In order to effectively model the behaviour of energetic materials under operational conditions it is essential to obtain detailed structural information for these compounds at elevated temperature and/or pressures. The structural characterisation of the high explosives RDX and CL-20 and a series of inorganic azides [Mn+(N3)n] at extreme conditions is described herein. In addition to the characterisation of a highly metastable β -form of RDX (1,3,5- trinitrohexahydro-1,3,5-triazine) at atmospheric pressure, the structure solution of a high-pressure/ high-temperature polymorph is described. This form, obtained above 4.3 GPa and 450 K, has been shown to be distinct from the β -form and has therefore been denoted - RDX. Furthermore, ε -RDX is sufficiently metastable to allow its recovery to ambient pressure at 150 K; it only transforms to the α -form upon warming to 230 K. Finally, the ambient-temperature compression of RDX has been investigated to a maximum pressure of 23.0 GPa, using methanol:ethanol (4:1) as the pressure-transmitting medium; no phase transition was observed under these conditions, other than the α → γ transition at 3.9 GPa. The structure of a high-pressure polymorph of CL-20 (2,4,6,8,10,12- hexanitrohexaazaisowurtzitane) has also been determined by a combination of powder and single-crystal X-ray diffraction. Compression of γ -CL-20 to above 0.7 GPa using Fluorinert (FC-77) as the pressure-transmitting medium results in a phase transition to the ζ -form, which has been found to display structural similarities with both theγ γ - and ε -forms. The high-pressure behaviour of CL-20, however, depends markedly on the starting polymorph and the pressure-transmitting medium selected. Compression of γ -CL-20 in MeOH:EtOH (4:1) results in the formation of a 2:1 CL-20:MeOH solvate at 0.5 GPa. This solvate is stable upon compression to P > 5.0 GPa. It may also be recovered to ambient pressure at 293 K. Meanwhile, no phase transition is observed during the compression of ε -CL-20 to a maximum pressure of 7.2 GPa. Finally, a series of inorganic azides [NaN3, CsN3, TlN3, NH4N3, AgN3 and Pb(N3)2] has been characterised under a range of pressure and temperature conditions. Of the six compounds studied, all displayed at least one polymorphic transition – 5 new forms have been structurally characterised in this work and evidence of another 5 is presented. The combined effect of pressure and temperature results in sodium azide adopting a tetragonal structure common to larger alkali metal azides. Caesium azide has been shown to undergo three phase transitions during compression to 6.0 GPa – the structure of the first high-pressure form is reported. A variable temperature X-ray powder diffraction study of TlN3 has allowed the structural characterisation of the low-temperature TlN3-IV (at 230 K) as well as providing evidence for a phase transition to a high-temperature form above 550 K. The high-pressure form III (obtained above 0.76 GPa) has also been determined by neutron powder diffraction. Silver, ammonium and lead(II) azides have all been shown to undergo a phase transition at high pressures. Compression of silver azide (P > 0.80 GPa) removes an orthorhombic distortion observed at atmospheric pressure, resulting in the tetragonal structure adopted by CsN3 and TlN3 under ambient conditions. Moreover, NH4N3 and Pb(N3)2 have been found to undergo phase transitions at 2.6 GPa, although their high-pressure structures have still to be determined.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:586213 |
| Date | January 2011 |
| Creators | Millar, David Iain Archibald |
| Contributors | Pulham, Colin; Robertson, Neil |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/8213 |
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