High pressure polymorph

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. 

Diamonds also occur in meteorites, probably as a result of high pressures produced dynamically by impact (10,11). The shock or explosive mode of synthesis is a viable process for fine diamond powders of both the cubic and hexagonal (lonsdaleite) polymorphs (12) naturally or otherwise. Some diamonds in space appear to have formed by processes more closely related to the low pressure chemical vapor deposition processes described later (see... 

Australia, is the doyen of materials scientists who study the elastic and plastic properties of minerals under hydrostatic pressure and also phase stability under large shear stresses (Paterson 1973). J.-P. Poirier, in Paris, a professor of geophysics, was trained as a metallurgist one of his special skills is the use of analogue materials to help understand the behaviour of inaccessible high-pressure polymorphs, e.g., CaTi03 perovskite to stand in for (Mg, FelSiOi in the earth s mantle (Poirier 1988, Besson el al. 1996). 

Many of the high-pressure forms of ice are also based on silica structures (Table 14.9) and in ice II, VIII and IX the protons are ordered, the last 2 being low-temperature forms of ice VII and III respectively in which the protons are disordered. Note also that the high-pressure polymorphs VI and VII can exist at temperatures as high as 80°C and that, as expected, the high-pressure forms have substantially greater densities than that for ice I. A vitreous form of ice can be obtained by condensing water vapour at temperatures of — 160°C or below. 

Pressure-induced phase transitions in the titanium dioxide system provide an understanding of crystal structure and mineral stability in planets interior and thus are of major geophysical interest. Moderate pressures transform either of the three stable polymorphs into the a-Pb02 (columbite)-type structure, while further pressure increase creates the monoclinic baddeleyite-type structure. Recent high-pressure studies indicate that columbite can be formed only within a limited range of pressures/temperatures, although it is a metastable phase that can be preserved unchanged for years after pressure release Combined Raman spectroscopy and X-ray diffraction studies 6-8,10 ave established that rutile transforms to columbite structure at 10 GPa, while anatase and brookite transform to columbite at approximately 4-5 GPa. 

High pressure polymorphs are naturally characterized by wider bands with a smaller gap between the upper and lower VBs. The upper VB width in columbite, baddeleyite and fluorite structures is 5.37 eV, 6.22 eV and 7.44 eV, respectively, while the lower VB width is 2.32 eV, 3.30 eV and A.60 eV, respectively. This trend is due to the increasing overlap between the 2s-states of oxygen under compression. 

Ice I is one of at least nine polymorphic forms of ice. Ices II to VII are crystalline modifications of various types, formed at high pressures ice VIII is a low-temperature modification of ice VII. Many of these polymorphs exist metastably at liquid nitrogen temperature and atmospheric pressure, and hence it has been possible to study their structures without undue difficulty. In addition to these crystalline polymorphs, so-called vitreous ice has been found within the low-temperature field of ice I. It is not a polymorph, however, since it is a glass, i.e. a highly supercooled liquid. It is formed when water vapour condenses on surfaces cooled to below — 160°C. 

Although the structure of CsCl is quite different from that of NaCl, even CsCl can be transformed into the sodium chloride structure when heated to temperatures above 445 °C. Some of the other alkali halides that do not have the sodium chloride structure under ambient conditions are converted to that structure when subjected to high pressure. Many solid materials exhibit this type of polymorphism, which depends on the external conditions. Conversion of a material from one structure to another is known as a phase transition. 

ArV is not necessarily positive, and to compare the relative stability of the different modifications of a ternary compound like AGSiOs the volume of formation of the ternary oxide from the binary constituent oxides is considered for convenience. The pressure dependence of the Gibbs energies of formation from the binary constituent oxides of kyanite, sillimanite and andalusite polymorphs of A SiOs are shown in Figure 1.10. Whereas sillimanite and andalusite have positive volumes of formation and are destabilized by pressure relative to the binary oxides, kyanite has a negative volume of formation and becomes the stable high-pressure phase. The thermodynamic data used in the calculations are given in Table 1.7 [3].1... 

Pressure-induced amorphization of solids has received considerable attention recently in physical and material sciences, although the first reports of the phenomenon appeared in 1963 in the geophysical literature (actually amorphization on reducing the pressure [18]). During isothermal or near isothermal compression, some solids, instead of undergoing an equilibrium transition to a more stable high-pressure polymorph, become amorphous. This is known as pressure-induced amorphization. In some systems the transition is sharp and mimics a first-order phase transition, and a discontinuous drop in the volume of the substance is observed. Occasionally it is strictly not an amorphous phase that is formed, but rather a highly disordered denser nano-crystalline solid. Here we are concerned with the situation where a true amorphous solid is formed. 

Their normal crystal structure, at ambient conditions, corresponds to the body-centred cubic cI2-W-type structure. At very low temperatures, the close-packed hexagonal hP2-Mg-type structure has been observed for Li and Na, while for Rb and Cs the face-centred cubic close-packed cF4-Cu-type structure is known at high pressure. No polymorphic transformation has been reported for potassium. 

The 5th group metals a summary of their atomic and physical properties Vanadium, niobium and tantalum have only the bcc, W-type, structure no high-temperature or high-pressure polymorphs are known. 

These non-existent allotropes, which are impurity-stabilized phases, are fee Sc, fee Y-Ce, the bcc Ho, Er, Tm and Lu and fee phases of Nd, Sm, Gd and Dy, some of which have been described as formed at room temperature during mechanical milling. A number of fee high-pressure polymorphs, for instance, are actually compounds, with a structure related to the NaCl-type, formed by reaction with O, N and/or H during mechanical milling (see also Alonso et al. 1992). 

Only with silica was the nature of the surface groups studied as extensively as with carbon. Silica, like carbon, has several polymorphs. Apart from the amorphous state, it is known to exist in numerous crystalline modifications. The most important forms are quartz, tridymite, and cristobalite. Each of these can occur in a low-temperature form and in a high-temperature form of somewhat higher symmetry. Tridymite is only stable if small amounts of alkali ions are present in the lattice 159). Ar. Weiss and Al. Weiss 160) discovered an unstable fibrous modification with the SiSj structure. Recently, a few high-pressure modifications have been synthesized keatite 161), coesite 162), and stishovite 16S). The high-pressure forms have been found in nature in impact craters of meteorites, e.g., in the Arizona crater or in the Ries near Nbrdlingen (Bavaria). 

Table 2.1 shows the crystal structure data of the phases existing in the Mg-H system. Pnre Mg has a hexagonal crystal structure and its hydride has a tetragonal lattice nnit cell (rutile type). The low-pressure MgH is commonly designated as P-MgH in order to differentiate it from its high-pressure polymorph, which will be discussed later. Figure 2.2 shows the crystal structure of p-MgH where the positions of Mg and H atoms are clearly discerned. Precise measurements of the lattice parameters of p-MgH by synchrotron X-ray diffraction yielded a = 0.45180(6) mn and c = 0.30211(4) nm [2]. The powder diffraction file JCPDS 12-0697 lists a = 0.4517 nm and c = 0.30205 nm. The density of MgH is 1.45 g/cm [3]. 

Walther J. V. and Helgeson H. C. (1977). Calculation of the thermodynamic properties of aqueous silica and the solubility of quartz and its polymorphs at high pressures and temperatures. Amer. Jour. Set, 277 1315-1351. 

Crystalline Silica Three principal polymorphic forms exist at atmospheric pressure. These are quartz, tridymite, and cristobalite. Quartz is stable below 870°C. It transforms to tridymite form at about 870°C. Tridymite is stable up to 1,470°C and transforms to cristobahte at 1,470°C. High cristobalite melts around 1,723°C. Other than these three polymorphs, there are also three high pressure phases of crystalline sihca keatite, coesite, and stishovite. 

Three high pressure crystalline sdica have been made in polymorph phas-... 

One might also point out that while the compound K2S itself has the antifluorite structure (Cl) under normal conditions, Cl often transforms to C23 under pressure, which may be expected to be the (not very) high-pressure form of K2S. Thus (a situation we shall return to) P-K2SO4 may be regarded as an anion-stuffed, high-pressure K2S polymorph. 

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