Chapter 12: Phase Transformations

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

(Austenite)

FCC

Fe C

3
Eutectoid
transformation (cementite)

(ferrite)

(BCC)

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 T
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 80-300C)

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

Chapter 12 - 3

Homogeneous Nucleation & Energy Effects

Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)

= surface tension

GT = Total Free Energy

= GS + GV
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
= surface free energy
Tm = melting temperature
Hf = latent heat of solidification
T = Tm - T = supercooling

Note: Hf and are weakly dependent on T

r*

decreases as T increases
For typical T

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

Fraction transformed, y

Rate of Phase Transformation

transformation complete

Fixed T

0.5

maximum rate reached now amount

unconverted decreases so rate slows
t0.5

rate increases as interfacial surface area

increases & nuclei grow

log t

Avrami equation => y = 1- exp (-kt n)

fraction
transformed

Fig. 12.10,
Callister &
Rethwisch 9e.

time

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.
135C 119C

10

113C 102C

102

88C

43C

104

(Reprinted with permission

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, 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

+ Fe3C
Eutectoid transf. (Fe-Fe3C system):
0.76 wt% C
6.7 wt% C
For transf. to occur, must
0.022 wt% C

cool to below 727C

(i.e., must undercool)
T(C)

Fig. 11.23, Callister &

Rethwisch 9e.

1600

+Fe3C

Eutectoid:
800

L+Fe3C

1148C

1000

Equil. Cooling: Ttransf. = 727C

727C
T
+Fe C
3

400
0
(Fe)

Undercooling by Ttransf. < 727C

0.76

600
0.022

ferrite

+L

(austenite)

Fe3C (cementite)

1400
1200

[Adapted from Binary Alloy Phase

Diagrams, 2nd edition, Vol. 1, T. B.
Massalski (Editor-in-Chief), 1990.
Reprinted by permission of ASM
International, Materials Park, OH.]

6.7

C, wt%C

Chapter 12 - 9

The Fe-Fe3C Eutectoid Transformation

Transformation of austenite to pearlite:

Adapted from
Fig. 11.14,
Callister &
Rethwisch 9e.

cementite (Fe3C)
Ferrite ()

For this transformation,

rate increases with
[Teutectoid T ] (i.e., T).

pearlite
growth
direction

100

y (% pearlite)

Austenite ()
grain
boundary

Diffusion of C
during transformation

600C
(T larger)

50
0

650C
675C
(T smaller)

Carbon
diffusion

Adapted from
Fig. 12.12,
Callister &
Rethwisch 9e.

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:

y,
% transformed

The Fe-Fe3C system, for C0 = 0.76 wt% C

A transformation temperature of 675C.
100

T = 675C

50
0

10 2

T(C)

Austenite (stable)

10 4

time (s)
TE (727C)

Austenite
(unstable)

600

Pearlite
isothermal transformation at 675C

500
400

%
100
te
50%pearli
0%

700

10

10 2 10 3 10 4 10 5

Fig. 12.13, 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.]

time (s)
Chapter 12 - 11

Austenite-to-Pearlite Isothermal Transformation

Eutectoid composition, C0 = 0.76 wt% C

Begin at T > 727C
Rapidly cool to 625C
Hold T (625C) constant (isothermal treatment)

T(C)

Austenite (stable)

700

Austenite
(unstable)

600

[Adapted from H. Boyer (Editor), Atlas of

Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
Reproduced by permission of ASM
International, Materials Park, OH.]

100

400

Fig. 12.14, Callister & Rethwisch 9e.

Pearlite

50% rlite
pea
0%

500

TE (727C)

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

600

1200

C
A

+L

L+Fe3C

(austenite)

1000

+Fe3C

800
600

500
1

10

102

103

time (s)

104

Fig. 12.16, 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.]

400
0
(Fe)

727C

+Fe3C
0.76

700

TE (727C)

1.13

+
A

1400

0.022

800

Fig. 11.23, Callister & Rethwisch 9e.

Fe3C (cementite)

1600

6.7

C, wt%C

[Adapted from Binary Alloy Phase Diagrams, 2nd edition, Vol.

1, T. B. Massalski (Editor-in-Chief), 1990. Reprinted by
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
-ferrite matrix
-- diffusion controlled
Isothermal Transf. Diagram,
C0 = 0.76 wt% C
800

Austenite (stable)

T(C)

5 m

100% pearlite

Fig. 12.17, Callister & Rethwisch 9e.

100% bainite
400

10

103

time (s)

(From Metals Handbook, Vol. 8, 8th edition,

Metallography, Structures and Phase Diagrams,
1973. Reproduced by permission of ASM
International, Materials Park, OH.)

%
100

10-1

50%

0%

200

(ferrite)

TE

600

Fe3C
(cementite)

105
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:

-- Fe3C particles within an -ferrite matrix (ferrite)

-- formation requires diffusion

Fe3C
-- heat bainite or pearlite at temperature
just below eutectoid for long times (cementite)
-- driving force reduction
of -ferrite/Fe3C interfacial area
60 m
Fig. 12.19, Callister &
Rethwisch 9e.
(Copyright United States Steel
Corporation, 1971.)

Chapter 12 - 15

Martensite: A Nonequilibrium
Transformation Product

Martensite:
Fe atom
sites

x
x
x

60 m

-- (FCC) to Martensite (BCT)

potential
C atom sites

x
x
x

Adapted from Fig. 12.20,

Callister & Rethwisch 9e.

Isothermal Transf. Diagram

800

Austenite (stable)

T(C)

600
Adapted from
Fig. 12.22,
Callister &
Rethwisch 9e.

400

200
10-1

TE

Fig. 12.21, Callister & Rethwisch 9e.

(Courtesy United States Steel Corporation.)

B
5
0% 0%

to martensite (M) transformation.

10
0%
0%
50%
90%

M+A
M+A
M+A

10

Martensite needles
Austenite

103

105

-- is rapid! (diffusionless)
-- % transformation depends only
on T to which rapidly cooled

time (s)

Chapter 12 - 16

Martensite Formation
(FCC) slow cooling

(BCC) + Fe3C

quench
M (BCT)

tempering

Martensite (M) single phase

has body centered tetragonal (BCT)
crystal structure
Diffusionless transformation
BCT

few slip planes

BCT if C0 > 0.15 wt% C

hard, brittle
Chapter 12 - 17

Phase Transformations of Alloys

Effect of adding other elements
Change transition temp.
Cr, Ni, Mo, Si, Mn
retard

+ 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,
for C0 = 0.45 wt% C

Isothermally treat at ~ 680C

800

-- all austenite transforms

to proeutectoid and
coarse pearlite.

T (C)

A+

P
B

600

A+ B

A
400

A+ P

50%

M (start)
M (50%)
M (90%)

200

Figure 12.39, Callister & Rethwisch 9e.

(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
of ASM International, Materials Park, OH.)

0
0.1

10

103

time (s)

105
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

Isothermally treat at ~ 590C T (C)

50% of austenite transforms
to fine pearlite.

P
B

600

Then isothermally treat

at ~ 470C
all remaining austenite
transforms to bainite.

A+

A+ B

A
400

A+ P

50%

M (start)
M (50%)
M (90%)

200

Figure 12.39, Callister & Rethwisch 9e.

(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
of ASM International, Materials Park, OH.)

0
0.1

10

103

time (s)

105
Chapter 12 - 22

Solutions to Parts (c) & (d) of Example

Problem
c) 100% martensite rapidly quench to room
Fe-Fe3C phase diagram,
temperature
for C0 = 0.45 wt% C
d) 50% martensite 800 A
A+
T (C)
& 50% austenite
-- rapidly quench to
~ 290C, hold at this
temperature

P
B

600

A+ B

A
400

A+ P

50%

M (start)
M (50%)
M (90%)

d)

200

c)
Figure 12.39, Callister & Rethwisch 9e.
(Adapted from Atlas of Time-Temperature Diagrams for Irons and
Steels, G. F. Vander Voort, Editor, 1991. Reprinted by permission
of ASM International, Materials Park, OH.)

0
0.1

10

103

time (s)

105
Chapter 12 - 23

Mechanical Props: Influence of C Content

Fig. 11.29, Callister & Rethwisch

9e.
(CourtesyofRepublicSteelCorporation.)

TS(MPa)
1100
YS(MPa)

C0 < 0.76 wt% C

Hypoeutectoid

Hypo

Hyper

C0 > 0.76 wt% C

Hypereutectoid
Hypo

%EL

Fig. 11.32, Callister & Rethwisch 9e.

(Copyright 1971 by United States Steel
Corporation.)

Hyper
80

100

900

hardness

40

700
50
500

0.5

wt% C

0.5

0.76

0.76

300

Impact energy (Izod, ft-lb)

Pearlite (med)
ferrite (soft)

Pearlite (med)
Cementite
(hard)

Fig. 12.29, Callister &

Rethwisch 9e.
[Data taken from Metals
Handbook: Heat Treating,
Vol. 4, 9th edition, V.
Masseria (Managing
Editor), 1981. Reproduced
by permission of ASM
International, Materials
Park, OH.]

wt% C

Increase C content: TS and YS increase, %EL decreases

Chapter 12 - 24

Mechanical Props: Fine Pearlite vs. Coarse

Pearlite vs. Spheroidite

Brinell hardness

320

Hyper
fine
pearlite

240

coarse
pearlite
spheroidite

160
80
0

Hardness:
%RA:

0.5

wt%C

90
Ductility (%RA)

Hypo

Hypo

spheroidite

60

coarse
pearlite
fine
pearlite

30

Hyper

fine > coarse > spheroidite

fine < coarse < spheroidite

0.5

wt%C

Fig. 12.30, Callister & Rethwisch 9e.

[Data taken from Metals Handbook: Heat
Treating, Vol. 4, 9th edition, V. Masseria
(Managing Editor), 1981. Reproduced by
permission of ASM International, Materials Park,
OH.]

Chapter 12 - 25

Mechanical Props: Fine Pearlite vs.

Martensite

Brinell hardness

Hypo
600

Hyper

martensite
Fig. 12.32, Callister & Rethwisch 9e.
(Adapted from Edgar C. Bain, Functions of the
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.)

400

200
0

fine pearlite
0

0.5

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
Fig. 12.34,
Callister &
Rethwisch 9e.
(Adapted from Edgar
C. Bain, Functions of
the Alloying
Elements in Steel,
1939. Reproduced
by permission of
ASM International,
Materials Park, OH.)

1400

TS
YS

1200
1000

60
50
%RA
40
30

%RA

800
200

400

9 m

1600

Figure 12.33,
Callister &
Rethwisch 9e.
(Copyright 1971 by
United States Steel
Corporation.)

600

Tempering T (C)

tempering produces extremely small Fe3C particles surrounded by .

tempering decreases TS, YS but increases %RA
Chapter 12 - 27

Summary of Possible Transformations

Austenite ()
slow
cool

moderate
cool

Adapted from
Fig. 12.36,
Callister &
Rethwisch 9e.

rapid
quench

Bainite

Martensite

( + Fe3C layers + a
proeutectoid phase)

( + elong. Fe3C particles)

(BCT phase
diffusionless
transformation)

Martensite
T Martensite
bainite
fine pearlite
coarse pearlite
spheroidite

reheat
Ductility

Strength

Pearlite

Tempered
Martensite
( + very fine
Fe3C particles)

General Trends
Chapter 12 - 28