Module 16:

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?

Chapter 17 - 1
 THE COST OF CORROSION
• Corrosion:
-- the destructive electrochemical attack of a material.
-- Al Capone's
ship, Sapona,
off the coast of
Bimini.

• Cost: Photos courtesy L.M. Maestas, Sandia

National Labs. Used with permission.
-- 4 to 5% of the Gross National Product (GNP)*
-- this amounts to just over $400 billion/yr**

Leaking battery Chapter 17 - 2

 Electrochemical Considerations
• Oxidation (anodic reaction)
M Mn+ + ne-

metal atoms lose or give

up electrons

• M
Reduction
n+ + ne- (Cathodic
M
reaction)
M n+ + e- M(n-1)-

metal ions gain electrons

Chapter 17 - 3
 CORROSION OF ZINC IN ACID
• Two reactions are necessary:
-- oxidation reaction: Zn  Zn 2  
-- reduction reaction: 2e  2e  H 2 (gas)
2H
H+
Oxidation
Zn
Zn2+
reaction H+
Acid
Zinc flow ofe- - H+
H+H
solution
in the metal 2e + Adapted from Fig. 17.1, Callister 7e.
H+ (Fig. 17.1 is from M.G. Fontana,
H2(gas) H+ Corrosion Engineering, 3rd ed.,
reduction reaction McGraw-Hill Book Company, 1986.)

• Other reduction reactions:

-- in an acid solution -- in a neutral or base solution
O  4H  4e  2H O O  2H O  4e  4(OH)
2 2 2 2
Chapter 17 - 4
Not all metallic materials oxidize to form ions with the same degree of ease.
Chapter 17 - 5
Galvanic couple: two metals eclectically connected in a liquid electrolyte
wherein one metal becomes an anode and corrodes, while the other acts as a
cathode.
Chapter 17 - 6
The magnitude of such a voltage is the driving force for the electrochemical
oxidation-reduction reaction.
Chapter 17 - 7
 STANDARD HYDROGEN (EMF) TEST
electromotive force
• Two outcomes:
--Metal sample mass --Metal sample mass

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

Platinum

Platinum
metal, M
metal, M

Mn+ H+ Mn+
ions + ions
H
25 °C 25 °C
1M H+ sol’n 1M H+ sol’n
1M Mn+ sol’n 1M Mn+ sol’n
--Metal is the anode (-) --Metal is the cathode (+)
o
V
 0 (relative to Pt) Vo
metal metal 0 (relative to Pt)
Adapted from Fig. 17.2, Callister 7e.
Standard Electrode Potential
Chapter 17 - 8
 STANDARD EMF SERIES
• EMF series • Metal
o with smaller
o
Vmetal V
metal metal corrodes.
Au +1.420 V • Ex: Cd-Ni
Cu +0.340 cell
- +
more cathodic

Pb - 0.126
Sn - 0.136
Ni - 0.250
Co - 0.277 V o =
Cd - 0.403 0.153V
Cd 25°C Ni
Fe - 0.440
Cr - 0.744
more anodic

Zn - 0.763 1.0 M 1.0 M

Al - 1.662
Cd 2+ solution Ni 2+ solution
Mg - 2.363
Na - 2.714
Data based on Table 17.1, Adapted from Fig. 17.2, Callister 7e.
K - 2.924 Callister 7e.
Chapter 17 - 9
 CORROSION IN A GRAPEFRUIT
Cathode Anode
+ -
Cu Zn
H+
H+ Zn2+

reduction oxidation
  2e-
2H  2e  H2(gas)
O  4H  4e  2H O H+
2 2 H+ Acid
H+
H+ H+

Chapter 17 - 10
 EFFECT OF SOLUTION
CONCENTRATION
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
Vo
N VCdo  0.153 VNi VCd  VNio VCd  RT ln X
- -
o nF
i
+ +
Y

Cd 25°C Ni Cd T Ni n = #e- per

unit
oxid/red
1.0 M 1.0 M XM YM reaction (=
Cd2+ solution Ni 2+ solution Cd2+ solution Ni 2+ solution 2 here) F
• Reduce VNi - VCd by =
Faraday's
--increasing X
constant
--decreasing Y = 96,500
C/mol.
Chapter 17 - 11
 GALVANIC SERIES
• Ranks the reactivity of metals/alloys in seawater

Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel Based on Table 17.2, Callister
Nickel (passive) 7e. (Source of Table 17.2 is
M.G. Fontana, Corrosion
Copper Engineering, 3rd ed., McGraw-
Nickel (active) Hill Book Company, 1986.)
Tin
Lead
more anodic

316 Stainless
(active)

Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium Chapter 17 - 12
 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 • Pitting
Preferred corrosion of one Forms Downward propagation
element/constituent of small pits & holes.
(e.g., Zn from brass (Cu-Zn)).
of Fig. 17.17,

• Intergranular
corrosi Callister 7e.
(Fig. 17.17 from M.G.

Corrosion along
on Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
grain boundaries, •Galvanic Company, 1986.)
often where special Dissimilar metals are •Crevice Between two
phases exist. physically joined. The pieces of the same metal.
g.b. more anodic one Rivet holes
prec.
corrodes.(see Table
17.2) Zn & Mg
attacked Fig. 17.15, Callister 7e. (Fig. 17.15 is
zones very anodic. courtesy LaQue Center for Corrosion
Technology, Inc.) Chapter 17 - 13
Fig. 17.18, Callister 7e.
 CONTROLLING CORROSION
Metal oxide
• Self-protecting metals! Metal (e.g., Al,
-- Metal ions combine with O stainless steel)
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 Zn 2+
Adapted from Fig. 17.22(a),
Adapted Cu wire Callister 7e. (Fig. 17.22(a) is from
from Fig.
zinc zinc steel e- M.G. Fontana, Corrosion
17.23, Mg Mg2+
Callister 2e - 2e - pipe anode
Engineering, 3rd ed., McGraw-Hill
Book Co., 1986.)
7e.
steel Earth Chapter 17 - 14
Chapter 17 - 15
 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 used in 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 a -- adding inhibitors
protective oxide layer -- painting
-- reducing T -- using cathodic protection.

Chapter 17 - 16