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Published on 08 August 2017 on http://pubs.rsc.org | doi:10.1039/9781788011891-FP001
From Synthesis to Applications

Biobased Smart Polyurethane Nanocomposites
.

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Smart Materials
Series editors:
Hans-Jörg Schneider, Saarland University, Germany
Mohsen Shahinpoor, University of Maine, USA
Titles in this series:

1: Janus Particle Synthesis, Self-Assembly and Applications
2: Smart Materials for Drug Delivery: Volume 1
3: Smart Materials for Drug Delivery: Volume 2
4: Materials Design Inspired by Nature
5: Responsive Photonic Nanostructures: Smart Nanoscale Optical Materials
6: Magnetorheology: Advances and Applications
7: F unctional Nanometer-Sized Clusters of Transition Metals: Synthesis,
Properties and Applications
8: M echanochromic Fluorescent Materials: Phenomena, Materials and
Applications
9: Cell Surface Engineering: Fabrication of Functional Nanoshells
10: Biointerfaces: Where Material Meets Biology
11: Semiconductor Nanowires: From Next-Generation Electronics to
Sustainable Energy
12: Supramolecular Materials for Opto-Electronics
13: Photocured Materials
14: Chemoresponsive Materials: Stimulation by Chemical and Biological
Signals
.
15: Functional Metallosupramolecular Materials

16: Bio-Synthetic Hybrid Materials and Bionanoparticles: A Biological
Chemical Approach Towards Material Science
17: Ionic Polymer Metal Composites (IPMCs): Smart Multi-Functional
Materials and Artificial Muscles Volume 1
18: Ionic Polymer Metal Composites (IPMCs): Smart Multi-Functional
Materials and Artificial Muscles Volume 2
19: Conducting Polymers: Bioinspired Intelligent Materials and Devices
20: Smart Materials for Advanced Environmental Applications
21: Self-cleaning Coatings: Structure, Fabrication and Application
22: Functional Polymer Composites with Nanoclays
23: Bioactive Glasses: Fundamentals, Technology and Applications
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24: Smart Materials for Tissue Engineering: Fundamental Principles

25: Smart Materials for Tissue Engineering: Applications
26: Biobased Smart Polyurethane Nanocomposites: From Synthesis to
Applications
.
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Biobased Smart Polyurethane

Nanocomposites
From Synthesis to Applications
By
Niranjan Karak
Tezpur University, India
Email: karakniranjan@gmail.com
.
Published on 08 August 2017 on http://pubs.rsc.org | doi:10.1039/9781788011891-FP001 View Online
Smart Materials No. 26
Print ISBN: 978-1-78801-180-8

PDF ISBN: 978-1-78801-189-1
EPUB ISBN: 978-1-78801-200-3
ISSN: 2046-0066
A catalogue record for this book is available from the British Library
© Niranjan Karak 2017
All rights reserved
Apart from fair dealing for the purposes of research for non-commercial purposes or for
private study, criticism or review, as permitted under the Copyright, Designs and Patents
Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may
not be reproduced, stored or transmitted, in any form or by any means, without the prior
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Preface
Polyurethane (PU) is one of the most versatile industrially important petro-

chemical-based products and finds applications in almost all sectors, such as
packaging, furniture, bedding, building, construction, coatings, adhesives,
sealants, elastomers, appliances, automobile, footwear, smart materials, bio-
medical, etc. However, the depletion of petroleum oil pools across the globe
and the stringent environmental rules and regulations as a result of global
warming are prompting the society to use biobased renewable resources to
sustain our civilization. Therefore, sustainable products based on such novel
polymeric material are the need of the hour to minimize our dependency on
fossil fuels and reduce the emission of greenhouse gases. Further, to meet
the demand of advanced applications, these biobased PUs need to be mod-
ified through novel and innovative techniques, as they are typically poor in
performance. Further, incorporation of branching in the chains enhances the
.
processing properties and other attributes of said polymers. Thus, biobased

hyperbranched PU has gained tremendous interest in recent times due to
its inherent advantages over conventional materials. Again, over the last two
decades or so, nanomaterials have appeared in every sphere of the materials
field because of their unique combination of properties. However, their size-
dependent nanostructural properties can only be explored if agglomeration can
be prevented. Therefore, in order to overcome their individual shortcomings,
as well as to exploit possible synergistic effects, these two unique categories of
materials must be combined together to tailor the structure and properties of
the resultant system. The approaches should also adopt the triple bottom line
concept, achieve a high carbon credit, and follow the tenets of green chemistry.
This book on “Biobased Smart Polyurethane Nanocomposites: From Synthe-
sis to Applications” is devoted to this endeavor. It is a book on biobased biode-
gradable PU nanocomposites with hyperbranched structural architecture and
their related technology. This book is written to provide the basic concepts

Biobased Smart Polyurethane Nanocomposites: From Synthesis to Applications
By Niranjan Karak
© Niranjan Karak, 2017
Published by the Royal Society of Chemistry, www.rsc.org
vii
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viii Preface
along with in-depth understanding on the subject. The purpose of the book
is to present biobased PU polymers with hyperbranched structural architec-
ture as the matrix for various nanomaterials to achieve nanocomposites with
unique combinations of properties, so that the demands on advanced sustain-
able polymeric products in fields such as active paints and coatings, shape
memory materials, self-healing materials, self-cleaning materials, biomateri-

als, packing materials, adhesives, construction materials, automobile mate-
rials, energy harvesting materials, appliance materials, etc. can be fulfilled.
Thus, this book will be useful for students at the graduate and postgraduate
level, including diploma holders in the field. Students in the fields of polymer
science and technology, chemical science and engineering, materials science
and engineering, medical science and technology, environmental science and
engineering, biochemical engineering, biotechnology, etc. can use this book
as a supplementary text material in the field of biobased PU nanocomposites.
The need for this book is very high at this moment, when the search for sus-
tainable products through ‘green’ approaches is at its peak.
Biobased biodegradable hyperbranched PU nanocomposites are one of
the most useful polymeric materials in the current scenario of advanced
materials for today’s civilized society. They are not only versatile owing to
their structural diversity, but they can also be produced by facile approaches.
Almost all sectors are currently in urgent need of environmentally friendly
sustainable materials and this book attempts to compile materials that fol-
low the principles of green chemistry with the triple bottom line approach
to realize a clean and safe environment for future generations. The book is
thus aiming to be a valuable document in this field for not only students and
.
teachers, but also the industry and R&D professionals.

The book covers basic concepts, preparation, characterization, properties,
processing, and applications of biobased biodegradable hyperbranched PUs,
different classes of nanomaterials, and their nanocomposites. It is divided in
two parts with a total of 10 chapters. The first part consists of three chapters
dealing with materials like PU, nanomaterials, and nanocomposites. Chapter 1
deals with the fundamentals such as the concept, classification, preparation,
modification, characterization, and properties of biobased PUs from raw
materials to applications. The second chapter covers the basic understand-
ing on various nanomaterials and includes classifications, preparation, mod-
ification, characterization, and properties, along with a few applications. The
last chapter of this part describes the concept, classification, preparation,
characterization, and properties of biobased PU nanocomposites with a brief
discussion of their applications. It focuses on the industrially relevant appli-
cations for such sustainable advanced polymeric materials. The second part
of this book elaborates on the applications of these novel polymeric materi-
als in various advanced fields. This part comprises seven chapters. Chapters
4 to 9 cover six important applications of this class of nanocomposites, while
the last chapter highlights other relevant applications as much as possible.
Chapter 4 deals with different types of paints and surface coatings required
for modern applications, where such materials can be used as binders.
It includes the concept, significance, classification, components, testing,
View Online
Preface ix
and analysis methods, properties, and applications of paints and coatings
and their current issues. Such unique smart polymeric materials are typi-
cally obtained from the most versatile polymers, such as PU, which exhibit
special structural contributions. Smart applications of PU like shape mem-
ory, self-healing, and self-cleaning are thus presented in Chapter 5, 6, and
7, respectively. All these chapters provide the basic understanding, signifi-

cance, classification, mechanism, testing methods, requirements, and appli-
cations on those topics. As PU is considered an important biomaterial and
health is currently the foremost issue, Chapter 8 discusses the importance,
definition, classification, biological characterization, fabrication, related
properties, and applications of biobased biodegradable PU nanocomposites
as biomaterials. Petrochemical-based polymeric packaging materials have
caused environmental havoc over the decades and, thus, in order to address
such detrimental issues, biobased biodegradable sustainable PU materials
are reaching the market as the need of the hour. Chapter 9 describes the
fundamentals, significance, testing and analysis, related properties, and
applications of a few commercially marketed packaging products based on
PU. The last chapter of the book is devoted to highlighting other important
applications of PU-based products in adhesives, automobiles, agriculture,
construction, electrical and electronic, energy, footwear, etc. A state of art
literature review on biobased biodegradable PU and its nanocomposites is
included in each chapter. The conclusions and future trends are highlighted,
and references are cited in each chapter to help the learner explore the topic.
This book is dedicated to my teachers and students, through whom I am
gaining knowledge on this subject. The author acknowledges with sincere
.
thanks all the writers, researchers, and publishers who actually performed and
published the work, advancing the understanding of the subject. The author
is also thankful to all his students, in particular the research scholars Dr Nan-
dini Dutta, Dr Jatishmoy Borah, Dr Sibdas Singha Mahapatra, Dr Suvangshu
Dutta, Dr Harekrishna Deka, Dr Uday Konwar, Dr Gautam Das, Dr Budhadev
Roy, Dr Rocktatpol Konwarh, Dr Hemjyoti Kalita, Dr Sujata Pramanik, Dr Shas-
wat Barua, Dr Beauty Das, Dr Suman Thakur, Dr Bibekananda De, Dr Satyabrat
Gogoi. Ms Rituporna Duarah, Ms Deepshikha Hazarika, Ms Aditi Saikia, Mr
Rajarshi Bayan, and Mr Gaurav Gogi, who carried out the laboratory work
and encouraged me to write this book. Special thanks go to my parents (Maya
Rani and Gopal Chandra), wife (Susmita), and son (Soham) for their blessing,
patience, and encouragement. The author also thanks the series editors and
the team members at the Royal Society of Chemistry for their whole-hearted
support, patience, and interest in this book. All the teachers, colleagues, and
friends, who directly or indirectly helped and encouraged me in various ways
to complete this book, are gratefully acknowledged. Last, but not the least, it
is the author's privilege to sincerely thank the Vice-chancellor of Tezpur Uni-
versity and the Heads of other organizations and institutes for allowing me to
use their libraries and other related facilities for the preparation of this book.
Niranjan Karak
Abbreviations and Symbols
AESO Acrylated epoxidized dL Deciliter(s)

soybean oil DMA Dynamic
AFM Atomic force microscopy mechanical
AgNP Silver nanoparticle analysis
AIBN Azobisisobutyronitrile DMAc Dimethylacet-
ASTM American society for amide
testing and materials DMF Dimethylforma-
BPO Benzoyl peroxide mide
bp Boiling point DMPA (bis-MPA) Dimethylol
cc Cubic centimeter(s) propionic acid
CD Carbon dot DMSO Dimethylsulfoxide
CEC Cation exchange capacity DNA Deoxyribonucleic
CHEM Cold hibernated elastic acid
.
memory DSC Differential scan-

cm Centimeter(s) ning calorimetry
CMC Carboxyl methyl cellulose e− electron(s)
CNSL Cashew nut shell liquid EDX Energy-dispersive
CNT Carbon nanotube X-ray
CTAB Cetyl tributyl ammonium EIS Electrochemical
bromide impedance
CVD Chemical vapor spectroscopy
deposition ESO Epoxidized
DB Degree of branching soybean oil
DBTDL Dibutyl tin dilaurate FESEM Field emission
DCO Dehydrated castor oil scanning electron
DP Degree of polymerization microscope
deg C/°C Degree centigrade FPU Fluorinated
dia. Diameter polyurethane

By Niranjan Karak
xi
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xii Abbreviations and Symbols

FTIR Fourier transform mm Millimeter(s)
infrared MMA Methylmethacrylate
g Gram(s) MMT Montmorillonite
GO Graphene oxide mol Mole(s)
GPC Gel permeation mp Melting point
chromatography Mn Number average molecu-

h Hour(s) lar weight
h+ Hole(s) Mw Weight average molecular
H-bonding Hydrogen bonding weight
HBI Hydrogen bond index MPa MegaPascal
HLB Hydrophilic–lipophilic MTT 3-(4,5-Dimethylthiazol-
balance 2-yl)-2,5-diphenyltetra-
HPLC High pressure liquid zolium bromide
chromatography MW Microwave
HPU Hyperbranched MWCNT Multi-walled carbon
polyurethane nanotube
HRTEM High resolution trans- N Newton
mission electron nm Nanometer(s)
microscopy NMR Nuclear magnetic
I Current resonance
IPA Isophthalic acid OMMT Organically modified
IPDI Isophorone montmorillonite
diisocyanate Pa Pascal
IPN Interpenetrating poly- PANi Polyaniline
mer network PBS Phosphate buffered saline
.
K Kelvin PCL Poly(ε-caprolactone) diol

kDa KiloDalton PCM Phase change material
kN KiloNewton PDI Polydispersity index
kV Kilovolt PDMS Polydimethylsiloxane
L Liter(s) PEG Poly(ethylene glycol)
lb Pound(s) PMDI Poly(diphenyl methane
LCA Life cycle analysis diisocyanate)
LDH Layer double hydroxide POSS Polyhedral oligomeric
LOI Limiting oxygen index silsesquioxane
LPU Linear polyurethane ppm Parts per million
m Meter(s) PTC Phase transfer catalyst
mA Milliampere(s) PU Polyurethane
MDI 4,4′-Diphenyl methane PUD Polyurethane dispersion
diisocyanate RBC Red blood cell
MF Melamine-formalde- RGO Reduced graphene
hyde resin oxide
MFFT Minimum film-forma- s Second(s)
tion temperature SAXS Small angle X-ray
min Minute(s) scattering
mg Milligram(s) SAED Selected area electron
mL Milliliter(s) diffraction
View Online
Abbreviations and Symbols xiii

SEM Scanning electron Tm Melting temperature
microscope TPU Thermoplastic
SMP Shape memory polymer polyurethane
SPR Surface plasmon UTM Universal testing machine
resonance UV Ultraviolet
SWCNT Single-walled carbon UVA Unmanned air vehicle

nanotube V Voltage
TDI Toluene diisocyanate VOC Volatile organic compound
TEA Triethylamine W Watt
TEC Thio–enol coupling WPU Waterborne polyurethane
TEM Transmission electron WAXD Wide angle X-ray diffraction
microscopy XRD X-ray diffraction
TEOS Tetraethoxysilane µm Micrometer(s)
Tg Glass transition µM Micromolar
temperature µL Microliter(s)
TGA Thermogravimetric ηinh Inherent viscosity
analysis λmax Wavelength maximum
THF Tetrahydrofuran θ Scattering angle
.
Contents
Chapter 1 Biobased Hyperbranched Polyurethane 1
1.1 I ntroduction 1
1.2 Historical Background 3
1.3 Classification 4
1.3.1 Structure 5
1.3.2 Source 6
1.3.3 Thermal Response 6
1.3.4 Properties and Applications 7
1.4 Raw Materials and Methods 10
1.4.1 Raw Materials 10
1.4.2 Preparative Methods 19
1.5 Modifications 21
1.6 Testing and Analysis 22
.
1.6.1 Spectroscopic Techniques 23

1.6.2 Diffraction/Scattering Techniques 24
1.6.3 Microscopic Techniques 25
1.6.4 Other Techniques 25
1.6.5 Molecular Weight 26
1.6.6 Testing Methods 27
1.7 Properties 28
1.7.1 Physical 29
1.7.2 Rheological and Mechanical 29
1.7.3 Thermal and Flame Retardancy 30
1.7.4 Electrical 31
1.7.5 Weather and Chemical Resistance 31
1.7.6 Biodegradability 31
1.7.7 Shape Memory 33
1.7.8 Self-Healing and Self-Cleaning 33

By Niranjan Karak
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xvi Contents
1.8 A pplications 33
1.8.1 Surface Coatings 34
1.8.2 Shape Memory Materials 34
1.8.3 Foams 35
1.8.4 Self-Healing Materials 35
1.8.5 Self-Cleaning Materials 35

1.8.6 Biomedical Applications 35
1.8.7 Packaging 36
1.8.8 Agriculture 36
1.8.9 Miscellaneous 36
1.9 Health and Safety 37
1.10 Concluding Remarks and Future Trends 37
References 38
Chapter 2 Nanomaterials for Polyurethane Nanocomposites 41
2.1 I ntroduction 41
2.2 Definition, Significance, and Historical Background 42
2.2.1 Definition 42
2.2.2 Significance 43
2.2.3 Historical Background 44
2.3.1 Zero Dimensional 45
2.3.2 One Dimensional 46
2.3.3 Two Dimensional 47
.
2.3.4 Hybrid 47
2.4 Raw Materials 47
2.5 Preparative Methods 47
2.5.1 Physical Approaches 49
2.5.2 Chemical Approaches 50
2.6 Characterization 50
2.6.1 UV-visible Spectroscopy 51
2.6.2 FTIR Spectroscopy 52
2.6.3 NMR Spectroscopy 53
2.6.4 X-ray Diffraction 53
2.6.5 Electron Microscopy 53
2.6.6 Raman Spectroscopy 54
2.7 Properties 55
2.7.1 Physical and Mechanical 57
2.7.2 Optical 57
2.7.3 Electrical and Magnetic 58
2.7.4 Catalytic 58
2.7.5 Chemical Sensing 59
2.7.6 Biological 59
2.8 Brief Account of Different Nanomaterials 59
2.8.1 Metal and Metal Oxides 59
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Contents xvii
2.8.2 Silicon-based Nanomaterials 63
2.8.3 Carbon-based Nanomaterials 65
2.8.4 Organic Nanomaterials 70
2.8.5 Nanohybrids 72
2.9 Safety and Ecological Balance 73
2.10 Applications 74
2.11 Conclusions and Future Trends 75
References 76
Chapter 3 Biobased Polyurethane Nanocomposites 80
3.2 Definition, Significance, and
Background 82
3.4 Techniques of Fabrication 83
3.4.1 Solution Technique 83
3.4.2 In situ Polymerization Technique 85
3.4.3 Melt Mixing Technique 86
3.5 Analysis and Testing 86
3.5.1 Chemical Structure 87
3.5.2 Physical Structure 88
3.6 Properties 92
3.6.1 Mechanical 93
3.6.2 Rheological 94
.
3.6.3 Thermal 94
3.6.4 Electrical 95
3.6.5 Barrier 96
3.6.6 Catalytic 97
3.6.7 Flame Retardancy 98
3.6.8 Biodegradation 98
3.6.9 Antimicrobial Activity 99
3.6.10 Shape Memory 100
3.6.11 Self-Healing 101
3.6.12 Self-Cleaning 101
3.7.1 Surface Coatings and Paints 102
3.7.2 Shape Memory Materials 103
3.7.3 Sensors 104
3.7.4 Self-Healing Materials 104
3.7.5 Self-Cleaning Materials 104
3.7.6 Biomaterials 105
References 106
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xviii Contents
Chapter 4 Surface Coatings and Paints 112

4.2 Basic Concepts and History 114
4.3.1 Waterborne 117

4.3.2 Others 124
4.4 Components 125
4.4.1 Binders 126
4.4.2 Pigments 128
4.4.3 Additives 128
4.6 Properties 135
4.6.1 Flow Behavior 135
4.6.2 Mechanical 136
4.6.3 Thermal 136
4.6.4 Abrasion and Mar Resistance 137
4.6.5 Blushing 138
4.6.6 Optical 138
4.6.7 Adhesion and Corrosion 138
4.7 Problems 140
4.7.1 Bio-Film Formation 140
4.7.2 Photo-Degradation 141
4.7.3 Chemical or Environmental Degradation 141
4.7.4 Adhesion Failure 142
.
4.7.5 Flammability 142

4.7.6 Toxicity and Air Pollution 143
4.7.7 Hiding 143
4.7.8 Leveling 143
4.7.9 Sagging 144
4.7.10 Crawling 144
4.7.11 Cratering 144
4.7.12 Wrinkling 145
4.7.13 Popping 145
4.7.14 Foaming 146
References 148
Chapter 5 Shape Memory Materials 154

5.2 Classification and Advantages 156
5.3 Background and Basic Understanding 159
5.4 Mechanism 162
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Contents xix
5.5 Criteria and Design Protocols 163
5.6 Factors Affecting Shape Memory Effects 167
5.6.1 Hard Segment 167
5.6.2 Soft Segment 168
5.6.3 Chain Extender 169
5.6.4 Moisture 169

5.6.5 Processing 169
5.6.6 Nanomaterials 170
5.6.7 Modifications 171
5.7 Testing Methods 173
5.7.1 Cyclic Thermo-Mechanical Test 174
5.7.2 Stretching–Shrinkage Test 175
5.7.3 Bending-Video Graphic Test 175
5.8 Biological Behavior 176
5.9.1 Biomedical 177
5.9.2 Smart Fabrics 179
5.9.3 Mechanical Devices 180
References 181
Chapter 6 Self-Healing Materials 187

6.2 Classification and Definition 189
.
6.3 Basic Understanding 192

6.4 Approaches 193
6.4.1 Reversible Covalent Bond Formation 194
6.4.2 Reversible Non-Covalent Bond or
Supramolecular Self-Assembly 196
6.4.3 Microencapsulation 197
6.4.4 Macro-Vascular Networks 198
6.4.5 Layer-by-Layer Strategy 198
6.4.6 Incorporation of Nanomaterials 199
6.4.7 Close-Then-Heal Strategy 201
6.5 Mechanism and Theory 202
6.6 Testing Methods 205
6.7.1 Encapsulation of Flexible Solar cells 207
6.7.2 Aerospace and Other Engineering 207
6.7.3 Super-Hydrophobic Coatings 207
6.7.4 Anticorrosion Coatings 208
6.7.5 Cellular Materials 209
References 211
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xx Contents
Chapter 7 Self-Cleaning Materials 216

7.2 Classes of Self-Cleaning Surfaces 218
7.3 Basics of Self-Cleaning Effects 219
7.4 Techniques to Produce Self-Cleaning Surfaces 221

7.5 Mechanism of Photo-Catalytic Effects in
Self-Cleaning Surfaces 223
7.6 Measurement of Self-Cleaning Behavior 225
7.7.1 Oil–Water Separation 227
7.7.2 Protection of Cultural Heritage 229
7.7.3 Special Coatings and Paints 230
7.7.4 Water Desalination and Purification 234
7.7.5 Solar Cells 234
7.7.6 Heterogeneous Catalysis 235
7.7.7 Sensors 235
References 237
Chapter 8 Biomaterials 241

8.2 Definition and Classification 243
8.2.1 Metals and Alloys 244
.
8.2.2 Ceramics 244

8.2.3 Polymers 245
8.2.4 Composites 246
8.3 Fabrication Process 246
8.4 Characterization 248
8.4.1 In vitro Cytotoxicity Assays 248
8.4.2 Cell Adhesion Assays 249
8.4.3 In vitro Immunocompatibility Assays 249
8.4.4 In vitro Hemocompatibility Assays 250
8.4.5 In vivo Assessment of Biocompatibility and
Inflammatory Response 250
8.4.6 Biodegradation Tests 250
8.4.7 Antimicrobial Tests 251
8.5 Properties 251
8.5.2 Surface 253
8.5.3 Thermal 253
8.5.4 Biological 254
8.6.1 Tissue Engineering 259
8.6.2 Wound Dressing 261
8.6.3 Drug Delivery 261
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Contents xxi
8.6.4 Catheters and Stents 261
8.6.5 Artificial Organs 262
8.6.6 Smart Biomedical Devices 263
8.6.7 Antimicrobial Bio-Device Coatings 263
References 265
Chapter 9 Packaging Materials 270

9.2 Definition and History 272
9.3 Significance 272
9.4 Advantages Over Other Packaging Materials 273
9.6 Properties 277
9.6.1 Barrier 278
9.6.3 Thermal and Flame Retardancy 280
9.6.4 Chemical Resistance and
Weathering 281
9.6.5 Antimicrobial 282
9.6.6 Sensing 283
9.6.7 Antistatic 283
9.7.1 Nuclear Material 287
.
9.7.2 Food Items 287

9.7.3 Photographic Films 288
9.7.4 Electronic Materials 288
9.7.5 Bio-Medical 289
9.8 Examples of Commercial Products 289
References 291
Chapter 10 Miscellaneous: Other Applications 294

10.2 Adhesives 295
10.2.1 Advantages 296
10.2.2 Disadvantages 297
10.2.3 Classification 297
10.2.4 Surface Treatment 300
10.2.5 Testing Methods 300
10.2.6 Applications 301
10.3 Automobiles 302
10.4 Agriculture 305
10.5 Construction 307
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xxii Contents
10.6 Electrical and Electronic Industries 309
10.7 Energy 312
10.8 Footwear 314
References 317
Subject Index 320

.
Published on 08 August 2017 on http://pubs.rsc.org | doi:10.1039/9781788011891-00001
Chapter 1
Biobased Hyperbranched
Polyurethane
1.1 Introduction
Polyurethane (PU) is one of the most versatile, industrially important, and
useful polymers, combining aromatic/aliphatic moieties covalently bound
through urethane as the main linkage (–OCONH) of the chains. Biobased
fully aliphatic PU is the most recent addition from the author’s laboratory.1
PU is one of the most important polymeric materials contributing to about
6% of the world polymer uses. This novel polymer is synthesized through
a polyaddition reaction of organic compounds containing reactive hydroxyl
groups, such as di/polyols, and di/polyisocyanates of both aromatic and
aliphatic nature. PU is available in almost all forms of polymers, including
.
thermoplastic, elastomeric, thermosetting, resinous, fibrous, etc. They can

be processed by all the common processing techniques of polymers, partic-
ularly both by melt and solution processing techniques. In the solution pro-
cessing technique, both solvent-borne and waterborne systems are employed
depending on their suitability. They are used by almost all related petrochem-
ical industries including construction, automobile, and consumer goods,
and in many diverse applications ranging from biomedical devices to surface
coatings.2 Even though it is difficult to estimate their market size, the total
amount of industrial consumption in 2015 has been determined as approxi-
mately 10 million tons. The main consumers of PU are found in the fields of
packaging, furniture, bedding, building, construction, coatings, adhesives,
sealants, elastomers, appliances, automobile, footwear, biomedical, etc. Due
to its extreme versatility, in the form of linear and cross-linked structures,
soft elastomers, and hard fibers including thermoplastics, PU is also used in

By Niranjan Karak
1
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2 Chapter 1
numerous other minor applications. It is used to make foams, films, water-
borne dispersions, and so on. With this incredible utility, it is not surprising
that PU is among the most ubiquitous man-made polymers on earth.
In the structure of PU, although the main linkage is urethane, also called
the carbamate group (–NH–C(=O)O–), other groups such as urea, esters,
ethers, allophanate, hydrocarbons with aromatic and aliphatic moieties,

etc. may also be present (Figure 1.1).3 The components used for the synthe-
sis of biobased PU are relatively high molecular weight (500–6000 g mol−1)
diols, known as macroglycols, aromatic and aliphatic diisocyanates, and low
molecular weight di/polyols or di/polyamines as chain extenders. Among
these, generally, the chain extender (at least partly) is chosen from biobased
components like vegetable oils (castor oil) or their immediate derivatives like
monoglyceride or dihydroxy fatty amides, tannic acid or its derivatives, citric
acid, starch or its derivatives, lignin, etc. Segmented PU generally contains
two incompatible structural units, namely soft and hard segments. The soft
segments are made of linear long-chain diol- or polyol-based macroglycols
and diisocyanates, whereas the hard segments are obtained from diiso
cyanates and low molecular weight chain extenders like diols or diamines.4
Therefore, the soft segments are flexible and poorly polar or non-polar in
nature, whereas the hard segments are rigid and highly polar. A wide range
of physico-chemical properties of PU can be tailored by judicious variation
of the composition and structure of the three basic building blocks, viz. the
macroglycol, diisocyanate, and chain extender.5 Thus, proper design of PU
with appropriate structure and composition of the components may result in
unique and useful properties for different end applications.
.
Further, hyperbranched polymers have been good candidatures for advanced

polymeric materials over the last couple of decades. These polymers are highly
functionalized three-dimensional globular, non-entangled macromolecules
with unique architectural features.6 Therefore, these polymers exhibit many
desirable properties like high solubility, low melt and solution viscosity, high
reactivity, and so on. These properties are useful for their different applications,
Figure 1.1 General structure of hypothetical PU with different possible linkages.

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Biobased Hyperbranched Polyurethane 3

in addition to the single-step preparative techniques. Hence, such novel
hyperbranched PU (HPU) may be the right choice for the current material-based
society. Again, in recent years, such biobased polymers obtained from renew-
able resources have gained increasing attention for a wide range of applica-
tions, from the social, environmental, and energy standpoints, with increasing
emphasis on issues concerning waste disposal and depletion of non-renewable

resources.7 Biobased raw materials possess many advantages like biodegradabil-
ity, sustainability, non-toxicity and, most importantly, environmentally benign
attributes.8 Along with the direct use of biobased materials, their modifications
like hydroxylation of vegetable oils, amidation of tannic acid, epoxidation of
unsaturated natural products, modification of starch with epichlorohydrin and
bisphenol A, glycerolysis of citric acid, etc. are the most important tactics to
obtain the required polyols to be used as chain extenders for the preparation
of biobased PU, including HPU. It is pertinent to mention here that, in order
to produce biobased HPU, at least one component should possess more than
two reactive functional groups to take part in the urethane reactions. Thus, the
versatility of HPU becomes much more significant when it is synthesized from
renewable resource-based raw materials. Despite the numerous advantages,
biobased PU suffers from poor mechanical performance. The presence of flex-
ible moieties, such as long hydrocarbon chains in vegetable oil derivatives pro-
vides PU and HPU with plasticizing effects, but deteriorates their mechanical
strength. However, the current trends in PU technology focus its application
on alternative feedstocks, improving its environmental, health, and safety pro-
files, incremental improvement of its properties by proper design of its struc-
ture, and efficiency optimization to further reduce costs.
.
The salient features of biobased PU are:

(i) The preparative protocols follow the tenets of green chemistry, achiev-
ing high carbon credit and maintaining the concept of the triple bot-
tom line approach, since at least one of the components is naturally
renewable, versatile in structure, and easy to modify.
(ii) These PU materials are mostly environment friendly, biocompatible,
and biodegradable.
(iii) The performance of such properly designed polymers may be similar
to those of conventional petrochemical PU materials.
(iv) The properties of such PU can be tuned by changing the structure and
composition of the biobased components.

Therefore, such biobased PU materials demand special exploration of
their utilities in the modern civilized society.
1.2 Historical Background

PU was prepared by Otto Bayer in 1937 for the first time.9 After a decade of
innovation, development of PU chemistry started rapidly with toluene diiso-
cyanate (TDI). However, the first commercial application of PU as a millable
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4 Chapter 1
elastomer, coating, and adhesive started in 1945–1947, followed by flexible
PU foams in 1953 and rigid foams in 1957. On the other hand, the hyper-
branched polymer was first designed by Kim and Webster in the late 1980s.10
However, HPU was first successfully prepared by Spindler and Frechet in 1993
using AB2 monomers containing one hydroxyl group (A) and two blocked iso-
cyanate groups (B).11 Following this initial study, HPU was synthesized via an
in situ generated AB2 monomer (3,5-dihydroxyphenyl isocyanate) from the
corresponding carbonyl azide precursor by Kumar and Ramakrishnan in the
same year.12 Another one-pot approach for the preparation of HPU was pro-
posed by Hong et al. employing an in situ generated dihydroxy isocyanate
monomer.13 Again, the potential of biobased raw materials like vegetable oils
for industrial uses was first presented by J. G. Kane, who is known as the father
of vegetable oil-based polymers.7 In 1925, Kienle and Hovey synthesized a
series of alkyd resins from vegetable oils, marking the beginning of vegetable
oil-based polymers. Vegetable oil-based PU was rapidly developed in the early
2000s, both in industry and academia. In 2008, soy-based PU was used by the
Ford Motor Company in automobile interiors, such as dashboards, side-pan-
els, etc.14 Petrovic et al. first reported vegetable oil-based hyperbranched poly-
ol-based PU from soybean oil.15 However, the first biobased HPU without gel
formation using a vegetable oil derivative directly as one of the reactants was
prepared in the author’s laboratory.16 Thereafter, a large number of biobased
PU and HPU have been continuously reported in the literature.
1.3 Classification
.
The versatility of PU is so widespread that it is difficult to classify on individ-

ual terms, unlike other polymers. Thus, PU materials are categorized in dif-
ferent classes based on their structure, source, thermal response, properties,
and applications (Figure 1.2).
Figure 1.2 Classification of PU materials.

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1.3.1 Structure
PU materials are classified into two main categories based on their struc-
ture line representation. These are linear PU (LPU), where the structure
consists of a linear chain without any pendent or side urethane chains;
and branched PU. Again, depending on the branching pattern, branched
PU can be of different types. However, HPU and PU dendrimers are the

most important among them. Other types include comb, brush, star, etc.
architectural PU materials. The line representations of LPU and HPU are
shown in Figure 1.3. HPU is a highly branched PU with a unique structure
containing a large number of structural defects and missing branches,
unlike perfectly branched PU dendrimers. It can be obtained like LPU by
a single pot preparative technique, thereby allowing large scale produc-
tion without difficulty. The most unique and common features of HPU are
the presence of three distinct structural units (Figure 1.3), namely den-
dritic (D), linear (L), and terminal (T) units.6 The amount of such struc-
tural units is directly related to the degree of branching (DB), which
strongly influences the ultimate properties of HPU. On the other hand,
.
Figure 1.3 General structures of biobased LPU, HPU, and a PU dendrimer.

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6 Chapter 1
−9
PU dendrimers are nanometer-sized (10 m) spherical highly branched
macromolecules with no entanglement and coiling within the molecular
chains, being also described as globular polymers. They also possess three
distinguishing structural features, namely (i) a central multifunctional
core unit, generated from a multifunctional component, (ii) interior layers
(generation) consisting of repeating units, propagating units, or building

blocks attached directly to the multifunctional central core, and (iii) an
exterior layer or surface of terminal functionalities exposed on the outer-
most part of the structure (Figure 1.3). These highly branched PU mate-
rials have greater significance than the analogous LPU, which include
(i) unique structural features, (ii) the presence of a large number of active
and free surface groups, (iii) no entanglement in the structure, except
those specially designed with long chain components, (iv) low polydisper-
sity indexes (PDIs), (v) they do not obey the well-known Mark–Houwink
equation (discussed later), (vi) they bring active functional groups in close
proximity in easily accessible form, and (vii) they are easily modifiable to
the desired structure. However, to achieve acceptable mechanical properties,
HPU is nowadays designed with long segment macroglycols, so that some
entanglement and coiling arise in the structure to achieve good mechanical
performance.
1.3.2 Source
PU can be divided into two main classes, depending on the source of their
components. Most PU is derived from petroleum-based components and is
.
thus termed synthetic PU, whereas PU obtained using biobased renewable

raw materials or their derivatives, fully or partly, is known as biobased or
bio-derived PU.7 Biobased PU has gained tremendous impetus over the last
two decades due to global environmental concerns and health risks. Further-
more, the concepts of green chemistry, triple bottom line approach, and car-
bon credit can be addressed through the development of biobased PU. This
book deals with these issues and so, further details are deliberated in the
subsequent sections and chapters.
1.3.3 Thermal Response

PU polymers, including biobased materials, are classified into two categories
depending on their response towards thermal energy, like any other polymer.
These are thermosetting and thermoplastic PU.17 Thermosetting PU flows
easily with or without heating in its original state, but set permanently once
chemically cross-linked with or without additional curing agents. They may
be low molecular weight PU resins or high molecular weight PU elastomers.
On the other hand, thermoplastic PU can be repeatedly softened upon heat-
ing (much below the decomposition temperature) and transformed to hard
dimensionally stable materials on cooling. In this connection, it is pertinent
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to mention that thermoplastic PU can also be judiciously chemically cross-
linked to transform it into thermosetting PU.
1.3.4 Properties and Applications

PU can be classified into a large variety of products based on the composition

and nature of its components, the presence and type of additional ingredi-
ents in the polymerization recipe, etc. These are elastomers, foams, adhe-
sives, ionomers, fibers, coatings, etc.2 Depending on their special attributes,
PU polymers are also classified as smart materials and biomaterials.
1.3.4.1 Elastomers
PU elastomers are like other elastomers, they have characteristic high elasticity
and, hence, possess high reversible deformation and relatively high molecular
weight. They also exhibit high abrasion resistance, chemical resistance,
mechanical strength, and thermal stability. They are obtained from flexible
long chain macroglycols with molecular weight 2000–5000 g mol−1, diisocya-
nates, and low molecular weight diol-based chain extenders maintaining the
NCO/OH ratio equal to unity.18 PU elastomers can again be of different types,
namely millable, castable, and thermoplastic. Millable PU can be processed
using polymer processing equipment like mechanical milling, extrusion,
calendering, compression, or injection molding depending on the require-
ments. Thermoplastic elastomeric PU is a biphasic segmental PU that exhib-
its a similar performance to that of vulcanized rubber (without any chemical
.
vulcanization or cross-linking), but the processing is similar to that for other

thermoplastic polymers. Castable PU, on the other hand, is obtained by mix-
ing relatively low molecular weight macroglycols (500–1500 g mol−1) and diiso-
cyanates using a pre-polymerization technique, followed by addition of the
desired chain extender in the second step; the resulting solution is poured into
a mold to obtain the desired article.19 Almost all thermoplastic PU has sim-
ilar hard segments and the differences in performance and price arise from
soft segment differences. Polyester-based soft segments are preferred for uses
where hydrolysis is not an issue for performance but the cost is the major con-
cern. On the other hand, thermoplastic PU elastomers have gained significant
industrial momentum because of their easy processing with standard polymer
processing equipment and recyclability attributes. In this context, cast PU
elastomers have achieved significant commercial acceptance.
1.3.4.2 Foams
One of the major applications of PU is in the foam sector. PU foams are cellu-
lar products obtained from low molecular weight polyols and aromatic diiso-
cyanates, along with an efficient blowing agent. They can be easily formed
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8 Chapter 1
by reaction between the moist polyol and isocyanate, producing volatiles
during the polymerization process, followed by growth and stabilization of
those gas bubbles as the PU solidifies. PU foams are again classified into two
types, namely, flexible and rigid foams. Flexible foams are made of relatively
low molecular weight PU (3000–6000 g mol−1) with an average functionality
of more than two and good load bearing capacity, while rigid PU foams are
based on polyols of high molecular weight and average functionality greater
than three. Flexible foams are the major commercial product of PU, and it
is the largest category of cellular polymeric products. The worldwide con-
sumption of flexible PU foams is about half the total volume consumption of
PU. The rest of PU products are divided almost equally between rigid foams
and coatings, adhesives, and elastomers. Out of these products, ‘Slab-stock’
foams are the highest produced flexible foams, accounting for ∼70% of the
foam production. These foams are used to make furniture (40%), carpet
underlayment (25%), bedding (15%), transportation cushioning (12%), and
packaging (5%).20
1.3.4.3 Fibers
The initial research on PU focused on the preparation of fiber-forming poly-
mers. PU fibers can be prepared from diisocyanates with low molecular
weight chain extenders like ethylene glycol, hydrazine, hydroxyl amine, etc.
under nitrogen atmosphere at elevated temperature. PU is then spun into
fibers by conventional melt and solution spinning techniques. These fibers,
in most cases, are used as blends along with some other fibers for improve-
.
ment of performance. For example, a highly elastic fiber known as ‘two-way

tricol’ is a blend of PU fibers with nylon or polyester fibers. Lately, elastic PU
fibers containing urethane–urea linkages of aromatic diisocyanates, known
as ‘Spandex’ fibers, have been reported to be composed of at least 85% ure-
thane linkages in the structure. They are based on low molecular weight diol
or diamine chain extenders and diisocyanates.21 Typically, Spandex fibers are
formed by urethane-urea block copolymers, where the polyurea blocks are
joined with blocks of urethane linkages employing diamine chain extenders,
aromatic diisocyanates, and either polyether or polyester soft segments. The
hard polyurea segments provide the desired thermostability, which is essen-
tial for clothing ironing.
1.3.4.4 Ionomers
PU containing ionic groups to a maximum extent of 15% are known as
ionomers. Further, depending on the nature of the ionic groups, PU ion-
omers can be classified as cationic, anionic, and zwitterionic or ampho-
lytic. The application of PU ionomers is growing rapidly, particularly in
the biomedical field and in modern pharmaceutics, including their use
as semi-permeable membranes. Further, specially prepared PU ionomers
can be made water dispersible and thus are non-toxic, non-flammable, and
non-pollutant.22
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1.3.4.5 Coatings
PU coatings, both protective and aesthetic ones, are often applied under ambient
conditions without post-curing.23 Furthermore, they can be of different types,
such as solvent-borne, waterborne, and 100% solid PU coatings. Waterborne
PU (WPU) has gained great attention because of its overall balance of proper-
ties and environmental friendliness. In addition to coatings, WPU is also found

in adhesives, finishing agents, paper and fiber surface treatment agents, etc.
However, waterborne PU dispersions (PUDs) are used commercially in coating
applications, where low viscosity properties are required and, most importantly,
they have limited VOC content, one of the inconvenients of conventional sol-
vent-borne systems. The details of all these coatings are discussed in Chapter 4.
1.3.4.6 Adhesives
PU adhesives have been known for a long time as reliable and high performing
industrial products owing to high shear and tensile strengths.24 This may be
due to their ability to wet surfaces, form H-bonding with different substrates,
allow them to permeate through porous substrates, and form covalent bonds
with substrates containing active hydrogen atoms or functional groups. The
factors that affect the performance of PU adhesives are the nature of the iso-
cyanates (aromatic isocyanates are better than aliphatic ones), nature of the
polyols (polyether polyols are poorer in performance than polyester polyols),
amount of aromatic and aliphatic groups, type of solvents used during cast-
ing, and the crystallinity of the polyols. PU adhesives and sealants are mainly
used in construction, automotive, packaging, and aerospace industries. For
.
structural PU adhesives, high functionality polyols and isocyanates are used

as components to improve the glass transition temperature and modulus.
PU-based adhesives are discussed in Chapter 10.
1.3.4.7 Smart Materials
Smart materials or intelligent materials are a unique class of materials with
the ability to perform special functions on their own, as and when required,
under application of a suitable stimulus.25 In this context, smart PU materials
can be of different types, such as shape memory polymers, self-healing poly-
mers, self-cleaning polymers, etc. Shape memory PU is a special type of poly-
mers with the ability to fix a desired temporary deformed shape and regain
their original shape as and when required upon exposure to a suitable stim-
ulus like heat, light, electric energy, magnetic field, ultrasound, microwave,
etc. The details of this class of PU are discussed in Chapter 5. On the other
hand, self-healing PU materials are polymers that can heal or repair damage
or cracks on their own, as and when required, with or without the application
of an appropriate external stimulus. This special class of PU is presented in
Chapter 6. Again, self-cleaning PU materials are able to clean their surface by
themselves upon exposure to a suitable stimulus or even without the use of
any external stimulus. They are described in Chapter 7 of this book.
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railroad across the desert begins. The ship is a sternwheeler, much
like those on some of our rivers. It is about twenty feet wide, one
hundred and fifty feet long, and draws only six inches. We make
about six miles per hour, and our pilot, a dark-faced, short-bearded
Nubian in turban and gown, corkscrews his course from one side of
the river to the other as we wind our way up the stream.
We fly the Egyptian and Sudanese flags, but the steamer belongs
to the government of the Sudan which means it is British. The
captain, however, is a German, and the rest of the crew are Nubians,
most of whom are as black as your shoes. The captain speaks
German, French, English, and Arabic. He attends to everything
connected with the steamer, even to the meals and the proper table
service. Our waiters are black-faced Nubians in long white gowns
and sashes of bright red. They wear white turbans, and their feet are
either bare or shod in red slippers.
I find the steamer comfortable and the company agreeable. The
boat has two decks. On the lower one are thirty cabins and the
dining room, where our meals are served table d’hôte. Over the
upper deck an awning is stretched, so that we can sit and watch the
scenery as we go up the river.
Our party consists of several commercial travellers, bound for the
Sudan and Central Africa; two missionaries who are going up the
Sobat River; a capitalist, largely interested in land development
enterprises about Khartum, and several people who are on their way
to the Blue Nile to hunt big game. Although we are far away in the
wilds of Nubia, with nothing but desert on each side, most of us
appear in evening clothes at dinner. Our meals are served in courses
with half-a-dozen changes of plates, knives, and forks.
Here is our bill of fare for one day. At seven this morning, while I
was yet in bed, my black boy appeared and handed me a cup of hot
tea, with two sweet crackers on each side of the saucer. At eight
o’clock the bell rang for breakfast in the dining room. The meal
consisted of fried fish fresh from the Nile, bacon and eggs, bread
and butter and jam, with tea or coffee. At one o’clock came
luncheon, a bountiful meal of rice, giblets, chicken, mutton chops,
and fruit, with bread and butter and cheese. Coffee, of course. At
eight o’clock we had dinner, and the menu was as follows: An
excellent soup, then a boiled fish just out of the Nile, followed by a
salmi of pigeons, roast lamb and mint sauce, with potatoes and
string beans. Then there was a course of tomato salad, and after
that a pudding and fruit.
I do not find travel in Africa at all cheap. If one travels along the
Nile he must expect to spend about fifteen dollars a day, the cost
increasing as he goes up the river. My trip from Shellal to Khartum
and back by rail and steamer, a distance not very much greater than
from New York to Chicago, will be one hundred and fifteen dollars, or
about six cents per mile, and I shall pay at Khartum a hotel rate of at
least five dollars per day.
If one attempts to travel economically he must expect many
discomforts. On this boat first-class passengers only are carried. We
have some second- and third-class passengers, but they stay on a
low barge which we tow alongside. This barge has a flat deck of
rough boards covered by a roof. The people carry their own bedding
and lay it down on the boards. They must supply their own food, and
as the servants of the first-class passengers, and natives, who are
far from clean, travel in that way, the company is not desirable.
Besides, it is very cold at night, and those who sleep on the decks
have the desert breezes blowing over them all night long. It is cooler
here than in Egypt, although we are nearer the Equator. I have a
woollen blanket on my bed, with a heavy travelling rug on top of that,
but still I am none too warm. In the early morning I wear an overcoat
on deck, although at noon it is so hot out of the breeze that I would
fain take off my flesh and sit in my bones.
Sailing up the Nubian Nile we are almost free from the flies such
as are found by millions in Egypt, but Nubia has a little fly of its own
which is almost unbearable. This is known as the nimetta, a small
midge, which appears in myriads during the winter season. Its bite
causes a slight fever, and the natives sometimes wear bunches of
smouldering grass twisted about their heads to keep it away.
The flies of Egypt are probably the descendants of those which the
Lord sent to afflict Pharaoh when he would not let the Children of
Israel go. They look not unlike the common fly of our country, but
they are bolder and hungrier. Their feet stick to one as though they
were glued and they will not move until forcibly brushed off, but the
Egyptian peasants have become so used to them that they let them
stick at will. Their favourite feeding place seems to be on one’s eyes.
This is especially true of the children, and it is a common sight to see
a child with its eyes so fringed with flies that it seems to have double
eyelashes. The flies cover the meat in the markets, they roost on the
buffaloes, camels, and donkeys, and attack the tourist to such an
extent that the selling of fly brushes has become an Egyptian
industry. The brushes are tassel-like affairs with long strings similar
to the hairs of a horse’s tail.
Everyone knows that flies carry disease and many of the troubles
of the Egyptians are due to them. Ophthalmia is especially prevalent.
There are blind people everywhere, while one-eyed men and women
are common. Diseases of the eye are so universal that one of the
charities of Lower Egypt is a company of travelling eye doctors, who
are supported by a rich Englishman. The doctors go from village to
village, carrying their tents with them. As they enter a town, word
goes out that the poor will be treated without charge, and crowds
come to their tents to have their eyes examined and cured. They
remain in one town for a month or so, serving the poor without
money and without price. The institution does great good.
The port of Shellal, where I took the steamer for Wady Halfa, lies
opposite the island of Philæ, and during my stay there I made
several trips to the island to take photographs of the ruined temples,
which have already been more or less affected by the backing up of
the water of the Aswan Dam. When the Aswan Dam was first
proposed a great outcry came from the savants and archæologists of
the world on account of the injury that it would do to Philæ, but the
material results have been so valuable to Egypt that the dam went
ahead, regardless of the preservation of these ancient ruins.
Something like one hundred thousand dollars was spent in fortifying
the structure during the building of the dam, and it is probable that
twice this amount would have sufficed to take up the temples and
carry them to the mainland, or even transport them to Cairo, where
all the world might see them.
The island of Philæ, which is on the edge of lower Nubia in the
centre of the Nile just above the first cataract, is reached by ferry
boat from Shellal or from Aswan and the dam. It is about fifteen
hundred feet long and five hundred feet wide, and almost covered
with temples built by the Ptolemies and others two or three centuries
before Christ.
The chief deity of Philæ was the goddess Isis, though Osiris,
Hathor, and the gods of the cataracts were also worshipped there.
Under the Roman emperors the temples were enlarged, but when
Egypt was converted to Christianity, the hermits and other fanatics
made their way into Nubia and took possession of it. They turned
some of the temples into Christian churches and their mutilations of
the splendid carvings made in honour of the gods of Old Egypt can
be plainly seen at low water.
The ruins are well worth a visit. Some of the structures have a
forest of columns about them. The Kiosk, which is known as
Pharaoh’s Bed, is one of the most beautiful of the Egyptian temples.
The stones are all of great size. They probably came from the Aswan
quarries, or it may be from the granite rocks that abound in the
desert. That region is almost all granite. I rode over it for thirty miles
on donkey back, making my way through the desert around and
about granite boulders worn smooth by the sandstorms of thousands
of years. The rocks are of all shapes and are piled, one upon
another, as if by the hands of a race of Titans. Here one stands high
over those surrounding it, as though on a pedestal; there others are
massed like fortifications; in another spot they rise in towers.
I visited the Aswan quarries, the great stone yards from which the
obelisks were taken, and from which came the mighty statues of
Rameses and the massive blocks of the greatest of the Theban
temples. The quarries to-day are much the same as they were when
the Egyptians left them two or three thousand years ago. One can
see the marks of their wedges on the rocks and the markings of the
old stone-cutters are plain. In one place there is an obelisk half
finished, lying on its side, just as the masons of the Pharaohs left it
ages ago. When the granite was taken out for the Aswan Dam, the
Italian workmen used many of the blocks that the ancient Egyptian
mechanics had begun to cut; indeed, that great granite structure was
made in partnership by two sets of mechanics born thousands of
years apart.
CHAPTER XVIII
FROM THE MEDITERRANEAN TO THE SUDAN
I am in the Sudan on the northern section of the Cape-to-Cairo

railroad. I am in the upper end of Nubia at the railroad station of
Halfaya, just opposite Khartum, and as far south of Alexandria as the
distance from New York to Denver.
In imagination come with me on the trip from the Mediterranean to
Khartum. We shall need four days to go from the sea to the junction
of the White and Blue Niles, where I now am, but the journey will for
the most part be comfortable and there are interesting sights for at
least part of the way. We start at Alexandria, the chief sea-port of the
whole valley, and in three hours our train carries us across through
the delta to Cairo, for there is frequent and rapid train service
between these two chief cities of Egypt.
As we go first class, we must pay three cents a mile. The second-
class fare is only half as much as the first, and the third is still
cheaper. Every train has first-, second-, and third-class cars. Those
of the first, which are divided into compartments, are patronized by
tourists and officials. The second-class car is much like the coach of
our American train, having an aisle through the centre. These cars
are used by merchants, commercial travellers, and well-to-do
natives. The third-class cars are cheaply made and their seats are
wooden benches. They are always filled with the common Egyptians,
and foreigners seldom travel in them. Our tickets are little blue cards
with the price printed upon them in English and Arabic. We have to
show them to the guard as we enter the train, and they are not
examined again until they are taken up at the gates of the station as
we go out.
We have some trouble with our baggage, for as usual with
Americans, we are loaded with trunks. Only fifty-five pounds can be
checked without extra charge, and my trunks often cost me more
than my fare. We notice that the English and Egyptian passengers
put most of their belongings into bundles and bags, which they can
bring into the cars with them. Many a single passenger is carrying
four or five valises, each holding as much as a small steamer trunk,
and the compartments are half filled with such luggage. Every first-
class car has a guard, or porter, who helps us off and on, and there
are always fellaheen at the depot ready to carry our effects for five
cents apiece.
Most of the Egyptian trains have a small car next to the engine, an
express car back of that, and also cars for animals. Our train carries
one in which are two blanketed horses, with Egyptian grooms to take
care of them. They probably belong to some rich nabob of Cairo, and
are going south by express.
The postal cars are carefully watched. The bags of mail are
carried to them on red trucks made for the purpose. The trucks are
pushed by the Arabs and mail is handled by them; but a dark-faced
soldier with rifle and sword marches along to see the bags taken in
and out. When a truck is loaded, the soldier goes with it to the post-
office wagons. There is always a guard on such Nile steamers as
carry mail, and the letters are never left without some armed official
to watch over them.
The Bisharin are desert folk, whose chief possessions are their wells and flocks.
They pity city dwellers and scorn those who till the soil. This aged warrior has his
short spear and rawhide shield.
Villages of mud huts spot the banks of the Upper Nile for hundreds of miles. The
dates grown along here are sweeter and larger than those from farther down the
river.
The Bisharin inhabit the desert beyond the narrow green strip along the Nile.
Their matting tents are easily moved from place to place in their search for
pasturage.
The railroads of Egypt and the Sudan are under the government,
and I find both systems pay. Those of Egypt earn about six per cent.
on their capital stock and their working expenses are only about
seventy-three per cent. of the gross receipts. The business is rapidly
increasing. They carry some twenty-six million passengers a year
and some five million tons of freight. Egypt now has something like
fifteen hundred miles of railroads which belong to the government,
and in addition more than seven hundred miles of agricultural roads
managed by private parties. The earnings of the latter are
increasing, for they carry more freight and passengers from year to
year.
The main lines are managed by Egyptian and European officials.
The superintendents of departments, who receive three thousand
dollars and upward a year each, are mainly Europeans, while the
inspectors and sub-inspectors, who get from eighty dollars to two
hundred and forty dollars a month, are in the main foreigners. Under
these men are the native guards, track workers, and mechanics of
various kinds, who receive smaller wages. They are almost all
Egyptians, there being some twenty-four hundred of them to about
one hundred and fifty Europeans.
The Sudan roads go through a thinly populated country, but the
receipts are already considerably more than their working expenses
and are rapidly increasing.
The Alexandria-Cairo division of the Cape-to-Cairo road taps one
of the richest countries on earth. I mean the delta of Egypt, which is
more thickly populated than most other parts of the globe. The
distance from Alexandria to Cairo is one hundred and thirty-three
miles, and all the way is through rich farm lands. There is no desert
in sight until you reach Cairo. Cotton is piled up at every depot, there
are vast loads of it on the canals which the track crosses, and at the
stations cars of cotton bales fill the side tracks.
The next division above Cairo goes to Asyut, which is two or three
hundred miles farther south. Then comes the road from Asyut to
Luxor, ending with the narrow-gauge line from Luxor to Aswan.
These divisions are through the narrow part of the Nile valley, with
the desert in sight all the time. The river winds this way and that, but
the railroad is comparatively straight, and is often far off from the
river amid the sand and rocks. Such parts of the line are
uncomfortable going. At times the sands are blinding, the dust fills
the cars, and our eyes smart. These discomforts are somewhat less
in the first-class cars. All of them have shutters and double windows
to keep out the dust, and the inner window panes are of smoked
glass to lessen the glare. With the shutters up it is almost dark and
when both windows are down the interior has the appearance of
twilight. When clear glass alone is used the rays are blinding and the
sun comes through with such strength that it is not safe to have it
strike the back of one’s neck. In addition to the double windows and
shutters there are wooden hoods over the car windows, so that the
direct rays of the sun may not shine in. The cars have also double
roofs, and the doors have windows of smoked glass. There is so
much dust that it comes in when everything is shut tight, and the
porter has to sweep up every hour.
I found the conditions even worse in the Nubian Desert, which I
crossed on the railroad from Wady Haifa, where I left the steamer
Ibis, to Berber. That region is about the dreariest and most desolate
on earth. It is all sand and rocks, with here and there a low barren
mountain. The Nubians themselves call it “the stone belly,” and the
name is well chosen.
The road through Nubia is a part of the Sudan military railway that
extends from Wady Halfa to Khartum. It is one of the iron gateways
to the Sudan, the other being the railway which the British have built
from Atbara to Port Sudan and Suakim on the Red Sea. The military
line is almost as long as from New York to Detroit and the Port
Sudan line from the Red Sea to Atbara, where it connects with the
military line, is less than half that length.
The Port Sudan road vies with the military railways in being one of
the dirtiest railroads ever constructed. Its whole route is across the
Nubian Desert. There is no vegetation at all between Atbara and the
Red Sea until within about nine miles of the coast, and then only a
scanty growth of thorn bush and scrub that feeds small flocks of
camels and sheep.
This Red Sea road was opened about 1905. Since then it has
been carrying a large part of the trade of the Sudan. Mohammedan
pilgrims from Central Africa and the Lower Nile valley use it on their
way to and from Mecca, and occasionally tourists come to Khartum
via the Suez Canal, the Red Sea, and this railroad.
The military line from Wady Halfa is the one built by General
Kitchener during the war with the Mahdi. Constructed in less than
eighteen months by the British engineers and soldiers, it is one of
the most remarkable examples of railroad building on record. A large
part of it was laid in the hottest time of the year and at the rate of one
and a quarter miles per day, and once, more than three miles were
laid in one day. Yet the work was so well done that heavy trains
could travel safely over it even when making twenty-five miles an
hour. It was built through a waterless desert which had never been
mapped until the railroad surveyors went over it. During its
construction the survey camp was kept about six miles in advance of
the rail head. The road was built through a hostile country where
there was constant danger of attack by the Dervishes.
To-day the cars move as smoothly over those tracks as they do
over those of Egypt, and give that country regular connection with
the Sudan. There is now a train de luxe connecting Khartum with
Wady Halfa equipped with sleeping and dining cars.
The sleepers are divided into compartments about seven feet
square with two berths to each. There is an aisle along the side of
the car from which the compartments are entered, and each of the
latter is large enough to enable one to have a wicker chair in it in
addition to the berths. Every little room has an electric fan and is
lighted by electricity.
The dining-car service is good and comparatively cheap. The
meals consist of a cup of tea and some crackers brought in by a
Nubian porter at daybreak; a breakfast in the dining car at eight
o’clock; a table d’hôte luncheon at one, and a dinner in the evening.
In riding over the Sudan military road we stopped for a time at
Atbara, where the Black Nile from Abyssinia flows into the main
stream. Here is the famous bridge built by Americans upon orders
given by General Kitchener. The contract was first offered to the
English, but they were not able to build the bridge in the time
required, so the Americans took the job and finished it. Atbara is now
an important division point where the road across the desert to the
Red Sea branches off. As we stopped at the station our engine
struck me as looking familiar. I walked to the front of the train and
examined it. Sure enough, it was a Baldwin, with the name
“Philadelphia” standing out in the full blaze of the Nubian sun. Later
on, when I crossed the Black Nile over the steel bridge put up by our
builders, I felt that I was not out of touch with home, after all. I was
being hauled by an American engine over an American bridge,
though I was in the heart of the Nubian Desert more than a thousand
miles up the Nile. The thought makes one proud of our American
enterprise and mechanical genius.
At Atbara I learned a great deal about the road, which starts here
on its three hundred and thirty mile journey through the Nubian
Desert to the Red Sea. This little town might be called one of the
railway centres of the Sudan. Lying at the junction of the two chief
railways, it has the principal railroad offices and shops and is the
home of the director, with whom I had a long talk about his line to the
Red Sea. He had a part in building the road and is now its manager.
We first visited the shops, which cover two or three acres of sandy
waste. They are great sheds with walls of galvanized iron and roofs
of iron and plate glass. I saw many locomotives, cars and steel ties,
and telegraph poles outside. Going in, I found all sorts of railway
repair and construction work under way. The machinists were a
mixture of whites, blacks, and yellows, representing a half-dozen
different nations and tribes. There were British overseers, Greek and
Italian mechanics, some Nubian blacksmiths, and many Nubian boys
taking a sort of manual-training course in order that they may serve
as locomotive engineers, under machinists and trackmen. The
machinery is of modern make and the shops are well equipped.
As we walked among the lathes and planing machines the director
pointed out to me some of the peculiarities of the wear and tear of
the desert upon railway materials.
“Here,” said he, as he pointed to the wheel of an American
locomotive, in which was cut a groove so deep and wide that I could
lay my three fingers in it, “is an example of how the sands ruin our
car wheels. The flint-like grains from the desert blow over the rails,
and as the cars move they grind out the steel as though they were
emery powder. Consequently, the life of a wheel is short, and we
have to cut down its tire every few months. Moreover, the sand gets
into the bearings, and there is a continual wearing which
necessitates almost constant repair.”
“How about your sandstorms? Are they serious obstacles to
traffic?”
“At times, yes. They come with such violence that they cover the
tracks; they cloud the sun so that when you are in one you cannot
see your hand before your face. They often spring up afar off, so that
you can watch them coming. At such times the sand gets into
everything and cuts its way through all parts of the machinery.
“Another thing we have to contend with,” continued the railway
manager, “is the extraordinary dryness of the air, which shrinks our
rolling stock so that it has to be tightened up again and again. One of
our passenger cars will shrink as much as eighteen inches in one
wall alone, and we have to put in extra boards to fill up the gaps. The
same is true of all sorts of woodwork.
“Another trouble is the white ant. That little termite eats anything
wooden. It chews up the insides of our cars and even attacks the
furniture. Where there is the least moisture the ants will go for the
railroad ties, and they will chew out the insides of the wooden
telegraph poles. They always work under cover, leaving a thin shell
of wood outside. The result is that a tie or pole may look sound then
all at once it will crumble to pieces. We have to inspect the road very
carefully at regular intervals and watch out for weak points. We now
use hollow steel tubes as ties. They do not make so smooth a road
as the wooden ties, but the ants cannot eat them. We also have
steel telegraph poles.”
“I noticed my train was pulled by an American locomotive. How do
they compare with those from Great Britain?” I inquired.
“Not well,” replied the railroad director. “We have some of your
engines which we bought seven years ago. We are still using them,
but most of them have been repaired and made over. You people
make locomotives, expecting to run them to their full capacity for four
or five years and then throw them on the scrap heap. This is not
advisable out here in the desert, where freight costs so much and
the trouble of getting our rolling stock is so great. We want
machinery that will stand all sorts of trials, including the climate. We
want it rustproof and rotproof and heavily made all around. We have
here not only the dry air and the sand to contend with, but also in the
neighbourhood of the Red Sea the salt air and the alkali water.”
“I suppose the lack of water is one of your chief difficulties, is it
not?” I asked.
“Yes. This railroad is over three hundred miles long and the track
is laid through the sand. For about one third of the distance inland
from the Red Sea the country is mountainous, but the rest of it is flat.
There are no streams, so we have to rely on artesian wells for our
water supply. We have bored a number, but we find that the water in
many places is salt. We struck one well which had three per cent. of
salt in it, and another in which the water was one per cent. salt. Of
course such water is useless for our locomotives.
“We are having trouble also in getting a good water supply at Port
Sudan. We sunk one well to a depth of eight hundred feet and struck
a good flow of fresh water. We had hardly completed, it, however,
before the salt water began to seep in, and we are now drilling again.
There are some stretches along the route where there is no water
whatever. In such places we have to carry our supply with us. For
this we have tanks of galvanized iron, each of which will hold about
fifteen hundred gallons.”
From Atbara I took a later train to continue my journey on toward
Khartum. About one hundred miles south of Atbara we stopped at
Shendi, where the Queen of Sheba is said to have lived. This is a
station on the east bank of the Nile five hours or more from Khartum.
It is a considerable town with railroad shops. I saw great piles of
steel ties such as Captain Midwinter mentioned.
The mud towers outside some Egyptian huts are used by whole families as cool
sleeping places out of reach of scorpions. Sometimes mothers leave their babies
in them while they are working in the fields.
The child so contentedly sucking sugar cane is, like four out of every hundred
children in Egypt, blind in one eye. This is due chiefly to the superstition and
ignorance of their parents.
Shendi consists of an old and a new town. The latter has been laid
out by the British and has a park in the centre watered by the Nile. In
ancient times there was a great city here, for it was the capital of the
country and the supposed residence of the Queen of Sheba, who
went from here down the Nile and crossed to Palestine. There she
had her famous flirtation with King Solomon. The Abyssinians say
that she went back by the Red Sea and stopped in their country; and
that while there she bore a son whose father was Solomon and who
became the head of the line of kings which rule Abyssinia to-day.
The Mohammedans, on the other hand, say that the Queen of
Sheba did not live here at all. They claim that her residence was in
Yemen, Arabia, and that Solomon went there to visit her. The
queen’s name was Balkis. As witty as she was beautiful, she gave
the wise Solomon many a riddle which he was puzzled to answer.
CHAPTER XIX
ACROSS AFRICA BY AIR AND RAIL
The airplane has completed the conquest of the Dark Continent. A

two-months’ journey from Cairo to the Cape of Good Hope has been
reduced to a possible fifty-two hours of flying, each hour
representing one hundred miles through the skies.
Cecil Rhodes died hoping that one day his countrymen would
finish the greatest of his African projects, an all-British route
traversing the continent. His dreams were based upon steam, and
compassed a route of rail and water transport taking advantage of
the Nile and the Great Lakes. Those dreams are becoming realities,
and to-day only a few gaps remain unfilled on the long way from the
north to the south. In the meantime, aircraft has sprung almost full
fledged into the skies, and the gasoline engine and the airplane have
beaten the steam locomotive and its steel track through the wilds.
The first flight from Cairo to the Cape was made by two officers of
the South African Air Force, Colonel P. Van Ryneveld and Lieutenant
C. J. Q. Brand. Of four competitors who started from Cairo, they
were the only ones to land at Cape Town. They had several
accidents and wrecked two machines on the way. Leaving Cairo on
February 10, 1920, they took twenty-eight days to reach Cape Town,
although their actual flying time was counted in hours. Their nearest
competitor covered only half the distance, while the two others did
not succeed in getting across the desert wastes of the Sudan.
In the airplane of our imagination, let us take the trip they made.
We may be sure of excitement, for even under favourable conditions
we are starting out on one of the most dangerous air journeys known
to the world. But let us first look at a map and pick out our route. It is
a jagged line, extending from north to south, the length of the
continent. It is marked with dots and triangles, each showing a place
where we may land. As we look at the map it seems quite simple
and easy, but actual experience proves its great difficulties.
We shall leave Cairo at dawn and follow the Nile to Khartum. This
is a flight of one thousand miles, but landing places have been
prepared along the entire route at intervals of two hundred miles. We
shall stop at one of these long before noon and spend several hours
to avoid the heat of the day, when gusts of hot air, rising from the
sun-baked desert, make it dangerous to fly at low altitudes. At the
start of our flight we shall rise a mile or more to avoid these
treacherous currents, which frequently take the form of “air spouts,”
often visible on account of the dust and sand they have sucked up
with them. Such currents have force enough to toss our plane about
like a leaf in the wind. With these great gusts of hot air spouting
upward are cold currents rushing downward. These are even more
dangerous, as they are always invisible. Consequently, we shall fly
high, to avoid a “bumpy” passage, as our pilot calls it, and in landing
must be careful lest we get caught in an air pocket.
From Khartum we start on the second, longest, and most
dangerous leg of the journey. This covers a distance of twenty-six
hundred miles, extending to Livingstone near Victoria Falls in
northern Rhodesia. We shall follow, in a general way, the Blue Nile to
Ehri, and then go almost due south to Uganda and Lake Victoria, the
second largest lake of the world. We shall skirt the eastern edge of
the Sudd, in which there is hardly a single safe landing place. Except
in the main channels, masses of papyrus completely hide the water,
and if we should come down in that treacherous region we could
hardly hope to get out alive. We should be unable to walk, swim, or
float in the dense tangle.
This second leg of our journey takes us into the heart of Africa.
The country is wooded and mountainous. It is very hot, for we are
nearing the Equator, which cuts across the upper edge of Lake
Victoria. In fact, our pilot will not fly after nine in the morning nor
earlier than four o’clock in the afternoon. The air is more “bumpy,”
and often terrific thunderstorms seem to fill the sky with sheets of
water. In dodging these storms, we must be careful not to fly so far
off our course as to be forced to land in the wilds. The country here

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Biobased smart polyurethane

nanocomposites from synthesis to

Glass nanocomposites : synthesis, properties and

Nanomaterials and Nanocomposites: Synthesis,

Iptycenes Chemistry From Synthesis to Applications 1st

Helicene Chemistry From Synthesis to Applications 1st

Smart Polymer Nanocomposites: Energy Harvesting, Self-

Electrically Conductive Polymers and Polymer Composites

Nanotechnology: Synthesis to Applications 1st Edition

Ferroic Materials for Smart Systems From Fundamentals

From Synthesis to Applications

Titles in this series:

15: Functional Metallosupramolecular Materials

24: Smart Materials for Tissue Engineering: Fundamental Principles

How to obtain future titles on publication:

For further information please contact:

Biobased Smart Polyurethane

Smart Materials No. 26

Print ISBN: 978-1-78801-180-8

© Niranjan Karak 2017

All rights reserved

permission in writing of The Royal Society of Chemistry or the copyright owner, or in

The Royal Society of Chemistry is a charity, registered in England and Wales,

For further information see our web site at www.rsc.org

Polyurethane (PU) is one of the most versatile industrially important petro-

processing properties and other attributes of said polymers. Thus, biobased

Smart Materials No. 26

memory materials, self-healing materials, self-cleaning materials, biomateri-

teachers, but also the industry and R&D professionals.

7, respectively. All these chapters provide the basic understanding, signifi-

Abbreviations and Symbols

AESO Acrylated epoxidized dL Deciliter(s)

memory DSC Differential scan-

Smart Materials No. 26

xii Abbreviations and Symbols

chromatography Mn Number average molecu-

K Kelvin PCL Poly(ε-caprolactone) diol

Abbreviations and Symbols xiii

SWCNT Single-walled carbon UVA Unmanned air vehicle

Chapter 1 Biobased Hyperbranched Polyurethane  1

1.6.1 Spectroscopic Techniques  23

Smart Materials No. 26

1.8.5 Self-Cleaning Materials  35

Chapter 2 Nanomaterials for Polyurethane Nanocomposites  41

Chapter 3 Biobased Polyurethane Nanocomposites  80

4.1 I ntroduction  112

4.3.1 Waterborne  117

4.7.5 Flammability  142

Chapter 5 Shape Memory Materials  154

5.1 I ntroduction  154

5.6.4 Moisture  169

Chapter 6 Self-Healing Materials  187

6.1 I ntroduction  187

6.3 Basic Understanding  192

7.1 I ntroduction  216

7.4 Techniques to Produce Self-Cleaning Surfaces  221

Chapter 8 Biomaterials  241

8.1 I ntroduction  241

8.2.2 Ceramics  244

Chapter 9 Packaging Materials  270

9.1 I ntroduction  270

9.7.2 Food Items  287

Chapter 10 Miscellaneous: Other Applications  294

AESO Acrylated epoxidized dL Deciliter(s)

memory DSC Differential scan-

chromatography Mn Number average molecu-

K Kelvin PCL Poly(ε-caprolactone) diol

SWCNT Single-walled carbon UVA Unmanned air vehicle

Chapter 1 Biobased Hyperbranched Polyurethane 1

1.6.1 Spectroscopic Techniques 23

1.8.5 Self-Cleaning Materials 35

Chapter 2 Nanomaterials for Polyurethane Nanocomposites 41

Chapter 3 Biobased Polyurethane Nanocomposites 80

4.1 I ntroduction 112

4.3.1 Waterborne 117

4.7.5 Flammability 142

Chapter 5 Shape Memory Materials 154

5.1 I ntroduction 154

5.6.4 Moisture 169

Chapter 6 Self-Healing Materials 187

6.1 I ntroduction 187

6.3 Basic Understanding 192

7.1 I ntroduction 216

7.4 Techniques to Produce Self-Cleaning Surfaces 221

Chapter 8 Biomaterials 241

8.1 I ntroduction 241

8.2.2 Ceramics 244

Chapter 9 Packaging Materials 270

9.1 I ntroduction 270

9.7.2 Food Items 287

Chapter 10 Miscellaneous: Other Applications 294

10.1 I ntroduction 294

Subject Index 320

Figure 1.1 General structure of hypothetical PU with different possible linkages.

1.2 Historical Background

Figure 1.2 Classification of PU materials.

Figure 1.3 General structures of biobased LPU, HPU, and a PU dendrimer.

1.3.3 Thermal Response

1.3.4 Properties and Applications