Chapter

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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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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Corrosion Inhibitors

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

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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].

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Corrosion Inhibitors

• 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.

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Corrosion Inhibitors
DOI: http://dx.doi.org/10.5772/intechopen.80542

Author details

Geethamani Palanisamy
Department of Chemistry, SNS College of Technology, Coimbatore, Tamil Nadu,
India

*Address all correspondence to: [email protected]

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

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Corrosion Inhibitors

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