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CHAPTER 17:

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.

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).
Chapter 17 - 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 Zn 2+ H+
Acid
Zinc flow of e- 2e - H+
in the metal H+ solution
H+
H+ Adapted from Fig. 17.1, Callister 7e.
H2(gas) (Fig. 17.1 is from M.G. Fontana,
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
O2 4H 4e 2H2O O2 2H2O 4e 4(OH)
Chapter 17 - 3
STANDARD HYDROGEN (EMF) TEST
Two outcomes:
--Metal sample mass --Metal sample mass

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

Platinum
Mn+

metal, M
metal, M

Mn+ H+
ions ions
H+
25C 25C
1M Mn+ soln 1M H + soln 1M Mn+ soln 1M H+ soln
--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, Callister 7e.
Standard Electrode Potential
Chapter 17 - 4
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
Pb - 0.126 - +
Sn - 0.136
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Cd 25C Ni
Fe - 0.440
more anodic

Cr - 0.744
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 - 5
CORROSION IN A GRAPEFRUIT
Cathode Anode
+ -
Cu H+ Zn
H+ Zn 2+

reduction 2e - oxidation
2H 2e H2 (gas)
H+
O2 4H 4e 2H2O H+
Acid H+
H+ H+

Chapter 17 - 6
EFFECT OF SOLUTION
CONCENTRATION
Ex: Cd-Ni cell with Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
RT X
VNio VCd
o
0.153 VNi VCd V V
o
Ni lno
Cd
- - nF Y
+ +
n = #e-
per unit
oxid/red
Cd 25C 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
Reduce VNi - VCd by
C/mol.
--increasing X
--decreasing Y
Chapter 17 - 7
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
more anodic

Lead
316 Stainless Steel
(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
Chapter 17 - 8
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 Forms Downward propagation
one element/constituent of small pits & holes.
of Fig. 17.17, Callister 7e.
(e.g., Zn from brass (Cu-Zn)).
corrosion (Fig. 17.17 from M.G.
Intergranular Fontana, Corrosion
Engineering, 3rd ed.,
Corrosion along McGraw-Hill Book
Company, 1986.)
grain boundaries, Galvanic
often where special Dissimilar metals are
Crevice Between two
phases exist. pieces of the same metal.
physically joined. The
Rivet holes
g.b. more anodic one
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 - 9
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
from Fig.
zinc zinc e- Callister 7e. (Fig. 17.22(a) is
17.23, steel Mg Mg 2+ from M.G. Fontana, Corrosion
Callister 2e - 2e - pipe anode
Engineering, 3rd ed., McGraw-Hill
Book Co., 1986.)
7e. steel Earth Chapter 17 - 10
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 -- adding inhibitors
a protective oxide layer -- painting
-- reducing T -- using cathodic protection.

Chapter 17 - 11
ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 17 - 12