ChE 4751

Corrosion Science and Engineering

Md. Jahirul Islam

Lecturer
Department of Chemical Engineering
Dhaka University of Engineering and Technology, Gazipur
Corrosion Mechanism

© Md. Jahirul Islam , Lecturer

 Components of Corrosion cell

For corrosion to take place, the formation of a corrosion cell is essential. A

corrosion cell is essentially comprised of the following four components

• Anode
represented as the negative terminal of the cell. Electrons are released at the anode, which is the
more reactive metal.
• Cathode
represented as a positive terminal of a cell. Reduction takes place at the cathode and electrons are
consumed.
• Electrolyte
It is the electrically conductive solution (e.g. salt solution) that must be present for corrosion to
occur. Positive electricity passes from anode to cathode through the electrolyte as cations
• Metallic path
The two electrodes are connected externally by a metallic conductor. In the metallic conductor,
‘conventional ’ current flows from (+) to (−) which is really electrons flowing from (−) to (+).

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Components of Corrosion cell

Figure: Corrosion cell in action

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Galvanic Cell

Figure: A galvanic cell (Daniel cell)

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 Anodic Reactions Characteristics

 The anode is the area where metal is lost.

 It represents oxidation of metal to an ion with a charge releasing electrons and
shifting to a higher valance state
 It includes precipitation of metal ions at the metal surface. For example Fe2+ +
2OH − → Fe(OH)2 .

What will be the anodic reactions?

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 Cathodic Reactions Characteristics

 Cathodic reactions are reduction reactions which occur at the cathode.

 Electrons released by the anodic reactions are consumed at the cathode surface.
 Unlike an anodic reaction, there is a decrease in the valence state.
The most common cathodic reactions in terms of electrons transfer:

So, for corrosion to occur,

should the metal act as anode
or cathode?

© Md. Jahirul Islam , Lecturer

 Types of Corrosion Cells

There are several types of corrosion cells:

(1) Galvanic cells (Dissimilar electrode cell) -dissimilar metals
(2) Salt concentration cell- difference in composition of aqueous environment
(3) Differential aeration cell – difference in oxygen concentration
(4) Differential temperature cell – difference in temperature distribution over the
body of the metallic material

© Md. Jahirul Islam , Lecturer

 Dissimilar electrode cell

When a cell is produced due to two dissimilar metals

it is called dissimilar electrode cell.
 Dry cell
 Local action cell
 A brass fitting connected to a
steel pipe
 A bronze propeller in contact
with the steel hull of a ship

Figure: Typical galvanic cell

© Md. Jahirul Islam , Lecturer
 Salt Concentration Cells

• This is similar to galvanic cells except with an anode and

cathode of the same metal in an aqueous solution of
different composition.
• Copper dissolves at the anode and is deposited at the
cathode until the concentration of CuSO4 reach the same
concentration.

© Md. Jahirul Islam , Lecturer

 Differential Aeration Cell

• Both electrodes are of same material and electrolyte conc.

in both chambers are same
• N2 is bubbled in one chamber and air O2 in another one
• Difference in O2 conc causes potential difference between
two electrodes and subsequent flow of current
• Electrode in contact with low O2 concentration act as
anode
• Electrode in contact with high O2 concentration solution act
as cathode
• Common example: Corrosion at the bottom of steel
electrical poles
© Md. Jahirul Islam , Lecturer
 Differential Aeration Cell

Concentration cell formation in an underground pipeline Corrosion at the bottom of the electrical poles

© Md. Jahirul Islam , Lecturer

 Differential Temperature Cell

• This is the type of cell when two identical electrodes are immersed in same

electrolyte, but the electrode are immersed into solution of two different

temperatures

• This type of cell formation takes place in the heat exchanger equipment where

temperature difference exists at the same metal component exposed to same

environment

• For example, for CuSO4 electrolyte & Cu electrode the electrode in contact with

hot solution acts as cathode.

© Md. Jahirul Islam , Lecturer

 Forms of Corrosion

1. General corrosion or uniform attack

2. Pitting
i. Impingement attack or erosion-corrosion
ii. Fretting corrosion
iii. Cavitation erosion
3. Selective Corrosion
4. Intergranular Corrosion
5. Cracking
i. Corrosion fatigue
ii. Stress corrosion cracking (SCC)

© Md. Jahirul Islam , Lecturer

 Uniform Corrosion

• Uniform corrosion is a type of corrosive attack in which the corroded areas

occur in a manner evenly distributed across the material being attacked.

• Uniform corrosion can render large amounts of material useless quite rapidly

because the attack occurs across the entirety of the exposed surface.

• Example: rusting of mild steel in water, tarnishing of silver in atmosphere,

fogging of nickel

© Md. Jahirul Islam , Lecturer

Uniform Corrosion

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 Corrosion Rate and Classification of Metals

• mm/y – millimeters penetration per year

• gmd – grams per square meter per day

• ipy – inches penetration per year

• mpy – mils penetration per year (1000 mil = 1 inch)

• mdd – milligrams per square decimeter per day

© Md. Jahirul Islam , Lecturer

Corrosion Rate and Classification of Metals

534W
Mils per year (mpy) =
DAT

87.6W
mm/y =
DAT

W = weight loss in mg
D = density of specimen material in g/cm3
A = area in cm2
T= exposure time in hours

© Md. Jahirul Islam , Lecturer

 Corrosion Rate and Classification of Metals

A. <0.005 ipy (<0.15 mm/y) – Metals in this category have

good corrosion resistance and can be used for critical parts
B. 0.005 to 0.05 ipy (0.15 mm/y to 1.5 mm/y) – Metals in this
group are satisfactory if a higher rate of corrosion can be
tolerated
C. >0.05 ipy (>1.5 mm/y) – Usually not satisfactory

© Md. Jahirul Islam , Lecturer

 Pitting

• This is a localized type of attack, with the rate of corrosion being greater at some
areas than at others.
• Deep Pit: Attack is confined to a relatively small, fixed area of metal, acting as
anode.
• Shallow Pit: Area of attack is relatively larger and not so deep.
• Iron buried in the soil corrodes with formation of shallow pits, whereas stainless
steels immersed in seawater characteristically corrode with formation of deep pits.
• Pitting is a dangerous form of corrosion as it is difficult to predict pit depths. Deep
pits might ultimately result in perforations causing harmful accident.

© Md. Jahirul Islam , Lecturer

 Pitting

• Depth of pitting is sometimes expressed by the pitting factor, the ratio of

deepest metal penetration to average metal penetration as determined by the
weight loss of the specimen.

Figure: Sketch of deepest pit in relation to average metal

penetration and the pitting factor

© Md. Jahirul Islam , Lecturer

Mathematical Problem

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 Different types of Pitting Corrosion

 Impingement attack
 Occurs when metals are subjected to high - velocity liquids
 Also called corrosion-erosion.
 Copper and brass condenser tubes, for example, are subject to this type of attack

 Fretting corrosion
 results from 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 pit become visible.

© Md. Jahirul Islam , Lecturer

 Different types of Pitting Corrosion

 Cavitation – erosion
 The loss of material caused by exposure to cavitation, which is the formation and
collapse of vapor bubbles at a dynamic metal – liquid
 For example, in rotors of pumps or on trailing faces of propellers.
 This type of corrosion causes a sequence of pits

© Md. Jahirul Islam , Lecturer

 Selective corrosion

 Dealloying
selective removal of an element from an alloy by corrosion.
Dezincification which is one form of dealloying, 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.
The alloy so corroded often retains its original shape, and may appear undamaged
except for surface tarnish, but its tensile strength and ductility are seriously reduced.

© Md. Jahirul Islam , Lecturer

 Selective corrosion

 Parting
similar to dezincification
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 noble metal alloys such as gold – copper or gold – silver
and is used in gold refining.
Example: An alloy of Au – Ag containing more than 65% gold resists concentrated nitric
acid as well as does gold itself. However, on addition of silver to form an alloy of
approximately 25% Au – 75% Ag, reaction with concentrated HNO3 forms silver nitrate
and a porous residue or powder of pure gold

© Md. Jahirul Islam , Lecturer

 Intergranular Corrosion

 A localized type of attack at the grain boundaries of a metal.

 Grain – boundary material of limited area, acting as anode,
is in contact with large areas of grain acting as cathode.
 The attack is often rapid, penetrating deeply into the metal
and sometimes causing catastrophic failures.
 At elevated temperatures, intergranular corrosion can occur
because, under some conditions, phases of low melting
point form and penetrate along grain boundaries

© Md. Jahirul Islam , Lecturer

 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, there is fatigue limit or endurance

limit for which metal will not fail by fatigue even after a very large, or infinite,
number of cycles

 A true endurance limit does not commonly exist in a corrosive environment

© Md. Jahirul Islam , Lecturer

 Stress - corrosion cracking

 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.

 Almost all structural metals (e.g., carbon - and low - alloy steels, brass, stainless
steels, Duralumin, magnesium alloys, titanium alloys, nickel alloys, and many
others) are subject to stress - corrosion cracking in some environments.

 Highly stressed metal structures must be designed with adequate assurance that
stress - corrosion cracking will not occur.

© Md. Jahirul Islam , Lecturer

Hydrogen Damage

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 Crevice Corrosion

 Crevice corrosion refers to the attack of metal surfaces by a stagnant solution in

crevices
 Crevice corrosion occurs in shielded regions where a small volume of stagnant
corrosive fluid is trapped between two surfaces, such as under loose paint
 Crevice corrosion is considered much more dangerous than uniform corrosion
since its rate is 10-100 times higher.
 Crevice corrosion is highly accelerated if chloride, sulphate or bromide ions are
present in the electrolyte solution.
 Stainless steels, Aluminum alloys and other metals forming a passive oxide
layers on their surfaces in electrolytes and atmosphere are sensitive to crevice
corrosion.
© Md. Jahirul Islam , Lecturer
 Crevice Corrosion

 Anodic reactions inside the crevice:

Fe = Fe2+ + 2e- (dissolution of iron)

 The electrons given up by the anode flow to the cathode (passivated

surface) where they are discharged in the cathodic reaction:

1/2O2 + H2O + 2e- = 2(OH-)

 As a result of these reactions the electrolyte enclosed in the crevice gains

positive electrical charge in contrast to the electrolyte surrounding the
crevice, which becomes negatively charged.

 The positively charged electrolyte in the crevice attracts negative ions of

chlorine Cl- increasing acidity of the electrolyte according to the reaction:

FeCl2 + 2H2O = Fe(OH)2 + 2HCl

 pH of the electrolyte inside the crevice decreases (acidity increases) from

6 to 2-3, which causes further acceleration of corrosion process.
© Md. Jahirul Islam , Lecturer
Failure Statistics in Germany (a) & USA (b)

© Md. Jahirul Islam , Lecturer