Surface Characterization of Advanced Polymers

Transcription

1 Surface Characterization of Advanced Polymers Edited by Luigia Sabbatini and Pier Giorgio Zambonin VCH Weinheim New York Basel Cambridge Tokyo

2 1 Spectroscopies for Surface Characterization 1 E. Desimoni and P. G. Zambonin 1.1 Introduction Surface Specificity and Vacuum Requirements X-Ray Photoelectron Spectroscopy Principles Escape Depth Instrumentation Sputtering and Depth-Profiles Spectral Features Data Acquisition and Analysis Quantification High Resolution Electron Energy Loss Spectroscopy Electron Energy Loss Spectroscopy Electron Scattering Mechanisms Instrumentation Data Analysis and Interpretation, Some Practical Examples Ion Scattering Spectroscopy Physical Principles and Quantification Instrumentation Applicative Examples Static Secondary Ion Mass Spectrometry Secondary Ion Mass Spectrometry Physical Principles and Quantification Instrumentation Applicative Examples References 43

3 VIII 2 Electron Induced Vibrational Spectroscopy (HREELS) 47 /./. Pireaux 2.1 Introduction The Experimental Set-Up Polymerie Materials and High-Resolution Electron Energy Loss Spectroscopy (HREELS) Theoretical Issues Three Interaction Mechanisms Very Low Electron Mean Free Path in Polymers Applications A New Spectroscopy Versus X-Ray Photoelectron Spectroscopy and (Time-of-Flight) Secondary Ion Mass Spectrometry [(TOF)SIMS] Resonance/Impact Effects Surface Sensitivity Polymer Chain Structure Surface Diffusion Conducting Polymers Metallized Polymers Developments Instrumental Aspects Theoretical Aspects; Computational Help Conclusions 79 t 2.8 Acknowledgements References 80 3 The Application of Static Secondary Ion Mass Spectrometry (SIMS) to the Surface Analysis of Polymer Materials 83 N. M. Reed and J. C. Vickerman 3.1 Introduction Acquisition of Static Secondary Ion Mass Spectra (SIMS) from Organic Materials Sample Charging What are Static Conditions for Organic Materials? Static Conditions - Ions Versus Atoms Static Conditions - Quadrupole Versus ToF SIMS Mechanism of Secondary Ion Generation Nascent Ion Molecule Model Desorption Ionization Experimental Observations Preformed Ions 98

4 IX Stabilized Ion Pairs Mass Spectrometer/Mass Spectrometer (MS/MS) Studies of the Ion Generation Process Spectral Interpretation Sub-Monomer Region «-Merlons ' Oligomer Ions Listing of Polymers Investigated to Date by SSIMS Quantification Surface Composition of Methacrylate Copolymers Polyether - Polyester Copolymers Ion Beam Effects and Quantification Quantification - Polystyrene/Polyhydroxystyrene - Matrix Effect Problems Low Mass Ion Ratios - a Measure of Elemental Compositions Direct Intensity Measurements - Special Situations Conclusions Static SIMS Studies of Copolymers of Biological Importance Methacrylate Copolymers Employed in Drug Delivery Surface Chemical Structure of Poly(orthoesters) Static SIMS Studies of Polymer Colloid Surfaces 132 t 3.8 Plasma Treated Surfaces Plasma Treated Polypropylene Surfaces Degree of Aromaticity Polymer/Ammonia Plasma Interactions Chain Scission Surface Interactions Related to Cluster Ion Formation Generation of SSIMS Clusters from Polycarbonates ToF SIMS Applied to Polymer Molecular Weight Determination Chemical Surface Modification Characterization of Surface Interactions Technological Applications of Static SIMS Characterization of the Preparation of Optical Discs Investigation of Contact Lens Properties Biosensors Drug Delivery Systems References 160

5 X 4 Low Energy Ion Scattering Spectrometry of Polymer Surface Composition and Structure 163 T.G. Vargo, J.A. Gardella, Jr., R.L. Schmitt, K.J. Hook, T.J. Hook, L. Salvati, Jr. 4.1 Introduction Ion Beam Methods Distinctions, Fundamentals Ion Beam Interactions for Analysis -SIMS, RBS, LEISS Fundamentas of LEISS Utility of Low Energy Ion Scattering Surface Sensitivity Shielding and Shadowing 166' Impact Collision Ion Scattering Spectrometry LEISS of Polymer Surfaces Sample Handling Damage and Static Conditions Instrumentation/Experimental LEISS Studies of Polymerie Systems Overview Studies of Homopolymer Surface Structure Multiple Technique Depth Profiles of Multicomponent Polymers Background and Inelastic Effects Contributing Physical Processes - Current Literature Experimental Investigations of Background and Sputtering in Crystalline Polymers Current Trends and Future Expectations ICISS with Alkali Metal Ions TOF-DRS References X-Ray Photoelectron Spectroscopy Analysis of Conducting Polymers 181 C. Malitesta, G. Morea, L. Sabbatini, P. G. Zambonin 5.1 Introduction Polypyrroles History, Preparation, and Properties X-Ray Photoelectron Spectroscopy Studies Polythiophenes History, Preparation, and Properties X-Ray Photoelectron Spectroscopy Studies Polyanilines 201

6 XI History, Preparation, and Properties X-Ray Photoelectron Spectroscopy Studies Miscellanea Conclusions References Chemical Derivatization Methods for Enhancing the Analytical Capabilities of X-Ray Photoelectron Spectroscopy and Static Secondary Ion Mass Spectrometry 221 A. Chilkoti and B. D. Ratner 6.1 Preface Chemical Derivatization X-Ray Photoelectron Spectroscopy (XPS) Introduction Derivatization XPS Literature Review Derivatization XPS Case Studies Hydroxyl Derivatization Reactions Hydrazine Derivatization Reaction Trifluorethanol/Di-Tertbutylcarbodiimide Derivatization Reaction Chemical Derivatization Static Secondary Ion Mass Spectrometry (SIMS) Introduction Derivatization Static SIMS Literature Review Derivatization Static SIMS Case Studies Analysis of Oxygen-Containing Plasma Deposited Films Derivatization of Conventional Polymers Conclusions Acknowledgements References Data Analysis in X-Ray Photoelectron Spectroscopy 257 P.M.A. Sherwood 7.1 Introduction Data-Collection Systems Software for Data Analysis Databases Simple Data Operations Satellite Removal Data Considerations The Fitting of Data 262

7 XII 7.9 Smoothing Curve Fitting - the Use of Splines Convolutional Algorithms Fourier Transform - Frequency Filtering The Analysis of Overlapping Spectral Features Derivative Spectra Deconvolution Methods Factor Analysis Method Pattern Recognition Method Spectral Ratioing Method The Use of the Kaiman Filter Difference Spectra Addition Spectra Curve Synthesis and Curve Fitting Fitting Functions Least-Squares Curve Fitting Fitting Theoretical Calculations to Valence Band Spectra Background Removal Linear Backgrounds Integral (Nonlinear) Backgrounds Backgrounds Based upon Elastic and Inelastic Loss Processes Acknowledgements References 293 Index 299