Metals molten salt properties

Many reviews of the properties of metal-molten salts have been published, of which can be mentioned Bredig [67], Cubicciotti [68], Ukshe and Bukun [69], Corbett [70], Warren [71,72], Haarberg and Thonstad [73],... 

Bredig [67] considered two categories of metal-molten salt mixtures metallic and nonmetallic solutions. In metallic solutions the metal dissolves without interacting strongly with the melt. Metal ions and partially free electrons are formed. The electrical conductivity of these mixtures increases strongly due to the presence of very mobile partially free electrons. Therefore an electronic conductivity appears in these melts. In nonmetallic solutions the metal reacts with the melt under the formation of subvalent ions or subvalent compounds. The electrical conductivity of these mixtures depends only to a small extent on the concentration of dissolved metal. The variation of properties of the metal-molten salt mixtures shows a continuous change from the metallic solutions to the nonmetallic if the temperature is sufficiently high. 

Absolute rate theory has been applied successfully to all types of problems. Current developments are concerned with explicit calculations of the transmission coefficient k. Liquid theory, although newer, is also widely applicable and has already had many successes in calculating the properties of ordinary liquids, molten metals, molten salts, and water. 

The pyrometallurgical methods were developed based on the differences between zirconium and hafnium in oxidation and reduction characteristics [11, 12] volatility [13-16] electrochemical properties [17-19] and molten metal-molten salt equilibrium [20, 21], The extractive distillation process, using carbochlori-nation of zircon [13], is in operation by CEZUS in France. Both chlorides are sublimated and run through a vertical distillation column containing molten aluminium chloride and potassium chloride. Both hafnium and zirconium tetrachloride chlorides dissolve, but hafnium tetrachloride has a higher vapour pressure and is therefore condensed from the top of the column in a hafnium-enriched mixture. The zirconium tetrachloride is partitioned to a liquid phase and recovered from a salt, typically containing less than 50 ppm hafnium. 

Young RE, O Connell JP (1971) Empirical corresponding states correlatitm of densities and transport properties of 1-1 alkali metal molten salts. Ind Eng Chem Fund 10 418-423... 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

As in die case of die diffusion properties, die viscous properties of die molten salts and slags, which play an important role in die movement of bulk phases, are also very stiiicture-seiisitive, and will be refeiTed to in specific examples. For example, die viscosity of liquid silicates are in die range 1-100 poise. The viscosities of molten metals are very similar from one metal to anodier, but die numerical value is usually in die range 1-10 centipoise. This range should be compared widi die familiar case of water at room temperature, which has a viscosity of one centipoise. An empirical relationship which has been proposed for die temperature dependence of die viscosity of liquids as an AiTlienius expression is... 

Good electrical conductance is one of the characteristics of many though not all molten salts. This characteristic has often been employed industrially. Various models have been proposed for the mechanism of electrical conductance. Electrolytic conductivity is related to the structure, although structure and thermodynamic properties are not the main subjects of this chapter. Electrolytic conductivities of various metal chlorides at the melting points are given in Table 4 together with some other related properties. "... 

Relatively little attention has been devoted to the direct electrodeposition of transition metal-aluminum alloys in spite of the fact that isothermal electrodeposition leads to coatings with very uniform composition and structure and that the deposition current gives a direct measure of the deposition rate. Unfortunately, neither aluminum nor its alloys can be electrodeposited from aqueous solutions because hydrogen is evolved before aluminum is plated. Thus, it is necessary to employ nonaqueous solvents (both molecular and ionic) for this purpose. Among the solvents that have been used successfully to electrodeposit aluminum and its transition metal alloys are the chloroaluminate molten salts, which consist of inorganic or organic chloride salts combined with anhydrous aluminum chloride. An introduction to the chemical, electrochemical, and physical properties of the most commonly used chloroaluminate melts is given below. 

The compatibility of each light metal cation with any low-melting molten salt electrolyte must be examined experimentally. It can be anticipated that at least some such combinations will have useable properties. 

Prospects for TR Electrolyte SBs. In view of the harmful effects often cited in the literature of even small traces of water on the operation of non-aqueous batteries with alkali metal anodes, it might be supposed that electrolytes of the TR composition cannot be applied in such batteries. This same idea may dominate when molten salt SBs are considered. Such a general conclusion cannot be justified. A dilute solution of water in a salt has the structure either of this salt proper or its adjacent hydrate, and the energy, properties and reactions of this water are quite different from those of pure water or of dilute solutions of various compounds in it. On the other hand, a small amount of water in the electrolyte system will decrease its melting point and increase its conductivity. Mixtures of water with such liquids as some alcohols or dioxane and other aprotic and even proton-forming substances, may open new prospects for... 

A novel application of ionic liquids in biochemistry involved duplex DNA as the anion and polyether-decorated transition metal complexes. When the undiluted liquid DNA-or molten salt-is interrogated electrochemically by a microelectrode, the molten salts exhibit cyclic voltammograms due to the physical diffusion (D-PHYS) of the polyether-transition metal complex. These DNA molten salts constitute a new class of materials whose properties can be controlled by nucleic acid sequence and that can be interrogated in undiluted form on microelectrode arrays (Leone et al., 2001). 

At one time solutions of metals in their molten salts were thought to be colloidal in nature, but this has been shown not to be true. However, no completely satisfactory theory has been advanced to account for oil the properties of these solutions. One hypothesis involves reduction of the cation of the molten salt to a lower oxidation state. For example, the solution of mercury in mercuric chloride undoubtedly involves reduction ... 

Metallic State. The actinide metals, like the lanthanide metals, are highly electropositive. They can be prepared by the electrolysis of molten salts or by the reduction of a halide with an electropositive metal, such as calcium or barium. Their physical properties are summarized in Table 3. 

The excellent insulating and dielectric properties of BN combined with the high thermal conductivity make this material suitable for a huge variety of applications in the electronic industry [142]. BN is used as substrate for semiconductor parts, as windows in microwave apparatus, as insulator layers for MISFET semiconductors, for optical and magneto-optical recording media, and for optical disc memories. BN is often used as a boron dopant source for semiconductors. Electrochemical applications include the use as a carrier material for catalysts in fuel cells, electrodes in molten salt fuel cells, seals in batteries, and BN coated membranes in electrolysis cells for manufacture of rare earth metals [143-145]. 

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