Velocity correlation analysis in polymer-solvent mixtures

The subject of this article is the combined interpretation of intradiffusion and mutual-diffusion data for polymer-solvent mixtures in terms of integrals over velocity self-correlation functions and velocity cross-correlation functions. The combination of mutual-diffusion, intradiffusion, and activity data allows the evaluation of velocity-correlation coefficients (VCCs) and distinct-diffusion coefficients in systems containing one monodisperse solute. This study is the first attempt to extend these approaches to polymers that are polydisperse solutes. Because of the polydispersity, this correlation analysis may become critical for polymers. Its application to polydisperse samples requires the reduction of intradiffusion and mutual-diffusion coefficients to the same average. After such a reduction, the VCCs and distinct-diffusion coefficients are evaluated for a homologous series of poly(ethylene glycol)s (PEGs). Attractive PEG-PEG interactions depend on the chain length and concentration of PEG. In this analysis, network formation in PEG-water systems appears to be a smooth process.