MSE561: Phase Transformations,

Kinetics, and Diffusion in Solids

4. Phase Equilibrium and Phase Diagrams

Yang Jiao

Materials Science & Engineering

School for Engineering of Matter, Transport and Energy
Arizona State University
Tempe, AZ 85287-6016

Lecture time T/Th 10:30 – 11:45 AM

https://asu.zoom.us/j/2759304275
 Topics Covered:

• Chemical potential and phase equilibrium

• Maxwell construction
• Si-Ge phase diagram
• Pb-Sn phase diagram (Eutectic phase diagram)
• Cu-Al phase diagram
• Fe-C phase diagram
 Condition for phase equilibrium

G_ice = G_water

What are the two phases that are in equilibrium in the

saturated sugar-water system on the right?

What determines phase equilibrium for an alloy?

3
 Condition for phase equilibrium

What determines phase equilibrium for an alloy?

4
 Condition for phase equilibrium

Separating into 2 phases lower the total free energy!

Phase separation stops (phase equilibrium is achieved)

when the chemical potential of the same type atoms in
different phase are the same!
5
 Condition for phase equilibrium

 A   A  B   B

The same type atoms have the same chemical potential

(molar free energy in mixture)!

6
Application to regular solutions

7
Construction of Phase Diagram --- Si-Ge

8
Construction of Phase Diagram --- Si-Ge

9
Phase diagrams display what phases exist as a function of temperature
and composition at fixed pressure (usually at 1 atm)

Example:
Liquidus
Silicon
germanium
phase diagram

Solidus

Question: In the Si – Ge phase diagram above:

Co-existence can occur over
What a range
phase(s) exist atofpoint
T inA?alloys, while
only occurs atWhata particular T inatpure
phase(s) exist metal!
point B and C?
What phase(s) exist at point D?
• 1) Germanium and silicon have melting points of 958 and 1430 oC,
respectively, and they form a continuous solid solution (totally
soluble, like Cu-Ni). Thermal analysis provides the following data:
• Alloy liquidus solidus
• (wt% Si) temp. (oC) temp. (oC)
• 20 1115 990
• 40 1227 1050
• 60 1315 1126
• 80 1370 1230

In practice, phase diagrams can be constructed based

on carefully collected and extrapolated themo data!
(Instead of doing free energy calculations)
Tie Line: The composition of each phase is given by the intersection of
the horizontal temperature line with the boundaries of each phase region.
This is shown in the figure.

The tie line in this solid solution phase diagram shows how the composition
of two separate phases can be found at 1200ºC.
 Phase Fraction
Definition: The fraction of the bulk material which exists as a given phase.
Example: A glass of ice water contains 25% ice by weight and 75% liquid by
weight
The phase fraction is determined using the lever rule. Think of the tie line as
a lever balanced on the vertical line which represents the overall composition.

L
L+ An illustration of using the
Temperature

Tie Line lever rule to determine the

weight fraction of solid and
 liquid.

Fs Fl
ws  w0
A wl w0 ws B
Phase fraction of liquid  Fl 
Weight Percent B
ws  wl
w0  wl
Fl Fs Phase fraction of solid  Fs 
ws  wl
 Deviation of lever rule
M  mS  mL

L
L+
0 (mS  mL )  S mS  L mL
Temperature

Tie Line


0  L  mL  S  0  mS
A wl
Fs w0
Fl w
s B
Weight Percent B
Liquid arm
Fl Fs

mL FL S  0 
 
mS FS 0  L 
Solid arm
Activity: In the silicon – germanium phase diagram, what are the weight
fractions of the solid and liquid present for the temperature of the tie line
shown (1200 C) and an overall composition of 30 wt. % Si?
Construction of Phase Diagram --- Pb-Sn

16
 Eutectic Alloys
Eutectic is Greek for “easily melted”, and a characteristic of eutectic alloys is
that their melting point is lower than the melting point of either component.
Evolution of microstructure along composition line A


 
L
L

T > 305 C 280 < T < 305 C 150 < T < 280 C T < 150 C
Evolution of microstructure along composition line A


 
L
L

T > 305 C 280 < T < 305 C 150 < T < 280 C T < 150 C
Evolution of microstructure along composition line A


 
L
L

T > 305 C 280 < T < 305 C 150 < T < 280 C T < 150 C
Evolution of microstructure along composition line A


 
L
L

T > 305 C 280 < T < 305 C 150 < T < 280 C T < 150 C
Evolution of microstructure along composition line C

L-S transition occur at a

single temperature as in pure
metal!
 Evolution of microstructure along composition line B

The Pb-Sn diagram has 3 single-phase regions: liquid, , and .

 The liquid is a homogeneous mixture of Pb and Sn.
 The  is a Pb-rich solid with a face centered cubic structure.
 The  is a Sn-rich solid with a body centered structure.
 Evolution of microstructure along composition line B

Question: 100g Pb-

Sn alloy with 40 wt
% Sn, find out
weight of Eutetic
The low-T microstructure
alpha?
composed both primary alpha
phase + Eutetic microstructure
 Engineering Application

With knowledge of phase diagrams and the effect of different phases on

the behavior of a material, an engineer can tailor a metal to suit the need of
a specific task.

Example: Al-Cu alloy: In the aircraft industry aluminum is one of the

primary structural materials. Pure Al is not strong enough for most
applications so copper is added in small quantities to strengthen it. The
copper form precipitates that block dislocation motion, which strengthens
the aluminum. Most Al alloys are 1 – 4 wt. % Cu because adding more Cu
increases the weight (Cu is denser than Al) and does not significantly
increase strength.
Steels: Typically Fe with 0.1 – 0.8 wt% C and other alloying elements
90 ％ of all metals used. Why? Strong, ductile, cheap ($500/ton);
properties can be varied widely by alloying & processing.

α: Nearly pure BCC

Fe; very soft
(Ferrite)

γ: FCC Fe with up
to 2% C dissolved
(Austenite)

: : High
temperature BCC
phase

Fe3C: hard, brittle

ceramic
Enlargement of Fe-C Phase Diagram
Schematically draw the evolution of the microstructure of Fe-C alloy as
T decreases from 1000C to 500C, with the following composition (wt %
of C)
(a) 0.5% of C (hypoeutectoid alloy)
(b) 0.76% of C (eutectoid alloy)
(d) 1.0% of C (hypereutectoid alloy)
 Topics Covered:

• Chemical potential and phase equilibrium

• Maxwell construction
• Si-Ge phase diagram
• Pb-Sn phase diagram (Eutectic phase diagram)
• Cu-Al phase diagram
• Fe-C phase diagram
Thank You!

Questions?

31
Evolution of microstructure along composition line C

L-S transition occur at a

single temperature as in pure
metal!