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Molecular Dynamics of Monomer, Oligomer, and Polymer Liquids in Porous Media: A Field-Cycling Nmr Relaxometry and NMR Field-Gradient Diffusometry Study

Published online by Cambridge University Press:  15 February 2011

R. Kimmich ,
S. Stapf ,
R.-O. Seitter ,
P. Callaghan  and
E. Khozina
R. Kimmich
Affiliation:
Universität Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany
S. Stapf
Affiliation:
Universität Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany
R.-O. Seitter
Affiliation:
Universität Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany
P. Callaghan
Affiliation:
Massey University, Department of Physics and Biophysics, Palmerston North, New Zealand
E. Khozina
Affiliation:
Universität Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany
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Abstract

The molecular dynamics of fluids in porous media has been studied using field-cycling NMR relaxometry and NMR field-gradient diffusometry. The frequency dependences of the 1H and 2H spin-lattice relaxation times T1 of various liquids in porous glass reveal weak and strong adsorption behaviour depending on the polarity of the adsorbates. Correlation times eight orders of magnitude longer than in bulk have been observed. The T1 dispersion moreover reflects geometrical details of the matrix in a length scale three orders of magnitude longer than the adsorbate molecules. The mean-square displacements of adsorbate molecules on the surface are only one order of magnitude less than in bulk. The global diffusivity is reduced by tortuosity and porosity effects. The observed phenomena may be explained by bulk-mediated surface diffusion, i.e., Lévy walks. The dynamics of polymer chains much longer than the pore size is characteristicly different from that in bulk melts. There is evidence that the reptation mechanism explains at least a part of the phenomena observed for the porous matrix in contrast to findings with bulk polymer melts.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 366: Symposium N – Dynamics in Small Confining Systems , 1994 , 189
Copyright
Copyright © Materials Research Society 1995

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