Chapter 10:

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?

1
 THE COST OF CORROSION
• Corrosion:
-- the destructive
electrochemical
attack of a material.
-- Ex: Rusting of
automobiles and

© EHStock/iStockphoto
other equipment

• 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).

2
 ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:
H+
Oxidation reaction
Zn Zn2+ H+
H+ Acid
Zinc flow of e- 2e -
in the metal H+ + solution
H
H+
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution

3
 STANDARD HYDROGEN ELECTRODE
• Two outcomes:
-- Corrosion -- Electrodeposition

e- e- e- e-

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

Platinum
Platinum

metal, M
metal, M

ions ions
H+
H2(gas)
25oC 25oC
1M M n+ sol’n 1M H + sol’n 1M M n+ sol’n 1M H + sol’n

-- Metal is the anode (-) -- Metal is the cathode (+)

(relative to Pt) (relative to Pt)

Standard Electrode Potential

4
 STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
V metal corrodes.
Au +1.420 V
Cu +0.340
• Ex: Cd-Ni cell
more cathodic

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

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, Fig. 17.2, Callister & Rethwisch 10e.
K - 2.924 Callister 10e.
5
EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE

• Ex: Cd-Ni cell with

standard 1 M solutions

- +

Cd 25°C Ni

1.0 M 1.0 M
Cd 2+ solution Ni 2+ solution
EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
• Ex: Cd-Ni cell with 𝑅𝑅𝑅𝑅
non-standard solutions 𝑉𝑉 = 𝑉𝑉𝑜𝑜 − ln(𝑄𝑄)
𝑛𝑛𝑛𝑛
- + 2.303𝑅𝑅𝑅𝑅
𝑉𝑉 = 𝑉𝑉𝑜𝑜 − l𝑜𝑜𝑜𝑜(𝑄𝑄)
𝑛𝑛𝑛𝑛
0.0592 1
Cd T Ni
𝑉𝑉 = 𝑉𝑉𝑜𝑜 − l𝑜𝑜𝑜𝑜 𝑛𝑛+
𝑛𝑛 [𝑀𝑀1 ]

XM YM 𝑛𝑛+
𝑜𝑜 𝑜𝑜
0.0592 [𝑀𝑀1 ]
Cd 2+ solution Ni 2+ solution ∆𝑉𝑉 = (𝑉𝑉2 − 𝑉𝑉1 ) − l𝑜𝑜𝑜𝑜 𝑛𝑛+
𝑛𝑛 [𝑀𝑀2 ]
• Increase ΔV by
-- increasing X Nernst Equation
-- decreasing Y F = Faraday’s constant = 96,500 C/mol.
-- increasing T
n = #e- per unit oxid/red reaction (= 2 here)
7
 Example
One-half of an electrochemical cell consists of a pure nickel electrode in a solution of Ni2+ ions. The other half is a
cadmium electrode immersed in a Cd2+ solution.

(a) If the cell is a standard one, write the spontaneous overall reaction and calculate the voltage that is generated.
(b) Compute the cell potential at 25oC if the Cd2+ and Ni2+ concentrations are 0.5 and 10-3 M, respectively. Is the
spontaneous direction still the same as the standard cell?

The cadmium electrode will be oxidized because it is lower in

- + the EMF series.

𝐶𝐶𝐶𝐶 → 𝐶𝐶𝐶𝐶2+ + 2𝑒𝑒 −

𝑁𝑁𝑁𝑁 2+ + 2𝑒𝑒 − → 𝑁𝑁𝑁𝑁

𝑁𝑁𝑁𝑁 2+ + 𝐶𝐶𝐶𝐶 → 𝑁𝑁𝑁𝑁 + 𝐶𝐶𝐶𝐶2+

Cd T Ni

𝑜𝑜 𝑜𝑜
∆𝑉𝑉 = 𝑉𝑉𝑁𝑁𝑁𝑁 − 𝑉𝑉𝐶𝐶𝐶𝐶 = −0.250 𝑉𝑉 − −0.43 𝑉𝑉 = +0.153 𝑉𝑉
XM YM
Cd 2+ solution Ni 2+ solution

8
 Example
One-half of an electrochemical cell consists of a pure nickel electrode in a solution of Ni2+ ions. The other half is a
cadmium electrode immersed in a Cd2+ solution.

(a) If the cell is a standard one, write the spontaneous overall reaction and calculate the voltage that is generated.
(b) Compute the cell potential at 25oC if the Cd2+ and Ni2+ concentrations are 0.5 and 10-3 M, respectively. Is the
spontaneous direction still the same as the standard cell?

Not sure which oxidizes/reduces… so must guess. Let’s assume the reverse is now true: Ni oxidizes and Cd reduces.

- + 0.0592 [𝑀𝑀1𝑛𝑛+ ]
∆𝑉𝑉 = (𝑉𝑉2𝑜𝑜 − 𝑉𝑉1𝑜𝑜 ) − l𝑜𝑜𝑜𝑜 𝑛𝑛+
𝑛𝑛 [𝑀𝑀2 ]

𝑜𝑜 𝑜𝑜 0.0592 [𝑁𝑁𝑁𝑁 2+ ]
∆𝑉𝑉 = (𝑉𝑉𝐶𝐶𝐶𝐶 − 𝑉𝑉𝑁𝑁𝑁𝑁 )− l𝑜𝑜𝑜𝑜
𝑛𝑛 [𝐶𝐶𝐶𝐶 2+ ]

Cd T Ni
0.0592 [10−3 ]
∆𝑉𝑉 = (−0.403 𝑉𝑉) − (−0.250 𝑉𝑉) − l𝑜𝑜𝑜𝑜
2 [0.5]

XM YM
∆𝑉𝑉 = −0.073 𝑉𝑉
Cd 2+ solution Ni 2+ solution

Since the change in potential is negative, the reaction as written is non-spontaneous.

Therefore, Ni reduces and Cd oxidizes.
9
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive) Table 17.2, Callister & Rethwisch
Nickel 200 (passive) 9e.
Source is Davis, Joseph R. (senior editor),
Copper ASM Handbook, Corrosion,
Nickel 200 (active) Volume 13, ASM International, 1987, p.
83, Table 2.
Tin
Lead
more anodic

316 Stainless Steel (active)

(active)

Cast Iron/Low-carbon Steel

Aluminum Alloys
Cadmium
Zinc
Magnesium
10
 FORMS OF CORROSION
• Stress corrosion
Corrosion at crack tips
• Uniform Attack when a tensile stress is • Erosion-corrosion
Oxidation & reduction 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 10e. (Photograph
• Intergranular courtesy of Rick Adler/Adler
Engineering LLC of Wyoming
Corrosion along USA)

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 10e.
zones
more anodic metal (Courtesy LaQue Center for Corrosion

Fig. 17.18, Callister & corrodes. Technology, Inc.)

11
Rethwisch 10e.
 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
Metal oxide
- These metals form a thin, Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.
• Lower the temperature (reduces rates of oxidation and
reduction)
• Apply physical barriers -- e.g., films and coatings

12
 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
Zn 2+ Cu wire
e-
zinc zinc steel Mg Mg 2+
2e - 2e - pipe anode
steel Earth
e.g., zinc-coated nail e.g., Mg Anode
13
 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

14