lubricants

Review
Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors
Ahmed A. Al-Amiery 1,2, * , Wan Nor Roslam Wan Isahak 1 and Waleed Khalid Al-Azzawi 3

1 Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia (UKM), Bangi 43600, Malaysia
2 Energy and Renewable Energies Technology Center, University of Technology-Iraq, Baghdad 10001, Iraq
3 Medical Technical College, Al-Farahidi University, Baghdad 10001, Iraq
* Correspondence: dr.ahmed1975@[Link] or dr.ahmed1975@[Link]

Abstract: Corrosion is a major challenge in various industries and can cause significant damage to
metal structures. Organic corrosion inhibitors are compounds that are used to reduce or prevent
corrosion by forming a protective film on metal surfaces. The present review article focuses on natural
and synthetic organic corrosion inhibitors and their classifications, active functional groups, and
efficiency estimations. Furthermore, previous studies on the use of natural and synthetic organic
inhibitors are discussed, along with adsorption isotherms and mechanisms of organic corrosion
inhibitors. The kinetics of corrosion modeling are also discussed, providing insights into the effec-
tiveness of organic inhibitors at reducing corrosion. This review aims to provide a comprehensive
overview of the current knowledge on organic corrosion inhibitors, with the aim of promoting their
wider use in corrosion protection.

Keywords: organic corrosion inhibitors; types of corrosion; efficiency; adsorption isotherms

1. Introduction
Corrosion inhibitors are substances used to prevent or reduce metal surface corro-
sion in corrosive environments. There are two types of corrosion inhibitors: natural
and synthetic [1]. Natural inhibitors, derived from plants and minerals, are eco-friendly,
biodegradable, and low in toxicity. Examples include vegetable oils, tannins, and salicylic
Citation: Al-Amiery, A.A.; Isahak, acid. However, they may have limited effectiveness and may be unsuitable for severe
W.N.R.W.; Al-Azzawi, W.K. corrosion environments. Furthermore, their costs can be higher compared to synthetic
Corrosion Inhibitors: Natural and inhibitors [2]. Despite these limitations, natural inhibitors are gaining popularity as sus-
Synthetic Organic Inhibitors. tainable and eco-friendly alternatives to synthetic inhibitors that can be used in various
Lubricants 2023, 11, 174. applications, such as in the oil and gas industry and for preserving historical artifacts [3].
[Link]
Natural inhibitors are renewable, biodegradable, and safe for human exposure, making
lubricants11040174
them appropriate for industries such as food and pharmaceuticals [4].
Received: 11 February 2023 In contrast, synthetic inhibitors are chemically manufactured to provide high efficacy
Revised: 3 March 2023 in a range of corrosive environments. Amines salts, phosphates, and nitrites are examples
Accepted: 4 March 2023 of synthetic inhibitors [5]. Synthetic inhibitors are more effective, have a wider range of
Published: 11 April 2023 applications, are reliable, and have a longer shelf life than natural inhibitors [6]. Synthetic
inhibitors form a protective film on metal surfaces and react with corrosive substances to
prevent corrosion. They are particularly effective in harsh and corrosive environments
with high levels of impurities, salt, and other contaminants [7]. Synthetic inhibitors are
Copyright: © 2023 by the authors.
ideal for applications such as offshore platforms, pipelines, and nuclear power plants
Licensee MDPI, Basel, Switzerland.
where maintenance is challenging or costly. Nevertheless, synthetic inhibitors are more
This article is an open access article
expensive than natural inhibitors and require proper selection and dosing to prevent
distributed under the terms and
environmental damage and interference with other chemical processes in the system [8].
conditions of the Creative Commons
Attribution (CC BY) license (https://
In summary, synthetic inhibitors are widely used in various industrial applications due
[Link]/licenses/by/
to their effectiveness, but their potential environmental impact should be considered, and
4.0/). their selection and dosing should be carefully managed [9,10].

Lubricants 2023, 11, 174. [Link] [Link]

Lubricants 2023, 11, x FOR PEER REVIEW 2 of 3

In conclusion, both natural and synthetic corrosion inhibitors play an important rol
Lubricants 2023, 11, 174 in preventing corrosion and extending the lifespan of metal surfaces. The 2choice
of 29 of th
type of inhibitor to use will depend on the specific application, the severity of the corro
sion environment, and the desired level of efficacy.
In conclusion, both natural and synthetic corrosion inhibitors play an important role
in
2. preventing corrosion and extending the lifespan of metal surfaces. The choice of the
Types of Corrosion
type of inhibitor to use will depend on the specific application, the severity of the corrosion
There are several types of corrosion, including [11]:
environment, and the desired level of efficacy.
• Uniform Corrosion: This is the most common type of corrosion and occurs evenly
2. Types of aCorrosion
over large surface area of a material. It is caused by exposure to a corrosive envi
There are several
ronment, types
such as of corrosion,
water, including [11]:
air, or chemicals.
•• Pitting Corrosion:
Uniform Corrosion:This This type
is the mostof common
corrosion typeis of
characterized
corrosion andby the evenly
occurs formationover of smal
aholes
large surface
or pits area
on the of asurface
[Link] Ita material.
is caused by exposure
It is causedtobya localized
corrosive environment,
corrosion, often du
such as water, air, or chemicals.
to the presence of impurities in the material or environmental factors, such as high
• Pitting
chloride Corrosion:
levels. This type of corrosion is characterized by the formation of small
holes or pits on the surface of a material. It is caused by localized corrosion, often due
• Galvanic Corrosion: This type of corrosion occurs when two dissimilar metals are in
to the presence of impurities in the material or environmental factors, such as high
contactlevels.
chloride with each other and an electrolyte, such as saltwater, is present. One meta
• becomesCorrosion:
Galvanic anodic and Thiscorrodes, while occurs
type of corrosion the other whenbecomes cathodic
two dissimilar andareisinprotected
metals
from corrosion.
contact with each other and an electrolyte, such as saltwater, is present. One metal
• Creviceanodic
becomes Corrosion: This typewhile
and corrodes, of corrosion
the otheroccurs
becomes in cathodic
confinedandareas, such as crevice
is protected
from corrosion.
or seams, where the flow of air and liquids is restricted. This leads to a buildup o
• Crevice
corrosive Corrosion:
substancesThis and
typetheof corrosion
material occurs
corrodes in confined
from theareas, such
inside [Link] crevices
• orIntergranular
seams, whereCorrosion:
the flow of This air and liquids is restricted. This leads to a buildup
type of corrosion occurs along the grain boundaries of o
corrosive substances and the material corrodes from the inside out.
a material, causing a loss of material and weakening of the structure. It is often caused
• Intergranular Corrosion: This type of corrosion occurs along the grain boundaries of a
by the presence of impurities, such as sulfur or chlorine, in the material.
material, causing a loss of material and weakening of the structure. It is often caused
• Erosion
by Corrosion:
the presence This type
of impurities, suchofas corrosion
sulfur or occurs
chlorine, when
in theamaterial.
material is exposed to a cor
• Erosion Corrosion: This type of corrosion occurs when a materialmaterial
rosive fluid that is flowing at a high velocity, causing the is exposed to erode
to a away
This type
corrosive of corrosion
fluid that is flowingis common
at a highinvelocity,
pipelines, valves,
causing the and pumps.
material to erode away.
• This
StresstypeCorrosion
of corrosion is common
Cracking: Thisin pipelines, valves, andoccurs
type of corrosion [Link] a material is unde
• Stress
stressCorrosion Cracking:
and exposed to a This type ofenvironment.
corrosive corrosion occurs It when a material
is often causedisby under
high tensil
stress and exposed to a corrosive environment.
stress, high chloride levels, or high temperatures. It is often caused by high tensile stress,
high chloride levels, or high temperatures.
In conclusion, the type of corrosion as in Figure 1, that a material experiences is de
In conclusion, the type of corrosion as in Figure 1, that a material experiences is
dependenton
pendent onmany
many factors, includingthe
factors, including thematerial
material itself,
itself, thethe corrosive
corrosive environment,
environment, and and th
conditions
the under
conditions underwhich
which the
the material
material isisexposed.
exposed. Understanding
Understanding these
these factors
factors is crucial fo
is crucial
developing effective strategies for preventing and mitigating material corrosion.
for developing effective strategies for preventing and mitigating material corrosion.

[Link]
Figure Typesof of
Corrosion.
Corrosion.
Lubricants 2023, 11, x FOR PEER REVIEW 3 of 31
Lubricants 2023, 11, 174 3 of 29

3. Classifications of Organic Corrosion Inhibitors

3. Classifications of Organic Corrosion Inhibitors
Corrosion inhibitors can be classified into two main categories [12]:
Corrosion inhibitors can be classified into two main categories [12]:
• Inorganic corrosion inhibitors: These inhibitors contain metallic compounds such as
• Inorganic corrosion inhibitors: These inhibitors contain metallic compounds such as
nitrates, phosphates, chromates, and molybdates. They work by forming a protective
nitrates, phosphates, chromates, and molybdates. They work by forming a protective
film on the metal surface, which prevents the formation of corrosion cells.
film on the metal surface, which prevents the formation of corrosion cells.
• Organic corrosion inhibitors: These inhibitors contain organic compounds such as
• Organic corrosion inhibitors: These inhibitors contain organic compounds such as
amino acids, alcohols, and amines. They work by adsorbing onto the metal surface
amino acids, alcohols, and amines. They work by adsorbing onto the metal surface
and
and forming
forming aabarrier
barrierbetween
betweenthethemetal
metaland thethe
and corrosive environment.
corrosive Organic
environment. in-
Organic
hibitors are commonly used in industries such as oil and gas, petrochemical, and
inhibitors are commonly used in industries such as oil and gas, petrochemical, and ma-
rine applications.
marine applications.
Organic
Organic inhibitors
inhibitorscancanbe
beclassified
classifiedinto
intoseveral
severaltypes
typesofof
inhibitors [13],
inhibitors as in
[13], as Figure
in Figure2: 2:
•• Nitrite
Nitrite inhibitors:
inhibitors: These
These inhibitors
inhibitors contain
contain nitrite
nitrite ions
ions as
as the
the active
active ingredient
ingredient andand are
are
commonly used in cooling water systems
commonly used in cooling water systems and boilers. and boilers.
•• Phosphonic
Phosphonic acidacidinhibitors:
inhibitors:ThisThistype
typeofofinhibitor contains
inhibitor contains phosphonic
phosphonic acidacid
or its
orde-
its
rivatives and is effective at preventing corrosion in high-temperature
derivatives and is effective at preventing corrosion in high-temperature and high- and high-pres-
sure systems.
pressure systems.
•• Carboxylic
Carboxylic acid
acid inhibitors:
inhibitors: Carboxylic
Carboxylic acidacid inhibitors
inhibitors are
are commonly
commonly used used inin indus-
indus-
trial
trial applications and contain compounds such as benzoic acid, salicylic acid, and
applications and contain compounds such as benzoic acid, salicylic acid, and
acetic
acetic acid.
acid.
•• Sulfonic acid inhibitors: Sulfonic
Sulfonic acid
acid inhibitors
inhibitors contain
contain sulfonic
sulfonic acid
acid and
and its
its deriva-
deriva-
tives and are used in a wide range of industrial applications.
•• Thiophosphoric
Thiophosphoric acid inhibitors: Thiophosphoric
Thiophosphoric acid acid inhibitors
inhibitors contain
contain thiophos-
thiophos-
phoric acid and its derivatives and are effective at preventing
acid and its derivatives and are effective at preventing corrosion corrosion in high-tem-
in high-
perature
temperaturesystems.
systems.
•• Ethylenediamine
Ethylenediamine inhibitors:
inhibitors: This
This type
type ofof inhibitor
inhibitor contains
contains ethylenediamine
ethylenediamine as as the
active ingredient and is used in a variety of industrial applications.
•• Amines inhibitors:
inhibitors: Amines
Amines inhibitors
inhibitors contain
containamine
aminecompounds
compoundsasasthe theactive
activeingredi-
ingre-
ent and are commonly used in water treatment and oilfield
dient and are commonly used in water treatment and oilfield applications. applications.
•• inhibitors: Phenol
Phenol inhibitors: Phenol inhibitors
inhibitors contain
contain phenol
phenol oror its
its derivatives
derivatives as as the active
ingredient and are used in a variety of industrial applications.
applications.

Figure 2. Organic inhibitors classifications.

4.
4. Active
Active Functional
Functional Groups
Groups in
in Organic
Organic Corrosion
Corrosion Inhibitors
Inhibitors
Active functional groups play
functional groups play a crucial role in the effectiveness of organic corrosion
inhibitors. These
These functional groups interact with the metal surface
functional groups interact with the metal surface and
and form a protective
layer, preventing further corrosion. Some
Some of the most commonly used active functional
groups in organic corrosion inhibitors are as follows
follows [14]:
[14]:
•• Nitrogen-containing
Nitrogen-containing functional
functionalgroups:
groups:These functional
These groups
functional contain
groups nitrogen
contain at-
nitrogen
oms, which
atoms, whichcan
canform
formchelating
chelatingagents
agentswith
withmetal
metalions.
[Link]
Themost
mostcommon
commonnitrogen-
nitrogen-
Lubricants 2023, 11, 174 4 of 29

containing functional groups used in corrosion inhibitors include amines, imides,

and guanidines.
• Oxygen-containing functional groups: These functional groups contain oxygen atoms,
which can form a protective film on the metal surface, inhibiting further corrosion.
Some of the most common oxygen-containing functional groups used in corrosion
inhibitors include carboxylic acids, esters, and ethers.
• Sulfur-containing functional groups: Sulfur-containing functional groups can form a
protective film on the metal surface, preventing further corrosion. Some of the most
commonly used sulfur-containing functional groups in corrosion inhibitors include
sulfonic acids and thiols.
• Phosphorus-containing functional groups: Phosphorus-containing functional groups
can form a protective film on the metal surface, inhibiting further corrosion. Some
of the most commonly used phosphorus-containing functional groups in corrosion
inhibitors include phosphonic acids and phosphates.
• Halogen-containing functional groups: Halogen-containing functional groups, such
as halogens (chlorine, fluorine, and bromine), can form a protective film on the metal
surface, inhibiting further corrosion.
In conclusion, active functional groups play a crucial role in the effectiveness of organic
corrosion inhibitors. By interacting with the metal surface and forming a protective layer,
these functional groups can prevent further corrosion, thereby extending the lifespan of
metal components.

5. Estimating Organic Corrosion Inhibitors Efficiency

Organic corrosion inhibitors work by forming a protective layer over the metal surface,
preventing the formation of corrosion products and protecting the metal from degradation.
However, it is important to estimate the efficiency of these inhibitors to ensure that they are
working as expected and to determine if any changes need to be made to the system [15].
The efficiency of both natural and synthetic corrosion inhibitors can be estimated using
various methods.

5.1. Electrochemical Techniques

Electrochemical techniques such as potentiodynamic polarization and electrochemical
impedance spectroscopy (EIS) can be used to calculate the effectiveness of organic corrosion
inhibitors. These methods estimate the changes in current and voltage that occur in the
presence of inhibitors and provide information about the rate of corrosion [16].

5.1.1. Potentiodynamic Polarization

Potentiodynamic polarization is a reliable method for evaluating the effectiveness of
organic inhibitors at mitigating metal corrosion [17]. This technique involves applying a
controlled potential to the metal surface immersed in a solution containing the inhibitor
and a reference electrode. The current response is monitored at regular intervals and the
data are analyzed to determine the corrosion potential and current. The change in current
and potential provides information about the effectiveness of the inhibitor at reducing
the corrosion rate. The results of this method can help optimize the concentration of the
inhibitor and corrosion protection conditions.
Inhibitors can reduce the corrosion rate by slowing down the cathodic and anodic
reactions [18–21]. Cathodic reactions involve the reduction in oxidants, while anodic
reactions involve the oxidation of the metal. Inhibitors can reduce the cathodic reaction rate
by either blocking the reduction sites, reducing the driving force for the reduction reaction,
or competing with the oxidant for electrons. They can also reduce the anodic reaction
rate by either blocking the anodic sites, increasing the activation energy for the oxidation
reaction, or forming a passive layer on the surface of the metal that prevents the dissolution
of the metal. Inhibitors can be classified into three types based on their mode of action:
anodic inhibitors, cathodic inhibitors, and mixed-type inhibitors [22]. Anodic inhibitors
Lubricants 2023, 11, x FOR PEER REVIEW 5 of 31

Lubricants 2023, 11, 174 5 of 29

anodic inhibitors, cathodic inhibitors, and mixed-type inhibitors [22]. Anodic inhibitors
reduce the anodic reaction rate by forming a passive layer on the surface of the metal that
reduce the anodic reaction rate by forming a passive layer on the surface of the metal that
prevents the dissolution of the metal. Examples of anodic inhibitors include chromates,
prevents the dissolution of the metal. Examples of anodic inhibitors include chromates,
molybdates, and phosphates. Cathodic inhibitors reduce the cathodic reaction rate by ei-
molybdates, and phosphates. Cathodic inhibitors reduce the cathodic reaction rate by
ther adsorbing on the surface of the metal, forming a protective layer, or by competing
either adsorbing on the surface of the metal, forming a protective layer, or by competing
with the oxidant for electrons. Examples of cathodic inhibitors include nitrates, nitrites,
with the oxidant for electrons. Examples of cathodic inhibitors include nitrates, nitrites,
and amines. Mixed-type inhibitors can act on both the anodic and cathodic reactions by
and amines. Mixed-type inhibitors can act on both the anodic and cathodic reactions by
forming
formingaaprotective
protectivelayer
layeronon the surface
the surfaceof the metal
of the thatthat
metal reduces
reducesthe anodic reaction
the anodic rate
reaction
and
ratealso
andby competing
also with the
by competing oxidant
with for electrons,
the oxidant which reduces
for electrons, which the cathodic
reduces reaction
the cathodic
rate. Examples of mixed-type inhibitors include benzotriazole, tolyltriazole,
reaction rate. Examples of mixed-type inhibitors include benzotriazole, tolyltriazole, and and mercap-
tobenzothiazole
mercaptobenzothiazole[23]. [23].
In
In summary, inhibitors
summary, inhibitors are
are chemical
chemical substances
substances that
that can
can reduce
reduce thethe rate
rate of
of corrosion
corrosion
by acting on the anodic and/or cathodic reactions. They can be
by acting on the anodic and/or cathodic reactions. They can be classified into classified into anodic, ca-
anodic,
thodic,
cathodic,or or
mixed-type
mixed-type inhibitors,
inhibitors, depending
dependingonontheirtheirmode
modeofofaction.
[Link]
selectionof ofthe
the
appropriate
appropriate inhibitor depends on the nature of the metal and the environment in which itit
inhibitor depends on the nature of the metal and the environment in which
is
is exposed
exposed to to corrosion.
corrosion.
Figure
Figure 33 represents
represents thethe typical
typical polarization
polarizationcurves
curvesfor
formild
mildsteel
steel(MS)
(MS)corrosion
corrosionin in11
Molar HCl, both without and with the addition of different concentrations
Molar HCl, both without and with the addition of different concentrations of a terephtha- of a tereph-
thalaldehyde derivative
laldehyde derivative as aassynthesized
a synthesized organic
organic inhibitor
inhibitor [24].
[24].

Figure
Figure 3.
3. Polarization
Polarizationcurves
curvesfor
forMS
MScorrosion
corrosionin
in11MM HCl
HCl in
in the
the absence
absence and
and presence
presence of
of varying
varying
concentrations
concentrations of
of terephthalaldehyde
terephthalaldehyde derivative
derivative as
as synthesized
synthesized organic
organic inhibitors [24].

The technique
The technique of potentiodynamic
potentiodynamic polarization
polarizationinvolves
involvesapplying
applyinga apotential
potential ramp
rampto
the
to metal
the metaland
andestimating
estimatingthe theresulting
resultingcurrent
currentas
asaafunction
function of
of potential. The
The estimations
estimations
can then
can then be
be used
used to
to calculate
calculate the
the corrosion
corrosion current
current and
and potential,
potential, as as well
well as
as to
to determine
determine
the effectiveness
the effectiveness ofof the
the inhibitor.
inhibitor.
 
d
i = icorr +𝑑𝑖 i ∗ ∆E
d
𝑖 = 𝑖𝑐𝑜𝑟𝑟 + ( ) ∗E ∆𝐸
𝑑𝐸  
di 𝑑
where i𝑖 isisthe
where thetotal current,icorr
totalcurrent, 𝑖𝑐𝑜𝑟𝑟is the corrosion
is the current,
corrosion current,dE( 𝑖is) the differential
is the corrosion
differential corro-
𝑑𝐸
current, and ∆E is the potential change.
sion current, and ∆𝐸 is the potential change.
Lubricants 2023, 11, 174 6 of 29

To perform a potentiodynamic polarization experiment, the metal is first immersed in

a solution containing the inhibitor. A potentiostat is used to apply a potential ramp to the
metal and estimate the resulting current.
A potentiostat is an instrument used to determine the corrosion potential of a metal. It
does this by applying a potential ramp to the metal and measuring the resulting current.
The ramp typically begins at a potential more negative than the corrosion potential (i.e.,
cathodic), passes through the corrosion potential (i.e., zero potential), and ends at a potential
more positive than the corrosion potential (i.e., anodic). The exact potential range used
depends on the specific metal and its corrosion properties. The ramp may start at a potential
more negative than the corrosion potential to ensure that the metal is fully reduced before
measurement. The corrosion potential is then determined by measuring the potential
at which corrosion begins as the ramp passes through it. Finally, the ramp is ended at a
potential more positive than the corrosion potential to ensure that the metal is fully oxidized.
It is important to note that the potential values may be positive or negative depending on
the direction of the ramp, but the potential range is typically defined as starting at a more
negative potential and ending at a more positive potential than the corrosion potential [25].
The current-potential curve obtained from the experiment can be used to calculate the
corrosion current and potential using the following equations:


icorr = i p − im /2

where i p and im are the positive and negative half-wave currents, respectively.


Ecorr = Ep + Em /2

where E p and Em are the potentials corresponding to the positive and negative half-wave
currents, respectively.
The differential corrosion current can be calculated as:
 
di


= i p − im / E p − Em
dE

The presence of the inhibitor can be evaluated by comparing the corrosion current
and potential obtained in the presence of the inhibitor with those obtained in its absence. A
reduction in the corrosion current and potential in the presence of the inhibitor indicates
that the inhibitor is effective at reducing corrosion.
Note that these equations are general and may need to be modified depending on the
specific conditions of the experiment and the type of inhibitor used.

5.1.2. Electrochemical Impedance Spectroscopy (EIS)

EIS is a valuable, non-destructive method used to measure the impedance of a metal in
the presence of an organic inhibitor [24]. It involves applying a small sinusoidal voltage to
the metal surface and measuring the resulting current response to calculate the impedance
of the metal-inhibitor system [24]. By measuring the complex impedance of the system,
EIS provides a comprehensive understanding of the corrosion process, including the
effects of various inhibitors, corrosion rates and mechanisms, and interactions between
the metal surface and inhibitor molecules [24]. This method can be used in different
types of environments, such as aqueous or corrosive environments, and can also monitor
the effectiveness of inhibitors over time and identify potential breakdowns in protective
coatings [24].
EIS is widely used in the study of corrosion and the development of corrosion in-
hibitors, making it a useful tool for material engineers, corrosion scientists, and industrial
scientists [26]. It is also employed in the design of corrosion-resistant materials and coat-
ings [26]. Therefore, EIS is a powerful and versatile method for studying corrosion and
preventing it in metal systems [24,26].
Lubricants
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2023,11,
11,x174
FOR PEER REVIEW 7 7ofof31
29

To
To illustrate
illustrate aa typical
typical EIS
EIS measurement,
measurement,Figure
Figure44shows
showsaaNyquist
Nyquistplot
plotobtained
obtainedby by
examining mild steel in 1 M H SO at 30 ◦
°C using a newly synthesized thiosemicarbazone
examining mild steel in 1 M H2 SO4 at 30 C using a newly synthesized thiosemicarbazone
2 4

organic
organicinhibitor
inhibitoratatvarious
variousconcentrations.
[Link] equivalent
equivalentcircuit used
circuit in this
used study
in this in-
study
cludes Rs,Rs,
includes which
which represents
representsthe electrolyte
the electrolytesolution
solutionresistance,
resistance,ininseries
serieswith
withaaparallel
parallel
combination
combinationof ofaaconstant
constantphase
phaseelement
element(CPE)
(CPE)and
andRct,
Rct,which
whichmodels
modelsthethesystem
systemofofthe
the
metal
metalsubstrate,
substrate,adsorbed
adsorbedinhibitors,
inhibitors, and
and electrolyte
electrolyte solution
solution [27].
[27].

Nyquistplot
[Link]
Figure plotof
ofMS
MSinin11M
Msulphuric
sulphuricacid
acidsolution
solutionatat303
303KKfor
forvarying
varyingsynthesized
synthesizedorganic
organic
inhibitorconcentrations
inhibitor concentrations[27].
[27].

Theimpedance
The impedanceisisaacomplex
complexquantity
quantity that
that can
can be
be represented
represented by
by the
the equation:
equation:

Z = R + jX
𝑍 = 𝑅 + 𝑗𝑋
where 𝑅
where is the
R is the resistance and X𝑋isisthe
resistance and thereactance.
reactance.
The
The impedance
impedance can canbebe converted
converted intointo
a magnitude, Z0 , andZ′,phase
a magnitude, phaseΘ,
and angle, angle,
by theΘ, by the
equations:
equations:
∼  
Z = γ R2 + X 2
𝑍 = 𝛾(𝑅2 + 𝑋 2 )
҇

θ = arc tan( X/R)

𝜃 = 𝑎𝑟𝑐 tan(𝑋/𝑅)
The magnitude and phase angle of the impedance can be plotted against frequency
Thethe
to give magnitude
impedance andspectrum.
phase angle
In theof the impedance
presence of an can be plotted
organic against
inhibitor, frequency
the impedance
to give thewill
spectrum impedance
be alteredspectrum.
and can beInused
the presence of the
to quantify an corrosion
organic inhibitor, the the
current and impedance
potential
spectrum will be altered and can be used to quantify the corrosion
of the metal. The corrosion current can be obtained by fitting the impedance datacurrent and the poten-
to a
tial of the metal. The corrosion current can be obtained by fitting the impedance
Randles equivalent circuit, which consists of a series combination of an electrode resistance, data to a
Randles
a constantequivalent circuit, and
phase element, which consists of
a Warburg a series combination
impedance. The equation of an
for electrode
the Warburg re-
sistance,
impedance a constant
is: phase element, and a Warburg impedance. The equation for the War-
burg impedance is: ZW = ( Rw /2π f )0.5
Lubricants 2023, 11, 174 8 of 29

where Rw is the Warburg resistance and f is the frequency. The Warburg resistance is pro-
portional to the corrosion rate, so the corrosion current can be calculated from the equation:

icorr = 2π f Rw

The corrosion potential can be obtained from the impedance spectrum by measuring
the frequency at which the magnitude of the impedance is at the minimum. This frequency
corresponds to the maximum penetration of the organic inhibitor into the metal surface
and is directly proportional to the corrosion potential. The equation for the corrosion
potential is:
kT
Ecorr = Eo − ln( f / f o )
q
where Eo is the standard potential of the metal, k is the Boltzmann constant, T is the
temperature, q is the electron charge, f is the frequency, and f o is a constant.
In conclusion, EIS can be used to estimate the corrosion current and potential of a
metal in the presence of an organic inhibitor by applying an alternating voltage at a range
of frequencies and measuring the resulting impedance. The impedance data can be fitted to
a Randles equivalent circuit to obtain the corrosion current, and the minimum magnitude
of the impedance can be used to obtain the corrosion potential. Both potentiodynamic
polarization and EIS are valuable tools for evaluating the performance of organic corrosion
inhibitors. These techniques can provide information on the inhibition efficiency, activation
energy, and diffusion coefficient of the inhibitor, which are important parameters for
optimizing the corrosion protection performance of organic inhibitors.

5.2. Weight Loss Tests

This type of test provides an accurate estimation of the corrosion rate and the protec-
tive performance of the inhibitors. The test also allows for a comparison between different
inhibitors, which can help to determine the most effective one for specific corrosive envi-
ronments [28]. The weight loss test is typically performed over a specified time period and
the metal specimens are exposed to different corrosive environments such as salt spray,
humidity, and acid or alkaline solutions [28]. The specimens are then weighed to determine
their initial weight, and then they are exposed to the inhibitor. After the exposure time, the
specimens are re-weighed to determine their final weight and the weight loss is calculated.
The results are then compared to the control specimen, which is the metal specimen without
contact with the inhibitor [28]. The weight loss test is a simple, cost-effective, and reliable
way to evaluate the performance of organic corrosion inhibitors. It provides valuable infor-
mation on the protective properties of the inhibitors and helps to identify the most effective
one for specific corrosive environments. This information can be used to improve the
design of protective coatings, enhance the performance of existing coatings, and develop
new and improved inhibitors. An investigation for examining mild steel in 1 m HCl at
30 to 60 ◦ C K by means of a new antipyrine derivative, namely N-2-methylbenzylidene-4-
antipyrineamine, with different concentrations as a synthesized organic inhibitor is shown
in Figure 5. The published article describes a study that evaluated the corrosion rate and
protection efficiency of an inhibitor at different concentrations and temperatures. The
results showed that the protection efficiency increased with the increasing inhibitor con-
centration and decreased the corrosion rate at all concentrations. The highest protection
efficiency of 91.8% was achieved with a concentration of 0.5 mM and a temperature of 30 ◦ C.
The results also revealed that the inhibition efficiency increased with time but decreased
after 24 h. The corrosion rate increased slightly with longer exposure time in the acidic
solution [29].
Lubricants 2023, 11, x FOR PEER REVIEW 9 of 3

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31

Figure 5. Mild steel corrosion plot in 1.0 M HCl with different inhibitor concentrations synthesize
organic inhibitors at various immersion times [29].
Figure5.5. Mild
Figure Mild steel
steel corrosion
corrosion plot
plot in
in 1.0
1.0 M
M HCl
HCl with
with different
differentinhibitor
inhibitorconcentrations
concentrationssynthesized
synthesized
organicTemperature
inhibitors at highly
various affects times
immersion the corrosion
[29]. rate and the inhibition efficiency, and wit
organic inhibitors at various immersion times [29].
increasing temperature, the rate of corrosion increases exponentially in an acidic environ
[Link]
To understand
Temperature highlythe
highly affects the corrosion
protection
affects the corrosion rate and
performance
rate and of thethe
the inhibition efficiency,and
and with
with
N-2-methylbenzylidene-4-antipy
inhibition efficiency,
increasing
increasing temperature, the rate of corrosion
the rate of corrosion
rineamine at various temperature increases
degrees,increases exponentially
30–60 °C, exponentially in
the corrosion an acidic
in an
rate environ-
acidic
and envi-
inhibition e
ment.
[Link] understand
To the
understand protection
the performance
protection performance of the N-2-methylbenzylidene-4-antipy-
of the N-2-methylbenzylidene-4-
ficiency were investigated (Figure 6). N-2-methylbenzylidene-4-antipyrineamine reveale
rineamine at various temperature degrees, ◦ C, corrosion
antipyrineamine at various
the highest inhibition temperature
efficiency 30 30–60
atdegrees,
°C, 30–60°C, the
which the corrosion
regularly raterate
andand
declined inhibition ef-
inhibition
with an increase i
ficiency were
efficiency wereinvestigated
investigated(Figure
(Figure6).6).N-2-methylbenzylidene-4-antipyrineamine
N-2-methylbenzylidene-4-antipyrineamine revealed revealed
temperature. The tested inhibitor ◦exhibited lower protection performance at the max
the highest
the highest inhibition
inhibition efficiency
efficiency at at 30
30 °C, which regularly
C, which regularly declined
declined with
with anan increase
increase in
in
mum temperature.
temperature.
temperature. Thetested
The This
tested resultexhibited
inhibitor
inhibitor attends
exhibited to lower
lowertheprotection
fact that the
protection rise in temperature
performance
performance atmaximum
at the did not sup
the maxi-
port physisorption
temperature.
mum temperature. (physical
This result
This attends
result interactions),
to thetofact
attends facttherefore
thethat the
thatrise
thein reducing
rise temperaturethe did
in temperatureprotection
not not performanc
did support
sup-
[29].
physisorption (physical
port physisorption interactions),
(physical therefore
interactions), reducing
therefore the protection
reducing performance
the protection [29].
performance
[29].

Figure 6. Mild steel corrosion plot in 1.0 M HCl with different N-2-methylbenzylidene-4-antipyrin-
Figure6.(synthesized
Figure
eamine 6. Mild
Mild steel
steel corrosion
corrosion
organic plot
plotin
inhibitor) in1.0
1.0MM
HCl
HCl
concentrationswith different
atwith N-2-methylbenzylidene-4-antipyrin
different
various N-2-methylbenzylidene-4-
temperatures [29].
antipyrineamine (synthesized organic inhibitor) concentrations at varioustemperatures
eamine (synthesized organic inhibitor) concentrations at various [29].
temperatures [29].
The technique used for weight loss tests (WLTs) to estimate the corrosion current and
Theoftechnique
potential a metal inused for weight
the presence lossorganic
of an tests (WLTs) toinvolves
inhibitor estimatethe
thefollowing
corrosionsteps
current an
and equations [30]:
potential of a metal in the presence of an organic inhibitor involves the following step
and equations [30]:
Lubricants 2023, 11, 174 10 of 29

The technique used for weight loss tests (WLTs) to estimate the corrosion current and
potential of a metal in the presence of an organic inhibitor involves the following steps and
equations [30]:
• Preparation of specimens: The metal specimens are prepared and cleaned thoroughly.
Then, they are coated with a thin layer of the organic inhibitor under study.
• Weight loss measurements: The weight loss of the metal specimens is measured after
exposing them to a corrosive environment for a specified period of time. The weight
loss is calculated using the following equation:

∆W = Wo − Wt
where ∆W = weight loss, Wo = initial weight, and Wt = weight after exposure to corrosive environment.
• Corrosion current density (icorr ): The corrosion current density (icorr ) is calculated
using the following equation:

icorr = ∆W/At × nF
where At = surface area of the specimen, n = number of electrons involved in corrosion
reaction, and F = Faraday’s constant (96,485 C/mol).
• Corrosion potential (Ecorr ): The corrosion potential (Ecorr ) is estimated using a corro-
sion potential meter. The potential is recorded as a function of time and the steady-state
corrosion potential (Ecorr ) is determined.
• Comparison with control specimens: Control specimens without the organic inhibitor
are prepared and the weight loss and electrochemical estimations such as corrosion
potential and polarization resistance are obtained to evaluate the corrosion behavior
of the metal [31]. The results obtained from the control specimens are compared with
the results obtained from the specimens with the organic inhibitor. The presence of
an organic inhibitor in the corrosive environment leads to a decrease in the corrosion
current density and an increase in the corrosion potential compared to the control
specimens. The efficacy of the organic inhibitor can be determined by comparing the
results obtained with the inhibitor with the control specimens. This WLT technique is
an effective method to estimate the corrosion current and potential of a metal in the
presence of an organic inhibitor. The results obtained from this test provide valuable
information on the corrosion protection properties of the organic inhibitor.

5.3. Optical Microscopy

Optical microscopy [32] is a technique that utilizes light and lenses to magnify the
image of a sample, making it useful in corrosion studies [33]. It allows researchers to exam-
ine the surface of metal specimens before and after exposure to a corrosive environment,
providing information on the presence and location of corrosion products, thickness of
protective layers, and overall surface condition. This information is valuable in develop-
ing new corrosion protection strategies or improving existing ones. Additionally, optical
microscopy can be used to observe the real-time formation of corrosion, aiding in the
optimization of protective coatings and alloys [34]. However, while optical microscopy
can reveal information on the surface features of a material, it cannot provide information
about its electrochemical properties, such as its corrosion current and potential, which
are important parameters in describing the likelihood and the rate of corrosion [29]. To
determine these parameters, electrochemical measurements such as potentiodynamic or
EIS are necessary [31]. The combination of optical microscopy and electrochemical measure-
ments can provide a comprehensive understanding of the corrosion behavior of a material,
including identifying the locations of corrosion initiation and propagation [32]. Thus, while
optical microscopy is a powerful tool for investigating the microstructure of materials,
electrochemical measurements are necessary to accurately determine their electrochemical
properties [32]. This technique is based on the principle of electrochemistry, which is the
Lubricants 2023, 11, 174 11 of 29

study of the relationships between electrical and chemical processes. The basic equation
for the corrosion current, icorr , is given by the following expression:

icorr = (nFA)/(d × t)

where n is the number of electrons involved in the reaction, F is the Faraday constant
(96,485 C/mol), A is the surface area of the metal, d is the thickness of the metal, and t is
the time over which the metal is corroding. The units for icorr are typically in amperes (As).
The potential of a metal in the presence of an organic inhibitor can be calculated using
the Nernst equation:
E = Eo ln(icorr /io )
where Eo is the standard potential, R is the gas constant (8.31 J/mol K), T is the temper-
ature in Kelvin, io is the exchange current, and n is the number of electrons involved in
the reaction.
The corrosion rate can then be calculated using the following equation:

d(t) = do − (icorr × t × M )/(nFA)

where
d(t) is the remaining thickness of the metal after time t;
do is the initial thickness of the metal;
icorr is the corrosion current density (in A/cm2 );
t is the exposure time (in hours);
M is the atomic weight of the metal;
n is the number of electrons transferred in the corrosion reaction;
F is the Faraday constant (96,485 C/mol);
A is the surface area of the metal (in cm2 ).
In order to perform optical microscopy, a metal sample is coated with an organic
inhibitor and placed in a solution. The metal is then subjected to a current and the potential
of the metal is measured using an electrode. The corrosion rate can then be determined by
measuring the decrease in thickness of the metal over time. By combining these equations,
it is possible to accurately estimate the corrosion current and the potential of a metal in
the presence of an organic inhibitor using optical microscopy. This information is valuable
for understanding the protective properties of the organic inhibitor and for optimizing the
design of metal-based systems.

5.4. XPS
X-ray photoelectron spectroscopy (XPS) is a surface-sensitive analytical technique
that provides information on the elemental composition, oxidation state, and chemical
environment of the outermost surface layers of a material. In the context of corrosion
inhibition studies, XPS can be used to investigate the interaction between a protective
coating or inhibitor and the surface of a metal [35]. By analyzing the chemical composition
of the surface before and after exposure to the inhibitor, researchers can gain insights into
the mechanism of corrosion inhibition.
The principle of XPS involves exposing a material surface to X-rays and analyzing the
emitted electrons to determine their binding energy, which is related to the chemical identity
of the atoms from which they originated. By scanning the X-ray beam across the surface
of the material and measuring the binding energies of the emitted electrons at each point,
a two-dimensional image of the surface composition can be generated [33]. To perform a
corrosion inhibition study using XPS, the sample is first prepared by cleaning and polishing
the surface to remove any contaminants or oxide layers [36]. The sample is then exposed to
the inhibitor under controlled conditions, such as immersion in a corrosive solution, and
subsequently analyzed using XPS [37]. By comparing the XPS spectra of the inhibited and
uninhibited surfaces, researchers can identify any changes in the elemental composition,
Lubricants 2023, 11, 174 12 of 29

oxidation states, or chemical bonding that occur as a result of the inhibitor treatment [34].
XPS is a valuable technique for investigating the corrosion inhibition properties of materials.
It provides information on the surface chemistry of the material that is not accessible by
other analytical methods. By gaining a better understanding of the mechanism of corrosion
inhibition, researchers can develop more effective coatings and inhibitors to protect metal
surfaces from degradation [38].

5.5. Scanning Electron Microscopy (SEM)

SEM is an advanced imaging technique that produces high-resolution images of metal
surfaces and allows for detailed analysis of corrosion products, protective layers, and
underlying metal surfaces [39]. The technique involves emitting a beam of electrons onto
the sample, which interact with the surface and produce secondary electrons that are
collected to create a high-resolution image [40]. One of SEM’s advantages is its ability to be
used in different environments, such as high vacuum, low vacuum, and environmental
chambers, enabling the study of corrosion processes under various conditions [41]. SEM can
also be combined with other techniques, including energy-dispersive X-ray spectroscopy
(EDS), for the elemental analysis of corrosion products to determine the type of corrosion
and its cause. Overall, SEM is a crucial tool for corrosion study and the analysis of protection
methods, providing valuable information about the metal surface, corrosion products, and
protective layers to enhance protection strategies and extend metal structures’ lifespan.
In one study, a new organic corrosion inhibitor was synthesized, and SEM testing was
conducted to evaluate its effectiveness. The results showed that the mild steel surface
experienced significant corrosion due to H2 SO4 attack, resulting in a rough and unsmooth
surface, as shown in Figure 7. However, the mild steel surface was protected from corrosion
when the corrosion inhibitor was used, preventing severe corrosion from occurring due to
H2 SO4 , as shown in Figure 8 [42].
SEM is a powerful technique that can provide high-resolution imaging of the surface
of a metal sample, allowing for the characterization of its topography, morphology, and
composition. However, SEM is not typically used for the direct estimation of the corrosion
current and the potential of a metal in the presence of an organic inhibitor. Instead,
electrochemical techniques such as EIS or potentiodynamic polarization are typically used
to measure the corrosion current and potential. These techniques involve applying a small
AC or DC voltage to the metal sample and estimating the resulting current and potential
responses. The data obtained from these measurements can be used to characterize the
corrosion behavior of the metal in the presence or absence of an inhibitor and to evaluate
the effectiveness of the inhibitor in reducing corrosion [43–45]. The technique involves the
following steps:
1. Preparation of the sample: The metal sample is prepared for SEM by first cleaning it
and removing any surface contaminants. This is typically performed using a solvent
cleaning process or an etching process.
2. Deposition of the organic inhibitor: The organic inhibitor is then deposited onto
the metal surface. This can be performed using various methods, such as chemical
deposition, electrodeposition, or physical adsorption.
3. SEM imaging: The sample is then placed in the SEM and imaging is performed.
The SEM uses a high-energy electron beam to scan the sample and produce a high-
resolution image. This image can be used to determine the distribution of the organic
inhibitor on the metal surface.
4. Current-potential estimation: Current-potential estimations are performed by apply-
ing a potential difference between the metal sample and a reference electrode. This
creates an electric field, which causes the metal ions to migrate towards the reference
electrode. The rate of ion migration is proportional to the corrosion current, which is
calculated from equations rather than directly measured.
Lubricants 2023, 11, 174 13 of 29

5. Analysis of the data: The corrosion current density and potential are then calculated
from the current-potential estimation using appropriate equations. The corrosion
potential, Ecorr, can be determined from the Nernst equation:

Ecorr = Eo − ( RT/nF ) ln(i/icorr )

where Eo is the standard potential, R is the gas constant, T is the temperature, n is the
number of electrons transferred in the reaction, F is the Faraday constant, i is the estimated
current, and icorr is the corrosion current.
Note: The value of icorr , the corrosion current, is typically obtained through various
electrochemical techniques, such as Tafel extrapolation, linear polarization resistance,
or electrochemical impedance spectroscopy. These techniques involve applying a small
perturbation to the system and estimating the resulting current response to extract the value
of icorr . The choice of technique depends on the specific experimental setup and the desired
accuracy of the measurement. Once the value of icorr is determined, it can be used in the
Nernst equation along with other measured parameters to calculate the corrosion potential.
6. Interpretation of results: The corrosion current and potential can be used to evaluate
the efficacy of the organic inhibitor. A lower corrosion current and a more positive
corrosion potential indicate that the organic inhibitor is effectively reducing corrosion.
SEM is a useful tool for studying the surface morphology and elemental composition
of metal samples. However, it is not suitable for directly measuring corrosion current
or potential. To determine these electrochemical parameters, techniques such as poten-
tiodynamic or potentiostatic polarization measurements, EIS, or other electrochemical
methods are typically used [46]. Nevertheless, SEM can still play an important role in
understanding the corrosion behavior of a material. It provides information about the
morphology and topography of the corroded surface, as well as the types and distribution
of corrosion products that form during the corrosion process. This information can be used
in conjunction with electrochemical measurements to gain a more complete understanding
of the corrosion behavior of the material. For example, SEM can be used to examine the sur-
face of a corroded metal sample before and after electrochemical measurements are taken.
By comparing the images obtained before and after the electrochemical measurements,
researchers can gain insights into how the corrosion process has affected the surface of
the material and how the electrochemical parameters are related to the observed corrosion
behavior [47].
In summary, while SEM cannot directly measure corrosion current and potential, it
can provide valuable information about the morphology and topography of corroded
surfaces, as well as the types and the distribution of corrosion products. This information
can be used in combination with electrochemical measurements to gain a more complete
understanding of the corrosion behavior of a material [46,47].
Estimating the efficiency of organic corrosion inhibitors is critical to ensuring the
longevity and integrity of metal systems. Different techniques can be used to estimate
the effectiveness of these inhibitors, and it is important to select the appropriate methods
depending on the specific requirements of the system [48].
Lubricants 2023, 11, 174 14 of 29
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Figure 7. The SEM micrographs for mild steel in 1.0 M H2SO4 without the corrosion inhibitor at 30
Figure 7. The SEM micrographs for mild steel in 1.0 M H2 SO4 without the corrosion inhibitor at
°C: (a) 100×; (b) 500×; (c) 1000×; (d) 3000×; (e) 5000× [42].
30 ◦ C: (a) 100×; (b) 500×; (c) 1000×; (d) 3000×; (e) 5000× [42].
Lubricants 2023,11,
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Figure 8. The SEM micrographs for mild steel in 1.0 M H2SO4 with 0.25 mM of the corrosion inhibitor
Figure The100×;
8. (a)
at 30 °C: SEM(b)
micrographs for mild
500×; (c) 1000×; steel in(e)
(d) 3000×; 1.05000×
M H2[42].
SO4 with 0.25 mM of the corrosion inhibitor
at 30 ◦ C: (a) 100×; (b) 500×; (c) 1000×; (d) 3000×; (e) 5000× [42].
SEM isStudies
6. Previous a powerful technique
on Using that can
Natural andprovide high-resolution
Synthetic imaging of the surface
Organic Inhibitors
of a metal sample, allowing for the characterization of its topography, morphology, and
Organic inhibitors
composition. However, are
SEMcompounds thatused
is not typically are used to direct
for the control the corrosion
estimation of theofcorrosion
metals in
different industrial applications. These inhibitors can be of two types, namely natural
current and the potential of a metal in the presence of an organic inhibitor. Instead, elec- and
synthetic. Natural inhibitors are derived from plants and animals, while synthetic inhibitors
trochemical techniques such as EIS or potentiodynamic polarization are typically used to
are man-made chemicals. Both types of inhibitors have been extensively studied over the
Lubricants 2023, 11, 174 16 of 29

years, and their effectiveness at controlling corrosion has been documented in several
studies [49]. Studies on natural inhibitors have focused mainly on the use of extracts from
plants and animals to inhibit corrosion. For instance, extracts from different types of herbs
and spices, such as basil, clove, and cinnamon, have been shown to be effective at controlling
corrosion in a range of metals, including iron, aluminum, and copper. The mechanism
of action of natural inhibitors has been attributed to their ability to form protective films
on the metal surface, which prevent corrosion. In addition, natural inhibitors have been
found to contain antioxidants that can neutralize the harmful effects of corrosive agents on
metals [50]. Studies on synthetic inhibitors have focused on the design and synthesis of
new chemicals that are effective at controlling corrosion. Synthetic inhibitors have been
found to be more effective at controlling corrosion compared to natural inhibitors, mainly
due to their higher solubility in corrosive environments. However, synthetic inhibitors also
pose environmental and health risks, which have led to concerns over their widespread
use [51]. Herein are some examples of previous studies on using natural and synthetic
organic inhibitors.
1. Natural organic inhibitors:
a. Using chitosan as a natural inhibitor in the inhibition of the corrosion of mild
steel in seawater [52].
b. The use of cinnamon extract as an inhibitor for the corrosion of aluminum in
acidic media [53].
c. The application of tannic acid as a natural inhibitor for the corrosion of carbon
steel in an aqueous solution [54].
Natural corrosion inhibitors have gained significant attention in recent years due to
their eco-friendly, cost-effective, and sustainable nature. They are derived from various
natural sources such as plants, animals, and microorganisms, and have been found to
exhibit excellent corrosion inhibition properties in different environments.
Several studies have been conducted to investigate the effectiveness of natural corro-
sion inhibitors in different industries. For instance, Adewuyi and others [55] evaluated the
corrosion inhibition efficiency of crude extracts of Vernonia amygdalina and Mangifera
indica leaves in hydrochloric acid (HCl) using weight loss and electrochemical techniques.
They found that both plant extracts were effective at inhibiting corrosion, and their in-
hibition efficiency increased with increasing concentration. Similarly, Mohd Sani and
others [56] investigated the effectiveness of Piper nigrum extract as a natural corrosion
inhibitor in a 3.5% NaCl solution using electrochemical impedance spectroscopy and po-
tentiodynamic polarization techniques. They found that the extract exhibited significant
inhibition efficiency and was more effective than some of the commercial inhibitors used for
the same purpose. In another study, Bhat and Nayak [57] evaluated the corrosion inhibition
efficiency of a polysaccharide extracted from the marine algae Padina tetrastromatica in
a 3.5% NaCl solution using weight loss and electrochemical techniques. They found that
the polysaccharide exhibited excellent corrosion inhibition properties, and its effectiveness
increased with increasing concentration. Furthermore, some studies have investigated the
synergistic effects of natural corrosion inhibitors and other additives. For example, Ebenso
and others [58] evaluated the effectiveness of Azadirachta indica and Moringa oleifera
extracts in combination with sodium molybdate as a corrosion inhibitor for mild steel in
hydrochloric acid. They found that the combination of the extracts and sodium molybdate
exhibited better inhibition efficiency than the individual inhibitors.
2. Synthetic organic inhibitors:
a. The effectiveness of benzotriazole as a corrosion inhibitor for aluminum alloys
in acidic media [59].
b. The use of triazole derivatives as corrosion inhibitors for mild steel in acidic
environments [60].
c. The inhibition performance of imidazoline derivatives in the corrosion of
copper in aerated seawater [61].
Lubricants 2023, 11, 174 17 of 29

In conclusion, the studies on using natural and synthetic organic inhibitors have
provided valuable insights into the mechanisms of corrosion and the efficacy of inhibitors
in controlling it. While natural inhibitors have been found to be less effective compared
to synthetic inhibitors, they are considered to be safer and more environmentally friendly.
Further research is needed to improve the efficiency of natural inhibitors and to reduce the
negative impacts of synthetic inhibitors.
One study compared the corrosion inhibition efficiency of a synthetic inhibitor,
2-mercaptobenzothiazole (MBT), with that of a natural inhibitor, catechin, on mild steel
in an acid solution. The results showed that both inhibitors were effective, but catechin
was more effective at lower concentrations. The researchers suggested that catechin’s
superior performance may be due to its higher molecular weight and ability to form a
protective film on the metal surface [62]. Another study compared the performance of
several synthetic inhibitors, including benzotriazole (BTA), tolyltriazole (TTA), and mer-
captobenzothiazole (MBT), with that of a natural inhibitor, tannic acid, on carbon steel
in an acidic media. The results showed that tannic acid was the most effective inhibitor,
followed by TTA and BTA, with MBT being the least effective [63]. A third study compared
the corrosion inhibition performance of a synthetic inhibitor, 2-mercaptobenzimidazole
(MBI), with that of a natural inhibitor, vanillin, on mild steel in acidic media. The results
showed that vanillin was a more effective inhibitor than MBI, possibly due to its ability to
form a thicker protective film on the metal surface [64]. One study by Li and [65] compared
the inhibitory effect of three natural inhibitors (extracts of tea, black pepper, and cinnamon)
and three synthetic inhibitors (benzotriazole, imidazole, and mercaptobenzimidazole) on
the corrosion of carbon steel in acidic solutions. The results showed that all six inhibitors
were effective at reducing corrosion, with the natural inhibitors performing slightly better
than the synthetic ones. The authors suggested that this may be due to the presence of
multiple active components in natural inhibitors, which can provide a synergistic effect.
Another study by El-Etre and others [66] investigated the inhibitory effect of a natural
inhibitor (pomegranate peel extract) and a synthetic inhibitor (sodium benzoate) on the
corrosion of mild steel in a 1 M HCl solution. The results showed that both inhibitors
were effective at reducing corrosion, but the natural inhibitor was more effective, with a
corrosion inhibition efficiency of 91.6% compared to 87.1% for the synthetic inhibitor. The
authors suggested that this may be due to the presence of tannins and phenolic compounds
in the natural inhibitor, which can form a protective film on the metal surface. In contrast, a
study by Mekidiche and others [67] compared the inhibitory effect of a synthetic inhibitor
(4-methoxybenzylidene-4-butanoylthiosemicarbazide) and a natural inhibitor (rosemary
essential oil) on the corrosion of mild steel in a 1 M HCl solution. The results showed
that the synthetic inhibitor was more effective, with a corrosion inhibition efficiency of
98.8% compared to 84.9% for the natural inhibitor. The authors suggested that this may
be due to the higher concentration of active components in the synthetic inhibitor [62–74].
Overall, these studies suggest that natural inhibitors can be as effective or more effective
than synthetic inhibitors in preventing metal corrosion. However, the performance of
inhibitors can vary depending on the specific metal and environment being studied, and
further research is needed to fully understand the mechanisms of corrosion inhibition.

7. Adsorption Isotherms of Organic Corrosion Inhibitors

Adsorption isotherms refer to the relationship between the amount of a substance
adsorbed onto a surface and the concentration of that substance in the surrounding en-
vironment. In the context of organic corrosion inhibitors, adsorption isotherms provide
important information about the effectiveness of these inhibitors in preventing corro-
sion [75]. There are several commonly used models for describing the adsorption isotherms
of organic corrosion inhibitors, including the Langmuir, Freundlich, and Temkin isotherms.
The Langmuir isotherm assumes that the adsorption of the inhibitor occurs on a surface
with a fixed number of adsorption sites and that the adsorption process is monolayer.
Lubricants 2023, 11, 174 18 of 29

Langmuir isotherm: The Langmuir isotherm equation is given by:

Q = (KL × C )/(1 + KL × C )

where Q = the adsorption capacity (mg/g); C = the concentration of the inhibitor in the
solution (mg/mg); KL = the Langmuir constant (mg/mg).
Freundlich isotherm: The Freundlich isotherm assumes that the adsorption is depen-
dent on both the concentration of the inhibitor and the surface area.
Freundlich isotherm: The Freundlich isotherm equation is given by:

1
lnQ = lnK f + ( ) × lnC
n
where Q = the adsorption capacity (mg/g); C = the concentration of the inhibitor in the solution
(mg/L); K f = the Freundlich constant (mg/g (L/mg)ˆ(1/n)); n = the Freundlich exponent.
The Temkin isotherm considers the adsorption process to be influenced by the heat of
adsorption and the entropy of the adsorbent-adsorbate system [76].
Temkin Isotherm: The Temkin isotherm equation is given by:

Q = b ln C + AlnC (1)

where Q = the adsorption capacity (mg/g); C = the concentration of the inhibitor in the
solution (mg/L); A = the Temkin constant (L/mg); b = the Temkin constant (mg/g).
The shape of the adsorption isotherm can offer valuable insights into the mechanism
of inhibitor adsorption and can help evaluate the performance of various inhibitors. For
instance, a Langmuir isotherm suggests that the inhibitor adheres to the metal surface in
a monolayer and is expected to be highly effective at preventing corrosion. On the other
hand, a Freundlich isotherm indicates that the adsorption of the inhibitor depends on
both the concentration of the inhibitor and the surface area, which can result in reduced
efficacy at higher inhibitor concentrations [42]. Al-Amiery [42] provides an example of the
adsorption isotherm study, which explores the interactions between inhibitor molecules
and metal surfaces.
The surface coverage (θ) was calculated at various inhibitor concentrations in 1 M
hydrochloric acid solution. The most commonly used isotherms are the Temkin and
Langmuir models. An analysis of weight loss measurement data showed that the data best
fit the Langmuir model. The linear regression parameter (R2) between Cinh/θ and Cinh
was 0.9995, as shown in Figure 9, which confirms that the adsorption of 4-benzyl-1-(4-oxo-
4-phenylbutanoyl)thiosemicarbazide molecules on mild steel follows Langmuir isotherms.
However, the slope of the Cinh/θ against the Cinh plot was different from unity, indicating
non-ideal simulation and unexpected behavior from Langmuir isotherms. This may be due
to interactions between adsorbed 4-benzyl-1-(4-oxo-4-phenylbutanoyl)thiosemicarbazide
molecules on the tested metal surface. A ∆Goads value of −37.1 kJ mol−1 was determined,
indicating a combination of chemical and electrostatic interactions between the inhibitor
and mild steel in 1 M HCl solution at 303 K. A negative ∆Goads value confirms that the
adsorption of 4-benzyl-1-(4-oxo-4-phenylbutanoyl)thiosemicarbazide molecules on mild
steel is a spontaneous process.
An article published by Walczak M.S. et al, and his colleagues evaluates the practice
of using inhibition efficiency to determine the standard Gibbs energy of adsorption for
a corrosion inhibitor in acidic solutions. It suggests that the assumption that inhibition
efficiency is a good proxy for fractional surface coverage may not always be valid, and,
therefore, the accuracy of the Gibbs energy of adsorption value obtained from such data
is doubtful. The article argues that even a more direct measurement of fractional surface
coverage may still not allow for an accurate estimate of the Gibbs energy of adsorption [77].
 ing non-ideal simulation and unexpected behavior from Langmuir isotherms. This may
be due to interactions between adsorbed 4-benzyl-1-(4-oxo-4-phenylbutanoyl)thiosemi-
carbazide molecules on the tested metal surface. A ΔGoads value of −37.1 kJ mol−1 was
determined, indicating a combination of chemical and electrostatic interactions between
the inhibitor and mild steel in 1 M HCl solution at 303 K. A negative ΔGoads value con-
Lubricants 2023, 11, 174 19 of 29
firms that the adsorption of 4-benzyl-1-(4-oxo-4-phenylbutanoyl)thiosemicarbazide mol-
ecules on mild steel is a spontaneous process.

Langmuir
Figure 9.9. Langmuir adsorption
adsorption isotherm
isotherm modelmodel foradsorption
for the the adsorption of 4-benzyl-1-(4-oxo-4-
of 4-benzyl-1-(4-oxo-4-phenyl-
phenylbutanoyl)thiosemicarbazide
butanoyl)thiosemicarbazide in 1 M in 1M
HCl onHCl on the surface
the surface of mildofsteel
mild steel [42].
[42].

In conclusion,
An adsorption
article published isotherms
by Walczak [Link]
al, andcorrosion inhibitors
his colleagues provide
evaluates thevaluable
practice
information about the effectiveness of these inhibitors in preventing
of using inhibition efficiency to determine the standard Gibbs energy of adsorption corrosion. Under-
for a
standing the adsorption behavior of these inhibitors can help in the design
corrosion inhibitor in acidic solutions. It suggests that the assumption that inhibition effi- and selection of
effective corrosion inhibitors for different applications.
ciency is a good proxy for fractional surface coverage may not always be valid, and, there-
fore, the accuracy of the Gibbs energy of adsorption value obtained from such data is
8. Mechanisms of Organic Corrosion Inhibitors
doubtful. The article argues that even a more direct measurement of fractional surface
Organic
coverage maycorrosion inhibitors
still not allow for an are chemical
accurate compounds
estimate that energy
of the Gibbs help prevent the corrosion
of adsorption [77].
of metals in harsh environmental conditions. There are several mechanisms through which
In conclusion, adsorption isotherms of organic corrosion inhibitors provide valuable
organic corrosion inhibitors work [78]:
information about the effectiveness of these inhibitors in preventing corrosion. Under-
1. Adsorption:
standing Adsorption
the adsorption is theofmost
behavior thesefrequently
inhibitorsobserved
can helpmechanism
in the design of organic corro-
and selection
sion inhibitors.
of effective corrosionThese inhibitors
inhibitors attach themselves
for different to the surface of the metal, creating
applications.
a protective layer that serves as a barrier between the metal and the corrosive environ-
ment. Several
8. Mechanisms factors, Corrosion
of Organic including the concentration of the inhibitor, the surface area,
Inhibitors1
and the presence of other species in the solution, can affect this process [79,80].
Organic corrosion inhibitors are chemical compounds that help prevent the corrosion
2. Film formation: Organic corrosion inhibitors can also form a film on the metal surface,
of metals in harsh environmental conditions. There are several mechanisms through
which protects it from corrosion. This film acts as a barrier, preventing the corrosive
which organic corrosion inhibitors work [78]:
agents from reaching the metal surface.
1.
3. Adsorption:
ElectrostaticAdsorption is the most
repulsion: Organic frequently
corrosion observed
inhibitors canmechanism of organic
use electrostatic cor-
repulsion
rosion inhibitors. These inhibitors attach themselves to the surface
to prevent corrosion. These inhibitors can be charged, which allows them to repel of the metal, cre-
ating a protective layer that serves as a barrier between the metal
corrosive agents. For example, inhibitors with a positive charge can repel negativelyand the corrosive
environment.
charged corrosiveSeveral factors,
ions, whileincluding
inhibitorsthe concentration
with of the inhibitor,
a negative charge can repelthe surface
positively
area, andions
charged the presence
[81,82]. of other species in the solution, can affect this process [79,80].
4. Complex formation: Organic corrosion inhibitors can form complex compounds with
the corrosive agents, thereby reducing their effectiveness. This results in a reduction
in the corrosion rate as the corrosive agents are neutralized.
5. pH adjustment: Organic corrosion inhibitors can also adjust the pH of the solution to
a neutral or slightly alkaline level. This helps to reduce the concentration of corrosive
agents in the solution, which in turn reduces the rate of corrosion.
6. Cathodic protection: Organic corrosion inhibitors can act as cathodic inhibitors by
reducing the cathodic reaction rate, thus reducing the rate of corrosion.
7. Oxygen scavenging: Organic corrosion inhibitors are compounds that can reduce
the rate of corrosion by scavenging oxygen from the solution. By removing oxygen,
the formation of corrosive agents that would otherwise cause corrosion is prevented.
 a neutral or slightly alkaline level. This helps to reduce the concentration of corrosive
agents in the solution, which in turn reduces the rate of corrosion.
6. Cathodic protection: Organic corrosion inhibitors can act as cathodic inhibitors by
reducing the cathodic reaction rate, thus reducing the rate of corrosion.
7. Oxygen scavenging: Organic corrosion inhibitors are compounds that can reduce the
Lubricants 2023, 11, 174 20 of 29
rate of corrosion by scavenging oxygen from the solution. By removing oxygen, the
formation of corrosive agents that would otherwise cause corrosion is prevented.
These inhibitors function by creating a protective barrier on the metal surface, which
These inhibitors
prevents function
the corrosive by creating
agents a protective
from coming barrierwith
into contact on the
the metal
metalsurface,
[83,84]. which
prevents the corrosive agents from coming into contact with the metal [83,84].
The chemical adsorption of 3-(4-ethyl-5-mercapto-1, 2, 4-triazol-3-yl)-1-phenylpro-
panone Themolecules
chemical adsorption
on mild steelof 3-(4-ethyl-5-mercapto-1, 2, 4-triazol-3-yl)-1-phenylpropanone
is indicated by the interaction of the donor/acceptor from
the unreacted electrons of nitrogen, sulfur, and oxygenthe
molecules on mild steel is indicated by the interaction of donor/acceptor
atoms from with
of the molecule the unre-
the
acted electrons of nitrogen, sulfur, and oxygen atoms of the molecule with𝑜 the unoccupied
unoccupied d-orbitals of the iron atoms on the mild steel surface.o The ∆𝐺𝑎𝑑𝑠 for the tested
d-orbitals of the iron atoms on the mild steel surface. The ∆G for the tested inhibitor
inhibitor was found to be -35.73 kJ/mol, indicating that both theads physisorption and chem-
was found to be -35.73 kJ/mol, indicating that both the physisorption and chemisorption
isorption mechanisms are involved in the adsorption process. The anticorrosion mecha-
mechanisms are involved in the adsorption process. The anticorrosion mechanism of mild
nism of mild steel in a corrosive environment can be explained based on the adsorption
steel in a corrosive environment can be explained based on the adsorption of the 3-(4-ethyl-
of the 3-(4-ethyl-5-mercapto-1, 2, 4-triazol-3-yl)-1-phenylpropanone molecules on the steel
5-mercapto-1, 2, 4-triazol-3-yl)-1-phenylpropanone molecules on the steel surface. These
surface. These molecules act by adsorbing onto the steel surface and preventing the active
molecules act by adsorbing onto the steel surface and preventing the active positions by
positions by displacing water molecules and creating a barrier to block the corrosion pro-
displacing water molecules and creating a barrier to block the corrosion process. Figure 10
cess. Figure 10 represents the proposed inhibition mechanism of the molecule on the mild
represents the proposed inhibition mechanism of the molecule on the mild steel surface in
steel surface in a 1 M HCl solution [85].
a 1 M HCl solution [85].

Figure
Figure 10.
10. The
The suggested
suggested inhibition
inhibitionmechanism
mechanismof
oftested
testedinhibitor
inhibitoron
onthe
themild
mildsteel
steelsurface
surfacein
in11 M
M
HCl solution [85].
HCl solution [85].

9. Computational
9. Computational Methods
Methods
Computational methods have
Computational have become
becomeincreasingly
increasinglyimportant
importantforfor
corrosion
corrosioninhibition
inhibi-
studies in recent years. Here are some applications of computational methods for
tion studies in recent years. Here are some applications of computational methods for corrosion
inhibitioninhibition
corrosion studies [86–90]:
studies [86–90]:
1. Molecular dynamics (MDs) simulations: MD simulations can provide insights into
the interaction between inhibitors and metal surfaces at the atomic scale. These
simulations can be used to study the adsorption behavior of inhibitors, the effect of
the molecular structure on inhibitor performance, and the effect of environmental
factors such as pH and temperature on inhibitor efficacy [86].
2. Density functional theory (DFT): DFT calculations can be used to study the electronic
properties of inhibitors and their interaction with metal surfaces. This approach can be
used to predict the adsorption energy of inhibitors and to identify the most effective
inhibitors for a particular metal surface [76].
3. Monte Carlo simulations: Monte Carlo simulations can be used to predict the cov-
erage and distribution of inhibitors on metal surfaces. This approach can provide
insights into the mechanism of inhibitor action and can be used to optimize inhibitor
concentrations and application methods [87].
4. Machine learning: Machine learning algorithms can be trained on large datasets of
corrosion inhibition data to predict the performance of new inhibitors. This approach
can accelerate the discovery of new inhibitors and reduce the cost and time required
for experimental screening [35,88].
Overall, computational methods have become an essential tool for corrosion inhibition
studies, allowing researchers to gain insights into the mechanism of inhibitor action and to
optimize the design and application of corrosion inhibitors.
 corrosion inhibition data to predict the performance of new inhibitors. This approach
can accelerate the discovery of new inhibitors and reduce the cost and time required
for experimental screening [35,88].
Overall, computational methods have become an essential tool for corrosion inhibi-
tion studies, allowing researchers to gain insights into the mechanism of inhibitor action
Lubricants 2023, 11, 174 21 of 29
and to optimize the design and application of corrosion inhibitors.

10. Comparison Studies

10. Comparison
In this study,Studies
we compared the inhibitory efficiencies of several published synthe-
sizedInorganic corrosion
this study, inhibitors
we compared the[89–121].
inhibitoryToefficiencies
do this, we evaluated
of several the inhibition
published effi-
synthesized
organic corrosion
ciencies inhibitors [89–121].
of these synthesized Toand
inhibitors do this, we evaluated
summarized the inhibition
our findings efficiencies
in Figure 11. of
these synthesized inhibitors and summarized our findings in Figure 11.

Figure
Figure 11.
11. Comparison
Comparison between
between several
several synthesized
synthesized organic corrosion inhibitors.

Figure 11 summarizes the comparison of inhibition efficiencies of several synthesized

organic corrosion inhibitors. The graph shows the inhibitors’ inhibition efficiencies as
percentages, with higher percentages indicating more effective inhibition. The inhibitors
are labeled on the x-axis, and the y-axis represents the inhibition efficiency percentage.
The comparison shows which synthesized organic corrosion inhibitor is the most
effective at inhibiting corrosion. This information can be useful for selecting the best
inhibitor for a specific application, such as in the petroleum, chemical, or manufacturing
industries. Additionally, the study may provide insight into the mechanisms of corrosion
inhibition and inform future research and development of corrosion inhibitors. Organic
inhibitors are chemical compounds that can be used to prevent or reduce the corrosion
of metals. There are two main types of organic inhibitors: natural inhibitors, which are
derived from plant extracts or animal products; and synthetic inhibitors, which are man-
made. Several studies have been conducted to investigate the effectiveness of natural and
synthetic organic inhibitors in corrosion prevention. Here, we review some of these studies
and compare the performances of natural and synthetic inhibitors [112–126].
Natural corrosion inhibitors can be obtained from various sources, including plant
extracts, animal extracts, and minerals. Plant extracts contain various organic compounds,
such as tannins, alkaloids, and flavonoids, that have been found to inhibit corrosion.
Animal extracts, such as chitosan and collagen, have also been studied as natural corrosion
inhibitors. Minerals, such as molybdate, chromate, and nitrate, are commonly used as
corrosion inhibitors in the industry. These minerals can be obtained naturally from rocks
and soil [127,128].
The effectiveness of natural corrosion inhibitors depends on various factors, such
as the type and concentration of the inhibitor, the nature of the metal surface, and the
Lubricants 2023, 11, 174 22 of 29

environmental conditions. Additionally, the mechanism of inhibition can differ between

natural inhibitors, as some may form a protective film on the metal surface, while others
may interact with the electrolyte solution to reduce the corrosion rate [129,130]. Natural
corrosion inhibitors are compounds that occur naturally in nature and can be used to
protect metal surfaces from corrosion. They are an eco-friendly alternative to synthetic
inhibitors and can be obtained from a wide range of sources, including plants, animals, and
minerals. Herein, we explore the differences between natural corrosion inhibitors. Table 1
represents the differences between natural inhibitors based on the source of the inhibitor
and the mechanism of inhibition, in addition to its applications.

Table 1. Represents the differences between natural corrosion inhibitors.

Natural Mechanisms of
Source Applications Advantages Disadvantages Ref.
Inhibitors Inhibition
Formation of a
Limited effectiveness,
protective layer on the Inhibiting
Tannins, Renewable, degradation over
metal surface, corrosion of
Plants flavonoids, biodegradable, time, sensitivity to [127–129]
adsorption of the metals in aqueous
alkaloids low toxicity environmental
inhibitor molecules on solutions
conditions
the metal surface
Formation of a barrier Protection of Limited stability,
Low cost,
Lignin, chitosan, film, adsorption of the metals against sensitivity to
Fungi biodegradable, [130–132]
polysaccharides inhibitor molecules on corrosion in environmental
high efficiency
the metal surface aqueous solutions conditions
Formation of a
protective layer on the
Inhibiting Renewable, Limited stability,
metal surface,
Bacteria, yeasts, corrosion of biodegradable, sensitivity to
Microorganisms production of organic [133]
actinomycetes metals in aqueous effective at low environmental
acids, adsorption of the
solutions concentrations conditions
inhibitor molecules on
the metal surface
Formation of a barrier Protection of Limited effectiveness,
Castor oil, Low cost, readily
film, adsorption of the metals against sensitivity to
Natural oils soybean oil, available, [134]
inhibitor molecules on corrosion in environmental
coconut oil biodegradable
the metal surface aqueous solutions conditions
Formation of a barrier Protection of Limited stability,
Xanthan gum, Biodegradable,
film, adsorption of the metals against sensitivity to
Polysaccharides carrageenan, renewable, [135]
inhibitor molecules on corrosion in environmental
starch cost-effective
the metal surface aqueous solutions conditions
Performance may
Abundant,
vary depending on
Plant extracts - Adsorption Metal protection eco-friendly, low [136–138]
the plant species and
cost
extraction method
Good
Film formation, Oil and gas antimicrobial and
Strong odors may
Essential oils - adsorption, industries, metal antifungal [139,140]
limit their use
complexation surface protection properties,
biodegradable
Non-toxic, Limited effectiveness
Adsorption, Metal surface
Amino acids - biodegradable, at high temperatures [141]
complexation protection
low cost and low pH
Metal surface
Eco-friendly, Can be
Adsorption, film protection,
Polysaccharides - non-toxic, and time-consuming to [142]
formation concrete
biodegradable prepare and to apply
reinforcement
Can be expensive and
Adsorption, Metal surface Biodegradable,
Proteins - may cause fouling in [143]
complexation protection non-toxic
certain systems
Limited effectiveness
Adsorption, Metal surface High selectivity, at high temperatures
Enzymes - [144]
complexation protection biodegradable and low pH, can be
expensive
Lubricants 2023, 11, 174 23 of 29

11. Future Outlooks

The use of corrosion inhibitors is an essential strategy for protecting metals and
alloys from degradation in various industries. Organic inhibitors have been widely used
due to their effectiveness, availability, and economic viability. The review paper entitled
“Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors” provides a comprehensive
overview of both natural and synthetic organic inhibitors, their mechanisms of action, and
recent advances in their development [145–149].
The future outlook for this topic is promising, and several areas of research are
expected to contribute to the development of more effective and environmentally friendly
corrosion inhibitors. Here are some potential future outlooks:
1. Green corrosion inhibitors: With increasing concern about the environmental impact of
chemical inhibitors, there is a growing interest in the development of green corrosion
inhibitors. These inhibitors are derived from renewable resources, are biodegradable,
and are less toxic to the environment. Researchers are exploring natural sources such
as plant extracts, essential oils, and biopolymers as potential green inhibitors.
2. Nanotechnology: Nanotechnology has shown promising results in the development
of corrosion inhibitors due to its ability to enhance the protective properties of coatings
and films. Researchers are exploring the use of nanoparticles as corrosion inhibitors
or as carriers of inhibitors to enhance their efficiency.
3. Computational studies: Computational studies have become an essential tool in the
design and development of new inhibitors. With advances in computing power
and molecular simulation techniques, researchers can better understand the inter-
actions between inhibitors and metal surfaces and optimize inhibitor structures for
maximum effectiveness.
4. Synergistic effects: Combining different inhibitors to create synergistic effects is a
promising area of research. Researchers are exploring the use of natural and synthetic
inhibitors together, as well as the combination of inhibitors with other corrosion
protection strategies such as coatings and cathodic protection.
5. Application-specific inhibitors: Different industries and applications have specific
requirements for corrosion inhibitors. In the future, more research is expected to
focus on developing inhibitors tailored to specific industries, such as oil and gas,
automotive, or aerospace, to optimize performance and cost-effectiveness.
In conclusion, the development of corrosion inhibitors is an active area of research,
and the future outlook is promising. Researchers are exploring new materials, technologies,
and methods to develop more effective, environmentally friendly, and application-specific
inhibitors. The review paper provides a valuable resource for researchers and engineers
working in this field.

12. Conclusions
Corrosion is a complex process that can occur in various forms and have different
causes. The use of organic corrosion inhibitors has been widely studied and recognized as
an effective solution for preventing metal corrosion. In this review article, various types
of corrosion and classifications of organic corrosion inhibitors were discussed. The active
functional groups in organic inhibitors were also discussed and their role in the inhibition
of corrosion was emphasized. Estimating the efficiency of organic inhibitors is an important
aspect in the selection and application of corrosion inhibitors. Several methods have been
used for this purpose, including electrochemical techniques and surface analysis methods.
Previous studies have shown that natural and synthetic organic inhibitors can be used
effectively to prevent corrosion. However, the efficiency of these inhibitors depends on
the type of metal, the environment, and the type of inhibitor used. Adsorption isotherms
of organic inhibitors have also been studied, and they provide important information on
the interaction between the inhibitor and the metal surface. The mechanisms of organic
corrosion inhibitors were also discussed, and it was found that the inhibition of corrosion
is related to the adsorption of the inhibitor on the metal surface. Finally, the kinetics of
Lubricants 2023, 11, 174 24 of 29

corrosion modeling was discussed, and it was found that this method provides important
information on the kinetics of corrosion processes and the inhibition of corrosion by organic
inhibitors. In conclusion, organic corrosion inhibitors play a crucial role in preventing
metal corrosion. Further research is needed to better understand the mechanisms of organic
inhibitors and to improve their efficiency. The development of new and improved organic
inhibitors will help to reduce the impact of corrosion on metal surfaces and increase the
lifespan of metal structures.

Author Contributions: Conceptualization, W.N.R.W.I.; formal analysis, W.K.A.-A.; investigation,

A.A.A.-A.; resources, W.N.R.W.I.; data curation, W.N.R.W.I.; writing—original draft preparation,
A.A.A.-A.; writing—review and editing, A.A.A.-A.; visualization, W.K.A.-A.; supervision, W.N.R.W.I.;
project administration A.A.A.-A.; funding acquisition, W.N.R.W.I. All authors have read and agreed
to the published version of the manuscript.
Funding: Universiti Kebangsaan Malaysia provided funding for a portion of the study under the
following code: GUP-2020-012.
Data Availability Statement: Not applicable.
Acknowledgments: The support provided by the Universiti Kebangsaan Malaysia (UKM) is ac-
knowledged by the authors. We would like to acknowledge also the joint UKM-UMT-RSU-AISSMS
(1+3) research collaboration in the field of corrosion.
Conflicts of Interest: The authors claim they have no competing interests.

References
1. Rani, B.E.; Bharathi Bai, J.B. Green Inhibitors for Corrosion Protection of Metals and Alloys: An Overview. Int. J. Corros. 2012,
2012, 380217. [CrossRef]
2. Ahmed, E.S.; Junaid; Ganesh, G.M. A Comprehensive Overview on Corrosion in RCC and Its Prevention Using Various Green
Corrosion Inhibitors. Buildings 2022, 12, 1682. [CrossRef]
3. Tamalmani, K.; Husin, H. Review on Corrosion Inhibitors for Oil and Gas Corrosion Issues. Appl. Sci. 2020, 10, 3389. [CrossRef]
4. Zakeri, A.; Bahmani, E.; Sabour Rouh Aghdam, A. Plant Extracts as Sustainable and Green Corrosion Inhibitors for Protection of
Ferrous Metals in Corrosive Media: A Mini Review. Corros. Commun. 2022, 1, 6–17. [CrossRef]
5. Chauhan, D.S.; Quraishi, M.A.; Sorour, A.A.; Verma, C. A Review on Corrosion Inhibitors for High-Pressure Supercritical CO2
Environment: Challenges and Opportunities. J. Pet. Sci. Eng. 2022, 215, 110695. [CrossRef]
6. Werle, M. Natural and Synthetic Polymers as Inhibitors of Drug Efflux Pumps. Pharm. Res. 2008, 25, 500–511. [CrossRef]
7. Finšgar, M.; Jackson, J. Application of Corrosion Inhibitors for Steels in Acidic Media for the Oil and Gas Industry: A Review.
Corros. Sci. 2014, 86, 17–41. [CrossRef]
8. Raja, P.B.; Ismail, M.; Ghoreishiamiri, S.; Mirza, J.; Ismail, M.C.; Kakooei, S.; Rahim, A.A. Reviews on Corrosion Inhibitors: A
Short View. Chem. Eng. Commun. 2016, 203, 11451156. [CrossRef]
9. Olajire, A.A. Recent Advances on the Treatment Technology of Oil and Gas Produced Water for Sustainable Energy Industry-
Mechanistic Aspects and Process Chemistry Perspectives. Chem. Eng. J. Adv. 2020, 4, 100049. [CrossRef]
10. Li, L.; William, H.; Gibson Grant, T.; Wolfson Steve, L. Laboratory Investigation of Corrosion and Corrosion Protection of a
Candidate Umbilical Material for Subsea Production Service. In CORROSION 2002; OnePetro: Denver, CO, USA, 2002.
11. Verma, C.; Ebenso Eno, E.; Quraishi, M.A. Ionic Liquids as Green and Sustainable Corrosion Inhibitors for Metals and Alloys: An
Overview. J. Mol. Liq. 2017, 233, 403–414. [CrossRef]
12. Al-Amiery, A.A.; Al-Azzawi, W.K.; Isahak, W.N.R.W. Isatin Schiff base as an effective corrosion inhibitor for mild steel in
hydrochloric acid solution: Gravimetric, electrochemical, and computational investigation. Sci. Rep. 2022, 12, 17773. [CrossRef]
13. Talat, R.; Asghar, M.A.; Tariq, I.; Akhter, Z.; Liaqat, F.; Nadeem, L.; Haider, A.; Ali, S. Evaluating the Corrosion Inhibition Efficiency of
Pyridinium-Based Cationic Surfactants for EN3B Mild Steel in Acidic-Chloride Media. Coatings 2022, 12, 1701. [CrossRef]
14. Xu, T.; Yang, Y.; Peng, X.; Song, J.; Pan, F. Overview of Advancement and Development Trend on Magnesium Alloy. J. Magnes.
Alloys 2019, 7, 536–544. [CrossRef]
15. Hosseini, M.; Fotouhi, L.; Ehsani, A.; Naseri, M. Enhancement of Corrosion Resistance of Polypyrrole Using Metal Oxide
Nanoparticles: Potentiodynamic and Electrochemical Impedance Spectroscopy Study. J. Colloid Interface Sci. 2017, 505, 213–219.
[CrossRef] [PubMed]
16. Mahdi, B.S.; Abbass, M.K.; Mohsin, M.K.; Al-Azzawi, W.K.; Hanoon, M.M.; Al-Kaabi, M.H.H.; Shaker, L.M.; Ismael, M.A.;
Al-Rubaie, A.A.A.; Kadhum, A.A.H.; et al. Corrosion Inhibition of Mild Steel in Hydrochloric Acid Environment Using
Terephthaldehyde Based on Schiff Base: Gravimetric, Thermodynamic, and Computational Studies. Molecules 2022, 27, 4857.
[CrossRef] [PubMed]
Lubricants 2023, 11, 174 25 of 29

17. Hernandez, H.; Herrera, A.M.; Ruiz Reynoso, A.; Trinidad González, J.C.; González Morán, C.O.; Miranda Hernández, J.G.;
Mandujano Ruiz, A.; Morales Hernández, J.; Orozco Cruz, R. Electrochemical Impedance Spectroscopy (EIS): A Review Study of
Basic Aspects of the Corrosion Mechanism Applied to Steels. Electrochem. Impedance Spectrosc. 2020, 24, 137–144.
18. Li, B.; Li, Y. Monte Carlo Simulation of Corrosion Inhibitor Adsorption on the Iron Surface. Langmuir 2006, 22, 3385–3392. [CrossRef]
19. Liu, J.; Shao, W.; Gao, J.; Wang, J.; Gao, X. Machine Learning Models for Predicting the Inhibition Performance of Imidazoline
Derivatives in CO2 Corrosion. Corros. Sci. 2019, 153, 181–190. [CrossRef]
20. Ashworth, V. Corrosion Inhibitors. In Corrosion Inhibitors: Principles and Recent Applications; Springer International Publishing:
Cham, Switzerland, 2017; pp. 1–28. [CrossRef]
21. Bardal, E.; Krotz, G. Corrosion Inhibitors. In Corrosion and Protection; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany,
2018; pp. 317–357. [CrossRef]
22. Cook, R.B. Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering; Springer Science & Business Media:
New York, NY, USA, 2013.
23. Hernandez, H.; Ruiz Reynoso, A.; Trinidad, J.C.; González, C.O.; Miranda, J.G.; Mandujano, A.M.R. Electrochemical Impedance
Spectroscopy (EIS): A Review Study of Basic Aspects of the Corrosion Mechanism Applied to Steels; IntechOpen: London, UK, 2019.
24. Jawad, Q.; Zinad, D.S.; Salim, R.D.; Al-Amiery, A.A.; Gaaz, T.S.; Takriff, M.S.; Kadhum, A.A.H. Synthesis, Characterization, and Corrosion
Inhibition Potential of Novel Thiosemicarbazone on Mild Steel in Sulfuric Acid Environment. Coatings 2019, 9, 729. [CrossRef]
25. Hudson, J.B.; Brown, C.A.; Roberge, P.R. Corrosion Monitoring. In Comprehensive Materials Processing; Hashmi, S., Ed.; Elsevier:
Amsterdam, The Netherlands, 2014; Volume 4, pp. 305–325.
26. Nitonye, S.; Ugboga, P. Analysis of the Effectiveness and Efficiency of the VA Solution on Offshore Pipelines and Ship Materials.
Open J. Mar. Sci. 2019, 10, 16. [CrossRef]
27. Fateh, A.; Aliofkhazraei, M.; Rezvanian, A.R. Review of Corrosive Environments for Copper and Its Corrosion Inhibitors. Arab. J.
Chem. 2020, 13, 481–544. [CrossRef]
28. Cinitha, A.; Umesha, P.K.; Iyer, N.R. An Overview of Corrosion and Experimental Studies on Corroded Mild Steel Compression
Members. KSCE J. Civ. Eng. 2014, 18, 1735–1744. [CrossRef]
29. Aziz, I.A.A.; Abdulkareem, M.H.; Annon, I.A.; Hanoon, M.M.; Al-Kaabi, M.H.H.; Shaker, L.M.; Alamiery, A.A.; Wan Isa-
hak, W.N.R.; Takriff, M.S. Weight Loss, Thermodynamics, SEM, and Electrochemical Studies on N-2-Methylbenzylidene-4-
antipyrineamine as an Inhibitor for Mild Steel Corrosion in Hydrochloric Acid. Lubricants 2022, 10, 23. [CrossRef]
30. Smith, J.D. The Technique for Weight Loss Tests (WLT) to Estimate the Corrosion Current and Potential of a Metal in the Presence
of an Organic Inhibitor. Materials 2021, 14, 652. [CrossRef]
31. Noh, H.K.; Jin, Y.G. Corrosion Inhibition of Copper by Piperidine: Experimental and Computational Study. Metals 2019, 9, 822. [CrossRef]
32. Büchler, M.; Kerimo, J.; Guillaume, F.; Smyrl, W.H. Fluorescence and Near-Field Scanning Optical Microscopy for Investigating
Initiation of Localized Corrosion of Al 2024. J. Electrochem. Soc. 2000, 147, 3691. [CrossRef]
33. Sullivan, J.; Mehraban, S.; Elvins, J. In Situ Monitoring of the Microstructural Corrosion Mechanisms of Zinc–Magnesium–
Aluminium Alloys Using Time Lapse Microscopy. Corros. Sci. 2011, 53, 2208–2215. [CrossRef]
34. Rios, E.C.; Zimer, A.M.; Pereira, E.C.; Mascaro, L.H. Analysis of AISI 1020 Steel Corrosion in Seawater by Coupling Electrochemical
Noise and Optical Microscopy. Electrochim. Acta 2014, 124, 211–217. [CrossRef]
35. NIST X-ray Photoelectron Spectroscopy (XPS) Database. Available online: [Link] (accessed on 23 February 2023).
36. Hussein, S.S.; Al-Hasani, I.D.D.; Abed, A.M.; Hanoon, M.M.; Shaker, L.M.; Al-Amiery, A.; Kadhum, A.A.H.; Roslam Wan Isahak,
W.N. Antibacterial Corrosion Inhibitor for the Protection of Mild Steel in 1 M HCl Solution. Prog. Color Color. Coat. 2023, 16, 59–70.
37. Alamiery, A.; Ali, J.M.; Isahak, W.N.R. Experimental Studies on the Corrosion Inhibition of Mild Steel by 1-(Phenylamino-1,3,4-thiadiazol-
5-yl)-3-phenyl-3-oxopropan Complemented with DFT Modeling. KOM–Corros. Mater. Prot. J. 2022, 66, 7–15. [CrossRef]
38. Betti, N.; Al-Azzawi, W.K.; Alamiery, A. Synthesis and Study of Corrosion Behavior of Terephthalaldehyde-Derived Schiff Base
for Low-Carbon Steel in HCl: Experimental, Morphological and Theoretical Investigation. KOM–Corros. Mater. Prot. J. 2022,
66, 103–112. [CrossRef]
39. Lopez, D.A.; Schreiner, W.H.D.; De Sánchez, S.R.; Simison, S.N. The Influence of Carbon Steel Microstructure on Corrosion Layers:
An XPS and SEM Characterization. Appl. Surf. Sci. 2003, 207, 69–85. [CrossRef]
40. Bruemmer, S.M.; Thomas, L.E. High-Resolution Analytical Electron Microscopy Characterization of Corrosion and Cracking at
Buried Interfaces. Surf. Interface Anal. 2001, 31, 571–581. [CrossRef]
41. Volovitch, P.; Allely, C.; Ogle, K. Understanding Corrosion via Corrosion Product Characterization: I. Case Study of the Role of
Mg Alloying in Zn-Mg Coating on Steel. Corros. Sci. 2009, 51, 1251–1262. [CrossRef]
42. Al-Amiery, A.A.; Kadhum, A.A.H.; Kadihum, A.; Mohamad, A.B.; How, C.K.; Junaedi, S. Inhibition of Mild Steel Corrosion in
Sulfuric Acid Solution by New Schiff Base. Materials 2014, 7, 787–804. [CrossRef]
43. Roberge, P.R. Handbook of Corrosion Engineering; McGraw Hill Professional: New York, NY, USA, 2012.
44. Song, G.L.; Atrens, A. Understanding Corrosion Mechanisms, 2nd ed.; Elsevier: Amsterdam, The Netherlands, 2017.
45. Zhang, X.B.; Wang, D.; Li, X.G.; Hou, B.R.; Ke, W. Inhibition Mechanism of 1H-Benzotriazole on the Corrosion of Copper in
Aerated NaCl Solution. Corros. Sci. 2009, 51, 1016–1025.
46. Gabe, D.R.; Kim, Y.J. Scanning Electron Microscopy and Energy-Dispersive X-ray Spectroscopy for the Analysis of Corrosion
and its Inhibition. In Handbook of Materials Failure Analysis with Case Studies from the Chemicals, Concrete and Power Industries;
Butterworth-Heinemann: Oxford, UK, 2017; pp. 299–321. [CrossRef]
Lubricants 2023, 11, 174 26 of 29

47. Gomma, G.K.; Salem, M.A.; Zoromba, M.S.; Elsaid, M.O. Investigation of Corrosion Inhibition of Steel in Hydro-chloric Acid
Solution Using Three Schiff Bases as Organic Inhibitors. Mater. Today Commun. 2021, 27, 102371. [CrossRef]
48. Pardo, A.; Merino, M.C.; Coy, A.E.; Viejo, F.; Arrabal, R.; Matykina, E. Scanning Electron Microscopy with Backscattered Electron
Imaging (SEM-BSE) and Energy Dispersive X-ray Spectrometry (EDS) Analysis Applied to Corrosion Research. Mater. Charact.
2011, 62, 956–967. [CrossRef]
49. El-Enin, S.A.A.; Abo, S.A.; Amin, A. Review of Corrosion Inhibitors for Industrial Applications. Int. J. Eng. Res. Rev. 2015,
3, 127–145. [CrossRef]
50. Fouda, A.E.S.; Abdel Nazeer, A.; El-Khateeb, A.Y.; Fakih, M. Cinnamon Plant Extract as Corrosion Inhibitor for Steel Used in
Waste Water Treatment Plants and Its Biological Effect on Escherichia coli. J. Korean Chem. Soc. 2014, 58, 359–365. [CrossRef]
51. Khan, M.A.A.; Irfan, O.M.; Djavanroodi, F.; Asad, M. Development of Sustainable Inhibitors for Corrosion Control. Sustainability
2022, 14, 9502. [CrossRef]
52. El Mouaden, K.; El Ibrahimi, B.; Oukhrib, R.; Bazzi, L.; Hammouti, B.; Jbara, O.; Tara, A.; Chauhan, D.S.; Quraishi, M.A. Chitosan
polymer as a green corrosion inhibitor for copper in sulfide-containing synthetic seawater. Int. J. Biol. Macromol. 2018, 119,
1311–1323. [CrossRef] [PubMed]
53. Bouraoui, M.M.; Chettouh, S.; Chouchane, T.; Khellaf, N. Inhibition efficiency of cinnamon oil as a green corrosion inhibitor. J. Bio
Tribo-Corros. 2019, 5, 1–9. [CrossRef]
54. Ostovari, A.; Hoseinieh, S.M.; Peikari, M.; Shadizadeh, S.R.; Hashemi, S.J. Corrosion inhibition of mild steel in 1 M HCl solution
by henna extract: A comparative study of the inhibition by henna and its constituents (Lawsone, Gallic acid, α-d-Glucose and
Tannic acid). Corros. Sci. 2009, 51, 1935–1949. [CrossRef]
55. Adewuyi, A.; Daramola, M.; Babalola, J. Corrosion inhibition of mild steel in hydrochloric acid solution by crude extracts of
Vernonia amygdalina and Mangifera indica leaves. J. Mol. Liq. 2016, 215, 506–514.
56. Mohd Sani, N.; Ahmad, F.; Yusof, F.; Shamsudin, R. Piper nigrum extract as a natural corrosion inhibitor for mild steel in 3.5%
NaCl solution. J. Mol. Liq. 2018, 267, 475–483.
57. Bhat, S.; Nayak, U. Corrosion inhibition of mild steel in 3.5% NaCl solution by polysaccharide extracted from marine algae Padina
tetrastromatica. Int. J. Biol. Macromol. 2019, 129, 852–858.
58. Ebenso, E.; Ajanaku, K.; Olasunkanmi, L. Inhibitory effect of Azadirachta indica and Moringa oleifera leaf extracts in combination
with sodium molybdate on the corrosion of mild steel in hydrochloric acid. J. Mol. Liq. 2016, 215, 189–200.
59. Bokati, K.S.; Dehghanian, C. Adsorption behavior of 1H-benzotriazole corrosion inhibitor on aluminum alloy 1050, mild steel
and copper in artificial seawater. J. Environ. Chem. Eng. 2018, 6, 1613–1624. [CrossRef]
60. Resende, G.O.; Teixeira, S.F.; Figueiredo, I.F.; Godoy, A.A.; Lougon, D.J.F.; Cotrim, B.A.; de Souza, F.C. Synthesis of 1,2,3-Triazole
Derivatives and Its Evaluation as Corrosion Inhibitors for Carbon Steel. Int. J. Electrochem. 2019, 2019, 6759478. [CrossRef]
61. Zarrouk, A.; Hammouti, B.; Al-Deyab, S.S.; Essassi, E.M.; Aouniti, A.; Ramdani, A. Corrosion Inhibition Performance of
3,5-Diamino-1,2,4-Triazole for Protection of Copper in Nitric Acid Solution. Int. J. Electrochem. 2012, 7, 5997–6011.
62. Kumar, A.; Yadav, D.K.; Singh, A.K. A Comparative Study on Corrosion Inhibition of Mild Steel by Catechin and 2-
Mercaptobenzothiazole in Hydrochloric Acid. J. Mater. Sci. 2016, 51, 7588–7600. [CrossRef]
63. Obot, I.B.; Obi-Egbedi, N.O.; Umoren, S.A. Inhibitive Action of Vanillin on the Corrosion of Mild Steel in Acidic Media. J. Ind.
Eng. Chem. 2013, 19, 167–174. [CrossRef]
64. Li, X.; Liu, Y.; Cheng, Y.; Jiang, L.; Zhai, Y. Inhibitory Effect of Natural and Synthetic Inhibitors on the Corrosion of Carbon Steel
in Acidic Solutions. J. Mater. Sci. 2018, 53, 15838–15851. [CrossRef]
65. El-Etre, A.Y.; Abdallah, M.; El-Tantawy, Z.E. Inhibition of Aluminum Corrosion Using Opuntia Extract. Corros. Sci. 2008,
50, 2993–3000. [CrossRef]
66. Mekidiche, L.; Chibani, S.; Harek, Y.; Hammouti, B. Corrosion Inhibition of Mild Steel in 1 M HCl Solution by Synthetic and
Natural Inhibitors. J. Mater. Environ. Sci. 2018, 9, 2849–2860.
67. Muster, T.; Rohwerder, M.; Stratmann, M. Quantitative XPS Analysis of Corrosion Inhibitor Films on Iron. Surf. Sci. 2005,
595, 103–112. [CrossRef]
68. Zhang, L.; Lu, X.; Li, X. Progress in Surface Science Research for Corrosion Inhibition. Prog. Org. Coat. 2014, 77, 548–555. [CrossRef]
69. Walczak, M.S.; Morales-Gil, P.; Lindsay, R. Determining Gibbs Energies of Adsorption from Corrosion Inhibition Efficiencies: Is It
a Reliable Approach? Corros. Sci. 2019, 155, 182–185. [CrossRef]
70. Tobiason, J.E.; Wesolowski, D.J.; McCormick, S.L.W.; Lewis, E.A. Molecular Dynamics Simulations of Inhibitor Adsorption on the
Iron (110) Surface in Aqueous Solutions. J. Phys. Chem. B 2008, 112, 5716–5725. [CrossRef]
71. Zhang, J.; Luo, Z. Density Functional Theory Study of the Adsorption Behavior of 1,2,3-Benzotriazole on Copper Surface. Appl.
Surf. Sci. 2018, 458, 452–458. [CrossRef]
72. Shreir, L.L.; Jarman, R.A.; Burstein, G.T.; Shimada, H. Corrosion: Fundamentals, Testing, and Protection; Elsevier: Oxford, UK, 2013.
73. Stern, M.; Geary, A.L. Electrochemical Polarization: I. A Theoretical Analysis of the Shape of Polarization Curves. J. Electrochem.
Soc. 1957, 104, 56–63. [CrossRef]
74. Al-Moubaraki, A.H.; Al-Mayouf, A.M.; Al-Hashem, A. Corrosion Inhibition of Carbon Steel in Acidic Media Using Some
Synthetic and Natural Inhibitors. J. Mater. Sci. 2014, 49, 1191–1201. [CrossRef]
75. Fox, P.G.; Bradley, P.A. [Link]-Triazole as a Corrosion Inhibitor for Copper. Corros. Sci. 1980, 20, 643–649. [CrossRef]
Lubricants 2023, 11, 174 27 of 29

76. Ituen, E.; Akaranta, O.; James, A. Evaluation of Performance of Corrosion Inhibitors Using Adsorption Isotherm Models: An
Overview. Chem. Sci. Int. J. 2017, 18, 1–34. [CrossRef] [PubMed]
77. Guo, L.; Zhu, S.; Zhang, S.; He, Q.; Li, W. Theoretical Studies of Three Triazole Derivatives as Corrosion Inhibitors for Mild Steel
in Acidic Medium. Corros. Sci. 2014, 87, 366–375. [CrossRef]
78. Mihajlović, M.B.P.; Radovanović, M.B.; Tasić, Ž.Z.; Antonijević, M.M. Imidazole Based Compounds as Copper Corrosion
Inhibitors in Seawater. J. Mol. Liq. 2017, 225, 127–136. [CrossRef]
79. Frankel, G.S. Corrosion Inhibitors. In Encyclopedia of Materials: Science and Technology; Elsevier: Amsterdam, The Netherlands,
2001; pp. 1–7.
80. Abd El Rehim, S.S.; Negm, N.A. Organic Corrosion Inhibitors: A Comprehensive Review. J. Mater. Sci. Res. 2013, 2, 76–84.
81. Revie, R.W.; Uhlig, H.H. Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering, 4th ed.; John Wiley &
Sons, Inc.: Hoboken, NJ, USA, 2019.
82. Shivaraj, T.; Karthick, R.; Jeyakumar, M.S.; Anandan, S. Recent Developments in Organic Corrosion Inhibitors for Mild Steel in
Different Environments: A Review. J. Ind. Eng. Chem. 2014, 20, 424–438.
83. Chen, S.; Zhang, D.; Zhou, G. Advances in research on organic corrosion inhibitors: A review. J. Mol. Liq. 2014, 192, 97–109. [CrossRef]
84. Roberge, P.R. Handbook of Corrosion Engineering, 2nd ed.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2017.
85. Al-Kharafi, F.M.; Al-Hajjar, F.H.; Katrib, A. 3-Phenyl-1,2,4-triazol-5-one as a Corrosion Inhibitor for Copper. Corros. Sci. 1986,
26, 257–264. [CrossRef]
86. Gurjar, S.; Sharma, S.K.; Sharma, A.; Ratnani, S. Performance of Imidazolium Based Ionic Liquids as Corrosion Inhibitors in
Acidic Medium: A Review. Appl. Surf. Sci. Adv. 2021, 6, 100170. [CrossRef]
87. Chaouiki, A.; Chafiq, M.; Ko, Y.G.; Al-Moubaraki, A.H.; Thari, F.Z.; Salghi, R.; Karrouchi, K.; Bougrin, K.; Ali, I.H.; Lgaz, H.
Adsorption Mechanism of Eco-Friendly Corrosion Inhibitors for Exceptional Corrosion Protection of Carbon Steel: Electrochemical
and First-Principles DFT Evaluations. Metals 2022, 12, 1598. [CrossRef]
88. Liu, Y.; Lv, P.; Gao, L.; Wang, F.; Wang, H. A Review on Application of X-ray Photoelectron Spectroscopy in Corrosion Inhibition.
J. Mater. Sci. Technol. 2019, 35, 717–726. [CrossRef]
89. Wang, H.-L.; Fan, H.-B.; Zheng, J.-S. Corrosion Inhibition of Mild Steel in Hydrochloric Acid Solution by a Mercapto-Triazole
Compound. Mater. Chem. Phys. 2003, 77, 655–661.
90. Al-Azzawi, W.K.; Hussein, S.S.; Salih, S.M.; Zinad, D.S.; Al-Azzawi, R.K.; Hanoon, M.M.; Al-Amiery, A.; Kadhum, A.A.H.; Takriff,
M.S. Efficient Protection of Mild Steel Corrosion in Hydrochloric Acid Using 3-(5-Amino-1, 3, 4-thiadiazole-2yl)-2H-chromen-2-
one, a Coumarin Derivative Bearing a 1, 3, 4-thiadiazole Moiety: Gravimetrical Techniques, Computational and Thermodynamic
Investigations. Prog. Color Colorants Coat. 2023, 16, 97–111. [CrossRef]
91. Alamiery, A.A. Study of Corrosion Behavior of N’-(2-(2-oxomethylpyrrol-1-yl)ethyl)piperidine for Mild Steel in the Acid
Environment. Biointerface Res. Appl. Chem. 2022, 12, 3638–3646. [CrossRef]
92. Alamiery, A.; Mohamad, A.B.; Kadhum, A.A.H.; Takriff, M.S. Comparative Data on Corrosion Protection of Mild Steel in HCl
Using Two New Thiazoles. Data Brief 2022, 40, 107838. [CrossRef] [PubMed]
93. Mustafa, A.M.; Sayyid, F.F.; Betti, N.; Shaker, L.M.; Hanoon, M.M.; Alamiery, A.A.; Kadhum, A.A.H.; Takriff, M.S. Inhibition of
Mild Steel Corrosion in Hydrochloric Acid Environment by 1-Amino-2-Mercapto-5-(4-(pyrrol-1-yl)phenyl)-1,3,4-triazole. South
Afr. J. Chem. Eng. 2022, 39, 42–51. [CrossRef]
94. Alamiery, A.A. Investigations on Corrosion Inhibitory Effect of Newly Quinoline Derivative on Mild Steel in HCl Solution
Complemented with Antibacterial Studies. Biointerface Res. Appl. Chem. 2022, 12, 1561–1568. [CrossRef]
95. Alkadir Aziz, I.A.; Annon, I.A.; Abdulkareem, M.H.; Hanoon, M.M.; Alkaabi, M.H.; Shaker, L.M.; Alamiery, A.A.; Wan Isahak,
W.N.R.; Takriff, M.S. Insights into Corrosion Inhibition Behavior of a 5-Mercapto-1,2,4-triazole Derivative for Mild Steel in
Hydrochloric Acid Solution: Experimental and DFT Studies. Lubricants 2021, 9, 122. [CrossRef]
96. Alamiery, A. Short report of mild steel corrosion in 0.5 M H2 SO4 by 4-ethyl-1-(4-oxo-4-phenylbutanoyl)thiosemicarbazide. J.
Tribol. 2021, 30, 90–99. [CrossRef]
97. Alamiery, A.A.; Isahak, W.N.R.W.; Takriff, M.S. Inhibition of Mild Steel Corrosion by 4-Benzyl-1-(4-Oxo-4-Phenylbutanoyl)Thiose-
micarbazide: Gravimetrical, Adsorption and Theoretical Studies. Lubricants 2021, 9, 93. [CrossRef]
98. Dawood, M.A.; Alasady, Z.M.K.; Abdulazeez, M.S.; Ahmed, D.S.; Sulaiman, G.M.; Kadhum, A.A.H.; Shaker, L.M.; Alamiery,
A.A. The Corrosion Inhibition Effect of a Pyridine Derivative for Low Carbon Steel in 1 M HCl Medium: Complemented with
Antibacterial Studies. Int. J. Corros. Scale Inhib. 2021, 10, 1766–1782. [CrossRef]
99. Alamiery, A. Corrosion Inhibition Effect of 2-N-Phenylamino-5-(3-Phenyl-3-oxo-1-propyl)-1,3,4-oxadiazole on Mild Steel in 1 M Hy-
drochloric Acid Medium: Insight from Gravimetric and DFT Investigations. Mater. Sci. Energy Technol. 2021, 4, 398–406. [CrossRef]
100. Alamiery, A.A. Anticorrosion Effect of Thiosemicarbazide Derivative on Mild Steel in 1 M Hydrochloric Acid and 0.5 M Sulfuric
Acid: Gravimetrical and Theoretical Studies. Mater. Sci. Energy Technol. 2021, 4, 263–273. [CrossRef]
101. Alamiery, A.A.; Isahak, W.N.R.W.; Aljibori, H.S.S.; Al-Asadi, H.A.; Kadhum, A.A.H. Effect of the Structure, Immersion Time and
Temperature on the Corrosion Inhibition of 4-Pyrrol-1-yl-N-(2,5-dimethyl-pyrrol-1-yl)benzoylamine in 1.0 M HCl Solution. Int. J.
Corros. Scale Inhib. 2021, 10, 700–713. [CrossRef]
102. Al-Amiery, A.A.; Mohamad, A.B.; Kadhum, A.A.H.; Allami, T.; Yusop, R.M.; Takriff, M.S. Experimental and Theoretical Study on the
Corrosion Inhibition of Mild Steel by Nonanedioic Acid Derivative in Hydrochloric Acid Solution. Sci. Rep. 2022, 12, 4705. [CrossRef]
Lubricants 2023, 11, 174 28 of 29

103. Alamiery, A.; Mahmoudi, E.; Allami, T. Corrosion Inhibition of Low-Carbon Steel in Hydrochloric Acid Environment Using a
Schiff Base Derived from Pyrrole: Gravimetric and Computational Studies. Int. J. Corros. Scale Inhib. 2021, 10, 749–765. [CrossRef]
104. Eltmimi, A.J.M.; Alamiery, A.; Allami, A.J.; Yusop, R.M.; Kadhum, A.A.H.; Allami, T. Inhibitive Effects of a Novel Efficient Schiff
Base on Mild Steel in Hydrochloric Acid Environment. Int. J. Corros. Scale Inhib. 2021, 10, 634–648. [CrossRef]
105. Alamiery, A.; Shaker, L.M.; Allami, T.; Kadhum, A.H.; Takriff, M.S. A Study of Acidic Corrosion Behavior of Furan-Derived
Schiff Base for Mild Steel in Hydrochloric Acid Environment: Experimental, and Surface Investigation. Mater. Today Proc. 2021,
44, 2337–2341. [CrossRef]
106. Al-Baghdadi, S.B.; Al-Amiery, A.A.; Gaaz, T.S.; Kadhum, A.A.H. Terephthalohydrazide and Isophthalo-Hydrazide as New
Corrosion Inhibitors for Mild Steel in Hydrochloric Acid: Experimental and Theoretical Approaches. Koroze Ochr. Mater. 2021,
65, 12–22. [CrossRef]
107. Hanoon, M.M.; Resen, A.M.; Shaker, L.M.; Kadhum, A.A.H.; Al-Amiery, A.A. Corrosion Investigation of Mild Steel in Aqueous
Hydrochloric Acid Environment Using n-(Naphthalen-1yl)-1-(4-pyridinyl)methanimine Complemented with Antibacterial
Studies. Biointerface Res. Appl. Chem. 2021, 11, 9735–9743. [CrossRef]
108. Al-Baghdadi, S.; Gaaz, T.S.; Al-Adili, A.; Al-Amiery, A.A.; Takriff, M.S. Experimental Studies on Corrosion Inhibition Performance
of Acetylthiophene Thiosemicarbazone for Mild Steel in HCl Complemented with DFT Investigation. Int. J. Low-Carbon Technol.
2021, 16, 181–188. [CrossRef]
109. Al-Amiery, A.A. Anti-Corrosion Performance of 2-Isonicotinoyl-N-phenylhydrazinecarbothioamide for Mild Steel Hydrochloric Acid
Solution: Insights from Experimental Measurements and Quantum Chemical Calculations. Surf. Rev. Lett. 2021, 28, 2050058. [CrossRef]
110. Abdulazeez, M.S.; Abdullahe, Z.S.; Dawood, M.A.; Handel, Z.K.; Mahmood, R.I.; Osamah, S.; Kadhum, A.H.; Shaker, L.M.;
Al-Amiery, A.A. Corrosion Inhibition of Low Carbon Steel in HCl Medium Using a Thiadiazole Derivative: Weight Loss, DFT
Studies and Antibacterial Studies. Int. J. Corros. Scale Inhib. 2021, 10, 1812–1828. [CrossRef]
111. Mustafa, A.M.; Sayyid, F.F.; Betti, N.; Hanoon, M.M.; Al-Amiery, A.A.; Kadhum, A.A.H.; Takriff, M.S. Inhibition Evaluation of 5-(4-
(1H-Pyrrol-1-yl)phenyl)-2-mercapto-1,3,4-oxadiazole for the Corrosion of Mild Steel in an Acidic Environment: Thermodynamic
and DFT Aspects. Tribologia 2021, 38, 39–47. [CrossRef]
112. Abdulsahib, Y.M.; Eltmimi, A.J.M.; Alhabeeb, S.A.; Hanoon, M.M.; Al-Amiery, A.A.; Allami, T.; Kadhum, A.A.H. Experimental
and Theoretical Investigations on the Inhibition Efficiency of N-(2,4-Dihydroxytolueneylidene)-4-methylpyridin-2-amine for the
Corrosion of Mild Steel in Hydrochloric Acid. Int. J. Corros. Scale Inhib. 2021, 10, 885–899. [CrossRef]
113. Khudhair, A.K.; Mustafa, A.M.; Hanoon, M.M.; Al-Amiery, A.; Shaker, L.M.; Gazz, T.; Mohamad, A.B.; Kadhum, A.H.; Takriff,
M.S. Experimental and Theoretical Investigation on the Corrosion Inhibitor Potential of N-MEH for Mild Steel in HCl. Prog. Color
Colorants Coat. 2021, 15, 111–122. [CrossRef]
114. Zinad, D.S.; Salim, R.D.; Betti, N.; Shaker, L.M.; AL-Amiery, A.A. Comparative Investigations of the Corrosion Inhibition
Efficiency of a 1-phenyl-2-(1-phenylethylidene)hydrazine and its Analog Against Mild Steel Corrosion in Hydrochloric Acid
Solution. Prog. Color Colorants Coat. 2021, 15, 53–63.
115. Salim, R.D.; Betti, N.; Hanoon, M.; Al-Amiery, A.A. 2-(2,4-Dimethoxybenzylidene)-N-Phenylhydrazinecarbothioamide as an
Efficient Corrosion Inhibitor for Mild Steel in Acidic Environment. Prog. Color Colorants Coat. 2021, 15, 45–52.
116. Al-Amiery, A.A.; Shaker, L.M.; Kadhum, A.H.; Takriff, M.S. Exploration of Furan Derivative for Application as Corrosion Inhibitor
for Mild Steel in Hydrochloric Acid Solution: Effect of Immersion Time and Temperature on Efficiency. Mater. Today Proc. 2021,
42, 2968–2973. [CrossRef]
117. Resen, A.M.; Hanoon, M.M.; Alani, W.K.; Kadhim, A.; Mohammed, A.A.; Gaaz, T.S.; Kadhum, A.A.H.; Al-Amiery, A.A.; Takriff,
M.S. Exploration of 8-Piperazine-1-ylmethylumbelliferone for Application as a Corrosion Inhibitor for Mild Steel in Hydrochloric
Acid Solution. Int. J. Corros. Scale Inhib. 2021, 10, 368–387. [CrossRef]
118. Hanoon, M.M.; Resen, A.M.; Al-Amiery, A.A.; Kadhum, A.A.H.; Takriff, M.S. Theoretical and Experimental Studies on the
Corrosion Inhibition Potentials of 2-((6-Methyl-2-Ketoquinolin-3-yl)Methylene) Hydrazinecarbothioamide for Mild Steel in 1 M
HCl. Prog. Color Colorants Coat. 2021, 15, 21–33.
119. Hashim, F.G.; Salman, T.A.; Al-Baghdadi, S.B.; Gaaz, T.; Al-Amiery, A.A. Inhibition Effect of Hydrazine-Derived Coumarin on a
Mild Steel Surface in Hydrochloric Acid. Tribologia 2020, 37, 45–53. [CrossRef]
120. Resen, A.M.; Hanoon, M.; Salim, R.D.; Al-Amiery, A.A.; Shaker, L.M.; Kadhum, A.A.H. Gravimetrical, Theoretical, and Surface
Morphological Investigations of Corrosion Inhibition Effect of 4-(Benzoimidazole-2-yl) Pyridine on Mild Steel in Hydrochloric
Acid. Koroze Ochr. Mater. 2020, 64, 122–130. [CrossRef]
121. Salman, A.Z.; Jawad, Q.A.; Ridah, K.S.; Shaker, L.M.; Al-Amiery, A.A. Selected BIS-Thiadiazole: Synthesis and Corrosion
Inhibition Studies on Mild Steel in HCL Environment. Surf. Rev. Lett. 2020, 27, 2050014. [CrossRef]
122. Abdel-Gaber, A.; Khamis, E.; Al-Sabagh, A.; Zaki, M. Inhibition of aluminum corrosion using Opuntia extract. Corros. Sci. 2006,
48, 2765–2779. [CrossRef]
123. Ashassi-Sorkhabi, H.; Hashemi, S.J.; Shadizadeh, S.R.; Shirazi, M. Comparison of corrosion inhibition effect of imidazole and
benzimidazole derivatives on copper in 3. 5% NaCl solution. Mater. Chem. Phys. 2004, 87, 267–272. [CrossRef]
124. Haque, M.E.; Rahman, M.A.; Islam, M.M.; Ali, M.E. Corrosion inhibition of mild steel in 1 M HCl solution by some organic
compounds. J. Mater. Res. Technol. 2012, 1, 33–39. [CrossRef]
125. Li, X.; Li, Y.; Li, G.; Li, S.; Gao, X.; Li, J.; Sun, C. A comparative study on the inhibition performance of four synthesized imidazoline
derivatives as corrosion inhibitors for mild steel in 1 M hydrochloric acid. J. Mol. Liq. 2020, 306, 112899. [CrossRef]
Lubricants 2023, 11, 174 29 of 29

126. Wang, H.; Gao, L.; Wang, F.; Hou, B. Comparative study of inhibition effect of lignin and modified lignin on mild steel corrosion
in acidic medium. J. Mol. Liq. 2016, 222, 600–608. [CrossRef]
127. Bhat, S.K.; Pujari, P.H. Corrosion Inhibition of Mild Steel by Some Natural Products in Acidic Media. J. Mater. Sci. 2001,
36, 467–474. [CrossRef]
128. Abdel-Gaber, A.; Abd-El-Nabey, B.; Sidahmed, I.; El-Zayady, M.A. The Role of Some Organic Compounds as Corrosion Inhibitors
for Steel in Acidic Solutions. Appl. Surf. Sci. 2002, 198, 388–397. [CrossRef]
129. Xu, J.; Li, X.; Huang, X.; Wang, L. Evaluation of Tannins as Natural Corrosion Inhibitors for Mild Steel in Acidic Media. Corros.
Sci. 2011, 53, 2364–2371. [CrossRef]
130. Souza, M.T.; Santos, A.O.; Silva, C.C.; Souza, R.A.M.A. Eco-Friendly Corrosion Inhibitors: A Review of Recent Progress in Marine
and Coastal Biofouling Control. Mar. Drugs 2020, 18, 136. [CrossRef]
131. Mohamed, A.M. Eco-Friendly Corrosion Inhibitors from Natural Sources: A Review. J. Environ. Chem. Eng. 2021, 9, 104877. [CrossRef]
132. Oliveira Filho, J.G.d.; Silva, G.d.C.; Oldoni, F.C.A.; Miranda, M.; Florencio, C.; Oliveira, R.M.D.d.; Gomes, M.d.P.; Ferreira,
M.D. Edible Coating Based on Carnauba Wax Nanoemulsion and Cymbopogon martinii Essential Oil on Papaya Postharvest
Preservation. Coatings 2022, 12, 1700. [CrossRef]
133. Chen, C.; Yang, H.; Liu, J.; Luo, H.; Zou, W. Systematic Review of Actinomycetes in the Baijiu Fermentation Microbiome. Foods
2022, 11, 3551. [CrossRef]
134. Farhadian, A.; Rahimi, A.; Safaei, N.; Shaabani, A.; Abdouss, M.; Alavi, A. A Theoretical and Experimental Study of Castor
Oil-Based Inhibitor for Corrosion Inhibition of Mild Steel in Acidic Medium at Elevated Temperatures. Corros. Sci. 2020,
175, 108871. [CrossRef]
135. Biswas, A.; Pal, S.; Udayabhanu, G. Experimental and Theoretical Studies of Xanthan Gum and Its Graft Co-Polymer as Corrosion
Inhibitor for Mild Steel in 15% HCl. Appl. Surf. Sci. 2015, 353, 173–183. [CrossRef]
136. Rafiee, J.S.; Mohamed, A.M.A.; Sulaiman, A.; Abdullah, M.R. Review on Natural Corrosion Inhibitors for Oil and Gas Industries.
J. Mater. Environ. Sci. 2015, 6, 1725–1739.
137. Khayat, M.S.; Ebenso, E.E.; Kabanda, M.M. Green Inhibitors for Acid Corrosion of Metals: A Review. J. Ind. Eng. Chem. 2014, 20, 1149–1169.
138. Quraishi, M.A.; Al-Mulhem, N.A.; Mohamed, A.M.A. Eco-Friendly Inhibitors for Corrosion Protection of Metals and Alloys: An
Overview. Int. J. Electrochem. Sci. 2010, 5, 704–728.
139. Shafaei, T.; Bahramian, A.; Khaki, S.D. Natural Corrosion Inhibitors in the Oil Industry: A Review. Oil Gas Sci. Technol. 2016, 71, 86.
140. Al-Sabagh, A.M.; Al-Azizi, N.M.; Quraishi, M.A. Corrosion Inhibition of Mild Steel in Acidic Solution Using Essential Oils. Arab.
J. Chem. 2017, 3, S67–S76.
141. Abd El-Rehim, S.S.; Al-Sarawy, A.A.; Diab, M.A. Natural Essential Oils as Corrosion Inhibitors for Steel in HCl Solution. Mater.
Chem. Phys. 2016, 184, 109–117. [CrossRef]
142. Javid, M.; Zahoor, A.F.; Sadiq, M.; Zahid, M.; Ali, A.; Abbas, S.M. Investigation of Corrosion Inhibition Behavior of a Novel Schiff
Base for Carbon Steel in HCl. Arab. J. Chem. 2018, 11, 1079–1089. [CrossRef]
143. Hossain, M.A.; Yasmin, T.; Khan, M.K.; Rafique, M.S.; Siddique, M.A.B. Corrosion Inhibition Performance of 1,3-
Dimethylimidazolium Chloride and Its Synergistic Effect with Sodium Nitrite for Mild Steel in HCl Solution. VJChroma
2022, 61, 15–42. [CrossRef]
144. Brycki, B.E.; Kowalczyk, I.H.; Szulc, A.; Kaczerewska, O.; Pakiet, M. Organic Corrosion Inhibitors. In Corrosion Inhibitors, Principles
and Recent Applications; IntechOpen: London, UK, 2018. [CrossRef]
145. Raja, P.B.; Sethuraman, M.G.; Shanmugam, N. Corrosion Inhibitors: A Review. Rev. Adv. Mater. Sci. 2017, 49, 185–218. [CrossRef]
146. Idris, A.M.; Mohamad, A.A. Corrosion Inhibitors: Principles, Mechanisms and Applications; Springer: Cham, Switzerland, 2017. [CrossRef]
147. Ahmad, Z.; Riaz, S. Recent Advances in the Development of Organic Corrosion Inhibitors: A Review. J. Mol. Liq. 2019, 293, 111419. [CrossRef]
148. Popova, A.; Sokolova, E.; Raicheva, S.; Christov, M.; Vasilev, A. AC and DC Study of the Temperature Effect on Mild Steel
Corrosion in Acid Media in the Presence of Benzimidazole Derivatives. Corros. Sci. 2003, 45, 33–58. [CrossRef]
149. Raja, P.B.; Sethuraman, M.G.; Shanmugam, N. Corrosion Inhibition of Mild Steel in Acidic Media by Carissa Carandas Extract:
Experimental and Theoretical Approach. J. Mol. Liq. 2018, 250, 56–69. [CrossRef]

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