Silica and Silicon

The element silicon, with its usual partner, oxygen, plays the same role on this planet relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO,) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO, tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature's cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide SiO, (analogous to its congener carbon in CO and CO,); a tetrachloride SiCl, (analogous to CC1,); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117°- 200°C but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures-such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao, et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert, et al., 1973; Pecora, 1960).