Corrosion and its Control

“Gradual eating away (or) disintegration (or) deterioration of a

metal by chemical or electrochemical reaction with the
environment”

Reasons for corrosion:

o As compounds, metals are more stable thermodynamically.

o Metal will always have a strong tendency to convert itself into

more stable compound state.

o Hence, metals will try to go to lower energy states through

formation of compounds and thus attain stability.
Corrosion (oxidation)
Metal Metallic compound + energy
Extraction of metals
 Types of corrosion
a) Chemical corrosion (dry corrosion)

b) Electrochemical corrosion (wet corrosion)

a) Dry corrosion (chemical):

o Classified depending on the corroding agent

i) oxidation corrosion
o Oxygen present in the atmosphere attacks the metal forming
oxide layer on the surface of the metal.
M M2+ + 2 e-
½ O2 + 2e- O2-

M + ½ O2 M2+ + O2-

o Oxidation corrosion will lead to an oxide film which may be porous or

non-porous.
 Mechanism of Dry Corrosion

• Fe  Fe2+ + 2 e- (oxidation)
• ½ O2 + 2e-  O2- (reduction)
• Fe + ½ O2  Fe2+ + O2- (total reaction)

• Oxidation corrosion results in the formation of an metal-

oxide (MO) film which may be porous or non-porous.

Outward diffusion of metal ions through

Fe2+ the scale (faster, due to small size of Fe2+)
Fe  Fe2+ + 2e- (oxidation)
Metal (M)

2e- Inward diffusion of oxide ions through the

O2 scale (slower, due to larger size of O2-)
O2-

Atmospheric oxygen
 Types of corrosion
Pilling-Bedsworth Rule:
o “If the volume of metal oxide is equal to or greater than the volume
of the metal getting corroded, then the oxide film is non-porous and
protects the metal from further corrosion; If the volume of the
metal oxide is less than the volume of the metal getting corroded, it
will promote further corrosion of the metal”. (Vmetal Oxide / Vmetal)
o Cu, Al, Ni, Cr form non-porous oxide layers while Li, Na, K, Mg form
porous oxide layers.
o [P-B<1: Non-protective (Mg); P-B 1-2 : Protective (Al, Ti, Cr);
P-B >2: Non-protective – too thick and chip off (Mo, W, Nb)]
oTypes of oxide layers:
i) Stable oxide layer:
o It is a fine grain of oxide layer which is non-porous and adheres strongly to the
metal.
o Oxides of Al, Sn, Cu forms such impervious layers which prevents oxygen from
diffusing through the metal and hence further attack is stopped.
 Types of corrosion
ii) Unstable oxide layer:

o These are produced on noble metal surfaces and these oxide layers
decompose back to the metal.

Metallic oxide Metal + Oxygen

o Pt, Au etc. form such oxide films.

Unstable
Exposed surface metal oxide

+ O2 Metal oxide
metal Of air metal metal + O2
decomposes

Unstable oxide layer

Types of corrosion
iii) Porous oxide layer:

o These oxide layers have minute pores and are not impervious
layers.
o Oxygen will diffuse through the pores and promote further
corrosion.
o Fe is a good example of this type of corrosion.

Exposed Porous
surface metal oxide

Further Attack
metal + O2 through pores &
Of air metal
cracks continues

Porous oxide layer

Types of corrosion
iv) Volatile oxide layer:

oThese are oxide layers which evaporate as soon as they are

formed and hence further corrosion is facilitated.

oAfter some time the metal itself will disappear.

oMolybdenum is an example of volatile oxide layer corrosion.

Exposed
Volatile Fresh surface
surface
metal oxide Exposed for
Further attack
+ O2 Metal
metal oxide
Of air metal volatalizes metal

Volatile metal oxide

Types of corrosion
ii) corrosion by other gases:

o CO2, Cl2, SO2, F2 etc. are gases which can attack the metal and corrode
o Extent of corrosion depends on the affinity of the metal to the gas.
o These gases chemically react with the metal forming either porous or non-
porous layers of films. Chlorine forms protective AgCl and volatile SnCl4
• Hydrogen corrosion: H2S gas attacks steel at high temperature and make
them brittle (hydrogen embrittlement) by forming FeS as porous scales.
Fe + H2S FeS + 2H (atomic hydrogen)

iii) liquid metal corrosion:

o Flowing liquid metal (Hg) can penetrate through another metal to corrode.
o Gold (Au) can be corroded by mercury (Hg).
o Such corrosion is found in nuclear devices
 Hydrogen Embrittlement
oAtomic hydrogen is a cathodic product of many
electrochemical reactions

oAtomic hydrogen, due to its small size and mass

will easily penetrate most metal surfaces and
occupy favorable sites to form small pressurized
cavities/cracks/large blisters, or it may react
with the base metal to form hydrides

oThe accumulation of hydrogen in high strength

alloys leads to stress cracking and is often
referred to as hydrogen induced cracking or
hydrogen embrittlement
Types of corrosion
b) Wet or Electrochemical Corrosion:

o In this type of corrosion, a conducting liquid is in contact with a

metal or two dissimilar metals or alloys
o One part becomes anode and the other part cathode.
o At the anodic part corrosion (oxidation) occurs while reduction
takes place at the cathode.

At the anode: M Mn+ + ne-

o Mn+ either dissolved in solution or forms compounds such as oxides.

The rate of the electrochemical corrosion will depend on:

a) If the corrosion product is soluble in the medium, rate of corrosion

will be high.
b) If the corrosion product is insoluble in the medium, rate of
corrosion will be very low.
Types of corrosion
Electrochemical corrosion is present in the following types:
1. Hydrogen evolution type corrosion
2. Oxygen consumption type corrosion
3. Galvanic corrosion
4. Concentration cell corrosion
5. Pitting corrosion
6. Stress corrosion

1. Hydrogen evolution type corrosion

occurs when base metals are in contact with an acidic solution.
Eg. Anode : Fe Fe2+ + 2e- (oxidation)

Cathode : 2H+ + 2e- H2

The overall reaction is:
Fe + 2H+ Fe2+ + H2

o Simultaneously, metal ion will be produced at the anode while hydrogen will
evolve at the cathode
 Hydrogen evolution type corrosion

H+ Acidic solution (electrolyte) H+

H+ Cathodic Reaction

2 H+ + 2e-  H2
Fe  Fe2+ + 2e- Fe  Fe2+ + 2e- Anodic Reaction

Anodic area
(large) Fe
Anodic area
Cathodic area
(large) Fe
(small)
Types of corrosion
2.Oxygen absorption type corrosion:

Occurs when base metals are in contact with neutral solutions like water with
Dissolved oxygen (DO).
Rusting of iron is an example of this.

Anode : Fe Fe2+ + 2e- (oxidation)

These electrons move from anode to cathode and react with the electrolyte and
oxygen giving:

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

The Fe2+ at the anode and OH- at the cathode diffuse and react to produce
Fe(OH)2: Fe + 2 OH- Fe(OH)2

If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)

4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3 H2O)

 Oxygen absorption type corrosion

aq. NaCl solution (electrolyte)

½ O2 + H2O + 2e-  2OH-

Thin oxide
film layer
rust rust

Cathodic area Cathodic area (large) Fe

(large) Fe
Small Anodic area
(caused by cracks in the oxide film)

Fe  Fe2+ + 2e-
• Irrespective of the medium, the anodic oxidation reaction
remains the same, whereas the cathodic reaction varies
with respect to the medium.
• In acidic medium, cathodic reaction is hydrogen evolution
reaction
• In neutral medium, cathodic reaction is absorption of
oxygen leading to the formation of hydroxide ion,
eventually getting converted to the corrosion product, rust
formed between anode and cathode.
• Large cathode and small anode is undesirable as larger
cathode demands more electrons which needs to be
supplied by continuous corrosion happening at the anode
• Cathodic reaction (H2 evolution; Absorption of O2) is an
indirect indication of corrosion occurring at the anode. Why?
• Large cathode and small anode causes excessive corrosion,
known as localised attack or pitting.
3. Galvanic corrosion:
Occurs when two dissimilar metals in the electrochemical series are in
contact with each other (Joined by rivetting or welding) and
exposed to corroding environment.
This can be avoided or minimized by:
a) coupling metals which are close in the electrochemical series.
b) Making the cathode metal smaller in area than the anodic metal
• This type of corrosion is called galvanic “corrosion”.
• Zn  Zn2+ + 2e-
• Copper acts as more noble (cathode) and is protected.
• The electron flows from anode to cathode.
• E.g. steel screws in a brass marine hardware; lead-antimony
solder around a copper wire; steel pipe connected to copper
plumbing
.
4. Concentration cell corrosion: (Differential aeration corrosion)

o When a metal is exposed to different concentration of oxygen or any

other electrolyte, a concentration cell is formed.
o The part of the metal exposed to lower concentration of
oxygen (or) electrolyte becomes anode and the one exposed
to higher concentration becomes cathode.
o Corrosion starts at the anode (dissolves).
o This type of corrosion occurs when metals are partly dipped in
solutions, partly covered with dust, oil marks, sand etc.
o Eg. Zinc rod dipped in brackish water solution, water line corrosion.

Anode: Zn Zn2+ + 2e-

½ O2 +H2O + 2 e- 2 OH- Zinc rod
More oxygenated part Cathode:½O2+ H2O+2e- 2 OH-
(Cathode)
Water-line

e- Flow of electrons
Zn2+ NaCl solution
Corroding anode
Zn2+
Zn2+ Zn Zn2+ + 2 e- (less oxygenated part)
(Anode)
 Cathode
(Protected part)
Anode Cathode Sand

Anode
Metal Metal (Less
Oxygenated
part)
Scale
(a) (b)
Metals partly covered with dirt, dust, sand, scale, oil marks become
oxygen deficient areas – Anodes ; M Mn+ + 2e-
The other area which is more exposed to oxygen becomes oxygen
rich and acts as cathode
 Stress corrosion (cracking):

• Stress corrosion is caused by the combined effect of (i) the presence

of static tensile stress and (ii) a specific corrosive environment.

o Mostly observed in fabricated items of certain alloys (high-zinc brasses

and nickel brasses) due to the presence of stresses caused by heavy
working like rolling, drawing and insufficient annealing.

o However, pure metals are relatively immune to stress corrosion.

o Brass in the presence of ammonia;

o Mild steel in the presence of caustic alkali (NaOH) at high
temperature;
o Stainless steel in the presence of an acid chloride.
 Passivity
Definition: Passivity or passivation is the phenomenon in which a
metal or an alloy exhibits a much higher corrosion-resistance than
expected from its position in the electrochemical series.

Reason of passivity formation: Passivity is due to the formation of a

highly protective, but very thin (0.4 micron thick) and quite invisible
film on the surface of the metal or an alloy, which makes it more
noble.

Characteristics of the passive film: The film is insoluble, non-

porous and self-healing in nature. When broken, it will repair itself on
re-exposure in the presence of oxygen. Examples: Ti, Al, Cr, and
Stainless steel containing Cr.

Passivity is not a constant state and they exist only in certain

environmental conditions.
 Pitting Corrosion

• Pitting corrosion is a localized accelerated attack, resulting in the

formation of cavities around which the metal is relatively unattached

• Pitting results due to the breakdown or cracking of the protective film

on a metal at specific points giving rise to the formation of small anodic
and large cathodic parts

• Breakdown is caused by: surface roughness; scratches or cut edges,

local straining or metal due to non-uniform stresses, alternating
stresses, sliding under load and chemical attack.

• Due to the above conditions, rapid penetration of oxygen takes place

through some cracks in the oxide film or pin holes on metallic surfaces,
and pitting takes place leading to corrosion on leading to the
destruction of their passivity
PITTING: Metals owing their corrosion resistance to passive state
undergo any of the above breakdown conditions and show a marked
pitting corrosion leading to the destruction of their passivity

Al, Ti and stainless steel undergo pitting corrosion in acidic environment.

• Pitting Corrosion (For Understanding)
• Attacks a local area of the metal and leads to the formation of holes.
• Occurs when a small area is affected by the environment and
becomes anodic. Meanwhile, another area in the metal acts as a
cathode.
• Leads to galvanic corrosion which begins at the surface of the metal
but can spread downwards and eventually lead to the structural
failure of the metal.

• Mechanism: Metal is exposed to an oxygen-rich sodium chloride

electrolyte. The surface of the metal acts as a cathode and the pit
acts as an anode.
• Local production of metal cations in the pit creates an excessive
positive charge that in turn attracts the chlorine anions of the
electrolyte.
• The resulting metal chloride molecules now react with the water in
the environment to give the metal hydroxide and hydrochloric acid
which further speeds up the rate of corrosion.
GALVANIC SERIES:
In electrochemical series (EMF Series)
→Reduction electrode potential is tabulated increasing downward.
→ A metal high in the series is more anodic and undergoes corrosion
faster than the metal below it.
i) Li>Mg ii) Zn>Fe iii) Cu>Ag
Exceptions: (Tl, Al, Cr, Mg, Ni, Co)
 Ti (above Ag in EC series) is less reactive than Ag.
 Zn –Al couple Zn (below Al in EC series) is more active and corrodes.
 Because Ti and Al develop strongly adhering oxide layers on their
surfaces and hence their effective electrode potential are more positive
→ For the study of corrosion of metal and alloys → galvanic series is more
useful rather than EC series.
→ It gives real and useful information to predict relative corrosion
tendencies of metals.
 Electrochemical series Galvanic series

1) Electrode potentials are measured 1) By studying corrosion of

by dipping pure metals in their metals and alloys in unpolluted
salt solution (1M Concn.) without sea-water, without their oxide
any oxide film on them. films, if any, removed.

2) Position of a metal is fixed in EC 2) Position may shift. It is different for

series its pure form and alloys

3) No information regarding positions 3) Corrosion of alloys can be

of alloys studied from this series

4) It deals with only metals and non- 4) It deals with metals and alloys
metals

5) It predicts the relative 5) It predicts relative corrosion

displacement tendencies. tendencies
 Factors influencing corrosion
Factors influencing corrosion depend on:
a) Nature of the metal
b) Nature of the corroding environment

Nature of the metal:

i) Position in the galvanic series:
When two dissimilar metals are in contact, the more anodic metal
(Higher up in the series) will corrode.
The extent of corrosion depends on how far apart are the two metals
in the galvanic series.

ii) Over voltage:

When a metal (eg. Zn) is dipped in 1 N sulphuric acid, the initial rate
of corrosion is quite slow since hydrogen evolution takes place on Zn
at 0.7V.
If a few drops of CuSO4 are added, the hydrogen over voltage
comes down to 0.33V and corrosion rate increases.
Reduction in hydrogen over voltage increases the rate of corrosion.
 Factors influencing corrosion – Nature of metal

iii) Relative areas of cathode and anode:

When two dissimilar metals are in contact, the rate of corrosion is directly
proportional to the ratio of cathodic part to anodic part.
If anodic area is small, the corrosion is rapid.
iv) Purity of the metal:

Purer the metal, lesser is the rate of corrosion.

Due to impurities, local galvanic cells are formed and anode gets corroded.
v) Physical state of the metal:

The rate of corrosion will depend on the physical state of the metal such
as grain size, orientation of crystals, stress etc.

vi) Nature of surface film: (Pilling-Bedsworth rule):

Corrosion depends on the nature of surface film i.e. the oxide film is stable
or unstable or volatile or porous or non-porous will decide the rate of
corrosion of the metal.
 Factors influencing corrosion - Metal
vii) Passive character of the metal:

Some metals eg. Tl, Al, Cr, Mg, Ni and Co are passive and show resistance
to corrosion.
They form highly protective oxide layers on their surfaces which gives the
metal passive character and protects it from further corrosion.

viii) Solubility of corrosion product:

If the corrosion product is soluble in the environment in which the metal is

working, then the corrosion will proceed faster.
If the product is insoluble in the environment, then the corrosion is very
slow since the corrosion product becomes a protective layer on the metallic
surface. Eg.PbSO4.

ix) Volatility of the corrosion product:

o If the corrosion product is volatile, it evaporates as soon as it is formed

exposing fresh metal for corrosion and hence the corrosion becomes very
rapid and the metal will disappear over a period of time.
 Factors influencing corrosion - Environment
b) Nature of the corroding environment:
i) Temperature:
As temp. increases, the rate of corrosion also increases.

ii) Humidity in environment:

“Critical humidity” is the humidity above which the metallic corrosion

rate increases sharply.
Critical humidity depends on the nature of the metal as well as the
corrosion product.
When the humidity is higher, the gases eg. CO2, O2 dissolved in the
moisture and provide the conducting medium for electrochemical couple
to get formed and anode corrodes.

iii) Presence of impurities in the atmosphere:

Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 which are present in
the industrial areas provide conductive environment for enhancing the
electrochemical corrosion.
In marine environment, the Cl- is responsible for enhanced rate of
corrosion.
 Factors influencing corrosion – Environment
iv) Presence of suspended solids in the environment:
Particles like NaCl, (NH)4SO4 together with moisture act as conductive
electrolyte and enhance the rate of electrochemical corrosion.
v) Effect of pH:
Acid medium facilitates corrosion than neutral and basic media as
general rule.
The corrosion rate of Fe in oxygen free water is very slow up to pH 5.0
but in the presence of oxygen, the corrosion at pH 5.0 enhances
greatly.
At pH 4.0, the corrosion rate of Fe is very high since Fe2+ gets oxidised
to Fe3+.
Zinc corrodes rapidly in acidic solutions but the rate of corrosion is low
in alkaline medium (pH 11.0).
Aluminium corrodes less at pH 5.5 but the rate of corrosion is very
high in pH 8.5.
vi) Nature of ions present:
Anions like silicates form insoluble salts in the medium and inhibit
further corrosion.
But, Cl- present in the atmosphere destroy the protective oxide film
and enhance rate of corrosion.
 Factors influencing corrosion - Environment
vii) Conductance of the corroding environment:
In corrosion of underground and submerged structures, the
conductance of the medium plays a critical role in corrosion.
Conductance due to stray currents through the soil will promote the
corrosion.

viii) Formation of oxygen concentration cell:

If one part of the metal is exposed to higher levels of oxygen, it
becomes cathode and the other part which is exposed to lesser levels of
oxygen will become anode.

This is called oxygen concentration cell which promotes corrosion by

anodic oxidation/dissolution.
2 H2O + O2 + 4e- 4 OH- (Cathodic reaction-higher O2)
This OH- will move to the cathode where Fe2+ reacts to form Fe(OH)2
which later converts into rust (Fe2O3.3H2O).
Buried pipelines, cables etc., experience this kind of electrochemical
corrosion.
 Factors influencing corrosion - Environment
• Flow velocity of process stream: Corrosion is a diffusion controlled
process. Increase in flow velocity of the corrosion medium (liquid in a
boiler) enhances diffusion rate, thereby increasing the corrosion rate.
Therefore, optimization of flow velocity may decrease corrosion rate.

• Polarization of electrodes: Corrosion rate can be controlled by

reducing the corrosion current (Icorr) flowing from anode to cathode by
adding suitable Inhibitors.
• Inhibitors reduce the corrosion current by polarizing the electrodes which
alters the potential of anode to less anodic (more cathodic) and that of
cathode to less cathodic (more anodic).
• As a result, the potential difference and the corrosion current between
anodic and cathodic areas decreases, thereby corrosion rate also
decrease.

• Corrosion current, Icorr is determined by the rate of production of

electrons by the anodic reaction and their consumption by the cathodic
reaction.
• higher the potential difference (corroding anode potential and the non-corroding
cathode potential), faster the rate of corrosion and hence, more Icorr