CORROSION AND OXIDATION OF METALS

ISSUES TO ADDRESS...
• Why does corrosion occur?
• What metals are most likely to corrode?
• How do environment affect corrosion rate?
• How do we suppress corrosion?
• What is oxidation?

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 Reading

– Textbook – Chapter 17
Section 17.1 Introduction
Section 17.2 Electrochemical considerations
Section 17.5 Passivity
Section 17.6 Environmental effects
Section 17.7 Forms of corrosion
Section 17.8 Corrosion Environments
Section 17.9 Corrosion prevention
Section 17.10 Oxidation (except section: kinetics)

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 Introduction

– Corrosion: Deterioration of a metal resulting

from chemical attack by its environment.

– Rate of corrosion depends upon temperature

and concentration of reactants and products.

– Metals have free electrons that setup

electrochemical cells within their structure.

– Metals have tendency to go back to low

energy state by corroding.

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 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)*

* 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.
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 Corrosion of Steel Structures

http://www.galvanizeit.org www.bensalem.ae/concrete.html

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 Oxidation-Reduction Reactions

e-

Anode Cathode
Oxidation reaction Reduction reaction
Production of e- Consumption of e-
M  Mn+ + n e- 2 H+ + 2 e-  H2

All the electrons produce during the oxidation

reaction are consumed during the reduction reaction
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 CORROSION OF ZINC IN ACID

• Two reactions are necessary:

-- oxidation reaction: Zn → Zn2+ + 2e−
-- reduction reaction: 2H+ + 2e− → H2 (gas)
H+
Oxidation reaction
Zn Zn2+ H+
H+ Acid
Zinc flow of e- 2e-
in the metal H+ + solution
H Adapted from Fig. 17.1, Callister 7e.
H+ (Fig. 17.1 is from M.G. Fontana,
H2(gas) Corrosion Engineering, 3rd ed.,
H+ McGraw-Hill Book Company, 1986.)
reduction reaction

• Other reduction reactions:

-- in an acid solution -- in a neutral or base solution
With dissolved oxygen O2 + 2H2O + 4e− → 4(OH)−
O2 + 4H+ + 4e− → 2H2O
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 CORROSION IN A GRAPEFRUIT

Cathode Anode
+ -
Cu H+ Zn
H+ Zn 2+

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

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 GALVANIC SERIES

• Ranks 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) 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 Steel

(active)

Iron/Steel
Aluminium Alloys
Cadmium
Zinc
Magnesium
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 Galvanic Cells

- +

Cd 25°C Ni

1.0 M 1.0 M
Cd 2+ solution Ni 2+ solution

Anode Cathode
Cd  Cd2+ + 2e- Ni2+ + 2 e-  Ni

Adapted from Fig. 17.2, Callister 7e.

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 Cell of Single Electrode

H+
Oxidation reaction
Zn Zn 2+ H+
H+
Acid
Zinc flow of e- 2e -
in the metal H+ solution
H+
H+
H2(gas)
H+
reduction reaction

Anode Cathode
Zn  Zn2+ + 2e- 2H+ + 2 e-  H2

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 Concentration Cells

- + - +

Fe 25°C Fe Fe 25°C Fe
Fe2+

Low concentration High concentration Low O2 High O2

Fe 2+ solution Fe2+ solution concentration concentration

Anode Cathode Anode Cathode

Fe  Fe2+ + 2e- Fe2+ + 2 e-  Fe Fe  Fe2+ + 2e- O2+2H2O + 4 e-  4OH-

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 Stress Concentration Cells

- +

Cold work
material Fe 25°C Fe
Annealed
material

Fe 2+ solution Fe2+ solution

Anode Cathode
Fe  Fe2+ + 2e- Fe2+ + 2 e-  Fe

Both side have the same

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concentration in Fe2+, initially Page 14
 Question Time 1

Iron nail 1

What would
Iron nail 2
happen if each
set of items
was placed in
a baker filled Iron nail
with seawater?

Zinc plate
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Copper wire Page 15
 Passivity

Under particular environmental conditions, some normally active metals or alloys lose
their chemical reactivity to become extremely inert

What happens?
Formation of a very thin and adhesive oxide film or scale on metal surface:
protective barrier to further corrosion

Ex: aluminium very corrosive resistant in most environments because it passivates (creation of
oxide layer on the surface – Al2O3)

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 Oxidation in Gaseous Atmospheres

– Oxidation can also happen in dry environment, i.e. air: formation of oxide
layer or scale
– Mechanism:

Acts as electrolyte and

electrical circuit

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 Stainless steel

– Composition: at least 11% weight Cr (but can be as much as 26%

weight Cr in harsh environments)
– Property: does not stain, corrode or rust as easily as other steels

WHY?
The chromium forms a passivation layer of chromium (III) oxide
(Cr2O3) when exposed to oxygen. The layer is too thin to be visible
(the metal remains lustrous) but is impervious to water and air,
protecting the metal beneath.

The 192 m high,

stainless-clad (type
304) Gateway Arch in
St. Louis, Missouri,
USA

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 Environmental Effects

Environment Corrosion factors Metals for applications

Moisture (contains O2) Aluminium and copper alloys,
galvanized steel
Air Acid rains (contain dilute sulfuric
acid solution)

Fresh: contains O2 Cast irons, steel, aluminium,

copper, brass and some
stainless steels

Water Titanium, brass, copper-nickel

alloys, Ni-Cr-Mo alloys
Seawater: contains salts (more
corrosive than fresh water)
Wide range of compositions and
susceptibilities to corrosion:
Soils moisture, oxygen, salts, acidity Cast irons, plain carbon steels

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 Environmental Considerations

– Rate of corrosion increases if:

 Fluid velocity increases (more turbulence)

 Temperature increases

 Concentration of corrosive species increases

 There are some stress concentration points

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 FORMS OF CORROSION

• Stress corrosion
• Uniform Attack • Erosion-corrosion

• Selective Leaching 10 • Pitting

Forms
of
• Crevice
corrosion
• Intergranular

• Fretting corrosion
• Cavitation damage
• Galvanic

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 Uniform Attack

The corrosion occurs with equivalent intensity over the entire surface
Ex: rusting of iron and steel
tarnishing of silverware
Most common type of corrosion

Can be predicted and designed for

- Protective coatings
- Using inhibitors
- Cathodic protection

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 Cathodic Protection or Sacrificial Anode

– Addition of another metal that will oxidize instead of the other one(s)
– From the Galvanic series look at which metals are the most anodic: Mg and
Zn

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

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 Galvanization of Steel

The process:
1) Surface preparation
2) Galvanazing: immersion of the material of a bath of 98% pure Zn at 449° C
3) Inspection

Protection:
During the use of the part, the zinc layer will be scratched or damaged but the exposed
area of steel will be protected by the oxidation of Zn. Process will be slow because the
anode to cathode surface ratio very large

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 Galvanic Corrosion

Happens when two metals of different compositions are electrically connected

One metal corrodes and one metal is inert
Ex: steel will corrode when in contact with brass in marine environment

Prevention measures:
- Choose two metals close in the galvanic series
- Use an anode with the largest area possible
- Electrically insulate metals from each other
- Cathodic protection: electrically connect a 3rd anodic metal to the two others.

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 Crevice Corrosion

Occurs as a consequence of ions or dissolved gas concentration differences in

the electrolyte solution between two regions of the same metal.
Ex: Riveted plates

Areas where
corrosion occurs

Prevention measures:
- Weld instead of using rivets or bolds
- Use non-absorbing gaskets when possible
- Remove accumulated deposits frequently
- Design vessels with no stagnant area and assure complete drainage

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 Pitting

Also localised corrosion occurring most probably with the same mechanisms as
crevice corrosion.
Small holes or pits form at the surface and grow downward due to gravity

Fig. 17.17, Callister 7e.

(Fig. 17.17 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)

Prevention measures:
- Avoid surface defects such as scratches (polish the surface)
- Avoid changes in composition at the surface
- For steel, add ~2% molybdenum to improve resistance to pitting

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 Intergranular Corrosion

Under some circumstances GB become more sensitive to corrosion than the rest of the
material.
Ex: During welding of steels, Cr and C atoms diffuse to GB and form precipitates of
chromium carbide making areas close to GB less resistant to corrosion than the bulk
material.

Prevention measures:
- Subject the material to a high temperature heat treatment to dissolve precipitates
- Lower carbon content
- Add Nb or Ti that will form more easily precipitates than Cr but more resistant than
to corrosion

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 Selective Leaching

Happens in solid solution alloys when one element or constituent is more sensitive to
corrosion and will be remove preferentially from the material
Ex: Brass Cu+Zn
Zn more sensitive to corrosion than Cu so it will be removed from the material
 Formation of porous copper: lost of mechanical properties

Prevention measures:
- Change the composition of the alloy
- Cathodic protection
- Change the corrosive environment

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 Errosion-Corrosion

Happens under the combined action of chemical attack and mechanical abrasion or
wear due to fluid motion.
Ex: form of corrosion found in piping especially at bends or elbows and abrupt
change in diameter turbulence

Prevention measures:
- Change design to limit fluid turbulence
- Use material that resists erosion

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 Stress Corrosion or Stress Corrosion Cracking

Happens under combined action of tensile stress and corrosion environment.

Formation of small cracks that propagate perpendicularly to loading direction failure

Prevention measures:
- Reduce applied stress or increase cross-sectional area subjected to load
- Heat treatment to cancel out any residual stress
- Change alloy
- Cathodic protection
- Add inhibitors

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 Question Time 2

What type of corrosion these two materials have been subjected to?

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 Hydrogen Embrittlment

– Reduction of ductility and TS in metals and alloys due to the presence of

hydrogen
– H diffuse interstitially through the crystal lattice forming cracks
 Brittle failure
This phenomenon can occur during surface treatment or welding cause of failure in
martensitic steels

Prevention measures:
- Reduce TS of alloy by heat treatment
- Remove H source
- “baking” alloy at high temperature to drive away the dissolved H
- Change alloy to one less sensitive to hydrogen embrittlement

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 CONTROLLING CORROSION

• Self-protecting metals! Metal oxide

-- Metal ions combine with O Metal (e.g., Al,
to form a thin, adhering oxide layer that slows corrosion. stainless steel)
• 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
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 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.
• 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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