Binary fluids in mesoporous materials: Phase separation studied by NMR relaxation and diffusion

Relaxation and diffusion measurements were carried out on single and binary liquids filling the pore space of controlled porous glass Vycor with an average pore size of about 4 nm. The dispersion of the longitudinal relaxation time T ₁ is discussed as a means to identify liquid-surface interaction based on existing models developed for metal-free glass surfaces. In addition, the change of T ₁ and T ₂ with respect to their bulk values is discussed, in particular T ₂ serves as a probe for the strength of molecular interactions. As the native glass surface is polar and contains a large amount of hydroxyl groups, a pronounced interaction of polar and protic adsorbate liquids is expected; however, the T ₁ dispersion, and the corresponding reduction of T ₂, are also observed for non-polar liquids such as alkanes and cyclohexane. Deuterated liquids are employed for simplifying data analysis in binary systems, but also for separating the respective contributions of intra- and intermolecular interactions to the overall relaxation rate. Despite the lack of paramagnetic impurities in the glass material, ¹H and ²H relaxation dispersions of equivalent molecules are frequently found to differ from each other, suggesting intermolecular relaxation mechanisms for the ¹H nuclei. The variation of the T ₁ dispersion when comparing single and binary systems gives clear evidence for the preferential adsorption of one of the two liquids, suggesting complete phase separation in several cases. Measurement of the apparent tortuosity by self-diffusion experiments supports the concept of a local variation of sample composition within the porespace.