Viscoelastic Properties of Polymers

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John Wiley & Sons, Sep 16, 1980 - Science - 641 pages
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Viscoelastic behavior reflects the combined viscous and elastic responses, under mechanical stress, of materials which are intermediate between liquids and solids in character. Polymers—the basic materials of the rubber and plastic industries and important to the textile, petroleum, automobile, paper, and pharmaceutical industries as well—exhibit viscoelasticity to a pronounced degree. Their viscoelastic properties determine the mechanical performance of the final products of these industries, and also the success of processing methods at intermediate stages of production. Viscoelastic Properties of Polymers examines, in detail, the effects of the many variables on which the basic viscoelastic properties depend. These include temperature, pressure, and time; polymer chemical composition, molecular weight and weight distribution, branching and crystallinity; dilution with solvents or plasticizers; and mixture with other materials to form composite systems. With guidance by molecular theory, the dependence of viscoelastic properties on these variables can be simplified by introducing certain ancillary concepts such as the fractional free volume, the monomeric friction coefficient, and the spacing between entanglement loci, to provide a qualitative understanding and in many cases a quantitative prediction of how to achieve desired results. The phenomenological theory of viscoelasticity—which permits interrelation of the results of different types of experiments—is presented first, with many useful approximation procedures for calculations given. A wide variety of experimental methods is then described, with critical evaluation of their applicability to polymeric materials of different consistencies and in different regions of the time scale (or, for oscillating deformations, the frequency scale). A review of the present state of molecular theory follows, so that viscoelasticity can be related to the motions of flexible polymer molecules and their entanglements and network junctions. The dependence of viscoelastic properties on temperature and pressure, and its descriptions using reduced variables, are discussed in detail. Several chapters are then devoted to the dependence of viscoelastic properties on chemical composition, molecular weight, presence of diluents, and other features, for several characteristic classes of polymer materials. Finally, a few examples are given to illustrate the many potential applications of these principles to practical problems in the processing and use of rubbers, plastics, and fibers, and in the control of vibration and noise. The third edition has been brought up to date to reflect the important developments, in a decade of exceptionally active research, which have led to a wider use of polymers, and a wider recognition of the importance and range of application of viscoelastic properties. Additional data have been incorporated, and the book’s chapters on dilute solutions, theory of undiluted polymers, plateau and terminal zones, cross-linked polymers, and concentrated solutions have been extensively rewritten to take into account new theories and new experimental results. Technical managers and research workers in the wide range of industries in which polymers play an important role will find that the book provides basic information for practical applications, and graduate students in chemistry and engineering will find, in its illustrations with real data and real numbers, an accessible introduction to the principles of viscoelasticity.
 

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Contents

The Nature
1
Description of Linear TimeDependent Experiments in Shear
8
Mechanical Model Analogies of Linear Viscoelastic Behavior
15
Illustrations
33
B Linear Viscoelastic Behavior in Bulk Voluminal Deformation
48
Conclusions
54
B The Relaxation and Retardation Spectra
60
Calculation of Viscoelastic Functions and Constants from
64
Interrelation of Effects of Temperature and Pressure
294
E Reduced Variables and FreeVolume Parameters from Other Than
301
Changes in Internal Structure due to Crystallinity
312
NonNewtonian Viscosity
315
The Transition Zone
321
B The Monomeric Friction Coefficient
328
Relation of fo to the Onset of the Transition Zone
342
Behavior of Copolymers and Polymer Mixtures
348

Evaluation of Viscoelastic Constants
70
H Relations from Nonlinear Constitutive Equations
76
B Interrelations between the Spectra
87
F Table of Correction Factors
94
Normal Stress Measurements
105
E Dynamic Oscillatory Measurements of Characteristic
116
G Dynamic Measurements on Liquids in Solid Matrices
124
Experimental Methods
130
Wave Propagation
144
Experimental Methods
154
Compound Resonance Vibration Devices
160
Experimental Methods
168
Partially Flexible Elongated Molecules
204
E Behavior at High Frequencies and in HighViscosity
214
Molecular Theory
224
B CrossLinked Networks
233
UncrossLihked Polymers of High Molecular Weight
241
Concentrated Solutions
248
E Nonlinear Behavior in UncrossLinked Polymers of High Molecular
257
Dependence
264
A Origin of the Method of Reduced Variables
266
B Procedure and Criteria for Applicability of the Method of Reduced
273
The WLF Equation and the Relation of Temperature Dependence
280
The WLF Equation
287
Behavior of Filled Systems
356
The Plateau
366
B Estimations of Entanglement Spacings
372
Behavior in the Terminal Zone
379
Behavior in the Plateau Zone
391
CrossLinked Polymers
404
The Classy State
437
Crystalline Polymers
457
Polymers with Low Degree of Crystallinity
469
and Gels
486
B The Plateau Zone
501
Linear Viscoelastic Behavior in the Terminal Zone
509
E Gels CrossLinked in Solution
529
F Gels Swollen after CrossLinking
539
Viscoelastic Behavior
545
Dynamic Properties in Bulk Compression
558
Applications
570
Rupture below the Glass Transition Temperature
587
Appendix B Applicability of Various Dynamic Methods
599
Appendix E Theoretical Viscoelastic Functions Reduced
610
Author Index
617
Subject Index
633
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About the author (1980)

JOHN D. FERRY is Farrington Daniels research professor of chemistry at the University of Wisconsin, where he was Chairman of the Chemistry Department from 1959 to 1967. He received his undergraduate and doctorate degrees at Stanford University and has held a National Science Foundation Senior Post-doctoral Fellowship three times. Dr. Ferry has been the recipient of seven distinguished awards and medals for his work in polymer science. He is a member of the American Chemical Society, American Society of Biological Chemists, National Academy of Sciences, Society of Rheology, American Physical Society, and American Academy of Arts and Sciences. A joint editor of Advances in Polymer Sciences, Dr. Ferry is the author of over 280 articles in chemical, physical, and biochemical journals.

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