TJ TJ TJ TJ

Phase Diagrams
TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ
Dr. Tariq Jamil
TJ TJ TJ TJ TJ

E-mail: tariqjamil@neduet.edu.pk
TJ TJ TJ TJ
Office: DICE Energy Lab, MED, NEDUET

1
 Books / Resource Material
TJ TJ TJ TJ

• Text book: “Materials Science and Engineering: An Introduction” by

TJ William D. Callister and
TJ David G. Rethwisch, 7thTJ
Edition TJ TJ
• Chapter #9

TJ TJ TJ TJ
• Reference book: Principles of Material Sciences & Engineering by
William F. Smith,
TJ 3 Edition
rd
TJ TJ TJ

• Online resources (Lectures and resource material on Google

TJ classroom, YouTube,TJWikipedia) TJ TJ TJ

TJ TJ TJ TJ

2
 Materials and Metallurgy (ME-209)
(According to Course Outline)
TJ TJ TJ TJ

Heat treatment and phase transformation in materials: Types of heat treatment

TJ processes, effects of TJ
heat treatment on material TJ structure and properties,
TJ concepts of TJ
phases in solids, solubility limit in solid solutions, strengthening mechanisms (solid solution
and precipitate strengthening), binary phase diagrams, iron-iron carbide phase diagram,
TJ
diffusional and non-diffusionalTJphase transformation, kinetics
TJ TJ
of phase transformation
TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

3
 TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

4
 Chapter 9: Phase Diagrams
TJ TJ TJ TJ
• When we combine two elements...
what is the resulting equilibrium state?
TJ
• In particular, TJ
if we specify... TJ TJ TJ
-- the composition (e.g., wt% Cu - wt% Ni), and
TJ -- the temperature (TTJ ) TJ TJ
then...
How
TJ many phases form? TJ TJ TJ
What is the composition of each phase?
What is the amount of each phase?
TJ TJ TJ TJ TJ

Phase A Phase B
TJ TJ TJ TJ

Nickel atom
Copper atom
5
 Phase Equilibria: Solubility Limit
TJ
• Solution – solid, liquid,TJor gas solutions, single
TJ
phase TJ

• Mixture – more than one phase Adapted from Fig. 9.1,

TJ TJ TJ TJ
Callister & Rethwisch 8e. TJ
Sugar/Water Phase Diagram
• Solubility Limit: 100
TJ TJ TJ TJ
Maximum concentration for Solubility
L

Temperature (ºC)
which
TJ only a single phase TJ 80 Limit
TJ TJ
solution exists. (liquid)
60 +
L
TJ Question: TJ
What is the TJ
40 (liquid solution TJ S TJ
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)
TJ TJ TJ TJ
Answer: 65 wt% sugar.
0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup
C = Composition (wt% sugar)

Sugar
Water
At 20ºC, if C > 65 wt% sugar:
syrup + sugar 6
 Components and Phases
TJ TJ TJ TJ
• Components:
The elements or compounds which are present in the alloy
TJ (e.g., Al and
TJ Cu) TJ TJ TJ
• Phases:
The physically and chemically distinct material regions
TJ TJ TJ TJ
that form (e.g., α and β).
TJ TJ TJ TJ
Aluminum- β (lighter
Copper
phase)
TJ Alloy TJ TJ TJ TJ

α (darker
TJAdapted from chapter- TJ TJ TJ
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.
7
 Effect of Temperature & Composition
• TJ TJ # of phases: pathTJA to B.
Altering T can change TJ

• Altering C can change # of phases: path B to D.

TJ TJ TJ B (100ºC,C = 70) DTJ(100ºC,C = 90) TJ
1 phase 2 phases
100
TJ TJ TJ TJ
80 L
Temperature (ºC)
TJ TJ TJ (liquid) TJ
water- 60 +
sugar L S
TJ TJ TJ
(liquid solution TJ TJ
system 40 (solid
i.e., syrup) sugar)
TJ 20
TJ TJ A (20ºC,C = 70) TJ
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar) 8
 Criteria for Solid Solubility
TJ TJ TJ TJ
Simple system (e.g., Ni-Cu solution)
TJ TJ TJ TJ TJ
Crystal electroneg r (nm)
Structure
TJ TJ TJ TJ
Ni FCC 1.9 0.1246
TJ Cu FCC TJ 1.8 TJ
0.1278 TJ

TJ TJ the same crystal structure

• Both have TJ (FCC) and have TJ TJ
similar electronegativities and atomic radii (W. Hume –
TJ
Rothery rules)TJsuggesting high mutualTJsolubility. TJ
• Ni and Cu are totally soluble in one another for all proportions.

•The copper–nickel system is termed isomorphous because of this complete

liquid and solid solubility of the two components. 9
 Phase Diagrams
• Indicate
TJ phases as a TJ
function of T, C, andTJ
P. TJ
• For this course:
TJ - binary TJ
systems: just 2 components.
TJ TJ TJ
- independent variables: T and C (P = 1 atm is almost always used).
T(ºC)
TJ 1600 TJ TJ• 2 phases: TJ
Phase
Diagram
TJ TJ LTJ(liquid) TJ
1500 L (liquid)
for Cu-Ni α (FCC solid solution)
system 1400 • 3 different phase fields:
TJ TJ TJ TJ TJ
L
1300 L+α
TJ 1200 TJ TJ α TJ
α Adapted from Fig. 9.3(a), Callister &
Tm Cu = 1,085 °C
Tm Ni = 1,455 °C 1100
(FCC solid Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,

solution) P. Nash (Ed.), ASM International,

Materials Park, OH (1991).
1000 10
0 20 40 60 80 100 wt% Ni
 Example of Information
TJ TJ TJ TJ

known as a tie line,

or sometimes as an
TJ TJ TJ TJ isotherm
TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

11
 Isomorphous Binary Phase Diagram
• Phase
TJ
diagram: T(ºC)
TJ TJ TJ
Cu-Ni system. 1600

• System is: 1500 (liquid)

TJ TJ TJ L TJ Cu-Ni TJ
-- binary phase
i.e., 2 components: 1400
diagram
TJ Cu and Ni. TJ TJ TJ
1300
-- isomorphous
TJi.e., complete TJ TJ TJ
1200 α
solubility of one
component in 1100
(FCC solid
TJ TJ TJ solution) TJ TJ
another; α phase
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
TJ TJ TJ TJ
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).
12
 Phase Diagrams:
Determination
TJ
of phase(s)TJ present TJ TJ
• Information 1: If we know T and Co, then we know:
TJ -- whichTJphase(s) is (are) present.
TJ TJ TJ
T(ºC)
• Examples: 1600
TJ TJ TJ
L (liquid) TJ
A(1100ºC, 60 wt% Ni):
1 phase: α 1500

B (1250ºC,35)
TJ TJ TJ Cu-Ni TJ
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + α diagram
TJ TJ 1300 TJ TJ TJ
α
(FCC solid
1200
TJ TJ TJ solution) TJ
Adapted from Fig. 9.3(a), Callister &
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 13
 Phase Diagrams:
Determination
TJ
of phase TJ
compositions TJ TJ
• Informaiton 2: If we know T and C0, then we can
determine: Cu-Ni
TJ TJ TJ TJ TJ
-- the composition of each phase. T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
TJ TJ TJ TJ
At TA = 1320ºC: 1300 L (liquid)
TJ Only Liquid (L) present
TJ TJ B TJ
CL = C0 ( = 35 wt% Ni) TB
α
At TD = 1190ºC:
TJ TJ TJ 1200 D TJ(solid) TJ
Only Solid (α) present TD
Cα = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
TJ TJ TJ
At TB = 1250ºC: C L C0 Cα wt%TJNi
Both α 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
Cα = C solidus ( = 43 wt% Ni) Park, OH (1991). 14
 Phase Diagrams:
Determination of phase weight fractions
• Information
TJ 3: If we know
TJ T and C0, then can
TJ TJ
determine: Cu-Ni
• Examples:
-- the weight fraction of each phase.T(ºC) system
TJ TJ TJ TJ TJ
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
TJ TJ TJ TJ
WL = 1.00, Wα = 0 B
AtTJTD : Only Solid ( α) present
TJ TB TJR S TJ
α
WL = 0, Wα = 1.00
1200 D (solid)
At TB : Both α and L present TD
TJ TJ TJ TJ TJ
S 43 − 35 20 3032 35 40 43 50
WL = = = 0.73 C L C0 Cα wt% Ni
TJ R +S TJ43 − 32 TJ TJ
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R Phase Diagrams of Binary Nickel Alloys, P.
Wα = = 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

15
 The Lever Rule
•TJTie line – connects TJ
the phases in equilibrium
TJ with TJ
each other – also sometimes called an isotherm
TJ T(ºC) TJ What fraction of each phase?
TJ TJ TJ
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
TJ BTJ TJ TJ
TB ML Mα
TJ αTJ TJ TJ
1200 (solid)
R S
TJ TJ TJ TJ TJ
20 30CL 40 50 R S
C0 Cα
wt% Ni Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e. Mα x S = ML x R
TJ TJ TJ TJ
ML S C − C0 R C − CL
WL = = = α Wα = = 0
M L + M α R + S C α − CL R + S C α − CL
16
 Ex: Cooling of
• Phase diagram:
a Cu-Ni
T(ºC)
Alloy
TJ TJ L (liquid) L: 35wt%Ni
TJ TJ
Cu-Ni system. Cu-Ni
system
TJ • Consider
TJ
130 0 A
L: 35 wt% Ni TJ TJ TJ
microstuctural α: 46 wt% Ni B
35 46
changes that 32 C 43
TJ TJ TJ TJ
accompany the D
24 36 L: 32 wt% Ni
cooling of a
TJ TJ TJ α: 43 wt% Ni
TJ
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
TJ TJ TJ TJ
α: 36 wt% Ni TJ
α
(solid)
TJ TJ TJ TJ
110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
17
 Cored vs Equilibrium Structures
TJ TJ TJ TJ
• Cα changes as we solidify.
• Cu-Ni case: First α to solidify has Cα = 46 wt% Ni.
TJ TJ TJ TJ TJ
Last α to solidify has Cα = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
TJ TJ TJ TJ
Equilibrium structure Cored structure
TJ Uniform Cα:TJ TJ TJ
35 wt% Ni First α to solidify:
46 wt% Ni
TJ TJ TJ TJ
Last α to solidify: TJ
< 35 wt% Ni

TJ TJ TJ TJ

18
 Mechanical Properties: Cu-Ni System
TJ TJ TJ TJ

• Effect of solid solution strengthening on:

TJ TJ TJ TJ TJ
-- Tensile strength (TS) -- Ductility (%EL)

TJ TJ 60TJ TJ
Tensile Strength (MPa)

%EL for pure Cu

Elongation (%EL)
400 50 %EL for
TJ TJ TJ TJ
TS for pure Ni
pure Ni 40
300
TJ TJ TJ TJ TJ
TS for pure Cu 30
200 20
TJ 0 20 40 TJ60 80 100 0 20
TJ 40 60 80 100 TJ
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.

19
 Binary-Eutectic Systems
A eutectic system is a homogeneous
mixture of substances that melts or solidifies
at a single temperature that is lower than the
melting point of either of the constituents.

has a special composition

TJ 2 components TJ TJ T.
with a min. melting TJ
Cu-Ag
T(ºC) system
TJ Ex.: Cu-Ag
TJ system 1200
TJ TJ TJ
• 3 single phase regions L (liquid)
(L, α, β) 1000
TJ TJ
• Limited solubility: α LTJ+ α 779ºC L+β β
TJ
α: mostly Cu TE 800 8.0 71.9 91.2
TJ TJ TJ TJ
β: mostly Ag 600
• TE : No liquid below TE α+β
TJ TJ TJ
400 TJ TJ
• CE : Composition at
temperature TE 200
TJ TJ 0 20
TJ 40 60 CE 80 100
TJ
• Eutectic reaction Cu , wt% Ag
L(CE) α(CαE) + β(CβE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) α(8.0 wt% Ag) + β(91.2 wt% Ag) 20
heating
 EX 1: Pb-Sn Eutectic System
• For
TJ a 40 wt% Sn-60 wt%
TJ Pb alloy at 150ºC,
TJ determine: TJ
-- the phases present Pb-Sn
Answer: α + β T(ºC) system
TJ TJ
-- the phase compositions TJ TJ TJ
300
Answer: Cα = 11 wt% Sn L (liquid)
TJ Cβ = 99TJ
wt% Sn TJ TJ
-- the relative amount α L+ α
200 183ºC L+β β
TJ of each phase TJ 18.3 TJ 61.9 97.8 TJ
Answer: 150
S Cβ - C0 R S
100
TJ W = TJ = TJ α+β TJ TJ
α R+S Cβ - Cα
99 - 40 59
= = = 0.67
TJ 99 - 11 88
TJ 0 11 20TJ 40 60 80 TJ
99100
C0 - C α Cα C0 Cβ
Wβ = R = C, wt% Sn
R+S Cβ - Cα Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 21
99 - 11 88
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
TJ
-- the phases present: TJ TJ
Pb-Sn
TJ

Answer: α + L T(ºC) system

TJ -- the phase
TJ compositions TJ TJ TJ
300
Answer: Cα = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ α
TJ TJ 220 TJ TJ
-- the relative amount 200
α R L+β β
TJ of each phase TJ TJ 183ºC TJ
Answer:
100
TJ
CL -TJC0 46 - 40 TJ α+β TJ TJ
Wα = =
CL - C α 46 - 17
6
TJ = = 0.21 TJ 0 17 20TJ 40 46 60 80 TJ 100
29 Cα C0 CL
C, wt% Sn
Adapted from Fig. 9.8,
C0 - Cα 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - C α 29
22
 Microstructural Developments
in Eutectic
TJ Systems
TJ I TJ TJ
• For alloys for which T(ºC)
400
L: C0 wt% Sn

TJ C0 <TJ2 wt% Sn TJ L TJ TJ
• Result: at room temperature α
300 L
-- polycrystalline with grains of
TJ TJ TJ TJ
α phase having L+ α
TJ composition C0 TJ 200
α TJ TJ
α: C0 wt% Sn
(Pb-Sn
TE
System)
TJ TJ TJ 100 TJ TJ
α+ β

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

23
 Microstructural Developments
in Eutectic
TJ Systems
TJ II TJ TJ
L: C0 wt% Sn
• For alloys for which 400
T(ºC)
TJ 2 wt% Sn TJ < C0 < 18.3 wt% Sn TJ
L TJ TJ
• Result: L

TJ
at temperatures TJ
in α + β range 300
TJ
α
TJ
L+α
-- polycrystalline with α grains α: C0 wt% Sn
and small β-phase particles
TJ TJ αTJ TJ
200
TE
α
β
TJ TJ TJ TJ TJ
100
α+ β Pb-Sn
TJ TJ TJ system
TJ
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)
24
 Microstructural Developments in Eutectic Systems III
• For
TJ alloy of composition
TJ C0 = CE TJ TJ
• Result: Eutectic microstructure (lamellar structure)
TJ
-- alternating
TJ
layers (lamellae)TJ
of α and β phases. TJ TJ
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
TJ TJ TJ TJ
300 L
Pb-Sn
TJ
system
L+ α TJ TJ TJ

200
α 183ºC L+β β
TE
TJ TJ TJ TJ TJ

100 160 µm
TJα +β β: 97.8 wt% Sn
TJ α: 18.3 wt%Sn
TJ Adapted from Fig. 9.14, TJ
Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn 25
Callister & Rethwisch 8e.
 Lamellar Eutectic Structure
TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ
Adapted from Figs. 9.14 & 9.15, Callister
& Rethwisch 8e.

26
 Microstructural Developments
in Eutectic
TJ
Systems
TJ
IV TJ TJ
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: α phase particles and a eutectic microconstituent
TJ TJ TJ TJT :
• Just above TJ
T(ºC) L: C0 wt% Sn E
α L Cα = 18.3 wt% Sn
L
TJ 300 TJ TJ CL = 61.9 wt% Sn TJ
L α
Pb-Sn S
TJ L+ α TJ =
WαTJ = 0.50 TJ
system R+S
α WL = (1- Wα) = 0.50
L+
β β
200 R S
TE S
R
TJ TJ TJ • Just belowTJTE : TJ
100 α+β Cα = 18.3 wt% Sn
TJ TJ
primary α Cβ = 97.8 wt% SnTJ
eutectic TJ
α
eutectic β Wα = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wβ = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn 27
 Hypoeutectic & Hypereutectic
300
TJ TJ L TJ TJ
Adapted from Fig. 9.8, T(ºC)
Callister & Rethwisch 8e. α L+ α
(Fig. 10.8 adapted from
200 L+β β (Pb-Sn
TE
TJ TJ
Binary Phase Diagrams, TJ TJ
System) TJ
2nd ed., Vol. 3, T.B. α+β
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)
TJ TJ TJ TJ
0 20 40 60 80 100 C, wt% Sn
TJ hypoeutectic: C0 = 50TJ
wt% Sn
eutectic TJ
hypereutectic: (illustration only)
TJ
61.9
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
TJ
Handbook, 9th ed.,
Vol. 9, TJ α TJ TJ β TJ
Metallography and α β
Microstructures, α α β β
American Society for α β
TJ Metals, Materials TJ
α TJ TJ
Park, OH, 1985.) β
175 µm 160 µm
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)
28
 Intermetallic Compounds
TJ TJ TJ TJ
Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.
TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ
Mg2Pb
TJ TJ TJ TJ

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

area - because of stoichiometry (i.e. composition of a compound
is a fixed value). 29
 Eutectic, Eutectoid, & Peritectic
•TJEutectic - liquid transforms
TJ to two solid phases
TJ TJ
L cool α + β (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat
TJ TJ TJ TJ TJ
• Eutectoid – one solid phase transforms to two other
solid phases
TJ TJ intermetallic compound
TJ TJ
S2 S1+S3 - cementite
TJ γ cool
α + Fe3CTJ(For Fe-C, 727ºC, TJ 0.76 wt% C) TJ
heat

TJ
• Peritectic
TJ
- liquid and oneTJsolid phase transform
TJ
to a TJ
second solid phase
TJ S1 + L TJS2 TJ TJ
cool
δ +L heat γ (For Fe-C, 1493ºC, 0.16 wt% C)

30
 Eutectoid & Peritectic Peritectic transformation γ + L δ
TJ TJ TJ TJ

Cu-Zn Phase diagram

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ
Adapted from Fig. 9.21,
Callister & Rethwisch 8e.
Eutectoid transformation δ γ+ε
31
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important
T(ºC)
TJ 1600 TJ TJ TJ
points δ
- Eutectic (A): 1400 L
TJ L ⇒ γTJ
+ Fe3C TJ TJ TJ
γ γ +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
Austenite
TJ γ ⇒ α + Fe3C TJ TJ TJ
Pearlite 1000 γ γ
cementite γ γ γ +Fe3C
TJ TJ TJ TJ
800
α B 727ºC = T eutectoid

TJ TJ 600 TJ α+Fe3C TJ TJ

400
0 1 2 3 4 5 6 6.7
TJ TJ (Fe) 0.76 TJ 4.30 C, wt% CTJ
120 µm
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
α and Fe3C phases α (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
32
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
 Ferrite
TJ TJ TJ TJ

• Ferrite or alpha iron (α-Fe) is a materials science term for iron, or a solid solution with
TJ TJ
iron as the main constituent, TJ
with a body centred TJ It is the
cubic crystal structure. TJ
component which gives steel and cast iron their magnetic properties, and is the classic
example of a ferromagnetic material.
TJ TJ TJ TJ
• It can be considered as pure iron practically (strength = 280N/mm ). Ferrite can be strictly
2

defined as TJa solid solution of iron inTJ TJ containing a maximum

body-centered cubic (BCC) TJ of
0.03% carbon at 723oC and 0.006% carbon at room temperature.
• Most "mild" steels (plain carbon steels with up to about 0.2 wt% C) consist mostly of
TJ TJ
ferrite, with increasing amounts of pearlite (aTJfine lamellar structure of
TJ
ferrite TJ
and cementite) as the carbon content is increased.
TJ TJ TJ TJ

33
 Austenite
TJ TJ TJ TJ

• Austenite (or gamma phase iron) is a metallic non-magnetic solid solution of iron and
TJ an alloying element. TJIn plain-carbon steel, austenite
TJ exists above theTJ TJ
critical eutectoid temperature of 1000 K (about 727 °C); other alloys of steel have different
eutectoid temperatures. It is named after Sir William Chandler Roberts-Austen (1843-
1902).
TJ TJ TJ TJ
• As austenite cools, it often transforms into a mixture of ferrite and cementite as dissolved
carbon falls out of solution. Depending on alloy composition and rate of
TJ
cooling, pearlite may form. If the rateTJof cooling is very fast, the
TJ alloy may experienceTJ
a
slight lattice distortion known as martensitic transformation, instead of transforming into a
mixture. In this industrially very important case, the carbon is not allowed to blend out in
TJ the remaining melt TJ due to the cooling speed,TJbut is captured inside the
TJ FCC-structure of TJ
austenite, creating tension in the crystal when the alloy cools. The result is
hard martensite. The rate of cooling determines the relative proportions of these materials
andTJtherefore the mechanical TJ properties (e.g. hardness,
TJ tensile strength) of the
TJ
steel. Quenching (to induce martensitic transformation), followed by tempering will
transform some of the brittle martensite into bainite. If a low-hardenability steel is
quenched, a significant amount of austenite will be retained in the microstructure.

34
 Pearlite
TJ TJ TJ TJ

• Pearlite is a two-phased, lamellar (or layered) structure composed of alternating layers

TJ of ferrite (87.5 wt%)TJand cementite (12.5 wt%) TJ that occurs in some steels
TJ and cast irons. TJ
During slow cooling of an iron-carbon alloy, pearlite forms by a eutectoid reaction
as austenite cools below 723 °C (1,333 °F) (the eutectoid temperature). Pearlite is a
TJ
microstructure occurring in TJ
many common grades ofTJ steels. TJ

• The eutectoidTJ composition of austenite

TJ is approximately 0.8% TJcarbon; steel with lessTJ
carbon content (hypoeutectoid steel) will contain a corresponding proportion of relatively
pure ferrite crystallites that do not participate in the eutectoid reaction and cannot
TJ TJ Likewise steels with TJ
transform into pearlite. TJ
higher carbon content (hypereutectoid steels) TJ
will form cementite before reaching the eutectoid point. The proportion of ferrite and
cementite forming above the eutectoid point can be calculated from the iron/iron—carbide
TJ TJ TJ TJ
equilibrium phase diagram using the lever rule.

35
 Cementite
TJ TJ TJ TJ

• Cementite (or iron carbide) is a compound of iron and carbon, more precisely an
TJ intermediate transitionTJ metal carbide with the TJformula Fe3C. By weight,
TJ it is 6.67% carbon TJ
and 93.3% iron. It has an orthorhombic crystal structure.[1] It is a hard, brittle
material,[1] normally classified as a ceramic in its pure form, and is a frequently found and
TJ TJ TJ TJ
important constituent in ferrous metallurgy. While cementite is present in most steels and
cast irons,[2]
TJ
it is produced as a rawTJmaterial in the iron carbide
TJ
process, which belongsTJ
to
the family of alternative ironmaking technologies. The name cementite originated from the
research of Floris Osmond and J. Werth, where the structure of solidified steel consists of
TJ a kind of cellular tissue as the nucleus and Fe3C
TJ in theory, with ferriteTJ TJthe envelope of the TJ
cells. The carbide therefore cemented the iron.[3]
•
TJ TJ TJ TJ

36
 Martensite
TJ TJ TJ TJ

• Martensite is a very hard form of steel crystalline structure. It is named after

TJ German metallurgist TJAdolf Martens. By analogy
TJ the term can also referTJ to any crystal TJ
structure that is formed by diffusionless transformation.[1]
• Martensite
TJ is formed in carbon
TJ steels by the rapid cooling
TJ (quenching) of TJ
the austenite form of iron at such a high rate that carbon atoms do not have time to diffuse
out of the crystal
TJ structure in large enough
TJ cementite (Fe3C). Austenite
quantities to formTJ TJ
is gamma-phase iron (γ-Fe), a solid solution of iron and alloying elements. As a result of
the quenching, the face-centered cubic austenite transforms to a highly strained body-
TJ centered tetragonalTJ TJ is supersaturated with
form called martensite that TJcarbon. The shear TJ
deformations that result produce a large number of dislocations, which is a primary
strengthening mechanism of steels. The highest hardness of a pearlitic steel is
TJ TJ TJ TJ
400 Brinell, whereas martensite can achieve 700 Brinell.[2]

37
 Hypoeutectoid Steel
T(ºC)
1600
TJ δ TJ TJ TJ
1400 L
γ γ (Fe-C
γ γ +L
TJ γ γ TJ
1200 1148ºC TJ L+Fe3C TJ
System) TJ
(austenite)

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

pearlite
TJ TJ TJ TJ
Hypoeutectoid
100 µm
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. 38
 Hypo-eutectoid steel has less than 0,8% of C in its composition. It is

Hypoeutectoid Steel composed by pearlite and α-ferrite. Hyper-eutectoid steel has between
0.8% and 2% of C, composed by pearlite and cementite.
T(ºC)
1600
TJ δ TJ TJ TJ
1400 L
(Fe-C
γ γ +L
TJ γ α TJ
1200 1148ºC TJ L+Fe3C TJ
System) TJ
αγ (austenite)

Fe3C (cementite)
γ αγ
1000
TJ TJ γ + Fe3C TJ Adapted from Figs. 9.24
TJ&
Wα = s/(r + s) and 9.29,Callister
Rethwisch 8e.
800 r s
Wγ =(1 -
TJ αW ) 727ºC
TJ TJ
(Fig. 9.24 adapted from
TJ
αRS Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
α α + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
TJ pearlite TJ TJ TJ Park, OH,
Materials TJ
400
0 1 2 3 4 5 6 6.7 1990.)
(Fe)C0 C, wt% C
0.76

Wpearlite = Wγ
TJ TJ TJ TJ
Wα’ = S/(R + S) 100 µm
Hypoeutectoid
steel
WFe3C =(1 – Wα’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. 39
 Hypereutectoid
T(ºC) Steel
1600
TJ δ TJ TJ TJ
1400 L (Fe-C
γ γ +L System)
TJ γ TJ γ
γ γ
1200 1148ºCTJ L+Fe3C TJ TJ
(austenite)

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

(Fe) C, wt%C
pearlite
TJ TJ TJ TJ
60 µmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 40
 Hyper-eutectoid steel will contain 0.77-2% carbon. Now coming

Hypereutectoid Steel
to properties, they differ due to the presence of different micro structures.
At temperatures above eutectoid temperature, the hyper eutectoid phase
contains γ-ferrite & cementite (Fe3C) whereas hypereutectoid
T(ºC) steel contains α-ferrite and γ-ferrite.
1600
TJ δ TJ TJ TJ
1400 L (Fe-C
γ +L System)
TJ TJ γ
1148ºC TJ TJ TJ
Fe3C 1200
γ γ L+Fe3C
(austenite)

Fe3C (cementite)
γ γ 1000
TJ TJ γ +Fe3C TJ Adapted from Figs. 9.24
TJ&
Wγ =x/(v + x) and 9.32,Callister
800 v x Rethwisch 8e. (Fig. 9.24
=(1-Wγ)
WFe3CTJ TJ TJ
adapted from Binary Alloy
TJ
α V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
α +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
TJ TJ
400 TJ TJ OH, 1990.)
Park, TJ
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = Wγ
TJ TJ TJ TJ
Wα = X/(V + X)
60 µmHypereutectoid
WFe =(1 - Wα) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 41
 The main difference between annealing and normalizing is that annealing
allows the material to cool at a controlled rate in a furnace. Normalizing
allows the material to cool by placing it in a room temperature environment
and exposing it to the air in that environment.

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

42
 TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

43
 Example Problem
TJ TJ TJ TJ

For a 99.6 wt% Fe-0.40 wt% C steel at a temperature just below the
TJ TJ
eutectoid, determine the following: TJ TJ TJ

a) The compositions of Fe3C and ferrite (α).

TJ TJ TJ TJ
b) The amount of cementite (in grams) that forms in 100 g of steel.
TJ
c) The amounts of pearlite andTJproeutectoid ferrite TJ
(α) in the 100 g. TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

44
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
TJ TJ TJ TJ
Cα = 0.022 wt% C
CFe3C = 6.70 wt% C
TJ TJ TJ TJ TJ
b) Using the lever rule with 1600

TJ
the tie line shown
TJ
δ
TJ TJ
1400 L
R C − Cα T(ºC)
WFe 3CTJ= = 0 TJ γ γ +L
TJ TJ
R + S CFe 3C − Cα

Fe3C (cementite)
1200 1148ºC L+Fe3C
(austenite)
0.40 − 0.022 1000
= = 0.057 γ + Fe3C
TJ TJ
6.70 − 0.022 TJ TJ TJ
800 727ºC
R S
TJ Amount of Fe3C inTJ100 g 600 TJ α + Fe3C TJ
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Cα C0 C , wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
45
 Solution to Example
c) Using Problem
the VX tie line just above (cont.)
the eutectoid and
TJ
realizing that TJ TJ TJ

C0 = 0.40 wt% C
TJ Cα = 0.022TJ wt% C TJ TJ TJ
Cpearlite = Cγ = 0.76 wt% C
1600
δ
TJ TJ 1400
TJ L TJ
V C − Cα T(ºC) γ +L
WpearliteTJ= = 0 TJ γ TJ TJ

Fe3C (cementite)
V + X Cγ − Cα 1200
(austenite)
1148ºC L+Fe3C

0.40 − 0.022 1000

TJ = TJ = 0.512 TJ
γ + Fe3C
TJ TJ
0.76 − 0.022
800 727ºC
VX
TJ Amount of pearliteTJin 100 g 600 TJ α + Fe3C TJ
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Cα C0 Cγ C, wt% C
= (100 g)(0.512) = 51.2 g
46
 Alloying with Other Elements
• Teutectoid
TJ changes:TJ • Ceutectoid changes:
TJ TJ

Ceutectoid (wt% C)
TJ TEutectoid (ºC) TiTJ Si TJ TJ TJ
Mo W Ni
Cr
TJ TJ Cr TJ Si TJ
Mn
TJ Mn TJ TJ W TJ
Ti Mo
Ni

TJ wt. % TJ
of alloying elements TJ wt. % of alloying elements
TJ TJ
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
TJ Metals, 1939, p. 127.)
TJ TJ
Metals, 1939, p. 127.)
TJ

47
 Summary
TJ TJ TJ TJ
• Phase diagrams are useful tools to determine:
-- the number and types of phases present,
TJ
-- the TJ TJ
composition of each phase, TJ TJ
-- and the weight fraction of each phase
TJ given the temperature
TJ and composition
TJ of the system.TJ
• TJ
The microstructure of
TJ an alloy depends on
TJ TJ
-- its composition, and
-- whether or not cooling rate allows for maintenance of
TJ TJ TJ TJ TJ
equilibrium.
• Important phase diagram phase transformations include
TJ TJ TJ TJ
eutectic, eutectoid, and peritectic.

48
 TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

49