❑ Concept of alloying

❑ Classification of alloys
❑ Introduction to the phase diagram
❑ Uses and limitations of phase diagrams
❑ Classification of phase diagrams
❑ Construction of phase diagrams

Reference:
1. Avner. Introduction to Physical Metallurgy, Ch. 5 and 6.
2. WD Callister, Jr. Materials Science and Engineering:
An Introduction,
MME 291 Lecture 1-2

Introduction to
the Phase Diagrams

Department of MME Sumit Bhowmick

BUET, Dhaka Lecturer
Dept. of MME
❑ Classifications based on:
 Crystal Structure (e.g., austenitic/FCC stainless steel)
 Shape of phase diagram (e.g., eutectic alloys)
To be
discussed
soon!

❑ In the solid state, there are three possible phases exist:

 Pure metal
 Intermediate alloy phase or compound
 Solid solution
❑ An alloy is a substance that has metallic properties and is
composed of two or more chemical elements, of which at least
one is a metal.
❑ Alloying elements are deliberately
introduced into a metal to enhance 60% Ni
properties (especially, mechanical
Monel
properties)

Note the difference

 Alloying element and impurity element Cu Wt % Nickel Ni
 Alloy and alloy system
Property Direction
Alloy systems Tensile strength Up
Yield Strength Up
 Binary system (Fe-C system, Cu-Zn system) % Elongation Down
 Ternary system (Fe-C-Mn system, Al-Si-Mg system) Electrical Conductivity Down
Solid Solutions
❑ Solution in the solid state where two kinds of atoms
are combined in one crystal lattice.

Distortion resulted during formation of solution causes

an increase in strength of the alloy. This is the primary
basis for strengthening of a metal by alloying.

❑ Solubility of solute in solution depends on temperature

and pressure of the system, and method of forming.
❑ Unsaturated, saturated, and supersaturated solutions.
Solid Solutions
❑ Substitutional and interstitial solid solutions

Interstitial
Substitutional

Hume-Rothery Rule for

forming substitutional solid
Example:
solution
Cu – Ni alloy  Completely soluble
 Crystal structure factor Cu – Zn alloy  Partially soluble
 Relative size factor Cu – Pb alloy  Completely insoluble
 Chemical affinity factor
 Relative valence factor
 Introduction to Phase Diagrams

 The properties of materials reflect their microstructures. The

microstructures are controlled by the composition of the material and
how it is processed.

 So it is important that we must know

 about the structure of a material that has been developed during its
manufacture, and
 the method of controlling (and/or modifying) the structure to enhance
its properties.

 Phase diagram is an important tool for materials scientists that

tells which phases are stable in a system under specified
conditions (e.g. of temperature, overall composition, pressure)
 Phase diagram is basically a map that
presents the domains of stability of phases
and the limits of stability of phases in a liquid
graphical form. solid
liquid-gas
gas equilibria
 Reading the map will tell you, at the
state when it comes to equilibrium, Temperature
1. what phases are present, Typical phase diagram for
2. the state of those phases, and one component system
3. the relative quantities of each phase. ‘Every zone of meeting is
a zone of coexistence’
 Reading a phase diagram will also tell what phase
transformations we can expect when we change one or more
parameters of the system (T, P, X).
What and how many phases materials
possess?

 Solid, liquid, or gas, (and plasma)?

 Is it possible to have more than one solid phases?

Iron, being an allotropic material, has more than one solid phases:
❑ When iron first freezes from its liquid state, it is BCC (d-iron)
❑ As it cools it changes to FCC (g-iron)
❑ Upon further cooling it changes to BCC (a-iron)
Definitions and Basic Concepts

Components
❑ Chemically recognisable species that are mixed to form the alloy.
 In Brass: Cu, Zn (element)
 In steels: Fe, C (element)
 In ceramics: SiO2, Al2O3 (compound)
❑ Binary alloy contains 2 components, ternary 3, etc.

Phase
❑ A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical
composition and structure.
 Equilibrium state and Metastable state

 A system is at equilibrium if, at

constant T, P and X
(composition), the system does
not change with time.
 The equilibrium state always has
the minimum free energy.

❑ Equilibrium state requires sufficient time to achieve. When this time is too long
(due to slow kinetics), another state along the path to the equilibrium may
appear to be stable. This is called a metastable state.

❑ A system at a metastable state is trapped in a local minimum of free energy,

which is not the global one.
Phase Diagram Nomenclatures

Concentration/Composition of alloy
❑ Relative amounts of each constituent
❑ It is the horizontal axis in all binary phase diagrams
❑ The scale can be in weight %, atomic % or mole %

Liquidus temperature
❑ Start of solidification (or, end of liquification) temperature

Solidus temperature
❑ End of solidification (or, start of liquification) temperature
 Liquidus

Liquid

Liquid +
Freezing range
Solid
Solidus

Solid

X % Y added Y
Phase diagram with complete solubility of one component into another
 The Cooling Curve

Alloy 1 ARREST

Temperature
Liquid Liquid POINTS
Liquid + start of solidification
Solid
Freezing Liquid + Solid
range
TX end of solidification
TX Solid Solid
Pure metal X Alloy 1

X % Y added Y Time
For alloys, at a fixed temperature within 2-phase (coexistence)
regions, there is a specific equilibrium ratio of two phases.
Chemical composition of Phases
❑ It is the chemical composition of each phase in the system.
❑ In a system having more than one phase, each phase will have a
unique chemical composition which will be different from each other,
and will also be different from the overall composition.
❑ Not to be confused with overall composition of the alloy.

Relative amounts of Phases

❑ When a system contains more than one phases, then it is the amount
of each phase relative to overall amount of the alloy.
❑ Depends on temperature and composition of the alloy.
❑ Not to be confused with composition of phases.
 In a system having more than
one phase, each phase will have
 Composition of each phase a unique chemical composition
which will be different from each
other, and will also be different
Phase diagram rule #2: from the overall composition of
Tie Line Rule the system.
Not to be confused with overall
If we know C0, then we can tell the composition of each phase at composition.
any temperature.

tie line
At TA: L phase only
CL = 35%Ni

At TB: L and a phases

CL = Cliquidus = 32%Ni
Ca = Csolidus = 43%Ni

At TD: a phase only

Ca = 35%Ni
 It is the relative amount
 Relative amount of each phase (as in kg) of each phase in
the whole alloy.

Phase diagram rule Not to be confused with

composition (i.e., %A and
#3: Lever Rule %B) of the alloy.
If we know C0, then we can tell the weight fraction of each
phase at any temperature.

Consider C0 = 35 wt.%Ni
 At TA, only L phase  WL = 100 wt.%
 At TD, only a phase  Wa = 100 wt.%
 At TB, both L and a phases 
100 S 100 (43-35)
WL = = = 73 wt.%
Lever R+S 43-32
Rule 100 R 100 (35-32)
Wa = = = 27 wt.%
R+S 43-32
The microstructural development depends on the overall
composition and the cooling rate
L A•
1300 L+a
Point E Point A 34 B• 46

T (°C)
L: 35 wt.%Ni
32 • 43
a: 35 wt.%Ni C
24 • 36
D
1200
Point B E• a
a: 46 wt.%Ni
L: 34 wt.%Ni
Point D
a: 36 wt.%Ni Point C 1100
L: 24 wt.%Ni 20 30 C0=35 40 50
a: 43 wt.%Ni
L: 32 wt.%Ni wt.% Ni
All microstructures at a glance

Summary of
Solidification
Process
Solidification begins at the liquidus
line and continues upon cooling

The composition and amount of the

solid and the liquid change
gradually during cooling

Solid phase grows by consuming all

the liquid and solidification ends at
the solidus line
Faster cooling rate Slower cooling rate
cored structure – a.k.a. microsegregation equilibrium structure

Ca changes during Ca composition is

solidification equals to C0 throughout
 98% Ni
L • •
• • 90% Ni
L+a 98
• • 90
• •
a
80
87 80% Ni
70
Wt.% Ni 70% Ni

Complete solidification Solid can’t freeze fast enough:

occurs at lower T and solidus line effectively shifted
higher Ni content than to higher Ni concentrations.
equilibrium at that T Shift increases with faster
cooling rates due to slower diffusion
 On re-heating, grain boundaries Lighter phase with
will melt first, as they are rich in low Al content
lower melting-point constituent. Darker phase with
This can lead to premature high Al content
mechanical failure!

Cored structure in Al-Cu alloy

Homogenising the cored structure

 Microsegregation of the cored structure can be eliminated
by reheating the material at a higher temperature.
 Diffusion of inhomogeneous element takes place.

 Macrosegregation, however, cannot be eliminated by reheating.

Construction of Phase Diagrams
Experimental Methods
 Thermal analysis
 Generation of cooling curves (temperature vs. time) for a number of alloys of
the alloy system to obtain arrest points (temperatures where a change in
slope is observed)
 Solid-state phase changes are difficult to obtained in this method
 Metallographic method
 Heating samples of an alloy to different temperatures, and quench them after
equilibrium to retain the high-temperature structure
 Observe the structure microscopically
 Rapidly cooled samples do not always retain high-temperature structures;
considerable skill is required to interpret the microstructure correctly
 Classification of Phase Diagrams
One component (unary) phase diagrams
❑ Also known as P-T diagrams.
❑ The simple case is Water.

 How many single-phase

regions?
 How many two-phase
regions?
 Is there any three-, or
more-phase regions?

Gibbs’ Phase Rule: F = # variables Unary phase diagram of water

C = # components
F = C–P+2 P = # phases
Two-component (binary) phase diagrams
Must follow the
Hume-Rothery Rule

❑ Example: Copper - Nickel, Silicon - Germanium

➔ Completely miscible/soluble phase diagrams
➔ Eutectic phase diagrams
 Completely immiscible/insoluble phase diagrams
 Partially miscible/soluble phase diagrams
 In the case of lead-rich
alloy (0-2 wt. % of tin)
solidification proceeds
in the same manner as
for isomorphous alloys
(e.g. Cu-Ni) that we
discussed earlier.

L ➔ L+ a ➔ a

Alloys with no Eutectic and forming Unsaturated Solid Solutions

 At compositions
between the minimum
and the maximum solid
solubility limit, β phase
nucleates as the α solid
solubility is exceeded
upon crossing the
solvus line.

L ➔ L+a
➔ a➔ a+b

Precipitates in Al-Si alloy

Alloys with no Eutectic and forming

Supersaturated Solid Solutions
alternate layers of
a and b crystals
The Eutectic Alloy
 Eutectic

Pro
eutectic

also known as
primary a or
proeutectic a

The Hypoeutectic Alloy

Problem

One kilogram of an alloy of 70% Pb and 30% Sn is slowly cooled

from 300ºC. Calculate the following:

1. Chemical composition
of the liquid and a
phases at 225ºC.

2. Weight % of liquid
and a at 225ºC.
CL = 45 wt.% Sn

Ca = 17 wt.% Sn

100 (45 – 30)

Wa =
45 - 17
= 54 wt.%

100 (30 – 17)

WL =
45 - 17
= 46 wt.%
Problem
For the Pb-Sn alloy system,
(a) What is the compositions and relative
amounts of the phases that constitute
the eutectic microstructure?
(b) For an alloy containing 30 % Sn,
(i) What are the relative amounts of
a and b phases present at the
eutectic temperature?
(ii) What are the relative amounts of
the eutectic and the proeutectic a
phase present at the same
temperature?
 L L

Temperature
Temperature
L
Temperature

L+a
L+a
L + (a+b)
a
(a + b) (a+b) + a

a+b

Time Time Time

alloys with no eutectic eutectic alloy hypo/hyper eutectic alloy
 1600 The Eutectic Reaction
L
cooling
L 12 Si (Al + Si)
Temperature, C

1200
heating
Al + L
L + Si
800
577 C

400
Al + Si
12
0
0 20 40 60 80 100
Al Wt.% Si Si

Aluminium – Silicon Phase Diagram

Completely immiscible/insoluble phase diagrams
Eutectic phase diagrams
Alloy 1 solidification
 Alloy 2 solidification

Relative amounts of phases

Microstructural changes
Alloy 3 solidification
Au-Si phase diagram (Completely insoluble)