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Nanoparticle directed domain orientation in thin films of asymmetric block copolymers

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Abstract

We investigated the thin film morphology of two different asymmetric block copolymers (BCP), polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(n-pentyl methacrylate)-block-poly(methyl methacrylate) (PPMA-b-PMMA), loaded with pre-synthesized iron oxide nanoparticles (NP). The chemical composition of the BCP constituents determines the strength of the interaction between polymer chains and nanoparticles. In the case of NP/PS-b-P4VP system, the nanoparticles interact preferentially with the P4VP block and hence localize selectively in the P4VP cylindrical microdomains. However, for the NP/PPMA-b-PMMA system, the nanoparticles have no significant preference for the copolymer blocks and segregate at the polymer/substrate interface. Interestingly, this changes the effective substrate surface energy and hence leads to a remarkable change in domain orientation from parallel to perpendicular with respect to the substrate. These results clearly demonstrate the importance of both enthalpic and entropic factors which determine spatial distribution of NP in BCP films and influence domain orientation.

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Abbreviations

BCP:

Block copolymer

PS:

Polystyrene

P4VP:

Poly(4-vinylpyridine)

PPMA:

Poly(n-pentyl methacrylate)

PMMA:

Poly(methyl methacrylate)

NP:

Nanoparticles

TOPO:

Tri-n-octylphosphine oxide

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Acknowledgments

Financial support by the German Research Council (Deutsche Forschungsgemeinschaft, project no. STA 324/38-1 and STA324/37) is gratefully acknowledged. The authors would like to thank DESY Hamburg, HASYLAB, beamline BW4 for measuring time, and Dr. J. Perlich for collaboration and assistance. We greatly acknowledge Dr. Mahmoud Al-Hussein from the University of Jordan for the helpful discussion.

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Authors and Affiliations

  1. Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069, Dresden, Germany

    Andriy Horechyy, Dieter Jehnichen, Michael Göbel, Manfred Stamm & Doris Pospiech

  2. Department of Textile Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India

    Bhanu Nandan

  3. Department of Material Science, University of Ioannina, 45110, Ioannina, Greece

    Nikolaos E. Zafeiropoulos

  4. Physical Chemistry of Polymer Materials, Technische Universität Dresden, 01062, Dresden, Germany

    Manfred Stamm

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  1. Andriy Horechyy
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  2. Bhanu Nandan
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  3. Nikolaos E. Zafeiropoulos
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  4. Dieter Jehnichen
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  5. Michael Göbel
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Correspondence to Andriy Horechyy.

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Horechyy, A., Nandan, B., Zafeiropoulos, N.E. et al. Nanoparticle directed domain orientation in thin films of asymmetric block copolymers. Colloid Polym Sci 292, 2249–2260 (2014). https://doi.org/10.1007/s00396-014-3251-7

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