Shelf-life of polyfurfuryl alcohol resin: an accelerated rheokinetics study

  • Abbas Behzadfar
  • Mohammad ImaniEmail author
  • Farhid Farahmandghavi
Original Paper


Thermosetting resins like polyfurfuryl alcohol (PFA) tend to get prematurely cured and viscous during storage. Understanding a resin shelf-life is very helpful but no definite and validated method could be found in both scientific literature and standard methods. Cure kinetics of PFA was determined through tracing the complex viscosity changes as a function of time at elevated temperatures of 160, 170, 180, 190 and 200 °C. Adopting an empirical statistical approach, shelf-life of PFA resin at ambient temperature was estimated using the accelerated cure profiles. To this end, two functions were fitted on experimental results and then the empirical cure reaction rate constants at different temperatures were extrapolated to 25 °C. Subsequently, the viscosity versus time profiles were built for curing the resin at ambient temperature. The time interval corresponding to a viscosity range of 10–12.5 Pa.s was considered as the practical shelf-life of the resin at ambient conditions. The findings were validated by comparing the model results to the real-time, experimentally-obtained values.


Rheokinetics Curing reaction Polyfurfuryl alcohol Shelf-life Model fitting 



Hereby, we express our sincere gratitude to Iran Polymer and Petrochemical Institute for supporting this research.


  1. 1.
    Kutz M (2015) Mechanical engineers’ handbook, vol 1: materials and engineering mechanics, 4th edn. Wiley, LondonGoogle Scholar
  2. 2.
    Mital A, Desai A, Subramanian A, Mital A (2014) Product development: a structured approach to consumer product development, design, and manufacture, 2nd edn. Butterworth-Heinemann, LondonGoogle Scholar
  3. 3.
    Dodiuk H, Goodman SH (2013) Handbook of thermoset plastics, 3rd edn. Elsevier Science, AmsterdamGoogle Scholar
  4. 4.
    NPCS Board of Consultants and Engineers (2014) Disposable products manufacturing handbook. NIIR Project Consultancy ServicesGoogle Scholar
  5. 5.
    Whelan T, Goff J (2012) Molding of thermosetting plastics. Springer, LondonGoogle Scholar
  6. 6.
    Pascault JP, Sautereau H, Verdu J, Williams RJJ (2002) Thermosetting polymers. CRC Press, AmsterdamCrossRefGoogle Scholar
  7. 7.
    De Miranda LF, Vale M, Júnior AHM, Masson TJ, e Silva LGDA (2016) Zinc chloride influence on the resins furan polymerization to foundry moulds. In: Ikhmayies SJ et al (eds) Characterization of minerals, metals, and materials. Springer, London, pp 771–778Google Scholar
  8. 8.
    Wang Z, Cao N, He J, Du R, Liu Y, Zhao G (2017) Mechanical and anticorrosion properties of furan/epoxy-based basalt fiber-reinforced composites. J Appl Polym Sci 134:44799. Google Scholar
  9. 9.
    Balasubramanian M (2017) Composite materials and processing. CRC Press, AmsterdamGoogle Scholar
  10. 10.
    Astrom BT (1997) Manufacturing of polymer composites. CRC Press, AmsterdamGoogle Scholar
  11. 11.
    Berins M (1991) SPI plastics engineering handbook of the society of the plastics industry. Springer, USACrossRefGoogle Scholar
  12. 12.
    Harper CA, Petrie EM (2008) Plastics materials and processes: a concise encyclopedia. Wiley, LondonGoogle Scholar
  13. 13.
    Halley PJ, Mackay ME (1996) Chemorheology of thermosets-an overview. Polym Eng Sci 36:593–609. CrossRefGoogle Scholar
  14. 14.
    Woo L, Palomo J, Ling MTK, Chan EK, Sandford C (1996) Shelf-life prediction methods and applications. Med Plast Biomater 3:36–40Google Scholar
  15. 15.
    Smith HM (1981) Shelf life determination of an epoxy resin by accelerated aging. Final report. Bendix Corp, Kansas CityGoogle Scholar
  16. 16.
    Zarrelli M, Skordos AA, Partridge IK (2010) Toward a constitutive model for cure-dependent modulus of a high temperature epoxy during the cure. Eur Polym J 46:1705–1712. CrossRefGoogle Scholar
  17. 17.
    Marefat Seyedlar R, Imani M, Mirabedini SM (2016) Curing of poly(furfuryl alcohol) resin catalyzed by a homologous series of dicarboxylic acid catalysts: kinetics and pot life. J Appl Polym Sci 133:44009. CrossRefGoogle Scholar
  18. 18.
    Christodoulides C, Christodoulides G (2017) Analysis and presentation of experimental results. Springer, LondonCrossRefGoogle Scholar
  19. 19.
    Hsich HSY (1978) A unified theory for studying chemical relaxation by using light scattering or ultrasonic absorption experiments. J Mater Sci 13:2560–2568. CrossRefGoogle Scholar
  20. 20.
    Hsich HSY (1980) Physical and thermodynamic aspects of the glassy state, and intrinsic non-linear behaviour of creep and stress relaxation. J Mater Sci 15:1194–1206. CrossRefGoogle Scholar
  21. 21.
    Hsich HSY, Yanyo LC, Ambrose RJ (1984) A relaxation model for property changes during the cure reaction of filled and unfilled silicone elastomers. J Appl Polym Sci 29:2331–2345. CrossRefGoogle Scholar
  22. 22.
    Maciel GE, Chuang IS, Gollob L (1984) Solid-state carbon-13 NMR study of resol-type phenol-formaldehyde resins. Macromol 17:1081–1087. CrossRefGoogle Scholar
  23. 23.
    Diels O, Alder K (1931) Synthesen in der hydroaromatischen Reihe. XII. Mitteilung. (“Dien-Synthesen” sauerstoffhaltiger Heteroringe. 2. Dien-Synthesen des Furans.). Justus Liebigs Ann Chem 490:243–257. CrossRefGoogle Scholar
  24. 24.
    Eggelte TA, de Koning H, Huisman HO (1973) Diels-Alder reaction of furan with some dienophiles. Tetrahedron 29:2491–2493. CrossRefGoogle Scholar
  25. 25.
    Berson JA, Swidler R (1953) The stereochemistry of the Furan–Maleic acid reaction. J Am Chem Soc 75:1721–1726. CrossRefGoogle Scholar
  26. 26.
    Choura M, Belgacem NM, Gandini A (1996) Acid-catalyzed polycondensation of furfuryl alcohol: mechanisms of chromophore formation and cross-linking. Macromol 29:3839–3850. CrossRefGoogle Scholar
  27. 27.
    Domínguez JC, Grivel JC, Madsen B (2012) Study on the non-isothermal curing kinetics of a polyfurfuryl alcohol bioresin by DSC using different amounts of catalyst. Thermochim Acta 529:29–35. CrossRefGoogle Scholar
  28. 28.
    Zarrelli M, Partridge IK, D’Amore A (2006) Warpage induced in bi-material specimens: coefficient of thermal expansion, chemical shrinkage and viscoelastic modulus evolution during cure. Compos Part A: Appl Sci Manuf 37:565–570. CrossRefGoogle Scholar
  29. 29.
    Zarrelli M, Skordos AA, Partridge IK (2008) Thermomechanical analysis of a toughened thermosetting system. Mech Compos Mater 44:181–190. CrossRefGoogle Scholar
  30. 30.
    Zhao L, Hu X (2007) A variable reaction order model for prediction of curing kinetics of thermosetting polymers. Polymer 48:6125–6133. CrossRefGoogle Scholar
  31. 31.
    Guigo N, Mija A, Vincent L, Sbirrazzuoli N (2007) Chemorheological analysis and model-free kinetics of acid catalysed furfuryl alcohol polymerization. Phys Chem Chem Phys 9:5359–5366. CrossRefGoogle Scholar
  32. 32.
    Dominguez JC, Alonso MV, Oliet M, Rodríguez F (2010) Chemorheological study of the curing kinetics of a phenolic resol resin gelled. Eur Polym J 46:50–57. CrossRefGoogle Scholar
  33. 33.
    Dominguez JC, Madsen B (2014) Chemorheological study of a polyfurfuryl alcohol resin system—pre-gel curing stage. Ind Crops Prod 52:321–328. CrossRefGoogle Scholar
  34. 34.
    Yang Y, Suspene L (1991) Curing of unsaturated polyester resins: viscosity studies and simulations in pre-gel state. Polym Eng Sci 31:321–332. CrossRefGoogle Scholar
  35. 35.
    Castro JM, Macosko CW (1982) Studies of mold filling and curing in the reaction injection molding process. AIChE J 28:250–260. CrossRefGoogle Scholar
  36. 36.
    Kamal MR (1974) Thermoset characterization for moldability analysis. Polym Eng Sci 14:231–239. CrossRefGoogle Scholar
  37. 37.
    Hale A, Garcia M, Macosko CW, Manzione LT (1989) Spiral flow modelling of a filled Epoxy–Novolac molding compound. In: ANTEC’89 Plastics Create a World of Difference, pp 796–799Google Scholar
  38. 38.
    Chiou PL, Letton A (1992) Modelling the chemorheology of an epoxy resin system exhibiting complex curing behaviour. Polymer 33:3925–3931. CrossRefGoogle Scholar
  39. 39.
    Dusi MR, May CA, Seferis JC (1983) Chemorheology of thermosetting polymers. ACS Symp Ser 301:1983Google Scholar
  40. 40.
    Montgomery DC, Peck EA, Vining GG (2012) Introduction to linear regression analysis. Wiley, LondonGoogle Scholar
  41. 41.
    Freund RJ, Wilson WJ, Sa P (2006) Regression analysis. Elsevier, AmsterdamGoogle Scholar
  42. 42.
    Rhinehart RR (2016) Nonlinear regression modeling for engineering applications: modeling, model validation, and enabling design of experiments. Wiley, LondonCrossRefGoogle Scholar
  43. 43.
    Rao RV (2010) Advanced modeling and optimization of manufacturing processes: international research and development. Springer, LondonGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Abbas Behzadfar
    • 1
  • Mohammad Imani
    • 1
    • 2
    Email author
  • Farhid Farahmandghavi
    • 1
  1. 1.Iran Polymer and Petrochemical InstituteTehranIran
  2. 2.Biobased Monomers and Polymers Division (BIOBASED Division)Iran Polymer and Petrochemical Institute (IPPI)TehranIran

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