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Chapter 12

CORROSION and
DEGRADATION

We may change the nature of the


environment, select a material that is
relatively nonreactive, and/or protect
the
material
from
appreciable
deterioration.
Rusting of an iron
is a corrosion rxn.

Introduction

Deteriorative mechanisms are different for 3


material types.
In metals, there is actual material loss
by dissolution (corrosion) or by the
formation of nonmetallic scale or film
(oxidation)
Ceramics are relatively resistant to
deterioration, which usually occurs at
high T or in extreme environments
corrosion term can be used
Polymers may dissolve when exposed to
a liquid solvent, or they may absorb the
solvent and swell. Also, electromagnetic

orrosion of Metals

Destructive and unintentional attack of a


metal.
Electrochemical and begins at the surface.

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).

orrosion of Metals
For metallic materials, the corrosion process is
normally electrochemical; chemical reaction in
which there is transfer of electrons from one
chemical
species
Metal
atoms
lose to
oranother.
give up electrons in what is
called an oxidation reaction.
For example, the hypothetical metal M that
has a valence of n (or n valence electrons) may
experience oxidation according to the reaction:

The site at which oxidation takes place is called the


anode; oxidation is sometimes called an anodic
reaction.

sion of Metals Electrochemical Corrosion


Ex: consider the corrosion of zinc in an acid solution
Two reactions are necessary:

-- oxidation reaction:
-- reduction reaction:

Zn Zn 2 2e
2H 2e H2 (gas)

H+
Oxidation reaction
Zn Zn2+
H+

Zinc

flow of e
2ein the metal

H+

H+ +
H
H+
H2(gas)
H+
reduction reaction

Acid
solution

Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution
O2 4H 4e 2H2O

-- neutral or basic solution


O2 2H2O 4e 4(OH)

Rusting

formed by the reaction of iron and


oxygen in the presence of water or air
moisture

he Galvanic Series

The relative reactivities of a number of


metals and alloys in seawater.
Comparison of the standard emf and the
galvanic series reveals a high degree of
correspondence
between
the
relative
positions of the pure base metals.
Most metals and alloys are subject to
oxidation or corrosion to one degree or
another in a wide variety of environments;
that is, they are more stable in an ionic state
than as metals.

Classified according to anotic an


catotic.Low corrosion resistance (more
anoticler)
Ranking of the reactivity of metals/alloys in seawater

more cathodic

(inert)

more anodic

(active)

alvanic Series

Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel (active)
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium

he Galvanic Series
The alloys near the
top are cathodic and
unreactive, whereas
those at the bottom
are most anodic; no
are
voltages
Two
notable
provided.
exceptions are the
noble metals gold
and platinum.
For them, oxidation
in
most
environments is not
favorable,
and,
therefore, they may

Forms of Corrosion

etallic corrosion is classified into 8 forms

Uniform attack
Galvanic corrosion
Crevice corrosion
Pitting corrosion
Intergranular
Selective-leaching
Erosion-corrosion
Stress corrosion

Forms
of
corrosion

g.b.
prec.
attacked
zones

Forms of Corrosion Uniform Attack


Uniform attack is a form of electrochemical
corrosion
Occurs over the entire exposed surface
oxidation and reduction rxns occur on the surface
Most common form of corrosion
Leaves behind a scale or deposit
Rusting of steel and iron, tarnishing of silverware

Forms of Corrosion Galvanic


Corrosion
Occurs when 2 metals or alloys having
different
compositions
are
electrically
coupled while exposed to an electrolyte.
The less noble (or more reactive) metal in a
specific environment will corrode, the more
inert metal (cathode) will be protected from
corrosion (more anodic metal will corrode)
Steel screws corrode when in contact with
brass in a marine environment.
If copper and steel tubing are joined in a
domestic water heater, the steel will
corrode.

Forms of Corrosion Galvanic


Corrosion
The rate of galvanic
attack depends on the
relative
anode-tocathode surface areas
that exposed to the
electrolyte.
The rate is related to the
cathode-anode
area
ratio.
For a given cathode
area, a smaller anode
will corrode more rapidly

Forms of Corrosion Galvanic


Corrosion
Measures may be taken to significantly reduce
the effects of galvanic corrosion.
More cathodic more anotic increase corrosion
1) If coupling of dissimilar metals is necessary,
choose 2 that are close together in the
galvanic series.
2) Avoid an unfavorable anode-to-cathode surface
area ratio; use an anode area as large as
possible.
3) Electrically insulate dissimilar metals from
each other.
4) Electrically connect a third, anodic metal to the

Forms of Corrosion Crevice


Corrosion

Electrochemical corrosion may also occur as a


consequence of concentration differences of
ions or dissolved gases in the electrolyte
solution, and btw the 2 regions of same
metal piece.

Occurs due to concentration differences For a


concentration cell, corrosion occurs where
the concentration is low.

Forms of Corrosion Crevice


Corrosion
After oxygen has
been depleted within
the
crevice,
oxidation
of
the
metal occurs at this
position
M Mn+ + ne-

Crevice corrosion may be prevented by using


welded instead of riveted or bolted joints, using
nonabsorbing gaskets when possible, removing
accumulated deposits, etc.

Forms of Corrosion Pitting


Corrosion
Very localized corrosion attack
in which small pits or holes
form.

They penetrate from the top


of
a
horizontal
surface
downward in a nearly vertical
direction.
Often going undetected and
with very little material loss
until failure occurs.
Stainless
susceptible

steels
to

are
pitting

Forms of Corrosion Intergranular


Corrosion

Occurs along grain boundaries (g.b.) for


some alloys in specific environment. Forms
materail loss
Macroscopic specimen disintegrates along
its g.b.
Some stainless steels are susceptible to
intergranular corrosion.

Forms of Corrosion Intergranular


Corrosion
When they heated btw 500-800C, the heat
treatment permits the formation of small
precipitate particles of Cr23C6 along the g.b.

Both Cr and C must diffuse to the g.b. to form


precipitates, which leaves a Cr-depleted zone
adjacent to the g.b. So, this g.b. region is now
highly susceptible to corrosion.

Forms of Corrosion Intergranular


Corrosion

Forms of Corrosion Intergranular


Corrosion
SS may be protected from intergranular
corrosion by the following measures:
1) Subjected to the sensitized material to high
T heat treatment in which all the Cr23C6
particles are dissolved.
2) Lowering the C content below 0.03 wt%
3) Alloying the steel with Ti or Nb, which has a
greater tendency to form carbides than does
Cr, so that the Cr remains in the solid
solution

Forms of Corrosion Selective


Leaching
Found in solid solution alloys
Occurs when one element is preferentially
removed as a consequence of corrosion
processes
Example: dezincification of brass, in which
Zn is selectively leached from a Cu-Zn brass
alloy.
Mechanical properties and color of the
materials change.

Forms of Corrosion ErosionCorrosion

Arises from the combined action of


chemical attack and mechanical
abrasion or wear as a consequence
of fluid motion.

The best way to reduce erosion-corrosion is


to change the design to eliminate fluid
turbulence and impingement effects.
Removal of particles or bubbles from the
solution will decrease its ability to erode.

Forms of Corrosion Stress


Corrosion
Stress
Corrosion
Corrosion

Stress

Cracking

Results from the combined action of an


applied tensile stress and a corrosive
environment
When a stress is applied, small cracks form
and then propagate in a direction
perpendicular to the stress.
Most stainless steels stress corrode in
solutions containing Cl- ions.
Brasses are vulnerable when exposed to

Forms of Corrosion Stress


Corrosion

Forms of Corrosion Stress


Corrosion
The stress that produces stress corrosion
cracking need not to be externally applied it may be residual one that results from
rapid T changes.

The best way to reduce stress corrosion is


to lower the magnitude of stress apply
some heat treatments reducing external
load, increasing the cross-sectional area,
appropriate heat treatment for annealing,
etc.

Corrosion Environments
Atmosphere, aqueous solutions, soils, acids,
bases, inorganic solvents, molten salts,
liquid metals, human body, etc.
Moisture containing dissolved oxygen is a
corrosion agent S compounds, NaCl may
contribute
Seawater (producing pitting and crevice
corrosion)
is
more
corrosive
than
freshwater.
Cast iron, steel, Al, Cu, brass, and some
stainless steels are suitable for freshwater
use

Corrosion Prevention
Material Selection
Environmental Alteration
Design
Coatings
Cathodic Protection
Changing the character of environment
Lowering the fluid T, velocity
Changing the concentration of species
Metallic or nonmetallic coatings, films are
physical barrier for corrosion

Corrosion Prevention - Inhibitors

Inhibitors can be added in low concentrations


to the environmet - decrease its corrosiveness
Reacts and eliminate chemically active
species in the solution (e.g. dissolved
oxygen)
Inhibitor molecules attach themselves and
to the corroding surface and prevent
either oxidation or reduction reactions.

Corrosion Prevention Cathodic


Protection
One of the most effective way.
It can be used for all 8 different forms of
corrosion
It may completely stop corrosion
M Mn+ + neCathodic protection involves supplying, from an
external source, electrons to metal to be
protected, making it cathode; the rxn is thus
forced in the reverse (or reduction) direction.

Corrosion Prevention Cathodic


Protection

This technique employs a galvanic couple: the


metal to be protected is electrically connected
to another metal that is more reactive in the
specific environment.

Another metal is experiences oxidation, upon


giving up electrons, protects the first metal
from corrosion.
The oxidized metal sacrificial anode
Mg and Zn are commonly used as such
because they lie at the anodic end of the
galvanic series.

Corrosion Prevention Cathodic


Protection

Cathodic protection of
an
underground
pipeline using a Mg
sacrificial anode

An underground tank
using an impressed
current.

Corrosion Prevention Cathodic


Protection

Galvanizing is simply one in which a layer of


zinc is applied to the surface of steel by hot
dipping.

In the atmosphere and most aqueous


environments, zinc is anodic to and will thus
cathodically protect the steel if there is any
surface damage.
Any corrosion of the zinc
coating will proceed at an
extremely slow rate bcs
the ratio of the anode-tocathode surface area is
quite large.

Corrosion Prevention Cathodic


Protection

Source of e- is an
impressed current from
an external dc power
source
for
an
underground tank.
The (-) terminal of the
An underground tank
power
source
is
using an impressed
connected
to
the
current.
A current path exists structure
btw the cathode
andbe
to
anode through the intervening
soil, completing
protected.
the electrical circuit.
The other terminal is joined to an inert anode
(often graphite), which is, in this case, buried in the
soil; high conductivity backfill material provides
good electrical contact btw the anode and

Corrosion Prevention Cathodic


Protection

Cathodic protection is useful in


preventing corrosion of water
heaters, underground tanks and
pipes, and marine equipment.