A Comprehensive Review of Corrosion Inhibitors

Journal of Molecular Liquids 364 (2022) 119992
Contents lists available at ScienceDirect
Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq
A comprehensive review of corrosion inhibitors employed to mitigate

stainless steel corrosion in different environments
R. Aslam a, M. Mobin a,⇑, S. Zehra a, J. Aslam b
a
Corrosion Research Laboratory, Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh 202002, India
b
Department of Chemistry, College of Science, Taibah University, Yanbu-30799, Al-Madina, Saudi Arabia
a r t i c l e i n f o a b s t r a c t
Article history: In view of the demand of the present day technology a wide variety of materials are being used for var-
Received 31 March 2022 ious industrial projects. The design engineer is responsible for selecting the appropriate material for each
Revised 26 July 2022 project. Aside from its physical properties, the choice of a material also depends on the mechanical and
Accepted 29 July 2022
environmental conditions of the project. One of the most important factors that a project should consider
Available online 4 August 2022
is the propensity of the metallic structures from corrosion and their possible protection. In addition to
other metals, stainless steel (SS) is widely used in various industries such as the petroleum industry
Keywords:
and subjected to various processes such as acid pickling, descaling, and acid cleaning. Some of the com-
Stainless steel corrosion
Green chemistry
mon types of mineral acids used in these processes include hydrochloric acid and sulphuric acid which
Organic compounds are very aggressive and may lead to corrosion if used as such. Various methods such as cathodic protec-
Corrosion inhibitors tion, application of protective coatings, corrosion inhibitors, or a combination of these have been used to
Computational studies prevent metal from corrosion. This review article targets different organic compounds used as inhibitors
to inhibit SS corrosion in different corrosive solutions. The organic compounds which have already been
reported in the literature as inhibitors include plant extracts, surfactants, amino acids, polymers, drug
molecules, ionic liquids, and essential oils. The review gives a vivid account of the contributions made
in recent years (2007 to 2022) based on the literature on the application of organic corrosion inhibitors
for SS in various aggressive environments such as H2SO4, HCl, H3PO4, sulphamic acid, CO2, H2S, and NaCl
at different temperatures. A perusal of literature revealed that most of the research on the corrosion inhi-
bition of SS has been examined in acidic medium. Limited literature is available on SS corrosion ihibition
in seawater condition, where SS suffers from localized corrosion such as pitting and stress corrosion
cracking (SCC). Among various SS examined in the literature austenitic SS 316 has found more attention.
Various research papers based on computational studies are also discussed in the review. The challenges
and outlooks in this area of research have been pointed out with future directions proposed.
Ó 2022 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Corrosion and its socio-economic consequences. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Stainless steel (SS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. Stainless steel properties and uses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4. The global SS market and impact of the recent pandemic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.5. Corrosion of SS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Abbreviations: GNP, Gross National Product; FHWA, United States Federal Highway Administration; NACE, National Association of Corrosion Engineers; TEA-21,
Transportation Equity Act for the Twenty-First Century; SS, Stainless steel; OCP, Open circuit potential; EIS, Electrochemical impedance spectroscopy; XPS, X-ray
photoelectron spectroscopy; STM, Scanning tunneling microscopy; AFM, Atomic force microscopy; XRD, X-ray diffraction; SEM, Scanning electron microscopy; EDS, Energy-
dispersive X-ray analysis; SAMs, Self-assembled monolayers; CYS, L-cysteine; MET, L-methionine; AISI, American Iron and Steel Institute; CV, Cyclic voltammetry; ICP-OES,
Inductively Coupled Plasma Optical Emission spectroscopy; PDM, Point Defect Model; ACADM, Anion-Catalyzed Active Dissolution Model; SCC, Stress corrosion cracking.
⇑ Corresponding author.
E-mail address: drmmobin@hotmail.com (M. Mobin).
https://doi.org/10.1016/j.molliq.2022.119992
0167-7322/Ó 2022 Elsevier B.V. All rights reserved.
R. Aslam, M. Mobin, S. Zehra et al. Journal of Molecular Liquids 364 (2022) 119992
1.6. Specialized types of SS corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2. Corrosion inhibition of SS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Organic corrosion inhibitors: Structural concerns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. The evaluation of corrosion inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3. Surface analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4. Theoretical studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5. Mechanistic aspects of corrosion inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Corrosion inhibitors for SS: A review of the literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1. Acidic environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Hydrochloric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3. Sulphuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.4. Other acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.5. Sodium chloride solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.6. CO2/H2S environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4. Environment containing microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6. Theoretical modeling in corrosion inhibition assessment of SS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7. Drawbacks and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1. Introduction and 5 % of national GNPs. According to previously published statis-

tics, global economic losses due to corrosion in the year 2016
1.1. Corrosion and its socio-economic consequences totaled the US$ 2.5 trillion, accounting for 3.5 % of global GDP
[4]. From 2011 to 2012, the Central Electrochemical Research Insti-
Corrosion destroys metallic and non-metallic materials over tute used the NBS input/output economic model to assess the cost
time because of chemical and electrochemical interactions with of corrosion in India. The direct cost was $26.1 billion, or 2.4 % of
their surroundings [1]. Refined metals which are considered in a gross domestic product. The cost of corrosion which could have
higher energy state release energy, thus reverting to their natural been avoided was US$ 9.3 billion, or 35 % of the total cost. The indi-
chemically combined state of lower energy in the form of ores rect cost was US$ 39.8 billion, or 3.6 % of gross domestic product
and stable compounds. Corrosion of iron and steel accounts for a [2]. According to the recently available corrosion cost study [2],
large portion of this loss, although many other metals can also cor- the cost of corrosion in India is projected to be 4.2 % of GDP. In
rode. Corrosion damage might result in fluid or gas leaks. Even addition to the direct financial costs of corrosion, there are indirect
more damaging is a structure’s loss of strength due to corrosion costs such as lost opportunities and natural assets, possible risks,
and eventually breakdown of structure. As a result, metal corrosion and so forth.
is of vast economic and industrial concern requiring sustained Most corrosion processes are electrochemical. The two primary
research for its potential solutions. Corrosion causes structural ubiquitous reactions that keep a corrosion process continuing are
damage to equipment and components made of metals and alloys hydrogen evolution (prevalent in acidic media) and oxygen reduc-
in construction plants, petrochemical refining, ore mining, fertil- tion (prevalent in neutral or alkaline environments). Corrosion is
izer production, energy generation, and other industrial units, caused by a variety of factors, the most prevalent of those are
resulting in flow interruptions, toxic leakages, and plant shut- the metal’s composition, atomic structure, micro,and macroscopic
downs, industrial downtime, and hefty renovation expenditures. imperfections, and stress response (tensile, compressive, and cyc-
Cost studies have been conducted in several nations to calculate lic); the environment and its chemical nature, quality, and quantity
the total monetary losses due to corrosion [2]. Considering the ear- of reactive species, pressure, temperature, the metal-environment
lier corrosion cost studies, in the late 1970 s, the first investigation interface, metal oxidation, and dissolution kinetics in solution [5].
on corrosion losses was undertaken in the United States. In 1978,
$70 billion was squandered, equal to around 5 % of the country’s
GNP (Gross National Product) [2]. In 2002, the United States Fed- 1.2. Stainless steel (SS)
eral Highway Administration (FHWA) produced ground-breaking
research quantifying the cost of direct corrosion in the industrial Because of its superior mechanical characteristics and abun-
sector. The study was initiated by the National Association of Cor- dance of ores, iron has played a significant role in human civiliza-
rosion Engineers (NACE) International as part of the Transportation tion since its initial production around 4,000 years ago. Iron is
Equity Act for the Twenty-First Century (TEA-21), which was man- employed in infrastructure, transportation, and manufacturing
dated by US Congress. The anticipated yearly direct cost of corro- more significantly than any other metallic commodity. Steel is
sion was estimated to be US$276 billion, implying a 3.1 % loss in extensively used in various applications such as desalination
GNP [3]. This estimate just considered the direct costs of mainte- plants, construction materials, the pharmaceutical industry, and
nance. Other expenses, including productivity losses, adverse envi- thermal power plants due to its stability, adequate corrosion resis-
ronmental effects, impeded transportation, fatalities, and injuries, tance, high strength, workability, and weldability. Thousands of
were calculated to be equal to the direct costs. Corrosion cost stud- steel grades, each with its chemical composition, have been recog-
ies were also undertaken in various nations. Australia, the United nized, registered, or standardized worldwide, and specific number-
Kingdom, Japan, Germany, Kuwait, Finland, India, China, and Swe- ing systems have been established in various countries to classify a
den. Annual corrosion expenses were estimated to be between 1 large number of alloys.
2
Stainless steel (SS), like steel, is an iron and carbon alloy. The architecture.It gives classic and modern spaces a sleek and contem-
word ‘‘stainless steel” refers to a group of iron-based alloys that porary aesthetic while maintaining their usefulness.
contain at least 11 % chromium and additional elements like nitro- Corrosion resistance:Because SS is very resistant to corrosion,
gen, sulfur, silicon, niobium, and molybdenum. Due to its charac- it may resist rust and water stains formation. Therefore, SS is used
teristics, SS is one of the most widely used construction in both outdoor and indoor applications under varying pressures
materials in today’s industrial society [6]. Stainless steel alloys and temperatures. This attribute of stainless steel is due to the
are available in four main types: austenitic, ferritic, martensitic, addition of chromium to the iron, which generates a fine layer over
and duplex, which are used in technological applications that the steel when exposed to oxygen to safeguard it.
demand strong corrosion resistance. Stainless steels are often used Recyclability: The majority of the stainless steel is recycled.
as construction materials in aggressive environments such as Its qualities do not deteriorate when recycled, allowing it to be
nuclear, chemical plants, biomedical implants, civil engineering reused continuously and therefore saving natural resources.
fixations, heat exchangers, oil extraction drilling rigs, the dairy Temperature tolerance: SS has high-temperature tolerance
industry, beverage industry, and wastewater treatment, etc. [7– depending on the type.
9]. The development of a protective layer on the surface with a
thickness of a few nanometers (1–4 nm) is credited with their
exceptional corrosion resistance [10]. Stainless steel elements react 1.4. The global SS market and impact of the recent pandemic
with oxygen in water and air to generate a thin, stable coating con-
taining corrosion products such as metal oxides and hydroxides. According to the report of Grand View Research, Inc., the global
When chromium combines with oxygen, it contributes signifi- SS market was worth USD 111.4 billion in 2019 and is expected to
cantly to the production of this corrosion product layer. The steel’s grow at a compound annual growth rate (CAGR) of 6.3 % in revenue
chromium reacts quickly with the atmospheric oxygen, which from 2020 to 2027 [11]. In that order, Asia Pacific contributes the
develop a thin oxide film on the surface. In contrast to iron oxide most revenue to the target market, followed by North America,
(Fe2O3), that develops flaky and corrosive rust, chromium oxide Europe, Latin America, and the Middle East and Africa. In the next
(Cr2O3) sticks to steel. As a consequence, it acts as a protective ten years, market growth is expected to be driven by several end-
layer. The chromium oxide acts as a passive layer, keeping the iron user industries such as automotive, energy & power, aerospace,
in the alloy safe from the environment’s air and water. This layer and industrial machines. Furthermore, over the forecast period, ris-
gives stainless steel its anti-rust properties as well as a smooth, ing demand for corrosion-resistant alloy in the defense sector is
tarnish-free surface. However, the alloy composition as well as expected to propel market expansion in the area. Consumer prod-
the environmental conditions to which such stainless steel is sub- ucts and heavy industry, according to the report, have the largest
jected impact the behavior of the passive film. market share of stainless steel in 2019 (Fig. 1) [11]. This is due to
a growth in the use of consumer goods such as kitchenware, med-
ical equipment, food and catering, and cars, which is expected to
1.3. Stainless steel properties and uses drive up product demand in the coming years. The need for build-
ings and infrastructure is anticipated to rise because of rapid
The following are the top benefits of utilizing SS: urbanization and a growing global population. According to the
Strength: The strength of stainless steel, which it retains at United Nations’ 2017 World Population Prospects, the global pop-
both very high and very low temperatures, is one of the main rea- ulation would reach 8.6 billion in 2030 and 1.2 billion more in
sons it is so popular. 2050. Building and construction are important end-use industries
Cleanliness: Because it is one of the most pristine materials, it for SS products because a large amount of SS is required to increase
is excellent for catering and therapeutic applications. Because it the structure’s visual appeal and corrosion resistance. The same, in
does not support bacterial growth and is easy to clean and sterilize, turn, is expected to boost SS demand in the upcoming years. Grow-
it requires minimal upkeep. It’s simple to clean with a swab and ing demand for auto products because of increased automobile
all-purpose cleanser, so it’s perfect for kitchens and hospitals. production increased export, and diversification of the auto sector
Aesthetics:Stainless steel’s strength isn’t its only advantage. It has all contributed to market expansion in recent years. Increasing
also has a beautiful appearance; hence it is frequently used in vehicle production, particularly in the Asia Pacific, the Middle East,
Fig. 1. Global stainless steel market share, by application, 2019 (%).
3
Table 1 ally, the pandemic had an impact on employment and consumer

Types of corrosion facing SS in aggressive media. expenditure. All regular industrial activity was halted for a certain
S. Types of Corrosion Description period, resulting in a fall in production and loss. As COVID-19
No. expanded worldwide, governments have been compelled to cancel
1. Pitting Cavities or holes are formed because of local- public events, travel, and significant infrastructure, construction,
ized corrosion.It occurs when SS is exposed to and rail projects causing steel inventories to surge. Steel prices fell
environments containing because of the increase in stock, which was accompanied by a
chlorides.pH
and the temperature of the surroundings are
decrease in demand. The metals market is expected to face supply
factors to consider. Some alloying elements, and demand disruptions as the number of COVID-19 cases rises
such as N, Mo, and Cr, boost pitting resistance [13].
substantially.
2. Crevice Localized corrosion occurs at the crevice
between two joining surfaces of metals or
between metal and non-metal.It
1.5. Corrosion of SS
happens when a crack between SS and
another material causes chlorides to collect Stainless steel, unlike conventional steel, does not corrode, rust,
or inhibits adequate oxygen levels from or tarnish when exposed to water. This isn’t to imply it’s impervi-
regenerating the steel’s oxide layer.
ous to stains. As we all know, there is no such thing as an ideal
Welding, correct drainage, and the use of
proper gaskets can all help to minimize cre- material. Corrosion might occur if the SS grade is not chosen cor-
vice corrosion by reducing or eliminating rectly. The native protective coating (chromium oxide) can be
accessibility to crevices. removed by caustic process fluids and cleaners, high humidity, or
Crevice corrosion can be prevented by a high saline environment such as seawater, leaving SS exposed
employing a flexible sealant or a more corro-
sion-resistant grade of metal.
to staining. Surface rust removal improves the aesthetic of sur-
3 Galvanic It is called as ‘bimetallic corrosion’. faces, but its significance extends beyond that. If left unchecked,
This happens whenever SS is utilised in a rust can cause pitting and structural damage to products and com-
moist environment with the other metals.Gal- ponents and affect instrumentation performance, contaminant
vanic corrosion has different features depend-
flow pathways, and endurance. However, the majority of SS reacts
ing on the metals employed, the
temperatures, the regions of contact, as well to a variety of substances in predictable ways.
as other
factors.It
can be prevented by using a nonmetallic insu- 1.6. Specialized types of SS corrosion
lator like rubber to separate the metals.
4 General SS has a lower general corrosion rate than
(uniform) other steels.It only happens when the pH of SS corrosion can take on a variety of specialized forms in addi-
corrosion the stainless steel is less than tion to general corrosion. Fortunately, most kinds can be addressed
1.0.At or avoided altogether. Pitting, crevice, galvanic, and uniform corro-
certain concentrations, hydrochloric and sul- sion (Table 1) are the most common types of corrosion in SS, while
phuric acids are very harsh on stainless steel.
5 Galling It occurs when SS parts are forced together.
other types of corrosion occur pretty rarely.
Corrosion isn’t obvious until the components
are removed or disassembled, which is com-
mon with nuts, bolts, and other fasteners.
2. Corrosion inhibition of SS
With threaded parts, lubrication and reduced
force can reduce galling.
4 Weld Decay The other name is intergranular corrosion. Corrosion mitigation strategies such as inhibitors or protective
When SS is heated to a specific temperature coatings that form a corrosion-resistant barrier on the metal sub-
range usually between 550 and 850 °C this strate have been used. Corrosion inhibitors have recently gained
type of corrosion happens. As a result, chro-
a lot of interest as an anti-corrosion approach for SS protection
mium precipitates from the SS and the passi-
vation layer’s ability to regenerate is reduced. because of their ease of use, low cost, and high effectiveness. Cor-
Welding with low carbon SS, such as 304L and rosion inhibitors are chemical substances applied to a corrosive
316L, can help to lessen the impact of weld environment in small doses to prevent metallic items from being
degradation.
corroded [14]. Most inhibitors are hazardous substances, and their
Additives such as titanium or niobium can aid
to stabilise the steel and reduce precipitation
use has been prohibited due to their negative impact on the envi-
during welding. ronment and humans. Corrosion inhibitors have traditionally
This can be mitigated by consistent heating raised safety and environmental concerns in industries [15].
and rapid cooling. Researchers have focused their efforts on developing organic and
6. Stress Corrosion Cracking is caused by tensile forces combined
environmentally sustainable corrosion inhibitors [16–22].
Cracking with corrosive environmental factors.Ferritic
or duplex (i.e. austenitic-ferritic) Using the search term ‘‘Corrosion Inhibitors for Stainless Steel,”
SS are resistant to SCC. a search on the scopus.com platform was undertaken for scholarly
material published between 1940 and 2021. The search’s outcome
is depicted in Fig. 2(a). In the present article, we’ve focused on the
reports published during the last 15 years (Fig. 2b). Fig. 2(b) depicts
and South America, is a major driving force for the SS market. the interest in SS inhibitors during the previous 15 years, as mea-
Many automakers have established offices in India because of gov- sured by the number of papers published during that timeframe.
ernment efforts such as ‘‘Skill India” and ‘‘Make in India,” which We summarize the research on the use of inhibitors for corrosion
have pushed many automakers to acquire high-quality products protection of SS in various aggressive media.
from SS vendors in India, which is expected to drive product Fig. 3 Shows examples of the most used organic corrosion inhi-
demand in the coming years [12]. bitors for SS including amino acids, surfactants biopolymers, drugs,
The COVID-19 is leading the globe into ‘‘uncharted territory,” ionic liquids, plant extracts, essential oils, and agricultural and bio-
which has had a significant impact on the global economy. Glob- mass wastes.
4
Fig. 2. (a) Number of scientific publications on SS corrosion inhibitors between 1940 and 2021. (b) Number of scientific publications on SS corrosion inhibitors between 2007
and 2021. Keyword ‘corrosion inhibitors for SS’ was used to retrieve the data from Scopus on 7/04/2021.
2.1. Organic corrosion inhibitors: Structural concerns organic compounds with polar characteristics having nitrogen,
sulphur, and/or oxygen atoms in the conjugated system have
Corrosion mitigation entails reducing material losses caused been discovered to have good corrosion inhibitory properties of
by corrosion of metallic parts using the most effective and cost- steel in acidic and alkaline circumstances. The most significant
effective method possible and maintaining the safety of operating influences for inhibitor adsorption on metallic surfaces appear
equipment that may fail, collapse, or break down due to corro- to be functional groups, steric factors, aromaticity, electron den-
sion, such as pressure vessels and boilers [23]. Corrosion can be sity at donor atoms, orbital character of donating electrons, and
controlled and prevented in various ways, but the most cost- the inhibitor’s electronic structure [28]. According to the findings,
effective method is to utilize corrosion inhibitors [24–27]. Anodic the inhibitory behavior of the compounds is mediated by some
inhibitors, cathodic inhibitors, passivating inhibitors, film-forming chemical species or molecules in the inhibiting substances, which
inhibitors, vapor phase inhibitors, and adsorption-based inhibi- provide a protective layer between the metal surface and the
tors are all types of corrosion inhibitors that are being used in inhibitors. The generated adsorbate layer shields the metal sur-
corrosion mitigation. The use of organic inhibitors has long been face from the aggressive solution, lowering the metal surface’s
acknowledged as a feasible and efficient approach. Several corrosion rate.
5
Fig. 3. Various sources for natural green corrosion inhibitors.
Fig. 4. Corrosion monitoring and detection methods.
2.2. The evaluation of corrosion inhibitors exacerbated by normal failure methods, for instance, atmospheric
rusting, oxidation, crystallization, chemical solution, galvanic cou-
Before deploying in actual application fields, a set of laboratory pling reactions, and so on, in infrastructures, plants, buildings,
experiments is recommended to evaluate the associated corrosion bridges, etc., utilizing corrosion ’probing’ techniques or devices.
inhibition performance of inhibitors. Fig. 4 shows a wide variety of The laboratory test conditions should be identical to, or as close
corrosion detection and monitoring techniques. Corrosion moni- to, the actual conditions as practicable. Standard methods for
toring is the process of probing, observing, and assessing the determining corrosion rates without and with corrosion inhibitors
change in materials (e.g., metal, concrete, wood, etc.) which are include non-destructive and destructive measuring techniques.
6
In corrosion inhibition testing, the weight loss method is the Adsorption models that are more complex consider issues like
simplest and highly well-recognized way of calculating corrosion surface heterogeneity and the presence of areas with varied
rates. It works by exposing a clean, weighed piece of metal or alloy adsorption energies (Temkin isotherm, expressed as eq. ii) or inter-
to a corrosive environment for a certain period of time, then wash- actions between adsorbed molecules (Frumkin isotherm,
ing the piece to eliminate rust and weighting it to determine loss of expressed as eq. iii). In Temkin adsorption isotherm, a represent
weight. The corrosion rate (typically measured in millimeters per the molecular interaction constant. If the values of a less than 0,
year) is determined. When an inhibitor is applied, the inhibitor lateral attraction interactions occurs between the adsorbed inhibi-
efficiency must be evaluated, considering the corrosion rates in tor compounds; and a greater than 0 indicates lateral repulsion
the absence and presence of the inhibitor [29]. Because imperfec- interactions between adsorbed inhibitor molecules. a takes into
tions in the studied metal sample could drastically alter the analy- the account of adsorbent-adsorbate interactions. Using Frumkin
sis, it is critical to include error bars in these results. As a result, the adsorption isotherm, if the value of ‘a’ comes out to be negative,
measurement’s repeatability should be examined. the repulsion between the adsorbate molecules occurs. In Fre-
Electrochemical methods are frequently used to assess the undlich adsorption isotherm (expressed by eq. iv), the value of
effectiveness of corrosion inhibitors in terms of measuring time. slope (1/n) lies between 0 and 1, measures the heterogeneity of
It can further offer not only corrosion resistance data but also addi- the surface. If the value of 1/n lies nearer to 0 i.e., the surface is
tional mechanistic insight. Potentiodynamic polarisation measure- more heterogeneous.A value of 1/n below unity implies
ments are destructive monitoring techniques that can collect chemisorption whereas 1/n above one is an indication of coopera-
information throughout anodic or cathodic scans in an electro- tive adsorption. Flory-Huggins isotherm model (expressed by eq. v)
chemical cell including both the metal to be studied and the envi- explains the feasibility and spontaneity of the adsorption process
ronment in which the polarisation scan will take place. The sample via the degree of surface coverage of adsorbate molecules.
surface must be prepared before each experiment so that the mea- Although it is evident that selecting the most appropriate model
surement’s initial state is well-defined and consistent from begin- while taking all the parameters into account is difficult, numerous
ning to end. The resulting current vs potential diagram depicts the studies have attempted to fit data using the simplest Langmuir
open circuit potential, active region, passivation area, and gas evo- model. Plotting C/h vs C and evaluating the linearity of the data
lution reactions. To compare data in the literature, statistical anal- can be used to determine whether the Langmuir model applies
ysis is necessary. Another excellent method of electrochemical to a certain set of data. The slope can be used to compute the equi-
measurement is linear polarization resistance. The technique can librium adsorption constant, Kads. As previously established, Kads
be used to estimate the corrosion rate by polarising the material, can be used to compute the free energy of adsorption. The lack
usually in the order of 10 mV, compared to its open circuit poten- of molecular interactions, inadequacy to account for multilayer
tial (OCP) in a three electrodes arrangement [30]. As the material’s coverage (together with all other generic models), and ignoring
potential is changed, a current flows between the working and of heterogeneous surface sites are some of the drawbacks of the
counter electrodes, and the material’s resistance to polarisation Langmuir model. Nonetheless, despite its flaws, it is surprisingly
may be determined by looking at the slope of the potential versus successful and widely utilised.
the current graph. The corrosion rate of the material can then be The determination of adsorption thermodynamic/kinetic
calculated using this resistance [31]. Another widely employed parameters can provide useful information regarding the corrosion
technique is EIS which stands for electrochemical impedance spec- inhibition process [35,36]. Undertaking adsorption investigations
troscopy, and it’s a non-destructive electrochemical technique. The at various temperatures and then plotting the free energy of
electrochemical behavior of a low AC voltage provided at various adsorption vs temperature is one method of calculating the
frequencies is measured by EIS. The electrochemical response is enthalpy and entropy of adsorption. Because enthalpy and entropy
used to build an equivalent circuit made up of electrical compo- are connected, plotting adsorption free energy vs absolute temper-
nents based on a reaction mechanism. In comparison to the weeks ature provides a slope equal to the entropy of adsorption and an
required for an exposure test, an EIS spectrum can be generated in intercept equal to the enthalpy of adsorption.
minutes. Because it comprises the construction of an equivalent The temperature dependency on the corrosion rate can be
circuit modeling the metal solution interface, the main challenges determined employing Arrhenius Eq. as given below:
are connected to data interpretation.
The study of the adsorption isotherm is essential to gain a better
understanding of the corrosion process. With the use of the Table 2
Different types of adsorption isotherm examined in the literature.
adsorption isotherm [32], we can acquire a sense of the equilib-
rium between inhibitor adsorbed and present in the bulk. One of Adsorption Isotherm equation Plot Eq.
the most important aspects in describing the interaction between isotherm
sample and inhibitor is adsorption isotherms. Building adsorption Langmuir C

h ¼ K1ads þ Cwhere C - inhibitor C/h versus (i)
isotherms can give information about the inhibitor’s interaction concentration, h-extent of surface 1/C
with the metal surface (physical or chemical, single or multilay- coverage, and Kads-the equilibrium
adsorption constant
ered, etc.) (Table 2).
Temkin e2ah ¼ Kads Cwhere a is molecular hversus log (ii)
In general, the Langmuir-type isotherm is generally followed in interaction constant C
most of the papers reported on corrosion inhibition of SS. The Frumkin logh
¼ Log b þ 2ahwhere a is the log[C(h/(1- (iii)
ð1hÞC
major assumptions of this isotherm are as follows: (i) Adsorbate coefficient of interaction and b analogues
h)] versus h
molecules adhere to the adsorbent surface’s active sites; (ii) the with the adsorption constant.
Langmuir calculation implies monolayer coverage; and (iii) all Freundluich logh ¼ logKf þ n1 logCwhere Kf and 1/n are log h (iv)
adsorbate-binding sites on the solid surface are the same size Freundlich coefficients versus log
C
and shape, and they have the same affinity for adsorbate molecules
Flory- log Ch ¼ logKads þ xlogð1 hÞWhere, x is logh/C (v)
[33,34]. Using the Langmuir model, the adsorbed adsorbate con- Huggins the number of water molecules replaced versus log
centration is expressed as Eq. (i) where C is the total concentration by the inhibitor (1-h)
of inhibitors in the aqueous solution, Kads is the adsorption equilib- Bockris- h/(1-h)n[h + n(1-h)n-1/nn = Ce-Kads/55.5 h/(1-h) (vi)
rium constant, and h is the surface coverage. Swinkels versus log
C
7
Table 3 reflected to be a successful, green, and cost-effective approach of

Significance of thermodynamic/kinetic parameters frequently calculated in corrosion corrosion measurement. The environmentally benign nature of
inhibition studies.
computational modeling comes from the fact that it does not inter-
Thermodynamic/ Significance fere with the laboratory synthesis of chemical compounds [40,41].
kinetic parameters Computational modeling gives valuable reactivity parameters in
DG°ads The interaction between inhibitor compounds and the relationship by which corrosion inhibition effect of every
metal are frequently categorized as physisorption chemical compound can be clarified prior to their preparations
due to electrostatic contact if G°ads is greater than
20 kJ/mol. When G°ads is greater than 40 kJ/mol,
[40]. By DFT, it can be examined that which molecular sites of com-
chemisorption occurs, which entails charge sharing pound is responsible for interactions with the surface of metal. DFT
or transfer between the inhibitor molecules and the gives many indices such as highest occupied molecular orbital
metal surface to establish coordination bonds. In case, energy (EHOMO), lowest unoccupied molecular orbital energy
20 kJ/mol DG0ads 40 kJ/mol, then there is the
(ELUMO), energy gap (DE), chemical hardness (g), softness (r), elec-
presence of both physical and chemical adsorption.
DH°ads The negative values of H°ads imply the exothermic tronegativity (v), electrophilicity (x), nucleophilicity (e) and
recation, while If H°ads is positive, the adsorption of charge transfer of electron (DN) via which relative potency of
inhibitor molecules is endothermic in nature. To metal/inhibitor interactions can be depicted [35,42,43]. MD or
classify the adsorption as physisorption, the DHoads MC simulations can be used to explain the inhibitor molecules ori-
data is normally less than 40 kJ mol1 and it is greater
entation on the surface of metal and the behavior of inhibitor-
than 100 kJ mol1 for chemisorption
DS°ads The positive value of DS revealed an increasing metal interactions in the mode of adsorption energy (Eads)
disorder and randomness at the solid-solution [44,45]. In recent times researchers and engineers are working
interface during the adsorption process. The on the theoretical modeling for planning of efficient corrosion inhi-
negative value of DS revealed the decreased
bitors. The implementations of investigational methods are costly
randomness at the solid/solution interface.
DEa If the value of Ea is greater than 20 KJ/mol, in behavior. These methods wield undesirable impacts on atmo-
chemisorption occurs, while if it is less than 20 sphere as they release contaminated chemicals and solvents. On
KJ/mol, the adsorption is physical. the contrary, the computational modeling tools (DFT, MD and
MC) are relatively inexpensive, quick, and eco-friendly in behavior.
log CR ¼ logA 2:303RT
Ea
(vii).
where CR is the corrosion rate, Ea is apparent activation energy,
A is the Arrhenius pre-exponential factor, R is the molar gas con- 2.5. Mechanistic aspects of corrosion inhibition
stant and T is the absolute temperature. The energy of activation
(Ea) at different temperatures is determined from the slope, equal The consensus among researchers is that the first stage in the
to -Ea/2.303R of each straight line of the plot log CR versus 1/T.The process of organic molecules inhibiting the corrosion of metals is
importance of thermodynamic/kinetic parameters is shown in their adsorption onto the surface of the metals (substrate) via their
Table 3. functional group (s). As a result, it is necessary to understand the
adsorption behavior of organic molecules (inhibitors) on the metal
surface to comprehend the mechanisms of corrosion inhibition.
2.3. Surface analysis The topography, uniformity, and physicochemical characteristics
(charge, conformation, and chemistry) of the metal surface, the
Metallic surfaces can be characterized using a variety of tech- propagation of the charge in the molecule, the hostile medium
niques, which include X-ray photoelectron spectroscopy (XPS), (electrolyte), and the chemical make-up of the organic molecule
scanning tunneling microscopy (STM), atomic force microscopy all play a role in the adsorption process. The mutual interactions
(AFM), X-ray diffraction (XRD), scanning electron microscopy of all the species present at the phase boundary control the adsorp-
(SEM), Kelvin probe atomic force microscopy, energy dispersive tion of ions or neutral molecules on bare metal surfaces submerged
X-ray analysis (EDS), etc. In the literature, the applicability of these in the solution. These include the adsorbate’s electrostatic, chemi-
techniques in the study of corrosion and inhibition of steels has cal, adsorbate-adsorbent, and adsorbate-solvent interactions with
been explored [37–39]. To overcome the limitations of individual the surface. Depending on the existence of the forces, there are
approaches, a combination of multiple surface analysis methods two forms of adsorption:
is essential in revealing corrosion and corrosion inhibition (a) Chemical adsorption: This kind of adsorption involves the
mechanisms. largely irreversible attachment of a single layer of molecules,
atoms, or ions to the surface through chemical bonds.
2.4. Theoretical studies (b) Physical adsorption: In this type of adsorption, bonds are
formed using weaker Van der Waals forces, whose energy levels
Various experimental methods, including gravimetric measure- are like those of condensation. Adsorption utilizing electrostatic/-
ments, electrochemical studies, and surface analytical measures, van der Waals forces has a lower heat of adsorption than
have widely been used to gain a better understanding of an inhibi- chemisorption. Coulombic interactions as well as other interac-
tor’s adsorption and protection capabilities. However, experimen- tions exist in the case of physisorption between the ions or dipoles
tal measurements are often time-consuming and difficult, as well of the inhibitor and the charged metal surface (Van der Waals
as expensive. Furthermore, the experimental methods for evaluat- forces, hydrogen bonding). Although the adsorption process in this
ing inhibitors often prove insufficient to achieve a thorough link instance is quick, the species that are adsorbing are easily wash-
between the molecular structure and their inhibitory performance. able off the surface. To donate electrons to the unoccupied d-
As a result, computational methodologies such as density func- orbital of transition metals, species with loosely bonded electrons,
tional theory (DFT) and classical Molecular Dynamics (MD) or such as p-electrons in aromatic rings, multiple bonds, or unpaired
Monte Carlo (MC) simulations can be used to quantify adsorption electrons in functional groups containing elements like oxygen,
of inhibitor molecules on metal surfaces. Computational analyses nitrogen, sulfur, or phosphorus, are frequently involved. The per-
are important in interpreting experimental data to understand cor- formance of corrosion inhibition of the sequence homology set of
rosion inhibition processes.The implementation of computational organic substances differing in the heteroatom is usually as fol-
modeling tools, for example, DFT, MD, and MC simulations are lows: Phosphorus > Sulfur > Nitrogen > Oxygen.
8
Furthermore, when a metal contains vacant electron orbitals of 3.2. Hydrochloric acid
low energy, the inhibitors are bonded to the metal surfaces by elec-
tron transfer to the metal to form a coordinate type of bond. There- Thymus vulgaris (T.V) plant leaves extract [47] was examined
fore, the electron transfer from the adsorbed species is favored by as a corrosion inhibitor for 304 L SS and was found to act as a mod-
the presence of the relatively loosely bound electrons. The reason- erate inhibitor. Electrochemical noise tests revealed that the
able elementary processes which were used as a basis to propose potential and current oscillate aperiodically (Fig. 5). With raising
an adsorptive interaction between the inhibitor molecules and inhibitor concentration, the mean potential values move toward
the vacant d-orbitals of the Fe atoms includes: higher positive values. Metastable pitting, an activation-
i) electrostatic attraction between the charged metal and the controlled mechanism, was attributed to the rise in birth–death
charged inhibitor molecules (physical adsorption), transients. Mixed inhibition action of the extract was reported by
ii) vacant d-orbitals of metal atoms such as Fe interacting with the authors. A statistical analysis, however, is not provided. Addi-
lone pair electrons of heteroatoms or protonated molecules such as tionally, no mechanism of action was suggested.
amine and phosphate, The interaction of three inhibitors namely, benzoic acid (C1),
iii) when possible, vacant d-orbital of Fe atoms in the metal para-hydroxybenzoic acid (C2), and 3,4-dihydroxybenzoic acid
interacts with p-electrons in the conjugated bond of inhibitor, and. (C3) procured from Sigma-Aldrich with austenitic AISI 316 SS sur-
iv) a combination of some of these three processes. face in 0.5 M HCl was studied by OCP, PDP, EIS and SEM analysis
The adsorbed inhibitor molecules may form a surface protective [56]. The observed corrosion rates were 0.176 mmpy, 0.103 mmpy
layer that could possibly act as a physical barrier between the and 0.079 mmpy at the 1.0 102 M of C1, C2, and C3 inhibitors,
metal surface and aggressive solution and protect the metal from respectively, suggesting the greatest protection exhibited by C3
further corrosion. These protective layers are also known as inhibitor than C1 and C2. It was found that the adsorption of inhi-
monomolecular layers which can affect both anodic and cathodic bitors followed Vilamil adsorption much better than Langmuir,
reactions and hence inhibit the electrochemical corrosion process. Temkin, Freundlich and El-awady isotherm.The authors added a
deeper theoretical study and therefore their assumption on the
mechanism of inhibition seems to be reliable.
3. Corrosion inhibitors for SS: A review of the literature The inhibition performance of another plant extract obtained
from Salvia officinalis (S. Officinalis) was evaluated and found to
3.1. Acidic environment increase on increasing its concentration and the concentration of
2 g/L of inhibitor showed 96.6% IE in 1 M HCl [57]. The adsorption
Acidic solutions are employed in a variety of industrial pro- process of S. Officinalis extract on 304 SS followed Langmuir
cesses, including acid pickling, cooling systems, chemical and elec- adsorption isotherm. Their work was quite well organized as they
trochemical etching, cleaning, descaling, oil well acidization and reported the exact constituent responsible for the inhibition mech-
petrochemical operations [46–48]. Hydrochloric acid is among anism present in the extract. They further supported their claim
the most frequently utilized acidic medium, with a concentration based on computational chemistry. In another study [58], 1.5 g/L
ranging from 5 to 15%. Sulfuric acid is effective at removing scale of date palm extract efficiently reduced the corrosion of 304 SS
deposits from SS surfaces used in the desalination process [49]. from 0.63 (mmpy) to 0.056 (mmpy) in 1 M HCl. The extract inhib-
Acid cleaning treatments may cause SS corrosion, resulting in sig- ited the anodic reaction of corrosion more efficiently. However, the
nificant financial and environmental losses [50–52]. The use of authors neither reported the characterization of extract nor the
organic compounds to inhibit corrosion of metals during the scale inhibition mechanism. As well as there was no report on the repro-
removal by acid solution is a well-known approach of corrosion ducibility of the experiments and standard deviation/error bars.
protection [53–55]. The anti-corrosive application of synthesized gemini surfactants
The organic inhibitors used to prevent SS corrosion in various i.e., 3-azamethyl-1,5-pentamethylene-bis (N-dodecyl- N,N-
aggressive environments are discussed in the section below: dimethylammonium bromide) (3N-12) and 3-azamethyl-1,5-penta
Fig. 5. In the absence and presence of different concentrations of T.V. plant, EN potential and current records of SS304 in 1.0 mol/L HCl solution [47].
9
methylene-bis(N-octadecyl-N,N-dimethylammonium bromide) from 1.5 mM to 3 mM, according to the EIS investigation. Based on
(3 N-18) differing in number of C = 12 and 18 were utilized to inhi- DGads values, different adsorption mechanism was suggested for
bit AISI 304 SS corrosion. 3 N-18 showed low CMC and higher pro- TMTN12Br and TMTN12I as the former adsorbed physically, how-
tection performance at 100 times lower concentration than 3 N-12. ever, later showed chemisorption. Immersion without an inhibitor
And the maximum protection ability for 3 N-12 was 95 % at 1 mM results in a corrosion rate (CR) of 20.77 mmpy, compared to 0.28
whereas for 3 N-18, 92 % inhibition efficiency was observed at mmpy for 1.5 Mm of TMTN12I and 0.51 mmpy for 3 mM
0.01 mM in 3 M HCl. SEM inspection (Fig. 6) of the sample surfaces TMTN12Br after 24 h.
following exposure to several inhibitory solutions revealed negligi- Shet et al., [61] prepared Schiff base, 4-{[4-(dimethylamino)
ble surface attack. However, the same is not evident on the com- benzylidene] amino}- 5-methyl-4H-1,2,4-triazole-3-thiol
parison of SEM micrographs obtained in blank and inhibited (DBAMTT) and tested its inhibition performance on 316 SS in
systems. 2 M HCl using the concentrations in the range of 0–2000 ppm. Inhi-
In similar condition, the same authors in another study, bition performance increased on increasing concentration, solution
reported the protection capability of four GS of two types namely, temperature (30–50 °C) and immersion test periods from 24 h
3-oxa-1,5-pentamethylene-bis(N-alkyl-N,Ndimethylammonium (82.37 %) to 72 h (91.39 %) at 2000 ppm at 30 °C. The positive val-
chloride) (12-O-12, R = C12H25; 18-O-18, R = C18H37), and 3-oxa- ues of enthalpy of adsorption suggested endothermic reaction
1,5-pentamethylene-bis(N-alkyl-N-hydroxyethyl- N- hence chemisorption of the inhibitor molecules. The capacitive
methylammonium chloride) (12-MOH-O-MOH-12, R = C12H25; loops in the Nyquist plots have a depressed nature with their cen-
18- MOH-O-MOH-18, R = C18H37) [59]. The reduction in surface ters lying below the real axis. This may be the result of frequency
roughness was measured using confocal laser scanning microscopy dispersion generally associated with porous/heterogeneous elec-
(CLSM) which confer that the occurrence of a shielding layer of trode surface which leads to a deviation from ideal capacitive
adsorbed molecules avoided corrosion by the acid. Analysis of behavior. Hamadi et al., [62] showed that the self–assembled
structure - inhibition efficiency relationships by PM5 semi empir- monolayer (SAMs) formed by the glutamic acid (Glu a) prevent
ical and DFT method showed that changes in the inhibiting ability corrosion of Fe-19Cr SS in 1 M HCl at 25 °C. As evident from
can be explained by changes in the inhibitor electronic properties. Fig. 7, the corrosion rate of SS increases with time. After 3 h of
The OCP of AISI 304 SS shifted on more positive direction with the immersion, the corrosion rate stabilizes and then decreases with
inhibitors as compared to without inhibitors. The adsorption pro- time. Glu (a) molecules adsorbed physically on the metal surface
cess for three of them (12-O-12, 12-MOH-O-MOH-12, and 18- by their polar groups following the Langmuir adsorption isotherm.
MOH-O-MOH-18) involves chemisorption and physisorption, However, Glu (a) acted as a moderate corrosion inhibitor show-
while 18-O-18 involves chemisorption. The authors also proposed ing 41.66 % efficiency at 500 ppm. Therefore, the performance of
the dependency of IE on CMC of the surfactants. However, the Glu (a) was improved by adding 0.06 M KI which caused an
determination of CMC method was missing, and other physico- increase in efficiency to 55 %. However, the system yet did not
chemical parameters were also not calculated and discussed. exhibit effective performance. The calculated value of free energy
In a work studying [60] the inhibition effect of two cationic of adsorption (-12.93 KJ/mol) of (Glu a) on the electrode Fe-19Cr
gemini surfactants namely N,N0 – didodecyl – N,N,N0 ,N0 – tetram- SS suggested that the adsorption was made physically. The results
ethyl – 1,5,9 – triazonanediodide (TMTN12I) and N,N0 – didodecyl of the polarization study [Fig. 8] revealed that the Glu (a) SAMs
– N,N,N0 ,N0 – tetramethyl – 1,5,9 – triazonane dibromide prefer working by slowing oxygen diffusion.
(TMTN12Br) on AISI 304 SS in 3 M HCl, the authors proved their Biosynthesized silver nanoparticles (AgNPs) using kolanut pod
highest inhibition efficiency near their CMC. For both TMTN12Br extract as a reducing agent were tested for their anti-corrosive
and TMTN12I, the diameter of the semicircle (in Nyquist plots) properties for mild steel, SS, and aluminum at the concentration
increased gradually as the surfactant concentration was increased of 0, 5, 10, 15, and 20 lg/ml [63]. AgNPs solution in 1 M HCl envi-
ronments exhibited 52 % IE for mild steel, 70 % for SS and 62 % for
aluminum. According to Fig. 9, the corrosion rates decreased with
the concentration of AgNPs and time of exposure. However, SS and
Fig. 6. SEM images of stainless-steel surface: a) before immersion; b) after

immersion in 3MHCl; c) after immersion in 3MHCl with 3 N-12 (1 mM); d) after Fig. 7. The corrosion rate of Fe-19Cr SS as a function of immersion time in a
immersion in 3MHCl with 3 N- 18 (0.01 mM) [58]. solution of 1 M HCl [62].
10
Fig. 10. Structure of New Fuchsin [64].
Recently, in 0.5 M HCl solution, new Fuchsin (NF) (Fig. 10)

Fig. 8. Tafel polarization curves for Fe-19Cr SS in 1 M HCl with various concen- obtained from Merck is reported to be a good mixed type of inhi-
trations of (Glu a) at 25 °C [62]. bitor for SS 304L corrosion [64].
The presence of the protonated species (NFH+) and the presence
aluminum’s inherent corrosion resistance also contributes to the of the delocalized p-electron ‘‘clouds” of the conjugated aromatic
decrease in their corrosion rates attributed to the quick formation rings, induced robust adsorption onto the polar surface which is
of the passive layer enhanced by the large amount of Cr and Al in suggestive of NF’s superior inhibitive proficiency. The formation
the SS and aluminum, respectively. Hydrogen evolution measure- of an insoluble layer on the metal was ascribed to the inhibitory
ment showed that the evolution of H2 was more rapid in the alu- mechanism; this idea has been further validated by corrosion pas-
minum sample than in the SS sample. The adsorption of AgNPs sivity models, such as Bi-Layer Point Defect Model (BLPDM) or the
was spontaneous, exothermic, and physisorbed. Anion Catalyzed Active Dissolution Model (ACADM). The results
Fig. 9. Corrosion rate of (a) mild steel (b) stainless steel and (c) aluminum samples against time of exposure in acidic medium with and without AgNPs [63].
11
Fig. 11. The most stable low energy configuration for the adsorption of New Fuchsine, H2O, and Cl- on a-Cr2O3 (0001) surface obtained through the Monte Carlo simulation,
Red Balls (O atoms), Gray Balls (Cr atoms), and Green Balls (Chloride) [64].
were further supported by DFT and MD simulation methods sug- the adsorption of plant extract. The anti-corrosive properties of
gesting the lateral adsorption of the compound on a-Cr2O3 Oryza sativa plant extract (OSPE) was studied on SS 410 in a
(0001) surface via electrostatic interaction (Fig. 11). 15 % HCl medium [70]. A maximum corrosion inhibition of
The methanolic extract of Cistus ladanifer to inhibit 304L SS 91.92 % was observed when 4 g/L of OSPE was added to the solu-
corrosion in 1 M HCl solution was tested employing weight loss tion. The results of the analysis revealed that the monolayer of
measurements and electrochemical measurements [65]. C. ladani- OSPE on the surface of SS 410 was formed following the Langmuir
fer extract reduced 304L SS corrosion with a 97.8 % inhibition effi- adsorption isotherm. The results of the theoretical study revealed
cacy, according to the results. The treated coupon surfaces became that the anti-corrosive effect was mainly related to the presence
hydrophobic as measured by the contact angle. Rct values in 1 M of a phytochemical known as 9,12,15-octadecatrienoic acid. In
HCl solutions improved from 106.9 cm2 in the blank solution to another study [71], the researchers explored the effects of Beta vul-
1693 cm2 in the solution containing 1 g/L extract. Lower Cdl values, garis peel extract on the corrosion properties of SS 410 in a 15% HCl
ranging from 186.69 to 62.71F cm2, were linked to higher Rct val- solution. The study revealed that the extract exhibited a maximum
ues, which may be due to a reduction in the local dielectric con- corrosion inhibition efficiency of 90.17 % at 4 g/L of B. vulgaris peel
stant and/or a rise in the thickness of the protective film on the extract. According to the computational and theoretical studies,
electrode surface that strengthen the corrosion resistance of the the presence of vitexin in the extract has the potential to con-
304L SS in 1 M HCl. tribute to the anti-corrosive effect.
An eco-friendly Curam drug was used as a corrosion inhibitor Table 4 shows the numerous other inhibitors [72–103] investi-
for 304 SS in 2.0 M HCl solution [66]. Weight loss measurements gated to inhibit SS corrosion in the HCl medium. Table 4 showed
data prove that with an increase in the temperature, Curam still the corrosion rate and the maximum inhibition efficiency for each
exhibits good anti-corrosion performance. The inhibition efficiency inhibitor when various experimental conditions were used, such as
of Curam can still be maintained at about 72% at 318 K. The data of temperature, inhibitor concentration, the concentration of aggres-
electrochemical measurements indicate that Curam is the mixed- sive media, adsorption isotherm, grade of SS, type of adsorption
type inhibitor. Curam adsorb on the SS 304 surface obeying Lang- mechanism, and so on. Ongoing through the data reported in
muir adsorption isotherm. FT-IR and AFM analysis showed the Table 4, some of the flaws were observed. Most of the compounds
excellent adsorption performance of Curam for SS 304 dissolution tested were synthesized, and some of them were obtained com-
in an acidic medium. mercially. However, few papers have not reported the whether
Recently, three synthesized ionic liquids namely (3-(2-ethoxy the studied compounds were procured commercially or synthe-
methyl)-1-octyl-1H-imidazol-3-ium chloride (IL1), 1-decyl-3-(2- sized for example references [75,81,83,89,90,92,93,95–97,99,101].
ethoxy methyl)-1H-imidazol-3-ium chloride (IL2) and 1-dodecyl- In one of the works, the authors did not report the characterization
3-(2-ethoxymethyl)-1H-imidazol-3-ium chloride) (IL3) were data [83]. In reference [73], the authors did not report the corro-
explored by Katori et al., [67] on 201 SS in 2 M HCl at 30 °C. Exper- sion rate of SS immersed in an acidic solution without inhibitors.
imental (PDP, EIS, EFM) and theoretical (DFT and MC simulation) In contrast, in several papers, the authors did not report the cor-
results confirmed IL3 to be most efficient, exhibiting 91.5 % IE than rosion rate in uninhibited and inhibited media [93,94,100–102]
IL2 (90.4 %) and IL1 (88.1 %).To locate the chemical nature of IL/SS and inhibition efficiency [93,94]. In one of the papers, units of cor-
interface, the authors also carried out XPS study. In another report, rosion rate was found missing [82], thus making it hard to under-
Bhardwaj et al. studied the inhibitory action of Phyllanthus stand the effectiveness of inhibitors in decreasing the corrosion
Emblica seed extract (PESE) [68] and Triticum aestivum [69] on rate of SS compared to uninhibited media.While performing the
SS 410 SS in 15% HCl solution. The inhibitor molecules adsorbed weight loss measurements majority of the authors did not provide
on the metal surface following Langmuir adsorption isotherm any data on the reproducibility of the experimental results. More-
and acted as mix type inhibitors. The main component of extracts over, inhibition performance calculated by gravimetric and electro-
responsible for the inhibition action was 3,4,8,9,10-pentahydroxy- chemical methods was not correlated by statistical analysis to
dibenzo[b,d] pyran-6-one in PESE and (+)-Lariciresinol in Triticum prove the non-significant behavior of tests. In some of the articles,
aestivum. The authors supported the inhibition mechanism offered the reaction condition like temperature, immersion, etc.
by 3,4,8,9,10- pentahydroxy-dibenzo[b,d] pyran-6-one employing [98,100,102], adsorption mode [98], and inhibition type [98] have
DFT calculations. SEM and AFM studies were undertaken to assess not been reported. In another paper [102], the concentration of
the morphological changes occurring on the metal surface through acid employed was not mentioned. Except for reference [78], the
12
Table 4
R. Aslam, M. Mobin, S. Zehra et al.

Summary of the main features of the cited corrosion inhibitors of SS in HCl solution.
SS type Chemical structure, name and abbreviation of Characterization techniques Conc. Experimental Corrosion Corrosion Highest Adsorption isotherm and Ref
inhibitor used of HCl condition Techniques rates protection nature
(mmpy) efficacy
FTIR, 1H, 13
C NMR 1M T- RT PDP, EIS, SEM-EDX, CRi-0.160 73 0.1% at Langmuir’s adsorption [66]
Immersion time- FT-IR, UV–visible, 0.5 mM isotherm/ mixed type
2h XRD, DFT (cathodic action)
methyl 2-((2-
hydroxybenzylidene)amino-3-(1H- indol-3-yl)
propanoate
(S1)
CRi-0.12 79.3 % at
0.5 mM
2-(((1-hydroxy-3-
(1H-indol-3-yl)-1,1-diphenylpropan-2-yl)
imino)methyl) phenol
(S2)
13
AISI 304 SS poly[2-(dimethylamino) ethylmethacrylate] gel permeation chromatography 10–3 T- RT PDP, EIS, ICP-OES, CRb- 91 % at 10– Langmuir’s adsorption [67]
(PDMA) (GPC), 1H NMR M PH- above 9 SEM-EDX, AFM 40640 2M isotherm/ mixed type
CRi-3708
poly[2-diethylamino) ethylmethacrylate] gel permeation chromatography 10–3 T- RT PDP, EIS, ICP-OES, CRi-5842 85 % at 10–2
(PDEA), (GPC), 1H NMR M PH- above 9 SEM-EDX, AFM M
poly[2-(diisopropylamino) ethyl methacrylate] gel permeation chromatography 10–3 T- RT PDP, EIS, ICP-OES, CRi-9550 76 % at 10–2
(PDPA) homopolymers (GPC), 1H NMR M PH- above 9 SEM-EDX, AFM M
poly[2-(dimethylamino)ethylmethacrylate]- gel permeation chromatography 10–3 T- RT PDP, EIS, ICP-OES, CRi-9296 77 % at 10–2
bpoly[ methylmethacrylate] (PDMA-b-PMMA), (GPC), 1H NMR M PH- above 9 SEM-EDX, AFM M
poly[2-(diethylamino)ethylmethacrylate]-b-poly gel permeation chromatography 10–3 T- RT PDP, EIS, ICP-OES, CRi-3784 90 % at 10–2
[methylmethacrylate](PDEA-b-PDMA) (GPC), 1H NMR M PH- above 9 SEM-EDX, AFM M
AISI 304 SS — 1M T- 20 °C PDP, EIS, WL, SEM- — less than Langmuir’s adsorption [68]
EDX 80 % at isotherm/ mixed type
1-octyl-3-
1 mol/m3 (anodic)

methylimidazolium bromide
— 1M T- 20 °C PDP, EIS, WL, SEM- — greater

EDX than 80 % at
1-dodecyl-3-
1 mol/m3
methylimidazolium bromide
316 SS 4-(p-methoxyphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 95.5 % at Temkin’s adsorption/ [69]
bromoethyl cyanoacetate)-3-phenyl-1,3- 7 10-3 M mixed type
thiazolidin-5-one
4-(o-methoxyphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 90.2 %
bromoethyl cyanoacetate)-3-phenyl-1,3-
thiazolidin-5-one
4-(m-methoxyphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 88.6 %
(continued on next page)

Table 4 (continued)
(mmpy) efficacy
thiazolidin-5-one
4-(p-methylphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 87.2 %
thiazolidin-5-one
4-(o-methylphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 86.0 %
thiazolidin-5-one
4-(m-methylphenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 82.0 %
thiazolidin-5-one
4-phenylazo-2-bromo-2-(a-bromoethyl — 1M T- 30 °C EIS, SEM-EDX, XPS — 81.0 %
cyanoacetate)-3-phenyl-1,3-thiazolidin-5-one
4-(m-nitrophenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 77.0 %
thiazolidin-5-one
4-(p-nitrophenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 75.0 %
thiazolidin-5-one
4-(o-nitrophenylazo)-2-bromo-2-(a- — 1M T- 30 °C EIS, SEM-EDX, XPS — 71.3 %
thiazolidin-5-one
SS 304 Obtained commercially from 1M T- 25–55 °C WL, EFM, EIS, PP, — 91.0 % at Temkin’s adsorption/ [70]
Aldrich company AFM 25 lm mixed type
14
Obtained commercially from 1M T- 25–55 °C WL, EFM, EIS, PP, — 76.2 % at —

Aldrich company AFM 25 lm
Obtained commercially from 1M T- 25–55 °C WL, EFM, EIS, PP, — 66.2 % at

Aldrich company AFM 25 lm

304 L SS Purchased from Merck 1M T- RT PDP, UV–vis — 67.9 % at Langmuir adsorption/ [71]
0.8 mmol/L mixed type
Metronidazole
Table 4 (continued)
(mmpy) efficacy
304 SS FTIR, 1H NMR, 13
C NMR, mass 0.1 M T- 22 °C WL, CV, PDP, AFM, — 92.49 % at [72]
spectroscopy DFT 1 mM
((E)-(Phenylimino)
methyl)phenol (1)
,
FTIR, 1H NMR, 13
C NMR, mass 0.1 M T- 22 °C WL, CV, PDP, AFM, — 94.30 % at
2-((E)-(p-
Tolylimino)methyl)phenol
(2)
FTIR, 1H NMR, 13
(E)-2-
(Hydroxybenzylideneamino)benzoic acid (3)

,
FTIR, 1H NMR, 13
15
(E)-2-
(Hydroxybenzylideneamino)benzoic acid (4)

,
FTIR, 1H NMR, 13
2-((E)-(2
Hydroxyphenylimino)methyl) phenol

(5)
FTIR, 1H NMR, 13
2-((E)-(2
Mercaptophenylimino)methyl)phenol
(6)
201 SS Elemental analysis, IR, NMR 1M T- 25–45 °C WL, PDP, EIS, EFM, CRb-0.645 86.3 % at Langmuir adsorption/ [73]
FTIR, AFM, DFT CRi-0.35 21 106 M mixed type/
T- 25 °C physisorption

Table 4 (continued)
(mmpy) efficacy
(A) 1-(1-
(cyclohexa-2,4-dienyl)ethylidene)-2-(1-
phenylethylidene)
hydrazine
Elemental analysis, IR, NMR 1M T- 25–45 °C WL, PDP, EIS, EFM, CRi-0.38 83.9 % at Langmuir adsorption/
FTIR, AFM, DFT 21 106 M mixed type/
1- T- 25 °C physisorption
benzylidene-2-(cyclohexa-2,4-
dienylmethylene)
hydrazine
304 SS purchased from Memphis 2M T- 30–45 °C, WL, EIS, PP, EFM, CRb-0.28 93 % at Langmuir adsorption/ [74]
company, Cairo, Egypt Immersion time- AFM, FTIR CRi-0.017 300 ppm at mixed type,
120 min 30 °C physisorption
316 SS — 2M T- 30–60 °C, EIS, PP, XPS, DFT CRb-0.03 94 % at Langmuir adsorption/ [75]
16
Immersion time- CRi- 300 ppm at mixed type,

120 min 0.0018 30 °C physisorption
— 1M T- 25–45 °C, WL, PP, EIS, EFM, — 71.7 % at Langmuir adsorption/ [76]
Immersion time- DFT 21 106 M mixed type,
120 min at 25 °C physisorption
— 1M T- 25–45 °C, WL, PP, EIS, EFM, — 81.5 % at Langmuir adsorption/

Immersion time- DFT 21 106 M mixed type,
120 min at 25 °C physisorption

super — 20 % T- RT WL, PP, EIS, SEM- — 97.70 % at Mixed type [77]
13Cr SS EDS 3%
3CR12 Ferritic SS Purchased from BOC Sciences, 2M T-25 °C PP, IR CRb-28.95 87.52 % at Langmuir adsorption/ [78]
USA, Immersion time- CRi-3.61 1.5 % mixed type,
240 h chemisorption
Table 4 (continued)
(mmpy) efficacy
304 SS Terminalia Catappa Leaves Leaves were obtained from 1M T- 30–50 °C WL, SEM CRb-0.209 97.88 % at Temkin adsorption/ [79]
American University of Nigeria, CRi-3.61 0.09 g/ml mixed type,
Yola chemisorption
201 SS Elemental analysis, IR, NMR 1M T- 25, 30, 35, 40, EIS, EFM, PP, WL, CRb-0.64 94.2 % at Langmuir adsorption/ [80]
45 °C FTIR, AFM, QCC CRi-0.020 21 106 M mixed type,
physisorption
Elemental analysis, IR, NMR 1M T- 25, 30, 35, 40, EIS, EFM, PP, WL, CRb-0.64 92.1 % at Langmuir adsorption/
Physisorption
Elemental analysis, IR, NMR 1M T- 25, 30, 35, 40, EIS, EFM, PP, WL, CRb-0.64 88.8 % at Langmuir adsorption/
physisorption
1 13
AISI 304 H, C NMR, FTIR 3M T- RT, immersion EIS, SEM, CLSM CRb-20.8 98 % at Langmuir adsorption [81]
time 24 h CRi-0.5 2.1 mM
PMTH2E8
1 13
H, C NMR, FTIR 3M T- RT, immersion EIS, SEM, CRb-20.8 98 % at Langmuir adsorption
17
PMTH2E10
1 13
H, C NMR, FTIR 3M T- RT, immersion EIS, SEM, CLSM CRb-20.8 97 % at Langmuir adsorption
PMTH2E12
SUS 304 Synthesized but No info on ch 1M T- 30 °C EIS, SEM, CV — 99.8 % at Langmuir adsorption/ [82]
0.25 mM mixed type

316 SS combined admixture of benzonitrile — 6M — PP, EIS, FTIR — 97.2 % at Langmuir and Frumkin [83]
andbenzothiazole 0.5 % adsorption isotherm. /
(BBZ) mixed type
304 SS Root Extracts of Ajuga chamaecistussubsp. — 6M T- 25, 35, 45, 55, WL, PP, EIS, SEM, CRb-4 92.3 % at Langmuir adsorption/ [84]
Scoparia 65 °C AFM CRi-0.3 5 g/L mixed type
Shoot Extract of Ajuga chamaecistussubsp. — 6M T- 25, 35, 45, 55, WL, PP, EIS, SEM, CRb-4 92.3 % at Langmuir adsorption/
Scoparia 65 °C AFM CRi-0.3 5 g/L mixed type

Table 4 (continued)
(mmpy) efficacy
316 SS FTIR 2M T- 30, 35, 40, 45, WL, PP, EIS, SEM- CRb-2.26 91.3 % at Langmuir adsorption/ [85]
50 °C, immersion EDX CRi-0.19 2000 ppm mixed
time- 24–72 h at 72 h type/chemisorption
304 SS Papaver somniferumL. extract — 0.2 M T- 25, 35, 45 °C WL, PP, SEM-EDX, CRb-142 93 % at Langmuir adsorption [86]
AFM CRi-0.99 500 ppm isotherm /mixed
at 25 °C type/physisorption
304 SS Tectona grandis leaf — 2M T- 40, 50, 65, 80 °C PP, EIS, FTIR, contact — 60.6 % at Langmuir adsorption [87]
Extract angle 1 g/L isotherm /mixed
type/chemisorption
AISI 321 Sigma-Aldrich, 99 % 1M T- 30 °C OCP, EIS, PP — — Florry-Huggins, Temkin [88]
isotherm/mixed type
AISI garlic extract — 0.5 M T- RT WL, OCP, PP, EN, EIS, CRb-1.98 88.6 % at Langmuir adsorption [89]
304 DFT, MC and MD CRi-0.22 8 cm3 L-1 isotherm /mixed
simulations at 25 °C type/chemisorption
304 SS — 1M T- 25 °C WL, PP, EIS CRb-1.98 77.0 % at Langmuir adsorption [90]
CRi-0.22 11 106 M isotherm /mixed
18
at 25 °C type/physisorption
— 1M T- 25, 35, 45, 55 °C WL, PP, EIS — 72.6 % at Langmuir adsorption

11 106 M isotherm /mixed
type/physisorption
— 1M T- 25 °C WL, PP, EIS — 68.1 % at Langmuir adsorption

11 106 M isotherm /mixed
type/physisorption

3CR12 DNA of Calf Thymus Gland — 1M T- 10, 25, 40, 55, WL, PP, SEM-EDS, CRb-0.18 75.7 % at Mixed [91]
(CTG DNA) 70 °C XRD CRi-0.012 20 mg/L type/chemisoprtion
at 25 °C
420 SS Shazab leaf extract (DSLE) FTIR, UV–vis 0.5 M — EIS, PP, — 85.1 % at — [92]
12.5 v/v%
304 L — 0.1, T- 25, immersion PP, SEM CRb-4.9 96.0 % at Mixed type [93]
1M time 2, 6, 8, 12 h CRi-0.04 5 % (0.1 M
(E)-3- (0.1 M HCl)
HCl) 84.6 % at
CRi-0.23 0.5 % (1 M
phenylprop-2-enal
(1 M HCl) HCl)
(Cinnamon Oil)
Table 4 (continued)
(mmpy) efficacy
SS316 poly (o-anthranilic acid) (PAA), graphene oxide XRD, SEM, TEM, FTIR, UV–vis 2M — EIS, PP, AFM, SEM — 91.8 % at Langmuir adsorption [94]
(GO) and functionalized multi-walled carbon 70 ppm isotherm /mixed type
nanotubes (f-MWCNT)
316SS NMR 2M T- 30 °C HE, WL, PDP, EIS, — 99.6 % at Langmuir adsorption [95]
SEM, EDX, DFT 1.0 10–4 isotherm /mixed type
1-
Methyl-4-[4́-(–OCH3)
-styryl] pyridinium iodide
NMR 2M T- 30 °C HE, WL, PDP, EIS, — 99.8 % at Langmuir adsorption

1-
19
Ethyl-4-[4́-(–OCH3)
-styryl] pyridinium iodide
NMR 2M T- 30 °C HE, WL, PDP, EIS, — 99.8 % at Langmuir adsorption

1-
Propyl-4-[4́-(–OCH3)
-styryl] pyridinium

iodide
1H, 13C and mass spectra — — SEM, EIS, EFM, FTIR, — 81.5 % at Langmuir adsorption [96]
DFT 0.5 mM isotherm /mixed type
N’,N’’’-
(thiophene-2,5-diylbis(methanylylidene))di
(isonicotinohydrazide)
(SS1)

calculation of pitting potential is scarce, however, in this paper, the
[97]
Ref
authors didn’t discuss the results of pitting potential.

Adsorption isotherm and
3.3. Sulphuric acid
Langmuir adsorption
type/chemisorption
isotherm /mixed
To use the agro-industrial waste products to improve their eco-
nomic viability and generate environmental benefits, acidic extract
of Barley agro-industrial waste (AW) [104] was studied as a corro-
nature
sion inhibitor for AISI 304 SS in 1.5 mol/L H2SO4. The concentration
studied were 1–5 g/L at the temperature of 32, 42, and 52 °C. The
—
AW, rich in phenolic compounds, glutathione, amino acids, and

protection
88.48 % at
ascorbic acid, exhibited the highest reduction in corrosion rate

0.1 g/L at
88.6 % at
0.5 mM
Highest
efficacy
(0.158 mm/y) compared to a blank (5.58 mm/y) at 5 g/L of AW

45 °C
extract concentration. The inhibition efficacies were in the range

of 78 % to 97.1 % in the above reported concentrations range. The
CRb-34.83
Corrosion
results of potentiodynamic polarization (Fig. 12) showed that at

CRi-4.01
(mmpy)
880 mV potential, the anodic reaction occurred showing two

rates
active regions. First, one is related to oxides and the second one
—
is associated with the sensitization of SS. AW promoted the shift

SEM, EIS, EFM, FTIR,
in potential towards a positive direction. With AW, the first active

PP, EIS, SEM-EDS
region remained unaffected; however, the second active region

presented lower current densities in the presence of the inhibitor,
Techniques
Corrosion
showing that the extract inhibited the SS sensitization process. The

anodic currents in the passivation region retained the same behav-
DFT
ior with the addition of the AW extract.

The inhibition performance was weakened on increasing tem-
T- 30, 35, 40, 45 °C
perature suggesting physical adsorption of AW extract on SS sur-

face which occurred through the electrostatic interaction
Experimental
between charged SS surface and charged inhibitor components.

condition
The EDX results exhibited the peaks of C, N, and O suggesting their

involvement in the inhibition process.
—
Loto et al., [105] employed PDP, optical microscopy, and FTIR

of HCl
0.5 M
spectroscopy methods in a comparative study of protective films

Conc.
formed on 2101 duplex SS and 301 austenitic SS at 37 °C upon

—
exposure of samples in a solution containing 6 M H2SO4 without

and with 0–1.25 % of 4-cyanobenzene (4CB). The inhibition perfor-
Characterization techniques
mance of 4CB was slightly higher for 2101SS. According to the

1H, 13C and mass spectra
polarization curve, the maximum corrosion potential in the pres-

ence of inhibitor was 156 mV for 2101SS and 155 mV for 301SS
compared to blank proving 4CB to act as an anodic type of inhibitor
for both the steels. The optical images of the uninhibited steel
specimens showed that the 2101SS surface (Fig. 13a) appears to
be smooth (due to its relatively higher oxidation resistance as sug-
gested by the corrosion rate results) and corrosive effect of SO2- 4
—
ions on 301SS was much more visible due to its intergranular

Chemical structure, name and abbreviation of
(thiophene-2,5-diylbis(methanylylidene))bis
2,20 -
(N-phenylhydrazinecarbothioamide)
Sinapis alba extract

inhibitor used
(SS2)
Table 4 (continued)
SS type
Fig. 12. Polarization curves obtained for AISI 304 SS in 1.5 mol/L H2SO4 in the
presence and absence of the AW acid extract with a 1 mV s1 scanning rate [104].
20
Fig. 13. Optical images of SS specimen after corrosion test without 4CB (a) 2101SS (b) 301SS and with 4CB (c) 2101SS (d) 301SS at mag. x100 [105].
corrosion (Fig. 13b). On exposing both the steels in the solution costic acid, 9.38 kX cm2 in the presence of ilicic acid at 103 mol/
containing 4CB compound, the change in surface morphology of L and 34.44 kX cm2 in the presence of 7.5 105 mol/L of
2101SS (Fig. 13c) was minimal due to its higher corrosion resis- tomentosin. Thermodynamic parameters suggested the
tance properties as compared to 301SS (Fig. 13d). chemisorption of ilicic acid and tomentosin while DVE and isocos-
In another study, Loto et al. [106] studied the corrosion preven- tic acid acted on anodic dissolution by physical adsorption follow-
tive behavior of butanol on austenitic SS type 304. Butanol pro- ing Langmuir adsorption isotherm.
tected SS moderately (exhibited 78.7 % IE at 0.002 M butanol) by The extract of honeycomb waste as an inhibitor was tested for
forming a barrier film by adsorbing through physisorption mecha- 304 SS in various concentrations of H2SO4 solutions [109]. Firstly,
nism via weak van der Waals forces. The XRD pattern of the surface honeycomb waste was characterized utilizing liquid
film (Fig. 14) confirmed the formation of corrosion products chromatography-mass spectrometry (Fig. 16) which exhibited nine
exhibiting the peak values at 2h = 89.4°and 111.2°, responsible components namely, Luteolin, Vitexin, Quercetin, Fisetin, Isoham-
for iron oxide. The XRD pattern of the surface film generated on netin, Isoferulic, Apigenin, Pinobanksin and Kaempferol. Quercetin
austenitic SS after immersion in 3 M H2SO4 with butanol was being the major component with 43.90%. The inhibition efficiency
devoid of these peaks, indicating its protective capabilities. of the inhibitor (concentration 2000 mg/L) reached 97.29 % in
The statistical analysis using ANOVA further confirmed that the 0.5 M H2SO4 and decreased with the acid concentration. The Frum-
inhibitor concentration and immersion time are significant model kin isotherm model was used to analyse the adsorption behaviour
terms that influenced butanol inhibition efficiency. of the extract.
Deyab [107] suggested that the cationic surfactant benzetho- In 0.5 M, 1.0 M, 1.5 M, and 2.0 M H2SO4 solutions, the 2000 mg/L
nium chloride (BCCS) (Fig. 15) could be deemed as good potential inhibitor limits the highest shift difference in Ecorr with the Ecorr
inhibitor owing to the electronegative heteroatoms and aromatic shift to the blank, which are 28.5 mV, 98.0 mV, 115.0 mV, and
systems on 316L SS in multistage flash (MSF) desalination plants 104 mV, respectively, confirming the anodic type inhibitor in
during the scales removing by sulfuric acid. The experiment was 1.0 M, 1.5 M, and 2.0 M H2SO4 solutions, while as mixed type inhi-
carried out at 25 °C after 5 hr immersion. The adsorption of proto- bitor in 0.5 H2SO4. Imidazole derivative was tested as corrosion
nated species was suggested by DFT study which showed that the inhibitor for 316 L SS in H2SO4 at room temperature [110]. The
HOMO and LUMO zones are localized on the cation part (proto- authors considered the compound a suitable inhibitor that can pro-
nated form) of BCCS (NR+4). The performance of BCCS enhances with tect SS from pitting corrosion if the SO2
4 ions cause the pitting cor-
its concentration attaining a maximum value of 92.3 % at rosion. However, this statement is at odds with other findings
3.5 104 M around the CMC value of BCCS. where the SO2 4 ion is believed to impede pitting on metals [111].
Considering the general corrosion of AISI 321 SS, Dittrichiavis- The inhibition of 304L SS in 0.5 M H2SO4 was recently studied
cosa extract (DVE) and its chief isolated component sesquiterpenes using expired levothyroxine drug [112]. It gave the best inhibition
namely tomentosin, a-costic acid (isocostic), and ilicic acid were efficiency of 94.3 %, at 150 ppm based on gravimetric measure-
examined as potential green alternative [108]. The inhibition effi- ments. The adsorption of expired levothyroxine drug on 304L SS
ciency attains 97 % at 5 104 mol/L for ilicic acid, 95 % at surface agreements with Langmuir. In the paper, the authors justi-
7.5 105 mol/L for tomentosin, 86 % at 2 102 mol/L for isocos- fied the employment of expired drugs based on the waste manage-
tic acid, and 92.39 % at 2.5 g/L for DVE. EIS confirms the increment ment and high costs of this kind of inhibitor.The potentiodynamic
in the charge-transfer resistance which increased from 2.17 to polarization measurement data show that levothyroxine drug
23.91 kX cm2 for DVE, reaches a value of 17.48 kX cm2 for iso- acted as inhibitor of mixed type for 304L SS. In another publication,
21
Fig. 14. XRD pattern of the surface film formed on austenitic SS after immersion in 3 M H2SO4 (a) without BTU (b) with butanol [106].
sodium dodecyl sulfate (SDS) [113] was tested as corrosion inhibition in the temperature range of 30–60 °C was examined.Concen-
tor of SUS304L, SUS304H, and SUS316H SS in 0.5 M H2SO4 solution. tration and temperature have been shown to increase extract
SDS was found to be a mixed-type inhibitor. SDS was found to inhibition efficiency. The XRD pattern (Fig. 17a-b) shows peaks at
adsorbed on SS surfaces following the Temkin adsorption isotherm 53.41, 57.16, 62.41 and 74.04 (2 h), suggesting the presence of iron
and was the result of a physical adsorption mechanism. From the oxides (Fe3O4), i.e., products of corrosion because of the deteriora-
adsorption isotherm, the thermodynamic parameters of SDS tion and breakdown of the alloy 304L sample. At the same time,the
adsorption were calculated.When the IE percent values for the introduction of the extract reveals the absence of iron oxide peaks.
three alloys were compared, it was noticed that the magnitudes Fig. 18 showed the main active phytochemical ingredients
of %IE decrease in the order: SUS316H > SUS304L > SUS304H. responsible for the inhibitive effect of this extract. Moreover, these
The inhibitive potency of Centrosemapubescens leaves extract phytochemical constituents contain many oxygen atoms in func-
[114], a bio-extract, on corrosion of UNS S30403 in 1 M H2SO4 solu- tional groups of –OH, –COOH, C@O, O-heterocyclic ring, etc., which
meet the conditions for standard corrosion inhibitors.
The tribological inhibition behavior of AISI 304L SS in 0.5 M sul-
furic acid in the presence of Thymus zygis subsp. gracilis essential
oil was tested [115]. 3 g/L of the inhibitor provided 84.3 % IE. In
another report by Yeganeh et al. [116], the inhibition effect of
methionine as anti-corrosive material on 316L SS in 0.1 M H2SO4
was tested. The studied inhibitor acted as an anodic type inhibitor.
The corrosion inhibition properties of many other inhibitors
[117–127]used for SS corrosion in H2SO4 medium are presented
in Table 5. One of the paper did not fit the data to any adsorption
Fig. 15. The benzethonium chloride (BCCS) chemical structure [107].
22
Fig. 16. (a) Chromatogram of honeycomb waste extract (b) molecular structure of quercetin [109].
port the claim. The value of the regression coefficient in the case of
Temkin adsorption isotherm was 0.742.
In a recent study [128], it was reported that the presence of
Piper nigrum leaves (PNL) extract in the solution of 0.5 H2SO4
can improve the corrosion resistance of SS 410. The potentiody-
namic polarization study revealed that the presence of PNL extract
in the solution exhibited the inhibition efficiency of 94.20 %. Two
compounds, thiosemicarbazone and semicarbazone sesquiterpene
were synthesized from sesquiterpene a,b-unsaturated ketone.
They were studied for their electrochemical activity and anti-
corrosion properties. Multiple analytical techniques were per-
formed to characterize these molecules. The performance of these
compounds against the corrosion of SS 321 in 1 M H2SO4 medium
was studied using various methods. It was revealed that they acted
as mixed-type inhibitors with dominant cathodic inhibition [129].
3.4. Other acids
Essential oil from aerial parts of Artemisia herba-alba (AHAO)

was characterized by capillary GC and GC/MS and its anti-
corrosive behavior for SS in 1 M H3PO4 was examined employing
PDP, EIS and SEM studies [130]. Among the 24 components
reported, 1,8-cineole (35.6 %) and camphor (24.1 %) were the major
components.The inhibition efficiency increased with inhibitor con-
centration and attained 88 % at 1 g.L1 of oil at 25 °C. Adsorption of
inhibitor is spontaneous, exothermic process according to thermo-
dynamic parameters and therefore supports physical adsorption.
Experimental data agrees with the Langmuir isotherm model well.
Fig. 17. (a) XRD pattern of the phases formed on the surface of Alloy 304L after The inhibitory effect of this essential oil has been attributed to its
immersion in 1 M H2SO4 without Centrosemapubescens leaves extract. (b) XRD synergistic effect of the majority constituents and minor compo-
pattern of the phases formed on the surface of Alloy 304L after immersion in 1 M
nents of its composition. Due to the higher dissolution of SS at
H2SO4 in the presence Centrosemapubescens leaves extract [114].
higher temperatures, the inhibition efficiency decreased as the
temperature increased from 25 to 80 °C. Deyab [131] used triethyl-
isotherm [117]. In some of the papers, the authors failed to report sulfonium bis(trifluoromethylsulfonyl)imide, ionic liquid referred
the temperature of the electrolytic solution [117], immersion per- to as TESFI as corrosion inhibitor for 304 SS in 5 % sulfamic acid.
iod [117], and corrosion rates [117–119,122]. In the case of plant On increasing temperature from 30 to 70 °C, some of the TESFI
extract employed, the characterization of phytochemical con- molecules get desorbed from the SS surface leading to the stripping
stituents was missing [120]. In most of the cases, the inhibition of metals surface and thus accelerating corrosion and decreasing IE
mechanism was not proposed. In another work [127], authors from 97.8 % to 88.3 %. This phenomenon reflected the physical
claimed chemisorption mechanism of inhibitor adsorption based adsorption of TESFI molecules on the metal surface. In terms of
on DG°ads values, however, the values of DG°ads were below 40 analyzing potential mechanisms, the work was well-organized
KJmol1.The authors further claimed that the adsorption of T3A and based on numerous theories regarding adsorption modes as
on SS surface occurred following Langmuir, Temkin, Frumkin, and well as computer research evaluating the HOMO-LUMO orbitals.
Freundlich adsorption isotherms with a correlation coefficient gen- In another study, 5-azidomethyl-7-morpholinomethyl-8-hydroxy
erally above 0.9. However, the data given in the Table did not sup- quinoline (AMH) was used in the corrosion inhibition of AISI 321
23
Fig. 18. Chemical structure of some of the active ingredients in the Centrosemapubescens leaves extract [114].
SS in presence of 5.5 M phosphoric acid. The techniques used were by causing it to lose its passivation, making it susceptible to dete-
hydrogen evolution, linear polarization, and impedance spec- rioration when chloride concentration exceeds a certain threshold.
troscopy [132]. It was calculated that the thickness of AISI 321 Chitosan was chemically functionalized with aminotriazolethiol
decreases by 0.05 mmpy at 5 mmol/L, corresponding to a 97.6 % (ATT-Cht), and its anti-corrosive use for AISI 304 SS in a 3.5 % NaCl
efficiency. Quantum chemistry calculations explained the adsorp- solution was described [133]. The results of cyclic voltammetry
tion and inhibition by this compound. (CV) measurements revealed that in the presence of the ATT-Cht,
the current oxidation densities on the SS surface decreased from
3.5. Sodium chloride solution 38 mAcm2 to 5 mAcm2, confirming the inhibitor molecule’s
adsorption and inhibitory action. The developed inhibitor layer
As a result of constant exposure to chloride solutions, rain, con- on the metal surface served as a shield against the mass and charge
densation, and water, the offshore structures continuously deteri- transfer processes occurring on the steel surface due to corrosion.
orate. Chloride ions cause pitting and localized corrosion in metal Icorr and pitting potential (Epit) values decreased with increasing
24
Table 5

Summary of some major reports published on corrosion inhibition potential of SS in H2SO4.
SS type Chemical structure, name and Characterization Conc. of Experimental Corrosion Techniques Corrosion Highest protection Adsorption isotherm and Ref
abbreviation of inhibitor used techniques HCl conditions rates efficacy at optimum nature
(mmpy) conc.
420 FT-IR, 1H NMR, 6M — PDP, ATF-FT-IR — 99.4 % at 0.63 % Langmuir and Freundlich [117]
13
C NMR isotherm / mixed type
304SS element 0.5 M T-30 °C PDP, EIS — 91.5 % at 100 ppm -/Anodic type [118]
inspection, FT-IR,
TGA and 1H
NMR
spectroscopy
3,3-(1,4-phenylenebis(methylene))bis(1-
octyl-1H-imidazol-3-ium)
tetrafluoroburate)
IL
element 0.5 M T-30 °C PDP, EIS — 98.4 % at 100 ppm -/Anodic type
inspection, FT-IR,
TGA and 1H
NMR
spectroscopy.
25
decyl-1H-imidazol-3-ium)
tetrafluoroburate)
IL
element 0.5 M T-30 °C PDP, EIS — 83.3 % at 100 ppm -/Anodic type
inspection, FT-IR,
TGA and 1H-
NMR
spectroscopy
dodecyl-1H-imidazol-3-ium)
tetrafluoroburate)
IL
316 SS FTIR 2.5 M T- 30, 60 °C, WL, EIS, PP, SEM-EDS, CRb-15.67 92.4 % at 2000 ppm Langmuir adsorption [119]
immersion time- DFT CRi-1.19 isotherm /mixed

24, 48, 72 h type/chemisorption
SS Cassia fistula — 0.5 M T- 30 °C PP, WL — 98.6 % at 2 g/L Langmuir adsorption [120]

Extract isotherm/anodic type
304 austenitic Natural honey — 0.5 M T- 25 °C WL, PP, SEM CRb-9.07 94 % at 10 v/v% Langmuir adsorption [121]
steel CRi-2.22 isotherm/mixed type
1
430 SS H NMR 0.5 M T- 30, immersion PP, WL, SEM, DFT — 46.5 % at 1 10-3 M Langmuir adsorption [122]
time- 24 h isotherm/mixed type
(predominantly anodic)

Table 5 (continued)
SS type Chemical structure, name and Characterization Conc. of Experimental Corrosion Techniques Corrosion Highest protection Adsorption isotherm and Ref
abbreviation of inhibitor used techniques HCl conditions rates efficacy at optimum nature
(mmpy) conc.
1,10-
Bis (1-methyl pyridinium-2-yl)

-4,40-dipyridinium dichloride di-iodide
1
430 SS H NMR 0.5 M T- 30 °C, PP, WL, SEM, DFT — 66.8 % at 1 10-3 M Langmuir adsorption
immersion time- isotherm/mixed type
24 h (predominantly anodic)
1,10-
dimethyl-4,40-dipyridinium di-iodide
316 SS MS 0.5 M Immersion time- WL, PP, SEM-EDX CRb-2.8 94.7 % at 10 g Langmuir adsorption [123]
24 h CRi-0.09 isotherm/mixed type
26
Egg shell powder

S40977 obtained from 3M T-30 °C PP, OCP, Optical — 88.3 % at 1.25 % Langmuir adsorption [124]
BOC Sciences, microscopy, IR isotherm/mixed type
USA
AISI309S BioShop Canada 1M Immersion time- EIS, PP, EN, SEM, AFM, — 97 % at 700 ppm Langmuir adsorption [125]
Inc. 1h XPS, power spectral isotherm/mixed type
density

304 austenitic — 0.5 M T-30 °C WL, PDP, LP, EIS, FTIR, — 75.4 % at 1 10-3 M -/Anodic type [126]
H2SO4 1 SEM-EDS
0.01 M H2S
0.5 M T-30 °C WL, PDP, LP, EIS, FTIR, — 85.6 % at 1 10-3 M —

H2SO4 1 SEM-EDS
0.01 M H2S
inhibitor concentration. ATT-Cht acted as a cathodic type of inhibi-
[127]
tor. The Epit value increased as the concentration was increased,
Ref
indicating a better resistance to pit nucleation.
Temkin adsorption isotherm /

Muthusamy and Kannan [134] synthesized polypyrrole–sul-
anodic type/chemisorption
fonated melamine formaldehyde nanocomposites (PPy–SMF NCs)
Adsorption isotherm and
varying the concentration of sulfonated melamine formaldehyde

and characterized using UV–visspectroscopy, FTIR, SEM, EDS, DLS,
TEM, XRD, TGA, DSC, and conductivity measurements. It’s anti-
corrosive applications on 316L SS was examined in 3.5 % NaCl solu-
tion. Subsequent studies showed conclusively that the introduc-
nature
tion of PPy–SMF NCs beneficially affects the protection efficiency

of 316 L SS exhibiting IE in the range of 86.1 % to 96.1 %. The pres-
—
ence of CAS, NAH, and O@S = O groups were confirmed by FT-IR

efficacy at optimum
92 % at 1 10-3 M
Highest protection
spectroscopy. Besides these data, no clear indication of the mech-

92.6 % at 1.5 %
anism was given. In another report the inhibition behavior of 5-

amino-1,3,4-thiadiazole-2-thiol to prevent pitting corrosion of A-
890-1B SS in 3.5 % NaCl solution [135] was explored. The data sug-
conc.
gest that increasing the inhibitor concentration leads to more pos-

itive pitting potentials.
Talebian et al., [136] tested the anti-corrosive applications of
Corrosion
CRi-0.53
(mmpy)
CRb-6.7
three newly synthesized Schiff base derivatives, namely sodium

rates
(E)-4-(nitrobenzylideneamino)-benzoate (SNBB), sodium (E)-4-(b

enzylideneamino)-benzoate (SBB), and sodium (E)-4-
(hydroxybenzylideneamino)- benzoate (SHBB) to prevent pitting
Corrosion Techniques
and crevice corrosion of 304 SS in 0.1 M NaCl.The inhibitory effi-

cacy of the Schiff base compounds was not affected by variations
in group functionality at the inhibitor’s terminal aromatic ring.
However, SNBB gave the best inhibitory efficacy; a larger potential
region of the stable passive regime and more positive pitting
PDP
potentials. SVET maps showed that in the inhibitor-free solution,

metastable pitting occurred. However, in the presence of SNBB,
the SVET images reveal that the compound prevents metastable
Experimental
pitting by preventing passive layer breakdown at the initial pit

conditions
nucleation step. The SNBB molecule is a potent chelator and can

form stable chelates with the Fe(II) ions; the SNBB molecules
may migrate to the pores created in the passive film to react with
the Fe ions and form chelates (with stability constants logK1 = 6.31
and log K2 = 5.26) which will deposit finally at these sites and
Conc. of
eventually plug them.

3M
HCl
The corrosion preventive capability of self-assembled monolay-

ers (SAMs), of L-cysteine (CYS) and L-methionine (MET) for 316L SS
in 0.5 M NaCl solution at room temperature was studied [137] by
Characterization
potentiodynamic polarization curves as well as EIS measurements,

techniques
FT-IR spectroscopy, and SEM. The results showed that the SAMs of
individual CYS and MET significantly retarded the corrosion rates
of 316L steel. Moreover, experimental results supported the better
performance of CYS than MET. Data on the joint use of CYS/MET
and sodium dodecyl benzene sulfonate (SDBS) suggested a notice-
able synergistic anticorrosion effect which increased the IE from
71.85 % to 83.49 % with CYS and 55.59 % to 64.59 % with MET,
Chemical structure, name and
abbreviation of inhibitor used
respectively. Presumably, Cl- is adsorbed on SS and modified the

surface, which then readily adsorbs protonated CYS/MET mole-
cules. Later, the formation of hydrogen bonds between head groups
of SDBS and –NH2, –COOH, and –SH (of CYS) will lead to the forma-
1-thia-3-azaindene
tion of denser and more compact SAMs.

The corrosion of 2205 duplex SS was prevented using chitosan
in 3.5 % NaCl solution [138]. Chitosan operated as a mixed-type
inhibitor, as seen by polarisation curves. After 4 h of immersion
in the 0.2 g/L chitosan solution, a dense and homogenous adsorp-
tion coating coated the sample surface, and the inhibitory effi-
ciency (IE) achieved its maximum value of 62.47 %. Compared
Table 5 (continued)
with the blank specime, the specimens with chitosan inhibitor

exhibited a smaller corrosion current density, a more significant
SS type
304 SS
pitting potential, and a more expansive anodic passivation zone,

which demonstrated the excellent inhibition effect of chitosan on
2205 SS.
27
1, 1.5, and 2 g/L) of locust bean gum (LBG) was recently investi-
gated [142]. The best inhibition was shown in 0.15 M
NaCl + 2gL–1 LBG solution. LBG reduced corrosion by slowing the
rate of reactions without changing anodic and cathodic reactions.
ICP-OES analyses suggested that the metal dissolution in NaCl
solution was more as compared to LBG inhibited media. In a recent
publication [143], electrochemical measurements are performed to
study the effects of l-lysines and arginine on the corrosion of
316LSS. Both of these compounds can restrain the corrosion of this
type of steel by acting as an inhibitor. However, depending on the
addition of I ions, either of these compounds can improve the per-
formance of the corrosion inhibition.
Fig. 19. The curves of corrosion, protection, and pitting potentials versus 2-MBI Table 6 reports details of inhibition efficacies of a few more
concentration for 316 SS at ambient temperature [139]. inhibitors used for SS in NaCl media [144–149].
Pitting corrosion of 316 austenitic SS has been investigated in 3.6. CO2/H2S environment
3.5 % NaCl solution at 25, 40 and 60 °C using 2-
mercaptobenzimidazole (2-MBI) polyethylenimine with different Challenging operating circumstances in sour oil and gas wells
concentrations [139]. Fig. 19 illustrates the curves of corrosion, generate substantial tubular steel corrosion during exploration.
protection, and pitting potentials versus 2-MBI concentration for Environmental factors, materials properties, and corrosion scales
316 SS, which showed that 2-MBI increased pitting potential have all been studied concerning sulphide stress corrosion cracking
towards noble values. (SSCC) in oil and gas wells where CO2 and H2S coexist [150]. Most
The inhibitor 2-MBI suppresses pitting on the alloy surface and reports, however, focus on internal corrosion [151] of tubular and
improves pitting corrosion resistance. Both inhibitors are adsorbed pipeline steels during oil and gas extraction and transportation,
on the surface using the Langmuir isotherm adsorption model, with little emphasis paid to H2S/CO2 corrosion in an annular envi-
which shows that a single layer of organic inhibitor molecules is ronment [152] between tubing steel and casing steel.The corrosion
adsorbed. The growth of an adsorbed film with a physical character inhibitors for SS in sweet and sour environments have been inves-
on the surface of 316 SS was indicated by the decreased inhibition tigated scarcely. The outcomes of inhibitors used to prevent SS cor-
efficiency with rising temperature and activation energy in the rosion in H2S/CO2 media has been discussed in the section below.
presence of inhibitors. The presence of inhibitors reduced the num- The inhibitive effects of imidazoline (IM), 1-butyl-2- thioben-
ber of pits, as evidenced by optical microscope photographs zylbenzimidazole (BTBBI) and lauric acid (LA) [153] on the galvanic
(Fig. 20). corrosion between N80 CS and 13Cr SS in CO2-H2O system condi-
In a 3% NaCl solution, Finsgar et al. [140] explored the impact of tions was studied. IM, BTBBI, and LA could inhibit the corrosion
Polyethyleneimine (PEI) on the uniform and pitting corrosion of of N80 CS no matter whether coupled with 13Cr SS. However,
AISI 420 SS. PEI efficiently protected SS against the uniform and the galvanic effect between N80 CS and 13Cr SS decreases the inhi-
pitting corrosion, according to the findings. bitive effects of inhibitors. In the solutions containing BTBBI or LA,
Santolina chamaecyparissus extract was tested as a natural severe pitting corrosion occurred with a high galvanic current den-
inhibitor on the corrosion of 304 SS in a 3.5% NaCl solution by sity. In contrast, IM had the maximum inhibition efficiency among
Shabani-Nooshabadi and Ghandchi [141]. The inhibition efficiency these three inhibitors with the lowest corrosion rate and galvanic
rose when the concentration of Santolina was raised, with the most current density. Under dynamic supercritical CO2 circumstances,
excellent inhibition efficiency of 86.9% achieved at 1.0 g /1. the inhibitory effects of these three inhibitors on galvanic corro-
The corrosion behavior of AISI 304 SS, E150 Al alloy, and copper sion of N80 CS coupled with 13Cr SS were in the order
in 0.15 M NaCl containing various concentrations (10–3, 10–2, 10–1, IM > BTBBI > LA.
Fig. 20. OM images of steel surface in 3.5 % NaCl solutions containing (a) without inhibitor, (b) 500 ppm MBI, (c) 750 ppm MBI, (d) 1000 ppm PEI and (e) 2500 ppm PEI [139].
28
Table 6

Summary of some major reports published on corrosion inhibition potential of SS in NaCl solution.
SS type Chemical structure, name and abbreviation of Characterization Conc. Experimental Corrosion Corrosion Highest protection efficacy Adsorption isotherm/ nature Ref
inhibitor used techniques of condition Techniques rates
NaCl (mmpy)
316 Aloe-Vera extract — 3% — WL, PDP, EIS — 90 % at 100 ppm -/ [144]
mixed type
AISI 304 austenitic elemental 0.1 M T- 25 °C PDP, SVET, — — — [145]
SS chemical OCP, SEM, XPS
analysis, FT-IR
and 1H NMR
elemental 0.1 M T- 25 °C PDP, SVET, — — —

chemical OCP, SEM, XPS
analysis, FT-IR
and 1H NMR
elemental 0.1 M T- 25 °C PDP, SVET, — — —

chemical OCP, SEM, XPS
analysis, FT-IR
and 1H NMR
29
13Cr stainless — 1% Immersion OCP, PDP, EIS, — 56.2 % -/ [146]

steel time- 1 h XPS, SEM-EDS Anodic type
304 SS sodium tungstate + penicillin G — 3.5 % T- 35, 52, PP, EIS, CV, — 93.5 % at 2.5 mM sodium Langmuir adsorption [147]
70 °C SEM tungstate + 50 ppm penicillin isotherm/mixed
G type/physisorption
AISI 304 Hydroxyethyl Cellulose — 3.5 % PP, EIS, SEM, 66 % at 600 ppm — [148]
DFT
UNS N08904 SS — 3.5 % Immersion WL, PP, EIS, CRb-5.02 — Langmuir adsorption [149]
time- 168 hrs SEM-EDS CRi-0.003 isotherm/mixed type/
physisorption
coconut

shell powder
(CSP)
Fig. 21. Synthesis of bis(2-((2-palmitoamidoetil) amino) etil) 1H-imidazol-4,5-dicarboxilate. R = alkyl chains of fatty acids contained in palm oil [154].
In H2S-containing environment, a nonionic gemini surfactant dye PI) appeared on the 14th day due to nutritional depletion, as
derived from palm oil, namely bis(2-((20palmitoamidoethyl) seen in Fig. 22C. From the first day of the experiment until the
amino) ethyl) 1H-imidazole 4,5-dicarboxilatto (Fig. 21), was used 14th day, CLSM pictures (Fig. 22A’, 2B0 , and 2C’) revealed no devel-
to inhibit the UNS S41425-type supermartensitic SS corrosion at oped biofilms on the surfaces in the inhibited medium.
rotating speeds of 0, 100, 500, 1000, and 2000 rpm at 50 °C Catechin hydrate (CH) inhibited biocorrosion of 304L SS with an
[154]. The layer of chromium oxide formed on the SS surface was excellent IE of 99.8 % [157] was studied. The electrochemical find-
found to be responsible for passivation behavior which remained ings revealed that P. aeruginosa accelerated 304L SS corrosion,
unaffected on increasing rotational speed. whereas CH hindered corrosion by creating a protective barrier
Ecorr values were unaffected by increasing rotational speed, on the coupon surfaces. The quantitative polymerase chain reac-
however Icorr and passivating current were increased. Under hydro- tion (qPCR) data in this work showed that CH downregulated the
dynamic conditions, the capacitive semicircle diameter, Rct, was expressions of genes lasI, rhlI and pslA by 82.7 ± 5.7 %, 73.1 ± 12.
moderately impacted by the rotating speed and was smaller than 5 % and 37.5 ± 9.2 %, respectively. This could be one of the reasons
that achieved under stagnant conditions, signaling that the corro- through which CH inhibited the formation of P. aeruginosa biofilms
sion rate accelerated as the rotational speed improved. and lowered the 304L SS MIC. Analysis of pit depth data as 3D
images are given in Fig. 23 which showed that surfaces of the cou-
pons in the CH inhibited medium were relatively smooth with the
4. Environment containing microorganisms
absence of pits confirming the excellent pitting corrosion protec-
tion by CH in comparison to presence of P. aeruginosa with a pit
Microbial attachment on material surfaces followed by biofilm
depth of 19.5 lm.
formation can cause electrochemical changes at the metal/biofilm
The application of garlic extract (GAE) as a green inhibitor to
interface, such as a drop in pH due to acidic metabolites secreted
control MIC of API 5LX CS and 316 SS in hypersaline-produced
by microorganisms, a decrease in dissolved oxygen due to micro-
water environment enriched with corrosive bacteria was carried
bial respiration beneath the biofilm, and localized high concentra-
out [158]. Weight loss and electrochemical analysis showed that
tions of electrolyte constituents [155], resulting in physical bio-
deterioration or biodegradation of the metal surface. Anodic and/
or cathodic corrosion reactions are accelerated when microorgan-
isms are present. Microbiologically influenced corrosion (MIC) is
the name of the phenomenon [156]. The prevention and control
of MIC have gotten a lot of attention in recent years, and they’re
primarily based on eliminating the microbial cell or blocking the
production of biofilms. Biocides are the most effective approach
for preventing the MIC among the strategies tried to avoid it.
Due to the high toxicity of biocides, researchers set out to develop
eco-friendly, renewable, and readily available bio corrosion inhibi-
tors and antimicrobial agents with excellent efficiency. The follow-
ing section list corrosion inhibitors for MIC corrosion of SS.
In a work by Lekbach et al., the ethanolic extract of Cistus ladan-
ifer (belonging to the Cistaceae family) leaves was utilized as a
potential green bio-corrosion inhibitor for 304L SS in the medium
containing P. aeruginosa [156]. In the case of 304L SS coupons
incubated in the inhibited medium, the EOCP and Ecorr underwent
a positive shift, accompanied by an increase of Rct values and a
decrease in the corrosion rates. The researchers observe that Cistus
ladanifer extract acted as a mixed inhibitor, controlling the anodic
response primarily. The inhibited medium has a substantially
lower icorr value than that of the abiotic environment. As a result,
the inhibition efficacy was around 99.36 %, indicating that the 304L
SS coupon surfaces were well protected against P. aeruginosa cor-
rosion. A CLSM test was used to analyze the biofilms’ survival and
thickness after 1, 7, and 14 days. The results showed that the bio-
film density and thickness increased from the first to the seventh Fig. 22. CLSM 3-D images of the P. aeruginosa biofilms on 304L SS coupon surfaces
after live/dead staining: (A) after 1 day in the biotic medium; (B) after 7 days in the
day of incubation (Fig. 22A, B). Live bacteria were the dominant biotic medium; (C) after 14 days in the biotic medium; (A0 ) after 1 day in the
microorganisms (green dots stained by the green-fluorescent dye inhibited medium; (B0 ) after 7 days in the inhibited medium; (C0 ) after 14 days in
SYTO 9). Dead bacteria (red dots, labeled with the red-fluorescent the inhibited medium [156].
30
Fig. 23. Images of the largest pit depth measured using CLSM on 304L SS coupon surfaces after 14 days of incubation in the (a) abiotic, (b) biotic and (c) inhibited media [157].
B. subtilis A1 and S. parvus B7 increased the corrosion in both met- mixed-type inhibitors with anodic preponderance. At 700 ppm,
als. GAE was shown to inhibit corrosion in both metals in the pres- the most efficacious compound had the highest inhibitory effi-
ence and absence of bacteria; inhibition efficiencies were about ciency (90%). Adsorption on the metal surface, according to the
81 ± 3 % and 75 ± 3 % for abiotic system while 72 ± 3 % and Langmuir adsorption isotherm, was considered to represent the
69 ± 3 % in the presence of mixed bacterial consortia for CS and mechanism of inhibition. Compounds 6, 7, and 8 had the highest
SS, respectively. In a recent report [159], the effect of D-cysteine efficiency (82, 84, and 90%, respectively) at 700 ppm. On the con-
(D-cys) on the microbiologically influenced corrosion (MIC) of trary, compound 9 showed higher inhibition efficiency values at
304 SS was studied. The results indicated that the addition of D- low concentrations and lower efficiencies at high concentrations.
cysteine inhibited the formation of P. aneruginosa biofilms on This suggests the steric hindrance for compound 9 molecule since
the surface of the SS. The results indicated that the presence of it contains two adjacent phenylene rings in the molecule’s center,
D-cys inhibited the growth of these bacteria. However, it did not resulting in a nonplanar molecular structure.
affect the corrosion rate of the steel. Through the use of X-ray pho- The inhibitive performances of six tertiary amine methacrylate
toelectron spectroscopy and scanning electrochemical microanaly- based water soluble diblock copolymers (structures are given in
sis, it was revealed that the presence of D-cys greatly reduced the Fig. 24) on AISI 304 SS in double distilled water (DDW, at pH 7.6)
destructive effect of the adhered P. aeruginosa cells on the passive
film of the SS, thus inhibiting the MIC of the SS.
5. Miscellaneous
Four triazine derivatives namely 2,20 -[(6-Chloro-1,3,5-triazine-

2,4-diyl)bis(azanediyl)]diacetic acid (1), 2,20 ,200 ,2000 -[[6,60 -[Ethane-
1,2-diylbis(azanediyl)]bis(1,3,5-triazine-6,4,2-triyl)]tetrakis(azane
diyl)]tetraacetic acid (6), 2,20 ,200 ,2000 -[[6,60 -(Piperazine-1,4-diyl)bis(
1,3,5-triazine-6,4,2-triyl)]tetrakis(azanediyl)]tetraacetic acid (7),
2,20 ,200 ,2000 -[[6,60 -[1,4-Phenylenebis(azanediyl)]bis(1,3,5-triazine-6,
4,2-triyl)]tetrakis(azanediyl)]tetraacetic acid (8), 2,20 ,200 ,2000 -[[6,60 -[
[1,10 -Biphenyl]-4,40 -diylbis(azanediyl)]bis(1,3,5-triazine-6,4,2-triy
l)]tetrakis(azanediyl)]tetraacetic acid (9) were employed to
improve 316L SS corrosion resistance for biomedical applications
by electrochemical measurements in simulated body fluid (SBF)
at 37 °C [160]. According to the findings, all the examined com- Fig. 24. The molecular structure some tertiary amine methacrylate monomer used
pounds showed good corrosion inhibition and functioned as in the synthesis of (co)polymers [161].
31
was investigated using potentiodynamic polarisation, EIS, SEM, corrosion inhibitors for industrial applications. This section pro-
EDX, AFM and ICP-OES methods [161]. Polymers studied showed vides a full explanation of the relationship between these theoret-
a mixed type of inhibitor property and adsorbed on the metal sur- ical characteristics and the corrosion inhibition ability of various
face physically following Langmuir adsorption equation. chemicals on SS corrosion.
In magnesium chloride complex electrolyte, 1-butyl-1- The DFT approach [167] was used to evaluate the inhibitory
methylpyrrolidinium chloride (Py1,4Cl) was investigated as an effect of 1-(4-nitrophenyl)-5-amino-1H-tetrazole on the corrosion
excellent corrosion inhibitor for 316L SS current collectors [162]. of 316L SS in H2SO4 solution. The authors investigated how donor–
By preventing the initiation of corrosion pits and passive film acceptor interactions between the p-electrons of heterocyclic com-
breakdown over prolonged electrochemical cycling on the SS, a pounds and the unoccupied d-orbitals of metal surface atoms can
0.2 wt% usage of Py1,4Cl increased anodic stability by 0.1–0.3 V lead to adsorption of 1-(4-nitrophenyl)-5-amino-1H-tetrazole on
in most current collectors while maintaining the initial coulombic SS surface. As a result, the energy of the frontier orbitals was eval-
efficiency for Mg deposition/stripping at more than 98 %. uated. The LUMO energy shows how a molecule can gain charge
Six choline based deep eutectic solutions (CDES) namely ChCl- when attacked by electron-pair donors. The HOMO energy explains
Ur (choline chloride-urea), ChCl-EG (choline chloride-ethylene gly- how a molecule can transfer charge when attacked by electron-
col), ChCl-Gl (choline chloride-glycerol), ChCl-MA (choline seeking reagents. Because the energy gap (DE) among the resulting
chloride-malonic acid), ChCl-Ph (choline chloride-phenol) and border orbitals is small, the interactions between the responding
ChCl-TG (choline chloride-triethyene glycol) has been demon- species become stronger. The electronic properties of synthesized
strated to be effective corrosion inhibitors for copper, MS and inhibitor, such as HOMO, LUMO energies, and frontier molecular
316 SS [163]. According to the study, the corrosion rate of these orbital coefficients, were reported in this regard. Fig. 25(a-d)
materials rose as the temperature and moisture content increased. showed structure, optimized, HOMU and LUMO sites respectively
At 25 °C, the corrosion inhibition of 316 SS was found to be highest of tested compound. The HOMO site (Fig. 25c) in the 1-(4-nitrophe
in the presence of pure ChCl-Ur. The characteristics of 1- nyl)-5-amino-1H-tetrazole molecule is frequently allocated
benzylimidazole have been studied to determine its effective cor- around N atoms. This diagram shows the inhibitor and SS surface’s
rosion inhibition against 316L SS in 2% HCl + 3.5% NaCl [164]. It reactive contact locations. The Mulliken population analysis, illus-
was a mixed-type inhibitor with greater anodic influence. The trated in Fig. 25(e), provides additional evidence for the interaction
effect of 1-benzylimidazole on the formation and protection of a between active inhibitor sites and SS surface. The N atoms of the
passive film has been studied. The weight loss and electrochemical inhibitor have a significantly higher negative charge than the other
measurements show that its efficiency is greater than 70% at atoms, as seen in Fig. 25(f). As a result of the displacement of water
1000 ppm. molecules from the metal surface and the sharing of electrons
between N atoms and the metallic surface, this corrosion inhibitor
can adsorb as a neutral molecule on the metal surface almost
6. Theoretical modeling in corrosion inhibition assessment of instantly. The positively charged N atoms of 1-(4-nitrophenyl)-5-
SS amino-1H-tetrazole adsorb predominantly by electrostatic interac-
tions, it should be highlighted.
Currently, several research papers are engrossed in computa- Koumya et al. [168] explored the corrosion inhibition behavior
tional modelling investigations of diverse chemical compounds of amino cadalene on 321 SS in H2SO4. In the study, the quantum
for metal corrosion prevention [165,166]. The goal of these studies chemical calculations using DFT with the B3LYP/6-31G (d, p) have
is to gain a better understanding of how organic compounds inter- been applied to correlate the molecular configuration, and IE mon-
act with metal surfaces at the molecular level. This method is par- itored from calculated investigational data. The difference in the
ticularly significant in the development of innovative and effective inhibitor molecule’s HOMO and LUMO energy levels is crucial in
Fig. 25. (a) Structure of 1-(4-nitrophenyl)-5-amino-1H-tetrazole; (b) optimized molecular structure of 1-(4-nitrophenyl)-5-amino-1H-tetrazole, H atoms have been omitted
for clarity; (c) the highest occupied molecular orbital (HOMO) of 1-(4-nitrophenyl)-5-amino-1H-tetrazole; (d) the lowest unoccupied molecular orbital (LUMO) of 1-(4-
nitrophenyl)-5-amino-1H-tetrazole; (e) Mulliken charge population analysis and vector of dipole moment of 1-(4-nitrophenyl)-5-amino-1H tetrazole; (f) natural charge
population analysis of 1-(4-nitrophenyl)-5-amino-1H-tetrazole [167].
32
Fig. 26. The optimized configurations of inhibitor molecules in gas phase (a) and aqueous phase (b) using DFT/B3LYP/6-31G++(2d,p) [56].
Fig. 27. (a) The most stable low energy configuration for the adsorption of New Fuchsine, H2O, and Cl- on a-Cr2O3 (0001) surface obtained through the Monte Carlo
simulation, Red Balls (O atoms), Gray Balls (Cr atoms), and Green Balls (Chloride). (b) The most stable low energy configuration for the adsorption of New Fuchsine, H2O, and
Cl- on a-Cr2O3 (0001) surface containing oxygen vacancy obtained through the Monte Carlo simulation, Red Balls (O atoms), Gray Balls (Cr atoms), and Green Balls (Chloride)
[64].
33
its inhibitory ability. It has been discovered that excellent corro- retical vibrational spectra have been received to show the func-
sion inhibitors can donate electrons to metal’s unoccupied d- tional hydroxyl groups (–OH) in the reported compounds.
orbitals and retrieve electrons from the metal. Furthermore, the Therefore, the optimized arrangement of tested inhibitors C1, C2,
IE is better when the DE is minimal. The most likely locations for and C3 in gas and aqueous phases was verified as exposed in the
electrophilic/nucleophilic attack, according to Fukui indices of Fig. 26 to find out the other local and global parameters. In agree-
amino cadalene, are 19 N, 15C, 22C, 28C, and 32C. ment with the investigational data, the theoretical findings exhib-
Alahiane et al. [56] reported the corrosion inhibition efficiency ited that the inhibition efficiency order was C3 > C2 > C1. MD
(IE) of benzoic acid (C1) and its derivatives, namely para- results suggested that C3 has the highest binding energy (Ebind)
hydroxybenzoic acid (C2), and 3,4-dihydroxybenzoic acid (C3), compared to the other compounds (Ebind (C3) = 79.42, Ebind
towards increasing the corrosion resistance of austenitic AISI 316 (C2) = 75.98 and Ebind (C1) = 71.36). A better IE of C3 was suggested
SS in 0.5 M HCl using experimental and theoretical approaches. due to a benzene ring and four oxygen atoms.
The quantum chemical calculations using DFT at the B3LYP level Ghelichkhah et al. [64] studied the corrosion inhibition effect of
of theory with 6-31G+(2d,p) and 6-31G++(2d,p) basis sets in gas new fuchsin (NF) for type 304 L SS corrosion in 0.5 M HCl by exper-
and aqueous phase and MC simulations were also applied for fur- imental and theoretical tools (DFT and MD). The theoretical data
ther insight into the adsorption mechanism of inhibitor molecules were interpreted in the Point Defect Model (PDM) and Anion-
on Fe (1 1 0). The theoretical parameters, namely ELUMO, EHOMO, DE, Catalyzed Active Dissolution Model (ACADM). Both account for
g, r, v, x, and e have been obtained, and the corrosion inhibition the investigational data. DFT and MD simulation exhibit that new
behavior of C1, C2 and C3 has been explained. Furthermore, theo- fuchsin molecules adsorb onto a-Cr2O3 (0001) by electrostatic
Fig. 28. The B3LYP/6-311G** optimized geometry, HOMO, and LUMO of neutral (top row) and protonated (bottom row) allicin, alliin, pyridoxal phosphate, and pyrrole
compounds [95].
34
Fig. 29. The frontier molecular orbital density distribution of 5-Azidomethyl-7-morpholinomethyl-8-hydroxyquinoline [132].
interaction augmented probably via a few donor bond formations, 6–31++G(d, p) basis set, provides the correct outcomes. Addition-
in a planar-manner with negative interaction energy. Moreover, ally, the anticorrosion behaviors of molecular Schiff based inhibi-
the presence of O vacancies in the oxide surface raises the affinity tors explain linear correlation with the EHOMO, ELUMO, DE, x, l, r,
of Cl and new fuchsin to absorb on the surface.The electrostatic g, and DN parameters. Anticorrosion performances of studied
bond length of chloride on Cr2O3 surface decreased from 5.083A° molecular Schiff based inhibitors have been chiefly verified via
to 3.504 A° when oxygen vacancies were created on the oxide sur- the molecules’ electron-donating capacities of HOMO states. The
face, as shown in Fig. 27(a-b), indicating a stronger affinity of chlo- higher energy of HOMO shows the more vital electron-donating
ride for the oxygen vacancies.The electrostatic bond length of the ability and hence the superior anticorrosion performance. Based
NH2 group on the oxide surface containing oxygen vacancies on resemblances in molecular arrangements, four different molec-
increased at the same time (3.184 A° to 4.174 A°), which could ular inhibitors have been preferred to predict their most related
be due to identical positive charges associated with surface oxygen structure–activity equations. By presenting HF results, it was found
vacancies and NH2 groups repelling each other.Moreover, from that M5 and M7 molecules confirmed outstanding anticorrosion
Fig. 27(b), it can be estimated that in the presence of an oxygen performances and that the predicted IE could reach 99 % for M5
vacancy, NF laterally absorbed on the a-Cr2O3 (0001) surface.The inhibitor. Thus, this study gives a theoretical process by which it
adsorption energy of NF on a surface with oxygen vacancies is probable to predict the anticorrosion performance of molecules
(-345.66 kJ/mol) is lower than the adsorption energy of NF on a with geometrical configurations such as Schiff based inhibitors.
surface without oxygen vacancies (-319.78 kJ/mol). This could be Katori et al. [67] reported the theoretical studies for three ionic
due to the positive charge associated with surface oxygen vacan- liquids.Various parameters like EHOMO, ELUMO, DE, and dipole
cies, which causes more electrostatic interactions with NF. moment were reported. Further, Fukui indices, Mulliken’s atomic
Asfia et al. [95] reported the corrosion inhibition of garlic charge, and molecular electrostatic potential mapping (MEP)
extract on AISI 304 SS in 0.5 M HCl medium using electrochemical (Fig. 30) were also reported.The data of Fukui indices exhibited
and computational tools such as DFT, MD, and MC studies. DFT was that the atoms C(1), N(2), C(3), C(4), N(5) for IL1, the atoms C(1),
explained via the donor–acceptor interaction, which showed that N(2), C(3), C(4), N(5) for IL2 and the atoms C(1), N(2), C(3), C (4),
N, O, S, and C atoms were responsible for inhibiting SS corrosion N(5) for IL3 are also approachable to acquire electrons. These
due to the formation of diverse bonds with the surface (Fig. 28). atoms (i.e., imidazolium moiety) have large values of (f+k). Whereas,
Negative adsorption energies obtained from the MD confirmed C(1), C(3), C(4), N(5), O(8) atoms for IL1, C(1), C(3), C (4), N(5), O(8)
the spontaneous adsorption of garlic molecules on the SS surface
and corrosion inhibition film formation for the surface protection.
Mazkour et al. [132] used experimental and theoretical investi-
gations to investigate the corrosion inhibition effect of 5-Azidome
thyl-7-morpholinomethyl-8-hydroxyquinoline for AISI 304 SS in
5.5 M H3PO4 solution. According to the DFT findings, 5-Azidome
thyl-7-morpholinomethyl-8-hydroxyquinoline has a high capacity
to adsorb on the surface of SS, implying increased complex stabil-
ity. The HOMO and LUMO orbitals for 5-Azidomethyl-7-morpholi
nomethyl-8-hydroxyquinoline are also centered around the aro-
matic rings and O atoms, as seen in Fig. 29. They appear to be
the preferred molecular fractions for improving adsorption on
metal surfaces.
Recently, Chen et al. [169] reported the anticorrosion effect of
some Schiff based inhibitors (M5, M6, M7, and M8) on 304 SS in
HCl medium by using three different theoretical ab initio methods,
namely Hartree-Fock (HF), Möller-Plesset perturbation theory on
the 2nd order (MP2), and density functional theory (DFT). The cor-
relations among IE of Schiff based inhibitors and several precise
molecular property-related parameters are calculated. Using linear
regression analysis, the correlations among IE and every parameter
are carefully analyzed to get the most efficient parameters for
excellent IE. As an outcome, the comparison among all the three
Fig. 30. Graphical presentation of the MEP of the ionic liquid’s molecules using
diverse theoretical ways confirms that the HF process, with the DMol3 module [67].
35
Table 7
Molecular structure, name and abbreviation of inhibitors, metals/medium, and DFT parameters reported in the literature.
Structure and abbreviation of inhibitor Metals and DFT parameters Ref.

Medium
304 SS/H2SO4 ELUMO (eV) = -3.40 [131]
EHOMO (eV) = -7.65
DE (eV) = 4.25
l (Debye) = 13.33
Triethylsulfoniumbis
(trifluoromethylsulfonyl)imide
(TESFI)
304LSS/sterile, ELUMO (eV) = -0.721 [157]
DE (eV) = 5.267
biotic and EHOMO (eV) = -5.987
inhibited
Catechin hydrate (CH)

SS/HCl I (eV) = 6.14A [102]
(eV) = 2.80
N’,N’’’- DE (eV) = 3.34
l (D) = 9.11
v (eV) = 4.47
g (eV) = 1.67
(thiophene-
DN = 0.75
2,5-diylbis(methanylylidene))di(isonicotinohydrazide)
(SS1)
I (eV) = 5.63A
(eV) = 2.46
0
2,2 -(thiophene-2,5-diylbis DE (eV) = 3.17
l (D) = 10.57
v (eV) = 4.05
(methanylylidene))bis g (eV) = 1.58
(N-phenylhydrazinecarbo thioamide) (SS2) DN = 0.92
SS/3M ELUMO (eV) = 0.281 (12-O-12), 0.283 (18-O-18), 0.328 (12-MOH-O- [59]
MOH-12), 0.327 (18-MOH-O-MOH-18)DE
3-oxa-1,5-pentamethylene-bis HCl (eV) = 5.177 (12-O-12), 5.178 (18-O-18), 5.580 (12-MOH-O-MOH-
12), 5.627 (18-MOH-O-MOH-18)
EHOMO (eV) = 4.896 (12-O-12), 4.895 (18-O-18), 5.252 (12-
(N-alkyl-N,Ndimethylammonium chloride
MOH-O-MOH-12), 5.300 (18-MOH-O-MOH-18)
r (eV1) = 0.386 (12-O-12), 0.386 (18-O-18), 0.358 (12-MOH-O-
MOH-12), 0.355 (18-MOH-O-MOH-18)
g (eV) = 2.58 (12-O-12), 2.58 (18-O-18), 2.79 (12-MOH-O-MOH-

12), 2.81 (18-MOH-O-MOH-18)I
3-oxa-1,5-pentamethylene-bis(N-alkyl-N-hydroxyethylN- (eV) = 4.89 (12-O-12), 4.89 (18-O-18), 5.25 (12-MOH-O-MOH-12),
methylammonium chloride) 5.30 (18-MOH-O-MOH-18)
E
(eV) = -0.281 (12-O-12), 0.283 (18-O-18), 0.328 (12-MOH-O-
MOH-12), 0.327 (18-MOH-O-MOH-18)
v (eV) = 2.30 (12-O-12), 2.30 (18-O-18), 2.46 (12-MOH-O-MOH-
12), 2.48 (18-MOH-O-MOH-18)
DN (eV) = -0.90 (12-O-12), 0.48(18-O-18), 0.81 (12-MOH-O-
MOH-12), 0.80 (18-MOH-O-MOH-18)
SS 201/1M HCl ELUMO (eV) = -0.78 (A), 0.73 (B), 0.68 (C) [86]
EHOMO (eV) = -9.14 (A), 9.12 (B), 9.10 (C)
DE (eV) = 8.36 (A), 8.39 (B), 8.42 (C)
(A) 2-(1-((1-(6- l (Debye) = 2.09 (A), 1.72 (B), 1.67 (C)
hydroxycyclohexa-2,4-dienyl)
ethylidene)hydrazono)ethyl)phenol
36
Table 7 (continued)

Medium
(B) 2-(((1-(6-hydroxycyclohexa-2,4-
dienyl)
ethylidene)hydrazono)methyl)phenol
(C) 2-((((6-hydroxycyclohexa-2,4-
dienyl)
methylene)hydrazono)methyl)phenol
SS/2 M HCl ELUMO (eV) = -5.90 (I-CH3), 5.87 (II-C2H5), 5.87 (III-C3H7) [101]
EHOMO (eV) = -8.67 (I-CH3), 8.73 (II-C2H5), 8.64 (III-C3H7)
DE (eV) = 2.77 (I-CH3), 2.86 (II-C2H5), 2.87 (II-C2H5)
Total Energy = -701.97 (I-CH3), 750.29 (II-C2H5), 789.61 (III-
C3H7)
l (Debye) = 8.89 (I-CH3), 8.40 (II-C2H5), 7.53 (III-C3H7)
1-Methyl-4-[4́-(–OCH3)-styryl] pyridinium iodide (I-CH3)
1-Ethyl-4-[4́-(–OCH3)-styryl] pyridinium iodide (II-C2H5)
1-Propyl-4-[4́-(–OCH3)-styryl] pyridinium iodide (III-C3H7)
SSl/1 M HCl I (eV) = 5.49 (S1), 5.43 (S2)A [72]

(eV) = 1.47 (S1), 1.93 (S2)
DE (eV) = 4.01 (S1), 3.50 (S2)
l (Debye) = 3.76 (S1), 4.94 (S2)
methyl 2-((2-hydroxybenzylidene)amino-3- v (eV) = 3.48 (S1), 3.68 (S2)
g (eV) = 2.00 (S1), 1.75 (S2)
DN (eV) = 0.87 (S1), 0.94 (S2)
(1Hindol-3-yl)propanoate
(S1)
2-(((1-hydroxy-3-(1H-indol-3-yl)-1,1-
diphenylpropan-2-yl)imino)methyl)phenol
(S2)
201 SS/1.0 M ELUMO (eV) = -0.27 (A), 0.51 (B) [79]
37
Table 7 (continued)

Medium
HCl EHOMO (eV) = -8.93 (A), 9.03 (B)
DE (eV) = 8.66 (A), 8.52 (B)
g (eV) = 4.33 (A), 4.26 (B)
r (eV) = 0.23 (A), 0.23 (B)
v (eV) = 4.6 (A), 8.52 (B)
(B) 1-(1-(cyclohexa-2,4-dienyl)ethylidene)-2-(1-phenylethylidene) l (Debye) = 0.15, 0.54 (B)
hydrazine
(C) 1-benzylidene-2-(cyclohexa-2,4-dienylmethylene)
hydrazine
304SS/0.1 M ELUMO (eV) = -2.09 (1), 2.02 (2), 2.51 (3), 2.28 (4), 2.31 (5), [78]
HCl 2.25 (6)
EHOMO (eV) = -6.23 (1), 6.11 (2), 6.47 (3), 6.39 (4), 6.15 (5),
(E)-(Phenylimino)methyl)phenol 6.07 (6)
DE (eV) = 4.14 (1), 4.09 (2), 3.96 (3), 4.11 (4), 3.84 (5), 3.82 (6)
(1)
2-((E)-(pTolylimino)methyl)
phenol
(2)
(E)-2-
(Hydroxybenzylideneamino)benzoic acid
(3)
(E)
-2-
(Hydroxybenzylideneamino)benzoic acid
(4)
2-((E)-(2 Hydroxyphenylimino)
methyl) phenol
(5)
2-((E)-(2 Mercaptophenylimino)methyl)phenol
(6)
304 SS/HCl ELUMO (eV) = -0.685 (C3), 1.179 (C4) [82]
38
Table 7 (continued)

Medium
EHOMO (eV) = -6.453 (C3), 6.290 (C4)
DE (eV) = 5.768 (C3), 4.411 (C4)
g (eV) = 2.8 (C3), 2.20 (C4)
r (eV) = 0.34 (C3), 0.45 (C4)
5-Ethyl-1,3,4-thiadiazol-2-amine (C3) v (eV) = 3.56 (C3), 4.08 (C4)
l (D) = 6.04 (C3), 6.58 (C4)
5-(p-Tolyl)-1,3,4-oxadiazole-2(3H)-thione (C4)
316 stainless ELUMO (eV) = 0.17005 ( [81]
steel/2MHCl HF/6–311++(d,p)), 0.23146 (B3LYP/6–311++(d,p)
EHOMO (eV) = -0.14571 (
HF/6–311++(d,p), 0.28652 (B3LYP/6-
311++(d,p)
DE (eV) = 0.41576 (HF/6–311++(d,p), 0.51798 (B3LYP/6-
ketamine drug
311++(d,p)I
(eV) = 0.24 (HF/6–311++(d,p), 0.28 (B3LYP/6-
311++(d,p)A
(eV) = -0.170 (HF/6–311++(d,p), 0.23 (B3LYP/6-
311++(d,p)
v (eV) = 0.037 (HF/6–311++(d,p), 0.027 (B3LYP/6-
311++(d,p)
l (eV) = 2.93 (HF/6–311++(d,p), 2.70 (B3LYP/6-
311++(d,p)
r (eV) = 4.81 (HF/6–311++(d,p), 3.86 (B3LYP/6-
311++(d,p)
x = 0.003 (HF/6–311++(d,p), 0.0014 (B3LYP/6-
311++(d,p)
e = 290.5 (HF/6–311++(d,p), 683.4 (B3LYP/6-
311++(d,p)
SS/ 1 M H2SO4 ELUMO (eV) = -0.08977 (A), 0.05644 (B), [108]
0.11984 (C)
EHOMO (eV) = -0.19275 (A), 0.25435 (B),
0.25837 (C)
DE (eV) = 0.10298 (A), 0.19791 (B), 0.13853 (C)
DN = 66.60 (A), 35.58 (B), 49.16 (C)
l (D) = 2.63 (A), 2.81 (B), 3.46 (C)
430 SS/0.5 M ELUMO (eV) = -10.2 (DPy), 1.5 (TPy) [122]

H2SO4 DE (eV) = 5.5 (DPy), 1.5 (TPy)
EHOMO (eV) = 15.5 (DPy),-2.8 (TPy)
1,10-dimethyl-4,40-dipyridinium di-
iodide
(DPy)
39
Table 7 (continued)

Medium
1,10-Bis (1-methyl
pyridinium-2-yl)-4,40-dipyridinium dichloride di-iodide

(TPy)
316L SS/1.0 M ELUMO (eV) = -1.018 [107]
H2SO4 EHOMO (eV) = -5.256
DE (eV) = 4.238
v (eV mol1) = 3.13
k (eV mol1) = 2.11
Benzethonium chloride (BCCS) DN = 0.91
AISI Type 321 ELUMO (eV) = 0.02 [170]
SS/ DE (eV) = 0.21
EHOMO (eV) = -0.19
DN = 31.71
l (D) = 1.72
316 SS/ 2.5 M ELUMO (eV) = -1.5409 [118]

H2SO4 DE (eV) = 3.9600
EHOMO (eV) = -5.5081
4-{[4-(dimethylamino)
benzylidene]amino}-5-methyl-4H-1,2,4-triazole-3-thiol
(DBTT)
304 SS/1 M HCl ELUMO (eV) = -0.06057 (I), 0.09862 (II), 0.12040 (III), 0.10454 [57]
(IV), 0.12038 (V), 0.11193 (VI)
DE (eV) = 0.14471 (I), 0.08699 (II), 0.08133 (III), 0.08394 (IV),
0.06958 (V), 0.06455 (VI)
EHOMO (eV) = -0.21528 (I), 0.18561 (II), 0.20173 (III), 0.18848
(IV), 0.18996 (V), 0.17648 (VI)
I- Carnosol
II- II- Luteolin 7-glucoronide
III-Luteolin 7-glucoside
IV-Rosmarinic acid
40
Table 7 (continued)

Medium
V-Sagecomarin
VI-Salvianolic acid
atoms for IL2 and C(1), C(3), C(4), N(5), O(8) atoms for IL3, which, as flow conditions, variation in the partial pressure of CO2, detailed
donate electrons for a coordinate bond for the empty d-orbital Fe. analysis of corrosion product formation/deposition in the presence
MEP revealed that the most significant positive areas in ionic liquid of inhibitor, and exploitation of functionalized amino acids and
molecules are primarily over the imidazolium moiety. Areas of natural polymers than the use of simple amino acids and natural
higher electron density in ionic liquid molecules may be excellent polymers. The use of nanotechnology in inhibiting SS corrosion is
for 201 SS surface interactions. IL3 molecules have a higher dEads/ highly suggested. Graphene/carbon nanotubes-amino acid-based
dNi value (-153.65 Kcal/mol) than IL1 and IL2 molecules (-130.55 nanocomposites, functionalized graphene oxides can be tested as
and 135.12 Kcal/mol, respectively), indicating that IL3 molecules corrosion inhibitors for SS. Moreover, the studies on combinations
have better adsorption than IL1 and IL2 molecules. of inhibitors like surfactant-surfactants, surfactant-polymer,
In Table 7, the theoretical parameters of some other inhibitors surfactants-amino acids, surfactants/halides, amino acid/halides,
for SS corrosion are listed [57,59,72,78,79,81,82,86,101,102,108, polymer-halides, can be worked together to increase inhibition
122,131,170]. effect, which could aid in the development of a realistic inhibitor
formulation.To clarify their inhibition mechanism by quantum
7. Drawbacks and future perspective chemical calculations and simulation using molecular mechanic
process is highly recommended before the laboratory experi-
A perusal of literature suggest that most of the research work ments.Despite the fact that researchers are working tirelessly to
done to discover corrosion inhibitors for SS corrosion was carried develop cheap, environmentally friendly, and readily available
out in acidic media. Limited references are available on the corro- green corrosion inhibitors from greener sources/ materials, many
sion prevention of SS in seawater conditions where SS suffers from industries are still using corrosion inhibitors that have been proven
localized corrosion, such as pitting and stress corrosion cracking to be costly and toxic. Future research should focus on wastes
(SCC). Among the natural ecofriendly products, plant extracts have derived from greener sources, which are an environmental hazard
been largely used as corrosion inhibitors to prevent localized cor- that impacts both humans and aquatic life. Eco-wastes can give
rosion of SS. Howevere, the fundamental flaw in exploring plant important substances at a low cost which may act as efficient cor-
extracts as corrosion inhibitor for SS is a lack of mechanistic under- rosion inhibitors. It is practical, cost-effective, and ecologically
standing of the implicated protection mechanism, which begins friendly to employ these bioactive leftovers as a foundation for
with a thorough characterization of the extract’s individual con- generating valuable compounds.
stituents. Many research groups focus on crude extracts, ignoring
the specificity of action of single compounds, both in terms of 8. Conclusion
the best impact and the physico-chemical mechanisms involved.
Most of the research predicted the inhibitors’ mixed type inhibi- SS is a critical component in many aspects of modern life
tion activity. Despite numerous attempts to link inhibition effi- because of its characteristic features. anti-rust qualities set it apart
ciency and organic inhibitor’s molecular structure, mechanistic from other metals like iron and carbon steel.
knowledge of corrosion and inhibition processes is still inadequate The current article gives a complete summary of different
in many published papers, making proper inhibitor selection diffi- organic inhibitors applied for SS corrosion that have been pub-
cult. Many studies in the literature do not include a standard devi- lished during the last 15 years.
ation in their weight loss and electrochemical measurements thus The major classes of the SS inhibitors include plant extracts,
putting a question mark on the reproducibility of results. Addition- surfactants, heterocyclic compounds, amino acids, ionic liquids,
ally, there was no statistical analysis offered.Theoretical studies and carbohydrate derivatives.
were applied to the limited extent to examine the compounds Each of the inhibitor classes has its own set of advantages, e.g.,
under investigation. plant extracts are generally favoured because of their greenness
The collected literature on SS corrosion inhibition shows further and abundance; amino acids having outstanding solubility and
scope to extend the study on mitigation of SS corrosion utilizing eco-friendliness; heterocycles, macrocycles, and polymers have
inhibitors by considering the effect of substituent groups, more excellent surface coverage; and expired drugs, ionic liquids, and
detailed studies on synergism, the effect of temperature, as well polymers are novel inhibitor options.
41
To investigate the performance of various compounds as corro- [9] M. Talha, C.K. Behera, O.P. Sinha, A review on nickel-free nitrogen containing
austenitic stainless steels for biomedical applications, Mater. Sci. Eng. C. 33
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A Comprehensive Review of Corrosion Inhibitors

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