A theory has been developed which predicts the minimum permeability that can be expected for a polymer filled with platelike particles. Models are also developed for the permeability of liquids through filled polymers when the liquid adsorbs or collects at the filler-polymer interface. Some of the cases discussed include different types of dispersions, orientation of filler particles, and the effects of filler aggregation. Permeability, especially of liquids, is extremely complex, and many different types of behavior can be expected.

Models for the Permeability of Filled Polymer Systems

Dispersing highly selective rigid “inserts” such as zeolites and carbons into polymers can produce novel membrane materials with improved gas mixture permselectivity. Rigid inserts frequently cause the permeability in an “interphase” surrounding individual inserts to differ markedly from the intrinsic permeability of the matrix polymer. While existing theoretical models describe permselectivity reasonably well, they fail to predict the absolute permeabilities for individual components in such hybrid media. In fact, the degree of deviation from the simple model predictions provides insight into the detailed properties of the interphase, which has been neglected in previous analyses of these hybrid materials. Extension of an existing model provides a framework to analyze gas permeation properties of model systems with rigid molecular sieve inserts in glassy matrices. Inhibited segmental motion due to surface attachment and matrix contraction at the interface during preparation of these materials is hypothesized as the key cause of the observed behavior. © 2004 American Institute of Chemical Engineers AIChE J, 50: 311–321, 2004

Hybrid membrane materials comprising organic polymers with rigid dispersed phases

Reinforcement mechanisms of fiber-glass reinforced plastics (FRP) under wet conditions are reviewed with emphasis on molecular structures of glass/matrix interfaces. Included are studies on glass surface, the glass/coupling agent interface, silane coupling agents on glass surfaces as well as in solution, the coupling agent/matrix interface, extending to the interphase of particulate-filled composites, and matrix resin. For a better understanding of wet strength of FRP, the structures under dry conditions are extensively, reviewed. The chemical bonding theory still dominates other reinforcement theories. The importance of other factors such as orientation of silane coupling agents and the restriction of matrix polymer conformations are also considered. Based on recent development in spectroscopy, molecular level research of the glass/matrix interfaces has been initiated in the past decade, yet only a few spectroscopic investigations on the function of water have appeared. It is concluded that the correlation between spectroscopic investigations and mechanical properties of a FRP is indispensable.

The reinforcement mechanism of fiber‐glass reinforced plastics under wet conditions: A review

Fourier transform infrared spectroscopic study of the silane coupling agent/porous silica interface

The concept of the diffusion coefficient, D, and Fick’s Laws are considered. Measurements of D and of solubility, s, of gases in polymers are outlined. The factors influencing D and s of gases in polymers are discussed. Methods for obtaining D and s of organic vapours in elastomeric polymers are given. The effects of concentration, temperature, diffusant size and polymer properties on D are correlated using free volume ideas. Equilibrium vapour uptake is discussed. Vapour sorption anomalies in glassy polymers and the reasons for these are outlined. D, s, and permeability, P, of water in both hydrophobic and hydrophilic polymers are considered and interpreted in terms of hydrogen bonding to polymer sites and water clustering by hydrogen bonding. D, s, and P in non-uniform polymers are considered and discussed in terms of the effects of fillers, crystallites and layer structures.

Transport Principles—Solution, Diffusion and Permeation in Polymer Membranes

The effect of pigments on the vapor sorption characteristics of a noncrosslinked polymer [poly(vinylacetate)] and a highly crosslinked polymer (epoxy type) were investigated. The fillers used in this study were a polar surface (titanium dioxide) and a nonpolar surface (copper phthalocyanine blue). With both polar and nonpolar fillers, a marked decrease in the sorption of organic vapors was noted at low relative pressures, even with very low filler content. At high vapor pressures, the sorption isotherm of the filled polymer approaches that of the unfilled polymer. It was also noted that the shape of the sorption isotherm of the filled polymer closely resembles that of the pure polymer below its glass transition temperature. The experimental results are discussed in terms of the partial immobilization of the polymer segments in the presence of fillers, as a result of the reduced number of possible configurations of the polymer chains.

Polymer–filler interaction: Vapor sorption studies

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Polymer–filler interaction: Vapor sorption studies