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• W1973162904 endingPage "1951" @default.
• W1973162904 startingPage "1937" @default.
• W1973162904 abstract "Viscoelastic and dielectric experiments were conducted for entangled binary blends of linear cis-polyisoprenes (PI) having widely separated molecular weights, M1 = 21.4 × 103 ≅ 4Me and M2 = 308 × 103 ≅ 62Me with Me (≅5 × 103) being the entanglement molecular weight. The PI chain had type-A dipoles and its global motion (end-to-end vector fluctuation) was dielectrically active. The volume fraction of the high-M chain, υ2, was varied from 0.005 to 1. The Struglinski-Graessley parameter for the blends, M2Me2/M13 = 0.79, was larger than a threshold value ≅0.5 necessary for the thermal constraint release (CR) mechanism to dominate the relaxation of the dilute high-M chains. Indeed, the Rouse-like CR relaxation was experimentally detected for the blends with small υ2 ≤ 0.01. For large υ2 (≥0.05), the high-M chains were entangled with each other (as well as with the low-M chains) and exhibited solution-like relaxation behavior at long times in their terminal regime. Comparison of viscoelastic and dielectric data suggested that the molecular picture of the dynamic tube dilation (DTD; with the dilation exponent d ≅ 1.3) incorporating the tube-edge fluctuation effect was valid in this regime. However, at intermediate times that were still longer than the relaxation time of the low-M chains, the moduli of the high-M chains were larger than the DTD prediction. In this intermediate regime, the CR equilibration of the entanglement segments in a dilated tube segment (the prerequisite of DTD) could not occur in time, thereby resulting in this failure of the DTD picture. In addition, the viscoelastic mode distribution of the high-M chains in the blends (with υ2 ≥ 0.05) agreed with that in the corresponding solutions only in time scales longer than the time required for the CR equilibration over the whole contour of the chain. These results demonstrated the importance of the CR equilibration in the entanglement dynamics." @default.
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• W1973162904 date "2004-02-04" @default.
• W1973162904 modified "2023-10-11" @default.
• W1973162904 title "Viscoelastic and Dielectric Behavior of Entangled Blends of Linear Polyisoprenes Having Widely Separated Molecular Weights: Test of Tube Dilation Picture" @default.
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• W1973162904 doi "https://doi.org/10.1021/ma030443y" @default.
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