Corrosion Inhibitors PDF

Chapter 01
Corrosion Inhibitors
Geethamani Palanisamy
Abstract
Corrosion is a natural process driven by energy consideration. Inhibition is a

preventive measure against corrosive attack on metallic materials. Corrosion inhibi-
tors have been frequently studied, since they offer simple solution for protection of
metals against corrosion in aqueous environment. Mineral acids like hydrochloric
and sulfuric acids are most widely used in pickling baths to remove the metal
oxides formed on the surface. The multidisciplinary aspect of corrosion problems
combined with the distributed responsibilities associated with such problems only
increase the complexity of the subject. Inhibitors are used in industrial and com-
mercial processes to minimize both the metal loss and acid consumption.
Keywords: corrosion inhibitors, acidic inhibitors, volatile inhibitors, vapor phase

inhibitor
1. Introduction
Corrosion is the primary means by which metals deteriorate. Corrosion

introduces itself into many parts of our lives [1, 2]. The great majority of us have
personal feeling for the importance of corrosion. Far too many have cringed at
the emergence of rust holes in the body panels of relatively new automobiles [3].
The outdoor rusting of steel, household and garden appliances is a common fact
of life. All have seen the strains on cooking utensils from hot foods or experienced
the metallic taste in acid foods stored too long on open cans. That these effects are
caused by corrosion is well known [4]. The glaring example related to corrosion is
the appearance of cracks in certain portions of Taj Mahal, was due to steel dowels
embedded inside had extensively corroded and rusted leading to fractures in the
stoned [5]. However, corrosion is just as common in other material classes such as
ceramics, plastics and rubber. Since, practically all environments are corrosive to
some degree and are major contributing causes of material failure and also are a
large economic cost to the society [6].
2. Historical background
Corrosion can be viewed as a universal phenomenon, omnipresent and omnipo-

tent. It is there everywhere, air, water, soil and in every environment, we encounter
[7]. Known to people as rust, corrosion is an undesirable phenomenon which
destroys the luster and beauty of the materials and lessens their life. Indian govern-
ment spending around 3.5% Lakscrores of the nation’s GDP per annum for losses of
corrosion [8]. Recent studies estimate that, not only in India, other countries also
rise their funds for demand of corrosion inhibitors [9].
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Corrosion costs manifest in the form of premature deterioration or failure necessi-

tating maintenance, repairs and replacement of damaged parts.. Corrosion has a vast
environmental and economic impact on all the surfaces of national infrastructure
like highways, bridges, buildings, chemical processing units, waste water treatment
and virtually on all metallic objects in our day to day life use [10]. Other than material
loss, corrosion interferes not only with environment, also affects human safety and
industrial operations severely. Awareness to corrosion and adaptation of timely and
appropriate control measures hold the key in the abatement of corrosion failures [11].
3. Corrosion definition
The spontaneous oxidation of metal is termed as corrosion [12], that is,

Corrosion is the deterioration or destruction of metals and alloys in the presence of
an environment by chemical or electrochemical means. The medium in which the
metal undergoes corrosion is termed as corrosive or aggressive medium. Corrosion
products formed are chemical compounds containing the metal in the oxidized
form with the exception of gold and platinum, all other metals corrode and trans-
form themselves into substances similar to the mineral ores from which they are
extracted [13].
4. Adverse economic and social effects of corrosion
The corrosion affects severely on the safe, reliable and efficient operation of
equipment and structures than the simple loss of a mass of metal [14]. Failures of
all kind of machineries and the need for expensive replacements may occur even
though the amount of metal destroyed is quite small. Some of the major harmful
effects of corrosion can be listed below:
Nuclear plant shutdown due to failure, for example, nuclear reactor during
decontamination process.
• Replacement of corroded equipment resulting in heavy expenditure.
• High cost preventive maintenance such as painting.
• Loss of efficiency.
• Loss of product from a corroded container.
• Safety requirement measures from a fire hazard or explosion or release of toxic

product.
• Health problems, for example, drinking water contamination with lead is likely
due to corrosion.
5. Chemistry of corrosion
In general, metals are having unique properties like opaque, lustrous, conductiv-
ity, malleable and ductile in nature and are readily forms metallic bonds with other
metals and ionic bonds with non-metals [15, 16]. The metals that have overlapping
conduction bands and valence bands in their electronic structure.
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DOI: http://dx.doi.org/10.5772/intechopen.80542
Figure 1.
Corrosion cycle process.
Metals are obtained from their ore by the expenditure of large amounts of
energy. Metals store heat as potential energy during the smelting and refining
process and release this energy during the corrosion process after reacting with
the environment. These metals can therefore be regarded as being in a metastable
state and will tend to lose their energy by reverting to compounds more or less
similar to their original states, for example the starting material for iron and
steel making and the corrosion product rust has the same chemical composition
(Fe2O3).
The energy stored during melting and released during corrosion supplies
the driving potential for the corrosion process to take place. Since most metallic
compounds, and especially corrosion products, have little mechanical strength, a
severely corroded piece of metal is quite useless for its original purpose [17]. Metals
such as Mg, Al, Zn, and Fe which require larger amount of energy for refining are
more susceptible to corrosion than metals which require lesser amount for refining
such as gold, silver, platinum. A corrosion cycle is shown below (Figure 1).
6. Classification
Corrosion has been classified into different methods. They are
• Low temperature corrosion and high temperature corrosion (or)
• Electrochemical corrosion and chemical corrosion (or)
• Wet and Dry corrosion.
Wet corrosion occurs when the metal is in contact with an electrolytic conduct-
ing liquid or when two dissimilar metals or alloys are either immersed or dipped
partially in the electrolytic conducting solutions. This is always associated with low
temperature conditions. The corrosion process involves two reactions.
At anode:
M (metal) → Mn+ + ne− (oxidation)

Mn + (metal ion) → Dissolves in solution
Mn + (metal ion) → Forms compound such as oxide
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At Cathode:
2H+ + 2e− → H2↑ (in acid solution)

2H2O + 2e− → H2↑ + 2OH− (in alkaline solution)
O2 + 2H2O + 4e− → 4OH− (in neutral solution)
Dry corrosion takes place mainly through the direct chemical action of atmo-
spheric gases and vapors present in the environment 30. This is most often associ-
ated with high temperature.
7. Forms of corrosion
Corrosion can manifest itself in many forms such as uniform corrosion or

general corrosion, galvanic corrosion, crevice corrosion, pitting corrosion, inter-
granular corrosion, selective leaching, erosion corrosion, stress corrosion, corrosion
fatigue and fretting corrosion [18]. In order to improve the understanding between
corrosion and design engineers it is classified into two broad categories. They are
expressed in flow chart (Figure 2).
7.1 General corrosion
This general corrosion also called as a uniform attack is the most common form
of corrosion. It is normally characterized by a chemical or electrochemical reaction
which proceeds uniformly over the entire exposed surface or over a large area [19].
The metal becomes thinner and eventually fails.
7.2 Galvanic corrosion
It occurs when a potential difference exists between two dissimilar metals

immersed in a corrosive solution. This potential difference produces a flow of
electrons between the metals. Several investigations have shown that, galvanic cor-
rosion is directly proportional to the area of the cathodic to the anodic metal [20].
A schematic diagram for galvanic corrosion is shown below(Figure 3).
Figure 2.
Forms of corrosion.
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Figure 3.
Schematic representation of galvanic corrosion.
Figure 4.
Schematic representation of crevice corrosion.
7.3 Crevice corrosion or deposit corrosion
This kind of corrosion is attacked generally within crevices associated with

small volumes of stagnant solution trapped in holes, surfaces, joints and crevices
under bolt and rivet heads (Figure 4) [21]. It is also known as deposit or gasket
corrosion.
7.4 Pitting corrosion or localized corrosion
Pitting corrosion is a localized attack resulting in the formation of holes in

the metals. These holes are relatively small and they are looks like a rough surface
(Figure 5), they were sometimes isolated or so close together. Pitting is one of the
most destructive and insidious forms of corrosion [22].
7.5 Intergranular corrosion
Most of the metals and alloys are susceptible to intergranular corrosion, when
exposed to specific corrosion environment which is shown in the Figure 6. Grain
boundaries are usually more reactive than grain matrix. Hence localized attack
occurs at and adjacent to grain boundaries with relatively little corrosion of the
matrix. This type of attack is usually rapid and penetrates deep into the metal
resulting in loss of strength and causes catastrophic failures. It is caused by,
• Impurities at the grain boundaries
• Enrichment of one of the elements in the alloy
• Depletion of one of the elements in the boundary area.
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7.6 Selective leaching
Selective leaching is the removal of an element from an alloy by corrosion.

Selective removal of zinc from brass is a prime example of this form of attack. A
similar attack has been observed with other alloys in which iron, aluminum, cobalt
and chromium are removed. This type corrosion is undesirable as it yields a porous
metal with poor mechanical properties (Figure 7).
7.7 Erosion corrosion
It is the increase of attack of a metal because of relative movement between a cor-

rosive medium and the metal surface. This type of erosion corrosion is usually associ-
ated with systems where high velocities of corrosive fluids or gases are encountered.
Figure 5.
Schematic representation of pitting corrosion.
Figure 6.
Schematic representation of intergranular corrosion.
Figure 7.
Schematic representation of selective leaching corrosion.
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Figure 8.
Schematic representation of erosion corrosion.
This corrosion can be observed in piping system such as bends, elbows, pumps and
condensers, etc. A Schematic representation of erosion corrosion is shown in Figure 8.
Factors affecting erosion corrosion are nature of surface film, corrosion environment
and presence of air bubbles with its size, chemical composition, suspended solids,
corrosion resistance and metallurgical properties of metals and alloys.
7.8 Stress corrosion
The cracking of metal or alloy by the combined action of a tensile stress and a
corrodent (Figure 9) is known as stress corrosion cracking. The susceptibility to
stress corrosion cracking is due to certain metallurgical factors such as,
• Chemical composition
• Preferential orientation of grains
• Composition and distribution of precipitates
• Dislocation structure and environmental factors and structure of metal.
7.9 Corrosion fatigue
It is defined as, “the reduction of the fatigue strength due to the presence of cor-
rosive environment”. Corrosion fatigue occurs due to the combined action of tensile
and compressive stress alternatively. Fatigue occurs at lower stress in corrosive
environment.
Figure 9.
Schematic representation of stress corrosion.
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7.10 Fretting corrosion
Fretting is a wear phenomenon enhanced by corrosion. It involves wear of a

metal or alloy when in contact with another solid material in dry or humid air.
Fretting is the result of abrasive wear surface oxide films, which form a contacting
surfaces under load in atmospheric air which is shown in Figure 10. The factors
which affect fretting corrosion are:
• Magnitude of relative motion
• Temperature
• Environment
• Metallurgical factors
Due to slight motion such as vibration, surface oxide and underlying metal, gets
spoiled. The metal particles as a result of wear get oxidized to hard oxides which act
as an additional abrasive medium. Further, the motion grinds the oxides particles
thus causing wear.
Figure 10.
Schematic representation of fretting corrosion.
Figure 11.
Schematic representation of cavitation corrosion.
7.11 Cavitations corrosion
It is a special type of erosion corrosion which is caused due to the formation

of vapor bubbles in a corrosive environment near a metal surface and when the
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bubbles collapse, attack arises for example, hydraulic turbulence, ship propellers,
etc. It is similar to pitting corrosion but the surface is rough and has many close
spaced pits (Figure 11).
8. Factors influencing corrosion
The extent and rate of corrosion depend on nature of the metals and the
environments.
8.1 Nature of the metal
1. Position of metals in EMF series
2. Overvoltage
3. Relative area of anodic and cathodic parts of the metal
4. Purity of the metal
5. Physical nature of the metal
6. Nature of the surface film
7. Solubility of products
8. Volatile corrosion products.
8.2 Nature of the environment
• Temperature range
• Humidity of air
• Impurities in water
• Presence of suspended particles in atmosphere
• Influence of pH
• Nature of dissolved gases, dissolved salts, pollutants, etc.
• Conductance of the corroding medium
• Formation of oxygen concentration cell
• Flow velocity of process steam
• Polarization of electrodes.
9. Factors controlling corrosion rate
Certain factors tend to accelerate the action of a corrosion cell which includes
the establishment of well-defined locations on the metal surface for the anodic
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and cathodic reactions. Metals having a more positive (noble) potential in the
galvanic series will tend to extract electrons from a metal which is in a more
negative (base) position in the series and hence accelerate its corrosion when in
contact with it [23]. Aggressive ions such as chloride tend to prevent the forma-
tion of protective oxide films on the metal surface and thus increase corrosion.
9.1 Corrosion rate
The rate of corrosion is expressed based on the loss per unit time. The rate at
which the attack takes place is of prime importance and is usually expressed in one
of the two ways:
• Weight loss per unit area per unit time, usually mdd (milligrams per square
decimeter per day).
• Decrease in thickness per unit time, that is, rate of penetration or the thickness
of metal lost. This may be expressed in American units, mpy (mils per year) or
in metric units or mmpy (millimeters per year).
10. Corrosion control methods
Corrosion is destructive and silent operating processes. It poses problems to

big as well as small industries. Since corrosion is inevitable to eliminate but can be
minimized by adopting certain anticorrosion method rather than preventing it [24].
The practical methods available for the protection of metal against corrosion are
diverse. They may be broadly based on,
• Modification of metal
• Modification of design
• Modification of corrosive environment
• Modification of metal environment potential
• Use of inhibitors
• Modification of surface
These methods can be used individually or in combination.. One of the best

known methods of corrosion protection is using corrosion inhibitors instead of
using the various methods to avoid or prevent destruction or degradation of metal
surface. Because using inhibitors is following stand up due to low cost and practice
method [25, 26].
11. Inhibitors
An inhibitor is a chemical substance or combination of substances which when

added in very low concentrations in a corrosive environment effectively prevents or
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reduces corrosion without significant reaction with the components of the envi-
ronment. Concentrations of corrosion inhibitors can vary from 1 to 15,000 ppm
(0.0001 to 1.5 wt %). Inhibitors play a vital role in closed environmental systems
that have good circulation so that an adequate and controlled concentration of
inhibitor is ensured [27]. Such conditions can be met, for instance in cooling water
recirculation systems, oil production, oil refining, and acid pickling of steel compo-
nents. One of the more recognizable applications for inhibitors is in antifreeze for
automobile radiators. Inhibitors may be organic or inorganic compounds and they
are usually dissolved in aqueous environments [28].
11.1 Definition of inhibitor
An inhibitor is a substance which when added to an environment in small

concentration minimizes the loss of metal, reduces the extent of hydrogen
embrittlement, protects the metal against pitting, reduces over pickling and
acid fumes resulting from excessive reaction between the acid and basic met-
als and reduces acid consumption. They reduce corrosion by either acting as a
barrier by forming an adsorbed layer or retarding the cathodic, the anodic or
both processes [10]. A schematic representation of inhibitor process is shown in
Figure 12.
Any corrosion retardation process or the reduction in the oxidation rate
of the metal by addition of a chemical compound to the system is caused by
corrosion inhibitors. Inhibitors are often easy to apply and offer the advantage
of in-situ application without causing any significant disruption to the process.
The use of corrosion inhibitors is one of the best methods of combating
corrosion [11].
In order that they can be used effectively, three factors must be considered, namely:
• Identification of the corrosion problems.

Generally, the components of a corrosion cell (anode, cathode, electrolyte and
electronic conductor) may be affected by corrosion inhibitors in order to reduce
corrosion. The inhibitor may cause:
• Anodic inhibition (increasing the polarization of the anode)
• Cathodic inhibition (increasing the polarization of the cathode)
• Resistance inhibition (increasing the electrical resistance of the circuit while

forming a thin or thick deposit on the surface of the metal)
• Diffusion restriction (restricting the diffusion of depolarizers, e.g., DO).
However there are several factors to be considered when choosing an inhibitor.
• Cost of the inhibitor.
• Toxicity of the inhibitor can cause ill effects on human beings and other living
species.
• Availability of the inhibitor determines the selection of it.
• Inhibitor should be environment friendly.
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In order to avoid or reduce the corrosion of metallic materials, inhibitors used in

cooling system must satisfy the following criteria
• It must give good corrosion protection at a very low concentration of inhibitor.
• It must protect all exposed materials from the attack of corrosion.
• It must remain efficient in extreme operating conditions (higher temperature

and velocity).
• In case of an under or over dosage of inhibitor, corrosion rate should not increase
drastically.
• The inhibitor or reaction products of the inhibitor should not form any deposits
on the metal surface particularly at locations where heat transfer takes place.
• It should suppress both uniform and localized corrosion.
• It should have long range effectiveness.
• It should not cause toxicity and pollution problems.
11.2 Definition of inhibition
One of the extensively studied topics in the field of corrosion is inhibition.

Inhibition is a process of preventive measure against corrosive attack on metallic
materials. Chemical compounds may be used which, when added in small concen-
trations to an aggressive environment, are able to decrease corrosion of the exposed
metal [12].
11.3 Corrosion inhibitors
Corrosion inhibitors can be any forms (solids, liquids and gases). Based
on the solubility or dispersibility in fluids corrosion inhibitors are selected
which are to be inhibited. Corrosion inhibitors have been found to be effective
and flexible means of corrosion mitigation. The use of chemical inhibitors to
decrease the rate of corrosion processes is quite variable. Corrosion inhibitors
are used in oil and gas exploration and production, petroleum refineries, chemi-
cal manufacturing, heavy manufacturing, water treatment and product additive
Figure 12.
Schematic representation of inhibition process.
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industries [29]. In the oil extraction, processing and chemical industries, cor-
rosion inhibitors have always been considered to be the first line of defense. A
great number of scientific studies have been devoted to the subject of corrosion
inhibitors [30, 31].
11.4 Role of inhibitors
Organic and inorganic compounds constitute a large class of corrosion inhibi-

tors, which as a general rule; affect the entire surface of a corroding metal when
present in sufficient concentration. Most of the organic/inorganic compounds
containing elements of groups V B, VI B or functional groups of the type amine,
carbonyl and alcoholic groups are more effective corrosion inhibitors. The inhibi-
tor is adsorbed on the entire metal surface of the corroding metal and so prevents
attack from the corrosion. Organic inhibitors are adsorbed on the metals surface
[32]. The inhibitors may be considered as two fundamental types, they are, those
which form a protective barrier film on anodes or cathodes by reaction between the
metal and the environment. This type of inhibitors function in neutral or in some
cases, alkaline solution in which the main cathodic reaction is an oxygen reduc-
tion reaction in which the corroding metal surface is covered by a film oxide or
hydroxide.
Another type is initially adsorbed directly onto the metal surface by interaction
between surface charges and ionic and/or molecular dipole charges. This division of
inhibitor types results principally from the pH of the solution where they operate.
Inhibitors must be present in a minimum concentration for them to be fully effec-
tive. This is very common with anodic inhibitors.
The efficiency of organic inhibitors can be improved in the presence of
certain halogen ions. Halogen ions are also known to inhibit corrosion to some
extent in acid solutions. The efficiency of the corrosion inhibition is in the order;
I- > Br- > Cl-. Fluoride does not show inhibition characteristics. Synergism of
halogen ions can be attributed to the fact that the metal adsorbs halogen ions whose
charge shifts the surface in a negative direction, thereby increasing adsorption of
the cationic organic inhibitor. Being able to discover possible compounds that can
be used as corrosion inhibitors requires a lot of hard work, innovation and labora-
tory analysis/synthesis [33].
Certain halogen ions present in the organic inhibitors are known to inhibit
corrosion to some extent in acid solutions. The efficiency of the corrosion inhibition
is following in the order of I− > Br− > Cl−. Fluoride does not shows any inhibition
characteristics. Synergism of halogen ions can be attributed to the fact that the
metal adsorbs halogen ions whose charge shifts the surface in a negative direction,
thereby increasing adsorption of the cationic organic inhibitor.
11.5 Classification of corrosion inhibitors
Corrosion inhibitors are briefly classified (Figure 13) as follows,
11.5.1 Based on electrode process
11.5.1.1 Anodic inhibitors
An anodic inhibitor increases the anodic polarization and hence moves the
corrosion potential to the cathodic direction and hence also called as passivat-
ing inhibitors. Anodic inhibitors such as chromates, phosphates, tungstates and
other ions of transition elements with high oxygen content are those that stifle the
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Figure 13.
Classification of corrosion inhibitors.
corrosion reaction occurring at the anode by forming a sparingly soluble compound

with a newly produced metal ion. They are adsorbed on the metal surface forming
a protective film or barrier, thereby reducing the corrosion rate. Anodic inhibitors
build a thin protective film along the anode and increasing their potential and thus
slow down the corrosion reaction [34].
Although, this type of control is affected, yet it may be dangerous since severe
local attack can occur, if certain areas are left unprotected by depletion of the
inhibitors. A number of inorganic inhibitors such as orthophosphates, silicates,
etc. fall under anodic type. Even though anodic inhibitors are widely used, a few of
them have some undesirable property. If such inhibitors are used in very low con-
centrations, they cause stimulation of corrosion such as pitting and for this reason
anodic inhibitors are denoted as dangerous.
There are two types of passivating inhibitors.
• The oxidizing anions such as chromates, nitrites and nitrates that can passivate
steel in the absence of oxygen.
• The non-oxidizing ions such as phosphates, tungstates and molybdates that

require the presence of oxygen to passivate steel.
In general, passivation inhibitors can actually cause pitting and accelerate corro-
sion when concentrations fall below minimum limits. For this reason, it is essential
to monitor the inhibitor concentration.
11.5.2 Cathodic inhibitors
Cathodic inhibitors reduce corrosion by slowing the reduction reaction rate of

the electrochemical corrosion cell. This is done by blocking the cathodic sites by
precipitation. Cathodic inhibitors are effective when they slow down the cathodic
reaction. Elements As, Bi and Sb are referred to as cathodic poisons which reduce
the hydrogen reduction reaction rate and lower the overall corrosion rate. Removal
of oxygen from the corrosive environment will significantly decrease the corrosion
rate. This can be done through
• The use of oxygen scavengers such as sodium sulfite and hydrazine which react
with the oxygen and remove it from the solution
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• Vacuum de-aeration or
• Boiling to lower the dissolved oxygen concentrations.
Cathodic inhibitors shift the corrosion potential to the anodic direction. [35, 36]
Here the cations migrate towards the cathode surfaces where they are precipitated
chemically or electrochemically and thus block these surfaces. The inhibiting action
of cathodic inhibitors takes place by three mechanisms,
• Cathodic poisons: The cathodic reduction process is suppressed by impeding

the hydrogen recombination and mode of protection discharge but increase the
tendency of the metal to be susceptible to hydrogen induced cracking.
• Cathodic precipitates: Compounds such as calcium, magnesium will precipitate

as oxides to form a protective layer which acts as a barrier on the metal surface.
• Oxygen scavenger: These compounds react with oxygen present in the system
to form a product and reduce corrosion. For example, As3+ and Sb3+ on dissolu-
tion of Fe in acids.
11.5.2.1 Mixed inhibitors
These inhibitors retard both the anodic and cathodic processes involved in the cor-
rosion process and are therefore called mixed inhibitors [37]. They are typically film
forming compounds that cause the formation of precipitates on the surface blocking
both anodic and cathodic sites indirectly. Anodic inhibitors are, for the most part, dan-
gerous inhibitors, especially if their concentrations are too less. But cathodic inhibitors
are generally safe. Mixed inhibitors are less dangerous than pure anodic inhibitors, and
in number of cases they may not increase the corrosion intensity. The most common
inhibitors of this category are the silicates and the phosphates. Such inhibitors will have
the more advantage that they control both the cathodic and anodic corrosion reactions.
11.5.3 Based on environment
11.5.3.1 Acidic environment inhibitors
11.5.3.2 Inorganic inhibitors
The compounds such as As2O3, Sb2O3 have been reported as inhibitors in acid
media. In this case, the protection is due to the reduction of electro positive ions and
deposition on the metal surface and lowering of the over voltage of main cathodic
depolarization reaction [38]. Recently it is shown that the addition of heavy metal
ions such as Pb2+, Ti+, Mn2+ and Cd2+ is found to inhibit corrosion of iron in acids.
11.5.3.2.1 Organic inhibitors
Organic compound containing oxygen, nitrogen, sulfur with multiple bonds

have been reported as good corrosion inhibitors. Many organic inhibitors such as
amines, aldehydes, alkaloids, nitro and nitroso compounds have been studied and
tried as corrosion inhibitors [39]. Organic inhibitors can be anodic, cathodic and
mixed type based on its reaction at the metal surface and potential. These are effec-
tive depending upon its size, carbon chain length, aromaticity, conjugation and
nature of bonding atoms [40].
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11.5.3.3 Alkaline inhibitors
Metals, which form amphoteric oxides, are prone to corrosion in alkaline solu-
tions. Many organic compounds are often used as inhibitors for metals in basic solu-
tions [41]. Compounds such as thiourea, substituted phenols, naphthol, β-diketone,
etc., have been used as effective inhibitors in basic solutions due to the formation of
metal complexes.
11.5.3.4 Neutral inhibitors
Inhibitors which are effective in acidic solutions do not function effectively in

neutral solutions, since the mechanism is different in the two solutions [42–44].
In neutral solutions, the interaction of inhibitors with oxide covered metal surface
and prevention of oxygen reduction reaction at the cathodic sites takes place. Such
inhibitors protect the surface layers from aggressiveness. Some surface active
chelating inhibitors have been found to be efficient inhibitors in near-neutral
solutions [45].
11.5.4 Based on mode of protection
11.5.4.1 Chemical passivators
Substances which usually have a sufficiently high equilibrium potential (redox

or electrode potential) and sufficiently low over potential decrease corrosion rate on
attainment of passivity and are called chemical passivators [46].
Example, nitrites are used as inhibitors for antifreeze cooling waters. Chromates
are mostly used as inhibitors for recirculating cooling waters. Zinc molybdate is
used as an inhibiting pigment for paints.
11.5.4.2 Adsorption inhibitors
These represent the most widely used class of inhibitors. In general, they are
organic compounds which get adsorbed on the metal surface and provide a blan-
keting effect over the entire surface, that is, both in cathodic and anodic cases.
Generally they effect both cathodic and anodic reactions equally, but in many
cases the effect may not be equal. These are commonly used in the acid pickling of
hot rolled products in order to remove the black mill scale and are thus known as
pickling inhibitors [47–49].
Examples: Compounds containing lone pairs of electrons such as nitrogen
atoms in amines, quinolines, sulfur atoms in thio compounds and oxygen atoms in
aldehydes.
11.5.4.3 Film forming inhibitors
In contrast to the adsorption inhibitors which form the straight forward

adsorbed film of the inhibiting species, many substances called film forming
inhibitors, appear to stop corrosion by forming a blocking or a barrier film of a
material other than the actual inhibiting species itself. Such materials tend to be
specific either to the cathode or to the anode. Zinc and calcium salts are the most
common examples of cathodic film forming inhibitors. Benzoate is the common
example of anodic film forming inhibitors, which inhibit corrosion during
voyages [50].
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11.5.4.4 Vapor phase inhibitors
Atmospheric corrosion of metals in closed spaces as in parcels during storage

and shipment can be prevented by the use of certain substances called vapor phase
inhibitors also called as volatile inhibitors [51–56]. These are substances of low but
significant vapor pressure. The vapor comes in contact with the surface of the metal
and the adsorption of the inhibitor takes place. The moisture then hydrolyses it and
releases protective ions which have corrosion inhibiting properties. Figure 14 shows
the schematic representation vapor phase inhibitors.
Examples,
Dicyclohexylamine chromate and benzotriazole for protecting copper.
Phenyl thiourea and cyclohexylamine chromate for brass.
Dicyclohexylamine nitrite for ferrous and nonferrous part.
11.5.4.5 Volatile inhibitors or vapor phase inhibitors
Volatile corrosion inhibitors (VCIs) are compounds which transferred in a closed

environment to the site of corrosion by volatilization from a source (Figure 15).
If the corrosion product is volatile, it volatilizes as soon as it is formed, thereby leav-
ing the underlying metal surface exposed for further attack. This causes rapid and
continuous corrosion leading to excessive corrosion. Example, Molybdenum oxide
(MoO3), the oxidation corrosion product of molybdenum is volatile. In closed vapor
process (shipping containers), volatile solids such as salts of dicyclohexylamine, cyclo-
hexylamine and hexamethylene amine are used as volatile corrosion inhibitors [52].
11.5.4.6 Synergistic inhibitors
These are single inhibitor which is used in cooling water systems. More often, a
combination of inhibitors (anodic and cathodic) is used to obtain better corrosion
protection properties [56]. Examples include chromate-phosphates, polyphosphate-
silicate, zinc-tannins, and zinc-phosphates.
11.5.4.7 Precipitation inhibitors
These are compounds that forms precipitates on the metal surface, thereby
providing a protective film. The most common inhibitors of this category are the
silicates and the phosphates. For example, Sodium silicate, is used in many domestic
water softeners to prevent the occurrence of rust [57, 58].
Figure 14.
Schematic representation of vapor phase inhibitors.
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Figure 15.
Schematic representation of volatile inhibitors.
11.5.4.8 Green corrosion inhibitors
There is no clear and accepted definition of “environmentally friendly” or

“green” corrosion inhibitors. In practice, corrosion inhibition studies have become
oriented towards human health and safety considerations. For this purpose
recently, the researchers have been focused on the use of eco-friendly compounds
such as plant extracts, expired nontoxic medicines, etc. which contains many
organic compounds [59–61]. Amino acids, alkaloids, pigments and tannins are used
as green alternatives for the toxic and hazardous compounds. Due to biodegrad-
ability, eco-friendliness, low cost and easy availability and the extracts of some
common plants and medicinal plant and its products have been studied as corrosion
inhibitors for various metals and alloys under different environmental conditions.
11.6 Mechanism of corrosion inhibition
The mechanism of the inhibition process of the corrosion inhibitors under

consideration is mainly due to the adsorption. The phenomenon of adsorption is
influenced by the nature and surface charge of the metal and by chemical structure
of inhibitors. The surface charge of the metal is due to the electrical field which
emerges at the interface on immersion in the electrolyte [62–64].
Inhibition usually results from one or more of the following mechanisms
• Adsorption of corrosion inhibitors onto metals

The inhibitive performance is usually depends on the fraction of the surface
covered, θ with adsorbed inhibitor. But, at low surface coverage (θ < 0.1), the
effectiveness of adsorbed inhibitor species in retarding the corrosion reactions may
be greater than at high surface coverage.
• Presence of surface charge on the metal

Adsorption of inhibitor on the metal surface may be due to dipoles of the
adsorbed species or electrostatic force of attraction between ionic charges and the
electric charge on the metal at the metal/solution interface.
• Effect of functional group and structure

Usually, when the metal contains vacant electron orbitals of low energy such as
transition metals. Inhibitors can also bond to metal surfaces by electron transfer to
the metal to form a coordinate type of bond. Electron transfer from the adsorbed
18
species is favored by the presence of relatively loosely bound electrons. Example:

Anions and neutral organic molecules containing lone pair of electrons or electron
systems associated with multiple bonds especially triple bonds or aromatic rings.
The electron density at the functional group is directly proportional to the inhibi-
tive efficiency in a series of related compounds.
• Inhibitor and water molecules interaction

Adsorbed water molecule are removed from the metal surface due to displace-
ment reaction of adsorbed inhibitor molecules and increases the size of hydrocarbon
part of inhibitor, which leads to decreasing solubility and increasing adsorption abil-
ity. This is consistent with the increasing inhibitive efficiency observed at constant
concentrations with increasing molecular size in a series of related compounds.
• Interaction between adsorbed inhibitor species

Lateral interactions between adsorbed inhibitor species may become signifi-
cantly increases the surface coverage and the adsorbed species. These interactions
either attractive or repulsive. If attractive interactions occur between molecules
containing large hydrocarbon components (e.g., n-alkyl chains), may the chain
length increases. Then the increasing Van der Waals attractive force between the
adjacent molecules leads to stronger adsorption at high coverage.
• Adsorbed inhibitors reaction

The adsorbed corrosion inhibitor may react usually by chemical or electro-
chemical reduction to form a product that may exhibit inhibitive action. A process
of added small quantity of substance is called as primary inhibition and that due to
the reaction product is secondary inhibition. In these cases, the inhibitive efficiency
may increase or decrease with time, it depends on the extent of secondary inhibi-
tion is more effective than the primary inhibition. For example, sulfoxides can be
reduced to sulfides which are more efficient inhibitors.
• Diffusion barrier formation

The absorbed inhibitor molecules may form a surface layer that acts as a physical
barrier to the diffusion of ions or molecules and to or from the metal surface, and
hence retard the rate of corrosion reactions. A surface film of these types of inhibi-
tors affects both anodic and cathodic reactions.
• Blocking of reaction sites

The blocking decreases the number of metal atoms at which corrosion reactions
can occur. During this, mechanisms of the reactions are not affected, and the Tafel
slopes of the polarization curves remain unaffected [65].
• Electrode reactions
Corrosion reactions involve the formation of adsorbed intermediate molecules
with surface metal atoms. The adsorbed inhibitors will forbid the formation of
these adsorbed intermediates, but the electrode processes may proceed by alter-
native paths through intermediates containing the inhibitor. In this process, the
inhibitor act as catalyst and remain unchanged. Such reactions of inhibitor are
characterized by an increase in the Tafel slope of the anodic dissolution of the
metal. Inhibitors may also retard the rate of hydrogen evolution on the metals by
affecting the mechanism of the reaction [66]. This effect has been observed on iron
in the presence of inhibitors such as phenylthiourea, aniline derivatives, benzalde-
hyde derivatives and pyridinium salts [67].
19
• Electrical double layer alteration

The adsorption of ions or species that can form ions on metal surfaces will change
the electrical double layer at the metal/solution interface, and this will affect the rates
of the electrochemical reactions [68]. The adsorption of cations such as quaternary
ammonium ions and protonated amines makes the potential more positive in the
plane of the closest approach to the metal ions from the solution. This positive poten-
tial shift hinders the discharge of the positively charged hydrogen ions. These effects
have been observed with sulfosalicylate ions and the benzoate ions [69, 70].
Conclusion
• Corrosion is a natural process which reduces the binding energy in metals and
degrades the useful properties of materials.
• The end result of corrosion involves a metal atom being oxidized, whereby it
loses one or more electrons.
• The corrosion manifests itself as a break-up of bulk metal to metal powder.

Corrosion.
• Corrosion inhibitors are a great effective method of preventing corrosion.
• The knowledge of the method of the action, facilitates the choice of the inhibi-
tors, improves efficiency, avoids the process is impaired and side effects.
• It is important in the choice of inhibitor whatever may be the method, ascertain

the subsequent effects of this towards the environment.
• The environmental friendly inhibitors have shown excellent results, outper-

forming conventional inhibitors.
20
21
References
[1] Jones T. International Iron and [12] Bentiss F, Lagrenee M, Traisnel M,

Steel Institute; steel industry and Hornez JC. Corrosion. 1999;55:968
the environment: Technical and
management issues. UNEP/Earthprint. [13] Yurt A, Balaban A, Kandemir SU,
1997 Bereket G, Erk B. Materials Chemistry
and Physics. 2004;85:420
[2] Boffardi BP. Corrosion inhibitors
in the water treatment industry. In: [14] Zaim S, Muralidharan S, Iyer S,
ASM Handbook. Vol. 13A. OH: ASM Muralidharan B, Vasudevan T. British
International, Materials Park; 2003 Corrosion Journal. 1998;33:297
[3] Holcomb R. Corrosion in [15] Cisse MB, Zerga B, El Kalai F,

supercritical water: Ultrasupercritical Touhami ME, Sfaira M, Taleb M, et al.
environments for power production. Surface Review and Letters. 2011;18:303
In: ASM Handbook. Vol. 13C. OH: ASM
International, Materials Park; 2006 [16] Musa AY, Jalgham RTT, Mohamad
AB. Corrosion Science. 2012;56:176
[4] Shreir LL, Jarman RA, Burnstein GT.
Principles of Corrosion and Oxidation. [17] Nataraja SE, Venkatesha TV, Tandon
Vol. 1. 1994 HC. Corrosion Science. 2012;60:214
[5] Geethamani P, Kasthuri PK. The [18] Thomas JGN. The Mechanism of

inhibitory action of expired asthalin Corrosion. Oxford, UK: Butterworths
drug on the corrosion of mild steel Heinemann; 1994
in acidic media: A comparative
study. Journal of the Taiwan [19] Geethamani, Kasthuri. Physical
Institute of Chemical Engineers. chemistry. Cogent Chemistry.
2016;63(4):490-499 2015;1:1091558
[6] Roberge PR. Corrosion Engineering [20] Ash M, Ash I. Handbook of

Principles and Practice. New York: Corrosion Inhibitors. Texas, Houston,
McGraw-Hill; 2008 USA: NACE; 2001
[7] Geethamani P, Kasthuri PK, [21] Schweitzer PA. Fundamentals of

Aejitha S. Journal of Applied Metallic Corrosion. 2nd ed. London:
Chemical Science International. CRC Press; 2007
2015;3(4):151-157
[22] Geethamani P, Kasthuri PK, Aejitha
[8] Geethamani P, Kasthuri PK, Aejitha S. IJCPS. 2015;3(1):1442-1448
S. Chemical Science Review and Letters.
2014;2(6):507-516 [23] Sastri VS. Corrosion Inhibitors:
Principles and Applications. Weinheim,
[9] Geethamani P, Kasthuri PK, Aejitha Germany: Wiley-VCH; 1998
S. Elixir Corrosion & Dye 762014.
pp. 28406-28410 [24] Mercer AD. Corrosion Inhibition:
Principles and Practice. Oxford, UK:
[10] Bentiss F, Traisnel M, Lagrenee M. Butterworths Heinemann; 1994
Corrosion Science. 2000;42:127
[25] Sharma SK. Front Matter, in Green
[11] Sharma S, Chaudhary RS. Bulletin Corrosion Chemistry and Engineering:
of Electrochemistry. 2000;16:267 Opportunities and Challenges.
22
Weinheim, Germany: Wiley-VCH Verlag [38] El Rehim SSA, Ibrahim MAM,

GmbH & Co. KGaA; 2011 Khaled KF. Corrosion Prevention &
Control. 1999;46:157
[26] Aejitha S, Kasthuri PK, Geethamani
P. Chemical Science Review and Letters. [39] Du T, Chen J, Cao DZ, Cao
2014;2(7):566-573 C. Bulletin of Electrochemistry.
1997;13:13
[27] Kelly RG, Scully R, Shoesmith
DW, Buchheit RG. Electrochemical
[40] Ita BI, Offiong OE. Journal of Pure
Techniques in Corrosion Science and
and Applied Science. 1999;5:497
Engineering. New York: Marcel Dekker
press; 2002
[41] Umoren SA, Obot IB, Odewunmi
[28] Bailey JC, Porter FC, Pearson NA. Journal of Dispersion Science and
AW, Jarman RA. Aluminum and Technology. 2014:922887
Aluminum alloys. In: Corrosion: Metal/
Environment Reactions. 3rd ed. London: [42] Mistry BM, Patel NS, Sahoo S,
Springer; 1994 Jauhari S. Bulletin of Materials Science.
2012;35:459
[29] Muralidharan S, Iyer S. Journal of
the Electrochemical Society of India. [43] Khaled KF. Electrochimica Acta.
1999;48:113 2008;53:3484
[30] Hariharaputhran R, Subramanian [44] Umoren SA, Li Y, Wang FH.

A, Antony AA, Sankar PM, Gopalan A, Corrosion Science. 2010:52, 2422
Vasudevan T, Venkatakrishna S, Iyer S.
British Corrosion Journal. 1998;33:214 [45] Aejitha S, Kasthuri PK, Geethamani
P. Indian Journal of Applied Research.
2014;4(12):218-220
P. Asian Journal of Chemistry.
2016;28(2):307-311
[46] Ebenso EE, Arslan T, Kandemirli F,
[32] Quraishi MA, Rawat J, Ajmal Love I. International Journal of
M. Journal of the Electrochemical Quantum Chemistry. 2010;10:2614-2636
Society of India. 2000;49:35
[47] Sorensen PA, Weinell CE, Dam-
[33] Lazarova EM, Yankova TN, Johansen K, Kiil S. Journal of Coating
Neykov GD. Bulgarian Chemical Technology and Research. 2010;7:773
Communications. 1996;28:647
[48] Aejitha S, Kasthuri PK,
[34] Al-Mayouf AM, Al-Suhybani Geethamani. International Journal of
AA, Al-Ameery AK. Desalination. Chemical Sciences. 2015;13(1):38-52
1998;116:25
[35] Touham F, Aouniti A, Abed Y,
P. International Journal of Advanced
Hammouti B, Kertit S, Ramdani
Technology In Engineering Science.
A. Bulletin of Electrochemistry.
2015;3(5):25-30
2000;16:245
[36] El-Rehim SS, Ibrahim AM, [50] Abdallah M, AL Jahdaly BA.

Khaled KF. Journal of Applied International Journal of Electrochemical
Electrochemistry. 1999;29:593 Science. 2015;10:9808
[37] Bastidas JM, Polo JL, Cano E, [51] Singh AK, Ji G, Prakash R, Ebenso
Torres CL. Journal of Materials Science. EE, Singh AK. International Journal of
2000;3:2637 Electrochemical Science. 2013;8:9442
23
[52] Singh A, Singh AK, Quraishib MA. [66] Jain T, Chowdhary R, Arora P.
The Open Electrochemistry Journal. Bulletin of Electrochemistry. 2005;21:1
2010;2:43
[67] Umoren SA, Obot IB, Obi-Egbedi
[53] Ansari KR, Quraishi MA, Prashant, NO. Journal of Materials Science.
Ebenso EE. International Journal of 2008;44:274
Electrochemical Science. 2013
[68] Umoren SA, Solomon MM, Eduok
[54] Umoren SA, Obot IB, Gasem ZM. UM, Obot IB, Israel AU. Journal of
Ionics. 2014:1280 Environmental Chemical Engineering.
2014;2:1048
[55] Verma CB, Quraishi MA, Singh
A. Journal of the Taiwan Institute of [69] Vinodkumar KP, Sethuraman MG.
Chemical Engineers. 2015;49:229 Transactions of the SAEST (Society
for Advancement of Electrochemical
[56] Fouda AS, Farahat MM, Abdallah Science and Technology). 1999;34:2
M. Research on Chemical Intermediates.
2014;40:1249 [70] Yoshida T, Namba O, Chen L, Okuda
T. Chemical & Pharmaceutical Bulletin.
[57] Hari Kumar S, Karthikeyan 1990;38:1113
S. Journal of Materials and
Environmental Science. 2013;4:675
[58] Karthik G, Sundaravadivelu

M. ISRN Electrochemistry. 2013:10
[59] Megalai SM, Manjula P,

Manonmani KN, Kavithaa A, Babyd
N. Electrochimica Acta. 2012;30:395
[60] Obi-Egbedi NO, Obot IB, Eseola

AO. Arabian Journal of Chemistry.
2014;7:197
[61] Singh P, Quaraishi MA. Indian

Journal of Life Sciences. 2012;7:12270
[62] Singh AK, Quraishi MA. Journal of

Materials and Environmental Science.
2010;1:101
[63] Sudhish KS, Quraishi MA,

Ebenso EE. International Journal of
Electrochemical Science. 2011;6:2912
[64] Junedi S. International Journal

of Electroanalytical Chemistry.
2012;7:3543
[65] Suraj B, Ade NV, Shitole S, Lonkar

M. International Journal of ChemTech
Research. 2014;6:974
24
Chapter 02
Structural Effect in Ionic Liquids

Is the Vital Role to Enhance the
Corrosion Protection of Metals in
Acid Cleaning Process
Perumal Kannan and Anitha Varghese
Abstract
Various kinds of methods have been developed and used to overcome differ-
ent types of corrosion throughout the world. One possible and easy way to avert
corrosion is use of an inhibitor. An inhibitor can be applicable to any type of metal
irrespective of medium (acid, alkaline, and neutral). Still, several inhibitors are
emerging day by day in the corrosion world and most of them are heterocyclic
compounds. In this respect, ionic liquid is attracting the attention of the research
community. Because of ionic liquid’s salient feature of melting and boiling points, it
is being employed as a solvent in various types of reaction. In recent years, synthe-
sizing and functionalizing the structure of ionic liquids in such a way to attain the
desire requirement have become significant key factors in the field. By altering the
cationic part or anionic part (halogen group), the chemical property of ionic liquids
will change considerably. Besides, it will enhance the tendency of the electron-
donating nature of the cationic part. This behavior equips them to be employed in
the field of corrosion. While it meets the metal surface in the aggressive medium it
will be attracted, leads to better surface protection from metal dissolution.
Keywords: ionic liquids, inhibitor, electrochemical analysis, structure effect,

surface protection
1. Introduction
Corrosion is defined as the destruction or deterioration of metal because of

its reaction with the environment. The age of corrosion is as old as the earth. It is
known that it had different names at different time. However, carbon steel is prone
to corrosion in an acid environment, which causes material damage and increases
downtime costs in industry. Hence, a periodical cleaning and descaling process
is performed using inorganic acids to remove the corrosion products. Due to acid
aggressiveness, inhibitors were used to reduce metal dissolution [1]. The study of
corrosion inhibition and mechanistic processes is a key area of research [2]. A large
number of organic compounds having nitrogen, oxygen, sulfur, and phosphorus
were synthesized to reduce the corrosion of metal in aggressive medium. The litera-
ture also revealed that the organic compounds containing π-bonds, electron density
on the heteroatom, planner structure, and aromaticity have supported the effects of
adsorption inhibitor molecules on the metal surface.
1
Over the last few decades, several types of organic compounds have been
synthesized and used as corrosion inhibitors to mitigate the corrosion process in
different environments [3–5]. More recently, ionic liquids have been recognized as
a better corrosion inhibitor for metal corrosion in an acid environment [6–9]. Due
to their unique properties such as non-flammability, very low vapor pressure, and
boiling and melting point, ionic liquids can be considered to be good corrosion
inhibitors. Recently, the software development in the theoretical analysis of mol-
ecules to describe plausible corrosion mechanisms has increased considerably [10].
Ionic liquids are salts, a combination of (organic) cation and (organic/inorganic)
anion as a liquid form at room temperature; in other words, they are called organic
salts, which have melting points below room temperature. The electronic configura-
tion of imidazolium (heterocyclic) depends on the heteroatom of the main carbon
skeleton and furthermore causes the interaction between the metal surface and
ionic liquid [11]. The significant features of its physical and chemical properties
such as liquid state, low vapor pressure, viscosity, and inflammability place ionic
liquids in the field of corrosion as inhibitors. The various kinds of cation and anion
govern the possibility to have property that required. Many ionic liquids are used as
solvents for batteries and organic reactions. The application of ionic liquids in the
corrosion field was first reported in 1996. The ionic liquid dissociation pattern gave
a clue to the adsorption mode on the metal surface. The adsorption combination of
ionic liquids depends on the metal nature and temperature.
The literature shows that inhibition effect mainly depends on alkyl chain length
substitution on the N1/N2 atoms. A heterocyclic compound containing a longer
alkyl chain length would offer better corrosion protection [12]. However, many
studies have implied that increasing the carbon chain length on N atoms does not
necessarily increase the inhibition effect [13, 14]. Murulana [15] supported the
above fact and described that not only does increasing alkyl chain length in the N
atom increase protection efficiency but also other atoms close by will enhance the
protection effect. The main reason for surface protection is the induction of alkyl
substitution on the cationic part of the ionic liquid.
2. Structural impact of ionic liquid in various aspects
2.1 Implication of ionic liquid alkylation in electrochemical studies
Since ionic liquids possess cations and anions, they are adsorbed onto the metal
surface anodes and cathodes, respectively. Because of this, metal dissolution con-
siderably decreases. The adsorbing efficiency of the inhibitor purely depends on the
electron-donating ability of the ionic liquid active site [16]. Likhanova et al. [17]
explained in his research that the electrochemical parameter showed the alkylation
of longer chain length on imidazolium and pyridinium and significantly improved
charge transfer resistance. Additionally, inhibitor concentration also improved metal
dissolution at the metal/solution interface. In the presence of ionic liquid, the anodic
and cathodic reactions were affected. ImDC18 Br and PyC18 Br inhibit the anodic
area more than the cathodic area, because of the adsorption between HSO4− and Br−,
and consequently, the cathodic reaction is also arrested. The increased polarization
resistance indicates the adsorption of ionic liquid on the metal surface to block the
active area for the mitigation of corrosion. This efficiency has increased due to the
presence of ethylbenzene at the N3 atom of the imidazole ring. Delocalization of
the electron is much favored in the 3-ethylbenzene form of imidazolium ionic liquid
than in the acetyl imidazolium form [18]. On the other hand, the (pyridiazinium
ionic liquid, S1) 1-(6-ethoxy-6-oxohexyl) pyridazin-1-ium bromide bears a higher
2
Structural Effect in Ionic Liquids Is the Vital Role to Enhance the Corrosion Protection of Metals…
charge transfer resistance value than the (S2) 1-(2-bromoacetyl) pyridiazinium

bromide, which is advocated for reasonable corrosion protection at elevated tem-
peratures. The causes behind better corrosion protection were increased frequency
of relaxation [19] as the concentration and temperature increased.
Long alkyl chain length improves the relaxation time at the interface of the
metal/ solution interface. Some authors [20] have reported the influence of nega-
tive ions of ionic liquids in electrochemical studies. According to Martin et al.,
corrosion rate decreased with an ionic liquid with the same alkyl chain length but
different counter ion (anionic). The surface coverage area obeys the following
order: PF6− > BF4− > Br− > Cl−. Hence, the ionic radius of the anions is increased by
the same amount. The larger anionic radius of PF6−turns out to have better protec-
tion than the others [14]. The negative ion contribution in the ionic liquid structure
could be evaluated through its corrosion protection performance. Saleh et al.
discussed the effect of Br− and Cl− ions with cetylpyridinium ions in sulfuric acid
over mild steel [8, 21].
Corrosion current has decreased considerably compared to the blank medium.
The bromide ion has a stronger effect on anodic dissolution than the chloride ion.
The anionic radius of bromine atoms is better suited for the bonding and surface
coverage area on the metal/solution interface. Likewise, the anionic effect of ethyl
sulfate and acetate ions on ethylmethylimidazolium can be deduced by comparing
its protection efficiency over mild steel. Among the ionic liquids, [EMIM] [EtSO4]
is better at mitigating the anodic curve current than the acetate ion. Most probably,
the inhibition efficiency is higher than the acetate ion, and this is attributed to the
increased number of electronegative (hetero) atoms in the ionic liquid. On the
other hand, the [EMIM] [Ac] ionic liquid showed reduced contribution compared
to the [BMIM] [Ac] ionic liquid because of its long alkyl chain length [22].
2.2 I mprovement in electrochemical noise resistance due to structural

modification of the inhibitor
Electrochemical noise is another technique to ensure corrosion protection of

the metal surface offered by ionic liquids. When the metal is exposed to the acid
medium, the electrochemical reaction commences as fast as it can. As a result, the
current is measured in the form of current deviation (σI). For the blank medium,
current noise appears with higher amplitude, vindicating the absence of passivation
over the metal surface. Also, the current transient width and amplitude designate
the available active surface area on the metal surface. Metal immersed in acid
medium afforded the noise resistance value of 1.474 × 104 Ω cm2. These active areas
were reduced due to the adsorption of ionic liquid ([BMMB]+Br−). Thus, the Rn
value increased from 5.29 to 27.7 × 104 Ω cm2, as the concentration increased from
150 to 250 ppm, respectively. On observing [23], the noise amplitude decreased at
each concentration level of ionic liquid. This ionic liquid contributed to corrosion
protection by governing its electron-rich center to form a bonding with the metal.
On the other hand [24], [BMEB]+BF4− ionic liquid influences the electrochemical
noise to reduce gradually that of [BMMB]+Br−, which is attributed to less electro-
chemical reaction taking place. As a result, current noise amplitude decreased and
concurrently noise resistance increased.
On comparing the noise resistance value of both ionic liquids, it clearly indicates
that ethyl-derived ionic liquid has a better tendency to protect the metal surface at
the interface than [BMMB]+Br−. [BMEB]+BF4− possesses higher noise value at each
concentration than [BMMB]+Br− at the same concentration. Ethyl and BF4 groups
were more susceptible to transferring electrons, which resulted in better corrosion
protection in acid medium as shown in Figure 1.
3
Figure 1.
Schematic representation of electrochemical noise analysis (ENA) of ionic liquids.
2.3 S
ignificance of carbon chain length on surface protection of metal in
acid medium
On comparing the surface protection effect of any ionic liquid with its alkyl-
ated and non-alkylated form, it would help to understand the structure effect
of surface protection. Gabler et al. [25] reported that strong binding between
metal surface and ionic liquid is key for corrosion reduction. In an electrochemi-
cal study of 2-hydroxy- and butylammonium sulfonyl imide, the C▬F bond
cleavage was reduced significantly in butyl form compared to the former. On the
other hand, Kaczerewska et al. [26] studied the structural effect of inhibition
efficiency on metal protection in acid medium. Interconnecting a gemini cation
with a bridged oxygen atom showed better surface coverage to avert corrosive
ion contact with metal surfaces. The 18-O-18 gemini cationic part of ionic liquid
offered improved protection resistance against metal dissolution [27]. Vastag
et al. suggested [12] that by increasing the alkyl chain number in N-substituted
cations would favor the inhibitor action of organic compounds to isolate metal
from further corrosion. Generally, the surface protection of ionic liquid on
carbon steel was improved when the N3 atom was alkylated with carbon chain
lengths from n-7 to n-9. Infrared spectra also confirmed the shift in wave
number [7]. Image examination of metal surfaces exposed to 1-ethyl [12] and
1-allyl [28] 3-butylimidazolium bromide ionic liquid expressed the inhibition
effect of ionic liquid. The inductive effect of the allyl group offered increased
electrons in its structure in the cation of ionic liquid. Hence, as resonance
increased, the adsorption of ionic liquids over the metal surface also increased.
Damage to the negative ions in the ionic liquids influenced corrosion protection
[29]. HSO4− has greater tendency to render protection on metal surfaces than
BF4−. Sometimes, iminium compounds reduce surface heterogeneity, caused by
adsorption of ionic liquid over the metal surface. Apparently, elemental analysis
of the inhibited metal showed that the inhibitor’s constituents were 15 wt%
of carbon and 10 wt% of oxygen, and also corroborated that dodecyl iminium
chloride is more favorably adsorbed than the non-alkylated form [30].
4
2.4 Study of hydrogen gas evolution over N1 atom of ionic liquid acid
The hydrogen gas evolution method is one of the ways to determine the corro-
sion rate of metal in an aggressive medium. Hydrogen gas evolution is a result of
a reduction (cathodic) reaction at the metal surface. The volume of hydrogen gas
produced in the medium is gradually reduced in the presence of ionic liquid. The
increment in alkyl chain length on N1 atoms of the benzimidazolium cation offers
maximum surface coverage on the active site. Thus, a lesser amount of hydrogen gas
will be produced than the blank medium [24]. As seen, the volume of hydrogen gas
is reduced for both methyl and ethyl benzimidazolium ionic liquid in concentration
[23]. Furthermore, it can be understood that each concentration of ethyl benzimid-
azolium ([BMEB]+BF4−) possesses a very low volume of H2 gas compared to methyl
benzimidazolium ([BMMB]+Br−).
From the above valid point, it is vindicated that the alkyl chain length offers
maximum energy or electrons to adhere to the cathode area, which is also the
route to sturdy passive film formation between the corrosive medium and the
metal surface. The general corrosion mechanism for carbon steel in 1 N HCl
acid is described below. As shown in the following equation the ionic liquid
is adsorbed onto the anodic and cathodic areas of the carbon steel surface,
respectively.
Anodic protection reaction of [BMMB]+Br−:
Fe + (Cl) −ads
   ⇋ (Fe Cl) −ads
    (1)
    + BMMB  ⇋ [Fe (Cl) − BMMB  ] ads

+ +
Fe (Cl) −ads
(2)
    +BMMB  → [Fe (Br) − BMMB  ] ads

+ +
Fe (Br) −ads
(3)
[BMEB]+BF4−:
    + BMEB  ⇋ [Fe (Cl) − BMEB  ] ads

+ +
Fe (Cl) −ads
(4)
    +BMEB  → [Fe (Br) − BMEB  ] ads

+ +
Fe (Br) −ads
(5)
Likewise in the cathodic area, the reduction (hydrogen gas formation) reac-
tion was considerably decreased due to the alkylation impact of ionic liquid on the
adsorption effect instead of H+, and thus hydrogen gas evolution was reduced.
Cathodic protection reaction of [BMMB]+Br−:
+
Fe + BMMB  ⇋ Fe ( BMMB) +ads
    (6)
Fe ( BMMB) +ads
    + e −→ Fe ( BMMB) ads (7)
[BMEB]+ BF4−:
+
Fe + BMEB  ⇋ Fe ( BMEB) +ads
    (8)
5
    + e −→ Fe (BMEB) ads
Fe (BMEB) +ads (9)
As seen in the above equations, the adsorption of the cationic part of ionic liquids
is favored in both anodic and cathodic reactive sites. The most favored cationic part
among the above three kinds of ionic liquids is [BMEB]+. The (CH3 − CH2−) ethyl
group, which effortlessly offered electrons to the metal surface, explains the reason for
the occurrence of reduced volume of hydrogen gas in the acid medium. Figure 2 shows
the hydrogen gas evolution reaction in the blank and benzimidazolium ionic liquid.
2.5 Influence of alkyl chain length on quantum chemical parameters
Quantum chemical studies have been used as an efficient method to evaluate the
corrosion inhibition performance of any kind of inhibitor. Since corrosion inhibi-
tion is adsorption related, dynamic and quantum studies are used to characterize
the electronic properties that help to understand the adsorptive properties of the
organic compound [31]. Many factors, including heteroatoms, π-electrons, aromatic
rings, and carbon chain length, influence the adsorption properties of the inhibitor
with metal surfaces [32]. The adsorption properties of ionic liquids will differ by
their structural nature, particularly in HOMO and LUMO energy levels. The higher
value of HOMO energy level contributes to the electron offering tendency to the
acceptor molecule or lower energy state. Gad et al. [33] reported that increasing
alkyl chain length increased HOMO energy level in pyridinium bromide ionic
liquid. The maximum HOMO level was attained for (C12) 4-mercapto-1-dodecyl-
pyridinium bromide compared to C8 and C10.
Likewise, the LUMO energy level of an inhibitor also depends on the functional
group present in the structure. The maximum LUMO value is acquired by (C8)
pyridinium bromide ionic liquid compared to the rest. A smaller alkyl chain length
will decrease HOMO energy level and increase LUMO energy level. LUMO defines
electron-accepting behavior of the molecule from the neighboring environments.
Since (C8) ionic liquid has a higher LUMO level, it can withdraw the electron from
the metal, and even from feedback bonding, and result in strong adsorption with the
metal surface. The change in energy gap is an important factor for measuring reactiv-
ity of ionic liquid to adsorb onto the metallic surface. The lower value of ∆E is the
reason for the higher inhibition efficiency in metal corrosion. This is attributed to the
Figure 2.
Pictorial representation of hydrogen gas evolution in the absence and presence of [BMMB]+Br− and
[BMEB]+BF4− in 1 N HCl medium.
6
minimum amount of energy used to transfer the electron from the highest occupied
orbital to the vacant “d” orbital of metal [34]. The ∆E value of the electrodeposition
of polyaniline using tetrabutyl phosphonium bromide is less than that using ethyl
tributyl phosphonium diethoxy phosphate. The above facts are the same as above
in the phosphonium bromide molecule. The energy difference is much higher when
substituting the 4-ethoxybenzyl group in the phosphonium [35] cationic part com-
pared to butyl substitution [36]. Likewise, increasing the carbon chain length on the
heterocyclic group also decreases the ∆E considerably [37]. The presence of methyl
and ethyl groups in the benzimidazolium groups will maintain the minimum energy
gap between the HOMO and LUMO groups as represented in Figure 3.
In addition, the binding energies of butyl and ethoxy-substituted phosphonium
bromide were 2040.9 and 25505.6 kJ, respectively. Ethoxy-substituted phosphonium
bromide possessed more negative than butyl-substituted phosphonium bromide.
Hence, the ionic liquid is more stable and there is less chance of spitting in the
medium because of better passive film on the metal surface. Still, many researchers
are studying the structure impact on its corrosion performance. By introducing an
alkyl functional group to imidazoline ionic liquid, the relationship between corrosion
protection and structure can be discussed. Apparently, partial atomic charges of each
atom in the compound describe structural influence using quantum chemical param-
eters on corrosion protection in the comparison study of [DMIM][BF4] and [BMIM]
[BF4] at corrosion inhibition efficiency; the partial atomic charges focus on cationic
moiety rather than anionic moiety, because cations possess large molecular size.
Finally, the carbon atom of the alkyl chain contains a negative charge. The C5 carbon
atom has a higher negative charge in [DMIM][BF4] than in [BMIM][BF4]. This makes
DMIM ionic liquid effective in adsorption on the metal surface against corrosion [38].
In addition, Ibrahim et al. noted their point on structural effect in their research
[18]. The adsorption of imidazolium ionic liquid took place through the nitrogen
atom of the ring. The coordinate bond occurs between nitrogen and iron. On
evaluating two ionic liquids (benzyl and ethyl acetate-substituted imidazolium
ionic liquids), benzyl-substituted imidazolium ionic liquid has a higher rate of
adsorption on the anodic curve area than ethyl acetate-substituted imidazolium
ionic liquid, because the former has a higher rate of relaxation of adsorbed ionic
liquid from the metal surface.
Figure 3.
Schematic representation of energy gap difference between various benzimidazolium ionic liquids.
7
3. Conclusion
On the basis of the above discussion of the alkylation effect on ionic liquids in
various analyses, it can be concluded that structural effect is a considerable key
factor in enhancing corrosion protection performance of metal in acid medium.
Alkylation of the heterocyclic cation in the ionic liquid, particularly on N1/N2 of
imidazolium, benzimidazolium, or N1 of pyridinium or P1 phosphonium, facili-
tates the physical/chemical properties of the ionic liquids compared to unalkyl-
ated ionic liquid. Not only had the physical/chemical properties changed but also
electrochemical properties. This effect has been discussed with respect to various
studies, such as electrochemical behavior, surface protection, electronic proper-
ties quantum chemical analysis (QCA), and hydrogen gas evolution. Adsorption
of ionic liquid is favored mostly when it is being structurally modified as a result
of passive film adsorption on the metal surface, which keeps the environment
corrosion free. The reason for the extraordinary maturity of the alkylated ionic
liquid could be described using theoretical study. This will support the alkylated
or structurally modified ionic liquid electronic properties. The electron-donating
nature of ionic liquid is being increased by alkylation. As a result, the resonance
effect also increased, which contributes to the stability of the ionic liquid com-
pared to the unalkylated form. The use of ionic liquid as a corrosion inhibitor is
predominant and more efficient for structural modification.
Acknowledgements
The author is thankful to his management for their help in assisting his work
on this chapter. Dr. P. Kannan is acknowledging Centre for Research, CHRIST
(Deemed to be University), Bengaluru for carrying out this work.
Conflict of interest
The author of this manuscript has no conflict of interest.
Notes/thanks/other declarations
I express my heartfelt thanks to my friends Mr. P. Mathavan, Dr. L. Mohan, and

Dr. K. Vidya for their constant support and encouragement on this endeavor.
8
9
References
[1] Morsi RE, Khamis EA, Al-Sabagh AM. of Molecular Liquids. 2017;229:396-404.
Polyaniline nanotubes: Facile synthesis, DOI: 10.1016/j.molliq.2016.12.092
electrochemical, quantum chemical
characteristics and corrosion inhibition [8] Atia AA, Saleh MM. Inhibition
efficiency. Journal of the Taiwan of acid corrosion of steel using
Institute of Chemical Engineers. cetylpyridinium chloride. Journal of
2016;60:573-581. DOI: 10.1016/j. Applied Electrochemistry. 2003;33:
jtice.2015.10.028 171-177. DOI: 10.1023/A:1024083117949
[2] Hegazy MA, Atlam FM. Three novel [9] El-Shamy AM, Zakaria K, Abbas MA,
bolaamphiphiles as corrosion inhibitors El Abedin SZ. Anti-bacterial and
for carbon steel in hydrochloric acid: anti-corrosion effects of the ionic
Experimental and computational liquid 1-butyl-1-methylpyrrolidinium
studies. Journal of Molecular Liquids. trifluoromethylsulfonate. Journal of
2016;218:649-662. DOI: 10.1016/j. Molecular Liquids. 2015;211:363-369.
molliq.2016.03.008 DOI: 10.1016/j.molliq.2015.07.028
[3] Farag AA, Ismail AS, Migahed MA. [10] El Belghiti M, Karzazi Y, Dafali A,
Inhibition of carbon steel corrosion Hammouti B, Bentiss F, Obot IB, et al.
in acidic solution using some newly Experimental, quantum chemical
polyester derivatives. Journal of and Monte Carlo simulation studies
Molecular Liquids. 2015;211:915-923. of 3,5-disubstituted-4-amino-1,2,4-
DOI: 10.1016/j.molliq.2015.08.033 triazoles as corrosion inhibitors on
mild steel in acidic medium. Journal of
[4] Zarrouk A, Hammouti B, Touzani R, Molecular Liquids. 2016;218:281-293.
Al-Deyab SS, Zertoubi M, Dafali A, DOI: 10.1016/j.molliq.2016.01.076
et al. Comparative study of new
quinoxaline derivatives towards [11] Zhang QB, Hua YX. Corrosion
corrosion of copper in nitric acid. inhibition of mild steel by
International Journal of Electrochemical alkylimidazolium ionic liquids in
Science. 2011;6:4939-4952 hydrochloric acid. Electrochimica Acta.
2009;54:1881-1887. DOI: 10.1016/j.
[5] Wang D, Yang D, Zhang D, Li K, electacta.2008.10.025
Gao L, Lin T. Electrochemical and
DFT studies of quinoline derivatives [12] Vastag G, Shaban A, Vraneš M,
on corrosion inhibition of AA5052 Tot A, Belić S, Gadžurić S. Influence of
aluminium alloy in NaCl solution. Applied the N-3 alkyl chain length on improving
Surface Science. 2015;357:2176-2183. DOI: inhibition properties of imidazolium-
10.1016/j.apsusc.2015.09.206 based ionic liquids on copper corrosion.
Journal of Molecular Liquids.
[6] Zhang QB, Hua YX. Corrosion 2018;264:526-533. DOI: 10.1016/j.
inhibition of aluminum in hydrochloric molliq.2018.05.086
acid solution by alkylimidazolium
ionic liquids. Materials Chemistry and [13] Guzmán-Lucero D, Olivares-Xometl
Physics. 2010;119:57-64. DOI: 10.1016/j. O, Martínet-Palou R, Likhanova NV,
matchemphys.2009.07.035 Domínguez-Aguilar MA, Garibay-
Febles V. Synthesis of selected
[7] Deyab MA, Zaky MT, Nessim MI. vinylimidazolium ionic liquids and their
Inhibition of acid corrosion of effectiveness as corrosion inhibitors for
carbon steel using four imidazolium carbon steel in aqueous sulfuric acid.
tetrafluoroborates ionic liquids. Journal Industrial & Engineering Chemistry
10
Research. 2011;50:7129-7140. DOI: et al. Pyridazinium-based ionic liquids

10.1021/ie1024744 as novel and green corrosion inhibitors
of carbon steel in acid medium:
[14] Yousefi A, Javadian S, Dalir N, Electrochemical and molecular
Kakemam J, Akbari J. Imidazolium- dynamics simulation studies. Journal of
based ionic liquids as modulators of Molecular Liquids. 2018;249:997-1008.
corrosion inhibition of SDS on mild DOI: 10.1016/j.molliq.2017.11.111
steel in hydrochloric acid solutions:
Experimental and theoretical studies. [20] Martins VL, Sanchez-
RSC Advances. 2015;5:11697-11713. Ramírez N, Calderon JA, Torresi
DOI: 10.1039/C4RA10995C RM. Electrochemistry of copper in
ionic liquids with different coordinating
[15] Murulana LC, Singh AK, Shukla SK, properties. Journal of Materials
Kabanda MM, Ebenso EE. Experimental Chemistry A. 2013;1:14177-14182. DOI:
and quantum chemical studies of some 10.1039/C3TA12992F
bis(trifluoromethyl-sulfonyl) imide
imidazolium-based ionic liquids as [21] Saleh MM. Inhibition of mild steel
corrosion inhibitors for mild steel in corrosion by hexadecylpyridinium
hydrochloric acid solution. Industrial bromide in 0.5M H2SO4.
& Engineering Chemistry Research. Materials Chemistry and Physics.
2012;51:13282-13299. DOI: 10.1021/ 2006;98:83-89. DOI: 10.1016/j.
ie300977d matchemphys.2005.08.069
[16] Kowsari E, Arman SY, Shahini MH, [22] Sasikumar Y, LO O, Bahadur I,

Zandi H, Ehsani A, Naderi R, et al. In situ Kabanda MM, Obot IB, Ebenso EE.
synthesis, electrochemical and quantum Experimental and theoretical studies on
chemical analysis of an amino acid- some selected ionic liquids with different
derived ionic liquid inhibitor for corrosion cations/anions as corrosion inhibitors
protection of mild steel in 1M HCl for mild steel in acidic medium. Journal
solution. Corrosion Science. 2016;112: of the Taiwan Institute of Chemical
73-85. DOI: 10.1016/j.corsci.2016.07.015 Engineers. 2016;64:252-268. DOI:
10.1016/j.jtice.2016.04.006
[17] Likhanova NV, Dominguez-Aguilar
MA, Olivares-Xometl O, Nava-Entzana [23] Kannan P, Rao TS, Rajendran N.
N, Arce E, Dorantes H. The effect of Anticorrosion behavior of
ionic liquids with imidazolium and benzimidazolium tetrafluoroborate
pyridinium cations on the corrosion ionic liquid in acid medium using
inhibition of mild steel in acidic electrochemical noise technique. Journal
environment. Corrosion Science. of Molecular Liquids. 2016;222:586-595.
2010;52:2088-2097. DOI: 10.1016/j. DOI: 10.1016/j.molliq.2016.07.116
corsci.2010.02.030
[24] Kannan P, Karthikeyan J, Murugan P,
[18] Ibrahim MAM, Messali M, Rao TS, Rajendran N. Corrosion
Moussa Z, Alzahrani AY, Alamry SN, inhibition effect of novel methyl
Hammouti B. Corrosion inhibition benzimidazolium ionic liquid for
of carbon steel by imidazolium and carbon steel in HCl medium. Journal of
pyridinium cations ionic liquids in Molecular Liquids. 2016;221:368-380.
acidic environment. Portugaliae DOI: 10.1016/j.molliq.2016.04.130
Electrochimica Acta. 2011;29:375-389.
DOI: 10.1016/j.corsci.2010.02.030 [25] Gabler C, Tomastik C, Brenner J,
Pisarova L, Doerr N, Allmaier G.
[19] El-Hajjaji F, Messali M, Aljuhani A, Corrosion properties of ammonium based
Aouad MR, Hammouti B, Belghiti ME, ionic liquids evaluated by SEM-EDX,
11
XPS and ICP-OES. Green Chemistry. steel in 1.0 M HCl medium. Corrosion

2011;13:2869-2877. DOI: 10.1039/ Science. 2004;46:2455-2466. DOI:
C1GC15148G 10.1016/j.corsci.2004.01.023
[26] Kaczerewska O, Leiva-Garcia R, [32] Obot IB, Gasem ZM, Umoren SA.
Akid R, Brycki B, Kowalczyk I, Understanding the mechanism of
Pospieszny T. Effectiveness of 2- mercaptobenzimidazole adsorption
O-bridged cationic gemini surfactants as on Fe (110), Cu (111) and Al (111)
corrosion inhibitors for stainless steel in surfaces: DFT and molecular dynamics
3 M HCl: Experimental and theoretical simulations approaches. International
studies. Journal of Molecular Liquids. Journal of Electrochemical Science.
2018;249:1113-1124. DOI: 10.1016/j. 2014;9:2367-2378
molliq.2017.11.142
[33] Gad EAM, Azzam EMS, Halim SA.
[27] Zuriaga-Monroy C, Oviedo-Roa R, Theoretical approach for the
Montiel-Sánchez LE, Vega-Paz A, performance of 4-mercapto-
Marín-Cruz J, Martínez-Magadán JM. 1-alkylpyridin-1-ium bromide
Theoretical study of the aliphatic- as corrosion inhibitors using
chain length’s electronic effect on DFT. Egyptian Journal of Petroleum.
the corrosion inhibition activity of 2018;27:695-699. DOI: 10.1016/j.
methylimidazole-based ionic liquids. ejpe.2017.10.005
Industrial & Engineering Chemistry
Research. 2016;55:3506-3516. DOI: [34] Ortaboy S. Electropolymerization
10.1021/acs.iecr.5b03884 of aniline in phosphonium-based
ionic liquids and their application as
[28] Luo L, Zhang S, Qiang Y, Chen N, protective films against corrosion.
Xu S, Chen S. Study on 1-allyl-3- Journal of Applied Polymer Science.
butylimidazalium bromine as corrosion 2016;133:43923-43935. DOI: 10.1002/
inhibitor for X65 steel in 0.5 M H2SO4 app.43923
solution. International Journal of
Electrochemical Science. 2016;11:8177- [35] Kumar S, Goyal M, Vashisht H,
8192. DOI: 10.20964/2016.10.52 Sharma V, Bahadur I, Ebenso EE.
Ionic salt (4-ethoxybenzyl)-
[29] Ma Y, Han F, Li Z, Xia C. Acidic- triphenylphosphonium bromide as a
functionalized ionic liquid as green corrosion inhibitor on mild steel
corrosion inhibitor for 304 stainless in acidic medium: Experimental and
steel in aqueous sulfuric acid. ACS theoretical evaluation. RSC Advances.
Sustainable Chemistry & Engineering. 2017;7:31907-31920. DOI: 10.1039/
2016;4:5046-5052. DOI: 10.1021/ C6RA27526E
acssuschemeng.6b01492
[36] Bhrara K, Kim H, Singh G.
[30] Masroor S, Mobin M, Alamb MJ, Inhibiting effects of butyl triphenyl
Ahmad S. The novel iminium surfactant phosphonium bromide on corrosion
p-benzylidene benzyldodecyl iminium of mild steel in 0.5 M sulphuric
chloride as a corrosion inhibitor acid solution and its adsorption
for plain carbon steel in 1 M HCl: characteristics. Corrosion Science.
Electrochemical and DFT evaluation. 2008;50:2747-2754. DOI: 10.1016/j.
RSC Advances. 2017;7:23182-23196. corsci.2008.06.054
DOI: 10.1039/C6RA28426D
[37] Kannan P. Synthesis,
[31] Wang HL, Liu RB, Xin J. Inhibiting characterization and corrosion
effects of some mercapto-triazole protection performance of
derivatives on the corrosion of mild benzimidazolium ionic liquids for
12
carbon steel in acid environment

[thesis]. Chennai: Anna University;
2017
[38] Manamela KM, Murulana LC,

Kabanda MM, Ebenso EE. Adsorptive
and DFT studies of some imidazolium
based ionic liquids as corrosion
inhibitors for zinc in acidic medium.
International Journal of Electrochemical
Science. 2014;9:3029-3046
13
Chapter 03
Exploring Musa paradisiaca Peel

Extract as a Green Corrosion
Inhibitor for Mild Steel Using
Factorial Design Method
Olusola S. Amodu, Moradeyo O. Odunlami,
Joseph T. Akintola, Seteno K. Ntwampe and Seide M. Akoro
Abstract
The suitability of Musa paradisiaca (banana) peel extract as a green corrosion

inhibitor for mild steel in acidic medium (1 M HCl) was investigated using facto-
rial method of the design of experiment. The effects of two independent variables
(concentration of banana peel extract and temperature) on the corrosion inhibition
efficiency were investigated. The physicochemical properties of the extract such
as surface tension, viscosity, flash point, and specific gravity were determined
using standardized methods provided by the American System of Testing Materials
(D-971). The relationship between the independent variables and the inhibitor
efficiency was modeled by gasometric and thermometric methods. The statisti-
cal analysis of the inhibition efficiency was carried out using the “Fit Regression
Model” of Minitab® 17.0, while the fitness of the models was assessed by the
coefficient of determination (R2) and the analysis of variance (ANOVA). From the
results obtained, gasometric method achieved a maximum inhibition efficiency
of 66.83%, with an R2 of 90.76%, whereas thermometric method gave a maximum
inhibition efficiency of 65.70%, with an R2 of 95.56%. This study shows that banana
peel extract has the capacity to prevent the corrosion of mild steel in acidic medium.
Keywords: banana peel extract, biomass, corrosion, inhibitors, factorial design
1. Introduction
In 2016, NACE International estimated the global cost of corrosion at US$ 2.5 trillion
annually. This accounts for about 3.4% of the global gross domestic product (GDP). In
the same study, it was discovered that if corrosion prevention best practices are imple-
mented, there could be global savings of between 15 and 35% of the cost of damage
[1]. In spite of the technological advancement of this generation, high profile cases of
corrosion have continued to emerge [2–4]. Moreover, the extensive application of acid
solutions in industrial cleaning and descaling of mild steel makes metal dissolution a
common phenomenon Gadiyar et al. [5]. In order to prolong the lifespan of mild steel,
to enhance its viability, and to reduce the high cost of production, practical steps need to
be employed in corrosion prevention. Failure to prevent or manage corrosion can result
to metal losses, loss of production time, leaking vessels, and unwarranted cleanup costs.
1
Corrosion is an electrochemical process; it is the propensity for metals to revert

to their natural ore state. It takes place in the presence of moisture and oxygen,
involving chemical reaction and the flow of electrons on the surface of the corroded
cells, which greatly accelerate the transformation of metal back to the low-grade
ore. The process involves the oxidation of a metal atom, whereby it loses one or
more electrons. The resultant effect of corrosion is metal degradation, that is, the
breakup of bulk metal, causing it to lose its useful properties [6]. This electrochemi-
cal process, often referred to as galvanic cell, occurs when two different metals in
physical or electrical contact are immersed in a common electrolyte with different
concentrations. Consequently, the more active metal (anode) gets corroded while
the more noble metal (cathode) is protected [7, 8]. The fundamental chemical reac-
tions occurring at the anode and cathode are:
−
Anode surface : Fe → Fe  2+ + 2 e 

− −
 1  O2   + H2  O + 2 e  → 2 OH 
Cathode surface : _

2
At anode : Fe  2+ + 2 OH −→ Fe  O . (H2  O)–hydrated iron oxide (brown rust)

Galvanic corrosion is the most common type of corrosion and it occurs regularly
in marine vessels, metal structures, and oil pipelines. Furthermore, the phenomenon
is commonly observed in water treatment plant, boilers, storage vessels, oil pipe-
lines, etc. In fact, what makes corrosion challenging is that it starts on the internal
part of the metal structure, which makes early detection difficult. Other than water
and oxygen, galvanic corrosion is affected by: types of metal, agitation, the presence
and type of inhibitors, and environmental factors (pH, temperature, humidity,
salinity, etc.) [9]. In addition, the dissolution of mild steel in HCl is given as:
+
2 F e + H  → F e 2+ + H 2

The rate of this reaction is dependent on: metal (its position in the electromotive
series), acidity, ferrous ion concentration (by the law of mass action, the increase in
ferrous ions should correspond to the decrease in rate of corrosion), and hydrogen
gas evolution.
Three techniques are often used for the assessment of corrosion rates namely,
weight loss technique, electrochemical impedance spectroscopy, and hydrogen gas
evolution method. The weight loss method is considered the most fundamental,
against which the accuracy of the other methods is determined. However, the
limitations of this method are: (1) the weight loss expressed is the average of the
weight of the corroding specimen over a period of time but the changes in corro-
sion rate over this period is not accounted for; (2) in order to accurately determine
the weight loss caused by corrosion, all the corroded particles need to be removed
from the specimen surface without removing the uncorroded metal, which practi-
cally is unrealistic. Electrochemical technique has been successfully used in many
corrosion studies to determine the rate of corrosion [4, 7, 10]. Particularly, it has
certain advantages over the weight loss method, due to its ease of corrosion rates
determination. With this method, instantaneous corrosion rates as well as changes
in corrosion rates over a period of time can be determined. However, during the
electrochemical dissolution process for some metals and metal alloys, the atypical
polarization performance at the anode is a challenge. Moreover, hydrogen removal
can occur in two ways: hydrogen gas evolution and depolarization via oxidation by
2
Exploring Musa paradisiaca Peel Extract as a Green Corrosion Inhibitor for Mild Steel Using…
dissolved oxygen or by some other oxidizing agent [11]. Hydrogen gas evolution
method seems to be the most significant and reliable in assessing the rate of corro-
sion as the mole of metal dissolved directly correlates to the amount of hydrogen gas
given off [12].
The application of inhibitors is one of the practical ways to protect metals
against corrosion, especially in acidic media. Basically, they function by serving as
integuments on metal surface thereby preventing it from chloride ions and oxygen
dissolution. Corrosion inhibitors find application in minimizing metallic waste in
engineering materials, in addition to the advantages of versatility and cost effective-
ness when compared to other corrosion protection methods [10, 13]. Most of the
effective inhibitors are either from biomass precursors or chemical compounds
containing hetero-atoms such as oxygen, nitrogen, and sulfur with multiple bonds
in their molecules through which they are adsorbed on the metal surface [14–16].
This adsorption depends on certain physiochemical properties of the inhibitors:
functional group, electron density at the donor atom, n-orbital character, and the
electron structure of the molecule. They contain electronegative functional groups
and π-electrons in their double bonds, which facilitate their adsorption onto the
metal surface. Hence, the strength of an inhibitor to either prevent corrosion reac-
tion from being initiated or slow down the rate of corrosion, is dependent upon the
molecular structure of the inhibitor molecules.
The major concern with most chemical inhibitors is their toxicity to the
environment. Although many of these synthetic compounds have shown good
anti-corrosive activity; their applications have been limited due to environmental
considerations [17–20]. Particularly, inorganic corrosion inhibitors such as lead
and chromium have been found to constitute significant health challenge to human
when released into the environment. This has necessitated the quest for environ-
mentally benign precursors as corrosion inhibitors, for which a plethora of organic
materials have been reported. Some of these materials are plant extracts of kola nut,
tobacco, Rosmarinus officinalis, Cassia auriculata, Argemone Mexicana, unripe fruit
of Musa acuminate, roasted coffee seed (Coffea arabica), Carica papaya leaves, can-
nabis plant, pomegranate, etc. [14, 19, 21–23]. Furthermore, research has revealed
that the basic components of plant extracts are alkaloids, steroids, sugars, gallic
acid, tannic acid, and flavonoids, which have been found to improve the protection
of metal surface against corrosion [24–26].
The use of natural organic plant extracts as corrosion inhibitors is sometimes
referred to as green corrosion prevention. These natural organic compounds are
relatively cheaper, nontoxic, and readily available, either as agro-waste and/or agro-
industrial waste [27]. Therefore, the aim of this study was to investigate the effec-
tiveness of Musa paradisiaca (banana) peel extract as a green corrosion inhibitor for
mild steel in acidic medium. The rate of corrosion was assessed using the hydrogen
gas evolution method. In addition, the interaction effects of concentration and
temperature variation on the corrosion inhibition were assessed using full factorial
design and analyzed with relevant statistical tools.
2. Materials and methods
2.1 Preparation of samples and corrosion test solutions
Banana peels were sourced locally. The peels were washed under running water
and air dried until a constant mass was recorded. It was milled into powder using a
hammer-mill and ball-mill to achieve finesse of powder (about 0.25 mm diameter
size). The powdered peel was extracted using 95% ethanol. Five grams of powder
3
Figure 1.
Flow process for banana peel extract (BPE) as corrosion inhibitor.
was dissolved in 200 ml ethanol for 14 days and thereafter filtered. The filtrate was
rotatory evaporated in order to remove excess ethanol, and then diluted with 1 M
HCl in distilled water to obtain the corrosion inhibition test solutions in the con-
centration ratio of 1.0, 2.5, 5, 7.5, and 10% (v/v). Figure 1 shows the various stages
involved in the extraction of banana peels.
In addition, the mild steel used was mechanically press-cut into coupons of
dimensions 4 × 2.5 × 0.1 cm. Each coupon was degreased by washing with ethanol,
dried in acetone, and immediately transferred into the simulated test solutions. Note
that the dried coupons can be preserved in a desiccator until use. Similarly, control
experiments were set up but without the addition of the inhibitor. All reagents used
were of analytical grade. Banana peel is composed of starch (3%), total dietary fiber
(43.2–49.7%), crude fat (3.8–11%), crude protein (6–9%), polyunsaturated fatty
acids, pectin, micronutrients (K, P, Ca, and Mg), and amino acid [28]. Also, the
mild steel sheet used has the following compositions (% wt): Fe—99.3, Mn—0.34,
Cu—0.069, Co—0.069, Ca—0.087, Ni—0.043 and Al—0.03.
2.2 Evaluating the physical properties of banana peel extract as a corrosion

inhibitor
2.2.1 Viscosity measurement
This was determined by the Cannon-Fenske viscometer and a circulatory bath with
temperature control. Viscosity was calculated using ASTM Method D445–97 [29]. The
viscosity η of each sample was calculated using the formula below:

η = k𝜌T, (1)
where k is the instrument constant, ρ is the density of banana peel extract

sample, and T efflux time (sec) for banana peel extract sample.
2.2.2 Specific gravity determination
The extract of banana peel was transferred into a narrow glass cylinder
(SP0121-V Osaka, Japan) and a hydrometer was set into the sample and allowed to
stabilize. The value of the specific gravity was taken from the markings on the stem
of the hydrometer at the surface of the extract sample.
2.2.3 Surface tension determination
This study employed the American System of Testing Materials D-971 [29]
method. Two grams of banana peel extract was added to 50 ml of distilled water in
4
a 100 ml beaker. A platinum ring was then lowered into the solution of banana peel
extract in the beaker. It was then brought up to the water sample interface, where
the actual measurement takes place. The force required to pull the ring through
the interface was measured by a tension meter as the surface tension of the extract
solution (dynes cm−1).
2.2.4 Flash point measurement
The measurement of the flash point for the BPE sample was done using ASTM D-92
method [29]. An open cup containing BPE sample was heated at a specific rate while
flame was periodically passed over its surface. The lowest temperature at which the BPE
vapor ignites without sustaining the flame was recorded as the flash point.
2.3 Evaluating the corrosion inhibition efficiency of banana peel extract
2.3.1 Gasometric method
This method was adopted in this study as described by Ekpe et al. [23], and
carried out at the following temperatures: 303, 308, 313, 318, and 323 K, which were
achieved using a water bath. The coupons immersed in the prepared test solutions
were recovered after 6 h, washed in detergent solution, and rinsed with distilled
water, and air dried. The volume of gas evolved from the cathodic reaction during
the corrosion process was determined. Hence, gasometric method correlates the
quantity of gas evolved to the rate of corrosion. The graph of the volume of gas lib-
erated per minute gives the rate of gas evolution, while the inhibition efficiency (𝓔)
and degree of surface coverage ( θ )were determined from Eqs. 2 and 3, respectively.
( V   H)
V ∗ 
ℰ = 1 − ____
  0H    × 100 (2)
( V   H)
V ∗ 
θ = 1 − ____
  0H   (3)
where V*H is volume of hydrogen gas evolved at time t in the presence of inhibi-
tor and V0H is the volume of hydrogen evolved in the absence of inhibitor.
2.3.2 Thermometric method
Temperature determination was carried out as reported by Ebenso et al. [30].

Using the value for the rise in temperature per minute, the reaction number (RN)
was calculated as shown in Eq. 4:
RN (  C / min)= ( Tm − Ti) / t

°
(4)
where Tm and Ti are the maximum and initial temperatures, respectively,

attained by the system and t is the time. Similarly, the inhibition efficiency was
determined by the reaction number correlation (Eq. 5).
ℰ = (________
R No  )
R N   − R N 
  o   i    × 100 (5)
where RNo is the reaction number of solution without inhibitor, while RNi is the
reaction number of solution with inhibitor.
5
2.4 Effects of concentration and temperature variations on corrosion inhibition
The data obtained from the banana peel extraction experiments were analyzed
statistically using factorial method to obtain a linear fit for the inhibition of mild
steel corrosion under varied concentration and temperature. The mathematical
model was generated by a MINITAB 17.0. Regression analysis was performed to
correlate the response variable to the independent variables. The quality of the fit of
the model was evaluated using analysis of variance (ANOVA), where the response
was the inhibition efficiency; while concentration and temperature of BPE solution
were the input variables.
3. Results and discussion
3.1 Physical properties of BPE
The physical properties determined for the banana peel extract are presented in
Table 1.
The viscosity of the banana peel extract (BPE) compares favorably well with
those previously reported for BPE and other biomaterials. For instance, similar
viscosities were reported for extracts from Citrullus lanatus, Phyllanthus, and
banana peels [31, 32]. Viscosity is the property of a fluid that makes it resist
flow and sustain frictional force. It is an important property of a good inhibitor,
which makes it stick to the surface of metals thereby forming a protective barrier
against corrosion. It represents the ability of the extract to adhere longer to metal
surfaces, thus enhancing corrosion inhibition. Corrosion inhibitors often contain
one or more surfactants, which lowers the surface tension of corrosive fluids [33].
Similarly, the flash point of BPE extract is within the range reported by Kliskic
et al. [34] and Betiku et al. [35]. This indicates the flammability or combustibility
of the inhibitor.
3.2 Evaluation of BPE efficiency as a corrosion inhibitor
3.2.1 Gasometric method
The efficiency of corrosion inhibition by BPE was determined using gasometric

method according to Eq. 1, for the various concentrations of 1.0, 2.5, 5.0, 7.5, and
10.0 g/L (Table 2).
Density Dynamic viscosity Surface tension Specific Flash point

(g/L cm3) (cp) (dynes cm−1) gravity (°C)
1.56 32.04 18.0 1.55 237
Table 1.
Physical properties of banana peel extract (BPE).
Levels 1 2 3 4 5
Concentration (g/L), X1 1.0 2.5 5.0 7.5 10.0
Temperature (K), X2 303 308 313 318 323
Table 2.
Experimental design.
6
Figure 2.
Volumetric rate of hydrogen gas during corrosion of mild steel in 1 M HCl acid solution.
The volume of gas evolved from the cathodic reaction during the corrosion study
(Figure 2) is correlated to inhibition efficiency by gasometric method.
As shown in Figure 2, the volume of H2 evolved decreased with increasing
concentration of the extract. This can be attributed to increased adsorption forces at
higher concentrations. However, hydrogen gas evolution increased with time, until
after 8 min before equilibration. This is expected since adsorption decreases with
time. From the chemical equation, the dissolution of 2 M of ferrous generates one
molecule of hydrogen gas. This means that the evolution of one molecule of hydro-
gen gas corresponds to the dissolution of 2 M of iron. Theoretically, by mole ratio, it
implies that the rate of iron dissolution doubles the rate of hydrogen gas evolution.
From the anodic and cathodic reactions, the flow of chloride ion from cathode
caused the dissolution of iron at the anode and the metal gets corroded, which is the
formation of hydrated iron (II) chloride. Hence, prevention of corrosion is possible
if the chloride ion is prevented from having contact with the metal surface. The
corrosion of mild steel in HCl solutions has been reported to be a first order reaction
[36], which increases with increased acid concentration. In addition, the dissolution
of iron steel in hydrochloric acid is dependent upon chloride ion over acidic range of
pH. Also, the pH of HCl solution decreased with increased immersion time of the
mild steel (Figure 3). This was obviously due to increased acidity of the solution.
Moreover, as described in Section 2.3, the volume of hydrogen gas evolution was
used to determine the corrosion inhibition efficiency at different temperatures and
concentrations of the biomass extract. Consequently, experimental design was used
to assess the effects of these independent parameters that ultimately led to peak pro-
cess performance and the discovery of optimum conditions. The experimental design
was generated using a MINITAB 17.0 software (Stat-Ease Inc., USA). Each variable
was analyzed at five levels with a total of 25 experiments being performed represent-
ing a full factorial. The system response, which is the corrosion inhibition efficiency,
was determined by gasometric and thermometric methods (Tables 3 and 4).
3.2.2 Thermometric method
Similarly, using thermometric method given in Eq. 4, the percentage corrosion

inhibition was evaluated for the concentrations 1.0, 2.5, 5.0, 7.5, and 10.0 g/L, and
7
Figure 3.
Variation of pH of HCl solution with immersion time of mild steel in the presence of banana peel extract
(BPE).
Run order Concentration (g/L) (X1) Temperature (K) (X2) Inhibition, Ɛ (%)
1 7.5 303 64.14
2 5.0 313 51.11
3 1.0 303 44.40
4 10.0 313 61.75
5 2.5 308 49.53
6 7.5 318 49.25
7 7.5 313 53.14
8 2.5 318 40.28
9 5.0 308 56.31
10 2.5 313 44.43
11 10.0 323 49.21
12 1.0 323 24.75
13 2.5 303 54.73
14 10.0 303 72.03
15 1.0 313 34.00
16 7.5 308 59.00
17 7.5 323 44.17
18 1.0 318 29.15
19 5.0 323 41.62
20 5.0 303 61.51
21 1.0 308 39.20
22 5.0 318 29.15
23 10.0 308 66.83
24 10.0 318 54.62
25 2.5 323 34.92
Table 3.
Corrosion inhibition efficiency determination using gasometric method.
8
Run order Concentration (g/L) (X1) Temperature (K) (X2) Inhibition, Ɛ (%)
1 7.5 303 62.4
2 5.0 313 41.93
3 1.0 303 41.58
4 10.0 313 59.85
5 2.5 308 49.25
6 7.5 318 44.98
7 7.5 313 51.73
8 2.5 318 33.94
9 5.0 308 54.13
10 2.5 313 40.31
11 10.0 323 48.77
12 1.0 323 21.75
13 2.5 303 51.75
14 10.0 303 71.56
15 1.0 313 29.95
16 7.5 308 57.92
17 7.5 323 40.86
18 1.0 318 24.86
19 5.0 323 37.72
20 5.0 303 60.01
21 1.0 308 35.32
22 5.0 318 41.93
23 10.0 308 65.70
24 10.0 318 53.62
25 2.5 323 31.56
Table 4.
Corrosion inhibition efficiency determination using thermometric method.
at various temperatures. The experimental results presented in Tables 3 and 4 show

that at constant concentration of the extract; say, at 10 or 7.5 g/L, corrosion inhibition
efficiency decreased with increasing temperature. In the same vein, it was observed
that at constant temperature; say, 303 K, corrosion inhibition efficiency increased
with increasing inhibitor concentration. In a similar study, Gunavathy and Murugavel
[37] have reported that the inhibition efficiency of mild steel corrosion in acid
medium by Musa acuminata fruit peel extract increases with the increase in concen-
tration but decreases with increase in temperature. The same trend was reported by
Mayanglambam et al. [38] for Musa Paradisiaca extract on mild steel in sulfuric acid
solution. Lai et al. [39] have also worked on the inhibition of mild steel in HCl acid solu-
tion with a synthetic inhibitor, and/or synthetic mixed-type inhibitors as revealed by
potentiodynamic polarization measurement. It was equally reported that the efficiency
of the inhibitors decreased with increasing temperature as well as acid concentration.
3.3 Modeling and statistical analysis
Suitable statistical models were chosen to model the interactions between

the different experimental variables and their effect on the efficiency of cor-
rosion inhibition, based on the “Fit Regression Model” of MINITAB 17.0 (Pen,
USA). The response was modeled with a response surface quadratic model and
9
further analyzed by analysis of variance (ANOVA) to assess the significance of

each variable on corrosion inhibition. An empirical model that could relate the
response measured to the independent variables was obtained using multiple
regression analysis. The response (Y), can be represented by the following
quadratic model:
n n−1 n
Y = α o + ∑ ni=1
    α i Xi  + ∑   α ii X 2 i +  ∑  ∑ 
   α ij Xi  Xj  + ε (6)
i=1 i=1  j=i+1
where X1, X2, X3, …, Xn are the independent coded variables, α0 is the offset
term, and αi, αii, and αij account for the linear, squared, and interaction effects,
respectively, and ε is the random error. A model reduction may be expedient, if
there are many redundant model terms [40].
The statistical model summary based on the Lack-of-Fit Test explained the fit-
ness of quadratic models. Using ANOVA to assess the significance of each variable
in the model, empirical quadratic models were obtained from Eq. 6. These models,
Eqs. (7) and (8), for gasometric and thermometric methods, respectively, were used
to predict the efficiencies of the corrosion inhibition at the various values of the
independent variables.

Y = 376.0 + 2.660 X 1 − 1.0910 X 2. (7)

Y = 376.4 + 2.928 X 1 − 1.1038 X 2. (8)
The ANOVA of the quadratic regression model for the corrosion inhibition
showed the significant level of the model at 90.72 and 95.56% for gasometric
and thermometric methods, respectively (Tables 5 and 6). It indicates how well
the model fits the experimental data, implying that the total variance in the
response could be explained using this model. The closeness in the values of R-sq
(adj) and R-sq (pred) in both methods also shows the significance of the model.
Source DF Adj SS Adj MS F-value P-value
Regression 2 3372.9 1686.45 107.59 0.000
Conc. of BPE (g/L) 1 1885.6 1885.59 120.30 0.000
Temperature (K) 1 1487.3 1487.31 94.89 0.000
Error 22 344.8 15.67
Total 24 3717.7
Model summary
S R-sq R-sq (adj) R-sq (pred)
3.95907 90.72% 89.88%
Coefficient
Terms Coef SE coef T-value P-value VIF
Constant 376.0 35.1 10.72 0.000
Conc. of BPE (g/L) 2.660 0.243 10.97 0.000 1.00
Temperature (K) −1.091 0.112 −9.74 0.000 1.00
Table 5.
ANOVA for corrosion inhibition efficiency of BPE (gasometric method).
10
Source DF Adj SS Adj MS F-value P-value
Regression 2 3807.7 1903.87 236.50 0.000
Conc. of BPE (g/L) 1 2284.8 2284.78 283.81 0.000
Temperature (K) 1 1523.0 1522.97 189.18 0.000
Error 22 177.1 8.05
Total 24 3984.9
Model summary
S R-sq R-sq (adj) R-sq (pred)
2.83731 95.56% 95.15% 94.36%
Coefficient
Terms Coef SE coef T-value P-value VIF
Constant 376.0 25.1 14.97 0.000
Conc. of BPE (g/L) 2.928 0.174 16.85 0.000 1.00
Temperature (K) −1.1038 0.0803 −13.75 0.000 1.00
Table 6.
ANOVA for corrosion inhibition efficiency of BPE (thermometric method).
Regression results often show the statistical correlation and importance between
the predictor and response. The coefficient of determination (R2) is the percent-
age of inhibition efficiency (%) variation that is explained by its relationship
with concentration (g/L) and temperature (K). Therefore, the adjusted R2 is the
percentage of inhibition efficiency (%) variation that is explained by its relation-
ship with concentration (g/L) and temperature (K), adjusted for the number of
predictors in the model. This adjustment is important because R2 for this model
increases when a new independent variable is added. The adjusted R2 is a useful
tool for comparing the explanatory power of models with different numbers of
predictors. P-value for each coefficient tests the null hypothesis that the coef-
ficient has no effect [40].
3.4 Graphical representation of the model
Graphical representation allows easy interpretation of experimental results and

the prediction of optimal conditions. From the contour plots, Figures 4 and 5, BPE
was most efficient at temperatures below 307.5 K and concentrations above 8 g/L. The
least inhibitory effect was observed at temperature of 318 K and at lower concentra-
tions. This corroborated the experimental results where the highest corrosion inhibi-
tion was 72.03 and 71.56%, for gasometric and thermometric methods, respectively.
This peak performance occurred when concentration was 10 mol/L and temperature
303 K. Other higher values determined for inhibition efficiency occurred in the
neighborhood of 303 and 308 K, and 10 mol/L. Furthermore, the interactive effect of
the concentration and temperature on the system’s response (inhibition efficiency)
was assessed by plotting three-dimensional curves of the response against the inde-
pendent variables (Figures 6 and 7). The response distribution in this experiment
with respect to the variation of the independent variables shows that temperature has
a greater effect.
Similar corrosion inhibition efficiencies have been reported for biomass
extracts [37, 41]. In some other studies, inhibition efficiencies in the range of
11
Figure 4.
Contour plot showing the effects of concentration and temperature on the efficiency of corrosion inhibition of
BPE (Gasometric method).
Figure 5.
Contour plot showing the effects of concentration and temperature on the efficiency of corrosion inhibition of
BPE (Thermometric method).
80–90 have been reported for mild steel in HCl solution [42–45]. In a study
carried out by Ong and Karim [46], where the extract of red onion was used to
inhibit corrosion of mild steel in HCl solution, an inhibition efficiency of 90%
was reported also at temperature of 303 K. Since a combination of factors such as
temperature, concentration of inhibitors, and immersion time affects inhibition
efficiency, it is pretty difficult to compare extracts of different biomass. However,
reports have shown that temperature and concentration of inhibitors are the
predominant factors [47].
12
Figure 6.
Surface plot of inhibition efficiency (%) against concentration (g/L) and temperature (K) for gasometric
method.
Figure 7.
Surface plot of inhibition efficiency (%) against concentration (g/L) and temperature (K) for thermometric
method.
4. Conclusion
Statistical analysis using full factorial and the Regression Fit Model of MINITAB
17.0 was carried out to assess the effectiveness of Musa paradisiaca (banana) peel
extract as a green corrosion inhibitor for mild steel in acidic medium. The effect
of concentration of inhibitor and reaction temperature was investigated while the
efficiency of corrosion inhibition was evaluated by gasometric and thermometric
methods. The system’s response (inhibition efficiency) showed a stochastic distri-
bution with respect to the independent variables, with the highest corrosion inhibi-
tion efficiency being 72.03 and 71.56%, for gasometric and thermometric methods,
respectively. This peak performance occurred when the concentration was 10 mol/L
13
and temperature 303 K. Furthermore, the ANOVA of the quadratic regression

model for the corrosion inhibition showed the significant level of the model at 90.72
and 95.56% for gasometric and thermometric methods, respectively. The response
surface as well as the contour plots indicated the extract from the agro-waste was
most efficient at temperature below 307.5 K and at concentrations between 8 and
10 g/L. The least inhibitory effect was observed at temperatures above 318 K and
at concentrations below 6 mol/L. Banana peel extract is one of those plant extracts
that have shown to be promising in green corrosion inhibition.
14
References
[1] NACE International. International corrosion. Bioresource Technology.

Measures of Prevention, Application 2015;190:395-401
and Economics of Corrosion Technology
(IMPACT) Study. 2016. Available from: [9] El Haleem SA, El Wanees SA, Bahgat
http://inspectioneering.com/ [Accessed: A. Environmental factors affecting the
May 23, 2018] corrosion behaviour of reinforcing steel.
VI. Benzotriazole and its derivatives as
[2] Liu Z, Kleiner Y. State of the art corrosion inhibitors of steel. Corrosion
review of inspection technologies for Science. 2014;87:321-333
condition assessment of water pipes.
Measurement. 2013;46(1):1-15 [10] Tan Y-J, Bailey S, Kinsella B. An
investigation of the formation and
[3] Kishawy HA, Gabbar HA. Review destruction of corrosion inhibitor
of pipeline integrity management films using electrochemical impedance
practices. International Journal spectroscopy (EIS). Corrosion Science.
of Pressure Vessels and Piping. 1996;38(9):1545-1561
2010;87(7):373-380
[11] Taneja JN. Dissolution of iron in
[4] Iribarren JI, Liesa F, Alemán C, hydrochloric acid [Electronic Theses
Armelin E. Corrosion rate evaluation and Dissertations]. Canada: University
by gravimetric and electrochemical of Windsor; 1967
techniques applied to the metallic
reinforcing structures of a historic [12] Song G, Atrens A, StJohn D. An
building. Journal of Cultural Heritage. hydrogen evolution method for the
2017;27:153-163 estimation of the corrosion rate
of magnesium alloys. Magnesium
[5] Gadiyar HS, Chintamani D, Technology. 2001;2001:254-262
Gaonkar KB. Chemical cleaning,
decontamination and corrosion. [13] Volk C, Dundore E, Schiermann J,
Bombay, India: Bhabha Atomic Research Lechevallier M. Practical evaluation
Centre; 1991 of iron corrosion control in a
drinking water distribution system.
[6] Rebak RB, Perez TE. Effect of Water Research. 2000;34(6):
Carbon Dioxide and Hydrogen Sulfide 1967-1974
on the Localized Corrosion of Carbon
Steels and Corrosion Resistant Alloys. [14] Verma C, Olasunkanmi LO, Ebenso
Paper Presented at the CORROSION EE, Quraishi MA, Obot IB. Adsorption
2017; 2017 behavior of glucosamine-based,
pyrimidine-fused heterocycles as green
[7] Snihirova D, Taryba M, Lamaka corrosion inhibitors for mild steel:
SV, Montemor MF. Corrosion Experimental and theoretical studies.
inhibition synergies on a model The Journal of Physical Chemistry C.
Al-Cu-Mg sample studied by 2016;120(21):11598-11611
localized scanning electrochemical
techniques. Corrosion Science. [15] Zheng X, Zhang S, Gong M, Li
2016;112:408-417 W. Experimental and theoretical study
on the corrosion inhibition of mild
[8] Kim BH, Lim SS, Daud WRW, steel by 1-octyl-3-methylimidazolium
Gadd GM, Chang IS. The biocathode L-prolinate in sulfuric acid solution.
of microbial electrochemical Industrial & Engineering Chemistry
systems and microbially-influenced Research. 2014;53(42):16349-16358
15
[16] Verma C, Quraishi M, Kluza K, [23] Ekpe U, Ibok U, Ita B, Offiong

Makowska-Janusik M, Olasunkanmi O, Ebenso E. Inhibitory action of
LO, Ebenso EE. Corrosion inhibition methyl and phenyl thiosemicarbazone
of mild steel in 1M HCl by D-glucose derivatives on the corrosion of
derivatives of dihydropyrido [2, 3-d: 6, mild steel in hydrochloric acid.
5-d′] dipyrimidine-2, 4, 6, 8 (1H, 3H, Materials Chemistry and Physics.
5H, 7H)-tetraone. Scientific Reports. 1995;40(2):87-93
2017;7:44432
[24] Gerengi H, Sahin HI. Schinopsis
[17] Bethencourt M, Botana F, lorentzii extract as a green corrosion
Calvino J, Marcos M, Rodriguez- inhibitor for low carbon steel in 1 M
Chacon M. Lanthanide compounds HCl solution. Industrial & Engineering
as environmentally-friendly Chemistry Research. 2011;51(2):780-787
corrosion inhibitors of aluminium
alloys: A review. Corrosion Science. [25] Muthumanickam S, Jeyaprabha
1998;40(11):1803-1819 B, Karthik R, Elangovan A, Prakash
P. Adsorption and corrosion inhibiting
[18] Morad M. Effect of amino acids behavior of Passiflora foetida leaf extract
containing sulfur on the corrosion of on mild steel corrosion. International
mild steel in phosphoric acid solutions Journal of Corrosion and Scale
containing Cl−, F− and Fe 3+ ions: Inhibition. 2015;4(4):365-381
Behavior under polarization conditions.
Journal of Applied Electrochemistry. [26] Alibakhshi E, Ramezanzadeh M,
2005;35(9):889-895 Bahlakeh G, Ramezanzadeh B,
Mahdavian M, Motamedi M. Glycyrrhiza
[19] Abiola OK, Oforka N, Ebenso E, glabra leaves extract as a green
Nwinuka N. Eco-friendly corrosion corrosion inhibitor for mild steel in 1 M
inhibitors: The inhibitive action of hydrochloric acid solution: Experimental,
Delonix Regia extract for the corrosion molecular dynamics, Monte Carlo and
of aluminium in acidic media. Anti- quantum mechanics study. Journal of
Corrosion Methods and Materials. Molecular Liquids. 2018;255:185-198
2007;54(4):219-224
[27] Amodu OS, Ntwampe SK, Ojumu
[20] Nnaji NJ, Ujam OT, Ibisi NE, TV. Emulsification of hydrocarbons
Ani JU, Onuegbu TO, Olasunkanmi by biosurfactant: Exclusive use
LO, et al. Morpholine and piperazine of agrowaste. BioResources.
based carboxamide derivatives as 2014a;9(2):3508-3525
corrosion inhibitors of mild steel in HCl
medium. Journal of Molecular Liquids. [28] Mohapatra D, Mishra S, Sutar N.
2017;230:652-661 Banana and its by-product utilisation:
An overview. Journal of Scientific and
[21] Odewunmi N, Umoren S, Gasem Industrial Research. 2010;69:323-329
Z. Watermelon waste products as green
corrosion inhibitors for mild steel in [29] ASTM. Standard Test Method
HCl solution. Journal of Environmental for Kinematic Viscosity of
Chemical Engineering. 2015;3(1):286-296 Transparent and Opaque Liquids (the
Calculation of Dynamic Viscosity).
[22] Ituen E, James A, Akaranta O, Sun West Conshohocken, PA: ASTM
S. Eco-friendly corrosion inhibitor International; 1997. www.astm.org
from Pennisetum purpureum biomass
and synergistic intensifiers for mild [30] Ebenso E, Eddy N, Odiongenyi
steel. Chinese Journal of Chemical A. Corrosion inhibition and adsorption
Engineering. 2016;24(10):1442-1447 properties of methocarbamol on mild
16
steel in acidic medium. Portugaliae Portugaliae Electrochimica Acta.

Electrochimica Acta. 2009;27(1):13-22 2011;2011, 29(6):405-417
[31] Okafor P, Ebenso E. Inhibitive action [39] Lai C, Xie B, Zou L, Zheng
of Carica papaya extracts on the corrosion X, Ma X, Zhu S. Adsorption and
of mild steel in acidic media and their corrosion inhibition of mild steel in
adsorption characteristics. Pigment & hydrochloric acid solution by S-allyl-O,
Resin Technology. 2007;36(3):134-140 O′-dialkyldithiophosphates. Results in
Physics. 2017;7:3434-3443
[32] Maneerat N, Tangsuphoom N,
Nitithamyong A. Effect of extraction [40] Amodu OS, Ntwampe SK, Ojumu
condition on properties of pectin TV. Optimization of biosurfactant
from banana peels and its function production by Bacillus licheniformis
as fat replacer in salad cream. Journal STK 01 grown exclusively on Beta
of Food Science and Technology. vulgaris waste using response
2017;54(2):386-397 surface methodology. BioResources.
2014b;9(3):5045-5065
[33] SPE. Oil and gas facilities: Corrosion
monitoring and mitigation technologies. [41] Akalezi CO, Enenebaku CK, Oguzie
Society of Petroleum Engineering. EE. Inhibition of acid corrosion of
2013;6(2):1-6 mild steel by biomass extract from
the Petersianthus macrocarpus plant.
[34] Kliškić M, Radošević J, Gudić Journal of Materials and Environmental
S, Katalinić V. Aqueous extract of Science. 2013;4(2):217-226
Rosmarinus officinalis L. as inhibitor
of Al–Mg alloy corrosion in chloride [42] Raja PB, Qureshi AK, Rahim AA,
solution. Journal of Applied Osman H, Awang K. Neolamarckia
Electrochemistry. 2000;30(7):823-830 cadamba alkaloids as eco-friendly
corrosion inhibitors for mild steel in
[35] Betiku E, Akintunde AM, Ojumu 1 M HCl media. Corrosion Science.
TV. Banana peels as a biobase catalyst 2013;69:292-301
for fatty acid methyl esters production
using Napoleon's plume (Bauhinia [43] Negm N, Kandile N, Aiad I,
monandra) seed oil: A process Mohammad M. New eco-friendly
parameters optimization study. Energy. cationic surfactants: Synthesis,
2016;103:797-806 characterization and applicability as
corrosion inhibitors for carbon steel
[36] Noor EA, Al-Moubaraki AH. in 1 N HCl. Colloids and Surfaces A:
Corrosion behavior of mild steel Physicochemical and Engineering
in hydrochloric acid solutions. Aspects. 2011;391(1-3):224-233
Science. 2008;3(1):806-818 [44] Gunasekaran G, Chauhan L. Eco
friendly inhibitor for corrosion
[37] Gunavathy N, Murugavel S. inhibition of mild steel in phosphoric
Corrosion inhibition studies of mild acid medium. Electrochimica Acta.
steel in acid medium using Musa 2004;49(25):4387-4395
acuminata fruit peel extract. Journal of
Chemistry. 2012;9(1):487-495 [45] Verma C, Quraishi M, Ebenso EE,
Bahadur I. A green and sustainable
[38] Mayanglambam RS, Sharma V, approach for mild steel acidic corrosion
Singh G. Musa Paradisiaca extract as a inhibition using leaves extract:
green inhibitor for corrosion of mild Experimental and DFT studies. Journal of
steel in 0.5 M sulphuric acid solution. Bio-and Tribo-Corrosion. 2018;4(3):33
17
[46] Ong CC, Karim KA. Inhibitory

effect of red onion skin extract on
the corrosion of mild steel in acidic
medium. Chemical Engineering
Transactions. 2017;56:913-918
[47] Bao J, Zhang H, Zhao X, Deng

J. Biomass polymeric microspheres
containing aldehyde groups:
Immobilizing and controlled-releasing
amino acids as green metal corrosion
inhibitor. Chemical Engineering
Journal. 2018;341:146-156
18
Chapter 04
Green Corrosion Inhibitory

Potentials of Cassava Plant
(Manihot esculenta Crantz) Extract
Nanoparticles (CPENPs) in
Coatings for Oil and Gas Pipeline
Funsho O. Kolawole, Shola K. Kolawole,
Oluwamayowa M. Olugbemi and Suleiman B. Hassan
Abstract
Internal and external corrosion affects oil and gas pipelines and were discussed
in this chapter. Corrosion inhibitors are one of the methods that can be used to
achieve corrosion control and prevention. The main discussion in this chapter was
the use of cassava plant (Manihot esculenta Crantz) extract nanoparticles (CPENPs)
as an additive in coatings to serve as a green corrosion inhibitor for oil and gas
pipeline. Trace elements, such as O, Si, Ca, K, Fe and S, which are hetero-atoms,
have been identified in CPENPs. Elements like Si and Ca would also improve the
strength of coatings as well as reduce corrosion rate of coated metals. It has also
been revealed that CPENPs is composed of the following compounds SiO2, CaCO3,
Ca2(SO4)2H2O and CaC2O4(H2O), which would help in improving the mechanical
properties of alloys, composites and coatings. SiO2 if added to coatings will improve
the coating hardness, while the presence of CaCO3 in coatings will form a precipi-
tate that will serve as a protective film on the surface of the metal, thereby protect-
ing the metal from corrosion. The nature of bond and organic compounds that exist
in the CPENPs was also discussed.
Keywords: cassava extract, coatings, corrosion, green inhibitor, nanoparticles
1. Introduction
Corrosion is the main problem affecting pipelines in the oil and gas industry.
Internal corrosion in oil and gas pipelines is primarily caused by the presence of
water together with acid gases or sulphate reducing bacteria. It can be categorized
into three: sweet corrosion, sour corrosion and microbiological influenced cor-
rosion. Conversely, in external corrosion the medium in the surrounding reacts
with the outer side of metal pipelines thereby causing certain damages. The soil is
complex three-phased system, which makes it a conductor to the metal pipelines.
The application of coating and inhibitors has help to solve the corrosion problem.
Coatings may be applied alone or may be used with other common methods such
1
as proper material selection, cathode protection (CP) and application of inhibi-

tors to modify the corrosive environment. In time past different types of coatings
have been used such as bituminous enamels, asphalt mastic, liquid epoxies and
phenolics, extruded plastic coatings, fusion-bonded epoxy (FBE), tape, three-
layer polyolefin, wax coatings, high performance composite coating system, low
temperature application technology for powder, thermotite flow assurance coating
technology and paint. Paints used as coatings have been very effective in reducing
the rate of corrosion in many industries, where various metals which are prone to
corrosion are put into use.
Use of some inhibitors, such as chromate, has been banned because of toxicity
and the environmental hazards they create [1]. Hence there is a need to make use of
environmental friendly, non-toxic extracts of naturally occurring plant materials
as corrosion inhibitors also known as green corrosion inhibitors. Extracts of plant
materials contain a wide variety of organic compounds. Most of them contain
hetero-atoms such as phosphorous, nitrogen, sulfur and oxygen. These atoms
coordinate with the corroding metal atom (their ions) through their electrons [2].
Hence protective films are formed on the metal surface, thereby preventing cor-
rosion. Some of the green corrosion inhibitors that have been used in the past are
extracts from Aloe vera, Banana Plant juice, Mango, Orange, Passion fruit, Cashew
peels, Tobacco leaves, etc. [1, 3–5].
Most researches have led to the discovering of new green corrosion inhibitors
from plant part, but few of them have provided practical coating application that
can solve corrosion problems as it applies to the oil and gas pipelines. Most green
corrosion inhibitors are extracted from food and fruit items e.g. mango, orange,
cassava, cashew juice and bitter leaf, which endangers food security. It is important
to identify the ingredients and nature of bonds that exist in plant part extracts
which are responsible for inhibiting corrosion in steel pipelines. The use of liquid
extracts from cassava tuber has been studied in the past for corrosion resistance for
mild steel [6]. But there is still work to be done in the area of coating using green
inhibitors. Cassava plant solid extract (bark, stem and leaf) which are dumped in
the environment can be processed and used as corrosion inhibitors because of the
presence of heteroatoms and organic compounds, which are responsible for inhibit-
ing corrosion. Processing of cassava plant solid extract (bark, leaf and stem) into
green corrosion inhibitor will provide a cheap, environmental friendly and efficient
green corrosion inhibitor and also solve environmental challenges caused by the
dumped cassava waste.
Paint which usually consists of four main parts includes: solvents, pigments,
binders and additives. In dealing with anticorrosive paints, red oxide pigment helps
in preventing corrosion. The additives in paints play vital roles, which include the
inhibition of corrosion. Inhibitors can be added to paint and it must be non-toxic,
environmentally friendly, cost effective and readily available. Extracts from plants
have been used as green inhibitors in the past and have been found to be envi-
ronmentally friendly, non-toxic, cheap and abundantly available. Nanoparticles
can improve paint property because of the unique properties of nanoparticles.
Incorporating nanosize additives in paint provide effective barrier performance,
reduce the amount of holiday in paint and also enhance the integrity and durability
of paint, since the fine particles dispersed in paint can fill cavities. Research has
been carried out on cassava starch as green corrosion inhibitors [7], and the modi-
fication of cassava starches as potential corrosion inhibitors has been used on steel
rods. Cassava starch which is sometimes a waste in most cassava processing plants,
shows considerable improvement in the prevention of corrosion [8].
This current chapter seeks to discuss green corrosion inhibitory potentials
of cassava plant (Manihot esculenta Crantz) extract nanoparticles (CPENPs) in
2
Green Corrosion Inhibitory Potentials of Cassava Plant (Manihot esculenta Crantz) Extract…
coatings for oil and gas pipeline. The cassava extract to be considered here are the
bark, leaf and stem, which is usually dumped all over the environment as waste.
Cassava extract can be processed into nanoparticles and added into coatings as a
green corrosion inhibitor.
2. Corrosion problems in oil and gas pipeline
Corrosion is the main problem affecting oil and gas pipelines. Understanding
the electro-chemical nature of corrosion was a major breakthrough, as shown in
Figure 1, and this made it possible for corrosion to be mitigated, if electric current
sufficient to offset the inherent corrosion current of a particular environment were
caused to flow in the opposite direction. The applied direct current was termed
“cathodic” protection because it made the pipe the cathode in a galvanic cell [10, 11].
The required current could be supplied by connecting a “sacrificial” anode (i.e., a
metal with a higher oxidation potential than iron) in an electrical circuit where soil
acted as the “electrolyte.” Alternatively, commercial current could be directed to the
pipe via an anode bed. The application of coating and inhibitors also help to solve
the corrosion problem [10, 11].
2.1 Internal corrosion in pipeline
Internal corrosion in oil and gas pipelines is primarily caused by the presence of
water together with acid gases (carbon dioxide or hydrogen sulphide) or sulphate
reducing bacteria [12]. It can be divided into three broad categories:
• Sweet corrosion
• Sour corrosion
• Microbiological influenced corrosion (MIC)
2.2 External corrosion in pipeline
The medium in the surrounding reacts with the outer side of metal pipelines
chemically, electrochemically and physically causing certain damages. These dam-
ages are called external corrosion of pipelines. The soil is complex three-phased
Figure 1.
Schematic of anodic site and cathodic site as they lead to corrosion [9].
3
system, which makes it a conductor to the metal pipelines. Plus, the oxygen concen-
tration cell caused by the oxygen concentration difference accelerates the pipeline
corrosion [13].
• Differential cell corrosion
• Galvanic corrosion
2.3 Control and prevention of corrosion in the oil and gas industry
Control and prevention of corrosion in the oil and gas industries has been on for
a long time. Although many methods have been suggested to arrest corrosion, they
can be classed broadly into four main categories; selection of appropriate materials,
use of inhibitors, use of protective coatings and cathodic protection [13].
3. Corrosion inhibitors
An inhibitor is a substance that, when added in small concentrations to an envi-

ronment, decreases the corrosion rate. In a sense, an inhibitor can be considered as
a retarding catalyst. There are numerous inhibitor types and compositions and are
generally classified into organic and inorganic inhibitors (Figure 2). Most inhibi-
tors have been developed by empirical experimentation, and many inhibitors are
proprietary in nature and thus their composition is not disclosed. The chemicals,
their concentration, and the frequency of injection depend on the process medium
and, normally, on the recommendations of the inhibitor manufacturer, since these
chemicals, although generic in nature, are generally proprietary items [10, 13, 15].
The inhibitors used are normally chromates, phosphates, and silicates, added fol-
lowing the recommendations of the manufacturer. The removal of oxygen from a
fluid medium improves the chances of corrosion resistance by materials in contact
with the fluid. Controlling and stabilizing the pH value of the medium is another
method of combating corrosion Inhibition is not completely understood because of
these reasons, but it is possible to classify inhibitors according to their mechanism
and composition. The corrosion rates of usefully resistant materials generally range
between 1 and 200 mpy [10, 13, 15].
3.1 Inorganic corrosion inhibitors
Substances, such as arsenic and antimony ions, specially retard the hydrogen-
evolution reaction. As a consequence, these substances are very effective in acid
Figure 2.
Classification of inhibitors [14].
4
solutions but are ineffective in environments where other reduction processes such
as oxygen reduction are the controlling cathodic reactions [15]. Scavengers are sub-
stances that act by removing corrosive reagents from solution. Oxidizers are sub-
stances as chromate, nitrate, and ferric salts also act as inhibitors in many systems.
In general, they are primarily used to inhibit the corrosion of metals and alloys that
demonstrate active-passive transitions, such as iron and its alloys and stainless steels
[15]. Vapor-phase inhibitors are very similar to the organic adsorption-type inhibi-
tors and possess a very high vapor pressure. Generally, the inorganic inhibitors have
cathodic actions or anodic.
3.1.1 Anodic inhibitors
Anodic inhibitors (also called passivation inhibitors) act by a reducing anodic

reaction, that is, blocks the anode reaction and supports the natural reaction of
passivation metal surface, also, due to the forming a film adsorbed on the metal. In
general, the inhibitors react with the corrosion product, initially formed, result-
ing in a cohesive and insoluble film on the metal surface [14, 16, 17]. The anodic
inhibitors reacts with metallic ions Men+ produced on the anode, forming generally,
insoluble hydroxides which are deposited on the metal surface as insoluble film
and impermeable to metallic ion, from the hydrolysis of inhibitors results in OH−
ions [16]. Some examples of anodic inorganic inhibitors are nitrates, molybdates,
sodium chromates, phosphates, hydroxides and silicates [14, 15]. Potentiostatic
polarization diagram showing electrochemical behavior of a metal in a solution
with anodic inhibitor (a) versus without inhibitor (b) is illustrated in Figure 3.
3.1.2 Cathodic inhibitors
As the corrosion process begins, the cathodic corrosion inhibitors prevent the
occurrence of the cathodic reaction of the metal. These inhibitors have metal ions
able to produce a cathodic reaction due to alkalinity, thus producing insoluble
compounds that precipitate selectively on cathodic sites. Deposit over the metal a
compact and adherent film, restricting the diffusion of reducible species in these
areas. Thereby, increasing the impedance of the surface and the diffusion restric-
tion of the reducible species, in this case, the oxygen diffusion and electrons con-
ductive in these areas. These inhibitors cause high cathodic inhibition [14, 16–18].
Figure 4 shows an example of a polarization curve of the metal on the solution with
a cathodic inhibitor. When the cathodic reaction is affected the corrosion, potential
Figure 3.
Potentiostatic polarization diagram: electrochemical behavior of a metal in a solution with anodic inhibitor
(a) versus without inhibitor (b) [14].
5
Figure 4.
Potentiostatic polarization diagram: electrochemical behavior of a metal in a cathodic inhibitor solution (a), as
compared to the same solution without inhibitor (b) [14].
is shifted to more negative values [15]. When cathodic inhibitors minimize the
release of hydrogen ions due to a phenomenon that can difficult the discharge of the
hydrogen, called overvoltage [14].
3.2 Organic corrosion inhibitors
Environmental concerns require corrosion inhibitors to be nontoxic and

environment friendly and acceptable. Green chemistry serves as a source of envi-
ronmental friendly green corrosion inhibitors. Corrosion inhibitors are extensively
used in corrosion protection of metals and equipment. Organic compounds with
functional groups containing nitrogen, sulfur, and oxygen atoms are generally used
as corrosion inhibitors. Most of these organic compounds are not only expensive
but also harmful to the environment. Thus, efforts have been directed toward the
development of cost effective and nontoxic corrosion inhibitors. Plant products
and some other sources of organic compounds are rich sources of environmentally
acceptable corrosion inhibitors. An example of such a system is the corrosion inhi-
bition of carbon steel by caffeine in the presence and absence of zinc. Plant prod-
ucts are a source of environment-friendly green inhibitors such as phthalocyanines
[2]. After the addition of the inhibitor, the corrosion potential remains the same,
but the current decreases from Icor to I’cor. Is showed in Figure 5 the mechanism of
actuation of organic inhibitors, when it is adsorbed to the metal surface and forms a
protector film on it.
The inhibitor efficiency could be measured by the follow equation:
R  − R 
Ef = _____
  i   o 
 x 100 (1)
Ro 
where Ef is inhibitor efficiency (percentage), Ri is corrosion rate of metal with

inhibitor and Ro is corrosion rate of metal without inhibitor [14].
3.3 Corrosion inhibitor mechanism
Corrosion inhibition mechanisms operating in an acid medium differs widely

from one operating in a near-neutral medium. Corrosion inhibition in acid solutions
can be achieved by halides, carbon monoxide, and organic compounds containing
functional group heteroatoms such as nitrogen, phosphorus, arsenic, oxygen, sulfur,
and selenium, organic compounds with multiple bonds, proteins, polysaccharides,
6
glue, bitumen, and natural plant products such as chlorophyll and anthocyanins
[19]. The initial step in the corrosion inhibition of metals in acid solutions consists
of adsorption of the inhibitor on the oxide-free metal surface followed by retarda-
tion of the cathodic and/or the anodic electrochemical corrosion reactions [19].
Corrosion inhibitors work by forming a protective film on the metal preventing
corrosive elements contacting the metal surfaces, as illustrated in Figure 6.
The action mechanisms of corrosion inhibitors are;
• By adsorption, forming a film that is adsorbed onto the metal surface,
• By inducing the formation of corrosion products such as iron sulfide, which is a

passivizing species,
• By changing media characteristics, producing precipitates that can be protective

and eliminating or inactivating an aggressive constituent.
It is well known that organic molecules inhibit corrosion by adsorption, forming

a barrier between the metal (pipeline) and the environment. Thus, the polar group
of the molecule is directly attached to metal and the non-polar end is oriented in a
vertical direction to the metal surface, which repels corrosive species as illustrated
in Figure 6, furthermore establishing a barrier against chemical and electrochemi-
cal attack by fluids on the metallic surface [20, 21].
Figure 5.
Theoretical potentiostatic polarization diagram: electrochemical behavior of a metal in a solution containing a
cathodic and anodic inhibitor (a) compared to the same solution without the inhibitor (b) [14].
Figure 6.
Schematic of modified inhibitor film prevents water contacting a pipeline surface.
7
An inhibitor may be effective in one system, while in another it is not, therefore,

it is convenient to consider the following factors: chemical structure of the inhibitor
component, chemical composition of the corrosive medium, nature of the metal
surface (pipeline), operating conditions (temperature, pressure and pH) thermal
stability of the inhibitor—corrosion inhibitors have temperature limits above which
lose their effectiveness because they suffer degradation of the containing compo-
nents, solubility of the inhibitor in the system—the solubility of the inhibitor in
the system is required to achieve optimum results in the metal surface protection;
this depends on the length of the hydrocarbon chain, the addition of surfactants
to enhance the dispersibility or solubility of inhibitors, and modification of the
molecular structure of the inhibitor by ethoxylation to increase the polarity, and
thus reach its solubility in the aqueous medium [21].
The main features of an inhibitor are:
• Ability to protect the metal surface.
• High activity to be used in small quantities (ppm).
• Low cost compounds.
• Inert characteristics to avoid altering a process.
• Easy handling and storage.
• Preferably with low toxicity.
• Non-contaminant.
• It should act as an emulsifier.
• It should act as a foaming agent [21].
4. Paints for corrosion protection
Paints are made up of a mixture of different components, although paints

designed for different purposes will have different formulations, they all have some
key features in common. Paints contain a pigment to give color, including white; a
film former that binds the pigment particles together and binds them to the surface
to be painted; a liquid that makes it easier to apply the paint and additives to make
the basic paint better to store and to use. There are two main types of paint, which
are gloss and emulsion [22]. Table 1 shows a typical gloss paint formulation.
4.1 Alkyd resin binder
The alkyd resins produced this way are referred to as oil-modified alkyd resins
and contribute about 70% to the conventional binders used in surface coating [23].
They determine the performance quality of surface coatings such as the rate of
drying, gloss, durability of the dry film and resistance of the dry film to abrasion
and chemicals. However, classification of alkyd resins is based on the oil length
and oil type [24]. The vegetable oils used in oil-modified alkyd resins are usually
extracted either by mechanical press or solvent extraction [25]. The natural oil in
the oil-modified alkyds reacts with atmospheric oxygen leading to the formation of
8
Component Mass (%)
Alkyd resin binder 30
Pigment 25
Solvent 40
Additives 5
Table 1.
A typical gloss paint formulation [22].
network of polymers cross-linked through the C=C bond. The oxidative drying of
the oil brings about the formation of film that shows improved properties with dry-
ing time, hardness or water resistance [26]. The oils used in surface coatings contain
linolenic and conjugated acid groups, such oils include linseed, perilla and tung oils
and possess pronounced drying abilities [27]. There has been tremendous increase
in the demand for alkyd resin production for use in the Nigerian surface coating
industry due to the rapid growth of the economy [27].
4.2 Red oxide pigment
The use of iron oxides as natural pigments has been practiced since earliest
times. The iron oxides such as magnetite, hematite, maghemite and goethite are
commonly used as pigments for black, red, brown and yellow colors respectively.
Predominantly natural red iron oxides are used in primers for steel constructions
and cars reducing corrosion problems. Iron oxide are strong absorbers of ultraviolet
radiation and mostly used in automotive paints, wood finishes, construction paints,
industrial coatings, plastic, nylon, rubber and print ink [28].
4.3 Solvent
Solvents are not the only means of removing low molecular weight compounds.
Heat can help evaporate saturated fatty acids, such as palmitic and stearic acids,
and an improperly stored or displayed painting can become embrittled by the loss
of these plasticizers. The long-term behavior of oil paints also seems to indicate that
a small amount of evaporation of fatty acids occurs over time. Improper tempera-
ture on a hot table may do so as well since the volatility of the fatty acids becomes
significant above 70–80°C [29].
The mechanical properties of a paint film depend upon its basic structure and
the presence of small organic molecules that may act as plasticizers. The original
structure of a paint film contains the ester bonds of the oil and the bonds produced
by the cross-linking of the unsaturated fatty acids through autoxidation. The loss
of any of these bonds results in weakening the film strength. Any loss of the ester
bonds must have a significant effect on the structure of the oil paint. After 6 years,
the paints made with varying degrees of hydrolyzed oil appear as coherent films,
but some disintegrate when solvents, such as acetone or toluene, are applied because
these solvents can remove the low molecular weight compounds that contribute to
the stability of the paints [29].
4.4 Additives
Additives are small amounts of substances that modify the paint properties,
additives might be driers anti-skin agents, anti-corrosive agents, antifreeze, dis-
persing aids, wetting agents, thickeners, biocides, low temperature drying aids,
9
anti-foam agent, and coalescing solvent. Driers accelerate the paints drying (hard-
ening) by catalyzing the oxidation of the binder, while plasticisers increase the
paints flexibility. Fungicides, biocides and insecticides prevent growth and attack
of fungi, bacteria and insects and flow control agents improve flow properties.
Defoamers prevent formation of air bubbles entrapped in the coatings, emulsifiers
are wetting agents increasing the colloidal stability of the paints in liquid state,
while UV stabilizers provide stability of the paints under ultra-violet light, and
anti-skinning agents prevent formation of a skin in the can. Adhesion promoters
improve the adhesion of the coating to the substrate, and texturizers impart tex-
tures to the coatings [29].
4.5 Nanoparticles
Nanoparticles are important scientific tools that have been and are being
explored in various biotechnological, pharmacological and pure technological
uses. They are a link between bulk materials and atomic or molecular structures.
While bulk materials have constant physical properties regardless of its size, among
nanoparticles the size often dictates the physical and chemical properties. Thus,
the properties of materials change as their size approaches the nanoscale and as
the percentage of atoms at the surface of a material becomes significant. For bulk
materials, those larger than 1 μm (or micron), the percentage of atoms at the surface
is insignificant in relation to the number of atoms in the bulk of the material.
Nanoparticles are unique because of their large surface area and this dominates the
contributions made by the small bulk of the material [30, 31].
In typical nanomaterials, the majority of the atoms located on the surface of
the particles, whereas they are located in the bulk of conventional materials. Thus,
the intrinsic properties if nanomaterials are different from conventional materials
since the majority of atoms are in a different environment. Nanomaterials represent
almost the ultimate in increasing surface area and they are chemically very active
because the number of surface molecules or atoms is very large compared with the
molecules or atoms in the bulk of the materials. Substances with high surface areas
have enhanced physical, chemical, mechanical, optical and magnetic properties
and this can be exploited for a variety of structural and non-structural application.
Nanoparticles/fillers find application in wear-resistant, erosion-resistant and corro-
sion resistant [31]. Coatings with nanostructure bring about a reduction in surface
contact tension, minimization of moisture penetration, and reduction in surface
roughness to 1 nm for better dirt repellence [31].
4.6 Synthesis of nanoparticles
Nanoparticles of various types has been synthesized; gold, silver, magnetite,

zinc oxide, silicon oxide, and others [32–35], which can be synthesized using
methods such as the breakdown (top-down) method and the build-up (bottom-up)
method [33].
5. Plant extracts
Plants naturally synthesize chemical compounds in defense against fungi,

insects and herbivorous mammals. Some of these compounds or phytochemicals
such as alkaloids, terpenoids, flavonoids, polyphenols and glycosides prove ben-
eficial to humans in unique manner for the treatment of several diseases. These
compounds are identical in structure and function to conventional drugs. Extracts
10
from parts of plants such as roots, stems, and leaves also contain such extraordi-
nary phytochemicals that are used as pesticides, antimicrobials, drugs and herbal
medicines [4, 36–38].
5.1 Plant extracts as green inhibitors
Plant extracts are excessively used as corrosion inhibitors. Plant extracts

contain a variety of organic compounds such as alkaloids, flavonoids, tannins,
cellulose and polycyclic compounds. The compounds with hetero atoms-N, O, S,
P coordinate with (corroding) metal atom or ion consequently forming a protec-
tive layer on the metal surface, which prevents corrosion. These serve as cheaper,
readily available, renewable and environmentally benign alternatives to costly and
hazardous corrosion inhibitors (e.g., chromates). Plant extracts serve as anticor-
rosion agents to various metals such as mild steel, copper, zinc, tin, nickel, alumi-
num and its alloys [37, 38].
There are exhaustive numbers of plant extracts that have shown proven anticor-
rosion activity as corrosion inhibitors. Examples are Swertia angustifolia, Acacia
concinna, Emblica officinalis, Terminalia chebula, Terminalia belivia, Sapindus trifo-
liatus, Pongamia glabra, Eucalyptus leaves, Annona squamosa, Eugenia jambolana,
Azadirachta indica, Acacia arabica, Vernonia amygdalina, Carica papaya, Rosmarinus
officinalis, Hibiscus sabdariffa, Opuntia extracted, Mentha pulegium, Ocimum viri-
dis, Datura metel, Ricinus communis, Chelidonium majus, Papaia, Poinciana pulcher-
rima, Cassia occidentalis and Datura stramonium seeds, Papaia, Calotropis procera B,
Azydracta indica, Justicia gendarussa, Artemisia pallens, Auforpio turkiale sap, Black
pepper extract, henna extract and several others [4, 36–38].
5.2 Cassava plant
Cassava can be grown on a wide range and can yield satisfactorily even in acidic
soils where most other crops fails [39], the crop has continually played very vital
roles, which include income for farmers, low cost food source for both the rural and
urban dwellers as well as household food security. In Nigeria, Cassava is gener-
ally believed to be cultivated by small scaled farmers with low resources. It also
plays a major role in the effort to alleviate the food crisis in Africa [39]. Cassava
with botanical name Manihot esculenta, is a woody shrub of the spurge family,
Euphorbiaceae, native to South America. It is extensively cultivated as an annual
crop in tropical and subtropical regions for its edible starchy tuberous root, a major
source of carbohydrates [40]. World production of cassava root was estimated to
be 245 million tonnes in 2012 [41]. Africa produces about 137 million tonnes, which
is the largest contribution to the world production; 75 million tonnes is produced
from Asia; and 33 million tonnes in Latin America and the Caribbean, specifically
Jamaica. Nigeria is the world’s largest producer of cassava, producing about 37.5
million tonnes annually [41]. A mature cassava root (hereafter referred to as ‘root’)
may range in length from 15 to 100 cm and weigh 0.5–2.5 kg. Circular in cross-
section, it is usually fattest at the proximal end and tapers slightly toward the distal
portion. It is connected to the stem by a short woody neck and ends in a tail similar
to a regular fibrous root.
5.2.1 Cassava bark (CB)
Cassava bark also known as cassava peels are always dumped in abundant as
waste. Although, it has been reported that both leaf and bark contains cyanogenic
glucosides, linamarin, lotaustralin, starch, amino acid, carbohydrate, proteins and
11
tannin [41]. Cassava bark (CB) consist of two layers namely; the outer skin and
inner skin [42], both layers combine together serves as agro-waste and since annual
production is high and it has been reported that the bark consist of 5–10% of the
cassava root [42–44], the amount of agro-waste that can be generated from cassava
bark is significant. CB is used for animal feed [42], biogas [43].
5.2.2 Cassava leaf (CL)
Cassava leaves are sometimes considered as agro-waste, though it has other

applications such as animal feed [42, 45], medicinal application (Aro, 2008) and
pack-cyaniding of mild steel [45]. Cassava leaves are also known for their high
HCN content, low energy, bulkiness and their high tannin content [42, 45]. Cassava
leaves are nutritionally valuable products and cassava plant could yield 7–15 tonnes
of leaves per hectare, which accounts for an additional 1 tonne of valuable protein
and 2.5 tonnes of carbohydrate per hectare [42]. Up to 6% of cassava leaves can be
obtained from the total production of cassava [42].
5.2.3 Cassava stem (CS)
Cassava stem is the largest waste generated from cassava plantation after
harvest, up to 400 bundles can be obtained per hectare (Information and
Communication Support for Agricultural Growth in Nigeria, 2015). From the
estimated amount of cassava stem waste generated it shows that enough can be
obtained for processing into useful application. Cassava stem can be fed to pigs,
poultry, dairy cattle [45] and biochar production [46].
5.3 Synthesis of cassava plant extract nanoparticles (CPENPs)
CPENPs which comprises of cassava bark nanoparticles (CBNPs) [47], cas-

sava leaf nanoparticles (CLNPs) [48] and cassava stem nanoparticles (CSNPs)
[48] were obtained by first soaking for 24 h, after which ball milling for 60 h
was carried out, to achieve a particles size below 100 nm which were estimated
by SEM/Gwyddion software, XRD and TEM [47, 48]. Trace elements such as O,
Si, Ca, K, Fe and S, were revealed using EDX, which are hetero-atoms and can
be added to coatings to help in inhibiting corrosion on metal surfaces [47, 48].
Elements like Si and Ca would improve the strength of coatings as well as reduce
corrosion rate of coated metals [47, 48]. XRD revealed compounds such as SiO2,
CaCO3, Ca2(SO4)2H2O and CaC2O4(H2O), these compounds would help in improv-
ing the mechanical properties of alloys or composites and coatings. SiO2 if added
to coatings will improve the coating hardness, while the presence of CaCO3 in
coatings will form a precipitate that will serve as a protective film on the surface of
the metal, thereby protecting the metal from corrosion. FTIR result revealed the
nature of bond that exist in the CLNPs and GC–MS result showed various organic
compounds that were presence in the CLNPs [48]. These organic compounds can
be classified as fats, waxes, alkaloids, proteins, phenolics, simple sugars, pectins,
mucilages, gums, resins, terpenes, starches, glycosides, saponins and essential
oils. All of which helps improve the properties of metallic coatings [47, 48]. This
chapter discuss the synthesis and characterization of CPENPs which can be used
as additives to coatings for corrosion protection, especially coatings for oil and
gas applications due to the properties as discussed by Kolawole et al. [46–48].
Therefore, CPENPs should not be left to waste as they are useful for additives
in coatings. These will add value to the CPENPs that is usually dumped in the
environment and also reduces environmental pollution.
12
6. Conclusions
Utilization of cassava plant extract (bark, leaf and stem) nanoparticles as green
corrosion inhibitors incorporated into paint or coatings as an additive. The cassava
plant part waste utilized will reduce the amount of waste contributing to environ-
mental nuisance. The cassava plant solid extract (bark, leaf and stem) will serve as
wealth creation to the farmers and value addition to the cassava waste. The devel-
oped corrosion resistant paint will enhance corrosion resistant of API 5 L X65 steel
pipeline used in the oil and gas industries. Since the world production of cassava is
about 268 million tonnes annually, the cassava waste generated will be significantly
high, therefore the developed corrosion resistant paint will be cheaper and efficient
because of the presence of heteroatoms and organic compounds which help in
inhibiting corrosion.
Acknowledgements
The authors will like to acknowledge Dr. Abdulhakeem Bello, Physics

Department, University of Pretoria, South Africa. Mr. Elakhame in the Ceramic
Department in FIIRO.
Authors have no conflict of interest.
13
14
References
[1] Eddy NO, Odoemelam SA. Inhibition Equipment: Operation, Control, and

of corrosion of mild steel in acidic Reliability. 1st ed. Hoboken, New Jersey,
medium using ethanol extract of Aloe United States: John Wiley & Sons, Inc;
vera. Pigment & Resin Technology. 2012
2009;38(2):111-115
[11] Kiefner JF, Trench CJ. Oil pipeline
[2] Sastri VS. Green corrosion inhibitors. characteristics and risk factors:
In: Theory and Practice. Hoboken, NJ: Illustrations from the decade of
John Wiley & Sons; 1998 construction. American Petroleum
Institute’s Pipeline Committee
[3] Bouyanzer A, Hammouti B, Publication. 2001:1-59
Majidi L. Pennyroyal oil from Mentha
pulegium as corrosion inhibitor for [12] Palmer-Jones R, Paisley D.
steel in M HCl. Materials Letters. Repairing internal corrosion defects
2006;60(23):2840-2843 in pipelines—A case study. In: 4th
International Pipeline Rehabilitation
[4] Satapathy AK, Gunasekaran G, and Maintenance Conference; Prague;
Sahoo SC, Amit K, Rodrigues PV. 2000. pp. 1-25
Corrosion inhibition by Justicia
gendarussa plant extract in hydrochloric [13] Liu X, Wang X. The research of
acid solution. Corrosion Science. oil and gas pipeline corrosion and
2009;51(12):2848-2856 protection technology. Advances
in Petroleum Exploration and
[5] Souza FS, Spinelli A. Caffeic acid as Development. 2014;7(2):102-105
a green corrosion inhibitor in mild steel.
Corrosion Science. 2009;5(3):642-649 [14] Dariva CG, Galio AF. Corrosion
inhibitors—Principles, mechanisms
[6] Jekayinfa SO, Waheed MA, Adebiyi and applications. Developments in
KA, Adebiyi FT. Effect of cassava fluid Corrosion Protection. 2014:365-379
on corrosion performance of mild steel.
Anti-Corrosion Methods and Materials. [15] Fontana MG. Corrosion
2005;52(5):286-292 Engineering. 3rd ed. Washington,
DC, United States: McGraw-Hill Book
[7] Szymońska J, Targosz-Korecka M, Company; 1986. pp. 1-277, 300-444
Krok F. Characterization of starch
nanoparticles. Journal of Physics: [16] Corrosão VG. Vicente Gentil.
Conference Series. 2009;146:012027 Corrosao. 6th ed. Rio de Janeiro: LTC;
2003
[8] Ochoa N, Bello M, Sancristobal
J, Balsamo A, Albornoz, Brito JL. [17] Roberge PR. Handbook of Corrosion
Modified cassava starches as potential Engineering. New York: McGraw-Hill;
corrosion inhibitors for sustainable 2000
development. Materials Research.
2013;16(6):1209-1219 [18] Talbot D, Talbot, e J. Corrosion
Science and Technology. Florida: CRC
[9] Rajput RK. Material Science and Press; 2000
Engineering. Nai – Saraki, Delhi:
S. K. Kataria & Sons; 2006. pp. 854-872 [19] Sangeetha M, Rajendran S,
Muthumegala TS, Krishnaveni A. Green
[10] Holloway MD, Nwaoha C, corrosion inhibitors—An overview.
Onyewuenyi OA. Process Plant Zastita Materijala. 2011;52(1)
15
[20] Hobbs J. Reliable corrosion studies of mild steel with carrier oil
inhibition in the oil and gas industry. In: stabilized of iron oxide nanoparticles
Health and Safety Executive. 2014 incorporated into a paint. International
Journal of ChemTech Research.
[21] Palou RM, Olivares-Xomelt O, 2015;7(4):1661-1664
Likhanova NV. Environmentally
friendly corrosion inhibitors. [29] Erhardt D, Tumosa CS,
Developments in Corrosion Protection. Mecklenburg MF. Can artists’ oil paints
2014:431-465 be accelerated aged? Polymer Preprints.
2000;41(2):1790-1791
[22] Paints: Gloss and Emulsion.
Available from: http://resources. [30] Mandal. Synthesis of Nanoparticles.
schoolscience.co.uk/ICI/14-16/paints/ 2012. Available from: http://www.
paintch1pg/ [Retrieved: 2016] news-medical.net/health/Synthesis-of-
Nanoparticles.aspx [Accessed: February
[23] Bajpai M, Seth S. Use of 14, 2015]
unconventional oils in surface coating
blends of alkyd resins with epoxy [31] Mathiazhagan A, Joseph R.
esters. Pigment & Resin Technology. Nanotechnology—A new prospective in
2000;29:82-87 organic coating—Review. International
Journal of Chemical Engineering and
[24] Micciche F. The Combination Applications. 2011;2(4):225-237
of Ascorbic Acid Derivative/Iron
Salts as Catalyst for the Oxidative [32] Ghandoor HE, Zidan HM, Khalil
Drying of Alky-Paints: A Biomimetic MMH, Ismail MIM. Synthesis and
Approach. Enschede, The Netherlands: some physical properties of magnetite
Technische Universiteit Eindhoven; (Fe3O4) nanoparticles. International
2005. http://alexandria.tue.nl/ Journal of Electrochemical Science.
extra2/200512801.pdf 2012;7:5734-5745
[25] Abulude FO, Ogunkoya MO, [33] Horikoshi S, Serpone N. Microwaves

Ogunleye RF. Storage properties of oils in Nanoparticle Synthesis. 1st ed.
of two Nigeria oil seeds Jatropha curcas Hoboken, New Jersey, United States:
(physic nut) and Helianthus annuus Wiley-VCH Verlag GmbH & Co: KGaA;
(sunflower). American Journal of Food 2013
Technology. 2007;2:207-211
[34] Lue JT. Physical properties of
[26] Akintayo CO. Synthesis and nanomaterials. Encyclopedia of
characterization of Albizia benth Nanoscience and Nanotechnology.
medium oil modification of alkyd resin 2007;X:1-46
and its chemically modified derivatives
[PhD thesis]. Ibadan, Nigeria: [35] Vanaja A, Rao KS. Sol-gel synthesis
University of Ibadan; 2004 and characterization of pure and
silver doped zinc oxide nanoparticles.
[27] Aigbodion AI, Okiemen FE, International Journal of Advanced
Obazee EO, Bakare IO. Utilization Engineering and Nano Technology.
of maleinized rubber seed oil and its 2015;2(8):11-14
alkyd resin as binders in water-borne
coatings. Progress in Organic Coatings. [36] Dahmani M, Et-Touhami A,
2003;46:28-31 Al-Deyab SS, Hammouti B, Bouyanzer
A. Corrosion inhibition of C38 steel in
[28] Palanisamy KL, Devabharathi V, 1 M HCl: A comparative study of black
Meenakshi SN. Corrosion inhibition pepper extract and its isolated piperine.
16
International Journal of Electrochemical [45] Noor NM, Shariff A, Abdullah

Science. 2010;5:1060-1069 N. Slow pyrolysis of cassava
wastes for biochar production
[37] Ostovari A, Hoseinieh SM, Peikari and characterization. Iranica
M, Shadizadeh SR, Hashemi SJ. Journal of Energy & Environment.
Corrosion inhibition of mild steel in 2012;3(Special Issue on Environmental
1 M HCl solution by henna extract: A Technology):60-65
comparative study of the inhibition by
henna and its constituents (lawsone, [46] Kolawole FO, Kolawole SK,
gallic acid, ǂ-D-glucose and tannic acid). Agunsoye JO, Bello SA, Adebisi JA,
Corrosion Science. 2009;51(9):1935-1949 Soboyejo WO, Hassan SB. Synthesis
and characterization of cassava bark
[38] Zucchi F, Omar IH. Plant extracts nanoparticles. Materials Research
as corrosion inhibitors of mild steel Society Advance. 2018:1-8
in HCl solutions. Surface Technology.
1985;24(4):391-399 [47] Kolawole FO, Kolawole SK,
Agunsoye JO, Bello SA, Adebisi JA,
[39] Claude F, Denis F. African cassava Okoye OC, Hassan SB. Cassava leaf
mosaic virus: Etiology, epidemiology, nanoparticles (CLNPs) as a potential
and control. Plant Disease. additive to anti-corrosion coatings
1990;74(6):404-411. DOI: 10.1094/ for oil and gas pipeline. Tribology in
pd-74-0404 Industry. 2017;39(1):63-72
[40] FAOSTAT: Production, Crops, [48] Kolawole FO, Agunsoye JO, Bello
Cassava, 2010 Data. Food and SA, Adebisi JA, Hassan SB. Particle
Agriculture Organization; 2012 size analysis and characterization of
cassava (Manihot esculenta Crantz) stem
[41] Aro SO. Improvement in the nanoparticles (CSNPs) via a top-down
nutritive quality of cassava and approach. Annals of Science and
its by-products through microbial Technology - B. 2016;1(1):52-55. DOI:
fermentation. African Journal 10.22366/ast.2016.01.008
of Biotechnology—Review.
2008;7(25):4789-4797
[42] Ofoefule AU, Uzodinma EO. Biogas

production from blends of cassava
(Manihot utilissima) peels with some
animal wastes. International Journal of
Physical Sciences. 2009;4(7):398-402
[43] Sonnenberg AS, Baars JJ, Obodai

M, Asagbra A. Cultivation of oyster
mushrooms on cassava waste. In:
Proceedings of the 8th International
Conference on Mushroom Biology and
Mushroom Products; 2014. pp. 286-291
[44] Adetunji AR, Isadare DA,

Akinluwade KJ, Adewoye OO. Waste-
to-wealth applications of cassava—A
review study of industrial and
agricultural applications. Advances in
Research. 2015;4(4):212-229
17
Chapter 05
Green Corrosion Inhibitors

Lipiar K. M. O. Goni and Mohammad A. J. Mazumder
Abstract
Corrosion is an unavoidable fact in everyday life but always receive attention

to control due to its technical, economical, and esthetical importance. Corrosion
inhibitors are one of the most widely used and economically viable methods protect-
ing metals and alloys against corrosion. Typical corrosion inhibitors are bio-toxic
organic compounds, which have serious issue on toxicity. Considering the toxicity
of the inhibitors, there is a tremendous interest in searching for an eco-friendly, and
non-toxic green corrosion inhibitor. This chapter briefly discusses the importance
and different methods of corrosion inhibitors with a particular emphasis given to the
discussion on the different characteristic feature of the green corrosion inhibitors
reported in the literature as a comparative view of organic inhibitors.
Keywords: corrosion inhibitors, mild steel, green corrosion, organic, adsorption
1. Introduction
Generally, corrosion is regarded as the loss of a metal by the influence of cor-

rosive agents [1]. However, in a broad sense, corrosion is the devastative consequence
of chemical reaction between a metal or metal alloy and its environment [2]. General
corrosion or uniform corrosion is the most prevalent form of corrosion that takes
place on an entirely exposed metal surface via the electrochemical reactions in atmo-
spheric or aqueous media and continues uniformly to cause the greatest destruction
of that metal [3]. Even though only metals come to mind when describing corrosion,
non-metallic materials, such as plastics, concrete, ceramics, rubber, etc. are prone to
corrosion as well when exposed to different corrosive environments [4].
The difference in the potential energies of the corroding metal and the corro-
sion product is the fundamental force that drives the corrosion reaction. A certain
amount of energy is required to be provided to naturally occurring minerals and
ores to extract metals from them. Therefore, it is natural that these metals tend to
revert back to their original state from which they were obtained when they are
exposed to their environments. It is noteworthy that each metal is different in terms
of the amount of energy required and stored in it or that is released during its corro-
sion. The greater the amount of energy needed during metal extraction, the more
thermodynamically unstable is the metal and the shorter is its temporary existence
in metallic form. Hence, corrosion has also been defined as the reverse of extractive
metallurgy [1, 5].The electrochemical dissolution of a metal is the most important
mechanism involved in its corrosion and makes the basis of all uniform and local-
ized corrosion types. However, there are some corrosion types, such as oxidation,
fretting corrosion, molten salt corrosion, etc. that can be described without refer-
ence to electrochemistry [1]. The mechanism of corrosion attack in an atmospheric
environment and in an aqueous environment will be always governed by some
1
aspect of electrochemistry. Electrons will be flowing from certain areas of a metal

surface to other areas through an electrolyte that is capable of conducting ions. This
stems from the incredible tendency of metals to react electrochemically with water,
oxygen, and other substances in the aqueous environment. In an electrochemical
corrosion process, the anode is that area of the metal surface that is corroding due
to the loss of electrons while the cathode is the area that consumes the electrons
generated by the corrosion reaction [6].
Almost all of us are familiar with corrosion happening to metal structures,
boats, steel pilings, household utensils, etc. Unfortunately, many of us are not
aware of corrosion that is deteriorating the properties of underground water, oil,
and gas pipelines crisscrossing our land or water pipes in the home where corrosion
occurs mostly from the inside. Successful enterprises put in considerable efforts in
controlling corrosion at the design stage and in the operational phase to avoid major
corrosion failures, such as unscheduled shutdowns, fatalities, personal injuries,
and environmental contamination in a modern business environment. However,
even the best design is unable to foresee all conditions that can allow corrosion
intruding into the life of a system [5]. Steel reinforced bar (rebar) can corrode in
concrete without being noticed at all and can cause damage to buildings, bridges,
parking structures, the collapse of electrical towers, failure of a section of highway,
etc., resulting in a huge amount of repairing cost and threatening public safety [7].
This is why regular maintenance of the metallic components that are susceptible to
corrosion is of paramount importance.
2. Impact of corrosion
Even though the main reasons for considering corrosion are economic and
ecological, losses due to corrosion or costs of corrosion can be actually divided into
three main categories as shown in Figure 1 [8].
2.1 Material and energy
The impact of corrosion on the equipment and its surrounding deserves a huge
attention when it comes to designing an industry. Corrosion is considered to be one
of the most challenging issues for most of the industrialized countries. Corrosion
of tanks, piping, metal components of machines, bridges, ships, etc. can incur a
massive material and economic losses upon a nation. Additionally, the safety of
operating equipment, such as boilers, pressure vessels, metallic containers for toxic
chemicals, bridges, turbine blades and rotors, automotive steering mechanisms, and
airplane components can be threatened by corrosion failure [8]. Furthermore, the
Figure 1.
Breakdown of corrosion costs.
2
devastative impact of corrosion goes beyond the metals and extends to energy, water,
and the manufacturing phase of the metal frames [9]. It has been reported that one
ton of steel turns into rust every 90 seconds, and, on the contrary, the energy needed
to manufacture one ton of steel is approximately equal to the energy an average
family consumes over 3 months. Approximately 50% of every ton of steel produced
by the world is used to replace rusted steel [10].
2.2 Economic
Economic losses are classified into two types: (i) direct losses and (ii) indirect
losses. Replacing the corroded structures and machinery of their components, for
instance, mufflers, condenser tubes, pipelines, metal roofing, including necessary
labor, repainting structures to prevent rusting, maintenance cost of cathodic pro-
tection system for underground pipelines, replacement cost of millions of domestic
hot-water tanks and automobile mufflers, extra cost of using corrosion-resistant
metals and alloys, galvanizing or nickel plating of steel, addition of corrosion
inhibitors to water, and dehumidifying cost of the metal equipment storage rooms
contribute to the direct losses. While it is quite difficult to assess the indirect losses,
they have still been reported to add several billion dollars to the direct losses.
Indirect losses include sudden shutdown of plants, loss of water, gas, or oil through
a corroded pipeline, loss of efficiency in the energy conversion systems imposed by
corrosion processes, contamination of water and food products in metal piping and
containers, and overdesign requiring equipment to be designed many times heavier
than normal operating pressure or applied stress to extend their lifetime [8]. Uhlig
made the first ever systematic study on the cost of corrosion in 1949 [11]. Uhlig's
report estimated the annual cost of corrosion in the United States to be US$ 5.5
billion or 2.1% of the 1949 gross national product (GNP). This study measured the
total costs by summing the costs related to anti-corrosion materials and corrosion-
induced maintenance and replacement handled by owners and operators (direct) as
well as those related to users (indirect) [5, 12].
Corrosion cost studies using different methods, such as Uhlig method invented
by Uhlig in 1949 [11], Hoar method invented by Hoar in 1971 [13], and economic
input/output model devised by National Bureau of Standards (NBS) collaborating
with Battelle Memorial Institute in 1978 [14] have been undertaken by several major
economies, including Australia, China, Finland, Germany, India, Japan, Kuwait,
the United Kingdom, and the United States [15]. A common observation of these
studies was that the costs of corrosion ranged from approximately 1–5% of the GNP
of each nation. The variation in the corrosion cost with respect to GNP was ascribed
to the methodology used by each study and the specifics of each country [12].
A study done by National Association of Corrosion Engineers (NACE) as part of
its International Measures of Prevention, Application, and Economics of Corrosion
Technologies Study (IMPACT) revealed that the global cost of corrosion in 2013
was estimated to be US$ 2.5 trillion which was equivalent to 3.4% of the global GDP
in that year [15]. This study utilized the World Bank economic sector and GDP
data to relate the cost of corrosion studies to a global cost of corrosion. In order to
address the economic sectors across the world, the global economy was divided
into economic regions with similar economies (according to World Bank). These
were: United States, European Region, India, Arab World (defined by the World
Bank), Russia, China, Japan, Four Asian Tigers plus Macau, and Rest of the World.
However, the costs estimated typically do not include environmental consequences
or individual safety. It is noteworthy that receiving additional funds for corrosion
studies, or updated information on these studies, more detailed and accurate global
costs can be assessed.
3
2.3 Human life and safety
Corrosion can take a toll more than imaginable in human life and safety. This
destructive phenomenon has been overlooked as the main reason of many fatal
accidents for reasons of liability or simply because the evidence disappeared in the
catastrophic event. The Silver Bridge collapse is one of the most dangerous and
discussed corrosion accidents [16]. On December 15, 1967, this bridge connecting
Point Pleasant, West Virginia and Kanauga, Ohio suddenly collapsed into the Ohio
River to claim 46 lives. Stress corrosion cracking (SCC) and corrosion fatigue were
determined to be responsible for this disaster. The Bhopal accident that took place in
Bhopal, India on the night of the December 2–3, 1984 is one of the worst industrial
accidents in terms of the lives lost and injuries. An unfortunate seepage of water
(500 liters) caused by the corrosion of pipelines, valves, and other safety equipment
into a methylisocyanate (MIC) storage tank at Union Carbide India Limited caused
the release of MIC and other toxic reaction products into the surrounding areas
that killed 3000 people and injured an estimated 500,000 people [17]. Swimming
Pool Roof Collapse is another infamous corrosion accident that took place in Uster,
Switzerland in 1985. The roof of this swimming pool was supported by stainless
steel rods that failed due to SCC and killed 12 people [18].
3. Techniques for corrosion measurement
3.1 Weight loss measurement
Weight loss analysis is known to the simplest, most reliable, and long-
established method of assessing corrosion losses in plant and equipment. A sample
of metal or alloy under experiment is weighed and then immersed into a corrosive
solution, and later removed from the corrosive medium after a predetermined time
interval. The metal specimen is then weighed again after cleaning all corrosion
products. The corrosion rate, surface coverage (θ), and corrosion inhibition effi-
ciency (η%) can be calculated using (Eqs. (1)–(3)):
m i − m f
Corrosion rate (____
 year )
mm    = 8.76 × 10 3 ______
        (1)
S𝜌t
CR   − CR
θ = _______
  o    
  (2)
CRo 
CR   − CR
η % = _______
  o       × 100% (3)
CRo 
where mi is the weight of the metal sample in grams before immersion, mf is the
weight of the metal sample in grams after immersion, S is the total area of metal in cm2
that has been exposed to corrosive solution, ρ is the density of metal sample in g/cm2, t
is the time in hours during which the sample was immersed, CR○ and CR represent the
corrosion rates (in mmpy) without and with the inhibitor, respectively [19, 20].
3.2 Polarization measurements
Since corrosion is a phenomenon that involves electrochemistry, electrochemi-

cal-based corrosion measuring experiments provide valuable information about the
4
rate of corrosion and mechanism of corrosion protection [20]. Polarization meth-

ods are based on changing the current or potential on a sample under investigation
and recording the corresponding potential or current change. This can be facilitated
with the help of either a direct current (DC) or an alternating current (AC) source
[5]. Some important and widely used techniques have been discussed briefly below.
3.2.1 Tafel extrapolation
Tafel curve is a current-potential plot that shows the anodic and cathodic
reactions in the electrochemical cell. In this method, the potential of the working
electrode (metal sample) varied over a range at a specific rate and the resulting
response in current is recorded. The anodic and cathodic reactions that are tak-
ing place simultaneously produce a total current that is represented by a curved
line. The linear portions of logarithmic Tafel plot are extrapolated to produce an
intersection that generates a point that signifies an approximation of the corrosion
current (icorr) and the corrosion potential (Ecorr). This icorr facilitates the calculation
of the corrosion rate based on (Eq. (4)) and the corrosion inhibition efficiency
(η%) based on (Eq. (5)):
i   × K × EW
Corrosion rate = ___________
  corr       (4)
ρ × A
i o    − i 
𝜂 % = _______
  corr o  corr 
  × 100% (5)
ic orr
   
where K is a constant that represents the units for the corrosion rate, EW is the
equivalent weight in gram/equivalent, ρ is density in g/cm3, A is the area in cm2
exposed to corrosive solution, i°corr and icorr are the corrosion currents in amperes
without and with the inhibitor, respectively.
3.2.2 Linear polarization resistance (LPR)
Because the linear polarization resistance (LPR) method is non-destructive

[21], it has quick application and can be used in the field test through portable
instrumentation [22], it is the most popular of the electrochemical techniques [23].
The principal of LPR is based upon introducing a small perturbative DC electri-
cal signal to disturb the corrosion equilibrium on the surface of metal specimen.
The response of the equilibrium to this perturbation is measured with respect to a
reference half-cell [24]. The polarization resistance (Rp) of a material is known to be
the ΔE/Δi slope of a potential-current density curve at the free-corroding potential.
The polarization resistance can be related to the corrosion current (icorr) using the
Stern-Geary approximation in which the anodic (ba) and cathodic (bc) Tafel slopes
can be experimentally obtained from real polarization plots.
3.2.3 Electrochemical impedance spectroscopy (EIS)
Electrochemical impedance spectroscopy (EIS) is a very powerful electrochemi-

cal technique that has wide applications in the evaluation of coatings in corro-
sion research. This technique provides valuable information about the corrosion
protection imparted by an inhibitor. In this technique, an AC voltage (in the case
of potentiostatic EIS) or current (in the case of galvanostatic EIS) is applied to the
system under investigation to receive response in the form of AC current (volt-
age) or voltage (current) as a function of the frequency. This technique can be
5
performed in a 2- or 3-electrodes system with the help of a potentiostat-galvanostat

and a frequency response analyzer (FRA) [25]. Usually, an AC voltage having
small perturbations ranging from 5 to 10 mV is applied in the system over a range
of frequencies typically starting from 100 kHz to 10 mHz. Based on the shape of
the Nyquist plot produced by the experiment, the electrochemical cell containing
the metal sample, adsorbed inhibitors, and the electrolyte medium is represented
by an equivalent circuit that includes information about the solution resistance Rs,
charge transfer resistance Rct, and the double layer capacitance Cdl. A large Rct value
and decreasing Cdl values with increasing inhibitor concentrations indicate better
corrosion protection [26].
4. Corrosion inhibitors
A corrosion inhibitor is known as a chemical constituent that can diminish or

prevent and control corrosion when added in small amount to the metal environ-
ment. Corrosion inhibitors are considered as the first line of defense against oil
and chemical industry corrosion [27]. Corrosion inhibitors are sought after giving
metals temporary protection during transportation and storage as well as local-
ized protection to prevent corrosion that may have resulted from accumulation of
small amounts of an aggressive phase. An effective corrosion inhibitor should be
cost-effective, compatible with the corrosive medium, and produce desired effect
when present in small concentrations [28]. Corrosion inhibitors act by (i) forming
a film that is adsorbed on the metal surface, (ii) producing corrosion products, for
example, iron sulfide (FeS) that acts as a passivator, and (iii) yielding precipitates
that can eliminate or inactivate an aggressive constituent [29].
Depending on which electrochemical reactions are being blocked, these
film-forming or interface inhibitors can be classified into anodic, cathodic, or
mixed-type [28, 30]. Anodic inhibitors, alternately known as passivation inhibi-
tors, suppress the rate of anodic reactions by producing sparingly soluble deposits,
such as hydroxides, oxides, or salts in close to neutral conditions. On the other
hand, cathodic inhibitors function by reducing the rate of cathodic or reduction
reactions by producing a protective layer on cathodic areas against hydrogen in
acidic conditions and oxygen in alkaline conditions. Mixed inhibitors influence
both the anodic and cathodic reaction sites by forming an adsorptive film on the
metal surface. About 80% of organic inhibitors fall into this category. Based on the
chemical nature of the inhibitors, they can be divided into organic and inorganic
[31]. Organic and inorganic inhibitors, based on their compositions and mechanism
of actions, can be further classified into neutralizing, scavenging, barrier or film-
forming, and other miscellaneous inhibitors [32].
4.1 Organic inhibitors
Organic inhibitors act through forming a film on the surface of the metals
and they can act as anodic, cathodic, or mixed inhibitors. The formation of this
protective film happens with the help of strong interactions, such as π-orbital
adsorption, chemisorption, and electrostatic adsorption that prevent the cor-
rosive species from attacking the metal surface [33]. This adsorption is usually one
molecular layer thick and does not penetrate into the bulk of the metal itself [34].
Physicochemical properties, such as functional groups, steric factors, aromaticity,
π-orbital character of donating electrons, electron density at the donor atoms, and
the electronic structure of the molecules govern the adsorption process [35, 36].
The corrosion inhibition efficiency of an organic inhibitor relies on its adsorption
6
ability and mechanical, structural, and chemical characteristics of the adsorption

layers formed under a specific environment [37]. An efficient organic inhibitor will
usually contain polar functional groups with S, O, or N atoms in the molecule and
a hydrophobic moiety that will repel the aqueous corrosive species away from the
metal surface. However, the polar head is considered to be responsible for estab-
lishing the adsorption layer [38]. Some chemical families of organic inhibitors are
pyridines, fatty amides, imidazolines, and 1,3-azoles [39].
4.2 Inorganic inhibitors
Inorganic inhibitors are those inhibitors in which the active substance is an

inorganic compound. The addition of electropositive metal salts to a corrosive
medium is one of the simplest ways to improve the passivity of a metal. However,
the protective metal ion must have a redox potential more positive than the one
to be protected and potentially more positive than that required for discharging
protons so that the protective metal ion can be discharged on the surface of the
metal in need of protection. Cathodic depolarization by overvoltage reduction and
subsequent formation of an adherent deposit take place through the deposition of
the protective metal on the surface of the metal susceptible to corrosion. Some of
the metals that serve this purpose are palladium (Pd), platinum (Pt), iridium (Ir),
rhodium (Rh), mercury (Hg), and rhenium (Re). Many inorganic anions, such as
chromates (CrO42−), molybdate (MoO3−), silicates (SiO44−), phosphate (H2PO3−),
and nitrate (NO2−) as well provide passivation protection to the metal surfaces
through their incorporation into the oxide layer [39].
Environmental friendliness, cost, availability, and toxicity are some factors that
should play an extremely important role when it comes to choosing an inhibitor for
a particular condition [40]. The toxicity, biodegradability, and bioaccumulation of
conventional corrosion inhibitors discharged into the environment are matter of
huge concern. Even though the environmental implications of commercial corro-
sion inhibitors are not fully understood, it is not unknown that their chemical com-
ponents have hazardous impact [41]. Inorganic inhibitors, for example, arsenates,
phosphates, chromates, and dichromates not only have shown promising inhibition
efficiency but also have been proved intolerant as well due to the threat they pose
to our social health in the long run [42]. Likewise, the ecological and health risks
associated with the organic inhibitors have pushed us towards finding or using non-
toxic or green corrosion inhibitors that would impart maximum protection to the
metallic structures but have least impact on mankind and nature [36].
4.3 Green corrosion inhibitors
Corrosion inhibitors are extensively used for the protection of metals and equip-
ment and they are required to be acceptable, non-toxic, and eco-friendly due to
environmental concerns. The cost and harmful effect associated with the commer-
cial organic and inorganic inhibitors have raised considerable awareness in the field
of corrosion mitigation. Thus, corrosion scientists and engineers are more inclined
towards the implication of green corrosion inhibitors that are inexpensive, readily
available, environmentally friendly and ecologically acceptable, and renewable.
Several classes of such inhibitors have been discussed briefly below.
4.3.1 Plant extracts
Umoren et al. investigated the inhibition efficiency (IE) of gum arabic (GA)
in absence and presence of halide ions on mild steel in 0.1 M H2SO4 at different
7
temperatures. In weight loss analysis, 0.05 M KCl, 0.05 M KBr, 0.05 M KI, and GA
(0.5 g/l) alone imparted IE of 27.7, 32.2, 53.6, and 37.9%, respectively, at a maximum
temperature of 60°C. At the same temperature and under similar technique, GA
mixed with all of these halide solutions individually showed increased efficiency
of 38.7, 47.1, and 59.1%, respectively. The ion-pair interactions between the organic
cations and the halide anions have contributed to increased surface coverage that
eventually led to better synergistic protection [43]. The IE of GA on AA1060 type
aluminum sheets with 98.5% purity was examined at 40°C. It was found that GA
(0.5 g/l) showed IE of 74.2 and 75.9% measured by hydrogen evolution and thermo-
metric methods, respectively [44]. Buchweishaija and Mhinzi [45] investigated the
IE of gum exudates from Acacia seyal var. seyal and Acacia gum from seyal var. seyal
on mild steel in chlorinated drinking water using potentiodynamic polarization
(PP) and electrochemical impedance spectroscopy (EIS) techniques. Gum exudates
showed maximum IE of 98.5% at a concentration of 1000 ppm at 30°C. On the
other hand, Acacia gum showed an IE of 96.8% at an elevated temperature of 80°C
at a concentration of 600 ppm.
The anticorrosive effect of a composite coating containing chitosan (CS; green
matrix), oleic acid (OA), and graphene oxide (GO; nanofiller) on mild steel in 3.5
wt.% NaCl solution has been studied by Fayyad et al. [46]. The IE of the nano-
composite coating was measured by PP and EIS techniques. It was observed that
oleic acid-modified chitosan/graphene oxide (CS/GO-OA) film showed corrosion
resistance 100 times better than pure chitosan (CS) coating. Additionally, oxygen
transmission rate (OTR) measured for the CS/GO-OA was found to decrease
by 35 folds in comparison to the pure chitosan film. This decreased OTR for the
CS/GO-OA coating demonstrates that an effective barrier between the metal
surface and the corrosive electrolyte species was developed. Alaneme et al. [47]
experimented the IE and adsorption characteristics of elephant grass (Pennisetum
purpureum) extract on mild steel in 1 M HCl solution. At room temperature (RT),
the inhibitor showed efficiency greater than 95% and increasing with increasing
concentration of the extract but decreasing with increasing temperature. The pres-
ence of hydroxyl (O-H) and unsaturated (C=C) groups that have inhibitory proper-
ties were confirmed in the extract by FT-IR investigation. The scanning electronic
micrographs showed significant pitting on the metal substrate that was immersed in
1 M HCl solution without the inhibitor and pitting was rarely present in the solution
that contained inhibitor. The lower rate of iron dissolution in the corrosive solu-
tion that contained inhibitor was further confirmed by a higher Fe peak by energy
dispersive spectroscopy (EDS) spectrum.
The inhibitory effect of hydroxyethyl cellulose (HEC) on 1018 c-steel corrosion
in 3.5% NaCl solution was studied by El-Haddad using PP, EIS, and electrochemi-
cal frequency modulation (EFM) techniques [48]. The PP study revealed that
HEC acted as a mixed inhibitor and the adsorption study showed that it followed
Langmuir adsorption isotherm. The fact that oxygen atoms donate unshared pair of
electrons to the vacant d-orbital of iron was established by the optimized geometry
of HEC obtained by DMol3 quantum chemical calculations that showed that oxygen
atoms of HEC have Muliken atomic charges with higher electron densities. The IEs
measured by PP, EIS, and EFM techniques were 96.7, 95.5, and 94.8%, respectively,
for the inhibitor concentration of 0.5 mM at 25°C. Mobin and Rizvi [49] explored
the anticorrosion behavior of xanthan gum (XG) as an eco-friendly corrosion
inhibitor for mild steel in 1 M HCl at 30, 40, 50, and 60°C, respectively. At a con-
centration of 1000 ppm at 30°C, XG showed the maximum IE of 74.2%. The addi-
tion of very small amounts of surfactants cetylpyridinium chloride (CPC), sodium
dodecyl sulfate (SDS), and Triton X-100 (TX) improved the IE. Quantum chemical
calculations found the energy differences between the highest occupied molecular
8
orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) to be 0.05
and 0.02 eV in XG alone and XG plus SDS, respectively. The smaller energy gap
between HOMO and LUMO indicated better inhibition efficiency for XG plus SDS
system. The formation of complex between XG and Fe2+ was further confirmed by
UV-Visible spectroscopic measurements. Scanning electronic microscopy (SEM)
study revealed an improved surface morphology of inhibited mild steel compared
to uninhibited mild steel. The plant extracts form a major class of green corrosion
inhibitors. Some recently reported plant extracts as green corrosion inhibitors and
their IEs have been summarized in Table 1.
4.3.2 Amino acids
Amino acids are molecules that contain at least one carboxyl (-COOH) group
and one amino (-NH2) group bonded to the same carbon atom (α- or 2-carbon).
Amino acids are considered as green corrosion inhibitors because they are non-
toxic, biodegradable, inexpensive, soluble in aqueous media, and easy to produce
at high purity. The presence of heteroatoms, such as N, O, and S and conjugated
π-electrons system have made amino acids a significant class of green corrosion
inhibitors thanks to their environmental aspect [60, 61]. El-Sayed investigated the
anti-corrosive effect of some amino acids, such as glycine, valine, leucine, cysteine,
methionine, histidine, threonine, phenylalanine, lysine, proline, aspartic acid,
arginine, and glutamic acid on carbon steel in stagnant naturally aerated chloride
solutions using PP and EIS techniques. All of the amino acids acted as mixed-type
inhibitor while cysteine, phenylalanine, arginine, and histidine showed remarkably
high corrosion inhibition efficiency at a concentration of 10 mM/dm3. The presence
Inhibitor Metal/alloy Test Maximum Test References

(concentration) condition efficiency technique
(η%)
Saraca asoca Mild steel 0.5 M 95.5 Tafel [50]

(100 mg/L) H2SO4, 25°C
Sida cordifolia Mild steel 0.5 M 99.0 Tafel [51]

(500 mg/L) H2SO4, 25°C
Myristica fragrans Mild steel 0.5 M 87.8 EIS [52]

(500 mg/L) H2SO4, 25°C
Ginkgo (200 mg/L) X70 steel 1 M HCl, 92.5 EIS [53]
45°C
Eriobotrya japonica Mild steel 0.5 M 96.2 Weight loss [54]

(100% v/v) H2SO4, 25°C
Turbinaria ornata Mild steel 1 M HCl, 94.5 EIS [55]

(25 g/L) 25°C
Pongamia pinnata Mild steel 1 N H2SO4, 94.6 Weight loss [56]
(100 ppm) 30°C
Prosopis juliflora Low-carbon 1 M HCl, 91.5 EIS [57]

(300 ppm) steel 25°C
Rollinia occidentalis Carbon 1.0 M HCl, 85.7 Tafel [58]

(1.0 g/L) steel 25°C
Xanthium strumarium Low-carbon 1 M HCl, 94.8 Weight loss [59]

(10 mL/L) steel 60°C
Table 1.
Some recent plant extracts as green corrosion inhibitors of different metals and alloys.
9
of functional groups such as OH, SH, or phenyl in the backbone of the amino
acid molecules help them undergo better adsorption [62]. Mobin et al. studied the
inhibitory behavior of mercapto group containing amino acid L-cysteine (CYS)
on mild steel in aerated and unstirred 1 M HCl solution using weight loss (WL),
PP, and EIS techniques. The maximum IE of 85.6% at 30°C was achieved with an
inhibitor concentration 500 ppm. The authors investigated the effect of surfactants
CPC, SDS, and TX by adding them to CYS and found that the surfactants increased
the IE. CYS separately and in combination with surfactants acted as mixed-type
inhibitor and obeyed Langmuir’s adsorption isotherm [63].
In their attempt to solve the “bronze disease”, Wang et al. studied the corrosion
behavior of bronze covered with CuCl patina in the presence of CYS using EIS and
X-ray photoelectron spectroscopy (XPS) techniques. EIS results revealed that CYS
can both inhibit the bronze substrate and stabilize the CuCl patina effectively. The
IE reached the highest value of 95.3% at a CYS concentration of 5 mmol/L. The
XPS investigation showed that the chemisorption of CYS on CuCl surface hap-
pened through sulfur atom in thiol and nitrogen atom in amino group [64]. Zeino
et al. investigated the mechanistic study of polyaspartic acid (PASP) on mild steel
in 3% NaCl solution. PASP alone showed a moderate IE of 61% at 2.0 g/L and zinc
ion added PASP showed a superb IE of 97% at a reduced PASP concentration of
0.5 g/L. The authors studied the surface morphology of mild steel utilizing SEM
and atomic force microscopy (AFM) techniques. Quantum calculation and Monte
Carlo simulation helped them achieve molecular level insights into the complex
adsorption mechanism [65]. Ituen et al. investigated the IE of N-acetyl cysteine
(NAC)-based formulation on J55, mild steel, and X80 steel at different temperatures
(30–90°C). NAC-based formulations showed IEs up to 91% at 90°C [66].
4.3.3 Drugs
The use of drugs as green corrosion inhibitors has been inspired by the fact
that they are non-toxic, cheap, eco-friendly, and green enough to compete with
other green corrosion inhibitors because most of these drugs can be synthesized
from natural products [67]. The presence of heteroatoms, benzene ring, and
heterocycles, such as thiophenes, pyridine, isoxazoles, etc. have made drug
molecules as a promising source of green corrosion inhibitors. Recently, Ali
investigated the inhibitory behavior of Candesartan drug on carbons steel (CS)
in 1 M HCl acidic medium using WL, PP, EIS, and EFM techniques. The surface
morphology of the inhibited CS was investigated by EDX, AMF, and SEM tech-
niques. The inhibitor showed an IE of 79.8% at a concentration of 300 ppm [68].
Matad et al. investigated the inhibitive properties of an anti-inflammatory drug
ketosulfone as green corrosion inhibitor of mild steel in 1 M HCl acidic medium
using chemical and electrochemical methods. Ketosulfone imparted a maximum
IE of 96.6% at 30°C for a concentration of 200 ppm. The inhibitor was found to
be of mixed-type and follow Langmuir adsorption isotherm determined by polar-
ization measurements and thermodynamic calculations, respectively [69]. Singh
et al. investigated the corrosion behavior of mild steel in 1 M HCl acidic medium
in presence of an expired atorvastatin drug using WL, PP, and EIS techniques
[70]. The expired drug showed an amazing IE of 99.1% at a concentration of 150
ppm. The inhibitor acted as mixed-type inhibitor with predominant cathodic
behavior. Dahiya et al. studied the anti-corrosive behavior of an expired drug
ethambutol on mild steel in 0.5 M HCl using WL, PP, EIS, SEM, and molecular
dynamics (MD) techniques. The inhibitor showed an IE more than 95% at a
concentration of 100 ppm and it acted as a mixed-type inhibitor and followed
Langmuir adsorption isotherm [71].
10
4.3.4 Rare earth (RE) metal compounds
Chromates have applications in deoxidizers, anodizing, conversion coatings,

chromate-inhibited primers, wash primers, and repair processes. Environmental
protection legislation was realized to prevent the use of unacceptable materials such
as chromium salts. Chromium (Cr6+) is highly toxic and carcinogenic [41, 72]. The
health problems associated with the use of chromates and the cost associated with
their safe use and disposal have led to efforts finding good alternatives such as rare
earth metal compounds. After the first paper was published by Hinton et al. [73] in
1984 on the use of cerium chloride salts as corrosion inhibitor, a lot of research papers
have been published by the researcher working in this area. In 1992, Hinton et al.
[74] published a review paper highlighting the use of some RE compounds as green
corrosion inhibitors of a wide range of metals. In this chapter, the authors pointed that
these RE salts work by producing an oxide film at the cathodic sites of the metal sub-
strate which prevent the supply of oxygen or electrons to the reduction reaction thus
reducing the corrosion rate. A comprehensive review of the recent developments in
corrosion inhibitors based on RE metal compounds can be gained from the two works
published by Forsyth et al. [75, 76] and the book edited by Forsyth and Hinton [77].
4.3.5 Others
Surfactant corrosion inhibitors are also known as green corrosion inhibitors

because they are highly efficient, cheap, and less/non-toxic. Surfactant molecules
consist of a polar hydrophilic group or “head” and a non-polar hydrophobic group
or “tail”. In aqueous solutions, the adsorption of surfactant occurs through either
chemisorption or physisorption. Critical micelle concentration (CMC) is the most
important parameter when it comes to studying the corrosion inhibition by surfac-
tants [78]. Recently, ionic liquids have gained widespread popularity as green corro-
sion inhibitors. By definition, ionic liquids are referred to as materials consisting of
ions having melting point below 100°C. Ionic liquids due to their some fascinating
properties, such as high polarity, lower melting point, low toxicity, lower vapor
pressure, very high thermal, and chemical stability have applications in some other
fields of chemical and chemical engineering researches as well [79].
5. Recent patents on green corrosion inhibitors
Corrosion inhibitors are an important and cost-effective way of dealing with

corrosion. A huge effort to produce green inhibitors and evaluate them successfully
is underway. Some recently patented green corrosion inhibitors that could indicate
the importance of this class of inhibitors are included in Table 2.
Inhibitor system Reference
Main chain type polybenzoxazine (MCTPB)-Chitosan (CHI) blend [80]
Polyaspartic acid-hydroxyphosphonoacetic acid-phosphinocarboxylic acid composition [81]
Polyaspartic acid-soluble Sn (II) or Sn (IV) compound blend [82]
At least (one fatty acid-one alkanolamine-one alkylamine-one organic sulfonic acid [83]
composition)
A corn stillage product [84]
Table 2.
Some recent patents on green corrosion inhibitors.
11
6. Conclusion
Corrosion is a destructive phenomenon that could strike badly at the heart of an

economy as it did on many occasions. The direct and indirect global costs associated
with corrosion are no longer ignorable. Corrosion is not a necessary curse because it
might be almost impossible to stop it but preventable. The use of inhibitors to miti-
gate corrosion is an economically viable option given the maintenance costs associ-
ated with the metals and equipment is already very high. However, recent trends
in the field of corrosion inhibition are more inclined towards finding not only an
effective inhibitor but also an eco-friendly one. This is because an effective inhibi-
tor may serve the purpose of mitigating corrosion well but could leave hazardous
impact on the health and ecology due to the harmful aspect associated with its
chemical formula. Green corrosion inhibitors in the form of plant extracts, drugs,
amino acids, rare earth metal compounds, ionic liquids, surfactants, etc. are not
only eco-friendly but also provide excellent corrosion prevention. The replacement
of the existing harmful organic and inorganic inhibitors that are used for different
industrial applications by the green ones is not merely a matter of concern anymore
but an agenda that has been in implementation and will continue to be realized.
Acknowledgements
The authors gratefully acknowledge the financial support and research facilities
provided by Deanship of Scientific Research, King Fahd University of Petroleum
and Minerals through internal project # IN131047.
The authors declare that there is no conflict of interest regarding the publication
of this article.
12
References
[1] Schofield MJ. Corrosion. In: Snow [9] Raja PB, Ismail M, Ghoreishiamiri
DA, editor. Plant Engineer's Reference S, Mirza J, Ismail MC, Kakooei S,
Book. 2nd ed. Oxford: Butterworth et al. Reviews on corrosion inhibitors:
Heinemann; 2002. pp. 961-986 10.1016/ A short view. Chemical Engineering
B978-075064452-5/50088-2 Communications. 2016;203:1145-1156.
DOI: 10.1080/00986445.2016.1172485
[2] Jones DA. Principles and Prevention
of Corrosion. 2nd ed. New Jersey: [10] Javaherdashti R. How corrosion
Prentice Hall; 1996. 572 p. ISBN: affects industry and life. Anti-Corrosion
0-13-359993-0 Methods and Materials. 2000;47:30-34.
DOI: 10.1108/00035590010310003
[3] Makhlouf ASH. Intelligent
stannate-based coatings of self-healing [11] Uhlig HH. The cost of corrosion to
functionality for magnesium alloys. In: the United States. Corrosion. 1950;6:29-
Tiwari A, Rawlins J, Hihara LH, editors. 33. DOI: 10.5006/0010-9312-6.1.29
Intelligent Coatings for Corrosion
Control. 1st ed. Oxford: Butterworth [12] Hou B, Li X, Ma X, Du C, Zhang D,
Heinemann; 2015. pp. 537-555. DOI: Zheng M, et al. The cost of corrosion
10.1016/B978-0-12-411467-8.00015-5 in China. Materials Degradation.
2017;1(4):1-10. DOI: 10.1038/
[4] Zarras P, Stenger-Smith JD. Smart s41529-017-0005-2
inorganic and organic pretreatment
coatings for the inhibition of corrosion [13] Hoar TP. Review lecture: Corrosion
on metals/alloys. In: Tiwari A, Rawlins of metals: Its cost and control.
J, Hihara LH, editors. Intelligent Proceedings of the Royal Society of
Coatings for Corrosion Control. 1st London. Series A: Mathematical and
ed. Oxford: Butterworth Heinemann; Physical Sciences. 1976;348:1-18. http://
2015. pp. 59-91. DOI: 10.1016/ www.jstor.org/stable/79113
B978-0-12-411467-8.00003-9
[14] Bennett LH, Kruger J, Parker RL,
[5] Roberge PR. Corrosion Engineering: Passaglia E, Reimann C, Ruff AW,
Principles and Practice. 1st ed. et al. Economic Effects of Metallic
New York: McGraw Hill; 2008. 734p. Corrosion in the United States: A
DOI: 10.1036/0071482431 Report to the Congress by the National
Bureau of Standards. National Bureau
[6] Corrosion Electrochemistry. 2018. of Standards. Washington D. C, USA:
Available from: https://corrosion- U. S. Government Printing Office; 1978.
doctors.org/Electrochemistry-of- Publication No. 511-1. 65p. [Google
Corrosion/Introduction.htm [Accessed: Books]
June 12, 2018]
[15] Koch G, Varney J, Thompson N,
[7] Davis J. Corrosion. In: Understanding Moghissi O, Gould M, Payer J.
the Basics. 1st ed. Ohio: ASM International Measures of Prevention,
International; 2000. 517p. ISBN: Application, and Economics of
0-87170-641-5 Corrosion Technologies Study. Houston:
NACE International; 2016. 216p.
[8] Revie RW, Uhlig HH. Corrosion and [IMPACT Report]
Corrosion Control: An Introduction to
Corrosion Science and Engineering. 4th [16] Lichtenstein AG. The silver
ed. New Jersey: Wiley; 2008. 512p. ISBN: bridge collapse recounted. Journal of
978-0-471-73279-2 Performance of Constructed Facilities.
13
1994;7:249-261. DOI: 10.1061/ [25] Orazem ME, Tribollet B.

(ASCE)0887-3828(1993)7:4(249) Electrochemical Impedance
Spectroscopy. 1st ed. New Jersey:
[17] Bowonder B. The Bhopal accident. Wiley-Blackwell; 2008. 525p. DOI:
Technological Forecasting and Social 10.1002/9780470381588
Change. 1987;32(2):169-182. DOI:
10.1016/0040-1625(87)90038-2 [26] EIS-Electrochemical Impedance
Techniques [Internet]. 2018. Available
[18] Stress Corrosion Cracking Failure from: https://www.gamry.com/
[Internet]. 2018. Available from: https:// application-notes/EIS/potentiostatic-
corrosion-doctors.org/Forms-SCC/ eis-tutorial/ [Accessed: February 25,
swimming.htm [Accessed: July 15, 2018] 2018]
[19] El-Haddad MN. Chitosan as a [27] Taghavikish M, Dutta NK,

green inhibitor for copper corrosion Choudhury NR. Emerging corrosion
in acidic medium. International inhibitors for interfacial coating.
Journal of Biological Macromolecules. Coatings. 2017;7(12):217-245. DOI:
2013;55:142-149. DOI: 10.1016/j. 10.3390/coatings7120217
ijbiomac.2012.12.044
[28] Papavinasam S. Corrosion
[20] Tiu BDB, Advincula RC. Polymeric Inhibitors. In: Revie RW, editor. Uhlig's
corrosion inhibitors for the oil and Corrosion Handbook. 3rd ed. New York:
gas industry: Design principles and Wiley; 2000. pp. 1021-1033. DOI:
mechanism. Reactive and Functional 10.1002/9780470872864.ch71
Polymers. 2015;95:25-45. DOI: 10.1016/j.
reactfunctpolym.2015.08.006 [29] Umoren SA, Ekanem UF. Inhibition
of mild steel corrosion in H2SO4 using
[21] Zou Y, Wang J, Zheng YY. exudate gum from pachylobus edulis
Electrochemical techniques for and synergistic potassium halide
determining corrosion rate of rusted additives. Chemical Engineering
steel in seawater. Corrosion Science. Communications. 2010;197:1339-1356.
2011;53:208-216. DOI: 10.1016/j. DOI: 10.1080/00986441003626086
corsci.2010.09.011
[30] Dariva CG, Galio AF. Corrosion
[22] Law DW, Millard SG, Bungey Inhibitors—Principles, Mechanisms
JH. Linear polarization resistance and Applications. In: Aliofkhazraei
measurements using a potentiostatically M, editor. Developments in Corrosion
controlled guard ring. NDT and E Protection. 1st ed. Rijeka: InTech; 2014.
International. 2000;33:15-21. DOI: pp. 365-381. DOI: 10.5772/57255
10.1016/S0963-8695(99)00015-8
[31] Rahuma MN, BK M. Corrosion in
[23] Andrade C, Alonso C. Corrosion oil and gas industry: A perspective on
rate monitoring in the laboratory corrosion inhibitors. Materials Science
and on-site. Constrion and Building and Engineering. 2014;3(3):110-110.
Materials. 1996;10:315-328. DOI: DOI: 10.4172/2169-0022.1000e110
10.1016/0950-0618(95)00044-5
[32] Garverick L. Corrosion in the
[24] Sadowski L. New non-destructive Petrochemical Industry. 2nd ed. Ohio:
method for linear polarisation resistance ASM International; 1994. 509p. [Google
corrosion rate measurement. Archves Books]
of Civil and Mechanical Engineering.
2010;10:109-116. DOI: 10.1016/ [33] Kelland MA. Production
S1644-9665(12)60053-3 chemicals for the oil and gas industry.
14
Chromatographia. 2010;72(1-2):199- production and its mitigation.

199. DOI: 10.1365/s10337-010-1557-2 International Journal of Industrial
Chemistry. 2013;4(35):1-15. DOI:
[34] Arthur DE, Jonathan A, Ameh PO, 10.1186/2228-5547-4-35
Anya C. A review on the assessment
of polymeric materials used as [41] Sastri VS, editor. Green Corrosion
corrosion inhibitor of metals and alloys. Inhibitors: Theory and Practice. 1st ed.
International Journal of Industrial New Jersey: Wiley; 2011. 310p. DOI:
Chemistry. 2013;4(2):1-9. DOI: 10.1002/9781118015438
10.1186/2228-5547-4-2
[42] Obot IB, Obi-Egbedi NO, Umoren
[35] Granese SL, Rosales BM, Oviedo SA, Ebenso EE. Synergistic and
C, Zerbino JO. The inhibition antagonistic effects of anions and
action of heterocyclic nitrogen ipomoea invulcrata as green corrosion
organic compounds on Fe and inhibitor for aluminium dissolution
steel in HCl media. Corrosion in acidic medium. International
Science. 1992;33(9):1439-1453. DOI: Journal of Electrochemical Science.
10.1016/0010-938X(92)90182-3 2010;5(7):994-1107. ISSN: 1452-38981.
www.electrochemsci.org
[36] Sabirneeza AAF, Geethanjali R,
Subhashini S. Polymeric corrosion [43] Umoren SA, Ogbobe O, Igwe
inhibitors for iron and its alloys: IO, Ebenso EE. Inhibition of mild
A review. Chemical Engineering steel corrosion in acidic medium
Communications. 2015;202:232-244. using synthetic and naturally
DOI: 10.1080/00986445.2014.934448 occurring polymers and synergistic
halide additives. Corrosion Science.
[37] Eddy NO, Ebenso EE, Ibok UJ. 2008;50:1998-2006. DOI: 10.1016/j.
Adsorption, synergistic inhibitive corsci.2008.04.015
effect and quantum chemical studies
of ampicillin (AMP) and halides for [44] Umoren SA, Ebenso EE, Okafor
the corrosion of mild steel in H2SO4. PC, Ogbobe O, Oguzie EE. Gum arabic
Journal of Applied Electrochemistry. as a potential corrosion inhibitor
2010;40(2):445-456. DOI: 10.1007/ for aluminium in alkaline medium
s10800-009-0015-z and its adsorption characteristics.
Anti-Corrosion Methods and
[38] Yaro AS, Khadom AA, Wael Materials. 2006;53(5):277-282. DOI:
RK. Apricot juice as green corrosion 10.1108/00035590610692554
inhibitor of mild steel in phosphoric
acid. Alexandria Engineering Journal. [45] Buchweishaija J, Mhinzi GS. Natural
2013;52:129-135. DOI: 10.1016/j. products as a source of environmentally
aej.2012.11.001 friendly corrosion inhibitors: The case
of gum exudate from Acacia seyal var.
[39] Palou RM, Olivares-Xomelt O, seyal. Portugaliae Electrochimica Acta.
Likhanova NV. Environmentally 2008;26(3):257-265. DOI: 10.4152/
friendly corrosion inhibitors. In: Sastri pea.2008032257
VS, editor. Green Corrosion Inhibitors:
Theory and Practice. 1st ed. New [46] Fayyad EM, Sadasivuni KK,
Jersey: Wiley; 2011. pp. 257-303. DOI: Ponnamma D, Al-Maadeed MAA. Oleic
10.1002/9781118015438.ch7 acid-grafted chitosan/graphene oxide
composite coating for corrosion
[40] Popoola L, Grema A, Latinwo protection of carbon steel. Carbohydrate
G, Gutti B, Balogun A. Corrosion Polymers. 2016;151:871-878. DOI:
problems during oil and gas 10.1016/j.carbpol.2016.06.001
15
[47] Alaneme KK, Olusegun SJ, Alo [54] Zheng X, Gong M, Li Q, Guo
AW. Corrosion inhibitory properties of L. Corrosion inhibition of mild steel
elephant grass (Pennisetum purpureum) in sulfuric acid solution by loquat
extract: Effect on mild steel corrosion (Eriobotrya japonica Lindl.) leaves
in 1 M HCl solution. Alexandria extract. Scientific Reports. 2018;8:1-15.
Engineering Journal. 2016;55:1069-1076. DOI: 10.1038/s41598-018-27257-9
DOI: 10.1016/j.aej.2016.03.012
[55] Krishnan M, Subramanian H,
[48] El-Haddad MN. Dahms HU, Sivanandham V, Seeni P,
Hydroxyethylcellulose used as an Gopalan S, et al. Biogenic corrosion
eco-friendly inhibitor for 1018 inhibitor on mild steel protection in
c-steel corrosion in 3.5% NaCl concentrated HCl medium. Scientific
solution. Carbohydrate Polymers. Reports. 2018;8:1-16. DOI: 10.1038/
2014;112:595-602. DOI: 10.1016/j. s41598-018-20718-1
carbpol.2014.06.032
[56] Bhuvaneswari TK, Vasantha VS,
[49] Mobin M, Rizvi M. Inhibitory Jeyaprabha C. Pongamia pinnata as a
effect of xanthan gum and synergistic green corrosion inhibitor for mild steel
surfactant additives for mild steel in 1N sulfuric acid medium. Silicon.
corrosion in 1 M HCl. Carbohydrate September 2018;10(5):1793-1807. DOI:
Polymers. 2016;136:384-393. DOI: doi.org/10.1007/s12633-017-9673-3
10.1016/j.carbpol.2015.09.027
[57] Fouda AS, El-Awady GY, El
[50] Saxena A, Prasad D, Haldhar R, Behairy WT. Prosopis juliflora plant
Singh G, Kumar A. Use of Saraca asoca extract as potential corrosion inhibitor
extract as green corrosion inhibitor for for low-carbon steel in 1 M HCl
mild steel in 0.5 M H2SO4. Journal of solution. Journal of Bio- and Tribo-
Molecular Liquids. 2018;258:89-97. DOI: Corrosion. 2018;4:1-12. DOI: 10.1007/
10.1016/j.molliq.2018.02.104 s40735-017-0124-x
[51] Saxena A, Prasad D, Haldhar R, [58] Alvarez PE, Fiori-Bimbi MV,

Singh G, Kumar A. Use of Sida cordifolia Neske A, Brandán SA, Gervasi
extract as green corrosion inhibitor for CA. Rollinia occidentalis extract as
mild steel in 0.5 M H2SO4. Journal of green corrosion inhibitor for carbon
Environmental Chemical Engineering. steel in HCl solution. Journal of
2018;6:694-700. DOI: 10.1016/j. Industrial and Engineering Chemistry.
jece.2017.12.064 2018;58:92-99. DOI: 10.1016/j.
jiec.2017.09.012
[52] Haldhar R, Prasad D, Saxena A.
Myristica fragrans extract as an eco- [59] Khadom AA, Abd AN, Ahmed NA.
friendly corrosion inhibitor for mild Xanthium strumarium leaves extracts
steel in 0.5 M H2SO4 solution. Journal of as a friendly corrosion inhibitor of
Environmental Chemical Engineering. low carbon steel in hydrochloric acid:
2018;6:2290-2301. DOI: 10.1016/j. Kinetics and mathematical studies.
jece.2018.03.023 South African Journal of Chemical
Engineering. 2018;25:13-21. DOI:
[53] Qiang Y, Zhang S, Tan B, Chen 10.1016/j.sajce.2017.11.002
S. Evaluation of Ginkgo leaf extract as
an eco-friendly corrosion inhibitor of [60] El Ibrahimi B, Jmiai A, Bazzi L,
X70 steel in HCl solution. Corrosion El Issami S. Amino acids and their
Science. 2018;133:6-16. DOI: 10.1016/j. derivatives as corrosion inhibitors for
corsci.2018.01.008 metals and alloys. Arabian Journal of
16
Chemistry. 23 September 2018. DOI: alloy in coastal-acidified medium. In:

10.1016/j.arabjc.2017.07.013. (In Press) Aliofkhazraei M, editor. Corrosion
Inhibitors, Principles and Recent
[61] Zhang DQ, Xie B, Gao LX, Cai Applications. 1st ed. Rijeka: InTech
QR, Joo HG, Lee KY. Intramolecular Open; 2018. pp. 79-94. DOI: 10.5772/
synergistic effect of glutamic acid, intechopen.72942
cysteine and glycine against copper
corrosion in hydrochloric acid solution. [68] Ali AH. Electrochemical study of
Thin Solid Films. 2011;520:356-361. candesartan drug as corrosion inhibitor
DOI: 10.1016/j.tsf.2011.07.009 for carbon steel in acid medium.
Journal of Advanced Electrochemistry.
[62] El-Sayed NH. Corrosion inhibition 2018;4(1):152-157. DOI: 10.30799/
of carbon steel in chloride solutions by jaec.050.18040101
some amino acids. European Journal
of Chemistry. 2016;7(1):14-18. http:// [69] Matad PB, Mokshanatha PB,
www.eurjchem.com/index.php/ Hebbar N, Venkatesha VT, Tandon
eurjchem/article/view/1331 HC. Ketosulfone drug as a green
corrosion inhibitor for mild steel
[63] Mobin M, Zehra S, Parveen in acidic medium. Industrial &
M. L-Cysteine as corrosion inhibitor for Engineering Chemistry Research.
mild steel in 1 M HCl and synergistic 2014;53:8436-8444. DOI: 10.1021/
effect of anionic, cationic and non- ie500232g
ionic surfactants. Journal of Molecular
Liquids. 2016;216:598-607. DOI: [70] Singh P, Chauhan DS, Srivastava
10.1016/j.molliq.2016.01.087 K, Srivastava V, Quraishi MA. Expired
atorvastatin drug as corrosion inhibitor
[64] Wang T, Wang J, Wu Y. The for mild steel in hydrochloric acid
inhibition effect and mechanism of solution. International Journal of
L-cysteine on the corrosion of bronze Industrial Chemistry. 2017;8:363-372.
covered with a CuCl patina. Corrosion DOI: 10.1007/s40090-017-0120-5
Science. 2015;97:89-99. DOI: 10.1016/j.
corsci.2015.04.018 [71] Dahiya S, Saini N, Dahiya N,
Lgaz H, Salghi R, Jodeh S. Corrosion
[65] Zeino A, Abdulazeez I, Khaled inhibition activity of an expired
M, Jawich MW, Obot IB. Mechanistic antibacterial drug in acidic media amid
study of polyaspartic acid (PASP) elucidate DFT and MD simulations.
as eco-friendly corrosion inhibitor Portugaliae Electrochimica Acta.
on mild steel in 3% NaCl aerated 2018;36(3):213-213. DOI: 10.4152/
solution. Journal of Molecular Liquids. pea.201803213
2018;250:50-62. DOI: 10.1016/j.
molliq.2017.11.160 [72] Damborenea JD, Conde A, Arenas
MA. Corrosion inhibition with rare
[66] Ituen EB, Akaranta O, Umoren earth metal compounds in aqueous
SA. N-acetyl cysteine based corrosion solutions. In: Forsyth M, Hinton B,
inhibitor formulations for steel editors. Rare Earth-Based Corrosion
protection in 15% HCl solution. Journal Inhibitors. 1st ed. Cambridge:
of Molecular Liquids. 2017;246:112-118. Woodhead Publishing; 2014. pp. 84-116.
DOI: 10.1016/j.molliq.2017.09.040 DOI: 10.1533/9780857093585.84
[67] Fayomi OSI, Anawe PAL, [73] Hinton BRW, Arnott DR, Ryan
Daniyan A. The impact of drugs as NE. Inhibition of aluminum alloy
corrosion inhibitors on aluminum corrosion by cerous cations. Metals
17
Forum. 1984;7(4):211-217. [Google States Patent Application No. [US

Scholar] 20170306506]
[74] Hinton BRW. Corrosion inhibition [82] Erickson DL, Johnson RA, LaBrosse
with rare earth metal salts. Journal of MR, Young PR. Corrosion inhibiting
Alloys and Compounds. 1992;180:15-25. methods; 2016. United States Patent
DOI: 10.1016/0925-8388(92)90359-H Application No. [US9290850B2]
[83] Meyer GR, Monk KA. Corrosion
[75] Forsyth M, Seter M, Tan MY, inhibitors for oil and gas applications;
Hinton B. Recent developments 2013. United States Patent Application
in corrosion inhibitors based on No. [US9382467B2]
rare earth metal compounds.
Corrosion Engineering, Science and [84] Kharshan M, Fursan A, Gillette K,
Technology. 2014;49:130-135. DOI: Kean R. Bio-based corrosion inhibitor;
10.1179/1743278214Y.0000000148 2013. United States Patent Application
No. [US8409340B1]
[76] Forsyth M, Seter M, Hinton
B, Deacon G, Junk P. New “Green”
corrosion inhibitors based on rare
earth compounds. Australian Journal
of Chemistry. 2011;64:812-819. DOI:
10.1071/CH11092
[77] Forsyth M, Hinton B, editors. Rare

Earth-Based Corrosion Inhibitors. 1st
ed. Cambridge: Woodhead Publishing;
2014. 338p. [Google Books]
[78] Badawi AM, Hegazy MA, El-Sawy

AA, Ahmed HM, Kamel WM. Novel
quaternary ammonium hydroxide
cationic surfactants as corrosion
inhibitors for carbon steel and as
biocides for sulfate reducing bacteria
(SRB). Materials Chemistry and Physics.
2010;124:458-465. DOI: 10.1016/j.
matchemphys.2010.06.066
[79] Verma C, Ebenso EE, Quraishi

MA. Ionic liquids as green and
sustainable corrosion inhibitors for
metals and alloys: An overview. Journal
of Molecular Liquids. 2017;233:403-414.
DOI: 10.1016/j.molliq.2017.02.111
[80] Hafiz TB, Almathami AA, Agrawal
G, Hoegerl M. Green high-efficiencey
corrosion inhibitor; 2018. United
States Patent Application No. [US
20180057947]
[81] Drewniak M, Steimel LH.

Composition and method for inhibiting
corrosion and scale; 2017. United
18
Chapter 06
Formation of Anticorrosive
Structures and Thin Films on
Metal Surfaces by Applying EDM
Pavel Topala, Alexandr Ojegov and Vitalie Besliu
Abstract
The methods of the formation of anticorrosive strata and thin films on metal
surfaces by applying electric discharge machining (EDM) are presented in this
chapter. The increase of anticorrosion resistance of metal surfaces by the formation
of palladium depositions, carbon films and oxide and hydroxide films has been
demonstrated. Corrosion and electrochemical behaviour of titanium with palladium
powder coatings were investigated in sulfuric acid solutions at temperatures of 80
and 100°C. In order to increase the diffusion of palladium in the base material and
to increase the layer homogeneity, after coating, the samples were annealed in
vacuum at 1150°C for 1 hour. The proposed method allows to reduce the corrosion
speed of titanium at least by two orders (from 18.7 to 0.3 g m2 h1); the corrosion
potential is changed towards positive values (from 0.56 mV to +0.3 V). The
research on surface electrical resistance and resistance to corrosion of oxide and
hydroxide films formed on steel C45 surfaces by applying EDM have shown that the
surface electrical resistance of the samples increased by 107 times, the potential of
corrosion increased from 0.44 mV to +0.4 V and the resistance to corrosion has
increased by about two times in 1% NaCl water solution and by about 10 times in
30% H2SO4 water solution. The less pronounced increase of anticorrosion proper-
ties has carbon films formed on the same steel C45 surface; instead they increase
superficial microhardness, the functional durability and processing productivity of
the active piece surfaces.
Keywords: electric discharge machining, corrosion, thin films, carbon,

microhardness
1. Introduction
Corrosion is a damaging process for the absolute majority of parts that work in
active environments, from the chemical point of view, and becomes even more
pronounced when they operate in energy fields of different types: high tempera-
tures, light, electrical action, etc. It consists in the destruction of metallic materials
under the chemical or electrochemical action of the environment or the substances
they come into contact with.
With the exception of noble metals, all other metals are unstable in contact with
the atmospheric air and aggressive environments. The way this instability manifests
1
itself, and the degree to which it occurs, depends on the nature of the metal and the
environment in which it is placed.
Two types of corrosion can be highlighted considering the deployment mecha-
nism: chemical corrosion [1] which refers to the processes of destruction of metals
and alloys produced in dry gases as well as in liquids without electrical conductivity
and in most organic substances and electrochemical corrosion [1–8] which causes
processes of metal and alloy degradation in electrolyte solutions in the presence of
humidity, accompanied by the flow of electric current through the metal.
In all cases, when talking about the functionality of the machines and appara-
tuses or the parts from which they are assembled and their durability, the process of
component degradation of different constructions is a damaging one. Throughout
the practical encountered corrosion problems, it is important to know the real speed
the process is taking place. If the corrosion process is possible, but has a very low
deployment speed, the material is considered corrosion resistant.
Taking into account that iron and its alloys are used in the contemporary con-
struction of machinery and apparatus as basic materials, and, on the other hand, a
material for the present and future is considered to be titanium and its alloys, in the
following, we will focus on the research of behaviour of these materials in different
working environments.
In the case of iron, its corrosion takes place in stages by its oxidation in the
atmosphere with the formation of iron oxides (rust).
In the course of the first stage of iron oxidation, FeO is formed, ferrous oxide,
which is stable only in the absence of oxygen. When atmospheric oxygen appears,
iron oxide is converted into iron hydroxide (Fe2O3H2O) or FeO(OH), of which two
phases are known:
• Phase 1 that corresponds to a large excess of oxygen
• Phase 2 characterized by an insufficient amount of oxygen, which is why

oxidation evolves slowly
Depending on their colour, there are three types of rust:
1. Fe(OH)2 white rust, formed after the reaction:
Fe þ 2H2 O ! FeðOHÞ2 þ 2H2
This type of rust quickly passes through oxidation to brown rust, which is why
it is rarely seen.
2. Brown rust occurs as a result of the following reaction
4FeðOHÞ2 þ O2 ! 4FeOðOHÞ þ 2H2 O
3. The black rust is made of ferrous and ferric oxide, being also called magnetite
because of its magnetic properties, and it is considered to be the most stable
form of iron oxide. It forms a protective layer on the surface of the metal, with
a homogeneous and adherent structure.
The reaction is as follows:
2FeOðOHÞ þ FeðOHÞ2 ! Fe3 O4 þ 2H2 O
2
Formation of Anticorrosive Structures and Thin Films on Metal Surfaces by Applying EDM
Iron and its alloys are reacted with electrochemically active acids and salts of
metals with the destruction of the workpiece surface in working environments:
Fe þ H2 SO4 ! FeSO4 þ H2
Fe þ 2HCl ! FeCl2 þ H2
Fe þ CuSO4 ! FeSO4 þ Cu
Fe þ 2NaCl ! FeCl2 þ 2Na
Titanium and its alloys are more resistant to corrosion, since, under normal
conditions in the atmosphere, the TiO2 oxide film is formed, which is stable in
different environments, other than those alkaline, for instance:
TiO2 þ Na2 CO3 ðK2 CO3 Þ ! Na2 TiO3 ðK2 TiO3 Þ þ CO2
Under certain conditions (high temperature, high concentration), titanium also

reacts with some acids:
Ti þ H2 SO4 ! TiSO4 þ H2
2Ti þ 3H2 SO4 ! Ti2 ðSO4 Þ3 þ 3H2
Ti þ 8HNO3 ! TiðNO3 Þ4 þ 4NO2 þ 4H2 O
2Ti þ 6HCl ! 2TiCl3 þ 3H2
2Ti þ 6HBr ! 2TiBr3 þ 3H2
2Ti þ 6HI ! 2TiI3 þ 3H2 , etc:
They destroy the base metal and cause further damage of the workpieces in
those environments.
The methods and techniques of anticorrosive protection are various and numer-
ous, and they can be grouped into the following categories [9]:
• Methods of preventing corrosion.
• The use of metals and alloys resistant to corrosion.
• Methods of influencing the corrosive medium [10, 11].
• Methods of covering metal surfaces with protective layers [12–14].
• Passivation of surfaces by depositing anticorrosive strata, etc. The essence of

preventing corrosion consists in [9].
• Correct choice of materials used in building devices, industrial equipment from

the point of view of resistance to corrosion.
• Avoiding the contact of two metals, one of which is more electronegative than
the other, e.g., aluminium and copper alloys or alloyed steel, bronze and steel,
etc.
• Avoiding the contact of cold-hardened metals with annealed or cast metals, for
the reason that due to the difference of electrochemical potential between
them, the last one corrodes in the presence of an electrolyte.
3
• A more careful processing of the metal surface, since hollows and scratches
favour and accelerate corrosion.
The group of metals and alloys resistant to corrosion contain noble metals and
their alloys, but their use becomes difficult because of the high cost. Self-protective
metals and alloys will be used instead. These are metals and alloys which, after an
initial corrosion, are covered with an isolating pellicle or film as a result of the
passivation phenomenon (e.g. the passivation of Ag in HCI by forming the AgCl film
of Fe in HNO3 concentrated through the formation of the Fe(NO3)3 pellicle, etc.).
In most cases, metals are alloyed with an adequate component. Sometimes the
relatively low concentration of the alloyed component considerably reduces the
corrosion speed (e.g., the introduction of such elements as Cu, Cr or Ni of 0.2–0.3%
in steels, etc.).
There are many cases when it is possible to influence the corrosive medium to
lower the speed of corrosion. There are many possibilities.
The following can be mentioned [9]:
• Modification of pH, which means bringing it to a convenient value for the

metal that is to be protected. This consists in the elimination from the medium
of corrosion, by the use of physical, chemical and mechanic methods (e.g.,
neutralization of waste water with chemical substances).
• Removal of gases (O2 and CO2), which increase the speed of corrosion in
corrosive media, particularly that of the water.
• The use of inhibitory elements (organic or inorganic substances) [10, 11],

which, being introduced in small quantities in the corrosive medium, lower or
completely annihilate its corrosive capacity.
• Cathode protection (electro-defence) means the use of galvanic methods of

metal protection with the help of auxiliary metal anodes, which take over the
corrosive capacity of the medium, thus protecting the material used for the
workpiece.
The protection realized by applying anticorrosive layers [9, 12–14] means to

cover the metal with a thin layer or self-protective material. The self-protective
layer should meet the following requirements: it should be compact and adherent, it
should be elastic and plastic enough, and its thickness should be uniform in addition
to being as small as possible. The protective layer may be metallic or nonmetallic.
Metallic deposits may be realized through different methods: galvanic, thermal,
through plating, laser radiation, bombarding with ions, alloying by means of electric
discharge machining (EDM), etc. The formed surface layers, except those obtained
through plating, usually present a certain porosity, which determines the appear-
ance of local portions of corrosion with all the consequences. Nonmetallic protective
layers may be organic or inorganic, realized with the help of varnish, paints,
enamels or plastic thin sheets.
The formation of inorganic thin films or pellicles (oxide or graphite) on the
workpiece surface is a progressive method of anticorrosive protection of superficial
layers. The oxide or the graphite, being much more passive than the proper metal,
in the interaction with the work media lowers the corrosive potential of the whole
piece. The key problem that should be solved is the one that deals with the forma-
tion of structurally stable deposits with a high mechanic and electric resistance,
having a uniform continuity and thickness on the whole surface.
4
The choice of the method to be used for the production of the protective layer
depends on [9]:
• The conditions and working surroundings of the piece
• The shape and the dimensions of the protective item
• The quality of the supportive material or of the protected item
• The functional technological parameters of the device
• The way the item to be protected is placed in the device
• The technologies of application and executive possibilities for anticorrosive

protection
2. Methodology of experimental investigations
2.1 Experimental setup
The experimental setup for the formation of anticorrosive coatings on the metal
surfaces of the parts by applying pulsed electric discharge machining (PEDM)
comprises the following electric blocks: the power pulse generator, the priming
block (intended for initiating the electrical discharge) and the control block, the
role of which is to synchronize the power and the priming discharge pulses.
As a result of the specialty bibliographic analysis [12, 13, 15–21], it was con-
cluded that, for the formation of these layers, RC-type generators, with parallel
priming, can be successfully used.
The deposition of layers of metallic powders with the use of electric fields is
produced as a result of interaction of the powder particles with the plasma jet and
the transport of the liquid and vapour phase on the surface of the piece-cathode
[12, 13]. The powder particles, having the dimensions of 20–200 μm, are inserted in
the 0.3–1.5 mm gap at a capacitor voltage of Uc = (80...400) V.
2.2 Methodology of anticorrosive coatings formation
Research on the interactions of the plasma channel of PEDM with the surfaces of
the electrodes have shown that for the phenomenon of electroerosion, two types of
effects are characterised as follows: type I, the appearance of the “cold” electrode
spots on the electrode surfaces, which give rise to the asperities and impurities on
their surface [12, 13] and cause both the cleaning of the surfaces of impurities and
their thermal interaction, producing structural changes in the superficial layers of
small thicknesses (just about the size of micro- and nanometers), and type II, on the
electrode surfaces, in which, after the “cold” electrode spots, the “warm” ones cause
the essential melting of the electrode, accompanied by the vaporization phenomena
and the dropping of the electrode material [13]. If type II interaction of the plasma
channel with electrode surfaces has found a rather wide application in dimensional
processing [22–27] and the deposition layer formation (both of the compact mate-
rials [21] and the powders [12, 13]), then type I actions are described in the litera-
ture only as scientific findings, and for this reason, it is necessary to elucidate the
conditions and the effects of surface thermal treatment and to reveal whether this
type of interaction is purely thermal or is a thermochemical one.
5
Analysing the results obtained by the author of the paper [13], it was established
that, in order to obtain a type I interaction with the plasma channel (in the absence
of surface melting) or type II interaction (when the liquid phase is attested) on the
surfaces of the workpieces, it is necessary that the energy density emitted on the
processed surface be lower or higher than the specific heat of melting of the mate-
rial, and the latter can be appreciated by the relation [13, 16, 28]:
4W 4W
2
<Q < 2
πdc S πdc S (1)
Q ¼ qρ,
where q and ρ are the specific heat of melting and the density of the workpiece
material, respectively, W is the energy emitted in the gap, dc is the diameter of the
plasma channel and S is the gap value.
As can be seen from the relation (Eq. 1), at the time of the energetic processing
regime, the size of the gap and the thermo-physical properties of the workpiece
material are known; the diameter of the plasma channel can be determined, which
coincides with the size of its trace on the processed surface. If a coefficient of
overlapping of the traces (of type I or type II) k = 0.5...1.0 and the frequency of the
electrical impulses f are known, the productivity of the technological process can be
determined by the relation:
kπd2c f
η¼ (2)
4
In the paper [13], it has been demonstrated that when PEDM is applied for
superficial processing, the erosion processes take place, accompanied by explosive
melting and vaporization of the electrode material for the vast majority of studied
metals and alloys, for the current pulse duration contained in the limits 104–109 s.
It results that, in order to obtain the expected effects, it is necessary to provide a
relatively low-duration pulses of discharge.
Effects on electrode surfaces are a function depending on the way of the work-
piece connection in the discharge circuit (as anode or as cathode) [13, 16, 21]. These
desiderata have been studied in [13], and it has been established that for short-term
discharge pulses, they are “cathodic” and for the long-term ones, they are “anodic”;
thus, in the case of superficial thermal treatments and deposition of materials, the
workpiece will be included in the discharge circuit as cathode. In the case of thermal
treatment of steel surfaces, their hardness increases by 2–3 times and for titanium
surfaces by 2–5 times, for the formed layers thicknesses from a few micrometres to
several dozens of micrometres. The depth of these layers reaches a maximum at three
passes of technological cycle for steels and at five passes for titanium and its alloys.
The interaction of the plasma channel with the surface of the electrode work-
piece is not always purely thermal; nonetheless the surface of the piece is often
enriched with elements contained in the environment and with the contents of the
tool-anode material. The penetration depth [13] of these elements in the superficial
layer of the piece is a function of both the energy of the discharge pulse and the size
of the gap and can be expressed with the relation:
kW S
h¼ (3)
AS
Ðτ
where W S ¼ U ðtÞIðtÞdt is the energy emitted in the gap during a singular
o
discharge; U and I are the voltage and the current in the gap, respectively; τ is the
6
pulse duration; A is the area of the workpiece surface processed at a singular

discharge; and k is a constant that depends on the thermo-physical properties of the
workpiece material.
2.2.1 Technology of powder deposition formation
From the results of the experimental researches carried out by the authors
[12, 13], it has been demonstrated that, in order to obtain the powder depositions, it
is necessary to introduce the powder in the anode zone of the gap. From a techno-
logical point of view, a parameter that needs to be predicted is the thickness of the
deposition layer. This parameter is quite important, because in some cases it is
determinant in the technological application of the method. Analysing the experi-
mental results of the authors of this chapter and those of the works [13, 18, 19, 29, 30],
in the case of the deposition layers of different materials, the following relationship
was deduced for the deposition thickness:

Pc f d W k a bS2 rm
H¼ n (4)
ρA
where P is the powder flow, f is the frequency of impulse discharges, r is the

equivalent radius of powder particles, W is the energy released in the gap, S is the
size of the gap, ρ is the density of the particles’ material, A is the area of the
processed surface, n is the number of passes of the tool-electrode on the workpiece
surface, a and b are individual constants of the deposition materials, and c, d, k, and
m are the power exponents that are experimentally established and constitute both
functions, of the properties of the powder material and of the processing conditions.
Taking into account the experimental results obtained by the authors of the
papers [13, 21] for the determination of the thickness of the deposition layer, the
relation (Eq. 4) can be written as
Δm
H¼ n (5)
ρA
where

Δm ¼ Pc f d W k a bS2 rm (6)
The uniformity of deposition of the layer is characterized by the thickness of the

deposited layer (or by the dimension Δm on each surface unit). If the processing
time is different during the manual processing on different surface portions, the
surface is not continuous; the mechanization of the process ensures the formation of
uniform deposition on the entire surface of the workpiece.
The compactness of the layers and the existence of recesses or asperities are
visually appreciated or measured using the microscope analysis method.
2.2.2 Technology of oxide films formation
In order to achieve the experimental researches, the pulse current generator

with priming from a high-voltage block with 12 kV voltage and 0.3 μA current was
used; the laboratory installation ensures the positioning, fixing and rotation of the
samples during the processing with an adjustable rotation frequency ranging from 0
to 150 rpm [28]. The used tool-electrode was made in the form of cylindrical bar,
rounded at the working end in the shape of a hemisphere and made of stainless steel.
7
The cathode piece was a cylindrical bar 13 mm in diameter. The piece was firmly
fixed to the tool-machine frame and the tool-electrode into the tool port. The
workpiece was connected to the pulse generator as cathode and the tool-electrode
as anode, their axes forming an angle of 90°. In the case of flat surface processing,
both the piece and the tool-electrode were made in the form of cylinders with a
diameter of 10 mm; they were firmly fixed to the tool-machine port with parallel
active surfaces and the electric discharge scanning the workpiece surface by migra-
tion of the plasma channel on these surfaces at a processing cycle. The materials for
the pairs of electrodes (workpiece/tool-electrode) were chosen: aluminium alloy
AlCu4Mg1, steel C45, titanium alloy TiAl6Mo4 and copper alloys.
2.2.3 Technology of graphite deposition formation
Experimental research on graphite deposits was carried out under normal con-
ditions in the air environment, under sub-excitation regime of PEDM. For the
purpose of realizing the experiments, the power supply having the following
parameters was used: the energy released in the gap WS = 0–4.8 J, the energy
accumulated on the capacitor battery Wc = 0–12 J, the voltage on the capacitor
battery Uc = 0–200 V, the capacity C = 100–600 μF with step of 100 μF, the gap
value S = 0.05–2.5 mm, discharge frequency f = 0–50 Hz and impulse duration
τ = 0–250 μs. Due to these parameters, we can provide the PEDM operation under
the regime of “hot” electrode spots (with the melting of the processed surfaces) and
under the regime of the “cold” electrode spots (without melting the surfaces
undergoing processing, although at nanometer scale it occurs).
Between the two electrodes, a graphite cathode and an anode made of the metal
specimen, microelectric discharge is applied. The microelectric arc that is produced
for a very short period of time—microseconds—has a very high temperature of
about 104°C. At this temperature the graphite erodes (in the form of separated
carbon atoms or chemical compounds of the type CO and CO2 which further
decompose into carbon and oxygen, the first being ionized is deposited in the form
of film on the metal surface, and the oxygen is released in the plasma [28]), and due
to the fact that it is in an electric field, the graphite particles in the vapour state are
transported to the opposite sign electrode (anode) made up of the metal specimen.
Thus, on the metal surface of the anode, a graphite layer of the micrometre dimen-
sion is deposited.
2.3 Methodology for determining the corrosion potential and speed of the
samples
In order to measure the potential and the speed of corrosion, a setup was
developed, the scheme of which is shown in Figure 1. In vessel 1 with electrolyte 2
(3% NaCl water solution for samples made of construction steels and 40% H2SO4
water solution for titanium, copper and aluminium alloy samples), the sample and
cathode 6 are fixed. The cathode joins at the “” pole and the sample at the “+” pole
of the DC source with smooth voltage regulation. A milliammeter is connected in
serial with the source and a voltmeter, in parallel, respectively. To measure the
corrosion potential of the superficial oxide layer 4, the base metal 3 is placed in a
rubber gasket 5 having a hole 7 so that only the oxidized surface of the sample is in
contact with the electrolyte. The voltage is gradually increasing until the current
appears, which will be indicated by the voltmeter—the value of the corrosion
potential and the milliammeter—the corrosion current. In order to increase the
measurement precision, several measurements are made for different parts of the
sample surface.
8
Figure 1.
Potential and speed of corrosion measurement scheme: (1) vessel, (2) electrolyte, (3) sample connected as
anode, (4) oxide layer, (5) rubber gasket, (6) cathode and (7) hole for contacting the oxidized surface with the
electrolyte in the water solution.
In order to perform the chemical corrosion resistance tests of the processed

samples (with PEDM-coated oxide films on the active surface), electrolytes from
distilled water and chemical agents with the respective concentration at room
temperature were prepared, or, in separate cases, the device was continuously fed
with an electrolyte of a certain temperature via a thermostat.
The samples were firmly fixed in the prepared device (Figure 1) so that only a
circle-shaped part of the processed surface was subjected to dissolution. This was
included in the anode dissolution circuit as the anode. The tests were carried out in
the operating mode of the experimental DC installation and the 0.1 V step-by-step
voltage change [28].
The corrosion speed is determined by weighing the samples before and after the
test at the analytical electronic balance KERN ABS-N ABJ-NM with the accuracy of
105 g.
The corrosion speed index is determined with the relation (Eq. 3):
Δm
K¼ ; (7)
St
where K is the speed of corrosion (mass indicator), gm2h1; S is the area of the
workpiece surface, m2; t is the test duration (work time), h; and Δm is the mass lost
(or the mass addition), g:
Δm ¼ mi mf (8)
where mi is the initial mass of the sample, g, and mf is the final mass of the
sample, g.
3. Results
3.1 Research on structural and phase transformations in superficial layers of

the workpiece
The formation of powder deposition layers is accompanied by a wide range of

structural and phase changes [13, 16, 29, 30]. The phase transformations are
9
conditioned by the occurrence of the liquid phase and the vapour of the deposited
particles interacting with the discharge channel, the environment, the cathode
material and the liquid phase and solid phase transfer and hardening processes. As it
has been shown, due to the electroerosion processes of the cathode material, it may
be in the liquid-vapour state and interact with the environment; therefore, usually
in the formed powder layer, besides oxides, nitrides and its intermetallic compo-
nents, cathode material can be introduced in its other phases, respectively [13, 16,
29, 30]. The mentioned phases may occur in the contact zone between the particle
and base material during the interaction of the liquid-vapour material of the cath-
ode with the gap medium and the deposited particle and also in the case of deposi-
tion of precursor particles, which do not come into direct contact with the material
of the piece but which have been influenced by plasma discharge. In particular, this
is the area of “cold” spots, whose dimension is larger than the contact area between
the sample and the particle (even for the maximum particle diameter of the depos-
ited powder), and this is clearly visible for S > 0.5 mm (see Figure 2).
The condition in which the deposited particles interact with the surface portion
of the workpiece, which has previously been in contact with the plasma discharge,
is more often achieved in obtaining the continuous deposition layers.
These conditions were achieved in the roentgen research of the phase compo-
nent of superficial layers for steels (steel 3, steel C45) and titanium (BT 1-0).
Plasma interaction was achieved in the continuous processing (without including
the powder in the processing area) when the interaction areas partially or variously
overlapped (the number of passes n on the same surface portion varied). The
cylindrical electrode-anode was made of graphite. The gap value was changed in the
range of 0.15–2 mm, and the other parameters were Uc = 240 V and f = 40 Hz.
The analysis of the change of the phase composition of the processed surfaces
(steel C45, titanium BT 1-0) has shown that the basic role in these changes is played
by rapid heating and cooling, and their interaction with the environment, during
the processing, is not so significant. The intensity of these changes is a function of
the deposition material properties and processing conditions, such as the gap value
(which, during the experiments, was modified for constant energy emitted in the
Figure 2.
Diffractograms of titanium BT 1-0 cathode sample surfaces processed by PEDM at a different number of passes,
n: (a) 2 passes, (b) 4 passes, (c) 6 passes and (d) 8 passes; the energy emitted in the gap W = 5,3 J; the gap
value S = 1.5 mm.
10
gap W = const). While processing BT-1-0 technical titanium, practically all the
phases that are possible in its interaction with the oxygen and nitrogen in the air,
under the action of discharge, have been experimented (Figure 2) [13]. Oxides
(TiO, Ti2O) and titanium nitride (TiN) form more intensively at gap values S
< 1 mm. For larger gaps (S ≥ 2 mm), only traces of TiO and TiN can be identified
(Figure 2). In the multiple action of plasma, even for large values of the gap, the
same phase component is formed on the surface of the titanium (Figure 2b), that is,
TiO, TiO2 and TiN. In this regard, less active is the steel surface; the increase of its
processing time (on the account of the number of n passes) changes nonessentially
its phase composition (Figure 3).
After the action of the discharge plasma on the surface of the steels on the
diffractograms, along with the characteristic lines for the ferrite phase, there are
also lines corresponding to the austenite phase. The maximum austenite quantity is
obtained for S ≤ 0.5 mm, i.e. when the outbreak surface is practically occupied by
the liquid sample material. Some of the lines of the diffractograms can be identified
as characteristic to carbide lines (Fe3C) and to iron nitrides lines (Fe3N-Fe4N).
The presence of austenite and cementite lines during the processing of samples
made of steel 3 is caused by the transfer on the surface of the anode material
(graphite). The absence of oxides for the investigated regimes according to the
roentgen method, at first estimation, under normal conditions, confirms the
Figure 3.
Diffractograms of steel C45 cathode sample surfaces processed by PEDM for different gap values: S = 0.15 mm
(a), S = 0.45 mm (b), S = 1.0 mm (c) and S = 2.0 mm (d).
11
hypothesis that the “cold” spots burn the oxides and impurities of the superficial
layer [31–33], i.e. the discharge channel theoretically “migrates” to these defects of
the surface, which finally condition their removal by vaporization (this is valid for
singular passes) and also for the reduction of oxides by carbon. The technological
process for steel surface cleaning by arc discharge in vacuum is developed based on
this phenomenon [34].
The detailed investigations [13] of the processed surfaces using the Mössbauer
method of the steel samples (Figure 4) indicate both spectra and represent an
elusive superposition of iron oxides and hydroxide doublets and confirm the pres-
ence of the γ-Fe phase for S = 0.5 mm. The distribution of iron, oxygen, carbon and
nitrogen in the sample depth is shown in Figure 5, which shows that carbon
Figure 4.
Mössbauer spectra of steel 3 sample after processing by PEDM: S = 2 mm (a) and S = 0.5 mm (b) [13].
Figure 5.
Elements distribution in steel 3 sample surface after processing by PEDM for gap and specific energy values:
S = 0.5 mm and P = 3.19 Jmm3 (a); S = 2 mm and P = 1.5 Jmm3 (b) [13].
12
aggregates to the surface. Its concentration decreases rapidly as the depth of the
investigated layer increases, and the oxygen concentration reaches up to 60%.
This increased oxygen concentration can be achieved in the formation of
hydroxides in the superficial layer of the sample. At a depth of layer of up to
240 nm, the nitrogen concentration is up to 5–6%.
For the value of gap S = 2 mm, the main components of the surface are iron and
oxygen, and the secondary are carbon and nitrogen, respectively (Figure 5b). The
oxygen concentration reaches 60% on the processed sample surface and lowers in
the depth of the sample; the variation can be explained by the fact that in the
superficial layer, hydroxides are formed and, in the depth of the sample, metastable
oxides are formed; according to roentgenograms FeO (a single paramagnetic iron
oxide at room temperature) is missing on the surface of the sample. Therefore, we
can accept meta-stability of some very thin layers of Fe2O3 and Fe3O, which is
known according to [13]. Moreover, the possibility of amorphous iron hydroxides
formation is not excluded [13]. Mössbauer spectra show that the complexity of
unambiguously identifying amorphous hydroxides is very difficult.
The physical composition of the titanium and steel surfaces, after the removal of
a layer of 5–10 nm thickness by means of rectification, changes nonessentially: the
amount of oxides decreases in titanium and in steels—the nitride component
decreases. Changing the energy regime does not condition the essential qualitative
changes, for constant values of the gap S = const, and only quantitative changes take
place.
Thus, the analysis of diffractograms has shown that among the elements of the
processing regimes, the most important that essentially influence the phase compo-
nent of the processed surface are the size of the gap, the energy density in it and the
time of interaction with the plasma (the impulse duration and the number of passes
of the plasma channel on the processed surface).
3.2 Determination of corrosion resistance of titanium and its alloys with

deposited layers of metallic powder
In the process of deposition with electrodes made of compact materials by

PEDM method, it is difficult to form layers with a full continuity, constant thick-
ness, without pores, without impurities, etc., important elements for obtaining
corrosion-resistant layers. The depositions obtained by the authors of the papers
[13, 16, 29, 30] have shown good results in their corrosion resistance. When depos-
iting metal powders, it is possible to form layers with highest thickness, but the
problem of porosity remains unresolved.
Up to now, detailed research has been carried out on the corrosion resistance of
titanium samples on which palladium (Pd), ruthenium (Ru) and nickel (Ni) depo-
sitions have been formed [29, 30]. The modification of the superficial titanium
chemical composition with these metals was performed in order to obtain anodes on
the base of titanium resistant to corrosion. The obtained results [29, 30] indicate
that deposits formed by this method increase the corrosion resistance of titanium by
about five times.
The corrosion and the electrochemical behaviour of titanium, with layers
formed with the use of metal powders, were investigated by the authors [30] for the
application of the 10% H2SO4 solution in distilled water at temperatures of 80 and
100°C, respectively. After the formation of the layers, some of the samples were
subjected to annealing in vacuum at 1150°C for 1 hour for the purpose of palladium
diffusion in the sample material. The corrosion and the electrochemical tests for the
annealed samples were carried out in 10% H2SO4 solution in distilled water at 80
and 100°C and in 20, 30 and 40% H2SO4 solution in distilled water at 100°C. The
13
palladium content was determined in the solution by the photo-calorimetric

method. In the annealed samples, the palladium content was 5.6 mgcm2.
The corrosion speed of titanium with powder depositions in 10% H2SO4 solution
in distilled water at 80°C was 0.2 gm2h1; at 100°C in the first 5 hours of testing,
the speed was 0.78 gm2h1; and then, during the tests, the speed decreased and,
in 50 hours of testing, has dropped to 0.3 gm2h1. This situation of diminishing
the corrosion speed can be caused by the dissolution of the unstable phases in the
first hours. The corrosion potential, under these conditions, is situated within the
passivity limits and equal to +400 mV in 10% H2SO4 solutions at 80°C (relative to
the standard hydrogen electrode) and at 100°C equal to +300 mV compared to the
titanium samples, without protecting depositions in the 10% H2SO4 solution in
distilled water, which actively dissolves at potential of 0.56 mV with the speed of
18.72 gm2h1. Thus, we can state that, in the case of deposits application, the
corrosion speed decreases up to 100 times.
After annealing, the corrosion speed has become even smaller.
For 10% H2SO4 solution in water at 80°C, this was 0.056 gm2h1, and at 100°
C the corrosion process was completely absent.
With the increase in the solution concentration to 20, 30 and 40% H2SO4,
respectively, in water, the corrosion rate at 100°C increased accordingly to 0.5, 0.9
and 1.8 gm2h1. The corrosion potentials, under these conditions, are situated
within the passivity limits and are equal to 10% H2SO4 solution in water at 80 and
100°C after 5 hours of testing to +700 mV, in addition, corresponding to solutions
containing 20, 30 and 40% H2SO4 in water; it ranged from +335 to +400 mV
(Figure 6). For comparison, it can be mentioned that the corrosion speed of Pd
layers in 10% H2SO4 solution in water at 100°C, depending on the specific
processing time and regime, varies from 0.1 to 0.8 g m2 h1. With increasing acid
concentration in water, the speed increases for 40% H2SO4 solution at 100°C for
different samples, ranging from 0.85 to 2.5 g m2 h1.
Figure 6.
Changing in time the corrosion potential of palladium-deposited samples (without annealing and after
annealing) in water solutions of 10, 20, 30 and 40% H2SO4 at 80°C and at 100°C: 1–10% H2SO4, 80°C,
without annealing; 2–10% H2SO4, 100°C, with annealing, 3–10% H2SO4, 80°C, without annealing; 4–40%
H2SO4, 100°C, with annealing; 5–30% H2SO4, 100°C, with annealing; 6–20% H2SO4, 100°C, with
annealing; and 7–10% H2SO4, 80°C, without annealing.
14
The research made by authors, in order to determine the corrosion resistance of

titanium and its alloys with the deposited metallic powders, has shown that their
corrosion speed can be reduced by 100 times in water solution containing 10–40%
H2SO4 at the temperature of 100°C, and, in the case of additional subjecting, the
annealing process and the corrosion speed can be reduced by more than 100 times,
with the intention of homogenizing the structure of the layer and developing the
diffusion processes of the elements deposited in the material of the piece. These
layers allow to increase the corrosion potential up to +400 mV in 10% H2SO4
solution at 80°C and up to +300 mV at 100°C, while the titanium, in the absence of
protective depositions, dissolves very actively at the potential of 0.56 mV.
Finally, we can conclude that the deposition of anticorrosive coatings on the
surfaces of titanium and its alloy pieces can be applied in the construction of
machines, ensuring a considerable duration of their functionality in aggressive
environments.
3.3 The results of research on the corrosion properties of oxide films
In the researches carried out by the authors, the results of the experimental
measurement of active electrical surface resistance for the samples made of C45
steel, processed by applying PEDM, under atmospheric conditions, at room tem-
perature, are presented both for the surface of the anode-electrode samples and for
the surface of cathode workpiece (Table 1).
The electrical surface resistance of the unprocessed samples by PEDM plasma
ranges from 0.05 to 0.09 Ω mm2. From the analysis of the experimental results
presented in Table 1, we can state that, in all cases, there is a substantial increase in
the surface active resistance of the electrodes (both of anode and cathode) that
participated in the PEDM process, but the active surface resistance of the anode-
electrode sample is about three times smaller than that of the cathode-workpiece
sample. The last finding can be explained by the fact that at the surface of the
anode, under the same conditions, a higher amount of energy is released, and
possibly more intense vaporization processes take place, and, on the other hand, the
oxygen ions are predominantly directed by the forces of the electric field from the
gap to the cathode surface, which is why the intensity of the oxide film formation is
less intense on the anode surface.
Sample Electrical surface resistance, 106 Ω mm2
Experimental data Average value
Cathode 0.88 0.72 1.46 0.71 0.98
0.97 1.52 0.68 0.72
0.73 1.09 0.76 0.83
1.33 1.10 1.04 0.73
1.07 0.88 1.21 0.78
Anode 0.81 0.26 0.46 0.31 0.33
0.11 0.14 0.56 0.34
0.29 0.11 0.62 0.38
0.87 0.38 0.11 0.15
0.12 0.13 0.27 0.17
Table 1.
Electrical surface resistance of oxide films for steel C45 samples.
15
Processed sample material Average value of surface resistance, 106 Ω mm2
Titanium alloy BT8 (TiAl6Mo4) 1.6
Duralumin Д16 (AlCu4Mg1) 0.25
Technically pure copper M0 0.15
Bronze БрА5 (Cu95Al5) 0.17
Brass Л63 (Cu63Zn37) 0.19
Table 2.
Electrical surface resistance of oxide films formed on the workpiece-cathode surfaces.
Further (Table 2), the measurements of the surface electrical resistance of the
superficial layer for cathode samples made from titanium, aluminium and copper
alloys were made.
As can be seen from the results presented in Tables 1 and 2, the electrical surface
resistance is a function of the material of the investigated samples and has higher
values for the materials with an increased oxygen avidity.
On the basis of the corrosion resistance tests, the volt-ampere characteristic was
constructed both for PEDM-treated surface samples under air conditions and for
samples with unprocessed surfaces (Figure 7).
If we compare the results presented in Figure 8, we can see that the anode
dissolution potential of the processed sample has increased by six times compared
to that of the unprocessed sample. As the voltage applied to the electrodes increases,
the anode dissolution table of the investigated pieces changes. For example, in the
case of voltage U = 2 V, the current in the circuit for the raw surface is 300 mA, and
for the sample with oxide films, it is only 161 mA.
From the volt-ampere characteristic shown in Figure 8, we can see that the volt-
ampere characteristics for the unprocessed and processed sample in the range
1.5–2.5 V are practically parallel, which shows the presence of an isolation film on
the surface of the processed sample which increases its active resistance.
If we take into account the results obtained [28] for the case of measuring the
surface active resistance, then we can conclude that the oxide layers formed on the
sample surfaces do not have a total continuity, which is why the anodic dissolution
process takes place more intensively than we expected.
Figure 7.
The volt-ampere characteristic of the corrosion process of the steel C45 samples in the electrolyte (3% NaCl
water solution): (1) the raw surface and (2) the processed surface.
16
Figure 8.
The volt-ampere characteristic of the electrochemical corrosion process: (a) unprocessed surface and
(b) processed surface.
No. Initial mass of the sample Final mass of the sample Δm, g Speed of corrosion K,
mi, g mf, g g m2 h1
1 12.8441 12.8237 0.0204 812.10
2 13.1458 13.1254 0.0204 812.10
3 13.3225 13.3025 0.0200 796.17
4 14.0610 14.0417 0.0193 768.31
5 13.0248 13.0031 0.0217 863.85
Table 3.
Speed of anodic dissolution of steel C45 samples with unprocessed surfaces [28].
m i, g mf, g g m2 h1
1 12.8569 12.8441 0.0128 509.55
2 13.1605 13.1458 0.0147 585.19
3 13.3338 13.3225 0.0113 449.84
4 14.0717 14.0610 0.0107 425.95
5 13.0366 13.0248 0.0118 469.74
Table 4.
Speed of anodic dissolution of steel C45 samples with oxidized surfaces [28].
For the purpose of determining the corrosion speed, five pairs of unprocessed
and processed by PEDM plasma samples were subjected to testing under the same
anodic dissolution conditions. Based on the measurements, Tables 3–6 were
completed.
If we analyse the obtained results, we can see that, for the case of processed
samples made of C45 steel, the corrosion speed in 3% NaCl water solution, at the
applied voltage of 2 V, is, practically in all cases, twice lower than for the
17
mi, g mf, g g m2 h1
1 1.6803 1.6700 0.0103 103
2 1.6700 1.6599 0.0101 101
3 1.6599 1.6466 0.0133 133
4 1.6466 1.6324 0.0142 140
5 1.6324 1.6198 0.0126 126
Table 5.
Speed of anodic dissolution of titanium BT8 samples with unprocessed surfaces.
mi, g mf, g g m2 h1
1 1.9582 1.9578 0.0004 4
2 1.6615 1.6613 0.0002 2
3 1.8829 1.8828 0.0001 1
4 1.8325 1.8324 0.0001 1
5 1.7648 1.7647 0.0001 1
Table 6.
Speed of anodic dissolution of titanium BT8 samples with oxidized surfaces.
unprocessed samples by oxidation. The speed of corrosion of titanium samples with

oxide films in 30% H2SO4 water solution at 80°C decreases by about 100 times
comparatively with the unprocessed titanium surfaces.
If it is taken into account that the potential for natural corrosion is tens and
hundreds of times less than in the case of the tests carried out, then the effectiveness
of the application of oxides and hydroxides, in the amorphous state, will increase
more significantly. For example, if we return to Figure 7, then we can see that,
for the voltages applied in the limits of 0 and +0.4 V, the current in the circuit,
formed by the workpiece, does not exist; consequently, the corrosion speed will be
zero, whereas, under the same conditions, for the raw piece, there are considerable
currents; therefore, the corrosion speed is significant. Finally, we can admit that the
application of amorphous oxides and hydroxides to metal surfaces by PEDM is
beneficial for increasing their active corrosion resistance.
3.4 The corrosion resistance of the graphite film
In order to determine the corrosion resistance of the graphite films, the method
of electrochemical research was chosen. This method was used because it allows the
acceleration of the corrosion process, which is nothing more than anodic dissolu-
tion, and, thus, it shortens the study of a sample [28].
The electrochemical installation is composed of an electrolysis cell containing a
1% NaCl water solution in which two electrodes are placed, a steel cathode and
anode, also made of steel or graphite film-coated steel. They are connected by
a voltmeter and an ampere metre at an adjustable DC source in the range of
0–40 V [28].
In order to determine the value for the potential of the electrochemical dissolu-
tion, it is necessary to build the volt-ampere characteristic, for the sample anode
steel C45 and for the sample anode steel C45 covered with graphite. The cathode
material, in both cases, is steel C45.
18
For the beginning, the samples were polished and rinsed with distilled water,
then placed in the electrolyte solution at a distance of 10 mm one from another.
A DC voltage, with an 0.4 V increments, is applied at a holding time of 3 min
(Figure 9). The values for the electric currents are recorded by the ammeter, and
they are presented in Figure 9.
When samples are placed in electrolyte, in the absence of external electric
current, a stationary potential is established.
In the case when both electrodes are made from the same type of steel, the
stationary potential is almost zero, and, in the case when the anode is covered with
graphite, the stationary potential is 0.1 V.
When an external potential is applied, curves are obtained (Figure 9 (curve 2)).
It is observed that, for the steel sample, with the increasing potential, an increase in
current intensity occurs as well, up to the value of 2 V, followed by an area where a
decrease of intensity occurs up to the value of 2.9 V.
This effect may be due to the oxidation and hydroxylation chemical reactions
that lead to the steel surface passivation, in the absence of the graphite film.
After this value, as shown in the chart, with the increase in the potential differ-
ence, the corrosion current decreases, and the corrosion process takes place at low
speed, i.e., passive film emerges, which does not allow anodic dissolution.
The passive state is maintained until the potential of 2.8 V; then the current
intensity increases considerably, accelerating the corrosion process.
An analogue behaviour is found while researching the graphite-coated steel
sample, excluding that the passivation area appears almost at the value of 5.6 V.
Within the field of 5.6–6.2 V, the destruction of the deposited graphite film is
observed, followed by an increase of corrosion currents.
The performance of the sample, covered with graphite film (Figure 10, curve 1),
demonstrates that the presence of carbon significantly enhances the surface poten-
tial of the passivation 3.2 V.
It is possible that the presence of graphite on metallic electrode surface generates
deoxidation reactions, and the porosity of graphite film ensures the electrical con-
tact between the electrolyte environment and the sample surface.
In Figure 10, the corrosion rate variation, depending on the time of immersion,
is shown for the samples processed with graphite electrode tool.
From the analysis results, related to corrosion speed variation, depending on the
duration of samples exposure in aggressive environment (Figure 10), we can
Figure 9.
Volt-ampere characteristic for the electrochemical process [28]: (1) steel С45 covered with graphite and
(2) unprocessed steel C45 surface.
19
Figure 10.
Corrosion speed variation depending on the time of immersion [28]: (1) steel С45 covered with graphite and
(2) unprocessed steel С45.
outline essentially higher corrosion rates for the initiation stage of corrosive process,
in the case of unprocessed steel 45 without a graphite pellicle (Figure 10, curve 2).
Afterwards, with the passing of time, the process of corrosion is attenuated; the
determined corrosion rate is smaller, when the time of immersion is longer.
Similarly, with the passing of time, the nature of the corrosion product is mod-
ified; oxides are most likely formed, having a low oxygen content and being more
stable (Fe3O4) (FeOFe2O3).
Simultaneously, it is acceptable that corrosion products form films on the metal
surface that insulate the metal from corrosive agents. For this reason, the curves
showing the variation of corrosion rate time show a trend of flattening.
These films are adherent and also compact enough so that the corrosion process
diminishes in time, but does not annihilate.
It should be noted that the determinations were made in a static regime. In
dynamic conditions, the formed oxide film can probably detach from the metal
surface, and, in this case, the corrosion process is conducted with higher corrosion
rates.
In the case of steel coated with graphite film, lower corrosion rates are found;
afterwards, they begin to rise due to degradation of graphite film, as a result of its
destruction.
Experimentation established that in acid solution of 30% HNO3, after 3 min, the
amount of uncovered graphite steel electrochemically dissolved 1.4 times greater
than graphite-coated steel—1.3 times greater in 10 min. In salt solution of 1% NaCl,
the amount of uncovered graphite steel electrochemically dissolved was 1.2–1.4
times greater than graphite-coated steel deposited by PEDM.
4. Conclusions
Analysing the results of the experimental researches, we can conclude the

following:
• Thermal treatment, in the absence of liquid phase formation on the processed

surface, can be performed only in the regime of maintenance of the electrical
discharge in impulse on “cold” electrode spots.
• Under superficial processing conditions, with the maintenance of electric spell

released on “cold” electrode spots, the mass transfer in the solid phase can
20
reach depths of dozens of μm diameters, which will allow the working surfaces
of the parts and cutting tools of the layers with prescribed physico-mechanical
properties that will provide them with high-performance features.
• The thermal and chemical-thermal processes that result in the surface layers of
the parts under the action of the plasma channel of the electrical discharges in
impulse cause not only the modification of their chemical composition but also
the modification of their physico-mechanical properties.
• Oxide films, formed as a result of interaction with PEDM plasma, increase the
resistance by 106–107 times, which, in turn, influences the corrosion resistance.
21
References
[1] Nanu A. Technology of Materials. Management and Technological

Chisinau: Ştiinţa; 1992. 552 p Engineering. 2008. CD-ROM Edition.
Edition of University from Oradea,
[2] Tian BR, Cheng YF. Electrochemical Romania. ISSN 1583-0691, CNCSIS
corrosion behaviour of X-65 steel in the “Class B+”;VII(XVII):1824-1829. DOI:
simulated oil sand slurry. I: Effects of 10.15660/AUOFMTE.2008.1213
hydrodynamic condition. Corrosion
Science. 2008;50(3):773-779 [10] Negm NA, Salem MA, Badawi AM,
Zaki MF. Corrosion inhibition
[3] LiuYing L, FuhuiWang L. properties of some novel n-methyl
Electrochemical corrosion behaviour of diethanolammonium bromide cationic
Nano crystalline materials: A review. surfactants. TESCE. 2004;30(2):853-869
Journal of Materials Science and
Technology. 2010;26(1):1-14 [11] Gogoi PK, Barhai B. Corrosion
inhibition of carbon steel in open
[4] Rihan RO. Electrochemical corrosion recirculating cooling water system of
behaviour of X52 and X60 steels in petroleum refinery by a multi-
carbon dioxide containing saltwater component blend containing zinc(II)
solution. Materials Research. 2013;16:1 diethyldithiocarbamate. Indian Journal
Epub Dec 04, 2012 of Chemical Technology. 2010;17:
291-295
[5] Kuphasuk C, Oshida Y, Andres CJ,
Hovijitra ST, Barco MT, Brown DT. [12] Topala P. Cercetări privind
Electrochemical corrosion of titanium obţinerea straturilor de depunere din
and titanium-based alloys. The Journal
pulberi metalice cu aplicarea
of Prosthetic Dentistry. 2001;85(2):
descărcărilor electrice în impuls. In:
195-202
Rezumatul Tezei de Doctorat. Bucureşti:
Universitatea Politehnica; 1993. p. 32
[6] Huang C-L, Chen T-H, Chiang C-C,
Lin S-Y. Electrochemical corrosion and
mechanical properties of two [13] Topală P. Cercetări privind
biomedical titanium alloys. obţinerea straturilor de depunere din
International Journal of Electrochemical pulberi metalice cu aplicarea
Science. 2018;13:2779-2790. DOI: descărcărilor electrice în impuls. In:
10.20964/2018.03.26 Teza de Doctorat în tehnică. Bucureşti:
Universitatea Politehnica; 1993. p. 161
[7] Song G-L. The grand challenges in
electrochemical corrosion research. [14] Abdulkareem MAA, Hani AA. The
Frontiers in Materials. 2014. DOI: effect of zinc, tin, and Lead coating on
10.3389/fmats.2014.00002 corrosion protective effectiveness of
steel reinforcement in concrete.
[8] Tian G et al. Investigation on American Journal of Scientific and
electrochemical corrosion characteristic Industrial Research. 2011;2(1):89-98.
of 2A14 aluminum alloy in nitric acid. ISSN: 2153-649X. DOI: 10.5251/
Surface Review and Letters. 2017; ajsir.2011.2.89.98
24(1850016):10. DOI: 10.1142/
S0218625X18500166 [15] Topală PA, Balcănuţă NP.
Caracteristicile electrodinamice ale
[9] Topala P, Ojegov A. Formation of descărcărilor electrice în impuls. In:
oxide thin pellicles by means of electric Tehnologii Moderne, Calitate,
discharges in pulse. Annals of the Restructurare. Chişinău: Universitatea
Oradea University. Fascicle of Tehnică a Moldovei; 2001. pp. 203-208
22
[16] Topala P. Conditions of thermic and порошковыми материалами. ЭОМ. 1980;

thermo-chemical superficial treatment (5):33-35
innards with the adhibition of electric
discharge in impulses. In: [24] Парканский НЯ, Гитлевич АЕ.
Nonconventional Technologies Особенности поверхности слоев катода
Review. Bucureşti: Editura BREN; 2005. при электроискровом нанесении
pp. 27-30 порошковых материалов. ЭОМ. 1981;
(1):32-35
[17] Topală P. Aplicări ale
electroeroziunii în dezvoltarea [25] Гитлевич АЕ и д. Электроискровое
tehnologiilor fine de prelucrare легирование металлических
superficială a pieselor. Analele Ştiinţifice поверхностей. Кишинев: Штиинца; 1985.
ale Universităţii de Stat “Alecu Russo” p. 196
din Bălţi.—Serie nouă. Fasc. A. 2004.
Tom XX, p. 66-69 [26] Немошкаленко ВВ и др.
Особенности формирования
[18] Топала ПA, Гитлевич AE, поверхностных слоев при искровых
Корниенко ЛП. Коррозионное разрядах. Киев: Металлофизика. 1990.
поведение титана с электроискровыми vol. 12. № 3. pp. 132-133. ISSN 0204-
покрытиями. Москва: Защита металлов, 3580
1989, vol. 29, № 3, рр. 351-356
[27] Мицкевич MK и др.
[19] Топала Пи др. Влияние отжига на Электроэрозионная обработка металлов.
коррозионное поведение титана с Минск: Наука и техника. 1988. p. 216
электроискровыми покрытиями.
Москва: Защита металлов. 1990. vol. 26. [28] Tiginyanu I, Topala P, Ursaki V,
№ 3. рр. 433-437 editors. Nanostructures and Thin Films
for Multifunctional Applications.
[20] Топала П и др. Упрочнение NanoScience and Technology.
металлических поверхностей на Switzerland: Springer International
участках для электроискрового Publishing; 2016. p. 576 p. ISSN
легирования. In: Машиностроение и 1434-4904, ISBN 978-3-319-30197-6.
техносфера Xxi века. Vol. 3. Донецк: DOI: 10.1007/978-3-319-30198-3
Сборник трудов XIII Международной
научно-технической конференции; [29] Корниенко ЛП и др.
2006. pp. 262-265 Электрохимическое и коррозионное
поведение титана с электроискровыми
[21] Topală P, Stoicev P. Tehnologii de покрытиями Pd и Cr-Pd. Москва:
Prelucrare a Materialelor Conductibile Защита металлов. 1991. vol. 29. № 3. pp.
cu Aplicarea descărcărilor Electrice în 351-358
Impuls. Chişinău: Editura Tehnica-Info;
2008. p. 265 [30] Chernova GP et al. The influence of
annealing on the corrosive behaviour of
[22] Парканский НЯ. Исследования titanium with electrospark palladium
процесса электроискрового нанесения surfaces. Metal Protection. 1990;26(3):
покрытий из порошковых материалов в 433-437
электрическом поле. Дис. канд. техн.
наук. Киев: Институт проблем [31] Любимов ГА, Раховский ВИ.
материаловедения АН УССР; 1979. p. 27 Катодное пятно вакуумной дуги. УФН.
1978;125(4):665-706
[23] Ливурдов ВИ и д. Структура и
эксплуатационные свойства деталей с [32] Бушик АИ. Исследование динамики
покрытиями, полученными процессов при импульсном разряде на
электроискровым легированием сложных электродах. Автореф. дис.
23
канд, ф.-м. наук. Минск: ФТИ АН БССР.

1973. p. 23
[33] Антонов СА и д. Дуговая эрозия

катодов, содержащих включения
эмиссионноактивной фазы. ЖТФ. 1982;
52(52):266-270
[34] Булат ВЕ, Эстерлив МХ. Очистка

металлических изделий от окалины,
окисной плёнки и загрязнений
электродуговым разрядом в вакууме.
ФХОМ. 1987;(3):49-53
24
Chapter 07
Investigation of Corrosion
Inhibitors Adsorption on Metals
Using Density Functional Theory
and Molecular Dynamics
Simulation
Ambrish Singh, Kashif R. Ansari, Mumtaz A. Quraishi and
Yuanhua Lin
Abstract
The use of computational chemistry as a tool in the design and development of

organic corrosion inhibitors has been greatly enhanced by the development of
density functional theory (DFT) and Molecular dynamic simulation (MD). Experi-
mentally corrosion inhibitor development requires lots of money and time. Thus, in
the era of hardware and software development, corrosion scientist can select a
potential inhibitor on the basis of theoretical analysis of molecular properties of
inhibitor molecules, which have reduced the cost. DFT and MD are capable to
accurately predict the inhibition characteristics of inhibitor molecules using molec-
ular/electronic properties and reactivity indices. The purpose of this book chapter is
to summarize some important features related to DFT and MD, giving a brief
background to the selected DFT/MD-based chemical reactivity concepts, calcula-
tions and their applications to organic corrosion inhibitor design. The impact of this
book chapter is to illustrate the enormous power of DFT and MD.
Keywords: corrosion, DFT, MD, inhibitor
1. Introduction
Corrosion of active metals such as iron (Fe), copper (Cu) and Aluminum (Al) can
be reduced by modifying their surface using organic/polymeric corrosion inhibitors.
The inhibitor molecules adsorbed onto the metal surface and form a protective
barrier against corrosion [1]. The corrosion protection ability of inhibitors depends
upon the extent of interaction between inhibitor molecules and metal surface [2]. The
basics mechanism through which adsorbed inhibitor molecules alter the corrosion
process consists of either changing the cathodic and anodic corrosion reactions or
physically blocking the active sites present on metal surface or by [3].
Perusal of the literature clearly reveals that huge number of publication exits
where experimental works have been carried out to understand the corrosion inhi-
bition process, however use of theoretical studies including density functional
1
theory (DFT) and molecular dynamic simulation (MD) appeared in recent years. In
traditional experimental work scientists has to test huge number of organic com-
pounds for selecting them as a potential corrosion inhibitor. This kind of search
takes more time and money. However, in the era of development in the field of
hardware and software technology make us capable to select organic compounds as
potential corrosion inhibitor without expensing huge amount of money on
chemicals. The corrosion inhibition efficiency of organic compounds based on
molecular and electronic properties can be predicted accurately using MD and DFT
calculations. In the recent years, scientist have devoted their positive efforts in the
field of corrosion using theoretical calculation [4–6]. To our knowledge, the review
exists in the literature only describing separately DFT and MD and not both in
relation to corrosion inhibition study [7, 8]. Here we are trying to describe both
DFT and MD on the same platform simultaneously.
In this chapter we will try to explore some recent studies and concept which can
provide some new concept in the field of computational chemistry related to corro-
sion inhibition phenomenon. Here, we summarize the adsorption of organic mole-
cules onto the metal surface especially iron, aluminum and copper in order to study
their corrosion inhibition properties using DFT and MD simulations.
2. Basic concepts related to molecular modeling
In literature, large number of publication/papers exits where corrosion inhibi-

tion property of inhibitors has been studied using theoretical study. In general
organic molecules have the ability to donate electrons to empty d-orbital of metal
surface and form covalent bond which is known as coordinate bond. However, they
also undergo back donation, where they accept the free electrons presenting in
filled metal orbitals and this is called as retrodonating bonds. Thus, these kinds of
bonds make the organic compounds a potential candidate for corrosion inhibition.
The theoretical parameters like highest occupied molecular orbital (HOMO), lowest
unoccupied molecular orbital (LUMO), dipole moment (μ), energy gap (ΔE), Fukui
indices, charge density, polarizability, softness, etc. [9–11] were discussed in DFT
calculation.
DFT study separately represents the organic compound and metal surface
[12–16]. In DFT, the interaction between the inhibitor molecule and metal surface
was not directly modeled. However, in MD the most reactive fragment of the
molecule that has greater affinity to interact with the metal surface is study using ab
initio method. This method provide a real picture which is actually going in the
corrosion process like interaction between inhibitor molecule and metal surface,
orientation of molecule towards metal and organization of molecules.
3. Inhibitor/surface interaction study using DFT
3.1 The basics of DFT: the Hohenberg-Kohn theorem
Quantum electrochemistry is the field which includes quantum mechanics,

electrochemistry and electrodynamics. In general, quantum electrochemistry is an
application of density functional theory (DFT) for studying the electrochemical
processes like transfer of electron towards electrode surfaces [17].
There are so many books and articles that exist in literature which describe about
the basis set used in DFT [18–31]. So, here we provide only very few pints of DFT
without using mathematics.
2
Investigation of Corrosion Inhibitors Adsorption on Metals Using Density Functional Theory…
3.2 Functional
The functional is a function of a function, i.e., electron. Therefore, on the basis

of fundamental quantum mechanics and from the experimental results different
functional have been developed and are listed in Table 1 [29].
There are several generations of density functional. First generation is known as
Xα method and it is the simplest one. This functional was developed by J.C. Slater,
who was working on the approximation of Hartree-Fock but unwillingly discovered
the simplest for DFT. In Xαfunctional electron exchange but not the correlation was
included. The results obtained from Xαmethod is as accurate as HF but in some
cases it is better than HF.
The functional of second generation uses both the density and its gradients. In
1986 first gradient-corrected energy functional was proposed in which Becke,
Perdew and Wang proposed exchange and Perdew correlation [32, 33]. In the
present time the most popular functionalis of Becke and Perdew for exchange and
correlation respectively [32], also Lee et al. [34] for correlation and Perdew and
Wang for exchange and correlation both [35]. These functional are collectively
known as “generalized gradient approximations (GGAs).”
The third generation is hybrid functional and it is more advanced than GGA. In
this, the functional consists of both Hartree-Fock type exchange and DFT exchange
calculated from the orbitals. In 1998, a hybrid functional called as B3LYP functional
was introduced. In 1994, Gaussian introduced this functional in in computational
package for first time and it is written by below equation:
EXC ¼ ao EX ðHFÞ þ a1 EX ðLSDÞþa2 EXðGGAÞ þ a3 EC (1)
where EX(HF) represent the Hartree-Fock exchange energy, EX(LSD) stands for
Dirac exchange energy and EX(GGA) and EC are the gradient corrections to exchange
energy, i.e., Be88form and Lee-Yang-Parr (LYP) functional respectively [34, 36].
3.3 Basis sets
In DFT calculation various basis sets are used [37]. The simplest one is STO-3G.
In this basis set, 1s is given by three Gaussians and 2s, 2px, 2py, and 2pz each by
Acronyms Name Type
Xα X alpha Exchange only
HFS Hartree-Fock Slater HF with LDA exchange
VWN Vosko, Wilks, and Nusair LDA
BLYP Becke correlation functional with Lee, Yang, Parr exchange Gradient-corrected
B3LYP Becke 3 term with Lee, Yang and Parr Hybrid exchange
PW91 Perdew and Wang 1991 Gradient-corrected
G96 Gill 1996 Exchange
P86 Perdew 1986 Gradient-corrected
B96 Becke 1996 Gradient corrected
B3P86 Becke exchange, Perdew correlation Hybrid
B3PW91 Becke exchange, Perdew and Wang Hybrid correlation
Table 1.
List of density functional [29].
3
another three. Improvement in the basis set can obtain by incorporating two 1s
functions for hydrogen and for 2nd row atoms like carbon two 2s and two 2p
functions has incorporated. These functional are called as split-valence basis sets.
Here valence and core orbitals are represented by two sets of functions and single
set of functions respectively. An example for this:
Carbon 3-21G: Three Gaussians for 1s combination, same two Gaussians for 2s
and 2p combination; plus 2s’ and 2p’ the same one Gaussian.
Carbon 6-31G: Six Gaussians for 1s combination, same three Gaussians for 2s
and 2p combination; plus 2s’ and 2p’ the same one Gaussian.
In general it can be represented as i-jk, here i denote the number of Gaussians

that are representing each core basis function, and j and k represent the numbers of
Gaussians for split-valence basis functions.
Further advancement generates triple-split-valence basis sets, for example
6-311G. In this basis set core functional consists of six Gaussians and three sets of
valence functions containing three, one, and one Gaussians, respectively.
Multiple zeta basis sets such as double zeta (DZ) and triple zeta (TZ) basis sets
has also introduced. The difference between multiple and split-valence basis sets is
that in multiple basis sets all of the orbitals are separated into either two or three
sets of functions, and so forth. Also, multiple basis sets used different α-coefficients
for s and p orbitals.
So, improvement in the electronic structure calculation can be achieved by adding
functions corresponding to orbitals with a higher angular momentum. This concept
Basis Options Atoms
STO-3G ∗ H–Xe
3-21G ∗ ∗∗ H–Cl
4-21G ∗ ∗∗
4-31G ∗ ∗∗ H–Ne
6-21G ∗ ∗∗
6-31G + ++ ∗ ∗∗ H–Cl
LP-31G ∗ ∗∗
LP-41G ∗ ∗∗
6-311G + ++ ∗ ∗∗ H–Ar
MC-311G None H–Ar
D95 + ++ ∗ ∗∗ H–Cl
D95V + ++ ∗ ∗∗ H–Ne
SEC + ++ ∗ ∗∗ H–Cl
CEP-4G + ++ ∗ ∗∗ H–Cl
CEP-31G + ++ ∗ ∗∗ H–Cl
CEP-121G + ++ ∗ ∗∗ H–Cl
LANLIMB None H–Bi

(except lanthanides)
LANLIDZ None H–Bi

(except lanthanides)
Table 2.
Common basis set.
4
can explained as follows: for hydrogen atom, p functions are added; for carbon,
nitrogen, oxygen, etc., d functions are added; and for transition metals, f functions
are introduced. These are represented by adding an asterisk to the basis set and also
specifying the p, d, f functions. This can be understood as per below example:
6-31G∗ or 6-31G(d): Adds d functions to 2nd row elements (C, N, O, etc.).
6.31G∗∗ or 6-31G(d,p): Adds d function to 2nd row elements (C, N, O, etc.) and
p functions to H.
The lone pair of electrons on the heteroatoms can be taken into confederation by
adding diffuse functions and these are represented in the basis set using + and ++
signs. For hydrogen atom polarization and diffuse functions are not very import but
for other atoms like carbon, nitrogen, oxygen it is important, for example,
6-31+G: represents that diffuse functions has been added to 2nd row elements
(C, N, O, etc.).
6-31++G: represents that diffuse functions has added to 2nd row elements and H.
In the case of transition elements which contain large number of electrons,

requires more time for calculation. So, the LanL2DZ basis set is used for transition
metal calculations. This basis set is derived by combining the valence electrons
using double zeta functions and Los Alamos ECP. The software used in corrosion
inhibition study with a wide range of basis sets are Spartan, Material Studio,
Gaussian 03, Gaussian 09 and most recently Gaussian 14 has been introduced.
Table 2 represents commonly used basis sets [37].
4. DFT parameters and their application in corrosion inhibition study
4.1 Frontier molecular orbitals
The optical and electronic property of organic compounds is explained by ana-

lyzing their frontier molecular orbitals (FMO) like highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) [38]. The inter-
action of organic compounds as corrosion inhibitor with the metal surface depends
upon the electron donation ability of the organic compounds, i.e., ionization poten-
tial (I.P.). However, the electron accepting ability of organic compounds corre-
sponds to the electron affinity (E.A.) [39]. So, HOMO is the electron donating
orbitals and LUMO is electron accepting orbitals [40]. In general for a good corro-
sion inhibitor HOMO value should high, LUMO should low and energy gap between
the LUMO and HOMO (ΔE) should low [40].
According to Koopmans’ theorem the negative value of HOMO corresponds to
the ionization potential (I.P.) and is given as follows [41–44]:
I:P: ¼ EHOMO (2)
Similarly negative value of LUMO corresponds to the electron affinity (E.A.)

and is given below [41–48]:
E:A: ¼ ELUMO (3)
In literature Singh et al. [45] has correlated some important quantum chemical
parameters of organic corrosion inhibitors using/B3LYP methods using 6-311G
(d, p) basis set with their corrosion inhibition efficiency. They studied three
triazine-based hydrazone derivatives and their molecular, orbital pictures and
quantum chemical parameters are represented in Figures 1–3.
5
Figure 1.
Molecular structure of the triazine-based hydrazone derivatives. Adapted from Ref. [45].
Figure 2.
HOMO orbitals of triazine-based hydrazone derivatives.
Figure 3.
LUMO orbitals of triazine-based hydrazone derivatives.
The HOMO and LUMO are represented in Figures 2 and 3.

From the figure, it could be said that HOMO regions are distributed on the
triazine ring, phenyl ring containing electron donating group, nitrogen and oxygen
atoms. These regions correspond to the electron donating areas and inhibitor mole-
cules interact with the metal surface through these regions and undergo adsorption
over it. However, the LUMO are distributed over the triazine and phenyl ring
respectively and these are corresponding to the electron accepting regions. From
these LUMO regions inhibitor accept electron from metal. Order of inhibition
efficiency is HT-1 > HT-2 > HT-3.
4.2. Electronegativity and the electronic chemical potential
One of the important global molecular property calculated by density functional

theory (DFT) which provide an idea for chemical reactivity and selectivity of
organic compound as corrosion inhibitor are electronegativity (χ) and chemical
potential (μ) [46]. Mathematical form of this is as follows [47, 48]:

∂E
χ ¼ μ ¼ (4)
∂N νðrÞ
6

I:P: þ E:A:
χ ¼ μ ¼ (5)
2
where I.P. and E.A. are ionization potential and electron affinity.
4.3 Global hardness and softness
According to Parr et al. global hardness (η) measures the resistance of an atom to
transfer the charge [49] and it can be calculated using below equation:
1
η ¼ ðEL þ EH Þ (6)
2
where EL and EH are the HOMO and LUMO energy.

The reciprocal of global hardness is global softness (σ) and given as [50]:
1
σ¼ (7)
η
4.4 Electric dipole polarizability
The electric dipole polarizability (α) is a measurement of the linear response of

the electron density in the presence of an infinitesimal electric field F and it
describes a second-order variation in energy:

∂2 E
α¼ 2 a, b ¼ x, y, z (8)
∂ F a ∂2 Fb
The polarizability (α) is calculated as the mean value and express through above
equation:
1
α¼ αxx þ αyy þ αzz (9)
3
It was discovered that polarizabilities are inversely proportional to the third
power of the hardness values [51–54].
4.5 Electrophilicity index
Parr et al. has introduced the concept of global electrophilicity index (ω) and is
given as follows [55, 56]:
μ2
ω¼ (10)
4η
The global electrophilicity index (ω) is also related to the ionization potential
(I.P.) and electron affinity (E.A.) and is given as follows [56]:
ðI:P: þ E:A:Þ2
ω¼ (11)
8ðI:P: þ E:A:Þ
The electrophilicity index accounts the ability of the molecule to accept elec-
trons. So, higher the ω value, greater would be the molecule to accept the electrons.
7
4.6 The fraction of electrons transferred
When the inhibitor and metal interaction occurs, flow of electron takes place
from the lower electronegativity molecule to the higher electronegativity metal.
This transfer of electron continues until the chemical potential becomes equal. The
fraction of electron transfer is given as follows [57]:
χm χi
ΔN ¼ (12)
2ðηm þ ηi Þ
where metal and inhibitor molecule are represented by m and i indices respec-
tively. The absolute electronegativity of metal and inhibitor molecule are
represented by χm and χi respectively. The absolute hardness of metals and inhibitor
molecule is given by ηm and ηi, respectively. In case of iron the theoretical values of
χm and ηm are 7 and 0 eV mol1 respectively [57]. However, the value of 7.0 eV
corresponds to the free electron gas Fermi energy of iron in the free electron gas
model. But the use of this value for χm is conceptually wrong because here electron-
electron interaction has been neglected [58]. Thus, work function (φm) of the metal
has been incorporated for an appropriate measurement of electronegativity. So, the
new formula for the estimation of N is as follows [59]:
φm χ i
ΔN ¼ (13)
2ðηm ηi Þ
The work function (φ) values for iron surface plan Fe (1 0 0), Fe (1 1 0) and Fe
(1 1 1) surfaces are 3.91, 4.82 and 3.88 eV, respectively [59, 60]. The surface energy
of iron planes for bcc structure are in order of Fe (110) < Fe (100) < Fe (111) and
out of these the most stable on plan is Fe (110). Thus, most commonly Fe (110) plan
is used in corrosion inhibition research [61].
4.7 Fukui function and local softness
In the field of corrosion research inhibition of corrosion is governed through

donation and acceptance of electron, which basically involves the nucleophilic and
electrophilic reactions. This can be achieved through the evaluation of the Fukui
indices [61–63]. Thus, by invoking the HSAB principle in a local sense, one may
establish the behavior of the different sites with respect to hard or soft reagents.
The Fukui function generated using the finite difference approximation is as follows:

δρðrÞ þ
fþ ¼ ¼ ρðNþ1Þ ρN (14)
δN ν

δρðrÞ þ
f ¼ ¼ ρðN Þ ρðN1Þ (15)
δN ν
where f+ is nucleophilic and f is electrophilic Fukui functions respectively,

ρ(N+1), ρ(N) and ρ(N-1) are the electronic densities of anionic, neutral and cationic
forms of the atoms with N+1, N and N-1 electrons.
Castro et al. [64] studied the series of isomers of the Schiff base (E)-2-
(2-hydroxybenzylideneamino) phenylarsonic acid as corrosion inhibitor. The author
has pictorially presented the negative Fukui, i.e., f function and is given as follows.
In Figure 4, the black region represents the area where inhibitor contains the
major portion of electrons for donating to the empty d orbitals of Fe metal. The
Fukui function represents the change of the electronic density in a given point with
8
Figure 4.
Isosurface plots for the electrophilic form of the Fukui function f.
respect to the change in the number of electrons N [65]. For the electrophilic attack
to occur, the contributing atoms are likely to be the carbon atoms on the OH-
substituted phenyl ring in all isomers, the oxygen atom in the isomer SBAs-OH-I,
the nitrogen atom of the imine group of isomer SBAs-OH-III, and a region located
in AsO(OH)2-substituted phenyl ring.
Local softness is calculated is using the equation [66]:

∂nðrÞ
sðrÞ ¼ (16)
∂μ νðrÞ
The integration of equation gives global softness value:

ð
S ¼ sðrÞdr (17)
Local softness and Fukui function are related as per below equation:
sðrÞ ¼ Sf ðrÞ (18)
The local softness contains information similar to those obtained from Fukui
function plus additional in-formation about the molecular softness, which is related
to the global reactivity with respect to a reaction partner.
4.8 Charge transfer: donation and back donation
The energy change in the molecule is attributed because of two processes either
electron donation to the metal or acceptance from the metal, i.e., back donation.
Gomez et al. [67] proposed a simple charge transfer model for donation and back
donation. In this model when the molecule receives certain amount of charge
(ΔN) the change in energy is given as follows:
ΔEþ ¼ δþ ΔN þ þ 0:5ηðΔN þ Þ
2
(19)
However, when the molecule back donate certain amount of charge (ΔN) the
change in energy is given as follows:
9
ΔE ¼ δ ΔN þ 0:5ηðΔN Þ2 (20)
If the total change in energy (ΔET) is the summation of ΔE+ and ΔE, and
assuming that the donation and back donation, i.e., (ΔN) and (ΔN+) are equal, than:
ΔET ¼ ΔE þ ΔEþ ¼ ðδ δ ÞΔN þ þ ηðΔN þ Þ

2
(21)
In a situation when the total energy change becomes a minimum with respect to
ΔN+, then
ΔN þ ¼ ðδþ δ Þ=2η (22)
and change in total energy becomes as follows:
ΔET ¼ ðδþ δ Þ=4η ¼ η=4 (23)
According to Guo et al. [68] the change in total energy are negative, i.e., Δ ET < 0.
This implies that the back donation of charge from metal surface to inhibitor mole-
cules is favorable.
5. Inhibitor/surface interaction study using molecular dynamic

simulation (MD)
Molecular dynamics is a computer-based modeling technique by which the

evolution as a function of time or trajectory of a molecule is described by the
principles of classical Newtonian mechanics [69]. In molecular dynamics, intramo-
lecular movements of inhibitor molecules are simulated in order to visualize the real
picture of corrosion inhibition process. Molecular dynamics simulation calculation
has two serve two purposes:
a. Intramolecular movements’ simulation and calculation of thermodynamic

properties such as entropy, free energy, etc.
b.Optimization of the molecular structures efficiently by avoiding multiple

minima by annealing the simulation process. The range of simulation time is
approximately between 1014 and 1010s per simulation.
Molecular dynamics simulation involves the implementation of initial steps: In

the first very step build molecular structure are introduced or immersed in a box
having solvent molecules, after that simulation process starts. The total energy of
the molecular system should be minimizing before the start of the simulation, in
order to avoid the generation of aberrant trajectories (when the initial forces are too
great). For achieving this, the steepest slope/steepest descent method and that of
the conjugated gradients have been frequently used.
6. Corrosion inhibitors studied using DFT
6.1 Adsorption behavior of inhibitors on mild steel surface
In literature, several DFT calculations are observed where inhibition efficiency

and molecular structure/electronic properties of organic corrosion inhibitors have
10
been correlated. Xu et al. [70] has studied corrosion inhibition property of Schiff’s
base derivatives via DFT calculation using GGA/BLYP method. The result indicates
that 2-PCT molecules adsorb strongly onto iron surface and provide higher inhibi-
tion efficiency.
Zhang et al. [71] investigated the inhibition of methionine (Met) and proline
(Pro) in PCMs solution using DFT and B3LYP/6-31G (d) method. The inhibition
efficiency of Met and Pro follow the order of Met > Pro.
The corrosion inhibition effects of thiourea (TU), methylthiourea (MTU) and
phenylthiourea (PTU) on mild steel in 0.1MH2SO4 was investigated by Ozcan et al.
[72]. The electronic properties were calculated using ab initio RHF/6-31G(d)
method. The energy of EHOMO, the energy of ELUMO and energy gap values supports
that PTU is best inhibitor.
The corrosion inhibition performance of three naphthyridines derivatives were
explored for mild steel in 1 M HCl by Singh et al. [73] using DFT methods. The
inhibition efficiencies of N-3 and N-2 are higher due to the presence of electron-
donating –OCH3 and –CH3 substituents respectively as compared to N-1, which has
no substituents.
Feng et al. [74], studied inhibition activity of an imidazoline derivative, namely
1-[N,N0 -bis(hydroxylethylether)- aminoethyl]-2-stearicimidazoline (HASI) for
carbon steel in 5% NaCl saturated with Ca(OH)2 solution using DMol3 module. DFT
calculations reveals that N=C-N region in imidazoline ring is the most active reac-
tion site.
6.2 Adsorption behavior of inhibitors on aluminum surface
The inhibitive action of poly ethylene glycol (PEG) against the corrosion of
aluminum surface in 1 M HCl was investigated by Awad et al. [75] using B3LYP/6–
31 + G(d,p) basis set. DFT was performed on repeating units of 1, 2, 3, 4 and 5. The
inhibition performance increases with increase in number of repeating unit.
The author Li et al. [76] studied the corrosion inhibition effect of three oxime
compounds on the corrosion of aluminum in HCl solution using BLYP in conjunc-
tion with double numerical plus d-functions (DND) basis set. In these inhibitors,
HOMO and LUMO electron densities are localized principally on C=N–OH, which
suggest that C=N–OH functional group could both accept and donate the electron.
Khaled et al. [77], investigated the corrosion effect of and adsorption character-
istics of three imidazole derivatives on aluminum in 1.0 M HCl using local density
functional (LDF) method with a double numeric polarization (DNP) basis set, and a
Becke–Perdew (BP) functional. A good correlation between the rate of corrosion
and EHOMO, as well as with energy gap (ΔE = ELUMO EHOMO).
Kaya et al. [78] applied HF and DFT/B3LYP methods with SDD, 6-31++G (d, p)
and 6-31 G basis sets both in gaseous and aqueous phase for studying the adsorption
and corrosion inhibition properties of some benzotriazole and phospono derivatives
on aluminum. The inhibition efficiency ranking of these molecules as:
PBA > PBTA>PAA > TBTA.
6.3 Adsorption behavior of inhibitors on copper surface
Corrosion inhibition of indazole (IA) and 5-aminoindazole (AIA) for copper in

NaCl solution was studied by Qiang et al. [79]. The molecular structures of IA and
AIA were geometrically optimized by density functional theory (DFT) using B3LYP
functional with 6-311++G(d,p) basis set in aqueous phase. The higher value of
HOMO and lower value of ΔE in case of AIA concludes that the interaction of AIA
with copper will be stronger than that between IA and copper.
11
Khalid and Madkour et al. [13, 80, 81] probe the interactions between
benzotriazole, methionine, phenol derivatives and copper via quantum calculations
respectively. The obtained results suggests that quantum parameters are very useful
in characterizing organic compounds as an adsorbate.
7. Corrosion inhibitors studied using MD
Feng et al. [74] performed the MD simulation of 1-[N,N0 -bis

(hydroxylethylether)- aminoethyl]-2-stearicimidazoline (HASI). The MD calcula-
tion suggests that adsorbed imidazoline molecule is parallel to the iron surface in
order to maximize its contact with the surface (Figure 5). The interaction energy
for Fe atom is 284 kJ/mol, for Fe3O4 is 226 kJ/mol and for Fe2O3 is 157 kJ/mol.
So, inhibitor adsorbed on Fe surface more strongly than Fe3O4 and Fe2O3.
MD calculation of adsorption of indazole (IA) and 5-aminoindazole (AIA) on
copper surface was studied Qiang et al. [79]. The optimized equilibrium configura-
tion of inhibitors molecules are shown in Figure 6 and inhibitors adsorption occurs
through parallel orientation. The adsorption energy between Cu (1 1 1) surface and
inhibitor molecule are 250.86 kJ/mol for IA and 307.86 kJ/mol for AIA.
Molecular level MD calculation of Benzotriazole and Phospono derivatives was
studied by Kaya et al. [78] on aluminum surface. The best adsorption configuration
of inhibitor molecules on Al (111) surface are represented in Figure 7. The parallel
configuration of inhibitor molecules suggests the stronger adsorption.
Figure 5.
Adsorption of imidazoline molecule on (a) Fe, (b) Fe3O4 and (c) Fe2O3 surfaces. The left is top view, and the
right is side view [74].
12
Figure 6.
Equilibrium adsorption configuration for IA and AIA on Cu (111) surface in 3% NaCl solution after
optimization (inset images show the on-top views) [79].
Figure 7.
Equilibrium adsorption configuration of inhibitors PBTA (a and b), TBTA (c and d), BPA (e and f), PAA
(g and h) on Al (1 1 1) surface. Top: top view and bottom: side view [78].
8. Conclusion and future work
Computational program provide an atomistic view for understanding the corro-

sion inhibition process and significantly contribute for the selection of adequate
inhibitor molecules. DFT calculations has made possible to characterize a suitable
inhibitor molecules using their intrinsic properties such as energies of HOMO and
LUMO orbitals, energy gap (ΔE), electronegativity, hardness, softness, etc. It helps
corrosion scientist to understand the inhibitor-metal interaction through the loca-
tions of HOMO and LUMO orbitals. The examination of local reactivity reveals the
nucleophilic and electrophilic centers which react with the metal surfaces.
The literature survey suggests that with help of quantum chemistry a good
understanding of corrosion system can be achieved when various metal surfaces
and various inhibitor molecules are compared. DFT has ability to perform
13
calculations for complex or large organic molecules that can be applied as a potential
corrosion inhibitor. In addition, DFT provide a platform to scientist for designing a
unique inhibitor molecule and understand their molecular structure at atomistic
level.
In recent years, computational modeling like DFT and MD provide real
inhibitor-metal interaction picture by performing calculation in aqueous phase.
Such an approach act as a benchmark for experimental study in the field of corro-
sion research.
Molecular dynamic simulation (MD) gives a representative image of inhibitor
molecule orientation on the metal surface. This helps to analyze the inhibition
activity of inhibitor molecules, i.e., inhibitor with parallel or flat orientation with
respect to metal surface will cover more surface area and provide a better corrosion
inhibition protection as compared to the inhibitor which have vertical orientation.
Future research includes modeling the electrochemical potential, generation of
alloy surface layers, addition of thin oxide film covering onto the metal surface,
calculation of more complex molecule, comprehension of solvent molecule role in
adsorption, understanding the defect role in adsorption process, etc.
Acknowledgements
The authors are thankful to the Sichuan 1000 Talent Fund and financial assis-
tance provided by the National Natural Science Foundation of China (No.
51274170).
There are no conflicts to declare.
14
References
[1] Mao ZJ, Jun L. Corrosion inhibition dynamics and Monte Carlo simulations
performance of carbon steel in brine as powerful tools for study of interfacial
solution containing H2S and CO2 by adsorption behavior of corrosion
novel Gemini surfactants. Acta Physico- inhibitors in aqueous phase: A review.
Chimica Sinica. 2012;28:623-629 Journal of Molecular Liquids. 2018;260:
99-120
[2] Obot IB, Ebenso EE, Kabanda MM.
Metronidazole as environmentally safe [9] Yang W, Parr RG, Pucci R. Electron
corrosion inhibitor for mild steel in 0.5 density, Kohn–Sham frontier orbitals,
M HCl: Experimental and theoretical and Fukui functions. The Journal of
investigation. Journal of Environmental Chemical Physics. 1954;81:2862-2863
Chemical Engineering. 2013;1:431-439
[10] Parr RG, Yang W. Density
[3] Trabanelli G. Chemical Industries
functional approach to the frontier-
Corrosion Mechanism. Vol. 3. New electron theory of chemical reactivity.
York: Marcel Dekker; 1987 Journal of the American Chemical
Society. 1984;106:4049-4050
[4] Gutiérreza E, Rodrígueza JA,
Borbollaa JC, Rodrígueza JGA,
[11] Armaković S, Armaković SJ, Vraneš
Thangarasu P. Development of a
M, Tot A, Gadžurić S. DFT study of 1-
predictive model for corrosion
butyl-3-methylimidazolium salicylate:
inhibition of carbonsteel by imidazole
A third-generation ionic liquid. Journal
and benzimidazole derivatives.
of Molecular Modeling. 2015;21:246-256
Corrosion Science. 2016;108:23-35
[12] Guo L, Zhang ST, Lv TM, Feng WJ.
[5] Shaban SM. N-(3-(dimethyl benzyl
ammonio)propyl) alkanamide chloride Comparative theoretical study on the
derivatives as corrosion inhibitors for corrosion inhibition properties of
mild steel in 1 M HCl solution: benzoxazole and benzothiazole.
Experimental and theoretical Research on Chemical Intermediates.
investigation. RSC Advances. 2016;6: 2015;41:3729-3742
39784-39800
[13] Madkour LH, Elshamy IH.
[6] Ramaganthan B, Gopiraman M, Experimental and computational studies
Olasunkanmi LO, Kabanda MM, on the inhibition performances of
Yesudass S, Bahadur I, et al. Synthesized benzimidazole and its derivatives for
photo-cross-linking chalcones as novel the corrosion of copper in nitric acid.
corrosion inhibitors for mild steel in International Journal of Industrial
acidic medium: Experimental, quantum Chemistry. 2016;7:195-221
chemical and Monte Carlo simulation
studies. RSC Advances. 2015;5: [14] Mousavi M, Mohammadalizadeh M,
76675-76688 Khosravan A. Theoretical investigation
of corrosion inhibition effect of
[7] Obot IB, Macdonald DD, Gasem ZM. imidazole and its derivatives on mild
Density functional theory (DFT) as a steel using cluster model. Corrosion
powerful tool for designing new organic Science. 2011;53:3086-3091
corrosion inhibitors. Part 1: An overview.
Corrosion Science. 2015;99:1-30 [15] Camacho RL, Montiel E, Jayanthi N,
Pandiyan T, Cruz J. DFT studies of
[8] Verma C, Lgaz H, Verma DK, Ebenso alpha-diimines adsorption over Fe-n
EE, Bahadur I, Quraishi MA. Molecular surface (n = 1, 4, 9 and 14) as a model
15
for metal surface coating. Chemical [26] Gross EKU, Dreizler RM. Density
Physics Letters. 2010;485(1–3):142-151 Functional Theory. New York: Springer
Science & Business Media; 1995
[16] Wang Y, Cheng X, Yang X, Yang X.
DFT study of solvent effects for some [27] Amador C. Density Functional
organic molecules using a polarizable Theory. Berlin, Heidelberg: Springer-
continuum model. Journal of Solution Verlag; 1983
Chemistry. 2006;35:869-878
[28] Hohenberg P, Kohn W.
[17] Dogonadze RR. Theory of molecular Inhomogeneous electron gas. Physics
electrode kinetics. In: Hush NS, editor. Review B. 1964;136:864-871
Reactions of Molecules at Electrodes.
London: Interscience Pub.; 1971. [29] Koch W, Holthausen MC. A
pp. 135-227 Chemist’s Guide to Density Functional
Theory. Weinheim: Wiley-VCH; 2000
[18] Sholl D, Steckel JA. Density
Functional Theory: A Practical
[30] Bel SL, Dines TJ, Chowdhry BZ,
Introduction. New York: Wiley; 2009
Withnall R. Computational chemistry
using modern electronic structure
[19] Enge E l, Dreizler RM. Density
methods. Journal of Chemical
Functional Theory: An Advanced
Education. 2007;84:1364-1368
Course. Berlin, Heidelberg: Springer-
Verlag; 2011
[31] Kohn W, Sham L. Self-consistent
equations including exchange and
[20] Parr RG, Weitao Y. Density-
correlation effects. Physics Review.
Functional Theory of Atoms and
1965;140:A1133-A1138
Molecules. USA: Oxford University
Press; 1989
[32] Perdew JP. Density functional
approximation for the correlation
[21] Marques MAL, Maitra NT, Nogueira
energy of an inhomogeneous electron
FMS, Gross EKU, Rubio A.
Fundamentals of Time-Dependent gas. Physical Review B. 1986;33:
8822-8824
Density Functional Theory.
Berlin, Heidelberg: Springer-Verlag;
2012 [33] Becke AD. Density functional
calculations of molecular bond energies.
[22] Fiolhais C, Marques MAL, Nogueira The Journal of Chemical Physics. 1986;
F. A Primer in Density Functional 84:4524-4529
Theory. Berlin, Heidelberg: Springer-
Verlag; 2003 [34] Lee C, Yang W, Parr RG.
Development of the Colle-Salvetti
[23] Sahni V. Quantal Density Functional correlation energy formula into a
Theory. Berlin, Heidelberg: Springer functional of the electron density.
Science & Business Media; 2004 Physical Review B. 1988;37:785-789
[24] Tsuneda T. Density Functional [35] Perdew J, Yang W. Accurate and

Theory in Quantum Chemistry. Japan: simple density functional for the
Springer; 2014 electronic exchange energy: Generalized
gradient approximation. Physical
[25] Gross E, Dreizler RM. Density Review B. 1986;33:8800-8802
Functional Theory: An Approach to the
Quantum Many-Body Problem. Berlin, [36] Becke AD. Density–functional
Heidelberg: Springer; 1990 exchange-energy approximation with
16
correct asymptotic behavior. Physical [44] Deng S, Li X, Xie X. Hydroxymethyl

Review A. 1988;38:3098-3100 urea and 1,3-bis(hydroxymethyl) urea
as corrosion inhibitors for steel in HCl
[37] Ramachandran KI, Deepa G, solution. Corrosion Science. 2014;80:
Namboori K. Computational chemistry 276-289
and molecular modeling, Principles and
Applications. Berlin, Heidelberg: [45] Singh A, Ansari KR, Haque J,
Springer; 2008;137 Dohare P, Lgaz H, Salghi R, et al. Effect
of electron donating functional groups
[38] Arshad MN, Bibi A, Mahmood T, on corrosion inhibition of mild steel in
Asiri AM, Ayub K. Crystal structures hydrochloric acid: Experimental and
and spectroscopic properties of triazine quantum chemical study. Journal of the
based hydrazone derivatives; a Taiwan Institute of Chemical Engineers.
comparative experimental-theoretical 2018;82:233-251
study. Molecules. 2015;20:5851-5874.
DOI: 10.3390/molecules20045851 [46] Mendoza-Huizar LH, Rios-Reyes
CH. Chemical reactivity of atrazine
[39] Zhan CG, Nichols JA, Dixon DA.
employing the Fukui function. Journal
Ionization potential, electron affinity,
of the Mexican Chemical Society. 2011;
electronegativity, hardness, and
55:142-147
electron excitation energy: Molecular
properties from density functional
[47] Chermette H. Chemical reactivity
theory orbital energies. The Journal of
indexes in density functional theory.
Physical Chemistry. A. 2003;107:
Journal of Computational Chemistry.
4184-4195
1999;20:129-154
[40] Singh A, Ansari KR, Kumar A, Liu
[48] Pearson RG. Absolute
W, Songsong C, Lin Y. Electrochemical,
surface and quantum chemical studies electronegativity and hardness
of novel imidazole derivatives as correlated with molecular orbital
corrosion inhibitors for J55 steel in sweet theory. Proceedings of the National
corrosive environment. Journal of Academy of Sciences. 1986;83:
Alloys and Compounds. 2017;712: 8440-8441
121-133
[49] Parr RG, Gadre SR, Bartolotti LJ.
[41] Tian H, Li W, Cao K, Hou B. Potent Local density functional theory of atoms
inhibition of copper corrosion in neutral and molecules. Proceedings of the
chloride media by novel non-toxic National Academy of Sciences of the
thiadiazole derivatives. Corrosion United States of America. 1979;76:
Science. 2013;73:281-291 2522-2526
[42] Hegazy MA, Badawi AM, Abd El [50] Haque J, Ansari KR, Srivastava V,
Rehim SS, Kamel WM. Corrosion Quraishi MA, Obot IB. Pyrimidine
inhibition of carbon steel using novel N- derivatives as novel acidizing corrosion
(2-(2-mercaptoacetoxy)ethyl)-N,N- inhibitors for N80 steel useful for
dimethyl dodecan-1-aminium bromide petroleum industry: A combined
during acid pickling. Corrosion Science. experimental and theoretical approach.
2013;69:110-122 Journal of Industrial and Engineering
Chemistry. 2017;49:176-188
[43] Kovacevic N, Kokalj A. The relation
between adsorption bonding and [51] Zevallos J, Labbé AT. A theoretical
corrosion inhibition of azole molecules analysis of the Kohn-Sham and Hartree-
on copper. Corrosion Science. 2013;73: Fock orbitals and their use in the
7-17 determination of electronic properties.
17
Journal of the Chilean Chemical Society. [61] Kokalj A. Is the analysis of

2003;48:39-47 molecular electronic structure of
corrosion inhibitors sufficient to predict
[52] Ghanty TK, Ghosh SK. Correlation the trend of their inhibition
between hardness, polarizability, and performance. Electrochimica Acta.
size of atoms, molecules, and clusters. 2010;56:745-755
The Journal of Physical Chemistry. 1993;
97:4951-4953 [62] Lewars EG. Computational
Chemistry Introduction to the Theory and
[53] Chattaraj PK, Sengupta S. Popular Applications of Molecular and Quantum
electronic structure principles in a Mechanics. London: Springer; 2011
dynamical context. The Journal of
Physical Chemistry. 1996;100: [63] Oláh J, Alsenoy CV. Condensed
16126-16130 Fukui functions derived from
stockholder charges: Assessment of their
[54] Hohm U. Is there a minimum performance as local reactivity
polarizability principle in chemical descriptors. The Journal of Physical
reactions? The Journal of Physical Chemistry. A. 2002;106:3885-3890
Chemistry. A. 2000;104:8418-8423
[64] Castro ME, Percino MJ, Cerón M,
[55] Parr RG, Sventpaly L, Liu S.
Soriano G, Chapela VM. Theoretical
Electrophilicity index. Journal of the
inhibition efficiency study of Schiff Base
American Chemical Society. 1999;121:
(E)-2-(2-hydroxybenzylideneamino)
1922-1924
phenylarsonic acid and its isomers.
[56] Geerlings P, De Proft F,
Science. 2014;9:7890-7903
Langenaeker W. Conceptual density
functional theory. Chemical Reviews.
2003;103:1793-1873 [65] López P, Méndez F. Fukui function
as a descriptor of the imidazolium
[57] Pearson RG. Absolute protonated cation resonance hybrid
electronegativity and hardness: structure. Organic Letters. 2004;6:
Application to inorganic chemistry. 1781-1783
Inorganic Chemistry. 1988;27:734-740
[66] Yang W, Parr RG. Hardness,
[58] Kovacˇević N, Kokalj A. DFT study softness and the Fukui function in the
of interaction of azoles with Cu(111) electronic theory of metals and catalysis.
and Al(111) surfaces: Role of azole Proceedings of the National Academy of
nitrogen atoms and dipole-dipole Sciences of the United States of
interactions. Journal of Physical America. 1985;82:6723-6726
Chemistry C. 2011;115:24189-24197
[67] Gomez B, Likhanova NV,
[59] Kokalj A. On the HSAB based Dominguez-Aguilar MA, Martinez-
estimate of charge transfer between Palou R, Vela A, Gazquez JL. Quantum
adsorbates and metal surfaces. Chemical chemical study of the inhibitive
Physics. 2012;393:1-12 properties of 2-pyridyl-azoles. The
Journal of Physical Chemistry. B. 2006;
[60] Cao Z, Tang Y, Cang H, Xu J, Lu G, 110:8928-8934
Jing W. Novel benzimidazole
derivatives as corrosion inhibitors of [68] Guo L, Ren X, Zhou Y, Xu S, Gong
mild steel in the acidic media. Part II: Y, Zhang S. Theoretical evaluation of
Theoretical studies. Corrosion Science. the corrosion inhibition performance of
2014;83:292-298 1,3-thiazole and its amino derivatives.
18
Arabian Journal of Chemistry. 2017;10: quantum chemical studies of the effect

121-130 of poly ethylene glycol as corrosion
inhibitors of aluminum surface. Journal
[69] Rives JT, Jorgensen WL. Molecular of Industrial and Engineering
dynamics of proteins with the OPLS Chemistry. 2014;20:796-808
potential functions. Simulation of the
third domain of silver pheasant [76] Li X, Deng S, Xie X. Experimental
ovomucoid in water. Journal of the and theoretical study on corrosion
American Chemical Society. 1990;112: inhibition of oxime compounds for
2773-2781 aluminium in HCl solution. Corrosion
Science. 2014;81:162-175
[70] Xu B, Yang W, Liu Y, Yin X, Gong
W, Chen Y. Experimental and [77] Khaled K, Amin MA.
theoretical evaluation of two Electrochemical and molecular
pyridinecarboxaldehyde dynamics simulation studies on the
thiosemicarbazone compounds as corrosion inhibition of aluminum in
corrosion inhibitors for mild steel in molar hydrochloric acid using some
hydrochloric acid solution. Corrosion imidazole derivatives. Journal of
Science. 2014;78:260-268 Applied Electrochemistry. 2009;39:
2553-2568
[71] Zhang Z, Tian N, Zhang W, Huang
X, Ruan L, Wu L. Inhibition of carbon [78] Kaya S, Banerjee P, Saha SK, Tüzün
steel corrosion in phase-change- B, Kaya C. Theoretical evaluation of
materials solution by methionine and some benzotriazole and phospono
proline. Corrosion Science. 2016;111: derivatives as aluminum corrosion
675-689 inhibitors: DFT and molecular dynamics
simulation approaches. RSC Advances.
[72] Ozcan M, Dehri I, Erbil M. Organic 2016;6:74550-74559
sulphur-containing compounds as
corrosion inhibitors for mild steel in [79] Qiang Y, Zhang S, Xu S, Li W.
acidic media: Correlation between Experimental and theoretical studies on
inhibition efficiency and chemical the corrosion inhibition of copper by
structure. Applied Surface Science. two indazole derivatives in 3.0% NaCl
2004;236:155-164 solution. Journal of Colloid and
Interface Science. 2016;472:52-59
[73] Singh P, Ebenso EE, Olasunkanmi
LO, Obot I, Quraishi M. [80] Khaled K, Amin MA, Al-Mobarak
Electrochemical, theoretical, and N. On the corrosion inhibition and
surface morphological studies of adsorption behaviour of some
corrosion inhibition effect of green benzotriazole derivatives during copper
naphthyridine derivatives on mild steel corrosion in nitric acid solutions: A
in hydrochloric acid. Journal of Physical combined experimental and theoretical
Chemistry C. 2016;120:3408-3419 study. Journal of Applied
Electrochemistry. 2010;40:601-613
[74] Feng L, Yang H, Wang F.
Experimental and theoretical studies for [81] Khaled K. Corrosion control of
corrosion inhibition of carbon steel by copper in nitric acid solutions using
imidazoline derivative in 5% NaCl some amino acids—A combined
saturated Ca(OH)2 solution. experimental and theoretical study.
Electrochimica Acta. 2011;58:427-436 Corrosion Science. 2010;52:3225-3234
[75] Awad M, Metwally M, Soliman S,

El-Zomrawy A. Experimental and
19
Chapter 08
Electrochemical Techniques for

Corrosion and Tribocorrosion
Monitoring: Fundamentals of
Electrolytic Corrosion
Abdenacer Berradja
Abstract
This first chapter aims at giving a brief framework for understanding the
principles of electrochemistry in corrosion and tribocorrosion, enabling potential
users and readers to quickly apprehend the electrochemical nature of corrosion.
The subsequent chapter will provide additional details on the methods derived
from these principles in a clear manner and ready-to-use format. In particular,
the implementation of electrochemical techniques for the study of tribocorrosion
allows, in situ and in real time, to monitor and control the corrosion conditions
during wear and to quantify the corrosion kinetics. An introductory to some of the
basic terms and concepts of electrochemistry and corrosion is first presented. Then,
an overview of the thermodynamic and kinetic parameters of relevance to corro-
sion electrochemistry is highlighted. A description on how the electrical nature of
corrosion reactions allows the interface to be modeled as an electrical circuit, as well
as how this electrical circuit can be used to obtain information on corrosion rates.
These prerequisites are necessary to better understand the surface reactivity of met-
als and other electronic conductive materials immersed in ionic electrolyte media
whether or not subjected to mechanical stimuli.
Keywords: corrosion, tribo-electrochemistry, tribocorrosion, standard potential,

electrode kinetics
1. Introduction
The corrosion science is a complex subject that is not well defined, and still contin-
ues to progress as the subject evolves from the simple traditional definition of “destruc-
tion of metals through oxidation and its prevention” to “degradation of a material that
involves one or more chemical and/or electrochemical reactions and its foresight”. This
latter material definition encompasses a wide range of environments, and all classes of
materials (ceramics, organics, composites), not just metals. The intentional conjunc-
tion with degradation due to non-chemical processes, such as tribology (i.e., science
of friction, wear and lubrication), has open up a new global perspective topic of a rare
universality that leads us to prospect many aspects of science and technology, namely
tribocorrosion. To better understand the specificity of tribocorrosion, it is necessary to
briefly recall what distinguishes corrosion from tribocorrosion.
1
Corrosion deals primarily with the electrochemical aspects related to physical-

chemical oxidation and reduction processes taking place at the surface of materi-
als and the effect of the reactivity of surfaces of materials with respect to their
environment, time, pH, temperature, pressure, and electrolyte composition. It is
almost without exception an irreversible heterogeneous reaction of a material with
the environment, which usually (but not always) results in a degradation of the
material or its properties (e.g., decadence of the functional properties of materi-
als). Examples of corrosion phenomena include the transformation of steel into
rust, oxidation of an electrical copper contact, cracking of brass in the presence of
ammonia, pipeline degradation by H2S, swelling of PVC in contact with a solvent,
alkaline attack on refractory bricks, and mineral glasses. Occasionally, in certain
cases, corrosion is valuable. For instance, the disposal of neglected metallic objects
in the nature is not an uncommon corrosion phenomenon. It is still common to
find beneficial corrosion reactions in the field practice. A typical example of cor-
rosion protection processes is the anodizing of aluminum. Anodizing strengthens
the passive oxide film on the surface of aluminum, and therefore its resistance to
corrosion, but also serves as a decorative effect. Likewise, corrosion reactions are
used to produce a smooth surface finish in chemical and electrochemical polishing
processes.
Tribocorrosion occurs when surfaces of materials subjected to mechanical
contacts and in relative motion and/or behaviors are affected by chemical, elec-
trochemical and/or biological environmental factors. Accordingly, tribocorrosion
damage (i.e., material loss) can be designated in a broad sense as a failure mecha-
nism due to the mutual interaction of corrosion, friction, and wear processes and
their synergy effects. It generates changes in surface and/or volume compositions
(e.g., alteration of materials properties, surface and sub-surface transformations,
cracking, tribo-chemical reactions, etc.), and often modifies the environment
(e.g., surface contamination by tribo-reaction products or corrosion-produced
compounds, pH changes, and so on), and ultimately can lead to system failure.
Such a physical-chemical deterioration is well described in the literature by the
following terms: corrosive wear, fretting-corrosion or corrosion-erosion [1–6].
Corrosion and wear often combine to cause aggressive damage and at last a shut-
down in a number of industries, such as mining, mineral processing, chemical
processing, metal components of machines, marine structures, pulp and paper
production, ships, bridges, biomechanics (e.g., orthopedics), civil engineering
structures and energy production, and so on. Although, corrosion can often occur
in the absence of mechanical wear, the opposite is rarely true. Corrosion accompa-
nies to some extent in all environments, except in vacuum and inert atmospheres.
The combined effects of friction (wear) and corrosion can result in total material
losses well above than that of the additive effects of each process taken apart,
which is attributed to their synergy [1–3, 7]. These effects are still difficult to
control. Knowledge of the tribological behavior of a material couple in the absence
of any chemical attack and the knowledge of the electrochemical behavior in the
absence of any mechanical impact are not sufficient to deduce the tribocorrosion
behavior of that couple system of materials. In many articulation systems, it has
been noticed that friction may alter the sensitivity, and modifies the composition
of the surfaces of materials in moving contacts to corrosion. In turn, corrosion can
affect the friction (and wear) process of moving contacting parts. This usually
accelerates the tribochemical degradation of the material, which may affect the
contact moving conditions, and thus the friction process and the coefficient of
friction too [1–6]. The contact motion can be a continuous or discontinuous one; it
can be a unidirectional or a reciprocating one. The complexity of a tribocorrosion
system is illustrated in Figure 1.
2
Electrochemical Techniques for Corrosion and Tribocorrosion Monitoring: Fundamentals…
Figure 1.
Schematic of main factors which define the complexity of a tribocorrosion system.
Tribocorrosion of moving solids immersed in an aggressive environment is,

just as friction, a system parameter. The tribo-electrochemical system consists of
implementing in-situ electrochemical techniques to a tribological designed system
under well-controlled conditions (i.e., tribometer type, and complete material
system) [3]. A properly designed laboratory mechanical system allows for the best
simulation as much as possible the entire material system used in the field, and
the constraints that have associated with it (e.g., vibration mode, similarity of the
wear mechanisms active in the laboratory test and in the field, such as abrasion,
adhesion, fatigue, existence or not of a third body, erosion, corrosion, their com-
binations, and so on) [3]. Both mechanical and electrochemical methods allows
for monitoring and recording in-situ and in real-time the following macroscopic
quantities as normal or tangential force, relative or rotational displacement, sliding
velocity, angular frequency, contact temperature, vibrations of the contacting parts
and in relative motion, noise eventually emitted during the test, and the measure-
ments of the electrochemical potential, the corrosion current and/or the imped-
ance of the working materials. In most cases, both wear and corrosion rates can be
determined ex-situ from a loss of material on one or both contacting materials by
surface characterization methods and Faraday’s law concepts respectively. Since the
chapter does not cover comprehensive information regarding tribocorrosion nor it
is the scope of the present work, a state-of-the art and critical reviews on tribocor-
rosion with specific discussions related to mechanisms, general procedures, and
technological aspects may be found elsewhere [1–6], and it is left to the reader to
locate further reading sources for that type of information.
The author assumes the reader is familiar with the background of corrosion
phenomena and of conventional electrochemical methods in corrosion research.
Many textbooks and review articles in the field are available but, for the sake of
readability, a reminder of some aspects is given here.
3
2. Importance of corrosion and tribocorrosion
One of the primary reasons for the importance of corrosion or tribocorrosion lies
on global economic losses. The destruction of nearly a quarter of the world’s annual
steel production is caused by corrosion. An estimate of about 150 million tons of
losses per year, i.e. 300 tons per minute! [8]. Corrosion is definitely not limited to
steel alloys but affects all sort of materials, namely metals, polymers, and ceramics.
Corrosion and wear damage to materials, both directly and indirectly, cost industri-
alized countries hundreds of billions of dollars annually. For example, wear failures
of metals costed the U.S. economy almost $20 billion per year (in 1978) compared to
about $80 billion annually for corrosion during the same period [6]. The economic
losses, due to friction and wear, related to these costs are estimated to be 6–10% of
the Gross National Product (GNP). Wear represent 30% of the causes of dysfunc-
tion of the global mechanical engineering systems [2]. A recent study commissioned
by the American Federal Highway Administration reveals that the annual direct
cost of corrosion was $ 276 billion in 1998, which represents 3.1% of the GNP [9].
Similarly, in the United Kingdom, Japan, Australia and Kuwait, the total annual cost
of corrosion was estimated to range between 1 and 5% of each country’s GNP [10].
Owing to many different types of expenses involved, in general, estimates of the
total cost of corrosion and wear evolve over time and are sometimes difficult and
uncertain. There is no doubt, however, that the cost is quite elevated. The direct
losses concern replacement of corroded materials and equipment. The indirect
losses are related to cost of repair and loss of production, cost of corrosion protec-
tion, and prevention. The direct losses are very often lower than indirect costs. For
example, it is estimated that the price of repairing or replacing a corroded heat
exchanger in a nuclear power plant is insignificant compared to the cost of lost
production time. Another important aspect among major influential factors that
contribute to corrosion or tribocorrosion relevance is related to reliability, or safety
and preservation. Corrosion and wear can compromise the reliability and security
of the operating equipment, leading to failure in-service, and at worst disasters,
e.g., pressure vessels, metal reactors for toxic chemicals, turbine rotors, nuclear
power plants, steering mechanisms for vehicles automobiles, and so on. Further, it
requires the rebuilding or replacing the corroded structures and machinery or their
components and an additional investment of the following supplies and facilities:
metals, energy, water and human efforts to design these metal structures, without
mentioning any other resources.
3. Relevance of corrosion and tribocorrosion monitoring
The importance of corrosion and/or tribocorrosion monitoring is that it allows

people of interest to study the extent of damage due chemical and/or mechano-
chemical attacks and to become aware of the rate at which such damage is progress-
ing so that the necessary measures can be taken to avoid trouble. Generally, the
application of continuous and adequate on-line corrosion or tribocorrosion moni-
toring includes the following advantages: enhanced security, ensuring operational
reliability on-time, minimizing process contamination and maximizing product
quality, providing a sentinel for equipment integrity, and preventing any further
risk related to material or production. The most convenient way to successfully
combat corrosion or tribocorrosion impact on materials and structures is (i) to
understand the main causes of corrosion and/or wear, (ii) to use all available means
to prevent it, (iii) and to implement a continuous improvement approach to corro-
sion and wear protection.
4
There are several factors that can come into play in the process of corrosion
or tribocorrosion [1–3, 8]. Among the common influential criteria on corrosion,
the following main parameters can generally be selected, namely the pH of the
medium, the presence of chlorides (and other alkyl halides), the oxidizing power,
the pressure, and the temperature. Fundamentally, corrosion depends on the
dominating deterioration mechanism of surfaces exposed to chemical environment.
The corrosion resistance properties can be characterized directly by the limits of
use of the materials, which can be expressed, for example, in terms of maximum
temperature in-service or maximum concentration of use. Under normal service
conditions, the understanding and control of corrosion are based on the electro-
chemical interpretation of corrosion phenomena and the consideration of the
relative ranking scales of materials in order to select, by successive approaches, the
materials best suited to each application of interest [3].
Conversely, a more obvious mechanism of tribocorrosion is the periodic exposure
of fresh bare surfaces when sliding friction between surfaces occurs in corrosive
liquids or gases [3]. This results in reaction products mainly driven by chemical and
electrochemical interactions. The surfaces of the materials are quickly covered by a
scale of the reaction product, the oxide in the case of metals and metallic alloys, act-
ing as a protective barrier layer. Often, the thinner the scale, the faster the reaction,
and the weaker the protectiveness [3]. Though, tribocorrosion processes are complex,
combining both wear and corrosion. Modern research has established a consensus on
four main forms of wear, namely, chemical wear (i.e., corrosion and corrosive wear),
adhesive wear, abrasive wear or surface fatigue wear [3, 11]. Each process obeys its
own laws and, to confuse things, one of the modes of wear acts to affect the others,
hence the complexity of corrosive wear [1–3]. As a general rule, there is a combina-
tion of competitive wear mechanisms in a dynamic mechanical-chemical contact.
3.1 Choice of technique (instrumentation)
There are many electrochemical and non-electrochemical techniques for the study
of corrosion or tribocorrosion and many factors must be taken into account when
choosing a technical method. The corrosion rate can be determined by extrapolation
of Tafel from a potentiodynamic polarization curve [12, 13]. It can also be determined
using the Stern-Geary equation from the polarization resistance derived from a linear
polarization experiment or from electrochemical impedance spectroscopy [12, 13].
Furthermore, among the recently developed techniques, those using electrochemi-
cal noise analysis as a method of determining the rate of corrosion and estimating
the tribocorrosion rate of some passive materials has been shown to be beneficial,
although scientists are struggling through the interpretation of some conflicting
results [2, 12–15]. Sensitivity to localized corrosion is often evaluated by determining
a breakdown potential and a repassivation potential for passivating materials.
3.2 Corrosion forms
Obviously, the most typically known mode of corrosion is the rusting of iron, or
iron oxide, and ordinary steel. Contemporary corrosion research has established sev-
eral forms of corrosion, all which are important to understanding, as the best methods
of preventing corrosion depend upon the form of corrosion, as shown in Figure 2.
• Uniform corrosion: the damage by general or uniform corrosion is fairly predict-

able; however, the damage caused by localized corrosion is rather unpredict-
able if no proper monitoring techniques are applied. When left uncontrolled,
corrosion will not only cause costly equipment maintenance and replacement
5
Figure 2.
Forms of corrosion.
but may be responsible for the loss of revenue from unexpected system shut-
down and the possibility for hazardous leaks causing major safety issues and
possible environmental contamination [16].
• Pitting is a form of localized corrosion that occurs when the thin passive
protective film on most corrosion-resistant engineering alloys is compromised.
The rate of attack at pits can be extremely high so pitting can lead to perfora-
tion of a structure or initiation of a crack [17].
• Localized corrosion often initiates at an occluded region where the environment

has limited access. This form of corrosion, so-called crevice corrosion, is extremely
important in fastened structures which often contain many crevices [17].
• Localized corrosion is sometimes observed at grain boundaries when the

composition of the grain boundary or region near the grain boundary is
different than that in the metal grain. This type of corrosion, so-called
intergranular corrosion is a severe problem, in particular for stainless steels
and aluminum alloys [17].
• Corrosive attack can be localized at one component of a structure made from dif-
ferent metals that are electrically connected as a result of galvanic corrosion [17].
• The corrosion of metal alloys often results in preferential reaction of one or

more of the alloying elements, so-called dealloying [17].
• A common by-product of the corrosion process is hydrogen. Hydrogen can

interact with metals in various ways to result in a degradation of properties,
primarily mechanical properties (e.g., pipeline gas transportation by H2S).
A generic name for such degradation is hydrogen damage [17].
6
• The mechanical properties of metals can be severely degraded by the combined

effects of the environment and an applied stress. Stress corrosion cracking is the
premature failure of metal structures as a result of these effects [17].
• Corrosion fatigue occurs when the applied stress is fluctuating rather than being
constant [17].
4. Aspects of corrosion prediction in aqueous media
Although, air in atmosphere is the most omnipresent environment, the aqueous

solutions (e.g., atmospheric moisture, acid rain, natural waters, artificial solutions,
and so on) are the most common environments associated with corrosion issues.
Due to the conditions under which a material, e.g., a metal or a metallic structure
is exposed to the environment, corrosion processes usually take place at the metal/
environment interface through ionic conduction processes. Corrosion is due to
electrochemical reactions involved in that interface and strongly affected by a
number of factors, among others, such as the power oxidizing (electrode equilib-
rium potential), hydrogen ion activity (pH, acidity level of the solution), driving
force for metal stability (Gibbs free energy change), rate-determining step reaction
or reaction rate (corrosion current), and temperature (Arrhenius oxidation rate or
the Pilling-Bedworth ratio).
The prediction of corrosion of a metal or an alloy in environments such as
aqueous solutions requires information on the expected state of the metallic
alloy (e.g., oxide or non-oxidized metal, etc.) and the rate at which the metallic
alloy moves to that state. So first, thermodynamic principles can be applied to
determine what processes can occur, and under which conditions the reactions
are at an electrochemical equilibrium and, in case of deviation from that equilib-
rium, in which directions the reactions can proceed and what is the driving force
involved. The kinetic laws then describe the reaction rates. These are strongly
related to the activation energies of the electrode processes, to the mass transport
and to the fundamental properties of the metal/environment interface, such as
the resistance of surface films. A general method, namely the mixed potential
theory, is implemented for interpreting or predicting the corrosion potential and
reaction rates.
In what follows, a very brief reminder of corrosion principles is given.
4.1 Electrochemical nature of metal/electrolyte exchange reaction
The corrosion process is electrochemical in nature. In a more general sense, a

corrosion process involving a metal/aqueous solution or any other metal/ionically
conducting medium exchange or interaction interface is defined as any process caus-
ing the metal, M, to loose one or more of its loosely bound electrons in the metallic
state (i.e., oxidation reaction) to generate a solvated cation in the solution, and it is
simultaneously balanced, in order to ensure an exact count of the electrons involved,
by a reduction reaction by which one or more atoms of a molecule or an ion (anion)
of species in solution gain one or more of these electrons (conservation criteria).
The aqueous corrosion sometimes requires that the oxidation product is either
an oxide of the metal itself according to (1):

2M + O 2= 2MO (1)
7
or is a metal hydroxide and the reduction product of hydrogen ions in solution is

gaseous hydrogen as claimed in the equation (2):

M + 2H 2 O = M (OH) 2 + H 2 (2)
However, it is of course not necessary for an oxide or hydroxide to be formed as

an oxidation product of the metal. For example, in the overall reaction of corrosion
of iron in a dilute chloridric acid, the ferrous chloride compound is generated as an
oxidation product according to the reaction (3),
Fe 0 (s) + HCl 0 (aq)= FeCl 0 2(s) + H 0 2(g)
(3)
The superscript associated at each reactant or reaction product refers to the

valence charge or the oxidation state. The subscript corresponds to the matter phase
state for each element of the reaction or compound.
The foregoing overall reaction involves vigorous oxidation and reduction (viz.
redox) processes. This requires that hydrogen gas is released, more likely by a
desorption process, and the solid Fe is oxidized by the acid, forming an ionic bond
with the chloride ions. The ferrous ions are removed from the metal lattice and get
solvated as they diffuse into the solution. The ferrous chloride compound can be
dissociated at normal concentrations.
It is worthy of note that the chloride ions are not actually involved in the redox
reaction, this equation (4) can be written in the simplified form as follows:
+
Fe 0 (s)  + 2H   (aq) = Fe 2+ (aq)  + H 0 2(g)
(4)
It is worthy of note that this also applies to aqueous corrosion involving other
acidic media (e.g., orthophosphoric acid, H2SO4, HF), and water-based organic
acids (e.g., methanoic or ethanoic acids). In each case, no more than hydrogen ion
is active, whereas the other ions such as phosphate, sulfate or acetate take no part in
the corrosion reaction. Hence, iron reacts with the hydrogen ions of the acid solu-
tion to form iron ions (oxidation process) and hydrogen gas (reduction of process).
Thus, Eq. (4) can be conveniently divided into two reactions (partial half-cell
reactions), namely the oxidation of iron and the reduction of hydrogen ions. This
provides the basis for the thermodynamic consideration of the overall corrosion
process as stated by equations (5), (6), and (7):
Oxidation or commonly referred to as the anodic reaction is indicated by an

increase in the valence charge or electron production. A decrease in the valence
charge or an electron consumption represents a reduction or commonly a cathodic
reaction.
Equations (5) and (6) outline the two half-cell electrode reactions-both need
to occur simultaneously and at the same speed on the metal surface otherwise it
would charge spontaneously electrically, which is impossible. This explains one of
the fundamental principles of corrosion, namely: the oxidation rate is equal to the
reduction rate (in terms of electron production and consumption).
8
The sites for the oxidation reactions are called anodes, and the sites for the reduc-
tion reactions are called cathodes. Anodes and cathodes can be spatially separated at
fixed locations associated with heterogeneities on the electrode surface. Otherwise,
the locations of the anodic and cathodic reactions can randomly fluctuate across the
electrode surface. The former case results in a localized form of corrosion, such as
pitting, crevice corrosion, intergranular corrosion, or galvanic corrosion, and the
latter case results in nominally uniform corrosion [17].
The above concept is illustrated in Figure 3. An iron atom undergoes a transforma-
tion into a ferrous ion and two electrons. These electrons, which remain in the metal,
are immediately consumed during the reduction of hydrogen ions. Figure 3 illustrates
the separation of these two processes in space, merely for the sake of transparency. In
fact, whether or not they separate or take place at the same surface location, this does
not impact the principle of charge conservation. In some cases, the oxidation reaction
takes place in a uniform manner on the surface. In other situations, the corrosion
reaction occurs at specific locations of the surface (i.e., localize corrosion).
It should be noted that there are several different cathodic reactions encountered
repeatedly during metallic corrosion. The most common are:
n is the number of electrons involved in the reaction. The evolution of

hydrogen is a common cathodic reaction because acidic media are frequently
encountered. Oxygen reduction is very common because any aqueous solution
in contact with air is able to produce this reaction. In nearly neutral electrolytes,
the reduction of oxygen is normally one of the most universal cathodic reactions.
Concentrations of ≈6 ppm dissolved oxygen are usually present in dilute aqueous
electrolytes at ambient temperature (25°C). The reduction of metal ions and the
deposition of metals are less frequent reactions and are most often encountered in
chemical processes.
4.2 Thermodynamic approach to corrosion
Thermodynamic data estimations are meaningful in corrosion field because

they can be used to predict the tendency of a metal to corrode in a given environ-
ment. Details on thermodynamic principles can be found in a number of manuals
[18, 19]. The Atlas of Electrochemical Equilibria in Aqueous Solutions by Marcel
Pourbaix provides a complete summary of the application of thermodynamic cor-
rosion for all elements in water [20]. Dr. Pourbaix originally developed “corrosion
maps or corrosion road charts” in the form of potential-pH diagrams [20], which
enables for displaying the stability of metals (the lowest free energy state) as a
function of the activity of hydrogen ions (pH) and equilibrium potential (oxidizing
power). So, the diagrams can, in principle, indicate under which conditions of pH
and equilibrium potential, an expected corrosion does not occur (immunity region,
e.g., pure Fe) or might cause the metal to transform to an ion (metal loss, state of
corrosion, e.g., ions of Fe and its compounds) or even indicate whether an oxidized
solid should be formed or not (possible passivity, e.g., oxides of Fe). A typical
example showing all of these common aspects of metal corrosion is depicted in
Figure 4 for Fe-H2O system [20].
9
Figure 3.
Reversible iron electrode.
Figure 4.
Pourbaix potential-pH diagram for Fe/H2O system at 25°C. Reprinted from [20] with permission from NACE
international.
4.2.1 Change in Gibbs free energy
A myriad of chemical oxidation-reduction reactions can be performed in

an electrochemical cell in which electrons released by the oxidation of species
at an electrode (anode) flow through an external conductor (e.g., electrolyte)
to a second electrode (cathode) where they are consumed by a reduction reac-
tion [19]. An equivalent ion current flows in the electrolyte which separates the
electrodes from the electrochemical cell. In such a device system, the change
of chemical energy results from the change of free energy. This change in free
10
energy or commonly termed Gibbs free energy, ΔG, can be defined as a direct
measurement of the maximum available electrical energy of a system or in other
words it is an indicative measure of the driving force for the reaction to proceed.
If the free energy change accompanying the transition of a system from one
state to another is negative (ΔG < 0), it indicates a loss of free energy as well as
the direction of spontaneous reaction of the system. In particular, if no external
force acts on the system, it will tend to transform into its lowest energy state
and for a given reaction, it will tend to proceed spontaneously. If the free energy
change is positive (ΔG > 0), it indicates that the transition represents an increase
in energy, which requires the addition of an extra energy to the system for the
reaction to proceed.
The free energy change accompanying an electrochemical reaction can be
calculated by the following equation:
ΔG = −nFE (13)
where ΔG is the standard free energy in the overall reaction, n the number of
electrons involved in the reaction, F the Faraday constant, and E equals the cell
potential or the difference between the two standard half-cell potentials. Noting
that the term “standard” potential is the potential of a metal or any reactant in
contact with its own ions at a concentration equal to the unit activity (i.e., approxi-
mately 1 g atom weight per 1 l solution) and at 25°C.
Although Eq. (13) forms the basis for thermodynamic calculations, it is rarely
used in studying corrosion phenomena. This is because it is not possible to accu-
rately predict the velocity of a reaction from the change in free energy. It is worth
remembering that in most cases, the true magnitude of free energy change is trivial
in corrosion applications. The most important factor is the sign of the free energy
change for a given reaction, because it indicates whether the reaction is spontane-
ous or not. Hence, this parameter only reflects the direction of reaction by its sign.
Reactions occur exceptionally in the direction that reduces the Gibbs free energy.
The more negative the value of ΔG, the greater the tendency for the reaction to
proceed. For example, for any overall corrosion reaction of Fe in dilute chloridric
acid solution to be thermodynamically possible, it is necessary that the anodic dis-
solution potential of Fe (i.e., oxidation of Fe) be more active (less noble) than that
of the cathodic reaction (i.e., hydrogen evolution). If the change in free energy is
positive, the reaction does not occur spontaneously.
4.2.2 Cell potentials
The cell potential of the overall electrochemical or corrosion reaction, as speci-

fied above for the example of Fe in a dilute HCl solution, is directly associated with
the change in free energy accompanying that reaction via Eq. (13) according to,
 ΔG  
E = − ___ (14)
nF
A simple rule can be derived from Eq. (14) to predict the spontaneous direction
of any electrochemical reaction. This rule can be clearly stated as: “In any electro-
chemical reaction, the most negative or active half-cell tends to be oxidized, and
the most positive or noble half-cell tends to be reduced”. Therefore, the potential is
a measure of the reaction (corrosion) tendency. Positive potential corresponds to
negative ∆G and hence to spontaneous reaction.
11
A potential can be assigned to each of the half-cell reactions (anodic oxidation

and cathodic reduction). In that respect, the choice of an appropriate reference
(half-cell reaction) will therefore allow the measurement of the potential between
two electrodes (i.e., working and reference electrodes). An arbitrary half-cell
reaction is used as a reference by setting its potential to zero and all other half-cell
potentials are calculated with respect to this zero reference. It is common to use
the normal or standard hydrogen electrode (SHE) as a universal reference when
enumerating the potential of a half-cell [19]. The SHE corresponds to the half-cell
reaction (15) given hereafter:
+
2H   + 2e −= H 2
(15)
under standard conditions, viz. the activity of the protons is unity (aH+ = 1), and
the partial pressure of H2(g) is 1 bar (p(H2) = 0.987 atm). The potential of the SHE is
arbitrarily set at zero (E°SHE = 0 V), and therefore ∆G° (aH+ = 1) is arbitrarily set to
0 as a reference free energy change. The superscript “0” in the SHE potential refers
to a standard or reversible potential.
Since it is not possible to manufacture an electrode from hydrogen, an inert
electrode is used. Generally, a platinum electrode acts as an inert metal substrate
for the electrochemical reaction. Consider an electrochemical cell containing iron
and platinum electrodes immersed in a sulfuric acid, both in equilibrium with
their reaction product ions and separated by a porous membrane to retard mixing,
as illustrated in Figure 5. In the reversible divided cell, equilibrium is established
between iron and its ions on the iron electrode and hydrogen gas and hydrogen ions
on the platinum electrode respectively.
At different locations on the platinum electrode, the hydrogen ions are reduced
to gaseous hydrogen and the gaseous hydrogen is oxidized to hydrogen ions,
with electron transfer occurring between these spots. It is worthy of note that
the platinum electrode does not participate in this reaction but merely serves as a
solid interface at which this reaction can occur. Many metals function as reversible
hydrogen electrodes (e.g., Hg/Hg2Cl2 (Calomel), Ag/AgCl, Hg/HgO, Hg/Hg2SO4,
Ag/Ag2SO4, Cu/CuSO4, etc.); platinum is generally preferred because of its inertia
Figure 5.
Electrochemical cell containing reversible iron and hydrogen electrodes (Pt.).
12
and the ease with which electron transfer occurs on its surface (e.g., properties of
catalytic surface exchange or easy current flow rate). As with the other half-cell
electrodes, at certain infinitesimal areas on the metal iron surface, iron atoms are
oxidized to ferrous ions, and at other spots ferrous ions are reduced to metallic
iron. Equilibrium conditions dictate that the rates of the reactions in each half-cell
compartment be equal; there is no net change in the system. Noting that the interac-
tions taking place at the metal electrode/electrolyte are quite complex and closely
related to electrochemical kinetics and physical phenomena (e.g., electrical double
layer, diffusion, etc.).
Consider now the case, under standard conditions, where two dissimilar metals
each immersed separately in their own ions in an aqueous medium and electri-
cally connected. Under these conditions, the corrosion control is governed by the
determination of the mechanisms involved in the redox reactions. Standard redox
potentials can be used to understand the corrosion tendency of metals. A disposi-
tion of metals based on their standard potentials has been established and known as
standard equilibrium oxidation-reduction potential or standard reversible potential
or electromotive force series. The standard potential series of metals is given in
Table 1. In this series, electrode potential values are invariant, given vs. SHE, and
attributed to reduction reactions. The same series can be developed on the basis of
the oxidation reactions, in which case the potential values will be the same but the
“signs” will be reversed.
Redox potentials are very useful for predicting corrosion behavior of metals
and upon certain conditions, the tendency of chemical degradation of pas-
sivating materials under sliding contacts [22]. Any electrochemical reaction
can, therefore, be studied on the basis of the half-cell reaction concept and the
foregoing potential standards involving the combination of metals in aqueous
solutions with or without any mechanical contact. For example, consider two
dissimilar metal pieces, namely silver and zinc, each immersed separately in a
dilute acid solution (e.g., H2SO4) with their own ions (Figure 6) and electri-
cally connected via a potentiostat (i.e., a high-resistance voltmeter). It is neces-
sary that the two electrodes are in equilibrium in their own compartment. The
positive terminal of the potentiostat must be connected to the silver electrode,
and the negative terminal must be connected to the zinc electrode to have the
potentiostat read on scale. According to data in Table 1, the standard redox
Figure 6.
Electrochemical reversible cell containing silver and zinc in equilibrium with their ions and electrically
interconnected via a high-resistance voltmeter.
13
Electrode red-ox reaction E° (volts)

3+
Au = Au + 3e +1.498
+
O2 + 4H + 4e = 2H2O +1.229
2+
Pt = Pt + 2e +1.2
Pd = Pd2+ + 2e +0.987
Ag = Ag+ + e +0.799
2Hg = Hg2+ + 2e +0.788
3+ 2+
Fe +e = Fe +0.771
−
O2 + 2H2O + 4e = 4 OH +0.401
2+
Cu = Cu + 2e +0.337
4+ 2+
Sn + 2e = Sn +0.15
+
2H +2e = H2 0.000
2+
Pb = Pb + 2e −0.126
2+
Sn = Sn + 2e −0.136
2+
Ni = Ni + 2e −0.250
Co = Co2+ + 2e −0.277
2+
Cd = Cd + 2e −0.403
2+
Fe = Fe + 2e −0.440
3+
Cr = Cr + 3e −0.744
2+
Zn = Zn + 2e −0.763
3+
Al = Al + 3e −1.662
2+
Mg = Mg + 2e −2.363
+
Na = Na + e −2.714
+
K = K + e −2.925
Reproduced from [21] and used with permission.
Table 1.
Electromotive force series (Emf or standard potentials redox in volts vs. SHE at 25°C).
potential of silver is +0.799 volts (vs. SHE) and that of zinc is −0.763 volts. In

this manner, zinc oxidation and silver reduction reactions are spontaneous at
+0.763 and +0.799 volts respectively. Their equivalent non-spontaneous reac-
tions occur at −0.763 volts for zinc reduction and at −0.799 volts for the oxida-
tion of silver.
The potentiostat shows a potential difference of approximately 1.562 volts when
the silver and zinc electrodes are connected. In this reversible electrochemical cell,
zinc is negative with respect to silver. Thus, zinc undergoes anodic oxidation (corro-
sion) while silver ions undergo cathodic reduction at the silver cathode. The use of
redox potentials greatly simplifies the calculation of potential cells and simultane-
ously allows to determine the trend in metal corrosion.
It follows from the above principle that all metals having a more active (nega-
tive) reversible potential than hydrogen will tend to be corroded by acid solutions.
Silver, with its higher positive and noble potential, is not corroded in acid media.
Though, the presence of dissolved oxygen may alter this latter rule, leading to oxy-
gen reduction (cathodic reaction) and silver oxidation (anodic reaction). Table 1
indicates that in the presence of oxygen, silver tends to corrode spontaneously.
14
In that respect, the following conclusions may be drawn from the outcome of the
standard redox potential series:
Ag + H 2 SO 4= ∅ or no reaction (Ag / Ag  more positive or noble than H 2 / H  )

+ +

(16)
2Ag + 2H 2 SO 4 + O 2= 2AgSO 4 + 2H 2 O (O 2 / H 2 O more positive or noble than

                                                Ag / Ag  )
+
(17)
As the reversible potential of a metal becomes more noble, its tendency to cor-
rode in the presence of oxidizing agents decreases.
It is important to note that all the above discussions refer to conditions for corrosion
systems at unit activity. Since half-cell potentials change with concentration, Nernst
calculations must be made before predicting spontaneous direction at concentrations
other than unit activity. To determine the potential of a metal in which the reactants
are not at a unit activity, the familiar Nernst equation has been formulated as follows,
a 
 2.303RT
E = E 0 + _______
     log [____ ed]
 ao rxid   (18)
nF
where E represents the potential of the half-cell reaction, E° the standard

potential of the redox reaction. R, T, n, and F are the gas constant, the absolute tem-
perature in kelvin, the number of electrons, and the Faraday’s constant respectively.
aoxid and ared represent the activities (concentrations) of both oxidized and reduced
species respectively.
As indicated in Eq. (18), the half-cell potential becomes more positive as the
amount of oxidized species increases. For each tenfold increase in oxidized reac-
tant, the half-cell potential increases by 59 mV for a single electron reaction (n = 1).
In practice, for corrosion to occur, it is not necessary for a metal to be in contact
with its own ions. Local anode and cathode zones may exist on the same surface
of the metal or alloy, thus acting as an electrical conductor of the electrochemical
flow. When such a metal is immersed in an electrolyte, it can no longer equilibrate
to experimental thermodynamic scales. Therefore, corrosion is a direct consequence
of a new equilibrium potential change, which depends on a myriad of physical
and chemical properties of these electrochemical systems (e.g., pH, temperature,
oxidizing agents and their power, IR drop of solution, etc.). This potential is called
corrosion potential or mixed potential, which is far different from the standard
potential. In this respect, corrosion will depend on the rate-limited electrode kinet-
ics (e.g., charge transfer rate, mass transport, diffusion, etc.).
4.3 Polarization (overvoltage)-exchange current density
The concept of polarization or overvoltage is very briefly addressed here because

of its importance for understanding corrosion reactions and its behavior. It repre-
sents a prerequisite for electrochemical methods. The rate of an electrochemical
reaction is limited by various physical and chemical factors. Therefore, an electro-
chemical reaction is said to be polarized or delayed by these environmental factors.
Consider an electrochemical half-reaction for an electrode M at equilibrium:
M n+ + n e −↔ M
(19)
When a reaction is at equilibrium, it does not necessarily mean that the system
is at rest and/or inactive. On the contrary, for a system in equilibrium, the reaction
15
rate in the forward direction is equal to that in the backward or reverse direction.
This equal rate at equilibrium is defined as the exchange current density, i0.
It is worth of note that i0 is dependent on surface concentrations of the reactants,
cR, and those of the products, cP, according to: i0 ∝ cRm cPn m and n are exponents.
As reported in the previous section (Section 4.1), the reaction of hydrogen evo-
lution is very often when a metal corrodes in an acidic environment. Interestingly,
the current exchange rate for this cathodic hydrogen evolution reaction strongly
depends on the catalytic properties of the metal surface on which the reaction
occurs. For example, it ranges from 10−12 A cm−2 for lead (Pb) to 10−3 A cm−2 for
palladium (Pd) at 25°C in 1 M H2SO4 [23]. This variability can have broad implica-
tions for the rate of corrosion. In fact, the rate of the reaction can be limited by the
rate of the cathodic reaction, which is highly dependent on the current exchange
rate of the reaction.
Figure 7 shows the point for an equilibrium of a given reaction at the electrode.
It suggests a finite exchange current density at a given potential (e.g., reversible
potential Erev or E°M/Mn+). Notwithstanding, in electrochemistry, potential and cur-
rent are interdependent. It is possible to control one and measure the other. Since
the former current density involves a “two-way” rate process (forward-backward),
the net current density is null. However, at a different potential of Erev (i.e., over-
voltage), the half-cell reaction will preferentially proceed in one direction and a net
current will be measured.
The overvoltage, η = E-Erev, is defined as a potential variation with respect to the
reversible potential in the equilibrium of a given electrode reaction. This change
in potential is associated with a change in the net reaction rate, and it is therefore
related to a change in the direction of the reaction taking place, so that the reaction
will mainly proceed in one direction according to the reaction rate. The current
is anodic (oxidizing or positive) for a potential change to a value greater than the
reversible potential (i.e., anodic polarization) and it is cathodic (reducing or nega-
tive) for a potential change to a value below the reversible potential (i.e., cathodic
polarization), cfr Figure 7.
Polarization can be conveniently divided into three different types, activation
polarization, concentration polarization, and ohmic potential drop (iR).
• Activation polarization refers to an electrochemical process controlled by the

reaction sequence at the metal/electrolyte interface (e.g., by possible steps of
Figure 7.
Illustration of the relation between the current density and the potential for a simple electrochemical reaction
under activation control.
16
adsorption, desorption, and charge transfer processes). It is caused by a slow

electrode reaction. In particular, an activation overvoltage or charge transfer
overvoltage alludes to an overvoltage resulting from a potential change when
the concentrations of the reactants and products at the electrode surface are
the same as in the bulk solution. This is because the charge transfer rate at the
electrode/electrolyte interface is not infinitely fast. Note that the concentration
at the surface of the electrode is equal to the bulk concentration when the mass
transport rate is fast compared to the rate of charge transfer.
• Concentration polarization (Diffusion Overpotential) refers to electrochemical

reactions controlled by the rate of diffusion in the electrolyte of ions on the
surface of the metal.
• iR drop occurs in a portion of the electrolyte surrounding the electrode, or

through a reaction product film on the surface of the metal, or in both cases
[24]. An ohmic potential drop takes place between the working electrode and
the capillary tip of the reference electrode. This contribution to polarization
is equal to iR, where i is the current density, and R, equal to l/κ, represents
the value in ohms of the resistance path of the solution of length l (cm) and
specific conductivity κ (Ω−1 cm−1). Therefore, the resistance of an electrolyte
of length measuring l (cm) with a cross-section S (cm2) is equivalent to l/κS
(ohms). Hence, the iR drop in volts equals il/κ. The product, iR, decays in
parallel with the shutting-off of the current, while the concentration polariza-
tion and the activation polarization generally decay at measurable speeds. For
instance, for a cathodic protection of steel in seawater (κ = 0.05 Ω−1 cm−1), it
is necessary to apply a current density of 0.1 A/m2, which may result in a iR
drop correction equal to (10−5 V)/(0.05) = 0.2 mV with respect to 1 cm separa-
tion of the probe from the cathode. This value is negligible with regards to the
critical minimum current density required for convenient cathodic protec-
tion. However, in certain soft/fresh waters, where κ can reach the value of
10−5 Ω−1 cm−1, the corresponding iR drop is equal 1 V/cm.
Noting that the concentration polarization decreases with stirring, whereas the
activation polarization and iR drop are not affected significantly.
5. Quantitative measurements of corrosion and tribocorrosion rates
5.1 Corrosion rate
The foregoing discussion on the thermodynamics of corrosion under equilib-

rium conditions yields information on the driving force of the corrosion process.
Since corroding systems are not always at equilibrium, therefore thermodynamic
calculations cannot be applied. Notwithstanding that the information on the corro-
sion tendency accessible from thermodynamic calculations is important and useful.
However, most scientific and technical aspects in the field of corrosion focus on the
knowledge and the reduction of corrosion rate. Thermodynamics does not address
the rate of corrosion.
Metals and non-metals are compared on the basis of their corrosion resistance.
For these comparisons to be meaningful, the attack rate of each material must be
expressed quantitatively. Corrosion rates can be given in a number of different units
using different measures of material loss. A convenient way to determine the rate of
corrosion is by the immersion of a sample in a corrosive environment for a period
17
of time and measure the weight loss during that time [25]. The weight loss should
be normalized to the exposed surface area of the sample in order to determine its
rate of corrosion. Therefore, among the set of units adapted to the corrosion rate
is the weight loss per unit area per unit of time; for example, mg cm−2 s−1. It is also
common to use the percentage of weight loss, milligrams per square centimeter per
day and grams per square inch per hour. Though, these do not express the corrosion
resistance in terms of penetration. From a technical point of view, the penetration
rate, or the thinning of a structural part, can be used to predict the lifetime of a
given component. An easy way is to divide this measurement by weight loss by the
density of the corroding material to obtain a corrosion rate in units of thickness
lost per unit of time. The term mils per year is the most desirable way to express
corrosion rates (mpy) or mm yr.−1. This expression can be easily calculated from the
weight loss of the metal sample during the corrosion test by the formula (20), given
below:
 CM   ic orr
r = ____ (20)
𝜌nF
where r is the rate of material loss (mm yr.−1), M the molecular weight of the
corroding metal (g mol−1), ρ the density of metal (g cm−3), icorr the corrosion cur-
rent density (A cm−2), and C a constant to change the units of thickness and time.
5.2 Tribocorrosion rate
Wear is an unavoidable and a potentially serious problem in all areas of

engineering [3]. Designers and engineers who have to make optimal decisions in
situations where tribocorrosion considerations are significant, need to know “how
long will a component last?”. To solve this question, numerous models have been
developed so far to distinguish this material loss due to tribocorrosion [3]. These
models usually correlate a wear volume or a wear rate with physical and geometrical
quantities. Various expressions have since been attributed to this material loss, of
which the material loss can be defined in terms of weight, volume, surface, depth,
width or even charge density or current density, per unit hardness, per unit fric-
tional dissipated energy (work due to the tangential force), per unit input energy
(work due to the normal force), or even per unit sliding distance, or sliding time,
sliding frequency, contact frequency, etc. [3]. It becomes readily understandable of
the complexity of comparing results between the various wear data published so far.
It is expected then that the terminology in this field is rather uncertain, and it will
remain so for a certain time, hence the need for a specific standardization, despite
some recent progress made in this area [3, 26].
One of the earlier attempts to predict the wear rate or wear volume loss of a mate-
rial in sliding contact is the commonly Archard wear criterion [27] used during the
second half of the 20th century. That criterion is usually expressed as follows [3],
 
F
Wv  = k ___
  N  = kAr  (21)
H
where Wv and Wr represent the volumetric loss (assigned as total volume of wear
debris produced), and the wear rate (usually expressed per unit sliding distance),
respectively. k is the dimensionless Archard wear coefficient, Ar the real area of
contact, FN the applied normal load, and H the hardness of the worn material.
This equation was originally used for the case of adhesive wear [28, 29], then it
was extended to more cases including that of tribocorrosion [3]. This is because the
k parameter in Eq. (21) exclusively remained the only flexible parameter consistent
18
with the case to which the wear may originate [3]. For example, unidirectional slid-
ing of mild steel against mild steel without any lubricant has a k of 10−2, whereas,
for stellite sliding against tool steel, k is 10−5 [3, 30]. Even more confusing is that,
according to literature, the Archard wear coefficient can vary by two orders of
magnitude for the same couple of materials just due to a slight change in load or
speed [31]. These findings should be taken with precautions in view of the number
of empirical error cases reported with respect to the wear reproducibility and
validation of test methods [3]. Friction and wear properties are often considered as
subjects of poor accuracy in comparison with materials intrinsic properties. Indeed,
comparative round robin studies on the topic have shown that the reproducibility
of wear derived from different inter-laboratories with the same material pairing
was often very poor [32]. Using the wear track width, the scattering was roughly
50% whereas the scatter in the wear coefficient was over three orders of magnitude.
No clear correlation was found between a single and constant parameter (type of
tribometer, normal force, and sliding velocity) and the wear rates measured in
inter-laboratories [3]. Interestingly, a good convergence was found between the
wear volume loss and the energy dissipated in the tribo-contact zone [33–37]. This
can readily be explained by the fact that the dissipation of frictional energy is one,
among others, of the main causes of tribo-electrochemistry, playing an essential
contributing role in wear mechanism, in this case entailing an acceleration (e.g.,
chemical wear rates) or modification of tribo-chemical reactions [3]. The yielded
frictional heat between interacting surfaces leads to a stationary rise in temperature
at surface contact asperities and flashes. Furthermore, such frictional energy can
take the form of high quantum excitations with short lifetime of surface and bulk
sites due to the mechano-chemical forces involved during the sliding process.
Those excitations are also responsible for the occurrence of triboluminescence and
triboelectricity [3].
Tribologists nowadays are seeking for an agreement due to the fact that there
is an unavoidably need to address more fundamental research towards the estab-
lishment of an original formulation or a universal methodology to define a “wear
criterion” in order to better understand the complexity of the wear process in a
tribocorrosion test [3]. Although, this aim has not yet been achieved, a fair amount
of progress has been made on this matter-oriented approach. This remains so far
valid only as part of the case-by-case study. To conclude, research must focus on
establishing a functional-mechanistic based approach that emphasizes the nature
of the dependence of the mechano-chemical wear rate (output) on the energetic
aspect of sliding friction, the electrochemical aspect of the exposure of bare metal
surface, and the transformation of the subsurface material (input). This usually
should incorporate materials properties, and behavior. If it does, this could be
very useful to help solving the issues and struggling difficulties encountered in the
specific field. This will lead to a better improvement of the reliability life of selected
material and design technologies when adopted in specific mechanical articulations
and under aggressive environments. Further, this could predict materials perfor-
mance in an environment where tribocorrosion plays a significant role [3].
In tribocorrosion phenomena, where tribological contacts are exposed to corrosive
environments, such as aqueous lubricants, the contact materials are subject to both
mechanical, and chemical/electrochemical solicitations, which contribute to material
removal from sliding surfaces [3]. The rate of material degradation/removal cannot
be predicted simply by adding the wear rate in absence of corrosion to the corrosion
rate in absence of wear. The reason is that corrosion and wear do not proceed inde-
pendently and synergistic effects usually (but not always) result in accelerated mate-
rial degradation (tribocorrosion) [3]. In that respect, theoretical models have been
developed so far with respect to mechanical, chemical, and electrochemical factors and
19
their mutual interactions, and which can be tested under well-controlled experimental
conditions. In general, modeling has followed either an empirical or a mechanistic
approach [3]. The empirical approach is based on the independent measurement
of material loss due to wear and corrosion. These parameters are summed up and
compared to the material loss due to tribocorrosion. The difference between the two is
termed synergy (ΔWsyn). A general equation for this approach is of the form [7, 38, 39],

Wtot = Wmec + Wcorr + ΔWsyn (22)
where Wmec represents the material loss due to wear measured in the absence of
corrosion, and Wcorr is the material loss due to corrosion only without any influence
of mechanical wear.
Although, the empirical approach is technically feasible which allows for the
ranking and the performance of materials based on their resistance to tribocor-
rosion in engineering systems, it is still time-consuming, quite economically not
justifiable in the long-term, and furthermore, it integrates a synergy term, which
has no physical meaning [3].
The advantage of a mechanistic approach is that it leads for a better understanding
of the physical processes involved in tribocorrosion by incorporating the notion of
synergism into the mechanical and electrochemical terms [3]. Many factors can be
responsible for the mutual dependence of mechanical and chemical material removal
in a tribocorrosion system [3]. For example, local abrasion of the passive film can lead
to wear accelerated corrosion due to rapid dissolution of the locally depassivated metal
surface, followed by repassivation [40]. The abrasive action of hard oxide particles
formed by corrosion can accelerate the mechanical metal removal by wear [41]. The
plastic deformation of the surface layer of a rubbing metal can lead to a transfer of
material to the opposite body resulting in a reduction of the corrosive wear rate [42].
Therefore, it is important to distinguish material loss due to chemical or electro-
chemical oxidation (i.e., wear accelerated corrosion) from material removed due to
mechanical wear (i.e., mechanical material removal from the sliding contact) [3]. The
former arises from the fact that an asperity sliding on a material surface produces a
fresh wear track zone of clean bare material (i.e., metal), which is usually more suscep-
tible to corrosion than the same surface subjected to free corrosion under no mechani-
cal plastic contact or sliding conditions [3]. The effect of repeated sliding may cause the
removal of metal particles by asperities burrowing beneath the surface [42, 43].
Therefore, the overall wear volume due to tribocorrosion, Wtot, can be defined as
follow:

Wt ot= W chem(wac)  + Wm
  ec (23)
where Wchem(wac) is the electrochemical contribution to wear; it is termed wear

accelerated corrosion and it reflects the material loss due to corrosion in the pres-
ence of wear. Wmec is the mechanical wear, and it reveals the material loss due to
wear in the presence of corrosion, and which can be related to processes as that for
the formation-ejection of oxide debris, oxide layers or any corrosion products, and
plastically detached metal [3].
Wtot can be determined by measuring the volume of the wear scar post-
experiment using, for instance, a laser non-contact profilometry or by on-line
measurement of the rate of moving down of the counter-body (e.g., a pin) on the
surface wear track during sliding. The latter method has the advantage of recording
an instantaneous wear rate, but it would only be applicable if no significant amount
of solid reaction products (such as third body particles) accumulate in the contact
zone during the tribocorrosion experiment [3]. Under potentiostatic control,
20
the electrochemical term (Wchem(wac)) can barely be related to the anodic corro-
sion current (Ia,tribocorr) measured under mechanical sliding wear (occasionally by
subtracting the background current) using Faraday’s law. The amount of anodically
oxidized metal under such conditions is calculated as follows [14]:
Mq
W chem(wac) =  ____   
(24)
𝜌nF
where Wchem(wac) is the volume of the metal transformed by anodic oxidation

in a tribo-electrochemical test. q represents the electric charge produced, which
results mainly from the integration of the measured current Ia,tribocorr under sliding
wear conditions over the duration of the tribo-electrochemical test. M, n, and F are
the molar mass of the metal, the valence for the anodic oxidation reaction, and the
Faraday’s constant respectively. ρ is the density of the metal.
The foregoing equation is credible and independent of whether the anodic oxida-
tion leads to the formation of dissolved metal ions or solid reaction products, such as
oxide films [3].
It is worthwhile to note that few assumptions must be met in order for Eq. (24)
to be used [3, 40], namely:
• The measured current must be equal to the anodic partial current for metal
oxidation, which means that cathodic partial currents due to the reaction of
oxidizing agents must be negligible. This can be performed by anodic polariza-
tion into the passive potential region.
• The charge number “z” for the oxidation reaction must be known [40, 42].
The mechanical wear (Wmec) is taken as the difference between the total wear
volume Wtot and the chemical wear volume Wchem(wac) determined from the electric
charge.
21
References
[1] Landolt D, Mischler S. [10] Kruger J. Cost of metallic corrosion.

Tribocorrosion of passive metals In: Revie RW, editor. Uhlig’s Corrosion
and coatings. Oxford, Philadelphia: Handbook. 2nd ed. New York: Wiley;
Woodhead Publishing Limited; 2011. 2000. pp. 3-10
ISBN: 978-1-84569-966-6
[11] Burwell JT. Survey of possible wear
[2] Celis JP, Ponthiaux P, editors. mechanisms. Wear. 1957;1:119-141
Testing tribocorrosion of passivating
materials supporting research and [12] Frankel GS. Electrochemical
industrial innovation. In: Handbook techniques in corrosion: Status,
EFC 62. Leeds, UK: Maney Pub; 2012. limitations, and needs. Journal of ASTM
ISBN: 9781907625202 International. 2008;5:101241. DOI:
10.1520/JAI101241
[3] Berradja A. Metallic glasses for
triboelectrochemistry systems, [13] Frankel GS, Rohwerder M.
Chap. 5. In: Huang H, editor. Metallic Electrochemical techniques for
Glasses-Properties and Processing. corrosion. In: Encyclopedia of
London, UK: Intech Open; 2018. ISBN: Electrochemistry. Weinheim Germany:
978-953-51-6208-7 Wiley VCH; 2007
[4] Uhlig HH. Mechanism of fretting [14] Berradja A, Déforge D, Nogueira

corrosion. Journal of Applied RP, Ponthiaux P, Wenger F, Celis JP.
Mechanics. 1954;21:401-407 An electrochemical noise study of
tribocorrosion processes of AISI 304L in
[5] Waterhouse RB. Fretting Corrosion. Cl− and SO42− media. Journal of Physics
Oxford: Pergamon; 1972. pp. 182-196 D: Applied Physics. 2006;39:3184-3192
[6] Matsumura M, editor. Erosion- [15] Wu P-Q , Celis J-P. Electrochemical

Corrosion: An Introduction noise measurements on stainless steel
to Flow Induced Macro-Cell during corrosion-wear in sliding
Corrosion. U.A.E., Japan: Bentham contacts. Wear. 2004;256:480-490
Science Publishers; 2012. DOI:
10.2174/97816080535131120101. ISBN: [16] Trenthewey KR, Camberlain J.
978-1-60805-497-8 Corrosion for Science and Engineering.
2nd ed. United States: Longman Group
[7] Madsen BW. Measurement of Limited; 1995. ISBN: 978-0582238695
erosion-corrosion synergism with
a slurry wear test apparatus. Wear. [17] Frankel GS, Landolt D.
1988;123:127-142 Fundamentals of corrosion. In:
Encyclopedia of Electrochemistry.
[8] Landolt D. Corrosion and Surface Weinheim, Germany: Wiley-VCH
Chemistry of Metals. Boca Raton, FL: Verlag GmbH & Co. KGaA; 2007. ISBN:
EFPL Press, Taylor and Francis Group, 9783527302505
LLC; 2007, Chap. 10. pp. 415-460
[18] Roberge PR. Handbook of Corrosion
[9] Koch GH, Brongers MPH, Thompson Engineering. New York: McGraw-Hill;
NG, Virmani YP, Payer JH. Corrosion 2000. p. 1140. ISBN: 978007-076516-2
Costs and Preventive Strategies in the
United States, Supplement to Materials [19] Frankel GS, Landolt D.
Performance, July 2002. Report No. Thermodynamics of electrolytic
FHWA-RD-01-156; Federal Highway corrosion. In: Encyclopedia of
Admin., McLean, VA; 2002 Electrochemistry. Weinheim, Germany:
22
Wiley-VCH Verlag GmbH & Co. KGaA; Friction and Wear. Metals Park, OH:
2007. ISBN: 9783527302505. DOI: American Society of Metals; 1980. p. 73
10.1002/9783527610426
[30] Quinn TFJ. Review of oxidational
[20] Pourbaix M. Atlas of wear, Part I. Tribology International.
Electrochemical Equilibria in Aqueous 1983;16(5):257-270
Solutions. Houston, TX: NACE
International; 1974 [31] Welsh NC. The dry wear of steel.
Part I. Philosophical Transactions of the
[21] DeBethune AJ, Loud NAS. Standard Royal Society A. 1965;A257:31-50
Aqueous Electrode Potentials and
Temperature Coefficients at 25°C, [32] Czichos H, Beeker S, Lexow J.
Clifford A. Skokie, Illinois: Hempel; 1964 International multilaboratory sliding
wear tests with ceramics and steel
[22] Celis J-P, Ponthiaux P, Wenger (VAMAS 2nd round robin). Wear.
F. Tribo-corrosion of materials: 1989;135:171
Interplay between chemical,
electrochemical, and mechanical [33] Berradja A, Bratu F, Benea L,
reactivity of surfaces. Wear. Willems G, Celis J-P. Effect of sliding
2006;261(9):939-946 wear on tribocorrosion behaviour of
stainless steels in a Ringer's solution.
[23] Bockris JO’M, Reddy AKN. Modern Wear. 2006;261:987-993
Electrochemistry. New York: Plenum
[34] Mohrbacher H, Celis JP, Roos JR.
Press; 1970
Laboratory testing of displacement
[24] Revie RW, Uhlig HH. Kinetics:
and load induced fretting. Tribology
Polarization and corrosion rates. In: International. 1995;28:269-278
Corrosion and Corrosion Control. 4th
[35] Huq Z, Celis J-P. Expressing
ed. Hoboken, New Jersey: John Wiley &
wear rate in sliding contacts
Sons, Inc.; 2008. ISBN: 9780470277270
based on dissipated energy. Wear.
2002;252:375-383
[25] Frankel GS, Landolt D. Kinetics of
electrolytic corrosion. In: Encyclopedia [36] Fouvry S, Kapsa P, Vincent
of Electrochemistry. Weinheim, L. Quantification of fretting
Germany: Wiley-VCH Verlag GmbH & damage. Wear. 1996;200:186-205
Co. KGaA.; 2007. ISBN: 9783527302505
[37] Matveevsky RM. The critical
[26] Diomidis N, Celis JP, Ponthiaux temperature of oils with point and line
P, Wenger F. A methodology for the contact machines. Transactions ASTM.
assessment of the tribocorrosion 1965;87:754
of passivating metallic materials.
Lubrication Science. 2009;21(2):53-67 [38] Watson SW, Friedersdorf FJ,
Madsen BW, Cramer SD. Methods of
[27] Archard JF. Contact and rubbing of measuring wear-corrosion synergism.
flat surface. Journal of Applied Physics. Wear. 1995;181-183:476-484
1953;24(8):981-988
[39] ASTM Standard: G119. Standard
[28] Rabinowicz E. Friction and Wear of guide for determining amount of
Materials. 2nd ed. New York: John Wiley synergism between wear and corrosion.
& Sons, Inc.; 1995. ISSN: 0021-8936 In: Annual Book of ASTM Standards
Vol. 03.02. Wear and Erosion, Metal
[29] Moore MA. Abrasive wear. In: Corrosion. West Conshohocken, PA:
Rigney DA, editor. Fundamentals of ASTM; 2001
23
[40] Mischler S, Debaud S, Landolt D.

Wear-accelerated corrosion of passive
metals in tribocorrosion systems.
Journal of the Electrochemical Society.
1998;145:750-758
[41] Stachowiak GW, Batchelor AW.

Corrosive and Oxidative Wear, Chap. 13.
In: Tribology Series. Vol. 24. 1993.
pp. 637-656. ISBN: 978-0-444-89235-5
[42] Zambelli G, Vincent L. Matériaux et

Contact, Une Approche Tribologique.
Lausanne: Press Polytechniques et
Universitaires Romandes; 1998
[43] Ponthiaux P, Wenger F, Drees D,

Celis JP. Electrochemical techniques
for studying tribocorrosion processes.
Wear. 2004;256:459-468
24
Chapter 09
Electrochemical Techniques for

Corrosion and Tribocorrosion
Monitoring: Methods for the
Assessment of Corrosion Rates
Abdenacer Berradja
Abstract
The corrosion mechanism taking place in an aqueous phase with or without

mechanical contact is electrochemical in nature. The electrochemical signal is one of
the primary sources of information that relates to behavior in potential, current,
and electrical charge of a corroding electrode. It arises from processes that cause
corrosion and other electrochemical reactions. In a sliding contact in an ionic elec-
trolyte medium, electrochemistry is more likely to interfere with the tribological
behavior of tribocorrosion systems. In recent years, attempts by researchers have
been made to control the material loss by electrochemical methods for various
engineering systems. Applied online for monitoring in-situ uniform, localized, gal-
vanic, or more forms of corrosion, such techniques are very convenient means to
measure corrosion rate of materials. Such methods can also be used in different
ways to evaluate their ability to protect materials (as inhibitors, protective layers,
coatings). In this chapter, theoretical and experimental applications, fundamental
aspects, limits of the electrochemical techniques for corrosion, and tribocorrosion
monitoring are presented. Standards developed, so far, by various standardization
organizations are reported. Fundamentals of traditional and advanced corrosion
methods are described, focusing on their advantages, i.e. sensitivity to low
corrosion rates, short experimental duration, and well-established theoretical
understanding.
Keywords: corrosion methods, tribo-electrochemistry, tribocorrosion,

electrochemical impedance spectroscopy, electrochemical noise analysis, linear
polarization resistance, Tafel extrapolation method
1. Application of electrochemical techniques for determining corrosion

rates
In the section below, practical examples are described of how a number of

electrochemical techniques could be used to forecast corrosion or tribocorrosion
behavior in practical case studies. The focus is on laboratory tests for rapid corro-
sion or tribocorrosion tests. The examples do not provide bit-by-bit procedures for
screening most or all potentialities. Also, the discussion is not about how to set up
and conduct electrochemical corrosion or tribocorrosion experiments. Such
1
information can be readily found in instruction guidelines manual or standard

references [1–17]. The accent is put on the interest and validity of combination
techniques to provide a better understanding of the corrosion process and more
reliable predictions.
1.1 Linear polarization resistance (LPR)
The concept of “polarization resistance” has presumably been initiated by

Bonhoeffer and Jena in 1951 [18]—a subsequent to Wagner and Traud’s works
[19, 20]. In their study of the electrochemical behavior of iron samples of different
carbon contents, they found that the slope of the polarization curve, i.e., the rate of
potential change E with external current i, at the corrosion potential (or open-
circuit potential of a mixed electrode), was low for some iron samples and large for
others. Defining this slope as “polarization resistance,” RP, as a result of Lange’s
suggestion, it was found that there was an unambiguous correlation between the
polarization resistance and the corrosion rate, whereas no correlation was found
between the carbon content and the rate of corrosion.
Subsequently, Stern and Geary [21] were the first authors to theoretically estab-
lish a linear relationship between the polarization resistance and the corrosion rate
based on the kinetics of electrochemical reactions (i.e., corrosion current at open-
circuit conditions) and the concept of mixed potential theory, first formulated by
Wagner and Traud in 1938 (i.e., parameters of the cathodic and anodic E/i rela-
tions) [19]. The advantages and limitations of their method have been discussed in a
series of published articles [19, 21, 22], and the linearity of the slope of current-
potential plot around the corrosion potential has been verified by experimental
evidence, thereby avoiding the problem of large current densities. Their theory has
been experimentally supported by other authors [19, 21, 22] for different materials
and under a variety of environmental conditions. From the 1960s, plenty of publi-
cations [23, 24] reported on the use of the polarization technique, which quickly
became one of the main electrochemical techniques routinely adapted to rapid
corrosion rate measurements, a condition necessary to its success in industrial
monitoring corrosion operations.
For a system in which electrode processes involve a slow reaction step at the
electrode surface, the rate of reaction is limited by activation overvoltage; the
relationship between the reaction rate, or net current density i, and the driving
force for the reaction, or potential E, is given by the Butler-Volmer equation.
This equation relates i, for a single electrode process, such as Eq. (1) to E by the
formula (2),
Fe $ Fe2þ þ 2e (1)

αnFη ð1 αÞnFη
i ¼ i0 exp exp
RT RT
(2)
αnFðE Erev Þ ð1 αÞnFðE Erev Þ
¼ i0 exp exp
RT RT
where η is the overpotential, i0 the exchange current density (rate of either the
forward or reverse half-cell reaction) at the equilibrium potential Erev, α the transfer
coefficient (usually close to 0.5, but must be between 0 and 1), and n the number of
electrons transferred.
The graphical representation of the Butler-Volmer equation, as shown in
Figure 1, is called the polarization curve.
2
Electrochemical Techniques for Corrosion and Tribocorrosion Monitoring: Methods…
Figure 1.
Current density (i)-overpotential (η) curves for the system O + e $ R at 25°C. α = 0.5, il,a = il,c = il. Partial
current densities: ia, ic (dashed line), il limit current density (horizontal line), and RP the polarization
resistance (circle).
Stern and Geary’s theory [21] is based on a simplified corrosion process assum-
ing that only one anodic reaction and one cathodic reaction are involved during the
corrosion process. It is therefore inevitable that erroneous results occur when the
corrosion process involves more than one anodic or cathodic reaction. To address
this problem, Mansfeld and Oldham [25] presented a modification of the
Stern-Geary equation by including more than one oxidation and one reduction
reaction in a complicated corrosion process. The current-overpotential relationship
at electrodes is set by a number of complex physical and chemical phenomena based
on experimental conditions. The reactions occurring at the electrode/electrolyte
interface are heterogeneous chemical processes that may involve elementary
electron-transfer steps (one or more steps) over the electrochemical double layer,
ion-transfer, potential independent or chemical steps, etc.
It is well known that the electrochemistry of corroding metals involves two or
more half-cell reactions. Suppose there is a simple corrosion system, such as an iron
metal (a corroding working electrode) immersed in a sulfuric acid solution, in
addition to Eq. (1), the following half-cell reaction (Eq. (3)) also occurs:
H2þ þ 2e $ H2 (3)
The dissolution of Fe takes place in the acid electrolyte. At equilibrium, the total
anodic rate is equal to the total cathodic rate. In this case, the net rate of either Fe
dissolution or hydrogen evolution can be measured at the electrode potential of the
steady-state freely corroding condition. This potential refers to the corrosion
potential Ecorr, which lies between the equilibrium potentials of the two individual
half-cell reactions. At Ecorr, the net rate corresponds to the uniform corrosion rate,
icorr, at free corrosion condition. In such system, the relationship between the
overpotential (η, applied potential minus corrosion potential) and the current
(flowing between the working electrode and the auxiliary counter electrode) is
governed by the fundamental Butler-Volmer equation given as follows:
3

αnFη ð1 αÞnFη
i ¼ i0 exp exp
RT RT
(4)
αnFðE Ecorr Þ ð1 αÞnFðE Ecorr Þ
¼ i0 exp exp
RT RT
In Figure 1, the linear relationship between the polarization resistance and the
corrosion rate can be easily illustrated graphically. In the small region near the
corrosion potential, Ecorr, only a very small perturbation potential, usually less than
30 mV (typically 10 mV), is applied above or below the corrosion potential,
yielding a linear relationship between the overpotential (η = E Ecorr) or the
polarization from the corrosion potential and the current. Due to this smooth
excitation, the LPR technique is not expected to interfere with corrosion reactions.
The slope of that linearized curve (i E) is defined as the polarization resistance,
RP, of a corroding electrode (in ohms cm2 if the current density is plotted or in
ohms if the current is plotted), which is mathematically interpreted as

∂η
RP ¼ (5)
∂i jEEcorr ¼0
where i is the current density corresponding to a particular value of E.

The corrosion current, Icorr, can be calculated when the overpotential approaches
zero and is related to RP as follows:
1 ba bc
Icorr ¼ : (6)
Rp 2:303ðba þ bc Þ
where ba and bc are the so-called anodic and cathodic Tafel slopes or Tafel
parameters, respectively (cf. infra). The corrosion current density, icorr, can thus be
calculated from Eq. (6) if RP and Tafel constants (ba and bc) are known.
ASTM G59 describes an experimental procedure required to carry out polariza-
tion resistance measurement [10]. In agreement with this standard, the potential
should be scanned from 30 mV to +30 mV of the corrosion potential at a rate of
0.167 mV s1.
Many of the foregoing determined corrosion key parameters are based on
empirical observations. As with any empirical method, due to the high number of
factors involved in a corrosion or tribocorrosion system (e.g., environmental
changes, temperature, pH, reagent as chloride ions, pressure, specimen geometry,
test setup configuration, etc.), it is not uncommon to observe that the values of ba,
bc, and RP are influenced by these operational parameters and are therefore subject
to change. Of significance, the slope generated from the i–E curve around the
corrosion potential may not be linear and may or may not be symmetrical in the
anodic and cathodic regions. The symmetry of the curve (i–E) at the point of
equilibrium or at open-circuit potential is obtained only when ba and bc are equal.
These values are required for computing the corrosion current and are usually
determined by the Tafel extrapolation method (cf. infra).
It is worthy to note that the measurements of Rp can be derived potentiody-
namically or by the method of stepwise potentiostatic polarization or by anodic step
pulse method. In the potentiodynamic method, the potential is swept at a constant
rate (typically 60 mV/h) from the active (cathodic) direction to the noble (anodic)
region passing through the corrosion potential while tracking the current density
continuously. More information regarding this method can be found elsewhere [3].
4
Similarly, in the step pulse method, an applied potential is incremented in steps of

5 or 10 or 20 mV, starting from a negative potential moving to a positive
potential through the corrosion potential. The value of Rp is determined from the
slope of the plot of the potential-current. Prior to the tests, a steady-state corrosion
potential is required. The open-circuit potential of the corrosion system is first
measured, typically for 1 hour (during which time the corrosion potential of most
electrodes is stabilized) or until it reaches a stationary state.
Progress is made through competitive advantages between different measure-
ment techniques, including a rapidity in current measurement (generally rather
quickly in a few minutes), where only a lower excitation is required (less than
30 mV, generally 10 mV), so that the corrosion rate would not be affected by
corrosion reactions, an easy measurement of low corrosion rates (less than 0.1 mil/
year (2.5 μm/year), and measurements taken repeatedly, the LPR technique can be
considered as a nondestructive technique and used for online corrosion monitoring
of uniform corrosion rates useful for the field.
The main drawback of this technique is that the Tafel parameters must be
known in advance in order to convert the polarization resistance into the corrosion
rate. To tackle this problem, several numerical methods [8, 9, 26–28] have been
proposed to obtain both Tafel parameters and corrosion rate from the same polari-
zation measurement in the vicinity of the corrosion rate. Nevertheless, the success is
limited since the Tafel parameters thus determined will not be very accurate, which
may compromise the nondestructive nature of the LPR technique. Another
disadvantage of the LPR method lays in the fact that it will not work properly in
low conductive media. Basically, the LPR technique can only be used to determine
uniform corrosion rates; it can hardly provide information about localized
corrosion.
1.1.1 Illustrative examples of the application of LPR in corrosion and tribocorrosion

systems
A modified electrochemical noise technique, namely, electrochemical emission

spectroscopy (EES) [29], offers one of the most convincing examples of the appli-
cation of the LPR technique in tribocorrosion [30]. Indeed, the analysis of noise
data in a potential-current plane shows the transposition of the statistical resistance
due to electrochemical noise to the resistance due to linear polarization. Noise
resistance is often considered equivalent to the polarization resistance, RP [31–33].
The noise resistance, RN, calculated using a method proposed by Eden et al. [33], for
mild steel passive alloy in 0.05 M H2SO4 (corrosion under activation control), is of
the order of 48 Ω without any sliding contact. The LPR measured on this mild steel
after EES monitoring is shown in Figure 2a. The comparative value of RP obtained
by the LPR technique is 50 Ω. The RN value obtained using the EES technique is
therefore very close to the RP obtained by the LPR technique. Under tribocorrosion
conditions (5 N normal force, 10 Hz sliding frequency, 200 μm peak-to-peak dis-
placement amplitude), the plane plot of the potential-current data under steady-
state wear-corrosion regime shows a best-fit line through the data points with a
positive slope of 54 Ω (see Figure 2b), which roughly corresponds to RN (48 Ω) or
RP (50 Ω in Figure 2a). Notwithstanding, no attempt has been made to relate these
resistance measurements with the breakdown (i.e., depassivation) or the buildup of
any kind of passive film (i.e., repassivation) on the mild steel surface subjected to
either a mechanical stimuli (e.g., active-passive wear track zone area or metastable
pit area) or in the absence of wear (free corrosion), characteristic phenomena of
localized corrosion.
5
Figure 2.
LPR measurements on the mild steel in 0.05 M H2SO4 solution; (a) under free corrosion state, (b) under wear-
corrosion steady-state phase. Reproduced from [30] with permission from Wiley Online Library.
1.2 Tafel extrapolation method
In 1905, Julius Tafel [34] presented the experimental relationship between the
current, I, and the overpotential, η, during an electrocatalytic test of the reduction
reaction of hydrogen (i.e., protons to form molecular hydrogen) on a number of
electrode metals such as Hg, Sn, Bi, Au, Cu, Ni, and so on:
η ¼ a þ b log I (7)
where the overpotential η is defined as the difference between the potential of

the working electrode, E, and the equilibrium potential.
The existence of a linear relationship between E and log I has been demonstrated
when the electrode is polarized at sufficiently large potentials, and far away from
the corrosion potential both in anodic and cathodic directions [34], as can be seen in
the polarization curve depicted in Figure 3. The portions in which such relation-
ships prevail are called Tafel portions or Tafel regions.
This can be mathematically expressed as

2:303η 2:303η
I ¼ Icorr exp exp
ba bc
(8)
2:303ðE Ecorr Þ 2:303ðE Ecorr Þ
¼ Icorr exp exp
ba bc
where Ecorr is the corrosion potential, E the applied potential, η the overpotential
(difference between E and Ecorr), I the current, Icorr the corrosion current, and ba
and bc are the Tafel constants or Tafel parameters derived from E log I plots as the
anodic and cathodic slopes in the Tafel regions, respectively.
Extrapolating from the Tafel portions of either anodic or cathodic or both, an
intersection point is obtained at Ecorr, from which Icorr is readily available from the
log I axis. Therefore, it is possible to obtain simultaneously the corrosion current,
Icorr, and the Tafel parameters (i.e., ba and bc) from this method.
In order to obtain the Tafel portions in the anodic and cathodic regions, the
electrode has to be polarized far away from its corrosion potential, e.g., 250 mV
away from Ecorr. Eq. (8) can be rearranged, as appropriate, to choose one single
polarization direction, either anodic or cathodic way.
At sufficiently larger values of η (100 mV ≤ η ≤ 500 mV), in the anodic direction
(i.e., η = ηa), Eq. (8) can be rearranged as,
6
Figure 3.
Electrode kinetics as expressed by the Butler-Volmer equation, plotted in a semilogarithm scale or Tafel plot
showing that the corrosion current density can be obtained from the intercept.
I
ηa ¼ ba log (9)
Icorr
Likewise, at sufficiently larger values of η, in the cathodic direction (i.e., η = ηc),

Eq. (8) can be modified as,
I
ηc ¼ bc log (10)
Icorr
The polarization curve can be measured either dynamically or statically (either

in the potential-controlled mode or in the current-controlled mode). The dynamic
polarization techniques can be carried out relatively fast, but the drawback is that
the Tafel parameters are scanning rate dependent. The static polarization tech-
niques may produce better Tafel parameters, but they are very time-consuming.
Tafel extrapolation measurements can be performed either by the
potentiodynamic method or by the stepwise potentiostatic polarization method
[35]. As in RP measurements, in both methods, corrosion potential is first measured,
typically for 1 h (during which time corrosion potentials of most electrodes are
stabilized) or until it stabilizes. After that, the potential step—at increments of 25
or 50 or 100 mV, every 5 min, recording the current at the end of each 5-min
period—is applied (potential-step method), or the potential is scanned at a constant
rate (typically 0.6 V/h) (potentiodynamic method). In both methods, the
7
experiment is started at the corrosion potential, and the cathodic polarization is first
conducted by applying an overpotential of approximately 500 mV or until gas
evolution (e.g., hydrogen) occurs at the electrode, at a constant rate of 0.6 V/h.
Following, the corrosion potential is measured again (typically for 1 h), and then
anodic polarization is conducted by applying an overpotential so that the potential
at the end of the anodic polarization reaches +1.6 V versus SCE. Tafel plots are
generated by plotting both anodic and cathodic data in a semilog paper as E-log I.
From the plot, three values are determined: the anodic Tafel slope, the cathodic
Tafel slope, and Icorr (from back-extrapolation of both anodic and cathode curves to
Ecorr). The main advantage of this method is that it provides a simple, straightfor-
ward method to determine Tafel parameters, namely, ba and bc.
The disadvantage of the Tafel technique is that large current densities are often
required to generate the complete Tafel plots. The use of large current densities can
alter the surface conditions of the specimen (e.g., permanent change or surface
damage), thereby distorting the results and increasing complications due to mass
transport and uncompensated electrolyte resistance. The measurement of current
density over a wide potential range may also distort the results if the adsorption of
some species is potential dependent. Since this method applies a large overpotential
to the metal surface (e.g., anodic polarization), therefore, the technique is rather
destructive and can hardly be used for online corrosion monitoring purposes and in
particular in the field. An ASTM G5 standard provides a procedure for constructing
an anodic polarization plot [36]. However, it does not supply a method to construct
a cathodic polarization plot nor a procedure to determine the corrosion current by
the Tafel extrapolation method.
1.3 Corrosion rate determination by electrochemical noise analysis (ENA)
Many of the electrochemical techniques, among those described earlier, measure

the electrochemical response of the corrosion system following the application of an
external disturbance. In the last 50 decades, an original concept has emerged where
it was possible to use the inherent noise of the electrochemical system as a stimulus
to measure both potential and current changes [31, 32, 37–43]. Broadly, measured
inconsistently in corrosion experiments, the electrochemical noise was first consid-
ered an unwanted or undesirable artifact that comes from measuring instruments or
pickups from the environment. This is why this misleading name was cast. This sort
of noise can be easily observed during corrosion potential measurements because
the measured corrosion potential always fluctuates slightly, usually randomly. Ran-
dom fluctuations result from stochastic processes [44], and, considering each
chemical process is stochastic in nature, it generates noise.
Since the pioneer work of Iverson [45], who has reported a relation between the
frequency or amplitude of the electrochemical noise and the inhibiting power of the
environment for a number of metals and alloys (e.g., aluminum alloys, magnesium,
mild steel, etc.), there has been a growing interest toward the measurement of
electrochemical noise and its peculiar relationship with localized corrosion [11, 12,
31, 32, 41, 46–51]. In this respect, electrochemical noise measurements obtained
from the analysis of corrosion potential or current fluctuations provide a new
approach to the study of corrosion processes in reactive environments such as
aqueous media or hot aggressive gases or even under the effect of mechanical
stimuli, e.g., tribocorrosion. Indeed, mechanical friction of solids in contact with a
corrosive environment is likely to generate (i) noise due to stochastic contact
between randomly distributed surface asperities and (ii) noise due to the synergy of
wear-corrosion processes resulting from the activity of the surfaces and controlled
by the response of potential-current transients and the configuration of the wear
8
track area, coordinated by the coupling effects of wear and corrosion in the tribo-
electrochemical cell. Among the possibilities offered by the measurement of elec-
trochemical noise sources during an electrochemical or a tribo-electrochemical sys-
tem, the following can be retained: adsorption–desorption processes, e.g., formation
and detachment of gas bubbles; fluctuations in the mass transport rate and in
temperature; interfacial nucleation and growth processes; degradation processes
due dielectric film disruption; kinetics of atom exchange at the surface sites, e.g.,
Johnson’s noise in the interfacial impedance; and so on.
While multiple case studies on electrochemical noise have been regularly
reported in recent years, even greater progress is possible, with the scope for
increased breakthrough in science and technology (e.g., novel materials, precision
tools on macro-to-nanoscopic scales, availability and intelligent use of these mate-
rials and tools, and so on). In particular, the main focus of these investigations is to
promptly obtain in situ mechanistic information on the repassivation and break-
down of passive films and to monitor any process associated with confined corro-
sion and/or tribo- or bio-tribocorrosion [46, 47, 51]. It has been, indeed, suggested
that the noise is caused by film breakdown and repassivation processes, and given
the dynamic competition between these two processes, pitting will initiate. However,
the foundation for using electrochemical noise analysis for determining the corrosion
rate of an electrode is still a subject of debate within the scientific community.
Indeed, the fundamental approach is not as robust as that of other techniques. On the
other hand, the advantage of the noise analysis is that it is not necessary to apply any
external polarization and the system is in natural corrosion conditions. This renders
the technique as nondestructive and nonintrusive, capable of monitoring basic
changes in an electrochemically active system. This makes it particularly suitable for
online corrosion monitoring in the laboratory, especially for localized corrosion
monitoring, detection of general corrosion, crevice investigation, stress corrosion
cracking [12, 52, 53], fretting corrosion, or be used in the assessment of anti-corrosive
organic coatings, and other surface inhomogeneity case studies [43, 46, 47]. Several
approaches extend the use of electrochemical noise measurements in both pilot plant
and field facilities, its use is not merely limited to the foregoing phenomena, but its
development is justified especially when measurements are performed in systems
with very low conductivity, where, for e.g., the impedance technique fails because of
the loss of signal in the high resistance of the solution (cf. infra).
1.3.1 Instrumentation for electrochemical noise measurements in corrosion and

tribocorrosion systems
Electrochemical noise is a generic term used to describe the naturally occurring

fluctuations in potential and current, which is due to spontaneous changes in elec-
trode kinetics and mechanisms [33]. When applied to corrosion studies, electro-
chemical noise may be redefined as the spontaneous fluctuations observed in
potential and current at the free corrosion potential. The electrochemical noise can
thus be classified into potential noise and current noise. There are three major
possible modes for measuring potential and current noise in a corrosion system, but
the most common mode uses two nominally identical working electrodes, WE1 and
WE2 (WE1 as the corroding metal and WE2 as a counter electrode), and a noise-free
reference noble electrode, RE [33] (see Figure 4a). The current flowing between
the two working electrodes is measured by a zero-resistance ammeter (ZRA), and
their potential is monitored versus the reference electrode through a voltmeter (V)
under free corrosion conditions. The two other leftover modes are two identical
working electrodes WE1 and WE2 with a bias potential [54] (not shown here) and
one WE coupled to a micro-counter electrode (MC, e.g., Pt wire tip) [29, 46, 47, 55]
9
Figure 4.
(a) Schematic view of a tribocorrosion experimental setup. Potential and current are measured on a working
electrode (WE1) sliding against a counterbody ball (unidirectional reciprocating sliding, sphere-on-flat) with
respect to a RE reference electrode (Ag/AgCl (3 M KCl)) via a V, high-impedance voltmeter, and CE (WE2)
via a zero-resistance ammeter (ZRA), respectively. FN, normal force; FT, tangential force; f, sliding frequency;
D, displacement amplitude. (b) Schematic view of a tribocorrosion experimental setup. Potential and current
are measured on a working electrode (WE) sliding against a counterbody ball (unidirectional reciprocating
sliding, sphere-on-flat) with respect to a RE reference electrode (Ag/AgCl (3 M KCl)) via a V, high-impedance
voltmeter, and CE micro-cathode (MC) via a zero-resistance ammeter (ZRA), respectively. FN, normal force;
FT, tangential force; f, sliding frequency; D, displacement amplitude.
(see Figure 4b). This last mode of electrochemical noise analysis seems to be a
promising way to obtain unambiguous estimates of the rate of chemical wear in a
tribocorrosion experiment as evidenced by some recent investigations [46, 47, 51]
but also to predict the corrosion rate of localized corrosion in a free corroding
system [29, 31, 32, 37–45, 47–50, 56].
1.3.2 Electrochemical noise data management process
The overall approach to analyzing noise data is the assessment of mechanistic

information from either time-domain analysis, frequency-domain analysis, or both,
using statistical methods [44, 57, 58]. If the information in the time-domain records
is evident, time-domain analysis is sufficient to distinguish different processes (e.g.,
different forms of corrosion).
In what follows, one assumes that all various types of noise are excluded from
this description, with the exception of the thermal noise. Except for the last noise,
all other noise sources can be minimized or eliminated using careful strategy within
reasonable limits of materiality. Effective and convenient ways include the removal
of unwanted environmental and instrumental noise from the electrochemical noise,
e.g., by shielding electrical connections/wires for coupling the electrodes to the
experimental apparatus, by using a Faraday cage to exclude electrostatic/electro-
magnetic influences, even by implementing analogue/digital filters to eliminate
systematic noise at frequencies different than the frequency of interest, and so on.
Guidelines for the calibration of noise measuring device can be found elsewhere
[13, 59].
1.3.3 Noise resistance
The basic quantitative approach is the time-domain analysis of the noise signal.
The noise resistance, RN, is defined as the ratio of the standard deviations of
potential/current noise signal time dependent, σ(t):
10
σ E ð tÞ
RN ¼ (11)
σ I ð tÞ
Eq. (11) implies that in the case where a low-driving force noise produces a high
current density noise between the two electrodes (WE1 and WE2), the yielding noise
resistance will be low. Noise resistance, RN, has been shown to correlate well with the
polarization resistance, RP, as determined by EIS for certain corrosion systems. This
latter being directly related to the corrosion current [14, 29, 60] is using the Stern-
Geary equation and Tafel slopes. Notwithstanding, much work has been devoted
trying to best match RN or the normalized RN (per unit of exposed surface area) to the
corrosion resistance or the corrosion rate [5, 14, 31, 32, 37–45, 48–50, 60]. Although
signal analysis in the time domain is well established, an approach based on spectral
analysis is gaining more and more importance in research laboratories. It consists of
transforming the potential and current noise fluctuations recorded in the frequency
domain using the Fast Fourier Transform (FFT) method [61].
The frequency range for which the FFT is commonly performed extends from 1
mHz up to 1 Hz. The spectral noise plots are similar to those of impedance plots.
The spectral noise resistance, RSN, is given by the ratio of the potential and current
FFTs at each frequency, and the limiting value, RSN0, can be used as a measure of
the corrosion resistance:

EFFT ð f Þ
RSN ð f Þ ¼ (12)
IFFT ð f Þ
The log–log plot of RSN versus f is similar to the impedance plot, and the spectral
noise resistance limit RSN0 is given by
R0SN ¼ lim RSN ð f Þ (13)

f !0
Another approach would be to examine the spectral noise response in terms of

power spectral densities (PSD). These latter are calculated from the FFT or using
the maximum entropy method (MEM) [62]. RSN is determined from the PSDs by
the relation (14):

EPSD ð f Þ 1=2
RSN ð f Þ ¼ (14)
IPSD ð f Þ
It has been shown that the use of a single data set of potential and current noise
[32] would yield identical values of RSN as calculated by either Eqs. (13) or (14). In
some cases, RSN0 is bound to RN or RP as,
RN ¼ RSN ð0Þ ¼ RP (15)
effective if the impedance of the two electrodes is identical and much higher
than the resistance of the test solution between them [5, 32, 63]. Experiments have
validated this relationship for several systems [5, 31, 63]. Nonetheless, there is no
agreement on the fundamental basis for the relationship between noise resistance
and corrosion rate.
1.3.4 Illustrative examples of the application of electrochemical noise in tribocorrosion

systems
Investigations into electrochemical kinetics make common point research

between tribocorrosion and corrosion. The study of localized phenomena of
11
depassivation and repassivation is essential to understand the mechanisms of

corrosion-wear as well as to reduce the material loss. The possibility of using the
electrochemical noise detection technique as a promising tool to study the electro-
chemical properties of well-controlled damaged surfaces has been widely considered
due to its nondestructive nature and its potential in online corrosion monitoring
applications. Time-spatially resolved measurements should provide more reliable
data on the electrochemical part of tribocorrosion. The noise analysis in relation to
depassivation-repassivation events randomly distributed in time and space can be
traced back to Oltra et al. [64]. The power spectral density (PSD) of the noise under
the impact of the jet particles was related to the Fourier transform of individual
repassivation transients obeying a Poisson distribution. Later, the application of
electrochemical noise analysis to tribocorrosion was reviewed. Investigations
involving PSD noise analyses on various tribo-electrochemical cells for passivating
materials were conducted by Ponthiaux et al. [65], by Déforge et al. [51], and in
more details by Berradja et al. [46, 66]. In this latter work, the noise spectra were
measured on AISI 304 L stainless steel versus corundum in a Ringer’s solution in a
pin-on-disk tribometer under stationary sliding-corrosion regime conditions, either
at open-circuit potential or at a controlled potential. The PSD of the current noise
has been interpreted as resulting from the overlap of the large number of discrete
repassivation transients at the contact junctions, including the double-layer charge
and the strong dependence of depassivation and repassivation kinetic rates of the
oxide surface film on the sliding frequency. This was consistent with the shift in the
PSD plots of the current noise fluctuations by about a decade when the sliding
frequency was varied from 0.1 to 1 Hz (see Figure 5). Similar findings were
obtained via Déforge et al. [51] by dividing open-circuit potential fluctuations to
the impedance of the electrode. A 1/f low-frequency noise is explained by a long-
term drift of the surface conditions. Only a minor influence of the applied normal
load was observed on the PSD plots, recommending reaching the limit rate of the
depassivation of the oxide surface film.
Application of the noise analysis to tribocorrosion offers the feasibility to record
in parallel the PSD of normal and tangential force fluctuations and their tie-in with
the current noise data (see Figure 6). Force fluctuations show an almost flat
Figure 5.
PSD record of current fluctuations measured on AISI 304L during continuous sliding-corrosion test in Ringer’s
solution at 0.1 Hz (gray) and 1 Hz (black) and at a constant normal load of 5 N. Reproduced with permission
from IOPScience [46].
12
Figure 6.
PSD record of tangential (gray) and normal (black) force components measured on AISI 304L during
continuous sliding-corrosion test in Ringer’s solutions at a normal load of 20 N and at 1 Hz frequency.
Reproduced with permission from IOPScience [46].
spectrum (white noise) as expected following short random mechanical interactions

between colliding asperities, whereas the current noise is consistent with finite
time-constant transient responses to the depassivation events.
1.4 Corrosion forecast by electrochemical impedance spectroscopy (EIS)
The EIS has matured greatly over the past 25 years as a tool in corrosion
protection research and has proven to be one of the most useful electrochemical
characterization techniques presently available. In practice, EIS has become a stan-
dardized research tool for corrosion prediction [15] and found wide applications in
both fundamental and applied laboratory researches [67]. Recent applications in
tribocorrosion reflect the steady progress of the EIS method in terms of research
and development [62]. Compared with the LPR technique, the EIS technique is
considered more advanced, since it has the ability to study high-impedance
systems, in which the conventional LPR technique has failed, such as coatings
and linings [16, 68], high pure water, and organic coating/metal systems [69] or
corrosion in a low conductive solution [70]. This technique is especially useful for
13
evaluating corrosion inhibitors [24, 71], analyzing the corrosion mechanisms

[72, 73], and so on.
A significant number of tutorials have been addressed on the EIS experimental
setup, the measurement methodology, and data analysis methods [27, 74–78]. The
technique has been of a great deal of concern to the extent that an ASTM standard,
i.e., ASTM G106-89, has been produced to provide the practitioner with a test
method to verify that the electronic equipment, the electrochemical cell, and the
spectrum generation algorithm impedance work properly [15].
1.4.1 Principle of the EIS technique
The EIS technique normally uses a typical three-electrode cell system controlled
by a potentiostat, similar to that used in the LPR technique. Unlike the previous
time-resolved techniques, where the current system response is either the conse-
quence of a large voltage perturbation from the steady-state condition (case of Tafel
extrapolation) or from a smaller perturbation (case of LPR method), in the EIS
approach, however, by applying a small varying perturbation over a range of fre-
quency, it is possible to probe the full response of the electrochemical system, and
not just the resistive components. In that respect, a small AC signal, i.e., alternating
potential or voltage V(ω) typically a sine wave of amplitude 10 mV of the corro-
sion potential, is applied over a wide range of frequency (typically from 105 down to
102 or 103 Hz) at a number of discrete frequencies (typically 5–10 frequencies per
decade), and the alternating current response, i(ω), is measured at each frequency,
ω (i.e., the ac polarization or angular frequency, ω = 2πf). For a linear system, the
current response signal will be a sine wave of the same frequency as the excitation
signal (voltage) but shifted in phase. This is transmitted to a frequency response
analyzer or a lock-in amplifier to calculate the impedance and phase shift. Full
frequency sweeps provide phase-shift information that can be used in combination
with equivalent circuit models to gain valuable information from the complex
interface of the corrosion system. The frequency-dependent impedance is deter-
mined by the relation: Z ðωÞ ¼ V ðωÞ=iðωÞ.
1.4.2 Electrode/electrolyte electrochemical interface circuit
Basically, the electrode/electrolyte interface is characterized by a separation of

charges resulting in the creation of parallel planes of electrical charges whose
behavior is similar to a circuit consisting of a capacitor and a resistor in parallel and
certainly not to a perfect capacitor. Indeed, the current flowing in a perfect capac-
itor would cease when the latter would be fully charged, hence the need to add a
resistor in parallel to let a weak current flow. An electrochemical interface can be
viewed as an electrical circuit, or called the equivalent circuit, composed of a
number of elements such as resistances (R), capacitances (C), and inductances (L)
[26]. Explanations of the EIS results are usually based on the equivalent circuit used.
Many software programs and packages are now available for fitting the impedance
spectra to analogous circuits [15], a strategy often used to analyze data. Further
information on the EIS measurements and instrumentation can be found elsewhere
[15, 17, 79, 80].
Not all the available proposed equivalent circuits to model electrochemical
interfaces can actually satisfy what is applied to a freely corroding system. In most
cases, the impedance corresponding to a simple corrosion process, under activation
control, can be represented by the well-known Randles’ [81] equivalent circuit (RC
circuit) which allows to describe the behavior of many electrochemical electrode/
electrolyte interfaces. A typical example is shown in Figure 7, where RS, RCT,
14
Figure 7.
A simple Randles-type equivalent circuit (RC).
and CDL represent labels for the solution resistor, the Faradaic charge transfer
resistor, and the double-layer capacitance, respectively. The capacity is associated
with the separation of charges at the electrode/electrolyte interface as in the case of
a working electrode having a surface film (e.g., AISI 304 stainless steel immersed
in a 0.5 M H2SO4 electrolyte), in which case the capacity of the equivalent circuit
can be associated with the capacity of the passive oxide surface film and the resistor
in parallel with the capacitor is considered as the charge transfer resistance, RCT (or
the polarization resistance, RP, under EIS-free corrosion conditions), while the ohmic
resistance in solution, RS, between the working electrode and the reference elec-
trode is in series with the parallel resistor and the capacitor. If the amplitude of the
perturbation signal is small enough (e.g., a voltage less than 20 mV), RCT can be
regarded as equivalent to the linear polarization resistance (RP).
The behavior of such an electrochemical interface can be described by Eq. (16):
Rp
Z ðωÞ ¼ Rs þ (16)
1 þ ðjωRP CDL Þβ
RCT or RP can be determined in several ways. A convenient way is to use the

Nyquist diagram. For the simple Randles-type equivalent circuit as shown in
Figure 7, the corresponding Nyquist diagram is displayed in Figure 8, in which a
perfect semicircle is observed. The high-frequency response is used to determine
the component of RS involved in the measurement. RS can be read directly from the
abscissa when the angular frequency ω (ω = 2πf) tends to be infinite (fmax or f ! ∞).
The total resistance (RP + RS) can also be read from the abscissa when ω approaches
zero (fmin or f ! 0). So, RP can be determined by subtracting the RS value from the
Figure 8.
The Nyquist diagram responding to the simple Randels-type equivalent circuit.
15
low-frequency measurement. The conversion of the polarization resistance into a

corrosion rate requires an independent empirical measurement of the Tafel slopes
using a potentiodynamic polarization method and/or harmonic distortion analysis
or otherwise taken from the literature. The double-layer capacitance, CDL, can also
be determined for a system exhibiting a behavior similar to that of a perfect RC
circuit from the values of RP and the maximum frequency, fmax, that corresponds to
the frequency of the point at which the imaginary component has a maximum
value, viz.:
1
CDL ¼ (17)
2πf max Rp
It is worth of note that in practice, f cannot really go as high as infinite; it is

inevitable that some extrapolation has to be made. Extrapolation at the high-
frequency limit usually presents few issues because the impedance becomes
nonreactive at frequencies as low as 10 kHz in most cases [82]. On the other hand,
reactance is still commonly observed at frequencies as low as 103 Hz [82]. There-
fore, special precautions must be taken to obtain reliable data and to avoid possible
artifacts [17, 83]. Furthermore, the measurement cycle time depends on the fre-
quency range used, in particular the low frequencies. For instance, a single-frequency
cycle at 103 Hz needs about 15 min of testing time. A high-to-low-frequency analysis
moving down to 103 Hz frequency likely requires more than 2 hours of scan time. In
order to perform a normal standard corrosion monitoring with the EIS technique,
assistance is needed to optimize the use of the high-frequency data and reduce
measurement time. There is a constant need to improve data processing and analysis
in order to minimize uncertainties and to allow the EIS technique becoming user-
friendly for corrosion monitoring in both laboratory and field facilities, though it
must be emphasized that the need for an easy-to-deploy field instrument has always
been an obstacle to online corrosion monitoring with the EIS technique.
An alternative to the impedance model in the Nyquist diagram involves the
conversion of the impedance into a complex number. The impedance can thus be
designated by an amplitude, |Z|, and a phase shift, ϕ, or by the sum of the real (Z0 )
and imaginary (Z″) components, such that,
Z ðωÞ ¼ Z 0 ðωÞ þ jZ”ðωÞ (18)
Both the log|Z| data and the phase angle ϕ are plotted against the angular fre-
quency, log ω, of the excitation signal, a format which substitutes for the Nyquist
diagram, i.e., the so-called Bode diagram. Figure 9 shows how the same data
(Nyquist plot) appears in a Bode plot format with respect to the equivalent circuit
of Figure 7.
Highest (ωH) and lowest frequencies (ωL) can be readily determined. As shown
in Figure 9, Z is independent of the frequency at ωH and ωL, limit values
represented by horizontal lines. From these lines, values of RS and (RS + RCT) can be
measured. This analysis forms the basis of the corrosion monitoring as proposed by
Tsuru et al. [74] to allow the determination of |Z| at each frequency in the horizontal
portions of the Bode diagram.
Sometimes, it is not convenient to perform impedance measurements at very
low frequencies (as in DC techniques such as linear polarization). However, it is still
possible to extrapolate the polarization resistance, RP, from the Bode diagram. In
Figure 9, the low- and high-frequency breakpoints (i.e., ωL and ωH, respectively)
can be determined from the 45° phase angle Bode diagram (see the pseudo-
Gaussian curve). The intersection point A can be determined from the log ωH
16
Figure 9.
Bode diagram with respect to the Randels-type equivalent circuit in Figure 7.
Figure 10.
A Randles-type equivalent circuit including Warburg impedance component, ZW.
and RS. By extrapolating from A toward the central linear portion of the |Z| curve,
a linear line can be determined. On this line, point B is obtained at log ωL. With the
projection of point B to the log|Z| axis, the total resistance (RS + RCT) can be
measured. In this way, RP can be determined. At intermediate frequencies, the
capacitor affects the response of the overall RC circuit.
The situation struggles when diffusion processes govern the corrosion behavior.
A convenient way to deal with this complication is to add a Warburg impedance.
The latter describes the impedance of the concentration and diffusion processes in
the equivalent circuit as shown in Figure 10.
The Warburg impedance, ZW, is given by the equation
σw σw
Z W ¼ pffiffiffiffi j pffiffiffiffi (19)
ω ω
where σw is the Warburg coefficient.

Eq. (19) implies that, whatever the frequency, the real and imaginary parts of
the Warburg impedance are equal and inversely proportional to σw ½
. In the Nyquist
plot, this impedance will result in a straight line at a constant phase angle at 45°, as
shown in Figure 10. However, the effect of the Warburg impedance can complicate
the correct estimate of the RP value in certain cases. Therefore, the impedance data
must be numerically adjusted to fit with the correct model to facilitate the extrac-
tion of the total resistance (RS + RP) from the abscissa or by using an appropriate
17
modeling software. However, the situation can readily become more complicated if
other effects, such as time-constant dispersion, adsorption processes, and so on, are
taken into account; the time-constant dispersion, which can be caused by inhomo-
geneities in the corroded surface, results in a depression of the semicircle [75, 76].
Adsorption, on the other hand, can reveal a second semicircle at low frequencies
[77]. All these effects can occur simultaneously [27], making the interpretation of
impedance data rather more difficult [78, 84] (Figure 11).
There is a need for an appropriate model equivalent circuit beyond the existing
model standards to remedy that shortcoming. An “appropriate” model is under-
stood not only as a good fit of the impedance data but also as a rational explanation
of the underlying corrosion mechanism. Moreover, the requirement of sophisti-
cated AC frequency generator and analyzer and the time needed to acquire the
complete impedance diagram (particularly in the range of low frequency) impose a
serious limitation in real-time corrosion monitoring applications. Other disadvan-
tages include a priori knowledge of the Tafel parameters in order to convert the
polarization resistance into a corrosion rate and the fact that it is too difficult to
detect and monitor localized corrosion, even if such applications have been
explored [85, 86].
Figure 11.
The Nyquist diagram responding to the equivalent circuit of Figure 10.
1.4.3 Illustrative examples of the application of EIS in corrosion and tribocorrosion

systems
Attempts were made to use the EIS technique in corrosion and corrosion-wear
monitoring of Fe-31% Ni electrode immersed in 0.5 M H2SO4 [87]. The
corresponding Nyquist impedance diagrams were recorded at an anodic potential of
675 mV/SSE (+100 mV/open-circuit potential) before and during sliding-
corrosion as shown in Figure 12. At this potential, the prevailing reaction is disso-
lution. At high frequency, under free corrosion and unloaded conditions, the
capacitive arc reveals the influence of the dielectric properties of the electrochemi-
cal double layer and the charge transfer due to electrochemical reactions. Under
18
Figure 12.
Nyquist plots recorded at E = 675 mV/SSE (I = 20 mA) on Fe—31% Ni in 0.5 M H2SO4 under free
(unloaded) and sliding conditions (against a corundum counterbody pin; 60 N normal force, sliding speed
0.031 m s1). Reproduced from [8] with permission from Elsevier.
sliding conditions, the size of the capacitive arc increases, suggesting an increase in
the transfer resistance and a decrease in the reactivity of the surface, consistent with
the effect of mechanical straining of the worn surface. At low frequency, however,
the inductive arc indicates the relaxation of the surface concentration of adsorbed
intermediate species involved in the dissolution mechanism. Under corrosion-wear
conditions, the kinetics of the dissolution process is apparently modified, as
revealed by the second inductive loop in the diagram. Given that not all of these
investigations have been concluded, a detailed explanation is not straightforward,
and further research is recommended. Although these impedance measurements
provide a convenient way to study the mechanism of electrochemical reactions
involved in tribocorrosion processes, still the interpretation of impedance records
during sliding-corrosion experiments is rather difficult because of the heteroge-
neous surface-state condition. Actually, a nonuniform distribution of the electro-
chemical impedance on the steel surface must be taken into account. The action of
friction can be analyzed thoroughly if this distribution is known. Equivalent elec-
trical circuit models or finite element models could be used to obtain impedance
distributions and to calculate the overall impedance.
2. Comparison of the techniques for the assessment of corrosion rate
The transposition of the foregoing electrochemical techniques to corrosion situ-

ations is illustrated in [63] for the assessment of corrosion rate. The results
presented in Table 1 summarize the data generated by the different techniques for
Fe electrodes in 0.5 M H2SO4 under well-controlled conditions and their
corresponding corrosion current densities, resistances, and required parameters
which determined those data.
All these techniques monitor the electrode response following the stimulation by
a potential variation in time or frequency domain with the exception of the electro-
chemical noise analysis technique. The extent of the potential stimulation and the
current response decreases in the order from Tafel extrapolation method, linear
polarization, EIS, to electrochemical noise. Each of these techniques provides the
necessary information for a given corroding system, and there are trade-offs
involved in the comparative decision of which is the best to use.
19
Techniques Parameters
ba bc icorr CDL RP RΩ Rn
[mV decade1] [mV decade1] [A cm2] [μF cm2] [Ω cm2] [Ω cm2] [Ω cm2]
Linear polarization — — 1.4 104 — 80 — —

(LPR)
Tafel extrapolation 34 114 1.8 104 — — — —

Cathodic
extrap.
7 105
Anodic
extrap.
Electrochemical — — 1.1 104 333 98 0.3 —

impedance (EIS) (Bode)
116
(Nyquist)
84 (fit)
Electrochemical noise — — — — — — 20 –40

(ENA)
Reproduced from [63] with permission from Wiley Online Library.
Table 1.
Data outcomes determined by different electrochemical techniques on Fe in 0.5 M H2SO4.
20
References
[1] Landolt D, Mischler S. Society for Testing and Materials; 1981.

Tribocorrosion of Passive Metals and pp. 167-186
Coatings. Sawston, Cambridge:
Woodhead Publishing Limited; 2011. [9] Epelboin I, Gabrielli C, Keddam M,
ISBN: 978-1-84569-966-6 Takenouti H. Alternating-current
impedance measurements applied to
[2] Celis JP, Ponthiaux P, editors. corrosion studies and corrosion-rate
Testing tribocorrosion of passivating determination. In: Mansfeld F, Bertocci
materials supporting research and U, editors. ASTM STP 727. Barr Harbor
industrial innovation. In: Handbook Drive, West Conshohocken, PA:
EFC 62. UK, France, Germany, Belgium: American Society for Testing and
Maney Publishing; 2012. ISBN: Materials; 1981. p. 110
9781907625202
[10] ASTM G59-97(2014). Standard Test
[3] Berradja A. Metallic glasses for Method for Conducting
triboelectrochemistry systems, Chap 5. Potentiodynamic Polarization
In: Huang H, editor. Metallic Glasses— Resistance Measurements. West
Properties and Processing. London, UK: Conshohocken, PA: ASTM
Intech Open; 2018. ISBN: 978-953-51- International; 2014
6208-7
[11] Mansfeld F, Xiao H. Electrochemical
[4] Landolt D. Corrosion and Surface Noise Measurements for Corrosion
Chemistry of Metals. EFPL Press; 2007. Applications, ASTM STP 1277.
pp. 415-460. Chap 10 Philadelphia, PA: American Society for
Testing and Materials; 1996
[5] Frankel GS. Electrochemical
techniques in corrosion: Status, [12] Dawson JL. Electrochemical noise
limitations, and needs. Journal of ASTM measurement: The definitive in-situ
International. 2008;5:101241. DOI: technique for corrosion applications? In:
10.1520/JAI101241 Kearns JR, Scully JR, Roberge PR,
Reichert DL, Dawson JL, editors.
[6] Trenthewey KR, Camberlain J. Electrochemical Noise Measurement for
Corrosion for Science and Engineering. Corrosion Applications. ASTM STP
2nd ed. United States: Longman Group 1277. pp. 3-35
Limited; 1995. ISBN-13: 978-0582238695
[13] Kearns JR, Eden DA, Yaffe MR, Fahey
[7] Roberge PR. Handbook of Corrosion JV, Reichert DL, Silverman DC. ASTM
Engineering. New York, Chicago, San standardization of electrochemical noise
Francisco, Lisbon, London, Madrid, measurement, ASTM STP 1277. In: Kearns
Mexico City, Milan, New Delhi, San JR, Scully JR, Roberge PR, Reichert DL,
Juan, Seoul, Singapore, Sydney, Dawson JL, editors. Electrochem. Noise
Toronto: McGraw-Hill Education; 2000. Meas. Corros. Appl. Philadelphia, PA:
ISBN: 007-076516-2 ASTM; 1996. pp. 446-470
[8] Haruyama S, Tsuru T. A corrosion [14] Reichert DL. Electrochemical noise

monitor based on impedance method. measurement for determining corrosion
In: Mansfeld F, Bertocci U, editors. rates. In: Kearns JR, Scully JR, Roberge
Electrochemical Corrosion Testing, PR, Reichert DL, Dawson JL, editors.
ASTM STP 727. Barr Harbor Drive, Electrochem. Noise Meas. Corros. Appl.
West Conshohocken, PA: American Philadelphia, PA: ASTM; 1996. pp. 79-92
21
[15] ASTM Standard: G106-89, Standard resistance measurements. Corrosion.

Practice for Verification of Algorithm 1973;29:397
and Equipment for Electrochemical
Impedance Measurements, Annual Book [24] Lorenze WJ, Mansfeld F.
of ASTM Standards. Wear and Erosion, Determination of corrosion rates by
Metal Corrosion. Vol. 03.02. West electrochemical DC and AC methods.
Conshohocken, PA: ASTM; 2001 Corrosion Science. 981;21:647-672
[16] Kamarchik. In: Scully JR, Silverman [25] Mansfeld F, Oldham KB. A
DC, Kendig MW, editors. modification of the Stern—Geary linear
Electrochemical Impedance: Analysis polarization equation. Corrosion
and Interpretation, ASTM STP 1188. Science. 1971;11:787
Philadelphia: American Society for
Testing and Materials; 1993. p. 463474
[26] Hladky K, Callow LM, Dawson JL.
Corrosion Rates from Impedance
[17] Macdonald DD, McKubre MCH.
Measurements: An Introduction. British
Electrochemical impedance techniques
Corrosion Journal. 1980;15:20
in corrosion science. ASTM STP 727.
1981:110-149
[27] Epelboin I, Keddam M, Takenouti
H. Use of impedance measurements for
[18] Bonhoeffer KF, Jena W. Über das
the determination of the instant rate of
elektromotorische Verhalten von Eisen.
metal corrosion. Journal of Applied
Zeitschrift für Elektrochemie und
angewandte physikalische Chemie. Electrochemistry. 1972;2:71-79
1951;55:151-154
[28] Boukamp BA. A non-linear least
[19] Wagner C, Traud W. Über die squares fit procedure for analysis of
Deutung von Korrosionsvorgängen immittance data of electrochemical
durch Überlagerung von systems. Solid State Ionics. 1986;20:
elektrochemischen Teilvorgängen und 31-44
über die Potentialbildung an
Mischelektroden. Zeitschrift für [29] Chen JF, Bogaerts WF.
Elektrochemie und angewandte Electrochemical emission spectroscopy
physikalische Chemie. 1938;44:391-402 for monitoring uniform and localized
corrosion. Corrosion. 1996;52:753-759
[20] Mansfeld F. The polarization
resistance technique for measuring [30] Wu P-Q, Quan ZL, Celis J-P.
corrosion currents (Chap 3). In: On-line corrosion and corrosion-wear
Fontana MG, Staehle RW, editors. monitoring using a modified
Advances in Corrosion Engineering and electrochemical noise technique.
Technology. Vol. 6. New York: Plenum; Materials and Corrosion-Werkstoffe
1976 und Korrosion. 2005;56(6):379
[21] Stern M, Geary AL. Electrochemical [31] Bertocci U, Gabrielli C, Huet F,

polarization. Journal of the Keddam M, Rousseau P. Noise
Electrochemical Society. 1957;104:56 resistance applied to corrosion
measurements II. Experimental tests.
[22] Application Note Corr-1, Basics of Journal of the Electrochemical Society.
Corrosion Measurements, EG&G 1997;144:37-43
Princeton Applied Research, 1982
[32] Bertocci U, Gabrielli C, Huet F,
[23] Mansfield F. Tafel slopes and Keddam M. Noise resistance applied to
corrosion rates from polarization corrosion measurements. I. Theoretical
22
analysis. Journal of the Electrochemical Electrochemical Society. 1997;144:

Society. 1997;144:31-37 2786-2793
[33] Eden DA, Hladky K, John DG, [42] Bertocci U, Frydman J, Gabrielli C,
Dawson JL. CORROSION’86, paper 274. Huet F, Keddam K. Analysis of
1986 electrochemical noise by power spectral
density applied to corrosion studies:
[34] Tafel J. Uber die Polarisation bei Maximum entropy method or fast
kathodischer Wasserstoffentwicklung fourier transform?. Journal of the
Zeitschrift für physikalische Electrochemical Society. 1998;145:2780
Chemie. Stochiometrie und
Verwandtschaftslehre. 1905;50:641 [43] Cottis RA. Interpretation of
electrochemical noise data. Corrosion.
2001;57(3):265-285. DOI: 10.5006/
[35] Papavinasam S. Electrochemical
polarization techniques for corrosion 1.3290350
monitoring (chap). In: Yang L editor.
[44] Coleman R, editor. Stochastic
Techniques for Corrosion Monitoring.
Processes. Springer, Dordrecht
Sawston, Cambridge: Woodhead
Publisher; 1974. ISBN: 978-0-
Publishing; 2008. ISBN: 9781845691875
04-519017-1. DOI: 10.1007/978-94-
010-9796-3
[36] ASTM G5-14. Standard Reference
Test Method for Making
[45] Iverson WP. Transient voltage
Potentiodynamic Anodic Polarization changes produced in corroding metals
Measurements. West Conshohocken,
and alloys. Journal of the
PA: ASTM International; 2014
Electrochemical Society. 1968;115:617
[37] Hladky K, Dawson JL. The [46] Berradja A, Déforge D, Nogueira

measurement of localized corrosion RP, Ponthiaux P, Wenger F, Celis JP. An
using electrochemical noise. Corrosion electrochemical noise study of
Science. 1981;21:317 tribocorrosion processes of AISI 304L in
Cl and SO42 media. Journal of Physics
[38] Hladky K, Dawson JL. The D: Applied Physics. 2006;39:3184-3192
measurement of corrosion using
electrochemical 1/f noise. Corrosion [47] Wu P-Q , Celis J-P. Electrochemical
Science. 1982;22:231 noise measurements on stainless steel
during corrosion-wear in sliding
[39] Searson PC, Dawson JL. Analysis of contacts. Wear. 2004;256:480-490
electrochemical noise generated by
corroding electrodes under open-circuit [48] Dawson JL, Hladky K, Eden DA.
conditions. Journal of the Electrochemical noise—Some new
Electrochemical Society. 1988;135:1908 developments in corrosion monitoring,
UK Corrosion, 83. In: Proceedings of the
[40] Mansfeld F, Xiao H. Conference. Exeter House, 48 Holloway
Electrochemical noise analysis of iron Head, Birmingham, UK: The Institution
exposed to nacl solutions of different of Corrosion Science and Technology;
corrosivity. Journal of the 1983. pp. 99-108
Electrochemical Society. 1993;140:2205
[49] Bertocci U, Mullen JL, Ye Y-X.
[41] Bertocci U, Huet F. Noise resistance Electrochemical noise measurement for
applied to corrosion measurements. III. the study of localized corrosion and
Influence of the instrumental noise on passivity breakdown. In: Froment M,
the measurements. Journal of the editor. Passivity of Metals and
23
Semiconductors. Amsterdam: Elsevier [58] Eden A, John DG, Dawson JL.

Science; 1983 International Patent W087/070222
[50] Hladky K, Lomas JP, John DG, Eden [59] Ritter S, Huet F, Cottis RA.
DA, Dawson JL. Corrosion monitoring Guideline for an assessment of
using electrochemical noise: Theory and electrochemical noise measurement
practice. In: Corrosion Monitoring and devices. Materials Science. 2012;63:
Inspection in the Oil, Petrochemical and 297-302. DOI: 10.1002/maco.201005839
Process Industries, Oyez Scientific and
Technical Services. London: Bath House. [60] Lengyel B, Mészáros L, Mészáros G,
p. 1984 Fekete E, Janaszik F, Szenes I.
Electrochemical methods to determine
[51] Déforge D, Huet F, Nogueira RP, the corrosion rate of a metal protected
Ponthiaux P, Wenger F. Electrochemical by a paint film. Progress in Organic
noise analysis of tribocorrosion Coating. 1999;36:11-14
processes under steady-state friction
regime. Corrosion. 2006;62:514-521 [61] Xiao H, Mansfeld F. Evaluation
of coating degradation with
[52] Leban M, Dolecek V, Legat A. electrochemical impedance
Comparative analysis of electrochemical spectroscopy and electrochemical noise
noise generated during stress corrosion analysis. Journal of the Electrochemical
cracking of AISI 304 stainless steel. Society. 1994;141:2332
Corrosion. 2000;56:921-927
[62] Keddam M, Ponthiaux P, Vivier V.
[53] Watanabe Y, Kondo T. Current and Tribo-electrochemical impedance: A new
potential fluctuation characteristics in technique for mechanistic study in
intergranular stress corrosion cracking tribocorrosion. Electrochimica Acta. 2013
processes of stainless steels. Corrosion.
2000;56:1250-1255 [63] Frankel GS, Rohwerder M.
Electrochemical techniques for
[54] Benish ML, Sikora J, Shaw B, Sikora corrosion. In: Encyclopedia of
E, Yaffe M, Krebs A, et al. A new Electrochemistry. Wiley VCH:
electrochemical noise technique for Weinheim Germany; 2007
monitoring the localized corrosion of
304 stainless steel in chloride- [64] Oltra R, Gabrielli C, Huet F,
containing solutions. Corrosion ‘98. Keddam M. Electrochemical
Paper No. 370 investigation of locally depassivated
iron. A comparison of various
[55] Berradja A, Bratu F, Benea L, techniques. Electrochimica Acta. 1986;
Willems G, Celis J-P. Effect of sliding 31(12):1505-1511. DOI: 10.1016/
wear on tribocorrosion behaviour of 0013-4686(86)87068-2
stainless steels in a Ringer’s solution.
Wear. 2006;261:987-993 [65] Ponthiaux P, Wenger F, Galland J,
Lederer G, Celati N. Du bruit
[56] Mohrbacher H, Celis JP, Roos JR. électrochimique pour déterminer la
Laboratory testing of displacement and surface dépassivée par frottement cas
load induced fretting. Tribology d’un acier z2cnd 17–13 en milieu
International. 1995;28:269-278 chloruré (NaCl 3%), Matériaux &
Techniques – numéro hors série1997.
[57] Bertocci U, Kruger J. Studies of pp. 43-46
passive film breakdown by detection
and analysis of electrochemical noise. [66] Celis JP, Berradja A, Deforge D,
Surface Science. 1980;101:608 Wenger F, Ponthiaux P, Nogueira RP.
24
Tribocorrosion of AISI 304L stainless [76] Epelboin I, Keddam M. Faradaic

steel under continuous sliding in impedances: Diffusion impedance and
Ringer’s medium. In: Conference on reaction impedance. Journal of the
Chemical, Electrochemical, and Electrochemical Society. 1970;117:1052
Mechanical Effects on CMP,
Tribocorrosion, and Biotribocorrosion, [77] Armstsrong RD, Henderson M.
207th Meeting; Quebec City, Canada; Impedance plane display of a reaction
May 15-20. 2005 with an adsorbed intermediate. Journal
of Electroanalytical Chemistry.
[67] Gabrielli C, Keddam M. Review of 1972;39:81
applications of impedance and noise
analysis to uniform and localized [78] Mansfeld F. Recording and analysis
corrosion. Corrosion. 1992;48:794-811 of ac impedance data for corrosion
studies. Corrosion. 1981;37:301
[68] Beavers A, Thompson NG,
Silverman DC. Corrosion 93, Paper No.
[79] EG&G. Basics of AC Impedance
348
Measurements, Application Note AC-1.
1990
[69] EG&G. Evaluation of Organic
Coatings by Electrochemical Impedance
[80] Hubrecht J. In: Helsen JA, Breme
Measurements, Application Note AC-2.
HJ, editors. Chap 14. Metals as
1990
Biomaterials. Electrochemical
Impedance Spectroscopy as a Surface
[70] Mansfeld F, Kendig MW.
Analytical Technique for Biomaterials.
Determination of the polarization
John Wiley & Sons Ltd.; 1998.
resistance from impedance
pp. 405-466
measurements. Materials and
Corrosion Werkstoffe und Korrosion.
1983;34:397 [81] Randles EB. Kinetics of rapid
electrode reactions. Discussions of the
[71] Mansfeld F, Kendig MW, Lorenz Faraday Society. 1947;1:11
WJ. Corrosion inhibition in neutral,
aerated media. Journal of the [82] Macdonald DD. Some advantages
Electrochemical Society. 1985;132:290 and pitfalls of electrochemical
impedance spectroscopy. Corrosion.
[72] Kilpatrick JM. Measuring corrosion 1990;46(3):229-242
rate-now. Oil and Gas Journal. 1964;62:155
[83] Syrett C, Macdonald DD. The
[73] Epelboin I, Wiart R. Mechanism of validity of electrochemical methods for
the electrocrystallization of nickel and measuring corrosion rates of copper-
cobalt in acidic solution. Journal of the nickel alloys in sea water. Corrosion.
Electrochemical Society. 1971;118:1577 1979;35:505
[74] Tsuru T, Haruyama S, Gijutsu B. [84] Titz J, Wagner GH, Spähn H, Ebert
Corrosion inhibition of iron by M, Jüttner K, Lorenz WJ.
amphoteric surfactants in 2M HCl. Characterization of organic coatings on
Japan Society of Corrosion Engineering. metal substrates by electrochemical
1978;27:573 impedance spectroscopy. Corrosion.
1990;46:221
[75] Cole SK, Cole RH. Dispersion and
absorption in dielectrics I. Alternating [85] Mansfeld F, Lin S, Kim S, Shih H.
current characteristics. The Journal of Pitting and surface modification of SIC/
Chemical Physics. 1941;9:341 Al. Corrosion Science. 1987;27:997
25
[86] Vera P, Nishikata CA, Tsuru T.

AC impedance monitoring of pitting
corrosion of stainless steel under a
wet-dry cyclic condition in chloride-
containing environment. Corrosion
Science. 1996;38:1397
[87] Ponthiaux P, Wenger F, Drees D,

Celis JP. Electrochemical techniques for
studying tribocorrosion processes.
Wear. 2004;256:459-468
26

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What are some of the major effects of corrosion?

What are some of the major effects of corrosion?

How does corrosion affect different materials?

How does corrosion affect different materials?

Chapter 01

Corrosion is a natural process driven by energy consideration. Inhibition is a

Keywords: corrosion inhibitors, acidic inhibitors, volatile inhibitors, vapor phase

Corrosion is the primary means by which metals deteriorate. Corrosion

Corrosion can be viewed as a universal phenomenon, omnipresent and omnipo-

Corrosion costs manifest in the form of premature deterioration or failure necessi-

The spontaneous oxidation of metal is termed as corrosion [12], that is,

4. Adverse economic and social effects of corrosion

• Replacement of corroded equipment resulting in heavy expenditure.

• High cost preventive maintenance such as painting.

• Loss of product from a corroded container.

• Safety requirement measures from a fire hazard or explosion or release of toxic

Corrosion has been classified into different methods. They are

• Low temperature corrosion and high temperature corrosion (or)

• Electrochemical corrosion and chemical corrosion (or)

• Wet and Dry corrosion.

M (metal) → Mn+ + ne− (oxidation)

2H+ + 2e− → H2↑ (in acid solution)

Corrosion can manifest itself in many forms such as uniform corrosion or

7.1 General corrosion

7.2 Galvanic corrosion

It occurs when a potential difference exists between two dissimilar metals

7.3 Crevice corrosion or deposit corrosion

This kind of corrosion is attacked generally within crevices associated with

7.4 Pitting corrosion or localized corrosion

Pitting corrosion is a localized attack resulting in the formation of holes in

7.5 Intergranular corrosion

• Impurities at the grain boundaries

• Enrichment of one of the elements in the alloy

• Depletion of one of the elements in the boundary area.

7.6 Selective leaching

Selective leaching is the removal of an element from an alloy by corrosion.

7.7 Erosion corrosion

It is the increase of attack of a metal because of relative movement between a cor-

7.8 Stress corrosion

• Preferential orientation of grains

• Composition and distribution of precipitates

• Dislocation structure and environmental factors and structure of metal.

7.9 Corrosion fatigue

7.10 Fretting corrosion

Fretting is a wear phenomenon enhanced by corrosion. It involves wear of a

• Magnitude of relative motion

7.11 Cavitations corrosion

It is a special type of erosion corrosion which is caused due to the formation

8. Factors influencing corrosion

8.1 Nature of the metal

1. Position of metals in EMF series

3. Relative area of anodic and cathodic parts of the metal

4. Purity of the metal

5. Physical nature of the metal

6. Nature of the surface film

8. Volatile corrosion products.

8.2 Nature of the environment

• Presence of suspended particles in atmosphere

• Nature of dissolved gases, dissolved salts, pollutants, etc.