Swelling domain morphology

Partial Molar Elastic Free Energy of Swelling. Leonard (8) calculated the partial molar elastic free energy of swelling for an interdomain tie molecule in a spherical domain morphology. He included the entropy... 

By way of comparison, the morphology of the sequential synthesis shows a much finer structure, the average domains being of the order of 300-600. Also, because of swelling restrictions, it was impossible to achieve materials having more than about 80% polystyrene (15). 

With increasing water content, the ionic domains swell from 40 to 50 A in diameter and the structure of fhe membrane is fhoughf to consist of spherical ionic domains joined by cylinders of wafer dispersed in fhe polymer matrix. Within this region of wafer confenf, proton conductivify steadily increases. At > 0.5, a morphological inversion occurs in which a connected network of aggregated polymer "rods" is now surrounded by water. This network continues to swell for X, = 0.5 —> 0.9 and fhe conductivify of fhe membrane approaches the values observed for Nafion solutions. 

Swelling. If water (or any polar solvent) can penetrate the bulk of the polymer, it should be preferentially located in the ionic domains, thereby, creating domains with a high dielectric constant. It could, therefore, produce a morphology of the ionic aggregates different from that of the anhydrous material. 

Further consequences of the yield stress [i.e., the plug flow] are (i) a drastic reduction of the extrudate swell, B = d/d (d is diameter of the extrudate, d that of the die) [see, e.g., Crowson and FoUces, 1980 Utracki et al, 1984], and (ii) significant increase of the entrance-exit pressure drop, Pg (also known as Bagley correction). For single-phase fluids, these parameters have been related to elasticity by molecular mechanisms [Tanner, 1970 Cogswell, 1972 Laun and Schuch, 1989]. However, in multiphase systems, both B and P depend primarily on the inter-domain interactions and morphology, not on deformation of the macromolecular coils. Thus, in multiphase systems [i.e., blends, filled systems, or composites], only direct measures of elasticity, such as that of Nj, or G should be used. It is customary to plot the measure of the elastic component versus that of the shear components, viz., vs. 

Effective conductivity of the membrane is related to its macroscopic morphology, viz. the random heterogeneous domain structure of polymer and solvent phases. On the basis of Gierke s cluster network model, a random network model of microporous PEMs was developed in [22]. This approach highlighted the importance of connectivity and swelling properties of pores. Random distributions of pores and channels as their interconnections were assumed. The connectivity between pores was considered as a phenomenological parameter. 

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