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 Polymer Science
S e c o n d E d i t i o n
Introduction to
Polymer Science
and Chemistry Introduction to

Introduction to Polymer
Science and Chemistry
A Problem-Solving Approach
S e c o n d E d i t i o n Polymer Science
Industry and academia remain fascinated with the diverse properties and applications
of polymers. However, most introductory books on this enormous and important field
do not stress practical problem solving or include recent advances, which are critical
for the modern polymer scientist-to-be. Updating the popular first edition of “the polymer
and Chemistry
book for the new millennium,” Introduction to Polymer Science and Chemistry: A
Problem-Solving Approach, Second Edition seamlessly integrates exploration of the
fundamentals of polymer science and polymer chemistry.

See what’s new in the second edition: A Problem-Solving Approach

• Chapter on living/controlled radical polymerization, using a unique
problem-solving approach
• Chapter on polymer synthesis by “click” chemistry, using a unique
problem-solving approach
• Relevant and practical work-out problems and case studies
• Examples of novel methods of synthesis of complex polymer molecules
by exciting new techniques
• Figures and schematics of the novel synthetic pathways described in
the new examples

Author Manas Chanda takes an innovative problem-solving approach in which the text
Manas Chanda
presents worked-out problems or questions with answers at every step of the development
of a new theory or concept, ensuring a better grasp of the subject and scope for
self study. Containing 286 text-embedded solved problems and 277 end-of-chapter
home-study problems (fully answered separately in a Solutions Manual), the book
provides a comprehensive understanding of the subject. These features and more set
this book apart from other currently available polymer chemistry texts. Second
Edition
K15289
ISBN-13: 978-1-4665-5384-2
90000

9 781466 553842

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 Introduction to
Polymer Science
and Chemistry
A Problem-Solving Approach

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This page intentionally left blank
 S e c o n d e d i t i o n

Introduction to
Polymer Science
and Chemistry
A Problem-Solving Approach

Manas Chanda

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

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CRC Press
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 Dedicated to the memory
of my beloved father and mentor
Narayan Chandra Chanda
This page intentionally left blank
Contents

Preface xvii

Author xxi

1 Introductory Concepts 1
1.1 Basic Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.3 Molecular Weight and Molar Mass . . . . . . . . . . . . . . . . . . . . . 3
1.1.4 End Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.5 Degree of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.6 Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Polymerization and Functionality . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Polymerization Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Addition or Chain Polymerization . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 Step Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.3 Supramolecular Polymerization . . . . . . . . . . . . . . . . . . . . . . 13
1.4 Molecular Architecture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.5 Classification of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.5.1 Thermoplastics and Thermosets . . . . . . . . . . . . . . . . . . . . . . 22
1.6 Plastics, Fibers, and Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.7 Polymer Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

2 Chain Dimensions, Structures, and Transitional Phenomena 35

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2 Polymer Chains: Structures and Dimensions . . . . . . . . . . . . . . . . . . . 35
2.2.1 Conformational Changes . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.1.1 Polyethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.1.2 Polyisobutylene . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.1.3 Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.2 Polymer Conformations in Crystals . . . . . . . . . . . . . . . . . . . . 40
2.2.3 Polymer Size in the Amorphous State . . . . . . . . . . . . . . . . . . . 42
2.2.3.1 Freely Jointed Chains . . . . . . . . . . . . . . . . . . . . . . 43
2.2.3.2 Real Polymer Chains . . . . . . . . . . . . . . . . . . . . . . 44

vii
viii Contents

2.3 Constitutional and Configurational Isomerism . . . . . . . . . . . . . . . . . . . 47

2.3.1 Constitutional Isomerism . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.2 Configurational Isomerism . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.2.1 Geometrical Isomerism . . . . . . . . . . . . . . . . . . . . . 50
2.3.2.2 Stereoisomerism . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4 Crystallinity in Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.4.1 Structure of Bulk Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.4.1.1 Spherulites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.5 Thermal Transitions in Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.5.1 Tg and Tm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.5.2 First- and Second-Order Transitions . . . . . . . . . . . . . . . . . . . . 63
2.6 Regions of Viscoelastic Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.7 Factors Affecting Tg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.8 Factors Affecting Tm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.9 Relation Between Tm and Tg . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.10 Theoretical Treatment of Glass Transition . . . . . . . . . . . . . . . . . . . . . 69
2.10.1 Quantitative Effects of Factors on Tg . . . . . . . . . . . . . . . . . . . . 74
2.11 Chain Movements in Amorphous State . . . . . . . . . . . . . . . . . . . . . . . 80
2.11.1 The Reptation Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.12 Thermodynamics of Rubber Elasticity . . . . . . . . . . . . . . . . . . . . . . . 83
2.12.1 Stress-Strain Behavior of Crosslinked Elastomers . . . . . . . . . . . . . 85
2.12.2 Nonideal Networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
2.12.2.1 Network Defects . . . . . . . . . . . . . . . . . . . . . . . . . 91
2.12.2.2 Elastically Active Chain Sections . . . . . . . . . . . . . . . . 91
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

3 Polymers in Solution 101

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2 Thermodynamics of Liquid Mixtures . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2.1 Low-Molecular-Weight Mixtures: van Laar Model . . . . . . . . . . . . 104
3.2.2 Polymer-Solvent Mixtures: Flory-Huggins Model . . . . . . . . . . . . 107
3.2.2.1 Flory-Huggins Expressions for Thermodynamic Functions . . 111
3.2.2.2 Colligative Properties and Interaction Parameter Χ . . . . . . . 113
3.2.2.3 Virial Coefficients . . . . . . . . . . . . . . . . . . . . . . . . 117
3.2.2.4 Modification of Flory-Huggins Theory . . . . . . . . . . . . . 119
3.2.2.5 Flory-Krigbaum Theory . . . . . . . . . . . . . . . . . . . . . 121
3.2.2.6 Excluded Volume Theory . . . . . . . . . . . . . . . . . . . . 122
3.3 Phase Equilibria in Poor Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.3.1 Upper and Lower Critical Solution Temperatures . . . . . . . . . . . . . 129
3.4 Solubility Behavior of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.5 Swelling of Crosslinked Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.5.1 Determination of Χ from Swelling . . . . . . . . . . . . . . . . . . . . . 142
3.6 Frictional Properties of Polymer Molecules
in Dilute Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.6.1 Viscosity of Dilute Polymer Solutions . . . . . . . . . . . . . . . . . . . 145
3.6.1.1 Determination of Polymer Molecular Dimensions from Viscosity 148
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Contents ix

Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

4 Polymer Molecular Weights 159

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2 Molecular Weight Averages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2.1 Arithmetic Mean . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2.2 Number-Average Molecular Weight . . . . . . . . . . . . . . . . . . . . 160
4.2.3 Weight-Average Molecular Weight . . . . . . . . . . . . . . . . . . . . . 162
4.3 Molecular Weights in Terms of Moments . . . . . . . . . . . . . . . . . . . . . 163
4.3.1 Ratio of First and Zeroth Moments . . . . . . . . . . . . . . . . . . . . . 164
4.3.2 Ratios of Higher Moments . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.4 Molecular Weight Determination . . . . . . . . . . . . . . . . . . . . . . . . . . 166
4.4.1 End-Group Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
4.4.2 Colligative Property Measurement . . . . . . . . . . . . . . . . . . . . . 168
4.4.2.1 Ebulliometry (Boiling Point Elevation) . . . . . . . . . . . . . 168
4.4.2.2 Cryoscopy (Freezing Point Depression) . . . . . . . . . . . . . 169
4.4.2.3 Membrane Osmometry . . . . . . . . . . . . . . . . . . . . . 169
4.4.2.4 Vapor-Phase Osmometry . . . . . . . . . . . . . . . . . . . . 176
4.4.3 Light-Scattering Method . . . . . . . . . . . . . . . . . . . . . . . . . . 180
4.4.3.1 Rayleigh Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . 181
4.4.3.2 Turbidity and Rayleigh Ratio . . . . . . . . . . . . . . . . . . 183
4.4.3.3 Turbidity and Molecular Weight of Polymer . . . . . . . . . . 184
4.4.3.4 Dissymmetry of Scattering . . . . . . . . . . . . . . . . . . . 188
4.4.3.5 Zimm Plots . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
4.4.4 Dilute Solution Viscometry . . . . . . . . . . . . . . . . . . . . . . . . . 194
4.4.4.1 Calibration of the Mark-Houwink-Sakurada Equation . . . . . 196
4.4.4.2 Measurement of Intrinsic Viscosity . . . . . . . . . . . . . . . 197
4.4.5 Gel Permeation Chromatography . . . . . . . . . . . . . . . . . . . . . 200
4.4.5.1 Data Interpretation and Calibration . . . . . . . . . . . . . . . 202
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208

5 Condensation (Step-Growth) Polymerization 213

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.2 Rates of Polycondensation Reactions . . . . . . . . . . . . . . . . . . . . . . . . 214
5.2.1 Irreversible Polycondensation Kinetics . . . . . . . . . . . . . . . . . . 216
5.2.2 Reversible Polycondensation Kinetics . . . . . . . . . . . . . . . . . . . 222
5.3 Number-Average Degree of Polymerization . . . . . . . . . . . . . . . . . . . . 224
5.4 Control of Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.4.1 Quantitative Effect of Stoichiometric Imbalance . . . . . . . . . . . . . . 228
5.5 Molecular Weight Distribution (MWD) . . . . . . . . . . . . . . . . . . . . . . 232
5.5.1 Breadth of MWD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
5.6 Nonlinear Step Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.6.1 Branching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.6.2 Crosslinking and Gelation . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.6.2.1 Statistical Approach . . . . . . . . . . . . . . . . . . . . . . . 246
5.6.2.2 Model for Gelation Process . . . . . . . . . . . . . . . . . . . 255
5.6.2.3 Molecular Size Distribution . . . . . . . . . . . . . . . . . . . 255
x Contents

5.6.2.4 Post-Gel Relations . . . . . . . . . . . . . . . . . . . . . . . . 258

5.7 Recursive Approach for Average Properties . . . . . . . . . . . . . . . . . . . . 260
5.7.1 Linear Step-Growth Polymerization . . . . . . . . . . . . . . . . . . . . 260
5.7.2 Nonlinear Step-Growth Polymerization . . . . . . . . . . . . . . . . . . 264
5.7.2.1 Polymerization of A f  f > 2 . . . . . . . . . . . . . . . . . . 264
5.7.2.2 Polymerization of A f ( f > 2) + B2 . . . . . . . . . . . . . . . 266
5.7.2.3 Polymerization of  Ai   B j . . . . . . . . . . . . . . . . . 268
5.7.3 Post-Gel Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
5.7.3.1 Polymerization of A f . . . . . . . . . . . . . . . . . . . . . . 272
5.7.3.2 Polymerization of A f  B2 . . . . . . . . . . . . . . . . . . . 276
5.8 Polycondensation of Ax B Monomers . . . . . . . . . . . . . . . . . . . . . . . . 278
5.8.1 Dendritic and Hyperbranched Polymers . . . . . . . . . . . . . . . . . . 279
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283

6 Free Radical Polymerization 289

6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
6.2 Scheme of Radical Chain Polymerization . . . . . . . . . . . . . . . . . . . . . 290
6.2.1 Overall Scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
6.2.2 Chain Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
6.2.3 Chain Propagation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
6.2.4 Chain Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
6.2.5 Rate of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
6.2.6 Overall Extent of Polymerization . . . . . . . . . . . . . . . . . . . . . 295
6.3 Experimental Determination of R p : Dilatometry . . . . . . . . . . . . . . . . . 298
6.4 Methods of Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
6.4.1 Thermal Decomposition of Initiators . . . . . . . . . . . . . . . . . . . . 300
6.4.1.1 Initiator Efficiency . . . . . . . . . . . . . . . . . . . . . . . . 301
6.4.2 Redox Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
6.4.3 Photochemical Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . 308
6.4.3.1 Direct Photoinitiation . . . . . . . . . . . . . . . . . . . . . . 308
6.4.3.2 Photosensitization . . . . . . . . . . . . . . . . . . . . . . . . 309
6.4.3.3 Rate of Photoinitiated Polymerization . . . . . . . . . . . . . . 310
6.4.4 Initiation by High-Energy Radiations . . . . . . . . . . . . . . . . . . . 311
6.4.5 Thermal Initiation in Absence of Initiator . . . . . . . . . . . . . . . . . 312
6.5 Dead-End Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
6.6 Determination of Absolute Rate Constants . . . . . . . . . . . . . . . . . . . . . 316
6.6.1 Nonsteady-State Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . 316
6.7 Chain Length and Degree of Polymerization . . . . . . . . . . . . . . . . . . . . 321
6.7.1 Kinetic Chain Length . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
6.7.2 Mode of Chain Termination . . . . . . . . . . . . . . . . . . . . . . . . 323
6.7.3 Average Lifetime of Kinetic Chains . . . . . . . . . . . . . . . . . . . . 325
6.8 Chain Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
6.8.1 Degree of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 328
6.8.2 Chain Transfer to Polymer . . . . . . . . . . . . . . . . . . . . . . . . . 334
6.8.3 Allylic Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
6.9 Deviations from Ideal Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
6.9.1 Primary Radical Termination . . . . . . . . . . . . . . . . . . . . . . . . 337
Contents xi

6.9.2 Initiator-Monomer Complex Formation . . . . . . . . . . . . . . . . . . 338

6.9.3 Degradative Initiator Transfer . . . . . . . . . . . . . . . . . . . . . . . 339
6.9.4 Autoacceleration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
6.10 Inhibition/Retardation of Polymerization . . . . . . . . . . . . . . . . . . . . . . 343
6.10.1 Inhibition/Retardation Kinetics . . . . . . . . . . . . . . . . . . . . . . . 345
6.11 Effects of Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
6.11.1 Rate of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
6.11.2 Degree of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 350
6.11.3 Polymerization-Depolymerization Equilibrium . . . . . . . . . . . . . . 351
6.12 Molecular Weight Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
6.12.1 Low-Conversion Polymerization . . . . . . . . . . . . . . . . . . . . . . 355
6.12.1.1 Termination by Disproportionation and/or Transfer . . . . . . . 356
6.12.1.2 Termination by Coupling . . . . . . . . . . . . . . . . . . . . 357
6.12.1.3 Termination by Coupling, Disproportionation, and Chain Transfer358
6.12.2 High-Conversion Polymerization . . . . . . . . . . . . . . . . . . . . . 359
6.13 Polymerization Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
6.13.1 Emulsion Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 361
6.13.1.1 Qualitative Picture . . . . . . . . . . . . . . . . . . . . . . . . 361
6.13.1.2 Kinetics of Emulsion Polymerization . . . . . . . . . . . . . . 364
6.13.1.3 Other Theories . . . . . . . . . . . . . . . . . . . . . . . . . . 371
6.13.2 Photoemulsion Polymerization . . . . . . . . . . . . . . . . . . . . . . . 372
6.13.3 “Grafting-From” Polymerization . . . . . . . . . . . . . . . . . . . . . . 373
6.14 Living Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377

7 Chain Copolymerization 383

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
7.2 Binary Copolymer Composition – Terminal Model . . . . . . . . . . . . . . . . 384
7.2.1 Significance of Monomer Reactivity Ratios . . . . . . . . . . . . . . . . 386
7.2.2 Types of Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . 387
7.2.2.1 Alternating Copolymerization . . . . . . . . . . . . . . . . . . 388
7.2.2.2 Ideal (random) Copolymerization . . . . . . . . . . . . . . . . 388
7.2.2.3 Random-Alternating Copolymerization . . . . . . . . . . . . . 388
7.2.2.4 Block Copolymerization . . . . . . . . . . . . . . . . . . . . . 389
7.2.3 Instantaneous Copolymer Composition . . . . . . . . . . . . . . . . . . 389
7.2.4 Integrated Binary Copolymer Equation . . . . . . . . . . . . . . . . . . 392
7.2.5 Evaluation of Monomer Reactivity Ratios . . . . . . . . . . . . . . . . . 396
7.2.5.1 Plot of r1 versus r2 . . . . . . . . . . . . . . . . . . . . . . . 396
7.2.5.2 Plot of F1 versus f1 . . . . . . . . . . . . . . . . . . . . . . . 397
7.2.5.3 Direct Curve Fitting . . . . . . . . . . . . . . . . . . . . . . . 399
7.2.6 The Q  e Scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
7.2.7 Sequence Length Distribution . . . . . . . . . . . . . . . . . . . . . . . 402
7.2.8 Rate of Binary Free-Radical Copolymerization . . . . . . . . . . . . . . 405
7.3 Multicomponent Copolymerization: Terpolymerization . . . . . . . . . . . . . . 409
7.4 Deviations from Terminal Model . . . . . . . . . . . . . . . . . . . . . . . . . . 413
7.4.1 Penultimate Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
7.4.2 Complex-Participation Model . . . . . . . . . . . . . . . . . . . . . . . 414
xii Contents

7.5 Copolymerization and Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . 415

7.5.1 Vinyl and Divinyl Monomers of Equal Reactivity . . . . . . . . . . . . . 415
7.5.2 Vinyl and Divinyl Monomers of Different Reactivities . . . . . . . . . . 418
7.5.3 One Group of Divinyl Monomer Having Lower Reactivity . . . . . . . . 419
7.6 Block and Graft Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . 420
7.6.1 Block Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 421
7.6.1.1 Producing Internal Peroxide Linkages . . . . . . . . . . . . . 421
7.6.1.2 Introducing Peroxide End Groups . . . . . . . . . . . . . . . . 421
7.6.1.3 Mechanical Cleaving of Polymer Chains . . . . . . . . . . . . 422
7.6.1.4 Controlled Radical Polymerization . . . . . . . . . . . . . . . 423
7.6.2 Graft Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 423
7.6.2.1 Chain Transfer Methods . . . . . . . . . . . . . . . . . . . . . 423
7.6.2.2 Irradiation with Ionizing Radiation . . . . . . . . . . . . . . . 424
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426

8 Ionic Chain Polymerization 429

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
8.2 Ionic Polymerizability of Monomers . . . . . . . . . . . . . . . . . . . . . . . . 430
8.3 Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
8.3.1 Anionic Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
8.3.1.1 Nucleophilic Attack . . . . . . . . . . . . . . . . . . . . . . . 433
8.3.1.2 Electron Transfer . . . . . . . . . . . . . . . . . . . . . . . . 434
8.3.2 Termination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
8.3.2.1 Living Polymerization . . . . . . . . . . . . . . . . . . . . . . 436
8.3.2.2 Termination by Transfer Agents . . . . . . . . . . . . . . . . . 436
8.3.2.3 Spontaneous Termination . . . . . . . . . . . . . . . . . . . . 438
8.3.3 Polymerization with Complete Dissociation of Initiator . . . . . . . . . . 438
8.3.3.1 Polymerization Kinetics . . . . . . . . . . . . . . . . . . . . . 439
8.3.3.2 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . 439
8.3.3.3 Average Kinetic Chain Length . . . . . . . . . . . . . . . . . 441
8.3.3.4 Average Degree of Polymerization . . . . . . . . . . . . . . . 441
8.3.3.5 Distribution of the Degree of Polymerization . . . . . . . . . . 443
8.3.3.6 Effects of Reaction Media . . . . . . . . . . . . . . . . . . . . 447
8.3.3.7 Effect of Excess Counterion . . . . . . . . . . . . . . . . . . . 451
8.3.4 Polymerization with Incomplete Dissociation of Initiator . . . . . . . . . 454
8.3.5 Polymerization with Simultaneous Propagation and Termination . . . . . 455
8.4 Anionic Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
8.4.1 Reactivity Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
8.4.2 Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
8.4.2.1 Sequential Monomer Addition . . . . . . . . . . . . . . . . . 460
8.4.2.2 Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . 461
8.5 Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
8.5.1 Cationic Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
8.5.1.1 Protonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 464
8.5.1.2 Lewis Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
8.5.2 Propagation of Cationic Chain . . . . . . . . . . . . . . . . . . . . . . . 465
8.5.3 Chain Transfer and Termination . . . . . . . . . . . . . . . . . . . . . . 466
Contents xiii

8.5.3.1 Chain Transfer to Monomer . . . . . . . . . . . . . . . . . . . 466

8.5.3.2 Spontaneous Termination . . . . . . . . . . . . . . . . . . . . 467
8.5.3.3 Combination with Counterion . . . . . . . . . . . . . . . . . . 467
8.5.3.4 Transfer to Solvents/Reagents . . . . . . . . . . . . . . . . . . 469
8.5.3.5 Chain Transfer to Polymer . . . . . . . . . . . . . . . . . . . 470
8.5.4 Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
8.5.4.1 Ions and Ion Pairs . . . . . . . . . . . . . . . . . . . . . . . . 471
8.5.4.2 Simplified Kinetic Scheme . . . . . . . . . . . . . . . . . . . 472
8.5.4.3 Degree of Polymerization . . . . . . . . . . . . . . . . . . . . 478
8.5.5 Molecular Weight Distribution . . . . . . . . . . . . . . . . . . . . . . . 479
8.5.6 Cationic Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . 482
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483

9 Coordination Addition Polymerization 487

9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
9.2 Ziegler-Natta Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
9.2.1 Catalyst Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
9.2.2 Nature of the Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
9.2.3 Evolution of the Titanium-Aluminum System . . . . . . . . . . . . . . . 489
9.3 Mechanism of Ziegler-Natta Polymerization . . . . . . . . . . . . . . . . . . . . 490
9.3.1 Mechanism of Stereospecific Placement . . . . . . . . . . . . . . . . . . 490
9.3.2 Bimetallic and Monometallic Mechanisms . . . . . . . . . . . . . . . . 491
9.3.2.1 Bimetallic Mechanism . . . . . . . . . . . . . . . . . . . . . . 492
9.3.2.2 Monometallic Mechanism . . . . . . . . . . . . . . . . . . . . 492
9.4 Kinetics of Ziegler-Natta Polymerization . . . . . . . . . . . . . . . . . . . . . . 495
9.4.1 Typical Shapes of Kinetic Curves . . . . . . . . . . . . . . . . . . . . . 495
9.4.2 Effect of Catalyst Particle Size . . . . . . . . . . . . . . . . . . . . . . . 497
9.4.3 Chain Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
9.4.4 Kinetic Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
9.4.4.1 Early Models . . . . . . . . . . . . . . . . . . . . . . . . . . 499
9.4.4.2 Adsorption Models . . . . . . . . . . . . . . . . . . . . . . . 502
9.4.4.3 Average Degree of Polymerization . . . . . . . . . . . . . . . 514
9.5 Supported Metal Oxide Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 515
9.5.1 Polymerization Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 515
9.5.1.1 Bound-Ion-Radical Mechanism . . . . . . . . . . . . . . . . . 516
9.5.1.2 Bound-Ion-Coordination Mechanism . . . . . . . . . . . . . . 520
9.6 Ziegler-Natta Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 521
9.7 Metallocene-Based Ziegler-Natta Catalysts . . . . . . . . . . . . . . . . . . . . 522
9.7.1 Catalyst Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
9.7.2 The Active Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
9.7.3 Polymerization Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 526
9.7.4 Kinetic Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
9.7.4.1 Ewen’s Model . . . . . . . . . . . . . . . . . . . . . . . . . . 526
9.7.4.2 Chien’s Model . . . . . . . . . . . . . . . . . . . . . . . . . . 527
9.7.4.3 Molecular Weight and Chain Transfer . . . . . . . . . . . . . 530
9.8 Immobilized Metallocene Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 531
9.9 Oscillating Metallocene Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 534
xiv Contents

References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537

10 Ring-Opening Polymerization 541

10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
10.2 Polymerization Mechanism and Kinetics . . . . . . . . . . . . . . . . . . . . . . 543
10.2.1 Cyclic Ethers/Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . 544
10.2.1.1 Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . 544
10.2.1.2 Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . 548
10.2.2 Lactams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
10.2.2.1 Hydrolytic Polymerization . . . . . . . . . . . . . . . . . . . 557
10.2.2.2 Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . 560
10.2.3 Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565

11 Living/Controlled Radical Polymerization 567

11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
11.2 Stable Free Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 571
11.2.1 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
11.2.2 Stable Nitroxide Radicals . . . . . . . . . . . . . . . . . . . . . . . . . 573
11.2.3 Mechanism and Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . 573
11.2.4 Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
11.2.5 Aqueous Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
11.3 Atom Transfer Radical Polymerization (ATRP) . . . . . . . . . . . . . . . . . . 593
11.3.1 ATRP Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
11.3.2 ATRP Initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
11.3.3 ATRP Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
11.3.4 ATRP Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
11.3.5 ATRP Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
11.3.6 ATRP Mechanism and Kinetics . . . . . . . . . . . . . . . . . . . . . . 602
11.3.7 Chain-End Functionality . . . . . . . . . . . . . . . . . . . . . . . . . . 607
11.3.8 Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
11.3.8.1 Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . 609
11.3.8.2 Graft Copolymers . . . . . . . . . . . . . . . . . . . . . . . . 618
11.3.8.3 Star and Hyperbranched Polymers . . . . . . . . . . . . . . . 621
11.3.9 Aqueous Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
11.4 Degenerative Chain Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
11.5 Reversible Addition-Fragmentation Chain Transfer . . . . . . . . . . . . . . . . 625
11.5.1 Mechanism and Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . 629
11.5.2 Theoretical Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . 635
11.5.3 Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
11.5.3.1 Sequential Monomer Addition . . . . . . . . . . . . . . . . . 636
11.5.3.2 Macro-CTA Method . . . . . . . . . . . . . . . . . . . . . . . 641
11.5.4 Star (Co)polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
11.5.5 Branched (Co)polymers . . . . . . . . . . . . . . . . . . . . . . . . . . 644
11.5.6 Surface Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
11.5.7 Combination of RAFT and Other Polymerization Techniques . . . . . . . 645
Contents xv

11.5.8 Transformation of RAFT Polymer End Groups . . . . . . . . . . . . . . 646

References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653

12 Polymer Synthesis by Click Chemistry 661

12.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
12.2 Copper-Catalyzed Azide-Alkyne Cycloaddition . . . . . . . . . . . . . . . . . . 665
12.2.1 Combination of ATRP and CuAAC Reactions . . . . . . . . . . . . . . . 675
12.2.1.1 Macromonomer Synthesis . . . . . . . . . . . . . . . . . . . . 675
12.2.1.2 End-Functionalization of (Co)polymer Chains . . . . . . . . . 680
12.2.1.3 Cyclization of Linear Polymers . . . . . . . . . . . . . . . . . 681
12.2.1.4 Moldular Synthesis of Block Copolymers . . . . . . . . . . . 682
12.2.1.5 Nonlinear Polymer Synthesis . . . . . . . . . . . . . . . . . . 683
12.2.2 Combination of RAFT Polymerization and CuAAC . . . . . . . . . . . . 690
12.3 Strain-Promoted Azide-Alkyne Coupling . . . . . . . . . . . . . . . . . . . . . 694
12.4 Diels-Alder Click Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
12.4.1 Copolymer Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
12.4.2 Thermoresponsive Systems, Dendrons, and Dendrimers . . . . . . . . . 702
12.4.3 Hetero-Diels-Alder (HDA) Cycloaddition . . . . . . . . . . . . . . . . . 707
12.5 Thiol-Ene Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
12.5.1 Mechanisms of Thiol-Ene Reactions . . . . . . . . . . . . . . . . . . . . 714
12.5.2 Synthesis of Star Polymers and Dendrimers . . . . . . . . . . . . . . . . 716
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Exercises
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 722

Appendix A Conversion of Units 727

Appendix B Fundamental Constants 729

Index 731
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Preface

A question asked during discussion, or even ahead of it, excites a student’s mind and rouses his
eagerness to probe, thus making the process of learning more thorough. During my teaching of
polymer science and chemistry over a period of nearly four decades, I have thus always believed
that learning becomes much easier if problem solving with a question-and-answer approach is in-
timately integrated with the text. It was this belief that motivated me to embark on writing this
new text on polymer science and polymer chemistry, even though I was fully aware that the field
was already crowded with more than a dozen well-written polymer texts. Adopting a distinctly
different and innovative approach, the text in this new polymer book has been laced with ques-
tions and answers at every step of the development of a theory or concept in each chapter. The
book thus features a significantly large number (286) of solved problems interspersed with the
text that is spread over 720 pages. In addition, a large number (277) of problems are included as
end-of-chapter exercises and these are fully worked out in a separate Solutions Manual. As my
experience in teaching has shown me the value of dealing with numbers to deepen one’s under-
standing, most of the problems with which the text is studded are numerical. The same is true for
exercise problems appended at the end of each chapter and each such problem is provided with
numerical answers that the reader can compare with his own.
To describe the present book briefly, it is a revised and enlarged second edition of Introduction
to Polymer Science and Chemistry: A Problem Solving Approach and it contains a total of 563 text-
embedded solved problems and chapter-end exercise problems. It has evolved from the first edition
by retaining all the latter’s ten chapters, which, however, have been fully relaid and restructured
to afford greater readability and understanding, and adding two new and large chapters to deal
with two recent topics that are said to have ushered in a renaissance in polymer chemistry, namely,
living/controlled radical polymerization and application of “click” chemistry in polymer synthesis.
The book thus has twelve chapters that fall into three distinct groups. The first four chapters
introduce the reader to polymers and their basic characteristics, both in solid state and in solution,
and the next six chapters are concerned with various polymerization reactions, mechanisms, and
kinetics, while the last two chapters are devoted to two recent topics, as cited above, of great
interest and importance in polymer chemistry. This division into groups is, however, notional and
is not made explicit by numbering these groups of chapters separately. Instead, for convenience, a
single sequence of numbers is used throughout the book.
Chapter 1 is devoted to introductory concepts and definitions, while Chapter 2 deals with
physical and molecular aspects of polymers, that is, those relating to molecular shape and size,
distinctive characteristics, conformational and configurational behavior, structural features, mor-
phology, thermal transitional phenomena, and relaxation properties. Chapter 3 discusses polymer
solution behavior, the emphasis being on thermodynamics, phase equilibria, solubility, swelling,
frictional properties, and viscosity. Molecular weight determination, which is one of the first steps
of polymer characterization and a centrally important topic of polymer science, mostly involves

xvii
xviii Preface

analysis of polymers in solution. The next chapter, Chapter 4, is therefore devoted to polymer
molecular weights with focus on the fundamentals of molecular weight statistics and methods of
measurement, their origins, and significance.
The chemistry part of the book focusing on polymerization reactions, mechanisms, and kinet-
ics starts with Chapter 5. Five main types of polymerization reactions — condensation (step), free
radical (chain), ionic (chain), coordination (chain), and ring-opening — are dealt with separately
in five essentially self-contained chapters. Copolymerization that may involve any of these poly-
merization mechanisms is included in respective chapters, an exception being free-radical chain
copolymerization which, in view of its great practical importance and considerable theoretical de-
velopment that has taken place in this field, has been accorded the space of one full chapter. While
polymerization reactions have been characterized on the basis of mechanisms and kinetic features,
emphasis has been placed on understanding the reaction parameters which are important in con-
trolling polymerization rates, degree of polymerization, and structural features, such as branching
and crosslinking.
The development of living/controlled radical polymerization (CRP) methods, which started
only in 1985, has been a long-standing goal in polymer chemistry because a radical process is
more tolerant of functional groups and impurities and is the leading industrial method to pro-
duce polymers, while the livingness of polymerization allows unprecedented control of polymer
types, architecture, end-functionalities, molecular weght, and distributions. CRP is thus among
the most rapidly developing areas of polymer chemistry, with the number of publications nearly
doubling each year in the initial phase of development. Presently, the most popular CRP meth-
ods are nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP),
and reversible addition/fragmentation chain transfer (RAFT) techniques, all of which are described
elaborately in the newly added Chapter 11, using once again the unique problem solving approach,
which is a hallmark of the book.
Since being introduced only in 2001, click chemistry, which may thus be called a new 21st
century technique, has made great advances in the realm of polymer chemistry over the last 10
years, giving access to a wide range of complex polymers (dendrimers, dendronized linear poly-
mers, block copolymers, graft copolymers, star polymers, etc.) and new classes of functionalized
monomers in a controlled fashion, which would be inaccessible or difficult to synthesize via con-
ventional chemistry. Chapter 12, which is the last chapter of this new edition, is fully devoted to
application of click chemistry in polymer synthesis, using the unique problem solving approach.
In writing the first ten chapters, which deal with conventional polymer science and chemistry,
I have received much inspiration and valuable guidance from the many well-known polymer texts
that are currently available. However, I should make particular mention of George Odian’s Princi-
ples of Polymerization (McGraw-Hill, New York, 1970), the first edition of which appeared when
I was still a student and it made a marked impression on me. Another book which influenced me
greatly was Rudin’s The Elements of Polymer Science and Engineering (Academic Press, Orlando,
Florida, 1982), a prescribed text at the University of Waterloo, Canada, where I taught during a
sabbatical year (1985–1986).
For writing Chapters 11 and 12 on the two recent topics, living/controlled radical polymeriza-
tion and polymer synthesis by click chemistry, which have not yet made a significant appearance in
polymer chemistry textbooks, I have depended exclusively on original articles that appeared, espe-
cially in the last ten years, in many reputed journals. Most of the articles have, however, appeared
in journals published by the American Chemical Society and John Wiley & Sons. I am grateful to
them for granting permission to reproduce some material in the book from these journals.
While SI units are being used increasingly in all branches of science, non-SI units like the older
cgs system are still in common use. This is particularly true of polymer science and chemistry.
Preface xix

In this book, therefore, both SI and non-SI units have been used. However, in most places where
non-SI units have been used, equivalent values are given in SI terms. A suitable conversion table
is also provided as an appendix.
Synthesized polymers are utilized increasingly in our daily life, and a myriad of industrial
applications have contributed to their phenomenal growth and expansion. As this requires poly-
mer chemists and specialists in polymers, many universities throughout the world have set up
teaching programs in polymer chemistry, science, and engineering. Their students are drawn from
various disciplines in science and engineering. The present book is designed primarily for both
undergraduate and graduate students and is intended to serve specially as a classroom text for a
one-year course in polymer science and chemistry. Moreover, as two chapters have been added in
the new edition focusing on recent advances in polymer chemistry over the last two decades, the
book will also be useful to students doing research in the area of polymers.
Polymer industry is the single largest field of employment for students of both science and
engineering. However, most workers entering the field have little background in polymer science
and chemistry and are forced to educate themselves in its basic principles. This book, with its
easy style and a large number of illustrative, worked-out problems, will be useful to them as a
self-contained text that guides a beginner in the subject to a fairly advanced level of proficiency.
The manuscript of the book originated from a course in polymers that I offered to graduate
students of chemistry and chemical engineering during my sabbatical year (1985-1986) at the
University of Waterloo, Ontario, Canada, where I have also been a summer-term visiting faculty
spanning over two decades (1980-2000). The manuscript has been tested since then and improved
year after year to its present state as the course has been offered every year to a mixed class of
students from various disciplines including chemistry, chemical engineering, metallurgy, civil en-
gineering, electrical engineering, electronics, and aerospace engineering at the Indian Institute of
Science, Bangalore, where I have served as a permanent faculty. A basic knowledge of mathemat-
ics, chemistry, and physics is assumed on the part of the reader, while the book has been written to
be self-contained, as far as possible, with most equations fully derived and any assumptions stated.
In the interest of time, I took up the onerous task of preparing the entire book electronically.
While I did all the (LaTex) typesetting, formatting, and page designing, I received valuable help
from two colleagues, Dr. Ajay Karmarkar and Ms. B. G. Girija, who prepared computer graphics
for all diagrams, chemical structures, and chemical formula-based equations. I thank both of
them. I am deeply indebted to Dr. P. Sunthar, an acknowledged software expert on the campus,
for guiding me patiently in the use of word processing softwares during this difficult venture
and to Shashi Kumar of Cenveo Publisher Services, Noida, India, for performing the necessary
conversions to font-embedded PDF for printing.
Several academicians have contributed, directly or indirectly, to the preparation of this book.
Among them I would like to mention Prof. K. F. O’Driscoll, Prof. G. L. Rempel, and Prof. Alfred
Rudin, all of the University of Waterloo, Waterloo, Ontario (Canada), Prof. Kenneth J. Wynne of
the Virginia Commonwealth University, Richmond, Virginia (USA), Prof. Harm-Anton Klok of
Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland), Prof. Premamoy Ghosh of
the Univeristy of Calcutta, Calcutta (India), and Prof. S. Ramakrishnan and Prof. M. Giridhar,
both of the Indian Institute of Science, Bangalore (India). I express my gratitude to all of them.
Interaction with students whom I met over the years during my long academic career, both
in India and abroad, contributed greatly to the evolution of the book to its present form featuring
a unique problem solving approach. It is not possible to thank them individually as the number
is too large. However, I should mention, gratefully, two of my erstwhile students, Dr. Amitava
Sarkar and Dr. Ajay Karmarkar, who were closely associated with me during the last few years
of my service at the Indian Institute of Science, Bangalore, and provided help in many ways in
xx Preface

the making of this book. Finally, a word of appreciation and gratitude is due to three persons very
close to me, namely, my wife Mridula, daughter Amrita, and little granddaughter Mallika, who
showed remarkable understanding and patience, and gladly sacrificed their share of my time to
facilitate my work.
Manas Chanda
Author

Manas Chanda has been a professor and is presently an emeritus professor in the Department of
Chemical Engineering, Indian Institute of Science, Bangalore, India. He also worked as a summer-
term visiting professor at the University of Waterloo, Ontario, Canada with regular summer visits
from 1980 to 2000. A five-time recipient of the International Scientific Exchange Award from the
Natural Sciences and Engineering Research Council, Canada, Professor Chanda is the author or
coauthor of more than 100 scientific papers, articles, and books, including Plastics Technology
Handbook, 4th Edition (CRC Press, Boca Raton, Florida). His biographical sketch is listed in
Marquis’ Who’s Who in the World Millennium Edition (2000) by the American Biographical So-
ciety. A Fellow of the Indian National Academy of Engineers and a member of the Indian Plastics
Institute, he received B.S. (1959) and M.Sc. (1962) degrees from Calcutta University, and a Ph.D.
(1966) from the Indian Institute of Science, Bangalore.

xxi
This page intentionally left blank
Chapter 1

Introductory Concepts

1.1 Basic Definitions

Many of the terms, definitions, and concepts used in polymer science are not encountered in other
branches of science and must be understood in order to fully discuss the synthesis, characterization,
structure, and properties of polymers. While most of these are discussed in detail in subsequent
chapters, some are of such fundamental importance that they must be introduced at the beginning.

1.1.1 Polymer
The term polymer stems from the Greek roots poly (many) and meros (part). The word thus means
“many parts” and designates a molecule made up by the repetition of some simpler unit called
a mer. Polymers contain thousands to millions of atoms in a molecule that is large; they are
also called macromolecules. Polymers are prepared by joining a large number of small molecules
called monomers.
The structure of polystyrene, for example, can be written as

(I)
or, more conveniently, as (II), which depicts the mer or repeating unit of the molecule within
parentheses with a subscript, such as n, to represent the number of repeating units in the polymer
molecule.

(II)

The value of n usually ranges from a few hundred to several thousand, depending on the
molecular weight of the polymer. The polymer molecular weight may extend, on the higher side,

1
2 Chapter 1

to several millions. Often the term high polymer is also used to emphasize that the polymer under
consideration is of very high molecular weight.

1.1.2 Monomer
Monomers are generally simple organic molecules from which the polymer molecule is made.
The structure of the repeating unit of a polymer is essentially that or closely related to that of
the monomer molecule(s). The formula of the polystyrene repeating unit (II) is thus seen to be
essentially the same as that of the monomer styrene CH2 CH-C6 H5 .
The repeating unit of a linear polymer is a small portion of the macromolecule such that linking
together these units one after another gives rise to the formula of the whole molecule. A repeating
unit may be a single component such as (II) for the polymer (I), or it may consist of the residues
of several components, as in poly(ethylene terephthalate), which has the structure :

(III)
The repeating unit in (III) may be written as

(IV)

Thus, the whole molecule of (III) can be built by linking the left-hand atom shown in (IV) to
the right-hand atom, and so on.
Though it has been stated above that structures of repeating units are essentially those of the
monomers from which the polymers are made, this is not always the case. Considering, for exam-
ple, poly(vinyl alcohol) :

(V)
the obvious precursor monomer for this polymer is vinyl alcohol, CH2 =CH-OH, which is an unsta-
ble tautomer of acetaldehyde and does not exist. Poly(vinyl alcohol) is instead made by alcoholysis
of poly(vinyl acetate),

CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH

OCCH3 OCCH3 OCCH3 OCCH3 OCCH3
O O O O O
(VI)
which, in turn, is synthesized by polymerization of the monomer vinyl acetate, CH2 =CHOOCCH3 .
Another example is cellulose, which is a carbohydrate with molecular formula (C6 H10 O5 )n ,
where n is a few thousand. The structure is
Introductory Concepts 3

CH2OH H OH CH2OH H OH
H O O H H O O H
H H
4 H 1 OH H H OH H
OH OH
H H
O H H O O H H O O
H OH CH2OH H OH CH2OH

(VII)

Complete hydrolysis of cellulose by boiling with concentrated hydrochloric acid yields D-glucose,
C6 H12 O6 , in 95% yield. Cellulose can thus be considered chemically as a polyanhydroglucose,
though it cannot be synthesized from glucose. The concept of the repeating unit is most useful for
linear homopolymers (see later).

1.1.3 Molecular Weight and Molar Mass

The term ‘molecular weight’ is frequently used in practice instead of the term ‘molar mass’, though
the former can be somewhat misleading. Molecular weight is really a dimensionless quantity
given by the sum of the atomic weights in the molecular formula. The atomic weights, in turn,
are dimensionless ratios of the masses of the particular atoms to 1/12 of the mass of an atom
of the most abundant carbon isotope 12 C6 to which a mass of 12 atomic mass units (AMU) is
assigned. (AMU, a unit used for expressing the atomic masses of individual isotopes of elements,
is approximately 1.66041024 g.) The molar mass of a substance, on the other hand, is the mass
of 1 mol of the substance and usually is quoted in units of g/mol or kg/mol. The numerical value of
molecular weight is multiplied by the specific units, such as g/mol, to convert it into an equivalent
value of molar mass in dimensions of g/mol. Thus, a molecular weight of 100,000 is equivalent to
a molar mass of 100,000 g/mol or 100 kg/mol.
In this book, we shall retain the term ‘molecular weight’ because of its widespread use in the
polymer literature. However, when using in numerical calculations we shall substitute the molec-
ular weight by its numerically equivalent molar mass (g/mol) to facilitate dimensional balancing.

1.1.4 End Groups

In none of the above examples of the structural representation of polymers have the end groups
been shown. This is partly because the exact nature of the end groups of polymer molecules is
often not known and partly because end groups constitute an insignificant fraction of the mass
of high molecular weight polymer and so usually have negligible effect on polymer properties of
major interest.

Problem 1.1 Calculate the end group content (weight fraction) of polystyrene of molecular weight 150,000,
assuming that phenyl (C6 H5 -) groups constitute both the end groups of an average polymer molecule.
Answer:
Molar mass of phenyl group  612  51  77 g mol1
2 77 g mol1 
Wt. fraction of end groups   0.001
1.5  105 g mol1 
4 Chapter 1

1.1.5 Degree of Polymerization

This term refers to the number of repeating units that constitute a polymer molecule. We shall use
the abbreviation DP for the degree of polymerization defined in this way. The subscript n used on
the parentheses in the foregoing structural formulas for polymers represents this DP. The relation
between degree of polymerization and molecular weight M of the same macromolecule is given
by

M  DP Mo (1.1)

where Mo is the formula weight of the repeating unit.

1.1.6 Copolymers
If a macromolecule is made from only one species of monomer, the product is a homopolymer,
referred to simply as a polymer. The word homopolymer often is used more broadly to describe
polymers whose structure can be represented by repetition of a single type of repeating unit con-
taining one or more species. Thus, a hypothetical polymer -[-AB-]-n made from A and B species is
also a homopolymer, e.g., poly(ethylene terephthalate) (III).
The formal definition of a copolymer is a polymer derived from more than one species of
monomer. The copolymer with a relatively random distribution of the different mers or repeating
units in its structure is commonly referred to as a random copolymer. Representing two different
mers by A and B, a random copolymer can be depicted as

—ABBABBBAABBAABAAABBA—

There are three other copolymer structures : alternating, block, and graft copolymer structures
(Fig. 1.1). In the alternating copolymer, the two mers alternate in a regular fashion along the
polymer chain :

—ABABABABABABABABABAB—

A block copolymer is a linear polymer with one or more long uninterrupted sequences of each
mer in the chain :

—AAAAAAAAAABBBBBBBBBB—

Block copolymers may have a different number of blocks in the molecule. Thus, Ax By , Ax By Ax ,
Ax By Ax By , (Ax By )n are referred to as AB diblock, ABA triblock, ABAB tetrablock, and AB
multiblock copolymers, respectively. Since there is a distribution of block lengths and number of
blocks along the copolymer chain, x and y as well as n represent average values.
A graft copolymer, on the other hand, is a branched copolymer with a backbone of one type of
mer and one or more side chains of another mer :
Introductory Concepts 5

(a )

(b)

(c)

(d)

Figure 1.1 Copolymer arrangements : (a) Two different types of mers (denoted by open and filled circles)
are randomly placed. (b) The mers are alternately arranged. (c) A block copolymer. (d) A graft copolymer.

AAAAAAAAAAAAAAAAAAA
B
B
B
B
B

Copolymerization, which, in its objective, may be compared to alloying in metallurgy, is very

useful for synthesizing polymer with the required combination of properties.

1.2 Polymerization and Functionality

Polymerization may occur only if the monomers involved in the reaction have the proper function-
alities. Functionality is a very useful concept in polymer science. The functionality of a molecule
is the number of sites it has for bonding to other molecules under the given conditions of the
polymerization reaction (Rudin, 1982). Thus, a bifunctional monomer, i.e., a monomer with func-
tionality 2, can link to two other molecules under suitable conditions. Styrene, C6 H5 CH=CH2 ,
for example, has functionality 2 because of the presence of a carbon-carbon double bond. The
minimum functionality required for polymerization is 2.
6 Chapter 1

A polyfunctional monomer is one that can react with more than two molecules under the con-
ditions of the polymerization reaction. Thus, divinyl benzene (VIII) is tetrafunctional in reactions
involving additions across carbon-carbon double bonds, while glycerol (IX) is trifunctional and
pentaerythritol, C(CH2 OH)4 , is tetrafunctional in polyesterification reactions.

HC CH2
HO CH2 CH CH2 OH
OH
(IX)

HC CH2
(VIII)

Functionality in polymerization is, however, defined only for a given reaction (Rudin, 1982).
Thus, a glycol, HOROH, has a functionality of 2 in esterification or ether-forming reactions, but
its functionality is zero in amidation reactions.

Problem 1.2 What is the functionality of the following monomers in reactions with (i) styrene, C6 H5 CH=CH2
and (ii) adipic acid, HOOC(CH2 )4 COOH ?

CH3
(a) H2C C
O C OCH3
(b) HO CH2CH2 OH
(c) H2C CH CH2 OH
(d) H2C C C O CH2 CH2O C C CH2
CH3 O O CH3
O
(e) O

Answer:
(i) In reaction with styrene, the functionalities of the monomers are :
(a) 2 (one reactive carbon-carbon double bond)
(b) 0 (-OH groups do not take part in addition reactions)
(c) 2 (one reactive carbon-carbon double bond; –OH group
nonreactive)
(d) 4 (two reactive carbon-carbon double bonds)
(e) 2 (one reactive carbon-carbon double bond)

(ii) In reaction with adipic acid, the functionalities of the monomers are :
(a) 0 (carbon-carbon double bond nonreactive)
(b) 2 (two reactive -OH groups)
Exploring the Variety of Random
Documents with Different Content
 Standing erect under his hands, she looked hard into his face.
“You could frighten me, horribly; but you couldn’t shatter me. You are
ambiguous, veiled, all in mists. I am as clear, as sharp—.”
Her dauntlessness, the old defiance, were a relief—a really delicious
relief. He was able to smile at her, a smile that pled for reassurance. “How
can I frighten you, then?”
Her somber gaze did not soften. “Your mists come round me, chill,
suffocating. They corrode my clearness.”
“No; no; it’s you who come into them. Don’t. Don’t. Keep away from
me.”
“I’m not so afraid of you as that,” she answered.
His hands were still on her shoulders and their eyes on each other—his
with their appealing, uncertain smile, and hers unmoved, unsmiling; and
suddenly that sense of danger came upon him: as if, in the mist, he felt upon
him the breathing, warm, sweet, ominous, of some unseen creature. And in
the fear was a strange delight, and like a hand drawn, with slow, deep
pressure, across a harp, the nearness drew across his heart, stirring its one
sad note—its dumb, its aching note—to a sudden ascending murmur of
melody.
He was caught swiftly from this inner tumult by its reflection in her face.
She flushed, deeply, painfully. She drew back sharply, pushing his hands
from her.
Gavan sought his own equilibrium in an ignoring of that undercurrent.
“Now you are not frightened; but why are you angry?” he asked.
For a moment she did not speak.
“Eppie, I am so sorry. What is it? You are really angry, Eppie!”
Then, after that pause of speechlessness, she found words.
“If I think of you as mist you must not think of me as glamour.” This she
gave him straight.
Only after disengaging her train from the settle, from his feet, after
wheeling aside his chair to make a clear passage for her departure, did she
add: “I have read your priggish Schopenhauer.”
She gave him no time for reply or protestation. Quite mistress of herself,
leaving him with all the awkwardness of the situation—if he chose to
consider it awkward—upon his hands, very fully the finished mondaine and
very beautifully the fearless and assured nymph of the hillside, she went to
the piano, turned and rejected, in looking over it, some music, and sitting
down, striking a long, full chord, she began to sing, in her voice of frosty
dawn, the old Scotch ballad.
He might go or listen as he liked. She had put him away, him and his
mists, his ambiguous hold upon her, his ambiguous look at her. She sang to
please herself as much as when she had gone up through the woodlands.
And if the note of anger still thrilled in her voice she turned it to the uses of
her song and made a higher triumph of sadness.
She was still singing when the general came in.

SHE had been quite right; she had seen with her perfect sharpness and
clearness indeed, and no wonder that she had been angry. He himself saw
clearly, directly the hand was off the harp. It was laughably simple. He was
a man, she a woman; they were both young and she was beautiful. That
summed it up, sufficiently and brutally; and no wonder, again, that she had
felt such summing an offense. It wasn’t in the light of such summings that
she regarded herself.
With him she had never, for a moment, made use of glamour. His was
the rudimentary impulse, and Gavan’s sensitive cheek echoed her flush
when he thought of it. Never again, he promised himself, after this full
comprehension of it, should such an impulse dim their friendship. He would
make it up to her by helping her to forget it.
But for all that, it was with the strangest mixture of relief and dismay
that he found upon the breakfast-table next morning an urgent summons for
his return home. It was the affable little rector of the parish in Surrey who
wrote to tell him of his father’s sudden breakdown,—softening of the brain.
When Eppie appeared, a little grave, but all clear composure, he was able to
show her the letter and to tell her of his immediate departure with a
composure as assured as her own, but he wondered, while he spoke, if to
her also the parting would mean any form of relief. At all events, for her, it
couldn’t mean any form of wrench.
Looking in swift glances at her face, while she questioned him about his
father, suggested trains and nurses, and gave practical advice for his
journey, he was conscious that the relief was the result of a pretty severe
strain, and that though it was relieved it hadn’t stopped aching.
The very fact that Eppie’s narrow face, the hair brushed back from brow
and temples, showed, in the clear morning light, more of its oddity than its
beauty, made its charm cling the more closely. Her eyes looked small, her
features irregular; he saw the cliff-like modeling of her temples, the cheeks,
a little flat, pale, freckled; the long, queer lines of her chin. Bare, exposed,
without a flicker of sunlight on her delicate analogies of ruggedness, of
weather-beaten strength, she might almost have been called ugly; and, with
every glance, he was feeling her as sweetness, sweetness deep and reticent,
embodied.
The general and Miss Barbara were late. She poured out his coffee, saw
him embarked on a sturdy breakfast, insisted, now with the irradiating smile
that in a moment made her lovely, that he should eat a great deal before his
journey, made him think anew of that maternal quality in her,—the
tolerance, the tenderness. And in the ambiguous relief came the sharpened
dismay of seeing how great was the cause for it.
He wanted to say a word, only one, about their little drama of last night,
but the time didn’t really seem to come for it; perhaps she saw that it
shouldn’t come. But on the old stone steps with their yellow lichen spots,
his farewells over to the uncle and aunt, and he and Eppie standing out there
in a momentary solitude, she said, shaking his hand, “Friends, you know.
Look me up when you are next in London.” She had her one word to say,
and she had said it when and how she wished. It wasn’t anything so crude
as reassurance; it was rather a sunny assurance, in which she wished him to
share, that none was needed.
He looked, like the boy of years ago, a real depth of gratitude into her
eyes. She had given him his chance.
“I’ll never frighten you again; I’ll never displease you again.”
“I know you won’t. I won’t let you,” Eppie smiled.
“I wish I were more worth your while—worth your being kind to me.”
“You think you are still—gloomy, tiresome, self-centered?”
“That defines it well enough.”
“Well, you serve my purpose,” said Eppie, “and that is to have you for
my friend.”
 She seemed in this parting to have effaced all memory of glamour, but
Gavan knew that the deeper one was with him.
It was with him, even while, in the long journey South, he was able to
unwrap film after film of the mirage from its central core of reality, to see
Eppie, in all her loveliness, in all her noblest aspects, as a sort of
incarnation of the world, the flesh, and the devil. He could laugh over the
grotesque analogy; it proved to him how far from life he was when its
symbol could show in such unflattering terms, and yet it hurt him that he
could find it in himself so to symbolize her. It was just because she was so
lovely, so noble, that he must—he must—. For, under all, was the wrench
that would take time to stop aching.

X
APTAIN PALAIRET had gone to pieces and was now as
unpleasant an object as for years he had been a pleasant one.
Gavan’s atrophied selfishness felt only a slight shrinking from
the revolting aspects of dissolution, and his father’s condition
rather interested him. The captain’s childish clinging to his son was like an
animal instinct suddenly asserting itself, an almost vegetable instinct, so
little more than mere instinct was it. It affected Gavan much as the suddenly
contracting tentacles of a sea-anemone upon his finger might have done. He
was not at all touched; but he felt the claim of a possible pang of loneliness
and desolation in the dimness of decay, and, methodically, with all the
appearances of a solicitous kindness, he responded to the claim.
The man, immersed in his rudimentary universe of sense, showed a host
of atavistic fears; fears of the dark, of strange faces, fears of sudden noises
or of long stillness. He often wept, leaning his swollen face on Gavan’s
shoulder, filled with an abject self-pity.
“You know how I love you, Gavan,” he would again and again repeat,
his lax lips fumbling with the words, “always loved you, ever since you
were a little fellow—out in India, you know. I and your dear mother loved
you better than life,” and, wagging his head, he would repeat, “better than
life,” and break into sobs—sobs that ceased when the nurse brought him his
wine-jelly. Then it might be again the tone of feeble whining. “It doesn’t
taste right, Gavan. Can’t you make it taste right? Do you want to starve me
between you all?”
Gavan, with scientific scrutiny, diagnosed and observed while he
soothed him or engaged his vagrant mind in games.
In his intervals of leisure he pursued his own work, and rode and walked
with all his usual tempered athleticism. He did not feel the days as a strain,
hardly as disagreeable; he was indifferent or interested. At the worst he was
bored. The undercurrent of pity he was accustomed to living with.
Only at night, in hours of rest, he would sink into a half-dazed disgust,
find himself on edge, nearly worn out. So the winter passed.
He was playing draughts with his father on a day in earliest spring, when
he was told that Mrs. Arley and Miss Gifford were below.
Gavan was feeling dull and jaded. The conducting of the game needed a
monotonous patience and tact. The captain would now pick up a draught
and gaze curiously at it for long periods of time, now move in a direction
contrary to all the rules of the game and to his own advantage. When such
mistakes were pointed out to him he would either apologize humbly or
break into sudden peevish wrath. To-day he was in a peculiarly excitable
condition and had more than once wept.
Gavan, after the servant’s announcement, holding a quietly expectant
draught in his thin, poised fingers, looked hard at the board that still waited
for his father’s move. He then felt that a deep flush had mounted to his face.
In spite of the one or two laconic letters that they had interchanged,
Eppie had been relegated for many months to her dream-place—a dream, in
spite of its high coloring, more distant than this nearer dream of ugly
illness. It was painful to look back at the queer turmoil she had roused in
him during the autumnal fortnight, and more painful to realize, as in his
sudden panic of reluctance now, that, though a dream, she was an abiding
and constant one.
Mrs. Arley he knew, and her motor-car had recently made her a next-
door neighbor in spite of the thirty miles between them. She was a friend
with whom Eppie had before stayed on the other side of the county.
Nothing could be more natural than that she and Eppie should drop in upon
a solitude that must, to their eyes, have all the finished elements of pathos.
Yet he was a little vexed by the intrusion, as well as reluctant to meet it.
 His father broke into vehement protest when he heard that he was to be
abandoned at an unusual hour, and it needed some time for Gavan and the
nurse to quiet him. Twenty minutes had passed before he could go down to
his guests, and he surmised that they would feel in this delay yet further
grounds for pity.
They were in the hall, before a roaring fire, Eppie standing with her back
to it, in a familiar attitude, though her long, caped cloak and hooded
motoring-cap, the folds of gray silk gathered under her chin and narrowly
framing her face, gave her an unfamiliar aspect. Her eyes met his as he
turned the spacious staircase and came down to them, and he felt that they
watched his every movement and noted every trace in him of fatigue and
dejection.
Mrs. Arley, fluent, flexible, amazingly pretty, for all the light powdering
and wrinkling of her fifty years, came rustling forward.
“Eppie is staying with me for the week-end,—I wrench her from her
slums now and then,—and we wanted to hear how you are, to see how you
are. You look dreadfully fagged; doesn’t he, Eppie? How is your father?”
Eppie gave him her hand in silence.
“My father will never be any better, you know,” he said. “As for me, I’m
all right. I should have come over to see you before this, and looked you up,
too, Eppie, but I can’t get away for more than an hour or so at a time.”
He led them into the library while he spoke,—Mrs. Arley exclaiming
that such devotion was dear and good of him,—and Eppie looked gravely
round at the room that he had described to her as the room that he really
passed his life in. The great spaces of ranged books framed for her, he
knew, pictures of his own existence. He knew, too, that her gravity was the
involuntary result of the impression that he made upon her. She was sorry
for him. Poor Eppie, their relationship since childhood seemed to have
consisted in that—in the sense of her pursuing pity and in his retreat before
it, for her sake. He retreated now, as he knew, in his determination to show
her that pity was misplaced, uncalled for.
Mrs. Arley had thrown off her wrap and loosened her hood in a manner
that made it almost imperative to ask them to stay with him for lunch—an
invitation accepted with an assurance showing that it had been expected,
and it wasn’t difficult, in conventional battledore and shuttlecock with her,
to show a good humor and frivolity that discountenanced pathetic
interpretations. What Mrs. Arley’s interpretations were he didn’t quite
know; her eyes, fatigued yet fresh, were very acute behind their trivial
meanings, and he could wonder if Eppie had shared with her her own sense
of his “horribleness,” and if, in consequence, her conception of Eppie’s
significance as the opponent of that quality was tinged with sentimental
associations.
Eppie’s gaze, while they rattled on, lost something of its gravity, but he
was startled, as if by an assurance deeper than any of Mrs. Arley’s, when
she rose to slip off her coat and went across the room to a small old mirror
that hung near the door to take off her cap as well.
In her manner of standing there with her back to them, untying her veils,
pushing back her hair, was the assurance, indeed, of a person whose feet
were firmly planted on certain rights, all the more firmly for “knowing her
place” as it were, and for having repudiated mistaken assumptions. She
might almost have been a new sick-nurse come to take up her duties by his
side. She passed from the mirror to the writing-table, examining the books
laid there, and then, until lunch was announced, stood looking out of the
window. Quite the silent, capable, significant new nurse, with many
theories of her own that might much affect the future.
The dining-room at Cheylesford Lodge opened on a wonderful old lawn,
centuries in its green. Bordered by beds, just alight with pale spring flowers,
it swept in and out among shrubberies of rhododendron and laurel, the
emerald nook set in a circle of trees, a high arabesque on the sky.
Eppie from her seat at the table faced the sky, the trees, the lawn. What a
beautiful place, she was thinking. A place for life, sheltered, embowered.
How she would have loved, as a child, those delicious rivulets of green that
ran into the thick mysteries of shadow. How she would have loved to play
dolls on a hot summer afternoon in the shade of the great yew-tree that
stretched its dark branches half across the sky. The house, the garden, made
her think of children; she saw white pinafores and golden heads glancing in
and out among the trees and shrubs, and the vision of young life,
blossoming, growing in security and sunlight, filled her thought with its
pictured songs of innocence, while, at the same time, under the vision, she
was feeling it all—all the beauty and sheltered sweetness—as dreadful in its
emptiness, its worse than emptiness: a casket holding a death’s-head. She
came back with something of a start to hear her work in the slums
enthusiastically described by Mrs. Arley. “I thought it was only in novels
that children clung to the heroine’s skirts. I never believed they clung in real
life until seeing Eppie with her ragamuffins; they adore her.”
This remark, to whose truth she assented by a vague smile, gave Eppie’s
thoughts a further push that sent them seeing herself among the golden
heads and white pinafores on the lawn at Cheylesford Lodge; and though
the vision maintained its loving aunt relationship of the slums, there was
now a throb and flutter in it, as though she held under her hand a strange
wild bird that only her own will not to look kept hidden.
These dreams were followed by a nightmare little episode.
In the library, again, the talk was still an airy dialogue, Eppie, her eyes
on the flames as she drank her coffee, still maintaining her ruminating
silence. In the midst of her thoughts and their chatter, the door opened
suddenly and Captain Palairet appeared on the threshold.
His head neatly brushed, a sumptuous dressing-gown of padded and
embroidered silk girt about him, he stood there with moist eyes and lips,
faintly and incessantly shaking through all his frame, a troubling and
startling figure.
Gavan had been wondering all through the visit how his father was
bearing the abandonment, and his appearance, he saw now, must have been
the triumphant fruit of contest with the nurse whose face of helpless
disapprobation hovered outside.
Gavan went to his side, and, leaning on his son’s arm, the captain said
that he had come to pay his respects to Mrs. Arley and to Miss Gifford.
Taking Mrs. Arley’s hand, he earnestly reiterated his pleasure in
welcoming her to his home.
“Gavan’s in fact, you know; but he’s a good son. Not very much in
common, perhaps: Gavan was always a book-worm, a fellow of fads and
theories; I love a broad life, men and things. No, not much in common,
except our love for his mother, my dear, dead wife; that brought us together.
We shook hands over her grave, so to speak,” said the captain, but without
his usual sentiment. An air of jaunty cheerfulness pervaded his manner.
“She is buried near here, you know. You may have seen the grave. A very
pretty stone; very pretty indeed. Gavan chose it. I was in India at the time.
A great blow to me. I never recovered from it. I forget, for the moment,
what the text is; but it’s very pretty; very appropriate. I knew I could trust
Gavan to do everything properly.”
Gavan’s face had kept its pallid calm.
“You will tire yourself, father,” he said. “Let me take you up-stairs now.
Mrs. Arley and Miss Gifford will excuse us.”
The captain resisted his attempt to turn him to the door.
“Miss Gifford. Yes, Miss Gifford,” he repeated, turning to where Eppie
stood attentively watching father and son, “But I want to see Miss Elspeth
Gifford. It was that I came for.” He took her hand and his wrecked and
restless eyes went over her face. “So this is Miss Elspeth Gifford.”
“You have heard of me?” Eppie’s composure was as successful as
Gavan’s own and lent to the scene a certain matter-of-fact convention.
The captain bowed low. “Heard of you? Yes. I have often heard of you. I
am glad, glad and proud, to meet at last so much goodness and wit and
beauty. You have a name in the world, Miss Gifford. Yes, indeed, I have
heard of you.” Suddenly, while he held her hand and gazed at her, his look
changed. Tears filled his eyes; a muscle in his lip began to shake; a flush of
maudlin indignation purpled his face.
“And you are the girl my son jilted! And you come to our house! It’s a
noble action. It’s a generous action. It’s worthy of you, my dear.” He tightly
squeezed her hand, Gavan’s attempt—and now no gentle one—to draw him
away only making his clutch the more determined.
“No, Gavan, I will not go. I will speak my mind. This is my hour. The
time has come for me to speak my mind. Let’s have the truth; truth at all
costs is my motto. A noble and generous action. But, my dear,” he leaned
his head toward her and spoke in a loud whisper, “you’re well rid of him,
you know—well rid of him. Don’t try to patch it up. Don’t come in that
hope. So like a woman—I know, I know. But give it up; that’s my advice.
Give it up. He’s a poor fellow—a very poor fellow. He wouldn’t make you
happy; just take that from me—a friend, a true friend. He wouldn’t make
any woman happy. He’s a poor creature, and a false creature, and I’ll say
this,” the captain, now trembling violently, burst into tears: “if he has been a
false lover to you he has been a bad son to me.”
With both hands, sobbing, he clung to her, while, with a look of sick
distress, Gavan tried, not too violently, to draw him from his hold on her.
 Eppie had not flushed. “Don’t mind,” she said, glancing at the helpless
son, “he has mixed it up, you see.” And, bending on the captain eyes severe
in kindly intention, like the eyes of a nurse firmly administering a potion,
“You are mistaken about Gavan. It was another man who jilted me. Now let
him take you up-stairs. You are ill.”
But the captain still clung, she, erect in her spare young strength,
showing no shrinking of repulsion. “No, no,” he said; “you always try to
shield him. A woman’s way. He won your heart, and then he broke it, as he
has mine. He has no heart, or he’d take you now. Give it up. Don’t come
after him. Sir, how dare you! I won’t submit to this. How dare you, Sir!”
Gavan had wrenched him away, and in a flare of silly passion he struck at
him again and again, like a furious child. It was a wrestle with the animal,
the vegetable thing, the pinioning of vicious tentacles. Mrs. Arley fluttered
in helpless consternation, while Eppie, firm and adequate, assisted Gavan in
securing the wildly striking hands. Caught, held, haled toward the door, the
captain became, with amazing rapidity, all smiles and placidity.
“Gently, gently, my dear boy. This is unseemly, you know, very childish
indeed. Temper! Temper! You get it from me, no doubt—though your
mother could be very spiteful at moments. I’ll come now. I’ve said my say.
Well rid of him, my dear, well rid of him,” he nodded from the door.
“Eppie! My dear!” cried Mrs. Arley, when father and son had
disappeared. “How unutterably hateful. I am more sorry for him than for
you, Eppie. His face!”
Eppie was shrugging up her shoulders and straightening herself as
though the captain’s grasp still threatened her.
“Hateful indeed; but trivial. Gavan understands that I understand. We
must make him feel that it’s nothing.”
“He’s quite mad, horrible old man.”
“Not quite; more uncomfortably muddled than mad. We must make him
see that we think nothing of it,” Eppie repeated. She turned to Gavan, who
entered as she spoke, still with his sick flush and showing a speechless
inability to frame apologies.
“This is what it is to have echoes, Gavan,” she said. “My little
misfortunes have reached your father’s ears.” She went to him, she took his
hand, she smiled at him, all her radiance recovered, a garment of warmth
and ease to cover the shivering the captain’s words might have made.
“Please don’t mind. I wasn’t a bit bothered, really.”
He could almost have wept for the relief of her smile, her sanity. The
linking of their names in such an unthinkable connection had given him the
nausea qualm of a terrifying obsession. He could find now only trite words
in which to tell her that she was very kind and that he was more sorry than
he could say.
“But you mustn’t be. It was such an obvious muddle for a twisted mind.
He knew,” said Eppie, still smiling with the healing radiance, “that I had
been jilted, and he knew that I was very fond of you, and he put together the
one and one make two that happened to be before him.” She saw that his
distress had been far greater than her own, that she now gave him relief.
Afterward, as she and Mrs. Arley sped away, her own reaction from the
healing attitude showed in a rather grim silence. She leaned back in the
swift, keen air, her arms folded in the fullness of her capes.
But Mrs. Arley could not repress her own accumulations of feeling. “My
dear Eppie,” she said, her hand on her shoulder, and with an almost more
than maternal lack of reticence, “I want you to marry him. Don’t glare
Medusa at me. I hate tact and silences. Heaven knows I would have scouted
the idea of such a match for you before seeing him to-day. But my hard old
heart is touched. He is such a dear; so lonely. It’s a nice little place, too, and
there is some money. Jim Grainger is too drab-colored a person for you,—
all his force, all his sheckles, can’t gild him,—and Kenneth Langley is
penniless. This dear creature is not a bit drab and not quite penniless. And
you are big enough to marry a man who needs you rather than one you
need. Will you think of it, Eppie?”
“Grace, you are worse than Captain Palairet,” said Eppie, whose eyes
were firmly fixed on the neat leather back of the chauffeur in front of them.
“Don’t be cross, Eppie. Why should you mind my prattle?”
“Because I care for him so much.”
“Well, that’s what I say.”
“No; not as I mean it.”
“He of course cares, as I mean it.”
Eppie did not pause over this.
 “It’s something different, quite different, from anything else in the
world. It can’t be talked about like that. Please, Grace, never, never be like
Captain Palairet again. You haven’t softening of the brain. I shall lose
Gavan if my friends and his father have such delusions too openly.”

XI
AVAN went down the noisy, dirty thoroughfare, looking for the
turning which would lead him, so the last policeman consulted
said, to Eppie’s little square.
It was a May day, suddenly clear after rain, liquid mud below,
and above a sharply blue sky, looking its relentless contrast at the reeking,
sordid streets, the ugly, hurrying life of the wide thoroughfare.
All along the gutter was a vociferous fringe of dripping fruit-and food-
barrows, these more haphazard conveniences faced by a line of gaudy,
glaring shops.
The blue above was laced with a tangle of tram-wires and cut with the
jagged line of chimney-pots.
The roaring trams, the glaring shops, seemed part of a cruel machinery
creative of life, and the grim air of permanence, the width and solidity of
the great thoroughfare, were more oppressive to Gavan’s nerves, its
ugliness fiercer, more menacing, than the narrower meanness of the streets
where life seemed to huddle with more despondency.
In one of these he found that he had, apparently, lost his way.
A random turn brought him to a squalid court with sloping, wet
pavement and open doors disgorging, from inner darkness, swarms of
children. They ran; tottered on infantile, bandy legs; locked in scuffling
groups, screaming shrilly, or squatted on the ground, absorbed in some
game.
Gavan surveyed them vaguely as he wandered seeking an outlet. His eye
showed neither shrinking nor tenderness, rather a bleak, hard, unmoved
pity, like that of the sky above. He was as alien from that swarming, vivid
life as the sky; but, worn as he was with months of nervous overstrain, he
felt rising within him now and then a faint sense of nausea such as one
might feel in contemplating a writhing clot of maggots.
 He threaded his way among them all, and at a corner of the court found a
narrow exit. This covered passage led, apparently, to another and fouler
court, and emerging from it, coming suddenly face to face with him, was
Eppie. She was as startling, seen here, as “a lily in the mouth of Tartarus,”
and he had a shock of delight in her mere aspect. For Eppie was as exquisite
as a flower. Her garments had in no way adapted themselves to mud and
misery. Her rough dress of Japanese blue showed at the open neck of its
jacket a white linen blouse; her short, kilted skirt swung with the grace of
petals; her little upturned cap of blue made her look like a Rosalind ready
for a background of woodland glade, streams, and herds of deer.
And here she stood, under that cruel sky, among the unimaginable
ugliness of this City of Dreadful Night.
In her great surprise she did not smile, saying, as she gave him her hand,
“Gavan! by all that’s wonderful!”
“You asked me to come and see you when I was next in London.”
“So I did.”
“So here I am. I had a day off by chance; some business that had to be
seen to.”
“And your father?”
“Slowly going.”
“And you have come down here, for how long?”
“For as long as you’ll keep me. I needn’t go back till night.”
Her eye now wandered away from him to the maggots, one of whom,
Gavan observed, had attached itself to her skirt, while a sufficiently dense
crowd surrounded them, staring.
“You have a glimpse of our children,” said Eppie, surveying them with,
not exactly a maternal, but, as it were, a fraternal eye of affectionate
familiarity.
“What’s that, Annie?” in answer to a husky whisper. “Do I expect you
to-night? Rather! Is that the doll, Ada? Well, I can’t say that you’ve kept it
very tidy. Where’s its pinafore?” She took the soiled object held up to her
and examined its garments. “Where’s its petticoat?”
“Please, Miss, Hemly took them.”
“Took them away from you?”
 “Yes, Miss.”
“For her own doll, I suppose.”
“Yes, Miss.”
Eppie cogitated. “I’ll speak to Emily about it presently. You shall have
them back.”
“Please, Miss, I called her a thief.”
“You spoke the truth. How are you, Billy? You look decidedly better.
Gavan, my hands are full for the next hour or so and I can’t even offer to
take you with me, for I’m going to sick people. But I shall be back and
through with all my work by tea-time, if you don’t mind going to my place
and waiting. You’ll find Maude Allen there. She lives down here, and with
me when I am here. She is a nice girl, though she will talk your head off.”
“How do I find her? I don’t mind waiting.”
“You follow this to the end, take the first turning to the right, and that
will bring you to my place. I’ll meet you there at five.”
Gavan, thus directed, made his way to the dingy little house occupied by
the group of energetic women whom Eppie joined yearly for her three
months of—dissipation? he asked himself, amused by her variegated vigor.
The dingy little house looked on a dingy little square—shell of former
respectable affluence from which the higher form of life had shriveled. The
sooty trees were thickly powdered with young green, and uneven patches of
rough, unkempt grass showed behind broken iron railings. A cat’s-meat man
called his dangling wares along the street, and Gavan, noticing a thin and
furtive cat, that stole from a window-ledge, stopped him and bought a large
three-penny-worth, upon which he left the cat regaling itself with an odd,
fastidious ferocity.
He entered another world when he entered Eppie’s sitting-room. Here
was life at its most austerely sweet. Books lined the walls, bowls of
primroses and delicate Japanese bronzes set above their shelves; chintz-
covered chairs were drawn before the fire; the latest reviews lay on a table,
and on the piano stood open music; there were wide windows in the little
room, and crocuses, growing in flat, earthenware dishes, blew out their
narrow chalices against the sunlit muslin curtains.
Miss Allen sat sewing near the crocuses, and, shy and voluble, rose to
greet him. She was evidently accustomed to Eppie’s guests—accustomed,
too, perhaps, to taking them off her hands, for though she was shy her
volubility showed a familiarity with the situation. She was almost as funny
a contrast to Eppie as the slum children had been an ugly one. She wore a
spare, drab-colored skirt and a cotton shirt, its high, hard collar girt about
by a red tie that revealed bone buttons before and behind. Her sleek, fair
hair, relentlessly drawn back, looked like a varnish laid upon her head. Her
features, at once acute and kindly, were sharp and pink.
She was sewing on solid and distressingly ugly materials.
“Yes, I am usually at home. Miss Gifford is the head and I am the hands,
you see,” she smiled, casting quick, upward glances at the long, pale young
man in his chair near the fire. “Miss Henderson, Miss Grey, and I live here
all year round, and I do so look forward to Miss Gifford’s coming. Oh, yes,
it’s a most interesting life. Do you do anything of the sort? Are you going to
take up a club? Perhaps you are going into the Church?”
Miss Allen asked her swift succession of questions as if in a mild
desperateness.
Gavan admitted that his interest was wholly in Miss Gifford.
“She is interesting,” Miss Allen, all comprehension, agreed. “So many
people find her inspiring. Do you know Mr. Grainger, the M.P.? He comes
here constantly. He is a cousin, you know. He has known her, of course,
ever since she was a child. I think it’s very probable that she influences his
political life—oh, quite in a right sense, I mean. He is such a conscientious
man—everybody says that. And then she isn’t at all eccentric, you know, as
so many fashionable women who come down here are; they do give one so
much trouble when they are like that,—all sorts of fads that one has to
manage to get on with. She isn’t at all faddish. And she isn’t sentimental,
either. I think the sentimental ones are worst—for the people, especially,
giving them all sorts of foolish ideas. And it’s not that she doesn’t care. She
cares such a lot. That’s the secret of her not getting discouraged, you see.
She never loses her spirit.”
“Is it such discouraging work?” Gavan questioned from his chair. With
his legs crossed, his hat and stick held on his knee, he surveyed Miss Allen
and the crocuses.
“Well, not to me,” she answered; “but that’s very different, for I have
religious faith. Miss Gifford hasn’t that, so of course she must care a great
deal to make up for it. When one hasn’t a firm faith it is far more difficult, I
always think, to see any hope in it all. I think she would find it far easier if
she had that. She can’t resign herself to things. She is rather hot-tempered at
times,” Miss Allen added, with one of her sharp, shy glances.
Gavan, amused by the idea that Eppie lacked religious faith, inquired
whether the settlement were religious in intention, and Miss Allen sighed a
little in answering no,—Miss Grey, indeed, was a Positivist. “But we
Anglicans are very broad, you know,” she said. “I can work in perfectly
with them all—better with Miss Grey and Miss Gifford than with Miss
Henderson, who is very, very Low. Miss Gifford goes in more for social
conditions and organization—trades-unions, all that sort of thing; that’s
where she finds Mr. Grainger so much of a help, I think.” And he gathered
from Miss Allen’s further conversation, from its very manner of vague
though admiring protest, a clearer conception of Eppie’s importance down
here. To Miss Allen, she evidently embodied a splendid, pagan force,
ambiguous in its splendor. He saw her slightly shrinking vision of an intent
combatant; no loving sister of charity, but a young Bellona, the latest
weapons of sociological warfare in her hands, its latest battle-cry on her
lips. And all for what? thought Gavan, while, with a sense of contrasting
approval, he looked at Miss Allen’s tidy little head against the sunlit
crocuses and watched the harmless occupation of her hands. All for life,
more life; the rousing of desire; the struggling to higher forms of
consciousness. She was in it, the strife, the struggle. He had seen on her
face to-day, with all its surprise, perhaps its gladness, that alien look of
grave preoccupation that passed from him to the destinies she touched. In
thinking of it all he felt particularly at peace, though there was the irony of
his assurance that Eppie’s efforts among this suffering life where he found
her only resulted in a fiercer hold on suffering. Physical degradation and its
resultant moral apathy were by no means the most unendurable of human
calamities. Miss Allen’s anodynes—the mere practical petting, soothing,
telling of pretty tales—were, in their very short-sightedness, more fitted to
the case.
Miss Allen little thought to what a context her harmless prattle was being
adjusted. She would have been paralyzed with horror could she have known
that to the gentle young man, sitting there so unalarmingly, she herself was
only a rather simple symptom of life that he was quietly studying. In so far
from suspecting, her shyness went from her; he was so unalarming—
differing in this from so many people—that she found it easy to talk to him.
And she still had a happy little hope of a closer community of interest than
he had owned to. He looked, she thought, very High Church. Perhaps he
was in the last stages of conversion.
She had talked on for nearly an hour when another visitor was
announced. This proved to be a young man slightly known to Gavan, a
graceful, mellifluous youth, whose artificiality of manner and great personal
beauty suggested a mingling of absinthe and honey. People had rather
bracketed Gavan and Basil Mayburn together; one could easily deal with
both as lumped in the same category,—charming drifters, softly disdainful
of worldly aims and efforts. Mayburn himself took sympathy for granted,
though disconcerted at times by finding his grasp of the older man to be on
a sliding, slippery surface. Palairet had, to be sure, altogether the proper
appreciations of art and literature, the rhythm of highly evolved human
intercourse; the aroma distilled for the esthete from the vast tragic comedy
of life; so that he had never quite satisfied himself as to why he could get no
nearer on this common footing. Palairet was always charming, always
interested, always courteous; but one’s hold did slip.
And to Gavan, Basil Mayburn, with his fluent ecstasies, seemed a
sojourner in a funny half-way house. To Mayburn the hallucination of life
was worth while esthetically. His own initial appeal to life had been too
fundamentally spiritual for the beautiful to be more to him than a second-
rate illusion.
Miss Allen greeted Mr. Mayburn with a coolness that at once
discriminated for Gavan between her instinctive liking for himself and her
shrinking from a man who perplexed and displeased her.
Mayburn was all glad sweetness: delighted to see Miss Allen; delighted
to see Palairet; delighted to wait in their company for the delightful Miss
Gifford; and, turning to Miss Allen, he went on to say, as a thing that would
engage her sympathies, that he had just come from a service at the Oratory.
“I often go there,” he said; “one gets, as nowhere else that I know of in
London, the quintessence of aspiration—the age-long yearning of the
world. How are your schemes for having that little church built down here
succeeding? I do so believe in it. Don’t let any ugly sect steal a march on
you.”
Miss Allen primly replied that the plans for the church were prospering;
and adding that Miss Gifford would be here in a moment and that she must
leave them, she gathered up her work and departed with some emphasis.
“Nice, dear little creature, that,” said Mayburn, “though she does so
dislike me. I hope I didn’t say the wrong thing. I never quite know how far
her Anglicanism goes; such a pity that it doesn’t go a little further and carry
her into a nunnery of the Catholic Church. She is the nun type. She ought to
be done up in their delicious costume; it would lend her the flavor she lacks
so distressingly now. Did you notice her collar and her hair? Astonishing
the way that Eppie makes use of all these funny, guindée creatures whom
she gets hold of down here. Have you ever seen Miss Grey?—dogmatic,
utilitarian, strangely ugly Miss Grey, another nun type corrupted by our
silly modern conditions. She reeks of Comte and looks like a don. And all
the rest of them,—the solemn humanitarians, the frothy socialists, the
worldly, benign old ecclesiastics,—Eppie works them all; she has a genius
for administration. It’s an art in her. It almost consoles one for seeing her
wasted down here for so much of the year.”
“Why wasted?” Gavan queried. “She enjoys it.”
“Exactly. That’s the alleviation. Wasted for us, I mean. You have known
her for a long time, haven’t you, Palairet?”
Gavan, irked by the question and by the familiarity of Mayburn’s
references to their absent hostess, answered dryly that he had known Miss
Gifford since childhood; and Mayburn, all tact, passed at once to less
personal topics, inquiring with a new earnestness whether Palairet had seen
Selby’s Goya, and expatiating on its exquisite horror until the turning of a
key in the hall-door, quick steps on the stairs leading up past the sitting-
room, announced Eppie’s arrival.
She was with them in a moment, cap and jacket doffed, her muddy shoes
changed for slender patent-leather, fresh in her white blouse. She greeted
Mayburn, turning to Gavan with, “I’m so glad you waited. You shall both
have tea directly.”
With all her crisp kindliness, Gavan fancied a change in her since the
greeting of an hour and a half before. Things hadn’t gone well with her. And
he could flatter himself, also, with the suspicion that she was vexed at
finding their tête-à-tête interrupted.
Mayburn loitered about the room after her while she straightened the
shade on the student’s lamp, just brought in, and made the tea, telling her
about people, about what was going on in the only world that counted,
telling her about Chrissie Bentworth’s astounding elopement, and, finally,
about the Goya. “You really must see it soon,” he assured her.
Eppie, adjusting the flame of her kettle, said that she didn’t want to see
it.
“You don’t care for Goya, dear lady?”
“Not just now.”
“Well, of course I don’t mean just now. I mean after you have burned out
this particular flame. But, really, it’s a sensation before you and you mustn’t
miss having it. An exquisite thing. Horror made beautiful.”
“I don’t want to see it made beautiful,” Eppie, with cheerful rudeness,
objected.
“Now that,” said Mayburn, drawing up to the tea-table with an
appreciative glance for the simple but inviting fare spread upon it—“now
that is just where I always must argue with you. Don’t you agree with me,
Palairet, that life is beautiful—that it’s only in terms of beauty that it has
significance?”
“If you happen to see it so,” Gavan ambiguously assented.
“Exactly; I accept your amendment—if you happen to have the good
fortune to see it so; if you have the faculty that gives the vision; if, like
Siegfried, the revealing dragon’s-blood has touched your lips. Eppie has the
gift and shouldn’t wilfully atrophy it. She shouldn’t refuse to share the
vision of the Supreme Artist, to whom all horror and tragedy are parts of the
picture that his eternal joy contemplates; she should not refuse to listen with
the ear of the Supreme Musician, to whom all the discords that each one of
us is, before we taste the dragon’s-blood,—for what is man but a
dissonance, as our admirable Nietzsche says,—to whom all these discords
melt into the perfect phrase. All art, all truth is there. I’m rather
dithyrambic, but, in your more reticent way, you agree with me, don’t you,
Palairet?”
Eppie’s eye, during this speech, had turned with observant irony upon
Gavan.
“How do you like your echo, Gavan?” she inquired, and she answered
for him: “Of course he agrees, but in slightly different terms. He doesn’t
care a fig about the symphony or about the Eternal Goya. There isn’t a
touch of the ‘lyric rapture’ about him. Now pray don’t ask him to define his
own conceptions, and drink your tea. And don’t say one word to me, either,
about your gigantic, Bohemian deity. You have spoken of Nietzsche, and I
know too well what you are coming to: the Apollonian spirit of the world of
Appearances in which the Dionysiac spirit of Things-in-Themselves mirrors
its vital ecstasy. Spare me, I’m not at all in the humor to see horror in terms
of loveliness.”
“Ay de mi!” Mayburn murmured, “you make me feel that I’m still a
dissonance when you talk like this.”
“A very wholesome realization.”
“You are cross with life to-day, and therefore with me, its poor little
appreciator.”
“I’m never cross with life.”
“Only with me, then?”
“Only with you, to-day.”
Mayburn, folding his slice of bread-and-butter, took her harshness with
Apollonian serenity. “At least let me know that I’ve an ally in you,” he
appealed to Gavan, while Eppie refilled her cup with the business-like air of
stoking an engine that paused for a moment near wayside trivialities.
Gavan had listened to the dithyrambics with some uneasiness, conscious
of Eppie’s observation, and now owned that he felt little interest in the
Eternal Goya.
“Don’t, don’t, I pray of you, let him take the color out of life for you,”
Mayburn pleaded, turning from this rebuff, tea-cup in hand, to Eppie; and
Eppie, with a rather grim smile, again full of reminiscences for Gavan,
declared that neither of them could take anything out of it for her.
She kept, after that, the talk in pleasant enough shallows; but Mayburn
fancied, more than once, that he heard the grating of his keel on an
unpropitious shore. Eppie didn’t want him to-day, that was becoming
evident; she wasn’t going to push him off into decorative sailing. And
presently, wondering a little if his tact had already been too long at fault,
wondering anew about the degree of intimacy between the childhood
friends, who had, evidently, secrets in which he did not share, he gracefully
departed.
Eppie leaned back in her chair, folded her arms, and closed her eyes as
though to give herself the relief of a long silence.
 Her hair softly silhouetted against the green shade and the flickering
illumination of the firelight upon her, her passive face showed a stern
wistfulness. Things had gone wrong with her.
Looking at her, Gavan’s memory went back to the last time they had
been together, alone, in firelight, to his impulse and her startlingly acute
interpretation of it. Her very aspect now, her closed eyes and folded arms,
seemed to show him how completely she disowned, for both of them, even
the memory of such an unfitting episode. More keenly than ever he
recognized the fineness in her, the generosity, the willingness to outlive
trifles, to put them away forever; and the contagion of her somber peace
enveloped him.
She remarked presently, not opening her eyes: “I should like to make a
bon-fire of all the pictures in the world, all the etchings, the carvings, the
tapestries, the bric-à-brac in general,—and Basil Mayburn, in sackcloth and
ashes, should light it.”
“What puritanic savagery, Eppie!”
“I prefer the savage puritan to the Basil Mayburn type; at least I do just
now.”
“What’s the matter?” Gavan asked, after a little pause.
“Do I show it so evidently?” she asked, with a faint smile. “Everything is
the matter.”
“What, in particular, has gone wrong?”
Eppie did not reply at first, and he guessed that she chose only to show
him a lesser trouble when she said, “I’ve had a great quarrel with Miss
Grey, for one thing.”
“The positivistic lady?”
“Yes; did Maude tell you that? She really is a very first-rate person—and
runs this place; but I lost my temper with her—a stupid thing to do, and not
suddenly, either, which made it the less excusable.”
“Are your theories so different that you came to a clash?”
“Of course they are different, though it was apparently only over a
matter of practical administration that we fought.” Eppie drew a long
breath, opening her eyes. “I shall stay on here this spring—I usually go to
my cousin Alicia for the season. But one can’t expect things to go as one
wants them unless one keeps one’s hand on the engine most of the time. She
has almost a right to consider me a meddling outsider, I suppose. I shall stay
on till the end of the summer.”
“And smash Miss Grey?”
Eppie, aware of his amusement, turned an unresentful glance upon him.
“No, don’t think me merely brutally dominant. I really like her. I only
want to use her to the best advantage.”
At this he broke into a laugh. “Not brutally dominant, I know; but I’m
sorry for Miss Grey.”
“Miss Grey can well take care of herself, I assure you.”
“What else has gone wrong?”
Again Eppie chose something less wrong to show him. “The factory
where some of my club-girls work has shut down half of its machinery.
There will be a great deal of suffering. And we have pulled them above a
flippant acceptance of state relief.”
“And because you have pulled them up, they are to suffer more?”
“Exactly, if you choose to put it so,” said Eppie.
He saw that she had determined that he should not frighten her again, or,
at all events, that he should never see it if he did frighten her; and he had
himself determined that his mist should never again close round her. She
should not see, even if she guessed at it pretty clearly, the interpretation that
he put upon the afternoon’s frictions and failures, and, on the plane of a
matter-of-fact agreement as to practice, he drew her on to talk of her
factory-girls, of the standards of wages, the organization of woman’s labor,
so that she presently said, “What a pleasure it is to hear you talking sense,
Gavan!”
“You have heard me talk a great deal of nonsense, I’m sure.”
“A great deal. Worse than Basil Mayburn’s.”
“I saw too clearly to-day the sorry figure I must have cut in your eyes. I
have learned to hold my tongue. When one can only say things that sound
particularly silly that is an obvious duty.”
“I am glad to hear you use the word, my dear Gavan; use it, even though
it means nothing to you. Glissez mortel, n’appuyez pas should be your
motto for a time; then, after some wholesome skating about on what seems
the deceptive, glittering surface of things you will find, perhaps, that it isn’t
an abyss the ice stretches over, but a firm meadow, the ice melted off it and
no more need of skates.”
He was quite willing that she should so see his case; he was easier to live
with, no doubt, on this assumption of his curability.
Eppie, still leaning back, still with folded arms, had once more closed
her eyes, involuntarily sighing, as though under her own words the haunting
echo of the abyss had sounded for her.
She had not yet shown him what the real trouble was, and he asked her
now, in this second lull of their talk, “What else is there besides the factory-
girls and Miss Grey?”
She was silent for a moment, then said, “You guess that there is
something else.”
“I can see it.”
“And you are sorry?”
“Sorry, dear Eppie? Of course.”
“It’s a child, a cripple,” said Eppie. “It had been ill for a long time, but
we thought that we could save it. It died this morning. I didn’t know. I
didn’t get there in time. I only found out after leaving you this afternoon.
And it cried for me.” She had turned her head from him as it leaned against
the chair, but he saw the tears slowly rolling down her cheeks.
“I am so sorry, dear Eppie,” he said.
“The most darling child, Gavan.” His grave pity had brought him near
and it gave her relief to speak. “It had such a wistful, dear little face. I used
to spend hours with it; I never cared for any child so much. What I can’t
bear is to think that it cried for me.” Her voice broke. Without a trace, now,
of impulse or glamour, he took her hand, repeating his helpless phrase of
sympathy. Yes, he thought, while she wept, here was the fatal flaw in any
Tolstoian half-way house that promised peace. Love for others didn’t help
their suffering; suffering with them didn’t stop it. Here was the brute fact of
life that to all peace-mongers sternly said, Where there is love there is no
peace.
It was only after her hand had long lain in his fraternal clasp that she
drew it away, drying her tears and trying to smile her thanks at him.
Looking before her into the fire, and back into a retrospect of sadness, she
said: “How often you and I meet death together, Gavan. The poor monkey,
and Bobbie, and Elspeth even, ought to count.”
“You must think of me and death together,” he said.
He felt in a moment that the words had for her some significance that he
had not intended. In her silence was a shock, and in her voice, when she
spoke, a startled thing determinedly quieted.
“Not more than you must think of me and it together.”
“You and death, dear Eppie! You are its very antithesis!”
She did not look at him, and he could not see her eyes, but he knew, with
the almost uncanny intuition that he so often had in regard to her, that a
rising strength, a strength that threatened something, strove with a sudden
terror.
“Life conquers death,” she said at last.
He armed himself with lightness. “Of course, dear Eppie,” he said; “of
course it does; always and always. The poor baby dies, and—I wonder how
many other babies are being born at this moment? Conquers death? I should
think it did!”
“I did not mean in that way,” she answered. She had risen, and, looking
at the clock, seemed to show him that their time was over. “But we won’t
discuss life and death now,” she said.
“You mean that it’s late and that I must go?” he smiled.
“Perhaps I mean only that I don’t want to discuss,” she smiled back.
“Though—yes, indeed, it is late; almost seven. I have a great many things
to do this evening, so that I must rest before dinner, and let you go.”
“I may come again?”
“Whenever you will. Thank you for being so kind to-day.”
“Kind, dear Eppie?”
“For being sorry, I mean.”
“Who but a brute would not have been?”
“And you are not a brute.”
The shaded light cast soft upward shadows on her face, revealing sweet
oddities of expression. In their shadow he could not fathom her eyes; but a
tenderness, peaceful, benignant, even a recovered gaiety, hovered on her
brow, her upper lip, her cheeks. It was like a reflection of sunlight in a deep
pool, this dim smiling of gratitude and gaiety.
He had a queer feeling, and a profounder one than in their former
moment when she had repudiated his helpless emotion, that she spared him,
that she restrained some force that might break upon this fraternal nearness.
For an instant he wondered if he wanted to be spared, and with the wonder
was once more the wrench at leaving her there, alone, in her fire-lit room.
But it was her strength that carried them over all these dubious
undercurrents, and he so relied on it that, holding her hand in good-by, he
said, “I will come soon. I like it here.”
“And you are coming to Kirklands this summer. Uncle expects it. You
mustn’t disappoint him, and me. I shall be there for a month.”
“I’ll come.”
“Jim Grainger will be there, too. You remember Jim. You can fight with
him from morning till night, but you and I will fight about nothing,
absolutely nothing, Gavan. We will—glisser. We will talk about Goya! We
will be perfectly comfortable.”
He really believed that they might be, so happily convincing was her
tone.
“Grainger is a great chum of yours, isn’t he?” he asked.
“You remember, he and his brother were old playmates; Clarence has
turned out a poor creature; he’s a nobody in the church. I’m very fond of
Jim. And I admire him tremendously. He is the conquering type, you know
—the type that tries for the high grapes.”
“You won’t set him at me, to mangle me for your recreation?”
“Do I seem such a pitiless person?”
“Oh, it would be for my good, of course.”
“You may come with no fear of manglings. You sha’n’t be worried or
reformed.”
They had spoken as if the captain were non-existent, but Gavan put the
only qualifying touch to his assurance of seeing her at Kirklands. “I’ll come
—if I can get there by then.”

XII
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