Corrosion & Degradation

Mechanisms, Types, Prevention

Prepared by: J G. Caliston

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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?

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THE COST OF CORROSION
• Corrosion:
-- the destructive electrochemical attack of a material.
-- Ex: 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)*
-- in the U.S. 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). 5
fig_17_02
fig_17_03
fig_17_04
fig_17_05
ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction: Zn → Zn2+ + 2e−
-- reduction reaction: 2H+ + 2e− → H2 (gas)
H+
Oxidation reaction
Zn Zn2+ H+
Adapted from Fig. 17.1,
Callister & Rethwisch 8e.

H+ Acid (Fig. 17.1 is from M.G.

Zinc flow of e- 2e- Fontana, Corrosion
in the metal H+ + solution Engineering, 3rd ed., McGraw-
H
H+ Hill Book Company, 1986.)
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution
O2 + 4H+ + 4e− → 2H2O O2 + 2H2O + 4e− → 4(OH)−
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 STANDARD HYDROGEN
• Two outcomes:
ELECTRODE
-- Corrosion -- Electrodeposition

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

Platinum
metal, M
metal, M

ions ions
H+
H2(gas)
25ºC 25ºC
1M Mn+ sol’n 1M H + sol’n 1M Mn+ sol’n 1M H+ sol’n
-- 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,
Standard Electrode Potential Callister & Rethwisch
11 8e.
 STANDARD
• EMF series
EMF SERIES
• Metal with smaller
o
Vmetal o
metal Vmetal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic

Cu +0.340 o o
Pb - 0.126 VCd < V Ni ∴ Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 ∆V o =
Cd - 0.403 0.153V
Fe - 0.440
Cd Ni
more anodic

Cr - 0.744 25ºC
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2+ solution Ni 2+ solution
Na - 2.714
Data based on Table 17.1, Adapted from Fig. 17.2,
K - 2.924 Callister 8e. Callister & Rethwisch
12 8e.
EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
o RT X
o
o o
V −V = 0.153 V
Ni Cd
VNi − VCd = V −V −
Ni ln
Cd
- - nF Y
+ +
n = #e-
per unit
oxid/red
Cd 25ºC 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
• Reduce VNi - VCd by = 96,500
C/mol.
-- increasing X
-- decreasing Y13
-- increasing T
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive) Based on Table 17.2, Callister &
Nickel (passive) Rethwisch 8e. (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)

(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium 14
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FORMS OF CORROSION
• Stress corrosion
Corrosion at crack tips
• Uniform Attack when a tensile stress • Erosion-corrosion
Oxidation & reduction is present. Combined chemical attack and
reactions occur uniformly mechanical wear (e.g., pipe
over surfaces. elbows).
• Selective Leaching • Pitting
Preferred corrosion of Forms Downward propagation
one element/constituent of of small pits and holes.
[e.g., Zn from brass (Cu-Zn)].
corrosion
Fig. 17.17, Callister &
Rethwisch 8e. (Fig. 17.17
• Intergranular from M.G. Fontana,
Corrosion Engineering,
Corrosion along 3rd ed., McGraw-Hill Book
Company, 1986.)
grain boundaries,
often where precip. • Galvanic • Crevice Narrow and
particles form. Dissimilar metals are confined spaces.
g.b. physically joined in the Rivet holes
prec. presence of an
electrolyte. The
attacked Fig. 17.15, Callister & Rethwisch 8e. (Fig. 17.15
zones more anodic metal 18 for Corrosion
is courtesy LaQue Center
Technology, Inc.)
Fig. 17.18, Callister & corrodes.
Rethwisch 8e.
fig_17_14
fig_17_15
fig_17_16
fig_17_17
fig_17_17
fig_17_19
fig_17_20
fig_17_21
CORROSION PREVENTION (i)

• Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
-- Use metals that passivate
- These metals form a thin, Metal oxide
Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.
• Lower the temperature (reduces rates of oxidation and
reduction) = environmental alteration
• Apply physical barriers -- e.g., films and coatings

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CORROSION PREVENTION (ii)
• Add inhibitors (substances added to solution that decrease
its reactivity)
-- 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.

• Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
Galvanized Steel Using a sacrificial anode
Adapted Zn 2+ Cu wire Adapted
from Fig. e- from Fig.
17.23, zinc zinc steel Mg Mg 2+ 17.22(a),
2e - 2e -
Callister &
Rethwisch pipe anode Callister &
Rethwisch
8e. steel Earth 8e.
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e.g., zinc-coated nail e.g., Mg Anode
fig_17_23
fig_17_22
 Degradation of Polymers
 Polymeric materials deteriorate by
physio-chemical means

 It means both physical as well as chemical

 Mechanisms for degradation are not well

understood due to the chemical
complexity of polymers

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 Types of Deterioration
A. Swelling and dissolution

a. swelling, the liquid or solute diffuses into and is absorbed

within the polymer

b. the small solute molecules fit into and occupy positions

among the polymer molecules

c. the macromolecules are forced apart such that the

specimen expands or swells

Dissolution - occurs when the polymer is completely soluble

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 Types of Deterioration
B. Bond Rupture (‘scission’)
- is the rupture or severance of chemical chain bonds
These are caused by:

a. Radiation Effects
- certain types of radiation can penetrate a
polymer and cause the removal of an orbital electron
(ionization) causing the breaking of a bond

b. Chemical Reaction Effects

- Ozone, oxygen etc. can cause scission as a result of
chemical reaction
Ex. rubber subjected to tensile stresses will show cracks

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 Types of Deterioration

c. Thermal Effects
- degradation happens when polymers are subjected to
high temperatures resulting in scission of molecular
chains

C. Weathering
- exposure to outdoor conditions which may be a
combination of several processes

- usually by means of oxidation

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SUMMARY
• Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction
• Metals and alloys are ranked according to their
corrosiveness in standard emf and galvanic series.
• Temperature and solution composition affect corrosion
rates.
• Forms of corrosion are classified according to mechanism
• Corrosion may be prevented or controlled by:
-- materials selection
-- reducing the temperature
-- applying physical barriers
-- adding inhibitors
-- cathodic protection
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End

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