Professional Documents
Culture Documents
PHASE TRANSFORMATIONS
Based on
Mass
transport
Diffusional
Involves long range mass transport
Diffusionless
E.g. Martensitic
PHASE TRANSFORMATIONS
Based on
order
1nd order
nucleation & growth
Transformations in Materials
Phase transformations are associated with change in one or more properties.
Hence for microstructure dependent properties we would like to additionally worry about
subtler transformations, which involve defect structure and stress state (apart from
phases).
Therefore the broader subject of interest is Microstructural Transformations.
Phases
Defects
Phase
Transformation
Defect Structure
Transformation
Stress-State
Transformation
Geometrical
Physical
Structural
Property
Phases
Phases Transformations
Residual stress
Microstructure
Microstructural Transformations
Revise concepts of surface and interface energy before starting on these topics
Interfacial energy
Strain energy
Important in solid to solid transformations
The origin of the strain energy can be understood using the schematics as below. Eshelby
construction is used for this purpose.
In general a solid state phase transformation can involve a change in both volume and
shape. I.e. both dilatational and shear strains may be involved. For simplicity we consider
only change in volume of the material, leading to an increase in the strain energy of the
system (in future considerations).
Bulk Gibbs free energy
Interfacial energy
Energies involved
Strain energy
(a)
(b)
(c)
Considering only
volume change
(d)
Schematic of the Eshelby construction to understand the origin of the stresses due to phase transformation
of a volume (V): (a) region V before transformation, (b) the region V is cut out of the matrix and allowed to
transform (the transformation could involve both shape and volume changes), (c) the transformed volume
(V- shown to be larger in the figure) is inserted into the hole (here only volume change is shown for
simplicity), (c) the system is allowed to equilibrate. The continuity of the system is maintained during the
transformation. The system is strained as a larger volume V is inserted into the hole of volume V.
Let us start understanding phase transformations using the example of the solidification of
a pure metal. (This process is a first order transformation*. First order transformations
involve nucleation and growth**).
There is no change in composition involved as we are considering a pure metal. If we
solidify an alloy this will involve long range diffusion.
Strain energy term can be neglected as the liquid melt can flow to accommodate the
volume change (assume we are working at constant T & P).
The process can start only below the melting point of the liquid (as only below the melting
point the GLiquid < GSolid). I.e. we need to Undercool the system. As we shall note, under
suitable conditions (e.g. container-less solidification in zero gravity conditions), melts can
be undercooled to a large extent without solidification taking place.
Bulk Gibbs free energy
Energies involved
Interfacial energy
Strain energy
1nd order
**
nucleation & growth
Trasformation
Solid-solid transformation
Nucleation
+
of
phase
Growth till
is
exhausted
Liquid
Solid
Growth of Crystal
Grain boundary
Crude schematic!
Solidification complete
Liquid stable
Gv
Solid (GS)
G ve
T
Liquid (GL)
G +ve
T - Undercooling
Tm
Solidification
Nucleation
of crystals from melt
Growth
of nucleated crystals till liquid is exhausted
Homogenous
Nucleation
Heterogeneous
Homogenous nucleation
Neglected in L S transformations
Reduction in bulk free energy increase in surface energy increase in strain energy
G (Volume).(GV ) (Surface).( )
f (r )
G r 3 .(Gv ) 4r 2 .( )
3
Gv f (T )
r3
r2
r 1
G r 3 .(Gv ) 4r 2 .( )
3
In the above equation, the r3 term is +ve and the r2 term is ve. Such kinds of equations
are often encountered in materials science, where one term is opposing the process and the
other is supporting it. Example of such processes are crack growth (where surface energy
opposes the process and the strain energy stored in the material supports crack growth).
In the current case it is the higher power is supporting the phase transformation. Since the
higher power dominates above 1, the function will go through a maximum as in fig.
below. This implies the G function will go through a maximum. I.e. if the process just
even starts it will lead to an increase in G! (more about this soon).
On the other hand the function with ve contribution from the lower power (to G) will
go through a minimum (fig. below) and such a process will take place down-hill in G and
stop.
1
4
0.6
0.4
2.5
0.2
f(x)
x^n
(x - x^2)
(x^2 - x)
0.8
x^2
x^3
3.5
1.5
-0.2
-0.4
-0.6
0.5
-0.8
0
0
0.2
0.4
0.6
0.8
1.2
1.4
1.6
-1
0.2
0.4
0.6
0.8
1.2
1.4
1.6
G r 3 .(Gv ) 4r 2 .( )
3
r*
r2*
Trivial solution
2
Gv
2
Gv
16
G
3 Gv2
3
G 0
3
r0
Gv
r1* 0
dr
G 0
r*
Embryos
r0
Supercritical nuclei
That the melting point is not the same as the freezing point!!
This energy (G) barrier to nucleation is called the nucleation barrier.
Decreasing G*
Tm
Gv f (T )
The bulk free energy reduction is a function of undercooling
r*
2
Gv
16 3
G
3 Gv2
*
Decreasing r*
Using the Turnbull approximation (linearizing the G-T curve
close to Tm), we can get the value of G interms of the enthalpy
of solidification.
Tm2
16 3
G
3
T 2 H 2
Turnbulls approximation
G H f
Solid (GS)
Tm T
T
H f
Tm
Tm
H f heat of fusion
16 3 Tm
*
G
H f T
3
Liquid (GL)
Tm
Jump
Quantum
Tm
T
r*
To cause nucleation (or even to form an embryo) atoms of the liquid (which are randomly moving
about) have to come together in a order, which resembles the crystalline order, at a given instant of
time.
Typically, this crystalline order is very different from the order (local order), which exists in the liquid.
This coming together is a random process, which is statistical in nature i.e. the liquid is exploring
locally many different possible configurations and randomly (by chance), in some location in the
liquid, this order may resemble the preferred crystalline order.
Since this process is random (& statistical) in nature, the probability that a larger sized crystalline
order is assembled is lower than that to assemble a smaller sized crystal.
Hence, at smaller undercoolings (where the value of r* is large) the chance of the formation of a
supercritical nucleus is smaller and so is the probability of solidification (as at least one nucleus is
needed which can grow to cause solidification). At larger undercoolings, where r* value is relatively
smaller, the chance of solidification is higher.
Funda Check
Melting point, undercooling, freezing point (in the realm of homogenous nucleation)
The plot below shows melting point of Au nanoparticles, plotted as a function of the particle radius. It is to
be noted that the melting point of nanoparticles decreases below the bulk melting point (a 5nm particle
melts more than 100C below Tmbulk). This is due to surface effects (surface is expected to have a lower
melting point than bulk!?*) actually, the current understanding is that the whole nanoparticle melts
simultaneously (not surface layer by layer).
Let us continue to use the example of Au. Suppose we are below Tmbulk (1337K=1064C, i.e. system is undercooled
w.r.t the bulk melting point) at T1 (=1300K T = 37K) and suppose a small crystal of r2 = 5nm forms in the liquid.
Now the melting point of this crystal is ~1200K this crystal will melt-away. Now we have to assemble a
crystal of size of about 15nm (= r1) for it not to melt. This needless to say is much less probable (and it is
better to undercool even further so that the value of r* decreases) . Thus the mystery of nucleation barrier
vanishes and we can think of melting point freezing point (for a given size of particle)!
Tm is in heating for the bulk material and in cooling if we take into account the size dependence of melting
point everything sort-of falls into place .
T1
r1
N * Nt e
G *
kT
The number of potential atoms, which can jump to make the critical nucleus supercritical are
the atoms which are adjacent to the liquid let this number be s*.
If the lattice vibration frequency is and the activation barrier for an atom facing the nucleus
(i.e. atom belonging to s*) to jump into the nucleus (to make in supercritical) is Hd , the
frequency with which nuclei become supercritical due atomic jumps into the nucleus is given
H
by:
*
' s e kT
d
Rate of nucleation =
dN
dt
N * Nt e
G *
kT
No. of particles/volume in L
' s* e
H d
kT
The nucleation rate (I = dN/dt) can be written as a product of the two terms as in the equation
below.
How does the plot of this function look with temperature?
At Tm , G* is I = 0 (as expected if there is no undercooling there is no nucleation).
At T = 0K again I = 0
This implies that the function should reach a maximum between T = Tm and T = 0.
A schematic plot of I(T) (or I(T)) is given in the figure below.
An important point to note is that the nucleation rate is not a monotonic function of
undercooling.
Tm
I Nt s* e
T (K)
Increasing T
T = Tm G* = I = 0
T=0I=0
G * H d
kT
G* I
Note: G* is a function of T
T I
Heterogenous nucleation
We have already talked about the nucleation barrier and the difficulty in the nucleation
process. This is all the more so for fully solid state phase transformations, where the strain
energy term is also involved (which opposes the transformation).
The nucleation process is often made easier by the presence of defects in the system.
In the solidification of a liquid this could be the mold walls.
For solid state transformation suitable nucleation sites are: non-equilibrium defects such
as excess vacancies, dislocations, grain boundaries, stacking faults, inclusions and
surfaces.
One way to visualize the ease of heterogeneous nucleation
heterogeneous nucleation at a defect will lead to destruction/modification of the defect
(make it less defective). This will lead to some free energy Gd being released thus
reducing the activation barrier (equation below).
Heterogenous nucleation
Consider the nucleation of from on a planar surface of inclusion .
The nucleus will have the shape of a lens (as in the figure below).
Surface tension force balance equation can be written as in equation (1) below. The contact angle
can be calculated from this equation (as in equation (3)).
Keeping in view the interface areas created and lost we can write the G equation as below (2).
Interfacial Energies
Created
Alens
Created
Acircle
(3)
Acircle
Lost
Cos
(1)
Alens = 2rh
h = (1-Cos)r
(2)
rcircle = r Sin
Using the procedure as before (for the case of the homogenous nucleation) we can find r* for
heterogeneous nucleation. Using the surface tension balance equation we can write the
formulae for r*and G* using a single interfacial energy (and contact angle ).
*
*
Further we can write down Ghetero
in terms of Ghomo
and contact angle .
dG
0
dr
G
*
hetero
*
hetero
2
Gv
*
Ghetero
2 3Cos Cos 3
2
3 Gv
1 *
Ghomo
2 3Cos Cos 3
4
*
Ghetero
1
2 3Cos Cos 3
*
Ghomo
4
Just a function of
the contact angle
Increasing
contact angle
= 0 f() = 0
*
Ghetero
1
2 3Cos Cos3 f ( )
*
Ghomo
4
= 90 f() =
Complete wetting
Partial wetting
= 180 f() = 1
No wetting
*
*
The plot of Ghetero
/ Ghomo
is shown in the next page.
Plot of G*hetero/G*homo is shown below. This brings out the benefit of heterogeneous nucleation vs homogenous nucleation.
If the phase nucleus (lens shaped) completely wets the substrate/inclusion (-phase) (i.e. = 0)
then G*hetero = 0 there is no barrier to nucleation.
On the other extreme if -phase does not we the substrate (i.e. = 180)
then G*hetero = G*homo there is no benefit of the substrate.
In reality the wetting angle is somewhere between 0-180
Hence, we have to chose a heterogeneous nucleating agent with a minimum value.
G*hetero / G*homo
0.75
G*hetero (0o) = 0
no barrier to nucleation
0.5
Cos
0.25
Complete wetting
No wetting
Partial wetting
0
0
30
60
90
120
(degrees)
150
180
Cos
Why does heterogeneous nucleation dominate? (arent there more number of homogenous nucleation sites?)
To understand the above questions, let us write the nucleation rate for both cases as a preexponential term and an exponential term. The pre-exponential term is a function of the
number of nucleation sites.
However, the term that dominates is the exponential term and due to a lower G* the
heterogeneous nucleation rate is typically higher.
0
I homo I homo
e
*
Ghomo
kT
0
I hetero I hetero
e
*
Ghetero
kT
BUT
the exponential term dominates
Ihetero > Ihomo
Growth
Diffusional transformations involve nucleation and growth. Nucleation involves the
formation of a different phase from a parent phase (e.g. crystal from melt). Growth
involves attachment of atoms belonging to the matrix to the new phase (e.g. atoms
belonging to the liquid phase attach to the crystal phase).
Nucleation we have noted is uphill in G process, while growth is downhill in G.
Growth can proceed till all the prescribed product phase forms (by consuming the parent
phase).
Transformation
= Nucleation of phase +
Growth of phase
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 than that for the forward jump.
Hd
Hd vatom Gv
phase
phase
Transformation rate
As expected transformation rate (Tr) is a function of nucleation rate (I) and growth rate
(U).
In a transformation, if X is the fraction of -phase formed, then dX/dt is the
transformation rate.
The derivation of Tr as a function of I & U is carried using some assumptions (e.g.
Johnson-Mehl and Avarami models).
We have already seen the curve for the nucleation rate (I) as a function of the
undercooling.
The growth rate (U) curve as a function of undercooling looks similar. The key difference
being that the maximum of U-T* curve is typically above the I-T curve*.
This fact that T(Umax) > T(Imax) give us an important handle on the scale of the
transformed phases forming. We will see examples of the utility of this information later.
Increasing T
Tm
dX
dt
f (I , U )
Tr
T (K)
I, U, Tr
[rate sec1]
Fraction of the product () phase forming with time the sigmoidal growth curve
Many processes in nature (etc.), e.g. growth of bacteria in a culture (number of bacteria
with time), marks obtained versus study time(!), etc. tend to follow a universal curve the
sigmoidal growth curve.
In the context of phase transformation, the fraction of the product phase (X) forming with
time follows a sigmoidal curve (function and curve as below).
1.0
X 1 e
0.5
I U3 t 4
From Rate to time: the origin of Time Temperature Transformation (TTT) diagrams
A type of phase diagram
The transformation rate curve (Tr-T plot) has hidden in it the I-T and U-T curves.
An alternate way of plotting the Transformation rate (Tr) curve is to plot Transformation
time (Tt) [i.e. go from frequency domain to time domain]. Such a plot is called the TimeTemperature-Transformation diagram (TTT diagram).
High rates correspond to short times and vice-versa. Zero rate implies time (no transformation).
This Tt-T plot looks like the C alphabet and is often called the C-curve. The minimum
time part is called the nose of the curve.
Tm
Rate f (T , t )
Tm
Small driving
force for nucleation
Tr
Replot
T (K)
T (K)
Tr (rate sec1)
Tt
Sluggish growth
Tt (time sec)
Clearly the picture of TTT diagram presented before is incomplete transformations may
start at a particular time, but will take time to be completed (i.e. between the L-phase field
and solid phase field there must be a two phase region L+S!).
This implies that we need two C curves one for start of transformation and one for
completion. A practical problem in this regard is related to the issue of how to define start
and finish (is start the first nucleus which forms? Does finish correspond to 100%?) . Since practically it is
difficult to find % and 100%, we use practical measures of start and finish, which can
be measured experimentally. Typically this is done using optical metallography and a
reliable resolution of the technique is about 1% for start and 99% for finish.
Another obvious point: as x-axis is time any transformation paths have to be drawn such
that it is from left to right (i.e. in increasing time).
TTT diagram phase transformation
Increasing % transformation
99% = finish
T (K)
1% = start
Fraction
transformed
volume fraction of at t
final volume of
f volume fractionof
t (sec)
Nucleation rate
Growth rate
f(t,T) determined by
f Nn 4 r 2 dr Nn 4 Ut Udt Nn 4U 3t 2 dt
2
This fraction (f) has to be corrected for impingement. The corrected transformed volume
fraction (X) is lower than f by a factor (1X) as contribution to transformed volume
fraction comes from untransformed regions only:
dX
1 X
dX
N n 4U 3t 2 dt
1 X
t t
dX
3 2
N
4
U
t dt
0 1 X t 0 n
X 1 e
4 Nn U3 t 3
Based on the assumptions note that the growth rate is not part of the equation it is only the
number of nuclei.
Pearlitic transformation
Cellular Precipitation
Massive Transformation
Recrystallization
4
4
3
f r 3 Id U (t ) Id
3
3
This fraction (f) has to be corrected for impingement. The corrected transformed volume
fraction (X) is lower than f by a factor (1X) as contribution to transformed volume
fraction comes from untransformed regions only:
dX
1 X
dX
4 3
4
3
r Id U (t ) Id
1 X 3
3
dX
4
3
U
(
t
)
Id X 1 e
0 1 X 0 3
I U3 t 4
1.0
I U3
APPLICATIONS
of the concepts of nucleation & growth
TTT/CCT diagrams
We have already seen the Fe-Fe3C phase diagram (please have a second look!)
Fe-Cementite diagram
Peritectic
L+
Eutectic
L + Fe3C
1493C
L+
0.1 %C
Eutectoid
+ Fe3C
1147C
2.06
+ Fe3C
723C
+ Fe3C
0.025 %C
%C
Fe
0.16
0.8
4.3
Fe3C
6.7
Above Eutectoid
temperature there is no
transformation
800
Eutectoid temperature
723C
700
Pearlite
600
+ Fe3C
Nose of C curve
500
400
Important points to be
noted:
The x-axis is log scale.
Pearlite + Bainite
Bainite
Austenite
300
200
100
Ms
Mf
Martensite
0.1
10
102
t (s)
103
104
105
As pointed out before one of the important utilities of the TTT diagrams comes from the
overlay of microconstituents (microstructures) on the diagram.
Depending on the T, the ( + Fe3C) phase field is labeled with microconstituents like
Pearlite, Bainite.
We had seen that TTT diagrams are drawn by instantaneous quench to a temperature
followed by isothermal hold.
Suppose we quench below (~225C, below the temperature marked Ms), then Austenite
transforms via a diffusionless transformation (involving shear) to a (hard) phase known as
Martensite. Below a temperature marked Mf this transformation to Martensite is complete.
Once is exhausted it cannot transform to ( + Fe3C).
Hence, we have a new phase field for Martensite. The fraction of Martensite formed is not
a function of the time of hold, but the temperature to which we quench (between Ms and
Mf).
800
Eutectoid steel (0.8%C)
Eutectoid temperature
723C
700
Pearlite
600
+ Fe3C
500
400
Pearlite + Bainite
Bainite
Austenite
300
200
100
Ms
Mf
Martensite
0.1
10
102
t (s)
103
104
105
Strictly speaking cooling curves (including finite quenching rates) should not be overlaid
on TTT diagrams (remember that TTT diagrams are drawn for isothermal holds!).
Isothermal hold at: (i) T1 gives us Pearlite, (ii) T2 gives Pearlite+Bainite, (iii) T3 gives
Bainite. Note that Pearlite and Bainite are both +Fe3C (but their morphologies are
different).
To produce Martensite we should quench at a rate such as to avoid the nose of the start C
curve. Called the critical cooling rate.
If we quench between Ms and Mf we
will get a mixture of Martensite and
(called retained Austenite).
800
723C Eutectoid temperature
700
600
500
Austenite
200
100
T
Not an isothermal
transformation
Coarse
Pearlite
T1
Fine
Pearlite + Bainite
T2
400
300
Bainite
T3
Ms
Austenite
Mf
Martensite
0.1
10
103
102
t (s)
104
105
Funda Check
For the transformations to both Pearlite and Bainite, why do we have only
one C curve?
C1
In hypo- (and hyper-) eutectoid steels (say composition C1) there is one more branch to the
C curve-NP (marked in red).
The part of the curve lying between T1 and TE (marked in figs. below) is clear, because in this range of
temperatures we expect only pro-eutectoid to form and the final microstructure will
consist of and .(E.g. if we cool to Tx and hold- left figure).
The part of the curve below TE is a bit of a mystery (since we are instantaneously cooling
steel
to below TE, we should get a mix of + Fe3C what is the meaning Hypo-Eutectoid
of a pro-eutectoid
phase in a TTT diagram? (remember pro- implies pre-).(Considered next)
Funda Check
C1
Similar to the hypo-eutectoid case, hyper-eutectoid compositions (e.g. C2 in fig. below) have a
+Fe3C branch.
For a temperature between T2 and TE (say Tm (not melting point- just a label)) we land up with +Fe3C.
For a temperature below TE (but above the nose of the C curve) (say Tn), first we have the
formation of pro-eutectoid Fe3C followed by the formation of eutectoid +Fe3C.
T2
TE
Hyper-Eutectoid steel
C2
T1
dT
T
dt
> T2
800
Eutectoid temperature
723
Start
600
Pearlite
Finish
500
400
Important points to be
noted:
As before the x-axis is
log scale.
Bainite cannot form by
continuous cooling.
Constant rate cooling
curves look like curves
due to log scale in xaxis. The higher cooling
rate curve has a higher
(negative) slope.
As time is one of the
axes, no treatment curve
can be drawn where time
decreases or remains
constant.
300
200
Cooling curves
Constant rate
Ms
Mf
100
Martensite
0.1
T2
T1
10
102
103
104
t (s)
105
Funda Check The CCT curves are to the right of the corresponding TTT curves. Why?
As the cooled sample has spent more time at higher temperature, before it intersects the
TTT curve (virtually superimposed) and the transformation time is longer at higher T
(above the nose) CCT curves should be to the right of TTT curves.
800
Eutectoid temperature
723
600
Pearlite
500
400
300
200
Cooling curves
Constant rate
Ms
Mf
100
0.1
T2
T1
Martensite
10
102
103
104
t (s)
105
Common cooling heat treatment labels (with increasing cooling rate) are:
Full anneal < Normalizing < Oil quench < Water quench
The microstructures produced for these treatments are:
Full Anneal (furnace cooling) Coarse Pearlite
Normalizing (Air cooling) Fine Pearlite
Oil Quench Matensite (M) + Pearlite (P)
Water Quench Matensite
To produce full martensite we have to avoid the nose of the TTT diagram (i.e. the
quenching rate should be fast enough).
Within water or oil quench further parameters determine the actual quench rate (e.g. was the
sample shaken?).
It is important to note that for a single composition, different cooling treatments give
different microstructures these give rise to a varied set of properties.
After even water quench to produce Martensite, further heat treatment (tempering) can be
given to optimize properties like strength and ductility.
800
Eutectoid steel (0.8%C)
723
600
zin
al
nne
ll a
Fu
ali
rm
No
ench
400
Water qu
500
ch
uen
lq
Oi
300
200
Coarse P
100
M
Pearlite
PP == Pearlite
M == Martensite
Martensite
M
0.1
M + P
10
103
102
t (s)
Fine P
104
105
Process
105 103
Air Cooling
1 10
Oil Quenching*
~100
Water Quenching*
~500
Splat Quenching
105
Melt-Spinning
106 108
Evaporation, sputtering
109 (expected)
Pearlite
+ Fe3C
(100)C || (1 11)
Orientation Relation:
Kurdyumov-Sachs
(010)C || (110)
(001)C || (112)
Branching mechanism
Bainite
+ Fe3C**
Bainite formed at high temperature (~ 350C) has a feathery appearance and is called
Feathery Bainite.
Bainite formed at lower temperature (~ 275C) has a needle-like appearance and is called
acicular Bainite.
The process of formation of bainite involves 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
AFM image
Martensite
Change in Crystal Structure
( FCC )
0.8 %C
Quench
' ( BCT )
0.8 %C
Martensitic transformation can be understood by first considering an alternate unit cell for the
Austenite phase as shown in the figure below.
If there is no carbon in the Austenite (as in the schematic below), then the Martensitic
transformation can be understood as a ~20% contraction along the c-axis and a ~12% expansion of
the a-axis accompanied by no volume change and the resultant structure has a BCC lattice (the
usual BCC-Fe) c/a ratio of 1.0.
In Pure Fe after
the Matensitic transformation
c=a
FCC BCC
Martensite
In the presence of Carbon in the octahedral voids of CCP (FCC) -Fe (as in the schematic below)
the contraction along the c-axis is impeded by the carbon atoms. (Note that only a fraction of the
octahedral voids are filled with carbon as the percentage of C in Fe is small).
However the a1 and a2 axis can expand freely. This leads to a product with c/a ratio (c/a) >1
1-1.1.
In this case there is an overall increase in volume of ~4.3% (depends on the carbon content) the
Bain distortion*.
C along the c-axis
obstructs the contraction
Tetragonal
Martensite
* Homogenous dilation of the lattice (expansion/contraction along crystallographic axis) leading to the formation of a new lattice is called
Bain distortion. This involves minimum atomic movements.
Slip
Average shape
remains undistorted
Hardness (Rc)
60
40
Harness of Martensite as a
function of Carbon content
20
% Carbon
0.2
0.4
0.6
Properties of 0.8% C steel
Hardness (Rc)
Coarse pearlite
16
710
Fine pearlite
30
990
Bainite
45
1470
Martensite
65
55
1990
Constituent
Solid solution
Substitutional
Element Added
Compound (new crystal structure)
Alloying elements
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
Brinell Hardness
Mn +0.1% C
180
Mn
Cr + 0.1%C
140
Cr
100
60
10
Temperature
0.35% Mn
6.5% Mn
0.4
Temperature
15% Cr
0.4
12% Cr
0.8
1.2
C (%)
1.6
0% Cr
5% Cr
0.8
1.2
C (%)
1.6
Cr is Ferrite stabilizer
Shrinking phase field with Cr
Austenite
600
500
400
300
200
100
Bainite
Ms
Mf
Martensite
~1 min
900
Tensile Test
400
300
200
100
0
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
450
Slowly cooled- 0.6%C
Quenched- 0.8% C
Slowly cooled- 0.8% C
Slowly cooled- 1.0% C
400
Hardness
Vikers Hardness
0.8% C - quenched
350
300
250
200
150
0.5
0.6
0.7
C%
0.8
0.9
1.1
Precipitation
Precipitation Hardening
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 with proper heat treatment (Al + 4% Cu + other alloying elements)
500 MPa
Al-Cu phase diagram: the sloping solvus line and the design of heat treatments
T (C)
600
400
200
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 ) CuAl 2 (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
B
A
4 % Cu
A
Hardness
100oC
Schematic curves
Real experimental curves
are in later slides
180oC
20oC
Log(t)
Higher temperature
Lower temperature
increased peak hardness
optimization between time and hardness required
Note: Schematic curves shown- real curves considered later
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/some solid solution
strengthening)
Peak-aged
Hardness
180oC
CRSS Increase
Log(t)
Particle
shearing
Particle
By-pass
r
r
Particle radius (r)
1
2
r f (t )
Hardness
A complex set of events are happening in parallel/sequentially during the aging process
These are shown schematically in the figure below
Log(t)
Increasing size of precipitates with increasing interparticle (inter-precipitate) spacing
Interface goes from coherent to semi-coherent to incoherent
Precipitate goes from GP zone
GP Zones
Cu rich zones fully coherent with the matrix low interfacial energy
(Equilibrium phase has a complex tetragonal crystal structure which has incoherent
interfaces)
Zones minimize their strain energy by choosing disc-shape to the elastically soft <100>
directions in the FCC matrix
The driving force (Gv Gs) is less but the barrier to nucleation is much less (G*)
2 atomic layers thick, 10nm in diameter with a spacing of ~10nm
The zones seem to be homogenously nucleated (excess vacancies seem to play an
important role in their nucleation)
5nm
Bright field TEM micrograph of an Al-4% Cu alloy
(solutionized and aged) GP zones.
5nm
Due to large surface to volume ratio the fine precipitates have a tendency to coarsen
small precipitates dissolve and large precipitates grow
Coarsening
in number of precipitate
in interparticle (inter-precipitate) spacing
reduced hindrance to dislocation motion (max = Gb/L)
''
Distorted FCC
10 nmthick ,100 nmdiameter
UC composition Al6Cu2 = Al3Cu
'
Becomes incoherent
as ppt. grows
Tetragonal
UC composition Al4Cu2 = Al2Cu
Schematic diagram showing the lowering of the Gibbs free energy of the system on sequential transformation:
GP zones
Phase Transformations in Metals and Alloys, D.A. Porter and K.E. Easterling,Chapman & Hall, London, 1992.
But, the free energy benefit in each step is small compared to the
overall single step process
Single step
(equilibrium) process
Schematic plot
Base
Al
Cu
Fe
Ni
Alloy
Precipitation Sequence
Al-Ag
Al-Cu
Al-Cu-Mg
Al-Zn-Mg
Cu-Be
Cu-Co
Fe-C
Fe-N
Ni-Cr-Ti-Al
' (Cubes/Spheres)
at start
Points to be noted:
In low T aging (130C) The aging curves have more detail than the single peak as discussed
schematically before.
In low T aging (130C) the full sequence of precipitation is observed (GPZ '' ').
At high T aging (190C) '' directly forms (i.e. the full precipitation sequence is not observed).
Peak hardness increases with increasing Cu%.
For the same Cu%, the peak hardness is lower for the 190C aging treatment as compared to the
130C aging treatment.
Peak hardness is achieved when the microstructure consists of a ' or combination of (' + '').
[1] J.M. Silcock, T.J. Heal and H.K. Hardy, J. Inst. Metal. 82 (1953-54) 239.
Particle/precipitate Coarsening
There will be a range of particle sizes due to time of nucleation and rate of
growth
As the curvature increases the solute concentration (XB) in the matrix adjacent to
the particle increases
Concentration gradients are setup in the matrix solute diffuses from near the
small particles towards the large particles
small particles shrink and large particles grow
with increasing time * Total number of particles decrease
* Mean radius (ravg) increases with time
Gibbs-Thomson effect
Gibbs-Thomson effect
3
avg
r0 ravg at t = 0
D Diffusivity
Xe XB (r = )
r kt
3
0
k D Xe
ravg
r0
t
Volume diffusion rate
Rate controlling
factor
dravg
dt
3
Linear ravg
versus t relation may break down due to diffusion short-circuits
Low Xe
ThO2 dispersion in W (or Ni) (Fine oxide dispersion in a metal matrix)
Oxides are insoluble in metals
Stability of these microstructures at high temperatures due to low value of Xe
The term DXe has a low value
Low D
ThO2 dispersion in W (or Ni) (Fine oxide dispersion in a metal matrix)
Cementite dispersions in tempered steel coarsen due to high D of interstitial C
If a substitutional alloying element is added which segregates to the carbide rate of
coarsening due to low D for the substitutional element