MM435_Corrosion, Degradation and Protection

Fall-2021

By

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Upcoming Topics….!!

➢Reference Electrodes

➢Pourbaix Diagrams

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Reference Electrodes:
Standard Hydrogen Electrodes:

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Reference Electrodes:
Ag/AgCl Electrode:

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Reference Electrodes:
The Colomel electrode (Hg/Hg2Cl2)

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Reference Electrodes:
Cu/CuSO4 Electrode:

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Ohmic Drop (IR drop):
The IR drop is the ohmic voltage that results from
the electric current flow in ionic electrolytes,
When the reference electrode for measurement
of potential is placed in the electrolyte, an
electrolytic resistance exists along the line
between the test and the reference electrode.

Because the ionic current flows through an

electrolyte resistance an ohmic voltage drop is
also automatically included in the measurement
of potential Current Interruption method

When there is no current flow there cannot be any IR

drop. However, when a current is flowing IR drop is
included in the measurement.
At a certain time, t, the current is interrupted so that
I=0, hence IR is also zero. The test electrode,
therefore, shows a potential free from IR drop.
Hence
IR drop Removal Methods: current interruption provides a good method for
measurement of IR free cell potential.
a. Extrapolation Method
b. Current Interruption Method
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Pourbaix Diagrams

Pourbaix diagram represents the stability of a

metal as a function of potential and pH.

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Pourbaix Diagram of Fe/Water system
Pourbaix diagram represents the stability of a metal as a function of potential and pH.
Characteristics…!! Pourbaix Diagram of Fe-H2O system
Types of Lines?? Four..!!
1. Horizontal to the X-axis:
Those depending only on E, but independent of pH .

The horizontal lines represent electron transfer

reactions.

2. Vertical to the X-axis:

Those dependent only on pH, but independent of E.

3. Slanted with definite slopes:

Those dependent on E and pH
4. Dotted lines
hydrogen and oxygen lines..!
Other Characteristics:
➢ Concentration of all metal ions is assumed to be 10−6 mol
per liter of solution
➢ The diagram is computed for the equilibrium conditions
at 25◦C
➢ The hydrogen and oxygen lines are indicated
in Pourbaix diagrams by dotted line.
Construction…..?? MM-435_Corrosion Degradation and Protection 9
Pourbaix Diagram of Fe/Water system

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Pourbaix Diagram of Fe/Water system

+2

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Pourbaix Diagram of Fe/Water system

This expression shows the relativity

between the pH and potential

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Pourbaix Diagram of Fe/Water system

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Pourbaix Diagram of Water (b)

(a)

➢ Above the oxygen line (b), oxygen liberation occurs

{water decomposes into hydrogen, oxygen and H+ (acidification)}.

➢ Below the hydrogen line (a), hydrogen liberation occurs.

{water decomposes into hydrogen and OH− (alkalization)}

➢ Water is stable between the two lines (a & b).

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Pourbaix Diagram of Fe/Water system

Without hydrogen & oxygen lines..!!

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MM-435_Corrosion Degradation and Protection
Pourbaix Diagram of Fe/Water system

Various regions…!!

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Pourbaix Diagram of Al/Water system

➢ The pH varies (x-axis) from acidic at low pH to

caustic at high pH.

➢ In acidic conditions Al dissolves as Al+3.

--
➢ In alkaline conditions Al dissolves as AlO2 .

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Pourbaix Diagrams for various metals

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Constructing Pourbaix Diagram of Iron

1. http://www.doitpoms.ac.uk/tlplib/pourbaix/pourbaix_construction.php

2. http://aluminium.matter.org.uk/content/html/eng/default.asp?catid=178&pageid=214
4416648

3. https://www.materialsproject.org/

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MM-435_Corrosion Degradation and Protection
Benefits and Problems of Pourbaix Diagrams
Benefits
• Thermodynamic information can be beneficially used
to control corrosion of pure metals in the aqueous
environment.

• By altering the pH and potential to the regions of

immunity and passivation, corrosion can be
controlled.

• For example, on increasing the pH of environment in

moving to slightly alkaline regions, the corrosion of
iron can be controlled

• Similarly, changing the potential of iron to more

negative values eliminate corrosion, this technique is
called cathodic protection.

• Also, raising the potentials to more positive values

reduces the corrosion by formation of stable films of
oxides on the surface of transition metals (Passivity).

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Benefits and Problems of Pourbaix Diagrams
Problems

• Purely based on thermodynamic calculations data

• No information on the kinetics and rates of the

reactions.

• Based on equilibrium conditions in specified

environment and factors.
Temp., velocity etc. not considered which may
seriously affect the corrosion rate.

• The activity of species is arbitrarily selected as

10−6 mol/L which is not realistic.

• Deal with pure metals only

• All insoluble products--assumed to be protective

which is not true, as porosity, thickness, and
adherence to substrate are important factors, which
control the protective ability of insoluble corrosion
products.

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 Assignment # 02 (Handwritten)

Search for the Pourbaix Diagrams for Ni and Zn from the literature and write the
characteristics of all types of lines present in the diagrams and prove with the Section-A
help of thermodynamic calculations the positions of these lines (at least one
line of each type) in each diagram.

Search for the Pourbaix Diagrams for Cu and Ti from the literature and write the
characteristics of all types of lines present in the diagrams and prove with the Section-B
help of thermodynamic calculations the positions of these lines (at least one
line of each type) in each diagram.
➢ The assignment should be hand written
General Instructions:
➢ Due date is Wednesday 10-11-2021 till 17:00 hours.
➢ Submit to our Teaching Assistant

Quiz#03 : Monday, 08-11-2021, 17:00hrs

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 Assignment # 02 (Handwritten)

Search for the Pourbaix Diagrams for Ni and Zn from the literature and write the
characteristics of all types of lines present in the diagrams and prove with the Section-A
help of thermodynamic calculations the positions of these lines (at least one
line of each type) in each diagram.

Search for the Pourbaix Diagrams for Cu and Ti from the literature and write the
characteristics of all types of lines present in the diagrams and prove with the Section-B
help of thermodynamic calculations the positions of these lines (at least one
line of each type) in each diagram.
➢ The assignment should be hand written
General Instructions:
➢ Due date is Wednesday 10-11-2021 till 17:00 hours.
➢ Submit to our Teaching Assistant

Quiz#03 : Monday, 08-11-2021, 17:00hrs

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