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Abstract. This paper provides an overview of the main developments over the past nine years in the study of the sensitivity of energetic materials (EM) to impact, shock, friction, electric spark, laser beams and heat. Attention is also paid to performance and to its calculation methods. Summaries are provided of the relationships between sensitivity and performance, the best representations for the calculation methods of performance being the volume heat of explosion or the product of crystal density and the square of detonation velocity. On the basis of current knowledge, it is possible to state that a single universal relationship between molecular structure and initiation reactivity does not yet exist. It is confirmed that increasing the explosive strength is usually accompanied by an increase in the sensitivity. In the case of nitramines this rule is totally valid for friction sensitivity, but for impact sensitivity there are exceptions to the rule, and with 1,3,5-trinitro-1,3,5-triazepane, 1,3,5-trinitro-1,3,5-triazinane, β−1,3,5,7-tetranitro-1,3,5,7-tetrazocane and the α−, β− and ε−polymorphs of 2, 4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane the relationship works in the opposite direction. With respect to the QSPR approach there might be reasonably good predictions but it provides little insight into the physics and chemistry involved in the process of initiation.

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Over the past 20 years, a number of scientists have conducted numerous fundamental investigations based on quantum chemistry theory into various mechanistic processes that seems to contribute to the sensitivity of energetic materials. A large number of theoretical methods that have been used to predict their mechanical and spark sensitivity are summarized in this article, in which the advantages and disadvantages of these methods, together with their scope of use are clarified. In addition, the theoretical models for thermal stability of explosives are briefly introduced as a supplement. It has been concluded that the current ability to predict sensitivity is merely based on a series of empirical rules, such as simple oxygen balance, molecular properties, and the ratios of C and H to oxygen for different classes of explosive compounds. These are valid only for organic classes of explosives, though some special models have been proposed for inorganic explosives, such as azides. An exact standard for sensitivity should be established experimentally by some new techniques for both energetic compounds and their mixtures. © 2013 Wiley Periodicals, Inc.

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Matrices based on polyisobutylene (PIB), polymethyl‐methacrylate (PA), Viton A 200, Dyneon FT 2481 (Fluorel), and polydimethyl‐siloxane binders were studied as desensitizers. A series of plastic explosives (PBXs) were prepared, based on four different nitramines, namely RDX (1,3,5‐trinitro‐1,3,5‐triazinane), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20), bonded by the matrices mentioned. For comparison, pentaerythritol tetranitrate and certain commercial explosives based on it, Semtex 1A, Semtex 10 and Sprängdeg m/46, were used. Detonation velocities, sensitivities to impact and friction, and peak temperatures of thermal decomposition by differential thermal analysis technique (DTA) for all the explosives studied were determined. Heat of detonation was calculated by means of a thermodynamic calculation program (EXPLO 5 code). Fluoroelastomers have a neutral to positive effect on the thermal stability of nitramines and they have a significant effect on decreasing the friction sensitivity. However, their anti‐impact efficiency is the lowest in this study although they have a positive effect on performance of the corresponding PBXs. PA and PIB matrices markedly decrease thermal stability of nitramines, the anti‐impact influences of PIB‐binders are better than those of PA‐binders, while PA‐binders have a higher anti‐friction effect and slightly less negative influence on the performance of the PBXs in comparison with PIB mixtures. The polydimethyl‐siloxane matrix has a neutral effect on thermal stability of the nitramines studied, it has an influence on the volume thermochemistry of detonation comparable with that of fluoroelastomers although it does not provide comparable performance, and its corresponding PBXs have optimum sensitivity parameters.