An experimentally validated model for quiescent multiphase primary and secondary crystallization phenomena in PP with low content of ethylene comonomer

Harm J.M. Caelers*, Anke de Cock*, Stan F.S.P. Looijmans, Ralf Kleppinger, Enrico M. Troisi, Martin van Drongelen, Gerrit W.M. Peters

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

4 Citations (Scopus)
103 Downloads (Pure)

Abstract

While crystallization behavior of isotactic polypropylene homopolymers had been subject to a wide range of experimental and modeling studies, this is not the case for propylene-ethylene random copolymers (PPR). This class of polymers offers up to now significant challenges, both from an experimental as well as a modeling perspective. The ethylene incorporation in the propylene chains, as well as the distribution of this comonomer, has a marked effect on the crystallization kinetics. Moreover, the presence of these defects causes a clear separation between primary crystallization (i.e. space filling) and subsequent secondary crystallization (increase of crystallinity in filled space) within the spherulitic skeletons, particularly subsequent at high primary crystallization temperatures. In this work, the underlying mechanism is first quantified by means of a combination of in-situ WAXD and SAXS experiments, as well as ex-situ WAXD experiments and calorimetric measurements. Based on these experiments an extended model framework is presented, capable of predicting multiphase non-isothermal crystallization kinetics as well as the final crystallinity as a function of the applied thermal conditions relevant for processing. The chemical composition distribution (CCD) of the ethylene comonomer serves as critical input to parameterize the model. Optical microscopy- and DSC experiments are used for parameterization of the primary crystallization model. The model developed in this study is, in principle, applicable to all polypropylenes, ranging from homo-polymers to random copolymers with variable comonomer content and/or CCD but, so far, only applied and validated on one PPR. To validate the model and the parameters for a given PPR, several non-isothermal and isothermal experiments (the latter followed by subsequent cooling) are conducted over a wide range of crystallization temperatures and cooling rates. The good match between experiments and model predictions demonstrates the power of the newly developed framework. The final crystallinity, the amount of α- and γ-phase, and the ratio between primary and secondary crystallization can be predicted as a function of the time-temperature history. To the best knowledge of the authors, it is the first time that such a direct connection with the CCD is incorporated in a crystallization model. Consequently, the model offers a new tool to bridge the gap between chemical structure and resulting product properties, which now has come one step closer for PPR systems.

Original languageEnglish
Article number124901
Number of pages20
JournalPolymer
Volume253
Early online date17 May 2022
DOIs
Publication statusPublished - 22 Jun 2022

Keywords

  • Calorimetry
  • Crystallization model
  • Optical microscopy
  • Polymorphism
  • Primary and secondary crystallization
  • Propylene-ethylene random copolymer
  • Structure and morphology
  • Synchrotron radiation
  • 22/2 OA procedure

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