Chapter 17:

Corrosion and Degradation of

Materials
Chapter Outline:
• Electrochemical Reactions in Metals

• Mechanisms of Corrosion in Metals

• Corrosion Prevention Techniques

• Corrosion of Ceramics

• Degradation of Polymers
Chapter 17 - 1
 THE COST OF CORROSION
• Corrosion:
-- the destructive electrochemical attack of a material.
-- Ex: The Scow (sand barge)
Niagara Falls, Ontario.

• Cost:
-- 4 to 5% of the Gross National Product (GNP)*
-- in the U.S. 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).
Chapter 17 - 2
 EFFECT OF CORROSION

1936 Deluxe Ford Sedan

Six stainless steel cars were

made to test the durability and
corrosion resistance of stainless
steel.

Chapter 17 - 3
 Corrosion of Metals

Why do metals corrode?

By definition: corrosion is the deterioration of a material or

its properties because of reaction with its environment.
• It could be a weight gain;
• It could be a weight loss;
• Sometimes the mechanical properties are affected.

Chapter 17 - 4
ELECTROCHEMICAL CORROSION

Four basic elements for electrochemical corrosion

 Anode
 Cathode
 Ion conductor
 Electron conductor

If any of these conditions is not met,

electrochemical corrosion will not occur!

Chapter 17 - 5
ELECTROCHEMICAL CORROSION
 Electrochemical corrosion - Corrosion produced by the
development of a current in an electrochemical cell that
removes ions from the material.
 Electrochemical cell - A cell in which electrons and ions
can flow by separate paths between two materials,
producing a current which, in turn, leads to corrosion or
plating.
 Oxidation reaction - The anode reaction by which electrons
are given up to the electrochemical cell.
 Reduction reaction - The cathode reaction by which
electrons are accepted from the electrochemical cell.

Chapter 17 - 6
 ELECTROCHEMICAL CORROSION
Ex: consider the 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
 Zn Zn2+ H+
Adapted from Fig. 17.1,
Callister & Rethwisch 8e.
Acid (Fig. 17.1 is from M.G.
Zinc flow of e
-
2e-
H+ Fontana, Corrosion
in the metal H+ + solution Engineering, 3rd ed., McGraw-
H
H+ Hill Book Company, 1986.)
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)
Chapter 17 - 7
 STANDARD HYDROGEN ELECTRODE
• Two outcomes: (SHE)
-- 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+
H2(gas)
25ºC 25ºC
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)
Adapted from Fig. 17.2,
Standard Electrode Potential Callister & Rethwisch 8e.

Chapter 17 - 8
 STANDARD EMF SERIES
• EMF series (oxidation) • Metal with smaller
o
Vmetal o
metal Vmetal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic

Cu +0.340 o o
Pb - 0.126 VCd < V Ni  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 25ºC 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
Data based on Table 17.1, Adapted from Fig. 17.2,
K - 2.924 Callister 8e. Callister & Rethwisch 8e.

Chapter 17 - 9
 EFFECT OF 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 25ºC 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
• Reduce VNi - VCd by = 96,500
C/mol.
-- increasing X
-- decreasing Y
-- increasing T Chapter 17 - 10
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive) Based on Table 17.2, Callister &
Nickel (passive) Rethwisch 8e. (Source of Table
17.2 is M.G. Fontana, Corrosion
Copper Engineering, 3rd ed., McGraw-
Nickel (active) Hill Book Company, 1986.)
Tin
more anodic

Lead
316 Stainless Steel (active)
(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
Chapter 17 - 11
 CORROSION IN A GRAPEFRUIT
Cu (cathode) Zn (anode)
+ -
H+
H+ Zn 2+

reduction reactions 2e - oxidation reaction

2H  2e  H2 (gas) H+ Zn  Zn2+  2e
  H+
O2  4H  4e  2H2O Acid H+
H+ H+


Chapter 17 - 12
 POLARIZATION AND PASSIVITY
• Polarization - Changing the voltage (from EMF value)
between the anode and cathode to reduce the rate of
corrosion (magnitude called overvoltage).

– Activation polarization is related to the energy required

to cause the anode or cathode reaction
– Concentration polarization is related to changes in the
composition of the electrolyte
– Resistance polarization is related to the electrical
resistivity of the electrolyte.

• Passivity – Active metals and alloys lose chemical

reactivity. Likely the result of highly adherent and thin
oxide layer as well as polarization
Chapter 17 - 13
 ACTIVATION POLARIZATION
• Overall reaction rate is
controlled by step having
slowest rate.
• Rate limiting step has
activation energy barrier.
• Overvoltage (ηa) given by:
i
 a    log
i0
Where,
β is a constant
i = current density
i0 = exchange current density
(equilibrium)
Chapter 17 - 14
 CONCENTRATION POLARIZATION
• Depletion of ions near
material-solution interface
reduces reaction rate.
• Diffusion of ions is rate
controlling process.
• Overvoltage (ηc) given
by:
2.3RT i
c  log( 1  )
nF iL
Where,
F= Faraday’s constant
i = current density
iL = limiting diffusion current
density Chapter 17 - 15
 TAFEL PLOTS AND CORROSION
CURRENT
• At equilibrium:
iox= ired = i0 itotal = 0

• Corrosion current cannot be

measured directly.
• Polarization overvoltage (controlled)
and current (measured) used to
produce “Tafel Plot”.
• Corrosion current (i0) found at
intersection point by:
ox  red
i0 
2.3Rp ( ox   red )
Where,
βox, βred = Tafel Constants for oxidation
and reduction reactions
Rp = Polarization resistance Chapter 17 - 16
 CORROSION RATE
Weight Loss Method Electrochemical Method
• Corrosion Penetration Rate • Utilizes corrosion current
(CPR): and Faraday’s Law

KW # of electrons in mass of reacting

CPR  reaction species
At nF W
Where, Q
W = weight loss after exposure time
A
atomic weight
(mg), (t (hr))
K = 87.6 (for CPR in mm/yr), • Where, Q = It, E.W.= A/n and
534 [for CPR in mpy] CR=W/t :
ρ = specimen density (g/cm3) 0.13 i 0 ( E.W .)
CR (mpy ) 
A = exposed specimen area (cm ) 2 
[in2]
Electrochemical method significantly faster in
finding corrosion rate! Chapter 17 - 17
 PASSIVITY-POLARIZATION CURVE
Obtained by Potentiodynamic Anode Polarization Measurements

2
3

Chapter 17 - 18
 OVERVIEW OF CORROSION
MECHANISMS
• Stress corrosion
• Uniform Attack • Erosion-corrosion

Forms
• Selective Leaching of • Pitting
.
corrosion

• Crevice.
• Intergranular
.
• Galvanic
Chapter 17 - 19
 UNIFORM ATTACK
• Electrochemical corrosion of metals where
oxidation and reduction reactions occur
uniformly over entire surface.

• Examples:
– General rusting of steel and iron
– Tarnishing of silverware

Chapter 17 - 20
 GALVANIC CORROSION
• Two metals/alloys of different Ex. Mg Shell Around Steel Core
compositions that are electrically
coupled in an electrolyte.

• The anodic material is corroded

by loss of electrons, while more
cathodic material protected.

Chapter 17 - 21
 CREVICE CORROSION
Small regions (between metals of same composition) where
solution is stagnant and there is a local depletion of dissolved
oxygen (concentration cell).

Anodic
M  M n   ne 

Cathodic
O2  2H 2O  4e   4OH 
Chapter 17 - 22
PITTING CORROSION
• Localized corrosion where
small pits form.

• Similar to crevice corrosion,

concentration cell formed
which transfers electrons to
adjacent surface.

• Can be initiated by surface

defect like scratches.

Pitting of a 304 Stainless steel

plate in an acid-chloride solution
Chapter 17 - 23
 INTERGRANULAR CORROSION
• Preferential chemical attack of grain boundaries
in certain environments. Why?
High Energy Region Stainless Steel: Cr Depletion
due to Cr23C6 Formation

When heated to between 500 and 800 oC

Chapter 17 - 24
INTERGRANULAR CORROSION

Weld decay in stainless steel.

Chapter 17 - 25
 SELECTIVE LEACHING
• Occurs in alloys where
one constituent is
preferentially removed by
corrosion.
• Mechanical properties
are impaired due to
porous mass in leached
region.
• Ex. Dezincification of
brass (Cu-Zn Alloy)

Chapter 17 - 26
 EROSION-CORROSION
• Combined chemical attack Example: Pipe Elbow
and mechanical abrasion
from fluid motion.
• Soft metals (Cu, Al) as well
as passivated metals
susceptible.
• Increased fluid velocity and
fluids with bubbles and
particulates increase
corrosion rate. Bends and changes in pipe diameter
• Common in parts that induce fluid turbulence making them
susceptible to erosion-corrosion
induce fluid turbulence.
Chapter 17 - 27
 STRESS CORROSION CRACKING
• Brittle fracture induced by
applied or residual tensile
stress on a component in
corrosive medium.

• Stress areas are regions of

higher energy (strain
energy) and thus anodic.

• Ejection of ions allows for

crack initiation in region at
stress levels much lower
than material strength.
Chapter 17 - 28
STRESS CORROSION CRACKING

Micrograph showing intergranular stress

corrosion cracking in brass.
Chapter 17 - 29
 HYDROGEN EMBRITTLEMENT
• Reduction in ductility and tensile strength when atomic
hydrogen penetrates into material.
Typically occurs in High Strength (BCC) and
Martensitic Steels (BCT).

• Hydrogen atoms diffuse interstitially into lattice and

prevent dislocation movement (reduced ductility).
• Hydrogen atoms serve as crack nucleation site (reduced
strength).
• Fracture usually occurs within grain interior (intergranular)
by cleavage but can also be along grain boundaries
(transgranular).
Chapter 17 - 30
 CORROSION PREVENTION (i)
• Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
-- Use metals that passivate
Metal oxide
- These metals form a thin, Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.
• Lower the temperature (reduces rates of oxidation and
reduction)
• Apply physical barriers -- e.g., films and coatings

• Increase the relative surface area of the anode compared

to the cathode
Chapter 17 - 31
 CORROSION PREVENTION (ii)
• Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.

• Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
Galvanized Steel Using a sacrificial anode
Adapted Zn 2+ Cu wire Adapted
from Fig. e- from Fig.
17.23, zinc zinc steel Mg Mg 2+ 17.22(a),
Callister &
Rethwisch 2e - 2e - pipe anode Callister &
Rethwisch
8e. steel Earth 8e.

e.g., zinc-coated nail e.g., Mg Anode Chapter 17 - 32

 CORROSION PREVENTION (iii)
Alter component design to eliminate crevices
(concentration cell) and composition cells

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Chapter 17 - 33
 CASE STUDIES(i)

?
Prevent base metal dilution

Chapter 17 - 34
CASE STUDIES(ii)

?
Crevise control

Chapter 17 - 35
CASE STUDIES(iii)

Provide proper drainage

Chapter 17 - 36
 CASE STUDIES(iv)

?
?
Prevent solutions from drying and concentrating

Chapter 17 - 37
CASE STUDIES(v)

Provide for inspection

Chapter 17 - 38
CASE STUDIES(vi)

Prevent galvanic couples

Chapter 17 - 39
 CASE STUDIES(vii)

Avoid incomplete weld penetration

Chapter 17 - 40
CASE STUDIES(viii)

Avoid water accumulation in

outdoor construction
Chapter 17 - 41
Corrosion of Ceramics

Chapter 17 - 42
 CERAMIC CORROSION
• Immune to almost corrosion in almost all
atmospheres, specifically at ambient
temperature.

• Ionic compound that can be thought of as a

bi-product of corrosion.

• Ceramic corrosion by chemical dissolution

(rather than electrochemical attack in metals)
can occur at high temperatures from molten
metals, salts, slags and glasses.

Chapter 17 - 43
Degradation of Polymers

Chapter 17 - 44
 SWELLING AND DISSOLUTION
• Liquid or solute is absorbed by polymer where they
reside in region between chains.
• Chains forced apart by solute, reducing secondary
bond strength. Polymer becomes softer and more
ductile.
• Higher molecular weight, crosslinking and
crystallinity reduces deterioration of polymer.

Chapter 17 - 45
 COVALENT BOND RUPTURE
• Rupture of main covalent Chemical Scission of
bonds called scission. Vulcanized Rubber
• Scission can occur due to:
– Radiation Effects
(Ionization of chain atoms)
– Chemical Reaction
(Cracks perpendicular to stress)
– Thermal Effects Scission of PVC at 200 oC
(Low energy bonds broken at
high temperature)

• Scission reduces molecular + Heat HCl

weight:
– Deleterious to strength
– Reduced resistance to chemical
attack. Chapter 17 - 46
 WEATHERING
• Any polymer degradation caused by
exposure to outdoor conditions.

• Can be a combination of several degradation

processes.
– Mainly caused by oxidation induced by
ultraviolet radiation (Sun).
– Water absorption (e.g. nylon, cellulose)
may reduce polymer stiffness.

Chapter 17 - 47
 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.
• 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

Chapter 17 - 48
Reading:

End of Chapter 17
Core Problems:

Questions?
Self-help Problems:
Suggested Problems: 17.5, 17.6

Chapter 17 - 49