Corrosion Engineering

Lecture 2
CHE 311
Definitions
 Corrosion: Corrosion is the destructive or deterioration of a
material by reaction with its environment.
 Metallic corrosion: Metallic Corrosion is the destructive attack of
metals by chemical or electrochemical reaction with its
environment.
 Aqueous Environment: All liquids are aqueous environments.
Examples: Seawater, acid solutions, alkaline solutions. This
leads to Aqueous Corrosion.
 Atmosphere environment: The air environment which is loaded
with substances such as oxygen, carbon dioxide, water vapor,
and sulfur, nitrogen and chlorine compounds; dust and ash. This
leads to Atmospheric Corrosion.
 Solid: All solid materials are solid environments. Examples: Soil,
concrete, and solid food.
 High temperature environment: All gaseous environments at
elevated temperatures are high temperature environments.
Examples: Steam, combustion gases, molten salts, and liquid
metals. This leads to High Temperature Corrosion (Dry
corrosion).
Metals and non metals
 Metallic Materials – Ferrous (Contain Iron)
 Carbon steel
 Low alloy steels
 Cast iron
 Stainless steels

 Metallic Materials – Non- Ferrous

 Copper and copper alloys
 Nickel and nickel alloys
 Aluminum and aluminum alloys
 High temperature alloys
 Titanium

 Non – Metallic
 Plastics
 Rubber
 Ceramic
 Concrete and Reinforced Concrete
General facts about corrosion
 Moist air is more corrosive than dry air.
 Hot air is more corrosive than cold air.
 Polluted air is more corrosive than clean air.
 Hot water is more corrosive than cold water.
 Salt water is more corrosive than fresh water.
 Acidic solution is more corrosive than alkaline solution.
 No corrosion will occur in vacuum, even at very high temperature

 Corrosion is a natural process in general

 Water flows downhill from high level at the top to low level at the bottom of the hill.
 A ball will roll downhill because it has high level of free energy at the top and it cannot roll uphill because it
has a lower free energy at the bottom of the hill than at the top
 All natural processes tend towards the lowest possible energy level
Example: Corrosion of Iron
 Q: Iron and steel have a natural tendency to return to their lowest energy
states which is iron oxide (rust). How?
 Answer: Iron and steel react with the environment containing oxygen and
water to from hydrated iron oxide (rust), similar chemical composition to
originate iron ore found in nature.

Natural corrosion cycle of Steel

Significance of Corrosion
 Cost
 Safety
 Material Conservation
 Energy Conservation
 Environmental Consideration
Direct cost of corrosion
 Replacement cost
 Repairing and maintenance cost
 Corrosion Control cost.

 This direct cost is related to direct losses and it is estimated to be 3 to

4% of the Gross national Product (GNP or GDP). It has been estimated
that 25 to 30% of the direct cost could be saved, if the modern
available corrosion prevention technology were applied.
 The direct economic costs are enormous, estimated to be 3.1% of the
U.S.
 In addition to capital expenditures, corrosion has many indirect costs.
 In addition to the direct and indirect costs, there are long-term
effects of corrosion on safety, health, and the environment that are
not readily quantifiable. Whatever the real cost and lost opportunities
are, corrosion severely impacts everyone's daily life, as well as the
economic, health and security of the nation.
Indirect cost of corrosion
It is difficult to assess a total estimate from direct corrosion losses . The indirect costs add several
billion dollars to the direct costs. The indirect cost includes the following:
 Shutdowns: the replacement of a corroded part in one unit in a plant leads complete shut down of
this unit. The shut down may cost $20,000 per hour.
 Loss of products: Losses of the valuable products (oil, gas, sweet water) from a corroded system
may cost billions of dollars.
 Loss of Efficiency: the accumulation of corrosion products (Scale formation) will decrease the heat
transfer or prevent the proper function of the equipment and as a result the efficiency of the unit
will decrease.
 Contamination of Products: The dissolution of metals in drinking water, canned food or mixing one
product with a second one, caused by leakage will spoil these final products which will be discarded.
One company using metal caps on glass food jars lost $0.5 million in one year. The caps soon got
damaged by corrosion.
 Corrosion allowance (Over design): This measure is common in design of reactors, boilers, buried
pipelines, water tanks. Over designing means to use more material than that specified in the actual
design for a certain component (e.g. to increase the wall thickness of a vessel). The reason is to
increase the service life of that unit before the failure occurs by corrosion.
 Corrosion allowance is subject to general corrosion only. Corrosion allowance has a safety factor
equivalent to 2.
 As an example, suppose a tank wall required a 5 mm (3 1/16 in.) wall thickness for mechanical
considerations. The designer has determined that the corrosion rate will be 15 mpy (0.4 mm/yr) and
the expected life of the equipment will be 10 yr. The total corrosion allowance is the corrosion rate
per year (0.4 mm, or 0.015 in.) × 10 yr = 4 mm (0.15 in.). The corrosion allowance is doubled to 0.3
in. (8 mm) as a safety consideration.
Safety of Corrosion
Safety is a vital factor. Safety should be considered at the stages of materials
selection, design and operation to avoid catastrophic consequence such as:
 Fire hazards
 Explosion hazards
 Mechanical failure (e.g. Pumps, ships component and airplane components)
 Release of toxic hazardous and radioactive materials to environment.
 Personal injury.
 Ignorance of the physical and chemical properties of fluids and corrosion
products (MSDS should filed).
 Civil failure (e.g.: collapse of bridges and buildings) and their interaction
must be known to stop any such catastrophe.
 In general short term and long term safety measure must be adopted to
ensure safety, smooth and profitable operation.
Material Conservation
 Corrosion is a serious problem. It contributes to depletion of the natural
resources. Some of these resources are in critical supply (chromium, nickel,
and manganese). These resources are diminishing very fast due to the world's
industrial development and increasing population. Huge efforts should be
carried out to prolong the service life of materials and as a result to save and
minimize the depletion of natural resources. This objective can be
approached, by using the proper corrosion prevention measures.

Environmental Conservation
Control of Environmental pollutants, contributes to the corrosion control. Air and water pollution
by aggressive and toxic species as well as thermal pollution (discharge of hot effluents to lakes,
rivers, sea, and soils) should be prevented by all means.
 Environmental Control will lead to,
 Less Corrosion failures.
 Less damage to animals, birds and fish life
 Less personal injury
Energy Conservation
 Conservation control also contributes to the conservation of energy. The
production of metals and alloys from their ores consume large amounts of
energy, e.g.: The production of aluminum from its ores requires 29.44 MJ/kg,
steel requires 6.1 MJ/kg. Table 2.1 lists some commonly used metals in order
of energy required to produce them form their ores.

 To prolong the service life of the material along with recycling make it possible to
save large amounts of energy. For example an average car has an energy content
of about 1.3MJ, of which a maximum of 33% can be recovered by recycling.
General approach to control corrosion

There are five general approaches to control corrosion. These are

 Material selection
 Change of Environment
 partially (using inhibitors)
 totally (replacing sea water by river water)
 Place a barrier between the material and the environment
 (Use paints and coating).
 Electrochemical methods
 Cathodic protection, CP
 Anodic protection, AP
 Consider the design at all stages (Design consideration).
Mechanism of Metallic Corrosion
 The mechanism of metallic corrosion in aqueous solutions
involves electrochemical reactions. During the corrosion
process, electrons and ions will be produced and transfer
freely through the system. As a result, there will be a flow of
current from one electrode to a second electrode in a
corrosion cell.
 For a corrosion cell to exist, so corrosion will proceed, the
corrosion cell must contain the following elements:
 Anode, cathode, electrolyte, and a contacting path.
Mechanism of Metallic Corrosion
Current flow (I) Electrical contact (Wire)

(-)
Electron flow (e)
(+)

C
A
A
N
T
O
Ionic current flow H
D
O
E
D
E
Electrolyte

 Electron current flows in the solid conductor (e.g. a wire)

 Ionic current flows in the conducting electrolyte (e.g. Liquid)
 Current (I) flow from the cathode to the anode
 Electron (e) flow from the anode to the cathode
 Definitions
 Anode
 The electrode of a corrosion cell at which oxidation occurs. Electrons flow from the anode
in the external circuit to the cathode. Corrosion usually occurs at the anode and the
metal ions leaves the anode and inter the electrolyte producing ionic current. It is the
negative electrode in the cell and it receives current from the cathode (positive
electrode).
 Cathode
 The cathode is the electrode of a corrosion cell at which reduction occurs. Ionic current
enters it from the electrolyte, and reduction occurs. It is the positive electrode in the cell
and it receives electrons from the anode and attracts the positive ions (cations). Usually it
will not corrode.
 Electrolyte
 It is a solution or medium which contains ions; therefore it is an ionic conductor which
conducts electric current through the transfer of ions. When ionization is complete the
solution is a strong electrolyte, while if the ionization is incomplete it is a week
electrolyte.
 Contacting path
 It is a metallic wire connecting the two separate electrodes in the electrochemical cell.
Daniell corrosion cell

 Daniell corrosion cell consists of, Zn electrode and Cu electrode, each is

immersed in its own solution.
Micro corrosion cell on the same metal surface

 Corrosion of same metal. Example a strip of steel immersed in Hydrochloric Acid (HCL).
Notice the formation of anodic and cathodic areas on the same metal. Notice the connecting
path between the cathode and the anode.
Corrosion driving force
 In a corrosion cell, If one electrode is magnesium (Mg) and the second one is
carbon steel (Fe), where the standard potential of Mg = - 2.37 volts and that
of Fe = - 0.44 volts. We notice that the Mg electrode is more active than Fe
electrode and Mg will be the anode and corrode (oxidation will occur on its
surface). The Fe will be the cathode and will not corrode but reduction
reaction will occur on its surface.
 An electrochemical corrosion cell can occur between two metals (two
separate electrodes, e.g.: magnesium and steel, immersed in water. One
metal will be the anode and the second one will be the cathode.
 In all corrosion cells, the anode usually corrodes and causes damage to the
system. The cathode does not normally corrode. All cathodic (reduction)
reactions occur on the surface of the cathode.
 The elimination or isolation of any of the elements of the corrosion cell will
reduce the corrosion process
 The driving force in the corrosion cell that causes the corrosion of the anode
is the potential difference between the anode and the cathode.
Corrosion driving force
 This potential difference is the difference between the single electrode
potentials which are measured against the standard hydrogen electrode which
has an arbitrarily zero potential.
 The driving force (potential difference) ∆E of the corrosion cell is related to
the free energy change ∆G through Faraday’s law: G = E(- nF)
 where n is the number of electrons, F is Faraday’s constant, and ∆E is the cell
potential. A reaction will occur only if there is a negative free energy change
(∆G).
Corrosion driving force
 For example, the standard reduction potential of copper electrode (Cu)
against the reference electrode is E = + 0.34 volts and the standard reduction
potential of zinc electrode (Zn) against the reference electrode is E = - 0.76
volts. If these two electrodes are used in a cell then this cell is termed
“Daniel corrosion cell",. The potential difference (the driving force) is ∆E =
0.34 – (-0.76) = +1.1 volt which is positive, therefore ∆G is negative.
 In this cell there is a tendency for corrosion of Zn, and the reaction is a
spontaneous one. The zinc electrode will corrode and, termed the active
metal. It is the anode (will corrode), and has negative polarity. The copper
electrode will not corrode (but reduction reaction occurs on its surface), and
termed the noble metal. It is the cathode and has positive polarity.
 This subject is called thermodynamics which is covered in chapter 8.
Anodic Processes (Oxidation)
 When corrosion occurs at the anode positively charged atoms (M +n) of metal
leave the metal surface and enter into solution as ions. These ions leave their
corresponding negative charges electrons which are able to transfer through
the metal (grain boundary boarder) or any external electronic
conductor(metallic copper wire) For example, in the corrosion of iron, each
iron atom (Fe) becomes an iron ion (Fe+2) and generates tow electrons. The
general oxidation reaction is
M M ne
0 n

 For iron the oxidation reaction is Fe Fe+2 + 2e

 The Fe+2 leave the metal surface and enter the solution. The two electrons
transfer to the cathode through the grain boundary or the metallic wire to
complete the circuit and to precede the reduction of positive ions that
consume these electrons.
Cathodic Processes (Reduction)
 What takes place at the cathode? The electrons produced during the anodic
processes and reached the cathode, through an electronic conductor, will
react with positive ions resulted from the cathodic reaction such as hydrogen
ions in the solution:
 2H+ +2e H2 (gas)
 Other cathodic reaction may produce hydroxyl ions (OH _), which migrate
through the solution towards the anodic surfaces to combine with the Fe +2 to
from ferrous hydroxide (rust) as one type of corrosion products of iron.
 Oxygen reduction in neutral solution

O2 + 2H2O + 4e− 4OH−

 Oxygen reduction in Acids
O2 + 4H+ + 2e− 2H2O
Cathodic Processes (Reduction)
 The electrochemical mechanism of corrosion will lead to, many forms (types)
of corrosion such as general (uniform corrosion), localized corrosion (pitting
and crevice), stress corrosion cracking (SCC), galvanic corrosion,
microbiologically induced Corrosion (MIC).
 There are four main types of corrosion cells that can take part in corrosion
reactions and leads to the failure of the metallic structures. These cells are:

 1. Galvanic cell (Dissimilar electrode cell)

 2. Differential aeration cell
 3. Concentration cell
 4. Differential temperature cell
Corrosion of Same metal
 Corrosion can happen even if only one metal is involved. An electrochemical
corrosion cell can occur on the same surface of the metal. Certain areas of a
metal surface are anodes and other areas cathodes through a conductive
solution, such as HCl solution or sea water. The conducing path is the grain
boundary on the same metal.

 Oxidation: Zn = Zn2+ + 2e (Anodic site )

 Reduction: 2H+ + 2e‐ = H2 (Cathodic site)
Corrosion of Same metal
 Corrosion of same metal. Example a strip of steel immersed in HCl. Notice
the formation of anodic and cathodic areas on the same metal. Notice the
connecting path between the cathode and the anode.
Corrosion of Same metal
A single piece of metal will corrode because of
 a) Anodes and cathodes may arise from differences
in constituent phases of the same metal.
 b) Anodes and cathodes arise from variations in the
surface deposits or coatings.
 c) Anodes and cathodes arise from variations in the
electrolyte.
 d) Anodes and cathodes arise from variations
differences in structure and grain size.
 e) Anodes and cathodes arise from variations of the
chemical composition and various impurities may be
present.
Example: The cathode surface may be an impurity,
such as an oxide inclusion, a gain of carbon based
materials such as graphite or a nobler phase.