Macroporous materials, relaxation

Some information can be obtained on porous media from conventional NMR spectroscopy, and this is discussed in Section 2. Relaxation time measurements have been widely used to characterize porous solids, and this technique is discussed in Section 3. Pulsed field gradient (PFG) methods may be used to probe the local structure of the pore space and to characterize transport within it, and these are discussed in Section 4. Magnetic resonance imaging (MRI) techniques can also be used to characterize the pore space and to measure transport, and applications are discussed in Section 5. The bulk of this review will be concerned with mesoporous and macroporous materials, as it is for these systems that NMR is particularly useful in characterizing the pore space. However, some applications of NMR techniques to probe the pore space and transport within microporous materials will be mentioned in Section 6. Finally, some general conclusions are given in Section 7. 

During the preparation of macroporous materials by crosslinking copolymerization in the presence of precipitants, phase separation takes place within a relatively short period of time. This fast phase separation naturally results in the formation of microdroplets of the rejected porogen. Since the conversion of comonomers at that moment is very low, the rapidly growing polymeric network fixes in the gel the emerging liquid droplets. The nonequilibrium microsyneresis thus transforms into the stable form of phase separation within a heterogeneous system. Thus, the fast arrival at the unstable local polymer-solvent relationship, as compared with the slow rates of solvent macrosyneresis and of network relaxation, leads to the formation of gel-included microdroplets and, finally, to a permanent macroporous structure of copolymers. 

Relaxation times are commonly measured for porous media that have been saturated with a fluid such as water or an aqueous brine solution. The observed relaxation times are strongly dependent on the pore size, the distribution of pore sizes, the type of material (e.g. content of paramagnetic ions) and the water content. While relaxation times in porous media have been modelled using random walk methods and finite-element methods, simplified models are usually needed to obtain information on pore space. Section 3.2 reviews the standard model used to analyse relaxation behaviour of fluid in macroporous samples such as rocks. Mesoporous materials such as porous silica will be discussed in Section 3.3. 

Porous silicas are usually mesoporous materials and they can be made with a variety of pore dimensions. In particular, silica glasses can be made with well-defined pore diameters, typically in the range 30-250 A, using sol-gel methods. Such a system provides a good model for testing the models of relaxation behaviour of fluids in porous solids. It is normally found that the two-site fast-exchange model for relaxation described above for macroporous systems is still valid. For instance, H and relaxation times have been measured during both adsorption and desorption of water in a porous silica. Despite hysteresis in the observed adsorption isotherms, it was found that the relaxation times depended solely on water content.For deuterated water in some porous silicas, multicomponent relaxation behaviour for T2 and Tip has been observed, and this has been attributed to the fractal nature of the pore structure. 

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