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 2nd order
nucleation & growth 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

Growth
Nucleation
Trasformation till
of +
=  is
→  phase
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

G
Solid (GS)

G → ve
G →

T Liquid (GL)
G → +ve
Tm “For sufficient
T → Undercooling”
T - Undercooling
 Solidification = Nucleation + Growth

Nucleation
Homogenous

Nucleation
 Liquid → solid
walls of container, inclusions
Heterogenous
 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
Homogenous nucleation transformations
Free energy change on nucleation 
Reduction in bulk free energy  increase in surface energy  increase in strain energy

ΔG  (Volume).( G )  (Surface). ( )

4 3
ΔG   r .(Gv )  4r 2 .( )  
3 

Gv  f (T )
r3
r2

1
 4 
 
ΔG   r 3 .(Gv )  4r 2 .( )
3 
 By setting dG/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

2 As Gv is ve, r*is +ve

dG
r1  0 r2  
*
0
*

dr Gv
Trivial
2
r 
*
dG
0
Gv dr
G  0
16  3
G *  
3 Gv2
G →

r* r0
3
G  0 r0   Embryos Supercritical nuclei
Gv
r →
Gv  f (T ) The bulk free energy reduction is a function of undercooling

Turnbull approximation
Tm
16 3 Tm2
G  


3 T 2 H 2
Decreasing G*

Decreasing r*
G →

r →
 No. of critical sized x Frequency with which they
Rate of nucleation = particles become supercritical

dN  G*   H d 
   
I  kT 
dt N  Nt e
*  
 ' s  e *  kT 

No. of particles/volume in L  → 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

  G *  H d   G* ↑  I ↓
 

I  Nt s  e
*  kT  T↑ I ↑

Tm T = Tm → G* =  → I = 0
Increasing T
T (K) →

0 T=0→I=0
I →
Heterogeneous nucleation
Consider the nucleation of  from  on a planar surface of inclusion 
Interfacial Energies
 
 Alens 
 Created

 
Created Acircle 

      Acircle 
Cos  Lost
 

Surface tension force balance   Cos      

ΔG  (Vlens )Gv  (A lens )   ( Acircle )    ( Acircle )  

Vlens = h2(3r-h)/3 Alens = 2rh h = (1-Cos)r rcircle = r Sin

 dG 2   
 
3
0 4
*
r  G *
  2  3Cos  Cos 3

Gv 3 Gv
hetero hetero
dr 2

G*
hetero
1 *
4

 Ghomo 2  3Cos  Cos 3 
G*hetero / G*homo →

1
G*hetero (0o) = 0
G*hetero (180o) = G*homo
no barrier to nucleation
0.75 no benefit
G*hetero (90o) = G*homo/2
0.5
    
Cos 
0.25  
Complete wetting Partial wetting No wetting
0
0 30 60 90 120 150 180
 (degrees) →
  Ghomo
*   Ghetero
* 
 


 

I homo  I  kT 
I hetero  I
0 0  kT 
homo e hetero e

= f(number of nucleation sites) = f(number of nucleation sites)

~ 1042 ~ 1026

BUT
the exponential term dominates

Ihetero > Ihomo

  


 
Choice of heterogeneous nucleating agent
     
Cos 
 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 Å) is used a heterogeneous nucleating agent in the
production of artificial diamonds (FCC, a = 3.57 Å) from graphite
 Growth
Trasformation Nucleation
till
= of +
→  is
 phase
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
 Transforma tion rate  f(Nucleati on rate, Growth rate)

 π I U3 t 4 
dX   

T  f (I , U )
Xβ  1  e  3 
dt

Tm Maximum of growth rate usually

U at higher temperature than
maximum of nucleation rate
Increasing T

I
T (K) →

0
I, U, T →
  π I U3 t 4 
 

Xβ  1  e  3 

1.0

0.5
X →

0
t →
 Time – Temperature – Transformation (TTT) diagrams A type of phase
diagram

Small driving
force for nucleation

Tm Tm
T (K) →

T (K) →
Time for transformation
Replot

0 0
T (rate  sec1) → t (sec) →
Growth
sluggish
TTT diagram  →  phase transformation

Increasing % transformation


T (K) →

99% = finish


1% = start

t (sec) →
Turnbull’s approximation
Δh  heat of fusion
Tm  T T 16 3  Tm 
2
G  h  h G   
*

Tm Tm 3  hT 

Solid (GS)
G
G →

T
Liquid (GL)
Tm
T →
 APPLICATIONS

Phase Transformations in Steel

Precipitation

Solidification and crystallization

Glass transition

Recovery recrystallization & grain growth

Phase Transformations in Steel
 Fe-Cementite diagram Eutectic
L →  + Fe3C
Peritectic L
L+→ 1493ºC

L+
0.1 %C  2.06 1147ºC

Eutectoid  + Fe3C
 →  + Fe3C
723ºC


0.025 %C  + Fe3C
T →

Fe Fe3C
0.16 0.8 4.3 6.7
%C →
Time- Temperature-Transformation (TTT) Curves – Isothermal Transformation
Eutectoid steel (0.8%C)
800
Eutectoid temperature
723
Austenite Coarse
600 Pearlite
Fine

500 Pearlite + Bainite

T →

400 Bainite

Not an isothermal
300

200
 Ms
Austenite

transformation
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
Time- Temperature-Transformation (TTT) Curves – Isothermal Transformation
Eutectoid steel (0.8%C)
800
Eutectoid temperature
723
Austenite
Pearlite
600
 + Fe3C
500 Pearlite + Bainite
T →

400 Bainite

300
Ms
200
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
 Continuous Cooling Transformation (CCT) Curves Eutectoid steel (0.8%C)

800
Eutectoid temperature
723

Austenite 600 Pearlite

500
Original TTT lines
T →

400

300
Ms
Cooling curves 200
Constant rate Mf
100
Martensite T1 T2
0.1 1 10 102 103 104 105
t (s) →
 Different cooling treatments Eutectoid steel (0.8%C)

800
723

M = Martensite 600

P = Pearlite 500
T →

400

300

200
Coarse P
100
M M +P Fine P

0.1 1 10 102 103 104 105

t (s) →
 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 ε 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 )  ' ( BCT )

Quench Possible positions of
0.8 %C 0.8 %C 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

Tetragonal In Pure Fe after

20% contraction of c-axis the Matensitic transformation
Martensite
12% expansion of a-axis c=a

Austenite to Martensite → 4.3 % volume increase 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
 60
Hardness (Rc) →

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 )  ( BCC ) Fe3C (OR )

Temper

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
 Tempering follows 800
Eutectoid temperature
723
Austenite
Pearlite
600
 + Fe3C
Martempering 500 Pearlite + Bainite

T →
400 Bainite

300
Ms

Austempering 200
Mf
100 Martensite
AUSTEMPERING
0.1 1 10 102 103 104 105
 To avoid residual stresses generated during quenching t (s) →

 Austenized steel is quenched above Ms

 Held long enough for transformation to Bainite
 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
Solid solution Substitutional
Element Added
Compound (new crystal structure)

• + Simplicity of heat treatment and lower cost

•  Low hardenability
Plain Carbon Steel •  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
Alloying elements • ↑ 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

Austenite Pearlite
600

500
T →

400

300 Bainite
Ms
200
Mf
100
Martensite
~1 min
t →
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

L
600

T (ºC) →

400

Sloping Solvus line
 high T → high solubility
200
low T → low solubility
of Cu in Al

Al 15 30 45 60
% Cu →
  →+
Slow equilibrium cooling gives rise to
+ coarse  precipitates which is not good
in impeding dislocation motion.*

4 % Cu

 ( FCC)   ( FCC)   CuAl2 (Tetragonal ) 

  slowcool    
 4 % Cu    0.5 % Cu    52 % 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
B

A C

+

4 % Cu
A Heat (to 550oC) → solid solution 

supersaturated solution
B Quench (to RT) →
Increased vacancy concentration

C Age (reheat to 200oC) → fine precipitates

 100oC
Hardness →

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
 180oC Peak-aged

Hardness →

Coarsening
Dispersion of of precipitates
fine precipitates with increased
(closely spaced) interparticle spacing

Underaged Overaged

Log(t) →
Region of precipitation
Region of solid solution hardening
strengthening (but little solid solution
(no precipitation hardening) strengthening)
 180oC Peak-aged

Hardness →

Log(t) →
CRSS Increase →

Particle
shearing
Particle
By-pass
r  f (t )
1 1

r 2
r
Particle radius (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 (max = Gb/L)
Solidification and Crystallization
 Metals
1
G* 
H 2fusion
Thermodynamic ↑ Hfusion 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

Tm
U
T (K) →

0
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

Nucleation
Tmaximum I
T →

Glass Partially crystallized Glass

t →

 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 →

Glass

Crystal

T → Tg Tm
Or other extensive
thermodynamic
property →
Glass transition temperature
S, H, E
 Change in slope
Volume →

T → 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

T1  T2

As more time for atoms to

arrange in closer packed
T1
Volume →

configuration

T2 Slower cooling

T → Lower volume

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

Crystal
Log (viscosity) →

Glass

Supercooled
liquid

T → Tg Tm
 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

dislocation ~ (10  10 )
6 9
dislocation ~ (1012  1014 )
 ↑ point defect density
Material tends to lose
Cold work Anneal the stored strain energy
↑ dislocation density

Increase in strength
of the material Softening of the material

Low temperature
Recovery

Cold work Anneal

Recrystallization
High temperature
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

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 lower
Region of higher dislocation density
dislocation density

Direction of grain
boundary migration
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

 Cold Work  Plastic deformation below TRecrystallization

Hot Work

Recrystallization temperature (~ 0.4 Tm)

Cold Work
 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 JUMP

Boundary moves towards its

centre of curvature
 Electical conductivity
Internal stress
Ductility

Tensile strength

Cold work Recovery Recrystallization Grain growth