Polymer Surface Characterization

Description

Polymer Surface Characterization provides a comprehensive approach to the surface analysis of polymers of technological interest by means of modern analytical techniques. Basic principles, operative conditions, applications, performance, and limiting features are supplied, together with current advances in instrumental apparatus. Each chapter is devoted to one technique and is self-consistent; the end-of-chapter references would allow the reader a quick access to more detailed information. After an introductory chapter, techniques that can interrogate the very shallow depth of a polymer surface, spanning from the top few angstroms in secondary ions mass spectrometry to 2-10 nm in X-ray photoelectron spectroscopy are discussed, followed by Fourier transform infrared spectroscopy and chapters on characterization by scanning probe microscopy, electron microscopies, wettability and spectroscopic ellipsometry. Techniques have been selected that are well suited for characterization of surfaces/interfaces of thin polymer-based films but also of more general applicability in materials science. Case studies are critically discussed by experts in the field. Cover Half Title Also of interest Polymer Surface Characterization Copyright Preface Contents Polymer Surface Characterization – 2nd Edition 1. Introductory remarks on polymers and polymer surfaces 1.1 Why polymers? 1.1.1 Generality 1.1.2 Synthesis 1.1.3 Classification and nomenclature 1.1.4 Morphology and properties 1.2 Why to investigate a polymer surface? 1.2.1 Nature and dynamics of polymer surfaces 1.2.1.1 Vibrational dynamics of macromolecules 1.2.1.2 Changes in thermodynamic properties on the surface 1.2.1.3 Rotation of functional groups on polymer backbones in response to different environmental conditions 1.2.1.4 Surface interdiffusion or segregation of copolymers or polymer blends 1.2.2 Surface modification of polymers 1.2.2.1 Improvement of wettability 1.2.2.2 Improvement of porosity or roughening 1.2.2.3 Improvement of adhesion 1.2.2.4 Interaction of polymer with biological environment: biocompatibility 1.2.2.5 Improvement of conductivity 1.2.3 Nanostructured polymers 1.2.4 Possibility of predicting polymer performances by means of surfa References Elvira De Giglio, Nicoletta Ditaranto, Luigia Sabbatini 2. Polymer surface chemistry: characterization by XPS 2.1 Introduction 2.2 Photoelectron spectroscopy: a brief history 2.2.1 Basic principles 2.2.2 Spectroscopic and X-ray notations 2.3 Photoelectron spectroscopy: a brief history 2.3.1 Vacuum system 2.3.2 X-ray sources 2.3.2.1 Dual Mg/Al anode X-ray tube 2.3.2.2 Monochromatic source 2.3.2.3 Synchrotron radiation source 2.3.3 Energy analyzers 2.3.4 Detectors 2.3.5 Charge compensation 2.3.6 Small-area XPS: imaging and mapping 2.3.7 Ambient-pressure photoelectron spectroscopy 2.4 Chemical information from XPS 2.5 Chemical shift and its significance in the analysis of polymers 2.6 Chemical derivatization techniques in conjunction with XPS 2.7 Polymers surface segregation 2.8 Polymers physical treatments/grafting 2.9 Polymers aging References 3. Polymer surface characterization by near-edge X-ray absorption fine structure spectroscopy 3.1 Introduction 3.1.1 Scope of chapter 3.1.2 Why NEXAFS? 3.1.3 History 3.2 Principles of NEXAFS 3.2.1 Physical processes 3.2.2 Theory 3.3 Techniques 3.3.1 Experimental aspects 3.3.2 Detection schemes 3.3.3 Surface-sensitive detection 3.4 Interpreting NEXAFS spectra 3.4.1 Common features of a NEXAFS spectrum 3.4.2 Polymer NEXAFS – fingerprinting and functional group identification 3.4.3 Linear dichroism – theory 3.4.4 Linear dichroism – examples 3.5 Examples 3.5.1 Pure polymeric materials 3.5.1.1 Fused aromatic rings 3.5.1.2 Polysaccharides 3.5.2 Surface versus bulk chain orientation 3.6 Spectromicroscopy of polymers 3.6.1 NEXAFS microscopy methods 3.6.1.1 X-ray photoemission electron microscopy (XPEEM) 3.6.1.2 Scanning transmission X-ray microscopy (STXM) 3.6.2 XPEEM of protein adsorption on PS/PMMA 3.6.3 STXM of protein (Fg) adsorption on a reinforced polyurethane 3.7 Summary References 4. Investigation of polymer surfaces by time-of-flight secondary ion mass spectrometry 4.1 Introduction 4.1.1 Analysis of surfaces 4.1.2 The SIMS process: a detailed approach of theory and instruments 4.2 TOF-SIMS investigations of polymer materials 4.2.1 General remarks 4.2.2 Polymers 4.2.3 Polymer additives 4.2.4 Copolymers 4.2.5 Multicomponent polymers (polymer blends) 4.2.6 Plasma modification and deposition 4.2.7 Other applications References 5. Advances in attenuated total reflection (ATR) infrared spectroscopy: a powerful tool for investigating polymer surfaces and interfaces 5.1 Principles of infrared (IR) spectroscopy 5.2 Theory of attenuated total reflection (ATR) IR spectroscopy 5.2.1 Propagation of IR radiation through a planar interface between 5.2.2 Propagation of IR radiation through stratified media 5.2.3 Penetration depth and effective thickness 5.2.4 Transmission IR versus ATR/IR spectroscopy 5.3 Experimental methods in ATR/IR spectroscopy 5.3.1 Internal reflection elements (IREs) 5.3.2 Internal reflection attachments (IRAs) 5.3.3 Metal underlayer ATR/IR spectroscopy 5.4 Potentials and limitations of ATR/IR spectroscopy 5.5 Applications of ATR/IR spectroscopy 5.5.1 ATR/IR spectroscopy in polymer science 5.5.2 Research applications of ATR/IR spectroscopy for studying the surface properties of hydrogels 5.5.3 In situ ATR/IR spectroscopy of tribochemical phenomena 5.5.4 Recent advances in time-resolved ATR/IR spectroscopy References 6. Scanning probe microscopy of polymers 6.1 Introduction 6.2 Sample preparation 6.3 Phase imaging 6.3.1 Background on phase imaging 6.3.2 Applications of phase imaging to polymer materials 6.4 Multifrequency imaging 6.5 Mapping of mechanical properties 6.6 Electrical measurements with AFM 6.7 Thermal/spectroscopic measurements 6.8 Environmental measurements 6.9 Conclusions References 7. Polymer surface morphology: characterization by electron microscopies 7.1 Introduction 7.2 Scanning electron microscopy 7.2.1 SEM: principles 7.2.1.1 Microscope and image formation 7.2.1.2 Interaction of electron beam with specimen 7.2.2 SEM: classical modes 7.2.2.1 SE imaging 7.2.2.2 BSE imaging 7.2.2.3 EDX spectra 7.2.2.4 Scanning transmission electron microscopy 7.2.3 SEM: Modern trends 7.2.3.1 Variable-pressure SEM 7.2.3.2 Variable-temperature SEM 7.2.3.3 Low-voltage SEM 7.2.3.4 Multidimensional SEM 7.2.4 SEM: further possibilities 7.3 Transmission electron microscopy 7.4 Sample preparation 7.4.1 Overview of polymer materials 7.4.2 Specific features of polymer materials 7.4.2.1 Charging and electron-beam damage 7.4.2.2 Skin-core effect 7.4.2.3 Low contrast between components 7.4.3 Preparation techniques for polymer materials 7.4.3.1 Direct observation of polymer surface 7.4.3.2 Fracturing 7.4.3.3 Etching 7.4.3.4 Cutting and staining 7.4.3.5 Special techniques 7.5 Applications 7.5.1 Homopolymers 7.5.2 Copolymers 7.5.3 Polymer blends 7.5.4 Polymer composites 7.5.5 Special applications 7.5.5.1 Low-voltage SEM in polymer science 7.5.5.2 Wet specimens in polymer science 7.5.5.3 Further applications References 8. Application of spectroscopic ellipsometry in the analysis of thin polymer films/polymer interfaces 8.1 Introduction 8.1.1 Basics of ellipsometry 8.2 Specific ellipsometric methods, techniques, and aspects relevant fo 8.2.1 The optical dispersion 8.2.2 In situ setups for experiments in solution 8.2.2.1 Liquid cells for measurements in solution in the VIS and the IR range 8.2.2.2 Coupling SE with quartz crystal microbalance 8.2.2.3 Total internal reflection ellipsometry (TIRE) 8.2.3 In-line monitoring of polymer thin films 8.2.3.1 Monitoring processes in a vacuum chamber 8.2.3.2 Roll-to-roll (r2r) fabrication processes 8.2.4 Micropatterned films – imaging ellipsometry 8.2.4.1 VIS imaging ellipsometry 8.2.4.2 Microfocus-mapping IR ellipsometry 8.3 Selected architectures of polymer films, blends, and composites 8.3.1 Polymer blends and cross-linked polymer films 8.3.2 Tg in thin polymer films of different architectures 8.3.3 Polymer–nanoparticle composites (PNC) 8.3.4 Polymers in nanostructured surfaces 8.4 Polymer films absorbing in the visible spectral range 8.4.1 Chemical modification of polymer films with dye molecules 8.4.2 Semiconducting polymers and blends for OPV and OLED 8.5 Swelling and adsorption processes: proteins and stimuli-responsive 8.5.1 Swelling of stimuli-responsive polymer layers 8.5.2 Protein adsorption at soft polymer surfaces References 9. Wettability of polymer surfaces: significance and measurements. Recent developments and applications 9.1 Introduction 9.2 Contact angle and surface energy 9.2.1 Surface energy evaluation 9.3 Contact angle hysteresis 9.4 Measurement methods for contact angle 9.4.1 Direct measurement by optical goniometry 9.4.2 Force tensiometry 9.4.3 Methods comparison 9.4.4 Particular case: granular materials 9.5 Application of wettability characterization 9.5.1 From hydrophobic to water- and oil-repellent materials 9.5.2 Hydrophilic to super-hydrophilic materials 9.5.3 Hydrophobic recovery of hydrophilic surfaces 9.5.4 Wettability of porous surfaces References 10. Nanoindentation: characterizing the mechanical properties of polymeric surfaces 10.1 Introduction and background 10.2 Mechanical properties of polymers 10.3 Nanoindentation 10.3.1 Basic concepts and approach toward the Oliver and Pharr methods 10.3.2 Indenter types 10.4 Factors affecting nanoindentation test results 10.4.1 Sample preparation and surface detection 10.4.2 The environment controls 10.4.3 The selection of distance 10.5 Nanoindentation of polymers 10.5.1 Nanoindentation using depth-sensing indentation systems 10.5.2 Nanoindentation using scanning probe microscopy systems 10.6 Determination of hardness and elastic modulus 10.7 Conclusions References Index