Multiply Nitrated High‐Energy Dense Oxidizers Derived from the Simple Amino Acid Glycine

Various energetic polynitro esters, carbamates, and nitrocarbamates that were derived from the amino acid glycine were fully characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Owing to their positive oxygen balance, the suitability of these compounds as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were calculated by using the Gaussian 09 program package at the CBS‐4M level of theory. From these values and the calculated densities (from the X‐ray data), several detonation parameters, such as detonation pressure, velocity, energy, and temperature, were computed by using the EXPLO5 code. Furthermore, their sensitivities towards impact, friction, and electrostatic discharge were tested by using a drop hammer, a friction tester (both BAM certified), and a small‐scale electrical‐discharge device, respectively.     

Energetic Silver Salts with 5-Aminotetrazole Ligands

Methylation of 5-amino-1H-tetrazole ( 1 ) gives 1-methyl-5-amino-1H-tetrazole ( 2 ) and 2-methyl-5-amino-1H-tetrazole ( 3 ). A new family of energetic silver complexes based on ligands 1 , 2 and 3 with perchlorate and nitrate anions ( 10 – 15 ) were synthesized and characterized by using IR, Raman, and NMR (¹H, ¹³C, ¹⁴N, and ³⁵Cl NMR) spectroscopy, elemental analysis, and mass spectrometry. The crystal structures of the compounds were determined where possible and reveal interesting structural details that are discussed herein. Additionally, differential scanning calorimetry was used to assess the thermal stability of the new salts, which showed excellent thermal stabilities at temperatures up to and above 225 °C. Standard tests were also used to assess the sensitivity of the materials towards impact and friction. All the silver complexes showed increased sensitivity values in comparison with analogous protonated 5-amino-1H-tetrazolium perchlorate and nitrate salts. Some of these materials have sensitivity values that are comparable to commonly used primary explosives and all of them either deflagrate ( 12 – 14 ) or detonate loudly ( 10 and 11 ) on contact with an open flame. Lastly, nitrate salt 11 is easily initiated by thermal shock. It shows reasonably low sensitivity in comparison with other silver salts (e.g., silver azide or silver fulminate), which makes handling it much less hazardous. Compound 11 also has good thermal stability, decomposing at ≈300 °C, and shows interesting properties as a more environmentally benign alternative to lead(II) diazide in initiation devices for civil and military applications.     

Hypergolic N,N‐Dimethylhydrazinium Ionic Liquids

N,N‐Dimethylhydrazinium dicyanamide and nitrocyanamide ionic liquids (ILs) were prepared by quaterization of N,N‐dimethylhydrazine with alkyl halides followed by metathesis reactions with silver dicyanamide or silver nitrocyanamide. The key physicochemical properties, such as melting point and decomposition temperatures, density, viscosity, heat of formation, detonation pressure and velocity, and specific impulse were measured/calculated. The impact of anions and alkyl‐substituted cations on these properties is demonstrated. Droplet tests with white‐fuming nitric acid (WFNA) as an oxidizer were utilized to show that the 14 new N,N‐dimethylhydrazinium salts are hypergolic with ignition delay (ID) times ranging from 22 to 1642 ms, thereby suggesting that some may have potential as bipropellants.     

Investigation of nitrogen‐rich energetic polymers based on alkylbridged bis‐(1‐methyl‐tetrazolylhydrazines)

Nitrogen‐rich energetic polymers were synthesized by the polyaddition reaction of 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1a ), 1‐methyl‐1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1b ), and 1,4‐bis(5‐mono‐methylhydrazinyl‐1H‐tetrazolyl)butane ( 1c ) with hexamethylene diisocyanate. The experiments showed that neither a polymerization from solution or bulk was possible. Therefore, a new method for the polymerization of tetrazolyl hydrazines had to be developed. The formed polymers were characterized by vibrational spectroscopy (IR) and elemental analysis. The energetic properties were investigated by bomb calorimetric measurements along with calculations using the EXPLO5 software. The thermal stability was investigated by DSC measurements. The properties render the polymers into promising compounds regarding an application as energetic binder. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 122–127, 2010     

Energetic properties of nio surface examined by heat-of-adsorption measurement

Heat of adsorption and isotherm of water vapor on NiO samples were measured simultaneously at 301 K to examine the energetic properties of the surface. They revealed that NiO has a relatively uniform surface. The heat of adsorption ranging 80–90 kJ·mol^–1 indicates the production of surface hydroxyl groups on the (100) plane of NiO. It is relatively small compared with that of other metal oxides, which suggests a weak nature of the Ni²⁺ ion sites for chemisorption of water. It is suspected that half of the surface Ni²⁺ ions are covered with hydroxyl groups and the remainings act as relatively strong physisorption sites for water molecules.The authors are grateful for the help of Prof. S. Kittaka of Okayama University of Science in taking electron micrographs. This work was partly supported by Grant-in-Aid for Scientific Research No. 02640348 from the Ministry of Education, Science and Culture of Japanese Government.     

Solar hard X-rays and gamma-rays

We briefly introduce our recent work on the spectral evolution of energetic protons, the beam property of accelerated electrons, the gamma-ray flare classification, the temporal features of the annihilation line, the hard X-ray delayed events, the hydrodynamic process, and the continuum emission in solar flares.     

冲击作用下凝聚态含能材料热点形成热－机械分析

应用动力有限元方法分析含能材料中热点形成机理。在假定凝聚态含能材料为可压缩的情况下，研究圆形和椭圆形微孔洞附近介质在冲击作用下热－机械响应过程，结果显示冲击波强度、空隙率、微孔洞尺寸和形状、熔点对热点温升有强烈影响，并讨论粘塑性功和固相压缩成为主要机制的条件。     

含能材料三轴动态压缩实验的一个计算机模拟方法

在含能材料单轴、受限三轴动态压缩实验的基础上，提出一种将计算机数值模拟和实验数据相结合，估算实验系统中钢筒与试件间的库伦摩擦力，从而正确确定含能材料的动态三轴力学性能（弹性模量Ｅ，泊桑比ν，屈服限Ｙ等）的方法。本方法用于ＴＮＴ炸药受限三轴动态压缩实验，通过建立钢筒－试件的库伦摩擦有限元模型，采用ＡＤＩＮＡ通用程序进行动力分析，估算了摩擦力对实验数据的影响，获得了考虑摩擦力修正后的ＴＮＴ三轴动态压缩响应，为含能材料三轴动态力学性能的确定提供了一种有效的方法。     

Ammonia–(Dinitramido)boranes: High‐Energy‐Density Materials

Two ammonia–(dinitramido)boranes were synthesized by the reaction of dinitroamine with ammonia–borane. These compounds are the first reported examples of (dinitramido)boranes. Ammonia–mono(dinitramido)borane is a perfectly oxygen‐balanced high‐energy‐density material (HEDM) composed of an ammonia–BH₂ fuel group and a strongly oxidizing dinitramido ligand. Although it is thermally not stable enough for practical applications, its predicted specific impulse as a solid rocket propellant would be 333 s. Its predicted performance as an explosive matches that of pentaerythtritol tetranitrate (PETN) and significantly exceeds that of trinitrotoluene (TNT). Its structure was established by X‐ray crystallography and vibrational and multinuclear NMR spectroscopy. Additionally, the over‐oxidized ammoniabis(dinitramido)borane was detected by NMR spectroscopy.