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MEC281 : MATERIALS SCIENCE

CHAPTER 2 :
PHASE DIAGRAM
Rasdi bin Deraman
Jabatan Kejuruteraan Mekanikal
UiTM Pulau Pinang
OBJECTIVE
After completing this chapter, students should be able
to :

• Understand how phase diagrams describe the equilibrium


state of binary alloys materials.

• Describe the characteristics of binary isomorphous and


binary eutectic alloys

• Use the lever rule technique to determine phase


compositions and phase amounts at any point on a binary
phase diagram.

• Understand the relation between cooling curve and phase


diagram.
PHASE DIAGRAM
SOLIDIFICATION OF PURE METALS &
ALLOYS

The solidification of metals and their alloys is


an important industrial process.

Not only do structure alloys start with the


casting of ingots for processing into
reinforcing bars or structural shape, but when
a metal is welded a small portion of metal near
the weld melts and resolidifies.
After pouring into the mold, the molten
metals/alloys cool and solidify.

Solidification is the most important phase


transformation because most of metals/alloys
undergo this transformation before becoming
useful products.

Solidification involve liquid-solid phase


transformation, e.g : casting process.

The solidification process differs depending


on whether the metal is a pure element or an
alloy.
Solidification Process
In general the solidification of metals or alloys can
be divided into the following steps:
i)      The formation of nuclei in the melt
(nucleation)
ii)     The growth of nuclei into crystal
iii) The formation of a grain structure
Liquid Grain boundaries
Liquid

Nuclei

Irregular grain Grain


a) b) c)
Formation of the grain zones
At the walls of the mold, the molten metals/alloys
cools rapidly. As a result, the casting develops small
equiaxed grains due to the large temp. gradient at the
surface.

As cooling continues, the grains grow in the direction


opposite to the heat flow where the grains grow
inwardly as needles is known as columnar grains.
For pure metals, columnar grains will stop to
grow until complete solidification has
occurred.

For alloys, further cooling of the molten alloy


will cause formation of large equiaxed
grains, showing segregation of alloying
components in the center of casting due to
the imbalance in composition between the
metal that has solidified and the remaining
molten metal.
Large
equiaxed
zone

Small
equiaxed
zone

Columnar
grains

a) b)

Figure : Schematic illustration of two cast structures of metals solidified in a square mold:
(a) pure metals; (b) alloys
METALLIC SOLID SOLUTION
Most metals are combined to form
alloy in order to impart specific
characteristic.

An alloy is a combination of two or


more elements (added impurity
atoms), at least one of which is a
metal.

The addition of impurity atoms to a


metal will result in the formation of a
solid solution which composed of
solvent (host atoms) and solute
(alloying elements).

E.g : Steel/cast iron (iron base


alloys), bronze/brass (copper base
alloys), Al alloys, Ni base alloys, Mg
base alloys, Ti alloys.
TYPES OF SOLID SOLUTION
Most engineering metals are combined
with other metals or nonmetals to provide
increased strength, higher corrosion
resistance or the desired properties.
The simplest type of alloy is a mixture of
two solution which is consists of two or
more elements atomically dispersed in a
single phase structure.

Two types of solid solutions:


i. Interstitial Solid Solution
ii. Substitutional Solid Solution
Interstitial Solid Solutions
A solid solution formed in which solute atoms
can enter the holes in the solvent-atom lattice.
The solute atoms fit into the spaces between
the solvent or parent atoms.

Examples of atoms that can


form Interstitial Solid
Solutions due to their small
size are hydrogen, carbon,
nitrogen, and oxygen.
The lattice distortion creates a strain along the slip planes and grains of the material,
which results in the increase of strength and hardness because it makes atom-by-
atom slip along those planes more difficult.

i) Substitutional solid solution ii) Interstitial solid solution

Figure : This is a schematic illustrating how the lattice is strained by the addition of
substitutional and interstitial solute. Notice the strain in the lattice that the solute atoms
cause.
2.2.2 Substitutional Solid Solutions

A solid solution in which solute atoms of one elements


can replace those of solvent atoms of another element.
It can be formed by two elements solute atoms can
substitute for parent solvent atoms in a crystal lattice.
The crystal structure of the solvent is unchanged, but
the lattice may be distorted by the present of the
solute atoms.

For example, in a Cu-Ni solid solution the Cu atoms


can replace the Ni atoms in the solid solution crystal
lattice.
This configuration can be tend to occur when the atoms
do not differ greatly in size and must be quite similar :

• Less than about 15% difference in atomic radii


• The same crystal structure
• Similar electronegativity (the ability of the atom to
attract an electron)
• The same valence.
2.3 SOLUTION
When two components combined they can either remain
separate entities or combine to form a single phase which
is referred to as a solution. Degree to which the two
components mix is referred to as the solubility.
Examples:
Alcohol and water – completely soluble
Hot choc – powder mix soluble in water but limited extent
Oil and vinegar – insoluble liquids can be temporarily mixed

Solutions can also occur in the solid state and with the
same range of solubility as described for liquids.

Examples: Cu and Ni are completely soluble


Zinc has limited solubility in copper
Pb insoluble in copper
2.4 THE PHASE DIAGRAMS

A phase diagram is a graphical representation of the phases


present, composition, and temperature at equilibrium of the
structure of an alloy or ceramics in which the phases are
stable. Phase Diagram most important tools available to
materials scientist and engineers.

2.4.1 Binary Phase Diagrams


A binary phase diagrams consist of two elements in
one alloy. There are three type of phase diagrams:
i. Complete Solid Solution
ii. No Solid Solution
iii. Limited Solid Solution
2.4.2 Binary Phase Diagrams for Complete Solid Solution
This phase diagram shows an isomorphous* system in
which only one solid phase forms. *Isomorphicity means
having same crystal structure or complete solid solublity
for all composition. Tm,B

The alloy is solid for all


composition at temperature
below Tm,A

The alloy is liquid for all


composition at temperature
above Tm,B

Tm,A
liquidus line
Solidus line
2.4.3 Binary Phase Diagrams for No Solid Solution
The elements are dissimilar that their solubility in other
is nearly can negligible.
The figure below shows element A and B cannot
dissolves with each other. The elements are only
completely soluble in the liquid state but completely
insoluble in the solid state.
Temperature
L
Liquidus line

A+L B+L

Eutectic
temperature Solidus line
Eutectic point
A+B
A B

Composition
2.4.4 Binary Phase Diagrams for Limited Solid Solution
The elements are dissimilar that their solubility in other is
nearly can negligible.

The figure below shows element A and B cannot dissolves


with each other. The elements are only completely soluble in
the liquid state but completely insoluble in the solid state.
Liquidus line

Temperature
Liquid, L

Solidus
Solidus line

α α +L β+L β
line
Eutectic
temperature
Solvus α +β Solvus
line
line Eutectic point
A B
Composition
2.5 THE GIBBS PHASE RULE
Phase diagram describe thermodynamic equilibrium
condition. Number of phases in equilibrium limited by
thermodynamics.
This is described by Gibbs phase rule:
p+f=c+n
p = number of phases present
f = number of degrees of freedom
(state variables : Temperature, Pressure
and composition)
c = no. of components
n = no. of noncompositional variables
(n= 1 for alloy/ceramic, n= 2 for condensate)
Examples
Ice-water-steam : 3 distinct phases

solid
liquid
Pressur
e

gas

Temperature
T1 T2 T3

P1
solid
liqui
Pressur

d
P2
e

Temperature

One phase – two degrees of freedom


solid
liqui
Pressur
d
P2
P1
e

T1 T2
Temperature

Two phases – one degree of freedom


solid
liqui
Pressur

d
P1
e

gas

T1

Temperatur
e
Three phases – zero degree of
freedom
When the degree of freedom is equal to zero, it is called
invariant point.
Phase rule for binary system , c=2 (A and B)

F=3-P

A single phase , P=1 , F=2


- composition and temperature can be changed
independently

Two-phase mixture F=1


- at a given temp, the composition of the liquid and solid
is fixed , given by the liquidus and solidus line
2.6 INTERPRETATION OF PHASE DIAGRAM BY USING
LEVER RULES METHOD

A phase diagram gives the following information:


• The phase present (solids and liquids or combinations)
• The composition (chemical makeup) of these phases
• The amount of each phase

2.6.1 The phase present


One just locates the temperature – composition point
on the diagram and notes the phase(s) with which the
corresponding phase field is labeled.
2.6.2 The composition
i. Draw the tie line across the two-phase region at the
temp. of the alloy.
ii. The intersections of the tie line & phase boundaries on
either side are noted.
iii. Draw the perpendicular line from these intersections to
the horizontal composition axis,
2.6.3 Determination of Phase Amount
The relative amounts of the phases present at equilibrium
can be determined by using Lever Rule method.
Mass fraction of α , Wα and
Mass fraction of Liquid, WL

S
WL =
R+ S
Cα − Co
WL =
Temperature = 1250 ºC
Cα − CL
Composition = 35 wt%Ni-65 wt % Ni
Phases present = α + Liquid
Example:
Based on the diagram below, determine the phase present,
the chemical composition and relative phase amount at the
composition and temperature 53 wt% Ni and 1300 ºC
respectively.

Solution:
Example:
Based on the diagram below, determine the phase present,
the chemical composition and relative phase amount at the
compo. and temp. 30 wt% Sn and 200 ºC respectively.
Solution:
Example:
Based on the diagram below, determine the phase
present, the chemical composition and relative phase
amount at the eutectic point and slightly below eutectic
temperature.
Solution:
Eutectic temp. (TE)
a.k.a. triple point.

Eutectic temp. (TE) :


No liquid below TE
and form 2 different
solid phases.

CE
Eutectic concentration (CE) :
Figure : Copper-silver phase diagram
Min. melting temp. composition (CE)
Microstructural development during slow cooling

Gradual solidification of the 50%A – 50%B composition


Figure : Pb-Sn system
COOLING CURVE DIAGRAM
Cooling curve – useful tools for studying the
solidification process.

In solidification of alloyed metals, the temp. of


phase changes will be different for every
composition (because alloy consists of 2 or more
metals).

 The temp. & comp. of phase changes can be


graphed so that all possible combination of two
pure metals are represented.

 This will produce a graph known as PHASE


DIAGRAM which shows the relationship among
temp., comp. & phases present in alloy system.
COOLING CURVE FOR
ISOMORPHOUS BINARY

DIAGRAM
For pure metal, the
cooling curves show
horizontal thermal
arrest at their 1
freezes points.

• Different composition
will give different L1
cooling curves. Freezing
zone S1

• The slope changes at


L1-S1 etc., are
correspond to the
liquidus and solidus.
A binary isomorphous cooling curves

equilibrium phase diagram


COOLING CURVE FOR EUTECTIC
BINARY DIAGRAM
Liquid

A B C D
Solid

Liquid

Liquid + Solid

Solid
2.8 VARIOUS TYPE OF ALLOY TRANSFORMATIONS
FOR BINARY PHASE DIAGRAMS
2.8.1 Eutectice Transformations
In the eutectic reaction the single liquid phase transforms
simultaneously into the two solid phases form at the eutectic
temperature. The eutectic reaction can be written as,
→ α +β
L cooling

The eutectic transformation occurs at 183oC at a comp. of 61% Sn.

+
2.8.2 Peritectic alloy transformations

In the peritectic reaction a liquid phase reacts with a


solid phase to form a new and different solid phase.
The peritectic reaction can be written as,
Liquid, L + α → β
cooling

For example,
L (5.4% Ni) + δ (4.0% Ni) 1517 C
γ (4.3% Ni)
o
2.8.3 Monotectic transformation
The monotectic reaction occurs where at a specific temp.
the liquid solution of composition L1 transforms into a solid
α -phase and a second liquid of composition L2 which is
different from L1. The equation reads:
L1 cooling
→ α + L2

The monotectic
transformation occurs
at 955oC at a comp.of
36% Pb. From 955oC
down, pockets of lead-
rich melt are entrapped
in the solid Cu alpha-
phase.
2.8.4 Eutectoid transformation

The eutectoid reaction is similar to the eutectic reaction in that


one phase decompose into two phases upon cooling.

A eutectoid reaction where the single solid phase transforms into


solid phases having different compositions from the phase.
The eutectic reaction can be written as, γ cooling
→α + β

2.8.5 Peritectoid transformation


A in peritectoid reaction the two solid phases transform into the
single solid phase. The peritectoid reaction can be written as,

γ + β cooling
→ α
2.8.6 Monotectoid transformation

The monotectoid reaction occurs where at a specific temp.


the solid solution of composition α 1 transforms into the
two solid phases . The equation reads: α 1    → α 2 + β
cooling

The transformation of a Eutectic, Peritectic and Monotectic


is consider as the transformation form liquid to solid phase.
While the transformation of a Eutectoid, Peritectoid and
Monotectoid is consider as the transformation form solid
to solid phase.
2.9 INVARIANT REACTIONS

When the degree of freedom is equal to zero, the reaction is


called invariant reaction.
· Invariant reactions are found in
phase diagrams of many binary
alloys. An alloy may have only
one invariant reaction ( e.g. Pb-
Sn) or have many invariant
reactions depending on
concentration and temperature
(see engineering alloys).

• Invariant reactions are always


determined in a neighborhood of
the triple point that pins the
invariant reaction. According to
Gibbs phase rule there is zero
degrees of freedom at these
reaction points.
EXAMPLE
Find the peritectic and eutectoid reactions in the Cu-Zn
system?
• TUTORIAL
• Bismuth (melting point 271°C) and cadmium (melting
point 321°C) are assumed to be completely soluble in
the liquid state and completely insoluble in solid
state. They form a eutectic at 144°C containing 40 %
cadmium.
• Draw the equilibrium diagram to scale on a piece of
graph paper labeling all points, lines and areas.
• For an alloy containing 70% cadmium,
• Determine the temperature of initial and final
solidification.
• Determine the chemical composition and relative
amounts of phases present at a temperature of
200°C.
• Sketch the microstructure at room temperature.
• Draw the cooling curve.
OCT 2004
The cooling curves obtained when two pure
metals and several of their alloys were cooled
from the liquid phase are shown in figure
below.
a)Draw the phase diagram for the alloy system
to scale on a piece of graph paper and label
all points, lines and areas.
b) For an alloy containing 40 wt%A,
determine the liquidus temperature, solidus
temperature and freezing range of the alloy.
c)Consider an alloy containing 10 wt%A.
During solidification, determine composition
of the first solid to form.
d)For an alloy containing 70wt% A, determine
the chemical composition and relative
amount of phases present at 600°C.
MAR 2002
Table 1.0 shows temperatures of the
beginning and ending of the solidification
for Germanium-Silicon system. Construct
a phase diagram to scale on a piece of
graph paper labeling all points, lines and
areas.
For an alloy containing 40wt%Ge which is cooled
from liquid phase to room temperature, determine:
i. the composition of the first liquid solidified.
ii. the composition of the last liquid solidified.
iii. Describe the solidification process
of a 40wt%Si
and determine its chemical
compositions and relative amounts
of phases present at a temperature
of 1250°C.
iv. Draw the cooling curve for the 40wt%Si alloy.

v. Describe the solidification process.


MAR 2004
A hypothetical A-B alloy of composition
55wt%B - 45wt%A at some temperature is
found to consist of relative amount fraction
of 0.5 for both a and (3 phases. If the
composition of the p phase is 90wt%B -
10wt%A, what is the composition of the a
phase?
OCT 2003
The Bismuth (Bi) and Cadmium (Cd) alloy system is
generally known as the system with no single phase
of solid solution. It forms eutectic at the composition
(CE) and temperature (TE) of 40wt%Cd and 114°C
respectively. Based on the information given,
answer the following questions :
i) Draw the phase diagram on the graph paper and
label all points,
lines and areas.
Given that the melting point for Bismuth and
Cadmium are 280°C and 310°C respectively.
(Assume all lines are straight).
ii) With the aid of neat sketches, distinguish the microstructure
at room temperature for the eutectic alloy from an alloy
containing 80wt%Cd.
Eg 1: For an alloy containing 75 wt%
aluminium, determine the relative amount:
a) The temperature just slightly below
577C.
b) The temperature just slightly above
577C. SOLUTION:
Iron Carbide Phase Diagram (Fe-
Fe3C)

54
The Iron-Iron Carbide Phase
Iron Carbide Phase Diagram (Fe-
Fe3C)
Alpha, α Ferrite: - -
-Very low
solubility
of carbon.
- BCC structure.
- Max solid
solubility of 0.022
wt% C at 727°C
and the solubility
of carbon in
ferrite decreases
to 0.008 wt%C at
0°C.

55
Iron Carbide Phase Diagram (Fe-
Fe3C)
Austenite, γ :
- Interstitial solid
solution of C
in γ iron.
- FCC structure.
- Solubility of C
is 2.11% at
1148°C and
0.77% at
727°C.

56
Iron Carbide Phase Diagram (Fe-
Delta, δ iron
Fe3C)
- BCC structure
- Max. %C : 0.09
at 1495 ℃
Cementite, Fe3C : -
Intermetallic
compound.
- 6.67% C and
93.33% Fe.
- Orthorombic
structure
- Brittle

57
• MICROSTRUCTURE
CHANGES

• Allotropic changes / Polymorphic transformation: Species with


the same chemical composition, but different crystal
structures 58
Invariant reactions in Fe – Fe3C
system
1) Peritectic reaction.
1495 ℃
L (0.53 %C) + δ (0.09 %C) γ (0.17
%C)
2) Eutectic reaction.
1148 ℃
L (4.3 %C) γ (2.11 %C) + Fe3C (6.67 %C)

3) Eutectoid reaction.
727 ℃
γ (0.77 %C) α (0.02 %C) + Fe3C (6.67
%C)

59
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• Belowaustenite.
eutectoid temperature,
layers of ferrite and cementite
are formed. Pearlite.

60
• The microstructure of eutectoid
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, γ .
• Further cooling gives rise to α and pearlite.
Pearlite

61
Slow Cooling of Plain Carbon Steel
(Cont..)
• Hypereutectoid plain carbon steel: If a
1.2% C sample is heated up to 9500C and
held for sufficient time, it entirely gets
austenitized.
• Further cooling results results in
eutectoid cementite and pearlite.

62
Formation of pearlite
• Two-dimensional morphology of pearlite, apparently
consisting of alternating layers of cementite and ferrite.

• Three-dimensional analogy to the


morphology of pearlite, i.e. the
cabbage represents a single crystal
of pearlite, and the water in the
bucket the single crystal of ferrite.

63
Eg 2: Sketch of microstructural changes for a
steel containing 0.4 % C as it is cooled from
within the austenite phase region to below
eutectoid temp.
SOLUTION:

(Ans: pearlite 51%)


64
Evolution of
Microstructure

Euctectoid

65
HYPOEUTECTOID STEEL
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ+L System)
γ γ 1200 L+Fe3C

Fe3C (cementite)
1148°C
(austenite)
γ γ 1000
γ γ γ+Fe3C
α r s
α γ
γ 800 727°C
γ αγ αR S
wα =s/(r+s) 600 α+Fe3C
wγ =(1-w α)
400
0.77

α 0 Co1 2 3 4 5 6 6.7
α pearlite C o, wt% C
α w
pearlite =wγ
wα =S/(R+S) 100µm Hypoeutectoid
wFe3C =(1-w α) steel

66
HYPEREUTECTOID STEEL
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ+L System)
γ γ 1200 L+Fe3C

Fe3C (cementite)
1148°C
(austenite)
γ γ 1000
γ γ γ+Fe3C
Fe 3C
γ γ 800 r s
γ γ α R S
wFe3C =r/(r+s)600 α+Fe3C
wγ =(1-w Fe3C)
400
0.77

0 1 Co 2 3 4 5 6 6.7
pearlite C o, wt% C
wpearlite =wγ
wα =S/(R+S) 60µm Hypereutectoid
wFe3C =(1-w α) steel
67
SUMMARY OF Fe-Fe3C P.D

68
A carbon steel alloy containing 0.3 wt% C when cooled
just below eutectoid temperature level. Determine:
a) The relative amount of proeutectoid α ferrite form.
b) The relative amount of eutectoid α ferrite form.
c) Sketch the microstructure of item (a) and (b)
respectively.
Mar 2005
With the aid of a neat sketch, describe the
microstructural changes which take place
when a 1.1 wt% plain carbon steel is slowly
cooled from the austenite region just above
the upper critical temperature line.

Sep 2001
A carbon steel alloy containing 0.5 wt% C when cooled
from the austenite region crosses the A3 line. Describe
with neat sketches the microstructural changes that take
place during the slow cooling of this steel from the
austenite region. 70
Example
3.
A 0.90% C hypereutectoid plain-carbon steel is slowly
cooled from 900°C to a temperature just slightly above
727°C. Calculate the weight percent proeutectoid
cementite and weight percent austenite present in the
steel.
Example 4
A 0.25% C hypoeutectoid plain-carbon steel is slowly cooled from
950°C to a temp. just slightly below 727°C. Calculate:
(a) the weight percent proeutectoid ferrite in the steel.
(b) the weight percent eutectoid ferrite and weight percent
eutectoid cementite in the steel.

71
Example
5.
What is the Carbon concentration of an iron-carbon alloy
for which the relative amount (fraction) of total ferrite is
0.94?

Example 4 (Due date:1/9/2008)


A 1.25% C hypereutectoid plain-carbon steel
is slowly cooled from 950°C to a temp. just
slightly below 727°C. Calculate:
(a) the weight percent proeutectoid cementite
in the steel.
(b) the weight percent eutectoid ferrite and
72
weight percent eutectoid cementite in the
End of the Chapter 2
OPEN BOOK QUIZ

1. Answer Tutorial 1 Q1.2


2. Answer Tutorial 2 Q2.3

Note: ; Angstrom = m

MARK = 3/100