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Principles, Designing and Applications

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 ECO-FRIENDLY
CORROSION INHIBITORS
 ECO-FRIENDLY
CORROSION
INHIBITORS
PRINCIPLES, DESIGNING AND
APPLICATIONS
Edited by

Lei Guo
School of Materials and Chemical Engineering, Tongren University, Tongren, China

Chandrabhan Verma
Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum and Minerals, Dhahran,
Saudi Arabia

Dawei Zhang
University of Science & Technology Beijing, Beijing, China
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 Contents

Contributors xi 3. Development process for eco-friendly

Preface xv corrosion inhibitors
MOHAMED RBAA, MOUHSINE GALAI, OMAR DAGDAG,
LEI GUO, BURAK TÜZÜN, ELYOR BERDIMURODOV,

Part 1 ABDELKADER ZARROUK, BRAHIM LAKHRISSI

Overview of industrial corrosion 3.1 Introduction 27

3.2 Process for development of eco-friendly synthesizing
and inhibition corrosion inhibitors 28
3.3 Process for development of eco-friendly extracting
1. General principles of industrial corrosion inhibitors 30
Conclusion 39
corrosion References 40
SHEERIN MASROOR

1.1
1.2
Introduction 3
Materials in industrial applications 3
Part 2
1.3 General principles or theories of industrial Industrial environments & corrosion
corrosion 4
1.4 Different types of corrosion in industries 5
inhibitors
1.5 Corrosion of metal in industries 10
References 12 4. Acidizing corrosion inhibitors
HAO LI, YUJIE QIANG, CHANDRABHAN VERMA
2. Corrosion prevention and
protection methods 4.1 Introduction of acidizing corrosion inhibitors 45
4.2 Acidizing inorganic corrosion inhibitor 46
SAMAN ZEHRA, MOHAMMAD MOBIN,
RUBY ASLAM 4.3 Acidizing organic corrosion inhibitor 46
4.4 New acidizing corrosion inhibitor 47
2.1 Introduction 13 Conclusion 52
2.2 Important considerations required for the corrosion References 53
prevention and control methods 14
2.3 Strategies of the corrosion prevention and control 5. Corrosion inhibitors used in alkaline
methods 18 environments
2.4 Methods of corrosion control 18 DAQUAN ZHANG, JUNYU YANG, PEI GAN, WENYUE ZHANG
Conclusion 25
Acknowledgment 26 5.1 Corrosion inhibitor used for alkaline metal-air
Useful books 26 battery 55
Useful websites 26 5.2 Corrosion inhibitors for rebar in concrete
References 26 reinforcement 64

v
vi Contents

5.3 Corrosion inhibitors in other alkaline media 65 8.5 Eco-friendly corrosion mitigation in the oil and
Summary and outlook 66 gas industry 116
Acknowledgments 67 8.6 Developing the corrosion inhibitor formulation 122
References 67 Conclusion 123
Useful links 124
6. Corrosion inhibitors in near neutral media References 124
K.R. ANSARI, AMBRISH SINGH, ABDULLAH K. ALANAZI,
M.A. QURAISHI 9. Vapor inhibitors for corrosion protection
K.R. ANSARI, AMBRISH SINGH,
6.1 Introduction 71 ABDULLAH K. ALANAZI, M.A. QURAISHI
6.2 Metals corrosion and their inhibition in a neutral
environment 72 9.1 Introduction 127
6.3 Heterocyclic corrosion inhibitors for neutral 9.2 Mechanism of VCI action 128
environments 72 9.3 Developed VCIs for ferrous and nonferrous
Acknowledgment 76 metals 130
References 76 9.4 Some important techniques used for corrosion
inhibition monitoring 133
7. Supramolecular corrosion inhibitors for 9.5 Advantages of VCIs 133
cooling water systems 9.6 Market growth 134
9.7 Methods of VCI application 134
BAOMIN FAN, HUA HAO
Acknowledgment 135
7.1 Introduction to supramolecular corrosion References 135
inhibitors 79
7.2 Preparation of supramolecular corrosion inhibitors 10. Inhibitors for microbiologically
via molecular recognition and self-assembly 82 influenced corrosion (MIC)
7.3 Assembly mechanism of the supramolecular LI FENG, HAILIN ZHU, XUEMEI MA, ZHIYONG HU,
corrosion inhibitor based on CDs 87 AMIR ZOMORODIAN
7.4 Characterizations of supramolecular corrosion
inhibitors 89 10.1 Introduction 137
7.5 Inhibition effect and mechanism of supramolecular 10.2 Microorganism species and MIC mechanism 138
corrosion inhibitors 99 10.3 MIC inhibitors 143
7.6 Supramolecular corrosion inhibitor used in Conclusion 149
industrial water treatment 105 References 150
Conclusions 109
Useful links 109 11. Corrosion inhibitors for Cu chemical
References 109 mechanical planarization (CMP)
BAIMEI TAN, LEI GUO, XINHUAN NIU, DA YIN, TENGDA
8. Corrosion inhibitors for oil and MA, SHIHAO ZHANG, CHENWEI WANG
gas systems
11.1 Benzotriazole (BTA) used for Cu CMP 155
BRAHIM EL IBRAHIMI
11.2 1,2,4-triazole (TAZ) used for Cu CMP 158
8.1 Well acidizing treatments in the oil and gas 11.3 2,2’-[[(methyl-1H-benzotriazol-1-yl) methyl]imino]
industry 111 diethanol (TT-LYK) used for Cu CMP 161
8.2 Materials used for well construction in the oil and 11.4 Other inhibitors used for Cu CMP 165
gas industry 112 11.5 The synergistic effects of mixed corrosion
8.3 Significance of corrosion and its associated agents inhibitor used for Cu CMP 165
in the oil and gas industry 113 Conclusions 167
8.4 Corrosion inhibitors and environmental Useful links 167
concerns 114 References 167
 Contents vii

Part 3 15. Pharmaceutical drugs protecting metals

in aggressive environments
Modern environmentally friendly RUBY ASLAM, MOHAMMAD MOBIN, JEENAT ASLAM,
corrosion inhibitor systems AFROZ ASLAM

15.1 Introduction 229

12. Heterocyclic corrosion inhibitors with 15.2 Corrosion inhibitors 233
multianchoring groups 15.3 Drugs as corrosion inhibitor: Literature survey 234
15.4 Experimental validation 251
MOUHSINE GALAI, MOHAMED RBAA, K. DAHMANI,
BRAHIM LAKHRISSI, M. EBN TOUHAMI, LEI GUO 15.5 Limitations and future directions 252
Conclusions 257
12.1 Introduction 173 Acknowledgments 257
12.2 Corrosion inhibition review of quinoline Abbreviations 257
derivatives 175 Useful links 257
12.3 Example of a complete study on the use of two References 258
heterocyclic inhibitors 178
Conclusion 190 16. Plant extracts as environmentally
References 190 sustainable corrosion inhibitors I
XIN ZHANG, BOCHUAN TAN, WENPO LI
13. Pharmaceutical drugs as corrosion
inhibitors I 16.1 Preparation of plant extracts 263
HASSANE LGAZ, MUSTAFA R. AL-HADEETHI, RACHID SALGHI, 16.2 Experimental methods of plant extracts 265
HAN-SEUNG LEE 16.3 Mechanism of plant extracts 268
16.4 Recent advances of plant extracts 269
13.1 Introduction 195 16.5 Modification of plant extracts 274
13.2 General overview on drug synthesis and reuse 196 Summary and outlook 275
13.3 Application of drugs and expired drugs as References 277
corrosion inhibitors 199
Conclusions and future outlook 204 17. Plant extracts as environmentally
Acknowledgments 205 sustainable corrosion inhibitors II
References 205
ABHINAY THAKUR, HUMIRA ASSAD, SAVAŞ KAYA,
ASHISH KUMAR
14. Pharmaceutical drugs as corrosion
inhibitors II 17.1 Introduction 283
SHVETA SHARMA, RICHIKA GANJOO, 17.2 Prominent metrics for extract preparation 285
SHIMAA M. ELSAEED, ASHISH KUMAR 17.3 Plant extract as corrosion inhibitor 288
17.4 Mode of inhibitor adsorption on substrate 300
14.1 Introduction 211 17.5 Effect of temperature and concentration 301
14.2 Industrial applications of drugs as corrosion 17.6 Techniques to evaluate corrosion inhibition
inhibitors 211 efficiency 302
14.3 Experimental section 212 17.7 Advantage and disadvantages of green corrosion
Conclusion 222 inhibitors 305
Useful links 222 17.8 Future outlooks 305
References 223 Conclusion 306
Useful links 306
References 307
viii Contents

18. Amino acids and their derivatives as Conclusion 406

corrosion inhibitor Useful links 406
References 406
JEENAT ASLAM, RUBY ASLAM, AFROZ ASLAM

18.1 Introduction 311 21. Applications of nanomaterials

18.2 Classification and properties of amino acids 314 in corrosion inhibitors
18.3 Corrosion inhibition mechanism by amino YUQIN TIAN, QI CHEN, XIAOYA SUN, JIAJIA ZHU,
acids 314 RENHUI ZHANG
18.4 Literature survey on amino acids and their
derivatives 316 21.1 Introduction 411
18.5 Challenges and recent progress 319 21.2 Nanomaterials and nanocomposites 411
Conclusions 326 21.3 Nanoparticles as corrosion inhibitors 415
Abbreviations 326 21.4 Important issues related with anticorrosive
Websites related to the topic 326 nanomaterials 421
References 326 References 421

19. Ionic liquids as green and sustainable

corrosion inhibitors I Part 4
ELYOR BERDIMURODOV, ABDUVALI KHOLIKOV, KHAMDAM
AKBAROV, LEI GUO, NURBEK UMIROV, DAKESHWAR KUMAR
Emerging trends in corrosion
VERMA, MOHAMED RBAA, OMAR DAGDAG, RAJESH inhibition
HALDHAR, SAVAŞ KAYA

19.1 ILs as environmental-friendly corrosion 22. Modern testing and analyzing techniques

inhibitors 331 in corrosion
19.2 ILs are corrosion inhibitors for steel materials 333 CHONG ZHU, ZHAOSEN ZHOU, YANG ZHOU, BIN XIANG
19.3 ILs are corrosion inhibitors for copper 369
19.4 ILs are corrosion inhibitors for magnesium 22.1 Traditional used corrosion testing techniques 429
materials 374 22.2 Potential corrosion detection approaches 443
19.5 ILs are corrosion inhibitors for other metallic Conclusions 447
materials 378 References 447
19.6 Inhibition mechanism of ILs 382
Conclusions 382 23. Development of high temperature
Abbreviations 383
corrosion inhibitors
References 383
ABDOLREZA FARHADIAN, LEI GUO

20. Ionic liquids as green and sustainable 23.1 Introduction 451

corrosion inhibitors II 23.2 Plant extracts 452
RICHIKA GANJOO, SHVETA SHARMA, BHARMAL 23.3 Ionic liquids 461
A. SHABBIRBHAI, SHIMAA M. ELSAEED, 23.4 Amino acids 465
ASHISH KUMAR
23.5 Carbohydrates 466
23.6 Vegetable oils 472
20.1 Introduction 391
23.7 Miscellaneous 475
20.2 ILs as corrosion inhibitors 394
Conclusions 478
20.3 Techniques for conducting corrosion experiments
Useful links 478
and deciphering the mechanism of corrosion 398
References 478
20.4 Contact angle measurements of ionic liquids 405
20.5 Mechanism for the corrosion inhibitive property
of ionic liquids 405
 Contents
24. Smart corrosion inhibitor: Present status
and future scenario
XINGWEN ZHENG, LEI GUO, DAWEI ZHANG
24.1 Introduction 485
24.2 Controlled release inhibitor 486
24.3 pH-responsive inhibitor 489
24.4 Ion exchange inhibitor 497
24.5 Other smart inhibitor 501
Summary and future scenario 502
References 502
25. Controllable fabrication of carbon
dots based corrosion inhibitors with
fluorescence properties
YU ZHANG, BOCHUAN TAN, LEI GUO, MENGYUE ZHU
25.1 Corrosion inhibitor used for metal protection 505
25.2 Introduction of carbon dots 508
25.3 Synthetic strategies of CDs 511
25.4 Corrosion inhibition performance of CDs 514
Conclusions and outlook 521
Useful links 522
References 522
26. Computational methods used in
corrosion inhibition research
SAVAŞ KAYA, AKPAN N. IKOT, ASHISH KUMAR, SELÇUK
ŞIMŞEK, MENGYUE ZHU, LEI GUO
26.1 Introduction 527
26.2 Conceptual density functional theory
(CDFT) 529
ix
26.3 Some electronic structure principles and rules for
corrosion inhibition research 531
26.4 Molecular dynamics and Monte Carlo simulations
approaches in corrosion science 533
26.5 The application of first-principles calculation
approach 534
Conclusions 536
References 536
27. Corrosion inhibition strategy:
Synergistic effects
PENG HAN, JIAWEI FAN, LINGHUI KONG, BUYUN ZHANG,
ZHIXUAN CHANG
27.1 Problems and challenges in the study of synergistic
effect of corrosion inhibitors 539
27.2 Advances of synergistic effect 543
27.3 Advances in theoretical research on synergistic
effect of corrosion inhibitors 545
27.4 Significance and prospect of synergistic effect of
corrosion inhibitor 548
Abbreviations 549
References 549
Index 553
 Contributors
Khamdam Akbarov Faculty of Chemistry, National
University of Uzbekistan, Tashkent, Uzbekistan
Mustafa R. Al-Hadeethi Department of Chemistry,
College of Education, University of Kirkuk, Kirkuk,
Iraq
Abdullah K. Alanazi Department of Chemistry,
College of Science, Taif University, Taif, Saudi Arabia
K.R. Ansari Center of Research Excellence in Corro-
sion, Research Institute, King Fahd University of
Petroleum and Minerals, Dhahran, Saudi Arabia
Ruby Aslam Corrosion Research Laboratory, Depart-
ment of Applied Chemistry, Faculty of Engineering
and Technology,Aligarh Muslim University,Aligarh,
India
Jeenat Aslam Department of Chemistry, College of
Science, Taibah University, Yanbu, Al-Madina, Saudi
Arabia
Afroz Aslam Department of Chemistry, Faculty of
Science, Aligarh Muslim University, Aligarh, India
Humira Assad Department of Chemistry, Faculty of
Technology and Science, Lovely Professional Uni-
versity, Phagwara, Punjab, India
Elyor Berdimurodov Faculty of Chemistry, National
University of Uzbekistan, Tashkent, Uzbekistan
Zhixuan Chang Department of Materials Science
and Engineering, China University of Mining &
Technology (Beijing), Beijing, China
Qi Chen School of Materials Science and Engineer-
ing, East China JiaoTong University, Nanchang,
People’s Republic of China
Omar Dagdag Institute of Nanotechnology and
Water Sustainability, College of Science, Engineering
and Technology, University of South Africa, Johan-
nesburg, South Africa
K. Dahmani Laboratory of Organic, Inorganic Chem-
istry, Electrochemistry and Environment, Faculty of
Sciences, Ibn Tofaïl University, Kenitra, Morocco
xi
Brahim El Ibrahimi Department of Applied Chemis-
try, Faculty of Applied Sciences, Ibn Zohr University,
Aït Melloul, Morocco; Team of Physical Chemistry
and Environment, Faculty of Sciences, Ibn Zohr Uni-
versity, Agadir, Morocco
Shimaa M. Elsaeed Petroleum Applications Divi-
sion, Egyptian Petroleum Research Institute (EPRI),
Nasr City, Cairo, Egypt
Baomin Fan College of Chemistry and Materials
Engineering, Beijing Technology and Business Uni-
versity, Beijing, China
Jiawei Fan Department of Materials Science and
Engineering, China University of Mining & Technol-
ogy (Beijing), Beijing, China
Abdolreza Farhadian Department of Polymer &
Materials Chemistry, Faculty of Chemistry and Petro-
leum Science, Shahid Beheshti University, GC, Tehran,
Iran; Department of Petroleum Engineering, Kazan
Federal University, Kazan, Russian Federation
Li Feng School of Chemical Engineering and Tech-
nology, North University of China, Taiyuan,
China
Mouhsine Galai Advanced Materials and Process
Engineering, Faculty of Sciences, Ibn Tofaïl Univer-
sity, Kenitra, Morocco
Pei Gan School of Environmental and Chemical
Engineering, Shanghai University of Electric Power,
Shanghai, China
Richika Ganjoo Department of Chemistry, Faculty
of Technology and Science, Lovely Professional Uni-
versity, Phagwara, Punjab, India
Lei Guo School of Materials and Chemical Engineer-
ing, Tongren University, Tongren, China
Rajesh Haldhar School of Chemical Engineering,
Yeungnam University, Gyeongsan, South Korea
Peng Han Department of Materials Science and Engi-
neering, China University of Mining & Technology
(Beijing), Beijing, China
xii Contributors
Hua Hao Institute of Chemistry, Chinese Academy of
Sciences, Beijing, China
Zhiyong Hu School of Chemical Engineering and
Technology, North University of China, Taiyuan,
China
Akpan N. Ikot Theoretical Physics Group, Depart-
ment of Physics, University of Port Harcourt, Choba,
Nigeria
Savaş Kaya Sivas Cumhuriyet University, Health
Services Vocational School, Department of
Pharmacy, Sivas, Turkey
Abduvali Kholikov Faculty of Chemistry, National
University of Uzbekistan, Tashkent, Uzbekistan
Linghui Kong Department of Materials Science and
Engineering, China University of Mining & Technol-
ogy (Beijing), Beijing, China
Ashish Kumar Department of Chemistry, Faculty of
Technology and Science, Lovely Professional Uni-
versity, Phagwara, Punjab, India
Brahim Lakhrissi Laboratory of Organic Chemistry,
Catalysis and Environment, Faculty of Sciences, Ibn
Tofail University, Kenitra, Morocco
Han-Seung Lee Department of Architectural Engi-
neering, Hanyang University ERICA, Sangrok-gu,
Ansan, Korea
Hassane Lgaz Department of Architectural Engi-
neering, Hanyang University ERICA, Sangrok-gu,
Ansan, Korea
Hao Li National Center for Materials Service Safety,
University of Science and Technology Beijing,
Beijing, China; Key Laboratory of Marine Materials
and Related Technologies, Zhejiang Key Laboratory
of Marine Materials and Protective Technologies,
Ningbo Institute of Materials Technology and Engi-
neering, Chinese Academy of Sciences, Ningbo,
China
Wenpo Li School of Chemistry and Chemical Engi-
neering, Chongqing University, Chongqing, China
Xuemei Ma School of Chemical Engineering and
Technology, North University of China, Taiyuan,
China
Tengda Ma School of Electronics and Information
Engineering, Hebei University of Technology,
Tianjin, China
Sheerin Masroor Department of Chemistry, A.N.
College, Patliputra University, Patna, Bihar, India
Mohammad Mobin Corrosion Research Laboratory,
Department of Applied Chemistry, Faculty of Engi-
neering and Technology, Aligarh Muslim University,
Aligarh, India
Xinhuan Niu School of Electronics and Information
Engineering, Hebei University of Technology,
Tianjin, China
Yujie Qiang National Center for Materials Service
Safety, University of Science and Technology Beijing,
Beijing, China
M.A. Quraishi Center of Research Excellence in Cor-
rosion, Research Institute, King Fahd University of
Petroleum and Minerals, Dhahran, Saudi Arabia
Mohamed Rbaa Laboratory of Organic Chemistry,
Catalysis and Environment, Faculty of Sciences, Ibn
Tofail University, Kenitra, Morocco
Rachid Salghi Laboratory of Applied Chemistry and
Environment, ENSA, University Ibn Zohr, Agadir,
Morocco
Bharmal A. Shabbirbhai Department of Chemistry,
Faculty of Technology and Science, Lovely Profes-
sional University, Phagwara, Punjab, India
Shveta Sharma Department of Chemistry, Faculty of
Technology and Science, Lovely Professional Uni-
versity, Phagwara, Punjab, India
Ambrish Singh School of New Energy and Materi-
als, Southwest Petroleum University, Chengdu,
Sichuan, China
Xiaoya Sun School of Materials Science and Engi-
neering, East China JiaoTong University, Nanchang,
People’s Republic of China
Baimei Tan School of Electronics and Information
Engineering, Hebei University of Technology,
Tianjin, China
Bochuan Tan School of Chemistry and Chemical
Engineering, Chongqing University, Chongqing, China
Abhinay Thakur Department of Chemistry, Faculty
of Technology and Science, Lovely Professional Uni-
versity, Phagwara, Punjab, India
Yuqin Tian School of Materials Science and Engi-
neering, East China JiaoTong University, Nanchang,
People’s Republic of China
M. Ebn Touhami Advanced Materials and Process
Engineering, Faculty of Sciences, Ibn Tofaïl Univer-
sity, Kenitra, Morocco
 Contributors
Burak Tüzün Department of Chemistry, Faculty of
Science, Sivas Cumhuriyet University, Turkey
Nurbek Umirov Faculty of Natural Sciences, Karshi
State University, Karshi, Uzbekistan
Chandrabhan Verma Interdisciplinary Research
Center for Advanced Materials, King Fahd University
of Petroleum and Minerals, Dhahran, Saudi Arabia
Dakeshwar Kumar Verma Department of Chemis-
try, Government Digvijay Autonomous Postgradu-
ate College, Rajnandgaon, Chhattisgarh, India
Chenwei Wang School of Electronics and Informa-
tion Engineering, Hebei University of Technology,
Tianjin, China
Bin Xiang School of Chemistry and Chemical Engi-
neering, Chongqing University, Chongqing, China
Junyu Yang School of Environmental and Chemical
Engineering, Shanghai University of Electric Power,
Shanghai, China
Da Yin School of Electronics and Information Engineer-
ing, Hebei University of Technology, Tianjin, China
Abdelkader Zarrouk Laboratory of Materials, Nan-
otechnology and Environment, Mohammed V Uni-
versity, Faculty of Sciences, Rabat, Morocco
Saman Zehra Corrosion Research Laboratory,
Department of Applied Chemistry, Faculty of Engi-
neering and Technology, Aligarh Muslim University,
Aligarh, India
Daquan Zhang School of Environmental and Chemi-
cal Engineering, Shanghai University of Electric
Power, Shanghai, China
Wenyue Zhang School of Environmental and Chemi-
cal Engineering, Shanghai University of Electric
Power, Shanghai, China
Shihao Zhang School of Electronics and Information
Engineering, Hebei University of Technology,
Tianjin, China
Xin Zhang School of Chemistry and Chemical Engi-
neering, Chongqing University, Chongqing, China
xiii
Renhui Zhang School of Materials Science and Engi-
neering, East China JiaoTong University, Nanchang,
People’s Republic of China
Dawei Zhang University of Science & Technology
Beijing, Beijing, China
Yu Zhang School of Chemistry and Chemical Engi-
neering, Chongqing University, Chongqing, China
Buyun Zhang Department of Materials Science and
Engineering, China University of Mining & Technol-
ogy (Beijing), Beijing, China
Xingwen Zheng School of Chemical and Environ-
mental Engineering, Sichuan University of Science &
Engineering, Zigong, China
Zhaosen Zhou Analytical and Testing Centre of
Chongqing University, Chongqing University,
Chongqing, China; Henan Chemical Technician
College, Henan, China
Yang Zhou Analytical and Testing Centre of Chongq-
ing University, Chongqing University, Chongqing,
China
Hailin Zhu School of Chemical Engineering and
Technology, North University of China, Taiyuan,
China
Jiajia Zhu School of Materials Science and Engineer-
ing, East China JiaoTong University, Nanchang,
People’s Republic of China
Chong Zhu School of Chemistry and Chemical
Engineering, Chongqing University, Chongqing,
China
Mengyue Zhu School of Materials Science and Engi-
neering, East China Jiaotong University, Nanchang,
China
Amir Zomorodian Department of Engineering,
University of Cambridge, Cambridge, United
Kingdom
Selçuk Şimşek Sivas Cumhuriyet University,
Faculty of Science, Department of Chemistry, Sivas,
Turkey
 Preface
It is well-known that corrosion has a huge eco-
nomic, environmental, and sustainability
impact on virtually all facets of metallic materi-
als, including power facilities, integrated cir-
cuits, chemical industries, desalination, bridges,
oil and gas pipeline, etc. Annual costs of corro-
sion and its consequences are estimated in the
region of 3–5% of GDP for industrialized coun-
tries of the world. Most of all, the disposal and
further substitution of the damaged elements
involve an additional consumption of energy
and resources. To face and solve this challenge,
an increasing number of studies have focused
on environmentally friendly, renewable, and
efficient corrosion inhibitors, which are promis-
ing alternatives to toxic corrosion inhibitors, in
order to control corrosion damage in diverse
corrosive environments. These materials range
from plant extracts to amino acids, expired
drugs, ionic liquids, carbohydrate polymers,
and zero-dimensional carbon quantum dots.
Although the subject of corrosion inhibition has
been a conventional research topic over the past
few decades, more advanced knowledge is still
required to win the battle. A comprehensive
understanding of this phenomenon will guar-
antee an improved design to reduce the dra-
matic consequences.
In this regard, the present book aims to shed
more light on the recent progress and advances
on the usage of green and sustainable inhibitors
to protect metallic materials against corrosion
in different corrosive conditions, such as acidic,
neutral, alkaline, and sweet/sour environ-
ments. A wide range of ecofriendly corrosion
xv
inhibitors have been presented and their poten-
tial applications in various industrial fields
were also discussed.
The book is divided into different parts,
where each part contains multiple chapters.
Part 1 “Overview of industrial corrosion and
inhibition” covers topics such as general prin-
ciples of industrial corrosion, corrosion preven-
tion, and protection methods, and the
development process for ecofriendly corrosion
inhibitors. Part 2 “Industrial environments &
corrosion inhibitors” entirely focuses on the
application of corrosion inhibitor in acidizing,
alkaline, and near neutral media, as well as the
inhibitors for cooling water systems, oil and gas
systems, and chemical mechanical planariza-
tion. Part 3 “Modern environmentally friendly
corrosion inhibitor systems” is specific about
the corrosion inhibitors based on pharmaceuti-
cal drugs, plant extracts, amino acids, ionic
liquids, nanomaterials, and synthetic com-
pounds. Part 4 “Emerging trends in corrosion
inhibition” gives a description of modern
testing and analyzing techniques in corrosion,
the smart and high temperature corrosion
inhibitors, the synergistic inhibition strategy,
and computational methods used in corrosion
inhibition research.
Overall, this book is written via a scientific
summary of modern corrosion inhibitors, and
is prepared for graduate students, researchers,
as well as practitioners in multiple industries
who require comprehensive knowledge of this
aspect. The editors and contributors are well-
known scientists with many years of research
xvi Preface

experience in corrosion inhibitors. Thank all the cal support for future research and innovation
hard-working project managers and acquisi- in the field of corrosion inhibition.
tions editor of this book for their enthusiasm
and help in the publishing process. We would Lei Guo
like to thank Elsevier for publishing this book, Chandrabhan Verma
which can provide theoretical basis and techni- Dawei Zhang
 P A R T 1

Overview of industrial corrosion

and inhibition
1 General principles of industrial corrosion 3
2 Corrosion prevention and protection methods 13
3 Development process for eco-friendly corrosion inhibitors 27
 C H A P T E R

1
General principles of industrial
corrosion
Sheerin Masroor
Department of Chemistry, A.N. College, Patliputra University, Patna, Bihar, India

1.1 Introduction warming and greenhouse emissions, all inter-

The economic development of any region,
state or country, depends not only on its natural
resources and productive activities, but also on
the infrastructure that account for the exploita-
tion, processing, and marketing of goods. Irriga-
tion systems, roads, bridges, airports, maritime,
land and air transport, school buildings, offices
and housing, industrial installations are affected
by corrosion and therefore susceptible to dete-
rioration and degradation processes.
Corrosion is a worldwide crucial problem
that strongly affects natural and industrial envi-
ronments. Today, it is generally accepted that
corrosion and pollution are interrelated harmful
processes since many pollutants accelerate cor-
rosion and corrosion products, such as rust, also
pollute water bodies. Both are pernicious pro-
cesses that impair the quality of the environ-
ment, the efficiency of the industry and the
durability of the infrastructure assets. Therefore,
it is essential to develop and apply corrosion
engineering control methods and techniques.
Other critical problems, that impact on infra-
structure and industry are climate change, global
related phenomena. This chapter presents
important aspects of corrosion in industrial
infrastructure, its causes, impacts, control, pro-
tection and prevention methods.
1.2 Materials in industrial applications
Earthly materials always keep an important
point which is for good development of any
economy we are living, that further be sustained
globally. The usage of metal depends upon the
characteristic properties it is having and its
important applications that it may be having in
society. Few were summarized below:
In the line of any metal production from its
ore, multiple processes applied are mineral
mining, manufacturing with application along
with production of various solids, liquids, and
gases that are having great impact on the society
and environment.
For specific industrial progress, in general the
metal and materials are produced in such a way
that they will not affect the environment at
greater level [1–7]. The metals or materials can

Eco-Friendly Corrosion Inhibitors

DOI: https://doi.org/10.1016/B978-0-323-91176-4.00013-1 3 Copyright © 2022 Elsevier Inc. All rights reserved.
4 1. General principles of industrial corrosion
be selected for production on the basis of their
demand or consumption inducing in the market.
There are many approaches to carry out these
things. The most general way is to research the
materials and apply them as per their use in
recommended technology. It can also to be note
that the materials which are allowed to recycle
mainly requires very less capital and energy
consumption, alternatively needs more man-
power for basic processing. In addition, the
price of pollution control mainly happens to be
low as required for primary processing’s
[8–10].
Also, the costs of pollution control are lower
than those required for primary processing of
minerals. Recycling becomes more intense, as
economies tend to be more sophisticated, since
viable quantities of recycled material must be
available for reuse [11].
Industries produce various things of our
daily use during processes waste material is
generated, these are those parts of material that
was left aside, during the production steps.
They may be named as Effluent, having waste
that comes from the procedures attached to the
technology in various step of production in
addition with main material. So many industrial
processes such as recovering metal from their
ore involves much technological steps which
may vary in different countries such as eco-
nomic, financial aspects with regulatory laws.
This explains how environmental impacts vary
much around the globe. The refinement of metal
from depends upon its quality, i.e., if the ore
contains very low amount of metal and needs
multiple steps to recover. This all increases the
cost of recovery and also needs huge amount of
raw mineral material. In addition of these things,
energy applied is also in much need. The other
processes involve mechanical or physical
removal of rock, transportation of material from
mines, concentration of ore at specific place. The
flow chart for material cycle is given here:
Raw Material Resource → Material Extrac-
tion → Material Processes → Different Forms of
Part 1 Overview of industrial corrosion and inhibition
Processed Material → Different Application of
Materials → Waste Material → Recycling of
Materials.
In the basic steps involved for mineral
extraction, the effluents of carbon, nitrogen,
sulfur and compounds such as NOx, SOx and
COx may come from different machines and
equipment’s. These all fill the land and under-
ground water. This contamination may also
cause severe corrosion of metals or alloys
present in vicinity.
1.3 General principles or theories of
industrial corrosion
There are three general principles or theories
to be follow for corrosion to happen in any
medium for metal or alloys:
Acid theory of corrosion
Dry or chemical theory of corrosion
Galvanic or Electrochemical or Wet theory
of corrosion
Acid theory of corrosion:
This theory mostly explains corrosion for that
metals or alloys which is in the vicinity of acid.
As per this theory, metal (iron) is specifically
corroded by carbon-di-oxide, water (moisture)
and oxygen. Products of corrosion includes
mixture of Fe (HCO3)2, Fe (OH)CO3 and Fe
(OH)3. The ongoing reactions for the corrosion
are given below:
Fe + 2CO 2 + H 2 O + 1 2 O 2 → Fe ( HCO 3 )2
2Fe ( HCO 3 )2 + H 2 O + 1 2 O 2 → 2Fe(OH)CO 3
+ 2CO 2 + 2H 2 O
2Fe ( OH ) CO 3 + 2H 2 O → 2Fe ( OH )3 + 2CO 2
This theory is supported by the analysis of
rust that gives the test for CO2 ion.
Dry or chemical theory of corrosion:
This type of corrosion mainly occurs on the
surface of metal and happens due to reactions
 1.4
of gases present in atmosphere such as oxygen,
halogens, oxides of nitrogen and sulfur, hydro-
gen sulphide, and fumes of chemicals along
with metal.
There are three general types of dry corrosion
which are given below:
Oxidation corrosion (reaction with oxygen)
Corrosion by other gases, such as Cl2, SO2,
H2S, NOx
Liquid metal corrosion
Oxidation corrosion (Reaction with oxygen):
As various metals directly make reactions in
presence of oxygen and in absence of moisture.
Examples are alkali and alkaline earth metals
that reacts with oxygen present at standard tem-
perature and generate oxides of corresponding
metals. In return metal oxides are in process of
making a thin film over metallic surface which
further protects metal to undergo corrosion. So,
the metal oxide always plays a major role in the
process of corrosion.
M → M + ne − ( n = 1)
− −
1 O 2 + 2e → O
2
Combining Eq. 1.1 and 1.2.
2M + 1 2 O 2 → M 2 O
Corrosion by gases such as Cl2, SO2, H2S, NOx
If the atmosphere is dry, so the gases like Cl2,
SO2, H2S, NOx may react with metal and alloys
to form corrosion products which may be pro-
tective or non-protective in nature.
Chlorine gas do react with silver (Ag) to form
silver chloride (AgCl) which may acts as protec-
tive layer.
Liquid metal corrosion:
In different industries, metal in molten form
which passes through metallic pipes happen to
cause corrosion might be due to dissolution or
due to internal penetration. The metal like liquid
mercury usually dissolves most other metals to
form amalgams, which alternatively corrodes
them.
Part 1 Overview of industrial corrosion and inhibition
Different types of corrosion in industries 5
Wet or Electrochemical theory of corrosion This
form of corrosion may occur when the metal
comes in contact with any form of conducting
liquid or when two dissimilar metals are immersed
or dipped partly in a solution. Here there is the
formation of a galvanic cell on the surface of
metals. Some parts of the metal surface act as
anode while other acts as cathode. The chemical
present in the environment and humidity percent-
age acts as an electrolyte. The oxidation of anodic
part takes place and it results in corrosion at
anode, while reduction takes place at cathode. The
corrosion product is formed on the surface of the
metal between anode and cathode.
1.4 Different types of corrosion in
industries
The basic corrosion involves some electro-
chemical reactions that lead to oxidation of
metal atom into the metal ions releasing elec-
trons at anode; those electrons were further con-
(1.1) sumed at cathode during simultaneous
reduction reaction. This can be known by given
(1.2)
reactions:
The anodic corrosion reactions:
Fe → Fe2 + + 2e −
Zn → Zn 2 + + 2e −
The cathodic corrosion reactions:
2H + + 2e − → H 2
H 2 O + 1 2 O 2 + 2e − → 2OH −
O 2 + 4H + + 4e − → 2H 2 O
That specific site where metal atoms release
electrons is called the anode while the site where
electrons are consumed to the reducing species
is called the cathode.
Corrosion can be considered as an electro-
chemical process where flow of electric current
along with the chemical reactions goes on simul-
taneously. Some general types of corrosion are
given here:
6 1. General principles of industrial corrosion

1.4.1 General or uniform corrosion TABLE 1.1 Metal and their uses in society.

It is a kind of corrosion occurring in indus- S. Material/

No substance Specific property Uses
tries where the metal is degraded uniformly
over a wide area of the metal surface which 1. Metals or alloys Mechanically Infrastructure,
iron carbon hard jewelery,
leads to thinning of substance. Here the rate of
or stainless- decorative
corrosion is indisputably calculated. The mate- steel assets, coins,
rial, which mainly undergo uniform corrosion non-ferrous transportation,
are equipment’s, different machineries, and alloys aircraft, tanks
industrial structures that are made up of carbon 2. Polymers Low dense, Textiles, packag-
steel and cast iron. This deprivation due to plastic rubber corrosion ing, stationary,
uniform corrosion may be decreased by apply- resistant paint, construc-
tion, aircraft
ing pertinent maintenance and reformation
approaches. The various schemes involve use of 3. Ceramics glass Hard, Pottery, titles,
silica temperature, bricks, cements,
inhibitors, paint, coating, and cathodic protec-
alumina and corrosion glass, cutting
tion which remarkably diminishes uniform cor- metallic resistant tools, refractory
rosion. The easiest way to calculate rate of carbides furnaces
corrosion is by utilizing gravimetric/weight loss 4. Composites Hard with high Aircraft compo-
measurements and electrochemical techniques. strength, light nent, construc-
in weight tion, car bodies

1.4.2 Galvanic/bimetallic corrosion
It occurs when the dissimilar metals or alloys
are joined together via electric circuit in the com-
panionship of an electrolyte. Most important
example comes from a cell, where anode is made
from zinc which is placed in electrolyte carrying
ions of zinc. Further these zinc ions are dis-
solved in the provided electrolyte, so that the
exchange of hydrogen ions can occur. While the
ion’s flow through the electrolyte to produce
electric current via carbon rod which acts as
cathode. At this position the hydrogen ions are
mostly deposited over the surface of the carbon
rod as hydrogen gas. In addition, if hydrogen
gas remains intact on the carbon rod it will act
as an insulator, which terminates flow of current.
This is called as Polarization, which is formation
of the film, while its removal is named as Depo-
larization. Here the current flow’s is from zinc
anode to the electrolyte, to the carbon rod
cathode and back to the metal zinc via external
wire which is connected to the battery. As the
current starts flowing in this circuit, the zinc is
decreasing while the carbon remains unharmed.
By this we can simply say, the anode is disman-
tled but the cathode is sheltered.
As described earlier, a hydrogen film is
formed on the cathode or carbon rod that helps
cathode to insulate from the electrolytic solution
and further stops flow of current. This happens
to stop corrosion, as the formation of hydrogen
film on the cathode took place. Corrosion starts
as soon as this layer if detach from the cathode.
In the case of cell or battery, the zinc case is
easily attacked and the carbon is protected. This
causes any metal to be attacked if present in
circuit and will not attacked when in circuit with
another. By different experiments and researches
a table was made earlier, called as Galvanic
Series wherein a metal present above can be
attacked by another metal present below in list
when present in common electrolytic environ-
ment like moist soil or water. The metal or alloys
present above are more susceptible to corrosion
or less noble compared to below present in table,
which are least susceptible to corrosion or con-
sidered as more noble, the table is shown below
as Table 1.2.

Part 1 Overview of industrial corrosion and inhibition

 1.4 Different types of corrosion in industries 7
TABLE 1.2 Metal or alloys present in Galvanic series. TABLE 1.3 Specific use of metal in industries.
S. No Metal or alloys S. No Metal Specific use
1. Magnesium or magnesium alloys 1. Silver Shielded coating in cables, contact
relays, and EMI gaskets
2. Zinc
2. Gold Coating /foil, circuits, miniature
3. Aluminum 2S
circuits
4. Cadmium
3. Magnesium Alloys of radar antenna, brackets
5. Aluminum 17ST Anodic or
corroded end 4. Iron Machinery components, magnetic
6. Steel or iron shielding, magnetic coating,
7. Cast iron disk

8. Chromium-iron (active) 5. Aluminum Armor equipment, mounting

frames, brackets
9. Ni-Resist
6. Copper Cables, tablets, circuits, nuts and
10. 18-8 Stainless steel (active) bolts, RF packaging

11. 18-8-3 Stainless steel (active) 7. Cadmium Sacrificial protective coating on

iron and electrical connectors
12. Hastelloy A 8. Nickel Coating layer for copper and gold
13. Hastelloy B components, electromagnetic
interference applications
14. Brass
9. Tin Corrosion protection of welding,
15. Copper electrical connectors, RF
16. Bronzes shielding filter, automatic
switching mechanism, welding,
17. Copper-nickel alloy
binding
18. Monel
19. Silver solder
Cathodic or develops this corrosion. Where the creviced area
20. Nickel (passive) behaves as anode, while left over surface/larger
protected end
21. Inconel (passive) area/bulk solution acts as cathode. This further
22. Chromium-iron (passive) enhances the corrosion reactions taken place
23. 18-8 Stainless steel (passive) around crevice. If any salt is added to the acidic
24. 18-8-3 Stainless steel (passive)
conditions, corrosion accelerates. Example is Fili-
form corrosion. This corrosion in industries can be
25. Silver
corrected by designing specifically for use and
26. Graphite avoiding sharp corners. Regular ablution of
27. Gold deposits and nonstagnant solution may be helpful
28. Platinum to decrease crevice corrosion.

1.4.3 Crevice corrosion 1.4.4 Pitting corrosion

This specific type of corrosion which occurs in
industries occurs in machineries where different
kind of parts are made having different geome-
tries like joints, threaded, bolted or any irregular
shape. The interaction between metal and non-
metal such as under the spacers or gaskets also
It’s a unique type of corrosion where there is
formation of small pin holes at various places.
Harsh perforation of the material causes leakage.
Generally, the material-environment duo can
make defensive passive film on the case copy
may suffer this corrosion. In turn the existence

Part 1 Overview of industrial corrosion and inhibition

8 1. General principles of industrial corrosion
of halide anions such as chlorides and thiosul-
fate ions may enter the suspected area and
bruise the passive layer and cause pin hole cor-
rosion. Pits become aggressively acidic with
elevated concentration of chloride compared to
bulk mixture. The reactions of pitting corrosion
are so similar to that of crevice corrosion. This is
very common in industries. We can eliminate
this corrosion by selecting pitting resistant
alloys. Researchers can check failure due to
pitting by knowing Pitting Resistance Equiva-
lent (PRE) Index by given formula:
PRE = 1 × % Chromium + 3.3 ×
% Molybdenum + 16 × % Nitrogen.
Some values of PRE index of some metal are:
AISI 316 stainless steel = 25.6.
AISI 304 = 18.
Some engineered alloys have the given
decreasing order such as:
Ti> Hastelloy C or Chlorimet> Hastelloy F,
Durimet 20> Type 316 stainless steel> Type 304
stainless steel.
1.4.5 Intergranular corrosion
It involves type of corrosion where there is
involvement of preferential attack on alloys
which are in contact with certain environment
along the grain boundaries. This clearly happens
due to micro segregation of impurities and dif-
ferent alloying elements present in grain’s
boundaries of any equipment used in industries.
The incentive for this kind of corrosion is the
generation of potential difference in between
grain boundary and the grain matrix, which
further develops galvanic cell in the vicinity of
electrolytes. The movement of corrosion is from
grain boundaries from the edge to the thickness
or middle. This all-causes disintegration of
metal and hence strength is lost. Mainly the
equipment’s or instruments made from nickel,
aluminum alloys and austenitic stainless steels
may suffer from intergranular corrosion in the
industries. If we talk especially corrosion of
Part 1 Overview of industrial corrosion and inhibition
austenitic steel at higher temperature which
ranges from 482-760°C, there is formation of
chromium carbide Cr23C6 along the grain bound-
aries. That causes overall depletion of chromium
and hence lost corrosion resistance. The ongoing
process is called as Sensitization. This process
generally occurs in industries at the time of
welding operations, solution annealing and
stress relieving processes. Intergranular corro-
sion can also be called best as Weld Decay
because sensitization is occurring at the heat
affected zones (HAZ) which were developed in
between weld joints. The intergranular corro-
sion of austenitic steel can be eliminated by
putting strong carbide formers and also by
decreasing carbon content in stainless steel
<0.03% (e.g., 304L/316L).
1.4.6 Stress corrosion cracking
Here the metal or alloy can be affected by
brittle cracking which are caused by majorly
three factors such as:
Tensile stress: It can be due to two forms
either operational or residual stresses in the
metal / materials or alloys. This all occurs
as a result of the metal formation, creation
and welding processes.
Susceptible materials: This is not applicable
to all kinds of metal or materials as pure
metals are mostly susceptible to this
corrosion type. While some metal or alloys
are susceptible to specific environment. For
example: Austenitic stainless steels are
greatly resistant for developing SCC when
they are kept in ammoniacal environment.
Susceptible environment: These are some
specific environments which generally
cause Stress Cracking Corrosion of the
metal mostly used in industries. For
example, if stainless steels are used in
chloride containing environment are crack
prone but not when used in acids such as
sulfuric acid, nitric acid, acetic acid or
pure water.
 1.4 Different types of corrosion in industries
The cracks develop during this corrosion may
run along preferential routes such as along grain
boundary called as Intergranular Stress Corro-
sion Cracking (IGSCC) or may be transversely
around grain boundary, which further called as
Trans granular Stress Corrosion Cracking
(TGSCC).
The corrosion happening here can also be
prevented by the replacement of austenitic stain-
less steels BY austenitic-ferritic (duplex) stain-
less steels, which have remarkably low
susceptibility to stress corrosion cracking com-
pared to previous one. Applying compressive
stresses and coating would also help to reduce
SCC.
1.4.7 Corrosion fatigue
Corrosion fatigue (CF) is propensity of alloys
used in industries or engineering applications.
It got fracture because of the presence of colle-
gial effects of cyclic loading and aggressive
environment. The collapse starts occurring at
places of stress levels present on material or at
the tolerance limits. It is a crucial deterioration
process which is highly responsible for the
damage caused in industries such as nuclear or
steam power systems, aircrafts, marine struc-
tures, bridges, pipelines and gas turbines. The
damage caused by corrosion fatigue mat occur
in four steps: deformation caused by cyclic
plastic, initiation of microcrack, growth of small
crack and propagation of macrocrack. The use
of different mediums and present environment
for specific work in industries promotes corro-
sion fatigue due to various factors (frequency,
stress ratio, electrode potential or stress inten-
sity range). Corrosion fatigue generally moves
in the trans granular manner and does not show
divarication which is important characteristics
feature of stress corrosion cracking. Corrosion
fatigue can be best reduced by eliminating the
stress on the industrial materials or can be
accomplished by changing the architecture and
heat treatment.
Part 1 Overview of industrial corrosion and inhibition
9
1.4.8 Erosion corrosion
It is a general term that relates to a corrosion
process caused by the relative motion of the
flowing fluids and materials surface. The usual
effect of the EC is localized attack which emerges
as gullies, grooves, rounded holes, and waves
etc. The most affected equipment’s by this kind
of corrosion in general industries are impellers,
under water components, steam turbine blades,
bends, inlets pipes in different tanks, pumps and
cyclones. Destruction of metal is Destruction of
metal is quick as the running liquid discard the
protective corrosion layer formed over the metal
surface, which further exposes the fresh metal
surface alternatively more prone to corrosion
with accelerated rate. In addition, the corrosive
suspended products which are added to the
aggressive medium or fluid cause extensive
coarse-grained action over metal surface leading
to enhanced corrosion rate.
In the industries the situation becomes worse
by the process of Cavitation (kind of erosion
corrosion) which is formed by unanticipated
crumble of vapor bubbles in a liquid and ema-
nating impact over metal surface. The collapsing
of bubbles may be having high value of more
than 1500 MPa which is adequate for the micro-
structural swapping in the underlying material
surface.
Due to regular cavity deficit passive film for-
mation is strenuous and hence metal cessation
is elevated. Specifically in industries the liquid
or processed fluid accommodates rigid solid
particles which serves and accelerates corrosive
reactions by their harsh actions. Special design-
ing and application of coatings to the suspected
components are useful methods to prevent
erosion and cavitation corrosion.
1.4.9 Selective leaching
It is very specific in industries where the
erosion of one constituent of an alloy in presence
of certain electrolyte may result due to electro-
chemical reactions. The main reason for this
10 1. General principles of industrial corrosion
corrosion to occur is the creation of large elec-
trode potential of constituents of alloy such as
zinc (Zn) and copper (Cu) in brass alloy or in
between iron (Fe) and graphite (C) in grey cast
iron.
The metal or element which has lower elec-
trode potential as a choice corrodes first and
diffuse in the electrolyte or liquid. While the one
which has higher electrode, potential remains
secured cathodically. The most customary alloys
vulnerable to corrosion are Silicon bronze
(desiliconification), Tin bronze (destannifica-
tion), Brasses (dezincification), Grey cast
irons (graphitic corrosion), Aluminum
bronze (dealuminification) and Copper-Nickels
(denickelification).
If we see on the percentage basis, the process
of dezincification occurs in brasses having more
than 15% of zinc, as zinc is chemically very
active element with very low standard electrode
potential, valued -0.763 while electrode poten-
tial of copper is much higher with value +0.337.
So, the difference between these two potentials
is the driving force for dezincification of brasses.
The metal in industries starts corroding with
cessation of zinc-to-zinc ion (Zn = Zn2++ 2e−)
quitting behind the network of copper.
1.4.10 Fretting corrosion
This kind of corrosion is amalgamation of
simple corrosion and abrasive wear. It can be
speeded by the correlative motion of approach-
ing surfaces in aggressive medium. The relative
motion between the exposed surfaces detaches
shielded films and may ends in enhanced corro-
sion. It has been noted that generally corrosion
products are eroding in nature and their exist-
ence in the aggressive fluid may increase the
confiscation of protective films. This corrosion
mostly affects the industrial equipment’s related
to aeroplane, ships and automobile assemblies
or the places where periodical loading is accom-
plished. Fretting corrosion can be more promi-
nent at places of vibration in blade system and
Part 1 Overview of industrial corrosion and inhibition
thermal expansion with frequent cycling. There
is development of fatigue cracks in the
components.
1.4.11 Microbiologically influenced
corrosion
This corrosion often infuriated by the pres-
ence of microorganisms and so secondarily
control the reactions of corrosion. Mostly places
of sewage, under bridges, buried structures and
water operated equipment’s where the microor-
ganism may be sheltered are influenced struc-
tures for this corrosion. As those microorganisms
are having propensity to excel in presence or
absence of oxygen environment done by popu-
larly known as aerobic and anaerobic bacteria.
The aerobic bacteria are sulfur oxidizing bacte-
ria (thiobacillis / thiooxidans) which oxidizes
the elemental sulfur or sulfur hearing compound
to sulfuric acid thus reduces the pH of the envi-
ronment. Likewise anaerobic or sulfate reducing
bacteria (deslfuricans) which reduces sulfate to
sulfide that influences the hydrogen evolution
and accelerates metal oxidation (anodic reac-
tion). The most accepted way to reduce micro-
biologically influenced corrosion is to apply
coating comprising enamel, plastic tape and
asphalt. The other way is addition of corrosion
inhibitors such as germicides (Chlorinated com-
pounds) that can be supplied to the corrosive
systems.
1.5 Corrosion of metal in industries
The components or equipment’s present in
machine that helps to function them are
extremely susceptible to corrosion as they are in
use for long time. This causes failure of compo-
nent of the things in use. The components are
made with high density are made light by
making their sections thin. This all causes
increase in corrosion. Furthermore, the corro-
sion rates of devices or equipment’s used in
 1.5 Corrosion of metal in industries
industries are enhanced to maximum when they
are encountered with harsh or aggressive envi-
ronments such as deserts, moist places, tropical
or sub-tropical environments mainly for things
in military use. Aircraft and submarine systems
are highly affected. Music player instruments on
the other hand are severely affected when
exposed to fuggy environments having chlo-
rides. This all happens in shipping those instru-
ments from manufacturing place to customer’s
location.
The formation of very thin layer made from
corrosion reactions alter the electrical properties
of the instruments, such as capacity, resistance
of electronic systems. Many cases has been
reported in electrical manufacturing industries
which causes alteration in inbuild circuits, fit-
tings, connectors, nichrome resistors along with
micro-electronic components which have been
glazed with metallic films. There are reported
cases where small amounts of moisture have
caused corrosion in tablets with printed circuits,
nichrome resistors, fittings, electrical connectors
and a wide range of components, and micro-
electronic components, which have been coated
with metallic films [12–13].
The corrosion of components in different
industries may occur at various stages such as:
Manufacturing
Storage
Shipping
Services
Important factors to initiate corrosion is the
development of moisture, pollutants, sweeping
of organic solvents or presence of elements such
as chlorides, fluorides, sulfides or nitrogen
compounds.
The input of pollutants for single machinery is
diverse like flux remnants used for welding,
vapors from electrolytic baths, micro plastics, vola-
tile organic adhesives from nearby environment.
Industrial applications need various metal,
out of them many remains in contact with each
other, at those places due to presence of
Part 1 Overview of industrial corrosion and inhibition
11
moisture bimetallic or galvanic corrosion occurs.
Keeping in view of these kinds of locations, the
following precautions must be greatly to take in
account:
Appropriate design: Here the exposed
metal or alloys are so made that the area of
the more noble cathodic metal or alloy must
be substantially smaller compared to the rea
of more active anodic metal. So, the most
expected way to reduce the area of cathode
is to apply coating or suitable paint over it.
Suitable Coating: The area in contact of
metal with each other can be coated with
appropriate metal.
Insinuation of dissimilar metals: There
must be an interpose in linking different
metals in a metal compatible packaging.
Clinching interfaces: All interfaces must be
properly sealed to avoid admittance of
moisture.
Proper setting: Mostly electronic devices
must be placed in hermetically sealed
arrangement.
1.5.1 Corrosion of metal by water
The water is most essential component of any
country’s manufacturing/industrial promotion.
The multiple application of water is to act as
coolant for equipment and machineries. Total
quantity of liquid or water used by each country
are almost different and depends on the percent-
age of industrial development. In the previous
time for the United States like country, the con-
sumption of water was around hundred billion
liters per day. Further these countries have opted
to reuse the water system by the application of
right treatment channel for its purification.
Water is always considered as an aggressive
environment for various metals and alloys, by
which they may encounter with corrosion which
is an electrochemical process.
The water may come from natural resources,
such as lakes, rivers, springs, or well which can
easily corrode metal or alloys used in industries.
12 1. General principles of industrial corrosion
The most important equity of water is that some
degree of material present in earth crust and
atmosphere has several unique properties and
one of these is its ability to dissolve to some
degree the substances found in the earth’s crust
and atmosphere allowing the water to contain a
certain number of impurities, which causes
problems of scale deposition on the metal surface,
e.g., in pipelines, boiler tubes and all kinds of
surfaces that are in contact with water [14–21].
1.5.2 Specific use of metal in industries
In lieu of corrosion that is happening in multi-
ple components of industrial assemblies, we have
to look specific remedies to tackle them. One best
possible way is to use selective metal for specific
place to avoid corrosion or to make it in minimal
percentage. Some of examples are given here:
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Cadmium, copper and zinc levels in rice and soil of
Japan, Indonesia and China by soil type, Bull. Env.
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[8] R. Garcia, et al, 2012, Lopez, G. 2011, Schorr, M., 2010.
[9] L.M. Al-Hadhrami, A. Quddus, A. Dhawi Al-Otaibi,
Calcium sulfate scale deposition oncoated carbon steel
and titanium, Desalination Water Treat. 51 (13–15)
(2013) 2521–2528.
Part 1 Overview of industrial corrosion and inhibition
[10] F. Smaïli, V.S. Vassiliadis, D.I. Wilson, Optimization of
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[11] M. Li, C. Dai, B. Yang, Y. Qiao, Z. Zhu, New and green
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[12] H. Ashassi-Sorkhabi, E. Asghari, M. Mohammadi,
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 C H A P T E R
2
Corrosion prevention and
protection methods
Saman Zehra, Mohammad Mobin, Ruby Aslam
Corrosion Research Laboratory, Department of Applied Chemistry, Faculty of
Engineering and Technology, Aligarh Muslim University, Aligarh, India
2.1 Introduction
Corrosion is a naturally occurring process
which is defined as the degradation or deterio-
ration of a substance and/or its properties,
usually a metal, over a period of time due to
environmental exposure [1]. This is an exergonic
process as the metal tends toward the lowest
possible energy state. Corrosion is a naturally
occurring process defined as the degradation or
deterioration of a substance and/or its qualities,
typically a metal, over time as a result of envi-
ronmental exposure [2]. As the metal tends to
the lowest possible energy state, this is an exer-
gonic process. As a result, when metals are
mixed with oxygen and water to create oxides,
they have a natural propensity to return to their
lowest energy state (corrosion products). These
corrosion products are the final state of pro-
cessed metals that degrade over time when
exposed to the elements. Thus, the life cycle
from mined and processed ores to industrial
products and eventually back to their natural
state is as shown in Fig. 2.1.
Eco-Friendly Corrosion Inhibitors
DOI: https://doi.org/10.1016/B978-0-323-91176-4.00023-4 13
Corrosion has a significant impact both eco-
nomically and environmentally on almost all the
world’s infrastructure. This includes highways,
bridges, automobiles, pipelines, chemical pro-
cessing, water/wastewater systems, and the
military [3]. Corrosion costs more than $ 1.8 tril-
lion per year globally. Studies done in China,
Japan, the United Kingdom, Europe, and South
America have shown corrosion costs similar to
the United States. This corrosion problem trans-
lates into 3–4% of the GDP of industrialized
nations worldwide. Corrosion is so prevalent
and manifests itself in such diverse forms in our
industrialized society that its occurrence and
associated costs can never be eliminated [4].
The environment to which metals are exposed
consists of the entire surroundings in contact
with the metal. The major factors used to
describe the environment are the physical state
of the environment, either gas, liquid or solid;
chemical composition, which includes constitu-
ents and concentrations; and temperature [5].
These three factors have a significant influence
on the rate of corrosion. However, additional
Copyright © 2022 Elsevier Inc. All rights reserved.
14 2. Corrosion prevention and protection methods
Crude steel Production
Raw Material Extraction
Post-consumer
scrap
End of Life
phase
FIG. 2.1 Flow of material through society.
factors such as the velocity of a solution (flow
rate) and mechanical stress and/or loads can
also play an important role in the corrosion of
metals. In order to understand and control cor-
rosion, one must take into account both the
material and the environment. Identifying both
of these components will determine effective
strategies for combating these destructive
processes.
The corrosion subject has witnessed an inevi-
table transition from the state of isolation and
obscurity to an established engineering disci-
pline. There have already been significant
advances over time in the field of corrosion and
corrosion prevention. There are, however, still
many problems that corrosion scientists/engi-
neers need to solve. Learned societies such as
NACE, the European Corrosion Federation, the
Japan Society of Corrosion Engineers, and others
play a prominent role in the growth of education
in corrosion engineering. Therefore, the primary
aim of the chapter is to cover the fundamentals
related to the prevention and control of corro-
sion in order to establish a basic understanding
Part 1 Overview of industrial corrosion and inhibition
Production of
iron and steel
products
Pre-consumer
scrap
Use Phase of
End Products
Sector X
to overcome this catastrophic phenomenon and
minimize its cost. The chapter will cover the
basic methods employed and the recent advances
in the field precisely.
2.2 Important considerations required
for the corrosion prevention and
control methods
The process of corrosion prevention and control
does not end with the selection of materials.
Instead, it lasts throughout a product’s lifespan,
from acquisition through maintenance. Some of
the elements that influence corrosion during the
life of a system are depicted in Fig. 2.2. Corrosion
prevention and control should begin with the
development of the design concept and continue
through the material selection process [6].
Through the detailed design phase, preventive
maintenance and monitoring/inspection plans
should be devised, and they should be main-
tained and updated as needed during the sus-
tainment phase. Table 2.1 depicts the important
 2.2 Important considerations required for the corrosion prevention and control methods 15

Design

Monitoring/ Material
Inspection Selection

Corrosion
Prevention And
Control
Considerations

Preventative Processing/
Maintenance Manufacturing

FIG. 2.2 Some consideration for corrosion prevention and control.

factors to consider when developing corrosion-
resistant components and/or systems. The sec-
tions that follow go through these topics in
further depth.
2.2.1 Design considerations
The particular design geometry is important
as areas where water and/or debris may accu-
mulate can experience increased corrosion rates.
Simply drilling holes in structures to allow drain-
age of water can help to mitigate this problem.
Eliminating sharp corners will help reduce
crevice attacks. Also, providing accessibility,
when possible, to corrosion-prone areas for clean-
ing and maintenance is important. The geometry
of components also influences erosion-corrosion
for systems exposed to flowing corrosive fluids.
This includes directional changes in piping and
the access ports for chemicals that are added into
the systems. The interfaces between adjacent
materials or components may contribute to cor-
rosion in the form of the galvanic, crevice, and
intergranular corrosion. The relative sizes of the
two materials affect the current density between
them, which factors into galvanic corrosion rates.
Fastened joints are areas that can trap electrolytes
resulting in crevice attack. Welded and brazed

Part 1 Overview of industrial corrosion and inhibition

16 2. Corrosion prevention and protection methods

TABLE 2.1 Important factors to consider when joints can increase susceptibility to intergranular
developing corrosion-resistant components and/or corrosion in certain alloys/heat treatments. The
systems. design along with the operation of the system,
S.No. Considerations Factors will determine the applied stress to the compo-
1. Design • Geometry nents that may result in stress corrosion cracking
• Material interfaces (SCC) or corrosion fatigue. And finally, systems
• Relative size operated in close proximity to electrically con-
• Joints ducting structures may experience stray-current
✓ Welded
corrosion [7,8].
✓ Fastened
✓ Brazed
• Applied stresses
• Stray current
2.2.2 Material selection considerations
2. Material selection • Base material The cost of maintaining a system is signifi-
• Heat treatment cantly influenced by the initial choice of materi-
3. Process or • Surface treatments als, heat treatment methods, and corrosion
manufacturing ✓ Conversion coatings prevention and control measures/materials.
✓ Cleaning The choice of heat treatment is crucial as numer-
✓ Anodization
✓ Shot or shock peening
ous corrosion forms, including stress corrosion
• Cold working cracking, corrosion fatigue, intergranular, and
✓ Fasteners exfoliation corrosion, can be strongly influenced
• Polishing by a material’s processing history.
• Coatings
• Quality control
✓ Impurities 2.2.3 Processing/manufacturing
✓ Defects
✓ Surface condition
considerations
✓ Joints Processing and manufacturing methods can
4. Preventive • Storage conditions also affect corrosion rates through the surface
maintenance ✓ Humidity roughness, quality of the material/component,
• Cleaning
✓ Agents
and the implementation of corrosion prevention
✓ Abrasives and control measures. Chemical surface treat-
✓ Inhibitors ments (conversion coatings and anodization) as
✓ Biocides well as corrosion resistant primers and topcoats
• Coating removal will influence all forms of corrosion by providing
• Recoating
• Corrosion preventative
barriers or sacrificial corroding layers to protect
the base materials. Mechanical surface treatments
5. Monitoring or • Electrochemical sensors
inspection ✓ Visual inspection
(shot peening or laser shock peening) increase
• Weight loss coupons resistance to stress corrosion cracking, corrosion
• Bacteria counts/cultures fatigue, and hydrogen assisted cracking (HAC).
• NDI Cold working, including oversized fasteners, is
✓ Thickness another form of mechanical processing which
✓ Cracks
increases resistance to cracking mechanisms. Pol-
ishing surfaces can reduce susceptibility to pitting
attack and increase resistance to crack initiation.
The quality of the material/component plays a

Part 1 Overview of industrial corrosion and inhibition

 2.2 Important considerations required for the corrosion prevention and control methods
role in any impurities within a material and any
defects on its surface or in a joint may increase
the risk of corrosion.
2.2.4 Preventive maintenance
considerations
By employing a preventive maintenance
schedule where a vehicle or structure is peri-
odically inspected and cleaned, as necessary,
will help to reduce corrosion. Salt and debris
buildup on vehicles or structures, for example,
can accelerate corrosion. Therefore, routinely
washing them to remove the contaminants is a
sound practice. Furthermore, touching up pro-
tective coatings or reapplying corrosion pre-
ventative compounds (CPCs) on a regular
basis would assist in the reduction of corro-
sion. Surface preparation is critical to coating
adhesion, although in most cases, recoated
systems will never adhere to the original
coating deposited in a controlled environment.
Often overlooked during a corrosion analysis
is the period in which a system is not in opera-
tion. Some materials, such as stainless steels,
are resistant to high velocity flowing liquids
and thus are used for certain piping applica-
tions. However, these same materials can be
susceptible to pitting, crevice, and microbio-
logically influenced corrosion (MIC) under
stagnant conditions. Introducing inhibitors
and/or biocides into piping during downtimes
can reduce these forms of corrosion. Storage
conditions are also very important. Reducing
relative humidity below 60% can drastically
prevent system corrosion during storage.
Reducing the temperature in hot/humid cli-
mates will also be beneficial.
2.2.5 Monitoring/inspection
considerations
Monitoring and inspection are often essential
preventive maintenance procedures. Visual
Part 1 Overview of industrial corrosion and inhibition
17
inspection has been widely practiced through-
out most any system. Hidden corrosion requires
a number of different tactics dependent upon
the system. Borescopes and fiberscopes are used
to visually inspect the inside of some systems
through access ports. The corrosivity of the
operational environment is monitored using
electrochemical sensors. Bacterium counts and
cultures are used to monitor microbiological
activity and to regulate the use of biocides. Cor-
rosion coupons are a low-technology technique
of placing metal samples within the system and
periodically measuring their weight loss. Per-
sonnel responsible for maintaining critical
systems may additionally use a host of nonde-
structive inspection methods to measure thick-
nesses or detect cracks. System design, materials
selection and manufacturing process actions
are interrelated where each weighs in on the
others as depicted in Fig. 2.3. Historically, there
have been many instances where costly designs
have been developed with little or no upfront
consideration of materials or manufacturing
concerns. This linear approach to developing a
new component or system can lead to compro-
mises that can be avoided with a concurrent
process where all issues are considered early
and simultaneously.
Design (Service
Conditions,
Function, and Cost)
Processing/Manufa
Materials
cturing (Equipment
(Properties,
Availability, and
Selection, Influence
on properties and
Cost)
Cost)
FIG. 2.3 Interdependence of design, material selection,
and processing/manufacturing.
18 2. Corrosion prevention and protection methods
2.3 Strategies of the corrosion
prevention and control methods
Design, maintenance, and material selection
can be strategically used to minimize the extent
to which a material, component or system cor-
rodes during its lifetime. Simple elements incor-
porated into a design can lessen the risk of
corrosion. For example, allowing for drainage of
water that otherwise might become trapped can
effectively reduce corrosion problems. Similarly,
employing seals to preclude water from enter-
ing a component or system will provide similar
results. Another effective way to minimize cor-
rosion is to use gaskets to electrically insulate
two dissimilar metals, thus eliminating the pos-
sibility of galvanic coupling between adjacent
components. Employing a maintenance sched-
ule where a vehicle or structure is periodically
cleaned to remove salt or debris buildup will
help reduce corrosion. In addition, regularly
touching up protective coatings or reapplying
corrosion prevention and control methods will
help reduce instances of corrosion. Perhaps the
most important way to prevent corrosion from
occurring in the first place is to make appropri-
ate material selection decisions upfront by care-
fully considering the application, environment,
and potential corrosion problems that might
occur. Selecting the appropriate materials and
associated corrosion prevention and control
practices can reduce maintenance costs and
system downtime over the life-cycle of a system.
There are a handful of material selection strate-
gies that are used by designers. These strategies
range from a broad selection process used to
establish a list of material classes that will be
applicable for a design down to detailed deci-
sion matrices to select specific materials/heat
treatments. The intent of this book is not to
address the various methods of selecting materi-
als themselves. Rather, the purpose is to supple-
ment existing processes with a ‘roadmap’ or
process that a designer can employ during mate-
rials selection to help reduce the risk of
Part 1 Overview of industrial corrosion and inhibition
corrosion-related problems later in a product’s
lifecycle. A comprehensive analysis starts by
employing a traditional process to examine the
mechanical, thermal, electrical, or physical
requirements to determine which material class
to employ and to subsequently select an initial
slate of candidate materials. The process
described here will be used to further examine
these candidates to identify the one that pos-
sesses the best combination of performance and
life-cycle costs.
2.4 Methods of corrosion control
Corrosion management requires the imple-
mentation of engineering principles and tech-
niques to, by the most economical method,
mitigate corrosion to an appropriate degree. To
mitigate or control corrosion, there are different
practices that could be used (illustrated in
Fig. 2.4). The use of the method relies upon
multiple parameters. For example, the type and
the location of the corrosion, the practical use of
the surface/structure to be protected, the local
environment, etc. The objective of the corrosion
control techniques is to minimize corrosion of
materials to an acceptable limit, so that they are
able to attain their normal desired lifetime. In a
limited number of cases, corrosion control
methods are designed to eliminate it completely.
The subsequent text summarizes the most
commonly used ways and methods to tackle
corrosion [9].
2.4.1 Proper selection of materials
The methodology involves the selection and
use of materials with high corrosion resistance
to increase a structure’s longevity in a specific
setting. While there are no materials that are
resistant to all corrosive conditions, it is impor-
tant to choose suitable materials to avoid certain
forms of corrosion failure. Corrosion may be
minimized by employing an appropriate design
 2.4 Methods of corrosion control 19

FIG. 2.4 An outline of various methods used in corrosion control.

as discussed. On the other hand, the selection of
appropriate materials in a given environment is
a key to corrosion control strategy.
Titanium, for instance, is a highly corrosion-
resistant material, but it is far more costly than
steel. Furthermore, it is not as ductile as steel.
Carbon steel is the material of choice in oil pro-
duction systems, especially for equipment such as
wells, pipelines, vessels and tanks, due to its good
mechanical properties and low cost. However,
options such as stainless steel can be used for situ-
ations where more corrosion-resistant material is
needed. The main parameters to be considered
when selecting materials for any equipment are:
• Operating conditions, including temperature,
pressure, and medium are contained,
• Availability
• Environment
• Legislation and internal regulations
• Cost
• Lead time
• Expected life time of the equipment
• Safety
In terms of materials, the selection criteria
normally translate into some of the following
parameters:
• Mechanical properties
• Cost
• Corrosion resistance to media and
environment
• Availability on request
• Temperature operating range
Although the mechanism of corrosion is highly
complex, the actual control of the majority of cor-
rosion reactions can be affected by the application
of relatively simple concepts. Indeed, the Com-
mittee on Corrosion and Protection concluded
that “better dissemination of existing knowl-
edge” was the most important single factor that
would be fundamental in decreasing the enor-
mous cost of corrosion in the UK [10].

Part 1 Overview of industrial corrosion and inhibition

20 2. Corrosion prevention and protection methods
2.4.2 Environmental modification
A chemical reaction between the corrosive
state of the metal and the local atmosphere
causes corrosion. Metal corrosion can be regu-
lated instantly by excluding the metal from, or
modifying, the state of the atmosphere. This can
be as simple as reducing contact with rain or
seawater via indoor storage of metal materials
or may be in the form of direct environmental
manipulation affecting the metal. The rate of
metal corrosion can be lowered by methods to
minimize the sulphur, chloride or oxygen
content of the surrounding atmosphere. For
example, in order to minimize corrosion in the
interior of the unit, feed water for water boilers
may be formulated with softeners or several
other chemicals in order to alter the hardness,
alkalinity or oxygen content. In boilers, in order
to remove the oxygen and other gases from the
feed water, deaerators are largely utilized.
Boiling water removes the majority of the oxygen
and is sufficient treatment in some boilers. When
water is used for cooling or other applications
where heating is not required, it is subjected to
a vacuum, which removes the majority of the
oxygen. For steam-generating boilers, however,
very low oxygen content is required, and steam
deaerators, as shown in Fig. 2.5, are used. The
Atmospheric
vent
Boiler
feedwater
Steam
Deaerated Feedwater
Deaerated water
to boilers
FIG. 2.5 Principle of steam deaerator.
Part 1 Overview of industrial corrosion and inhibition
feedwater is sprayed or formed into a thin film
and exposed to a steam atmosphere, where it
quickly heats up. This process reduces the solu-
bility of all dissolved gases, removing them
from the feedwater. The released gases are then
released into the atmosphere along with the
excess steam. The deaerated water falls into the
vessel’s storage section. This system reduces
the concentration of dissolved oxygen to less
than 7 ppb and completely eliminates the con-
centration of carbon dioxide. This water can
then be used to generate steam without further
treatment.
In atmospheric corrosion, water and oxygen
are the primary corrosive agents. Because
removing oxygen is impractical, methods that
focus on reducing moisture content are used.
There is negligible corrosion of the major engi-
neering metals at relative humidity levels below
about 50%, and there are a number of ways to
reduce humidity.
• Air can be heated in warehouses and
storerooms to reduce relative humidity
below this level, but this causes a problem
when cold objects are brought into the
room. Any surface with a temperature
below the dew point will condense,
resulting in severe corrosion.
• A better solution is to chill the air before it
is circulated in a warehouse, allowing water
to precipitate. The residual water content of
such freeze drying can be extremely low.
• Desiccants (also known as moisture
scavengers) like silica gel and activated
alumina can be used to dry the air in
packages and small storage areas.
2.4.3 Cathodic protection
Cathodic protection involves polarization of
the structure, to be protected, to potentials more
negative than the corrosion potential, thus ther-
modynamically preventing the occurrence of
anodic reaction. For this purpose, an external
power source is used. Another common way is
 2.4
to use “sacrificial anodes.” In this method, the
anode is made of a more active metal (e.g. mag-
nesium) than the structure to be protected (e.g.
iron or carbon steel). Thus, the structure which
needs to be protected acts as the cathode of a
new corrosion cell [5]. This type of protection is
widely used to protect some underground struc-
tures, for example, water storage tanks, buried
pipelines, ship hulls, and marine facilities. There
are two methods of cathodic protection:
2.4.3.1 Impressed current method
Impressed current cathodic protection tech-
niques are widely used for the protection of
buried pipelines and the hulls of ships immersed
in seawater. A DC electrical circuit is used to
apply electric current to the metallic structure.
Methods of corrosion control 21
The negative terminal of the current source is
connected to the metal requiring protection. The
positive terminal is connected to an auxiliary
anode immersed in the same medium to com-
plete the circuit. The electric current charges the
structure with excess electrons and hence
changes the electrode potential in the negative
direction until the immunity region is reached.
The layout for a typical impressed current
cathodic protection system is shown in Fig. 2.6.
Impressed current cathodic protection is the
most specialized technology and can be very
effective if correctly designed and operated.
Typical materials used for anodes are graphite,
silicon, titanium, and niobium plated with plati-
num. Coatings are often used in conjunction
with impressed current cathodic protection

DC POWER SUPPLY

+ –

WIRE WIRE

SOIL SURFACE

CURRENT

CATHODE
IMPRESSED ANODE (METAL STRUCTURE
(E.g., GRAPHITE) TO BE PROTECTED)

FIG. 2.6 A general representation of the impressed current cathodic protection method.

Part 1 Overview of industrial corrosion and inhibition

22 2. Corrosion prevention and protection methods

systems to minimize the effect of corrosion on magnesium-base and aluminum-base alloys

marine structures. One of the difficulties in
designing a combined coating and an impressed
current cathodic protection system is that coat-
ings deteriorate with time. Precious metals are
used for impressed current anodes because they
are highly efficient electrodes and can handle
much higher currents. Precious metal anodes
are platinized titanium or tantalum anodes; the
platinum is either clad in or electroplated on the
substrate. Impressed current systems are more
complex than sacrificial anode systems and
mostly used to protect pipelines.
2.4.3.2 Sacrificial anode method
The principle of this technique is to use a
more reactive metal in contact with a steel struc-
ture to drive the potential in the negative direc-
tion until it reaches the immunity region. Fig. 2.7
illustrates the principle in which sacrificial
metals used for cathodic protection consist of
and, to a lesser extent, zinc.
No external power source is needed with this
type of protection system and much less main-
tenance is required. These metals are alloyed to
improve long-term performance and dissolu-
tion characteristics. Sacrificial anodes serve
essentially as sources of portable electrical
energy. For cathodic protection of offshore plat-
forms, aluminum anodes, made from alu-
minum-zinc alloys, are the preferred material.
Most offshore petroleum-production platforms
use sacrificial anodes because of their simplicity
and reliability, even though the capital costs
would be lower with impressed-current
systems. Magnesium anodes have been used
offshore in recent years to polarize the struc-
tures to a protecting potential faster than zinc
or aluminum alloy anodes. Magnesium tends to
corrode quite readily in salt water, and most
designers avoid the use of magnesium for

NO POWER SOURCE IS NEEDED

LEAD WIRE
SOIL SURFACE

Protective Current

SACRIFICIAL ANODE CATHODE

(E.g., MAGNESIUM) (METAL STRUCTURE TO
BE PROTECTED)

FIG. 2.7 A general representation of the sacrificial anode cathodic protection method.

Part 1 Overview of industrial corrosion and inhibition

 2.4 Methods of corrosion control
permanent long-term marine cathodic protec-
tion applications. Zinc anodes are also used to
protect ballast tanks, heat exchangers, and
many mechanical components on ships, coastal
power plants, and similar structures. In seawa-
ter, passivity can be avoided by alloying addi-
tions, such as tin, indium, antimony, or mercury.
The three most common types of sacrificial
anodes are: activated aluminum, zinc and mag-
nesium. Aluminum is the most widely-used
material for anodes, as it has a higher current
capacity in comparison to the other metals.
Magnesium should be considered when the
chloride content is less than 10,000 ppm.
2.4.4 Anodic protection
Anodic protection, which is an electrochemi-
cal method of controlling corrosion based on the
phenomenon of passivity, is a comparatively
new method suggested by Edeleanu [9,10]. To
build a protective oxidized layer on the pro-
tected base material, also known as the sub-
strate, an electrical current is used in the process.
The passive potential is automatically main-
tained, usually electronically, by an instrument
called the potentiostat. The method is applicable
to metals having active passive transitions like
nickel, titanium, iron, chromium and their
alloys. Its usefulness and its low current demand
in highly corrosive environments are the signifi-
cant benefits of anodic protection.
2.4.5 Coating, linings, and nonmetallic
piping
A coating is a thin material applied as a liquid
or powder, which, on solidification, is firmly
and continuously attached to the material, to be
protected. For internal use, this method might
be called lining. Coatings need to be flexible,
resistant to chemical fluid attacks, to have strong
adhesion, to have low or no porosity, and to be
stable at working temperatures. The coatings
Part 1 Overview of industrial corrosion and inhibition
23
are often applied in conjunction with cathodic
protection systems to take care of any damage
caused to the coating material. Application of
non-metallic piping is also good in many appli-
cations as they do not corrode, but the limitation
is that they may deteriorate or it weakened by
attack from their environment. Polyvinyl chlo-
ride (PVC) is one example of this type of piping;
this material is usually repeatedly reheated, sof-
tened and reshaped without destruction.
However, where mechanical/structural integ-
rity is important, such in cases of high internal
or external pressures and loads, PVC and other
polymer-based materials cannot be used, and
the use is then usually confined to metals. Metal
coatings can also be incorporated into this cat-
egory. For example, corrosion susceptible metals
(e.g. carbon steels) could be coated with a thin
chromium coating. Chromium is a highly corro-
sion resistant material, and as long as the chro-
mium coating is compact, it will protect the
underlying structure from corrosion.
2.4.5.1 Organic coatings
Such coatings afford protection by providing a
physical barrier between the metal and the envi-
ronment. The substrate material and the environ-
ment are separated by a rather thin barrier. Paints,
varnishes, lacquers, and other similar coatings
undoubtedly preserve more metal per ton than any
other corrosion-prevention technique. Although
most people are familiar with outside surfaces,
inside coatings or linings are also extensively used.
Organic coatings cost approximately $2 billion per
year in the United States. There are several sorts of
products involved, some of which are backed by
ludicrous claims. For good performance, extensive
understanding of this difficult area is necessary. For
the uninformed, the best course of action is to seek
advice from a recognized organic coatings manu-
facturer. As a general rule, these coatings should
not be utilized in environments where the sub-
strate material will be rapidly attacked by the
environment.
24 2. Corrosion prevention and protection methods
2.4.5.2 Inorganic coatings
To provide a barrier between the atmosphere
and the metal, these coatings are often used.
Enamel, glass linings, and conversion coatings
are all inorganic coatings. The treatment trans-
forms the metal surface into a metallic oxide film
or a compound that is more resistant to corrosion
than the natural oxide film and provides an effec-
tive base or additional safety key, such as paints.
2.4.5.3 Metallic coatings
Another type of coating is metallic coatings
that provide a barrier between the metal sub-
strate and the atmosphere. Furthermore, when
the coating is damaged, metallic coatings can
often provide cathodic protection. Using a
variety of techniques, including hot dipping,
electroplating, cladding, thermal spraying, and
chemical vapor deposition, metallic coatings
and other inorganic coatings are developed.
2.4.6 Use of corrosion inhibitors
In different industries, among the most efficient
methods of effectively reducing corrosion is by
using corrosion inhibitors. Corrosion inhibitors
are chemical substances which stop or retard cor-
rosion of the metallic surface when added to the
corrosive medium in small quantities. Most of the
inhibitors actively employed are organic mole-
cules [11]. Via adsorption on the metallic surface,
these inhibitors work to protect the surface by
forming a film that minimizes the contact between
Fe2+
O2 O2
Cathode Anode Cathode
e– e–
(A)
FIG. 2.8 Illustration of mechanism of protection of metals by (A) an anodic inhibitor and (B) a cathodic inhibitor.
Part 1 Overview of industrial corrosion and inhibition
the metal surface and the aggressive environment.
The physical blockage effect or the effects of the
inhibitor on the mechanisms and kinetics of the
corresponding corrosion reactions can be related
to this minimization. Inhibitors are typically deliv-
ered from a solution or dispersion, but some are
used in preparations for protective coating.
Inhibitors are defined by the International
Standard Organization as “a chemical compound
that, when given to an environment in a tiny quan-
tity, retards corrosion without substantially affect-
ing the concentration of any other corrosive agent.”
According to this definition, a chemical added to
an environment to neutralize an acidic constituent
or oxygen scavengers added to water to remove
oxygen from the electrolytes are not inhibitors,
despite the fact that they help to reduce corrosion
rates. For a corrosion regulating chemical to be
called a corrosion inhibitor, it must be adsorbed at
the corroding interface in the form of a molecule or
as ions (anions or cations). Inhibitors usually work
by adsorbing oneself to the metallic surface and
producing a film to protect it. Inhibitors are usually
dispersed or diffused from a solution. Some are
incorporated into the formulation of a protective
coating. The schematic diagram of adsorption
inhibitors can be seen in Fig. 2.8. Adsorption inhibi-
tors establish a chemisorptive interaction with the
metal surface, prohibiting electrochemical dissolu-
tion processes from proceeding.
Metal and alloy corrosion is caused by the
creation of minute electrochemical cells at the
metal-electrolyte interface, as already known.
O2 O2
Fe2+
Cathode Anode
e–
(B)
 Conclusion
Corrosion inhibitors work by influencing any of
the corrosion reactions, either anodic or cathodic.
Corrosion is slowed by inhibitors for the follow-
ing reasons [12]:
1. Increasing the behavior of anodic or cathodic
polarization (by altering the Tafel slopes),
2. Ion diffusion or migration to the metallic
surface is reduced, and
3. Increasing the metallic surface’s electrical
resistance.
Various scholars have categorized inhibitors
in different ways. Some authors choose to clas-
sify inhibitors into the categories as anodic,
cathodic, or mixed inhibitors based on their pre-
ferred role in controlling the anodic, cathodic, or
impacting both reactions [12,13].
2.4.6.1 Anodic inhibitors
They are also called passivators or passivat-
ing corrosion inhibitors. They generate a signifi-
cant anodic shift in the corrosion potential,
causing the metallic surface to passivate. There
are two types of passivating inhibitors: oxidiz-
ing anions like chromate, nitrite, and nitrate,
which may passivate steel in the absence of
oxygen, and non-oxidizing ions like phosphate,
tungstate, and molybdate, which require oxygen
to passivate steel. Because these inhibitors are
the most effective, they are also the most exten-
sively utilized. Chromate-based inhibitors are
the cheapest inhibitors and have been employed
in a range of applications until recently (e.g.,
recirculation-cooling systems of internal com-
bustion engines, rectifiers, refrigeration units,
and cooling towers). For these applications,
sodium chromate was employed at concentra-
tions ranging from 0.04 to 0.1 percent. Higher
amounts are required at higher temperatures or
in fresh water with chloride concentrations
above 10 ppm. Sodium hydroxide is used to
modify the pH to a range of 7.5 to 9.5 if neces-
sary. Corrosion will be increased if the chromate
concentration goes below 0.016 percent. As a
result, it is critical to do periodic colorimetric
Part 1 Overview of industrial corrosion and inhibition
25
analysis to prevent this from happening. When
concentrations fall below required levels, pas-
sivation inhibitors can actually promote pitting
and accelerate corrosion. As a result, it’s crucial
to keep track of the inhibitor concentration.
2.4.6.2 Cathodic inhibitors
Cathodic inhibitors either impede the cathodic
reaction or precipitate selectively on cathodic
sites, increasing surface impedance and limiting
the diffusion of reducible species to these areas.
Cathodic inhibitors work in three ways to provide
inhibition: (1) as cathodic poisons, (2) as cathodic
precipitates, and (3) as oxygen scavengers. Some
cathodic inhibitors, including arsenic and anti-
mony compounds, act by making hydrogen
recombination and discharge more difficult.
Other cathodic inhibitors, such as calcium, zinc,
or magnesium, can form oxides on the metal and
form a protective layer. By inhibiting cathodic
depolarization induced by oxygen, oxygen scav-
engers aid in corrosion prevention. At room tem-
perature, sodium sulfite is arguably the most
often used oxygen scavenger (Na2SO3).
Conclusion
Over time there has been significant progress
in the development of corrosion prevention and
control methods, understanding of basic mecha-
nisms by which corrosion occurs, and the imple-
mentation of mitigation techniques. This progress
has allowed for the current state of material
usage in both common and harsh environments.
The primary drivers for corrosion research have
been industrial and government needs. Address-
ing these needs has led to advances in science, as
well as further practical improvements, which
then provide for further scientific advances.
Several strategies for retarding or preventing
corrosion in diverse environments have been
described in depth in this chapter. The greatest
way to avoid corrosion is to use the right materi-
als, which are inert to the environment in which
26 2. Corrosion prevention and protection methods
they are used. Corrosion allowances should be
included at the equipment design stage. Corro-
sion has an impact on the material selection.
Higher alloyed materials should be more cost
effective if the rate of corrosion is high. In addi-
tion to these concerns, a variety of additional
techniques are used to avoid corrosion. Protective
paints, protective metal and organic coatings,
protective films generated as a result of chemical
reactions, regulating the pH of the aqueous solu-
tion toward more alkaline, and applying electri-
cal potential to the equipment are some of these
ways (which needs to be protected).
The interior and external equipment environ-
ments, such as moisture content, sunshine,
outdoor temperature, chemical reaction, salts,
galvanic response, wear, abrasion, and stress, all
influence the choice of cost-effective corrosion
solutions. Understanding and knowledge of
corrosion’s causes is essential for successful cor-
rosion prevention and management.
Acknowledgment
Authors acknowledge the financial support from Council of
Scientific & Industrial Research (CSIR), New Delhi, India,
through the major research project [file number: 22(0832)/20/
EMR-II].
Useful books
1. Metals Handbook - Volume 13A, 13B, 13C, Corrosion,
9th Ed., ASM International, Metals Park, Ohio, (2006).
2. M.G. Fontana, Corrosion Engineering, 3rd Ed.,
McGraw-Hill, New York, (1986).
3. Denny A. Jones, Principles and Prevention of
Corrosion, 2nd Ed., Prentice Hall, Upper Saddle River,
NJ, USA, (1996).
4. Shrier’s Corrosion, 4 Volumes (ed. T.J.A. Richardson),
Elsevier Science, (2009).
5. P.R. Roberge, Corrosion Basics - An Introduction, 2nd
Ed., NACE, Houston, Texas, (2005).
6. Joseph R. Davis, Corrosion: Understanding the Basics,
ASM International, (2000) The above five books are
perhaps the best corrosion textbooks.
7. C.G. Munger & L. Vincent, Corrosion Prevention by
Protective Coatings, 2nd Ed., NACE, Houston, Texas,
(1999).
Part 1 Overview of industrial corrosion and inhibition
8. A.W. Peabody, Control of Pipeline Corrosion, 2nd Ed.,
NACE, Houston, Texas, (2001).
Useful websites
https://www.icorr.org/souces-of-information/
https://www.nace.org/resources/general-resources/
corrosion-basics
https://eoncoat.com/corrosion-prevention-methods/
https://www.corrosionpedia.com/corrosion-companies
References
[1] M.G. Fontana, N.D. Greene, The eight forms of corro-
sion, Corros. Eng. 2nd ed. (1978) 137–148.
[2] M.G. Fontana, Corrosion Engineering, 3rd ed. McGraw-
Hill; Singapore, 1987.
[3] W.D. Callister (2007). Materials science and engineer-
ing- an introduction.
[4] L.H. Bennet, J. Kruger, R.I. Parker, E. Passiglia, C.
Reimann, A.W. Ruff, H. Yakowitz, E.B. Berman, Eco-
nomic effects of metallic corrosion in the United States,
Nat. Bur. Stand. Spec. Publ. 511 (1978) 1–72.
[5] G.H. Koch, M.P.H. Brongers, N.G. Thompson, Y.P.
Virmani, J.H. Payer, Corrosion costs and preventive
strategies in the United States, Mater Perform 42 (2002)
2–11.
[6] T.P. Hoar, Review lecture: corrosion of metals: its cost
and control, Proceedings of the Royal Society of
London. Series A, Mathematical and Physical Sciences,
348, The Royal Society Publishing 1976, pp. 1–18.
[7] M. Aliofkhazraei, Developments in Corrosion Protec-
tion, InTechOpen; London, 2014, p. 978.
[8] M. Aliofkhazraei, Developments in Corrosion Protec-
tion b, InTech, 2014, p. 978.
[9] C. Edeleanu, Method for the Study of Corrosion Phe-
nomena, Nature 173 (1954).
[10] C. Edeleanu, & Metallurgia. (1954). 50.
[11] M. Mobin, R. Aslam, J. Aslam, Non toxic biodegradable
cationic gemini surfactants as novel corrosion inhibitor
for mild steel in hydrochloric acid medium and synergis-
tic effect of sodium salicylate: Experimental and theoreti-
cal approach, Mater. Chem. Phys. 191 (2017) 151–167,
https://doi.org/10.1016/j.matchemphys.2017.01.037.
[12] M. Mobin, S. Zehra, R. Aslam, L-Phenylalanine methyl
ester hydrochloride as a green corrosion inhibitor for
mild steel in hydrochloric acid solution and the effect
of surfactant additive, RSC Adv. 6 (7) (2016) 5890–5902,
https://doi.org/10.1039/c5ra24630j.
[13] M. Mobin, S. Zehra, M. Parveen, L-Cysteine as corro-
sion inhibitor for mild steel in 1 M HCl and synergistic
effect of anionic, cationic and non-ionic surfactants,
J. Mol. Liq. 216 (2016) 598–607, https://doi.org/10.
1016/j.molliq.2016.01.087.
 C H A P T E R

3
Development process for eco-
friendly corrosion inhibitors
Mohamed Rbaaa, Mouhsine Galaib, Omar Dagdagg,
Lei Guoc, Burak Tüzünd, Elyor Berdimurodove,
Abdelkader Zarroukf, Brahim Lakhrissia
a
Laboratory of Organic Chemistry, Catalysis and Environment, Faculty of Sciences,
Ibn Tofail University, Kenitra, Morocco
b
Advanced Materials and Process Engineering, Faculty of Sciences, Ibn Tofaïl
University, Kenitra, Morocco
c
School of Materials and Chemical Engineering, Tongren University, Tongren, China
d
Department of Chemistry, Faculty of Science, Sivas Cumhuriyet University, Turkey
e
Faculty of Chemistry, National University of Uzbekistan, Tashkent, Uzbekistan
f
Laboratory of Materials, Nanotechnology and Environment, Mohammed V
University, Faculty of Sciences, Rabat, Morocco
g
Institute of Nanotechnology and Water Sustainability, College of Science,
Engineering and Technology, University of South Africa, Johannesburg, South Africa

3.1 Introduction At the present times, the coatings and corrosion

The metallic materials are main used materi-
als, because, their physical properties, such as
electrical conduction, thermal conduction, and
mechanical performances. The steel based
metallic materials are most common in the gas
and oil industry [1–3]. However, a high percent-
age of the steel materials are damaged by corro-
sion in acidic environments [4]. Therefore, to
protect steel materials is ongoing problem. Cur-
rently, many researches are interested to going
research in the corrosion protection.
inhibitors are widely used to protect the metallic
materials from the corrosion destruction. The
metal surface is covered with the coatings, as a
result, the covered metal surface is effectively
insulated from the corrosion environments. The
corrosion inhibitors are performed to protect the
metal surface from the oxidation and corrosion
destruction in the aqueous phase [5,6]. Currently,
the researchers are focusing more on inhibiting
corrosion development, because, the corrosion
protection is ongoing issue in the chemical indus-
try [7–9]. The corrosion inhibitors are based on the

Eco-Friendly Corrosion Inhibitors

DOI: https://doi.org/10.1016/B978-0-323-91176-4.00026-X 27 2022 Published by Elsevier Inc.
28 3. Development process for eco-friendly corrosion inhibitors
organic or inorganic chemical compounds are
need to become an environmentally and economi-
cally effective [10,11]. Also, the application of syn-
thetic compounds as corrosion inhibitors is limited,
because of the increasing ecological awareness
and strict environmental regulations. The tradi-
tional corrosion inhibitors are synthesized using
expensive and toxic chemicals or solvents. In view
of this, recently, the glucose and their derivatives
are being used as green corrosion inhibitors as
they are available at the economic and commercial
level [12]. This is due to their natural and biologi-
cal origin; they can be regarded as one of the
greenest sources of the chemical compounds as
corrosion inhibitors. Therefore, the presence of
numerous polar functional groups, such as –OH,
further enhance their corrosion inhibition effec-
tiveness by increasing their molecular size as well
as increase solubility in the polar electrolytes.
These polar functional groups can also serve as
adsorption centers during the meta-inhibitor
interactions. Looking at the greenness of glucose
and their derivatives along with their high protec-
tion efficiency, the synthesis, characterization and
utilization in all fields of science and technology,
including in the area of metallic corrosion inhibi-
tion should be further explored [13].
In order to preserve the health of users of
these chemical compounds, when the corrosion
inhibitor are tested, it is important task to use
non-toxic and biodegradable chemicals. Several
international organizations and committees
have spoken out against the use of toxic chemi-
cal products [12,13]. In particular, the World
Health Organization (WHO) [14], which is the
most active on this side. The World Health
Organization has published a list of chemicals
that are the greatest source of danger to health.
Asbestos, benzol, cadmium, ammonia, mercury,
lead are among these substances. The plastic
material products, cosmetics, foodstuffs include
chemicals, which some are harmful. Most of the
chemical compounds are toxic, they cause the
death of millions of people around the world
every year.
Part 1 Overview of industrial corrosion and inhibition
The main objectives in the extraction and
syntheses, the method of syntheses, characteri-
zation, and purification, discussion of obtained
results and inhibition mechanism of eco-
friendly corrosion inhibitors with the relevant
examples are discussed and reviewed in this
chapter.
3.2 Process for development of
eco-friendly synthesizing corrosion
inhibitors
Rbaa et al. [15] have synthesized new com-
pound derivatives of D-glucose biodegrada-
ble and non-toxic as corrosion inhibitors for
steel in 1.0 M HCl. These compounds were
synthesized by easy and selective methods,
and characterized by the usual spectroscopic
methods, namely, infrared (IR) and nuclear
magnetic resonance (1H NMR, 13C NMR). The
anticorrosion effect of these two compounds
was studied using gravimetric and electro-
chemical methods, such as potentiodynamic
polarization (PDP) and impedance spectros-
copy (EIS). The metal surface was character-
ized by SEM and EDS techniques and the
gravimetric solutions were analyzed by
ICP-OES and UV-visible spectrometry.
The authors were synthesized the biodegrad-
able epoxy-glucose derivatives were synthe-
sized with good selectivity in five steps:
The first step is the reaction of D-glucose 1 with
acetone in sulfuric acid (H2SO4) as a catalyst at 0°C
to obtain compound 2. The second step is to add
alkyl bromide to compound 2 in a toluene-DMSO
mixture (4:1, v/v) as solvent to obtain compounds
3a,b. The third step is a partial deprotection of
compound 3in a mixture of EtOH-H2O (95:5, v/v)
in the presence of H2SO4 (0.2 N) at 40°C to provide
compounds 4a,b. The fourth step is the reaction of
compound 4 with tosyl chloride in toluene-pyri-
dine (1:1, v/v) as solvent at a temperature between
0°C and -5°C for 72 hours to give compounds 5a,b.
The last step consists in treating the compounds
Another random document with
no related content on Scribd:
 10 qu’il volsissent priier au conte Derbi qu’il les
volsist prendre à merci, salve leurs corps et leurs
biens, et en avant il se metteroient en l’obeissance
dou roy d’Engleterre. Li contes de Pennebruch et li
contes de Kenfort respondirent qu’il en parleroient
15 volentiers; et puis demandèrent il où li contes de
[Lille] et li aultre baron estoient. Il respondirent:
«Certainnement nous ne savons, car il cargièrent et
toursèrent très le mienuit tout le leur et se partirent,
mès point ne nous disent quel part il se trairoient.»
20 Sus ces parolles, se partirent li doi conte dessus
nommet, et vinrent au conte Derbi, qui n’estoit mies
loing de là, et li moustrèrent tout ce que les gens de
Bregerach voloient faire. Li dis contes Derbi, qui fu
moult nobles et très gentilz de coer, respondi: «Qui
25 merci prie, merci doit avoir. Dittes leur qu’il oevrent
leur ville et nous laissent ens: nous les assegurons
de nous et des nostres.» Adonc retournèrent li doi
signeur dessus dit, et recordèrent à chiaus de Bregerach
tout ce que vous avés oy: dont il furent moult
30 joiant, quant il veirent qu’il pooient venir à pais. Si
vinrent ou le place et sonnèrent les sains, et se
[53] assamblèrent tout, hommes et femmes, et fisent ouvrir
leurs portes, et vinrent à grant pourcession et moult
humlement contre le conte Derbi et ses gens, et le
menèrent à le grant eglise. Et là li jurèrent il feaulté
5 et hommage et le recogneurent à signeur, ou nom
dou roy d’Engleterre, par le vertu de le procuration
qu’il en portoit. Ensi eut en ce temps li contes Derbi
le bonne ville de Bregerach, qui se tint toutdis depuis
englesce. Or, parlerons nous des signeurs de Gascongne
10 qui estoient retrait en le ville et ou chastiel
de le Riolle, et vous conterons comment il se
maintinrent.

§ 212. Celle propre nuitie et le journée ensievant

 que li contes de [Lille] et li baron et chevalier, qui
15 avoecques lui estoient, furent venu en le Riolle, il
regardèrent et avisèrent li un par l’autre qu’il se departiroient
et se trairoient ens ès garnisons, et guerrieroient
par forterèces, et metteroient sus les camps
entre quatre cens ou cinq cens combatans dont il
20 feroient frontière: si en seroient chief et meneur li
contes de Comignes et li viscontes de Quarmaing.
Adonc se departirent il. Si se traist li contes de
Pieregorth en [Perigueux[292]], li seneschaus de Thoulouse
à Montalben, li viscontes de Villemur à Auberoce,
25 messires Bertrans des Prés à Pellagrue, messires Phelippes
de Dyon à Montagrée, li sires de Montbrandon
à Maudurant, Ernaus de Dyon à [Lamongis[293]],
Bobers de Malemort à Byaumont en [Lillois], messires
[54] Charles de Poitiers à Pennes en Aginois, et ensi
les chevaliers de garnison en garnison. Si se departirent
tout li un de l’autre, et li contes de [Lille] demora
en la Riolle. Et fist remparer et rabillier le
5 ville et le forterèce, telement que elle n’avoit garde
d’assaut que on y fesist sus un mois ne deux. Or,
retourrons nous au conte Derbi qui estoit en
Bregerach.

§ 213. Quant li contes Derbi eut pris le possession

10 et le saisine de le ville de Bregerach, et il s’i fu
rafrescis par deux jours, il demanda au senescal de
Bourdiaus quel part il se [trairoit[294]], car mies ne voloit
sejourner. Li seneschaus respondi que ce seroit
bon d’aler devers Pieregort et en le haute Gascongne.
15 Dont fist li dis contes Derbi ordonner toutes
ses besongnes et traire au chemin par devers [Perigueux[295]],
et laissa en Bregerach un chevalier à chapitainne,
qui s’appelloit messires Jehans de la Souce.
Ensi que li Englès chevauçoient, il trouvèrent en
20 leur chemin un chastiel qui s’appelle Lango, dont li
 vigiers de Thoulouse estoit chapitaine, une moult
aperte armeure de fier. Il s’arrestèrent là, et disent
qu’il ne lairoient pas che chastiel derrière. Si le commença
li bataille des mareschaus à assallir, et y furent
25 un jour tout entier. Et là eut mervilleusement dur
et fort assaut, car li Englès assalloient de grant volenté,
et cil dou fort se deffendoient moult vassaument.
Nequedent, ce premier jour il n’i fisent riens.
[55] A l’endemain, priès que toute li hos fu devant. Et
recommencièrent à assallir telement et par si forte
manière, avoech ce que on avoit jetté ens ès fossés
grant fuison de bois et de velourdes par quoi on
5 pooit bien aler jusques as murs sans dangier, que cil
de dedens se commencièrent à esbahir. Adonc leur
fu demandé de messire Franke de Halle, se il se renderoient,
et que il y poroient bien tant mettre qu’il
n’i venroient point à temps. Il requisent à avoir conseil
10 de respondre. Ce leur fu acordé. Il se consillièrent;
et me samble qu’il se partirent de le forterèce
et riens n’enportèrent, et s’en alèrent devers Montsach
qui se tenoit françoise. Ensi eurent li Englès le
chastiel de Lango. Si y establi li contes Derbi un escuier
15 à chapitainne, qui s’appelloit Aymon Lyon, et
laissa laiens avoecques lui jusques à trente arciers.
Si se partirent de Lango, et cheminèrent devers une
ville qui s’appelle le Lach.

§ 214. Quant cil de le ville dou Lach sentirent

20 les Englès venir si efforciement, et qu’il avoient pris
Bregerach et le chastiel de Lango, si en furent si
effraet qu’il n’eurent mies conseil d’yaus tenir. Et
s’en vinrent au devant dou conte Derbi, et li aportèrent
les clefs de le ville, et le recogneurent à
25 signeur, ou nom dou roy d’Engleterre. Li contes
Derbi prist le feaulté d’yaus, et puis passa oultre, et
s’en vint à Maudurant, et le gaegna d’assaut sus
 chiaus dou pays. Et y fu pris uns chevaliers dou pays,
qui [s’appelloit[296]] li sires de Montbrandon. Si laissa li
[56] dis contes Derbi gens d’armes dedens le forterèce; et
puis passèrent oultre, et vinrent devant le chastiel de
[Lamongis[297]]. Si l’assallirent, et le prisent d’assaut tantost,
et le chevalier qui estoit dedens, et l’envoiièrent
5 tenir prison à Bourdiaus. Puis chevaucièrent devers
Pinac et le conquisent, et en apriès le ville et le
chastiel de Laliene, et s’i rafreschirent par trois jours.
Au quatrime, il s’en partirent et vinrent à Forsach,
et le gaegnièrent assés legierement, et en apriès le
10 tour de Prudaire. Et puis chevaucièrent devers une
bonne ville et grosse, que on appelle Byaumont en
[Lillois], qui se tenoit liegement dou conte de [Lille].
Si furent li Englès trois jours par devant, et y fisent
tamaint grant assaut, car elle estoit bien pourveue
15 de gens d’armes et d’artillerie, qui le deffendirent
tant qu’il peurent durer. Finablement elle fu prise,
et y eut grant occision de chiaus qui dedens furent
trouvet. Et le rafreschi li contes Derbi de nouvelles
gens d’armes, et puis chevauça oultre, et vint devant
20 Montagrée. Si le prist ossi d’assaut et le chevalier
qui estoit dedens, et l’envoia tenir prison à
Bourdiaus.
Et ne cessèrent li Englès de chevaucier; si vinrent
devant [Lille], la souverainne ville dou conte, dont
25 messires Phelippes de Dyon et messires Ernaulz de
Dyon estoient chapitainne. Quant li contes Derbi et
ses gens furent venu par devant, si l’avironnèrent et
regardèrent que elle estoit bien prendable. Si fisent
traire leurs archiers avant, et approcier jusques as
30 barrières. Cil commencièrent à traire si fortement
[57] que nulz de chiaus de le ville n’osoient apparoir
pour deffendre. Et conquisent li Englès ce premier
jour les bailles et tout jusques à le porte, et sus le
soir il se retraisent. Quant ce vint au matin, de rechief
 5 il commencièrent à assallir fortement et despertement
en pluiseurs lieus, et ensonniièrent si
chiaus de le ville qu’il ne savoient au quel entendre.
Li bourgois de le ville, qui doubtèrent le leur à
perdre, leurs biens, leurs femmes et leurs enfans,
10 regardèrent que à le longe il ne se poroient tenir. Si
priièrent as deux chevaliers qui là estoient, qu’il
trettiassent à ces signeurs d’Engleterre, par quoi il
demorassent à pais et que li leurs fust sauvés. Li
chevalier, qui assés bien veoient le peril où il estoient,
15 s’i acordèrent assés legierement. Et envoiièrent un
hiraut de par yaus au conte Derbi, pour avoir respit
un jour tant seulement et parlement de composition.
Li hiraus vint devers le dit conte qu’il trouva sus les
camps assés priès de le ville, et li remoustra ce pour
20 quoi il estoit là envoiiés. Li contes s’i acorda et fist
retraire ses gens, et s’en vint jusques as barrières
parlementer à chiaus de le ville, dalés lui le baron de
Stanfort et le signeur de Mauni. Là furent il en grant
parlement ensamble, car li contes Derbi voloit qu’il
25 se rendesissent simplement, et il ne l’euissent jamais
fait. Toutes fois, accors se porta que cil de [Lille] se
metteroient en l’obeissance dou roy d’Engleterre. Et
de ce envoieroient il douze de leurs plus honnourables
hommes en le bonne cité de Bourdiaus, en nom
30 de crant. Et sur ce li chevalier et li escuier françois,
qui là estoient, se pooient partir et traire quel part
qu’il voloient. Ensi eut li contes Derbi en ce temps
[58] le ville de [Lille] en Gascongne; et se partirent sus
son saufconduit les gens d’armes qui dedens estoient,
et s’en alèrent devers le Riolle.

§ 215. Apriès le conquès de [Lille], et que li contes

5 Derbi y eut laissiés gens d’armes et arciers de par
lui, et envoiiés douze bourgois de la ville en ostagerie,
pour plus grant seurté, en le cité de Bourdiaus, il
 chevauca oultre et vint devant Bonival. Là eut grant
assaut et dur, et pluiseurs hommes bleciés dedens et
10 dehors. Finablement, li Englès le prisent et le misent
à merci, et le rafreschirent de gens d’armes et de
chapitainne. Et puis chevaucièrent oultre, et entrèrent
en le conté de Pieregorth, et passèrent devant
Bourdille, mais point n’i assallirent, car il veirent
15 bien qu’il euissent perdu leur painne. Si esploitièrent
tant qu’il vinrent jusques à [Perigueux[298]]. Par dedens
estoient li contes de Pieregorth et messires Rogiers
de Pieregorth ses oncles, et li sires de Duras et bien
six vingt chevaliers et escuiers dou pays, qui tout
20 s’estoient là recueilliet sus le fiance dou fort liu, et
ossi li uns pour l’autre. Quant li contes Derbi et se
route parfurent venu devant, il avisèrent et imaginèrent
moult bien comment, ne par quel voie à leur
avantage il le poroient assallir. Si le veirent forte
25 durement: si ques, tout, consideret, il n’eurent mies
conseil d’emploiier y leurs gens, mais se retraisent
arrière sans riens faire. Et s’en vinrent logier à deux
liewes de là, sus une petite rivière, pour venir devant
le chastiel de Pellagrue.
[59] Ces gens d’armes, qui estoient dedens le chastiel
de Perigueux, parlèrent ce soir ensamble, et disent
ensi: «Cil Englès nous sont venu veoir et aviser de
priès, et puis se sont parti sans riens faire. Ce seroit
5 bon que à nuit nous les alissions resvillier, car il ne
sont pas logiet trop loing de ci.» Tout s’acordèrent
à ceste oppinion, et issirent de Perigueux environ
mienuit bien deux cens lances, montés sus fleur de
chevaus; et chevaucièrent radement, et furent devant
10 le jour ou logeis des Englès. Si se ferirent dedens
baudement; si en occirent et mehagnièrent grant
fuison. Et entrèrent ou logeis le conte de Kenforth,
et le trouvèrent qu’il s’armoit. Si fu assallis vistement
et pris par force; aultrement il euist estet mors, et
 15 ne sçai trois ou quatre chevaliers de son hostel. Puis
se retraisent li Gascon sagement, ançois que li hos
fust trop estourmis, et prisent le chemin de [Perigueux].
Si leur fu bien besoins qu’il trouvassent les
portes ouvertes et apparillies, car il furent sievoit
20 caudement et rebouté durement dedens leurs barrières.
Mais si tretost que li Gascon furent en leur
garde, il descendirent de leurs chevaus et prisent
leurs glaves, et s’en vinrent franchement combatre
main à main as Englès; et tinrent leur pas souffisamment,
25 et fisent tant qu’il n’i eurent point de damage.
Adonc se retraisent li Englès tout merancolieus de
ce que li contes de Kenfort estoit pris, et vinrent à
leur logeis; si se deslogièrent bien matin, et cheminèrent
devers Pellagrue.

30 § 216. Tant chevaucièrent li Englès qu’il vinrent

devant le chastiel de Pellagrue. Si l’environnèrent
[60] de tous lés et le commencièrent à assallir fortement,
et cil de dedens à yaus deffendre comme gens de
grant volenté, car il avoient un bon chevalier à chapitainne
que on appelloit monsigneur Bertran des
5 Prés. Et furent li Englès six jours devant Pellagrue,
et y fisent tamaint assaut. Là en dedens furent tretties
les delivrances dou conte de Renfort et de ses
compagnons, en escange dou visconte de Boskentin,
dou visconte de Chastielbon, dou signeur de [Lescun[299]]
10 et dou signeur de Chastielnuef, parmi tant encores
que la terre dou conte de Pieregorth demorroit trois
ans en pais. Mais bien se pooient armer li chevalier
et li escuier de celle terre, sans fourfait; mès on ne
pooit prendre, ardoir ne exillier, piller ne rober
15 nulle cose, le terme durant, en la ditte conté. Ensi
revinrent li contes de Kenfort et tout li prisonnier
englès qui avoient estet pris de chiaus de Pieregorth.
Et ossi li chevalier de Gascongne furent delivret
 parmi le composition dessus ditte.
20 Et se partirent li Englès de devant Pellagrue, car
la terre est tenue dou conte de Pieregort, et chevaucièrent
devers Auberoce, qui est uns biaus chastiaus
et fors de l’archevesquié de Thoulouse. Si trestost
que li Englès furent venu devant Auberoce, il s’i logièrent
25 ossi faiticement que donc qu’il y vosissent
demorer et sejourner une saison. Et envoiièrent segnefiier
et dire à ceulz qui dedens estoient, qu’il se
rendesissent et mesissent en l’obeissance dou roy
d’Engleterre; ou aultrement, s’il estoient pris par
[61] force, il seroient tout mort sans merci. Cil de le ville
et dou chastiel d’Auberoce doubtèrent leurs biens et
leurs corps à perdre, et veirent qu’il ne leur apparoit
nul confort de nul costé. Si se rendirent, salve leurs
5 corps et leurs biens, et se misent en l’obeissance
dou conte Derbi, et le recogneurent à signeur, ou nom
dou roy d’Engleterre, par le vertu d’une procuration
qu’il en avoit. Adonc s’avisa li contes Derbi qu’il se
retrairoit tout bellement devers le cité de Bourdiaus.
10 Si laissa dedens Auberoce en garnison monsigneur
Franke de Halle, monsigneur Alain de Finefroide et
monsigneur Jehan de Lindehalle.
Puis s’en vint li contes à Liebrone, une bonne
ville et grosse, en son chemin de Bourdiaus, à douze
15 liewes d’illuech; et l’assega, et dist bien à tous chiaus
qui oïr le vorrent, qu’il ne s’en partiroit si l’aroit.
Quant cil de Liebrone veirent assegie leur ville, et le
grant effort que li contes Derbi menoit, et comment
tous li pays se rendoit à lui, si alèrent li homme de
20 le ville ensamble en conseil à savoir comment il se
maintenroient. Tout consideret [et yaulx consilliet[300]],
et peset le bien contre le mal, il se rendirent et ouvrirent
leurs portes, ne point ne se fisent assallir ne
heriier. Et jurèrent feaulté et hommage au conte
25 Derbi, ou nom dou roy d’Engleterre, et à demorer
 bons Englès de ce jour en avant. Ensi entra li contes
Derbi dedens Liebrone, et y fu quatre jours, et là
ordonna il de ses gens quel cose il feroient. Si ordonna
tout premierement le conte de Pennebruch
30 et se route à aler à Bregerach, et messire Richart de
[62] Stanfort et messire Estievene de Tonrbi et messire
Alixandre Ansiel et leurs gens à demorer en le ville
de Liebrone. Chil li acordèrent volentiers. Dont se
partirent li contes Derbi, li contes de Kenfort, messires
5 Gautiers de Mauni et li aultre, et chevaucièrent
devers Bourdiaus, et tant fisent qu’il y parvinrent.

§ 217. Au retour que li contes Derbi fist en le

cité de Bourdiaus, fu il liement recueillés et recheus
de toutes gens. Et vuidièrent li clergiés et li bourgois
10 de le ville à grant pourcession contre lui, et li
fisent tout honneur et reverense à leur pooir. Et li
abandonnèrent vivres et pourveances et toutes aultres
coses, à prendre ent à sen aise et volenté. Li
contes les remercia grandement de leur courtoisie
15 et de ce qu’il li offroient. Ensi se tint li contes Derbi
en le cité de Bourdiaus avoecques ses gens; si s’esbatoit
et jewoit entre les bourgois et les dames de
le ville.
Or lairons nous un petit à parler de lui, et parlerons
20 dou conte de [Lille], qui se tenoit en le Riolle,
et savoit bien tout le couvenant des Englès et le conquès
que li contes Derbi avoit fait, et point n’i avoit
peut pourveir de remède. Si entendi li dis contes de
[Lille] que li contes Derbi estoit retrais au sejour en
25 Bourdiaus et avoit espars ses gens et romput se chevaucie,
et n’estoit mies apparant que de le saison il
en fesist plus. Si s’avisa li dis contes qu’il feroit une
semonse et un mandement especial de gens d’armes,
et iroit mettre le siège devant Auberoce. Ensi qu’il
30 l’avisa, il le fist. Si escrisi devers le conte de Pieregort,
 celi de Quarmaing, celi de Commignes, celi de
[63] Brunikiel, celi de Villemur et devers tous les barons
de Gascongne, qui François se tenoient, qu’il fuissent
sus un jour qu’il leur assigna, devant Auberoce, car
il y voloit aler et mettre le siège. Li dessus dit conte,
5 visconte et baron de Gascongne obeirent à lui, car
il estoit comme rois ens ès marces de Gascongne.
Et assamblèrent leurs gens et leurs hommes, et furent
tout appareilliet au jour qui assignés y fu. Et vinrent
devant Auberoce telement que li chevalier dessus
10 nommé, qui le gardoient, ne s’en donnèrent de garde;
si se veirent assegiet de tous costés. Ensi que gens
de bon couvenant et de grant arroy, il ne furent de
riens esbahi, mès entendirent à leurs gardes et à
leurs deffenses. Li contes de [Lille] et li aultre baron,
15 qui là estoient venu moult poissamment, se logièrent
tout à l’environ, telement que nulz ne pooit entre[r],
ne issir en le garnison, qu’il ne fust aperceus. Et envoiièrent
querre quatre grans engiens à Thoulouse,
et les fisent là achariier et puis drecier devant le forterèce.
20 Et n’assalloient li François d’autre cose, fors
de ces engiens, qui nuit et jour jettoient pières de fais
ou chastiel. Che les esbahissoit plus c’autre cose, car
dedens six jours il desrompirent le plus grant partie
des combles des tours. Et ne s’osoient li chevalier
25 ne cil dou chastiel tenir, fors ens ès cambres votées,
par terre. Et estoit li intentions de chiaus de l’host
qu’il les occiroient là dedens, ou il se renderoient
simplement. Bien estoient venues les nouvelles à
Bourdiaus au conte Derbi et à monsigneur Gautier
30 de Mauni, que leur compagnon estoient assegiet dedens
Auberoce; mais point ne savoient qu’il fuissent
si apressé, ne si constraint qu’il estoient.

[64] § 218. Quant messires Franke de Halle et messires

Alain de Finefroide et messires Jehans de Lindehalle
 veirent le oppression que li François leur faisoient,
et si ne leur apparoit confors ne ayde de nul
5 costé, si se commencièrent à esbahir, et se consillièrent
entre yaus comment il se poroient maintenir.
«Il ne poet estre, disent il, que se li contes Derbi
savoit le dangier où cil François nous tiènent, qu’il
ne nous secourust, à quel meschief que ce fust. Si
10 seroit bon que nous li feissiens savoir, mès que nous
peuissions trouver messag[e].» Adonc demandèrent il
entre leurs varlès se il en y avoit nul qui volsist
gaegnier et porter ceste lettre qu’il avoient escript, à
Bourdiaus, et baillier au conte Derbi. Lors s’avança
15 uns varlès, et dist qu’il li porteroit bien et volentiers;
et ne le feroit mies tant, pour le convoitise de gaegnier,
que pour yaus delivrer de ce peril. Li chevalier
furent moult liet dou varlet qui s’offroit de faire le
message.
20 Quant ce vint au soir par nuit, li varlés prist la
lettre que li chevalier li baillièrent, qui estoit seellée
de leurs trois seaulz; et li encousirent en ses draps,
et puis le fisent avaler ens ès fossés. Quant il fu au
fons, il monta amont et se mist à voie parmi l’ost,
25 car aultrement ne pooit il passer. Et fu encontrés
dou premier get, et ala oultre, car il sçavoit bien
parler gascon, et nomma un signeur de l’host, et dist
qu’il estoit à lui. On le laissa passer par tant; et cuida
bien estre escapés, mès non fu, car il fu repris au
30 dehors des tentes, d’aultres varlès, qui l’amenèrent
devant le chevalier dou ghet. Là ne peut il trouver
nulle excusance qui riens li vaulsist. Si fu tastés et
[65] exquis, et la lettre trouvée sur lui. Si fu menés en
prison et gardés jusques au matin, que li signeur de
l’host furent tout levet; si furent tantost enfourmé
de le prise dou varlet. Adonc se traisent il tout ensamble
5 en le tente dou conte de [Lille]. Là fu la lettre
leute que li chevalier d’Auberoce envoioient au conte
 Derbi. Si eurent tout grant joie, quant il sceurent de
vérité que li chevalier d’Auberoce et li compagnon
englès qui dedens se tenoient estoient si astraint et
10 qu’il ne se pooient plus tenir: si ques, pour yaus
plus agrever, il prisent le varlet, et li pendirent les
lettres au col, et le misent tout en un mont et en le
fonde d’un engien, et puis le renvoiièrent dedens
Auberoce. Li varlès chei tous mors devant les chevaliers
15 qui là estoient, et qui furent esbahi et desconforté
quant il le veirent: «Ha! disent il, nostre
messagier n’a pas fait son message. Or ne savons
nous mès que viser, ne quel conseil avoir qui nous
vaille.»
20 A ces cops estoient montés à cheval li contes de
Pieregorth et messires Rogiers de Pieregorth ses oncles,
messires Charles de Poitiers, li viscontes de
Quarmaing et li sires de Duras, et passèrent devant
les murs de le forterèce au plus priès qu’il peurent.
25 Si escriièrent à chiaus dedens, et leur disent en gabois:
«Signeur, signeur englès, demandés à vostre
messagier où il trouva le conte Derbi si apparilliet,
quant à nuit se parti de vostre forterèce, et jà est
retournés de son voiage.» Adonc respondi messires
30 Frankes de Halle, qui ne s’en peut astenir, et dist:
«Par foy, signeur, se ceens nous sommes enclos,
nous en isterons bien, quant Diex vorra et li contes
[66] Derbi. Et pleuist à Dieu qu’il seuist en quel parti
nous sommes! Se il le savoit, il n’i aroit si avisé des
vostres qui ne ressongnast à tenir les camps. Et
se vous li volés segnefiier, li uns des nostres se mettera
5 en vostre prison pour rançonner, ensi que on
rançonne un gentil homme.» Dont respondirent li
François: «Nennil, nennil! Les pareçons ne se porteront
mies ensi. Li contes Derbi le sara tout à
temps, quant par nos engiens nous arons abatu rés
10 à rés terre che chastiel, et que vous, pour vos vies
 sauver, vous vos serés rendu simplement.»
—«Certainnement, ce respondi messires Franke de Halle, ce
ne sera jà que ensi nous nos doions rendre, pour
estre tout mort ceens.» Adonc passèrent li chevalier
15 françois oultre, et revinrent à leur logeis. Et li troi
chevalier englès demorèrent dedens Auberoce tout
esbahi, au voir dire; car ces pières d’engien leur
buskoient si grans horions, que ce sambloit effoudres
qui descendist dou ciel, quant elles frapoient contre
20 les murs dou chastiel.

§ 219. Toutes le[s] parolles et les devises et le

couvenant dou messagier, comment il avoit esté pris
devant Auberoce, et l’estat de la lettre, et le neccessité
de chiaus dou chastiel furent sceues et raportées à
25 Bourdiaus au conte Derbi et à monsigneur Gautier
de Mauni, par une leur espie qu’il avoient envoiiet
en l’ost, et qui leur dist: «Mi signeur, à ce que j’ai
pout entendre, se vo chevalier ne sont conforté dedens
trois jours, il seront ou mort ou pris. Et volentiers
30 se renderoient, se on les voloit prendre à merci,
mès il me samble que nennil.» De ces nouvelles ne
[67] furent mies li contes Derbi et messires Gautiers de
Mauni bien joiant, et disent entre yaus: «Ce seroit
lasqueté et villonnie, se nous [laissons[301]] perdre trois
si bons chevaliers que cil sont, qui si franchement
5 se sont tenu dedens Auberoce. Nous irons ceste part
et nous esmouverons tout premièrement, et manderons
au conte de Pennebruch, qui se tient à Bregerach,
qu’il soit dalés nous à cèle heure, et ossi à monsigneur
Richart de Stanfort et à monsigneur Estievene
10 de Tombi qui se tient à Liebrone.»
[Adoncques ly contes Derby se hasta durement, et
envoia ses messages et ses lettres devers le conte de
Pennebruk. Et se parti de Bourdiaux à ce qu’il avoit
de gens, et chevaucha tout couvertement devers Auberoche;
 15 bien avoit qui le menoit et qui congnissoit
le pais. Si vint ly contes Derby à Liebrone[302]] et là
sejourna un jour, attendans le conte de Pennebruch,
et point ne vint. Quant il vei qu’il ne venroit point,
si fu tous courouciés et se mist au chemin, pour le
20 grant desir qu’il avoit de conforter ses chevaliers qui
en Auberoce se tenoient, car bien [sçavoit[303]] qu’il en
avoient grant mestier.
Si issirent de Liebrone li contes [Derbi[304]] li contes
de Renfort, messires Gautiers de Mauni, messires
25 Richars de Stanfort, messires Hues de Hastinghes,
messires Estievenes de Tombi, li sires de Ferrières
et li aultre compagnon. Et chevaucièrent toute
[68] nuit, et vinrent à l’endemain à deux petites liewes
d’Auberoce. Si se boutèrent en un bois, et descendirent
de leurs chevaus; et les alloiièrent as arbres
et as foellies, et les laissièrent pasturer en l’erbe,
5 toutdis attendans le conte de Pennebruch. Et furent
là toute la matinée, et jusques à nonne. Si s’esmervilloient
trop durement de ce qu’il n’ooient nulle
nouvelle dou dit conte. Quant ce vint sus l’eure de
remontière, et il veirent que point ne venoit li
10 contes, si disent entre yaus: «Que ferons nous?
Irons nous assallir nos ennemis, ou nous retourons?»
Là furent en grant imagination quel cose il
en feroient, car ilz ne se veoient mies gens pour
combatre une tèle hoost qu’il y avoit devant Auberoce,
15 car il n’estoient non plus de trois cens lances
et de six cens arciers. Et li François pooient estre
entre dix mille et onze mille hommes. A envis ossi
le la[i]ssoient, car bien savoient, se il se partoient sans
le siège lever, il perd[r]oient le chastiel d’Auberoce et
20 les chevaliers leurs compagnons qui dedens estoient.
Finablement, tout consideret, et peset le bien contre
le mal, il s’acordèrent à ce que, ou nom de Dieu et
de saint Jorge, il iroient combatre leurs ennemis.
 Or avisèrent il comment; et l’avis là où le plus il
25 s’arrestèrent, il leur vint de monsigneur Gautier de
Mauni, qui dist ensi: «Signeur, nous monterons
tout à cheval, et costierons à le couverte ce bois où
nous sommes à present, tant que nous serons sus
l’autre cornée, au lés delà qui joint moult priès de
30 leur host. Et quant nous serons priès, nous feri[r]ons
chevaus des esporons et escrierons nos cris hautement;
nous y enterons droit sus l’eure dou souper:
[69] vous les verés si souspris et si esbahis de nous, qu’il
se desconfiront d’eulz meismes.» Adonc respondirent
li chevalier qui furent appellet à ce conseil: «Nous
le ferons ensi que vous l’ordonnés.» Si reprist cescuns
5 son cheval, et les recenglèrent estroitement; et
fisent restraindre leurs armeures, et ordonnèrent
tous leurs pages, leurs varlès et leurs malètes à là
demorer. Et puis chevaucièrent tout souef au loing
dou bois, tant qu’il vinrent sus l’autre cornée où li
10 hos françoise estoit logie assés priès, en un grant val,
sus une petite rivière. Lors qu’il furent là venu, il
desvolepèrent leurs banières et leurs pennons, et ferirent
chevaus des esperons, et s’en vinrent tout de
front sus le large planter et ferir en l’ost de ces signeurs
15 de Gascongne, qui furent bien souspris, et
leurs gens ossi; car de celle embusche ne se donnoient
il nulle garde, et se devoient tantos seoir au
souper. Et li pluiseur y estoient jà assis comme gent
asseguret, car il ne cuidaissent jamais que li contes
20 Derbi deuist là venir ensi à tèle heure.

§ 220. Evous les Englès venant frapant en celle

host, pourveus et avisés de ce qu’il devoient faire, en
escriant: «[D]erbi[305], [D]erbi au conte!» et «Mauni,
Mauni au signeur!» Puis commencièrent à coper et à
25 decoper tentes, trés et pavillons, et reverser l’un sus
l’autre, et abatre et occire et mehagnier gens, et mettre
 en grant meschief; ne [les François[306]] ne savoient auquel
entendre, tant estoient il quoitiet et fort hastet. Et
[70] quant il se traioient sus les camps pour yaus recueillier
et assambler, il trouvoient arciers tous appareilliés
qui les traioient et bersoient et occioient sans
merci et sans pité. Là avint soudainnement sus ces
5 chevaliers de Gascongne uns grans meschiés, car il
n’eurent nul loisir d’yaus armer ne traire sus les
camps. Mais fu li contes de [Lille] pris en son pavillon
et moult durement navrés, et li contes de Pieregorch
ossi dedens le sien, et messires Rogiers, ses oncles,
10 et occis li sires de Duras et messires Aymars
de Poitiers, et pris li contes de Valentinois ses frères.
Briefment, on ne vit onques tant de bonnes gens,
chevaliers et escuiers qui là estoient, perdu à si peu
de fait, car cescuns fuioit que mieulz mieulz. Bien
15 est verité que li contes de Commignes et li viscontes
de Quarmaing et cil de Villemur et cils de Brunikiel
et li sires de la Barde et li sires de Taride, qui estoient
logiet d’autre part le chastiel, se recueillièrent
et misent leurs banières hors, et se traisent vassaument
20 sus les camps. Mais li Englès, qui avoient jà
desconfis le plus grant partie de l’ost, s’en vinrent
en escriant leurs cris celle part, et se boutèrent e[n]s
de plains eslais, ensi que gens tous reconfortés et
qui veoient bien, se fortune ne leur estoit trop contraire,
25 que li journée estoit pour yaus. Là eut fait
mainte belle apertise d’armes, mainte prise et mainte
rescousse. Quant messires Franke de Halle et messires
Alains de Finefroide [et messires Jehans de Lindehalle[307]],
qui estoient ens ou chastiel [de Auberoche[308]],
[71] entendirent le noise et le hue, et recogneurent les
banières et les pennons de leurs gens, si s’armèrent
et fisent armer tous chiaus qui avoecques euls
estoient. Et puis montèrent à cheval, et issirent de le
5 forterèce d’Auberoce, et s’en vinrent sus les camps
et se boutèrent ou plus fort de le bataille: ce rafresci
 et resvigura grandement les Englès.

§ 221. Que vous feroi je lonch parlement? Chil

de le partie le conte de [Lille] furent là tout desconfi,
10 et priès que tout mort et tout pris. Jà ne s’en fust
nulz escapés, se la nuis ne fust si tost venue. Là y
ot pris, que contes que viscontes, jusques à neuf, et
des barons et des chevaliers tel fuison qu’il n’i avoit
homme d’armes des Englès qui n’en euist deux ou
15 trois dou mains, des quelz il eurent depuis grant
pourfit. Ceste bataille fu desous Auberoce, le nuit
Saint Laurens en aoust, l’an de grasce Nostre Signeur
mil trois cens quarante quatre.

§ 222. Apriès le desconfiture qui fu là si grande

20 et si grosse pour les Gascons et si adamagable, car
il estoient là venu en grant arroi et en bonne ordenance,
mais petite songne les fist perdre ensi qu’il
apparu, li Englès, qui estoient mestre et signeur
dou camp, entendirent à leurs prisonniers, et, comme
25 gens qui leur ont toutdis estet courtois, leur fisent
très bonne compagnie, et en recrurent assés sus leurs
fois à revenir dedens un certain jour à Bourdiaus ou
à Bregerach; [et] il se retraisent dedens Auberoce. Et
là donna à souper li contes Derbi le plus grant partie
30 des contes, des viscontes, qui prisonnier estoient, et
[72] ossi les chevaliers de se compagnie. Si devés croire
et savoir qu’il furent celle nuit en grant reviel, et rendirent
grans grasces à Nostre Signeur de le belle journée
qu’il avoient eu, quant une puignie de gens qu’il
5 estoient, environ mil combatans parmi les arciers,
uns c’autres, en avoient desconfi dix mil et plus, et
rescous le ville et le chastiel d’Auberoce, et les chevaliers
leurs compagnons qui dedens estoient moult
astraint, et qui dedens deux jours euissent esté pris
10 et en le volenté de leurs ennemis.
 Quant ce vint au matin, un peu apriès soleil levant,
li contes de Pennebruch vint à bien trois cens lances
et quatre cens archiers, qui jà avoit esté enfourmés
sus son chemin de l’avenue de le bataille. Si estoit
15 durement courouciés de ce qu’il n’i avoit esté; et en
parla par mautalent au conte Derbi, et dist: «Certes,
cousins, il me samble que vous ne m’avés fait maintenant
point d’onneur ne de courtoisie, quant vous
avés combatus vos ennemis sans moy, qui m’aviés
20 mandé si acertes. Et bien poiés savoir que je ne me
fuisse jamais souffers que je ne fuisse venus.» Donc
respondi li contes Derbi, et dist tout en riant: «Par
ma foy, cousins, nous desirions bien vostre venue.
Et nous souffresi[o]ns toutdis, en vous sourattendant
25 dou matin jusques as vespres. Et quant nous veimes
que vous ne veniés point, nous en estions tout
esmervilliet. Si n’osames plus attendre que nostre
anemi ne seuissent nostre venue. Car, se il le seuissent,
il euissent eu l’avantage sur nous. Et, Dieu
30 merci, nous l’avons eu sur yaus; si les nous aiderés
à garder et à conduire jusques à Bourdiaus.» Adonc
se prisent par les mains, et entrèrent en une cambre,
[73] et issirent de ce pourpos. Tantost fu heure de disner;
si se misent à table; si mengièrent et burent,
tout aise et à grant loisir, des pourveances des François
qu’il avoient amené devant le chastiel de Auberoce,
5 dont il estoient bien raempli. Tout ce jour et le
nuit ensievant, se tinrent il en Auberoce, et se reposèrent
et rafreschirent grandement. Et l’endemain
au matin, il furent tout armé et tout monté. Si se
partirent de Auberoce, et y laissièrent à chapitainne
10 et à gardiien un chevalier gascon, qui toutdis avoit
estet de leur partie, qui s’appelloit messires Alixandres
de Chaumont. Et chevaucièrent devers Bourdiaus,
et emmenèrent le plus grant partie de leurs
prisonniers.
 15 § 223. Tant chevaucièrent li dessus dit Englès et
leurs routes qu’il vinrent en le cité de Bourdiaus où
il furent recheu à grant joie. Et ne savoient li Bourdelois
comment bien festiier le conte Derbi et monsigneur
Gautier de Mauni, car li renommée aloit que
20 par leur emprise avoient esté devant Auberoce li
Gascon desconfi, et pris li contes de [Lille] et plus
de deux cens chevaliers. Si leur faisoient grant joie
et haute honneur. Ensi se passèrent il cel yvier qu’il
n’i eut nulles besongnes ens ès marces par de delà
25 qui à recorder face. Si ooit souvent li rois d’Engleterre
bonnes nouvelles dou conte Derbi, son cousin,
qui se tenoit à Bourdiaus sus Gironde et là environ.
Si en estoit tous liés et à bonne cause, car li contes
Derbi faisoit tant qu’il estoit amés de tous ses amis
30 et ressongniés de tous ses ennemis.
Quant ce vint apriès Paskes, que on compta l’an
[74] mil trois cens quarante cinq, environ le moiiené de
may, li contes Derbi, qui s’estoit tenus et yvrenés
tout le temps à Bourdiaus ou là priès, fist une coeilloite
et un amas de gens d’armes et d’arciers, et dist
5 qu’il voloit faire une chevaucie devers le Riolle que
li François tenoient, et le assegeroit, car elle estoit
bien prendable. Quant toutes ses besongnes furent
ordenées et ses gens venus, il se partirent de Bourdiaus
en bon arroy et en grant couvenant, et vinrent
10 ce premier jour en le ville de Bregerach. Là trouvèrent
il le conte de Pennebruch, qui avoit fait ossi
sen assamblée d’autre part.
Si furent cil signeur et leurs gens dedens Bregerach
trois jours; au quatrime, il s’en partirent.
15 Quant il furent sus les camps, il esmèrent leurs gens
et considerèrent leur pooir, et se trouvèrent mil
combatans et deux mil archiers. Si chevaucièrent
 tout ensi, et fisent tant qu’il vinrent devant un chastiel
que on claime Sainte Basille. Quant il furent
20 là venu, il le assegièrent de tous lés, et fisent grant
apparant de l’assallir. Chil de Sainte Basille veirent
les Englès et leur force, comment il tenoient les
camps, et que nulz ne lor aloit au devant. Mès encores
estoient prisonnier de le bataille de Auberoce
25 tout li plus grant de Gascongne, dont il deuissent
estre aidié et conforté: si ques, tout consideret, il
se misent en l’obeissance dou conte Derbi qui representoit
adonc là le personne dou roy d’Engleterre,
et li jurèrent feaulté et hommage, et le recogneurent
30 à signeur.
Par ensi il passa oultre bellement, et prist le chemin
de Aiguillon; mais, ançois qu’il y parvenist, il
[75] trouva en son chemin un chastiel que on appelle le
Roce Millon, qui estoit bien pourveus de bons saudoiiers
et d’arteillerie. Non obstant ce, li contes commanda
que li chastiaus fust assallis. Donc s’avancièrent
5 Englès et arcier, et le commencièrent à assallir
fortement et durement, et chil de dedens à yaus
deffendre vassaument. Et jettoient pières et baus et
grans barriaus de fier, et pos plains de cauch: de
quoi il blechièrent pluiseurs assallans qui montoient
10 contremont et s’abandonnoient folement, pour leurs
corps avancier.

§ 224. Quant li contes Derbi vei que ses gens se

travilloient et tuoient sans riens faire, si les fist retraire
et revenir as logeis. A l’endemain, il fist par les
15 villains dou pays achariier et aporter grant fuison de
busce et de velourdes et d’estrain, et tout jetter et
tourner ens ès fossés, et mettre ossi grant plenté de
terre. Quant une partie des fossés furent tout empli,
que on pooit bien aler seurement jusques au piet
20 dou mur, il fist arouter bien trois cens arciers, et par