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Eco-Friendly Corrosion Inhibitors :

Principles, Designing and Applications


Lei Guo
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Eco-Friendly Corrosion Inhibitors : Principles,


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Heterocyclic Organic Corrosion Inhibitors: Principles


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Organic Corrosion Inhibitors: Synthesis,


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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
Elsevier
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our understanding, changes in research methods, professional practices, or medical treatment may become
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Typeset by Aptara, New Delhi, India


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 ix

24. Smart corrosion inhibitor: Present status 26.3 Some electronic structure principles and rules for
and future scenario corrosion inhibition research 531
26.4 Molecular dynamics and Monte Carlo simulations
XINGWEN ZHENG, LEI GUO, DAWEI ZHANG
approaches in corrosion science 533
24.1 Introduction 485 26.5 The application of first-principles calculation
24.2 Controlled release inhibitor 486 approach 534
24.3 pH-responsive inhibitor 489 Conclusions 536
24.4 Ion exchange inhibitor 497 References 536
24.5 Other smart inhibitor 501
Summary and future scenario 502 27. Corrosion inhibition strategy:
References 502 Synergistic effects
PENG HAN, JIAWEI FAN, LINGHUI KONG, BUYUN ZHANG,
25. Controllable fabrication of carbon ZHIXUAN CHANG

dots based corrosion inhibitors with 27.1 Problems and challenges in the study of synergistic
fluorescence properties effect of corrosion inhibitors 539
YU ZHANG, BOCHUAN TAN, LEI GUO, MENGYUE ZHU 27.2 Advances of synergistic effect 543
27.3 Advances in theoretical research on synergistic
25.1 Corrosion inhibitor used for metal protection 505 effect of corrosion inhibitors 545
25.2 Introduction of carbon dots 508 27.4 Significance and prospect of synergistic effect of
25.3 Synthetic strategies of CDs 511 corrosion inhibitor 548
25.4 Corrosion inhibition performance of CDs 514 Abbreviations 549
Conclusions and outlook 521 References 549
Useful links 522
References 522
Index 553
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
Contributors

Khamdam Akbarov Faculty of Chemistry, National Brahim El Ibrahimi Department of Applied Chemis-
University of Uzbekistan, Tashkent, Uzbekistan try, Faculty of Applied Sciences, Ibn Zohr University,
Mustafa R. Al-Hadeethi Department of Chemistry, Aït Melloul, Morocco; Team of Physical Chemistry
College of Education, University of Kirkuk, Kirkuk, and Environment, Faculty of Sciences, Ibn Zohr Uni-
Iraq versity, Agadir, Morocco
Abdullah K. Alanazi Department of Chemistry, Shimaa M. Elsaeed Petroleum Applications Divi-
College of Science, Taif University, Taif, Saudi Arabia sion, Egyptian Petroleum Research Institute (EPRI),
Nasr City, Cairo, Egypt
K.R. Ansari Center of Research Excellence in Corro-
sion, Research Institute, King Fahd University of Baomin Fan College of Chemistry and Materials
Petroleum and Minerals, Dhahran, Saudi Arabia Engineering, Beijing Technology and Business Uni-
versity, Beijing, China
Ruby Aslam Corrosion Research Laboratory, Depart-
Jiawei Fan Department of Materials Science and
ment of Applied Chemistry, Faculty of Engineering
Engineering, China University of Mining & Technol-
and Technology,Aligarh Muslim University,Aligarh,
ogy (Beijing), Beijing, China
India
Abdolreza Farhadian Department of Polymer &
Jeenat Aslam Department of Chemistry, College of
Materials Chemistry, Faculty of Chemistry and Petro-
Science, Taibah University, Yanbu, Al-Madina, Saudi
leum Science, Shahid Beheshti University, GC, Tehran,
Arabia
Iran; Department of Petroleum Engineering, Kazan
Afroz Aslam Department of Chemistry, Faculty of Federal University, Kazan, Russian Federation
Science, Aligarh Muslim University, Aligarh, India
Li Feng School of Chemical Engineering and Tech-
Humira Assad Department of Chemistry, Faculty of nology, North University of China, Taiyuan,
Technology and Science, Lovely Professional Uni- China
versity, Phagwara, Punjab, India
Mouhsine Galai Advanced Materials and Process
Elyor Berdimurodov Faculty of Chemistry, National Engineering, Faculty of Sciences, Ibn Tofaïl Univer-
University of Uzbekistan, Tashkent, Uzbekistan sity, Kenitra, Morocco
Zhixuan Chang Department of Materials Science Pei Gan School of Environmental and Chemical
and Engineering, China University of Mining & Engineering, Shanghai University of Electric Power,
Technology (Beijing), Beijing, China Shanghai, China
Qi Chen School of Materials Science and Engineer- Richika Ganjoo Department of Chemistry, Faculty
ing, East China JiaoTong University, Nanchang, of Technology and Science, Lovely Professional Uni-
People’s Republic of China versity, Phagwara, Punjab, India
Omar Dagdag Institute of Nanotechnology and Lei Guo School of Materials and Chemical Engineer-
Water Sustainability, College of Science, Engineering ing, Tongren University, Tongren, China
and Technology, University of South Africa, Johan- Rajesh Haldhar School of Chemical Engineering,
nesburg, South Africa Yeungnam University, Gyeongsan, South Korea
K. Dahmani Laboratory of Organic, Inorganic Chem- Peng Han Department of Materials Science and Engi-
istry, Electrochemistry and Environment, Faculty of neering, China University of Mining & Technology
Sciences, Ibn Tofaïl University, Kenitra, Morocco (Beijing), Beijing, China

xi
xii Contributors

Hua Hao Institute of Chemistry, Chinese Academy of Mohammad Mobin Corrosion Research Laboratory,
Sciences, Beijing, China Department of Applied Chemistry, Faculty of Engi-
Zhiyong Hu School of Chemical Engineering and neering and Technology, Aligarh Muslim University,
Technology, North University of China, Taiyuan, Aligarh, India
China Xinhuan Niu School of Electronics and Information
Akpan N. Ikot Theoretical Physics Group, Depart- Engineering, Hebei University of Technology,
ment of Physics, University of Port Harcourt, Choba, Tianjin, China
Nigeria Yujie Qiang National Center for Materials Service
Savaş Kaya Sivas Cumhuriyet University, Health Safety, University of Science and Technology Beijing,
Services Vocational School, Department of Beijing, China
Pharmacy, Sivas, Turkey M.A. Quraishi Center of Research Excellence in Cor-
Abduvali Kholikov Faculty of Chemistry, National rosion, Research Institute, King Fahd University of
University of Uzbekistan, Tashkent, Uzbekistan Petroleum and Minerals, Dhahran, Saudi Arabia
Linghui Kong Department of Materials Science and Mohamed Rbaa Laboratory of Organic Chemistry,
Engineering, China University of Mining & Technol- Catalysis and Environment, Faculty of Sciences, Ibn
ogy (Beijing), Beijing, China Tofail University, Kenitra, Morocco
Ashish Kumar Department of Chemistry, Faculty of Rachid Salghi Laboratory of Applied Chemistry and
Technology and Science, Lovely Professional Uni- Environment, ENSA, University Ibn Zohr, Agadir,
versity, Phagwara, Punjab, India Morocco
Brahim Lakhrissi Laboratory of Organic Chemistry, Bharmal A. Shabbirbhai Department of Chemistry,
Catalysis and Environment, Faculty of Sciences, Ibn Faculty of Technology and Science, Lovely Profes-
Tofail University, Kenitra, Morocco sional University, Phagwara, Punjab, India
Han-Seung Lee Department of Architectural Engi- Shveta Sharma Department of Chemistry, Faculty of
neering, Hanyang University ERICA, Sangrok-gu, Technology and Science, Lovely Professional Uni-
Ansan, Korea versity, Phagwara, Punjab, India
Hassane Lgaz Department of Architectural Engi- Ambrish Singh School of New Energy and Materi-
neering, Hanyang University ERICA, Sangrok-gu, als, Southwest Petroleum University, Chengdu,
Ansan, Korea Sichuan, China
Hao Li National Center for Materials Service Safety, Xiaoya Sun School of Materials Science and Engi-
University of Science and Technology Beijing, neering, East China JiaoTong University, Nanchang,
Beijing, China; Key Laboratory of Marine Materials People’s Republic of China
and Related Technologies, Zhejiang Key Laboratory
Baimei Tan School of Electronics and Information
of Marine Materials and Protective Technologies,
Engineering, Hebei University of Technology,
Ningbo Institute of Materials Technology and Engi-
Tianjin, China
neering, Chinese Academy of Sciences, Ningbo,
China Bochuan Tan School of Chemistry and Chemical
Wenpo Li School of Chemistry and Chemical Engi- Engineering, Chongqing University, Chongqing, China
neering, Chongqing University, Chongqing, China Abhinay Thakur Department of Chemistry, Faculty
Xuemei Ma School of Chemical Engineering and of Technology and Science, Lovely Professional Uni-
Technology, North University of China, Taiyuan, versity, Phagwara, Punjab, India
China Yuqin Tian School of Materials Science and Engi-
Tengda Ma School of Electronics and Information neering, East China JiaoTong University, Nanchang,
Engineering, Hebei University of Technology, People’s Republic of China
Tianjin, China M. Ebn Touhami Advanced Materials and Process
Sheerin Masroor Department of Chemistry, A.N. Engineering, Faculty of Sciences, Ibn Tofaïl Univer-
College, Patliputra University, Patna, Bihar, India sity, Kenitra, Morocco
Contributors xiii
Burak Tüzün Department of Chemistry, Faculty of Renhui Zhang School of Materials Science and Engi-
Science, Sivas Cumhuriyet University, Turkey neering, East China JiaoTong University, Nanchang,
Nurbek Umirov Faculty of Natural Sciences, Karshi People’s Republic of China
State University, Karshi, Uzbekistan Dawei Zhang University of Science & Technology
Chandrabhan Verma Interdisciplinary Research Beijing, Beijing, China
Center for Advanced Materials, King Fahd University Yu Zhang School of Chemistry and Chemical Engi-
of Petroleum and Minerals, Dhahran, Saudi Arabia neering, Chongqing University, Chongqing, China
Dakeshwar Kumar Verma Department of Chemis- Buyun Zhang Department of Materials Science and
try, Government Digvijay Autonomous Postgradu- Engineering, China University of Mining & Technol-
ate College, Rajnandgaon, Chhattisgarh, India ogy (Beijing), Beijing, China
Chenwei Wang School of Electronics and Informa- Xingwen Zheng School of Chemical and Environ-
tion Engineering, Hebei University of Technology, mental Engineering, Sichuan University of Science &
Tianjin, China Engineering, Zigong, China
Bin Xiang School of Chemistry and Chemical Engi- Zhaosen Zhou Analytical and Testing Centre of
neering, Chongqing University, Chongqing, China Chongqing University, Chongqing University,
Junyu Yang School of Environmental and Chemical Chongqing, China; Henan Chemical Technician
Engineering, Shanghai University of Electric Power, College, Henan, China
Shanghai, China Yang Zhou Analytical and Testing Centre of Chongq-
Da Yin School of Electronics and Information Engineer- ing University, Chongqing University, Chongqing,
ing, Hebei University of Technology, Tianjin, China China
Abdelkader Zarrouk Laboratory of Materials, Nan- Hailin Zhu School of Chemical Engineering and
otechnology and Environment, Mohammed V Uni- Technology, North University of China, Taiyuan,
versity, Faculty of Sciences, Rabat, Morocco China
Saman Zehra Corrosion Research Laboratory, Jiajia Zhu School of Materials Science and Engineer-
Department of Applied Chemistry, Faculty of Engi- ing, East China JiaoTong University, Nanchang,
neering and Technology, Aligarh Muslim University, People’s Republic of China
Aligarh, India Chong Zhu School of Chemistry and Chemical
Daquan Zhang School of Environmental and Chemi- Engineering, Chongqing University, Chongqing,
cal Engineering, Shanghai University of Electric China
Power, Shanghai, China Mengyue Zhu School of Materials Science and Engi-
Wenyue Zhang School of Environmental and Chemi- neering, East China Jiaotong University, Nanchang,
cal Engineering, Shanghai University of Electric China
Power, Shanghai, China Amir Zomorodian Department of Engineering,
Shihao Zhang School of Electronics and Information University of Cambridge, Cambridge, United
Engineering, Hebei University of Technology, Kingdom
Tianjin, China Selçuk Şimşek Sivas Cumhuriyet University,
Xin Zhang School of Chemistry and Chemical Engi- Faculty of Science, Department of Chemistry, Sivas,
neering, Chongqing University, Chongqing, China Turkey
Preface

It is well-known that corrosion has a huge eco- inhibitors have been presented and their poten-
nomic, environmental, and sustainability tial applications in various industrial fields
impact on virtually all facets of metallic materi- were also discussed.
als, including power facilities, integrated cir- The book is divided into different parts,
cuits, chemical industries, desalination, bridges, where each part contains multiple chapters.
oil and gas pipeline, etc. Annual costs of corro- Part 1 “Overview of industrial corrosion and
sion and its consequences are estimated in the inhibition” covers topics such as general prin-
region of 3–5% of GDP for industrialized coun- ciples of industrial corrosion, corrosion preven-
tries of the world. Most of all, the disposal and tion, and protection methods, and the
further substitution of the damaged elements development process for ecofriendly corrosion
involve an additional consumption of energy inhibitors. Part 2 “Industrial environments &
and resources. To face and solve this challenge, corrosion inhibitors” entirely focuses on the
an increasing number of studies have focused application of corrosion inhibitor in acidizing,
on environmentally friendly, renewable, and alkaline, and near neutral media, as well as the
efficient corrosion inhibitors, which are promis- inhibitors for cooling water systems, oil and gas
ing alternatives to toxic corrosion inhibitors, in systems, and chemical mechanical planariza-
order to control corrosion damage in diverse tion. Part 3 “Modern environmentally friendly
corrosive environments. These materials range corrosion inhibitor systems” is specific about
from plant extracts to amino acids, expired the corrosion inhibitors based on pharmaceuti-
drugs, ionic liquids, carbohydrate polymers, cal drugs, plant extracts, amino acids, ionic
and zero-dimensional carbon quantum dots. liquids, nanomaterials, and synthetic com-
Although the subject of corrosion inhibition has pounds. Part 4 “Emerging trends in corrosion
been a conventional research topic over the past inhibition” gives a description of modern
few decades, more advanced knowledge is still testing and analyzing techniques in corrosion,
required to win the battle. A comprehensive the smart and high temperature corrosion
understanding of this phenomenon will guar- inhibitors, the synergistic inhibition strategy,
antee an improved design to reduce the dra- and computational methods used in corrosion
matic consequences. inhibition research.
In this regard, the present book aims to shed Overall, this book is written via a scientific
more light on the recent progress and advances summary of modern corrosion inhibitors, and
on the usage of green and sustainable inhibitors is prepared for graduate students, researchers,
to protect metallic materials against corrosion as well as practitioners in multiple industries
in different corrosive conditions, such as acidic, who require comprehensive knowledge of this
neutral, alkaline, and sweet/sour environ- aspect. The editors and contributors are well-
ments. A wide range of ecofriendly corrosion known scientists with many years of research

xv
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-


related phenomena. This chapter presents
The economic development of any region, important aspects of corrosion in industrial
state or country, depends not only on its natural infrastructure, its causes, impacts, control, pro-
resources and productive activities, but also on tection and prevention methods.
the infrastructure that account for the exploita-
tion, processing, and marketing of goods. Irriga-
tion systems, roads, bridges, airports, maritime, 1.2 Materials in industrial applications
land and air transport, school buildings, offices
and housing, industrial installations are affected Earthly materials always keep an important
by corrosion and therefore susceptible to dete- point which is for good development of any
rioration and degradation processes. economy we are living, that further be sustained
Corrosion is a worldwide crucial problem globally. The usage of metal depends upon the
that strongly affects natural and industrial envi- characteristic properties it is having and its
ronments. Today, it is generally accepted that important applications that it may be having in
corrosion and pollution are interrelated harmful society. Few were summarized below:
processes since many pollutants accelerate cor- In the line of any metal production from its
rosion and corrosion products, such as rust, also ore, multiple processes applied are mineral
pollute water bodies. Both are pernicious pro- mining, manufacturing with application along
cesses that impair the quality of the environ- with production of various solids, liquids, and
ment, the efficiency of the industry and the gases that are having great impact on the society
durability of the infrastructure assets. Therefore, and environment.
it is essential to develop and apply corrosion For specific industrial progress, in general the
engineering control methods and techniques. metal and materials are produced in such a way
Other critical problems, that impact on infra- that they will not affect the environment at
structure and industry are climate change, global 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 Processed Material → Different Application of
demand or consumption inducing in the market. Materials → Waste Material → Recycling of
There are many approaches to carry out these Materials.
things. The most general way is to research the In the basic steps involved for mineral
materials and apply them as per their use in extraction, the effluents of carbon, nitrogen,
recommended technology. It can also to be note sulfur and compounds such as NOx, SOx and
that the materials which are allowed to recycle COx may come from different machines and
mainly requires very less capital and energy equipment’s. These all fill the land and under-
consumption, alternatively needs more man- ground water. This contamination may also
power for basic processing. In addition, the cause severe corrosion of metals or alloys
price of pollution control mainly happens to be present in vicinity.
low as required for primary processing’s
[8–10].
Also, the costs of pollution control are lower 1.3 General principles or theories of
than those required for primary processing of industrial corrosion
minerals. Recycling becomes more intense, as
economies tend to be more sophisticated, since There are three general principles or theories
viable quantities of recycled material must be to be follow for corrosion to happen in any
available for reuse [11]. medium for metal or alloys:
Industries produce various things of our
Acid theory of corrosion
daily use during processes waste material is
Dry or chemical theory of corrosion
generated, these are those parts of material that
Galvanic or Electrochemical or Wet theory
was left aside, during the production steps.
of corrosion
They may be named as Effluent, having waste
that comes from the procedures attached to the Acid theory of corrosion:
technology in various step of production in This theory mostly explains corrosion for that
addition with main material. So many industrial metals or alloys which is in the vicinity of acid.
processes such as recovering metal from their As per this theory, metal (iron) is specifically
ore involves much technological steps which corroded by carbon-di-oxide, water (moisture)
may vary in different countries such as eco- and oxygen. Products of corrosion includes
nomic, financial aspects with regulatory laws. mixture of Fe (HCO3)2, Fe (OH)CO3 and Fe
This explains how environmental impacts vary (OH)3. The ongoing reactions for the corrosion
much around the globe. The refinement of metal are given below:
from depends upon its quality, i.e., if the ore
contains very low amount of metal and needs Fe + 2CO 2 + H 2 O + 1 2 O 2 → Fe ( HCO 3 )2
multiple steps to recover. This all increases the 2Fe ( HCO 3 )2 + H 2 O + 1 2 O 2 → 2Fe(OH)CO 3
cost of recovery and also needs huge amount of
+ 2CO 2 + 2H 2 O
raw mineral material. In addition of these things,
energy applied is also in much need. The other 2Fe ( OH ) CO 3 + 2H 2 O → 2Fe ( OH )3 + 2CO 2
processes involve mechanical or physical
removal of rock, transportation of material from This theory is supported by the analysis of
mines, concentration of ore at specific place. The rust that gives the test for CO2 ion.
flow chart for material cycle is given here: Dry or chemical theory of corrosion:
Raw Material Resource → Material Extrac- This type of corrosion mainly occurs on the
tion → Material Processes → Different Forms of surface of metal and happens due to reactions

Part 1 Overview of industrial corrosion and inhibition


1.4 Different types of corrosion in industries 5
of gases present in atmosphere such as oxygen, Wet or Electrochemical theory of corrosion This
halogens, oxides of nitrogen and sulfur, hydro- form of corrosion may occur when the metal
gen sulphide, and fumes of chemicals along comes in contact with any form of conducting
with metal. liquid or when two dissimilar metals are immersed
There are three general types of dry corrosion or dipped partly in a solution. Here there is the
which are given below: formation of a galvanic cell on the surface of
metals. Some parts of the metal surface act as
Oxidation corrosion (reaction with oxygen)
anode while other acts as cathode. The chemical
Corrosion by other gases, such as Cl2, SO2,
present in the environment and humidity percent-
H2S, NOx
age acts as an electrolyte. The oxidation of anodic
Liquid metal corrosion
part takes place and it results in corrosion at
Oxidation corrosion (Reaction with oxygen): anode, while reduction takes place at cathode. The
As various metals directly make reactions in corrosion product is formed on the surface of the
presence of oxygen and in absence of moisture. metal between anode and cathode.
Examples are alkali and alkaline earth metals
that reacts with oxygen present at standard tem-
perature and generate oxides of corresponding 1.4 Different types of corrosion in
metals. In return metal oxides are in process of industries
making a thin film over metallic surface which
further protects metal to undergo corrosion. So, The basic corrosion involves some electro-
the metal oxide always plays a major role in the chemical reactions that lead to oxidation of
process of corrosion. metal atom into the metal ions releasing elec-
trons at anode; those electrons were further con-
M → M + ne − ( n = 1) (1.1) sumed at cathode during simultaneous
− − reduction reaction. This can be known by given
1 O 2 + 2e → O (1.2)
2
reactions:
The anodic corrosion reactions:
Combining Eq. 1.1 and 1.2.
2M + 1 2 O 2 → M 2 O Fe → Fe2 + + 2e −

Corrosion by gases such as Cl2, SO2, H2S, NOx Zn → Zn 2 + + 2e −


If the atmosphere is dry, so the gases like Cl2, The cathodic corrosion reactions:
SO2, H2S, NOx may react with metal and alloys
to form corrosion products which may be pro- 2H + + 2e − → H 2
tective or non-protective in nature. H 2 O + 1 2 O 2 + 2e − → 2OH −
Chlorine gas do react with silver (Ag) to form
silver chloride (AgCl) which may acts as protec- O 2 + 4H + + 4e − → 2H 2 O
tive layer. That specific site where metal atoms release
Liquid metal corrosion: electrons is called the anode while the site where
In different industries, metal in molten form electrons are consumed to the reducing species
which passes through metallic pipes happen to is called the cathode.
cause corrosion might be due to dissolution or Corrosion can be considered as an electro-
due to internal penetration. The metal like liquid chemical process where flow of electric current
mercury usually dissolves most other metals to along with the chemical reactions goes on simul-
form amalgams, which alternatively corrodes taneously. Some general types of corrosion are
them. given here:

Part 1 Overview of industrial corrosion and inhibition


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 By this we can simply say, the anode is disman-
It occurs when the dissimilar metals or alloys tled but the cathode is sheltered.
are joined together via electric circuit in the com- As described earlier, a hydrogen film is
panionship of an electrolyte. Most important formed on the cathode or carbon rod that helps
example comes from a cell, where anode is made cathode to insulate from the electrolytic solution
from zinc which is placed in electrolyte carrying and further stops flow of current. This happens
ions of zinc. Further these zinc ions are dis- to stop corrosion, as the formation of hydrogen
solved in the provided electrolyte, so that the film on the cathode took place. Corrosion starts
exchange of hydrogen ions can occur. While the as soon as this layer if detach from the cathode.
ion’s flow through the electrolyte to produce In the case of cell or battery, the zinc case is
electric current via carbon rod which acts as easily attacked and the carbon is protected. This
cathode. At this position the hydrogen ions are causes any metal to be attacked if present in
mostly deposited over the surface of the carbon circuit and will not attacked when in circuit with
rod as hydrogen gas. In addition, if hydrogen another. By different experiments and researches
gas remains intact on the carbon rod it will act a table was made earlier, called as Galvanic
as an insulator, which terminates flow of current. Series wherein a metal present above can be
This is called as Polarization, which is formation attacked by another metal present below in list
of the film, while its removal is named as Depo- when present in common electrolytic environ-
larization. Here the current flow’s is from zinc ment like moist soil or water. The metal or alloys
anode to the electrolyte, to the carbon rod present above are more susceptible to corrosion
cathode and back to the metal zinc via external or less noble compared to below present in table,
wire which is connected to the battery. As the which are least susceptible to corrosion or con-
current starts flowing in this circuit, the zinc is sidered as more noble, the table is shown below
decreasing while the carbon remains unharmed. 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 It’s a unique type of corrosion where there is
industries occurs in machineries where different formation of small pin holes at various places.
kind of parts are made having different geome- Harsh perforation of the material causes leakage.
tries like joints, threaded, bolted or any irregular Generally, the material-environment duo can
shape. The interaction between metal and non- make defensive passive film on the case copy
metal such as under the spacers or gaskets also 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- austenitic steel at higher temperature which
fate ions may enter the suspected area and ranges from 482-760°C, there is formation of
bruise the passive layer and cause pin hole cor- chromium carbide Cr23C6 along the grain bound-
rosion. Pits become aggressively acidic with aries. That causes overall depletion of chromium
elevated concentration of chloride compared to and hence lost corrosion resistance. The ongoing
bulk mixture. The reactions of pitting corrosion process is called as Sensitization. This process
are so similar to that of crevice corrosion. This is generally occurs in industries at the time of
very common in industries. We can eliminate welding operations, solution annealing and
this corrosion by selecting pitting resistant stress relieving processes. Intergranular corro-
alloys. Researchers can check failure due to sion can also be called best as Weld Decay
pitting by knowing Pitting Resistance Equiva- because sensitization is occurring at the heat
lent (PRE) Index by given formula: affected zones (HAZ) which were developed in
between weld joints. The intergranular corro-
PRE = 1 × % Chromium + 3.3 ×
sion of austenitic steel can be eliminated by
% Molybdenum + 16 × % Nitrogen.
putting strong carbide formers and also by
Some values of PRE index of some metal are:
decreasing carbon content in stainless steel
AISI 316 stainless steel = 25.6.
<0.03% (e.g., 304L/316L).
AISI 304 = 18.
Some engineered alloys have the given 1.4.6 Stress corrosion cracking
decreasing order such as:
Ti> Hastelloy C or Chlorimet> Hastelloy F, Here the metal or alloy can be affected by
Durimet 20> Type 316 stainless steel> Type 304 brittle cracking which are caused by majorly
stainless steel. three factors such as:
Tensile stress: It can be due to two forms
either operational or residual stresses in the
1.4.5 Intergranular corrosion metal / materials or alloys. This all occurs
It involves type of corrosion where there is as a result of the metal formation, creation
involvement of preferential attack on alloys and welding processes.
which are in contact with certain environment Susceptible materials: This is not applicable
along the grain boundaries. This clearly happens to all kinds of metal or materials as pure
due to micro segregation of impurities and dif- metals are mostly susceptible to this
ferent alloying elements present in grain’s corrosion type. While some metal or alloys
boundaries of any equipment used in industries. are susceptible to specific environment. For
The incentive for this kind of corrosion is the example: Austenitic stainless steels are
generation of potential difference in between greatly resistant for developing SCC when
grain boundary and the grain matrix, which they are kept in ammoniacal environment.
further develops galvanic cell in the vicinity of Susceptible environment: These are some
electrolytes. The movement of corrosion is from specific environments which generally
grain boundaries from the edge to the thickness cause Stress Cracking Corrosion of the
or middle. This all-causes disintegration of metal mostly used in industries. For
metal and hence strength is lost. Mainly the example, if stainless steels are used in
equipment’s or instruments made from nickel, chloride containing environment are crack
aluminum alloys and austenitic stainless steels prone but not when used in acids such as
may suffer from intergranular corrosion in the sulfuric acid, nitric acid, acetic acid or
industries. If we talk especially corrosion of pure water.

Part 1 Overview of industrial corrosion and inhibition


1.4 Different types of corrosion in industries 9
The cracks develop during this corrosion may 1.4.8 Erosion corrosion
run along preferential routes such as along grain
boundary called as Intergranular Stress Corro- It is a general term that relates to a corrosion
sion Cracking (IGSCC) or may be transversely process caused by the relative motion of the
around grain boundary, which further called as flowing fluids and materials surface. The usual
Trans granular Stress Corrosion Cracking effect of the EC is localized attack which emerges
(TGSCC). as gullies, grooves, rounded holes, and waves
The corrosion happening here can also be etc. The most affected equipment’s by this kind
prevented by the replacement of austenitic stain- of corrosion in general industries are impellers,
less steels BY austenitic-ferritic (duplex) stain- under water components, steam turbine blades,
less steels, which have remarkably low bends, inlets pipes in different tanks, pumps and
susceptibility to stress corrosion cracking com- cyclones. Destruction of metal is Destruction of
pared to previous one. Applying compressive metal is quick as the running liquid discard the
stresses and coating would also help to reduce protective corrosion layer formed over the metal
SCC. surface, which further exposes the fresh metal
surface alternatively more prone to corrosion
with accelerated rate. In addition, the corrosive
1.4.7 Corrosion fatigue suspended products which are added to the
aggressive medium or fluid cause extensive
Corrosion fatigue (CF) is propensity of alloys coarse-grained action over metal surface leading
used in industries or engineering applications. to enhanced corrosion rate.
It got fracture because of the presence of colle- In the industries the situation becomes worse
gial effects of cyclic loading and aggressive by the process of Cavitation (kind of erosion
environment. The collapse starts occurring at corrosion) which is formed by unanticipated
places of stress levels present on material or at crumble of vapor bubbles in a liquid and ema-
the tolerance limits. It is a crucial deterioration nating impact over metal surface. The collapsing
process which is highly responsible for the of bubbles may be having high value of more
damage caused in industries such as nuclear or than 1500 MPa which is adequate for the micro-
steam power systems, aircrafts, marine struc- structural swapping in the underlying material
tures, bridges, pipelines and gas turbines. The surface.
damage caused by corrosion fatigue mat occur Due to regular cavity deficit passive film for-
in four steps: deformation caused by cyclic mation is strenuous and hence metal cessation
plastic, initiation of microcrack, growth of small is elevated. Specifically in industries the liquid
crack and propagation of macrocrack. The use or processed fluid accommodates rigid solid
of different mediums and present environment particles which serves and accelerates corrosive
for specific work in industries promotes corro- reactions by their harsh actions. Special design-
sion fatigue due to various factors (frequency, ing and application of coatings to the suspected
stress ratio, electrode potential or stress inten- components are useful methods to prevent
sity range). Corrosion fatigue generally moves erosion and cavitation corrosion.
in the trans granular manner and does not show
divarication which is important characteristics
feature of stress corrosion cracking. Corrosion
1.4.9 Selective leaching
fatigue can be best reduced by eliminating the It is very specific in industries where the
stress on the industrial materials or can be erosion of one constituent of an alloy in presence
accomplished by changing the architecture and of certain electrolyte may result due to electro-
heat treatment. chemical reactions. The main reason for this

Part 1 Overview of industrial corrosion and inhibition


10 1. General principles of industrial corrosion

corrosion to occur is the creation of large elec- thermal expansion with frequent cycling. There
trode potential of constituents of alloy such as is development of fatigue cracks in the
zinc (Zn) and copper (Cu) in brass alloy or in components.
between iron (Fe) and graphite (C) in grey cast
iron.
The metal or element which has lower elec- 1.4.11 Microbiologically influenced
trode potential as a choice corrodes first and corrosion
diffuse in the electrolyte or liquid. While the one This corrosion often infuriated by the pres-
which has higher electrode, potential remains ence of microorganisms and so secondarily
secured cathodically. The most customary alloys control the reactions of corrosion. Mostly places
vulnerable to corrosion are Silicon bronze of sewage, under bridges, buried structures and
(desiliconification), Tin bronze (destannifica- water operated equipment’s where the microor-
tion), Brasses (dezincification), Grey cast ganism may be sheltered are influenced struc-
irons (graphitic corrosion), Aluminum tures for this corrosion. As those microorganisms
bronze (dealuminification) and Copper-Nickels are having propensity to excel in presence or
(denickelification). absence of oxygen environment done by popu-
If we see on the percentage basis, the process larly known as aerobic and anaerobic bacteria.
of dezincification occurs in brasses having more The aerobic bacteria are sulfur oxidizing bacte-
than 15% of zinc, as zinc is chemically very ria (thiobacillis / thiooxidans) which oxidizes
active element with very low standard electrode the elemental sulfur or sulfur hearing compound
potential, valued -0.763 while electrode poten- to sulfuric acid thus reduces the pH of the envi-
tial of copper is much higher with value +0.337. ronment. Likewise anaerobic or sulfate reducing
So, the difference between these two potentials bacteria (deslfuricans) which reduces sulfate to
is the driving force for dezincification of brasses. sulfide that influences the hydrogen evolution
The metal in industries starts corroding with and accelerates metal oxidation (anodic reac-
cessation of zinc-to-zinc ion (Zn = Zn2++ 2e−) tion). The most accepted way to reduce micro-
quitting behind the network of copper. biologically influenced corrosion is to apply
coating comprising enamel, plastic tape and
asphalt. The other way is addition of corrosion
1.4.10 Fretting corrosion
inhibitors such as germicides (Chlorinated com-
This kind of corrosion is amalgamation of pounds) that can be supplied to the corrosive
simple corrosion and abrasive wear. It can be systems.
speeded by the correlative motion of approach-
ing surfaces in aggressive medium. The relative
motion between the exposed surfaces detaches 1.5 Corrosion of metal in industries
shielded films and may ends in enhanced corro-
sion. It has been noted that generally corrosion The components or equipment’s present in
products are eroding in nature and their exist- machine that helps to function them are
ence in the aggressive fluid may increase the extremely susceptible to corrosion as they are in
confiscation of protective films. This corrosion use for long time. This causes failure of compo-
mostly affects the industrial equipment’s related nent of the things in use. The components are
to aeroplane, ships and automobile assemblies made with high density are made light by
or the places where periodical loading is accom- making their sections thin. This all causes
plished. Fretting corrosion can be more promi- increase in corrosion. Furthermore, the corro-
nent at places of vibration in blade system and sion rates of devices or equipment’s used in

Part 1 Overview of industrial corrosion and inhibition


1.5 Corrosion of metal in industries 11
industries are enhanced to maximum when they moisture bimetallic or galvanic corrosion occurs.
are encountered with harsh or aggressive envi- Keeping in view of these kinds of locations, the
ronments such as deserts, moist places, tropical following precautions must be greatly to take in
or sub-tropical environments mainly for things account:
in military use. Aircraft and submarine systems
Appropriate design: Here the exposed
are highly affected. Music player instruments on
metal or alloys are so made that the area of
the other hand are severely affected when
the more noble cathodic metal or alloy must
exposed to fuggy environments having chlo-
be substantially smaller compared to the rea
rides. This all happens in shipping those instru-
of more active anodic metal. So, the most
ments from manufacturing place to customer’s
expected way to reduce the area of cathode
location.
is to apply coating or suitable paint over it.
The formation of very thin layer made from
Suitable Coating: The area in contact of
corrosion reactions alter the electrical properties
metal with each other can be coated with
of the instruments, such as capacity, resistance
appropriate metal.
of electronic systems. Many cases has been
Insinuation of dissimilar metals: There
reported in electrical manufacturing industries
must be an interpose in linking different
which causes alteration in inbuild circuits, fit-
metals in a metal compatible packaging.
tings, connectors, nichrome resistors along with
Clinching interfaces: All interfaces must be
micro-electronic components which have been
properly sealed to avoid admittance of
glazed with metallic films. There are reported
moisture.
cases where small amounts of moisture have
Proper setting: Mostly electronic devices
caused corrosion in tablets with printed circuits,
must be placed in hermetically sealed
nichrome resistors, fittings, electrical connectors
arrangement.
and a wide range of components, and micro-
electronic components, which have been coated
with metallic films [12–13]. 1.5.1 Corrosion of metal by water
The corrosion of components in different The water is most essential component of any
industries may occur at various stages such as: country’s manufacturing/industrial promotion.
The multiple application of water is to act as
Manufacturing
coolant for equipment and machineries. Total
Storage
quantity of liquid or water used by each country
Shipping
are almost different and depends on the percent-
Services
age of industrial development. In the previous
Important factors to initiate corrosion is the time for the United States like country, the con-
development of moisture, pollutants, sweeping sumption of water was around hundred billion
of organic solvents or presence of elements such liters per day. Further these countries have opted
as chlorides, fluorides, sulfides or nitrogen to reuse the water system by the application of
compounds. right treatment channel for its purification.
The input of pollutants for single machinery is Water is always considered as an aggressive
diverse like flux remnants used for welding, environment for various metals and alloys, by
vapors from electrolytic baths, micro plastics, vola- which they may encounter with corrosion which
tile organic adhesives from nearby environment. is an electrochemical process.
Industrial applications need various metal, The water may come from natural resources,
out of them many remains in contact with each such as lakes, rivers, springs, or well which can
other, at those places due to presence of easily corrode metal or alloys used in industries.

Part 1 Overview of industrial corrosion and inhibition


12 1. General principles of industrial corrosion

The most important equity of water is that some [10] F. Smaïli, V.S. Vassiliadis, D.I. Wilson, Optimization of
degree of material present in earth crust and cleaning schedulesin heat exchanger networks subject
to fouling, Chem. Eng. Commun. 189 (11) (2002)
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[12] H. Ashassi-Sorkhabi, E. Asghari, M. Mohammadi,
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the formation of green rust compounds during
In lieu of corrosion that is happening in multi- cathodic protection, Electrochim. Acta 54 (13) (2009)
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[3] J.H. Duffus, Heavy metals-a meaningless term? Pure ing, extractive, metallurgy, 3 (2010) 125–12.
Appl. Chem. 74 (5) (2002) 793–807. [17] S.B. Valdez, R. Zlatev, K. Schorr, M.W. Rosas, N.G. Ts,
[4] Bradl H., (Eds.), Heavy Metals in the Environment: M. Dobrev, I. Monev, Krastev, Rapid, method, for, cor-
Origin, Interaction and Remediation Volume 6. London: rosion, protection, determination, of V. C. I., Films-
Academic Press; 2002. Corrosion, Anti, Methods, Materials, United, &
[5] Z.L. He, X.E. Yang, P.J. Stoffella, Trace elements in agro- Kingdom, Vol. November 6 (2006) 362–366.
ecosystems and impacts on the environment, J. Trace [18] B.G. Lopez, S.B. Valdez, K.R. Zlatev, P.J. Flores, B.M.
Elem. Med. Biol. 19 (2–3) (2005) 125–140. Carrillo, Corrosion of metals at indoor conditions in the
[6] R.A. Goyer, Toxic effects of metals, in: CD Klaassen electronics manufacturing industry, Anti-Corrosion
(Ed.), Cassarett and Doull’s Toxicology: The Basic Methods and Materials; Bradford 54 (6) (2007) 354–359.
Science of Poisons, McGraw-Hill Publisher, New York, DOI:10.1108/00035590710833510.
2001, pp. 811–867. [19] B. Valdez, M. Schorr, M. Quintero, R. Garcia, N. Rosas,
[7] N. Herawati, S. Suzuki, K. Hayashi, I.F. Rivai, K.H. Effect of climate change on durability of engineering
Cadmium, copper and zinc levels in rice and soil of materials in hydraulic infrastructure: An overview,
Japan, Indonesia and China by soil type, Bull. Env. Corros. Eng. Sci. Technol. 45(1)(2010)34–41.
Contam. Toxicol. 64 (2000) 33–39. [20] B. Valdez, M. Schorr (Eds.), Environmental and
[8] R. Garcia, et al, 2012, Lopez, G. 2011, Schorr, M., 2010. Industrial Corrosion: Practical and Theoretical Aspects,
[9] L.M. Al-Hadhrami, A. Quddus, A. Dhawi Al-Otaibi, London: IntechOpen Press; 2012.
Calcium sulfate scale deposition oncoated carbon steel [21] A.R. Rakitin, V.I. Kichigin, Electrochemical study of
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(2013) 2521–2528. anion, Electrochim. Acta 54 (9) (2009) 2647–2654.

Part 1 Overview of industrial corrosion and inhibition


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 has a significant impact both eco-


nomically and environmentally on almost all the
Corrosion is a naturally occurring process world’s infrastructure. This includes highways,
which is defined as the degradation or deterio- bridges, automobiles, pipelines, chemical pro-
ration of a substance and/or its properties, cessing, water/wastewater systems, and the
usually a metal, over a period of time due to military [3]. Corrosion costs more than $ 1.8 tril-
environmental exposure [1]. This is an exergonic lion per year globally. Studies done in China,
process as the metal tends toward the lowest Japan, the United Kingdom, Europe, and South
possible energy state. Corrosion is a naturally America have shown corrosion costs similar to
occurring process defined as the degradation or the United States. This corrosion problem trans-
deterioration of a substance and/or its qualities, lates into 3–4% of the GDP of industrialized
typically a metal, over time as a result of envi- nations worldwide. Corrosion is so prevalent
ronmental exposure [2]. As the metal tends to and manifests itself in such diverse forms in our
the lowest possible energy state, this is an exer- industrialized society that its occurrence and
gonic process. As a result, when metals are associated costs can never be eliminated [4].
mixed with oxygen and water to create oxides, The environment to which metals are exposed
they have a natural propensity to return to their consists of the entire surroundings in contact
lowest energy state (corrosion products). These with the metal. The major factors used to
corrosion products are the final state of pro- describe the environment are the physical state
cessed metals that degrade over time when of the environment, either gas, liquid or solid;
exposed to the elements. Thus, the life cycle chemical composition, which includes constitu-
from mined and processed ores to industrial ents and concentrations; and temperature [5].
products and eventually back to their natural These three factors have a significant influence
state is as shown in Fig. 2.1. on the rate of corrosion. However, additional

Eco-Friendly Corrosion Inhibitors


DOI: https://doi.org/10.1016/B978-0-323-91176-4.00023-4 13 Copyright © 2022 Elsevier Inc. All rights reserved.
14 2. Corrosion prevention and protection methods

Production of
iron and steel
Crude steel Production products

Raw Material Extraction

Pre-consumer
Post-consumer scrap
scrap

End of Life Use Phase of


phase End Products
Sector X
FIG. 2.1 Flow of material through society.

factors such as the velocity of a solution (flow to overcome this catastrophic phenomenon and
rate) and mechanical stress and/or loads can minimize its cost. The chapter will cover the
also play an important role in the corrosion of basic methods employed and the recent advances
metals. In order to understand and control cor- in the field precisely.
rosion, one must take into account both the
material and the environment. Identifying both
of these components will determine effective 2.2 Important considerations required
strategies for combating these destructive for the corrosion prevention and
processes. control methods
The corrosion subject has witnessed an inevi-
table transition from the state of isolation and The process of corrosion prevention and control
obscurity to an established engineering disci- does not end with the selection of materials.
pline. There have already been significant Instead, it lasts throughout a product’s lifespan,
advances over time in the field of corrosion and from acquisition through maintenance. Some of
corrosion prevention. There are, however, still the elements that influence corrosion during the
many problems that corrosion scientists/engi- life of a system are depicted in Fig. 2.2. Corrosion
neers need to solve. Learned societies such as prevention and control should begin with the
NACE, the European Corrosion Federation, the development of the design concept and continue
Japan Society of Corrosion Engineers, and others through the material selection process [6].
play a prominent role in the growth of education Through the detailed design phase, preventive
in corrosion engineering. Therefore, the primary maintenance and monitoring/inspection plans
aim of the chapter is to cover the fundamentals should be devised, and they should be main-
related to the prevention and control of corro- tained and updated as needed during the sus-
sion in order to establish a basic understanding tainment phase. Table 2.1 depicts the important

Part 1 Overview of industrial corrosion and inhibition


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- when possible, to corrosion-prone areas for clean-
resistant components and/or systems. The sec- ing and maintenance is important. The geometry
tions that follow go through these topics in of components also influences erosion-corrosion
further depth. for systems exposed to flowing corrosive fluids.
This includes directional changes in piping and
the access ports for chemicals that are added into
2.2.1 Design considerations the systems. The interfaces between adjacent
The particular design geometry is important materials or components may contribute to cor-
as areas where water and/or debris may accu- rosion in the form of the galvanic, crevice, and
mulate can experience increased corrosion rates. intergranular corrosion. The relative sizes of the
Simply drilling holes in structures to allow drain- two materials affect the current density between
age of water can help to mitigate this problem. them, which factors into galvanic corrosion rates.
Eliminating sharp corners will help reduce Fastened joints are areas that can trap electrolytes
crevice attacks. Also, providing accessibility, 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 17
role in any impurities within a material and any inspection has been widely practiced through-
defects on its surface or in a joint may increase out most any system. Hidden corrosion requires
the risk of corrosion. a number of different tactics dependent upon
the system. Borescopes and fiberscopes are used
to visually inspect the inside of some systems
2.2.4 Preventive maintenance through access ports. The corrosivity of the
considerations operational environment is monitored using
By employing a preventive maintenance electrochemical sensors. Bacterium counts and
schedule where a vehicle or structure is peri- cultures are used to monitor microbiological
odically inspected and cleaned, as necessary, activity and to regulate the use of biocides. Cor-
will help to reduce corrosion. Salt and debris rosion coupons are a low-technology technique
buildup on vehicles or structures, for example, of placing metal samples within the system and
can accelerate corrosion. Therefore, routinely periodically measuring their weight loss. Per-
washing them to remove the contaminants is a sonnel responsible for maintaining critical
sound practice. Furthermore, touching up pro- systems may additionally use a host of nonde-
tective coatings or reapplying corrosion pre- structive inspection methods to measure thick-
ventative compounds (CPCs) on a regular nesses or detect cracks. System design, materials
basis would assist in the reduction of corro- selection and manufacturing process actions
sion. Surface preparation is critical to coating are interrelated where each weighs in on the
adhesion, although in most cases, recoated others as depicted in Fig. 2.3. Historically, there
systems will never adhere to the original have been many instances where costly designs
coating deposited in a controlled environment. have been developed with little or no upfront
Often overlooked during a corrosion analysis consideration of materials or manufacturing
is the period in which a system is not in opera- concerns. This linear approach to developing a
tion. Some materials, such as stainless steels, new component or system can lead to compro-
are resistant to high velocity flowing liquids mises that can be avoided with a concurrent
and thus are used for certain piping applica- process where all issues are considered early
tions. However, these same materials can be and simultaneously.
susceptible to pitting, crevice, and microbio-
logically influenced corrosion (MIC) under
stagnant conditions. Introducing inhibitors Design (Service
Conditions,
and/or biocides into piping during downtimes Function, and Cost)
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.
Processing/Manufa
Materials
cturing (Equipment
2.2.5 Monitoring/inspection (Properties,
Availability, and
Selection, Influence
on properties and
considerations Cost)
Cost)
Monitoring and inspection are often essential FIG. 2.3 Interdependence of design, material selection,
preventive maintenance procedures. Visual and processing/manufacturing.

Part 1 Overview of industrial corrosion and inhibition


18 2. Corrosion prevention and protection methods

2.3 Strategies of the corrosion corrosion-related problems later in a product’s


prevention and control methods lifecycle. A comprehensive analysis starts by
employing a traditional process to examine the
Design, maintenance, and material selection mechanical, thermal, electrical, or physical
can be strategically used to minimize the extent requirements to determine which material class
to which a material, component or system cor- to employ and to subsequently select an initial
rodes during its lifetime. Simple elements incor- slate of candidate materials. The process
porated into a design can lessen the risk of described here will be used to further examine
corrosion. For example, allowing for drainage of these candidates to identify the one that pos-
water that otherwise might become trapped can sesses the best combination of performance and
effectively reduce corrosion problems. Similarly, life-cycle costs.
employing seals to preclude water from enter-
ing a component or system will provide similar
results. Another effective way to minimize cor- 2.4 Methods of corrosion control
rosion is to use gaskets to electrically insulate
two dissimilar metals, thus eliminating the pos- Corrosion management requires the imple-
sibility of galvanic coupling between adjacent mentation of engineering principles and tech-
components. Employing a maintenance sched- niques to, by the most economical method,
ule where a vehicle or structure is periodically mitigate corrosion to an appropriate degree. To
cleaned to remove salt or debris buildup will mitigate or control corrosion, there are different
help reduce corrosion. In addition, regularly practices that could be used (illustrated in
touching up protective coatings or reapplying Fig. 2.4). The use of the method relies upon
corrosion prevention and control methods will multiple parameters. For example, the type and
help reduce instances of corrosion. Perhaps the the location of the corrosion, the practical use of
most important way to prevent corrosion from the surface/structure to be protected, the local
occurring in the first place is to make appropri- environment, etc. The objective of the corrosion
ate material selection decisions upfront by care- control techniques is to minimize corrosion of
fully considering the application, environment, materials to an acceptable limit, so that they are
and potential corrosion problems that might able to attain their normal desired lifetime. In a
occur. Selecting the appropriate materials and limited number of cases, corrosion control
associated corrosion prevention and control methods are designed to eliminate it completely.
practices can reduce maintenance costs and The subsequent text summarizes the most
system downtime over the life-cycle of a system. commonly used ways and methods to tackle
There are a handful of material selection strate- corrosion [9].
gies that are used by designers. These strategies
range from a broad selection process used to
2.4.1 Proper selection of materials
establish a list of material classes that will be
applicable for a design down to detailed deci- The methodology involves the selection and
sion matrices to select specific materials/heat use of materials with high corrosion resistance
treatments. The intent of this book is not to to increase a structure’s longevity in a specific
address the various methods of selecting materi- setting. While there are no materials that are
als themselves. Rather, the purpose is to supple- resistant to all corrosive conditions, it is impor-
ment existing processes with a ‘roadmap’ or tant to choose suitable materials to avoid certain
process that a designer can employ during mate- forms of corrosion failure. Corrosion may be
rials selection to help reduce the risk of minimized by employing an appropriate design

Part 1 Overview of industrial corrosion and inhibition


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


and exposed to a steam atmosphere, where it
A chemical reaction between the corrosive quickly heats up. This process reduces the solu-
state of the metal and the local atmosphere bility of all dissolved gases, removing them
causes corrosion. Metal corrosion can be regu- from the feedwater. The released gases are then
lated instantly by excluding the metal from, or released into the atmosphere along with the
modifying, the state of the atmosphere. This can excess steam. The deaerated water falls into the
be as simple as reducing contact with rain or vessel’s storage section. This system reduces
seawater via indoor storage of metal materials the concentration of dissolved oxygen to less
or may be in the form of direct environmental than 7 ppb and completely eliminates the con-
manipulation affecting the metal. The rate of centration of carbon dioxide. This water can
metal corrosion can be lowered by methods to then be used to generate steam without further
minimize the sulphur, chloride or oxygen treatment.
content of the surrounding atmosphere. For In atmospheric corrosion, water and oxygen
example, in order to minimize corrosion in the are the primary corrosive agents. Because
interior of the unit, feed water for water boilers removing oxygen is impractical, methods that
may be formulated with softeners or several focus on reducing moisture content are used.
other chemicals in order to alter the hardness, There is negligible corrosion of the major engi-
alkalinity or oxygen content. In boilers, in order neering metals at relative humidity levels below
to remove the oxygen and other gases from the about 50%, and there are a number of ways to
feed water, deaerators are largely utilized. reduce humidity.
Boiling water removes the majority of the oxygen
and is sufficient treatment in some boilers. When • Air can be heated in warehouses and
water is used for cooling or other applications storerooms to reduce relative humidity
where heating is not required, it is subjected to below this level, but this causes a problem
a vacuum, which removes the majority of the when cold objects are brought into the
oxygen. For steam-generating boilers, however, room. Any surface with a temperature
very low oxygen content is required, and steam below the dew point will condense,
deaerators, as shown in Fig. 2.5, are used. The resulting in severe corrosion.
• A better solution is to chill the air before it
is circulated in a warehouse, allowing water
Atmospheric to precipitate. The residual water content of
vent
such freeze drying can be extremely low.
• Desiccants (also known as moisture
Boiler
feedwater scavengers) like silica gel and activated
alumina can be used to dry the air in
Steam packages and small storage areas.

2.4.3 Cathodic protection


Cathodic protection involves polarization of
Deaerated Feedwater
the structure, to be protected, to potentials more
negative than the corrosion potential, thus ther-
Deaerated water modynamically preventing the occurrence of
to boilers anodic reaction. For this purpose, an external
FIG. 2.5 Principle of steam deaerator. power source is used. Another common way is

Part 1 Overview of industrial corrosion and inhibition


2.4 Methods of corrosion control 21
to use “sacrificial anodes.” In this method, the The negative terminal of the current source is
anode is made of a more active metal (e.g. mag- connected to the metal requiring protection. The
nesium) than the structure to be protected (e.g. positive terminal is connected to an auxiliary
iron or carbon steel). Thus, the structure which anode immersed in the same medium to com-
needs to be protected acts as the cathode of a plete the circuit. The electric current charges the
new corrosion cell [5]. This type of protection is structure with excess electrons and hence
widely used to protect some underground struc- changes the electrode potential in the negative
tures, for example, water storage tanks, buried direction until the immunity region is reached.
pipelines, ship hulls, and marine facilities. There The layout for a typical impressed current
are two methods of cathodic protection: cathodic protection system is shown in Fig. 2.6.
Impressed current cathodic protection is the
2.4.3.1 Impressed current method most specialized technology and can be very
Impressed current cathodic protection tech- effective if correctly designed and operated.
niques are widely used for the protection of Typical materials used for anodes are graphite,
buried pipelines and the hulls of ships immersed silicon, titanium, and niobium plated with plati-
in seawater. A DC electrical circuit is used to num. Coatings are often used in conjunction
apply electric current to the metallic structure. 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 and, to a lesser extent, zinc.
designing a combined coating and an impressed No external power source is needed with this
current cathodic protection system is that coat- type of protection system and much less main-
ings deteriorate with time. Precious metals are tenance is required. These metals are alloyed to
used for impressed current anodes because they improve long-term performance and dissolu-
are highly efficient electrodes and can handle tion characteristics. Sacrificial anodes serve
much higher currents. Precious metal anodes essentially as sources of portable electrical
are platinized titanium or tantalum anodes; the energy. For cathodic protection of offshore plat-
platinum is either clad in or electroplated on the forms, aluminum anodes, made from alu-
substrate. Impressed current systems are more minum-zinc alloys, are the preferred material.
complex than sacrificial anode systems and Most offshore petroleum-production platforms
mostly used to protect pipelines. use sacrificial anodes because of their simplicity
and reliability, even though the capital costs
2.4.3.2 Sacrificial anode method would be lower with impressed-current
The principle of this technique is to use a systems. Magnesium anodes have been used
more reactive metal in contact with a steel struc- offshore in recent years to polarize the struc-
ture to drive the potential in the negative direc- tures to a protecting potential faster than zinc
tion until it reaches the immunity region. Fig. 2.7 or aluminum alloy anodes. Magnesium tends to
illustrates the principle in which sacrificial corrode quite readily in salt water, and most
metals used for cathodic protection consist of 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 23
permanent long-term marine cathodic protec- are often applied in conjunction with cathodic
tion applications. Zinc anodes are also used to protection systems to take care of any damage
protect ballast tanks, heat exchangers, and caused to the coating material. Application of
many mechanical components on ships, coastal non-metallic piping is also good in many appli-
power plants, and similar structures. In seawa- cations as they do not corrode, but the limitation
ter, passivity can be avoided by alloying addi- is that they may deteriorate or it weakened by
tions, such as tin, indium, antimony, or mercury. attack from their environment. Polyvinyl chlo-
The three most common types of sacrificial ride (PVC) is one example of this type of piping;
anodes are: activated aluminum, zinc and mag- this material is usually repeatedly reheated, sof-
nesium. Aluminum is the most widely-used tened and reshaped without destruction.
material for anodes, as it has a higher current However, where mechanical/structural integ-
capacity in comparison to the other metals. rity is important, such in cases of high internal
Magnesium should be considered when the or external pressures and loads, PVC and other
chloride content is less than 10,000 ppm. polymer-based materials cannot be used, and
the use is then usually confined to metals. Metal
coatings can also be incorporated into this cat-
2.4.4 Anodic protection egory. For example, corrosion susceptible metals
Anodic protection, which is an electrochemi- (e.g. carbon steels) could be coated with a thin
cal method of controlling corrosion based on the chromium coating. Chromium is a highly corro-
phenomenon of passivity, is a comparatively sion resistant material, and as long as the chro-
new method suggested by Edeleanu [9,10]. To mium coating is compact, it will protect the
build a protective oxidized layer on the pro- underlying structure from corrosion.
tected base material, also known as the sub-
strate, an electrical current is used in the process. 2.4.5.1 Organic coatings
The passive potential is automatically main- Such coatings afford protection by providing a
tained, usually electronically, by an instrument physical barrier between the metal and the envi-
called the potentiostat. The method is applicable ronment. The substrate material and the environ-
to metals having active passive transitions like ment are separated by a rather thin barrier. Paints,
nickel, titanium, iron, chromium and their varnishes, lacquers, and other similar coatings
alloys. Its usefulness and its low current demand undoubtedly preserve more metal per ton than any
in highly corrosive environments are the signifi- other corrosion-prevention technique. Although
cant benefits of anodic protection. most people are familiar with outside surfaces,
inside coatings or linings are also extensively used.
Organic coatings cost approximately $2 billion per
2.4.5 Coating, linings, and nonmetallic year in the United States. There are several sorts of
piping products involved, some of which are backed by
A coating is a thin material applied as a liquid ludicrous claims. For good performance, extensive
or powder, which, on solidification, is firmly understanding of this difficult area is necessary. For
and continuously attached to the material, to be the uninformed, the best course of action is to seek
protected. For internal use, this method might advice from a recognized organic coatings manu-
be called lining. Coatings need to be flexible, facturer. As a general rule, these coatings should
resistant to chemical fluid attacks, to have strong not be utilized in environments where the sub-
adhesion, to have low or no porosity, and to be strate material will be rapidly attacked by the
stable at working temperatures. The coatings environment.

Part 1 Overview of industrial corrosion and inhibition


24 2. Corrosion prevention and protection methods

2.4.5.2 Inorganic coatings the metal surface and the aggressive environment.
To provide a barrier between the atmosphere The physical blockage effect or the effects of the
and the metal, these coatings are often used. inhibitor on the mechanisms and kinetics of the
Enamel, glass linings, and conversion coatings corresponding corrosion reactions can be related
are all inorganic coatings. The treatment trans- to this minimization. Inhibitors are typically deliv-
forms the metal surface into a metallic oxide film ered from a solution or dispersion, but some are
or a compound that is more resistant to corrosion used in preparations for protective coating.
than the natural oxide film and provides an effec- Inhibitors are defined by the International
tive base or additional safety key, such as paints. Standard Organization as “a chemical compound
that, when given to an environment in a tiny quan-
2.4.5.3 Metallic coatings tity, retards corrosion without substantially affect-
Another type of coating is metallic coatings ing the concentration of any other corrosive agent.”
that provide a barrier between the metal sub- According to this definition, a chemical added to
strate and the atmosphere. Furthermore, when an environment to neutralize an acidic constituent
the coating is damaged, metallic coatings can or oxygen scavengers added to water to remove
often provide cathodic protection. Using a oxygen from the electrolytes are not inhibitors,
variety of techniques, including hot dipping, despite the fact that they help to reduce corrosion
electroplating, cladding, thermal spraying, and rates. For a corrosion regulating chemical to be
chemical vapor deposition, metallic coatings called a corrosion inhibitor, it must be adsorbed at
and other inorganic coatings are developed. 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
2.4.6 Use of corrosion inhibitors producing a film to protect it. Inhibitors are usually
In different industries, among the most efficient dispersed or diffused from a solution. Some are
methods of effectively reducing corrosion is by incorporated into the formulation of a protective
using corrosion inhibitors. Corrosion inhibitors coating. The schematic diagram of adsorption
are chemical substances which stop or retard cor- inhibitors can be seen in Fig. 2.8. Adsorption inhibi-
rosion of the metallic surface when added to the tors establish a chemisorptive interaction with the
corrosive medium in small quantities. Most of the metal surface, prohibiting electrochemical dissolu-
inhibitors actively employed are organic mole- tion processes from proceeding.
cules [11]. Via adsorption on the metallic surface, Metal and alloy corrosion is caused by the
these inhibitors work to protect the surface by creation of minute electrochemical cells at the
forming a film that minimizes the contact between metal-electrolyte interface, as already known.

Fe2+ O2 O2
O2 O2 Fe2+

Cathode Anode Cathode Cathode Anode


e–
e– e–

(A) (B)
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


Conclusion 25
Corrosion inhibitors work by influencing any of analysis to prevent this from happening. When
the corrosion reactions, either anodic or cathodic. concentrations fall below required levels, pas-
Corrosion is slowed by inhibitors for the follow- sivation inhibitors can actually promote pitting
ing reasons [12]: and accelerate corrosion. As a result, it’s crucial
to keep track of the inhibitor concentration.
1. Increasing the behavior of anodic or cathodic
polarization (by altering the Tafel slopes),
2. Ion diffusion or migration to the metallic 2.4.6.2 Cathodic inhibitors
surface is reduced, and Cathodic inhibitors either impede the cathodic
3. Increasing the metallic surface’s electrical reaction or precipitate selectively on cathodic
resistance. sites, increasing surface impedance and limiting
the diffusion of reducible species to these areas.
Various scholars have categorized inhibitors
Cathodic inhibitors work in three ways to provide
in different ways. Some authors choose to clas-
inhibition: (1) as cathodic poisons, (2) as cathodic
sify inhibitors into the categories as anodic,
precipitates, and (3) as oxygen scavengers. Some
cathodic, or mixed inhibitors based on their pre-
cathodic inhibitors, including arsenic and anti-
ferred role in controlling the anodic, cathodic, or
mony compounds, act by making hydrogen
impacting both reactions [12,13].
recombination and discharge more difficult.
2.4.6.1 Anodic inhibitors Other cathodic inhibitors, such as calcium, zinc,
or magnesium, can form oxides on the metal and
They are also called passivators or passivat-
form a protective layer. By inhibiting cathodic
ing corrosion inhibitors. They generate a signifi-
depolarization induced by oxygen, oxygen scav-
cant anodic shift in the corrosion potential,
engers aid in corrosion prevention. At room tem-
causing the metallic surface to passivate. There
perature, sodium sulfite is arguably the most
are two types of passivating inhibitors: oxidiz-
often used oxygen scavenger (Na2SO3).
ing anions like chromate, nitrite, and nitrate,
which may passivate steel in the absence of
oxygen, and non-oxidizing ions like phosphate, Conclusion
tungstate, and molybdate, which require oxygen
to passivate steel. Because these inhibitors are Over time there has been significant progress
the most effective, they are also the most exten- in the development of corrosion prevention and
sively utilized. Chromate-based inhibitors are control methods, understanding of basic mecha-
the cheapest inhibitors and have been employed nisms by which corrosion occurs, and the imple-
in a range of applications until recently (e.g., mentation of mitigation techniques. This progress
recirculation-cooling systems of internal com- has allowed for the current state of material
bustion engines, rectifiers, refrigeration units, usage in both common and harsh environments.
and cooling towers). For these applications, The primary drivers for corrosion research have
sodium chromate was employed at concentra- been industrial and government needs. Address-
tions ranging from 0.04 to 0.1 percent. Higher ing these needs has led to advances in science, as
amounts are required at higher temperatures or well as further practical improvements, which
in fresh water with chloride concentrations then provide for further scientific advances.
above 10 ppm. Sodium hydroxide is used to Several strategies for retarding or preventing
modify the pH to a range of 7.5 to 9.5 if neces- corrosion in diverse environments have been
sary. Corrosion will be increased if the chromate described in depth in this chapter. The greatest
concentration goes below 0.016 percent. As a way to avoid corrosion is to use the right materi-
result, it is critical to do periodic colorimetric als, which are inert to the environment in which

Part 1 Overview of industrial corrosion and inhibition


26 2. Corrosion prevention and protection methods

they are used. Corrosion allowances should be 8. A.W. Peabody, Control of Pipeline Corrosion, 2nd Ed.,
included at the equipment design stage. Corro- NACE, Houston, Texas, (2001).
sion has an impact on the material selection.
Higher alloyed materials should be more cost Useful websites
effective if the rate of corrosion is high. In addi- https://www.icorr.org/souces-of-information/
tion to these concerns, a variety of additional https://www.nace.org/resources/general-resources/
techniques are used to avoid corrosion. Protective corrosion-basics
paints, protective metal and organic coatings, https://eoncoat.com/corrosion-prevention-methods/
https://www.corrosionpedia.com/corrosion-companies
protective films generated as a result of chemical
reactions, regulating the pH of the aqueous solu-
tion toward more alkaline, and applying electri- References
cal potential to the equipment are some of these [1] M.G. Fontana, N.D. Greene, The eight forms of corro-
ways (which needs to be protected). sion, Corros. Eng. 2nd ed. (1978) 137–148.
The interior and external equipment environ- [2] M.G. Fontana, Corrosion Engineering, 3rd ed. McGraw-
Hill; Singapore, 1987.
ments, such as moisture content, sunshine,
[3] W.D. Callister (2007). Materials science and engineer-
outdoor temperature, chemical reaction, salts, ing- an introduction.
galvanic response, wear, abrasion, and stress, all [4] L.H. Bennet, J. Kruger, R.I. Parker, E. Passiglia, C.
influence the choice of cost-effective corrosion Reimann, A.W. Ruff, H. Yakowitz, E.B. Berman, Eco-
solutions. Understanding and knowledge of nomic effects of metallic corrosion in the United States,
Nat. Bur. Stand. Spec. Publ. 511 (1978) 1–72.
corrosion’s causes is essential for successful cor-
[5] G.H. Koch, M.P.H. Brongers, N.G. Thompson, Y.P.
rosion prevention and management. Virmani, J.H. Payer, Corrosion costs and preventive
strategies in the United States, Mater Perform 42 (2002)
2–11.
Acknowledgment [6] T.P. Hoar, Review lecture: corrosion of metals: its cost
Authors acknowledge the financial support from Council of and control, Proceedings of the Royal Society of
Scientific & Industrial Research (CSIR), New Delhi, India, London. Series A, Mathematical and Physical Sciences,
through the major research project [file number: 22(0832)/20/ 348, The Royal Society Publishing 1976, pp. 1–18.
EMR-II]. [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.
Useful books [9] C. Edeleanu, Method for the Study of Corrosion Phe-
1. Metals Handbook - Volume 13A, 13B, 13C, Corrosion, nomena, Nature 173 (1954).
9th Ed., ASM International, Metals Park, Ohio, (2006). [10] C. Edeleanu, & Metallurgia. (1954). 50.
2. M.G. Fontana, Corrosion Engineering, 3rd Ed., [11] M. Mobin, R. Aslam, J. Aslam, Non toxic biodegradable
McGraw-Hill, New York, (1986). cationic gemini surfactants as novel corrosion inhibitor
3. Denny A. Jones, Principles and Prevention of for mild steel in hydrochloric acid medium and synergis-
Corrosion, 2nd Ed., Prentice Hall, Upper Saddle River, tic effect of sodium salicylate: Experimental and theoreti-
NJ, USA, (1996). cal approach, Mater. Chem. Phys. 191 (2017) 151–167,
4. Shrier’s Corrosion, 4 Volumes (ed. T.J.A. Richardson), https://doi.org/10.1016/j.matchemphys.2017.01.037.
Elsevier Science, (2009). [12] M. Mobin, S. Zehra, R. Aslam, L-Phenylalanine methyl
5. P.R. Roberge, Corrosion Basics - An Introduction, 2nd ester hydrochloride as a green corrosion inhibitor for
Ed., NACE, Houston, Texas, (2005). mild steel in hydrochloric acid solution and the effect
6. Joseph R. Davis, Corrosion: Understanding the Basics, of surfactant additive, RSC Adv. 6 (7) (2016) 5890–5902,
ASM International, (2000) The above five books are https://doi.org/10.1039/c5ra24630j.
perhaps the best corrosion textbooks. [13] M. Mobin, S. Zehra, M. Parveen, L-Cysteine as corro-
7. C.G. Munger & L. Vincent, Corrosion Prevention by sion inhibitor for mild steel in 1 M HCl and synergistic
Protective Coatings, 2nd Ed., NACE, Houston, Texas, effect of anionic, cationic and non-ionic surfactants,
(1999). J. Mol. Liq. 216 (2016) 598–607, https://doi.org/10.
1016/j.molliq.2016.01.087.

Part 1 Overview of industrial corrosion and inhibition


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


inhibitors are widely used to protect the metallic
The metallic materials are main used materi- materials from the corrosion destruction. The
als, because, their physical properties, such as metal surface is covered with the coatings, as a
electrical conduction, thermal conduction, and result, the covered metal surface is effectively
mechanical performances. The steel based insulated from the corrosion environments. The
metallic materials are most common in the gas corrosion inhibitors are performed to protect the
and oil industry [1–3]. However, a high percent- metal surface from the oxidation and corrosion
age of the steel materials are damaged by corro- destruction in the aqueous phase [5,6]. Currently,
sion in acidic environments [4]. Therefore, to the researchers are focusing more on inhibiting
protect steel materials is ongoing problem. Cur- corrosion development, because, the corrosion
rently, many researches are interested to going protection is ongoing issue in the chemical indus-
research in the corrosion protection. 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 The main objectives in the extraction and
need to become an environmentally and economi- syntheses, the method of syntheses, characteri-
cally effective [10,11]. Also, the application of syn- zation, and purification, discussion of obtained
thetic compounds as corrosion inhibitors is limited, results and inhibition mechanism of eco-
because of the increasing ecological awareness friendly corrosion inhibitors with the relevant
and strict environmental regulations. The tradi- examples are discussed and reviewed in this
tional corrosion inhibitors are synthesized using chapter.
expensive and toxic chemicals or solvents. In view
of this, recently, the glucose and their derivatives
are being used as green corrosion inhibitors as 3.2 Process for development of
they are available at the economic and commercial eco-friendly synthesizing corrosion
level [12]. This is due to their natural and biologi- inhibitors
cal origin; they can be regarded as one of the
greenest sources of the chemical compounds as Rbaa et al. [15] have synthesized new com-
corrosion inhibitors. Therefore, the presence of pound derivatives of D-glucose biodegrada-
numerous polar functional groups, such as –OH, ble and non-toxic as corrosion inhibitors for
further enhance their corrosion inhibition effec- steel in 1.0 M HCl. These compounds were
tiveness by increasing their molecular size as well synthesized by easy and selective methods,
as increase solubility in the polar electrolytes. and characterized by the usual spectroscopic
These polar functional groups can also serve as methods, namely, infrared (IR) and nuclear
adsorption centers during the meta-inhibitor magnetic resonance (1H NMR, 13C NMR). The
interactions. Looking at the greenness of glucose anticorrosion effect of these two compounds
and their derivatives along with their high protec- was studied using gravimetric and electro-
tion efficiency, the synthesis, characterization and chemical methods, such as potentiodynamic
utilization in all fields of science and technology, polarization (PDP) and impedance spectros-
including in the area of metallic corrosion inhibi- copy (EIS). The metal surface was character-
tion should be further explored [13]. ized by SEM and EDS techniques and the
In order to preserve the health of users of gravimetric solutions were analyzed by
these chemical compounds, when the corrosion ICP-OES and UV-visible spectrometry.
inhibitor are tested, it is important task to use The authors were synthesized the biodegrad-
non-toxic and biodegradable chemicals. Several able epoxy-glucose derivatives were synthe-
international organizations and committees sized with good selectivity in five steps:
have spoken out against the use of toxic chemi- The first step is the reaction of D-glucose 1 with
cal products [12,13]. In particular, the World acetone in sulfuric acid (H2SO4) as a catalyst at 0°C
Health Organization (WHO) [14], which is the to obtain compound 2. The second step is to add
most active on this side. The World Health alkyl bromide to compound 2 in a toluene-DMSO
Organization has published a list of chemicals mixture (4:1, v/v) as solvent to obtain compounds
that are the greatest source of danger to health. 3a,b. The third step is a partial deprotection of
Asbestos, benzol, cadmium, ammonia, mercury, compound 3in a mixture of EtOH-H2O (95:5, v/v)
lead are among these substances. The plastic in the presence of H2SO4 (0.2 N) at 40°C to provide
material products, cosmetics, foodstuffs include compounds 4a,b. The fourth step is the reaction of
chemicals, which some are harmful. Most of the compound 4 with tosyl chloride in toluene-pyri-
chemical compounds are toxic, they cause the dine (1:1, v/v) as solvent at a temperature between
death of millions of people around the world 0°C and -5°C for 72 hours to give compounds 5a,b.
every year. The last step consists in treating the compounds

Part 1 Overview of industrial corrosion and inhibition


Another random document with
no related content on Scribd:
repitió: “¿Estás contenta de que tu padre haya vuelto y de que ya no
se marche?”. La muchacha, que había mirado con suma atención a
los labios de su padre, tratando hasta de ver el interior de la boca,
respondió con soltura: “Sí, estoy contenta de que ha-yas vuel-to y de
que no te mar-ches ya nun-ca ja-más”. El padre la abrazó
impetuosamente, y luego, a toda prisa, le abrumó a preguntas.
“¿Cómo se llama tu madre?”. “Antonia”. “¿Cómo se llama tu
hermana pequeña?”. “A-de-laida”. “¿Cómo se llama este colegio?”.
“De sor-do-mudos”. “¿Cuántos son diez y diez?”. “Veinte”. De
pronto, y mientras que nosotros creíamos que iba a reír de placer,
se echó a llorar. ¡Pero también las lágrimas eran de alegría! “Ánimo
—le dijo la maestra—; tiene usted motivo para alegrarse, pero no
para llorar. Mire que hace usted llorar también a su hija. ¿Está
contento?”. El jardinero cogió fuertemente la mano de la maestra y
se la llenó de besos, diciendo: “Gracias, gracias, cien veces gracias,
mil veces gracias, querida señora maestra! Y perdóneme... que no
sepa decirle a usted otra cosa...”. “Pero no sólo habla—le dijo la
maestra—; su hija de usted sabe escribir. Sabe hacer cuentas.
Conoce los nombres de todos los objetos usuales. Sabe un poco de
Historia y algo de Geografía. Ahora está en la clase normal. Cuando
haya hecho los otros dos años, sabrá mucho, mucho más. Saldrá de
aquí en disposición de ejercer una profesión. Ya tenemos discípulos
que están colocados en las tiendas para servir a los parroquianos, y
cumplen en sus oficios como los demás”. El jardinero se quedó aún
más maravillado que antes. Parecía que de nuevo se le confundían
las ideas. Miró a su hija y comenzó a rascarse la frente. La
expresión de su semblante pedía claramente alguna mayor
explicación.

Entonces la maestra se volvió al portero, y dijo: “Llame usted a una


niña de la clase preparatoria”. El portero volvió al poco rato con una
sordomuda de ocho a nueve años, que hacía pocos días había
entrado en el Instituto. “Ésta—dijo la maestra—es una de aquéllas a
quienes enseñamos los primeros elementos. He aquí cómo se hace.
Quiero hacerle decir e. Esté usted atento”. La maestra abrió la boca
como se abre para pronunciar la vocal e, e hizo señas a la niña para
que abriese la boca de la misma manera.
La niña obedeció. Entonces la maestra le indicó que echase fuera la
voz. Lo hizo así la niña; pero en lugar de e, pronunció o. “No—dijo la
maestra; no es eso”. Y cogiendo las dos manos a la niña, se puso
una de ellas abierta contra su garganta y la otra contra el pecho, y
repitió: “e”. La niña, que había sentido en sus manos el movimiento
de la garganta y del pecho de la maestra, volvió a abrir de nuevo la
boca y pronunció muy bien: “e”. Del mismo modo la maestra le hizo
decir c y d, manteniendo siempre las dos manos de la niña, una en
el pecho y otra en la garganta: “¿Ha comprendido usted ahora?”,
preguntó.

El padre había comprendido, pero parecía aún más asombrado que


cuando no entendía. “¿Enseñan ustedes a hablar de este modo?—
preguntó al cabo de estarlo pensando un minuto y sin quitar su vista
de la maestra—. ¿Tienen la paciencia de enseñar a hablar de esta
manera, poco a poco, a todos? ¿uno por uno...? ¿años y años...?
¡Pero ustedes son unas santas! ¡Son más bien ángeles del Paraíso!
¡No hay recompensa para ustedes! ¿Qué más tengo que decir...?
¡Ah, sí! Déjenme un poco con mi hija ahora. Siquiera cinco minutos
que esté sola conmigo”.

Y habiéndola separado hacia un lado, se sentaron y comenzó a


preguntarle; la muchacha respondía, y él reía, con los ojos
humedecidos y pegándose puñetazos sobre las rodillas, cogía a su
hija por las manos, mirándola fuera de sí por la alegría que le
causaba el oírla, como si fuese una voz que viniese del cielo; luego
preguntó a la maestra: “¿Me sería permitido dar las gracias al señor
director?”. “El director no está—respondió la maestra—. Pero está
otra persona a quien debería usted dar las gracias. Aquí cada niña
pequeña está al cuidado de una compañera mayor, que hace como
de hermana y madre... Su hija está confiada a una sordomuda, de
diecisiete años, hija de un panadero, que es buena y la quiere
mucho; hace dos años va a ayudarla a vestir todas las mañanas, la
peina, le enseña a coser, le arregla la ropa, le hace compañía.
Luisa, ¿cómo se llama tu madre de colegio?”. La muchacha,
sonriéndose, respondió: “Ca-ta-li-na Jor-dán”. Luego dijo a su padre:
“Muy, muy buena”.
El empleado, que había salido a una indicación de la maestra, volvió
casi en seguida con una sordomuda rubia, robusta, de cara alegre,
también vestida de tela de rayas rojizas, con delantal gris: se detuvo
en el umbral y poniéndose colorada, inclinó su cabeza sonriendo.
Tenía cuerpo de mujer y parecía una niña.

La hija de Jorge corrió en seguida a su encuentro, la cogió por un


brazo como a una niña, y la trajo delante de su padre, diciendo con
su gruesa voz: “Ca-ta-li-na Jor-dán”. “¡Ah! ¡La excelente niña!—
exclamó el padre alargando la mano como para acariciarla, pero
pronto la retiró, repitiendo—: La buena muchacha, que Dios la
bendiga y que le dé todo género de venturas, todos los consuelos,
haciéndola feliz, y a todos los suyos; ¡es un honrado operario, un
pobre padre de familia quien se lo desea de todo corazón!”.

La muchacha grande acariciaba a la pequeña, siempre con la


cabeza baja y sonriéndose; el jardinero seguía mirándola como a
una virgen. “Hoy se puede llevar a su hija”, dijo la maestra. “¡Sí, me
la llevo!—respondió el jardinero—. Hoy la llevaré a Condove, y
mañana temprano la volveré a traer. ¡Figúrese si no me la he de
llevar!”. La hija se fué a vestir. “¡Después de tres años que no la veo!
—replicó el jardinero—. ¡Y ahora que habla...! A Condove me la
llevo en seguida. Pero antes quiero dar una vuelta por Turín, con mi
mudita del brazo, para que todos la vean, y llevarla a que la oigan
mis cuatro conocidos. ¡Ah! ¡Hermoso día! ¡Esto se llama un
consuelo! ¡Venga acá ese brazo, Luisa mía!”. La muchacha, que
había vuelto con una manteleta y una cofia, dió el brazo a su padre.
“¡Y gracias a todos!—dijo el padre ya desde la puerta—. ¡Gracias a
todos con toda mi alma! ¡Volveré otra vez para repetir a todos las
gracias!”. Se quedó un momento pensativo: luego, separándose
bruscamente de la muchacha, volvió pies atrás, hurgándose con una
mano en el bolsillo del chaleco y gritando como un furioso: “Pues
bien: soy un pobre diablo; pero aquí están veinte liras para el
Instituto: ¡una moneda de oro bien hermosa!”. Y dando un gran
golpe sobre la mesa, dejó el doblón sobre ella. “No, no, buen
hombre—dijo conmovida la maestra—. Recoja usted su dinero. A mí
no me corresponde recibirlo. Ya vendrá cuando esté el director.
Tampoco él lo aceptará, esté seguro. Ha trabajado usted tanto para
ganarlo, ¡pobre hombre...! Todos le quedaremos agradecidos, lo
mismo que si lo recibiéramos”. “No, yo lo dejo—repitió el jardinero—;
y luego... ya veremos”. Pero la maestra le volvió la moneda al
bolsillo, sin darle tiempo para rechazarla. Entonces se resignó,
meneando la cabeza; envió con toda rapidez un beso, con la mano,
a la muchacha grande, saludó a la maestra, y cogiendo de nuevo a
su hija, se lanzó fuera de la puerta. “Ven, ven, hija mía, ¡pobre hija
mía, mi tesoro!”. La hija le decía con su voz gruesa: “¡Oh, qué sol
tan her-mo-so!”.
JUNIO

GARIBALDI
MAÑANA ES FIESTA NACIONAL

Junio 3
OY es día de luto nacional. “¡Ayer noche ha muerto
Garibaldi! ¿Sabes quién era? Es el que libertó a diez
millones de ciudadanos de la tiranía de los Borbones de
Italia. ¡Ha muerto a los sesenta y cinco años! Nació en
Niza, y era hijo de un capitán de barco. A los ocho años
libró la vida a una mujer; a los trece sacó a salvo una barca llena de
compañeros náufragos; a los veintisiete salvó de las aguas, en
Marsella, a un jovencito que se ahogaba; a los cuarenta y uno evitó
el incendio de un barco, en el océano. Combatió diez años en
América por la libertad de un pueblo extranjero; luchó en tres
guerras contra los austríacos por la libertad de la Lombardía y del
Trentino; defendió a Roma contra los franceses en 1849; libró a
Palermo y a Nápoles en 1860; volvió a combatir por Roma en 1867;
guerreó en 1870 contra los alemanes en defensa de Francia. Tenía
en su alma la llama del heroísmo y el genio de la guerra. Entró en
combate cuarenta veces, y salió victorioso treinta y siete. Cuando no
peleó, trabajó para vivir, encerrándose en una isla solitaria, a cultivar
la tierra. Fué maestro, marinero, trabajador, negociante, soldado,
general, dictador. Era grande, sencillo y bueno. Odiaba a todos los
opresores, amaba a todos los pueblos, protegía a todos los débiles;
no tenía otra aspiración que el bien; rechazaba los honores,
despreciaba la muerte, adoraba a Italia. Cuando lanzaba el grito de
guerra, legiones de valerosos corrían a él de todas partes: hubo
señores que abandonaron sus palacios, artesanos sus talleres y
jóvenes sus aulas, para ir a combatir, iluminados por el sol de su
gloria. En la guerra usaba blusa roja. Era fuerte, rubio, hermoso; en
el campo de batalla, un rayo; en los sentimientos, un niño; en los
dolores, un santo. Miles de italianos han muerto por la patria, felices
en la agonía al verle pasar a lo lejos victorioso; millares hubieran
dado su vida por él; millones le bendijeron y le bendecirán. ¡Ha
muerto! El mundo entero le llora. Tú ahora no lo comprendes. Pero
leerás sus hazañas, oirás hablar de él continuamente en tu vida, y
según vayas creciendo, su imagen crecerá ante tu vista; cuando
seas hombre, le verás gigante; y cuando no estés tú ya en este
mundo, ni vivan los hijos de tus hijos, ni los que nazcan de ellos,
todavía las generaciones verán en lo alto su cabeza luminosa de
redentor de los pueblos, coronada con los nombres de sus victorias,
como si fueran círculo de estrellas, y les resplandecerá la frente y el
alma a todos los italianos al pronunciar su nombre.—Tu padre.”

EL EJÉRCITO
FIESTA NACIONAL

Se retardó siete días a causa de la muerte de Garibaldi

Domingo 11.—Hemos ido a la plaza del Castillo, para ver la revista


de los soldados que desfilaron ante el comandante del cuerpo de
ejército en medio de dos grandes filas de pueblo. Según iban
desfilando al compás de las cornetas y músicas, mi padre me
indicaba los cuerpos y los recuerdos gloriosos de cada bandera.
Iban primero los alumnos de la Academia, que serán oficiales de
ingenieros y de artillería, trescientos aproximadamente, vestidos de
negro, desfilando con una elegancia firme y desenvuelta de
soldados y de estudiantes. Después de ellos pasó la infantería: la
brigada de Aosta, que combatió en Goito y en San Martín, y la
brigada Bérgamo, que combatió en Castelfidardo; cuatro
regimientos, compañía tras compañía, millares de pompones rojos
que semejaban otras tantas dobles guirnaldas larguísimas color de
sangre, tendidas y agitadas por los dos extremos y llevadas a través
de la multitud. Después de la infantería avanzaron los soldados de
ingenieros, los obreros de la guerra, con sus penachos negros de
crin y los galones rojos; y mientras éstos desfilaban, se veían tras de
ellos centenares de largas y derechas plumas que sobresalían por
encima de las cabezas de los espectadores: eran los alpinos, los
defensores de las puertas de Italia, todos ellos altos, sonrosados y
fuertes, con sus sombreros calabreses y las divisas de hermoso
color verde vivo como la hierba de sus montañas. Aún desfilaban los
alpinos, cuando se dejó sentir un estremecimiento en la multitud, y
los cazadores de infantería, el antiguo duodécimo batallón, los
primeros que entraron en Roma por la brecha de Puerta Pía,
morenos avispados, vivos, con los penachos agitados por el viento,
pasaron como una oleada de negro torrente, haciendo retumbar
toda la plaza con agudos sonidos de tromba que semejaban gritos
de alegría. Pero el sonido de su corneta, fué cubierto bien pronto por
un estrépito sordo e ininterrumpido, que anunciaba la artillería de
campaña. Pasaron, gallardamente sentados sobre altos cajones
arrastrados por trescientas parejas de caballos impetuosos, los
bravos soldados de cordones amarillos y los largos cañones de
bronce y de acero, que saltaban y resonaban haciendo temblar la
tierra. Vino luego adelantándose lenta, grave, bella en su apariencia,
fatigosa y ruda, con sus altos soldados y sus poderosos mulos, la
artillería de montaña, que lleva la desolación y la muerte allí donde
llega la planta humana. Pasó por fin al galope, con los cascos
refulgentes, con las lanzas derechas, con las banderas al viento,
deslumbrador de oro y de plata, llenando el aire de polvo y de
relinchos, el magnífico regimiento de caballería de Génova, que diez
veces cayó como un torbellino sobre los campos de batalla, desde
Santa Lucía a Villafranca. “¡Qué hermoso es!”, exclamé yo. Pero mi
padre casi me echó un regaño por haber usado aquella palabra, y
me dijo: “No hay para qué considerar el ejército como un bello
espectáculo. Todos estos jóvenes, llenos de fuerza y de esperanzas,
pueden de un día a otro ser llamados a defender nuestro país, y en
pocas horas caer hechos trizas por las balas y la metralla. ¡Siempre
que oigas gritar en una fiesta ¡viva el ejército!, ¡viva Italia!,
represéntate más allá de los regimientos que pasan, una campiña
cubierta de cadáveres y hecha un lago de sangre, y entonces el viva
al ejército te saldrá de lo más profundo del corazón, y la imagen de
Italia te aparecerá más severa y más grande!”.

ITALIA
Martes 13.—“Saluda a la patria de este modo en los días de sus
fiestas: Italia, patria mía, noble y querida tierra donde mi padre y mi
madre nacieron y serán enterrados, donde yo espero vivir y morir,
donde mis hijos crecerán y morirán; hermosa Italia, grande y
gloriosa desde hace siglos, unida y libre desde ha pocos años; que
esparciste sobre el mundo tanta luz de divinas inteligencias, y por la
cual tantos valientes murieron en los campos de batalla y tantos
héroes en el patíbulo; madre augusta de trescientas ciudades y de
treinta millones de hijos; yo, niño, que todavía no te comprendo y no
te conozco por completo, te venero y te amo con toda mi alma, y
estoy orgulloso de haber nacido de ti y de llamarme hijo tuyo. Amo
tus mares espléndidos y tus sublimes Alpes; amo tus monumentos
solemnes y tus memorias inmortales; amo tu gloria y tu belleza; amo
y venero a toda como a aquella parte preferida donde por vez
primera vi el sol y oí tu nombre. Os amo a todas con el mismo cariño
y con igual gratitud, valerosa Turín, Génova soberbia, docta Bolonia,
encantadora Venecia, poderosa Milán; con la misma reverencia de
hijo os amo, gentil Florencia y terrible Palermo, Nápoles inmensa y
hermosa, Roma maravillosa y eterna. ¡Te amo, sagrada patria! Y te
juro que querré siempre a todos tus hijos como a hermanos; que
honraré siempre en mi corazón a tus hombres ilustres vivos y a tus
grandes hombres muertos; que seré ciudadano activo y honrado,
atento tan sólo a ennoblecerme para hacerme digno de ti, y
cooperar con mis mínimas fuerzas para que desaparezcan de tu faz
la miseria, la ignorancia, la injusticia, el delito; para que puedas vivir
y desarrollarte tranquila en la majestad de tu derecho y de tu fuerza.
Juro que te serviré en lo que pueda, con la inteligencia, con el brazo
y con el corazón, humilde y valerosamente; y que si llega un día en
el que deba dar por ti mi sangre y mi vida, daré mi vida y mi sangre
y moriré elevando al cielo tu santo nombre y enviando mi último
beso a tu bendita bandera.—Tu padre.”

¡TREINTA Y DOS GRADOS!


Viernes 16.—En los cinco días siguientes a la fiesta nacional, el
calor ha ido creciendo hasta tres grados más. Ya estamos en pleno
verano: todos comienzan a estar cansados, a perder los hermosos
colores sonrosados de la primavera; las piernas y los cuellos se
adelgazan, las cabezas se tambalean y los ojos se cierran. El pobre
Nelle, que siente mucho el calor y tiene ya una cara de color de
cera, se queda alguna vez dormido profundamente con la cabeza
sobre el cuaderno; pero Garrón siempre está atento para ponerle
delante un libro abierto, derecho, para que el maestro no lo vea.
Crosi apoya su roja cabeza sobre el banco, de modo que parece
que la han separado del tronco y puesto allí. Nobis se lamenta de
que somos demasiados y viciamos el aire. ¡Ah! ¡Qué esfuerzo hay
que hacer para ponerse a estudiar! Yo miro desde las ventanas de
casa aquellos hermosos árboles que hacen una sombra tan
obscura, donde de muy buena gana iría a correr, y me da tristeza y
rabia el tener que ir a encerrarme entre los bancos de la clase.
Luego me reanimo cuando veo que mi pobre madre se queda
siempre mirándome cuando salgo de la escuela para ver si estoy
pálido; y a cada página de trabajo me dice: “¿Te sientes con fuerza
todavía?”. Y todas las mañanas, al despertarme a las seis para
estudiar la lección: “¡Ánimo! No faltan ya más que tantos días; luego
quedarás libre y descansarás, irás a la sombra de los árboles”. Sí;
tiene sobrada razón mi madre al recordarme los muchachos que
trabajan en los campos bajo los rayos de un sol que abrasa, o en las
arenas blancas a orillas de los ríos, que ciegan y queman, o de las
fábricas de vidrios, que se pasan todo el día inmóviles con la cara
inclinada sobre una llama de gas; todos se levantan más pronto que
nosotros, y ninguno de ellos tiene vacaciones. ¡Valor, por
consiguiente! También en esto es el primero de todos Deroso, que
no siente ni el calor ni el sueño, siempre vivo y alegre, con sus rizos
largos como en el invierno, estudiando sin cansarse y manteniendo
despiertos a todos los que tiene alrededor, como si refrescase con
su voz el aire. Otros dos hay que siempre están atentos y
despiertos: el testarudo Estardo, que se pincha en los labios para no
dormirse, y cuanto más cansado está y más calor hace, tanto más
aprieta los dientes y abre los ojos que parece que se quiere comer
al maestro; y el traficante Garofi, enteramente ocupado en fabricar
abanicos de papel rojo, adornados con figuritas de cajas de cerillas,
que luego vende a dos céntimos cada uno. Pero el más valiente es
Coreta: ¡pobre Coreta, que se levanta a las cinco para ayudar a su
padre a llevar leña! A las once, en la escuela, ya no puede tener los
ojos abiertos, y se le dobla la cabeza sobre el pecho. Y sin embargo,
se sacude, se pega cachetes en la nuca, pide permiso para salir, y
se lava la cara, y hace que los que están cerca le empujen y le
pellizquen. Pero esta mañana no pudo resistirlo, y se durmió con
profundísimo sueño. El maestro le llamó fuertemente: “¡Coreta!”. No
le oyó. El maestro, irritado repitió: “¡Coreta!”. Entonces el hijo del
carbonero, que vive al lado de su casa, se levantó y dijo: “Ha estado
trabajando desde las cinco hasta las siete, llevando haces de leña”.
El maestro le dejó dormir, y continuó explicando la lección durante
otra media hora. Luego se fué al banco de Coreta, y soplándole muy
despacio en la cara, le despertó. Al verse delante al maestro,
retrocedió amedrentado. Pero el maestro le cogió la cabeza entre
las manos y le dijo besándole: “No te regaño, hijo mío. No es el
sueño de la pereza el que sientes, sino el sueño del cansancio”.
MI PADRE
Sábado 17.—“Seguramente que ni tu compañero Coreta ni Garrón
responderían a su padre como tú has respondido esta tarde al tuyo,
Enrique. ¿Cómo es posible? Tienes que jurarme que no volverá a
pasar esto nunca mientras yo viva. Siempre que a una reprensión
de tu padre te venga a los labios una mala respuesta, piensa en
aquel día, que llegará irremisiblemente, en que tenga que llamarte a
su lecho para decirte: ‘Enrique, te dejo’. ¡Oh, hijo mío! Cuando oigas
su voz por última vez, y aun después por mucho tiempo; cuando
llores en su cuarto abandonado, en medio de todos los libros que él
ya no abrirá más, entonces, recordando que alguna vez le faltaste al
respeto, te preguntarás a ti mismo: ‘¿Cómo es posible?’. Entonces
comprenderás que él ha sido siempre tu mejor amigo, que cuando
se veía obligado a castigarte sufría más que tú, y que siempre que
te ha hecho llorar ha sido por tu bien; entonces te arrepentirás y
besarás llorando aquella mesa sobre la cual ha trabajado y sobre la
cual gastó su vida en bien de sus hijos. Ahora no comprendes; él te
esconde todo su interior, excepto su bondad y su cariño. Tú no
sabes que a veces está tan quebrantado por el cansancio, que
piensa que vivirá pocos días, y que en tales momentos no habla
más que de ti, y no tiene más pena en su corazón que el dejarte sin
protección y pobre. ¡Y cuántas veces, pensando en esto, entra en tu
cuarto mientras duermes y se queda mirándote con la luz en la
mano, y haciendo un esfuerzo, cansado y triste, vuelve a su trabajo!
Y ni siquiera te das cuenta de que en muchas ocasiones te busca,
está contigo porque tiene una amargura en el corazón y disgustos
que todos los hombres sufren en el mundo, y te busca a ti como a
un amigo para confortarse y olvidar, sintiendo necesidad de
refugiarse en tu cariño, para volver a encontrar la serenidad y el
valor. Piensa, por consiguiente, ¡qué doloroso debe ser para él
cuando, en lugar de encontrar afecto en ti, encuentra frialdad e
irreverencia! ¡No te manches jamás con tan terrible ingratitud!
Piensa que aun cuando fueses bueno como un santo, no podrías
nunca recompensarlo bastante, por lo que ha hecho y hace
continuamente por ti. Y piensa a la vez que sobre la vida no se
puede contar: una desgracia te podría arrebatar a tu padre, mientras
todavía eres muchacho, dentro de dos años o tres meses, o quizá
mañana mismo. ¡Ah! ¡Pobre Enrique mío! ¡Cómo verías cambiar
todo a tu alrededor entonces! ¡Qué vacía y desolada te parecería la
casa, solo, con tu pobre madre, vestida de negro. Vete, hijo; ve
donde está tu padre: está trabajando en su cuarto: ve de puntillas
para que no te sienta entrar; ve a poner tu frente sobre sus rodillas y
a decirle que te perdone y te bendiga.—Tu madre”.

EN EL CAMPO
Lunes 19.—Mi buen padre me perdonó una vez más y me dejó ir a
la jira que habíamos proyectado con el padre de Coreta, el vendedor
de leña. Todos teníamos necesidad de alguna bocanada de aire en
las colinas. Fué una diversión. Ayer a las dos nos encontramos en la
plaza de la Constitución, Deroso, Garrón, Garofi, Coreta padre e
hijo, Precusa y yo, con nuestras provisiones de frutas, de salchichón
y de huevos duros, teníamos vasitos de cuero y de hoja de lata;
Garrón llevaba una calabaza con vino blanco; y el pequeño Precusa,
con su blusa de maestro herrero, tenía bajo el brazo un pan de dos
kilos. Fuimos en ómnibus hasta la Gran Madre de Dios, y luego,
arriba, a escape por las colinas. ¡Había una sombra, un verde y una
frescura...! Dábamos volteretas en la pradera, metíamos la ara en
todos los arroyuelos y saltábamos a través de todos los fosos.
Coreta padre nos seguía a lo lejos, con la chaqueta al hombro,
fumando en su pipa de yeso y de cuando en cuando nos
amenazaba con la mano para que no nos desgarrásemos los
pantalones. Precusa silbaba; nunca le había oído silbar; Coreta, hijo,
hacía de todo, según andábamos; sabe hacer de todo aquel
hombrecillo, con su navajita de un dedo de larga: ruedas de molino,
tenedores, jeringuillas; y quería llevar las cosas de los demás, e iba
cargado que sudaba de firme, pero siempre ligero como una cabra.
Deroso a cada paso se detenía para decirnos los nombres de las
plantas y de los insectos; yo no sé cómo se arregla para saber tanta
cosa. Garrón iba comiendo su pan en silencio; pero no es el mismo
que pegaba aquellos mordiscos que era un gusto verlo, ¡pobre
Garrón!, después que perdió a su madre. Siempre es excelente,
bueno como el pan: cuando uno de nosotros tomaba carrera para
saltar un foso, corría al otro lado para tenderle las manos; y porque
Precusa tenía miedo de las vacas, porque siendo pequeño le habían
atropellado, siempre que pasaba una, Garrón se le ponía delante.
Subimos hasta Santa Margarita, y luego abajo por la pendiente
dando saltos y echándonos a rodar. Precusa, trabándose en un
arbusto, se hizo un rasgón en la blusa, y allí se quedó avergonzado
con su jirón colgando, hasta que Garofi, que tiene siempre alfileres
en la chaqueta, se lo sujetó de manera que no se veía, mientras que
él no cesaba de decirle: “¡Perdóname! ¡Perdóname!”. Luego, vuelta
a correr de nuevo. Garofi no perdía su tiempo en el viaje: cogía
hierbas para ensalada, caracoles y todas las piedras que brillaban
algo se las metía en el bolsillo, pensando en que podrían tener algo
de oro o de plata. Siempre adelante corriendo, echándonos a rodar,
trepando a la sombra y al sol, arriba y abajo por todas las
elevaciones y senderos, hasta que llegamos sin fuerzas y sin aliento
a la cima de una colina, donde nos sentamos a merendar en la
hierba. Se veía una llanura inmensa y todos los Alpes azules con
sus crestas blancas. Todos nos moríamos de hambre, y parecía que
el pan se evaporaba. Coreta, padre, nos presentaba los pedazos de
salchichón sobre hojas de calabaza. Todos nos pusimos a hablar a
la vez de los maestros, de los compañeros que no habían podido
venir y de los exámenes. Precusa se avergonzaba algo de comer, y
Garrón le metía en la boca lo mejor de su parte a la fuerza. Coreta
estaba sentado al lado de su padre con las piernas cruzadas, más
bien parecían dos hermanos que no padre e hijo, al verlos
colocados tan inmediatamente los dos, y alegres y con los dientes
tan blancos... El padre trincaba que era un gusto; apuraba hasta los
vasos que nosotros dejábamos mediados, diciéndonos: “A vosotros,
estudiantes, sin duda os hace daño el vino; los vendedores de leña
son los que tienen necesidad de él”. Luego, cogiendo por la nariz a
su hijo, le zarandeaba, diciéndonos: “Muchachos, quered mucho a
éste, que es un perfecto caballero: ¡os lo digo yo!”. Todos nos
reíamos, excepto Garrón. Y seguía bebiendo. “¡Qué lástima! Ahora
estáis todos juntos como buenos amigos, y dentro de algunos años,
¡quién sabe! Enrique y Deroso serán abogados o profesores, o qué
sé yo, y vosotros cuatro en una tienda, o en un oficio, o el diablo
sabe dónde. Entonces, buenas noches, camaradas”. “¡Qué!—
respondió Deroso:—para mí, Garrón será siempre Garrón; Precusa
será siempre Precusa, y los demás lo mismo; aun cuando llegase a
ser emperador de todas las Rusias, donde estén ellos iré yo”.
“¡Bendito seas!—exclamó Coreta, padre, alzando la cantimplora—;
así se habla, ¡vive Cristo! ¡Venga esa mano! ¡Vivan los buenos
compañeros, y viva también la escuela, que crea una sola familia
entre los que tienen y entre los que no tienen!”. Tocamos todos la
cantimplora con los vasos de cuero y de hoja de lata, y bebimos por
última vez. Y él gritó, poniéndose en pie y apurando el último sorbo:
“¡Viva el cuadro del cuarenta y nueve! Y si alguna vez vosotros
tuviéseis que formar el cuadro, mucho cuidado con mantenerse
firmes como nosotros, ¡muchachos!”. Ya era tarde: bajamos
corriendo y cantando, y caminando largos trechos cogidos del brazo.
Cuando llegamos al Po obscurecía, y millares de moscas luminosas
cruzaban los aires. No nos separamos hasta llegar a la plaza de la
Constitución, y después de haber combinado el encontrarnos para ir
todos juntos al teatro de Víctor Manuel para ver la distribución de
premios a los alumnos de las escuelas de adultos. ¡Qué hermoso
día! ¡Qué contento hubiera vuelto a casa si no hubiese encontrado a
mi pobre maestra! La encontré al bajar las escaleras de nuestra
casa, casi a obscuras; apenas me reconoció, me cogió ambas
manos, diciéndome al oído: “¡Adiós, Enrique; acuérdate de mí!”.
Advertí que lloraba. Subí y se lo dije a mi madre: “He encontrado a
mi maestra”. “Sí, iba a acostarse”, respondió mi madre, que tenía los
ojos encendidos. Luego, mirándome fijamente, añadió con gran
tristeza: “Tu pobre maestra... está muy mal”.

LA DISTRIBUCIÓN DE PREMIOS A LOS


ARTESANOS
Domingo 25.—Según habíamos convenido, fuimos todos juntos al
teatro de Víctor Manuel a ver la distribución de premios a los
artesanos. El teatro estaba adornado como el día 14 de marzo y
lleno de gente; pero casi todas eran familias de obreros. El patio
estaba ocupado por los alumnos y alumnas de la escuela de canto
coral, los cuales cantaron un himno a los soldados muertos en
Crimea, tan hermoso, que cuando terminó todos se levantaron
palmoteando y gritando hasta que lo repitieron. Inmediatamente
comenzaron a desfilar los premiados ante el alcalde, el gobernador
y otros muchos que les daban libros, libretas de la Caja de Ahorros,
diplomas y medallas. Allá, en un rincón del patio, vi al albañilito,
sentado al lado de su madre; en otro lado estaba el director, y detrás
de él, la cabeza roja de mi maestro de segundo año. Primeramente
fueron pasando los alumnos de las escuelas nocturnas de dibujo:
plateros, escultores, litógrafos y también carpinteros y albañiles;
luego, los de la Escuela de Comercio; después, los del Liceo
Musical, entre los cuales iban varias muchachas, obreras, vestidas
con los trajes del día de fiesta, siendo saludadas con grandes
aplausos. Por fin pasaron los alumnos de las escuelas nocturnas
elementales, y era un bonito espectáculo verles desfilar, de todas
edades, de todos los oficios y vestidos de muy diversos modos:
hombres con el pelo entrecano, muchachos y operarios de larga
barba negra. Los pequeños se presentaban con mucha
desenvoltura, los hombres algo turbados, la gente aplaudía a los
más viejos y a los más jóvenes. Pero ninguno reía entre los
espectadores: al contrario de lo que sucedía el día de nuestra fiesta,
todos estaban atentos y serios. Muchos de los premiados tenían a
su mujer y a sus hijos en el patio, y había niños que al ver pasar a
su padre por el escenario, le llamaban por su nombre y en alta voz,
señalándole con la mano y riendo fuertemente. Pasaron labradores
y mozos procedentes de la escuela Boncompañi. De la escuela de
la Ciudadela se presentó un limpiabotas, a quien conoce mi padre, y
el gobernador le dió un diploma. Tras él veo venir un hombre tan
grande como un gigante, y a quien me parecía haber visto otras
veces... ¡Era el padre del albañilito, que había ganado el segundo
premio! Me acordé de cuando le había visto en la buhardilla, al lado
de la cama de su hijo enfermo; busqué a éste con la vista en las
butacas: ¡pobre albañilito! Estaba mirando a su padre con los ojos
brillantes, y para esconder la emoción, ponía el hocico de liebre. En
aquel momento oí un estallido de aplausos; miré al escenario: un
pequeñito deshollinador, con la cara lavada, pero con el traje de
trabajo; el alcalde le hablaba, teniéndole cogida una mano. Después
del deshollinador vino un cocinero. Luego se presentó a recoger la
medalla un barrendero del Ayuntamiento, de la escuela Raniero.
Sentí en mi corazón un no sé qué, algo así como un grande afecto y
un gran respeto al pensar cuánto habían costado aquellos premios a
todos aquellos trabajadores, padres de familia y llenos de
preocupaciones; cuántas fatigas añadidas a las suyas, cuántas
horas robadas al sueño, que tanto necesitan, y también cuántos
esfuerzos de parte de su inteligencia, sin tener hábitos de estudios,
y de sus manos encallecidas por el trabajo. Pasó un muchacho de
taller, al cual se veía que su padre le había prestado la chaqueta
para aquella ocasión: le colgaban las mangas tanto, que no tuvo
más remedio que recogérselas allí mismo para poder coger su
premio; muchos rieron, pero pronto quedó sofocada la risa por los
aplausos. Apareció luego un viejo con la cabeza calva y la barba
blanca. Más tarde, soldados de artillería de los que venían a la
escuela de adultos de nuestra sección; luego, guardas de
Consumos y vigilantes municipales de los que dan la guardia en
nuestras escuelas. Por fin los alumnos de la escuela de música
coral cantaron otra vez el himno a los muertos en Crimea; pero con
tanto vigor, con tal fuerza de expresión que brotaba francamente del
alma, que la gente no aplaudió más y salieron todos conmovidos,
lentamente y sin producir ruido. A los pocos minutos la calle estaba
llena de gente. Delante de la puerta del teatro estaba el
deshollinador, con su libro encuadernado en tela roja, y una porción
de señores que le rodeaban, haciéndole mil preguntas. Muchos
operarios, muchachos, guardias, maestros, se saludaban de un lado
a otro de la calle. Mi maestro de segundo año salió entre dos
soldados de artillería. Se veían mujeres de obreros con sus niños en
brazos, los cuales llevaban en sus manitas el diploma del padre,
enseñándolo orgullosos a las gentes.
MI MAESTRA, MUERTA
Martes 27.—Mientras nosotros estábamos en el teatro de Víctor
Manuel, mi pobre maestra agonizaba. Murió a las dos. El director
estuvo ayer mañana a darnos la noticia en la escuela. Y añadió:
“Los que de vosotros hayan sido alumnos suyos, saben qué buena
era y cuánto quería a los niños; fué una madre para ellos. ¡Ahora ya
no existe! Una terrible enfermedad venía consumiéndola hacía
mucho tiempo. Si no hubiese tenido que trabajar para ganarse el
pan, se hubiera curado, o, a lo menos, su vida acaso se habría
podido prolongar algunos meses con el descanso de una licencia.
Pero quiso estar entre sus niños hasta el último día. El sábado 17
por la tarde, se despidió de ellos con la seguridad de no volver a
verlos, les aconsejó, besó a todos y se fué sollozando. ¡Ya ninguno
volverá a verla! Niños, acordaos de ella”. El pequeño Precusa, que
había sido alumno suyo de enseñanza primaria superior, inclinó la
cabeza sobre el banco y se echó a llorar. Ayer tarde, después de
clase, fuimos todos juntos a la casa mortuoria para acompañar el
cadáver a la iglesia. Había en la calle un carro fúnebre con dos
caballos, y mucha gente alrededor que hablaba en voz baja. El
director, los maestros y las maestras de nuestra escuela, y también
de otras secciones donde ella había enseñado años atrás, estaban
todos allí, los niños de su clase; llevados de la mano por sus
madres, iban con velas; y muchísimos de otras, y unas cincuenta
muchachas de la sección Bareti, bien con coronas, bien con ramitos
de rosas en la mano. Sobre el ataúd habían colocado ya muchos
ramos de flores, y pendiente del carro una corona grande de
siemprevivas, con la siguiente inscripción en caracteres negros: A
su maestra, las antiguas alumnas de la cuarta. Bajo esta corona
grande iba colocada otra pequeña, llevada por sus niños. Se veían
entre la multitud muchas criadas de servicio enviadas por sus amos,
con velas, y dos lacayos de librea con antorchas encendidas; un
señor, rico, padre de un alumno de la maestra, había hecho ir su
carruaje, forrado de seda azul. Todos se apiñaban ante la puerta.
Varias niñas enjugaban sus ojos llenos de lágrimas. Estuvimos
esperando largo rato en silencio. Finalmente, bajaron la caja.
Cuando algunos niños vieron la mortaja, se echaron a llorar, y
comenzó a gritar uno, como si sólo en aquel momento se hubiera
penetrado de que su maestra había muerto dando unos sollozos tan
convulsivos, que tuvieron que retirarle. La procesión se puso en
orden lentamente y comenzó a moverse: Iban primero las hijas del
Refugio de la Concepción, vestidas de verde; luego, las hijas de
María, de blanco con lazos azules; luego, los sacerdotes; detrás del
carro, los maestros y las maestras, los alumnos de la primera
superior y los demás, y, por fin, la muchedumbre en tropel. La gente
se asomaba a las ventanas y las puertas, y al ver a todos los
muchachos y la corona, decían: “Es una maestra”. Aun entre las
mismas señoras que acompañaban a los más pequeños, había
algunas que lloraban. Así que llegamos a la iglesia, bajaron la caja
del carro y la pusieron en el centro de la nave, delante del altar
mayor; las maestras depositaron en ella sus coronas, los niños la
cubrieron de flores, y la gente toda que se había colocado alrededor,
con las hachas encendidas, en medio de la obscuridad del templo,
comenzó a cantar las oraciones. En seguida el sacerdote dijo el
último amén, apagaron todas las hachas y salieron
apresuradamente, quedándose sola la maestra. ¡Pobre maestra, tan
buena como ha sido conmigo, tan paciente, con tantos años como
ha trabajado! Ha dejado sus pocos libros a los alumnos, a uno un
tintero, a otro un cuadrito, todo lo que poseía. Dos días antes de
morir, dijo al director que no dejase ir a los más pequeños
acompañándola, porque no quería que llorasen. Ha hecho siempre
el bien, ha sufrido, ha muerto. ¡Infeliz maestra, ha quedado sola en
la obscura iglesia! ¡Adiós! ¡Adiós para siempre, mi buena amiga,
dulce y triste recuerdo de mi infancia...!

GRACIAS
Miércoles 28.—Mi pobre maestra ha querido terminar el año escolar;
tres días antes de terminar las lecciones se ha ido. Pasado mañana
iremos todavía a clase para oír leer el último cuento mensual,
Naufragio; luego... se acabó. El sábado 1.º de julio, los exámenes.
Otro año; por consiguiente, ¡ha pasado el cuarto! Y si no se hubiese
muerto la maestra, habría pasado bien. Reflexiono sobre lo que
sabía el pasado octubre, y me parece que sé bastante más:
encuentro varias cosas nuevas en la mente; soy capaz de decir y
escribir mejor que entonces lo que pienso; podría también hacer
cuentas para muchos mayores que no las saben sacar y ayudarles
así en sus negocios; comprendo con más claridad casi todo lo que
leo. Estoy contento... Pero ¡cuántos me han impulsado y ayudado a
aprender, quien de un modo, quien de otro, en casa, en la escuela,
por la calle, en todas partes donde he ido y he visto algo! Yo doy
gracias a todos en este momento. Doy gracias a ti en primer lugar,
mi buen maestro, que has sido tan indulgente y afectuoso conmigo,
y para quien representa un trabajo cada uno de los conocimientos
nuevos de que ahora me vanaglorio. Te doy gracias a ti, Deroso, mi
admirable compañero, que con tus explicaciones prontas y amables
me has hecho comprender tantas veces cosas difíciles, y salvar
muchos escollos en los exámenes; a ti también, Estardo, fuerte y
valeroso, que me has mostrado cómo una voluntad de hierro es
capaz de todo; a ti, Garrón, generoso y bueno, que haces generosos
y buenos a todos los que te conocen, y también a vosotros, Precusa
y Coreta, que me habéis dado siempre ejemplo de valor en los
sufrimientos y de serenidad en el trabajo; y al daros gracias a
vosotros, doy gracias a todos los demás. Pero sobre todos, te doy
gracias a ti, padre mío, a ti, mi primer maestro, mi primer amigo, que
me has ofrecido tantos buenos consejos y enseñado tantas cosas
mientras trabajabas para mí, ocultándome siempre tus tristezas y
buscando de todas maneras cómo hacerme fácil el estudio y
hermosa la vida; a ti, dulce madre mía, mi querido y bendito ángel
custodio, que has gozado con todas mis alegrías y sufrido todas mis
amarguras; que has penado y estudiado conmigo, acariciándome la
frente con una mano mientras que con la otra señalabas al cielo. Yo
hinco mis rodillas ante ti, como cuando era niño, y os doy gracias
con toda la ternura que pusísteis en mi alma durante doce años de
sacrificios y de amor.

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