Capillary instabilities in thin polymer films Harkema, Stephan
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1 Capillary instabilities in thin polymer films Harkema, Stephan IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2006 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Harkema, S. (2006). Capillary instabilities in thin polymer films: Mechanism of structure formation and pattern replication [Groningen]: [S.n.] Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date:
2 Capillary Instabilities in Thin Polymer Films Mechanism of Structure Formation and Pattern Replication Stephan Harkema
3 Capillary Instabilities in Thin Polymer Films Mechanism of Structure Formation and Pattern Replication S. Harkema Department of Polymer Physics, University of Groningen, The Netherlands. December, 2005 Cover: Compilation of Optical Microscopy and Atomic Force Microscopy images that are described in this thesis. Cover design by Paul Verspaget. Copyright c 2005 by S. Harkema This research was financially supported by: The Materials Science Centre (MSC) De Stichting voor Fundamenteel Onderzoek der Materie (FOM) The Foundation for Fundamental Research on Matter (FOM) MSC Ph.D.-thesis series ISSN ISBN (Print) ISBN (Online) NUR 926
4 Rijksuniversiteit Groningen Capillary Instabilities in Thin Polymer Films Mechanism of Structure Formation and Pattern Replication Proefschrift ter verkrijging van het doctoraat in de Wiskunde en Natuurwetenschappen aan de Rijksuniversiteit Groningen op gezag van de Rector Magnificus, dr. F. Zwarts, in het openbaar te verdedigen op vrijdag 3 februari 2006 om 16:15 uur door Stephan Harkema geboren op 2 augustus 1977 te Leeuwarden
5 Promotores: Prof.Dr.U.Steiner Prof. Dr. G. ten Brinke Beoordelingscommissie: Prof.Dr.T.P.Russell Prof. Dr. K. Jacobs Dr. W.T.S. Huck ISBN
6 The hierarchy of substances is abolished A single one replaces them all The whole world can be plasticized Roland Barthes Opgedragen aan Petra
7
8 Contents 1 Introduction 1 2 Principles of Liquid Polymer Films Polymers in History Polymers & Properties Wetting & Capillarity Capillary waves Van der Waals forces and Hamaker constant Thin film stability Dewetting Linear Stability Analysis Concluding Remarks Experimental Techniques & Materials Experimental set-up Polymers Substrates Snow-jet cleaning Spin-coating Surface energy modification Thermal Annealing & Vapor Sorption Annealing Optical Microscopy on thin polymer films Atomic Force Microscopy Ellipsometry Confinement of Capillary Instabilities in a Polymer Blend Film Introduction Film Destabilization PVME and PS/PVME blends Surface Enrichment
9 4.5 Nature of the Instability Experimental Pattern Formation by Confined Dewetting Conclusion Electrohydrodynamic Instabilities in Thin Polymer Films Electrohydrodynamics Electrohydrodynamic Instability Experimental Data Pattern Formation in Thin Polymer Films Induced by Electric Fields Introduction Experimental Spontaneous pattern formation Nucleated Instability Rim Profile of a Nucleated Instability Cascading Rim Profiles Ordering of a Nucleated Instability Conclusion Pattern Formation in Thin Polymer Films Induced by Temperature Gradients Introduction Experimental Procedure Morphology Theory of the Thermomechanical Interfacial Pressure Temperature Dependent Surface Tension Acoustic Quality Factor Morphology Selection Mechanism of the Formation of the Linear Morphology Spiraling fingers Phonon Pressure vs. Electrostatic Pressure Conclusion Pattern Replication in Externally Applied Fields Photolithography and Soft-lithography Soft-Lithography by Externally Applied Fields Experimental Section Periodicity Mismatch: Small Wavelength Regime Periodicity Match: Similar Wavelength Regime Periodicity Mismatch: Large Wavelength Regime Surface Wave Migration Exploring the Parameter Space D Simulations Conclusions Free Volume Considerations of Vapor Sorption Introduction Glass Transition Depression
10 9.3 Film thickness Free Volume Theories Diffusion of diluents into a polymer glass Vrentas-Duda Free Volume Model Polymer Internal Viscosity Free Volume Swelling Prediction Conclusions Pattern Formation in an Electric Field using Vapor Sorption Surface Enrichment Pattern Replication using Vapor Sorption Experimental Results and Discussion Hierarchy of Pattern Formation Excess Polymer Uptake Conclusions Structure Formation and Replication by Triboelectrification Experimental Observations Triboelectrostatic Lithography Prospects and Conclusions Summary 239 Samenvatting 243 List of Publications 247 Dankwoord 249
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