Chapter 6:

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

Fe Fe C
g Eutectoid 3
transformation (cementite)
(Austenite) +
a
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?
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

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)

3
Homogeneous Nucleation & Energy Effects
Surface Free Energy - destabilizes
the nuclei (it takes energy to make
an interface)
GS  4r 2 g
g = 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. 4
Solidification
r* = critical radius
 2gTm g = surface free energy
r* 
Hf T Tm = melting temperature
Hf = latent heat of solidification
T = Tm - T = supercooling

Note: Hf and g are weakly dependent on T

 r* decreases as T increases

For typical T r* ~ 10 nm

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

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
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!

8
Transformations & Undercooling
• Eutectoid transf. (Fe-Fe C system): g  a + Fe3C
3
• 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.
d 9.24,Callister & Rethwisch
8e. (Fig. 9.24 adapted from
1400 L Binary Alloy Phase
Diagrams, 2nd ed., Vol. 1,
g g +L T.B. Massalski (Ed.-in-
1200 L+Fe3C Chief), ASM International,

Fe3C (cementite)
1148ºC
(austenite) Materials Park, OH, 1990.)

1000
a Eutectoid: g +Fe3C
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727ºC
T a +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
9
The Fe-Fe•3Transformation
C Eutectoidof Transformation
austenite to pearlite:
Diffusion of C
Austenite (g) cementite (Fe3C) during transformation
grain a Ferrite (a)
a a
boundary g
g a
a g
Adapted from
a pearlite g
Fig. 9.15,
a growth a
Callister &
Rethwisch 8e. direction
a
• For this transformation, 100
Carbon
diffusion

y (% pearlite)
rate increases with 600ºC
[Teutectoid – T ] (i.e., T). (T larger)
650ºC
50 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
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 H.
isothermal transformation at 675ºC Boyer (Ed.) Atlas of Isothermal
500 Transformation and Cooling
Transformation Diagrams, American
Society for Metals, 1977, p. 369.)
400
time (s)
1 10 10 2 10 3 10 4 10 5 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 &
g g Rethwisch 8e. (Fig. 10.14
adapted from H. Boyer
g g g g (Ed.) Atlas of Isothermal
Transformation and
500 Cooling Transformation
Diagrams, American
Society for Metals, 1997,
p. 28.)
400

1 10 10 2 10 3 10 4 10 5
time (s)
12
Transformations Involving
Noneutectoid Compositions
Consider C = 1.13 wt% C 0

T(ºC) T(ºC)
900 1600
d
A 1400 L

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

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
Adapted from Fig. 10.16, Adapted from Fig. 9.24,
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Hypereutectoid composition – proeutectoid cementite

13
Bainite:• Another
Bainite:
Fe-Fe3C Transformation Product
-- elongated Fe3C particles in
a-ferrite matrix
-- diffusion controlled Fe3C
• Isothermal Transf. Diagram, (cementite)
C0 = 0.76 wt% C a (ferrite)
800 Austenite (stable)
T(ºC) A
TE
P
600 100% pearlite 5 mm
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

10-1 10 103 105

Adapted from Fig. 10.18, time (s)
Callister & Rethwisch 8e.
14
Spheroidite: Another Microstructure for the Fe-Fe3C System
• Spheroidite: a
-- Fe3C particles within an a-ferrite matrix (ferrite)
-- formation requires diffusion
-- heat bainite or pearlite at temperature Fe3C
just below eutectoid for long times
(cementite)
-- driving force – reduction
of a-ferrite/Fe3C interfacial area

60 mm
Adapted from Fig. 10.19, Callister &
Rethwisch 8e. (Fig. 10.19 copyright
United States Steel Corporation,
1971.)

15
Martensite: A Nonequilibrium Transformation Product
• Martensite:
-- g(FCC) to Martensite (BCT)

60 mm
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 • g to martensite (M) transformation..
Rethwisch 8e.
-- 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) 16
Martensite Formation
slow cooling
g (FCC) a (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

17
PhaseEffectTransformations
of adding other elements
of Alloys
Change transition temp.

Cr, Ni, Mo, Si, Mn

retard g  a + Fe3C
reaction (and formation of pearlite,
bainite)

Adapted from Fig. 10.23,

Callister & Rethwisch 8e.
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

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

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+a
T (ºC) A
-- all austenite transforms
to proeutectoid a 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

Wa  = 1  0.58 = 0.42
 Adapted from 0
Fig. 10.29, 0.1 10 103 105
Callister 5e. time (s)
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+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)
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+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%) d)
M (90%)
200

c)
Adapted from 0
Fig. 10.29, 0.1 10 103 105
Callister 5e. time (s)
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.)
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
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.)

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.

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.

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

Pearlite Bainite Martensite

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

Martensite reheat
T Martensite
Strength

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

General Trends 28