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Organizing Nanoparticles in Semicrystalline Polymers by Modifying Particle Diffusivity.

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Area of Science:

  • Materials Science
  • Polymer Science
  • Nanotechnology

Background:

  • Semicrystalline polymers can be reinforced by incorporating nanoparticles (NPs).
  • NP ordering within polymer matrices can be controlled by crystallization processes.
  • Previous work established NP ordering in amorphous interlamellar regions below a critical spherulite growth rate.

Purpose of the Study:

  • To investigate the role of nanoparticle (NP) diffusivity in their ordering within semicrystalline polymer matrices.
  • To understand how polymer matrix viscosity, altered by molecular weight, affects NP ordering during crystallization.

Main Methods:

  • Utilized poly(ethylene oxide) (PEO) with four molecular weights (5.4–46 kDa) to vary matrix viscosity.
  • Incorporated 10 vol % bare 14 nm diameter silica NPs into PEO samples.
  • Controlled and fixed spherulite growth rates across different PEO molecular weights to isolate NP ordering effects.

Main Results:

  • At high spherulite growth rates (12 μm/s), lower molecular weight PEO (higher NP mobility) showed the highest NP order.
  • At slower growth rates, intermediate molecular weight PEO samples exhibited maximum NP ordering.
  • Evidence suggests NP segregation into grain boundaries at slow growth rates, leading to diffusion-controlled growth in low molecular weight PEO.

Conclusions:

  • NP diffusivity significantly impacts ordering within semicrystalline polymers during crystallization.
  • The interplay between NP mobility and polymer crystallization kinetics dictates the final NP arrangement.
  • NP segregation into inter-spherulitic regions is a key mechanism governing ordering at reduced crystallization rates.