Advertisement

Characterization of critical gel state of polyamides by viscoelastic, thermal, and IR measurements

  • Takaya Hirayama
  • Takashi Uneyama
  • Yuichi MasubuchiEmail author
Original Contribution
  • 52 Downloads

Abstract

We examined the liquid-solid transition for polyamides (PA) 6, 66, and 610 by the Chambon-Winter method under cooling. The polyamides exhibited the transition via the critical gel, for which the critical exponent and the stiffness were consistent with those reported under the isothermal measurements for the other polymers. The DSC measurements showed that, for a few materials, the crystallinity at the gelation φgel was very small. This result implies that the hydrogen bonding partially stabilizes the critical gel of such polyamides. The FT-IR measurements demonstrated that the hydrogen bonding was formed cooperatively around the gelation temperature. However, we also found that with increasing the molecular weight, the gelation temperature decreased and φgel increased for PA6. Besides, φgel was smaller for PA66 and PA610 than that for PA6. The mechanism is unknown for these results that locate in the opposite side to the suggested role of hydrogen bonding.

Keywords

Viscoelasticity Gelation Rheology Semi-crystalline polymers 

Notes

Acknowledgments

The authors appreciate the supports from Dr. Yoshifumi Amamoto, Prof. Atsushi Noro, Prof. Atsuhiko Yamanaka, and Prof. Tetsuya Yamamoto.

Funding information

This study is partly supported in part by Grant-in-Aid for Scientific Research (A) (17H01152) from JSPS and by Council for Science, Technology, and Innovation, Cross-ministerial Strategic Innovation Promotion Program, Structural Materials for Innovation from JST.

References

  1. Acierno S, Grizzuti N, Winter HH (2002) Effects of molecular weight on the isothermal crystallization of poly(1-butene). Macromolecules 35:5043–5048.  https://doi.org/10.1021/ma0200423 CrossRefGoogle Scholar
  2. Acierno S, Di Maio E, Iannace S, Grizzuti N (2006) Structure development during crystallization of polycaprolactone. Rheol Acta 45:387–392.  https://doi.org/10.1007/s00397-005-0054-2 CrossRefGoogle Scholar
  3. Boutahar K, Carrot C, Guillet J (1998) Crystallization of polyolefins from rheological measurements—relation between the transformed fraction and the dynamic moduli. Macromolecules 31:1921–1929.  https://doi.org/10.1021/ma9710592 CrossRefGoogle Scholar
  4. Chambon F, Winter HH (1987) Linear viscoelasticity at the gel point of a crosslinking PDMS with imbalanced stoichiometry. J Rheol 31:683–697.  https://doi.org/10.1122/1.549955 CrossRefGoogle Scholar
  5. Coleman MM, Skrovanek DJ, Painter PC (1986) Hydrogen bonding in polymers: III further infrared temperature studies of polyamides. Makromol Chem Macromol Symp 5:21–33.  https://doi.org/10.1002/masy.19860050104 CrossRefGoogle Scholar
  6. Coppola S, Acierno S, Grizzuti N, Vlassopoulos D (2006) Viscoelastic behavior of semicrystalline thermoplastic polymers during the early stages of crystallization. Macromolecules 39:1507–1514.  https://doi.org/10.1021/ma0518510 CrossRefGoogle Scholar
  7. Dijkstra DJ (2009) Guidelines for rheological characterization of polyamide melts (IUPAC Technical Report). Pure Appl Chem 81:339–349.  https://doi.org/10.1351/PAC-REP-08-07-22 CrossRefGoogle Scholar
  8. Fornes TD, Yoon PJ, Keskkula H, Paul DR (2001) Nylon 6 nanocomposites: the effect of matrix molecular weight. Polymer (Guildf) 42:09929–09940.  https://doi.org/10.1016/S0032-3861(01)00552-3 CrossRefGoogle Scholar
  9. Gelfer M, Horst RH, Winter HH, Heintz AM, Hsu SL (2003) Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers. Polymer 44:2363–2371.  https://doi.org/10.1016/S0032-3861(03)00077-6 CrossRefGoogle Scholar
  10. Harings J (2009) Shielding and mediating of hydrogen bonding in amide-based (macro)molecules. Technische Universiteit EindhovenGoogle Scholar
  11. Hess W, Vilgis TA, Winter HH (1988) Dynamical critical behavior during chemical gelation and vulcanization. Macromolelcules 21:2536–2542.  https://doi.org/10.1021/ma00186a037 CrossRefGoogle Scholar
  12. Inoue M, Company TR (1963) Studies on crystallization of high polymers by differential thermal analysis. J Polym Sci Part A 1:2697–2709.  https://doi.org/10.1002/pol.1963.100010813 Google Scholar
  13. Ishisaka A, Kawagoe M (2004) Examination of the time-water content superposition on the dynamic viscoelasticity of moistened polyamide 6 and epoxy. J Appl Polym Sci 93:560–567.  https://doi.org/10.1002/app.20465 CrossRefGoogle Scholar
  14. Itoh T, Miyaji H, Asai K (1975) Thermal properties of α- and γ-forms of nylon 6. Jpn J Appl Phys 14:206–215.  https://doi.org/10.1143/JJAP.14.206 CrossRefGoogle Scholar
  15. Izuka A, Winter HH, Hashimoto T (1992) Molecular weight dependence of viscoelasticity of polycaprolactone critical gels: Macromolecules 25:2422–2428Google Scholar
  16. Laun HM (1979) Das viskoelastisch Verhalten von Polyamid-6-Schmelzen. Rheol Acta 18:478–491CrossRefGoogle Scholar
  17. Lin YG, Winter HH, Mailin DT, Chien JCW (1991) Dynamic mechanical measurement of crystallization-induced gelation in thermoplastic elastomeric poly(propylene). Macromolecules 24:850–854.  https://doi.org/10.1021/ma00004a006 CrossRefGoogle Scholar
  18. Lopez Mayorga O, Freire E (1987) Dynamic analysis of differential scanning calorimetry data. Biophys Chem 27:87–96CrossRefGoogle Scholar
  19. Mannella GA, La Carrubba V, Brucato V, Zoetelief W, Haagh G (2011a) No‐flow temperature and solidification in injection molding simulation. AIP Con Proc 1353:689–693.  https://doi.org/10.1063/1.3589595
  20. Mannella GA, La Carrubba V, Brucato V et al (2011b) No-flow temperature in injection molding simulation. J Appl Polym Sci 119:3382–3392.  https://doi.org/10.1002/app.32987 CrossRefGoogle Scholar
  21. Marchildon K (2011) Polyamides—still strong after seventy years. Macromol React Eng 5:22–54.  https://doi.org/10.1002/mren.201000017 CrossRefGoogle Scholar
  22. Mours M, Henning Winter H (1995) Viscoelasticity of polymers during heating/cooling sweeps. Ind Eng Chem Res 34:3217–3222.  https://doi.org/10.1021/ie00037a006 CrossRefGoogle Scholar
  23. Mours M, Winter HH (1994) Time-resolved rheometry. Rheol Acta 33:385–397.  https://doi.org/10.1007/BF00366581 CrossRefGoogle Scholar
  24. Muthukumar M (1989) Screening effect on viscoelasticity near the gel point. Macromolecules 22:4656–4658.  https://doi.org/10.1021/ma00202a050 CrossRefGoogle Scholar
  25. Muthukumar M, Winter HH (1986) Fractal dimension of a cross-linking polymer at the gel point. Macromolecules 19:1284–1285.  https://doi.org/10.1021/ma00158a064 CrossRefGoogle Scholar
  26. Nichetti D, Cossar S, Grizzuti N (2005) Effects of molecular weight and chemical structure on phase transition of thermoplastic polyurethanes. J Rheol 49:1361–1376.  https://doi.org/10.1122/1.2071987 CrossRefGoogle Scholar
  27. Pogodina NV, Winter HH (1998) Polypropylene crystallization as a physical gelation process. Macromolecules 31:8164–8172.  https://doi.org/10.1021/ma980134l CrossRefGoogle Scholar
  28. Pogodina NV, Winter HH, Srinivas S (1999) Strain effects on physical gelation of crystallizing isotactic polypropylene. J Polym Sci Part B Polym Phys 37:3512–3519.  https://doi.org/10.1002/(SICI)1099-0488(19991215)37:24<3512::AID-POLB12>3.0.CO;2-#
  29. Pogodina NV, Lavrenko VP, Srinivas S, Winter HH (2001) Rheology and structure of isotactic polypropylene near the gel point: quiescent and shear-induced crystallization. Polymer 42:9031–9043.  https://doi.org/10.1016/S0032-3861(01)00402-5 CrossRefGoogle Scholar
  30. Richtering HW, Gagnon KD, Lenz RW, Fuller RC, Winter HH (1992) Physical gelation of a bacterial thermoplastic elastomer. Macromolecules 25:2429–2433.  https://doi.org/10.1021/ma00035a021 CrossRefGoogle Scholar
  31. Sandeman I, Keller A (1956) Crystallinity studies of polyamides by infrared, specific volume and X-ray methods. J Polym Sci 19:401–435.  https://doi.org/10.1002/pol.1956.120199303 CrossRefGoogle Scholar
  32. Schwittay C, Mours M, Winter HH (1995) Rheological expression of physical gelation in polymers. Faraday Discuss 101:93.  https://doi.org/10.1039/fd9950100093 CrossRefGoogle Scholar
  33. Skrovanek DJ, Howe SE, Painter PC, Coleman MM (1985) Hydrogen bonding in polymers: infrared temperature studies of an amorphous polyamide. Macromolecules 18:1676–1683.  https://doi.org/10.1021/ma00151a006 CrossRefGoogle Scholar
  34. Tanner RI (2002) A suspension model for low shear rate polymer solidification. J Nonnewton Fluid Mech 102:397–408.  https://doi.org/10.1016/S0377-0257(01)00189-6 CrossRefGoogle Scholar
  35. Watanabe K, Nagatake W, Takahashi T, Masubuchi Y, Takimoto J, Koyama K (2003) Direct observation of polymer crystallization process under shear by a shear flow observation system. Polym Test 22:101–108.  https://doi.org/10.1016/S0142-9418(02)00057-0 CrossRefGoogle Scholar
  36. Winter HH, Chambon F (1986) Analysis of linear viscoelasticity of a crosslinking polymer at the gel point. J Rheol 30:367–382.  https://doi.org/10.1122/1.549853 CrossRefGoogle Scholar
  37. Winter HH, Mours M (1997) Rheology of polymers near liquid-solid transitions. Neutron Spin Echo Spectrosc Viscoelasticity Rheol 134:165–234.  https://doi.org/10.1007/3-540-68449-2_3 CrossRefGoogle Scholar
  38. Yao Y, Xia X, Mukuze KS, Zhang Y, Wang H (2014) Study on the temperature-induced sol–gel transition of cellulose/silk fibroin blends in 1-butyl-3-methylimidazolium chloride via rheological behavior. Cellulose 21:3737–3743.  https://doi.org/10.1007/s10570-014-0349-5 CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Takaya Hirayama
    • 1
  • Takashi Uneyama
    • 2
  • Yuichi Masubuchi
    • 3
    Email author
  1. 1.Department of Applied PhysicsNagoya UniversityNagoyaJapan
  2. 2.Center of Computational ScienceNagoya UniversityNagoyaJapan
  3. 3.Department of Materials PhysicsNagoya UniversityNagoyaJapan

Personalised recommendations