Polymeric Liquids & Networks
Structure and Properties
Hardcover | 20 November 2003 | Edition Number 1
At a Glance
801 Pages
22.9 x 17.8 x 3.81
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Polymeric Liquids and Networks: Structure and Properties is the first book of two by William W. Graessley that presents a unified view of flexible-chain polymer liquids and networks. The topics of both volumes range from equilibrium properties to dynamic response, finite deformation behavior and non-Newtonian flow. The second book will be titled Polymeric Liquids and Networks: Dynamics and Rheology. These various aspects of the field were developed over the past 70 years by researchers from many academic disciplines. The infusion of fresh viewpoints continually invigorated and enriched the field, making polymeric liquids and networks a truly interdisciplinary subject. The lack of a common terminology and perspective, however, has led to compartmentalization, making it difficult for a newcomer, even one technically trained, to gain a broad appreciation of the field and to see the relationships among its various parts. The aim of these two books, without diluting the substance, is to achieve a desired unity.
Polymeric Liquids and Networks emphasizes fundamental principles and a molecular viewpoint. The conceptual basis of theories underlying each topical area is explained with derivations sometimes outlined briefly and sometimes given in detail. Technical terminology is kept to a minimum necessary for coherent presentation. The goal of the text is to provide an informed understanding rather than detailed technical proficiency. Theory, experiment, and simulation are woven together as appropriate for achieving a balanced view. The books are designed to serve academic and industrial needs, consolidating the understanding of topics with both practical and fundamental significance, and written from a technical but non-specialized perspective.
The books deal mainly with non-polar and weakly polar species and largely with results derived from experiments on structurally well-defined systems. The objective is not to ignore the more complex systems, which are pervasive in both nature and industry and important in their own right. Much space is devoted to structural distributions, their characterization and their effect on properties. It is rather to provide a framework for better understanding of all polymeric liquids by identifying, in the simplest possible circumstances, the universal attributes of a chain-like and flexible molecular structure.
Industry Reviews
The attractive feature of Polymeric Liquids and Networks is that it starts from an elementary viewpoint emphasizing molecular chemical structure. Graessley then integrates this chemistry-dominated description with one that focuses on the universal properties of polymers.... ...Organized as a field guide to polymer science... The text is a wealth of information on the more technical matters of characterizing the structure and interactions of polymer solutions and understanding the miscibility of polymer blends in terms of polymer structural properties and measures of interpolymer interaction. ...A valuable resource for newcomers who are trying to understand essential concepts of polymer science, learn some history of the field, and find direction for further reading.
-- Physics Today
The attractive feature of Polymeric Liquids and Networks is that it starts from an elementary viewpoint emphasizing molecular chemical structure. Graessley then integrates this chemistry-dominated description with one that focuses on the universal properties of polymers.... ...Organized as a field guide to polymer science... The text is a wealth of information on the more technical matters of characterizing the structure and interactions of polymer solutions and understanding the miscibility of polymer blends in terms of polymer structural properties and measures of interpolymer interaction. ...A valuable resource for newcomers who are trying to understand essential concepts of polymer science, learn some history of the field, and find direction for further reading."
-- Physics Today
Introduction | p. xiii |
Introduction | p. 1 |
Molecular Nature of Polymers | p. 1 |
Polymeric Structure | p. 6 |
Chemical Microstructure | p. 7 |
Chemical Macrostructure | p. 10 |
Rotational States | p. 10 |
Polymeric Properties | p. 12 |
Species Dependence | p. 13 |
Architectural Dependence | p. 14 |
Viscosity | p. 14 |
Viscoelastic behavior | p. 16 |
Macromolecular Heterogeneity | p. 17 |
Averages | p. 18 |
Distribution Functions | p. 20 |
Exponential distribution | p. 21 |
Distributions from branching and scission | p. 22 |
Empirical distribution functions | p. 25 |
Molecular Simulations | p. 27 |
Molecular Liquids | p. 29 |
Microscopic Origin of Liquid Properties | p. 35 |
Intermolecular Forces | p. 35 |
Terminology | p. 38 |
Statistical Thermodynamics | p. 40 |
Pair Distributions and Intermolecular Energy | p. 43 |
Principles of Elastic Scattering | p. 46 |
The Structure Factor | p. 52 |
Liquid Structure and Properties | p. 55 |
Scattering by Pure Liquids | p. 55 |
The van der Waals Liquid | p. 59 |
Hard Sphere Liquids | p. 61 |
Generalized van der Waals Theory | p. 63 |
The Longuet-Higgins and Widom Model | p. 64 |
Cell Models | p. 66 |
Lattice Models | p. 67 |
Reduced Equations of State | p. 69 |
Cohesive Energy and Internal Pressure | p. 70 |
Molecular Mixtures | p. 77 |
Thermodynamics of Liquid Mixtures | p. 77 |
Liquid-Liquid Phase Behavior | p. 83 |
Molecular Aspects of Mixing | p. 89 |
Simple Mixtures | p. 94 |
Properties of the Interaction Parameter | p. 96 |
Phase Behavior | p. 98 |
Observations | p. 100 |
Regular Mixtures | p. 103 |
Commentary | p. 105 |
Volume Change on Mixing | p. 107 |
The Free Volume Effect | p. 109 |
Modified FOV Theory | p. 111 |
The Free Volume Interaction Parameter | p. 114 |
Commentary | p. 116 |
The Random Coil Model | p. 121 |
Random Walks | p. 123 |
Average End-to-End Distance | p. 124 |
Radius of Gyration | p. 125 |
Polymer Chains | p. 128 |
Locally Restricted Conformations | p. 129 |
Step Length Definitions | p. 132 |
Nonlinear Molecules | p. 136 |
Branched Chains | p. 137 |
Macrocycles | p. 140 |
Random Coil Asymmetry | p. 142 |
Conformational Distributions | p. 142 |
The End-to-End Vector Distribution | p. 143 |
The Gaussian Form | p. 147 |
Mass Distribution for Gaussian Coils | p. 148 |
Properties of Random Coil Ensembles | p. 149 |
Mechanical Properties | p. 149 |
Thermodynamic Properties | p. 150 |
Scattering Properties | p. 152 |
Form Factors | p. 152 |
Random coil molecules | p. 154 |
Pair distributions | p. 155 |
General properties | p. 156 |
Structure Factors | p. 158 |
One-component systems | p. 159 |
Two-component systems | p. 160 |
Incompressible mixtures | p. 160 |
Dilute Solution Characterization | p. 167 |
Thermodynamic Characterization Methods | p. 167 |
Osmotic Pressure | p. 168 |
Light Scattering | p. 171 |
Fundamentals | p. 172 |
Dilute solutions | p. 175 |
Scattering method comparisons | p. 182 |
Dynamic Characterization Methods | p. 184 |
Dynamic Light Scattering | p. 185 |
Viscometry | p. 189 |
Chromatographic Methods | p. 192 |
Size Exclusion Chromatography | p. 192 |
Multidetector Methods | p. 197 |
Dilute Solution Properties | p. 203 |
Intramolecular Interactions | p. 203 |
Excluded Volume | p. 204 |
Pervaded volume and self-concentration | p. 206 |
Self-exclusion | p. 208 |
Hydrodynamic Interaction | p. 217 |
Linear Polymers | p. 222 |
Limiting Size Ratios | p. 223 |
Expansion Factors | p. 224 |
Good Solvent Master Curves | p. 227 |
Master curve forms | p. 231 |
Onset molecular weights | p. 232 |
Branched and Macrocyclic Polymers | p. 235 |
Lightly Branched Model Structures | p. 237 |
Regular stars | p. 237 |
Rings | p. 239 |
H-Polymers | p. 243 |
Combs | p. 243 |
Lightly Branched Statistical Structures | p. 247 |
Highly Branched Structures | p. 249 |
Daoud-Cotton model | p. 251 |
Many-arm star properties | p. 254 |
Colloidal analogies | p. 255 |
Concentration Regimes | p. 257 |
Polymer Solutions | p. 265 |
Coil Size Beyond Overlap | p. 266 |
Chain Dimensions in Polymer Melts | p. 266 |
Chain Dimensions in Semidilute Solutions | p. 269 |
Excluded volume screening | p. 269 |
Concentration dependence | p. 273 |
Semidilute-concentrated crossover | p. 274 |
Observations | p. 276 |
Osmotic Pressure Beyond Overlap | p. 278 |
Flory-Huggins Predictions | p. 280 |
Scaling Analysis | p. 283 |
Experimental Observations | p. 284 |
Scattering Beyond Overlap | p. 286 |
Correlation Length | p. 286 |
The Random Phase Approximation | p. 293 |
Interpretation Alternatives | p. 295 |
Branch-Induced Ordering | p. 296 |
The Interaction Parameter | p. 297 |
Evaluation of x | p. 298 |
Vapor composition and sorption | p. 298 |
Osmometry | p. 299 |
Inverse chromatography | p. 300 |
Scattering | p. 300 |
Interpretation of x | p. 304 |
Free volume effects | p. 306 |
Impact on dilute solutions | p. 312 |
Athermal solutions | p. 313 |
Liquid-Liquid Phase Behavior | p. 314 |
Upper Critical Behavior | p. 314 |
Lower Critical Behavior | p. 320 |
Scattering and Criticality | p. 323 |
The Ginzburg Criterion | p. 329 |
Polymer Blends | p. 341 |
Molecular Interactions | p. 343 |
Isotopic Blends | p. 347 |
Isotopic Interactions | p. 348 |
Experimental aspects | p. 349 |
Temperature Dependence of the Interactions | p. 352 |
Some Properties of x[subscript HD] | p. 355 |
Polyolefin Blends | p. 356 |
Measurements | p. 357 |
Observations | p. 359 |
Solubility Parameters | p. 364 |
Molecular considerations | p. 367 |
PVT measurements | p. 369 |
Simulations | p. 372 |
Interaction Properties | p. 375 |
Temperature dependence | p. 375 |
Pressure dependence | p. 377 |
Molecular weight dependence | p. 378 |
Composition dependence | p. 379 |
Irregular Blends | p. 381 |
Hydrocarbon Polymer Blends | p. 385 |
Inter-Family Blends | p. 388 |
Intra-Family Blends | p. 389 |
Commentary | p. 391 |
Blends of Copolymers | p. 393 |
Sequencing Effects | p. 393 |
Mean Composition Effects | p. 394 |
Blends with Specific Associations | p. 399 |
Network Structure and Elasticity | p. 409 |
Equal Reactivity and Random Linking | p. 411 |
Network Connectivity | p. 413 |
Strand Dimensions | p. 418 |
Linking Statistics | p. 418 |
Structurally Related Observables | p. 420 |
Pre-Gelation Region | p. 421 |
The Gel Curve | p. 423 |
Elasticity-Related Properties | p. 427 |
Active Junctions and Strands | p. 428 |
Topological and Dynamics-Related Properties | p. 431 |
Architectural Characterization | p. 435 |
General Considerations on Network Elasticity | p. 436 |
The Affine Network | p. 441 |
The Logarithmic Contribution | p. 443 |
Effects of Temperature and Volume Change | p. 445 |
Network Pressure | p. 446 |
The Phantom Network | p. 447 |
The Entangled Network | p. 452 |
Modulus Magnitude | p. 453 |
Experimental Tests | p. 456 |
Comments | p. 466 |
Network Properties | p. 471 |
Stress-Strain Behavior | p. 472 |
The Mooney-Rivlin Form | p. 476 |
Swelling and Supercoiling Effects | p. 479 |
The Ferry-Kan Formulation | p. 487 |
Swelling Equilibrium | p. 490 |
Thermoelasticity | p. 501 |
Observations on Networks | p. 508 |
Microscopic Features | p. 509 |
Orientational correlations | p. 509 |
Neutron scattering | p. 509 |
Macroscopic Features | p. 514 |
Modeling Uncrossability | p. 514 |
Topological Classification | p. 519 |
Slip-Links | p. 522 |
Constrained Junction Models | p. 524 |
Tube Models | p. 524 |
Affine models | p. 526 |
Constant mesh density models | p. 527 |
Empirical models | p. 528 |
Nonaffine models | p. 528 |
Tube model comparisons | p. 530 |
Commentary | p. 530 |
Symbols | p. 537 |
Subject Index | p. 543 |
Author Index | p. 549 |
Table of Contents provided by Rittenhouse. All Rights Reserved. |
ISBN: 9780815341697
ISBN-10: 0815341695
Published: 20th November 2003
Format: Hardcover
Language: English
Number of Pages: 801
Audience: College, Tertiary and University
Publisher: Taylor & Francis Inc
Country of Publication: US
Edition Number: 1
Dimensions (cm): 22.9 x 17.8 x 3.81
Weight (kg): 1.32
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