Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

The role of β relaxations in controlling compressive properties in hyperbranched polymer-modified epoxy networks


In this work, a largely miscible second-generation aliphatic polyester hyperbranched polymer (HBP) is used as a modifier in a cured epoxy amine network to explore molecular mobility in the glassy state and its impact on compressive properties. The β relaxation determined by dynamic mechanical analysis is used as a measure of short-range motion in the glassy state and is related to the compressive modulus and yield properties. The parameters explored include an increased HBP concentration, enhanced HBP, and epoxy matrix interactions through pre-reaction via a rigid covalent linkage and a modified epoxy network of flexible butanediol diglycidyl ether (BDDGE) and highly crosslinkable tetraglycidyl diamino diphenyl methane (TGDDM). The β relaxation peaks are analyzed in terms of their area, FWHM, and position (Tβ) and are observed to correlate strongly with changes in the modulus, yield stress, and strain.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others


  1. Vidil T, Tournilhac F, Musso S, Robisson A, Leibler L. Control of reactions and network structures of epoxy thermosets. Prog Polym Sci. 2016;62:126–79.

    Article  CAS  Google Scholar 

  2. Francois C, Pourchet S, Boni G, Rautiainen S, Samec J, Fournier L, et al. Design and synthesis of biobased epoxy thermosets from biorenewable resources. Comptes Rendus Chim. 2017;20:1006–16.

    Article  CAS  Google Scholar 

  3. Tian N, Ning RC, Kong J. Self-toughening of epoxy resin through controlling topology of cross-linked networks. Polymer. 2016;99:376–85.

    Article  CAS  Google Scholar 

  4. Wu JH, Xiao CD, Yee AF, Klug CA, Schaefer J. Controlling molecular mobility and ductile-brittle transitions of polycarbonate copolymers. J Polym Sci Part B-Polym Phys. 2001;39:1730–40.

    Article  CAS  Google Scholar 

  5. Fei XM, Wei W, Tang YY, Zhu Y, Luo J, Chen MQ, et al. Simultaneous enhancements in toughness, tensile strength, and thermal properties of epoxy-anhydride thermosets with a carboxyl-terminated hyperbranched polyester. Eur Polym J. 2017;90:431–41.

    Article  CAS  Google Scholar 

  6. Liu HC, Zhang JQ, Gao XX, Huang GS. Simultaneous reinforcement and toughness improvement of an epoxy-phenolic network with a hyperbranched polysiloxane modifier. Rsc Adv. 2018;8:17606–15.

    Article  CAS  Google Scholar 

  7. Misasi JM, Jin QF, Knauer KM, Morgan SE, Wiggins JS. Hybrid poss-hyperbranched polymer additives for simultaneous reinforcement and toughness improvements in epoxy networks. Polymer. 2017;117:54–63.

    Article  CAS  Google Scholar 

  8. Wang YM, Chen SF, Chen XC, Lu YF, Miao MH, Zhang DH. Controllability of epoxy equivalent weight and performance of hyperbranched epoxy resins. Compos Part B-Eng. 2019;160:615–25.

    Article  CAS  Google Scholar 

  9. Cook WD, Mayr AE, Edward GH. Yielding behaviour in model epoxy thermosets—ii. Temp Depend, Polym. 1998;39:3725–33.

    Google Scholar 

  10. Mayr AE, Cook WD, Edward GH. Yielding behaviour in model epoxy thermosets—i. Effect of strain rate and composition. Polymer. 1998;39:3719–24.

    Article  CAS  Google Scholar 

  11. Espuche E, Galy J, Gerard JF, Pascault JP, Sautereau H. Influence of cross-link density and chain flexibility on mechanical-properties of model epoxy networks. Macromol Symposia. 1995;93:107–15.

    Article  CAS  Google Scholar 

  12. Urbaczewskiespuche E, Galy J, Gerard JF, Pascault JP, Sautereau H. Influence of chain flexibility and cross-link density on mechanical-properties of epoxy amine networks. Polym Eng Sci. 1991;31:1572–80.

    Article  CAS  Google Scholar 

  13. Oleinik EF. Epoxy-aromatic amine networks in the glassy state structure and properties. Adv Polym Sci. 1986;80:49–99.

    Article  CAS  Google Scholar 

  14. Heux L, Halary JL, Laupretre F, Monnerie L. Dynamic mechanical and c-13 nmr investigations of molecular motions involved in the beta relaxation of epoxy networks based on dgeba and aliphatic amines. Polymer. 1997;38:1767–78.

    Article  CAS  Google Scholar 

  15. Heux L, Laupretre F, Halary JL, Monnerie L. Dynamic mechanical and c-13 nmr analyses of the effects of antiplasticization on the beta secondary relaxation of aryl-aliphatic epoxy resins. Polymer. 1998;39:1269–78.

    Article  CAS  Google Scholar 

  16. Shi JF, Inglefield PT, Jones AA, Meadows MD. Sub-glass transition motions in linear and cross-linked bisphenol-type epoxy resins by deuterium line shape nmr. Macromolecules. 1996;29:605–9.

    Article  CAS  Google Scholar 

  17. Hardis R, Jessop JLP, Peters FE, Kessler MR. Cure kinetics characterization and monitoring of an epoxy resin using dsc, raman spectroscopy, and dea. Compos Part a-Appl Sci Manuf. 2013;49:100–8.

    Article  CAS  Google Scholar 

  18. Scherzer T. Ftir-rheo-optical characterization of the molecular orientation behaviour of amine cured epoxy resins during cyclic deformation. Polymer. 1996;37:5807–16.

    Article  CAS  Google Scholar 

  19. Scherzer T. Characterization of the molecular deformation behavior of glassy epoxy resins by rheo-optical ftir spectroscopy. J Polym Sci Part B-Polym Phys. 1996;34:459–70.

    Article  CAS  Google Scholar 

  20. Heinz S, Tu JW, Jackson M, Wiggins J. Digital image correlation analysis of strain recovery in glassy polymer network isomers. Polymer. 2016;82:87–92.

    Article  CAS  Google Scholar 

  21. Ramsdale-Capper R, Foreman JP. Internal antiplasticisation in highly crosslinked amine cured multifunctional epoxy resins. Polymer. 2018;146:321–30.

    Article  CAS  Google Scholar 

  22. Tu JW, Tucker SJ, Christensen S, Sayed AR, Jarrett WL, Wiggins JS. Phenylene ring motions in isomeric glassy epoxy networks and their contributions to thermal and mechanical properties. Macromolecules. 2015;48:1748–58.

    Article  CAS  Google Scholar 

  23. Jin QF, Misasi JM, Wiggins JS, Morgan SE. Simultaneous reinforcement and toughness improvement in an aromatic epoxy network with an aliphatic hyperbranched epoxy modifier. Polymer. 2015;73:174–82.

    Article  CAS  Google Scholar 

  24. Pham S, Burchill PJ. Toughening of vinyl ester resins with modified polybutadienes. Polymer. 1995;36:3279–85.

    Article  CAS  Google Scholar 

  25. Lee SE, Jeong E, Lee MY, Lee MK, Lee YS. Improvement of the mechanical and thermal properties of polyethersulfone-modified epoxy composites. J Ind Eng Chem. 2016;33:73–9.

    Article  CAS  Google Scholar 

  26. Matejka L, Amici Kroutilova I, Lichtenhan JD, Haddad TS. Structure ordering and reinforcement in poss containing hybrids. Eur Polym J. 2014;52:117–26.

    Article  CAS  Google Scholar 

Download references


This work was partially supported by The Australian Research Council (DP180100094).

Author information

Authors and Affiliations


Corresponding author

Correspondence to Russell J. Varley.

Ethics declarations

Conflict of interest

The authors declares that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Reyes, L.Q., Swan, S.R., Gan, H. et al. The role of β relaxations in controlling compressive properties in hyperbranched polymer-modified epoxy networks. Polym J 53, 393–401 (2021).

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links