CORROSION

CORROSION

CORROSION AND DEGRADATION OF

MATERIALS
Cost of Corrosion

Fundamentals of Corrosion

Electrochemical reactions

EMF and Galvanic Series

Concentration and Temperature (Nernst)

Corrosion rate

Corrosion prediction (likelihood)

Polarization

Protection Methods

ost of

What is the.

Corrosion

The Cost of Corrosion

THE CONSEQUENCES OF CORROSION

The consequences of corrosion are many

and varied and the effects of these on
the safe, reliable and efficient operation
of equipment or structures are often
more serious than the simple loss of a
mass of metal. Failures of various kinds
and the need for expensive
replacements may occur even though
the amount of metal destroyed is quite
small.

Reduction of metal thickness leading to loss of

mechanical strength and structural failure or breakdown.
When the metal is lost in localised zones so as to give a
crack like structure, very considerable weakening may
result from quite a small amount of metal loss.
Hazards or injuries to people arising from structural
failure or breakdown (e.g. bridges, cars, aircraft).
Reduced value of goods due to deterioration of
appearance.
Contamination of fluids in vessels and pipes).

Perforation of vessels and pipes allowing

escape of their contents and possible harm to
the surroundings. For example a leaky domestic
radiator can cause expensive damage to
carpets and decorations.
Mechanical damage to valves, pumps, etc, or
blockage of pipes by solid corrosion products.
Added complexity and expense of equipment
which needs to be designed to withstand a certain
amount of corrosion, and to allow corroded
components to be conveniently replaced.

Significance of Corrosion
on Infrastructure

Engineer finds corrosion in collapsed bridge

at North Carolina speedway (2000)

Corrosion & Catastrophic Failure.

A Concrete bridge failure

WHAT IS CORROSION

Corrosion is the deterioration of

materials by chemical interaction with
their environment.
The term corrosion is sometimes also
applied to the degradation of plastics,
concrete and
wood, but generally refers to metals. The
most widely used metal is iron (usually
as steel)

Fundamental Components

15

Corrosion can be defined as the deterioration of

material by reaction to its environment.
Corrosion occurs because of the natural tendency
for most metals to return to their natural state;
e.g., iron in the presence of moist air will revert to
its natural state, iron oxide.
4 required components in an electrochemical
corrosion cell: 1) An anode; 2) A cathode; 3) A
conducting environment for ionic movement
(electrolyte); 4) An electrical connection between
the anode and cathode for the flow of electron
current.
If any of the above components is missing or
disabled, the electrochemical corrosion process
will be stopped.

CHEMISTRY OF CORROSION
Virtually all corrosion reactions are electrochemical
in nature, at anodic sites on the surface the iron
goes into solution as ferrous ions, this constituting
the anodic reaction. As iron atoms undergo
oxidation to ions they release electrons whose
negative charge would quickly build up in the metal
and prevent further anodic reaction, or corrosion.
Thus this dissolution will only continue if the
electrons released can pass to a site on the metal
surface where a cathodic reaction is possible. At a
cathodic site the electrons react with some
reducible component of the electrolyte and are
themselves removed from the metal.

Mechanism of corrosion

The corroding piece of metal is described as

a mixed electrode because simultaneous
anodic and cathodic reactions are
proceeding on its surface. The mixed
electrode is a complete electrochemical cell
on one metal surface.

Electrochemical reactions

Anodic reaction
Fe

Fe2+ + 2e-

Cathodic reaction
2H+ + 2e
H2
H2O + 1/2O2 + 2e
2OHFe2+ + 2OHFe(OH)2 iron (II) hydroxide
Fe(OH)2 + H2O + 1/2O2
Fe(OH)3 Hydrated iron (III)oxide

Further hydration and oxidation reactions can occur and

the reddish rust that eventually forms is a complex
mixture whose exact constitution will depend on other
trace elements which are present.

TYPES OF CORROSION

. ELECTROCHEMICAL CORROSION
. HIGH TEMPERATURE CORROSION

.GENERAL SURFACE CORROSION

.PITTING CORROSION.
.CONCENTRATION CELL CORROSION.
Metal Ion Concentration Cells.
.
Oxygen Concentration Cells.
.GALVANIC CORROSION.
.STRESS CORROSION CRACKING

1. GENERAL SURFACE CORROSION

General surface corrosion (also

referred
to as Uniform Etch or Uniform Attack
Corrosion)
is the most common form of corrosion
and results
from a direct chemical attack on a
metal surface and involves only the
metal surface. General surface
corrosion usually occurs
over a wide area and is more or less
equal in
dispersion. On a polished surface, this
type of
corrosion is first seen as a general
dulling of the
surface, and if allowed to continue,
the surface

Uniform Corrosion
22

Formerly a ship

2. PITTING CORROSION.
Pitting corrosion
is one of the most destructive and
intense
forms of corrosion. It can occur in any
metal but
is most common on metals that form
protective
oxide films, such as aluminum and
magnesium alloys.
It is first noticeable as a white or gray
powdery
deposit, similar to dust, which
blotches the
surface. When the deposit is cleaned
away, tiny
holes or pits can be seen in the
surface. These small surface openings
may penetrate deeply into structural

Pitting can cause failure, yet the total

corrosion, as measured by weight loss,
may be minimal.

3. CONCENTRATION CELL CORROSION.

Concentration cell corrosion, (also known as Crevice

Corrosion) is corrosion of metals in a metal-to-metal
joint, corrosion at the edge
of a joint even though the joined metals are identical, or
corrosion of a spot on the metal surface covered by a
foreign material.
Metal ion concentration cells and oxygen
concentration cells are the two general types of
concentration cell corrosion.

a. Metal Ion
Concentration Cells
Metal Ion Concentration Cells.
The solution may consist of water and ions of the
metal
which is in contact with metal. A high concentration
of the metal ions will normally exist under faying
surfaces where the solution is stagnant, and a
low concentration of metal ions will exist adjacent
to the crevice which is created by the faying surface.
An electrical potential will exist between the
two points; the area of the metal in contact with
the low concentration of metal ions will be anodic
and corrode, and the area in contact with the high
metal ion concentration will be cathodic and not
show signs of corrosion.

b. Oxygen Concentration
Cells
Oxygen Concentration Cells.
The solution in contact with the metal surface will normally
contain dissolved oxygen. An oxygen cell can develop at any
point where the oxygen in the air is not allowed to diffuse into
the solution, thereby creating a difference in oxygen
concentration between two points. Typical locations of oxygen
concentration cells are under gaskets, wood, rubber, and
other materials in contact with the metal surface. Corrosion
will occur at the area of low oxygen concentration (anode).
Alloys are particularly susceptible to this type of crevice
corrosion.

4. GALVANIC CORROSION
GALVANIC CORROSION.
Galvanic corrosion occurs when two
dissimilar metals make contact in the
presence of an electrolyte. It is
usually recognizable by the
presence of a build-up of corrosion at
the joint
between the metals.

Galvanic
c16f14
Dissimilar metals are physically
joined in the presence of an
electrolyte.
The more anodic metal corrodes.

Bilge pump Magnesium shell cast

around a steel core.

5.STRESS CORROSION CRACKING.

This form of corrosion involves

constant or
cyclic stress, acting in conjunction
with a damaging chemical
environment. The
stress may be caused by internal or
external loading.

Stress Corrosion Cracking, SCC

A structure that has SCC

sensitivity, if subjected to stresses
and then exposed to a corrosive
environment, may initiate cracks.
Consequently, no corrosion
products are visible, making it
difficult to detect or prevent; fine
cracks can penetrate deeply into
the part.

a. Internal stress
Internal stress may be trapped in a part of structure during
manufacturing processes such as cold working or by unequal
cooling from high temperatures. Most manufacturers follow up
these processes with a stress relief operation. Even so,
sometimes stress remains trapped.
b.

External stress
The stress may be externally introduced by welding, clamping,
press fit, etc.

c16f20

Erosion-corrosion
Combined chemical attack and
mechanical wear (e.g., pipe
elbows).

Brass water pump

Corrosion protection

Electroplating
Galvanization
1.
2.

Cathodic protection
1.
2.

Galvanization of Zinc
Galvanization of Tin
Sacrificial anode
Impressed current

Anodizing
Phoaphatizing

Galvanization of Zinc

This a very common way of protecting

steel from corrosion is to coat it with a
thin layer of zinc; this process is known
as galvanizing.
The zinc coating, being less noble than
iron, tends to corrode selectively.
Dissolution of this sacrificial coating
leaves behind electrons which
concentrate in the iron, making it
cathodic and thus inhibiting its
dissolution

Zinc plating

Galvanization of Tin

The effect of plating iron with a less active metal

provides an interesting contrast. The common
tin-plated can is a good example. As long as the
tin coating remains intact, all is well, but
exposure of even a tiny part of the underlying
iron to the moist atmosphere initiates corrosion.
The electrons released from the iron flow into
the tin, making the iron more anodic so now the
tin is actively promoting corrosion of the iron!
Example:tin cans disintegrate very rapidly when
left outdoors.

Tin plating

Cathodic protection
The approach is to apply a slight negative
charge to the metal, thus making it more
difficult for the reaction M M2+ + 2 e to take
place.
This can be done by using a sacrificial anode
made from a more reactive metal, or using an
external power supply to change the amount of
charge on the metal surface.
Cathodic protection is well suited to steel
structures in marine or underground
environments.

a. Impressed current
This technique is widely used for the protection of
buried pipelines and the hulls of ships immersed
in seawater.
The negative terminal of the current source is
connected to the metal requiring protection. The
positive terminal is connected to an auxiliary
anode immersed in the same medium to
complete the circuit. The electric current charges
the structure with excess electrons and hence
changes the electrode potential in the negative
direction.
It is important that the anode be completely
separated from the cathode so that a true electric

b. Sacrificial anode
This technique is frequently used for ships
in seawater and for offshore oil and gas
production Platforms.
The principle here is to use a more
reactive metal in contact with the steel
structure. Zinc is often used as the
sacrificial anode. If a zinc electrode is now
attached, it produces an anodic
dissolution current at a more negative
potential.

Corrosion prevention
Sacrificial Anode

Applied Voltage

Anodizing & Phosphatizing

They provides an effective base or key

for supplementary protection such as
paints. In some instances, these
treatments can also be a preparatory
step prior to painting.

They help to prevent the spreading of

rust under layers of paint.

Anodizing
This treatment change the immediate surface layer of
metal into a film of metallic oxide or compound which
has better corrosion resistance than the natural oxide
film.
The difference between plating and anodizing is that
the oxide coating is integral with the metal substrate
as opposed to being a metallic coating deposition. The
oxidized surface is hard and abrasion resistant, and it
provides some degree of corrosion resistance.

Background

Anodizing process first used in industry

in 1923 to protect Duralumin seaplane
parts from corrosion using chromic acid.
Aluminum is most widely anodized metal
Magnesium, Titanium, and Zinc are
capable of being anodized but not used
to a wide extent
Other metals such as tin and copper can
be anodized, but rarely practiced

Anodizing Basics

Basic Concept
Creates or thickens an oxide layer on
surface of metal
Allows electrical insulation of the given
metal
Creates opportunity of various
decorative effects: dyeing, brightening,
preservation of surface texture
Increases hardness of the metal,
improves corrosion and wear resistance

Areas of Application

Entertainment Industry

Military/Aerospace

Commercial

Purpose of Anodizing

Grow an aluminum oxide layer on the aluminum so it can be dyed

Corrosion and wear resistance
Hardening
Color cosmetic

Photo by Ron Newman, http://www.focuser.com/anodize.html

Overview

Aluminum part immersed in acid electrolyte

Apply electrical current, DC, ~12V
The part is the anode (+) (thus the name)
Electrolysis and chemical reaction occurs
Porous aluminum oxide layer grows on the aluminum
Up to 3000 times thicker than naturally occuring
Al2O3 layer
Dye goes into pores, results in bright colors
Place in boiling water to seal pores

Electrochemistry

Electrolyte in Solution: Free ions ,conductive

Anode

Sulfuric, oxalic, or phosphoric acid typically used

Evolution of oxygen
2Al + 3H20 Al203 + 6H+ + 6e-

Cathode

Evolution of hydrogen
6H20 + 6e- 3H2 (g) + 6OH-

Pore growth

Acid electrolyte acts as solvent for oxide

Dissolves portions of barrier oxide layer
Rate of growth dependent on current, concentration,
temperature, voltage

Photo from Artists Anodizing Aluminum, D. LaPlantz, 1988, p. 17

Reasons to anodize

Appearance: Products look finished,

cleaner, better
Corrosion resistance: A smooth
surface is retained while weathering is
retarded. Useful for food handling and
marine products
Abrasion resistance: The treated
metal is tough, harder than many
abrasives.
Anodizing treatments are also
available for magnesium and titanium

Phosphatizing

Phosphatizingis a method of
protecting asteelsurface fromcorrosion
and increasing its resistance to wear
through the application of an
electrochemical
phosphate conversion coating.
It cannot be used on non-ferrous metals
such asaluminum,brass, orcopper. It
similarly cannot be applied tosteels
containing a large amount ofnickel, or
onstainless steel.

Phosphatizing

They are applied by brushing, spraying

or prolonged immersion in an acid
orthophosphate solution containing iron,
zinc or manganese. For example a
solution might contain Zn(H2PO4)2.2H2O
with added H3PO4. The coatings consist
of a thick porous layer of fine phosphate
crystals, tightly bonded to the steel.
When forming steel sheet, the parts are
often phosphatized in order to improve
the surface properties of the sheet.

Itis commonly used onfirearmsas a

more effective alternative tobluing
(magnetite, Fe3O4), which is another
electrochemical conversion coatingthat
was developed earlier. It is also used
extensively on automobiles to protect
unfinished metal parts from corrosion

Prevention of Corrosion
Basic goal protect the metal avoid localized corrosion
When possible chose a nobler metal
Avoid electrical / physical contact between metals with very different electrode
potentials (avoid formation of a galvanic couple)
If dissimilar metals are in contact make sure that the anodic metal has a larger
surface area / volume
In case of microstructural level galvanic couple, try to use a course
microstructure (where possible) to reduce number of galvanic cells formed
Modify the base metal by alloying
Protect the surface by various means
Modify the fluid in contact with the metal
Remove a cathodic reactant (e.g. water)
Add inhibitors which from a protective layer
Cathodic protection
Use a sacrificial anode (as a coating or in electrical contact)
Use an external DC source in connection with a inert/expendable electrode