Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch
The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter.
Conversion of batch to molten glass, II: Dissolution of quartz particles
Quartz dissolution during the batch-to-glass conversion influences the melt viscosity and ultimately the temperature at which the glass forms. Batches to make a high-alumina borosilicate glass (formulated for the vitrification of nuclear waste) were heated as 5°C min-1 and quenched from the temperatures of 400-1200°C at 100°C intervals. As a silica source, the batches contained quartz with particles ranging from 5 to 195 µm. The content of unreacted quartz in the samples was determined with x-ray diffraction. Most of fine quartz has dissolved during the early batch reactions (at temperatures <800°C), whereas coarser quartz dissolved mostly in a continuous glass phase via diffusion. The mass-transfer coefficients were assessed from the data as functions of the initial particle sizes and the temperature. A series of batch was also tested that contained nitrated components and additions of sucrose known to accelerate melting. While sucrose addition had no discernible impact on quartz dissolution, nitrate batches melted somewhat more slowly than batches containing carbonates and hydroxides in addition to nitrates.
Hygroscopic Expansion of some Casting Investments
CREDIT is generally given to Taggart1 for introducing the cast gold inlay to the dental profession. Although he realized that gold shrinks when cooled from molten state to solid state of room temperature, the investment available to him did not supply sufficient compensation. In 1910, Van Horn2 published a paper dealing with a method by which he obtained the compensation by means of wax expansion. The next major research in connection with this problem was the work of Coleman3 at the National Bureau of Standards. He determined the gold shrinkage to be 1.25 per cent and presented a casting technic with compensation values of quantitative nature. The total compensation for the gold shrinkage was obtained by the combination of the setting and thermal expansion of the mold. This procedure is the general practice followed at the present time for compensation. There are some disadvantages to this method. Skinner has indicated the difficulty of obtaining smooth castings and the improper compensation for the casting shrinkage.4 It has been found by Hollenback5 and Scheu6a that castings made at a high temperature are rougher than those made at a low temperature (450° C.), depending upon the great difference in thermal expansion between plaster of Paris and silica, which causes a poor union of the fine particles. This may also result in friability and there may be some warpage due to the differential expansion. A method which provides sufficient compensation at a low mold temperature is the hygroscopic casting technic.b Wilson7 showed that certain plasters expand as much as 0.0044 inch to the inch by taking up moisture from the air. With this information at hand, Scheula, b tested some commercial investment to determine what results the addition of moisture would have. He found6b: (1) All of the casting investments that were tested expanded. (2) The thicker the mix, the greater the expansion. (3) A mix with hot water expanded more than one with cold water. (4) The time at which the mix is placed in the water is of great importance. It was found that if the mix is placed in the water early, it would not expand so much as when placed in a little later. It was also found that if the mix was placed in the water after a certain time, it could not expand to the maximal amount. (5) The temperature of the water in which the mix is placed is important, for two reasons; (a) the temperature of the water controls slightly the expansion of the investment, and (b) water at a temperature of 1000 F. slightly softens the wax pattern so that the fine margins are not marred while expansion is taking place. The mix should remain in the water at least 20 minutes to obtain the full expansion, after which time no further expansion is obtained.