Chapter 17:

Corrosion and Degradation of

Materials
ISSUES TO ADDRESS...
How does corrosion occur?
Which metals are most likely to corrode?
What environmental parameters affect
corrosion rate?
How do we prevent or control corrosion?
Chapter 17 - 1
THE COST O CORROSIO!
Corrosion:
-- the destructive electrochemical attack of a material.
-- !: "l Capone#s
ship$ %apona$
off the coast
of &imini.
Cost:
-- ' to () of the *ross +ational ,roduct -*+,./
-- in the 0.%. this amounts to 1ust over 2'33 4illion5yr//
Chapter 17 - 6
Chapter 17 - 7
6
6
H
H
H

E"ECTROCHEMICA" CORROSIO!
!: consider the corrosion of 8inc in an acid solution
9wo reactions are necessary:
-- o!idation reaction:
:n :n
6+
+ 6e

-- reduction reaction:
+
+ 6e

H
;
H
6
-<as.
=!idation reaction
:n
:n
6;
H
;
;
"cid
"dapted from >i<. 17.1$
Callister & Rethwisch 8e.
->i<. 17.1 is from ?.*.
:inc
flow of e
-
6e
-
H
;
H
solution
>ontana$ Corrosion
in the metal
;
H
;
H
6
-<as.
H
;
Engineering$ 7rd ed.$ ?c*raw-
Hill &ook Company$ 1@AB..
reduction reaction
=ther reduction reactions in solutions with dissolved o!y<en:
-- acidic solution -- neutral or 4asic solution
= + '
+
+ 'e

6H
6
= =
6
+ 6H
6
= + 'e
'-=H.

Chapter 17 - '
Ele#trode $otentials
Carious electrode pairs have different volta<es -as drivin< force for
electrochemical reactions..
?etallic materials may 4e rated as their tendency to e!perience
o!idation -losin< electrons..
ne
-
?
n;
H
;
6e
-
ions
6(
1? ?
n;
solDn
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EC
1? H
;
solDn
V
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Chapter 17 - (
STA!DARD H%DRO&E! E"ECTRODE
9wo outcomes:
-- Corrosion
e
-
e
-
-- lectrodeposition
e
-
e
-
ne
-
H
6
-<as.
6e
-
?
n;
H
;
ions
H
;
6(EC
1? ?
n;
solDn 1? H
;
solDn
-- ?etal is the anode --.
-- ?etal is the cathode -;.
o
<
metal
-relative to ,t.
o
>
metal
-relative to ,t.
%tandard lectrode ,otential
"dapted from >i<. 17.6$
Callister & Rethwisch 8e.
,4 - 3.16B
%n - 3.17B
+i - 3.6(3
Co - 3.677
Cd - 3.'37
>e - 3.''3
Cr - 3.7''
:n - 3.7B7
"l - 1.BB6
?< - 6.7B7
+a - 6.71'
F - 6.@6'
metal
STA!DARD EM SERIES
emf series
o
?etal with smaller
o
V
metal
V
metal
corrodes.
"u ;1.'63 C
Cu ;3.7'3
Cd-
o
cell
o
!:
V
Cd
+i
G V
+i
Cd corrodes
-
;
V
o
H
3.1(7C
Cd 6(EC +i
1.3 ?
m
o
r
e

a
n
o
d
i
c
m
o
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e

c
a
t
h
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d
i
c
Cd
6;
solution
1.3 ?
+i
6;
solution
Iata 4ased on 9a4le 17.1$
Callister 8e.
"dapted from >i<. 17.6$
Callister & Rethwisch 8e.
Cd 6(EC +i
1.3 ? 1.3 ?
Cd
6;
solution +i
6;
solution
EECT O SO"UTIO! CO!CE!TRATIO! A!D
TEM$ERATURE
!: Cd-+i cell with
standard 1 ? solutions
!: Cd-+i cell with
non-standard solutions
o

V
o
=
3.1(7 C V

V
=
V
o

V
o

RT
ln

X
V
+i Cd
+i Cd +i Cd
-
;
-
;
nF Y
Cd
T
X ?
n H Je
-
per unit
o!id5red
+i
reaction
-H 6 here.
F H
Y ?
>araday#s
Cd
6;
solution +i
6;
solution constant
Keduce V
+i
- V
Cd
4y
-- increasin< X
-- decreasin< Y
-- increasin< T
H @B$'A(
C5mol.
Chapter 17 - 7
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.
&A"'A!IC SERIES
Kankin< of the reactivity of metals5alloys in seawater
,latinum
*old
*raphite
9itanium
%ilver
71B %tainless %teel -passive.
+ickel -passive.
Copper
+ickel -active.
9in
Lead
71B %tainless %teel -active.
Mron5%teel
"luminum "lloys
Cadmium
:inc
?a<nesium
&ased on 9a4le 17.6$ Callister
& Rethwisch 8e. -%ource of
9a4le
17.6 is ?.*. >ontana$ Corrosion
Engineering$ 7rd ed.$ ?c*raw-
Hill &ook Company$ 1@AB..
Chapter 17 - A
ORMS O CORROSIO!
%tress corrosion
Corrosion at crack tips
0niform "ttack
=!idation N reduction
reactions occur uniformly
over surfaces.
%elective Leachin<
,referred corrosion of
one element5constituent
when a tensile stress
is present.
>orms
of
rosion-corrosion
Com4ined chemical attack and
mechanical wear -e.<.$ pipe
el4ows..
,ittin<
Iownward propa<ation
of small pits and holes.
Oe.<.$ :n from 4rass -Cu-:n.P.
Mnter<ranular
Corrosion alon<
<rain 4oundaries$
corrosion
>i<. 17.17$ Callister &
Rethwisch 8e. ->i<. 17.17
from ?.*. >ontana$
Corrosion Engineering$
7rd ed.$ ?c*raw-Hill &ook
Company$ 1@AB..
often where precip.
particles form.
<.4.
prec.
*alvanic
Iissimilar metals are
physically 1oined in the
presence of an
electrolyte. 9he
Crevice +arrow and
confined spaces.
Kivet holes
>i<. 17.1A$ Callister &
Rethwisch 8e.
attacked
8ones
more anodic metal
corrodes.
>i<. 17.1($ Callister & Rethwisch 8e. ->i<. 17.1(
is courtesy LaQue Center for Corrosion
9echnolo<y$ Mnc..
Chapter 17 - @
CORROSIO! $RE'E!TIO! (i)
?aterials %election
-- 0se metals that are relatively unreactive in the
corrosion environment -- e.<.$ +i in 4asic solutions
-- 0se metals that passivate
- 9hese metals form a thin$
adherin< o!ide layer that
slows corrosion.
?etal o!ide
?etal -e.<.$ "l$
stainless steel.
Lower the temperature -reduces rates of o!idation and
reduction.
"pply physical 4arriers -- e.<.$ films and coatin<s
Chapter 17 - 13
CORROSIO! $RE'E!TIO! (ii)
"dd inhi4itors -su4stances added to solution that decrease
its reactivity.
-- %low o!idation5reduction reactions 4y removin< reactants
-e.<.$ remove =
6
<as 4y reactin< it w5an inhi4itor..
-- %low o!idation reaction 4y attachin< species to
the surface.
Cathodic -or sacrificial. protection
-- "ttach a more anodic material to the one to 4e protected.
"dapted
from >i<.
*alvani8ed %teel
:n
6;
0sin< a sacrificial anode
e
-
Cu wire
"dapted
from >i<.
17.67$
Callister &
Rethwisch
8inc
6e
-
6e
-
8inc steel
pipe
?<
anode
?<
6;
17.66-a.$
Callister &
Rethwisch
8e.
steel
arth
8e.
e.<.$ 8inc-coated nail e.<.$ ?< "node
Chapter 17 - 11
SUMMAR%
?etallic corrosion involves electrochemical reactions
-- electrons are <iven up 4y metals in an o!idation reaction
-- these electrons are consumed in a reduction reaction
?etals and alloys are ranked accordin< to their
corrosiveness in standard emf and <alvanic series.
9emperature and solution composition affect corrosion
rates.
>orms of corrosion are classified accordin< to mechanism
Corrosion may 4e prevented or controlled 4y:
-- materials selection
-- reducin< the temperature
-- applyin< physical 4arriers
-- addin< inhi4itors
-- cathodic protection
Chapter 17 - 16