Glass transition and crystallization of low-temperature amorphous condensates of the water-propane mixture

Abstract

Interest in gas hydrates stems from the existence of vast reserves of hydrocarbons on the earth in the form of gas hydrates, prospects for using them as a fuel source, and the possibility of storage and transporta� tion of gas in the gas hydrate state. The known meth� ods of production of gas hydrates are based on rela� tively small deviations from the equilibrium condi� tions of gas dissolution. They require the use of high pressures in laboratory or manufacturing equipment. For example, the pressure corresponding to the for� mation conditions of methane hydrate at temperatures near 0°С amounts to tens of bars. In addition, forma� tion of the crystal hydrate requires dispersion of water, which is afforded by longterm and vigorous stirring of the water-gas mixture. In this work, we have proposed another approach implying that hydrates are formed under conditions far from thermodynamic equilibrium. The approach is based on lowtemperature molecularbeam deposi� tion in a vacuum onto a surface cooled by liquid nitro� gen. During this process, amorphous (glassy) layers of the water-gas mixture are initially formed, which are stabilized by high viscosity. Heating of the amorphous layers is accompanied by avalanchetype nucleation and growth of gas hydrate crystallization sites. This method requires neither high pressures nor stirring of the water-gas system. Its advantage is that it is univer� sal and can be used for producing various gas hydrates. This work deals with studying the glass transition and crystallization of amorphous condensates of the binary water-propane system obtained by lowtem� perature condensation to determine the conditions of crystal hydrate formation. Amorphous solid (glassy) layers of lowmolecular� weight substances can be obtained by molecularbeam deposition onto a cooled surface. At low temperatures, the amorphous state of these substances is stabilized by the high viscosity. Molecularbeam deposition onto a copper substrate cooled by liquid nitrogen affords amorphous layers of water and simple molecular com� pounds (1), as well as of aqueous solutions of organic liquids (2). Cooling rates under these conditions are as high as 10 5 -10 7 K/s. On heating, the condensates undergo glass transition (softening) and subsequent spontaneous crystallization. In the course of the latter, a decisive role for phase transformation is played by homogeneous nucleation. The crystallization of amorphous water-gas condensates can result in the formation of gas hydrates (3-5). Hydrate formation is facilitated by the low chemical affinity of the hydrate� forming substance, as well as by the size and shape of its molecules corresponding to the geometry of cavi� ties in the arising clathrate framework. Among such substances, there are light hydrocarbons of the meth� ane series. Experiments with lowtemperature con� densates of the water-methane mixture showed the possibility of producing massive samples of crystal hydrates with high gas content capable of sustained burning (5).