Phase Equilibrium and Diagrams!

Phenomenon!

Quantitative description!

Ice melts into water at 0C and

evaporates into gas at 100C!
Al becomes liquid at 660C!
Fe is BCC-structured (-Fe)
below 912C, but FCCstructured (-Fe) between 912
and 1394C!
Al-Cu alloys can be
strengthened by precipitation!
Fe can be hardened by
quenching!

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)

MCEN90014: Materials

!Dr. K. Xia!

!1!

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!

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: -Fe + Fe3C!
precipitation strengthened AlCu 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

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!2!

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
minimum energy state (with
of
amounts do not change with Concept
minimum free energy) and is
free energy
time!
will be taught said to be stable!
in thermo e.g. ice in water at 0C!
dynamics
when a system at equilibrium
if no heat exchange
contains multiple phases, the
with the environment!
phases are at equilibrium with
dynamic: any ice
each other or phase equilibrium
melting will absorb heat
is reached!
and cause freezing of
Phase equilibrium may be
water at the same time,
destroyed if conditions are
i.e. although the total
changed, most notably by
amount of ice does not
change, the melting
temperature changes!
and freezing processes
liquid water changes into
proceed at the same
vapour if T is raised to 100C!
rate to keep the

Fe changes from BCC to FCC

equilibrium!
when T is raised to 912C!
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!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

in A

particles

too high for the change to take
place at any detectable rate)!!
microstructure is important as it

We will discuss the topic of phase

transformation in more details later

MCEN90014: Materials

!Dr. K. Xia!

often determines the properties

of materials (e.g. nominally same
materials with same
compositions and phases may
have very different strengths)!
!

!4!

Phase Equilibrium and Diagrams!

Binary isomorphous systems!

involving two components!
at ambient atmosphere (P = 1 atm)!
two axes are needed: T and C!

Equilibrium Phase Diagrams!

What phases are there under a

certain conditions ( e.g. T) for a
given alloy (i.e. composition) and
what changes will occur if T is
pure Cu

altered (phase transformation)?!
Other
For pure metals (i.e. one
conditions
component system)!
such as
pressure are
Al (melting T = 660C)! usually
solid (FCC): <660C! constant

liquid: > 660C!
Fe (melting T = 1538C)!
solid (BCC): < 912C!
solid (FCC): 912-1394C!
solid (BCC): 1394-1538C!
Tm of
liquid: > 1538C!

Tm of
pure
Ni

liquid field

+ L two
phase field

lower limit of
the liquid field

upper limit of
the solid field

alpha field

: solid solution of
Cu and Ni (FCC)

pure Cu

A diagram is necessary if a system

consists of 2 or more components

MCEN90014: Materials

pure Ni

!Dr. K. Xia!

!5!

Phase Equilibrium and Diagrams!

Phase present!
A: Cu-60Ni at 1100C!
B: Cu-35Ni at 1250C!
The T and composition define the point in the diagram

Compositions of phases present!

A: = 40 wt% Cu-60 wt%Ni
(same as the alloy composition)!
B:!
CL
L = 68.5 wt% Cu-31.5 wt%Ni!
C
= 57.5 wt% Cu-42.5 wt%Ni!
CL and C are different from the alloy composition Co

a mixture of
and L

100% phase

IMSE:
Phase
Diagrams

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!Dr. K. Xia!

!6!

Phase Equilibrium and Diagrams!

Amounts of phases present!

A: 100% (single phase)!
B: using the lever law!
S
C Co
42.5 35
=
=
= 68%
R + S C C L 42.5 31.5
R
C CL
35 31.5
W =
= o
=
= 32%
R + S C C L 42.5 31.5
WL =

mass fraction
of liquid

W + WL = 100%

mass fraction
of

If there are 100 g of alloy B, the amount of

liquid phase at 1250C is 68 g and that of is
32 g.

Total amount of Cu in liquid = CLCu x 68 g =

68.5% x 68 g = 46.6 g

Total amount of Cu in = CCu 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

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Phase Equilibrium and Diagrams!

very slow cooling, i.e. the system is given as much time
Diffusion is
Microstructures!
as needed to reach equilibrium at each temperature

necessary
following equilibrium
which is a
cooling of Cu-35Ni from
slow process

To

~1300C!
How can such a change of
To to T1: cooling of starting
temperature

composition be realised in ?

liquid (35Ni)!
T1

just under T1:
T2

(~46Ni) nucleation
starts (L: ~35Ni)!
T3

at T2:!
L: 32Ni!
T4

: 43Ni!
W: 27.3%!
using
lever law
W : 72.7%!
L
at T3: solidification
finishes (100% :
35Ni)!
alloy

T3 to T4: cooling of !

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Phase Equilibrium and Diagrams!

cooling is fast, allowing little diffusion in (diffusion in liquid is
Microstructures!
taken to be still fast enough to allow equilibrium to be reached)

following nonequilibrium
cooling!
To

To to T1: cooling of liquid
The core
average
(35Ni)!
with 46Ni

composition
just under T1: (~46Ni)
of

T1

nucleation starts (L:
The
solidifying
~35Ni)! average: 46Ni

T2

layer with
at T2: L (29Ni) and :
40Ni

T3

40Ni! average: 42Ni

The
T4

solidifying
at T3: L (24Ni) and :
layer with
35Ni! average: 38Ni

35Ni

T5

at T4: L (21Ni) and :

The
solidifying
31Ni! average: 35Ni

layer with
31Ni

T4 to T5: cooling of
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?

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!
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!9!

Phase Equilibrium and Diagrams!

Binary eutectic systems!

Eutectic isotherm

: solid
solution
based on
Cu with
dissolved
Ag

: solid
solution
based on
Ag with
dissolved
Cu

Eutectic or
invariant point

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

~3

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Phase Equilibrium and Diagrams!

Eutectic or
invariant point

Eutectic isotherm

L (CE) = (C E) + (C E)

Eutectic
reaction

The eutectic reaction takes place at a constant temperature (TE = 779C).
At the end of the reaction, all liquid has become and and their relative
amounts can be calculated by using the lever law (W=19.3/83.2 = 23.2%
and W = 76.8%).

Alloy: Cu-71.9Ag

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!11!

Phase Equilibrium and Diagrams!

Examples 9.2 and
9.3!

Pb-40Sn alloy at
150C!
+ two
phases!
C: Pb-10Sn!
C: Pb-98Sn!
W = 58/88 =
66%!
W: = 30/88 =
34%!

Homework: do the same for alloy A (20Sn) at 250C, alloy D (90Sn) at

200C, and alloy X (50Sn) at TE just before the eutectic reaction and just
after the completion of the eutectic reaction, respectively.

A
D

TE = 183C

18.3

X
61.9

97.8

Hint: just before the

eutectic reaction
there are two phases,
L + ; just after the
reaction there are
two phases, + .

MCEN90014: Materials

!Dr. K. Xia!

!12!

Phase Equilibrium and Diagrams!

Microstructures following
equilibrium cooling!
alloy C1!
T > T1: 100% L!
at T1: solidification of
starts!
at T2 solidification of
finishes!
< T2: 100% !

MCEN90014: Materials

T1

T2

!Dr. K. Xia!

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Phase Equilibrium and Diagrams!

alloy C2!
T > T1: 100% L!
at T1: solidification of
starts!
at T2 solidification of
finishes!
at T3: precipitation of
starts (in the matrix)!
< T3: W as T (using
the lever law)!
< T4: no more change!

Composition of L

T1

T2

T3

Composition
of

Compositions of
are out of range

T4

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!14!

Phase Equilibrium and Diagrams!

alloy C3!
T > TE: 100% L!
just reach TE:
co-solidification
of + starts!
at TE: eutectic
reaction
continues until
all L has
become the
alternating
eutectic
and
structure!
lamellae

< TE: C and
C change
along the
respective
solvus lines!

MCEN90014: Materials

The relative amount of each phase at

a particular temperature can be
calculated by using the lever law

TE

!Dr. K. Xia!

!15!

Phase Equilibrium and Diagrams!

alloy C4!

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

Just before TE:

At T1,
solidification
starts

+ L

W = 21.9/43.6 = 50.2%

T1

WL = 21.7/43.6 = 49.8%

at TE:

TE

18.3

L (61.9) =
(18.3)+
(97.8)

61.9

97.8

eutectic structure

Just after TE:

+

W = 57.8/79.5 = 72.7%

W = 21.7/79.5 = 27.3%

This microstructure consists

of primary and a eutectic
+ (lamellar) structure

HW: what happens during

cooling from TE to room
temperature?

HW: how much of the eutectic

structure in the final material?

MCEN90014: Materials

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!16!

Phase Equilibrium and Diagrams!

Homework:
plot the
microstructure
at TR

Alloy Pb-40Sn: 100 g

just above
TE

Primary
(Pb-18.3Sn): 50.2 g

TE

Primary
(Pb-18.3Sn): 50.2 g

18.3

just
below
TE

Liquid
(Pb-61.9Sn): 49.8 g

61.9

Eutectic
(Pb-61.9Sn):
49.8 g

97.8

Eutectic
(Pb-18.3Sn):
22.5 g (45.2%)

Eutectic
(Pb-97.8Sn):
27.3 g (54.8%)

TR

Primary (Pb~3Sn): 42.1 g
(83.9%)

Secondary (Pb~98Sn): 8.1 g

(16.1%)

MCEN90014: Materials

at TR

Eutectic (Pb~3Sn): 18.9 g

(38%)

!Dr. K. Xia!

Eutectic (Pb~98Sn): 30.9 g

(62%)

!17!

!18!

Phase Equilibrium and Diagrams!

Binary systems with intermediate intermetallic compounds!

Intermetallic
compound

MCEN90014: Materials

!Dr. K. Xia!

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

+ L =

Terminal solid solution

Eutectoid reaction

MCEN90014: Materials

!Dr. K. Xia!

= +
!

!19!

Phase Equilibrium and Diagrams - Summary!

Terminology!
system!
component!
phase!
microstructure!
equilibrium!
Equilibrium phase diagram (binary)!
fields: single phase, two phase!
tie lines!
phases present!
composition of each phase!
amount of each phase - the lever
law!
eutectic reaction!
segregation due to nonequilibrium
cooling!
MCEN90014: Materials

!Dr. K. Xia!

Microstructure!
upon cooling from liquid to room
temperature!
process!
change of composition during
cooling!
change of amount of each
phase during cooling!
change of microstructure during
cooling and the final microstructure!

!20!

10