Journal of Materials Science

, Volume 47, Issue 8, pp 3493–3503 | Cite as

Characterization of double network epoxies with tunable compositions



This article reports the processing and characterization of epoxy resins with near constant molar cross-link density prepared from sequentially reacted amine cross-linking agents. Stoichiometric blends of curing agents with compositions ranging from all polyetheramine to all diaminodiphenylsulfone (DDS) are reacted with an epoxy monomer in a staged curing procedure. The low reactivity of the aromatic amine permits the selective reaction of the aliphatic amine in the first stage. The residual aromatic amine and epoxide functionality are reacted in a second stage at higher temperature. Above approximately 50% DDS content the first stage produces sol glasses which have not reached the gel point. The glass transition temperatures of the partially cured networks decrease monotonically with increasing DDS content. The partially cured networks can be characterized thermally and mechanically above their respective glass transitions without significantly advancing the reaction of the residual DDS and epoxide functionality. The networks formed after the second stage of the cure exhibit thermal and mechanical properties intermediate between those of the two individual amine cured networks, according to composition. The blends do not show any evidence of phase separation across the entire composition range in either the partially cured or fully cured state.


True Stress Aliphatic Amine Dynamic Mechanical Thermal Analysis Entanglement Density PEAs 


  1. 1.
    Ellis B (1993) Chemistry and technology of epoxy resins. Chapman and Hall, New YorkGoogle Scholar
  2. 2.
    Bucknall CB, Partridge IK (1983) Polymer 24(5):639CrossRefGoogle Scholar
  3. 3.
    Wu WL, Bauer BJ (1989) Polymer 30:1384CrossRefGoogle Scholar
  4. 4.
    Beck Tan NC, Bauer BJ, Plestil J, Barnes JD, Liu D, Matejka L et al (1999) Polymer 40:4603CrossRefGoogle Scholar
  5. 5.
    Wu WL, Hu JT, Hunston DL (1990) Polym Eng Sci 30(14):835CrossRefGoogle Scholar
  6. 6.
    Philipson J (1959) Method and composition for curing epoxy resins. Patent 2891927Google Scholar
  7. 7.
    Lahlali N, Naffakh M, Dumon M (2005) Polym Eng Sci 45:1581CrossRefGoogle Scholar
  8. 8.
    Wiggins PL (1988) Epoxy curing agent composition. USA patent 4,775,736Google Scholar
  9. 9.
    Tesch H, Heym M, Doerflinger W, Stutz H, Neumann P, Nissen D, et al (1988) Curable compositions based on epoxy resins. USA patent RE32,628Google Scholar
  10. 10.
    de Nograro FF, Llano-Ponte R, Mondragon I (1996) Polymer 37(9):1589CrossRefGoogle Scholar
  11. 11.
    Nakajima T, Furukawa H, Tanaka Y, Kurokawa T, Osada Y, Gong JP (2009) Macromolecules 42:2184CrossRefGoogle Scholar
  12. 12.
    Singh NK, Lesser AJ (2010) Macromolecules 44:1480Google Scholar
  13. 13.
    Thiele JL, Cohen RE (1979) Polym Eng Sci 19(4):284CrossRefGoogle Scholar
  14. 14.
    Bellenger V, Dhaoui W, Verdu J (1990) Polym Eng Sci 30(6):321CrossRefGoogle Scholar
  15. 15.
    Jordan C, Galy J, Pascualt JP (1992) J Appl Polym Sci 46:859CrossRefGoogle Scholar
  16. 16.
    Detwiler AT, Lesser AJ (2010) J Appl Polym Sci 117:1021CrossRefGoogle Scholar
  17. 17.
    Flory PJ (1941) J Am Chem Soc 63:3083CrossRefGoogle Scholar
  18. 18.
    Cook WD, Scott TF, Quay-Thevenon S, Forsythe JS (2004) J Appl Polym Sci 93:1349CrossRefGoogle Scholar
  19. 19.
    Adam G, Gibbs JH (1965) J Chem Phys 43(1):139CrossRefGoogle Scholar
  20. 20.
    Boyer RF (1963) Rubber Chem Technol 46:1303CrossRefGoogle Scholar
  21. 21.
    Hale A, Macosko CW, Bair HE (1991) Macromolecules 24:2610CrossRefGoogle Scholar
  22. 22.
    Lovell R, Windle AH (1990) Polymer 31(4):593CrossRefGoogle Scholar
  23. 23.
    Wu Wl, Bauer BJ (1986) Polymer 27:169CrossRefGoogle Scholar
  24. 24.
    Arruda EM, Boyce MC (1993) Int J Plasticity 9:697CrossRefGoogle Scholar
  25. 25.
    Kovacs AJ, Aklonis JJ, Hutchinson JM, Ramos AR (1979) J Polym Sci: B Polym Phys 17:1097Google Scholar
  26. 26.
    Lesser AJ, Calzia KJ (2004) J Polym Sci B: Polym Phys 42:2050CrossRefGoogle Scholar
  27. 27.
    Crawford ED, Lesser AJ (1998) J Polym Sci: B Polym Phys 36:1371CrossRefGoogle Scholar
  28. 28.
    van Melick HGH, Govaert LE, Meijer HEH (2003) Polymer 44:2493CrossRefGoogle Scholar
  29. 29.
    Cross A, Haward RN (1978) Polymer 19:677CrossRefGoogle Scholar
  30. 30.
    Treloar LRG (1975) The physics of rubber elasticity. Clarendon Press, OxfordGoogle Scholar
  31. 31.
    Arruda EM, Boyce MC, Jayachandran R (1995) Mech Mater 19:193CrossRefGoogle Scholar
  32. 32.
    Haward RN, Thackray G (1968) Proc R Soc Lond A 302:453CrossRefGoogle Scholar
  33. 33.
    Tervoort TA, Govaert LE (2000) J Rheol 44(6):1263CrossRefGoogle Scholar
  34. 34.
    Charlesworth JM (1988) Polym Eng Sci 28(4):230CrossRefGoogle Scholar
  35. 35.
    Porter RS, Johnson JF (1966) Chem Rev 66(1):1CrossRefGoogle Scholar
  36. 36.
    Hoy RS, Robbins MO (2006) J Polym Sci: B Polym Phys 44:3487CrossRefGoogle Scholar
  37. 37.
    Haward RN, Young RJ (1997) The physics of glassy polymers. Chapman and Hall, New YorkCrossRefGoogle Scholar
  38. 38.
    Wendlandt M, Tervoort TA, Suter UW (2010) J Polym Sci: B Polym Phys 48:1464CrossRefGoogle Scholar
  39. 39.
    Govaert LE, Engels TAP, Wendlandt M, Tervoort T, Suter UW (2008) J Polym Sci: B Polym Phys 46:2475CrossRefGoogle Scholar
  40. 40.
    Lesser AJ, Crawford E (1997) J Appl Polym Sci 66:387CrossRefGoogle Scholar
  41. 41.
    Fox TG, Loshaek S (1955) J Polym Sci 15:371CrossRefGoogle Scholar
  42. 42.
    Espuche E, Galy J, Gerard JF, Pascualt JP, Sautereau H (1995) Macromol Symp 93:107CrossRefGoogle Scholar
  43. 43.
    Robertson RE (1966) J Chem Phys 44(10):3950CrossRefGoogle Scholar
  44. 44.
    Calzia KJ, Lesser AJ (2007) J Mater Sci 32:5229. doi: 10.1007/s10853-006-1268-0 CrossRefGoogle Scholar
  45. 45.
    Bree HW, Heijboer J, Struik LCE, Tak AGM (1974) J Polym Sci: B Polym Phys 12:1857Google Scholar
  46. 46.
    Charlesworth JM (1988) Polym Eng Sci 28(4):221CrossRefGoogle Scholar
  47. 47.
    G’Sell C, McKenna GB (1992) Polymer 33(10):2103CrossRefGoogle Scholar
  48. 48.
    Wang X, Gillham JK (1993) J Appl Polym Sci 47:447CrossRefGoogle Scholar
  49. 49.
    Boyce MC, Arruda EM (2000) Rubber Chem Technol 73(3):504CrossRefGoogle Scholar
  50. 50.
    Rivlin RS, Saunders DW (1951) Philos Trans R Soc Lond A 243:251CrossRefGoogle Scholar
  51. 51.
    Bicerano J (2002) Prediction of polymer properties, 3rd edn. Marcel Dekker, Inc., New YorkCrossRefGoogle Scholar
  52. 52.
    Bicerano J, Sammler RL, Carriere CJ, Seitz JT (1996) J Polym Sci: B Polym Phys 34:2247CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  1. 1.University of Massachusetts AmherstAmherstUSA

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