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The rotational relaxation of the solvent chlorinated biphenyl, also known as Aroclor 1248, has been measured in solutions containing either 1,2-polybutadiene or other polymers by photon correlation spectroscopy. The data shows the solvent relaxation time decreases with the addition of 1,2-polybutadiene, which is unexpected from the reduction of solution-free-volume as indicated by the bulk polymer having a higher glass transition temperature than that of the neat solvent. This anomalous observed behavior, a reversal of the trend set by other polymer solutions, should have deep implications in the search for the correct method for accounting for changes in local friction in polymer solutions. We show that the coupling model provides a consistent interpretation of the data as well as related data of tracer diffusion in polymer solutions.
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Rizos et al. (1992) studied this question.
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