CORROSION AND DEGRADATION

ISSUES TO ADDRESS...
Why does corrosion occur?
What metals are most likely to corrode?
How do temperature and environment affect
corrosion rate?
How do we suppress corrosion?

THE COST OF CORROSION

Corrosion:
--the destructive electrochemical attack of a material.
--Al Capone's
ship, Sapona,
off the coast
of Bimini.
Photos courtesy L.M. Maestas, Sandia
National Labs. Used with permission.

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).
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The Rusting Mechanism

(Peel)

4Fe + 6H2O + 3O2 4Fe(OH)3

gives ferric hydroxide

2Fe(OH)3 Fe2O3 3H2O

gives iron oxide (rust) and water

Basic rusting or corrosion requirements

1. The metal is oxidized at the anode of an electrolytic
cell
2. Some ions are reduced at the cathode
3. There is a potential or voltage difference between the
anode and cathode
4. An electrolyte (fluid) must be present
5. The electrical path must be completed
2

CORROSION OF ZINC IN ACID

Two reactions are necessary:
-- oxidation reaction: Zn Zn2 2e
-- reduction reaction: 2H 2e H2(gas)
H+
oxidation reaction
Zn
Zn2+
H+

Zinc

flow of e2ein the metal

H+
H+

Acid
solution

H+
H+

H2(gas)
H+
reduction reaction

Adapted from Fig. 17.1, Callister

6e. (Fig. 17.1 is from M.G.
Fontana, Corrosion Engineering,
3rd ed., McGraw-Hill Book
Company, 1986.)

Other reduction reactions:

-- in an acid solution

O2 4H 4e 2H2O

-- in a neutral or base solution

O2 2H2O 4e 4(OH)
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STANDARD HYDROGEN (EMF) TEST

Two outcomes:
e-

H2(gas) 2e
Mn+ H+
ions
H+

Platinum

metal, M

ne-

e-

25C

1M Mn+ soln 1M H+ soln

--Metal is the anode (-)

o
Vmetal
0 (relative to Pt)

e-

nemetal, M

e-

--Metal sample mass

Mn+
ions

H+ 2eH+

Platinum

--Metal sample mass

25C

1M Mn+soln 1M H+ soln

--Metal is the cathode (+)

o
Vmetal
0 (relative to Pt)

Standard Electrode Potential

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STANDARD EMF SERIES

EMF series
metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K

o
Vmetal

Metal with smaller

o

Vmetal corrodes.

+1.420 V
Ex: Cd-Ni cell
+0.340
+
- 0.126
- 0.136
- 0.250
o
- 0.277 V =
- 0.403 0.153V
Cd
Ni
25C
- 0.440
- 0.744
- 0.763
1.0 M
1.0 M
- 1.662
Cd 2+ solutionNi 2+solution
- 2.262
- 2.714
Data based on Table
- 2.924 17.1, Callister 6e.
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CORROSION IN A GRAPEFRUIT
Cathode
Cu +

Anode

H+
H+
Zn2+
2e-

reduction
2H 2e H2(gas)
O2 4H 4e 2H2O

H+
H+

Zn

oxidation
H+

Acid

H+

H+

EFFECT OF SOLUTION CONCENTRATION

Ex: Cd-Ni cell with
Ex: Cd-Ni cell with
standard 1M solutions
non-standard solutions
RT X
o
o
o
o
VNi
VCd
0.153
VNi VCd VNi VCd
ln
nF Y
-

Cd

25C

Ni

1.0 M
1.0 M
Cd2+ solution Ni2+solution

n = #eper unit
oxid/red
Cd
Ni
T
reaction
(=2 here)
F=
XM
YM
Faraday's
Cd2+ solution Ni2+solution constant
Reduce VNi - VCd by =96,500
C/mol.

--increasing X
--decreasing Y

Factors affecting Corrosion

Material properties
Metallurgical factors
Passivity
Environment

Metallurgical factors
Chemical segregation
Presence of multiple
phases
Inclusions
Cold Work
Non-uniform stresses

(Peel)

Passivity
Example with steel in
nitric aciddilute
solutions will cause
rapid attack, strong
solutions have little
visible effect.
Surface film can be
formed
Some types of steel
may do this with rust
Aluminum does this
Need to watch passive
film, but can be used for
simple protection
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GALVANIC SERIES

(
a
c
t
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e
)

(
i
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r
t
)

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

Based on Table 17.2,

Callister 6e. (Source of
Table 17.2 is M.G. Fontana,
Corrosion Engineering, 3rd
ed., McGraw-Hill Book
Company, 1986.)

FORMS OF CORROSION
Stress corrosion

Stress & corrosion

Uniform Attack work together
Erosion-corrosion
Oxidation & reduction at crack tips.
Break down of passivating
occur uniformly over
layer by erosion (pipe
surface.
elbows).

Selective Leaching

Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).

Intergranular

Forms
of
corrosion

Pitting

Downward propagation
of small pits & holes.

Fig. 17.8, Callister 6e.

(Fig. 17.8 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)

Corrosion along
grain boundaries,
Galvanic
often where special Dissimilar metals are Crevice Between two
pieces of the same metal.
phases exist.
physically joined. The
Rivet holes
g.b.
more anodic one
prec.
corrodes.(see Table
17.2) Zn & Mg
attacked
Fig. 17.6, Callister 6e. (Fig. 17.6 is
very
anodic.
zones
courtesy LaQue Center for Corrosion
Fig. 17.9, Callister 6e.

Technology, Inc.)

CONTROLLING CORROSION
Metal oxide
Metal (e.g., Al,
stainless steel)

Self-protecting metals!

--Metal ions combine with O2

to form a thin, adhering oxide layer that slows corrosion.
Reduce T (slows kinetics of oxidation and reduction)
Add inhibitors
--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 (e.g., paint it!).
Cathodic (or sacrificial) protection
--Attach a more anodic material to the one to be protected.
e.g., zinc-coated nail
e.g., Mg Anode
Zn2+

zinc

2e- 2esteel

zinc

steel
pipe

e-

Cu wire
Mg Mg2+
anode
Earth

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SUMMARY
Corrosion occurs due to:
--the natural tendency of metals to give up electrons.
--electrons are given up by an oxidation reaction.
--these electrons then are part of a reduction reaction.

Metals with a more negative Standard Electrode

Potential are more likely to corrode relative to
other metals.
The Galvanic Series ranks the reactivity of metals in
seawater.
Increasing T speeds up oxidation/reduction reactions.
Corrosion may be controlled by:
-- using metals which form -- adding inhibitors
a protective oxide layer -- painting
-- reducing T
--using cathodic protection.
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Homework
Thisproblemasks,forseveralpairsofalloysthatare
Reading:
immersedinseawater,topredictwhetherornotcorrosionis
possible,andifitispossible,tonotewhichalloywillcorrode.
Inordertomakethesepredictionsitisnecessarytousethe
galvanicseries,Table17.2.Ifbothofthealloysinthepair
residewithinthesamesetofbracketsinthistable,then
galvaniccorrosionisunlikely.However,ifthetwoalloysdo
notresidewithinthesamesetofbrackets,thenthatalloy
Self-help Problems:
appearinglowerinthetablewillexperiencecorrosion.
(d)Forthetitanium304stainlesssteelpair,the
stainlesssteelwillcorrode,inasmuchasitisbelowtitaniumin
bothitsactiveandpassivestates.
(e)Forthecastiron316stainlesssteelcouple,the
castironwillcorrodesinceitisbelowstainlesssteelinboth
activeandpassivestates.

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Homework
Reading:
This problem asks for us to calculate the CPR in both mpy and mm/yr for a thick
steel sheet of area 100 in.2 which experiences a weight loss of 485 g after one year.
Employment of Equation (17.23) leads to

(534)(485 g) 103 mg / g
KW
CPR =
CPR =
3
A t
7.9 g / cm 100 in.2 (24 h / day)(365 day / yr)(1 yr)

Self-help Problems:
= 0.952 mm/yr
Also
CPR =

(87.6)(485 g) 10 3 mg / g

7.9 g / cm 3 100 in.2 (2.54 cm / in.)2 (24 h / day)(365 day / yr)(1 yr)
= 37.4 mpy
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