Computational study on nitronium and nitrosonium oxalate: potential oxidizers for solid rocket propulsion?

The enthalpies of formation for solid ionic nitrosonium oxalate, [NO](2)[O(2)C-CO(2)], nitronium oxalate, [NO(2)](2)[O(2)C-CO(2)], as well as covalent bis(nitroso)oxalic acid, ON-O(2)C-CO(2)-NO, and oxalic acid dinitrate ester, O(2)N-O(2)C-CO(2)-NO(2), were calculated using the complete basis set (CBS-4M) method of Petersson and coworkers to obtain very accurate energies. For the nitrosonium species, the ionic form ([NO](2)[O(2)C-CO(2)]) was identified as the more stable isomer, whereas for the nitrosonium compound, the covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was found to be more stable. The combustion parameters with respect to possible use as ingredients in solid rocket motors for both stable species were calculated using the EXPLO5 and the ICT code. The performance of an aluminized formulation with covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was shown to be comparable to that of ammonium perchlorate/aluminum. This makes oxalic acid dinitrate ester a potentially interesting perchlorate-free and environmentally benign oxidizer for solid rocket propulsion.

Photothermal initiation of hybrid organic/inorganic metastable interstitial composites: synergistic effects on the dynamics of energy release.

The organic high-energy material pentaerythritol tetranitrate (PETN) was incorporated at low concentrations into Al (100 nm)/Fe(2)O(3) metastable intersitital composites (MIC) to form a hybrid organic/inorganic high-energy material. Studies of the dynamics of energy release were carried out by initiating the reaction photothermally with a single 8 ns pulse of the 1064 nm fundamental of a Nd:YAG laser. The reaction dynamics were measured using time-resolved spectroscopy of the light emitted from the deflagrating material. Two parameters were measured: the time to initiation and the duration of the deflagration. The presence of small amounts of PETN (16 mg/g of MIC) results in a dramatic decrease in the initiation time. This is attributed to a contribution to the temperature of the reacting system from the combustion of the PETN that, at lower loadings, appears to follow an Arrhenius dependence. The presence of PETN was also found to reduce the energy density required for single-pulse photothermal initiation by an order of magnitude, suggesting that hybrid materials such as this may be engineered to optimize their use as an efficient photodetonation medium.