MME504 L9 30 Sept & 22 November 2022

Homogeneous Nucleation
MME 504 Lecture 8 Prof. S. Das 30 September 2022

2
Homogeneous Nuclation

3
Critical radius critical free energy
4 3 
ΔG  -  r .( Gv )  4r 2 .( )  
3 
d G
d G 0
0 dr
G
→
dr G  0
Total FE
Curve
2
r 
*
critical radius r* r0
Gv
of the nuclei
3
G  0 r0 
16  3
 16 T 2
Gv
G   *
G   3 m
3 Gv T 2 H 2
2
3
Critical radius critical free energy
Recall the expressions for critical radius
of the nuclei and the critical free energy
for homogeneous nucleation in the
previous slide,
r*= (2 γTm/ ΔHf) (1/ ΔT)
ΔG*= 16 πγ3 Tm2/ 3 ΔHf (1 / ΔT 2)
r* α (1/ ΔT) ΔG* α (1/ ΔT)2

r* and ΔG* decreases with increasing ΔT
Decreasing G*
r* r*
G →
r →

Definitions of Cluster / Embryo and Critical size
Cluster: a group of atoms that have the structure
of the one phase (say solid) in another (say melt);
for example, any group of atoms that form a
close packed structure in a melt will be called a
cluster
Embryo: a cluster
Critical nuclei: a cluster or embryo which has
reached a size at which even the addition of one
atoms makes it stable and even the removal of
one atom makes it unstable

Variation of r* and rmax with Undercooling
The figure clearly shows how rmax
varies with ΔT. Larger cluster than
rmax is possible in large enough system
one has to give sufficient time for
larger cluster to form. However the
probability to find slightly larger than rmax is
extremely small. The critical nucleus size
r* is shown decreases with increasing
undercooling.
It is observed that at small undercooling r* is so
large that there will be no probability of forming
a stable nucleus. However, at higher
undercooling r* decreases and at
supercoiling ΔTN or greater some cluster
reaching r* and growing into stable solid
particle.

8
Prob: (i)Calculate the critical radius of homogeneous nucleus from
pure liquid Cu. Assume: ΔT =0.2 Tm, ϒsl=0.177x10-4, Tm
=1083 oC ΔH =1826 j/cm3 (ii) Calculate the number of atoms in
critical sized nucleus at this undercooling
Assignment Due date: 7th October 2022

Homogeneous Nucleation Rate as a function
of undercooling.
Homogeneous Nucleation rate means
(Ihom) how fast a solid nuclei will appear
in the liquid at a given undercooling
(ΔT).
Let Co =No. of atom in a liquid per unit vol.
C* = No. of cluster of critical size per
unit vol. C* =Co exp( - ΔGhom/ KT
(K=Boltzmann’s Constant)
If we add one more atom to C*, then the
cluster will become a stable solid nuclei
Let fo = Frequency of formation of solid
nuclei
Ihom (Nucleation Rate) = fo Co exp( - ΔGhom/
KT )
[No. of stable nuclei/m3 .s]

fo Co = B1 DL/DLM = 10 33
B1 = 10 33 DL Diif. Coeff. of liquid DLM at MP

DL /DLM =1
ΔGhom = 16π (γsL )3 (TM )2 /3. (Lv)2 (ΔT)2
As soon as ΔT approaches ΔTN there is a tremendous

increase in the nucleation rate of solid (ΔTN = 0.2
TM ) for most metals ~ 200 K
HETEROGENEOUS NUCLEATION
LG Gas (G)
 Liquid(L)
SG LS Solid
ϒGS = ϒLS + ϒLG COSƟ

COS ϴ = ϒGS – ϒLS / ϒLG (Young’s Equation)
ϴ = Contact Angle
ϒGS = Surface energy of solid
ϒLG = Surface tension of Liquid
MME 504 Prof. S. Das 22 November 2022

Contact Angle
Mercury on a Glass Plate Water on a Glass Plate

Non-Wetting Condition Wetting Condition
2   
 
3
4
r *
 G
*
  2  3Cos   Cos 3

Gv 3 Gv
hetero hetero 2
d G
0
dr
1
G*hetero / G*homo →
G*hetero (0o) ~ 0
G*hetero (180o) = G*homo
very less barrier to nucleation
no benefit
0.75
G*hetero (90o) = G*homo/2
0.5
0.25
Complete wetting Partial wetting No wetting

0
0 30 60 90 120 150 180
 (degrees) →
Applications
Synthesis of Metal Matrix Composites: Need Lower ϴ
Metal and Ceramic combination The contact angle is
more than 90o (Non-wetting condition). To enhance
wettability (i) surface tension of the liquid has to
reduce and (ii) surface energy of the solid is to increase.
Self Cleaning Materials: Need Higherϴ ϴ
(Lotus Leaf-Inspired Nanotechnology)
(i) Synthesis of TiO2 Nano- Solution as

Self Cleaning Materials
(ii) Use of Mercury in Thermometer
(no wetting clearly visible)

MME504 L9 30 Sept & 22 November 2022

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Homogeneous Nucleation

MME 504 Lecture 8 Prof. S. Das 30 September 2022

MME 504 Lecture 8 Prof. S. Das 30 September 2022

Critical radius critical free energy

r* α (1/ ΔT) ΔG* α (1/ ΔT)2

MME 504 Lecture 8 Prof. S. Das 30 September 2022

MME 504 Lecture 8 Prof. S. Das 30 September 2022

MME 504 Lecture 8 Prof. S. Das 30 September 2022

MME 504 Lecture 8 Prof. S. Das 30 September 2022

MME 504 Lecture 8 Prof. S. Das 30 September 2022

B1 = 10 33 DL Diif. Coeff. of liquid DLM at MP

ΔGhom = 16π (γsL )3 (TM )2 /3. (Lv)2 (ΔT)2

As soon as ΔT approaches ΔTN there is a tremendous

LG Gas (G)

SG LS Solid

ϒGS = ϒLS + ϒLG COSƟ

MME 504 Prof. S. Das 22 November 2022

Mercury on a Glass Plate Water on a Glass Plate

Complete wetting Partial wetting No wetting

(i) Synthesis of TiO2 Nano- Solution as

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