Materials Science

I3592IS

Equilibrium phase diagrams

Prof. O. T. Johnson
(Department of Mechanical and Metallurgical Engineering)
 Outline
• Lesson Objectives

• Definitions and Basic Concepts

• Binary Phase Diagrams

• The Iron-Carbon System

• Summary
2
Lesson Objectives

3
 Lesson Objectives
At the end of this lesson, you should be able to do the following:

1. Schematically sketch simple isomorphous and eutectic phase diagrams.

(a) On these diagrams label the various phase regions,
(b) Label liquidus, solidus, and solvus lines.

2. Given a binary phase diagram, the composition of an alloy, its

temperature, and assuming that the alloy is at equilibrium, determine
(a) what phase(s) is (are) present,
(b) the composition(s) of the phase(s), and
(c) the mass fraction(s) of the phase(s).

4
 Lesson Objectives
At the end of this lesson, you should be able to do the following:

3. For some given binary phase diagram, do the following:

(a) locate the temperatures and compositions of all eutectic,

eutectoid, peritectic, and congruent phase transformations; and
(b) write reactions for all these transformations for either heating
or cooling.

5
 Lesson Objectives
At the end of this lesson, you should be able to do the following:

4. Given the composition of an iron–carbon alloy containing between

0.022 wt% C and 2.14 wt% C, be able to
(a) specify whether the alloy is hypoeutectoid or hypereutectoid,
(b) name the proeutectoid phase,
(c) compute the mass fractions of proeutectoid phase and pearlite, and
(d) make a schematic diagram of the microstructure at a temperature
just below the eutectoid

6
Why study Phase Diagrams?
The understanding of phase diagrams for alloy
systems is extremely important because there is
a strong correlation between microstructure
and mechanical properties, and the
development of microstructure of an alloy is
related to the characteristics of its phase diagram
(i.e. number of phases, their proportions and the
way they are arranged).
7
Why study Phase Diagrams?

In addition, phase diagrams provide

valuable information about melting,
casting, crystallization, and other
phenomena

8
Definitions and Basic
Concepts

9
 Equilibrium
• A system is at equilibrium if its free energy is at a
minimum, given a specified combination of
temperature, pressure and composition.
• The (macroscopic) characteristics of the system do
not change with time — the system is stable.
• A change in T, P or C for the system will result in an
increase in the free energy and possible changes to
another state whereby the free energy is lowered.

10
10
 Equilibrium Phase Diagrams

• Phase diagrams show how two or more

different elements can co-exist together
over a range of compositions and
temperatures.
• Elements co-exist after they have either:
• Dissolved in each other to form a Solid
Solution, or
• Chemically combined to form a
Compound.
FPL Kavishe 1
1 11
 Alloys

• When a metal coexists with another

element, it forms an Alloy. Two different
elements form a Binary Alloy.
• Usually an Alloy is made up of a
combination of Solid solutions and a
Chemical Compound.
• When two metals combine, they form an
Intermetallic Compound.

FPL Kavishe 1
2 12
Solid Solutions

Interstitial Solid solutions

Interstitial solute atom

Substitutional Solid solutions

Substitutional solute atom

FPL Kavishe 1
3 13
 Hume-Rothery Rules
Rules for Substitutional Solid Solutions:
(i) The solute and solvent atoms must have
similar atomic size (within 15%).
(ii) The solute and solvent atoms must have
similar crystal structure.
(iii) The solute and solvent atoms must have
similar valence.
(iv) The solute and solvent atoms must have
similar electronegativity (ability of an atom to
attract an electron).

FPL Kavishe 1
4 14
 Rules of Solubility
• Solute atoms dissolve into the solvent atom
structure.
• Usually, solubility increases with increasing
temperature.
• Solute atoms dissolve until a Saturated
Solution is formed.
• If solute atoms dissolve beyond saturation
point, Super-saturated Solution is formed.

FPL Kavishe 1
5 15
 Solubility limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Sugar/Water Phase Diagram
• Solubility Limit:
Maximum concentration for
which only a single phase
solution exists.

Question: What is the

solubility limit for sugar in
water at 20°C?

Answer: 65 wt% sugar. 65

At 20°C, if C < 65 wt% sugar: syrup

Sugar
Water

At 20°C, if C > 65 wt% sugar: syrup + sugar C = Composition (wt% sugar)

16
 Phases and Grains
• Since an alloy consists of solid solutions and
compounds, these will appear as regions of
different structures under the microscope.

• Regions of different structures are called phases,

and these are made up of Crystals.

• A Phase is a distinct part of a material with the

same physical and chemical properties as well as
the same chemical composition.

• Groups of Crystals with the same orientation are

called Grains.
FPL Kavishe 17
17
Grains of Ferrite (solid solution) and Pearlite
(solution + compound) in a 0.2%C Steel,x500

Grain
Boundaries

FPL Kavishe 18
18
Phase Diagrams
 Components and Phases
• Components:
The elements or compounds that are mixed initially (Al and Cu).
• Phases:
A phase is a homogenous, physically distinct and mechanically separable
portion of the material with a given chemical composition and structure
( and ).
Aluminum-
Copper
Alloy

20
20
Components & Phases

21
Types of Phase
Diagrams

22
One Component Phase
Diagram

23
23
 Outline
• Lesson Objectives

• Definitions and Basic Concepts

• Binary Phase Diagrams

• The Iron-Carbon System

• Summary
2
Binary Phase
Diagrams

3
 Binary Phase Diagrams
Binary phase diagrams involving two components
are maps that represent the relationships between
temperature and the compositions and quantities
of phases at equilibrium, which influence the
microstructure of an alloy.
• Binary Isomorphous System
• Binary Eutectic System
• Binary Eutectoid System
• Binary Peritectic System 4
Binary Isomorphous System
Alloys of Copper and Nickel
• Nickel and Copper satisfy all Hume-Rothery rules. Ni
and Cu have complete solubility in each other (100%).
Ni and Cu show complete miscibility in solid and
liquid states.
• Alloys of copper and nickel are called monels.

Element Atomic Radius Crystal Valence

(nm) Structure
Copper (Cu) 0.128 fcc 1+, 2+

Nickel (Ni) 0.125 fcc 2+

5
Binary Isomorphous System
Cu-Ni system:
• The liquid L is a homogeneous liquid solution composed of
Cu and Ni.
• The α phase is a substitutional solid solution consisting of
Cu and Ni atoms with an FCC crystal structure.
• At temperatures below 1080 C, Cu and Ni are mutually
soluble in each other in the solid state for all compositions.
• The complete solubility is explained by their FCC structure,
nearly identical atomic radii and electro-negativities, and
similar valences.
• The Cu-Ni system is termed isomorphous because of this
complete liquid and solid solubility of the 2 components.
28
6
Cu-Ni Alloys/System

7
Cu-Ni Alloys/System

8
Cu-Ni Alloys/System

9
Cu-Ni Alloys/System

10
Cu-Ni Alloys/System

11
 Cooling Curves
Cooling curves of a Pure Metal and a Binary Alloy

(a) Pure Metal (b) BinaryAlloy

Temp Liquid (L) Temp

Liquid state

L+ S Liquidus Liquid +
Tm Solid
Solid (S)

Solidus
Solid state

Time Time
A Phase Diagram is constructed by plotting Liquidus and
Solidus Temperatures at different Chemical Compositions.
FPL Kavishe 18
12
Cooling Curves

19
13
Construction of phase diagrams
Equilibrium Phase Diagram of a System with Complete Solubility

LIQUID (L) TB
Liquidus
Tie line a L+ 
Temperature C

c
L+ 
TA Solidus

SOLID ()

A Clf Cl Co Cs Csi B
Composition (wt % B)

FPL Kavishe 20
14
Binary Isomorphous System
• Phase diagram: T(°C)
Cu-Ni system. 1600
Cu-Ni
• System is: 1500 L (liquid) phase
-- binary diagram
2 components: 1400
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 
solubility of one (FCC solid
component in 1100
solution)
another;  phase 1000
field extends from 0 20 40 60 80 100 wt% Ni
0 to 100 wt% Ni.

37
15
Binary Isomorphous System
• Indicate phases as a function of Temp, Comp and Pressure.
• Focus on:
- binary systems: 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(°C)
1600 • 2 phases:
L (liquid)
1500 L (liquid)  (FCC solid solution)

1400
• 3 different phase fields:
Cu-Ni L
system 1300 L+ 

1200 
(FCC solid
1100
solution)
1000
0 20 40 60 80 100 wt% Ni 24
16
 Effect of Temperature &
Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
T(°C)
1600

1500 L (liquid)

1400
B D
Cu-Ni
system 1300

1200 
(FCC solid solution)
1100 A

1000
Cu 0 wt% Ni
20 40 60 80 100 39
17
Binary Isomorphous System

FPL Kavishe 23
18
 Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
--how many phases and which phases are present.

• Examples:

Cu-Ni
phase
diagram

Melting points: Cu =
1085°C, Ni = 1453 °C

Solidus - Temperature where alloy is completely solid. Above this line, liquefaction begins.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification begins.
41
19
Determination of composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
• Examples: system

At TA = 1320°C:
Only Liquid (L) present
CL = C0 ( = 35 wt% Ni)
At TD = 1190°C:
Only Solid () present
C = C0 ( = 35 wt% Ni)
At TB = 1250°C:
Both  and L present
CL = C liquidus ( = 32 wt% Ni)
C = C solidus ( = 43 wt% Ni)
42
20
 Lever Rule

• Relative amounts of phases present in an alloy at a

given temperature may be calculated using the lever
rule, which states:
fs = Co - Cl
Cs - Cl

fl = Cs - Co
Cs - Cl
• Where fs is the proportion of solid phase and fl is the
proportion of the liquid phase
43
FPL Kavishe
21
 Illustration of the Lever Rule
Illustration of the Lever Rule

Cs - Cl

Cl Cs

Co - Cl Cs - Co

Co

44
FPL Kavishe
22
 Determination of weight fractions of
phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).
• Examples:
Cu-Ni system

WL 43 − 35
= = 73 wt %
43 − 32

W = 27wt %

23
Development of Microstructure in
Isomorphous Systems

24
 Limited Solubility with  AND 

• The binary alloy formed from limited solid

solubility of say element A in element B
has two different solid phases designated
as  and  phases.
• The  phase is the solid solutions of B
atoms in element A.
• The  phase is the solid solution of A
atoms in element B.

FPL Kavishe 47
5
 Invariant Reactions
• Invariant points in a binary alloy system define points
where three different phases coexist in equilibrium.

• When temperature is reduced slightly below the

invariant point, the high temperature phase will fully
transform to the low temperature phases.

• Transformations that occur at the invariant points are

isothermal and reversible. They are called invariant
reactions.

FPL Kavishe 48
6
Typical Invariant Reactions
(a) EutecticReaction

Liquid solid + solid  [ L +  ]

(b) EutectoidReaction

Solid  solid + solid  [  +  ]

(c) PeritecticReaction

Liquid + solid  solid  [ L +  ]

(d) PeritectoidReaction

Solid  + solid  solid  [  +  ]

FPL Kavishe 49
7
 Eutectic

• A eutectic or eutectic mixture is a mixture of two or more

phases at a composition that has the lowest melting point.
• It is where the phases simultaneously crystallize from molten
solution.
• The proper ratios of phases to obtain a eutectic is identified by
the eutectic point on a binary phase diagram.
• The term comes from the Greek 'eutektos', meaning 'easily
melted.‘

6
Binary Eutectic Phase Diagrams
• In a binary eutectic phase diagram, there
exists an invariant point called the
eutectic point at which a liquid of
eutectic composition CE solidifies
isothermally to produce two distinct solid
phases  and .

• The temperature at which the eutectic

transformation takes place is called the
eutectic temperature T .
FPL Kavishe E 9
Hypothetical Binary Eutectic
Phase Diagram
TB
LIQUID (L)
Liquidus
TA
Temperature

Liquidus E is the
Solidus Solidus
Eutectic Point
 L+ E L +
and CE
TE  TE
C

the Eutectic
Composition
Solvus Solvus
 +

RT

0 CE 100%B
(100% A) (0% A)
Composition (wt % B)
FPL Kavishe
10
 Binary Eutectic System
2 components has a special composition
with a min. melting T.
Cu-Ag system T(°C)
1200
• 3 single phase regions L (liquid)
(L, , ) 1000
• Limited solubility:  L + 
TE 800 779°C L + 
: mostly Cu 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE  + 
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C , wt% Ag
L(CE) (CE) + (CE)
cooling
L(71.9 wt% Ag) (8.0 wt% Ag) + (91.2 wt% Ag)
heating 11
Copper-Silver Phase Diagram

12
 Copper-Silver Phase Diagram
• Solvus – (solid solubility line) BC, GH
• Solidus – AB, FG, BEG (eutectic isotherm)
• Liquidus – AEF
• Maximum solubility: α = 8.0 wt% Ag, β = 8.8 wt %Cu
• Invariant point (where 3 phases are in equilibrium) is at E; CE =
71.9 wt% Ag, TE = 779C (1434F).
• An isothermal, reversible reaction between two (or more) solid
phases during the heating of a system where a single liquid
phase is produced.
Eutectic reaction
L(CE) (CE) + (CE)

cooling
L(71.9 wt% Ag) (8.0 wt% Ag) + (91.2 wt% Ag)
heating
13
Lead-Tin Phase Diagram
350
327 LIQUID (L)
300
Temperature C

250 L+
 232C
200 183C L +
19.2% 61.9% 95%
150 (Eutectic)

100
 +
50

0
0 20 40 60 80 100%
Pb Sn
(100% Pb) (0% Pb)
Composition (wt% Sn)

(Adopted from Metals Handbook, volume 8: Metallography, Structures and Phase

Diagrams, 8th edition, ASM International, 1986)

FPL Kavishe
14
 Lead-Tin Eutectic Alloy
• Eutectic alloys have many engineering uses since
these alloys have melting points much lower than
the melting points of the pure elements.
• The lead-tin eutectic system produces the material
for joining metals called solder.
• The eutectic alloy has a composition of 61.9% Sn
(38.1%Pb) and a melting point of 183C.
• The maximum solubility of tin in lead is 19.2%.
This occurs at the eutectic temperature of 183C.
• The maximum solubility of lead in tin is about 5%.
FPL Kavishe
15
 Exercise 1

(1)Referring to the given Pb-Sn binary equilibrium

phase diagram, calculate the proportion of α-phase and
β-phase in a lead-tin alloy of eutectic composition just
below the eutectic temperature.
(2)Referring to the given Pb-Sn binary equilibrium
phase diagram, calculate the proportion of α and β
phases in an alloy of lead and tin that contains 40% Sn
at a temperature of 182C.
Use the Lever rule.

FPL Kavishe
16
Lead-Tin Equilibrium Phase Diagram: Tie Line (red) and
Composition lines (blue) for the given Exercise
350
327 LIQUID (L)
300

250 L+
Temperature

 232 C
200 183C L +
19.2% 61.9% 95%
C

150 (Eutectic)

100
 +
50

0
0 20 40 60 80 100%
Pb Sn
(100% Pb) (0% Pb)
Composition (wt% Sn)

(Adopted from Metals Handbook, volume 8: Metallography, Structures and Phase

Diagrams, 8th edition, ASM International, 1986)

FPL Kavishe
17
Lead-Tin Phase Diagram

Liquidus
Solidus
Solidus

Solidus

Solvus Solvus

18
Solidification of Eutectic Mixtures
• Mixtures of some metals, such as copper & nickel, are completely soluble in
both liquid and solid states for all concentrations of both metals. Copper &
nickel have the same crystal structure (FCC) and have nearly the same
atomic radii. The solid formed by cooling can have any proportion of copper
& nickel. Such completely miscible mixtures of metals are called
isomorphous.

• By contrast, a mixture of lead & tin that is eutectic is only partially soluble
when in the solid state. Lead & tin have different crystal structures (FCC
versus BCT) and lead atoms are much larger. No more than 18.3 weight %
solid tin can dissolve in solid lead and no more than 2.2% of solid lead can
dissolve in solid tin (according to previous phase diagram).

• The solid lead-tin alloy consists of a mixture of two solid phases, one
consisting of a maximum of 18.3 wt% tin (the alpha phase) and one
consisting of a maximum of 2.2 wt% lead (the beta phase).
19
 Pb-Sn Phase Diagram
Ex. 1
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer:  +  T(°C) system
-- the phase compositions
Answer: C = 11 wt% Sn 300 L (liquid)
C = 99 wt% Sn
L+ 
-- the relative amount 
200 183°C L + 
of each phase 18.3 61.9 97.8
Answer: 150
C - C0 100
W =  +
 C - C

= 99 - 40 = 59 = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C C0 C
W  = C0 - C C, wt% Sn
C - C
29 = 0.33
= 40 - 11 =
99 - 11 88 20
 Pb-Sn Phase Diagram
Ex. 2
•For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present: T(°C)
Answer:  + L
-- the phase compositions
Answer: C = 17 wt% Sn 300 L (liquid)
CL = 46 wt% Sn L+ 
220 
-- the relative amount 200 L + 
of each phase 183°C
Answer:
100
CL - C0 46 - 40  +
W = =
CL - C  46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 C C0 CL C, wt% Sn
29
C0 - C 23
WL = = = 0.79
CL - C  29
21
 Pb-Sn Phase Diagram

• For lead & tin the eutectic composition is 61.9 wt%

tin and the eutectic temperature is 183ºC -- which
makes this mixture useful as solder.
• At 183ºC, compositions of greater than 61.9 wt% tin
result in precipitation of a tin-rich solid in the liquid
mixture, whereas compositions of less than 61.9 wt%
tin result in precipitation of lead-rich solid.

22
Microstructural Developments in
Eutectic System - 1
T(°C) L: C0 wt% Sn
400
•For alloys where L

C0 < 2 wt% Sn 300 L
•Result at room temperature is a
L+
polycrystalline with grains of  200 
phase having composition C0 TE : C0 wt% Sn

+ 
100

Pb-Sn
system 0 10 20 30
C0 C , wt% Sn
2
(room T solubility limit)

23
Microstructural Developments in
Eutectic System - 2
L: C0 wt% Sn
Pb-Sn T(°C)
400
system
L
L
2 wt% Sn < C0 < 18.3 wt% Sn 300 
L +
•Results in polycrystalline : C0 wt% Sn
microstructure with  grains and 200

small -phase particles at lower TE

temperatures. 
100
 +

0 10 20 30
2 C0 C , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
24
 Microstructural Developments in
Eutectic System - 3

•Co = CE
•Results in a
eutectic
microstructure
with alternating
layers of  and
 crystals.
Pb-Sn
system

cooling
L(61.9 wt%Sn)  (18.3 wt% Sn) +  (97.8 wt% Sn)
heating
25
 Lamellar Eutectic Structure
❑A 2-phase microstructure
resulting from the
solidification of a liquid
having the eutectic
composition where the Pb-rich
phases exist as a lamellae
that alternate with one Sn-rich
another.
❑Formation of eutectic layered
microstructure in the Pb-Sn
system during solidification at
the eutectic composition.
Compositions of α and β
phases are very different.
Solidification involves
redistribution of Pb and Sn
atoms by atomic diffusion. 26
Pb-Sn Microstructures

26
 Ni-Al Copper phosphorus eutectic

Pb-Sn 20mol% CeO2-80mol% CoO.

Ir-Si

28
Microstructural Developments in
Eutectic System - 4
• For alloys with18.3 wt% Sn < C0 < 61.9 wt% Sn
Pb-Sn
• Result:  phase particles and a eutectic microconstituent system
T(°C)
• Just above TE :
L: C0 wt% Sn  L C = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
 C -C
L + W  = L 0 = 0.50
 CL - C 
200 L+  
TE WL = (1- W  ) =0.50
• Just below TE :
100 +  C  = 18.3 wt% Sn
Primary α
eutectic  C  = 97.8 wt% Sn
eutectic  Cβ - C0
W =
Cβ - C  = 0.727
0 20 40 60 80 100
18.3 61.9 97.8
C, wt% Sn W  = 0.273 wt% Sn
29
Binary Peritectic Phase Diagrams
• In the binary peritectic diagram, an alloy of
composition Co undergoes a peritectic reaction in
such a way that a mixture of liquid of composition ClP
and solid  of composition CP transforms at the
peritectic temperature TP to form solid  of
composition CP.

• The invariant reaction is:

Liquid + solid  solid 

FPL Kavishe
31
Binary Peritectic Phase Diagrams
TA LIQUID (L)

a Liquidus
Temperature C

Solidus +L
TP b TP
 +L
TB
+ Solidus

Solvus
Solvus

A CP Co CP ClP B

Ci Composition (wt% B)

FPL Kavishe
31
Cu-Zn (Brass) Phase Diagrams

Cartridge brass:
70 wt% Cu

32
Section of Cu-Zn Phase Diagrams
1200
LIQUID (L)
1084
X
1000 + L  +L
Temperature

Y
  +L
800
+  
 +
C

600   

400 ’

(Adopted from Metals

200  + Handbook, volume 8:
Metallography, Structures and
Phase Diagrams, 8 t h edition,
A S M International, 1986)
0
Cu 20 40 60 80% Zn
( 100% Cu)
Composition (wt% Zn)

X: Alloy of composition 36.8% Zn at a temperature of 903  C.

Liquid (37.5%Zn) + Solid  (32.5%Zn)  Solid  (36.8%Zn).

FPL Kavishe
33
 Eutectoid & Peritectic
Peritectic transformation  + L 

Cu-Zn Phase diagram

Eutectoid transformation  +

34
Intermetallic Compounds

19 wt% Mg-81 wt% Pb

Mg2Pb

Note: intermetallic compounds exist as a line on the diagram - not a phase

region. The composition of a compound has a distinct chemical formula.
35
Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool  +  (For Pb-Sn, 183C, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other solid phases

Solid1 Solid2 + Solid3
 cool  + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat

• Peritectic - liquid and one solid phase transform to a 2nd solid

phase Solid1 + Liquid Solid2
cool
 +L heat ε (For Cu-Zn, 598°C, 78.6 wt% Zn)

36
37
 Outline
• Lesson Objectives

• Definitions and Basic Concepts

• Binary Phase Diagrams

• The Iron-Carbon System

• Summary
2
The Iron-Carbon
System

3
 Iron - Carbon System
• Pure iron when heated experiences 2 changes
in crystal structure before it melts.
• At room temperature the stable form, ferrite
( iron) has a BCC crystal structure.
• Ferrite experiences a polymorphic
transformation to FCC austenite ( iron) at 912
˚C (1674 ˚F).
• At 1394˚C (2541˚F) austenite reverts back to
BCC phase  ferrite and melts at 1538 ˚C
(2800 ˚F).
• Iron carbide (cementite or Fe3C) an
intermediate compound is formed at 6.7 wt%
C.
• Typically, all steels and cast irons have carbon
contents less than 6.7 wt% C.
• Carbon is an interstitial impurity in iron and
forms a solid solution with the    phases
4
Iron - Carbon System

5
Though carbon is present in relatively low concentrations, it
significantly influences the mechanical properties of ferrite: (a) α
ferrite, (b) austenite.
6
Four Solid Phases

7
 Iron Carbide (Cementite / Fe3C)

• Forms when the solubility limit of carbon in  ferrite is

exceeded at temperatures below 727 ˚C.
• Mechanically, cementite is very hard and brittle.
• For ferrous alloys there are 3 basic types, based on
carbon content:
❑ Iron (ferrite phase): <0.008 wt% C room temp
❑ Steel ( + Fe3C phase): 0.008 to 2.14 wt% C
❑ Cast iron: 2.14 to 6.70 wt% C

8
9
Iron-Iron Carbide Phase Diagrams
1600
1537
1495  + L
(P e ri te c tic) L I Q U I D (L)
 -ir o n 1394C

1300  + L

1200 Austenite ()

1133
2% C 4.3%C
(E u te c tic )
1000

910 Austenite () + Cementite (Fe3C)

800
 + 723C
0.8%C 723
(Eutectoid)
600
-iron
 + Fe3C
C e m e n t i te
400
STEELS CAST IRONS

RT

0 1 2 3 4 5 6 6.67

Composition (wt% C)

100% Fe 100% Fe3C

FPL Kavishe
10
Steel Portion of Fe-C System

1133
Acm
Temperature C

Austenite () Austenite +

910 A3 Cementite
+ ( + Fe3C)
A1
723 Ec

Ferrite () + Cementite (Fe3C)
500

RT +P P Pearlite (P) + Fe3C

0 .2 .4 .6 .8 1.0 1.2 1.4 1.6 1.8 2.0

(100% Fe)
Weight % Carbon

FPL Kavishe
11
Eutectoid Reaction in Steels

• The eutectoid reaction takes place at a

temperature of 723C (A1 temperature) for
steels that contain 0.8%C by weight.
• Reaction involves isothermal decomposition of
the high temperature solid phase called
austenite () to produce two solid phases called
ferrite () and cementite (Fe3C).
• For all temperatures below the eutectoid
temperature, the microstructure consists of a
eutectoid mixture of ferrite and cementite,
which is called pearlite.
FPL Kavishe
12
 Eutectoid Reaction in Steels

   + Fe3C [at 723C]

Austenite Pearlite

• In the eutectoid reaction, the austenite

contains 0.8%C in solution, the ferrite
formed contains 0.025%C in solution and
the cementite contains 6.67% combined
carbon.
• A steel consisting of 100% pearlite (a fully
pearlitic steel) is called a eutectoid steel.
FPL Kavishe
13
 Iron - Carbon System
T(°C)
• 2 important points 1600

- Eutectic (A): 1400 L
L  + Fe3C   +L A
1200 1148°C L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  + Fe3C 1000  
   +Fe3C
800 B 727°C = T eutectoid

600
+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 m
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
 and Fe3C phases,  (ferrite-soft)
not a separate phase.
14
Eutectoid reaction:
  + Fe3C
Pearlite

Redistribution of carbon by diffusion

Austenite – 0.76 wt% C
Ferrite - 0.022 wt% C
Cementite - 6.70 wt% C

15
 Hypoeutectoid Steel
T(°C)
1600

1400 L

   +L
  1200 1148°C L+Fe3C
(austenite)
 

Fe3C (cementite)
1000
C - C 0  + Fe3C
W =
C - C  800 727°C
W =(1 - W) 

600
 + Fe3C
pearlite 400
0 1 2 3 4 5 6 6.7
(Fe) C0 C, wt% C
0.76

pearlite =  + Fe3C
CFe3C - C0
W’ =
CFe3C - C Microstructures for iron-iron carbide alloys that are below
W pearlite = (1 – W’) the eutectoid with compositions between 0.022 and 0.76
wt% Carbon are hypoeutectoid.
16
 Hypoeutectoid Steel
T(°C)
1600

1400 L
   +L
  1200 
1148°C L+Fe3C
(austenite)

Fe3C (cementite)
  1000
   + Fe3C


800 727°C
  
600
 + Fe3C
400
0 1 2 3 4 5 6 6.7
 (Fe) C0 C, wt% C
0.76

pearlite

17
 Proeutectoid
• Formed before the eutectoid
• Ferrite that is present in the pearlite is called eutectoid ferrite.
• The ferrite that is formed above the Teutectoid (727°C) is proeutectoid.

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 Hypereutectoid Steel
T(°C)
1600

1400 L
Fe3C   +L
1200
  (austenite)
1148°C L+Fe3C

Fe3C (cementite)
 1000
 +Fe3C
W =x/(v + x)
800 v x
WFe3C =(1-W)
 V X
600
 +Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
W = X/(V + X)
Microstructures for iron-iron carbide alloys that have
WFe3C’=(1 - W)
compositions between 0.76 and 2.14 wt% carbon are
hypereutectoid (more than eutectoid).
19
 Hypereutectoid Steel
1600

1400 L
    +L
1200
  (austenite)
1148°C L+Fe3C

Fe3C (cementite)
  1000
   +Fe3C
Fe3C
  800
 
600
 +Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

20
Hypereutectoid Steel (1.2 wt%C)

pearlite

Proeutectoid: formed above the Teutectoid (727°C)

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Hypoeutectic & Hypereutectic
300
L
T(°C)
 L +
200 L +  (Pb-Sn
TE
 +
System)
100

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)

eutectic: C0 = 61.9 wt% Sn

 
 
   
 

 160 m
175 m eutectic micro-constituent

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Microstructure of Annealed
Plain Carbon Steels
• Steels with 0.8%C (Eutectoid steels)
Microstructure is 100% pearlite.
• Steels with less than 0.8%C (Hypoeutectoid steels)
Microstructure is a mixture of primary ferrite and
pearlite.
• Steels with more than 0.8%C, but up to 2%C
(Hypereutectoid steels)
Microstructure is a mixture of primary cementite and
pearlite

FPL Kavishe
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 Exercise
Calculate the proportions of ferrite and pearlite in a
0.5%C steel just below 723C.

Solution:
Note: Just below 723oC, ferrite contains 0.025%C and
pearlite contains 0.8%C.
% Ferrite = 0.8 – 0.5 x 100% = 38.7%
0.8 – 0.025

% Pearlite = 0.5 – 0.025 x 100% = 61.3%

0.8 – 0.025
FPL Kavishe
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 Exercise

Calculate the proportions of ferrite and cementite in a

0.5%C steel just below 723oC.
Solution:
The ferrite present is the primary ferrite plus the ferrite
contained in pearlite, i.e. the eutectoid ferrite. It contains
0.025%C in solution. The cementite is contained in the
pearlite, i.e. it is eutectoid cementite. Cementite contains
6.67%C.
% Ferrite = 6.67 – 0.5 x 100% = 92.85%
6.67 – 0.025
% Cementite = 0.5 – 0.025_ x 100% = 7.15%
6.67 – 0.025
FPL Kavishe
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26
 Exercise
For a 99.6 wt% Fe-0.40
wt% C steel at a
temperature just below
the eutectoid,
determine the
following:
a) The compositions of
Fe3C and ferrite ().
b) The amount of
cementite (in grams)
that forms in 100 g of
steel.

27
 Exercise

C = 0.022 wt% C
CFe3C = 6.70 wt% C
b) Using the lever rule with
the tie line shown 1600

1400 L
R C0 − C
WFe 3C = = T(°C)
  +L
R +S CFe 3C − C 1200
(austenite)
1148°C L+Fe3C

Fe3C (cementite)
0.40 − 0.022
= = 0.057 1000
 + Fe3C
6.70 − 0.022
800 727°C
R S
Amount of Fe3C in 100 g 600  +Fe3C
= (100 g)WFe3C 4000 6 6.7
1 2 3 4 5
C C0 CFe C
C, wt% C
= (100 g)(0.057) = 5.7 g 3

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 Gibbs Phase Rule
• Phase diagrams and phase equilibria are subject to the laws of thermodynamics.
• Gibbs phase rule is a criterion that determines how many phases can coexist within a
system at equilibrium.
P + F = C +N
P: # of phases present
F: degrees of freedom (temperature, pressure, composition)
C: components or compounds
N: noncompositional variables
For the Cu-Ag system @ 1 atm for a single phase P:
N=1 (temperature), C = 2 (Cu-Ag), P= 1 ( , L)
F = 2 + 1 – 1= 2

This means that to characterize the alloy within a single phase

field, 2 parameters must be given: temperature and composition.
If 2 phases coexist, for example, +L  +L, + then according to GPR, we have 1
degree of freedom: F = 2 + 1 – 2= 1. So, if we have Temp or composition, then we can
completely define the system.
If 3 phases exist (for a binary system), there are 0 degrees of freedom. 29
Gibbs Phase Rule

30
Gibbs Phase Rule

31
Gibbs Phase Rule

32
Gibbs Phase Rule

33
 Summary
• Phase diagrams are useful tools to determine:
-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
For a given temperature and composition of
the system.

• The microstructure of an alloy depends on

-- its composition, and
-- rate of cooling equilibrium

34
 Classwork
1. A 0.8% C eutectoid plain-carbon steel is slowly cooled from 750oC to a temperature
just slightly below 723oC. Assuming that the austenite is completely transformed to α ferrite
and cementite:
(a) Calculate the weight percent eutectoid ferrite formed.
(b) Calculate the weight percent eutectoid ferrite formed

2. A 0.4% C hypoeutectoid plain-carbon steel is slowly cooled from 940oC to a

temperature just slightly above 723oC:
(a) Calculate the weight percent austenite present in the steel.
(b) Calculate the weight percent proeutectoid ferrite present in the steel.

35
 Classwork

3. A 0.4% C hypoeutectoid plain-carbon steel is slowly cooled from 940oC to a

temperature just slightly below 723oC:
(a)Calculate the weight percent austenite proeutectoid ferrite present in the steel.
(b)Calculate the weight percent eutectoid ferrite and eutectoid cementite present in the
steel.

4. A hypoeutectoid plain-carbon steel that was is slowly cooled from the austenitic
region to room temperature contains 9.1 wt% eutectoid ferrite. Assuming no change in
structure on cooling from just below the eutectoid temperature to room temperature, what is
the carbon content of the steel?

36