A new model for Brownian dynamics simulations of entangled polymeric liquids is proposed here. Chains are coarse grained at the level of segments between consecutive entanglements; hence, the system is in fact a network of primitive chains. The model incorporates not only the “individual” mechanisms of reptation and tube length fluctuation, but also collective contributions arising from the 3D network structure of the entangled system, such as constraint release. Chain coupling is achieved by fulfilling force balance on the entanglement nodes. The Langevin equation for the nodes contains both the tension in the chain segments emanating from the node and an osmotic force arising from density fluctuations. Entanglements are modeled as slip links, each connecting two chain strands. The motion of monomers through slip links, which ultimately generates reptation as well as tube length fluctuations, is also described by a suitable Langevin equation. Creation and release of entanglements is controlled by the number of monomers at the chain ends. In a creation event, the partner chain segment is chosen randomly among those spatially close to the advancing chain end. To validate the model, equilibrium dynamics simulations were run for monodisperse linear chains containing up to entanglements. The results show, in agreement with experiments, (i) a dependence of the longest relaxation time, (ii) a dependence of the self-diffusion coefficient, and (iii) a relaxation modulus proportional to the square of the end-to-end vector correlation function, consistently with the dynamic tube dilation concept.
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1 September 2001
Research Article|
September 01 2001
Brownian simulations of a network of reptating primitive chains
Yuichi Masubuchi;
Yuichi Masubuchi
Department of Polymer Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan
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Jun-Ichi Takimoto;
Jun-Ichi Takimoto
Department of Polymer Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan
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Kiyohito Koyama;
Kiyohito Koyama
Department of Polymer Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan
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Giovanni Ianniruberto;
Giovanni Ianniruberto
Dipartimento di Ingegneria Chimica, Università degli studi di Napoli “Federico II”, Piazzale Tecchio 80-80125 Napoli, Italy
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Giuseppe Marrucci;
Giuseppe Marrucci
Dipartimento di Ingegneria Chimica, Università degli studi di Napoli “Federico II”, Piazzale Tecchio 80-80125 Napoli, Italy
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Francesco Greco
Francesco Greco
Istituto per la Tecnologia dei Materiali Compositi-CNR, Piazzale Tecchio 80-80125 Napoli, Italy
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J. Chem. Phys. 115, 4387–4394 (2001)
Article history
Received:
January 17 2001
Accepted:
June 14 2001
Citation
Yuichi Masubuchi, Jun-Ichi Takimoto, Kiyohito Koyama, Giovanni Ianniruberto, Giuseppe Marrucci, Francesco Greco; Brownian simulations of a network of reptating primitive chains. J. Chem. Phys. 1 September 2001; 115 (9): 4387–4394. https://doi.org/10.1063/1.1389858
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