Prediction of linear viscoelastic properties for polydisperse mixtures of entangled star and linear polymers: Modified tube-based model and comparison with experimental results

Ruymbeke, Evelyne Van; Keunings, Roland; Bailly, Christian

doi:10.1016/j.jnnfm.2005.01.006

Cited by 97 publications

(150 citation statements)

References 41 publications

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“…This specification requires a sophisticated model that explicitly combines the reptation, CLF, and AR mechanisms in the consistently coarse-grained length and time scales. Larson and coworkers 61 and van Ruymbeke and coworkers 62,63 formulated the DTD models incorporating this concept of consistent coarse-graining, but the predictions of the current models do not appear to agree satisfactorily with the viscoelastic and dielectric data. Their models may serve as a good starting point for further refinement of the DTD model.…”

Section: Test Of Partial-dtd Picturementioning

confidence: 95%

Slow Dynamics in Homopolymer Liquids

Watanabe

2009

Polym. J.

139

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Dynamic physical properties of homopolymer liquids relax through global motion of the polymer chains over their dimension. This motion is affected by a variety of factors. For high molecular weight (M) chains, the entanglement retards the global motion to affect the properties. This entanglement effect changes with the chain architecture as well as the molecular weight distribution. The effect of the chain architecture on the global chain dynamics is found also for non-entangled low-M chains as well. This article gives a very brief summary of the experimental facts and molecular interpretations for these effects.KEY WORDS: Homopolymer Liquid / Relaxation / Slow Dynamics / Entanglement / Viscoelastic Property / Dielectric Property / Type-A Dipole / Needless to say, flexible polymer chains are composed of monomeric units covalently connected in a thread-like structure. In a local length scale, they have their own chemical functionalities such as the polorizability and electron susceptibility to exhibit intrinsic spectroscopic properties, for example, optical and electronic properties. In this sense, chemically different polymers cannot be regarded as the same class of materials. At the same time, however, the threadlike structure of polymer chains allows such chemically different chains to exhibit some universal properties. For example, flexible linear polymer melts exhibit the universal power law dependence of the zero-shear viscosity 0 on the molecular weight M, 0 / M with ¼ $ 1 and ¼ $ 3:5 in low-and high-M regimes, respectively.1 This dependence and related slow viscoelastic relaxation of polymer melts are believed to result from the fundamental thread-like structure of polymer chains irrespective of their chemical details. Scientifically, it is very interesting to explore a relationship(s) between such universal behavior of flexible polymer chains and their slow dynamics and further examine the factors that affect the slow dynamics and properties.This article follows the above viewpoint to give a very brief review of slow viscoelastic and dielectric relaxation behavior of homopolymer liquids. We place our main focus on homopolymer systems where the entanglement resulting from mutual uncrossability of real polymer chains plays the essential role. The entanglement, often modeled as mutual winding/hooking of threads, is equivalent to a topological constraint for thermal motion of the polymer chains that changes its magnitude according to the time and length scales. The linear and nonlinear viscoelastic behavior and related dielectric behavior of homopolymer melts/solutions are summarized on the basis of this molecular understanding. BASICS Molecular Expression of Viscoelastic Relaxation FunctionFor a series of chemically identical linear polymer melts having different molecular weights M, Figure 1 schematically shows the relaxation behavior of shear stress ðtÞ under a small step shear strain :1 The relaxation modulus, GðtÞ ðtÞ=, is double-logarithmically plotted against the time t after imposition of strain. The...

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Section: Test Of Partial-dtd Picturementioning

confidence: 95%

Slow Dynamics in Homopolymer Liquids

Watanabe

2009

Polym. J.

139

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“…Although the Hierarchical and BoB algorithms very much belong to the same immediate family (descended directly from Larson's work), the Time‐Marching Algorithm of van Ruymbeke is more distantly related. Within this model, the relaxation function

ϕ (t)

is written as:

ϕ (t) = \int p_{rept} false(x, t false) p_{fluc} false(x, t false) d x,

where

p_{rept} (x, t)

is the probability that a given segment (labelled with x ) has not relaxed by reptation, and

p_{fluc} (x, t)

is the probability that it has not relaxed by arm fluctuations.…”

Section: From Molecules To Rheologymentioning

confidence: 99%

From reactor to rheology in industrial polymers

Read

2014

J Polym Sci B Polym Phys

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This article reviews current efforts towards quantitative prediction of rheological properties of industrial polymer resins, based upon their polydisperse branched molecular structure. This involves both an understanding of how reactor and reaction conditions influence the distribution of chain lengths and branch placement (which is the province of reactor engineering) and an understanding of how the molecular structures in turn give rise to the rheology (the province of polymer physics). Both fields are reviewed at an introductory level, focussing in particular on developments in theoretical prediction of rheology for both entangled model polymers and industrial polymers. Finally, we discuss three classes of reaction for which the fields of reactor engineering and polymer physics have been truly combined to produce predictions from reactor to rheology.

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“…[51][52][53] As detailed in refs. [54][55][56][57], tube models are usually used for predicting the rheology of polymer melts, knowing their composition.…”

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Controlling the melt rheology of linear entangled metallo-supramolecular polymers

et al. 2015

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We study in the melt the linear viscoelastic properties of supramolecular assemblies obtained by adding different amounts of nickel ions to linear entangled poly(ethylene oxide) (PEO) building blocks end-functionalized by a terpyridine group. We first show that the elasticity of these supramolecular assemblies is mainly governed by the entanglement dynamics of the building blocks, while the supramolecular interactions delay or suppress their relaxation. By adjusting the amount of metal ions, the relaxation time as well as the level of the low-frequency plateau of these supramolecular assemblies can be controlled. In particular, the addition of metal ions above the 1:2 metal ion/terpyridine stoichiometric ratio allows secondary supramolecular interactions to appear, which are able to link the linear supramolecular assemblies and thus, lead to the reversible gelation of the system. By comparing the rheological behavior of different linear PEO samples, bearing or not functionalized chain-ends, we show that these extra supramolecular bonds are partially due to the association between the excess of metal ions and the oxygen atoms of the PEO chains. We also investigate the possible role played by the terpyridine groups in the formation of these secondary supramolecular interactions.

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Prediction of linear viscoelastic properties for polydisperse mixtures of entangled star and linear polymers: Modified tube-based model and comparison with experimental results

Cited by 97 publications

References 41 publications

Slow Dynamics in Homopolymer Liquids

Slow Dynamics in Homopolymer Liquids

From reactor to rheology in industrial polymers

Controlling the melt rheology of linear entangled metallo-supramolecular polymers

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