ChE 409

Chapter 2

Corrosion Mechanism and forms

of corrosion
Instructor:
Dr. Md. Easir Arafat Khan
Associate Professor
Department of Chemical Engineering, BUET, Dhaka-1000

July 2023
Examples of corrosion
Simplest Example: Dry Cell Battery
 Faraday’s Law
• The mass of an element discharged at an electrode is
directly proportional to the amount of electrical charge
passed through the electrode

weight of metal reacting = kIt

 What Happens if the Battery is Not in Use?

• There will be some “local action current” generated by “local

action cells” because of other metallic impurities in zinc

• Shelf life of an ordinary zinc-carbon rod battery is limited

Local Action Cell
 Anode & Cathode
• Anode
– Loss of electron in oxidation
– Oxidation always occurs at the anode

• Cathode
– Gain of electron in reduction
– Reduction always occurs at the cathode
 Corrosion Classification

Corrosion can be classified in different ways, such as

 Chemical and electrochemical

 High temperature and low temperature

 Wet corrosion and dry corrosion.

Dry corrosion occurs in the absence of aqueous environment, usually in the presence of gases and
vapours, mainly at high temperatures.

Electrochemical nature of corrosion can be understood by examining zinc dissolution in dilute

hydrochloric acid.

Zn + 2HCl = ZnCl2 + H2 (gas)

 Corrosion of Zn in HCl
HCl
Zn++
Reaction:
e-
Zn + 2HCl = ZnCl2 + H2 (gas)
Zn H
H+

Anodic Reaction (oxidation):

Zn – 2e- = Zn++

Cathodic Reaction (reduction):

2H+ + 2e- = H2 (gas)

1. Anode
For corrosion to occur: 2. Cathode
3. Electrolyte
4. Conductor
Corrosion Basics

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

1. Anode
essential. 2. Cathode
A corrosion cell is essentially comprised of the following four 3. Electrolyte
components 4. Conductor
 Corrosion Cells
• Galvanic cell (Dissimilar electrode cell) – dissimilar metals

• Salt concentration cell – difference in composition of aqueous environment

• Differential aeration cell – difference in oxygen concentration

• Differential temperature cell – difference in temperature distribution over

the body of the metallic material
 Dissimilar Electrode Cell
• When a cell is produced due to two
dissimilar metals it is called dissimilar
electrode cell
– Dry cell
Zn anode Cu cathode
– Local action cell HCl Solution

– A brass fitting connected to a steel pipe

– A bronze propeller in contact with the steel
hull of a ship
Salt Concentration Cell
Corrosion at the bottom of the electrical poles
 Differential Temperature Cell
• This is the type of cell when two identical electrodes are immersed in same
electrolyte, but the electrodes 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.
 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)
Forms of Corrosion
Differential Aeration Cell
Forms of Corrosion
Forms of Corrosion
Uniform Corrosion
 Uniform Corrosion
• The rate of corrosion is same over the exposed metal
surface
• Thickness is reduced informally
• Cast irons and steels corrode uniformly when exposed to
open atmospheres, soils and natural waters, leading to the
rusty appearance.

How to prevent uniform corrosion?

Uniform corrosion can be prevented through a number of methods

 Use thicker materials for corrosion allowance
 Use paints or metallic coatings such as plating, galvanizing or anodizing
 Use Corrosion inhibitors or modifying the environment
 Cathodic protection (Sacrificial Anode or Impressed Current -ICCP) and Anodic Protection
Corrosion Rate

• 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
Corrosion Rate

• Mils per year (mpy) = 534W/DAT

• mm/y =87.6W/DAT

– W = weight loss in mg
– D = density of specimen material in g/cm3
– A = area in cm2
– T= exposure time in hours
 Classification of metallic materials according to their rate
of uniform attack
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
Galvanic Corrosion
Galvanic Corrosion
• Known as "Bimetallic Corrosion" or "Dissimilar
Metal Corrosion"
• The potential difference (i.e., the voltage) between
two dissimilar metals is the driving force for the
destructive attack on the active metal (anode).
• The most severe attack occurs at the joint between
the two dissimilar metals.

How to prevent galvanic corrosion?

 Select metals/alloys as close together as possible in the galvanic series.

 Avoid unfavorable area effect of a small anode and large cathode.
 Insulate dissimilar metals wherever practical
 Apply coatings with caution. Paint the cathode (or both) and keep the
coatings in good repair on the anode.
 Avoid threaded joints for materials far apart in the galvanic series.
Selective Corrosion
Galvanic Corrosion
• Dealloying is the selective corrosion of one or more components
of a solid solution alloy.
• It is also called parting, selective leaching or selective attack.
• Common dealloying examples are decarburization,
decobaltification, denickelification, dezincification, and graphitic
corrosion.

How to prevent dealloying corrosion?

 Select metals/alloys that are more resistant to dealloying. For

example, inhibited brass 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
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.
• Pitting corrosion is one of the most damaging forms of
corrosion.
• Outside the gap or without the gap, both metals are
resistant to corrosion
How to prevent pitting corrosion?
 Proper selection of materials with known resistance to the
service environment
 Cathodic protection and/or Anodic Protection
 Use higher alloys (ASTM G48) for increased resistance to
pitting corrosion
Erosion Corrosion
• The mechanical effect of flow or velocity of a fluid
combined with the corrosive action of the fluid
causes accelerated loss of metal.
• Erosion-corrosion is usually found at high flow rates
around tube blockages, tube inlet ends, or in pump
impellers.

How to prevent erosion corrosion?

 streamline the piping to reduce turbulence

 control fluid velocity
 using more resistant materials
 using corrosion inhibitors.
Fretting Corrosion
Cavitation Erosion
Intergranular Corrosion
Corrosion Fatigue
Corrosion fatigue
• Corrosion Fatigue is caused by crack development
under the simultaneous action of corrosion and
cyclic stress.
• As stress is increased, the number of cycles
required to cause fracture decreases.
• The usual case involves rapidly fluctuating stresses
that may be well below the tensile strength.

How to prevent Corrosion fatigue:

• reducing the fatigue by minimizing vibration and pressure fluctuation.

• reducing the corrosion by using high-performance alloys resistant to corrosion
fatigue
• reducing the corrosion by using coatings and inhibitors to delay the initiation of
corrosion fatigue cracks
Stress Corrosion Cracking
Stress Corrosion Cracking
• Stress-corrosion cracking (SCC) is a cracking process that
requires the simultaneous action of a corrodent and
sustained tensile stress.
• Stress corrosion cracking results from the conjoint action of
three components: (1) a susceptible material; (2) a specific
chemical species (environment) and (3) tensile stress.

How to prevent stess corrosion cracking?

 Avoid the chemical species that causes SCC.

 Control of hardness and stress level (residual or load).
 Introduce compressive stress by shot-peening for example.
 Use of materials known not to crack in the specified environment.
 Control operating temperature and/or the electrochemical potential of the alloy.
https://www.youtube.com/watch?v=aHYKd6eKJxk
Crevice Corrosion
 Crevice Corrosion
• Localized attack on a metal surface at, or immediately
adjacent to, the gap or crevice between two joining
surfaces
• The gap or crevice can be formed between two metals
or a metal and non-metallic material.
• Outside the gap or without the gap, both metals are
resistant to corrosion
How to prevent crevice corrosion?
 Use welded butt joints instead of riveted or bolted joints in new
equipment
 Eliminate crevices in existing lap joints by continuous welding or
soldering
 Avoid creating stagnant conditions and ensure complete
drainage in vessels
Hydrogen Damage
Hydrogen Induced Cracking
• Hydrogen-induced cracking results from atomic
hydrogen being absorbed by solid metals.
• This can occur during elevated-temperature
thermal treatments and in service during
electroplating, contact with maintenance
chemicals and operating in high-pressure
hydrogen-containing environments.

How to prevent hydrogen induced corrosion

cracking?
1. Control of stress level (residual or load) and hardness.
2. Avoid the hydrogen source.
Failure Statistics in Germany (a) & USA (b)

a b
 Rusting: Corrosion of Fe

Reaction: Fe + 2H2O + O2 = 2Fe(OH)2

Anodic Reaction (oxidation):

Fe – 2e- = Fe++

Cathodic Reaction (reduction): O2 + 2H2O + 4e- = 4 (OH) ̶