Corrosion,

Prevention
and Control
Monteclaro, Richard B.
Nave, John Christian R.
Obias, Cherry Mae V.
What is Corrosion ?
How can Corrosion be prevented?
How can Corrosion be controlled?
Introduction :
Corrosion is the slow but continuous eating away of
metallic components by chemical or electrochemical
attack.
Three factors govern corrosion.
1. The metal from which the component is made.
2. The protective treatment the component surface
receives.
3. The environment in which the component is kept.
All metals corrode to a greater or lesser degree;
even precious metals like gold and silver tarnish in
time, and this is a form of corrosion.

Prevention processes are unable to prevent the

inevitable failure of the component by corrosion;
they only slow down the process to a point where
the component will have worn out or been
discarded for other reasons before failing due to
corrosion. Let's now look at the three ways in which
metals corrode.
Three ways in which
metals corrode

1. Dry Corrosion
2. Wet Corrosion
3. Galvanic Corrosion
1. Dry corrosion
This is the direct oxidation of metals which occurs
when a freshly cut surface reacts with the oxygen
of the atmosphere.

Most of the corrosion-resistant metals such as

lead, zinc and aluminum form a dry oxide film
which protects the metal from further
atmospheric attack.
2. Wet corrosion
This occurs in two ways:
a. The oxidation of metals in the presence of air and
moisture, as in the rusting of ferrous metals.

b. The corrosion of metals by reaction with the

dilute acids in rain due to the burning of fossil
fuels (acid rain) - for example, the formation of
the carbonate 'patina' on copper. This is the
characteristic green film seen on the copper clad
roofs of some public buildings.
3. Galvanic corrosion
This occurs when two dissimilar metals, such as
iron and tin or iron and zinc, are in intimate
contact.

They form a simple electrical cell in which rain,

polluted with dilute atmospheric acids, acts as an
electrolyte as generated and circulates within the
system. Corrosion occurs with (depending upon its
position in the electrochemical series) being eaten
away.
 Fortunately the reactivity of a metal and the rate at
which it corrode is not related. For example, although
aluminum is chemically more reactive than iron, as
soon as it is exposed to the atmosphere it forms an
oxide film which seals the surface and prevents
further corrosion from taking place.

On the other hand, iron is less reactive and forms

its to oxide film more slowly. Unfortunately, the iron
hydroxide film (rust) is porous and the process
continues unabated until the metal is destroyed.
ELECTROCHEMICAL CELL
 ANODE REACTIONS
Anode metal corrodes and metal ions get into solution
as:
If steel is corroding,
If Aluminum is corroding,
These reactions are also called Oxidation reactions.
CATHODE REACTIONS
The cathodic reaction consumes the electrons generated
by the anodic reaction.
In nature, and neutral or basic environments containing
oxygen, the cathodic reaction is:
Rusting of Iron - Video
Electrochemical Cell -
Video
Electrochemical Corrosion -
Video
 Types of Corrosion
1. Atmospheric Corrosion
2. Galvanic Corrosion
3. Corrosion Accelerated by Mechanical Stresses
a. Stress Corrosion
b. Corrosion Fatigue
c. Fretting Corrosion
d. Impingement Corrosion
Atmospheric corrosion

Any metal exposed to normal atmospheric conditions

become covered with an invisible, thin film of
moisture. This moisture film is invariably
contaminated with dissolved solids and gases which
increase the rate of corrosion.

The most common example of corrosion due to

dissolved oxygen from the atmosphere is the rapid
surface formation of 'red rust' on unprotected ferrous
metals.
Galvanic corrosion

It has already been stated that when two

dissimilar metals come into intimate association in
the presence of an electrolyte that a simple
electrical cell is formed resulting in the eating
away of one or other of the metals.

Metals can be arranged in a special order called

the electrochemical series.
Corrosion accelerated by mechanical stresses

We have seen that failure of a component may

take place due to corrosion arising from
electrolytic action between two different phases in
a microstructure, or between two different
materials in a fabricated structure. Failure of a
component may also occur as a result of the
complementary effects of chemical corrosion and
mechanical stress.
Forms of corrosion in which stress plays a part can
be classified as follows:

Stress Corrosion
Corrosion takes place in these regions of high energy
and the locked-up stresses give rise to the formation
of cracks which grow progressively with the
continuance of corrosion. A similar process may take
place in components in which unequal heating or
cooling has given rise to the presence of locked-up
stresses, as, for example, near to welded joints.
Corrosion Fatigue. As might be expected, any
component which is subjected to alternating
stresses and is working in conditions which
promote corrosion may fail at a stress well
below the normal fatigue limit (3.72). The
action of the corrosive medium will tend to be
concentrated at any surface flaw and behave
as a focal point for the initiation of a fatigue
crack.
Fretting Corrosion is allied to corrosion
fatigue and occurs particularly where closely
fitting machine parts are subjected to
vibrational stresses. In steel this form of
corrosion appears as patches of finely divided
ferric oxide (Fe203).
Impingement Corrosion refers to the
combined effects of mechanical abrasion and
chemical corrosion on a metallic surface.
Mechanical wear can be caused by the
impingement of entrained air bubbles or
abrasive particles suspended in the liquid.

This type of corrosion is encountered in pump

mechanism turbine and tuber carrying sea-
water.
Typical micro cracks formed during SCC
of sensitized AISI 304 SS

Surface morphology
 Example of crack propagation during
transgranular stress corrosion cracking (TGSCC)
brass
Example of crack
propagation during
intergranular stress
corrosion cracking
(IGSCC) ASTM A245
carbon steel
 Fracture surface of
intergranular SCC on
carbon steel in hot nitric
solution

Fracture surface of
transgranular SCC on
austenitic stainless steel in
hot chloride solution
Fracture surface due Fracture surface due to
to intergranular SCC local stress has reached
its tensile strength value
on the remaining section
Factors affecting
Corrosion
1. Structural Design
2. Environment
3. Applied or internal stresses
4. Composition and structure
5. Temperature
1. Structural Design
The design should avoid crevices and corners where
moisture may become trapped, and adequate
ventilation and drainage should be provided.
The design should allow for easy washing down and
cleaning.
Joints which are not continuously welded should be
sealed, for example, by the use of mastic
compounds or impregnated tapes.
Where dissimilar metals have to be joined, high-
strength epoxy adhesives should be considered
since they insulate the metals from each other and
prevent galvanic corrosion.

Materials which are inherently corrosion resistant

should be chosen or, if this is not possible, an anti-
corrosive treatment should be specified.
2. Environment
The environment in which the component or
assembly is to spend its service life must be carefully
studied so that the materials chosen, or the anti-
corrosion treatment specified, will provide an
adequate service life at a reasonable cost.
 3. Applied or internal
stresses
Chemical and electrochemical corrosion is intensified
when a metal is under stress. This applies equally to
externally applied and internal stresses, although more
common in the latter case. Internal stresses are usually
caused by cold working and, if not removed by stress-relief
heat treatment, results in corrosive attack along the
crystal boundaries. This weakens the metal considerably
more than simple surface corrosion.
An example of intercrystalline corrosion is the 'season
cracking' of a brass after severe cold working.
 4. Composition and
structure
The presence of impurities in non-ferrous metals reduces
their corrosion resistance. Hence the high level of
corrosion resistance exhibited by high- purity copper,
aluminum and zinc. The importance of grain structure has
also been mentioned above, and a fine-grain structure is
generally less susceptible to corrosion than a coarse-grain
structure. The inclusion of certain alloying elements such
as nickel and chromium can also improve corrosion
resistance
- for example, the stainless steels and cupro-nickel alloys.
 5. Temperature
For all chemical reactions there is a critical temperature
below which they will not take place. Since corrosion is
the result of chemical or electrochemical reactions,
corrosion is retarded or stopped altogether at low
temperatures. On the other hand, corrosion is at its
worst in the hot.
 PREVENTION OF
CORROSION
The huge annual loss due to corrosion is a national waste and
should be minimized
Materials already exist which, if properly used, can eliminate
80 % of corrosion loss
Proper understanding of the basics of corrosion and
incorporation in the initial design of metallic structures is
essential
METHODS
Material selection
Improvements in material
Design of structures
Alteration of environment
Cathodic & Anodic protection
Coatings
MATERIAL SELECTION
(selection of proper material for a particular
corrosive service)

Metallic [metal and alloy]

Nonmetallic [rubbers (natural and synthetic),
plastics, ceramics, carbon and graphite, and
wood]
Metals and Alloys
No Environment Proper material
1 Nitric acid Stainless steels

2 Caustic Nickel and nickel

alloys

3 Hydrofluoric acid Monel (Ni-Cu)

4 Hot hydrochloric Hastelloys (Ni-Cr-
acid Mo) (Chlorimets)

5 Dilute sulfuric acid Lead

No Environment Proper material
6 Nonstaining Aluminium
atmospheric
exposure
7 Distilled water Tin
8 Hot strong oxidizing Titanium
solution
9 Ultimate resistance Tantalum
10 Concentrated Steel
sulfuric acid
E.g : Stainless Steels

Stainless steels are

Dissolution rate, cm/sec

iron base alloys that
contain a minimum of
approximately 11% Cr,
the amount needed to
prevent the formation
of rust in unpolluted
atmosphere.
wt.% Cr
Alloying elements of stainless steel :
Other than Ni, Cr and C, the following alloying elements may also
present in stainless steel: Mo, N, Si, Mn, Cu, Ti, Nb, Ta and/or W.

Main alloying elements (Cr, Ni and C):

1. Chromium
Minimum concentration of Cr in a stainless steel is 12-14wt.%
Structure : BCC (ferrite forming element)

* Note that the affinity of Cr to form Cr-carbides is very high.

Chromium carbide formation along grain boundaries may induce
intergranular corrosion.
 2. Nickel

Structure: FCC (austenite forming element/stabilize austenitic

structure)
Added to produce austenitic or duplex stainless steels.
These materials possess excellent ductility, formability and
toughness as well as weld-ability.
Nickel improves mechanical properties of stainless steels
servicing at high temperatures.
Nickel increases aqueous corrosion resistance of materials.
3. Carbon
Very strong austenite forming element (30x more
effective than Ni). I.e. if austenitic stainless steel 18Cr-
8Ni contains 0.007%C, its structure will convert to
ferritic structure. However the concentration of carbon
is usually limited to 0.08%C (normal stainless steels)
and 0.03%C (low carbon stainless steels to avoid
sensitization during welding).
 Minor alloying elements :
Manganese
Austenitic forming element. When necessary can be used to
substitute Ni. Concentration of Mn in stainless steel is usually 2-3%.

Molybdenum
Ferritic forming element. Added to increase pitting corrosion
resistance of stainless steel (2-4%).
Molybdenum addition has to be followed by decreasing chromium
concentration (i.e. in 18-8SS has to be decreased down to 16-18%) and
increasing nickel concentration (i.e. has to be increased up to 10-14%).
Improves mechanical properties of stainless steel at high
temperature. Increase aqueous corrosion resistance of material
exposed in reducing acid.
Tungsten
Is added to increase the strength and toughness of
martensitic stainless steel.
Nitrogen (up to 0.25%)
Stabilize austenitic structure. Increases strength and
corrosion resistance. Increases weld ability of duplex SS.
Titanium, Niobium and Tantalum
To stabilize stainless steel by reducing susceptibility of
the material to intergranular corrosion. Ti addition > 5x
%C. Ta+Nb addition > 10x%C.
Copper
Is added to increase corrosion resistance of stainless steel
exposed in environment containing sulfuric acid.

Silicon
Reduce susceptibility of SS to pitting and crevice corrosion
as well as SCC.
 Five basic types of stainless steels :
Austenitic - Susceptible to SCC. Can be hardened by only by cold
working. Good toughness and formability, easily to be welded and
high corrosion resistance. Nonmagnetic except after excess cold
working due to martensitic formation.

Martensitic - Application: when high mechanical strength and wear

resistance combined with some degree of corrosion resistance are
required. Typical application include steam turbine blades, valves
body and seats, bolts and screws, springs, knives, surgical
instruments, and chemical engineering equipment.

Ferritic - Higher resistance to SCC than austenitic SS. Tend to be

notch sensitive and are susceptible to embrittlement during
welding. Not recommended for service above 300 0C because they
will loss their room temperature ductility.
Duplex (austenitic + ferritic) has enhanced resistance to SCC with
corrosion resistance performance similar to AISI 316 SS. Has higher
tensile strengths than the austenitic type, are slightly less easy to
form and have weld ability similar to the austenitic stainless steel.
Can be considered as combining many of the best features of both
the austenitic and ferritic types. Suffer a loss impact strength if held
for extended periods at high temperatures above 3000C.

Precipitation hardening - Have the highest strength but require

proper heat-treatment to develop the correct combination of
strength and corrosion resistance. To be used for specialized
application where high strength together with good corrosion
resistance is required.
 Alteration of Environment
Typical changes in medium are :

Lowering temperature but there are cases where increasing T

decreases attack. E.g hot, fresh or salt water is raised to boiling T
and result in decreasing O2 solubility with T.

Decreasing velocity exception ; metals & alloys that passivate

(e.g stainless steel) generally have better resistance to flowing
mediums than stagnant. Avoid very high velocity because of
erosion-corrosion effects.
 Removing oxygen or oxidizers e.g boiler feedwater was deaerated by
passing it thru a large mass of scrap steel. Modern practice vacuum
treatment, inert gas sparging, or thru the use of oxygen scavengers.
However, not recommended for active-passive metals or alloys. These
materials require oxidizers to form protective oxide films.

Changing concentration higher concentration of acid has higher

amount of active species (H ions). However, for materials that exhibit
passivity, effect is normally negligible.
Environment factors affecting corrosion design :
Dust particles and man-made pollution CO, NO, methane,
etc.
Temperature high T & high humidity accelerates
corrosion.
Rainfall excess washes corrosive materials and debris but
scarce may leave water droplets.
Proximity to sea
Air pollution NaCl, SO2, sulfurous acid, etc.
Humidity cause condensation.
 Design Dos & Donts
Wall thickness allowance to accommodate for corrosion effect.
Avoid excessive mechanical stresses and stress concentrations in
components exposed to corrosive mediums. Esp when using
materials susceptible to SCC.
Avoid galvanic contact / electrical contact between dissimilar
metals to prevent galvanic corrosion.
Avoid sharp bends in piping systems when high velocities and/or
solid in suspension are involved erosion corrosion.
Avoid crevices e.g weld rather than rivet tanks and other
containers, proper trimming of gasket, etc.
Avoid sharp corners paint tends to be thinner at sharp corners and
often starts to fail.
Provide for easy drainage (esp tanks) avoid remaining liquids collect at
bottom. E.g steel is resistant against concentrated sulfuric acid. But if
remaining liquid is exposed to air, acid tend to absorb moisture,
resulting in dilution and rapid attack occurs.
Avoid hot spots during heat transfer operations localized heating and
high corrosion rates. Hot spots also tend to produce stresses SCC
failures.
Design to exclude air except for active-passive metals and alloys coz
they require O2 for protective films.
 Protective Coatings / Wrapping
Provide barrier between metal and environment.
Coatings may act as sacrificial anode or release substance that inhibit corrosive
attack on substrate.
Metal coatings :
Noble silver, copper, nickel, Cr, Sn, Pb on steel. Should be free of
pores/discontinuity coz creates small anode-large cathode leading to rapid
attack at the damaged areas.
Sacrificial Zn, Al, Cd on steel. Exposed substrate will be cathodic & will be
protected.
Application hot dipping, flame spraying, cladding, electroplating, vapor
deposition, etc.
Surface modification to structure or composition by use of
directed energy or particle beams. E.g ion implantation and laser
processing.
Inorganic coating : cement coatings, glass coatings, ceramic
coatings, chemical conversion coatings.
Chemical conversion anodizing, phosphatizing, oxide coating,
chromate.
Organic coating : paints, lacquers, varnishes. Coating liquid
generally consists of solvent, resin and pigment. The resin
provides chemical and corrosion resistance, and pigments may
also have corrosion inhibition functions.
Rust Prevention and Treatment
- Video
 Corrosion,
Prevention
and Control
Monteclaro, Richard B.
Nave, John Christian R.
Obias, Cherry Mae V.