CH10-2 Gibbs Free Energy Composition and Phase

Diagrams of Binary Systems

RTX A( l ) = RT ln X A( s ) − Gm ( A) …..#3
Check page #20, 22 of CH10-1 Lecture
RTX B (l ) + Gm ( B ) = RT ln X B ( s ) …..#4
 −Gm ( A) 
#3 can be expressed as X A(l ) = X A( s ) exp   …..#5
 RT
 
X B (l ) = 1 − X A(l )
 −Gm ( B ) 
#4 can be expressed as (1 − X A(l ) ) = (1 − X A( s ) ) exp  RT  …..#6
 
 −Gm ( B )    −Gm ( B )    −Gm ( A) 
1 − exp 
 RT  1 − exp     exp  
Combine #5 and #6 we can get X A( s ) =   ; X A(l ) =   RT    RT 
 −Gm ( A)   −Gm ( B )   −Gm ( A)   −Gm ( B ) 
exp  − −
 RT   RT 
exp 
 RT   RT 
       
   −Gm ( B )    −Gm ( A)   −Gm ( B ) 
1 − exp 
1 − exp     exp    RT 
  RT    RT   
X A(l ) = X A( s ) =
 −Gm ( A)   −Gm ( B ) 
 −Gm ( A)   −Gm ( B )  exp  −
exp 
 RT   RT 
−  RT   RT 
       

Tm(B)
L
XA(l)
T
XA(s)

S
Tm(A)
XB(l) XB XB(s)
=1-XA(l) =1-XB(s)
 Miscibility Gap

Let’s relate γ and ɑ using ln  i = (1 − X i )
2

RT

>

<
Miscibility Gap

Δ Δ

Δ Δ
 
 G / X = 0 at XA=0.5 when
2 M 2
B
=2
RT
This is the critical value of ɑ/RT above which phase
separation occurs.

Tcr =
2R
 Binary System without a Miscibility Gap

β+L β
600K ɑ+L
ɑ
ɑ β
Homogeneous solid phase, no
miscibility gap ɑ+L β+L
L
 Binary Eutectic (共晶) System

Ex.: Cu-Ag system T(°C)

1200
L (liquid)
• Limited solubility: 1000
: mostly Cu  L+ L+ 
800 779°C A miscibility gap
: mostly Ag TE 8.0 71.9 91.2
usually refers to that
600 the two phases at two
• TE : No liquid below TE + ends are structurally
dissimilar
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) (CE) + (CE) Adapted from Fig. 9.7,
Callister 7e.

9
 ɑ ɑ+L β+L β

ɑ
ɑ+L β ɑ+β
β+L ɑ β
Tb L
correction
Binary Eutectic System & Miscibility gap & Gibbs free energy

Why not two separate curves?

ɑ1 、 ɑ2 usually
refers to that they
are structurally
similar, so we are
allowed to use a
single Gibbs
energy curve to
present the two
phases
 Microstructures in Eutectic Systems: I

• Co < 2 wt% Sn T(°C)

400
L: Co wt% Sn

• Result: L

--at extreme ends
300 L
--polycrystal of  grains
i.e., only one solid phase. L+ 
200

: Co wt% Sn
(Pb-Sn
TE
System)

+ 
100

0 10 20 30
Co Co, wt% Sn
Adapted from Fig. 9.11,
Callister 7e. 2
(room T solubility limit)

12
 Microstructures in Eutectic Systems: II

L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(°C)
• Result: L
▪ Initially liquid +  L

▪ then  alone 300
L+
▪ finally two phases : Co wt% Sn

➢  polycrystal 200
TE
➢ fine -phase inclusions 

100
+  Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at T room ) 18.3
(sol. limit at TE)
13
 Exercise (page 353, Fig. 10.21)
Bi-Cd phase diagram (around Eutectic point)

H m (Cd ) = 6400 J (i) Calculate InXBi(l) & InXCd(l) assuming the

Tm (Cd ) = 594 K mixing solid solution is ideal (i.e., use equations
H m ( Bi ) = 10900 J
to present the two dashed lines).
Tm ( Bi ) = 544 K
GBi ( s ) = G Bi (l ) = GBi (l ) + RT ln aBi
GBi ( s ) = G Bi (l )
Gm ( Bi ) = − RT ln aBi

GCd ( s ) = G Cd ( l ) If the solution is ideal

Gm ( Bi ) = − RT ln X Bi
cP , Bi ( s ) = 18.8 + 22.6  10−3 TJ / K
cP , Bi ( l ) = 20 + 6.15  10−3 T + 21.1 105 T −2 J / K

 cP , Bi (l ) − cP , Bi ( s ) = cP , Bi = 1.2 − 16.45 10−3 T + 21.1105 T −2 J / K

 Exercise (continued)
H T S
T
 T
cP , Bi 
Gm ( Bi ) = H m ( Bi ),544 +  cP , Bi dT − T  S m ( Bi ),544 + 
  
dT 
544  544
T 
 10900

H m ( Bi ),544 = 10900 J Sm ( Bi ),544 = = 20.0 J / K
544
Gm ( Bi ) = −16560 − 23.79T − 1.2 ln T + 8.225  10−3 T 2 − 10.22  105  T −1
= − RT ln X Bi (l )
5
1992 10
 ln X Bi (l ) =− + 2.861 + 0.144 ln T − 9.892  10−4 T + 1.269  2 Red dashed line
T T

495
Similarly, we can get
ln X Cd (l ) = − − 4.489 + 0.90 ln T − 7.397  10−4 T Blue dashed line
T
( cP,Cd = 7.5 − 12.3 10−3 T )
 Exercise (continued)

(ii) Calculate the actual  Bi ,  Cd

The actual eutectic temp is 419K
Gm ( Bi ),419 = −16560 − 23.79T − 1.2 ln T
+8.225  10−3 T 2 − 10.22  105  T −1 = 2482 J

Gm ( Cd ),419 = 4155 + 37.32T − 7.5T ln T

+6.15  10−3 T 2 = 1898 J
 −2842 
Gm ( Bi ) = − RT ln aBi  aBi ,419 = exp   = 0.49
 8.314  419 
 −1898 
Gm (Cd ) = − RT ln aCd  aCd ,419 = exp   = 0.58
actual mixing temp  8.314  419 
Ideal mixing temp 0.49
  Bi , 419 = = 1.09( X Bi = 0.45)
0.45
0.58
 Cd ,419 = = 1.05( X Cd = 0.55)
0.55
積體電路 (IC, Integrated Circuit)
 3-dimensional Integrated Circuits (3DIC)

https://www.youtube.com/watch?v=XJBqAwUsOnc
 Intermetallic Compounds (介金屬化合物)

Adapted from
Fig. 9.20, Callister 7e.

Unstable phase, causing

unpredictable properties
Mg2Pb

Note: intermetallic compound forms a line - not an area -

because stoichiometry (i.e. composition) is exact. 19
HW 9.3, 9.11, 9.13 (regular solutions), 10.1, 10.3, 10.8,
10.11

2nd Midterm on 5/9

 ∆𝐻𝑚 58160
𝑇 =𝑇 = 37.21𝑇
𝑇𝑚 1563

1328.62K
0.546