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Springer Series in Materials Science 313

Kamal K. Kar Editor

Handbook
of Nanocomposite
Supercapacitor
Materials III
Selection
Springer Series in Materials Science

Volume 313

Series Editors
Robert Hull, Center for Materials, Devices, and Integrated Systems, Rensselaer
Polytechnic Institute, Troy, NY, USA
Chennupati Jagadish, Research School of Physics and Engineering, Australian
National University, Canberra, ACT, Australia
Yoshiyuki Kawazoe, Center for Computational Materials, Tohoku University,
Sendai, Japan
Jamie Kruzic, School of Mechanical & Manufacturing Engineering,
UNSW Sydney, Sydney, NSW, Australia
Richard M. Osgood, Department of Electrical Engineering, Columbia University,
New York, USA
Jürgen Parisi, Universität Oldenburg, Oldenburg, Germany
Udo W. Pohl, Institute of Solid State Physics, Technical University of Berlin,
Berlin, Germany
Tae-Yeon Seong, Department of Materials Science & Engineering,
Korea University, Seoul, Korea (Republic of)
Shin-ichi Uchida, Electronics and Manufacturing, National Institute of Advanced
Industrial Science and Technology, Tsukuba, Ibaraki, Japan
Zhiming M. Wang, Institute of Fundamental and Frontier Sciences - Electronic,
University of Electronic Science and Technology of China, Chengdu, China
The Springer Series in Materials Science covers the complete spectrum of materials
research and technology, including fundamental principles, physical properties,
materials theory and design. Recognizing the increasing importance of materials
science in future device technologies, the book titles in this series reflect the
state-of-the-art in understanding and controlling the structure and properties of all
important classes of materials.

More information about this series at http://www.springer.com/series/856

Kamal K. Kar
Editor

Handbook of Nanocomposite
Supercapacitor Materials III
Selection
Editor
Kamal K. Kar
Advanced Nanoengineering Materials Laboratory
Department of Mechanical Engineering
and Materials Science Programme
Indian Institute of Technology Kanpur
Kanpur, Uttar Pradesh, India

ISSN 0933-033X ISSN 2196-2812 (electronic)

Springer Series in Materials Science
ISBN 978-3-030-68363-4 ISBN 978-3-030-68364-1 (eBook)
https://doi.org/10.1007/978-3-030-68364-1

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
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Dedicated to my wife, Sutapa, and my little
daughter, Srishtisudha for their loving
support and patience, and my mother, late
Manjubala, and my father, late
Khagendranath
Preface

The global energy scene, which is one of the largest and most diversified fields
in the world, is in a state of flux. These include the moving consumption away
from non-renewable energy sources, rapid deployment of major renewable energy
technologies and deep decline in their costs, and a growing shift towards electricity
in energy use across the globe. This power and energy system is experiencing its
greatest ever changes and challenges due to the shift from traditional power and
energy networks to smart power/energy grids. As long as the energy consumption
is intended to be more economical and more environment-friendly, electrochemical
energy production is under serious consideration as an alternative energy/power
source. In other words, a large amount of electricity can be generated from natural
sources like solar, wind and, tidal energy and it is imperative to stock the produced
energy since man has constrained control over these natural wonders. Batteries, fuel
cells, and supercapacitors belong to the same family of energy storage devices, which
are ubiquitous in our day-to-day life. But the supercapacitor is a step-up device in
the field of energy storage and has a lot of research and development scope in terms
of design, parts fabrication, and energy storage mechanisms.
Various types of supercapacitors have been developed such as electrochemical
double-layer capacitors (EDLC), pseudocapacitors (or, redox capacitors), and capaci-
tors. They store charges electrochemically and exhibit high power densities, moderate
to high energy densities, high rate capabilities, long life, and safe operation. The elec-
trode, electrolyte, separator, and current collectors are the key parts for the super-
capacitors for energy storage to determine the electrochemical properties, energy
storage mechanism, and mechanical properties of the supercapacitor devices. There-
fore, many significant breakthroughs for a new generation of supercapacitors have
been reported in recent years through the development of these materials and novel
device designs. But the performance of devices is still challenging in terms of capaci-
tance, flexibility, cycle life, etc. These deciding factors depend on the characteristics
of materials used in the devices. The key objective is to select the right materials
with new technologies and developments for the electrodes, electrolytes, separators,
and current collectors, which are the essential components of supercapacitors with
an aim to enhance the performance of supercapacitors.

vii
viii Preface

The book Handbook of Nanocomposite Supercapacitor Materials with a theme of

Selection focuses on the various characteristics of prospective materials and how to
select the right materials with the concept of various material indices using Ashby’s
chart. This book provides a comprehensive study on several architectural carbon
materials, transition metal oxides, conducting polymers, and their binary and ternary
composite electrodes that are using in the current era of supercapacitors. Finally,
it highlights the advantages, challenges, applications, and future directions of the
supercapacitors. Therefore, this book will provide the readers with a complete and
composed idea about the fundamentals of supercapacitors, the recent development
of electrode materials for supercapacitors, and the design of their novel flexible
solid-state devices. This book will be useful to graduate students and researchers
from various fields of science and technology, who wish to learn about the recent
development of supercapacitor and to select the right material for high-performance
supercapacitor.
Chapter 1 discusses about the differences between other energy storage devices
and supercapacitor, historical developments of supercapacitors, Faradaic and non-
Faradaic processes, types of supercapacitors i.e., electric double layer capacitors,
pseudocapacitors, asymmetric supercapacitors, hybrid supercapacitors, quantum
supercapacitors, on-chip supercapacitors, hybrid energy storage systems, etc.,
various components of supercapacitor i.e., electrodes, electrolytes, separators and
current collectors, various materials used in these components i.e., activated carbon,
graphene/reduced graphene oxide, carbon nanotubes, carbon nanofibers, conducting
polymers, transition metal oxides, metal-organic frameworks, covalent organic
frameworks, MXenes, black phosphorous, aqueous electrolytes, non-aqueous elec-
trolytes, organic electrolytes, ionic liquids, solid state or quasi-solid state electrolytes,
solid/dry polymer electrolytes, gel polymer electrolytes, inorganic solid state elec-
trolytes, polyelectrolytes, redox active electrolytes, etc., and various electrochemical
characterization techniques.
As supercapacitors deliver excellent electrochemical performances such as high
capacitance, high power density, and long cyclic stability at low cost. In contrast
with other energy storage devices, its charge storage mechanism is simple, which
makes its charging and discharging process highly reversible. Based on the charge
storage mechanism, its electrode material can be categorized as EDLC and pseudo-
capacitor. EDLC capacitor stores charge electrostatically whereas, reversible redox
reaction occurs in pseudocapacitance. The charge is stored via the Faradaic process.
The further improvement in the performance is done by the formation of composite
electrode material, the introduction of nanostructure electrode, assembling a hybrid
capacitor by introducing battery electrode material, and assembly of an asym-
metric supercapacitor. Various combinations of electrode and electrolyte material
in different types of configuration provide a synergistic effect of both types of charge
storage mechanism and wide operating potential range. The main aim is to obtain a
high energy density device without compromising other parameters such as power
density, rate capability, and cyclic stability. Chapter 2 extensively deals the various
materials used in supercapacitors, types of charge storage mechanisms, types of
Preface ix

supercapacitor assembly i.e., symmetric supercapacitors, asymmetric supercapaci-

tors, battery-supercapacitor hybrid devices, etc., and their performance to the type
of electrode material.
Nowadays flexible solid-state supercapacitors (FSSCs) are the most emerging
energy storage devices in modern miniatured technologies. With increasing the use of
micro and flexible electronic devices such as, wearable electronic suits, microsensors,
and biomedical equipment, the demand for FSSCs is increasing exponentially. These
electronic devices focused on the integration of many components in a single compact
system that must be flexible in nature, lightweight, smaller in dimension, unbreak-
able and should be available at a competitive price. Chapter 3 mainly focuses on the
advancement of FSSCs devices with its all components such as current collector, elec-
trode materials, and electrolytes. This chapter also discusses the strategies of fabrica-
tion techniques, types of FSSCs, design, evaluation of performance, and applications
of FSSCs device step-by-step.
CPs are known for their astonishing electrical and electrochemical properties.
Characteristic features such as tunable conductivity, structural flexibility, mild
synthesis and processing conditions, chemical and structural diversity make them an
excellent candidate for different fields of interest. Chapter 4 aims to revisit the journey
and recent advancements of CPs in the field of energy storage systems like super-
capacitors. CPs have been considered as one of the excellent candidates for super-
capacitor as they show miscellaneous redox nature, amazing electrical conductivity,
good flexibility, and many others. Therefore, a substantial discussion is required to
discuss the supercapacitors and their advantages and disadvantages, recent advance-
ments, future challenges, and new possibilities. Chapter 4 focuses on the synthesis,
processing, and chemical modifications of various CPs with various interesting prop-
erties and their electrodes used for the advancements of supercapacitors which is the
need of the hour.
Among all the components i.e., electrode, electrolyte, separator, and current
collector, the electrode plays a major role to store a large amount of charge at its
surface. So, characteristics of the electrode such as porosity, surface morphology,
surface area, electrical conductivity, etc., are taken into account for selecting suit-
able electrode material for supercapacitor. Activated carbon, CNT, graphene, carbon
aerogel, metal compounds, conducting polymers, and their composites are among
various materials, which have been commonly used as electrodes and discussed in
detail to select the best material with the concept of various material indices using
Ashby’s chart in Chap. 5.
Electrode stores charges, electrolyte provide necessary ions, current collector
transfer the charge from the electrode to external circuit and separator acts as a
membrane, which prevents the device from short-circuit. The separator’s main func-
tion is to separate cathode and anode electrode material in supercapacitors to prevent
short circuits and mainly present in the form of a porous membrane in order to provide
x Preface

easy ion transfer. The common material used as separator includes glass fiber, cellu-
lose, ceramic fibers, or polymeric film materials. Chapter 6 mainly describes func-
tions served and characteristics required for separators and their materials, respec-
tively, which are chosen according to those functions. Finally, the selection of sepa-
rator material is justified with the help of various material indices using Ashby’s
chart.
A lot of research is being done to improve the efficiency and performance of
supercapacitors by making the right choice for electrodes, electrolytes, separators,
and current collectors. Among all the components, electrolytes serve the purpose
of balancing charge in supercapacitor and provide necessary ions to form an elec-
trical connection between electrodes. The electrolyte materials used in supercapac-
itor can be classified as organic, aqueous, ionic liquids, solid-state, and redox-active
electrolytes and are chosen according to their properties, ultimate applications, and
physical state of the supercapacitor. Chapter 7 explains the functions of electrolytes,
classification of electrolytes i.e., aqueous electrolytes, organic electrolytes, ionic
electrolytes, etc., characteristics required for electrolytes i.e., conductivity, viscosity,
ionic concentration, electrochemical stability, thermal stability, dissociation, toxicity,
volatility and flammability, cost, etc., performance of various electrolytes, perfor-
mance metrics and their relationships, selection of electrolyte material in detail with
the support of various material indices using Ashby’s chart.
The main function of the current collector is to collect and conduct electric
current from electrodes to power sources. It also provides mechanical support to
electrodes. To meet the required properties of the current collector materials should
have minimum contact resistance, high electric conductivity, and good bonding
capacity with electrodes. Most commonly used conventional metals like copper,
aluminum, nickel, etc. are being replaced by advanced materials such as nanostruc-
tured or composite materials. In addition to this, the demand for flexible electronics is
growing rapidly nowadays, these devices require a material with enhanced properties.
Different types of materials used for the current collector are thoroughly discussed
in Chap. 8, where the selection of materials depends upon the cost of materials and
their suitability toward particular applications. Comparative study of properties for
various current collector materials has been done to suggest suitable material for
supercapacitor applications. The selection of the current collector is discussed with
the help of various material indices using Ashby’s chart.
Supercapacitor management systems have been developed for supercapacitor
usage during demand within safe operating limits. Supercapacitors and batteries are
used together with the help of hybrid energy management configurations. Rule-based,
optimization-based, and artificial intelligence-based energy management strategies
for hybrid energy storage systems are discussed in Chap. 9. The main parameters
are adaptability, reliability, and robustness. Computational complexity is a driving
parameter for using these techniques in online or offline mode.
The global supercapacitor market is expected to grow at a rapid rate in the
coming years owing to the rising demand for supercapacitors in various applica-
tions. These supercapacitors are available in varying sizes, capacitances, voltage
ranges, etc., and are sometimes tailor-made for certain applications. At present, the
Preface xi

market is currently dominated by a few major players such as Murata Technology,

Maxwell Technologies, Eaton Corporation, Nippon Chemi-Con, Nesscap among
others. Chapter 10 deals with the trends in the supercapacitor market and also sheds
light on the properties of supercapacitor cells and modules manufactured by key
market players.
The last Chap. 11 provides a brief insight into the commercially available super-
capacitors and the applications in various fields like wearable electronics, portable
electronic devices, transportation, industrial applications, military, defense, and
national security, renewable energy sector, power electronics, communication, arti-
ficial intelligence, internet of things, cyber-physical system, soft robotics, comple-
mentary metal-oxide-semiconductor, very-large-scale integration, memory, medical
and healthcare, buildings, gas sensors, and futuristic applications along with few
selected manufactures for the said applications around the globe.
The editor and authors hope that readers from materials science, engineering, and
technology will be benefited from the reading of these high-quality review articles
related to the characteristics of materials and their selections used in supercapacitor.
This book is not intended to be a collection of all research activities on composites
worldwide, as it would be rather challenging to keep up with the pace of progress in
this field. The editor would like to acknowledge many material researchers, who have
contributed to the contents of the book. The editor would also like to thank all the
publishers and authors for permitting us to use their published images and original
work. I also take this opportunity to thank Viradasarani, Zachary, and Viradasarani
Natarajan, and Adelheid Duhm, and the editorial team of Springer Nature for their
helpful advice and guidance.
There were lean patches when I felt that 1 would not be able to take time out and
complete the book, but my wife Sutapa, and my little daughter Srishtisudha, played
a crucial role to inspire me to complete it. I hope that this book will attract more
researchers to this field and that it will form a networking nucleus for the community.
Please enjoy the book and please communicate to the editor/authors any comments
that you might have about its content.

Kanpur, India Kamal K. Kar

Contents

1 Introduction to Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Ravi Nigam, Prerna Sinha, and Kamal K. Kar
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 Differences Between Other Energy Storage
Devices and Supercapacitors . . . . . . . . . . . . . . . . . . . . . . 2
1.2 History of Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Faradaic and Non-faradaic Processes . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Types of Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.1 Electric Double-Layer Capacitor (EDLC) . . . . . . . . . . . 6
1.4.2 Pseudocapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.4.3 Asymmetric Supercapacitors . . . . . . . . . . . . . . . . . . . . . . 11
1.4.4 Hybrid Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4.5 Quantum Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.5 Hybrid Energy Storage Systems (HESS) . . . . . . . . . . . . . . . . . . . . . 13
1.6 On-Chip Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.7 Components of Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.7.1 Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.7.2 Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.7.3 Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.7.4 Current Collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.8 Electrochemical Characterization Techniques . . . . . . . . . . . . . . . . . 31
1.8.1 Electrochemical Impedance Spectroscopy . . . . . . . . . . . 31
1.8.2 Cyclic Voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.8.3 Galvanostatic Charge/Discharge . . . . . . . . . . . . . . . . . . . 32
1.8.4 Electrode System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.9 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2 Supercapacitor Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Prerna Sinha and Kamal K. Kar
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2 Materials Used in Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . 41

xiii
xiv Contents

2.3 Types of Charge Storage Mechanisms . . . . . . . . . . . . . . . . . . . . . . . 42

2.4 Types of Supercapacitor Assembly . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.4.1 Symmetric Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . 45
2.4.2 Asymmetric Supercapacitors . . . . . . . . . . . . . . . . . . . . . . 59
2.4.3 Battery Supercapacitor Hybrid Devices . . . . . . . . . . . . . 69
2.5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3 All Types of Flexible Solid-State Supercapacitors . . . . . . . . . . . . . . . . . 81
Souvik Ghosh, Prakas Samanta, and Tapas Kuila
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.2 Flexible SCs Device Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2.1 Current Collector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2.2 Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2.3 Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.3 Device Fabrication Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.1 Pencil Drawing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.2 Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.3.3 Ink-Jet Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.3.4 Dip Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.4 Types of Flexible SCs Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.4.1 Stretchable SCs Device . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.4.2 Compressible SCs Device . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.4.3 Transparent SCs Device . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.4.4 Flexible Micro-SCs Device . . . . . . . . . . . . . . . . . . . . . . . 105
3.5 Various Design of FSSCs Devices . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.5.1 Sandwiched-Type Device . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.5.2 Planer-Type Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.5.3 Fiber-Type Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.6 Evaluation of Flexible Solid-State SC Device Performance . . . . . 108
3.6.1 Cell Capacitance Measurement . . . . . . . . . . . . . . . . . . . . 109
3.6.2 Internal Resistance Calculation . . . . . . . . . . . . . . . . . . . . 110
3.6.3 Energy and Power Calculation . . . . . . . . . . . . . . . . . . . . . 111
3.6.4 Cycle Life Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4 Conducting-Polymer-Based Supercapacitors . . . . . . . . . . . . . . . . . . . . . 119
Pallab Bhattacharya
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.2 Conducting Polymers and Their Characteristics . . . . . . . . . . . . . . . 123
4.2.1 Polyacetylene (PA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.2.2 Polyaniline (PANI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.2.3 Polypyrrole (PPy) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2.4 Polythiophene (PTh) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2.5 Poly(Ethylenedioxythiophene) (PEDOT) . . . . . . . . . . . . 126
Contents xv

4.2.6 Other Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . 126

4.3 Synthesis of Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.3.1 Chemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.3.2 Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . 129
4.3.3 Metathesis Process of Polymerization . . . . . . . . . . . . . . . 130
4.3.4 Emulsion Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.3.5 Inclusion Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.3.6 Solid-State Polymerization . . . . . . . . . . . . . . . . . . . . . . . . 131
4.3.7 Plasma Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.3.8 Matrix Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.4 Electrical Properties of Conducting Polymers . . . . . . . . . . . . . . . . 132
4.5 Electrochemical Supercapacitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4.5.1 Fabrication Procedures of Supercapacitors . . . . . . . . . . . 139
4.5.2 Performance Characteristics and Parameters . . . . . . . . . 140
4.6 Conducting-Polymer-Based Supercapacitor . . . . . . . . . . . . . . . . . . 141
4.6.1 PANI-Based Supercapacitors . . . . . . . . . . . . . . . . . . . . . . 142
4.6.2 PPy-Based Supercapacitor . . . . . . . . . . . . . . . . . . . . . . . . 146
4.6.3 PEDOT-Based Supercapacitor . . . . . . . . . . . . . . . . . . . . . 148
4.6.4 PTh-Based Supercapacitor . . . . . . . . . . . . . . . . . . . . . . . . 151
4.6.5 Conducting-Polymer-Based Composites . . . . . . . . . . . . 153
4.7 Conclusion with Challenges and Possibilities . . . . . . . . . . . . . . . . . 154
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
5 Electrode Material Selection for Supercapacitors . . . . . . . . . . . . . . . . . 159
Alka Jangid, Kapil Dev Verma, Prerna Sinha, and Kamal K. Kar
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
5.2 Functions of Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.3 Characteristics Required for Electrodes . . . . . . . . . . . . . . . . . . . . . . 162
5.3.1 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.3.2 Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.3.3 Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
5.3.4 Surface Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
5.3.5 Wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
5.3.6 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
5.3.7 Cycling Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
5.3.8 Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.4 Performance of Materials Used as Electrodes . . . . . . . . . . . . . . . . . 169
5.4.1 Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.4.2 CNT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.4.3 Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
5.4.4 Carbon Aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
5.4.5 Carbon Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
5.4.6 Carbide Derived Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.4.7 Anodized Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.4.8 Metal Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
xvi Contents

5.4.9 Metal Nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

5.4.10 Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
5.4.11 Composite Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
5.5 Electrode Materials Used in Commercial Supercapacitors . . . . . . 179
5.6 Emerging Electrode Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.7 Methods of Fabricating Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . 185
5.8 Electrode Material Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5.8.1 Objectives for Electrode Material Selection . . . . . . . . . . 188
5.8.2 Screening Using Constrains . . . . . . . . . . . . . . . . . . . . . . . 188
5.8.3 Governing Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
5.8.4 Material Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
5.8.5 List of Material Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.9 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
6 Separator Material Selection for Supercapacitors . . . . . . . . . . . . . . . . 201
Alka Jangid, Kapil Dev Verma, Prerna Sinha, and Kamal K. Kar
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
6.2 Functions of Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
6.3 Commercial Manufacturers of Separators . . . . . . . . . . . . . . . . . . . . 204
6.4 Characteristics Required for Separators . . . . . . . . . . . . . . . . . . . . . . 205
6.4.1 Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
6.4.2 Permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
6.4.3 Chemical Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
6.4.4 Dimensional Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
6.4.5 Wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
6.4.6 Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
6.4.7 Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
6.4.8 Surface Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
6.5 Performance of Various Materials Used for Making
Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
6.5.1 Polymer Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.5.2 Woven Ceramic Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.5.3 Woven Glass Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
6.5.4 Composite Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
6.5.5 GO Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
6.5.6 Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
6.5.7 Eggshell Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
6.5.8 Piezoelectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
6.6 Design of Separator in Supercapacitors . . . . . . . . . . . . . . . . . . . . . . 216
6.7 Separator Material Selection for Supercapacitors . . . . . . . . . . . . . . 216
6.7.1 Objectives for Selection of Separator Material . . . . . . . 218
6.7.2 Screening Using Constrains . . . . . . . . . . . . . . . . . . . . . . . 218
6.7.3 Governing Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.7.4 Material Indexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
 Another Random Document on
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The Project Gutenberg eBook of The Great
Implication
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and most other parts of the world at no cost and with almost no
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Title: The Great Implication

Author: Stanley R. Lee

Illustrator: Virgil Finlay

Release date: March 22, 2024 [eBook #73231]

Language: English

Original publication: New York, NY: Ziff-Davis Publishing Company,

1961

Credits: Greg Weeks, Mary Meehan and the Online Distributed

Proofreading Team at http://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK THE GREAT

IMPLICATION ***
 The GREAT IMPLICATION

By STANLEY R. LEE

Illustrated by FINLAY

Pendelton outlined an experiment to test the existence

of the God-idea. The question then became obviously:
was the experiment Pendelton's idea—or God's?

[Transcriber's Note: This etext was produced from

Amazing Stories August 1961.
Extensive research did not uncover any evidence that
the U.S. copyright on this publication was renewed.]
Was there something contagious about ignorance? Pendelton
wondered aloud that day. Was it inevitable, was it in the air the
same as ideas were? He thought that might be the answer because
what else could explain the fact that a couple of accomplished
physicists were about to fall into a time-honored trap that was
already gorged with old, rancid science fiction writers; and not only
rancid, but crooked: they accepted pay for writing about a subject
they knew nothing of and wasn't that stealing?
Pendelton wasn't actually trying to be obnoxious. In fact he liked to
make good impressions. He smiled a lot, for instance. And he kept
his hands in his pockets so he wouldn't point. He had a peculiar
blunt-subtle mind, half of which could split hairs with a Jesuit while
the other half couldn't distinguish between a pat on the back and a
punch in the jaw.
He rolled right along, smiling and telling them they knew nothing
about time travel. Nothing. They were babes in the temporal woods!
Having a time machine under construction meant that they were in
the possession of what he referred to as mathematical conceptuosity
plus above average hardware skills. But that didn't necessarily raise
them above the level of the science fiction writers when it came to
applications. Or the editors. The readers too, for that matter, all
blithely playing their cosy little after-the-fact parts in a fantastic
world-wide conspiracy of ignorance.
Blackburn and Shaheen, of course, thought he was out of his mind.
They'd only agreed to listen to him because he had a letter from the
Humanities department head, that and a wild, intense expression on
his face which made them think it would be easier to hear him out
than throw him out, so they sat at their back-to-back desks glancing
at each other occasionally while Pendelton rambled on about the
Great Implication and how it was one day going to separate the
logical men from the paradoxical boys—and after about twenty
minutes of this they were actually listening to him.
So that six months later Blackburn and Shaheen got into a violent
argument in the office of the university president, Dr.
Freylinghuysen, the two mathematical-physicists completely unable
to agree on the color of a girl's dress, a girl they'd not only never
seen in their lives before ten that morning, but one who
subsequently leveled charges of assault and malicious mischief and
attempted rape at the university along with a civil suit for $50,000.
Although it had to be said in Pendelton's defense that it wasn't his
fault. It was Chaplain Rowan who sprinted across Voltaire Mall and
attempted to strip Miss Ethel Chattinger, purely in the interest of
science of course but the young lady couldn't quite see it that way,
especially since Rowan, the university chaplain, had gotten away
with quite a swatch, a large jagged piece of knit woolen dress which
he later on triumphantly deposited on Dr. Freylinghuysen's desk,
only to find that he hadn't really proved anything at all other than
that perhaps Miss Chattinger—otherwise known as the either/or
proposition—was not a quick change artist and the Humanities
department's 35-year-old prodigy of an air conditioner repairman
Leopold Pendelton wasn't a practical joker.

"The first thing," Pendelton said that first day, "is for you to forget
about paradox. Paradox has nothing to do with time travel. Nothing.
It's a monkeying around with words for purposes of profit and it has
no place in the office of two experimental physicists. Anyone who
answers an honest question with a paradox is a guaranteed shifty
character and the chances are he's writing on the sly."
Preoccupied with not sounding obnoxious, Pendelton missed
Blackburn's ostentatiously bored expression, didn't notice the
enormous sarcastic attention that Shaheen was giving him. Instead,
he remarked: "Feel free to interrupt me with questions. I want to
finish off paradox so we can get on to the Great Implication. Will
that be a satisfactory procedure?" He hovered over the desks staring
at them with big eyes until they slowly nodded their heads up and
down.
"Okay. Now. A man travels in time," he said. "He travels in time and
fifty million years ago he steps on a moth. Fantastic. You wouldn't
believe the effect one humble moth could have! The man returns to
the present and finds to his guilty astonishment that the Empire
State building is now flying the Bolivian flag and gargoyles are
sticking out of the 79th floor. This is cute so be careful of it. Boy
meets moth, boy loses moth—gargoyles! Except that all those not
completely devoid of common sense or debauched by poetic license
would know that if the gargoyles were there they were there before
he went back in time. His own body is a part of a continuum of
which those gargoyles are a prior sequential segment; his entire life
is so inextricably wrapped up in those gargoyles that he couldn't
possibly be surprised by them, or by any other change he'd caused.
As he returned to the present his memory would alter. To take any
other view of this—to close your eyes and hide behind paradox—is
going to get us all in trouble because you've got yourselves a real
time traveler now and it's about time you started thinking about
these things."
("Well why didn't you say so," Blackburn murmured. "Be glad to
think about it, give it every consideration. We'll be in touch."
"I don't think he heard you," Shaheen said.)
"I won't even bother discussing the suicide-by-killing-old-grandpa
myth," Pendelton buzzed on with a great deal of imperturbability,
"other than to point out there is no such thing as negative feedback
as applied to human beings. I realize that's only a small nuance. But
then, take care of the nuances and the breakthroughs will take care
of themselves, I always say."
("Oh Lord," Blackburn whispered.)

"Another small point. I hate to verbalize the obvious like this but it
clears the ground, don't you think? I realize you two might like to
traipse back through time and have a friendly chat with, say, Mike
Faraday. But that's exactly what you can't do. You know a little too
much about time machines. He'd pick your brains in half an
afternoon and beat you back to your own office. As I say that's only
a nuance. It's a nuance that eliminates 75% of all time travel science
fiction ever written but that's still only a nuance, wait till I get to the
Great Implication."
It was a curious word for him to have used—nuance—because six
months later in Dr. Freylinghuysen's office Blackburn and Shaheen
were to tangle over the nuance of blue versus green, a matter of
observation which compared in subtlety to apples versus bananas,
Shaheen saying heatedly: "The dress was blue. I'm not color blind
and I have twenty-twenty vision. I'll stake my reputation as an
experimental physicist on it." Blue! And this was a lucid well defined
statement of his position, a statement rivaled in lucidity only by that
of Blackburn who had in all sincerity to insist that the dress was blue
—but only 10:31 that morning at which time it turned green; and if
that wasn't bad enough a panting red faced chaplain Rowan had to
dash in, carefully locking the door behind him and taking out a huge
swatch of dress which he plunked down on the desk shouting:
"Green, green, green! Green as the envious devils of hell! Green I
say! Green before, green after, green for eternity!"
"I think, in spite of all," Blackburn remarked, "you've managed to
find a way."
"No, but that's interesting," Shaheen said. "Semantically, anyway. I
will did. Curious."
"A grammatical revolution!" Pendelton was telling them that first day.
"I do, I did do, I will do. I have done, I will have done. I do, I did
do, I will do. I have done, I will have done, I should have done, I
will did! They're all the same now! So you see, I'm not really wasting
your time. The future and the past are now united in a fantastic
tenseless embrace. At some time in the future I can in the past save
Caesar's life. Thus, there being no more future and past, how can I
be wasting your time?"
"More than curious," Pendelton replied. "Practical. The Greeks as you
may know thought that no man could be sure he had a happy life
until it was over. I on the other hand assert that Caesar's
assassination is still in doubt because of the future-past equivalence,
that he has not yet successfully crossed the Rubicon, that he is still
swimming to the Alexandrian lighthouse, that he is not yet emperor
of a Rome that has not yet fallen! Not emperor and yet ... emperor.
Not yet fallen and yet ... fallen and gone like—what? The wind? No,
not even the wind. Nothing is gone, it's all still there moiling and
seething around in temporal abeyance. Waiting to be resolved! Give
me a time machine and I can mold every second of Caesar's
existence and, incidentally, by extension, my own. The Greeks
therefore were wrong. A man can no longer be sure he was happy
even when he's dead!"

Blackburn leaned back in his chair and inquired blandly: "Did we get
to the great implication yet?"
"If you were listening we did," Pendelton answered. "Elementary
theology: if man's fate is determined there must of necessity be a
Determiner whom we will call for the sake of convention, God.
Determinism without a God, needless to say, is eighteenth century
mechanistic twaddle. But suppose now that a man can determine his
own fate? Run it through your machine again and again until he gets
it down the way he wants it with all degrees of freedom and
irrespective of his merit or karma or sinlessness or however our
cosmic report cards are supposed to be made out? In that case man
becomes his own determiner, the individual conscious mind becomes
the deity and that which we have heretofore referred to as God
becomes what is known as an outdated archetype."
"Good God," Shaheen said.
"But spelled with a small g," Pendelton replied. "That is the Great
Implication."
"You mean to say he was proposing to disprove God's existence?"
Dr. Freylinghuysen said to them that day. "And with university
equipment? Don't you gentlemen realize I have trouble enough with
the trustees as it is?" And Chaplain Rowan, who had long since lost
the ability to react spontaneously—slipping back and forth almost on
schedule between catatonia and St. Vitus dance—said: "Why are you
sitting there doing nothing? Why isn't the city being scoured? If that
dress isn't proof enough for you, that man is loose somewhere with
colored motion pictures of the whole thing. What more do you
want?" "A little illumination is all," Freylinghuysen replied. "All I've
heard so far is some rather loose discussion about free will and
determinism and it wasn't very convincing. Didn't anyone bother to
point out to this Leopold Pendelton that you can't prove or disprove
anything about your own determined existence since the proof or
disproof itself could be determined?" "Yes," Blackburn answered.

Blackburn had thought over the Great Implication for about two
seconds. "You have been wasting our time," he said. "You cannot
actively disprove determinism because the disproof—the experiment
itself—could be a part of your own determined existence, arranged
by your Determiner. God might, for instance, allow the experiment to
be successful merely to test your faith in Him, the same way he
allowed you to get the idea in the first place."
An odd smile crossed Pendelton's face. "You really think so?" he
asked. "You figure He'd try and cross me up like that? Let's go back
and take this a step at a time. Specifically, why can't I play God with
Caesar's life?"
"Wouldn't prove anything," Shaheen said. "God could have
determined you in the selection of Caesar's name. The change would
therefore be His doing, not yours, it would still be old God playing
God with Caesar's fortunes."
"But it doesn't have to be Caesar. That was only an example, it could
be anyone. Control anyone's destiny, anyone at all, and you've
proven the point. We could select our man by means of a computer,
by random sampling over which only the physical laws of the
universe had control, thus eliminating determinacy in the selection."
"But God could alter the laws of chance. After all, they are His laws.
A second-rate miracle would force you into selecting His man."
"You mean," Pendelton asked, "that if I selected a name every
morning at 10:04-1/2 God would do a miracle at the same time?"
"Ye-es," Shaheen answered.
"But if one morning I changed my mind and waited until a quarter
past two to select the name, He'd hold off and wait for me, wouldn't
He?"
There was rather a long silence.
"He couldn't very well perform His miracle until I'd picked my name,
could He?"
"Hmmmmm," Shaheen said.
"And if I decided to wait until 3:15, He'd have to wait too. And if I
decided not to pick a name we'd do without a miracle that day. The
fact is, I'd be telling Him what to do. Put me in the possession of a
random sampling computer and a time machine and I, Leopold
Pendelton, would be the bigger God!"
"And the point was well taken," Shaheen had to admit, pouring off
some of Dr. Freylinghuysen's ice water. "We could for example use a
computer to select at random any one of all the phone books in the
United States, then a page in that one book, then a line. That one
name would then truly be randomly selected." "Assuming of course,"
Blackburn said, "that you had first used the computer to randomly
select the country whose phone books were to be used." "And also
the particular year's edition," Freylinghuysen murmured. "It was
fairly ingenious," Shaheen said, "especially when you consider that
knowing how to do it meant you didn't have to bother. It was
enough just to know we could. The only point that needed
experimental verification was: could we in fact alter the past?
Change something, anything at all and everything else followed,
including the death of God." "You mean the death of the concept of
God," Blackburn added. "Ah yes," Shaheen answered, glancing
guiltily at Chaplain Rowan. "The question was, what were we going
to change and how were we going to know it changed?"

Chaplain Rowan had been Shaheen's idea.

It had occurred to him one day as he and Blackburn were crossing
the campus and he had observed to his colleague that things were
looking bad for God. "It's every man for Himself," Blackburn had
replied. "If I'm not mistaken that's one of His own laws. After all,
who invented survival of the fittest?"
"Seriously," Shaheen said. "A, we've got a time machine. B, having
A, there's no reason that I can see why we can't change the past.
And C, if we do, well, they'll be using cathedrals for bowling alleys."
"Maybe now we'll see what kind of a loser He makes."
"Look here Blackburn, you needn't parade your atheism so
ostentatiously. I'm well aware of it. In fact that's what's bothering
me. You're an atheist whereas I ... well, I never did make up my
mind about God. That's not very astute of me, I suppose, but I
haven't. I'm betwixt and between, and so I was wondering if it
wouldn't be only fair to have a representative of the other side in on
this."
For a few seconds there was only the sound of their shoes on the
bluestone walk that threaded across the stunted fall grass of the
campus.
"Fair? You're using the word fair in connection with a scientific
experiment?"
"Only because its outcome seems so obvious to us. We have strong
preconceptions and because of them we're liable to overlook
possibilities. I think we should have someone with us who expects
the experiment to work out differently, someone who believes
implicitly in His existence."
Blackburn thought about it as they rose in the Physics building
elevator. "Well why not," he said, smiling in his peculiar catastrophic
fashion. "You and I have an aggregate of 70 years experience in the
laboratory, why not bring in a clergyman to check our techniques, be
in keeping with the general tone of this whole thing. Hell, yes!"

Later that day Brokley L. Rowan listened with a frozen serious face
as they declared their intentions to him. A young and conscientious
man who spent a great deal of time telling budding undergraduate
physicists that God was every bit as ubiquitous as Planck's constant,
he listened without one word of complaint, not protesting that they'd
put him in a theologically impossible position, a position in which the
only two alternatives were to either refuse to look after His interests
or else participate in a piece of sacrilegion the purpose of which was
to demonstrate that the first alternative was not a valid one. And
when he met Pendelton a week later in the Physics building,
Pendelton told him: "You and I'll get along fine. I want it to be
clearly understood that I have nothing against the church."
Chaplain Rowan took his glasses off and began cleaning them.
"And there's absolutely nothing for you to worry about. Even if we
do disprove Him there'll always be doubters. You count on a certain
percentage of people who won't believe our evidence. You'll get all
the skeptics showing up on Sunday morning as usual."
Shaheen spoke with compensating soberness. "What I thought we'd
do," he said, "is hold daily discussions on strategy. That way you can
question any assumptions we make, check our logic, object as you
see fit."
"What we're trying to be about this thing is fair," Blackburn said.
"Of course," Rowan replied.
"Now the first point I wish to raise," Shaheen said, "is in regard to
the gargoyles. They're very important, the gargoyles."
Chaplain Rowan sat down on the window sill.
"If the gargoyles are a product of the past-change," Blackburn put
in, anticipating the problem, "how are we going to know it? How are
we going to perceive the change? That the question?"
"Aren't you going to ask what gargoyles have to do with this?"
Pendelton said to Chaplain Rowan.
"I don't believe I will," Rowan replied, lighting up his pipe.
"The answer," Blackburn said, "is this: the experimental observer, not
the one who takes the time trip, must be standing in plain view of
the building. He must be expecting gargoyles to appear. When they
do, he will not be tempted to call the phenomenon a miracle. When
the gargoyles suddenly pop out—in apparent defiance of various
physical laws—he can intelligently conclude that a specific time
experiment has been performed and that a change in the past has in
fact occurred, a conclusion that will restore the appearance of the
gargoyles to the realm of non-miraculous events."
"Then the change we make must be so specific, must have such
easily deducible consequences, that we'll be able to anticipate our
equivalent of the gargoyles."
"Sort of like an either/or proposition," Blackburn said. "Find an event
that can go only one of two ways. Switch this event from its already
proceeding alternative to the bypassed, the not-used, the
temporally-no-longer-existing possibility. The independent observer,
watching the one disappear and the other take its place, will then
know that the past has changed. It will prove the principle that man
can determine his fate and is therefore alone."
Rowan nodded, chewing on his pipe. "I'll wait'll it's over, though," he
said.
President Freylinghuysen filled a glass with ice water.
"'You cannot take God's photograph,'" he said. "Surrealism. Sheer
surrealism. Was he smiling when he said it?"
"Of course he was smiling," Blackburn replied bleakly. "He's always
smiling."
"After making man's first trip through time," Freylinghuysen said,
"he stepped out of the physics building to find your either/or
proposition yelling its head off and Rowan here standing in the
center of Voltaire Mall with half a dress in his hand. So I'm surprised
he was smiling. But what was he talking about?"
"And why," Shaheen said, "did he push Blackburn into the shrubbery
and run off with the camera? I don't understand that at all." He
turned away. "Oh, I suppose there's plenty I don't understand."
"What about on the trip," Freylinghuysen offered. "Could something
have happened—"
"What?" Blackburn replied. "He went back in time exactly one hour.
He was to walk to Ethel Chattinger's apartment." ("That fabulous
woman," Freylinghuysen murmured.) "All he had to do was spill india
ink over one of the two new dresses she'd bought. Apparently, the
most trying problem of her recent existence was to decide which of
the two to wear to her Spanish coach this morning. But he'd be
ruining the dress he'd already seen her wearing an hour later on the
Mall."
"And that's as subtle a way of getting a girl's dress off as you're
likely to find," Freylinghuysen remarked. "Although tearing them off
has its points too," he added, looking at the ceiling.
"Then what could have gone wrong?" Blackburn asked.
"As far as I can see," Freylinghuysen answered, "the only flaw in this
experiment was the scientists themselves. Your observations
positively reek with subjectivity. To Rowan, the dress was green,
always green. This just happens to prove Rowan's original belief,
namely that the past can't be altered and therefore He exists. The
atheist on the other hand," he glanced at Blackburn, "has seen what
looks like a miracle—a material object changing a basic physical
quality right before his eyes. Strangely enough this miracle goes to
prove that there are no such things as miracles. Blackburn's case is
also proven. You saw what you wanted to. Take Shaheen here. He
was positive the dress was blue all the time—until he saw Rowan's
experimenter's sample—and so now he's back at his old stand: the
fence."

There was an embarrassed silence, since two scientists had quietly

to own up to the crime of subjectivity in the laboratory while the
theologian had to somehow dispose of a piece of spurious rationality
that might be forgiven but would never be forgotten.
And then the door opened and a smiling face appeared.
"What'd everyone run away for?" Pendelton said.
The president was the first to recover.
"Everyone will please remain seated and calm," he said to the
others.
"Calm be damned!" Blackburn answered. "This one has a punch in
the nose coming—and where the devil's my camera?"
"Should have told me you were going to take pictures," Pendelton
said, gingerly handing it over. "Would have saved us a lot of trouble.
And if you're interested in facts it wasn't me that snatched it, it was
a law student. I guess he figured it might have some legal use.
There's some interesting footage in it starring Chaplain Rowan and a
disturbing young creature named Ethel." He tossed a yellow box on
the desk. "You see chaplain, I'm not anti-clerical after all."
Rowan's eyes flicked from Pendelton to the box and back again.
"That's the film?" he said.
Pendelton nodded.
Shaheen wet his lips. "You develop it?" he said.
"Yep."
"He's playing with us," Freylinghuysen said. "Well, I can't say I
blame him. After all, how many times in a man's life does he get a
scoop like this? Look," he said, turning to Pendelton, "there seems to
have been some disagreement about what happened on the Mall
this morning. We've got eyewitnesses proving anything you want.
You've seen the film, maybe you'd like to tell us." He thumbed the
desk top, trying to think of a decorous way to phrase it. "Oh hell, is
He or isn't He?"
Pendelton pursed his lips and thought a moment.
"I'm not in a position to say at this time," he said.
Four of the five men sat frowning because, in conversations with the
fifth, time had continually to be allowed for recovering. Then
Rowan's eyes brightened and he jumped up.
"I take it you mean by that the dress was green all the time," he
said, giving a rhetorical answer.
"But don't start ringing bells over it," Pendelton said, smiling. "I
ought to explain that it had to be green. Not because there's a God,
but because it had to. Couldn't be anything else. Except always blue,
of course. Always blue, always green, but nothing in between. It
rhymes." He shrugged his shoulders. "Because when you change the
past, why then you change the past and that includes cameras and
film which are often also a part of the past."
"Green all the time," Rowan said, looking around at the others.
"Green."
"Green and immaterial!" Pendelton replied. "Green and irrelevant,
green and so what! We took the wrong approach. I didn't realize it
until I saw Blackburn getting it down on film. Film is part of the past,
so it changes. But our heads are also a part of the past. They
change too." There was a flash of white teeth against his flushed
face as he said: "Depressing, isn't it?"
"Wait a minute," Shaheen said.
"But it's true. The man watching the gargoyles pop out of the
Empire State Building would not have noticed anything. Quite
suddenly the gargoyles would always have been there. The human
mind can be toyed with as though it were a piece of film, a coating
of silver nitrate crystals on celluloid. It's positively degrading!"
"Wait a minute," Shaheen said, pressing his head between his fists.
"Something's wrong. You spilled ink on one of that girl's dresses.
The blue one apparently."
"I spilled ink on a co-temporally-earlier edition of the dress the girl
was wearing on Voltaire Mall," Pendelton said, "but can you
guarantee she wasn't wearing the green dress to begin with? You
can't. Now I'll say this slowly. If you change the past then you can
have no memory of what it was before you changed it and therefore
you can never prove that you have changed it." He sighed and sat
down. "I'd like that to be known as Pendelton's Exclusion Principle."
"It's a shame really," Rowan remarked, "you went to an awful lot of
trouble."
"Well," the president said slowly, "I don't know but that it might be
better to keep physics and metaphysics apart after this. Like church
and state. Metaphysical questions, after all, are those that don't
have answers."
A frown passed briefly over Pendelton's countenance. "Wait a
minute," he said. "As I recall it, I said something about the wrong
approach, I don't remember saying the jig was up. As far as I'm
concerned, we've only tried the past so far, we haven't scratched the
future.
"Take the year 2068 for example," Pendelton said, smiling at them,
trying not to sound obnoxious. "If existence is really determined the
events of that year are already written down ... sort of."
He suddenly whirled on Rowan. "There is no question of God
changing his mind between now and then since there is nothing that
could possibly happen between now and then that would surprise
Him, give Him a reason for changing His mind, because if He did He
would be violating His own definition which includes absolute
knowledge of all events past and future."

Rowan, immovable, stared back at him.

"But we need two time machines," Pendelton resumed. "I know,
these things are expensive but if you're really interested you'll ram it
past the trustees."
"Stop!" Freylinghuysen said. "No, go ahead. Damn!"
"I won't go through this again," Rowan shouted, rising. "All he's
going to do is play more tricks with words!"
"Won't hurt to listen to him," Freylinghuysen replied.
"Now we send one time machine back to 1868 by means of the
other. Then one of us travels to 2068 from 1868 while another goes
to that allegedly same year 2068 from the present, from 1968. See
what I'm getting at?"
Shaheen slowly nodded his head and then closed one eye.
"If there's free will," Blackburn mumbled, "they won't meet."
"Let's look for exclusion principles," Freylinghuysen commented,
putting the balls of his fingers together and staring at the ceiling.
Rowan, ignored, watched them for a few seconds and sat down
again. After a while he began to wonder how many experiments it
would take before Pendelton found the proof he was looking for.
THE END
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