Surface and Interfacial Aspects of Biomedical Polymers

Transcription

1 Surface and Interfacial Aspects of Biomedical Polymers Volume 1 Surface Chemistry and Physics Edited by Joseph D. Andrade University of Utah Salt Lake City, Utah PLENUM PRESS NEW YORK AND LONDON

2 Contents 1. Introduction to Surface Chemistry and Physics of Polymers 1 J. D. Andrade 1. Sources 1 2. Objectives 5 3. Overview 9 4. Limitations References Polymer Surface Dynamics J. D. Andrade, D.. Gregonis, and L. M. Smith Introduction Polymer Transitions and Relaxations Probing Polymer Motions and Transitions Bulk Methods Inverse Gas Chromatography (IGC) Polymer Surface Motions Inverse GC Filled Systems Contact Angle Methods Other Methods Conclusions Summary 39 Acknowledgments 39 References Model Polymers for Probing Surface and Interfacial Phenomena D. E. Gregonis and J. D. Andrade 1. Introduction Stereoregular Polymers Purpose (Stereochemistry) 44 ix

3 x CONTENTS 2.2. Chemistry Bulk Properties Surface Characterization Hydroxyethyl Methacrylate Copolymers Purpose (Systemic Hydradon) Chemistry Bulk Properties Surface Characteristics Block Copolymers Purpose (Morphology) Styrene-Hydroxylated Butadiene-Styrene Triblocks HEMA-Styrene-HEMA Triblocks Alkyl Methacrylates Purpose (Systematic Change in! ) Chemistry Bulk Characteristics Surface Characteristics Derivatized Agarose Purpose (Modification for Systemic Hydrophobicity) Chemistry Bulk Characteristics Surface Characteristics Polyurethanes Purpose (Practical Biomedical Elastomers) Chemistry Bulk Properties Surface Characteristics Poly(a-Amino Acids) Purpose (Naturally Occurring Repeat Units) Chemistry Surface Analysis Summary/Conclusions 71 Acknowledgments 72 References Polymerie Oriented Monolayers and Multilayers as Model Surfaces B. Hupfer and H. Ringsdorf 1. Introduction Biological Membranes Models for Biomembranes 79

4 CONTENTS xi 1.3. Characterization of Mono-and Multilayers Stability of Conventional Model Membrane Systems Polymerized Model Membranes Polymerizable Lipids Polymerized Monolayers Monolayers with One Component Mixed Monolayers Polymerie Multilayers Polymerie Black Lipid Membranes Polymerie Vesicles (Liposomes) Conclusions 99 References X-ray Photoelectron Spectroscopy (XPS) J. D. Andrade 1. Introduction Basic Principles of XPS The Photoelectric Effect Basic Experiment Instrument X-ray Source Sample Analyzer/Detector Instrument Sources Charging and Energy Referencing Spectra and Spectral Features Elemental Analysis Qualitative and Semiquantitative Analysis Quantitative Elemental Analyses Basics X-ray Flux, I Differential Photoionization Cross Section, cr ik Instrument Transmission or Throughput Function, T,, k Mean Free Path, X itk Measured Intensities, N ijc Quantitative Analysis Summary Chemical Bonding Chemical Shifts Energy Referencing Initial and Final States 151

5 xii CONTENTS 4.4. Auger Processes Shake-up Satellites Multiplet Splitting Molecular Orbitals Summary Functional Group Labelling Data Processing Curve Resolution Smoothing Derivatives Deconvolution Summary Variable Angle Methods Introduction Mean Free Paths Uniform Overlayers Patchy Overlayers Surface Concentration Gradients Limitations 190 Acknowledgments 190 References Surface Infrared Spectroscopy K. Knutson and D. J. Lyman 1. Introduction Infrared Spectroscopy Principles of Internal Reflection Electromagnetic Radiation Described as Waves Vectorial Properties of Electromagnetic Waves Energy Flux of Electromagnetic Radiation Reflection and Refraction of Electromagnetic Waves at an Interface Total Internal Reflection Presence of an Electromagnetic Field in the Second Medium Sampling the Electromagnetic Field in the Second Medium Sampling Depth of Electromagnetic Field in the Second Medium Sampling Depth as a Function of Experimental Variables

6 CONTENTS xiii 4. Polymer Applications of Total Internal Reflection Infrared Spectroscopy Surface Molecular Structure Surface Orientation Surface Morphology Summary 241 Acknowledgment 242 References The Contact Angle and Interface Energetics J. D. Andrade, L. M. Smith, and D. E. Gregonis 1. Introduction Fundamentals Surface and Interface Conventions, Definitions, and Semantics Two-Phase Equilibria The Liquid/Vapor and Liquid/Liquid Interfaces Three-Phase Equilibria Ideally Deformable Phases: The L/L/V Interface Ideally Nondeformable Phases: The S/L/V Interface Equilibrium Surface and Interfacial Tension Measurement Contact Angle Measurement Assumptions Methods Critical Surface Tension, y c Captive Bubble (Underwater) Method Contact Angle Hysteresis Background Hysteresis Roughness Surface Heterogeneity Deformation Swelling and Penetration Surface Reorientation and Mobility Surface Entropy Interfacial Energetics Charge Effects Conclusions 288 Acknowledgments 288 References 289

7 x/v CONTENTS 8. Interfacial Electrochemistry of Surfaces with Biomedical Relevance J. Lyklema 1. Introduction Basic Electrical Parameters Charge Potential Other Important Electrical Characteristics Double Layer Models The Molecular Condenser The Diffuse Double Layer The Gouy-Stern Double Layer Porous Double Layers Double Layer Theory Gouy-Chapman Theory Inner Layer Theory Porous Double Layers Interpretation of Electrokinetic Potentials Experimental The Surface Charge The Electrokinetic Charge and Potential Conclusions 334 References Interface Acid-Base/Charge-Transfer Properties F. M. Fowkes 1. The Acid-Base Character of "Polar" Interactions The Surface Acidity or Basicity of Polymers InfraredMeasurementsof Acid-Base Polymer Interactions Contact Angle Measurements of Surface Acidity or Basicity The Surface Acidity or Basicity of Inorganic Surfaces Adsorption of Polymers on Inorganic Surfaces Heats of Adsorption of Organic Acids and Bases on Inorganic Powders Charge Transfer between Phases Charge Transfer between Inorganic Solids and Organic Liquids Charge Injection into Organic Polymers Semiconductor Devices for Sensing Charge Injection into Polymers 361 Acknowledgment 371 References 371

8 CONTENTS xv 10. Graft Copolymer and Block Copolymer Surfaces B. D. Ratner 1. Introduction Graft Copolymer Surfaces Block Copolymer Surfaces Segmented Polyurethanes 388 Acknowledgments 391 References Interfacial Tensions at Amorphous Polymer-Water Interfaces: Theory M. S. Jhon and Y. Oh 1. Introduction The Theory of Surface and Interfacial Tensions of Amorphous High Polymers Lattice Theories Significant Structure Theory Scaled Particle Theories Self-Consistent Field Theory Thermodynamic Theory Geometrie Mean and Harmonie Mean Theories Regulär Solution Theory The Theory of Interfacial Tension at Polymer-Water Interfaces Surface Tension of Water Interfacial Tension at Polymer-Water Interfaces References Surface Raman Spectroscopy W. M. Reichert and J. D. Andrade 1. Introduction ' Raman Scattering Effect Surface and Thin Film Raman Spectroscopy External Reflection Total Internal Reflection (TIR) Waveguide Methods Plasmon Enhancement Surface-Enhanced Raman Spectroscopy (SERS) Instrumental Improvements 438

9 XVI CONTENTS 5. Conclusion 439 Acknowledgments 439 References Polymer Surface Analysis: Conclusions and Expectations J. D. Andrade 1. Introduction Microscopy Expectations Ion Beam Methods SIMS and ISS Photoelectron Microscopy and Imaging XPS Surface Fluorescence Spectroscopy Surface Modification Reference Surfaces Scanning Ellipsometry Other Conclusions 457 References 457 Index 461