PMMA highlights the layering transition of PDMS in Langmuir films

C. Bernardini, S.D. Stoyanov, M.A. Cohen Stuart, L.N. Arnaudov, F.A.M. Leermakers

Research output: Contribution to journalArticleAcademicpeer-review

11 Citations (Scopus)


We report a system consisting of a mixed Langmuir monolayer, made of water-insoluble, spreadable, fluid-like polymers polydimethylsiloxane (PDMS) and polymethylmethacrylate (PMMA) with a minority P(DMS-b-MMA) copolymer. We have performed both Langmuir trough pressure/area isotherm measurements and Brewster angle microscopy (BAM) observations and complement the experiments with molecularly detailed self-consistent field (SCF) calculations. PDMS undergoes a layering transition that is difficult to detect by BAM. Addition of PMMA gives contrast in BAM, now showing a two-phase system: if this would consist of separate two-dimensional (2D) PMMA and PDMS phases, a PDMS-PMMA diblock should accumulate at the phase boundary. However, the diblock copolymer of PDMS-PMMA failed to show the expected “lineactant” behavior, i.e., failed to accumulate at the phase boundary. The calculations point to a nontrivial arrangement of the polymer chains at the interface: in mixtures of the two homopolymers, in a rather wide composition ratio, we find a vertical (with respect to the air/water interfacial plane) configuration, with PMMA sitting preferably at the PDMS/water interface of the thicker PDMS film, during the PDMS layering phase transition. This also explains why the diblock copolymer is not a lineactant. Both PMMA and P(DMS-b-MMA) are depleted from the thin-thick PDMS film interface, and the line tension between the phases is, consequently, increased, in the binary mixtures as well as in the ternary ones
Original languageEnglish
Pages (from-to)2501-2508
Issue number6
Publication statusPublished - 2011


  • air-water-interface
  • molecular layers
  • polymer-films
  • surface
  • poly(dimethylsiloxane)
  • methacrylate
  • ellipsometry
  • behavior
  • spread


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