Effect of Metal Sequestrants on the Decomposition of Hydroxylammonium Nitrate

Hydroxylammonium nitrate (HAN) is an energetic salt used in flight-proven green monopropellants such as ASCENT (formerly AF-M315E), flown in NASA’s 2019 Green Propellant Infusion Mission, and SHP163, flown in JAXA’s Rapid Innovative Satellite Technology Demonstration-1. The decomposition of HAN is catalyzed by metals commonly found in storage tanks, a factor limiting its use. This work investigates the ability of metal-sequestering chelating agents to inhibit the decomposition of HAN. Isothermal and dynamic thermogravimetric analysis (TGA) were used to find isothermal decomposition rates, decomposition onset temperatures, and first-order Arrhenius reaction rate parameters. In the present research, 2,2′-bipyridine (Bipy), triethanolamine (TEA), and ethylenediaminetetraacetic acid (EDTA) were studied as 0.05, 0.1, 0.5, 1, and 5% by weight additives in 90% aqueous HAN. An isothermal decomposition rate of 0.137%/h at 348 K was observed for HAN. The addition of 1% Bipy and 1% TEA reduced the isothermal decomposition rate by 20.4% to 0.109%/h, and by 3.65% to 0.132%/h, respectively, showing that Bipy can inhibit decomposition. The addition of 1% EDTA increased the isothermal decomposition rate by 12.4% to 0.154%/h. Bipy was found to increase the decomposition onset temperature from 454.8 K to 461.8 K, while the results for TEA and EDTA were inconclusive. First order reaction rates calculated by the Ozawa-Flynn-Wall method were found to be insufficient to capture the effects of the tested additives. Bipy was found to inhibit the decomposition of HAN, while TEA and EDTA produced little or negative effect, a result believed to be due to poor metal complex stability at low pH and high acidity, respectively. Spectrophotometry, used for colorimetric analysis of Bipy+iron complexes, showed that Bipy forms chelate complexes with trace iron impurities when added to HAN solutions.

Decomposition of Hydroxylammonium Nitrate Solution Over Nanoporous CuO Supported on Honeycomb

We investigated the influence of a copper loading strategy over a honeycomb structure on the catalytic performance during the decomposition of a hydroxylammonium nitrate (HAN) aqueous solution. Copper was supported on the honeycomb surface by means of a metal coating method (MC), i.e., a method of directly coating a metal, and a metal alumina coating method (MAC), i.e., a method of coating a mixture of metal and alumina. The properties of the catalysts were analyzed by N2 adsorption, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The Cu(16.8)/honeycomb-MC catalyst showed a lower decomposition onset temperature during the decomposition of the HAN aqueous solution compared to that over the Cu(7.0)/honeycomb- MAC catalyst, an outcome ascribed to the higher copper loading and the higher dispersion of copper in the Cu(16.8)/honeycomb-MC catalyst compared to that in the other catalyst. The Cu(16.8)/honeycomb-MC catalyst was confirmed to have both excellent activity and heat resistance during the decomposition of a HAN aqueous solution.

Thermochemistry of Combustion in Polyvinyl Alcohol + Hydroxylammonium Nitrate

A mixture of polyvinyl alcohol (PVA) and hydroxylammoniun nitrate (HAN) forms a gummy solid known as a plastisol, which is ionically conducting. When an electrostatic potential of 200 V DC is applied across the plastisol, it ignites. Combustion ceases upon removal of the applied voltage. The products of PVA + HAN combustion are known to include the molecular gases carbon monoxide, carbon dioxide, water, nitrogen, and hydrogen. When the electric field within the plastisol is spatially uniform, combustion occurs preferentially at the anode. The fact that HAN is an ionic conductor suggests that the mechanism of combustion is electrolytic in origin. Consistent with the preference for combustion at the anode and the known gaseous products, we consider two reaction mechanisms. One involves atomic oxygen as the oxidizing agent at the anode and hydroxyl radical as the oxidizing agent at the cathode. The other involves ozone as the oxidizing agent at the anode and hydrogen peroxide as the oxidizing agent at the cathode. Each mechanism is applied to a scenario where the products are rich in the carbon oxides and to a second scenario where the products are poor in the carbon oxides. In the rich case, the heat of the overall reaction is −808.33 kJ per mole of HAN consumed and the electrical energy is converted to thermal energy with an efficiency of 4.2%. In the poor case, the corresponding figures are −567 kJ per mole of HAN and efficiency is 2.9%. The combustion reactions at the electrodes are uniformly exothermic with the exception of the reaction involving hydrogen peroxide at the cathode. When the products are poor in the carbon oxides, this reaction is actually endothermic.

Decomposition of Energetic Ionic Liquid Over IrCu/Honeycomb Catalysts

The objective of this study is to elucidate the influence of a loading procedure of iridium and copper oxides over cordierite honeycomb support on catalytic performance during the decomposition of a hydroxylammonium nitrate (HAN) solution. Iridium and copper composite oxides were successfully supported on the cordierite honeycomb at the same time by repeating the wash coating process more than 2 times. Through the wash coating process, Cu and Ir were supported up to 43.4% and 4.9%, respectively. The cordierite honeycomb without active metal plays little role as a catalyst to lower the decomposition temperature. It was found that IrCu/honeycomb-2 catalyst, which was prepared by repeating the wash coating procedure twice, is an optimal catalyst for the decomposition of HAN solution. The IrCu/honeycomb-2 catalyst had the effect of lowering the decomposition onset temperature by 27.1°C compared to thermal decomposition.