buildings

Review
Review of Corrosion Inhibitors in Reinforced Concrete:
Conventional and Green Materials
Amir Zomorodian 1, * and Ali Behnood 2

1 Renishaw PLC, Gloucestershire GL12 8JR, UK

2 Assets Logics, Mermaid Waters, QLD 4218, Australia; [email protected]
* Correspondence: [email protected]

Abstract: The corrosion of metals has been a major technical, environmental, and financial challenge
for many industries and has become a widespread problem in concrete structures and buildings.
Various techniques such as utilization of synthetic corrosion inhibitors have been developed to pro-
vide sufficient corrosion protection to reinforcing steel. The application of green corrosion inhibitors,
however, has recently attracted increasing attention since these sustainable materials decrease the rate
of corrosion and increase the durability and service life of reinforced concrete structures effectively.
Considering the emerging field of sustainable corrosion management, many researchers have eval-
uated various green corrosion inhibitors, reporting scattered results. Consequently, there is a need
for a comprehensive study to review, compare, and consolidate their findings in order to identify
research gaps and critical trends for further research. This article reviews the properties and effects
of various inhibitors including those nontoxic environmentally friendly inhibitors functioning at
high pH in concrete. It classifies a broad range of corrosion inhibitors and identifies their advantages
and disadvantages. Furthermore, it proposes a set of selection criteria to choose the appropriate
inhibitors based on their characteristics and sustainability requirements. It can be concluded that
natural corrosion inhibitors show promising potential for extending the service life of reinforced
concrete structures as a cost-effective and sustainable solution. Further investigation, however, is
demanded for evaluating their technical properties including modelling functional groups for cor-
rosion protection and their effectiveness under combined attack of corrosive ions. The findings of
this paper identify the main research trends and can guide researchers to develop further research
in the identified gaps towards sustainable progress in the field of civil engineering and corrosion
Citation: Zomorodian, A.;
management. It also helps practitioners in all relevant disciplines to gain effective knowledge on
Behnood, A. Review of Corrosion emerging green corrosion inhibitors.
Inhibitors in Reinforced Concrete:
Conventional and Green Materials. Keywords: corrosion; green inhibitors; reinforced concrete; sustainability
Buildings 2023, 13, 1170. https://
doi.org/10.3390/buildings13051170

Academic Editor: Elena Ferretti

1. Introduction
Received: 16 March 2023 The corrosion of reinforcing steel in civil infrastructure such as bridges, offshore
Revised: 11 April 2023
structures, and buildings affects their service life significantly. The main cause of the
Accepted: 22 April 2023
corrosion of reinforcing steel is the availability of chloride ions above the critical content
Published: 28 April 2023
in the vicinity of the reinforcement. These harmful ions originate from different sources
such as road-deicing or airborne sea salts [1]. It has been reported that around 10 percent
of bridges in the United States are not functioning properly due to corrosion of their
Copyright: © 2023 by the authors.
reinforcing steel [2]. According to the National Association of Corrosion Engineers (NACE),
Licensee MDPI, Basel, Switzerland. the total cost of corrosion is estimated to be USD 2.5 trillion, which is equivalent to 3.4% of
This article is an open access article the global GDP. However, selecting appropriate corrosion protection techniques can save
distributed under the terms and 15%–35% of the cost of corrosion, which is estimated to be between USD 375 and 875 billion
conditions of the Creative Commons annually on a global basis [3].
Attribution (CC BY) license (https:// Various techniques have been developed for corrosion protection and increasing the
creativecommons.org/licenses/by/ service life of reinforcing steel. Table 1 summarizes the main techniques which are used for
4.0/). corrosion protection.

Buildings 2023, 13, 1170. https://doi.org/10.3390/buildings13051170 https://www.mdpi.com/journal/buildings

Buildings 2023, 13, 1170 2 of 20

Table 1. The main techniques for corrosion protection of reinforced concrete.

Technique Description
This method works by inducing a small electrical current
Cathodic protection from the anode to the corroding steel; subsequently, this
current protects the steel from further deterioration [4].
This method works by removing the chloride ions from
Electrochemical techniques Re-alkalization (ER) contaminated concrete using direct and high-density
current for a limited period (days to weeks) [5].
This method restores the alkalinity of the concrete close to
Electrochemical chloride the reinforcing steel by introducing hydroxyl ions into the
removal (ECR) concrete, which subsequently passivates the
reinforcing steel [6].
This method is based on using chemical materials which
are physically or chemically adsorbed over the metal
Corrosion inhibitors
surface and change the interface chemistry, forming a
protective film on the surface.
Layered double hydroxides (LDHs) such as hydrotalcite
and hydrocalumite physically adsorb the chloride ions,
Non-electrochemical techniques Chloride capturing materials and pozzolanic materials such as fly ash and silica fume
chemically react with chloride ions due to a higher content
of aluminum, forming Friedel’s salt or Kuzel’s salt [7,8].
Intercalation of chemical corrosion inhibitors with
chloride-capturing materials provides both chloride
Hybrid system
capturing and a chemical reaction to form a protective
film on steel [9].

Facilities and equipment, however, for the electrochemical techniques are relatively
expensive and need highly trained staff to perform and monitor them. Furthermore,
interruption in the operation of infrastructures during maintenance, repair, or monitoring
creates other hidden costs. Therefore, these techniques are more applicable in specific
conditions where severe corrosion is expected or when immediate action is necessary.
Corrosion inhibitors have been used to mitigate corrosion in reinforced concrete for
several decades. They provide sufficient corrosion protection even in the presence of high
concentrations of aggressive chloride ions. These materials are beneficial in comparison
to some electrochemical techniques which prolong the service life of concrete structures.
Furthermore, corrosion inhibitors are commercially available with extensive ranges of
products. The efficiency of corrosion inhibitors depends on their corrosion mechanisms
and active groups. These active groups either physically/chemically adsorb chloride ions
to prevent them from direct access to the reinforcing steel or chemically interact with
the surface of steel to form a protective film. Nevertheless, the majority of the common
corrosion inhibitors on the market are synthetic, which has negative environmental impact
as well as health and safety risks. Therefore, many researchers have investigated the per-
formance and effectiveness of green corrosion inhibitors as well as different mechanisms
and types of compounds. It is also understood that only a few papers [10] have been
published to review green corrosion inhibitors while the global concerns about the envi-
ronmental impacts of synthetic corrosion inhibitors have been growing fast; consequently,
providing a state-of-the-art review is needed. Therefore, this paper focuses on elaborating
on the types and characteristics of environmentally friendly corrosion inhibitors, which
are also known as green inhibitors. Furthermore, the published results are scattered and
sometimes inconsistent. To overcome this challenge, this article reviews the properties
and effects of various inhibitors including non-toxic environmentally friendly inhibitors
functioning at high pH in concrete. It also classifies a broad range of corrosion inhibitors
and identifies their advantages and disadvantages as well as a set of selection criteria. The
findings of this paper illustrate important trends and assist researchers to develop further
Buildings 2023, 13, 1170 3 of 20

research towards sustainable progress in the fields of civil engineering and corrosion man-
agement. It also helps practitioners in all relevant disciplines to gain effective knowledge
on emerging green corrosion inhibitors. To achieve the aim of this review paper, different
databases such as Web of Science and Scopus were searched using keywords such as green
corrosion inhibitors, sustainability, and reinforced concrete. Consequently, more than 80
peer-reviewed journal papers were collected and analyzed for this study. The findings are
critically reviewed and discussed in the following sections.

2. Corrosion Mechanism
Corrosion is an electrochemical process which consists of oxidation and reduction
reactions. Generally, oxidation occurs when a metal loses an electron(s) and forms an oxi-
dized ion(s) (Equation (1)) in anodic sites and simultaneously free electrons are consumed
in cathodic sites and form reduced products. The nature of these new products depends on
the acidity or basicity of the system.
Hydrogen gas, hydrogen evolution, and hydroxide ions, OH− , are the main cathodic
products in acidic and alkaline systems, respectively (Equation (2)) [11]. The corrosion
process not only causes a reduction in rebars’ cross-section but also forms expansive
products, which results in the initiation of cracking in concrete.

Fe → Fe2+ + 2e (1)

2e + 2H + → H2

inacidicenvironment
(2)
O2 + 2H2 O + 4e → 4OH − inbasicandnaturalenvironment
Carbonation-induced corrosion is another form of corrosion of reinforcing bars in
concrete structures [8]. In this type of corrosion, interaction between diffused carbon
dioxide (CO2 ) and the concrete pore solution forms carbonic acid, which reduces pH
levels and consequently causes de-passivation of the protective layer over steel rebars and
initiates corrosion.
Microbiologically induced corrosion can also make significant problems for the in-
tegrity of concrete structures, particularly sewer pipelines where such microbial organisms
can produce organic and inorganic acids resulting in the degradation of concrete elements.

3. Corrosion Inhibitors
Inhibitors are materials that prevent either oxidation or reduction processes. The
corrosion inhibitors can be classified based on different criteria such as their mechanisms of
Buildings 2023, 13, x FOR PEER REVIEW 4 of 21
action, types of compounds, or ways of production. Figure 1 summarizes a general classifi-
cation of major corrosion inhibitors. According to the mechanism of corrosion inhibition,
anodic inhibitors can hinder the anodic reactions by forming a protective oxide film on the
metal surface. A successful application of the anodic inhibitors requires identification of
the critical concentration of inhibitors since a low concentration of anodic inhibitors can
accelerate corrosion.

Corrosion
inhibitors

Type of Type of
Mechanism
compound manufacturing

Hybrid Green (Nature-

Anodic Cathodic Organic Inorganic Synthetic
(combined) based)

Figure 1. General classification of corrosion inhibitors from different perspectives.

Figure 1. General classification of corrosion inhibitors from different perspectives.

The anodic inhibitors hinder anodic reactions based on two different mechanisms
depending on the availability of oxygen:
Buildings 2023, 13, 1170 4 of 20

The anodic inhibitors hinder anodic reactions based on two different mechanisms
depending on the availability of oxygen:
(1) The first mechanism occurs in the absence of oxygen forming a protective film of
rg. nitrates or chromates on the steel [12].
(2) The second mechanism occurs in the presence of oxygen forming a protective film
of rg. phosphates or silicates [13].
Cathodic inhibitors act by either slowing down the cathodic reaction or selectively
precipitating on the cathodic regions to interrupt the flow of electrons from the anode to
the cathode. Unlike the anodic inhibitors, the cathodic inhibitors are not corrosive, even at
low concentrations.
Typical examples for this group of inhibitors are arsenic trioxide (As2 O3 ), zinc sulfate
(ZnSO4 ), and nickel sulfate (NiSO4 ) [14,15]. Hybrid inhibitors are organic compounds that
adsorb on the metal surface and form a protective film which prevents both anodic and
cathodic reactions [14,16]. It is generally accepted that adsorption (physisorption and/or
chemisorption) of the organic corrosion inhibitors onto the metal surface occurs through
the polar head of the organic compound, and then the non-polar tail is oriented in a vertical
direction to the metal surface. This adsorption forms a dense protective film against the
corrosive ions and the corrosive environment [16]. The tail of these organic inhibitors may
have hydrophobic properties and can form a repulsive action against the corrosion ions
and enhance the protective performance of the passive film.
The other major classification of corrosion inhibitors is based on their origin either
from nature or synthetic production. Table 2 summarizes different types of inhibitors
which are classified as synthetic and green corrosion inhibitors, indicating the main active
groups and their general structure. In general, appropriate selection of corrosion inhibitors
depends on the effectiveness of corrosion inhibitors and subsequent active groups, effective
concentration, toxicity, cost, and commercial availability. Although, due to environmental
concerns, many more attempts have been made to develop green corrosion inhibitors with
low toxicity and high inhibitor efficiency, and production of this type of inhibitors demands
further investigation. In the following sections, the main types of synthetic and green
corrosion inhibitors are discussed in detail.
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Table 2. Various types of corrosion inhibitors based on availability of the active groups.
Table 2. VariousTable
types2.ofVarious
corrosion inhibitors
types basedinhibitors
of corrosion on availability of the active groups.
Corrosion In- General Structure of Substrate and Refer- based on availability of the active groups.
Active Group Studied Materials Advantages Disadvantages
hibitorsIn- ActiveStructure
General Groupsof ences and
Substrate
Corrosion
Corrosion Inhibitors In-
Active Group General Structure of Substrate and Refer- Studied Materials Advantages Disadvantages
Active
Active Group
Group Active Groups References Studied
Studied Materials
Materials Advantages
Advantages Disadvantages
Disadvantages
hibitors Active Groups ences NaNO2 [18]
Nitrites Steel rebar [17–22] • Most of them are • Non-environmentally
Ca(NO
NaNO 2)2 [19]
NaNO
NaNO 22 [18]
2 2 [18]
[18] commercially available. friendly.
Nitrites
Nitrites SteelSteel
rebarrebar [17–22]
[17–22]
Alkanolamine, Ca(NO
Ca(NO
Ca(NO 22))2
)[19]
2 [19]
22 [19]
monoethanolamide
2 • Easy to apply for a wide • Non-degradable in
(MEA), diethanolamine (DEA), triethan- range of applications. the environment
Amines Steel rebar [23–26] Alkanolamine, monoethanolamide • Higher market • Non-environmentally friend
of application.
Alkanolamine,
olaminemonoethanolamide
(TEA)
(MEA), diethanolamine (DEA), triethan- • Most of them are commer- •
acceptability • HighNon-degradable
health and safety in the envir
Amines Steel rebar [23–26] (MEA), diethanolamine (DEA),
[23–26] •• riskNon-environmentally
Non-environmentally friendl
friend
Amines Amines SteelSteel
rebar [23–26]
rebar [23–26]
olamine (TEA)(TEA)
triethanolamine
• Generally provide higher
cially available. ment of application. friendl
of dispersion of
Cycloexancarboxyl,[23–26] succinate, glutarate, •• corrosion
Most
Easy
protection.
of them
to apply
are commer-
for control
a wide
•
•
toxicNon-degradable
materials into
High health
envir
in the enviro
and safety risk o
[23–26] • Consistent quality environment especially
tartrate, citrate, fumarate, benzoate, cially available. ment of application.
Cycloexancarboxyl, succinate, glutarate, • range of applications.
and assurance for persion
in marine of toxic materials int
industries.
Synthetic cor- Carboxylates Steel rebar [26–29] Cycloexancarboxyl,
acrylic acid, allylacetic acid, succinate,
heptenoic • Easy to apply for a wide • • High health and safety risk o
Synthetic corrosion tartrate, citrate, fumarate, Higher market
production acceptability
process. Needsvironment especially in mari
rosion inhibi- glutarate, tartrate, citrate,benzoate,
fumarate, range of applications. persion of toxic materials into
non-environmentally int
int
inhibitors Synthetic cor- Carboxylates Steel rebar [26–29] acid, undecylenic acid, and oleic acid • Generally provide higher cor- dustries.
tors Carboxylates
Carboxylates SteelSteel
rebarrebar [26–29] acrylic
[26–29] acrylic acid,
acid, allylacetic
benzoate, acrylic acid,acid,
allylacetic acid, heptenoic
allylacetic acid, •
heptenoic Higher market acceptability vironment
friendly solvent especially in mari
rosion inhibi- [26–28,30] and • rosion protection. • Needs non-environmentally
acid,heptenoic
acid, undecylenic
undecylenicacid, undecylenic
acid,
acid, and and oleicacid,acid
oleic acid •• Generally
Generally provide higher cor- dustries.
or catalyst.
tors
tors oleic acid [26–28,30]
[26–28,30] Consistentprovide
quality higher
controlcor-
• •
dustries.
friendly
Unwanted solvent or catalyst.
byproducts
rosion protection. Needs non-environmentally
for production ••
[26–28,30] rosion protection. Needs non-environmentally
Urea (U), thiourea (TU), thioacetamide • and assurance Unwanted
during synthesis.byproducts durin
• Consistent
Consistent quality control friendly solvent
solvent or
or catalyst.
Amides Steel rebar [29,31–33] (TA), thiosemicarbazide (TSC), N-oleoyl process. quality control • High friendly
risk of soil
thesis. catalyst.
UreaUrea(U),(U),
thiourea (TU), thioacetamide
thiourea (TU), thioacetamide
and
and assurance
assurance for production •••
for production Unwanted
Unwanted
contamination. byproducts
byproducts durin
durin
High risk of soil contaminati
sarcosine [29,31–33] process. thesis.
AmidesAmides SteelSteel
rebar [29,31–33]
rebar [29,31–33](TA), thiosemicarbazide
(TA), thiosemicarbazide (TSC),(TSC),
N-oleoyl
N-oleoyl sarcosine
sarcosine [29,31–33] [29,31–33] • contaminati
High risk of soil contaminatio
contaminati
Ring structure with
Imidazolines, thiazoles, triazoles, ben-
Heterocyclic at least two different Steel rebar [11,34–40]
Ring
Ring structure
structure withwith
at least zotriazoles and pyrazoles
Imidazolines, [11,34]
thiazoles, triazoles,
Heterocyclic elements Steel rebar [11,34–40] Imidazolines, thiazoles, triazoles, ben-
Heterocyclic
Heterocyclic at two
at least two
different
least elements Steel
two different
different Steel rebar
rebar [11,34–40]
[11,34–40] benzotriazoles and pyrazoles [11,34]
elements
zotriazoles and pyrazoles [11,34]
• Extracts generally contain
• Most of them are not availab
elements Ginger extract, methanol extraction from • • Most of them are not
Extracts
multiple generally
functional contain commercially.
Mainly carbox- Ginger extract, methanol extraction •• available
Most
Most commercially.
of
of them
them are
are not
not availab
availab
olive leaves,
Gingerfrom oliveplant
leaves,extraction
plant of esfand
extraction of multiple functional groups•
groups which • Tedious
Tedious process,process,
as it as it involve
ylates but based extract, methanol extraction from • Extracts generally contain commercially.
Mainly
Mainly carbox-
Mainly carboxylates
carbox- seed,esfand
green seed,
tea extract,
green tea Juglans
extract,regia,
Juglans co- • Extracts
enhance
which generally
enhance contain
effectiveness.
effectiveness. commercially.
eral steps.
involves several steps.
on the type of olive leaves, plant extraction of esfand multiple
multiple functional
functional groups
groups •• Tedious
Tedious process,
process, as it involve
be as itbeinvolve
Green corrosion
but based
Green corro- on the
ylates
ylates type
but
but based
based Steel rebarSteeland
rebar and nifer cone,
alumi- regia,tannins,
conifer cone,
gumtannins,
Arabic,gum Fatsia •• Sustainable, non-toxic
Sustainable, non-toxic and
and • • Toxic solvent
Toxic might
solvent might used
green
of green material,
material, aluminum seed, green
Arabic,tea extract,
Fatsia japonica Juglans
leavesregia,
extractco- which enhance effectiveness.
environmentally eral steps.
used for extraction.
on the type
inhibitors sion inhibitors on the type of of num alloys [41–53] japonica(FJLE), leavesguarextract (FJLE), gluten
guar gum, environmentally friendly traction.
other active
Green corro- groups
other active Steel rebaralloys
and[41–53]
alumi- nifer cone, tannins, gum,
gummaize Arabic, Fatsia • friendly compounds.
Sustainable, non-toxic and • • Some extraction
Toxic solvent might be used
may alsogreen
green material,
material,
be available maize gluten mealmealextracts, extracts, • compounds.
Locally accessible • Some
solvents areextraction
quite solvents are
sion inhibitors groups may also num alloys [41–53] japonica leaves extract (FJLE), guar gum, environmentally friendly traction.
other
other active
active areca catechu,
areca catechu, chitosan,
chitosan, sesame
sesame cas- •
oil,oil, Locally
materialsaccessible materials expensive.
expensive.
be available maize
castorgluten meal extracts, compounds. • Somevariation
extractionin solvents are
groups
groups maymay also
also
oil, casein [41–47,53–61]
tor oil, casein [41–47,53–61] •• Cost effective.
Cost effective. • • Potential
Potential variation in quality
areca catechu, chitosan, sesame oil, cas- • Locally accessible materials expensive.
quality of
tracts. extracts.
be available
be available •• Cost ••
tor oil, casein [41–47,53–61] Cost effective.
effective. Potential
Potential variation
variation in
in quality
quality
tracts.
tracts.
Buildings 2023, 13, x FOR PEER REVIEW 6 of 21

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4. Synthetic Corrosion Inhibitors

4.1.
4. Nitrites Corrosion Inhibitors
Synthetic
Various nitrite components have been used as effective corrosion inhibitors, espe-
4.1. Nitrites
ciallyVarious
in chloride-contaminated
nitrite components environments.
have been usedThe presencecorrosion
as effective of nitriteinhibitors,
ions increases Fe(II)
especially
content in the oxide film, which results in the formation of a thicker and
in chloride-contaminated environments. The presence of nitrite ions increases Fe(II) content more protective
oxide
in the layer.
oxide This
film,mechanism
which results decreases the donor of
in the formation density of chloride
a thicker and more ions, which reduces
protective oxide
the high
layer. Thissusceptibility of localized
mechanism decreases thecorrosion
donor densityand increases
of chlorideprotective
ions, whichperformance
reduces thegrad-
high
ually with aging [17]. It has also been reported that nitrite-based corrosion
susceptibility of localized corrosion and increases protective performance gradually with inhibitors such
as sodium
aging [17]. nitrite (NaNO
It has also been2) reported
in a dosagethatofnitrite-based
3% by weight of cement
corrosion hinder such
inhibitors the diffusion
as sodium of
the chloride (Cl −) and sulphate (SO42−) ions in the concrete matrix significantly [18]. Sideris
nitrite (NaNO2 ) in a dosage of 3% by weight of cement hinder the diffusion of the chloride
(Cl − )reported
et al. and sulphate (SO4 2−effect
the positive ) ionsofin
Ca(NO 2)2 on the
the concrete corrosion
matrix protection[18].
significantly of theSideris
reinforcing
et al.
steel, butthe
reported thispositive
effect strongly
effect of depends
Ca(NO2 )2ononthethetype of cement
corrosion [19]. Figure
protection 2 shows that
of the reinforcing in-
steel,
creasing
but the dosage
this effect stronglyof depends
Ca(NO2)2on lowers theof
the type corrosion rate of
cement [19]. the reinforcing
Figure 2 shows that steel and in-
increasing
creases
the the of
dosage chloride
Ca(NOthreshold
2 )2 lowersforthecorrosion
corrosioninitiation
rate of the[20].
reinforcing steel and increases the
chloride threshold for corrosion initiation [20].

3 on corrosion rate of reinforcing steel [20].

Figure 2. Influence
Figure 2. Influence of
of nitrite
nitrite concentration
concentration (3,
(3, 6,
6, 12
12 L/m
L/m3))on corrosion rate of reinforcing steel [20].

However,
However, using
using nitrite-based
nitrite-based inhibitors
inhibitors for
for increasing
increasing corrosion
corrosion resistance
resistance may
may affect
affect
other
other properties of concrete. For instance, long-term compressive strength is decreased by
properties of concrete. For instance, long-term compressive strength is decreased by
adding
adding aa nitrite-based
nitrite-based inhibitor
inhibitor higher
higher than
than 4%
4% by
by the
the weight
weight ofof cement
cement toto the
the concrete
concrete
mix
mix [21]. In addition,
[21]. In addition, concrete
concrete resistivity
resistivity associated
associated with
with diffusion
diffusion ofof the
the chloride
chloride ions
ions
decreases in the presence of a nitrite-based inhibitor due to a higher chloride diffusion
decreases in the presence of a nitrite-based inhibitor due to a higher chloride diffusion
coefficient. On the other hand, the beneficial effect of sodium nitrite in raising the chlo-
coefficient. On the other hand, the beneficial effect of sodium nitrite in raising the chloride
ride threshold level may be offset by increasing the chloride transport [20]. This may be
threshold level may be offset by increasing the chloride transport [20]. This may be at-
attributed to the competition between adsorption of nitrite and chloride ions on the surface
tributed to the competition between adsorption of nitrite and chloride ions on the surface
of the hydrated products in concrete. High adsorption of chloride to the hydrated products
of the hydrated products in concrete. High adsorption of chloride to the hydrated
in concrete allows more free nitrites to participate actively in the corrosion inhibition of the
reinforcing steel [22].
The corrosion protection mechanism of the nitrites as an anodic inhibitor is based on
assisting the cathodic process by providing a protective oxide film. Nitrite functions as an
Buildings 2023, 13, 1170 7 of 20

oxidizing agent to oxidize iron (II) into iron (III), resulting in the formation of a stable passive
film of maghemite (γ-Fe2 O3 ) on the metal surface according to the following equation [19]:

2Fe2+ + 2OH− + 2NO2 − →2NO +Fe2 O3 +H2 O (3)

As nitrites can react with the amines available on the lubricants, which are commonly
used as additives in metalworking, they can form nitrosamines. These materials are known
as carcinogenic agents, and their possible toxicity has limited the application of these
materials as corrosion inhibitors [62]. However, some research has reported minimizing
the harmful effect of these materials by intercalating nitrites into hydrotalcite. In this way,
nitrites are hidden in the interlayer space of hydrotalcite, and they are released only when
chloride ions migrate to the reinforcing steel; in this situation, the rate of release is lower
than by adding nitrate directly to the concrete [63].

4.2. Amines
Amines, such as alkanolamine, monoethanolamine (MEA), diethanolamine (DEA), and
triethanolamine (TEA) are widely used as corrosion inhibitors because they (for example,
alkanolamine) move through the pore structure of the concrete to reach the surface of the
reinforcing steel and form a protective film. In addition, it has been reported that these types
of inhibitors can reduce migration of the chloride ions in concrete and have been classified
as mixed corrosion inhibitors by hindering anodic and cathodic reactions [23]. However, the
mechanical properties of the concrete have considerably decreased with using these types of
inhibitors. According to Söylev et al., a maximum dosage of 1% of inhibitor has decreased
the compressive strength of mortar more than 20%, especially in the early ages of 3 and
7 days after casting due to the retarding cement hydration [64]. The inhibition efficiency of
organic amino inhibitors is still insufficient, and the development of amino-based inhibitors
with higher inhibition performance is highly desired. Generally, using hybrid inhibitors,
which are a mix of two or more types of inhibitors, can be a good approach to provide
better corrosion protection efficiency. For instance, amino alcohols can be obtained based
on mixing alkanolamines with amines or, alternatively, with organic acids [24].
The amino alcohol inhibitors can be used either as admixture or repair products for
the concrete structures in service since their main component in the form of gas or liquid
phase can diffuse into the hardened concrete and hinder anodic and cathodic reactions of
the reinforcing steel [24]. This can form a protective film and increases the critical chloride
concentration while other components of amino alcohols form insoluble salts within the
pore of concrete structure and prevent further ingress of the chloride ions [25]. According
to Tritthart et al., this type of inhibitor is completely soluble in the pore solution with high
mobility in the concrete matrix and therefore guarantees corrosion protection.
Figure 3 shows the concentration of amino alcohol in the pore solution of three different
cements, and it shows that the concentration of amino alcohol in the pore solution is much
higher than in the mixing water. This suggests that the amino alcohol is not bonded with
the cement and remains in the pore solution.
However, amino alcohol in the presence of phosphorous components forms early pre-
cipitated salts and does not provide corrosion protection [65]. There are various formulae
for producing these types of inhibitors; for instance, the mixture of the orthoboric acid and
alkanoletheramine forms an excellent corrosion inhibitor with high efficiency and high solu-
bility in water without foaming [11]. Other examples of high-efficiency corrosion inhibitors
in this group are 1,3,6-triamino-methylhexane and 1,2,3-triaminoethylpropane, which have
been used in acidic aqueous media [11], but they may have different performance in
alkaline solutions.
Buildings 2023, 13, x FOR PEER REVIEW 8 of 21
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Figure 3. Amino alcohol in the pore solution in three different cement: normal Portland cement
Figure 3. Amino
(PZ-375-EZ), alcohol
Portland in thewith
cement pore30solution
mass% in three
blast different
furnace cement:
(EPZ), normal Portland
and sulfate-resisting cement
cement (PZ-
versus
375-EZ), Portland cement with 30 mass% blast furnace (EPZ), and sulfate-resisting cement versus
total inhibitor content [65].
total inhibitor content [65].
4.3. Carboxylates
However, amino
Carboxylates alcohol in the by
are characterized presence of phosphorous
a carboxylic components
group (–COOH) in their forms early
structure.
precipitated salts and does not provide corrosion protection [65]. There
These materials are considered proton donors through the de-localized electrical chargeare various for-
mulae
on the for
twoproducing
oxygen atoms theseoftypes of inhibitors;
the carboxylic for instance,
group which formthe mixture
a bond withof thethe
orthoboric
metallic
acid and alkanoletheramine forms an excellent corrosion inhibitor
surface. Carboxylates are divided into two main groups of mono-carboxylates and with high efficiency
poly-
and high solubility
carboxylates. in water without
The corrosion inhibitionfoaming [11]. Other
performance examples
of these of high-efficiency
materials is well studiedcor-
by
rosion inhibitors
Ormellese et al. [27].inThey
thisfound
groupthatare 1,3,6-triamino-methylhexane
poly-carboxylates and 1,2,3-triami-
such as cycloexancarboxyl, succi-
noethylpropane,
nate, which have
glutarate, tartrate, been
citrate, andused in acidic
fumarate showaqueous
better media [11], but
performance andthey may have
significantly
different
delay theperformance in alkaline
localized corrosion solutions.
in the 0.3 M sodium chloride in the pore solution [26]. The
number of carboxylate groups and carbon length in the structure play an important role in
4.3. protection
the Carboxylates and performance of these types of inhibitors. Hence, increasing the number
of carboxylate groups
Carboxylates areand intermediate
characterized bycarbon length group
a carboxylic with carboxylate
(–COOH) enhances inhibitor
in their structure.
efficiency. This isare
These materials due to the factproton
considered that the longerthrough
donors chains have shown lower
the de-localized solubility
electrical and
charge
greater
on the twohydrophobicity
oxygen atoms in the
of pore solution. For
the carboxylic example,
group whichcitrate
form and glutarate
a bond with have the op-
the metallic
timum
surface.number of carboxylic
Carboxylates groups
are divided andtwo
into carbon-length
main groups chains to prevent pitting and
of mono-carboxylates corrosion
poly-
of the reinforcing steel (Figure 4) [26]. Furthermore, Johari et al. reported
carboxylates. The corrosion inhibition performance of these materials is well studied by that the presence
of sodium–potassium
Ormellese tartrate
et al. [27]. They and that
found trisodium citrate in thesuch
poly-carboxylates concert mix enhances corrosion
as cycloexancarboxyl, suc-
protection due to the existence of carboxylate groups in their
cinate, glutarate, tartrate, citrate, and fumarate show better performance structures. They
andalso reported
significantly
that
delay thethe
synergy of using
localized tartrate
corrosion in and citrate
the 0.3 with sixchloride
M sodium times less insodium
the porenitrate compared
solution to
[26]. The
the singleofuse
number of sodiumgroups
carboxylate nitrateand
can carbon
result inlength
almostinsimilar corrosion
the structure protection
play [30]. role
an important
in the protection and performance of these types of inhibitors. Hence, increasing the num-
ber of carboxylate groups and intermediate carbon length with carboxylate enhances in-
hibitor efficiency. This is due to the fact that the longer chains have shown lower solubility
 corrosion of the reinforcing steel (Figure 4) [26]. Furthermore, Johari et al. reported that
the presence of sodium–potassium tartrate and trisodium citrate in the concert mix en-
hances corrosion protection due to the existence of carboxylate groups in their structures.
They also reported that the synergy of using tartrate and citrate with six times less sodium
Buildings 2023, 13, 1170 nitrate compared to the single use of sodium nitrate can result in almost similar corrosion
9 of 20
protection [30].

Figure 4. Pitting potential of the reinforcing steel with respect to chain length for bi-carboxylates [26].
Figure 4. Pitting potential of the reinforcing steel with respect to chain length for bi-carboxylates
[26].It has been accepted that carboxylates form chelate with calcium and iron ions on
the surface which hinder migration of the chloride ions to the reinforcing steel [26,28].
Lin etItal.has been accepted
studied the effectthat carboxylates
of carbon chain form
length chelate
on thewith calcium
corrosion and iron of
inhibition ions
theon the
five
types of organic acids, namely acrylic acid, allylacetic acid, heptenoic acid, undecylenicet
surface which hinder migration of the chloride ions to the reinforcing steel [26,28]. Lin
al. studied
acid, and oleicthe acid.
effectThey
of carbon
found chain
thatlength
as the on the corrosion
alkylene inhibition
chain length of the five
increases, types of
the surface
organic acids, namely acrylic acid, allylacetic acid, heptenoic acid,
adsorption increases, and then the whole system acts as a mix-type corrosion inhibitor. Theundecylenic acid, and
oleic acid. They found that as the alkylene chain length increases, the
effectiveness of the undecylenic acid, a colorless oil, for pitting and general corrosion was surface adsorption
increases,
higher thanandthe then
otherthe whole
types system actsand
of inhibitors, as aits
mix-type
optimizedcorrosion inhibitor.
concentration wasThe effective-
1000 ppm
inness
theof the solution
pore undecylenic
[28].acid, a colorless
Generally oil, for pitting
the long-chain and
fatty general
acids, suchcorrosion was higher
as oleic acid, soya
than the other types of inhibitors, and its optimized concentration was
fatty acid, and tall oil fatty acid (TOFA), have been well recognized as corrosion inhibitors, 1000 ppm in the
pore solution [28]. Generally the long-chain fatty acids, such as oleic
but short-chain fatty acids may accelerate corrosion [11]. Ormellese et al. evaluated the acid, soya fatty acid,
and most
nine tall oil fattyorganic
used acid (TOFA), haveinbeen
inhibitors well recognized
concrete such as aminesas corrosion inhibitors, but short-
(dimethylethanolamine and
chain fatty acids may
triethylentetramine), accelerate
amino acids corrosion
(aspartate,[11]. Ormellese
asparagine, et al. evaluated
glutamate, the nine most
and glutamine), and
used organic
carboxylate inhibitors(tartrate,
compounds in concrete such as
benzoate and amines
EDTA)(dimethylethanolamine and triethy-
in the synthetic pore solution, and
lentetramine),
after five years of amino acids
testing, (aspartate,
the asparagine,
most efficient inhibitorsglutamate, and glutamine),
which prevented and carbox-
chloride-induced
ylate compounds
corrosion were those (tartrate, benzoate and
with carboxylate EDTA)
groups. Forin the synthetic
example, EDTApore solution,
increased and after
the chloride
five years of testing, the most efficient inhibitors which prevented
threshold by about 50% with respect to the reference condition [27]. A similar study chloride-induced
showed that methacrylate-co-acrylamide polymer can form a polycarboxylate film on
the steel surface, which on this film significantly enhanced pitting and general corrosion
resistance of the reinforcing steel in the synthetic pore solution [29].

4.4. Amides
Amides are amine derivatives of carboxylic acids, and imide-type corrosion inhibitors
contain a high density of electrons in the imide group, which promotes adhesion to the
metallic substrate. The substrate acts as an electrophile, and imide inhibitors provide
electrons to form a bond with the substrate. Atoms that provide electrons for sharing in the
Buildings 2023, 13, 1170 10 of 20

imide structures are mostly O, N, and/or S [31]. Some amides and derivatives such as urea
(U), thiourea (TU), thioacetamide (TA), and thiosemicarbazide (TSC) are known as effective
inhibitors for mild steel in acidic solutions. The structure of inhibitors and the location of
the imide group significantly change the inhibitor’s efficiency and performance. It has been
found that when the oxygen atom in a urea molecule becomes replaced by a sulfur atom
(to form a thiourea), the corrosion inhibition efficiency increases dramatically [31].
The polarization of the amide group strongly affects the inhibiting performance. For
example, the polarizability of the phenyl derivative is higher than the methyl derivative.
Consequently, transfer of the electrons from the phenyl derivative to the metal is eas-
ier than that of the methyl derivative; therefore, inhibitors with a phenyl group such as
benzointhiosemicarbazone (BZOTSC) are more efficient than benzilthiosemicarbazone
(BZITSC) [32]. N-oleoyl sarcosine is another corrosion inhibitor with high corrosion per-
formance, which is soluble in mineral oil. However, this inhibitor in high concentrations
may be toxic to skin, which causes irritation, but at the lower concentration it shows
antimicrobial properties [33].

4.5. Heterocyclic Inhibitors

Heterocyclic inhibitors have a cyclic structure with a ring containing carbon, oxygen,
nitrogen, and sulfur. The number of possible heterocyclic systems is unlimited since it is
possible to produce different structures with these elements. However, the most common
corrosion inhibitors with this structure belong to the imidazolines, thiazoles, triazoles,
benzotriazoles, and pyrazoles [11,34]. This class of inhibitors can be used in very small
concentrations to inhibit steel corrosion. Imidazolines are widely used in oil and gas
industries, and it has been shown that they can effectively hinder corrosion in neutral,
acidic, and alkaline conditions [35]. Fei et al. studied the effect of imidazoline quaternary
ammonium salt (IQS) on the corrosion of reinforcing steel, and they found that this inhibitor
can effectively increase the corrosion resistance and chloride threshold value for corrosion
initiation. The performance of 2% IQS is slightly lower than 2% of sodium nitrite while
it is much better than 2% of amino alcohol [36]. Furthermore, the concentration of IQS
influences long-term corrosion protection. The SEM analysis indicated that increasing the
concentration of IQS is associated with the agglomeration of IQS on the surface of the
steel (Figure 5), which is not suitable for short-term corrosion protection. However, these
Buildings 2023, 13, x FOR PEER REVIEW 11 of 21
agglomerated particles can disperse gradually and cover the active sites of the steel surface
in long-term immersion.

Figure 5. SEM images of 1% and 2% IQS solution [36].

Figure 5. SEM images of 1% and 2% IQS solution [36].

The mechanism
The mechanism of of the
the corrosion
corrosion inhibition
inhibition inin IQS
IQS was
was based
based on
on the
the absorption
absorption ofof the
the
hydrophilic imidazoline
hydrophilic imidazolineheterocycle
heterocycleonon thethe steel
steel surface,
surface, which
which formsforms a homogeneous
a homogeneous film.
film. Furthermore, the hydrophobic tail of this inhibitor acted as a barrier against
Furthermore, the hydrophobic tail of this inhibitor acted as a barrier against diffusion diffusion
of the
of the aggressive
aggressive ions towards
ions towards the steelthe
andsteel and simultaneously
simultaneously avoided diffusion
avoided diffusion of the ironofions
thefrom
iron
ions from the surface to the pore solution [37]. It was reported that imidazoline
the surface to the pore solution [37]. It was reported that imidazoline can be loaded into can be
loaded into zeolite and be used as admixture in concrete. The electrochemical testing of
the reinforcing steel with loaded zeolite showed that incorporation of 1% wt inhibitor by
mass of cement provides 92% corrosion inhibition efficiency after 142 days of immersion
in the chloride solution. This excellent corrosion resistance efficiency was explained by the
enhanced binding capacity of the zeolite and formation of a protective film due to the
Buildings 2023, 13, 1170 11 of 20

zeolite and be used as admixture in concrete. The electrochemical testing of the reinforcing
steel with loaded zeolite showed that incorporation of 1% wt inhibitor by mass of cement
provides 92% corrosion inhibition efficiency after 142 days of immersion in the chloride
solution. This excellent corrosion resistance efficiency was explained by the enhanced
binding capacity of the zeolite and formation of a protective film due to the exchange
of the chloride ions and inhibitor in the zeolite [38]. The imidazoline amide is another
corrosion inhibitor which has been tested in the basic solution with a high concentration
of carbon dioxide, and only 20 ppm of this inhibitor provided an inhibitor efficiency of
97% in the pore solution with 3% chloride. It has been demonstrated that the pendant side
chain in the imidazoline played an important role in inhibiting the corrosion of Fe [39].
Haque et al. synthesized an ecofriendly imidazolium corrosion inhibitor by mixing amino
acids, glyoxal, formaldehyde, and acetic acid. This synthesized imidazolium presented
two carboxylic groups in the structure for the enhanced adsorption of the metallic ions Fe2+
and therefore showed an excellent corrosion inhibition with more than 95% efficiency in
acidic solution [40].
Imidazoline can be synthesized from vegetable oil, and only 100–200 ppm of vegetable-
oil-based inhibitors effectively decreases the corrosion rate of steel [32]. Yoo et al. synthe-
sized imidazoline from palm oil, soybean oil, and castor oil as a source of olefinic esters, and
then amidation of the olefinic ester with polyamine was performed at a high temperature.
The corrosion inhibition efficiency of the synthesized imidazoline is ranked as follows:
corrosion inhibition of soybean oil > corrosion inhibition of palm oil > corrosion inhibition
of castor oil [34]. It is also possible to synthesize the imidazoline from rice oil, and it was
found that a 20 ppm concentration showed efficiency above 99% in the brine–CO2 satu-
rated solution at 50 ◦ C [66]. In addition, the corrosion potential shifted to a more negative
value by increasing the concentration of the inhibitor indicating that the rice-oil-based
imidazoline can be classified as a cathodic inhibitor [66].

4.6. Green Corrosion Inhibitors

Environmentally friendly corrosion inhibitors are based on natural products and plant
extracts which are widely used for the corrosion protection of metals due to their renewa-
bility, accessibility, and relatively low cost. The diversity of green corrosion inhibitors
is indeed high, and many of them have the potential to be considered as efficient and
practical corrosion inhibitors in the field. The inhibition efficiency of these materials de-
pends on many factors such as the pH of the corrosive environment, type of aggressive
ions available in the environment, and the molecular state of the corrosion inhibitors. The
major challenge is to identify which active components in natural products are responsible
for a reduction in the corrosion activity in metals [67]. The protonated components of
the inhibitor absorb aggressive anions electrostatically and consequently inactivate those
aggressive ions. This mechanism of corrosion protection is categorized as a physisorption
mechanism, which is the case for the majority of commercial inhibitors. The inhibitor
efficiency of the physisorption inhibitors decreases with the increase in the temperature
since the electrostatic force between the aggressive ions and the active component weakens
with the rising of temperature [67]. An example of this type of inhibitor is carboxymethyl
cellulose (CMC), which was studied by Solomon et al., in acidic solutions. This study
reported that the efficiency of the corrosion inhibitor improves by increasing the CMC
content while it decreases with the increase in the temperature [68]. Inhibitors which form
chemical bonds with the surface of the metal or corroding metal, covalent or co-ordinate,
are categorized as chemisorption inhibitors. The inhibitor efficiency of this type of inhibitor
increases at higher temperatures by enhancing formation of the chemical bonds. These
two mechanisms may occur simultaneously on the surface of the metals.
Plant extraction is one of the techniques which is commonly used for producing green
corrosion inhibitors. Liu et al. have studied the effect of ginger extract on the chloride-
induced corrosion of carbon steel in a simulated concrete pore solution. They found that 2%
of the ginger extract delayed the corrosion initiation due to the forming of a carbonaceous
Buildings 2023, 13, 1170 12 of 20

organic film on both the anodic and cathodic areas of the steel surface. Nevertheless,
inhibition efficiency of the ginger extract in comparison to traditional corrosion inhibitors
such as sodium nitrites is significantly lower [41]. Methanol extraction from olive leaves
is another plant-based material which provides a highly effective corrosion protection in
basic chloride solutions. The inhibitor efficiency of the olive leaves was reported up to 91%,
which can be related to the presence of N, O, and p-electrons in its structure [42]. Qihui
Wang et al. studied the performance of Fatsia japonica leaves extract (FJLE) and reported it
having corrosion inhibition efficiency as high as 89.6% at 1000 mg/L. This improvement
increased by immersion time and reached the value of 91.2%. The mechanism of corrosion
inhibition enhancement over time was explained by electrostatic gravity of FJLE and its
adsorption on the steel surface. In the second stage, the interaction of unpaired electrons
of heteroatoms (of FJLE) with the “d” orbitals of Fe occurs, and finally “d” orbitals of Fe
interact with the electrons of the inhibitor molecule [69].
Researchers have reported that extracts of different parts of plants have the potential
to be considered as corrosion inhibitors, and this property is not limited to their leaves. For
example, plant extraction of esfand seed showed formation of protective complexes and
chelates film on the surface of carbon steel. This formed layer had a hydrophilic nature,
which was attributed to the presence of organic compounds such as mercapto, amine,
hydroxyl, phosphate, and carboxylic components of the extract. The inhibitor efficiency of
esfand with a concentration of 1000 ppm was more than 93% after 219 h of immersion in 3.5%
chloride solution, which is comparable with other synthetic organic inhibitors [43]. Another
study which was conducted by Pradipta compared the inhibitor efficiency of green tea
extract (GT) against commercial calcium nitrite in sodium chloride solution. This research
showed that the corrosion rates of calcium nitrite and GT specimens were not significantly
different when a similar inhibitor concentration was used for testing of the reinforcing
samples, regardless of their inhibition mechanisms [44]. Another study showed that an
addition of 1000 ppm of Juglans regia (JRS) extraction increased the inhibition efficiency of
tested steel plates to 94% in 3.5% sodium chloride solution. This considerable inhibition
efficiency was attributed to functional groups such as hydroxyl, carboxyl, and carbonyl
which exist in the phenolic-based components of the Juglans regia extract (Figure 6).
These functional groups enhance the capability of the JRS to adsorb electrostatically and/or
covalently on the metal surface and subsequently restrict remarkably the corrosion reactions
of the metal substrates [45]. In a similar research work, Conifer Cone extraction was used at
a concentration of 1000 mg·L−1 in NaCl (0.8 M) synthetic pore solution for 720 h, and it was
found that the corrosion inhibition efficiency of this concentration is more than 81%. The
identified two-stage mechanism of corrosion inhibition of Conifer Cone consists of physical
adsorption in its initial stage, considering the presence of various types of the carboxylic
and amin groups in the extract, and then chemical adsorption as the second stage over
longer immersion time [46].
Tannins are also known as corrosion inhibitors, which are extracted from renewable
resources, and their bone structure consists of garlic acid residues, which are linked to
glucose via glycosidic bonds, and includes different functional groups such as hydroxyl
and carboxyl. Tannins can be adsorbed on the surface of the corroding metallic materials
due to the presence of these active compounds [47]. The inhibitor efficiency of tannin with
a concentration of 140 ppm was reported to be around 72%, which is higher than some
conventional corrosion inhibitors such as H3 PO4 in 1 M HCl [47]. The application of tannins
is not limited to acidic environments, and it has been reported that tannin as a major part
of Gossipium hirsutum extract sufficiently decreased the corrosion rate of aluminum alloys
in 2 M sodium hydroxide [48]. The performance of tannins in seawater with wet/dry cyclic
conditions was evaluated, and its inhibition efficiency was reported as 86% due to the
blocking of the cathodic reaction on the surface of the steel and the formation of a dense
layer of ferric tannates. Furthermore, FeOOH which was formed during cathodic reduction
in the wet/dry cycle reacted with tannin within the solution (Figure 7) [49].
 Buildings 2023, 13, x FOR PEER REVIEW 13 of 21

solution for 720 h, and it was found that the corrosion inhibition efficiency of this concen-
tration is more than 81%. The identified two-stage mechanism of corrosion inhibition of
Buildings 2023, 13, 1170 Conifer Cone consists of physical adsorption in its initial stage, considering the presence of 13 of 20
various types of the carboxylic and amin groups in the extract, and then chemical adsorp-
tion as the second stage over longer immersion time [46].

Buildings 2023, 13, x FOR PEER

Figure 6. REVIEW
Figure 6. ATR-FT-IR
ATR-FT-IR spectra spectra
of theofmild
the mild steel plates
steel plates immersed in the in
immersed testthe
solutions
test containing
solutions14 of
JRS 21
containing
extract [45].
JRS extract [45].
Tannins are also known as corrosion inhibitors, which are extracted from renewable
resources, and their bone structure consists of garlic acid residues, which are linked to
glucose via glycosidic bonds, and includes different functional groups such as hydroxyl
and carboxyl. Tannins can be adsorbed on the surface of the corroding metallic materials
due to the presence of these active compounds [47]. The inhibitor efficiency of tannin with
a concentration of 140 ppm was reported to be around 72%, which is higher than some
conventional corrosion inhibitors such as H3PO4 in 1 M HCl [47]. The application of tan-
nins is not limited to acidic environments, and it has been reported that tannin as a major
part of Gossipium hirsutum extract sufficiently decreased the corrosion rate of aluminum
alloys in 2 M sodium hydroxide [48]. The performance of tannins in seawater with wet/dry
cyclic conditions was evaluated, and its inhibition efficiency was reported as 86% due to
the blocking of the cathodic reaction on the surface of the steel and the formation of a
dense layer of ferric tannates. Furthermore, FeOOH which was formed during cathodic
reduction in the wet/dry cycle reacted with tannin within the solution (Figure 7) [49].

Figure 7. Schematic
Figure 7.ofSchematic
the corrosion mechanism
of the corrosion during
mechanism wet/dry
during cyclic
wet/dry cyclic condition
condition tests
tests in in seawater
seawater
(a) and tannic-acid-containing seawater
(a) and tannic-acid-containing (b) [49].
seawater (b) [49].

In another study, the effect of tannin on the corrosion protection of steel in the pore
solution was evaluated, and the formation of tannin-Fe(III) chelate on the steel was re-
ported. However, this film was much thinner than those in the tannin-free solutions; there-
fore, the corrosion protection of tannin-Fe(III) was not significant [50].
Gum Arabic (GA) is another green corrosion inhibitor that is soluble in water and has
been used for the protection of metallic materials in acidic and basic solutions. The struc-
ture of gum Arabic is a mixture of complex polysaccharides containing a hydroxyl func-
Buildings 2023, 13, 1170 14 of 20

In another study, the effect of tannin on the corrosion protection of steel in the pore
solution was evaluated, and the formation of tannin-Fe(III) chelate on the steel was reported.
However, this film was much thinner than those in the tannin-free solutions; therefore, the
corrosion protection of tannin-Fe(III) was not significant [50].
Gum Arabic (GA) is another green corrosion inhibitor that is soluble in water and has
been used for the protection of metallic materials in acidic and basic solutions. The structure
of gum Arabic is a mixture of complex polysaccharides containing a hydroxyl functional
group (–OH) and carboxyl functional group (–COOH), as well as calcium, magnesium, and
potassium salts [54]. The first application of gum Arabic for corrosion protection of steel
was not successful, and its inhibitor efficiency was only around 37% in the acidic solution at
a concentration of 0.5 g/L in chloride solution [51]. However, other researchers showed that
increasing the concentration of gum Arabic to higher than 0.5 g/L significantly increased
its inhibitor efficiency to 92%. Nevertheless, when its concentration exceeded 2 g/L, no
significant enhancement was detectable [70]. The mechanism of corrosion inhabitation in
GA was based on physical and chemical adsorption due to donor and acceptor interactions
with the metallic surface in acidic solutions; therefore, GA was considered a mixed-type
inhibitor which suppresses both anodic and cathodic processes [52]. Gum Arabic inhibited
the corrosion of aluminum in NaOH, and it was found that the inhibition efficiency of
GA increased with increasing the GA concentration and temperature. Furthermore, a
synergistic effect was observed between GA and iodide ions in the sodium hydroxide
solution [71]. The addition of GA with a dosage of 0.5% by weight of cement to the
mortar revealed an enhanced mechanical strength and physical properties of the mortar
as well. This behavior can be related to the formation of new mineral phases such as
sepiolite, tobermorite, and wollastonite due to the transformation of K, Na, Mg, Ca, Cu,
Zn, and Fe ions which are available in the GA and mortar matrix [72]. The application
of GA nanoparticles in reinforced concrete exposed to a carbon dioxide environment was
studied by Asaad, and it was found that addition of 3% GA nanoparticles (GA-NPs) to
the concrete mix decreased the corrosion rate and had an inhibitor efficiency up to 94.5%.
In presence of a GA-NPs inhibitor, the ratio of Ca/Si reduced due to the consumption of
calcium hydroxide, which subsequently resulted in the development of C-S-H gel and
increasing pH [73].
Another green corrosion inhibitor is guar gum, which is widely used in food industries.
It is a heavy molecular weight polysaccharide with a molecular weight ranging from 1 to
2 MDa [53]. The corrosion inhibition efficiency of guar gum in 2 M H3 PO4 was reported
to be around 85%, which was enhanced by increasing its concentration to the maximum
value of 1.0 g/L. However, its inhibitor efficiency decreased slightly by increasing the
temperature [70]. It is worth noting that there is no information about inhibition efficiency
of guar gum in alkaline solutions. Venkatesh et al. blended guar gum with 0.5%, 1.0%,
1.4%, and 1.5% in concrete with a constant water/binder (w/b) ratio of 0.45. They reported
that the addition of 1.4% of guar gum protected structural steel from corrosion effectively.
The corrosion protection mechanism of this inhibitor according to the density of states
(DOS) analysis is based on negatively charging the metal surface before electrostatically
absorbing protonated inhibitor molecules over the steel surface. In the second stage,
electrons from O atoms and pi-electrons from rings in inhibitors were adsorbed on the
metal surface, reducing anodic metal dissolution. This study shows that guar gum not
only enhanced corrosion protection but also resulted in an increase in the mechanical
properties of concrete including compressive strength (up to 23.2%) and splitting tensile
strength [74]. Zhang et al. studied maize gluten meal extract, which is a cheap by-product
of maize wet milling that is used for animal feed. They used this extract as a corrosion
inhibitor in a 3% sodium chloride solution and reported that maize gluten meal extracts
were an effective and promising corrosion inhibitor for steel with an inhibition efficiency
of 62.71–88.10% depending on the extract content. The highest inhibitor efficiency was
obtained at the concentration of 2 g/L, which was attributed to the adsorption of the amide
groups in both anodic and cathodic parts of the reinforcing steel [55]. The diversity of green
Buildings 2023, 13, 1170 15 of 20

corrosion inhibitors is indeed high and many of them have the potential to be considered
as efficient and practical corrosion inhibitors in the field. For example, Ghoreishiamiri et al.
studied the addition of 2% areca palm in concrete mix and evaluated its mechanical and
corrosion behavior against sodium nitrite, which is a commercial corrosion inhibitor [56].
They reported that the performance of the areca catechu in concrete was comparable to
sodium nitrite, and this behavior is related to the formation of gypsum with a dense texture.
However, this research did not report the main active group of the corrosion inhibitor in
Buildings 2023, 13, x FOR PEER REVIEW 16 of 21
its extraction.
Chitosan is a natural polymer that can be considered a satisfactory substitute for
conventional inhibitors due to its biodegradable nature, but chitosan is not soluble in
environments.
basic solutions andHowever, other natural
forms precipitation polymers
which limits such as alginates
its application as and pectates
a natural are soluble
polymer in
in high-alkaline solutions and can be used in both acidic and basic solutions
basic environments. However, other natural polymers such as alginates and pectates as an inhibi-
are
tor. The
soluble chemical structures
in high-alkaline solutionsofand
alginates
can beandusedpectates
in both are similar,
acidic and solutions
and basic the difference
as anbe-
tween them
inhibitor. is relatedstructures
The chemical to the position of the two
of alginates and C-2 and C-3
pectates hydroxyl
are similar, groups
and which have
the difference
cis-position
between them isinrelated
alginates andposition
to the trans-position in pectates,
of the two C-2 and C-3respectively (Figurewhich
hydroxyl groups 8) [57].have
cis-position in alginates and trans-position in pectates, respectively (Figure 8) [57].

Figure 8. Schematic structure of the alginate and pectate and the differences in the location of
Figuregroups
hydroxyl 8. Schematic
which structure
influence of
thethe alginateinhibition
corrosion and pectate
[57].and the differences in the location of hy-
droxyl groups which influence the corrosion inhibition [57].
Both natural polymers contain carboxylate groups which form an anionic charge.
Both natural
Furthermore, polymers contain
these polysaccharides carboxylate
(pectin groups
and alginates) arewhich
assumed form andeprotonated
to be anionic charge.
Furthermore,
in alkaline theseand
solutions polysaccharides
form reactive (pectin
alkoxides. and A alginates)
thin filmareof assumed
inhibitor is to adsorbed
be deproto-
on nated in alkaline
the surface solutions
of metal due to and
theform reactive
presence of alkoxides.
carboxylate A thin filmand
groups of inhibitor
preventsisfurther
adsorbed
on the processes,
corrosion surface ofand metal due tocan
alkoxide themake
presence
anotherof carboxylate
repulsive actiongroups and other
against prevents further
negative
ionscorrosion processes,Zaafarany
in the solution. and alkoxide
et al.can make another
studied repulsiveofaction
the application against
alginate and other nega-
pectates
tive corrosion
in the ions in theprotection
solution. Zaafarany
of aluminum et al.alloys
studied the applicationsolution
in high-alkaline of alginate
andand pectates
reported
thatinthe
theinhibitor
corrosionefficiency
protection ofof
the pectates was
aluminum higher
alloys than alginates.
in high-alkaline This and
solution wasreported
related tothat
differences in theefficiency
the inhibitor polysaccharide structures.
of the pectates wasIndeed,
higherthe than presence of the
alginates. ThisOH groups
was relatedin to
thedif-
cis-position
ferences in in the
alginates tends to decrease
polysaccharide structures. theIndeed,
adsorption ability ofofthe
the presence theinhibitors
OH groups on in
Althe
surface, while ininthe
cis-position pectates’tends
alginates OH groups existing
to decrease theinadsorption
the trans-position
ability ofpromote adsorption
the inhibitors on Al
to the aluminum
surface, whilesurface. The concentration
in the pectates’ OH groups ofexisting
1.6% pectate
in theintrans-position
alkaline solution showed
promote an
adsorp-
inhibitor efficiency of approximately 88%, which was slightly higher
tion to the aluminum surface. The concentration of 1.6% pectate in alkaline solution than alginates [57]. A
similar study using sodium pectate was performed in an acidic solution
showed an inhibitor efficiency of approximately 88%, which was slightly higher than al- to understand in
detail the mechanism
ginates [57]. A similarof corrosion
study usingprotection
sodiumofpectate
this natural polymer for
was performed aluminum
in an alloys, to
acidic solution
andunderstand
it was found inthat thethe
detail inhibition
mechanism efficiency of this polymer
of corrosion protection decreased
of this to 48%. Although
natural polymer for
increasing
aluminum the alloys,
concentration of the
and it was sodium
found thatpectate enhanced
the inhibition the inhibitor
efficiency of thisefficiency
polymer slightly,
decreased
increasing the temperature resulted in a reduction in the
to 48%. Although increasing the concentration of the sodium pectate enhanced inhibitor efficiency [58].
theThe
inhib-
itor efficiency slightly, increasing the temperature resulted in a reduction in the inhibitor
efficiency [58]. The inhibitor efficiency of the pectate was much higher in the alkaline so-
lution, and it was explained that this behaviour may be related to the formation of positive
alkanium ions in acidic solutions instead of negative alkoxides in alkaline solutions, which
Buildings 2023, 13, 1170 16 of 20

inhibitor efficiency of the pectate was much higher in the alkaline solution, and it was
explained that this behaviour may be related to the formation of positive alkanium ions
in acidic solutions instead of negative alkoxides in alkaline solutions, which do not show
repulsive action against negative ions [58]. Obot et al. reported that the sodium alginate
inhibited the corrosion of the steel in 3.5% NaCl solution effectively and reported an
inhibitor efficiency of 81% at the alginate concentration of 1000 ppm [59].
Oil-based corrosion inhibitors are mainly used in acidic or brine solutions since the
fatty acids in the alkaline solution initiate a foaming reaction. However, Oyekunle et al.
reported sesame and castor oils as effective corrosion inhibitors for steel in brine solution
due to unsaturated compounds such as oleic, steric, and palmitic acids, which interact
with iron ions and form a protective film on the surface of steel [60]. Various types of
bio-friendly plant oils such as linseed, sunflower, castor, tung (TO), soybean (SBO), and
coconut oils (CCO) have been used in industries as the main components of paints or
plasticizers [75]. The fatty acids inside these oil molecules, which have different types of
carbon bonds, double and triple bonds, cause various physical and chemical properties. In
general, more unsaturated double bonds in the oil structure cause more reactions toward
oxygen, which leads to the formation of a solid and adherent film on the surface. Since more
unsaturated fatty acid is available in linseed and TOs, these two oils are more susceptible
to auto-oxidation in comparison to soybean or other vegetable oils [76]. Therefore, the
application of linseed oil attracted more attention than other vegetable oils, especially in
cracked coatings or mortar, as a crack healer or sealing agent in a matrix [77,78]. In another
study, rapeseed oil (RO) or LO as a healing agent was encapsulated with relatively high
fill content using ethyl cellulose polymer [79]. The mixture of linseed oil and other types
of corrosion inhibitors, such as MBT mercaptobenzothiazole, showed a very promising
corrosion protection in coatings [80].
The field of green corrosion inhibitors is an emerging and fast-growing research area,
and different researchers have reported the feasibility of using some other green materials
as corrosion inhibitors which still need to be investigated further in reinforced concrete.
For example, casein as a protein of milk has been widely used in many industries such
as glue, plastics, and paper production due to the presence of functional groups in its
structure [81]. The solubility of casein in an alkaline solution activates many polar groups
in casein structure such as amino acids and carboxylates, which are adsorbed on the surface
of metals [61,81]. The application of casein with the concentration of 0.6 g/L as a corrosion
inhibitor for aluminum alloys in alkaline solution enhanced the corrosion resistance by at
least one order of magnitude with an inhibitor efficiency of 81% [61]. However, Rabizadeh
et al. reported that casein enhanced the corrosion resistance of steel in acid solutions via
both physical and chemical adsorption processes [81]. Another example is glutamine (Gln),
which was studied by Jassim et al. using density functional theory (DFT) calculations to
evaluate its capability and derivative chemicals as inhibitors for the anticorrosive behavior
of iron. This research showed that the adsorption of small-scale peptides and glutamine
amino acids on Fe surfaces (111) is highly possible and provided the highest stability
and lowered energy, which means the highest inhibitor efficiency. This research paves
the way for introducing various type of green corrosion inhibitors containing small-scale
peptides and glutamine amino acids [82]. Nevertheless, further investigation is demanded
to consider practical applications of such green materials in concrete.

5. Conclusions
Green corrosion inhibitors have emerged as a new field in cement and concrete re-
search. The diversity of green corrosion inhibitors is indeed high, and many of them have
the potential to be considered as efficient and practical corrosion inhibitors. This review
provides a comprehensive study to demonstrate the effectiveness of these green materials
in the corrosion protection of reinforcing steel. It classifies a broad range of corrosion
inhibitors and identifies their advantages and disadvantages. In addition, it proposes
a set of selection criteria to choose appropriate inhibitors based on their characteristics
Buildings 2023, 13, 1170 17 of 20

and sustainability requirements. They can be functional even in areas with high levels
of chloride contamination. The inhibition efficiency of these materials depends on many
factors such as the pH of the corrosive environment, type of aggressive ions available in
the environment, and the molecular state of the corrosion inhibitors. Their mechanism
of corrosion protection is based on the availability of active groups such as carboxylates,
amines, and hydroxide in the structure of these green materials. These active groups are
physically/chemically or physico-chemically adsorbed on the reinforcing steel and form
a protective film and hinder cathodic, anodic, or both reactions. The new protective film
may show repulsive action against chloride ions and offers further corrosion protection.
However, the concentration of these active groups influences the mechanism of protection
and the inhibitor efficiency. In general, some types of green corrosion inhibitors can show a
corrosion protection efficiency up to 94%, which is comparable with common synthetic in-
hibitors. The corrosion protection efficiency can be enhanced even up to 99% by extracting
the functional group from such green organic materials. Further investigation, however, is
needed for evaluating their technical properties including modelling functional groups for
corrosion protection and their effectiveness under the combined attack of corrosive ions.
Furthermore, it is recommended that the effect of those green inhibitors which already
showed acceptable functionality in a high pH environment is studied in cement and con-
crete matrices. Furthermore, a detailed lifecycle cost analysis of these green inhibitors is
needed, which is important for commercial applications.

Author Contributions: A.Z.: conceptualization, methodology, data collection, analysis, writing

(original draft, review and editing). A.B.: conceptualization, methodology, data collection, analysis,
writing (original draft, review and editing). All authors have read and agreed to the published
version of the manuscript.
Funding: The authors declare that there was no funding for this study.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare that they have no competing interests.

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