MSE 424 Corrosion and Materials Protection

(Room 323, Block 3)

Week-6-10 Lectures
Abdul Wadood (PhD), Assistant Professor
Department of Materials Science and
Engineering
Room# 211 (MSE)
Visiting Hours: 13:00 15:00
Attendance: 80% as per Institute policy
1

MSE-424 Corrosion and Materials Protection

Grading Policy:
Quizes: 5 (15%); Next Quiz = Wed; 9/3/2016

Presentation: 1 (5%)
Assignment: 1 (3%)
3 OHTs: 27%

Final: 50%
2

 Presentation:
Select some incident due to corrosion.
Find out the literature survey/investigation
report related to this incident. Remedies to
ovoid such incidents.
Your own comments/critical analysis is
also required.
Presentations in Week-8

Reference Book

Text Book

 The most important rule is that the designer,

fabricator, and galvanizer should work
together before the product is manufactured.
This three-way communication can
eliminate most galvanizing problems.
The designer can better appreciate hot dip
galvanizing design requirements if the basic
steps of the galvanizing process are
understood.

Zero Resistance Ammeter (ZRA)

A zero resistance ammeter (ZRA) is a current to voltage converter
that produces a voltage output proportional to the current flowing
between its input terminals while imposing a 'zero' voltage drop to
the external circuit.
In corrosion test a ZRA is typically used to measure the galvanic
coupling current between two dissimilar electrodes.
An interesting application is when the coupling current between
two nominally identical electrodes is measured. If both electrodes
were identical then very little coupling current would flow.
In real situations these electrodes will be slightly different, one
being more anodic or cathodic than the other and a small coupling
current will exist.

 Anodic reactions in corrosion :

Metal Corrosion : M M+n + ne Ferrous ion oxidation : Fe2+ Fe3+ + e Oxygen evolution : 2H2O O2+ 4H+ + 4e Cathodic reactions in corrosion :
hydrogen evolution in acid sol. : 2H+ + 2e H2
oxygen reduction in acid sol. : O2 + 4H+ + 4e 2H2O
oxygen reduction in neutral or basic sol. : O2+ 2H2O +
4e 4OH metal ion reduction : M+3 + e M+2
metal deposition : M+ + e M
Increasing the total reduction rate increases the rate of
corrosion. Thus, it is possible to reduce corrosion by
reducing the rate of either reaction:
- removing oxidizer
- coating the surface of metal with paint or nonconducting film.
- addition of corrosion inhibitors

-- Cost: 4 to 5% of the Gross National Product (GNP)*

-- this amounts to just over $400 billion/yr**
* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction to
Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc., 1985.
**Economic Report of the President (1998).

 The term 'polarization' derives from the early 19th-century

discovery that electrolysis causes the elements in an electrolyte to
be attracted towards one or the other pole.
Thus, initially 'polarization' was a description of electrolysis
itself.
In time, as more electrochemical processes were invented, the
term 'polarization' evolved to denote any (potentially
undesirable/desireable) side-effects that occur at the interface
between electrolyte and electrodes.
Polarization isolate the electrode from the electrolyte,
impeding/delaying reaction and charge transfer between the two.

 In electrochemistry, polarization is a collective term for

certain mechanical side-effects (of an electrochemical
process) by which isolating barriers develop at the
interface between electrode and electrolyte.
These side-effects influence the reaction mechanisms, as
well as the chemical kinetics of corrosion and metal
deposition.
These mechanical side-effects are:
activation polarization: the accumulation of gasses (or
other products) at the interface between electrode and
electrolyte.
concentration polarization: uneven depletion of reagents in
the electrolyte cause concentration gradients in boundary
layers.

Passivity

Passivity

Presentation
Marks Distribution

1.
2.
3.
4.
15%
5.
6.
10%
7.
10%

Team Work
20%
Formal dress on presentation day
10%
Literature Survey/Reports about Incident 20%
Technical Discussion
Critical Analysis
15%
Time Management (In time Presentation)
Answers to Questions
Total Marks

100
31

 Presentation:
Select some incident due to corrosion. Find
out the literature survey/investigation report
related to this incident. Remedies to ovoid
such incidents.
Your own comments/critical analysis is also
required.
Presentations in Week-8

Reference Book

Text Book

 The PillingBedworth ratio (PB ratio), in corrosion of

metals, is the ratio of the volume of the metal oxide to the
volume of the corresponding metal (from which the oxide is
created).
On the basis of the PB ratio, it can be judged if the metal
is likely to passivate in dry air by creation of a protective
oxide layer.

N.B. Pilling and R.E. Bedworth suggested in 1923 that metals can be classed into two categories:
those that form protective oxides, and those that cannot.

They ascribed the protectiveness of the oxide to the volume the oxide takes in comparison to the
volume of the metal used to produce this oxide in a corrosion process in dry air.

The oxide layer would be un-protective if the ratio is less than unity because the film that forms on
the metal surface is porous and/or cracked.

Conversely, the metals with the ratio higher than 1 tend to be protective because they form an
effective barrier that prevents the gas from further oxidizing the metal.

RPB < 1: the oxide coating layer is too thin, likely broken and provides no protective effect (for
example magnesium)

RPB > 2: the oxide coating chips off and provides no protective effect (example iron)
1 < RPB < 2: the oxide coating is passivating and provides a protecting effect against further
surface oxidation (examples aluminium, titanium, chromium-containing steels).
However, the exceptions to the above P-B ratio rules are numerous. Many of the exceptions can
be attributed to the mechanism of the oxide growth: the underlying assumption in the P-B ratio is
that oxygen needs to diffuse through the oxide layer to the metal surface; in reality, it is often the
metal ion that diffuses to the air-oxide interface.

Metal
Zinc
Calcium
Magnesium
Aluminium
Lead
Platinum
Zirconium
Hafnium
Nickel
Iron
Titanium
Chromium
Iron
Iron
Silicon
Tantalum
Vanadium

Metal oxide
Zinc oxide
Calcium oxide
Magnesium oxide
Aluminium oxide
Lead(II) oxide
Platinum(II) oxide
Zirconium(IV) oxide
Hafnium(IV) oxide
Nickel(II) oxide
Iron(II) oxide
Titanium(IV) oxide
Chromium(III) oxide
Iron(II,III) oxide
Iron(III) oxide
Silicon dioxide
Tantalum(V) oxide
Vanadium(V) oxide

RPB
1.58
0.64
0.81
1.28
1.28
1.56
1.56
1.62
1.65
1.7
1.73
2.07
2.10
2.14
2.15
2.47
3.25

Selective leaching

Removal of one element from a solid alloy by corrosion process is called

selective leaching, e.g. dezincification, graphitizing, de-aluminizing, decobaltification etc.
Dezincification
Selective removal of zinc from brass, leaving a red copper color appearance
is an example of dezincification.
Dezincification can be either uniform (<15% Zn) and localized (low brasses)
Uniform attacked is common in acidic environments while localized is found
in neutral and alkaline environments (preferably under stagnant conditions)
Mechanism:
Zinc dissolve and cause vacancy in lattice structure
Under deficient condition of oxygen in a corrosion system
(metal/environment), there is race to get oxygen. More reactive species will
act preferentially
Prevention
Reducing environment aggressiveness (oxygen removing)
Cathodic protection is economical
Selecting proper material for certain environment
Alloying additions (Sn, As etc.)

Anodic/cathodic electrodes

Anodic/cathodic phases at the

microstructural level

How can galvanic cells form?

Differences in the concentration of the

Metal ion
Differences in the concentration of
oxygen

Difference in the residual stress levels

 Different phases (even of the same metal) can form a galvanic couple at the
microstructural level (In steel Cementite is noble as compared to Ferrite)

Galvanic cell may be set up due to concentration differences of the metal ion in the
electrolyte A concentration cell
Metal ion deficient anodic
Metal ion excess cathodic
A concentration cell can form due to differences in oxygen concentration
Oxygen deficient region anodic
O2 + 2H2O + 4e 4OH
Oxygen rich region
cathodic

A galvanic cell can form due to different residual stresses in the same metal
Stressed region more active anodic
Stress free region
cathodic

 De-aluminization is a type of corrosion that consists of the

selective loss of aluminum in aluminum bronzes (Cu-Sn)
and nickel-aluminum bronzes.
Adverse effects on the ultimate tensile strength of
components
Potential for non-ductile failure
Loss of leak tightness
It is a concern for nuclear power generation facilities that
utilize aluminum-bronze alloy piping and piping
components for the transportation.
Some aluminum alloys are susceptible to this form of
corrosion, particularly in seawater.

De-cobaltification
De-cobaltification is a corrosion process in which cobalt is
selectively leached from cobalt-base alloys.
It creates problems in the tooling/machining industries
where cobalt is leached by many of the amino alcohols
and amine-based additives found in almost all watermiscible machining fluids. Cobalt leaching is hazardous to
carbide tools as well.
De-cobaltification problems:
Reduced performance and life of the tool
Health problems in some workers, causing dermatitis and
respiratory problems
Disposal of contaminated wastewater

MICROSTRUCTURAL
mechanicallyEFFECTS
deformed metal or alloy

A
can experience galvanic corrosion due to
differences in atomic plane distortion and a
high dislocation density

 Improper heat treatment can cause

nonuniform microstructure and therefore,
galvanic-phase corrosion is enhanced in
corrosive media.
Galvanic corrosion can occur in a
polycrystalline alloys, such as pearlitic steels,
due to differences in microstructural phases.
Pearlite consists of ferrite and cementite ----galvanic microcells between ferrite (anode )
and cementite (cathode) are generated.

Standard emf series

EMF series
o
Vmetal
metal
Au
+1.420 V
Cu
+0.340
Pb
- 0.126
Sn
- 0.136
Ni
- 0.250
o
DV =
Co
- 0.277
0.153V
Cd
- 0.403
Fe
- 0.440
Cr
- 0.744
Zn
- 0.763
Al
- 1.662
Mg
- 2.262
Na
- 2.714
K
- 2.924

Metal with smaller

o
Vmetal
corrodes.

Ex: Cd-Ni cell

Galvanic series
Ranks the reactivity of metals/alloys in seawater
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
8

Inconel (super alloy): an alloy of nickel

containing chromium and iron, resistant
to corrosion at high temperatures

e flow

Galvanic Cell

Anode
Zn
(0.76)

Zn Zn2+ + 2e
oxidation

Cathode
Cu
(+0.34)

Cu2+ + 2e Cu
Reduction

Zn will corrode at the expense of Cu