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Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends

Publication ,  Journal Article
Rubinstein, M; Colby, RH
Published in: The Journal of Chemical Physics
October 15, 1988

The effects of polydispersity on the linear viscoelastic properties of concentrated polymer solutions and melts are analyzed. Existing theories for the dynamics of linear polymers, based on the idea of each polymer confined in a fixed tube, are shown to be incapable of describing observed rheological response of polydisperse polymers. A model is proposed which, in a self-consistent manner, solves the many chain problem given the solution to the single chain problem. Two types of polymer relaxation are incorporated in the model. The first type is escape of a polymer from its tube by motion of the polymer itself. It includes all dynamic modes available to the single chain in a tube—those due to its reptation—as well as other modes, such as fluctuations in tube length. The second type is relaxation of a polymer chain by the motions of the surrounding polymers forming its tube (constraint release). The relaxation modulus is then the product of two functions μ(t) and R(t). μ(t) is the fraction of tube occupied at time t=0 that has not been evacuated at time t, thereby representing escape of the polymer from its tube (solution to the single chain problem). R(t) represents relaxation by the constraint release process, which is modeled by a Rouse chain with random bead mobilities. The probability distribution of these mobilities is determined, in a self-consistent way, from the disentanglement rates due to the tube evacuation processes of the surrounding chains. Thus R(t) is calculated from the spectrum of relaxation rates of the μ(t) processes for the surrounding chains. The predictions of the model with some single chain solutions μ(t) from the literature are compared with oscillatory shear data for binary blends of nearly monodisperse polybutadiene, in which both components are well entangled.

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Published In

The Journal of Chemical Physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

October 15, 1988

Volume

89

Issue

8

Start / End Page

5291 / 5306

Publisher

AIP Publishing

Related Subject Headings

  • Chemical Physics
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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Rubinstein, M., & Colby, R. H. (1988). Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends. The Journal of Chemical Physics, 89(8), 5291–5306. https://doi.org/10.1063/1.455620
Rubinstein, Michael, and Ralph H. Colby. “Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends.” The Journal of Chemical Physics 89, no. 8 (October 15, 1988): 5291–5306. https://doi.org/10.1063/1.455620.
Rubinstein M, Colby RH. Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends. The Journal of Chemical Physics. 1988 Oct 15;89(8):5291–306.
Rubinstein, Michael, and Ralph H. Colby. “Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends.” The Journal of Chemical Physics, vol. 89, no. 8, AIP Publishing, Oct. 1988, pp. 5291–306. Crossref, doi:10.1063/1.455620.
Rubinstein M, Colby RH. Self-consistent theory of polydisperse entangled polymers: Linear viscoelasticity of binary blends. The Journal of Chemical Physics. AIP Publishing; 1988 Oct 15;89(8):5291–5306.

Published In

The Journal of Chemical Physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

October 15, 1988

Volume

89

Issue

8

Start / End Page

5291 / 5306

Publisher

AIP Publishing

Related Subject Headings

  • Chemical Physics
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences