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CHE 211

ADVANCED
THERMODYNAMICS
Lecture 06 / 07
Week 8 (10/12)
Lilian Chang

Ideal solid and liquid 2-component mixtures (lens phase diagram)


Liquidus Boundary:
xB(l) vs. T as given by
common tangent
construction for
Tm(B) < T < Tm(A)

liquidus

Fixed p
solidus

Solidus Boundary:
xB(s) vs. T as given by
common tangent
construction for
Tm(B) < T < Tm(A)

Source: Gaskell D. R., Introduction to the Thermodynamics of Materials

Examples:
Cu Ni
Si Ge
Roughly same size
crystal structure,
chemically not so
different

Eutectic Phase Diagrams

Solid dont like to mix


Liquid mixtures stable for all compositions above elemental melting
temperatures
Liquid mixtures stable over some composition range below lowest
elemental melting temperature
Lowest temperature where single phase liquid is stable is the eutectic
temperature (TE)
composition of eutectic liquid is xBE
Below TE, we have homogeneous solids () and () and regions
where 2-phase equilibrium between solids exists (+)
A-rich solid
B-rich solid

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)

Eutectic Phase Diagrams

Solid dont like to mix

Source: Gaskell D. R., Introduction to the Thermodynamics of Materials

Source: Gaskell D. R., Introduction to the Thermodynamics of Materials

Binary Eutectic Phase Diagram


Features:
3 single
phase regions
, , and
liquid
Limited
solubility:
: Mostly Cu
: Mostly Ag
3 two phase
regions
( + L),
( + L),
( + )

Callister & Rethwisch 9th ed. Wiley, 2013.

Binary Eutectic Phase Diagram

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.

Binary Eutectic Phase Diagram


Features:
3 single
phase regions
, , and
liquid
Limited
solubility:
: Mostly Cu
: Mostly Ag
3 two phase
regions
( + L),
( + L),
( + )

Eutectic Isotherm

Eutectic Reaction:

8.0 wt%

CE = 71.9 91.2 wt%


Callister & Rethwisch 9th ed. Wiley, 2013.

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Binary Eutectic Phase Diagram


Binary
2 components
Eutectic (Greek for easily melted)
Has a special composition with minimum melting temperature, Tm
Examples:
Cu (FCC) Ag (FCC)
Pb (FCC) Sn (tetragonal)
Fe (BCC) C (graphite hexagonal)

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Example: Pb - Sn

L+
L+
+

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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

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Example: Pb - Sn
For 40 wt% Sn 60 wt%
Pb alloy at 150C:
a) The phases present
L+

L+

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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

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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) The relative amount of each phase

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 =

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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?

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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

Development of Microstructure: Case 1


Cooled slowly from 350C at composition C1
point a : liquid
point b: solidification of the phase
point c: complete solidification

Pb Sn
system

Callister & Rethwisch 9th ed. Wiley, 2013.

At room temperature:
polycrystalline

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Development of Microstructure: Case 2


Cooled slowly at composition C2
point d : liquid
point e: solidification of the phase
point f: grains
point g: formation of small -phase particles

CL

Callister & Rethwisch 9th ed. Wiley, 2013.

Pb Sn
system

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Development of Microstructure: Case 3

Eutectic
Structure

Callister & Rethwisch 9th ed. Wiley, 2013.

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Development of Microstructure: Case 3


Photomicrograph of Pb-Sn alloy of eutectic
composition

-phase is Pb-rich (dark)


-phase is Sn-rich (light)

Callister & Rethwisch 9th ed. Wiley, 2013.

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Eutectic Structure example (Organic


System)

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Source: https://www.youtube.com