Synergistic Toughening of Epoxy Modified by Graphene and Block Copolymer Micelles

Research output: Contribution to journalArticlepeer-review

33 Scopus citations


Binary composites formed by individually mixing exfoliated graphene oxide modified with amine-terminated poly(butadiene-acrylonitrile) (GA) and a spherical micelle forming poly(ethylene oxide)-b-poly(ethylene-alt-propylene) (OP) diblock copolymer with a thermoset epoxy, and the associated GA/OP/epoxy ternary composites, were prepared and studied as a function of the molecular weight Mc between cross-links. The rigid GA filler dispersed well in the cured epoxies as established by transmission electron microscopy (TEM). The toughening efficacy of GA alone was found to depend strongly on the modifier concentration and the matrix cross-link density with an optimal 1.7-fold increase in the critical strain energy release rate (GIc) over the neat epoxy obtained with a 0.04 wt % loading in the most lightly cross-linked (Mc = 6100 g/mol) material. Addition of 5 wt % OP to this epoxy resin enhanced GIc by a factor of 12. Combining the hard GA and soft OP modifiers at the same loading levels (0.04 and 5 wt %, respectively) resulted in 18 times the GIc of the unmodified material, a 31% improvement over the effect anticipated by simple addition of the fracture properties of the binary composites. Decreasing Mc to 700 g/mol eliminated this synergistic effect while reducing the overall improvement in GIc to just 3 times that of the neat epoxy. Topological features on the fracture surfaces, imaged using a scanning electron microscope (SEM), suggest that the synergistic toughening of the GA/OP/epoxy ternary composite involves concurrent mechanisms operating on different length scales, including micelle cavitation and graphene debonding, resulting in simultaneous shear yielding, crack pinning, and crack deflection.

Original languageEnglish (US)
Pages (from-to)9507-9520
Number of pages14
Issue number24
StatePublished - Dec 27 2016

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation through the University of Minnesota MRSEC under Award Number DMR-1420013. T.L. acknowledges support from the University of Minnesota Doctoral Dissertation Fellowship program.

Publisher Copyright:
© 2016 American Chemical Society.

Copyright 2017 Elsevier B.V., All rights reserved.

How much support was provided by MRSEC?

  • Partial

Reporting period for MRSEC

  • Period 3

Fingerprint Dive into the research topics of 'Synergistic Toughening of Epoxy Modified by Graphene and Block Copolymer Micelles'. Together they form a unique fingerprint.

Cite this