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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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Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden
our understanding, changes in research methods, professional practices, or medical treatment may become
necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and
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material herein.
ISBN: 978-0-323-91176-4
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
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
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
1
General principles of industrial
corrosion
Sheerin Masroor
Department of Chemistry, A.N. College, Patliputra University, Patna, Bihar, India
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
1.4.1 General or uniform corrosion TABLE 1.1 Metal and their uses in society.
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.
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.
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
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)
atmosphere has several unique properties and 1517–1549.
one of these is its ability to dissolve to some [11] M. Li, C. Dai, B. Yang, Y. Qiao, Z. Zhu, New and green
degree the substances found in the earth’s crust multi-component scaling and corrosion inhibitor for
and atmosphere allowing the water to contain a the cooling water of central air conditioners, J. Mater.
certain number of impurities, which causes Eng. Perform. 26 (2) (2017) 764–772.
[12] H. Ashassi-Sorkhabi, E. Asghari, M. Mohammadi,
problems of scale deposition on the metal surface, Effects of solution hydrodynamics on corrosion inhibi-
e.g., in pipelines, boiler tubes and all kinds of tion of steel by citric acid in cooling water, J. Mater. Eng.
surfaces that are in contact with water [14–21]. Perform. 23 (8) (2014) 2992–3000.
[13] C. Barchiche, C. Deslouis, O. Gil, S. Joiret, P. Refait,
B. Tribollet, Role of sulphate ions on the formation
1.5.2 Specific use of metal in industries of calcareous deposits on steel in artificial seawater;
the formation of green rust compounds during
In lieu of corrosion that is happening in multi- cathodic protection, Electrochim. Acta 54 (13) (2009)
ple components of industrial assemblies, we have 3580–3588.
to look specific remedies to tackle them. One best [14] G.I. Ramses, B. Valdez, M. Kharshan, A. Furman, Mi-
possible way is to use selective metal for specific Schorr, Interesting behavior of Pachycormus discolor
place to avoid corrosion or to make it in minimal Leaves Ethanol Extract as a Corrosion Inhibitor of
Carbon Steel in 1M HCl. A preliminary study.
percentage. Some of examples are given here: Research Article, Hindawi Publishing Corporation,
Int. J. Corros. 8 (2012) 2012. Article ID 980654.
References [15] L. Gustavo, H. Tiznado, G.S. Herrera, W.D. Cruz, B.
Valdez, M. Schorr, Z. Roumen, Use of AES in corrosion
[1] R. Raichev, L.V.B. Valdez, Corrosión de metales y degrada- of copper connectors of electronic devices and equip-
ción de materiales. In: Principios y prácticas de laborato- ments in arid and marine environments, Anti Corros.
rio, Editorial UABC, 2009. 978-6-07775-307-0. Method Mater. 58 (6) (2011) 331–336.
[2] Fergusson J.E., (Eds.), The Heavy Elements: Chemistry, [16] M. Schorr, B. Valdez, R. Zlatev, M. Stoytheva, N. Santillan,
Environmental Impact and Health Effects. Oxford: Per- O. Phosphate, Processing, for phosphoric, acid, produc-
gamon Press; 1990. tion, classical, and, novel, technology, mineral, process-
[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
and titanium, Desalination Water Treat. 51 (13–15) calcium carbonate deposition on iron. Effect of the
(2013) 2521–2528. anion, Electrochim. Acta 54 (9) (2009) 2647–2654.
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
Production of
iron and steel
Crude steel Production products
Pre-consumer
Post-consumer scrap
scrap
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
Design
Monitoring/ Material
Inspection Selection
Corrosion
Prevention And
Control
Considerations
Preventative Processing/
Maintenance Manufacturing
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
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
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].
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.
LEAD WIRE
SOIL SURFACE
Protective Current
FIG. 2.7 A general representation of the sacrificial anode cathodic protection method.
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+
(A) (B)
FIG. 2.8 Illustration of mechanism of protection of metals by (A) an anodic inhibitor and (B) a cathodic inhibitor.
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.
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
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
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
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.”
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”.
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.