Chapter 10:

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 10 - 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 10 - 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 10 - 3

Homogeneous Nucleation & Energy Effects

Surface Free Energy - destabilizes
the nuclei (it takes energy to make
an interface)
GS 4r 2
= surface tension

GT = Total Free Energy

= GS + GV
Volume (Bulk) Free Energy
stabilizes the nuclei (releases energy)
4
GV r 3 G

volume free energy

unit volume

r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
Adapted from Fig.10.2(b), Callister & Rethwisch 8e.

Chapter 10 - 4

Solidification
2Tm
r*
Hf T

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 asT increases

For typicalT

r* ~10nm

Chapter 10 - 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 10 - 6

Fraction transformed, y

Rate of Phase Transformation

transformation
complete

Fixed T

0.5

t0.5

maximum rate reached now

amount
unconverted decreases so rate
slows
rate increases as surface area
increases
& nuclei grow

log t

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

fraction
transformed

Adapted from
Fig. 10.10,
Callister &
Rethwisch 8e.

time

k & n are transformation specific parameters

By convention

rate = 1 / t0.5
Chapter 10 - 7

Temperature Dependence of
Transformation Rate
135C 119C

10

113C 102C

102

88C

43C

104

Adapted from Fig.

10.11, Callister &
Rethwisch 8e.
(Fig. 10.11 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 10 - 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)

1600

1200

L+Fe3C

1148C

1000

+Fe3C

Eutectoid:

Equil. Cooling: Ttransf. = 727C

727C
T
+Fe C

800

400
0
(Fe)

Undercooling by Ttransf. < 727C

0.76

600
0.022

ferrite

+L

(austenite)

Fe3C (cementite)

1400

Adapted from Fig.

9.24,Callister & Rethwisch
8e. (Fig. 9.24 adapted from
Binary Alloy Phase
Diagrams, 2nd ed., Vol. 1,
T.B. Massalski (Ed.-inChief), ASM International,
Materials Park, OH, 1990.)

6.7

C, wt%C

Chapter 10 - 9

The Fe-Fe3C Eutectoid Transformation

Transformation of austenite to pearlite:

Adapted from
Fig. 9.15,
Callister &
Rethwisch 8e.

For this transformation,

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

cementite (Fe3C)
Ferrite ()

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. 10.12,
Callister &
Rethwisch 8e.

Coarse pearlite formed at higher temperatures relatively soft

Fine pearlite

formed at lower temperatures relativelyhard

Chapter 10 - 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

time (s)

Adapted from Fig. 10.13,Callister &

Rethwisch 8e. (Fig. 10.13 adapted from
H. Boyer (Ed.) Atlas of Isothermal
Transformation and Cooling
Transformation Diagrams, American
Society for Metals, 1977, p. 369.)

Chapter 10 - 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

100

400

Adapted from Fig.

10.14,Callister &
Rethwisch 8e. (Fig. 10.14
adapted from H. Boyer
(Ed.) Atlas of Isothermal
Transformation and
Cooling Transformation
Diagrams, American
Society for Metals, 1997,
p. 28.)

Pearlite

50% rlite
pea
0%

500

TE (727C)

10

10 2

10 3

10 4

10 5

time (s)
Chapter 10 - 12

Transformations Involving
Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(C)

T(C)

900

A
+

1200

C
A

+L

L+Fe3C

(austenite)

1000

+Fe3C

800
600

500
1

10

102

103

time (s)

Adapted from Fig. 10.16,

Callister & Rethwisch 8e.

104

400
0
(Fe)

0.76

600

TE (727C)

1.13

700

1400

0.022

800

727C

+Fe3C
2

Adapted from Fig. 9.24,

Callister & Rethwisch 8e.

Fe3C (cementite)

1600

6.7

C, wt%C

Hypereutectoid composition proeutectoid cementite

Chapter 10 - 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
100% bainite

400

10

103

Adapted from Fig. 10.18,

Callister & Rethwisch 8e.

Adapted from Fig. 10.17, Callister &

Rethwisch 8e. (Fig. 10.17 from Metals
Handbook, 8th ed., Vol. 8, Metallography,
Structures, and Phase Diagrams, American
Society for Metals, Materials Park, OH,
1973.)

%
100

10-1

50%

0%

200

(ferrite)

TE

600

Fe3C
(cementite)

105

time (s)
Chapter 10 - 14

Spheroidite: Another Microstructure

for the Fe-Fe3C System

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

Spheroidite:

-- 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

Adapted from Fig. 10.19, Callister &

Rethwisch 8e. (Fig. 10.19 copyright
United States Steel Corporation,
1971.)

Chapter 10 - 15

Martensite: A Nonequilibrium
Transformation Product

Martensite:
Fe atom
sites

x
x

x
x

60 m

-- (FCC) to Martensite (BCT)

potential
C atom sites

Adapted from Fig. 10.20,

Callister & Rethwisch 8e.

Isothermal Transf. Diagram

800

Austenite (stable)

T(C)

600
Adapted from
Fig. 10.22,
Callister &
Rethwisch 8e.

400

200
10-1

B
5
0% 0%

10

TE

103

Adapted from Fig. 10.21, Callister &

Rethwisch 8e. (Fig. 10.21 courtesy
United States Steel Corporation.)

to martensite (M) transformation..

10
0%

M+A
M+A
M+A

Martensite needles
Austenite

0%
50%
90%

105

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

time (s)

Chapter 10 - 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 10 - 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)

Adapted from Fig. 10.23,

Callister & Rethwisch 8e.

Chapter 10 - 18

Continuous Cooling
Transformation Diagrams
Conversion of isothermal
transformation diagram to
continuous cooling
transformation diagram

Adapted from Fig. 10.25,

Callister & Rethwisch 8e.

Cooling curve

Chapter 10 - 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 10 - 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.
Wpearlite

C0 0.022
0.76 0.022
=

T (C)

A+

P
B

600

A+ B

A
400

0.45 0.022
= 0.58
0.76 0.022

A+ P

50%

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

200

W = 1 0.58 = 0.42
Adapted from
Fig. 10.29,
Callister 5e.

0
0.1

10

103

time (s)

105
Chapter 10 - 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

Adapted from
Fig. 10.29,
Callister 5e.

0
0.1

10

103

time (s)

105
Chapter 10 - 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)
Adapted from
Fig. 10.29,
Callister 5e.

0
0.1

10

103

time (s)

105
Chapter 10 - 23

Mechanical Props: Influence of C Content

Adapted from Fig. 9.30,

Callister & Rethwisch 8e.

TS(MPa)
1100
YS(MPa)

C0 < 0.76 wt% C

Hypoeutectoid

Hypo

Hyper

C0 > 0.76 wt% C

Hypereutectoid
Hypo

%EL

Adapted from Fig. 9.33,

Callister & Rethwisch 8e.

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)

Adapted from Fig.

10.29, Callister &
Rethwisch 8e. (Fig.
10.29 based on data
from Metals
Handbook: Heat
Treating, Vol. 4, 9th
ed., V. Masseria
(Managing Ed.),
American Society for
Metals, 1981, p. 9.)

wt% C

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

Chapter 10 - 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

Adapted from Fig. 10.30, Callister &

Rethwisch 8e. (Fig. 10.30 based on
data from Metals Handbook: Heat
Treating, Vol. 4, 9th ed., V. Masseria
(Managing Ed.), American Society for
Metals, 1981, pp. 9 and 17.)

Chapter 10 - 25

Mechanical Props: Fine Pearlite vs.

Martensite

Brinell hardness

Hypo
600

Hyper

martensite
Adapted from Fig. 10.32,
Callister & Rethwisch 8e. (Fig.
10.32 adapted from Edgar C.
Bain, Functions of the Alloying
Elements in Steel, American
Society for Metals, 1939, p. 36;
and R.A. Grange, C.R. Hribal,
and L.F. Porter, Metall. Trans. A,
Vol. 8A, p. 1776.)

400

200
0

fine pearlite
0

0.5

wt% C

Hardness: fine pearlite << martensite.

Chapter 10 - 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
Adapted from
Fig. 10.34,
1400
Callister &
Rethwisch 8e.
1200
(Fig. 10.34
adapted from
Fig. furnished 1000
courtesy of
Republic Steel
800
Corporation.)

200

TS
YS
60
50
%RA
40
30

%RA

400

9 m

1600

Adapted from Fig.

10.33, Callister &
Rethwisch 8e. (Fig.
10.33 copyright by
United States Steel
Corporation,
1971.)

600

Tempering T (C)

tempering produces extremely small Fe3C particles surrounded by

tempering decreases TS, YS but increases %RA
Chapter 10 - 27

Summary of Possible Transformations

Austenite ()
slow
cool

moderate
cool

Adapted from
Fig. 10.36,
Callister &
Rethwisch 8e.

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
General Trends

reheat
Ductility

Strength

Pearlite

Tempered
Martensite
( + very fine
Fe3C particles)
Chapter 10 - 28

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Chapter 10 - 29