Constraint release in polymer melts: tube reorganization versus tube dilation

Viovy, Jean Louis; Rubinstein, Michael; Colby, Ralph H.

doi:10.1021/ma00012a020

Cited by 215 publications

(356 citation statements)

References 24 publications

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“…This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe's end-to-end vector in polydisperse systems. We follow the CR picture of (Viovy et al, 1991) and refine the effective chain friction in the thin and fat tubes based on (Read et al, 2012). The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers.…”

Section: Understanding Effect Of Constraint Release Environment On Enmentioning

confidence: 99%

“…An analysis of this was presented in ref., 22 building on the earlier work of Viovy. 28 This analysis assumed independence between diffusive transport processes along thin and fat tubes, giving an equation for the friction coefficient per bead of the chain constrained by blinking and permanent entanglements: For the present SSp simulations, the analysis is made more complicated by the two specific issues identified above in section 6.1 and detailed in Appendices A and B: (i) the fact that the dilution factor f for the number of slip-links is not the same as the dilution factor for tube diameter, and (ii) the contribution of slip-links to the sliding friction. We detail the corrections which must be made to the analysis by Read 22 for the SSp simulations in Appendix C. The resulting final expressions for the separate frictions contributions to motion along thin and fat tubes are given in equations C6 to C8 (of Appendix C).…”

Section: Two-tube System With a Fraction Of Never Relaxing Entanglemementioning

confidence: 99%

“…9 proposed to combine both CR pictures and defined the effective tube diameter as a crossover between mean squared displacement of the free chain and motion of the tube described by Rouse dynamics. Finally, Viovy and coworkers 28 further extended the original tube rearrangement picture for the case of binary linear melts. They proposed that CR motion of the tube should be effectively separated in two regimes:…”

Section: Introductionmentioning

confidence: 99%

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Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

et al. 2017

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In this study we propose and verify methods based on the slip-spring (SSp) model (Likhtman, 2005) for predicting the effect of any monodisperse, binary or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic 2 and dielectric response of monodisperse and binary mixtures of type-A polymers, based on published experimental data. We also report the synthesis of new binary and ternary Polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes, and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe's end-to-end vector in polydisperse systems. We follow the CR picture of (Viovy et al., 1991) and refine the effective chain friction in the thin and fat tubes based on (Read et al., 2012). The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.

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Section: Understanding Effect Of Constraint Release Environment On Enmentioning

confidence: 99%

Section: Two-tube System With a Fraction Of Never Relaxing Entanglemementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

et al. 2017

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“…0031-9007=09=103(13)=136001 (4) 136001-1 Ó 2009 The American Physical Society entanglements can act as elastic constraints [4,7]. In this Letter we shall examine the dilution exponent, since (as we shall see) it is important for the effective stretch relaxation time also.…”

mentioning

confidence: 97%

“…It might be that, before a test chain has escaped from its tube, one of the constraining chains moves out of the way, releasing the entanglement constraint. This constraint release process provides a second relaxation mechanism, commonly modeled as a local sideways hop of the tube at each constraint release event [3][4][5][6]. Accounting for constraint release has been essential in understanding the experimental lack of shear banding in strong flows of monodisperse melts [5,6].…”

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confidence: 99%

Elongational Flow of Blends of Long and Short Polymers: Effective Stretch Relaxation Time

et al. 2009

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Capillary electrophoresis of DNA in uncrosslinked polymer solutions: Evidence for a new mechanism of DNA separation

Barron

Sunada

Blanch

2000

Biotechnol. Bioeng.

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The electrophoretic separation of DNA molecules is usually performed in thin slabs of agarose or polyacrylamide gel. However, DNA separations can be achieved more rapidly and efficiently within a microbore fused silica capillary filled with an uncrosslinked polymer solution. An early assumption was that the mechanism of DNA separation in polymer solution(SINGLEBOND)capillary electrophoresis (PS(SINGLEBOND)CE) is the same as that postulated to occur in slab gel electrophoresis, i.e., that entangled polymer chains form a network of “pores” through which the DNA migrates. However, we have demonstrated that large DNA restriction fragments (2.0(SINGLEBOND)23.1 kbp) can be separated by CE in extremely dilute polymer solutions, which contain as little as 6 parts per million [0.0006% (w/w)] of uncrosslinked hydroxyethyl cellulose (HEC) polymers. In such extremely dilute HEC solutions, far below the measured polymer entanglement threshold concentration, pore‐based models of DNA electrophoresis do not apply. We propose a transient entanglement coupling mechanism for the electrophoretic separation of DNA in uncrosslinked polymer solutions, which is based on physical polymer/DNA interactions. © 1996 John Wiley & Sons, Inc.

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Constraint release in polymer melts: tube reorganization versus tube dilation

Cited by 215 publications

References 24 publications

Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

Elongational Flow of Blends of Long and Short Polymers: Effective Stretch Relaxation Time

Capillary electrophoresis of DNA in uncrosslinked polymer solutions: Evidence for a new mechanism of DNA separation

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