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Dynamic Intrinsic Viscosity of Macromolecules with Internal Viscosity. III. Effect of Molecular Weight, Excluded Volume, and Hydrodynamic Interaction

 

作者: A. Peterlin,   Chr. Reinhold,  

 

期刊: Transactions of the Society of Rheology  (AIP Available online 1967)
卷期: Volume 11, issue 1  

页码: 15-37

 

ISSN:0148-6055

 

年代: 1967

 

DOI:10.1122/1.549086

 

出版商: The Society of Rheology

 

数据来源: AIP

 

摘要:

The frequency dependence of the complex intrinsic viscosity and elastic modulus of a macromolecule with internal viscosity is calculated for the Gaussian coil and the coil with excluded volume in a wide range of molecular weight and hydrodynamic interaction. Due to limitations in eigenvalues and because of coil rotation in laminar flow the results obtained are sufficiently accurate only for a large number of coil segments and for small internal viscosity. Hydrodynamic interaction enhances the effect of internal viscosity so that the macromolecule seems to be stiffer than in the free‐draining case. The non‐Gaussian character of intrachain distances has a very small effect. Finite internal viscosity yields a nonvanishing limiting viscosity atω→∞which at sufficiently largeMincreases asM1/6.The relative limiting viscosity[η]∞′/[η]0as a function of molecular weight(Z∼M),hydrodynamic interaction (h), non‐Gaussian character of the coil (ε), and internal viscosity (φ) can be well represented by a single master curve if plotted againstν1φ/Zf.The eigenvalueν1is unity for the free‐draining coil and asymptotically increases as a linear function ofhand ε. Molecular weight enters the abscissa of the master curve implicitly throughν1and explicitly throughZ.

 

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