxide-tetrahydrofuran copolymer (PTPET) was synthesized. Then, PTPET and low-molecular-weight ester-terminated glycidyl azide polymer (GAP) were reacted by the click reaction without using [...] Read more.
Energetic binders are a research hot-spot, and much emphasis has been placed on their mechanical properties. In this study, propargyl-terminated ethylene oxide-tetrahydrofuran copolymer (PTPET) was synthesized. Then, PTPET and low-molecular-weight ester-terminated glycidyl azide polymer (GAP) were reacted by the click reaction without using catalysts to obtain a polyether polytriazole elastomer. Through tensile tests, where R = 0.5, the tensile strength reached 0.332 MPa, with an elongation at break of 897.1%. Swelling tests were used to measure the cross-linked network and showed that the cross-linked network regularity was reduced as R increased. The same conclusions were confirmed by dynamic mechanical analysis (DMA). In DMA curves, Tg was around −70 to −65 °C, and a small amount of crystallization appeared at between −50 and −30 °C, because locally ordered structures were also present in random copolymers, thereby forming localized crystals. Their thermal performance was tested by Differential Scanning Calorimeter (DSC) and Thermal Gravimetric Analyzer (TG), and the main mass loss occurred at around 350 to 450 °C, which meant that they were stable. In conclusion, the polyether polytriazole elastomer can be used as a binder in a composite propellant. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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11 pages, 2141 KiB  
Article
A Powdered Simulant of Triacetone Triperoxide (TATP) for Safe Testing of X-ray Transmission Screening Equipment
by Mitja Vahčič, David Anderson, John Seghers, Hanne Leys, Miguel Ruiz Oses, Grzegorz Rarata, Maximino Fernández García, Rosana Prados Román and Daniel Pellico Escudero
Molecules 2020, 25(6), 1473; https://doi.org/10.3390/molecules25061473 - 24 Mar 2020
Cited by 1 | Viewed by 8918
Abstract
Explosives detection systems (EDS) based on X-ray are used at airports to screen baggage for the presence of explosives. Once EDS are installed in airports, however, it can be challenging to test the EDS equipment and verify that it continues to perform at [...] Read more.
Explosives detection systems (EDS) based on X-ray are used at airports to screen baggage for the presence of explosives. Once EDS are installed in airports, however, it can be challenging to test the EDS equipment and verify that it continues to perform at the highest level, because of the impracticality of introducing bulk explosives into civil aviation airports. The problem is particularly acute for sensitive homemade explosives, such as triacetone triperoxide (TATP). This paper describes our work to develop a safe, accurate and stable simulant for TATP for EDS based on X-ray transmission. Bulk quantities of TATP were synthesised and characterised especially for this project, and we describe the unique challenges and safety considerations of collecting this data. Our calculations show that the expanded measurement uncertainty with a coverage factor of k = 2 is 5.7% for bulk density and 1.0% for Zeff at 24 months. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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10 pages, 1547 KiB  
Article
Structure and Thermal Properties of 2,2′-Azobis(1H-Imidazole-4,5-Dicarbonitrile)—A Promising Starting Material for a Novel Group of Energetic Compounds
by Rafał Lewczuk, Maria Książek, Katarzyna Gańczyk-Specjalska and Katarzyna Cieślak
Molecules 2020, 25(2), 314; https://doi.org/10.3390/molecules25020314 - 13 Jan 2020
Cited by 4 | Viewed by 2993
Abstract
A high-nitrogen compound, 2,2′-azobis(1H-imidazole-4,5-dicarbonitrile) (TCAD), was synthesized from commercially available 2-amino-1H-imidazole-4,5-dicarbonitrile. It was characterized with infrared and nuclear magnetic resonance spectroscopy. Its structure was determined by single crystal X-ray diffraction. The crystal of TCAD tetrahydrate is monoclinic, with space [...] Read more.
A high-nitrogen compound, 2,2′-azobis(1H-imidazole-4,5-dicarbonitrile) (TCAD), was synthesized from commercially available 2-amino-1H-imidazole-4,5-dicarbonitrile. It was characterized with infrared and nuclear magnetic resonance spectroscopy. Its structure was determined by single crystal X-ray diffraction. The crystal of TCAD tetrahydrate is monoclinic, with space group P21/c with crystal parameters of a = 10.2935(2) Å, b = 7.36760(10) Å, c = 20.1447(4) Å, V = 1500.27(5) Å3, Z = 4, and F(000) = 688. Computational methods were used in order to fully optimize the molecular structure, calculate the electrostatic potential of an isolated molecule, and to compute thermodynamic parameters. TCAD has very high thermal stability with temperature of decomposition at 369 °C. Kinetics of thermal decomposition of this compound were studied and apparent energy of activation as well as the maximum safe temperature of technological process were determined. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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15 pages, 2152 KiB  
Article
Corrections of Molecular Morphology and Hydrogen Bond for Improved Crystal Density Prediction
by Linyuan Wang, Miao Zhang, Jie Chen, Liang Su, Shicao Zhao, Chaoyang Zhang, Jian Liu and Chunyan Chen
Molecules 2020, 25(1), 161; https://doi.org/10.3390/molecules25010161 - 31 Dec 2019
Cited by 13 | Viewed by 2513
Abstract
Density prediction is of great significance for molecular design of energetic materials, since detonation velocity linearly with density and detonation pressure increases with the density squared. However, the accuracy and generalization of former reported prediction models need further improvement, because most of them [...] Read more.
Density prediction is of great significance for molecular design of energetic materials, since detonation velocity linearly with density and detonation pressure increases with the density squared. However, the accuracy and generalization of former reported prediction models need further improvement, because most of them are derived from small data sets and few molecular descriptors. As shown in this paper, for molecules presenting brick-like shape or containing more hydrogen-bond donors the predicted densities have large negative deviations from experimental values. Thus, a molecular morphology descriptor η and a hydrogen-bond descriptor Hb are introduced as correction items to build 3 new QSPR models. Besides, 3694 nitro compounds are adopted as data set by this work. The accuracies are obviously improved, and the generalizations are verified by an independent test set. At the level of B3PW91/6-31G(d,p), the effective ratios (ERs) of the 3 Equations, for Δρ < 5%, are 92.7%, 91.8%, and 93.3%; for Δρ < 2%, the values are 53.5%, 51.3%, and 54.7%. At the level of B3LYP/6-31G**, for Δρ < 5%, the values are 92.3%, 91.4% and 92.9%; for Δρ < 2%, the values are 53.7%, 51.4% and 53.2%. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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11 pages, 4373 KiB  
Article
The Effect of Metal Film Thickness on Ignition of Organic Explosives with a Laser Pulse
by Alexander V. Khaneft, Vadim A. Dolgachev and Svyatoslav A. Rybin
Molecules 2019, 24(24), 4600; https://doi.org/10.3390/molecules24244600 - 16 Dec 2019
Cited by 2 | Viewed by 1990
Abstract
The results of numerical ignition simulation of pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) by aluminium (Al) and molybdenum (Mo) films heated by nanosecond laser pulses in a three-layer system: glass–metal–explosive material (EM) are presented. Influence of metal [...] Read more.
The results of numerical ignition simulation of pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) by aluminium (Al) and molybdenum (Mo) films heated by nanosecond laser pulses in a three-layer system: glass–metal–explosive material (EM) are presented. Influence of metal film thickness on the time of EM ignition delay was considered. A non-linier dependence of time of delay of ignition of EM from thickness of a metal film is shown. The greatest critical thicknesses of Al and Mo metallic films at which ignition of EM is still possible were determined. It was established that the greater the thickness of the metal film and heat resistance of EM, the greater the heat reserve needed in EM ignition film. It was established that the ignition delay time of EM increases in the sequence of PETN, RDX, HMX and TATB. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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13 pages, 2700 KiB  
Article
Development of Inert, Polymer-Bonded Simulants for Explosives Detection Systems Based on Transmission X-ray
by Mitja Vahčič, David Anderson, Miguel Ruiz Osés, Grzegorz Rarata and Gabriela Diaconu
Molecules 2019, 24(23), 4330; https://doi.org/10.3390/molecules24234330 - 27 Nov 2019
Cited by 5 | Viewed by 3812
Abstract
Explosives detection systems (EDS) based on X-ray are used at airports to screen baggage for the presence of explosives. In Europe and the United States, EDS equipment is tested extensively by specialist test centres prior to approval for operational use in airports. Once [...] Read more.
Explosives detection systems (EDS) based on X-ray are used at airports to screen baggage for the presence of explosives. In Europe and the United States, EDS equipment is tested extensively by specialist test centres prior to approval for operational use in airports. Once EDS are installed in airports, however, it can be challenging to test the EDS equipment and verify that it continues to perform at the highest level, because of the impracticality of introducing bulk explosives into civil aviation airports. We have developed inert, non-toxic polymer-bonded simulants and validated them against real explosives using EDS equipment. The accuracy of our simulants is within 1% of the target bulk density, and within 2% of the target effective atomic number, and the materials have a stability of at least 4 years, with an uncertainty of 0.5%. The simulants generate alarms in almost 100% of cases on a wide range of commercial EDS models, and we consider the simulants fit for purpose for use during testing of EDS equipment at airports. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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15 pages, 3297 KiB  
Article
Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane
by Pengcheng Zhang, Dheeraj Kumar, Lei Zhang, Daniel Shem-Tov, Natan Petrutik, Ajay Kumar Chinnam, Chuang Yao, Siping Pang and Michael Gozin
Molecules 2019, 24(23), 4324; https://doi.org/10.3390/molecules24234324 - 26 Nov 2019
Cited by 18 | Viewed by 3701
Abstract
Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material—3,7-diamino-2,6-dinitro-1H,5H [...] Read more.
Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material—3,7-diamino-2,6-dinitro-1H,5H-pyrazolo-[1,2-a]pyrazole-1,5-dione (4), the structure of which was comprehensively analyzed by a variety of advanced spectroscopic methods and by X-ray crystallo-graphy (with density of 1.845 g·cm−3 at 173 K). Although obtained crystals of 4 contained solvent molecules in their structure, state-of-the-art density functional theory (DFT) computational techniques allowed us to predict that solvent-free crystals of this explosive would preserve a similar tightly packed planar layered molecular arrangement, with the same number of molecules of 4 per unit cell, but with a smaller unit cell volume and therefore higher energy density. Explosive 4 was found to be heat resistant, with an onset decomposition temperature of 328.8 °C, and was calculated to exhibit velocity of detonation in a range of 6.88–7.14 km·s−1 and detonation pressure in the range of 19.14–22.04 GPa, using for comparison both HASEM and the EXPLO 5 software. Our results indicate that the trans-bimane explosophore could be a viable platform for the development of new thermostable energetic materials. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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18 pages, 5177 KiB  
Article
Comparative Theoretical Studies on a Series of Novel Energetic Salts Composed of 4,8-Dihydrodifurazano[3,4-b,e]pyrazine-based Anions and Ammonium-based Cations
by Binghui Duan, Ning Liu, Bozhou Wang, Xianming Lu and Hongchang Mo
Molecules 2019, 24(18), 3213; https://doi.org/10.3390/molecules24183213 - 4 Sep 2019
Cited by 11 | Viewed by 2552
Abstract
4,8-Dihydrodifurazano[3,4-b,e]pyrazine (DFP) is one kind of parent compound for the synthesis of various promising difurazanopyrazine derivatives. In this paper, eleven series of energetic salts composed of 4,8-dihydrodifurazano[3,4-b,e]pyrazine-based anions and ammonium-based cations were designed. Their densities, [...] Read more.
4,8-Dihydrodifurazano[3,4-b,e]pyrazine (DFP) is one kind of parent compound for the synthesis of various promising difurazanopyrazine derivatives. In this paper, eleven series of energetic salts composed of 4,8-dihydrodifurazano[3,4-b,e]pyrazine-based anions and ammonium-based cations were designed. Their densities, heats of formation, energetic properties, impact sensitivity, and thermodynamics of formation were studied and compared based on density functional theory and volume-based thermodynamics method. Results show that ammonium and hydroxylammonium salts exhibit higher densities and more excellent detonation performance than guanidinium and triaminoguanidinium salts. Therein, the substitution with electron-withdrawing groups (–NO2, –CH2NF2, –CH2ONO2, –C(NO2)3, –CH2N3) contributes to enhancing the densities, heats of formation, and detonation properties of the title salts, and the substitution of –C(NO2)3 features the best performance. Incorporating N–O oxidation bond to difurazano[3,4-b,e]pyrazine anion gives a rise to the detonation performance of the title salts, while increasing their impact sensitivity meanwhile. Importantly, triaminoguanidinium 4,8-dihydrodifurazano[3,4-b,e]pyrazine (J4) has been successfully synthesized. The experimentally determined density and H50 value of J4 are 1.602 g/cm3 and higher than 112 cm, which are consistent with theoretical values, supporting the reliability of calculation methods. J4 proves to be a thermally stable and energetic explosive with decomposition peak temperature of 216.7 °C, detonation velocity 7732 m/s, and detonation pressure 25.42 GPa, respectively. These results confirm that the derivative work in furazanopyrazine compounds is an effective strategy to design and screen out potential candidates for high-performance energetic salts. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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Review

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19 pages, 8335 KiB  
Review
CL-20-Based Cocrystal Energetic Materials: Simulation, Preparation and Performance
by Wei-qiang Pang, Ke Wang, Wei Zhang, Luigi T. De Luca, Xue-zhong Fan and Jun-qiang Li
Molecules 2020, 25(18), 4311; https://doi.org/10.3390/molecules25184311 - 20 Sep 2020
Cited by 31 | Viewed by 4466
Abstract
The cocrystallization of high-energy explosives has attracted great interests since it can alleviate to a certain extent the power-safety contradiction. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), one of the most powerful explosives, has attracted much attention for researchers worldwide. However, the disadvantage of CL-20 has increased sensitivity [...] Read more.
The cocrystallization of high-energy explosives has attracted great interests since it can alleviate to a certain extent the power-safety contradiction. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), one of the most powerful explosives, has attracted much attention for researchers worldwide. However, the disadvantage of CL-20 has increased sensitivity to mechanical stimuli and cocrystallization of CL-20 with other compounds may provide a way to decrease its sensitivity. The intermolecular interaction of five types of CL-20-based cocrystal (CL-20/TNT, CL-20/HMX, CL-20/FOX-7, CL-20/TKX-50 and CL-20/DNB) by using molecular dynamic simulation was reviewed. The preparation methods and thermal decomposition properties of CL-20-based cocrystal are emphatically analyzed. Special emphasis is focused on the improved mechanical performances of CL-20-based cocrystal, which are compared with those of CL-20. The existing problems and challenges for the future work on CL-20-based cocrystal are discussed. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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45 pages, 8909 KiB  
Review
Glycidyl Azide Polymer and its Derivatives-Versatile Binders for Explosives and Pyrotechnics: Tutorial Review of Recent Progress
by Tomasz Jarosz, Agnieszka Stolarczyk, Agata Wawrzkiewicz-Jalowiecka, Klaudia Pawlus and Karolina Miszczyszyn
Molecules 2019, 24(24), 4475; https://doi.org/10.3390/molecules24244475 - 6 Dec 2019
Cited by 34 | Viewed by 6944
Abstract
Glycidyl azide polymer (GAP), an energetic binder, is the focus of this review. We briefly introduce the key properties of this well-known polymer, the difference between energetic and non-energetic binders in propellant and explosive formulations, the fundamentals for producing GAP and its copolymers, [...] Read more.
Glycidyl azide polymer (GAP), an energetic binder, is the focus of this review. We briefly introduce the key properties of this well-known polymer, the difference between energetic and non-energetic binders in propellant and explosive formulations, the fundamentals for producing GAP and its copolymers, as well as for curing GAP using different types of curing agents. We use recent works as examples to illustrate the general approaches to curing GAP and its derivatives, while indicating a number of recently investigated curing agents. Next, we demonstrate that the properties of GAP can be modified either through internal (structural) alterations or through the introduction of external (plasticizers) additives and provide a summary of recent progress in this area, tying it in with studies on the properties of such modifications of GAP. Further on, we discuss relevant works dedicated to the applications of GAP as a binder for propellants and plastic-bonded explosives. Lastly, we indicate other, emerging applications of GAP and provide a summary of its mechanical and energetic properties. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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21 pages, 5936 KiB  
Review
A Review on the Reactivity of 1-Amino-2-Nitroguanidine (ANQ)
by Jinghua Wang, Meng Cai, Fengqi Zhao and Kangzhen Xu
Molecules 2019, 24(19), 3616; https://doi.org/10.3390/molecules24193616 - 8 Oct 2019
Cited by 6 | Viewed by 3884
Abstract
1-Amino-2-nitroguanidine (ANQ) is a high-energy nitrogen-rich compound with good detonation properties and low sensitivities. ANQ has only a central carbon atom with three small groups around it, including an amino, a hydrazine and a nitroxyl group. Though the molecular structure of ANQ is [...] Read more.
1-Amino-2-nitroguanidine (ANQ) is a high-energy nitrogen-rich compound with good detonation properties and low sensitivities. ANQ has only a central carbon atom with three small groups around it, including an amino, a hydrazine and a nitroxyl group. Though the molecular structure of ANQ is very simple, its reactivity is surprisingly abundant. ANQ can undergo various reactions, including reduction reaction, acylation reaction, salification reaction, coordination reaction, aldimine condensation reaction, cyclization reaction and azide reaction. Many new energetic compounds were purposely obtained through these reactions. These reactions were systematically summarized in this review, and detonation properties of some energetic compounds were compared. In the field of energetic materials, ANQ and some derivatives exhibit good application prospects. Full article
(This article belongs to the Special Issue Advanced Chemistry of Energetic Materials)
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