(Corrosion Engineering) Chapter#1 2: Instructor: Dr. Ihsan-Ul-Haq Toor Office: 63-358/phone:7493

ME 472
(Corrosion Engineering)
Chapter#1 ~2
Instructor: Dr. Ihsan-Ul-Haq Toor

 Office: 63-358/Phone:7493
Lecture Contents
 What is corrosion?
 Importance of the subject?
 Why Corrosion?
 Environmental factors for corrosion?
 How corrosion takes place
 Electrochemical nature of corrosion
 Forms of Corrosion
ME 472: CORROSION ENGINEERING

Copyright@ Dr. Ihsan Toor
What is Corrosion?
The destruction of a metallic material by chemical,

electrochemical, or metallurgical interaction with the
environment ”
Fig-1. Corrosion of a deserted boat (left) and a tank (right).

[1] P.R. Roberge, Corrosion Engineering Principles and Practice, first ed., McGraw-Hill, USA, 2008.
[2] Z. Ahmad, Principles of Corrosion Engineering and Corrosion Control, first ed., Elsevier, UK, 2006.

Importance of this subject?
Almost every engineer/scientist at one time or another will be

exposed to MATERIALS /especially metals (design, synthesis,
application etc)
Examples: Petrochemical industry (oil and gas), Structures, Desalination

industry, , power industry, Nuclear industry, and so on;
Metals are the most abundant and each has different properties
(80 known elements are metals)
These different elements have been combined to develop roughly

> 40000 different alloys and still going on

Importance of this subject?
Economic Impact
3~5% of GNP of Development country

Economic Impact of Corrosion
 Direct loss :
Approximately 3 - 5% of GNP in developed countries. About 15 - 25% of
this expense could be avoided if currently available corrosion technology
were effectively applied.
 Cost of corrosion in U. S. about $ 276 billion in 2002 that is equivalent
to 3.1 % of GNP.
 Cost of corrosion to oil and gas producers in U. S.  $ 2 billion that are
increasing because of deeper wells and more hostile env.(500 F, H2S).
 Indirect loss
 Plant shutdown.
 Loss of product.
 Loss of efficiency
 Contamination.

Why Corrosion?
Corrosion is natural process and

it returns the metal to its oxidized
state or combined state in the
form of chemical compound
that are similar to the mineral
from which they are extracted

Materials & Environment

Defining the environment is very important
Some environments are more corrosive than others,

but there can be exceptions
Moist air is more corrosive than dry air
Hot water is more corrosive than cold water
Polluted air is more corrosive than clean air
Acids are more corrosive than bases (alkalies) to steels
Salt water is more corrosive than fresh water
No corrosion will occur in a vacuum, even at very high temperatures

How Corrosion Takes Place?
Corrosion process requires a complete
corrosion cell/circuit, which includes;
1. Anode
2. Cathode
3. Electrolyte
4. Electrical path
Galvanic Cell

Anodic reactions/Oxidation reaction takes place at anode (Loss

of electrons/generation of electrons)
General Reaction (metal oxidation)

MMn+ + ne- (gives off electrons))
Zn  Zn2+ + 2e- (Zn corrosion)
Fe  Fe2+ + 2e- (Fe corrosion)
Al  Al3+ + 3e- (Al corrosion)
Fe2+  Fe3+ + e- (Ferrous ion oxidation)

Cathodic reactions/reduction reaction (gain/consumption of electrons)
O2 + 2H2O + 4e- → 4OH- (oxygen reduction in water/bases)
O2 + 4H+ + 4e- → 2H2O (oxygen reduction in acids)
2H+ + 2e- → H2 (hydrogen evolution in acids)
Cu2+ + 2e- → Cu (metal deposition=>copper plating)
Fe3+ + e- → Fe2+ (metal/ferric ion reduction)


Behavior of Water
pH = - log [H+]
Neutral= - log [1* 10-7]= 7
Acidic?
Alkaline?

Corrosion of Metals
 Behavior of Active and Passive metals
Passive Active

Corrosion of Metals
1: Change in Gibbs Free Energy
 The change in Gibbs free energy, ΔG , for any chemical reaction indicates the
tendency of that reaction to go.
 Reactions occur in the direction that lowers the Gibbs free energy. The more
negative the value of free energy , the greater the tendency for the reaction to
go.
2: Pilling–Bedworth Ratio
PB Ratio= Md / nmD
 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
 n is the number of metal atoms in a molecular formula of scale; for example, for
Al 2 O 3 , n = 2.

Corrosion of Metals
2: Pilling–Bedworth Ratio
If Md / nmD < 1, film would be expected to contain cracks and pores and be
relatively nonprotective.
If Md / nmD > 1, film/scale will be in compression, protective of the underlying

metal.
If Md / nmD >> 1, the scale that forms may buckle and detach from the
surface because of the higher stresses that develop.

Corrosion Types

Corrosion Types

Corrosion Types-Uniform/General
 Rates of uniform attack are reported in various units;

millimeters penetration per year (mm/y); grams per
square meter per day (gmd), inches penetration per
year (ipy), mils (1 mil = 0.001 inch) per year (mpy),
and milligrams per square decimeter per day (mdd).
 Steel, for example, corrodes at a relatively uniform rate

in seawater of about 0.13 mm/y, 2.5 gmd, 25 mdd, or
0.005 ipy. These represent time -averaged values.
 Generally, for uniform attack, the initial corrosion rate

is greater than subsequent rates .

Corrosion Types-Uniform/General
Metals are classified into three groups according to their corrosion rates and
intended application.
A. < 0.15 mm/y ( < 0.005 ipy) — Metals in this category have good corrosion
resistance to the extent that they are suitable for critical parts, for example,
valve seats, pump shafts and impellors, springs.
B. 0.15 to 1.5 mm/y (0.005 to 0.05 ipy) — Metals in this group are satisfactory
if a higher rate of corrosion can be tolerated, for example, for tanks, piping,
valve bodies, and bolt heads.
C. > 1.5 mm/y ( > 0.05 ipy) — Usually not satisfactory.

Corrosion Types-Pitting
 “Ratio of deepest metal penetration to average metal penetration”

as determined by the weight loss of the specimen, is called pitting
factor .
 A pitting factor of unity represents uniform attack.

Corrosion Types- Fretting
 FC is the result of “slight relative motion (as

in vibration) of two substances in contact,
one or both being metals.

Corrosion Types- Cavitation
 Cavitation – erosion is the loss of material caused

by exposure to cavitation, which is the “formation
and collapse of vapor bubbles” at a dynamic metal
– liquid interface.
 Example, in rotors of pumps or on trailing faces of

propellers.

Corrosion Types- Dealloying
 Dealloying is the “selective removal of an element from an alloy by corrosion”.
 One form of dealloying, dezincification, is a type of attack occurring with zinc

alloys (e.g., yellow brass) in which zinc corrodes preferentially, leaving a porous
residue of copper and corrosion products.
 The tensile strength and ductility are seriously reduced.

Corrosion Types- Intergranular
 This is a localized type of attack at the grain

boundaries of a metal, resulting in loss of
strength and ductility.
 Improperly heat - treated 18 - 8 stainless

steels or Duralumin - type alloys (4% Cu – Al) are
among the alloys subject to intergranular corrosion.

Corrosion Types- Cracking
 “ A brittle failure of a metal/alloy caused by the simultaneous action of a tensile

stress and a specific corrosion environment” [Stress corrosion cracking]
 Mechanical damages of a metal caused by the presence of, or interaction with,

hydrogen are as follows : [Hydrogen induced cracking]
 When a metal is subjected to cyclic stress in a corrosive environment, the

number of cycles required to cause failure at a given stress may be reduced
well below the dotted line obtained for the same metal in air. [Corrosion
Fatigue]

Corrosion Cells

Faraday’s Law
 The greater the flow of electricity through the cell,

the greater the amount of METAL that corrodes.
 This relationship is showed by Faraday ’ s law:

Weight of metal reacting = kIt
where I is the current in amperes (A), t is in seconds
(s), and k is a constant called the electrochemical
equivalent g/c. [Columb=1As]
OR
m=Iat/ zF
Where;
I= Current involved during a reaction
a= Atomic weight of the material
T= time of reaction
Z= number of equivalents exchanged
F= Faraday’s constant

Types of Cells
1: Dissimilar Electrode Cells/Galvanic cell/Voltaic cell

A potential difference exists when two dissimilar metals, electrically
connected, are immersed in a corrosive solution. A cell that
produces electricity as a result of the spontaneous cell reaction.
Cell notation
Zn(s) I ZnSO4 (aq) II CuSO4 (a) I Cu(s)

Salt bridge: is used for:
 Electrical connection between
the two half cells
 Prevents mixing of the electroly
tes
 Keep the electrical neutrality in
each half-cell as ions flow into and
out of the salt bridge

Types of Cells
2: Concentration Cells
-Difference in the composition/salt, content of the soil or solution, Change in oxygen
concentration

Types of Cells
2: Concentration Cells
 Differential aeration cells can also cause pitting damage under rust (Fig. 2.5 ) and at the
water line — that is, at the water – air interface (Fig. 2.6 )..
Differential aeration cell formed

by rust on iron Water-line corrosion, showing
differential aeration cell

Types of Cells
3: Electrochemical Cells
A cell in which non spontaneous reaction is

driven by an external power source.
For example: Electrolysis

M+ M
m+

Material Selection to avoid the corrosion issue
To solve the problem, we can say that;
i) Use more corrosion resistant material
ii) Use a corrosion prevention strategy such as coating, or

cathodic protection or use inhibitors
However to decide the best suitable method, which is

effective and economical, we need to consider many things
such as

Estimating the corrosion

performance of a material

Material selection
depends on:

Risk Management
R (risk) = P (probability) × C (consequences)
 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 financial 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.

Risk Management
R (risk) = P (probability) × C (consequences)


(Corrosion Engineering) Chapter#1 2: Instructor: Dr. Ihsan-Ul-Haq Toor Office: 63-358/phone:7493

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ME 472

Instructor: Dr. Ihsan-Ul-Haq Toor

ME 472: CORROSION ENGINEERING

The destruction of a metallic material by chemical,

Fig-1. Corrosion of a deserted boat (left) and a tank (right).

ME 472: CORROSION ENGINEERING

Almost every engineer/scientist at one time or another will be

Examples: Petrochemical industry (oil and gas), Structures, Desalination

These different elements have been combined to develop roughly

ME 472: CORROSION ENGINEERING

3~5% of GNP of Development country

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

Corrosion is natural process and

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

Some environments are more corrosive than others,

Moist air is more corrosive than dry air

Hot water is more corrosive than cold water

Polluted air is more corrosive than clean air

Acids are more corrosive than bases (alkalies) to steels

Salt water is more corrosive than fresh water

No corrosion will occur in a vacuum, even at very high temperatures

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

Anodic reactions/Oxidation reaction takes place at anode (Loss

General Reaction (metal oxidation)

Zn  Zn2+ + 2e- (Zn corrosion)

Fe  Fe2+ + 2e- (Fe corrosion)

Al  Al3+ + 3e- (Al corrosion)

Fe2+  Fe3+ + e- (Ferrous ion oxidation)

ME 472: CORROSION ENGINEERING

Cathodic reactions/reduction reaction (gain/consumption of electrons)

O2 + 2H2O + 4e- → 4OH- (oxygen reduction in water/bases)

O2 + 4H+ + 4e- → 2H2O (oxygen reduction in acids)

2H+ + 2e- → H2 (hydrogen evolution in acids)

Cu2+ + 2e- → Cu (metal deposition=>copper plating)

Fe3+ + e- → Fe2+ (metal/ferric ion reduction)

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

pH = - log [H+]

Neutral= - log [1* 10-7]= 7

ME 472: CORROSION ENGINEERING

 Behavior of Active and Passive metals

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

If Md / nmD > 1, film/scale will be in compression, protective of the underlying

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

ME 472: CORROSION ENGINEERING

 Rates of uniform attack are reported in various units;

 Steel, for example, corrodes at a relatively uniform rate

 Generally, for uniform attack, the initial corrosion rate

ME 472: CORROSION ENGINEERING

C. > 1.5 mm/y ( > 0.05 ipy) — Usually not satisfactory.

ME 472: CORROSION ENGINEERING

 “Ratio of deepest metal penetration to average metal penetration”

 A pitting factor of unity represents uniform attack.

ME 472: CORROSION ENGINEERING

 FC is the result of “slight relative motion (as

ME 472: CORROSION ENGINEERING

 Cavitation – erosion is the loss of material caused

 Example, in rotors of pumps or on trailing faces of