CHAPTER 5

5.1
5.2
5.3

DEFINITIONS AND BASIC CONCEPTS

PHASE DIAGRAM
MICROSTRUCTURE

What can you explain about the map shown in the above figure?

Showing the region of sea (liquid phase) and land (solid phase)
Showing boundaries lines between sea and land; and between countries (such
as Malaysia, Thailand, Indonesia etc.)

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ISSUES TO ADDRESS...
When we combine two elements...
what equilibrium state do we get?
In particular, if we specify...
a composition (e.g., wt%Cu - wt%Ni), and
a temperature (T)
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

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Example of metal alloy system phase diagram (Figure 5.1), showing the
region of liquid phase, solid phase and the mixture of the two phases.

L liquid phase
and solid phase
Figure 5.1 : Binary phase diagram

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5.1

DEFINITIONS AND BASIC CONCEPTS

It is fundamental to materials science and engineering that
properties of materials reflects their microstructure.
Microstructures are controlled by the composition of the
materials and how it is processed.
Manufacturing shaping + assembling engineering
product & devices + provides the materials properties
required.
Most materials processing involves thermal history.
Important to understand how processing history
(particularly temperature) control microstructure and
properties.

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SOME ESSENTIAL DEFINITIONS :

Phase Diagram MAP of materials phases
or a diagram with temperature and composition as axes
provide some fundamental knowledge of what the
equilibrium structure of a metallic (or ceramic) alloy.
Metallic Alloy a mixture of metals with other metals or nonmetals.
Example : Brass a mixture of copper (Cu) and zinc (Zn)
Components the chemical elements (or compounds) which
make up alloys.
Example : in brass the main components are Cu and Zn.

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 Binary alloy contains two (2) components.

Ternary alloy contains three (3) components.
Quarternary alloy contains four (4) components.
Phase all parts of an alloy microstructure which has a
homogeneous atomic structure and the same composition.
For example, in a binary alloy (solid state) the
microstructure can take one of four forms;
(a) a single solid solution;
(b) two separated pure components;
(c) two separated solid solutions;
(d) chemical compounds, together with solid solution.

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Solid solution a solid in which an element is dissolves in another so

that it is homogeneously dispersed, at an atomic scale.

Alloy are described by stating the components and their

concentrations, in weight or atom %.
The weight % of component A :
weight of component A
100%
WA =
weight of all components

The atom (or mol) % of component A :

XA =

number of atoms (or mols) of component A

100%
number of atoms (or mols) of all components

No. of mols = (weight in grams)/(atomic or molecular wt in grams/mol)

Wt in grams = (No. of mols) x (atomic or molecular wt in grams/mol)
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Constitution the constitution of an alloy is described by :

(a) the phases present
(b) the weight fraction of each phase
(c) the composition of each phase

Equilibrium constitution there is no further tendency for

the constitution of a sample of given composition to change
with time at a constant temperature (T) and pressure (p).

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5.2

PHASE DIAGRAM

Processing of engineering materials always involves materials

in liquid or solid state.
In these states, pressure p only has a small influence on the
equilibrium constitution, and can be neglected.
In phase diagram, we will only be concerned with material
states which are controlled by the remaining two state
variables : temperature and composition.
The phase diagram of the components A and B is determined
(at a standard pressure of 1 atm) by the temperature T and the
composition XB (or WB) or XA (or WA).
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Some of the important information obtainable from phase

diagrams is :
1.

2.
3.

4.

To show what phases are present at different

compositions and temperatures under slow cooling
(equilibrium) conditions.
To indicate the equilibrium solid solubility of one
element (or compound) in another.
To indicate the temperature at which an alloy cooled
under equilibrium conditions starts to solidify and the
temperature range over which solidification occurs.
To indicate the temperature at which different phases
start to melt.

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Liquidus line
Solidus line
-rich solid ()

Solidus line

Solvus line

-rich solid ()
Solvus line

hypoeutectic

hypereutectic

Figure 5.7 :The Ag-Cu equilibrium system, showing types of lines

in the binary phase diagram.
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Figure 5.7 shows the types of line in the phase diagram :

Liquidus line the phase boundary which limits the bottom
of the liquid field
Solidus line the line giving the upper limit of the single
phase solid field.
Solvus line the line which separates the two phase field
with the single phase solid field.

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TYPES OF INVARIANT REACTIONS :

Eutectoid a phase transformation in which a solid phase

transforms on cooling into two solid phases isothermally.
+
Eutectic a phase transformation in which all the liquid phase
transforms on cooling into two solid phases isothermally.
L+
Peritectic a phase transformation in which, upon cooling, a
liquid phase combines with a solid phase to produce a new
solid phase.
+L

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Table 5.1 : Types of Three-Phase Invariant Reactions Occurring in Binary

Phase Diagrams

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5.2.1 Reading a phase diagram

(A) The constitution point
The state variables, temperature and composition,
define a point on the phase diagram.
Find the constitution
point, given that :
Temperature : 800C
Composition : 80% Cu

Figure 5.9 : The Ag-Cu

equilibrium system
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QUESTIONS 1 ;

Use the Pb-Sn diagram below to answer the following question.

L + (Pb)
(Pb)

(Sn)

2
L+ (Sn)

3
(Pb) + (Sn)

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1.

What are the values of the two state variables at point 1?

Composition : ..........
Temperature : ..

2.

Mark the constitution points for Pb-70 wt% Sn and Pb-20

wt% Sn alloys at 250C.
What does the alloy consist of in each case?
Pb-70 wt% Sn : .
Pb-20 wt% Sn : .

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3.

The alloy corresponding initially to the constitution point 1 is

cooled very slowly to room temperature.
At which temperatures do changes in the number or type of
phases occur?
What phases are present at point 2?
.......
What phases are present at point 3?
...

4.

Similarly, the alloy corresponding to the constitution point 4

is cooled to room temperature. Identify the following :
Initial composition & temperature : ..
Initial phase(s) :
Temperature at which change the phase occurs :
Final phase(s) : .
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(B) Composition of the phases

In a single-phase region, the phase composition and
alloy composition coincide.
In a two-phase region, the compositions of the phases
are found at the ends of the isothermal line spanning
the field through the constitution point. This line is
called the tie-line.

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QUESTIONS 2 ;

Use the Pb-Sn diagram below to answer the following question.

L + (Pb)

(Sn)

(Pb)

L+ (Sn)

(Pb) + (Sn)

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1.

The constitution point for a Sn-70 wt% Pb alloy at 250C lies

in a two-phase field. Construct a tie-line on the figure and
read off the two phases and their compositions.
Phases : ..
Composition of phase 1 :
Composition of phase 2 :

2.

The alloy is slowly cooled to 200C. At this temperature,

identify the :
Phases : .
Composition of phase 1 :
Composition of phase 2 : ...

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3.

The alloy is cooled further to 150C. At this temperature,

identify the :
Phases :
Composition of phase 1 : ...
Composition of phase 2 :

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QUESTIONS 3 ;

Use the Pb-Sn diagram to determine the phases and the composition
of each phases for alloy at point 1.

L + (Pb)

(Sn)

(Pb)

L+ (Sn)

1
(Pb) + (Sn)

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(C) Proportion of the phases (Amount of phases) in two-phase

alloys
This will achieved by using LEVER RULE.
(Lever rule a useful tool for determining the weight
fraction for each phases in a two-phase field)
Steps in finding the weight percentages of the phases in
a two-phases region.
1.
construct a tie-line through the constitution point
2.
read off the three compositions (for the alloy, and
the two ends of the tie-line)
3.
apply the lever rule.
Note : Wphase 1 + Wphase 2 = 1 @ 100%
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Determine the proportion (amount) by weight of each phase for alloy

at point 1 by using lever rule.
Phase : Liquid + (Pb)

L + (Pb)

(Sn)
1

(Pb)

L+ (Sn)

(Pb) + (Sn)

17

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QUESTIONS 4 ;

Use the Pb-Sn phase diagram to answer the following questions.

1.

A lead (Pb) tin (Sn) alloy with composition WPb = 80% is

held at a temperature T.
(a) At T = 270C which is the dominant phase?
(b) At T = 200C which is the dominant phase?
(c) At T = 150C which is the dominant phase?

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2.

The alloy is cooled to 100C (WPb = 80% ).

(a) How many phases are present?
(b) Give the approximate composition of the phase(s).
(c) Which is the dominant phase?
(d) What are the proportions by weight of each phase?

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MICROSTRUCTURES IN EUTECTIC SYSTEMS - III

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MICROSTRUCTURES IN EUTECTIC SYSTEMS - IV

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Problems
Consider the Pb-Sn diagram, make a phase analysis for the
plumbum alloy equilibrium solidification for each composition
below ;
(i) Point d with 40% Sn at 183C + T.
(ii) Point e with 40% Sn at 183C - T.

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(i)

Phase

liquid (L)

Proeutectic-

Phase
composition

61.9% Sn in liquid

19.2% Sn in proeutectic-

Amount of
phase

40 19.2 (100%)= 49%

61.9 19.2

61.9 40 (100%)=51%.
61.9 19.2

Total

Beta(
)

Phase
composition

19.2% Sn in

97.5% Sn in

Amount of
phase

97.5 40 (100%) = 73%

97.5 19.2

40 19.2 (100%) = 27%

97.5 19.2

(ii) Phase

% eutectic = % total % proeutectic

= 73 % - 51% = 22%
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TTT Diagram
Means Time-Temperature-Transformation
Also known as an Isothermal Transformation
Diagram
Microstructure and property changes in Fe-C
alloys is an example of a real application of phase
transformation knowledge.

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 Study a eutectoid steel annealed just below the

eutectoid temperature
Experiment for following the microstructural
changes which occur during the isothermal
transformation of an eutectoid plain-carbon steel
at 705oC
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Isothermal
transformation
microstructure

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 Valid only for eutectoid steels, and constant

temperature transformations
Two solid line : start and end of transformation
Dashed line : 50% transformation
Eutectoid temperature a horizontal line (above
which is austenite)
Transformation rate increases with decreasing
temperature

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Austenite Transformation

Possible transformation involving the decomposition of austenite.

Solid arrow : transformation involving diffusion
Dashed arrow : diffusionless transformation
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 Slow cooling, coarse pearlite formed with thick

ferrite and cementite layers
Increased cooling rate, lamellar thickness
decreases
Increased cooling rate still allows formation of
bainite
Faster cooling rate allow formation of martensite

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Properties of phases
Properties of pearlite
Fairly tough
Fairly ductile
Depends on size of lamellae

Properties of bainite
Tough
Structure between pearlite
and martensite ( + Fe3C)

Properties of martensite
Very hard HRC 45-55
Brittle
bc tetragonal structure
Supersaturated solution of C in Fe
High residual stresses
Metastable
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Pearlite microstructure
Alternate
plates of
carbide and
ferrite.
Normally the
structure
cannot be
resolved.
Particularly slow
cooling has been
used.
Coarse Pearlite

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Bainite Microstructure
Upper Bainite
Formed from 350oC to 550oC
Cementite in form of rod

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Lower Bainite
Formed from 250oC to 350oC
Low diffusion rate produced iron carbide
precipitate within ferrite plates predominantly
along single orientation (55o to longitudinal axis of
ferrite)

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Formation of martensite
High cooling rates - quenching
Rapid cooling with water or oil
Diffusion of carbon inhibited
Neither ferrite nor pearlite have sufficient
time to form
Shear transformation
Body centred tetragonal structure
Carbon evenly distributed

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Microstructure of martensite
Martensite is created
when austenite transforms
by a shear mechanism
instead of by nucleation
and growth.
The shear transformation
products are acicular.
In this case, because of
high carbon (1.2%) there is
retained austenite.

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Heat treatment
Definition of heat treatment is a controlled
heating and cooling cycles intended to adjust the
microstructure and mechanical properties of a
material for a specific purpose.
Examples: annealing, normalizing, quenching and
tempering

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Annealing
Material exposed to elevated temperature for
extended period of time, and then slowly cooled.
Used to relieve stresses, increase softness,
ductility and toughness, or to
produce specific microstructure
Full annealing : Transformation to austenite, then
furnace cooled to coarse pearlite (relatively soft
and ductile material)

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Normalizing
Used to refine grains and produce more uniform
distribution in steels which have been plastically
deformed (e.g. rolling) resulting in tougher steel.
Complete transformation to austenite, then air
cooled to a fine pearlite

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Microstructure Variations due to Cooling

Rates
A: Slow cooling in furnace
-- lamellar coarse pearlite
B: Cooling in still air
-- fine pearlite
C: Split transformation
-- fine pearlite and martensite
D: Rapid cooling
-- martensite
E: Critical cooling rate
-- slowest rate to produce no
pearlite (full martensite)
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Tempering
Heating martensite to between 100 & 600C
Softens & toughens martensite
Effects dependent on temperature and include
Stress relief
Epsilon carbide precipitates from martensite
Cementite precipitates from martensite
Epsilon carbide converts to cementite
Retained austenite transforms to bainite

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Effect of tempering
Increases ductility and toughness
Reduces hardness and strength
Solid solution elements have little effect on
tempering
Ni, Si, Al, Mn
Strong carbide formers raise tempering
temperature for equivalent hardness
Cr, Mo, V

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Martempering (Marquenching)
Modified quench to minimize distortion of heat treated steel:
1) austenitize steel
2) quench in hot oil or molten salt just above martensite
start temperature
3) hold in quenching medium until uniform temperature in
steel (but before austenite to bainite transformation
begins)
4) cool at moderate rate to prevent thermal gradients
====> usually, parts are later tempered to toughen steel

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Martempering (Marquenching)

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Austempering
1) Austenitize steel
2) Quench in hot salt
bath just above
martensitic
temperature
3) Isothermal hold
4) Cooled to room
temperature in air

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Austempering
Isothermal heat treatment process to produce Bainite
Alternative to quenching and tempering
Improved ductility and impact strength for particular
hardness
Decreased cracking and distortion quenching
Particularly advantageous for thin sections (<3/8")
{thicker sections have non-uniform properties due to
different cooling rates}

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SUMMARY
Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
Binary eutectics and binary eutectoids allow for
a range of microstructures.

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