Corrosion and its prevention

electrochemical Interpretation
 Introduction

Corrosion is the deterioration of materials by chemical interaction with their

environment. The term corrosion is sometimes also applied to the
degradation of plastics, concrete and wood, but generally refers to metals.
The most widely used metal is iron (usually as steel) and the following
discussion is mainly related to its corrosion.
E.g.
1) Rusting conversion of iron in to its oxide (Fe2O3 Heamatite)
2) Tarnishing silver is converted in its sulfide (Ag2S –Silver
glance)
3) Conversion of copper in to its green colored carbonate
(malachite)
 Why do metals corrode?

Any spontaneous reaction in the universe is associated with a lowering

in the free energy of the system. All metals except the noble metals
have free energies greater than their compounds. So they tend to
become their compounds through the process of corrosion.

Except noble metal, all metals are unstable to varying degrees in a

terrestrial atmosphere. The most widely used metals, namely, Iron,
aluminium, copper, nickel, silver and alloys of these metals all decay
and lose good mechanical properties.
 General scheme of corrosion

The surfaces of all metals (except gold) in air are covered with oxide films.
When such a metal is immersed in an aqueous solution, the oxide film
tends to dissolve. If the solution is acidic, the oxide film may dissolve
completely leaving a bare metal surface, which is said to be in the active
state. In near-neutral solutions, the solubility of the oxide will be much
lower than in acid solution and the extent of dissolution will tent to be
smaller.

If the near-neutral solution contains inhibiting anions, this dissolution of the

oxide film may be suppressed and the oxide film stabilized to form a
passivating oxide film which can effectively prevent the corrosion of the
metal, which is then in the passive state.
 Continuation ….

When the oxide-free surface of a metal becomes exposed to the solution,

positively charged metal ions tend to pass from the metal into the solution,
leaving electrons behind on the metal, i.e.

M Mn+ + ne-
Atom in the metal surface ion in solution electron(s) in metal

The accumulation of negative charge on the metal due to the residual electrons
leads to an increase in the potential difference between the metal and the
solution. This potential difference is called the electrode potential which thus
becomes more negative. This change in the potential tends to retard the
dissolution of metal ions but to encourage the deposition of dissolved metal
ions from the solution on to the metal, i.e. the reverse of reaction(1).

RT
0 + ln a M n+
E r,Mn+/M = E Mn+/M
nF
Continuation ….

Continuation of the dissolution and deposition of metal ions would

result in the metal reaching a stable potential such that the rate of
dissolution becomes equal to the rate of deposition. This potential is
termed the reversible potential Er and its value depends on the
concentration of dissolved metal ions and the standard reversible
potential Eo for unit activity of dissolved metal Ions, aM n+, i.e.,

Mn+ + ne- M (2)

 Continuation ….
In acid solutions, electrons can react with hydrogen ions, adsorbed on the metal
surface from the solution, to produce hydrogen gas.

2H + + 2e- H2 (4)
adsorbed on metal surface in metal gas

The occurrence of reaction (4) permits the continued passage of an equivalent quantity of
metal ions into solution, leading to corrosion of the metal. Reaction (4) is also reversible
and has a reversible potential given by

P 1/2
0 RT H2
E = E - ln
r, H+/H2 H+/H2
nF a H+
Continuation ….

In neutral solutions, the concentration of hydrogen ions is too low to allow reaction
(4) to proceed at a significant rate, but electrons in the metal can react with oxygen
molecules, adsorbed on the metal surface from air dissolved in the solution, to
produce hydroxyl ions

O2 + 2H2O + 4 e- 4OH-
Adsorbed on metal surface in metal in solution (6)

P4 -
RT OH
E = E0 - ln
r, O2 / OH - O2 / OH
-
4F P O2
 Electrochemistry of corrosion
For corrosion to take place, the formation of a corrosion cell is essentially
comprised of the following four components.
a) Anode
b) Cathode
c) Electrolyte
d) Metallic path.

Anode:
An anode is an electrode through which electric current flows in to a
polarized electrical device.
The misconception is that anode polarity is always positive (+). This is
often incorrectly inferred from the correct fact that in all electrochemical
device negatively charged anions moves towards the anode (or oppositely
charged cations move away from it). Anode polarity depends on the device
type and sometimes even in which mode it operates.
Cathode:
One of the two electrodes in an electrolytic cell represented as a positive
terminal of a cell. Reduction takes place at the cathode and electrons are
consumed.
Electrolyte:
It is the electrically conducting solution (e.g. salt solution) that must be present for corrosion
to occur. Note that pure water is a bad conductor of electricity. Positive electricity passes
from anode to cathode through the electrolyte as cations, e.g. Zn++ ions dissolve from a zinc
anode and thus carry positive current away from it, through the aqueous electrolyte.

Metallic Path:
The two electrodes are connected externally by a metallic conductor. In the metallic
conductor, 'conventional' current flows from (+) to (—) which is really electrons flowing
from (—) to (+). Metals provide a path for the flow of conventional current which is actually
passage of electrons in the opposite direction.
Current Flow:
Conventional current flows from anode (—) to cathode (+) as Zn++ ions
through the solution. The current is carried by these positive charged ions.
The circuit is completed by passage of electrons from the anode (—) to the
cathode (+) through the external metallic wire circuit (outer current).
 Mechanism of corrosion

The mechanism of rusting is found to be electrochemical in nature: Anode and

cathode are involved: electrons flow from anode to cathode, oxidation of iron to Fe
(I1) occurs at the anode, and several reduction reactions occur at the cathode.

At anode areas of iron, the iron is electrochemically oxidized to Fe(II). In an oxygen

environment, the Fe(II) is quickly oxidized to Fe(III) which is subsequently changed
to Fe(OH)3 and finally to a hydrated ferric oxide.
 Types of corrosion

Corrosion may be classified in different ways

Wet / aqueous Corrosion

Temperature Corrosion
 Type I

Wet / Aqueous corrosion

Wet / aqueous corrosion is the major form of corrosion. Based on the appearance of
the corroded metal, wet corrosion may be classified as

Uniform or General

Galvanic or Two-metal

Crevice

Pitting

Intergranular

Velocity-assisted

Environment-assisted cracking
UNIFORM CORROSION
Corrosion over the entire exposed surface at a uniform rate. e.g.. Atmospheric
corrosion.
Maximum metal loss by this form. Not dangerous, rate can be measured in the laboratory.

GALVANIC CORROSION
When two dissimilar metals are joined together and exposed, the more active of the two
metals corrode faster and the nobler metal is protected. This excess corrosion is due to the
galvanic current generated at the junction.
Prevention of galvanic corrosion:

(1) Do not have the area of the more active metal

smaller than the area of the less active metal.
(2) If dissimilar metals are to be used, insulate them.
(3) Use inhibitors in aqueous systems whenever
applicable and eliminate cathodic depolarizers
Crevice corrosion :

Intensive localized corrosion within crevices &

shielded areas on metal surfaces Small volumes of
stagnant corrosive caused by holes, gaskets, surface
deposits, lap joints
PITTING
1) A form of extremely localized attack causing holes in the metal
2) Most destructive form Autocatalytic nature
3) Difficult to detect and measure Mechanism

Prevention of pitting corrosion :

(1) Use materials with appropriate alloying elements designed to minimize
pitting susceptibility. e.g. molybdenum in stainless steel.
(2) Provide a uniform surface through proper cleaning, heat treating and surface
finishing.
(3) Reduce the concentration of aggressive species in the test medium, such as
chlorides, sulfates, etc.
(4) Use inhibitors to minimize the effect of pitting, wherever possible.
(5) Make the surface of the specimen smooth and shiny and do not allow any
impurities to deposit on the surface.
Intergranular corrosion:
The grain boundaries in metals are more active than the grains because of
segregation of impurities and depletion of protective elements. So preferential
attack along grain boundaries occurs. e.g. weld decay in stainless steels
Method of Prevention
The following are the methods of prevention of austenitic nickel chromium
stainless steels from intergranular corrosion:
(a) Purchase and use stainless steel in the annealed condition in which there is
no harmful precipitate. This only applies when the steel is not to be exposed to
the sensitizing temperature.
(b) Select low carbon grade steel with a maximum of 0.03% C, such as 304 L.
This would prevent the formation of harmful chromium carbide during
fabrication
Velocity Assisted corrosion :

Fast moving corrosives cause

a) Erosion-Corrosion,
b) Impingement attack , and
c) Cavitation damage in metals

Cavitation Damage :
Cavitation is a special case of Erosion-corrosion. In high velocity
systems, local pressure reductions create water vapour bubbles which
get attached to the metal surface and burst at increased pressure,
causing metal damage
Environment Assisted Cracking:
When a metal is subjected to a tensile stress and a corrosive medium, it may experience
Environment Assisted Cracking. Three types:
1) Stress Corrosion Cracking
2) Hydrogen Embrittlement
3) Liquid Metal Embrittlement

Stress Corrosion Cracking:

Static tensile stress and specific environments produce cracking
Examples:
1) Stainless steels in hot chloride
2) Ti alloys in nitrogen tetroxide
3) Brass in ammonia
Hydrogen Embrittlement:
High strength materials stressed in presence of hydrogen crack at reduced stress levels.
(a) Film rupture model
(b) Slip step dissolution model
Hydrogen may be dissolved in the metal or present as a gas outside. Only ppm levels of H
needed
liquid metal embrittlement:
Certain metals like Al and stainless steels undergo brittle failure when stressed in contact
with liquid metals like Hg, Zn, Sn, Pb Cd etc.
Molten metal atoms penetrate the grain boundaries and fracture the metal.
Fig. Shows brittle IG fracture in Al alloy by Pb
Type II

Temperature corrosion:
Generally corrosion rates increase with increases in temperature. This is due to
several interrelated factors:
1. Higher temperatures tend to promote the corrosion reaction kinetics. Therefore
except in cases where oxygen is free to escape, higher temperatures boost the
corrosion rate.
2. Corrosive by products will have a higher diffusion rate at higher temperatures
and thus will be delivered to the corroding surface more efficiently.
(a) High Temperature corrosion
(b) Low temperature corrosion
High temperature corrosion
High temperature corrosion is a form of corrosion that does not
require the presence of a liquid electrolyte. Sometimes, this type of
damage is called "dry corrosion" or "scaling".
High temperature metals requires neither moisture nor dissolved
electrolytes (salts, acids) to proceed.

Low temperature corrosion:

Low-temperature corrosion appears in the boiler as well as on other
surfaces where the temperature is under approx. 135°C. It is caused
by condensation of the acidic sulphur and chlorine-containing
gases.
This type of corrosion is temperature-dependent. New plants are
being designed differently in order to avoid low-temperature
corrosion
 Causes of corrosion
Failures of various kinds and the need for expensive replacements may occur even though the
amount of metal destroyed is quite small.

Some of the major harmful effects of corrosion can be summarized as follows:

1. Reduction of metal thickness leading to loss of mechanical strength and structural failure or
breakdown.

2. Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges,
cars, aircraft).
3. Loss of time in availability of profile-making industrial equipment.
4. Reduced value of goods due to deterioration of appearance.
5. Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when small quantities
of heavy metals are released by corrosion).
6. Perforation of vessels and pipes allowing escape of their contents and possible harm to the
surroundings.
7. Loss of technically important surface properties of a metallic component.
8. Mechanical damage to valves, pumps, etc, or blockage of pipes by solid corrosion products.
 10) Buried gas or water supply pipes can suffer severe corrosion which is not
detected until an actual leakage occurs, by which time considerable damage may be
done.

11) In electronic equipment it is very important that there should be no raised resistance at
low current connections.
12) The lower edge of this aircraft skin panel has suffered corrosion due to leakage and
spillage from a wash basin in the toilet.
13) Sea water is a highly corrosive electrolyte towards mild steel. This ship has suffered
severe damage in the areas which are most buffeted by waves, where the protective coating
of paint has been largely removed by mechanical action
 Prevention of
corrosion
There are many methods of protecting metals against corrosion.
They are

1) Barrier protection
2) Sacrificial protection
3) Cathodic protection.
Barrier protection :
Here, a thin barrier is developed between the surface of iron and
atmosphere by one of the following methods:
a) Painting of the surface
b) Coating the surface with a thin film of oil or grease
c) Developing a thin layer of some non –corrosive metal like nickel,
chromium copper etc., by electroplating.

Sacrificial protection:
In this case, the surface of iron is covered with a more electropositive metal like
zinc or aluminum. Since this metal loses electrons more readily than iron, rusting
is prevented. As long as metal is present, iron does not get rusted. This type of
protection is called ‘sacrificial production’.
Cathodic protection (Electrical protection):
This method is especially used for underground iron pipes. Here, the iron
pipe or tank is connected to a more electropositive metal like magnesium or
aluminum. The more electropositive metal acts like anode (supplies electrons) and
iron acts like cathode (receives electrons). Thus, iron is protected by turning it as a
cathode. Hence, the method is called ‘cathodic protection’ .
Conditioning the Metal
By retarding either the anodic or cathodic reactions the rate of corrosion can
be reduced. This can be achieved in several ways:
This can be sub-divided in to two main groups:
(a) Coating the metal
(b) Alloying the metal

Coating the metal :

In order to prevent corrosion, resistant coating is made between metal and
environment.
Hot dipping
Electroplating
In thermal spraying
Organic coatings
(b) Alloying the metal
Alloying the metal is to produce a more corrosion resistant alloy, e.g.
stainless steel, in which ordinary steel is alloyed with chromium and nickel.
Stainless steel is protected by an invisibly thin, naturally formed film of chromium
sesquioxide Cr2O3
In general, the corrosion behavior of alloys depends on the interaction of:
1. The alloy of specific chemical composition and metallurgical structure.
2. The film on the alloy surface.
3. The environment, whether it is sufficiently aggressive to break down the
protectiveness of the surface film, thereby initiating localized corrosion.
4. The alloy/environment combination, controlling whether the film self
repairs after breakdown and, if not, the type and rate of corrosion that
propagates after initiation has occurred