Chapter 15 Nucleation and growth kinetics

15.4 The following data are relative to the freezing of the pure metal copper: the melting point of
copper is 1356 K; its latent heat of fusion is 2.117105 J/kg; its atomic weight is 0.06355
kg/mol; the surface energy of the liquid-solid interface is 0.177 J/m2; and the density is
8.35103 kg/m3. (N: 6.0221023 atoms/mol)
(a) Compute hls, the heat of fusion per atom, in J.
(b) Evaluate the coefficients of both n and n2/3 in Eq. 15.17 (Gn = ngls + lsn2/3).
(c) Determine the number of atoms in a critical nucleus when the supercooling is 5, 50, and
200 degrees.
(a) H ls  2.117  105 J / kg , M  0.06355kg / mol , N  6.022  1023 atoms / mol
H ls M
hls 
N
 J   kg 
  2.117  105    0.06355 
 kg   mol  J
 h 
ls
 2.234  10 20
atoms atom
6.022  1023
mol

(b) M  0.06355kg / mol , D  8.35  103 kg / m3 , N  6.022  1023 atoms / mol , T0  1356 K

 ls  0.177 J / m 2
kg
0.06355 3
M mol  29 m
vl    1.264  10
DN  3 kg   23 atoms  atom
 8.35  10 3    6.022  10 
 m   mol 
  4 1 / 3 3vl 2 / 3  4 1 / 3  3  1.264  10 29 m3 
2/3
 2.624  1019 m 2
hls T
 g ls 
T0
 h ls T 
Gn  ng ls   ls n 2 / 3   n   ls n 2 / 3
 T0 

 Gn  

  2.234  10  20 T   
19

 n  2.624  10  0.177 n
2/3

 1356 
 
 Gn   1.648  10 T n  4.644  10 20 n 2 / 3 ( J )
 23

(c)  Gn   1.648  10 23 T n  4.644  10 20 n 2 / 3 ( J )

dGn 2
 1.648  10 23 T   4.644  10 20 nc1 / 3  0
dn n  nc 3
 1.648  1023 T
 nc1 / 3   5.321  10 4 T
2  20
 4.644  10
3
3
 6.637  10
9
 1
 nc    
4
 5.321  10 T  T 3
6.637  109
T  5K  nc  3
 5.31  107
5
6.637  109
T  50 K  nc   5.31  104
503
6.637  109
T  200 K  nc  3
 8.296  102
200

15.9 In the case of pure silver (FCC lattice), according to Table 14.1, the maximum supercooling
that has been observed is 227 degrees. Determine the homogeneous nucleation rate in silver at
this degree of supercooling using the following data. Note, to determine vs, use the volume of
the unit cell of silver divided by the number of atoms per unit cell in this metal. In the
following table the lattice parameter, a, is given for 1233 K.
a = 4.1710-10 m k = 1.3810-23 J/K
Tm = 1234.9 K  = 1013 Hz
ls = 0.123 J/m2 N = 6.0221023 atoms/mol
Hls = 11,960 J/mol ga = 6.410-20 J

J atoms J
a  4.17  1010 m, H ls  11960 , N  6.022  1023 ,  ls  0.123 2
mol mol m
J
Tm  1234.9 K ,  1013 s 1 , g a  6.4  10 20 J , T  227 K , k  1.38  10 23
K

vs 
a3


4.17  1010 m 3

 1.813  10 29 m3
4 4
  4 1 / 3 3vs 2 / 3  4 1 / 3  3  1.813  10 29 m3 
2/3
 3.337  1019 m 2
J
11960
H ls
mol J
hls    1.986  10 20
N atoms atom
6.022  1023
mol
3

4  lsTm
3 3 2  
m
J 
19 2 3

4  3.337  10 m   0.123 2   1234.9 K 
2

A     3.961  1014 J  K 2
27 h ls 2
  20
27  1.986  10 J
2
 
 3.96110 14 J  K 2 
  6.4 10  20 J  

  g a 
A    227 K 2 

  T 2    23 J 
 
 
 1.38 10   1234 .9  227 K
I  Ne kT
 1013 s 1  6.022  1023 mol 1  e  K

 I  6.022  1036 s 1mol 1  e  59.872  5.993  1010 s 1mol 1

15.13 (a) Suppose that an iron specimen containing 0.09 atomic percent carbon is equilibriated at
720C (993 K) and then rapidly quenched to 300C (573 K). Determine the length of the time
needed for one side of a plate-shaped carbide precipitate to grow out by 103 nm. (R: 8.314
J/molK)
(b) How wide a layer of the matrix next to a plate would have its carbon concentration
lowered from 0.09 percent carbon to that corresponding to n to form a layer of cementite
103 nm thick?
(c) How long would it take to increase one side of the plate by 10 nm?
Note: (1) In the case of ferrite in equilibrium with cementite, Cc = 11.2e-77,300/RT, where Cc is
the equilibrium concentration of carbon atoms (nc/nFe). (2) The diffusion coefficient for carbon
in -iron is D = 210-6e-84,100/RT (m2/s).

(a) nc  0.09%  9  10 4 , nc  25%  0.25

77 , 300 77 , 300

 Cc  11.2e RT
 nc  11.2  e 8.314 573
 1.005  10  6 (@ 300C )
nc  nc 9  10  4  1.005  10 6
1*  
n c


 nc nc  nc  0.25  1.005  10 0.25  9  10 
6 4

 1*  3.602  10 3

 84 , 000  84, 000
6 6 m2 4
D  2  10 e RT
 2  10 e 8.314 573
 4.399  10 ( )(@ 300C )
s
x2
 x  1* Dt  t 
  D
* 2
1
2
 3 9 m 
10 nm  10 
 nm 
t  1.752  106 s  486.6hours
 
 
2
2 m
3.602  10 3   4.399  10 4 
 s 

(b) 10 3

 x  A  nc  x  A  nc  103  A  nc

 
 x nc  nc  103 nc  nc  
nc  nc 0.25  9  10 4
 x  103   
 10 3
 4 6
 2.77  105 (nm)
nc  nc 9  10  1.005  10
 2
 9 m 
10nm  10 
 nm 
(c) t  175.2s
 4 m 
 
2
3 2
3.602  10   4.399  10 
 s 