(MS511)

Thermodynamics and Phase Equilibria

Chapter 10:

Binary Phase Diagram I

Phase Equilibrium in Binary System:
• The state of lowest Gibbs free energy is the stable state.
• When phases coexist in equilibrium,
𝐺̅! has the same value in all of the coexisting phases.

\ Gibbs free energy-composition çè Phase diagram

Spinodal decomposition Complete lig/sol solution

Image obtained from Alloy Phase Diagram Database
G of Formation of Regular Solution:
DG M = WX AX B + RT (X A ln X A + X B ln X B )
E AA + E BB
W = zNO (E AB - )
2
G of Formation of Regular Solution:

W = RTa
Criteria for Phase Stability:
A critical value of a = acritical
below which a homogeneous solution is stable over the entire composition
above which phase separation occurs
Spinodal Decomposition:
1.2 800K

900K
1.0

1000K
0.8

1100K
a 0.6 (c)
B

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1.0
A XB B
Ideal Liquid & Solid Solution:
DG M = WX AX B + RT (X A ln X A + X B ln X B )
E AA + E BB
W = zNO (E AB - )
2

a: ideal solution, W=0 & gi=1

b: regular solution, W>0 & gi>1

c: regular solution, W<0& gi<1

Ideal Liquid & Solid Solution:
(liq)
Tm(B)
T
Tm(A)
(s)
ΔGM
A e f B
i x l iq GB°(l)
u nm

GA°(l)0 0

A B
Ideal Liquid & Solid Solution:
for Tm(A)<T<Tm(B), GA°(l)<GA°(s), GB°(s)<GB°(l)
ΔGm°(A) = GA°(l) - GA°(s) = ΔHm°(A) - TΔSm°(A)
Binary Phase Diagrams: C.S.S
The complexity of P.D. depends on the similarity b/w endmembers.
e.g., crystal structure, ionic size, chemical properties, etc.

Liquidus: the boundary b/w the single-phase liquid and two-phase field
Solidus: the boundary b/w the single-phase solid solution and two-phase field
 Binary Phase Diagrams: C.S.S

Fig. 1.29 from Phase Transformations in Metals and Alloys 3rd edition
Systems with a Miscibility Gap
In regular solution model:

DG M = WX AX B + RT (X A ln X A + X B ln X B )
E AA + E BB
W = zNO (E AB - )
2

a: ideal solution, W=0 & gi=1

b: regular solution, W>0 & gi>1

c: regular solution, W<0& gi<1

 Systems with a Miscibility Gap
∆𝐺 ! ∆𝐺 !

∆𝐺 !

Fig. 1.30 from Phase Transformations in Metals and Alloys 3rd edition
14
Limited Solid Solubility: Eutectic
System
Limited Solid Solubility: Eutectic
System
Intermediate Compounds
Peritectic Diagrams
Incongruent melting:
A solid substance does not melt uniformly, decomposing into
another solid and a liquid with different compositions.

Peritectic reaction:
A liquid and solid phase of fixed proportions react at a fixed temp.
to yield a single solid phase
 Derivation of Gibbs Phase Rule:

J.E. Trevor, J. Phys. Chem., 1902, 6 (3),

pp 185–189
Derivation of Gibbs Phase Rule:
C = # of components, P = # of phases
21
 (MS511) Thermodynamics of Materials

Lecture 9-2:

Pop Quiz
 Pop quiz #1
T

A B

a) Draw a microstructure when a1 is lowered along a2 and a3

b) Draw a microstructure when b1 is lowered along b2 and b3

c) Using a lever rule, describe the composition at b2

 Solution of pop quiz #1
a)

𝑙 a1

𝑙+𝛼
𝑙+𝛽
a2
𝛼1 𝛽1
a3
𝛼
𝛽
𝛼+𝛽

A XB B
 Solutions
b & c)

𝑙 b1

𝑙+𝛼
𝑙+𝛽
𝐿1 b2
𝛽1
𝛼2 𝛽2
𝛼 b3
𝛽
𝛼+𝛽

A XB B
 Solutions
b)

𝑙 b1

𝑙+𝛼
𝑙+𝛽
𝐿1 b2
𝛽1
𝛼2 𝛽2
𝛼 b3
𝛽
𝛼+𝛽

A XB B
 Solutions
c)

𝑙+𝛼
𝑙+𝛽
𝐿1 b2
𝛽1

𝛼
𝛽
𝛼+𝛽

60 78 90
A B
Metals handbook, 9th, Vol.9 Metallography and microstructures
28
Pop quiz #2
Describe G curves of each phase at given temperature.

XB
Pop quiz #3
Draw the phase diagram of a A-B binary system using the G curves
according to the temperature below.
 A Bit of History
Nanotubes and fibers (whiskers) have been observed throughout
the age of modern microscopy-aided technology development.

Single crystal nanowires result from compressive stresses

- heating of metals on Si substrates
- electromigration
These continue to be a nuisance.

Uncatalyzed single crystal whiskers have been observed in both

gas phase and liquid phase processes
- spiral growth on screw dislocations
- growth velocity anisotropy, amplified through ‘poisoning’ of
specific facets

Wires purposely grown via the vapor-liquid solid mechanism were

first studied, as a ‘novelty’, at Bell labs in the 1960’s.

Growth of C-based filaments were first identified in 1890, and were studied in detail
in the 1960’s and 1970’s, due to their role in poisoning catalysts.
 VLS mechanism or VLS growth

• CVD of SiCl4 or SiI2

• Reactant adsorbs and

decomposes on surface of Au
‘dot’s

• Si goes into solution in Au and

Au melts

• Vapor is supersaturated so
liquid is supersaturated so Si
precipitates

• Si can grow only from solution

in Au, so crystal diameter is
limited by dot size
 How to Provide Vapors
wth is catalyzed by a solid catalyst particle

REVIEW
talyst droplet. Whether wire growth proceeds
mechanism depends on catalyst material and
t is often difficult to judge and even more
Si nanowire growth
which of the two growth modes actually
ence of in situ characterization methods, only
process
e catalyst particle can give a hint. It is often
https://www.youtube
re growth the radius R of the catalyst droplet
offfiffithe
r ffiffiffiffi"ffiffinanowire.
ffi. ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiOne ffiffi can easily derive that, in
ffiffiffiffiffi#
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1 1 " ðs ls =s l Þ , with sl and sls being 2 [8]

gkpdLy0o
of the liquid catalyst and the interface tension
nterface, respectively. But the most remark-
VLS mechanism is that it works well over a
from wires several hundreds of micrometers
owires of just a few nanometers in diameter
ig. 8).

owth Techniques

e details of wire and nanowire growth, a short

erent growth methods is given below.

r Deposition (CVD)
, CVD derives its name from the way the
wire growth, is provided. In CVD, a volatile
ecursor, such as silane, SiH4, or silicon
serves as the silicon source. It is transported
urface at which the precursor reacts, and is
tituents as depicted in Figure 3a. Originally,
for the deposition of high-purity films.
Figure 3. Schematics of experimental setups for silicon nanowire growth.
h as gold particles, however, were found to a) CVD, b) annealing in reactive atmosphere, c) evaporation of SiO,
owth of silicon, that is, the growth of silicon d) MBE, e) laser ablation, and f) solution-based growth. (Schmidt)
epitaxial growth of silicon wires, with the
"2 þ3 "1 [9,10]
 Nanowires: Why Au catalysts?
Part of the answer: because the Au-Si system is a simple eutectic system,
and the eutectic temperature is very low, the VLS mechanism can operate at
low temperatures.
 liquidus
L

b+L

a+L

a+b

37
 Nanowire Growth
- Vapor-Liquid-Solid (VLS) Growth -

Wagner and Ellis, Appl. Phys. Lett. 4, 89 (1964)

38
 But Au is a Deep Level Trap
- It kills Si device performance -

Hopkins and Rohatgi, J. Crystal Growth (1986).

 Other Catalysts for Si Wire

Tm,Si=1410C

Known catalysts :
Pt, Ni, Al, Cu, etc

Atwater et al, Appl. Phys. Lett. 91, 103110 (2007)