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CHAPTER

3
3.1 DEFINITIONS AND BASIC
CONCEPTS
3.2 PHASE DIAGRAM
3.3 MICROSTRUCTURE
3.4 TTT DIAGRAM
3.5 HEAT TREATMENT

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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Example of metal alloy system phase diagram (Figure 3.1), showing the
region of liquid phase, solid phase and the mixture of the two phases.

L liquid phase
and solid phase
Figure 3.1 : Binary phase diagram

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3.1 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 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
non-metals.
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 with
the same physical properties, 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.
Solid solution a solid in which an element is dissolves in another so
that it is homogeneously dispersed, at an atomic scale.
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Alloy are described by stating the components


and their
concentrations, in weight or atom %.
The weight % of component A :
1

WA

weight of component A
100%
weight of all components

The atom (or mol) % of component A :


2

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)
4
Wt in grams = (No. of mols) x (atomic or molecular wt in
grams/mol)
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Constitution
described by :
(a)
(b)
phase
(c)

the constitution of an alloy is


the phases present
the weight fraction of each
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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QUESTIONS
1.

A 1.5 kg sample of -brass contains 0.45 kg of Zn and the rest is Cu.


The atomic weight of Cu is 63.5 and Zn is 65.4.
70%
The concentration of Cu in -brass, in wt % : WCu =
71%
The concentration of Cu in the -brass, in atom % : XCu =
29%

The concentration of Zn in the -brass, in atom % : XZn = .


2.

A special brazing alloy contains 63 wt% gold (Au) and 37 wt% of


nickel (Ni) (which is written Au-37 wt% Ni)
The atomic weight of Au (197.0) is more then three times that of Ni
(58.7).
At a glance, which of the two compositions, in atom %, is likely to be
the right one?
(a) XAu = 0.33,
XNi = 0.67
(b)

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XAu = 0.67,

XNi = 0.33

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3.

An alloy consists of XA atom% of A with an atomic weight of aA, and


XB atom% of B with an atomic weight of aB.
Derive an equation for the concentration of A in wt%. By symmetry,
write down the equation for the concentration of B in wt%.
WA

4.

WB

aBX B
a A X A aB X B

On heating, pure copper starts to melt at 1083C. While it is melting,


solid and liquid copper co-exist.
Using the definitions of a phase, are one or two phases present?
Why?
Ans ;

5.

aA X A
a A X A aB X B

2 phases : solid and liquid. Although they have the same


chemical composition, they differ in physical properties.

Three components A, B and C of an alloy dissolve completely when


liquid but have no mutual solubility when solid. They do not form any
chemical compounds.
How many phases, and of what compositions, do you think would
appear in the solid state?
Ans ;

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3 phases : pure A, pure B and pure C.


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3.2 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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BUILDING A PHASE DIAGRAM;


Example : Water-Salt System
Consisting of two (2) components (each
is a
compound with a
definite chemical composition)
Equilibrium phase diagram for binary alloy
system (Figure 3.2b) can be built from solidliquid cooling curve (Figure 3.2a).

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Figure 3.2 :
(a) Solid-liquid cooling curve
(b) Phase diagram for binary alloy
system (Cu-Ni)

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Some of the important information obtainable


from phase
diagrams is :
1. To show what phases are present at different
compositions and temperatures under slow
cooling (equilibrium) conditions.
2. To indicate the equilibrium solid solubility of
one element (or compound) in another.
3. To indicate the temperature at which an alloy
cooled under equilibrium conditions starts to
solidify and the temperature range over which
solidification occurs.
4. To indicate the temperature at which different
phases start to melt.
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GIBBS PHASE RULE

An equation that enables the number of phases


that can coexist in equilibrium in a chosen system
to be computed.
P+F=C+2
where
P = no. of phase which coexist in a chosen system
C = number of components in the system
F = degrees of freedom

F no. of variables (pressure, temp. ,


composition) which can be changed independently
without changing the state of the phase or phases
in equilibrium in the chosen system.

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Example : Consider the application of Gibbs


1) At point 1 (the triple point three
phase) :
P + F = C + 2
3 + F = 1 + 2
F = 0 (zero degrees of
freedom)
3

to keep the 3 phases


coexistence, none of the variables
can be changed this point is
called invariant point

Figure 3.3 : Approximate pressure-temperature


(PT) equilibrium phase diagram for pure water.
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2) At point 2 :
P + F = C + 2
2 + F = 1 + 2
F = 1 (one degree of
freedom)

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Most binary phase diagrams used in materials


science are temperature-composition diagram
(in which pressure is kept constant), in this
case, the phase rule is given by
P+F=C+1

TYPES OF SYSTEMS IN PHASE DIAGRAM


1) Complete solid solubility - examples : Ag-Au,
Figure 3.4 :
The Cu-Ni equilibrium
system

Cu-Ni, Ag-Pt

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2) Limited solid solubility examples : Cu-Ag, Pb-Sn

3) None solid solubility


- examples : Bi-Cd

Eutectic point
Eutectic point

Figure 3.5 :
The Ag-Cu equilibrium system

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Figure 3.6 :
The Bi-Cd equilibrium system

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Liquidus
line
Solidus
line
-rich solid
()

Solvus
line

Solidus
line
-rich solid
()
Solvus
line

Figure 3.7 :The Ag-Cu equilibrium system, showing types of lines


in the binary phase diagram.
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Figure 3.7 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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Peritectic
point

Eutectic
point

Eutectoid
point

Figure 3.8 :The Fe-Fe3C metastable system, there are three important invariant
Materials Science
reactions ; peritectic (1453C),
eutectic (1148 C) and eutectoid (723 C) 21

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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.
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Eutecticor invariant point. Liquid and two solid phases exist in


equilibrium at the eutectic composition and the eutectic
temperature.
Eutectoid (eutectic-like) reaction is similar to the eutectic reaction
but occurs from one solid phase to two new solid phases. It also
shows as V on top of a horizontal line in the phase diagram.
There are associated eutectoid temperature (or temperature),
eutectoid phase, eutectoid and proeutectoid microstructures.
Solid Phase 1 Solid Phase 2 + Solid Phase 3
Peritectic reaction also involves three solid in equilibrium, the
transition is from a solid + liquid phase to a different solid phase
when cooling. The inverse reaction occurs when heating.
Solid Phase 1 + liquid Solid Phase 2

Table 3.9 : Types of Three-Phase Invariant Reactions Occurring in Binary


Phase Diagrams

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3.2.1

Reading a phase diagram

(A) The constitution point


The state variables, temperature and
composition, define a point on the phase diagram.
Constitution point

Find the constitution


point, given that :
Temperature : 800C
Composition : 80% Cu

Figure 5.9 : The Ag-Cu


equilibrium system
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