Polydispersity is inevitable in industrially produced polymers. Established theories of polymer dynamics and rheology, however, were mostly built on monodisperse linear polymers. Dynamics of polydisperse polymers is yet to be fully explored—specifically how chains of different lengths affect the dynamics of one another in a mixture. This study explored the dynamics of bidisperse polymer melts using molecular dynamics and a bead–spring chain model. Binary mixtures between a moderately entangled long-chain species and an unentangled or marginally entangled short-chain species were investigated. We found that adding short chains can significantly accelerate the dynamics of the long chains by substantially lessening their extent of entanglement. Meanwhile, although introducing long chains also hinders the motion of the short chains, it does not qualitatively alter the nature of their dynamics—unentangled short chains still follow classical Rouse dynamics even in a matrix containing entangled chains. Detailed Rouse mode analysis was used to reveal the effects of entanglement at chain segments of different scales. Stress relaxation following a step shear strain was also studied, and semi-empirical mixing rules that predict the linear viscoelasticity of polydisperse polymers based on that of monodisperse systems were evaluated with simulation results.
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Dynamics and stress relaxation of bidisperse polymer melts with unentangled and moderately entangled chains
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June 2021
Research Article|
June 23 2021
Dynamics and stress relaxation of bidisperse polymer melts with unentangled and moderately entangled chains
Special Collection:
Celebration of Robert Byron Bird (1924-2020)
Oluseye Adeyemi
;
Oluseye Adeyemi
Department of Chemical Engineering, McMaster University
, Hamilton, Ontario L8S 4L7, Canada
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Shiping Zhu (朱世平)
;
Shiping Zhu (朱世平)
Department of Chemical Engineering, McMaster University
, Hamilton, Ontario L8S 4L7, Canada
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Li Xi (奚力)
Li Xi (奚力)
a)
Department of Chemical Engineering, McMaster University
, Hamilton, Ontario L8S 4L7, Canada
a)Author to whom correspondence should be addressed: xili@mcmaster.ca. URL: https://www.xiresearch.org
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a)Author to whom correspondence should be addressed: xili@mcmaster.ca. URL: https://www.xiresearch.org
Note: This paper is part of the special topic, Celebration of Robert Byron Bird (1924–2020).
Physics of Fluids 33, 063105 (2021)
Article history
Received:
April 11 2021
Accepted:
May 25 2021
Citation
Oluseye Adeyemi, Shiping Zhu, Li Xi; Dynamics and stress relaxation of bidisperse polymer melts with unentangled and moderately entangled chains. Physics of Fluids 1 June 2021; 33 (6): 063105. https://doi.org/10.1063/5.0053790
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