Abstract

On the >1 µm scale the morphology of semicrystalline plastics like polyethylene or Nylon features spherulites, “shish-kebabs”, cylinddrites and other crystalline aggregates which strongly affect mechanical and other material properties. Current imaging techniques give only a 2D picture of these objects. Here we show how they can be visualized in 3D using fluorescent labels and confocal microscopy. As a result, we see spherulites in 3D, both in neat polymers and their nanocomposites, and observe how unevenly nanoparticles and other additives are distributed in the material. Images of i-polypropylene and biodegradable poly(lactic acid) reveal previously unsuspected morphologies such as “vases” and “goblets”, nonspherical “spherulites” and, unexpectedly, “shish-kebabs” grown from quiescent melt. Also surprisingly, in nanocomposite sheets spherulite nucleation is seen to be copied from one surface to another, mediated by crystallization-induced pressure drop and local melt-flow. These first results reveal unfamiliar modes of self-assembly in familiar plastics and open fresh perspectives on polymer microstructure.

Highlights

  • On the >1 μm scale the morphology of semicrystalline plastics like polyethylene or Nylon features spherulites, “shish-kebabs”, cylinddrites and other crystalline aggregates which strongly affect mechanical and other material properties

  • We were inspired by the work of Calvert et al.[24–26] who used fluorescence microscopy (FM) to view the distribution of a UV absorber in isotactic polypropylene (iPP) and observed a lowered concentration of the additive within the spherulites

  • In Fig. 1(a2, a4) we show FM images recorded during the same crystallization run and from the same area as in the polarized optical microscopy (POM) images in Fig. 1(a1, a3)

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Summary

Introduction

On the >1 μm scale the morphology of semicrystalline plastics like polyethylene or Nylon features spherulites, “shish-kebabs”, cylinddrites and other crystalline aggregates which strongly affect mechanical and other material properties. Spherulites, shish-kebabs, cylindrites, and other morphological features of bulk semicrystalline polymers (SCP) have so far been studied using methods such as polarized optical microscopy (POM)[1], transmission electron (TEM)[2], or atomic force microscopy (AFM)[3]. For these studies either thin films or thin sections were used, giving 2D but not 3D pictures. More exotic 3D imaging techniques have been tried, such as using X-rays based on the minute difference in X-ray refractive index in polymer blends[12] and foams[13] Despite some success, these methods suffer from low contrast and require highly specialized and scarce coherent synchrotron X-ray beamlines. Our preliminary 2D studies using labeled NPs have shown that, contrary to theoretical predictions, large NPs are to a considerable extent pushed ahead of growing spherulites and deposited at their boundaries[16] with potentially serious consequences for material integrity

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