MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

 Corrosion Kinetics
Upcoming Topics…
➢ Electrical Double Layer

➢ Exchange Current Density

➢ Corrosion Rate Calculations (Faradays Laws of Electrolysis)

➢ Polarization (Evans Diagrams)

➢ Kinetics of Passivity

➢ Corrosion Testing

MM-435_Corrosion Degradation and Protection 2

 Electrical Double Layer
Distribution of anions and cations at a metal – solution interface (Double Layer):

A compact layer (Helmholtz)

closest to metal surface in which
charge distribution and hence

Metal Surface
potential varies linearly with
distance

A more diffuse inter layer (G. C.

layer) where potential changes
exponentially
Electrolyte Solution

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Electrical Double Layer

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Electrical Double Layer

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Energy-Distance Profile
These are plots of free energy (ΔG) v/s the distance representing the progress of reaction
through the double layer.

➢ The metal atoms are located in energy wells

associated with lattice structure.

➢ A metal atom cannot be detached from

the lattice and pass into the solution until it
crosses an energy barrier, called activation
energy.

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Reversible and Irreversible Processes
Reversible:

where K1 is the constant depending on

temperature, time and activity.

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Reversible and Irreversible Processes
Irreversible:

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Exchange Current Density:
it implies rates of dissolution and deposition reactions are equal when metal
in solution is at equilibrium (Reversible Process)

Exchange current density of Hydrogen (H2) Evolution on various surfaces..??

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Exchange Current Density:
Exchange current density (io) is dependent on:

a) Nature of the redox reaction

b) Electrode composition / surface
c) Concentration ratio of oxidized and reduced species
d) Temperature.

For example,
➢ io for H+ / H2 reaction on platinum
-2
is about 10 A/cm2 and
➢ io for H+ / H2 reaction on mercury
-13 2
is about 10 A/cm ,
➢ This means it is easier to reduce
hydrogen ions from acidic
electrolyte on a platinum
electrode unlike on mercury,
which possesses a high
Hydrogen-overvoltage. MM-435_Corrosion Degradation and Protection 10
 Faraday’s Laws and corrosion rate calculation:
1st Law
The mass of primary products formed at an electrode by electrolysis is directly proportional to the
quantity of electricity passed
I = current in amperes
t = time in seconds
m = mass of the primary product in grams
Z = constant of proportionality (electrochemical equivalent). It is the mass of a substance liberated by 1 ampere-second of a current (1
coulomb).
nd
2 Law
The masses of different primary products formed by equal amounts of electricity are
proportional to the ratio of molar mass to the number of electrons involved with a
particular reaction:

m1, m2 = masses of primary product in grams

M1, M2 = molar masses (g.mol−1)
n1, n2 = number of electrons
Z1, Z2 = electrochemical equivalents.

Combining the first and second laws,

Substituting for Z from 2nd law OR

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Applications of Faraday’s Laws:

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Applications of Faraday’s Laws:

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Applications of Faraday’s Laws:

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 Applications of Faraday’s Laws:
Determination of Penetration depth:

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Applications of Faraday’s Laws:

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Problem
A sample of zinc corrodes uniformly with a current density of 4.2 ×10−6 A/cm2
in an aqueous solution.

(a) What is the corrosion rate of zinc in mdd (mg/dm2/day)?

(b) What is the corrosion rate of zinc in mm/year?
[MZn = 65.38 g/mol, ρ(Zn) = 7.1 g/cm3, F =96 500 Coulombs/mol ]

Solution
(a) What is the corrosion
rate of zinc in mdd (mg/dm2/day)?

MM-435_Corrosion Degradation and Protection 17

 (b) What is the corrosion rate of
zinc in mm/year?

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Applications of Faraday’s Laws:
Current density Penetration rates Mass/Weight loss

Current density

Penetration
rates

Mass/Weight loss

MM-435_Corrosion Degradation and Protection 19

Applications of Faraday’s Laws:
Corrosion rate determination of an alloy..??

(in mpy)

Composition Atomic Weight Density, ρ

Element
(%) (g/mol) (g/cm2)
Cr 18 52.01 7.10
Ni 10 58.68 8.9
Mo 03 95.95 10.2
Fe 67 55.85 7.86
Mn 02 54.94 7.45

MM-435_Corrosion Degradation and Protection 20

Corrosion rate determination by Weight Loss Method…!

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Kinetics of Corrosion
Corrosion Evaluation/Calculation Strategies

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Experimental Methods for Corrosion Testing/Monitoring/Determination

Objectives:

I. To determine the best material for a typical requirement

II. To predict the portable service life of a metal component or
structure
III. To evaluate the new alloy and processes for commercial
operation/utilization
IV. To develop materials with improved corrosion resistance
V. To control the quality and allow acceptance after meeting the
specifications
VI. To evaluate and regulate environmental variations at controls
(inhibitors etc.)
VII. To study the corrosion mechanism
MM-435_Corrosion Degradation and Protection 23
Experimental Methods for Corrosion Testing/Monitoring/Determination

Types of Corrosion Tests:

Corrosion tests can be classified into two categories:

1) Laboratory Tests: Produce conditions close to plant or service conditions

They may be sub-divided into:

❑ Simulated Services Tests or Long Term Tests
❑ Accelerated Tests or Short Term Tests

2) In- service TestsCarried out in actual process streams or natural environments

These may be sub-divided into:
❑ Plant Tests
❑ Field Tests

MM-435_Corrosion Degradation and Protection 24

Experimental Methods for Corrosion Testing/Monitoring/Determination

Standards and Codes

➢ASTM Standards
most commonly used
➢NACE Standards
➢API Standards
➢British Standards

MM-435_Corrosion Degradation and Protection 25

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests:

Conventional methods of corrosion rate determinations:

➢ Weight loss method

➢ Immersion Test
➢ Atmospheric Corrosion Test
➢ Salt Spray/Fog Test Qualitative

Modern methods (Electrochemical):

➢ Tafel Extrapolation/Potentiodynamic Polarization

➢ Linear Polarization Resistance (LPR) methods
➢ Open Circuit Potential (OCP) Method Qualitative
➢ Electrochemical Impedance Spectroscopy (EIS)

MM-435_Corrosion Degradation and Protection 26

 Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

➢ Weight loss method

➢ Immersion Test
➢ Atmospheric Corrosion Test
➢ Salt Spray/Fog Test Qualitative

Weight loss calculation

MM-435_Corrosion Degradation and Protection 27

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Weight loss method

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Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Weight loss method

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Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Weight loss method

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Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Immersion Test

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Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Immersion Test

MM-435_Corrosion Degradation and Protection 32

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Immersion Test

MM-435_Corrosion Degradation and Protection 33

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Immersion Test

MM-435_Corrosion Degradation and Protection 34

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Immersion Test

MM-435_Corrosion Degradation and Protection 35

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Atmospheric Corrosion Test

MM-435_Corrosion Degradation and Protection 36

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Atmospheric Corrosion Test

MM-435_Corrosion Degradation and Protection 37

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Atmospheric Corrosion Test

MM-435_Corrosion Degradation and Protection 38

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Salt Spray/Fog Test

MM-435_Corrosion Degradation and Protection 39

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Salt Spray/Fog Test

MM-435_Corrosion Degradation and Protection 40

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Salt Spray/Fog Test

MM-435_Corrosion Degradation and Protection 41

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Salt Spray/Fog Test

MM-435_Corrosion Degradation and Protection 42

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests: Conventional methods of corrosion rate determinations:

Salt Spray/Fog Test

MM-435_Corrosion Degradation and Protection 43

Kinetics of Corrosion
POLARIZATION

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Polarization:
When electrode reactions take place, the potential will no longer be at equilibrium due to
current flow through an electrochemical cell-causing a change in the electrode reversible
potential. This electrochemical phenomenon is termed as POLARIZATION.
Corroding systems are not in equilibrium → deviation from
thermodynamics.
The Deviation of the potential from its reversible value is
referred to as POLARIZATION.

It is given by:

η = E − Erev
where:
η is the Polarization or deviation of the potential,
E is applied/measured potential and
Erev is the reversible potential.

MM-435_Corrosion Degradation and Protection 45

Polarization:
The Deviation of the potential from its reversible value is referred to as POLARIZATION.

Types of Polarization:

Polarization of anode – anodic polarization Types of polarization

Polarization of cathode – cathodic polarization w.r.t type of electrodes

Sub Types:
1. Activation Polarization (Over Potential)
2. Concentration Polarization

Total Polarization:

MM-435_Corrosion Degradation and Protection 46

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Kinetics of Corrosion
POLARIZATION

MM-435_Corrosion Degradation and Protection 2

Polarization:
When electrode reactions take place, the potential will no longer be at equilibrium due to
current flow through an electrochemical cell-causing a change in the electrode reversible
potential. This electrochemical phenomenon is termed as POLARIZATION.
Corroding systems are not in equilibrium → deviation from
thermodynamics.
The Deviation of the potential from its reversible value is
referred to as POLARIZATION.

It is given by:

η = E − Erev
where:
η is the Polarization or deviation of the potential,
E is applied/measured potential and
Erev is the reversible potential.

MM-435_Corrosion Degradation and Protection 3

 measured

(Hg/Hg2Cl2)/

Solution η = E − Erev

MM-435_Corrosion Degradation and Protection 4

Polarization:
The Deviation of the potential from its reversible value is referred to as POLARIZATION.

Types of Polarization:

Polarization of anode – anodic polarization Types of polarization

Polarization of cathode – cathodic polarization w.r.t type of electrodes

Sub Types:
1. Activation Polarization (Over Potential)
2. Concentration Polarization

Total Polarization:

MM-435_Corrosion Degradation and Protection 5

Polarization:
Activation Polarization (Over-potential)
Activation polarization is caused by a slow step in the electrode reaction (electrode reaction
requires activation energy in order to reach the final state)
The magnitude of shift of potential in the noble direction is called ‘over potential’ or
‘Activation Polarization’ (ηAct) .
The relationship between activation polarization (over-potential) and the rate of the reaction
(ia and io) is given as:

Tafel relationship.

MM-435_Corrosion Degradation and Protection 6

Polarization:
Activation Polarization (Over-potential)

Magnitude of io (exchange current density) will indicate as to whether the redox reaction is
reversible or irreversible.

Lower io denotes higher over-potential Irreversibility

Higher io indicates lower over-potential Reversibility

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Polarization:
Concentration Polarization

Polarization resulting from concentration gradients is termed as concentration polarization

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Polarization:
Resistance Polarization

The contribution to polarization due to IR drops is referred to as Resistance polarization

MM-435_Corrosion Degradation and Protection 9

Polarization:
1. Mass Transport Processes
Transport Processes 2. Charge Transport Processes
Mass transport to metal surface involves forces such as convection, diffusion and migration,
depending on presence or absence of electric field and flow conditions
Charge transport is basically the charge transfer governed by kinetic factors like activation
energy barrier and equilibrium current density (exchange current density).

Activation polarization involves kinetic

factors related to charge transfer, such as
activation energy barrier and equilibrium
current density
→ Charge transport processes.
Concentration polarization is controlled by
diffusion gradients (Fick’s law)
→ Mass transport processes.

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Polarization:
The polarisation of an anode is always positive and that of a cathode always negative

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Polarization:
However, it often is the case that two or more electrode reactions can take place
simultaneously at an electrode, e.g. a cathode reaction, whose equilibrium potential is E01 and
an anode reaction, whose equilibrium potential is E02.

Reversible potential
for cathode reaction

Reversible potential
for anode reaction

Over potential curves for two electrode reactions, occurring simultaneously

at an electrode surface; E = electrode potential, i = current density.

MM-435_Corrosion Degradation and Protection 12

Polarization:

Activation Polarization

Tafel relationship.

Concentration Polarization…???

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 Concentration Polarization

C0 = surface concentration of electro active species.

b

Cb = Bulk concentration.

δ= diffusion layer thickness

(thickness of the concentration gradient)

Concentration – distance profile at electrode – solution interface

for a limiting current situation

For well-mixed solutions, the concentration

is constant in the bulk region.

For stirred aqueous solutions the thickness

of the diffusion layer varies between 0.01
and 0.001 mm.

MM-435_Corrosion Degradation and Protection 14

 Concentration Polarization

C0 = surface concentration of electro active species.

Cb = Bulk concentration.

δ= diffusion layer thickness

(thickness of the concentration gradient)

Concentration – distance profile at electrode – solution interface

for a limiting current situation

MM-435_Corrosion Degradation and Protection 15

Concentration Polarization

(in terms of Faraday’s law)

(C0 =0 when current reaches steady state)

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Concentration Polarization

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Polarization:
Polarization and Corrosion rate determination

Polarization behaviour of a metal (M) in de-

aerated acid solution

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Polarization:

When polarization occurs mostly at anodes, corrosion

reaction is said to be Anodically Controlled

When polarization occurs mostly at

cathodes, corrosion reaction is said
to be Cathodically controlled

MM-435_Corrosion Degradation and Protection 19

Polarization:
Resistance control: when electrolyte /
electrode resistance is so high that the
current is insufficient to polarise either of the
electrodes.

Mixed control refers to the condition where

both anode and cathode are polarized.

MM-435_Corrosion Degradation and Protection 20

Problem Given

Solution

MM-435_Corrosion Degradation and Protection 21

Problem
day-1

Solution

MM-435_Corrosion Degradation and Protection 22

Polarization of a metal in aerated acid solution

Polarization behaviour of metal M in unstirred

aerated near neutral solution Polarization behaviour of a metal (M) in
de-aerated acid solution

MM-435_Corrosion Degradation and Protection 23

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Kinetics of Corrosion
POLARIZATION

MM-435_Corrosion Degradation and Protection 2

Polarization of a metal in aerated acid solution

Polarization behaviour of metal M in unstirred

aerated near neutral solution Polarization behaviour of a metal (M) in
de-aerated acid solution

MM-435_Corrosion Degradation and Protection 3

Problem

Solution

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Concentration Polarization

Factors

1. Agitation

2. Temperature

3. Velocity

4. Concentration of Ionic Species

5. Geometry

MM-435_Corrosion Degradation and Protection 5

Activation Polarization

Factors

1. Agitation

2. Temperature

3. Materials

4. Surface Roughness

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Kinetics of Corrosion
Mixed Potential Theory

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Mixed Potential Theory (Evans Diagram)_Assumptions

1) Electrochemical Reactions are composed of two or more partial anodic and cathodic
reactions

Anodic and cathodic half – cell reactions occurring

simultaneously on a corroding metal, M

MM-435_Corrosion Degradation and Protection 8

 Mixed Potential Theory (Evans Diagram)_Assumptions
2) No accumulation of Charges….Conservation of charges
i.e. Sum of anodic oxidation currents = sum of cathodic reduction currents (OR)
Total rate of oxidation = Total rate of reduction.

Anodic and cathodic half – cell reactions occurring Polarization of anodic and cathodic reactions to yield a
simultaneously on a corroding metal, M mixed potential

Ecorr is corrosion potential which is a mixed potential.

At Ecorr, rates of anodic and cathodic reactions are equal.
ic= ia = icorr, at Ecorr MM-435_Corrosion Degradation and Protection 9
Mixed Potential Theory (Evans Diagram)

Example: Corrosion of Zn in HCl

MM-435_Corrosion Degradation and Protection 10

Applications of Mixed Potential Theory EMF Series

Corrosion of Fe and Zn

Thermodynamics says:

Zn is more active than Fe

But….
Actually
Fe oxidizes/corrodes more than Zn

How….???

MM-435_Corrosion Degradation and Protection 11

Applications of Mixed Potential Theory

Corrosion of Fe and Zn

Fe

Zn Fe+Zn

MM-435_Corrosion Degradation and Protection 12

Applications of Mixed Potential Theory

Corrosion of Fe and Zn

Comparison of electrochemical parameters for iron and zinc

MM-435_Corrosion Degradation and Protection 13

 Applications of Mixed Potential Theory
Coupling of active to noble metal

Galvanic coupling of active to noble metal

MM-435_Corrosion Degradation and Protection 14

 Applications of Mixed Potential Theory
Coupling of active to noble metal

If the area ratio of platinum to iron (larger cathode in contact with smaller anode), is increased, the effect of coupling
with platinum on the corrosion rate of iron will be magnified.

Effect of Area ratio

Effect of change in cathodic surface area on the corrosion rate of an active metal
MM-435_Corrosion Degradation and Protection 15
Applications of Mixed Potential Theory
Galvanic Coupling

Au – Zn and Pt – Zn couples

Exchange current density for hydrogen

reduction on platinum and gold are 10-2
A/cm2 and 10-6 A/cm2 respectively.

Under the circumstances, higher

corrosion rate (icorr) for zinc can be
expected when coupled to platinum than
when contacted with gold (cathodic
surface area remaining similar in both
Effect of galvanic coupling of zinc with gold and platinum
cares)

MM-435_Corrosion Degradation and Protection 16

Applications of Mixed Potential Theory

Effect of an Oxidizer

Effect of oxidizer on polarization

behaviour of a metal

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Applications of Mixed Potential Theory

Effect of Oxygen

MM-435_Corrosion Degradation and Protection 18

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Kinetics of Corrosion
Corrosion Evaluation/Calculation Strategies

MM-435_Corrosion Degradation and Protection 2

Experimental Methods for Corrosion Testing/Monitoring/Determination

Laboratory Tests:

Conventional methods of corrosion rate determinations:

➢ Weight loss method

➢ Salt Spray/Fog Test Qualitative
➢ Immersion Test
➢ Atmospheric Corrosion Test

Modern methods (Electrochemical):

➢ Tafel Extrapolation
➢ Polarization resistance methods
➢ Open Circuit Potential (OCP) Method Qualitative
➢ Electrochemical Impedance Spectroscopy (EIS)

MM-435_Corrosion Degradation and Protection 3

Experimental Methods for Corrosion Testing/Monitoring/Determination

Modern methods (Electrochemical):

➢ Tafel Extrapolation
➢ Polarization resistance methods
➢ Open Circuit Potential (OCP) Method Qualitative
➢ Electrochemical Impedance Spectroscopy (EIS)

MM-435_Corrosion Degradation and Protection 4

Modern methods (Electrochemical):
Tafel Extrapolation Method
In this technique, the polarization curves for the anodic and cathodic reactions are obtained by applying
potentials about 300 mV (against SCE) well away from the corrosion potential and recording the
current. Plotting the logarithms of current (log I) vs potential (E) and extrapolating the currents in the
two Tafel regions gives the corrosion potential (Ecorr) and the corrosion current (icorr ) . A hypothetical
Tafel plot is shown in Figure.
Knowing icorr, the rate of corrosion can be calculated in desired units by using Faraday’s law

Potential – current diagram depicting acid corrosion of zinc

MM-435_Corrosion Degradation and Protection 5
Tafel Extrapolation Method

Tafel polarization curves for Ni-Zn-P, Cd, and Zn-Ni coatings in

0.5 M Na2SO4+0.5 M H3BO3 solution at pH 7.0

Comparison of Tafel polarization plots for different coatings.

Numbers in the parenthesis correspond to the weight
percentage of metals
MM-435_Corrosion Degradation and Protection 6
Tafel Extrapolation Method

Corrosion Corrosion
Tafel Constants Corrosion Potential
Current Rate
Ecorr
Icorr C.R.
Sample ID βa (mV/decade) -βc (mV/decade) (mV against
(µA) (mpy)
Hg/Hg2Cl2 )
Substrate_Low Carbon Steel 105 473 -597 22.866 2.612
E70_Pure Epoxy Coated 91 292 -506 0.634 0.072
E70_(60% epoxy + 8% Silica) 86 593 -524 1.067 0.121
E200_(60% epoxy + 6% Silica) 84 238 -528 0.777 0.089
E250_(60% epoxy + 6% Silica) 95 323 -436 0.153 0.017
E300_(60% epoxy + 6% Silica) 103 369 -530 9.765 1.110

MM-435_Corrosion Degradation and Protection 7

Tafel Extrapolation Method

Tafel plots of the carbon steel specimens in

Tafel plots of the carbon steel specimens in the
the Pseudomonas sp. SWP-4 inoculated medium after
deionized sterile water (DI water) and in the
different exposure periods
oil–cell-free fermentation broth.
MM-435_Corrosion Degradation and Protection 8
 Modern methods (Electrochemical):
Linear polarization Method
Polarization resistance (Rp) of a corroding
metal is defined using Ohm’s Law as:
The slope of the linear portion of the potential (E) vs
current density (log i) plot around the corrosion
potential (Ecorr) is termed as the linear polarization
(Rp). i.e. Rp = (ΔE)/(ΔI ) at E= 0.

The potential–current density plot is approximately linear

in a region of within ±10 mV of the corrosion potential.

By measuring this slope, the rate of corrosion can

be measured. The correlation between icorr and
slope (ΔE)/(ΔI) is given by:
Stern & Geary Equation

As the slope of the plot has the units of resistance, this

technique is called ‘Polarization Resistance’ technique. Hypothetical Linear polarization curve
MM-435_Corrosion Degradation and Protection 9
Modern methods (Electrochemical):
Linear polarization Method

Hypothetical Linear polarization curve

MM-435_Corrosion Degradation and Protection 10

 Modern methods (Electrochemical):
Linear polarization Method

The linear polarization technique estimates

instantaneous corrosion rates under various
process conditions.

This technique accurately measures corrosion rates

<0.1 mpy.

It is of a great importance in water distribution

systems and food industries that face problems with
traces of impurities and contamination.

It can be used to measure the corrosion rates in civil

engineering structures that cannot be subjected to
weight loss measurements.

MM-435_Corrosion Degradation and Protection 11

Modern methods (Electrochemical):
Linear polarization Method

Linear polarization plots for Zn-Ni-Cd, Zn-Ni, and Cd coatings

Linear polarization studies of Ni-Zn-P, Zn-Ni, and Cd coatings in 0.5 M

Na2SO4 + 0.5 M H3BO3 solution
MM-435_Corrosion Degradation and Protection 12
Example 1
From a given plot of polarization resistance
(Fig. 3.22), calculate the rate of corrosion.

MM-435_Corrosion Degradation and Protection 13

Problem

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 Modern methods (Electrochemical):
Open Circuit Potential Method (OCP Method)
➢ The change in the OCP vs. time of the corroding
metal is determined by monitoring the OCP as a
function of time.

➢ Figure presents the OCPs vs. time of various

sacrificial and barrier coatings that are commonly
used for corrosion protection

➢ The coating stability is controlled by:

• the severity of the corroding solution,

• the thickness of the coating
• the potential difference of the underlying metal
and that of the sacrificial or barrier coating.

➢ The OCP reaches the value for the protected metal

when the sacrificial coating is completely removed Open circuit potential vs. time of various coatings on steel in 0.5 M
Na2SO4+0.5 M boric acid solution at a pH of 7.0
from its surface.

MM-435_Corrosion Degradation and Protection 15

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Kinetics of Corrosion

Passivity

MM-435_Corrosion Degradation and Protection 2

Passivity
Loss of reactivity of a metal due to formation of a protective layer

If a metal is converted to an oxide and the oxide formed is stable, the metal is considered
passive because this oxide forms a barrier between the metal and the environment.
The passive films may be as thin as 2–10 nm

Active-Passive Metals??
Metals, such as Fe, Cr, Ni, Ti, Al etc. etc.
demonstrate an active–passive behaviour in
aqueous solutions. Such metals are called
active–passive metals.

Polarization curves for active passive metals??

Active Passive metals exhibit S-shaped

polarization curves.

Polarization diagram for active–passive metal

MM-435_Corrosion Degradation and Protection 3
Active-Passive Metals

Pitting Potential
Ep

Flade Potential
Ef

Anodic dissolution behavior of a metal with more details

MM-435_Corrosion Degradation and Protection 4

Active-Passive Metals
Critical current density (icrit).
The maximum current density observed in the active region for a metal or alloy that exhibits
an active–passive behavior.
Passive potential (Epassive).
The potential of an electrode where a
change from an active to a passive state
occurs.
Passive current density (ip).
The minimum current density required to Ep
maintain the thickness of the film in the
passive range. Ef
Flade potential (EF).
The potential at which the current becomes
virtually independent of potential and remains
virtually stationary is called the flade potential
(EF)
Pitting potential (Ep).
It is the potential at which there is a sudden Anodic dissolution behavior of a metal with more details

increase in the current density due to

breakdown of passive film on the metal
surface in the anodic region. MM-435_Corrosion Degradation and Protection 5
Active-Passive Metals

Decrease

Decrease

Decrease
MM-435_Corrosion Degradation and Protection 6
Active-Passive Metals
Once passivity has initiated, a small current is required to maintain it in a passive state.

There is no change in current density until a point is reached which marks the end of the passive region.

At ip, the metal dissolution occurs at a constant

rate and the oxide film begins to thicken.

In the passive region,

As the potential is increased in
the noble direction, what keeps the
Current density (passive current
density) constant..???

It’s the growing thickness of the layer

The film which is dissolved is immediately

Anodic dissolution behavior of a metal with more details
replaced by a new film and a net balance is
maintained between dissolution and film
reformation
MM-435_Corrosion Degradation and Protection 7
Thermodynamics of Passivity (Pourbaix diagrams)

The stability of different metals or their oxides is

estimated by using potential-pH diagrams (Pourbaix
diagrams).

Pourbaix diagrams show:

➢ the values of pH and the potential at which
the metal reacts to form complex anions or
oxides.
➢ They also indicate where metal passivates
or is immune to corrosion.

The dissolution of a metal and the existence of a

passivation potential and stability of the passive
products in an aqueous solution depend on the:

➢ nature of the metal,

➢ solution’s pH and,
➢ solutions’ oxidizing power.

MM-435_Corrosion Degradation and Protection 8

Effect of chromium on the transpassive region
MM-435_Corrosion Degradation and Protection 9
 Passivity and Flade Potential

The Flade potential is used to evaluate the

conditions for passive film formation and to
determine the stability of the passive film.

Example
The Flade potentials of three important
engineering materials are (approx.):

+0.63 V for iron (Fe),

+0.2 V for nickel (Ni) and,

-0.2 V for chromium (Cr)

The negative value of the Flade potential for

chromium (-0.2 V) indicates that chromium has
favourable Gibbs free energy for the formation of
passive oxide film on its surface. The oxide film is
formed at much lower potentials than in other
engineering materials.
MM-435_Corrosion Degradation and Protection 10
 Passivity and Flade Potential
The Flade potential for iron (+0.63 V) indicates that only very strong and concentrated oxidizing agents will
form passive films on its surface.

However, even weak oxidizing agents form thin and very stable corrosion-resistant surface films on
chromium.

The 12-30% chromium content in stainless steel gives excellent corrosion resistance properties to steel
due to formation of a stable chromium oxide passive film on its surface.

Figure shows the standard Flade potential measured

for stainless steels with different
chromium contents.

As the chromium content in the alloy increases from

8% to 13%, the corrosion rate of iron decreases from
0.08 mm/year to very low values.

Other metals that have favorable reversible Flade

potentials and form passive film on
their surfaces include:
titanium, nickel, silicon, aluminum, tantalum, and
niobium etc..
MM-435_Corrosion Degradation and Protection 11
Factors affecting Passivity

1. Alloying addition
2. Anodic and Cathodic behavior
3. Chloride Ion concentration
4. Temperature
5. Velocity
6. Oxidizer Concentration

MM-435_Corrosion Degradation and Protection 12

Alloying addition

Decrease

Decrease

Decrease
ip.cd
Ef
Epp

icrit

MM-435_Corrosion Degradation and Protection 13

Anodic and Cathodic Behaviours

Change of Anodic Behavior

Change of Cathodic Behavior

MM-435_Corrosion Degradation and Protection 14

 -
Cl Concentration (or the effect of an inhibitor ion concen.)

MM-435_Corrosion Degradation and Protection 15

Temperature

An increase in temperature:

Increases the critical current density (icritical).

Decreases polarization and enhances the dissolution kinetics.
Decreases the passive range.

MM-435_Corrosion Degradation and Protection 16

Velocity
When a metal is under cathodic diffusion
control, agitation of the electrolyte increases
the current density and the rate of corrosion
increases up to a certain point.

At a particular velocity (critical velocity), the

rate becomes activation controlled rather than
diffusion controlled, and, hence, the rate of
corrosion becomes independent of velocity
(Fig).

Beyond a certain point agitation has no effect.

As icritical is exceeded, the metal attains passivity
and corrodes only very slowly.

MM-435_Corrosion Degradation and Protection 17

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention

MM-435_Corrosion Degradation and Protection 2

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Materials Selection

6. Protective Coatings

MM-435_Corrosion Degradation and Protection 3

Forms of Corrosion

1. Uniform Corrosion, 5. Intergranular Corrosion,

2. Galvanic Corrosion, 6. Selective leaching Corrosion,

3. Crevice Corrosion, 7. Erosion–Corrosion

4. Pitting Corrosion, 8. Stress Corrosion

MM-435_Corrosion Degradation and Protection 4

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

It often leaves behind a scale or deposit.

Examples include general rusting of steel and
iron.

This is probably the most common form of

corrosion.

It is also the least

objectionable because it can be predicted and
designed for with relative ease.

In a microscopic sense, the oxidation and

reduction reactions occur randomly over the
surface.

MM-435_Corrosion Degradation and Protection 5

Forms of Corrosion
Uniform Corrosion

Prevention:
• Paint
• Plate
• Sacrificial anode/Cathodic Protection

MM-435_Corrosion Degradation and Protection 6

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.

Described by Galvanic Series MM-435_Corrosion Degradation and Protection 7

Forms of Corrosion
Galvanic Corrosion
Causes:
Dissimilar metals
Electrolyte
Current Path

Prevention:
• Choose metals close in galvanic series
• Have large anode/cathode ratios
• Insulate dissimilar metals
• Use “Cathodic protection”

MM-435_Corrosion Degradation and Protection 8

Forms of Corrosion
Crevice Corrosion

this is a localized type of corrosion that 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

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

MM-435_Corrosion Degradation and Protection 9

Forms of Corrosion
Crevice Corrosion

Causes: concentration gradients in

electrolyte cause some areas high in ion
concentrations that accelerate oxidation

Prevention:
Weld – don’t rivet
Use non-absorbing gaskets
Polish surfaces
Add drains – avoid stagnant water

MM-435_Corrosion Degradation and Protection 10

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 11

Forms of Corrosion
Pitting Corrosion

Causes: A pit may be initiated by:

• a localized surface defect such as a scratch
• a slight variation in composition (concentration gradient)

Prevention:
Polish surfaces
Adjust composition; e.g., add Mo to SS

MM-435_Corrosion Degradation and Protection 12

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

Solutions: High temp heat treat to re-dissolve carbides

Lower carbon content (in SS) to minimize carbide formation
Alloy with a material that has stronger carbide formation (e.g., Ti or Nb)
MM-435_Corrosion Degradation and Protection 13
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

Prevention:
•Change design to minimize or eliminate fluid
turbulence and impingement effects.
•Use other materials that resist erosion
•Remove particulates from fluids

MM-435_Corrosion Degradation and Protection 14

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

Solution:
• Use protective coating to protect surfaces
• Use alternative materials

MM-435_Corrosion Degradation and Protection 15

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 nut and-bolt assembly. While
immersed in seawater, stress corrosion cracks formed along the bend at those
regions where the tensile stresses are the greatest.

Solution:
Reduce stress levels
Heat treatment
Atmosphere control
MM-435_Corrosion Degradation and Protection 16
 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

Solution:
Can be removed by “baking” the alloy

MM-435_Corrosion Degradation and Protection 17

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Materials Selection

6. Protective Coatings

MM-435_Corrosion Degradation and Protection 2

Corrosion Control by Inhibition
Outline….

1. What is inhibition

2. Scope and selection of inhibitors

3. How inhibitors work?

4. Inhibitors and polarization behaviors

5. Classification of inhibitors

6. Efficiency and Quantity of inhibitors

7. Application methods of inhibitors

MM-435_Corrosion Degradation and Protection 3

Corrosion Control by Inhibition
The practice of corrosion prevention by adding substances which can
significantly retard corrosion when added in small amounts is called inhibition.
Inhibitor:
Any reagent / substance capable of converting an active corrosion process into a
passive process and resulting in the suppression of corrosion.

Corrosion inhibitors market size, by end-use (USD Million) 2012

Consumption of Inhibitors: 2023

➢ Oil and gas exploration and production

➢ Petroleum refineries,
➢ Power Generation
➢ Chemical manufacturing,
➢ Heavy manufacturing,
➢ Water treatment and
➢ Product additive industries.
4
MM-435_Corrosion Degradation and Protection
Corrosion Control by Inhibition
Consumption of Inhibitors:

Total annual consumption in USA

alone doubled from approx. $600
million in 1982 to nearly $1.1 billion
in 1998.

Consumption grew annually at rate of

about 3% during 2013–2018.

MM-435_Corrosion Degradation and Protection 5

Corrosion Control by Inhibition
Scope of Inhibitors:
Corrosion control by use of inhibitors is extremely useful in many environments, however,
there are certain exceptions, such as:

1. Equipment and components subjected to turbulent flow

2. Systems operating above the stability limits of inhibitor

3. Equipment subjected to high velocity (beyond 4 m/s)

Caution..!!
In case of moving medium (environment):

erosion–corrosion
MM-435_Corrosion Degradation and Protection 6
Corrosion Control by Inhibition
Selection of Inhibitors (Considerations)

➢ The magnitude of suppression of uniform and localized corrosion.

➢ Long range effectiveness.

➢ Effect on bimetallic coupling to other metals joined to the main system.

➢ Effect of temperature and concentration on the performance of inhibitors.

➢ Effect on the existing condition of the system to be protected. For instance, a metallic
structure may be partly corroded; the important point would be to observe the effect
of inhibitor on the corroded areas.

➢ Effect of inhibitor on heat transfer characteristics.

➢ Toxicity and pollution problems.

➢ Economically and technically competitive with other considered inhibitors.

MM-435_Corrosion Degradation and Protection 7

Corrosion Control by Inhibition
Important Terms Related to Inhibitors

1. Additives. A typical reagent/inhibitor for treatment of a corrosive fluid contains

one main active constituent and one or more additives which assist in achieving
the purpose of the reagent.

2. Solvent. Keeps the active reagents in the liquid form and controls their viscosity.

3. Solubility. The active reagent should have the ability to dissolve in the solvent.

4. Dispersibility. It is a measure of the reagent’s ability to be transported by fluids

or gases. The treating reagents must exhibit a high dispersibility.

5. Emulsion. A heterogeneous system consisting of an immiscible liquid dispersed

in another liquid in the form of droplets.

6. Surfactants. It is a molecule with two components, each having different

chemical properties, one end is polar (hydrophillic), and the other end non-
polar (hydrophobic).
MM-435_Corrosion Degradation and Protection 8
Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Materials Selection

6. Protective Coatings

MM-435_Corrosion Degradation and Protection 9

Corrosion Control by Inhibition
Outline….

1. What is inhibition

2. Scope and selection of inhibitors

3. How inhibitors work?

4. Classification of inhibitors

5. Inhibitors and polarization behaviors

6. Efficiency and Quantity of inhibitors

7. Application methods of inhibitors

MM-435_Corrosion Degradation and Protection 10

Corrosion Control by Inhibition
How Inhibitors Work..??
Basic Components of a corrosion cell:

1. Anode
2. Cathode All these components should be present
3. Electrolyte in an electrochemical corrosion cell
4. Electrical connection

How many of these four components of a corrosion cell, may be

affected by a corrosion inhibitor to retard corrosion…??
3-components…!
The inhibitor may cause:

• increased polarization of the anode (anodic inhibition)

• increased polarization of the cathode (cathodic inhibition)

• increase in the electrical (ionic) resistance of the circuit (electrolyte) by

forming a thick deposit on the surface of the metal.

The resistance of the electronic conductor connecting the anode and cathode (i.e. the resistance of the
metal itself) is an intrinsic property and cannot be changed by corrosion inhibitors.
MM-435_Corrosion Degradation and Protection 11
Corrosion Control by Inhibition
Classification of Inhibitors

MM-435_Corrosion Degradation and Protection 12

Corrosion Control by Inhibition
Classification of Inhibitors based on certain functions
Passivating inhibitors:
➢ They have tendency to passivate the metal surface.
➢ They belong to the Anodic class of Inorganic Inhibitors

Precipitators:
➢ They remove undesirable suspended particles from the system, such as iron particles, by
precipitation.
➢ They belong to the Cathodic class of Inorganic Inhibitors

Vapour phase inhibitors :

➢ Certain types of inhibitors are used in the gas phase so they are called “vapour phase
inhibitors (VPIs)”
➢ They consist of heterocyclic compounds, such as cyclohexylamine.
➢ These inhibitors are used within packing crates during transportation by sea.
MM-435_Corrosion Degradation and Protection 13
Corrosion Control by Inhibition
Anodic Inhibitors
The class of inhibitors which decrease the rate of anodic reaction at the metal surface are
called ‘anodic inhibitors’.
➢ The number of metal ions dissolving is effectively reduced by anodic inhibitors.

➢ In terms of potential, addition of anodic inhibitors

reduces the difference of potential between the
anodic and cathodic sites.

➢ The potential of the anode shifts to the potential of

the cathode (towards noble direction).

➢ Consequently there is reduction in the driving force

for corrosion reaction to occur.

➢ The number of metal ions dissolving as a result of

anodic reaction is reduced.

MM-435_Corrosion Degradation and Protection 14

Corrosion Control by Inhibition
Anodic Inhibitors

(inhibited)

(Un-inhibited)

Icorr of the uninhibited electrolyte is higher than the Icorr’ of the electrolyte to which an anodic
inhibitor is added.

MM-435_Corrosion Degradation and Protection 15

Corrosion Control by Inhibition
Cathodic Inhibitors
The class of inhibitors which decrease the rate of cathodic reaction in a metal surface are
called ‘cathodic inhibitors’.

➢ Contrary to anodic inhibitors, the

cathodic inhibitors shift the
potential of the cathode to the
potential of the anode in the more
negative direction.

➢ Consequently there is reduction in

the driving force for corrosion
reaction to occur.

MM-435_Corrosion Degradation and Protection 16

Corrosion Control by Inhibition
Cathodic Inhibitors

(inhibited)

(Un-inhibited)

Icorr of the uninhibited electrolyte is higher than the Icorr’ of the electrolyte to which an
cathodic inhibitor is added.

MM-435_Corrosion Degradation and Protection 17

Corrosion Control by Inhibition
Mixed Inhibitors Mixed inhibitors show the characteristics of both the types of inhibitors (Anodic & Cathodic)

➢ The mixed inhibitors shift the open circuit

potential of anode to the more positive
direction; and that of the cathode to the
more negative direction.

➢ Consequently there is reduction in the

driving force for corrosion reaction to
occur.

MM-435_Corrosion Degradation and Protection 18

Corrosion Control by Inhibition

Mixed Inhibitor
MM-435_Corrosion Degradation and Protection 19
Corrosion Control by Inhibition

Anodic Inhibitors Cathodic Inhibitors Mixed Inhibitors

Examples: Examples: Examples:

➢ chromate, nitrite, ➢ Cu(HCO3)2, ➢ organic inhibitors containing
➢ molybdate, ➢ ZnSO4, Cr4(SO4)3, NiSO4, nitrogen and/or sulfur like:
➢ tungstate, ➢ polyphosphate, ➢ amines, triazoles, lkythiourea
➢ orthophosphate, ➢ Aminoethylene
➢ silicate, benzoate ➢ phosphate
MM-435_Corrosion Degradation and Protection 20
Corrosion Control by Inhibition
Inhibitors and Polarization Behaviour

Effect of Chloride Ion Concen & Sulphates.

Schematic representation of the effect of aggressive ions (Cl−) and

inhibitive ions (SO2 4−) on passivation of stainless steel

➢ Chloride ions break down the passivity and increase the rate of anodic
dissolution.

➢ Sulphates restore the passive behaviour by retarding rate of anodic

dissolution.
MM-435_Corrosion Degradation and Protection 21
Corrosion Control by Inhibition
Inhibitors and Polarization Behaviour

Effect of Chloride Ion Concen.

The three points, a, b and c, represent an anodic dissolution current corresponding to

a reduction current (cathodic current)

MM-435_Corrosion Degradation and Protection 22

Corrosion Control by Inhibition
Inhibitors and Polarization Behaviour Case-I
electrolyte composition and anodic polarization
behaviors

The cathodic curve intersects the anodic

polarization curve in the active region.

The corrosion potential is in the active

region, E1.

A high rate of metal dissolution is expected..!

MM-435_Corrosion Degradation and Protection 23

Corrosion Control by Inhibition
Inhibitors and Polarization Behaviour Case-II

The cathodic curve intersects the anodic

polarization curve at points E2 and E2’

This shows an unstable state of potential

which oscillates between E2 and E2’.

It represents a case of serious corrosion..!

MM-435_Corrosion Degradation and Protection 24

Corrosion Control by Inhibition
Inhibitors and Polarization Behaviour Case-III

The cathodic curve intersects at E3 in the

passivation range.

The potential is stable.

It represents a case of low corrosion..!

MM-435_Corrosion Degradation and Protection 25

Corrosion Control by Inhibition

The inhibitors (anodic or cathodic or mixed) protect

the metal in three possible ways:

(a) Physical adsorption

(b) Chemisorption

(c) Film formation / Synergistic adsorption

MM-435_Corrosion Degradation and Protection 26

Corrosion Control by Inhibition

(a) Physical adsorption

“caused by electrostatic forces between the inhibitor and the metal surface”
The metal surface can be either positively charged or negatively charged.

When a metal surface is positively charged, negative charged Adsorption

(anionic) inhibitor is adsorbed on the metal surface.

Adsorption

When a metal surface is negatively charged, positive charged

(cationic) inhibitor is adsorbed on the metal surface.

Physically adsorbed species can be removed from the surface by a

physical force (e.g. temperature and velocity).
MM-435_Corrosion Degradation and Protection 27
Corrosion Control by Inhibition

(a) Physical adsorption

No Adsorption
But, cationic species would not be adsorbed on a
positively charged surface..!!

No Adsorption

And anionic species would not be adsorbed on a

negatively charged surface..!!

Solution…??
MM-435_Corrosion Degradation and Protection 28
Corrosion Control by Inhibition

(b) Chemisorption
No Adsorption
➢ Chemisorption results in a strong binding of the
inhibitors with the metal surface.

➢ Positively charged ions can be adsorbed on a

positively charged metal surface in the
presence of negative ions which act as a bridge
between the two.

No Adsorption
+
➢ The process of chemisorption is accelerated
+
with time and temperature. +

MM-435_Corrosion Degradation and Protection 29

Corrosion Control by Inhibition

(a) Film formation

➢ The process of film formation is highly complex and the properties of films are dependent
upon its thickness, composition, solubility, temperature and other physical forces.

➢ These films help in the increased

passivation behaviour of the metal…!!

➢ Thin and Thick films…!!

MM-435_Corrosion Degradation and Protection 30

Corrosion Control by Inhibition
Efficiency of Inhibitors

➢ The efficiency of corrosion inhibition can be expressed as:

➢ Where;

Einh = efficiency of a corrosion inhibitor

CR0 = corrosion rate with zero inhibitor

CRI = corrosion rate in the presence of an inhibitor

MM-435_Corrosion Degradation and Protection 31

Corrosion Control by Inhibition
Quantity of Inhibitors

➢ The quantity of inhibitor required for a fluid to be inhibited can be obtained

by the relationship:

➢ Where;

Qinh = quantity of inhibitor, kg

Vfluid = volume of fluid to be inhibited

Cinh = inhibitor concentration, ppm

MM-435_Corrosion Degradation and Protection 32

Corrosion Control by Inhibition
Quantity of Inhibitors

➢ Example Problem
Calculate the dosage of sodium chromate required to be added to 500,000 litres of
water, if the concentration of sodium chromate is 5 ppm.

Solution

H 2O

(Liters)

1ppm = mg/L
= 1000ug/L
= 1ug/mL
MM-435_Corrosion Degradation and Protection 33
Corrosion Control by Inhibition
Techniques for applying the Inhibitors

➢ There are three well-known inhibitor application techniques

(1) Continuous injection
(2) Batch treatment
(3) Squeeze treatment

(1) Continuous Injection

inhibitors are injected in the system with a controlled rate to achieve inhibition objectives.
➢ Injection is achieved by means of an electric or gas driven chemical pump.

➢ The inhibitor is added at the point of turbulence to achieve uniform mixing.

➢ This method is used for municipal water supplies, cooling towers and oil wells, to
minimize scaling and corrosion problems

➢ It is a cost-effective system and widely practiced in oil industry.

MM-435_Corrosion Degradation and Protection 34
Corrosion Control by Inhibition
Techniques for applying the Inhibitors

(2) Batch Treatment / Slug Treatment

This is a periodic treatment in which a large quantity of chemicals is used
for an extended period of time. Commonly used to treat flowing oil wells.

➢ For batch treating, the tube displacement method is employed:

Several barrels of inhibitor are pumped into the tubing at the top. The
inhibitor is displaced to the bottom of the tubing with the fluids in the
oil well.

➢ It is applied in areas where continuous injection is not practical.

➢ The process is not economical as substantial amount of chemicals

may be wasted.
MM-435_Corrosion Degradation and Protection 35
Corrosion Control by Inhibition
Techniques for applying the Inhibitors
(3) Squeeze Treatment
This is a continuous treatment in which the liquid inhibitor is pumped down through the
tubing into the oil producing geological formation under low pressure which acts as a
chemical reserve.

➢ Continuous treatment of oil wells by inhibitors is achieved by this method.

➢ In oil wells, 1–2 drums of inhibitor is mixed with 10–20 bbl of water [1bbl
(British barrel) = 36 gallons], and is pumped into the well.

➢ The inhibitor is absorbed by the formation.

➢ It slowly escapes from the formation over a period of time to inhibit the
corrosive fluids

➢ A continuous slow release of the inhibitor from this producing formation

into the corrosive fluids is the key to the success of this method.

MM-435_Corrosion Degradation and Protection 36

Corrosion Control by Inhibition
Very brief detail on the following inhibitors can be found in the book:

➢ Scavengers

➢ Neutralizers

➢ Scale Inhibitors

➢ Rebar Inhibitors (reinforced concrete)

➢ Biocides

➢ Vapor phase inhibitors

MM-435_Corrosion Degradation and Protection 37
MM435_Corrosion Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Protective Coatings

6. Materials Selection

MM-435_Corrosion Degradation and Protection 2

Cathodic Protection
Electrochemical Corrosion Cell

1. Anode
2. Cathode Basic Components of a corrosion cell
3. Electrolyte
4. Electrical connection

An electrochemical corrosion cell between two areas A simple electrochemical corrosion cell
on single metal surface.
MM-435_Corrosion Degradation and Protection 3
Cathodic Protection
Basic Principle of CP

Anodic and cathodic reactions on a metal surface

Increased cathodic reaction and decreased anodic reaction (insignificant)

caused by introducing electrons from an external source
MM-435_Corrosion Degradation and Protection 4
Cathodic Protection
Sources of External Current

2 1
External Power Source Sacrificial Anode

5
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Electrical Basis of Cathodic Protection

If Ra + Rc is controlling resistance, and Ea − Ec has a finite value

of circuit resistance, the corrosion current (Icorr) would flow.

If complete freedom from corrosion is desired, Icorr must be made “0”

The corrosion current can be made zero by:

➢ making Ra + Rc equal to infinity or

➢ by equalizing the potential difference between Ec and Ea or
making (Ec − Ea) equal to zero.

The structure can be made cathode (negative) by supplying an electric current from outside
until its potential becomes equal to the potential of the anode, and the difference between
Ec and Ea completely disappears.
6
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Electrical Basis of Cathodic Protection

If corrosion is not to occur, I1 must be zero, therefore,

The above relationship suggests that enough current must be

provided by an external anode/source to flow through the
cathode resistance RC to make the cathode potential (EC) equal
to the anode potential (EA)

Complete Partial
Protection Protection

7
MM-435_Corrosion Degradation and Protection
Cathodic Protection
CP Systems

2
Impressed Current System 1
Galvanic Anode/ Sacrificial Anode System

9
MM-435_Corrosion Degradation and Protection
Cathodic Protection
1- Sacrificial Anode/Galvanic Current System

Vertical Anodes
Bed

Typical vertical galvanic anodes in soil

(arrows show the direction of convention positive current flow)
Typical 14.5 kg magnesium galvanic anode
10
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Sacrificial Anode/Galvanic Current System

Horizontal Anodes
Bed

Typical galvanic anode installation layout and test points

MM-435_Corrosion Degradation and Protection 11
Cathodic Protection
Sacrificial Anode/Galvanic Current System
Current out put of galvanic anodes:

➢ A 70 lb Mg anode practically gives a current of more

than 300 mA in a soil of average resistivity of 2000
ohms-cm

➢ Bare steel sometimes requires about 15 mA/ft2.

➢ So a single Mg anode can protect about 20 square feet
of the pipe in this case.

But…
➢ By applying a coating on steel, the current requirement
is reduced to 0.05 mA/ft2 ,
➢ And hence now one Mg anode can protect up to 6000 Typical 14.5 kg magnesium galvanic anode
square feet of the pipe surface.

MM-435_Corrosion Degradation and Protection 12

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Current out put of galvanic anodes:

➢ Is affected by the resistivity of the soil.

A higher current would be drawn in a low resistivity soil.

➢ Depends on geometry of the anode,

longer the length of the anode, higher the current output
would be.

➢ Depends on overall efficiency of the anodes.

The Mg anodes, for instance, does not have an efficiency Typical 14.5 kg magnesium galvanic anode

higher than 50%.

MM-435_Corrosion Degradation and Protection 13

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of Current Output of Mg anode
The current output of a magnesium alloy can be determined by the following relationships:

(That depends on anode weight)

MM-435_Corrosion Degradation and Protection 14

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of Current Output of Mg anode
Calculate the current output for a 32 pound packaged magnesium anode buried in a 1750 ohm-cm
soil for the protection of a bare pipeline where the expected resultant pipe-to-soil potential is −0.85 V.

For multiple anodes??

the current output obtained for a
single anode should be multiplied by
an adjusting factor (Table 5.5)

For 4 parallel anodes, 10 ft apart:

MM-435_Corrosion Degradation and Protection 15

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of No. of Anodes required
Suppose 10 000 ft of a bare 4 inch diameter pipeline is to be protected and if the resistance of soil is
1000 ohms per cubic centimeter, the pipe requires 1 mA/ft2 for protection. The anode output curve
shows 100 mA per anode in this type of soil. Calculate the number of anodes required.

Solution

105 anodes

MM-435_Corrosion Degradation and Protection 16

MM435_Corrosion Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Protective Coatings

6. Materials Selection

MM-435_Corrosion Degradation and Protection 2

Cathodic Protection
Electrochemical Corrosion Cell

1. Anode
2. Cathode Basic Components of a corrosion cell
3. Electrolyte
4. Electrical connection

An electrochemical corrosion cell between two areas A simple electrochemical corrosion cell
on single metal surface.
MM-435_Corrosion Degradation and Protection 3
Cathodic Protection
Basic Principle of CP

Anodic and cathodic reactions on a metal surface

Increased cathodic reaction and decreased anodic reaction (insignificant)

caused by introducing electrons from an external source
MM-435_Corrosion Degradation and Protection 4
Cathodic Protection
Sources of External Current

2 1
External Power Source Sacrificial Anode

5
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Electrical Basis of Cathodic Protection

If Ra + Rc is controlling resistance, and Ea − Ec has a finite value

of circuit resistance, the corrosion current (Icorr) would flow.

If complete freedom from corrosion is desired, Icorr must be made “0”

The corrosion current can be made zero by:

➢ making Ra + Rc equal to infinity or

➢ by equalizing the potential difference between Ec and Ea or
making (Ec − Ea) equal to zero.

The structure can be made cathode (negative) by supplying an electric current from outside
until its potential becomes equal to the potential of the anode, and the difference between
Ec and Ea completely disappears.
6
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Electrical Basis of Cathodic Protection

If corrosion is not to occur, I1 must be zero, therefore,

The above relationship suggests that enough current must be

provided by an external anode/source to flow through the
cathode resistance RC to make the cathode potential (EC) equal
to the anode potential (EA)

Complete Partial
Protection Protection

7
MM-435_Corrosion Degradation and Protection
Cathodic Protection
CP Systems

2
Impressed Current System 1
Galvanic Anode/ Sacrificial Anode System

9
MM-435_Corrosion Degradation and Protection
Cathodic Protection
1- Sacrificial Anode/Galvanic Current System

Vertical Anodes
Bed

Typical vertical galvanic anodes in soil

(arrows show the direction of convention positive current flow)
Typical 14.5 kg magnesium galvanic anode
10
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Sacrificial Anode/Galvanic Current System

Horizontal Anodes
Bed

Typical galvanic anode installation layout and test points

MM-435_Corrosion Degradation and Protection 11
Cathodic Protection
Sacrificial Anode/Galvanic Current System
Current out put of galvanic anodes:

➢ A 70 lb Mg anode practically gives a current of more

than 300 mA in a soil of average resistivity of 2000
ohms-cm

➢ Bare steel sometimes requires about 15 mA/ft2.

➢ So a single Mg anode can protect about 20 square feet
of the pipe in this case.

But…
➢ By applying a coating on steel, the current requirement
is reduced to 0.05 mA/ft2 ,
➢ And hence now one Mg anode can protect up to 6000 Typical 14.5 kg magnesium galvanic anode
square feet of the pipe surface.

MM-435_Corrosion Degradation and Protection 12

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Current out put of galvanic anodes:

➢ Is affected by the resistivity of the soil.

A higher current would be drawn in a low resistivity soil.

➢ Depends on geometry of the anode,

longer the length of the anode, higher the current output
would be.

➢ Depends on overall efficiency of the anodes.

The Mg anodes, for instance, does not have an efficiency Typical 14.5 kg magnesium galvanic anode

higher than 50%.

MM-435_Corrosion Degradation and Protection 13

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of Current Output of Mg anode
The current output of a magnesium alloy can be determined by the following relationships:

(That depends on anode weight)

MM-435_Corrosion Degradation and Protection 14

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of Current Output of Mg anode
Calculate the current output for a 32 pound packaged magnesium anode buried in a 1750 ohm-cm
soil for the protection of a bare pipeline where the expected resultant pipe-to-soil potential is −0.85 V.

For multiple anodes??

the current output obtained for a
single anode should be multiplied by
an adjusting factor (Table 5.5)

For 4 parallel anodes, 10 ft apart:

MM-435_Corrosion Degradation and Protection 15

Cathodic Protection
Sacrificial Anode/Galvanic Current System
Calculation of No. of Anodes required
Suppose 10 000 ft of a bare 4 inch diameter pipeline is to be protected and if the resistance of soil is
1000 ohms per cubic centimeter, the pipe requires 1 mA/ft2 for protection. The anode output curve
shows 100 mA per anode in this type of soil. Calculate the number of anodes required.

Solution

105 anodes

MM-435_Corrosion Degradation and Protection 16

Cathodic Protection
Sources of External Current

2 1
External Power Source Sacrificial Anode

17
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Sacrificial Anode/Galvanic Current System

(a) Advantages (b) Disadvantages

1. It requires no external source, which 1. It has limited applications compared to
might fail. impressed current.
2. It is economical. 2. Driving voltage is fixed and cannot be
3. It can be easily installed & maintained. manipulated, except by selecting Mg
4. It can be used in areas where the soil instead of Zn for example.
resistivity is low. 3. The cost of protection is high for bare
5. Lesser interference with the other systems (uncoated structures).
metallic structures is caused because of a 4. As no above-ground equipment is used,
relatively low current output. it is difficult to trace the protected
6. The current is evenly distributed system, unless contact posts are
provided.
MM-435_Corrosion Degradation and Protection 18
Cathodic Protection
CP Systems

2
Impressed Current System

19
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Impressed Current Cathodic System (ICCS)
In contrast to the galvanic anode system, the flow of current is forced from a DC source in the
impressed current system.

A transformer rectifier is the most important

component of the system.

Schematic diagram of impressed current

cathodic protection system
MM-435_Corrosion Degradation and Protection 20
Cathodic Protection
Impressed Current Cathodic System (ICCS)

MM-435_Corrosion Degradation and Protection 21

Cathodic Protection
Impressed Current Cathodic System (ICCS)

22
MM-435_Corrosion Degradation and Protection
 Cathodic Protection
Impressed Current Cathodic System (ICCS)

The negative terminal is attached to the structure (S) and

positive terminal to the ground-bed.

The anodes are made of:

➢ silicon cast iron,
➢ steel scrap,
➢ platinized titanium,
➢ graphite or
➢ lead silver.

➢ The individual anode leads are brought

into a junction box (J) which allows the
measurement of current output of individual
anodes.

➢ The anodes can also be connected directly to

the positive terminal of the rectifier by a ring
main cable system (direct connecting system)
Details of typical power impressed ground-bed
MM-435_Corrosion Degradation and Protection installation 23
Cathodic Protection
Backfill
The backfill for Cathodic Protection anodes serves the following
purposes:

➢ It isolates the anode from the surrounding soil and protects the anode from the effect
of chemicals contained in the soil.

➢ It provides a lower anode-to-earth resistance because of its low resistivity.

For impressed current anodes, the For Galvanic anodes, backfil is usually a
standard material is coke. mixture of gypsum, bentonite clay.

MM-435_Corrosion Degradation and Protection 24

 vertical anode installation
Cathodic Protection
ICCP-Ground Bed Designs

A heavy-wall deep impressed

current anode ground-bed

horizontal
MM-435_Corrosion Degradation and Protection anode installation 25
Cathodic Protection
Monitoring / Inspection of CP Systems

MM-435_Corrosion Degradation and Protection 26

Cathodic Protection
Matrix of CP Monitoring Techniques

MM-435_Corrosion Degradation and Protection 27

Cathodic Protection
Matrix of CP Monitoring Techniques

1) Close Interval Potential Survey (CIPS).

Assessing the level of CP on the pipeline

➢ CIPS is accomplished by making a direct connection

to the pipeline then measuring the polarized
2) AC Voltage Gradient (AC-VG) and DC Voltage Gradient (DC-VG). potential between the pipeline and an electrode
Coating integrity assessment test. on the ground.
➢ This works by creating a pulsed electrical signal on the pipeline.
Then the surveyor walks above it with two electrodes and looks ➢ The voltage is recorded to compare with the CP
criterion to ensure that adequate levels of CP are
for changes in the electrical current flowing through the ground.
reaching the pipeline.
➢ Anywhere there is a local change in voltage at the same frequency ➢ These readings are repeated by the surveyor
as the signal generator, there is likely a defect in the coating. walking above the pipeline and recording the
results.
➢ The surveyor then notes the location for further investigation.
28
MM-435_Corrosion Degradation and Protection
Cathodic Protection
Matrix of CP Monitoring Techniques
3) Pipe to Soil Potential (PSP) Survey

➢ Measure the voltage between the pipeline and the

adjacent soil electrolyte w.r.t. Copper/Coper Sulphate
Reference Electrode to assess the protection level.

➢ The protection criteria is generally followed by NACE RP -

01-69-2002

4) C-Scan Survey
Coating assessment

➢ Surveying the condition of the wrap or coating on

buried metal pipelines, and locating faults in the
wrap.

➢ C-SCAN uses two 3-dimentional field sensors to give

magnitude and direction of field.

➢ Instant results, enabling the user to immediately identify

areas of poor coating.
MM-435_Corrosion Degradation and Protection 29
Cathodic Protection
Remote Monitoring of CP Systems

MM-435_Corrosion Degradation and Protection 30

Cathodic Protection
Impressed Current Cathodic System (ICCS)

(a) Advantages (b) Disadvantages

1. One installation can protect a large area 1. Possibility of interference effects on
of metal. other buried structures.

2. The system can be used for a wide variety 2. Regular maintenance is essential.
of voltage and current requirement.
3. Electrical power cost is high.
3. Schemes can be designed for life in
excess of 20 years, if required. 4. Power failures can cause serious
problems, and faults may go unnoticed
4. Can be applied to a wide range of for long times.
structures.

5. Requires generally a small total number

of anodes. Alternate sources of Energy
for CP Systems
6. Automated controls

7. The use is less restricted by soil resistivity

MM-435_Corrosion Degradation and Protection 31

Cathodic Protection
Alternate sources of Energy for CP Systems

TR Units with battery Backup System

An integrated battery backup system with TR-Unit in
Corrosion Control Centre.
The system is designed to charge the battery bank when
AC supply is available & efficiently shifts the load to
battery backup during load shedding hours.

Solar Powered CP System enables to produce Direct

Current electricity from sun light which can be used to
charge/ re-charge a battery bank for further energizing
the CP system; independent of WAPDA supply.

Thermoelectric Generators
Facilitates in providing un-interrupted power supply to
operate CP System by converting heat energy into
electrical energy by taking the natural gas as inlet fuel
from existing gas network.
MM-435_Corrosion Degradation and Protection 32
Cathodic Protection
Cathodic Protection in Waters

Bracelet type of anode for

marine application.

MM-435_Corrosion Degradation and Protection 33

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Corrosion Prevention by Design

5. Protective Coatings

6. Materials Selection

MM-435_Corrosion Degradation and Protection 34

Anodic Protection
The corrosion protection achieved by maintaining an active-passive metal or alloy in
its passive state by applying an external anodic current.

The corrosion rate of a metal with an active-passive behaviour can be significantly

reduced by shifting the potential of the metal in the passive range.

Only a few systems exhibit this behavior in

an appreciable and usable way…e.g.
Titanium,
Stainless steels,
Steel and,
Nickel-based alloys

To produce passivation the critical current

density (icc) must be exceeded. The anodic
potential must then be maintained in the
passive region without allowing it to fall
back in the active region or getting into the
transpassive region
else protective anodic film can be damaged and even break down completely.
MM-435_Corrosion Degradation and Protection 35
Anodic Protection
Although a high current density may be required to cause passivation (> icc), only a
small current density is required to maintain it, and that in the passive region the
corrosion rate corresponds to the passive current density (ip)

Anodic protection’s unique features:

➢ the applied current is usually equal to

the corrosion rate of the protected
system. Thus, anodic protection not only
protects but also offers a direct means for
monitoring the corrosion rate of a system.

➢ low current requirements;

➢ large reductions in corrosion rate

(typically 10,000-fold or more)

➢ applicability to certain strong, hot

acids and other highly corrosive media.

MM-435_Corrosion Degradation and Protection 36

Anodic Protection
Since the potential must be maintained within the passive region, it is necessary to
use a potential controller capable of maintaining a constant electrode potential by
controlling the anodic current (Fig.)
Limitations

➢ Anodic protection can only be used in

relatively well-behaved or understood
environments since the composition of the
electrolyte and its temperature can greatly
influence the passive/active behaviour of a
metal or an alloy.

➢ The relative tendency for passivation is

strongly dependent on the interactions
between a metal and its environment and it
may vary extensively with changes in either.

The presence of impurities in the environment that retard the formation of a passive
film or accelerate its degradation is often detrimental.

MM-435_Corrosion Degradation and Protection 37

MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Protective Coatings

5. Corrosion Prevention by Design

6. Materials Selection

MM-435_Corrosion Degradation and Protection 2

Corrosion Control by Coatings
A coating is a covering that is applied to the surface of an object, usually referred to as the
substrate.
➢ The purpose of applying the coating may be decorative, functional, or both.

Conventional use of coatings: decorative and identification purposes

Industrial importance of coatings: recognized after World War II

The total amount of paint sold annually amounts to billions of gallons

In 2000, USA alone manufactured about 3.5 billion gallons of paint

About one-third of the production of paint is used to protect and decorate metal surfaces.

Applications of Coatings:
Forms of transport: Buried structures: Miscellaneous:
• trains, • tanks, • offshore structures,
• ships, • oil and gas pipelines • Iron structures and,
• automobiles, • all metallic equipment
• aeroplanes

MM-435_Corrosion Degradation and Protection 3

Corrosion Control by Coatings
Coatings & Corrosion Protection
➢ Coating can hardly be ignored in any corrosion protective scheme

➢ By applying coatings of high resistivity, such as epoxies, vinyls, chlorinated rubbers, etc.
the flow of electric current to the metal surface is impeded and corrosion cell can be
avoided

➢ Also, the higher the thickness of the coating, the higher would be the electrical
resistance of the coating.

Characteristics of Coatings for good corrosion resistance:

▪ a high degree of adhesion to the substrate

▪ minimum discontinuity in coating (porosity)
▪ a high resistance to the flow of electrons
▪ a sufficient thickness (the greater the thickness, the more the resistance)
▪ a low diffusion rate for ions such as Cl− and for H2O.
MM-435_Corrosion Degradation and Protection 4
Corrosion Control by Coatings
Objectives of Coatings
(1) Pleasant appearance

(2) Reduction in friction between two contacting surfaces.

marine fouling
(3) Change in light intensity; by selection of appropriate coatings the light intensity in
rooms and buildings can be varied as desired.

(4) Visibility; many combinations of colours are visible from large distances

(5) Modification of chemical, mechanical, thermal, electronic and optical properties of

materials.

(6) Application of thin coatings on low-cost substrates results in increased efficiency and cost
savings.

(7) Protection of equipment and structures from the environment by acting as a barrier
between the substrate and the aggressive environment, such as the marine and industrial
environments.

(8) Control of marine fouling; certain constituents in coating control the growth of
mildew (fungus) and marine fouling in seawater.
MM-435_Corrosion Degradation and Protection 5
Corrosion Control by Coatings
Classification of Coatings

Coatings can be classified in the following categories according to

corrosion resistance:

➢ (a) Barrier coatings

➢ (b) Conversion coatings

➢ (c) Anodic coatings

➢ (d) Cathodic coatings

MM-435_Corrosion Degradation and Protection 6

Corrosion Control by Coatings
Classification of Coatings
(a) Barrier coatings are of four types: –

1. anodic oxides: (e.g Al2O3)

A layer of Al2O3 is produced on aluminium surface. As the oxides are porous, they are
sealed by a solution of potassium dichromate. The object of sealing is to minimize porosity.

2. inorganic coatings
These include coatings/glazes like ceramics and glass. Glass coatings are virtually
impervious to water. Cement coatings are impervious as long as they are not mechanically
damaged.

3.organic coatings
Epoxy, polyurethane, chlorinated rubber and polyvinyl chloride coatings are extensively
used in industry. They serve as a barrier to water, oxygen, and prevent the occurrence of a
cathodic reaction beneath the coating.

4. inhibitive coatings
In several instances, inhibitors are added to form surface layers which serve as barriers to
the environment.
MM-435_Corrosion Degradation and Protection 7
Corrosion Control by Coatings
Classification of Coatings
(b) Conversion coatings

➢ Phosphate and chromate coatings are examples of conversion coatings.

➢ Conversion coatings are so-called because the surface metal is converted into
a compound having the desired porosity to act as a good base for a paint.

➢ If iron, phosphate (phosphating) is used where the following reaction takes place:

➢ The corrosion resistance is enhanced by phosphating.

MM-435_Corrosion Degradation and Protection 8

Corrosion Control by Coatings
Classification of Coatings
(c) Anodic coatings
➢ These are the coatings which are anodic (electronegative) to the substrate.
➢ For example: zinc, aluminium or cadmium coatings on steel substrate.
➢ Such coatings are generally called sacrificial coatings as they protect the
substrate at the expense of their own corrosion and oxidation.
(d) Cathodic coatings
➢ In this type of coatings, the metals which are deposited are electropositive (cathode) to
the substrate.
➢ For instance, for copper coated steel, copper (E◦=+0.337 V) is positive to steel (E◦=−0.440 V).

(e) Miscellaneous coatings

➢ These include glass coatings, porcelain coatings and high-temperature coatings.

MM-435_Corrosion Degradation and Protection 9

Corrosion Control by Coatings
Paints, Coatings & Linings
(a) Paints
➢ A paint is a pigmented liquid composition containing drying oils alone or drying
oils in combination with resins which form a solid protective and adherent film
after application as a thin layer.
(b) Coatings
➢ A coating is any material composed of metals or any synthetic resin or
inorganic silicate polymer which forms a continuous film over a surface after
application and is resistant to corrosive environments.

(c) Linings
➢ A lining is essentially a film/layer of material applied to the
inner surface of a vessel or pipeline designed to hold the
liquids or slurries. MM-435_Corrosion Degradation and Protection 10
Corrosion Control by Coatings
Paints, Coatings & Linings

(a) Paints

MM-435_Corrosion Degradation and Protection 11

Corrosion Control by Coatings
Paints, Coatings & Linings
(a) Paints

MM-435_Corrosion Degradation and Protection 12

Corrosion Control by Coatings
Paints, Coatings & Linings
(b) Coatings (metallic)
➢ The use of metallic coatings is only justified by longer life as they are
substantially more expensive than the organic coatings.

➢ Metallic coatings protect the substrate either by acting as a barrier between

the environment and the substrate or by corroding preferentially with
reference to the substrate.

➢ Methods for applying metallic coatings:

(a) Electroplating/electrodeposition (e) Diffusion

(b) Chemical vapor deposition (f) Spraying
(c) Physical vapor deposition (g) Welding, cladding, bonding
(d) Hot dipping (h) Miscellaneous methods.
MM-435_Corrosion Degradation and Protection 13
Corrosion Control by Coatings
Paints, Coatings & Linings
(b) Coatings (metallic)

MM-435_Corrosion Degradation and Protection 14

Corrosion Control by Coatings
Paints, Coatings & Linings
(b) Coatings (metallic)

MM-435_Corrosion Degradation and Protection 15

Corrosion Control by Coatings
Paints, Coatings & Linings
(b) Coatings (metallic)

Hot dip galvanizing process

MM-435_Corrosion Degradation and Protection 16

Corrosion Control by Coatings
Paints, Coatings & Linings
(b) Coatings (metallic)

MM-435_Corrosion Degradation and Protection 17

Corrosion Control by Coatings
Failures of Paints and Coatings
A mechanistic understanding of failures of paints and coatings is important.

The failures can be divided in four categories:

(a) Formulation-related failures

(b) Adhesion-related failures
(c) Application-related failures
(d) Design-related failures

Selected failure categories are described on next slides...!!

MM-435_Corrosion Degradation and Protection 18

Corrosion Control by Coatings
Failures of Paints and Coatings
(a) Formulation Failures
Chalking: It is the failure of a coating by the formation of a powdery
layer on a coating surface.
As the powder is white, the failure is referred to as chalking.
Mechanism: The binder of the coating disintegrates due to severe
sunlight and leaves the pigments which were held by it.
The binder continues to disintegrate until corrosion starts to develop
on the substrate and the coating surface is worn out.
A pigment may interact with ultraviolet radiation and breakdown.
A change in the color of a pigment indicates chalking.
Prevention (1) Select an appropriate combination of binder and pigment on the basis of
experience.
(2) Select pigments with a least tendency for chalking.
(3) Remove loose chalk deposits and apply a new coating system.
MM-435_Corrosion Degradation and Protection 19
Corrosion Control by Coatings
Failures of Paints and Coatings
(a) Formulation Failures
Erosion: It is the failure of a coating due to erosion by high winds
and sand particles, mostly encountered in deserts.

Mechanism:
In erosion, it is the high winds or sand particles which hit
the coating and disintegrate it.

Once the coating is disintegrated and the substrate is Erosion

exposed, corrosion proceeds rapidly on the substrate,

particularly in a humid environment.

MM-435_Corrosion Degradation and Protection 20

Corrosion Control by Coatings
Failures of Paints and Coatings
(a) Formulation Failures
Checking:
Small check-board patterns are formed on the surface of a
coating as it ages. The coating becomes harder and the
brittleness increases as it ages.
Checking

Alligatoring:
It is a film rupture caused by the application of a
hard dry brittle film over a more softer and
extensible film. The failed surface of the coating
resembles the hide of an alligator, hence the name
alligatoring.
It is also called crazing.
MM-435_Corrosion Degradation and Protection 21
Corrosion Control by Coatings
Failures of Paints and Coatings
(a) Formulation Failures
Cracking:
The surface of a coating cracks due to weathering and aging
similar to alligatoring.
Cracking may also be caused by a fast curing rate.

Wrinkling:
It is the appearance of wrinkles on the
surface of the coating

The basic reason in Checking, alligatoring, cracking and

wrinkling is the introduction of stresses in the coating Wrinkling
due to shrinkage.

MM-435_Corrosion Degradation and Protection 22

Corrosion Control by Coatings
Failures of Paints and Coatings
(b) Adhesion Related Failures
These failures occur due to the lack of adhesion of the coatings to the metal.

The reasons for lack of adhesion may be due to:

1) Poor surface preparation

2) Poor application method
3) Higher Film thickness

Examples:
Blistering, Peeling, Flaking, Inter coat Delamination.

MM-435_Corrosion Degradation and Protection 23

Corrosion Control by Coatings
Failures of Paints and Coatings
(b) Adhesion Related Failures
Blistering:
This is the failure of a coating by the development of
large or small round hemispherical pimples from the
surface either dry or filled with a liquid.

Peeling
Peeling:
Peeling is the loss of adhesion resulting in
detachment and curling out of the paint film from
the substrate or between inter-coats.

MM-435_Corrosion Degradation and Protection 24

Corrosion Control by Coatings
Failures of Paints and Coatings
(b) Adhesion Related Failures
Flaking: Flaking

Flaking is the pulling away of the coating from the

substrate because of the hard and brittle nature of the
coating.

MM-435_Corrosion Degradation and Protection 25

 Pin Holes
Corrosion Control by Coatings
Failures of Paints and Coatings
(c) Failures due to Improper Applications
Holidays and Pin Holes:
This is a particular area in which a portion of the
substrate has been left uncoated while the rest of
Holidays
the surface has been coated.
‘Holidays’ includes pinholes.

Spatering and Cratering:

Spatering
Spatering is the defect caused when only droplets of
the paint reach the substrate and a gap of bare metal
exists between the droplets.
Cratering is the formation of small bowl shaped
depressions in the paint or varnish film.
MM-435_Corrosion Degradation and Protection Cratering 26
Corrosion Control by Coatings
Selection of Coatings

Selection of an appropriate coating system is a prerequisite for the durability of coating.

The major factors that would influence the choice:

(1) Cost and life to the first maintenance

(2) Compatibility with the environment.

(3) Resistance to atmospheric pollution.

(4) Resistance to extreme climates.

(5) Ease of maintenance.

(6) Safety problem.

MM-435_Corrosion Degradation and Protection 27

MM435_Corrosion Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Corrosion Prevention Strategies

1. Corrosion Control by Inhibition (Inhibitors)

2. Cathodic Protection

3. Anodic Protection

4. Protective Coatings

5. Corrosion Prevention by Design

6. Materials Selection

MM-435_Corrosion Degradation and Protection 2

Corrosion Control by Design
“It is easier to erase a line on the drawing than replacing the component”

“corrosion prevention must start at the

blackboard, at the design stage”

A good design at the blackboard is no more costly

than a bad designed component in the finished
structure..!
The designers must have an understanding and
awareness of corrosion problems.
Materials Selection and Design..??
Materials and design are complimentary to each other and
neither of the two can be ignored.

Even a material, like 90-10 copper–nickel may fail prematurely as a condenser tube
material, if the flow velocity of salt water or seawater is not given a due
consideration for a smooth flow in the tube design.
MM-435_Corrosion Degradation and Protection 3
Corrosion Control by Design
Service Life of Equipment

MM-435_Corrosion Degradation and Protection 4

Corrosion Control by Design
Service Life of Equipment
A good design to prevent corrosion must be compatible with the corrosive environment.

Major contributors to corrosive environments

MM-435_Corrosion Degradation and Protection 5
Corrosion Control by Design
Service Life of Equipment

A good engineering design should:

➢ provide a maintenance-free service

➢ satisfy the end user

➢ be Cost effective

However, there are several areas that can cause equipment failures even with good design
as shown below:

➢ Breakdown of protective system

➢ Poor fabrication
➢ Lack of accessibility (for maintenance)
➢ Structural heterogeneity in materials
➢ Operating conditions
MM-435_Corrosion Degradation and Protection 6
Corrosion Control by Design
Areas Requiring Attention at Design Stage

■ Bimetallic contacts ■ Features which reduce the paint thickness

■ Faying surface ■ Contact with moisture absorbent materials
■ Crevices ■ Welds & Joints (threaded, riveted and screwed)
■ Moisture traps ■ Oil, grease and rust patches
■ Water traps ■ Closed sections and entrapment areas
■ Fluid movements ■ Mechanical factors
■ Inaccessibility ■ Corrosion awareness
■ Areas of condensation

MM-435_Corrosion Degradation and Protection 7

Corrosion Control by Design
Bimetallic Contact

a) Difference of potential

➢ Dissimilar metals

➢ Concentration gradients

MM-435_Corrosion Degradation and Protection 8

Corrosion Control by Design
Bimetallic Contact

b) Difference of Area Ratios

MM-435_Corrosion Degradation and Protection 9

Corrosion Control by Design
Deposition of impurities, deposits, debris, dirt

MM-435_Corrosion Degradation and Protection 10

Corrosion Control by Design
Deposition of impurities, deposits, debris, dirt

Not Good for dirt removal Good for dirt removal

MM-435_Corrosion Degradation and Protection 11

Corrosion Control by Design
Preventing water residence time
Rain water

Rain Water

MM-435_Corrosion Degradation and Protection 12

Corrosion Control by Design
Preventing water residence time

Rain water

Rain Water

MM-435_Corrosion Degradation and Protection 13

Corrosion Control by Design
Preventing water residence time

MM-435_Corrosion Degradation and Protection 14

Corrosion Control by Design
Preventing water residence time

Better

Better

MM-435_Corrosion Degradation and Protection 15

Corrosion Control by Design
Corrosion due to insulations

Initiation of corrosion of water heaters

by ingress of moisture in insulation

MM-435_Corrosion Degradation and Protection 16

Corrosion Control by Design
Corrosion due to insulations

MM-435_Corrosion Degradation and Protection 17

Corrosion Control by Design
Corrosion due to Crevices

MM-435_Corrosion Degradation and Protection 18

Corrosion Control by Design
Accessibility for Maintenance

MM-435_Corrosion Degradation and Protection 19

Corrosion Control by Design
Uniform Protective Coatings

MM-435_Corrosion Degradation and Protection 20

Corrosion Control by Design
Uniform Protective Coatings

Shapes difficult for coating

MM-435_Corrosion Degradation and Protection 21

Corrosion Control by Design
Uniform Protective Coatings

MM-435_Corrosion Degradation and Protection 22

Corrosion Control by Design
Incomplete drainage
Designs for Liquid Containers
Sharp corners

complete drainage (b) (a)

Sharp corners

complete drainage

(d) (c) No
Sharp corners

(e)
MM-435_Corrosion Degradation and Protection 23
Corrosion Control by Design
Designs for Liquid Containers Bimetallic couple

Stagnant Area
No couple

(a)

Clear flow
No stagnancy
(b)
MM-435_Corrosion Degradation and Protection 24
Corrosion Control by Design
Joints & Faying Surfaces

Copper

Aluminum

Steel rivet

Bad design bolted/riveted Joint

Good design bolted joint
MM-435_Corrosion Degradation and Protection 25
Corrosion Control by Design
Joints & Faying Surfaces

MM-435_Corrosion Degradation and Protection 26

Corrosion Control by Design
Joints & Faying Surfaces

MM-435_Corrosion Degradation and Protection Better 27

Corrosion Control by Design
Joints & Faying Surfaces

MM-435_Corrosion Degradation and Protection 28

Corrosion Control by Design
Joints & Faying Surfaces

MM-435_Corrosion Degradation and Protection 29

Corrosion Control by Design
Joints & Faying Surfaces

MM-435_Corrosion Degradation and Protection 30

Corrosion Control by Design
Joints & Faying Surfaces

How would be the practice of putting dissimilar pipes in the same trench..??

MM-435_Corrosion Degradation and Protection 31

Corrosion Control by Design
Flowing Water systems

MM-435_Corrosion Degradation and Protection 32

Corrosion Control by Design
Flowing Water systems

MM-435_Corrosion Degradation and Protection 33

Corrosion Control by Design
Concrete foundation of metallic structures

MM-435_Corrosion Degradation and Protection 34

Corrosion Control by Design
Bottom of metallic Tanks

MM-435_Corrosion Degradation and Protection 35

 Grading Policy Confirmed..!
Provisional..!
Assignments/Case Studies ( 2/4 ) = 4% Assignments (3) = 07%

Quizzes ( 6 ) = 20% Quizzes ( 4 ) = 16%

Midterm Exam = 30%
Midterm Exam = 30%
Course Project/CEP = 6%
Final Exam = 40% Course Project/CEP = 05%

Final Exam = 42%

Finals’ Course:
➢ Contents discussed in the classes..!!

➢ Corrosion Monitoring/Testing

➢ Chapters # 3 (Corrosion Kinetics) + 5 (Cathodic Protection) + 6 (Inhibitors) + 7 (Coatings)

+ 8 (Design) from book “Principles of Corrosion Engineering and Corrosion Control”
by Zaki Ahmad

Do practice the numericals..! 36

MM-435_Corrosion Degradation and Protection
 That’s it from me…!!

Now its your turn to perform in the finals…!!

Any suggestions for the improvement of the course ( contents + delivery )…Welcome!

Good Luck for the Finals…!!

MM-435_Corrosion Degradation and Protection 37