Correlated Diffusivities, Solubilities, and Hydrophobic Interactions in Ternary Polydimethylsiloxane–Water–Tetrahydrofuran Mixtures

Abstract

Bulk thermodynamic and kinetic properties of mixtures are generally composition dependent, often in complicated ways, especially for partially miscible and multicomponent systems. Combined 1H chemical shift, 1H diffusion NMR, and surface forces analyses establish the compositional dependences of water solubility and self-diffusion in ternary polymeric polydimethylsiloxane–water–tetrahydrofuran (THF) mixtures. The addition of THF significantly increases the solubility of water, while decreasing its diffusivity, in hydrophobic polydimethylsiloxane. Minimum values for the self-diffusivities of both water and THF coincide with a minimum in the hydrophobic adhesion energy between silicone polymer thin films near the same binary composition of 0.20 mole fraction THF. Such interrelated diffusivities, solubilities, and hydrophobic interactions are analyzed with respect to hydrogen bonding among the constituent species to account for the bulk physical properties of technologically important mixtures of silicone polymers with water and/or cosolvents.