Molten solid phase

The major differences between polymer and liquid electrolytes result from the physical stiffness of the PE. PEs are either hard-to-soft solids, or a combination of solid and molten in phases equilibrium. As a result, wetting and contact problems are to be expected at the Li/PE interface. In addition, the replacement of the native oxide layer covering the lithium, under the... 

When HgCl2, Hg and AICI3 are taken in the mole ratios 1 2 2 and heated above the mp at 240°C for 6 d the melt becomes yellow. Yellow needles of Hg3(AlCl4)2 can be obtained from this mixture by establishing a thermal gradient between the molten phase (at 210°C) and solid phase (at 195°C) ... 

In most unit operations it is of considerable importance that material is transferred from one phase to another across a boundary. The transfer of material from a solid phase to a liquid phase (as typically in leaching), or the transfer of material between one liquid phase to another liquid phase (as typically in molten metal and molten slag phases), extraction or between liquid and vapor phases (as typically in distillation) are well-known examples encountered in practice. 

Fig. 2. Phase diagram for the AlCl -EtMeImCl molten salt ( ) liquid-solid phase transitions and (O) glass transitions. Adapted from Fannin et al. [33] by permission of the American Chemical Society, Inc.

Alloys are classified broadly in two categories, single-phase alloys and multiple-phase alloys. A phase is characterized by having a homogeneous composition on a macroscopic scale, a uniform structure, and a distinct interface with any other phase present. The coexistence of ice, liquid water, and water vapor meets the criteria of composition and structure, but distinct boundaries exist between the states, so there are three phases present. When liquid metals are combined, there is usually some limit to the solubility of one metal in another. An exception to this is the liquid mixture of copper and nickel, which forms a solution of any composition between pure copper and pure nickel. The molten metals are completely miscible. When the mixture is cooled, a solid results that has a random distribution of both types of atoms in an fee structure. This single solid phase thus constitutes a solid solution of the two metals, so it meets the criteria for a single-phase alloy. 

Supercooling has been observed in an extreme form in molten ibuprofen if the molten solid is allowed to cool from the melting point to room temperature without vibration in a smooth-lined container [48]. For instance, undisturbed rac-ibuprofen can exist as an oil phase for several hours to a few days. If disturbed, however, an exothermic recrystallization proceeds and bulk crystalline material rapidly grows vertically out of the oil phase so energetically that the system emits an audible cracking sound. 

An interesting difference between the samples is found in the behaviour of the samples during destabilisation. While for the sample under a deuterium pressure, LiBD4 is not destabilised until both phases are molten, in the vacuum sample LiD is destabilised in the solid phase, and at much lower temperatures (ca. 360°C). This is primarily due to the improved diffusion kinetics of Li species over that of LiBD4. There is also the possibility that LiD precipitation out of the liquid phase at nucleation sites on the Mg particles allows improved mixing over the solid Mg and liquid LiBD4 observed in the sealed sample. 

Figure 7.2 G-X and T-X plots for a binary system with a molten phase with complete miscibility of components at all T conditions and a solid phase in which components are totally immiscible at all proportions (mechanical mixture, 7 = 7 + V )-...

Subject areas for the Series include solutions of electrolytes, liquid mixtures, chemical equilibria in solution, acid-base equilibria, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, equilibria in analytical chemistry, dissolution of gases in liquids, dissolution and precipitation, solubility in cryogenic solvents, molten salt systems, solubility measurement techniques, solid solutions, reactions within the solid phase, ion transport reactions away from the interface (i.e. in homogeneous, bulk systems), liquid crystalline systems, solutions of macrocyclic compounds (including macrocyclic electrolytes), polymer systems, molecular dynamic simulations, structural chemistry of liquids and solutions, predictive techniques for properties of solutions, complex and multi-component solutions applications, of solution chemistry to materials and metallurgy (oxide solutions, alloys, mattes etc.), medical aspects of solubility, and environmental issues involving solution phenomena and homogeneous component phenomena. 

Heat is conducted from the outer surface through the melt to the free interface, where some of the heat is absorbed as heat of fusion, melting some more solid, and the rest is conducted into the solid phase. The densities of melt and solid are usually different. We denote the melt phase with subscript l and the solid with subscript s. The thickness of the molten layer increases because of melting, and there is also a slight increase due to a decrease in density as the solid melts. If there were no decrease in density, the thickness of the molten layer would remain Xs. Thus, the relationship between Xt and Xs is given by... 

Recent advances on the Ca-Br cycle were presented in an ANL paper. The original concept for this cycle involved solid phase reactions in a semi-continuous batch operation. The ANL paper reported on experiments that used a direct sparging reactor in the hydrolysis reaction to allow continuous production of HBr which is then electrolytically decomposed to produce hydrogen. The sparging steam was introduced into the molten bath of CaBr2 which yielded HBr in a stable and continuous operation. 

In this chapter we discuss preparative routes for inorganic materials in three basic types of systems involving the presence of a distinct solid-liquid interface those in which the liquid and solid phases are of the same chemical identity (solidification and vitrification processes), those in which the liquid and solid phases are not of the same chemical identity (crystallization, precipitation), and the special case in which the liquid phase is a pure ionic liquid or molten salt. Ionic liquids can serve as the solvent as well as a templating agent, and the liquid components may or may not become incorporated into the final solid product. We also discuss two areas where the distinct solid-liquid interface becomes somewhat blurred namely, sol-gel and solvothermal processes. 

High modulus polyethylenes have also been produced by the application of pressure to the polymer when it is molten under conditions of extrusion through a narrow capillary. It appears that in one case at least these methods differ in kind from those which involve stretching the molecules either in solution, or in the solid phase. 

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