Understanding the Relationships Between Architecture, Chemistry, and Energy Release of Energetic Nanocomposites
DeLisio, Jeffery Brandon
Zachariah, Michael R
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Energetic nanocomposites are a class of reactive material that incorporate nanosized materials or features in order to enhance reaction kinetics and energy densities. Typically, these systems employ metal nanoparticles as the fuel source and have demonstrated reactivities orders of magnitude larger than more traditionally used micron-sized metal fuels. One drawback of using nanosized metals is that the nascent oxide shell comprises a significant weight percent as the particle size decreases. This shell also complicates the understanding of oxidation mechanisms of nanosized metal fuels. In this dissertation, I apply a two-fold approach to understanding the relationships between architecture, chemistry, and energy release of energetic nanocomposites by 1) investigating alternative metal fuels to develop a deeper understanding of the reaction mechanisms of energetic nanocomposites and 2) creating unique microstructures to tailor macroscopic properties allowing for customizability of energetic performance. In order to accurately study these systems, new analytical techniques capable of high heating rate analysis were developed. The oxidation mechanisms of tantalum nanoparticles was first probed using high heating rate TEM and Temperature-Jump Time-of-Flight Mass Spectrometry (T-Jump TOFMS) and shell crystallization was found to plan an important role in the mechanism. An air-sensitive sample holder was developed and employed to analyze the decomposition and oxidation of molecular aluminum compounds, which theoretically can achieve similar energy release rates to monomolecular explosives in addition to much higher energy densities. In order to obtain simultaneous thermal and speciation data at high heating rates, a nanocalorimeter was integrated into the TOFMS system and measurements were performed on Al/CuO nanolaminates to probe the effect of bilayer thickness on energy release. An electrospray based approach to creating energetic nanocomposites with tunable architectures is also described. An in depth study on the electrospray synthesized nAl/PVDF thin film reaction mechanism was performed using T-Jump TOFMS. The nAl/PVDF system was also studied using a Molecular Beam Sampling Time-of-Flight Mass Spectrometer designed and built primarily to investigate the reaction mechanisms of energetic nanocomposites at 1 atm in both aerobic and anaerobic environments.