www.covenantuniversity.edu.

ng

Raising a new Generation of Leaders

CHE 431 CORROSION OF

METALS AND ALLOYS

Lecturers: OLAYEMI ODUNLAMI

(PhD) AND AJIBOLA OGUNBIYI

COURSE COMPACT

College:
Department:
Program:
Course Title:
Course Code:
Unit:

College Of Engineering
Chemical Engineering
Chemical Engineering
CORROSION OF METALS AND ALLOYS

CHE 431
2

Ajibola Ogunbiyi

 Course Lecturer:
Ajibola Ogunbiyi

Dr. Olayemi Odulami & Mr

Semester:

Alpha

Time:

Wednesdays: 8am 10am

Location:
Chemical Engineering
Building, Room C37
Ajibola Ogunbiyi

Methods of Lecture Delivery/Teaching Aids:

It will be both instructive and participatory.
Examples will be drawn from the current and
relevant issues in the society. Students will have
access to the lecture note on the Moodle
platform. Illustrative materials will be used and
made available in class to facilitate learning. The
teaching aids shall include Laptop, removable
drive, smartboard and projector.
Ajibola Ogunbiyi

OUTLINE

Week 1: Introduction:
Week 2: Meaning, Effects and Causes of Corrosion
Week 3: Principles of Corrosion
Week 4: Forms of Corrosion
Week 5: Test 1
Week 6: Corrosion Testing
Week 7: Selection of Materials
Week 8: Corrosion Prevention
Week 9: Corrosion in Chemical Industries
Week 10: Test 2
Week 11: Corrosion in Petroleum Industries
Week 12: Corrosion in Automobile Industries
Week 13: Revision
Week 14: Examination
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 Tutorials:
Tutorial questions will be given to students. Students will be
expected to try their hands on these questions. Some of these will be discussed in
the classroom.
Structure Of The Programme/ Method Of Grading:
Mid-semester test is 10 marks, Assignment is 10marks and Tutorial questions is
10marks. All these make up the Continuous Assessment of 30marks. Examination is
70 marks.
Ground Rules And Regulations:
Students are expected to comport themselves well during lecture hours so as to
derive the maximum benefit from the lectures.
No student will be allowed into the class fifteen (15) minutes after the
commencement of the lecture. Students causing distraction or disturbance will be
sent out of the lecture room. Only students that are physically present for each
lecture will sign the attendance sheet. It is a grave offence to sign the attendance
sheet for another student.
Ajibola Ogunbiyi

The 75% minimum attendance rule for eligibility to take the

exam will be STRICTLY ENFORCED. On no account will any
student be given a concession.
Topics For Term papers/Assignments/Students Activities:
Practical and relevant questions will be given to students as term
papers, assignments and tutorials.
Alignment With Covenant University Vision/Goals:
One important goal of Covenant University is to raise generational
leaders through mental productivities; the lecturers conducts and
mode of teaching will be tailored in this pattern. Emphasis will be
laid on the enforcement of this goal among the students.

Ajibola Ogunbiyi

RECOMMENDED TEXTS
Corrosion Control by Samuel A. BradfordGerald
Kiely (2003).
A Textbook of Engineering Chemistry by S.S. Dara
(2006). S. Chand And Company Limited.
Corrosion: Understanding the Basics (Second
Edition) by J.R. Davis (2003).
Corrosion and Corrosion Control, by R. Winston
Revie and Herbert H. Uhlig Copyright 2008 John
Wiley & Sons, Inc.
Ajibola Ogunbiyi

E-learning platform
From time to time in this semester, students will be
directed to the Universitys e-learning platform
called Moodle for lecture notes, assignments, ebooks, quizzes, important instructions, etc. The
Moodle has the URL:
www.moodle2.covenantuniversity.edu.ng
Students are advised to always frequent this website
for important information. The login access to the
Moodle can be obtained from the CSIS.
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Important points

Message to carryover students (clashes)

Reading groups
Start early
You can succeed!

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QUESTIONS

?
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MODULE 1 - INTRODUCTION
Preambles
What is corrosion ?
Roles of corrosion scientists and engineers.
Importance or effects of corrosion with respect
to appearance, performance, safety and cost.
Risk Management (a brief look)
Causes of corrosion at a glance

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Preambles
Undoubtedly, corrosion joined the league of mans numerous
concerns/challenges soon after the first metals were made.
One solution always gives rise to another problem.
Corrosion was not likely to have been controlled any better than
with the use of maxims like bring your tools in out of the rain,
clean the blood off your sword right after battle etc
Now that the mechanisms of corrosion are better understood, more
techniques have been developed to control it.
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Introduction
Global challenges for 21st Century are:
Energy
Water
Air
i.e.
(a) enough energy to provide a good standard of living,
(b) clean water to drink, and
(c) clean air to breathe
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 Management of corrosion is critical in using materials

effectively and efficiently to meet these challenges.
Materials reliability is of utmost importance to
(a) assure safety and
(b) prevent failure.
For example, materials reliability is crucial in:
High- pressure steel pipelines that must operate for decades
without failure so that neither air nor groundwater is polluted.
Nuclear waste disposal for the safety of posterity.
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Automobiles
Chemical plants
Refineries
Water vessels e.g. ships

Zero failures or no failures are slogans adopted by senior management

of engineering firms.
To ensure the realization of this policy is achieved, corrosion engineers and
other stakeholders must use established strategies, innovative approaches and
experimental trials

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High-pressure steel pipelines

High- pressure steel pipelines
that must operate for decades
without failure so that neither
air nor groundwater is polluted.

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Nuclear power plant

The Bruce Nuclear Generating Station, the largest nuclear power facility in the world
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Nuclear waste disposal

Nuclear waste disposal for the safety

of posterity.
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Corrosion in automobiles

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Corrosion in process plant

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Water vessels

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Refineries and corrosion

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What is Corrosion ?
Corrosion is the destructive attack of a metal
by chemical or electrochemical reaction with its
environment.
Is deterioration by physical means corrosion ?

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It is called erosion or wear.

Chemical attack may occur together with
physical deterioration, e.g:
corrosion erosion,
corrosive wear, or
fretting corrosion
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 Non-metals do not corrode

Although plastics may swell or crack, wood may
split or rot, granite may erode, and Portland cement
may leach away, but, the term corrosion is
restricted to chemical attack of metals.
Rusting refers to the corrosion of iron or iron base alloys.
Hence, non-ferrous metals do not rust but corrode.
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Corrosion science and engineering:

Sine qua nons to understanding corrosion (a chemical
change) :
Familiarity with the principles of chemistry (in order to
understand corrosion reactions)
Good knowledge of electrochemistry (since corrosion
processes are majorly electrochemical)
Conversance with the fundamentals of physical
metallurgy as well (since structure and composition of a
metal often determine corrosion behaviour)
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A corrosion scientist studies and uses corrosion

mechanisms to improve
(a) the understanding of the causes of corrosion,
and
(b) the ways to prevent or at least minimize
damage caused by corrosion.
The corrosion engineer, on the other hand,
applies scientific knowledge to control corrosion.
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For example, the corrosion engineer

uses cathodic protection on a large scale to prevent corrosion of buried pipelines,
tests and develops new and better paints,
prescribes proper dosage of corrosion inhibitors, or
recommends the correct coating.
The corrosion scientist, in turn,
develops better criteria of cathodic protection,
outlines the molecular structure of chemical compounds that behave best as inhibitors,
synthesizes corrosion- resistant alloys, and
recommends heat treatment and compositional variations of alloys that will improve
their performance.
Both the scientic and engineering viewpoints supplement each other in the diagnosis of
corrosion damage and in the prescription of remedies.
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Importance of Corrosion

Economics
Safety
Conservation*
Appearance
Performance*

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Economics
Corrosion of piping, tanks, metal components of machines, ships,
bridges, marine structures, etc, causes:
Reduction in material
economic losses
That is:
Loss of metal by corrosion is a waste not only of the metal, but also of
the energy, the water, and the human effort that was used to produce
and fabricate the metal structures in the first place.
In addition, rebuilding corroded equipment requires further
investment of all these resources metal, energy, water, and human.

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Direct Losses
Direct losses include the costs of :
(a) replacing corroded structures and machinery or their components,
such as condenser tubes, mufers, pipelines, and metal roong,
including necessary labor.
(b) repainting structures where prevention of rusting is the prime
objective and
(c) the capital costs plus maintenance of cathodic protection systems
for underground pipelines.
Sizable direct losses are illustrated by the necessity to replace several
million domestic hot- water tanks each year because of failure by
corrosion and the need for replacement of millions of corroded
automobile mufers.
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(d) the extra cost of using corrosion - resistant metals and alloys
instead of carbon steel where the latter has adequate mechanical
properties but not sufcient corrosion resistance;
(e) costs of galvanizing or nickel plating of steel, of adding corrosion
inhibitors to water, and of dehumidifying storage rooms for metal
equipment.
The economic factor is a very important motivation for much of the
current research in corrosion.
Studies have shown that costs of corrosion to top developed
countries are found to be approximately 3 4 % of the Gross
National Product.
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Indirect Losses
Shutdown
Loss of product
Loss of efficiency

Contamination of products
Overdesign

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 Shutdown: The shutdown of a unit in a plant while repairs are going

on may cost a significant amount of money on hourly basis.
Loss of products: Losses of oil, gas, or water occur through a
corroded pipe system until repairs are made.
Loss of efficiency
Corrosion processes can impose limits on the efciencies of energy
conversion systems, e.g.
1. Diminished heat transfer through accumulated corrosion products
2. Clogging of pipes with rust necessitating increased pumping
capacity.
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Contamination of Products
Spoilage of food in corroded metal containers
Copper salts accelerate rancidity of soaps and shorten the time that
they can be stored before use.
Traces of metals may similarly alter the color of dyes.
Overdesign
Equipment is often designed many times heavier than normal
operating pressures or applied stresses would require in order to
ensure reasonable life.
E.g. reaction vessels, boilers, condenser tubes, oil-well sucker rods,
pipelines transporting oil and gas at high pressure, water tanks, and
marine structures.
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 Indirect losses are a substantial part of the

economic tax imposed by corrosion, although it is
difcult to arrive at a reasonable estimate of total
losses.
In the event of loss of health or life through
explosion, unpredictable failure of chemical
equipment, or wreckage of airplanes, trains, or
automobiles through sudden failure by corrosion of
critical parts, the indirect losses are still more
difcult to assess and are beyond interpretation in
terms of dollars.
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Safety
Corrosion can compromise the safety of operating
equipment by causing failure (with serious
consequences) of, for example, pressure vessels,
boilers, metallic containers for toxic chemicals,
turbine blades and rotors, bridges, airplane
components, and automotive steering mechanisms.
Safety is a critical consideration in the design of
equipment for nuclear power plants and for disposal
of nuclear wastes.
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RISK MANAGEMENT
In general, risk, R , is dened as the probability, P , of an occurrence
multiplied by the consequence, C , of the occurrence; that is,
R=PC
Hence, the risk of a corrosion-related failure equals the probability that such
a failure will take place multiplied by the consequence of that failure.
Consequence is typically measured in nancial terms that is, the total cost
of a corrosion failure, including the cost of replacement, clean-up, repair,
downtime, and so on.
Any type of failure that occurs with high consequence must be one that
seldom occurs. On the other hand, failures with low consequence may be
tolerated more frequently. Figure 1 shows a simplied approach to risk
management.

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 Managing risk is an important part of many engineering

undertakings today. Managing corrosion is an essential
aspect of managing risk. Firstly, risk management must
be included in the design stage, and then, after
operation starts, maintenance must be carried out so
that risk continues to be managed.
Engineering design must include corrosion control
equipment, such as cathodic protection systems and
coatings. Maintenance must be carried out so that
corrosion is monitored and signicant defects are
repaired, so that risk is managed during the operational
lifetime.
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Fig. 1: A simplied approach to risk management, indicating qualitatively the areas of high risk,
where both consequence and probability are high
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CAUSES OF CORROSION
Although many causes of corrosion will be
looked into in detail in the subsequent lectures,
in this introductory lecture, two parameters are
mention are worthy of mention here:
the change in Gibbs free energy G and
the Pilling Bedworth ratio.
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The change in Gibbs free energy

The change in Gibbs free energy, G , for any
chemical reaction indicates the tendency of that
reaction to proceed. Reactions occur in the
direction that lowers the Gibbs free energy. The
more negative the value of G , the greater the
tendency for the reaction to go.

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The Pilling-Bedworth ratio

The first basic understanding of oxidation
mechanisms came in 1923 when N.B. Pilling and
R.E. Bedworth divided oxidizable metals into
two groups: those that form protective oxide
scales and those that do not. They proposed that
a scale will be unprotective if the oxide layer on
the metal occupies a smaller volume than the
volume of metal reacted.
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 The Pilling-Bedworth ratio is a parameter that can be

used to predict the extent to which oxidation may occur.
The Pilling-Bedworth ratio is Md / nmD , where M and D
are the molecular weight and density, respectively, of the
corrosion product scale that forms on the metal surface
during oxidation; m and d are the atomic weight and
density, respectively, of the metal, and n is the number of
metal atoms in a molecular formula of scale
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 The Pilling-Bedworth ratio indicates whether the volume of the

corrosion product is greater or less than the volume of the metal
from which the corrosion product formed.
If Md / nmD < 1 , the volume of the corrosion product is less than
the volume of the metal from which the product formed. A lm of
such a corrosion product would be expected to contain cracks and
pores and be relatively non-protective.
On the other hand, if Md / nmD > 1, the volume of the corrosion
product scale is greater than the volume of the metal from which the
scale formed, so that the scale is in compression, protective of the
underlying metal. A Pilling-Bedworth ratio greater than 1 is not
sufcient to predict corrosion resistance.

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 If Md / nmD >> 1, the scale that forms may buckle and

detach from the surface because of the higher stresses that
develop. For aluminum, which forms a protective oxide and
corrodes very slowly in most environments, the Pilling
Bedworth ratio is 1.3, whereas for magnesium, which tends to
form a non-protective oxide, the ratio is 0.8.
If the ratio is much greater than 2, and the scale is growing at
the metal-oxide interface, large compressive stresses build up
in the scale so that if the scale grows thick it will likely buckle
and spall off, leaving the metal unprotected.

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 Although the Pilling-Bedworth ratio is a gross

oversimplification, which is not always correct,
it provides information about the protective
nature of metal oxides as a rough rule of thumb.
In other words, there are exceptions and
limitations to the predictions of the Pilling B
edworth ratio.
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Example Problem

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Questions

?
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Assignment Problems
1.

A manufacturer provides a warranty against failure of a carbon

steel product within the rst 30 days after sale. Out of 1000 sold, 10
were found to have failed by corrosion during the warranty
period. Total cost of replacement for each failed product is
approximately N1,200,000, including the cost of environmental
clean-up, loss of product, downtime, repair, and replacement.

(a) Calculate the risk of failure by corrosion, in Naira.

(b) If a corrosion - resistant alloy would prevent failure by corrosion,
is an incremental cost of N1200 to manufacture the product using such
an alloy justied? What would be the maximum incremental cost that
would be justied in using an alloy that would prevent failures by
corrosion?
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2. Linings of tanks can fail because of salt contamination of the surface

that remains after the surface is prepared for the application of the
lining. Between 15% and 80% of coating failures have been attributed
to residual salt contamination. The cost of reworking a failed lining of a
specic tank has been estimated at N9,000,000. [Reference: H. Peters,
Monetizing the risk of coating failure, Materials Performance 45 (5),
30 (2006).]
(a ) Calculate the risk due to this type of failure assuming that 20% of
failures are caused by residual salt contamination.
(b ) If the cost of testing and removal of contaminating salts is
N450,000 is this additional cost justied based on the risk calculation
in (a)?
(c ) Calculate the minimum percentage of failures caused by residual
salt contamination at which the additional cost of N450,000 for testing
and removal of these salts is justied.
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