Phase Equilibrium and Diagrams
• Phenomenon
– Ice melts into water at 0°C and
evaporates into gas at 100°C
– Al becomes liquid at 660°C
– Fe is BCC-structured (a-Fe)
below 912°C, but FCC-
structured (g-Fe) between 912
and 1394°C
– Al-Cu alloys can be
strengthened by precipitation
– Fe can be hardened by
quenching
MCEN90014: Materials Dr. K. Xia
Phase Equilibrium and Diagrams
Concepts and Definitions
• Alloy: not pure metal
– Al-4 wt% Cu alloy
– Fe- 0.1 wt% C alloy (a carbon
steel)
• Component: elementary
constituent of an alloy
– Al and Cu
– Fe and C
• System: alloys of the same
components with various
compositions
– Al-Cu system (a series of alloys
containing Al and Cu)
– Fe-C system
MCEN90014: Materials Dr. K. Xia
• Quantitative description
– equilibrium phase diagrams
– what phases are present and
how much of each phase at a
certain temperature and
alloying composition
• Equilibrium microstructures
– prediction from phase diagrams
– in typical systems
Reading: 9.1-9.9 (5th ed) 9.1-9.13 (6th ed)
1
• Phase: a homogeneous portion of
a system that has uniform physical
and/or chemical characteristics
(i.e. you cannot tell any one part
from any other part)
– chocolate bar with nuts
(chocolate + nut)
– ice water: ice + water
– oil in water: oil + water
– too much sugar in coffee (solid
sugar + sweet liquid coffee)
– Pearlite steel: a-Fe + Fe3C
– precipitation strengthened Al-
Cu alloy: Al + fine particles of
CuAl2
A system may contain only one phase or multiple
phases depending on the composition,
temperature, pressure and other conditions
2
1
 Phase Equilibrium and Diagrams
• Phase equilibrium – when a system is at
– a system is at equilibrium if the equilibrium, it attains a
number of phases and their Concept of minimum energy state (with
amounts do not change with free energy minimum free energy) and is
will be taught
time in thermo- said to be stable
• Chamber set and kept at dynamics – when a system at equilibrium
0°C at all times. What will
contains multiple phases, the
happen if each of the
following items is placed in phases are at equilibrium with
it? each other or phase equilibrium
– water at room T is reached
» water drop to 0°C • Phase equilibrium may be
(but still liquid) destroyed if conditions are
– ice at –10°C changed, most notably by
» ice rise to 0°C (but temperature changes
still solid) – liquid water changes into
– ice water at 0°C vapour if T is raised to ≥ 100°C
» the solid/liquid – Fe changes from BCC to FCC
mixture would when T is raised to ≥ 912°C
remain at 0°C

MCEN90014: Materials Dr. K. Xia 3

Phase Equilibrium and Diagrams

• Metastable state • Microstructure
– an observed state of a system – in addition to the number of
does not necessarily indicate phases and the amount of each
that the system has attained phase, microstructure tells the
the lowest energy possible, e.g. shape and size of each phase
diamond (C) has higher free and their distribution in space
energy than graphite (C) at
ambient conditions, but do not
lose your sleep as your
precious diamond is not going
to become cheap pencil lead A: host A: host A: host
overnight (the energy barrier is B: dissolved B: fine B: lamellae
too high for the change to take in A particles

place at any detectable rate)! – microstructure is important as it

We will discuss the topic of phase
transformation in more details later
often determines the properties
of materials (e.g. nominally
same materials with same
compositions and phases may
have very different strengths)

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 Phase Equilibrium and Diagrams
Equilibrium Phase Diagrams Binary isomorphous systems
• What phases are there under a • involving two components
certain conditions ( e.g. T) for a • at ambient atmosphere (P = 1 atm)
given alloy (i.e. composition) and • two axes are needed: T and C
what changes will occur if T is pure Cu pure Ni
altered (phase transformation)?
Other
• For pure metals (i.e. one conditions liquid field
Tm of
pure
component system) such as Ni
pressure are a + L two
– Al (melting T = 660°C) usually phase field
• solid (FCC): <660°C constant lower limit of
the liquid field
• liquid: > 660°C
upper limit of
– Fe (melting T = 1538°C) the solid field
• solid a (BCC): < 912°C
• solid g (FCC): 912-1394°C alpha field
• solid d (BCC): 1394-1538°C a : solid solution of
• liquid: > 1538°C Tm of Cu and Ni (FCC)
pure Cu
A diagram is necessary if a system
consists of 2 or more components
MCEN90014: Materials Dr. K. Xia 5

Phase Equilibrium and Diagrams

• Phase present • Compositions of phases present
– A: Cu-60Ni at 1100°C – A: a = 40 wt% Cu-60 wt%Ni
– B: Cu-35Ni at 1250°C (same as the alloy composition)
The T and composition define the point in the diagram – B:
CL • L = 68.5 wt% Cu-31.5 wt%Ni
Ca • a = 57.5 wt% Cu-42.5 wt%Ni
CL and Ca are different from the alloy composition Co

a mixture of
a and L

100% a phase
IMSE:
Phase
Diagrams

MCEN90014: Materials Dr. K. Xia 6

3
 Phase Equilibrium and Diagrams
• Amounts of phases present
– A: 100% a (single phase)
– B: using the lever law
S C − Co 42.5 − 35 mass fraction
WL = = α = = 68% of liquid
R + S Cα − C L 42.5 − 31.5
R C − CL 35 − 31.5
Wα = = o = = 32% mass fraction Wα + WL = 100%
R + S Cα − C L 42.5 − 31.5 of a
€ If there are 100 g of alloy B, the amount of
liquid phase at 1250°C is 68 g and that of a is
€ 32 g. €
Cu
Total amount of Cu in liquid = CL x 68 g =
68.5% x 68 g = 46.6 g
Total amount of Cu in a = Ca
Cu
x 32 g = 57.5%
x 32 g = 18.4 g
Total amount of Cu in alloy B is 46.6 + 18.4 =
65 g
This is the same if we calculate the total
amount of Cu using 100 g x 65% = 65 g
Referring to example 9.1

MCEN90014: Materials Dr. K. Xia 7

Phase Equilibrium and Diagrams

• Microstructures very slow cooling, i.e. the system is given as much time Diffusion is
as needed to reach equilibrium at each temperature necessary
– following equilibrium which is a
cooling of Cu-35Ni from slow process
To
~1300°C
starting How can such a change of
• To to T1: cooling of temperature composition be realised in a?
liquid (35Ni)
T1
• just under T1: a
T2
(~46Ni) nucleation
starts (L: ~35Ni)
T3
• at T2:
L: 32Ni T4
a: 43Ni
using Wa: 27.3%
lever law WL: 72.7%
• at T3: solidification
finishes (100% a:
35Ni)
alloy
• T3 to T4: cooling of a
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 Phase Equilibrium and Diagrams
• Microstructures cooling is fast, allowing little diffusion in a (diffusion in liquid is
taken to be still fast enough to allow equilibrium to be reached)
– following nonequilibrium
cooling
To
• To to T1: cooling of liquid
The core (35Ni) average
with 46Ni composition
• just under T1: a (~46Ni) of a
T1
The nucleation starts (L:
solidifying ~35Ni) a average: 46Ni T2
layer with
40Ni • at T2: L (29Ni) and a:
T3
The 40Ni a average: 42Ni
T4
solidifying
layer with
• at T 3: L (24Ni) and a:
35Ni 35Ni a average: 38Ni
T5
The • at T4: L (21Ni) and a:
solidifying 31Ni a average: 35Ni
layer with
31Ni • T4 to T5: cooling of a solidification
with an average 35Ni finishes at T4,
Segregation/ (consisting of layers of not T3 !
coring different compositions) alloy
Can the extent of segregation be reduced?
MCEN90014: Materials Dr. K. Xia 9

Phase Equilibrium and Diagrams

Binary eutectic systems

Eutectic isotherm

a : solid Eutectic or b : solid

solution invariant point solution
based on solubility limit (how much based on
Cu with solute can be dissolved in Ag with
dissolved the host). e.g. at 600°C, Cu dissolved
Ag can dissolve a maximum of Cu
~3 wt% Ag

~3

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 Phase Equilibrium and Diagrams

Eutectic or
invariant point

Eutectic isotherm
L (CE) = a (Ca E) + b (Cb E)
Eutectic
reaction

The eutectic reaction takes place at a constant temperature (TE = 779°C).

At the end of the reaction, all liquid has become a and b and their relative
amounts can be calculated by using the lever law (Wa = 19.3/83.2 = 23.2%
and Wb = 76.8%).

Alloy: Cu-71.9Ag

MCEN90014: Materials Dr. K. Xia 11

Phase Equilibrium and Diagrams

Examples 9.2 and
Homework: do the same for alloy A (20Sn) at 250°C, alloy D (90Sn) at
9.3 200°C, and alloy X (50Sn) at TE just before the eutectic reaction and just
Pb-40Sn alloy at after the completion of the eutectic reaction, respectively.
150°C
• a + b two
phases
• Ca: Pb-10Sn A
• Cb: Pb-98Sn
• Wa = 58/88 = D
TE = 183°C
66%
18.3 X 61.9 97.8
• Wb: = 30/88 =
34%
Hint: just before the
eutectic reaction
there are two phases,
L + a; just after the
reaction there are
two phases, a + b.

MCEN90014: Materials Dr. K. Xia 12

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 Phase Equilibrium and Diagrams
• Microstructures following
equilibrium cooling
– alloy C1 T1
• T > T1: 100% L T2
• at T1: solidification of a
starts
• at T2 solidification of a
finishes
• < T2: 100% a

MCEN90014: Materials Dr. K. Xia 13

Phase Equilibrium and Diagrams

– alloy C2
• T > T1: 100% L Composition of L
• at T1: solidification of a
starts T1
• at T2 solidification of a
finishes
• at T3: precipitation of b T2
starts (in the a matrix)
• < T3: Wb ­ as T ¯ (using T3
the lever law)
• < T4: no more change

Composition
of a
Compositions of b
T4 are out of range

MCEN90014: Materials Dr. K. Xia 14

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 Phase Equilibrium and Diagrams
– alloy C3
• T > TE: 100% L The relative amount of each phase at
a particular temperature can be
• just reach TE: calculated by using the lever law
co-solidification
of a + b starts
• at TE: eutectic
reaction
continues until
all L has
become the
alternating
a and b eutectic TE
lamellae structure
• < TE: Ca and
Cb change
along the
respective
solvus lines

MCEN90014: Materials Dr. K. Xia 15

Phase Equilibrium and Diagrams

– alloy C4 HW: do the same analysis for alloy Pb-90Sn

Just before TE: At T1, a

a+L solidification
starts
Wa = 21.9/43.6 = 50.2%
WL = 21.7/43.6 = 49.8%
T1

at TE: TE
18.3 61.9 97.8
L (61.9) =
a (18.3)+ b
(97.8)
eutectic structure

Just after TE:

a+b
HW: what happens during This microstructure consists
Wa = 57.8/79.5 = 72.7%
cooling from TE to room of primary a and a eutectic a
Wb = 21.7/79.5 = 27.3% temperature? + b (lamellar) structure

HW: how much of the eutectic

structure in the final material?

MCEN90014: Materials Dr. K. Xia 16

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 Phase Equilibrium and Diagrams
Homework:
plot the
microstructure
at TR
Alloy Pb-40Sn: 100 g

Primary a (Pb- just above Liquid (Pb-

18.3Sn): 50.2 g TE 61.9Sn): 49.8 g
TE
18.3 61.9 97.8
Primary a (Pb- just Eutectic (Pb-
18.3Sn): 50.2 g below 61.9Sn): 49.8 g Eutectic a (Pb- Eutectic b (Pb-
TE 18.3Sn): 22.5 g
(45.2%)
+ 97.8Sn): 27.3 g
(54.8%)

TR
Primary a (Pb- Secondary b Eutectic a (Pb- Eutectic b (Pb-
~3Sn): 42.1 g (Pb-~98Sn): 8.1 at TR ~3Sn): 18.9 g ~98Sn): 30.9 g
(83.9%) g (16.1%) (38%) (62%)

MCEN90014: Materials Dr. K. Xia 17

Phase Equilibrium and Diagrams

Binary systems with intermediate intermetallic compounds

Intermetallic
compound

MCEN90014: Materials Dr. K. Xia 18

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 Phase Equilibrium and Diagrams
Binary systems with intermediate phases and reactions Read 9.8 & 9.9 (5th ed),
9.12 & 9.13 (6th ed)

Intermediate solid solution

Peritectic reaction
d+L=e

Terminal solid solution

Eutectoid reaction

MCEN90014: Materials Dr. K. Xia d=g+e 19

Phase Equilibrium and Diagrams - Summary

Terminology Microstructure
• system • upon cooling from liquid to room
• component temperature
• phase • process
• microstructure – change of composition during
• equilibrium cooling
– change of amount of each
phase during cooling
Equilibrium phase diagram (binary)
• change of microstructure during
• fields: single phase, two phase cooling and the final microstructure
• tie lines
• phases present
• composition of each phase
• amount of each phase - the lever
law
• eutectic reaction
• segregation due to nonequilibrium
cooling
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