An Introduction to Corrosion

DEFINITION OF CORROSION
Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with its environment.

Deterioration by physical causes is not called corrosion, but is described, erosion, galling, or wear.

If both it will be called corrosion – erosion, corrosive wear, or fretting corrosion.

Nonmetals are not included in this definition of corrosion. Plastics may swell or crack, wood may
split or decay, granite may erode, and Portland cement may leach away, but the
term corrosion, in this book, is restricted to chemical attack of metals.
IMPORTANCE OF CORROSION
The three main reasons for the importance of corrosion are: economics, safety, and conservation

Economic losses are divided into (1) direct losses and (2) indirect losses
Ex for direct losses: replacing parts or tanks, coils ,repainting,……etc
Ex of indirect: shutdown,losse of products and activity , contamination and overdesign
 Extreme Risk. Extensive risk controls must be applie
High-Consequence Risk. Risk controls required.

RISK MANAGEMENT Moderate Risk. Some risk controls required.

Low Risk. Risk controls may be justified.
 CAUSES OF CORROSION
Change in Gibbs Free Energy:
The change in Gibbs free energy, ΔG , for any chemical reaction indicates the tendency of that reaction to go.
Reactions occur in the direction that lowers the Gibbs free energy. The more negative the value of ΔG , the
greater the tendency for the reaction to go
Pilling–Bedworth Ratio:
The Pilling – Bedworth ratio is Md / nmD , where M and D are the molecular weight and density, respectively, of
the corrosion product scale that forms on the metal surface during oxidation; m and d are the atomic weight and
density, respectively, of the metal, and n is the number of metal atoms in a molecular formula of scale; for
example, for Al 2 O 3 , n = 2.
Md / nmD < 1, the volume of the corrosion product is less than the volume of the metal from
which the product formed. A film of such a corrosion product would be expected to contain
cracks and pores and be relatively nonprotective. On the other hand,
Md / nmD > 1, the volume of the corrosion product scale is greater than the volume of the metal
from which the scale formed, so that the scale is in compression, protective of the underlying
metal. A Pilling – Bedworth ratio greater than 1 is not sufficient to predict corrosion resistance.
Md / nmD >> 1, the scale that forms may buckle and detach from the surface because of the
higher stresses that develop.
Electrochemical Mechanisms
THE DRY- CELL ANALOGY AND FARADAY’ S LAW:

Weight of metal reacting = kIt

the coulomb being defined as the amount of electricity

represented by 1 A fl owing for 1 s

local - action current, and

the corresponding cells are called local - action cells
local - action current, and the corresponding cells are called
local - action cells
Whenever impurities in a metal constitute the
electrodes of local - action cells, their removal, as
might be expected, appreciably improves corrosion
resistance
DEFINITION OF ANODE AND CATHODE
A galvanic cell converts chemical energy into electrical energy.
positive current flows through the metallic path from positive electrode to negative electrode
only negative carriers, or electrons, move in a metal.
Within the electrolyte, current is carried by both negative and positive carriers, known as ions.
The electrode at which chemical reduction occurs (or + current enters the electrode from the
electrolyte) is called the cathode

The electrode at which chemical oxidation occurs (or + electricity leaves the electrode and
enters the electrolyte) is called the anode .

In galvanic cells, the cathode is the positive pole, whereas the anode is the negative pole
TYPES OF CELLS
There are three main types of cells that take part in
corrosion reactions. Cathode

1-Dissimilar Electrode Cells. anode

Ex. Dry cell ( metals containing impurities of other

metals). A copper pipe connected to an iron pipe,
and a bronze propeller in contact with the steel hull
of a ship. Dissimilar electrode cells also include cold -
worked metal in contact with the same metal
annealed, grain – boundary metal in contact with
grains.
2-Concentration Cells.
Two kinds of concentration cell:
i- Salt conc. Cell Crevice
ii-differential aeration cell corrosion
Examples :
3-Differential Temperature Cells.

Components of these cells are electrodes of the same metal, each of which is at a different
temperature.

These cells are found in heat exchangers, boilers, immersion heaters, and similar equipment.
In copper sulfate solution, the copper electrode at the higher temperature is the cathode, and
the copper electrode at the lower temperature is the anode.

Lead acts similarly, but for silver the polarity is reversed.

For iron immersed in dilute aerated sodium chloride solutions, the hot electrode is anodic to
colder metal of the same composition; but after several hours, depending on aeration, stirring
rate, and whether the two metals are short - circuited, the polarity may reverse
TYPES OF CORROSION DAMAGE
1. General Corrosion, or Uniform Attack.
Ex: rusting of iron or tarnishing of silver. “ Fogging ” of nickel and high - temperature oxidation of
metals
Rates of uniform attack are reported in various units,
millimeters penetration per year (mm/y)
grams per square meter per day (gmd).
inches penetration per year (ipy), mils (1 mil = 0.001 inch) per year (mpy), and milligrams per
square decimeter per day (mdd).
metals are classified into three groups according to their corrosion rates
2. Pitting.( localized attack)
the rate of corrosion being greater at some areas than at others.
attack is confined to a relatively small, fixed area of metal, acting as anode
If the area of attack is relatively larger and not so deep, the pits are called shallow
pitting factor

The ratio of deepest metal penetration to average metal penetration as determined by the
weight loss of the specimen.
A pitting factor of unity represents uniform attack
Many metals, when subjected to high - velocity liquids, undergo a pitting type of corrosion
called impingement attack , or sometimes corrosion - erosion. ( ex. Copper and brass)
Fretting corrosion: slight relative motion (as in vibration) of two substances in contact, one or
both being metals, usually leads to a series of pits at the metal interface. Metal - oxide debris
usually fills the pits so that only after the corrosion products are removed do the pits become
visible.
Cavitation – erosion is the loss of material caused by exposure to cavitation, which is the
formation and collapse of vapor bubbles at a dynamic metal – liquid interface — for example, in
rotors of pumps or on trailing faces of propellers.

3. Dealloying, Dezincifi cation, and Parting. Dealloying is the selective removal of an element
from an alloy by corrosion. One form of dealloying, dezincification, is a type of attack occurring
with zinc alloys (e.g., yellow brass)in which zinc corrodes preferentially, leaving a porous residue
of copper and corrosion products
Parting is similar to dezincification in that one or more reactive components
of the alloy corrode preferentially, leaving a porous residue that may retain the
original shape of the alloy. Parting is usually restricted to such noble metal alloys
as gold – copper or gold – silver and is used in gold refining
4. Intergranular Corrosion.
This is a localized type of attack at the grain boundaries of a metal, resulting in loss of
strength and ductility.
Ex. Improperly heat - treated 18 - 8 stainlesssteels or Duralumin - type alloys (4% Cu – Al),
also at high temperature nickel - base alloys are exposed to sulfur - bearing gaseous
environments, nickel sulfide can form and cause catastrophic failures [7] . This type of attack
is usually called sulfidation .

5. Cracking.
If a metal cracks when subjected to repeated or alternate tensile stresses in a corrosive
environment, it is said to fail by corrosion fatigue
In the absence of a corrosive environment, the metal stressed similarly, but at values
below a critical stress, called the fatigue limit or endurance limit , will not fail by fatigue even
after a very large,or infinite cycles.
If a metal, subject to a constant tensile stress and exposed simultaneously to a specific
corrosive environment, cracks immediately or after a given time, the failure is called stress -
corrosion cracking .
Thermodynamics and Kinetics
of Corrosion Processes
Oxidation and Reduction Processes in Aqueous Solution
In neutral water, the anodic reaction produces a soluble ion, Fe2+ as an intermediate
product and although the final product is a solid, it is precipitated from solution and
does not protect the metal, whereas in alkaline water, the anodic reaction converts
the iron surface directly into a thin protective solid layer. Such effects can be
explained by thermodynamic assessments.
Oxidation state:

The overall change in oxidation state in a completed reaction must be zero so that,
four iron atoms all increase in oxidation state from +II to +III and this is balanced by
a reduction in the oxidation state of the two atoms in molecular oxygen from 0 to –
II in the form of the oxide. This illustrates the principle that in any complete system
an oxidation reaction must be compensated by an equivalent reduction reaction.
Electrodes
The oxidation state of species can also be changed by the intervention of an
electrically conducting surface at which electrons can be transferred
( Electrode)
Anode ( oxidation)

Cathode ( reduction)

Net reaction
Equilibria at Electrodes and the Nernst
Equation
Van’t Hoff reaction isotherm:
 The Standard Hydrogen Electrode

The sign to be given to the potential is determined by the direction of the

spontaneous reaction at the electrode when it is coupled to a standard hydrogen
electrode. If the reaction is in the direction of reduction, the potential is positive
and if it is in the direction of oxidation, it is negative, as the following examples
illustrate:
Example 1 Calculate the solubility product, Ks, for silver chloride from the measured potential,
0.222 V (SHE) of the silver/silver chloride standard cell, saturated with AgCl.
Pourbaix (Potential-pH) Diagrams
Objective:
Represent the relative stabilities of solid phases and soluble ions that are produced by reaction between a
metal and an aqueous environment as functions of two parameters, the electrode potential, E, and the pH of
the environment.
Example of the Construction of a Diagram — The Iron-Water System:

In Reactions 1 to 7, the solid phases and also the solvent, water,

are present at unit activity and do not influence the equilibria. The
equilibria are therefore governed by the following factors:

1. The charge transferred,, E. This applies only to reactions

involving electrons, Reactions 1 to 6 but not Reaction 7.
2. The activity of hydrogen ions, i.e., the pH of the solution.
3. The activities of other soluble ions, e.g., Fe2+ and Fe3+.
 pH independent
Horizontal lines

All dependent
Iron activity independent -ve slope lines
Single –ve slope line
All dependent Iron activity independent
-ve slope lines Single –ve slope line

pH independent
Horizontal lines E independent
Vertical lines
The Domain of Stability for Water

For combinations of potential

and pH above the top line,
water is unstable and
decomposes evolving oxygen.
For combinations below the
bottom line, it is also
unstable and decomposes
evolving hydrogen
 Application of Pourbaix Diagrams to Corrosion Problems

1. Domains of immunity, in which the metal is

the stable species and is immune to
corrosion in the terms for which the diagram
is drawn.
2. Domains of corrosion in which the stable
species is a soluble ion and the metal is
expected to corrode if the kinetics are
favorable.
3. Domains of passivity in which the stable
species is an insoluble solid that can protect
the metal if it forms an impervious,
adherent layer.
Pourbaix (Potential-pH) Diagrams for Some Common Metals
Cu+ (aq) ion is unsustainable at the value, 10–6, for which the diagram is
prepared, whereas the oxide Cu2O has a domain of stability
Example 7 In the Pourbaix diagram of the copper-water system for a Cu2+ = 10–6 at 25° C, the +II oxidation state is
represented by both a soluble ion, Cu2+(aq), and an oxide, CuO, but the +I state is represented only by the oxide
Cu2O. Show that the activity of the Cu+ (aq) ion is unsustainable at the value, 10–6, for which the diagram is
prepared, whereas the oxide CuO has a domain of stability.

Soluble species, Cu+ (aq) and Cu2+ (aq):

The negative value for (∆G o) 1 indicates that

the reaction is spontaneous
Limitations of Pourbaix Diagrams

• The diagrams are derived from thermodynamic considerations and yield no kinetic
information. There are situations in which zones of corrosion suggest that a metal
dissolves and yet it does not, due, for example, to the formation of a metastable
solid phase or to kinetic difficulties associated with a complementary cathodic
reaction.

• Domains in which solid substances are considered to be the stable species relative
to arbitrary soluble ion activities smaller than 10-6 give good indications of
conditions in which a metal may be passive. Whether particular metals are
actually passivated within these nominal domains and to what extent a useful
passive condition can extend beyond their boundaries depends on the nature,
adherence and coherence of the solid substance.
• The diagrams yield information only on the reactions considered in their
construction and take no account of known or unsuspected impurities in the
solution or of alloy components in the metal that may modify the reactions. For
example, Cl– or SO42– ions present in solution may attack, modify or replace
oxides or hydroxides in domains of passivity, diminishing the protective power of
these substances and small quantities of alloy components can introduce
microsructural features of the metal that resist passivation

• The form and interpretation of a Pourbaix diagram are both temperature-

dependent
Kinetics of Aqueous Corrosion
Arrhenius’ equation: activation energy, ∆G*

Kinetic View of Equilibrium at an Electrode

Ions transported across an electrode carry electric
charge, so that the reaction rate, r, can be replaced
by an electric current, i. The energy of the process is
the product of the charge and the potential drop, E,
through which it is carried = (zFE)
At equilibrium the rate of deposition = the rate of dissolution
The currents leaving and entering the metal, respectively, are called the partial
currents. Their magnitude at equilibrium is called the exchange current density, i0
Polarization( activation, concentration and resistance)
If equilibrium at an electrode is disturbed, a net current flows across its surface displacing the
potential in a direction and to an extent depending on the direction and magnitude of the
current. The shift in potential is called polarization and its value, η, is the overpotential
=0.5 if the maximum is equidistant from the two minima
1-Activation Polarization

• Activation polarization is a manifestation of the relative

changes in the activation energies for dissolution and
deposition
• The polarization will be positive, i.e., anodic, or negative, i.e.,
cathodic, according to whether the net current is a
dissolution or deposition current.

anodically polarized
Butler-Volmer equation
 For the electrode at equilibrium, the activation energies for dissolution
and deposition were both equal to G* but for the polarized electrode, the

Tafel or High-Field Approximation

If the polarization is anodic, with overpotential > 0.1 V so that

relationships are the same for forward and reverse currents, so that the
electrode cannot act as a rectifier for AC current. This is the usual situation.
However, it is found by experiment that certain electrodes do act as rectifiers
and the phenomenon is called Faradaic rectification. This implies that
for those particular electrodes the curve is not symmetrical about the origin,
and so α is not equal to 0.5.
Concentration Polarization

1- As the potential of an electrode is altered further and further away from its equilibrium
potential, the net current flowing, whether anodic, ia , or cathodic, ic, increases at first
according to the Tafel equation

2-the current cannot be increased indefinitely because there are limits to the rate at which
ions can carry charges through the solution to and from the electrode

3-The effect arises because ions are produced or consumed at the electrode surface faster
than they can diffuse to or from the bulk of the solution

4-the concentration of ions in the immediate vicinity of the electrode is raised above that in
the bulk solution; conversely, in a cathodic reaction, the local concentration is depressed

5-As a consequence, the polarization for a given current is greater than that predicted by
the Tafel equation. The excess potential is called the concentration polarization, ηC
For the reverse (cathodic) reaction:
 3-Resistance
Polarization
• For some electrode reactions the effects of ohmic resistance can be very considerable
especially if the reaction produce film on the electrode surface

• The total potential drop across such resistance is called resistance polarization, ηR.

The effects of these forms of polarization are illustrated by the

characteristics of hydrogen evolution and oxygen reduction reactions that
feature prominently in corrosion processes.
The Hydrogen Evolution Reaction and Hydrogen
Overpotential
Z=1 α=0.5
so that b=0.118
Example
Table 3.4 gives representative results from measurements of potential, E,
versus current density, i, for the evolution of hydrogen on platinum. They
apply to 0.1 M hydrochloric acid at 25C. Do they yield a value for b comparable
with the value given in Equation 3.53?
The overvoltage,, is E – E , yielding
-

the values given in the middle row

Linear plot above 0.06 volt and deviate
as overpotential approach zero so we can
calculate Io

Slope=b=0.11 in good agreement

The Oxygen Reduction
Reaction
The reduction of oxygen dissolved in water at metal surfaces exemplifies the
influences of concentration and resistance polarization. It is a common cathodic
process supporting corrosion of metals because natural waters are constantly
replenished with dissolved oxygen by recycling through air as rain. In acidic water,
the reduction reaction is predominantly

The reduction of oxygen at metal surfaces is difficult to characterize. One problem

is its sensitivity to concentration polarization due to the low solubility of oxygen in
water.
Corrosion Velocity Diagrams: Evans
Diagram
The method is to display on the
same diagram the polarization
characteristics of all electrode
processes that contribute anodic
and cathodic reactions in a
particular corroding system.
Example 9
Using the following data, show that the absorption of oxygen is the dominant
cathodic reaction sustaining the corrosion of iron in neutral water in equilibrium
with air.
Passivity
In appropriate conditions, some base metals can develop a surface condition that
inhibits interaction with aqueous media. The condition is described as passivity
and its development is called passivation.
Spontaneous Passivation
 Some metals passivate spontaneously in water if the pH is within ranges corresponding to
potential-independent domains of stability for oxides or hydroxides.
 These domains appear in the Pourbaix diagrams, e.g., within the pH ranges 3.9–8.5 for
aluminum and 8.5–10.5 for zinc,.
 The effect is due to the formation of thin protective oxide or hydroxide films.
 The existence of a domain of stability for an oxide or hydroxide in the Pourbaix diagram is
not the sole condition for passivation.
 To be protective, the solid product must not only be coherent and adherent to the metal
surface but also its integrity must not be impaired by impurities contributed by the metal
or the environment
 Impurities and extraneous inclusions in the metals can contribute minority phases that
breach the passive surface.
 Anodic Passivation
For some transition metals and their alloys, passivation is both pH and potential dependent.
 In these circumstances, the metal may corrode actively at low potentials but can be
passivated by raising its potential to a more positive value.
 The phenomenon is described as “anodic passivation”.

1. In aerated neutral water, i.e., with pH 7, the oxygen absorption

reaction polarizes the iron anodically to a potential of
approximately – 0.45 V SHE,

2. The iron-water Pourbaix diagram shows that these coordinates for

pH and potential define a point in the domain of stability for Fe2+, so
that dissolution of iron is expected as happens in practice.

If the anodic polarization is increased to impose a potential more

positive than –0.15 V SHE, the new coordinates define a point in the
domain of stability for Fe2O3, indicating a possible passive condition.
( can be obtained by using external source or adding oxidizer)
 Theories of Passivation
1- Film Theory ( by Faraday )
There is experimental evidence for tangible oxide films on some but not all kinds of passivated
metal surfaces. When the film is established, its ability to protect the metal depends on the
degree of restraint it imposes on dissolution of the metal.
The dissolution is the combined result of three processes:
1. Entry of metal atoms into the film as cations at the metal/film interface.
2. Transport of the metal cations or of oxygen anions through the oxide.
3. Dissolution of metal cations from the film at the film/environment interface.
At ambient temperatures, the processes are driven by the electric field across the film and so the
following properties of a film commend it as a passivating agent:
1. Stability over a wide potential range.
2. Mechanical integrity.
3. Low ionic conductivity.
4. Good electron conductivity to reduce the potential difference across the film.
5. Low solubility and slow dissolution in the prevailing aqueous medium.
 Adsorption Theory (Kolotyrkin and Uhlig)
 The theory recognizes that strong anodic passivation is a characteristic of alloys
of metals in the transition series, notably iron, chromium, nickel, molybdenum,
and cobalt and it is natural to associate it with the partly filled 3d or 4d shells in
their electron configurations.

 singly occupied or unfilled atomic orbitals offer the facility for the highly
polarized water molecules and anions in immediate contact with the metal to
bind to the surface metal atoms by sharing electrons, creating the passive
condition that protects the metal.
in the active range, surface atoms of the metal, M, are assumed to lose
electrons and become solvated by first row water molecules, forming soluble
cations:
Compatibility of Film and Adsorption

 The main criticism of the adsorption theory is that although it can explain
instantaneous passivation by very thin films, the passive state is more often
associated with a film thicker than a monolayer,

 The two theories are not incompatible and it is best to regard each as
revealing part of the truth,

 the film theory dealing with the nature of the film.

 and the adsorption theory drawing attention to the nature of the metal and
to the relation between the kinetics of dissolution and the kinetics of
passivation.
Breakdown of Passivity
when the prevailing conditions cannot maintain passivity, the whole surface
becomes active and attack is by uniform dissolution (general).
 Ex. stainless steels, the passive condition is terminated at an upper potential, the
breakdown potential, and higher potentials are designated transpassive
potentials.
 If isolated sites become active in an otherwise passive surface they are
selectively attacked. Local dissolution at the active sites is often very intense due
to the establishment of active/passive cells
 Ex, Crevices Pitting

 Mechanical Breakdown of Passivity

Passivity can be broken down by mechanical means to produce damaging effects,
by stress-corrosion cracking, corrosion fatigue and erosion corrosion
Corrosion Inhibitors
a chemical substance that decreases the corrosion rate when present in the corrosion
system at suitable concentration, without significantly changing the concentration of any
other corrosion agent

Some occur naturally and others are introduced artificially as a strategy for corrosion control:
Application examples :
1. Preserving existing iron or steel delivery systems for municipal water supplies.
2. Maintaining clean thermal transfer surfaces in closed heating and cooling circuits.
3. Protecting mixed metal systems.
4. Enhancing the protective value of paints
Inhibitors intervene in corrosion kinetics in various ways. Some inhibit cathodic reactions,
others inhibit anodic reactions and yet others, mixed inhibitors, do both
 Cathodic Inhibitors
Cathodic inhibitors produce adherent compact deposits on metal surfaces that suppress the
cathodic reaction, by creating a barrier to oxygen diffusion and preventing transfer of electrons
from the metal

Ex: solutes in hard water that yield scales. Calcium and magnesium carbonate, zinc and
manganese form a protective scales. In soft water do not form scales so addition of lime and
phosphate or silecates which can protect iron.

Anodic Inhibitors
Anodic inhibitors suppress anodic reactions by assisting the natural passivation tendencies of
metal surfaces or forming deposits that are impermeable to the metal ions
Nitrite, and chromate, ions can impose redox potentials on the metal by reactions such as:

Even in small concentrations, the available potentials are sufficient to passivate iron by producing
a coherent film of γ- Fe2O3.
Anodic inhibitors cathodic inhibitors
Cathodic inhibitors
Safe and Dangerous Inhibitors

 The concept of safe and dangerous inhibitors is important

 Cathodic inhibitors are safe in the sense that if they are present at insufficient
concentration, they simply fail to protect completely and do not stimulate
corrosion on unprotected areas.

 In contrast, anodic inhibitors are dangerous because cathodic reactions are

not suppressed on protected areas. Therefore, if by inadequate initial
additions or subsequent poor maintenance the supply of inhibitor fails locally,

 corrosion is stimulated on the depleted areas because they become anodes in

active/passive cells supported by large cathodic currents collected by the
passive area.