High-temperature phase

The fractionation of these refractory elements is beheved to be the result of relative efficiencies of incorporation of condensed sohds rich in early high temperature phases into the meteorite parent bodies at different times and locations in the solar nebula. The data are taken from Reference 3. 

When the host is a single oxide, incorporation is best achieved during a high temperature phase transition of the host lattice such as when Ti02 goes from anatase to mtile, or during formation from carbonates or other salts. 

Reactions Between Refractories. In Table 17, the compatibilities of various refractories are given over a range of temperatures. Dissimilar refractories can react vigorously with each other at high temperatures. Phase diagrams are an excellent source of information concerning the reactivity between refractories. 

The use of a and P to denote the forms of quartz has not always been uniform in the Hterature, particularly in older references. Although some authors have used P to denote the low form, usage as of the 1990s has the stable low temperature phase as a and the high temperature phase as p. 

Linear N2 molecules adsorbed on graphite show a transition from a high-temperature phase with orientational disorder to a low-temperature phase with herringbone ordering of the orientational degrees of freedom (see Sec. lie and Fig. 11). 

The small effects and the progressive evolutions observed seem to be in agreement with a second order phase transition. The lack of coexistence of the low- and high-temperature phases in the temperature range close to the transition temperature and the apparent lack of thermal hysteresis confirm this conclusion. 

A conformationally disordered mesomorphic form is present, for instance, in the high-temperature phase I of PTFE. In this form, a long-range 3-D order is present only in the periodic pseudohexagonal placement of the chain axes [49]. In fact intramolecular helix reversals would produce the conformational disorder [50-52] and a complete intermolecular rotational disorder would be also present [49, 52,53]. 

The nonmesogenic compound CB2 is described here, because it shows a reversible distortive solid-solid phase transition at 290.8 K (transition enthalpy 0.9 kj/mol) from the centrosymmetric low temperature phase I to the noncentrosymmetric high temperature phase II. The crystal structures of both solid phases I and II are very similar [45] as demonstrated in Fig. 2. The molecules are arranged in layers. The distances between the cyano groups of adjacent molecules are 3.50 A Ncyano-Ncyano and 3.35 A Ncyano-C ano for phase I and 3.55 A Ncyano-Ncyano and 3.43 A Ncyano-Ccyano for phase II. In the two... 

Still, the question has to be addressed as to which of the many modifications of Prl2 is thermodynamically stable under standard conditions. So far, it is clear that Prl2-IV must be a high-temperature phase as it is produced in pure and single-phase by annealing just below the peritectic temperature (with an excess of praseodymium metal in order to avoid the formation of Pr2ls) and rapid cooling to ambient temperature. 

Following the high-temperature syntheses used for these compounds according to the reaction (4), a phase transition into the low-temperature modification may occur on slow cooling. The high-temperature phase, on the other hand, may be frozen out at room temperature through fast quenching (Fig. 8.5). 

The low-temperature (/1-)AE3(BN2)2 phases exhibit two distinct structures for AE = Ca and Sr that can be derived from the cation disordering in their respective high-temperature phases. For / -Ca3(BN2)2 an orthorhombic (Cmca) superstructure of the cubic cell with fi-a bo a, Cq ly l a was obtained, in which the former 8f sites are occupied by seven calcium ions in an ordered fashion. In contrast, the structure of / -Sr3(BN2)2 is simply the result of a transition from a cubic body-centered (Im3m) into a primitive structure (Pm3m), in which the former 2 a position (0, 0, 0 1/2, 1/2, 1/2) is split into two independent positions, of which only one is occupied by strontium (Fig. 8.6). 

Fig. 8.4 Crystal structures of a-Ca3(BN2)2 (a) and a-Sr3(BN2)2 (b) high-temperature phases. Striped atoms indicate partial occupations on special positions 8f (occupied by 7/8) and 2a (occupied by 1 /2).

An alloy is said to be of Type II if neither the AC nor the BC component has the structure a as its stable crystal form at the temperature range T]. Instead, another phase (P) is stable at T, whereas the a-phase does exist in the phase diagram of the constituents at some different temperature range. It then appears that the alloy environment stabilizes the high-temperature phase of the constituent binary systems. Type II alloys exhibit a a P phase transition at some critical composition Xc, which generally depends on the preparation conditions and temperature. Correspondingly, the alloy properties (e.g., lattice constant, band gaps) often show a derivative discontinuity at Xc. 

However at elevated temperatures (T2 > Tj, Figure 9) the increased entropy (TAS) associated with an open shell structure overcomes the ti —ti enthalpy of dimerisation associated with these distorted Ti-stacked structures and they undergo a solid-solid phase transition (Figure 9) The high temperature phase is typically associated with a Ti-stack of regularly spaced radicals which exhibit longer inter-radical S- S contacts (ca. 3.7 A). This process was first observed by Oakley60 in the DTA radical thiadiazolopyrazine-l,3,2-dithiazolyl 26, and a number of other derivatives have subsequently been identified which exhibit similar behaviour. These are compiled in Table 1. 

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