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Role of entanglements in polymer networks elasticity

Good day, dear colleges.

 I would like to propose a discussion about the entanglements in polymer networks. Undoubtely, they this type of topological constraints has a great influense on the statistics of the cross-linked polymers and in particular affects their elastic properties. The problem seems to be of long-lasting interest to the polymer mechanics community, though yet not resolved. I would highlight the two theories treating this phenomena: the constrained junction theory (Ronca & Allegra, Flory, Erman) and the tube constraint model (Deam, Edwards, Vilgis, Heinrich, Straube et.al.). The two theories follow quite dissimilar approaches and have different basic postulates. Hence I would first like to question the relevance of the two theories to the physical phenomenon of concern, the significance of the entanglement mechanisms considered ("hindered fluctuation of the junctions" vs "the confined fluctuation of the long chains") and the overall validity of the models ( the tube model is well grounded for the uncross-link polymers, melts and solutions; how one can reason its applicability and significance for the cross-linked systems).

Look  forward to an interesting and fruitful discussion.

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Related works:

 

 

Ronca, G. & Allegra, G. (1975). An approach to rubber elasticity with internal constraints. The Journal of Chemical Physics, 63, 4990-4997. http://dx.doi.org/doi:10.1063/1.431245

Flory, P. J. (1977). Theory of elasticity of polymer networks. The effect of local constraints on junctions. The Journal of Chemical Physics, 66, 5720-5729. http://dx.doi.org/doi:10.1063/1.433846

Erman, B. & Flory, P. J. (1978). Theory of elasticity of polymer networks. II. The effect of geometric constraints on junctions. The Journal of Chemical Physics, 68, 5363-5369. http://dx.doi.org/doi:10.1063/1.435714

Deam, R. T. & Edwards, S. F. (1976). The theory of rubber elasticity. Philosophical Transactions of the Royal Society A, 280, 317-353. http://dx.doi.org/doi: 10.1098/rsta.1976.0001

Edwards, S. F. & Vilgis, T. A. (1988). The tube model theory of rubber elasticity. Reports on Progress in Physics, 51, 243-297. http://dx.doi.org/doi:10.1088/0034-4885/51/2/003

Heinrich, G. & Straube, E. (1983). On the strength and deformation dependence of the tube-like topological constraints of polymer networks, melts and concentrated solutions, I. The polymer network case. Acta Polymerica, 34, 589-594.  http://dx.doi.org/doi:10.1002/actp.1983.010340909

 

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