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Structure-Property Relationship in Isotactic Polypropylene Under Contrasting Processing Conditions.

Edin Suljovrujic1, Dejan Milicevic1, Katarina Djordjevic1

  • 1Vinca Institute of Nuclear Sciences-National Institute of the Republic of Serbia, University of Belgrade, 11351 Belgrade, Serbia.

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Summary

This study reveals how cooling rates dramatically alter isotactic polypropylene (iPP) properties. Rapid cooling yields flexible iPP, while slow cooling produces brittle iPP, offering insights for material design.

Keywords:
crystallizationpolymorphismpolypropyleneprocessing conditionssemicrystalline polymers

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Area of Science:

  • Polymer Science
  • Materials Science
  • Crystallization Behavior

Background:

  • Isotactic polypropylene (iPP) is a widely used synthetic polymer valued for its physical, thermal, and mechanical properties.
  • The properties of semicrystalline polymers like iPP are critically dependent on their morphology, which is shaped by crystallization conditions.
  • Understanding the impact of processing conditions on iPP's structure-property relationship is vital for tailoring materials for specific industrial applications.

Purpose of the Study:

  • To investigate the effects of extreme cooling conditions (rapid quenching vs. very slow cooling) on the morphology, structure, thermal, and mechanical properties of isotactic polypropylene (iPP).
  • To explore the limits of iPP processability and how preparation conditions influence its final characteristics.
  • To apply dynamic dielectric spectroscopy (DDS) for the first time to differentiate molecular mobility in processing-dependent iPP structural forms.

Main Methods:

  • Preparation of iPP samples under two extreme cooling conditions: rapid quenching (Q samples) and very slow cooling (SC samples).
  • Comprehensive characterization using optical microscopy (OM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic dielectric spectroscopy (DDS), and mechanical testing.
  • Analysis of molecular mobility differences using DDS, focusing on mesomorphic (smectic) and α-monoclinic forms.

Main Results:

  • Slowly cooled (SC) iPP exhibited significantly higher crystallinity (≥ 55%) and larger crystallites (≈ 20 nm) compared to quenched (Q) samples (< 30% crystallinity, ≤ 3 nm crystallites).
  • Mechanical testing revealed a stark contrast: Q samples showed > 500% elongation at break, while SC samples exhibited brittle behavior (< 15% elongation at break).
  • DDS analysis showed that α relaxation in SC samples had enhanced intensity and a temperature shift, indicating greater structural constraints due to higher crystallinity and larger crystallite size.

Conclusions:

  • Cooling rate is a critical factor in determining the morphology and properties of isotactic polypropylene.
  • Extreme processing conditions lead to distinct structural forms with vastly different mechanical behaviors, from highly ductile to brittle.
  • The findings provide crucial insights into the structure-property-processing relationships of iPP, essential for optimizing material design in industrial applications.