Skip to main content
SpringerLink
Log in

Miscibility and Phase Separation of Epoxy/Rubber Blends

  • Reference work entry
  • First Online:
Handbook of Epoxy Blends

Abstract

The incorporation of functionalized liquid rubbers is one of the most successful methods to toughen epoxies. These rubbers are initially miscible with epoxy oligomers at a given temperature, however, the reaction-induced phase separation occurs because of the increment in the molecular weight of the epoxy matrix as the curing reaction proceeds, thereby resulting in the precipitation of rubber as a dispersed phase. The properties of the resultant epoxy/rubber blends depend largely on their final morphologies, which in turn are determined by the phase separation of the epoxy/rubber blends in the curing process. In this chapter, we first introduce the thermodynamics of phase separation based on the Flory-Huggins solution theory and then discuss the miscibility of epoxy oligomers with liquid rubbers and some factors affecting the phase separation of epoxy/rubber blends, such as the structural properties of rubber, curing agent, and curing procedure. We also discuss the techniques used to study phase separation. Finally, some critical comments and conclusions are given.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 649.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 849.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • Abadyan M, Bagheri R, Kouchakzadeh MA (2012) J Appl Polym Sci 125:2467

    Article  CAS  Google Scholar 

  • Akbari R, Beheshty MH, Shervin M (2013) Toughening of dicyandiamide-cured DGEBA-based epoxy resins by CTBN liquid rubber. Iran Polym J 22:313–324

    Article  CAS  Google Scholar 

  • Amendt MA, Chen L, Hillmyer MA (2010) Macromolecules 43:3924

    Article  CAS  Google Scholar 

  • Araki T, Tran-Cong Q, Shibayama M (1998) Structure and properties of multi-phase polymeric materials. Dekker, New York, p 155

    Google Scholar 

  • Auad ML, Borrajo J, Aranguren MI (2003) Morphology of rubber-modified vinyl ester resins cured at different temperatures. J Appl Polym Sci 89(1):274–283

    Article  CAS  Google Scholar 

  • Barham B, Fosser K, Voge G, Waldow D (2001) Macromolecules 34:514

    Article  CAS  Google Scholar 

  • Bascom W, Ting R, Moultn RJ, Riew CK, Siebert AR (1981) J Mater Sci 16:2657

    Article  CAS  Google Scholar 

  • Ben Saleh AB, Mohd Ishak ZA, Hashim AS, Kamil WA, Ishiaku US (2014) Synthesis and characterization of liquid natural rubber as impact modifier for epoxy resin. Phys Procedia 55:129–137

    Article  Google Scholar 

  • Bonnet A, Pascault JP, Sautereau H, Camberlin Y (1999) Macromolecules 32:8524

    Article  CAS  Google Scholar 

  • Brandrup J, Immergut EH (1989) Polymer handbook, 3rd edn. Wiley, New York

    Google Scholar 

  • Bucknall CB, Gilbert AH (1989) Toughening tetrafunctional epoxy resins using polyetherimide. Polymer 30(2):213–217

    Article  CAS  Google Scholar 

  • Bucknall C, Partridge I (1983) Phase separation in epoxy resins containing polyethersulphone. Polymer 24(5):639–644

    Article  CAS  Google Scholar 

  • Bucknall CB, Partridge IK (1986) Phase separation in crosslinked resins containing polymeric modifiers. Polym Eng Sci 26(1):54–62

    Article  CAS  Google Scholar 

  • Chan LC, Gillham JK, Kinloch AJ, Shaw SJ (1984) Chapter 15, Chapter 16: Rubber-modified epoxies morphology, transitions, and mechanical properties. In: Riew C et al (eds) Rubber-modified thermoset resins, Advances in chemistry. American Chemical Society, Washington, DC

    Google Scholar 

  • Chen JP, Lee YD (1995) A real-time study of the phase-separation process during polymerization of rubber-modified epoxy. Polymer 36(1):55–65

    Article  CAS  Google Scholar 

  • Chen D, Sautereau H, Pascault JP, Vigier G (1993) Rubber modified epoxies: II. A reaction induced phase separation observed in situ and a posteriori with different methods. Polym Int 32:369

    Article  CAS  Google Scholar 

  • Chen D, Pascault JP, Sautereau H, Ruseckaite RA, Williams RJJ (1994) Rubber-modified epoxies: III. Influence of the rubber molecular weight on the phase separation process. Polym Int 33:253–261

    Article  CAS  Google Scholar 

  • Choe Y, Kim M, Kim W (2003) Macromol Res 11:267

    Article  CAS  Google Scholar 

  • Choi JJ, Bae YC (1999) Liquid-liquid equilibria of polydisperse polymer systems. Eur Polym J 35(9):1703–1711

    Article  CAS  Google Scholar 

  • De Graaf LA, Hempenious MA, Moller M (1995) Polym Prepr 36:787

    CAS  Google Scholar 

  • Dean KM, Cook WD, Lin MY (2006) Small angle neutron scattering and dynamic mechanical thermal analysis of dimethacrylate/epoxy IPNs. Eur Polym J 42:2872–2887

    Article  CAS  Google Scholar 

  • Garg AC, Mai YW (1988) Failure mechanisms in toughened epoxy resins-a review. Compos Sci Technol 31(3):179–223

    Article  CAS  Google Scholar 

  • Gilbert AH, Bucknal CB (1991) Epoxy resin toughened with thermoplastic. Makromol Chem Macromol Symp 45(1):289–298

    Article  CAS  Google Scholar 

  • Girard-Reydet E, Vicard V, Pascaul JP, Sautereau H (1997) Polyetherimide modified epoxy networks: influence of cure conditions on morphology and mechanical properties. J Appl Polym Sci 65(12):2433–2445

    Article  CAS  Google Scholar 

  • Girard-Reydet E, Sautereau H, Pascault JP, Keates P, Navard P, Thollet G, Vigier G (1998) Polymer 39:2269

    Article  CAS  Google Scholar 

  • Grillet AC, Galy J, Pascault JP (1992) Influence of a two-step process and of different cure schedules on the generated morphology of a rubber-modified epoxy system based on aromatic diamines. Polymer 33(1):34–43

    Article  CAS  Google Scholar 

  • Guo Q, Eigueiredo P, Thomann R, Gronski W (2001) Phase behavior, morphology and interfacial structure in thermoset thermoplastic elastomer blends of poly(propylene glycol)-type epoxy resin and polystyrene-b-polybutadiene. Polymer 42:10101–10110

    Article  CAS  Google Scholar 

  • Heng Z, Chen Y, Zou H, Liang M (2015) Simultaneously enhanced tensile strength and fracture toughness of epoxy resins by a poly(ethylene oxide)-block-carboxyl terminated butadiene-acrylonitrile rubber dilock copolymer”. RSC Adv 5:42362

    Article  CAS  Google Scholar 

  • Ho TH, Wang CS (1994) Dispersed acrylate rubber-modified epoxy resins for electronic encapsulation. J Polym Res 1(1):103–108

    Article  CAS  Google Scholar 

  • Hoy KL (1970) J Paint Technol 46:76

    Google Scholar 

  • Inoue T (1995) Prog Polym Sci 20:119

    Article  CAS  Google Scholar 

  • Jenninger W, Schawe JEK, Alig I (2000) Calorimetric studies of isothermal curing of phase separating epoxy networks. Polymer 41:1577–1588

    Article  CAS  Google Scholar 

  • Jiang M (1988) Physical chemistry of polymer blends (Chinese). Sichuan Education Press, Chengdu

    Google Scholar 

  • Jyotishkumar P, Özdilek C, Moldenaers P, Sinturel C, Janke A, Pionteck J, Thomas S (2010) Dynamics of phase separation in poly(acrylonitrile-butadiene-styrene)-modified epoxy/DDS system: kinetics and viscoelastic effects. J Phys Chem B 114:13271–13281

    Article  CAS  Google Scholar 

  • Kiefer J, Hilborn JG, Hedrick JL (1996) Chemically induced phase separation: a new technique for the synthesis of macroporous epoxy networks. Polymer 37(25):5715–5725

    Article  CAS  Google Scholar 

  • Kim DS, Kim SC (1994) Rubber modified epoxy resin. II: phase separation behavior. Polym Eng Sci 34(21):1598–1604

    Article  CAS  Google Scholar 

  • Kim BS, Chiba T, Inoue T (1993) Polymer 34:2809

    Article  CAS  Google Scholar 

  • Kinloch AJ, Shaw SJ, Tod DA, Hunston DL (1983) Deformation and fracture behaviour of a rubber-toughened epoxy: 1. Microstructure and fracture studies. Polymer 24(83):1341–1354

    Article  CAS  Google Scholar 

  • Koningsveld R, Staverman AJ (1968) Liquid-liquid phase separation in multicomponent polymer solutions. I. Statement of the problem and description of methods of calculation. J Polym Sci A Polym Chem 6(2):305–323

    CAS  Google Scholar 

  • Lee BL, Lizak CM, Riew CK, Moulton RJ (1982) Rubber toughening of tetrafunctional epoxy resin. BF Goodrich internal report

    Google Scholar 

  • Liu Y (2013) Polymerization-induced phase separation and resulting thermomechanical properties of thermosetting/reactive nonlinear polymer blends: a review. J Appl Polym Sci 127(5):3279–3292

    Article  CAS  Google Scholar 

  • Liu XY, Zhan GZ, Yu YF, Li SJJ (2006) J Polym Sci B Polym Phys 44:3102

    Article  CAS  Google Scholar 

  • Liu XQ, Xin WB, Zhang JW (2009) Green Chem 11:1018–1025

    Article  CAS  Google Scholar 

  • Liu Y, Wang J, Xu S (2014) Synthesis and curing kinetics of cardanol-based curing agents for epoxy resin by in-situ depolymerisation of paraformaldehyde. J Polym Sci A Polym Chem 52(4):472–480

    Article  CAS  Google Scholar 

  • Mathew VS, Sinturel C, George SC, Thomas S (2010) Epoxy resin/liquid natural rubber system: secondary phase separation and its impact on mechanical properties. J Mater Sci 45:1769–1781

    Article  CAS  Google Scholar 

  • Mathew VS, George SC, Parameswaranpillai J, Thomas S (2014) Epoxidized natural rubber/epoxy blends: phase morphology and thermomechanical properties. J Appl Polym Sci 131(4):39906

    Article  Google Scholar 

  • Mezzeng R, Plummer CJG, Boogh L, Månson JAE (2001) Morphology build-up in dendritic hyperbranched polymer modified epoxy resins: modelling and characterization. Polymer 42:305–317

    Article  Google Scholar 

  • Mohan P (2013) Polym Plast Technol Eng 52:107–125

    Article  CAS  Google Scholar 

  • Montarnal S, Pascault JP, Sautereau H (1986) In: Mé1anges de Polymères. GFP, Trasbourg, p 279

    Google Scholar 

  • Müller Y, Häußler L, Pionteck J (2007) Macromol Symp 254:267

    Article  Google Scholar 

  • Olabisi O, Robeson LM, Shaw MT (1979) Polymer-polymer miscibility. Academic, New York

    Google Scholar 

  • Park JW, Kim SC (1997) In: Kim SC, Sperling LH (eds) IPNs around the world, science and engineering. Springer, Chichester, p 27

    Google Scholar 

  • Parker DS, Sue HJ, Huang J, Yee AF (1990) Toughening mechanisms in core-shell rubber modified polycarbonate. Polymer 31:2267–2277

    Article  CAS  Google Scholar 

  • Plummer CJG, Mezzenga R, Boogh L, Månson JAE (2001) Polym Eng Sci 41:43

    Article  CAS  Google Scholar 

  • Rao BS, Pathak SK (2006) J Appl Polym Sci 100:3956–3965

    Article  CAS  Google Scholar 

  • Ratna D (2001) Phase separation in liquid rubber modified epoxy mixture. Relationship between curing conditions, morphology and ultimate behavior. Polymer 42:4209–4218

    Article  CAS  Google Scholar 

  • Ratna D, Banthia AK (2004) Rubber toughened epoxy. Macromol Res 12(1):11–21

    Article  CAS  Google Scholar 

  • Remiro PM, Marieta C, Riccardi CC, Mondragon I (2001) Influence of curing conditions on the morphologies of a PMMA-modified epoxy matrix. Polymer 42(25):9909–9914

    Article  CAS  Google Scholar 

  • Rohde BJ, Robertson ML, Krishnamoorti R (2015) Concurrent curing kinetics of an anhydride-cured epoxy resin and polydicyclopentadiene. Polymer 69:204–214

    Article  CAS  Google Scholar 

  • Romo-Uribe A, Arcos-Casarrubias JA, Flores A, Valerio-CáRdenas C, González AE (2014) Influence of rubber on the curing kinetics of DGEBA epoxy and the effect on the morphology and hardness of the composites. Polym Bull 71:1241–1262

    Article  CAS  Google Scholar 

  • Sanchez IC, Stone MT (2000) Chapter 2: Statistical thermodynamics of polymer solutions and blends. In: Paul DR, Bucknall CB (eds) Polymer blends. Wiley, New York

    Google Scholar 

  • Serrano E, Kortaberria G, Arruti P, Tercjak A, Mondragon I (2009) Eur Polym J 45:1046

    Article  CAS  Google Scholar 

  • Small PA (1953) J Appl Chem 3:71

    Article  CAS  Google Scholar 

  • Soulé ER, Eliçabe GE, Borrajo J, Williams RJJ (2007) Analysis of the phase separation induced by a free-radical polymerization in solutions of polyisobutylene in isobornyl methacrylate. Ind Eng Chem Res 46:7535–7542

    Article  Google Scholar 

  • Sperling LH (2006) Introduction to physical polymer science, 4th edn. Wiley, New York

    Google Scholar 

  • Stefani PM, Riccardi CC, Remiro PM, Mondragón I (2001) Morphology profiles generated by temperature gradient in PMMA modified epoxy system. Polym Eng Sci 41(11):2013–2021

    Article  CAS  Google Scholar 

  • Sue H (1991) J Polym Eng 31:275

    Article  CAS  Google Scholar 

  • Tanaka H (2000) Viscoelastic phase separation. J Phys Condens Matter 12(15):R207–R264

    Article  CAS  Google Scholar 

  • Tang XL, Zhao L, Li L, Zhang HD, Wu PY (2007) Acta Chim Sin 65:2449

    CAS  Google Scholar 

  • Thomas R, Abraham J, Selvin P, Thomas S (2004) Influence of carboxyl-terminated (butadiene-coacrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends. J Polym Sci B Polym Phys 42:2531–2544

    Article  CAS  Google Scholar 

  • Tian X, Geng Y, Yin D, Zhang B, Zhang Y (2011) Polym Test 30:16

    Article  Google Scholar 

  • Verchère D, Sautereau H, Pascault JP, Moschiar SM, Riccardi CC, Williams RJJ (1989) Miscibility of epoxy monomers with carboxyl-terminated butadiene acrylonitrile random copolymers. Polymer 30:107–115

    Article  Google Scholar 

  • Wang TT, Zupko HM (1981) Phase separation behavior of rubber-modified epoxies. J Appl Polym Sci 26:2391–2401

    Article  CAS  Google Scholar 

  • Wàtzquez A, Rojas AJ, Adabbo HE, Borrajo J, Williams RJJ (1987) Polymer 28:1156

    Article  Google Scholar 

  • Williams RJJ, Rozenberg BA, Pascault JP (1997) Adv Polym Sci 128:95

    Article  CAS  Google Scholar 

  • Wise CW, Cook WD, Goodwin AA (2000) Rubber phase precipitation in model epoxy resins. Polymer 41:4625–4633

    Article  CAS  Google Scholar 

  • Wu S, Guo Q, Kraska M, Bernd S, Mai YW (2013) Toughening epoxy thermosets with block ionomers: the role of phase domain size. Macromolecules 46:8190–8202

    Article  CAS  Google Scholar 

  • Xu SA, Wang GT, Mai YW (2013) Effect of hybridization of liquid rubber and nanosilica particles on the morphology, mechanical properties, and fracture toughness of epoxy composites. J Mater Sci 48(9):3546–3556

    Article  CAS  Google Scholar 

  • Yahyaie H, Ebrahimi M, Tahami HV, Mafi ER (2013) Toughening mechanisms of rubber modified thin film epoxy resins. Prog Org Coat 76:286–292

    Article  CAS  Google Scholar 

  • Yamanaka K, Inoue T (1990) Phase separation mechanism of rubber-modified epoxy. J Mater Sci 25:241–245

    Article  CAS  Google Scholar 

  • Yamanaka K, Takagi Y, Inoue T (1989) Reaction-induced phase separation in rubber-modified epoxy resins. Polymer 30:1839–1844

    Article  CAS  Google Scholar 

  • Yee AF, Du J (2000) Toughening of epoxies. In: Polymer blends, Paul DR, Bucknall CB (eds) vol 2. Wiley, New York, p 225

    Google Scholar 

  • Yee AF, Pearson RA (1986) Toughening mechanisms in elastomer-modified epoxies. Part 1 Mechanical studies. J Mater Sci 21:2462–2474

    Article  CAS  Google Scholar 

  • Yu YF, Wang MH, Gan WJ, Tao QS, Li SJ (2004) J Phys Chem B 108:6208

    Article  CAS  Google Scholar 

  • Zhang J, Zhang H, Yan D, Zhou H, Yang Y (1997) Reaction-induced phase separation in rubber-modified epoxy resin. Sci China B 40(1):15–23

    Article  CAS  Google Scholar 

  • Zhao K, Song XX, Liang CS, Wang J, Xu SA (2015a) Morphology and properties of nanostructured epoxy blends toughened with epoxidized carboxyl-terminated liquid rubber. Iran Polym J 24(5):425–435

    Article  CAS  Google Scholar 

  • Zhao K, Wang J, Song XX, Liang CS, Xu SA (2015b) Curing kinetics of nanostructured epoxy blends toughened with epoxidized carboxyl-terminated liquid rubber. Thermochim Acta 605:8–15

    Article  CAS  Google Scholar 

  • Zhou HS, Song XX, Xu SA (2014) Mechanical and thermal properties of novel rubber -toughened epoxy composite prepared via in-situ pre-crosslinking. J Appl Polym Sci 131(22):41110

    Article  Google Scholar 

  • Zielinski JM, Vratsanos MS, Laurer JH, Spontak RJ (1996) Phase-separation on studies of heat-cured ATU-flexibilized epoxies. Polymer 37(1):75–84

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Polymer Engineering and Science, School of Materials Science and Engineering, East China University of Science and Technology, 130 Mei-Long Road, P.O. Box 289, 200237, Shanghai, China

    Shi-Ai Xu

Authors
  1. Shi-Ai Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shi-Ai Xu .

Editor information

Editors and Affiliations

  1. Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi, India

    Jyotishkumar Parameswaranpillai

  2. Institute for Frontier Materials, Deakin University, Geelong, Victoria, Australia

    Nishar Hameed

  3. Leibniz-Institut für Polymerforschung Dresden e.V., Dresden, Germany

    Jürgen Pionteck

  4. Department of Chemical Engineering, National Cheng Kung University, Taiwan, China

    Eamor M. Woo

Rights and permissions

Reprints and permissions

Copyright information

© 2017 Springer International Publishing AG

About this entry

Cite this entry

Xu, SA. (2017). Miscibility and Phase Separation of Epoxy/Rubber Blends. In: Parameswaranpillai, J., Hameed, N., Pionteck, J., Woo, E. (eds) Handbook of Epoxy Blends. Springer, Cham. https://doi.org/10.1007/978-3-319-40043-3_3

Download citation

Publish with us

Policies and ethics

Search

Navigation