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PHASE TRANSFORMATIONS

Nucleation
Growth
APPLICATIONS
Transformations in Steel
Precipitation
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
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
Time Temperature Transformation (TTT) diagrams A type of phase
diagram

Small driving
force for nucleation

Tm Tm

T
T (K)

T (K)
Time for transformation
Replot

0 0
T (rate sec1) t (sec)
Growth
sluggish
TTT diagram phase transformation

Increasing % transformation


T (K)

99% = finish

1% = start

t (sec)
APPLICATIONS

Phase Transformations in Steel

Precipitation

Recovery recrystallization & grain growth


Phase Transformations in Steel
Fe-Cementite diagram Eutectic
L + Fe3C
Peritectic L
L+ 1493C

L+
0.1 %C 2.06 1147C

Eutectoid + Fe3C
+ Fe3C
723C

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 T1 T2
0.1 1 10 102 103 104 105
t (s)
Different cooling treatments Eutectoid steel (0.8%C)

800
723

M = Martensite 600

Water qu
P = Pearlite 500

Fu
No

ll a
T

rm
400

nne
ali
ench

zin

al
300

Oi

g
lq
uen
200
Coarse P
ch
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 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 ) 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


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 ) 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
Tempering follows 800
Eutectoid temperature
723
Austenite
Pearlite
600
+ Fe3C
Martempering 500 Pearlite + Bainite

T
400 Bainite

300
Ms

Austempering 200
Mf
100
AUSTEMPERING Martensite

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 (C)

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 )



4 % Cu 0.5 % Cu
slow cool
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

In

s)
Hardness -c

ne
oh
er

zo
e nt

P
(p

(G
re
cip
nt
re ita
te
he
s)
Co

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)
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

Po
lyg
on
iza Low angle grain boundaries
tio
n
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


EFFECT OF
ALLOYING
CARBON

http://www.asminternational.org/documents/10192/1849770/ACF180B.pdf
Distribution of Alloying Elements
In alloy steels, alloying elements can be found,
1.in the free state
2.As intermetallic compounds with iron or with each
other
3.As oxides, sulphides, amd other nonmetal
inclusions
4.In the carbide phase as a solution in cementite or
in the form of independent compounds with carbon
5.As a solution in iron
Alloying elements ma be divided into two
groups:
1.Elements that do not form carbides in
steel, such as Ni, Si, Co, Al, Cu and N
2.Elements that form stable carbides in
steel, such as Cr, Mn, Mo, W, V, Ti, Zr, and
Nb
Alloying elements
Whose affinity for oxygen is greater than
iron, are capable to forming oxides and
other nonmetal compounds. (Al, Si, V, Ti)
and become fine nonmetal inclusions.

Whose affinity for sulfur is greater than iron,


are capable to forming sulfides.
Alloy Carbides
Carbides are formed in steels only by iron and metals that stand to the
left of iron in the periodic table.
Possible variants of carbide formation
in Steels
Effects on Transformation Diagrams
Effect on Ferrite Hardness
Effect on Martensite
Transformation Temperature
Nitride-forming Elements
Time Temperature Transformation (TTT)
Diagrams
Time Temperature Transformation (TTT) Diagrams
Time Temperature Transformation (TTT) Diagrams
For this particular steel want to cool from about 1400 F to <400 F in about 1
second!
Time Temperature Transformation (TTT) Diagrams
Time Temperature Transformation (TTT) Diagrams
Applications of TTT diagrams
Martempering
Austempering
Isothermal Annealing
Patenting
Time Temperature Transformation (TTT) Diagrams
Time Temperature Transformation (TTT) Diagrams
Time Temperature Transformation (TTT) Diagrams
Time Temperature Transformation (TTT) Diagrams
160

140 The complete


isothermal
120 transformation
diagram for an iron-
carbon alloy of
100
eutectoid composition.

80 A: austenite
B: bainite
60
M: martensite
40 P: pearlite

20

0
1 10 100
Example Problem

Using the isothermal transformation diagram for an


iron-carbon alloy of eutectoid composition, specify the
nature of the final microstructure of a small specimen
that has been subjected to the following time-
temperature treatments.
The specimen begins at 760C and that it has been
held at this temperature long enough to have achieved
a complete and homogeneous austenitic structure.
(a) Rapidly cool to 250C, hold for 100s, and quench to
room temperature
(b) Rapidly cool to 600C, hold for 104 s, and quench to
room temperature
Example Problem

160 (a) Rapidly cool to 250C,


hold for 100s, and quench
140 to room temperature
(b) Rapidly cool to 600C,
120
hold for 104 s, and quench
100
to room temperature

80

60

40

20

0
1 10 100
A
The time-temperature-transformation diagram
for an iron-carbon alloy of eutectoid composition
and the isothermal heat treatments
Example Problem
(a) Rapidly cool to 250C,
hold for 100s, and quench
to room temperature

At 760C: in the austenite


region () 100%
austenite

Rapidly cool from 760C


to 250C: 100% austenite

Hold for 100 seconds at


250C: 100% austenite

Quench to room temp.:


100% martensite
Example Problem
(b) Rapidly cool to 600C,
hold for 104 s, and cool to
room temperature

At 760C: in the austenite


region () 100%
austenite
Rapidly cool from 760C
to 600C: 100% austenite

Hold for 104 s at 250C:


100% pearlite

Quench to room temp.:


100% pearlite
Continuous Cooling Transformation (CCT)
Diagrams
Continuous Cooling Transformation (CCT)
Diagrams
Continuous Cooling Transformation (CCT)
Diagrams
Continuous Cooling Transformation (CCT)
Diagrams