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Terminal relaxation and diffusion of entangled three-arm star polymers: Temperature and molecular weight dependencies

✍ Scribed by K. L. Ngai; C. M. Roland


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
147 KB
Volume
35
Category
Article
ISSN
0887-6266

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✦ Synopsis


Recent experimental investigation of the terminal relaxation in high molecular weight polyisoprenes by dynamic mechanical measurements (C. A. Bero and C. M. Roland, Macromolecules, 29, 1562 (1996)) has found the terminal relaxation times to be more sensitive to changes in temperature for three-arm stars than for the linear polyisoprenes. Moreover, these measurements, carried out with significantly higher molecular weight samples than heretofore, show that the molecular weight dependence of the terminal relaxation times for three-arm star polyisoprenes is much weaker than the exponential dependence previously proposed (L. J. Fetters, et al., Macromolecules, 26, 647 (1993)). Tracer diffusion of labeled linear and three-arm star polyethylenelike diffusant molecules in a highly entangled linear polyethylene matrix exhibit temperature and molecular weight dependencies similar to those observed spectroscopically from bulk polymers. Both the temperature and molecular weight dependencies for the star-branched polymers are at variance with the predictions of the reptation model. It is shown here, however, that these observations can be reconciled through application of the coupling model of relaxation.