Modeling the crystallization kinetics of polymers displaying high levels of secondary crystallization

Catherine Kelly, Michael Jenkins

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The isothermal crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) was evaluated using a range of models, namely, Avrami, simplified Hillier, Tobin, Malkin, Urbanovici–Segal, Velisaris–Seferis, and Hay. Two methods of model evaluation were used: determination of the parameters through traditional double log plots and curve fitting via nonlinear, multivariable regression. Visual inspection of the cumulative crystallization curves, calculation of the R 2 value and standard error of the regression, and evaluation of the returned parameters were used to assess which model best describes the experimental data. The Hay model was found to generate the best fit, closely followed by the Velisaris–Seferis parallel model, suggesting that primary and secondary crystallization occur concurrently. The Avrami, Malkin, and Tobin models were found to perform well when the data is restricted to the region where primary crystallization dominates; however, they could not be used to successfully model the entire crystallization process. This work highlights the importance of selecting the most appropriate model for analyzing kinetics, especially when high levels of lamellar thickening and infilling occur during crystallization.

Original languageEnglish
Pages (from-to)249–257
JournalPolymer Journal
Issue number3
Early online date19 Nov 2021
Publication statusPublished - Mar 2022

Bibliographical note

Publisher Copyright:
© 2021, The Author(s).

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry


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