High-speed visible supercontinuum laser absorption spectroscopy of metal oxides.

Supercontinuum laser absorption spectroscopy is applied to energetic material combustion fireball environments using the visible spectrum for temperature and column density measurements of key metal combustion intermediates TiO and AlO. Fireballs are produced by igniting metal/ammonium perchlorate powder beds on a thermal-jump apparatus. This work marks, to our knowledge, the first quantitative absorption measurement of TiO (B2Πr-X2Δr, Δv=0) and demonstrates the feasibility of broadband visible metal-oxide absorption thermometry at rates up to 100 kHz. We also demonstrate the capability for single laser-shot absorption measurements. The mean AlO (B2Σ+-X2Σ+, Δv=0) temperature is 3010 K, whereas TiO has a mean temperature of 2095 K; both agree well with previous literature. Typical signal-to-noise ratios for the TiO and AlO absorption spectra are 22. The 100 kHz measurement rate reveals the time dynamics of titanium combustion-illustrating the potential for broadband multispecies monitoring in dynamic fireball environments.

Smart Electromagnetic Thermites: GO/rGO Nanoscale Thermite Composites with Thermally Switchable Microwave Ignitability.

This effort demonstrates the development of a novel, graphene oxide nanoscale thermite composite with thermally tunable microwave ignitability. A model thermite system containing nanoscale aluminum and nanoscale iron(II) oxide in a stoichiometric ratio (30/70 wt %) was combined with sheets of graphene oxide (GO) or reduced graphene oxide (rGO) using an immiscible two-fluid sonication and tape casting process. The samples were microwave irradiated within a single-mode resonant microwave cavity to determine the microwave ignition delay. Neat thermites were found to ignite after 4.34 s of microwave illumination, whereas 30 wt % rGO thermite composite ignition delay was an order of magnitude shorter (0.43 s). For most samples (4 of 6 trials), it was found that application of a 30 wt % GO coating inhibits microwave ignition of the thermite. Thermal treatment of the GO thermite composite led to switching of thermites from unignitable to ignitable with microwave field application as short as 0.24 s due to GO reduction. Optimum heat treatment time and GO content are explored with SEM, DSC/TGA-MS, Raman, and XPS deconvolution. This effort demonstrates the use of GO and rGO addition to achieve thermally switchable microwave ignitability to electromagnetically shield or enhance nanoscale energetic ignition by microwave energy.

Removing hydrochloric acid exhaust products from high performance solid rocket propellant using aluminum-lithium alloy.

Hydrochloric acid (HCl) pollution from perchlorate based propellants is well known for both launch site contamination, as well as the possible ozone layer depletion effects. Past efforts in developing environmentally cleaner solid propellants by scavenging the chlorine ion have focused on replacing a portion of the chorine-containing oxidant (i.e., ammonium perchlorate) with an alkali metal nitrate. The alkali metal (e.g., Li or Na) in the nitrate reacts with the chlorine ion to form an alkali metal chloride (i.e., a salt instead of HCl). While this technique can potentially reduce HCl formation, it also results in reduced ideal specific impulse (ISP). Here, we show using thermochemical calculations that using aluminum-lithium (Al-Li) alloy can reduce HCl formation by more than 95% (with lithium contents ≥15 mass%) and increase the ideal ISP by ∼7s compared to neat aluminum (using 80/20 mass% Al-Li alloy). Two solid propellants were formulated using 80/20 Al-Li alloy or neat aluminum as fuel additives. The halide scavenging effect of Al-Li propellants was verified using wet bomb combustion experiments (75.5±4.8% reduction in pH, ∝ [HCl], when compared to neat aluminum). Additionally, no measurable HCl evolution was detected using differential scanning calorimetry coupled with thermogravimetric analysis, mass spectrometry, and Fourier transform infrared absorption.