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.
 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 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 Au / Au3+ +1.5
Increasing propensity to dissolve 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
 TYPES OF CORROSION

1. DRY
2. WET
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 covalent 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
High temperature allows oxide layer to grow rapidly & thicker films
tend to crack exposing new metal
 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

Oxidation occurs
at air-oxide
interface
Metal
Oxidation occurs
at metal-oxide
interface
 WET OR ELECTROCHEMICAL CORROSION
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 (pH<7) Neutral or alkaline (pH7)

2H+ + 2e- H2 2H2O + O2 + 4e- 4OH-
In From Hydrogen From Hydroxyl
solution metal gas cathode ions
 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
 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
 CONCENTRATION CELL CORROSION
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
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 holes on a metal surface.
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 due to
film/coating breakdown at isolated surface sites.
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
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
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 Parts 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, Mg, 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.
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 since
gases such as O2, CO2 and 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
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.
 CORROSION CONTROL
Must be addressed at the design stage
Understand the exposure (environment)
pollution, repeated wetting & drying,
humidity, the presence of salts etc.
Design life maintenance programmes
repair & replacement
Methods of control longest life for the
minimum cost
 CORROSION PROTECTION
Corrosion occurs at ambient temperatures in the
presence of moisture
Design to protect from exposure
Previously rusted steel left on site will be liable to
further corrosion as rust pits are difficult to remove
even after aggressive cleaning protect site steel
with primer prevent initial corrosion
 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 done on 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
Recently aluminium oxides have become more popular
due to better performance to weight
Pipelines buried underground are protected in this way
Method relies on conductive pathways through the soil
 Impressed Current (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 non-consumable insulated from
structure
Early anodes made from scrap steel but most modern ICCP
systems use lead silver alloy, titanium or niobium
Has been used in the protection of steel reinforcement in
concrete
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
Impressed Current System
 CORROSION CONTROL
Basic goal Protect the metal & avoid localized corrosion

When possible choose 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 use a course
microstructure (where possible) 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 electrode
 "Rust's A Must"
Mighty ships upon the ocean
Suffer from severe corrosion,
Even those that stay at dockside
Are rapidly becoming oxide.
Alas, that piling in the sea
Is mostly Fe2O3.
And where the ocean meets the shore,
You'll find there's Fe3O4.
'Cause when the wind is salt and gusty,
Things are getting awful rusty.

We can measure, we can test it,

We can halt it or arrest it.
We can gather it and weigh it,
We can coat it, we can spray it.
We examine and dissect it,
We cathodically protect it
We can pick it up and drop it.
But heaven knows we'll never stop it!
So here's to rust, no doubt about it,
Most of us would starve without it.

Late Mr. T. R. B Watson of Corrosion Services Co., Ltd. in Toronto is believed to be the author.