The vibrational spectroscopy of polymers
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1 D. I. BOWER Reader in Polymer Spectroscopy Interdisciplinary Research Centre in Polymer Science & Technology Department of Physics, University of Leeds W.F. MADDAMS Senior Visiting Fellow Department of Chemistry, University of Southampton The vibrational spectroscopy of polymers CAMBRIDGE UNIVERSITY PRESS
2 Contents Preface xiii 1 Introduction Vibrational spectroscopy Molecular vibrations Infrared and Raman spectroscopy Fundamentals of polymers Addition polymers Step growth polymers Regular chains and defect structures Polymer morphology and crystallization The infrared and Raman spectra of polymers The electromagnetic spectrum - symbols and units Spectrometers and experimental methods in infrared spectroscopy Introduction The dispersive infrared spectrometer The Fourier transform spectrometer Sources, detectors and polarizers The preparation of samples for transmission spectroscopy Reflection spectroscopy Spectrometers and experimental methods in Raman spectroscopy Introduction Sources and optical systems Monochromators and detectors Sample preparation and mounting Mathematical techniques for processing spectra Further reading 41 2 Symmetry and normal modes of vibration Interatomic forces and molecular vibrations Interatomic forces Normal modes of vibration 44 vn
3 Vlll Contents 2.2 Symmetry and small molecules Point symmetry operations and symmetry elements Point groups Group representations Representation of groups by matrices Reducible, irreducible and equivalent representations Symmetry species and character tables Notation for symmetry species The number of normal modes of each symmetry species A reducible 3JV-dimensional representation of the point group Reduction of the 3JV-dimensional representation by the use of normal coordinates The number of normal modes of each symmetry species Symmetry coordinates and internal coordinates Further reading 78 3 The vibrational modes of polymers The vibrations of regular polymer chains Introduction Line group and factor group: polyethylene Polyethylene and the vinyl polymers: descent in symmetry Helical molecules The vibrations of polymer crystals The nature of the factor group modes Factor group modes for crystalline PVC and polyethylene Further reading Infrared and Raman spectra Semiclassical treatment of origins of spectra Polarizability tensors and dipole moments Infrared absorption - mechanism and selection rule The origin of Raman scattering Raman scattering and the rule of mutual exclusion Selection rules for Raman activity: Raman tensors 117
4 Contents ix 4.2 Polarization effects Polarized infrared spectroscopy - dichroic ratios Polarized Raman spectroscopy - depolarization ratios Vibrational assignments Introduction Factor group analysis - chain or local symmetry Group vibrations Model compounds Isotope substitution Force fields and vibrational calculations The vibrational problem in Cartesian coordinates Generalized coordinates - the Wilson G and F matrices Mass-weighted Cartesian coordinates and normal coordinates The solution in principle; potential energy distributions Symmetry coordinates and internal symmetry coordinates Force fields and force constants Application to polymers Finite chains Overtone and combination frequencies; Fermi resonance Further reading The characterization of polymers Introduction The interpretation of polymer spectra: factor group analysis Polyethylene Polyvinyl chloride) Poly(vinylidene chloride) Polytetrafluoroethylene Polystyrene Polyethylene terephthalate) The interpretation of polymer spectra: group frequencies Introduction
5 X Contents Hydrocarbon polymers: polypropylene, polyisobutene Polyesters: acetates, acrylates, methacrylates Other oxygen-containing polymers: phenolic resins Nitrogen-containing polymers: amides, polyurethanes Quantitative analysis Introduction Copolymers of vinyl chloride or ethylene with vinyl acetate Styrene/acrylonitrile copolymers and crosslinking in polystyrene Polybutadienes and styrene/butadiene copolymers Monomers and additives Caprolactam in Nylon 6; monomer and water in poly(methyl methacrylate) Additives in polyethylene and polypropylene The characterization of oxidation and degradation Hydrocarbon polymers: polyethylene, polypropylene Resonance Raman studies of degradation in PVC Further reading The microstructure of polymers The distribution of copolymerized units in the polymer chain General principles The determination of overall copolymer composition The characterization of sequence lengths Configurational and conformational isomerism Introduction Configurational isomerism: polypropylene Conformational isomerism Chain branching Introduction Polyethylene Polyvinyl chloride) Head-to-head placements in vinyl polymers End groups Polyethylene 252
6 Contents Vinyl polymers Other polymers Hydrogen bonding Introduction Polyamides Polyurethanes Biopolymers Chain order and crystallinity Introduction Polyethylene Polyoxymethylene Poly (vinyl chloride) Lattice modes in polyethylene and polytetrafluoroethylene Differentiation between crystallinity and chain order Chain folding in polyethylene Longitudinal acoustic modes Molecular orientation Introduction Theoretical background Orientation in polyethylene and poly(ethylene terephthalate) Further reading XI References for chapters 5 and A note on the use of the indexes 307 Index of spectra illustrated 308 Index of point groups 309 Index of group modes 309 Index of polymers 311 Main index 313
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