High-Temperature Interactions of Metal Oxides and a PVDF Binder.

Interactions between energetic material relevant nanoscale metal oxides (SiO2, TiO2, MgO, Al2O3, CuO, Bi2O3) and poly(vinylidene fluoride) (PVDF) at high temperature were investigated by temperature-jump/time-of-flight mass spectrometry (T-jump/TOFMS) and thermogravimetric-differential scanning calorimetry (TGA-DSC). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology of the compositions, while X-ray diffraction (XRD) was utilized to analyze the condensed phase crystalline species at temperatures of interest. The exergonicity and exothermicity of HF gas with hydroxyl-terminated metal oxide surfaces make HF the likely fluorine-bearing moiety and primary mode of the fluorinating reactions, where terminal OH- configurations are replaced by F- in the formation of a stronger metal-fluorine bond. However, not all compositions produce corresponding stable metal fluoride. The results show that while some of the investigated metal oxide-PVDF compositions enhance PVDF decomposition and release HF in larger quantities than PVDF, others release HF in smaller quantities than PVDF and even retard PVDF decomposition. The former compositions demonstrate exothermic, multistep mass loss modes prior to neat PVDF mass loss, and the relative intensity of HF gas increases as the temperature of the release point decreases, implying a correlation between HF release and the progression of exothermic behavior. An interplay dynamic where surface interactions both lower the onset of HF release and engage exothermically with HF gas subsequently is proposed.

Carbon Fibers Enhance the Propagation of High Loading Nanothermites: In Situ Observation of Microscopic Combustion.

A major challenge in formulating and manufacturing energetic materials lies in the balance between total energy density, energy release rate, and mechanical integrity. In this work, carbon fibers are embedded into ∼90 wt % loading Al/CuO nanothermite sticks through a simple extrusion direct writing technique. With only ∼2.5 wt % carbon fiber addition, the burn rate and heat flux were promoted >2×. In situ microscopic observation of combustion shows that the carbon fiber intercept ejected hot agglomerates near the burning surface and enhanced heat feedback to the unreacted material. This study outlines how these approaches may enhance the propagation and reduce the two-phase flow losses.

Carbothermal shock synthesis of high-entropy-alloy nanoparticles.

The controllable incorporation of multiple immiscible elements into a single nanoparticle merits untold scientific and technological potential, yet remains a challenge using conventional synthetic techniques. We present a general route for alloying up to eight dissimilar elements into single-phase solid-solution nanoparticles, referred to as high-entropy-alloy nanoparticles (HEA-NPs), by thermally shocking precursor metal salt mixtures loaded onto carbon supports [temperature ~2000 kelvin (K), 55-millisecond duration, rate of ~105 K per second]. We synthesized a wide range of multicomponent nanoparticles with a desired chemistry (composition), size, and phase (solid solution, phase-separated) by controlling the carbothermal shock (CTS) parameters (substrate, temperature, shock duration, and heating/cooling rate). To prove utility, we synthesized quinary HEA-NPs as ammonia oxidation catalysts with ~100% conversion and >99% nitrogen oxide selectivity over prolonged operations.