MODERN SIZE-EXCLUSION LIQUID CHROMATOGRAPHY -- CONTENTS -- Foreword -- Preface -- 1 Background -- 1.1 Introduction -- 1.2 History -- 1.3 Utility of SEC -- 1.4 Molar Mass Averages and Molar Mass Distribution -- 1.5 Structure of The Book -- References -- 2 Retention -- 2.1 Introduction -- 2.2 Solute Retention in LC -- 2.3 Solute Retention in SEC -- 2.4 SEC Retention Mechanism -- 2.5 Theoretical Models of SEC Separation -- 2.5.1 Hard-Sphere Solute Model -- 2.5.2 Rigid Molecules of Other Shapes -- 2.5.3 Random-Coil Solute Model -- 2.6 Other Considerations -- 2.6.1 Factors Influencing SEC Retention -- 2.6.2 Failure to Define an Effective Polymer Radius -- 2.6.3 Hydrodynamic Chromatography Effects in SEC -- 2.6.4 Slalom Chromatography Effects in SEC -- References -- 3 Band Broadening -- 3.1 Introduction -- 3.1.1 Basic Column-Dispersion Processes -- 3.1.2 Peak Variance -- 3.2 LC Plate Theory -- 3.2.1 Basic Plate Theory -- 3.2.2 The van Deemter Equation -- 3.2.3 Flow-Diffusion Coupling -- 3.2.4 Reduced Plate Height -- 3.3 Mechanism of SEC Band Broadening -- 3.3.1 Experimental Verification -- 3.3.2 Rate Theory -- 3.3.3 Theoretical Inferences -- 3.4 Influencing Factors -- 3.4.1 Column Parameters -- 3.4.2 Kinetic Factors -- 3.4.3 Experimental Factors -- 3.5 Experimental Methods -- 3.5.1 Plate Number -- 3.5.2 Column-Dispersion Calibration -- References -- 4 Resolution -- 4.1 Introduction -- 4.1.1 Chromatographic Resolution -- 4.1.2 Peak-Capacity Concept -- 4.2 Resolution Concept in SEC of Polymers -- 4.3 Molar Mass Accuracy Criterion -- 4.4 Applications of Column Performance Criteria -- 4.5 Pore Geometry and Operational Effects -- 4.5.1 Connecting Columns -- 4.5.2 Separation Capacity of Single Pores -- 4.5.3 Effect of Packing Pore-Size Distribution -- 4.5.4 Effect of Operating Parameters -- References -- 5 Equipment -- 5.1 Introduction.

5.2 Extra-Column Effects: General -- 5.3 Mobile-Phase Reservoirs, Inlet Filters, and Degassers -- 5.4 Solvent-Metering Systems (Pumps) -- 5.4.1 General Pump Specifications -- 5.4.2 Reciprocating Pumps -- 5.5 Sample Injectors and Autosamplers -- 5.6 Miscellaneous Hardware -- 5.7 Laboratory Safety -- References -- 6 The Column -- 6.1 Introduction -- 6.2 Column Packings -- 6.2.1 Semirigid Organic Gels -- 6.2.2 Rigid Inorganic Packings -- 6.3 Column-Packing Methods -- 6.3.1 Particle Technology -- 6.3.2 Basis of Column-Packing Techniques -- 6.4 Column Performance -- References -- 7 Experimental Variables and Techniques -- 7.1 Introduction -- 7.2 Solvent Effects -- 7.2.1 Sample Solubility -- 7.2.2 Other Solvent Effects -- 7.2.3 Flow-Rate Effects -- 7.2.4 Temperature Effects -- 7.3 Substrate Effects -- 7.4 Sample Effects -- 7.4.1 Sample Volume -- 7.4.2 Sample Weight or Concentration -- 7.5 Laboratory Techniques -- 7.6 Solvent Selection and Preparation -- 7.6.1 Convenience -- 7.6.2 Sample Type -- 7.6.3 Effect on Column Packing -- 7.6.4 Operation -- 7.6.5 Safety -- 7.6.6 Solvent Purification and Modification -- 7.7 Selection and Use of Standard Reference Materials -- 7.8 Detector Selection -- 7.9 Column Selection and Handling -- 7.9.1 Optimum Single Pore-Size Separations -- 7.9.2 Bimodal Pore-Size Separations: Optimum Linearity and Range -- 7.9.3 Other Column Selection Guidelines -- 7.9.4 Column Handling -- 7.10 Chromatographic Design Considerations -- 7.11 Making the Separation -- 7.11.1 Dissolving the Sample and Standards -- 7.11.2 Sample Solution Filtration -- 7.11.3 Sample Injection -- 7.11.4 Baseline Stability -- 7.11.5 Obtaining and Using a Chromatogram Baseline -- 7.12 Troubleshooting -- 7.12.1 Excessively High Pressure -- 7.12.2 Column Plugging -- 7.12.3 Air Bubbles and Leaks -- 7.12.4 Poor Resolution -- 7.12.5 Low Solute Recovery.

7.12.6 Constancy of Separation -- 7.12.7 Peak Shape -- References -- 8 Calibration -- 8.1 Introduction -- 8.2 Calibration with Narrow-MMD Standards -- 8.2.1 Peak-Position (Calibrant-Relative) Calibration -- 8.2.2 Universal Calibration -- 8.2.3 Mark-Houwink Calibration -- 8.3 Calibration with Broad-MMD Standards -- 8.3.1 Integral-MMD Method -- 8.3.2 Linear Calibration Methods -- 8.4 Accuracy of Calibration Methods -- 8.5 Actual Molar Mass Across the SEC Elution Curve -- 8.6 Linear Calibration Ranges -- 8.7 Recent Developments and Recommendations on Band-Broadening Correction -- 8.7.1 Algorithm for BBC in Conventional SEC Analysis with Only a Concentration-Sensitive Detector -- 8.7.2 Algorithm for BBC in Dual-Detector SEC Using an Online Static Light-Scattering Detector -- 8.7.3 Algorithm for BBC in Universal Calibration Using an Online Viscosity Detector -- 8.7.4 Algorithm for BBC in Triple-Detector SEC Using Online Static Light Scattering, Viscosity, and Concentration Detectors -- References -- 9 Physical Detectors -- 9.1 Introduction -- 9.2 Concentration-Sensitive Detectors -- 9.2.1 Differential Refractometers -- 9.2.2 UV/Visible Detectors -- 9.2.3 Evaporative-Type Detectors -- 9.3 Static Light-Scattering Detection -- 9.3.1 Multiangle Light Scattering -- 9.3.2 Low-Angle Light Scattering -- 9.3.3 Off-Line, Batch-Mode MALS -- 9.3.4 Depolarized MALS -- 9.4 Quasielastic Light-Scattering Detection -- 9.4.1 QELS Instrumentation -- 9.5 Viscometric Detection -- 9.5.1 Single-Capillary Viscometers -- 9.5.2 Differential Viscometers -- 9.5.3 Intrinsic Viscosity and the Viscometric Radius -- 9.5.4 Viscometry Instrumentation -- 9.6 SEC(3) -- References -- 10 Chemical Detectors -- 10.1 Introduction -- 10.2 Mass Spectrometry -- 10.2.1 Electrospray Ionization Mass Spectrometry -- 10.2.2 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.

10.2.3 Inductively Coupled Plasma Mass Spectrometry -- 10.3 Fourier Transform Infrared Spectroscopy -- 10.3.1 FTIR as a Pseudophysical Detector: Short-Chain Branching Distribution of Polyolefins -- 10.3.2 FTIR as a Chemical Detector -- 10.3.3 Comparison of Online and Continuous Off-Line SEC/FTIR -- 10.4 Nuclear Magnetic Resonance Spectroscopy -- 10.5 Other Chemical Detectors -- 10.5.1 Ultraviolet Detection -- 10.5.2 Fluorescence -- 10.5.3 Conductivity -- 10.5.4 Dynamic Surface Tension Detection -- 10.5.5 Microscale Molecular Mass Sensor -- 10.6 Coupling of Chemical Detectors -- References -- 11 Polymer Architecture and Dilute Solution Thermodynamics -- 11.1 Introduction -- 11.2 Long-Chain Branching -- 11.2.1 Quantitating the Long-Chain Branching Distribution by SEC/MALS -- 11.2.2 Qualitative and Semiquantitative Descriptions of the Long-Chain Branching Distribution by SEC/VISC -- 11.2.3 Average Molar Mass Between Long-Chain Branches -- 11.3 Determining the Short-Chain Branching Distribution -- 11.4 Polymer Architecture: Conformation and Topology -- 11.4.1 Determining the Fractal Dimension -- 11.4.2 Dimensionless Radii Ratios -- 11.4.3 Dimensionless Functions -- 11.4.4 Caveats Regarding Dimensionless Parameters -- 11.5 Star Polymers -- 11.6 Determining the Persistence Length -- 11.7 Determining the Characteristic Ratio -- 11.8 Local Polydispersity -- References -- 12 Aqueous SEC -- 12.1 Introduction -- 12.2 Aqueous SEC Columns -- 12.3 Non-Size-Exclusion Effects and Mobile-Phase Additives -- 12.4 Select Applications of Aqueous SEC -- 12.4.1 Polysaccharides -- 12.4.2 Proteins and Peptides -- 12.4.3 Synthetic Polymers -- 12.4.4 Polyelectrolytes -- 12.4.5 Inorganic Compounds -- References -- 13 Oligomeric SEC -- 13.1 Introduction -- 13.2 What is an Oligomer? -- 13.3 Preliminary Considerations -- 13.3.1 Advantages over Polymeric SEC.

13.3.2 Difficulties as Compared to Polymeric SEC -- 13.4 Oligomeric SEC Columns -- 13.5 Select Applications of Oligomeric SEC -- 13.5.1 Characterization of Tackifiers, Resins, and Resin Prepolymers -- 13.5.2 Characterization of Antioxidant Lubricant Additives -- 13.5.3 Characterization and Quantitation of Plasticizers -- 13.5.4 Polymer Exemption Data -- 13.5.5 SEC of Oligosaccharides -- 13.5.6 Determining the Solution Conformational Entropy of Oligomers -- 13.5.7 Determining Molar Masses of Oligomers by SEC/MALS -- 13.6 Optimizing Resolution in Oligomeric SEC -- References -- 14 SEC in 2D-LC Separations -- 14.1 Introduction -- 14.2 Principles of 2D Polymer Separations -- 14.2.1 Separation Angle and Percent Synentropy -- 14.3 Designing an Experimental 2D-LC Protocol -- 14.4 Eluent Transfer in 2D-LC -- 14.5 Stop-Flow SEC × LC -- 14.6 Select Applications of 2D-LC -- 14.6.1 HPLC -- 14.6.2 Liquid Chromatography at the Critical Condition -- 14.6.3 Other Methods -- 14.7 SEC in 3D Separations -- References -- 15 Special Techniques -- 15.1 Introduction -- 15.2 Preparative SEC -- 15.2.1 Experimentation -- 15.2.2 Applications -- 15.3 Recycle SEC -- 15.3.1 Theory -- 15.3.2 Equipment -- 15.3.3 Uses of the Recycle Method -- 15.4 High-Speed SEC -- 15.5 Inverse SEC -- 15.6 Vacancy and Differential SEC -- 15.7 Size-Exclusion Electrochromatography -- References -- 16 High-Temperature SEC and Rheological Connections -- 16.1 Introduction -- 16.2 High-Temperature SEC -- 16.2.1 HT-SEC Instrumentation -- 16.3 Complementarity of SEC and Rheology -- 16.3.1 Obtaining the MMD from Rheological Measurements -- 16.3.2 Obtaining Rheological Properties from SEC Measurements -- 16.3.3 Behavior of Dilute Oligomer Solutions -- References -- Symbols -- Abbreviations -- Index.