PHASE TRANSFORMATIONS

Nucleation
Growth
APPLICATIONS
Transformations in Steel
Precipitation
Solidification & crystallization
Glass transition
Recovery, Recrystallization & Grain growth
Phase Transformations in Metals and Alloys
David Porter & Kenneth Esterling
Van Nostrand Reinhold Co. Ltd., New York (1981)
Diffusional
PHASE TRANSFORMATIONS
Martensitic
1
nd
order
nucleation & growth
PHASE TRANSFORMATIONS
2
nd
order
Entire volume transforms
Based on
Mass
transport
Based on
order
Energies involved
Bulk Gibbs free energy
Interfacial energy
Strain energy
Solid-solid transformation
Volume of transforming material
New interface created
The concepts are illustrated using solidification of a metal
Nucleation
of
| phase
Trasformation
o |
+
Growth
till
o is
exhausted
=
1
nd
order
nucleation & growth
Liquid Solid phase transformation
Solid (G
S)

Liquid (G
L
)
T
m

T
G

AT
AG
Liquid stable Solid stable
AT - Undercooling
t
For sufficient
Undercooling
On cooling just below T
m
solid becomes stable
But solidification does not start
E.g. liquid Ni can be undercooled 250 K below T
m

AG ve
AG +ve
Nucleation
The probability of nucleation occurring at point in the parent phase is
same throughout the parent phase
In heterogeneous nucleation there are some preferred sites in the
parent phase where nucleation can occur
Homogenous
Heterogenous
Nucleation
Nucleation Solidification
+
Growth
=
Liquid solid
walls of container, inclusions
Solid solid
inclusions, grain boundaries,
dislocations, stacking faults
Homogenous nucleation
) ( (Surface). ) (Volume).( G + A = G
( ) ) .( 4 ) .(
3
4
G
2 3
t t r G r
v
+ A
|
.
|

\
|
=
r
2

r
3

1
Neglected in L S
transformations
) ( T f G
v
A = A
energy strain in increase energy surface in increase energy free bulk in Reduction
nucleation on change energy Free
+ +
=
( ) ) .( 4 ) .(
3
4
G
2 3
t t r G r
v
+ A
|
.
|

\
|
=
By setting dAG/dr = 0 the critical values (corresponding to the maximum)
are obtained (denoted by superscript *)
Reduction in free energy is obtained only after r
0
is obtained
0 =
A
dr
G d
0
*
1
= r
v
G
r
A
=
2
*
2
Trivial
v
G
r
A
=
2
*
2
3
*
3
16
v
G
G
A
= A

t
As AG
v
is ve, r
*
is +ve
r
A
G

0 =
A
dr
G d
0 = AG
*
r
0
r
0 = AG
v
G
r
A
=
3
0
Supercritical nuclei Embryos
) ( T f G
v
A = A
The bulk free energy reduction is a function of undercooling
r
A
G

Decreasing r
*

D
e
c
r
e
a
s
i
n
g

A
G
*

T
m

2
3
2 2
16
3
m
T
G
T H
t
-
A =
A A
Turnbull approximation
No. of critical sized
particles
Rate of nucleation
x
Frequency with which they
become supercritical
=
dt
dN
I =
|
|
.
|

\
|
A

=
kT
G
t
e N N
*

*
|
.
|

\
|
A

=
kT
H
d
e s '
*
v v
Critical sized nucleus
s
*
atoms of the liquid facing the nucleus
Critical sized nucleus
Jump taking particle to supercriticality
nucleated (enthalpy of activation = AH
d
)
No. of particles/volume in L
v lattice vibration frequency (~10
13
/s)
|
|
.
|

\
|
A + A

=
kT
H G
t
d
e s N I
*

*
v
I
T

(
K
)

I
n
c
r
e
a
s
i
n
g

A
T

T
m

0
T = T
m
AG
*
= I = 0
AG
*
I
T I
T = 0 I = 0
Heterogeneous nucleation
Consider the nucleation of | from o on a planar surface of inclusion o

o|

oo

o
|
o

|o

u
oo |o o|
) ( ) ( ) (A ) (V G
lens lens circle circle v
A A G + + A =
A
lens

o|

A
circle

|o

A
circle

oo

Created
Created
Lost
oo |o o|
u = + Cos
Surface tension force balance
Interfacial Energies
V
lens
= th
2
(3r-h)/3 A
lens
= 2trh h = (1-Cosu)r r
circle
= r Sinu
o|
|o oo

u

= Cos
0
0.25
0.5
0.75
1
0 30 60 90 120 150 180
v
hetero
G
r
A
=
o|
2
*
( ) u u

t
o|
3
2
3
*
3 2
3
4
Cos Cos
G
G
v
hetero
+
A
= A
0 =
A
dr
G d
( ) u u
3
homo
*
3 2
4
1
Cos Cos G G
*
hetero
+ = A
u (degrees)
A
G
*
h
e
t
e
r
o

/

A
G
*
h
o
m
o

AG
*
hetero
(0
o
) = 0
no barrier to nucleation
AG
*
hetero
(90
o
) = AG
*
homo
/2
AG
*
hetero
(180
o
) = AG
*
homo

no benefit
Complete wetting No wetting
Partial wetting
o|
|o oo

u

= Cos
|
|
.
|

\
|
A

kT
G
e I I
*
homo

0
homo homo
|
|
.
|

\
|
A

kT
G
e I I
*
hetero

0
hetero hetero
= f(number of nucleation sites)
~ 10
42

= f(number of nucleation sites)
~ 10
26

BUT
the exponential term dominates
I
hetero
> I
homo

Choice of heterogeneous nucleating agent
Small value of u
Choosing a nucleating agent with a low value of
|o
(low energy |o interface)
(Actually the value of (
oo

|o
) will determine the effectiveness of the
heterogeneous nucleating agent high
oo
or low
|o
)
low value of
|o

Crystal structure of | and o are similar and lattice parameters are as close as
possible
Seeding rain-bearing clouds AgI or NaCl nucleation of ice crystals
Ni (FCC, a = 3.52 ) is used a heterogeneous nucleating agent in the
production of artificial diamonds (FCC, a = 3.57 ) from graphite

o|

oo
o
|
o

|o
u
o|
|o oo

u

= Cos

o|

oo
o
|
o

|o
u
o|
|o oo

u

= Cos
Nucleation
of
| phase
Trasformation
o |
+
Growth
till
o is
exhausted
=
AH
d
v
atom
AG
v

AH
d

o phase
| phase
At transformation temperature the probability of jump of atom from o |
(across the interface) is same as the reverse jump
Growth proceeds below the transformation temperature, wherein the activation
barrier for the reverse jump is higher
Growth
rate) Growth rate, on f(Nucleati rate tion Transforma =
) , ( U I f
dt
dX
T = =
|
|
|
.
|

\
|

=
3
t U I

4 3
e 1 X
I, U, T
T

(
K
)

I
n
c
r
e
a
s
i
n
g

A
T

T
m

0
U
T
I
Maximum of growth rate usually
at higher temperature than
maximum of nucleation rate
t
X
|

0
1.0
0.5
|
|
.
|

\
|

=
3
t U I

4 3
e 1 X
Time Temperature Transformation (TTT) diagrams
A type of phase
diagram
T (rate sec
1
)
T

(
K
)

T
T
m

0
t (sec)
T

(
K
)

T
m

0
Time for transformation
Small driving
force for nucleation
Growth
sluggish
Replot
t (sec)
T

(
K
)

99% = finish
Increasing % transformation
o
|
TTT diagram o | phase transformation
1% = start
T
G

Turnbulls approximation
T
m

Solid (G
S)

Liquid (G
L
)
AT
AG
m m
m
T
T
h
T
T T
h G
A
A =

A = A
sion heat of fu h
2
3 *
3
16
|
|
.
|

\
|
A A
= A
T h
T
G
m
t
APPLICATIONS
Phase Transformations in Steel
Precipitation
Solidification and crystallization
Glass transition
Recovery recrystallization & grain growth
Phase Transformations in Steel
%C
T

Fe
Fe
3
C
6.7
4.3
0.8 0.16
2.06
Peritectic
L + o
Eutectic
L + Fe
3
C
Eutectoid
o + Fe
3
C
L
o
L +

+ Fe
3
C
o
1493C
1147C
723C
Fe-Cementite diagram
0.025 %C
0.1 %C
o + Fe
3
C
Austenite
Austenite
Pearlite
Pearlite + Bainite
Bainite
Martensite
100
200
300
400
600
500
800
723
0.1
1
10
10
2
10
3
10
4

10
5

Eutectoid temperature

Not an isothermal
transformation
M
s

M
f

Coarse
Fine
t (s)
T

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation
Eutectoid steel (0.8%C)
Austenite
Pearlite
Pearlite + Bainite
Bainite
Martensite
100
200
300
400
600
500
800
723
0.1
1
10
10
2
10
3
10
4

10
5

Eutectoid temperature
M
s

M
f

t (s)
T

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation
Eutectoid steel (0.8%C)
o + Fe
3
C
Continuous Cooling Transformation (CCT) Curves Eutectoid steel (0.8%C)
Austenite
Martensite
100
200
300
400
600
500
800
723
0.1
1
10
10
2
10
3
10
4

10
5

Eutectoid temperature
M
s

M
f

t (s)
T

Original TTT lines
Cooling curves
Constant rate
Pearlite
1
T

2
T

Eutectoid steel (0.8%C)

100
200
300
400
600
500
800
723
0.1
1
10
10
2
10
3
10
4

10
5

t (s)
T

Different cooling treatments
M = Martensite
P = Pearlite
Coarse P
P
M
M +
Fine P
Pearlite
Nucleation and growth
Heterogeneous nucleation at grain boundaries
Interlamellar spacing is a function of the temperature of transformation
Lower temperature finer spacing higher hardness
o + Fe
3
C
[1] Physical Metallurgy for Engineers by Donald S Clark and Wilbur R Varney (Second Edition) Affiliated EastWest Press Pvt. Ltd., New Delhi, 1962
[1]
[1]
Bainite
Nucleation and growth
Acicular, accompanied by surface distortions
** Lower temperature
carbide could be carbide (hexagonal structure, 8.4% C)
Bainite plates have irrational habit planes
Ferrite in Bainite plates possess different orientation relationship
relative to the parent Austenite than does the Ferrite in Pearlite
o + Fe
3
C
**

Bainite formed at 348
o
C
Bainite formed at 278
o
C
[1] Physical Metallurgy for Engineers by Donald S Clark and Wilbur R Varney (Second Edition) Affiliated EastWest Press Pvt. Ltd., New Delhi, 1962
[1]
[1]
Martensite
FCC
Austenite
FCC
Austenite
Alternate choice of
Cell
Tetragonal
Martensite
Austenite to Martensite 4.3 % volume increase
Possible positions of
Carbon atoms
Only a fraction of
the sites occupied
20% contraction of c-axis
12% expansion of a-axis
Refer Fig.9.11 in textbook
In Pure Fe after
the Matensitic transformation
c = a
C along the c-axis
obstructs the contraction
C
BCT
C
FCC
Quench
% 8 . 0
) ( '
% 8 . 0
) ( o

Martensite
The martensitic transformation occurs without composition change
The transformation occurs by shear without need for diffusion
The atomic movements required are only a fraction of the interatomic
spacing
The shear changes the shape of the transforming region
results in considerable amount of shear energy
plate-like shape of Martensite
The amount of martensite formed is a function of the temperature to
which the sample is quenched and not of time
Hardness of martensite is a function of the carbon content
but high hardness steel is very brittle as martensite is brittle
Steel is reheated to increase its ductility
this process is called TEMPERING
% Carbon
H
a
r
d
n
e
s
s


(
R
c
)

20
40
60
0.2 0.4 0.6
Harness of Martensite as a
function of Carbon content
Properties of 0.8% C steel
Constituent Hardness (R
c
) Tensile strength (MN / m
2
)
Coarse pearlite 16 710
Fine pearlite 30 990
Bainite 45 1470
Martensite 65 -
Martensite tempered at 250
o
C 55 1990
Tempering
Heat below Eutectoid temperature wait slow cooling
The microstructural changes which take place during tempering
are very complex
Time temperature cycle chosen to optimize strength and toughness
Tool steel: As quenched (R
c
65) Tempered (R
c
45-55)
Cementite
OR F
Ferrite
BCC
Martensite
BCT
Temper
) ( C e ) ( ) ( '
3
+
o o
Austenite
Pearlite
Pearlite + Bainite
Bainite
Martensite
100
200
300
400
600
500
800
723
0.1 1 10
10
2
10
3
10
4

10
5

Eutectoid temperature
M
s

M
f

t (s)
T

o + Fe
3
C
MARTEMPERING
AUSTEMPERING
To avoid residual stresses generated during quenching
Austenized steel is quenched above Ms for homogenization of temperature
across the sample
The steel is then quenched and the entire sample transforms simultaneously
Tempering follows
To avoid residual stresses generated during quenching
Austenized steel is quenched above M
s

Held long enough for transformation to Bainite
Martempering
Austempering
ALLOY STEELS
Various elements like Cr, Mn, Ni, W, Mo etc are added to plain carbon
steels to create alloy steels
The alloys elements move the nose of the TTT diagram to the right
this implies that a slower cooling rate can be employed to obtain
martensite increased HARDENABILITY
The C curves for pearlite and bainite transformations overlap in the
case of plain carbon steels in alloy steels pearlite and bainite
transformations can be represented by separate C curves
ROLE OF ALLOYING ELEMENTS
+ Simplicity of heat treatment and lower cost
Low hardenability
Loss of hardness on tempering
Low corrosion and oxidation resistance
Low strength at high temperatures
Plain Carbon Steel
Element Added
Segregation / phase separation
Solid solution
Compound (new crystal structure)
hardenability
Provide a fine distribution of alloy carbides during tempering
resistance to softening on tempering
corrosion and oxidation resistance
strength at high temperatures
Strengthen steels that cannot be quenched
Make easier to obtain the properties throughout a larger section
Elastic limit (no increase in toughness)
Alloying elements
Alter temperature at which the transformation occurs
Alter solubility of C in o or Iron
Alter the rate of various reactions
Interstitial
Substitutional
Austenite Pearlite
Bainite
Martensite
100
200
300
400
600
500
800
M
s

M
f

t
T

TTT diagram for Ni-Cr-Mo low alloy steel
~1 min
Precipitation
The presence of dislocation weakens the crystal easy plastic deformation
Putting hindrance to dislocation motion increases the strength of the crystal
Fine precipitates dispersed in the matrix provide such an impediment
Strength of Al 100 MPa
Strength of Duralumin (Al + 4% Cu + other alloying elements) 500 MPa
Al
% Cu
T

(

C
)

200
400
600
15
30 45 60
L
o
u
Sloping Solvus line
high T high solubility
low T low solubility
of Cu in Al
Al rich end of the Al-Cu phase diagram
o
4 % Cu
o + u
o o + u
Slow equilibrium cooling gives rise to
coarse u precipitates which is not good
in impeding dislocation motion.
*

|
|
|
.
|

\
|
+
|
|
|
.
|

\
|

|
|
|
.
|

\
|
RT
Cu
Tetragonal CuAl
RT
Cu
FCC
C
Cu
FCC
cool slow
o
% 52
) (
% 5 . 0
) (
550
% 4
) (
2

u o o
*Also refer section on Double Ended Frank-Read Source in the chapter on plasticity: t
max
= Gb/L
C
A
B
Heat (to 550
o
C) solid solution o
Quench (to RT)
Age (reheat to 200
o
C) fine precipitates
o
4 % Cu
o + u
C
A
B
To obtain a fine distribution of precipitates the cycle A B C is used
Note: Treatments A, B, C are for the same
composition
supersaturated solution
Increased vacancy concentration
Log(t)
H
a
r
d
n
e
s
s

180
o
C
100
o
C
20
o
C
Higher temperature less time of aging to obtain peak hardness
Lower temperature increased peak hardness
optimization between time and hardness required
Log(t)
H
a
r
d
n
e
s
s

180
o
C
T
m

Overaged
Underaged
Peak-aged
Region of solid solution
strengthening
(no precipitation hardening)
Region of precipitation
hardening
(but little solid solution
strengthening)
Dispersion of
fine precipitates
(closely spaced)
Coarsening
of precipitates
with increased
interparticle spacing
Log(t)
H
a
r
d
n
e
s
s

180
o
C
Peak-aged
Particle radius (r)
C
R
S
S

I
n
c
r
e
a
s
e

2
1
r
r
1

Particle
shearing
Particle
By-pass
) (t f r =
Due to large surface to volume ratio the fine precipitates have a tendency
to coarsen small particles dissolve and large particles grow
Coarsening
in number of particles
in interparticle spacing
reduced hindrance to dislocation motion (t
max
= Gb/L)
Solidification and Crystallization
AH
fusion

AH
d
~ Log [Viscosity (q)]
Crystallization favoured by
High (10-15) kJ / mole
Low (1-10) Poise
Metals
Enthalpy of activation for
diffusion across the interface
Difficult to amorphize metals
Thermodynamic
Kinetic
Very fast cooling rates ~10
6
K/s are used for the amorphization of alloys
splat cooling, melt-spinning.
2
*
1
fusion
H
G
A
A
Fine grain size bestows superior mechanical properties on the material
High nucleation rate and slow growth rate fine grain size
Cooling rate lesser time at temperatures near T
m
, where the peak
of growth rate (U) lies nucleation rate
Cooling rates ~ (10
5
10
6
) K/s are usually employed
Grain refinement can also be achieved by using external nucleating agents
Single crystals can be grown by pulling a seed crystal out of the melt
I, U
T

(
K
)

T
m

0
U
I
AH
fusion

AH
d
~ Log [Viscosity (q)]
Crystallization favoured by
low
High (1000) Poise
Silicates
Enthalpy of activation for
diffusion across the interface
Easily amorphized
Thermodynamic
Kinetic
Certain oxides can be added to silica to promote crystallization
In contrast to metals silicates, borates and phosphates tend to form glasses
Due to high cation-cation repulsion these materials have open structures
In silicates the difference in total bond energy between periodic and
aperiodic array is small (bond energy is primarily determined by the
first neighbours of the central cation within the unit
A composite material of glass and ceramic (crystals) can have better
thermal and mechanical properties
But glass itself is easier to form (shape into desired geometry)
Glass-ceramic (pyroceram)
Shaping of material in glassy state
Heterogenous nucleating agents (e.g. TiO
2
) added (dissolved) to molten glass
TiO
2
is precipitated as fine particles
Held at temperature of maximum nucleation rate (I)
Heated to temperature of maximum growth rate
t
T

Nucleation
Growth
T
maximum I
T
maximum U
Glass
Partially crystallized Glass
Even at the end of the heat treatment the material is not fully crystalline
Fine crystals are embedded in a glassy matrix
Crystal size ~ 0.1 m (typical grain size in a metal ~ 10 m)
Ultrafine grain size
good mechanical properties and thermal shock resistance
Cookware made of pyroceram can be heated directly on flame
Glass Transition
All materials would amorphize on cooling unless crystallization intervenes
T
V
o
l
u
m
e

Or other extensive
thermodynamic
property
S, H, E
Glass
Crystal
T
g
T
m

Glass transition temperature
T
V
o
l
u
m
e

Change in slope
T
f

Fictive temperature (temperature at which glass is metastable
if quenched instantaneously to this temperature)
can be taken as T
g

T
V
o
l
u
m
e

Effect of rate of cooling
1
T

2
T

2 1
T T

>
Slower cooling
Slower cooling Higher density
Lower T
g

Lower volume
As more time for atoms to
arrange in closer packed
configuration
T
L
o
g

(
v
i
s
c
o
s
i
t
y
)

Glass
Crystal
T
g
T
m

Supercooled
liquid
On crystallization the viscosity abruptly changes from ~100 ~10
20
Pa s
A solid can be defined a material with a viscosity > 10
12
Poise
T
g

Heat glass
Cool liquid
T
x

Often metallic glasses crystallize before T
g

Please read up paragraph on glassy polymers p228 in text book
Recovery, Recrystallization & Grain Growth
Cold work
dislocation density
point defect density
Plastic deformation in the temperature range (0.3 0.5) T
m
COLD WORK
Point defects and dislocations have strain energy associated with them
(1 -10) % of the energy expended in plastic deformation is stored in the
form of strain energy
) 10 10 ( ~

) 10 10 ( ~

14 12
n dislocatio

9 6
n dislocatio



material Stronger material Annealed
work Cold
Cold work
dislocation density
point defect density
Anneal
Material tends to lose
the stored strain energy
Increase in strength
of the material
Softening of the material
Cold work Anneal
Recrystallization
Recovery
Low temperature
High temperature
Cold work Anneal
Recrystallization
Recovery
Grain growth
Cold work
Hardness
Strength
Changes occur to almost all physical and mechanical properties
X-Ray diffration
Laue patterns of single crystals show pronounced asterism
due to lattice curvatures
Debye-Scherrer photographs show line broadning
Residual stresses + deformations

Electrical resistance
Ductility
Recovery
Recovery takes place at low temperatures of annealing
Apparently no change in microstructure
Excess point defects created during Cold work are absorbed:
at surface or grain boundaries
by dislocation climb
Random dislocations of opposite sign come together and annihilate each
other
Dislocations of same sign arrange into low energy configurations:
Edge Tilt boundaries
Screw Twist boundaries
POLYGONIZATION
Overall reduction in dislocation density is small
POLYGONIZATION
Bent crystal
Low angle grain boundaries
Recrystallization
T
recrystallization
e (0.3 0.5) T
m

Nucleation and growth of new, strain free crystals
Nucleation of new grains in the usual sense may not be present and
grain boundary migrates into a region of higher dislocation density
AG (recrystallization) = G (deformed material) G (undeformed material)
T
Recrystallization
is the temperature at which 50 % of the material
recrystallizes in 1 hour
Region of lower
dislocation density
Region of higher
dislocation density
Direction of grain
boundary migration
Further points about recrystallization
Deformation recrystallization temperature (T
recrystallization
)
Initial grain size recrystallization temperature
High cold work + low initial grain size finer recrystallized grains
cold work temperature lower strain energy stored
recrystallization temperature
Rate of recrystallization = exponential function of temperature
T
recrystallization
= strong function of the purity of the material
T
recrystallization
(very pure materials) ~ 0.3 T
m

T
recrystallization
(impure) ~ (0.5 0.6) T
m


T
recrystallization
(99.999% pure Al) ~ 75
o
C
T
recrystallization
(commercial purity) ~ 275
o
C
The impurity atoms segregate to the grain boundary and retard their
motion Solute drag (can be used to retain strength of materials at
high temperatures)

The impurity atoms seggregate to the grain boundary and retard their
motion Solute drag (can be used to retain strength of materials
at high temperatures)
Second phase particles also pin down the grain boundary during its
migration
Hot Work and Cold Work
Hot Work Plastic deformation above T
Recrystallization

Cold Work Plastic deformation below T
Recrystallization

C
o
l
d

W
o
r
k

H
o
t

W
o
r
k

Recrystallization temperature (~ 0.4 T
m
)
Grain growth
Globally
Driven by reduction in grain boundary energy
Locally
Driven by bond maximization (coordination number maximization)
Bonded to
4 atoms
Bonded to
3 atoms
Direction of grain
boundary migration
Boundary moves towards its
centre of curvature
JUMP
Cold work Recovery Recrystallization Grain growth
Tensile strength
Ductility
Electical conductivity
Internal stress