Corrosion Engineering Notes (P.E-409)

Prepared by: Sheikh Mubin Ashraf (B.
E in Petroleum NED Batch: 2010-11)

What is Corrosion?

It is the degradation of materials properties due to the interaction with their environments.
It is the deterioration of a metal as a result of chemical reactions between it & the surrounding.
It is the spontaneous reaction between a material and its environment which results in the degradation
of that material.
Metallic corrosion is the oxidization of the metal at metal/ environment interface which subsequently
results in a deterioration of the mechanical properties of the metal.

Corrosion Attacks:

Corrosion occurs on an exposed surface.
It can be concentrated locally to form a pit or a crack.
It can extend across a wide area, more or less uniformly corroding the surface.

Corrosion Rate Determination

In order to compare the corrosion resistance of each metal & non-metal, the rate of attack of each metal
must be expressed quantitatively.

Corrosion rate is the speed at which metals undergo deterioration within a particular environment. This rate
depends on environmental conditions and the condition or type of metal. In the U.S., corrosion rate is
typically computed using Mils Penetration per Year (MPY). MPY is a unit of measurement equal to one
thousandth of an inch. Corrosion can be expressed as following:

Percentage Weight Loss (%W) MPY mg/cm
2
.day g/in
2
.hr.

To calculate corrosion rate, the following must be determined:
Weight loss (reduction in weight during reference time), [W in mg]
Area (initial surface area), [A in sq. in]
Time (length of reference time), [T in hr.]
Density, [D in g/cm
3
]
MPY =

This measurement can be used to measure the thickness of items such as:
Paint Paper Wires Foil Plastic sheets

Mils can be very useful in terms of manufacturing tolerances and dimensions, such as in the production of
vehicle engines' head gaskets or the amount of material to remove from the automobile head in order to
make adjustments to the cylinders compression ratio.

Prepared by: Sheikh Mubin Ashraf (B.E in Petroleum NED Batch: 2010-11)
Polarization

Polarization is a deviation of the electrochemical process from equilibrium due to an electric current passing
through the galvanic cell that causes a change in the electrode potential. It is referred as a potential shift
away from the open circuit potential of the system. The deviation from equilibrium causes an electrical
potential difference between the polarized & equilibrium (un-polarized) potential known as over-potential.

Examples:
Zinc in air-free hydrochloric acid,
Magnesium in neutral water,
Zinc in aerated hydrochloric acid occur over a single metallic surface

Equilibrium State [Non Polarized State]
At the equilibrium (non-polarized) state the rates of oxidation and reduction reactions proceeding at any
electrode are equal. For example the ions of Cu are receiving electrons on the electrode surface and transfer
from the electrolyte to the copper deposit. In parallel, the same number of copper atoms gives up their
electrons and dissolves in the electrolyte.

Reduction: Oxidation:
Cu
++
+ 2e
Cu Cu Cu
++
+ 2e

The processes produce two equal electric currents in opposite directions. The current passing through the
electrode surface in the equilibrium (non-polarized) state at any direction is called exchange current.

The electrode potential may be calculated according to the Nernst equation: E = E
0
-
(C
ion
)

Processes occurring at Electrochemical Interface:
Mass transport to a surface is governed by three
forces

1. Diffusion,
2. Migration and
3. Convection

In the absence of an electrical field, the migration
term, that only affects charged ionic species, is
negligible while the convection force disappears in
stagnant conditions while the diffusion of the ions
through the layers controls the electrochemical
reaction (corrosion, Electroplating).

Types of Polarization:
Polarization may occur either at the cathode (cathodic polarization) or at the anode (anodic polarization). It
is said to be Anodic when the anodic processes on the electrode are accelerated by changing the specimen
potential in the positive (noble) direction and Cathodic when the cathodic processes are accelerated by
moving the potential in the negative (active) direction.
There are three distinct types of polarization.

Activation polarization Concentration polarization Resistance polarization


Concentration Polarization
It is the polarization component that is caused by the
concentration changes in the environment adjacent to the
surface that results in the loss of voltage.
The chemical species participating in a corrosion process is
in short supply. Hence the cathodic processes depend on
the reduction of dissolved oxygen since it is usually in low
concentration (ppm).
It is associated with the concentration of ions in solution
which shields the metal, thereby causing a decrease in
the electrical potential of the cell.
Concentration polarization of an electrode is a result of
formation of a Diffusion layer adjacent to the electrode
surface due to the gradient of the ion concentration.
It may be lowered by increasing agitation and rising the
electrolyte temperature.

Activation Polarization
Activation polarization is the formation of a layer containing absorbed hydrogen atoms that block the
metal's surface from the corrosion process. It is associated with high concentration of active species.
It is the over-potential (change of the electrode potential) caused by overcoming the energy barrier of
the slowest step of the electrochemical reaction.

Example Phenomenon:
Common cause of cathodic activation polarization is the reaction of Hydrogen formation and evolution at
the cathode surface:

Step 1: Reduction of the hydrogen ions resulted in formation of atomic hydrogen on the cathode surface.
H
+
+ e
[H]

Step 2: Formation of molecules of gaseous hydrogen.
2[H] H
2

Step 3: Formation of hydrogen bubbles.
H
2
+ H
2
+ H
2
+H
2
+ ... nH
2

The cathode is polarized by the hydrogen atoms producing a film covering the cathode surface. The film
affects the process kinetic: it slows down the reaction between the electrons and hydrogen ions dissolved in
the electrolyte resulting in Activation Polarization.

Resistance polarization [Ohmic or IR Drop]
Resistance polarization refers to the potential drop due to either the high resistivity of the electrolyte
surrounding the electrode or an insulation effect of the film on the electrode surface formed by the reaction
products. Resistance polarization may be expressed by the Ohms Law.

Importance of Polarization:
Knowing the kind of polarization which is occurring can be very helpful, since it allows an assessment of the
determining characteristics of a corroding system.
Concentration polarization usually predominates when the concentration of the active species is low; for
example, in dilute acids or in aerated waters where the active component, dissolved oxygen, is only
present at very low levels.
If corrosion is controlled by concentration polarization, then any change that increases the diffusion rate
of the active species (e.g., oxygen) will also increase the corrosion rate. In such a system, it would
therefore be expected that agitating the liquid or stirring it would tend to increase the corrosion rate of
the metal.
If a corrosion reaction is activation controlled then stirring or agitation will have no effect on the
corrosion rate.
The ohmic drop becomes an extremely important factor when studying corrosion phenomena for which
there is a clear separation of the anodic and cathodic corrosion sites, e.g. crevice corrosion.
The ohmic drop is also an important variable in the application of protective methods such as anodic
and cathodic protection that force a potential shift of the protected structure by passing a current in the
environment.
Activation polarization is usually the controlling factor during corrosion in strong acids.

Different Aspects of Corrosion

Thermodynamic Electrochemical Metallurgical Physical

Thermodynamic Aspects of Corrosion:
Thermodynamic considerations allow the determination of whether a reaction can occur spontaneously.
If metal dissolution is unfavorable thermodynamically in a given set of circumstances the job of the
corrosion engineer is done.

Free Energy of a Corrosion Reaction:
In electrical and electrochemical processes, electrical work is defined as the product of charges moved (Q)
times the potential (E) through which it is moved. If this work is done in an electrochemical cell in which the
potential difference between its two half-cells is E, and the charge is that of one mole of reaction in which n
moles of electrons are transferred, then the electrical work (-w) done by the cell must be nE. In this
relationship, the Faraday constant F is required to obtain coulombs from moles of electrons. In an
electrochemical cell at equilibrium, no current flows and the energy change occurring in a reaction is
expressed in equation:
EnF G

G- Gibbs Free Energy (Joules) E-Emf (volts)
n-number of electrons involved in the reaction F-Faraday (96500 C/equivalent)

The larger the value of E for any cell more is the tendency for the overall cell reaction to proceed.

E
cell
= E
cathode
- E
anode

When a metal M is immersed in an aqueous electrolyte, it acquires a certain potential. If the activity of the
metal ions M
n+
in aqueous environment is unity, then the acquired potential is known as Standard Potential

The Law of Thermodynamics states that: The direction of a reaction is governed by the requirement of a
material to be in a lower or more stable energy state.


Standard Hydrogen Electrode (SHE)
The potential of the electrode equals zero if the hydrogen ion activity and the pressure of hydrogen gas
in the atmospheres are both unity. This is the standard hydrogen potential.
The half - cell potential for any electrode is equal to the emf of a cell with the standard hydrogen
electrode as the other electrode.
The half - cell potential for any electrode expressed on this basis is said to be on the normal hydrogen
scale or on the standard hydrogen scale, sometimes expressed as
H
or (S.H.E)

EMF Series
All metals have been arranged in a series according to their standard potential (
0
) values.
The more positive value corresponds to noble metals and the more negative value corresponds to more
reactive metals (when arranged according to reduction potential)
Of the EMF series if two metals make up a cell, the more active metal acts as the anode and the more
noble metal of the two will act as cathode

Pourbaix Diagram [Potential pH Diagrams]
Marcel Pourbaix developed potential-pH diagrams
to show the thermodynamic state of most metals
in dilute aqueous solutions.
With pH as abscissa and potential as ordinate,
these diagrams have curves representing chemical
and electrochemical equilibria between metal and
aqueous environment.
These diagrams ultimately show the conditions for
immunity, corrosion and passivation.
Pourbaix diagrams offer a large volume of
thermodynamic information in a very efficient and
compact format.
The information in the diagrams can be beneficially
used to control corrosion of pure metals in the
aqueous environment
By altering the pH and potential to the regions of immunity and passivation, corrosion can be
controlled. For example, on increasing the pH of environment in moving to slightly alkaline regions,
the corrosion of iron can be controlled
Changing the potential of iron to more negative values eliminate corrosion, this technique is called
cathodic protection.
Raising the potentials to more positive values reduces the corrosion by formation of stable films of
oxides on the surface of transition metals
These diagrams are purely based on thermodynamic data and do not provide any information on the
reaction rates
Pourbaix diagrams deal with pure metals which are not of much interest to the engineers

Electrochemical Aspects of Corrosion:
When the oxide-free surface of a metal becomes exposed to the solution, positively charged metal ions tend
to pass from the metal into the solution, leaving electrons behind on the metal, i.e.

The accumulation of negative charge on the metal due to the residual electrons leads to an increase in the
potential difference between the metal and the solution. This potential difference is called the Electrode
Potential. This change in the potential tends to retard the dissolution of metal ions but to encourage the
deposition of dissolved metal ions from the solution onto the metal, i.e. the reverse of reaction occurs.
Continuation of the dissolution and deposition of metal ions would result in the metal reaching a stable
potential such that the rate of dissolution becomes equal to the rate of deposition. This potential is termed
as Reversible Potential Er and its value depends on the concentration of dissolved metal ions and the
standard reversible potential Eo for unit activity of dissolved metal ions.

The potential of a metal in a solution does not usually reach the reversible potential but remains more
positive because electrons can be removed from the metal by alternative reactions. In acid solutions,
electrons can react with hydrogen ions, adsorbed on the metal surface from the solution, to produce
hydrogen gas.

This reaction permits the continued passage of an equivalent quantity of metal ions into solution, leading to
corrosion of the metal. Normally hydrogen escapes from the system, so that the potential remains more
negative than the reversible potential and corrosion continues.

In neutral solutions, the concentration of hydrogen ions is too low to allow reaction to proceed at a
significant rate, but electrons in the metal can react with oxygen molecules, adsorbed on the metal surface
from air dissolved in the solution, to produce hydroxyl ions.

Again, the potential of the metal remains more negative than the reversible potential for reaction.

In Electrochemical terminology, an electrode at which an oxidation reaction occurs is called an anode. The
process of oxidation involves a loss of electrons by the reacting species, as occurs in the metal dissolution
reaction. Thus an area of a corroding metal where metal dissolution occurs is an anode and metal
dissolution is the anodic reaction of corrosion. An electrode at which a reduction reaction occurs is called a
cathode. Reduction involves a gain in electrons. The reduction of hydrogen ions and oxygen are thus the
cathodic reactions of corrosion and the area of a corroding metal where these reactions occur is a cathode.


Economic Considerations for Corrosion Control

Studies had shown that the annual corrosion costs range from approximately 1 to 5 percent of the GNP of
each nation. Several studies separated the total corrosion costs into two parts:

Avoidable Costs: The costs that could be avoided if better corrosion control practices were used
Unavoidable Costs: Costs where savings required new and advanced technology.

Estimates of avoidable corrosion costs in these studies have varied widely with a range from 10 to 40
percent of the total cost.

Factors that need to be considered in calculating Net
Present Value (NPV) include:
1. Initial cost
2. Best estimate of expected life
3. Length of typical shutdown for emergency repair
4. Cost of planned maintenance during scheduled
shutdowns
5. Effect of failure on total plant operation

Study identified ten elements of the cost of corrosion:
Replacement of equipment or buildings Loss of product

Excess capacity
Maintenance and repair Redundant equipment Design
Corrosion control Technical support Insurance
Parts and equipment inventory

Economic problems result from damage to
pipes, storage tanks, valves, and
meters. Damage to pipes is the most
prevalent, consisting of leaks and reduced
carrying capacity. These pipe corrosion
problems often result from tuberculation,
which is the production of mounds of rust on
the inside of the pipe. These mounds reduce
the space in the pipe available to carry
water, just as scaling does. In addition,
tubercles are usually associated with pits in
the pipe wall, which may go all the way
through the pipe and cause leaks.

Passivity
Passivity is defined as the loss of chemical reactivity. It is the characteristic of a metal exhibited when the
metal does not become active in the corrosion reaction.

Cause of Passivity: [Formation of a Protective Layer]
Passivity is caused by the buildup of a stable, tenacious layer of metal oxide (30
o
A or less thick) on the
surface of the metal. Once the layer, or film, is formed, it acts as a barrier separating the metal surface
from the environment.
Numerous metals and their alloys with a high affinity for oxygen have the characteristic of covering
themselves with a protective layer of oxide which prevents their corrosion in corrosive environments.
These conditions are described as passivity conditions and determine the state of inertia of the metal,
which behaves like a noble metal.

Examples:
An oxide or nitride film naturally forms due to exposure. However, Rust is not a passive layer.
Fe, Cr, Ni, Ti, and alloys containing significant quantities of these elements exhibit passive behavior in
specific environments. E.g. Stainless steel in oxygen in specific environment or iron in 70% nitric acid
possesses intrinsic corrosion resistance.
Stainless steel owes its passivity due to the formation of a very protective chromium oxide layer on its
surface which makes it resistant to many environments where iron or carbon and low alloy steels may
suffer even very severe corrosion.
The reinforcement bars of reinforced concrete are perfectly passivated by the alkalinity of the hydrated
cement mixture. The iron in concrete (alkaline solutions) behaves like stainless steel in fresh water.
Aluminium and titanium are resistant to corrosion thanks to their ability to passivate since oxides such
as Al
2
O
3
, TiO
2
, and Cr
2
O
3
are very effective passive films.

Behavior of Oxide Films in Metals:
The surfaces of all metals (except for gold) in air are covered with oxide films. When such a metal is
immersed in an aqueous solution, the oxide film tends to dissolve. If the solution is acidic, the oxide film may
dissolve completely leaving a bare metal surface, which is said to be in the active state. In near-neutral
solutions, the solubility of the oxide will be much lower than in acid solution and the extent of dissolution
will tend to be smaller. The underlying metal may then become exposed initially only at localized points
where owing to some discontinuity in the metal, e.g. the presence of an inclusion or a grain boundary, the
oxide film may be thinner or more prone to dissolution than elsewhere. If the near-neutral solution contains
inhibiting anions, this dissolution of the oxide film may be suppressed and the oxide film stabilized to form a
passivating oxide film which can effectively prevent the corrosion of the metal, which is then in the passive
state.

Overpassivation: It results from the formation of higher oxides of the metal, which dissolve completely to
give anions, for example, CrO
4
2-
, or supply the solution with their own cations, which decompose with the
release of oxygen; NiO
2
is a typical higher oxide that supplies cations. The oxygen that participates in
forming the passivated layer can be supplied by such oxidizing agents as H
2
O
2
or HNO
3
. Passivation may be
facilitated by anions that give sparingly soluble salts or mixed oxides of the metal that is being passivated.
However, the most widespread source of passivating oxygen is water, which reacts either chemically or
electrochemically with the metal.

Active Passive Behavior of Metals:
Transition metal such as Fe, Cr, Ni, Al and Ti demonstrate an activepassive behavior in aqueous
solutions such metals are called active-passive metals. They exhibit S-shaped polarization curves. In
active materials, it is a straight line with a slight slope.

Active Region:
The potential of an electrode in an electrolyte when no current is passed and forward rate of reaction is
equal to the rate of reverse reaction is called as Equilibrium Potential (E
eq
or E
M/M
+
or E
)
The current density (i) increases with E i.e. the corrosion rate increases with increasing oxidizing power
until primary passive potential is achieved.
Critical current Density (i
critical
) the maximum current density observed in active region for metal or
alloys that exhibits an active Passive behavior.
Passive Region:
The potential of an electrode where a change from an
active to a passive state occurs is known as Passive
Potential (E
p
).
A passive film is formed and the current density drops
to i
pass
which is very small but sufficient enough to
maintain a protective film on the metal. The corrosion
current remains constant with increasing potential so
there is no effect on corrosion of the metal.

Transpassive Region:
The protective anodic film is damaged and may break
down completely.
Flade Potential (E
F
) the potential at which metal changes from a passive state to an active state.
Transpassive Potential (E
t
) the potential corresponding to the end of passive region which corresponds
to the initial point of anodic evolution of Oxygen. This may correspond either to breakdown
(electrolysis) voltage of water or to the pitting potential
Pitting Potential (E
pitting
) It is the potential at which there is a sudden increase in the current density due
to breakdown of passive film on the metal surface in the anodic region.

Stainless Steel Passivation
Stainless passivation is the process by which stainless steel will spontaneously form a chemically inactive
surface when exposed to air or other oxygen-containing environments.
Steels containing more than 11% Chromium are capable of
forming an invisible, inert or passive, self-repairing oxide
film on their surface. It is this passive layer that gives
stainless steels their corrosion resistance.
If a stainless steel surface is scratched, then more Chromium
is exposed which reacts with oxygen allowing the passive
layer to reform.
If a particle of carbon steel is embedded in the scratch then
the passive layer cannot reform and corrosion will occur
when the metal is wetted or exposed to a corrosive
environment.
Passivating stainless steel is the removal of exogenous iron
or iron compounds from the surface by means of a chemical
dissolution, most typically by a treatment with mild oxidant
like citric acid passivation solution that will remove the
surface contamination but will not significantly affect the stainless steel itself.
Passivation also is accomplished by Electropolishing. Electropolishing is an electrochemical process that
is a super passivator of stainless steel and results in a more passive surface.

ENVIRONMENTAL EFFECTS

Effect of Oxidizer Concentration:
For metals that demonstrate active-passive transition,
passivity is achieved only if a sufficient quantity of oxidizer
is added to the medium. Increasing concentration increases
the corrosion rate in active region followed by a rapid
decrease that is essentially independent of oxidizer
concentration.

When Active-Passive metal is initially passive in corrosive
medium then the effect of concentration is negligible. This
condition frequently occurs when the metal is immersed in
a strong oxidizing medium like Nitric Acid or Ferric Chloride.

The Transpassive region is observed usually in hot nitrating
mixtures containing conc. Sulfuric Acid.

Example: 18Cr-8Ni Stainless Steel in H
2
SO
4
& HNO
3
shows the typical behavior at elevated temperatures.

Effect of Solution Velocity:

Curve B: For corrosion processes that are controlled by
Activation Polarization, Agitation & velocity have no effect on
corrosion rate.

Curve A: If the corrosion process is under cathodic diffusion
control (concentration polarization), then agitation increases
the corrosion rate. This generally occurs when oxidizer is in
small amount e.g. dissolved oxygen in acids or water. At a
specific velocity the corrosion rate drops and becomes
independent of the velocity as the metal is now in passive
state. E.g. Stainless steel and titanium.

Curve C: Some metals owe their corrosion resistance in certain
mediums due to the formation of massive bulk protective films on their surfaces. E.g. Lead & Steel are
protected from attack in in sulfuric acid by insoluble sulfate films. However, if they are exposed to extremely
high corrosive velocities then mechanical damage or removal of the films can occur resulting in accelerated
attack. This is called Erosion Corrosion. Before mechanical damage the effect of velocity is negligible.

Effect of Temperature:
Temperature increases the rate of almost all chemical reactions.

Curve A: It represents an exponential rise in corrosion rate with
increasing temperature.

Curve B: It shows initially almost negligible effect on CR at low
temperatures followed by a very rapid rise in CR at high
temperatures. E.g. 18Cr-8Ni stainless steel in nitric acid shows the
typical behavior. Increasing the temperature of HNO
3
greatly
increases its oxidizing power. At low or moderate temperatures,
stainless steel exposed to nitric acid is in the passive state very
close to Transpassive region.

An increase in temperature of a corroding system has four main effects:
The rate of chemical reaction is increased.
The solubility of gases in the solution is decreased.
The solubility of some reaction products may change that result in different corrosion products.
Viscosity is decreased.

Effect of Oxygen [Oxygen as a Depolarizer]
The presence of oxygen in water increases the corrosion rate. This due to the rapid reaction between
oxygen and the polarized layer of atomic hydrogen absorbed on the oxide layer. Therefore, oxygen is
known as a Depolarizer.
Oxygen, therefore, has two effects:
It removes the polarizing layer of atomic hydrogen, and
It can react directly with the metal or metal oxide; thus, the corrosion rate increases.
Having hydrogen in the water helps minimize the amount of corrosion by eliminating the amount of
oxygen in the system.

Effect of pH
PH also affects the corrosion rate. In the range of pH
4-10, the corrosion rate of iron is relatively
independent of the pH of the solution.
At lower pH the film cannot accumulate in the
surface of metal. Corrosion takes place at higher rate.
At pH>10 corrosion rate decreases. This is believed to
be due to an increase in the rate of the reaction of
oxygen with Fe (OH)
2
(hydrated FeO) in the oxide
layer to form the more protective Fe
2
O
3
(note that
this effect is not observed in deaerated water at high
temperatures).
For pH<4.0, ferrous oxide (FeO) is soluble. The oxide
dissolves as it is formed rather than depositing on the metal surface to form a film. Formation of H
2
at
lower pH means that depolarization with oxygen & hydrogen evolution are both playing a role.
A pH between 7 and 10 gives a lower rate of corrosion.
The pH is always maintained alkaline to minimize corrosion rate.

Remedial Measures for Corrosive Environments

1. De-Aeration: It is the process of removing air from the corrosive environment where the presence of
oxygen accelerates the corrosion rate. It is frequently used in boiler feed water operating at high
temperatures and also used in Water Supply Systems.

2. De-Gasification: It is the process of removing dissolved gases from the corrosive environment such as
CO2, H2S etc. The presence of CO2 in wet environment forms carbonic acid that may react with the steel
surface forming corrosion product called ferric carbonate (scale deposition). The presence of H2S in the
environment causes Hydrogen embrittlement (hydrogen induces cracks in the steel body).

3. Water Softening: It is the process of removal of calcium, magnesium and other cations from Hard
Water. The Lime & Soda Ash processes remove dissolved CO2 from water which decreases the pH of
water and hence also reduces corrosion.

4. Addition of Inhibitors: These are chemical substances added in the corrosive environment to prevent
the occurring of corrosion reaction.


Uniform Corrosion (General Attack Corrosion)
A corrosive attack proceeding evenly over the entire surface area, or a large fraction of the total area.
It is relatively uniform reduction of thickness over the surface of a corroding material (decrease in metal
thickness per unit time or a weight loss per unit area per unit time).
It is the uniform thinning of a metal without any localized attack, corrosion does not penetrate very
deep inside, and the most familiar example is the rusting of steel in air.
It is relatively easy to measure, predict and design against this type of corrosion damage.
While uniform corrosion may represent only a small fraction of industrial corrosion failures, the total
tonnage wasted is generally regarded as the highest of all forms.

Mechanism: What causes Uniform Corrosion?
The anodic reaction in the corrosion process is always the oxidation reaction: M M
+
+ e

In acidic environments, i.e., pH<7, the cathodic process is mainly the reduction of hydrogen ions.
In alkaline or neutral environment, i.e., pH=7 or pH>7, reduction of dissolved oxygen is the predominant
cathodic process that causes uniform corrosion.
2H
+
+ 2e
H
2
O
2
+ 2H
2
O + 4e
4OH

With uniform distribution of cathodic reactants over the entire exposed metal surface, reactions take place
in a "uniform" manner and there is no preferential site or location for cathodic or anodic reaction. The
cathodes and anodes are located randomly and alternating with time resulting in uniform loss of dimension.

Common Examples:
Aqueous corrosion of iron (Fe) in H
2
SO
4
solution:
Fe is dissolved (oxidize) at a uniform rate according
to the following anodic and cathodic reactions.

Atmospheric Corrosion of Aluminium:
It is due to a passive oxide film formation instead of
a porous layer. The gray/black-color film may form.

Tarnishing of silver ware.
Tarnishing of electrical contacts.
Corrosion of underground pipes
(Composite asphalt coated).
Corrosion of offshore drilling platforms.
Corrosion of galvanized steel stairways.
Corrosion of automobile bodies.
Atmospheric Corrosion of Zinc:
Zinc can uniformly corrode forming a White Rust.
The compound Zn
4
CO
3
. (OH
6
) or ZnCO
3
.Zn (OH)
2
is
zinc carbonate or white rust or wet-storage stain
(porous).

Atmospheric corrosion of a steel structureRusting
It is a common example of uniform corrosion, which
is manifested as a brown-color corrosion layer on
the exposed steel surface. This layer is a ferric
hydroxide compound known as Rust. The compound
precipitates as a solid.

Facts about Uniform Corrosion:
Uniform corrosion is the most commonly found form of corrosion.
Rust formed on low alloyed steel is a special form of uniform corrosion.
Uniform corrosion occurs mainly on very active metals (low Reversible potential).
Noble metals (gold, platinum) are immune against uniform corrosion.
Chromium, Titanium, Nickel, stainless steel are protected by a passive film and are therefore not
concerned by uniform corrosion.

Prevention:
Uniform attack can be controlled or prevented by:
Proper Material Selection including Coatings
Inhibitors
Cathodic Protection

Galvanic Corrosion (Dissimilar Metal or Bimetallic Corrosion)
It is an accelerated corrosion of an active metal because of an electrical contact with a more noble metal in a
corrosive electrolyte. The contact of two dissimilar metals constitutes a Galvanic Couple.
When two electrochemically dissimilar metals are in contact, a conductive path occurs for electrons and ions
move from one metal to the other due to which one metal corrodes as its ions are deposited onto the other
metal. This is known as Galvanic Action.

In general, the reactions which occur are similar to those that would occur on single, uncoupled metal, but
the rate of attack is increased, sometimes dramatically.

Mechanism:
The driving force for corrosion is a potential difference b/w electrochemical potential of different materials.

Anode & Cathode:
In a bimetallic couple, less noble material being less corrosion resistant become the anode of the corrosion
cell & tends to corrode at an accelerated rate while the more noble material act as cathode in the corrosion
cell and will undergo relatively reduced or no corrosion. The effect of coupling the two metals together
increases the corrosion rate of the anode and reduces or even suppresses corrosion of the cathode.

Galvanic Series
Galvanic corrosion potential is a measure of how dissimilar metals will corrode when placed against
each other in a series.
Galvanic series is an arrangement of both metals and alloys according to their actual measured
potentials in a particular environment. There would be one galvanic series for each environment.
Metals and alloys showing active-passive behavior are listed in both active and passive states.

Factors Influencing Galvanic Corrosion:
1. Electrode Potential: The position of metal in the galvanic series significantly affects the magnitude of
galvanic corrosion. Metals close to one another in the list generally do not have a strong effect on one
another, but the farther apart are any two metals, the stronger the corroding effect on the higher metal.

2. Distance Effect: Solution conductivity varies inversely with the length of the conduction path. Most
corrosion damage is caused by current which cover short paths. Hence, the greatest galvanic damage is
likely to be encountered near the junction of the two metals and the severity would be decreased with
increased length. If two different metals are far away from each other, there would be no risk of galvanic
corrosion, because of very little current flow.

3. Area Effect: The area ratio is very important in consideration of the likelihood of bimetallic corrosion. The
larger the cathode compared to anode, more oxygen reduction can occur & hence greater galvanic current
& corrosion. Under static conditions, where bimetallic corrosion current is often dependent upon rate of
diffusion of dissolved oxygen to the cathode, the amount of bimetallic corrosion is independent of the size
of anode & is proportional to the area of cathodic metal surface. This is sometimes known as catchment
area principle, & has important implications in designing to minimize the risk of bimetallic corrosion. For a
constant area of cathode metal the amount of corrosion of anode metal is constant, but intensity of
corrosion is increased as the area of the anodic metal is decreased.

4. The nature of the environment: The severity of galvanic corrosion largely depends upon the type &
amount of moisture in the environment. Water containing copper ions, like seawater, are likely to form
galvanic cells on a steel surface of the tank. If the water in contact with steel is either acidic or contains salt,
the galvanic reaction is accelerated because of the increased ionization of the electrolyte. In marine
environments, galvanic corrosion may be accelerated due to increased conductivity of the electrolyte. In
cold climates, galvanic corrosion of buried material is reduced because of the increased resistivity of soil. In
warm climates, on the other hand, it is the reverse because of the decreased resistivity of the soil.
Methods of Preventing Galvanic Corrosion
Methods of preventing or minimizing bimetallic corrosion are based upon following factors:

Breaking the electrical path in the metallic or electrolyte parts of the system.
Excluding oxygen from electrolyte Adding inhibitors to electrolyte Sacrificial corrosion

Electrical Insulation:
Galvanic corrosion can be prevented by the use of electrical insulation between different metals thus
stopping formation of the electrical circuit. Insulation can be achieved by the use of plastic bushes and
washers such as nylon or PTFE or rubber gaskets.

Use of Inhibitors:
Inhibitors are often injected to reduce corrosion of the carbon steel and this will also minimize corrosion at
bimetallic junctions. Galvanic action in systems containing copper can sometimes be controlled by a specific
inhibitor such as benzotriazole.

Metallic Coatings:
A wide range of paint and taping systems are available for protecting metals; paints can contain inhibitors or
sacrificial metals such as zinc. Ideally both members of a bimetallic couple should be painted, but where this
is impracticable the cathodic member should be coated in preference; treating only the anodic metal
increases the risk of severe localized bimetallic corrosion at any defect in the coating.

Metal coatings can be applied by electroplating, dipping or spraying to give close identity with the
second metal; an example is the Aluminium coating of steel in contact with Aluminium.
Alternatively compatibility between two metals can be obtained by coating one of them with a third
metal such as zinc or cadmium.
In some cases it is preferable to coat both metals with a third metal.
In industrially polluted atmospheres zinc coatings on steel are superior to those of cadmium, while the
latter are preferred where high humidity and condensation occur.
In case of microbial corrosion, materials can be protected by coating with resistant synthetic polymers or
inhibited paints, by dosing with biocides or by designing to avoid conditions that favor microbial growth.

Sacrificial Anodic Protection:
Galvanic corrosion can be used to advantage in certain cases if an anodic metal is deliberately exposed to
corrosion and sacrificed in order to protect part of the structure. Sacrificial anodes tend to reduce the
difference of the potentials of the metals involved by polarization. They can be used to protect stainless
steel. Since they corrode, sacrificial anodes need periodic inspection and replacement to maintain the
protection. In practice magnesium and carbon steel are used for sacrificial anodes. Zinc and Aluminium can
also be used but their corrosion products are often not acceptable.

Preventive Measures: [Important Considerations]
Select metals, close together, as far as possible, in the galvanic series.
The area of the more active metal must be kept smaller than the area of the less active metal.
If dissimilar metals are to be used, insulate them.
Use inhibitors in aqueous systems whenever applicable and eliminate cathodic depolarizers.
Apply coatings with judgment. Do not coat the anodic member of the couple as it would reduce the
anodic area and severe attack would occur at the inevitable defect points in the coating. Therefore, if
coating is to be done, coat the more noble of the two metals in the couple which prevents electrons
being consumed in a cathodic reaction and likely to be corrosion rate controlling.
Avoid joining materials by threaded joints.
Use a transition piece (third metal) in the couple that must have similar properties than the two metals.
Use Sacrificial Anodic material, such as zinc or magnesium. For instance, zinc anodes are used in cast
iron water boxes of copper alloy water-cooled heat exchangers.
In designing the components, use replaceable parts so that only the corroded parts could be replaced
instead of the whole assembly.

Crevice Corrosion

Crevice corrosion refers to corrosion occurring in confined spaces to which the access of the working
fluid from the environment is limited. These spaces are generally called crevices.
Crevice corrosion is a form of localized attack that occurs in zones of restricted flow where a metallic
material surface is in contact with a small volume of confined, stagnant liquid.
It is encountered particularly in metals and alloys which owe their resistance to the stability of a passive
film, since these films are unstable in the presence of high concentrations of Cl
and H
+
ions.
Crevice zones may result from the design of the component or from the formation of deposits during
service, shutdown, or even fabrication. These deposits may come from suspended solids in the
environment, corrosion products, or biological activity. Low-flow areas are prone to the formation of
such deposits.

Examples of crevices: Gaps and contact areas between parts, under gaskets or seals, inside cracks and
seams, spaces filled with deposits and under sludge piles. (Green corrosion product called Patina is formed)

Examples of Crevice Corrosion: Stainless steels, nickel-base alloys, aluminum alloys, and titanium alloys
in aerated chloride environments, particularly in sea or brackish water, but also in environments found in
chemical, food, and oil industries. Other cases of crevice corrosion are also known such as the so-called
corrosion by differential aeration of carbon steels, which does not require the presence of chloride in the
environment. Other examples include crevice corrosion of steels in concentrated nitric acid and inhibited
cooling water and of titanium alloys in hot sulfuric environments.

The major factors influencing crevice corrosion are:
Crevice type: metal-to-metal, metal-to-non-metal
Crevice geometry: gap size, depth, surface roughness
Material: alloy composition (e.g. Cr, Mo), structure
Environment: pH, temperature, halide ions, oxygen

Basic Mechanism: The specificity of the crevice zones arises as a result of:
1. Limited mass transport by diffusion & convection between the inside of crevice & the bulk environment
due to the local accumulation of corrosion products, and secondly due to
2. The difference in solution resistivity between the inside and the outside of the crevice.

This results in the buildup of a galvanic cell between crevice and external surfaces.

Explaining the Mechanism:
Stage 1: Corrosion occurs as normal both inside and outside the crevice (uniformly over the entire surface):
The overall reaction involves dissolution of metal and reduction of oxygen to hydroxide ion.

Anodic reaction: MM
n+
+ ne, Cathodic reaction: O2+2H2O+4e 4OH
.

The positively charged metallic ions are electrostatically counterbalanced by OH ions.

Stage 2: At this stage, the cathodic reaction inside the crevice consumed most of the oxygen available. So
oxygen within the crevice is depleted because of the restricted convection due to which the oxygen
reduction ceases in the area. However, the overall rate of oxygen reduction remains the same since crevice
area is very small.

Stage 3: Dissolution of metal continuous, therefore Cl ions diffuse into the crevice to maintain a minimum
potential energy resulting in formation of a Metal chloride. Hydrolysis of metal chloride lowers the pH.
MCln + nH2O M (OH) n + nHCl

Stage 4: More M
n+
ions attack more Cl
ions leads to lower pH inside the crevice, metal dissolution

accelerates and more M
n+
ions will be produced that will lower the pH.

As the corrosion within the crevice increases the rate of oxygen reduction on the adjacent surface also
increases. This cathodically protects the external surface. Thus during crevice corrosion the attack is
localized within the shaded area while the remaining surface suffers little or no corrosion.

Crevice corrosion is initiated by a difference in concentration of some chemical constituents, usually oxygen,
which set up an electrochemical concentration cell (differential aeration cell in the case of oxygen). Outside
of the crevice (the cathode), the oxygen content and the pH are higher - but chlorides are lower.

Chlorides concentrate inside the crevice (the anode), worsening the situation. Ferrous ions form ferric
chloride and attack the stainless steel rapidly. The pH and the oxygen content are lower in the crevice than
in the bulk water solution, just as they are inside a pit. The pH inside the crevice may be as low as 2 in a
neutral solution. Once a crevice has formed, the propagation mechanism for crevice corrosion is the same as
for pitting corrosion.

Factors Affecting Crevice Corrosion

Combating Crevice Corrosion:
Use Welded butt joints instead of riveted or bolted joints. Sound welds and complete penetration are
necessary to avoid porosity and crevices on the inside.
Close crevices in existing lap joints by continuous welding, caulking or soldering.
Design vessels for complete drainage; avoid sharp corners and stagnant areas. Complete drainage
facilities, washing & cleaning tends to prevent solids from settling on the bottom of the vessel.
Inspect equipment and remove deposits frequently.
Remove solids in suspension early in the process.
Provide uniform environments as in the case of backfilling a pipeline trench.
Use solid non-absorbent gaskets such as Teflon, wherever possible.
Weld instead of rolling in tubes in tube sheets.

Pitting Corrosion
Pitting Corrosion is the localized corrosion of a metal surface confined to a point or small area that takes
the form of cavities. It is one of the most damaging forms of corrosion.
Pitting corrosion occurs at passivated metal surfaces during the access of aggressive anions.
Many metals and their alloys are subject to this type of corrosion (e.g., iron, nickel, copper, aluminium,
steels), whereas chromium is one of the few exceptions that resists pitting in aggressive environments.
The restriction of the dissolution to pits within a large passivated metal surface, which may serve as a
large cathode for the reduction of oxidants such as dissolved oxygen, leads to fast perforation of the
metal, which weakens the construction and thus causes large economic losses and safety problems.

The main reasons for localized corrosion failures are:
Insufficient passive film stability (for stainless steel, insufficient chromium content cannot prevent
chemical dissolution at the oxide-solution interface)
Design errors: the presence of areas with stagnant solution will accelerate the generation of local
aggressive conditions
Inadequate surface preparation: the presence of deep scratches or defects during surface preparation
can act as pit initiation sites.

Steps involved in Pitting:
Pitting at passivated metal surfaces is a complex process with a sequence of steps which are as follows:
1. Breakdown of passivity 2. Early stages of pit growth
3. Late stages of pit growth 4. Re-passivation phenomena

Pit initiation [Breakdown of Passivity]
The first stage of the pitting process called pit initiation is related to the breakdown of the protecting passive
oxide. Different mechanisms have been proposed for the various passive materials depending on the
thickness of their oxides and also on the chemical stability at the oxide-solution interface.

1) The penetration mechanism: the Cl- ions (or other halides anions) are integrated instead of OH- and
migrate through the passive film inducing hole formation at the metal-oxide interface. It is assumed that
cation vacancies migrate from the oxide electrolyte to the metal-oxide interface. The related voids lead to
stresses within the passive film and its final breakdown. The inward diffusion or migration of cation
vacancies is affected by the incorporation of Cl ions at the oxide-electrolyte interface. This causes a critical
concentration for breakdown at the pitting potential.
This type of initiation process is typical of corrosion resistant material with very thin thermodynamically
stable oxides like Chromium.

2) The adsorption mechanism: the Cl- ions (or other halides anions) adsorbs locally on the surface replacing
OH- and decreases the stability of the oxide surface. The passive layer dissolves faster until the metal
surface is exposed. This process is typical of less corrosion resistant materials such as stainless steels where
the passive oxide is in a dynamic formation-dissolution state.

3) The oxide cracking mechanism: in this case, the surface oxides (hydroxides) film cracks open due to
stresses (internal or applied). This initiation mode is rarer and implies as prerequisite a poorly passivating
surface (thicker oxide) or the presence of a thick anodized layer for example. Magnesium in the alkaline
domain would be such an example of a material able to passivate but forming a thick oxide layer that can
crack in presence of chlorides.

The pitting potential is defined by the threshold potential at which the measured current rapidly increases
because of the growth of a stable localized attack. Pit formation can however already occur at potentials
lower than the pitting potential.

Pit growth:
Once a metastable pit reached stabilized growth, in-depth propagation will occur. Pit usually grows in the
direction of gravity. Most pits develop and grow downwards from horizontal surface.

The question is now why a localized attack can be so detrimental. The answer becomes clear when
considering the electrochemical reactions involved.

Reaction steps during pit growth processes:
Dissolved metallic ions are hydrolyzed. As a result, large amount of protons (H3O+) are formed and the
pH will drop quickly in the pit.
M
n+
+ H
2
O Mn (OH) + H
3
O
+

The electro-neutrality in the local pit solution volume has to be achieved at any time so that fast Cl-
migration in the pit will occur producing locally more aggressive HCl solutions.
Cl
+ H
3
O
+
HCl + H
2
O
The diffusion of O2 is more difficult in the occluded pit area resulting in local O2 depletion.
When an active-passive transition is present for the passive material, a decrease of the pH will result in
an increase of the critical current density (icrit); the re-passivation process is therefore even more
hindered.
The combination of all these phenomena induces an autocatalytic process for the localized attack where
the dissolution rate is accelerating during a first phase.
If the pH drops below a value of 4, it is also necessary to take into account an additional cathodic
reaction taking place only in the pit, the hydrogen reduction (H-type corrosion process). This cathodic
reaction is charge transfer controlled so that it can induce very high dissolution rate in the pits and
acidification will accelerate the pit growth rate.
2H
+
+ 2e
H
2

Setting up of a Galvanic Cell:
For a passive metal, an active passive element (micro-galvanic coupling) is furthermore created and
maintained during the pit growth phase:
Active anode (pit)
Passive cathode (intact passive layer around the pit)
Concerning the galvanic coupling conditions, the area ratio is catastrophic with a small anode surrounded by
a very large cathode. If the electrolyte conductivity is good and the passive film supports oxygen reduction,
then the pits will grow very fast!

Effect of Halides:
Halides very effectively attack passivating thin oxide layers, leading to an intense localized dissolution of
the metal surface.
Chlorides cause the most serious problems due to their presence in many environments such as
seawater and salt on roads, in food, and in the chemical industry.
Hypo-chlorides (HOCl) are difficult to handle because of their strong pitting tendencies.
Halides of non-oxidizing metals such as NaCl and CaCl
2
causes pitting but, to much lesser degree.
Cupric, Ferric and mercuric halides are extremely aggressive. They dont even require oxygen to
promote attack because cations are cathodically reduced as follows:
Cu
3+
+ 3e
Cu

Effect of Velocity on Pitting:
Pitting is usually associated with stagnant conditions such as a liquid in a tank or liquid trapped in a low pipe
system. Increase in velocity often decreases pitting attack. E.g. Stainless steel pump would give good service
handling of sea water if it were to run continuously but would start pitting if shutdown for an extended
period.

Effect of Metal Composition on Pitting:
Stainless steel alloys are most susceptible to pitting than any other group of metals & alloys. E.g. presence of
Cr, Ni, Mo, N increases pitting while Si, S, Se, C decreases pitting.

Evaluating Pitting Damage:
Pitting factor is the ratio of the depth of the deepest pit resulting from corrosion divided by the average
penetration as calculated from weight loss.
Conventional weight loss (%) methods cant be used to quantify the corrosion rate in case of pitting
because usually the associated metal loss is small and doesnt indicate the depth and penetration of pit.
Measurement of pit depths is complicated by the fact that there is a statistical variation in depth of pits
on an exposed specimen.
Average Pit depth is a poor way of estimating the damage since the deepest pit causes the fracture.
Measurement of maximum pit depth would be a more reliable way of expressing pitting corrosion.

Prevention:

No. of Pits
Pit Depth
Max. Pit Depth

Stress Corrosion Cracking (SCC)

Stress corrosion cracking (SCC) is a catastrophic cracking failure of a susceptible material in a particular
environment. This phenomenon can produce cracking at stress levels well below a materials rated tensile
strength. The crack or fracture will appear brittle, with no localized yielding, plastic deformation or
elongation. Rather than a single crack, a whole network of fine, feathery, branched cracks will form. Pitting
is frequently seen and will often serve as a stress concentrator to initiate cracking. One or more cracks will
grow from the pit, eventually leading to the failure.
SCC is the initiation and slow growth of cracks under the simultaneous influence of tensile stresses and
aggressive environment.

Stresses to consider include:
Operational (Applied)

Thermally induced (temperature gradients, differential thermal expansion and contraction)

Induced by build-up of (voluminous) corrosion products

Assembly
- Poor fit up (tolerancing problems) - Torqueing - Press and shrink fits
- Fastener interference - Joining (see below)

Residual (due to manufacturing processes)
- Joining (welding, brazing, soldering) - Casting - Machining
- Forming and shaping - Cutting and shearing
- Surface treatment (plating, mechanical cleaning, etc.)
- Heat treatment (e.g. quenching, phase changes)

Mechanisms:
SCC is the result of a combination of three factors:

1. A susceptible material,
2. Exposure to a corrosive environment, and
3. Tensile stresses above a threshold.

Cracking Morphology: [Type of crack propagation]
Intergranular: Attack at the grain boundaries under tensile stress.
Transgranular: Attack through (with in) the grains.
There is no unified mechanism for stress corrosion cracking in the literature. Various models have been
proposed which include the following:

Adsorption model: the specific species adsorb and interact with strained bonds at the crack tip which
causes in a reduction of the bond strength or in thermodynamic term, the reduction in surface energy
resulting in a brittle fracture.
Film rupture model: The protective film present at the crack tip is ruptured by continued plastic
deformation and thus exposing the metal to environment at a very small area (crack tip) setting up an
active-passive cell. The small area behaves as anode and rest of the walls of the crack behaves as
cathode. The cathode to anode area ratio is very high and a localized type of attack takes place.
Pre-existing active path model: Pre-existing path such as grain boundaries where intermetallics and
compounds are formed. Localized preferential corrosion (dissolution) at the crack tip, along a
susceptible path, with the bulk of the material remaining in a more passive state. At the crack tip,
adsorbed or species diffused in the metal weaken the metallic binding forces.
Embrittlement model: Hydrogen embrittlement is a major mechanism of SCC for steels and other alloys
such as titanium. Hydrogen atoms diffuse to the crack tip and embrittle the metal.

Mechanism Type Process Pictorial View
Hydrogen Embrittlement

Dissolved H-atoms dilate lattice &
Weaken atomic bonds.

Adsorption Induced Cleavage Adsorption of A weakens crack tip
bonds.

Surface Mobility Atoms migrate out of the crack tip.

Film Rupture Crack grows by anodic dissolution at
crack tip where film is ruptured.

Film Induced Cleavage First brittle crack initiates in brittle
film and propagates in ductile crack
tip metal.

Localized Surface Plasticity Brittle crack propagates into crack tip
metal weakened by anodic
dissolution resulting from film
rupture.


Controlling Factors in SCC Crack:
Corrosion film characteristics
(i.e., passivation) and local
anodic attack (i.e., de-
passivation) serve as
controlling factors in SCC crack
initiation and growth.
Localized corrosion can
promote SCC making exposure
geometry and specimen
design important factors.
Mechanical straining or
electrochemical inducements
such as crevices or controlled
potential are utilized to
overcome the problems and
uncertainties of SCC initiation.

HYDROGEN EMBRITTLEMENT:
[Hydrogen Induced Cracking (HIC), Stepwise Cracking (SWC) or Blister Cracking]
Hydrogen embrittlement occurs when atomic hydrogen diffuses into the metal structure and interacts
within the metal to form a brittle material. This brittle material then fails by brittle cracking due to the
internal stresses created by the entrapped hydrogen molecules.

Mechanism:
Hydrogen dissolves in all metals to a moderate extent. Being in smaller in size it fits in between the metal
atoms in the crystals of the metal. Consequently it can diffuse much more rapidly than larger atoms.
Hydrogen tends to be attracted to regions of high triaxial tensile stress where the metal structure is dilated.
Thus, it is drawn to the regions ahead of cracks or notches that are under stress. The dissolved hydrogen
then assists in the fracture of the metal, possibly by making cleavage easier or possibly by assisting in the
development of intense local plastic deformation. These effects lead to embrittlement of the metal.


Sulfide Stress Cracking (SSC):
Sulfide stress cracking (Wet H
2
S cracking) is a special case of hydrogen embrittlement that occurs when H
2
S
dissociates, in the presence of water, into hydrogen and sulfide ions.
Hydrogen absorption is clearly responsible for SCC of high-strength steels in aqueous environments, notably
in the presence of H
2
S, where the fraction of discharged hydrogen that is absorbed by the metal can
approach 100% owing to poisoning of the recombination reaction (H + H H
2
) by sulfur adsorption.

Sulfide stress cracking (SSC) has special importance in gas and oil industry, as the materials being processed
there (natural gas and crude oil) often contain considerable amount of hydrogen sulfide. SSCC is a low
temperature (temperature where water is liquid) effect of H
2
S in an aqueous environment and Sulfidation is
the term used for the high temperature (>450F) sulphur corrosion.

Chloride Stress Corrosion Cracking (CSC):
Chloride stress corrosion involves selective attack of the metal along grain boundaries. It is the most widely
encountered form of SCC.
In the formation of the steel, a chromium-rich carbide precipitates at the grain boundaries leaving these
areas low in protective chromium, and thereby, susceptible to attack. Stainless steels are covered with a
protective oxide film. The chloride ions rupture the film at weak spots setting up a galvanic cell which
produces accelerated attack at the sites, which when combined with tensile stresses produces cracking. The
minimum stress level required for chloride SCC for 300 series stainless is extremely low and most commonly
used fabrication techniques (welding, bending, rolling, etc.) will produce residual stress exceeding the
minimum value.
This form of corrosion is controlled by maintaining low chloride ion and oxygen content in the environment
and the use of low carbon steels.

Caustic Embrittlement:
Caustic embrittlement is generally encountered in boilers or steam systems where sodium or calcium scales
form on heated surfaces [Occurs in zircalloy and ferrous alloys]. The susceptibility of a welded steel structure
to SCC is a well-defined function of sodium hydroxide concentration and temperature. The cracking is
associated with the presence of sodium hydroxide. However, the metal away from the cracks is ductile. The
cracking is predominantly intercrystalline while in some cases they may be transcrystalline.

The concentrated basic conditions are caused by boiling (basic solution concentrates in crevices). The
caustic material plates out of solution. When it is remoistened it creates a region with a highly caustic
environment. Strict pH control is the only solution.
Nickel cladding has been used successfully to prevent caustic embrittlement.
Corrosion Fatigue Cracking [Low Amplitude Cyclic (or Ripple) Loading]
It is a Special case of Stress Corrosion Cracking (SCC)
Applied stress is not constant (not static) but experiences cyclic
variations aggravated SCC attack
Results in Transgranular crack propagation
The cyclic loading can induce constant de-passivation of the
material.
At the induced micro notches, additional gliding and accelerated
corrosion is induced.
The cracks are generally transgranular in nature, with little
tendency for branching. However, a few small secondary cracks
may appear in the vicinity of the main crack.

Factors Affecting CF
The corrosion fatigue crack initiation and growth of a metal/alloy, depends on the following factors:
Amplitude of cyclic load or stress intensity factor
Ratio of stress intensity factor
Frequency of fluctuating load
Corrosiveness of environment,
Geometry of crack tip or stress concentration.

Corrosion Fatigue (CF) Control
All most all the techniques used in SCC control can be used for fatigue crack initiation and growth. There is
an old rule of thumb about fatigue tests which says that 10% of damage occurs in 90% of time and 90% of
the damage in the last 10% of the time. This means that more importance should be given in controlling
initiation than the propagation of corrosion fatigue. The following consideration should be taken into
account to reduce the possibilities of fatigue failures:
1. Materials choice: Strong alloys exhibit poor resistance to C.F.
2. Design aspects: Stress concentrations such as flaws, grooves, pits notch etc. are potent sites for CF
initiation
3. Cold working: Shot peerning or grit blasting provide compressional stresses and control C.F.
4. Nitriding: Certain special steels containing elements like Cr and Mo possess affinity towards nitrogen.
When they are heated in ammonia, the surface is converted into nitrides and the product is voluminous
than the base alloy surface. This provides compressive stress and raises fatigue strength of the material.

Intergranular Corrosion
It is a localized attack at and adjacent to grain boundaries with relatively little or no corrosion of the grains.
Penetration of the corroding medium follows grain boundaries and destroys the bond between grains. This
action can seriously affect the strength of an alloy. When severe, this corrosion causes a loss of strength and
ductility which is out of proportion to the amount of metal actually destroyed by corrosion. It may
eventually result in intergranular - stress corrosion - cracking (IGSCC) along the metal's grain boundaries.

Mechanism:
Intergranular corrosion occurs when grain boundaries and matrix (inner part of grains) have different
electrochemical behavior.
It is either due to the presence of impurities in the boundaries, or due to local enrichment or depletion
of one or more alloying elements.
This situation can happen in corrosion-resistant alloys, when the grain boundaries are depleted (grain
boundary depletion) of the corrosion-inhibiting elements such as chromium by some mechanism.
For a given materials, grain boundaries or areas near grain boundaries are less noble (less corrosion
resistant) compared to the inner part of grains because of a differing composition and formation of
carbides. As a result, the corrosive attack is localized at these less noble areas.

Damage:
The observed damages are not only the attack and dissolution of grain boundary areas but also result in
severe falling out of entire grains inducing macroscopic damages. The degradation processes are:
1. Electrochemical material removal evolving at relatively small rate with local increased corrosion at
grain boundaries.
2. Removal of undermined grains is the most dangerous aspect regarding fast damages.

Weld Decay [Sensitization]
It is the most well-known form of intergranular corrosion caused by inadequate heat-treatment or welding
procedures which result in the precipitation of intergranular compounds (e.g., austenitic stainless steels).

Sensitization refers to the precipitation of carbides at grain boundaries in a stainless steel or alloy, causing
the steel or alloy to be susceptible to intergranular corrosion or stress corrosion cracking (Weld Decay).

In nickel alloys and austenitic stainless steels, where chromium is added for corrosion resistance, the
mechanism involved is precipitation of chromium carbide at the grain boundaries when cooling from
welding temperatures, resulting in the formation of chromium-depleted zones adjacent to the grain
boundaries. These zones are highly subject to corrosion attack and also act as local galvanic couples, causing
galvanic corrosion.

The combination of chromium and carbon in the stainless steel provide the necessary ingredients to form
chromium carbide; of atomic composition Cr
23
C
6
. The other necessary ingredient is thermal treatment. The
carbide is stable between the ranges of 950 and 1450
o
F, but requires some time to grow due to the
nucleation and growth required for second phases. The nucleation site of the chromium carbide is the
austenite grain boundaries. The second phase therefore grows on the grain boundaries. The distribution of
the chromium in the steel then becomes important. Chromium can only diffuse by substitutional diffusion in
the matrix which is slow or along grain boundaries which is faster but limits the location of the chromium for
the carbides to regions near the grain boundaries. The carbon diffuses by interstitial diffusion, which is much
faster and easier than substitutional or again along the boundaries.

1. Vacancy controlled also Substitutional a vacancy or missing atom on its lattice site is needed for the
atom to jump into. As one atom jumps into a vacancy it leaves a vacancy.
2. Interstitial diffusion involves small atoms diffusing in a matrix of large atoms. For metallic atoms, the H,
C, N, O, B atoms are the ones small enough to fit in the spaces between the large metallic atoms.
3. Grain boundary diffusion uses defect structure of grain boundary so much faster than vacancy or
substitutional diffusion rates

Knifeline Attack (KLA)
KLA is a specific intergranular corrosion phenomenon of stabilized austenitic stainless steels. The attacked
areas have been found to contain precipitated chromium carbides; the stabilizing elements niobium
(columbium) or titanium failed "to do their job" in tying up the carbon in the alloy. KLA is similar to weld
decay in that they both result from intergranular corrosion and both are associated with welding. The two
major differences are that:

1. KLA occurs in presumably stabilized steels;
2. KLA occurs in a very narrow band in the parent metal immediately adjacent to the weld, whereas weld
decay develops at a greater distance from the weld.

Mechanism:
The mechanism for KLA is based on the high-temperature solubility of niobium (columbium) carbides in
stainless steel. Niobium and niobium carbides dissolve in the metal when it is heated to a very high
temperature and they remain in solution when cooled rapidly from this temperature. The niobium stays in
solution when the metal is subsequently heated into the chromium carbide precipitation range, niobium
carbide does not form, and the metal behaves (sensitizes) as though it were austenitic steel without niobium
stabilizer.

Remedy:
The remedy for avoiding KLA is to heat the completed structure (after welding) to around 1065C. Chromium
carbide dissolves and niobium carbide forms - which is the condition desired for resistance to KLA and weld
decay. The rate of cooling after the 1065C treatment is not important.

Exfoliation
A unique form of intergranular corrosion is observed in aluminum alloys. Intergranular attack proceeds
laterally through plate and sheet in planes parallel to the surface (direction of cold work). The corrosion
products force the metal away from the body of the materials and give rise to a layered or leaf-like
appearance ("exfoliation") in un-recrystallized alloys.
Example: In Al-Mg alloys, the magnesium tends to segregate or preferentially collect at the grain
boundaries. As magnesium is a very active element, then the grain boundaries become active and dissolve.
The grain surface area that is not being attacked becomes cathodic with a resulting large cathode to small
anode ratio which increases the corrosion rate for the grain boundary regions.

Measures to avoid intergranular corrosion:

From a materials perspective:
Heat treatment at higher temperature (1100C) followed by Solution quenching or Quench annealing
(Rapid cooling from the solution welding temperature).
Decrease of the carbon content of steel (not always possible because it decreases the machinability of
the steel). However, low carbon content makes carbide formation impossible. Lowering the carbon to
below 0.03% is referred to as Extra Low Carbon (ELC).
Use Stabilized steels by the addition of Titanium, Niobium, and Tantalum known as Stabilizers (have
higher affinity for carbide formation than Chromium). Alloying with titanium (Ti = 5 * C concentration)
leads to formation of (non-interfering) titanium carbides, and the chromium content remains unchanged
through the whole grain boundary.

From a design and construction perspective:
Controlling the temperature flow during welding, Heat affected zones away from the weld areas are often
the location of IGC failure. This problem is by far the most acute as it is not easy to avoid the intermediate
temperature domain during welding. It is currently the major still remaining cause of IGC failure for steel.

Selective Leaching
(De-alloying or De-Metalification or Parting or Selective Corrosion)

Selective leaching is the preferential dissolution of one element from an alloy.
It is also known as de-alloying as it results in the breaking of an alloy.
It may occur uniformly or locally, often without a measurable change in dimension.
The less noble metal is removed from the alloy by microscopic-scale galvanic corrosion mechanism.
The most susceptible alloys are the ones containing metals with high distance between each other in the
galvanic series, e.g. copper and zinc in brass.
The elements most typically undergoing selective removal are Zn, Al, Fe, Co, Cr etc.

What causes de-alloying? Different metals and alloys have different electrochemical potentials (or
corrosion potentials) in the same electrolyte. Alloys contain a number of different alloying elements that
exhibit different corrosion potentials. The potential difference between the alloying elements is the driving
force for the preferential attack on the more "active" element in the alloy.

1. Dezincification
It is the selective removal of zinc from zinc-containing alloys (Brass). The zinc is separated by dissolution
from copper & can be observed by naked eyes because alloy changes color from yellow to red.

Mechanism:
Dissolution of Brass Zn ions stay in solution Cu plates back on.

Zn is quite reactive, whereas Cu is nobler. Zn can corrode slowly in pure water by cathodic ion reduction into
H
2
and hydroxide ions. Therefore, de-zincification can proceed even in the absence of O
2
. The analysis shows
90-95% Cu with some present as copper oxide. The amount of CuO is related to the oxygen content in the
environment.

Types of Dezincification Mechanisms:
1. Uniform (Layer) Type 2. Localized (Plug) Type
It seems to favor the high brasses (i.e. High Zn
content) and acidic environments.
It seems to occur in the low brasses (low Zn
content) and neutral, alkaline or slightly acidic
environment (high in salt).
Uniform-layer dezincification leaches zinc from a
broad area of the surface.
Plug-type dezincification is localized within
surrounding surfaces mostly unaffected by
corrosion.
This type of dezincification uniformly reduces the
wall thickness of the valve or fitting.
This type of dezincification penetrates deeply into
the sidewalls of valves and fittings.
A complex set of conditions must be present for
dezincification to occur, and the occurrence is often
related to region of the country. E.g. Slow H
2
O flow
or stagnant H
2
O especially when O
2
& CO
2
is high in
H
2
O makes a material more susceptible to uniform
corrosion. Slightly acidic water that is low in salt & at
room temperature also facilitates selective leaching.
Common failures associated with plug-type
attack include penetration through the sidewalls
that causes water seepage or loss of mechanical
strength in threaded sections to the point of
fracture.

2. Graphitization (Graphitic corrosion)
It is the deterioration of gray cast iron in which the metallic constituents are selectively leached or
converted to corrosion products leaving the graphite intact.
Graphitic corrosion should not be confused with another term graphitization, which is used to describe
the formation of graphite in iron or steel, usually from decomposition of iron carbide at elevated
temperatures.

Mechanism:
The gray cast iron show the effect of selective leaching out of iron in mild corrosive environments.
During Graphitic Corrosion, the porous graphite network that makes up to 4-5% of the total mass of the
alloy is penetrated by the insoluble corrosion products. As a result cast Iron retains its shape and
appearance but this weakens its internal structure.
The corrosion process is a Galvanic Action between C and Fe with Carbon acting as the least noble so
anode while Iron acting as the most noble so act as a cathode.
The surface layer of the iron becomes like graphite and it can be easily cut with a knife. Iron is dissolved
and leaves behind an interlocking nobler graphite network and a porous mass of voids and complex iron
oxides. This graphitized cast iron loses its strength and other metallic properties, but unchanged in the
shape.

How to prevent de-alloying? De-alloying, selective leaching and graphitic corrosion can be prevented
through the following methods:
Select metals/alloys that are more resistant to de-alloying. For example, inhibited brass (Red brass
15% Zn) is more resistant to dezincification than alpha brass; ductile iron is more resistant to graphitic
corrosion than gray cast iron.
Control the environment to minimize the selective leaching.
Use sacrificial anode cathodic protection or impressed current cathodic protection
Decarburization: It is the selective loss of carbon from the surface layer of a carbon-containing alloy
due to reaction with one or more chemical substances in a medium that contacts the surface.

Denickelification: It is the selective leaching of nickel from Ni based alloys. E.g. Cu-Ni alloys.

Decobaltization: It is the selective leaching of cobalt from Co based alloys. E.g. Stellite
EROSION CORROSION
It is a degradation of material surface due to mechanical action, often by impinging liquid, abrasion by
slurry, particles suspended in fast flowing liquid or gas, bubbles or droplets, cavitation, etc.
Erosion corrosion is acceleration in the rate of corrosion attack in metal due to the relative motion of a
corrosive fluid and a metal surface. The increased turbulence caused by pitting on the internal surfaces
of a tube can result in rapidly increasing erosion rates and eventually a leak.
Erosion corrosion occurs due to the velocity of the fluids around the metal components. The removal of
the ionic species promotes the rapid dissolution of the anode material. In addition the removal of
protective films by the flowing solution can decrease the protection they offer.

Erosion-corrosion is most prevalent in soft alloys (i.e. copper, aluminum and lead alloys). Alloys which form a
surface film in a corrosive environment commonly show a limiting velocity above which corrosion rapidly
accelerates. With the exception of cavitation, flow induced corrosion problems are generally termed
erosion-corrosion, encompassing flow enhanced dissolution and impingement attack. The fluid can be
aqueous or gaseous, single or multiphase. There are several mechanisms described by the conjoint action of
flow and corrosion that result in flow-influenced corrosion:

Mass transport-control: Mass transport-controlled corrosion implies that the rate of corrosion is
dependent on the convective mass transfer processes at the metal/fluid interface. When steel is
exposed to oxygenated water, the initial corrosion rate will be closely related to the convective flux of
dissolved oxygen towards the surface, and later by the oxygen diffusion through the iron oxide layer.
Corrosion by mass transport will often be streamlined and smooth.

Phase transport-control: Phase transport-controlled corrosion suggests that the wetting of the metal
surface by a corrosive phase is flow dependent. This may occur because one liquid phase separates from
another or because a second phase forms from a liquid. An example of the second mechanism is the
formation of discrete bubbles or a vapor phase from boiler water in horizontal or inclined tubes in high
heat-flux areas under low flow conditions. The corroded sites will frequently display rough, irregular
surfaces and be coated with or contain thick, porous corrosion deposits.

Erosion-corrosion may be enhanced by particles (solids or gas bubbles) and impacted by multi-phase flows.
The morphology of surfaces affected by erosion-corrosion may be in the form of shallow pits or horseshoes
or other local phenomena related to the flow direction.

Effect of Velocity [Flow Induced Mechanical Removal & Shearing]
Velocity strongly influences mechanics of corrosion. It exhibits mechanical wear effect at higher values
and particularly when solution contains solids in suspension. At first effect of Velocity may be negligible
but when critical velocity is reached then the attack increases at a rapid rate.
Erosion-corrosion is associated with a flow-induced mechanical removal of the protective surface film
that results in a subsequent corrosion rate increase via either electrochemical or chemical processes.
It is often accepted that a critical fluid velocity must be exceeded for a given material. The increase in
fluid velocity usually increases the erosion corrosion rate.
The mechanical damage by the impacting fluid imposes disruptive shear stresses or pressure variations
on the material surface and/or the protective surface film.

Example: Velocity may increase attack on steel by increasing supply of O2, CO2, H2S in contact with metal
surface or It may decrease diffusion (i.e. transfer) of ions by reducing thickness of stagnant film at the
surface. If the passive film is removed from stainless steel then it will corrode uniformly. Other cases exist
for example stainless steel in fuming nitric where the erosion corrosion rate decreases due to removal of
nitrous acid at increased velocity. When this component remains at low or static conditions it promotes
attack of the steel.

Jet of Fluid Impacts Surface When Bubble Contacts
Turbulent Flow [Inlet Corrosion]
Turbulent flow leads to a phenomenon called inlet corrosion. It results in greater agitation of liquid at metal
surface than in case of laminar flow. The most frequently occurring example of this type of failure occurs at
inlet ends of tubing in condenser and similarly in Shell end tube heat exchanger. The extra turbulence at an
inlet or change in direction will produce turbulent flow. The material loss is greatest nearest the inlet as the
flow and agitation is highest leading to enhanced erosive reaction. Impeller and propeller are typical
components operating under turbulent conditions.

Impingement [Localized Erosion Corrosion]
Impingement attack is related to the cavitation damage, and has been defined as localized erosion-
corrosion caused by turbulence or impinging flow.
Entrained air bubbles tend to accelerate this action, as do suspended solids.
This type of corrosion occurs in pumps, valves, orifices, on `heat-exchanger tubes, and at elbows and
tees in pipelines.
Impingement corrosion usually produces a pattern of localized attack with directional features. The pits
or grooves tend to be undercut on the side away from the source of flow, in the same way that a sandy
river bank at a bend in the river is undercut by the oncoming water.
When a liquid is flowing over a surface (e.g. in a pipe), there is usually a critical velocity below which
impingement does not occur and above which it increases rapidly.
In practice, impingement and cavitation may occur together, and the resulting damage can be the result
of both. Impingement may damage a protective oxide film and cause corrosion, or it may mechanically
wear away the surface film to produce a deep groove.

Impact Erosion Corrosion [Micro Machining Operation]
When particulate matter is added to the flow an additional surface damage mechanism is additive to the
erosion process. The particles act as small machine tools and remove the surface material in a micro-
machining operation.
The angle of impact that is most deleterious is 30 to 45
o
for metals and 90
o
for ceramics. Elbows and
bends are particularly prone to this type of damage.

Cavitation
Cavitation occurs when a fluid's operational pressure drops below its vapor pressure causing gas
pockets and bubbles to form and collapse.
Cavitation erosion is due to either the bubbles in a fluid flow or droplets in an air stream impacting a
surface at high velocity.
In this case the bubble collapses on to the surface of the material and causes a small portion of material
to be removed from the surface. The corrosive environment will attack the highly anodic material
exposed by the cavitation damage.
Cavitation sometimes is considered a special case of erosion-corrosion and is caused by the formation
and collapse of vapor bubbles in a liquid near a metal surface. Cavitation removes protective surface
scales by the implosion of gas bubbles in a fluid.
The subsequent corrosion attack is the result of hydro-mechanical effects from liquids in regions of low
pressure where flow velocity changes, disruptions, or alterations in flow direction have occurred.
Cavitation damage often appears as a collection of closely spaced, sharp-edged pits or craters on the
surface.

Micro-machined crater during impact erosion corrosion
Machined Lip
Effect of Environment:
pH: Variation in pH can result in abnormalities in behavior. For example, one pH may induce passivation and
another may not. This is the case for iron, which is very resistant to erosion at pH of 6 and 10 but poor at
other pH conditions as the films former are non-passive.

Oxygen: If oxygen promotes a stable film formation then it will be advantageous. One case is titanium in
which increasing oxygen promotes a stable film formation. For brass and copper, brass formed a gray CuO
film while copper formed a CuCl
2
film which was not stable under identical environmental conditions.

Prevention

1. Choose erosion resistant metals:
Choose materials that are strengthened by solid solution rather than by second phase strengthening. These
materials generally do better in erosion. In addition the removal of second phases often decreases the
corrosion rate of the material as no galvanic contacts are available.

2. Design:
Try not to provide enhanced erosion conditions. For example,
Try to avoid sharp elbows when a particulate flow is present.
Thicken sections so more erosion is possible before refitting is necessary.
Make component that is going to suffer erosion corrosion easily replaceable or repairable.
Design a portion that can be employed while the other pipe is being repaired or redundant design.
It is generally desirable to reduce the fluid velocity and promote laminar flow; increased pipe diameters
are useful in this context.
Rough surfaces are generally undesirable.
Designs creating turbulence, flow restrictions and obstructions are undesirable.
Abrupt changes in flow direction should be avoided.
Tank inlet pipes should be directed away from the tank walls, towards the center.
Welded and flanged pipe sections should always be carefully aligned.
Impingement plates of baffles designed to bear the brunt of the damage should be easily replaceable.

3. Change environment:
Slow flow by wider diameters. Use filters to remove particles. Change impellor speed to reduce cavitation.

4. Electrochemical Protection:
Use impressed currents to reduce anodic effects on erosion. De-aeration and corrosion inhibitors are
additional measures that can be taken. Cathodic protection and the application of protective coatings may
also reduce the rate of attack.

Offshore Well Systems:
In offshore well systems, the process industry in which components come into contact with sand-bearing
liquids, this is an important problem. Materials selection plays an important role in minimizing erosion
corrosion damage. Caution is in order when predicting erosion corrosion behavior on the basis of hardness.
High hardness in a material does not necessarily guarantee a high degree of resistance to erosion corrosion.
Design features are also particularly important.

Corrosion Inhibitors
A corrosion inhibitor is a substance that when added in small conc. to an environment decreases the
corrosion rate. It is a material that attaches or coats the metal surface, providing a protective barrier film,
which in turn stops the corrosion reaction from developing.

Choosing a Corrosion Inhibitor
When choosing the corrosion inhibitor for your application several things need to be considered.
Materials to be protected
Protection effectiveness timeframe (1week, 1 month, 1 year, etc.).
Method of application (dip, spray, brush, etc.)
Type of protection required (in process, storage or shipping)
Part handling and fingerprint suppression
Type and thickness of coating residue desired
Storage, packaging and/or shipping conditions (temperature, humidity & seasonal conditions)
Removal methods (if required)
Interaction with subsequent processes, if not removed
Environment, health and safety requirements
Type of product (Oil/Solvent or Water-based) desired

1. Scavengers (Environmental Conditioners):
Inhibitors that decrease corrosivity of the medium by removing the aggressive substances (corrosive
reagents) from the solution are called Scavengers. In near-neutral and alkaline solutions, oxygen reduction is
a common cathodic reaction. In such situations, corrosion can be controlled by decreasing the oxygen
content using scavengers (e.g., hydrazine, Sodium sulfite etc.). For example, hydrazine removes oxygen by
the following reaction:

2Na
2
SO
3
+ O
2
2Na
2
SO
4

2. Interface Inhibitors
Interface inhibitors control corrosion by forming a film at the metal/environment interface. Interface
inhibitors can be classified into liquid- and vapor-phase inhibitors.

2.1 Liquid-Phase Inhibitors:
Liquid-phase inhibitors are classified as anodic, cathodic, or mixed inhibitors, depending on whether they
inhibit the anodic, cathodic, or both electrochemical reactions.
2.1.1 Anodic inhibitors:
Anodic inhibitors are usually used in near-neutral solutions where sparingly soluble corrosion products, such
as oxides, hydroxides, or salts, are formed. They form, or facilitate the formation of, passivating films that
inhibit the anodic metal dissolution reaction. Anodic inhibitors are often called passivating inhibitors. When
the concentration of an anodic inhibitor is not sufficient, corrosion may be accelerated, rather than
inhibited. The critical concentration above which inhibitors are effective depends on the nature and
concentration of the aggressive ions.

2.1.2 Cathodic inhibitors:
Cathodic inhibitors control corrosion by either decreasing the reduction rate (cathodic poisons) or by
precipitating selectively on the cathodic areas (cathodic precipitators). Cathodic poisons, such as sulfides
and selenides, are adsorbed on the metal surface; whereas compounds of arsenic, bismuth, and antimony
are reduced at the cathode and form a metallic layer. In near-neutral and alkaline solutions, inorganic
anions, such as phosphates, silicates, and borates, form protective films that decrease the cathodic reaction
rate by limiting the diffusion of oxygen to the metal surface.

Hydrogen Poisoning: Cathodic inhibitors can cause hydrogen blisters & hydrogen embrittlement due to the
absorption of hydrogen into steel. This problem may occur in acid solutions, where the reduction reaction is
hydrogen evolution, and when the inhibitor poisons, or minimizes, the recombination of hydrogen atoms to
gaseous hydrogen molecules. In this situation, the hydrogen, instead of leaving the surface as hydrogen gas,
diffuses into steel causing hydrogen damage, such as hydrogen-induced cracking (HIC), hydrogen
embrittlement or sulfide stress cracking. Cathodic precipitators increase the alkalinity at cathodic sites and
precipitate insoluble compounds on the metal surface. The most widely used cathodic precipitators are the
carbonates of calcium and magnesium.

2.1.3 Adsorption Type Inhibitors: (Mixed inhibitors)
About 80% of inhibitors are organic compounds that cannot be designated specifically as anodic or cathodic
and are known as mixed inhibitors. The effectiveness of organic inhibitors is related to the extent to which
they adsorb and cover the metal surface. Adsorption depends on the structure of the inhibitor, the surface
charge of the metal, and the type of electrolyte.

Mixed inhibitors protect the metal in three possible ways: physical adsorption, chemisorption and film
formation.

Physical (or electrostatic) adsorption is a result of electrostatic attraction between the inhibitor and the
metal surface. When the metal surface is positively charged, adsorption of negatively charged (anionic)
inhibitors is facilitated. Anions, such as halide ions, in solution adsorb on the positively charged metal
surface, and organic cations subsequently adsorb on the dipole. Corrosion of iron in sulfuric acid
containing chloride ions is inhibited by quaternary ammonium cations through this synergistic effect.
Increase in temperature generally facilitates desorption of physically adsorbed inhibitor molecules. The
most effective inhibitors are those that chemically adsorb (chemisorb), a process that involves charge
sharing or charge transfer between the inhibitor molecules and the metal surface. Chemisorption takes
place more slowly than physical adsorption. As temperature increases, adsorption and inhibition also
increase. Chemisorption is specific and is not completely reversible.
Adsorbed inhibitor molecules may undergo surface reactions, producing polymeric films. Corrosion
protection increases markedly as the films grow from nearly two-dimensional adsorbed layers to three-
dimension films up to several hundred angstroms thick. Inhibition is effective only when the films are
adherent, are not soluble, and prevent access of the solution to the metal. Protective films may be non-
conducting (sometimes called ohmic inhibitors because they increase the resistance of the circuit,
thereby inhibiting the corrosion process) or conducting (self-healing films).

2.2 Volatile Corrosion Inhibitors (VCI) / Vapor Phase Inhibitor (VPI)
They are compounds transported in a closed environment to the site of corrosion by volatilization from
a source. E.g. Oil Tank, shipment etc.
It is desirable, for an efficient VCI, to provide inhibition rapidly while lasting for long periods. Both
qualities depend on the volatility of these compounds; fast action wanting high volatility while enduring
protection requires low volatility.

Mechanism:
The process of vapor-phase inhibition involves two steps: transport of inhibitor to the metal surface (by
sublimation or condensation) and interaction of inhibitor ions on the metal surface.
A VPI may vaporize either in the molecular form or it may first dissociate and then vaporize. Amines
vaporize in the undissociated molecular form.
Subsequent reaction with water, present as moisture at the surface, dissociates the inhibitor.
When these inhibitors come in contact with the metal surface, the vapor of these salts condenses and is
hydrolyzed by any moisture to liberate protective ions.

Limitation of Inhibitors:
Inhibitors are used to great advantage to suppress corrosion of metals in many environments. However,
there are certain limitations that needed to be carefully handled while inhibiting corrosion.
Inhibitors cant be added to every environment as it may possibly contaminate that environment that
may even promote further corrosion.
Many Inhibitors are toxic in nature and their applications are limited to the specific mediums only. They
cannot be used directly or indirectly in the preparation of food or other products that will come in
contact with humans. Arsenic salts having strong inhibiting effect in acids have limited applications for
this reason.
Inhibitors are primarily used in closed system, when the corrosive environment is either contained for
long periods or recirculated.
Inhibitors are not usually practical in once through system.
Inhibitors generally use their effectiveness rapidly as concentration and temperature of environment
increases.

Corrosion Coatings
Construction metals are expected to have excellent mechanical properties and machinability at a low price,
while at the same time they should be corrosion resistant. These properties can seldom be met in one and
the same material. Separating the base metal with good mechanical properties from the corrosive
surrounding by applying a surface layer can solve this problem. These layers can be:
1. Metallic layers
2. Nonmetallic inorganic layers such as conversion layers, anodized layers, some ceramic chemical vapor
deposition (CVD) and physical vapor deposition (PVD) layers, and enamel layers
3. Organic layers such as paints, lacquers, and polymer sheets

Pre-Requisites for Effective Coating Application [Ensuring Good Protective Action of Applied Layers]
1. First of all, in order to achieve good protective action of the applied layers, it is important to obtain
excellent adhesion of the coating to the base metal. For this reason the substrate surface must be
cleaned very well before further surface treatment and application of the surface layer.
Cleaning is often performed in two stages. First, the organic impurities such as oil, grease, and paint are
removed from the surface. Then solid inorganic material such as rust, mill scales and other corrosion
products can be removed.

The organic impurities can be removed in various ways:
With organic solvents With strongly alkaline solution
With emulsion baths By steam cleaning

The solid inorganic material can be removed by:
Mechanical treatment including brushing, grinding, polishing, and sandblasting and shot peening
with various kinds of shot, such as metallic particles, corundum, and glass beads
Heat treatment with flames or induction heating followed by fast cooling to obtain scaling
Chemical picking with strong acids. Pickling in acid will probably be used less intensively in the
coming years because of environmental problems. In many cases, optimized mechanical treatment
(e.g., micro-peening, an optimized form of shot peening with glass beads) will then be the
substitute.)

2. Primer Coatings should be applied after cleaning. A primer or undercoat is a preparatory coating put on
materials before painting. Priming ensures better adhesion of paint to the surface, increases paint
durability, and provides additional protection for the material being painted.

3. Coating combination must have high electrical resistance to the environment.

4. Foreign metal, dust and moisture reduce the effectiveness of the coating.

5. Application tools must be selected carefully and must be cost effective and ensure good functionality.

6. No matter how good the metal is, if its not handled properly then cracks may form and may get damage
by mismanaging, mishandling e.g. backfilling in underground pipelines causes scratching.

Organic Coatings
The use of organic coatings for the protection of metals against corrosion is widespread in building,
construction, food packaging, automotive, and marine applications. Organic coatings may protect metal
structures against a specific otherwise corrosive environment in a relatively economical way.

Basic Constituents of Organic Coatings: Binder, Pigments, Fillers, Additives & Solvents.


1. Wood Stain:
Stain is composed of three primary ingredients same as the paint (pigment, solvent, and binder).
Wood stain is designed to add color to the substrate of wood and other materials.
Colored or 'stained' finishes do not penetrate the pores of the wood to any significant degree and will
disappear when the finish itself deteriorates or is removed intentionally.
Pigments & dyes are largely used as colorants. The difference b/w the two is in the size of the particles.
Dyes are microscopic that dissolve in the vehicle & pigments being larger are suspended in the vehicle.
Dyes can thus color very fine grained wood which pigments cannot. Pigments contain a binder to help
attach them to the wood.

2. Varnishes:
Varnish is a transparent, hard, protective film primarily used in wood finishing & also for other materials
Varnish is traditionally a combination of a drying oil, a resin, and a thinner or solvent.
Varnish finishes are usually glossy. It has no added pigment, as opposed to paints or wood stains.
Varnishes are also applied over wood stains as a final step to achieve a film for gloss and protection.

3. Lacquer:
Lacquer refers to quick-drying, solvent-based varnishes or paints. Lacquer is not dissolved in alcohol it is
dissolved in a thinner, which is a highly flammable solvent typically containing toluene. Lacquer is typically
sprayed on, within a spray booth that evacuates overspray and minimizes the risk of combustion.

4. Enamel:
Enamel is a paint that air dries to a hard, usually glossy, finish, used for coating surfaces that are outdoors or
otherwise subject to hard wear or variations in temperature. Enamel paint is also used on wood to make it
resistant to the elements via the waterproofing and root-proofing properties of enamel. Generally, treated
surfaces last much longer and are much more resistant to wear than untreated surfaces.

5. Mastics:
It is a term used for a mixture of coating which is formed by combining sand or any other inert material with
insulating compound such as asphalt. They are applied by hot coating method and are normally thicker than
other coatings. Protective or Di-electric wrappers are not needed under normal pipeline conditions because
of their thickness and hardness.

6. Greases:
Inhibited greases are used as protective coatings particularly in distributed pipelines. They are particularly
applied by smearing or gloved hands. They are used as a sole protection and are more commonly used as a
wrapper having di-electric membrane to give mechanical & electrical strength to the system.

7. Waxes:
They are similar in performance to asphalt & coal tar enamels. They are easily applied in thinner coats than
the enamels & are used with wrappers for mechanical strength & improvement of electrical strength of coat

8. Tapes:
Tape materials have been increasingly used in pipeline coatings. The advantage of Tape coating system is
that field application requires substantially less equipment and smaller crew than for example systems
involving hot apply coating material. This means significant savings can be made on contact installation costs
on pipeline projects.

9. Cold Applied Liquid Coatings:
They are usually applied to protect pipeline corrosion. They set on the surface and solidify either by
evaporation or chemical reaction. Wrappers are reinforced to give proper prevention and multiple layers
can be coated.
Coating Application Techniques
1. Electrodeposition: (Electroplating)
Its a process using electrical current to reduce cations of a desired material from a solution and coat
that material as a thin film onto a conductive substrate surface.
Electrodeposition is the process of coating a thin layer of one metal on top of a different metal to
modify its surface properties.
E.D. is a surface coating method. It is applied to achieve the desired electrical and corrosion resistance,
to reduce wear & friction, improve heat tolerance and for decoration purposes.

The process is as follows:
Migration: The hydrated metal ions in the solution migrate
towards the cathode under the influence of impressed
current as well as by diffusion and convection.
Electron transfer: At the cathode surface, a hydrated metal
ion enters the diffused double layer where the water
molecules of the hydrated ion are aligned. Then the metal
ion enters the Helmholtz double layer where it is deprived
of its hydrate envelope.
The dehydrated ion is neutralized and adsorbed on the
cathode surface.
The adsorbed atom then migrates or diffuses to the growth
point on the cathode surface.
Thickness of the electroplated layer on the substrate is determined by the time duration of the plating.
In other words, the longer the time the object remains in the operating plating bath, the thicker the
resulting electroplated layer will be. Typically, layer thicknesses may vary from 0.1 to 30 microns.

2. Electrostatic Spraying:
Electrostatic Spray is an application process in which an electric charge is applied to the coating as it leaves
the gun, and the opposite charge is applied to the object to be coated. Spray particles are attracted to the
object, reducing over spray and providing uniform coverage.
The first step of the process involves mixing formulated paint with a chemical catalyst to produce a positive
charge. The metal object that needs to be painted will then be grounded through attached wiring. It
generally proves to be more durable than other liquid paints. In addition, it is an eco-friendly process since it
does not use any solvents that can evaporate or contaminate drainage water. However, electrostatic
painting can produce unpleasant odors and so it is recommended that painting is done outdoors.

3. Flame Spraying (Metalizing)

Flame Spraying is a thermal spray coating process that produces high quality surface coatings using heat to
melt a spray coating material which is propelled onto a substrate.
The process relies on the chemical reaction between oxygen and a fuel of combustion to produce a heat
source. This heat source creates a gas stream with a temperature in excess of 3,000C with correctly
balanced conditions between oxygen and acetylene. The feed stock material (metal) to be sprayed is fed
into the flame in the form of a powder to melt and the thermal expansion of the combustion is then used to
atomize and accelerate the particles onto the substrate.
The coatings are porous and are usually not protective under severe wet corrosive environments.

4. Vacuum Metalizing Process (Vapor Deposition)
It is the most common PVD (Physical Vapor Deposition) process used to apply metal alloys under
vacuum.
Vacuum Metalizing is the process of evaporating metals (most commonly aluminum) inside a vacuum
chamber which then bonds to the desired substrate to achieve a uniform metalized layer.
Vacuum metallizing involves heating the coating metal to its boiling point in a vacuum chamber, then
letting condensation deposit the metal on the substrate's surface.
Resistance heating, electron beam, or plasma heating is used to vaporize the coating metal.
Vacuum metallizing was used to deposit aluminum on the large glass mirrors of reflecting telescopes.

5. Hot Dip Galvanizing (HDG):
It is the process of coating iron, steel or aluminium with a layer of zinc (sometimes Sn, Pb) by immersing
the metal in a bath of molten zinc at a temperature of around 860 F (460 C).
When exposed to the atmosphere, the pure zinc (Zn) reacts with oxygen (O
2
) to form zinc oxide (ZnO),
which further reacts with carbon dioxide (CO
2
) to form zinc carbonate (ZnCO
3
), a usually dull grey, fairly
strong material that stops further corrosion in many circumstances, protecting the steel below from the
elements.
Galvanized steel is widely used in applications where corrosion resistance is needed without the cost of
stainless steel, and can be identified by the crystallization patterning on the surface (often called a
"spangle").
The process of hot-dip galvanizing results in a metallurgical bond between zinc and steel with a series of
distinct iron-zinc alloys.
Galvanizing protects steel by acting as a barrier between steel and the atmosphere. However, zinc is a
more electronegative metal in comparison to steel; this is a unique characteristic for galvanizing which
means that when a galvanized coating is damaged and steel is exposed to the atmosphere, zinc can
continue to protect steel through galvanic corrosion.

6. Cladding:
Cladding is the bonding together of dissimilar metals. It is different from fusion welding or gluing as a
method to fasten the metals together. Cladding is often achieved by extruding two metals through a die as
well as pressing or rolling sheets together under high pressure.
E.g. Nickel and steel sheets are hot rolled together to produce a composite sheet of 1/8
th
inch in Ni and 1 in
of steel.

Coating Damages/Defects
Skips are usually made by coating surfaces e.g. uneven coatings.
Cracks from excessive mechanical or thermal stresses.
Scratches from tools used during subsequent handling of the coated pipes.
Penetration by rocks, stones or debris in the backfilling surrounding the pipeline.
Penetration by growing roots.
Action of chemicals in soil surrounding the pipelines (such as leaks from a corroded pipeline)
Action of bacteria present in the soil surrounding the pipeline.
Damage from subsequent construction and other facilities causing damage or removal of coatings.

Corrosion in Petroleum Industry

Corrosion in the hydrocarbon industries may be divided into two types, "wet corrosion" and "dry corrosion."
At low temperature (i.e., below the boiling point or dew point of water), material corrodes due to the
presence of an aqueous phase (wet corrosion). At higher temperature (above the boiling point of water),
corrosion occurs in the absence of an aqueous phase (dry corrosion). Wet corrosion is influenced by
pressure, temperature, and compositions of aqueous, gaseous, and oil phases.

In refineries and petrochemical plants, the amount of water is usually small, but the corrosivity is high and is
localized at regions where the aqueous phase contacts the metal. The water may contain dissolved
hydrogen sulfide (H2S), carbon dioxide (CO2), and chloride ions (Cl ~). Corrosion may occur even when the
produced water content is as low as 0.1%.

Petroleum Production

Gas condensate wells may produce gas, hydrocarbons, formation water, acid gases (CO
2
and H
2
S) and
organic acids.
Wells that produce formation water, or allow it to condense, are likely to corrode; this may occur
anywhere in the tubing string, wellhead or flow-line. Corrosion increases with water salinity up to about
5% of sodium chloride. Above this, the solubility of oxygen in the water decreases reducing corrosion
rates. In fact, when the salt content is above 15%, the rates are lower than with fresh water.
Higher temperatures accelerate the corrosion rate.
The greater the fluid velocity the greater will be the abrasive and erosive action and hence increased
corrosion.
When water and acid gases are present, the corrosion rates rise rapidly. Water dissolves CO2 or H2S and
becomes acidic.
In highly corrosive environments, carbon steel can be protected by corrosion inhibitors during
production. Like acid corrosion inhibitors, these adhere to casing and completion strings to form a
protective film.
Inhibitors can be continuously introduced into a producing well by a capillary tube run on the outside of
the tubing as part of the completion design. Other methods include batch treatment where inhibitor is
pumped down the tubing regularly, say every six weeks, or squeeze treatments, where inhibitor is
pumped into the formation.
To protect wells and pipelines from external corrosion, cathodic protection is used. In remote areas
sacrificial ground beds may be used for both wells and pipelines

Corrosion due to Stimulation & Secondary recovery fluids:
Water and carbon dioxideproduced or injected for secondary recoverycan cause severe corrosion of
completion strings.
Acidused to reduce formation damage around the well or to remove scalereadily attacks metal.

Drillpipe corrosion:
While a well is being drilled, stress is applied not only to the rig structure, but also to the drilling equipment.
Drillpipe is probably the most harshly treated of all equipment.
It is exposed to formation fluids and drilling mud, subjected to stress corrosion and erosion by cuttings.
Joints of drillpipe are made from hardened high-strength steel and are likely to suffer from fatigue
failures started by deep corrosion pits caused by oxygen, either from the mud or from being stacked wet
Drillpipe is sometimes coated internally, with baked resins or fusion bonded epoxies, to counteract
corrosion.
A common area where drillpipe leaks or washouts occur is in the threaded drillpipe connections called
tool joints. The threads provide ideal places for crevice corrosion. Special grease, commonly known as
dope, lubricates the threads and helps prevent corrosion.

Mud corrosion: Drilling mud plays a key role in corrosion prevention and inhibition. In addition to its well-
known functions, mud must also remain noncorrosive. Drilling muds, left untreated, will corrode not only
well casing, but also drilling equipment, pipelines and mud handling equipment.

Corrosion problems occur due to the lower pH of polymer muds. Low pH means more acidic and hence
more corrosive.
Oil-base muds are usually noncorrosive.
Water-base muds are used with relatively high pH of 10 or greater to reduce their corrosivity.
Dissolved gases are the primary cause of corrosion in drilling fluids. The most common are oxygen,
carbon dioxide and hydrogen sulfide.

Well Completion:
After casing has been put in a well, it is usually cemented in place. Cement itself provides primary
external protection against corrosion, especially near the surface where circulating aquifer water
supplies unlimited oxygen.
Inhibitors are mixed with acid to provide a protective film over exposed completion strings.
Completions and surface pipelines can be eroded away by high production velocities or blasted by
formation sand.

Protection of Offshore structures:
The zone above the high tide mark (splash zone) is constantly in and out of water. The most severe
corrosion occurs here. Any protective coating or film is continually eroded by waves and there is an
ample supply of oxygen and water. Common methods of controlling corrosion in this zone include
coating (sheathing) with Monel and also increasing metal thickness to compensate for higher metal loss.
The part of the structure in the tidal zone is subjected to less severe corrosion than the splash zone and
can benefit from cathodic protection systems at high tide. Cathodic protection works by forcing anodic
areas to become cathodes. To achieve this, a reverse current is applied to counteract the corrosion
current.
Addition of inhibitors to the stagnant water.
Paints and other organic coatings applied to the structures exposed over the splashed zone.

Drilling Bit Corrosion:
Friction
Abrasive action
Fluid erosion

Diamond Wear
Diamond bit wear can occur in the diamonds, the matrix, or other areas. Diamond wear can result from any
one or a combination of the following failure modes:
Graphitization
Oxidation
Gross breakage
Abrasion (microscopic chipping)

Graphitization occurs when a diamond is subjected to temperatures exceeding 2,500oF in an inert
atmosphere. At this temperature point, the diamond degenerates to graphite crystal, which is more stable.
Graphitization apparently occurs on the surface of the diamond while it is drilling. It also occurs inside the
diamond with heat sufficient to cause the carbon atoms inside the diamond to crystallize, allowing the
diamond to reform, or graphitize. Because the graphite crystal occupies a greater space than the diamond
crystal, the diamonds outer crystal lattice cracks to allow the graphite crystals growth. This is one cause of
stone breakage, and should not be confused with thermal stress cracking.

Oxidation of the diamond begins to occur at temperatures between 900 and 1,400o F in the presence of
oxygen. Carbon and free oxygen are converted into carbon dioxide, both of which are gases. Free oxygen is
present in drilling fluid. Since the temperature needed for oxidation are present, oxidation downhole occurs.
Some experts feel that oxidation is the most significant form of diamond wear.

Gross breakage occurs when the diamonds strength is exceeded or when a fracture or cleavage plane is
oriented such that some impact or tangential force on the diamond is string enough to cause failure. Sine
most diamonds used in drill bits contain fracture planes, this type of failure is likely, although infrequent, on
a large scale.

Abrasion (microscopic chipping) is caused by the continual buffeting of the diamond by the formation, by
the sand that has been dislodged, and by the solids being carried by the drilling fluid. After a small piece of
diamond has been chipped away, the sharp exposed areas are then ground back down. This repeated
chipping and grinding causes the diamond to lose mass and a wear flat begins to develop.

Matrix Wear
Matrix wear is caused by:
Fluid erosion
Heat

Fluid erosion is responsible for most matrix wear. All diamond bits will exhibit fluid erosion to some extend
after they have been run. The amount of war is proportional to the length of time the bit was run and the
hydraulic conditions under which it was subjected.
Fluid erosion is caused the drilling fluid passing over the bit face at high energy levels with solids chipping
away at the bit matrix. The energy expended increases as the velocity of the fluid increases. High energy
levels help the bit drill faster by tending to destroy and remove the formation, but at the same time, they
also accelerate the rate of matrix attrition. Rate the matrix attrition can also be increased by adding fine
abrasive solids to the drilling fluid. Even though these solids can be so small that they are not detectable on
a mud report (-200 mesh), they are present and highly detrimental to bit life.

Matrix degradation can also be caused by heat. When the drilling fluid cannot reach some part of the bit to
cool it, the heat buildup cannot be dissipated and can result in heat checking or spalling; this can adversely
affect both bit life and ROP.

Corrosion Engineering Notes (P.E-409)

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Corrosion Engineering Notes (P.E-409)

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Prepared by: Sheikh Mubin Ashraf (B.

E in Petroleum NED Batch: 2010-11)

ions leads to lower pH inside the crevice, metal dissolution

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