High-temperature dissolution

Fig. 7.9. Measurements of the degree of conversion of ct p silicon nitride at a fixed time and various temperatures are thought to show the strong influence of shock modification on the high temperature dissolution [84B01].

The effect of pressure on high-temperature dissolution has been investigated. The solubility of NiO in Na20-2Si02 glass was found to decrease with applied pressure, indicating that the entry rate of atoms from a solute into a solvent is decreased by increased pressure. The saturation concentration as measured with the electron beam microprobe is an accurate measurement of the liquidus concentration for a given temperature. 

The Courtaulds semicommercial production system is iUustrated in Figure 8. Dissolving-grade woodpulp is mixed into a paste with NMMO and passes through a high temperature dissolving unit to yield a clear viscous solution. This is filtered and spun into dilute NMMO whereupon the ceUulose fibers precipitate. These are washed and dried, and finally baled as staple or tow products as required by the market. The spin bath and wash Uquors are passed to solvent recovery systems which concentrate the NMMO to the level required for reuse in dissolution. 

The molecular weight and its distribution have been determined by laser light scattering, employing a new apparatus for ETFE dissolution and solution clarification at high temperature diisobutyl adipate is the solvent at 240°C. The molecular weight of molten ETEE is determined by high temperature rheometry (21). 

Commercial condensed phosphoric acids are mixtures of linear polyphosphoric acids made by the thermal process either direcdy or as a by-product of heat recovery. Wet-process acid may also be concentrated to - 70% P2O5 by evaporation. Liaear phosphoric acids are strongly hygroscopic and undergo viscosity changes and hydrolysis to less complex forms when exposed to moist air. Upon dissolution ia excess water, hydrolytic degradation to phosphoric acid occurs the hydrolysis rate is highly temperature-dependent. At 25°C, the half-life for the formation of phosphoric acid from the condensed forms is several days, whereas at 100°C the half-life is a matter of minutes. 

Solvent. The solvent properties of water and steam are a consequence of the dielectric constant. At 25°C, the dielectric constant of water is 78.4, which enables ready dissolution of salts. As the temperature increases, the dielectric constant decreases. At the critical point, the dielectric constant is only 2, which is similar to the dielectric constants of many organic compounds at 25°C. The solubiUty of many salts declines at high temperatures. As a consequence, steam is a poor solvent for salts. However, at the critical point and above, water is a good solvent for organic molecules. 

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 most common form of corrosion is uniform corrosion, in which the entire metal surface degrades at a near uniform rate (1 3). Often the surface is covered by the corrosion products. The msting of iron (qv) in a humid atmosphere or the tarnishing of copper (qv) or silver alloys in sulfur-containing environments are examples (see also SiLVERAND SILVER ALLOYS). High temperature, or dry, oxidation, is also usually uniform in character. Uniform corrosion, the most visible form of corrosion, is the least insidious because the weight lost by metal dissolution can be monitored and predicted. 

Fig. 7.8. High temperature conversion of a-silicon nitride with an MgO additive to the p-pha.se is thought to be a consequence of dissolution of the a phase in a magnesium silicate with subsequent recrystallization from the melt. Enhanced dissolution rate should then strongly influence a. p conversion [84B01].

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