2015-10-12

By:
Dr. Irannejad

2015-10-12

1.

E.E.

Stansbury

and

R.A.

Buchanan,

Fundamentals

of

Electrochemical Corrosion, First edition, 2000.

2.

P.R. Roberge, Handbook of Corrosion Engineering, McGraw-Hill,

2000.

3.

L.L.

Shreir,

R.A.

Jarman,

G.T.

Burstein,

Corrosion

Metal/Environment Reactions, third edition, 2000.

4.

ASM Metals Handbook, vol. 13 (corrosion).

5.

Roberge, P.R. Handbook of Corrosion Engineering, McGraw-Hill,

2000.

6.

Philip A. Schweitzer, Fundamentals of corrosion- Mechanisms,

Causes, and preventative methods. Taylor & Francis Group, 2010.

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7.

Zaki Ahmad, Principles of Corrosion Engineering and Corrosion Control,

Elsevier Science & Technology Books, 2006.

8.

E. McCafferty, Introduction to Corrosion Science, Springer Science, 2010.

9.

L L Shreir, R A Jarman, and G T Burstein. Corrosion- Metal/Environment

reactions (Volume 1), 2000.

10. L L Shreir, R A Jarman, and G T Burstein. Corrosion- Corrosion Control

(Volume 2), 2000.
11. H.M. Shalaby, A. Al-Hashem, M. Lowther and J. Al-Besharah, Industrial
corrosion and corrosion control technology, Kuwait Institute for Scientific
Research, 1996.

: . . : -12
.
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Introduction

What is Corrosion?

Why does metal undergo corrosion?

Importance of Corrosion
Examples of Corrosion
Forms of corrosion
Classification of corrosion
Electrochemical potential
Overview of Electrochemical Corrosion

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Corrosion:
Deterioration of materials by interaction with their environment.

The term materials refers to those substances used in the

construction

of

machines,

process

equipment,

and

other

manufactured products.
These materials include metals, polymers, and ceramics.

The environments are liquids or gases, although under special

circumstances certain solid-solid reactions might be included as
corrosion.
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Corrosion is extractive metallurgy in reverse.

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Only few elements exist in free element state in natural circumstance.

Corrosion of metal, i.e. conversion of element to stable compound, is
thermodynamically favored.

Naturally occurring
copper single crystals.

Naturally occurring gold.

Naturally occurring
copper sheet

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The need to control corrosion almost always reduces to considerations of

safety and economics.

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Machines, equipment, and functional products may fail due to

corrosion in such a manner as to result in personal injury.

Aloha Incident

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One-fifth of the iron and steel produced annually in the world is used to
replace rusted metal.

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Corroded metal often loses its structural integrity and attractiveness.

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Motor Vehicles: $23.4 Billion per year + safety issues

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Highways & Bridges: $8.3 Billion per year + safety issues

Before

After

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Rusting of steel and cast iron in water

Corrosion of copper, aluminum, and cast iron in automotive cooling systems
Corrosion of iron-base, copper-base, nickel-base, alloys in the chemical process
Corrosion of automobile exhaust systems by direct reaction of the metal with
high-temperature gases
Corrosion of turbine blades in gas turbines by hot combustion gases
Corrosion of metallic surgical implant materials used in orthopedic
Corrosion of iron-base and nickel-base alloys by liquid metals used as heat transfer
agents
Enhanced deterioration of structural concrete and stone by interaction with
condensed moisture and acidic contaminants in the air
Stress-corrosion cracking (SCC) of gold and brass by mercury
SCC and pitting of stainless steel in sea water

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Railway bridge

Brass sculpture

White marble

Waterline corrosion
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Corrosion at sea

Corrosion of plastics
Corrosion of Aluminium
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Corrosion of Concrete
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1) Based on materials:

Corrosion of metals;

Corrosion of non-metals (wood, plastic, concrete, stone, etc).

2) Based on Media:
Natural corrosion;
Industrial corrosion (e.g. solution containing acid, base, H2S, etc).

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3) Based on uniformity:

General corrosion;

Local corrosion.

4) Based on mechanism:

Chemical corrosion (2Fe + O2 = 2FeO);

Electrochemical corrosion;

Biochemical corrosion.
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1.

Direct Chemical Corrosion or Dry Corrosion

This type of corrosion occurs mainly through the direct chemical

action of atmospheric gases such as O2, halogens, H2S, CO2, SO2, N2,
H2 or liquid metals on metal surface in the absence of moisture.

2.

Electrochemical Corrosion or Wet Corrosion

This type of corrosion occurs when :

a. A metal is in contact with a conducting liquid.
b. Two dissimilar metals or alloys are immersed partially in a
conducting solution.
Corrosion and its Control, Dr. Priyabrat Dash, NIT Rourkela, India

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1. Corrosion by O2
or Oxidation corrosion

Dry Corrosion

2. Corrosion by H2
and other gases

3. liquid metals corrosion

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Mechanism of corrosion is the actual atomic,

molecular, or ionic transport process that
takes place at the interface of a material.

Since electrochemical corrosion involves the

release of ions to the environment and
movement of electrons within the material.

This mechanism can occur only if the

environment

can

contain

ions

and

the

material can conduct electrons.

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Anodic Reaction (oxidation): liberating electrons

Zn Zn2+ + 2e-

zinc corrosion

Fe Fe2+ + 2e-

iron corrosion

Al Al3+ + 3e-

aluminium corrosion

Fe2+

Fe3+

e-

H2 2H+ + 2e2H2O O2 + 4H+ + 4e-

ferrous ion oxidation

hydrogen oxidation
oxygen evolution

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Cathodic Reaction (reduction): accept electrons

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Anode (anodic area):

The site where the metal is being oxidized.

Cathode (cathodic area):

The site where oxygen, water, or some other species is being reduced.

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Mechanism of rusting of iron

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Electrochemical Corrosion requires four elements:

1- Anode

2. Cathode

3. Electrolyte

4. Electrical Path

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An electrolyte is a compound that ionises when dissolved in suitable

ionising solvents such as water.

This includes most soluble salts, acids, and bases.

Strong electrolytes produce ions and conduct an electric current.

Weak electrolytes produce a few ions.

Nonelectrolytes do not produce ions.

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Corrosion Mechanisms
Particularly under the broad definition of corrosion as the deterioration of
materials by reaction with the environment, the number of mechanisms whereby
deterioration occurs is large.
In general, a mechanism of corrosion is the actual atomic, molecular, or ionic
transport process that takes place at the interface of a material.
These processes usually involve more than one definable step, and the major
interest is directed toward the slowest step that essentially controls the rate of
the overall reaction.
When electrochemical corrosion is occurring, mechanisms may be inferred from
measurements of electrical potential and current.

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Since electrochemical corrosion involves the release of ions

to the environment and movement of electrons within the
material, this mechanism can occur only if the environment

can contain ions and the material can conduct electrons.

The most important case of electrochemical mechanisms is

the simple corrosion of metals in aqueous solutions, where
atoms at the surface of the metal enter the solution as metal
ions and electrons migrate through the metal to a site where,
to sustain the reaction, they are consumed by species in
contact with the metal.

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In more complicated cases, the metal ions move into solution by forming
complex ions, or they combine with other species in the solution and
precipitate compounds such as hydroxides, oxides, or sulfides.

At sufficiently high temperatures, metals corrode in gases, particularly

oxygen to form oxides. Whereas the mechanism in this case appears to be
one of direct chemical attack, the mechanism may still be electrochemical in
nature, with ions and electrons moving in the oxide which acts as the
electrolyte supporting the electrochemical mechanism.

Polymeric and ceramic materials generally do not support electron

conduction and hence corrode by either direct chemical or physical
mechanisms.

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Electrochemical Corrosion Processes and Variables

Before examining in detail the theories of aqueous corrosion and
quantitative calculations of corrosion rates, it will be useful to
develop qualitatively the major phenomena involved.

The

following

sections

review

several

general

types

of

metal/corrosive-environment combinations, the chemical reactions

involved, idealized mechanisms for the transfer of metal ions to the
environment, and the electrochemical processes occurring at the
interface between the metal and the aqueous environment.

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Uniform Corrosion with pH as the Major Variable

For metals, M, that are thermodynamically unstable in water, the
simplest corrosion reactions are:

Thus, the metal passes from the metallic state to ions of valence m
in solution with the evolution of hydrogen.

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Because the metallic phase is an electron conductor, it supports the

electron transfer, allowing the two processes to occur at separate sites on
the metal surface.

In limiting cases, these processes occur within a few atom diameters on the
surface with the sites constantly changing with time, thus producing
uniform corrosion.
Otherwise, the corrosion is nonuniform.

Uniform corrosion supported by pH is represented schematically in Fig. 1.1.

In this example, oxygen is excluded by a nitrogen gas purge and
overblanket.

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Uniform Corrosion with pH and Dissolved Oxygen as Variables

When dissolved oxygen is present in the solution, usually from contact with air, the following
reactions apply in addition to those just considered.

Uniform corrosion supported by dissolved oxygen and pH is represented schematically in Fig. 1.2.

Since electrons are now consumed by two reactions, the rate of corrosion of the metal increases.

In the case of iron, dissolved oxygen is more important in supporting corrosion than the presence of
hydrogen ions when the pH is greater than approximately 4.

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Uniform Corrosion with Corrosion Product Formation

An example of corrosion product formation is the rusting of iron as

illustrated in Fig. 1.3.

When the pH is greater than approximately 4, and under aerated

conditions, a layer of black Fe3O4, and possibly Fe(OH)2, forms in contact
with the iron substrate.

In the presence of the dissolved oxygen, an outer layer of red Fe2O3 or

FeOOH forms.

The adherence and porosity of these layers change with time and can be
influenced by other chemical species in the environment, such as chloride
and sulfate ions.

In any case, the formation of the corrosion product layer influences the
corrosion rate by introducing a barrier through which ions and oxygen
must diffuse to sustain the corrosion process.

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Electrochemical reactions involve transfer of charge.

Hence, we expect that the voltage of the metal with

respect to the solution will affect electrochemical
reactions.

Voltage of metal with respect to solution is known as

the electrochemical potential.
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Standard Hydrogen Electrode

E = 0 V
(by definition; arbitrarily selected)
2H+ + 2e- H2

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e-

e-

Zn
anode

Cu cathode

Salt
bridge

Zn2+

Cu2+

Zn Zn2+ + 2e-

Cu2+ + 2e- Cu
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Cu

Zn

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more anodic

more cathodic

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metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K

o
Vmetal

+1.420 V
+0.340
- 0.126
- 0.136
- 0.250
- 0.277
- 0.403
- 0.440
- 0.744
- 0.763
- 1.662
- 2.363
- 2.714
- 2.924

Ex: Cd-Ni cell

o
o
VCd
< VNi Cd corrodes

Cd

25C

Ni

1.0 M
1.0 M
Cd 2 + solution Ni 2+ solution

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more anodic
(active)

more cathodic
(inert)

Ranking the reactivity of metals/alloys in seawater

Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel (active)
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
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Very Base Metals

emf < -0.4V
Corrode in neutral aqueous solutions, even without oxygen
Includes Na, Mg, Be, Al, Ti, and Fe

Base Metals
emf between -0.4V and 0.0 V
Corrodes in neutral aqueous solutions with oxygen
Corrodes in acids to produce hydrogen, even without oxygen
Includes Cd, Co, Ni, Sn, and Pb
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Semi-Noble Metals
emf between 0.0 V and +0.7V
Corrodes in aqueous solutions only with the presence of oxygen
Includes Cu, Hg, Ag

Noble Metals
emf between > +0.7V
Includes Pd, Pt, Au

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Galvanic corrosion
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Polarization is a deviation of the electrochemical process from

equilibrium due to an electric current passing through the galvanic
cell.

Polarization

may

occur

either

at

the

cathode

(cathodic

polarization) or at the anode (anodic polarization). Cathodic

polarization is common.

There are three types of polarization:

1.

Activation polarization

2.

Concentration polarization

3.

Resistance polarization
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Common cause of cathodic activation polarization is the reaction of

Hydrogen formation and evolution at the cathode surface:

First step: reduction of the hydrogen ions resulted in formation of atomic

hydrogen on the cathode surface.
H+ + e- = H

Second step: formation of molecules of gaseous hydrogen.

2H = H2

Third step: formation of hydrogen bubbles.

H2 + H2 + H2 +H2 + ... = nH2

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Concentration polarization:
Concentration polarization of an electrode is a result of formation of a Diffusion
layer adjacent to the electrode surface where there is a gradient of the ion
concentration.

Diffusion of the ions through the layers controls the electrochemical reaction
(corrosion, Electroplating).

Resistance polarization:
Resistance polarization refers to the potential drop due to either the high
resistivity of the electrolyte surrounding the electrode or an insulation effect of
the film on the electrode surface formed by the reaction products.

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A protective film in oxidizing atmospheres

chromium, titanium, aluminum

Metal oxide layer adheres to parent metal

barrier against further damage
self-healing if scratched

Sensitive to environmental conditions

passivated metal may have high corrosion rates
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Types of Tests
ANODIC POLARIZATION CURVE
this curve is usually scanned from 20mV below the Eoc upwards
by scanning at a slow rate (.2mV/s) this curve can be used to identify
several corrosion mechanisms shown below

ip -

passive current density

Epp -

primary passivation potential

icrit -

critical current density

Etrans - transpassive potential

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pitting

cracking
zones

passive

active

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Weight Loss Measurement

Thickness loss Measurement

Measurement of electrical current density

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Stress corrosion
Uniform Attack
Oxidation & reduction
occur uniformly over
surface.

Stress & corrosion

work together
at crack tips.

Erosion-corrosion
Break down of passivating
layer by erosion (pipe
elbows).

Selective Leaching
Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).

Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.

Pitting
Downward propagation
of small pits & holes.

Galvanic
Dissimilar metals are
physically joined. The
more anodic one
Corrodes.

Crevice Between two

pieces of the same metal.

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Underground corrosion

Electronic components

Corrosion influenced by flow (Cavitation Corrosion and Erosion Corrosion)

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Galvanic corrosion
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O2

Fe

Cl

Cl OH
Fe2+
Fe2+
Cl
Fe2+
Cl
Fe2+

O2 + 2H2O + 4e 4OH
Impurity

Fe = Fe2+ + 2e

Pitting Corrosion

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Pitting Corrosion
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Crevice Corrosion
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Selective Leaching

Stress Corrosion

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Intergranular Corrosion

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