❑ Binary Phase Diagrams

❑ Classification of Binary Phase Diagrams

❑ Binary (Isomorphous) Phase Diagrams
❑ What is a Solid Solution
❑ Hume-Rothery Rules
❑ Lever Rule
❑ Examples
❑ Binary Eutectic Phase Diagrams
❑ Lever Rule and Examples
2 COMPONENT (BINARY) PHASE DIAGRAMS
Temperature (T)

Temperature (T)

Gas

Liquid

Solid

A
2 COMPONENT (BINARY) PHASE DIAGRAMS

Temperature (T)

Gas

Liquid

Solid

1 atm
A
2 COMPONENT (BINARY) PHASE DIAGRAMS

SLICE TAKEN AT 1 atm constant pressure

Liquid (L)
TB
TA
L+A L+B

Te

A+B

100 % A 100 % B
%B➔
Classification of Binary Phase Diagrams (1)

Liquid Liquid (L)

TB
L+A L+B TA
L+A L+B
A+B
Te
Liquid is composed of both A and B
A+B

100 % A %B➔ 100 % B

Classification of Binary Phase Diagrams (2)

TB
Liquid Liquid
L+A
TA
L+B
L+β
L+α
α+β β
α Teutectic
Partial Solubility of A and B
within each other α+β
Liquid is composed of both α and β

Both α and β composed of A + B

100 % A %B➔ 100 % B
EUTECTIC TYPE WITH PARTIAL SOLUBILITY
Classification of Binary Phase Diagrams (3)

Liquid
Liquid is composed of both A and B TB
α is composed of A + B
Liquid + α

ISOMORPHOUS
TA
Solid Solution (α)

100 % A 100 % B
BINARY ISOMORPHOUS PHASE DIAGRAMS

Component 1 ➔ A

Component 2 ➔ B Liquid
TB
Melting Point A ➔ TA (C)
Melting Point B ➔ TB (C)

α : Solid solution
composed of A and B
TA
Solidus line
Solid (α)
Liquidus line

A Composition (wt % ) B
wt % B 0 20 40 60 80 100
wt % A 100 80 60 40 20 0
SOLID SOLUTION:a solution as a homogeneous mixture in which the atoms or molecules of
one substance are dispersed at random into an other substance
When foreign atoms are incorporated into a crystal structure, whether in
substitutional or interstitial sites, the resulting phase is a solid solution of the
matrix material (solvent) and the foreign atoms (solute)

A A A A (1)
A A

A A A A

Component 1 (A) “Substitutional Solid Solution”

B B B B (2)

B B B B

B B B B

“Interstitial Solid Solution”

Component 2 (B)
 Hume-Rothery Rules

Substitutional Solid Solution Rules

1. The atomic radii of the solute and solvent atoms must differ by no
more than 15%
2. The crystal structures of solute and solvent must match.
William Hume – Rothery
3. Complete solubility occurs when the solvent and solute
1899–1968
Oxford University have the same valency. A metal will dissolve a metal of
higher valency to a greater extent than one of lower valency.
4. The solute and solvent should have similar electronegativity.
If the electronegativity difference is too great, the metals will
tend to form intermetallic compounds instead of solid
solutions.

Interstitial Solid Solution Rules

1. Solute atoms must be smaller than the interstitial sites in the solvent lattice.
2. The solute and solvent should have similar electronegativity.
TYPES OF SOLID SOLUBILITY

Unlimited Solid Solubility:

Solute and solvent are mutually soluble at all concentrations, e.g., Cu-Ni system

Meets the requirements of the Hume-Rothery Rules

Result is a “single phase alloy”

Limited or Partial Solid Solubility:

There is a limit to how much of the solute can dissolve in the solvent before “saturation” is
reached, e.g., Pb-Sn and most other systems

Does not meet the requirements of the Hume-Rothery Rules

Results in a “multi-phase alloy”

Ionic Radius of Some Important Ions
 Complete Solid Solution
(NiO-MgO system)

RNi : 0.69 Å RMg : 0.65 Å

 Partial Solid Solution
(MgO-CaO system)

RMg : 0.65 Å RCa : 0.99 Å

 1 All Liquid
L TB

2 Liquid +
Crystallites
of SS (α)

TA
3 Polycrystalline
α Solid (α)

A Composition (wt % ) B

A A A A A B A A B B A B B B B B

A A A B B B B A B B B B

A A A A B A A A B A B B B B B B
HOMEWORK : APPLY GIBBS PHASE RULE FOR ALL THE POINTS GIVEN
IN THE DIAGRAM
F=C–P+1
L
1 TB

4
TA
Solid (α)
5

A Composition (wt % ) B
0 20 40 60 80 100
100 80 60 40 20 0
TIE LINE AND LEVER RULE
The Composition of α (C0):

60 wt. % B - 40 wt. % A
L
Tie Line TB

L+α
TA

α R S

A CL C0 Cα B

0 20 40 60 80 100
100 80 60 40 20 0
COOLING TEMPERATURE : T1

100 % Liquid

The composition of the alloy is X0

Alloy of composition (xo) originally liquid at temperature T1, is cooled, it remains liquid until the
temperature reaches the liquidus temperature at point 2. At this temperature T2, the first particle of
solid appears.
COOLING TEMPERATURE : T2

The composition of liquid is x0

The composition of solid is x2’

At this temperature T2, the first particle of solid appears. This solid does not have the
same composition as the parent liquid. The composition of the first solid formed at T2 is
found by constructing an isothermal line from 2 to 2’ (TIE LINE)
COOLING TEMPERATURE : T3

x3’ – x0
WL = x 100
x3’ – x3

x0 – x3
WS = x 100
x3’ – x3

WS < WL

Upon further cooling to T3, the composition of the liquid has shifted to the left along
the liquidus to x3, and the composition of the solid has shifted to the left along the
solidus to x3' because at T3, the only liquid and solid compositions that can be in
equilibrium with one another are x3 and x3' respectively.
COOLING TEMPERATURE : T4

x4’ – x0
WL = x 100
x4’ – x4

x0 – x4
WS = x 100
x4’ – x4

WS > WL
COOLING TEMPERATURE : T5

The solid Composition X0

The liquid composition X5

As the temperature approaches the solidus temperature T5, the solid composition
approaches xo and the last quantity of liquid of composition x5 freezes.
COOLING TEMPERATURE : T6

The solid composition X0

100 % SOLID SOLUTION (α)

An Example of Equilibrium Crystallization From a Melt

1
POINT – 1

100 % Liquid composed of

(30 % Ca, 70 % A)
An Example of Equilibrium Crystallization From a Melt

POINT – 2

100 % Liquid composed of

2
(30 % Ca, 70 % A)

Ppm % α composed of

(72 % Ca, 28 Na)

4
An Example of Equilibrium Melting of a Material

POINT – 2

100 % Solid (SS) composed of

(60 % Ca, 30 % A)

2 Ppm % liquid composed of

(16 % Ca, 84 % Na)

1
EXAMPLE

T1

Temperature Phase Proportions Phases (%) % Composition of Phases

22 units melt (L) 100 % MgO 40

T1 NiO 60
ε units crystals (SS) ε MgO 63
NiO 37
EXAMPLE

T2

Temperature Phase Proportions Phases (%) % Composition of Phases

13 units melt (L) 56.5 % MgO 30

T2 NiO 70
10 units crystals (SS) 43.5 MgO 53
NiO 47
Total : 23
EXAMPLE

T3

Temperature Phase Proportions Phases (%) % Composition of Phases

ε units melt (L) ε MgO 20

T2 NiO 80
20 units crystals (SS) 100 MgO 40
NiO 60
Equilibrium Cooling
Non - Equilibrium Cooling
BINARY EUTECTIC SYSTEMS

Liquidus Line TB
Liquid (L)
TA TA: Melting Temp. A
L+A L+B TB: Melting Temp. B
Te : Eutetic Temp.
Te
Solidus Line

A+B

Eutectic Composition

100 % A 100 % B
%B➔
BINARY EUTECTIC SYSTEMS

Liquid (L) TB F=C–P+1

TA F=2–P+1
F=3-P
F=3-1

F=2
T C
100 % A 100 % B
%B➔

For a single phase the number of the variables which must be specified to define the system
is 2. Both temperature and composition must be given in order to define the system.
BINARY EUTECTIC SYSTEMS

F=C–P+1
TB
F=2–P+1
TA
L+A L+B F=3-P
F=3-2

F=1

T or C

100 % A 100 % B
%B➔

For two phase fields the number of the variables which must be specified to define the
system is 1. A given temperature or composition is enough to define the system.
BINARY EUTECTIC SYSTEMS

F=C–P+1
TB
F=2–P+1
TA
F=3-P
F=3-3

F=0

100 % A 100 % B
%B➔

For three phase fields the number of the variables which must be specified to define the
system is 0. As a result at eutectic point all the variables are fixed.
Basic Terms Binary System – Tie Line

Tie Lines
A1 – X1

A2 – M2

A3 – M3

B1 – N1
 Binary Eutectic System – Lever Rule

30
X1

Temperature Phase Proportions Phases (%) % Composition of Phases

T1 30 units melt (L) 100 % 70 A

30B

ε units crystals (A) ε 100 A

 Binary Eutectic System – Lever Rule

30
X2
15

Temperature Phase Proportions Phases (%) % Composition of Phases

T2 30 units melt (L) 67 % 55 A

45 B

15 units crystals (A) 33 100 A

TOTAL : 45
 Binary Eutectic System – Lever Rule

30 32.5
X3

Temperature Phase Proportions Phases (%) % Composition of Phases

T3 30 units melt (L) 48 % 37.5 A

62.5 B

32.5 units crystals (A) 52 100 A

TOTAL : 62.5
 Binary Eutectic System – Lever Rule

30
X4
40

Temperature Phase Proportions Phases (%) % Composition of Phases

T4 30 units melt (L) 43 % 30 A

70 B
40 units crystals (A) 57 100 A

TOTAL : 70
WHAT IS HAPPENING AT THE EUTECTIC POINT?

TA

TB

cooling
Liquid A crystal + B crystal
heating

100 % A 100 % B
%B➔

The eutectic reaction: is an isothermal three phase reaction in which a

liquid is in equilibrium with two phases
 EXAMPLES
EUTECTIC CERAMIC ALLOYS EUTECTIC METALLIC ALLOYS

GALINSTAN

68.5% Ga 21.5% In 10% Sn

Freezin point of alloy is – 19°C

Turbine Blades prepared by UBE - JAPAN Liquid Mirror for telescopes

Coolant paste for CPUs & GPUs

 Binary Isomorphous Systems Binary Eutectic Systems

Complete Solubility between Components No Solubility between components

If there is a partial solubility between components…

Binary Eutectic Systems with Partial Solubility

TB
Liquid
TA
L+β
X
L+α Y
α β
Teutectic

α+β

100 % A 100 % B
%B➔

Composition of α ≈ A  + B
Composition of β ≈ A  + B