Corrosion and

Degradation of
Materials
Chapter 16
 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?
The Cost of Corrosion

4
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
 Electrochemical Corrosion
Corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction: Zn  Zn2  2e
-- reduction reaction: 2H  2e  H2 (gas)
H+
Oxidation reaction
flow of e  Zn
-
Zn2+ H+
in the metal
Acid
Zinc 2e- H+ H+ solution
H +
H+
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution
O2  4H  4e  2H2O O2  2H2O  4e  4(OH)
11
 Standard Hydrogen Electrode
• Two outcomes:
-- Corrosion -- Electrodeposition

e- e- e- e-
H2(gas) H+ 2e -
ne - 2e - ne -
H+
Platinum

Platinum
Mn+

metal, M
metal, M

Mn+ H+
ions ions
H+
25°C 25°C
1M Mn+ sol’n 1M H + sol’n 1M Mn+ sol’n 1M H+ sol’n
-- Metal is the anode (-) -- Metal is the cathode (+)
o
Vmetal  0 (relative to Pt) o
Vmetal  0 (relative to Pt)

Standard Electrode Potential

12
 Standard EMF Series
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic

Cu +0.340 o o
Pb - 0.126 VCd < VNi  Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Fe - 0.440
more anodic

Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2+ solution Ni 2+ solution
Na - 2.714
K - 2.924
13
 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
 Galvanic Series
• Ranking the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
more anodic

Lead
316 Stainless Steel (active)
(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
16
 Solution Concentration and Temperature
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
RT X
VNio VCd
o
 0.153 V VNi  VCd  VNi  VCd 
o o
ln
- - nF Y
+ +
n = #e-
per unit
oxid/red
Cd 25°C Ni Cd T Ni reaction
(= 2 here)
F=
1.0 M 1.0 M XM YM Faraday's
Cd 2+ solution Ni 2+ solution Cd 2+ solution Ni 2+ solution constant
= 96,500
C/mol.

18
 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
• This curve is usually
scanned from 20 mV
Types of Tests below the Eoc (open circuit
potential) upward.
ANODIC POLARIZATION CURVE
•The curve can be used to
•this curve is usually scanned from 20mV below the
identify Eocfollowing
the upwards
•by scanning at a slow rate (.2mV/s) this curve can beregions:
corrosion used to identify
several corrosion mechanisms shown below

ip - passive current density

Epp - primary passivation potential

icrit - critical current density

Etrans - transpassive potential

 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

Formerly a ship

23
 Galvanic
 Dissimilar metals are
physically joined in the
presence of an electrolyte.
 The more anodic metal
corrodes.

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.
Crevice Corrosion

Narrow and confined spaces.

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 304
stainless
measured by weight loss, may be steel / acid
minimal. chloride
solution

5th Century sword

Boiler tube
 Intergranular
Corrosion along
grain boundaries,
often where precipitate
particles form.
Erosion-corrosion
Combined chemical attack and
mechanical wear (e.g., pipe
elbows).

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
 measurements are especially suited to it 8

Zinc HCl solution

Zn+2

e-
Corrosion Test
Types
Methods •Open Circuit Potential Scans
e- H+
H+
H2
Cl-
H+

H+ H+ Cl
•Polarization Resistance -

•Potentiodynamic Curves
1: The measurement•Galvanic
of the •they are extremely
open circuit potential is very fast compared
Corrosion Tests to other corrosion tests and the
easy and inexpensive, but is not
•Electrochemical considered
Impedence toarebeeasily
results veryanalyzed to find
Spectroscopy (EIS) corrosion rates
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.

35
 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 I
 Equipment material
E
 Reference electrode
 Maintains constant potential

Secondary Electrode
Reference Electrode
Working Electrode
• Even at large currents
 Counter (Secondary) electrode
 Allows infinite current
Test Samples
EG&G Instruments: Potentiostat/Galvanostat
Model 273A
 Comparison of Corrosion Potential vs Time
for MCI Treated Concrete with Untreated Samples

100

RF1-untreated MR1-rebar treated

50
MS1-surface treated MM1-mortar coated surface
0
Potential, (mV)

-50

-100

-150

-200

-250

-300
0 50 100 150 200 250
Time of Submersion (Days)
 Corrosion Potential vs Time, ASTM C876-91, Cortec MCI 2022 & 2021
Compared with Unprotected Concrete (Various Concrete Densities)
L=low density, H=high density
0

-100

-200
Potential, (mV)

-300
L untreated

L2021
-400
L2022

H untreated
-500
H2021

H2022
-600
0 50 100 150 200 250 300 350 400 450

Time of Submersion (Days)

 EIS Results, Bode Plots
LD=untreated low density concrete, 2S=MCI 2022/high density, 2L=MCI 2022/low density;
3 3
Concrete densities: low = 130 lbs/ft , high = 150 lbs/ft .

1.00E+05
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

1.00E+04
l Z l (Ohms)

1.00E+03

1.00E+02

1.00E+01
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)
Concrete Exterior & Interior
Concrete Interior (untreated)
 Useful Parameters

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.
 Types of Tests
Open Circuit Potentials
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

Aluminum (FS)

Zinc (BHD)

•these measurements are made under equilibrium conditions (ie. absence

of current flow ) to describe the thermodynamic equilibrium of an
electrochemical system 8

46
 Polarization Resistance, Rp
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
Types (Ecorrof
). The slope expresses the
Tests
value of the polarization resistance (Rp) if the increment is close to
zero. Polarization Resistance
This Rp value is related to the corrosion current (Icorr) by means of
•Now that we have found Rp we can sub it into the Stern-Geary
the expression:equation:
1 BaBc - Ba and Bc are the Tafel
icorr 
Rp 2.303( Ba  Bc ) Slopes and are
approximated to both be
.1 V

•Using the icorr value, we can now solve for a

Where A is the area of metal surface
corrosion evenly
rate as wepolarized and B is a
did before
constant that may vary from 13 to 52 mV. For steel embedded in
concrete, the best fit with•itparallel
has been found that
gravimetric there
losses is good
results correlation
in B= 26 b/w
mV for actively corrodingcorrosion
steel , andrates obtained
a value of B= by
52 polarization
mV, when theresistance
steel is passivated. and those obtained by weight loss10
 Types of Tests
Galvanic Corrosion Tests
Types of Tests
In Seawater
Graphite
Galvanic Corrosion Tests Pt
In Seawater
Ti
Stainless Steel
•whenGalvanic
Graphite
two different metals areTests
Corrosion electrically Ni-Cu
Ag Ti
Ptalloys

Types of Tests
coupled in the presence of a conductive
•when two different metals are electrically
solution, one of them corrodes at an
coupled in the presence of a conductive
More
Noble
More
Ni alloys
Cu-Ni
Bronze
Stainless Steel
Ni-Cu alloys
Ag
In Seawater
Brass Ni alloys
Noble
accelerated rate while the other is protected
solution, one of them corrodes at an
Pb-Sn Cu-Ni
solder
Graphite
Bronze
Galvanicaccelerated
Corrosion Tests More
Cu
SnPt Brass
•this is important in sacrificial coatings
rate while the other is protected Ti Pb-Sn
Low solder
alloys steel
Cu
Active Stainless
Low Steel
carbon steel
Sn
whenbecause theiscoating
two different
•this acts
metals
important as
inarethe anode and the
electrically
sacrificial coatings More AlNi-Cu
alloys alloys
AlAg
Low alloys steel
Active
More Low carbon steel
substrate
coupled in the acts
because as
thethe
presence cathode
of a acts
coating conductive
as the anode and the BeNi Al
alloys
alloys
Noble Zn Al
Cu-Ni
substrate
solution, one of them actscorrodes
as the cathode
at an Mg Be
Bronze
Zn
Brass
coating Mg
accelerated rate while the other is protected Pb-Sn solder
Cu
coating

this is important in sacrificial coatings •in order to correctly

Sn
substrate More assess a sacrificial
Low alloys steel
substrate •in order
coating to correctly
look at assess
Active
we must a sacrificial
the galvanic
Low carbon steel
because the coating acts as the anode and the
coating
couple that we must
exists look at the
between
Al alloys
the galvanic
coating and
Al
substrate acts as the cathode Be
couple that exists between the coating an
the substrate Zn
11
the substrate11 Mg

coating

•in order to correctly assess a sacrificia

48
coating we must look at the galvanic
 Types of Tests
Potentiodynamic
Potentiodynamic Curves
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 coating’s

e-
corrosion protection

+
M+
2H
+


E +2

M
e- E
 net +
H current
Ecorr - 2
Ecorr
e 2H net -
+ + +
M + current
 iapplied 2e
-
M 
H
2
icorr icorr log i
log i
Evan’s Diagram Polarization Curve

49
 Types of Tests
Tafel Extrapolation
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

icorr Anodic Tafel Slope (Ba)

Ecorr

•A straight portion of 1 order of magnitude is suggested for

accuracy9
50
 Electrochemical Impedance Spectroscopy (EIS)
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.

51
Proposed Relationship between Corrosion Rate
and Remaining Service Life

icorr (mA/cm2) 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

 Metal oxide
Corrosion Prevention Metal (examples: Al,
stainless steel)

 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
O2 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.
Galvanized Steel
Zn2+
zinc zinc
2e- 2e-
steel
e.g., zinc-coated nail 53
 Passivation Process
 Stainless steel was “discovered” around 1900–1915. 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

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

55
 "Salt water isn't good for anything."

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)

56
57
 Summary
• 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
58
 "Rust's A Must"
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 Fe2O3.
And where the ocean meets the shore, The origin of this epic
You'll find there's Fe3O4. poem is a bit
'Cause when the wind is salt and gusty, fuzzy. We have seen
Things are getting awful rusty. a reference to the late
Mr. T. R. B Watson of
Corrosion Services
We can measure, we can test it,
Co., Ltd. in Toronto
We can halt it or arrest it. and we believe that he
We can gather it and weigh it, is the author.
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.

59
 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