MODULE ONE: INTRODUCTION

CORROSION: A NATURAL PROCESS

Corrosion can occur as a natural process. Metals have the natural tendency
to combine with other chemical elements to return to their most stable
natural forms. For example, iron and steel combine with oxygen and
water (present in its natural environment) to form hydrated iron oxides
(rust) similar in chemical composition to the original iron ore (from which
iron metal is produced).

Smeltin
g &
Refinin
g of Ore

Finishe
d Iron
product

Iron in
contact
with Air
&
moistur
e

Minning
process
of Ore
Iron
Oxide
(Ore &
Rust)

FIGURE 1: The Corrosion Cycle of Iron

Whenever corrosion is being mentioned, it is important to think of a

combination of a material and an environment. The corrosion
behavior of a material cannot be described unless the environment in
which the material is exposed to is identified and defined.
Also, the corrosivity or aggressiveness of an environment cannot be
described unless the material that is to be exposed to that environment is
identified. It is important to note that these combinations can be natural
combinations and/or unnatural combinations.

it has been postulated that the downfall of the Roman Empire

can be attributed in part to a corrosion problem, specifically
the storage of wine in lead-lined vessels(acetic acid in
wine attack lead). Lead dissolve in the wine and
consumed by the Roman hierarchy resulted in instanity
(lead poisoning) and contributed to the subsequent
eventual downfall.

WHAT IS CORROSION?
Corrosion can be defined in many ways. Some definitions are very narrow
and deal with a specific form of corrosion, while others are quite broad and
cover many forms of deterioration.
The word corrode is derived from the latin corrodere which means to
gnaw/chew to pieces. The general definition of corrode is to eat into or
wear away gradually, as if by gnawing.
Corrosion can be defined as a chemical or electrochemical reaction between
a
material, usually a metal, and its environment that produces deterioration
and alteration of the material and its properties.
The environment consists of the entire surrounding in contact with the
material. Corrosion is the damage or gradual eating away (disintegration) of
metal caused by reaction with its environment.
The environment that corrodes a metal can be anything; air, water and soil
are common ------- but everything from tomato juice to blood that contacts
metals contributes to the corrosive environment. [All these materials are
chemical substances].

The main factors used to describe the environment are:

Physical state
Chemical composition
Temperature

----------- gas, liquid or solid

----------- constituents and concentration

Other important factors in specific cases include

Relative velocity of a solution
Mechanical loads on material

(due to flow or agitation)

(internal residual stress)

FORMS OF CORROSION
The classification of the different forms of corrosion is based on:
a. Nature of the Corrodents
b. Mechanism of corrosion
c. Appearance of the corroded metal
NATURE OF THE CORRODENT: Corrosion can be classified as Wet or
Dry. A liquid or moisture is required for wet corrosion while dry corrosion
involves reaction with high temperature gases.
MECHANISM OF CORROSION: This involves either indirect electrochemical
or direct chemical reactions.
APPEARANCE OF THE CORRODED METAL: this classification is based on
visual observation with either the naked eye or magnification. In this case,
corrosion is either uniform (i.e. metal corrodes at the same rate over the
entire surface) or it is localized (i.e. small areas are affected).
Here, the corrosion forms are:
Uniform or General corrosion
Pitting corrosion (sharply defined holes are produced)
Crevice corrosion (occurs at narrow openings between metals or
metal and non-metal)
Galvanic corrosion (occurs when metals, even non-metals, are
electrically coupled
together)
Erosion corrosion (corrosion accelerated by mechanical wear or
abrasive)
Intergranular corrosion (selective dissolution of grain boundaries)

 Dealloying (selective leaching or parting corrosion of more active

metal from an alloy)
Environmentally assisted cracking (e.g. stress-corrosion cracking,
corrosion fatique)
The schematic diagram of the classification of corrosion thus

Corrosio
n

Localised
Macroscopic
(by naked
Eye)
1. Galvanic
2. Erosioncorrosion
3. Crevice
4.
Pitting
5.
Dealloying

Microscopic
(by
Magnificatio
n)
1.
Intergranular
2. Stresscorrosion
cracking

Uniform

Figure 2: The schematic diagram of the classification of

corrosion

THE EFFECTS OF CORROSION

The corrosion of metals costs the U.S economy almost $300
billion
per year at current prices. Approximately one-third of these could
be
reduced by broader application of corrosion-resistant materials
and
the application of best corrosion-related technical practices. This
estimate resulted from an update of findings of the 1978 study
Economic Effects of Metallic Corrosion in the United States. The
study was performed by Battele Columbus Laboraties and the
National Institute of Standards and Technology (NIST) and
published in April 1995.
At home, the effects of corrosion in our daily lives are both direct and
indirect. Direct, in the sense that corrosion affects the useful lives of our
possessions (our belongings). And indirect, in the sense that producers and
suppliers of goods and services include corrosion costs in their overall
production costs which eventually determine their products price.
In the public, the corrosion of steel reinforcing bar in concrete can proceed
out of sight and suddenly result in failure of a section of highway, the

collapse of electrical towers, damage to buildings and bridges and ships. All
these lead to significant repair costs and loss of lives and properties.

Corrosion, among many other factors, contributed to the

Maintenance/
repair work carried out on the Lagos Third Mainland bridge.
Do you have an idea of the total sum of money involved?
In our major industrial plants, such as electrical power plants or chemical
processing plants, plant shutdown can and do occur as a result of corrosion.
An entire machine may have to be scrapped because of the corrosion of one
small vital part. The industrial plants that suffer greatly from corrosion
include chemical industries, automobile industries, petro-chemical industries
and shipping industries.
Corrosion leads to a depletion (or loss) of resources. Many metals, especially
those essential in alloying, such as Chromium and Nickel, cannot be recycled
by todays technology. Energy resources are also lost to corrosion because
energy must be used to produce new metals to replace the corroded ones.
Human resources (lives and time) are wasted. Industrial accidents, claiming
the lives of people, can occur as a result of corrosion failure of an expansion
joint of pipes transporting very ignitable, explosive fluid in chemical plants.
Environmental damage is a very serious problem of corrosion. Corrosion of
pipes can cause oil pipeline leakage which makes life unbearable for aquatic
animals and man.

Corrosion is one of the major factors that contributed to

Niger Delta Crises. Do you agree with this statement?

In Summary,
Economic Consequences of Corrosion include:

Replacement of corroded equipment

Overdesign to accommodate corrosion
Preventive maintenance (e.g. painting)
Shutdown of equipment or plants due to corrosion failure
Contamination of a product

 Loss of efficiency (e.g. corrosion products decrease the heat transfer

rate in heat exchangers)
Loss of valuable products (corroded container can cause this loss)
Social Consequences of corrosion include:
Threat on Safety/Health e.g. sudden failure can cause fire explosion,
release of toxic substances (pollution) from corroded equipment
Appearance ------ corroded materials become unpleasing to the eyes

Factors that can increase or decrease the costs of corrosion are:

Applied current technology

Hostile environments
Environmental regulations
Research and development
Technology transfer
Increased performance requirements
Deferred maintenance

FACTORS INFLUENCING METAL CORROSION

Most metals exist in nature (in ores or minerals) as compounds, such
as oxides, sulfides, sulfates, because these are their
thermodynamically stable state. Metals are extracted from these
compounds after expending lot of energy.
Hence, unless the nature of the metal is substantially changed (e.g. by
alloying), the metal will have a natural tendency to revert back to its
natural thermodynamically stable state. This is the basic reason for
metallic corrosion.
When a metal is exposed to the atmosphere, an oxide film is formed on
its surface due to its interaction with atmospheric air. Further attack of
corrosion will not occur, if this protective oxide film is maintained on
the entire metal surface. But, however, if this oxide film breaks down
due to electro-chemical action on the metal surface due to the
presence of moisture or any electrolyte, corrosion proceeds further.
Factors influencing metal corrosion can be broadly classified into two.
These are
1. The Nature of the metal
2. The Nature of the environment

1.
[A]

NATURE OF THE METAL

Oxidation Potential

The extent of corrosion depends upon the position of the metal in the
electrochemical series. When two metals are in electrical contact in presence
of an electrolyte, the metal higher up in the electrochemical series becomes
anodic and suffer corrosion.
The more the two metals are apart in the series, the greater the difference in
their oxidation potential and hence the faster the corrosion of the anodic
metal will be.
[B]

Relative Areas of the Anode and Cathode

When two steel plates of the same area are separately connected, one to a
copper plate (cathode) having the same area and the other to a copper plate
having a much smaller area, the corrosion rate of the one with larger area of
cathodic copper is greater. Corrosion of the anode is directly proportional to
the area of the cathode.
The great demand for electrons by the larger cathodic area will have to be
met by the smaller steel anode forming more Fe2+ ions and hence the attack
will be more severe.
[C]

Purity of the Metal

The impurities in a metal form galvanic cells with the metal under
appropriate environment and the anodic part gets corroded. The rate of
corrosion increases with the increasing exposure of the impurities.
The effect of even traces of impurities on the rate of corrosion of zinc can be
seen from the data given below
Metal
Zinc
Zinc
Zinc
[D]

% Purity
99.999
99.99
99.95

Physical State of the Metal

Corrosion rate
1
2,650
5,000

The smaller the grains size of the metal or alloy, the greater the solubility.
The orientation of the crystals at the metal surface also affects the corrosion
rate. And residual stress in a metal influences the corrosion rate.
[E]

Solubility of the Corrosion Products

If the corrosion product is soluble, corrosion of the metal will proceed faster.
On the other hand, if the corrosion product is insoluble (e.g. metal oxides)
the protective film formed tends to suppress corrosion.

2.
[A]

NATURE OF THE ENVIRONMENT

Presence of Moisture

Atmospheric corrosion of iron is rather slow in dry air but increases rapidly in
the presence of moisture. This is because, moisture acts as the solvent for
oxygen in the air, gases or salts to furnish the electrolyte essential for setting
up a corrosion cell.
Moisture also reacts with the metal or the oxide in some cases. Metal like
Mg, Al, Zn and Fe may be corroded in the presence of water even in the
absence of oxygen.

[B]

Temperature

The rate of chemical reactions and the rate of diffusion increase with
temperature. In general, corrosion increases with increase temperature
Y
metals, B = Trans-passive metal

A = Active

C = Passive metal
Y = Corrosion

rate,

X = Temperature
B
C

X
[C]

Effect of pH

The hydrogen ion concentration of the medium is another important factor in

corrosion reactions as well as corrosion control. Acidic media are generally
more corrosive than alkaline and neutral media.
The corrosion of iron is slow in oxygen-free water, except the pH falls below 5
when there is increase in the corrosion rate.
[D]

Impurities Present in the Atmospheric Air

In marine atmosphere, the presence of electrolytes such as NaCl in the

humid atmospheric air leads to increase in corrosion of the metals.
Similarly, the atmospheric air near industrial areas is contaminated with acid
fumes and gases, such as H2S, SO2, SO3 and CO2. If the water in which these
gases or fumes are dissolved comes in contact with a metal surface, its
electrical conductivity increases. This naturally increases the corrosion
current flowing in the local and tiny electrochemical cells on the exposed
areas on the metal surface.
Enhanced corrosion rates are observed in marine atmosphere and industrial
areas. The presence of suspended particles in the atmospheric air also
influences corrosion.

[E]

Nature of Anions and Cations present

Chloride ions present in the medium destroy the passive film and corrode
many metals and allys. On the contrary, some anions like silicate may form
an insoluble reaction product (e.g. silica gel) which inhibits corrosion.
Traces of Cu or more noble metals accelerate the corrosion of the iron pipes
carrying mine water. Many metals including iron corrode more rapidly in
ammonium salts than in sodium salts of identical concentrations.
[F]

Flow Velocity of Process Streams

The relative velocity between metal and environment can profoundly affect
the corrosion rate. Either metal or environment can be moving: the metals in
the case of a solution flowing through a pipe. Going from stagnant conditions
to moderate velocity may lower corrosion by distributing a more uniform
environment through the system.
If inhibitors are added, they are distributed more evenly and therefore may
be more effective. On the other hand, increasing velocity may increase the
supply of reactant (usually O2) to the cathodes. For metals that can
passivate, increasing velocity could increase corrosion.

Y=
Corrosion rate
X=
Velocity

MODULE TWO
PRINCIPLES OF CORROSION
THEORIES OF CORROSION
[1]

Direct Chemical Attack Theory

This theory explains the chemical or dry corrosion. Direct chemical attack of
metal by dry gases at atmospheric temperature is rather uncommon.
However, whenever corrosion takes place by direct chemical attack, a solid
film of the corrosion product is usually formed on the surface of the metal,
this film protects the metal from further corrosion. For instance, the attack of
chlorine or iodine of silver forms a protective film of silver halide. But if a
soluble or liquid corrosion product is formed, the metal is exposed to further
attack.
One common way in which metals are attacked by direct action is by
interaction with oxygen. Alkali and alkaline earth metals, such as Na, Ca, Mg,
suffer extensive oxidation even at low temperatures, whereas at high
temperatures all metals, except Ag, Au and Pt are oxidized.
Alkali and alkaline earth metals on oxidation produce oxide deposits of
smaller volume when compare to the metals from which they were formed.
This results in the formation of a porous layer through which oxygen can
diffuse to bring about further attack of the metal.
But heavy metals and Al form non-porous oxide layers of greater volume
than the metal from which they were produced. These non-porous
continuous oxide films prevent the diffusion of oxygen and hence the rate of
further attack decreases with increase in the thickness of the oxide film.
However, as the films grow thicker, their tendency to crack and scale out
becomes greater and particularly at high temperature, intermittent attack of
metal may take place at the exposed parts of the metal (due to cracking of
the oxide film).
The thickness of the film oxides varies with metal and temperature. At high
temperatures, the scale formation proceeds in a two-way process: one is by
the diffusion of O2 to the metal through the oxide layers already formed and
the other is by the diffusion of the metal (e.g. Fe, Al, Zn) outward through the
oxide layers.
Aluminium and Chromium form extremely protective oxide layers and hence
these metals are usually employed for alloy formation with other metals that
are more readily attacked, to provide increased resistance to oxidation.

[2]

The Electrochemical Theory

This theory explains the indirect or wet corrosion. It is based on the

fact that all metals have a tendency to pass into solution.
If a Zn electrode is dipped in a solution of Zinc sulfate, the positive Zinc ions
in the metal electrode are in a continuous vibration and occasionally an ion
receives sufficient energy to escape from the metal and pass into
surrounding solution. The Zinc metal losses equal number of electrons to
attain equilibrium and the process continues provided that the electrons lost
is being utilized at the cathode.
In the case of copper, the tendency of Cu++ to go into solution is lesser and
their tendency to plate out on the copper electrode is greater.
The tendency of a metal to pass into solution when immersed in a
solution of its salt is measured in terms of its electrode potential.
The standard electrode potentials of the various metals have been
determined in comparison with the standard electrode potential of hydrogen
taken as zero.
If a metal having a higher electrode potential comes into contact
with another metal having a lower electrode potential, a galvanic
cell is set up and the metal having higher electrode potential
becomes anodic and goes into solution to a measurable extent.

Standard Electrode Potentials, E0

These are the potentials for half cells with the ions at 1M concentration and
gases at 1 atm pressure, at equilibrium, measured against the standard
hydrogen electrode (0V) at 250C.
E0 (V)
Au3+(aq) + 3e- Au(s)
+ 1.50
Cl2(g) + 2e- 2Cl-(aq)
+ 1.36
O2(g) + 4H+(aq) + 4e- 2H2O
+ 1.23

Br2(l) + 2e- 2Br(aq)

+ 1.07
NO-3(aq) + 4H+(aq) + 3e- NO(g) + 2H2O
+ 0.96
2Hg2+(aq) + 2e- Hg2+(aq)
+ 0.92
Ag+(aq) + e- Ag(s)
+ 0.80
Fe3+(aq) + e-
+ 0.77

Fe2+

(aq)

O2(g) + 2H+(aq) + 2e- H2O2(aq)

+ 0.68
Cu2+ + 2e- Cu(s)
+ 0.34
2H+(aq) + 2e- H2(g)
+ 0.00
Pb2+(aq) + 2e- Pb(s)
- 0.13
Fe2+(aq) + 2e- Fe(s)
- 0.44
Zn2+(aq) + 2e- Zn(s)
- 0.76
2H2O

2e- H2(g) + 2OH-(aq)

- 0.83
Al3+(aq) + 3e- Al(s)
- 1.66
Na+(aq) + e- Na(s)
- 2.71
Ca2+(aq) + 2e- Ca(s)
- 2.87

K+(aq) + e- K(s)
- 2.92
Li+(aq) + e- Li(s)
- 3.03

Electrochemical Series of Metals

Electrochemical series of the metals is the arrangement of metals in the
order of their standard electrode potentials.

Equilibrium

E (volts)
-3.03
-2.92
-2.87
-2.71
-2.37
-1.66
-0.76
-0.44
-0.13
0
+0.34
+0.80
+1.50

Oxidation / Reduction
Oxidation and reduction in terms of electron transfer

Let us apply this to one of the redox equilibria:

When solid magnesium forms its ions, it loses electrons. The magnesium is
being oxidised.
Taking another example . . .

When the copper(II) ions gain electrons to form copper, they are being
reduced.
Reducing agents and oxidising agents:
A reducing agent reduces something else. That must mean that it gives
electrons to it.
Magnesium is good at giving away electrons to form its ions. Magnesium
must be a good reducing agent.
An oxidising agent oxidises something else. That must mean that it takes
electrons from it.
Copper doesn't form its ions very readily, and its ions easily pick up electrons
from somewhere to revert to metallic copper. Copper(II) ions must be good
oxidising agents.
Summarizing this on the electrochemical series
Metals at the top of the series are good at giving away electrons. They are
good reducing agents. The reducing ability of the metal increases as you go
up the series.
Metal ions at the bottom of the series are good at picking up electrons. They
are good oxidising agents. The oxidising ability of the metal ions increases as
you go down the series.

Oxidising or Reducing ability of Metal Using E values

The more negative the E value, the more the position of equilibrium lies to
the left - the more readily the metal loses electrons. The more negative the
value, the stronger reducing agent the metal is. Such metals easily undergo
electrochemical reaction to get corroded.
The more positive the E value, the more the position of equilibrium lies to
the right - the less readily the metal loses electrons, and the more readily its
ions pick them up again. The more positive the value, the stronger oxidising
agent the metal ion is. Such metals do not get corroded easily. Infact,
corrosion products are formed at such sites.

CORROSION REACTIONS
Two metals having different electrode potentials form a galvanic cell when
they are immersed in a conducting solution. The E.M.F. of the cell is given by
the difference between their electrode potentials.
Every electrochemical corrosion cell has:
ANODE

------- the metal that is corroding

 CATHODE ------ metal or electronic conductor (which is built up)

whose surface provides sites for the environment to react.
ELECTROLYTE -------- the aqueous environment which is in
contact with both anode and cathode to provide a path for ionic
conduction.
ELECTRICAL CONNECTION -------- between the anode and the
cathode to allow electrons to flow between them.
eElectron
conductor

Anode

Cathode

Electrolyte

Corrosion reactions can be split into the Anode reactions and Cathode
reactions:

ANODE REACTIONS
At the anode, the metal atoms lose their electrons to the environment and
pass into solution in the form of positive ions (oxidation).
E.g.

Fe

2e-

Fe2+

OR

Fe

Fe2+

2e-

This will continue as long as the electrons and ions are removed to the
environment. If they are not removed, the corrosion will not proceed further.
Hence the happening at the cathode plays a significant role in determining
the happening at the anode.
In general, for corroding metals, M
M

Mn+

newhere n is the number of electron

(e ) released by metal.

The electrons produced do not flow into solution but migrate through the
conductor to the cathode.

CATHODE REACTIONS
The electrons released at the anode are conducted to the cathode and are
responsible for the various cathode reactions:
1. Electroplating: The metal ions at the cathode collect the electrons
and plate out (deposit) on the cathode surface.
E.g.
Cu2+ + 2e Cu
2.
Liberation of Hydrogen:
In acid solution (in the absence of
oxygen) hydrogen ions acquire electrons and H2 gas is formed.

OR

2H3O+

2H +

2e-

2e-

H2

H2

+ H2O

In neutral and alkaline media, (in the absence of oxygen) the reaction will be
2H2O

2e-

H2

2OH-

Corrosion in which H2 gas is evolved is called Hydrogen type.

3. Formation of hydroxyl ions:
a. In the presence of dissolved oxygen and in neutral or
alkaline media.
This is the most common reaction
2H2O + O2 + 4e 4OHb. In the presence of dissolved oxygen and in acid media

4H+ + O2 + 4e 2H2O
involving O2 are called Oxygen type.

Corrosion process

Note that the above mentioned reactions only represent the

predominant reactions. In some cases, these reactions may take
place simultaneously.

Let us consider the corrosion of iron metal which is in contact with water
droplets containing dissolved air.

Water droplet

O2, H2O, Fe2+

Cathode
Rust

H 2O

H+, O2,
e-2+
Fe

Fe 2+
Anode eMETAL
LEGEND
Rust:

Fe2O3.nH2O

Anode: Oxidation of Fe forms a pit

and yields electrons, which travel
through the metal.
Cathode: Electrons migrate to the cathode reduce O2 and H2O.
Fe2+ migrate through the droplet and
reacts with O2 and H2O to form rust,
Fe2O3.nH2O
Corrosion of iron metal can equally be described thus

AIR
OHOH-

OH-

OH-

OH-

OH-

Iron oxide layer (cathode)

e-

Fe2+

Fe2+

Anode
Rust
The iron pipe is incompletely covered by an oxide surface layer (cathodic
with respect to the metal part). Though the electronic conductivity of oxide
layer is small and different in electrode potential is small, but flow of electric
current (e-) is measurable.
The exposed metal gets corroded and Fe2+ passes into solution. The cathode
reaction is
2H2O

+ O2

4e-

4OH-

As the corrosion proceeds, Fe2+ and OH- accumulate in solution and combine
to form insoluble Fe(OH)2 which eventually oxidizes to hydrous ferric oxide,
Fe2O3.nH2O (rust).
If the cathode has a very large surface area, the cathode reaction may be
considerable. And this puts forth a higher demand of e- on the relatively
small anode, hence heavy corrosion takes place at the anode, leading to
even perforation of the pipe where oxide film is defective.

MEASUREMENT OF CORROSION RATE

Measurement of corrosion in a process plant is usually done to achieve the
following objectives:
a) Monitoring the corrosion process taking place in the plant
b) Evaluation of the quality of a specific lot of material being used (e.g.
whether correct heat treatment has been given or not)
c) Evaluation of materials and environmental effects to serve as
guidelines for future use.
d) Studying the mechanism of corrosion.
The measurement of corrosion is usually done by the following methods:
A. WEIGHT LOSS METHOD
Weight Loss test is the most commonly used for measurement of
corrosion. In this method, a clean metal or a standard test piece is
measured, weighted and exposed to corrodent for a particular period of
time. The piece is then taken out, cleaned to remove the corrosion
products and reweighed.
The rate of corrosion of the metal, R , is then calculated using
R=
where

KW
ATD

K = constant,

T = Time of exposure,
W = Weight loss,
Area,
D = Density

A=

Relationship between R and K is given below

Corrosion Rate, R
Millimeters per year (mpy)
Inches per year (in/yr)
Inches per month (ipm)
Micrometer per year (mpy)
Picometers per second (pps)

Constant, K
3.45 X 106
3.45 X 103
2.87 X 102
8.76 X 107
2.78 X 106

B. MICROSCOPIC EXAMINATION
The main objective of this examination on the specimen is to check the
nature of the corroded surface, the number of pits formed and their
depth and the presence of inter-granular corrosion.
C. MEASUREMENT OF ELECTRICAL RESISTANCE
If the test sample is in the form of a thin wire or strip, its electrical
resistance increases as corrosion decreases its cross-section. Hence,
periodic or continuous measurement of the resistance between the
ends of the specimen can be used to monitor the corrosion.

ENVIRONMENTAL CELLS
One drop of water sitting on a metal surface creates an electrochemical cell.
The metal may be approximately uniform in composition but the water drop
is not, and that is all that is required to start localized attack. The
environment needs only to vary in concentration, velocity or
temperature to set up local anode and cathode areas on the metal.

Oxygen Concentration Cells

The most common cathode reaction of all is the reduction of oxygen from air
2H2O

+ O2

4e-

4OH-

The drop of water sets up an electrochemical cell because the water surface
dissolves oxygen from air, while in the center of the drop the oxygen
concentration is lowest. In this way an oxygen concentration cell develops,

with the metal at the circumference of the drop being the cathode and the
metal at the center the anode.
Air
O2
O2

H 2O

OH

Cathode
Cathode

H2O

OH-

Anode

Any place that the metal contacts solution having an exceptionally high
oxygen concentration will be a cathode, and any place where the oxygen is
especially low will tend to be anodic.

Other Concentration Cells

Though oxygen concentration cells are the most common, but any cathode
reactant that varies in concentration on the metal surface can create a
corrosion cell. A variation in pH, for example, can establish a cathode region
where pH is low, provided it is low enough (say pH<4) to make hydrogen
reduction an important cathode process
(i.e.

2H+

2e-

H2(g))

If corrosion is caused by a strong oxidizer, the cathodes will tend to be

located at regions of high oxidizer concentration. Oxidizers commonly used
in the chemical industries include O2, nitric acid (HNO3), hot concentrated
H2SO4, Hydrogen peroxide (H2O2) and solution s containing ferric ion (Fe3+),
permanganate (MnO-4) or perchlorate (ClO-4).

PASSIVITY
A metal is said to be passive in a certain environment if it exhibits much
lower corrosion rate than what is expected thermodynamically or from its
position in the electrochemical series. A passivated metal can be rendered
active by a change in the environmental conditions. Metals which exhibit
passivity include iron, chromium, nickel and alloys of those metals.

Passivation is characterized by the formation of a very thin protective oxide

films. However, a metal when is passive in one environment may not
necessarily be so in a different environment because passivity results from a
continuous reaction between a metal and its environment.
When a metal is passive, it corrodes at a very slow rate, hence, passivity
offers an excellent method of corrosion control.

MODULE THREE
FORMS OF CORROSION
Corrosion problems can be divided into eight categories, based on the
appearance of the corrosion damage or the mechanism of attack.
They are:
1)
2)
3)
4)

Uniform or General Corrosion

Pitting Corrosion
Crevice Corrosion
Galvanic Corrosion

5)
6)
7)
8)

Erosion Corrosion
Inter-granular Corrosion
De-alloying Corrosion
Stress Corrosion Cracking

The corrosion classification scheme listed above appears convenient, it

should be noted that it is arbitrary and by no means perfect. May corrosion
problems are due to more than one form of corrosion acting simultaneously.
For example, in some metal systems where dealloying may occur, this form
of corrosion may be a precursor to stress-corrosion cracking. Also, deep pits
can act as stress raisers and serve as nucleation sites for corrosion fatigue
failures.
Despite the shortcomings, the classification of corrosion forms based on
physical appearance or attack mechanism allows a large and complex
technology to be broken down into more usable and understandable pieces.

[1]

UNIFORM CORROSION

This results in a fairly uniform penetration (or thinning) over the entire
exposed metal surface. The general attack results from local corrosion cell
action; that is multiple anodes and cathodes are operating on the metal
surface at any given time. The locations of the anodic and cathodic areas
continue to move above on the surface, resulting in uniform corrosion.
Uniform corrosion often results from atmospheric exposure (especially
polluted industrial environments): exposure in fresh and salt waters, or
exposure in soils and chemicals.
All metals are affected by uniform corrosion, although passive materials,
such as stainless steels or nickel-chromium alloys are normally subjected to
localized forms of attack.
In some metals, such as steel, uniform corrosion produces a somewhat rough
surface by removing a substantial amount of metal, which either dissolves in
the environment or reacts with it to produce a loosely adherent, porous
coating of corrosion products. In such reactions, thin tightly adherent
protective films are produced and the metal surface remains smooth.

Washed away part

METAL

Prevention Of Uniform Corrosion

Uniform corrosion can be prevented or reduce by proper materials selection,
the use of coatings or inhibitors, or cathodic or anodic protection. These
corrosion prevention methods can be used individually or in combination.
Uniform corrosion is often treated by building a corrosion allowance into the
structure. If the corrosion rate is 100m per year, then the addition of 500m
to the thickness of metal will provide 5 years of operation before corrosion of
the actual area of the material can occur.
The measure of uniform corrosion rate required for determination of the
corrosion allowance is estimated from prior conditions in similar service, data
presented in the corrosion literature and experimental data determined from
exposures.

[2]

PITTING CORROSION

Pitting is a highly localized form of corrosion that produces sharply

defined holes. These holes may be small or large in diameter, but in most
cases, they are relatively small. Pits may be isolated from each other on the
surface or so close together that they resemble a roughened surface.
Metal surface

Every engineering metal or alloy is susceptible to pitting. Pitting occurs

when one area of a metal becomes anodic with respect to the rest of
the surface or when corrodent is in contact with the metal, as in
crevices, leading to accelerated localized attack.
Pitting is one of the most dangerous forms of corrosion. It is characterized
by greater depth of penetration compared to area affected. It can
cause failure by perforation while producing only a small weight loss on the
metal. Also, pits are generally small and often remain undetected.
A small number of isolated pits on a surface are easily overlooked, a large
number of very small pits on a surface may not be detected by simple visual
examination or their potential, for damage may be underestimated.
Immediately after a pit has initiated, the local environment and any surface
films on the pit- initiation site are unstable, and the pit may become inactive
after just a few minutes if convection currents sweep away the locally high
concentration of hydrogen ions, chloride ions or other ions that initiated the
local attack. Stagnant solution favours continous development of pits.
Major causes of pitting include local inhomogeneity on the metal surface,
local loss of passivity, mechanical or chemical rupture of a protective oxide
coating, galvanic corrosion from a relatively distant cathode, and the
presence of biological organisms. The rate of penetration into the metal by
pitting can be 10 to 100 times that of general corrosion.

Prevention Of Pitting Corrosion

This can be minimized by:
Reduce the aggressiveness of the environment, for example reduce
chloride ions concentration, lower temperature, reduce acidity and
reduce oxidizing agents concentration.
Upgrade the materials of construction, for example, use molybdenum
containing (4 6% Mo) stainless steel, over alloy welds and use
corrosion-resistant alloy linings.
Modify the design of the system, for example, avoid crevices and
formation of deposits, circulate/stir to eliminate stagnant solutions and
ensure proper drainage.
Add inhibitor, but in sufficient amounts, to protect the entire surface.

[3]

CREVICE CORROSION

This is a form of localized attack that occurs at narrow openings or

spaces (gaps) between metal-to-metal or nonmetal-to-metal
components.
The crevice can be created in 3 different ways
1. A tight metal-metal joint that is just loose enough to allow
moisture to penetrate, such as in the threads of nuts and
bolts, under rivets, between lapped joints, in wire screens
where the wire cross.
2. Metal containing absorbent non metallic materials, such as
valve packing.
3. Metal surfaces where deposits have formed. These deposits
may be dirt, rust, precipitated salts.
Crevice corrosion results from a concentration cell formed between the
electrolyte within the crevice, which is oxygen starved and the electrolyte
outside the crevice, where oxygen is more. The material within the crevice
acts as the anode and the exterior material becomes the cathode.
Crevice corrosion is usually attributed to changes in acidity in the crevice and
lack of O2 in the crevice. This is commonly observed in lap joints, bolt holes,
threaded joints, riveted seams, overlapping screen wires, beneath coatings.

Crevice corrosion
Non metal

Metal

Metal or

Prevention Of Crevice Corrosion

[4]

Proper design to minimize crevices

Selection of corrosion resistant materials
Maintaining clean surface to remove deposits
Water treatment to remove suspended solids
Cathodic protection
Protective coatings

GALVANIC CORROSION

Galvanic corrosion occurs when a metal or alloy is electrically

coupled to another metal or conducting nonmetal in the same
electrolyte.
The three essential components of galvanic corrosion are:
a) Materials possessing different surface potential
b) A common electrolyte

c) A common electrical path

A mixed metal system in a common electrolyte that is electrically isolated
will not experience galvanic corrosion, regardless of the proximity of the
metals or their relative potential or size.
During galvanic coupling, corrosion of the less corrosion-resistant metal
increases and the surface becomes anodic, while corrosion of the more
corrosion-resistant metal decreases, and the surface becomes cathodic. The
driving force for corrosion or current flow is the potential developed between
the dissimilar metals.
The extent of accelerated corrosion resulting from galvanic coupling is
affected by the following factors:
The nature of the environment
The polarization behavior of the metals or alloys

Prevention of Galvanic Corrosion

Select combination of metals that are so close together, as much as
possible, in the galvanic series suitable for a particular application.

 Avoid combination in which the area of the less corrosion-resistant

material is relatively small.
It is good practice to
Insulate dissimilar metals, if possible insulate them completely
Apply coatings with caution
If only one surface can be painted, the more corrosion-resistant surface
should be chosen to reduce or eliminate the cathode area
In cases where the metals cannot be painted and are connected by a
conductor external to the liquid, the electrical resistance of the liquid
path may be increase by keeping the metals far apart, as much as
possible.
If possible, add chemical inhibitors to the corrosion solution according
to the nature of the solution to be inhibited. This reduces the
corrosiveness of the environment.
Employ cathodic protection measure
Avoid contaminating one metal with the corrosion products of another.

[5]

EROSION CORROSION

Is the accelerated or increase in the rate of deterioration or attack on a metal

because of mechanical wear or abrasive contributions in combination with
corrosion.
The combination of wear and corrosion results in more severe attack than
what would be realized with either mechanical or chemical corrosive action
alone. Metal is removed from the surface as dissolved ions, as particles of
solid corrosion products, or as elemental metal.
The spectrum of erosion-corrosion ranges from primarily erosive attack (such
as sandblasting, filling or grinding of a metal surface) to corrosion failures.
Movement of a corrodent over a metal surface increases the rate of attack
on such metal.
The major cause of erosion is the removal of protective surface films. Erosion
corrosion generally occurs during high velocity conditions, turbulence etc.
and is frequently observed on pump impellers, agitators and piping at bends
and albows.

Direction of flowing water

corrosion film
metal surface

corrosion pit

original

metal tube wall

Critical Factors Influencing Erosion Corrosion

Surface Films:
The nature and properties of the protective films
that form on some metals and alloys are very important from the
standpoint of resistance t erosion-corrosion.
Velocity:
Because erosion-corrosion involves movement between
a metal and its environment, the velocity of the environment plays an
important role. High velocities and environments containing solids in
suspension result in a corrosion mechanism that is more mechanical in
nature.
Nature of Metal or Alloy:
Heat Treatment Effects:
Hardening by heat treatment results in
changes in microstructure and usually in heterogeneity. Quite often
this decreases corrosion [

Prevention Of Erosion Corrosion

To prevent or minimize damage due to erosion corrosion, methods to engage
are:

Use of materials with better resistance to erosion corrosion

Good design
Alteration of the environment (e.g. de-aeration, use of inhibitors)
Coating
Cathodic protection

[6]

INTERGRANULAR CORROSION

Real metals contain many non-homogeneities, most of them deliberately put

in to achieve high strength. A perfectly pure metal crystallized in a perfect
crystal structure would be both incredibly strong and highly corrosion
resistant, but no such metal exists.
In addition to the presence of impurity atoms, metals contain many atom
vacancies, that is, sites where atoms should be present but are not. The
vacancies permit some diffusion of atoms within the crystal.
Also, all real crystals contain linear flaws called dislocation where atoms
are crowded too closely on one side of the line and are packed too loosely on
the other side. These dislocation lines (crystal defect) corrode the metal
more rapidly than the surrounding crystal.
Atoms at the grain boundaries are easily corroded because they are not
bounded as strongly as atoms within the grains. The grain boundaries serve
as collecting sites for impurity atoms that do not fit well inside the crystals.
Rolling, hammering, drawing and some other operations on metals distort
the shape of the metal grains; rolling for example, flattens the grains and
elongates them in the rolling direction. Corrosion attack on the loosely
packed grain boundaries, due to cut, is more severe.
High temperatures, as a result of casting, welding etc., deform the grain
sizes and shapes.
Intergranular corrosion is defined as the selective dissolution of grain
boundaries, or closely adjacent regions, without appreciable attack of the
grains themselves. This dissolution is caused by potential differences
between the grain boundary region and any precipitates, intermetallic
phases, or impurities that form at the grain boundaries. The actual
mechanism differs with each alloy system.
Precipitates that form as a result of the exposure of metals at elevated
temperatures (for example, during production, fabrication and welding) often
nucleate and grow preferentially at grain boundaries. If these precipitates are
rich in alloying elements that are essential for corrosion resistance, the
regions adjacent to the grain boundary are depleted of these elements. The
metal is thus sensitized and is susceptible to inter-granular attack in a
corrosive environment.

PREVENTION OF INTERGRANULAR CORROSION

Adding carbide-stabilizing elements, such as titanium, along with a
stabilizing heat treatment where necessary.
Keeping the metal surface clean of impurities or precipitates.
Limiting interstitial elements, primarily carbon and nitrogen, to the
lowest practical levels.

[7]

DEALLOYING CORROSION

Dealloying, also referred to as selective leaching, is a corrosion process in

which the more active metal is selectively removed from an alloy, leaving
behind a porous weak deposit of the more active noble metal.
Specific categories of dealloying often carry the name of the dissolved
element. For example, the preferential leaching of zinc from brass is called
dezincification. If aluminium is removed the process is called
dealuminification. In the case of gray iron, dealloying is called graphitic
corrosion.
In dealloying process, the metal is left brittle, spongy and porous, hence
loses much of its strength, hardness and ductility.

The table below shows the combination of alloys and environments subject
to dealloying and elements preferentially removed.

ALLOY
Brasses/Zinc
Gray Iron
Aluminium bronzes
Silicon bronzes
Copper nickels

Tin bronzes

ENVIRONMENT
Water, especially
stagnant water
Soils, water
Hydrofluoric acid, acids
containing chloride ions
High temperature steam
and acidic species
High heat flux and low
water velocity (refinery
condenser tubes)
Hot brine or steam

ELEMENT REMOVED
Zinc (dezincification)
Iron (graphic orrosion)
Aluminium
(dealuminification)
Silicon
(desiliconification)
Nickel (denickelification)

Tin (destannification)

PREVENTION OF DEALLOYING CORROSION

Use of Inhibitors
Avoidance of stagnant water
Raise water pH to neutral or slightly alkaline level to decrease attack.

[8]

STRESS CORROSION CRACKING

The combined action of a tensile stress and a corrodent sometimes bring

about cracking of a metal or alloy. Many alloys are susceptible to this type of
cracking. Stresses that causes cracking result from welding, hammering,
thermal treatment or applied loads during service. In such cases, the metal
under stress becomes more anodic and tends to increase the rate of
corrosion.

For stress corrosion cracking to occur on an engineering structure, three

conditions must be met simultaneously, namely:
A specific crack-promotion environment must be present [e.g.
hammering]
The metallurgy of the material must be susceptible to stress corrosion
cracking
The tensile stresses must be above some threshold value
The stresses can be externally applied, but residual stresses often cause
stress corrosion cracking. Material factors influencing stress corrosion
cracking behavior are the alloy composition and microstructure. It is
important to note that stress corrosion cracking of susceptible alloys is
environment specific.
Environments that cause stress corrosion cracking are usually, but not
necessarily, aqueous and specific environmental parameters must be in
specific ranges for cracking to occur. These include (but not limited to)

Temperature
pH
Electrochemical potential
solute species
Solute concentration
Oxygen concentration

Prevention of Stress Corrosion Cracking

Changing the environment

Changing the material
Applying protective coatings
Changing applied or residual stress levels

MODULE FOUR
CORROSION TESTING
PURPOSES OF CORROSION TESTING
Corrosion tests are conducted in order to accomplish the followings:
1)
2)
3)
4)
5)

Evaluation and selection of materials.

Obtaining reference or database information.
Determining quality control and material acceptance requirements.
Monitoring corrosion control programs.
Identifying research parameters and corrosion mechanisms. i.e. to
validate various corrosion mechanisms and model corrosion behavior.

STEPS IN A CORROSION TEST PROGRAM

The logical steps to be taken when designing and conducting a corrosion test
program are identified thus:
1. Define The Test Objectives
What is to be learned by the test program? How will the data be used?
How will the results be assimilated into the overall decision process?
These questions are best developed and answered before the test
program is initiated in order to obtain the most effective and efficient
use of the test results.
2. Identify the Time And Cost/Budget Contraints
The timing of the corrosion tests must be compatible with the overall
decision-making process. There are often challenges when relating the
available time and money and the approach to the corrosion tests. And
those time and cost constraints can severely limit the options available
in a corrosion test program.

As the development cycle for products and processes is shortened, the

time constraint on the corrosion test program becomes even more
restrictive. The option of longer term corrosion tests to aid in material
selection, for example, becomes impractical.
3. Select Test Methods And Procedures To Meet Program
Objectives
The service conditions, candidate alloys and the possible corrosion
failure modes for each type of material guide the selection of the
appropriate test procedures of the material evaluation.
The staff, equipment and facility requirements for those test
procedures can then be determined. A decision can be made as to
whether to conduct in-house corrosion tests or to contract them to
others. Often, dedicated and specialized corrosion test equipment or
analytical facilities are required for corrosion testing.
One option is to develop the required technology and skills in-house.
Obviously, the degree of complexity, initial start up costs, and the
frequency of use for the particular test procedure are important factor
in this decision.
Another option is to utilize facilities that are available for the hire and
have the resources to conduct almost any type of corrosion test.
4. Prepare Test Plan And Specimens
First, a detailed test plan that includes timing and cost information is
developed. Next, test specimens are prepared and the necessary test
equipment is assembled. The procurement of test materials and the
desired configurations of test specimens can present a challenge.
Various companies specialize in corrosion test specimen preparation,
and they often stock a variety of materials used for corrosion tests in
common shapes.
5. Perform The Testing
The next step is to carry out the test program as planned. Adjustments
can be made along the way. The documentation of test conditions is
required throughout the exposure.
Standard tests and practices should be chosen when available and
applicable.
6. Evaluate The Specimen And The Environment
After the test exposures, the specimens are evaluated for the degree
and morphology of corrosion attack.

Useful information can be obtained by evaluating the environment

after the test. A determination of the chemistry and structure of the
corrosion products and deposits on test specimens after exposure can
be particularly informative.
7. Analyse The Results
The final step of corrosion test program involves analyzing the test
results, documenting and reporting those results and incorporating the
results into the overall program.

Preparation And Cleaning Of Test Specimens

The sampling of test materials and the preparation of test specimens are
extremely important variables in corrosion testing, because corrosion
behavior can be significantly influenced by variations in metallurgical
structure and the condition of the metal surface.
The uniformity of the metal sample should be checked in advance as part
of the plan for preparation of the test specimens.
The primary consideration should be the use of test specimens that are
truly representative of the specified materials.
Surface preparation by various grinding or polishing methods and various
chemical treatments can be a source of considerable variation in test
results and must be controlled.
As a general rule, the corrosion testing standards contain specific
recommendations regarding appropriate surface treatments, depending
on the metal alloy system. Judicious use of proper or standardized surface
treatments reduces variability in corrosion test results.
Specimen Cleaning
After the test, specimens must be cleaned and evaluated. In order to
determine the amount of corrosion damage, all non-protective corrosion
products should be removed, so that the amount of weight loss during the
exposure can be measured. The goal is to remove all of these products
without removing any of the underlying metal.

The options for removing corrosion products include scraping with a

rubber stopper, chemical descaling or electrochemical descaling. The
recommended descaling solutions for each material and alloy system are
identified in the corrosion testing standards.

CLASSIFICATION OF CORROSION TESTING

There are three general categories of corrosion tests:
Laboratory Tests
Pilot plant Tests
Field Tests

Laboratory Corrosion Tests

These are used to predict corrosion behavior when service history is
lacking and when time or budget constraints prohibit field testing. They can
also be used as screening tests prior to field testing.
Laboratory tests are particularly suited for quality control, material selection,
material and environment combinations, and the study of corrosion
mechanisms. These tests range from simple immersion tests to various kinds
of cabinet-controlled and autoclave-controlled environments to sophisticated
electrochemical tests.
Most laboratory tests are accelerated (short time) tests by design. The goal
of any accelerated laboratory test is to provide reliable information on the
performance of materials or coatings in service. The ranking of materials in
accelerated tests should be the same as that which would be observed in
service, and the relative life in the accelerated test should be translatable to
the useful life in service. Establishing this reliable bridge between
accelerated test data and expected performance life in service is a great
challenge.
Typically, accelerated laboratory corrosion tests increase the severity of the
environment by exposing the materials to more concentrated solutions,
higher temperature solutions, or increased period of wetness.

The danger associated with any laboratory test is that the accelerated
condition will substantially change the mechanism of corrosion and therefore
break all ties of reality and service performance.

Pilot Plant Corrosion Tests

They are usually more desirable than laboratory tests but they are also more
expensive. Here, the tests are made in a small scale plant that essentially
duplicates the intended large scale operation.
It is built so that design problems can be recognized and corrected, operators
can be trained and materials can be tested in authentic environmental
conditions. Because a pilot plant is constantly being modified in order to
determine optimum operating conditions, the solution temperature,
velocities and concentrations fluctuate more than they do in a full scale
operation.
Although these fluctuating environmental conditions facilitate testing of
materials under the worst possible conditions, careful and thorough record
keeping of the specimen exposure history is required.
Lack of accurate documentation of the specimen conditions to which the
specimens have been exposed can lead to erroneous results and/or
assumptions regarding the suitability of a given material for a specific
application.

Field Corrosion Tests

This is also referred to as simulated-service testing. It is the most reliable
predictor of corrosion behaviour because of actual service experience. This
includes exposures of either structural components, for example, welded
pipes, or test specimens in outdoor environments that are representative of
many general service situations.
Test materials are subjected to the cyclic effects of the weather,
geographical influences and bacteriological factors that cannot be
realistically duplicated in the laboratory.
Field tests range in duration from several months to many years. This type of
testing is important for such objectives as materials selection, predicting the

probable service life of a product or structure, evaluating new commercial

alloys and processes and calibrating laboratory corrosion tests.

Specific Types Of Laboratory Tests

Wetting of the Surface by condensing media in humid
atmosphere
Spraying of Aggressive media (Salt spray tests)
Immersion into corrosive liquid (immersion tests)

MODULE FIVE
CORROSION CONTROL BY CATHODIC AND
ANODIC PROTECTION
INTRODUCTION
Both cathodic and anodic protection methods involve modification of a metal
potential. In these methods, the potential of the metal to be protected is
shifted, either by the application of a direct current from a power supply or
by galvanic action from the connection of dissimilar metals.
The potential can be shifted into a region of immunity or into a region of
passivity for the metal. Shifting the potential to more reducing or more
negative potentials favours immunity of the metal and is referred to as
CATHODIC PROTECTION. Shifting the potential to more oxidizing or more
positive potentials within a region of passivity is referred to as ANODIC
PROTECTION.

E (+)

E(+)

PASSIVE

PASSIVE

ACTIVE

ACTIVE

IMMUNE

pH

IMMUNE

pH
ANODIC PROTECTION
CATHODIC PROTECTION

CATHODIC PROTECTION
Cathodic protection is a technique that can be applied to structures that are
exposed to a continuos bulk electrolyte (i.e structures that are immersed in
water, buried in the soil or encased in concrete). Common applications
include protection from soil corrosion (e.g. underground pipeline) and marine
corrosion (pipelines, ship hulls and offshore drilling platforms).
Cathodic protection is defined as the reduction or elimination of corrosion by
making the metal a cathode by means of an impressed current or
attachments to a sacrificial (galvanic) anode.
That is, cathodic protection is achieved
By connecting a corrodible anode to the metal that is to be protected.
This method is called sacrificial protection or galvanic protection.
By applying an electric current from a separate power source, a
technique called Impressed Current Cathodic protection.
Cathodic protection cannot be used in the following situations:

i.
ii.
iii.

Above the water line, in vapour. Electric current will not flow through a
gas, atleast not at the moderate voltages used in cathodic protection.
In non-conducting liquids, such as oil. An electrolyte is one of the
essential ingredients of an electrochemical cell.
In electrically screened area.

Insulat
ed wire

Anode

Tank [cathode]

SACRIFICIAL PROTECTION
The electrical arrangement of a sacrificial anode used to protect the inside of
a tank containing an electrolyte is shown above.
The anode in the center of the tank is electrically connected to the tank by
an insulated wire. The anode is made of a metal more corrodible than the
tank so that a galvanic cell is set up with the tank as the cathode. If the
insulated wire and its connections remain intact, cathodic protection
continues until the anode metal corrodes away.
Sacrificial protection is inexpensive because it has the obvious advantage
that it does not need any external power source. It also gives a fairly uniform
distribution of current, but the current output is low and can be increased if
more anodes is used.
Little or no maintenance is required, except the replacement of the anode
which is done after several years. But the cheap and simple arrangement of
the system does not allow good monitoring of the amount of protection being
given.

The sacrificial anodes normally use are Magnessium, Zinc or Aluminium.

Sacrificial anodes, also called Galvanic anodes, are most commonly used
where

Current requirements are relatively low

Soil resistivity is relatively low
Electrical power is not available
Short term protection is needed (usually 10 25 years)
Interference problems could occur
Stray currents put out by impressed-current cathodic protection anodes
can corrode other metal in the vicinity if they are not part of the
system.

Cathodic protection for underground pipe can be arranged thus

Ground level

Insulated copper wire

soil
current

Active metal anode

pipeline

Impressed - Current Cathodic Protection

V
A
Ground level
Insulated wire

soil

Anode bed

Coated pipe

The diagram above shows an impressed-current system used to protect a

pipeline. The buried anode(s) and the pipeline are both connected to an
electrical rectifier, which supplies direct current, from alternating current
source, to the buried electrodes (anodes and protected cathode) of the
system.
Unlike sacrificial anodes, impressed-current anodes need not be naturally
anodic, in fact most impressed-current anodes are made from nonconsumable electrode materials that are naturally cathodic. If these
electrodes were wired directly to a structure (i.e. without being electrically

rectified), they would act as cathodes and would cause accelerated corrosion
of the structure they are intended to protect.
The direct current source reverses the natural polarity and allows the
materials to acts as anodes.

ANODE MATERIALS REQUIREMENTS FOR CATHODIC PROTECTION

[1]

SACRIFICIAL ANODE

The anode must be a metal that is more active than the metal/alloy to
be protected.
The potential difference between the structure to be protected and the
sacrificial anode must be large enough to provide the necessary
cathodic protection current.
The sacrificial anodes must be of sufficient size and have sufficient
efficiency to provide the necessary usable life.
[2]

IMPRESSED-CURRENT ANODES

The anodes must be corrosion resistant

The anodes must have low consumption rate when connected to a
cathodic protection source.

ADVANTAGES OF IMPRESSED CURRENT OVER SACRIFICIAL ANODES

1) Impressed current is versatile. A wide range of voltage settings allows
the protection current to be adjusted precisely.
2) It is effective in high resistance environments.
3) Knowledge of the status of the system is continually available. The
protection current can be read on an ammeter at the power source.
4) Maintenance can be performed at rectifier stations. A bad anode is
easily found and replaced. Contrast that with walking along a pipeline
with a magnetic detector trying to find sacrificial anodes.

DISADVANTAGES OF IMPRESSED CURRENT WHEN COMPARED TO

SACRIFICIAL PROTECTION
1) Impressed current requires a source of electric power.

2) A high potential develops close to the anodes that may cause

interference on nearby structures.
3) Finding a suitable location for the anode ground bed can be difficult.

ANODIC PROTECTION
Anodic Protection is corrosion protection achieved by maintaining an active
passive metal or alloy in the passive region by an externally applied anodic
current. The potential of the metal to be protected is made more positive to
shift the conditions from a region of active corrosion to a region of passive
behaviour (see Potential-pH diagram).
Through the application of an anodic protection current, the potential of the
anode is raised from the active region into the passive region. The corrosion
rate is significantly reduced through the onset of passivity.
Anodic protection is effective only for metal/environment combinations
where passivity is achievable and maintainable. If for any reason, the passive
film is damaged and break down, the application of anodic protection can
result in greater damage than would be observed with no protection at all.
Anodic protection is used to passivate storage tanks and process vessels
containing highly corrosive electrolytes. The environment must be uniform so
that all the metal passivates, this rules out environments such as soils that
vary greatly in composition.

A
C

An Anodic Protection System

LEGEND
A = Potential sensing device,
power source,

B = Potential controller,

C = DC

D = Reference Electrode, E = Cathode, F = Tank (Anode)

An anodic protection system for a storage vessel is shown above. One or

more cathodes, a reference electrode, a potential sensing and controlling
circuit and a DC supply are required for each anodic protection system. The
vessel wall becomes the anodes of the circuit and the currents are controlled
so that the potential of the wall with respect to the reference electrode is
shifted and maintained in the passive region.

EQUIPMENT REQUIRED FOR ANODIC PROTECTION

[1]

THE CATHODE

The cathode should be a permanent-type electrode that is not dissolved by

the solution or the current impressed between the vessel wall and electrode.
Because the overall circuit resistance between cathode and vessel wall is
proportional to the electrode surface area, it is advantageous to use large
surface area electrodes.

The electrode size is chosen to conform to the geometry of the vessel and to
provide as large a surface area as possible. The location of the cathode is not
a critical factor in simple geometries, such as storage vessels, but in heat
exchangers, it is necessary to extend the electrode around the surface to be
protected.
[2]

REFERENCE ELECTRODES

Reference electrodes must be used in anodic protection systems because the

potential of the vessel wall as the anode must be controlled. The reference
electrode must have an electrochemical potential that is constant with
respect to time and that is minimally affected by changes in temperature
and solution composition. Many solutions have recommended reference
electrodes.
[3]

POTENTIAL CONTROL

The potential of the vessel wall with respect to the reference electrode must
be controlled in anodic protection installations. The potential control circuit
has two functions. First, the potential must be measured and compared with
the desired present value. Secondly, a control signal must then be sent to
the power supply to force the direct current between the cathode and vessel
wall. The amount of current forced through the circuitry is required to
maintain the potential at the present control point. A potentiostat is required
at the installation.
[4]

DC POWER SUPPLY

This has the identical design and requirements as the rectifiers for cathodic
protection with one exception. Because of the nature of the active passive
behavior of the vessel, the currents required to maintain the potential of the
vessel wall the passive range can become very small.
The packaging of these electronic components occasionally involves special
requirements because most of the installations are made in chemical plants.
Explosion proof enclosures are sometimes required, and chemically
resistant enclosures are necessary in other installations.

ADVANTAGES OF ANODIC PROTECTION OVER CATHODIC PROTECTION

1) It can be used in extremely corrosive environment where power costs
of cathodic protection would be prohibitive.

2) The corrosion rate of the protected system is directly proportional to

the current density applied so that the corrosion rate can be
continually monitored.
3) The current requirements are low once the metal has passivated.
However, a great deal of current is required to passivate. For example,
316 stainless steel requires 6500 A/m2 to passivate in 67% H2SO4 at
room temperature but only 1 mA/m2 is needed to maintain passivation.
4) Operating conditions can be determined precisely by laboratory
experiments, whereas cathodic protection often requires fine tuning
adjustments over periods of months to get the proper protection.
5) Current distribution is excellent.

DISADVANTAGES OF ANODIC PROTECTION

1)
2)
3)
4)
5)
6)

7)
8)
9)

Anodic protection will not work if the metal does not passivate well.
Corrosion is not completely stopped, unlike cathodic protection.
Metal in vapour zone does not passivate.
High currents are often requires to passivate.
Anodic protection costs almost as much to protect a small system as a
large one.
All protection equipment must work properly or disaster can strike. A
potential a little too high (transpassive) or a little too low (active) will
destroy the metal that is supposed to be protected.
Anodic protection will not work in non-electrolyte, such as oil or air.
Anodic protection cannot be used in an inhomogeneous environment,
such as soil or unstirred solutions.
It cannot be used for a mixture metals. Corrosion of some might be
increased at the protection potential.

MODULE SIX

CORROSION CONTROL BY MATERIALS

SELECTION
Selection of the optimal material of construction for any component can be a
big money saver, but the selection process is usually not straight forward.
The challenge of materials selection is to achieve adequate performance at
the lowest possible cost.
Corrosion resistance is not the only property to consider in making materials
selection, but it is of major importance in many industries, such as chemical
processing or pulp and paper industries. Other factors to consider include the
technical performance and economic factors. Eventual choice of material is
the result of several compromises.
In specifying a material the selection process usually necessitates listing the
requirements, selecting and evaluating materials and choosing the most
economical material (often based on life cycle costs, not initial costs).
Typical requirements and some of the procedures involved in making a
selection are given in Table 6.1 below. And some of the factors that must be
considered when determining the corrosion performance of a given material
are listed in Table 6.2.

Table 6.1: Material Selection Requirements

[A]

[B]

Requirements To Be Met
Properties [corrosion, mechanical, physical, appeareance]
Fabrication [ability to be formed, welded, machined]
Compatibility with existing equipment or fluids
Maintainability
Specification coverage
Availability of design data
Experience base with this or similar materials
Selection Considerations
Expected total life of plant or process
Estimated service life of material
Reliability [safety and economic consequences of failure]
Availability and delivery time
Need for further testing
Material costs

 Fabrication costs
Maintenance and inspection costs

Table 6.2: Information Necessary for Estimating Corrosion

Performance
[A]

[B]

Corrodent Variables
Environment type [marine, industrial, internal fluid etc]
Main constituents [identity and amount]
Temperature
pH
Degree of aeration
Velocity or agitation
Pressure
Mechanism Of Reaction With Fluids

Catalytic reaction [catalytic decomposition of fluid]

Fluid degradation [reactions in which the physical or chemical
characteristics of the fluid are altered]

[C]

Type Of Application

What is the function of part or equipment?

Are size change, appearance or corrosion product problem?
What effect will uniform corrosion have on serviceability?
What effect will localized corrosion have on usefulness?
Will there be stresses present?
Is design compatible with the corrosion characteristics of the
materials?
What is the desired service life?

[D]

Experience

Has material been used in an identical situation? What were the

results?
Has material been used in a similar situation? What was the
performance?
Was there any pilot experience?
Are there any plant corrosion test data?

 What literature or database information is available?

THINGS TO CONSIDER BEFORE MATERIALS SELECTION

[1] The choice of the material should be made not only on its cost and
structure, but also on its chemical properties and its environment.
[2] Noble metals are not immune to corrosion but they cannot be used for
general purposes for economic reasons. The purest possible metal will be
used.. for minutes amounts of some impurities may lead to severe
corrosion.
[3] Both corrosion resistance and strength of many metals can be improved
by alloying. Several corrosion resistant alloys have been developed for
specific purposes and environments.
For example,
Highly stressed Nimonic alloys (Ni Cr Mo alloys) used in gas
turbines are resistant to hot gases.
Cupro nickel (70%Cu + 30%Ni) alloy containing 0.2%Fe are now
being used extensively for condenser tubes and for bubble trays used
in fractionating columns in oil refineries.
[4] If an active metal is used, it should be insulated from more cathodic
metals.
[5] If two metals have to be in contact, they should be so selected that their
oxidation potentials are as near as possible.
[6] Moisture should be excluded wherever practicable. If moisture or
electrolyte solution cannot be avoided, suitable inhibitors should be
employed.
[7] Each metal shows a minimum corrosion at a specific pH. Therefore,
corrosion can be controlled by suitably adjusting the acidity or alkalinity of
the environment. When control of pH is not practicable, corrosion can be
reduced by using inert coating and inactive metals.
[8] When contact of dissimilar metals is unavoidable, suitable insulators
should be inserted between them to reduce current flow and attack on the
anode.

[9] When a structure consists of two dissimilar metals, it is beneficial to use

a more active third metal in contact so that the structure will be saved from
corrosion at the expense of the third metal.

MATERIALS SELECTION
Most corrosion problems originate from either improper design or improper
materials selection. However a good choice of material can overcome severe
environmental conditions.
[A]

STAINLESS STEELS

Stainless steels are usually the first choice for a probably corrosive
environment with unknown properties, because these alloys are resistant to
a wide range of oxidizers but they may not completely withstand strong
reducing solutions, such as hydrochloric acid.
A stainless steel is defined as a ferrous alloy containing enough chromium to
passivate in some environment, such as air and water. At least (10 -12)% Cr
is required to form a passive film (mainly Cr2O3). The carbon content is
typically quite low in stainless steels, so the terms carbon steels and
steels refer to non-stainless steels, since stainless steels have nothing in
common with ordinary steels in terms of corrodibility.
Stainless steels are classified into five general groups, according to their
metallurgical structures. They are:

Martensitic types
Ferritic types
Duplex (Ferritic-Austenitic) types
Precipitation-Hardening types
Austentic types

The alloys are formed by rolling, drawing, forging etc.

UNS

Cr %

Ni %

C%

Others %

Uses

MARTENSITIC TYPES
S40300

11.5 13.0

0.15 max

Turbine

S41000

11.5 13.5

0.15 max

S41400

11.5 13.0

S41600

12.0 14.0

0.15 max

S41040

11.5 13.5

0.15 max

1.25 2.5

0.15 max
0.6 Mo
max
0.5 Nb
max

valve
Furnace
parts
Petroleum
towers
Screws,
bolts
Aircraft
parts

FERRITIC TYPES
S40500

11.5 14.5

S43035

17.0 19.0

S44600

23.0 27.0

0.5 max

0.8 max

0.2 Al

0.07 max

0.1 Al, 1 Ti

0.2 max

0.25 N

Boiler
tubing
Welded
equipment
Burner
nozzles

DUPLEX [FERRITIC AUSTENITIC] TYPES

S32900
S32304

23.0 28.0
21.5 24.5

2.5 5.0
3.3 - 5.5

0.2 max
0.03 max

0.2 Mo
0.3 Mo, 0.3
Cu, 0.1 N

Chutes
[inclined
plane]

PRECIPITATION HARDENING TYPES

S13800
S17700

12.25
13.25
16.0 18.0

7.5 8.5

0.05 max

2 Mo, 1Al

6.5 7.75

0.09 max

1Al

Pressure
vessels
Aircraft

AUSTENTIC TYPES
S30403
S34700

[B]

18.0 20.0
17.0 19.0

8.0 10.5
9.0 13.0

0.03 max
0.08 max

1 Nb

Dairy tanks
Kitchen
sinks

NICKEL AND NICKEL ALLOYS

Commercially pure nickel has high corrosion resistance and good weldability.
Nickel and Nickel alloys are widely used in the food industry and are
frequently selected for service in chlorine, hydrogen chloride and chlorinated
hydrocarbons. They are very resistant to high temperature air and stress
corrosion cracking.

However, Nickel alone cannot withstand strong oxidizing solutions such as

nitric acid, ferric chloride and is not resistant to seawater. Thus some nickel
alloys have been specially formulated to overcome these deficiencies.
Nickel Copper Alloys
These alloys resist seawater well and can handle caustics without stress
corrosion cracking.
Nickel Molybdenum Alloys
They are unique in resisting hydrochloric acid at all concentrations and all
temperatures up to boiling, as well as other acids.
Other Nickel Alloys include Nickel- Chromium Iron Alloys, Nickel Chromium
Molybdenum Alloys.
Other metal alloys of good corrosion resistant include
Cast Iron . (2 4)% Carbon, (0.5 2.5)% Silicon
Aluminium and Magnesium Alloys
Lead and Zinc Alloys.

NON METALLIC MATERIALS

[A]

PLASTICS

Plastics are another class of materials that can be used in place of some
metals and alloys to prevent corrosion occurrence. Generally, plastics are
either thermoplastic or thermosets.
Examples of plastics are
Polyvincyl chloride (PVC) . Rigid PVC is used for piping, fans etc.
Flexible PVC is used for tubing and sheeting.
Nylons are used for coatings, and mechanical parts and have excellent
abrasion resistance.
Thermoplastic elastomers are used for hoses, cable insulation, linings,
coating.

Fiber reinforced plastics . To achieve high tensile strength used in

aerospace applications, gives high corrosioj resistance.
[B]

CERAMICS

Are compounds of metallic and non metallic materials, and have wide range.
These compounds have outstanding high temperature stability and chemical
resistance. They are hard, electrical insulators, resistant to erosion
corrosion. But they are brittle hence they can withstand only low tensile
stress.
[C]

CONCRETE

Concrete are used for large tanks, for large diameter pipe and as a lining for
vessels and steel pipes. It is commonly reinforced with steel in all types of
construction work where tensile stresses might occur.
[D]

WOOD

Well treated and highly polished wood can be used in form of container, to
avoid corrosion. Examples include wooden tanks, cooling towers.

MODULE SEVEN
CORROSION CONTROL BY PROTECTIVE
COATINGS AND INHIBITORS
COATINGS
Organic coatings [paints and plastic or rubber linings]
Metallic coatings
Non - metallic inorganic coatings [cements, ceramics, glasses].
The coatings applied to often are multifunctional, providing corrosion control,
an aesthetic surface appearance, abrasion and impact resistance, electrical
insulation and other important properties.

Coatings and lining may protect metals/alloys through three basic

mechanisms:
Barrier protection
Chemical inhibition
Galvanic (sacrificial) protection
Barrier protection is achieved when coatings completely isolate the substrate
from the environment.
Chemical inhibition is achieved by the addition of inhibitive pigments to
paints.
Sacrificial protection is achieved by coating the metal with a more active
metal.

INHIBITORS
An inhibitor is a chemical substance or combination of substances that,
when present in the environment, prevents or reduces corrosion without
significant reaction with the components of the environment.
Inhibitors find major use in closed environment systems that have good
circulation, so that an adequate and controlled concentration of inhibitor is
ensured. Such conditions can be met, for instance, in cooling water recirculating systems, oil production, oil refining and acid picking of steel
components. An example is the inhibitor being used as antifreeze for
automobile radiators.
The application of inhibitors must be viewed with caution by the user
because inhibitors may provide excellent protection for one metal in a
specific system but can aggravate corrosion for other metals in the same
system. Since many closed systems contain a variety of metals and alloys,
this fact should be remembered.
Inhibitors can be organic or inorganic compounds, and they are usually
dissolved in aqueous environments. Some of the most effective inorganic
inhibitors are chromates, nitrites, silicates, carbonates, phosphates.
The organic inhibitors are many and include amines, heterocyclic nitrogen
compounds, sulfur compounds, some natural compounds (such as glue
proteins) and mixtures of two or more compounds.

TYPES OF INHIBITORS
Commonly used inhibitors are:

Anodic
Cathodic
Ohmic
Precipitation
Vapour phase

The protection provided by these inhibitor types can result in

The presence of adsorbed films
The formation of bulky precipitates
The promotion of passivity of the metal to be protected.
ANODIC (PASSIVATING) INHIBITORS
These function by selectively covering anodic sites on the metal surfaces.
The effect is shown using mixed potential diagrams for the anodic and
cathodic reaction kinetics in Figure 7.1 below, i.e graph of E(+) against log
i
E(+)
Note: A = Anodic inhibitor
A

B = No Inhibitor

The addition of an inhibitor on the potential versus log (current density)

diagram promotes a shift of the anodic polarization curve from the solid line
to the dashed line, with little or no effect on the cathodic polarization curve.
The net effect is a decrease in the corrosion rate.
Anodic inhibitors are considered dangerous, because insufficient
concentrations can lead to accelerated localized attack at
unprotected sites. Generally, a critical concentration for anodic
inhibitors must be maintained.
Typical anodic inhibitors include oxidizing chemicals, such as chromates,
nitrites, nitrates and phosphates.

CATHODIC INHIBITORS
These reduce corrosion by slowing the reduction reaction rate of the
electrochemical corrosion cell. This is done by blocking the cathodic
sites by precipitation. For example, calcium, magnesium and zinc ions will
precipitate hydroxides on cathodic sites as the local environment becomes
more alkaline due to the reduction reaction at these sites. As the pH
increases, hydroxide precipitation occurs.
Cathodic inhibitors are effective when they slow down the cathodic reaction
rate. Removal of oxygen from the corrosive environment will significantly
decrease the corrosion rate. This can be done through
a) The use of oxygen scavangers, such as sodium sulphite and
hydrazine, which react with the oxygen and remove it from the
solution.
b) Vacuum deaeration
c) Boiling to lower the dissolved oxygen concentrations.

OHMIC INHIBITORS
They are also referred to as general filming inhibitors, reduce the
corrosion rate by decreasing the mobility of ionic species between
anodes and cathodes on the corroding metal surface. By decreasing
the ionic conductivity of the solution, the corrosion rate is reduced.
These inhibitors function through strong adsorption to the metal surface.
Ohmic inhibitors include amines, which are cationic and sulfonates, which are
anionic.
PRECIPITATION INHIBITORS
They promote the formation of a bulky precipitation film over the entire
surface. Silicates and phosphates are examples of such inhibitors.

VAPOUR - PHASE INHIBITORS

These are chemical compounds that have relatively high vapour pressures
and that adsorb on metal surfaces. Once adsorbed, they either neutralise

moisture, promote the formation of passive films, or protect through the

formation of a general film on the surface.
Most vapour-phase inhibitors provide protection by multiple means. A caution
is that vapour-phase inhibitors are metal specific and if used with wrong
metal, they can lead to accelerated attack. The protection is most effective
in closed spaces with little ventilation.

APPLICATION OF INHIBITORS
Inhibitor application techniques include:
continuous injection
batch treatment and
incorporation of inhibitors into protective coatings or primers.
The latter method provides protection by allowing the inhibitor to leach from
the protective coating into the environment as it comes in contact with the
metal surface.

MODULE EIGHT
CORROSION IN AUTOMOBILE, CHEMICAL AND
PETROLEUM INDUSTRIES