Nucleation and Growth

Lecture 03
Solidification
2. Nucleation and Growth of Solids
Ref: A. Ohno, The Solidification of Metals, Chijin Shokan Co. Ltd., 1976
MME
materials & metallurgical engineering
© B. Rashid. October, 2013
Department of MME, BUET, Dhaka
3.0 Nucleation of solids

3.1 Homogeneous nucleation
3.2 Heterogeneous nucleation
3.3 Growth of nucleated crystals
© B. Rashid, DMME, BUET Lec #3: Nucleation & growth of solids Page 2 of 22
 If and when conversion from liquid to solid occurs, it is by a
process first of nucleation, and then of growth.
 Nucleation is a process of aggregation of clusters of atoms

representing the first appearance of the new phase.
kinetic energies of several atoms of molten metal reaches a low enough value so that
they form a short-range order, called a nucleus.
 Growth means getting bigger

As more heat is extracted, this newly formed nucleus continues to grow.
Surface free energy r* = critical radius

SL  free energy requirement
G* is the maximum.
FREE ENERGY, G
For r < r* :
 system lowers its free
r* RADIUS, r
energy by dissolution
of solid.
Total free energy  unstable nucleus.
G
Volume free energy
For r > r* :
GV
 free energy decreases
if the solid grows.
free energy change associated with nucleation
of a solid nucleus of radius r inside the liquid  stable nucleus.
 If the temperature is
sufficiently low, size of a
randomly nucleated embryo
will reach above the critical
size and its further growth will
be encouraged by a reduction
in energy.
thus growth will enter a ‘runaway’
condition
 Nucleation of solid of this type

is called homogeneous effect of decreasing temperature on critical radius for
nucleation nucleation and on free energy change for nucleation
 The temperature at which this event

can occur is called the homogeneous
nucleation temperature.
 For iron and nickel, this temperature is

hundreds of degrees below Te.
How such low temperatures are

attained by the liquid during freezing?
 Such low points are usually attained (a) Metal-mould interface at an early stage
during casting at the localised high when solid is nucleating at points of good
thermal contacts
point of mould wall where cooling is
so intense that homogeneous (b) The casting gains strength, both casting
nucleation is likely to occur and mould deform, reducing contact to
isolated points
 For a spherical embryo of radius
r, the energy equation: G*
G  (4/3) p r 3 . GV  4p r 2 .  SL
 2 SLTe  1 
r*     
 L  T 
T
 16p  SL 2 Te 2  1  2  r* varies inversely with T
G*   
3L 2  T   G* varies inversely with (T)2
 
 A melt is always in contact with the mould material,

 the area of the largest T (and the minimum G*)
must always exist at the metal-mould interface
nucleation occurs most readily at the mould interface
 Although we now know the critical values for an embryo

to become a nucleus, we do not know the rate at which
nuclei will appear in a real system
 To estimate the nucleation rate, we need to know the

population density of embryos of the critical size and the
rate at which such embryos are formed.
 The population (concentration) of critical embryos is

given by
G r k = Boltzmann factor

kT No = total number of atoms in the system
n r  n oe ∆Gr = excess of free energy associated with the cluster
Taking a ∆G equal to ∆G*,then the concentration of clusters to reach the
critical size can be written as:
G*

kT
C*  C o e clusters/m3
The addition of one more atom to each of these clusters would convert
them into stable nuclei If this happens with a frequency fo,
G *

kT
N hom  f 0 C o e nuclei/m3
A

( T ) 2
N hom  f 0 C o e nuclei/m3
16p 3sl Tm2

A
3L2 kT
 Besides, during actual melting, some foreign particles

(e.g. mould wall, inclusion/foreign particles, surface film)
are always present in the liquid
 nucleation occurs preferentially on these pre-existing surfaces
 the positive interfacial energy component in energy relation can be
reduced or even eliminated
 Nucleation of solid of this type is called heterogeneous

nucleation
 for a very favourable circumstance, nucleation can even be started at Te
 Homogeneous nucleation is only observed when no

heterogeneous nucleation sites are available in the liquid
 Not all foreign particles in liquid are favourable nuclei
for the formation of solid phase
(a) on a plane (b) along the edge (c) at a point
In case (a), total surface energy to overcome for heterogeneous

nucleation
s = solid, l = liquid
total = 6a2 sl – (a2 sl + a2 fl) + a2 sf
f = foreign body
Then, hom > het ; Ghom > Ghet
Thus, the more active the surface of foreign substrate, the smaller the value of ,
and the easier will be the nucleation to occur heterogeneously.
 Consider the nucleation of a spherical cup of solid on

a flat substrate
cl Liquid, l
Volume of the embryo sl 

crystal, c h
= (1/3)ph2 (3r – h) cs

substrate, s
= (1/3) pr3 (2 – 3cos + cos3)
 = contact angle between the
embryo and the substrate
r = radius of the embryo
Surface area of the embryo
h = height of embryo
= 2prh
 sl   cs
= 2pr2 (1 – cos) cos  
 cl
 Then the overall change in free energy
Ghet = (1/3) pr3 (2 – 3cos + cos3) Gv

+ 2pr2 (1 – cos) cl + pr2 (1 – cos2) (cs – cl)
surface area added at the Replacing substrate-liquid interface

new liquid-solid interface with solid-substrate interface
Ghet = S () . Ghom
(2 + cos ) (1 – cos )2

S () =
4
 For  = 180° (i.e., surface of substrate is non-wetted by the liquid):

Ghom = Ghet
 Oxides are, therefore, not good nuclei for heterogeneous
nucleation of solids because of their non-wetting surface
 For all other cases, where 0 <  <180°

Ghom > Ghet
and the substrate will aid nucleating the solid
 For  = 0° (i.e., surface of substrate is completely wetted by the liquid),

the energy barrier to nucleation is the minimum
To summarise:
 For a second phase to act as a nucleus must be
capable of being wetted by the liquid, forming a low
contact angle, and must possess some structural
affinity with the crystalline solid.
 Materials with good metallic properties (e.g. borides,

nitrides, carbides, intermetallic compounds) always
wetted by the liquid and are served as better nucleus.
 Also, foreign particles must remain as the solid form in

the liquid metal.
 The growth of an embryo will only occur if heat is

extracted through the solid, cooling the freezing front
below the equilibrium value
 As the rate of heat extraction increases, the temperature

of the solidification front falls, and the rate of advance, R,
of the front correspondingly increases.
 The mode of growth of individual crystal as well as of the

general solid mass depends mainly on two factors:
1. thermal conditions in the freezing zone,
2. constitution of the alloy,
3. shapes of the melt, solid, and mould
The solid - liquid Interface
 can be ‘smooth’ (when the boundary is discrete) or ‘rough’ (when the

transition extends over a number of atomic layers)
 the structure and form of the growing interface influences

both the microstructural morphology of the resultant solid
and also the number and distribution of imperfections
within the solid
 affects thermal and constitutional changes in the adjacent

liquid
the interaction between these effects can in turn lead to growth modifications
 A solid crystal is nucleated at the mould wall

because undercooling is maximum at the mould wall
 A nucleus makes contact with a foreign solid in

different ways (such as with the plane, edge, or point)
 Since crystal grows opposite to the direction of heat flow

and, thus, perpendicular to the mould wall, the growth
directions are different for those crystals having different
types of contact with the foreign solids
 In all those growth directions, there exists a preferential
growth of the nucleated crystal at the mould wall
The interface is not microscopically

uniform (presence of oxide film and
rough sand grains)
melt does not come in contact

uniformly with the mould wall and
wetting is different in different
positions
 Those nuclei having good

contact to the mould wall
will have higher T and will Irregular contact of molten metal with mould wall
and nucleation of crystal on the mould wall
grow preferentially
 A chill zone of randomly nucleated crystals is, therefore,

always found in the outer region of cast metals.
 Among all those

chill crystals only
a few have the
most preferential
growth directions,
and, therefore,
grow further
Preferential growth direction of crystal on the mould wall
To summarise:
 Since undercooling is the maximum at the mould
wall solid crystal is always nucleated at the mould
wall and form equiaxed chill zone.
 Since the mould wall is rough, those nuclei

having good contact with the mould wall will grow
preferentially and form columnar zone.
Next Class
Lecture 04
Solidification
3. Solidification of Pure Metals and Alloys

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Lecture 03

3.0 Nucleation of solids

 Nucleation is a process of aggregation of clusters of atoms

 Growth means getting bigger

Surface free energy r* = critical radius

 Nucleation of solid of this type

 The temperature at which this event

 For iron and nickel, this temperature is

How such low temperatures are

 A melt is always in contact with the mould material,

nucleation occurs most readily at the mould interface

 Although we now know the critical values for an embryo

 To estimate the nucleation rate, we need to know the

 The population (concentration) of critical embryos is

16p 3sl Tm2

 Besides, during actual melting, some foreign particles

 Nucleation of solid of this type is called heterogeneous

 Homogeneous nucleation is only observed when no

(a) on a plane (b) along the edge (c) at a point

In case (a), total surface energy to overcome for heterogeneous

 Consider the nucleation of a spherical cup of solid on

Volume of the embryo sl 

= (1/3)ph2 (3r – h) cs

Ghet = (1/3) pr3 (2 – 3cos + cos3) Gv

surface area added at the Replacing substrate-liquid interface

Ghet = S () . Ghom

(2 + cos ) (1 – cos )2

 For  = 180° (i.e., surface of substrate is non-wetted by the liquid):

 For all other cases, where 0 <  <180°

 For  = 0° (i.e., surface of substrate is completely wetted by the liquid),

 Materials with good metallic properties (e.g. borides,

 Also, foreign particles must remain as the solid form in

 The growth of an embryo will only occur if heat is

 As the rate of heat extraction increases, the temperature

 The mode of growth of individual crystal as well as of the

 can be ‘smooth’ (when the boundary is discrete) or ‘rough’ (when the

 the structure and form of the growing interface influences

 affects thermal and constitutional changes in the adjacent

 A solid crystal is nucleated at the mould wall

 A nucleus makes contact with a foreign solid in

 Since crystal grows opposite to the direction of heat flow

The interface is not microscopically

melt does not come in contact

 Those nuclei having good

 A chill zone of randomly nucleated crystals is, therefore,

 Among all those

 Since the mould wall is rough, those nuclei

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