MM435_Corrosion Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Classes Schedule

10:40-11:55 12:05-13:20
(LH1, FMCE) (LH1, FMCE)
Mond
MM435 B MM435 A
ay
Tuesd
MM435 B
ay
Wedn
MM435 B MM435 A
esday
Thurs
MM435 B
day
Friday -

MM-435_Corrosion, Degradation and Protection 2

 Course outline
1. Introduction: Corrosion definition and basics, Corrosion Science and Engineering, Corrosion
Environments, Corrosion Damage, Corrosion Classification, , Electrochemical Aspects of corrosion.
Role of a corrosion engineer.
2. Corrosion Kinetics and Thermodynamics: The Driving Force of Corrosion, Gibbs free Energy of
Chemical Reactions, Rate of Corrosion Factors Effecting Corrosion Rate, Modern electrochemical
theory and thermodynamics of corrosion, electrochemical cell, Electrode potential/emf series,
Nernst equation, Pourbaix diagrams for Fe system, electrode kinetics, passivity, Polarization and
types, Ohmic drop at electrolyte/metal interface, exchange current density and its measurement,
3. Common types of Corrosion: Corrosion types and their preventive measures, weld decay, selective
leaching/dealloying, dezincification, graphitization, velocity induced corrosion, Mechanically
assisted attack, stress corrosion cracking, Hydrogen damage and embrittlement, Microbiologically
influenced corrosion.
4. Corrosion Monitoring: Salt spray/fog test, corrosion rate (MPY) and penetration rate calculations,
electrochemical corrosion testing, limiting current density, polarization diagrams (Evans diagram)
and corrosion data analysis,Tafel extrapolation, Tafel slopes determination from polarization curve,
linear polarization resistance (LPR), potentiodynamic and potentiostatic polarization resistance,
electrochemical impedance spectroscopy (EIS).

5. Corrosion of Ceramics and Degradation of Polymers

6. Corrosion Protection: Measures of corrosion control, cathodic protection, anodic protection, types
of coatings, corrosion inhibitors, Corrosion control by design…etc.
MM-435_Corrosion, Degradation and Protection 3
 Text & Reference Books

1. Pierre R. Roberge, Ph. D., P.Eng, “Corrosion Engineering Principles and

Practice” 1st Edition,, McGrawHill, 2008.

2. Zaki Ahmad, “Principles of Corrosion Engineering and Corrosion Control”

Elsevier, 2006

3. H. Uhlig and W. Revie, “Corrosion and Corrosion Control” Wiley, 4th Edition,
New York, 2008.

4. Mars Fontana, “Corrosion Engineering” , 1987. McGraw Hills.

4
MM-435_Corrosion, Degradation and Protection
 Learning Outcomes
Blooms
Learning Outcome PLOs Taxonomy
Level
Students will:
Be able to the basic principles & practices of corrosion, its
CLO_1 thermodyunderstand and relate namics, and chemistry of PLO1 C-3
corrosion, kinetics and factors involved in corrosion.
Be able to analyze and evaluate the corrosion behavior of
CLO_2 materials by using the laws of thermodynamics and kinetics of PLO2 C-5
corrosion and by modern corrosion analysis tools.
Be able to analyze the risks of corrosion damages by applying the
knowledge of the mechanisms of various types of corrosion and
CLO_3 PLO3 C-4
develop solutions to control and avoid/minimize the overall
corrosion by applying corrosion preventive strategies.

PLOs
Bloom Taxonomy Level (BTL) 1. Engineering Knowledge
2. Problem Analysis
1. Remembering 3. Design/Development of
2. Understanding solutions
3. Applying 4. Investigation
4. Analyzing 5. Modern Tool Usage
6. The Engineer and Society
5. Evaluating 7. Environment and Sustainability
6. Creating 8. Ethics
9. Individual and Team Work
10. Communication
What Is Outcome Based Engineering Education? 11. Project Management
12. Lifelong Learning 5
MM-435_Corrosion, Degradation and Protection
 Grading Criteria
Assignments/Case Studies ( 2/4 ) = 4%
Quizzes ( 6/8 ) = 20%
Midterm Exam = 30%
Course Project/CEP = 6%
Final Exam = 40%

General Instructions
• 80% Attendance to Qualify for Exams
• Come within the first five minutes of the class
• Note down your own attendance
• Not to proxy for any one
• No retake of quizzes/exams..!
• Not to sleep, talk, or make disturbance in the class
• Be precise, to the point, brief, explicit in examination
• Use dimensions and units
• No Exchange of calculators and other stuff during quizez and exams 6
MM-435_Corrosion, Degradation and Protection
 Corrosion
“It is an interaction between a material, usually a metal, and its environment that
results in deterioration of the material, and the environment.”
Anything Common…??
Anything Different…??
Corrosion Definition.??

It is the oxidation of a metal due to an ELECTROCHEMICAL reaction. The oxidizing agent is

most often O2 (atmospheric corrosion) or H+ (chemical corrosion) or both. 7
MM-435_Corrosion Degradation and Protection
 Corrosion
Corrosion is based on the Latin word “corrodere” which means to eat away

“It is an interaction between a material, usually a metal, and its environment that results
in deterioration of the material, and the environment.”
(A Groysman, Corrosion for everybody, 2010)

OR
It is extractive metallurgy in reverse.
OR
An electrochemical process between a metal/non metal and its environment that leads to
the deterioration of properties of the material
(MG Fontana, Corrosion Engg. 1987)

Think about:
• Dissolution of sugar and salt in water
• Burning (oxidation) of wood or paper Corrosion..??

• Dissolution of metals in hydrochloric acid,

• Oxidation of metals in a furnace/atmosphere Corrosion..??

8
MM-435_Corrosion Degradation and Protection
Corrosion Product

▪a reddish brown “corrosion product” formed

on iron (Fe) surfaces Rust
▪For deterioration of other metals, the term “corrosion product” is used, and not “rust”.

For example,
▪white corrosion products are formed on aluminium and zinc,
▪blue and blue-green on copper,
▪green on nickel,
▪pink on cobalt, etc.

9
MM-435_Corrosion Degradation and Protection
 Corrosion Product

• Can we always observe a corrosion product?

NO..!

Sometimes pits in a metal surface

as a result of the reaction between a

metal and the environment, but we
do not see the corrosion product.

10
MM-435_Corrosion Degradation and Protection
 Problems due to Corrosion

Metals lose their:

➢ Pleasant appearance,

➢ Dimensions

➢ Mechanical, thermal, and optical properties

MM-435_Corrosion Degradation and Protection 11

 Corrosive Environments
Corrosion Vs. Environment
Magnitude of Corrosion depends upon the sensitivity of a certain metal/alloy to a
specific Environment

Common Types of Environments

1) Air and humidity
2) Water (fresh, distilled, salt and marine)
3) Atmospheres (Natural/urban/marine/ industrial
steam and gases (Cl2, NH3, H2S, SO2 etc)
4) Acids
5) Alkalies
6) Liquids
7) Soils

High temperatures and pressures…???

They usually become causes of more severe corrosion
12
MM-435_Corrosion Degradation and Protection
 Corrosion Classification
The corrosion may be wet or dry corrosion in simple classification
(based on state of the environment).

Wet Corrosion ( liquid / aqueous solutions / electrolyte)

Dry Corrosion (No liquid, gases / vapours)
Dry and moist chlorine…??? (steel / titanium)

Dry chlorine is noncorrosive to ordinary steel but

in moisture, chlorine rapidly and severely attacks steels, and other

metals and alloys.

The reverse is true for titanium.

13
MM-435_Corrosion Degradation and Protection
 Corrosion Science and Engineering

•Corrosion Science covers theories, laws and explanation of

corrosion phenomena confirmed by the observations or experiments.

➢Corrosion science is a ‘knowing why’ of corrosion.

•Corrosion Engineering is the application of science and art to

prevent or control corrosion damage safely and economically.

➢Corrosion engg. is ‘knowing how’ to control/prevent corrosion.

14
MM-435_Corrosion Degradation and Protection
 Corrosion Science and Engineering
What a Corrosion Engineer should be capable of? ➢ Well acquainted with corrosion
science and corrosion engineering.
Corrosion engineer should know:
➢Chemical, metallurgical, physical and
mechanical properties of materials.

➢Practices and principles of corrosion

➢Nature of corrosive environments

➢Corrosion problems by corrosion

testing

➢Design of the engineering structure.

➢Corrosion prevention and control

methods

15
MM-435_Corrosion Degradation and Protection
 Corrosion Damages
• Plant shutdowns:
• nuclear plants,
• process plants, unexpected corrosion failure How to avoid..??
• power plants and plant shutdown
• refineries

• Loss of products:
• Containers
• storage tanks, Leakage due to unexpected
• fuel tanks corrosion failure
• water and oil transportation lines
25% of H2O is lost due to leakage problems..!!

• Loss of efficiency:
Insulation of heat exchanger tubing's and pipelines due to corrosion
products…thus loosing the heat exchanging efficiency
16
MM-435_Corrosion Degradation and Protection
 Corrosion Damages
• Contamination:
• Corrosion products may contaminate chemicals, pharmaceutical packaged goods,
etc. with dire consequences to the consumers.

• The market value of a product depends on its purity and quality.

• A very small amount of corrosion may introduce certain metals ions in the solution
which may catalyse the decomposition of the product.

• Nuclear hazards:
• The Chernobyl disaster (1986) is a continuing example of transport of radioactive
corrosion products in water, fatal to human, animal and biological life.

• Appearance:
• Structures have to be painted in order to avoid the rust appearance which is
unpleasing to the eyes.
• Outside surfaces of buildings are often made of stainless steel Al or Cu for the
sake of appearance and corrosion prevention.

17
MM-435_Corrosion Degradation and Protection
 Corrosion Damages
• Maintenance and operating costs
• Substantial cost savings can be made in plants by using corrosion resistant
materials in construction.
A poor choice of joining materials e.g. a bolt can lead to heavy costs.
e.g. Failure of a small component may lead to the destruction of the entire
structure.
• Design engineer and corrosion engineers must collaborate to devise a
combined strategy for an efficient corrosion prevention protocol because:
It is easier and cheaper to erase line on a drawing than to repair or replace a
failed equipment in the plant.

• Effect on safety and reliability:

• Handling of hazardous materials such as toxic gases, HF, concentrated sulfuric
and nitric acids, explosive and flammable compounds, radioactive
substances, and chemicals at high temperature and pressure demand the use
of construction materials that minimize corrosion failures.
• Health:

• Depletion of resources…!!! 18
MM-435_Corrosion Degradation and Protection
Managing Corrosion Risk
Corrosion Risk managing Stages:
• Design Stage,
• During Operation (maintenance and control)

A simplified approach to risk management, indicating qualitatively the areas of

high risk, where both consequence and probability are high.

19
MM-435_Corrosion Degradation and Protection
Question?

How Chromium (Cr) will protect Iron in stainless steel when

Cr is only 13% compared to Fe >50% ?

Ans:
Basically as the steel first corrodes the iron will be lost into
solution while the chromium oxide (Cr2O3) will stay on the
surface.
After a few atomic layers have been oxidised the surface
will be covered by a continuous layer of chromium oxide.
Although the steel is corroded on the atomic level, it
appears stainless.
21
MM-435_Corrosion Degradation and Protection
Corrosion….

Extractive metallurgy in reverse..!!

MM-435_Corrosion Degradation and Protection 23

 Corrosion product of iron (Fe),

Primary: Fe(OH)2 (or more likely FeO·nH2O),

Corrosion…. Secondary:
• Fe2O3·H2O {Fe(OH)3} or hydrous ferrous oxide,
Extractive metallurgy in reverse..!! red-brown rust, called hematite.

• Fe3O4·H2O or hydrated magnetite,

most often green

• Fe3O4 or magnetite
black.

24
MM-435_Corrosion Degradation and Protection
 Why Corrosion Occurs??
Pt, Au (noble metals) = stable in most corrosive environments,

Whereas,

Fe and Zn corrode in the same environment.

How can we predict if a particular metal will corrode

under specific conditions/environments?

Answer lies in the study of thermodynamics of corrosion

process..!!

Gibbs Free Energy

25
MM-435_Corrosion Degradation and Protection
 Why Corrosion Occurs

Corrosion….

Why it occurs…??

Gibbs Free Energy..!

Change in Free Energy (G)

MM-435_Corrosion Degradation and Protection 26

Driving force behind a chemical reaction
G o =  ni .G of ( products) −  ni .G of (reac tan ts )
• If

G To  o
Reaction will be spontaneous and corrosion is more likely
If
GT  o
•
o

The corrosion reaction will not occur.

• There is also the yellow light situation, when

GT = oo

Which means that the sum of chemical potentials

(Gibbs energies) of reactants equals the sum of chemical potentials of
products. In other words chemical equilibrium is established.
27
MM-435_Corrosion Degradation and Protection
Why Corrosion Occurs

Occurrence of corrosion……….. ∆ G

The rate of corrosion…………????

28
MM-435_Corrosion Degradation and Protection
 Why Corrosion Occurs
How can we predict if a particular metal will corrode
under specific conditions?

(∆G) tells us that if a certain chemical process can occur

spontaneously under certain environmental conditions or not.

∆ G = − n F Eocell

∆ G = − R T lnK

29
MM-435_Corrosion Degradation and Protection
 Electrochemical Nature of Corrosion
Daniel Cell..!

This situation leads to a Galvanic Corrosion Cell

(bimetallic corrosion)

Zn

Bubbling, or “plating out of
hydrogen” on zinc immersed
in 0.1 M HCl solution.
𝑍𝑛 → 𝑍𝑛+2 + 2e-
2𝐻 + + 2e- → 𝐻2
𝑍𝑛 + 2𝐻𝐶𝑙 → 𝑍𝑛+2 + 2Cl- +𝐻2
𝑍𝑛 + 2𝐻𝐶𝑙 → 𝑍𝑛Cl2 + 𝐻2
MM-435_Corrosion Degradation and Protection 31
Electrochemical Nature of Corrosion

Oxidation

Fe rod immersed in HCl

Reduction

MM-435_Corrosion Degradation and Protection 33

Electrochemical Nature of Corrosion

MM-435_Corrosion Degradation and Protection 34

 Electrochemical Nature of Corrosion
Corrosion of Fe, Mechanism

MM-435_Corrosion Degradation and Protection 35

 Electrochemical Nature of Corrosion
Anodic/Corrosion Reactions for metals

Generalized Anodic Reaction

Cathodic Reactions

aerated

MM-435_Corrosion Degradation and Protection 36

 Electrochemical Nature of Corrosion
Corrosion of Zn in HCl

MM-435_Corrosion Degradation and Protection 37

 Electrochemical Nature of Corrosion
Corrosion of Zn in aerated HCl

Anodic Reaction

Cathodic Reactions

MM-435_Corrosion Degradation and Protection 38

 Electrochemical Nature of Corrosion
Corrosion of Mg in neutral water

MM-435_Corrosion Degradation and Protection 39

 Electrochemical Nature of Corrosion
Surface Area Effect

MM-435_Corrosion Degradation and Protection 40

Next Topics:

➢Introduction to different forms of corrosion

➢Corrosion Cells

41
MM-435_Corrosion Degradation and Protection
Forms of Corrosion

1. Uniform Corrosion, 5. Intergranular Corrosion,

2. Galvanic Corrosion, 6. Selective leaching,

3. Crevice Corrosion, 7. Erosion–Corrosion and

4. Pitting Corrosion, 8. Stress Corrosion

MM-435_Corrosion Degradation and Protection 42

Forms of Corrosion
Uniform Corrosion
Corrosion that occurs with equivalent intensity over the entire exposed surface

It often leaves behind a scale or deposit.

In a microscopic sense, the oxidation and

reduction reactions occur randomly over the
surface.

Examples include general rusting of steel and

iron.

This is probably the most common form of

corrosion.

MM-435_Corrosion Degradation and Protection 43

Forms of Corrosion
Galvanic Corrosion
Galvanic corrosion occurs when two metals or alloys having different compositions are electrically
coupled while exposed to an electrolyte.

More reactive metal in the particular environment

experiences corrosion; the more inert metal, the
cathode, is protected from corrosion.

Examples:
Steel screws corrode when in contact with brass
in a marine environment

Copper and steel tubing are joined in a domestic water

heater, the steel corrodes in the vicinity of the
junction.

MM-435_Corrosion Degradation and Protection 44

Forms of Corrosion
Crevice Corrosion

this type of corrosion occurs in crevices

and recesses or under deposits of dirt or
corrosion products where the solution becomes
stagnant. Corrosion preferentially
occurring at these positions is called crevice
corrosion

Causes: concentration gradients in

electrolyte cause some areas high in ion
concentrations that accelerate oxidation

This plate was immersed in seawater, crevice corrosion has occurred at the
regions that were covered by washers.

MM-435_Corrosion Degradation and Protection 45

Forms of Corrosion
Pitting Corrosion
Pitting is another form of very localized corrosion attack in which small pits or holes are formed.

They ordinarily penetrate from the top of a horizontal surface downward in a nearly vertical direction.

The mechanism for pitting is same as for crevice

corrosion, in that oxidation occurs within the pit itself

MM-435_Corrosion Degradation and Protection 46

Forms of Corrosion
Intergranular Corrosion
Occurs in specific alloys – precipitation of corrosive specimens along grain
boundaries and in particular environments
e.g. : Chromium carbide forming in SS, leaving adjacent areas depleted in Cr

Chromium carbide forming in SS

MM-435_Corrosion Degradation and Protection 47

Forms of Corrosion
Erosion Corrosion
Erosion–corrosion arises from the combined action of chemical attack and mechanical
abrasion or wear as a consequence of fluid motion.

Causes: abrasive fluids impinging on surfaces

Commonly found in piping, propellers, turbine
blades, valves and pumps

MM-435_Corrosion Degradation and Protection 48

Forms of Corrosion
Selective Leaching
one element or constituent is preferentially removed as a
consequence of corrosion processes

• Occurs in alloys – e.g., in Brass, Zinc is electrically active

and is removed, leaving behind porous Copper
(dezincification of brass)
• Occurs in other metals, such as Al, Fe, Co, Cr

MM-435_Corrosion Degradation and Protection 49

Forms of Corrosion
Stress Corrosion Cracking
results from the combined action of an applied
tensile stress and a corrosive environment

Cracks grow along grain boundaries as a result

of residual or applied stress or trapped gas or
solid corrosion products
e.g., brasses are sensitive to ammonia
Stress levels may be very low
A bar of steel bent into a horseshoe shape using a nutand-bolt assembly. While
immersed in seawater, stress corrosion cracks formed along the bend at those
regions where the tensile stresses are the greatest.

MM-435_Corrosion Degradation and Protection 50

 Hydrogen Embrittlement
Various metal alloys, specifically some steels, experience a significant reduction in ductility
and tensile strength when atomic hydrogen (H) penetrates into the material.

• Metals loose strength when Hydrogen is absorbed

through surface, especially along grain boundaries
and dislocations

• Often occurs as a result of decorative plating

• High strength steels particularly susceptible

MM-435_Corrosion Degradation and Protection 51