Melting intermediates

FIOURE 16.42 E hase diagram for the binary system La203-Nb205, containing four congruently melting intermediate compounds [114]. 

The concentration dependence of viscosity of the system KF-K2NbF7 shows positive deviations from the ideal behavior, most probably due to formation of the congruently melting intermediate compound KsNbFg. This compound is, however, not stable and dissociates partially according to the reaction... 

By a similar procedure, the mathematical model obtained for the decomposition temperature of incongruently melted intermediate compounds between rare earth and nontransition metals obtained by SVR computation can be expressed as follows ... 

In just the proportion to give a sharp-melting eutectic mixture is so remote that this possibility may be neglected. [Occasionally arbitrary mixtures of two substances which (usually) are chemically related may melt fairly sharply at temperatures intermediate between the melting-points of the two components, but this phenomenon is rarely encountered.]... 

The term distillation is applied to vaporisation and subsequent condensation according to (i) it should also be applied to (ii) since it is really the liquid which is converted into vapour and is first formed by condensation. Strictly speaking, the term sublimation should be applied to changes according to (iii). However, in practice, a substance when heated may first melt and then boil, but on cooling it may pass directly from the vapour to the solid the process is then also called sublimation. Indeed the mode of vaporisation, whether directly from solid to vapour or through the intermediate formation of a liquid, is of secondary importance it is the direct conversion of vapour to solid which is really the outstanding feature of sublimation in the laboratory. 

Hexafluoropropylene—tetrafluoroethylene copolymers are available in low melt viscosity, extmsion grade, intermediate viscosity, high melt viscosity, and as dispersions. The low melt viscosity (MV) resin can be injection molded by conventional thermoplastic molding techniques. It is more suitable for injection molding than other FEP resins (51). 

Properties. As prepared, the polymer is not soluble in any known solvents below 200°C and has limited solubiUty in selected aromatics, halogenated aromatics, and heterocycHc Hquids above this temperature. The properties of Ryton staple fibers are in the range of most textile fibers and not in the range of the high tenacity or high modulus fibers such as the aramids. The density of the fiber is 1.37 g/cm which is about the same as polyester. However, its melting temperature of 285°C is intermediate between most common melt spun fibers (230—260°C) and Vectran thermotropic fiber (330°C). PPS fibers have a 7 of 83°C and a crystallinity of about 60%. 

Isomerization. Maleic acid is isomerized to fumaric acid by thermal treatment and a variety of catalytic species. Isomerization occurs above the 130 to 140°C melting point range for maleic acid but below 230°C, at which point fumaric acid is dehydrated to maleic anhydride. Derivatives of maleic acid can also be isomerized. Kinetic data are available for both the uncatalyzed (73) and thiourea catalyzed (74) isomerizations of the cis to trans diacids. These data suggest that neither carbonium ion nor succinate intermediates are involved in the isomerization. Rather, conjugate addition imparts sufficient single bond character to afford rotation about the central C—C bond of the diacid (75). 

The Cams Hquid-phase oxidation process is similar in principle however, it is operated continuously, its oxidation reaction vessels are of a much larger scale, and the separation of the manganate intermediate from the caustic melt is accompHshed without dilution by means of filtration (qv) (121—123). 

Since successful commercialization of Kapton by Du Pont Company in the 1960s (10), numerous compositions of polyimide and various new methods of syntheses have been described in the Hterature (1—5). A successful result for each method depends on the nature of the chemical components involved in the system, including monomers, intermediates, solvents, and the polyimide products, as well as on physical conditions during the synthesis. Properties such as monomer reactivity and solubiHty, and the glass-transition temperature,T, crystallinity, T, and melt viscosity of the polyimide products ultimately determine the effectiveness of each process. Accordingly, proper selection of synthetic method is often critical for preparation of polyimides of a given chemical composition. 

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