MSE561: Phase Transformations,

Kinetics, and Diffusion in Solids

3. Regular Solutions --- Model of Binary Alloy

Yang Jiao

Materials Science & Engineering

School for Engineering of Matter, Transport and Energy
Arizona State University
Tempe, AZ 85287-6016

Lecture time T/Th 10:30 – 11:45 AM

https://asu.zoom.us/j/2759304275
 Topics Covered:

• Regular Solution
• Enthalpy of Mixing
• Effects of Temperature, Mixing vs De-mixing
• Activity
• Real Solutions
• Ordered Phase & Intermetallic Compounds
 Solution vs. Phase Separated State

Which phase (i.e., separated vs. mixing) is

thermodynamically more stable?
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Solution vs. Phase Separated State

Enthalpy of Mixing

Entropy of Mixing

Free Energy of Mixing

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 Regular Solution

Enthalpy of Mixing

H mix  0

Free Energy of Mixing

Entropy of Mixing plays the same role as for

ideal solutions!

What is the effect of Enthalpy of Mixing?

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Simple model for enthalpy of mixing

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 Simple model for enthalpy of mixing

Enthalpy before mixing:

H1  nA AA  nB BB

nAA – number of A-A bonds

nBB – number of B-B bonds

Each A atom has 4 bonds; Each bond is shared by 2 atoms

nAA = 2NA (number of A atoms)

nBB = 2NB (number of B atoms)

H1  2 N A AA  2 N B BB

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 Simple model for enthalpy of mixing

Enthalpy after mixing:

H 2  PAA AA  PBB BB  PAB AB

PAA – number of A-A bonds
PBB – number of B-B bonds
PAB – number of A-B bonds

Each A-A bond contributes to ½ A atom;

Each B-B bond contributes to ½ B atom;

Each A-B bond contributes to ¼ A atom and ¼ B atom;

1 1 1 1
N A  PAA  PAB N B  PBB  PAB
2 4 2 4
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 Simple model for enthalpy of mixing

H1  2 N A AA  2 N B BB H 2  PAA AA  PBB BB  PAB AB

1 1 1 1
NA  PAA  PAB N B  PBB  PAB
2 4 2 4
Enthalpy of Mixing
H1  PAA AA  PBB BB  P 1
AB 2  A   B 

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Simple model for enthalpy of mixing

Enthalpy of Mixing

H1  PAA AA  PBB BB  PAB 1

2  A   B 
H 2  PAA AA  PBB BB  PAB AB

epsilon = 0 -> Ideal Solution!

Need to find how PAB depends on XA

and XB!

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 Simple model for enthalpy of mixing

Na – Avogadro’s number
z – coordination number
XA – molar fraction of A atoms
XB – molar fraction of B atoms

This equation also holds for non-zero epsilon, given its value
is not too large!

Most real alloys do not meet this requirement, thus, insights

obtained here are only qualitative!

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Simple model for enthalpy of mixing

Enthalpy of Mixing

The sign of Omega, inherited from epsilon,

determines the enthalpy of mixing!

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Solution vs. Phase Separated State

Free Energy of Mixing

Enthalpy vs. Entropy, which would play a

more important role?

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 Free energy of solid solution

Both Enthalpy and Entropy favors mixing!

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 Free energy of solid solution

Enthalpy and Entropy are competing with one another!

Temperature induced phase transition is expected! 15

 Free energy of the solid solution

Can we write these in a similar form as ideal solutions?

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 Chemical Potential of Regular Solution and Activity
Introducing Activity:

Activity includes effects of both atomic interactions

(enthalpy) and molar fraction (entropy)! 17
Brief overview of real solutions

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 Brief overview of real solutions

Superlattice: alloying atoms take the original crystal lattice

Superlattice (superalloy) only occurs at certain

compositions! 19
 Brief overview of real solutions
Intermetallic compounds: alloying atoms take a new crystal
structure, distinct from original structures

Intermetallic compound only occurs at certain compositions! 20

 Topics Covered:

• Regular Solution
• Enthalpy of Mixing
• Effects of Temperature, Mixing vs De-mixing
• Activity
• Real Solutions
• Ordered Phase & Intermetallic Compounds
Thank You!

Questions?

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