CHAPTER 11

PHASE TRANSFORMATIONS
NELLO D. SANSONE
ISSUES TO ADDRESS
• Transforming One Phase into Another Takes Time
• How does the Tate 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?

do it on weekend
nucleationtheory
classical

UNIVERSITY OF TORONTO
INTRODUCTION
What are Phase Transformations?
• Changes in the Arrangement or Structure of Atoms within a Material, Leading to Alterations in its Physical and
Chemical Properties.

Three Classifications
1. Simple Diffusion-Dependent Transformations
o No Change in the Number or Composition of the Present Phases

2. Diffusion-Dependent Transformations
o Some Alterations in the Phase Compositions and the Number of Phases Present
o Typically, the Final Microstructure consist of Two Phases

3. Diffusionless Transformations
o Metastable Phase is Produced

stable butnofullyLex diamond

Adapted from Callister & Rethwisch 6e. 2

CLASSICAL NUCLEATION THEORY
•
D
Nucleation and Growth dothhappen simultaneouslygrowthoverstightafter ystablenucleiforms
D
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 for Nucleation Increases as ∆" Increase

• Supercooling (eutectic, eutectoid)
• Efferena
Superheating (peritectic)
from
previousmoststable thistemp
stateand
• Small Supercooling → Slow Nucleation Rate → Few Nuclei → Large Crystals
• Large supercooling → Rapid Nucleation Rate → Many Nuclei → Small CrystalsColette structure

t.it
totemp

Diffusion

Adapted from Callister & Rethwisch 6e. 3

 ( 3)
4 = = 137 unit cells
3 πr ∆Gυ + 4πr γ
3 2
∆G = (11.1) (0.413 nm) 3

CLASSICAL NUCLEATION THEORY

Because of the equivalence of four atoms per FCC unit cell (Section 3.4), the total number of
atoms per critical nucleus is just
ume, surface, and total free energy contributions are plotted schematically
(137 unit cells/critical nucleus)(4 atoms/unit cell) = 548 atoms/critical nucleus
on of nucleus radius in Figures 11.2a and 11.2b. Figure 11.2a shows that for
id
Ffs
Homogeneous
corresponding Nucleation
to the first term on the right-handnot
it's
sidepractical
of Equation 11.1, the
y (which is negative) decreases with the third power of r. Furthermore, for
• Nuclei
resulting from Form Uniformly
the second term inThroughout
Equation 11.1, theenergy
Bulk values
of Liquid Metal
are positive
Heterogeneous Nucleation
Although levels of supercooling for homogeneous nucleation may be significant (on
se •withRequires
the squareConsiderable Supercooling
of the radius. Consequently, 80 −associated
the( curve 300℃ ) with the occasion several hundred degrees Celsius), in practical situations they are often on
the order of only several degrees Celsius. The reason for this is that the activation
th terms (Figure 11.2b) first increases, passes through a maximum, and finally
distort
energy (i.e., energy barrier) for nucleation (∆G* of Equation 11.4) is lowered when
In a physical sense, this means that as a solid particle begins to form as atoms nuclei form on preexisting surfaces or interfaces, because the surface free energy (γ

Heterogeneous Nucleation
id cluster together, its free energy first nucleiform
increases. If this preferentially
cluster reaches
ding to the critical radius r*, then growth will continue with the accompani-
a size ofstructural

heterogeneous.
at grain
boundaries
Equation 11.4) is reduced. In other words, it is easier for nucleation
homogeneities
leg
to occur at
surfaces and interfaces than at other sites. Again, this type of nucleation is termed

• More Favourable since Stable “Nucleating Surface” is Already Present

In order to understand this phenomenon, let us consider the nucleation, on a flat
decrease in free energy. However, a cluster of radius less than the critical
shrink oandMold Wall/Surfaces,
redissolve. Insoluble
This subcritical Impurities,
particle is an embryo, Grain
and theBoundaries,
particle Dislocations
solid
etc
surface, of a solid particle from a liquid phase. It is assumed that both the liquid and
phases “wet” this flat surface—that is, both of these phases spread out and cover
the surface; this configuration is depicted schematically in Figure 11.5. Also noted in
greater than r* is termed a nucleus. A critical free energy, ∆G*, occurs at the
• Only Very Slight Supercooling ( 0.1 − 10℃ ) the figure are three interfacial energies (represented as vectors) that exist at two-phase
dius and, consequently, at the maximum of the curve in Figure For 11.2b. This
heterogeneous boundaries—γSL, γSI, and γIL—as well as the wetting angle θ (the angle between the γSI
nucleation of a solid and γSL vectors). Taking a surface tension force balance in the plane of the flat surface
Homogeneous Nucleation
particle, relationship leads Heterogeneous Nucleation
to the following expression:
among solid–surface,
.1 Schematic diagram showing the 4 3
solid–liquid, and
liquid–surface
γIL = γSI + γSL cos θ (11.12)
of a spherical solid particle in a liquid. Volume = 𝜋r interfacial energies
3 Liquid
and the wetting angle

Liquid Figure 11.5 Heterogeneous

𝛾 SL
r nucleation of a solid from a liquid.
The solid–surface (γSI), solid–liquid
Solid 𝜃 (γSL), and liquid–surface (γIL)
𝛾 IL
interfacial energies are represented
𝛾 SI by vectors. The wetting angle (θ) is
Solid also shown.
Area = 4𝜋 r2 Surface or interface

Solid-liquid
interface

takes
of alot
Adapted from Callister & Rethwisch 6e.energy GFsc x placediagramshowsthis4
 11.3 The Kinetics of Phase Transformations • 445
CLASSICAL NUCLEATION THEORY
Surface Free Energy

HIIIIIS
• Destabilizes the Nuclei (It Takes Energy to Make an Interface)
+
• ∆*! = 4-. " /
and • / = Surface Tension
.r*∗ ofode
Free energy change, 𝛥G

pygmy Volume (Bulk) Free Energy

𝛥G*
• Stabilizes the Nuclei (Releases Energy)
$
0 • ∆*# = -. % ∆*&
radius, r %
• ∆*& = Volume Free Energy per Unit Volume
Total Free Energyso idsfree
• ∆*' = ∆*( + ∆*#
G energy

Critical Nucleus (.(b)

∗
∗) volume freeEnergy Bak
For . <
ee•energy . ,surface
and Nuclei Shrink
free energy siedissolves
contributions
enmity to the total free
• For . > . ∗
, Nuclei Grow (To Reduce to
Energy)
cal embryo/nucleus during solidification. (b) Schematic plot of
nucleus
b
h is shown the critical freegrow
energy change (∆G*) and the critical
spontaneously
Criticalfree
energysore if 316 transformation
phase occurs

Adapted from Callister & Rethwisch 6e. 5

 red
and
sumof
blue

slohmé
of
cluster group
RATE OF TRANSFORMATION
Kinetics
• Study of Reaction Rates of Phase Transformations
• To Determine Reaction Rate – Measure Degree of Transformation as Function of Time (while Holding Temperature
Constant)

How is the Degree of Transformation Measured?

• X-Ray Diffraction – Many Specimens Required
Electrical Conductivity Measurements – On Single Specimen destructivetest
• Non
• Measure Propagation of Sound Waves – On Single Specimen

Adapted from Callister & Rethwisch 6e. 6

 lectrical conductivity) whose magnitude is distinctive
ed as the fraction of transformed material versus the

KINETIC BEHAVIOR FOR SOLID-STATE REACTIONS

ve similar to that in Figure 11.10 represents the typical

1.0
Transformation Complete
CONSTANTTEMP
Fraction of transformation, y3

lessvolume
ThisGraph
0.5 Maximum Rate Reached - Now Amount Unconverted Decreases,
Rate Slows Because wehavelessvolume

9+.- crystallization halftime

t0.5 Rate Increases - Interfacial Surface Area Increases and Nuclei Grow
0
atcenter of transformation

he
Nucleation Growth to.sealways

herewe Logarithm of heating time, t

atlerstgggenucleix 9
Fraction of Transformation (Avrami Equation) Rate of Phase Transformation
transforming
* 1
3 = 1 − exp(−89 )
K property ofthethots .<9= =
9 = Time 9+.-
8 & ; = Transformation Specific Parameters

Adapted from Callister & Rethwisch 6e. 7

 11.3 The Kinetics of Phase Transformations
TRANSFORMATION RATE TEMPERATURE DEPENDENCE
100

Percent recrystallized
80

60 135°C 119°C 113°C 102°C 88°C 43°C

40

20

0
1if 10 102 104
Time (min)
(Logarithmic scale)
.
• Figure
Since the >?@A = 11.11 Percent recrystallization
, the Recrystallization
/
as a function
Rate Increases of time and
with Increasing at constant temperature for pure copper.
Temperature
!.#
(Reprinted with permission from Metallurgical Transactions, Vol. 188, 1950, a publication of The Metallurgical Society of A
• Rate Often Warrendale,
so Slow thatPA.Attainment of Equilibrium
Adapted from State
B. F. Decker and Not Possible!
D. Harker, “Recrystallization in Rolled Copper,” Trans. AIME, 188, 1950, p

kinetic behavior for most solid-state reactions. Nucleation and growth stages a
indicated in the figure.
For solid-state transformations displaying the kinetic behavior in Figure 11
Avrami equation— fraction of transformation y is a function of time t as follows:
dependence
Adapted from Callister & Rethwisch 6e. of 8
n
 composition (0.76 wt% C) above and below the and Microstructures, American Society for
eutectoid temperature. Metals, Materials Park, OH, 1985.)

THE FE-FE3C EUTECTOID TRANSFORMATION

phases [ferrite (0.022 wt% C) and cementite (6.70 wt% C)], and the phase transformation
requires that there be a redistribution of the carbon by diffusion. Figure 10.32 illustrates
Tutorial Video: microstructural changes that accompany this eutectoid reaction; here the directions of
How Do the Eutectoid
carbon diffusion are indicated by arrows.
10.20 Carbon atoms
Development diffuse away
of Microstructure from the 0.022-wt%
in Iron–Carbon Alloys • 423
Microstructures Form?
ferrite regions and to the 6.70-wt% cementite layers, as the pearlite extends from the
• Pearlite: Equilibrium Microstructure of Alternating Lamellae of B-Ferrite and CA0 D 1100

Austenite grain Figure 10.32 Schematic

boundary representation of the
Austinite (FCC) 1000 γ
γ + Fe3C formation of pearlite from Pearlite
austenite; the direction of
α carbon diffusion is indicated
900
by arrows.
γ γ
x Ferrite (α)

Temperature (°C)
γ Austenite
800 a γ ( γ)
Austenite Ferrite ( α )
α + γ ( γ)
727°C
b Ferrite ( α )
α
700
Cementite Growth direction
(Fe3C) α
Ferrite ( α ) of pearlite

α
456 • Chapter 11 / Phase Transformations
50 µm
600
Fe3C
Carbon diffusion 20 µm

20 μm
Figure 11.12 For an iron–carbon alloy of 100 500 α + Fe3C 0
Figure 10.31 Photomicrograph of a

Pfk
eutectoid composition (0.76 wt% C), isothermal eutectoid steel showing the pearlite
fraction reacted versus the logarithm of time fine
400
x′
perlite
microstructure consisting of alternating
for the austenite-to-pearlite transformation. 0 1.0
Composition (wt% C)
2.0
coarse layers of α-ferrite (the light phase) and
Fe3C (thin layers, most of which appear

Percent austenite
dark). 500×.

Percent pearlite
∆" Large
727075
Figure 10.30 Schematic representations of the (Reproduced with permission from Metals
microstructures for an iron–carbon alloy of eutectoid
7
Handbook, 9th edition, Vol. 9, Metallography
50 composition (0.76 wt%650°C
600°C 675°C
C) above and below the 50Microstructures, American Society for
and
eutectoid temperature. Metals, Materials Park, OH, 1985.)
∆" Small
statue
finer phases [ferrite (0.022 wt% C) and cementite (6.70 wt% C)], and the phase transformation
requires that there be a redistribution of the carbon by diffusion. Figure 10.32 illustrates
Tutorial Video:
microstructural changes that accompany this eutectoid reaction; here the directions of

• Coarse Pearlite → Formed at Higher Temperature → Soft whybecauseits notfine How Do the Eutectoid
Microstructures Form?
carbon diffusion are indicated by arrows. Carbon atoms diffuse away from the 0.022-wt%
ferrite regions and to the 6.70-wt% cementite layers, as the pearlite extends from the
100

• Fine Pearlite → Formed at Lower Temperature → Hard lessnuclei 0 1 10 102 103

Austenite grain Figure 10.32 Schematic
Time (s) boundary representation of the

Rate Increases with [F12/13/456 transfor- − F]

formation of pearlite from
austenite; the direction of
Temperature plays an important role in the rate of the austenite-to-pearlite α carbon diffusion is indicated
mation. The temperature dependence for an iron–carbon alloy of eutectoid composition by arrows.
Don't forgetdiffusionhas
Adapted from Callister & Rethwisch 6e.
tohappenforallthisthingto occur
is indicated
versus the logarithm of time at three different temperatures.Austenite
For
( γ)
Ferrite (α)
in Figure 11.12, which plots S-shaped curves of the percentage
each
transformation
Austenite
( γ)
Ferrite (α ) curve, data were 9
collected after rapidly cooling a specimen composed of 100% austenite to the temperature
meltingtemp
forus7272

sum ofred
andgreen

TTTdiagram
timetemperature ons
formation
ure was maintained constant throughout the course of the reaction.
way of representing both the time and temperature depend-

ISOTHERMAL TRANSFORMATION DIAGRAMS

tion is shown in the bottom portion of Figure 11.13. Here, the
axes are, respectively, temperature and the logarithm of time.
lotted; one represents the time required at each temperature 458 • Chapter 11 / Phase Transformations
Consider a Steel with H7 = 0.76 wt. % Carbon and a Transformation
1s
Temperature of 675℃.
1 min 1h 1 day
100
transformed to pearlite

Eutectoid 1400
Percent of austenite

Transformation A 𝛾 Austenite (stable) temperature

Transformation 727°C
temperature 675°C ends
50 700 𝛾 𝛾
YstepO
𝛾 𝛾
Transformation to.s 𝛾 𝛾 𝛼 Ferrite Coarse pearlite

here it
begins
1200
0 www.poaterite C

Temperature (°C)

Temperature (°F)
1 10 2 103 104 105
10
B D
Time (s) 600 Fe3C

Fine pearlite

to noooo
Austenite (stable) Eutectoid temperature
1400
1000

700 Austenite
(unstable) 500 Austenite → pearlite

É
transformation Denotes that a transformation

ii
1200 is occurring
Pearlite
Temperature (°C)

Temperature (°F)
600
50% Completion curve 800

1000 1 10 102 103 104 105

500 Completion curve aaEptiiistitiows Time (s)

(~100% pearlite)
Figure 11.14 Isothermal transformation diagram for a eutectoid iron–carbon alloy, with superimposed
Begin curve 800 isothermal heat treatment curve (ABCD). Microstructures before, during, and after the austenite-to-pear
womtempsoyopailite.soa.us

(~ 0% pearlite) finite
transformation are shown.
400 points
[Adapted from H. Boyer (Editor), Atlas of Isothermal Transformation and Cooling Transformation Diagrams, Americ
for Metals, 1977, p. 28.]
1 10 102 103 104 105
Time (s)
Figure 11.15
10
Adapted from Callister & Rethwisch 6e.
if uwant epondfpPhotomicrographs
ureguireztertment
ofedit
temperatures
FE-FE3C T460 MICROSTRUCTURES
• Chapter 11 / Phase Transformations
RANSFORMATION
• Pearlite: Alternating Figure 11.18
Lamellae of BIsothermal transformation
-Ferrite and CA0 D 800
diagram for an iron–carbon alloy of eutectoid A Eutectoid temperature
1400
the Nose, 540℃
o Formation Above composition, <P
including < 727℃
austenite-to-pearlite
(A–P) and austenite-to-bainite
Course Pearlite Fine Pearlite
transformations.
(A–B)
Perliteonly 510
700
t A coarseeutectoidcompositi
1200
[Adapted from H. Boyer (Editor), Atlas of Isothermal A
+ P
Transformation and Cooling Transformation 600
P
Diagrams, American Society for Metals, 1977, p. 28.]
Nose suo
eutectoidcomposition fine 1000
N

Temperature (°C)

Temperature (°F)
500
10 µm
too.ua o.fatso
10 µm
A+B B 800

f
400
• Bainite: Elongated CA0 D Particles in a B-Ferrite Matrix
A
o Formation Below the Nose, 215℃ < P < 540℃ 300
600

Bainite
Tutorial Video: as
200 50% 400
How Do I Read cementite
a TTT Diagram?
100
10–1 1 10 102 103 104 105
1 µm Time (s)
ferrite
Adapted from Callister & Rethwisch 6e. 11
In addition, the phase that surrounds the needle is martensite, the topic addressed by a
 o
e
ender
T
ece
 FE-FE3C T460 MICROSTRUCTURES
• Chapter 11 / Phase Transformations
RANSFORMATION
• Spheroidite: CA0 D Particles Figure 11.18 Isothermal
in a B-Ferrite transformation
Matrix 800
diagram for an iron–carbon alloy of eutectoid A Eutectoid temperature
1400
o Heat Bainite or Pearlite at a Temperature
composition, around P = 700℃
including austenite-to-pearlite
for 18 − 24 h (A–P) and austenite-to-bainite (A–B) 700
A
transformations.
o Formation Requires Diffusion A
1200
[Adapted from H. Boyer (Editor), Atlas of Isothermal
Development of Microstructure in Iron–Carbon Alloys • 423 + P
o Driving Force for Transformation Transformation and is the Reduction
Cooling Transformationof 600
P
B-Ferrite / CA0 D interfacial area. Diagrams, American Society for Metals, 1977, p. 28.]
1000
N

Temperature (°C)

Temperature (°F)
γ + Fe3C Pearlite Bainite 500

A+B B 800
400
α

A
600
300
Fe3C 20 µm 1 µm

20 μm
Spheroidite
Figure 10.31 Photomicrograph of a Tutorial Video: 50%
eutectoid steel showing the pearlite 200 400
microstructure consisting of alternating How Do I Read
2.0 layers of α-ferrite (the light phase) and
Fe3C (thin layers, most of which appear a TTT Diagram?
dark). 500×.
s of the (Reproduced with permission from Metals
eutectoid Handbook, 9th edition, Vol. 9, Metallography 100
w the and Microstructures, American Society for
Metals, Materials Park, OH, 1985.)
10–1 1 10 102 103 104 105
Time (s)
022 wt% C) and cementite (6.70 wt% C)], and the phase transformation
e be a redistribution of the carbon by diffusion. Figure 10.32 illustrates 10 µm
hanges that accompany this eutectoid reaction; here the directions of
are indicated by arrows. Carbon atoms diffuse away from the 0.022-wt%
Adapted
6.70-wt% from Callister & Rethwisch
pearlite extends 6e.
12
d to the cementite layers, as the from the
In addition, the phase that surrounds the needle is martensite, the topic addressed by a
FE-FE3C T460 MICROSTRUCTURES
• Chapter 11 / Phase Transformations
RANSFORMATION
• Figure 11.18
Spheroidite: CA0 D Particles Isothermal
in a B-Ferrite transformation
Matrix 800
diagram for an iron–carbon alloy of eutectoid A Eutectoid temperature
1400
o Heat Bainite or Pearlite at a Temperature around H = 700℃
Efp
composition, including austenite-to-pearlite
for 18 − 24 h (A–P) and austenite-to-bainite (A–B) 700
on spheroid
A
transformations.
o Formation Requires Diffusion i A
1200
[Adapted from H. Boyer (Editor), Atlas of Isothermal
+ P
o Driving Force for Transformation
Transformation and is the Reduction
Cooling Transformationof 600 sP
Diagrams, American Society for Metals, 1977, p. 28.] i
B-Ferrite / CA0 D interfacial area. n
1000
N

Temperature (°C)
austin.it

Temperature (°F)
tohereitsnot
Up
transformedfrom
Spheroidite sphetpggifpeisfoxmedf 500

A+B B 800
400

A
600
300

Tutorial Video: 50%

200 400
How Do I Read
a TTT Diagram?
100
10–1 1 10 102 103 104 105
10 µm Time (s)

Adapted from Callister & Rethwisch 6e. 13

In addition, the phase that surrounds the needle is martensite, the topic addressed by a
Hesitate
FE-FE3C TRANSFORMATION M ICROSTRUCTURES 462 • Chapter 11 / Phase Transformations
11.5 Iso

•
fine very
Martensite: Martensite Needles in a Austinite Matrix
slender
of
piece metal at
withapoint one
endand
aholeaeye 800 Figure 11.22 Photomi-
crograph
A showing the 1400
Eutectoid temperature
o Single Phase → Body Centered Tetragonal martensitic microstructure.
The needle-shape grains are
700
Structure the martensite phase, and
Athe white regions are
c 1200
o Diffusionless Transformation, if I8 > 0.15 wt. % C A
austenite +that failed to P
600
transform during the rapid
o Transformation Depends Only on the Temperature P
quench. 1220×.
to which the Austinite is Quenched a
a
500
(Photomicrograph courtesy
of United States Steel
1000

rapidcoolingprocess thata11.21
lters The body-

Temperature (°C)

Temperature (°F)
Corporation.)
Figure B
ed
sperificpropertiesof
Martensite materials
diffusion
p manipulating the
centered
by
tetragonal unit
A 800
cooling rate
cell for martensitic
showing iron atoms
steel 400 +
B
(circles) and sites that
may be occupied by carbon A
Metastablematerial 300 600
atoms (×s). For this
tetragonal unit cell, c > a.
1 A 200
M(start)
50% 400
supergood M(50%)
M+A

properties become appreciable.M(90%)Many steels, however, retain their martensitic struc

jg
indefinitely
100 at room temperature.
200
The martensitic transformation is not, however, unique to iron–carbon
found in other systems and is characterized, in part, by the diffusionless tran
Because the martensitic transformation does not involve diffusion, it oc
0
instantaneously;
10–1 the
1 martensite
10 grains102nucleate
103and grow
104at a very
105rapid rate
ity of sound within the austenite matrix. Thus the martensitic transformation
Time (s)
toxins
10 µm practical purposes, is time independent.

Only from
austin
Adapted from Callister & Rethwisch 6e.
Martensite grains take on a platelike or needlelike appearance, as i
Figure 11.22. The white phase in the micrograph is austenite (retained aus
14
did not transform during the rapid quench. As already mentioned, martensi
o
EXAMPLE 01: FE-FE3C EUTECTOID SYSTEM 11.5 Iso

800
Using the isothermal transformation diagram for an iron–carbon A 1400
Eutectoid temperature
alloy of eutectoid composition, specify the nature of the final 700
microstructure (in terms of microconstituents present and A
1200
approximate percentages) of a small specimen that has been 600 +
A
P
subjected to the following time–temperature treatments. In each P

case, assume that the specimen begins at 760℃ and that it has 500
1000

been held at this temperature long enough to have achieved a

Temperature (°C)

Temperature (°F)
B

complete and homogeneous austenitic structure. 400

A
+
800

(A) Rapidly cool to 350℃, hold for 10! s , and quench to room
B

i
temperature. 300
A 600

M(start)
50%
(B) Rapidly cool to 250℃, hold for 100 s, and quench to room
200 M+A 400
M(50%)

temperature. M(90%)

100
200

(C) Rapidly cool to 650℃, hold forModel

20 s, rapidly cool to 400℃, hold 0
10–1 102 103 104 105
for 103 s, and quench to room temperature. 1 10
Time (s)

Adapted from Callister & Rethwisch 6e. 15

y
so Ptso A

loptso.la soPtzsAtzs B
gso do 1Esopt5o B
D
I

61 Totroinite
MY.F
nsité 504Perlite Yogfinite

901
i
Martensite
lootbustinite
 this temperature for 1 to 2 s, and then rapidly
oling
re wasa
ure
oling specimen
specimen composed
a maintained constant
composed
quench
of 100%
throughout
of to
100% austenite to
to the
the course
roomaustenite
temperature
temperature
of the
the reaction.
temperature
ure
ure was
wasofmaintained
way maintained constant
representing boththroughout
constant the time and
throughout the
the course of
temperature
course of the
the reaction.
depend-
reaction.
(B) Rapidly heat the specimen to about 675°C,

HYPO-EUTECTOID ISOTHERMAL TRANSFORMATION DIAGRAMS

tion is shown in the bottom
way of representing hold bothattheportion
thistime
of Figure 11.13.
and temperature
temperature
Here, the
depend-
for 1 to 2 s, then rap-
axes are, respectively,
tion is shown in the bottom temperature
idly quenchportion and the
of Figure
to room logarithm of time.
11.13. Here, the
temperature
lotted;
axes
axes are,one represents
respectively,
are, respectively, the time
temperature
temperature required
and at
the each temperature
logarithm of
of time.
g isothermal (C) Austenitize theand the logarithm
specimen time.
at approximately
wt% •
lotted;
C Consider
one
iron– a
represents Steel
the
775°C, with
time I
required
rapidly cool
8 =
to 0.45
at each
lotted; one represents the time required at each temperature
about wt. % Carbon
temperature
500°C, hold at and a Transformation Temperature of 675℃.
ould be 100
used this temperature for 1 to 2 s, and then rapidly
ure that con- quench to room temperature
to pearlite
of austenite

100
pearlite100
into Transformation Transformation
(D) Austenitize the specimen ends at approximately
to pearlite
of austenite

d ferrite and temperature 675°C

to pearlite

775°C, rapidly coolTransformation

to about 675°C, hold at
of austenite

Transformation
50 Transformation
temperature 675°C Transformation
ends
this temperature for 1 to 2 s, and then rapidly
transformed

temperature ends
675°C to room temperature
Percent

pproximately
50 quench
Transformation
transformed

5°C, hold50at begins

Percent
transformed

Transformation
Percent

0 begins
Transformation
1 10
begins 102 103 104 105
0
1 10 Time
10 2 (s) 103 104 105
900
0
no
1 10 Time
10 2 (s) 103
104 1051600
800 Time (s)
A+F 1400
A Austenite (stable) Eutectoid temperature 1400
1400
700 Austenite (stable)
Austenite Eutectoid temperature
t, 700
(unstable)
You
700 Austenite
Austenite (stable)A + P xp 1400
1200
Eutectoid temperature 1200
600 (unstable) P
typ
Pearlite
caso.az
(°C) (°C)

Austenite B 1200 (°F) (°F)

700
600 Pearlite 1000
p
Temperature (°F)
Temperature (°C)

(unstable)
Temperature
Temperature

up gypo.o
500 50% Completion
A+B curve
600
Temperature
Temperature

A 50% Completion
1200
1000
Pearlite curve 800
todetermine
(°C)

(°F)

400 50%
Completion curve 1000

mm
500
600 M(start)
(~100% pearlite)
Temperature
Temperature

500
300
M(50%)
(~
50% Completion
Completion
100%
curve curve
pearlite)
600ofperlitenot
Begin curve 800
1000
thea'xpthis
oneisforpates is
(~ 0% pearlite)
M(90%)
400 Begin curve 800
500
200 Completion curve
(~ 0% pearlite)
400
400 (~100% pearlite)
1 10 102 103 104 105
100 200
Begin curve 800
1 (~ 0% pearlite)
10 Time
10 2 (s) 103
104 105
400
Adapted0 from Callister & Rethwisch 6e.(s)
Time 17
 700°C, rapidly cool to about 675°C, hold at

EXAMPLE 02: FE-FE3C HYPO-EUTECTOID SYSTEM

Isothermal transformation diagram for 900
Using the isothermal transformationa 0.45 diagram for a 0.45
wt% C iron–carbon wt.A,% C steel
alloy: 1600
alloy, specify the nature of the final microstructure
austenite; (in terms of
B, bainite; F, proeutectoid 800

i
A+F
ferrite; M, martensite;
microconstituents present and approximate P, pearlite.of a small
percentages) A 1400
(Adapted from Atlas of Time-Temperature
specimen that has been subjected to the
Diagrams following
for Irons time–
and Steels, G. F. Vander Voort, 700

temperature treatments. In each case, assume that the specimen

Editor, 1991. Reprinted by permission of ASM i
International, Materials Park, OH.)
ni A+P
atp 1200

begins at 800℃ and that it has been held at this temperature long 600
n P

enough to haveto achieved a complete and homogeneous austenitic B

1000

Temperature (°F)
Temperature (°C)
structure.
loopy spit
500
11p A+B
ioo B
to
(A) Rapidly cool to 650℃, hold for 10! s, and quench to room i
A g
n 50% 800
400 I l
temperature. 12 M(start)
2 t 584 p M(50%) 600
(B) Rapidly cool to 590℃, hold for 1 s, then rapidly cool to 470℃, 300

s
hold for 10! s, and quench to room temperature. M(90%)

j
200 400
(C) Rapidly cool to 290℃, hold indefinitely at this temperature.
5o Mtso A 100 200

0 a'tip Footuselevertulecgoslidett
0.1 1 10 102 103 104 105
Time (s)

wp.EEas.o.us
o.oz o.uzz
0.7o 0.58

Adapted from Callister & Rethwisch 6e.

17 0.42
wa 0.58 18
 homogeneous
re wasa maintained
ure austenitic
constant structure. the course of the reaction.
throughout
Time (s)
(b) 50% martensite and 50% austenite
oling specimen composed of 100% austenite to the temperature
way of (a) Cool rapidly
representing to
both 350°C
the (660°F),
time andhold for 103 s,
temperature depend-
ure was maintained
an important constant
role in tothe throughout
ratetemperature. the course of the reaction.
of the austenite-to-pearlite transfor- (c) 50% coarse pearlite, 25% bainite, and 25%
then quench room

HYPER-EUTECTOID ISOTHERMAL TRANSFORMATION DIAGRAMS

tion
e way is shown in the
of representing
dependence bottom portion
both the time
for an iron–carbon of
alloyand Figure 11.13.
temperature
of eutectoid Here,
depend-
compositionthe
martensite
axes
12, are,
which (b) Rapidly cooltemperature
respectively,
plots S-shaped to 625°C of
curves (1160°F),
theand hold
the
percentagefor 10transformation
s,
logarithm of time.
tion is shown in thetobottom
then quench room
portion of Figure 11.13. 11.21
temperature.
Here,Using
the the isothermal transformation diagram for
time at one
lotted; three different
represents temperatures.
the time required For each curve,
at logarithm
each dataa were
1.13 wt% C steel alloy (Figure 11.50), determine
temperature
axes are, respectively,
oling a specimen composed
temperature
of 100%
and the
austenite
of time.
(c) Rapidly cool to 600°C (1110°F), hold toforthe
4 s, temperature
the final microstructure (in terms of just the micro-
ure was Consider
• maintained
lotted; one represents
rapidly a 450°C
Steel
coolconstant
to with
the throughout
time
(840°F), I"the
required
hold =course
for 1.13
at
10 each wt.
of
s, then the % Carbon and a Transformation Temperature
temperature
reaction.
constituents present) of a small specimen that has
of 675℃.
way of representing
quench
100 to room both the time and temperature depend-
temperature. been subjected to the following time–temperature
tion is shown in the bottom portion of Figure 11.13. Here, the
to pearlite

(d) Reheat the specimen in part (c) to 700°C treatments. In each case assume that the specimen
of austenite

100
axes are, respectively, temperature and the logarithm ofbegins
Transformation time.at 920°C (1690°F) and that it has been held
(1290°F)Transformation
for 20 h.
pearlite to pearlite

endseach temperature
of austenite

lotted; one represents

temperature the
675°Ctime required at
Transformation at this temperature long enough to have achieved
Transformation
(e) Rapidly cool to 300°C (570°F), holdends
for 20 s,
50 temperature 675°C a complete and homogeneous austenitic structure.
totransformed

then
100
quench to room temperature in water.
Percent

50
Reheat to 425°C (800°F) for 103 s and slowly cool
Transformation (a) Rapidly cool to 250°C (480°F), hold for 103 s,
transformed
austenite

begins
to room Transformation
temperature. Transformation then quench to room temperature.
Percent ofPercent

Transformation ends
temperature 675°C
(f) begins
0 Cool rapidly to 665°C (1230°F), hold for 103 s, (b) Rapidly cool to 775°C (1430°F), hold for 500 s,
50
102 103 104 105then quench to room temperature.
transformed

then 1 10
quench to room temperature.
0 Transformation
1 10 Time
10 2 (s) 103 104 105
begins
900 Figure 11.50 Isothermal transformation
Time (s) 1600
0
2
diagram for a 1.13 wt% C iron–carbon alloy:
1 10 10 103 104 105
A A, austenite; B, bainite; C, proeutectoid

a
800 A+C Time (s)
1400 cementite; M, martensite; P, pearlite.
Austenite (stable) Eutectoid temperature 1400
1400 [Adapted from H. Boyer (Editor), Atlas
700 Austenite (stable)
Austenite Eutectoid temperature of Isothermal Transformation and Cooling
700 1400
(unstable)
Austenite (stable) Eutectoid temperature 1200 Transformation Diagrams, 1977. Reproduced
700 Austenite A + P
(unstable) 1200 by permission of ASM International, Materials
Austenite
7
4
700
600
(unstable) PPearlite Park, OH.]
(°C) (°C)

1200
1000
1200
(°F) (°F)
600 Pearlite

it
Temperature (°C)

Temperature (°F)
Temperature
Temperature

A+B Pearlite
(°C)

(°F)
500 50% Completion curve
600
600
Temperature
Temperature

Temperature
Temperature

50%
50% Completion
Completion curve
curve 1000
800
400 B 1000
500 Completion curve 1000
500 ~100% pearlite)
(Completion curve
500 A ~100% pearlite)
(Completion curve 600
300
Begin (~ 100% pearlite) 50 %
Begin curve
curve 800
800
((~
~ 0%
0% pearlite)
pearlite)
400 Begin
M(start)
curve 800
400
200 (~ 0% pearlite)
400
1M(50%) 10 102 103 104 105
1 10 102 103 104 105
belowandthe 0.022 changes
phasesinside weswitch
100 Time (s) 200

for
M(90%)
1 10 Time
10 2 (s)
103 104 105
Adapted from Callister & Rethwisch 6e.(s)
Time 20
0
 Reheat to 425°C (800°F) for 10 s and slowly cool (a) Rap
to room temperature. then que

EXAMPLE 03: FE-FE3C HYPER-EUTECTOID SYSTEM

(f) Cool rapidly to 665°C (1230°F), hold for 103 s, (b) Rap
then quench to room temperature. then que
900
Using the isothermal transformation diagram for a 1.13 wt. % C steel I 1600

alloy, specify the nature of the final microstructure (in terms of 800 1i A
A+C
microconstituents present with approximate percentages, and
it
1400

phases with proportions) of a small specimen that has been 700

subjected to the following time–temperature treatments. In each A+P 100 sphadite1200
case, assume that the specimen begins at 920℃ and that it has 600
P
i
been held at this temperature long enough to have achieved a i 1000

Temperature (°C)
i

Temperature (°F)
A+B
500
complete and homogeneous austenitic structure. i
i
(A) Rapidly cool to 250℃, hold for 10# s, and quench to room 400 B
800

temperature.
904Mt look A or too hM
Bothworks 300
A
I 50 % 600

I
M(start) 400
200
M(50%)
l
(B) Rapidly cool to 700℃, hold for 10$ s, and quench to room 100 M(90%) I 200

temperature. 1
demise of thetemperature 0 ao M loutospherodite
100 spherodite 1 10 noon
102 103 104 105 106
Time (s)
10 s or greater is spherodite slide
phrodite
ferriteandcementite atfest gotopier
wa 75
Adapted from Callisterto o.gggig
& Rethwisch 6e. wise 4 0.8 0.100 21
 mpoilal Reheat to 425°C (800°F) for 10 s and slowly cool (a) Rap
to room temperature. then que

EXAMPLE 03: FE-FE3C HYPER-EUTECTOID SYSTEM

(f) Cool rapidly to 665°C (1230°F), hold for 103 s, (b) Rap
then quench to room temperature. then que
900
Using the isothermal transformation diagram for a 1.13 wt. % C steel 1600

alloy, specify the nature of the final microstructure (in terms of H A

I
800 A+C
microconstituents present with approximate percentages, and 1400

t
phases with proportions) of a small specimen that has been 700
subjected to the following time–temperature treatments. In each i A+P
1200

case, assume that the specimen begins at 920℃ and that it has 600

1
P
been held at this temperature long enough to have achieved a 1000

Temperature (°C)

Temperature (°F)
A+B
500
complete and homogeneous austenitic structure.
(C) Rapidly cool to 700℃, hold for 10 s, and quench to room 400
I B
800

temperature. peggiogutegtoidncementite rightoniediedline usetes I

1

my
y
naphases.tt A 600
300 50 %

We.itfe o 00z6.2 fesC't93.84oMoto.z fesc'toy.ua

mtgzo 200 A M(start) 400
recuse 727
(D) Rapidly cool to 650℃, hold for 2 s, and quench to room
temperature. xfesc't
perlitecomponents t M(50%)

yMtzP
Now webreakdownPlandswithlinedown100 200

tf
M(90%)

p Wa 877
853,083 te
0
1 10 102 103 104 105 106

11 15 8 n
this
Time (s)

1,1
o.zfescituty.pt 47ohm
wee
fi goss o.n
ox
o.z fe.it
Adapted from
olot4 soloat42
Callister & Rethwisch 6e.
solom 23
 tiontion of concentration
of concentration for for several
several other
other alloying
alloying elements.
elements. Thus,
Thus, other
other alloyalloy additions
additions
alteralter
not not
onlyonly
the the temperature
temperature of the
of the eutectoid
eutectoid reaction,
reaction, but but
alsoalso
the the relative
relative fractions
fractions

THE INFLUENCE OF ALLOYING ELEMENTS of pearlite

of pearlite andand
the the proeutectoid
proeutectoid phasephase
thatthat
form.form. Steels
Steels are are normally
normally alloyed
alloyed for other
for other to
resistance
improve
reasons,
reasons, however—usually
however—usually either
either to improve
to improve theirtheir corrosion
corrosion resistance
resistance or toor render
to render
them them amenable
amenable to heat
to heat treatment
treatment (see(see Section
Section 14.6).temp mechanical
14.6).
• Consider
formations 4340 Steel which contains 0.40 wt. % Carbon and 1.8 wt. % of andimprove
Nickel-Chromium-Molybdenum. properties
800
A
Ti Ti 24002400 0.8 0.8
1400
Eutectoid temperature Mo Mo W W Ni Ni
12001200 22002200

C)

Eutectoid composition (wt% C)

(wt. %)
Eutectoid temperature (°C)

Eutectoid temperature (°F)

(°C)

(°F)
j
700 Si Si

temperature(℃)

temperature(℉)

Composition(wt%
20002000 0.6 0.6

EutectoidTemperature
EutectoidTemperature
A+F F+P 1200
A+F

Eutectoidcomposition
A +P 10001000
600 18001800 Cr Cr

tionstantions
Cr Cr 0.4 0.4
mandiffusion
phase 16001600
1000 tonic slower

Eutectoid
Eutectoid
Si Si
500 pyrogen
800 800

Eutectoid
twitter.onoun.ee
eitinttiaigimm 14001400 Mo Mo Mn Mn
I lowertdiffusionas
Temperature (°C)

W W

Temperature (°F)
0.2 0.2
Mn Mn12001200 Ti Ti
800
400 600 600
A+B
NiNi10001000
50% 0 0
B 0 02 24 46 68 810 10 12 12 14 14 0 02 24 46 68 10 10
8 12 12 14 14
600
300 M(start) Concentration of alloying
Concentration
Composition elements
ofofAlloying
alloying (wt%)
elements
Elements (wt%)
(wt. %) Concentration of
Concentration
Composition alloying elements
of alloying
of Alloying (wt%)
elements
Elements (wt. %)(wt%)
M+A
Figure 10.38 TheThe
dependence of eutectoid
• Figure 10.38
M(50%)
M(90%) The
temperature
Addition ofdependence
on alloy
Alloying of eutectoidSlows Figure
Elements
concentration for several
Down 10.39V→
the10.39
Figure BThe
The + CA D reaction
dependence of of
dependence %
200 400 temperature on alloy concentration for several eutectoid composition
eutectoid (wt%
composition C) on
(wt% C) on
(and
alloying
alloying formation
elements in steel.
elements of
in steel. Pearlite, Bainite) alloyalloy
concentration for several alloying
concentration for several alloying
(From Edgar
(From C. Bain,
Edgar Functions
C. Bain, of theofAlloying
Functions the Alloying elements in steel.
M Elements in Steel, American Society for Metals,
elements in steel.
100 200 Elements in Steel, American Society for Metals, (From Edgar C. Bain, Functions of theofAlloying
1939,1939,
p. 127.) (From Edgar C. Bain, Functions the Alloying
p. 127.) Elements in Steel, American Society for Metals,
Elements in Steel, American Society for Metals,
0 If uput2 alloys which to
eutectoidpoint
oneisgoing affect 1939,1939,
p. 127.)
p. 127.) exam Q
1 10 102 103 104 105 106
M
Adapted from Callister & Rethwisch 6e.
Time (s)
3
The3The
termterm
metastable makesure
equilibrium
metastable is used
equilibrium answer
in this
is used discussion
in this because
discussion Fe3CFeis3C
because only a metastable
is only compound.
a metastable compound.
this II 25
MECHANICAL PERFORMANCE STRUCTURE-PROPERTY RELATIONS
470 470
• Increasing the Carbon Content Increases the Tensile and Yield Strength, and Hardness
•

• But, Reduces the Ductility and Impact Strength

•

Percent Fe3C

103 psi
0 3 6 9 12 15

MPa MPa
Percent Fe33C Percent Fe3C

103 psi
0 3 6 9 12 15 0 3 6 9 12 15
Percent Fe3C 1200 Percent Fe3C 120 Pearlite + ferrite
3 6 9 12 15 Pearlite
1200 120 0 3Pearlite +6ferrite
Pearlite + ferrite
9 12 15
120 80
1100 160 350 Pearlite + ferrite + Fe3C
Pearlite
Pearlite
Pearlite + ferrite Pearlite
Pearlite + ferrite + C
+ Fe 80 100 80
3501100 160 + Fe3C
Pearlite 1000 Fe33C 350
Pearlite
+ 140
100 + Izod impact
100 60
Fe3C 300 energy
1000 Fe3C
900 Tensile strength

(ft-lbf) (ft-lbf)
140 Izod impact Izod impact
60 80 60

number
300 energy energy
300
Tensile strength 120 Tensile strength

f)
900

(%) (%)

energyenergy
strength

800

energy (ft-lb
80 80 40
Brinell hardness number

hardness number
250

s
Ductility
Izod impact hardness
120
Ductility (%)

I
strength

800

Izod impact
700 40 60 40
100
and tensile

250 250

Ductility
Reduction

Izod impact
BrinellBrinell
700 60 Brinell hardness 60 in area 20
100
tensile

600 200
80 Reduction Reduction
Brinell hardness Brinell hardness 20 40
Yield

in area in area 20
600
Yield and

200 500 200

80
40 40 0
500 60 150

ji
400
Yield strength 0 20 0
150 60 150 Elongation
400
300 20 20
Yield strength 40 Yield strength
Elongation 100 Elongation
300 0
400

É
0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
100 100
0 Composition (wt% C) 0 Composition (wt% C)
0.2 0.4 0.6 0.8 1.0 00 0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 1.0
1.0 0 0.2 0.4 0.6 0.8 1.0
(a) (b)
Composition (wt% C) Composition
Composition(wt%
(wt%C)
C) Composition (wt% C)
Adapted from(a) Figure
Callister & Rethwisch 6e. 11.30 (a) Yield strength, tensile
(a) strength, and Brinell hardness versus carbon concentration
(b) (b) for plain carbon steels
26
 Fppgepas

Bcc Sittwe Edit I than

stronger a

C D B A
 Fcc

Étest
If Effie'd m

A D B E

Fey

Ktiff
ductility
good

Betterthanspherodite

Howimprove martensite roomT

gotoGsoE relaxand stiff
structurebecomesless
 ofoot'll 1 8 at
relation eutectoid
pearlite x

I 0
Check3Dprinterdesign
slides

Ghadeststrongest
material metastable
if reheat300000 we get softerbutmore
ductile material

A BB DSC
C B D A