Phase transitions in porous media studied by NMR

Abstract: This Thesis presents studies of phase transitions ocurring in porous media. The investigated phase transitions include melting/crystallization, surface pre-melting and liquid-liquid phase separation of binary mixtures. A combination of NMR techniques, already existing and newly developed and ranging from cryoporometry to elaborate self-diffusion and spin-relaxation experiments, was applied in order to detect and quantify the effect of finite size constraints on those phase transitions. By relating the results to physico-chemical models, the difference in behaviour with respect to that of bulk was exploited and related to pore morphology and surface properties in diverse porous systems.NMR cryoporometry is based on the detection of the melting/freezing temperature shifts with respect to those in the bulk state to obtain mean pore size and pore size distribution. We extended the size range in which this can be done in porous matrices of both hydrophilic and hydrophobic nature to a 1 μm-600 nm upper limit. This was achieved by introducing two new probe liquids namely octamethylcyclotetrasiloxane (OMCTS) and zinc nitrate hexahydrate Zn(NO)3•H2O.The thickness of the pre-molten surface layer that appears at the interface of frozen octamethylcyclotetrasiloxane (OMCTS) to the matrix in controlled porous glasses was quantified and modeled including its temperature and wall-curvature dependence. The results reveal that the layer thickness depends logarithmically on the deviation from the pore melting point, while for the largest pore investigated this turns into a power law with the exponent of –1/2. Diverse NMR techniques were used not only to detect solely the surface layer and the evolution of the surface melting, but also to distinguish the latter from the volume melting transition within the pores.The morphologies of two nanostructured materials, sintered films of TiO2 nanoparticles and a mesoporous foam obtained by surfactant-templated synthesis, were investigated. These two porous matrices have very different structures but fall into the size range accessible by NMR cryopormetry and their characterization plays an important role in their future applications. They were studied by exploiting the difference between melting and freezing temperature shifts ΔTm and ΔTf, respectively, with respect to that of bulk. NMR cryoporometry was shown to be a suitable alternative and an excellent complement to other porosimetry techniques, namely mercury intrusion and gas sorption porosimetries to analyze the pore structure and pore size distribution because of the unique and model-independent access to information about pore shape. By combining NMR cryoporometry with NMR diffusion experiments holds great potential for accessing information about pore interconnectivity.By diverse NMR techniques we provided experimental evidence that corroborate that liquid-liquid phase separation of a binary mixture imbibed in porous media actually occurs within the individual pores. The size distribution of the phase-separated domains was measured.