2015 Fall

“Phase Transformation in Materials”

09. 23. 2015

Eun Soo Park

Office: 33-313
Telephone: 880-7221
Email: [email protected]
Office hours: by an appointment 1
- Equilibrium in Heterogeneous Systems

G0β > G0α > G0α+β α + β separation unified chemical potential

- Binary phase diagrams

1) Simple Phase Diagrams ∆H mix
L
= 0 ∆H mix
S
=0
Assume: (1) completely miscible in solid and liquid.
(2) Both are ideal soln.

2) Variant of the simple phase diagram

α
α
∆H mix > ∆H mix
l
>0 ∆H mix < ∆H mix
l
<0

miscibility gab Ordered phase

2
1.5 Binary phase diagrams

5) Phase diagrams containing intermediate phases

3
1.5 Binary phase diagrams

5) Phase diagrams containing intermediate phases

4
The Gibbs Phase Rule 1 single phase
F=C-P+1
=2-1+1
For Constant Pressure, =2
P+F=C+1 can vary T and
composition
independently

2 two phase
1 F=C-P+1
=2-2+1
3 =1
2 2 can vary T or
1 composition
2
1 3 eutectic point
F=C-P+1
=2-3+1
=0
can’t vary T or
composition
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* Vacancies increase the internal energy and entropy → Gibb’s free energy
Equilibrium concentration will be that which gives the minimum free energy.
: adjust so as to reduce G to a minimum
at equilibrium  dG 
  =0
 V  XV
dX = XeV

∆HV − T∆S V + RT ln XeV =0

A constant ~3, independent of T Rapidly increases with increasing T

∆S V −∆HV
=X e
exp
V ⋅ exp
R RT
putting ∆GV =∆HV − T∆S V
−∆GV
X = exp
e
V
RT

• In practice, ∆HV is of the order

e
of 1 eV per atom and XV
reaches a value of about 10-4~10-3
Fig. 1.37 Equilibrium vacancy concentration.
at the melting point of the solid : adjust so as to reduce G to a minimum
 a. Effect of T on solid solubility
 Q 
X Be = A exp−  a) T ↑ X Be ↑
 RT 
b) It is interesting to note that, except at absolute zero,
XBe can never be equal to zero, that is, no two compo
-nents are ever completely insoluble in each other.

“ T ↓ →Solid solution α→ precipitate β ”

A is virtually insoluble in B.

b. Influence of Interfaces on Equilibrium: extra ΔG

2γVm
Gibbs-Thomson effect ΔG = ΔP·V ∆G =
(capillarity effect): r
For small values of the exponent,

X Br = r 2γVm 2γVm
= exp( ) ≈ 1 +
X Br =∞ RTr RTr
Ex) γ=200mJ/m2, Vm=10-5 m3,T=500K
Xr 1
= 1+
X∞ r (nm)
7
For r=10 nm, solubility~10% increase
 Gibbs-Duhem equation: Calculate the change in (dμ) that results from a change in (dX)

Gibbs-Duhem equation
for a binary solution

X Ad µ A + X B d µB =
0

Comparing two similar triangles,

dµ A dµ B d ( µ B − µ A ) dG µ − µA d2G/dX2
− = = = B , 2
XB XA 1 dX B 1 d G/dXB2=d2G/dXA2
Substituting right side Eq. d 2G
& Multiply XAXB − X Ad µ A = X B d µB = X A X B 2
dX B Eq. 1.65
“ Gibbs-Duhem Equation ”
dX
XA, XB vs. dμA, dμB d 2G  d ln γ A   d ln γ B 
γA, γB X AXB 2
=
RT 1 +  =
RT 1 + 
aA, aB
dX  d ln X A  d ln X B  8
 Total Free Energy Decrease per Mole of Nuclei ∆G0
: Driving force for phase transformation of system

Driving Force for Precipitate Nucleation ∆GV

∆G1 = µ αA X Aβ + µ Bα X Bβ
: Decrease of total free E of system
by removing a small amount of material
with the nucleus composition (XBβ) (P point)

∆G2 = µ Aβ X Aβ + µ Bβ X Bβ
: Increase of total free E of system
by forming β phase with composition XBβ
(Q point)

∆Gn = ∆G2 − ∆G1 (length PQ)

∆G Grβ
∆GV = n per unit volume of β
Vm : driving force for β precipitation
For dilute solutions,
∆GV ∝ ∆X where ∆X= X 0 − X e
∆GV ∝ ∆X ∝ ∆T 9
∝undercooling below Te
Contents for today’s class

What are ternary phase diagram?

Diagrams that represent the equilibrium

between the various phases that are formed
between three components, as a function of
temperature.

Normally, pressure is not a viable variable in

ternary phase diagram construction, and is
therefore held constant at 1 atm.

www.sjsu.edu/faculty/selvaduray/page/phase/ternary_p_d.pdf
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Gibbs Phase Rule for 3-component Systems

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 Gibbs Triangle
An Equilateral triangle on which the pure
components are represented by each corner.

Concentration can be expressed as

either “wt. %” or “at.% = molar %”.

XA+XB+XC = 1

Used to determine
the overall composition

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Overall Composition

13
Overall Composition

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 Ternary Isomorphous System

Isomorphous System: A system (ternary in this case)

that has only one solid phase. All components are
totally soluble in the other components. The ternary
system is therefore made up of three binaries that
exhibit total solid solubility.

The Liquidus surface: A plot of the temperatures

above which a homogeneous liquid forms for
any given overall composition.

The Solidus Surface: A plot of the temperatures

below which a (homogeneous) solid phase forms
for any given overall composition.

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 Ternary Isomorphous System

TC
TB

TA TA

TC
TB

TB TC

TA TA 16
Ternary Isomorphous System

TC

TB

TA

17
 Ternary Isomorphous System

TC TC

TB TB

TA TA

18
 Ternary Isomorphous System

TC

TB
TB
TC
TA

TA

19
 Ternary Isomorphous System
Isothermal section → F = C - P

TC

TB

TA

20
 Ternary Isomorphous System
Isothermal section

TC

TB

TA

21
 Ternary Isomorphous System
Isothermal section → F = C - P

Fig. 1.41 (a) Free energy surface of a liquid (b) A tangential plane construction to the (c) Isothermal section through
and three solid phases of a free energy surfaces defined equilibrium a ternary phase diagram
ternary system. between s and l in the ternary system

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 Ternary Isomorphous System
Locate overall composition using Gibbs triangle

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24
 Ternary Eutectic System
(No Solid Solubility)

TA TA
TC
TB

TA

TB

TB
TA

25
TC TC
 Ternary Eutectic System
(No Solid Solubility)

Liquidus projection
TA TC

TB

26
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

27
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

28
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

29
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

30
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

31
 Ternary Eutectic System
(No Solid Solubility)

TA
TC

TB

32
 Ternary Eutectic System
(No Solid Solubility)

T= ternary eutectic temp.

A C

L+A+C

L+A+B L+B+C

B 33
Ternary Eutectic System
(with Solid Solubility)

34
 Ternary Eutectic System
(with Solid Solubility)

TA
TC

TA TC

TB TB 35
 Ternary Eutectic System
(with Solid Solubility)

TB TC

TA

36
 Ternary Eutectic System
(with Solid Solubility)

TB
TC

TA

37
 Ternary Eutectic System
(with Solid Solubility)

TB

TC

TA

38
 Ternary Eutectic System
(with Solid Solubility)

TB

TC

TA

39
 Ternary Eutectic System
(with Solid Solubility)

TC
TB

TA

40
 Ternary Eutectic System
(with Solid Solubility)

TB
TC

TA

41
Ternary Eutectic System
(with Solid Solubility)

T= ternary eutectic temp.

C
L+β+γ

L+α+β L+α+γ

42
 Ternary Eutectic System
(with Solid Solubility)

TB

TC

TA

정해솔 학생 제공 자료 참조: 실제 isothermal section의 온도에 따른 변화 43

http://www.youtube.com/watch?v=yzhVomAdetM
 Ternary Eutectic System
3) Solidification Sequence: liquidus surface

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 Ternary Eutectic System
* Vertical section

* The horizontal lines are not tie lines.

(no compositional information)
* Information for equilibrium phases at
different tempeatures 45
 < Quaternary phase Diagrams >

Four components: A, B, C, D

Assuming isobaric conditions,

Four variables: X A, X B, X C and T

A difficulty of four-dimensional geometry

→ further restriction on the system

Most common figure:

“ equilateral tetrahedron “
4 pure components
6 binary systems
4 ternary systems
A quarternary system

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* Draw four small equilateral tetrahedron
→ formed with edge lengths of a, b, c, d

a+b+c+d=100

%A=Pt=c,
%B=Pr=a,
%C=Pu=d,
%D=Ps=b

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* Incentive Homework 1

Please submit ternary phase diagram model which

can clearly express 3D structure of ternary system
by October 17 in Bldg. 33-313.
You can submit the model individually or
with a small group under 3 persons.

* Homework 1 : Exercises 1 (pages 61-63)

Good Luck!!

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