Corrosion

Richard D. Sisson, Jr.

George F. Fuller Professor
Director of Manufacturing & Manufacturing Engineering
Mechanical Engineering Department
Worcester Polytechnic Institute
Worcester, MA 01609
508-831-5335
Sisson@wpi.edu
 CORROSION AND
DEGRADATION

• Why does corrosion occur?

• What metals are most likely to corrode?
• How do temperature and environment affect
corrosion rate?
• How do we suppress corrosion?
Keep it dry and cool!

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).
2
 8 FORMS OF CORROSION
• Uniform Attack
Oxidation & reduction
occur uniformly over
surface.
• Selective Leaching
Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).
• Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.
g.b.
prec.
attacked
zones
Fig. 17.9, Callister 6e.
• Stress corrosion • Erosion-corrosion
Stress & corrosion Break down of passivating
work together layer by erosion (pipe
at crack tips. elbows).
• Pitting
Forms Downward propagation
of of small pits & holes.
Fig. 17.8, Callister 6e.
corrosion (Fig. 17.8 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)
• Galvanic
Dissimilar metals are
• Crevice Between two
pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
corrodes.(see Table
17.2) Zn & Mg
Fig. 17.6, Callister 6e. (Fig. 17.6 is courtesy
very anodic. LaQue Center for Corrosion Technology,
Inc.) 9
 Uniform Corrosion
& Corrosion Products
• Anode reaction
Fe Æ Fe +2 + 2 e-
• Cathode Reaction
O2 + 2 H2O + 4e- Æ 4OH-
• Solubility Product
– Fe(OH)2 Æ Fe+2 + 2OH-
– Ksp = [Fe+2] [OH]2 = some constant (T)
• Corrosion Product = Rust = Fe(OH)2 etc.
– Rust is much more complicated chemically!
CORROSION OF ZINC IN ACID
• Two reactions are necessary:
-- oxidation reaction: Zn → Zn 2 + + 2e −
-- reduction reaction: 2H+ + 2e − → H2 (gas )
H+
oxidation reaction
Zn Zn 2+ H+
H+
Acid
Zinc flow of e -
2e - H+ solution
in the metal H+
H+ Adapted from Fig. 17.1, Callister 6e.
H2 (gas) (Fig. 17.1 is from M.G. Fontana,
H+ Corrosion Engineering, 3rd ed.,
re duction reaction McGraw-Hill Book Company, 1986.)

• Other reduction reactions:

-- in an acid solution -- in a neutral or base solution
O 2 + 4H+ + 4 e − → 2H2 O O 2 + 2H2 O + 4 e − → 4(OH) −
3
 Galvanic Corrosion
• Two different metals electrochemically
coupled
– Anode
– Cathode
– Conductive path
– Electrolyte!
 CORROSION IN A
GRAPEFRUIT or Potato!
Cathode Anode
Cu +
-
H+ Zn
H+ Zn 2+
2H+ + 2e − → H2 (gas )
+ − reduction 2e - oxidation
O 2 + 4H + 4 e → 2H2 O
H+
H+
Acid H+
H+ H+

6
 STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V • Ex: Cd-Ni cell
Cu +0.340
- +
more cathodic

Pb - 0.126
Sn - 0.136
Ni - 0.250 o
Co - 0.277 ∆V =
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 - 2.262
Na - 2.714
Data based on Table 17.1,
K - 2.924 Callister 6e.
5
 GALVANIC SERIES
• Ranks the reactivity of metals/alloys in seawater
Platinum
Gold
more cathodic

Graphite
(inert)

Titanium
Silver
316 Stainless Steel Based on Table 17.2, Callister
Nickel (passive) 6e. (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 Steel

(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
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 Crevice Corrosion
• Regions of restricted flow
– Beneath bolt heads
– Overlapping joints
– Rivets
• Leads to pitting
 Intergranular Corrosion
• Attack at or near grain boundaries
• Typically associated with welding or heat
treating problems
Stress Corrosion Cracking
 Corrosion protection
• Galvanic couples
– Galvanized steel
– Tin Cans?
• Impressed current
• Paint
• Vapor Phase Inhibitors
 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. 17.13(a),
Adapted
e- Cu wire Callister 6e. (Fig. 17.13(a) is
from Fig. zinc zinc steel
17.14, Mg Mg 2+ from M.G. Fontana, Corrosion
Callister 2e - 2e - pipe anode
Engineering, 3rd ed., McGraw-Hill
Book Co., 1986.)
6e. steel Earth
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 8 FORMS OF CORROSION
• Uniform Attack
Oxidation & reduction
occur uniformly over
surface.
• Selective Leaching
Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).
• Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.
g.b.
prec.
attacked
zones
Fig. 17.9, Callister 6e.
• Stress corrosion • Erosion-corrosion
Stress & corrosion Break down of passivating
work together layer by erosion (pipe
at crack tips. elbows).
• Pitting
Forms Downward propagation
of of small pits & holes.
Fig. 17.8, Callister 6e.
corrosion (Fig. 17.8 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)
• Galvanic
Dissimilar metals are
• Crevice Between two
pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
corrodes.(see Table
17.2) Zn & Mg
Fig. 17.6, Callister 6e. (Fig. 17.6 is courtesy
very anodic. LaQue Center for Corrosion Technology,
Inc.) 9
 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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