METB113 EMat 13 Corrosion

METB113/1
Corrosion and Protection Methods

METB113
ENGINEERING MATERIALS
CORROSION AND PROTECTION METHODS
METB113/2

Types and Its Mechanisms
Protection & Control Methods
Structure Analysis

METB113/3
Corrosion: -- the destructive and unintentional electrochemical
attack of a materials.
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.

-- Ex: Al Capone's
ship, Sapona,
off the coast
of Bimini.
Cost:
-- 4 to 5% of the Gross National Product (GNP)*
-- in the U.S. this amounts to just over $400 billion/yr**
Photos courtesy L.M. Maestas, Sandia
National Labs. Used with permission.
Introduction
METB113/4
Oxidation Reduction Reactions
A metal (Eg Zn) placed in HCl undergoes corrosion.

Zn + 2HCl ZnCl
2
+ H
2
or
Zn + 2H
+
Zn
2+
+ H
2
also
Zn Zn
2+
+ 2e
-
(oxidation half cell reaction)
2H
+
+ 2e
-
H
2
(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.

13-3
METB113/5
5
Two reactions are necessary:
-- oxidation half-cell reaction:
-- reduction half-cell reaction:

Zn Zn
2
2e

2H 2e H
2
(gas)
Other reduction reactions in solutions with dissolved oxygen:
-- acidic solution -- neutral or basic solution

O
2
4H 4e 2H
2
O

O
2
2H
2
O 4e 4(OH)
ELECTROCHEMICAL CORROSION
Zinc
Oxidation reaction
Zn
Zn
2+
2e
-
Acid
solution
reduction reaction
H
+
H
+
H
2
(gas)
H
+
H
+
H
+
H
+
H
+
flow of e
-

in the metal
Ex: consider the corrosion of zinc in an acid solution
METB113/6
Standard electrode Half-Cell Potential of Metals
Oxidation/Reduction half cell potentials are compared with
standard hydrogen electrode
half cell potential.
Voltage of metal (Ex: 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)

Figure 12.3
13-4
METB113/7
7
Standard Hydrogen Electrode
Oxidation/Reduction half cell potentials are compared with
standard hydrogen electrode half cell potential.

Two outcome:
0
o
metal
V
(relative to Pt)
Standard Electrode Potential
Adapted from Fig. 16.2,
Callister & Rethwisch 3e.
-- Electrodeposition
-- Metal is the cathode (+)
M
n+

ions
ne
-
e
-
e
-
25 C
1M M
n+
soln 1M H
+
soln
P
l
a
t
i
n
u
m

m
e
t
a
l
,

M

H
+
H
+
2e
-
0
o
metal
V (relative to Pt)
-- Corrosion
-- Metal is the anode (-)
P
l
a
t
i
n
u
m

m
e
t
a
l
,

M

M
n+

ions
ne
-
H
2
(gas)
25 C
1M M
n+
soln 1M H
+
soln
2e
-
e
-
e
-
H
+

H
+

METB113/8
8
Standard EMF Series
metal
o
Metal with smaller
V corrodes.
EMF series
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K
+1.420 V
+0.340
- 0.126
- 0.136
- 0.250
- 0.277
- 0.403
- 0.440
- 0.744
- 0.763
- 1.662
- 2.363
- 2.714
- 2.924
metal
V
metal
o
Data based on Table 17.1,
Callister 7e.
m
o
r
e

a
n
o
d
i
c

m
o
r
e

c
a
t
h
o
d
i
c

V =
0.153V
o
Adapted from Fig. 16.2,
Callister & Rethwisch 3e.
-
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
25 C Ni Cd
Ex: Cd-Ni cell

V < V Cd corrodes
Cd
o
Ni
o
METB113/9
9
Effect of Solution Concentration and Temperature
Ex: Cd-Ni cell with
standard 1 M solutions

V
Ni
o
V
Cd
o
0.153 V
-
Ni
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
Cd 25 C
Ex: Cd-Ni cell with
non-standard solutions
Y
X
ln
nF
RT
V V V V
o
Cd
o
Ni Cd Ni
n = #e
-

per unit
oxid/red
reaction
(= 2 here)
F =
Faraday's
constant
= 96,500
C/mol.
Reduce V
Ni
- V
Cd
by
-- increasing X
-- decreasing Y
-- increasing T
-
+
Ni
Y M
Ni
2+
solution
X M
Cd
2 +
solution
Cd
T
METB113/10
Microscopic galvanic cell can exist in metals or alloys due to
difference in structure, composition and stress concentration.
When single electrode is immersed in an air-free electrolyte,
microscopic cathodes and anodes are formed on the surface due
to difference in structure and composition.
Oxidation reaction occurs at local anode and reduction reaction
at local cathode.

If iron is immersed in
oxygenated water,

2Fe + 2H
2
O + O
2
2Fe
2+
+ 4OH
-
2Fe(OH)
2

Microscopic Galvanic Cell Corrosion of Single Electrode
Fe Fe
2+
+ 2e
-

O
2
+ 2H
2
O + 4e
-
4OH
-
13-8
METB113/11
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.

Cartridge Brass
Grain
Boundary
Grain boundary
(anode)
Grain boundary
(cathode)
anode
Figure 12.9
13-11
METB113/12
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
leading to corrosion.
Figure 12.10
After Metals handbook, vol. 7, 8
th
ed., American Society for Metals, 1972, p.83.

13-12
METB113/13
Rate of Uniform Corrosion
Faradays equation:

W = weight of metal (g), corroded or electroplated in an
aqueous solution in time t, seconds.
I = Current flow A, i = current density A/cm
2
M = atomic mass of metal g/mol
n = number of atoms/electron produced or consumed
F = Faradays Constant, A = area, cm
2
Corrosion rate is expressed as weight loss per unit area per
unit time or loss in depth per unit time.

nF
iAtM
nF
ItM
W
13-13
METB113/14
Corrosion Reaction and Polarization
When a metal corrodes, the potentials of local cathode and
anode are not at equilibrium.
Polarization: Displacement of electrode potential from
their equilibrium values to some
intermediate value and
creation of net current flow.
Magnitude of displacement:
(overvoltage)
Point A : equilibrium potential
and current density of Zn
Point B : equilibrium potential
and current density of H
Point C : Intermediate point
Zn in acid
solution
13-14
METB113/15
Activation and Concentration Polarization
Activation polarization: Electrochemical reactions that are controlled by
the slowest step in the reaction sequence.
There is a critical activation energy to surmount energy barrier associated
with slowest step.
Figure 12.15
After M. G. Fontana and N. D. Greene, Corrosion Engineering, 2
nd
ed., McGraw-Hill, 1978, p.15.

13-15
Polarization controls the corrosion rate.
1. Adsorption of H
+
from solution
onto zinc surface.
2. Electron transfer from zinc to
hydrogen atom.
3. Reduction of hydrogen.
4. Combining two atom hydrogen
together.
5. Coalescence of many hydrogen
molecules to form bubbles.

The slowest of these steps control
the overall reaction.
METB113/16
Concentration polarization:
exists when the reaction rate is limited by the diffusion of ions in the
solution.
Example: Reduction rate of H
+
ions at surface is controlled by diffusion
of H
+
ions onto metal surface.
Activation and Concentration Polarization
METB113/17
Passivation
Passivation is loss of chemical reactivity in
presence of an 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.
13-16
METB113/18
18
Uniform Attack
Oxidation & reduction
reactions occur uniformly
over surfaces.
Selective Leaching
Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-Zn)].
Stress corrosion
Corrosion at crack tips when a
tensile stress is present.
Galvanic
Dissimilar metals are
physically joined in the presence
of an electrolyte. The
more anodic metal
corrodes.
Erosion-corrosion
Combined chemical attack and
mechanical wear (e.g., pipe
elbows).
FORMS OF CORROSION
Forms
of
corrosion
Crevice Narrow and
confined spaces.
Fig. 16.15, Callister & Rethwisch 3e. (Fig.
16.15
is courtesy LaQue Center for Corrosion
Technology, Inc.)
Rivet holes
Intergranular
Corrosion along
grain boundaries,
often where precip.
particles form.
Fig. 16.18, Callister &
Rethwisch 3e.
attacked
zones
g.b.
prec.
Pitting
Downward propagation
of small pits and holes.

Fig. 16.17, Callister &
Rethwisch 3e. (Fig.
16.17 from M.G.
Fontana, Corrosion
Engineering,
3rd ed., McGraw-Hill
Book
Company, 1986.)
METB113/19
Uniform and Galvanic 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.
13-19
METB113/20
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.
Pitting of stainless steel
Figure 12.20
Courtesy of LaQue Center for Corrosion Technology, Inc.

13-20
METB113/21
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).
Figure 12.21
nd
ed., McGraw-Hill, 1978 13-21
METB113/22
Figure 12.21
nd
ed., McGraw-Hill, 1978 13-21
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
+
+ e
-
Cathode:O
2
+ 2H
2
O + 4e
-
4OH
-
As 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.

Figure 12.23
nd
ed., McGraw-Hill, 1978.

13-22
METB113/23
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-
800
0
C) chromium carbide precipitate along grain
boundaries.
When exposed to corrosive environment, the
region next to grain boundaries become anodic
and corrode.

Figure 12.24
13-23
METB113/24
Stress Corrosion
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.
Figure 12.27
After R. W. Staehle.

13-24
METB113/25
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.
13-25
METB113/26
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.
13-26
METB113/27
Oxidation- Protective Oxide Films
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.
13-27
METB113/28
Mechanisms of Oxidation
Oxidation partial reaction: M M
2+
+ 2e
-
Reduction partial reaction: O
2
+ 2e
-
O
2-
Oxidation starts by lateral expansion of discrete oxide nuclei.
Metal diffuses as electrons or cations across oxide films.
Sometimes O
2-
ions diffuse to oxide metal interface and
electrons diffuse to oxide gas interface.
Figure 12.30
After L.L. Shreir (ed.) Corrosion, vol.1, 2
nd
ed., Newnes-Butterwirth, 1976, p. 1:242.

13-28
METB113/29
Oxidation Rates
Oxidation rate is expressed
as weight gained per unit area.
Linear oxidation behavior
W = K
L
t

If ion diffusion is controlling the step (Eg Fe, Cu)
W2 = K
p
t+C K
p
= Parabolic rate constant, C = constant
Some metals follow logarithmic rate law
W = K
e
Log(Ct + A) C, A = constants, K
e
= logarithmic
rate constant
Examples:- Al, Cu, Fe (at slightly elevated temperature)
W=weight gained
per unit area
KL = linear rate
constant.
T = time
Figure 12.31
13-29
METB113/30
Corrosion Control Material Selection
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.
13-30
METB113/31
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.
13-31
METB113/32
Design
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.
13-32
METB113/33
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.
13-33
METB113/34
Cathodic Protection
Electrons are supplied to the metal structure to
be protected.
Example: Fe in acid
Fe Fe
2+
+ 2e
-
2H
+
+ 2e
-
H
2
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.

Figure 12.33
nd

13-34
METB113/35
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.

Figure
12.34
nd

13-35

METB113 EMat 13 Corrosion

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METB113/1

Corrosion and Protection Methods

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