Molecular Characterization of Polymers A Fundamental Guide : A Fundamental Guide

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Front Matter Copyright Contributors Foreword Preface References Basic principles of size exclusion and liquid interaction chromatography of polymers Liquid chromatography of polymers Theory of polymer chromatography Size exclusion chromatography Interaction chromatography or liquid adsorption chromatography Liquid chromatography at critical conditions Thermodynamics of polymer chromatography Equipment and materials Solvent delivery and injector Column dimensions Stationary phases Mobile phases Detectors Concentration sensitive detectors Selective detectors Universal detectors RI detector Density detector Evaporative light scattering detector Molar mass sensitive detectors Typical situations in liquid chromatography of complex polymers Multidimensional separation of complex polymers Typical applications of different modes of liquid chromatography of polymers Size exclusion chromatography Interaction chromatography Liquid chromatography at critical conditions Liquid exclusion-adsorption chromatography Liquid chromatography at limiting conditions Coupled and hyphenated liquid chromatographic methods Coupling of different modes of liquid chromatography with SEC as the second dimension Coupling of different modes of IC Hyphenation of liquid chromatography with spectroscopic techniques Liquid chromatography-Fourier transform infrared spectroscopy Liquid chromatography-mass spectrometry Liquid chromatography-nuclear magnetic resonance spectroscopy Summary References Multidetector size exclusion chromatography of polymers Physical detectors Detection of solution viscosity using viscosity detector Determination of the molar mass using universal calibration Advantages and limits of the calibration methods Absolute detection of molar mass using static light scattering detector Determination of macromolecular dimensions MALS for determination of radius of gyration DLS for determination of hydrodynamic radius Visco-detector for determination of viscosity radius Hyphenation of physical detectors for conformation distribution analysis dRI-MALS detection dRI-MALS-DLS detection dRI-MALS-Visco detection dRI-MALS-DLS-Visco detection Chemical detectors Analysis concepts UV/Vis detection FTIR detection NMR detection Mass spectrometry Commercially available detector and software solutions Summary References Temperature gradient interaction chromatography of polymers Separation mechanism Instrumentation Applications TGIC of linear homopolymers and the resolution of TGIC vs SEC TGIC separation of polymer mixtures Separation by functionality Analysis of nonlinear polymers Branched polymers Cyclic polymers Analysis of copolymers Random copolymers Block copolymers Outlook References Field-flow fractionation techniques for polymer characterization Separation mechanism and retention theory (normal mode) Sample relaxation and overloading in FFF Sample relaxation Sample overloading Flow FFF Retention theory Instrumentation Methodology Solvent selection Sample preparation and loading and overloading Flow rates and sample focusing in AF4 Advances in flow FFF instrumentation High-temperature AF4 Microstructured membranes Semipreparative AF4 Miniaturized AF4 Applications Polymer nanoparticles for drug delivery Macromolecules in food and beverages Proteins and protein aggregation Environmental pollution Thermal field-flow fractionation (ThFFF) Analyte retention Methodology Solvent selection Field strength Temperature field programming Cold wall temperature Flow rate Instrumentation Advances in ThFFF instrumentation Microfluidics Online detection Applications Composition Architecture Microgels Summary Acknowledgments References Characterization of polyolefins Molecular heterogeneity of polyolefins Crystallization-based fractionation techniques Temperature rising elution fractionation (TREF) Principles and instrumentation Typical applications Crystallization analysis fractionation (CRYSTAF) Principles and instrumentation Typical applications Crystallization elution fractionation (CEF) Principle and instrumentation Typical applications Column chromatographic techniques High temperature-size exclusion chromatography (HT-SEC) Principle and instrumentation Typical applications HT-SEC-multiple detection Coupled HT-SEC-FTIR Coupled HT-SEC-NMR High-temperature interaction chromatography (HT-IC) Principle and instrumentation Typical applications High temperature-liquid chromatography at critical conditions (HT-LCCC) High temperature-solvent gradient interaction chromatography (HT-SGIC) High temperature-temperature gradient interaction chromatography (HT-TGIC) Two-dimensional high temperature-liquid chromatography High temperature field-flow fractionation (HT-FFF) Principles and instrumentation Typical applications Summary and outlook References Analytical ultracentrifugation and combined molecular hydrodynamic approaches for polymer characterization Basic characteristics of macromolecules (end-to-end distance, radius of gyration, counter length, molar mass and pol ... Key hydrodynamic approaches in polymer science: The concept of hydrodynamic interactions of particles moving in a so ... Sedimentation velocity: Sedimentation coefficient, Gralen coefficient, concentration dependence Translational diffusion The synthetic boundary experiments Dynamic light scattering Concentration dependence of D Viscometry Viscometry of charged linear macromolecules Degree of dilution Size exclusion chromatography-Universal calibration Analytical ultracentrifugation for study of macromolecules Sedimentation velocity experiments Sedimentation velocity experiments and data analysis Analysis of the sedimentation data Sedimentation equilibrium Partial specific volume Consistency of the experimental data-Hydrodynamic invariants: Hydrodynamic invariant and sedimentation parameter Molar mass, hydrodynamic size, evaluation of dispersity parameter from velocity sedimentation data Conformation and conformational characteristics of macromolecules in solution Conformational characteristics-Equilibrium rigidity and diameter of the polymer chains Multi-HYDFIT (Monte Carlo simulations) Summary and outlook References Dilute solution viscometry of polymers Intrinsic viscosity and its measurement Relationship between intrinsic viscosity and molecular weight Estimation of polymer chain dimensions and conformational characteristics from intrinsic viscosity Recent developments and applications in viscosity of polymer solutions Conclusions and outlook Instrument Companies References Characterization of long-chain branching in polymers Use of NMR to detect and quantify long-chain branching Characterization of long-chain branching via dilute solution properties Theory Radius of gyration Intrinsic viscosity Hydrodynamic radius Comparison with experiments for model polymers Radius of gyration Intrinsic viscosity Hydrodynamic radius The parameter Characterization of long-chain branching by SEC with molecular weight/size-sensitive detectors Recent advances in long-chain branching characterization Conclusions and outlook References Mass spectrometry of polymers Evolution of polymer ionization techniques Electrospray ionization Limitations New trends Matrix-assisted laser desorption/ionization Limitations New trends Modern mass analyzers for polymer characterization Common MS/MS fragmentation techniques for polymer characterization Collision-induced dissociation Surface-induced dissociation Recent trends Electron capture dissociation and electron transfer dissociation New trends Infrared multiphoton photodissociation and ultraviolet photodissociation New trends Ion mobility separations Ion mobility separation of polymers New trends Selected polymer mass spectrometry applications Intractable polymers and industrial solids analysis Future outlook Polyolefins Future outlook Conclusions and outlook Acknowledgments References Vibrational spectroscopy of polymers Applications of vibrational spectroscopic analysis General polymeric structure analysis Analysis of chain conformation in the crystalline state Analysis of structural unit size Analysis of disordered chains Analysis of polymer blends; example PMMA-PEO blends and impact on technology Analysis of heterophase polyurethanes Characterization of polymer films on surfaces Polymer aging-Characterization of structural transformations Summary and outlook References Characterization of polymers by NMR Basic principles of NMR spectroscopy Magnetic resonance [2, 3] Internal magnetic interactions [2, 3, 7] High-resolution NMR in solid state [2, 3, 7, 8] Magic angle spinning [2, 3, 12] Cross-polarization [12] 1H high-power dipolar decoupling [12] Two-dimensional NMR spectroscopy [2, 3, 12, 20] Application of NMR to polymers Microstructure of synthetic polymers by solution- and melt-NMR Chain packing, conformation, chemical defects of semicrystalline polymers Chain trajectory of semicrystalline polymer Chemical reaction and decomposition of synthetic polymers Energy materials Supramolecular polymers Molecular dynamics of synthetic polymers Summary and outlook Acknowledgment References Characterization of polymers by dynamic light scattering The geometry of typical scattering experiments Quick start for the DLS newcomer Extracting quantitative information from DLS How DLS works DLS details: Assumptions and shortcuts we have made Instrument design for photon correlation: Mandatory compromise DLS lab: Just as important as the equipment Depolarized dynamic light scattering DLS in the overall scheme of things Alternative methods Tricks Case studies Conclusion Acknowledgment References Characterization of polymers by static light scattering Quick start for the SLS newcomer Extracting quantitative information from the SLS experiment How SLS works SLS in the overall scheme of things Copolymers and other multicomponent systems Polydispersity Design considerations Circling back to DLS and combining it with SLS Case studies Conclusion Acknowledgments References Characterization of polymers by LenS3 multiangle light scattering The LenS3 instrument and design principles Direct measurement of molecular weight Absolute normalization process Application of LenS3 for broadly polydisperse mixtures Application of LenS3 to low-molecular weight monodisperse samples Rg measurements using the LenS3 Analysis of biological samples using the LenS3 Summary and outlook LenS3 related technical presentations and applications (as of April 2020) References X-ray and neutron scattering of polymers Length scales accessible for neutrons, X-rays, and light Comparison of X-rays and neutrons Extracting structural information from scattering curves The importance of scattering contrast Novel sample environments Specific examples of structure from scattering of polymers Conformation of polymer chain in the bulk Structural development in 3D printed crystalline polymers Monitoring morphology development in printing organic semiconductors Controlling transport between droplets in emulsions Structure development in solvent vapor Structure of nanoparticles in an electric field Summary and outlook Acknowledgment References Microscopy of polymers Microscopy in the study of polymers Optical microscopy Principles of optical microscopy Specimen preparation of polymers for optical microscopy Imaging modes of optical microscopy Bright-field microscopy Dark-field microscopy Phase contrast Differential interference contrast Applications of optical microscopy in polymer science Laser scanning confocal microscopy for nanoimaging of polymers Scanning near field optical microscopy for nanoimaging of polymers Transmission electron microscopy Principle of TEM Specimen preparation of polymers for TEM Imaging modes of TEM Bright-field and dark-field images Phase contrast Applications of TEM in polymer science Conventional TEM of bulk polymers Sectioning Staining Cryo-TEM and freeze-fracture TEM of solutions Direct imaging cryo-TEM Freeze-fracture replication Scanning electron microscopy Principles of SEM Specimen preparation of polymers for SEM Types of SEM High resolution scanning electron microscopy Low voltage scanning electron microscopy Variable pressure scanning electron microscopy Applications of SEM in polymer science Atomic force microscopy Working principles of AFM Specimen preparation of polymers for AFM Modes of AFM Contact mode Noncontact mode Tapping mode Applications of AFM in polymer science Imaging of polymer morphology Molecular imaging Crystallization kinetics Wetting and dewetting Block copolymers Measuring physical properties Scanning probe lithography Summary and outlook References Index