Phase Transformation

& Microstructure Evolution

Nokeun Park

Pyuck-Pa Choi

2020.03.27-31
1) Thermodynamics & Phase Diagrams
2) Diffusion
3) Crystal Interfaces & Microstructure
4) Solidification
5) Diffusional Transformations in Solids
6) Diffusionless Transformations

2
Outline of Today´s Lecture

 Ideal Solution Model

 Chemical Potential
 Regular Solution Model

3
Ideal Solution Model

 The simplest type of mixing is described by the ideal solution model, which
assumes that:

i.) Volumes of A & B atoms are equal & do not change during mixing.

ii.) Interatomic distances & bond energies are independent of composition.

iii.) ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 0 ⇒ ∆𝐺𝐺𝑚𝑚𝑚𝑚𝑚𝑚 = −𝑇𝑇∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚

 Mixing of A & B to an ideal A-B solution leads to a decrease in Gibbs free energy
for 𝑇𝑇 > 0 due to an increase in entropy.

4
Chemical Potential
 If a small amount of A (𝑑𝑑𝑛𝑛𝐴𝐴 mol) is added to an alloy at constant temperature
𝑇𝑇 & pressure 𝑃𝑃, the Gibbs free energy of the system increases by:

𝑑𝑑𝑑𝑑𝑑 = 𝜇𝜇𝐴𝐴 𝑑𝑑𝑛𝑛𝐴𝐴 (1.58)

𝜕𝜕𝐺𝐺𝐺
⇒ 𝜇𝜇𝐴𝐴 = (1.59) (partial molar Gibbs free energy
𝜕𝜕𝑛𝑛𝐴𝐴 𝑇𝑇,𝑃𝑃,𝑛𝑛𝐵𝐵 or chemical potential of A)

 Considering changes in A & B in

a binary alloy at constant 𝑇𝑇 & 𝑃𝑃 : 𝑑𝑑𝑑𝑑𝑑 = 𝜇𝜇𝐴𝐴 𝑑𝑑𝑛𝑛𝐴𝐴 + 𝜇𝜇𝐵𝐵 𝑑𝑑𝑛𝑛𝐵𝐵 (1.60)

 Considering more than two elements & changes in 𝑇𝑇 & 𝑃𝑃:

𝑑𝑑𝐺𝐺 ′ = −𝑆𝑆𝑆𝑆𝑆𝑆 + 𝑉𝑉𝑉𝑉𝑉𝑉 + 𝜇𝜇𝐴𝐴 𝑑𝑑𝑛𝑛𝐴𝐴 + 𝜇𝜇𝐵𝐵 𝑑𝑑𝑛𝑛𝐵𝐵 + 𝜇𝜇𝐶𝐶 𝑑𝑑𝑛𝑛𝐶𝐶 + … (1.61)

5
Molar Gibbs Free Energy
 Consider an alloy A-B, containing 𝑋𝑋𝐴𝐴
mol of A & 𝑋𝑋𝐵𝐵 mol of B (𝑋𝑋𝐴𝐴 + 𝑋𝑋𝐵𝐵 = 1).

 If 1 mol of A & B atoms are added (at

constant 𝑇𝑇 & 𝑃𝑃) according to the ratio
𝑑𝑑𝑛𝑛𝐴𝐴 𝑋𝑋
𝑑𝑑𝑛𝑛𝐵𝐵
= 𝑋𝑋𝐴𝐴, then the overall alloy
𝐵𝐵

composition, 𝜇𝜇𝐴𝐴 & 𝜇𝜇𝐵𝐵 do not change.

 The Gibbs free energy of the system is 𝐺𝐺 = 𝜇𝜇𝐴𝐴 𝑋𝑋𝐴𝐴 + 𝜇𝜇𝐵𝐵 𝑋𝑋𝐵𝐵 [𝐽𝐽𝑚𝑚𝑚𝑚𝑚𝑚 −1 ] (1.62)
increased by: (molar Gibbs free energy)

 Derivation of eq. (1.62) with respect to 𝑋𝑋𝐵𝐵 shows that 𝜇𝜇𝐴𝐴 & 𝜇𝜇𝐵𝐵 can be obtained
from extrapolation of the tangent to the Gibbs free energy curve to both ends of
the 𝐺𝐺 = 𝐺𝐺(𝑋𝑋𝐵𝐵 ) diagram.
6
Chemical Potentials in Ideal Solution
 Recall the molar Gibbs free energy of an ideal solution:

𝐺𝐺 = 𝑋𝑋𝐴𝐴 𝐺𝐺𝐴𝐴 + 𝑋𝑋𝐵𝐵 𝐺𝐺𝐵𝐵 + 𝑅𝑅 (𝑋𝑋𝐴𝐴 ln 𝑋𝑋𝐴𝐴 + 𝑋𝑋𝐵𝐵 ln 𝑋𝑋𝐵𝐵 )

𝑅𝑅
 Comparison between the above
eq. & eq. (1.62) gives the
chemical potentials of A & B for
an ideal solution:

𝜇𝜇𝐴𝐴 = 𝐺𝐺𝐴𝐴 + 𝑅𝑅 ln 𝑋𝑋𝐴𝐴 (1.63)

𝑅𝑅
𝜇𝜇𝐵𝐵 = 𝐺𝐺𝐵𝐵 + 𝑅𝑅 ln 𝑋𝑋𝐵𝐵 (1.64)
𝑅𝑅
7
Regular Solution Model
 The assumption that ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 0 (ideal solution model) is not valid for most
materials.

 The ideal solution model can be extended to the regular solution model.

 Mixing of A & B results in a change in enthalpy ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 ≠ 0 & an increase in

entropy by ∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚 .

 ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 is only due to nearest neighbor atom bonding. Higher orders of bonding
are not considered.

 If ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 > 0 heat is absorbed (endothermic reaction).

If ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 < 0 heat is released (exothermic reaction).

 Volumes of A & B atoms are equal & do not change during mixing.

 Interatomic distances & bond energies are independent of composition.

8
Regular Solution Model

 Three types of atomic bonds exist

in a binary A-B solution:

i) A-A bonds with energy 𝜀𝜀𝐴𝐴𝐴𝐴 .

ii) B-B bonds with energy 𝜀𝜀𝐵𝐵𝐵𝐵 .
iii) A-B bonds with energy 𝜀𝜀𝐴𝐴𝐴𝐴 .

 The internal energy 𝑈𝑈 of such an A-B

solution is:

𝑈𝑈 = 𝑃𝑃𝐴𝐴𝐴𝐴 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝑃𝑃𝐵𝐵𝐵𝐵 𝜀𝜀𝐵𝐵𝐵𝐵 + 𝑃𝑃𝐴𝐴𝐵𝐵 𝜀𝜀𝐴𝐴𝐵𝐵 (1.65) 𝑃𝑃𝐴𝐴𝐴𝐴 , 𝑃𝑃𝐵𝐵𝐵𝐵 , 𝑃𝑃𝐴𝐴𝐴𝐴 : number of A-A, B-B, A-B bonds

9
Regular Solution Model
 For calculating the internal energy of the regular A-B solution one needs to know
the number of A-A, B-B & A-B bonds (𝑃𝑃𝐴𝐴𝐴𝐴 , 𝑃𝑃𝐵𝐵𝐵𝐵 & 𝑃𝑃𝐴𝐴𝐴𝐴 ).

 Number of A atoms × number of bonds per atom = number of A-B bonds +

2 × number of A-A bonds:

𝑁𝑁𝐴𝐴 𝑧𝑧 𝑃𝑃𝐴𝐴𝐴𝐴
𝑁𝑁𝐴𝐴 𝑧𝑧 = 𝑃𝑃𝐴𝐴𝐴𝐴 + 2𝑃𝑃𝐴𝐴𝐴𝐴 (1.66) ⇒ 𝑃𝑃𝐴𝐴𝐴𝐴 = − (1.67)
2 2
𝑧𝑧: number of nearest neighbor bonds per atom
(coordination number)

 Accordingly, for the B-Atoms:

𝑁𝑁𝐵𝐵 𝑧𝑧 𝑃𝑃𝐴𝐴𝐴𝐴
𝑁𝑁𝐵𝐵 𝑧𝑧 = 𝑃𝑃𝐴𝐴𝐴𝐴 + 2𝑃𝑃𝐵𝐵𝐵𝐵 (1.68) ⇒ 𝑃𝑃𝐵𝐵𝐵𝐵 = − (1.69)
2 2

10
Regular Solution Model

 Inserting eq. (1.67) & (1.69) into eq. (1.65) yields the internal energy of A-B:

𝑁𝑁𝐴𝐴 𝑧𝑧 𝑃𝑃𝐴𝐴𝐴𝐴 𝑁𝑁𝐵𝐵 𝑧𝑧 𝑃𝑃𝐴𝐴𝐴𝐴

𝑈𝑈 = − 𝜀𝜀𝐴𝐴𝐴𝐴 + − 𝜀𝜀𝐵𝐵𝐵𝐵 + 𝑃𝑃𝐴𝐴𝐵𝐵 𝜀𝜀𝐴𝐴𝐵𝐵
2 2 2 2

1 1 1
= 𝑧𝑧𝑁𝑁𝐴𝐴 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝑧𝑧𝑁𝑁𝐵𝐵 𝜀𝜀𝐵𝐵𝐵𝐵 + 𝑃𝑃𝐴𝐴𝐴𝐴 [(𝜀𝜀𝐴𝐴𝐴𝐴 − 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 ]
2 2 2

before mixing increase in 𝑈𝑈 after mixing

 In the same way as for the ideal solution model, mixing of A & B to a regular
A-B solution is done in two steps.

11
Regular Solution Model

 The internal energy of mixing of a regular A-B solution can be expressed as:

1
∆𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑃𝑃𝐴𝐴𝐴𝐴 [(𝜀𝜀𝐴𝐴𝐴𝐴 − 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 ] (1.70)
2

∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = ∆𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 + 𝑃𝑃 ∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 , where ∆𝑉𝑉𝑚𝑚𝑚𝑚𝑚𝑚 = 0 for regular solutions

1
⇒ ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = ∆𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑃𝑃𝐴𝐴𝐴𝐴 [(𝜀𝜀𝐴𝐴𝐴𝐴 − 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 ] = 𝑃𝑃𝐴𝐴𝐴𝐴 𝜀𝜀 (1.71)
2

1
, where 𝜀𝜀 = 𝜀𝜀𝐴𝐴𝐴𝐴 − (𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 ) (1.72)
2

12
Regular Solution Model

 𝜀𝜀, termed the exchange energy, gives the

1
difference between the A-B bond energy & 𝜀𝜀 = 𝜀𝜀𝐴𝐴𝐴𝐴 − (𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 )
2
the average A-A & B-B bond energies:

 𝜀𝜀 = 0, ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 0: ideal solution (special

case of regular solution)

1
⇒ 𝜀𝜀𝐴𝐴𝐴𝐴 = (𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 )
2

 The average A-A, B-B bond energy is equal to the A-B bond energy.

 Thus, atoms show completely random arrangement.

13
Regular Solution Model
 If 𝜀𝜀 ≠ 0 but small ( ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 ≤ 𝑅𝑅𝑅𝑅) the atomic arrangement is nearly random &
the number of A-B bonds can be approximated as:

1 𝑁𝑁𝑎𝑎 = 6.022 × 1023 𝑚𝑚𝑚𝑚𝑚𝑚 −1

𝑃𝑃𝐴𝐴𝐴𝐴 = 𝑁𝑁𝑎𝑎 𝑧𝑧 2𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 = 𝑁𝑁𝑎𝑎 𝑧𝑧 𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 (bonds mol-1)
2
𝑧𝑧: coordination number
(1.73)

Number of atom pairs in 1 mol

Probability of an A-B pair

 Similarly, one can derive for A-A & B-B bonds:

1 1
𝑃𝑃𝐴𝐴𝐴𝐴 = 𝑁𝑁𝑎𝑎 𝑧𝑧 𝑋𝑋𝐴𝐴 2 (1.74) 𝑃𝑃𝐵𝐵𝐵𝐵 = 𝑁𝑁𝑎𝑎 𝑧𝑧 𝑋𝑋𝐵𝐵 2 (1.75)
2 2

14
Regular Solution Model
 Recall that for a (nearly) random A-B solution:

1
∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑃𝑃𝐴𝐴𝐴𝐴 [(𝜀𝜀𝐴𝐴𝐴𝐴 − 𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 ] = 𝑃𝑃𝐴𝐴𝐴𝐴 𝜀𝜀
2

 Inserting eq. (1.73) into the above equation: ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑁𝑁𝑎𝑎 𝑧𝑧𝜀𝜀 𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 (1.76)

 Defining the parameter Ω: Ω = 𝑁𝑁𝑎𝑎 𝑧𝑧 𝜀𝜀 (1.77)

⇒ ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = Ω𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 = Ω(1 − 𝑋𝑋𝐵𝐵 )𝑋𝑋𝐵𝐵 (1.79)

(see Gaskell, p. 245-249)

15
Regular Solution Model

 Solutions that closely obey eq. (1.79)

are known as regular solutions.

 ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 (𝑋𝑋𝐵𝐵 ) is a parabolic

function, where its sign is determined
by 𝜀𝜀 or Ω.

∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 = Ω𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 = Ω(1 − 𝑋𝑋𝐵𝐵 )𝑋𝑋𝐵𝐵

16
Regular Solution Model

 The Gibbs free energy change of mixing of a regular solution is given by:

∆𝐺𝐺𝑚𝑚𝑚𝑚𝑚𝑚 = Ω 𝑋𝑋𝐴𝐴 𝑋𝑋𝐵𝐵 + 𝑅𝑅𝑅𝑅 (𝑋𝑋𝐴𝐴 ln 𝑋𝑋𝐴𝐴 + 𝑋𝑋𝐵𝐵 ln 𝑋𝑋𝐵𝐵 ) (1.80)

∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 − 𝑇𝑇 ∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚

Ω = 𝑁𝑁𝐴𝐴 𝑧𝑧 𝜀𝜀 𝑁𝑁𝐴𝐴 = 6.022 × 1023 𝑚𝑚𝑚𝑚𝑚𝑚−1 (Avogadro constant)

𝑧𝑧: number of nearest neighbor bonds per atom (coordination number)

1
𝜀𝜀 = 𝜀𝜀𝐴𝐴𝐴𝐴 − (𝜀𝜀𝐴𝐴𝐴𝐴 + 𝜀𝜀𝐵𝐵𝐵𝐵 )
2

17
Regular Solution (Exothermic Reaction)

𝜀𝜀 < 0, ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 < 0 (exothermic): A−B bonding preferred to A−A & B−B bonding.

 Mixing results in Gibbs free energy decrease for all temperatures.

18
Regular Solution (Endothermic Reaction)
𝜀𝜀 > 0, ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 > 0 (endothermic): A−A & B−B bonding preferred to A−B bonding.

 Occurrence of mixing depends on whether ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 or − 𝑇𝑇 ∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚 term is dominant.

 At high temperatures (for dominating − 𝑇𝑇 ∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚 ) mixing occurs for all compositions.

 At low temperatures (for dominating ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 ) a miscibility gap exists.

miscibility gap

19
Summary
 The chemical Potential 𝜇𝜇𝐴𝐴 (𝜇𝜇𝐵𝐵 ) gives the increase in Gibbs free energy of the system upon
adding of a small amount of A (or B) at constant pressure & temperature without changing the
overall A-B composition. It is also termed the partial molar free energy.

 The regular solution model assumes that A & B atoms assume the same crystal structure,
have identical volumes & do not change during mixing.

 The internal energy of mixing ∆𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 & enthalpy of mixing ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 can be expressed by the
exchange energy 𝜀𝜀. If 𝜀𝜀 < 0 A-B bonds are preferred, if 𝜀𝜀 > 0 A-A & B-B bonds are preferred.

 ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 of a regular solution is only due to nearest neighbor bonds & is a parabolic function of
concentration.

 A miscibility gap can prevail in regular solutions if ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 > 0 & if the temperature 𝑇𝑇 is low. In
this case, ∆𝐻𝐻𝑚𝑚𝑚𝑚𝑚𝑚 dominates over −𝑇𝑇 ∆𝑆𝑆𝑚𝑚𝑚𝑚𝑚𝑚 in ∆𝐺𝐺𝑚𝑚𝑚𝑚𝑚𝑚 .

20