Exploring the Application of Advanced Chromatographic Methods to Characterize the Surface Physicochemical Properties and Transition Phenomena of Polystyrene--poly(4-vinylpyridine).

The linear diblock copolymer polystyrene--poly(4-vinylpyridine) (PS-P4VP) is an important copolymer recently used in many applications such as optoelectronics, sensors, catalysis, membranes, energy conversion, energy storage devices, photolithography, and biomedical applications. (1) Background: The surface thermodynamic properties of PS-P4VP copolymers are of great importance in many chemical and industrial processes. (2) Methods: The inverse gas chromatography (IGC) at infinite dilution was used for the experimental determination of the retention volumes of organic solvents adsorbed on copolymer surfaces as a function of temperature. This led to the variations in the free energy of interaction necessary to the evaluation of the London dispersive and polar acid-base surface energies, the polar enthalpy and entropy, the Lewis acid-base constants, and the transition temperatures of the PS-P4VP copolymer. (3) Results: The application of the thermal Hamieh model led to an accurate determination of the London dispersive surface energy of the copolymer that showed non-linear variations versus the temperature, highlighting the presence of two transition temperatures. It was observed that the Lewis acid-base parameters of the copolymer strongly depend on the temperature, and the Lewis base constant of the solid surface was shown to be higher than its acid constant. (4) Conclusions: An important effect of the temperature on the surface thermodynamic properties of PS-P4VP was proven and new surface correlations were determined.