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MATERIALS
KINETICS
Transport and Rate Phenomena
This book belongs to Alice Cartes
(throwawayforali@gmail.com)
Copyright Elsevier 2023

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This book belongs to Alice Cartes (throwawayforali@gmail.com) Copyright Elsevier 2023

MATERIALS
KINETICS
Transport and Rate Phenomena
JOHN C. MAURO
The Pennsylvania State University
University Park, Pennsylvania

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About the Cover Art: “Moments in Love: Mean, Variance, Skew, Kurtosis”
Jane Cook, 2018 Corning, New York
Acrylic and tissue paper on canvas, 61 cm x 45 cm
The title of this painted collage is a word-play on the title of the song “Moments in Love” by the
1980s new wave band Art of Noise. The canvas is painted red and overlaid with crinkled red
tissue, over which four roughly rectangular forms are positioned essentially squared with each
other and the canvas. The piece is the artist’s nerdy commentary on the utility and futility of
analysis in matters of the heart. One might find joy amongst the scattered, undulating hills and
valleys of the underlying “function” of love without knowing more details of that function; or,
one can deploy a knowledge of statistics to extract the moments of the distribution of highs and
lows. Neither method of experience is superior e they each provide unique insights.
Publisher: Matthew Deans
Acquisitions Editor: Dennis McGonagle
Editorial Project Manager: Chiara Giglio
Production Project Manager: Nirmala Arumugam
Cover Designer: Miles Hitchen
Typeset by TNQ Technologies

Dedicated to my loving wife and daughter,
Yihong and Sofia Mauro


Contents
Foreword xvii
Preface xxi
Acknowledgments xxv
1. Thermodynamics vs. Kinetics 1

1.1. What is Equilibrium? 1
1.2. Thermodynamics vs. Kinetics 3
1.3. Spontaneous and Non-Spontaneous Processes 6
1.4. Microscopic Basis of Entropy 8
1.5. First Law of Thermodynamics 11
1.6. Second Law of Thermodynamics 12
1.7. Third Law of Thermodynamics 13
1.8. Zeroth Law of Thermodynamics 15
1.9. Summary 15
Exercises 16
References 17
2. Irreversible Thermodynamics 19
2.1. Reversible and Irreversible Processes 19
2.2. Affinity 22
2.3. Fluxes 24
2.4. Entropy Production 26
2.5. Purely Resistive Systems 26
2.6. Linear Systems 27
2.7. Onsager Reciprosity Theorem 28
2.8. Thermophoresis 29
2.9. Thermoelectric Materials 31
2.10. Electromigration 33
2.11. Piezoelectric Materials 34
2.12. Summary 35
Exercises 36
References 38
3. Fick’s Laws of Diffusion 39

3.1. Fick’s First Law 39
3.2. Fick’s Second Law 41
3.3. Driving Forces for Diffusion 45
vii

viii Contents
3.4. Temperature Dependence of Diffusion 46

3.5. Interdiffusion 49
3.6. Measuring Concentration Profiles 52
3.7. Tracer Diffusion 53
3.8. Summary 55
Exercises 56
References 58
4. Analytical Solutions of the Diffusion Equation 59

4.1. Fick’s Second Law with Constant Diffusivity 59
4.2. Plane Source in One Dimension 60
4.3. Method of Reflection and Superposition 62
4.4. Solution for an Extended Source 63
4.5. Bounded Initial Distribution 67
4.6. Method of Separation of Variables 68
4.7. Method of Laplace Transforms 71
4.8. Anisotropic Diffusion 75
4.9. Concentration-Dependent Diffusivity 77
4.10. Time-Dependent Diffusivity 78
4.11. Diffusion in Other Coordinate Systems 79
4.12. Summary 80
Exercises 81
References 84
5. Multicomponent Diffusion 85
5.1. Introduction 85
5.2. Matrix Formulation of Diffusion in a Ternary System 87
5.3. Solution by Matrix Diagonalization 88
5.4. Uphill Diffusion 93
5.5. Summary 96
Exercises 97
References 98
6. Numerical Solutions of the Diffusion Equation 99

6.2. Dimensionless Variables 100
6.3. Physical Interpretation of the Finite Difference Method 101
6.4. Finite Difference Solutions 103
6.5. Considerations for Numerical Solutions 106
6.6. Summary 107

Contents ix
Exercises 107
References 108
7. Atomic Models for Diffusion 109

7.2. Thermally Activated Atomic Jumping 110
7.3. Square Well Potential 112
7.4. Parabolic Well Potential 116
7.5. Particle Escape Probability 117
7.6. Mean Squared Displacement of Particles 118
7.7. Einstein Diffusion Equation 120
7.8. Moments of a Function 121
7.9. Diffusion and Random Walks 123
7.10. Summary 125
Exercises 126
References 127
8. Diffusion in Crystals 129

8.1. Atomic Mechanisms for Diffusion 129
8.2. Diffusion in Metals 131
8.3. Correlated Walks 134
8.4. Defects in Ionic Crystals 135
8.5. Schottky and Frenkel Defects 137
8.6. Equilibrium Constants for Defect Reactions 139
8.7. Diffusion in Ionic Crystals 141
8.8. Summary 144
Exercises 145
References 146
9. Diffusion in Polycrystalline Materials 147

9.1. Defects in Polycrystalline Materials 147
9.2. Diffusion Mechanisms in Polycrystalline Materials 148
9.3. Regimes of Grain Boundary Diffusion 150
9.4. Diffusion Along Stationary vs. Moving
Grain Boundaries 153
9.5. Atomic Mechanisms of Fast Grain Boundary Diffusion 156
9.6. Diffusion Along Dislocations 157
9.7. Diffusion Along Free Surfaces 157
9.8. Summary 158
Exercises 159
References 160

x Contents
10. Motion of Dislocations and Interfaces 161

10.1. Driving Forces for Dislocation Motion 161
10.2. Dislocation Glide and Climb 165
10.3. Driving Forces for Interfacial Motion 168
10.4. Motion of Crystal-Vapor Interfaces 169
10.5. Crystalline Interface Motion 173
10.6. Summary 174
Exercises 174
References 175
11. Morphological Evolution in Polycrystalline Materials 177

11.1. Driving Forces for Surface Morphological Evolution 177
11.2. Morphological Evolution of Isotropic Surfaces 178
11.3. Evolution of Anisotropic Surfaces 181
11.4. Particle Coarsening 182
11.5. Grain Growth 184
11.6. Diffusional Creep 189
11.7. Sintering 190
11.8. Summary 195
Exercises 196
References 197
12. Diffusion in Polymers and Glasses 199

12.2. Stokes-Einstein Relation 200
12.3. Freely Jointed Chain Model of Polymers 201
12.4. Reptation 202
12.5. Chemically Strengthened Glass by Ion Exchange 203
12.6. Ion-Exchanged Glass Waveguides 211
12.7. Anti-Microbial Glass 211
12.8. Proton Conducting Glasses 212
12.9. Summary 213
Exercises 213
References 215
13. Kinetics of Phase Separation 217

13.1. Thermodynamics of Mixing 217
13.2. Immiscibility and Spinodal Domes 222
13.3. Phase Separation Kinetics 224
13.4. Cahn-Hilliard Equation 226

Contents xi
13.5. Phase-Field Modeling 229

13.6. Summary 230
Exercises 232
References 232
14. Nucleation and Crystallization 235

14.1. Kinetics of Crystallization 235
14.2. Classical Nucleation Theory 235
14.3. Homogeneous Nucleation 236
14.4. Heterogeneous Nucleation 238
14.5. Nucleation Rate 241
14.6. Crystal Growth Rate 242
14.7. Johnson-Mehl-Avrami Equation 244
14.8. Time-Temperature-Transformation Diagram 246
14.9. Glass-Ceramics 248
14.10. Summary 251
Exercises 251
References 252
15. Advanced Nucleation Theories 255

15.1. Limitations of Classical Nucleation Theory 255
15.2. Statistical Mechanics of Nucleation 257
15.3. Diffuse Interface Theory 259
15.4. Density Functional Theory 260
15.5. Implicit Glass Model 263
15.6. Summary 264
Exercises 266
References 267
16. Viscosity of Liquids 269

16.2. Viscosity Reference Points 270
16.3. Viscosity Measurement Techniques 271
16.4. Liquid Fragility 272
16.5. Vogel-Fulcher-Tammann (VFT) Equation for Viscosity 274
16.6. Avramov-Milchev (AM) Equation for Viscosity 275
16.7. Adam-Gibbs Entropy Model 276
16.8. Mauro-Yue-Ellison-Gupta-Allan (MYEGA) Equation for Viscosity 279
16.9. Infinite Temperature Limit of Viscosity 284
16.10. Kauzmann Paradox 286

xii Contents
16.11. Fragile-to-Strong Transition 287

16.12. Non-Newtonian Viscosity 288
16.13. Volume Viscosity 290
16.14. Summary 291
Exercises 291
References 294
17. Nonequilibrium Viscosity and the Glass Transition 295

17.2. The Glass Transition 295
17.3. Thermal History Dependence of Viscosity 299
17.4. Modeling of Nonequilibrium Viscosity 301
17.5. Nonequilibrium Viscosity and Fragility 304
17.6. Composition Dependence of Viscosity 306
17.7. Viscosity of Medieval Cathedral Glass 309
17.8. Summary 312
Exercises 313
References 313
18. Energy Landscapes 315

18.1. Potential Energy Landscapes 315
18.2. Enthalpy Landscapes 319
18.3. Landscape Kinetics 322
18.4. Disconnectivity Graphs 324
18.5. Locating Inherent Structures and Transition Points 327
18.6. ExplorerPy 336
18.7. Summary 338
Exercises 339
References 339
19. Broken Ergodicity 341

19.1. What is Ergodicity? 341
19.2. Deborah Number 343
19.3. Broken Ergodicity 346
19.4. Continuously Broken Ergodicity 351
19.5. Hierarchical Master Equation Approach 355
19.6. Thermodynamic Implications of Broken Ergodicity 357
19.7. Summary 360
Exercises 361
References 361

Contents xiii
20. Master Equations 363

20.1. Transition State Theory 363
20.2. Master Equations 365
20.3. Degenerate Microstates 368
20.4. Metabasin Approach 370
20.5. Partitioning of the Landscape 375
20.6. Accessing Long Time Scales 383
20.7. KineticPy 385
20.8. Summary 386
Exercises 386
References 387
21. Relaxation of Glasses and Polymers 389

21.2. Fictive Temperature 390
21.3. Tool’s Equation 390
21.4. Ritland Crossover Effect 392
21.5. Fictive Temperature Distributions 392
21.6. Property Dependence of Fictive Temperature 396
21.7. Kinetic Interpretation of Fictive Temperature 396
21.8. Stretched Exponential Relaxation 397
21.9. Prony Series Description 399
21.10. Relaxation Kinetics 404
21.11. RelaxPy 406
21.12. Stress vs. Structural Relaxation 406
21.13. Maxwell Relation 411
21.14. Secondary Relaxation 413
21.15. Summary 415
Exercises 416
References 417
22. Molecular Dynamics 419

22.1. Multiscale Materials Modeling 419
22.2. Quantum Mechanical Techniques 420
22.3. Principles of Molecular Dynamics 422
22.4. Interatomic Potentials 424
22.5. Ensembles 426
22.6. Integrating the Equations of Motion 426
22.7. Performing Molecular Dynamics Simulations 430

xiv Contents
22.8. Thermostats 433

22.9. Barostats 434
22.10. Reactive Force Fields 434
22.11. Tools of the Trade 438
22.12. Summary 439
Exercises 440
References 441
23. Monte Carlo Techniques 443

23.2. Monte Carlo Integration 444
23.3. Monte Carlo in Statistical Mechanics 446
23.4. Markov Processes 447
23.5. The Metropolis Method 448
23.6. Molecular Dynamics vs. Monte Carlo 450
23.7. Sampling in Different Ensembles 451
23.8. Kinetic Monte Carlo 452
23.9. Inherent Structure Density of States 457
23.10. Random Number Generators 460
23.11. Summary 463
Exercises 464
References 465
24. Fluctuations in Condensed Matter 467

24.1. What are Fluctuations? 467
24.2. Statistical Mechanics of Fluctuations 468
24.3. Fluctuations in Broken Ergodic Systems 470
24.4. Time Correlation Functions 474
24.5. Dynamical Heterogeneities 476
24.6. Nonmonotonic Relaxation of Fluctuations 477
24.7. Industrial Example: Fluctuations in High Performance
Display Glass 480
24.8. Summary 482
Exercises 485
References 485
25. Chemical Reaction Kinetics 487

25.1. Rate of Reactions 487
25.2. Order of Reactions 489
25.3. Equilibrium Constants 490

Contents xv
25.4. First-Order Reactions 491

25.5. Higher Order Reactions 493
25.6. Reactions in Series 494
25.7. Temperature Dependence of Reaction Rates 495
25.8. Heterogeneous Reactions 496
25.9. Solid State Transformation Kinetics 496
25.10. Summary 498
Exercises 499
References 500
26. Thermal and Electrical Conductivities 501

26.1. Transport Equations 501
26.2. Thermal Conductivity 502
26.3. Electrical Conductivity 504
26.4. Varistors and Thermistors 506
26.5. Summary 509
Exercises 510
References 511
Index 513


Foreword
Tis true without lying, certain & most true.
That which is below is like that which is above & that which
is above is like that which is below to do the miracles of one
only thing
And as all things have been & arose from one by the
mediation of one: so all things have their birth from this
one thing by adaptation.
Sir Isaac Newton, excerpt from “The Emerald Tablet”
The original author of “The Emerald Tablet,” a seminal work of

alchemical thinking, was a now-unknown 6th-8th Century Arabic mystic.
A millennium later, Newton made his translation from version in Latin,
with the first key lines given above.
Although the phrase “As above, so below” is now popularized in
contemporary metaphysical lore, I think it likely that Newton could sense,
if not know, that a deeper truth of Nature was at the core of this concept.
But it would be 300 years before Albert Einstein, another genius who
could see beyond the common dimensional and mathematical restrictions
of his time, would unite the “above” and “below” in his diffusion equation
that connected the microscopic motion of individual atoms to the
macroscopic flow of large systems.
And that “one thing,” from which this scale-bridging understanding
arises, is what floats now before your eyes: Materials Kinetics.
In the song “Heaven” by the Talking Heads, David Byrne croons:
Heaven
Heaven is a place
A place where nothing ever happens.
This view of a heavenly state is a state of thermodynamic equilibrium.

There are no reservoirs of potential energy to dissipate. No chemical
reactions to go forward; no elevated weights on pulleys waiting to do work;
no electrons waiting to discharge from capacitive plates. It would seem an
engineering student’s Heaven.
xvii

xviii Foreword
But reality is the here-and-now. And stuff is happening! And if it’s not
happening, it’s probably trying to. Things ARE kinetics!
We live life in a universe in motion. We, and all around us, are verbs, as
Buckminster Fuller pointed out: “.integral functions of Universe.” We
are motivated fundamentally by the possibilities of change.
Thermodynamics tells us what can be, what is favored, what is desired.
But it is Kinetics that tells us how it can happen, what it’ll take, the
ultimate, integrated “pain vs. gain.”
It is the traffic report for the freeways of materials science.
I grew up in the 1970s in the suburbs north of Los Angeles, a city
famous for its Car Culture. A sprawling megalopolis, LA offered 16 year-
old Me uncountable worlds to explore. But along with mastering the
critical skills of safe vehicle operation, I needed to know the freeways,
highways, boulevards, side streets – and even the alleyways – to get to
places safely, timely, and with low-stress. I had a paper map in my bedroom
that I would study before heading out, and another in the glovebox. But
maps were never enough. I also needed the radio’s traffic reports – the real-
time data – so I’d know, for example, that the southbound I-405 over the
pass was backed up to Victory Boulevard due to a vehicle fire, and so it
would, surprisingly, be faster to take I-5 through downtown to I-10 to get
to the beach.
Thermodynamics told me I wanted to get to the beach, that there I’d be
chill and at deep local equilibrium; my “heaven” was a spot of sand just north
of Pepperdine University in Malibu. Kinetic pathways of maps and traffic
reports provided the options for roads to take. It was the complex interplay
of those two, moment to moment on that journey that defined the actual
lowest energy pathway that my car should take: Reality is our thermo-
dynamic motivations playing out on the diamond lanes, stoplights,
fender-benders, and alleyway shortcuts of serial/parallel kinetic mechanisms.
This textbook unites the elegant potentialities of thermodynamics with
the real universe of shifting chemical activity gradients, thermal transients,
alternating electromagnetic fields, and deviatoric stresses. Materials Kinetics
shows how “one thing by adaptation” from Newton’s alchemical picture
manifests the Einsteinian “miracle of the one thing,” the astonishing myriad
subtlety of the physical universe.
Jane B. Cook
The Pennsylvania State University, University Park, PA,
United States of America

Foreword xix
Notes:
http://webapp1.dlib.indiana.edu/newton/mss/norm/ALCH00017.
“Heaven” lyrics by David Byrne and Jerry Harrison, on “Fear of Music”
1979, Sire Records.
“I Seem to be a Verb” by Buckminster Fuller, ISBN-13 : 978-1127231539.


Preface
Kinetic processes are the agents of change in materials science and

engineering. Despite the ubiquitous importance of kinetics in materials
science, a comprehensive textbook on this topic has been sorely lacking. I
hope the current volume will fill this gap, providing a textbook that covers
the full breadth of materials kinetics, spanning all classes of materials and
covering both the liquid and solid states from the macroscale down to the
atomic level. In writing this book, I have attempted to strike a balance
among fundamental theory, modeling and simulation techniques,
experimental methods, and practical applications in materials design.
The book is written in a pedagogical fashion, aiming to provide a rigorous
treatment of materials kinetics in a format that is accessible to both first-year
graduate students and upper-level undergraduates in materials science and
engineering. It should also be useful as a reference for professionals in the field.
Emphasis has been placed on developing the fundamental concepts of
materials kinetics and the importance of these concepts in the understanding
and design of materials. Real-world examples are given throughout the text,
and each chapter ends with a series of exercises that are meant to stimulate
critical and creative thinking around relevant concepts.
This volume emerged from teaching MATSE 503, “Kinetics of
Materials Processes,” my first-year graduate course at Penn State. The
organization of the book follows exactly how I teach the course. I am
happy to provide additional course contentdincluding lecture slidesdto
any instructors who ask. Please feel free to email me at jcm426@psu.edu to
request a copy of this material.
The book begins with an overview of important thermodynamic
concepts and the difference between thermodynamics and kinetics
(Chapter 1). Thermodynamics is an elegant subject, but one that is often
difficult to grasp for many students. I hope the overview provided in
Chapter 1 will help students develop an intuitive understanding of some
key thermodynamic concepts which are vital to materials science and
engineering. One of my goals with this book is to provide a seamless
connection between the thermodynamics and kinetics of materials. With
respect to transport and rate phenomena, thermodynamics can often be
viewed as the “cause” while kinetics is the “effect.”
xxi

xxii Preface
With this foundation in place, we introduce the subject of irreversible

thermodynamics (Chapter 2), which provides the thermodynamic driving
force for kinetic processes. Aside from the excellent chapter in Callen’s
classic thermodynamics textbook, there is almost no good overview of
irreversible thermodynamics in the literature that is both physically rigorous
and clearly accessible to introductory readers. Such was my goal with
Chapter 2, which took me more time to write than any other chapter in
this book. I hope the reader will find this to be a lucid and useful intro-
duction to Onsager’s formulation of irreversible thermodynamics, as well as
its practical importance in materials science.
In Chapter 3, we introduce Fick’s laws of diffusion. Chapter 4 is devoted
to analytical solutions of the diffusion equation. Here, I have tried to select an
assortment of solutions that I have seen most commonly used in practical
problems. Next, in Chapter 5 we consider multicomponent diffusion, a
problem first rigorously addressed by my advisor (Arun Varshneya) during his
Ph.D. studies at Case Western Reserve University. Of course, many diffusion
problems are too difficult to be solved analytically. Chapter 6 is, therefore,
devoted to numerical solutions of the diffusion equation using the finite
difference method.
While Chapters 1e6 deal with macroscopic thermodynamics and
kinetics, in Chapter 7 we dive into the microscopic description of diffusion
in terms of atomic jumping. The connection between the microscopic and
macroscopic descriptions of diffusion is made via the Einstein diffusion
equation. Then in Chapter 8 we specifically deal with atomic jumping and
diffusion in single crystals, starting first with perfect crystals and then
moving to those having point defects. In Chapter 9 we cover diffusion in
polycrystalline materials, accounting for the impact of grain boundaries and
free surfaces. Chapter 10 then deals with the kinetics of dislocation and
interfacial motion. Chapter 11 concludes our treatment of polycrystalline
materials by studying various types of morphological evolution, including
particle coarsening, grain growth, diffusional creep, and sintering. In
Chapter 12, we turn our attention to diffusion in polymers and glasses,
including reptation and ion exchange processes.
Next, in Chapter 13 we cover the thermodynamics and kinetics of
phase separation, including droplet nucleation and spinodal decomposition.
Chapters 14 and 15 are devoted to crystal nucleation and growth. Chapter
14 presents classical nucleation theory, while Chapter 15 covers several
types of advanced nucleation theories.
In Chapter 16 we turn our attention to liquid viscosity, including
fundamental theory, experimental measurement techniques, and models

Preface xxiii
describing the viscosity-temperature relationship. This naturally leads to the

topics of nonequilibrium viscosity and the glass transition in Chapter 17.
The glass transition is a particularly interesting topic since it is intrinsically a
kinetic transition, and one with profound thermodynamic consequences,
i.e., kinetics is the “cause” and thermodynamics is the “effect”!
Chapter 18 introduces the notion of an energy landscape, which is one
of the most powerful and versatile ways of describing both the thermo-
dynamics and kinetics of materials. In Chapter 19, we cover the vitally
importantdbut usually overlookeddtopic of broken ergodicity, which is
of critical importance for nonequilibrium systems displaying long relaxation
times. The kinetics of broken ergodic systems can be rigorously calculated
in terms of master equations, which are detailed in Chapter 20. Next,
Chapter 21 applies this knowledge to the study of long-time relaxation in
glasses and polymers. This chapter includes detailed coverage of fictive
temperature and the stretched exponential relaxation function.
The next pair of chapters focuses on useful computer simulation tech-
niques for modeling kinetic phenomena at the atomic level. Chapter 22
covers the fundamentals of molecular dynamics, and Chapter 23 is devoted
to Monte Carlo techniques, including the kinetic Monte Carlo approach
for accessing long time scales.
In Chapter 24, we discuss fluctuations in condensed matter. Atomic
scale fluctuations in time and space are critically important across all of
materials science and engineering. However, this topic is rarely given much
attention in standard materials science curricula. With Chapter 24, I hope to
bring more attention to this important topic.
Chapter 25 provides an introduction to chemical reaction kinetics, i.e.,
kinetics from the perspective of chemistry and chemical engineering.
Finally, we conclude the book with a brief chapter on thermal and electrical
conductivities (Chapter 26), topics that are already part of the standard
curriculum in solid state physics courses. More in-depth treatment is left for
solid state physics textbooks (see either of the canonical texts by Kittel or by
Ashcroft and Mermin).
Whether you are an experimentalist or theorist, a metallurgist, ceramist,
glass scientist, or polymer scientist, I hope there is something of interest here
for you, and I hope that you will enjoy reading this book as much as I have
enjoyed writing it!
John C. Mauro


Acknowledgments
I am blessed with an amazing group of students here at Penn State, whose

passion for materials research and making the world a better place is a daily
inspiration to me. I would like to thank all my students for making my role as
a professor such a fulfilling experience. With respect to the current volume, I
would especially like to thank the following Penn State students who
provided figures from their research to help elucidate various concepts
throughout this book: Sun Hwi Bang, Nicholas Clark, Anthony DeCeanne,
George Kotsonis, Rebecca Welch, Collin Wilkinson, and Yongjian Yang. I
would also like to thank all the students in my MATSE 503 “Kinetics of
Materials Processes” class for all their great questions and enthusiasm for
learning. I would especially like to thank my teaching assistant, Karan Doss,
who is a wellspring of great ideas and insights. Discussions with Karan have
improved both the course itself and the content of this textbook. I would
also like to thank Matthew Mancini and Daniel Cassar for their helpful
suggestions on this book. I owe an ocean of thanks to Brittney Hauke, who
designed 37 of the figures in this book. I really appreciate Brittney’s ability to
clearly capture key concepts in her illustrations, which will be greatly helpful
to students learning the course content for the first time. Brittney has also
been amazingly generous with her time, providing careful word-by-word
proofreading of most of this book. Thank you, Brittney!
Thanks also to my colleagues at Penn State for all of their support and
encouragement. In particular, Venkat Gopalan has been a huge source of
encouragement throughout the writing of this book. Sorry for clogging
your email with so many chapter files! I’d also like to thank Susan Sinnott,
Long-Qing Chen, Jon-Paul Maria, and Clive Randall for their ongoing
support and for sharing some of their exciting new research for inclusion as
part of this volume. I also owe a huge thanks to Carlo Pantano, Seong Kim,
and John Hellmann for their amazing support of both me personally and
my research group at Penn State.
I am deeply thankful to Jane Cook for all of her encouragement,
inspiration, and friendship over so many years, first at Corning Incorporated
and now here at Penn State. It is difficult to express how deeply meaningful
it is to me that she would write the Foreword for this book and also offer
her beautiful artwork, “Moments in Love,” both as the cover for this book
and as one of the figures in Chapter 7. Jane’s work at the intersection of art
and science is profoundly inspirational to me, as I know it is to our students.
xxv

xxvi Acknowledgments
I am also very fortunate to have a wonderful network of friends and

collaborators from around the globe. I appreciate all the good times working
together to address our latest research challenges. In the context of the
current book, I would like to extend special thanks to Roger Loucks (Alfred
University); Morten Smedskjaer (Aalborg University, Denmark); Edgar
Zanotto (Federal University of São Carlos, Brazil); Doug Allan, Adam
Ellison, Ozgur Gulbiten, and Matt McKenzie (Corning Incorporated); Ken
Kelton (Washington University in St. Louis); and Prabhat Gupta (The Ohio
State University). Prabhat, in particular, has been like a second advisor to me.
We worked very closely together in developing many of the models and
techniques described in this book, including the MYEGA equation for liquid
viscosity, temperature-dependent constraint theory, the statistical mechanics
of continuously broken ergodicity, and a general technique for solving large
sets of master equations over disparate time scales.
I would also like to express my deepest gratitude to my advisor, Arun
Varshneya from Alfred University, who is both my “glass guru” and my
academic father. I owe so much to him, for everything he has taught me
directly and for all the doors of opportunity he has opened for me. Arun has
taught me that being an academic advisor is a lifelong commitment. He is
the role model whom I am striving to follow, in his engaging teaching style,
his outstanding research at the interface of science and engineering, and
(most importantly) in his deep commitment to his students.
I would also like to thank my family for their unfailing love and support.
From birth to the present day, my parents, Ron and Susie Mauro, have
always been such wonderful role models for how to live my life. Finally,
the biggest thanks of all goes to my wife, Yihong, and our daughter, Sofia,
for their unbounded love and support, especially during the countless hours
I’ve spent writing this book. I struggle to find the words to express the
depth of my love and gratitude for you.
John C. Mauro

CHAPTER 1
Thermodynamics vs. Kinetics
1.1 What is Equilibrium?

The field of classical thermodynamics is primarily concerned with equi-
librium states, i.e., the states to which systems will eventually evolve and
become stable. Although the concept of equilibrium is seemingly intuitive,
this simplicity can be deceptive. Perhaps the most insightful definition of
equilibrium is given by Richard Feynman [1], who said that equilibrium is
“when all the fast things have happened but the slow things have not.”
“Surely you’re joking, Mr. Feynman!” we may be tempted to reply.
While Feynman’s definition may seem somewhat flippant at first, it inci-
sively captures the importance of time scale in determining what constitutes
equilibrium.
Perhaps we should rephrase our response to Mr. Feynman. If equilib-
rium is “when all the fast things have happened but the slow things have
not,” this begs the questions, “What is fast?” and “What is slow?” Indeed,
“fast” and “slow” are intrinsically relative terms and depend on your
perspective as an observer [2].
Maybe some caffeine will help accelerate our understanding of the
relative nature of equilibrium. Let us consider the simple example of a
mixture of coffee and cream in a mug, depicted in Figure 1.1. Initially the
coffee and the cream are two separate phases. When the cream is poured
into the coffee, the mixture homogenizes on a time scale of several seconds.
Hence, the coffee-cream mixture achieves an equilibrium within the mug
on a fairly short time scale. This would be an appropriate time to take a sip,
because if we wait longer, the hot coffee-cream mixture will cool and reach
thermal equilibrium with the room temperature environment. This second
equilibrium occurs on a longer time scale, e.g., on the order of tens of
minutes. Now let us extend the time scale again, this time to several days.
On this much longer time scale, the thermally equilibrated coffee-cream
mixture will reach a vapor equilibrium with the atmosphere, and our
thirsty reader will be left with only some residue of what was formerly
coffee in the bottom of the mug.
Materials Kinetics
ISBN 978-0-12-823907-0 © 2021 Elsevier Inc.
https://doi.org/10.1016/B978-0-12-823907-0.00002-9 All rights reserved. 1

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on which those citizens have granted power to that legislature to
command them.
That we may intelligently so insist, and that our insistence may be
made in the proper place and at the proper time, let us briefly
consider on what subjects, in the making of our Constitution, our
predecessors, as American citizens, granted their enumerated
national powers to our only government of all Americans. Like those
predecessors, assembled in their conventions, we find all those
enumerated powers in the First Article of the Constitution proposed
from Philadelphia.
In substance they are the war power; the power of making treaties;
the power of regulating commerce between ourselves and all people
outside of America and between the citizens of the different states;
the power of taxation; and all other incidental and supplementary
powers necessary to make laws in the execution of these
enumerated and granted powers.
Noticeably absent from these enumerated powers granted to the
only general government of the citizens of America is that power,
then existing and still in the national government of each nation or
state, known (rather inaccurately) as the police power or the power
to pass any law, in restraint of individual human freedom, reasonably
designed, in the judgment of that particular legislature, to promote
the general welfare of its own citizens. It seems hardly necessary, at
this moment, to refer to the innumerable decisions of the Supreme
Court that such power was not among those enumerated and
granted to the American government by its citizens. It was solely
because such power had definitely not been granted by them to it
that the government of the American citizens made its famous
proposal that a portion of such power, in relation to one subject, be
granted to it in the supposed Eighteenth Amendment of our
Constitution.
As a matter of fact, the police power of any government is really all
its power to pass any laws which interfere with the exercise of
individual freedom. In that respect, the American people made a
marked distinction between the quantum of that kind of power which
they granted to their one general national government and the
quantum they left in the national government of the citizens of each
state. The quantum they granted to their own government was
definitely enumerated in the First Article. On the other hand, except
for the limitations which they themselves imposed upon the
respective governments of each state, they left the citizens of each
state to determine what quantum the government of that state should
have.
In other words, the police power of the American Congress is
strictly limited to the enumerated powers of that kind granted by the
citizens of America. And, although the fact does not seem to be
generally known, it is because the First Article vests in the sole
Legislature of the whole American people nothing but enumerated
powers to interfere with the freedom of the individual American that
our American government has received its universal tribute as a
government of nothing but enumerated powers over a free people,
who are its citizens.
In the Constitution are provisions in separate Articles for the
three great departments of government,—legislative,
executive, and judicial. But there is this significant difference
in the grants of powers to these departments: the First Article,
treating of legislative powers, does not make a general grant
of legislative power. It reads: “Article one, section one. All
legislative powers herein granted shall be vested in a
Congress,” etc.; and then, in Article 8, mentions and defines
the legislative powers that are granted. By reason of the fact
that there is no general grant of legislative power it has
become an accepted constitutional rule that this is a
government of enumerated powers. (Justice Brewer, in the
Supreme Court, Kansas v. Colorado, 206 U. S. 46.)
Among the national powers, which are enumerated in the First
Article, there is one which (whenever operative) approximates the
extensive police power of a state government to interfere with the
freedom of its citizens. That is the war power of the Government of
America. As the purpose of the Constitution of the American
Government is to protect the freedom of the American and as such
freedom needs effective protection from foreign attack, the
Americans of that earlier generation made the war power of their
government almost as unlimited as that of a despotic government. All
history and their own human experience had taught them that the
war power, if it was to be effective for their protection, must be
practically unlimited. If we grasp this extent of the American war
power, we realize why our sole American government, without the
grant of a new national power to it, could validly enact what we know
as the War Time Prohibition Statute, although without such a new
grant, it was powerless to enact what we know as the Volstead Act
or National Prohibition for time of peace. It is because the citizens of
each state, in their Constitution of their national government, had
given to it a general (although specifically limited) ability to interfere
with their own human freedom in most matters, that each state
government could validly make prohibition laws for its own citizens. It
is because the American citizens had not given to their government
any such general ability to interfere with their freedom, that the
American Government, for any time except that of war, could not
validly enact National Prohibition for the American people without a
new grant of a new national power directly from its own citizens. In
the days of those earlier Americans, the legal necessity of deriving
such power directly from the American citizens themselves was “felt
and acknowledged by all.” In our day, among our leaders and our
“constitutional” lawyers, there was none so humble as to know or
honor this basic legal necessity.
The other enumerated national powers, which American citizens
ever gave their national government, are few in number, although
they vested a vast and necessary ability in that government to
protect the freedom of its citizens and promote their happiness and
welfare by laws in certain matters. For our present purpose, they
need only be mentioned. They require no present explanation. They
are the power to make all treaties with foreign nations or
governments; the power to regulate commerce, except the
commerce within any one particular state; and the power of taxation.
Having now some accurate conception of the limited and specific
quantum of national power which American citizens consented to
grant in those earlier days, it is pertinent to our inquiry, as to whether
we (their posterity) have again become subjects, to dwell briefly
upon the reluctance with which they made even those grants. In
considering that attitude, it is essential always to keep in mind the
status of the citizens of each state, at that time, and their relation to
their own national government and the relation of each state to the
federal government of all the states. Under the existing system of
governments, the citizens of each state were subject to no valid
interference whatever with their own individual freedom except by
laws of a legislature, every member of which they themselves
elected and to which they themselves granted every power of such
interference which that legislature could validly exercise. To those
free men in those free states, men educated in the knowledge of
what is real republican self-government, these two facts meant the
utmost security of their human rights. No government or
governments in the world, except their own one state government
could interfere at all directly with those rights, and they had given to,
and they could take from, that government any power of that kind. As
for the respective states and the relation of each to the federal
government of all, each state had an equal voice in the giving to or
taking from that government any federal power and each had an
equal voice, in the federal legislature, in exercising each valid federal
power. These existing facts, respectively of vast importance to the
citizens of each state and to its government, influenced, more than
any other facts, the framing of the new Articles, particularly the First
Article, at Philadelphia and the opposition to those Articles in the
conventions in which the people of America assembled.
The First Article, as we know it, starts with the explicit statement
that all national powers, which are granted by Americans in that
Constitution, are granted to the only American legislature, Congress.
It then provides how the members of each of the two bodies in that
legislature shall be elected. It then enumerates the granted powers,
confining them to specific subjects of interference with the human
freedom of the American citizen. It then, for the particular security of
that human freedom, imposes specific restraints upon that legislature
even in the exercise of its granted national powers. Finally, it
prohibits the further exercise of specific powers by any state
government.
No American, who reads the debates of the Philadelphia
Convention of 1787, can fail to realize that the grant of any national
power,—power to interfere with human freedom—is the constitution
of government. The First Article was the subject of almost all the
discussion of those four months at Philadelphia. Seemingly invincible
differences of desire and opinion, as to who should elect and the
proportion (for citizens of the new nation and for states of the
continuing federation) in which there should be elected the members
of the legislature which was to exercise the granted national powers,
almost ended the effort of that Convention. This was in the early part
of July. For exhausting days patriotic men had struggled to reconcile
the conflict of desire and opinion in that respect. One element,
mainly from the larger states, insisted that the members (from each
state) of both branches of the new legislature should be proportioned
to the number of Americans in that state. The other element, mainly
from the smaller states, insisted that the Americans in each state
should have an equal representation in each branch of the new
legislature. Each element was further divided as to who should
choose the members of that legislature. Some held that the people
should choose every member. Others held that the state legislatures
should choose every member. Still others held that each state
should, by its legislature, choose the members of one branch, so that
those members might speak for that state, and that the American
people themselves, divided into districts, should choose the
members of the other branch, so that those members might speak
for the general citizens of America.
Mason of Virginia, later one of the great opponents of the adoption
of all the Articles, insisted that election by the people was “the only
security for the rights of the people.” (5 Ell. Deb. 223.)
Madison “considered an election of one branch, at least of the
legislature by the people immediately, as a clear principle of free
government.” (5 Ell. Deb. 161.)
Wilson of Pennsylvania “wished for vigor in the government, but
he wished that vigorous authority to flow immediately from the
legitimate source of all authority.” (5 Ell. Deb. 160.) Later he said, “If
we are to establish a national government, that government ought to
flow from the people at large. If one branch of it should be chosen by
the legislatures, and the other by the people, the two branches will
rest on different foundations, and dissensions will naturally arise
between them.” (5 Ell. Deb. 167.)
Dickenson of Delaware “considered it essential that one branch of
the legislature should be drawn immediately from the people, and
expedient that the other should be chosen by the legislatures of the
states.” (5 Ell. Deb. 163.)
Gerry of Massachusetts, consistent Tory in his mental attitude
toward the relation of government to people, insisted that “the
commercial and moneyed interest would be more secure in the
hands of the state legislatures than of the people at large. The
former have more sense of character, and will be restrained by that
from injustice.” (5 Ell. Deb. 169.)
On June 25, Wilson, at some length, opposed the election of
senators by the state legislatures. He stated that: “He was opposed
to an election by state legislatures. In explaining his reasons, it was
necessary to observe the two-fold relation in which the people would
stand—first, as citizens of the general government; and, secondly, as
citizens of their particular state. The general government was meant
for them in the first capacity; the state governments in the second.
Both governments were derived from the people; both meant for the
people; both therefore ought to be regulated on the same
principles.... The general government is not an assemblage of
states, but of individuals, for certain political purposes. It is not meant
for the states, but for the individuals composing them; the
individuals, therefore, not the states, ought to be represented in it.”
(5 Ell. Deb. 239.)
There came a day, early in that memorable July, when all hope of
continuing the Convention was almost abandoned, by reason of the
difference of desire and opinion on this one subject. Let us average
Americans of this generation remember that this one subject was
merely the decision whether the people were to choose all the
members of the legislature which was to exercise granted national
powers to interfere with the human freedom of the citizens of
America. Happily for all of us, there were many patriotic as well as
able leaders at Philadelphia. From their patriotism and ability they
evolved the compromise, on that question, which is expressed in
their First Article. When it came from Philadelphia, it provided that
each state should have equal representation in the Senate, senators
to be chosen by the state legislatures, and that the House of
Representatives should consist of members chosen directly by the
citizens of America, in districts proportioned to the number of those
citizens in it.
No one has read the recorded debates of the Convention which
proposed and the conventions which adopted our Constitution
without learning that the Americans in those conventions knew that
the grant of enumerated national powers in the First Article was the
constitution of the American government of men. In and out of the
Philadelphia Convention, the greatest and most persistent attack
upon its proposal was the insistent claim that it had acted wholly
without authority in proposing an Article which purported to grant any
such national power to interfere with the human freedom of all
Americans. Since July 4, 1776, no legislature or legislatures in the
world had possessed any national powers over all Americans. The
Americans in each existing nation elected every member of the one
legislature which had any such power over them. It was felt and
stated at Philadelphia, it was felt and urged and insisted upon,
sometimes with decency and reason, sometimes with bitterness and
rancor and hatred, between the closing day at Philadelphia and the
assembling of various Americans in each state, that the Americans
in each state would be unwilling to give any such national power
over themselves to any legislature whose members were not all
elected by the people in that state. In all the conventions which
adopted the Constitution, the one great object of attack was the
grant even of enumerated powers of a national kind to a legislature
whose members would not all be chosen by the Americans in the
state in which the convention was held. The record of the Virginia
convention fills one entire volume of Elliot’s Debates. Almost one-
half of the pages of that volume are claimed by the eloquent attacks
of Patrick Henry upon those grants of enumerated powers in that
First Article. The basis of all his argument was the fact that this grant
of national power in the First Article would make him and all his
fellow Virginians, for the first time since the Declaration of
Independence, citizens of a nation—not Virginia—who must obey
the laws of a legislature only some of whose members Virginians
would elect.
“Suppose,” he says, “the people of Virginia should wish to alter”
this new government which governs them. “Can a majority of them
do it? No; because they are connected with other men, or, in other
words, consolidated with other states. When the people of Virginia,
at a future day, shall wish to alter their government, though they
should be unanimous in this desire, yet they may be prevented
therefrom by a despicable minority at the extremity of the United
States. The founders of your own Constitution made your
government changeable: but the power of changing it is gone from
you. Whither is it gone? It is placed in the same hands that hold the
rights of twelve other states; and those who hold those rights have
right and power to keep them. It is not the particular government of
Virginia: one of the leading features of that government is, that a
majority can alter it, when necessary for the public good. This
government is not a Virginian, but an American government.” (3 Ell.
Deb. 55.)
How forceful and effective was this objection, we average
Americans of this generation may well realize when we know that the
Constitution was ratified in Virginia by the scant majority of ten votes.
In New York and Massachusetts and other states, the adoption was
secured by similar small majorities. In North Carolina, the first
convention refused to adopt at all.
Furthermore, it is recorded history that, in Massachusetts, in
Virginia, in New York, and elsewhere, the vote of the people would
have been against the adoption of the Constitution, if a promise had
not been made to them by the advocates of the Constitution. It was
the historic promise that Congress, under the mode of procedure
prescribed in Article V, would propose new declaratory Articles,
suggested by the various conventions and specifically securing
certain reserved rights and powers of all Americans from all ability of
government to interfere therewith. This historic promise was fulfilled,
when the first Congress of the new nation proposed the suggested
declaratory Articles and ten of them were adopted. These are the
Articles now known as the first ten Amendments. It has been settled
beyond dispute, in the Supreme Court, that every one of the
declarations in these ten Articles was already in the Constitution
when it was originally adopted by the citizens of America.
The most important declaration in those amazingly important ten
declarations, which secured the adoption of our Constitution, is the
plain statement that every national power to interfere with the human
freedom of Americans, not granted in Article I, was reserved to the
American people themselves in their capacity as the citizens of
America. That is the explicit statement of what we know as the Tenth
Amendment. In itself, that statement was but the plain and accurate
echo of what was stated by the American people (who made the
enumerated grants of such powers in Article I) in the conventions
where they made those grants. Their statement was nowhere more
accurately expressed, in that respect, than in the resolution of the
Virginia Convention, which ratified the Constitution. That resolution
began, “Whereas the powers granted under the proposed
constitution are the gift of the people, and every power not
granted thereby remains with them, and at their will, etc.” (3 Ell.
Deb. 653.)
After the same statement had been expressly made (with
authoritative effect as part of the original Constitution) in that Article
which we know as the Tenth Amendment, it was again and again
echoed, in the plainest language, from the Bench of the Supreme
Court.
As far back as 1795, in the case of Vanhorne’s Lessee vs.
Dorrance, 2 Dall. 304, Justice Patterson stated that the Constitution
of England is at the mercy of Parliament, but “in America, the case is
widely different.”... A Constitution “is the form of government,
delineated by the mighty hand of the people, in which certain first
principles of fundamental laws are established. The Constitution is
certain and fixed; it contains the permanent will of the people, and is
the supreme law of the land; it is paramount to the power of the
legislature, and can be revoked or altered only by the authority that
made it. The life-giving principle and the death-dealing stroke must
proceed from the same hand.... The Constitution fixes limits to the
exercise of legislative authority, and prescribes the orbit within which
it must move.... Whatever may be the case in other countries, yet in
this there can be no doubt, that every act of the legislature,
repugnant to the Constitution, is absolutely void.”
To us average Americans, who have lived with those earlier
Americans through the days in which they constituted their nation
and distributed all granted national powers between governments in
America and reserved all other general American national powers
exclusively to themselves, the Virginia Resolution, the Tenth
Amendment, and the quoted language of the Circuit Court are in
strict conformity with the education we have received.
What, however, are we to think of the Tory education of so many of
our leaders and “constitutional” lawyers, who have calmly accepted
and acted upon the amazing assumption that state governments in
America can exercise and can grant to other governments any or all
general national powers to interfere with the human freedom of
American citizens, including even the national powers expressly
reserved by those citizens to themselves in the Tenth Amendment?
If they adopt their familiar mental attitude that all these statements
were made more than a hundred years ago and have no meaning or
weight now, we refer them to the Supreme Court, in 1907, when it
stated:
The powers the people have given to the General
Government are named in the Constitution, and all not there
named, either expressly or by implication, are reserved to the
people and can be exercised only by them, or upon
further grant from them. (Justice Brewer in Turner v.
Williams, 194, U. S. 279.)
For ourselves, we average Americans turn now to examine in
detail how clearly the Americans at Philadelphia in 1787 did know
and obey the basic law of America that all national powers to
interfere with individual freedom are the powers of the people
themselves and can be exercised only by them or upon direct grant
from them. We find their knowledge, in that respect, evidenced by an
examination of the reasoning by which they reached the correct legal
conclusion that their proposed grants of general national powers, in
their First Article, could only be made by the citizens of America
themselves, assembled in their “conventions”—that grants of such
powers could not be made even by all the legislatures of the then
independent states.
CHAPTER VII
PEOPLE OR GOVERNMENT?—CONVENTIONS
OR LEGISLATURES?
It is no longer open to question that by the Constitution a

nation was brought into being, and that that instrument was
not merely operative to establish a closer union or league of
states. (Justice Brewer, in Supreme Court, Kansas v.
Colorado, 206 U. S. 46 at page 80.)
Instructed by living through the education of the earlier Americans
to their making of that Constitution, we accurately know that they
themselves, by their own direct action, brought that new nation into
being. Through our course in their education, we have their
knowledge that only the men, who are to be its first members, can
create a new political society of men, which is exactly what any
American nation is. “Individuals entering into society must give up a
share of liberty to preserve the rest.” So said the letter which went
from Philadelphia with the proposed Articles whose later adoption
created the new nation and vested the delegated and enumerated
national powers of its government to interfere with the liberty of its
citizens, (1 Ell. Deb. 17.)
Furthermore, through our own personal experience, we
understand how all societies of men are brought into being. There
are few of us who have not participated in the creation of at least one
society of men. Most of us have personally participated in the
creation of many such societies. For which reason, we are quite well
acquainted with the manner in which all societies of men are brought
into being. We know that ourselves, the prospective members of the
proposed society, assemble and organize it and become its first
members and constitute the powers of its government to command
us, its members, for the achievement of the purpose for which we
create it.
For one simple reason, the Americans, through whose education
we have just lived, were “better acquainted with the science of
government than any other people in the world.” That reason was
their accurate knowledge that a free nation, like any other society of
individuals, can be created only in the same manner and by its
prospective members and that the gift of any national powers to its
government can only be by direct grant from its human members.
This is the surrender “of a share of their liberty, to preserve the rest.”
The knowledge of those Americans is now our knowledge. For
which reason, we know that they themselves created that new nation
and immediately became its citizens and, as such, gave to its
government all the valid and enumerated national powers of that
government to interfere with their and our human freedom. We know
that they did all these things, by their own direct action, “in the only
manner, in which they can act safely, effectively or wisely, on such a
subject, by assembling in conventions.”
Thus, whatever may have been the lack of knowledge on the part
of our leaders and “constitutional” lawyers for the last five years, we
ourselves know, with knowledge that is a certainty, that the ratifying
conventions of 1787 and 1788 were the American people
themselves or the citizens of the new nation, America, assembled in
their respective states.
Our Supreme Court has always had the same knowledge and
acted upon it.
The Constitution of the United States was ordained and
established, not by the states in their sovereign capacities
[the respective peoples or citizens of each State] but
emphatically, as the preamble of the Constitution declares, by
“the people of the United States” [namely the one people of
America].... It was competent to the people to invest the
general government with all the powers which they might
deem proper and necessary; to extend or restrain these
powers according to their own good pleasure, and to give
them a paramount and supreme authority.... The people had a
right to prohibit to the states the exercise of any powers which
were, in their judgment, incompatible with the objects of the
general compact [between the citizens or members of the
new nation], to make the powers of the state governments, in
given cases, subordinate to those of the nation, or to reserve
to themselves those sovereign authorities which they might
not choose to delegate to either. (Supreme Court, Martin v.
Hunter’s Lessee, 1 Wheat. 304, at p. 324.)
Instructed by experience, the American people, in the
conventions of their respective states, adopted the present
Constitution.... The people made the Constitution and the
people can unmake it. It is the creature of their will, and lives
only by their will. But this supreme and irresistible power to
make or to unmake resides only in the whole body of the
people, not in any subdivisions of them. (Marshall, in
Supreme Court, Cohens v. Virginia, 6 Wheat. 264.)
The Constitution was ordained and established by the
people of the United States for themselves, for their own
government, and not for the government of the individual
states. Each state established a constitution for itself, and in
that constitution provided such limitations and restrictions on
the powers of its particular government as its judgment
dictated. The people of the United States framed such a
government for the United States as they supposed best
adapted to their situation, and best calculated to promote their
interests. The powers they conferred on this government were
to be exercised by itself; and the limitations on power, if
expressed in general terms, are naturally, and, we think,
necessarily, applicable to the government created by the
instrument. They are limitations of power granted in the
instrument itself; not of distinct governments, framed by
different persons and for different purposes. (Marshall, in
Supreme Court, Barron v. Mayor of Baltimore, 7 Peters, 243.)
When the American people created a national legislature,
with certain enumerated powers, it was neither necessary nor
proper to define the powers retained by the states. These
powers proceed, not from the people of America, but from the
people of the several states; and remain, after the adoption of
the Constitution, what they were before, except so far as they
may be abridged by that instrument. (Marshall, in the
Supreme Court, Sturges v. Crowninshield, 4 Wheat. 122.)
We average Americans know and will remember the clear
distinction, the substantial distinction, recognized by the great jurist,
between “the people of America” and “the people of the several
states,” although they happen to be the same human beings acting
in different capacities, as members of different political societies of
men. It is a matter of constant mention in the Supreme Court that we
ourselves, in addition to our capacity as human beings, have two
other distinct capacities, that of citizen of America and that of citizen
of our respective state; that, as citizens of America, we alone validly
give to its government any power to command us, and, as citizens of
our particular state, we alone validly give to its government all its
national power to command us. The decisions of the Supreme Court,
in that respect, are mentioned elsewhere herein. Meanwhile, we
average Americans understand these matters perfectly and will not
forget them. We are quite accustomed, while retaining our status as
free human beings, to be members of many different societies of
men and, as the members of some particular society, to give to its
government certain powers to interfere with our freedom.
We have in our political system a government of the United
States and a government of each of the several states. Each
one of these governments is distinct from the others, and
each has citizens of its own who owe it allegiance, and whose
rights, within its jurisdiction, it must protect. The same person
may be at the same time a citizen of the United States and a
citizen of a state, but his rights of citizenship under one of
these governments will be different from those he has under
the other.... Experience made the fact known to the people of
the United States that they required a national government for
national purposes.... For this reason, the people of the United
States ... ordained and established the government of the
United States, and defined its powers by a Constitution, which
they adopted as its fundamental law, and made its rules of
action. The government thus established and defined is to
some extent a government of the states in their political
capacity. It is also, for certain purposes, a government of the
people. Its powers are limited in number, but not in degree.
Within the scope of its powers, as enumerated and defined, it
is supreme and above the states; but beyond, it has no
existence. It was erected for special purposes and endowed
with all the powers necessary for its own preservation and the
accomplishment of the ends its people had in view.... The
people of the United States resident within any state are
subject to two governments, one state, and the other national;
but there need be no conflict between the two. Powers which
one possesses, the other does not. They are established for
different purposes, and have separate jurisdictions. Together
they make one whole, and furnish the people of the United
States with a complete government, ample for the protection
of all their rights at home and abroad. (Justice Waite, in
Supreme Court, United States v. Cruikshank, 92 U. S. 542.)
It must seem remarkable to us average Americans, with the
education we have acquired at this point, to realize that our leaders
and “constitutional” lawyers have not known why only we ourselves,
in our capacity as citizens of America, can give any new national
power to interfere with our freedom and that we, for such new giving,
must act, in the only way in which the citizens of America “can act
safely, effectively, or wisely, on such a subject, by assembling in
convention,” in our respective states, the very “conventions”
mentioned for valid grant of such national power in the Fifth Article of
the Constitution made by the citizens of America, so assembled in
such “conventions.” Before dwelling briefly upon the accurate
appreciation of that legal fact displayed by those first citizens in
everything connected with the making of that Constitution and that
Fifth Article, let us realize how well the leaders and great
constitutional lawyers of other American generations between that
day and our own did know this settled legal fact.
After the Americans in nine states had created the new nation and
had become its citizens and had (in that capacity) granted the
national powers of its First Article, the Americans in Virginia
assembled to determine whether they also would become citizens of
the new nation. As the president of the convention, in which they
assembled, they chose Edmund Pendleton, then Chancellor of
Virginia.
Very early in the debates, Henry and Mason, great opponents of
the Constitution, attacked it on the ground that its Preamble showed
that it was to be made by the people of America and not by the
states, each of which was then an independent people. Henry and
Mason wanted those peoples to remain independent. They wanted
no new nation but a continuance of a mere union of independent
nations. They knew that a constitution of government ordained and
established by the one people of America, assembled in their
respective “conventions,” as the Preamble of this Constitution
showed it to be, created an American nation and made the ratifying
Americans, in each state, the citizens of that new nation. For this
reason, the opening thunder of Henry’s eloquence was on that
Preamble. “My political curiosity, exclusive of my anxious solicitude
for the public welfare, leads me to ask, Who authorized them to
speak the language of We, the people, instead of, We, the states?
States are the characteristics and the soul of a confederation. If the
states be not the agents of this compact, it must be one great,
consolidated, national government, of the people of all the states.”
(Henry, 3 Ell. Deb. 22.)
The learned Pendleton, sound in his knowledge of basic American
law and quick to grasp the plain meaning of the Fifth Article of the
new Constitution, quickly answered Henry. “Where is the cause of
alarm? We, the people, possessing all power, form a government,
such as we think will secure happiness; and suppose, in adopting
this plan, we should be mistaken in the end; where is the cause of
alarm on that quarter? In the same plan we point out an easy and
quiet method of reforming what may be found amiss. No, but say
gentlemen, we have put the introduction of that method in the hands
of our servants, who will interrupt it for motives of self-interest. What
then?... Who shall dare to resist the people? No, we will assemble in
convention; wholly recall our delegated powers or reform them so as
to prevent such abuse; and punish those servants who have
perverted powers, designed for our happiness, to their own
emolument.... But an objection is made to the form; the expression,
We, the people, is thought improper. Permit me to ask the gentlemen
who made this objection, who but the people can delegate
powers? Who but the people have the right to form government?...
What have the state governments to do with it?” (3 Ell. Deb. 37.)
We average Americans know and will remember that this learned
American lawyer, only twelve years earlier a subject of an
omnipotent legislature, already knew the basic American principle to
be that the delegation of national power was the constitution of
government of a free people and that only the people, assembled in
convention, could delegate such power and that the state
governments, under basic American law, never can have the ability
to delegate that kind of power. We regret that our “constitutional”
lawyers, all born free citizens of a free republic, have not the same
accurate knowledge of basic American law.
But the knowledge of Henry and of Pendleton, that the document
under consideration was the Constitution of a nation whose citizens
alone could give to its government any valid power to interfere with
their human freedom, was the knowledge of all in that and the other
“conventions,” in which the one people of America assembled and
adopted that Constitution. Let us note another distinct type in that
Virginia convention, the famous Light-horse Harry Lee of the
Revolution. “Descended from one of the oldest and most honorable
families in the colony, a graduate of Princeton College, one of the
most daring, picturesque, and attractive officers of the Revolution, in
which by sheer gallantry and military genius he had become
commander of a famous cavalry command, the gallant Lee was a
perfect contrast to the venerable Pendleton.” (Beveridge, Life of
Marshall, Vol. I, page 387.) Lee also replied to Henry’s attack on the
expression “We, the people” and not “We, the states.” In his reply,
there was shown the same accurate knowledge of basic American
law. “This expression was introduced into that paper with great
propriety. This system is submitted to the people for their
consideration, because on them it is to operate, if adopted. It is not
binding on the people until it becomes their act.” (3 Ell. Deb. 42.)
In the Massachusetts convention, General William Heath, another
soldier of the Revolution, showed his accurate conception of the
legal fact of which we average Americans have just been reading in
the decisions of our Supreme Court. “Mr. President, I consider
myself not as an inhabitant of Massachusetts, but as a citizen of the
United States.” (2 Ell. Deb. 12.)
In the North Carolina convention, William Goudy seems to have
had some prophetic vision of our own immediate day. Speaking of
the document under discussion and clearly having in mind its First
Article, this is the warning he gave us: “Its intent is a concession of
power, on the part of the people, to their rulers. We know that private
interest governs mankind generally. Power belongs originally to the
people; but if rulers [all governments] be not well guarded, that
power may be usurped from them. People ought to be cautious in
giving away power.... Power is generally taken from the people by
imposing on their understanding, or by fetters.” (4 Ell. Deb. 10.)
In that same North Carolina convention, James Iredell, later a
distinguished judge of our Supreme Court, in replying to the common
attack that the Constitution contained no Bill of Rights, displayed
clearly the general accurate knowledge that, in America, any grant of
national power to interfere with human freedom is the constitution of
government and that the citizens of any nation in America are not
citizens but subjects, if even a single power of that kind is exercised
by government without its grant directly from the citizens themselves,
assembled in their conventions. “Of what use, therefore, can a Bill of
Rights be in this Constitution, where the people expressly declare
how much power they do give, and consequently retain all that they
do not? It is a declaration of particular powers by the people to their
representatives, for particular purposes. It may be considered as a
great power of attorney, under which no power can be exercised but
what is expressly given.” (4 Ell. Deb. 148.)
When we average Americans read the debates of those human
beings, the first citizens of America, one thing steadily amazes us, as
we contrast it with all that we have heard during the past five years.
Some of those first citizens were distinguished lawyers or statesmen,
quite well known to history. Some of them bore names, then
distinguished but now forgotten. Most of them, even at that time,
were quite unknown outside of the immediate districts whence they
came. All of them, twelve years earlier, had been “subjects” in an
empire whose fundamental law was and is that its legislative
government can exercise any power whatever to interfere with
human freedom and can delegate any such power to other
governments in that empire. The object of the American Revolution
was to change that fundamental law, embodying the Tory concept of
the proper relation of government to human being, into the basic law
of America, embodying the American concept of that relation
declared in the great Statute of ’76, that no government can have
any power of that kind except by direct grant from its own citizens.
During that Revolution, human beings in America, in conformity with
their respective beliefs in the Tory or the American concept of the
relation of human being to government, had been divided into what
history knows as the Tories and the Americans. Many of the human
beings, assembled in those conventions of ten or twelve years later,
had been sincere Tories in the days of the Revolution.
Yet, if we average Americans pick up any volume of their recorded
debates in those “conventions,” we cannot scan a few pages
anywhere without finding the clearest recognition, in the minds of all,
that the American concept had become the basic American law, that
the Tory concept had disappeared forever from America. All of them
knew that, so long as the Statute of ’76 is not repealed and the result
of the Revolution not reversed, no legislatures in America can
exercise any power to interfere with human freedom, except powers
obtained by direct grant from the human beings over whom they are
to be exercised, and that no legislatures can give to themselves or to
another legislature any such power. It was common in those
“conventions” of long ago to illustrate some argument by reference to
this admitted legal fact and the difference between the fundamental
law of Great Britain and of America, in these respects. In that North

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Copyright Elsevier 2023

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1. Thermodynamics vs. Kinetics 1

3. Fick’s Laws of Diffusion 39

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3.4. Temperature Dependence of Diffusion 46

4. Analytical Solutions of the Diffusion Equation 59

6. Numerical Solutions of the Diffusion Equation 99

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7. Atomic Models for Diffusion 109

8. Diffusion in Crystals 129

9. Diffusion in Polycrystalline Materials 147

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10. Motion of Dislocations and Interfaces 161

11. Morphological Evolution in Polycrystalline Materials 177

12. Diffusion in Polymers and Glasses 199

13. Kinetics of Phase Separation 217

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13.5. Phase-Field Modeling 229

14. Nucleation and Crystallization 235

15. Advanced Nucleation Theories 255

16. Viscosity of Liquids 269

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16.11. Fragile-to-Strong Transition 287

17. Nonequilibrium Viscosity and the Glass Transition 295

18. Energy Landscapes 315

19. Broken Ergodicity 341

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20. Master Equations 363

21. Relaxation of Glasses and Polymers 389

22. Molecular Dynamics 419

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22.8. Thermostats 433

23. Monte Carlo Techniques 443

24. Fluctuations in Condensed Matter 467

25. Chemical Reaction Kinetics 487

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25.4. First-Order Reactions 491

26. Thermal and Electrical Conductivities 501

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The original author of “The Emerald Tablet,” a seminal work of

A place where nothing ever happens.

This view of a heavenly state is a state of thermodynamic equilibrium.

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Kinetic processes are the agents of change in materials science and

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With this foundation in place, we introduce the subject of irreversible

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describing the viscosity-temperature relationship. This naturally leads to the

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