Metastable liquid-liquid and solid-liquid phase boundaries in polymer-solvent-nonsolvent systems

P. van de Witte, P.J. Dijkstra, J.W.A. van den Berg, J. Feijen

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In general liquid-liquid demixing processes are responsible for the porous morphology of membranes obtained by immersion precipitation. For rapidly crystallizing polymers, solid-liquid demixing processes also generate porous morphologies. In this study, the interference of both phase transitions has been analyzed theoretically using the Flory-Huggins theory for ternary polymer solutions. It is demonstrated that four main thermodynamic and kinetic parameters are important for the structure formation in solution: the thermodynamic driving force for crystallization, the ratio of the molar volumes of the solvent and the nonsolvent, the polymer-solvent interaction parameter, and the rate of crystallization of the polymer compared to the rate of solvent-nonsolvent exchange. An analysis of the relevance of each of these parameters for the membrane morphology is presented.
Original languageEnglish
Pages (from-to)763-770
JournalJournal of polymer science. Part B: Polymer physics
Issue number5
Publication statusPublished - 1997


  • METIS-106377
  • IR-71366
  • liquid-liquid demixing
  • immersion precipitation
  • nonequilibrium phenomena
  • Melting transitions
  • Membranes


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