Decay of imprinted surface waves in polymers [Elektronische Ressource] : a method to probe near-surface dynamics / Kirstin Petersen

DECAY OF IMPRINTED SURFACE WAVES IN POLYMERS:A METHOD TO PROBE NEAR-SURFACE DYNAMICSDissertationzur Erlangung des Grades”Doktor der Naturwissenschaften”am Fachbereich Chemie und Pharmazieder Johannes Gutenberg-Universitat¨in MainzKirstin Petersengeboren in AachenMainz 2003”If you don’t make mistakes you are not working on hard enough problems,and that’s a big mistake.”Frank WilczekiiContentsTABLE OF CONTENTS 11 INTRODUCTION 22 LITERATURE OVERVIEW: Current Status 43 EXPERIMENTAL TECHNIQUES AND MODES OF MEASUREMENT 103.1 Experimental Techniques 103.1.1 Sample and Master Preparation 103.1.2 Experimental Setup 173.1.3 Hot Embossing 213.2 Modes of Measurement 253.2.1 Quasi-Static:Temperature Ramps and an Estimate for Surface Glass Temperature - 253.2.2 Dynamic:Constant Temperature, Mastering, Activation Energies and Fragilities 304 THEORETICAL BACKGROUND 324.1 Surface Waves 324.2 Theoretical Models for Polymer Dynamics 374.2.1 Bead-Spring Model 374.2.2 Reptation Model 414.3 Time-Temperature Superposition 444.4 Relaxation Processes and Activation Energy 474.5 Fragility 564.6 Free Volume and Expansion Coefficients 585 RESULTS 625.1 Temperature Ramps 635.1.1 Temperature Ramps with Diffraction 635.1.2 Tature with Atomic Force Microscopy (AFM) 745.2 Decay Experiments with Diffraction: Surface Dynamics 795.2.1 Mastering 795.2.2 Activation Energies 855.2.3 Determination of Fragility 925.2.