2017年1月21日星期六

Porous Media NMR Analysis

Recent years have seen a significant progress in the study of porous media of natural and industrial sources. This paper provides a brief outline of the recent technical development of NMR in this area. These progresses are relevant for NMR application in material characterization.
The wettability conditions in a porous media containing two or more immiscible fluid phases determine the microscopic fluid distribution in the pore network. Nuclear magnetic resonance measurements are sensitive to wettability because of the strong effect that the solid surface has on promoting magnetic relaxation of the saturating fluid. The idea of using NMR as a tool to measure wettability was presented by Brown and Fatt in 1956. The magnitude of this effect depends upon the wettability characteristics of the solid with respect to the liquid in contact with the surface.Their theory is based on the hypothesis that molecular movements are slower in the bulk liquid than at the solid-liquid interface. In this solid-liquid interface the diffusion coefficient is reduced, which correspond to a zone of higher viscosity. In this higher viscosity zone, the magnetically aligned protons can more easily transfer their energy to their surroundings. The magnitude of this effect depends upon the wettability characteristics of the solid with respect to the liquid in contact with the surface.
NMR Cryoporometry (NMRC) is a recent technique for measuring total porosity and pore size distributions. It makes use of the Gibbs-Thomson effect : small crystals of a liquid in the pores melt at a lower temperature than the bulk liquid : The melting point depression is inversely proportional to the pore size. The technique is closely related to that of the use of gas adsorption to measure pore sizes (Kelvin equation). Both techniques are particular cases of the Gibbs Equations (Josiah Willard Gibbs): the Kelvin Equation is the constant temperature case, and the Gibbs-Thomson Equation is the constant pressure case.
To make a Cryoporometry measurement, a liquid is imbibed into the porous sample, the sample cooled until all the liquid is frozen, and then warmed slowly while measuring the quantity of the liquid that has melted. Thus it is similar to DSC thermoporosimetry, but has higher resolution, as the signal detection does not rely on transient heat flows, and the measurement can be made arbitrarily slowly. It is suitable for measuring pore diameters in the range 2 nm–2 μm.
Nuclear Magnetic Resonance (NMR) may be used as a convenient method of measuring the quantity of liquid that has melted, as a function of temperature, making use of the fact that the {\displaystyle T_{2}} T_{2} relaxation time in a frozen material is usually much shorter than that in a mobile liquid. The technique was developed at the University of Kent in the UK.It is also possible to adapt the basic NMRC experiment to provide structural resolution in spatially dependent pore size distributions, or to provide behavioural information about the confined liquid.porous media NMR

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