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)

PHASE TRANSFORMATIONS
Based on
Mass
transport

Diffusional

Martensitic

PHASE TRANSFORMATIONS
Based on
order

1nd order
nucleation & growth

2nd order
Entire volume transforms

Bulk Gibbs free energy

Energies involved

Interfacial energy
Strain energy

Solid-solid transformation

New interface created

Volume of transforming material

The concepts are illustrated using solidification of a metal

1nd order
nucleation & growth

Trasformation

Nucleation
of
phase

Growth
till
is
exhausted

Liquid Solid phase transformation

On cooling just below Tm solid becomes stable
But solidification does not start
E.g. liquid Ni can be undercooled 250 K below Tm
t
Solid stable

Liquid stable

Solid (GS)
G ve
T

G +ve
Tm

T - Undercooling

Liquid (GL)
For sufficient
Undercooling

Solidification

Nucleation

Nucleation

Growth

Homogenous

Nucleation
Heterogenous

Liquid solid
walls of container, inclusions
Solid solid
inclusions, grain boundaries,
dislocations, stacking faults

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

Neglected in L S
transformations

Homogenous nucleation
Free energy change on nucleation

Reduction in bulk free energy increase in surface energy increase in strain energy

G (Volume).( G ) (Surface).( )

4 3
2
G r .(Gv ) 4r .( )
3

Gv f (T )

r3

r2
1

4 3
r .(Gv ) 4r 2 .( )
3

By setting dG/dr = 0 the critical values (corresponding to the maximum)

are obtained (denoted by superscript *)
Reduction in free energy is obtained only after r0 is obtained

dG
0
dr

2
r
Gv

As Gv is ve, r*is +ve

2
*
*
r1 0 r2
Gv
Trivial

dG
0
dr

G 0

3
r0
Gv

G 0

3
16

G *
3 Gv2

r*
Embryos

r0
Supercritical nuclei

Gv f (T ) The bulk free energy reduction is a function of undercooling

Turnbull approximation

Tm2
16 3
G
3
T 2 H 2

g
n
i
s
ea
r
c
In

Decreasing G*

Tm

Decreasing r*

No. of critical sized

Rate of nucleation =
particles

dN
I
dt

Frequency with which they

become supercritical

N * Nt e

kT

No. of particles/volume in L

' s e

H d

kT

lattice vibration frequency (~1013 /s)

s* atoms of the liquid facing the nucleus

Critical sized nucleus
Jump taking particle to supercriticality
nucleated (enthalpy of activation = Hd)
Critical sized nucleus

I Nt s e
*

G * H d

kT

G* I

T I

T = Tm G* = I = 0

T (K)

Increasing T

Tm

T=0I=0

Heterogeneous nucleation
Consider the nucleation of from on a planar surface of inclusion

Interfacial Energies

Created

Alens

Created

Acircle

Lost

Acircle

Cos

Surface tension force balance

Cos

G (Vlens )Gv (A lens ) ( Acircle ) ( Acircle )

Vlens = h2(3r-h)/3

Alens = 2rh

h = (1-Cos)r

rcircle = r Sin

dG
0
dr

*
rhetero

*
Ghetero

Gv

G
G*hetero / G*homo

*
hetero

G*hetero (0o) = 0
no barrier to nucleation

Complete wetting

3
Cos

Cos

2
3 Gv

1 *
Ghomo 2 3Cos Cos 3
4
G*hetero (180o) = G*homo
no benefit

G*hetero (90o) = G*homo/2

Cos

Partial wetting

(degrees)

No wetting

I homo I

0
homo

*
Ghomo

kT

= f(number of nucleation sites)

I hetero I

0
hetero

*
Ghetero

kT

= f(number of nucleation sites)

~ 1026

~ 1042

BUT
the exponential term dominates

Ihetero > Ihomo

Choice of heterogeneous nucleating agent

Small value of
Choosing a nucleating agent with a low value of (low energy interface)
(Actually the value of ( ) will determine the effectiveness of the
heterogeneous nucleating agent high or low )
low value of
Crystal structure of and 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

Trasformation

Nucleation
of
phase

Growth
till
is
exhausted

Growth
At transformation temperature the probability of jump of atom from
(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

Hd

Hd vatom Gv

phase
phase

Transformation rate f(Nucleation rate, Growth rate)

T

dX
dt

T (K)

Increasing T

Tm

f (I , U )

X 1 e

I U3 t 4

Maximum of growth rate usually

at higher temperature than
maximum of nucleation rate

I, U, T

X 1 e

I U3 t 4

1.0

0.5

Time Temperature Transformation (TTT) diagrams

A type of phase
diagram

Small driving
force for nucleation

Tm

T
Replot

T (rate sec1)

T (K)

T (K)

Tm

Time for transformation

t (sec)

Growth
sluggish

TTT diagram phase transformation

T (K)

Increasing % transformation

99% = finish

1% = start
t (sec)

Turnbulls approximation

h heat of fusion

Tm T
T
G h
h
Tm
Tm

Solid (GS)

Liquid (GL)
Tm

16 3 Tm

G
3
hT
*

APPLICATIONS

Phase Transformations in Steel

Precipitation
Solidification and crystallization
Glass transition
Recovery recrystallization & grain growth

Phase Transformations in Steel

Fe-Cementite diagram
Peritectic
L+

Eutectic
L + Fe3C
L

1493C

0.1 %C

L+

Eutectoid
+ Fe3C

1147C

2.06
+ Fe3C

723C

+ Fe3C

0.025 %C

Fe

0.16 0.8

4.3
%C

Fe3C
6.7

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation

Eutectoid steel (0.8%C)

800
Eutectoid temperature

723

Austenite
Pearlite

600

T
Not an isothermal
transformation

400

200
100
0.1

Fine

Pearlite + Bainite

500

300

Coarse

Bainite

Ms

Austenite

Mf
Martensite
1

102
10
t (s)

103

104

105

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation

Eutectoid steel (0.8%C)

800
723

Eutectoid temperature

Austenite

Pearlite

600
+ Fe3C

500

Pearlite + Bainite

400

Bainite

300
200
100
0.1

Ms
Mf
Martensite
1

102
10
t (s)

103

104

105

Continuous Cooling Transformation (CCT) Curves

Eutectoid steel (0.8%C)

800
723
Austenite

Eutectoid temperature

600

Pearlite

500
Original TTT lines

400
300

Cooling curves
Constant rate

200
100
0.1

Ms
Mf
Martensite
1

T2

T1

102
10
t (s)

103

104

105

Different cooling treatments

Eutectoid steel (0.8%C)

800
723
M = Martensite 600

uen

Coarse P

ch

200
100
0.1

lq
Oi

300

zin
ali
rm
No

400

M
1

Fine P

M +P
102
10
t (s)

al
nne
ll a
Fu

500

ench
Water qu

P = Pearlite

103

104

105

Pearlite

[1]

[1]

+ Fe3C

Nucleation and growth

Heterogeneous nucleation at grain boundaries
Interlamellar spacing is a function of the temperature of transformation
Lower temperature finer spacing higher hardness
[1] Physical Metallurgy for Engineers by Donald S Clark and Wilbur R Varney (Second Edition) Affiliated EastWest Press Pvt. Ltd., New Delhi, 1962

Bainite

[1]

[1]
Bainite formed at 348oC

Bainite formed at 278oC

+ Fe3C**

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
[1] Physical Metallurgy for Engineers by Donald S Clark and Wilbur R Varney (Second Edition) Affiliated EastWest Press Pvt. Ltd., New Delhi, 1962

Martensite

( FCC ) Quench ' ( BCT )

0.8 %C
0.8 %C

Possible positions of
Carbon atoms
Only a fraction of
the sites occupied

FCC
Austenite

C along the c-axis

obstructs the contraction
FCC
Austenite
Alternate choice of
Cell

20% contraction of c-axis

12% expansion of a-axis

Tetragonal
Martensite

Austenite to Martensite 4.3 % volume increase

In Pure Fe after
the Matensitic transformation
c=a
Refer Fig.9.11 in textbook

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

Hardness (Rc)

60
Harness of Martensite as a
function of Carbon content

40
20

% Carbon
0.2

0.4

0.6
Properties of 0.8% C steel

Constituent

Hardness (Rc)

Tensile strength (MN / m2)

Coarse pearlite

16

710

Fine pearlite

30

990

Bainite

45

1470

Martensite

65

Martensite tempered at 250 oC

55

1990

Tempering

' ( BCT ) Temper ( BCC ) Fe 3C (OR)

Martensite
Ferrite Cementite

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 (Rc 65) Tempered (Rc 45-55)

MARTEMPERING

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
800
Tempering follows
Eutectoid temperature
723
Austenite

Pearlite

600

Pearlite + Bainite

Martempering

+ Fe3C

500
400
300

Austempering
AUSTEMPERING

Bainite
Ms

200
Mf
100

Martensite
0.1

10

To avoid residual stresses generated during quenching

Austenized steel is quenched above Ms
Held long enough for transformation to Bainite

102
t (s)

103

104

105

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

Interstitial
Segregation / phase separation

Element Added

Plain Carbon Steel

Alloying elements

Solid solution

Substitutional

Compound (new crystal structure)

+ Simplicity of heat treatment and lower cost

Low hardenability
Loss of hardness on tempering
Low corrosion and oxidation resistance
Low strength at high temperatures
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)
Alter temperature at which the transformation occurs
Alter solubility of C in or Iron
Alter the rate of various reactions

TTT diagram for Ni-Cr-Mo low alloy steel

800
Pearlite

Austenite
600

500
400
300
200
100

Bainite
Ms
Mf
Martensite
~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 rich end of the Al-Cu phase diagram

T (C)

600

400

200

Al

Sloping Solvus line

high T high solubility
low T low solubility
of Cu in Al
15

30
% Cu

45

60

+
Slow equilibrium cooling gives rise to
coarse precipitates which is not good
in impeding dislocation motion.*

4 % Cu

( FCC )
( FCC ) CuAl2 (Tetragonal )

slow cool
52 % Cu
4 % Cu 0.5 % Cu

550o C

RT
RT

*Also refer section on Double Ended Frank-Read Source in the chapter on plasticity: max

= Gb/L

To obtain a fine distribution of precipitates the cycle A B C is used

Note: Treatments A, B, C are for the same

composition

C
+

4 % Cu
A

Heat (to 550oC) solid solution

supersaturated solution

Quench (to RT)

Age (reheat to 200oC) fine precipitates

Increased vacancy concentration

Hardness

100oC

180oC
20oC

Log(t)
Higher temperature less time of aging to obtain peak hardness
Lower temperature

increased peak hardness

optimization between time and hardness required

Hardness

180oC

Peak-aged

Dispersion of
fine precipitates
(closely spaced)

Coarsening
of precipitates
with increased
interparticle spacing
Overaged

Underaged

Log(t)
Region of solid solution
strengthening
(no precipitation hardening)

Region of precipitation
hardening
(but little solid solution
strengthening)

Peak-aged

CRSS Increase

Co
he
re
nt
(G
P

Hardness

zo
ne
s)

180oC

In
-c
oh
er
e

nt

(p
re
cip

ita
te
s)

Log(t)
Particle
shearing

Particle
By-pass

r
r
Particle radius (r)
1
2

r f (t )

 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 (max = Gb/L)

Solidification and Crystallization

G *

Thermodynamic Hfusion

1
H 2fusion

Metals
High (10-15) kJ / mole

Crystallization favoured by
Kinetic

Hd Log [Viscosity ()]

Low (1-10) Poise

Enthalpy of activation for

diffusion across the interface
Difficult to amorphize metals
Very fast cooling rates ~106 K/s are used for the amorphization of alloys
splat cooling, melt-spinning.

 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 Tm , where the peak
of growth rate (U) lies nucleation rate
Cooling rates ~ (105 106) 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

T (K)

Tm

I, U

Silicates
Thermodynamic Hfusion

low

Crystallization favoured by
Kinetic

Hd Log [Viscosity ()]

High (1000) Poise

Enthalpy of activation for

diffusion across the interface
Easily amorphized
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

Glass-ceramic (pyroceram)
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)
Heterogenous nucleating agents (e.g. TiO2) added (dissolved) to molten glass
Shaping of material in glassy state
TiO2 is precipitated as fine particles
Held at temperature of maximum nucleation rate (I)
Heated to temperature of maximum growth rate

Growth

Tmaximum U

Tmaximum I

Nucleation

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

Volume

id
u
q
Li

Or other extensive
thermodynamic
property
S, H, E

Glass

Crystal
T

Tg

Tm

Glass transition temperature

Volume

Change in slope

Tf

Fictive temperature (temperature at which glass is metastable

if quenched instantaneously to this temperature)
can be taken as Tg

Effect of rate of cooling

Volume

T1 T2
As more time for atoms to
arrange in closer packed
configuration

T1
T2

Slower cooling
Lower volume

T
Slower cooling

Higher density
Lower Tg

 On crystallization the viscosity abruptly changes from ~100 ~1020 Pa s

A solid can be defined a material with a viscosity > 1012 Poise

Log (viscosity)

Crystal
Glass

Supercooled
liquid

Tg

Tm

Liquid

Cool liquid

Heat glass
Tg
Tx

Often metallic glasses crystallize before Tg

Please read up paragraph on glassy polymers p228 in text book

Recovery, Recrystallization & Grain Growth

Plastic deformation in the temperature range (0.3 0.5) Tm COLD WORK

point defect density
Cold work
dislocation density

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

Annealed material
Stronger material
Cold work

6
9
dislocation ~ (10 10 )
dislocation ~ (1012 1014 )

 point defect density

Anneal

Cold work

Material tends to lose

the stored strain energy

dislocation density
Increase in strength
of the material

Low temperature
Cold work

Softening of the material

Recovery

Anneal
High temperature

Recrystallization

Cold work

Anneal

Recovery

Recrystallization

Grain growth

 Strength
Hardness
Cold work
Electrical resistance
Ductility
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

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

Po
lyg

on
iza
tio
n

Low angle grain boundaries

Recrystallization
Trecrystallization (0.3 0.5) Tm
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
G (recrystallization) = G (deformed material) G (undeformed material)
TRecrystallization is the temperature at which 50 % of the material
recrystallizes in 1 hour

Region of higher
dislocation density
Direction of grain
boundary migration

Region of lower
dislocation density

Further points about recrystallization

Deformation recrystallization temperature (Trecrystallization)
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
Trecrystallization = strong function of the purity of the material
Trecrystallization (very pure materials) ~ 0.3 Tm
Trecrystallization (impure) ~ (0.5 0.6) Tm

Trecrystallization (99.999% pure Al) ~ 75oC

Trecrystallization (commercial purity) ~ 275oC

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 TRecrystallization

Hot Work

Cold Work Plastic deformation below TRecrystallization

Cold Work

Recrystallization temperature (~ 0.4 Tm)

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

Electical conductivity
Internal stress
Ductility

Tensile strength

Cold work

Recovery

Recrystallization

Grain growth