THE ANALYTICAL CHEMISTRY OF THE NOBLE METALS

By ELIZABETH JONES

CONTENTS SECTION I: INTRODUCTION 1 INTRODUCTION 1 THE ANALYTICAL COMPETENCE 2 CONTENTS AND STRUCTURE 3 PRACTICAL CONSIDERATIONS IN THE MULTI-TECHNIQUE APPROACH REFERENCES 2 POLYMER CHEMISTRY AND MICROSTRUCTURE 1 INTRODUCTION 2 POLYMER: DE?NITIONS 3 FROM MOLECULES TO MACROMOLECULES 4 FUNDAMENTALS OF POLYMER CHEMISTRY 5 POLYMER DEGRADATION 6 SUMMARY 3 POLYMERIC MATERIALS: COMPOSITION, USES AND APPLICATIONS 2 MODE OF POLYMERISATION 3 POLYMER MATERIALS: TYPES AND FORMS 4 POLYMER ADDITIVES 5 SUMMARY BIBLIOGRAPHY SECTION II: POLYMER CHAIN ANALYSIS 4 CHAIN STRUCTURE CHARACTERIZATION 1 INTRODUCTION TO STRUCTURE IN SYNTHETIC MACROMOLECULES 2 LOCAL STRUCTURE AND ITS RAMI?CATIONS 3 SUMMARY 5 CHAIN END CHARACTERISATION 2 END GROUPS IN FREE RADICAL POLYMERS 3 END GROUPS IN CONDENSATION POLYMERS 4 END GROUPS IN POLYMERS FROM IONIC POLYMERISATION 5 CLOSING REMARKS ACKNOWLEDGEMENTS 6 DETERMINATION OF MOLECULAR WEIGHTS AND THEIR DISTRIBUTIONS 2 DISTRIBUTION FUNCTIONS AND AVERAGES 3 METHODS BASED ON COLLIGATIVE PROPERTIES 4 VISCOMETRY 5 SCATTERING TECHNIQUES 6 LIQUID CHROMATOGRAPHY 7 ANALYTICAL ULTRACENTRIFUGE 8 OTHER METHODS 9 PRACTICAL EXAMPLES 10 CONCLUSION SECTION III: POLYMER MORPHOLOGY AND STRUCTURE 7 PHASE STRUCTURE AND MORPHOLOGY 1 PHASE STRUCTURE AND MORPHOLOGY 2 SUPERMOLECULAR MORPHOLOGY 3 CONCLUDING REMARKS 8 CHARACTERIZATION OF MOLECULAR ORIENTATION 2 THEORY 3 BIREFRINGENCE 4 INFRARED LINEAR DICHROISM (IRLD) 5 RAMAN SPECTROSCOPY AND MICROSPECTROSCOPY 6 FLUORESCENCE SPECTROSCOPY 7 NMR SPECTROSCOPY 8 X-RAY DIFFRACTION AND ABSORPTION 9 CONCLUSION 9 POLYMER NETWORKS: ELASTOMERS B ERMAN AND J E MARK 1 INTRODUCTION 2 STRUCTURE OF A TYPICAL NETWORK 3 ELEMENTARY AND MORE ADVANCED MOLECULAR THEORIES 4 PHENOMENOLOGICAL THEORIES 5 SOME RELEVANT SIMULATIONS 6 SWELLING OF NETWORKS AND RESPONSIVE GELS 7 ENTHALPIC AND ENTROPIC CONTRIBUTIONS TO RUBBER ELASTICITY: THE FORCE–TEMPERATURE RELATIONS 8 MULTIMODAL ELASTOMERS 9 LIQUID–CRYSTALLINE ELASTOMERS 10 NOVEL REINFORCED ELASTOMERS 11 FURTHER COMMENTS ON SOME CHARACTERIZATION TECHNIQUES ACKNOWLEDGEMENT SECTION IV: POLYMER DEGRADATION 10 POLYMER DEGRADATION AND OXIDATION: AN INTRODUCTION 2 STANDARD TESTS AND COMPARATIVE METHODS 3 SPECTROSCOPIC TECHNIQUES 4 THERMAL METHODS 5 CHROMATOGRAPHIC ANALYSIS 6 CLOSING REMARKS 11 THE ROLE OF OXIDATION IN DEGRADATION OF POLYMERS: THE RELATION OF OXIDATION TO THE LIGHT EMISSION FROM OXIDIZED POLYMERS 1 INTRODUCTION, HISTORICAL OVERVIEW AND TERMINOLOGY ASSOCIATED WITH THE DEGRADATION AND AGEING OF POLYMERS 2 METHODOLOGY AND ANALYTICAL TECHNIQUES IN POLYMER STABILITY STUDIES 3 MECHANISMS LEADING TO THE LIGHT EMISSION FROM THERMALLY OXIDIZED POLYMERS (CHEMILUMINESCENCE), SIMILARITIES AND DIFFERENCES WITHIN RESPECTIVE GROUPS OF POLYMERS 4 GENERAL CLASSI?CATION OF CHEMILUMINESCENCE FROM POLYMERS 5 COMPARISON OF CHEMILUMINESCENCE FOR ISOTHERMAL AND NON-ISOTHERMAL CONDITIONS WITH THOSE OBTAINED BY DSC 6 THE EFFECT OF INITIAL MOLAR MASS ON CHEMILUMINESCENCE RUNS 7 THE EFFECT OF TEMPERATURE ON CHEMILUMINESCENCE INTENSITY; THE MUTUAL RELATION OF ISOTHERMAL AND NON-ISOTHERMAL STUDIES 8 RELAXATION EXPERIMENTS (JUMP CHANGES OF CONCENTRATION OF OXYGEN, TEMPERATURE AND HUMIDITY) AND RATE CONSTANTS OF RESPECTIVE ELEMENTARY REACTION STEPS 9 THE EFFECT OF ANTIOXIDANTS AND POLYMER STABILIZERS 10 ISOTHERMAL KINETICS OF POLYMERS OXIDATION AND ITS RELATION TO THE CONCENTRATION OF OXYGEN IN SURROUNDING ATMOSPHERE 11 THE EFFECT OF ALKALINE ADDITIVES ON CHEMILUMINESCENCE RUNS: A POSSIBLE IMPACT 12 CONCLUSIONS AND OUTLINE OF THE FURTHER PERSPECTIVES 12 ESR AND ESR IMAGING METHODS FOR THE STUDY OF OXIDATIVE POLYMER DEGRADATION 1 INTRODUCTION: POLYMER DEGRADATION IN THE PRESENCE OF OXYGEN 2 FUNDAMENTALS OF ESR AND ESR IMAGING 3 ESR AS A TOOL FOR THE STUDY OF POLYMER DEGRADATION 4 ESR IMAGING: A NONDESTRUCTIVE METHOD FOR SPATIALLY RESOLVED POLYMER DEGRADATION 5 CONCLUDING REMARKS SECTION V: POLYMER PRODUCT ANALYSIS 13 SPATIAL IMAGING/HETEROGENEITY 2 RAMAN AND FTIR MICROSCOPY 3 EXAMPLES OF HETEROGENEOUS POLYMERS INVESTIGATED BY IR AND RAMAN MICROSCOPY 4 OTHER METHODS AND COMPARISON OF METHODS 5 CONCLUSIONS 14 ADDITIVE ANALYSIS 2 ANALYTICAL TECHNIQUES FOR ADDITIVE ANALYSIS 3 ANALYSIS OF SPECI?C ADDITIVES 4 FUTURE DEVELOPMENTS IN ANALYTICAL METHODOLOGY 15 FAILURE, DEFECT, AND CONTAMINANT ANALYSIS 2 CASE STUDIES 16 SURFACE ANALYSIS 2 A SURFACE AND SPATIAL RESOLUTION 3 ADHESION 4 POLYMER DEGRADATION 5 POLYMER FRACTURE 6 CHARACTERIZING POLYMER SURFACES 7 DELAMINATION 8 CURE 9 CLOSING REMARK SECTION VI: POLYMER AND POLYMER PRODUCT DEVELOPMENT: SUPPORT TECHNIQUES 17 THE SUPPORTING ROLE OF MOLECULAR MODELLING AND COMPUTATIONAL CHEMISTRY IN POLYMER ANALYSIS 2 METHODOLOGIES 3 INFRARED AND RAMAN SPECTROSCOPY 4 PHOTOELECTRON SPECTROSCOPY AND AUGER ELECTRON SPECTROSCOPY (AES) 5 MASS SPECTROMETRY 6 X-RAY DIFFRACTION 7 NUCLEAR MAGNETIC RESONANCE 8 ELECTRON SPIN RESONANCE 9 SUMMARY 18 HIGH-THROUGHPUT ANALYSIS 2 SOME GENERAL CONSIDERATIONS ON MTE AND THE CORRESPONDING ANALYTICAL NEEDS 3 ANALYTICAL TECHNIQUES FOR MEDIUM-THROUGHPUT POLYMER ANALYSIS 4 OUTLOOK