A theory of the linear viscoelastic properties of dilute solutions of coiling polymers. II. A first-order mechanical thermodynamic property
A theory of the linear viscoelastic properties of dilute solutions of coiling polymers. II. A first-order mechanical thermodynamic property
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DOI：
10.1063/1.476306
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发表时间：
1998-10
影响因子：
4.4
通讯作者：
P. E. Rouse
中科院分区：
文献类型：
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作者：
P. E. Rouse
这一理论经过修正，包括了与之前所考虑的构型扩散在性质上根本不同的松弛过程。这些过程涉及相对持久的分子内“隐晶”。粘性流动对这些范德华键簇施加压力，从而储存自由能。在随后的向平衡方向漂移过程中，这种能量的耗散导致了粘性损失。这些准化学的标量过程和构型扩散的矢量过程彼此独立地进行。在易于形成许多“隐晶”的体系中，这些团簇对粘度的贡献几乎与聚合物的浓度成正比。如果不太可能形成持久的团簇，则团簇对粘度的贡献将随着分子量的增加而增加，最终与聚合物浓度成正比。讨论了影响这些溶液粘度和粘弹性的所有过程。
The theory is corrected to include relaxation processes fundamentally different in character from the configurational diffusion considered before. These processes involve relatively persistent intramolecular “cryptocrystallites.” Viscous flow places stress on these clusters of van der Waals bonds, storing free energy. Dissipation of this energy during the ensuing drift toward equilibrium contributes to the viscous losses. These quasichemical, scalar processes and the vectorial process of configurational diffusion proceed independently of one another. In systems in which many “cryptocrystallites” tend to form, these clusters make a contribution to viscosity almost directly proportional to the concentration of the polymer. If formation of persistent clusters is less likely, the contribution of clusters to the viscosity will increase with increasing molecular weight, finally becoming proportional to polymer concentration. All processes contributing to viscosity and viscoelasticity of these solutions are trea...