HeatTreatment

Dr.SantoshS.Hosmani
Temperature Time Transformation (TTT) diagrams p ( ) g
Phase Transformation
Solid
Solid state phase
transformation
Solid 2 1
transformation
Physical metallurgy
Liquid
Gas
condensation
q
evaporation
Wh t i th d i i f f h What is the driving force for any phase
transformation?
> Decrease in Gibbs free energy
Liquid ->Solid Liquid ->Solid
G
s
- G
l
= G <=>If this is ve, then only this transformation
will occur. will occur.
G
e
n
e
r
g
y
,

G
1
Energy barrier
E
a
F
r
e
e

e
Reactants
G = G
2
G
1
Course of reaction
Products
G
2
Course of reaction
G
G
L
Gibbs free energy as a function of temperature,
G
S
G
S
T
G
p
=

T
C
T
G
p
p
=

2
2
Liquid is stable Solid is stable
G
S
<G
L
G
L
<G
S
G
S
G
L
G
S
T
m
T
T
freesing
The second derivative of a function measures the
concavity of the graph of .
A function whose second derivative is positive will be p
concave up, meaning that the tangent line will lie below the
graph of the function.
Similarly, a function whose second derivative is negative
will be concave down, and its tangent lines will lie above
the graph of the function.
R
e
f
.
:

W
i
k
i
R
The tangent line is blue where the curve is concave up, green
where the curve is concave down, and red at the inflection points
How does solidification
b i ? begins?
Usually at the walls of the
container
Heterogeneous
nucleation.
Why?
To be discussed later.
Spherical ball of solid of radius r
in the middle of the liquid at a
temperature below T
m
Homogeneous nucleation
G = free energy of liquid r G
L
= free energy of liquid
per unit volume
G
S
= free energy of solid
r
G
S
free energy of solid
per unit volume
G = G
S
- G
L
G G
S
G
L
Change in free energy of the
system due to formation of the
lid b ll f di
) (
3
4
3
L s
G G r f =
2
4 r
+
solid ball of radius r :
) (
3
L s
f
+ve: barrier to
nucleation

2
4 r +
r
At constant
Temperature
r
f
r
r
*
) (
3
4
3
L s
G G r
V
3
3
4
G r f =
2
4 r
+
Solid balls of radius r <r*
t it ill l d
V
3
f
cannot grow as it will lead
to increase in the free
energy of the system !!!

2
4 r +
Solid balls of radii r >r*
will grow
At constant
Temperature
r
f
will grow
r* is known as the
r
r
*
r* is known as the
CRITICAL RADIUS OF
HOMOGENEOUS
NUCLEATION
V
3
3
4
G r
NUCLEATION
V
3
3
4
G r f =

2
4 r +

2
4 r
+
V
3
f
f
0
*
=

=r r
r
f
* f
r
r
*
f
r r
2
V
3
3
4
G r
V
2
*
G
r

=

3
2
3
) ( 3
16
*
G
f

=

2
V
) ( 3 G
f

Driving force for solidification:

L S
G G G =
V ) ( ) ( ) ( T S T T H T G =
0 ) ( ) ( ) ( = = T S T T H T G
G
0 ) ( ) ( ) ( = =
m m m m
T S T T H T G
m
m
m
T
T H
T S
) (
) (

=
G
G (T)
) ( ) (
m
T H T H = ) ( ) (
m
T S T S =
m
) ( ) ( ) (
m m m
T S T T H T G = ) ( ) ( ) (
m m m
m
m
m
T
T H
T T H
) (
) (

=
G
L G
S
) (
m
m
m
T H
T
T T

=
T
T
T
m
T
m
m
H
T
T
T G

= ) (
G r f =
3
3
4

2
4 r
+
f
f
3

) (
4
) (
3
T G r T f =
2
4 r
+
f
1
*
) (
3
) ( T G r T f =
4 r
+
r
T
r
1
*
f
2
*
r
2
*
m
m
H
T
T
T G

= ) (
1 2
G
r

=
2
*
m
H T
T
r

=
2
*
T
1
T
2
<
G
2
3
16
* f =

m
H T
2 3
16
*
m
T
f =

2
) ( 3 G
f

2 2
) ( ) ( 3
m
H T
f

=
Formation of critical nucleus
by statistical fluctuation
Atoms surrounding the
critical particle
by statistical fluctuation
Critical
particle
Diffuse jump of a Diffuse jump of a
surrounding atom
to the critical
particle makes it
l ti a nucleation
The Nucleation Rate
N =total number of clusters of atoms per unit volume N
t
=total number of clusters of atoms per unit volume
N* =number of clusters of critical size per unit volume
By Maxwell-Boltzmann statistics:

f
N N
*
*

=
RT
f
N N
t
exp *

=
RT
f
N N
t
*
exp *

RT
s*=no. of liquid phase
t f i th atoms facing the
critical sized particle
H
d
=activation energy for diffusive jump from liquid to the
solid phase
=atomic vibration frequency
The rate of successful addition of an atomto a critical The rate of successful addition of an atom to a critical
sized paticle

H
d

=
RT
H
s v
d
exp * '
Rate of nucleation, I , (m
3
s
-1
) =No. of nucleation events per m
3
per sec
=number of critical clusters per unit volume (N*) =number of critical clusters per unit volume (N )
x
rate of successful addition of an atom to the critical
cluster ()
' * N I =
cluster ( )

=
RT
H
s
RT
f
N
d
t
exp *
*
exp

+
=
RT
H f
s N
d
t
*
exp *
T
With decreasing T
1. Driving force increases
T
m
2. Atomic mobility decreases
I
*
f

f *
exp
I

RT
p

H
d

RT
H
d
exp
Growth
Increase in the size of a product particle after it has nucleated
dr
U
T
dt
U =
UU
Overall Transformation Kinetics
T
I : Nucleation
rate
U
dX/dt
U : Growth rate
dr
dX/dt
dt
dr
=
Overall transformation rate
I
Overall transformation rate
(fraction transformed per
second)
) , ( I U f
dT
dX
=
dT
X=fraction of product phase
Fraction transformed as a function of time
X
Slow due to final
i i t impingement
Slow due to very few
nuclei
t
nuclei
t
s t
f
TTT Diagram for liquid-to-
solid transformation
X
1
solid transformation
1
log t t
s
t
f
0
T
Stable liquid
T
og
s f
T
m
crystal
Under
Cooledliquid
crystal
Cooled liquid
dX/dt log t
TTT Diagram for liquid-to-solid transformation
T
U
T
Stable liquid
Under
Cooledliquid
T
m
I
Cooled liquid
I
Coarse
i d
Fine grained
crystals
grained
crystals
crystals
log t
glass
log t
T t metals T t
s
metals
t
s
SiO
2
log t Silica glass
Metallic
l
+ H f *
glass

+
=
RT
H f
s N I
d
t
*
exp *
2 2
2 3
) ( ) (
16
*
m
T
f =

Metals: high H lowviscosity
SiO
2
: low H
m
, high viscosity
2 2
) ( ) ( 3
m
H T
f

H
d
log (viscosity)
Metals: high H
m
, low viscosity
Inertgaspressure
Q b
Melt Spinning for metallic glass ribbons
Moltenalloy
Heater coil
Quartztube
Heater coil
Jetof moltenmetal
Ribbonof
glassymetal
Rotatingcooled
metal drum
Cooling rate 10
6
C s
-1
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap (McGraw-Hill, 2002)
http://Materials.Usask.Ca
T
T
m
Log (viscosity)
crystal
30
log t
18
glass
12
18
Undercooled
li id
Stable liquid
liquid
T
T
m
T
g
Specific
volume
Stable liquid
Undercooled liquid
Fast cool Fast cool
Slow cool
T
T
gf
crystal
T
T
m
T
gs T
T
Stable liquid
T
Glass
ceramics
Undercooled liquid
T
m
ceramics
devitrification
glass
crystal
log t
U
T
T Liquid
gass
crystal
U
nucleation
growth
Very fine
crystals
I
nucleation
time
glass Glass ceramic
Steels
30
How steels are produced?
31
Crystal Structure of Pure Iron
32
TheIroncarbonsystem
Mildsteel
00.3wt%C
Bicycleframe
Shiphull
C b d
1410
1150
Carbody
MediumCsteel
910
steel Castiron
0.40.7wt%C
Railwheel
0.8
725
0 02
railaxle
rails
0.02
HighCsteel
0.81.4wt%C
R bl d Razorblades
scissors,knives
33
Heat-Treatment of Steels
HEAT TREATMENT
Heating a material to a high temperature, holding it
at that temperature for certain length of time
followed by cooling at a specified rate is called
heat treatment
holding
T
AT
A
N
AT
T
Q
time
Annealing Furnace cooling RC 15
Normalizing Air cooling RC 30
Quenching Water cooling RC 65 Quenching Water cooling RC 65
Tempering Heating after quench RC 55
Austempering Quench to an inter- RC 45
mediate temp. and hold
Eutectoid Reaction
C F
C
o
725
C Fe
C
3
725
+
0.8 0.02 6.67
cool
Pearlite
Ammount of Fe
3
C in Pearlite
Red Tie Line below eutectoid temp
78 0 02 0 8 0
117 . 0
65 . 6
78 . 0
02 . 0 67 . 6
02 . 0 8 . 0
3
= =

=
pearlite
C F
f
Phasediagramsdonothaveanyinformation
abouttimeorratesoftransformations.
WeneedTTTdiagramforunderstandingthe
possible transformation from austenite. possibletransformationfromaustenite.
Stableaustenite
TTTdiagramforeutectoidsteel
unstable
austenite
Stableaustenite
U
T
TTTdiagramforeutectoidsteel
Annealing:
U
g
coarse
pearlite
Normalizing:
fi lit
I
finepearlite
unstable
austenite