Corrosion; Forms, Mitigation And

Surface Protection Technologies

Course

Eng. Amr Saleh

OGS
OIL & GAS SKILLS
 Chapter 2:

Basics of Corrosion
Electrochemistry
 Corrosion Occurs Through
Electrochemical Reactions
Electrochemical reactions occur:
•In electrolytes , which are liquids that can carry an
electrical current
• Through the exchange of electrons

The exchange of electrons in electrochemical

reactions occurs at separate sites. The electrons
flow through the metal from one of these separate
sites to another.
 Terms Used in Corrosion and
Electrochemistry
Matter
anything that occupies space. (Solid, Liquid or Gas)

Element
Substance that cannot be broken down through chemical
reactions.
Elements are the basic building blocks of all matter
There are 92 naturally occurring elements, ranging from the
lightest, hydrogen, to the heaviest, uranium. Iron, oxygen,
and gold are also elements.
 Terms Used in Corrosion and
Electrochemistry
Compound
● Combination of two or more elements.
● is a pure substance and has a fixed composition.
 Terms Used in Corrosion and
Electrochemistry
Mixture
a combination of elements, compounds, or both held
together by physical (rather than chemical) forces.

Mixture does not have a fixed composition.

Air, for example, is roughly 20% O2 and 78% N2. It also
contains other substances, such as Argon (about 1%) and
varying amounts of carbon dioxide and water vapor.
Soil is a mixture of minerals formed from elements
and compounds like salts and water.
 Terms Used in Corrosion and
Electrochemistry
Atom
● is the smallest chemical unit of an element.
● The number of electrons in an
atom always equals the number
of protons in the nucleus.
● Atoms have a net electrical
charge of zero, and are therefore
electrically neutral.
 Terms Used in Corrosion and
Electrochemistry
Molecule
molecule is the smallest particle of an element or
compound that retains all the chemical properties of that
compound or element.
Electrolyte
An electrolyte is a liquid that contains ions. It can conduct
electricity through the flow of ions.
Anions flow toward the anode and cations flow toward the
cathode.
 Terms Used in Corrosion and
Electrochemistry
Ion
An ion is a charged atom or molecule. An ion may either
be an anion (negatively charged) or a cation (positively
charged). Some examples of ions are shown in Table
 Oxidation/Reduction Reactions
● Most corrosion reactions are electrochemical reactions,
called oxidation/reduction reactions.

● Oxidation/reduction reactions occur through an

exchange of electrons.
● In corrosion reactions, these exchanges occur at specific
sites.

● Oxidation occurs at sites called anodes and reduction

occurs at sites called cathodes.
Oxidation/Reduction Reactions
Corrosion Cycle
 Corrosion Cell
Anions flow toward anode and cations flow toward cathode
 Thermodynamics
● Thermodynamics is the science of the flow of energy.
● In some chemical reactions, such as in the burning of
wood or oil, the energy is in the form of heat.
● In corrosion, energy flows in corrosion reactions ,
usually in the form of electrical energy.
 Thermodynamics
Metals are usually extracted and purified from their ores via
high-energy input processes.
For example : Thermal energy (high furnace for Fe)
Metals tend to corrode in order to retain their natural
form (ore).
Active free metals tend to react easily to produce
compounds, such as salts and oxides.
Metals in the compounded forms have less energy
content, i.e. stable state.
 Thermodynamics
The stored (Gained) energy within the metal is released
(Lost) upon its corrosion.
Thermodynamics
Thermodynamics
Thermodynamics
 Thermodynamics
Comparison of Potentials Measured Using Different
Reference Electrodes

Reference Electrode Potential

Saturated Hydrogen Electrode (SHE) (Volts)
0.000
Saturated Calomel Electrode (SCE) +0.2451
Silver/Silver-Chloride (sat. KCl) +0.2250
Copper/Copper-Sulfate (sat. CuSO4) +0.3160
 Thermodynamics
The Galvanic Series
● The galvanic series is a listing of metals in order of their
potentials in one specific environment.
● The most commonly seen galvanic series is for metals in
seawater.
● There is a general tendency for the active metals to corrode
more rapidly than the metals that are less active
 Thermodynamics
Nernst Equation
The Nernst equation is an electro chemical equation that
relates the potentials of pure metals in solutions containing
various concentrations of ions.
 Thermodynamics
Nernst Equation

Where:
•Eº = Standard state half-cell electrode potential
• E = Electrode potential in existing solution
•aM n+ = Activity of metal ions in solution
•aM = Activity of the metal (aM = 1 for pure metal)
• n = Number of electrons transferred
 Thermodynamics
EMF Series
● The electromotive force (EMF) series is similar to the
galvanic series in that it lists metal oxidation potentials in
order of their potential.
● The galvanic series lists the metals in the order of their
potentials in a single environment.
● The EMF series lists the metals in order of their potentials in
solutions of standard (1 M) ion concentrations.
● The EMF series is also called the standard oxidation-
reduction (redox) Series.
 Thermodynamics
Pourbaix Diagrams
● Pourbaix diagrams are used to predict the stability of metals
and corrosion products in environments of varying pH (pH
is the relative acidity or alkalinity of a solution).
● Pourbaix diagrams are very useful for :
Predicting whether or not corrosion can occur under certain
conditions of pH and potential
Estimating the corrosion product composition
Predicting what changes in pH and potential can increase,
reduce, or eliminate corrosion
 Kinetics
● Kinetics is the study of speed.
● Applied to corrosion, kinetics determines the rates of the
chemical processes responsible for corrosion.
● The rates of the electrochemical reactions responsible for
corrosion is determined by measuring current flow.
● The amount of current flowing can be used to determine
the corrosion rate; the total amount of current flowing
over a period of time can be used to calculate the total
amount of material lost.
 Kinetics
Faraday’s Law
Faraday’s law gives the relationship between the flow of
current and the amount of material corroded.
Faraday’s law is:
Key:
• W = weight of material reacted
• M = atomic weight of material reacted
• t = time in seconds
• I = current flow in amperes
• n = number of electrons exchanged
• F = Faraday’s constant = 96,500 coulombs (Ampere Seconds)
 Kinetics
● For example, say that a current of 2 A flows in a
corrosion cell for a period of 24 hours. If the anode in the
cell is iron and is reacting to form Fe++, what is the
weight of iron reacted?
Where:
• M = 55.85 g/mol
• t = 86,400s
•I = 2A
• n = 2 electrons exchanged
• F = 96,500 coul/g at. wt.
The same current flowing for a year would corrode 365 x 50 or 18,250
grams
 Kinetics
E log i Curves (Evans Diagrams)

● Evans diagrams are useful for showing how

electrochemical cells function.
● Potential is typically plotted on the vertical axis and
logarithm of current flow is plotted on the horizontal axis.
● The Evans diagram shows the effect of polarization on
corrosion behavior.

● Polarization is the change in potential on a metal surface

due to current flow.
 Kinetics
E log i Curves (Evans Diagrams)

● Both anode and cathode in a corrosion cell are subject to

polarization of varying degrees.

● The polarization behaviors of the anodes and cathodes in

a corrosion cell greatly affect the current flow in the cell
and thus greatly affect the corrosion rate of the anode.
 Kinetics
E log i Curves (Evans Diagrams)

In an Evans diagram, the open-circuit (uncoupled) potentials of the anode

and the cathode are represented by points on the vertical axis.
 Kinetics
E log i Curves (Evans Diagrams)

As current is allowed to flow from the anode, the potential of the anode
changes with increased current.

Note that the potential of the anode becomes less negative with current
flow.
 Kinetics
E log i Curves (Evans Diagrams)

Since current also flows from the cathode, the cathode also polarizes with
increasing current
 Kinetics
E log i Curves (Evans Diagrams)

Combined Polarization of Complete Corrosion Cell

 Kinetics
Electrochemical Cells

When there is a difference in potential between two electrodes in an

electrochemical cell, and the electrodes are electrically connected and
exposed to an electrolyte, corrosion can occur.

Galvanic Corrosion Concentration Cell Corrosion

When the potential difference is When the potential difference is
created by a difference in the created by a difference in
chemical compositions of the environment between different
electrodes, the resulting areas on the same metal, the
corrosion is called galvanic resulting corrosion is called
corrosion. concentration cell corrosion.
 Kinetics
Electrochemical Cells

Active/Passive Cells
● When a portion of the surface of a metal is covered with a film of
corrosion products that inhibits corrosion, the potential difference
between the portion of the metal covered with the film and the portion of
the metal that is not covered can create a corrosion cell.

● The area covered by the corrosion products is cathodic with respect to

the uncovered areas.
● The “active” position represents the uncovered material and the “passive”
position is that of the covered material. The potential difference between
the active and passive areas can cause very rapid localized attack if the
anode-to-cathode area ratio is small
 Kinetics
Electrochemical Cells

Thermogalvanic Corrosion
● Temperature can affect the corrosion potentials of metals.
● Metal exposed to a higher temperature will have a more active (negative)
potential than the same metal at a lower temperature.

● One result of this effect is the thermo galvanic corrosion between hot and
cold domestic copper water pipes when both are buried in the soil under
a house.
 Passivity
● Passivity is the reduction of chemical reactivity of a metal or alloy
under certain circumstances.
● Film formation occurs naturally in air and can provide a very
substantial reduction in the corrosion of these materials.

Aluminum, with its very active position in the galvanic and EMF series,
is expected to corrode rapidly. Because of the presence of a thin,
tightly adherent film of aluminum oxide that forms on the aluminum
upon exposure to air, aluminum alloys have good resistance to
corrosion in many environments where the oxide film responsible for
their passivity is stable.
 Passivity

In some cases, such as in stainless steels, active metals, such as

chromium are added to iron. The active chromium helps to form the
tightly adherent film responsible for the corrosion resistance of
stainless steels in many environments. The addition of other elements,
such as nickel and molybdenum, to the chromium-iron alloys further
improves the stability of this passive film and improves corrosion
resistance in a wide variety of environments.
Passivity
 pH Scale
● One factor in the corrosivity of liquids is pH.
● pH has been mentioned before in this course, but not completely
defined.

● pH is a measure of the acidity or alkalinity of an aqueous solution.

Pure water is very slightly ionized by the breakdown of a few of the
water molecules to form hydrogen ions (H+) and hydroxyl ions (OH–)
through the reaction.
Thanks for your Attention