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Intra‐ and inter‐chain fluctuations in entangled polymer melts in bulk and confined to pore channels
Author(s) -
Kimmich Rainer,
Fatkullin Nail,
Seitter RalfOliver,
Fischer Elmar,
Beginn Uwe,
Möller Martin
Publication year - 1999
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19991460116
Subject(s) - reptation , relaxometry , polymer , chain (unit) , relaxation (psychology) , power law , materials science , thermodynamics , chemical physics , diffusion , condensed matter physics , statistical physics , physics , nuclear magnetic resonance , mathematics , quantum mechanics , medicine , psychology , social psychology , statistics , spin echo , magnetic resonance imaging , radiology
It is known that topological restraints by “chain entanglements” severely affect chain dynamics in polymer melts. In this field‐cycling NMR relaxometry and fringe‐field NMR diffusometry study, melts of linear polymers in bulk and confined to pores in a solid matrix are compared. The diameter of the pore channels was 10 nm. It is shown that the dynamics of chains in bulk dramatically deviate from those observed under pore constraints. In the latter case, one of the most indicative signatures of the reptation model is verified 28 years after its prediction by de Gennes: The frequency and molecular mass dependencies of the spin‐lattice relaxation time obey the power law T ! ∝ M 0 v 3/4 on a time scale shorter than the longest Rouse relaxation time τ R . The mean squared segment displacement in the pores was also found to be compatible to the reptation law < r 2 >∝ M −1/2 t 1/2 predicted for τ R < t < τ d , where τ d is the so‐called disengagement time. Contrary to these findings, bulk melts of entangled polymers show frequency and molecular mass dependencies significantly different from what one expects on the basis of the reptation model. The data can however be described with the aid of the renormalized Rouse theory.