Skip to main content
Log in

Molecular relaxation phenomena during accelerated weathering of a polyurethane coating

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

Results from a polyester-urethane (PU) coating system under accelerated weathering showed that crosslink density, obtained from high-temperature modulus data, diminished due to chain scission. However, T g and room-temperature tensile modulus both increased with weathering. Molecular relaxation phenomena in polymers have long been investigated to explore changes occurring in a polymer at temperatures below its glass transition and were explored for an explanation to supplement chemical degradation for these observations. Relaxation was quantified using “enthalpy recovery” which first increased with exposure, then diminished. The concurrent physical and chemical aging effects were characterized by tracking nonexponentiality in the spectrum of relaxation times, and the size of “co-operatively relaxing regions” deduced from relaxation around the glass transition. Mechanical relaxation in this coating extended longer than cycle periods typical of accelerated weathering, suggesting that frequency effects might be important when comparing accelerated to natural weathering.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

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

References

  1. H Ochs, J Vogelsang, G Meyer Enhanced Surface Roughness of Organic Coatings due to UV-Degradation: An Unknown Source of EIS-Artifacts. Prog. Org. Coat., 46(3), 182–190 (2003)

    Article  CAS  Google Scholar 

  2. Hinderliter, B, Croll, S, Allahar, K, Stafford, O, Bierwagen, G, Tallman, D, “Using Ionic Liquids to Measure Coating Properties Via Electrochemical Impedance Spectroscopy (EIS).” J. Coat. Technol. Res., Accepted for publication

  3. AD Skaja, BMD Fernando, SG Croll Mechanical Property Changes and Degradation During Accelerated Weathering of Polyester-Urethane Coatings. J. Coat. Technol. Res., 3(1), 41–51 (2006)

    CAS  Google Scholar 

  4. G Wypch, Handbook of Material Weathering, 2nd ed. ChemTech Publishing, Toronto, Canada, p. 252 (1995)

    Google Scholar 

  5. (a) Struik, LCE, Physical Aging in Amorphous Polymers and Other Materials. Elsevier Scientific Publications Co., Amsterdam (1978); (b) Angell, CA, Ngai, KL, McKenna, GB, McMillan, PF, Martin, SW, “Relaxation in Glassforming Amorphous Solids,” J. Appl. Phys., 88 (6) 3113–3157 (2000)

    Google Scholar 

  6. JM Hutchinson Physical Aging of Polymers. Prog. Polym. Sci., 20(4), 703–760 (1995)

    Article  CAS  Google Scholar 

  7. SL Simon, JW Sobieski, DJ Plazek Volume and Enthalpy Recovery of Polystyrene. Polymer, 42(6), 2555–2567 (2001)

    Article  CAS  Google Scholar 

  8. AY Belov, HU Jäger Relaxation Kinetics in Amorphous Carbon Films: An Insight From Atomic Scale Simulation. Thin Solid Films, 482(1–2), 74–78 (2005)

    Article  CAS  Google Scholar 

  9. DY Perera Physical Ageing of Organic Coatings. Prog. Org. Coat., 47, 61–76 (2003)

    Article  CAS  Google Scholar 

  10. S Montserrat, Y Calventus, JM Hutchinson Physical Aging of Thermosetting Powder Coatings. Prog. Org. Coat., 55(1), 35–42 (2006)

    Article  CAS  Google Scholar 

  11. MD Ediger, JL Skinner Single Molecules Rock and Roll Near the Glass Transition. Science, 292, 233–234 (2001)

    Article  CAS  Google Scholar 

  12. C Donati, SC Glotzer, PH Poole, W Kob, SJ Plimpton Spatial Correlations of Mobility and Immobility in a Glass-Forming Lennard-Jones Liquid. Phys. Rev. E., 60(3), 3107–3119 (1999)

    Article  CAS  Google Scholar 

  13. Moynihan, CT, “Phenomenology of the Structural Relaxation Process and the Glass Transition.” In: Seyler, RJ (ed.) Assignment of the Glass Transition, ASTM STP 1249, pp. 32–49. ASTM, PA (1994)

  14. TS Ellis, FE Karasz, GJ Ten Brinke The Influence of Thermal Properties on the Glass Transition Temperature in Styrene/Divinylbenzene Network-Diluent Systems. J. Appl. Polym. Sci., 28(1), 23–32 (1983)

    Article  CAS  Google Scholar 

  15. R van der Linde, EG Belder, DY Perera Effect of Physical Aging and Thermal Stress on the Behavior of Polyester/TGIC Powder Coating. Prog. Org. Coat., 40(1), 215–224 (2000)

    Article  Google Scholar 

  16. A Lee, GB McKenna Effect of Crosslink Density on Physical Ageing of Epoxy Networks. Polymer, 29(10), 1812–1817 (1988)

    Article  CAS  Google Scholar 

  17. IM Hodge Enthalpy Relaxation and Recovery in Amorphous Materials. J. Non-Cryst. Solids, 169(3), 211–266 (1994)

    Article  CAS  Google Scholar 

  18. Y Calventus, S Montserrat, JM Hutchinson Enthalpy Relaxation of Non-Stoichiometric Epoxy-Amine Resins. Polymer, 42(16), 7081–7092 (2001)

    Article  CAS  Google Scholar 

  19. H Lu, S Nutt Restricted Relaxation in Polymer Nanocomposites Near the Glass Transition. Macromolecules, 36(11), 4010–4016 (2003)

    Article  CAS  Google Scholar 

  20. OS Narayanaswamy A Model of Structural Relaxation in Glass. J. Am. Ceram. Soc., 54, 491–498 (1971)

    Article  CAS  Google Scholar 

  21. CT Moynihan, AJ Eastel, MA DeBolt, J Tucker Dependence of the Fictive Temperature of Glass on Cooling Rate. J. Am. Ceram. Soc. 59(1), 12–16 (1976)

    Article  CAS  Google Scholar 

  22. S Montserrat, JM Hutchinson On the Measurement of the Width of the Distribution of Relaxation Times in Polymer Glasses. Polymer, 43(2), 351–355 (2002)

    Article  CAS  Google Scholar 

  23. H Lu, S Nutt Restricted Relaxation in Polymer Nanocomposites Near the Glass Transition. Macromolecules, 36(11), 4010–4016 (2003)

    Article  CAS  Google Scholar 

  24. G Adam, JH Gibbs On the Temperature Dependence of Cooperative Relaxation Properties in Glass-Forming Liquids. J. Chem. Phy., 43(1), 139–146 (1965)

    Article  CAS  Google Scholar 

  25. E Donth The Size of Cooperatively Rearranging Regions in Polystyrene and Styrene-Dimethylsiloxane Diblock Copolymers at the Glass Transition Temperature. Acta Polym., 35(2), 120–123 (1984)

    Article  CAS  Google Scholar 

  26. S Krause, M Iskandar, M Iqbal Properties of Low Molecular Weight Block Copolymers. 1. Differential Scanning Calorimetry of Styrene-Dimethylsiloxane Diblock Copolymers. Macromolecules, 15(1), 105–111 (1982)

    Article  CAS  Google Scholar 

  27. AT Metters, CN Bowman, KS Anseth A Statistical Kinetic Model for the Bulk Degradation of PLA-b-PEG-b-PLA Hydrogel Networks. J. Phys. Chem. B, 104(30), 7043–7049 (2000)

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This work was supported by the Air Force Office of Scientific Research, contract number FA9599-04-1-0368.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to S. G. Croll.

Additional information

This paper was awarded Third Place in the John A. Gordon Best Paper competition, presented as part of 2006 FutureCoat! Conference, sponsored by Federation of Societies for Coatings Technology, November 1–3, 2006, in New Orleans, LA.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Fernando, B.M.D., Shi, X. & Croll, S.G. Molecular relaxation phenomena during accelerated weathering of a polyurethane coating. J Coat Technol Res 5, 1–9 (2008). https://doi.org/10.1007/s11998-007-9077-1

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-007-9077-1

Keywords

Navigation