Thermodynamics of ethylene-vinyl acetate copolymer blends

The purpose of this study was to characterise the miscibility of several poly(ethylene-co-vinyl acetate), EVA, based polymer blends. EVA has many industrial applications and is often present as one of several polymeric components. Consequently, there is considerable interest in the thermodynamics of these blend systems. The thermodynamics of these blends was studied using several techniques: differential scanning calorimetry; phase contrast optical microscopy; small angle neutron scattering and wide angle X-ray scattering. Characterisation was also to include assessing the relative enthalpic and entropic thermodynamic contributions to the Rory-Huggins interaction parameter (%) of these blends. To determine the enthalpic interaction parameter, a "mixing calorimeter" was designed and constructed to measure accurately the "heat of mixing" values on blending these polymers. Free energy interaction parameters were determined from melting point depression and small angle neutron scattering measurements. In all the blends studied, the heat of mixing was endothermic and consequently, the enthalpic interaction parameters were positive i.e. unfavourable to miscibility. Miscibility in these blends can therefore only be achieved by a dominant entropic contribution, favourable to miscibility. Using phase contrast optical microscopy, both miscible and immiscible phase behaviour was observed in this series of blends. This shows good agreement with predictions of miscibility from heat of mixing, melting point and small angle neutron scattering measurements, based on the classical Flory-Huggins lattice theory. Wide angle X-ray scattering and differential scanning calorimetry results have associated miscible blends with crystallisation effects between the blend components. Small angle neutron scattering has been used to determine the concentration and temperature dependence of interaction parameters in a miscible blend. From these values the upper critical solution temperature (UCST) of the blend was predicted. The enthalpic contributions to these interaction parameters show good agreement with experimental values determined from heat of mixing measurements. It was concluded that the classical Flory-Huggins lattice theory (despite its many well documented Limitations) appears to be particularly suited to the thermodynamic characterisation of miscibility in these polymer blends.