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Glasses and the Glass Transition 1st Edition Ivan S.
Gutzow Digital Instant Download
Author(s): Ivan S. Gutzow, Oleg V. Mazurin, Jürn W. P. Schmelzer, Snejana
V. Todorova, Boris B. Petroff, Alexander I. Priven
ISBN(s): 9783527636563, 3527636560
Edition: 1
File Details: PDF, 4.86 MB
Year: 2011
Language: english
 Schmelzer · Gutzow
Jürn W.P. Schmelzer and Ivan S. Gutzow
Written by renowned researchers in this field, this up-to date advanced
treatise fills a gap in the literature on glasses. It gives an overview of
basic experimental data, of its collection, prediction and theoretical in-
terpretation, thereby paving the way to a deeper understanding of these
topics. The present monograph covers the whole spectrum of problems
involved in the interpretation of glasses and their properties like e.g.
glass transition, relaxation, viscosity, existing and possible unexpected
Glasses and the
Glass Transition
future applications of glasses. The book is recommended to students, to
both young and experienced researchers interested in materials science,
in particular in glasses and glass-ceramics, classical and non-equilibri-
um thermodynamics. It will become a source of new ideas and inspira-
tion for a wide circle of readers working in other areas of science.

From the contents:

G Basic Properties and the Nature of Glasses: An Overview
G Generic Theory of Vitrification of GlassForming Melts

G Generic Approach to the Viscosity of Glass-Forming Melts

G Thermodynamics of Amorphous Solids, Glasses, and

Disordered Crystals
G Principles and Methods of Collection and Analysis of

Glass Property Data

G Methods of Prediction of Glass Properties from Chemical

Glasses and the Glass Transition

Compositions
G Glasses as Accumulators of Free Energy and other

Unusual Applications of Glasses

G Glasses and the Third Law of Thermodynamics

G Etymology of the Word “Glass”

Jürn W. P. Schmelzer studied theoretical physics at the Universities of Odessa (Ukraine) and
Rostock (Germany). He taught this discipline for many years at the Universities of Rostock
and Addis Ababa (Ethiopia). Since 1995, he has been working simultaneously at the Joint In-
stitute for Nuclear Research in Dubna near Moscow, organizing there since 1997 international
research workshops on the theory of phase transitions and possible applications, in particular
to materials science. In 2009, Dr. Schmelzer was awarded the Marin Drinov Medal of the
Bulgarian Academy of Sciences for his longstanding cooperation with Bulgarian scientists, the
present book being one of the results of this fruitful work.

Ivan S. Gutzow has been working at the Institute of Physical Chemistry of the Bulgarian
Academy of Sciences (BAS), Sofia, since his graduation. In 1998, he founded there and headed
till 2004 the Department of Amorphous Materials. He has been a Full Member of BAS since
2003. Simultaneously, he worked as a lecturer at universities in Bulgaria, Germany, the USA,
and Brazil. Professor Gutzow’s scientific interests focus on structure, thermodynamics and
crystallization of glass-forming systems. He described nucleation in glasses as a non-stationary
process, developed methods of nucleation catalysis and synthesis of glass-ceramics, and formu-
lated glass transition models, based on thermodynamics of irreversible processes.
In 2002, Professor Gutzow was awarded the
Alexander von Humboldt Research Prize (Germany).

www.wiley-vch.de
Jürn W. P. Schmelzer and
Ivan S. Gutzow
Glasses and the Glass Transition
Related Titles

Slezov, V. V. Drummond, C. H. (ed.)

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Number 1
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Jürn W. P. Schmelzer and Ivan S. Gutzow

Glasses and the Glass Transition

With the collaboration of

Oleg V. Mazurin
Alexander I. Priven
Snejana V. Todorova
Boris P. Petroff

WILEY-VCH Verlag GmbH & Co. KGaA

The Authors All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. habil. Jürn W.P. Schmelzer publisher do not warrant the information
Institut für Physik contained in these books, including this book, to
Universität Rostock be free of errors. Readers are advised to keep in
Rostock, Germany mind that statements, data, illustrations,
procedural details or other items may
Prof. Ivan S. Gutzow inadvertently be inaccurate.
Bulgarian Academy of Sciences
Institute of Physical Chemistry Library of Congress Card No.: applied for
Sofia, Bulgaria
British Library Cataloguing-in-Publication Data:
Prof. Oleg V. Mazurin A catalogue record for this book is available
Thermex from the British Library.
St. Petersburg, Russian Federation
Bibliographic information published by the
Deutsche Nationalbibliothek
Dr. Snejana V. Todorova
The Deutsche Nationalbibliothek lists this
Bulgarian Academy of Sciences
publication in the Deutsche Nationalbibliografie;
Geophysical Institute
detailed bibliographic data are available on the
Sofia, Bulgarien
Internet at http://dnb.d-nb.de.
Dr. Boris B. Petroff © 2011 WILEY-VCH Verlag GmbH & Co. KGaA,
Bulgarian Academy of Sciences Boschstr. 12, 69469 Weinheim, Germany
Institute of Solid State Physics
Sofia, Bulgarien All rights reserved (including those of translation
into other languages). No part of this book may
Prof. Alexander I. Priven be reproduced in any form – by photoprinting,
Thermex microfilm, or any other means – nor transmitted
St. Petersburg, Russian Federation or translated into a machine language without
written permission from the publishers. Regis-
Cover tered names, trademarks, etc. used in this book,
even when not specifically marked as such, are
The cover-picture shows a sample of diopside not to be considered unprotected by law.
glass heat-treated at 870ı C for about one hour.
In the bulk of the sample, one can observe a Typesetting le-tex publishing services GmbH,
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 V

Foreword

First I would like to stress that the main authors of this monograph – Jürn W.P.
Schmelzer and Ivan Gutzow – are renowned experts on properties of glasses, re-
laxation and phase formation processes in glasses that include glass transition,
liquid–liquid phase separation, crystal nucleation, crystal growth and overall crys-
tallization processes. In the present book, their attention is concentrated on the
description of glasses and glass transition. In analyzing this circle of problems, of
special relevance is their strong background on thermodynamics; they always bring
their research projects into a solid thermodynamic framework. Their new mono-
graph Glasses and the Glass Transition is no exception; it could be also be named,
for instance, Thermodynamics of the Vitreous State. In this book, they review, orga-
nize and summarize – within a historical perspective and discussing alternative
approaches – the results of their own publications on different thermodynamic
aspects of the vitreous state performed after the publication of their book, The Vit-
reous State: Thermodynamics, Structure, Rheology, and Crystallization published by
Springer in 1995.
After the introduction, in Chapter 2, Schmelzer and Gutzow disclose their ideas
on the nature of glasses through an overview of the basic laws of classical ther-
modynamics, the description of nonequilibrium states, phase transitions, crystal-
lization, viscosity of glass-forming systems, thermodynamic properties of glass-
forming melts, glass transition, and on the overall thermodynamic nature of the
glassy state. Most of the presented concepts are discussed within a thermodynamic
perspective.
In Chapter 3, they present and discuss in detail a “generic theory of vitrification
of liquids” and explain the application of thermodynamics of irreversible processes
to vitrification. Then, the authors review relaxation of glass-forming melts, define
the glass transition, comment on the entropy at very low temperatures, the Kauz-
mann paradox, the Prigogine–Defay ratio – including several quantitative estimates
of this parameter – the concept of fictive temperature as a structural order param-
eter, the viscosity and relaxation time at Tg , and finally frozen-in thermodynamic
fluctuations. Once more, all these important characteristics of the vitreous state are
discussed within thermodynamic insights. These concepts are developed in more
detail in the application to relaxation and the pressure dependence of the viscosity
in Chapter 4, and an analysis of systems with a glass-like behavior in Chapter 5.
VI Foreword

In order to apply thermodynamic methods, in general, and to glasses and glass

transition, in particular, the thermodynamic properties of the respective systems,
such as the equations of state, must be known. In order to give an overview on the
present state in this direction, the book also comprises two special chapters: Chap-
ter 6, authored by Oleg Mazurin on the collection and analysis of glass property
data; and Chapter 7, written by Alexander Priven, discusses the available models to
correlate certain glass properties to their chemical composition.
Mazurin was the head of the famous Laboratory of Glass Properties of the
Grebenshchikov Institute of Silicate Chemistry of the Russian Academy of Sci-
ences in the former USSR, for almost 40 years. Then he retired and dedicated his
efforts to his present passion: collection and critical analysis of glass property da-
ta. He worked intensively and published numerous papers on many types of glass
properties, and perhaps most importantly, from the early stages he started to collect
property data from his own group and from published literature to finally master-
mind the assembly of an impressive and most useful glass database – SciGlass –
which currently contains the properties of more than 350 000 glass compositions.
In my opinion this database is a must in the library of any active glass research
group in the world. I am particularly proud to say that my students and I have
been using the SciGlass database for several years from its very beginning. In this
chapter, Mazurin discusses the power of SciGlass, which is regularly updated on
an annual basis, and its multiple utilities. The author emphasizes how one can and
should use SciGlass to compare the values of properties measured by any author
against all the available data. He also stresses a nasty and frequent problem; that
is, the poor quality of data published by some research groups.
Having at one’s disposal such a comprehensive overview on existing experimen-
tal data on glass properties, the next question arises whether it is possible to the-
oretically predict – based on such knowledge – some properties of glass-forming
systems, for which experimental data are not available. This task is reviewed in the
chapter written by Priven. It is probably fair to say that Priven dedicated almost
his entire career to this very important scientific and technological theme: develop-
ment and testing of models to predict the compositional dependence of important
glass properties, such as density, thermal expansion coefficient, refractive index,
liquidus and viscosity, to their chemical composition. Priven has been involved
in the arduous and complex quest of what he calls the “silver bullet.” Although
I never carried out any specific research on this particular subject, I have always
been a keen user of Appen’s model, and lately of Priven’s model, to calculate glass
properties from chemical composition for the development of new glasses and
glass-ceramics (which always have a residual glass matrix). Priven discusses the
strengths and weaknesses of several available models, for example, Winkelman and
Schott’s, Gelhoff and Thomas’s, Gilard and Dubrul’s, Huggins and Sun’s, Appen’s,
Demkina’s, Mazurin’s, Fuxi’s, Lakatos’s and of his own model. He also discusses
the numerous difficulties to develop an accurate model due to the nonexistence of
data for many compositions and nonlinear effects, such as the anomalous effects
of boron and alumina, which fortunately have been already solved by some of these
models. At present one can use Priven’s model and some others for surprisingly
 Foreword VII

good predictions (say within 5–10%) of several properties of glasses containing up

to 30 elements. But the “silver bullet” – to accurately predict the properties of all
possible glasses with combinations of all the 80 “friendly” elements of the period-
ical table – is far from being found (please check the Zanotto paper on this topic
published in the Journal of Non-Crystalline Solids, 347 (2004) 285–288).
After completion of the general task, that is, the thermodynamic description of
glasses and the glass transition, the overview on existing data on glasses and the
methods of prediction of glass properties, Schmelzer and Gutzow go over to a more
detailed discussion of some peculiar properties of glasses and glass-like systems
and their possible technological applications. Chapter 8 deals with “glasses as ac-
cumulators of free energy, of increased reactivity and as materials with unusual
applications,” whereas Chapter 9 is devoted to the third law of thermodynamics
and its application to the vitreous state. It is usually stated that the third law is not
applicable to glasses as they never reach equilibrium for temperatures tending to
zero. Therefore, their entropy has to be larger than zero for T ! 0. The authors
present a detailed historical development, describe the application of thermody-
namics to nonequilibrium states, show some thermodynamic and kinetic invari-
ants at Tg and give an extended discussion on the current controversial issue of
zero-point entropy of glasses. The book is completed by an interesting analysis of
the etymology of the word “glass.”
Summarizing, the present book presents a thorough discussion about the nature
of glass, with a rich historical background (a characteristic of Ivan Gutzow) on the
most basic properties of glasses including vitrification kinetics, relaxation and glass
transition. It cites more than 650 articles. This book will certainly be a very useful
reference for experienced researchers as well as for post-graduate students who are
interested in understanding the nature of glass and the application of the laws of
thermodynamics to nonequilibrium materials such as glasses.

Edgar D. Zanotto Head of the Vitreous Materials Laboratory

August 2010 Federal University of São Carlos, Brazil
Member of the Brazilian Academy of Sciences
Member of the World Academy of Ceramics
Fellow of the British Society of Glass Technology
 IX

Contents

Foreword V
Preface XVII
Contributors XIX
1 Introduction 1
Jürn W. P. Schmelzer and Ivan S. Gutzow
2 Basic Properties and the Nature of Glasses: an Overview 9
Ivan S. Gutzow and Jürn W. P. Schmelzer
2.1 Glasses: First Attempts at a Classification 9
2.2 Basic Thermodynamics 14
2.2.1 The Fundamental Laws of Classical Thermodynamics
and Consequences 14
2.2.2 Thermodynamic Evolution Criteria, Stability Conditions
and the Thermodynamic Description of Nonequilibrium States 22
2.2.3 Phases and Phase Transitions:
Gibbs’s Phase Rule, Ehrenfest’s Classification, and the Landau Theory 26
2.3 Crystallization, Glass Transition and Devitrification
of Glass-Forming Melts: an Overview of Experimental Results 36
2.4 The Viscosity of Glass-Forming Melts 46
2.4.1 Temperature Dependence of the Viscosity 46
2.4.2 Significance of Viscosity in the Glass Transition 54
2.4.3 Molecular Properties Connected with the Viscosity 57
2.5 Thermodynamic Properties of Glass-Forming Melts and Glasses:
Overview on Experimental Results 59
2.5.1 Heat Capacity 59
2.5.2 Temperature Dependence of the Thermodynamic Functions:
Simon’s Approximation 65
2.5.3 Further Methods of Determination of Caloric Properties
of Glass-Forming Melts and Glasses 74
2.5.4 Change of Mechanical, Optical and Electrical Properties
in the Glass Transition Range 76
X Contents

2.6 Thermodynamic Nature of the Glassy State 82

2.7 Concluding Remarks 88
3 Generic Theory of Vitrification of Glass-Forming Melts 91
Jürn W. P. Schmelzer and Ivan S. Gutzow
3.1 Introduction 91
3.2 Basic Ideas and Equations of the Thermodynamics of Irreversible
Processes
and Application to Vitrification and Devitrification Processes 95
3.2.1 Basic Assumptions 95
3.2.2 General Thermodynamic Dependencies 96
3.2.3 Application to Vitrification and Devitrification Processes 100
3.3 Properties of Glass-Forming Melts: Basic Model Assumptions 103
3.3.1 Kinetics of Relaxation 103
3.3.2 Thermodynamic Properties: Generalized Equation of State 105
3.4 Kinetics of Nonisothermal Relaxation as a Model of the Glass Transition:
Change of the Thermodynamic Functions
in Cyclic Cooling-Heating Processes 107
3.4.1 Description of the Cyclic Processes under Consideration 107
3.4.2 Temperature Dependence of the Structural Order Parameter
in Cyclic Cooling and Heating Processes 108
3.4.3 Definition of the Glass Transition Temperature
via the Structural Order Parameter: the Bartenev–Ritland Equation 110
3.4.4 Structural Order Parameter and Entropy Production 113
3.4.5 Temperature Dependence of Thermodynamic Potentials
at Vitrification 115
3.4.5.1 Configurational Contributions to Thermodynamic Functions 115
3.4.5.2 Some Comments on the Value of the Configurational Entropy
at Low Temperatures and on the Kauzmann Paradox 121
3.4.6 Cyclic Heating-Cooling Processes: General Results 123
3.5 The Prigogine–Defay Ratio 125
3.5.1 Introduction 125
3.5.2 Derivation 127
3.5.2.1 General Results 127
3.5.2.2 Quantitative Estimates 133
3.5.2.3 An Alternative Approach:
Jumps of the Thermodynamic Coefficients in Vitrification 135
3.5.3 Comparison with Experimental Data 137
3.5.3.1 The Prigogine–Defay Ratio 137
3.5.3.2 Change of Young’s Modulus in Vitrification 140
3.5.4 Discussion 142
3.6 Fictive (Internal) Pressure and Fictive Temperature
as Structural Order Parameters 143
3.6.1 Brief Overview 143
 Contents XI

3.6.2 Model-Independent Definition of Fictive (Internal) Pressure

and Fictive Temperature 146
3.7 On the Behavior of the Viscosity and Relaxation Time
at Glass Transition 149
3.8 On the Intensity of Thermal Fluctuations
in Cooling and Heating of Glass-Forming Systems 152
3.8.1 Introduction 152
3.8.2 Glasses as Systems with Frozen-in Thermodynamic Fluctuations:
Mueller and Porai-Koshits 153
3.8.3 Final Remarks 158
3.9 Results and Discussion 158
4 Generic Approach to the Viscosity and the Relaxation Behavior
of Glass-Forming Melts 165
Jürn W. P. Schmelzer
4.1 Introduction 165
4.2 Pressure Dependence of the Viscosity 166
4.2.1 Application of Free Volume Concepts 166
4.2.2 A First Exception: Water 169
4.2.3 Structural Changes of Liquids and Their Effect
on the Pressure Dependence of the Viscosity 171
4.2.4 Discussion 173
4.3 Relaxation Laws and Structural Order Parameter Approach 174
4.3.1 Basic Equations: Aim of the Analysis 174
4.3.2 Analysis 175
4.3.3 Discussion 177
5 Thermodynamics of Amorphous Solids, Glasses,
and Disordered Crystals 179
Ivan S. Gutzow, Boris P. Petroff, Snejana V. Todorova, and Jürn W. P.
Schmelzer
5.1 Introduction 179
5.2 Experimental Evidence on Specific Heats and Change of Caloric Properties
in Glasses and in Disordered Solids: Simon’s Approximations 182
5.3 Consequences of Simon’s Classical Approximation:
the ΔG(T ) Course 194
5.4 Change of Kinetic Properties at Tg
and the Course of the Vitrification Kinetics 195
5.5 The Frenkel–Kobeko Postulate in Terms
of the Generic Phenomenological Approach
and the Derivation of Kinetic and Thermodynamic Invariants 198
5.6 Glass Transitions in Liquid Crystals
and Frozen-in Orientational Modes in Crystals 208
5.7 Spectroscopic Determination of Zero-Point Entropies
in Molecular Disordered Crystals 212
XII Contents

5.8 Entropy of Mixing in Disordered Crystals, in Spin Glasses

and in Simple Oxide Glasses 213
5.9 Generalized Experimental Evidence on the Caloric Properties
of Typical Glass-Forming Systems 215
5.10 General Conclusions 219
6 Principles and Methods of Collection of Glass Property Data and Analysis
of Data Reliability 223
Oleg V. Mazurin
6.1 Introduction 223
6.2 Principles of Data Collection and Presentation 225
6.2.1 Main Principles of Data Collection 225
6.2.2 Reasons to Use the Stated Principles of Data Collection 228
6.2.3 Problems in Collecting the Largest Possible Amounts
of Glass Property Data 230
6.2.4 Main Principles of Data Presentation 231
6.3 Analysis of Existing Data 232
6.3.1 About the Reliability of Experimental Data 232
6.3.2 Analysis of Data on Properties of Binary Systems 233
6.3.2.1 General Features of the Analysis 233
6.3.2.2 Some Factors Leading to Gross Errors 237
6.3.2.3 Some Specific Examples of the Statistical Analysis
of Experimental Data 239
6.3.2.4 What is to Do if the Number of Sources Is Too Small? 243
6.4 About the Reliability of the Authors of Publications 246
6.4.1 The Moral Aspect of the Problem 246
6.4.2 An Example of Systematically Unreliable Experimental Data 247
6.4.3 Concluding Remarks 251
6.5 General Conclusion 253
7 Methods of Prediction of Glass Properties
from Chemical Compositions 255
Alexander I. Priven
7.1 Introduction: 120 Years in Search of a Silver Bullet 255
7.2 Principle of Additivity of Glass Properties 257
7.2.1 Simple Additive Formulae 257
7.2.2 Additivity and Linearity 258
7.2.3 Deviations from Linearity 259
7.3 First Attempts of Simulation of Nonlinear Effects 260
7.3.1 Winkelmann and Schott: Different Partial Coefficients
for Different Composition Areas 260
7.3.2 Gehlhoff and Thomas: Simulation of Small Effects 260
7.3.3 Gilard and Dubrul: Polynomial Models 262
7.4 Structural and Chemical Approaches 264
7.4.1 Nonlinear Effects and Glass Structure 264
7.4.2 Specifics of the Structural Approach to Glass Property Prediction 266
 Contents XIII

7.4.3 First Trials of Application of Structural and Chemical Ideas

to the Analysis of Glass Property Data 267
7.4.4 Evaluation of the Contribution of Boron Oxide to Glass Properties 267
7.4.4.1 Model by Huggins and Sun 268
7.4.4.2 Models by Appen and Demkina 268
7.4.5 Use of Other Structural Characteristics
in Appen’s and Demkina’s Models 271
7.4.6 Recalculation of the Chemical Compositions of Glasses 272
7.4.7 Use of Atomic Characteristics in Glass
and Melt Property Prediction Models 278
7.4.8 Ab Initio and Other Direct Methods of Simulation
of Glass Structure and Properties 279
7.4.9 Conclusion 280
7.5 Simulation of Viscosity of Oxide Glass-Forming Melts
in the Twentieth Century 280
7.5.1 Simulation of Viscosity as a Function
of Chemical Composition and Temperature 280
7.5.2 Approaches to Simulation of Concentration Dependencies
of Viscosity Characteristics 282
7.5.2.1 Linear Approach 282
7.5.2.2 Approach of Mazurin: Summarizing of Effects 283
7.5.2.3 Approach of Lakatos: Redefinition of Variables 284
7.5.2.4 Polynomial Models 284
7.5.3 Conclusion 285
7.6 Simulation of Concentration Dependencies of Glass and Melt Properties
at the Beginning of the Twenty-First Century 286
7.6.1 Global Glass Property Databases as a Catalyst
for Development of Glass Property Models 286
7.6.2 Linear and Polynomial Models 286
7.6.3 Calculation of Liquidus Temperature: Neural Network Simulation 289
7.6.4 Approach of the Author 291
7.6.4.1 Background 291
7.6.4.2 Model 292
7.6.4.3 Comparison with Previous Models 294
7.6.4.4 Conclusion 296
7.6.5 Fluegel: a Global Model as a Combination of Local Models 296
7.6.6 Integrated Approach: Evaluation of the Most Probable Property Values
and Their Errors by Using all Available Models
and Large Arrays of Data 297
7.7 Simulation of Concentration Dependencies of Glass Properties
in Nonoxide Systems 299
7.8 Summary: Which Models Were Successful in the Past? 301
7.9 Instead of a Conclusion: How to Catch a Bluebird 306
XIV Contents

8 Glasses as Accumulators of Free Energy

and Other Unusual Applications of Glasses 311
Ivan S. Gutzow and Snejana V. Todorova
8.1 Introduction 311
8.2 Ways to Describe the Glass Transition, the Properties of Glasses
and of Defect Crystals: a Recapitulation 313
8.3 Simon’s Approximation, the Thermodynamic Structural Factor,
the Kinetic Fragility of Liquids and the Thermodynamic Properties
of Defect Crystals 318
8.4 The Energy, Accumulated in Glasses and Defect Crystals:
Simple Geometric Estimates of Frozen-in Entropy and Enthalpy 324
8.4.1 Enthalpy Accumulated at the Glass Transitions 324
8.4.2 Free Energy Accumulated at the Glass Transition
and in Defect Crystals 327
8.5 Three Direct Ways to Liberate the Energy, Frozen-in in Glasses:
Crystallization, Dissolution and Chemical Reactions 331
8.5.1 Solubility of Glasses and Its Significance in Crystal Synthesis
and in the Thermodynamics of Vitreous States 332
8.5.2 The Increased Reactivity of Glasses and the Kinetics of Chemical Reactions
Involving Vitreous Solids 339
8.6 The Fourth Possibility to Release the Energy of Glass:
the Glass/Crystal Galvanic Cell 340
8.7 Thermoelectric Driving Force at Metallic Glass/Crystal Contacts:
the Seebeck and the Peltier Effects 344
8.8 Unusual Methods of Formation of Glasses in Nature
and Their Technical Significance 348
8.8.1 Introductory Remarks 348
8.8.2 Agriglasses, Glasses as Nuclear Waste Forms
and Possible Medical Applications of Dissolving Organic Glasses 350
8.8.3 Glasses as Amorphous Battery Electrodes, as Battery Electrolytes
and as Battery Membranes 352
8.8.4 Photoeffects in Amorphous Solids and the Conductivity of Glasses 353
8.9 Some Conclusions and a Discussion of Results and Possibilities 354
9 Glasses and the Third Law of Thermodynamics 357
Ivan S. Gutzow and Jürn W. P. Schmelzer
9.1 Introduction 357
9.2 A Brief Historical Recollection 360
9.3 The Classical Thermodynamic Approach 363
9.4 Nonequilibrium States and Classical Thermodynamic Treatment 366
9.5 Zero-Point Entropy of Glasses and Defect Crystals:
Calculations and Structural Dependence 368
9.6 Thermodynamic and Kinetic Invariants of the Glass Transition 369
9.7 Experimental Verification of the Existence of Frozen-in Entropies 371
 Contents XV

9.8 Principle of Thermodynamic Correspondence

and Zero-Point Entropy Calculations 376
9.9 A Recapitulation: the Third Principle of Thermodynamics
in Nonequilibrium States 377
10 On the Etymology of the Word “Glass” in European Languages
and Some Final Remarks 379
Ivan S. Gutzow
10.1 Introductory Remarks 379
10.2 “Sirsu”, “Shvistras”, “Hyalos”,“Vitrum”, “Glaes”, “Staklo”, “Cam” 380
10.3 “Vitreous”, “Glassy” and “Glasartig”, “Vitro-crystalline” 382
10.4 Glasses in Byzantium, in Western Europe, in Venice,
in the Balkans and Several Other Issues 384
10.5 Concluding Remarks 385
References 387
Index 407
 XVII

Preface

Nearly all authors of modern science-based books aspire to write the definitive sum-
mary of a chosen subject, a field of inquiry, or the history or future of an emerging
discipline. Books such as the Theory of Metals and Alloys by N. Mott and H. Jones,
Introduction to Solid State Physics by C. Kittel, and The Nature of the Chemical Bond
by L. Pauling readily come to mind in this regard. This book, more correctly a trea-
tise, by Jürn W.P. Schmelzer and Ivan S. Gutzow, with collaboration by Oleg V.
Mazurin, Alexander I. Priven, Snejana V. Todorova, and Boris P. Petroff, rises to
this level in its comprehensive summary of the field of glass science. Drawing
heavily on thermodynamics, kinetic theory, and the physical sciences, virtually all
aspects of the material glass including the transition of an undercooled melt to the
glassy state, are summarized in an authoritative, scholarly, and convincing manner.
Not only is the scope and volume of material examined for this treatise impressive,
so is the way in which it was compiled. That is, the compilation was made through
an exhaustive, comprehensive review and evaluation of the major literature on this
subject from the present day contributions back to the beginning of the last century.
The authors were aided immeasurably by a facility to read articles as they ap-
peared in their original language thereby helping to gain special and even essential
historical insight into the value and scientific correctness of the material being re-
viewed. This in turn allowed a more global approach in direct support of producing
an authoritative discourse on glass and the glass transition. Worthy of exceptional
praise is their discussion of glass and third law of thermodynamics found in Chap-
ter 9. It gives credence to accepting glass science as a major field in its own right
and the need for nearly all theorists to understand what glass is.
The completion of this task is, in fact, a life-long labor of love for these authors,
one which could only be undertaken by a handful of scientists across the globe who
have shared a similar devotion to this subject throughout their professional lives.
In short, they have accomplished their intended purpose in preparing this treatise:
writing the definitive description of glass and the glass transition. It holds potential
to be recognized as a remarkable milestone.
And what might be the expected outcomes of this Herculean task? As a university
professor, I use to make sure my students understood that the penultimate essence
of science is to predict – to predict facts that are known and can be measured, to
predict those that are unknown, and make sure the predictions are quantitative.
XVIII Preface

That is, science must be quantified through mathematical treatment. Through the
authors’ mathematical description of the material of glass and its properties includ-
ing the glass transition, practicing glass scientists and engineers will find this book
invaluable in helping them understand and predict the behavior of glass in a wide
range of settings and applications. It will no doubt be a springboard to the develop-
ment of advanced and possibly even more mathematically rigorous theories of the
vitreous state as new observations are recorded, and their meaning explored.
Additionally, it will be difficult to prepare a manuscript or professional presen-
tation on glass or the glass transition without understanding or referencing this
contribution to the scientific literature. In a similar way, countless students en-
gaged in thesis work on glass will surely become familiar with this treatise, if their
academic work involves fabrication, characterization, or application.
For all of these reasons, it is confidently predicted this treatise will gain inter-
national recognition – not only across the entire materials spectrum – but also in
the broader fields of physics and chemistry. And for this potential, the authors and
their collaborators should take a well-deserved bow.

L. David Pye Professor of Glass Science, Emeritus, Alfred University, USA

August 2010 Past President of the International Commission on Glass
Past President of the American Ceramic Society
Honorary Member of the German Society of Glass Technology
Honorary Fellow, the British Society of Glass Technology
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Arithmetic is not her strong point.
“I don’t think it’s fair,” she declared. “He just meant to muddle us.
The idea of making up such stuff out of his own head! There isn’t
any key, or any way to prove ’em, and the answers are not even in
the back of Miss Horton’s teacher’s book. I know, because——”
“Because?” questioned Mary Hobart. And Lulu dropped her eyes,
and coloured uncomfortably.
It was after her public disgrace that Ernie wrote out the entire set
of problems in a blank-book purchased for the purpose, so that she
might study them quietly at home. And how the child did wrestle!—
shutting herself in the workshop Saturday after Saturday, till finally
she discovered the correct solution! There could be no doubt.
Worked out along certain intricate lines the problems could be
proved!
The next morning, which happened to be the very day before
examination, Ernie carried her precious book down to school.
“Coo-ee!” she yodeled to Mary Hobart, who formed one of a
group of chattering girls on the second landing. “I have the
answers!”
“Not to the Visiting Board’s problems?” returned Mary, excitedly.
“Yes,” Ernie replied, unable to repress her glee. “They are here!”
tapping the book as she spoke. “And they are right, too. They prove!
—all those I’ve had time for!”
At that moment Lulu Jennings brushed past the excited pair.
Apparently she was deep in conversation with a friend, and noticed
nothing.
“If only she guessed!” chuckled Ernestine.
“Well, for goodness’ sake don’t tell her!” warned Mary, the
cautious. “I wouldn’t trust that girl with her own grandmother’s
plated spoons.”
“Do you take me for a goose?” asked Ernie. “Let’s put our books
up, and perhaps we’ll have time to eat an apple before the bell
rings. I have a beauty in my blouse!”
 So the two girls ran up to the classroom, where they found that
Lulu had preceded them, slipped their books into their respective
desks, and, returning to the schoolyard, divided the apple.
“I wish I could explain the problems to you, Mary dear,” Ernie
said. “But, of course, it wouldn’t be fair. It was quite by chance I hit
on the right way. You can imagine my joy! I have only had time to
prove the first six, but the others must be right. I’ll work on them at
noon.”
However, long before noon, Ernie slipped her hand into her desk
to take out the beloved book, and reassure herself by a hasty glance
through its pages. She owns several blank-books; one for spelling, a
second for “home-work,” and a third for English. These were
successively dragged out, and hastily thrust back again. With a
queer little shock it became certain that the book containing the
solution to the all-important problems was missing!
Ernie was puzzled, startled, but, just at first, she felt no suspicion.
Perhaps she had not put the book into her desk, after all. Perhaps
she had dropped it on the landing in the hall. It was impossible to
communicate her loss to Mary Hobart, who had been sent to the
blackboard to demonstrate a proposition. So Ernie raised her hand
and asked Miss Horton’s permission to leave the room to look for
something. The request was granted.
Yet a hurried search of the stairways revealed nothing; and the
more Ernie reflected, the more anxious she became. She returned to
the classroom thoroughly puzzled and distressed.—When what was
her amazement to discover the missing book lying in plain view on
her desk!
Ernie took it up incredulously,—and was instantly conscious of a
faint scent of musk.
She turned to Mary Hobart, who was just about to resume her
seat, having finished her work at the board, and fairly hissed:—
“Smell of Lulu, Mary. Smell her! quick!!!”
Mary looked at Ernie in bewilderment. “I don’t want to,” she
whispered back. “Why should I, I’d like to know?”
 “Go on,” commanded Ernie, too excited to explain. “Smell her!
You must!”
So Mary, with a puzzled and somewhat resentful air, inclined her
head stiffly toward Lulu Jennings and began to sniff.
“Well?” questioned Ernie, with dilating eyes.
“Well,” returned Mary, crossly; “she smells of cheap perfume, as
usual. It’s musk to-day. I hope you’re satisfied.”
“Yes,” returned Ernie, quietly. “And so, I haven’t a doubt, is Lulu.
She has copied my problems! I’ll tell you after school.”
Certainly the evidence seemed conclusive enough, and Mary
added still other links to the chain.
“Don’t you remember?” she said. “Lulu was at her desk when we
put our things away this morning. While we were eating that apple,
she must have taken the book; and no sooner did you leave the
room to look for it, than she asked permission to put some stuff in
the wastepaper-basket. I noticed, from the blackboard, that she
paused at your desk on her way back. She must certainly have
returned it then.”
Yet what was to be done? The affair was entirely too complicated
to take to Miss Horton, even if Ernie could have made up her mind
to that course.
“No,” she returned to Mary’s suggestion. “I just won’t. I’m no tell-
tale. I’d rather give up all thought of the prize, even if I have worked
so hard for it. If Lulu Jennings can enjoy the books earned this way,
she’s welcome to ’em!” And Ernie thrust the fatal blank-book into the
very bottom of her school-satchel, and snapped to the catch with a
click!
The next morning examinations began, with arithmetic first as
usual. Every girl in the class surveyed her paper anxiously, in search
of the famous problem. It was there,—the ninth,—one of the four
which Ernie had neglected to prove. At first this was rather a
disappointment; but, having given up all hope of winning the prize,
Ernie quickly dismissed the matter and set quietly to work, merely
determining to pass as creditably as she could.
 The moments flew quickly by. Absorbed in her calculations, Ernie
forgot all feeling of pique or disappointment; nor did she again think
of Lulu Jennings till, having finished her paper, she passed it under
final review, when something struck her eye!
She gave a little bounce in her seat, and caught her breath
sharply. The answer obtained to the all-important problem was
different to-day from that which she had written out before!
She remembered distinctly what that other answer was, and went
hastily over the work before her to see where the mistake lay. But it
was right. It proved! Figure by figure Ernie followed the intricate
proposition, to which, without a doubt, she had at last obtained the
correct solution! What had been wrong before she did not know, nor
did she much care.
Instinctively her glance sought Lulu Jennings, who sat with head
bent low above her desk. At the same moment Lulu raised her eyes.
She did not look at Ernie, but cautiously toward Miss Horton, who
was standing at the blackboard with her back toward the class. Lulu,
seeing this, darted a stealthy hand into her desk, and brought out a
little roll of paper which she placed in her lap, at the same moment
throwing her handkerchief over it.
Ernie did not wait for anything further, but, rising from her seat,
carried her paper to Miss Horton’s desk. No one paid any attention,
as it is customary for the girls to put up their papers when finished.
On her way back Ernie stopped beside Lulu just long enough to
whisper,—
“I wouldn’t bother to copy that. It’s wrong.”
Lulu turned first white, then red. She clutched the paper in her
lap. Whether she heeded Ernie’s warning makes little difference. The
mark she received was not especially creditable; and Ernie, who
passed a nearly perfect examination, came out head, and was
awarded the prize, after all.
“Just think, Elizabeth!” she chortled. “Five dollars’ worth of books!
We’ll fill up the bottom shelf of the mahogany bookcase, again. I
have my list all made out:—Water Babies, for Robin; The Conquest
of Granada, for Hazard; Longfellow’s poems for you, dear,—and The
Autocrat of the Breakfast Table, for mother. The Visiting Board read
the titles aloud from the platform, and said it was ‘a remarkably
comprehensive selection.’”
“But, Ernie,” I expostulated, “what have you for yourself?”
“Pshaw!” says Ernie—“I told you I was going to use them for
birthday presents. My birthday is past; and besides I wanted nice
editions, and I really think I’ve made the money go as far as
anybody could!”
“It is very sweet of you, honey,” I said; “but we will share that
Longfellow. Aren’t Mary and the other girls delighted?”
“Indeed they are,” admitted Ernie, with an ingenuous little skip.
“I’m quite the Heroine of their young hearts! It’s lots of fun,
Elizabeth. Only, I’m sorry for Lulu. It must be horrid for her to look
back and think how mean she has been,—and all for nothing, too!”
 Wednesday, February 11.

Our precious Robin has been far from well, lately. For some time
now he has almost given up trying to walk. His crutches seemed to
tire him more and more, and his left side has become so helpless
that when he did attempt to get about it reminded one of a little
lame bird trailing a broken wing.
The greater part of the day he has passed propped up with
pillows in the big rocker in the window, or lying in his little crib,
because he was “too tired” to sit up. And the deepening shadows
beneath his eyes have quite wrung our hearts.
Dr. Porter has been very kind and attentive, but far from satisfied;
and last week the stern edict went forth. Robin was to go to bed and
stay there for no less a period than six weeks, with a heavy weight
attached to his little thin leg.
Well, there is one comfort. Our darling baby seems more like
himself since he has been forced at last to give up. He has lost some
of the languor and gentle indifference that seemed to be growing on
him. His merry grin flashes forth with reassuring frequency, followed
by the deep dimple high in his cheek.
“He is resting,” said the doctor, “and he needs it. That boy is grit
clear through,—a quality of which I don’t approve in patients, Miss
Elizabeth.”
“Would you rather have them whine?” I asked.
“Yes,” returned the doctor, uncompromisingly. “I would.”
But Robin will never do that. In the first place, everybody is too
good to him;—Mrs. Burroughs, Miss Brown, and the three Lysles.
Indeed, Mr. Lysle is kind as kind can be. He has brought fruit for
Bobsie several times, and seems quite distressed because “the little
invalid” has not a better appetite. To-day he declared that he really
did not see “how the child managed to survive on such a small
amount of sustenance.” Whereat Ernie giggled, and I had some
difficulty controlling my countenance, for it was at the table the
observation was rumbled forth, just as the kind “Hippopotamus” was
finishing his third helping of turkey.
Yes, turkey! if you please; though certainly it did seem some
weeks ago as if the little Grahams could never again claim even so
much as a bowing acquaintance with that royal bird. And after the
turkey came ice cream and mince pie, served by Rose in a spotless
cap and apron, while Rosebud purred upon the warm hearth in the
kitchen, waiting his turn to lick the plates! For no sooner did plenty
begin to smile again upon our household than Ernie (naughty
Indian-giver!), demanded back her pet. “Mary would just as soon
have one of the grocer’s new kittens,” she affirmed. “I’ve asked him
about it, and he says we may take our pick.” So the compromise was
effected. Rosebud, sleek and debonair as ever, returned to grace our
home,—and such a welcome as the children gave him! Indeed, we
were all glad. Things have not been so comfortable for months,—
which reminds me of Robin’s poem.
It was this morning, while I was washing his face, that Bobs
repeated it to me. A little soap got into his eyes. He screwed them
up, and then remarked,—
“You must be more careful, Elizabeth, when you wash me, else
my poem won’t stay true.”
“Your poem, Bobsie?” I repeated. Though, certainly, by this time I
should be accustomed to the family weakness.
“Yes,” answered Robin, shyly. “Ernie wrote one, you know, and
Haze, too,—so I thought I would. Shall I say it?”
And, without waiting to be pressed, he graciously began:—
“Oh, what a lucky child am I,
As here upon my bed I lie
With all my needs and wants supplied,
My food, and everything beside;—
Clams, and white mice, and kittens, all!
And when I’m cold my mother’s shawl.”
 “Isn’t that pretty?”
“Indeed it is, honey,” I answered. “How did you come to think of
it?”
“Well,” confessed Robin, “I’d been crying just a little yesterday,
Ellie, because I wanted to pertend to play tag and I couldn’t see out
the window, and so I had to blow my nose; and I felt for my
hankersniff under the pillow, and there it was! I didn’t have to ring
or anything! And that made me think how lucky I am, and so I made
up the poem. Is it nice enough to be written down?”
“It certainly is,” I answered. “I will put it in my diary, and some
day when you are a big fat man Ellie will read it aloud to you, and
we will both laugh.”
“Why will we laugh, Ellie dear?” asked Robin, innocently.
“Because we will be so glad that the little sick boy who composed
it grew up strong and well,” I answered.
And so I have written “the poem” here, that I may be able to fulfil
my part of the prophecy.
But now I want to talk a little of Geoffrey, for we are really
anxious about him. There is no doubt the boy is very much changed.
Yesterday afternoon he dropped in to see Ernie nearly an hour
before school was out.
“Why, Geof,” I said, “what are you doing here so early? It is
scarcely two o’clock. Ernie isn’t home yet. Did you have a half-
holiday?”
Geoffrey looked confused. “’Guess your clocks are wrong,” he
answered. “Can you give a fellow a bit of lunch, Elizabeth?”
“I thought you got your lunch at school,” I returned. “But, of
course,—if you are hungry. Rose has just finished baking. Isn’t that
luck?” And I ran down to the kitchen, where a glass of milk, a couple
of bananas, and a plate of hot ginger-bread were quickly collected.
Geof ate in silence, crumbling his ginger-bread over the tray cloth
on the library table.
 “Geoffrey!” I remonstrated. “That’s too good to waste. What you
don’t want I am going to take up to Robin.”
“All right,” answered Geof, pushing his plate indifferently toward
me. “How is the kid?” Then he broke into a short chuckle. “I say,
Elizabeth,” he remarked, “there’s a trained bear out at the zoo that
would tickle Bobs most to death. I’ve been feeding it peanuts all the
morning. It’s gentle as a kitten, the keeper says,—jolly good sort he
seems, too,—and——”
“Geoffrey!” I accused, in sudden shocked enlightenment. “You
have been playing hookey.”
Geof flushed angrily, and bit his lip. “Well, and if I have?” he
blustered. “It’s nobody’s business but my own, I suppose!”
“It certainly is somebody’s business,” I answered, decidedly. “And
you ought to be ashamed of yourself. After all the trouble you were
in last term over hockey and athletics, I should think you would have
learned that such foolishness doesn’t pay.”
Geof sprang to his feet. “Now see here, Elizabeth,” he said, “I’m
not going to be jawed by you. I get enough of that sort of talk at
home. If you can’t be pleasant, I’ll go somewhere else. There are
plenty of other places where a chap can spend the afternoon, and
Hollister and Sam Jacobs are glad enough to show ’em to me.”
“Very well, Geoffrey,” I answered. “If you choose to treat the
matter so! Only, I warn you frankly, in that case I shall go directly
upstairs and tell mother,—I shan’t feel that I have any choice,—and
she will tell Uncle George, I know.”
Geof turned on me incredulously. “You sneak!” he cried. “If that
doesn’t sound exactly like Meta!”
“Oh, Geof dear!” I expostulated, hurt and shocked by his violence.
“Don’t let’s quarrel, or misunderstand each other. You know very well
I don’t want to get you into trouble. But Sam Jacobs and Jim
Hollister are not the sort of fellows you ought to associate with. I
don’t believe you really enjoy the places they take you to, either,—
and in the end it can’t help but be found out. You are doing yourself
an injustice, Geoffrey,—truly you are! Come, let’s sit down and talk
things over quietly.”
I laid my hand on his arm. He tried to shake it off,—but the next
instant his face changed.
“Hang it all, Elizabeth!” he blurted out. “If I had sisters like you
and Ernie,—or a mother!”
And the first thing I knew big, strong, manly Geof had broken
down, and was sobbing like a baby, his head buried in his arms on
the library table.
And presently the whole wretched story came out. It seems that
things have been going from bad to worse ever since last
September. It was only by unusual pressure brought to bear by Aunt
Adelaide, and equally unusual acquiescence on the part of the school
authorities, that Geof managed to be promoted with his class this
year, and he entered the new grade heavily conditioned in nearly all
his studies. This, in itself, was bad; but what made the matter still
harder was that in his case a weekly report has been substituted for
the customary monthly one; he tutors three afternoons a week; and
his progress is kept under rigid supervision.
“So if I’m not nagged about French, I am about Latin,” said poor
Geoffrey; “and I tell you, Elizabeth, the schedule I’m carrying this
year is enough to daze a Solomon.”
“But do you really try to study, Geof?” I asked. “Have you made
one honest effort to set things right?”
Geof flushed. “Yes; I have,” he answered, sullenly. “But nobody
believes it. And recently I’ve had so many headaches, and I don’t
sleep well nights, and——”
“If Aunt Adelaide knew that?” I suggested.
“She’d think I was faking,” concluded Geof, hardily. “And I don’t
know that I blame her much,” he admitted, the next minute. “You
see, we never have gotten along. I was seven when my own mother
died, and nine when the governor remarried,—just old enough to
resent it. I remember for three weeks I wouldn’t call her ‘mamma,’
till finally the matter was taken to headquarters, and I had to. And
then Meta didn’t make things any easier. We fought from the very
start. And they’ve managed to set the governor against me, till now
—Well, the latest threat is, if my March reports don’t show ‘marked
improvement’ I’m to be packed off to the Catskills for the summer to
a little tin soldier camp, where the fellows wear toy uniforms and
tutor all through vacation. Pleasant prospect!”
“Then, Geoffrey, why in the world play hookey,” I asked, “and
throw away your last possible chance of avoiding it?”
Geof was silent.
“Come, be sensible,” I urged. “Things do look black, I admit, but
if for the next few weeks you learn the lessons set each day, and
look neither forward nor back——”
“That’s just it,” interrupted Geof. “You’ve hit the nail on the head.
There’s too much behind me, Elizabeth. I can’t learn what we are
having now, because I didn’t last term, or the year before. And,—
and, you haven’t any idea how hard it is when everybody is down on
a chap. Now that I’m out of athletics the fellows I used to go with
have no further use for me; I never did get along with the grinds;
and Hollister, Jacobs, and their set are always cordial and pleasant,
at least. I’ve got to associate with somebody, I suppose? You don’t
know what you are talking about,—that’s all.”
“Yes, I do, Geoffrey,” I replied. “It won’t be easy to turn round, I
know;—but what is the use of complicating matters still further?
Right is right, and wrong wrong; and hookey never paid yet. Will you
give me your word that you will go to school to-morrow?”
Again Geof was silent, and I waited. It seemed hard,
unsympathetic,—yet what was I to do? “Will you give me your word,
Geof?” I reiterated.
“All right,” he muttered, sullenly, at last. “You have the whip-hand.
I’ll go to school to-morrow and the day after. I won’t promise more
than that. And Saturday, if I haven’t seen the governor myself, you
are welcome to go and tell him anything you please. Does that
satisfy you?”
 It did not, entirely; but in Geof’s stubborn mood it was the best I
could hope for, and at least he will have time to think things over till
the end of the week. Poor, foolish fellow! I hope I shan’t be obliged
to tell!
 Saturday, February 14.

Geoffrey has run away! So that was what he meant by promising to

go to school till Saturday! Oh, I feel as if I were partly responsible;—
and yet, how could I have suspected?
He was over here late yesterday afternoon. I did not have a
chance to see him, as mother was out, and Robin rather feverish
and fretful; but Ernie and he talked together in the workshop for
nearly a couple of hours, and after he went Ernie came down to
dinner with such red eyes.
“What is it, dear?” I asked, at last, when she and I were
undressing together in our little room. “Was Geof in one of his
moods again?” For Ernie had been on the verge of tears all the
evening.
She dropped upon the bed then, with a little wail, and buried her
face in the pillows. “I should say he was,” she sobbed. “I couldn’t do
a thing with him. That hateful military camp! It’s enough to drive
anybody to desperation!”
“Is it settled?” I asked. “Must Geof really go?”
“Oh, don’t bother, Elizabeth,” returned Ernie, almost crossly. “He’s
going to talk to Uncle George to-night. He gets his allowance
Fridays, you know; and to-morrow we’ll hear.”
Then she turned her face to the wall and pretended to go to
sleep; but she was restless for hours, and once she cried out wildly
in her dreams:
“Geoffrey! you mustn’t! You mustn’t, I tell you!”
No wonder she was anxious, poor child; for it seems that
Geoffrey, after having first obtained a promise of secrecy, confided
his plans to her yesterday afternoon. She is the only person who
knows where he is now, and entreaties and arguments are equally of
no avail. We simply cannot get her to tell.
 The first alarm reached us this morning, just as we had risen from
the breakfast table. There was a sharp ring at the door-bell; and
Rose, answering the summons, found Maria, one of Aunt Adelaide’s
maids, outside.
“Is Master Geoffrey here?” asked Maria, rather breathlessly. And,
upon receiving Rose’s denial, she cried out:
“Then Lord-a-mercy knows what’s become of him! For he ain’t
been home all the morning, not even to his breakfast, and missis
and the boss, too, are in a great taking!”
Mother and I, who were on our way upstairs, overheard the
exclamation and turned back.
“What is it, Maria?” asked mother, after having sent Rose down to
the kitchen again. “Master Geoffrey has not been here since
yesterday. You say he was not home to breakfast?”
“No, ma’am,” answered Maria; and proceeded to pour forth her
tale. It seems that Geoffrey has been in the habit of over-sleeping
recently, which indulgence greatly irritated Aunt Adelaide.
“Mrs. Graham thinks it’s only manners for the family to sit down
to meals together,” Maria explained. “So this morning when Master
Geoffrey did not come, she sent Jennie up to knock at his door, and
Jennie, she knocked, and knocked again, and got no answer. So
after a bit she came down, and said she could not make Master
Geoffrey hear, and Mr. Graham jumped up.
“‘I’ll wake him myself,’ he says. ‘We’ve had enough of this sort of
nonsense.’ And he went and called very angry-like at the foot of the
stairs; but still there was no reply;—and I was rather sorry for
Master Geoffrey when his pa snatched off one of his slippers and ran
upstairs and threw open the bedroom door.
“‘He’s going to catch it, sure enough, like any babby,’ I thought;
but he didn’t, because the room was empty. The bed had not even
been slept in.
“‘Hello!’ says Mr. Graham, in a disturbed sort of way. And he put
on his slipper and came downstairs again; and directly breakfast was
over they sent me here.”
 “Can Ernie know anything of this?” asked mother, turning to me.
“She is Geoffrey’s usual confidante. Run upstairs and get her,
Elizabeth. I believe she has taken Robin his tray.”
All the colour died out of Ernie’s face when she saw me enter the
nursery; but it flooded back again in a crimson wave as she listened
to mother’s message. However, she settled Bobsie to his breakfast,
and quietly followed me downstairs.
“Have you any idea where Geoffrey is, Ernie?” asked mother,
gravely.
Ernie’s long lashes swept her cheeks. “Isn’t he at home?” she
returned, in a tone that was intended to sound innocent.
Mother smiled, just a little. “Don’t be foolish, dear,” she replied. “If
you know anything about Geoffrey it is only right for you to tell us.
We are not his enemies.”
For a moment Ernie stood silent; then she said, very low, “I know,
but I can’t tell. I’ve promised.”
At that instant there sounded a second peal at the bell. This time
it was Uncle George. Never before in my life have I seen him so
upset, though it was evident he tried to appear indifferent.
His first words were addressed to Maria.
“Go home to your mistress, my good girl,” he said.
Then, turning to mother,—“It does not answer to send servants
on such errands. They simply stand and gossip.”
Mother flushed a little. “Maria is quite blameless,” she replied. “I
desired to hear all she knew in regard to Geoffrey. Have you any
further news?”
Uncle George laid his hat carefully upon a chair, and felt in his
coat pocket.
“It seems the young scamp left a note,” he said, in a voice that
was husky, despite his assumption of unconcern. “It was not in his
room, or we would have found it earlier. He gave it to Georgie last
night, telling him to give it to me this morning as soon as he had
finished breakfast in the nursery.” And Uncle George handed mother
a folded sheet of paper.
“Dear father,” we read,—I was looking over her shoulder,—
“I find that I shall have to go away for I ment what I
said wen you gave me my money tonight. It would be
beastly to go to that miletary-camp and I cant studdy and
keep things up in the way that is expected it makes my
headache. Perhaps there is something the matter with that
part of my bran wich I have inherited from you. But dont
worry this will not keep me from being a good bizness man
wich has always been the fate I have most wished for. I
am sorry to have made so much trubble and Ill come back
some day. Dont let Georgie forget me and dont you forget
me either
“Your loving son
“Geoffrey Meadows Graham.”
I wanted to cry as I read it. Poor, blundering, affectionate Geof,
with his atrocious spelling and his “inherited bran.”
Mother handed the note to Uncle George again, without a word.
“Well?” he asked, shortly.
“It is very like Geoffrey,” she said; “though I never could have
supposed he would run away. What are you going to do?”
“I, myself,” returned Uncle George, “would prefer to wait and give
the young beggar a chance to grow tired of his experiment. That’s
the medicine he needs. A chap who can throw over a good home
such as Geoffrey has, ought to be made to rough it a bit. But the
women folk won’t hear of it. Meta and her mother are in a great
taking. They imagine all sorts of foolishness, and it’s on account of
them, more especially, that I have come over to interview your
Ernie. Come, young woman! What have you got to say for yourself?
Do you know anything of Geoffrey’s whereabouts?”
Again Ernie flushed crimson, lowered her eyelids, and remained
silent.
 “I have already questioned Ernestine,” said mother. “She
undoubtedly knows certain facts which would be very useful. I hope
that I shall be able to convince her it is her duty to tell us.”
Uncle George looked from mother to Ernie in blank amazement.
“Do you mean to say she won’t tell?” he demanded. “Then there is
only one way out of it. She must be made to.”
“I shall try to show Ernie that it is the only way in which she can
be of any help to Geoffrey,” answered mother, quietly.
Uncle George frowned impatiently.
“I’ll tell you what,” he said, after a moment’s thought. “I’ll give
her a five-dollar gold piece for the first bit of information she has to
give us. What’s more, I’ll make it twenty-five dollars, if it leads to
Geoffrey’s capture before night. What do you say to that, my girl?”
It would be impossible to describe the look of horror depicted in
Ernie’s features. Betray Geof, her dear chum, her more than brother,
for a sordid money reward! If Uncle George had only known it, our
last chance of winning Ernie was lost when he uttered those hateful
words. But he did not know, and it would have been impossible to
make him understand. On the contrary, he picked up his hat with a
satisfied expression of having set things on the right track, at last,
and after a final injunction “to keep him informed,” left us.
Mother and I looked hopelessly at one another as the front door
closed behind him.
“Ernie, dear,” said mother, very gently, “setting aside all thought of
Uncle George’s offer, for, of course, it is out of the question that you
should accept any money,—I expect you to tell me at once all you
know in regard to Geoffrey’s plans. It may be the means of saving
him great hardship, and discomfort.”
“Yes, Ernie,” I urged. “And everybody is agreed that it is much
better to break a bad promise than to keep it. Doesn’t your own
common-sense tell you that?”
But reason, command, entreat as we might, Ernie remained
obdurate.
 She sat on the top stair leading down to the basement, the big
tears welling in her blue eyes and trickling along her nose till they
dropped from the tip with a little splash into her lap; listening
plaintively to all we said, replying nothing,—a moving picture of
stubborn misery.
At last mother desisted.
“Ernie,” she said, “I want you distinctly to understand that I am
both disappointed and displeased with you. You are the one person
who can be of any help to Geoffrey; but I shall ask you no further
questions. When your own good feeling and sense of right prompt
you to follow my wishes, I shall be ready to listen to you.”
Then mother dressed and went to see Aunt Adelaide; I ran up to
the nursery to Robin; and Ernie locked herself in the workshop,
where she set to work painting a gorgeous family of Japanese paper
dolls for Mary Hobart’s birthday,—spattering their beflowered
kimonos ever and again with a salty drop. She was very forlorn, poor
darling;—distressed beyond measure to feel that her family
disapproved of her. Yet she had given her word to Geof.
So the morning passed. Lunch time came, and still there was no
news. The afternoon dragged even more heavily; and when Hazard
came home from the office in the evening he told us that Uncle
George had three detectives looking for Geof, but as yet they had
found no clue.
Dinner was somewhat of an ordeal. I had the head of the table,
as mother did not feel she could leave Aunt Adelaide, who is in a
very apprehensive and nervous state. We tried to keep the
conversation to general topics, but the anecdotal vein of the
boarders was not to be stemmed. It seems that Geoffrey’s escapade
reminded everybody of some long-forgotten incident in his or her
own family, or the family of a friend, or even a friend’s friend.
Nothing was too far-fetched to be appropriate, every possible
climax to the adventure was predicted, and the same heartening
conversation continued when we gathered in the parlour after dinner
to wait for news. Till, finally, about half-past ten or so, the boarders
began to disperse to their rooms;—yet not before Mr. Lysle had
made a brief, though painful, effort to win Ernie’s confidence; for she
is a favourite with the kind “Hippopotamus,” and it grieved him to
know her in disgrace.
Therefore, interrupting his sister, who was condoling with Miss
Brown over the sad fate of a nephew of the latter’s mother’s aunt,
who eloped with a sea captain’s daughter some sixty years ago, and
was finally eaten up by whales off the Cape of Good Hope (I believe
it was thus the thrilling story ran), Mr. Lysle, with a sly wink at his
wife over the top of his newspaper, began:
“Miss Ernie! ahem!”
Ernie looked up from her “home-work,” and the “Hippopotamus”
continued ponderously:
“I suppose you are familiar with the famous anecdote of George
Washington and his hatchet? How, when still a young boy, the
Father of Our Country found it impossible, even with the fear of
stern chastisement before him, to tell a—er—a—lie?”
Ernie cautiously refusing to commit herself to any previous
acquaintance with the incident, Mr. Lysle continued blandly:—
“Now, my dear child, a similar opportunity is presented to you,—
an opportunity such as you may never meet again—a grand
opportunity! a great one! The path of truth is a path of roses, for all
that it has its thorns,—even, if I may say so, because of them!”
He paused impressively, and looked Ernie firmly in the eye. We,
the audience, waited breathless, but still Mr. Lysle did not speak. So,
supposing, at last, the homily must be concluded, we were about to
return to our various avocations, when he positively thundered forth:
“Where is your Cousin Geoffrey? Where is that wilful lad? Speak! I
command you!”
Everybody in the room jumped, and Miss Lysle, who is nervous,
uttered an hysterical little squawk, like a frightened hen.
Ernie alone remained undaunted. The poor “Hippopotamus”
continued to gaze at her, triumph fading to chagrin, till, finally, he
turned to his wife with such a disappointed air:—
“I thought I could surprise it out of her,” he said; “but, evidently, I
—er—couldn’t!” And a few moments later he bade us a subdued
“good-night” and was soon followed upstairs by the rest of the
boarders.
It seems too strange to be sitting here writing these things, with
no idea where Geoffrey may be! If only I did not feel my own
responsibility so keenly! I can see now that I should have told
mother last Tuesday when first I heard of Geof’s trou——. There is
the bell! It may be news....

Yes! and good news, too. Geoffrey is found! He was brought

home about eleven o’clock by one of Uncle George’s detectives, who
ran across him in a little out-of-the-way cottage in Elizabeth, where
he had spent the day with a German woman, who was once a cook
at Uncle George’s when Geoffrey’s own mother was alive. She is
married now, and has a neat little home of her own, with three fat
German babies.
There Geoffrey arrived late last night, and to-morrow morning he
had planned to set out again on his travels and beat his way to
South Dakota, where Mrs. Prendergast, the German woman, has a
brother who works on a cattle ranch! Think of it!
Dear little Ernie broke down completely when she heard of
Geoffrey’s capture. She threw herself into mother’s arms, sobbing
convulsively:—
“I didn’t mean to be naughty, mother dear! I didn’t! And, of
course, you know best—only I had given my word, you see, and
then Uncle George might have made me take that hateful money!
Oh, what are they going to do to Geoffrey!”
“There! there, dear!” said mother. “Don’t cry so. It is all over now.
And as to Geoffrey, you need not worry. Aunt Adelaide and Uncle
George are only too anxious to forgive him. He has acted very
wrongly, and given us all a great fright; but it has been a lesson to
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