Pulsed and Steady Field Gradient NMR Diffusion Measurements in Polymers

Some twenty years after the development of the steady and pulsed gradient spin-echo NMR methods of measuring self-diffusion, these techniques are now maturing and experiencing a surge of interest, much of it concentrated on polymer systems. The methods are briefly reviewed here, together with the most important results in polymers, with particular concentration on work described within the last few years. The research is divisible into three categories: diffusion of diluent and penetrant molecules in rubbery high polymers, diffusion of polymer molecules in dilute and semidilute solutions with liquid solvents, and diffusion of macromolecules dissolved in concentrated solutions or melts of equivalent or different polymers of arbitrary molecular weight. The review includes the main theoretical interpretations of the experiments, particularly the free-volume theory in its various forms and power-law behaviors postulated by recent refinements of tube/reptation and scaling theory. This article represents an updated elaboration of an earlier review.