Chapter 16

Corrosion and
Degradation of
Materials
CORROSION AND DEGRADATION OF
MATERIALS
Cost of Corrosion
Fundamentals of Corrosion
Electrochemical reactions
EMF and Galvanic Series
Concentration and Temperature (Nernst)
Corrosion rate
Corrosion prediction (likelihood)
Polarization
Protection Methods
2
What is the.
Cost of Corrosion?


4
The Cost of Corrosion
Significance of Corrosion
on Infrastructure
Engineer finds corrosion in collapsed bridge at
North Carolina speedway (2000)
Corrosion & Catastrophic Failure.
A Concrete bridge failure
Fundamental Components
Corrosion can be defined as the deterioration of material
by reaction to its environment.
Corrosion occurs because of the natural tendency for
most metals to return to their natural state; e.g., iron in the
presence of moist air will revert to its natural state, iron
oxide.
4 required components in an electrochemical corrosion
cell: 1) An anode; 2) A cathode; 3) A conducting
environment for ionic movement (electrolyte); 4) An
electrical connection between the anode and cathode for
the flow of electron current.
If any of the above components is missing or disabled,
the electrochemical corrosion process will be stopped.
10
11
Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:


Zn Zn
2+
+ 2e

2H
+
+2e

H
2
(gas)
Other reduction reactions in solutions with dissolved oxygen:
-- acidic solution -- neutral or basic solution


O
2
+4H
+
+4e

2H
2
O


O
2
+2H
2
O+4e

4(OH)

Electrochemical Corrosion
Zinc
Oxidation reaction
Zn
Zn
2+
2e
-
Acid
solution
reduction reaction
H
+
H
+
H
2
(gas)
H
+
H
+
H
+
H
+
H
+
flow of e
-

in the metal
Corrosion of zinc in an acid solution
12
Standard Hydrogen Electrode
Two outcomes:
0
o
metal
< V
(relative to Pt)
Standard Electrode Potential
-- Electrodeposition
-- Metal is the cathode (+)
M
n+

ions
ne
-
e
-
e
-
25C
1M M
n+
soln 1M H
+
soln
P
l
a
t
i
n
u
m

m
e
t
a
l
,

M

H
+
H
+
2e
-
0
o
metal
> V (relative to Pt)
-- Corrosion
-- Metal is the anode (-)
P
l
a
t
i
n
u
m



m
e
t
a
l
,

M



M
n+

ions
ne
-
H
2
(gas)
25C
1M M
n+
soln 1M H
+
soln
2e
-
e
-
e
-
H
+

H
+

13
Standard EMF Series
metal
o
Metal with smaller
V corrodes.
EMF series
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K
+1.420 V
+0.340
- 0.126
- 0.136
- 0.250
- 0.277
- 0.403
- 0.440
- 0.744
- 0.763
- 1.662
- 2.363
- 2.714
- 2.924
metal
V
metal
o
m
o
r
e

a
n
o
d
i
c

m
o
r
e

c
a
t
h
o
d
i
c

AV =
0.153V
o
-
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
25C Ni Cd
Cd
o
Ni
o
Ex: Cd-Ni cell
V < V Cd corrodes
Driving force
A driving force is necessary for electrons to
flow between the anodes and the cathodes.
The driving force is the difference in potential
between the anodic and cathodic sites.
This difference exists because each oxidation
or reduction reaction has associated with it a
potential determined by the tendency for the
reaction to take place spontaneously. The
potential is a measure of this tendency.
15
16
Galvanic Series
Ranking the reactivity of metals/alloys in seawater
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel (active)
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
m
o
r
e

a
n
o
d
i
c

(
a
c
t
i
v
e
)

m
o
r
e

c
a
t
h
o
d
i
c

(
i
n
e
r
t
)

18
Solution Concentration and Temperature
Ex: Cd-Ni cell with
standard 1 M solutions


V
Ni
o
V
Cd
o
= 0.153 V
-
Ni
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
Cd 25C
Ex: Cd-Ni cell with
non-standard solutions
Y
X
ln
nF
RT
V V V V =
o
Cd
o
Ni Cd Ni
n = #e
-

per unit
oxid/red
reaction
(= 2 here)
F =
Faraday's
constant
= 96,500
C/mol.
-
+
Ni
Y M
Ni
2+
solution
X M
Cd
2 +
solution
Cd
T
Kinetics, Polarization, Corrosion Rates
While it is necessary to determine corrosion tendencies by
measuring potentials, it will not be sufficient to determine
whether a given metal or alloy will suffer corrosion under a given
set of environmental conditions.
Even though the tendency for corrosion may be high, the rate of
corrosion may be very low, so corrosion may not be a problem.
Corrosion rates are determined by applying a current to produce
a polarization curve (the degree of potential change as a function
of the amount of current applied) for the metal surface whose
corrosion rate is being determined.
The variation of potential as a function of current (a polarization
curve) enables the study of concentration and activation
processes on the rate at which anodic or cathodic reactions can
transfer electrons.
Polarization measurements can thereby determine the rate of
the reactions that are involved in the corrosion process (the
corrosion rate).
19
Anodic Polarization Curve -1
Types of Tests
ANODIC POLARIZATION CURVE
this curve is usually scanned from 20mV below the Eoc upwards
by scanning at a slow rate (.2mV/s) this curve can be used to identify
several corrosion mechanisms shown below
i
p
- passive current density
E
pp
- primary passivation potential
i
crit
- critical current density
E
trans
- transpassive potential
This curve is usually
scanned from 20 mV
below the E
oc
(open circuit
potential) upward.
The curve can be used to
identify the following
corrosion regions:
The degree of polarization is a measure of how the rates for anodic
and cathodic reactions are slowed by various environmental factors
(concentration of metal ions, dissolved oxygen in solution, diffusion
limitations; referred to as concentration polarization) and/or surface
process (activation polarization).
All electrochemical reactions consist of a sequence of steps that occur
in series at the interface between the metal electrode and the solution.
Activation polarization is where the reaction is limited (controlled) by
the slowest rate reaction of the steps (adsorption H
+
, film formation,
ease of release of electrons, called the activation polarization).
Types of Corrosion
Uniform Attack General Corrosion
Galvanic Corrosion
Crevice Corrosion
Pitting
Intergranular Corrosion
Selective Leaching
Erosion Corrosion
Stress Corrosion
Uniform Corrosion
23
Formerly a ship
Dissimilar metals are
physically joined in the
presence of an electrolyte.
The more anodic metal
corrodes.
Galvanic
Bilge pump -
Magnesium shell cast
around a steel core.
Aluminum Alloys
Traditionally, structural aluminum alloys in
aircraft have been 2024-T3 in damage critical
areas and 7075-T6 in strength critical areas.
As aircraft structures became more complex,
skin materials became an integral part of the
structure and SCC became more prevalent.
The high performance aircraft designed since
1945 have made extensive use of skin
structures machined from thick plates and
extrusions. The residual stresses induced by
heat treatment in conjunction with those from
machining made these materials sensitive to
SCC.
Stress Corrosion Cracking, SCC
A structure that has SCC sensitivity, if
subjected to stresses and then exposed
to a corrosive environment, may initiate
cracks and crack growth well below the
yield strength of the metal.
Consequently, no corrosion products
are visible, making it difficult to detect or
prevent; fine cracks can penetrate
deeply into the part.
Narrow and confined spaces.
Crevice Corrosion
Pitting
Pitting is a localized form of
corrosive attack. Pitting corrosion
is typified by the formation of holes
or pits on the metal
surface. Pitting can cause failure,
yet the total corrosion, as
measured by weight loss, may be
minimal.
5th Century sword
Boiler tube
304
stainless
steel / acid
chloride
solution
Corrosion along
grain boundaries,
often where precipitate
particles form.
Intergranular
Combined chemical attack and
mechanical wear (e.g., pipe
elbows).
Erosion-corrosion
Brass water pump
Selective Leaching
Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-
Zn)]. Dezincification.
32
33
Energy Technology Developments
Using Gamry Electrochemical Instrumentation
Electrochemical cells used in energy technology include:
Batteries
Fuel Cells
Supercapacitors
Solar Cells
Batteries are the ultimate electrochemical device, so typically,
battery scientists understand and use electrochemistry as a
routine tool to develop and improve their products.
The challenge for these engineers is to higher energy densities
at lower prices.
A battery is a very active electrochemical device, so safety is an
important issue.
34
35
Types of Tests
3. Electrochemical Tests
because corrosion of metals is an electrochemical process, electrochemical
measurements are especially suited to it
8
they are extremely fast compared
to other corrosion tests and the
results are easily analyzed to find
corrosion rates
Open Circuit Potential Scans
Polarization Resistance
Potentiodynamic Curves
Galvanic Corrosion Tests
Electrochemical Impedence
Spectroscopy (EIS)
Types
Zn
+2 HCl solution
H
+
H
+
H
+
H
+
H
+
H
2
Cl
-
Cl
-
Zinc
e
-
e
-
Corrosion Test Methods
1: The measurement of the open circuit potential is very
easy and inexpensive, but is not considered to be very
reliable, since the potential tells nothing about the kinetics
of the process.
2: Linear polarization measurements are encumbered by
IR effects from the concrete; there is so much potential
drop in the concrete, that an accurate determination of the
potential of the rebar surface is very difficult.
3: Electrochemical impedance spectroscopy (EIS) can
overcome the difficulties of the concrete resistance.
Electrochemical Basics
Corrosion is an electrochemical phenomena
The simultaneous combination of electrical & chemical processes
Techniques involve either or both of:
Measuring voltage difference (thermodynamic)
Measuring current flow (kinetic)
Working electrode
Equipment material
Reference electrode
Maintains constant potential
Even at large currents
Counter (Secondary) electrode
Allows infinite current
E
I
R
e
f
e
r
e
n
c
e

E
l
e
c
t
r
o
d
e
W
o
r
k
i
n
g

E
l
e
c
t
r
o
d
e
S
e
c
o
n
d
a
r
y

E
l
e
c
t
r
o
d
e
E
I
R
e
f
e
r
e
n
c
e

E
l
e
c
t
r
o
d
e
W
o
r
k
i
n
g

E
l
e
c
t
r
o
d
e
S
e
c
o
n
d
a
r
y

E
l
e
c
t
r
o
d
e
Test Samples
EG&G Instruments: Potentiostat/Galvanostat
Model 273A
Comparison of Corrosion Potential vs Time
for MCI Treated Concrete with Untreated Samples
-300
-250
-200
-150
-100
-50
0
50
100
0 50 100 150 200 250
Time of Submersion (Days)
P
o
t
e
n
t
i
a
l
,

(
m
V
)
RF1-untreated MR1-rebar treated
MS1-surface treated MM1-mortar coated surface
Corrosion Potential vs Time, ASTM C876-91, Cortec MCI 2022 & 2021
Compared with Unprotected Concrete (Various Concrete Densities)
L=low density, H=high density
-600
-500
-400
-300
-200
-100
0
0 50 100 150 200 250 300 350 400 450
Time of Submersion (Days)
P
o
t
e
n
t
i
a
l
,

(
m
V
)
L untreated
L2021
L2022
H untreated
H2021
H2022
EIS Results, Bode Plots
LD=untreated low density concrete, 2S=MCI 2022/high density, 2L=MCI 2022/low density;
Concrete densities: low = 130 lbs/ft
3
, high = 150 lbs/ft
3
.
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04 1.00E+05
FREQUENCY (Hz)
l

Z

l


(
O
h
m
s
)
2L-Day 1 2L-Day 238 2L-Day 325
L-Day 1 L-Day 233 L-Day 332
2S-Day 1 2S-Day 236 2S-Day 327
Concrete Exterior & Interior
Concrete Interior (untreated)
The potential, polarization resistance and
current density data can provide useful
information about:

Corrosion state of the metal (active or
passive).

Estimates of the Tafel constants for input into
LPR analysis, corrosion rate measurement or
cathodic protection criteria.

Useful Parameters
Open Circuit Potentials
46
Types of Tests
Open Circuit Potentials
is a summation of the half-cell reaction potentials in a specific electrolyte
using a potentiostat it measures the potential of the working electrode with
respect to the reference electrode potential vs. time
these measurements are made under equilibrium conditions (ie. absence
of current flow ) to describe the thermodynamic equilibrium of an
electrochemical system
8
Aluminum (FS)
Zinc (BHD)
This electrochemical technique enables the measurement of the
instantaneous corrosion rate. It quantifies the amount of metal per unit
of area being corroding in a particular instant.
The method is based on the observation of the linearity of the
polarization curves near the potential (E
corr
). The slope expresses the
value of the polarization resistance (Rp) if the increment is close to
zero.
This Rp value is related to the corrosion current (Icorr) by means of
the expression:
Where A is the area of metal surface evenly polarized and B is a
constant that may vary from 13 to 52 mV. For steel embedded in
concrete, the best fit with parallel gravimetric losses results in B= 26
mV for actively corroding steel , and a value of B= 52 mV, when the
steel is passivated.
Polarization Resistance, Rp
Types of Tests
Now that we have found Rp we can sub it into the Stern-Geary
equation:
) ( 303 . 2
1
Bc Ba
BaBc
Rp
icorr
+
=
- Ba and Bc are the Tafel
Slopes and are
approximated to both be
.1 V
Using the icorr value, we can now solve for a
corrosion rate as we did before
it has been found that there is good correlation b/w
corrosion rates obtained by polarization resistance
and those obtained by weight loss
10
it is also non-destructive and little time is required
Polarization Resistance
Galvanic Corrosion Tests
48
Types of Tests
Galvanic Corrosion Tests
when two different metals are electrically
coupled in the presence of a conductive
solution, one of them corrodes at an
accelerated rate while the other is protected
this is important in sacrificial coatings
because the coating acts as the anode and the
substrate acts as the cathode
Graphite
Pt
Ti
Stainless Steel
Ni-Cu alloys
Ag
Ni alloys
Cu-Ni
Bronze
Brass
Pb-Sn solder
Cu
Sn
Low alloys steel
Low carbon steel
Al alloys
Al
Be
Zn
Mg
in order to correctly assess a sacrificial
coating we must look at the galvanic
couple that exists between the coating and
the substrate
11
In Seawater
More
Noble
More
Active
coating
substrate
Types of Tests
Galvanic Corrosion Tests
when two different metals are electrically
coupled in the presence of a conductive
solution, one of them corrodes at an
accelerated rate while the other is protected
this is important in sacrificial coatings
because the coating acts as the anode and the
substrate acts as the cathode
Graphite
Pt
Ti
Stainless Steel
Ni-Cu alloys
Ag
Ni alloys
Cu-Ni
Bronze
Brass
Pb-Sn solder
Cu
Sn
Low alloys steel
Low carbon steel
Al alloys
Al
Be
Zn
Mg
in order to correctly assess a sacrificial
coating we must look at the galvanic
couple that exists between the coating and
the substrate
11
In Seawater
More
Noble
More
Active
coating
substrate
Types of Tests
Galvanic Corrosion Tests
when two different metals are electrically
coupled in the presence of a conductive
solution, one of them corrodes at an
accelerated rate while the other is protected
this is important in sacrificial coatings
because the coating acts as the anode and the
substrate acts as the cathode
Graphite
Pt
Ti
Stainless Steel
Ni-Cu alloys
Ag
Ni alloys
Cu-Ni
Bronze
Brass
Pb-Sn solder
Cu
Sn
Low alloys steel
Low carbon steel
Al alloys
Al
Be
Zn
Mg
in order to correctly assess a sacrificial
coating we must look at the galvanic
couple that exists between the coating and
the substrate
11
In Seawater
More
Noble
More
Active
coating
substrate
Potentiodynamic Curves
49
Types of Tests
Potentiodynamic Curves
An electrochemical test that measures the current response to an
applied potential over a large potential range
this test is used to analyze the overall behavior of the coatings
corrosion protection
Evans Diagram Polarization Curve
2
H
+
+
2
e
-

H
2
M

M
+
+
e
-
E
log i
E
corr
i
corr
net +
current
net -
current
log i
i
applied
E
2
H
+
+
2
e
-

H
2
M

M
+
+
e
-
i
corr
E
corr
Tafel Extrapolation
50
Types of Tests
ANODIC POLARIZATION CURVE
another use of the polarization curve is for Tafel extrapolation
by extrapolating the straight portion of the curve back to the Ecorr we can
calculate the icorr and then corrosion rate
A straight portion of 1 order of magnitude is suggested for
accuracy
9
Anodic Tafel Slope (Ba)
icorr
Ecorr
Electrochemical Impedance Spectroscopy (EIS)
51
EIS has been successfully applied to the study
of corrosion systems and been proven to be a
powerful and accurate method for measuring
corrosion rates.
To access the charge transfer resistance or
polarization resistance that is proportional to
the corrosion rate at the monitored interface,
EIS results have to be interpreted with the help
of a model (see simple circuit model) of the
interface.
An important advantage of EIS over other
laboratory techniques is the possibility of using
very small amplitude signals without significantly
disturbing the properties being measured. To
make an EIS measurement, a small amplitude
signal, usually a voltage between 5 to 50 mV, is
applied to a specimen over a range of
frequencies of 0.001 Hz to 100,000 Hz.
The EIS instrument records the real (resistance)
and imaginary (capacitance) components of the
impedance response of the system.
Proposed Relationship between Corrosion Rate
and Remaining Service Life

icorr (A/cm
2
)
Severity of Damage
<0.5
no corrosion damage expected
0.5-2.7
corrosion damage possible in 10 to 15 years
2.7-27
corrosion damage expected in 2 to 10 years
>27
corrosion damage expected in 2 years or less
53
Use metals that passivate, form a thin, adhering oxide layer that
slows corrosion.
Use metals that are relatively unreactive in the corrosion environment.
Use inhibitors (substances added to solution that decrease
reactivity); slow oxidation/reduction reactions by removing reactants like
O
2
gas by reacting it w/an inhibitor).
Slow oxidation reaction by attaching species to the surface. Apply
physical barriers: films and coatings, paint
Reduce T (slows kinetics of oxidation and reduction)
Cathodic (or sacrificial) protection; attach a more anodic material to the
one to be protected.
Corrosion Prevention
steel
zinc zinc
Zn
2+
2e
-
2e
-
e.g., zinc-coated nail
Galvanized Steel
Metal (examples: Al,
stainless steel)
Metal oxide
Passivation Process
Stainless steel was discovered around 19001915. A result of
multiple scientific efforts in England, France and Germany on alloys
with compositions that would later be known as the 410, 420, 430, 442,
446 and 440C grades.
Stainless steels must have a very low level of carbon; difficult to obtain
(low carbon) for many years, which explains the late arrival of good
ferritic grades in the 1980s.
Chromium (Cr) is by far the most important alloying element in the
production of stainless steel. It forms the passive surface film
(chromium oxide) that makes stainless steel corrosion resistant and
increases scaling resistance, wear resistance and tensile strength.
A minimum of 10.5% chromium content (by weight)
is required for the protective, self-repairing surface
layer of chromium oxide to form reliably. The higher
the chromium content, the stronger the passive
layer.
If the stainless steel surface is machined or
accidentally damaged, the passive layer quickly re-
forms, in the presence of air or water.
Sacrificial Anodes
55
This field is located in Viosca Knoll, block 786, southeast of New Orleans. It lies in water depths of
approximately 1754 feet (535 meters). Petronius is the largest free-standing structure in the world. Texaco's
choice was Galvotec-CW-III Aluminum Sacrificial Anodes for their Petronius cathodic protection
system. http://www.galvotec.com/img/texaco.jpg
"Salt water isn't good for anything."
56
A man blamed a low-flying pelican and a dropped cell phone for veering his million-dollar (French-
built Bugatti Veyron) sports car off a road and into a salt marsh near Galveston. The car was half-
submerged in the brine about 20 feet from the road when police arrived (Nov 11, 2009).

WORLD'S FASTEST: Bugatti Veyron Busts Out With 1,000-hp and $1.3 Million Price Tag
The Veyron's 16-cylinder engine develops a shade over 1,000 horsepower, giving it a 0-60 time of
fewer than 3 seconds and a 252-mph top speed. Those staggering stats make the Veyron the world's
fastest production car. It's also the most expensive (2005 stats).
$1.95 Million (2009)
57
58
Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction
Metals and alloys are ranked according to their
corrosiveness in standard emf and galvanic series.
Temperature and solution composition affect corrosion
rates. Increasing T, speeds up oxidation/reduction reactions.
Forms of corrosion are classified according to mechanism
Corrosion may be prevented or controlled by:
-- materials selection
-- reducing the temperature
-- applying physical barriers
-- adding inhibitors
-- cathodic protection
using metals that form a protective oxide layer
Painting/coating
Summary
"Rust's A Must"
59
Mighty ships upon the ocean
Suffer from severe corrosion,
Even those that stay at dockside
Are rapidly becoming oxide.
Alas, that piling in the sea
Is mostly Fe
2
O
3
.
And where the ocean meets the shore,
You'll find there's Fe
3
O
4
.
'Cause when the wind is salt and gusty,
Things are getting awful rusty.

We can measure, we can test it,
We can halt it or arrest it.
We can gather it and weigh it,
We can coat it, we can spray it.
We examine and dissect it,
We cathodically protect it
We can pick it up and drop it.
But heaven knows we'll never stop it!
So here's to rust, no doubt about it,
Most of us would starve without it.

The origin of this epic
poem is a bit
fuzzy. We have seen
a reference to the late
Mr. T. R. B Watson of
Corrosion Services
Co., Ltd. in Toronto
and we believe that he
is the author.

More Information
http://www.electrochem.org/
The Journal of The Electrochemical Society (JES) is the leader in the
field of solid-state and electrochemical science and technology. This
peer-reviewed journal publishes an average of 450 pages of 70 articles
each month. Articles are posted online, with a monthly paper edition
following electronic publication in the following areas:
Batteries and Energy Storage
Fuel Cells and Energy Conversion
Corrosion, Passivation, and Anodic Films
Electrochemical/Chemical Deposition and Etching
Electrochemical Synthesis and Engineering
Physical and Analytical Electrochemistry
Dielectric Science and Materials
Semiconductor Devices, Materials, and Processing
Sensors and Displays: Principles, Materials, and Processing
Nanostructured Materials, Carbon Nanotubes, and Fullerenes
Interdisciplinary Topics
60