Ch3 - BBM 10103 Phase Diagram

CHAPTER 3:
PHASE
DIAGRAMS
#Mr. Muhammad Azri Bin Othman#BBM 10103# Pemilihan Bahan# SEM1 SESI 2013/2014# 1
Introduction to Phase Diagram
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?
Phase A Phase B
Nickel atom
Copper atom
A phase diagrams is a temperature (C) versus composition (wt%)
diagram shows the phases formed ( such as liquid, solid, solid solution,
compound etc) in differing mixtures (in terms of composition) of alloy
systems (two or more elements) over a range of temperatures
Most Phase diagram are

• Constructed by using equilibrium conditions. Its determined by using slow
cooling rate conditions.
• Used by engineers and scientists to understand and predict many aspects of
the behavior of materials, especially metals and alloys
Some of the important information obtainable from phase diagrams is:
i. To show what phases are present at different compositions and
temperature under slow cooling (equilibrium) condition
ii. To indicate the equilibrium solid solubility of one element in
another
iii. To indicate the temperature at which an alloy cooled under
equilibrium conditions starts to solidify and the temperature
range over which solidification occurs
iv. To indicate the temperature at which different phases start to
melt
The application of phase diagram for alloy systems are:
1. Design and control heat treating procedures of materials, such
as thermal histories (heat treatment process) and composition of
alloys.
2. Predict the crystal growth and phase transformation during
cooling/solidification process (in terms of alloys microstructure).
3. Improve the design of metals and alloys product, especially an
engineer whose involve in R&D and metal based industries
Two(2) common type of phase diagrams, which are:

1. Binary phase diagrams
A temperature (C) versus composition (wt%) diagram shows the
phases formed in differing mixtures of alloy systems (only two
elements) over a range of temperatures.
2. Ternary Phase
A temperature (C) versus composition (wt%) diagram shows the
phases formed in differing mixtures of alloy systems (more than
two elements) over a range of temperatures.
Phase Diagrams
• Indicate phases as function of T, Co, and P.
• For this course:
-binary systems: just 2 components.
-independent variables: T and Co (P = 1 atm is almost always used).
T(°C)
• Phase 1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 phase fields:
L
1300 L+ a
a
1200 a Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase Diagrams
1100
(FCC solid of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH (1991).
solution)
1000
0 20 40 60 80 100 wt% Ni
Phase Equilibria: Solubility Limit
Introduction
– Solutions – solid solutions, single phase
– Mixtures – more than one phase Adapted from Fig. 9.1,
Callister 7e.
Sucrose/Water Phase Diagram

• Solubility Limit: 10 0
Max concentration for Solubility
L
Temperature (°C)
which only a single phase 80 Limit
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 60 65 80 100
If Co > 65 wt% sugar: syrup + sugar.
Water
Sugar
Co =Composition (wt% sugar)
Pure
Pure
Components and Phases
• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g., a and b).
Aluminum- b (lighter
Copper
phase)
Alloy
a (darker
phase)
Adapted from
chapter-opening
photograph,
Chapter 9, Callister
3e.
#Mr. Muhammad Azri Bin Othman#BBM 10103# Pemilihan Bahan# SEM1 SESI 2013/2014#
Effect of T & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100°C,70) D (100°C,90)
1 phase 2 phases
100
80 L
(liquid)
Temperature (°C)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,70)
2 phases
Adapted from Fig. 0
9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)
How to build a Phase Diagram
•From figure, the x-axis shows the

composition (wt%) of mixture alloy
systems and the y-axis shows the
temperature (C)
•Compositions run from 100% Element A on the left of the diagram,

through all possible mixtures, to 100% Element B on the right. The
composition of an alloy is given in the form A - x%B. For example, Cu -
20%Al is 80% copper and 20% aluminium.
•Weight percentages are often used to specify the proportions of the

alloying elements, but atomic percent may be used.
•The type of percentage is specified e.g. Cu - 20wt%Al for weight

percentages and Cu - 20at%Al for atomic percentages.
•Alloys tend to solidify over a temperature range, rather than at a specific
temperature like pure elements.
• From figure, at each end of the phase diagram only one of the elements is
present (100% A or 100% B) and therefore a specific melting point exists.
•Sometimes there is a mixture of the constituent elements which produces

solidification at a single temperature like a pure element. This is called
the eutectic point.
•The eutectic point can be found

experimentally by plotting cooling
rates over ranges of alloy
composition
•By cooling alloys from the liquid
state and recording their cooling rates,
the temperature at which they start to
solidify can be determined and then
plotted on the phase diagram.
•If enough experiments are performed

over a range of compositions, a start
of solidification curve can be plotted
onto the phase diagram.
•This curve will join the three single

solidification points and is called
the liquidus line.
•In the same way that sugar dissolves into hot tea (a liquid solution) it is
possible for one element to dissolve in another, whist both remain inn the
solid state.
•This is called solid solubility and is characteristically up to a few

percent by weight.
•This solubility limit will normally change with temperature.

•The extent of the solid solubility
region can be plotted onto the phase
diagram and labelled appropriately.
•A solid solution of B in A (i.e. mostly

A) is called alpha and a solid solution
of A in B (i.e. mostly B) is called beta.
•If an alloy's composition does not place it within the small solid solution
regions at either side of the phase diagram, the alloy will become fully
solid at the eutectic temperature, shown as the eutectic line on the phase
diagram.
•At alloy compositions and temperatures between the start of solidification

and the point at which it becomes fully solid (the eutectic temperature)
a mushy mix of either alpha or beta will exist as solid lumps with a liquid
mixture of A and B. These partially solid regions are marked on the phase
diagram.
•The region below the eutectic line, and
outside the solid solution region, will be a
solid mixture of alpha and beta, and is
labelled to reflect this.
•These binary eutectic phase diagrams
normally only occur when two different
components are being alloyed e.g , CU-Ag phase diagram
•A phase diagram is a
temperature - composition
map which indicates the
phases present at a given
temperature and
composition.
•It is determined experimentally by recording cooling rates over a

range of compositions.
•These diagrams used to understand and predict the alloy

microstructure obtained at a given composition.
•Very simple binary phase diagrams do
not have a eutectic point.
•The liquid mixture will cool through a

solidification region (temperature
range) and become a solid solution of
the two constituent elements.
•These simple phase diagrams normally only occur when two very similar
elements are being alloyed or as part of a more complex phase diagram.
•There are three (3) different phases appear on the diagram, which are:
1. Liquid, L phase [single-phase region]
2. a + L phase [ two phase region]
3. Alpha, a phase or solid solution phase [single phase region]
•The phase boundaries are separated by two lines, which are:

1. Liquidus line – the line separating L and (a + L ) regions
2. Solidus line – the line separating a and (a + L) line
Phase Diagrams:
# and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60): L (liquid)
1 phase: a 1500
B (1250°C,35)
Cu-Ni
B(1250°C, 35): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase Diagrams 1100 A(1100°C,60)
of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991).
1000
0 20 40 60 80 100 wt% Ni
Phase Diagrams:
composition of phases
--the composition of each phase. Cu-Ni
T(°C) system
• Examples:
TA A
C o = 35 wt% Ni tie line
At T A = 1320°C: 1300 L (liquid)
Only Liquid (L) B
C L = C o ( = 35 wt% Ni) TB
a
At T D = 1190°C:
1200 D (solid)
Only Solid ( a) TD
C a = C o ( = 35 wt% Ni )
20 3032 35 40 4 3 50
At T B = 1250°C: C LC o C a wt% Ni
Both a and L Adapted from Fig. 9.3(b), Callister 7e.
(Fig. 9.3(b) is adapted from Phase Diagrams
C L = C liquidus ( = 32 wt% Ni here) of Binary Nickel Alloys, P. Nash (Ed.), ASM
C a = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Phase Diagrams:
weight fractions of phases
--the amount of each phase (given in wt%). Cu-Ni
• Examples: T(°C) system
C o = 35 wt% Ni TA A
tie line
At T A: Only Liquid (L) 1300 L (liquid)
W L = 100 wt%, W a = 0 B
At T D: Only Solid ( a) TB R S
a
W L = 0, W a = 100 wt%
1200 (solid)
At T B : Both a and L TD
D
S 43  35
WL 
20 3032 35 40 4 3 50
  73 wt % C LC o C a wt% Ni
R + S 43  32
Adapted from Fig. 9.3(b), Callister 7e.
R
Wa 
(Fig. 9.3(b) is adapted from Phase Diagrams of Binary
= 27 wt% Nickel Alloys, P. Nash (Ed.), ASM International,
R +S Materials Park, OH, 1991.)
The Lever Rule
• Tie line – connects the phases in equilibrium with each
other - essentially an isotherm
T(°C) How much of each phase?
tie line
Think of it as a lever (teeter-totter)
1300 L (liquid)
ML Ma
B
TB
a
1200 (solid)
R S R S
20 30C C
L o
40 C
a
50
M a S  M L R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.
ML S Ca  C0 R C0  CL
WL    Wa  
ML + M a R + S Ca  CL R + S Ca  CL
Ex: Cooling in a Cu-Ni Binary
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: 130 0 A
system
--binary L: 35 wt% Ni
a: 46 wt% Ni B
i.e., 2 components: 35 46
Cu and Ni. 32 C 43
--isomorphous 24 D
36 L: 32 wt% Ni
i.e., complete a: 43 wt% Ni
solubility of one 120 0 E
L: 24 wt% Ni
component in
another; a phase a: 36 wt% Ni
a
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
Cored vs Equilibrium Phases
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C a:
First a to solidify:
46 wt% Ni 35 wt% Ni
Last a to solidify:
< 35 wt% Ni
Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)
60
%EL for pure Cu
Elongation (%EL)
Tensile Strength (MPa)
400 50 %EL for

TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Callister 7e. Adapted from Fig. 9.6(b), Callister 7e.
--Peak as a function of Co --Min. as a function of Co
Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779°C L+b b
800
a: mostly Cu TE 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a+b
• CE : Min. melting TE 400
composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister 7e.
EX: Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: a+b Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
L (liquid)
Cb = 99 wt% Sn
--the relative amount a L+ a
200 183°C L+b b
of each phase: 18.3 61.9 97.8
S C -C 150
Wa = = b O R S
R+S Cb - Ca 100
a+b
99 - 40 59
= = = 67 wt%
99 - 11 88
C -C 0 11 20 40 60 80 99100
Wb = R = O a Ca Co Cb
R+S Cb - Ca C, wt% Sn
Adapted from Fig. 9.8,
40 - 11 29 Callister 7e.
= = = 33 wt%
99 - 11 88
EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
--the phases present: a+L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+a
--the relative amount 220
200
a R S L+b b
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
CL - Ca 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - Ca 23 C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - Ca 29 Callister 7e.
Microstructures
in Eutectic Systems: I
• Co < 2 wt% Sn T(°C) L: Co wt% Sn
400
• Result: L
a
--at extreme ends
300 L
--polycrystal of a grains
i.e., only one solid phase. L+ a
200
a
a: Co wt% Sn
(Pb-Sn
TE
System)
a+ b
100
0 10 20 30
Co Co , wt% Sn
Callister 7e. 2
(room T solubility limit)
Microstructures
in Eutectic Systems: II
L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn T(°C)
400
• Result: L
 Initially liquid + a L
a
 then a alone 300
L+a
 finally two phases a: Co wt% Sn
a
 a polycrystal 200
TE
 fine b-phase inclusions a
b
100
a+ b Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at T room ) 18.3
(sol. limit at TE)
Microstructures
in Eutectic Systems: III
• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.
Micrograph of Pb-Sn
T(°C) eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183°C L+b b
TE
100 160 m
a+b b: 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
a: 18.3 wt%Sn
0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn
Callister 7e.
Lamellar Eutectic Structure
Adapted from Figs. 9.14 & 9.15, Callister 7e.
Microstructures
in Eutectic Systems: IV
• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and a eutectic microstructure
L: Co wt% Sn
• Just above TE :
T(°C) a L
L
C a = 18.3 wt% Sn
300 a CL = 61.9 wt% Sn
L
Pb-Sn
L+a Wa = S = 50 wt%
system R+S
200
a R S L+ b b WL = (1- Wa) = 50 wt%
TE S
R
• Just below TE :
100 a+b C a = 18.3 wt% Sn
primary a C b = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 27 wt%
Callister 7e. Co, wt% Sn 31
Hypoeutectic & Hypereutectic
300
L
T(°C)
L+ a
Callister 7e. (Fig. 9.8 adapted a L+b b
from Binary Phase Diagrams,
200
TE
(Pb-Sn
2nd ed., Vol. 3, T.B. Massalski System)
(Editor-in-Chief), ASM a+b
International, Materials Park, 100
OH, 1990.)
0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: Co = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9, Metallography
a b
and Microstructures, a b
American Society for a a b b
Metals, Materials a b
Park, OH, 1985.)
a b
175 m 160 m
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister 7e. Adapted from Fig. 9.14, Callister 7e. (Illustration
Callister 7e. only)
Intermetallic Compounds
Adapted from
Fig. 9.20, Callister 7e.
Mg2Pb
Note: intermetallic compound forms a line - not an area -

because stoichiometry (i.e. composition) is exact.
Eutectoid & Peritectic
• Eutectic - liquid in equilibrium with two solids
L cool a + b
heat
• Eutectoid - solid phase in equation with two solid phases

S2 S1+S3
intermetallic compound -
 a + Fe3C (727ºC)
cementite
cool
heat
• Peritectic - liquid + solid 1  solid 2 (Fig 9.21)

S1 + L S2
cool
 + L heat  (1493ºC)
Eutectoid & Peritectic
Peritectic transition  + L 
Cu-Zn Phase diagram
Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition  +
Iron-iron carbide phase diagram
Introduction
• Metal and alloys have many useful engineering properties and have
widespread application in engineering design
• A variety of metal alloys such a plain carbon steels, alloy steels,
stainless steels, cast iron and copper alloys are used in
manufacturing various gears
• For example
1. Chromium steels – automobile transmission gears
2. Chromium molybdenum steels – aircraft gas turbine gears
3. Copper alloys- gear for low load levels
• Metals and alloys are divided into 2 categories:
1. Ferrous alloys – alloy based on iron
2. Nonferrous alloys- alloy based on the other metals
• Steel (or ferrous alloys) account for 90% of the world production of
metal because:
Good strength, toughness, ductile and relatively low cost
• Metals and alloys are divided into 2 categories:
1. Ferrous alloys – alloy based on iron
2. Nonferrous alloys- alloy based on the other metals
• Steel (or ferrous alloys) account for 90% of the world production of
metal because:
Good strength, toughness, ductile and relatively low cost
General operation of steelmaking
Iron-Carbon (Fe-C) Phase Diagram
•This is one of the most important alloys for structural applications. The
diagram Fe—C is simplified at low carbon concentrations by assuming
it is the Fe—Fe3C diagram. Concentrations are usually given in weight
percent. The possible phases are:
 a-ferrite (BCC) Fe-C solution

 -austenite (FCC) Fe-C solution
 -ferrite (BCC) Fe-C solution
 liquid Fe-C solution
 Fe3C (iron carbide) or cementite. An intermetallic compound.
•The maximum solubility of C in a- ferrite is 0.022 wt%. ferrite is

only stable at high temperatures. It is not important in practice
•Austenite has a maximum C concentration of 2.14 wt %. It is not stable
below the eutectic temperature (727 C) unless cooled rapidly (Chapter
10). Cementite is in reality metastable, decomposing into a-Fe and C
when heated for several years between 650 and 770 C.
•For their role in mechanical properties of the alloy, it is important to

note that:
Ferrite is soft and ductile
Cementite is hard and brittle
Thus, combining these two phases in solution an alloy can be obtained

with intermediate properties. (Mechanical properties also depend on the
microstructure, that is, how ferrite and cementite are mixed.)
• 2 important T(°C)
1600
points 
-Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148°C
A L+Fe3C
-Eutectoid (B): (austenite)
R S
Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C
a
800 727°C = T eutectoid
B
R S
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 m
Fe3C (cementite-hard)
C eutectoid
Result: Pearlite =
alternating layers of a (ferrite-soft)
a and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.) Adapted from Fig. 9.24,Callister 7e.
Iron Iron-Carbon Diagram
Peritectic Reaction Eutectic Reaction
Eutectoid
Reaction
Pearlite and
Cementine
Austenite
Ferrite
Pearlite and
Carbide
Pearlite
Steel Cast iron

Definition of structures
Various phases that appear on the Iron-Carbon
equilibrium phase diagram are as under:
•Austenite
•Ferrite
•Pearlite
•Cementite
•Martensite*
•Ledeburite
Unit Cells of Various Metals
• FIGURE - The unit cell for (a) austentite, (b) ferrite, and (c) martensite. The effect
of the percentage of carbon (by weight) on the lattice dimensions for martensite is
shown in (d). Note the interstitial position of the carbon atoms and the increase in
dimension c with increasing carbon content. Thus, the unit cell of martensite is in
the shape of a rectangular prism.
Microstructure of different phases of steel
• Ferrite is known as α solid solution.
• It is an interstitial solid solution of a small amount
of carbon dissolved in α (BCC) iron.
• stable form of iron below 912 deg.C
• The maximum solubility is 0.025 % C at 723C
and it dissolves only 0.008 % C at room
temperature.
• It is the softest structure that appears on the
diagram.
Ferrite
• Average properties are:
– Tensile strength = 40,000 psi;
– Elongation = 40 % in 2 in;
– Hardness > Rockwell C 0 or
> Rockwell B 90
• Pearlite is the eutectoid mixture
containing 0.80 % C and is formed
at 723°C on very slow cooling.
• It is a very fine platelike or lamellar
mixture of ferrite and cementite.
• The white ferritic background or
matrix contains thin plates of
cementite (dark).
Pearlite
– Elongation = 20 % in 2 in.;
– Hardness = Rockwell C 20, Rockwell B
95-100, or BHN 250-300.
• Austenite is an interstitial solid solution of

Carbon dissolved in  (F.C.C.) iron.
• Maximum solubility is 2.0 % C at 1130°C.
• High formability, most of heat treatments begin
with this single phase.
• It is normally not stable at room temperature.
But, under certain conditions it is possible to
obtain austenite at room temperature.
Austenite
– Elongation = 10 percent in 2 in.;
– Hardness = Rockwell C 40,
approx; and
– toughness = high
• Cementite or iron carbide, is very hard, brittle
intermetallic compound of iron & carbon, as
Fe3C, contains 6.67 % C.
• It is the hardest structure that appears on the
diagram, exact melting point unknown.
• Its crystal structure is orthorhombic.
• It is has
– low tensile strength (approx. 5,000 psi), but
– high compressive strength.
• Ledeburite is the eutectic

mixture of austenite and
cementite.
• It contains 4.3 percent C and is
formed at 1130°C.
Martensite - a super-saturated solid solution of
carbon in ferrite.
It is formed when steel is cooled so rapidly that the
change from austenite to pearlite is suppressed.
The interstitial carbon atoms distort the BCC ferrite
into a BC-tetragonal structure (BCT).; responsible for
the hardness of quenched steel
The Iron-Iron Carbide Diagram
• A map of the temperature at which different phase
changes occur on very slow heating and cooling in
relation to Carbon, is called Iron- Carbon Diagram.
• Iron- Carbon diagram shows
– the type of alloys formed under very slow
cooling,
– proper heat-treatment temperature and
– how the properties of steels and cast irons can be
radically changed by heat-treatment.
Various Features of Fe-C diagram
Phases present
L
a ferrite
 BCC structure
BCC structure Ferromagnetic
Paramagnetic Fairly ductile
 austenite Fe3C cementite

FCC structure Orthorhombic
Reactions Non-magnetic Hard
ductile brittle
Peritectic L +  = 
Max. solubility of C in ferrite=0.022%
Eutectic L =  + Fe3C
Eutectoid  = a + Fe3C Max. solubility of C in austenite=2.11%

Three Phase Reactions
• Peritectic, at 1490 deg.C, with low wt% C

alloys (almost no engineering importance).
• Eutectic, at 1130 deg.C, with 4.3wt% C, alloys
called cast irons.
• Eutectoid, at 723 deg.C with eutectoid
composition of 0.8wt% C, two-phase mixture
(ferrite & cementite). They are steels.
Iron Iron-Carbon Diagram
Peritectic Reaction Eutectic Reaction
Eutectoid
Reaction
Pearlite and
Cementine
Austenite
Ferrite
Pearlite and
Carbide
Pearlite
Steel Cast iron

The Iron-Iron Carbide Diagram
The diagram shows three horizontal lines which indicate
isothermal reactions (on cooling / heating):
• First horizontal line is at 1490°C, where peritectic
reaction takes place:
Liquid +  ↔ austenite
• Second horizontal line is at 1130°C, where eutectic
liquid ↔ austenite + cementite
• Third horizontal line is at 723°C, where eutectoid
austenite ↔ pearlite (mixture of ferrite &
cementite)
Delta region of Fe-Fe carbide diagram
Liquid +  ↔ austenite
Ferrite region of
Fe-Fe Carbide
diagram
Simplified Iron-Carbon phase diagram
austenite ↔ pearlite (mixture of ferrite &
cementite)
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
The Austenite to ferrite / cementite
transformation in relation to Fe-C diagram
In order to understand the transformation processes,
consider a steel of the eutectoid composition. 0.8%
carbon, being slow cooled along line x-x‘.
• At the upper temperatures, only austenite is present,
with the 0.8% carbon being dissolved in solid
solution within the FCC. When the steel cools
through 723°C, several changes occur
simultaneously.
• The iron wants to change crystal structure

from the FCC austenite to the BCC ferrite,
but the ferrite can only contain 0.02%
carbon in solid solution.
• The excess carbon is rejected and forms the
carbon-rich intermetallic known as
cementite.
Pearlitic structure
• The net reaction at the

eutectoid is the formation of
pearlitic structure.
• Since the chemical
separation occurs entirely
within crystalline solids, the
resultant structure is a fine
mixture of ferrite and
cementite.
Schematic picture of the formation
and growth of pearlite
Cementite
Ferrite
Austenite
boundary
Nucleation & growth of pearlite
The Austenite to ferrite / cementite transformation in relation
to Fe-C diagram
• Hypo-eutectoid steels: Steels having less than 0.8%
carbon are called hypo-eutectoid steels (hypo means
"less than").
• Consider the cooling of a typical hypo-eutectoid alloy
along line y-y‘.
• At high temperatures the material is entirely austenite.
• Upon cooling it enters a region where the stable
phases are ferrite and austenite.
• The low-carbon ferrite nucleates and grows, leaving
the remaining austenite richer in carbon.
• Hypo-eutectoid steels- At
723°C, the remaining austenite
will have assumed the eutectoid
composition (0.8% carbon), and
further cooling transforms it to
pearlite.
• The resulting structure, is a
mixture of primary or pro-
eutectoid ferrite (ferrite that
forms before the eutectoid
reaction) and regions of pearlite.
Hypoeutectoid Steel
T(°C)
1600

1400 L
  (Fe-C
  +L
  1200 1148°C L+Fe3C System)
(austenite)
Fe3C (cementite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister 7e. (Fig.
a 9.24 adapted from Binary
a  800 r s 727°C Alloy Phase Diagrams, 2nd
 a aRS ed., Vol. 1, T.B. Massalski
(Ed.-in-Chief), ASM
w a =s /(r +s ) 600
w  =(1- wa )
a + Fe3C International, Materials
Park, OH, 1990.)
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76
C0
pearlite
w pearlite = w 
w a =S /(R +S ) 100 m Hypoeutectoid
steel
w Fe3C =(1- w a )
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e.
to Fe-C diagram
• Hyper-eutectoid steels (hyper means "greater

than") are those that contain more than the
eutectoid amount of Carbon.
• When such a steel cools, as along line z-z' , the
process is similar to the hypo-eutectoid steel,
except that the primary or pro-eutectoid phase is
now cementite instead of ferrite.
Hypereutectoid Steel
T(°C)
1600

1400 L (Fe-C
    +L System)
 
1200
(austenite)
1148°C L+Fe3C
Fe3C (cementite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister 7e. (Fig.
Fe3C
 
9.24 adapted from Binary
800 r s Alloy Phase Diagrams, 2nd
  a R S
ed., Vol. 1, T.B. Massalski
(Ed.-in-Chief), ASM
w Fe3C =r/(r +s ) 600
a +Fe3C International, Materials
Park, OH, 1990.)
w  =(1- w Fe3C )
400
0 1 Co 2 3 4 5 6 6.7
0.76
(Fe)
pearlite Co , wt%C
w pearlite = w 
w a =S /(R +S )
w Fe3C =(1- w a ) 60 m Hypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e.
to Fe-C diagram
• As the carbon-rich phase nucleates and grows, the

remaining austenite decreases in carbon content,
again reaching the eutectoid composition at 723°C.
• This austenite transforms to pearlite upon slow
cooling through the eutectoid temperature.
• The resulting structure consists of primary
cementite and pearlite.
• The continuous network of primary cementite will
cause the material to be extremely brittle.
Hypo-eutectoid steel showing primary cementite along grain boundaries

pearlite
• It should be noted that the transitions as
discussed, are for equilibrium conditions,
as a result of slow cooling.
• Upon slow heating the transitions will

occur in the reverse manner.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
• When the alloys are cooled rapidly, entirely
different results are obtained, since sufficient time
may not be provided for the normal phase reactions
to occur.
• In these cases, the equilibrium phase diagram is no
longer a valid tool for engineering analysis.
• Rapid-cool processes are important in the heat
treatment of steels and other metals (to be discussed
later in H/T of steels).
Principal phases of steel and their
Characteristics
Crystal
Phase Characteristics
structure
Ferrite BCC Soft, ductile, magnetic
Soft, moderate
Austenite FCC strength, non-
magnetic
Compound of Iron
Cementite Hard &brittle
& Carbon Fe3C
Alloying Steel with more Elements
• Teutectoid changes: • Ceutectoid changes:
24
Cast Irons
-Iron-Carbon alloys of 2.11%C
or more are cast irons.
-Typical composition: 2.0-
4.0%C,0.5-3.0% Si, less than
1.0% Mn and less than 0.2%
S.
-Si-substitutes partially for C
and promotes formation of
graphite as the carbon rich
component instead Fe3C.
Example: Phase Equilibria
For a 99.6 wt% Fe-0.40 wt% C at a temperature just
below the eutectoid, determine the following
a) composition of Fe3C and ferrite (a)
b) the amount of carbide (cementite) in grams that
forms per 100 g of steel
c) the amount of pearlite and proeutectoid ferrite (a)
Solution: a) composition of Fe3C and ferrite (a)
b) the amount of carbide (cementite) CO = 0.40 wt% C
in grams that forms per 100 g of Ca = 0.022 wt% C
steel CFe C = 6.70 wt% C
3
1600

Fe3C Co  Ca 1400 L
 x100 T(°C)
Fe3C + a CFe 3C  Ca   +L
1200 1148°C L+Fe3C
Fe C (cementite)
(austenite)
0.4  0.022
 x 100  5.7g 1000
6.7  0.022  + Fe3C
800 727°C
R S
Fe3C  5.7 g 600 a + Fe3C
a  94.3 g 400
0 1 2 3 4 5 6 6.7
Ca CO Co , wt% C CFe
3C
c. the amount of pearlite and proeutectoid ferrite (a)
note: amount of pearlite = amount of  just above TE
Co = 0.40 wt% C
Ca = 0.022 wt% C 1600
Cpearlite = C = 0.76 wt% C 
1400 L
T(°C)
 Co  Ca   +L
 x 100  51.2 g 1200 1148°C L+Fe3C
 + a C  Ca
Fe C (cementite)
(austenite)
1000
 + Fe3C
800 727°C
RS
pearlite = 51.2 g 600 a + Fe3C
proeutectoid a = 48.8 g 400
0 1 2 3 4 5 6 6.7
Ca CO C Co , wt% C
Alloying Steel with More Elements
• Teutectoid changes: • Ceutectoid changes:
C eutectoid (wt%C)
Ti
T Eutectoid (°C)
Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni
wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34 from Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35 from
Edgar C. Bain, Functions of the Alloying Elements in Edgar C. Bain, Functions of the Alloying Elements in
Steel, American Society for Metals, 1939, p. 127.) Steel, American Society for Metals, 1939, p. 127.)
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.

Ch3 - BBM 10103 Phase Diagram

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Ch3 - BBM 10103 Phase Diagram

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CHAPTER 3:

Most Phase diagram are

Two(2) common type of phase diagrams, which are:

Sucrose/Water Phase Diagram

•From figure, the x-axis shows the

•Compositions run from 100% Element A on the left of the diagram,

•Weight percentages are often used to specify the proportions of the

•The type of percentage is specified e.g. Cu - 20wt%Al for weight

•Sometimes there is a mixture of the constituent elements which produces

•The eutectic point can be found

•If enough experiments are performed

•This curve will join the three single

•This is called solid solubility and is characteristically up to a few

•This solubility limit will normally change with temperature.

•A solid solution of B in A (i.e. mostly

•At alloy compositions and temperatures between the start of solidification

•It is determined experimentally by recording cooling rates over a

•These diagrams used to understand and predict the alloy

•The liquid mixture will cool through a

•The phase boundaries are separated by two lines, which are:

400 50 %EL for

--Peak as a function of Co --Min. as a function of Co

Adapted from Figs. 9.14 & 9.15, Callister 7e.

0 20 40 60 80 100 Co, wt% Sn

Note: intermetallic compound forms a line - not an area -

• Eutectoid - solid phase in equation with two solid phases

• Peritectic - liquid + solid 1  solid 2 (Fig 9.21)

Cu-Zn Phase diagram

Good strength, toughness, ductile and relatively low cost

Good strength, toughness, ductile and relatively low cost

 a-ferrite (BCC) Fe-C solution

•The maximum solubility of C in a- ferrite is 0.022 wt%. ferrite is

•For their role in mechanical properties of the alloy, it is important to

Thus, combining these two phases in solution an alloy can be obtained

Steel Cast iron

• Austenite is an interstitial solid solution of

• Ledeburite is the eutectic

 austenite Fe3C cementite

Eutectoid  = a + Fe3C Max. solubility of C in austenite=2.11%

• Peritectic, at 1490 deg.C, with low wt% C

Steel Cast iron

• The iron wants to change crystal structure

• The net reaction at the

• Hyper-eutectoid steels (hyper means "greater

• As the carbon-rich phase nucleates and grows, the

Hypo-eutectoid steel showing primary cementite along grain boundaries

• Upon slow heating the transitions will

• Teutectoid changes: • Ceutectoid changes:

wt. % of alloying elements wt. % of alloying elements

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