Diffusional Transformation

Dr. Deni Ferdian, M.Sc

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Precipitation hardening – θ Al2Cu

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Micrograph showing θ’ precipitates in Micrograph showing θ precipitates in

Al-4%Cu, aged for 2 hours at 200 °C Al-4%Cu, aged for 45 mins at 450 °C.

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 Outline
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 Introduction
 Homogeneous nucleation
 Heterogeneous nucleation
 Precipitate growth
 Transformation kinetics
 Precipitation in age hardening alloy
 Eutectoid transformation
 TTT and CTT Diagram

INTRODUCTION

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 Key energy contributions

Chemical Driving force ∆Gm (Alloy thermodynamics)

Interfacial energy γαβ (Interface structure)

Elastic strain energy ∆Gε (State of coherency and misfit)

Coherent interfaces

Phase α

Phase β

Coherent Interface
Boundary α/β

Interfacial energy γch

3
 Semi-coherent interfaces

Phase α

Phase β

Semi-coherent Interface
Boundary α/β

b Interfacial energy
α − αβ D= γ =γ +γ
δ= α
αα δ sch ch D

Misfit dislocations

Incoherent interfaces

Phase α

Interfacial energy γich

Incoherent Interface
boundary α/β

4
 Interfacial energies

Interface boundary Interfacial energy (mJ/m2)

Coherent 1-200
Semi-coherent 200-500
Incoherent 500-1000

10

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 11

 Diffusional transformations are solid-state

transformations taking place by thermally activated
atomic movements.
 Types of phase transformations that are possible can
be roughly divided into:
 precipitation reactions;
 eutectoid transformations;
 ordering reactions;
 massive transformations; and polymorphic changes

Precipitation reactions
12

 Generally expressed in term:

’   + 
where ’ is a metastable supersaturated solid solution,  is a stable or
metastable precipitate, and  is a more stable solid solution with the same
crystal structure as ’, but with a composition closer to equilibrium.

6
 Ex. Copper precipitate
13

Eutectoid transformations
14
 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
long-range diffusion.

7
 Ex. Pearlite formation
15

16

Reaction
occurred without
any composition
change or long
range diffusion.

 (disordered)  ’ (ordered)

8
 17

The original phase

decomposes into one or
more new phases which
have the same
composition as the
parent phase, but
different crystal Massive transformation can
structures : proceed without any
 composition change or long-
range diffusion

Massive transformation – steel (δ→)

18

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 19

 Occur in a single component

system when different crystal
structures are stable over
different temperature ranges: 

E.g. bcc-fcc transformation in Fe 
Polymorphic change can A
proceed without any
composition change or long-
range diffusion.

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NUCLEATION

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 Homogeneous nucleation
21
 Consider the precipitation of B-rich β in
an A-rich α matrix. 

 B atoms have to cluster together in the α 
matrix to form a region of composition 

close to β and then further atomic re-

arrangements might be required for the
crystal structure to change to that of β.
  Creation of α/β interface

• At temperatures where the β phase is stable, the creation of a

volume V of β will cause a volume free energy reduction of VΔGV.
• Assuming for the moment that the α/β interfacial energy is
isotropic the creation of an area A of interface will give a free energy
increase of Aγ.

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 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.
 Thus, free energy change associated with nucleation has 3
contributions:
ΔG = −VΔGV + Aγ +VΔGS
 Volume free energy reduction;
 Interfacial energy; and
 Strain energy
With solid/liquid interface, γ can be treated as roughly the
same for all interfaces, but for nucleation in solids, γ can vary
widely from very low values for coherent interfaces to high
values for incoherent interfaces.

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 23

 Origin of strain energy: transformed volume will not

fit perfectly in the gap in the matrix  gives rise to
misfit strain.
 Also, the interfacial energy is not isotropic anymore
(unlike solid/liquid interfaces) but varies with
orientation
 Therefore summation over all surfaces is required, of
the nucleus ΣγiAi

Homogeneous Nucleation in Solids

 Homogeneous nucleation for spherical
nucleus
- Assumptions
Interfacial energy  is isotropic.
Spherical nucleus has a radius of curvature r.
- Free energy
Ghom  V  GV  A V  GS disappear grow
 Ghom  V  GV  GS  
 A  4r A
2

4 3
V  r
3
4
G hom   r 3  G V  G S   4r 2
3
GV: free energy reduction per unit volume.
Fig. The variation of G with r for a
GS: Increase of misfit strain energy per
homogeneous nucleus. There is
unit volume. an activation energy barrier G*.
Let r* = 1
r < 1  r2 > r3  G 
6
r > 1  r2 < r3  G 

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 Homogeneous Nucleation in Solids
- Critical radius of curvature r*
dGhom
0
dr r r *

 4r * 2 GV  GS   8r*   0

2
 r*  (5.7)
GV  GS

16
3
 G hom
*
 (5.8)
3  GV  G S2
- If r > r*, the nucleus will grow.
If r < r*, the embryo will disappear. The variation of ΔG with r for a
homogenous nucleus. There is
an activation energy barrier,
ΔG*

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 In the homogeneous nucleation, it

is assumed that the nucleation
rate is constant and the nuclei are
spherical with the equilibrium
composition and structure.

 In practice, however, nucleation

will be dominated by whatever
nucleus has the minimum energy
barrier and the rate is not
constant, and thus it will be hard
to achieve.

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In practice, homogeneous nucleation will be hard to

achieve, unless:
 Nucleus has orientation relationship with the
matrix.
 System that only has lattice parameter difference of
about 2%, e.g. Cu + 1-3 at% Co alloys - Cu and Co
exhibit FCC structure with a 2% mismatch in lattice
parameters
 Some other metastable phases which is not present
in the equilibrium phase diagram such as GP zones.

Heterogeneous nucleation
28

 Nucleation in solids, as in liquids, is almost always heterogen.

 Suitable nucleation sites are non-equilibrium defects such as

excess vacancies, dislocations, stacking faults, grain boundaries,
inclusions, and free surfaces, all which increase the free energy
of the materials.

 If the creation of a nucleus results in the destruction of defect,

some of free energy (Gd ) will be released thereby reducing (or
even removing) the activation energy barrier.
Ghet V GV GS AGd

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 Nucleation on grain boundaries
29

 The nucleus shape will be

the one that minimizes the
interfacial energy (ignoring
misfit strain energy effects)

 For incoherent grain

boundary nucleus, this
shape will be two spherical
caps joined at the grain
boundary

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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.

(a) The double hemispherical cap

model for the expected shape of an
incoherent precipitate at an -
grain boundary showing the
destroyed - grain boundary as
the dashed line.
(b) The Wulff construction for this
situation.

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 31
 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

Nucleation on grain boundaries

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 The main effect of dislocation is to reduce the ∆GS-contribution

to ∆G* by reducing the total strain energy of the embryo
 A coherent nucleus with a negative misfit can reduce its ∆G* by
forming in the region of compressive strain above an edge
dislocation.
 Nucleation on dislocations may be assisted by solute segregation
which can raise the composition of the matrix to nearer that of
the precipitate.
 The dislocation can assist in growth of an embryo beyond the
critical size by providing a diffusion pipe with a lower ∆Gm.
 Dislocations are not very effective for reducing the interfacial
energy contribution to ∆G*.

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 33

• This means that nucleation on dislocations usually requires

rather good matching between precipitate and matrix on at
least one plane, or that low-energy coherent or semicoherent
interfaces can form.
• High-angle grain boundaries are very effective nucleation
sites for incoherent precipitates with high γαβ.
• If the β precipitate can form low energy facets with the α
matrix, on one side of the grain boundary, then the critical
nucleus size can be further reduced.
• The nucleus will then have an orientation relationship with
one of the grains.

Nucleation on dislocations
34

 Lattice distortion in the vicinity of dislocations assists in

nucleation
 The main effect of dislocations is to reduce the ΔGs --
contribution to ΔG* by reducing strain energy of the embryo.
 Dislocations can also assist in nucleation by acting as diffusion
pipes -- short-circuit paths for diffusion -- lower ΔGm.
 Dislocations are not very effective in reducing interfacial energy
– This means that nucleation in dislocations usually requires
formation of a low energy coherent or semi-coherent interface
can be formed between precipitate and matrix (good matching
on at least one plane between precipitate and matrix)

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 Nucleation On Excess Vacancies
35
 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),

 small volume strain energy, and

 high driving force.

 These are essentially the same conditions that must be fulfilled for
homogeneous nucleation.

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PRECIPITATE GROWTH

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 Precipitate growth
37

• Critical nucleus that forms is the one with the smallest

nucleation barrier - smallest critical volume
• Ignoring strain energy effects the shape adopted is the one
with minimum interfacial energy
• Usually nuclei will be bounded by a combination of
coherent, semicoherent and incoherent interfaces
• Coherent and semi-coherent interfaces - specific
crystallographic relationship - usually planar faceted
interfaces
• Incoherent interfaces - smoothly curved

Precipitate growth
38

 When two phases have different crystal structures

semicoherent interfaces have very low mobility and are forced
to migrate by a ledge mechanism.

 Incoherent interfaces on the other hand are highly mobile.

 If there are problems in maintaining a constant supply of

ledges the incoherent interfaces will be able to advance faster
than the semicoherent interface and a nucleus with one plane
of good matching should grow into a thin disc or plate.

 This is the origin of the so-called Widmanstãtten morphology.

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Growth of Widmanstaetten ferrite in steel
39

Precipitate morphology – interface type

The effect of interface type on the morphology of a

growing precipitate. (A) Low-mobility
coherent/semicoherent interfaces. (B) High-mobility
semicoherent/incoherent interfaces.

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 Precipitate morphology
41

HAADF-STEM images of θ′ precipitates showing (a) the microstructure and

location of the coherent (C) and semi-coherent (SC) interfaces, displayed at
high resolution in (b) and (c) along [100] and [110] respectively. Both
interfaces exhibit structures that are not simple combinations of the structures
of the bulk phases θ′ and α (Al matrix).

Bourgeois et al., TMS meeting, 2015

Growth behind planar incoherent interfaces

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 Planar interfaces in crystalline solids will usually not

be incoherent.
 However, one situation where approximately planar
incoherent interfaces may be found is after grain
boundary nucleation.
 If many incoherent nuclei form on a grain boundary
they might subsequently grow together to form a slab
of β precipitate

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 43
 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.

Zener’s approximation (Linearized gradients)

44
 Clarence Zener* originated the approximation of linearizing the
concentration gradient.
 Simplify the concentration gradient by the sawtooth below:
conservation of solute dictates that the two shaded areas are equal (x is
now the thickness of the precipitate!):
 
 β 0 → =

Diffusion controlled thickening of a x’

precipitate plate

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 Calculation
45
 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

46

 Eq. 4 into Eq. 2:

2
 Rearrangement:

 Integration of the equation gives the distance, x

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 47
 The growth rate becomes:

 If it is assumed that the molar volume (Vm)

is constant, the concentration can be
replaced by mole fractions (X = CVm); and
for the simplicity, it can be assumed that (C
- C0)  (C - Ce).
 Thus the previous equation can be written in
the form:
The velocity change with undercooling;
the velocity is maximum at intermediate
undercooling because at high
undercoolings difusivity is high but
supersaturation is low, whereas at low
undercooling difusivity is low but
supersaturation is high.

Δ Δ x  (Dt); i.e. precipitate thickening

t obeys a parabolic growth law.
2 v  X0  (D/t); i.e. for a given time
the growth rate is proportional to the
supersaturation.
C. Zener, Journal of Applied Physics, Vol. 20, pp. 950-953, 1949

Overlap
48

 When the diffusion fields

separate precipitates begin
to overlap (a), the equation
will no longer apply, but
growth will decelerate and
finally cease when matrix
concentration is everywhere
(b).

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 Grain boundary diffusion
49

 Usually grain boundary

precipitates do not form a
continuous layer along the
boundary but remain as
isolated particles.
 The growth of such
precipitates can occur at
rates faster than allowed by
volume diffusion because
grain boundary can act as a
collector plate for solute.
This is also called allotriomorph,
involves three steps:
 Volume diffusion of solute to the
grain boundary
 Diffusion of solute along the grain
boundary with some attachment at
the precipitates rim, and
 Diffusion along the / interfaces
allowing accelerate thickening.

Lengthening of plates/needles
50
 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(C-Cr)}

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 Lengthening of plates/needles
51

 Given ΔX = ΔX0(1- r*/r)

Where ΔX0 =X0 –Xr
 The growth rate will be given by:

DX 0 1  r *
v . 1 
k( X   X r ) r  r 

where k is a constant (~1), r and r* are radius and

critical radius, respectively.

Ledge controlled thickening

52

 Turning now to the problem of how a platelet precipitate

can coarsen, i.e. increase in thickness, we consider the
effect of ledges on the flat surfaces.
 Each ledge is a line of incoherent interface, on which
solute can be readily attached.
 Velocity = uh/.

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 Ledge control, contd.
53
D X 0
u
 Velocity = uh/. 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(X - Xe)h be Xe and growth will be diffusion controlled
 Combining these equs:
v = D∆X0 / k(X - Xe)
 Thickening rate, v, inversely
proportional to ledge spacing, 
provided diffusion fields do not
overlap.
 Evidence suggests that actual
thickening rates are dependent
on nucleation of ledges.

54

AGE HARDENING

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 55

Alloys Evolution
56

Evolution of wing upper skin alloys and

The first age hardening curve tempers for passenger aircraft (Lukasak
published by Alfred Wilm and Hart, 1991)
(courtesy of J.W. Martin,
Precipitation Hardening,
Pergamon Press, Oxford, 1968)

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 Precipitation Heat Treatment

 Solution treatment, the sample is heated

at the temperature above solvus and
holding for a long time in order to make
all solute to be dissolved in the matrix.
 Quenching, the sample is then cooled
rapidly to a low temperature at which
the diffusion of solute is very slow. The
sample is now supersaturated.
 The supersaturated a solid solution is
usually heated to an intermediate
temperature T2 within the a+b region
(diffusion rates increase). The b
precipitates (PPT) begin to form as
finely dispersed particles. This process is
referred to as aging. After aging at T2,
the alloy is cooled to room temperature.
 Strength and hardness of the alloy
depend on the ppt temperature (T2) and
the aging time at this temperature.

Precipitation Heat Treatment

 PPT behavior is represented

in the diagram:
 With increasing time, the
hardness increases, reaching a
maximum (peak), then
decreasing in strength.
 The reduction in strength and
hardness after long periods is Small solute-enriched regions in a solid
overaging (continued particle solution where the lattice is identical or
growth). somewhat perturbed from that of the solid
solution are called Guinier-Preston zones.
Guinier-Preston (GP) zones - Tiny clusters
of atoms that precipitate from the matrix
in the early stages of the age-hardening
process.

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Several stages in the formation of the equilibrium PPT () phase.
(a) supersaturated  solid solution;
(b) transition (”) PPT phase;
(c) equilibrium  phase within the  matrix phase.

Precipitation in age hardening Al-4Cu alloy

60
 If an alloy, for example Al-4
wt% Cu, is heated to a
temperature of about 540 oC all
copper will be in solute solution
as a stable fcc  phase
 By quenching the specimen
rapidly into water there is no
time for any transformation to
occur so that the solid solution
is retained largely unchanged to
room temperature.
 Now the solid solution is
supersaturated with Cu and
there is a driving force for
precipitation of the equilibrium
 phase, Al2Cu.

30
 Precipitation in Aluminum-Copper Alloys
 Precipitation in Al-Cu alloys: transition phases
- The formation of GP zones is usually followed by the precipitation of so-called
transition phases.

- The equilibrium  phase is proceeded by ” and ’. The total precipitation process can
be
 1 GP  2 "  3 ' 4 
: the original supersaturated solid solution.
1: the composition of the matrix in equilibrium with GP
zones.
2: the composition of the matrix in equilibrium with ”.
3: the composition of the matrix in equilibrium with ’.
4: the composition of the matrix in equilibrium with .
GP zones ” phases ’ phases  phases

Fig. Microstructures at different stages during ageing of Al-Cu alloys. (a) GP zones. (b) ”. (c)
’. (d) .

Precipitation in Aluminum-Copper Alloys

- The free energy of the alloy undergoing the above precipitation sequence decreases
as shown in Fig. 5.27.
G0 G1 G2 G3 G4
Transformation stops when the minimum free energy equilibrium state G4 is reached, i.e.,
4 + .

Fig. A schematic molar free

energy diagram for the Al-Cu
system.

31
 Precipitation in Aluminum-Copper Alloys
- Transition phases form because they have a lower activation energy barrier for nucleation
than equilibrium phase.

The free energy of the alloy therefore decreases more rapidly via the transition phases than
by direct transformation to the equilibrium phase.

Fig. (a) The activation

energy barrier to the formation
of each transition phase is very
small in comparison to the
barrier against the direct
precipitation of the equilibrium
phase. (b) Schematic diagram
showing the total free energy
52
of the alloy vs. time.

GP Zone – θ‐Al2Cu
64
 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.

 Three metastable precipitates of GP-I, GP-II (θ”-phase), and θ’-phase can

be produced in addition to the stable θ-phase.

 In general, the process takes place according to the sequence of GP-I zone
→ GP-II zone (θ"-phase) → θ'-phase → θ-phase.

 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.

32
 Crystal structure of transition phases: θ” 
precipitates
- θ” has a tetragonal unit cell which is essentially a distorted fcc
structure in θ” which the Cu and Al atoms are ordered on (001) planes.
- Note that the atomic structure of the (001) planes is identical to that
in the matrix, and (010) and (100) planes are very similar, apart from a
small distortion in the [001] direction.
- θ” forms as fully coherent plate-like precipitates with a {001}α habit
plane and the following orientation relationship to the matrix:
(001)θ” // (001) α [100] θ” // [100]α
.

Crystal structure of transition phases: θ’ 

precipitates
66

- θ’ is tetragonal with an approximate composition Al2Cu and has (001)

planes that are identical with {001} α.
- The (100) and (010) planes have a different crystal structure to the
matrix and a large misfit in the [001] direction.
- θ’ forms as plates on {001} α with the same orientation relationship as
θ”.
- θ’ plates are ~1 µm diameter.

33
 Crystal structure of transition phases: θ
precipitates
67

- θ phase has the approximate composition Al2Cu and a complex

body-centered tetragonal structure.
- There are no planes of good matching with the matrix and only
incoherent interfaces are possible.

Al-Cu precipitate structures

GP zone structure

34
 Precipitation in Aluminum-Copper Alloys
 Full sequence of transition precipitates
- The full sequence of GP zones and transition precipitates is only possible when alloy is
aged at a temperature below the GP zones solvus.

- If ageing is carried out at a temperature above ”, heterogeneously but below the ’
solvus, the first precipitate will be ’, heterogeneously nucleated on dislocations.

- If an alloy containing GP zones is heated to above the GP zone solvus, the zones
will dissolve. This is known as reversion.

Fig. (a) Metastable solvus

lines in Al-Cu (schematic).
(b) Time for start of precipitation
at different temperatures for
57
alloy X in (a).

Precipitation in Aluminum-Copper Alloys

- For the case ”/’, the Cu concentration in the matrix close to the precipitates ” (2) will be
higher than that close to ’ (3). Therefore Cu will tend to diffuse through the matrix from
”, which thereby dissolves, and towards ’, which grows

Fig. Matrix in equilibrium with ” (2)

contains more Cu than matrix in
equilibrium with ’ (3). Cu diffuses as
shown causing ” to shrink and ’ to grow.

35
 Aging temperature effect – Al2Cu
71

Water quench + Water quench + Water quench + Water quench +

180oC for 6 hour 200oC for 2 hour 350oC for 45 min 450oC for 45 min

Precipitate Precipitate Precipitate Precipitate

GP zones +θ” θ’ θ’ + θ θ

Properties Properties Properties Properties

TS : 470 MPa TS : 436 MPa TS : 206 MPa TS : 190 MPa
Hardness : 160 HV Hardness : 144 HV Hardness : 66 HV Hardness : 60 HV

Al-Cu microstructures
72

 Different ppt types are associated with which part of the hardening
curve.

GP zones

’

36
 GP zone – β‐Mg2Si
73

GP Zone – Different Alloys

37
 Sequence in Age-Hardening Alloys

Mechanical properties of some commercial precipitation-hardening alloys.

Nucleation sites in Al-Cu alloys

76

b c

(a) ”  ’. ’ nucleates at dislocation; (b) 

nucleation on grain boundary; and (c) ’  . 
nucleates at ’ / matrix interface.

38
 Quench-in vacancies
77
 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.

Precipitate free zones (PFZs)

78
 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.

39
 79
 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.

80

Grain boundary precipitates and PFZ in Al-Mg2Si

aged at 310oC for 4 hours

40
 81

82

SPINODAL DECOMPOSITION

41
 Spinodal decomposition
83

 When there is no barrier in

nucleation, spinodal mode of
transformation can occur.
 Alloys between the spinodal
points are unstable and can
decompose into two coherent
phase 1 and 2 without
overcoming an activation
energy barrier.
 Alloys between the coherent
miscibility gaps and the
spinodal are metastable and
can decompose only after
nucleation of the other phase.

Spinodal Decomposition
- Chemical spinodal
The locus of the points on the phase diagram where
the free energy curve has a negative curvature.
d 2G
0 (5.42)
dx 2

Fig. Schematic composition profiles at increasing times in an

alloy quenched into the spinodal region (X0 i. 66

42
 Spinodal Decomposition
- If the alloy lies outside the spinodal, small variations in composition lead to increase in free
an energy and the alloy is metastable.

Outside the spinodal, the transformation must proceed by a

process of nucleation and growth. Normal down-hill diffusion
occurs in this case.

Fig. Schematic composition profiles at increasing times in an alloy

outside the spinodal region (X’0 ). 67

Spinodal Decomposition
 Chemical spinodal
- The rate of spinodal transformation is controlled by the
interdiffusion coefficient D.

- Within the spinodal, D < 0 and the composition fluctuations will

increase exponentially with time, with a characteristic time constant .
2
 
4 2 D
: wavelength of the composition
modulations.
The rate of transformation can become very high by making 
as small as possible. However, there is a minimum value of 
below which spinodal decomposition cannot occur.

- Two important factors that have been omitted must be

considered.
1. Interfacial energy effects.
2. Coherency strain energy defects.

43
 Spinodal decomposition
87
- 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
88

 Spinodal decomposition is of interest primarily due to its

inherent simplicity, and thus represents one of the few phase
transformations in solids for which there is any plausible
quantitative theory.
 Since there is no thermodynamic barrier to the reaction inside
of the spinodal region, the decomposition is determined solely
by diffusion.
 Spinodal decomposition is also of interest from a more
practical standpoint, as it provides a means of producing a
very finely dispersed microstructure that can significantly
enhance the physical properties of the material.
 A lot of examples of materials in real practice require such
defined phase segregation.

44
 Comparison Nucleation vs Spinodal

Nucleation & Growth Spinodal

A continuous change of composition
The composition of the second phase
occurs until the equilibrium values are
remains unaltered with time
attained
The interfaces between the nucleating The interface is initially very diffuse but
phase and the matrix is sharp eventually sharpens
There is a marked tendency for random
A regularity- though not simple- exists both
distribution of both sizes and positions of
in sizes and distribution of phases
the equilibrium phases
The separated phases are generally non-
Particles of separated phases tend to be
spherical and posses a high degree of
spherical with low connectivity
connectivity

Spinodal - Microstructure
90

A spinodal structure in a
specimen of Al-22.5 Zn-0.1 Mg
(at%) solution treated
at 400C and aged 20 h at 100C.
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.

45
Spinodal Decomposition : Cahn–Hilliard equation
model (1961)
91
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.

Notice that the mixture starts

out as an even mixture, and
after some time, becomes an
inhomogeneous mixture.
Although the patterns formed
are not completely
symmetric, they are also not
random.

Spinodal Decomposition in Fe-Cr

92

46
 93

PARTICLE COARSENING

Particle Coarsening
94
 Another consequence of the Gibbs-Thomson effect is that, even at
constant volume fraction (all the available precipitate volume fraction
has precipitated) there is a driving force for coarsening of the
precipitates. The reason for this is that smaller particles have a higher
solubility than larger particles.
 Mass conservation means that, if one particle grows then another
particle somewhere in the system must shrink.
 The mechanism for coarsening is diffusion, hence the kinetics follow an
Arrhenius law.
 The average increases with time because a shrinking small particle will
eventually disappear at which point the number of precipitates
decreases by one (and the average size increases).
 In most systems, coarsening starts immediately after nucleation.

47
 95

 The microstructure of two-phase alloy is always unstable if

the total interfacial energy is not minimum.
 Thus, a high density of small precipitates will tend to coarsen
into a lower density of larger particles with a smaller total
interfacial area.
 Such coarsening often produces an undesirable degradation
of properties such as loss of strength or the disappearance of
grain boundary pinning effects.
 The rate of coarsening increases with the temperature and is
particular concern in the design of materials for high
temperature applications.

Coarsening: thermodynamics
96
 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.

48
 Coarsening, contd.
97
 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 D  Xe 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

98

 Assuming that volume diffusion is the rate

controlling factor, it can be shown that:
̅
where ∝ and ( ̅ ) is the mean radius, r0 is the
mean radius at time t = 0; D is the diffusion
coefficient,  is the interfacial energy, and Xe is the
equilibrium solubility of very large particles.

49
 Coarsening, example of W-Ni-Fe
99

• r  t1/3 verified
• See extensive discussion
in Martin, Doherty & Cantor,
pp 239-298.

Coarsening - practical impact

100
 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).

50
 Coarsening (Ostwald ripening)
101

Suery, 2009

3D Tomography - Dendrite Growth and

coarsening

51
 103

EUTECTOID
TRANSFORMATION

Pearlite
104

52
 Eutectoid transformation
105

When autenite, for example,

containing about 0.8 wt% C is
cooled below the A1 temperature,
it becomes simultaneously
supersaturated with respect to
ferrite and cementite and
eutectoid transformation results,
i.e.    + Fe3C.

Nucleation and growth of pearlite

106

 The manner in which this reaction occurs is very

similar to a eutectic transformation where the
original phase is a liquid instead of a solid.
 In the case of Fe-C alloys, the resultant
microstructure comprises lamellae, or sheets, of
cementite embedded in ferrite, known as pearlite.

53
 Nucleation and growth of pearlite
107
On a grain boundary:
(i) Cementite nucleates on grain boundary with
coherent interface and orientation relationship
with 1 and incoherent interface with 2.
(ii)  nucleates adjacent to cementite also with a
coherent interface and orientation relationship
with 1.
(iii) The nucleation process repeats sideways,
while incoherent interfaces grow into 2.
(iv) New plates can also form by a branching
mechanism.

(b) When proeutectoid phase (cementite or

ferite) already exists on that boundary, pearlite
will nucleate and grow on the incoherent side
(2).
(c) Pearlite colony at a later stage of growth.

108

Figure. Growth and structure of pearlite: (a) redistribution of carbon and

iron, and (b) photomicrograph of the pearlite lamellae (2000). (From ASM
Handbook, Vol. 7, (1972), ASM International, Materials Park, OH 44073.)

54
 109

Figure. The evolution of the microstructure of hypoeutectoid and hypoeutectoid

steels during cooling. In relationship to the Fe-Fe3C phase diagram.

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.)

- Smaller T: - Larger T:

colonies are colonies are
larger smaller

55
 (a) Coarse pearlite and (b) fine pearlite
111

112

 When austenite is cooled to large

supersaturations below the nose of
the pearlite transformation curve, a
new eutectoid product called
bainite is produced.
 Like pearlite, bainite is a mixture of
ferrite and carbide, but its
microstructure is quite distinct
from pearlite; its microstructure
depends mainly on the
temperature at which it forms.

56
 Bainite Transformation
Upper bainite (a)
• At high temperatures (350C-550C) 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’.

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 ~350C.
• 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.

Fig. (a) Lower bainite in 0.69 wt% C low-alloy steel. (b) A

possible growth mechanism. / interface advances as fast
as carbides precipitate at interface thereby removing the
excess carbon in front of the .
(b)

57
 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 350C. The contrast is due to surface relief. (a) 14.75 min; (b) 16.2 min;
(c) 17.25 min; (d) 19.2 min.

116

58
Schematic Growth of Pearlite and Bainite
117

Bainite transformation
118

59
 119

TRANSFORMATION KINETICS

Transformation kinetics
120

 The progress of an isothermal phase transformation

can be conveniently represented by plotting the
fraction transformation (f) as a function of time and
temperature, i.e. TTT diagram.
 Among the factors determine f(t,T) are the nucleation
rate, the growth rate, the density and distribution of
nucleation sites, the overlap of diffusion fields from
adjacent transformed volumes, and the impingement
of adjacent transformed volumes.

60
 121

(a) Nucleation at a constant

rate during the whole
transformation,
(b) site saturation, all
nucleation occurs at the
beginning of
transformation, and
(c) a cellular transformation
(pearlite, massive
transformation,
recrystallization).

122

 As a simple example of derivation of f(t,T) consider

a cellular transformation () in which  cells are
continuously nucleated throughout the
transformation at a constant rate, N.
 If the cells grows as spheres at a constant rate, v,
the volume of a cell nucleated at time zero will be
given by:
4 4
3 3

61
 123

 A cell which does not nucleate until time  will have

a volume:
4
3
 The number of nuclei that formed in a time
increment of d will be Nd per unit volume of
untransformed .

124

 Thus, if the particles do not impinge on one

another, for a unit total volume:
4
3

3
 this equation only valid for f << 1.

62
 125

 For randomly distributed nuclei,

1 exp
3

 This is known as: Johnson-Mehl-Avrami equation.

126

 General form of Johnson-Mehl-Avrami equation can

be written in the form:
1 exp
where n is a numerical exponent whose value can
vary from ~1 to 4.
 n is independent of temperature, while k is depends
on the nucleation and growth rates and is therefore
very sensitive to temperature.

63
 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
 colony  

T just below TE T moderately below TE T way below TE

Nucleation rate low Nucleation rate med  Nucleation rate high
Growth rate high Growth rate med. Growth rate low

The Kinetics of Phase Transformation-

Kinetic considerations of solid-state transformation

 Rate of transformation : r = 1/ t0.5

 t 0.5 = time required for halfway to completion.
 Temperature will affect the rate of transformation:

Q
( )
r  Ae RT
 Q = activation energy
 Phase transformation is a thermal activated process.

128

64
 Rate of Phase Transformations
135C 119C 113C 102C 88C 43C

1 10 102 104
Pure Cu
Adapted from Fig. 10.11, Callister

 In general, rate increases as T  7e. (Fig. 10.11 adapted from B.F.

Decker and D. Harker,
"Recrystallization in Rolled Copper",

r = 1/t0.5 = A e -Q/RT Trans AIME, 188, 1950, p. 888.)

 R = gas constant Arrhenius expression

 T = temperature (K)
 A = ‘preexponential’ rate factor
 Q = activation energy
 r is often small so equilibrium is not possible!

The Kinetics of Phase Transformation-

Kinetic considerations of solid-state transformation

 Solid-state transformation did not occur

instantly.
 Need composition redistribution or atomic
rearrangement
 Energy increase for nucleation or new phase boundaries.
 Time-dependent process (kinetics): Avrami equation.

y  1  exp(  kt n )
k, n = time-independent constant ; k relates to r.

130

65
 131

TTT AND CTT DIAGRAM

Isothermal Transformation Diagrams

• Fe-C system, Co = 0.76 wt% C
• Transformation at T = 675°C.
100
% transformed

T = 675°C
y,

50

0
1 10 2 10 4 time (s)
T(°C)
Austenite (stable)
TE (727C)
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

66
 TTT diagrams
133

TTT diagram stands for “time-temperature-transformation” diagram. It is also

called isothermal transformation diagram

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

Ae1 Minimum incubation

T2 period t0 at the nose of
the TTT diagram,
Pearlite
T1
t1 t2 t3 t4 t5 Fine pearlite
t0
Hardness

50% very fine pearlite + 50% upper bainite MS=Martensite

start temperature
M50=temperature
Temperature

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

67
 Temperature versus composition in which various morphologies
are dominant at late reaction time under isothermal condition

Volume % of retained austenite

Austenite W=Widmanstätten
Ae3 plate
M=massive
0.0218 Ae1 0.77 CmW P=pearlite
αM αub=upper bainite
αW αlb =lower bainite
Temperature

Pearlite

Upper bainite

Lower bainite
MF
MS
Volume % of retained
Mix martensite austenite at room
temperature
Lath martensite Plate martensite
135 % carbon
Weight

TTT Curves showing the Bainite Transformation (a) Plain

Carbon Steels; (b) Alloy Steel w/ distinct Bainite “Nose”

From: George Krauss, Steels: Processing, Structure, and

Performance, ASM International, 2006.

68
 Metastable versus Equilibrium states
137

 Phase transformation is a time-dependent

process, long time is required to reach
equilibrium stage.
 Speed or rate of cooling is designed to produce specific
microstructure which the phase may not the
equilibrium one.  metastable phase.
 Supercooling or superheating happens very often in
practical purpose.

Isothermal Transformation Diagrams

138

 T~< 727oC (slightly lower):

 Phase transformation needs longer time
 Microstructure becomes coarse pearlite.

 T << 727oC (much lower):

 Phase transformation is quick.
 Microstructure is fine pearlite.

 which is called isothermal transformation

diagram. (Time-temperature-transformation,
T-T-T plot)

69
 Effect of Cooling History in Fe-C System
139
• Eutectoid composition, Co = 0.76 wt% C
• Begin at T > 727°C
• Rapidly cool to 625°C and hold isothermally.

Continuous Cooling Transformation Diagrams

70
 TTT and CCT Correlation
141

 The cooling curves refer

various distances from
the quenched end of a
Jominy end-quench
specimen
 Transformation occurs
along the hatched part of
the lines

Jominy Test
142

Measuring hardness on the

Jominy specimen and plotting the
Jominy hardenability curve.

71
 References
143

 D. A Porter, and K.E Easterling, Phase

Transformation in Metals and Alloys, 2nd ed.
Chapman and Hall, London, 1992.
 R.W. Chan, P. Haasen, Physical Metallurgy, North-
Holland, 1996.

72