Tailoring the physical properties of energetic materials
Ward, Daniel W.
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Energetic materials are a class of material that have large amounts of chemical energy stored within their molecular structure. This energy is released upon decomposition, generally in the form of rapidly expanding, hot gases. They are therefore used for a wide range of applications such as; mining, military, and space exploration, and there is therefore a strong desire to improve the overall performance and safety of such materials. On account of reduced sensitivity to initiation by shock and impact, 2,4-dinitroanisole (DNAN) is a potential replacement for 2,4,6-trinitrotoluene (TNT) in melt-cast formulations for military applications. However, up to 15 % irreversible growth of DNAN has been previously observed upon thermal cycling and is a key reason why DNAN has not yet been universally accepted as a replacement for TNT. DNAN exhibits a complex system of polymorphism. One particular transition from DNAN-II to DNAN-III, which occurs at 266 K, has been observed in these studies to cause 8 - 10 % growth of DNAN-II pellets when temperature cycled for 30 cycles between 256 K and 276 K. What was even more concerning was the appearance of cracking of DNAN pellets after being temperature cycled. Doping the crystal structure of DNAN-II with related molecules, such as 2,4-dinitrotoluene or 2,4-dinitroaniline, was investigated in order to probe how steric and electronic factors affect the transition. The addition of varying amounts of 2,4-dinitroaniline suppressed this transition to varying extents and ultimately as low as 150 K with 10 mol% 2,4-dinitroaniline, and potentially eliminated entirely. This doped material has been designated as phase-stabilised DNAN (PS-DNAN). Temperature cycling of PS-DNAN was conducted over the same 256-276 K range, and this material showed no evidence of irreversible growth compared to undoped DNAN pellets, on account of suppression of the II-III transition. The production of PS-DNAN is therefore a possible route to avoiding problematic irreversible growth in DNAN formulations. Melt-casting of DNAN in a sealed environment consistently results in the metastable form-II, which has proven to be stable for in excess of 32 weeks. However, exposure to seeds of form-I, either via deliberate or accidental seeding, rapidly converted the material to the thermodynamically more stable form-I. This transition was accelerated by increasing temperature which rapidly converted pellets of DNAN-II to DNAN-I. When DNAN-I pellets were temperature cycled, they did not undergo a transition to form-III, and as a result did not illustrate irreversible growth. This presents another approach to avoiding problematic growth in DNAN-based materials. Whilst being one of the most widely used oxidisers in propellant formulations, ammonium perchlorate (AP) has several issues; the formation of porous ammonium perchlorate (PAP) can seriously affect the sensitivity of propellants, the hygroscopicity of AP makes handling and manufacture of formulations difficult, and spherical AP exhibits poor binding properties to the polymer binders used in propellant formulations. Several different approaches were taken to combat these issues. Co-crystallisation of AP was attempted in order to produce new AP co-crystals with reduced reactivity towards the formation of PAP. A theoretical based approach using COSMOtherm was used for rapid screening and selection of potential co-formers to be used in lab-based co-crystallisation trials. Co-crystallisation was attempted using multiple stoichiometries and multiple solvents by solvent evaporation, cooling crystallisation, and Resonant Acoustic Mixing methods. Unfortunately no new co-crystals were obtained, presumably on account of the ionic nature of AP which makes co-crystallisation difficult. The mass of untreated AP increased by 0.027% in a humid environment (90% RH) due to the uptake of water, which resulted in significant caking and hence hindering the processability of AP. In an attempt to counteract the hygroscopicity and improve the processability of AP, particles of AP were coated in graphene nanoplatelets using the technique of Resonant Acoustic Mixing. Low mixing energy (G-force) (30 G) resulted in poor coating of AP, but the flowability of this mixure after exposure to moisture was significantly enhanced, most probably as a result of graphene acting as an effective lubricant. Higher mixing energy (90-100 G) was required to break up agglomerates of graphene nanoplatelets and resulted in AP particles efficiently coated with graphene (APGR). Differential scanning calorimetry showed that the energy released upon decomposition of APGR was greater than pure AP, or AP mixed with graphene, due to the intimacy of the AP particle surface and the graphene coating.