MT 41013

Corrosion and Environmental

Degradation of Materials
3-0-0

Text books:
 ‘Corrosion Engineering’ by Mars G. Fontana
 Principle and Prevention of Corrosion by Denny A. Jones

1
Factors affecting choice of an engineering material

Corrosion
resistance
Availability Cost

Materials

Strength Appearance

Fabricability

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 12-13 2
 Corrosion

 Corrosion is an irreversible interfacial reaction of a

material with its environment which results in
consumption of the material or in dissolution into the
material of a component of the environment

 Corrosion is the destructive result of electrochemical

reaction between a metal or alloy and its environment

 Corrosion is often called as ‘ Extractive Metallurgy in

reverse’

3
Factors affecting corrosion resistance of a material

Electrochemical

Physical Corrosion
chemistry Resistance Metallurgical

Thermodynamic

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 12-13
4
 Costs of Corrosion

Economic

Direct Indirect

Human life & safety

https://www.youtube.com/watch?v=gc8qXTh6tTY
https://www.youtube.com/watch?v=z7a9JHmxavc
https://www.youtube.com/watch? 5
 Costs of Corrosion: Economy aspect
 The global cost of corrosion is estimated to be US $2.5
trillion, which is equivalent to 3.4% of global GDP (2013).

Production & COST OF CORROSION UTILITIES:

Manufacturing Drinking Water &
13%
Sewerage
Utilities
35% Gas distribution
Government Electrical utilities etc.
15%
TRANSPORTATION:
Ships & Aircrafts
Transportation Railroad & vehicles
21%

INFRASTRUCTURE:
Infrastructure Gas & liquid
16% transmission
Airports, Waterways

PRODUCTION & MANUFACTURING: GOVERNMENT:

Chemical, Petrochemical, Pharmaceutical, food, paper, metal, Defense
oil& gas Exploration etc. Nuclear etc.
 Effect of Corrosion Cost on US Economy

Direct Corrosion Costs: $276 billion (3.1% of

U.S. GDP)

Landmark NACE
study on cost of Add in growth in
15 years
corrosion

$276B : Annual =$1Trillion

$449B : : Total
Direct cost of $276B : Annual
Inflation Annual
corrosion Indirect cost of
and Growth cost of
calculated by corrosion : what
from 1998 corrosion
1998 NACE consumers pay
to 2013 in U.S.
study

Indirect cost to Today, corrosion is one

Society (what you of the biggest unseen
and I pay) to industry costs to society

NACE Cost of Corrosion study: http://www.nace.org/publications/cost-of-corrosion-study

 Estimating the Cost of Corrosion for India
 According to National Association of Corrosion Engineers (NACE,
India chapter) the corrosion cost of India is 4.2% of the GDP

 This is about half of our defense budget and perhaps double of

our total annual expenses on education.
Agriculture & Allied Activities:
19.911
Agriculture, Forestry & fishing etc.
Mining, Manufacturing

Mining, Manufacturing &

13.973
Transportation
12.496 Construction: Metal & Non-Metallic
Products, Chemicals, Paper etc.
& Construction

Other Services
& Storage
Allied Activities
Agriculture &

Transporatation & Storage:

Rail, Road, Water & Air Transport,
Transmission Pipelines
2.392
Other Services:
Food Services, Electricity, Water
Supply, Defense etc.

Sector wise forecasted corrosion cost of India, 2012 (US$

Billion)
Assessment of Global Cost of Corrosion: http://impact.nace.org/economic-impact.aspx
 Corrosion-related Employment in Ohio (2016)

• NACE conducted survey to

determine company’s
workforce dedicated to
corrosion-related activities in
Ohio.

• Metals sector is the largest

producer of corrosion-related
jobs due to the presence of
metal production and metal
working companies in Ohio

• The second largest sector

producing corrosion related
jobs is coating industry.

Direct corrosion employment in industry sector (State of

Ohio)
Economics of the Corrosion Industry: State of Ohio Report (2016) 9
 Recent major accidents due to corrosion
Year Case Cause

2019 Eurocopter EC135T1 accident (Cayman Pitting corrosion leading to

Islands) intergranular cracking
2018 Flooding and sinking of towing vessel Corrosion followed by loss
MS NANCY C (Tennessee) of watertight integrity

2017 In-flight engine shutdown (California) Corrosion leading to fatigue

cracking
2017 Malfunction of amusement park ride Excessive corrosion on
(Ohio) support beam, reducing wall
thickness

2016 Rupture of natural gas transmission Corrosion along two

pipeline (Pennsylvania) circumferential welds
leading to fracture

2014 Bae systems JETSTREAM 31 (England) Stress corrosion cracking

on lading gear mounts

https://www.gscsg.com/corrosion-accidents.html
 Recent major accidents due to corrosion

Year Case Cause Cost of

Corrosion
2013 Cruise ship (Alabama) Severe corrosion $2.9 million
prior to ductile rupture
2012 Rupture of natural gas Ineffective cathodic $2.9 million
transmission pipeline Columbia protection
Gas Transmission Co.(Virginia )

2011 Light fixture fell in the travel Aluminum components $200 million
lanes "Big Dig" I-93 Northbound to contact stainless
Tunnel steel (Galvanic
(Boston, Massachusetts ) corrosion)
2009 Rupture of a high-pressure Stress Corrosion 50 million Yen
vessel at Nihon Dempa Kogyo Cracking (SCC) of the
(NDK) Co., Ltd (Illinois) walls

2009 Rupture of a natural gas Cracking under a de- $606,360.00

transmission pipeline (Florida bonded coating
Gas Transmission Company)
Organizations focusing on corrosion & its control

 World Corrosion Organization (WCO)

 Australasian Corrosion Association
 Chinese Society for Corrosion and Protection
 European Federation of Corrosion
 National Association of Corrosion Engineers (NACE)

Mission of the WCO

To promote education and best practices in corrosion control
for the socio-economic benefit of society, preservation
of resources, and protection of the environment
 Costs of Corrosion

Plant Downtime

Loss of Product

Indirect
Economic Loss of Efficiency

Contamination

Overdesign

13
 Costs of Corrosion

Loss of production while the plant is

Plant Downtime
inoperable during repairs (Example: Cost
to replace power from a shutdown nuclear
power plant)

Loss of Product Leaking tank, containers and pipelines

Accumulated corrosion products on heat

Loss of Efficiency exchanger tubing and pipelines
decreases the efficiency of heat transfer
and reduces the pumping efficiency

14
 Costs of Corrosion

Soluble corrosion products

Contamination Radioactive corrosion products
 Toxic corrosion products

In absence of adequate corrosion rate

Overdesign information, overdesign is required
resulting in wasted resources and greater
power requirements for moving parts.

Geological storage of high-level nuclear

waste in deep repositories requires
container that will maintain their integrity
for 300 to 700 years
15
 Electrochemical Reactions

Zn + 2HCl Zncl2 + H2

Zn + 2H+ Zn2+ + H2

Zn Zn2+ + 2e . . . . . . .Oxidation (anodic reaction)

2H+ + 2e H2 ...... Reduction (cathodic reaction)

 During metallic corrosion, the rate of oxidation equals the rate

of reduction (in terms of electron production and consumption)

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 14-15 16
 Electrochemical Reactions

Electrochemical reactions occurring during corrosion of Zn

in air-free HCl acid

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 15 17

 Electrochemical Reactions

Electrochemical reactions occurring during corrosion of a

metal (M) in air-free HCl acid
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 6 18
 Anodic Reactions

M Mn+ + ne

Fe Fe2+ + 2e

Ni Ni2+ + 2e

Al Al3+ + 3e

19
Cathodic Reactions

2H+ + 2e H2

Fe3+ + e Fe2+
Redox reaction

Sn4+ + 2e Sn2+

20
 Electrochemical Reactions in aerated solution

Electrochemical reactions occurring during corrosion of Zn

in aerated HCl acid
M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 18 21
 Cathodic Reactions

O2 + 4H+ + 4e– 2H2O . . . . . . .Acid solution

O2 + 2H2O + 4e– 4OH – ..... Neutral solution

In the absence of all other reduction reaction, water

will be reduced by

2H2O + 2e– H2 + 2OH –

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 16

22
 Formation of rust due to corrosion

Fe Fe2+ + 2e

O2 + 2H2O + 4e– 4OH –

2Fe + O2 + 2H2O 2Fe2+ + 4OH –

2Fe(OH)2

2Fe(OH)3

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 17

23
Summary: What’s need for corrosion to happen

 An anode: This is where the damage occurs.

Oxidation takes place.

 A cathode: Here’s where the reduction reaction

takes place.

 An electrolyte: (Almost any moisture will do.)

 Current Path: A current path between the cathode

and anode.

24
 Eight Forms of Corrosion
Uniform or General attack

Galvanic or Two-metal corrosion

Crevice Corrosion

Pitting

Intergranular corrosion

Selective leaching or parting

Erosion corrosion

Stress corrosion

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 39 25

 Uniform or General attack

Schematic illustration of uniform attack

 Uniform corrosion accounts for the greatest

tonnage
of metal consumed

 Yet this form of corrosion is not difficult to predict

and control!
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 26
 Uniform or General attack

 For uniform corrosion to happen, the corrosive

environment must have the same access to all parts
of the metal surface

 Metal must be metallurgically and compositionally

uniform

 Uniform corrosion is preferred from technical

viewpoint as it is predictable and thus acceptable
for design

27
 Galvanic or Two-metal corrosion

 The less resistant metal becomes anodic

 The more resistant metal becomes cathodic

 The driving force for current and corrosion is

the potential developed between the two metal

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 28
 Crevice Corrosion

 Intensive localized corrosion frequently occurs within the

crevices and other shielded areas on metal surface exposed
to corrosives

 This type of attack usually associated with small volumes of

stagnant solution caused by holes, gasket surfaces, lap joints,
surface deposits, crevices under bolt and river heads
– As a result, this form of corrosion is called crevice
corrosion
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 29
 Crevice Corrosion……mechanism

M Mn+ + ne . . . . . . .Oxidation

O2 + 2H2O + 4e– 4OH –

...... Reduction

 Initially the reaction occurs

uniformly over the entire
surface, including the crevice
area

 After some interval, the O2

within the crevice is depleted
Crevice corrosion…..initial stage

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 53-54 30
 Crevice Corrosion……mechanism

 After O2 is depleted, no further O2 reduction occur although

dissolution of M continues to happen

 This tends to produce in excess of M+ which is balanced by

the migration of Cl–

M+Cl- + H2O = MOH + H+Cl-

 Both Cl- and H+ accelerates the dissolution rates

 This increase in dissolution increases the dissolution, and

the result is rapidly accelerating or autocatalytic process

31
 Crevice Corrosion……mechanism

Crevice corrosion
….. Later stage

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 53-55 32
 Pitting Corrosion

Schematic illustration of pitting corrosion

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 33
 Pitting Corrosion
 Pitting is a extremely localized form of attack that results in
holes in the metal

 A pit may be described as a cavity or hole with the surface

diameter about the same or less than the depth

Pitting of 18-8 stainless steel

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 63-64 34
 Autocatalytic Nature of Pitting
 Pits initiate at certain locations where local dissolution of
metal is momentarily high due to a surface scratch,
emerging dislocations or other defects, or random
variations in chemical composition

 The dissolution of metal

within the pit tends to
produce excess positive
charge

 This leads to migration of

chloride ions to maintain
the electro-neutrality

Autocatalytic processes occurring in a corrosion pit

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 66-67 35
 Autocatalytic Nature of Pitting
 Pits also have high concen-
tration of H+ ions due to
M+Cl- + H2O = MOH + H+Cl- hydrolysis

 Both hydrogen and chloride

ions stimulate the dissolution
of metals within the pit and it
accelerates with time

 Since the solubility of O2 in

concentrated solution is
virtually zero, no O2 reduction
occurs within the pit but it
happens in adjacent to pits

 Pits cathodically protect rest of

the surface
Autocatalytic processes in a corrosion pit

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 66-67 36
 Intergranular Corrosion

Schematic illustration of intergranular corrosion

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 37
 Miller or Miller-Bravais Indices

Schematic illustration of the relationship between the crystal and

specimen axes for the (110)[001], that is, the normal to (110) is parallel
to the specimen ND, or Z axis and [001] is parallel to the specimen
RD, or X axis.

38
 Different type of grain boundary

 Based on misorientation angle ()

 Low angle grain boundary (≤15°)

 High angle grain boundary (>15°)

 Coincidence Site Lattice (CSL) boundary

39
 Energy of high angle grain boundary

 High angle boundaries are of high surface energy of about

600 – 800 mJ/m2

 Energy of a twin boundary is only about 25 mJ/m 2

High energy grain boundaries

serve as preferential site for
solid state reactions such as:
 Diffusion
 Phase Transformation
 Precipitation

40
 Selective leaching

Schematic illustration of selective leaching

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 41
 Erosion Corrosion

Schematic illustration of erosion corrosion

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 42
 Stress corrosion cracking

Schematic illustration of stress corrosion cracking

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 10 43
 Free Energy

Mechanical analogy of free-energy change

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 446 44

 Free Energy

It is not possible to
accurately predict the
velocity of reaction from
the change of free energy

Effect of reaction path on reaction rate

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 447 45

 Cell potential

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 44-45 46
 Free Energy and Electrode Potential

Zn + 2HCl Zncl2 + H2

Zn + 2H+ Zn2+ + H2

Zn Zn2+ + 2e . . . . . . .Oxidation (anodic reaction)

2H+ + 2e H2 ...... Reduction (cathodic reaction)

G = -nFE

E = Ea + Ec
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 42-43 47
 Electromotive force or emf series

Standard half-cell
electrode potential

Single electrode
potential

Redox potential

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 43-45 48
 Cell potential

E = Ea + Ec

G = -nFE

A positive E corresponding to a negative G indicates

that the reaction is spontaneous in the written direction

Zn Zn2+ + 2e

2H+ + 2e H2

E = +0.762 + 0= +0.762
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 43-45 49
 Cell potential

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 447-448 50
 Cell potential

3Pb + 2Al3+ 3Pb2+ + 2Al

Pb Pb2+ + 2e

Al3+ + 3e Al

E =  1.662 + 0.126 = 1.532

Reaction will occur in reverse

direction

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 43-45 51
 Prediction of corrosion behaviour

Cu + H2SO4 No reaction

2Cu + 2H2SO4 + O2 2CuSO4 + 2H2O

Cu/Cu2+ more +ve than H2/H+

O2/H2O more +ve than Cu/Cu2+

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 44 52

 Take home thoughts!!!!!
As the redox potential of metal become more positive
 Tendency to corrode decreases
 Tendency decreases even in presence of oxidizers

The metals at the uppermost part of the redox series is

extremely inert (e.g. Pt and Gold)

Redox potential can be used to state a criterion for

corrosion
 Corrosion will not occur until the spontaneous
direction of the reaction is metal oxidation

Major use of thermodynamic as far as corrosion is

concerned
 It tells unambiguously that corrosion will not occur
 It does not tell about the rate of corrosion
53
 Concentration effects on electrode potential

It is known that

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 45-47 54
 Concentration effects on electrode potential

Substituting and

Substituting

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 45-47
55
 Polarization

 Cathodic Polarization

 Anodic Polarization

56
 Cathodic Polarization

2H+ + 2e H2 ...... Reduction (cathodic reaction)

If electrons are available, the potential at the surface becomes

negative — the excess electrons accumulate at the interface
waiting for reaction — Reaction is not fast enough to accommo-
date all the available electron

The negative potential change is called ‘cathodic polarization’

57
 Anodic Polarization

Zn Zn2+ + 2e . . . . . . .Oxidation (anodic reaction)

A deficiency of electrons produces a positive potential change

called ‘anodic polarization’

As the deficiency (polarization) becomes greater, the tendency

for anodic dissolution becomes greater — Anodic polarization
basically represents a driving force for corrosion by the anodic
reaction

58
 Polarization

 Activation Polarization

 Concentration Polarization

59
 Activation Polarization
Activation polarization refers to an electrochemical process
that is controlled by the reaction sequence at the metal-
electrolyte interface

 Let us consider the hydrogen – evolution reaction on Zn surface

during corrosion in strong acid solution

Hydrogen reduction
reaction under activation
control (schematic
representation)

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 19-20 60
 Activation Polarization

Step 1: H+ diffuse to the metal

surface and adsorbed or attached
there

Step 2: Electron transfer occur

resulting in reduction of H+ to H

Step 3: Two H atoms combine

together to form H2

Step 4: H2 molecules combine

together to form H2 bubbles
The speed of reduction of hydrogen ions will be
controlled by the slowest of these steps
M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 19-20 61
 Concentration Polarization

Concentration polarization refers to electrochemical reactions

that are controlled by the diffusion in the electrolyte

 Let us consider the hydrogen – evolution reaction on Zn surface

during corrosion in dilute acid solution

Concentration
polarization during
hydrogen reduction
(schematic
representation)

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 19-20 62
 Concentration Polarization

 Acid solution is dilute

 The number of H+ ions in

solution is quite small

 Reduction rate is controlled by

diffusion of H+ ions into the
metal surface

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 19-20 63
 Activation vs. Concentration Polarization

Activation polarization is predominant during

corrosion in media containing a high concentration
of active species (e.g. concentrated acids)

Concentration polarization is predominant when the

concentration of reducible species is low
(e.g. dilute acids)

In most instances, concentration polarization during

metal dissolution is small and can be neglected;
it is important during reduction reactions

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 20 64

Influence of environmental parameters on Polarization
 Depending on what kind of polarization is controlling the
reduction rate, environmental variables produce different
effects

 For example, any changes in the system that increase the

diffusion rate will decrease the effects of concentration
polarization and hence increase the corrosion rate

 Thus, increasing the velocity or agitation of the corrosive

medium will increase the rate only if the cathodic process is
controlled by concentration polarization

 If both the cathodic and anodic processes are controlled by

activation polarization, agitation will have no influence on
corrosion rate

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 21 65

 Passivity

 Passivity refers to the loss of chemical reactivity experienced

by certain metals and alloys under particular environmental
condition

 That is, certain metal and alloys become essentially inert and
act as if they are noble metal such as gold or platinum

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 21-22 66
 Behaviour of normal metal without passivity

Corrosion rate of a metal as a function of solution oxidising

Power (electrode potential)

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 21 67

 Passivity

Passivity at oxidizing potentials above Ep

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 8-9 68
 Passivity

The corrosion resistance above Ep, despite a high driving

force for corrosion (i.e. high anodic polarization), is defined
as ‘passivity’.

Passive corrosion rate is very low — a reduction of 103 to 106

times below the corrosion rate in the active state.

 Passivity is caused by formation of thin, protective, oxide film

that acts as a barrier to the anodic dissolution.

 Passive film is thin — a breakdown in film results very high

rate of corrosion.

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 8-9 69
 Environmental effect – Effect of O2 and Oxidizer

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 23-24 70
 Environmental effect – Effect of Velocity
Type A, Part 1: if the corrosion
process is under cathodic diffusion
control
Type A, Part 1 & 2: if the
corrosion process is under
cathodic diffusion control and the
metal is passivated subsequently
Type B: if the corrosion process
is controlled by activation
polarization
Type C: if the material is protected
by massive, less tenacious film
which breaks at high velocity –
erosion corrosion

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 24-25 71
 Environmental effect – Effect of Temperature

Type A: A very rapid or

exponential rise in corrosion
rate with temperature

Type B: A negligible
temperature effect followed
by exponential rise in
corrosion rate with
temperature – associated
with passive – transpassive
behaviour

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 26 72

 Corrosion rate

Ita m = mass reacted

m I = current
nF a = atomic weight

Zn Zn2+ + 2e

m Ia ia A = surface area
r   i = current density
tA AnF nF
Current density rather than current is proportional to
corrosion rate

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 76 73
 Exchange current density

ia
r r  0
i0 = exchange
nF
oxid red
current density

Exchange current density is a convenient way of

representing rates of oxidation & reduction at equilibrium

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 456 74

 Exchange current density

Exchange current density is a fundamental kinetic parameter

Hydrogen-hydrogen ion exchange current densities

 G is not affected by the electrode surface

 Exchange current density is affected by the electrode surface

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 456-457 75
 Electrode Kinetics

Deviation from equilibrium potential is called as polarization

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 454-455 76
 Polarization

Polarization can be defined as the displacement of electrode

potential from the net current

 Cathodic Polarization

 Anodic Polarization

77
 Activation Polarization
 is overvoltage
Anodic Polarization

Cathodic Polarization

Tafel equation
Activation polarization curve of a hydrogen electrode
b represents the expression 2.3RT/nF and known as Tafel
constant
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 80-82 78
 Concentration Polarization

Low reduction or High reduction or

High concentration Low concentration

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 459-461 79
 Concentration Polarization

iL = Limiting current density

CB = bulk concentration of ions
x = thickness of the diffusion layer

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 459-461 80
 Concentration Polarization

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 459-461 81
 Combined Polarization

Applies to all cathodic reaction

Applies to almost all dissolution process

except the metal showing active-passive
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 86 82
 Combined cathodic polarization

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 451-462 83
 Mixed potential theory

Any electrochemical reaction can be divided into two

or more partial reduction & oxidation reductions

There can be no net accumulation of electrical charge

during an electro-chemical reaction

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 462-463 84
 Mixed Electrode

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 87 85
 Mixed Electrode – Example of Zn

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 463-464 86
 Mixed Electrode – Example of Fe

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 464-465 87
 Corrosion rate and exchange current density

Corrosion rate of Fe is more than Zn in identical condition

This is due to higher exchange current density of H2

evolution on Fe surface as compared to Zn surface
M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 463-465 88
 Mixed Electrode – effect of external current

Corrosion rate on M surface decreased significantly due to applied

external current (which causes an cathodic overvoltage C)
A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., pp. 94-95 89
 Combined activation & concentration polarization

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 468 90

 Effect of stirring during combined polarization

Effect of stirring during corrosion on i L and icorr

A. D. Jones, Principles and Prevention of Corrosion, Macmillan Publishing Company, 2nd ed., p. 93 91
 Passivity

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 469 92

 Active – passive metal

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., p. 470 93

 Effect of exchange current density on passivity

Case 1: Ti in dilute air free

sulfuric or HCl acid

Case 2: Fe in dilute nitric

acid

Case 3 : Stainless steel in

acid solution containing
oxidizer or dissolved O2

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 472-473 94
 Effect of passivity on engineering design

Case 3 is the most desirable

from engineering viewpoint

Case 2 is the least desirable

from engineering viewpoint

Case 1 is particularly not

desirable as corrosion rate is high

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 472-473 95
 Effect of oxidizer concentration on corrosion

Let us assume that

exchange current density of
the oxidizer remain constant

The only effect of the oxidizer is

to shift the reversible potential
in the passive direction

Effect of oxidizer concentration on the

electrochemical behavior of an active-
passive metal

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 483-484 96
 Effect of oxidizer concentration on corrosion

Amount of oxidizer necessary

to cause passivation is greater
than that required to maintain it

To safely maintain passivity, the

oxidizer concentration should be
equal to or greater than the
minimum amount necessary to
cause spontaneous passivation

Effect of oxidizer concentration on

the corrosion rate of an active-passive
metal

M. G. Fontana, Corrosion Engineering, McGraw-Hill International Edition, 3rd ed., pp. 484-485 97
 Effect of stirring velocity on corrosion
Active metal

Active-passive metal

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