Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers

Cody T. Bezik; Erica M. Redline; Jeffrey C. Foster; Amalie L. Frischknecht

doi:10.1021/acs.macromol.3c00924

Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers

Cody T. Bezik, Erica M. Redline, Jeffrey C. Foster, Amalie L. Frischknecht

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

1 Scopus citations

Abstract

This work explores the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks, focusing on the glass transition temperature (T_g) and Young’s modulus (Y). We used coarse-grained molecular dynamics simulations to simulate varying compositions of stiff and flexible components in epoxy monomer blends with varying excess of curative. We find that, without hydrogen bonding, networks of any composition show a monotonically increasing T_g with decreasing excess curative, consistent with theory. In contrast, we find that when hydrogen bonding is introduced, the binary blend networks show significant enhancement in T_g for lightly crosslinked systems. This result contributes to an explanation of the anomalous T_g behavior observed experimentally in these systems. We further find that Y is generally enhanced by hydrogen bonds, especially below T_g, demonstrating that hydrogen bonding has a significant influence on mechanical properties and can allow access to other desirable dynamic behavior, especially self-healing.

Original language	English
Pages (from-to)	5268-5277
Number of pages	10
Journal	Macromolecules
Volume	56
Issue number	14
DOIs	https://doi.org/10.1021/acs.macromol.3c00924
State	Published - Jul 25 2023
Externally published	Yes

Funding

This work was supported by the Laboratory Directed Research and Development program at Sandia National Laboratories. This work was performed in part at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U. S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by the National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy (DOE) or the U.S. Government.

Funders	Funder number
U.S. Department of Energy
Office of Science
National Nuclear Security Administration	DE-NA-0003525
Sandia National Laboratories
Laboratory Directed Research and Development

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10.1021/acs.macromol.3c00924

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title = "Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers",

abstract = "This work explores the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks, focusing on the glass transition temperature (Tg) and Young{\textquoteright}s modulus (Y). We used coarse-grained molecular dynamics simulations to simulate varying compositions of stiff and flexible components in epoxy monomer blends with varying excess of curative. We find that, without hydrogen bonding, networks of any composition show a monotonically increasing Tg with decreasing excess curative, consistent with theory. In contrast, we find that when hydrogen bonding is introduced, the binary blend networks show significant enhancement in Tg for lightly crosslinked systems. This result contributes to an explanation of the anomalous Tg behavior observed experimentally in these systems. We further find that Y is generally enhanced by hydrogen bonds, especially below Tg, demonstrating that hydrogen bonding has a significant influence on mechanical properties and can allow access to other desirable dynamic behavior, especially self-healing.",

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PY - 2023/7/25

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AB - This work explores the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks, focusing on the glass transition temperature (Tg) and Young’s modulus (Y). We used coarse-grained molecular dynamics simulations to simulate varying compositions of stiff and flexible components in epoxy monomer blends with varying excess of curative. We find that, without hydrogen bonding, networks of any composition show a monotonically increasing Tg with decreasing excess curative, consistent with theory. In contrast, we find that when hydrogen bonding is introduced, the binary blend networks show significant enhancement in Tg for lightly crosslinked systems. This result contributes to an explanation of the anomalous Tg behavior observed experimentally in these systems. We further find that Y is generally enhanced by hydrogen bonds, especially below Tg, demonstrating that hydrogen bonding has a significant influence on mechanical properties and can allow access to other desirable dynamic behavior, especially self-healing.

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Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers

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