DYNAMICS OF POLYMERIC LIQUIDS Volume 1. Fluid Mechanics Volume 2 Kinetic TheoryDYNAMICS OF POLYMERIC LIQUIDS VOLUME 1 FLUID MECHANICS SECOND EDITION R. BYRON BIRD Chemical Engineering Department and Rheology Research Center University of Wisconsin-Madison Madison, Wisconsin ROBERT C. ARMSTRONG Chemical Engineering Department Massachusetts Institute of Technology Cambridge, Massachusetts OLE HASSAGER Institutet for Kemiteknik Danmarks tekniske Hojskole Lyngby, Danmark A Wiley-Interscience Publication JOHN WILEY & SONS York * Chichester * Brisbane * Toronto * SingaporeCopyright © 1987 by John Wiley & Sons, Inc. All rights reserved. Publi shed simultaneously in Canada, Reproduction or translation of any part of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging-in- Publication Data: Dynamics of polymeric liquids. “A Wiley-Interscience publication” Contents: v. 1. Fluid mechanics/R. Byron Bird, Robert C. Armstrong, Ole Hassager~ v. 2. Kinetic theory/R. Byron Bird...[et al.} 1. Polymers and polymerization—Mechanical properties. 2. Polymers and polymerization. 1. Bird, R. Byron (Robert Byron), 1924~ TA3S7.D95 1987 620.192 86-13230 ISBN 0-471-80245-X (v. 1) Printed in the United States of America 10987654321PREFACE Liquid motion has fascinated many generations of scientists and engineers. Although many years of research have been devoted to the study of fluids of low molecular weight, which are well described by the Navier-Stokes equations, many challenging problems in both theory and applications remain. But even more challenging are polymeric liquids, whose motions cannot be described at all by the Navier-Stokes equations. In Volume 1, Fluid Mechanics, we summarize the key experiments that show how polymeric fluids differ from structurally simple fluids, and we then present, in rough historical order, various methods for solving polymer fluid dynamics problems; in Volume 2, Kinetic Theory, we use molecular models and the methods of statistical mechanics to obtain relations between bulk flow behavior and polymer structure. Table 1 shows how we have chosen to organize the material of the two volumes. Understanding polymer fluid dynamics is important in connection with plastics manufacture, performance of lubricants, application of paints, processing of foodstuffs, and movement of biological fluids. Rapid advances in all these areas, as well as in the associated fundamental sciences, have made it desirable to have an introductory textbook for students and research workers. Examples and problems have been included to assist the beginner and almost all the material in both volumes has been classroom tested. These volumes should also be useful as an introduction to the advanced monographs and research literature on continuum physics, rheometry, molecular theory, and polymer processing. Literature citations have been supplied throughout the text for the interested reader. Although these volumes have been prepared with fourth or fifth year chemical engineering and chemistry students in mind, they may also be of interest to students or research workers. in polymer engineering and science, molecular biology, mechanical engineering, materials science, and applied mechanics. Both experiment and theory in this field have undergone rapid development in recent years. Except for a few papers of historical interest, the literature citations are from the period after 1950, and many are from the 1970s and 1980s. These volumes summarize the efforts of our many colleagues around the world; they also contain a number of developments and ideas heretofore unpublished. Unfortunately the following subjects have had to be omitted from the text: optical and electrical phenomena, computer simulation techniques, boundary-layer theory, two-phase systems, thermodynamics, and liquid crys- tals. Research is going on in all these areas, but we have had to rule them outside the scope of these volumes. In these two books there is enough material for two one-semester courses: a fluid dynamics course (Chapters 1 to 10), followed by a kinetic theory course (Chapters 11 to 20). Needless to say, many points can be better understood by working through the details ofTABLE 1 Contents of Volumes 1 and 2 VOLUME 1 FLUID DYNAMICS Part I. Newtonian versus Non-Newtonian Behavior Chapter 1 Review of Newtonian Fluid Dynamics Chapter 2 Flow Phenomena in Polymeric Liquids Chapter 3 Material Functions for Polymeric Liquids Part Il. Elementary Constitutive Equations and Their Use in Solving Fluid Dynamics Problems Chapter 4 The Generalized Newtonian Fluid Chapter 5 The General Linear Viscoelastic Fluid Part III. Nonlinear Viscoelastic Constitutive Equations and Their Use in Solving Fluid Dynamics Problems Chapter 6 The Retarded Motion Expansion Chapter 7 Differential Constitutive Equations Chapter 8 Single-Integral Constitutive Equations Part IV. Continuum Mechanics and Its Use in Solving Fluid Dynamics Problems Chapter 9 Continuum Mechanics Concepts Chapter 10 Fluid Dynamics of Rheometry VOLUME 2 KINETIC THEORY Part V. Polymer Models and Equilibrium Properties Chapter 11 Mechanical Models for Polymer Molecules Chapter 12 Equilibrium Configurations of Polymer Molecules Part VI. Elementary Approach to Kinetic Theory Chapter 13 Elastic Dumbbell Models Chapter 14 The Rigid Dumbbell and Multibead Models Chapter 15 The Bead-Spring-Chain Models Chapter 16 General Bead-Rod-Spring Models Part VII. A General Phase-Space Kinetic Theory Chapter 17 Phase-Space Theory of Polymeric Liquids Chapter 18 Phase-Space Theory for Dilute Solutions Chapter 19 Phase-Space Theory for Concentrated Solutions and Melts Part VIII. Elementary Kinetic Theory for Network Models Chapter 20 Network Theories for Polymer Melts and Concentrated Solutions viPREFACE vii specific problems, and to this end many illustrative examples have been included. Of particular importance are the problems at the end of the chapters, which are divided into four classes: Class A Numerical calculations using equations from the chapter. Class B- Analyses similar to those in the text. Class C More difficult or lengthy analyses. Class D Mathematical developments. Many of these problems are used to augment the material in the main text, and quite a few of them are referred to later in the book. No effort has been spared to provide generous crossreferencing within each volume and between the two volumes, and appendices are included to assist the reader in problem solving. Everywhere in the text and problems we have used SI units; viscosities are given in Pa-s (1 poise = 0.1 Pa-s = 0.1 N-s/m?) and molecular dimensions are given in nm (1A = 0.1 nm). Volumes 1 and 2 cut across several fields and it is impossible to find notation that pleases everyone. Our aim has been to follow the recommendations of the Society of Rheology for the notation for rheological quantities: y* = '— in” for the complex viscosity, for the shear-rate-dependent viscosity, 7 for the zero-shear-rate viscosity, Y, and ’, for the normal-stress coefficients, and } for the shear rate. Like many workers in kinetic theory and transport phenomena we write the total stress tensor as m = pd + t, where p is the pressure, 8 is the unit tensor, and t is that part of the stress tensor that vanishes at equilibrium; that is, both p and 1;; are positive in compression, and furthermore t obeys the well-established sign convention that is used for heat and mass fluxes. Usually continuum mechanicists and mechanical engineers use a sign convention opposite to ours for x and t. Bear in mind that misunderstandings can also arise because of differences in definitions of tensor operations; we use (Vv), = (/Ox,)vj, and [V+]; = Yy(0/Ox,)tq- In addition, we define the rate-of-strain tensor as ¥ = Vv + (V»)' and the vorticity tensor as @ = Vv —(Vv)', with no factors of 4 included. Lists of notation are included at the beginning of each volume; Appendices A and E, dealing with vector and tensor operations, should also provide assistance in interpreting the notation. In preparing these volumes we have drawn extensively on the research literature of the recent decades; we acknowledge with deep appreciation our many colleagues who have been working at the frontiers of the subject. Several of the staff members of the Rheology Research Center of the University of Wisconsin (Professors A. S. Lodge, M. W. Johnson, Jr., J. D. Ferry, J. L. Schrag, S. Kim, D. S. Malkus, and M. Renardy) have provided us with considerable assistance, as did several of our colleagues at the Massachusetts Institute of Technology (Professors R. A. Brown, J. F. Brady, and H. Brenner). Also, we wish to thank Professor M. Tirrell (University of Minnesota), Professor D. G. Baird (Virginia Polytechnic Institute), and their students, who used these volumes in manuscript form and supplied us with extensive lists of improvements. Especially helpful have been the detailed criticisms provided by those who have used the manuscript: H. C. Ottinger, John M. Wiest, Steven R. Burdette, Lewis E. Wedgewood, Tony W. Liu, Jay D. Schieber, Xi-Jun Fan, and Hassane H. Saab from the University of Wisconsin, Miguel A. Bibbo, Lidia M. Quinzani, Ali Nadim, Anthony N. Beris, John V. Lawler, Susan J. Muller, Robert C. King, Minas R. Apelian, and William P. Raiford from the Massachussetts Institute of Technology, and Sue Hirz, Neil A. Dotson, Mike Kent, Ted Frick, Gibson Batch, Robert Secor, and Kurt Hermann from the University of Minnesota. Very special thanks are due the various organizations without whose financial support our basic research would not have been possible: the National Science Foundation,PREFACE the U.S. Office of Naval Research, the Petroleum Research Fund, and the Vilas Trust Fund of the University of Wisconsin. Undertaking the preparation of the manuscript for the second edition was made easier by the support provided by the Vilas Trust Fund and the John D. MacArthur Professorship made available to Dr. Bird; in addition Dr. Armstrong wishes to thank Exxon Research and Engineering for financial support during part of the sabbatical year used for writing these volumes, Dr. Curtiss acknowledges financial support provided by the Graduate School of the University of Wisconsin, and Dr. Hassager’s stay at the University of Wisconsin for 11 months in 1984 was made possible by salary support provided by the Technical University of Denmark and the Mathematics Research Center at the University of Wisconsin and by a travel grant from the NATO Science Fellowship Program. Manuscript preparation was made easier by our various expert secretaries: Miss Jane A. Smith (University of Wisconsin), Mrs. Glorianne Collver-Jacobson (MIT), and Miss Helga Wolff (DTH). R. Byron Bird Madison, Wisconsin Robert C. Armstrong Cambridge, Massachusetts Ole Hassager Lyngby, Denmark Charles F. Curtiss Madison, Wisconsin January 1987Comments on Volume 1 During the decade that has elapsed since the first edition of Volume 1 was published, many advances have been made in polymer fluid dynamics; consequently the second edition of the book has been almost completely rewritten. Even the outline of the book has been altered in a major way by postponing the most difficult subjects to the later chapters so that more material will be easily accessible to those persons entering the field. Differences in content between the first and second editions are largely the result of our desire to devote proportionately more space to the solution of fluid dynamics problems and less to rheology and continuum mechanics. In the first three chapters and in Appendix A we provide background material for the study of polymer fluid dynamics. Chapter | provides a review of some of the main ideas of fluid dynamics as well as some important results for Newtonian fluids that are needed later. Appendix A on vectors and tensors is included primarily as reference material. The subject of polymer fluid dynamics is introduced in Chapter 2 through a series of photographs and drawings to show what effects have been seen in the laboratory. Experimentally observed phenomena must be kept in mind at all times as we proceed to the theoretical discussions that follow. Despite the great advances made in recent decades in the theoretical aspects of the subject, polymer fluid dynamics is still very much a field that relies heavily on experimental observations. The experimentally measured rheological properties such as viscosity, normal stresses, stress relaxation, and recoil are discussed in Chapter 3, and frequent reference is made in later chapters to the data summarized here. Once the background material of Chapters 1-3 has been presented, we are ready to go on to the study of polymer fluid dynamics calculations. The accompanying table lists types of flow problems that we show how to solve. Here we set forth the scope and aims of Chapters 4-9. Each chapter features a certain class of constitutive equations (ie., stress tensor expressions) as well as the kinds of flows for which it is appropriate. Many important industrial problems involve flows that are approximately steady- state shear flows, and for these problems we can use the relatively simple generalized Newtonian fluid of Chapter 4. Engineers have used models of this type for over 50 years to get approximate solutions to flow problems as well as heat- and mass-transter problems. Many time-dependent problems, of interest to polymer chemists, are well described by the linear viscoelastic fluid, which is the subject of Chapter 5. Of course modeling of this sort is limited strictly to motions with vanishingly small displacement gradients. “Retarded motions”—those in which the velocity gradients and their time derivatives are small—can be studied in a satisfying way by the retarded-motion expansion as described in Chapter 6. Yielding as they do to analytical solutions, these retarded-motion flows provide insight into the onset of elastic effects and, in particular, into the elucidation of interesting secondary flow phenomena. Of greatest current interest in polymer fluid dynamics, however, are the nonlinear differential models of Chapter 7 and the nonlinear integral models of Chapter 8; these chapters are designed to describe arbitrary flow fields and to some extent they include the ixSMOY [eUONRIOII snosuasowoy Apeaig uonenbo uyary—s9U19y smog zvays smog uonenba faqi Apeays ul syoayo ssouis [PUON, aeays Apeaig —uasyolig-a]eUlwD, suonenba uoisuedxe 2AIINILISUOD Jo VON] Axesuquy Jesfoqur-Arowsyy 6 SMOY ONSE[JOISIA Jo VOHEINUIG pny 214-4 Joxuod Arend) ping sx meg—unAry, sjepowr Blep [oIZojooys Jo uoNEIeI01Uy Aresiqay —_ pinbyy oy139qqna o8po7] [exoruy 8 snyasarp SMOY SHSE[SOISIA JO UONE|NWIS phospio (Buzuuids soqy “3'2) Suypoui ssov0id ysnoy, JOUZIOW-O1Y AN soskyeue Aupiqeig sKoiyor paroauod sjepour suonenofeo onsepsoosia K10yeI0|dxy, Aremqay Temxey paysauo> renuasayid L smoy Aresique Jo saseo Sunwry jews smoy Asepuogss Jo 19SUQ, axe SOANBALIOP uorsuedxo suoisuadsns ut uonequatio ajonieg aun 3104) pue PIN} JopsQ-pug uonow sdoxp pur sojqqnq jo uonow swusipesd A1190]9,, PIN|y 19p3Q-Puz popieioy 9 WOISSIWUSURI DALAL [apo omxey Jonuos Aupendy pozijesousn ping uoneziojoeseyo pint squaiped repo; shaayor ONSEIOOOSIA suonejer Kuadosd-ainyonyg = quowaoe|dsip jews Tepopy [lemxeyy aeouy es0UID $ Jgjsuesy sew pur Two PPoW suonejnojes moy SuysouIsus Y3Noy (4quo epnse {-neoue), ping Ayoojoa re{NBue snssoA anbs0 sioayo snoosta) PPO weysuig uejuoIMoN doup oinssoid snsioa oe1 MOY OUINIOA smoy seays Apearg [POW MeT-19MOg poziyerouo , suoneoyddy wey poquosoq, smoLy sojdurexgy POW PINLy soidey T aTaviCOMMENTS ON VOLUME 1 xi models of Chapters 4, 5, and 6 as special cases. For the most part the constitutive equations presented in these chapters are empirical nonlinear extensions of the linear viscoelastic models of Chapter 5, but the most successful ones are those that have at least some molecular basis. Just about all of the constitutive relations that we emphasize in these chapters have been extensively tested by comparison with rheological data, and many have been used for fluid dynamics calculations. After completing Chapter 8 the reader will have had a fairly thorough introduction to polymer fluid dynamics and constitutive modeling. Moreover the reader can get through Chapter 8 with only a modest knowledge of differential equations, tensors, and matrices, since the continuum mechanics basis for the earlier chapters is not given until Chapter 9. Effectively what we have done is to make the study of polymer fluid dynamics somewhat more accessible by using the main results of Chapter 9 prior to giving the mathematical justification. Students of polymer fluid dynamics will ultimately want to learn more about the fundamentals of continuum mechanics, and Chapter 9 provides a short introduction to this branch of classical mechanics. Giving a brief survey of the analysis of the rheometric experiments in Chapter 10 serves to introduce the reader to another very large subject that is very important in polymer fluid dynamics. Only after the reader is familiar with constitutive equations and continuum mechanics is it really possible to understand the fluid dynamics description of the key measuring instruments that provide us with the basic rheological data. Last, but not least, we point out that Appendices A, B, and C contain considerable tabular material that can facilitate the setting up and solving of fluid dynamics problems. Deletion of all the material on the corotational description of continuum mechanics in Chapters 7 and 8 of the first edition represents a major change in viewpoint, which perhaps requires some comment. Relatively few researchers nave chosen to use the corotational formalism, and furthermore molecular theories seem to favor the codeforma- tional point of view, which leads to the convected derivatives and finite strain tensors that we use in Chapters 6-10 of the second edition. Of course, in the retarded motion expansion of Chapter 6 and in the differential models of Chapter 7, either system may be used equally well, and interrelating the two systems involves only notational changes. Yet situations may arise where the use of a corotational point of view may be advantageous, in which case the reader will have to consult the first edition of this book. Despite extensive checking and rechecking by the authors, some errors will inevitably creep into the final published book; we hope that readers will assist us by letting us know of errors that they come across. R.B.B. RCA, O.H.