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Journal of Bio- and Tribo-Corrosion (2022) 8:35
https://doi.org/10.1007/s40735-022-00636-6
A Review onGreen Corrosion Inhibitors forProtection ofArcheological
Metal Artifacts
AmalM.Abdel‑Karim1· AshrafM.El‑Shamy1
Received: 9 August 2021 / Revised: 5 January 2022 / Accepted: 19 January 2022
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022
Abstract
Because of their toxicity, traditional corrosion inhibitors are no longer allowed due to an increase in environmental awareness
and a change in the laws. Environmentally friendly corrosion inhibitors are becoming more popular. Corrosion inhibitors
derived from natural products are a good choice because they contain a wide range of active elements that can be used in
organic compounds to bind to metal surfaces and form a protective film that prevents further corrosion. These active ele-
ments are found in abundance in natural extracts, making them a good starting point for developing new green corrosion
inhibitors. Several natural ingredients are investigated, as well as their usage in different techniques, such as steel reinforce-
ment incorporated in concrete. Ionic liquids, which are regarded to be new corrosion green inhibitors, are described in this
research using unique synthetic techniques. This research also discusses the adsorption process, the action of these green
inhibitors in diverse fluids, and their protective function for various metal alloys. A look at how vapor-phase inhibitors
are used in industry and how they work is also explored. The researchers used inhibitors to prevent metal artifacts against
corrosion in general and the corrosion of metal artifacts from corrosion. As a result, one of the most significant strategies
for protecting our metal cultural legacy is the use of corrosion inhibitors. Unfortunately, the inhibitors of preservatives are
dangerous as well. More and more people are becoming concerned about the environment and the need to develop more
ecologically friendly technology, which has led to an increase in the focus on developing renewable solutions. To conserve
metallic cultural heritage, the use of green corrosion inhibitors has become one of the most used ways. The effects of eco-
nomic, safety, and environmental factors on corrosion of metal artifacts and methods used for their protection, metal types
and their chemical and electrochemical properties, practical steps for treating the pre-surface before inhibitor use; types
of green inhibitors and their features; a review aimed at clarifying the most important key topics in this crucial research
area. Techniques for conducting electrochemical and surface examination of metal artifact surfaces before and during the
application of inhibitor are outlined.
Keywords Green chemistry· Corrosion inhibitors· Archeologically artifacts· Corrosion control· Conservation approach
Abbreviations
BTA Benzotriazole
BTAH+ Protonated form of benzotriazole
IE Inhibition efficiency
EIS Electrochemical impedance spectroscopy
OCP Open circuit potential
NMR Nuclear magnetic resonance
SEM Scanning electron microscopy
EDX Energy-dispersive X-ray spectroscopy
OM Optical microscopy
FTIR Fourier transform infrared
XRD X-ray diffraction analysis
PMI Phenyl 4-methyl-imidazole
MTI 4-Methyl p-tolyl-imidazole
MAcT 2-Mercapto 5-acetylamino-thiadiazole
MAT 2-Mercapto-amino-thiadiazole
MBI 2-Mercapto benz imidazole
TMI 1-(P-tolyl)-4-methyl imidazole
MMeT 2-Mercapto-methyl thiadiazole
MAcAT 2-Mercapto-acetyl amino-thiadiazole
MPhAT 2-Mercapto-phenyl amino-thiadiazole
BiTA Bi-tri azole
ATA Amino-tri azole
PTS 3-Phenyl 1, 2, 4-triazole-5 thione
MBT Methyl benzotriazole
* Ashraf M. El-Shamy
elshamy10@yahoo.com
1 Physical Chemistry Department, National Research Centre,
33 El Bohouth Street, P.O. 12622, Dokki, Giza, Egypt
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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Cys Cysteine
Lys Lysine
Arg Arginine
Gly Glycine
Val Valine
1 Introduction
Egypt retains a broad historical cache that contains several
significant observations. Testaments to the riches of the
Egyptian dunes are such as the Rosetta Pillar, the Valley
of the Kings, the famous religious great pyramid, beauti-
ful ancient temples, and even an enticing array of majestic
temples. Archeologists strive to explore other significant
historical ancient artifacts and sites spanning the Middle
Ages. With something in mind, archeological antiquities
of metal should be covered. Enough that now, we should
describe the definition, the form, and the corrosion factor.
Rust is described as the unavoidable strong interaction of a
metal with its environments which results in a significant
improvement in the chemical and physical properties of
the steel and its landscapes [1]. For example, in Fig.1, the
metal corroded in various forms: (a) general corrosion or
uniform corrosion layer on the metal surface [2]; (b) pitting
corrosion, where small, localized areas are quickly corroded,
and the surface of the metal is free of corrosion; (c) stress
corrosion cracking, where a crack is formed in the metal
structure; and (d) galvanic corrosion, where different met-
als are immersed in a corrosive media, one of them acts as
an anode (metal active), and the other as a cathode (Nobel
metal). Corrosion is a natural phenomenon that affected eco-
nomics, safety, and the environment. Each nation loses 3–5%
of its gross national product [3]. The corrosion is damage
of metal or alloys by chemical and electrochemical reac-
tions. In the industrial field, the corrosion of metals can be
expressed in economic terms, due to the costs involved in
the repairs of metallic objects or their replacement, but in
the case of cultural heritage, every object is unique and,
therefore, any loss is irreplaceable. So, metallic artifacts
corrosion prevention is one of the important issues in the
protection of ancient and historical artifacts. It is impor-
tant to know the factors affecting metal artifacts corrosion
to control or prevent the corrosion process. Metallic objects
can damage through the phenomenon of deterioration at
indoor and outdoor corrosive environments throughout gal-
lery presentation or preservation in unregulated climate and
excavation in surface sediments even after relocation. This
degradation can also occur even after the treatment because
of unsuitable treatment methods. All metals are subject to
degradation by the chemical reactions that occur between
the metal and the surrounding environment [4]. The main
causes of metal artifacts corrosion in the museum are rela-
tive humidity, temperature, atmospheric pollutants, and dust
Fig. 1 Forms of corrosion. A
General corrosion, B Pitting
corrosion, C Stress corrosion
cracking, and D Galvanic cor-
rosion
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[5]. Active corrosion causes harmful effects on archeologi-
cal objects, from minor changes to severe form (complete
transformer). Archeological artifacts usually have a complex
mechanism and different corrosion products can be formed
in corrosive environments. Metals are corroded by contact
with water, acids, and alkali, as well as by metals. The most
important problem facing the metal effects in the Mediter-
ranean basin is the high humidity [6]. Water is an electrolyte
that allows the ions to move freely increasing the reaction
rate. The archeological objects in wet air may not have any
visible water on them, but there are microscopically thin
layers of water adsorbed on the surfaces. The higher the
relative humidity level of these materials and the more ions
it can pass, the more the corrosion reaction rate increases.
The amount of weathering agent produced on the metal arti-
fact surfaces that are exposed to external air depends on the
level of pollutant such as reduced sulfur species (hydrogen
sulfide, carbonyl sulfide, dimethyl sulfide, and sulfur diox-
ide), organic acids (formic acid and acetic acid), formalde-
hyde, chlorides, nitrogen oxides, and amines that have a vital
influence on the color, composition, and rate of corrosion
of the metal artifacts. The corrosion protection systems are
extra vital when the main aim is to protect archeological
metal artifacts, which represent a historical richness. Such
treatment options should conform to the cultural heritage
protection rules. Many studies have been done to select the
best materials that can prevent and stop the degradation of
the metal and do not harm the metal and the health of the
restorer. The materials must be applied with no change of the
surface appearance and easily removed returning the object
to its original state. These can be achieved by inhibitors of
corrosion that are chemical compounds when a small con-
centration can reduce or prevent the corrosion of the metal
that is contacting corrosive content [7, 8]. A new role has
been taken in the study of corrosion inhibitors, and new laws
govern their uses [9]. Through removing toxic inhibitors
such as chromium, mercury, arsenic, nitrites, and non-toxic
benzoates, environmentally stable, more biocompatible, and
low cost, green (eco-friendly) inhibitors have been created.
The use of inhibitors passed from economic toward green
concepts. This means it is not enough that the inhibitor has
high inhibition efficiency. The new legislation for chemical
substances needs that substances must be environmentally
acceptable and safe to humans [10]. So, scientific research-
ers are devoting great effort to creating new non-toxic high-
efficiency compounds. This sort is known as green or envi-
ronmentally friendly inhibitors. This review represents the
corrosion behavior of metal artifacts. The detailed survey of
new environmentally friendly green inhibitors as organic,
amino acid, polymer, ionic liquid, and plant extracts and
their effect on the corrosion of archeological metal artifacts
was discussed. Different assessment techniques have been
used to determine the adsorption capacities of the used
corrosion inhibitors and to survey microstructure and the
inhibition mechanism.
2 Corrosion andConservation ofMetal
Artifacts
2.1 Nature ofMetal Artifacts
There are three stages, namely, the ages of stone, bronze, and
iron, which explain the close correlation between the human
culture developments. Luster, hardness, and strength are the
metal's physical properties; they were manipulated in the
construction, structures, and making of metallic surfaces.
Archeological metal is the type of material that consists of
or includes a metallic element such as copper and its alloy,
iron and alloy, silver and alloy, gold, and lead. On the surface
of the metal exposed to the outside or indoor, environment-
specific corrosion products are created. These products con-
tain a huge number of compounds that affect the appearance
and behavior of metal artifacts.
2.2 Copper andIts Alloys
Copper has a light reddish color, relatively soft, and occurs
naturally as an ore. Copper or its alloys have a wide range
of applications. Copper alloyed with zinc is known as brass,
whereas copper/tin is bronze. Copper and bronze represent
one of the main cultural heritages of metal artifacts. When
copper and its alloy corrode, there is an initial porous layer
of cuprous oxide Cu2O (cuprites) formed on its surface and
it is reddish brown. In the presence of CO2, an external layer
of basic green blue carbonates layer is formed. Copper-based
artifacts are characterized by stable degradation products
formed on the metal substrate, thus creating a greenish pas-
sive protective layer that enhances the object’s appearance
known as noble patina as in Fig.2. The composition of
patina depends on the composition of the alloy and envi-
ronmental conditions [11–13].
The patinas have been formed naturally or could have
been created by the artist for esthetic reasons [14]. The
growth of patina is induced by degradation processes on
the metal surface that forms reactive compounds, as oxides,
chlorides, carbonates, hydroxyl chlorides, sulfides, nitrates,
and sulfates [15]. Chloride, which is responsible for the
bronze disorder in the contact with water and oxygen, where
it is in the shape of holes that distort the composition of
the body, must be taken for protection. Brass may lose the
alloying element (zinc) through a process named dezinci-
fication. Copper-tin alloys can suffer selective elimination
of the copper (de-cuprification) or removal of the tin (de-
stannification) as shown in Fig.3.
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2.3 Iron andIts Alloys
Iron is the most essential metal; it is white and brilliant in
its pure form. It is used as alloyed with other elements as
archeological iron. Various corrosion outputs can be devel-
oped on the iron surface depending on the environment (soil,
sea water, and atmosphere). The composition of the cor-
rosion layers is very important to manage the preservation
of prehistoric iron artifacts with a proper chemical reagent.
In air and oxygen three oxides occur in iron: FeO, Fe3O4,
and Fe2O3; in the presence of moisture, Fe2O3 converts to
FeO(OH) [16, 17]. The separated salts act as an electrolyte.
Iron oxidizes to ferrous chloride at the positive electrode
and the reduction of hydrogen has occurred at the negative
electrode. Iron hydroxyl chloride, β-Fe2 (OH)3Cl, which
consists of a mixture of β- and γ-Fe2(OH)3Cl, is also com-
mon in iron artifacts retrieved from a sea environment [18].
Alloy objects that contain iron/copper may be at additional
risk. Copper corrodes less than iron, and this effect is named
galvanic corrosion [19].
2.4 Silver andIts Alloys
Silver is a shiny white noble metal, unusually soft and
spongy. It has lower electric resistance and greater heat
conductivity than any other metal. Silver and its alloy have
been used in artifacts, coins, and decorative elements. Silver
is tarnished by oxygen which forms a layer of black silver
oxide and a thin layer of dark silver sulfide (Ag2S) is formed
in the presence of hydrogen sulfide [19]. The sulfide and
oxide layers provide silver a degree of protection from fur-
ther corrosion. However, in presence of the chloride, silver
chloride or horn silver is formed, does not protect the metal,
and all the silver is converted to chloride making this corro-
sion destructive [20].
2.5 Lead andIts Alloys
Pure lead is a silver-blue, lustrous metal. It is very elas-
tic, very dense, and has a low melting point. Lead was also
added to copper alloys to improve their casting. Lead is a rel-
atively corrosion-resistant metal. On exposure to air quickly,
a thin layer of gray lead oxide is formed which acts as a bar-
rier and gives good protection from further corrosion [21].
2.6 Conservation Treatment
The definition of corrosion provides us with different strat-
egies that can be used to prevent or decrease corrosion.
Firstly, being a reaction of a metal with its surroundings,
the option is changing the metal or the environment. While
changing the metal does not apply to metal artifacts, the
modification of the environment is probably the best option.
This plan is simply applied in indoor museums environ-
ments, where the relative humidity and pollution can be
controlled. For outdoor environments, it is more difficult to
apply due to the atmospheric humidity that cannot be con-
trolled. The ideal stopping of corrosion reactions by remov-
ing the oxygen, water, salts, or pollutants from an environ-
ment, is technically difficult. However, Corrosion control is
generally more possible, by reducing humidity or pollution
concentrations. When exhibiting the metal artifact, specific
situations should be avoided to reduce the effect on the envi-
ronment. As gaseous and particulate pollutants may enter
the environment, avoid leaving doors and windows open,
Fig. 2 Two artifacts of different
appearances: A Nobel patina
and B Vile patina
Fig. 3 Schematic representation of the two main types of corrosion
structures found on archeological bronzes
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keep away from lighting fixtures, and avoid using hardwoods
which can release acidic fumes and corrode silver and lead
metals. Conservation processes must follow reliable and
reproducible measures to protect the surface of the artifacts
to avoid further degradation caused by the contaminated
atmosphere. In addition, environmental control and the
conservation of occupational health should be tackled for
a viable rational method [22]. Surface treatments include
two steps: cleaning and coatings can be a significant point
of a metal artifact to improve the appearance of the object.
2.6.1 Cleaning
Archeological metal objects are cleaned by mechanical and
chemical methods, and the best way is electrolytic reduction
cleaning as shown in Fig.4. Sometimes the chemical clean-
ing is used to clean lead, silver, and gold objects that are eas-
ily damaged by mechanical cleaning, and it is very important
that objects are carefully rinsed with water to eliminate any
remains of the chemicals.
2.6.2 Coating
The coating is a method used to protect the metal, to avoid
its contact with the environment, hence reducing the rate of
electrochemical reaction. Many treatments fall in this group,
being the most usual organic coatings, such as waxes, lac-
quers, paints, and varnishes where isolation of the formed
metallic artifacts through the environment and the homoge-
neous protected layer of the metallic surfaces are applied.
The most protective coatings for archeological metal objects
are Paraloid B-72 and Cosmoloid H80 [23, 24]. Many cor-
rosion inhibitors can also be included to protect metal since
they form a protective layer that avoids the interaction of
the metallic artifacts through the environment. The inhibi-
tors for corrosion are chemical compounds that are spread
on metallic surfaces to manage the corrosion process. The
provided adsorbed layer can give extra protection where the
wax or resin can be scratched. In copper and its alloys, the
greatest communal applied inhibitor in the preservation pro-
cess is benzotriazole (BTA). Generally, BTA has excellent
inhibitive properties in neutral/alkaline solutions compared
with other tested inhibitors [25]. This is outstanding due
to its good spreading on the metallic surfaces through the
physical or chemical adsorption process. The adsorption of
BTA decreases in an acidic solution, due to less strongly
chemisorbed protonated form of BTAH+ on the surface. So,
it is not efficient in this case and the necessity for novel
acidic corrosion inhibitors became a must [26]. In addition,
it explained through his tests on isopropyl benzylidene thia-
zole and its use as a copper inhibitor in acidic media [27].
The compound was given high resistance against corrosion
with inhibition efficiency reaching 96%.
2.6.3 Inhibitors Evaluation
Several techniques are used independently or simultaneously
for physical, chemical, morphological, and metallurgical
characterization of metal artifacts in different conservation
conditions. The corrosion rate and protection efficiency of
metal and its alloys were measured using weight loss and
electrochemical methods. These methods provide valuable
information to design strategies for the protection of metals
and their alloys. Electrochemical techniques have been used
in the field of metal artifacts protection, either using test and
analysis techniques or through treatment and conservation
techniques. It is also evaluating the efficiency of corrosion
inhibitors used in the protection of artifacts, both in an out-
door and indoor environment. The best materials are selected
to be applied to the metal artifacts. The key source of recy-
cling agents is in the form of coatings or dried films, bound
to the metal sheet. While archeological metal artifacts have
distinctive properties as their formulation, the history of use,
the environment in which the rust product was formed, and
the preservation circumstances. Even though there are sev-
eral metal artifacts, it is not permissible for scientific stud-
ies to modify or damage them. Therefore, it is essential to
identify a quintessential alloying element of metal artifacts
to assess the inhibition properties of new compounds [28].
3 Corrosion Rate Measurements
3.1 Weight Loss Techniques
Assessments of weight loss are easy to understand, get an
average rate of corrosion, and needed long times concern-
ing electrochemical testing. Corrosion assessment by weight
fluctuations is accurate when applied to uniformly corroded
coupons. A weight change for a metal object implies an effi-
cient application of corrosion. While also going to compare
Fig. 4 Schematic description of the electric circuit of electrolytic
reduction cleaning
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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the weight of an inhibited coupon with the weight of an
uninhibited coupon over the same period the percentage of
the IE percent inhibition efficiency was calculated using the
formula:
Under which, W0 and Wi are the weight reported when
inhibitors are absent and present.
It should be noticed that, in the case of heritage artifacts,
the weight measurements might not reflect the damage suf-
fered by the object, which is more complex, and it is related
to the notion of loss of value (that could be esthetic, sym-
bolic, historic, socioeconomic, scientific, technologic, etc.)
[29].
3.2 Measurements ofPotentiodynamic Polarization
Potentiodynamic tests were carried using potentiostat in
a conventional tri-electrode glass cell. The potential of
the working electrode was detected in contradiction of
SCE as a reference electrode and a sheet of pure Pt metal
as a counter electrode. For every experiment, the work-
ing electrode was etched using multiple types of emery
paper, then rinsed into acetone and distilled water and
swiftly engrossed with and without inhibitor in the test
solution. Measurements of potentiodynamic polarization
were conducted to test the inhibiting influence of corrosion
on the anodic and cathodic electrode reactions. From the
(1)
IE%
=
W
0
−W
i
W
0
×
100
intersection of the linear anodic and cathodic divisions of
the Tafel plots as seen in Fig.5, the corrosion parameters
such as corrosion current icorr and corrosion potential Ecorr
are calculated. Using this formula, the IE percent inhibi-
tion efficiency was calculated:
where io and i are the current density of corrosion when
inhibitors are absent and present.
3.3 Measurements ofElectrochemical Impedance
Spectroscopy (EIS)
Electrochemical impedance spectroscopy (EIS) has been
used in the field of archeological artifacts to evaluate pati-
nas, corrosion products, and coatings. EIS was performed
at potential corrosion (Ecorr). The impedance diagrams are
given in the interpretation of the Nyquist and Bode plots
as seen in Fig.6. EIS detects the changes in resistance on
the substrate as well as how the charge carriers are rear-
ranged at the metal-electrolyte interfacial capacitance. By
using the following equation, the inhibition efficiency (IE
percent) was determined from the resistance values.
which, in the absence and the presence of inhibitors R and
Rinh are the resistance of defensive material.
(2)
IE%
=
i
0
−i
i
0
×
100
(3)
IE
%=
R
inh
−R
R
inh
100
Fig. 5 Tafel plots for metal (a)
without (b–f) with different
concentrations of inhibitor
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4 Mode ofAction ofCorrosion Protection
4.1 Adsorption ofInhibitor ontheMetal Surface
Isotherms of adsorption are very essential for estimating
the organo-electrochemical reaction mechanisms. Surface
adsorption may be physical adsorption (physisorption)
or chemical adsorption (chemisorption), or a combined
adsorption mechanism that becomes quite for efficient
corrosion suppression. Other very frequently utilized iso-
therms include Langmuir, Temkin, and Freundlich. It was
found that isothermal Langmuir adsorption is enough for
the most rigorous results.
where plotting of C/θ against C for corrosion of metals
where, θ = the degree of superficial exposure determined
from electrochemical polarization, K is the adsorption cycle
equilibrium constant, and C is the concentration [30]. The
adsorption free energy (WG) provides details on the physical
or chemisorption process method of adsorption.
at which R is the general gas constant (8.314J/mol.), T is
the absolute temperature, and the value of 55.5 is the water
concentration in mol/L solution.
(4)
C
𝜃
=
1
K
+
C
(5)
Δ
G
o
=−RT ln
(
55.5Kads
)
4.1.1 Active Corrosion Protection
The goal of active corrosion prevention is to have a posi-
tive impact on the reactions that occur because of the pres-
ence of corrosion. Active corrosion prevention is a method
of preventing corrosion from occurring. Corrosion may
be completely prevented if not only the contents of the
package and the corrosive chemical are well regulated, but
also the reaction process itself is carefully monitored and
controlled as well. In this sector, for example, the crea-
tion of corrosion-resistant alloys as well as the addition
of inhibitors to aggressive media, among other things, are
two strategies that are now being explored.
4.1.2 Passive Corrosion Protection
Damage to the package contents is prevented when passive
corrosion prevention is applied. This is accomplished by
physically separating the package contents from aggres-
sive corrosive chemicals during the production process.
Protective layers, films, or other coatings may be added to
the contents of the package to accomplish this. This type of
corrosion protection is known as passive corrosion protec-
tion because it does not alter either the overall ability of the
package contents to corrode or the aggressiveness of the
corrosive agent. It is known as passive corrosion protection
Fig. 6 Represents A Nyquist plots and B Bode diagrams for metal (a) without and (b–f) with different concentrations of inhibitor
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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because it does not alter either of the two characteristics
mentioned previously. passive corrosion protection is also
known as passive corrosion protection. Protection layers,
films, and other layers may be lost at any point over the
course of the corrosion process. This will very certainly
result in corrosion within a reasonably short amount of time
if this happens.
4.1.3 Permanent Corrosion Protection
Permanently installed corrosion prevention systems are
meant to offer protection at the point of use, which is the
primary function of these devices. Stresses brought on by
environmental elements such as climatic, biotic, and chemi-
cal causes are normally mild under these circumstances. In
industrial sheds, for example, machinery is protected from
extreme temperature fluctuations, which are a common
source of condensation in these situations. Extreme fluctua-
tions in humidity are also avoided from having an impact on
the machinery. Listed below are some examples of passive
corrosion prevention strategies to take into consideration:
Tin plating and galvanization are two forms of galvaniza-
tion that may be distinguished. Examples of coatings include
enameling and copper plating, to name just a few of them.
4.1.4 Temporary Corrosion Protection
The magnitude of the stresses that occur during shipping,
handling, and storage is much larger than the size of the
stresses that occur at the application site. The effects of
stress may present themselves in a variety of ways, including
substantial temperature fluctuations that increase the likeli-
hood of condensation. When water and air are combined to
form the so-called sea salt aerosols, the high salt content
of the water and air may cause significant damage. These
aerosols are particularly hazardous in marine transport since
salts have a very powerful corrosion-promoting effect. The
following are the most common temporary corrosion preven-
tion solutions that are now accessible to you:
4.2 Surface Analysis Techniques
Techniques for surface investigation have been applied for
description of the inhibitor layers formed on the metals
allowing the study of the layer composition formed on
metals following the procedures used by conservators and
after exposure of the coated metals to the atmospheric
environment [31]. Morphological characterizations were
achieved by (SEM) joined to (EDX), optical micros-
copy (OM), (FTIR) and (XRD). For more significance of
SEM in the imaging and analysis of archeological sam-
ples through the EDX module it gets much information,
which helps during the treatment and preservation. SEM
is a powerful tool to study the corrosion process where
it can study both the properties of the metal surface as
well as the study of active local corrosion. XRD is a non-
destructive of great importance tool for information of
compounds in the study of metal before restoration. In
addition to the knowledge of the subsurface decoration,
identify the places of cracks.
5 Green Corrosion Inhibitors
Efforts to protect metal artifacts against corrosion involve
two approaches: treating the surface and /or diminishing the
corrosive substances in the environment. So, using corrosion
inhibitors should create a low-cost, stable, reversible, and
esthetically suitable coating. Thus, the need to choose the
suitable condition to protect the metal artifacts becomes an
essential object as the method of application, environmen-
tal, health, and safety requirements thickness of the coat-
ing of inhibitors. Unfortunately, we encountered several
failures in using the corrosion inhibitors due to synthetic
problems as difficult synthetic routes, and low yield, low
solubility, toxicity: formation of a colored solution, cost of
production, and time-consuming. In addition, some inhibi-
tors have been found to obscure the appearance of corro-
sion products on metal surfaces, which is a huge problem
when dealing with archeological artifact preservation [32,
33]. Ideal inhibitors should have high efficiency in inhibi-
tion, cheap, biodegradable, low toxicity, environmentally
friendly behavior, and have long-term stability [34–36]. And
if inhibitors are applied on real archeological artifacts which
represent a historical richness of a culture other conserva-
tion requirements as the preservation of the esthetic value,
ease of application, economic cost, and reversibility. Several
efforts have been made to discover green corrosion inhibitors
suitable for different corrosion environments [37]. Recently
corrosion research has been highly interesting as shown in
Fig.7 [38, 39]. Although most investigations into corrosion
inhibitors, there are several projects aimed at studying green
compounds for metal artifacts protection. The environmental
advantages of green inhibitors, it has become the focus of
many researchers in the protection of cultural and archeo-
logical heritage [40]. Corrosion inhibitors are divided into
inorganic and organic inhibitors according to their chemi-
cal composition. The heterocyclic compounds containing
N, O, and S behave as metal dissolution inhibitors through
the complexing operation of the heterocyclic compound that
forms a shield on the surface of a metal. Inhibition efficiency
follows that sequence: sulfur-containing > nitrogen-contain-
ing > oxygen-containing inhibitors [41]. Detailed surveys of
new environmentally friendly green corrosion inhibitors for
metal artifacts were discussed.
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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5.1 Types ofGreen Inhibitors
Green inhibitors can be categorized into two different types:
inorganic and organic as shown in Fig.8 [42].
5.1.1 Non‑toxic Organic Inhibitors
The inhibiting efficiency of non-toxic imidazole derivative
as 2-mercapto- benzimidazole (MBI) of copper corrosion in
sulfuric acid and near-neutral chloride solutions is consid-
ered employing two major techniques the first one is weight
loss and the second one is corrosion measurements by elec-
trochemical polarization. The suppressing characteristics of
substitute imidazoles depend upon the composition of the
molecules. The best coverage (93%) is due to the physical
adsorption of the imidazole phenyl ring to the metal surface.
Bronze artifacts are exposed in an outdoor or indoor envi-
ronment forming green patinas. Several studies have been
performed on different artificial patinas to examine the deg-
radation mechanisms of protective layers of metal artifacts.
The consequence of an innovative composite, sodium (Z)-
4-oxo-4-p-tolyl-2-butenoat is investigated as a corrosion
inhibitor for bronze artifacts, the corrosion performance
by electrochemical study demonstrated that the maximum
suppression efficacy of 92% is realized at 200ppm [43].
The protection efficiency of mercapto benzimidazole MBI is
more protective than BTA especially after immersion 24h in
acid rain forming the nitrate and sulfide patina [44]. Moreo-
ver, they suggest that the use of four composites as corro-
sion suppressors for Cu–Sn alloy shielded with useful patina
these compositions were like archeological bronzes. Four
non-toxic organic compounds were examined as inhibitors
Year of Publicaons
19901995 2000 2005 2010 2015 2020
Number of Publicaons
0
500
1000
1500
2000
2500
Corrosion Inhibitors
(A)
Year of Publicaons
1990 1995 2000 2005 2010 2015 2020
Number of Publicaons
0
20
40
60
80
100
120
140
160
Green Inhibitors
(B)
Fig. 7 Represent the number of publications of A corrosion inhibitors and B green corrosion inhibitors
Fig. 8 Diagram of different
types of green corrosion inhibi-
tors
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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35 Page 10 of 21
compared with BTA: phenyl 4-methyl- imidazole (PMI),
4-methyl p-tolyl- imidazole (MTI), 2-mercapto 5-acety-
lamino- thiadiazole (MAcT), and 2-mercapto –amino- thia-
diazole (MAT). The results show that TMI and MAcT were
originated to be good corrosion inhibitors, but their recitals
are lesser than that of BTA. But PMI has not any corrosion
protection see Table1.
However, MAT is a good corrosion inhibitor of bronze
antiquities. It was found that the film obtained may be MAT
itself, or copper-MAT complex Cu (C2H2N3S2)2.H2O with
a small variation in the color of the surfaces. The calcu-
lated suppression efficacy is 84% which makes it suitable
for conservation purposes. The (EIS) and (SEM with EDX)
have been used to measure the suppressing activity of thia-
diazole complexes MAT, 2-mercapto-methyl thiadiazole
(MMeT), 2-mercapto-acetylamino-thiadiazole (MAcAT),
and 2-mercapto-phenylamino-thiadiazole (MPhAT) on
patinated bronze pitting corrosion. MMeT and MAT have
been found to enable the stabilization of the patina base,
contributing to bronze substratum defense. With increas-
ing the immersion time, the efficiency increases [45]. The
consequences of former revisions have been revealed that
approximately imidazole compounds give continuing for-
tification to patinated copper alloys in replicated acid rain
phenomenon [46]. TMI, MAcT, and additional numerous
derivatives of thiadiazole are well-organized for protection
bronze artifact covered with patina and ready to be used
in museums. These substances are safe for human beings
and the environment [47]. Three blue-green patinas were
produced by chemical approaches in chloride and sulfate
solutions and a sulfate/carbonate solution. Structural and
morphological characterizations were achieved by SEM,
EDX, and spectroscopy of Raman techniques. Non-toxic
corrosion inhibitor TMI was used on three patinas, in an
electrolyte simulated to acid rain in the municipal situation.
The inhibition actions were measured by extrapolation of
Table 1 Chemical structures of
toxic BTA and some non-toxic
corrosion inhibitors
Chemical structure Name Abbreviation
Benzotriazole BTA
2-mercaptobenzimidazol
eM
BI
1-phenyl-4-methyl imidazole PMI
1-(p-tolyl)-4-methyl
imidazole
TMI
2-mercapto-5-R-acetylamino-
1,3,4-thiazole
MAcT
2-mercapto-5-R-amino-1,3,4-
thiazole
MAT
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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Page 11 of 21 35
Tafel, or potentiodynamic polarization resistance, and EIS.
This study showed that inhibitor progresses the steadiness
of all types of protected patinas. So TMI can be suggested
for the fortification of bronze artifacts [48]. The inhibition
effect of benzotriazole and non-toxic imidazole are exam-
ined and reported [49]. It was found that both investigated
compounds inhibited the corrosion of formed chloride patina
but were ineffective in the case of nitrate patina. Some tria-
zole derivatives used as toxic BTA, and non-toxic bi-triazole
(BiTA), amino- triazole (ATA) were established as corro-
sion suppressors of bronze protected with perfect patina
deposit. Artificial patinas were synthesized on (Cu–Sn–Pb)
bronze consuming a configuration like archeological coins
from bronze. Triazole compounds on the bronze coins give
good protective effects. BTA in an artificial patina and an
old bronze coin covered with a patina layer is the most effec-
tive inhibitor but BTA is a toxic compound. The BiTA has
exhibited only a slight inhibiting effect on the old bronze
coin. The ATA is also the most important barrier for the
defense of ancient bronze objects protected by native patina
deposits. Some electrochemical studies are conducted and
chemical tests on the use of triazole derivatives as amino
phenyl triazole thiol and amino nitrophenyl triazole thiol
as inhibitors of copper corrosion in 3.5% NaCl [50]. The
results of the test showed that the two compounds have great
protection against copper. Two artificial patinas were exam-
ined in two inhibitor systems, the first one is azole-based
suppressors in an alcoholic solvent and the second one in the
wax coating was studied. The efficiency of these protective
systems was evaluated by EIS. The consequences displayed
that, the fortification of perfect patinated copper alloy by
the inhibitor ethanol interfaces became the greatest opera-
tive system. It was found that the protective properties of
the investigated inhibitor/paraloid B44 systems depend on
the concentration of patina and inhibitor in the coating [51].
Synthesized organic product 3-phenyl 1,2,4-triazole-5 thione
(PTS) as good corrosion inhibitor able protects archeological
bronzes and historical steel against corrosion in neutral chlo-
ride medium [52]. The effect of phenothiazine compounds as
decomposition suppressors for copper corrosion in the acid
environment are studied and the results indicated that it was
given a high prevention efficiency of 90% [53].
5.1.2 Drugs
Archeological artifacts exposed to urban environments suf-
fer corrosion. By using corrosion inhibitors keep corrosion
under control. The consequence of four formulas of antibi-
otics (amoxicillin, ciprofloxacin, doxycycline, and strepto-
mycin,) on copper alloy decomposition in acidic solution
(pH 4) was studied. Antibiotics act as corrosion inhibitors
forming protective films on the metal surface [54–61].
Open circuit potential (OCP), linear polarization curves,
electrochemical impedance spectroscopy (EIS), UV–vis-
ible, FTIR, and NMR spectroscopy techniques explored the
inhibition effects of Irbesartan drug on steel corrosion in
HCl and H2SO4 solutions. The adsorption was followed by
Langmuir isotherm with 94 percent and 83 percent inhibi-
tion efficiency respectively [62].
5.1.3 Biopolymers
The possibility and toxicity of inhibitors of organic and inor-
ganic corrosion contributed to the hunt for green corrosion
inhibitors as anticoagulants to shield metals and their alloys
from corrosion [63]. A smart approach for developing active
protective coatings is the use of green polymeric materi-
als extracted from renewable sources as corrosion inhibi-
tors. The incorporation of polymer matrix with corrosion
inhibitors offers two advantages, using a low concentration
of inhibitors and long-term protective films. Choosing solu-
ble polymeric materials to prevent using dangerous solvents
that are required for commercial protective coatings to be
applied and removed [64]. For the protection of indoor
bronze objects, chitosan as active coatings with two dis-
tinct corrosion inhibitors, toxic BTA and non-toxic MBT, is
investigated. A copper alloy was used as the metallic layer,
with a chemical composition identical to bronze artifacts.
BTA has been selected as an inhibitor of corrosion, while
MBT is considered a promising low toxic alternative [65].
The results obtained revealed that the chitosan-based coat-
ing containing BTA and MBT can inhibit the corrosion of
bronze alloys, increase the inhibition of steel alloys by physi-
cal and chemical protection by the polymer matrix and by
the inhibitors respectively [66–68].
5.1.4 Surfactants
Cellulose was extracted from rice husk and degraded into
oligomers that reacted with different aliphatic diamines
forming oligoglucose amines, which ethoxylated polyeth-
ylene glycols with different molecular weights to obtain a
series of ethoxylated oligoglucose amine surfactants. Sur-
factants as corrosion inhibitors have many advantages: they
are inexpensive, simple to prepare, non-toxic, and have high
performance in inhibition. Surfactants have a polar hydro-
philic group, connected to a hydrophobic nonpolar group
[69]. An elemental analysis, FTIR, and NMR were used to
synthesize and characterize non-toxic cationic Gemini sur-
factants with ester linkages. The efficiency of synthesized
compounds in 1M HCl solution in the corrosion inhibi-
tion was evaluated using potentiodynamic polarization and
impedance measurements [70–73].
5.1.4.1 Green Surfactant Synthesis Methods In the labora-
tory, three cationic surfactants generated from alginic acid
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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were synthesized and evaluated. To better understand the
corrosion inhibitory effects of these chemicals, three sepa-
rate methodologies were used: weight loss experiments,
polarization experiments, and electrochemical impedance
spectroscopy. As a corrosive medium, one milliliter of con-
centrated HCl was utilized in a 1:1 ratio. The corrosion rate
of mild steel in 1.0M HCl was determined by using gravi-
metric analysis at four different temperatures: 25, 40, 55,
and 70 degrees Celsius. At a temperature of 25 degrees Cel-
sius, electrochemical validation was used to determine the
corrosion rate of mild steel. On the other hand, it has been
shown that the efficiency of produced corrosion inhibitors
is directly proportional to the length of their hydrophobic
chains and the number of inhibitors present in the solu-
tion. Temperature increases have a favorable influence on
inhibitory effectiveness because of chemical absorption in
the solution (chemisorption). It was discovered by the find-
ings of the potentiostatic polarization experiment that the
green cationic surfactants under investigation function as
mixed type inhibitors, with the cathodic reaction serving as
the predominant mechanism of action. It has been shown
that increasing the thickness of a manufactured double layer
is linked with a reduction in double layer capacitance, as
assessed by electrochemical impedance measurements of a
manufactured double layer. It was observed that the appar-
ent activation energy of the inhibited solution was lower
than the apparent activation energy of the uninhibited solu-
tion, which served as an indication of chemical sorption.
5.1.5 Amino Acids
Amino acids are highly pure, non-toxic, biodegradable,
cheap, and easy to make. They are particularly effective in
avoiding corrosion of archeological metal artifacts [74–80].
New protection solutions were investigated, based on long-
chain carboxylic acids. On many metals, these solutions
are well known to have good inhibition properties. They
are also environmentally friendly and are reversible. These
inhibitors were tested on coupons made of iron and cop-
per. Electrochemical tests were conducted to determine the
inhibitor's efficiency against corrosion. The successful effi-
ciency of the therapies against ozone degradation has been
proven by artificial aging in the temperature room. Surface
characterization of treated samples by X-ray diffraction and
Raman spectroscopy proved that, due to the formation of a
thin hydrophobic film of metallic carboxylate on the metal
surface, the inhibitive effect is. In nitric acid solution α-
amino acids serve as corrosion inhibitors for copper [81]. A
series of amino acids such as cysteine (Cys), lysine (Lys),
arginine (Arg), glycine (Gly), and valine (Val) for copper
corrosion are tested in 1M HNO3 by weight loss and electro-
chemical polarization measurements [82]. Cysteine is good
corrosion of copper in nitric with inhibition efficacy 96%.
The inhibition efficacies were found to vary in the order Val
˂ Gly ˂Arg ˂ Lyc ˂Cys. Cysteine is one of the most effec-
tive inhibitors in acid solutions and chlorides because of
the good condensation on the metal surface. It also indi-
cated that it is environmentally acceptable and therefore
a safe alternative to the harmful corrosion inhibitors used
to protect the bronze. In addition, it stated that cysteine is
also employed as a respectable weathering suppression for
copper in both alkaline and neutral solutions and that its
surface adsorption process is subject to Langmuir isotherm
adsorption theory [83]. Cysteine is non-toxic and an envi-
ronmentally acceptable weathering suppressor for alloys of
copper. The cysteine formula is chemically having the fol-
lowing structural formula C3H7NO2S Table2.
The corrosion mechanism is based on the amino acid
adsorption at the active corrosion sites. Cysteine obeys the
isotherm of Langmuir adsorption, and the calculated free
adsorption energy on Cu reveals strong physical adsorption
of the metal surface inhibitor. It is understood that a heter-
oatoms such as nitrogen, oxygen, arsenic, and phosphorus
will adsorb the most organic material on the metal surface.
For cysteine, the amino and thiol groups strengthen cysteine
adsorption on the copper sheet. On the metal surface, a
stable film of copper—cysteine complexes is formed that
retards the corrosion process. Since cysteine is an amino
acid, depending on pH, it may have either a negative or a
positive charge. The amino acid will mainly have a positive
charge in acidic surroundings. It means that the presence of
chloride will improve the adsorption of cysteine to copper,
making cysteine an effective deterrent for bronze-illness arti-
facts. Past work has shown that small amounts of cysteine
(0.015M) serve as a stronger inhibitor of corrosion than
BTA on copper in a very acidic hydrochloric acid environ-
ment and have a direct impact on the appearance of bronzes
as shown in Figs.9 and 10 [84]. Cysteine is one of the most
effective inhibitors in acid solutions and chloride because of
the good condensation on the metal surface. It also indicated
that it is environmentally acceptable and, therefore, a safe
alternative to the harmful corrosion inhibitors used to protect
the bronze effects from corrosion [85].
5.1.6 Ionic Liquid
Over the last decade, ionic liquids had interesting properties
such as non-inflammability, non-toxicity, low volatility, high
thermal and chemical stability, and their ability to adsorb
metal surfaces. The ionic liquids are used in many electro-
lyte media for various metals and alloys, such as mild steel,
copper, zinc, and magnesium. The ionic liquids are prom-
ising, noble, green, and sustainable candidates to replace
traditional volatile corrosion inhibitors and can be adsorbed
effectively on metal surfaces. The high cost of ionic liquid
limits the use of ionic liquid on artifacts so far [86–90].
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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5.1.7 Plant Extracts Inhibitors
Eco-friendly compounds, nowadays, especially plant
extracts, play an important role as inhibitors of corrosion due
to their biodegradability, non-toxic nature, and being rela-
tively less expensive. Biodegradability, however, restricts
plant extracts' preservation and long-term use. However, it
is proposed that microorganisms can prevent the decomposi-
tion of plant extracts by adding biocides [76–80]. Improve-
ment in the inhibitive capacity of plant extracts in various
conditions has been tested for different metals [91–95]. The
properties of extracted oil from seeds of Nigella Sativa as an
iron corrosion inhibitor are investigated in acid rain solution
[96–98]. Measurements for open circuit potential (OCP),
polarization, and impedance spectroscopy have been used.
The tests of impedance validate the potentiodynamic results.
The strong protective effect of the extract is due to the for-
mulation of the film on the iron surface with 99 percent
inhibition efficiency. Alqasmi based on test results observed
that both fig and olive extracts have a high efficiency of 97.8
percent for HCl copper safety and room temperature sulfuric
solutions [99–102]. The electrochemical experiments tested
Aloe Vera extract as a corrosion agent for copper and brass
alloy; studies indicate that Aloe Vera contains, in addition
to its dietary ingredients, hormones, polysaccharides, amino
acids, essential elements, such as nitrogen, and tannins. In
aloe vera extract, tannin compounds can be adsorbed on
the metal surface and block the active sites. Reducing the
rate of corrosion gave a high corrosion efficiency, reach-
ing 88 percent in NaCl [103]. Rauf and Mahdi observed
Table 2 The molecular structure
of amino acids
Molecular structure Name Abbreviation
Valin Va
Glycin
eG
l
Arginine Ar
Lysine Ly
Cysteine Cy
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that it was more effective to use Green Tea as a corrosion
inhibitor for Brass in acid and alkaline conditions than using
Nicotine [104]. The extracts gave the archeological objects
good resistance as antifungal materials for the fungal attack.
The use of green tea extracts as a historical copper inhibi-
tor in NaCl solution also provided reasonable efficiency in
inhibition [105]. The use of Allium Cepa onion extract as a
corrosion inhibitor is clarified against iron, nickel, and cop-
per corrosion which gave the extract a high iron output that
exceeded 92% of Nickel 88% and its copper output to 46%
[106]. Coconut water is used for iron corrosion elimination
and cure [107]. With hydrochloric acid at room temperature,
Indian Seder is used as a corrosion agent for copper and
aluminum [108]. Electrochemical studies have shown that
corrosion efficiency improved by increasing the concentra-
tion of the inhibitor. Copper's corrosion efficiency was 88.58
percent. This means that it is adsorbed to the surface creat-
ing a strong barrier to corrosion, and it obeys isothermal
adsorption by Langmuir. It is reported that the results of his
tests on Cannabis as a sulfuric acid inhibitor of copper cor-
rosion gave a good inhibition. Increasing its concentration
increases the efficiency of inhibitions [109]. Tannic acid is
a good inhibitor of corrosion, particularly with high-per-
formance copper in aqueous solutions and its performance
was reduced with both zinc and iron [110]. Shah observed
that tannin extract in the acidic media serves as a cathodic
inhibitor as a corrosion inhibitor for copper, with an inhibi-
tion efficiency of 82 percent [111]. The use of caffeic acid
as a copper corrosion inhibitor in sodium chloride solution
and the results showed that the corrosion rate in the base
solution decreased to form a protective layer of caffeic acid
on the surface as a result of physical adsorption [112]. The
use of Mimusops Elengi papers as a corrosion agent for cop-
per in the natural seawater was shown by his experimental
research [113]. The results revealed that it is a good inhibitor
Fig. 9 Archeological bronzes A before treatment, B after inhibited
with 0.26M BTA, and C after treatment with 10% Paraloid B-72 in
ethanol
Fig. 10 Archeological bronzes A before treatment, B after inhibited
with 0.15M cysteine, and C after treatment with 10% Paraloid B-72
in ethanol
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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of corrosion with a performance of 86.84 percent. Gum Ara-
bic Acacia [GA] is one of the most common natural gums,
extracted from acacia trees. Because of its non-toxic and
biocompatible characteristics, it has been used for multiple
applications; the inhibition action was studied [114–117].
5.2 Inorganic Green Inhibitors
The organic inhibitors are generally used in acidic condi-
tions, whereas inorganic inhibitors are used in an almost
neutral medium. The higher concentrations of many metals
are causing toxicity to all life forms. High-toxicity chromates
were used as highly efficient corrosion inhibitors. Alterna-
tives to chromate inhibitors in search for green inhibitor lan-
thanide salts is the use of the rare earth compounds CeCl3
in aerated NaCl Solution as a steel barrier. Due to the dif-
ficulty of separating rare earth elements from each other in
the extraction process, the use of rare earth elements as cor-
rosion inhibitors is limited, because it involves a lot of acids
and ammonia waste. The yellow color of the formed layer
limits its uses for artifact protection [118–121].
5.3 General Characteristic ofGreen Inhibitors
Green inhibitors are environmentally friendly, non-toxic,
lower in cost, and biodegradable. Green inhibitors have the
same properties as the 'non-green' inhibitors. Most of the
green inhibitors were adsorbed by physical and/or chemical
adsorption to the metal surface. The efficiency of inhibi-
tors decreases or increases in the corrosive environment
with extended exposure. Efficiency reduces with increasing
time in most situations, which means the inhibitor mole-
cules become adsorbed by physical interactions. The dos-
age shall be administered at a low concentration. And, too,
the efficiency of inhibition decreases with rising concentra-
tion to maximum concentration. That increase is due to the
adsorbed inhibitor layer's stability. It is necessary to know
the structure and source of the synthesis or natural inhibitor,
by comparing the activity of various inhibitors. The syner-
gistic effect of halide derivatives such as KCl, KBr, and KI
on plant extracts inhibit acid corrosion of mild steel. Typi-
cally speaking, certain drawbacks such as the active compo-
nent and biodegradability for natural plant extracts have not
been established, which restricts the storage and long-term
extract usage [122]. Nevertheless, biocides such as sodium
dodecyl sulfate, can inhibit decomposition. The use of envi-
ronmentally friendly extracts as green corrosion inhibitors
represents a trend that is very up to date. Sadly, they have a
complex chemical nature which makes it difficult to know
the mechanisms of seed inhibition oils or extracts or leaves
which yield various chemical compositions and properties.
Some extra features are required to use the promising green
corrosion inhibitors to protect metal artifacts as they must
be easily removed from the surface (i.e., its reversibility) and
prevent artifacts from changing color.
5.4 Mechanism ofAction ofGreen Inhibitors
There is an electrochemical nature to corrosion. They involve
two or more reactions to the electrode: anodic and cathodic.
Furthermore, as seen in Fig.11, the corrosion requires an
ionic connection between the anode and the cathode, water
provides an electrolyte, e.g., from humid air, seawater, and
rain. The anodic oxidation reaction of metallic structure is
as follows:
The cathodic reaction:
In neutral or basic solutions
The metal cations, like aqueous ions, can enter the atmos-
phere and precipitate away from the surface, and the surface
begins to corrode. Otherwise, the metal cations that react
with surrounding anions that form corrosion products such
as oxides, hydroxides, carbonates, sulfates, etc. cover the
metal surface. It can be classified into three different types
according to the corrosion reaction: cathodic, anodic, and
mixed inhibitor. Cathodic blockers behave while exacerbat-
ing cathodic areas preferentially and by obstructing them.
Additionally, the anodic inhibitors induce a broad anodic
change of the potential for corrosion to create a protective
oxide layer on the metal surface. Mixed or adsorbed inhibi-
tors affect both cathodic and anodic reactions, shaping the
surface of adsorbed material. Inorganic inhibitors are gen-
erally either cathodic or anodic, whereas organic inhibitors
have both cathodic and anodic actions as shown in Fig.12.
(6)
M
→
Mn++ne
(7)
2
H
+
+2e
−
→H
2
(8)
1
2
O2+H2O+2e−→2OH
−
Fig. 11 Schematic depiction of the electrochemical mechanisms of
corrosion in an underwater environment
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The corrosion is also a surface reaction; the introduction
of a low inhibitor concentration will reduce the corrosion
rate of the metal that is subjected to the corrosive environ-
ment. There are three inhibition pathways as given below in
general [123]:
• Adsorption: the receptor is adsorbed chemically to the
metal surface creating a thin shielding layer.
• Surface layer: A metal surface forming a covered oxide
film.
• Passivation: the inhibitor interacts with aqueous media
corrosive elements which form a protective precipitate.
The adsorption of the corrosion inhibitor on the metal-
lic superficiality is contingent on the formula of chemi-
cal configuration and physiochemical properties for the
compound such as functional groups, electronic density,
molecular structure, chain length, and the strength of adhe-
sion to the surface and depends on the temperature and pH
[124]. Organic compounds act as good inhibitors due to
their heteroatom structures such as S, N, P and O in the
π-electrons-conjugated system. These functional groups
are bonded to the metal surface either by physisorption or
chemisorptions. The efficiency surveys the O < N < S < P
sequence. Most organic inhibitors adsorbed on the sur-
face of the metal forming a compact barrier by displac-
ing surface water molecules. The single pair of inhibitor
molecules enables the movement of electrons from inhibi-
tor to metal and improve inhibition when an H atom is
replaced by substituent groups (–NH2, –NO2, –CHO, or
–COOH). In addition, the inhibition increases to about 10
carbons with increasing carbon numbers in the chain [44,
125, 126]. Thus, by adsorption of ions/molecules on the
metal surface, the inhibitors decrease the corrosion rate.
Organic receptor adsorption pathways consist of one or
more finishing steps. In the first step, organic inhibitor
adsorption on a metal surface usually involves replacing
one or more water molecules that were initially adsorbed
at the metal surface.
where inhsoln and inhads are the suppressors and adsorbed
inhibitors on the metallic superficial, respectively. As a result
of the metal oxidation or dissolution process, the inhibitor
may then combine with newly generated metal ions M+ [2]
on the surface, forming a complex of metal inhibitors.
Commonly, in the absence of corrosion protection, the
aggressive solution has always been in touch with both the
metal and porous film affects the stock metal dissolution
during which, just like in the existence of a suppressed solu-
tion, the active sites are almost blocked by the adsorption
of the inhibitor forming a passive layer which suppresses
further corrosion. The inhibitors' defensive function is
creating a shield against hostile media from one or more
molecular levels. This behavior is consistent with chemical
and/or physical adsorption involving charge transfer from
one step to the next. The degree of corrosion protection
increases with increased concentration of the inhibitor up
to optimum concentration. The amino acids as an exam-
ple of green corrosion inhibitors that have shown a strong
ability to regulate corrosion in various metallic materials
in diverse conditions. These compounds' inhibitive effect
was attributed to the accumulation of inhibitor molecules
through adsorption on the metal surface, which reduces the
metal's contact with the solution's corrosive agents. Through
one configuration, the neutral blocker can be protonated
via a chemisorption method on the substrate, and then in
another mode, the compensated blocker can electrostati-
cally meet charged metal substrate [127–134]. If the metal
surface is charged negatively, the protonated amino acids
would be adsorbed immediately on the surface of the metal
as in Fig.13a and to the positively charged metal surface
via the already adsorbed anions (e.g., halide ions) as shown
in Fig.13b. If metal surface charge becomes zero, however,
none of the cations or anions on the surface will be adsorbed.
In this case, the amino acid molecule is chemically adsorbed
by unshared electron pairs of heteroatoms (i.e., O, N and
S) and/or the p electrons of the amino acid aromatic ring
(electron donors) transferred to the empty d orbital of the
surface metal atoms (electron acceptors) in Fig.13c. On
the other hand, the inhibiting effect of some amino acids on
metal corrosion was attributed to the formation of insoluble
(9)
inhsol +xH2Oads
→
inhads +H2Oads
(10)
M+2
+inhads →Minh
+2
ads
Fig. 12 Mechanism of corrosion inhibitors
Journal of Bio- and Tribo-Corrosion (2022) 8:35
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complexes between the surface metal ions and the amino
acid through functional groups as in Fig.13d.
6 Conclusion
Technically, economically, and environmentally, it is impor-
tant to reduce or control metal corrosion, which is a major
problem especially for the protection of archeological arti-
facts, most of which focus on illustrating the benefits of syn-
thetic compounds as tremendous inhibitors of corrosion, but
most of them are very toxic and pose a serious threat to
both humans and the environment. However, recent stud-
ies have demonstrated green inhibitors as the best inhibitor
for the most metal in different corrosive environments. The
major advantages are non-toxicity, biodegradability, cheep,
and eco-friendliness. Several experimental methodologies
have been used to investigate the inhibition efficiency of
green inhibitors in various media including the gravimet-
ric method, the technique of potentiodynamic polariza-
tion, method of electrochemical impedance spectroscopy,
and method of hydrogen evaluation. Innumerable surface
properties have been studied with the help of AFM, FTIR,
UV, fluorescence spectra, and SEM with energy disperse
spectroscopy (EDS), all of which demonstrate the produc-
tion of green inhibitor mechanisms that suggest that ions/
compounds are chemisorbed to metal substrates, interact
with anodic and/or cathodic reactions, and decrease the
diffusion rate of reactants. Alternatively, green corrosion
inhibitors are very effective in combating corrosion with het-
eroatom and π-electron moieties. They include many organic
compounds that have polar atoms such as O, N, P, and S.
Through these polar atoms they are adsorbed upon the metal
surface and protective films are formed. Adsorptions of these
ingredients obey the different isotherms of adsorption. Lat-
est corrosion inhibition experiments are reviewed and sum-
marized according to the category of inhibitors. Despite the
very interesting properties of ionic liquid, very few reports
have been released about their application to protect met-
als from corrosion. In most cases, the low thickness of the
inhibitor protective layers makes them invisible, but in other
cases, the inhibitors produce visible changes, and all these
layers are chemically stable in the environment. Due to their
low thickness, they are not resistant to mechanical removal.
Another advantage of green inhibitors in metallic heritage
conservation is that they can be used in many cases in com-
bination with protective coatings, increasing the protective
function of the whole system. We hope that these products
will be able to replace, soon, the toxic commercial products
that are still being used for many archeological artifacts.
Funding Not applicable.
Declarations
Conflict of interest The authors declare that there is no conflict of in-
terest.
Fig. 13 Simplified schema
of some interaction modes of
amino acid with the metallic
surface in the inhibition process
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