Self-Organized Al2Cu Nanocrystals at the Interface of Aluminum-Based Reactive Nanolaminates to Lower Reaction Onset Temperature.

Nanoenergetic materials are beginning to play an important role in part because they are being considered as energetic components for materials, chemical, and biochemical communities (e.g., microthermal sources, microactuators, in situ welding and soldering, local enhancement of chemical reactions, nanosterilization, and controlled cell apoptosis) and because their fabrication/synthesis raises fundamental challenges that are pushing the engineering and scientific frontiers. One such challenge is the development of processes to control and enhance the reactivity of materials such as energetics of nanolaminates, and the understanding of associated mechanisms. We present here a new method to substantially decrease the reaction onset temperature and in consequence the reactivity of nanolaminates based on the incorporation of a Cu nanolayer at the interfaces of Al/CuO nanolaminates. We further demonstrate that control of its thickness allows accurate tuning of both the thermal transport and energetic properties of the system. Using high resolution transmission electron microscopy, X-ray diffraction, and differential scanning calorimetry to analyze the physical, chemical and thermal characteristics of the resulting Al/CuO + interfacial Cu nanolaminates, we find that the incorporation of 5 nm Cu at both Al/CuO and CuO/Al interfaces lowers the onset temperature from 550 to 475 °C because of the lower-temperature formation of Al-Cu intermetallic phases and alloying. Cu intermixing is different in the CuO/Cu/Al and Al/Cu/CuO interfaces and independent of total Cu thickness: Cu readily penetrates into Al grains upon annealing to 300 °C, leading to Al/Cu phase transformations, while Al does not penetrate into Cu. Importantly, θ-Al2Cu nanocrystals are created below 63% wt Cu/Al, and coexist with the Al solid solution phase. These well-defined θ-Al2Cu nanocrystals seem to act as embedded Al+CuO energetic reaction triggers that lower the onset temperature. We show that ∼10 nm thick Cu at Al/CuO interfaces constitutes the optimum amount to increase both reactivity and overall heat of reaction by a factor of ∼20%. Above this amount, there is a rapid decrease of the heat of reaction.