Chapter 11 Corrosion

CHAPTER
11
Corrosion
1
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display
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.
Ceramics and polymers suffer corrosion
by direct chemical attack.
Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi
Oxidation Reduction Reactions
A metal (Eg Zn) placed in HCL undergoes corrosion.
Zn + 2HCL
ZnCl2 + H2
or
Zn + 2H+
Zn2+ + H2
also
Zn
Zn 2+ + 2e- (oxidation half cell reaction)
2H+ + 2eH2 (Reduction half cell reaction)
Oxidation reaction: Metals form ions at local anode.
Reduction reaction: Metal is reduced in local charge at
Local cathode.
Oxidation and reduction takes place at same rate.
3
Standard electrode Half-Cell Potential of Metals
Oxidation/Reduction half cell potentials are compared

with standard hydrogen ion
half cell potential.
Voltage of metal (Eg-Zn) is
directly measured against
hydrogen half cell electrode.
Anodic to hydrogen
More tendency to corrode
Examples:- Fe (-0.44), Na (-2.74)
Cathodic to hydrogen
Less tendency to corrode
Examples:- Au (1.498), Cu (0.33)
Macroscopic Galvanic Cells with 1M Electrolyte
Two dissimilar metal electrodes immersed in solution of their

own ions.
Electrode that has more
negative oxidation potential
will be oxidized.
Oxidized
Reduced
Zn
Zn2+, Cu2+
Cu
Half cell reactions are
Zn
Zn 2+ + 2e- E0 = -0.763 V
Cu
Cu2+ + 2e- E0 = + 0.337 V
Or Cu2+ + 2eCu E0 = -0.337 V (negative sign)
Adding two reactions,
Zn + Cu2+
zn2+ + Cu E0cell = -1.1V
5
Galvanic Cells With Electrolytes not 1M
If the concentration of electrolyte surrounding anode is

not I molar, driving force for corrosion is greater.
There will be more negative emf half cell reaction
M
Mn+ + ne Nernst Equation:
EE
0
0.0592
n
log Cion
E = Net efm of half cell
E0 = Standard emf of half cell
N = Number of electrons transferred
Cion = Molar concentration of ions.
Galvanic Cells With Acid or Alkaline Electrolytes
Consider iron and copper electrodes in acidic electrolyte.

Since standard electrode potential of Fe to oxidize is
0.44 , compared to 0.337 of copper,
Fe
Fe2+ + 2e-
Since there are no copper ions to reduce

2H+ + 2eH2
If electrolyte contains oxidizing agent

O2 + 4H4+ + 4e2H2O
If electrolyte is neutral or basic,

O2 + 2H2O + 4e4OH-
Microscopic Galvanic Cell Corrosion of Single Electrode
When single electrode is immersed in an electrolyte,

microscopic cathodes and anodes are formed due to
structural irregularities.
Oxidation reaction occurs at local anode and reduction
reaction at local cathode.
If iron is immersed in
oxygenated water,
Fe
Fe2+ + 2e-
O2 + 2H2O + 4e-
4OH-
2Fe + 2H2O + O2
2Fe2+ + 4OH-
2Fe(OH)2
Concentration of Galvanic Cells
If a concentration cell is created by immersing 2 electrodes in

electrolytes of different concentrations of same ion, electrode
in dilute electrolyte will be anode.
Example:- 2 Fe electrodes
immersed in electrolytes
of 0.001M and 0.01 M
Fe 2+ electrolyte.
E fe2+ = E0 + 0.0296 log Cion
for 0.001M E Fe2+ = -0.44V + 0.0296 log 0.001 = -0.529 V
for 0.01M
E Fe2+ = -0.44V + 0.0296 log 0.01 = -0.499 V
Since 0.529 V is more negative than 0.499 V, electrode in
0.001 M solution is anode and gets corroded.
9
Oxygen Concentration Cells
If two electrodes are immersed in electrolytes of different

oxygen concentrations, electrode in low-oxygen content
electrolyte is anode.
Example: Two iron electrodes, one in low oxygen
concentration water and another in high oxygen
concentration water.
Anode reaction : Fe
Fe2+ + 2eCathode reaction: O2 + 2H2O + 4e4OH
10
Since cathode reaction requires O2 and electrons, high

concentration oxygen is cathode.
Grain Grain boundary Electrochemical cells
Grain boundaries are more anodic and hence get

corroded by electrochemical attack.
Grain boundaries are at higher energy.
Impurities migrate to grain boundaries.
Solute segregation might cause grain boundaries to
become more cathodic.
Grain
Boundary
Grain boundary
(anode)
Grain boundary
(cathode)
anode
Cartridge Brass
11
Multiple Phase Electrochemical Cells
In multiple alloys, one phase is more anodic than another.

Corrosion rates are higher in multiphase alloys.
Example: In pearlite gray cast iron, graphite flake is
cathodic than surrounding pearlite matrix.
Anodic pearlite corrodes
Steel, in martensitic condition

(single phase) after quenching
from austenitic condition, has
better corrosion resistance.
Impurities in metals leads to precipitation of intermetallic
phases and hence forms anodic and cathodic regions Figure 12.10
leading to corrosion.
12
Rate of Uniform Corrosion
Faradays equation:
ItM iAtM
W
nF
nF
W = weight of metal (g), corroded or electroplated in an

aqueous solution in time t, seconds.
I = Current flow A, i = current density A/cm2
M = atomic mass of metal g/mol
n = number of atoms/electron produced or consumed
F = Faradays Constant, A = area Cm2
Corrosion rate is expressed as weight loss per unit area
per unit time or loss in depth per unit time.
13
Corrosion Reaction and Polarization
When a metal corrodes, the potentials of local cathode and

anode are not at equilibrium.
Polarization: Displacement of
Zn in acid
solution
electrode potential from their
equilibrium values to some
intermediate value and creation of net current flow.
14
Point A : equilibrium potential and current density of Zn

Point B : equilibrium potential and current density of H
Point C : Intermediate point
Activation and Concentration Polarization

Activation polarization:
15
Electrochemical reactions that

are controlled by a slow step in
a reaction sequence.
There is a critical activation
energy to surmount energy
barrier associated with slowest
step.
Concentration polarization:
Associate with electrochemical
reaction and controlled by diffusion
of ions.
Example: Reduction rate of H+ ions
at surface is controlled by diffusion
of H+ ions into metal surface.
Passivation
Passivation is loss of chemical reactivity in presence of a

environmental condition.
Formation of surface layer of reaction products that
inhibit further reaction.
Oxide film theory: Passive film is always a diffusion
barrier of reaction products.
Adsorption theory: Passive metals are covered by
chemisorbed films of oxygen.
Examples:- Stainless steel, nickel alloys, titanium and
aluminum alloys.
16
Polarization Curve
Polarization curve shows how the potential of a metal

varies with current density.
As the electrode potential
is made more positive, the
metal behaves as an active
metal.
When potential reaches Epp
(primary passive potential)
current density decreases an
hence the corrosion rate.
Further increase in potential makes metal active again.
17
The Galvanic Series.
Many metals do not

behave as galvanic cells
due to passive films.
Galvanic series gives the
cathodic, anodic
relationship between the
metals.
In flowing seawater,
Zinc is more active than
aluminum.
Series is determined
experimentally for every
corrosive environment.
18
Types of Corrosion
Uniform or general attack corrosion: Reaction proceeds

uniformly on the entire surface.
Controlled by protective coatings, inhibitors and
cathodic protection.
Galvanic or two metal corrosion: Electrochemical
reaction leads to corrosion of on metal.
Zinc coatings on steel protects steel as zinc is
anodic to steel and corrodes.
Large cathode area to small anode area should be
avoided.
19
Pitting Corrosion
Pitting: Localized corrosive attacks that produces holes or

pits in a metal.
Results in sudden unexpected failure as pits go undetected
(covered by corrosion products).
Pitting requires an initiation
period and grows in
direction of gravity.
Pits initiate at structural
and compositional
heterogeneities.
20
Pitting of stainless steel

Growth of Pit
Growth of pit involves dissolution of metal in pit

maintaining high acidity at the bottom.
Anodic reaction at the
bottom and cathodic
reaction at the metal
surface.
At bottom, metal chloride + water
Metal hydroxide +
free acid.
Some metals (stainless steel) have better resistance than
others (titanium).
21
Crevice Corrosion
Localized electrochemical corrosion in crevices and under

shielded surfaces where stagnant solutions can exist.
Occurs under valve gaskets, rivets and bolts in alloy
systems like steel, titanium and copper alloys.
Anode: M M+ + eCathode:O2 + 2H2O + 4e4OHAs the solution is
stagnant, oxygen is used up
and not replaced.
Chloride ions migrate to
crevice to balance positive charge and form metal
hydroxide and free acid that causes corrosion.
22
Intergranular Corrosion
Localized corrosion at and/or adjacent to highly reactive

grain boundaries resulting in disintegration.
When stainless steels are heated to or cooled through
sensitizing temperature range (500-8000C) chromium
carbide precipitate along grain boundaries.
When exposed to corrosive environment, the region next
to grain boundaries become anodic and corrode.
23
Stress Corrosion
24
Stress corrosion cracking (SCC): Cracking caused by

combined effect of tensile stress and corrosive
environment.
Stress might be residual and applied.
Only certain combination
of alloy and environment
causes SCC.
Crack initiates at pit or
other discontinuity.
Crack propagates perpendicular
to stress
Crack growth stops if either stress or corrosive
environment is removed.
Erosion Corrosion and Cavitation Damage

Erosion corrosion: Acceleration in rate of corrosion due
to relative motion between corrosive fluid and surface.
Pits, grooves, valleys appear on surface in direction of
flow.
Corrosion is due to abrasive action and removal of
protective film.
Cavitation damage: Caused by collapse of air bubbles or
vapor filled cavities in a liquid near metal surface.
Rapidly collapsing air bubbles produce very high pressure
(60,000 PSI) and damage the surface.
Occurs at metal surface when high velocity flow and
pressure are present.
25
Fretting Corrosion and Selective Leaching
Fretting corrosion: Occurs at interface between materials

under load subjected to vibration and slip.
Metal fragments get oxidized and act as abrasives
between the surfaces.
Selective leaching: Selective removal of one element of
alloy by corrosion.
Example: Dezincification
Selective removal of
zinc from copper and brasses.
Weakens the alloy as single metal might not have
same strength as the alloy.
26
Hydrogen Damage
27
Load carrying capacity of a metallic component reduced

due to interaction with atomic/molecular hydrogen.
Happens in low carbon and alloy steels, aluminum alloys
and titanium alloys.
Cracking, blistering, hydride formation, reduced ductility
(hydrogen embrittlement).
Caused due to the diffusion of hydrogen into metal.
Bakeout is a process applied to the component to diffuse
the hydrogen out of the metal.
Oxidation- Protective Oxide Films
28
Oxides form on metals due to reaction with air.

Degree to which oxide films form depends on following
factors.
Volume ratio of oxide to metal consumed after oxidation
should be close to 1.
Good adherence.
High melting point of the film.
Low oxide pressure.
Coefficient of expansion equal to that of metal.
High temperature plasticity.
Low conductivity and diffusion coefficients of metal ions
and oxygen.
Mechanisms of Oxidation
Oxidation partial reaction: M

M 2+ + 2eReduction partial reaction: O2 + 2eO2-
Oxidation starts by lateral expansion of discrete oxide

nuclei.
Metal diffuses as electrons or cations across oxide films.
Sometimes O2- ions diffuse to oxide metal interface and
electrons diffuse to oxide gas interface.
29
Oxidation Rates
Oxidation rate is expressed

as weight gained per unit area.
Linear oxidation behavior
W=weight gained
W = KLt
per unit area
KL = linear rate
constant.
T = time
If ion diffusion is controlling the step (Eg Fe, Cu)

W2 = Kpt+C Kp = Parabolic rate constant, C = constant
Some metals follow logarithmic rate law
W = Ke Log(Ct + A) C, A = constants, Ke = logarithmic rate
constant
Examples:- Al, Cu, Fe (at slightly elevated temperature)
30
Corrosion Control Material Selection
31
Metallic Metals:
Use proper metal for particular environment.
For reducing conditions, use nickel and copper
alloys.
For oxidizing conditions, use chromium based
alloys.
Nonmetallic Metals:
Limit use of polymers in presence of strong
inorganic acids.
Ceramics have better corrosion resistance but are
brittle.
Coatings
Metallic Coatings: Used to protect metal by separating

from corrosive environment and serving as anode.
Coating applied through electroplating or roll
bonding.
might have several layers.
Inorganic coatings: Coating with steel and glass.
Steel is coated with porcelain and lined with glass.
Organic coatings: Organic polymers (paints and
varnishes) are used for coatings.
Serve as barrier but should be applied carefully.
32
Design
33
General design rules:

Provide allowance for corrosion in thickness.
Weld rather than rivet to avoid crevice corrosion.
Avoid dissimilar metals that can cause galvanic
corrosion.
Avoid excessive stress and stress concentration.
Avoid sharp bends in pipes to prevent erosion
corrosion.
Design tanks and containers for early draining.
design so that parts can be easily replaced.
Design heating systems so that hot spots do not occur.
Alteration Environment
Lower the temperature

Reduces reaction rate.
Decrease velocity of fluids Reduces erosion
corrosion.
Removing oxygen from liquids reduces
corrosion.
Reducing ion concentration
decreases corrosion
rate.
Adding inhibitors
inhibitors are retarding
catalysts and hence reduce corrosion.
34
Cathodic Protection
Electrons are supplied to the metal structure to be

protected.
Example: Fe in acid
Fe
Fe2+ + 2e2H+ + 2eH2
Corrosion of Fe will be
prevented if electrons
are supplied to steel
structure.
Electrons can be supplied by external DC supply or
galvanic coupling with more anodic metal.
35
Anodic Protection
Externally impressed anodic currents form protective

passive films on metal and alloy surfaces.
Anodic currents are applied by potentiostat to protect
metals that passivate.
Current makes them more passive and decreases the
corrosion rate.
36
Exercise
1. Define corrosion as it pertains to materials.
2. What are some of the factors that affect the corrosion of
metals?
3. What is a standard half-cell oxidation-reduction potential?
4. A standard galvanic cell has electrodes of zinc and tin.
Which electrode is the anode? Which electrode corrodes?
What is the emf of the cell?
5. Briefly describe the following theories of metal passivity:
(a) the oxide theory and (b) the adsorption theory.
6. What is crevice corrosion? Describe an electrochemical
mechanism for the crevice corrosion of a stainless steel in
an aerated sodium chloride solution.
37
Exercise
7. What is intergranular corrosion? Describe the
metallurgical condition that can lead to intergranular
corrosion in an austenitic stainless steel.
8. Describe three methods of avoiding intergranular
corrosion in austenitic stainless steels.
9. What is stress-corrosion cracking (SCC)? Describe a
mechanism of SCC.
10. What is erosion corrosion? What is cavitation damage?
11. Describe fretting corrosion.
12. Define and give an example of (a) activation polarization
and (b) concentration polarization
38

Chapter 11 Corrosion

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Chapter 11 Corrosion

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CHAPTER

Corrosion: Deterioration of a metal

Oxidation Reduction Reactions

A metal (Eg Zn) placed in HCL undergoes corrosion.

Standard electrode Half-Cell Potential of Metals

Oxidation/Reduction half cell potentials are compared

More tendency to corrode

Examples:- Fe (-0.44), Na (-2.74)

Less tendency to corrode

Examples:- Au (1.498), Cu (0.33)

Macroscopic Galvanic Cells with 1M Electrolyte

Two dissimilar metal electrodes immersed in solution of their

Galvanic Cells With Electrolytes not 1M

If the concentration of electrolyte surrounding anode is

Galvanic Cells With Acid or Alkaline Electrolytes

Consider iron and copper electrodes in acidic electrolyte.

Since there are no copper ions to reduce

If electrolyte contains oxidizing agent

If electrolyte is neutral or basic,

Microscopic Galvanic Cell Corrosion of Single Electrode

When single electrode is immersed in an electrolyte,

Concentration of Galvanic Cells

If a concentration cell is created by immersing 2 electrodes in

Oxygen Concentration Cells

If two electrodes are immersed in electrolytes of different

Since cathode reaction requires O2 and electrons, high

Grain Grain boundary Electrochemical cells

Grain boundaries are more anodic and hence get

Multiple Phase Electrochemical Cells

In multiple alloys, one phase is more anodic than another.

Steel, in martensitic condition

Rate of Uniform Corrosion

W = weight of metal (g), corroded or electroplated in an

Corrosion Reaction and Polarization

When a metal corrodes, the potentials of local cathode and

Point A : equilibrium potential and current density of Zn

Activation and Concentration Polarization

Electrochemical reactions that

Passivation is loss of chemical reactivity in presence of a

Polarization curve shows how the potential of a metal

The Galvanic Series.

Many metals do not

Uniform or general attack corrosion: Reaction proceeds

Pitting: Localized corrosive attacks that produces holes or

Pitting of stainless steel

Growth of pit involves dissolution of metal in pit

Localized electrochemical corrosion in crevices and under

Localized corrosion at and/or adjacent to highly reactive

Stress corrosion cracking (SCC): Cracking caused by

Erosion Corrosion and Cavitation Damage

Fretting Corrosion and Selective Leaching

Fretting corrosion: Occurs at interface between materials

Load carrying capacity of a metallic component reduced

Oxidation- Protective Oxide Films

Oxides form on metals due to reaction with air.

Oxidation partial reaction: M

Oxidation starts by lateral expansion of discrete oxide

Oxidation rate is expressed

If ion diffusion is controlling the step (Eg Fe, Cu)

Corrosion Control Material Selection

Metallic Coatings: Used to protect metal by separating

General design rules:

Lower the temperature

Electrons are supplied to the metal structure to be