Dissolution mechanism of glassy

Experimental studies involved measurement of the various moving fronts in the polymer-solvent system. In addition, mathematical models were developed to understand the dissolution mechanism of both rubbery as well as glassy polymers and the model predictions were compared to the experimental results. 

The reptation idea could account for the effect of polymer molecular weight and solvent concentration on the dissolution rate. However the key concentration identified in this approach [57,59] is one at the surface. This implies independence of the solvent concentration history. This may not be true as the disentanglement of polymer chains does not commence till the local solvent concentration is greater than a critical value at which the local glass transition temperature is lowered below the experimental temperature so that the glassy polymer changes into a gel. Also, all of the efforts discussed so far failed to take into account the effect of the viscoelastic properties of the polymer on the dissolution mechanism. 

An in depth study of the deposition mechanism was carried out by Sun et al. who studied the 1 1 [EMIMJCl/ZnCf system at various temperatures on glassy carbon (GC), nickel and platinum electrodes [106], The GC electrode required the largest overpotential for deposition. The stripping process showed a single peak on GC, whereas on Ni two oxidation processes were observed, separated by ca. 0.6V. Itwas proposed that the more positive oxidation process corresponded to the dissolution of an intermetallic compound formed during electrodeposition. 

Several different mechanisms are operant in the deterioration of brick masonry through the action of acid rain. The bricks are susceptible to acid rain through the selective dissolution of their glassy phase. The mortar is affected mainly by the reaction of its calcareous components. The soluble salts resulting from these reactions, in solution with rain water or condensed moisture, will migrate through the porous matrix of the masonry. In the places where the water evaporates the salts will be deposited. 

This mechanism is similar to the one occurring during liquid-phase sintering, where the dissolution of crystalline material into the glassy phase occurs at the interfaces loaded in compression and their reprecipitation on interfaces loaded in tension. The rate-limiting step in this case can be either the dissolution kinetics or transport through the boundary phase, whichever is slower. This topic was discussed in some detail in Chap. 10, and will not be repeated here. 

Figure 7.7 Schematic illustration of a) dissolution-precipitation and b) liquid redistribution mechanisms in a material containing a grain boundary glassy phase.

FIGURE 17.17 Illustration of the dissolution-precipitation mechanism that could be operative in ceramics containing a glassy phase at the GB. 

---