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Network structure of polyfluorene sheets as a function of alkyl side chain length

M. Knaapila1,*, D. W. Bright2, R. Stepanyan3, M. Torkkeli4, L. Almásy5,6, R. Schweins7, U. Vainio8, E. Preis9, F. Galbrecht9 et al.

U. Scherf9 and A. P. Monkman2

  • 1Physics Department, Institute for Energy Technology, NO-2027 Kjeller, Norway
  • 2Department of Physics, University of Durham, DH1 3LE Durham, United Kingdom
  • 3Materials Science Centre, DSM Research, NL-6160 MD Geleen, The Netherlands
  • 4Department of Physics, FI-00014 University of Helsinki, Finland
  • 5Research Institute for Solid State Physics and Optics, Budapest-1525, Hungary
  • 6Laboratory for Neutron Scattering, PSI, CH-5232 Villigen, Switzerland
  • 7Institut Laue-Langevin, DS / LSS group, FR-38042 Grenoble CEDEX 9, France
  • 8HASYLAB am DESY, DE-22607 Hamburg, Germany
  • 9Fachbereich Chemie, Bergische Universität Wuppertal, DE-42097 Wuppertal, Germany

  • *matti.knaapila@ife.no
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Phys. Rev. E 83, 051803 – Published 19 May, 2011

DOI: https://doi.org/10.1103/PhysRevE.83.051803

Abstract

The formation of self-organized structures in poly(9,9-di-n-alkylfluorene)s ∼1 vol % methylcyclohexane (MCH) and deuterated MCH (MCH-d14) solutions was studied at room temperature using neutron and x-ray scattering (with the overall q range of 0.000 58–4.29 Å−1) and optical spectroscopy. The number of side chain carbons (N) ranged from 6 to 10. The phase behavior was rationalized in terms of polymer overlap, cross-link density, and blending rules. For N=6−9, the system contains isotropic areas and lyotropic areas where sheetlike assemblies (lateral size of >400 Å) and free polymer chains form ribbonlike agglomerates (characteristic dimension of >1500 Å) leading to a gel-like appearance of the solutions. The ribbons are largely packed together with surface fractal characteristics for N=6−7 but become open networklike structures with mass fractal characteristics for N=8−9, until the system goes through a transition to an isotropic phase of overlapping rodlike polymers for N=10. The polymer order within sheets varies allowing classification for loose membranes and ordered sheets, including the so-called β phase. The polymers within the ordered sheets have restricted motion for N=6−7 but more freedom to vibrate for N=8−9. The nodes in the ribbon network are suggested to contain ordered sheets cross-linking the ribbons together, while the nodes in the isotropic phase appear as weak density fluctuations cross-linking individual chains together. The tendencies for macrophase separation and the formation of non beta sheets decrease while the proportion of free chains increases with increasing N. The fraction of β phase varies nonlinearly, reaching its maximum at N = 8.

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      Phys. Rev. E 83, 051803– Published 19 May, 2011
      • Received 2 February 2011

      ©2011 American Physical Society

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