Reactive metal nanolaminates, most notably aluminum/zirconium composites, have been developed as fuels to aid combustion in explosive formulations. Thus far, however, their energy density is limited by incomplete oxidation. An in situ x-ray diffraction (XRD) study was performed on a 40 µm thick Al:Zr (atomic ratio 1:1) multilayer foil to track the growth of reaction products during ignition, combustion, and cooling (over approximately 5 s) to determine the mechanisms that prevent complete combustion from occurring. Simultaneous pyrometry provides the ability to relate the observed phase progression to the foil temperature throughout the reaction, and post-reaction cross-sectional electron microprobe and transmission electron microscopy (TEM) of the combusted foils identify the location, composition, and microstructure of each product phase. We have used the combined results to develop an understanding of the growth mechanisms at play during the rapid reactions. The most significant finding is that the primary combustion product, orthorhombic ZrO2, grows linearly throughout the first 1.3 s of the reaction, indicating interface-limited growth, but then switches to slower diffusion-controlled growth. The transition in growth rate coincides with the abrupt end of a temperature plateau that is associated with self-sustained combustion. A thick (≈8 µm) Al2Zr layer is observed beneath the oxidized exterior in cross-sections of the reacted foil and is likely responsible for the reaction “turning off” before complete combustion is achieved. This underlying Al-rich intermetallic layer prevents the diffusion of aluminum away from the oxide interface, causing an increasing proportion of aluminum to oxidize. The resulting alumina creates a barrier to oxygen diffusion and is responsible for the incomplete combustion in air. © 2017 The Combustion Institute