Science in China Ser. E Engineering & Materials Science 2004 Vol.47 No.

4 391397 391
The mathematical model of wetting angle of
heterogeneous nucleation
HUANG Cheng
1
, SONG Bo
1
, MAO Jinghong
2
& ZHAO Pei
3
1. School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Bei-
jing 100083, China;
2. School of Material Science, University of Science and Technology Beijing, Beijing 100083, China;
3. Central Iron and Steel Research Institute, Beijing 100081, China
Correspondence should be addressed to Huang Cheng (email: schonheitsfehler@sohu.com)
Received July 18, 2003
Abstract The heterogeneous nucleation has been analyzed in terms of the
thermodynamic theory, and the mathematical model of wetting angle of heterogeneous
nucleation has been developed based on the dynamic requirements of hetero- and
homogeneous nucleation. With the wetting angel model, the wetting angles of different
catalysts in liquid iron have been calculated. The result shows that the wetting angle of
most catalysts is smaller than 40, and the value of f() is far less than 1. The wetting
angles of TiN, TiC and RE
2
O
3
are smaller, while the wetting angle of MnO is bigger
among the ordinary nucleation catalysts. The wetting angles calculated by this model are
in agreement with the results of other research work.
Keywords: heterogeneous nucleation, mathematical model, wetting angle, undercooling.
DOI: 10.1360/ 03ye0364
According to the classical theory of nucleation, the nucleation of the metal can take
place through either heterogeneous nucleation or homogeneous nucleation. The homo-
geneous nucleation is a process in which there are not any foreign particles or objects
available, and all the nuclei are formed in pure liquid metal. When the melt contains
solid particles, or it contacts a crystalline surface or voids, the nucleation is facilitated
because the activation energy required for nucleation decreased, which is the so-called
heterogeneous nucleation. Compared with the homogeneous nucleation, the heteroge-
neous nucleation has the same nucleation radius, smaller activation energy of nucleation,
because the heterogeneous nucleation is heavily influenced by the wetting angle between
the catalyst and nucleus. So heterogeneous nucleation is easier than homogeneous
nucleation. When the wetting angle is equal to 180, the heterogeneous nucleation is the
same as the homogeneous nucleation. In practice, metal materials are produced through
the heterogeneous nucleation. Up to date there has been little report concerning the
model of wetting angle. In this paper, based on the theory of nucleation, a mathematical
model of wetting angle has been developed, so as to calculate the wetting angle of dif-
Copyright by Science in China Press 2004
392 Science in China Ser. E Engineering & Materials Science 2004 Vol.47 No.4 391397
ferent catalysts in liquid iron.
1 Theoretical analysis
The classical model of heterogeneous nucleation assumes that the solid nucleus is
formed as a spherical cap-shaped particle at the catalyst-liquid interface, as shown
schematically in fig. 1. According to the classical theory
[1]
, the angle between nucleus
and catalyst is called wetting angle. When a nucleus is formed on the catalyst, there are
three types of interface energy, o
LS
(liquid-solid), o
LC
(liquid-catalyst), o
SC
(solid-
catalyst), as seen in fig.1.

Fig. 1. The heterogeneous nucleation.

The equilibrium condition of the interface energy can be expressed by

LC SC LS
cos , o o o u = + (1)
where o
LC
is the interface energy between catalysts and liquidJgm
2
; o
SC
is the in-
terface energy between catalyst and nucleusJgm
2
; o
LS
is the interface energy be-
tween catalysts and liquid, Jgm
2
; u in degrees is the wetting angle,

LC SC
LS
cos .
o o
u
o

= (2)
The wetting angle can be calculated with eq. (2) with the data of interface energy.
However, the data of interface energy between liquid and catalysts, especially the inter-
face energy data between catalyst and nucleus are sparse, and the data calculated from
some interface energy model are not accurate. In this paper, the mathematical model of
wetting angle is derived from thermodynamics and dynamics.
2 Modeling
When the temperature of a melt descends to a certain degree, the nucleus would be
formed in the melt. As the nucleus is different from atoms in size in the melt, the nucleus
and the atoms of melt are likely to mix, through which the entropy increases and the
systems Gibbs free energy decreases. In a closed system, the process of the entropy in-
creasing is a spontaneous process to decrease the Gibbs free energy. So, the Gibbs free
energy change between the mixed system (including solid nucleus and liquid atoms) and
pure liquid system (only liquid atoms contained) can be expressed as
[1]

Copyright by Science in China Press 2004
The mathematical model of wetting angle of heterogeneous nucleation 393
(3) ,
e n n
G N G T S A = A A
where AG
e
is the Gibbs free energy change between the mixed system and pure liquid
system, J; N
n
is the number of nucleus in the melt; AS
n
is the configurational entropy,
JgK
1
; AG is the Gibbs free energy change to form a nucleus, J.
Still more, AS
n
can be calculated by
( )
1
ln !/ ! ! ,
n n n
S k N N N N
1
( A = +

(4)
where N
1
is the number of liquid atoms; N
n
is the number of nuclei; and K is the Boltz-
mann constant, 1.38 10
23
JgK
1
.
Combining eq. (3) and eq. (4), we get
(5)
1
ln( )! ln( )! ln( )!.
e n n n
G N G kT N N kT N kT N A = A + + +
1
As eq. (5) can be simplified into ln ! ln , N N N N ~
(6)
1 1 1 1 1
[ ln( ) ln( ) ln ln( )].
e n n n n n n
G N G kT N N N N N N N N N N A = A + + +
The Gibbs free energy change AG
e
has a minimum value under a certain under-
cooling. When AG
e
reaches this minimum point, the system is in the most stable state
and the corresponding N
n
is the equilibrium number of nuclei under certain undercooling.
Differentiating eq. (6) with respect to N
n
and letting / 0,
e n
d G dN A = we have

1
[ln( ) ln ] 0,
n n
G kT N N N A + = (7)
or
(8)
1
/( ) exp( / ).
n n
N N N G kT + = A
As the equation above can be written as
1
,
n
N N >>

| |
1
/ exp /
n
N N G kT = A . (9)
Thus, the number of nuclei with the critical radius of nucleation is

* *
1
exp / ,
n
N N G kT
(
= A

(10)
where AG
*
is the nucleus-forming activation energy, J; and is the number of nuclei
with the critical radius.
*
n
N
Substituting into eq. (6), we can calculate the minimum value of Gibbs free
energy change AG
*
n
N
e
.
The dynamic requirement for the nucleation of melt is that there is at least one sta-
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394 Science in China Ser. E Engineering & Materials Science 2004 Vol.47 No.4 391397
ble nucleus with the critical radius formed in the melt, whether for homogeneous or het-
erogeneous nucleation. When a stable nucleus is formed in the melt, the nucleation and
further solidification start to take place. The temperature at which the first nucleus is
formed is called the critical temperature.
For the homogeneous nucleation, the dynamic requirement of nucleation can be
expressed by
(11)
* *
1
exp / 1.
ho
n
N N G kT
(
= A

The activation energy of homogeneous nucleation is

3
LS
2
16
,
3
V
G
G
to
-
A =
A
(12)
where o
LS
is the interface energy between solid and liquid, Jgm
2
; and AG
v
is the nu-
cleation driving force of per unit volume melt, Jgm
3
.
Combining eq. (11) and eq. (12), we can obtain

3
* LS
1
2
16
exp 1.
3
ho
ho
n
V ho
N N
G KT
to
(
=
A
(

( (13)
The activation energy of heterogeneous nucleation is

3
LS
2
16 ( )
,
3
V
f
G
G
to u
-
A =
A
(14)
where f

(u ) is a factor of the contact angle and is given by

3
1
( ) (2 3cos cos ).
4
f u u = + u (15)
Combining eq. (10) and eq. (14), we get

3
* LS
1
2
16
exp ( ) .
3
he
he
n
V he
N N f
G KT
to
u
(
= (
A
(

(16)
For the heterogeneous nucleation, the dynamic requirement of nucleation can be
expressed by

3
*
1
2
16
exp ( ) 1.
3
he
he
n
V he
N N f
G KT
to
u
(
=
A
(

( (17)
At the critical state, both the homogeneous nucleation and heterogeneous nuclea-
tion have only one stable nucleus in the melt. Combining eq. (13) and eq. (17), we get
Copyright by Science in China Press 2004
The mathematical model of wetting angle of heterogeneous nucleation 395
(18)
2
( ) .
ho he
V ho V he
G T f G T u A = A
2
The thermodynamic driving force per unit volume G
v
is

3
10
,
v m
G G
m

A = A (19)
where is the density of metal, kggm
3
; m is the atomic weight of metal, kggmole
1
;
and AG
m
is the nucleation driving force per mole, Jgmole
1
.
Substituting eq. (19) into eq. (18), we get

2
2
( ) ,
he
ho
m he
m ho
G T
f
G T
u
A
=
A
(20)
in which T
he
and T
ho
are the critical temperature of heterogeneous and homogeneous nu-
cleation respectively.
AG
m
can be calculated by
( ) ,
m m
c c
T T
PL PS
m m PL PS m
T T
C C
G H C C dT T S dT
T
( | |

| ( A = A A
|
(
\ .
) )
(21)
where AH
m
is the latent heat of fusion, Jgmol
1
; T
m
is the melting temperature, K; T
c
is
the solidifying temperature, K; AS
m
is the entropy of fusion, Jgmol
1
gK
1
; C
PL
is the
specific heat of undercooled liquid metal, Jgmol
1
gK
1
, and C
PS
is the specific heat of
solid metal, Jgmol
1
gK
1
.
If C
PL
= C
PS
, eq. (20) can be simplified to
,
m m m
m
T
G H H
T

A
A = A = A (22)
where AT is the undercooling, K; and is the relative undercooling.
If AG
m
is calculated by eq. (22), eq. (20) can be further simplified to

2
2
( ) .
he he
ho ho
T
f
T

= (23)
Refs. [2, 3]

theoretically studied the undercooling of homogeneous nucleation, and
the results showed that the maximum value of undercooling is 2/3T
m
, and the tempera-
ture of homogeneous nucleation is only one third of the melting temperature, i.e. 603 K.
Eqs. (20) and (23) are the mathematical model of the wetting angle. In one melt, if
catalyst 1 has wetting angel u
1
and critical undercooling
1
, and catalyst 2 has wetting
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396 Science in China Ser. E Engineering & Materials Science 2004 Vol.47 No.4 391397
angel u
2
and critical undercooling
2
, based on eq. (23), the following relationship can
be obtained:

1 1
2 2
2
1
2
2
( )
.
( )
he he
he he
T
f
f T

u
u
= (24)
3 The application of the model
From eq. (20), it can be seen that if the critical temperatures of different catalysts in
liquid iron are available, then the wetting angle of different catalysts can be calculated.
The critical temperatures of different catalysts are shown in table 1, and the parameters
for calculation are listed in table 2.

Table 1 The critical temperatures and relative undercoolings of different catalysts in liquid steel
Type of catalysts Undercooling/K Critical temperature/K Relative undercooling
TiN
[4]
1.7 1807.3 0.00094
TiC
[4]
1.8 1807.2 0.001
SiC
[4]
4.2 1804.8 0.0023
ZrN
[4]
7 1802 0.0039
ZrC
[4]
13.6 1795.4 0.0075
WC
[4]
16.2 1792.8 0.009
Al
2
O
3
[5]
13.9 1795.1 0.0077
SiO
2
[5]
29.5 1779.5 0.016
RE
2
O
3
[5]
3.0 1806 0.0017
MnO
[5]
52.7 1756.3 0.029

Table 2 Physical parameters used for the calculation in this work
[68]
Metal
Melting
point/K
C
PS
/Jgmol
1
gK
1
C
PL
/Jgmol
1
gK
1
AH
m
/KJgmol
1
AS
m
/Jgmol
1
gK
1
o
LS
/Jgm
12
Q/J T
ho
[2,3]
Fe 1809 24.635 + 0.009904T 48.6 15.2 8.4 0.254 1.110
-19
T
m
/3

Based on the data in table 1 and table 2 and eq. (20), the wetting angles of different
catalysts in liquid iron are calculated and the results are shown in table 3. The results
show that the wetting angle of most catalysts is smaller than 40, and f

(u

) of most effec-
tive catalysts is far less than 1, meaning that the activation energy of heterogeneous nu-
cleation with such catalysts is smaller than that of homogeneous nucleation. The wetting
angles of TiN, TiC and the RE
2
O
3
are relatively small, while the wetting angle of MnO
is bigger among the ordinary nucleation catalysts. In this paper, we suppose that the dy-
namic requirement of nucleation is that there is at least one stable nucleus in the melt, so
the result obtained from this model is accurate and convincing. It can be seen from table
3 that the wetting angle calculated by this model is in agreement with the results of other
research work.
Copyright by Science in China Press 2004
The mathematical model of wetting angle of heterogeneous nucleation 397
Table 3 Calculated wetting angle of different catalysts in liquid iron
Calculated results Result from ref. [5]
Type of catalysts
f

(u

) u

u


TiN 0.000044 7.1
TiC 0.000049 7.3
SiC 0.000268 11.2
ZrN 0.000743 14.4
ZrC 0.00278 20.2
WC 0.0039 22.1
Al
2
O
3
0.0029 20.5 18.3
SiO
2
0.013 30.1 26.8
RE
2
O
3
0.000137 9.4 8.5
MnO 0.04 40.7 36.5

4 Conclusions
() In this paper, the mathematical model of the wetting angle of heterogeneous
nucleation was developed.
() Based on this model, the wetting angle of different nucleation catalysts in liq-
uid iron was calculated. The result shows that the wetting angles of TiN, TiC and RE
2
O
3

are smaller, while the wetting angle of MnO is bigger among the ordinary nucleation
catalysts.
() The relationship of f

(u

) with undercooling of different catalysts was devel-
oped.
() The wetting angles calculated by this model are in good agreement with other
researchers results.
Acknowledgements This work was supported by the National 973 Research Program of China (Grant No.
J1998061511-2).
References
1. Hu Hanqi, Fundamentals of Metal Solidification (in Chinese), Beijing: Mechanical Industry Press, 1991, 42
55.
2. Liang Guoxian, Wang Erde, Huo Wencan, Relationships between degree of undercooling in solidification and
thermal properties of metals, Materials Science Progress, 1991, 5(4): 277283.
3. Jian Zengyun, Chang Fange, Ma Weihong, Nucleation and undercooling of metal melt, Science in China, Se-
ries E, 2000, 43(2): 113119.
4. Branfutt, B., The effect of carbide and nitride additions on the heterogeneous nucleation behavior of liquid
iron, Metallurgical Transactions, 1970, (1): 19871995.
5. Ohashi, T., Hiromoto, T., Fuju, H. et al., Effect of oxides on nucleation behavior in supercooled iron, Iron and
Steel, 1976, (6): 614623.
6. Liang Yinjiao, Che Yinchang, Inorganic Thermodynamic Data Book (in Chinese), Shenyang: Northeast Uni-
versity Press, 1993, 145146.
7. Brandes, E. A., Smithells, C. J., Metals Reference Handbook, 7th ed., London: Butterworths, 1980, 1396.
8. Wei Binbo, Wang Bin, Barthm, Herlach, D. M., The thermodynamic driving force of rapidly solidification of
liquid metal, Acta Metallurgical Sinica (in Chinese), 1994, 30(7): 289293.
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