CORROSION

Introduction: -

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.
Definition: -

Any process of deterioration or destruction and consequent loss of a solid

metallic material through an unwanted chemical or electrochemical attack by
its environment at its surface is called corrosion.

Corrosion is a natural process that converts a refined metal into a more

chemically stable form such as oxide, hydroxide, or sulfide. It is the gradual
destruction of materials (usually a metal) by chemical and/or electrochemical
reaction with their environment.

Thus corrosion is a reverse process of extraction of metals.

Examples:-

i) Rusting of iron – when iron is exposed to the atmospheric conditions, a layer

of reddish scale and powder of Fe3O4 is formed.

ii) Formation of green film of basic carbonate- [CuCO3 + Cu(OH)2] on the

surface of copper when exposed to moist air containing CO2.

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.

CAUSES OF CORROSION:

In nature, metals occur in two different forms.

1) Native State (2) Combined State

Native State: The metals exist as such in the earth crust then the metals are
present in a native state. Native state means free or un combined state. These
metals are non-reactive in nature. They are noble metals which have very good
corrosion resistance. Example: Au, Pt, Ag, etc.,
Combined State: Except noble metals, all other metals are highly reactive in
nature which undergoes reaction with their environment to form stable
compounds called ores and minerals. This is the combined state of metals.
Example: Fe2O3, ZnO, PbS, CaCO3, etc.,

Metallic Corrosion:

The metals are extracted from their metallic compounds (ores). During the
extraction, ores are reduced to their metallic states by applying energy in the
form of various processes. In the pure metallic state, the metals are unstable
as they are considered in excited state (higher energy state). Therefore as soon
as the metals are extracted from their ores, the reverse process begins and
form metallic compounds, which are thermodynamically, stable (lower energy
state). Hence, when metals are used in various forms, they are exposed to
environment, the exposed metal surface begin to decay (conversion to more
stable compound). This is the basic reason for metallic corrosion.
 Although corroded metal is thermodynamically more stable than pure
metal but due to corrosion, useful properties of a metal like malleability,
ductility, hardness, lustre and electrical conductivity are lost.
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 dry or chemical corrosion.

1) Corrosion by oxygen (or) oxidation corrosion.

2) Corrosion by other gases like SO2, CO2, H2S and F2 etc.

3) Liquid metal corrosion.

Oxidation corrosion:-
It is brought about by direct action of oxygen at low (or) high temperatures,
usually in the absence of moisture.

At high temperatures all metals are attacked by oxygen and are oxidized –
except noble metals like Ag, Au, and Pt.

At ordinary temp generally all the metals are slightly attacked. However alkali
metals – Li, Na, K, Rb etc. and alkaline earth metals – Be, Ca, Sr etc. are
attacked very rapidly and get oxidized readily.

Mechanism of oxidation corrosion: - Oxidation occurs first at the surface of the

metal and a scale of metal oxide is formed on the surface of the metal and it
tends to act as a barrier for further oxidation.

Therefore, for oxidation to continue either the metal must diffuse outwards
through the scale to the surface or the oxygen must diffuse inwards through
the scale to the underlying metal. Both transfers occur, but the outward
diffusion of the metal is generally much more rapid than the inward diffusion
of oxygen. Since the metal ion is appreciably smaller than the oxide ion,
therefore the metal ion has much higher mobility

Metal oxide
Nature of the oxide formed: - It plays an important role in further oxidation
corrosion process.

Metal + oxygen ……….metal oxide (corrosion product)

When the oxide film formed is

i) Stable layer: - A stable layer is fine grained in structure and can get adhered
tightly to the parent metal surface. Such a layer will be impervious in nature
and hence behaves as protective coating, thereby shielding the metal surface.
Consequently further oxidation corrosion is prevented.

E.g.: Al, Sn. Pb, Cu, etc. form stable oxide layers on surface thus preventing
further oxidation.

ii) Unstable Layer: - The oxide layer formed decomposes back into metal and
oxygen
Metal oxide………. .metal + oxygen

Consequently oxidation corrosion is not possible in such cases.

Eg: Ag, Au and Pt do not undergo oxidation corrosion.

iii) Volatile Layer: The oxide layer formed is volatile in nature and evaporates as
soon as it is formed. There by leaving the under lying metal surface exposed
for further attack. This causes rapid continuous corrosion, leading to excessive
corrosion

eg: Mo- molybdenum forms volatile MoO3 layer.

iv) Porous Layer: Contains pores and cracks. In such a case the atmospheric
oxygen has access to the underlying surface of the metal through the pores or
cracks of the layer, there by corrosion continues until the entire metal is
converted to its oxide.

Eg: Iron when attacked by H2S at high temperature forms porous FeS layer.
Pilling – Bedworth rule: the specific volume ratio of metal oxide to metal

The oxide layer acts as a protective or non–porous barrier, if the volume of the
oxide is at least as greater than the volume of the metal from which it is
formed.

On the other hand -if the volume of the oxide layer is less than the volume of
metal, the oxide layer is porous and hence non-protective. Because it cannot
prevent the access of oxygen to the fresh metal surface below.

If the specific volume ratio is small, then rate of corrosion is large.

For eg: alkali and alkaline earth metals like Li, Na, K, Mg forms oxides of
volume less than volume of metals. These layers are porous and non-
protective. Hence these undergo corrosion more rapidly. On the other hand
metals like Al forms oxide whose volume is greater than the volume of the
metal. Therefore Al forms a tightly – adhering non-porous protective layer.
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 –--------> Mn+ + ne –

 At cathode Mn+ + ne – –--------> M

 In cathodic area, reduction reaction (gain of e – s) takes place. The metal

which is acting as cathode is in its reduced form only. Therefore it
cannot be further reduced. Therefore cathodic reactions do not affect
the cathode.
 So at cathodic part dissolved constituents in the conducting medium
accept the electrons to form some ions like OH-, O2- etc.
 The metallic ions from anodic part and non- metallic ions from cathodic
part diffuse towards each other through conducting medium and form a
corrosion product somewhere between anode and cathode.
 The electrons which are set free at anodic part flow through the metal
and are finally consumed in the cathodic region.(product of corrosion)
 Thus we may sum up that electrochemical corrosion involves:

Mechanism of wet or electrochemical corrosion:-

In a electrochemical corrosion the electronic current flow from anode to
cathode

In wet corrosion the anodic reaction involves-

The dissolution of metal as corresponding metal ions with the liberation of free
electrons:

M –--------> Mn+ + ne

Whereas the cathodic reaction consumes electrons either by

a) Evolution of hydrogen
or

b) By absorption of oxygen depending on the nature of the corrosive

environment
Evolution of hydrogen: occurs in acidic environments.

For ex: in the corrosion of iron metal the anodic reaction is dissolution of Fe as
ferrous ions with liberation of electrons.

Fe –-----> Fe+2 + 2e- oxidation.

These electrons flow through the metal from anode to cathode (acidic region)
where H+ ions are eliminated as H2 gas.
2H+ + 2e- –------> H2 reduction.

The overall reaction is Fe + 2H+ –------> Fe2+ + H2

This type of corrosion causes “displacement of hydrogen ions from the acidic
solution by metal ions. In hydrogen evolution type corrosion, the anodes are
very large areas, where as cathodes are small areas.

All metals above hydrogen in the electrochemical series have a tendency to

get dissolved in acidic solution with simultaneous evolution of hydrogen.
Absorption of oxygen type corrosion:

Rusting of Fe in neutral aqueous solution of electrolytes like NaCl in the

presence of atmospheric oxygen is a common example of this type of
corrosion.

The surface of iron will be usually coated with a thin film of iron oxide.
However if this oxide film develops some cracks, anodic areas are created on
the surface.

While pure metal parts act as cathode.

Thus anodic areas are very small surface parts.

The rest of the surface of the metal forms cathodes.

Thus at the anodic part iron metal dissolves as Fe+2 ions with the liberation of
e-.

Fe –-----> Fe+2 + 2e-

The liberated e- flow from anodic to cathodic areas through iron metal during
which they interact with dissolved oxygen and moisture.

½ O2 + H2O + 2e- → 2OH-

The Fe+2 ions and OH ions diffuse and form ferrous hydroxide precipitate
when they meet with each other

Fe+2 + 2OH- –------> Fe (OH)2

If enough O2 is present Fe (OH)2 is easily oxidized to Fe(OH)3 (ferric hydroxide)

4 Fe (OH) 2 + O2 + 2H2O –-----> 4Fe (OH)3

 The product called ( yellow rust) actually corresponds to Fe(OH)3.H2O.

If the supply of O2 is limited, the corrosion product may be even

 Black rust (anhydrous magnetite Fe3O4.)

GALVANIC SERIES:-

Electrochemical series will give useful information regarding chemical

reactivity of metal and may not be able to provide sufficient information in
predicting the corrosion behavior of metal in a particular set of environmental
conditions. Passivation makes effective electrode potential of some metals
more passive and acts as cathodic and exhibit noble behavior. This behavior is
exactly opposite to that predicted by electrochemical series. For more practical
series called Galvanic series, have been prepared by studying the corrosion of
metals and alloys in a given environment like in sea water.

Galvanic series gives real and useful information about corrosion behavior of
metals and alloys in a given environment.
(Mg Zn ) ( Zn—Cu)

TYPES OF ELECTROCHEMICAL CORROSION

The electrochemical corrosion is classified into the following two types:

(i) Galvanic (or Bimetallic) Corrosion

(ii) Differential aeration or concentration cell corrosion.

Galvanic Corrosion:

When two dissimilar metals (eg., zinc and copper) are electrically connected
and exposed to an electrolyte, the metal higher in electrochemical series
undergoes corrosion. In this process, the more active metal (with more
negative electrode potential) acts as a anode while the less active metal (with
less negative electrode potential) acts as cathode.
In the above example, zinc (higher in electrochemical series) forms the anode
and is attacked and gets dissolved; whereas copper (lower in electrochemical
series or more noble)acts as cathode.

Mechanism: In acidic solution, the corrosion occurs by the hydrogen evolution

process; while in neutral or slightly alkaline solution, oxygen absorption occurs.
The electron-current flows from the anode metal, zinc to the cathode metal,
copper.

Thus it is evident that the corrosion occurs at the anode metal; while the
cathodic part is protected from the attack.
Example:

(i) Steel screws in a brass marine hardware

(ii) Lead-antimony solder around copper wise;

(iii) A steel propeller shaft in bronze bearing

(iv) Steel pipe connected to copper plumbing.

Differential aeration or concentration cell corrosion.

It is due to electrochemical attack on the metal surface, exposed to an

electrolyte of varying concentrations or of varying aeration. It occurs when one
part of metal is exposed to a different air concentration from the other part.
This causes a difference in potential between differently aerated areas. It has
been found experimentally that poor-oxygenated parts are anodic.

Examples:

i) The metal part immersed in water or in a conducting liquid is called water

line corrosion.

ii) The metal part partially buried in soil.

Explanation: If a metal is partially immersed in a conducting solution the metal
part above the solution is more aerated and becomes cathodic. The metal part
inside the solution is less aerated and thus becomes anodic and suffers
corrosion. Example:

If a metal (say Zn) is partially immersed in a dilute solution of a neutral salt (say
NaCl) and the solution is not agitated properly, then, the parts above and
closely adjacent to the waterline are more strongly aerated, because of easy
access of oxygen and hence, become cathodic. On the other hand, parts
immersed to greater depth, which have less access of oxygen, show a smaller
oxygen concentration and thus, become anodic. So, a difference of potential is
created, which causes the flow of current between the two differentially-
aerated areas of the same metal. Zinc will dissolve at the anodic area, and
oxygen will take up electrons at the cathodic area to form hydroxyl ions.

Zinc will dissolve at the anodic area, and oxygen will take up electrons at the
cathodic area to form hydroxyl ions.
Pitting is a localized attack, which results in the formation of a hole around
which the metal is relatively un attacked. The mechanism of this corrosion
involves setting up of differential aeration or concentration cell. Metal area
covered by a drop of water, dust, sand, scale etc. is the aeration or
concentration cell.
Pitting corrosion is explained by considering a drop of water or brine solution
(aqueous solution of NaCl) on a metal surface, (especially iron). The area
covered by the drop of salt solution as less oxygen and acts as anode. This area
suffers corrosion, the uncovered area acts as cathode due to high oxygen
content. It has been found that the rate of corrosion will be more when the
area of cathode is larger and the area of the anode is smaller. Hence there is
more material around the small anodic area results in the formation hole or
pit.

At anode: Fe is oxidized to Fe2+ and releases electrons. Fe Fe2+ +2e

At cathode: Oxygen is converted to hydroxide ion ½ O2 + H2O + 2e- 2OH

The net reaction is Fe + 2OH- Fe (OH)2

Factors affecting corrosion:
There are two factors that influence the rate of corrosion.

i) Nature of metals

ii) Nature of the corroding environment.

Nature of metals:

1) Position in galvanic series:-The metal higher in series is more active and

suffers corrosion. The rate and extent of corrosion is directly proportional to
electrode potential difference between them.

2) Over voltage: - when a metal, which occupies a high position in galvanic

series (say Zinc), is placed in H2SO4 , it undergoes corrosion forming a film and
hydrogen gas. The initial rate of reaction is quite slow, because of high over
voltage (0.70 V) of the zinc metal, which reduces the effective electrode
potential to a small value. However, if few drops of copper sulphate (CuSO4)
are added, the corrosion rate of zinc is accelerated, because some copper gets
deposited on the zinc metal forming minute cathodes, where the hydrogen
over voltage is only 0.33 V, thus, reduction in over voltage of the corroding
metal/ alloy accelerates the corrosion rate.

Zn has over hydrogen voltage due to which the rate of corrosion of Zn is very
slow (Zn rod dipped in ZnSO4). But when CuSO4 solution is added to H2SO4 Cu
gets deposited on Zn rod and acts as small cathode. For Cu higher over
hydrogen voltage value is less. Hence rate of corrosion of Zn in presence of cu
becomes more. Thus metals which have higher over voltages, the rate of
corrosion is high.

Ex: corrosion of Zn rod dipped in H2SO4 is very slow. When small amount of
CuSO4 solution is added to H2SO4 , Cu gets deposited on the Zn rod and acts
as cathode and the rate of corrosion of Zn increases. (Over voltage of Zn metal
is 0.73)

3) Purity of metal: - Impurity of a metal generally causes heterogeneity and

form minute electrochemical cells and the anodic part gets corroded.

For eg: Zn metal containing impurity such as Pb ( or) Fe undergoes corrosion .

The rate and extent of corrosion increases with extent of impurities.

4) Nature of the surface film: - when metals are exposed to atmosphere,

practically all metals get covered with a thin surface film of metal oxide. The
ratio of the volume of metal oxide to the metal is known as specific volume
ratio. Greater the specific volume ratio, lesser is the oxidation corrosion rate.
For eg: the specific volume ratio of Ni, Cr, Ware 1.6, 2.0 and 3.6 respectively.
Consequently the rate of oxidation corrosion is least for (w) tungsten.

5) Nature of the corrosion product:-

a) Solubility of corrosion products: If the corrosion product is soluble in the

corroding medium, then corrosion proceeds at a faster rate otherwise if it is
insoluble, corrosion will be suppressed

e.g: PbSO4 formation in case of Pb in H2SO4.

b) Volatility of corrosion products: - If the corrosion product is volatile, it

evaporates as soon as it is formed, there by leaving the underlying metal
surface exposed for further attack. This causes rapid and continuous corrosion.

For eg: Mo forms MoO3 volatile oxide.

Nature of the corroding environment:-

i) Temperature: With increase of temperature, the corrosion rate also

increases because the reaction as well as diffusion rate of ions in the corrosion
medium increases.

ii) Humidity: The higher the humidity of the atmosphere the greater is rate and
extent of corrosion because the moisture acts as medium for O2 in air and
behaves as an electrolyte.

For eg: atmospheric corrosion of iron is slow in dry air compound to moist air.
Iron combines with O2 and water to form ferrous hydroxide which combines
with atmospheric CO2 to form ferrous bicarbonate.

2Fe + O2 + 2H2O –-------> 2Fe(OH)2

Fe(OH)2 + CO2 –------>Fe(HCO3)2

iii) Effect of pH: - Generally acidic media are more corrosive than alkaline and
neutral media. Hence metals may be virtually classified according to pH range
in which they will be affected (or) resistant. However atmospheric metals like
Al, Pb etc. are corroded in alkaline medium and the corrosion rate of iron in O2
free water is slow, until the pH is below Zn is rapidly corroded in weakly acidic
solutions.

iv) Presence of impurities or suspended particles in atmosphere: Atmosphere

in industrial areas contains corrosive gases like CO2 , H2S, SO2 and fumes of
HCl, H2SO4 etc. In presence of these gases, the acidity of the liquid adjacent to
the metal surfaces increases and its electrical conductivity also increases,
thereby the rate of corrosion increases.

In case of atmospheric corrosion:

(i) if the suspended particles are chemically active in nature (like NaCl,
Ammonium sulphate),they absorb moisture and act as strong electrolytes,
thereby causing enhanced corrosion;

(ii) if the suspended particles are chemically inactive in nature (eg., charcoal),
they absorb both sulphur gases and moisture and slowly enhance corrosion
rate.

CORROSION CONTROL
1) Cathodic protection : The principle involved in this method is to force the
metal to be protected to behave like a cathode thereby corrosion doesn’t
occur.
There are two types of cathodic protection. Both corrosion protection systems,
however, operate on the same basic concept of bimetallic/galvanic corrosion.

Sacrificial anodic protection method: -

In this method the metallic structure to be protected is connected by a wire to

a more anodic metal, so that all the corrosion is concentrated at this more
active metal implies the more active metal itself gets corroded slowly. While
the parent structure which is cathodic is protected .The more active metal so
employed is called “sacrificial anodic” whenever the sacrificial anode is
consumed completely. It is replaced by a fresh one.

Metal commonly employed as sacrificial anodes are Mg, Zn, Al and their alloys.
Application: Sacrificial anodes are used for the protection of buried pipe lines
underground cables, marine structures, ship hulls, water tanks etc.
ii) Impressed current cathodic protection: - In this method an impressed
current is applied in opposite direction to nullify the corrosion current and
convert the corroding metal from anode to cathode.

Usually the impressed current is derived from a direct current source (like
battery or rectifier on ac line) with an insoluble anode, like graphite, high silica
iron, scrap iron, stainless steel or platinum.
Usually a sufficient d.c is applied to an insoluble anode, buried in the soil (or
immersed in the corroding medium) and connected to the metallic structure to
be protected.

The anode is buried is a backfill such as coke breeze or gypsum to increase the
electrical contact between itself and the surrounding soil.

Some common backfill materials include:

Coal coke breeze

Petroleum coke breeze

Bentonite clay

Gypsum

Sodium sulphate

What does Backfill mean?

Backfill refers to products or materials used to fill excavations. The most common
form is composed of a mixture of gypsum and calcium bentonite.
Apart from filling holes, one of the primary purposes is to mantle sacrificial anodes
under the ground. This enhances the ability of the anode to lessen electrical
resistance, thus reducing corrosion as well.
Applications:- This type of protections is used in buried structures such as tanks
and pipelines, transmission line towers, marine piers, laid up ships etc.,

Advantages: - They can be automatically controlled which reduce maintenance

and operational costs.

Example:

Impressed Current Cathodic Protection

(ICCP)
ICCP Systems are corrosion control methods which produce a powerful
external current to suppress natural electrochemical activity by supplying a
controlled amount of DC current to submerged surfaces, using zinc
 reference anodes and metal oxide anodes. The electrical current is
continuously monitored and regulated by the system itself to prevent the
electrochemical action of galvanic corrosion before it can begin. This is
therefore a widely preferred method of Cathodic Protection as it requires
little to no maintenance and reduced overall costs as a result, as well as the
advantage of a long service life. Once installed and activated, ICCP systems
can provide upwards of 30 years corrosion protection to a given structure.

Steel framed buildings with masonry cladding are often subjected to

corrosion of the steelwork due to water ingress; if the stone or brick
masonry is in contact with the steel frame, the corrosion will often cause
extensive cracking in the building facades. Therefore uniquely design
and install ICCP systems can be used for a number of steel framed
buildings which are at risk of deterioration as a result of corrosion

Overpass on Division
St. in Kingston, Ontario (Canada) where one the very first installations of an
impressed cathodic protection system in North America is still in operation.
The Internet of Things (IoT) and cathodic protection
identifies early pipe failure

A common technique to control the corrosion of underground steel pipes

is called cathodic protection. A sacrificial piece of metal (anode) is
connected to the pipe and this anode corrodes selectively instead of the
steel pipe.

As such, the sacrificial anode must be periodically replaced. Routine

inspection of sacrificial anodes is necessary to establish when they are due
for replacement.
To remove the need for manual inspections, Melbourne Water, in
collaboration with Green Technology Services (GTS) Group, Sigfox
network operator Thinxtra and IBM, has developed an Internet of Things
(IoT) system to monitor these cathodic protection installations.
GTS group was responsible for the IoT device design, building the firmware
and creating the prototype. Thinxtra supplied the connectivity, as well as
providing support to set everything up correctly. IBM provided the IoT
gateway and systems to monitor the data.
The prototype devices have performed without fault and Melbourne Water
is now planning to roll out the system across its network of pipes.
Additionally, similar technology is being developed for its drainage
infrastructure to provide real-time insight into system operation.
Prevention of corrosion by other methods:
Metallic coatings:

Anodic coatings (galvanization):

Galvanizing is the process of coating iron or steel sheets with a thin coat of zinc
to prevent them from rusting.

For carrying out galvanizing firstly the iron or steel article such as sheet, pipe or
wire is cleaned by pickling with dil H2SO4 solution for 15-20 mts at 60-900C. In
pickling any scale, dirt, oil, grease or rust and any other impurities are removed
from the metal surface. The article is washed well and then dried. It is then
dipped in bath of molten zinc maintained at 425- 430oC. The surface of bath is
kept covered with ammonium chloride – flux to prevent oxide formation. The
article is covered with a thin layer of zinc when it is taken out of bath. It is then
passed through a pair of hot rollers, which removes any excess of zinc and
produces a thin film of uniform thickness then it is annealed and finally
collected slowly
Uses: - Roofing sheets, wires, pipes, nails, bolts, screws, buckets, tubes etc.
which are made of iron are protected from atmospheric corrosion by
galvanizing them. But galvanized utensils cannot be used for preparing and
storing food stuffs, especially acidic ores since zinc gets dissolved in all acids
forming highly toxic compounds.