Kinetic evaluation of the Arrhenius equation for artificial ageing of polymers
DOI:
https://doi.org/10.17268/sel.mat.2025.02.09Keywords:
Ageing of polymers, Arrhenius equation, kinetic parameters, thermogravimetric analysisAbstract
Artificial ageing of polymers is a crucial and complex issue, especially considering that critical infrastructures such as nuclear power plants have lifespans varying from 40 to 60 years or even longer. Controlled artificial ageing allows the evaluation of polymer lifetimes while ensuring that their properties are preserved. However, a unified and validated methodology for artificially ageing polymers is still lacking.
One of the most extended methodologies for the artificial ageing of polymers is the Arrhenius methodology. This methodology is based on the application of the Arrhenius equation, which is extensively applied in the study of thermal decomposition reactions. Nevertheless, the Arrhenius methodology requires the estimation of activation energy, and the lack of a unified method introduces variability in results obtained using different methods. Furthermore, the Arrhenius ageing methodology assumes that the kinetic parameters do not change during ageing, meaning that aged and non-aged materials should exhibit the same activation energy.
The present work aims to analyse the hypothesis of unvariable activation energy during ageing. This was investigated using both new and artificially aged PVC samples, evaluating the activation energy through various mathematical models based on thermogravimetric analysis.
References
IAEA Nuclear Energy Series No. NP-T-3.24 Handbook on Ageing Management for Nuclear Power Plants, Vienna; 2017.
Celina M, Clough RL, Gillen KT. Limitations of the Arrhenius Methododolgy. Albuquerque, NM, and Livermore, CA: Sandia National Laboratories; 1998.
Celina M, Gillen K. Nuclear Power Plant Cable Materials: Review of Qualification and Currently Available Aging Data for Margin Assessments in Cable Performance. SAND2013-2388; 2013.
Gillen K, Bernstein R, Celina M. Non-Arrhenius behavior for oxidative degradation of chlorosulfonated polyethylene materials. Polym. Degrad. Stab. 2005; 87:335–346.
Gillen K, Celina M, Bernstein R. Validation of improved methods for predicting long-term elastomeric seal lifetimes from compression stress-relaxation and oxygen consumption techniques. Polym. Degrad. Stab. 2003; 82:25–35.
Gillen K, Bernstein R, Derzon D. Evidence of non-Arrhenius behavior from laboratory aging and 24-year field aging of polychloroprene rubber materials. Polym, Degrad. Stab. 2005; 87(1):57–67.
Witkowski A, Stec A, Hull T. Chapter 7. Thermal Decomposition of Polymeric Materials. SFPE Handbook of Fire Protection Engineering, 5th ed. New York, USA, Springer; 2016. p. 1-3493.
Sharp J, Wentworth S. Kinetic analysis of thermogravimetric data. Anal. Chem. 1969; 41(14):2060–2062.
Freeman E, Carroll B. The application of thermoanalytical techniques to reaction kinetics. The thermogravimetric evaluation of the kinetics of the decomposition of calcium oxalate monohydrate. J. Phys. Chem. 1958; 62(4):394–397.
Coats A, Redfern J. Kinetic parameters from thermogravimetric data. Nature. 1964; 201:68-69 https://doi.org/10.1038/201068a0.
Simon P. Isoconversional methods: Fundamentals, meaning and application. J. Therm. Anal. Calorim. 2004; 76(1):123–132.
Vyazovkin S. Computational aspects of kinetics analysis. Part C. The ICTAC Kinetic Project – the light at the end of the tunnel?. Thermochimica Acta. 2000; 355:155-163.
Flynn F, Wall J. A quick, direct method for the determination of activation energy from thermogravimetric data. Polym. Lett. 1966; 4(5):323-328. https://doi-org/10.1002/pol.1966.110040504
Friedman H. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J. Polym. Sci. Part C Polym. Symp. 1964; 6(1):183–195.
Vyazovkin S. Modification of the integral isoconversional method to account for variation in the activation energy. J. Comput. Chem. 2001; 22(2):178–183.
Akahira T, Sunose T. Method of determining activation deterioration constant of electrical insulating materials. Research Report Chiba Institute of Technology (Science Technology); 1971.
Matala A, Lautenberger C, Hostikka S. Generalized direct method for pyrolysis kinetic parameter estimation and comparison to existing methods. J. Fire Sci. 2012; 30(4):339-356.
Vyazovkin S, Burnham A.K, Criado J.M, Perez-Maquedac L.A, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochimica Acta. 2011; 520(1-2):1-19.
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