Chapter 12: Phase Transformations

ISSUES TO ADDRESS...
• Transforming one phase into another takes time.

Fe Fe C
3
Eutectoid
γ transformation (cementite)
(Austenite) +
α
C FCC (BCC)
(ferrite)

• How does the rate of transformation depend on

time and temperature ?
• Is it possible to slow down transformations so that
non-equilibrium structures are formed?
• Are the mechanical properties of non-equilibrium
structures more desirable than equilibrium ones?
Chapter 12 - 1
 Phase Transformations
Nucleation
– nuclei (seeds) act as templates on which crystals grow
– for nucleus to form rate of addition of atoms to nucleus must be
faster than rate of loss
– once nucleated, growth proceeds until equilibrium is attained
Driving force to nucleate increases as we increase ΔT
– supercooling (eutectic, eutectoid)
– superheating (peritectic)

Small supercooling  slow nucleation rate - few nuclei - large crystals

Large supercooling  rapid nucleation rate - many nuclei - small crystals

Chapter 12 - 2
 Solidification: Nucleation Types

• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling
(typically 80-300°C)

• Heterogeneous nucleation
– much easier since stable “nucleating surface” is
already present — e.g., mold wall, impurities in
liquid phase
– only very slight supercooling (0.1-10°C)

Chapter 12 - 3
 Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)

γ = surface tension

ΔGT = Total Free Energy

= ΔGS + ΔGV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)

r* = critical nucleus: for r < r* nuclei shrink; for r > r* nuclei grow (to reduce energy)
Adapted from Fig.12.2(b), Callister & Rethwisch 9e.
Chapter 12 - 4
 Solidification
r* = critical radius
γ = surface free energy
Tm = melting temperature
ΔHf = latent heat of solidification
ΔT = Tm - T = supercooling

Note: ΔHf and γ are weakly dependent on ΔT

 r* decreases as ΔT increases

For typical ΔT r* ~ 10 nm

Chapter 12 - 5
 Rate of Phase Transformations

Kinetics - study of reaction rates of phase

transformations
• To determine reaction rate – measure degree
of transformation as function of time (while
holding temp constant)
How is degree of transformation measured?
X-ray diffraction – many specimens required
electrical conductivity measurements –
on single specimen
measure propagation of sound waves –
on single specimen

Chapter 12 - 6
 Rate of Phase Transformation
Fraction transformed, y
transformation complete
Fixed T
0.5 maximum rate reached – now amount
unconverted decreases so rate slows
rate increases as interfacial surface area
t0.5 increases & nuclei grow

log t Fig. 12.10,

Callister &
Rethwisch 9e.
Avrami equation => y = 1- exp (-kt n)
fraction time
transformed
– k & n are transformation specific parameters

By convention rate = 1 / t0.5

Chapter 12 - 7
 Temperature Dependence of
Transformation Rate
Fig. 12.11, Callister &
Rethwisch 9e.
(Reprinted with permission
135C 119C 113C 102C 88C 43C from Metallurgical
Transactions, Vol. 188, 1950,
a publication of The
Metallurgical Society of AIME,
Warrendale, PA. Adapted
from B. F. Decker and D.
Harker, “Recrystallization in
Rolled Copper,” Trans. AIME,
1 10 102 104 188, 1950, p. 888.)

• For the recrystallization of Cu, since

rate = 1/t0.5
rate increases with increasing temperature

• Rate often so slow that attainment of equilibrium

state not possible!
Chapter 12 - 8
 Transformations & Undercooling
• Eutectoid transf. (Fe-Fe3C system): γ  α + Fe3C
• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727°C 0.022 wt% C
(i.e., must “undercool”)
T(°C)
1600 Fig. 11.23, Callister &
δ Rethwisch 9e.
[Adapted from Binary Alloy Phase
1400 L Diagrams, 2nd edition, Vol. 1, T. B.
Massalski (Editor-in-Chief), 1990.
Reprinted by permission of ASM
γ γ +L International, Materials Park, OH.]
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. =
727°C 727°C
ΔT α +Fe3C
600 Undercooling by Ttransf. < 727°C
0.022

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C
Chapter 12 - 9
 The Fe-Fe3C Eutectoid Transformation
• Transformation of austenite to pearlite:
Diffusion of C
Austenite (γ) cementite (Fe3C) during transformation
grain α Ferrite (α)
boundary α α
γ
γ α
α γ
Adapted from
α
pearlite γ
Fig. 11.14,
α growth α
Callister &
Rethwisch 9e. direction
α
• For this transformation, 100
Carbon
diffusion
rate increases with y (% pearlite) 600°C
(ΔT larger)
[Teutectoid – T ] (i.e., ΔT). 50 650°C
Adapted from
675°C Fig. 12.12,
(ΔT smaller) Callister &
Rethwisch 9e.
0

Coarse pearlite  formed at higher temperatures – relatively soft

Fine pearlite  formed at lower temperatures – relatively hard

Chapter 12 - 10
 Generation of Isothermal Transformation
Diagrams
Consider:
• The Fe-Fe3C system, for C0 = 0.76 wt% C
• A transformation temperature of 675ºC.
% transformed

100
T = 675°C
y,

50

0 Fig. 12.13, Callister & Rethwisch 9e.

1 10 2 10 4 time (s) [Adapted from H. Boyer (Editor), Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
T(°C) Austenite (stable)
Reproduced by permission of ASM
International, Materials Park, OH.]
TE (727°C)
700 Austenite
(unstable)

600 Pearlite
isothermal transformation at 675°C
500

400
time (s)
1 10 10 2 10 3 10 4 10 5 Chapter 12 - 11
Austenite-to-Pearlite Isothermal Transformation
• Eutectoid composition, C0 = 0.76 wt% C
• Begin at T > 727°C
• Rapidly cool to 625°C
• Hold T (625°C) constant (isothermal treatment)
T(ºC) Austenite (stable)
TE (727°C)
700 Austenite
(unstable)

Fig. 12.14, Callister & Rethwisch 9e.

600 Pearlite [Adapted from H. Boyer (Editor), Atlas of
γ γ Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
γ γ γ γ
Reproduced by permission of ASM
International, Materials Park, OH.]
500

400

1 10 10 2 10 3 10 4 10 5
time (s)
Chapter 12 - 12
 Transformations Involving
Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(°C) T(°C)
900 1600
δ
A 1400 L
800

Fe3C (cementite)
A TE (727°C) γ +L
+ 1200 γ L+Fe3C
700 A C (austenite)
P 1000
+ P a γ +Fe3C
600 A
800
727°C
500 600 α +Fe3C

0.022
0.76
1 10 102 103 104 400

1.13
time (s) 0 1 2 3 4 5 6 6.7
(Fe)
C, wt%C
Fig. 12.16, Callister & Rethwisch 9e. Fig. 11.23, Callister & Rethwisch 9e.
[Adapted from H. Boyer (Editor), Atlas of Isothermal Transformation [Adapted from Binary Alloy Phase Diagrams, 2nd edition, Vol.
and Cooling Transformation Diagrams, 1977. Reproduced by 1, T. B. Massalski (Editor-in-Chief), 1990. Reprinted by
permission of ASM International, Materials Park, OH.] permission of ASM International, Materials Park, OH.]

Hypereutectoid composition – proeutectoid cementite

Chapter 12 - 13
 Bainite: Another Fe-Fe3C
Transformation Product
• Bainite:
-- elongated Fe3C particles in
α-ferrite matrix
-- diffusion controlled Fe3C
• Isothermal Transf. Diagram, (cementite)
C0 = 0.76 wt% C α (ferrite)
800 Austenite (stable)
T(°C) A
TE
P
600 100% pearlite 5 μm
Fig. 12.17, Callister & Rethwisch 9e.
(From Metals Handbook, Vol. 8, 8th edition,
100% bainite Metallography, Structures and Phase Diagrams,
1973. Reproduced by permission of ASM
400 A B International, Materials Park, OH.)

200

10-1 10 103 105

time (s) Fig. 12.18, Callister & Rethwisch 9e. [Adapted
from H. Boyer (Editor), Atlas of Isothermal Transformation
and Cooling Transformation Diagrams, 1977. Reproduced
by permission of ASM International, Materials Park, OH.]
Chapter 12 - 14
 Spheroidite: Another Microstructure
for the Fe-Fe3C System
• Spheroidite: α
-- Fe3C particles within an α-ferrite matrix (ferrite)
-- formation requires diffusion
-- heat bainite or pearlite at temperature Fe3C
just below eutectoid for long times (cementite)
-- driving force – reduction
of α-ferrite/Fe3C interfacial area

60 μm
Fig. 12.19, Callister &
Rethwisch 9e.
(Copyright United States Steel
Corporation, 1971.)

Chapter 12 - 15
 Martensite: A Nonequilibrium
Transformation Product
• Martensite:
-- γ(FCC) to Martensite (BCT)
x

60 μm
Fe atom potential
x x
sites x x C atom sites
x Adapted from Fig. 12.20,
Callister & Rethwisch 9e.

• Isothermal Transf. Diagram

800 Austenite (stable) Martensite needles
T(°C) A TE Austenite
P Fig. 12.21, Callister & Rethwisch 9e.
600 (Courtesy United States Steel Corporation.)

Adapted from
Fig. 12.22,
Callister & 400 A B • γ to martensite (M) transformation.
Rethwisch 9e.
-- is rapid! (diffusionless)
200 M+A
0% -- % transformation depends only
50%
M+A 90% on T to which rapidly cooled
M+A
10-1 10 103 105 time (s) Chapter 12 - 16
 Martensite Formation

slow cooling
γ (FCC) α (BCC) + Fe3C
quench
tempering
M (BCT)

Martensite (M) – single phase

– has body centered tetragonal (BCT)
crystal structure

Diffusionless transformation BCT if C0 > 0.15 wt% C

BCT  few slip planes  hard, brittle

Chapter 12 - 17
 Phase Transformations of Alloys
Effect of adding other elements
Change transition temp.

Cr, Ni, Mo, Si, Mn

retard γ  α + Fe3C
reaction (and formation of
pearlite, bainite)

Fig. 12.23, Callister & Rethwisch 9e.

[Adapted from H. Boyer (Editor), Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
Reproduced by permission of ASM
International, Materials Park, OH.]

Chapter 12 - 18
 Continuous Cooling
Transformation Diagrams
Conversion of isothermal
transformation diagram to
continuous cooling
transformation diagram

Fig. 12.25, Callister & Rethwisch 9e.

[Adapted from H. Boyer (Editor), Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
Reproduced by permission of ASM
International, Materials Park, OH.]
Cooling curve

Chapter 12 - 19
Isothermal Heat Treatment Example
Problems
On the isothermal transformation diagram for
a 0.45 wt% C, Fe-C alloy, sketch and label
the time-temperature paths to produce the
following microstructures:
a) 42% proeutectoid ferrite and 58% coarse
pearlite
b) 50% fine pearlite and 50% bainite
c) 100% martensite
d) 50% martensite and 50% austenite

Chapter 12 - 20
 Solution to Part (a) of Example
Problem
a) 42% proeutectoid ferrite and 58% coarse pearlite
Fe-Fe3C phase diagram,
Isothermally treat at ~ for C0 = 0.45 wt% C
680°C 800 A+α
T (°C) A

-- all austenite transforms

A+P
to proeutectoid α and 600 P
coarse pearlite. B
A+B
A
400 50%
M (start)
M (50%)
M (90%)
200

0
Figure 12.39, Callister & Rethwisch 9e. 0.1 10 103 105
(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
time (s)
of ASM International, Materials Park, OH.) Chapter 12 - 21
 Solution to Part (b) of Example
Problem
b) 50% fine pearlite and 50% bainite
Fe-Fe3C phase diagram,
for C0 = 0.45 wt% C
800 A+α
Isothermally treat at ~ 590°CT (ºC) A
– 50% of austenite transforms
to fine pearlite. P
A+P
600
B
Then isothermally treat A+B
A
at ~ 470°C 50%
400
– all remaining austenite M (start)
transforms to bainite. M (50%)
M (90%)
200

0
Figure 12.39, Callister & Rethwisch 9e. 0.1 10 103 105
(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
time (s)
of ASM International, Materials Park, OH.) Chapter 12 - 22
 Solutions to Parts (c) & (d) of Example
Problem
c) 100% martensite – rapidly quench to room
temperature Fe-Fe3C phase diagram,
for C0 = 0.45 wt% C
d) 50% martensite 800 A
A+α
T (°C)
& 50% austenite
A+P
-- rapidly quench to 600 P
B
~ 290°C, hold at this
A+B
temperature A
400 50%
M (start)
M (50%)
M (90%)
d)
200

c)
0
Figure 12.39, Callister & Rethwisch 9e. 0.1 10 103 105
(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
time (s)
of ASM International, Materials Park, OH.) Chapter 12 - 23
 Mechanical Props: Influence of C Content
Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
Fig. 11.29, Callister & Rethwisch 9e. C0 < 0.76 wt% C C0 > 0.76 wt% C Fig. 11.32, Callister & Rethwisch 9e.
(Courtesy of Republic Steel Corporation.) (Copyright 1971 by United States Steel
Hypoeutectoid Hypereutectoid Corporation.)

Hypo Hyper Hypo Hyper

TS(MPa) %EL 80
1100

Impact energy (Izod, ft-lb)

YS(MPa) 100 Fig. 12.29, Callister &
Rethwisch 9e.
900 [Data taken from Metals
hardness Handbook: Heat Treating,
40 Vol. 4, 9th edition, V.
700 Masseria (Managing
50 Editor), 1981. Reproduced
by permission of ASM
500 International, Materials
0 Park, OH.]

300
0
0.76

0.76
0 0.5 0 0.5 1
wt% C wt% C
• Increase C content: TS and YS increase, %EL decreases

Chapter 12 - 24
 Mechanical Props: Fine Pearlite vs. Coarse
Pearlite vs. Spheroidite

Hypo Hyper 90 Hypo Hyper

320 fine
pearlite

Ductility (%RA)
spheroidite
60
Brinell hardness

240 coarse
pearlite
spheroidite
160 30 coarse
pearlite
fine
80 pearlite
0
0 0.5 1 0 0.5 1
wt%C wt%C
Fig. 12.30, Callister & Rethwisch 9e.
• Hardness: fine > coarse > spheroidite [Data taken from Metals Handbook: Heat
Treating, Vol. 4, 9th edition, V. Masseria
• %RA: fine < coarse < spheroidite (Managing Editor), 1981. Reproduced by
permission of ASM International, Materials Park,
OH.]

Chapter 12 - 25
 Mechanical Props: Fine Pearlite vs.
Martensite

Hypo Hyper

600
Brinell hardness

martensite
Fig. 12.32, Callister & Rethwisch 9e.
(Adapted from Edgar C. Bain, Functions of the
400 Alloying Elements in Steel, 1939; and R. A.
Grange, C. R. Hribal, and L. F. Porter, Metall.
Trans. A, Vol. 8A. Reproduced by permission
of ASM International, Materials Park, OH.)

200
fine pearlite
0
0 0.5 1
wt% C
• Hardness: fine pearlite << martensite.

Chapter 12 - 26
 Tempered Martensite
Heat treat martensite to form tempered martensite
• tempered martensite less brittle than martensite
• tempering reduces internal stresses caused by quenching
TS(MPa)
YS(MPa)
1800

1600 TS
Fig. 12.34, Figure 12.33,

9 μm
Callister & 1400 YS Callister &
Rethwisch 9e. Rethwisch 9e.
(Adapted from Edgar (Copyright 1971 by
C. Bain, Functions of 1200 60 United States Steel
the Alloying Corporation.)
Elements in Steel,
1939. Reproduced 1000 50
by permission of %RA %RA
ASM International,
40
Materials Park, OH.) 800 30
200 400 600
Tempering T (°C)
• tempering produces extremely small Fe3C particles surrounded by α.
• tempering decreases TS, YS but increases %RA
Chapter 12 - 27
Summary of Possible Transformations
Adapted from
Austenite (γ) Fig. 12.36,
Callister &
Rethwisch 9e.
slow moderate rapid
cool cool quench

Pearlite Bainite Martensite

(α + Fe3C layers + a (α + elong. Fe3C particles) (BCT phase
proeutectoid phase) diffusionless
transformation)

Martensite reheat
T Martensite
Strength

Ductility
bainite Tempered
fine pearlite Martensite
coarse pearlite (α + very fine
spheroidite Fe3C particles)

General Trends
Chapter 12 - 28
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 12 - 29