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ACS Appl Mater Interfaces. 2016 Mar;8(12):8201-12. doi: 10.1021/acsami.5b12382. Epub 2016 Mar 15.

Microphase-Separated PE/PEO Thin Films Prepared by Plasma-Assisted Vapor Phase Deposition.

ACS applied materials & interfaces

Andrei Choukourov, Ivan Gordeev, Jessica Ponti, Chiara Uboldi, Iurii Melnichuk, Mykhailo Vaidulych, Jaroslav Kousal, Daniil Nikitin, Lenka Hanyková, Ivan Krakovský, Danka Slavínská, Hynek Biederman

Affiliations

  1. Charles University in Prague , Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovi?kách 2, 180 00 Prague, Czech Republic.
  2. Jan Evangelista Purkyne University in Usti nad Labem , Faculty of Science, Department of Physics, ?eské mládeže 8, Usti nad Labem 400 96, Czech Republic.
  3. European Commision Joint Research Centre, Institute for Health and Consumer Protection , Nanobiosciences, via Fermi 2749, 21027 Ispra, Italy.

PMID: 26953817 DOI: 10.1021/acsami.5b12382

Abstract

Immiscible polymer blends tend to undergo phase separation with the formation of nanoscale architecture which can be used in a variety of applications. Different wet-chemistry techniques already exist to fix the resultant polymeric structure in predictable manner. In this work, an all-dry and plasma-based strategy is proposed to fabricate thin films of microphase-separated polyolefin/polyether blends. This is achieved by directing (-CH2-)100 and (-CH2-CH2-O-)25 oligomer fluxes produced by vacuum thermal decomposition of poly(ethylene) and poly(ethylene oxide) onto silicon substrates through the zone of the glow discharge. The strategy enables mixing of thermodynamically incompatible macromolecules at the molecular level, whereas electron-impact-initiated radicals serve as cross-linkers to arrest the subsequent phase separation at the nanoscale. The mechanism of the phase separation as well as the morphology of the films is found to depend on the ratio between the oligomeric fluxes. For polyolefin-rich mixtures, polyether molecules self-organize by nucleation and growth into spherical domains with average height of 22 nm and average diameter of 170 nm. For equinumerous fluxes and for mixtures with the prevalence of polyethers, spinodal decomposition is detected that results in the formation of bicontinuous structures with the characteristic domain size and spacing ranging between 5 × 10(1) -7 × 10(1) nm and 3 × 10(2)-4 × 10(2) nm, respectively. The method is shown to produce films with tunable wettability and biologically nonfouling properties.

Keywords: bicontinuous structure; copolymer; nucleation and growth; plasma polymerization; spinodal decomposition

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