We report results on the linear viscoelasticity (oscillatory shear in the temperature range Tg (glass-transition temperature) ≤ T ≤ Tg + 90 K) of miscible blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) and segmental relaxations, measured by dielectric spectroscopy. The Flory−Huggins interaction parameter of this blend is weakly negative, and the glass transitions of the pure components are quite disparate (ΔTg = 125 K). PS/PVME blends have been found to be consistently thermorheologically complex at both the segmental and terminal levels:  the empirical time−temperature superposition (tTS) principle applies to neither their oscillatory shear response nor their dielectric response. Using the tube model, we quantitatively compare dielectric and mechanical results. At low temperatures, the effective time scale for motion of a Kuhn segment (the shortest Rouse mode) is near the long-time end of the distribution of segmental relaxation times of PVME, in both the pure and blended states. The slow...

Dynamics in Miscible Blends of Polystyrene and Poly(vinyl methyl ether)

The surface compositions of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends have been investigated using x‐ray photoelectron spectroscopy (XPS). The XPS results demonstrate that there are significant differences between the composition of the surfaces (e.g., outmost ∼6 nm) and the bulk of both miscible and immiscible blends. The surfaces of PS/PVME films dip‐coated from either toluene or trichloroethylene solutions are found to be enriched in PVME. An additional enrichment in the PVME content of the surface is also observed when miscible PS/PVME blends are phase separated by heating them above the lower critical solution temperature. The average composition profile of a miscible 50/50(w) blend has been obtained by angular‐dependent XPS measurements. This experiment suggests that the enrichment is the result of a concentration gradient rather than a monolayer coating. These results are discussed in terms of the surface free energies of PS and PVME and the degree of mixing in the surface layer.

Surfaces of polymer blends: X‐ray photoelectron spectroscopy studies of polystyrene/poly(vinyl methyl ether) blends

The relation between rheology and the time dependent morphology of a phase-separating binary blend of polystyrene and poly(vinyl methyl ether) was investigated by heating a sample from the single-phase (at 90 °C) into the two-phase regime (at 124 °C, 16 K above the LCST) and maintaining its temperature there while measuring the evolution of the dynamic moduli G‘ and G‘‘. Morphological changes occurred slowly so that there was sufficient time to cycle the dynamic mechanical measurements repeatedly over five decades in frequency. The morphology was observed on length scales from 1 mm down to 1 nm by conventional optical microscopy combined with digital image analysis, Hoffman modulation microscopy, TEM, and WISE NMR with spin diffusion. NMR shows that major compositional changes occur mostly in the first 20 min and then the composition remains constant at about 60:40 PS/PVME for the PS-rich matrix and 5:95 PS/PVME for the PVME-rich microdomains. The PVME-rich microdomains are separated by thin layers of the...

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Late Stages of Phase Separation in a Binary Polymer Blend Studied by Rheology, Optical and Electron Microscopy, and Solid State NMR

Polymers which are miscible with each other are so because they are of low molecular weight, because they are similar chemically and physically, or because of specific interactions between the polymers. Not surprisingly a large percentage of those mixtures which are of practical use belong to the last group. This review attempts to present a critical assessment of methods of studying homogeneous blends and some recent work on polymer mixtures with a particular emphasis on those systems which are influenced by specific interactions.

The miscibility of high polymers: The role of specific interactions

Studies of polyester/chlorinated poly(vinyl chloride) blends

Homogeneous films comprised of mixtures of polystyrene and poly(vinyl methyl ether) can be obtained by evaporation from a ternary solution containing toluene as the solvent. Heterogeneous films result when the solvent is trichloroethylene. The possibility that a heterogeneous film cast from trichloroethylene can be transformed to a homogeneous one by physical means is a logical expectation when the polymer-polymer interaction is favorable, though as yet no comprehensive report has appeared in the literature. We have accomplished the transformation by increasing the temperature. Optical microscopy and glass transition experiments were employed to observe the effects.

T. K. Kwei

Papers

Phase transformation in mixtures of polystyrene and poly(vinyl methyl ether)