Review of

Phase Transformation
Diagrams

Binary Phase Diagrams

Solidification of alloy Co starts on

cooing at T1. The first solid formed has
a composition of Cs1 and the liquid
Co. On further cooling the solid
particles grow larger in size and change
their composition to Cs2 and then Co,
following the solidus whereas the liquid
decrease in volume and changes its
composition from Co to CL3 following
the liquidus. The solidification
completes at T3.

Temperature

The simplest type of binary phase

diagrams is the isomorphous system, in
which the two constituents form a
continuous solid solution over the
entire composition range. An example
is the Ni-Cu system.

1455C

liquid phase Solution of

Cu and Ni

T1
T2

Co
CL

T3 CL 2
3
1085C

Cu

CS
Co

2
phase (fcc) Solid solution
of Cu and Ni

Composition
L

CS

Ni

The simplest type of binary phase

diagrams is the isomorphous system, in
which the two constituents form a
continuous solid solution over the
entire composition range. An example
is the Ni-Cu system.

Temperature

Binary Phase Diagrams

liquid phase Solution of
Cu and Ni

T*

CL

Compositions of phases is determined

by the tie line
The relative fractions of the phases are
determined by the lever rule
1085C
W1

1455C
Co

CS

phase (fcc) Solid solution

of Cu and Ni

W2

L1

L2

Cu

Composition

Ni

Example
At temperature T1, alloy Co is in the dual phase region,

CL

comprising the liquid phase and the -phase.

CS
Co

(i) Determine the compositions of the two phases;

(ii) Determine the weight fractions of the two phases
Read from the tie line:
Liquid phase:Cu-30%Ni
-phase:
Cu-55%Ni

1455C
C0

WL =

Cs Co 55 50
=
= 0.2 = 20%
Cs CL 55 30

T1

W =

Co CL 50 30
=
= 0.8 = 80%
Cs CL 55 30

1085C

CS

or
W = 1 WL = 1 0.2 = 0.8 = 80%

CL

30%Ni
Cu

55%Ni
50%Ni

Ni

Cooling Curves

determination of Phase diagrams

II
1455C

1085C

Liquidus

(thermal arrest)

T1
Solidus

T2

I
T1

1085C

T2

II
Cu

I
%

III
Ni

Eutectic Systems
Pb-Sn phase diagram

Pb has a fcc structure and Sn has

a tetragonal structure. The
system has three phases: L, and
.

Liquid

300
Liquidus

Temperature

The Pb-Sn system is

characteristic of a valley in the
middle. Such system is known as
the Eutectic system. The
central point is the Eutectic
point and the transformation
though this point is called
Eutectic reaction: L+

350

250

Eutectic
point

+L

200

L+

150

solidus

100

phase: solid
solution of Sn
in fcc Pb

50
0

20

solvus

solvus

0 10
Pb
(Fcc)

phase: solid
solution of Pb in
tetragonal Sn

30

40

50

60

Wt%

70

80

90 100
Sn
(Tetra)

Solidification of Eutectic Systems

Pb-Sn phase diagram

The cooling curve of this alloy is

similar to cooling curve I shown in
slide 9.

350

II

III

Liquid

300

Temperature

Alloy I:
At point 1: Liquid
Solidification starts at liquidus
At point 2: L+
The amount with T
Solidification finishes at solidus
At point 3:
Precipitation starts at solvus
At point 4: +
Further cooling leads to formation
and growth of more precipitates
whereas Sn% in decreases
following the solvus.

250
200

2
3

150
4

100
50
0

0 10
Pb
(Fcc)

20

30

40

50

60

Wt%

70

80

90 100
Sn
(Tetra)

(1)

(a)

(2)

(3)

Precipitates in a Al-Si alloy;

(a) optical microscopy,
(b) scanning electron
microscopy of fracture surface

(4)

(b)

Solidification of Eutectic Systems

The cooling curve of this alloy is

similar to cooling curve II shown
in slide 9.

Pb-Sn phase diagram

350

III

II

Liquid

300

Temperature

Alloy II:
At point 1: Liquid
Solidification starts at eutectic
point (where liquidus and solidus
join)
At point 2: L(+) (eutectic
reaction)
The amounts of and increase
in proportion with time.
Solidification finishes at the same
temperature.
At point 3: +
Further cooling leads to the
depletion of Sn in and the
depletion of Pb in .

250
200

150
100

50
0

0 10
Pb
(Fcc)

20

30

40

50

60

Wt%

70

80

90 100
Sn
(Tetra)

(1)

(2)

L
L

Nucleation of colonies
of and laminates

(3)

Pb-Sn eutectic

Eutectic structure of
intimate mix of and to
minimise diffusion path

Solidification of Eutectic Systems

The cooling curve of this alloy is a

combination of the two cooling curves
shown in slide 9.

Pb-Sn phase diagram

350

III

300

Temperature

Alloy III:
At point 1: Liquid
Solidification starts at liquidus
At point 2: LL+ (pre-eutectic )
The amount with T
At point 3: L (+) (eutectic
reaction)
Solidification finishes at the eutectic
temperature
At point 4: + (pre-eutectic +
(+) eutectic mixture)
Further cooling leads to the depletion
of Sn in and the depletion of Pb in
.

II

Liquid

250
200

150

100
50
0

0 10
Pb
(Fcc)

20

30

40

50

60

Wt%

70

80

90 100
Sn
(Tetra)

(1)

Cooling curve

(2)

(3)

(3)

Cu-Ag alloy

Pr
e-

eu

Eut

tec
tic

Eutectic laminate
of and

Solidification of Eutectic Systems

350

300
Can you describe the
solidification process of alloy IV,
including microstructure
evolution, morphology of phases
and cooling curve?

III

II

IV

Liquid

250
200

150
100
50

0
Pb

Sn

Hypoeutectic

Hypereutectic

Non-Equilibrium Solidification
Some transformations do not cause changes in composition, such as the
solidification of a pure metal, whereas some other do, such as the
solidification of an alloy into a solid solution. The former is known as
congruent
transformation
and
the
latter
incongruent
transformations. Congruent transformations are cooling rate insensitive
and incongruent transformations are cooling rate sensitive they rely on
interdiffusion to proceed. Solidification under a fast cooling rate, where
diffusion is insufficient to homogenise the composition simultaneously
during the process is known as the non-equilibrium solidification.
A common consequence of non-equilibrium solidification is coring.

Coring
Alloy Co starts solidification at T1. The first
solid formed has composition Cs1. On
further cooling to T2, an outer shell of
composition Cs2 is formed surrounding
Cs1. Due to inadequate diffusion on fast
cooling, a composition difference is created.
The average composition of the solid
composite at T2 is, thus, somewhere
between Cs1 and Cs2: Cs2*. The same
situation continues throughout the process.
Under equilibrium condition solidification
completes at T3. However, under nonequilibrium
condition,
the
average
composition of solid at T3 is Cs3* <Co,
indicating that solidification is not completed
yet. Solidification actually ends when the
average composition of solid equals Co, i.e.,
at T4.

Equilibrium
solidus
Co
T1 (start of solidification)

Cs1
Cs

T2

2
Cs
*
2
Cs
*
3

T3 (end of solidification
under equilibrium)
T4 (actual end of
solidification)

Effective
solidus

%B

Non-equilibrium solidification lowers

effective melting temperature.

Coring
T1
T2

Cs1

L
Equilibrium
solidus

Cs1

Co

Cs2
T3

Average solid
composition: Cs2*

T1 (start of solidification)

Cs1
Cs

T2

2
Cs
*
2

Average solid
composition: Cs3*

Cs
*
3

T3 (end of solidification
under equilibrium)
T4 (actual end of
solidification)

Effective
solidus

T4

Average solid
composition:
Co

A
%B
The cored structure: composition segregation,
enrichment of high-Tm constituent in the core

Coring in Eutectic Systems

co

According to the lever rule, the

weight fraction of the eutectic
products can be computed as:

Under equilibrium condition:

Weut

cb
=
d b

Under non-equilibrium condition:

*
eut

ca
=
d a

*
Weut
> Weut

Coring leads to increase of weight fraction

of eutectic products

Constitutional Supercooling
Co
S
C

L
CS

CL

CL
Co

CS
T

x
Tm

%B

T
S
Supercooling window caused by
rising Tm, resulting in unstable
interface

Dendrite Structure of Metals

A consequence of constitutional supercooling and destabilisation of solid-liquid interface is
the formation of dendritic structure, as commonly found in alloy castings. In such structure,
gaps between dendrites and between dentitic fingers are regions rich of low-melting
temperature phases and impurities. Dendritic branches themselves are often cored, too.
This often require post-casting heat treatment to homogenise the structure.