http://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/93443/1/j.polymer.2007.11.031.pdf

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

This paper summarizes current literature on the migration of monomeric and polymeric PVC plasticizers from medical materials, food packaging, and toys. Especially highlighted is macromolecular engineering as a tool to increase the plasticizing efficiency and migration resistance for polymeric plasticizers. The effect of branching, molecular weight, end-group functionality, and polydispersity on plasticizer performance was evaluated by quantification of low-molecular-weight hydrolysis products, measurements of mechanical properties, weight loss, surface segregation, as well as the preservation of material properties during aging. A more migration-resistant polymeric plasticizer that also better preserved its material properties during aging was obtained by combining a low degree of branching, hydrolysis-protecting end-groups, and higher molecular weight.

Migration of monomeric and polymeric PVC plasticizers

The behaviour of miscible blends of polystyrene (PS)/poly(vinyl methyl ether)(PVME) of varying compositions has been investigated at temperatures where PS and PVME are miscible. The PVME is seen to enrich the polymer–air surface, forming a layer with a width that is comparable to the correlation length. Further heating close to the demixing temperature results in the formation of a capillary instabilities at the polymer surface exhibiting a spinodal-like pattern with a characteristic wavelength that depends on the blend composition. Formation of these instabilities is seen for all blend compositions. We propose that these wetting induced instabilities result from coupled height and composition fluctuations in the PVME enriched surface layer, driving the build-up of long wavelength fluctuations.

Wetting induced instabilities in miscible polymer blends

Surface aggregation states in miscible blends of monodisperse polystyrene (PS) and poly(vinyl methyl ether) (PVME) were studied by X-ray photoelectron spectroscopy (XPS) in conjunction with neutron reflectivity (NR). In the case of symmetric blends in terms of degree of polymerization, N, PVME and PS were preferentially segregated at the film surface and the interface with a silicon wafer, respectively, to minimize free energy of the system. The concentration profile near the surface obtained by experiments was consistent with a mean-field prediction. Also, the surface composition in symmetric blends composed of PS terminated by fluoroalkyl groups at both ends (α,ω-PS(Rf)2) and PVME was examined. In this case, the surface enrichment of PVME was suppressed by virtue of the surface localization of fluoroalkyl end groups, and the composition was strongly dependent on N. The surface in asymmetric α,ω-PS(Rf)2/PVME blend, in which N of α,ω-PS(Rf)2 was much smaller than that of PVME, was mostly covered with the ...

Surface Composition Control via Chain End Segregation in Blend Films of Polystyrene and Poly(vinyl methyl ether)

The effect of the interplay between bulk and surface free energy terms on surface segregation in miscible blends is probed by comparing angle-dependent x-ray photoelectron spectroscopy (ADXPS) measurements for polystyrene/polyvinylmethylether (PS/PVME) blends of with those for perdeuteropolystyrene/polyvinylmethylether (dPS/PVME) blends. The magnitudes of the bulk interaction parameters for the two systems differ markedly while the surface interactions are essentially identical. Experimental concentration depth profiles are almost identical for the two systems indicating that their surface properties are little affected by bulk interactions and dominated by surface energy effects. These data and previous data from our group are compared to the predictions of the square gradient theory developed by Schmidt and Binder in order to gain a more quantitative understanding of the factors that control surface segregation in miscible blends. While there is general qualitative agreement between theory and experiment, predicted surface compositions fall significantly below experimental values and predicted composition depth profiles decay more gradually than what is observed experimentally, especially for low PVME contents. The use of the more appropriate Sanchez-Lacombe-Balazs equation of state does not yield any significant improvement over the use of the Flory-Huggins lattice model for representing the bulk free energy terms. Careful analysis of the experimental behavior suggests that configurational effects associated with the flattening of surface adsorbed chains and differences in mer-mer interaction parameters in the bulk and near surface regions are possible origins for the discrepancies between theory and experiment.

Surface Segregation in Miscible Blends of Polystyrene and Poly(vinylmethyl ether): Comparison of Theory and Experiment

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Surface Segregation in Miscible Blends of Polystyrene and Poly(vinylmethyl ether): Comparison of Theory and Experiment