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CORROSION AND ITS

CORROSION CONTROL
A wide variety of metals/alloys are being used in daily life, equipment, plant
machineries, industrial structures, bridges, building etc… and all these have natural
tendency to get tarnished or deteriorated by the environment to which
they are exposed.

Definition:
Corrosion is the process of gradual deterioration of a metal from its
surface due to an unwanted chemical or electrochemical interaction of metal with
its environment. The surfaces of almost all metals begin to decay more or
less rapidly, when e x p o s e d t o g a s e o u s a t m o s p h e r e , w a t e r o r a n o t h e r
r e a c t i v e l i q u i d m e d i u m . A s a result of the decay, the metals are converted
to their oxides, hydroxides, carbonates, s u l p h i d e s e t c . T h e p r o c e s s o f
d e c a y o f m e t a l b y e n v i r o n m e n t a l a t t a c k i s c a l l e d corrosion.Ex:
formation of reddish brown scale and powder of rust (Fe2O3.3H2O) on the
surface of iron and formation of green film of basic carbonate
[CaCO3+Cu(OH)2] on the surface of copper.

Cause of corrosion:
Most metals (with the exception of noble metals such as Au,Pt, etc.) exist
in nature in combined forms as their oxides, carbonates,

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hydroxycarbonates, sulphides, chlorides and silicates. These chemically
combined states of metal known as ‘ores’.
These chemically combined states of metal are thermodynamically
m o r e stable states for metal. These are reduced to their metallic states
from their ores, during their extraction processes. During extraction of metals,
considerable amounts of energy are required in metallurgy. Consequently,
isolated pure metals can be regarded in a higher energy state which are
thermodynamically unstable than their corresponding ores, and they have a
natural tendency to revert back to combined state (
thermodynamically more stable state).

ORE → METAL → CORRODED METAL

As a result when metals are put into use, in various forms, they are exposed to
environment such as dry gases, moisture, liquids, etc. the exposed metal surfaces
begin to decay and forms more stable compounds of metals like oxides,
carbonates, etc. Thus, corrosion is a process “reverse of extraction of metals”.

Effects of corrosion:
•The valuable metallic properties like conductivity, malleability, ductility
etc. are lost due to corrosion and thus loss of efficiency.
•The process of corrosion is not incurred and is responsible for the enormous
wastage of machines, equipment and different type of metallic products.
•Losses occurring due to corrosion cannot be measured in terms of the cost
of metals alone, but the high cost of fabrication into equipment/machine
tool/structures should also be considered.
•The approximate estimate of loss of metal due to corrosion, as 2 to 2.5
billiondollars per annum all-over the world.

In view of the above, an engineer must understand the mechanism of corrosion so

that the effects of corrosion can be minimized by avoiding the corrosion conditions
and provide simultaneous protection against corrosion.

Types of corrosion (Theories of corrosion):

The corrosion process proceeds in two types by chemical and electrochemical
attack of environment.

CHEMICAL CORROSION (DRY CORROSION):

This type of corrosion occurs mainly through the direct chemical action
of e n v i r o n m e n t / a t m o s p h e r i c gases such as oxygen, halogen,
hydrogen sulphides, Sulphur dioxide, nitrogen or anhydrous
i n o r g a n i c l i q u i d w i t h m e t a l s u r f a c e s i n immediate proximity.
A tarnished surface of a metal is the best example of dry corrosion.
Metals like Al, Zn and even Fe etc. have a natural tendency to get oxidized and
form a thin f i l m o f t h e i r o x i d e s o n t h e s u r f a c e o f m e t a l w h e n t h e y
e x p o s e d t o a t m o s p h e r i c oxygen.
Dry corrosion may be due to a) Oxidation corrosion, b) Corrosion by
other gases.

1. Oxidation corrosion:
Direct action of oxygen at high or low temperatures on metals in the absence of
moisture is called oxidation corrosion. The alkali (Li, N a , K , R b e t c . ) a n d
alkaline earth (Be, Ca, Sr etc.) metals are rapidly oxidized at low
temperatures, while metals like Fe, Al etc. (except noble metals
Au, Pt etc.) are oxidized at high temperatures by interaction
o f oxygen.

2M → 2Mn+ + 2e (Loss of electron : Oxidation)

(Metals Ion)

n/2 O2 + 2e → n O2- (Gain of electron : Reduction)

2M + n/2 O2 → 2Mn+ + n O2-

Mechanism: The oxidation of the metal occurs at the surface

first resulting the formation of metal oxide layer. The nature of
o x i d e l a y e r f o r m e d o n t h e m e t a l surface decides the further action with the
environment.
If the oxide film formed is continues and rigidly adhered to the surface
of metal is impervious in nature, and is called stable oxide layer. It is
protective and shields the metal from further corrosion.
Ex: oxide films on Cu or Al acts as a protective coating and further corrosion is
prevented.
If unstable oxide film is formed decomposes back into the metal and oxygen.
Ex: noble metals like Pt, Au etc. corrosion is not possible, since oxide layer formed
is very unstable and decomposes back to metal and oxygen.

If oxide layer formed is porous or volatile is non-protective and more feasiblefor

further attack of environment, hence corrosion continues till the entire
metal is converted to metal oxide. Ex: Mo forms a volatile oxide layer.

Pilling Bedworth rule : Greater is the specific volume ratio, lesser it the
rate of corrosion. If the volume of the metal oxide layer is at least as great as the
volume of metal from which it is formed is non-porous and becomes protective
layer by tightly adhering to the base metal.

Volume of metal oxide formed

Specific volume ratio = ----------------------------------
Volume of the metal

For example, the specific volume ratios of W, Cr and Ni are 3.6, 2.0 and
1.6 respectively. Hence, the rate of corrosion is least in Tungsten (W).
If the volume of metal oxide is less than the volume of the metal, the
oxide layer is porous, non continuous and non-protective and faces strains. Hence
cracks and pores are developed in the layer, creating access to
atmospheric oxygen to r e a c h t h e u n d e r l y i n g m e t a l . I n t h i s c a s e
c o r r o s i o n i s c o n t i n u o u s a n d r a p i d l y increases.
For example: Li, Na and K.

2. Corrosion by other gases:

In the absence of moisture a few gases likeSO2, CO2, Cl2, H2S a n d F 2
e t c a t t a c k t h e m e t a l . T h e d e g r e e o f c o r r o s i o n depends on the
formation of protective or non-protective films on the metal surface.
If the film formed is protective or non-porous, the intensity or
e x t e n t o f attack decreases, because the film formed protects the metal from
further attack.Ex: AgCl film, resulting from the attack of Cl2 on Ag.
If the film formed is non-protective or porous, the surface of the whole metalis
gradually destroyed. Ex: dry Cl2 gas attacks on tin (Sn) forming volatile SnCl4.

ELECTROCHEMICAL CORROSION (WET CORROSION):

Wet corrosion or electrochemical corrosion takes place under wet or
moist conditions through the formation of short circuited tiny
electrochemical cells. Wet corrosion is more common than dry corrosion.
This type of corrosion can be observed
(i) w h e n a metal is in contact with conducting
liquid.
( ii)When two dissimilar metals are dipped partially in a
solution.
This corrosion occurs due to the existence of separate ‘anodic’ and
‘cathodic’ areas. Impact of corrosive environment on a portion of metal, changes
its electrode potential compared to its original value of the electrode
potential of the metal. This creates a potential difference within the metal
system. The area of lower reduction potential created in the metal is
known as the ‘anodic area’ and that with higher reduction potential value is
called ‘cathodic area’.
The current flows from the anodic area to the cathodic area
t h r o u g h t h e conducting solution. A galvanic cell is created in the metal.
At anodic area, oxidation reaction takes place, so metal is destroyed by either
dissolving or assuming combined state. Hence, corrosion always occurs
at anodic area.
At anodic area: M -------- Mn++ n e- (Oxidation)
Mn+ ----- → dissolves in solution or forms compound such as oxide.
At cathodic area, reduction reaction takes place. Usually, cathode reactions do not
affect the cathode, since most metals cannot be further reduced. So, at cathodic
part, dissolved constituents in the conducting medium accept the electrons to form
some ions like OH-, O2-.The metallic ion formed at anodic part and non-metallic
ion formed at cathode part diffuse towards each other through conducting
medium and form a corrosion p r o d u c t s o m e w h e r e b e t w e e n a n o d e a n d
c a t h o d e . T h e e l e c t r o n s s e t f r e e a t t h e anode flow through the metal and
are finally consumed in the cathodic reaction.
Thus, we may sum up that electrochemical corrosion involves:
i)the formation of anodic and cathodic areas
o r p a r t s i n c o n t a c t w i t h each other,
i i ) p r e s e n c e o f a c o n d u c t i n g m e d i u m ,
i i i ) c o r r o s i o n o f a n o d i c a r e a s o n l y ,
iv)Formation of corrosion product somewhere
b e t w e e n a n o d i c a n d cathodic areas.

Electrochemical corrosion involves flow of electron-current

b e t w e e n t h e anodic and cathodic areas. The anodic reaction involves in
dissolution of metal as corresponding metallic ions with the liberation of free
electrons.
At anodic area: M --------Mn+ + n e- (Oxidation)

The anodic reaction consumes electrons with either by

 i) e v o l u t i o n o f hydrogen, or
ii) ii) absorption of oxygen depending on the nature of the
c o r r o s i v e environment.

i) Evolution of hydrogen:

In absence of oxygen.
In acidic medium: 2 H+ + 2e- → H2 ↑ (Reduction)
In neutral or alkaline medium: 2H2O + 2 e- → H2 ↑ + 2OH-
Considering metal like Fe,
At the anodic reaction is dissolution of iron as ferrous ion with the liberation
of electrons.
Fe -------→ Fe2+ +2 e- (oxidation)
These electrons flow through the metal, from anode to cathode, where
H+ ions are eliminated as hydrogen gas from acidic solution.

2 H+ + 2e- → H2 (Reduction)

Thus, this type of corrosion causes “displacement of hydrogen ions from the
acidic solution by metal ions. “ Consequently, all metals above
hydrogen in the electrochemical series have a tendency to get
d i s s o l v e d i n a c i d i c s o l u t i o n w i t h simultaneous evolution of hydrogen.

The overall reaction:

Fe + 2H+ → Fe2+ + H2 ↑

ii)Absorption of oxygen: in presence of dissolved oxygen.

In acidic medium: 4H+ + O2 + 4e- → 2H2O

In neutral or alkaline medium: 2H2O + O2+ 4e- → 4OH-
By considering

Rusting of iron in neutral aqueous solution of electrolytes in the presence

of atmospheric oxygen.

At the anodic areas of the metal (iron) dissolve as ferrous ions with liberation of
electrons.
Fe --------→ Fe2+ + 2e- (Oxidation)

The liberated electrons flow from anodic to cathodic areas,

t h r o u g h i r o n metal, where electrons are intercepted by the dissolved oxygen as:
½ O2 + H2O + 2e- -------→ 2 OH- (Reduction)

The Fe2+ ion at anode and OH- ions at cathode diffuse and when they
meet, ferrous hydroxide is precipitated.

Fe2+ + 2OH- --------→ Fe(OH)2

Figure : Wet Corrosion Mechanism

If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric

hydroxide.
4 Fe(OH)2 + O2 + H2O --------→ 4 Fe(OH)3

This product is called yellow rust, actually corresponds to Fe2O3. H2O

If the supply of oxygen is limited the corrosion product may be even
black anhydrous magnetite, Fe3O4.

Galvanic corrosion:
When two dissimilar metals are in contact with each other in a corrosive
conducting medium. The two metals differ in their tendencies to undergo
oxidation; the one with lower electrode potential or the more active metal (higher
up in electrochemical series) acts as anode and the one with higher electrode
potential acts as cathode. The potential difference between two metals is the cause
or driving force for corrosion. The anodic metal undergoes corrosion and the
cathodic metal is generally unattacked.
Ex: When Zn and Cu are connected and exposed to corroding atmosphere Zn
becomes anodic because of its higher oxidation potential or higher
position in the e l e c t r o c h e m i c a l s e r i e s . Z n u n d e r g o e s o x i d a t i o n
a n d c o r r o d e d , w h e r e a s C u undergoes reduction and protected. The
electrons released by Zn reach Cu through the metal.

Figure of Galvanic Corrosion

Anodic metal: Zn ---------- Zn2+ + 2 e- (Oxidation) (More active metal)
At cathodic metal: depending on nature of the corrosion environment the
cathode reaction (reduction) may be either hydrogen evolution or oxygen
absorption.
i) 2 H+ + 2 e- → H2 ↑
ii) ½ O2 + H2O + 2e- -------→2 OH-

Galvanic corrosion can be minimized by

1. Avoiding galvanic couples.
2. Providing an insulating material between two metals.

Some more examples:

•Steel screws/ rivets in copper sheet.
•Steel pipe connected to copper plumbing.
•Lead antimony solder around copper wire.

Differential aeration corrosion:

W h e n a m e t a l i s e x p o s e d t o d i f f e r e n t a i r concentrations or
oxygen concentrations, the part of the metal exposed to higher oxygen
concentration acts as cathodic region, and part of the metal exposed to lower
oxygen concentration acts as anodic region. Consequently, the poorly
oxygenated region undergoes corrosion. Corrosion of metals arising as a result of
the formation of a oxygen concentration cell due to the uneven supply of air on the
metal surface.
Figure of Corrosion due to Partial immersion of metal in solution

Ex: The Zn metal partially immersed in a NaCl solution. The parts above the
waterline more oxygenated are more strongly aerated and hence, become cathodic.
On the other hand, parts immersed to greater depth show a
s m a l l e r o x y g e n concentration and thus become anodic. So, a difference of
potential is created, which c a u s e s a f l o w o f c u r r e n t b e t w e e n t h e t w o
differently aerated areas of the same metal.
Zn will dissolve at anodic area, and oxygen will take up electrons
at the cathode areas to form hydroxyl ions. Thus, Zn undergoes
c o r r o s i o n a t p o o r l y oxygenated part.

At anode: Zn ----------→ Zn2+ + 2 e- (poorly oxygenated part)

At cathode: ½ O2 + H2O + 2e- -------→ 2OH- (well oxygenated part)

Examples:
•P a r t s o f t h e n a i l i n s i d e t h e w a l l , b e i n g e x p o s e d t o l o w e r
o x y g e n concentration than the exposed part, undergo corrosion.
•Window rods inside the frame suffer corrosion but not the exposed
region.
•Paper pins inside the paper gets corroded, and the exposed parts is free
from corrosion.
•Metal under dirt, dust, scale or water undergoes corrosion.
•P a r t i a l l y b u r i e d p i p e l i n e i n s o i l o r s u b m e r g e d i n w a t e r u n d e r g o e s
corrosion below the soil or water where as the exposed part is free from
corrosion.
Waterline corrosion: It is a case of differential aeration corrosion. More prevalent
in cases such as ocean going ships, water storage steel tanks etc, in which a portion
of metal is always under water. T h e w a t e r l i n e c o r r o s i o n t a k e s p l a c e d u e
t o t h e f o r m a t i o n o f d i f f e r e n t i a l oxygen concentration cell. The part of the
metal below the water line exposed only to t h e dissolved oxygen
while the part above the water is exposed to higher
concentration of the atmosphere of the atmosphere. Thus, part of the
metal below the water acts as anode and undergoes corrosion and the part above
the water line is free from corrosion.
A distinct brown line is formed just blow the water line due to the deposition of
rust.
At anode: Fe -------- Fe2+ + 2e- (Oxidation)
At cathode: ½ O2+ H2O + 2e- ------- 2 OH-

Example of Water storage

Pitting Corrosion:
Pitting corrosion is a localized and accelerated corrosion,
resulting in the formation of pits or pin holes around which the metal is
relatively unattacked. It is characterized by small anodic and large
cathodic areas, resulting in accelerated corrosion at the anodic area. It is
an auto catalytic process, with the initially formed pit produces conditions
which are both stimulating and necessary for the continuing activity of the pit.
It is generally initiated by the deposition of extraneous matter such as sand, scale,
water drop, dust etc, or due to the break down of the protective film on metal
surface. The metal below the deposit is exposed to lower oxygen concentration,
acts as anode and undergoes corrosion. The metal surrounding the deposit
acts as cathode since it is exposed to higher concentration of oxygen. Consider a
drop of water resting on the surface of metal, the metal surface w h i c h i s
covered by the drop has low oxygen concentration and thus acts
as an a n o d e a n d s u f f e r s c o r r o s i o n . T h e u n c o v e r e d m e t a l
s u r f a c e d u e t o h i g h O 2 concentration acts as cathode.

At anode: Fe -------- Fe2+ + 2e- (Oxidation)

At Cathode: ½ O2 + H2O + 2e- ------- 2 OH- (Reduction)

Oxidation Fe2+ + 2OH- -- Fe(OH)2 ------- Fe(OH)3

Because of small anode and large cathode accelerated corrosion takes
place below the deposit. Once the corrosion product is formed, it further
provides the condition for differential aeration below the corrosion
product and the surrounding metal parts. The pit grows and ultimately may
cause failure of metal.
Pitting is one of the most destructive forms of corrosion. It causes equipment t o
fail because of perforation with only a small percent weight loss
of the entire structure. It is often difficult to detect pits because
o f t h e i r s m a l l s i z e a n d a l s o because pits are covered with corrosion
products
Pitting is dangerous because it is localized and intense of
c o r r o s i o n a n d failures often occur with extreme suddenness. As such, it is
rather difficult to asses precisely the life of metal component undergoing pitting
corrosion. Loss of metal due t o p i t t i n g i s o f t h e l i t t l e s i g n i f i c a n c e w h e n
c o m p a r e d t o i n d i r e c t l o s s e s s u c h a s production, repairs and replacements.

FACTORS AFFECTING THE RATE OF CORROSION:

Position of metal in the Galvanic series:

W h e n t h e m e t a l i s h i g h e r u p i n t h e galvanic series, greater is the
oxidation potential. Thus, greater is its tendency to become anodic and
hence greater is the rate of corrosion. Thus, extent of corrosion depends upon the
position of the metal in the galvanic series. When two metals are in electrical
contact, greater is the difference in their positions in the electrochemical series,
faster is the corrosion of anodic metal.

Relative areas of anode and cathode:

If a metal has small anodic area and large cathodic area, then the corrosion is more
intensive and faster is the corrosion rate at the anodic region.

Cathodic area
Rate of corrosion of anodic region ά -------------------------
Anodic area

As this ratio increases, the corrosion rate increases rapidly.

A t a n o d e , oxidation takes place and electrons are liberated.
At the cathode, these electrons are c o n s u m e d .
When anode is smaller and cathode region is large all the
e l e c t r o n s liberated at the anode are rapidly consumed at the cathode. This
process makes the anodic reaction to take place at its maximum rate, thus
increasing the corrosion rate. I f t h e c a t h o d e i s s m a l l e r , t h e c o n s u m p t i o n
o f e l e c t r o n s w i l l b e s l o w e r a n d t h e corrosion reaction as a whole will be
slower.

Nature of corrosion product: The nature of the corrosion product largely decides
the rate of further corrosion. The corrosion product formed on the surface
of the metal may or may not act as a protective film.
If the corrosion product deposited is insoluble, stable, uniform and nonporous,
it acts as a protective film preventing the further corrosion of metal. A thin,
invisible, impervious, continuous film formed on the surface acts as a
barrier between the fresh metal surface and the corrosion environment.
Ex; in oxidizing environments, metals like Al, Cr, Ti etc. are highly passive as
their oxides as corrosion products form protective films on the
m e t a l s u r f a c e preventing further corrosion. If the corrosion product is
soluble, unstable, non uniform and porous, the corrosion continues unabated.
In such cases the fresh metal surface is continuously exposed to the corrosion
environment and corrosion of the metal surface takes place continuously. When the
corrosion product formed is either soluble in the medium or formed away from the
anodic and cathodic sites, and then also the corrosion product does not have any
protective value. Ex; metals such as Fe, Zn, Mg etc. do not form any
protective film and are highly susceptible for continuous corrosion when
exposed to oxidizing environments.

Temperature:
The rate of a chemical reaction, in general, increases with rise in
temperature. Corrosion process is one such chemical reaction. Therefore, the rate
of corrosion increases as the temperature increases. Increase in temperature
increases the conductance of the corrosion medium, which also contributes to the
increase rateof corrosion.

Humidity:
The greater is humidity, the greater is the rate and extent of corrosion. This is due
to the fact that the moisture or vapors present in atmosphere acts as a solvent for
O2, H2S, SO2 and NaCl etc. to furnish the electrolyte essential for settin gup an
electrochemical cell.