Chapter 9: Phase Diagrams

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

Phase A Phase B

Nickel atom
Copper atom Chapter 9 - 1
 What is a phase?
o Phase
A phase is a homogeneous portion of a system that has uniform physical and
chemical characteristics.
Every pure material and every solid, liquid, and gaseous solution is considered
to be a phase.

When two phases are present in a system, it is not necessary that there be a
difference in both physical and chemical properties; a disparity in one or the
other set of properties is sufficient.
Example: Water and ice (physically dissimilar)
BCC Iron and FCC Iron

Systems composed of two or more phases are termed “mixtures” or

“heterogeneous systems.” Chapter 9 - 2
 What are Phase Diagrams?
They are Pressure-Temperature or Composition-Temperature
Diagrams depending on the no. of components.
Phase diagrams are also called
o Equilibrium Diagrams
o Constitutional Diagrams
Phase diagrams are essentially stability maps.

Phase Equilibrium
A system is at equilibrium if its free energy (a thermodynamic
quantity) is at a minimum under some specified combination of
temperature, pressure, and composition.
In a macroscopic sense, this means that the characteristics of the
system do not change with time but persist indefinitely, i.e., the
system is stable. 3
 What, How and Why?
Why are phase diagrams needed?
1. For design and control of heat-treating procedures; some
properties of materials are functions of their microstructures,
and, consequently, of their thermal histories.
2. Even though most phase diagrams represent stable (or
equilibrium) states and microstructures, they are nevertheless
useful in understanding the development and preservation of
non-equilibrium structures and their attendant properties

How are they obtained?

They are obtained from –
Experimentally: thermal analysis, metallography, XRD, and many
other indirect methods.
Theoretically: Thermodynamic calculations of free energy.
4
Who uses Phase Diagrams?

Any discipline dealing with materials

o Materials science

o Engineering (Civil, Electrical,

Mechanical…..)

o Mineralogy

o Physical chemistry

5
 Variables in Phase Diagrams

Composition

Temperature

Pressure

6
 Types of Phase Diagrams
Based on number of components

One component Two Component Three Component

(Unary) (Binary) (Ternary)

• Water • Water-NaCl • Al-Si-Mg

• Carbon dioxide • Water-Sugar • Fe-C-Cr
• Carbon • Al-Si • Ti-Ni-Zr
• Pb-Sn • Mg-Al-Zn
• Al-Cu
• Ti-Ni
• Fe-C

In reality, most systems are multi-component. ASM

Handbook (Vol 3.) has nearly 3000 phase diagrams. 7
Example: Unary phase diagram of H2O Composition
is fixed.

ao: sublimation curve, bo: melting curve, co: vapourisation curve,

c: critical point, o: Triple point or invariant point
8
Example: Binary phase diagram of Pb-Sn

Pressure is generally kept constant at 1 atm.

9
Example: Ternary phase diagram

Pressure is generally
maintained constant at 1
atm.
10
 Definitions
o Components are pure metals and/or compounds of which an alloy is

composed.

o System relates to the series of possible alloys consisting of the same

components, but without regard to alloy composition.

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.
11
 Phase Equilibria: Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

• Solubility Limit: 100
Maximum concentration for Solubility

Temperature (ºC)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup

Sugar
Water

C = Composition (wt% sugar)

At 20ºC, if C > 65 wt% sugar:
syrup + sugar Chapter 9 - 12
 Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
Chapter 9 - 13
 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally soluble in one another for all proportions.

Chapter 9 - 14
 Binary Phase Diagrams
• Indicate phases as a function of T, C, and P.
• For this course:
- binary systems: just 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(ºC)
Phase
1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni Chapter 9 - 15
 Information from Binary Phase
Diagrams

Phases present

Composition of the phases

Relative amount of phases

Chapter 9 - 16
 Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
Cu-Ni system. 1600

• System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400
diagram
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 a
solubility of one
component in 1100
(FCC solid
another; a phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).
Chapter 9 - 17
 Isomorphous Binary Phase
Diagram
The line separating the L liquid phase and the a+L phase is
called the liquidus line.

The line separating the solid a phase from the a+L

phase is called the solidus line.

The solidus and liquidus lines for an isomorphous phase

diagram meet at the two composition extremities; these
correspond to the melting point of the pure components.

Chapter 9 - 18
 P: Melting point of Cu
R: Melting point of Ni
Single phase: Liquid, α
R
Two phase: α + L
Liquidus Line: PQR
Solidus Line: PSR
Q Cu and Ni are
S
completely soluble in
the solid state, i.e.,
P they form a continuous
solid solution at all
compositions.
Chapter 9 - 19
 Phase Diagrams:
Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a

B (1250ºC,35)
1500
Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 20
 Phase Diagrams:
Determination of phase compositions
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C0 Ca wt% Ni
Both a and L present Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Ca = C solidus ( = 43 wt% Ni) Park, OH (1991).

Chapter 9 - 21
 Phase Diagrams:
Determination of phase weight fractions
• Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43  35
WL 
20 3032 35 40 43 50
  0.73 CL C 0 Ca wt% Ni
R +S 43  32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
Wa 
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

Chapter 9 - 22
 Summary: Tie Line Rule
1. A tie line is constructed across the
two-phase region at the temperature of
the alloy.

2. The intersections of the tie line and

the phase boundaries on either side
are noted.

3. Perpendiculars are dropped from

these intersections to the horizontal
composition axis, from which the
composition of each of the respective
phases is read.

Tie line Rule is used to determine the composition of the phases.

Chapter 9 - 23
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other – also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 30CL R S
C0 40 Ca 50

wt% Ni Ma x S  ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL    a Wa   0
ML  M a R  S Ca  CL R  S Ca  CL
 Chapter 9 - 24
 Summary: Lever Rule
1. The tie line is constructed across
the two-phase region at the
temperature of the alloy.
2. The overall alloy composition is
located on the tie line.
3. The fraction of one phase is
computed by taking the length of tie
line from the overall alloy
composition to the phase boundary
for the other phase, and dividing by
the total tie line length.
4. The fraction of the other phase is
determined in the same manner. S Ca  C 0
WL  
5. If phase percentages are desired, R  S Ca  C L
each phase fraction is multiplied by
R C  CL
100. Wa   0
R  S Ca  C L
Lever Rule is used to determine the amount of the phases (in wt. %).
Lever Rule is also called Inverse Lever Rule. Chapter 9 - 25
 Development of Microstructure:
Equilibrium Cooling of a Cu-Ni Alloy
• Phase diagram: T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
system
• Consider 130 0 A
L: 35 wt% Ni
microstuctural a: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
Example: a
(solid)
extreme slow cooling in a
110 0
furnace, cooling in sand 20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
mould Callister & Rethwisch 8e.
Chapter 9 - 26
 Development of Microstructure:
Equilibrium Cooling of a Cu-Ni Alloy
• During cooling in the region between the solidus and
the liquidus lines, the fraction of the a phase increases
with continued cooling
• Overall alloy composition remains unchanged during
cooling
• There is a redistribution of the component i.e. in this
case Cu and Ni atoms between the phases.

•The solidification process is almost completed as the

composition reaches the solidus line.
•Upon crossing the solidus line, the remaining liquid
solidifies forming the polycrystalline a phase, having
unifrom composition.
•Subsequent cooling will produce no microstructural or
Chapter 9 - 27
compositional alterations..
Development
of
microstructur
Non-Equilibrium
eCooling
Assumption:
diffusion rates in the
liquid phase are
sufficiently rapid such
that equilibrium is
maintained in the liquid
Example:
Rapid/Fast cooling,
Rapid Solidification Processing
Chapter 9 - 28
Development of Microstructure: Non-
Equilibrium Cooling of a Cu-Ni Alloy
• No change during cooling to liquidus line, when compared to
equilibrium cooled microstructure.

• During cooling in the region between liquidus and solidus

lines:
•The diffusion in the solid a phase is relatively slow
• A greater proportion of liquid is present compared to
equilibrium cooling.

• Solidus line is shifted to higher nickel content.

• The degree of displacement of the non-equilibrium solidus

curve depends on the rate of cooling.
Chapter 9 - 29
 Cored vs Equilibrium Structures
• 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.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 30
 Elimination of coring
• Non-equilibrium cooling results in coring.
• Coring may be eliminated by a homogenization heat
treatment carried out at a temperature below the solidus
point for the particular alloy composition. During this
process, atomic diffusion occurs, which produces
compositionally homogeneous grains.

The dashed line shows

the temperatures for
homogenization heat
treatment to eliminate
coring.

Chapter 9 - 31
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
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), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Chapter 9 - 32
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE ab
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag)
Chapter 9 - 33
heating
 Binary Cu – Ag Phase Diagram
• The a phase is a solid solution rich in Cu. It has Ag as the
solute component, and has a FCC crystal structure
• The b phase is a solid solution rich in Ag, and has Cu as
solute. The crystal structure is also FCC.
• The solid solubility limit line separating the a and ab phase
regions is called the solvus line.
• The boundary between a and a+ L phase regions is the
solidus line.
•The boundary between L and a+ L phase regions is the
liquidus line.
• Solidus, liquidus and solvus lines also exist for b phase.
• The horizontal line parallel to the composition axis is also a
solidus line. This is also called the eutectic isotherm.
• The point at which the two liquidus lines meet on the phase
diagram lies on the horizontal line. This is the eutectic point,
Chapter 9 - 34
and also called the invariant point.
 EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
100
W =
a R+S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Ca Ca C0 Cb
Wb = R = C, wt% Sn
R+S Cb - Ca Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 Chapter 9 - 35
99 - 11 88
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220
200
a R S L+b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
Chapter 9 - 36
 Microstructural Developments
in Eutectic Systems I

• For alloys for which T(ºC)

400
L: C0 wt% Sn

C0 < 2 wt% Sn L
• Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)

Chapter 9 - 37
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which 400
T(ºC)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
a
b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12, 0 10 20 30
Callister & Rethwisch 8e. 2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 38
 Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183ºC Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
Adapted from Fig. 9.14,
a: 18.3 wt%Sn Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn Chapter 9 - 39
Callister & Rethwisch 8e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

Chapter 9 - 40
 Microstructural Developments
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
a
b b
200 R S L+ WL = (1- Wa) = 0.50
TE S
R
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn Chapter 9 - 41
 Hypoeutectic & Hypereutectic
300
L
T(ºC)
L+ a
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. a L+b b
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. a+b System)
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 m 160 m
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)
Chapter 9 - 42
 Intermetallic Compounds

Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg2Pb

Note: intermetallic compound exists as a line on the diagram - not an

area - because of stoichiometry (i.e. composition of a compound
Chapter 9 - 43
is a fixed value).
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other

solid phases
intermetallic compound
S2 S1+S3 - cementite

 cool a + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

heat

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
 +L heat  (For Fe-C, 1493ºC, 0.16 wt% C)

Chapter 9 - 44
 Eutectoid & Peritectic
Peritectic transformation  + L 
Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation  +
Chapter 9 - 45
 Gibbs Phase Rule
• A criterion for the number of phases to co-
exist within a system at equilibrium.

PF C N
• P : Number of phases present
• F: Number of degrees of freedom
• C: Number of components
• N: Number of non-compositional variables
i.e. pressure and/or temperature
• For binary temperature-composition
phase diagrams, pressure is constant,
hence N =1 Chapter 9 - 46
 Degrees of Freedom (F)
• Number of externally controlled variables (e.g.,
temperature, pressure, composition) which must be
specified to completely define the state of a system
• Or, F is the number of these externally controlled
variables that can be changed independently without
altering the number of phases that coexist at
equilibrium.

Chapter 9 - 47
 Example: Application of Gibbs
Phase Rule
• C = 2 ; N =1
A B • At point A:
T(ºC) o P=1
1200
o F=C+N–P=2
L (liquid)
1000 o To completely describe the
a L + a 779ºC L+b b
characteristics of an alloy in
800 the single-phase region, two
8.0 71.9 91.2
X parameters need to be
600 specified, composition and
ab temperature
400 • At point B, P = 2, F =1
200 o To completely describe the
0 20 40 60 CE 80 100 characteristics of an alloy in
• At point X: the two-phase region, one
o P = 3. Therefore F = 0 parameter needs to be
o Composition of all three phases and specified, composition or
temperature are fixed. temperature Chapter 9 - 48
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(ºC)
1600
points 
- Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C

a
800 727ºC = T eutectoid
B
600
a+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
a and Fe3C phases a (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
Chapter 9 - 49
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
 Hypoeutectoid Steel
T(ºC)
1600

1400 L
  (Fe-C
  +L
  1200 1148ºC L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister &
a Rethwisch 8e.
a  800 727ºC (Fig. 9.24 adapted from
 a a Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400 1990.)
a 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 m
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 50
 Hypoeutectoid Steel
T(ºC)
1600

1400 L
(Fe-C
a   +L
System)
a  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
 a
1000
 + Fe3C Adapted from Figs. 9.24
Wa = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
800 r s 727ºC
W =(1 - Wa) (Fig. 9.24 adapted from

aRS Binary Alloy Phase

Diagrams, 2nd ed., Vol.
a 600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
pearlite Materials Park, OH,
400 1990.)
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Wpearlite = W
Wa’ = S/(R + S) 100 m
Hypoeutectoid
steel
WFe3C =(1 – Wa’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 51
 Hypereutectoid Steel
T(ºC)
1600

1400 L (Fe-C
  +L System)
 
 
1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
Fe3C
 
Rethwisch 8e. (Fig. 9.24
800 adapted from Binary Alloy
  a Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 52
 Hypereutectoid Steel
T(ºC)
1600

1400 L (Fe-C
 +L System)
Fe3C 
  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
 +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
W =x/(v + x) Rethwisch 8e. (Fig. 9.24
800 v x adapted from Binary Alloy
WFe3C =(1-W)
a V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
Wa = X/(V + X)
60 mHypereutectoid
WFe =(1 - Wa) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 53
 Example Problem
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 (a).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (a) in the 100 g.

Chapter 9 - 54
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown 
1400 L
R C  Ca T(ºC)
WFe3C   0   +L
R  S CFe3C  Ca

Fe C (cementite)
1200 1148ºC L+Fe3C
(austenite)
0.40  0.022
  0.057 1000
 + Fe3C
6.70  0.022
800 727ºC
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 55
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C
1600

1400 L
V C  Ca T(ºC)  +L
Wpearlite   0 

Fe C (cementite)
V  X C  Ca 1200
(austenite)
1148ºC L+Fe3C

0.40  0.022 1000

  0.512  + Fe3C
0.76  0.022
800 727ºC
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g
Chapter 9 - 56
 VMSE: Interactive Phase Diagrams
Microstructure, phase compositions, and phase fractions respond interactively

Change alloy composition Chapter 9 - 57

 Alloying with Other Elements

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt% C)
Ti
T Eutectoid (ºC)

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 & Rethwisch 8e. Adapted from Fig. 9.35,Callister & Rethwisch 8e.
(Fig. 9.34 from Edgar C. Bain, Functions of the (Fig. 9.35 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American Society for Alloying Elements in Steel, American Society for
Metals, 1939, p. 127.) Metals, 1939, p. 127.)

Chapter 9 - 58
 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
given the temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
• Important phase diagram phase transformations include
eutectic, eutectoid, and peritectic.

Chapter 9 - 59