11/5/13

Chapter 10: 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 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 ΔT
– ____________ (eutectic, eutectoid)
– ____________ (peritectic)

Small supercooling à _____________ - few nuclei - ______crystals

Large supercooling à ______________ - many nuclei - _____ crystals

Chapter 10 - 2

Solidification: Nucleation Types

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

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

Chapter 10 - 3

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Homogeneous Nucleation & Energy Effects

Surface Free Energy- ___________
the nuclei (it takes energy to make
an _____________)
ΔGS = 4π r 2γ
γ = surface ______________

ΔGT = Total _______________

= ΔGS + ΔGV

Volume (Bulk) Free Energy –

_________ the _____ (releases energy)
4 3
ΔGV = π r ΔGυ
3
volume free energy
ΔGυ =
unit volume
r* = critical nucleus: for r < r* nuclei ______; for r > r* nuclei grow (to reduce energy)
Adapted from Fig.10.2(b), Callister & Rethwisch 9e.
Chapter 10 - 4

Solidification
r* = critical radius
−2γTm
r* = γ = surface free energy
ΔHf ΔT Tm = melting temperature
ΔHf = latent heat ___________
ΔT = Tm - T = supercooling

Note: ΔHf and γ are ________ dependent on ΔT

∴ r* _____________ as ΔT increases

For typical ΔT 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 _____________ as function of time (while
holding temp constant)
How is degree of __________ measured?
__________ – many specimens required
electrical conductivity measurements –
on _________ specimen
Measure ___________ of sound waves –
on single specimen

Chapter 10 - 6

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Rate of Phase Transformation

Fraction transformed, y

____________________
Fixed T
0.5 ________ rate reached – now amount
unconverted _________ so rate slows
rate ________ as interfacial surface area
t0.5 increases & nuclei _______

log t Fig. 10.10,

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

By convention rate = 1 / t0.5

Chapter 10 - 7

Temperature Dependence of
Transformation Rate
Fig. 10.11, 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 _________________ of Cu, since

rate = 1/t0.5
rate __________ with ___________ temperature

• Rate often so ______ that attainment of ___________

state not possible!
Chapter 10 - 8

Transformations & Undercooling

• ________ transf. (Fe-Fe3C system): γ ⇒
α + Fe3C
• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below ________ 0.022 wt% C
(i.e., must “__________”)
T(°C)
1600 Fig. 9.24, 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 10 - 9

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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 pearlite γ
Adapted from
α γ
Fig. 9.15,
α growth α
Callister &
Rethwisch 9e. direction
α
• For this transformation, 100
Carbon
diffusion
y (% pearlite)

rate __________ with 600°C

(ΔT larger)
__________________. 50 650°C
Adapted from
675°C Fig. 10.12,
(ΔT smaller) Callister &
Rethwisch 9e.
0

Coarse ________ à formed at higher temperatures – relatively ____

Fine _______ à formed at lower temperatures – relatively _____

Chapter 10 - 10

Generation of Isothermal Transformation

Diagrams
Consider:
• The Fe-Fe3C system, for C0 = _____ wt% C
• A transformation temperature of ________.
% transformed

100
T = 675°C
y,

50

0 Fig. 10.13, 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
100
50%pearli

500
0%

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 > ________
• Rapidly ____________________
• Hold T (625°C) ___________ (__________ treatment)

T(ºC) Austenite (stable)

TE (727°C)
700 Austenite
(unstable)

Fig. 10.14, Callister & Rethwisch 9e.

600 Pearlite [Adapted from H. Boyer (Editor), Atlas of
γ γ Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
Reproduced by permission of ASM
γ γ γ γ International, Materials Park, OH.]
100
50% rlite

500
0%

%
pea

400

1 10 10 2 10 3 10 4 10 5
time (s)
Chapter 10 - 12

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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

0 1 2 3 4 5 6 6.7
1.13

time (s) (Fe)

C, wt%C
Fig. 10.16, Callister & Rethwisch 9e. Fig. 9.24, 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 – __________cementite

Chapter 10 - 13

Bainite: Another Fe-Fe3C

Transformation Product
• __________:
-- elongated Fe3C ____________ in
α-ferrite __________
-- __________ controlled Fe3C
• Isothermal Transf. ___________, (cementite)
C0 = 0.76 wt% C α (ferrite)
800 Austenite (stable)
T(°C) A
TE
P
600 100% pearlite 5 µm
Fig. 10.17, 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
100
0%

50%

10-1 10 103 105

Fig. 10.18, Callister & Rethwisch 9e. [Adapted
from H. Boyer (Editor), Atlas of Isothermal Transformation
time (s)
and Cooling Transformation Diagrams, 1977. Reproduced
by permission of ASM International, Materials Park, OH.] Chapter 10 - 14

Spheroidite: Another Microstructure

for the Fe-Fe3C System
• Spheroidite: α
-- Fe3C particles within _______________ (ferrite)
-- formation requires _______________
-- heat ____________________________ Fe3C
just below eutectoid for long times (cementite)
-- driving force – reduction
of α-ferrite/Fe3C _________ area

60 µm
Fig. 10.19, Callister &
Rethwisch 9e.
(Copyright United States Steel
Corporation, 1971.)

Chapter 10 - 15

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Martensite: A Nonequilibrium
Transformation Product
• ___________:
-- γ(FCC) to ___________ (BCT)
x

60 µm
Fe atom potential
x x
sites x x C atom sites
x Adapted from Fig. 10.20,
Callister & Rethwisch 9e.

• Isothermal Transf. Diagram

800 Austenite (stable) Martensite needles
T(°C) TE Austenite
A
P Fig. 10.21, Callister & Rethwisch 9e.
600 (Courtesy United States Steel Corporation.)

Adapted from
Fig. 10.22,
Callister & 400 A B 10 • γ to _________ (M) transformation.
Rethwisch 9e. 5 0%
0% 0% -- is rapid! (________________)
200 M+A
0% -- % transformation depends only
50%
M+A 90% on __ to which rapidly _____
M+A
10
-1 10 10
3 5
10 time (s) Chapter 10 - 16

Martensite Formation

γ (FCC) slow cooling α (BCC) + Fe3C

quench
_________
M (BCT)

_________(M) – single phase

– has body centered tetragonal (BCT)
crystal structure

__________ transformation BCT if C0 > 0.15 wt% C

BCT à few slip planes à hard, brittle

Chapter 10 - 17

Phase Transformations of Alloys

Effect of adding other _________
Change transition temp.

Cr, Ni, Mo, Si, Mn

retard γ à α + Fe3C
reaction (and formation of
_________________)

Fig. 10.23, 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 10 - 18

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

Fig. 10.25, 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 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 _______ for C0 = 0.45 wt% C
800 A+α
A
-- all _________ transforms T (°C)
to proeutectoid α and
A+P
coarse pearlite. 600 P
B
C0 − 0.022 A+B
Wpearlite =
0.76 − 0.022 A
400 50%
M (start)
M (50%)
M (90%)
______________
200

Wα ! = 1 − 0.58 = ______
0
Figure on p. 407, Chapter 10, 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 10 - 21

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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°C T (ºC) A
– __________________________
to fine pearlite. P
A+P
600
B
Then _______________ treat A+B
A
at ~ 470°C 50%
400
– all remaining ___________ M (start)
transforms to __________. M (50%)
M (90%)
200

0
Figure on p. 407, Chapter 10, 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 10 - 22

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

Problem
c) 100% _________– rapidly quench to ______
____________ Fe-Fe3C phase diagram,
for C0 = 0.45 wt% C
d) 50% _________ 800 A+α
T (°C) A
& 50% austenite
A+P
-- rapidly quench to 600 P
__________, hold at this B
A+B
temperature A
400 50%
M (start)
M (50%)
M (90%)
d)
200

c)
0
Figure on p. 407, Chapter 10, 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 10 - 23

Mechanical Props: Influence of C Content

_________(med)
Pearlite (med) ____________
ferrite (soft) (hard)
Fig. 9.30, Callister & Rethwisch 9e. C0 < 0.76 wt% C C0 > 0.76 wt% C Fig. 9.33, 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. 10.29, 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
1 0
0.5
0.76

0
0.76

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

Chapter 10 - 24

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

Chapter 10 - 25

Mechanical Props: Fine Pearlite vs.

Martensite

Hypo Hyper

600
Brinell hardness

martensite
Fig. 10.32, 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: ___________________________.

Chapter 10 - 26

Tempered Martensite
Heat treat martensite to form tempered martensite
• tempered martensite ____ brittle than martensite
• tempering reduces internal stresses caused by ________
TS(MPa)
YS(MPa)
1800

1600 TS
Fig. 10.34, Figure 10.33,
YS
9 µm

Callister & Callister &

Rethwisch 9e.
1400 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 __________ TS, YS but __________ %RA
Chapter 10 - 27

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Summary of Possible Transformations

Adapted from
Austenite (γ) Fig. 10.36,
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 10 - 28

10