ADVANCED
THERMODYNAMICS
Lecture 06 / 07
Week 8 (10/12)
Lilian Chang
liquidus
Fixed p
solidus
Solidus Boundary:
xB(s) vs. T as given by
common tangent
construction for
Tm(B) < T < Tm(A)
Examples:
Cu Ni
Si Ge
Roughly same size
crystal structure,
chemically not so
different
Regular Eutectics
and have some crystal structure and are separated by solid-state miscibility gap
Tm(A)
liquid
Tm(B)
TC
+l
+l
TE
Stable phase
boundaries
Metastable
extension of
solid
miscibility gap
xB(s)(TE)
xB
xBE
xB(s)(TE)
Ag , Tm(Cu)
Cu , Tm(Ag)
TE =
779C
Eutectic Reaction:
Features:
3 single
phase regions
, , and
liquid
Limited
solubility:
: Mostly Cu
: Mostly Ag
3 two phase
regions
( + L),
( + L),
( + )
No liquid
below TE
CE = 71.9
Callister & Rethwisch 9th ed. Wiley, 2013.
Eutectic Isotherm
Eutectic Reaction:
8.0 wt%
10
11
Example: Pb - Sn
L+
L+
+
12
Example: Pb - Sn
L+
L+
+
For 40 wt% Sn 60 wt% Pb alloy at 150C,
determine:
(a) The phases present
(b) The phase compositions
(c) The relative amount of each phase
13
Example: Pb - Sn
For 40 wt% Sn 60 wt%
Pb alloy at 150C:
a) The phases present
L+
L+
14
Example: Pb - Sn
For 40 wt% Sn 60 wt%
Pb alloy at 150C:
a) The phases present
L+
L+
b) The phase
compositions
S
C = 11 wt% Sn
+
C
C = 99 wt% Sn
C
15
Example: Pb - Sn
For 40 wt% Sn 60 wt%
Pb alloy at 150C:
a) The phases present
L+
L+
b) The phase
compositions
S
C = 11 wt% Sn
+
C
C = 99 wt% Sn
C
C - C 0
S
=
W =
R+S
C - C
=
99 - 40
59
=
= 0.67
99 - 11
88
C - C
R
= 0
C - C
R+S
40 - 11
29
=
= 0.33
=
99 - 11
88
W =
16
Example Problem:
SiO2 melts at 1723C, and TiO2 melts at 1842C. SiO2 and
TiO2 are immiscible in the solid state, and the SiO2-TiO2
binary system contains a monotectic equilibrium at 1794C,
at which essentially pure TiO2 is in equilibrium with 2 liquids
containing mole fractions of SiO2 of 0.04 and 0.76. Assume
that the compositions of the two liquids are XSiO2 = 0.24 and
XSiO2 = 0.76 and the liquid solutions are regular in behavior,
What is the value of l and at what temperature does the
liquid immiscibility gap disappear?
17
Example Problem:
Gold and silicon are mutually insoluble in the solid state
and form a eutectic system with a eutectic temperature of
636 K and a eutectic composition of Xsi = 0.186. Calculate
the Gibbs free energy of the eutectic melt relative to
(a) Unmixed liquid Au and liquid Si, and
(b) Unmixed solid Au and solid Si
Given:
Tm,Au = 1338 K, Hm,Au = 12600 J
Tm,Si = 1658 K, Hm,Si = 12600 J
Pb Sn
system
At room temperature:
polycrystalline
18
CL
Pb Sn
system
19
Eutectic
Structure
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21
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