Glasses dissolution, phase-separated

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

Solubility and speciation. Minimum requirements for reliable thermodynamic solubility studies include (i) solution equilibrium conditions (ii) effective and complete phase separation (iii) well-defined solid phases and (iv) knowledge of the speciation/oxidation state of the soluble species at equilibrium. Ideally, radionuclide solubilities should be measured in both oversaturation experiments, in which radionuclides are added to a solution untU a solid precipitates, and undersaturation experiments, in which a radionuchde solid is dissolved in aqueous media. Due to the difference in solubilities of crystalline versus amorphous solids and different kinetics of dissolution, precipitation, and recrystalhzation, the results of these two types of experiments rarely agree. In some experiments, the maximum concentrahon of the radionuchde source term in specific water is of interest, so the sohd that is used may be SF or nuclear waste glass rather than a pure radionuclide solid phase. 

The process of solution mediated transformation can be considered the result of two separate events, (a) dissolution of the initial phase, and (b) nucleation/growth of the final, stable phase. If crystals do not grow as expected from a saturated solution, the interior of the vessel can be scratched with a glass rod to induce crystallization by distributing nuclei throughout the solution. Alternatively, crystallization may be promoted by adding nuclei, such as seed crystals of the same material. For example, Suzuki showed that the a-form of inosine could be obtained by crystallization from water, whereas isolation of the 3-form required that seeds of the 3-form be used [13]. 

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