Module 9:

Phase Transformations

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

Fe Fe C

3
Eutectoid
transformation (cementite)
(Austenite) +

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 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 80-300ºC)

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

Chapter 10 - 3
 Homogeneous Nucleation & Energy Effects
Surface Free Energy - destabilizes
the nuclei (it takes energy to make
an interface)
GS  4r 2 
 = surface tension

GT = Total Free Energy

= GS + GV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
4
GV  r 3 G
3
volume free energy
G 
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
r* = critical radius
 2Tm = surface free energy
r* 
Hf T 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 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
 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 surface area increases
t0.5 & nuclei grow

log t Adapted from

Fig. 10.10,
Callister &
Avrami equation => y = 1- exp (-kt n) Rethwisch 8e.

fraction time
transformed
– k & n are transformation specific parameters

By convention rate = 1 / t0.5

Chapter 10 - 7
 Temperature Dependence of
Transformation Rate
Adapted from Fig.
10.11, Callister &
Rethwisch 8e.
135C 119C 113C 102C 88C 43C (Fig. 10.11 adapted
from B.F. Decker and
D. Harker,
"Recrystallization in
Rolled Copper", Trans
AIME, 188, 1950, p.
888.)
1 10 102 104

• 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
• Eutectoid transf. (Fe-Fe3C system):    + Fe3C
• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727ºC 0.022 wt% C
(i.e., must “undercool”)
T(ºC)
1600 Adapted from Fig.
 9.24,Callister & Rethwisch
8e. (Fig. 9.24 adapted from
1400 L Binary Alloy Phase
Diagrams, 2nd ed., Vol. 1,
  +L T.B. Massalski (Ed.-in-
1200 1148ºC L+Fe3C Chief), ASM International,

Fe3C (cementite)
(austenite) Materials Park, OH, 1990.)

1000
 Eutectoid:  +Fe3C
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727ºC
T  +Fe C 3
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 10 - 9
 The Fe-Fe3C Eutectoid Transformation
• Transformation of austenite to pearlite:
Diffusion of C
Austenite () cementite (Fe3C) during transformation
grain  Ferrite ()
boundary  

 
 pearlite 
Adapted from
 
Fig. 9.15,
 growth 
Callister &
Rethwisch 8e. direction

• For this transformation, 100
Carbon
diffusion
rate increases with y (% pearlite) 600ºC
(T larger)
[Teutectoid – T ] (i.e., T). 50 650ºC
Adapted from
675ºC Fig. 10.12,
(T smaller) Callister &
Rethwisch 8e.
0

Coarse pearlite  formed at higher temperatures – relatively soft

Fine pearlite  formed at lower temperatures – relatively hard
Chapter 10 -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 = 675ºC
y,

50

0
1 10 2 10 4 time (s)
T(ºC) Austenite (stable)
TE (727ºC)
700 Austenite
(unstable)

600 Pearlite Adapted from Fig. 10.13,Callister &

Rethwisch 8e. (Fig. 10.13 adapted from
isothermal transformation at 675ºC H. Boyer (Ed.) Atlas of Isothermal
10 0

Transformation and Cooling

50%pearli

500
0%

Transformation Diagrams, American

%

Society for Metals, 1977, p. 369.)

400
time (s)
te

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

Adapted from Fig.

600 Pearlite 10.14,Callister &
  Rethwisch 8e. (Fig. 10.14
adapted from H. Boyer
    (Ed.) Atlas of Isothermal
10 0

Transformation and
5 0 % r l it e

500
0%

Cooling Transformation
pea

Diagrams, American
Society for Metals, 1997,
p. 28.)
400

1 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(ºC) T(ºC)
900 1600

A 1400 L
800

Fe3C (cementite)
+
A TE (727ºC)   +L
1200 L+Fe3C
700 A C (austenite)
P 1000
A
+ P   +Fe3C
600
800
727ºC
T  +Fe3C
500 600

0.022
0.76
1 10 102 103 104 400
0 1 2 3 4 5 6 6.7

1.13
time (s) (Fe)
C, wt%C
Adapted from Fig. 10.16, Adapted from Fig. 9.24,
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Hypereutectoid composition – proeutectoid cementite

Chapter 10 -13
 Bainite: Another Fe-Fe3C
Transformation Product
• Bainite:
-- elongated Fe3C particles in
-ferrite matrix
-- diffusion controlled  Fe3C
• Isothermal Transf. Diagram, (cementite)
(ferrite)
C0 = 0.76 wt% C
800 Austenite (stable)
T(ºC) A
TE
P
600 100% pearlite 5 m
Adapted from Fig. 10.17, Callister &
Rethwisch 8e. (Fig. 10.17 from Metals
100% bainite Handbook, 8th ed., Vol. 8, Metallography,
400 A B Structures, and Phase Diagrams, American
Society for Metals, Materials Park, OH,
1973.)

200
1 00
0%

50%

10-1 10 103 105

Adapted from Fig. 10.18, time (s)
Callister & Rethwisch 8e.
Chapter 10 -14
 Spheroidite: Another Microstructure
for the Fe-Fe3C System
• Spheroidite: 
-- Fe3C particles within an -ferrite matrix (ferrite)
-- formation requires diffusion
-- heat bainite or pearlite at temperature Fe3C
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:
-- (FCC) to Martensite (BCT)
x

60 m
Fe atom potential
x x
sites x x C atom sites
x Adapted from Fig. 10.20,
Callister & Rethwisch 8e.

• Isothermal Transf. Diagram

800 Austenite (stable) Martensite needles
T(ºC) TE Austenite
A
P Adapted from Fig. 10.21, Callister &
600 Rethwisch 8e. (Fig. 10.21 courtesy
United States Steel Corporation.)
Adapted from
Fig. 10.22,
Callister & 400 A B 10 •  to martensite (M) transformation..
Rethwisch 8e. 5 0 %
0 % 0% -- is rapid! (diffusionless)
200 M+A
0% -- % transf. depends only on T to
50%
M+A 90% which rapidly cooled
M+A
10-1 10 103 105 time (s) Chapter 10 -16
 Martensite Formation

 (FCC) slow cooling  (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 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,
Isothermally treat at ~ 680ºC for C0 = 0.45 wt% C
800 A+
T (ºC) A
-- all austenite transforms
to proeutectoid  and
A+P
coarse pearlite. 600 P
B
C0  0.022 A+B
Wpearlite  A
0.76  0.022 50%
400
M (start)
0.45  0.022 M (50%)
= = 0.58 M (90%)
0.76  0.022
200

W = 1  0.58 = 0.42

Adapted from 0
Fig. 10.29, 0.1 10 103 105
Callister 5e. time (s)
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 A+
Isothermally treat at ~ 590ºC T (ºC) A
– 50% of austenite transforms
to fine pearlite. P
A+P
600
B
Then isothermally treat A+B
A
at ~ 470ºC 50%
400
– all remaining austenite M (start)
transforms to bainite. M (50%)
M (90%)
200

Adapted from 0
Fig. 10.29, 0.1 10 103 105
Callister 5e. time (s)
Chapter 10 -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+
T (ºC)
& 50% austenite
A+P
-- rapidly quench to 600 P
B
~ 290ºC, hold at this
A+B
temperature A
400 50%
M (start)
M (50%)
M (90%)
d)
200

c)
Adapted from 0
Fig. 10.29, 0.1 10 103 105
Callister 5e. time (s)
Chapter 10 -23
 Mechanical Props: Influence of C Content
Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
Adapted from Fig. 9.30, C0 < 0.76 wt% C C0 > 0.76 wt% C Adapted from Fig. 9.33,
Callister & Rethwisch 8e. Callister & Rethwisch 8e.
Hypoeutectoid Hypereutectoid
Hypo Hyper Hypo Hyper
TS(MPa) %EL 80
1100

Impact energy (Izod, ft-lb)

YS(MPa) 100 Adapted from Fig.
10.29, Callister &
900 Rethwisch 8e. (Fig.
hardness 10.29 based on data
40
700 from Metals
50 Handbook: Heat
Treating, Vol. 4, 9th
500 ed., V. Masseria
0 (Managing Ed.),
American Society for
300
Metals, 1981, p. 9.)
1 0
0.76

0 0.5

0.76
0 0.5 1
wt% C wt% C
• Increase C content: TS and YS increase, %EL decreases
Chapter 10 -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
Adapted from Fig. 10.30, Callister &
• Hardness: fine > coarse > spheroidite Rethwisch 8e. (Fig. 10.30 based on
data from Metals Handbook: Heat
• %RA: fine < coarse < spheroidite 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

Hypo Hyper

600
Brinell hardness

martensite
Adapted from Fig. 10.32,
Callister & Rethwisch 8e. (Fig.
400 10.32 adapted from Edgar C.
Bain, Functions of the Alloying
Elements in Steel, American
Society for Metals, 1939, p. 36;
200 and R.A. Grange, C.R. Hribal,
fine pearlite and L.F. Porter, Metall. Trans. A,
Vol. 8A, p. 1776.)
0
0 0.5 1
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

1600 TS
Adapted from Adapted from Fig.
YS

9 m
Fig. 10.34, 1400 10.33, Callister &
Callister & Rethwisch 8e. (Fig.
Rethwisch 8e. 10.33 copyright by
(Fig. 10.34 1200 60 United States Steel
adapted from Corporation,
Fig. furnished 1000 50 1971.)
courtesy of %RA %RA
Republic Steel
40
Corporation.) 800 30
200 400 600
Tempering T (ºC)
• tempering produces extremely small Fe3C particles surrounded by 
• tempering decreases TS, YS but increases %RA
Chapter 10 -27
Summary of Possible Transformations
Adapted from
Austenite () Fig. 10.36,
Callister &
Rethwisch 8e.
slow moderate rapid
cool cool quench

Pearlite Bainite Martensite

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

Martensite reheat
T Martensite
Strength

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

General Trends Chapter 10 -28