Tridymite,

Thenardite, see Sodium sulfate Thionyl, see Sulflnyl Thorianite, see Thorium dioxide Topaz, see Aluminum hexafluorosilicate Tridymite, see Silicon dioxide Troilite, see Iron(II) sulflde... 

Except for siUca and natural abrasives containing free siUca, the abrasive materials used today are classified by NIOSH as nuisance dust materials and have relatively high permissable dust levels (55). The OSHA TWA allowable total dust level for aluminum oxide, siUcon carbide, boron carbide, ceria, and other nuisance dusts is 10 mg/m. SiUca, in contrast, is quite toxic as a respkable dust for cristobaUte [14464-46-1] and tridymite [15468-32-3] the allowable TWA level drops to 0.05 mg/m and the TWA for quartz [14808-60-7] is set at 0.1 mg/m. Any abrasive that contains free siUca in excess of 1% should be treated as a potential health hazard if it is in the form of respkable dust. Dust masks are requked for those exposed to such materials (see Industrial hygene). 

Results obtained at high temperatures indicate that the solubihties of the crystalline modifications of sihca are in the order tridymite > cristobahte > quartz, an order that parallels to some extent the chemical reactivity of these forms. Lower values for solubihty of crystalline as compared to amorphous sihca are consistent with the free-energy differences between them. 

Crystalline Silica. Sihca exists in a variety of polymorphic crystalline forms (23,41—43), in amorphous modifications, and as a Hquid. The Hterature on crystalline modifications is to some degree controversial. According to the conventional view of the polymorphism of siHca, there are three main forms at atmospheric pressure quart2, stable below about 870°C tridymite, stable from about 870—1470°C and cristobaHte, stable from about 1470°C to the melting point at about 1723°C. In all of these forms, the stmctures are based on SiO tetrahedra linked in such a way that every oxygen atom is shared between two siHcon atoms. The stmctures, however, are quite different in detail. In addition, there are other forms of siHca that are not stable at atmospheric pressure, including that of stishovite, in which the coordination number of siHcon is six rather than four. 

The transformations are aided by or may requke the presence of impurities or added mineralizers such as alkaH metal oxides. Indeed, it has been suggested that tridymite cannot be formed at all in the absence of impurities, and some texts assert that pure Si02 occurs in only two forms quartz and cristobaHte... 

Another representation of the stabiUty relations of the siUca minerals is shown in Figure 4. This diagram, developed in the classical studies early in the twentieth century (51), illustrates the relationship of vapor pressure to temperature. It is assumed that vapor pressure increases with temperature and that the form having the lowest vapor pressure is the most stable. The actual values of the vapor pressures are largely unknown. Therefore, the ordinate must be considered only as an indication of relative stabiUties. This diagram does not show all the various forms of tridymite that have been identified. 

In addition to the three principal polymorphs of siUca, three high pressure phases have been prepared keatite [17679-64-0] coesite, and stishovite. The pressure—temperature diagram in Figure 5 shows the approximate stabiUty relationships of coesite, quart2, tridymite, and cristobaUte. A number of other phases, eg, siUca O, siUca X, sihcaUte, and a cubic form derived from the mineral melanophlogite, have been identified (9), along with a stmcturaHy unique fibrous form, siUca W. 

Tridymite. Tridymite is reported to be the siUca form stable from 870—1470°C at atmospheric pressure (44). Owing to the sluggishness of the reconstmctive tridymite—quart2 conversion, which requites minerali2ers such as sodium tungstate, alkah metal oxide, or the action of water under pressure, tridymite may persist as a metastable phase below 870°C. It occurs in volcanic rocks and stony meteorites. 

The stmcture of tridymite is more open than that of quart2 and is similar to that of cristobaUte. The high temperature form, probably S-IV, has a hexagonal unit cell containing four Si02 units, where ttg = 503 pm and Cg = 822 pm > 200° C, space group Pb./mmc. The Si—O distance is 152 pm. 

The existence of tridymite as a distinct phase of pure crystalline siUca has been questioned (42,58—63). According to this view, the only tme crystalline phases of pure siUca at atmospheric pressure are quart2 and a highly ordered three-layer cristobaUte having a transition temperature variously estimated from 806 250°C to about 1050°C (50,60). Tridymites are considered to be defect stmctures in which two-layer sequences predominate. The stabihty of tridymite as found in natural samples and in fired siUca bricks has been attributed to the presence of foreign ions. This view is, however, disputed by those who cite evidence of the formation of tridymite from very pure siUcon and water and of the conversion of tridymite M, but not tridymite S, to cristobahte below 1470°C (47). It has been suggested that the phase relations of siUca are deterrnined by the purity of the system (42), and that tridymite is not a tme form of pure siUca but rather a soHd solution of minerali2er and siUca (63). However, the assumption of the existence of tridymite phases is well estabUshed in the technical Hterature pertinent to practical work. 

Fig. 1. Phase equilibria ia the C—A—S (CaO—AI2O2—Si02) system (3,4) temperatures are ia °C. Shaded areas denote two Hquids compositional index marks on the triangle are indicated at 10% intervals B denotes cristobaUte [14464-46-17, and D denotes tridymite [15468-32-3] both of Si02 composition E is anorthite [1302-54-17, Al2CaSi20g G is muUite [55964-99-3]-, H, gehlenite [1302-56-3], Ca2Al2Si02 and J is the area of Pordand cement compositions.

Respiratory fibrogens Fibrogenic dusts e.g. Free crystalline silica, (quartz, tridymite, cristobalite), asbestos (chrysotile, amosite, crocidolite etc.), talc. 

Silica, Crystalline (Respirable) Cristobalite Quartz Tridymite Tripoli... 

The a-form of each of the three minerals can thus be obtained at room temperature and, because of the sluggishness of the reconstructive interconversions of the -forms, it is even possible to melt -quartz (1550 ) and -tridymite (1703 ) if they arc heated sufficiently rapidly. The bp of Si02 is not accurately known but is about 2800 C. 

When water freezes the crystalline form adopted depends upon the detailed conditions employed. At least nine structurally distinct forms of ice are known and the phase relations between them are summarized in Fig. 14.9. Thus, when liquid or gaseous water crystallizes at atmospheric pressure normal hexagonal ice If, forms, but at very low temperatures (—120° to — 140°) the vapour condenses to the cubic form, ice Ic. The relation between these structures is the same as that between the tridymite and cristobalite forms of SiOa (p. 342), though in both forms of ice the protons are disordered. 

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