Nonlinear Elongation Flows in Associating Polymer Melts: From Homogeneous to Heterogeneous Flow

Mohottalalage, Supun; Senanayake, Manjula; Clemmer, Joel; Perahia, Dvora; Grest, Gary S.; O'Connor, Thomas

doi:10.1103/physrevx.12.021024

Cited by 10 publications

(14 citation statements)

References 44 publications

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“…However, these studies were performed on telechelic systems, and the role of molecular architecture and placement of stickers on the chain remains unknown. Several recent simulation studies of telechelic and star-like polymers with stickers revealed specific details of linear and non-linear rheological properties of these systems. − These simulations also suggested that an increase in the energy of the stickers interactions up to ∼5RT will lead to their phase separation from the polymer matrix for both, linear and star chains …”

Section: Introductionmentioning

confidence: 94%

Influence of Molecular Architecture on the Viscoelastic Properties of Polymers with Phase-Separated Dynamic Bonds

Carden

Zhao

et al. 2023

Macromolecules

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Polymers with dynamic bonds attract significant attention due to their many unique properties, such as self-healing and recycling. However, understanding microscopic mechanisms controlling their dynamics and viscoelastic properties, especially in the case of phase-separated dynamic bonds, remains rather limited. We present analysis of model polymer systems with phase-separating dynamic bonds (stickers) placed along the chain (pendant stickers) or at the end of the chain (telechelic systems). We demonstrate that the bond rearrangement process in these systems is controlled by the pullout of a sticker from a cluster, with the characteristic time defined by structural relaxation in clusters and miscibility of stickers in the polymer matrix. This enables decoupling of terminal relaxation from segmental dynamics of the polymer. The analysis revealed the critical role of the total concentration of stickers that controls dynamics of the polymer in the broad time range from segmental relaxation up to the time of sticker pullout from a cluster, regardless of the sticker placement on the chain and the length of the chain. Only at longer time scales, the molecular length and sticker placement influence viscoelastic properties. Based on these results, we suggest a general scenario for mechanisms controlling the dynamics and viscoelasticity of polymers with phase-separated dynamic bonds. This scenario can be helpful in guiding the design of dynamic polymers with desired viscoelastic properties.

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Section: Introductionmentioning

confidence: 94%

Influence of Molecular Architecture on the Viscoelastic Properties of Polymers with Phase-Separated Dynamic Bonds

Carden

Zhao

et al. 2023

Macromolecules

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“…Associative polymers form a transient network, and their elongational rheology is crucial to their processing and application. − Extensive studies have been conducted to understand the elongational rheology of associative polymers. − These associative polymers include water-soluble polymers associating through hydrophobically modified end groups − or ionic bridges and polymer melts associating through ionic (salt) attractions or hydrogen bonds. − We have been focusing on ionomers and have found, in a recent study, that unentangled low- M ionomers exhibited either ductile or brittle behavior under fast elongation according to the degree of gelation and strength of association. − Nevertheless, the rheology–structure relationship of entangled high- M ionomers is yet to be better understood. The entangled ionomers should form two types of transient networks through either the entanglements or the physical cross-links, and mutual penetration of these two networks would result in an interesting synergetic effect(s) on the nonlinear elongational rheology, as expected from their linear viscoelastic (LVE) behavior. − …”

Section: Introductionmentioning

confidence: 99%

Elongational Rheology of Entangled Ionomers Based on Poly(hexyl methacrylate)

Wu,

Yang,

Zhang

et al. 2023

Macromolecules

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“…They showed that in melts, dynamics of the polymer depends on the counterion and cluster morphology. A direct correlation between flow response and clustering has been recently demonstrated, where the flow viscosity is directly impacted by the size, shape and distribution of the clusters. , …”

Section: Introductionmentioning

confidence: 99%

“…A direct correlation between flow response and clustering has been recently demonstrated, where the flow viscosity is directly impacted by the size, shape and distribution of the clusters. 12,30 Early NSE studies of SPS with low sulfonation levels in THF and DMSO solvents resolved the polymer relaxation time in terms of a correlation length ξ that captures interchain correlations. 31 These studies have provided a glimpse into the correlation of chain relaxation and viscosity, providing the knowledge base that underlies the current studies.…”

Section: ■ Introductionmentioning

confidence: 99%

From Molecular Constraints to Macroscopic Dynamics in Associative Networks Formed by Ionizable Polymers: A Neutron Spin Echo and Molecular Dynamics Simulations Study

Kosgallana,

Wijesinghe,

Senanayake

et al. 2024

ACS Polym. Au

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The association of ionizable polymers strongly affects their motion in solutions, where the constraints arising from clustering of the ionizable groups alter the macroscopic dynamics. The interrelation between the motion on multiple length and time scales is fundamental to a broad range of complex fluids including physical networks, gels, and polymer−nanoparticle complexes where long-lived associations control their structure and dynamics. Using neutron spin echo and fully atomistic, multimillion atom molecular dynamics (MD) simulations carried out to times comparable to that of chain segmental motion, the current study resolves the dynamics of networks formed by suflonated polystryene solutions for sulfonation fractions 0 ≤ f ≤ 0.09 across time and length scales. The experimental dynamic structure factors were measured and compared with computational ones, calculated from MD simulations, and analyzed in terms of a sum of two exponential functions, providing two distinctive time scales. These time constants capture confined motion of the network and fast dynamics of the highly solvated segments. A unique relationship between the polymer dynamics and the size and distribution of the ionic clusters was established and correlated with the number of polymer chains that participate in each cluster. The correlation of dynamics in associative complex fluids across time and length scales, enabled by combining the understanding attained from reciprocal space through neutron spin echo and real space, through large scale MD studies, addresses a fundamental long-standing challenge that underline the behavior of soft materials and affect their potential uses.

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Nonlinear Elongation Flows in Associating Polymer Melts: From Homogeneous to Heterogeneous Flow

Cited by 10 publications

References 44 publications

Influence of Molecular Architecture on the Viscoelastic Properties of Polymers with Phase-Separated Dynamic Bonds

Influence of Molecular Architecture on the Viscoelastic Properties of Polymers with Phase-Separated Dynamic Bonds

Elongational Rheology of Entangled Ionomers Based on Poly(hexyl methacrylate)

From Molecular Constraints to Macroscopic Dynamics in Associative Networks Formed by Ionizable Polymers: A Neutron Spin Echo and Molecular Dynamics Simulations Study

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