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Lecture 2 Phase Transformations in Metal and Alloys

The document discusses phase transformations in metals and alloys, focusing on the effects of pressure and temperature on Gibbs free energy. It introduces the Clausius-Clapeyron equation and explores the driving forces for solidification, including the concepts of binary solutions and ideal solutions. Additionally, it covers the chemical potential in alloys and how free energy changes with the addition or removal of atoms.

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Fazli subhan
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8 views

Lecture 2 Phase Transformations in Metal and Alloys

The document discusses phase transformations in metals and alloys, focusing on the effects of pressure and temperature on Gibbs free energy. It introduces the Clausius-Clapeyron equation and explores the driving forces for solidification, including the concepts of binary solutions and ideal solutions. Additionally, it covers the chemical potential in alloys and how free energy changes with the addition or removal of atoms.

Uploaded by

Fazli subhan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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PHASE TRANSFORMATIONS

in Metal and Alloys

By Dr. Feroz Shah

Lecture No.2
Pressure Effect

• We rewrite the equation 1.9 for gibbs free energy when


temperature and pressure varies

At constant temperature

• If the two phases in equilibrium have different molar volumes their


respective free energies will increase with different amounts
Continued

• If the two phases in equilibrium are and , application of


Equation 1.9 can be written for 1 mol of both phases

• In equilibrium condition = and =


Continued

• In simplified form it can be written


as:

This is known as the


Clausius‑Clapeyron equation

Figure 7
The driving force for solidification

• Phase transformations we are often


concerned with the difference in free
energy at temperatures other than
equilibrium temperature

• If a liquid metal is undercooled by ΔT


below Tm before it solidifies,
solidification will be accompanied by a
decrease in free energy ΔG

• This free energy decrease provides the


Figure 1
The driving force for solidification

The free energies of liquid and solid at constant temperature are given by:

Therefore at a temperature

Where and

At the equilibrium melting temperature the free energies of solid and


liquid are equal, i.e.
The driving force for solidification
As a result ,

Therefore at melting temperature ,

This is known as entropy of fusion, for most metals its value is


Combining eq. 3 and 4, we get:

For small
Binary Solutions

• So for we considered single component (one element) only

• All phases had the same composition

• Equilibrium involved pressure and temperature variation

• Now we consider interaction between two elements

• Equilibrium will involve alloy composition too as variable


Binary Solutions

• Lets consider a binary


system with element A and B

• Lets consider mole fraction


of A and mole mole of B for
the purpose of analysis

• Imagine that 1 mole of solid


solution is formed by the
combination of A and B:
Figure 2
Binary Solutions

• The free energy of the system before


mixing, when kept separately:

and are the molar of pure A and B

For all alloy composition lies on the


straight line between and as shown
in Figure 3 Figure 3
Binary Solutions
• After mixing there will be a change in the free energy of the system

• Total Free energy after mixing:

Where is the change in free energy due to mixing

Since

Putting
Ideal solution

• A solution is said to be ideal if there is no heat loss or gain during


mixing, i.e.

• In this case the free energy change will only be due to change in
entropy:

• In statistical thermodynamics, quantitatively entropy is given by:

Where k is Boltzmann’s constant and ω is a measure of randomness


Ideal solution

• There are two contributions to the entropy of a solid

• , and a configurational contribution

• In case of , is the number of ways in which the thermal energy of solid


can be divided among the atoms

• In case of , is the number of ways of arranging the atom in the


solution

• In case of ideal solution with no volume change or heat change during


mixing the only contribution to is the change in configuration
entropy
Ideal solution
Where is the number of A atoms and is the number of B atoms

As we have consider 1 mole of the system, The number of atoms in 1 mole will
be equal to Avogadro number,

and

By substituting into eqs. 11 and 12, using Stirling's approximation

and the relationship = R (the universal gas constant)


Ideal solution

Since and are less than unity, is


positive

Hence there is an increase in entropy


on mixing

The free energy of mixing, is obtained:

Figure 4 shows as a function of


Figure 4
composition and temperature
Ideal solution
• As there was only one way of arranging the atoms before mixing:

or

Therefore,

Assuming that A and B mix to form a substitutional solution

• The number of distinguishable ways of arranging the atoms on


the atom sites is:
Ideal solution

The actual free energy of the solution G


will also depend on GA and GB

Note that as the temperature increases


and decreases and the free energy
curve assume a greater curvature

Figure
5
Chemical potential
In alloys it is of interest to know how the free energy of a given phase will

change when atoms are added or removed

Let a small quantity of A, mol, is added to a large amount of a phase at

constant temperature and pressure, the size of the system will increase by

The total free energy of the system will also increase by a small amount

If is small enough, will be proportional to the amount of A added

Therefore,

The proportionality constant , is called the partial molar free energy of A or

alternatively the chemical potential of A in the phase


Chemical potential

• For a small amount it can be rewritten as:

• The symbol has been used for the Gibbs free energy to emphasize the fact
that it refers to the whole system

• The usual symbol will be used to denote the molar free energy and is
therefore independent of the size of the system

• For a binary solution at constant temperature and pressure, we can write:

•
Chemical potential

• If variation in and are also allowed, then we can write:

• If 1 mol of the original phase contained mol of A and mol


of B, the size of the system can be increased without
altering its composition if A and B are added in the correct
proportion

• For molar free energy, we can write eq. 18 as:


Chemical potential

• When is know as a function


and as shown in Figure 6

• and can be obtained by


extrapolating the tangent to
the curve to the sides of the
molar free energy diagram

Figure 6
Chemical potential

Comparing Equation 15 and 18, for


an ideal solution, we can write:

As shown in Figure 7

Figure 7
Thank you

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