One of the open questions in understanding the reactivity of nanometric metal/metal oxide particulate composites is the relative role of gas-solid vs. condensed state reactions. This work is an investigation of several nano-Al based thermites subjected to very rapid heating rates. The ignition temperature of thermites, as measured by the onset of optical emission, was measured using a rapidly heated Pt wire. Generally, ignition was seen to occur above the melting temperature of aluminum. The exception was Al/Bi(2)O(3) which ignited slightly below this point. Samples were also rapidly heated in situ within electron microscopes to provide direct imaging before and after heating. The sintering of aggregated and/or agglomerated particles into characteristically larger structures was experimentally observed in all cases, and the fuel and oxidizer were found to be in surface contact suggesting that a condensed-phase reactive sintering mechanism had occurred. High resolution image sequences of thermites ignited on the Pt wire were collected using a real time phase contrast imaging technique at the Advanced Photon Source of Argonne National Lab. The results suggest that reactive sintering occurs on a fast timescale, and relatively early in the reaction, leading to rapid melting and coalescence of aggregated particles. This dramatically changes the initial size and morphology of the constituents before the remainder of the material burns. The results question the idea that a decrease in particle size will necessarily lead to an enhancement in reactivity, since large amounts of sintering occurs early in the reaction, and alters the morphology. It is suggested that improvements in reactivity can be achieved by designing architectures to improve the interfacial contact upon sintering, as well as by selecting oxidizers based on their ability to liberate and transport oxygen in the condensed phase, while producing volatile species to assist in convective energy transport. (C) 2011 Published by Elsevier Inc. on behalf of The Combustion Institute.