CORROSION

& ITS CONTROL

 INTRODUCTION
Any process of deterioration or destruction and consequent loss of a
solid metallic material, through an unwanted or unintentional chemical
or electrochemical attack by its environment, starting at its surface, is
called Corrosion. Corrosion is a process reverse of extraction of metals.
The term corrosion is sometimes also applied to the degradation of
plastics, concrete and wood, but generally refers to metals.
 TYPES OF CORROSION

1. DRY or chemical (O2, Cl2, SO2 etc.)

2. WET or electrochemical
3. GALVANIC
4. CONCENTRATION CELL
5. PITTING
 DRY OR CHEMICAL CORROSION
•Direct chemical combination – Metals combine directly with gases
such as oxygen, chlorine, sulphur gases & carbon dioxide
•In an environment containing oxygen ------bonds are formed
between metals & oxygen at the surface
•Once exposed to air oxidation starts – slow process at normal
temperatures – rate of corrosion increases with increased
temperature
•Rate restricted by the difficulty in the gas reaching the underlying
metal atoms
•Rate of oxidation reduces with time, & destruction ceases
•Dry atmospheres allow steel components to last for many years
 MECHANISM OF DRY CORROSION
•The free energy of the system is reduced by oxidation
•Therefore as a consequence almost all metals should revert
to their oxides, especially at high temperature
•Oxidation is a diffusion process
M + O
MO
Metal Oxygen Oxide

Oxygen anions Oxide Metal Cations

Metal
Diffusion across the MO interface is the rate limiting step.
2M → 2M n + + 2ne −
n
O 2 + 2 ne − → nO 2−
2
 Case-1 Stable or impervious/non-porous oxide layer (oxides of Al etc.)
Metal oxide layer

O2
Metal

Case-2. Pervious/porous/ and volatile oxide layer (though a difference exist)

O2

Pilling-Bedworth rule: An oxide is protective or non-porous, if the molar volume of oxide

is at least as great as the molar volume of the metal from which it is formed.
(If less then, porous….)
Q. What about the case if the oxide layer is unstable?

Metal oxide= metal +Oxygen

Examples: Pt, Au etc.
 Electrode Potential
 When an electrode (e.g. Fe) is immersed in a solvent (e.g. H2O) some metal
ions leave the electrode and –ve charge builds up in the electrode
 The solvent becomes +ve and the opposing electrical layers lead to a
dynamic equilibrium wherein there is no further (net) dissolution of the
electrode
 The potential developed by the electrode in equilibrium is a property of the
metal of electrode → the electrode potential
 The standard electrode potential is measured with the electrode in contact
with a solution containing an unit concentration of the ions of the same
metal with the standard hydrogen electrode as the counter electrode (whose
potential is taken to be zero)

Metal
-ve ions

+ve
 Standard electrode potential of metals

System Potential in V
Cathodic Noble end
Increasing propensity to dissolve Au / Au3+ +1.5
Ag / Ag+ +0.80
Cu / Cu2+ +0.34
H2 / H+ 0.0
Pb / Pb2+ −0.13
Ni / Ni2+ −0.25
Fe / Fe2+ −0.44
Cr / Cr3+ −0.74
Zn / Zn2+ −0.76
Al / Al3+ − 1.66
Anodic Active end Li / Li+ −3.05
 WET OR ELECTROCHEMICAL CORROSION
•Occurs when (1) a conducting liquid is in contact with metal
•(2) two dissimilar metals or alloys) are dipped in solution.
• Electrochemical corrosion – oxygen may assist the process –
results mainly from a tendency of metals to ionise (dissolve)
when placed in water or an aqueous environment
• Ionisation – interaction between surface atoms of a metal &
ions in the water – electrons on the metal cause it to become
negatively charged – this charge increases as the metal dissolves
– reaches electrode potential – charge sufficient to prevent
further positive ions leaving the metal & ionisation corrosion
ceases
•Further corrosion will only take place if the negative charge on
the metal is reduced
 WET OR ELECTROCHEMICAL CORROSION

Anode Fe

Cathode Cu
Electrolyte

At the anode: M M+ + e-
Surface Positive Electron
metal metal remains
atom ion on metal

At the cathode: Reaction depends upon the ions present in the solution & pH

Acid solution Neutral or alkaline

2H+ + 2e- H2 2H2O + O2 + 4e- 4OH-
Hydrogen From Hydroxyl
In From
gas cathode ions
solution metal
 I. Hydrogen type corrosion (acidic)
-- ------ ------ ---------------- -------------------------- +
Acid medium 2H +2e--
H2
---- ------ ----- ----- -- ----------- ---------- ---
------ ------ ------ ------ ------- --------- ----------
Fe----
Fe2+ +2e

Anodic area
(Large)

II Absorption of oxygen (neutral aqueous)

Via O2
 Summarizing electrochemical corrosion

1. Formation of anodic and cathodic parts in contact

2. Presence of a conducting medium

3. Corrosion of anodic areas

4. Formation of corrosion products somewhere between anodic

and cathodic part
 GALVANIC CORROSION
• Galvanic corrosion is either a chemical or an electrochemical
corrosion. The latter is due to a potential difference between
two different metals connected through a circuit for current
flow to occur from more active metal (more negative
potential) to the more noble metal (more positive potential)
• Galvanic coupling is a galvanic cell in which the anode is the
less corrosion resistant metal than the cathode
• Galvanic corrosion can be predicted by using the
electromotive force (emf) or standard potential series
• In selecting two metals or two alloys for a galvanic coupling,
both metals should have similar potentials or be close to each
other in the series in order to suppress galvanic corrosion
 Anode Fe

Cathode Cu
Electrolyte

At the anode: M M+ + e-
Surface Positive Electron
metal metal remains
atom ion on metal
 CONCENTRATION CELL CORROSION
• It is due to electrochemical attack on metal surface
exposed to electrolyte of varying conc. or varying
aeration
• Preferential corrosion due to variations in the
electrolyte – the reaction removes electrons & these
are supplied by adjacent areas which are deficient in
oxygen – these areas act as the anode & hence
corrode
• Riveted or bolted connections – corrosion occurs in
oxygen poor areas
• Waterline corrosion of steel sheet piles in stagnant
water – oxygen rich at the surface, with oxygen
deficient layers becoming anodic – corrosion occurs
CONCENTRATION CELL CORROSION
A concentration cell can form due to differences in oxygen concentration
Oxygen deficient region → anodic, Oxygen rich region → cathodic

Zn Rod

Waterline

NaCl solution
More oxygenated
part (cathode)
Flow of electron
½ O2 + H2O + 2e-
2OH-
(REDUCTION) e-
Zn2+ Less oxygenated
part (Corroding anode)
Zn
Zn2+ + 2e-
Zn2+
(OXIDATION
ZnCl2
 PITTING CORROSION
• This form of corrosion is extremely localized and it
manifests itself as cavities/pits on a metal surface.
• Results from the breakdown or cracking of the
protective film on a metal at specific points
• The initial formation of pits is difficult to detect due
to the small size, but it requires a prolong time for
visual detection.
• This form of corrosion can be found on aluminum
and its alloys and automobile chromium-plated
bumpers or body coated (painted) parts
• Pits vary in shape, but are very small surface holes
due to the extremely localized anodic reaction sites
 Pit in Metal Plate

METAL Cathodic

Oxygen poor at
base of crack

Anodic

• The initiation of pits occurs at localized sites on a

metal surface defects, which may be due to coating
failure, mechanical discontinuities or microstructural
phase heterogeneities such as secondary phases
FACTORS AFFECTING CORROSION
2. Nature of the Corroding Environment
• Temperature
Corrosion rate increases with increase in temperature of environment due to the
increase in reaction and diffusion rate
• Humidity of air
Atmospheric corrosion of metal increases sharply in humid atmosphere. Vapors
present in atmosphere furnish water to the electrolyte, essential for setting up an
electrochemical corrosion cell.
• Presence of impurities in atmosphere
Atmosphere in the industrial areas contain corrosive gases such as CO2, H2S & SO2,
plus acid fumes of HCl, H2SO4. In presence of these gases, the acidity of the liquid
adjacent to the metal surface increase along with its electrical conductivity, which
eventually leads to increased corrosion
• Presence of suspended particles in atmosphere
Particles like NaCl, (NH4)2SO4 etc. absorb moisture and may act as strong
electrolyte, causing enhanced corrosion.
• Influence of pH
Acidic media pH<7 are more corrosive than alkaline and neutral media. Thus
corrosion can be reduced by increasing the pH of the attacking media.
 FACTORS AFFECTING CORROSION
Nature of the Corroding Environment (contd.)
• Nature of ions present
Presence of anions like silicates in the medium leads to the formation of insoluble
products such as silica gel, which inhibits further corrosion. Anions such as Cl- destroy the
protective and passive surface film, exposing the metal surface to further corrosion
• Conductance of corroding medium (for submerged structures)
Conductance of dry and sandy soil is lower than clayey and mineralized one. Stray currents
from power leakage causes more damage to the metallic structure under clayey soil.
• Formation of oxygen concentration cell
increase in supply of oxygen/air to the moist metal surface, corrosion is promoted. Less
oxygen parts become anodic, and more oxygenated region becomes cathodic, leading to
formation of oxygen concentration cell, where anodic part suffers corrosion
• Polarization of electrodes
The potential difference between the anode and cathode is the driving force of an
electrochemical corrosion process, but the corrosion rate is controlled by the current
flowing in the circuit. Addition of certain organic/inorganic substances (inhibitors) cause
certain irreversible changes which tend to oppose the corrosion current flow. As a result
the potential difference between the anode and cathode decreases, thereby decreasing
the overall corrosion.
 FACTORS AFFECTING CORROSION
1. Nature of Metal
• Position in galvanic series
More active metal suffers corrosion. The rate & severity depend on the difference in
their position; greater the difference, faster is the corrosion on the anodic metal
• Overvoltage
When a metal at higher position in galvanic series (Zn) is placed in 1N H2SO4, it suffers
corrosion forming a film and evolving H2 gas. The initial rate is quiet slow due to high
overvoltage of (0.70 V) of Zn. If few drops of CuSO4 are added, the corrosion rate of Zn
is increased since some of the Cu gets deposited on the Zn surface forming minute
cathodes, where overvoltage is only 0.33 V. Reduction of overvoltage accelerates the
corrosion rate
• Relative areas of anodic & cathodic parts
When two dissimilar metals or alloys are in contact, the corrosion of the anodic part is
directly proportional to the ratio of areas of cathodic part and anodic part. Corrosion is
and sever more rapid and severe and highly localized if the anodic area is small
• Purity of metal
Impurities in a metal causes heterogeneity. And form tiny electrochemical cells and the
anodic part gets corroded
 FACTORS AFFECTING CORROSION
Nature of Metal (contd.)
• Physical state of metal
Corrosion depends on the grain size, orientation of crystals and stress. Smaller grain size
means greater solubility, hence greater corrosion.
• Nature of surface film
In presence of air most of the metals form thin surface film of metal oxide. Ratio to of
volume of metal oxide to metal is termed as specific volume ratio. Greater the specific
volume ratio, lesser the oxidation corrosion.
• Passive character of metal
Metals like Tl, Al, Cr, Ni and Co are passive and exhibit higher corrosion resistance than
expected from the position in galvanic series. Highly protective thin film of oxide on the
surface makes the metal resistant.
• Solubility of corrosion products
In electrochemical corrosion, if the corrosion product is soluble in the corroding
medium, corrosion proceeds at a faster rate.
• Volatility of corrosion products
If the corrosion product is volatile, once it forms, it leaves the surface exposing the metal
for further attack. This is a continuous process which enhances further corrosion.
 CORROSION CONTROL
• Must be addressed at the design stage

(minimize localized corrosion; some principles are)

(a)Avoid contact of dissimilar metals in Corr. Environ.

(b) Large anodic area and small cathodic area

(c) Smaller gap in Galvanic series

• Understand the exposure (environment) – pollution, repeated wetting & drying, humidity, the presence of
salts etc. (minimize the corroding capacity of the environment)

• De-aeration

• De-activation by substances such as Sodium-sulphite (it consumes O2)

• Design life – maintenance programmes – repair & replacement

• Methods of control – longest life for the minimum cost

 Isolation Methods
• Application of protective coatings to specially prepared
surfaces
• Metallic coatings:
protective barrier - steel protected by nickel or chromium
Anodic coatings – sacrificial protection – steel protected by
zinc, cadmium or aluminium
Organic coatings – protective barrier - paints, pitch & tar –
usually applied over a metallic primer
Application must be to clean & dry surfaces that have been
properly prepared
 Cathodic Protection
• This can be achieved in two ways:
1.) Sacrificial Anode
2.) Impressed current
• It has been shown that a combination of
cathodic protection & coating is the most
economical means of protecting steel
structures
 Sacrificial Anode
• Use of sacrificial anodes – Zinc, lead, etc.
• Used on small structures
• Anodes welded or bolted to fixtures
• Need regular checks for wastage
• Pipelines buried underground are protected in this way
• Method relies on conductive pathways through the soil
• Recently aluminium oxides have become more popular
due to better performance to weight
 Impressed Current Cathodic protection (ICCP)

• Involves the use of an external power source – metal to be

protected is made cathodic to its surroundings – inert anodes
used which are virtually insoluble – insulated from structure
• Early anodes made from scrap steel but most modern ICCP
systems use lead silver alloy, titanium or niobium
• The use of modern electronics makes the system self regulating
• Very costly to run – mainly used in marine applications – oil rigs
– large anodes placed on sea bed approximately 100m away
• Has been used in the protection of steel reinforcement in
concrete
Impressed Current System
 CORROSION CONTROL
Basic goal → • protect the metal • avoid localized corrosion
When possible chose a nobler metal
 Avoid electrical / physical contact between metals with very different electrode
potentials (avoid formation of a galvanic couple)
 If dissimilar metals are in contact make sure that the anodic metal has a larger
surface area / volume
 In case of microstructural level galvanic couple, try to reduce number of galvanic
cells formed
 Modify the base metal by alloying
 Protect the surface by various means
 Modify the fluid in contact with the metal
• Remove a cathodic reactant (e.g. water)
• Add inhibitors which from a protective layer
 Cathodic protection
• Use a sacrificial anode (as a coating or in electrical contact)
• Use an external dc source in connection with a inert/expendable electrode
 CATHODIC PROTECTION: Galvanic coupling can be used for
cathodic protection purposes
GALVANIC SERIES

more cathodic
Platinum
Gold

(inert)
Graphite
Titanium
Silver
e− flow 316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Anode Cathode
Tin

more anodic
Zn Cu
Lead
(−0.76) (+0.34)

(active)
Iron/Steel
Aluminum Alloys
Cadmium
Zn → Zn2+ + 2e− Zinc
Cu2+ + 2e− → Cu
oxidation Magnesium
Reduction
Zn will corrode at the expense of Cu