Materials Science

Lecture 7 : Phase Diagrams

Reading: Chapter 9
9.1-9.14, 9.18-9.20

Introduction
Phase: A region in a material that differs in structure and
function from other regions.
Phase diagrams:
Represents phases present in metal at different conditions
(Temperature, pressure and composition).
Indicates equilibrium solid solubility of one element in
another.
Indicates temperature range under which solidification
occurs.
Indicates temperature at which different phases start to
melt.

Basic Concepts

Component: Pure metals of which an alloy is

composed.
System: Relate to the series of possible
alloys consisting of the same components,
but may have different compositions.
e.g. Fe-C system: Fe-1%C, Fe-5% C
Components: Pure Fe and pure C
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Basic Concepts
Solute: impurity atoms
Solvent: matrix
Solubility limit
maximum concentration of solute atoms
that may dissolve in solvent to still form a
solid solution
(without the formation of a new or second
phase)

Basic Concepts
Phase a homogeneous portion of a
system that has uniform physical (e.g.
crystal structure) and chemical
characteristics (e.g. composition).
Eg., In sugar-water system, two phases:
1. Syrup (water and sugar) liquid phase
2. Sugar solid phase

Microstructure of each phase is typically different

Aluminum-Copper Alloy

0.38 Wt% C steel

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Phase Diagram Water-Sugar System

What is the
solubility limit at
20oC?

How many phases does the system have when

(1) Co < 65wt% sugar
(2) Co > 65wt% sugar

Phase diagrams of pure substances

Pure substance exist as solid, liquid and vapor.
Phases are separated by phase boundaries.
Example : Water, Pure Iron.

Different phases coexist at triple point.

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Cooling Curves
Used to determine phase transition temperature.
Temperature and time data of cooling molten metal
is recorded and plotted.

Pure Metal
Iron

Thermal arrest : heat lost = heat supplied by

solidifying metal
Alloys solidify over a range of temperature (no
thermal arrest)
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What can we find from phase diagrams?

For any alloy at any temperature
1. What phases are present

Type of phases (liquid, solid (which solid))

2. What are their compositions?

Composition of each phase is how much of an alloying element

that phase have.
Composition could be in weight% or in Atomic%

3. What is the amount of each phase?

Weight fraction or volume fraction of the phase

Or volume fraction

4. What will happen if the temperature or composition of

the system is changed?

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Phase Diagrams
Binary alloy

Two component system

We will consider two types of binary phase diagrams:

Isomorphous phase diagrams
Eutectic phase diagrams

Isomorphous

Eutectic
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Binary Isomorphous Alloy System

Isomorphous system: Two

elements completely soluble
in each other in liquid and
solid state.
Example: Cu-Ni solution.

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Phase Diagrams from Cooling Curves

Series of cooling curves at different metal composition

are first constructed.
Points of change of slope of cooling curves (thermal
arrests) are noted and phase diagram is constructed.
More the number of cooling curves, more accurate is the
phase diagram.

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Weight Fraction of phases (Lever Rule)

The Lever rule gives the weight % (fraction) of phases in
any two phase regions.
Wt fraction of solid phase
= Xs = w0 w1
ws w1
Wt fraction of liquid phase
= X1 = ws w0
ws w1

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# 1: Number and type of phases

A (1100oC, 60% Ni)

1 phase -
B (1250oC, 35% Ni)
2 phases: L +

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# 2. Composition of phases
For CO = 35wt% Ni

at TA:
CL =CO =35wt%Ni
(only L phase)
at TD:
C =CO =35wt%Ni
(only phase)
at TB: both L phase and phase (Tie Line)
CL = 32 wt% Ni, C = 43 wt% Ni

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# 3. Amount of phases (wt%)

For CO = 35wt% Ni
at TA: only L phase
WL = 100 wt%
W = 0 wt%

at TD: only phase

W = 100 wt%
WL = 0 wt%

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#3. cont. Amount of phases (wt%)

At TB: both L phase and phase

S
43 35

73wt %
WL
43 32
R S
R
W
= 27wt%
R S

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Equilibrium Cooling

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Binary Eutectic Systems

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Analysis of eutectic Cu-Ag phase diagram

Invariant point E, coordinate = (TE, CE)

TE no liquid phase below TE (minimum Tm)
CE concentration at minimum Tm
line BEG also called eutectic isotherm
Eutectic reaction
cooling

L (CE)

(C E) + (C E)

heating

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Eutectic Reaction
Eutectic reaction in Cu-Ag system
cooling
L (71.9%Ag)

(8%Ag) + (91.2%Ag)

heating

Important observations:
(1) Within a phase field, only one or at most two phases may
be in equilibrium.
(2) Three phase in equilibrium only along eutectic isotherm
(3) Single-phase regions are always separated by a two-phase
region.

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Another Example of Binary Eutectic system: Pb-Sn

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Team Activity (Pb-Sn phase diagram)

Identify the invariant point using coordinate
Identify the eutectic isotherm
What is the eutectic reaction in Pb-Sn system
For Pb-40wt%Sn, at 150oC,
(1) what phases are present?
(2) what are their compositions?
(3) what is the mass fraction of each phase?

For Pb 20wt%Sn, at 175oC, answer the above three

questions.

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Structure Evolution: Example Pb-Sn system

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Structure Evolution 1
Co < 2wt%Sn
Result:

--polycrystal of grains.

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Structure Evolution 2

2wt%Sn < Co < 18.3wt%Sn

Result:
-- polycrystal with fine
crystals.

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Structure Evolution 3
18.3wt%Sn < Co < 61.9wt%Sn
Result: crystals and a eutectic microstructure

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Microstructure Evolution 3

Just above TE :
C = 18.3wt%Sn
CL = 61.9wt%Sn
S
W =
=50wt%
R+S
WL = (1-W) =50wt%

Just below TE :

C = 18.3wt%Sn
C = 97.8wt%Sn
W = S =73wt%
R+S
W = 27wt%

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Structure Evolution 4: Eutectic structure

Co = CE
Result: Eutectic microstructure

--alternating layers of and crystals.

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Eutectoid Reaction

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Eutectoid Reaction

cooling

heating

Eutectoid (eutectic like reactions)

Eutectoid: solid

solid1 + solid 2

Eutectic: liquid

solid1 + solid 2
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Fe-C system

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Fe-C System
One of the most important binary alloy phase
diagrams with wide applications.
Two basic components: Fe and C
Single phase regions:
1. - ferrite (bcc)
2. - austenite (fcc)
3. - ferrite (bcc)
4. Fe3C cementite
5. L liquid phase

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Iron-Carbide (Fe-Fe3C) Phase Diagram

Equlibrium Phases in Iron-Carbide phase diagram
Ferrite: Very low solubility
of carbon. Max 0.02 % at 7230C
and 0.005% at 00C.
Austenite: Interstitial solid
solution of carbon in
iron. Solubility of C is
2.08% at 11480C and 0.8%
at 7230C.
Cementite (Fe3C): Intermetallic compound.
6.67% C and 93.3% Fe.
Pearlite: Consists of alternating layers
of Ferrite and Cementite.
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Fe-C System
For pure Fe (100 wt% Fe)
Polymorphic transformations:
ferrite

912oC

- austenite

1394oC

ferrite

Fe C system (up to 6.7 wt% C) or

Fe-Fe3C system (up to 100wt% Fe3C)

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Solubility of C in different phases

Maximum solubility of C in - ferrite (bcc):

0.022wt%C
Maximum solubility of C in austenite (fcc):
2.14wt%C
The solubility of C in austenite is much higher.
This is because that interstitial position in FCC
crystal is larger than that in BCC crystals

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Octahedral Interstices

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Invariant Reactions in Fe-Fe3C diagram

Peritectic reaction:
1495C
Liquid (0.53%C ) (0.09%C )
(0.17%C )

Eutectic reaction:
1148C
Liquid (4.3%C )
austenite (2.14%C ) Fe3C (6.67%C )

Eutectoid reaction:

723C
Austenite (0.76%C )
Ferrite (0.022%C ) Fe3C (6.67%C )

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Development of Microstructure in Iron-Carbon alloy

Hypoeutectoid
Steel

Less than 0.8%

0.8% C More than 0.8%

Eutectoid Steel

Hypereutectoid
Steel

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Slow Cooling of Plain Carbon Steel

Eutectoid plain carbon steel: If a sample is heated up to

7500C and held for sufficient time, structure will become
homogeneous austenite.
Below eutectoid temperature,
layers of ferrite and cementite
are formed.
Pearlite.

Eutectoid steel

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Slow Cooling of Plain Carbon Steel (cont..)

Hypoeutectoid plain carbon steel: If a sample of 0.4% C is
heated up to 9000C, it gets austenitized.
Further cooling gives rise to and pearlite.

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Slow Cooling of Plain Carbon Steel (cont..)

Hypereutectoid plain carbon steel: If for example a 1.2% C sample is heated up

to 9000C and held for sufficient time, it entirely gets austenitized.
Further cooling results in eutectoid cementite and pearlite.

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