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A systematic overview of melt cast explosives is given. The research on melt cast explosives over several decades can be divided into three broad areas: (i) aromatic compounds with CCH3, NCH3, OCH3 CNO2, NNO2 and ONO2 groups, (ii) improved synthesis of compounds, which are currently used in formulations or which have shown promise for such use and (iii) the preparation of melt cast formulations with various compositions. Exudation, high volume change from liquid to solid, super cooling, irreversible growth, fragility and unpredictable sensitivity are the disadvantages of existing melt cast formulations.

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The review describes the recent developments in the green synthetic methods of nitro compounds involving environmentally benign approaches such as, use of solid‐supported reagents, microwave‐assisted reactions, ionic liquids, ultrasound assisted nitration reactions, gas phase nitration and vapor phase nitration.

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TKX‐50 (Dihydroxylammonium 5,5’‐bistetrazolate‐1,1’‐dioxide) and ABTOX (Diammonium salt of 5,5’‐bistetrazole‐1,1′‐diolate) being simple and cheap to prepare from commonly available chemicals, are emerging as promising energetic materials along with the advantages like required thermal insensitivity, low toxicity and safe handling. In order to synthesize such powerful materials with utmost care, it is essential to know about the precursors and reaction intermediates involved. Therefore, the detailed thermal analyses of various precursors such as glyoxime (I), dichloroglyoxime (II), diazidoglyoxime (III) and bistetrazoledihydroxide (IV) and final products viz., TKX‐50 (V) and ABTOX (VI) were carried out using differential scanning calorimetric and thermal gravimetric analysis experiments. The relative trend of band gap values calculated from the difference of HOMO and LUMO is well correlated with the decomposition temperatures (Tmax) values at a heating rate of 10 °C min−1 indicating the relative thermal stability of I–VI. The impact and friction sensitivity of ABTOX and TKX‐50 indicated that these compounds are safer than the currently known powerful explosives such as CL‐20. The calculated density impulse of TKX‐50 in rocket propellant formulations was found to be 499 g m−2 s−1 which is similar as that of HMX (494 g m−2 s−1). The theoretical performance prediction of TKX‐50 as the potential ingredient in gun propellant formulations indicated that the TKX‐50 could yield higher force constant (1471 J K−1) in comparison to currently known explosive such as RDX (1412 J K−1).

During the last twenty years military explosives, and energetic materials in general, have changed significantly. Worldwide, research and development programs are active in developing promising insensitive HEMs with higher performance. This has been due to several factors, which include new operational requirements such as Insensitive Munitions (IM), but it is also due to the availability of new materials and to new assessment and modelling techniques. The present review focuses on the basic idea and necessity for IM, and the conditions, technical requirements and tests for IM. The review also explains the various promising insensitive high explosives, their synthesis and formulation used in different propellants.

Dihydroxyl ammonium 5,5′‐bistetrazole‐1,1′‐diolate (TKX‐50) is a promising energetic material with predicted performance similar to RDX as well as to CL‐20. In the present study, TKX‐50 was evaluated as a possible replacement for RDX in TNT‐based, aluminized as well as non‐aluminized melt cast formulations. Thermal analysis reveals the compatibility of TKX‐50 with benchmark explosives like RDX and TNT in explosive formulations. This paper describes the thermal and sensitivity study of TKX‐50 with RDX and TNT‐based melt cast explosives. The result indicated that TKX‐50 can be effectively used as a RDX replacement in melt cast explosive formulations. TKX‐50/TNT‐based aluminized composition shows more thermal stability than RDX/TNT based composition, which clearly indicated the usefulness of TKX‐50 in melt cast explosive formulations.