期刊
PHYSICAL REVIEW LETTERS
卷 97, 期 20, 页码 -出版社
AMER PHYSICAL SOC
DOI: 10.1103/PhysRevLett.97.207803
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We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t greater than or similar to tau(alpha)) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817 000 g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size M(R)similar or equal to 500 and entanglement weight M(e)similar or equal to 2000; the Rouse spectrum saturates at M(max)similar or equal to 4000. The local order parameter S approximate to 0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature T(g), obtained from dielectric relaxation spectra, shows distinctive kinks at M(R) and M(e).
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