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Polymeric Materials in
Corrosion Inhibition
Fundamentals and Applications
Polymeric Materials in
Corrosion Inhibition
Fundamentals and Applications

Saviour A. Umoren
Interdisciplinary Research Center for Advanced Materials, King Fahd
University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia

Moses M. Solomon
Department of Chemistry, Covenant University, Ota, Nigeria

Viswanathan S. Saji
Interdisciplinary Research Center for Advanced Materials, King Fahd
University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia
Elsevier
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Contents
About the authors ....................................................................................................xv
Preface .................................................................................................................. xvii
Acknowledgments ..................................................................................................xxi

PART I The Fundamentals................................................... 1

CHAPTER 1 Basic polymer concepts I ............................................. 3
1.1 Introduction ....................................................................................3
1.2 Classification of polymers .............................................................4
1.2.1 Classification based on source............................................ 4
1.2.2 Classification based on structure of polymers ................... 4
1.2.3 Classification based on mode of polymerization ............... 7
1.2.4 Classification based on molecular forces ........................... 8
1.3 General properties of polymers....................................................11
1.3.1 Thermal properties ............................................................ 11
1.3.2 Mechanical properties ....................................................... 13
1.3.3 Solubility properties.......................................................... 13
1.3.4 Optical properties.............................................................. 14
1.4 Polymerization reactions ..............................................................14
1.4.1 Chain-growth or addition polymerization reactions......... 14
1.4.2 Step-growth or condensation polymerization reaction..... 23
1.4.3 Ionic polymerization ......................................................... 25
1.4.4 Coordination polymerization ............................................ 31
1.4.5 Controlled radical polymerization .................................... 35
1.5 Polymerization techniques ...........................................................41
1.5.1 Gas phase polymerization................................................. 42
1.5.2 Bulk polymerization.......................................................... 42
1.5.3 Solution polymerization.................................................... 44
1.5.4 Suspension polymerization ............................................... 45
1.5.5 Emulsion polymerization .................................................. 45
1.5.6 Solid phase polymerization............................................... 47
Further reading ............................................................................ 48

CHAPTER 2 Basic polymer concepts II.......................................... 49

2.1 Molecular weight and molecular weight distribution .................49
2.1.1 Methods of molecular weight determination ................... 51

v
vi Contents

2.2 Copolymerization .........................................................................57

2.2.1 Types of copolymers......................................................... 58
2.2.2 Copolymer composition.................................................... 59
2.3 Biodegradable polymers...............................................................64
2.4 Uses of polymers..........................................................................65
2.4.1 Polymers in corrosion control........................................... 66
2.4.2 Polymers as scale inhibitors ............................................. 66
2.4.3 Polymers as adsorbents ..................................................... 68
2.4.4 Polymers in biomedical applications................................ 72
2.4.5 Polymers for enhanced oil recovery................................. 72
2.4.6 Other applications ............................................................. 75
References.................................................................................... 78
Further reading ............................................................................ 81

CHAPTER 3 Basic concepts of corrosion ...................................... 83

3.1 Introduction ..................................................................................84
3.2 Definition......................................................................................84
3.3 Types of corrosion........................................................................84
3.3.1 Uniform or general corrosion ......................................... 84
3.3.2 Galvanic or bimetallic corrosion .................................... 85
3.3.3 Pitting corrosion.............................................................. 85
3.3.4 Crevice corrosion ............................................................ 85
3.3.5 Intergranular corrosion.................................................... 86
3.3.6 Dealloying ....................................................................... 86
3.3.7 Flow-assisted corrosion................................................... 86
3.3.8 Stress corrosion cracking ................................................ 87
3.3.9 Microbiologically influenced corrosion ......................... 87
3.3.10 Filiform corrosion ........................................................... 87
3.3.11 Exfoliation....................................................................... 88
3.3.12 Corrosion fatigue............................................................. 88
3.3.13 Hydrogen embrittlement corrosion................................. 88
3.3.14 Fretting corrosion............................................................ 88
3.3.15 Sweet and sour corrosion................................................ 89
3.3.16 Top of the line corrosion ................................................ 90
3.4 Factors influencing corrosion.......................................................91
3.4.1 Physical factors ................................................................. 91
3.4.2 Chemical factors ............................................................... 92
3.4.3 Biological factors .............................................................. 92
3.4.4 Surface area effect ............................................................ 92
3.5 Consequences and cost of corrosion............................................92
3.6 Theories of corrosion ...................................................................93
 Contents vii

3.7 Corrosion mitigation approaches .................................................96

3.7.1 Protective coatings ............................................................ 96
3.7.2 Material selection and design ........................................... 98
3.7.3 Cathodic protection ........................................................... 98
3.7.4 Corrosion inhibitors .......................................................... 98
References.................................................................................... 99
Further reading .......................................................................... 102

CHAPTER 4 Fundamentals of corrosion inhibition ...................... 103

4.1 Introduction ................................................................................103
4.2 Corrosion inhibitors....................................................................104
4.3 Classes of corrosion inhibitors...................................................104
4.3.1 Passivating inhibitors ...................................................... 104
4.3.2 Cathodic inhibitors.......................................................... 105
4.3.3 Organic inhibitors ........................................................... 105
4.3.4 Precipitation inhibitors.................................................... 106
4.3.5 Volatile corrosion inhibitors ........................................... 106
4.3.6 Adsorption inhibitors ...................................................... 106
4.3.7 Surface reaction product inhibitors ................................ 106
4.3.8 Interphase inhibitors........................................................ 107
4.3.9 Interface inhibitors .......................................................... 107
4.4 Factors affecting corrosion inhibitor effectiveness ...................107
4.5 Mechanism of corrosion inhibition............................................109
4.6 Techniques for corrosion rate and inhibition efficiency
determination..............................................................................110
4.6.1 Chemical techniques ....................................................... 110
4.6.2 Electrochemical methods ................................................ 114
4.7 Surface analysis methods ...........................................................122
4.7.1 Atomic force microscopy................................................ 122
4.7.2 X-ray photoelectron spectroscopy .................................. 122
4.7.3 Scanning electron microscopy ........................................ 123
4.7.4 Energy dispersive spectroscopy...................................... 124
References.................................................................................. 125
Further reading .......................................................................... 127

Part II Natural Polymers in Corrosion Inhibition............ 129

CHAPTER 5 Chitosan..................................................................... 131
5.1 Introduction ................................................................................131
viii Contents

5.2 Synthesis and properties of chitosan .........................................132

5.2.1 Preparation ...................................................................... 132
5.2.2 Properties......................................................................... 134
5.3 Application of chitosan as corrosion inhibitor in diverse
media ..........................................................................................136
5.3.1 Acid media ...................................................................... 137
5.3.2 Other corrosive media..................................................... 142
5.4 Enhancement of corrosion inhibition performance
of chitosan ..................................................................................145
5.4.1 Combination for synergistic effect ................................. 145
5.4.2 Modification by compositing.......................................... 147
References.................................................................................. 148

CHAPTER 6 Chitosan derivatives ................................................. 155

6.1 Introduction ................................................................................155
6.1.1 Synthesis and characterization of chitosan
derivatives ....................................................................... 156
6.2 Application of chitosan derivatives as corrosion inhibitors
in different media .......................................................................169
6.2.1 Chitosan derivatives with diverse heteroatoms .............. 171
6.2.2 Chitosan Schiff bases in corrosion inhibition ................ 175
6.2.3 Other chitosan derivatives in corrosion inhibition ......... 175
6.3 Enhancement of corrosion inhibition by chitosan
derivatives...................................................................................177
References.................................................................................. 181

CHAPTER 7 Cellulose and its derivatives.................................... 187

7.1 Introduction ................................................................................187
7.1.1 Carboxymethyl cellulose ................................................ 189
7.2 Other cellulose derivatives.........................................................197
7.2.1 Other cellulose derivatives as corrosion inhibitors ........ 201
7.2.2 Enhancement of corrosion inhibition performance
of other cellulose derivatives.......................................... 201
References.................................................................................. 204

CHAPTER 8 Natural gums and their derivatives.......................... 209

8.1 Introduction ................................................................................209
8.1.1 Classification of gums .................................................... 211
8.2 Application of gums as corrosion inhibitors .............................213
 Contents ix

8.2.1 Gum Arabic..................................................................... 213

8.2.2 Gum Arabic in corrosion inhibition ............................... 216
8.3 Guar gum....................................................................................221
8.3.1 Preparation ...................................................................... 222
8.3.2 Properties......................................................................... 223
8.3.3 Guar gum in corrosion inhibition ................................... 224
8.4 Xanthan gums.............................................................................225
8.4.1 Xanthan gums in corrosion inhibition ............................ 227
8.5 Gellan gum .................................................................................230
8.5.1 Preparation ...................................................................... 230
8.5.2 Properties......................................................................... 231
8.5.3 Gellan gum in corrosion inhibition ................................ 231
References.................................................................................. 232

CHAPTER 9 Other natural gums and gum modifications............. 237

9.1 Introduction ................................................................................237
9.2 Carrageenan................................................................................237
9.2.1 Carrageenan in corrosion inhibition ............................... 240
9.3 Other exudate gums in corrosion inhibition ..............................240
9.4 Enhancement of the corrosion inhibition performance
of gums .......................................................................................248
9.4.1 Chemical modification.................................................... 248
9.4.2 Synergism........................................................................ 250
References.................................................................................. 251

CHAPTER 10 Pectin and derivatives .............................................. 255

10.1 Introduction ................................................................................255
10.2 Classification of pectin...............................................................256
10.3 Sources and preparation of pectin .............................................257
10.4 Properties of pectin ....................................................................259
10.5 Application of pectin as a corrosion inhibitor...........................261
10.6 Enhancement of the corrosion inhibition performance
of pectin......................................................................................266
References.................................................................................. 267

CHAPTER 11 Alginate and its derivatives...................................... 271

11.1 Introduction ................................................................................271
11.2 Preparation of alginate ...............................................................271
11.3 Properties of alginates................................................................274
x Contents

11.4 Application of alginates as corrosion inhibitors........................276

11.5 Enhancement of corrosion inhibition performance of
alginates......................................................................................277
References.................................................................................. 284

CHAPTER 12 Starch and its derivatives ........................................ 287

12.1 Introduction ................................................................................287
12.2 Preparation of starch ..................................................................288
12.3 Properties of starch.....................................................................290
12.3.1 Physical properties ........................................................ 290
12.3.2 Chemical properties ...................................................... 291
12.4 Application of starch as a corrosion inhibitor ...........................296
12.5 Enhancement of the corrosion inhibition performance
of starch ......................................................................................296
References.................................................................................. 301

CHAPTER 13 Other natural polymers: gelatin, dextrin, and

dextran....................................................................... 303
13.1 Gelatins.......................................................................................303
13.1.1 Preparation and properties of gelatin ........................... 304
13.2 Dextrin ........................................................................................308
13.2.1 Preparation and properties of dextrin ........................... 308
13.3 Dextran .......................................................................................310
13.3.1 Preparation and properties of dextran .......................... 311
13.4 Application of gelatin, dextrin, and dextran as corrosion
inhibitors.....................................................................................313
13.5 Gelatin, dextrin, and dextran corrosion inhibition ....................314
References.................................................................................. 320

Part III Synthetic Polymers in Corrosion Inhibition ....... 323

CHAPTER 14 Polyglycols................................................................ 325
14.1 Introduction ................................................................................325
14.2 Polyethylene glycol ....................................................................326
14.2.1 Preparation .................................................................... 326
14.2.2 Properties....................................................................... 327
14.3 Polypropylene glycol..................................................................328
14.3.1 Preparation .................................................................... 328
14.3.2 Properties....................................................................... 329
 Contents xi

14.4 Corrosion inhibition by polyethylene glycol and

polypropylene glycol..................................................................329
14.5 Enhancement of corrosion inhibition performance of
polyethylene glycol and polypropylene glycol..........................333
14.5.1 Chemical modification.................................................. 333
14.5.2 Enhancement through compositing and combination
with synergists............................................................... 334
References.................................................................................. 340

CHAPTER 15 Acrylic polymers ....................................................... 343

15.1 Introduction ................................................................................343
15.2 Polyacrylic acid ..........................................................................344
15.2.1 Synthesis and properties ............................................... 345
15.2.2 Polyacrylic acid and sodium polyacrylate as
corrosion inhibitors ....................................................... 346
15.2.3 Enhancement of corrosion inhibition properties .......... 350
15.3 Polymethacrylic acid ..................................................................350
15.3.1 Synthesis and properties ............................................... 350
15.3.2 Polymethacrylic acid as a corrosion inhibitor.............. 353
15.3.3 Enhancement of corrosion inhibition effect ................. 353
15.4 Polyacrylamide ...........................................................................356
15.4.1 Preparation .................................................................... 357
15.4.2 Physical properties ........................................................ 359
15.4.3 Chemical properties ...................................................... 359
15.4.4 Polyacrylamide as a corrosion inhibitor....................... 362
15.4.5 Ways to improve corrosion inhibition performance .... 364
References.................................................................................. 368

CHAPTER 16 Vinyl polymers .......................................................... 373

16.1 Introduction ................................................................................373
16.2 Polyvinyl alcohol........................................................................374
16.2.1 Preparation and properties ............................................ 374
16.2.2 Polyvinyl alcohol as a corrosion inhibitor ................... 379
16.2.3 Enhancement of corrosion inhibition performance...... 380
16.3 Polyvinyl pyrrolidone.................................................................384
16.3.1 Preparation .................................................................... 384
16.3.2 Polyvinyl pyrrolidone as corrosion inhibitor................ 388
16.3.3 Ways to enhance corrosion inhibition performance .... 392
References.................................................................................. 395
xii Contents

CHAPTER 17 Polyethers ................................................................. 399

17.1 Introduction ................................................................................399
17.2 Polyethylene oxide .....................................................................400
17.2.1 Preparation of polyethylene oxide................................ 400
17.2.2 Properties of polyethylene oxide .................................. 401
17.3 Polypropylene oxide...................................................................403
17.3.1 Preparation of polypropylene oxide ............................. 403
17.3.2 Properties of polypropylene oxide................................ 404
17.4 Polyethers as corrosion inhibitors..............................................405
17.4.1 Enhanced performance of polyether-potassium
iodide mixture ............................................................... 407
17.4.2 Enhanced performance of polyethers
nanocomposites and copolymers .................................. 408
17.4.3 Corrosion inhibition property of macrocyclic
polyethers ...................................................................... 416
References.................................................................................. 416

CHAPTER 18 Resin based polymers............................................... 419

18.1 Introduction ................................................................................419
18.2 Synthesis and properties of resin-based polymers.....................420
18.2.1 Epoxy resins .................................................................. 420
18.2.2 Preparation and properties ............................................ 424
18.3 Resin-based polymers in corrosion inhibition ...........................427
References.................................................................................. 439

CHAPTER 19 Conducting polymers ................................................ 443

19.1 Introduction ................................................................................443
19.2 Classification of conducting polymers ......................................444
19.2.1 Polyacetylenes............................................................... 444
19.2.2 Polyphenylenes.............................................................. 446
19.2.3 Polythiophene................................................................ 447
19.2.4 Polypyrrole .................................................................... 447
19.2.5 Poly(arylene vinylenes) ................................................ 453
19.2.6 Polyaniline..................................................................... 454
19.3 Conducting polymers in corrosion inhibition............................460
References.................................................................................. 462

CHAPTER 20 Dendrimers ................................................................ 467

20.1 Introduction ................................................................................467
20.1.1 Classification/types of dendrimers ............................... 468
 Contents xiii

20.2 Synthesis and properties of dendrimers.....................................470

20.2.1 Synthesis........................................................................ 470
20.2.2 Properties....................................................................... 475
20.3 Dendrimers as corrosion inhibitors............................................479
References.................................................................................. 485

CHAPTER 21 Copolymers................................................................ 489

21.1 Introduction ................................................................................489
21.1.1 Random or statistical copolymers ................................ 489
21.1.2 Alternating copolymers................................................. 490
21.1.3 Block copolymers ......................................................... 490
21.1.4 Graft copolymers........................................................... 493
21.1.5 Copolymer synthesis ..................................................... 493
21.2 Synthetic polymer
based copolymers as corrosion
inhibitors.....................................................................................497
21.3 Natural polymer
based copolymers as corrosion
inhibitors.....................................................................................504
21.4 Conducting polymer
based copolymers as corrosion
inhibitors.....................................................................................510
21.5 Other polymer-based copolymers as corrosion inhibitors.........513
References.................................................................................. 515

CHAPTER 22 Polyaspartic acid and poly(vinylpyridine)

polymers .................................................................... 521
22.1 Introduction ................................................................................521
22.1.1 Polyaspartic acid/polyaspartate..................................... 521
22.1.2 Polyaspartic acid/polyaspartate preparation ................. 522
22.2 Poly(4-vinylpyridine) .................................................................523
22.2.1 Properties....................................................................... 524
22.3 Application of polyaspartic acid and poly(vinylpyridine)
polymers as corrosion inhibitors................................................524
22.3.1 Polyaspartic acid as a corrosion inhibitor .................... 524
22.3.2 Poly(vinylpyridine) as a corrosion inhibitor ................ 533
References.................................................................................. 538

CHAPTER 23 Other synthetic polymers .......................................... 541

23.1 Introduction ................................................................................541
23.2 Polyethyleneimine ......................................................................541
23.2.1 Preparation and properties ............................................ 542
xiv Contents

23.3 Polyamides .................................................................................543

23.3.1 Properties....................................................................... 544
23.3.2 Preparation .................................................................... 545
23.4 Polyvinyl acetate ........................................................................546
23.4.1 Preparation and properties ............................................ 546
23.5 Other synthetic polymers ...........................................................547
23.6 Application of synthetic polymers as corrosion inhibitors .......547
23.6.1 Polyamide as a corrosion inhibitor............................... 547
23.6.2 Polyethyleneimine as a corrosion inhibitor .................. 551
23.6.3 Corrosion inhibition performance of other
synthetic polymers ........................................................ 560
References.................................................................................. 561

CHAPTER 24 Mechanism of corrosion inhibition by polymers ..... 565

24.1 Introduction ................................................................................565
24.2 Adsorption mechanism of polymers ..........................................567
24.3 Quantum chemical calculations .................................................572
24.4 Molecular dynamics and Monte Carlo simulations...................579
24.4.1 Molecular dynamics...................................................... 579
24.4.2 Monte Carlo simulation ................................................ 584
References.................................................................................. 586

Index ......................................................................................................................591
About the authors
Dr. Saviour A. Umoren is currently an associate professor/a
research scientist at the Interdisciplinary Research Center for
Advanced Materials, King Fahd University of Petroleum &
Minerals (KFUPM), in Saudi Arabia. He has 24 years of
experience in teaching and research in both university and
industrial environments in the field of corrosion inhibition,
leading many research projects in the area of corrosion miti-
gation. He has authored or coauthored over 150 research
articles published in international peer-reviewed journals,
edited one book, contributed to 10 book chapters, was
granted three US patents, and is on the editorial board of
13 international journals. Dr. Umoren’s research interests cover the investigation
of corrosion and corrosion inhibition phenomena in different environments.
His current research focuses on polymer composites and nanocomposites for
corrosion protection and the development of environmentally friendly corrosion
inhibitors for industrial metals.
Dr. Moses M. Solomon is currently a senior lecturer in
the Department of Chemistry, Covenant University Otta,
in Nigeria. He was a postdoctoral research fellow at
Duzce University, Turkey (2016
17) and at the
Interdisciplinary Research Center for Advanced Materials,
KFUPM, Saudi Arabia (2018
20). His research interests
focus primarily on the development of green corrosion
inhibitors for diverse kinds of aggressive environments
using polymeric materials. Dr. Solomon has authored
over 65 journal publications and has contributed to six
book chapters.
Dr. Viswanathan S. Saji is a research scientist III/an
assistant professor at the Interdisciplinary Research
Center for Advanced Materials, King Fahd University of
Petroleum & Minerals (KFUPM), Saudi Arabia. He has
more than 18 years of post-doctoral research experience
in various universities and industrial sectors in India, the
Republic of Korea, and Australia. Dr. Saji’s research
interests lie in electrochemistry, corrosion science, and
smart/bio/energy materials, and he has authored 80 journal
publications, edited or authored 9 books, and contributed
15 book chapters.

xv
Preface
Polymeric materials have become indispensable in our daily lives because of their
great versatility and their resulting unique material properties. Polymers have
seen tremendous development since the pioneering work of Staudinger. In the
years since then, polymer science has developed to become both technically
demanding and industrially extremely important. Polymers find usage in a wide
range of industries, including the electrical and electronics, construction, automo-
bile, and packaging industries. Biodegradable polymers are indispensable in bio-
medical applications, including tissue engineering and drug delivery. In the field
of environmental science and engineering, polymers are used as adsorbents to
remove contaminants from wastewater. Polymers are useful in controlling scale
and corrosion in cooling water systems and oil fields, and they play an important
role in enhanced oil recovery in the petroleum industry.
Metal corrosion is a worldwide problem. The utilization of chemical inhibitors
is one of the most common corrosion control methods in various industrial sec-
tors. Inhibitors are essential additives in refinery processing units, oil and gas pro-
duction units, gas oil separation units, petroleum products
transporting pipelines,
cooling water systems, steam generators, and several other industries. Among the
different classes of inhibitors, the organic polymeric inhibitors have attracted a
great deal of attention, owing to their inherent stability, cost-effectiveness, superb
adhesion properties, and high corrosion inhibition attributes. This book aims to
provide a comprehensive overview of the fundamentals and applications of poly-
meric corrosion inhibitors. To the best of our knowledge, there is no dedicated
textbook dealing with polymeric materials used as corrosion inhibitors to control
corrosion in diverse corrosive environments.
The book covers both fundamentals and most of the recent advancements in
this field. It is organized into three parts. Part I concentrates on the basic concepts
of polymers as well as corrosion and corrosion inhibition. Part II deals with natu-
ral polymers in corrosion inhibition. Part III is devoted to synthetic polymers in
corrosion inhibition.
Even though the chapters are framed on the basis of the corrosion inhibition
characteristics, the book’s primary aim is to provide clear fundamentals on the
synthetic pathways and properties of various polymers of interest. With this
objective, Chapters 1 and 2 are dedicated to the basics of polymeric materials,
including the definition of polymer, classification of polymers, the concept of
molecular weight and molecular weight distribution, polymerization reactions,
polymerization techniques, and utilization of polymeric materials as antiscalants
and adsorbents. Chapters 3 and 4 give clear descriptions of the fundamentals of
corrosion and corrosion inhibition, including types of corrosion, the costs and
consequences of corrosion, factors affecting corrosion rates, theories of corrosion,
classification of corrosion inhibitors, factors influencing corrosion inhibitor effec-
tiveness, and techniques for evaluating corrosion inhibition.

xvii
xviii Preface

Part II of the book, comprising Chapters 5
13, deals with natural polymers as
corrosion inhibitors. Natural polymers are macromolecules whose molecular units
are linked in a continuous chain of complex structures in living systems.
Depending on their applications, that is, food or nonfood, most natural polymers
are produced in various amounts all over the world. Polysaccharide biopolymers,
for instance, make up between 60% and 85% of the two billion tons of the
world’s renewable resources that are produced annually, and more than half of
them come from natural sources. Most of these polymers are readily modified
(physically and/or chemically) to attain the practical requirements for their end
use with interesting and unique properties. Examples include chitosan, carboxy-
methyl cellulose, starch, pectin, dextran, alginates, hydroxyethyl cellulose, gum
arabic, xanthan gum, and guar gum. Each natural polymer has its own unique
range of molecular and electronic structures, in contrast to simple structures.
Electron-rich species such as free amines, hydroxyls, carboxylic acids, and car-
boxymethyl groups in repeating units can bond to metal surfaces and subse-
quently inhibit corrosion via coordinate linkages. These groups can donate
electrons to the partially occupied orbitals of iron, yielding anticorrosion proper-
ties. On the topic of natural polymers, Chapters 5 and 6 are dedicated to chitosan
and chitosan derivatives, cellulose and its derivatives are covered in Chapter 7,
and gums and their derivatives are discussed in Chapters 8 and 9. Pectin and its
derivatives, alginate and its derivatives, starch and its derivatives, and other natu-
ral polymers, including gelatin and dextrin/dextran, are discussed in Chapters
10
13, respectively. Each chapter covers details of preparation, properties, and
applications of the different polymers as corrosion inhibitors, including ways to
enhance their inhibition performance for diverse industrial metal substrates in dif-
ferent corrosive environments.
Part III, with nine chapters (Chapters 14
23), examines synthetic polymers in
corrosion inhibition. On the topic of synthetic polymers, polyglycols, acrylic poly-
mers, and vinyl polymers are covered in Chapters 14
16, respectively.
Chapter 17 is devoted to polyethers, and resin-based polymers are discussed in
Chapter 18. The utilization of conducting polymers, dendrimers, copolymers,
polyaspartic acid and poly(vinylpyridine) polymers, and other synthetic polymers
is covered in Chapters 19
23, respectively. Each chapter begins with a brief
introduction followed by details of preparation and properties and concludes by
examining the applications of the various polymers as corrosion inhibitors and
methods used to improve their corrosion inhibition performance.
Chapter 24 is dedicated to the mechanism of inhibition of polymeric inhibi-
tors. Polymers can be adsorbed on a metal surface through physical, chemical,
and electrostatic adsorption mechanisms in addition to hydrogen bonding.
Chapter 24 discusses these various polymer adsorption mechanisms. The applica-
tion of theoretical approaches such as the density functional theory, molecular
dynamics simulation, and Monte Carlo simulation in the understanding of
inhibitor
metal surface interactions is also considered in Chapter 24, and the
criticisms of these approaches are highlighted.
 Preface xix

The book is likely to be of considerable interest to the broad and interdisci-

plinary audience of chemistry, engineering, and materials science. We hope that it
will be a handy reference tool for students and researchers working in the field of
polymeric materials and corrosion inhibition.

Saviour A. Umoren1, Moses M. Solomon2 and Viswanathan S. Saji1

1
Interdisciplinary Research Center for Advanced Materials,
King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia
2
Department of Chemistry, Covenant University, Ota, Nigeria
Acknowledgments
We would like to express our gratitude to King Fahd University of Petroleum &
Minerals (KFUPM), Saudi Arabia, and Covenant University, Ota, Nigeria, for the
moral support they provided. We would also like to express our gratitude to all
the authors of the books and articles we have referenced and to all the publishers
and sources that have granted us the copyright permissions for reproducing illus-
trations. Our sincere thanks to the Elsevier team for helping this book to evolve
into its final shape.
We gratefully acknowledge those closest to us: our families, our spouses, and
of course our children. We are indebted to them for their patience, guidance, and
perseverance and most of all for their love during the preparation of this book.

xxi
 PART

The Fundamentals
I
Another random document with
no related content on Scribd:
[453]

Howard, Bull. Dep. Agric. Ent. N.S. No. 4, 1896.

[454]

Schimkewitsch, Zool. Anz. vii. 1884, p. 673.

[455]

P. Boston Soc. xxvi. 1894, pp. 312-355.

[456]

Monographie der Ordnung Thysanoptera, Königgrätz, 4to, 1895.

[457]

Bull. Essex Inst. xxii. 1890, p. 24; also Amer. Natural. xxx. 1896, p.
591.

[458]

Jordan in an interesting paper, Zeitschr. wiss. Zool. xlvii. 1888, p.

573, says that in the division "Terebrantia" there are only three
pairs of stigmata.

[459]

Insect Life, i. 1888, p. 138.

[460]

See Lindeman, Bull. Soc. Moscou, lxii. 1886, No. 2, p. 296, and
Uzel, Mon. 1895, pp. 397, 398.

[461]

Entomological Magazine, iii. 1836, p. 439, and iv. 1837, p. 144.

[462]

Zeitschr. wiss. Zool. xvi. 1866, p. 389.

[463]

Arb. Inst. Wien. iv. 1882, p. 415.

[464]

Tr. Amer. Phil. Soc. xix. 1896, p. 176.

[465]

P. ent. soc. Washington, iii. 1895, p. 241.

[466]

Ent. Nachr. xxii. 1896, p. 173.

[467]

Zool. Anz. 1897, No. 527, p. 73.

[468]

Arch. Anat. Physiol. 1874, p. 313, and 1875, p. 309.

[469]

For the structure and development of the Hemipterous trophi, see

Mayer, Arch. Anat. Physiol. 1874 and 1875; Mecznikow, Zeitschr.
wiss. Zool. xvi. 1866, p. 389; Geise, Arch. Naturgesch. xlix. 1,
1883, p. 315; Wedde, op. cit. li. 1, 1885, p. 113; Mark, Arch. mikr.
Anat. xiii. 1877, p. 31: Smith, Tr. Amer. Phil. Soc. xix. 1896, p. 176.

[470]

Ent. Nachr. xix. 1893, p. 369.

[471]

Naturhist. Tidskr. (3) vi. 1896; translated in Ann. N. Hist. (4), vi.
1870, p. 225.

[472]

Ent. Zeit. Stettin, xxvii. 1866, p. 321.

[473]

Ent. Nachr. xix. 1893, p. 375.

[474]

On this subject, see Reuter, Ann. Soc. ent. France (5) v. 1875, p.
225.

[475]

Ann. Soc. ent. France (4) vii. 1867, p. 45.

[476]

The chief work on the internal anatomy of Hemiptera is still

Dufour's Recherches anatomiques et physiologiques sur les
Hémiptères, Mem. Savans Étrangers, Paris, iv. 1833, p. 129.

[477]

Künckel, Ann. Soc. ent. France (4) vii. 1867, p, 45, and C.R. Ac.
Paris, cxx. 1895, p. 1002.

[478]

In Slingerland's Cornell Univ. Bull. No. 58, 1893, p. 222.

[479]

SB. Ak. Wien. xci. 1 Abth., 1885, p. 275.

[480]

Les Insectes fossiles, etc., 1894, p. 452.

[481]

Ann. Nat. Hist. (4) vi. 1870, p. 225.

[482]

A table of the families is given by Ashmead, but does not work out
quite satisfactorily, Entom. Americana, iv. 1888, p. 65; a brief table
of the characters of the British families is given by Saunders,
Hemiptera-Heteroptera of the British Islands, 1892, p. 12.

[483]

Those who wish to see tables of the families are referred to

Ashmead, loc. cit.; to Pascoe, Ann. Nat. Hist. (5) ix. 1882, p. 424;
to Stål's Hemiptera Africana, vol. iv. 1866; and for the families
found in Britain to Edwards, Hemiptera-Homoptera of the British
Islands. For a discussion in Danish on the value of the characters
used, cf. Hansen, Ent. Tidskr. xi. 1890, pp. 19-76.

[484]

Ent. Mag. vii. 1870, p. 53.

[485]

Insect Life, i. 1889, p. 234.

[486]

C.R. Ac. Sci. Paris, cxviii. 1894, p. 1282.

[487]

Verh. Ges. Wien. iii. 1858, p. 157.

[488]

Ent. Mag. xxix. 1893, p. 227.

[489]

Wien. ent. Zeit. xi. 1892, p. 169.

[490]

Monograph of Phymatidae: Handlirsch, Ann. Hofmus. Wien, xii.

1897, p. 127.

[491]
Ent. Zeit. Stettin, li. 1890, p. 281.

[492]

Naturalist's Voyage, ed. 1884, p. 330; chap. xv.

[493]

Thesaurus ent. Oxoniensis, 1874, p. 197.

[494]

Ind. Mus. Notes, iii. No. 5, 1894, p. 53.

[495]

Ferrari, Monograph of Nepa, Ann. Hofmus. Wien, iii. 1888, p. 171.

[496]

Bull. Soc. Philomat. (8) v. 1893, p. 57. There is some diversity of

opinion as to the respiratory orifices, and some authorities say that
thoracic stigmata exist even in the imago.

[497]

Acta Ac. German. li. 1887, p. 224, and Zeitschr. wiss. Zool. xliii.
1886, p. 537.

[498]

Korschelt, Acta. t.c. p. 245. Compare the remarks we have made

on p. 559 as to the peculiarities of eggs of many other Hemiptera.

[499]

Bull. Mus. Paris, 1896, p. 238.

[500]

See Carpenter, Irish Naturalist, iv. 1895, p. 59.

[501]
See remarks on pp. 543, 544.

[502]

We must refer those who may wish for further information as to

this complex and difficult question to the writings of the late
Professor Riley, especially to Bulletin No. 8, 1885, U.S.
Department of Agriculture, division of entomology; and to the more
recent report by Marlatt, Bull. Dep. Agric. Ent., N.S. No. 14, 1898.

[503]

Some entomologists consider that this "railway-whistle" note is the

result of the combined efforts of several individuals. Cf. Mathew,
Ent. Mag. xi. 1875, p. 175.

[504]

It is unnecessary to say that the poet was not Sappho, but one of
the baser sex, named Xenarchus.

[505]

Swinton claims that one of the membranes in the vocal apparatus

is an auditory organ; if so, the male would be deafened by his own
noise, while the females, not possessing the organ, should not
hear the song.

[506]

P. ent. Soc. London, 1883, p. 20.

[507]

A considerable variety of these extraordinary creatures are figured

in Biol. Centr. Amer. Rhynch. Homopt. ii.

[508]

Riley, P. ent. Soc. Washington, iii. 1895, p. 88. For the younger
stages of Membracis foliata, see Tijdschr. Ent. (2) iv. 1869, pl. viii.
[509]

Tr. ent. Soc. London, 1886, p. 329.

[510]

Verh. z.-b. Ges. Wien, xxvi. 1876, p. 167.

[511]

Cornell Univ. Agric. exp. station Bulletin, 44, 1892, and Bull. 108,
1896.

[512]

Zeitschr. wiss. Zool. xlii. 1885, pp. 569-638.

[513]

Zeitschr. Naturw. (2) xii. 1875, p. 438.

[514]

Réaumur, Mém. iii. 1737, Dixiéme Mémoire.

[515]

P. ent. soc. Washington, iv. 1897, p. 66.

[516]

For list see Scott, Ent. Mag. xviii. 1882, p. 253.

[517]

There is some doubt on this point, as the earlier observers seem

to have supposed that a winged individual appearing in a
generation chiefly apterous was ipso facto, a male; it seems,
however, to be certain that perfect winged males appear in some
species in generations producing no perfect sexual females.
Speaking generally, the course of events seems to be that in
summer there exist only wingless and winged parthenogenetic
females, and that the sexually perfect forms appear for the first
time in autumn.

[518]

Mitt. Schweiz. ent. Ges. iv. 1876, p. 529.

[519]

The term pseudovum is applied, as a matter of convenience, to the

earlier condition of the viviparously-produced form, and the term
pseudovarium to the ovary producing it.

[520]

Balbiani, Ann. Sci. Nat. Zool. (5) xi. 1869, p. 29. For concise recent
remarks on the early embryonic states, see Lemoine, Bull. Soc.
ent. France, 1893, p. lxxxix.

[521]

Acta Ac. German. xxxiii. 1869, No. 2, p. 81.

[522]

Seventeenth Rep. Insects Illinois, 1891, p. 66.

[523]

Kessler, Acta Ac. German. li. 1887, pp. 152, 153.

[524]

In connection with this the absence of a functional mouth in the

imago state of numerous Lepidoptera, and of Oestrid Diptera,
should not be forgotten.

[525]

Horae Soc. ent. Ross. xxiv. 1890. p. 386.

[526]
Ent. Zeit. Stettin, xxxvi. 1875, p. 368.

[527]

Zool. Anz. xv. 1892, p. 220.

[528]

Arb. Inst. Wien, iv. 1882, Heft iii. p. 397; see on this organ also
Mordwilko, Zool. Anz. xviii. 1895, p. 357.

[529]

Biol. Centralbl. xi. 1891, p. 193.

[530]

See, inter alia, Webster, J. New York ent. Soc. i. 1893, p. 119.

[531]

J. New York Ent. Soc. i. 1893, p. 120. See also as to knowledge

on the part of ants, Forbes, Eighteenth Rep. Insects Illinois, 1894,
pp. 66, etc.

[532]

Monograph by Buckton, Ray Society, 4 vols. 1879-1883.

[533]

Tr. New Zealand Inst. xxviii. 1895.

[534]

A catalogue of Coccidae has recently been published by Mr. T. D.

A. Cockerell in Bull. Illinois Lab. iv. 1896, pp. 318-339.

[535]

Signoret's papers are to be found in eighteen parts in Ann. Soc.

ent. France, 1868 to 1876: the most considerable subsequent
systematic papers are those by Maskell in the Transactions of the
New Zealand Institute from 1878 to the present time.

[536]

Coccidae of Ceylon, pt. 1, 1896, p. 16.

[537]

C. R. Ac. Sci. Paris, civ. 1887, p. 449.

[538]

Arch. Naturgesch. li. i. 1885, p. 169.

[539]

Zeitschr. wiss. Zool. xliii. 1886, p. 156.

[540]

For summary as to our present knowledge of this curious condition

of Insect life, see Mayet, Ann. Soc. ent. France, 1896, p. 419.

[541]

For additional information as to useful Coccidae, see Blanchard,

Bull. Soc. Zool. France, viii. 1883, p. 217.

[542]

Rubsaamen's paper on these Insects gives references to most of

the previous literature, Berlin. ent. Zeitschr. xxxix. 1894, p. 199.

[543]

Ent. Meddel. iii. 1891, p. 82.

[544]

Cf. Graber, Zeitschr. wiss. Zool. xxii. 1872, p. 165, and Landois in
the same Journal, xiv. 1864, p. 24.
[545]

Ann. Nat. History (3), xvii. 1866, p. 213.

[546]

N. York Ent. Soc. vii. March 1899, p. 45.

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