Overcoming mechanical stability-flow processability trade-off of vitrimers using ionic interactions

Harmandeep Singh; Mary Danielson; Ryan Peterson; Ivan Popov; Alexei P. Sokolov; Tomonori Saito; Md Anisur Rahman; Catalin Gainaru

doi:10.1016/j.xcrp.2026.103417

Overcoming mechanical stability-flow processability trade-off of vitrimers using ionic interactions

Harmandeep Singh
, Mary Danielson
, Ryan Peterson
, Ivan Popov
, Alexei P. Sokolov
, Tomonori Saito
, Md Anisur Rahman
, Catalin Gainaru

Soft Materials and Membranes

Research output: Contribution to journal › Article › peer-review

Abstract

It is well established that the macroscopic flow of dynamic covalent networks involves mesoscopic rearrangement of crosslinkers; however, its relationship with local, segmental motions remains under debate. In this vein, the present study investigates how tuning the segmental (α) dynamics using salt doping impacts the viscoelastic behavior of two vinylogous urethane-based vitrimers. Our analyses show that additional ionic interactions significantly slow down the α relaxation in these materials, driving them into the glassy state at room temperature, while having a much weaker impact on their global dynamics. This disparity allows the separation of the individual contributions of segmental dynamics and network rearrangements to their terminal flow. In addition, our results demonstrate that tuning segmental dynamics, as an alternative to the popular approach of adjusting network rearrangements, can be used for the development of vitrimers that are mechanically rigid and creep resistant at ambient conditions yet flow-processable at moderately high temperatures.

Original language	English
Article number	103417
Journal	Cell Reports Physical Science
Volume	7
Issue number	7
DOIs	https://doi.org/10.1016/j.xcrp.2026.103417
State	Published - Jul 15 2026

Funding

This research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, under contract no. DE-AC05-00OR22725, for the US Department of Energy (DOE). PET macromonomer synthesis was supported by the US DOE , Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. A.P.S. acknowledges financial support for data analysis and manuscript revision from the NSF Polymer program (award DMR-2515834 ). H.S. acknowledges partial support from “Fast and Cooperative Ion Transport in Polymer-Based Materials (FaCT),” an Energy Frontier Research Center funded by the US DOE, Office of Science, Basic Energy Sciences, for its contribution to conductivity measurements, data analysis, and interpretation. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US DOE. The US government retains, and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Keywords

creep-resistant materials
ion doping
ionic interactions
processability
rheology
segmental dynamics
terminal flow
vinylogous urethane
vitrimers

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10.1016/j.xcrp.2026.103417

Cite this

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title = "Overcoming mechanical stability-flow processability trade-off of vitrimers using ionic interactions",

abstract = "It is well established that the macroscopic flow of dynamic covalent networks involves mesoscopic rearrangement of crosslinkers; however, its relationship with local, segmental motions remains under debate. In this vein, the present study investigates how tuning the segmental (α) dynamics using salt doping impacts the viscoelastic behavior of two vinylogous urethane-based vitrimers. Our analyses show that additional ionic interactions significantly slow down the α relaxation in these materials, driving them into the glassy state at room temperature, while having a much weaker impact on their global dynamics. This disparity allows the separation of the individual contributions of segmental dynamics and network rearrangements to their terminal flow. In addition, our results demonstrate that tuning segmental dynamics, as an alternative to the popular approach of adjusting network rearrangements, can be used for the development of vitrimers that are mechanically rigid and creep resistant at ambient conditions yet flow-processable at moderately high temperatures.",

keywords = "creep-resistant materials, ion doping, ionic interactions, processability, rheology, segmental dynamics, terminal flow, vinylogous urethane, vitrimers",

author = "Harmandeep Singh and Mary Danielson and Ryan Peterson and Ivan Popov and Sokolov, \{Alexei P.\} and Tomonori Saito and Rahman, \{Md Anisur\} and Catalin Gainaru",

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AU - Singh, Harmandeep

AU - Danielson, Mary

AU - Peterson, Ryan

AU - Popov, Ivan

AU - Sokolov, Alexei P.

AU - Saito, Tomonori

AU - Rahman, Md Anisur

AU - Gainaru, Catalin

PY - 2026/7/15

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N2 - It is well established that the macroscopic flow of dynamic covalent networks involves mesoscopic rearrangement of crosslinkers; however, its relationship with local, segmental motions remains under debate. In this vein, the present study investigates how tuning the segmental (α) dynamics using salt doping impacts the viscoelastic behavior of two vinylogous urethane-based vitrimers. Our analyses show that additional ionic interactions significantly slow down the α relaxation in these materials, driving them into the glassy state at room temperature, while having a much weaker impact on their global dynamics. This disparity allows the separation of the individual contributions of segmental dynamics and network rearrangements to their terminal flow. In addition, our results demonstrate that tuning segmental dynamics, as an alternative to the popular approach of adjusting network rearrangements, can be used for the development of vitrimers that are mechanically rigid and creep resistant at ambient conditions yet flow-processable at moderately high temperatures.

AB - It is well established that the macroscopic flow of dynamic covalent networks involves mesoscopic rearrangement of crosslinkers; however, its relationship with local, segmental motions remains under debate. In this vein, the present study investigates how tuning the segmental (α) dynamics using salt doping impacts the viscoelastic behavior of two vinylogous urethane-based vitrimers. Our analyses show that additional ionic interactions significantly slow down the α relaxation in these materials, driving them into the glassy state at room temperature, while having a much weaker impact on their global dynamics. This disparity allows the separation of the individual contributions of segmental dynamics and network rearrangements to their terminal flow. In addition, our results demonstrate that tuning segmental dynamics, as an alternative to the popular approach of adjusting network rearrangements, can be used for the development of vitrimers that are mechanically rigid and creep resistant at ambient conditions yet flow-processable at moderately high temperatures.

KW - creep-resistant materials

KW - ion doping

KW - ionic interactions

KW - processability

KW - rheology

KW - segmental dynamics

KW - terminal flow

KW - vinylogous urethane

KW - vitrimers

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ER -

Overcoming mechanical stability-flow processability trade-off of vitrimers using ionic interactions

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