Journal of Chemical Physics, Vol.110, No.17, 8730-8741, 1999
Extent of reaction in energetic particulate mixtures: Role of composition and particle size ratio
The extent of reaction in reactive solid mixtures, comprising two or more particulate components, can be significantly affected by the presence of unavoidable compositional fluctuations in these systems. This is particularly the case where the size of the reaction zone is of the order of a few particle diameters. Results of detailed computer simulations, aimed at investigating the influence of composition and particle size ratios, on the fluctuations and thus the extent of reaction in reactive solid mixtures, are reported here. These data are complemented by analytical calculations performed for systems in certain limiting cases. In accord with experimental observations on certain classes of such systems, namely pyrotechnics, both the simulation and the analytical results show that the extent of reaction attains its maximum value at compositions, which compared to the stoichiometric ratio, are somewhat richer in the minor component. The deviation of the optimal composition from stoichiometry becomes more pronounced for small reaction zone sizes, where the relative compositional fluctuations are larger. The effect of altering the particle size ratio, for systems where the stoichiometric volume ratio is different to 1:1, is found to be markedly asymmetric. Reducing the size of the particles of the minor component is seen to dramatically improve the extent of reaction in the system. In contrast, any observed improvements, arising from a reduction in the size of the major component, are found to be at best marginal. The analytical calculations allow an insight into these result to be gained.