Entanglement effects in polyethylene melts: C-13 NMR relaxation experiments

TitleEntanglement effects in polyethylene melts: C-13 NMR relaxation experiments
Publication TypeJournal Article
Year of Publication2002
AuthorsQiu, X. H., and M. D. Ediger
JournalMacromoleculesMacromoleculesMacromolecules
Volume35
Pagination1691-1698
Date PublishedFeb
Type of ArticleArticle
ISBN Number0024-9297
Accession NumberWOS:000174036600033
KeywordsATACTIC POLYPROPYLENE MELTS, COEFFICIENT, GLOBAL DYNAMICS, NUCLEAR-MAGNETIC-RESONANCE, POLYMER-CHAIN, RELAXATION, ROTATING FRAME, SEGMENTAL DYNAMICS, SELF-DIFFUSION, SPIN-LATTICE RELAXATION, TRANSVERSE, VISCOSITY
Abstract

C-13 NMR T-1, NOE, and T-1rho were measured for two entangled polyethylene melts (M = 16K and 37K) at 5 and 75 MHz C-13 Larmor frequencies from the melting point up to 530 K. Two models for entanglement dynamics are tested against the experimental data. This comparison shows that entanglements not only stretch out those relaxation times longer than the entanglement time tau(e) but also have a spatial effect in restricting the motion of entangled points on the time scale of tau(e). For polyethylene, the amplitude of residual orientation on the time scale of tau(e) is lower than the theoretical prediction fox a Gaussian chain of the entanglement length with both ends fixed. The opposite conclusion was drawn from recent double quantum NMA experiments on polybutadiene. The magnetization decay curve for the T-1rho experiment is nonexponential, indicating that the loss of orientation on long time scales depends on position along the chain backbone.

Short TitleMacromoleculesMacromolecules
Alternate JournalMacromolecules