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Diffusional Transformation
1
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1
Outline
3
Introduction
Homogeneous nucleation
Heterogeneous nucleation
Precipitate growth
Transformation kinetics
Precipitation in age hardening alloy
Eutectoid transformation
TTT and CTT Diagram
I NT RO D U C T I O N
2
5
Precipitation reactions
6
3
Ex. Copper precipitate
7
Eutectoid transformations
8
Involve the replacement of a
metastable phase by a more
stable mixture of two other
phase, and generally expressed
as:
+
Metastable phase (γ) replaced by
a more stable mixture of α + β +
Both precipitation and eutectoid
involve the formation of phases
with different composition to the
matrix and therefore require A B
long-range diffusion.
4
Ex. Pearlite formation
9
10
Reaction occurred
without any
composition change or
long range diffusion.
(disordered) ’
(ordered) ’
A B
5
11
6
13
14
NU C LEA T I O N
7
Homogeneous nucleation
15
16
In general, the transformed volume will not fit perfectly into
the space originally occupied by the matrix and this gives rise
to a misfit strain energy ΔGS, per unit volume of β.
8
17
18
For simplicity, assuming a
spherical nucleus,
4
Δ Δ Δ 4
3
∗
2
Δ Δ
∗
16
Δ
3 Δ Δ
9
19
20
10
Heterogeneous nucleation
21
11
23
The critical nucleus size (V*) for
grain boundary nucleation. The
ability of a grain boundary to
reduce ΔG*het, i.e. its potency as
a nucleation site, depends on
cos θ, i.e. on the ratio γαα/2γαβ.
24
cos θ determines the effectiveness of the
grain boundary nucleation site for
heterogeneous nucleation
Also, compared to grain boundary, grain
edges and grain corners can often act as
more effective nucleation sites, Why?
• If the matrix and
precipitate are
sufficiently compatible
to allow formation of
lower energy facets,
then G het reduced .
The critical nucleus size can
be reduced even further by • The nucleus will then
forming a low- energy Critical nucleus shape for
nucleation on a grain edge have an orientation
coherent interface with one relationship with one
grain. and corner.
of the grain
12
25
Nucleation on dislocations
26
13
Excess Vacancies
27
When an age-hardening alloy is quenched from a high temperature,
excess vacancies are retained during the quench.
These vacancies can assist nucleation by increasing diffusion rates or
by relieving misfit strain energies.
They may influence nucleation either individually or collectively by
grouping into small clusters.
Since ΔGd, is relatively small for vacancies, nucleation will only take
place when a reasonable combination of the following conditions is
met:
low interfacial energy (i.e. fully coherent nuclei),
These are essentially the same conditions that must be fulfilled for
homogeneous nucleation.
28
P REC I P I T A T E GRO W T H
14
Precipitate growth
29
Precipitate growth
30
15
Growth of Widmanstaetten ferrite in steel
31
16
Precipitate morphology
33
17
35
Imagine that such a slab of solute-rich
precipitate has grown from zero thickness
with the instantaneous growth rate of v.
Since the concentration of solute in the
precipitate (C) is higher than in the bulk
(C0) so the matrix adjacent to the v
precipitate will be depleted of solute.
Since the interface is incoherent diffusion-
controlled growth and local equilibrium at
the interface can be assumed, i.e. the solute
concentration in the matrix adjacent to the y
will be the equilibrium value, Ce. x
The growth rate will depend on the
concentration gradient at the interface
dC/dx.
18
Calculation
37
If J is number of atoms passing by an area of 1 m2/s, then
− = − (Eq. 1)
Minus sign means that the diffusion moves to the left side.
For solute conservation, A1 = A2:
−
− = − (Eq. 2)
2
Fick’s law states that = −
and from the profile, it can be seen that:
( − ) −
= or = − (Eq. 3)
− −
Eq. 3 into Eq. 1:
−
− = (Eq. 4)
−
38
−
=
− −
19
39
The growth rate becomes:
Overlap
40
20
Grain boundary diffusion
41
Lengthening of plates/needles
42
Imagine precipitate is a plate of
constant thickness having a
cylindrical curved incoherent edge of
radius r.
Due to Gibss-Thomson effect, the
equilibrium concentration in the
matrix increased to Cr.
For the (diffusion controlled)
lengthening of plates/needles, we
have to be concerned with the effect
of curvature.
Why? Because for a plate of constant
thickness, the curvature at the
growing tip remains constant and
small.
Why this shape? Because the Characteristic diffusion distance, L;
interface is coherent (and difficult to
grow) on one face (plates) but dC/dx = ∆C/L; L=kr (k~1)
incoherent around the edge (tip). v = D∆C/{kr(Cb-Cr)}
21
Lengthening of plates/needles
43
DX 0 1 r *
v . 1
k( X X r ) r r
22
Ledge control, contd.
45
D X 0
u
Velocity = uh/l. k X X h
Ledge speed, u If the edges of the ledges are incoherent, the
matrix composition in contact with the ledges will
= D∆X0 / k(Xb- Xe)h be Xe and growth will be diffusion controlled
Combining these equs:
v = D∆X0 / k(Xb- Xe)l
Thickening rate, v, inversely
proportional to ledge spacing, l,
provided diffusion fields do not
overlap.
Evidence suggests that actual
thickening rates are dependent
on nucleation of ledges.
23
In-situ solidification Al6.5Si1Fe
(reconstructed47
volume)
Ø = 1 mm
t=158.6 sec (609.4°C) t=183.9 sec (606.3°C) t=208.2 sec (602.4°C) t=241.5 sec (596.4°C)
Cooling rate 10°C/min t=258.7 sec (593.1°C) t=266.8 sec (591.8°C) t=275.8 (590.5°C) t=283.9 sec (589.4°C)
t=292 sec (588.5°C) t=300 sec (587.0°C) t=308.2 sec (585.4°C) t=359.7 sec (575.2°C)
24
Beta phase - Lateral growth
49
450
I II III
400
350
300
beta phase length (µm)
250
200
150
1
2
100
3
4
50
5
0
0 10 20 30 40 50 60 70
I – initial stage time (second)
II – peak stage
III – saturation stage The beta growth occurs continuously (error bar)
1.E+06
576.7°C
583.8°C
589.4°C
1.E+05
593.1°C
1.E+04
583.8°C 576.7°C
pixel count
1.E+03
1.E+02
1.E+01
25
Lateral and thickening growth rates
of beta51phase
60 2
lateral growth rate
thickening rate
50
1.5
40
1
30
0.5
20
0
10
0 -0.5
0 20 40 60 80 100 120
time (second)
52
T RA NS F O RM A T I O N K I NET I C S
26
Transformation kinetics
53
54
27
55
56
28
57
=
3
this equation only valid for f << 1.
58
= 1 − exp −
3
29
59
60
A GE H A RD ENI NG
30
61
Alloys Evolution
62
31
Precipitation Heat Treatment
32
Several stages in the formation of the equilibrium PPT (θ) phase.
(a) supersaturated α solid solution;
(b) transition (θ”) PPT phase;
(c) equilibrium θ phase within the α matrix phase.
33
GP Zone – θ-Al2Cu
67
If the alloy is now aged by holding for a period of time at room
temperature or some other temperature below 180 oC the precipitate will
form (coherent Cu-rich GP zones).
This zone is fully coherent and therefore has low interfacial energy. The
formation of GP zones is followed by precipitation of transition phases.
GP zones of the first kind (GP-I) are platelike arrays of copper layers
oriented parallel to {100} planes in the aluminum matrix, while GP zones
of the second kind (GP-II) consist of an ordered tetragonal structure of
aluminum and copper layers arrangements.
34
Crystal structure of transition phases: θ’
precipitates
69
35
Al-Cu precipitate structures
GP zone structure
36
Al-Cu microstructures
73
Different ppt types are associated with which part of the hardening
curve.
GP zones
θ’
GP zone – β-Mg2Si
74
37
GP Zone – Different Alloys
38
Nucleation sites in Al-Cu alloys
77
b c
Quench-in vacancies
78
When an alloy is rapidly quenched from high temperature
there will be no time for the new equilibrium concentration
to be established and high vacancy concentration becomes
quenched-in.
Given time, those vacancies in excess of the equilibrium
concentration will anneal out.
There will be tendency for a vacancies to be attracted
together into vacancy cluster, and some clusters collapse
into dislocation loops which can grow by absorbing more
vacancies.
Excess vacancies are able to provide heterogeneous
nucleation sites and can greatly increase the rate at which
atoms can diffuse at the ageing temperatures, and thus
speeds up the process of nucleation and growth GP zones.
39
Precipitate free zones (PFZs)
79
Excess vacancies also have an important
effect on the distribution of precipitates
that form in the vicinity of grain
boundaries on subsequent ageing.
When a critical vacancy concentration is
not exceeded, there will be no
nucleation, results in precipitate free
zone (PFZ) formation.
The width of PFZ is thus determined by
the vacancy concentration.
At low temperature, or high quench
rate, results in low critical vacancy
concentration narrow PFZs.
Wide PFZs are undesirable because they
adversely affect the mechanical and
corrosion properties of the alloy.
80
PFZs also can be caused by
nucleation and growth of
grain boundary precipitates
during cooling from the
solution treatment
temperature.
This cause solute to be
drained from the
surrounding matrix and
PFZs results. Figure shows PFZs around grain boundaries in a high
strength commercial Al-Zn-Mg-Cu alloy. Precipitate
on grain boundaries have extracted solute from
surrounding matrix.
40
81
82
41
83
S P I NO D A L D EC O M P O S I T I O N
Spinodal decomposition
84
42
Spinodal decomposition
85
- Miscibility gap
The miscibility gap that
normally appears on an
equilibrium phase diagram is
the incoherent miscibility gap.
This corresponds to the
equilibrium compositions of
incoherent phases, i.e. in the
absence of strain fields.
- Coherent miscibility gap
This is the line defining the
equilibrium compositions the Schematic phase diagram for a clustering system.
Region 1: homogeneous αα stable.
coherent phases that result from Region 2: homogeneous α metastable, only incoherent phases can
spinodal decomposition. nucleate.
Region 3: homogeneous α metastable, coherent phases can nucleate.
Region 4: homogeneous α unstable, no nucleation barrier, spinodal
decomposition occurs.
Spinodal Decomposition
86
43
Comparison Nucleation vs Spinodal
Spinodal - Microstructure
88
A spinodal structure in a
specimen of Al-22.5 Zn-0.1 Mg
(at%) solution treated
at 400C and aged 20 h at 100C.
The wavelength in the structure is
25 nm, but this is greater than the
initial microstructure due to
coarsening which occurs on
holding long times at high
temperatures.
44
Spinodal Decomposition : Cahn–Hilliard equation
model (1961)
89
The color represents the
concentration of the two
metals.
Green corresponds to an even
mixture of metal A and metal
B.
Red corresponds to all metal
A, Blue to all metal B.
45
Spinodal Decomposition in Fe-Cr
91
92
P A RT I C LE C O A RS ENI NG
46
Particle Coarsening
93
94
47
Coarsening: thermodynamics
95
The smaller particle with size r2 has a higher solubility (Gibbs-Thomson)
than the larger particle, r1, and so there is a concentration gradient that
causes solute to flow from particle 2 to particle 1.
Coarsening, contd.
96
The rate at which coarsening (also known as Ostwald Ripening)occurs is
clearly proportional to the driving force and the kinetic factors. Thus
higher coarsening rates should be associated with higher interfacial
energies, higher diffusion coefficients, and higher solubilities.
The kinetics of coarsening were worked out by Wagner and also by Lifshitz
and Slyozov. The quasi-steady-state distribution of sizes that emerges from
their analysis, while not a particularly good fit to experimentally
determined data, is known as the LSW Distribution.
The particle size varies as (time)1/3, in contrast to grain growth, which
follows a t1/2 dependence. The full equation is:
8 DXe 1 Xe Vm
r t rt 0
3 3
t
RT
2
9 Darken X Xe
ln B
Darken, or thermodynamic factor: Darken 1
ln XB
48
97
• r t1/3 verified
• See extensive discussion
in Martin, Doherty & Cantor,
pp 239-298.
49
Coarsening - practical impact
99
The practical impact of particle coarsening is highly significant.
Exposure to high temperatures will coarsen almost any system
and decrease strength (based on resistance to dislocation
motion).
Particle coarsening also reduces resistance to grain growth
(particles pin grain boundaries).
Sintering of powders is the basic consolidation process for
ceramics: coarsening limits minimum grain size (especially in
liquid-phase sintering because of enhanced diffusion rates).
Coarsening minimized in systems with low interfacial energies
and solubilities (e.g. Ni superalloys).
Suery, 2009
50
3D Tomography - Dendrite Growth and
coarsening
102
EU T EC T O I D
T RA NS F O RM A T I O N
51
Pearlite
103
Eutectoid transformation
104
52
Nucleation and growth of pearlite
105
53
107
108
54
Pearlite Morphology
• Ttransf just below TE (727oC) • Ttransf well below TE
--Larger T: diffusion is faster --Smaller T: diffusion is slower
--Pearlite is coarser. --Pearlite is finer.
10 m
Adapted from Fig. 10.6 (a) and (b),Callister 6e. (Fig. 10.6 from R.M. Ralls et al., An Introduction to
Materials Science and Engineering, p. 361, John Wiley and Sons, Inc., New York, 1976.)
55
111
Bainite Transformation
Upper bainite (a)
• At high temperatures (350C-550C) bainite
consists of needles or laths of ferrite with
cementite precipitates between the laths. This is
known as upper bainite.
• The ferrite nucleates on a grain boundary with a
Kurdjumov-Sachs orientation relationship with
one of the austenite grains, 2.
• Since the undercooling is very large the nucleus
grows most rapidly into the 2 grain forming
ferrite laths with low energy semicoherent
interfaces.
• As the laths thicken the carbon content of the
austenite increases and finally reaches such a level
that cementite nucleates and grows.
• The greatest difference between pearlite and
bainite lies in their crystallography.
• In the case of pearlite the cementite and ferrite
have no specific orientation relationship to the
austenite grain in which they are growing,
whereas the cementite and ferrite in bainite do (b)
have an orientation relationship with the grain in (c)
which they are growing.
(b) Schematic of growth mechanism. Widmanstätten ferrite laths
growth into 2. cementite plates nucleate in carbon-enriched
austenite. (c) Illustrating the shape of a ‘lath’.
56
Bainite Transformation
Lower bainite
• At sufficiently low temperatures the microstructure of
bainite changes from laths into plates and the carbide
dispersion becomes much finer, rather like in tempered
martensite
• The temperature at which the transition to lower
bainite occurs depends on the carbon content in a
complex manner.
• For carbon levels below ~0.5 wt% the transition
temperature increases with increasing carbon, from
0.5-0.7 wt% C it decreases and above ~0.7 wt% C it is
constant at ~350C.
• The carbides are either cementite or metastable
transition carbides such as ε-carbide and they are an
aligned at approximately the same angle to the plane of
the ferrite plate
• The habit plane of the ferrite plates in lower bainite is
the same as that of the martensite that forms at lower
temperatures in the same alloy.
Bainite Transformation
Transformation shears
• If a polished specimen of austenite is transformed to bainite (upper or lower)
it is found that the growth of bainite laths or plates produces a surface relief
effect like that of martensite plates.
• The bainite plates form by a shear mechanism in the same way as the growth
of martensite plates. There is, however, much uncertainty regarding the
mechanism by which bainitic ferrite grows, and the nature of the austenite-
ferrite interface in martensite and bainite.
Fig. Photos taken with a hot-stage microscope showing the nucleation and growth of
bainite plates at 350C. The contrast is due to surface relief. (a) 14.75 min; (b) 16.2 min;
(c) 17.25 min; (d) 19.2 min.
57
115
58
Bainite transformation
117
118
T T T A ND C T T D I A GRA M
59
Nucleation and Growth
• Reaction rate is a result of nucleation and growth of crystals.
100
% Pearlite Growth
Nucleation rate increases with T
50 Nucleation
regime Growth rate increases with T
regime
Adapted from
0 t0.5 log(time) Fig. 10.10, Callister 7e.
• Examples:
pearlite
γ colony γ γ
Q
( )
r Ae RT
Q = activation energy
Phase transformation is a thermal activated process.
120
60
Rate of Phase Transformations
135C 119C 113C 102C 88C 43C
1 10 102 104
Pure Cu
Adapted from Fig. 10.11, Callister
r = 1/t0.5 = A e -Q/RT
"Recrystallization in Rolled Copper",
Trans AIME, 188, 1950, p. 888.)
y 1 exp( kt n )
k, n = time-independent constant ; k relates to r.
122
61
Avrami Equation
Avrami rate equation => y = 1- exp (-ktn)
•The initial slow rate can be attributed to the time required for a significant
number of nuclei of the new phase to form and begin growing.
•During the intermediate period the transformation is rapid as the nuclei grow into
particles and consume the old phase while nuclei continue to form in the
remaining parent phase.
•Once the transformation begins to near completion there is little untransformed
material for nuclei to form in and the production of new particles begins to slow.
Further, the articles already existing begin to touch one another, forming a
boundary where growth stops.
(austenite)
1000
α Eutectoid: γ +Fe3C
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727°C
∆T
600 α+Fe3C
Undercooling by ∆Ttransf. < 727C
0.022
0.76
400
0 1 2 3 4 5 6 6.7
(Fe)
Co , wt%C
62
Phase Transformations of Alloys
100
T = 675°C
y,
50
0
1 10 2 10 4 time (s)
T(°C) Austenite (stable)
TE (727C)
700 Austenite
(unstable) Adapted from Fig. 10.13,Callister 7e.
(Fig. 10.13 adapted from H. Boyer (Ed.) Atlas of
600 Pearlite Isothermal Transformation and Cooling
isothermal transformation at 675°C Transformation Diagrams, American Society for
Metals, 1977, p. 369.)
500
400
time (s)
1 10 10 2 10 3 10 4 10 5
63
TTT diagrams
127
Time temperature transformation (schematic) diagram for plain carbon eutectoid steel
% of Phase
100
T1 T2 At T1, incubation
50%
period for pearlite=t2,
0 Pearlite finish time =t4
Upper bainite
for 50% martensite
formation
MF= martensite
finish temperature
Lower bainite
MS, Martensite start temperature
M50,50% Martensite
Metastable austenite +martensite
MF, Martensite finish temperature
Martensite
Log time
64
Temperature versus composition in which various morphologies
are dominant at late reaction time under isothermal condition
Pearlite
Temperature
Upper bainite
Lower bainite
MF
MS
Volume % of retained
Mix martensite austenite at room
temperature
Lath martensite Plate martensite
129 % carbon
Weight
65
Metastable versus Equilibrium states
131
66
Effect of Cooling History in Fe-C System
133
• Eutectoid composition, Co = 0.76 wt% C
• Begin at T > 727°C
• Rapidly cool to 625°C and hold isothermally.
67
TTT and CCT Correlation
135
Jominy Test
136
68
References
137
69