Silicon molten

Silicon (3), which resembles metals in its chemical behavior, generally has a valence of +4. In a few compounds it exhibits a +2 valence, and in silicides it exists as a negative ion and largely violates the normal valency rules. Silicon, carbon, germanium, tin, and lead comprise the Group 14 (IVA) elements. Silicon and carbon form the carbide, SiC (see Carbides). Silicon and germanium are isomorphous and thus mutually soluble in all proportions. Neither tin nor lead reacts with silicon. Molten silicon is immiscible in both molten tin and molten lead. 

Many of the applications of group IV element NMR are relatively straightforward from a spectroscopic point of view and are therefore not discussed here. Worthy of special note, however, are Si studies of aqueous silicates and silicones, molten silicates, and silyl transition metal derivatives the use of Si/ H 2D correlation spectra to make assignments and the substantial and growing body of body of Si MAS and/or CP work on solid materials such as zeolites, other silicate minerals, polysilanes, and surface-immobilized materials. The potential of solid-state NMR for Sn and Pb has yet to be fully realised, although solid trimethyl stannyl hydroxide and tributyl stannyl fluoride have been studied. 

Elastomeric shield materials (ESM) have been developed as low density flexible ablators for low shear appHcations (49). General Electric s RTV 560 is a foamed silicone elastomer loaded with silicon dioxide [7631-86-9] and iron oxide [1317-61 -9] particles, which decomposes to a similar foam of Si02, SiC, and EeSiO. Silicone resins are relatively resistant to thermal decomposition and the silicon dioxide forms a viscous Hquid when molten (50) (see... 

Molten silicon is not a semiconductor, and has no commercial use, although because of the high heat of fusion, it has been considered as a heat storage medium. The Hquid (molten) siUcon properties summarized in Table 6 are nevertheless of importance because these affect single-crystal growth, an operation through which essentially all semiconductor-grade siUcon must pass. 

Vanadium—Silicon. Vanadium—shicon ahoy is made by the reduction of vanadium oxides with shicon in an electric furnace. Apphcation is essentiahy the same as that of the titanium ahoys. Vanadium ahoys sometimes offer the most economical way of introducing vanadium into molten steel. 

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. 

The bath is normally at a temperature in the range 620-710°C, depending on whether the coating material is an aluminium-silicon alloy (for use in high-temperature conditions) or pure aluminium (for corrosion prevention). It is heated by inductors, by resistance heaters or by an external flame. The pot will usually be refractory lined unless cast-iron pots are needed to ensure adequate heat transfer from an external flame. As molten aluminium is extremely aggressive towards ferrous metals, replacement of cast-iron pots is fairly frequent. Refractory-lined pots obviously do not have this drawback, although the bath hardware, in particular the sinker roll and support mechanism, will still be attacked and need replacement at intervals. 

Heating with the following solids, their fusions, or vapours (a) oxides, peroxides, hydroxides, nitrates, nitrites, sulphides, cyanides, hexacyano-ferrate(III), and hexacyanoferrate(II) of the alkali and alkaline-earth metals (except oxides and hydroxides of calcium and strontium) (b) molten lead, silver, copper, zinc, bismuth, tin, or gold, or mixtures which form these metals upon reduction (c) phosphorus, arsenic, antimony, or silicon, or mixtures which form these elements upon reduction, particularly phosphates, arsenates,... 

Attention has been given for some time to the use of lithium alloys as an alternative to elemental lithium. Groups working on batteries with molten salt electrolytes that operate at temperatures of 400-450 °C, well above the melting point of lithium, were especially interested in this possibility. Two major directions evolved. One involved the use of lithium-aluminium alloys [5, 6], whereas another was concerned with lithium-silicon alloys [7-9]. 

The lithium-silicon system has also been of interest for use in the negative electrodes of elevated-temperature molten salt electrolyte lithium batteries. A composition containing 44 wt.% Li, where Li/Si=3.18, has been used in commercial... 

To a 50-mL three-necked flask (Fig. 3.18b) equipped with a stirrer (comprised of a stainless steel shaft and paddle), a head for the distillation of water, and a nitrogen inlet is added 20 g of purified 11-aminoundecanoic acid. The flask is then purged with nitrogen for 5 min. The flask is warmed in a silicon oil bath to 220° C and maintained at this temperature for 10 h. After raising the stirrer from the molten mass, the reaction is cooled under nitrogen and the resultant polymer removed by breaking the glass. The Tm of the polymer is 185—190° C and the rjmh in m-cresol (0.5% at 35°C) is 0.6—0.7. 

Metallic magnesium is produced by either chemical or electrolytic reduction of its compounds. In chemical reduction, first magnesium oxide is obtained from the decomposition of dolomite. Then ferrosilicon, an alloy of iron and silicon, is used to reduce the MgO at about 1200°C. At this temperature, the magnesium produced is immediately vaporized and carried away. The electrolytic method uses seawater as its principal raw material magnesium hydroxide is precipitated by adding slaked lime (Ca(OH)2, see Section 14.10), the precipitate is filtered off and treated with hydrochloric acid to produce magnesium chloride, and the dried molten salt is electrolyzed. 

The carbides are generally not resistant to molten slags and fused salts. Their resistance to molten metal is usually poor. For instance, TiC is attacked by nickel, cobalt, chromium, and silicon. SiC is attacked by aluminum. 

Other useful refractory nitrides for corrosion protection are silicon nitride (Si3N4) and boron nitride (BN). Silicon nitride has good corrosion resistance and is not attacked by most molten metals as shown in Table 17.6 (see Ch. 10). 

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