화학공학소재연구정보센터
Journal of Supercritical Fluids, Vol.13, No.1, 357-362, 1998
Silica transfer and beta-quartz growth from supercritical aqueous fluids
Methods used to grow beta-quartz crystals include, gas and hydrothermal high-pressure vessels (10-12 ml internal volume) and autoclaves (20, 75 and 100 ml internal volume). The crystals were grown on bar-like alpha-quartz seeds at temperatures up to 900 degrees C and pressures from 20 to 500 MPa, under isothermal and thermal gradient conditions. Pure water and aqueous solutions of NaOH, K2CO3, NaCl, NH4F, AlF3, HF, Li3PO4 were used as solvents. The nutrient was similar quartz bars or amorphous silica. Impurity elements (Fe, Al, P, Ti, Ge etc.) were added to the nutrient in the form of oxides. The details of silica transfer during the crystal growth process, under supercritical conditions, have been analyzed. It was demonstrated for the first time that in pure water and nearly neutral or alkaline fluids, the direction of silica transfer always coincides with the direct temperature gradient. However, in acidic fluoride fluids and pressures below 80-100 MPa, the direction of silica transfer undergoes inversion and is opposite to the direct temperature gradient. This phenomenon is related to the nonmonotonous and relatively strong temperature and density dependence of the HF dissociation constant which affects quartz solubility. The intensity and direction of silica transfer is substantially dependent on temperature, temperature gradient, density and alkalinity of the solutions, as well as being dependent on the fluoride ion concentrations in acidic solutions. It was shown that only faces {1010} and {1011}, as well as higher indexed pyramidal {h0hl} faces are stable under experimental conditions. The growth rates of faces {1010} and {1011} are about the same (similar to 0.02 mm day(-1)). Impurity elements, except for Ge, are scarce (similar to 0.001%) in the quartz structure. The results obtained provide an explanation for the growth peculiarities of beta-quartz crystals in natural environments.