UNIT III: Concepts of corrosion

Concepts of Corrosion
Thermodynamics and Kinetics of electrochemical corrosion – Theory for corrosion, galvanic series, thermodynamics aspects
of corrosion reactions, Nernst equation, dry and wet corrosion and the cell formation, potential- pH diagram (Fe and Al),
kinetics of corrosion reactions, Butler-Volmer equation, polarization, passivity, immunity.
Types of corrosion – Galvanic corrosion, pitting, crevice corrosion, and intergranular corrosion.

Corrosion measurements – Weight loss method, by tafel extrapolation plots.

Corrosion control – Cathodic protection (Sacrificial anode and impressed current methods), Anodic protection
Protective coatings – Metal coatings (hot dip: tinning and galvanizing), spray techniques, role of inhibitors

Introduction

The term corrosion is used to denote a change. A metal changes from its elementary state to the
combined state, more or less rapidly, when it comes into contact with the gaseous/liquid medium. This is
actually owing to the chemical interaction between the metal and the environment.

Definition

Corrosion* “The spontaneous destruction and consequent loss of a metal/alloy due to unavoidable
chemical/electrochemical attack by the environment”
Many metals exist in nature in combined form as their oxides, carbonates, sulphides, chlorides and
silicates (except noble metals) such as Au (gold), Pt (Platinum) etc. During extraction process these are
reduced to their metallic state from their ores and during extraction of ores considerable amount of
energy is required. Compounds are in lower energy state than the metals. Hence when metals are put into
use in various forms, they get exposed to environment such as dry gases, moisture, liquids etc. and
slowly the exposed metal surface begin to decay by conversion into a compound.
Example:
1. When Cu is exposed to the industrial environment it forms an adherent protective green deposit
which isolates the metal from the environment, hence the further action is very slow.
2. When iron metal is exposed to the industrial environment, the metal forms a loosely adherent
product of hydrated ferric oxide called rust, which is relatively non-protective.

Hence, the fundamental approach to the phenomena of corrosion, the structural features of the metal,
reactions which occur at the interface and nature of the environment are to be considered.

Disadvantages of corrosion:

The process of corrosion is slow and occurs only at surface of metals but the losses incurred are
enormous. Destruction of machines, equipment, building materials and different types of metallic
products, structures etc. Thus the losses incurred are very huge and it is estimated that the losses due to
corrosion are approximately 2 to 2.5 billion dollars per annum all over the world.

Theories of corrosion:

- Corrosion can be explained by the following two theories. 1. Dry or chemical corrosion. 2. Wet or
electrochemical corrosion.

Dry or Chemical corrosion:

This type of corrosion occurs mainly by the direct chemical action of the environment i.e., by the direct
attack of atmospheric gases such as O2, halogens, H2S, SO2, N2 or anhydrous inorganic liquids on the
metal surface with which they are in contact. There are 3 main types of chemical corrosion. 1) Corrosion
by oxygen (or) oxidation corrosion.

2) Corrosion by other gases like SO 2 , CO 2 , H2 S and F2 etc.

3) Liquid metal corrosion.

Wet (or) electrochemical corrosion: This type of corrosion is observed when,

A conducting liquid is in contact with a metal (or)

 When two dissimilar metals (or) alloys are either immersed (or) dipped partially in a solution.

 The corrosion occurs due to the existence of separate anodic and cathodic areas or parts between
which current flows through the conduction soln.

 In the anodic area oxidation reaction takes place so anodic metal is destroyed by dissolving (or)
forming a compound such as an oxide.

 Hence corrosion always occurs at anodic areas

  At Anode M –--------> M n+ + ne –

 At cathode M n+ +ne – --------> M

Electrochemical theory of corrosion

 Most of the corrosion cases are electrochemical in nature, taking place by an electrochemical attack
on the metal in the presence of moisture/conducting medium- called wet corrosion.
 According to the theory, when a metal is in contact with the conducting medium or when dissimilar
metals/alloys are either immersed partially/completely in a solution, a large number of galvanic cells
with the existence of anodic and cathodic area on the metal, are formed.
 In this corrosion, oxidation of the metal and reduction of species present in solution takes place at
anodic and cathodic parts, respectively.
 The electrons are transferred through the metal from anode to cathode.
 The anodic part of the metal suffers from corrosion and cathode is protected from corrosion.
 Corrosion reactions are:
At anode (oxidation reaction): M →Mn+ + ne-
The reaction at cathode (reduction reaction) depends on the nature of the environment:
If the medium is acidic,
(a) In the presence of dissolved oxygen: 2H+ + ½O2 + 2e-→H2 O
(b) In the absence of dissolved oxygen: 2H+ + 2e-→ H2 
If the medium is alkaline/neutral,
(a) In the presence of dissolved oxygen: H2 O+½ O 2 + 2e-→2 OH 
(b) In the absence of dissolved oxygen: 2H2 O+2e-→2 OH  + H2 
Example: Rusting of an Iron in the presence of moist air
At anode: Fe→Fe+2 + 2e-
 At cathode: H2 O+½ O2 + 2e-→2 OH 
Net reaction: Fe+2 +2 OH  →Fe (OH) 2
In the presence of excess of oxygen: 2Fe (OH) 2 + ½ O 2 →Fe2 O 3 .2H2 O
(rust)

In the limited supply of oxygen: 3Fe (OH) 2 +½ O2 →Fe3 O4 .3H2 O

Galvanic series

The galvanic series determines the nobility of metals and semi-metals. When two metals are submerged
in an electrolyte, while also electrically connected by some external conductor, the less noble (base) will
experience galvanic corrosion. When two metals are submerged in an electrolyte, while also electrically
connected by a metallic conductor, the less noble will experience galvanic corrosion. The rate of
corrosion is determined by the electrolyte, the difference in nobility, and the relative areas of the anode
and cathode exposed to the electrolyte.

The galvanic series is a chart showing the relationships and a guide for selecting metals that can be
joined, with the aim of helping in the decision-making process. The use of the galvanic series has to be
done with caution and basic knowledge of the environments that are a necessary part of this serious form
of corrosion. These series determine the electrochemical potential and nobility of metals and metal
alloys. It is a list of metal and alloys based on their relative potentials in a specified environment. The
environment generally used is seawater.

The characteristics of this series are as follows:

 It indicates the relative positions of metals and alloys instead of potentials.

 The practical measurement of corrosion potential at equilibrium is the basis of arranging the
series.
 According to this series, we can connect two alloys without any corrosion.

Thermodynamics aspects of corrosion reactions

Corrosion reactions inevitably involve electron transfer. For this reason, the reactions may be considered
electrochemical in nature. Thermodynamics can provide a basis for the understanding of the energy
changes associated with the corrosion reaction. It can, in general, predict when corrosion is possible.
Thermodynamics cannot predict corrosion rates. The rate at which the reaction proceeds is governed by
kinetics.

Corrosion reactions of metallic materials are of electrochemical nature, that is, the reaction can be
divided into an oxidation reaction (anodic reaction) and a reduction reaction (cathodic reaction). In the
case of corrosion, metal oxidation reaction (eqn [I]) is coupled with the reduction of species in the
environment/electrolyte – the two most typical reactions taking place in aqueous environments are the
reduction of protons (eqn [II]) or reduction of oxygen dissolved in water (eqn [III]).

The anodic and the cathodic reactions can either take place statistically distributed all over the surface,
leading to uniform corrosion, or be separated at specific cathodic and anodic sites of the surface, leading
to localized corrosion. The latter phenomena (localized corrosion) take place when heterogeneities exist
either on the material surface (e.g., different phases of a multiphase alloy) or in the environment (e.g.,
water-line corrosion of partially immersed objects owing to inhomogeneous oxygen distribution in the
depth).
Owing to the electroneutrality requirement (i.e., all electrons produced in the anodic reaction must be
consumed in the catholic reaction), the oxidation and reduction reactions must take place simultaneously
and with an equal rate. To complete the circuit, the anodic and the cathode sites must be electrically and
electrolytically connected.
With the help of simple thermodynamic considerations as described in eqns [1] and [2], a first assessment
of the risk of corrosion can be made by looking at the electrode potentials of the oxidation (anodic) and
reduction (cathodic) reactions
here ΔG is the change in the Gibbs free energy, n is the number of electrons exchanged in the
reaction, F is the Faraday constant, V is the cell voltage, EC is the potential of the cathodic reaction,
and EA is the potential of the anodic reaction.
The electrode potentials for the partial reactions are obtained from the standard potentials with the help of
the Nernst equation
Nernst Equation
The potential values of a metal are modified by the environment. Concentrations of anodic and cathodic
reactants will alter the balance between the oxidation and reduction reactions. The Nernst equation allows
us to calculate metal potentials under differing metal ion or oxidation/reduction conditions. The Nernst
equation may be stated as follows:

Where : Ecell = Cell potential under environmental conditions (Volts)

Eo =Standard reduction potential at 25 O C (Volts)
R = Universal gas constant (8.3143 J/mol o K)
T = Absolute temperature (degrees kelvin )
n = Electrons transferred in the reaction
F = Faradays constant (96500 coulombs/mol)
(oxid.) = activity of oxidized species(M)
(red.) = activity of reduced species(M)

Butler-Volmer equation

A knowledge of the rate at which a metal will corrode, especially under different solution conditions and
pH is essential when trying to design systems that will prevent or slow down corrosion processes. Since
the kinetics of corrosion essentially the kinetics of electron transfer, the equations used to understand
electrode kinetics can be used. Most importantly, the Butler-Volmer equation since this relates current
(rate of interfacial reaction) with both applied voltage and the Eo for a specific system.
The corrosion form of the Butler-Volmer equation:

In corrosion studies, it is important to be able to accurately calculate the rate of corrosion. The corrosion
rate is directly proportional to the exchange current density at zero applied potentials. In corrosion studies,
the exchange current density, io is referred to as the corrosion current:
io = icorr ∝ k
where k is the corrosion rate.
Hence, a determination of icorr is of fundamental importance.

Types of corrosion

1.Galvanic corrosion, 2.pitting corrosion 3.crevice corrosion, 4. Intergranular corrosion.

Galvanic corrosion or Differential metal corrosion

 When two dissimilar metals are in direct contact with one another and exposed to a corrosive
conducting medium, the metal higher up in the electrochemical series behaves as anode and suffers
from corrosion, whereas the metal lower in the electrochemical series becomes cathode and protected
from corrosion. This type of corrosion is also known as Galvanic corrosion.
 If the potential difference between the electrodes is high, greater the extent of corrosion.
 Oxidation /reduction takes place at anode/cathode respectively.
 The reduction at cathode depends on the nature of the corrosive environment. In acidic medium,
corrosion occurs by hydrogen evolution; while in alkaline/neutral solution, oxygen absorption takes
place.
 When Zn and Cu metals are electrically connected and exposed to an electrolyte, Zn (higher in
electrochemical series) forms anode and suffers from corrosion whereas Cu (lower in electrochemical
series) forms cathode and protected from corrosion.
 Examples: Steel screws in a brass marine hardware
Steel pipe connected to copper plumbing

Differential aeration corrosion

 This type of corrosion is due to the formation of differential aeration cell or oxygen concentration
cell.
 When a metal surface is exposed to differential air or oxygen concentrations- forms differential
aeration cell.
 The more oxygenated part of the metal behaves as cathode and less oxygenated part becomes
cathode.
 Differential aeration of metal causes a flow of current called the differential current and the corrosion
is called differential aeration corrosion. Example (a): Rusting of an iron.
 Example (b): Consider a piece of Zn metal is partially immersed in a dilute solution of neutral salt
(NaCl), and the solution is not agitated properly. The part of the metal above and closely adjacent to
the water-line are more oxygenated, because of easy access of oxygen and hence become cathodic.
The part of the Zn metal immersed to greater depth, which have less access of oxygen and becomes
anode. Hence a difference in potential between the electrodes is created, which causes a flow of
current between the two differentially aerated areas of the same metal and causes corrosion at anode.
 Differential aeration accounts for the corrosion of metals partially immersed in a solution, just below
the water line. This type of differential aeration corrosion is also known as water line corrosion.
 Consider a steel tank containing water. The maximum corrosion takes place along a line just beneath
the level of water meniscus. The area above the waterline is highly oxygenated and acts as the
cathodic and completely unaffected by corrosion. (Eg. Marine plants attacking themselves in the
sides).

Poor oxygenated more oxygenated

Area (anode) area (cathode)

Pitting corrosion
 Is a localized accelerated attack in which only small areas of the metal surface are attacked while the
remainder is largely unaffected. This localized attack results in pitting. The pits may initiate and
propagate to a certain depth resulting in the formation of cavities and becomes inactive.
 Pitting is very destructive and frequently ruins the tubes, pipes etc.
 Pitting is due to breakdown or cracking of the protective film on a metal at specific points. The
presence of impurities like sand, dust, scale, etc., on the surface of metal leads to pitting.

 Pitting corrosion is due to the formation of differential aeration cell.

 This attack becomes more intensified with time.

CREVICE CORROSION

Crevice corrosion is a localized attack on a metal surface at, or immediately adjacent to, the gap or
crevice between two joining surfaces when exposed to a stagnant electrolyte.

This can occur between two metals or a metal and nonmetal material -- even if both materials would
otherwise resist corrosion without the presence of a gap.
 Typically, the electrolyte won’t pose a problem at first. However, as it remains in the crevice, oxygen
levels will deplete.

This then triggers a surplus of positive metal ions within the crevice, turning the interior of the crevice
into an anodic node.

The surrounding solution will then attempt to balance this situation by sending negative ions into the
crevice (often in the form of chloride ions) further enhancing acid creation and attacking the metal.

Left unchecked, the process can feed itself, accelerating corrosion at an astounding rate -- even for alloys
such as stainless steel with a strong passive layer.

Common areas subject to crevice corrosion include:

 Bolted and riveted connections

 Under washers, gaskets, and clamps
 Under insulation
 At lap joints
 In fastener threads

If this all sounds a little complicated, just remember that when electrolyte can settle in a small area
between a piece of metal and another surface (metal or non-metal), the risk for crevice corrosion
increases.

This simple description gives you multiple ways to reduce the risk of corrosion occurring.

PREVENTING CREVICE CORROSION

As the definition of crevice corrosion describes, there are two primary methods of reducing crevice
corrosion risks:

1. Eliminate small gaps which might trap electrolyte and lead to stagnation
2. Keep electrolyte flowing freely or at high enough rates to prevent stagnation

However, a range of factors can influence both overall risk levels and the severity of the corrosion’s
progression

Inter granular corrosion

Stainless steel, like many other metals and alloys, is composed of a crystallite structure.

This means the metal itself is composed of grains of various sizes. Where these grains meet are called the
grain boundaries.

Also known as weld decay, inter granular corrosion attacks these boundaries, causing damage to the
metal at a molecular level.

Cracking and grain loss can occur, leading to reduced structural integrity, ability to withstand pressure,
and further encouraging additional corrosion.
Much like stress corrosion cracking, this can occur with little to no visual indication of a corrosive
attack.

As such, not accounting for inter granular corrosion risks can lead to catastrophic failure of impacted
piping processes and stainless steel components.

WHAT CAUSES INTERGRANULAR CORROSION?

Inter granular corrosion occurs when certain metals and alloys reach temperatures between 425°C and
870°C (887°F to 1598°F.)

These temperatures are most common during welding, heat treatment, or operation in high-temperature
environments.
When the metal endures such extreme temperatures, it changes at a structural level.

Chromium present in the alloy reacts with carbon to create chromium carbide near the grain boundaries.

This carbide formation essentially converts the boundaries into anodic cells. The grain interiors then
function as cathodic cells, and the inter granular corrosion begins.

PREVENTING AND REPAIRING INTERGRANULAR CORROSION DAMAGE

Material choice is an essential element of risk mitigation and ensures long-lasting safety and performance
of pipes and components.

When looking for stainless steels with excellent inter granular corrosion resistance, consider low-carbon
alloys (often designated with an L.).

When choosing low-carbon alloys, options with carbon percentages below 0.03 percent will ensure that
insufficient carbon is available for carbide formation.

Corrosion measurements – Weight loss method by tafel extrapolation plots.

A Tafel plot is a graphical plot (usually logarithmic) showing the relationship between the current
generated in an electrochemical cell and the electrode potential of a specific metal. These plots are
usually generated based on electrochemical experiments performed under controlled conditions.

Tafel plots are used by electrochemists to predict specific corrosion-related information including
corrosion rate, passivity and pitting vulnerability.

Traditional methods of studying and predicting corrosion rates, such as weight loss analyses, are usually
a long-term affair. Electrochemical techniques, like the Tafel equation and Tafel plots, are quickly
gaining popularity due to the speed at which results can be attained. Compared to conventional corrosion
studies, which may take days or weeks to complete, Tafel plots obtained from electrochemical
experiments can be used to achieve results in a few hours. Tafel plots are especially useful for predicting
corrosion activity in metals or alloys that are highly corrosion resistant.
Predicting Corrosion Rates
Armed with the Tafel equation and Tafel plots, it is now possible to predict whether a particular setup
will result in corrosion and if so how fast the corrosion will be.

In order for corrosion to occur, there must be a suitable anodic reaction and an appropriate cathodic
reaction. This is manifested as an intersection of a cathodic branch and an anodic branch on a Tafel plot.
The point of intersection gives the corrosion potential and the corrosion current (or, more accurately the
log of the corrosion current density).

The rate of corrosion is governed by all the factors discussed previously. When all the effects are taken
into account, Tafel plots get quite complicated and some interesting effects occur:

Faraday’s law allows the current density to be expressed as the mass of material lost per unit time.

The calculation involves a few simple steps. For a corrosion reaction:

1. The current is converted into a rate of electron consumption using the electronic charge constant.
2. The number of electrons is divided by the stoichiometric number of electrons in the corrosion
reaction, giving the number of metal atoms lost per unit time.
3. This answer is then divided by Avogadro’s number to give the number of moles of metal atoms
lost per unit time.
 4. The number of moles is then converted to mass lost per unit time, using the molar mass.
5. The mass is then converted to a volume using the density.
6. The volume is then converted to a thickness lost per unit time by dividing by the area that the
current passes over. If a current density was given, this step has already been done.

Overall, the thickness of metal lost per unit time is given by the formula:

t = imM/ρezNA

where t = thickness (m), i = current density (A m-2 ), mM = molar mass (kg mol-1 ),

e = electronic charge (C), z = stoichiometric number of electrons in oxidation reaction, NA is Avogadro’s

number.

Factors affecting the rate of corrosion

The rate and extent of corrosion is depends on the following factors

1.Primary factors
 Nature of the metal

 Nature of the corrosion product

 Ratio of anode to cathode

 Polarization.

Polarization

 The anodic and cathodic reactions take place simultaneously during corrosion, and causes polarization
of the electrodes.

 Anodic polarization occurs due to accumulation of metal ions in the vicinity of anodic region. This
retards the formation of new metal ion. Thus corrosion processes is retarded.

 Cathodic polarization occurs due to accumulation of hydroxyl ions in the vicinity of cathodic region.
This accumulation retards the movement of oxygen towards the cathodic surface. Thus the reduction
of oxygen is decreased. Therefore polarization of anode or cathode decreases the corrosion rate
substantially
 The presence of depolarizers reduces the polarization effect and thereby increases the rate of
corrosion.
 The addition of complexing agents around anode and/or the presence of oxidizing agents around
cathode, acts as depolarizers.

2. Secondary factors:

 pH of the medium

 Temperature:

 Humidity

Potential- pH diagram OR Pourbiax diagram:

A Pourbaix diagram provides information about the stability of a metal as a function of pH and
potential. These diagrams are available for over 70 different metals. Pourbaix diagrams have several
uses, including in corrosion studies.
A Pourbaix diagram is also known as a potential/pH diagram, equilibrium diagram describing
various chemical phase formation at different pH and potential. Pourbaix diagrams are plotted by
using the Nernst equation (an equation used to calculate electrode potential). As the Nernst equation
is derived entirely from thermodynamics, the Pourbaix diagram can be used to determine which
species (metals or alloys) is thermodynamically stable at a given electrode potential (E) and pH

Characteristics of Pourbaix diagram:

A Pourbaix diagram is divided in regions of “immunity”, “corrosion” and “passivity”. These regions
provide information about the stability of a particular metal or alloy in a specific aqueous
electrochemical environment under certain pH, E vs SHE, pressure and temperature conditions.
 The immunity region is the region in which there is no metal dissolution.
 The corrosion region is the region in which there is active metal dissolution.
 The passivation region is the region in which a protective metal-oxide film that prevents metal
dissolution is formed.
  Horizontal lines represent electron transfer reactions. They are pH-independent, but potential-
dependent.
 Vertical lines are potential-independent but pH-
dependent and not accompanied by any electron
transfer.
 Sloping, straight lines give the redox potentials of a
solution in equilibrium. This equilibrium indicates
electron transfer as well as pH.
 The diagram is computed for the equilibrium
conditions at 25°C.
The main objectives of the Pourbaix diagrams are:
 1. To show the directions of the various reactions at given pH and potential.
 2. To make a basis for estimation of the corrosion product compositions at various pH and
potential combinations.
 3. To show which environmental pH and potential changes will reduce or prevent corrosion.

Pourbaix diagram of water

As water is the medium in the electrochemical or wet corrosion we must understand the stability region
of H2 O in the Pourbaix diagram. From the diagram below we see the stability region of water.

When the E is increased or decreased the water

undergoes oxidation or reduction. This appears along
with all metal system.

Water is thermodynamically stable at the range of

zero to 1.23 V of potential.

Pourbaix diagram of Aluminium `

In the Pourbaix diagram of Aluminum, the water is shown as dotted lines. The region below and above
the line water is not stable. In the above Pourbaix diagram, in the Passivation region Al is covered by the
Al2 O3 layer. The Al2 O 3 layers protect the base Al from further corrosion in the particulate pH and E
conditions. However, when the pH increases or decreases beyond the passivation zone the passive layers
undergo dissolution and Al3+ appears in the solution as corroded products. From the Pourbaix diagram it
is obvious that Al (immune zone) is stable only in more cathodic region, even at neutral conditions.

The reactions corresponding to lines in the diagram are as follows.

1. Al → Al3+ + 3e (Redox reaction it is Potential dependent and pH independent)

2. 2Al + 3 H2 O→ Al2 O3 + 6H+ (Acid base reaction it is pH dependent and Potential independent)

3. 1/2Al2 O3 + 3H++ 3e- →Al + 3/2 H2 O (both redox and acid base reaction, it depends both pH and
Potential)

In both acidic and alkali medium Aluminum undergo corrosion at higher potentials (pH between 1-4 and
8-14). In neutral condition Aluminum forms thin layer on the surface called passive layer.

Pourbaix diagram of Iron

Iron is the most common and hard engineering

material. But this undergoes severe corrosion and
forms various corrosion products at different potential
and pH conditions. The below Pourbaix illustrates the
immune zone in more cathodic and acidic pH. It is
obvious that pure Iron is relatively stable than Al in
E-pH diagram. In the oxidative or positive potential
and acidic (pH <6) condition iron undergoes
dissolution and corroded products ( Fe+2 and Fe3+)
remains in the solution.

In neutral and slight basic conditions

formation Fe(OH)2 is observed in Poubaix diagram.
As the potential increases Fe(OH)3 and oxide formation is observed in the E-pH diagram.
 Rust formation is observed more oxidative condition with higher pH conditions. In highly
basic and cathodic potential conditions (in boiler corrosion – caustic embrittlement) formation of
FeO 2- is observed.

From the Pourbaix diagram it is obvious that Iron undergoes various phase formation with change in
pH and potentials.

The reactions corresponding to lines in the diagram are as follows.

1. Fe+2 +2e- →Fe (pure redox reaction, it is pH independent and Potential dependent)

2. 2Fe3++3H2 O →Fe2 O3 +6H+(Pure acid base reaction, it is pH dependent and Potential

independent)

3. 2Fe+2 +3H2 O→Fe2 O3 +6H++2e-(Both redox and acid base reaction, it depends on both pH and
Potential)

The knowledge and understanding the stability of these engineering metals is very important in device,
construction and engineering material applications.

Corrosion control

As the corrosion process is very harmful and losses incurred are tremendous, it becomes
necessary to minimize or control corrosion of metals. Corrosion can be stopped completely only under
ideal conditions. But the attainment of ideal conditions is not possible. However, it is possible only to
minimize corrosion considerably. Since the types of corrosion are so numerous and the conditions under
which corrosion occurs are so different, diverse methods are used to control corrosion. As the corrosion
is a reaction between the metal or alloy and the environment, any method of corrosion control must be
aimed at either modifying the metal or the environment.

Corrosion control

Corrosion can be completely avoided only under ideal conditions. Since it is impossible to attain such
conditions, it can be minimized by using various corrosion control methods. They are:
a) by protective coatings
 b) by corrosion inhibitors
c) by cathodic protection
d) by anodic protection
Cathodic Protection:

The principle is to force the metal to be protected, to behave as cathode. There are two types of cathodic
protections namely,
1) Sacrificial anodic protection
2) Impressed current cathodic protection
Sacrificial anodic protection

 The metallic structure to be protected is connected to a more anodic metal using a metallic wire.
 The more active metal gets corroded, while the parent structure is protected from corrosion.
 The more active metal so employed is called sacrificial anode.
 The sacrificial anodes to be replaced by fresh ones as and when it is required.
 Commonly used sacrificial anodes are: Mg, Zn, Al etc.
 This method is generally used for the protection of buried pipelines, ship hulls, water tanks, etc.
Example: steel pipe is protected by connecting it to a block of Mg or Zn. In such cases steel acts as a
cathode and is unaffected Mg or Zn acts anode and undergoes sacrificial corrosion

Impressed current cathodic protection

 The metallic structure to be protected is made as cathode by impressing the current.
 The current is applied in the opposite direction to nullify the corrosion current.
 The impressed current is obtained from a source like battery.
  An insoluble anode (ex: graphite, high silicon content iron, etc.) is buried in the soil, and connected

to the structure to be protected.

The anode is usually placed in a backfill, to provide a better electrical contact with the surroundings.
This method is suitable for large structures and for long term operations

Anodic protection

The principle is to force the metal to be passive, to behave as anode.

Metals like titanium, chromium, iron, nickel and their alloys show passivity.

Metals become passive on applying potential greater than passivating potential by maintaining constant
current using potentiostat.

Passivity is due to the formation of oxide film on the surface in an oxidizing environment

The passivation can be explained by plotting a graph

The plot of corrosion current as a function of applied potential shows as the potential is increased the
corrosion current increases first (region AB),then decreases (region BC),then remains constant(region
CD),then increases again(region DE)

Region CD is passive region at this region rate of corrosion is very slow, but not

Protective coatings

 Corrosion is prevented by the application of protective coating on the surface of metal, thereby the
metal surface is isolated from the corrosive environment.
 The coatings being chemically inert to the environment under specific conditions of temperature and
pressure, forms a physical barrier between the coated surface and its environment.
 Coatings are not only preventing corrosion but also decorate the surface of the metal.
 Important types of protective coatings are:
 (i) Metal coatings
(ii) Inorganic coatings and
(iii) Organic coatings

 Metal coatings

 Metal coatings can be applied on the base metal by hot dipping process.
 This method is used for producing a coating of low melting metals such as Zn, Al, Sn etc., on iron
/ steel metals which have relatively high melting point.
 The process involves immersing of the base metal in a molten bath of coating metal covered by a
flux layer. The flux cleans the surface of the metal base metal and prevents the oxidation of
molten coating metal. The coating metal may be anodic or cathodic to the base metal.
 Example: Galvanizing and Tinning
Galvanization or Galvanizing:

Galvanisation or galvanization (or galvanizing as it is most commonly called) is the process of

applying a protective zinc coating to iron or steel, to prevent rusting. The most common method is
hot dip galvanizing, in which steel sections are submerged in a bath of molten zinc.

Hot-dip galvanizing is the process of immersing iron or steel in a bath of molten zinc to produce a
corrosion resistant, multi-layered coating of zinc-iron alloy and zinc metal. While the steel is immersed
in the zinc, a metallurgical reaction occurs between the iron in the steel and the molten zinc. This
reaction is a diffusion process, so the coating forms perpendicular to all surfaces creating a uniform
thickness throughout the part.
Tinning:
Tinning is the process of thinly coating sheets of wrought iron or steel with tin, and the resulting product
is known as tinplate. The term is also widely used for the different process of coating a metal with solder
before soldering.
It is most often used to prevent rust, but is also commonly applied to the ends of stranded wire used as
electrical conductors to prevent oxidation (which increases electrical resistance), and to keep them from
fraying or unraveling when used in various wire connectors like twist-ons, binding posts, or terminal
blocks, where stray strands can cause a short circuit.

Galvanizing Tinning
 Coating of zinc on iron or steel, by hot  Coating of tin on iron or steel, by hot
dipping process is called galvanizing. dipping process is called tinning. (M.P
(M.P of Zn = 419o C) of Sn = 232o C).
 The article is washed with organic  The metal surface is washed with
solvents to remove oil/grease, with organic solvents to remove oil/grease,
sulphuric acid to remove scale/rust, with sulphuric acid to remove scale/rust
 then with water and dried, before then with water and dried, before
coating. coating.
 Coating metal is anodic to iron/steel,  Coating metal is cathodic to iron/steel,
called anodic coating. called cathodic coating.
 The molten metal bath is covered with  The molten metal bath is covered by a
a flux of Ammonium chloride, which flux of Zinc chloride.
prevents the oxidation of the coated  The clean and dry sheet is passed
metal. through flux layer, molten tin, finally
 The article is dipped in a molten bath removed out through palm oil, which
of Zn. The excess of coated metal is prevents the oxidation of the coated tin.
removed by passing through a pair of  It possesses more resistance against
hot rollers and cooled gradually. atmosphere.
 Galvanizing is applied to nails, bolts,  It is non-toxic in nature and more noble
pipes, roofing sheets etc. than the base metal.
 Galvanized sheets cannot be used for  Tinning is widely used for coating the
preparing/storing food stuffs, since Zn steel sheets, Cu and brass sheets used
dissolves in acidic medium and forms for manufacturing containers for
toxic compounds. storing/packing food materials, cooking
 If any crack is produced on the utensils, refrigeration equipments, etc.
galvanized sheets, causes severe  If any crack is produced on the tinned
corrosion on the coated Zn metal and sheets, causes severe corrosion of the
the base metal is protected. base metal.
 Zn is chosen as a protective coating for  Tin coatings form a useful preparation
iron/steel because of its natural for protective painting in general
resistance against corrosion in most applications.
atmospheric conditions, and Zn is
electronegative to iron and can protect
it sacrificially.
 Corrosion Inhibitors

Definition, mechanism and types

 Definition of corrosion inhibitors:

Corrosion inhibitors are substances that are added in small amount (e.g 0.1%) to the corrosive
medium stop or slow down electrochemical corrosion reactions on a metal surface.
 Mechanism:

Corrosion inhibitors work by one or more of the following mechanisms.

• They adsorb on metal surfaces to form protective films.

 • They combine with corrosion product films to protect metal surfaces.

• They form precipitates, which visibly coat and protect metal surfaces.

Types of inhibitors:

 Inhibitors can be divided into two main categories—inorganic and organic.

 Inorganic inhibitors are used mainly in boilers, cooling towers, and fractionation units.

 Organic inhibitors are used mainly in oil field systems.

As shown in the figure, inorganic inhibitors are further divided into anodic and cathodic
classifications. These classifications describe the part of the electrochemical process that is interrupted
by the inhibitor. Organic film- forming inhibitors interrupt both the anodic and cathodic processes.

Classification of corrosion inhibitors

Inorganic inhibitors

1. Cathodic inhibitors:
Cathodic inhibitors are chemical compounds which inhibit the cathodic reaction of the corrosion cell.
Examples of cathodic inhibitors:-
a. Compounds such as ZnSO 4 , MgSO 4 and Ca(HCO 3 )2 , these compounds inhibit the cathodic
reaction by forming insoluble Zn(OH)2 film or Mg(OH)2 film or CaCO 3 film with the
cathodically formed 𝑂𝐻− ions (in neutral solutions) the insoluble film isolates the cathodic
regions of the corrosion cells from the corrosive medium and stops corrosion.
b. Oxygen scavengers, these are compounds which react with dissolved oxygen and remove it
from the neutral or alkaline corrosive environment such as sodium sulphite or hydrazine (used to
inhibit boiler corrosion and are called high temperature oxygen scavengers)
𝑁𝑎 1 𝑦i𝑒𝑙𝑑𝑠
𝑆𝑂 +
 2 3 𝑂2 −−−−→ 𝑁𝑎2𝑆𝑂4
2

𝑦i𝑒𝑙𝑑𝑠

𝑁2𝐻4 + 𝑂2 −−−−→ 𝑁2 + 2𝐻2𝑂

Oxygen depolarize the cathode

c. Compounds such as arsenic (As), mercury (Hg), antimony (Sb) salts which are added to acidic
corrosive environments to slowdown the cathodic H2 evolution reaction.

 These compounds prevent the hydrogen atoms from forming hydrogen gas, and are called
cathodic poisons.
 Cathodic poisons are used advantageously as corrosion inhibitors by stifling the cathodic
reduction processes that must balance the anodic corrosion reaction. However cathodic
poisons can also increase the susceptibility of a metal to hydrogen induced cracking since
hydrogen can also be absorbed by metal during aqueous corrosion or cathodic charging.

When corrosion occurs in a low-pH solution, some of the reduced hydrogen does not form gaseous
hydrogen, but instead, diffuses into the metal as atomic hydrogen and form metal hydride causing
hydrogen embrittlement.
Note:

Also substances such as sulfur, selenium, tellurium, and cyanide ions do the same effect.

2. Anodic inhibitors: Are chemical compounds which inhibit the anodic reaction of the
corrosive cells.
Examples

a. Compounds such as Na2 SiO 3 , Na2 CO 3 and Na3 PO 4 , these compounds form with the
anodically formed Fe++ an insoluble film of iron silicate or iron carbonate or iron phosphate
which isolates the anodic sites of the corrosion cells from the corrosive solution.
b. Passivators: these are oxidizing agents such as chromate inhibitors (Na 2 Cr2 O 7 ) or nitrite
inhibitors (NaNO 2 ) which react with the anodically formed Fe ++ to form a passive oxide film
on the anodic sites of the corrosion cells.
Na2 Cr2 O7 +2Fe ++ 𝐻2𝑂 −−−−→ 𝐶𝑟2𝑂3 + 𝐹𝑒2𝑂3 + 2𝑁𝑎𝑂𝐻

NaNO 2 +2Fe+++ 2𝐻 2𝑂 −−−−→ 𝑁𝐻 3 + 𝐹𝑒2𝑂3 + 𝑁𝑎𝑂𝐻

Chromate inhibitors are the most effective of the anodic inhibitors. They were used for many years in
cooling towers and other recirculating cooling water systems; however, they are toxic to most
organisms. Chromate inhibitors contain sodium chromate, Na 2 CrO 4 , or sodium dichromate, Na2 Cr2 O7 .
Chromate, or dichromate, ions accept electrons that are lost in ferrous iron oxidation reactions. This
reduction reaction forms chromium (III) oxide (𝐶𝑟2 𝑂3 ). The chromium oxide combines with iron oxide
to form a mixed oxide. This combination of iron oxide and chromium oxide makes chromium
inhibitors effective. Normally, iron oxide deposits are loosely attached to metal surfaces. However, the
combination of iron oxide and chromium oxide forms a deposit that tightly attaches to the metal
surface.

𝑁𝑎2 𝐶𝑟2 𝑂7 (0.2%, PH =8) was used widely in industry to protect the cooling system of the plant
against corrosion. Recently chromate has been replaced by a mixture of Zn++, polyphosphate
and chromate which is less harmful to the environment because the mixture uses a lower doze of the
toxic 𝐶𝑟𝑂−−. More recently zinc phosphate is being used without chromates.
4

Nitrite inhibitors may be used to replace the more toxic chromates. Sodium nitrite (NaNO 2 ) is used in
closed, recirculating cooling water systems with a pH between 7 and 9. Nitrites perform similarly to
chromates. They form a protective iron oxide film that passivates steel surfaces. They are
environmentally acceptable and easy to monitor.

Note:

Nitrites easily oxidize to nitrates. Nitrates are not effective corrosion inhibitors. That is why nitrites are
used in closed systems.
Spray techniques

Thermally sprayed metal coatings of zinc, aluminum, and zinc-aluminum alloys can provide long-term
corrosion protection to steel structures exposed to aggressive environments. The metal, in powder or wire
form, is fed through a special spray gun containing a heat source, which can be either an oxygas flame or
an electric arc. Molten globules of the metal are blown by a compressed air jet onto the previously grit
blast cleaned steel surface. No alloying occurs and the coating consists of overlapping platelets of metal
and is porous. The pores are subsequently sealed by applying a thin organic coating, which penetrates
into the surface. It is essential that the sealer completely satisfies the filling of all porosity in the metal
coating.