Nitrogen tetroxide became the storable liquid propellant of choice from the late 1950's. Nitrogen tetroxide consists principally of the tetroxide in equilibrium with a small amount of nitrogen dioxide (NO2). The purified grade contains less than 0.1 per cent water. Nitrogen tetroxide (N2O4) has a characteristic reddish-brown colour in both liquid and gaseous phases. The solid tetroxide is colorless. N2O4 has an irritating, unpleasant acid-like odour. N2O4 is a very reactive, toxic oxidiser. It is non-flammable with air; however, it will inflame combustible materials. It is not sensitive to mechanical shock, heat, or detonation. Nitrogen dioxide is made by the catalytic oxidation of ammonia; steam is used as a diluent to reduce the combustion temperature. Most of the water is condensed out, and the gases are further cooled; the nitric oxide is oxidised to nitrogen dioxide, and the remainder of the water is removed as nitric acid. The gas is essentially pure nitrogen tetroxide, which is condensed in a brine-cooled liquefier. 1959 production amounted to 60,000 tonnes per year. In carload lots of one-ton cylinders, the price was $ 0.15 per kg. By 1990 NASA was paying $ 6.00 per kg due to environmental regulations.
Hydyne was a propellant blend pushed rather vigorously by the Redstone arsenal in the late 1950's, but it found little application. Hydyne, which is also known as MAF-4, is a 60 per cent, by weight, mixture of UDMH and 40 weight percent diethyltrianine (DETA). The normally occurring impurities are dimethylamine, beta-aminoethyl-N-piperazine, and water. Hydyne is a clear, colourless liquid which may become discoloured on exposure to air during storage. Both UDMH and DETA have an ammoniacal odour; the odour is not so sharp or fishy as that of UDMH. Hydyne is a hygroscopic liquid which will absorb carbon dioxide and oxygen from air. It is completely miscible with water and ethanol; the solubility of gasoline and JP-4 in Hydyne are somewhat limited. It forms flammable explosive mixtures with air. Amines generally yellow during storage due to oxidation followed by polymerisation induced by air (O2)· reaction is believed to form an intermediate amine oxide which undergoes polymerisation. The cost of Hydyne in 1959 was $ 0.80 per kg.