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Structural Changes in Semi-Crystalline Ethylene-Based Ionomers During the Heating Process.

Shunsuke Murayama1, Go Matsuba1

  • 1Graduate School of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan.

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|January 11, 2025
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Summary

Heating ethylene-based ionomers with varying Zn/Na ratios reveals how ionic aggregates and crystal structures change. Optimal ion ratios maximize melting enthalpy, showing combined ion presence benefits crystallite growth.

Keywords:
X-ray scattering measurementscrystallizationdifferential scanning calorimetry (DSC)ethylene-based polymersionic aggregatesionomermicrostructural evolutionpolyethylenepolyethylene crystalssemi-crystalline polymerssmall-angle X-ray scattering (SAXS)thermal behaviorwide-angle X-ray scattering (WAXS)

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Area of Science:

  • Polymer Science
  • Materials Science
  • Physical Chemistry

Background:

  • Semi-crystalline ethylene-based ionomers possess ionic aggregates influencing material properties.
  • Understanding the thermal behavior of these aggregates is crucial for material applications.

Purpose of the Study:

  • To investigate the structural evolution of ionic aggregates in ethylene-based ionomers upon heating.
  • To determine the impact of varying zinc (Zn) and sodium (Na) ion ratios on ionomer thermal properties and microstructure.

Main Methods:

  • Differential Scanning Calorimetry (DSC) for thermal transitions and melting behavior.
  • In situ Wide-Angle X-ray Scattering (WAXS) to observe temperature-dependent crystal structure changes.
  • Small-Angle X-ray Scattering (SAXS) with the Yarusso-Cooper equation to analyze ionic aggregate dimensions.

Main Results:

  • Melting point remained largely unaffected by Zn/Na ratio, but melting enthalpy peaked at specific ratios (3:7 and 5:5).
  • WAXS showed monoclinic crystals melting and recrystallizing into orthorhombic forms before complete melting.
  • SAXS indicated ionic aggregates expand upon polyethylene crystal melting, which normally compresses them.

Conclusions:

  • The Zn/Na ion ratio significantly influences the melting enthalpy and crystallite growth in ethylene-based ionomers.
  • Temperature-induced structural transitions involve distinct crystalline phase changes and ionic aggregate rearrangements.
  • Polyethylene crystal melting dictates the observed expansion of ionic aggregates, impacting overall material behavior.