Void dissolution

Whether or not stable nuclei and mechanically trapped voids grow or redissolve depends on several factors. Growth may occur via diffusion of air or water vapor or by agglomeration with neighboring voids. Dissolution may occur if the changes in temperature and pressure cause an increase in solubility in the resin, as we shall see. 

Although the void behavior is calculated through Stage 5, it is likely that the viscosity rises sufficiently high in Stage 4 so that the model assumptions are no longer valid. The void dissolution calculated in Stages 4 and 5 will therefore probably not occur in reality. 

The following brief account is concerned with factors that affect the acces-sibihty of the OH groups of cellulose, since this is the determining factor for its dissolution, hence subsequent derivatization. Electron microscopy. X-ray scattering and porosimetry of cellulose fibers have clearly shown the presence of non-uniform pores, capillaries, voids and interstices in the fiber surface [25]. Consequently, the total surface area of cellulose fibers exceeds by far the geometrical outer surface. Pore structure determines the internal... 

The surface area of a solid material is important in that it provides information on the available void spaces on the surfaces of a powdered solid [48]. In addition, the dissolution rate of a solid is partially determined by its surface area. The most reproducible measurements of the surface area of a solid are obtained by adsorbing a monolayer of inert gas onto the solid surface at reduced temperature and subsequently desorbing this gas at room temperature. The sorption isotherms obtained in this technique are interpreted using the equations developed by Brunauer, Emmett, and Teller, and therefore the technique is referred to as the B.E.T. method [49]. The surface area is obtained in units of square meters of surface per gram of material. 

In the pharmaceutical industry, surface area is becoming more important in the characterization of materials during development, formulation, and manufacturing. The surface area of a solid material provides information about the void spaces on the surfaces of individual particles or aggregates of particles [5], This becomes important because factors such as chemical activity, adsorption, dissolution, and bioavailability of the drug may depend on the surface on the solid [3,5]. Handling properties of materials, such as flowability of a powder, can also be related to particle size and surface area [4],... 

Apparently, the formation of the microporous structure within the PVdF—HFP copolymer was of critical importance to the success of Bellcore technology, and the ion conductivity was proportional to the uptake of the liquid electrolyte. To achieve the desired porosity of PVdF film, Bellcore researchers prepared the initial polymer blend of PVdF with a plasticizer dibutylphthalate (DBP), which was then extracted by low boiling solvents after film formation. Thus, a pore-memory would be left by the voids that were previously occupied by DBP. However, due to the incomplete dissolution of such high-melting DBP during the extraction process, the pore-memory could never be restored at 100% efficiency. Beside the total volume of pores thus created by the plasticizer. 

The mechanism of action by which silane and siloxanes reduce expansion has been attributed to water repellence and air entrainment. Phosphate addition or coatings may interfere with the dissolution of silica gel and the formation of gel. It is also possible that phosphate reduces the osmotic potential and the swelling pressure in the gel. The manner in which air entrainment reduced expansion was attributed to the accommodation of alkali-silica gel in the air void system. For example, it was found that air-entrained concrete with 4% air voids could reduce AAR expansion by 40% [23]. 

The model framework for describing the void problem is schematically shown in Figure 6.3. It is, of course, a part of the complete description of the entire processing sequence and, as such, depends on the same material properties and process parameters. It is therefore intimately tied to both kinetics and viscosity models, of which there are many [3]. It is convenient to consider three phases of the void model void formation and stability at equilibrium, void growth or dissolution via diffusion, and void transport. 

Figure 6.5 Equilibrium void stability map for a typical epoxy resin system. Curves indicate stable void equilibrium states for liquid-resin pressures indicated. Growth takes place above the lines and dissolution occurs below the lines for any given resin pressure...

Figure 6.6 shows the effect of the processing cycle on the void diameter for pure water and air-water voids of 0.1 cm initial diameter under the specified cycle conditions. It was assumed that the air—water void initially consists of pure air, even though there is likely to be a small but finite water partial pressure. This plot can be divided into the various stages of void growth and dissolution and interpreted as follows. 

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