Light scattering, size exclusion chromatography, and asymmetric flow field flow fractionation : powerful tools for the characterization of polymers, proteins, and nanoparticles

This book focuses on three important methods of polymer analysis: light scattering, size exclusion chromatography (SEC) and asymmetric flow field flow fractionation (A4F). These methods are important primarily in polymer science, but also in advanced materials science and emerging technologies. Readers will learn how light scattering measurements can easily provide absolute molar mass and size without any calibration or using reference standards and how its potential can be multiplied by the combination with a separation technique. Current users of conventional SEC will learn that a light scattering detector effectively solves the crucial problem of SEC, i.e. the column calibration, significantly improves reproducibility of SEC measurements and provides much additional information. In addition, they will see that A4F can overcome many traditional SEC problems, such as interactions of polymers with column packing, shearing degradation and limited separation of ultra-high molar mass polymers.The book also provides understanding the basic theory and principles of light scattering, SEC and A4F. The theoretical part is accomplished by numerous examples of the real applications of particular methods and their combinations for various synthetic and natural polymers, proteins and nanoparticles. Special attention is paid to the characterization of branched polymers.The book targets beginners as well as the experienced users who need to confirm their own understanding or help interpret their results. Light Scattering, Size Exclusion Chromatography and Asymmetric Flow Field Flow Fractionation......Page 2 Contents......Page 6 Preface......Page 10 1.1 Introduction......Page 14 1.2 Molecular Structure of Polymers......Page 15 1.2.1 Macromolecules in Dilute Solution......Page 17 1.3 Molar Mass Distribution......Page 23 1.3.1 Description of Molar Mass Distribution......Page 26 1.3.1.1 Distribution Functions......Page 30 1.3.1.2 Molar Mass Averages......Page 34 1.4.1 Method of End Groups......Page 36 1.4.2.1 Vapor Pressure Osmometry......Page 37 1.4.2.2 Membrane Osmometry......Page 38 1.4.3 Dilute Solution Viscometry......Page 39 1.4.3.1 Properties of Mark-Houwink Exponent......Page 43 1.4.3.2 Molecular Size from Intrinsic Viscosity......Page 44 1.4.3.3 Dependence of Intrinsic Viscosity on Polymer Structure, Temperature, and Solvent......Page 46 1.4.4 Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry......Page 47 1.4.5 Analytical Ultracentrifugation......Page 48 1.6 References......Page 49 2.1 Theory and Basic Principles......Page 50 2.2 Types of Light Scattering......Page 52 2.2.1 Static Light Scattering......Page 53 2.2.1.1 Particle Scattering Functions......Page 60 2.2.1.3 Processing the Experimental Data......Page 67 2.2.2 Dynamic Light Scattering......Page 72 2.3 Light Scattering Instrumentation......Page 76 2.4 Specific Refractive Index Increment......Page 78 2.5 Light Scattering in Batch and Chromatography Mode......Page 85 2.6 Parameters Affecting Accuracy of Molar Mass Determined by Light Scattering......Page 91 2.7 Examples of Light Scattering Measurement in Batch Mode......Page 97 2.8 Keynotes......Page 109 2.9 References......Page 110 3.1 Introduction......Page 112 3.2.1 Steric Exclusion......Page 115 3.2.3 Separation by Flow......Page 116 3.2.4 Peak Broadening and Separation Efficiency......Page 118 3.2.5 Secondary Separation Mechanisms......Page 126 3.3 Instrumentation......Page 127 3.3.1 Solvents......Page 131 3.3.2 Columns and Column Packing......Page 135 3.3.3 Detectors......Page 140 3.3.3.1 UV Detector......Page 143 3.3.3.2 Refractive Index Detector......Page 144 3.3.3.3 Infrared Detector......Page 146 3.3.3.4 Evaporative Light Scattering Detector......Page 147 3.3.3.5 Viscosity Detector......Page 148 3.3.3.6 Light Scattering Detector......Page 153 3.3.3.7 Other Types of Detectors......Page 155 3.4 Column Calibration......Page 156 3.4.1 Universal Calibration......Page 162 3.4.2 Flow Marker......Page 165 3.5.1 Sample Preparation......Page 167 3.5.2 Determination of Molar Mass and Molar Mass Distribution......Page 172 3.5.3 Reporting Results......Page 186 3.5.4 Characterization of Chemical Composition of Copolymers and Polymer Blends......Page 187 3.5.5 Characterization of Oligomers......Page 188 3.5.6 Influence of Separation Conditions......Page 197 3.5.7 Accuracy, Repeatability, and Reproducibility of SEC Measurements......Page 205 3.6 Applications of SEC......Page 211 3.7 Keynotes......Page 217 3.8 References......Page 218 4.1 Introduction......Page 220 4.2 Data Collection and Processing......Page 221 4.2.1 Processing MALS Data......Page 232 4.2.1.2 Zimm Fit Method......Page 233 4.2.1.5 Influence of Light Scattering Formalism on Molar Mass and RMS Radius......Page 234 4.2.2 Determination of Molar Mass and RMS Radius Averages and Distributions......Page 245 4.2.3 Chromatogram Processing......Page 248 4.2.5 Repeatability and Reproducibility......Page 253 4.2.6 Accuracy of Results......Page 255 4.3.1 Determination of Molar Mass Distribution......Page 256 4.3.2 Fast Determination of Molar Mass......Page 260 4.3.3.1 Branched Polymers......Page 264 4.3.3.2 Copolymers and Polymer Blends......Page 265 4.3.4 Conformation Plots......Page 267 4.3.5 Mark-Houwink Plots......Page 268 4.5 References......Page 270 5.1 Introduction......Page 272 5.2 Theory and Basic Principles......Page 274 5.2.1 Separation Mechanisms......Page 284 5.2.2 Resolution and Band Broadening......Page 286 5.3 Instrumentation......Page 290 5.4 Measurements and Data Processing......Page 294 5.4.1 Influence of Separation Conditions......Page 298 5.4.1.1 Isocratic and Gradient Experiments......Page 300 5.4.1.2 Overloading......Page 301 5.4.2 Practical Measurements......Page 302 5.5 A4F Applications......Page 304 5.6 Keynotes......Page 314 5.7 References......Page 316 6.1 Introduction......Page 320 6.2 Detection and Characterization of Branching......Page 324 6.2.1 SEC Elution Behavior of Branched Polymers......Page 331 6.2.2 Distribution of Branching......Page 334 6.2.3 Average Branching Ratios......Page 343 6.2.4 Other Methods for the Identification and Characterization of Branching......Page 346 6.3 Examples of Characterization of Branching......Page 350 6.4 Keynotes......Page 357 6.5 References......Page 358 Symbols......Page 360 Abbreviations......Page 366 Index......Page 368 A comprehensive, practical approach to three powerful methods of polymer analysis and characterization. This book serves as a complete compendium of three important methods widely used for the characterization of synthetic and natural polymers—light scattering, size exclusion chromatography (SEC), and asymmetric flow field flow fractionation (A4F). Featuring numerous up-to-date examples of experimental results obtained by light scattering, SEC, and A4F measurements, Light Scattering, Size Exclusion Chromatography and Asymmetric Flow Field Flow Fractionation takes an all-in-one approach to deliver a complete and thorough explanation of the principles, theories, and instrumentation needed to characterize polymers from the viewpoint of their molar mass distribution, size, branching, and aggregation. This comprehensive resource: Is the only book gathering light scattering, size exclusion chromatography, and asymmetric flow field flow fractionation into a single text. Systematically compares results of size exclusion chromatography with results of asymmetric flow field flow fractionation, and how these two methods complement each other. Provides in-depth guidelines for reproducible and correct determination of molar mass and molecular size of polymers using SEC or A4F coupled with a multi-angle light scattering detector. Offers a detailed overview of the methodology, detection, and characterization of polymer branching. Light Scattering, Size Exclusion Chromatography and Asymmetric Flow Field Flow Fractionation should be of great interest to all those engaged in the polymer analysis and characterization in industrial and university research, as well as in manufacturing quality control laboratories. Both beginners and experienced can confidently rely on this volume to confirm their own understanding or to help interpret their results "Light scattering measurements bring valuable information about the molecular size and intensity of interactions of polymer molecules with a solvent. The book provides understanding of the basic theory and principles of light scattering, size exclusion chromatography, and asymmetric flow field fractionation."--Pub. desc