Chapter 10:

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 T ?
• How can we slow down the transformation so that
we can engineering non-equilibrium structures?
• Are the mechanical properties of non-equilibrium
structures better?
Chapter 10 - 1
Phase transformations are divided into three classifications:

1. simple diffusion-dependent transformations in which there is no

change in either the number or composition of the phases present.
( Ex. Solidification of a pure metal, allotropic transformations,
recrystallization and grain growth)

2.another type of diffusion-dependent transformation, there is some

alteration in phase compositions and often in the number of phases
present; the final microstructure ordinarily consists of two phases
( Ex. The eutectoid reaction)

3. The third kind of transformation is diffusionless, wherein a

metastable phase is produced.( Ex. martensitic transformation)

Chapter 10 - 2
The progress of a phase transformation may be broken
down into two distinct stages:

1. nucleation: involve the appearance of very small particles, or

nuclei of the new phase which are capable of growing. Favorable
positions for the formation of these nuclei are imperfection sites,
especially grain boundaries.

2. growth : the nuclei increase in size; during this process, of

course, some volume of the parent phase disappears. The
transformation reaches completion if growth of these new phase
particles is allowed to proceed until the equilibrium fraction is
attained.

Chapter 10 - 3
 Phase Transformations
Nucleation
– nuclei (seeds) act as template to grow crystals
– for nucleus to form rate of addition of atoms to
nucleus must be faster than rate of loss
– once nucleated, grow until reach equilibrium
Driving force to nucleate increases as we increase T
– supercooling (eutectic, eutectoid)
– superheating (peritectic)

Small supercooling  few nuclei - large crystals

Large supercooling  rapid nucleation - many nuclei,
small crystals

Chapter 10 - 4
 Solidification: Nucleation Processes

• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires supercooling (typically 80-300°C max)
• Heterogeneous nucleation
– much easier since stable “nucleus” is already
present
• Could be wall of mold or impurities in the liquid
phase
– allows solidification with only 0.1-10ºC
supercooling

Chapter 10 - 5
 Homogeneous nucleation
•Related to Gibbs free energy G

•Free energy is a function of other thermodynamics parameters:

─ internal energy of the system ( the enthalpy H)
─ a measurements of the randomness or disorder of the atoms
( the entropy )

• Transformation will occur spontaneously only when ∆G has a

negative value

Chapter 10 - 6
•There are two contributions to the total free energy change that
accompany a solidification transformation:
1.Free energy difference between the solid and liquid phases(or the
volume free energy ∆Cv : negative if the T is below the equilibrium
solidification temperature;
- the magnitude = ∆Gv x Volume of the spherical nucleus(4/3πr3 )
2. The second energy results from the formation of the solid-liquid
phase boundary during the solidification transformation( or the
surface free energy γ) which is positive
- the magnitude = γ x The surface area of the nucleus(4πr2 )
3. The total free energy change ∆G = 4/3πr3 ∆Gv + 4πr2 γ

• A critical free energy ∆G* occurs at the critical radius and,

consequently at the maximum of the curve. This ∆G* corresponds to an
activation free energy, which is the free energy required for the
formation of a stable nucleus. Equivalent, it may be considered an
energy barrier to the nucleation process.
Chapter 10 - 7
 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 radius of nucleus: nuclei < r* shrink; nuclei>r* grow (to reduce energy)
Chapter 10 - 8
Since r* and ∆G* appear at the maximum on the free energy-versus-
radius curve, we can find r* and ∆G* by derivation equ.

d G  4
dr 3
 
 Gv 3r 2  4 2r   0

2
r  
*
and
Gv
16 3
G * 
3Gv 
2

This volume free energy change ∆Gv is the driving force for the
solidification transformation, and its magnitude is a function of
temperature Tm, the value of ∆Gv is zero, and with diminishing
temperature its value becomes increasingly more negative.
Chapter 10 - 9
 Solidification
r* = critical radius
 2 Tm = surface free energy
r* 
HS T Tm = melting temperature
HS = latent heat of solidification
T = Tm - T = supercooling

Note: HS = strong function of T

 = weak function of T

 r * decreases as T increases
 ∆G* decreases as T increases

For typical T r* ca. 100Å

Chapter 10 - 10
There are two important parameters ( temperature-dependent)
influence nucleation:

1.The number of stable nuclei n* ( having radii greater than r* )

 G *

n  k1 exp 
*

 kT 
2. the clustering of atoms by short – range diffusion during the
formation of nuclei
 Qd 
 d  K 2 exp  
 kT 
Qd – activation energy for diffusion ( temp. independent)
K2 temp.independent constant Chapter 10 - 11
 Nucleation rate N
- it has units of nuclei per unit volume per second

  G *
  Qd 

N  k3 n  d  K1 K 2 K 3 exp 
*
 exp  
  kT   kT 
Nucleation rate expression for homogeneous nucleation
K3 – the number of atoms on a nucleus surface
Comments:
• This method may be applied to any shape with the same final result
• May be utilized for types of transformations other than solidification
( ex. Solid-vapor, solid-solid)
• For solid – solid transformation, there may be volume changes
attendant to the formation of new phases, consequently will affect the
magnitudes of r* and ∆G*
Chapter 10 - 12
 Tm

νd

temperature N
n*

Supercooling (undercooling): when during the cooling of liquid an

appreciable nucleation rate ( i.e., solidification) will begin only after
the temperature has been lowered to below the equilibrium
solidification
( or melting) temperature Tm .
The degree of supercooling
Superheating: may be
Heating to above significant.
a phase transition temperature
without the occurrence of the transformation. Chapter 10 - 13
 Heterogeneous nucleation
It is a nucleation which occurs at surfaces and interfaces( which is easier
than other sites, because of the activation energy ( energy barrier) for
nucleation is lowered when nuclei form on preexisting surfaces or
interfaces, since the surface free energy is reduced.
liquid  SL
θ
 IL
solid
 SI
     cos 
IL SI SL

2 SL
r 
*

Gv
S(θ) is a function only of θ ( the
16 3
S  
shape of nucleus), which will
G  * SL

3G  2 have a numerical value between

v zero and unity. Chapter 10 - 14
 r*

∆G
Ghom
*

Ghet
*

0 r

G *
het  G *
hom S  

Heterogeneous nucleation occurs more readily

Chapter 10 - 15
Tm

Nhet

Nhom

Nucleation rate

Chapter 10 - 16
 Growth
• The growth step in a phase transformation begins once an embryo
has exceeded the critical size, r* and becomes a stable nucleus. The
nuclei increase in size; during this process, of course, some volume of
the parent phase disappears. The transformation reaches completion if
growth of these new phase particles is allowed to proceed until the
equilibrium fraction is attained

• The growth rate G is determined by the rate of diffusion, and

its temperature dependence is the same for the diffusion coefficient

  Q
G  C exp  , Q  activation energy
 kT 

Chapter 10 - 17
 Overall transformation rate

Tm
Growth rate, G

Overall transformation rate

Nucleation rate, N

Rate
Overall transformation rate is equal to some product of N and G.
• the size of product phase is particles will depend on
transformation temperature.
Chapter 10 - 18
 Rate of Phase Transformations

Kinetics - measure approach to equilibrium vs.

time
• Hold temperature constant & measure
conversion vs. time
How is conversion measured?
X-ray diffraction – have to do many samples
electrical conductivity – follow one sample
sound waves – one sample

Chapter 10 - 19
 Rate of Phase Transformation
Fraction transformed, y
All out of material - done
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
Logarithm of heating time, t

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

fraction time
transformed
– k & n fit for specific sample(time independent constant
The rate of transformation r is taken as the
By convention r = 1 / t0.5 reciprocal of time required to
Chapter 10 - 20
Proceed halfway completation
 Rate of Phase Transformations

135C 119C 113C 102C 88C 43C

1 10 102 104

• In general, rate increases as T 

r = 1/t0.5 = A e -Q/RT
– R = gas constant
Arrhenius
– T = temperature (K) expression
– A = preexponential factor
– Q = activation energy
• r often small: equilibrium not possible! Chapter 10 - 21
 Eutectoid Transformation Rate

• Growth of pearlite from austenite: Diffusive flow

of C needed
Austenite () cementite (Fe3C)
grain  Ferrite () 
boundary  
  

 pearlite 

 growth
direction 

• Recrystallization 100
y (% pearlite)

rate increases 600°C

(T larger)
with T. 50 650°C
675°C
(T smaller)
0

Course pearlite  formed at higher T - softer

Fine pearlite  formed at low T - harder Chapter 10 - 22
 Nucleation and Growth
• Reaction rate is a result of nucleation and growth
of crystals.
100 Nucleation rate increases with T
% Pearlite Growth
regime Growth rate increases with T
50 Nucleation
regime

0 t 0.5 log (time)

• Examples:
pearlite
 colony  

T just below TE T moderately below TE T way below TE

Nucleation rate low Nucleation rate med  Nucleation rate high
Growth rate high Growth rate med. Growth rate low

Chapter 10 - 23
 Transformations & Undercooling
• Eutectoid transf. (Fe-C System):    + Fe3C
• Can make it occur at: 0.76 wt% C 6.7 wt% C
...727ºC (cool it slowly) 0.022 wt% C
...below 727ºC (“undercool” it!)
T(°C)
1600

1400 L
  +L
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
1000
 Eutectoid:  +Fe3C
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727°C
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) Co , wt%C
Chapter 10 - 24
Microstructure and property changes
in Iron – Carbon Alloys
• Pearlite

• Bainite

• Spheroidite

• Martensite

Chapter 10 - 25
 Isothermal Transformation Diagrams
Consider again the iron–iron carbide eutectoid reaction

which is fundamental to the development of microstructure in steel

alloys. Upon cooling, austenite, having an intermediate carbon
concentration, transforms to a ferrite phase, having a much lower carbon
content, and also cementite, with a much higher carbon concentration.
Pearlite is one microstructural product of this transformation
• Temperature and time play an important role in the rate of the
austenite-to- pearlite transformation

Chapter 10 - 26
Chapter 10 - 27
 Isothermal Transformation Diagrams

• Fe-C system, Co = 0.76 wt% C

• Transformation at T = 675°C.
% transformed

100
T = 675°C Transformation end
y,

50
Transformation
0
1 10 2 10 4 time (s) beginning
T(°C) Austenite (stable)
TE (727C)
700 Austenite
(unstable)

600 Pearlite
isothermal transformation at 675°C
10 0
50%pearli

500
0%

400
time (s)
te

1 10 10 2 10 3 10 4 10 5 Chapter 10 - 28
Several constraints are imposed on using diagrams like
Figure before:

• This particular plot is valid only for an iron–carbon

alloy of eutectoid composition; for other compositions,
the curves will have different configurations

• These plots are accurate only for transformations in

which the temperature of the alloy is held constant
throughout the duration of the reaction
such as Figure are referred to as isothermal transformation
diagrams, or sometimes as time–temperature–transformation
(or T–T–T) plots.
Chapter 10 - 29
Effect of Cooling History in Fe-C System
• Eutectoid composition, Co = 0.76 wt% C
• Begin at T > 727°C
• Rapidly cool to 625°C and hold isothermally.
T(°C) Austenite (stable)
A TE (727C)
700 Austenite
(unstable)
625 B C D
600

Pearlite An actual


isothermal heat
  
10 0

treatment curve
5 0 % r l it e

500
0%

(ABCD) on the
pea

400
TTT diagram

1 10 10 2 10 3 10 4 10 5
time (s)
Chapter 10 - 30
Coarse pearlite: This microstructure has relatively
thick layers of both the -ferrite and Fe3C –phases at
temperatures just below the eutectoid

Fine pearlite: The thin-layered structure produced in

the vicinity of 540C because of decreasing
temperature, and so the decrease of carbon diffusion
rate

Chapter 10 - 31
 Transformations with
Proeutectoid Materials
CO = 1.13 wt% C
T(°C) T(°C)
900 1600

A 1400 L
800

Fe3C (cementite)
+
A TE (727°C)   +L
1200 L+Fe3C
700 A C (austenite)
P 1000
A
+ P   +Fe3C
600
800
727°C
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)
Co , wt%C

Hypereutectoid composition – proeutectoid cementite

Chapter 10 - 32
 Non-Equilibrium Transformation
Products: Fe-C
• Bainite:
-- lathes (strips) with long
rods of Fe3C
 Fe3C
--diffusion controlled.
(cementite)
• Isothermal Transf. Diagram (ferrite)
800 Austenite (stable)
T(°C) A
TE
P
600 100% pearlite
pearlite/bainite boundary 5 m
100% bainite It occurs at temperatures below those at
400 A B which pearlite forms; begin-, end-, and
half-reaction curves are just extensions of
those for the pearlitic transformation
200
1 00
0%

Pearlite forms above the nose—that is, over

50%

the temperature range of about 540 to 727.

10-1 10 103 105 At temperatures between about 215 and
time (s) 540C Bainite is the transformation product.
Chapter 10 - 33
 Spheroidite: Fe-C System
• Spheroidite is formed when a steel
alloy having either pearlitic or bainitic 
(ferrite)
microstructures is heated to, and left
at, a temperature below the eutectoid
Fe3C
for a sufficiently long period of time—
(cementite)
for example, at about 700C (1300F) for
between 18 and 24 h
•The Fe3C phase appears as spherelike
60 m
particles embedded in a continuous α
phase matrix.
• Spheroidite:
-- grains with spherical Fe3C
--diffusion dependent.
--heat bainite or pearlite for long times
--reduces interfacial area (driving force) Chapter 10 - 34
 Martensite: Fe-C System
• Martensite:
--(FCC) to Martensite (BCT)
(involves single atom jumps)

60 m
x
Fe atom potential
x x
sites x x C atom sites
(Adapted from Fig.
x
10.20, Callister, 7e.

• Isothermal Transf. Diagram

800 Austenite (stable) Martensite needles
T(°C) TE Austenite
A
P
600

400 A B 10 •  to M transformation..
5 0 %
0 % 0% -- is rapid!(quenching process)
200 M+A
0% -- % transf. depends on T only
50%
M+A 90% -- time independent
M+A
10-1 10 103 105 time (s) Chapter 10 - 35
 Martensite Formation
Is formed when austenitized iron–carbon alloys are rapidly cooled (or
quenched) to a relatively low temperature (in the vicinity of the ambient)

 (FCC) slow cooling  (BCC) + Fe3C

quench
tempering
M (BCT)

M = martensite is body centered tetragonal (BCT)

Diffusionless transformation BCT if C > 0.15 wt%

BCT  few slip planes  hard, brittle

Martensite is a nonequilibrium single-phase structure that results

from a diffusionless transformation of austenite(rapid cooling
prevent carbon diffusion). Chapter 10 - 36
Chapter 10 - 37
 Phase Transformations of Alloys
Effect of adding other elements
1. Change transition temp.
2. changes in the positions and
shapes of the curves in the
isothermal transformation
diagrams .

Cr, Ni, Mo, Si, Mn

retard    + Fe3C
transformation

Chapter 10 - 38
 CONTINUOUS COOLING
TRANSFORMATION DIAGRAMS
• An isothermal transformation diagram is valid only for conditions
of constant temperature, which diagram must be modified for
transformations that occur as the temperature is constantly
changing. For continuous cooling, the time required for a reaction to
begin and end is delayed. A plot containing such modified beginning
and ending reaction curves is termed a continuous cooling
transformation (CCT) diagram.

Chapter 10 - 39
Cooling Curve
plot temp vs. time

Chapter 10 - 40
 Dynamic Phase Transformations
On the isothermal transformation diagram for
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 - 41
 Example Problem for Co = 0.45 wt%
a) 42% proeutectoid ferrite and 58% coarse pearlite

first make ferrite 800 A

A+

then pearlite T (°C)

A+P
600 P
B
coarse pearlite A+B
A
 higher T 400
M (start)
50%

M (50%)
M (90%)
200

0
0.1 10 103 105
time (s)
Chapter 10 - 42
 Example Problem for Co = 0.45 wt%
b) 50% fine pearlite and 50% bainite

800 A+
first make pearlite A
T (°C)
then bainite A+P
600 P
B
A+B
fine pearlite A
50%
400
 lower T M (start)
M (50%)
M (90%)
200

0
0.1 10 103 105
time (s)
Chapter 10 - 43
 Example Problem for Co = 0.45 wt%
c) 100 % martensite – quench = rapid cool
d) 50 % martensite
and 50 % 800
A
A+
austenite T (°C)
A+P
600 P
B
A+B
A
400 50%
M (start)
M (50%)
M (90%)
d)
200

c)
0
0.1 10 103 105
time (s)
Chapter 10 - 44
 Mechanical Prop: Fe-C System
• Pearlite:
-- Cementite is much harder but more brittle than ferrite
-- increasing the fraction of Fe3C in a steel alloy while
holding other microstructural elements constant will
result in a harder and stronger material
-- Fine pearlite is harder and stronger than coarse pearlit
because of different in the layer thickness of each of
the ferrite and cementite phases
-- Coarse pearlite is more ductile than fine pearlite,
because of the greater restriction to plastic
deformation of the fine pearlite

Chapter 10 - 45
• Spheroidite:
-- Alloys containing pearlitic microstructures have greater strength
and hardness than do those with spheroidite. This behavior is explained
in terms of reinforcement at, and impedance to, dislocation motion
across the ferrite–cementite boundaries as discussed above. There is less
boundary area per unit volume in spheroidite, and consequently plastic
deformation is not nearly as constrained, which gives rise to a relatively
soft and weak material. In fact, of all steel alloys, those that are softest
and weakest have a spheroidite microstructure

-- spheroidized steels are extremely ductile, much more than either

fine or coarse pearlite .In addition, they are notably tough because any
crack can encounter only a very small fraction of the brittle cementite
particles as it propagates through the ductile ferrite matrix.

Chapter 10 - 46
• Bainite:

-- Because bainitic steels have a finer structure (i.e., smaller -ferrite

and Fe3C particles), they are generally stronger and harder than
pearlitic ones; yet they exhibit a desirable combination of strength and
ductility.

• Martinsite:

-- Martensite is the hardest and strongest and, the most brittle; it has,
in fact, negligible ductility. Its hardness is dependent on the carbon
content, up to about 0.6 wt%. these properties are attributed to the
effectiveness of the interstitial carbon
atoms in hindering dislocation motion (as a solid-solution effect) and
to the relatively few slip systems (along which dislocations move) for
the BCT structure.
Chapter 10 - 47
 Mechanical Prop: Fe-C System (1)
Pearlite (med)
• Effect of wt% C Cementite (hard)

Pearlite (med)
ferrite (soft)

Co < 0.76 wt% C Co > 0.76 wt% C

Hypoeutectoid Hypereutectoid

Chapter 10 - 48
 Hypo Hyper Hypo Hyper
TS(MPa)
1100
%EL 80
YS(MPa) 100

Impact energy (Izod, ft-lb)

900
hardness
40
700
50
500
0
300

0 0.5 1 0
0.76

wt% C 0.5 1

0.76
0
wt% C

• More wt% C(or equivalent Fe3C): TS and YS increase, %EL decreases.

Chapter 10 - 49
 Mechanical Prop: Fe-C System (2)
• Fine vs coarse pearlite vs spheroidite
Hypo Hyper 90 Hypo Hyper
320
fine

Ductility (%AR)
spheroidite
pearlite 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
• Hardness: fine > coarse > spheroidite
• %RA: fine < coarse < spheroidite

Chapter 10 - 50
 Mechanical Prop: Fe-C System (3)
• Fine Pearlite vs Martensite:

Hypo Hyper

600
Brinell hardness

martensite

400

200
fine pearlite
0
0 0.5 1
wt% C
• Hardness: fine pearlite << martensite.

Chapter 10 - 51
 Tempering Martensite
• reduces brittleness of martensite, enhanced ductility and tough.
• reduces internal stress caused by quenching.
TS(MPa)
YS(MPa)
1800

1600 TS

1400 YS

9 m
1200 60
1000 50
%RA %RA
40
800 30
200 400 600
Tempering T (°C)

• produces extremely small Fe3C particles surrounded by 

• decreases TS, YS but increases %RA
Chapter 10 - 52
Tempering is accomplished by heating a martensitic steel to a
temperature below the eutectoid for a specified time period.
Normally, tempering is carried out at temperatures between 250
and 650C ; internal stresses, however, may be relieved at
temperatures as low as 200C.This tempering heat treatment allows,
by diffusional processes, the formation of tempered martensite,
according to the reaction

• The size of the cementite particles influences the mechanical behavior

of tempered martensite; increasing the particle size decreases the ferrite–
cementite phase boundary area and, consequently, results in a softer and
weaker material yet one that is tougher and more ductile
• Heat treatment variables are temperature and time, and most
treatments are constant-temperature processes. Since carbon diffusion is
involved in the martensite-tempered martensite transformation,
increasing the temperature will accelerate diffusion, the rate of cementite
particle growth, and, subsequently, the rate of softening. Chapter 10 - 53
 Summary: Processing Options
Austenite ()

slow moderate rapid

cool cool quench

Pearlite Bainite Martensite

( + Fe3C layers + a ( + Fe3C plates/needles) (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 - 54