We present a systematic experimental study of the shear rheology of metallosupramolecular assemblies based on entangled telechelic star polymers comprising one (single dynamic network) or two (double dynamics network) types of physical bonds with the aim to unravel the role of concentration and strength of these bonds on the nonlinear response. Model dynamic networks functionalized with terpyridine ligands were formed by adding different metal ions with increasing bonding strength, zinc, copper, and cobalt. The dynamics are driven by entanglement/disentanglement processes and a ligand exchange mechanism. Steady-state viscosities of single and double dynamics networks collapse onto a universal curve over a wide range of Weissenberg numbers based on terminal time (up to about 300 for single and 1000 for double), exhibiting stronger shear thinning (with an exponent of −0.76) compared to entangled neutral star polymers. Double dynamics networks consisting of two different metal ions (with different lifetimes) exhibit stronger mechanical coherence (rate-dependent fractional viscosity overshoot) and accumulate larger strain at steady-state flow compared to single-ion counterparts. The shear stress growth function signals exhibit weak, albeit unambiguous shear strain hardening, which becomes more pronounced for stronger associations. They also exhibit double overshoot, which reflects the interplay of association strength and chain deformation. Increasing the strength of associations leads to the failure of the Cox–Merz rule, which is more severe for single dynamic networks. The markedly different behavior of double dynamics networks is attributed to the fact that at sufficiently high ion content, the weaker bond acts as a sacrificial component, which provides local energy dissipation and enhances the overall deformability. This bears analogies with their linear viscoelastic response, which has revealed that the arm disentanglement (delayed due to the reversible bonds) effectively interpolates between the two single dynamic network components, depending on composition. Our results suggest ways to tailor the mechanical properties of this class of materials by judicious choice of the type and content of the ion.
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November 2022
Research Article|
November 01 2022
Nonlinear shear rheology of single and double dynamics metal-ligand networks
Special Collection:
Double Dynamics Polymeric Networks
Christina Pyromali;
Christina Pyromali
1
Institute of Electronic Structure and Laser, FORTH
, Heraklion 70013, Crete, Greece
2
Department of Materials Science and Technology, University of Crete
, Heraklion 71003, Crete, Greece
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Yanzhao Li;
Yanzhao Li
3
Bio- and Soft Matter, Institute of Condensed Matter and Nanosciences, Université catholique de Louvain
, Croix du Sud 1, Louvain-la-Neuve B-1348, Belgium
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Flanco Zhuge;
Flanco Zhuge
3
Bio- and Soft Matter, Institute of Condensed Matter and Nanosciences, Université catholique de Louvain
, Croix du Sud 1, Louvain-la-Neuve B-1348, Belgium
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Charles-André Fustin
;
Charles-André Fustin
3
Bio- and Soft Matter, Institute of Condensed Matter and Nanosciences, Université catholique de Louvain
, Croix du Sud 1, Louvain-la-Neuve B-1348, Belgium
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Evelyne van Ruymbeke
;
Evelyne van Ruymbeke
3
Bio- and Soft Matter, Institute of Condensed Matter and Nanosciences, Université catholique de Louvain
, Croix du Sud 1, Louvain-la-Neuve B-1348, Belgium
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Dimitris Vlassopoulos
Dimitris Vlassopoulos
a)
1
Institute of Electronic Structure and Laser, FORTH
, Heraklion 70013, Crete, Greece
2
Department of Materials Science and Technology, University of Crete
, Heraklion 71003, Crete, Greece
a)Author to whom correspondence should be addressed; electronic mail: dvlasso@iesl.forth.gr
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a)Author to whom correspondence should be addressed; electronic mail: dvlasso@iesl.forth.gr
Note: This paper is part of the special issue on Double Dynamics Polymeric Networks
J. Rheol. 66, 1223–1235 (2022)
Article history
Received:
December 28 2021
Accepted:
March 10 2022
Citation
Christina Pyromali, Yanzhao Li, Flanco Zhuge, Charles-André Fustin, Evelyne van Ruymbeke, Dimitris Vlassopoulos; Nonlinear shear rheology of single and double dynamics metal-ligand networks. J. Rheol. 1 November 2022; 66 (6): 1223–1235. https://doi.org/10.1122/8.0000429
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