Interplay of entanglement and association effects on the dynamics of semidilute solutions of multisticker polymer chains

Shivokhin, Maksim; Narita, Tetsuharu; Talini, Laurence; Habicht, Axel; Seiffert, Sebastian; Indei, Tsutomu; Schieber, Jay D.

doi:10.1122/1.4997740

Cited by 17 publications

(25 citation statements)

References 29 publications

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“…This part of our model shares some features with the model described earlier by Shivokhin et al [76] for entangled sticky polymers, and may be considered a special case of that model.…”

Section: Modeling Of Linear Shear and Nonlinear Extensional Rhe-osupporting

confidence: 70%

“…The chain motions associated with these two interactions, respectively, can be expected to behave differently as temperature is varied leading to a breakdown of TTS. To what degree TTS still approximately holds for a particular supramolecular system will depend on the specific material and interaction details and it is not uncommon for TTS to be applied to supramolecular systems [20, 63-67, 70, 75], even though alternative techniques that permit data to be obtained over extended dynamic range can preclude the use of TTS [76].…”

Section: Introductionmentioning

confidence: 99%

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Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate based polymers for which the concentration of randomly distributed supramolecular side-groups are systematically varied. We perform a detailed investigation of the appplicability of Time Temperature Superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the "stickyRouse" model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the "sticky-Rouse" model, which includes more realistic assumptions with regards to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends and (iii) the chain motion upon dissociation of a sticker and re-association with a new co-ordination which involves a finite sized "hop" of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology. * k.j.l.mattsson@leeds.ac.uk 2

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“…This part of our model shares some features with the model described earlier by Shivokhin et al [76] for entangled sticky polymers, and may be considered a special case of that model.…”

Section: Modeling Of Linear Shear and Nonlinear Extensional Rhe-osupporting

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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“…In addition, it has been recently shown that the effect of entanglement on the dynamics is quite different from the presence of stickers. 106 Moreover, the molecular weight dependence of terminal relaxation time in entangled polymers is different from transient networks (Figure 14). 49 More recently, the relaxation of similar supramolecular polymers was modeled by a modified sticky Rouse model whereby the effect of sticker distribution was taken into account.…”

Section: Sticker Positionmentioning

confidence: 99%

“…In entangled systems, it has been recently shown that the presence of entanglements does not affect the stickers dynamics, but stickers do affect disentanglement by delaying the relaxation process. 106 In several studies, the strength of the metal–ligand interaction was studied, 119,120 whereas some other research compared the association strength of different types of stickers (based on hydrogen bonding or metal–ligand interaction) (see Figure 8). It was shown that the association strength has a direct influence on the formation of a plateau and delay in the terminal relaxation time.…”

Section: Sticker Positionmentioning

confidence: 99%

A Critical Approach to Polymer Dynamics in Supramolecular Polymers

Golkaram

Loos

2019

Macromolecules

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Over the past few years, the concurrent (1) development of polymer synthesis and (2) introduction of new mathematical models for polymer dynamics have evolved the classical framework for polymer dynamics once established by Doi–Edwards/de Gennes. Although the analysis of supramolecular polymer dynamics based on linear rheology has improved a lot recently, there are a large number of insecurities behind the conclusions, which originate from the complexity of these novel systems. The interdependent effect of supramolecular entities (stickers) and chain dynamics can be overwhelming depending on the type and location of stickers as well as the architecture and chemistry of polymers. This Perspective illustrates these parameters and strives to determine what is still missing and has to be improved in the future works.

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“…There are subtle differences between the meaning of these terms, for example, entanglement is the inter-penetration of polymer chains [71] while association is the formation of transient cross-links between polymer chains [72]. However, they are used somewhat generically in the VM literature to indicate an increase in viscosity through the collective action of multiple polymers [1,14,15,28,53,73,74].…”

Section: Association and Entanglementmentioning

confidence: 99%

Review of Viscosity Modifier Lubricant Additives

2018

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This article reviews viscosity modifiers, additives that increase the viscosity of lubricating oils. Viscosity modifiers are high molecular weight polymers whose functionality is derived from their thickening efficiency, viscosity-temperature relationship, and shear stability. There are now many different additive chemistries and architectures available, all of which have advantages and disadvantages, and affect solution viscosity through different mechanisms. Understanding these mechanisms and how they impart additive function is critical to the development of new viscosity modifiers that enable lubricants to function more efficiently over a wide range of temperatures.

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Interplay of entanglement and association effects on the dynamics of semidilute solutions of multisticker polymer chains

Cited by 17 publications

References 29 publications

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

A Critical Approach to Polymer Dynamics in Supramolecular Polymers

Review of Viscosity Modifier Lubricant Additives

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