DEPARTMENT OF CHEMICAL ENGINEERING

CORROSION OF METALS AND ALLOYS (CHE 431)

LECTURE NOTES

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).

Smelting &
Refining of
Ore

Finished
Iron
product

Iron in
contact
with Air &
moisture

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 (due to flow or agitation)
Mechanical loads on material (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

Corrosion

Localised

Macroscopic (by
naked Eye)
1. Galvanic

Microscopic (by
Magnification)

2. Erosioncorrosion

1. Intergranular

3. Crevice

4.
5.

Pitting

Uniform

2. Stresscorrosion
cracking

Dealloying

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.

NATURE OF THE METAL

[A] 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 Fe 2+ 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

% Purity
99.999
99.99
99.95

Corrosion rate
1
2,650
5,000

[D] Physical State of the Metal

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

A = Active metals, B = Trans-passive metal

A

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, SO 3 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
alloys. 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 O 2) 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
chloride 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 O 2 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

Br2(l) + 2e- 2Br(aq)
NO-3(aq) + 4H+(aq) + 3e- NO(g) + 2H2O
2Hg2+(aq) + 2e- Hg2+(aq)

+ 1.23
+ 1.07
+ 0.96
+ 0.92

Ag+(aq) + e- Ag(s)
Fe3+(aq) + e-

Fe2+

+ 0.80
+ 0.77

(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).
Fe - 2e- Fe2+

E.g.

OR Fe Fe2+ + 2eThis 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+ + ne-

where 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 H 2 gas is formed.
2H+ + 2eOR 2H 3O+

H2
+ 2e-

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 Corrosion process involving O 2
are called Oxygen type.
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

Fe2+

H2 O

H+, O2, e-

Fe2+
Anode e-

METAL

LEGEND
Rust:

Fe2O 3.nH2O

Anode: Oxidation of Fe forms a pit and yields

electrons, which travel through the metal.
Cathode: Electrons migrate to the cathode reduce O 2 and H2O.
Fe2+ migrate through the droplet and reacts with O 2
and H2O to form rust, Fe2O 3.nH2O
Corrosion of iron metal can equally be described thus

AIR
OH-

OH-

OH-

OH-

OH-

OHIron 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, , is then calculated using

=
K = constant,

T = Time of exposure,

where

W = Weight loss,

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)

A = Area,

D = Density

Constant, K
3.45 X 10 6
3.45 X 10 3
2.87 X 10 2
8.76 X 10 7
2.78 X 10 6

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 intergranular 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

Cathode

OH

H 2O
H H2O

Anode

OH -

Cathode

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 O 2,
nitric acid (HNO 3), 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)
5)
6)
7)
8)

Uniform or General Corrosion

Pitting Corrosion
Crevice Corrosion
Galvanic Corrosion
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 pitinitiation 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 O 2 in the
crevice. This is commonly observed in lap joints, bolt holes, threaded joints, riveted seams,
overlapping screen wires, beneath coatings.

Crevice corrosion

Metal or Non metal

Metal

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 siz e.
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

corrosion pit

original metal surface

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 erosioncorrosion.
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
resistance because local anodic and cathodic areas are more readily formed.

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

IMMUNE
pH

ANODIC PROTECTION

pH
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.

Insulated 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

pipeline

Active metal anode

Impressed - Current Cathodic Protection

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 non-consumable 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.

An Anodic Protection System

LEGEND
A = Potential sensing device, B = Potential controller, C = DC power source,
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/m 2
to passivate in 67% H 2SO4 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)

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.
7) Anodic protection will not work in non-electrolyte, such as oil or air.
8) Anodic protection cannot be used in an inhomogeneous environment, such as soil or
unstirred solutions.
9) 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] 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

[B] 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] Corrodent Variables

Environment type [marine, industrial, internal fluid etc]

Main constituents [identity and amount]
Temperature
pH
Degree of aeration
Velocity or agitation
Pressure

[B] 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

0.6 Mo max
0.5 Nb max

Turbine valve
Furnace parts
Petroleum
towers
Screws, bolts
Aircraft parts

MARTENSITIC TYPES
S40300
S41000
S41400

11.5 13.0
11.5 13.5
11.5 13.0

S41600
S41040

12.0 14.0
11.5 13.5

1.25 2.5

0.15 max
0.15 max
0.15 max
0.15 max
0.15 max

FERRITIC TYPES
S40500
S43035

11.5 14.5
17.0 19.0

S44600

23.0 27.0

0.5 max

0.8 max
0.07 max

0.2 Al
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

12.25 13.25

7.5 8.5

0.05 max

2 Mo, 1Al

S17700

16.0 18.0

6.5 7.75

0.09 max

1Al

Pressure
vessels
Aircraft

1 Nb

Dairy tanks
Kitchen sinks

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

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 re-circulating 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 vapourphase 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