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Question 1: If copper (which has a melting point of 1085°C) homogeneously nucleates at 849°C, calculate the critical radius. Given the values of 1.77 × 10 9

J/m 3 and 0.2 J/m 2 , respectively, for the latent heat of fusion and the surface free

energy.

Solution:

This problem states that copper homogeneously nucleates at 849°C, and that we are to calculate the critical radius given the latent heat of fusion (1.77 × 10 9 J/m 3 ) and the surface free energy (0.2 J/m 2 ).

Question 2:

(a) For the solidification of iron, calculate the critical radius r* and the activation

free energy ΔG* if nucleation is homogeneous. Values for the latent heat of fusion and surface free energy are 1.85 × 10 9 J/m 3 and 0.204 J/m 2 , respectively. Use the

supercooling value is 295° C (or 295 K). The melting temperature for iron is 1538°

 C. (b) Calculate the number of atoms found in a nucleus of critical size. Assume a

lattice parameter of 0.292 nm for solid iron at its melting temperature.

For computation of the activation free energy

(b) In order to compute the number of atoms in a nucleus of critical size (assuming a spherical nucleus of radius r*), it is first necessary to determine the number of unit cells, which we then multiply by the number of atoms per unit cell. The number of unit cells found in this critical nucleus is just the ratio of critical nucleus and unit cell volumes. Inasmuch as iron has the BCC crystal structure, its unit cell volume is just (a 3 ) where a is the unit cell length (i.e., the lattice parameter); this value is 0.292 nm, as cited in the problem statement. Therefore, the number of unit cells found in a radius of critical size is just

Inasmuch as 2 atoms are associated with each BCC unit cell, the total number of atoms per critical nucleus is just (414 unit cells / critical nucleus) × (2 atoms / unit cell) = 828 atoms / critical nucleus.

Question 3: (a) Assume for the solidification of iron (Question 2) that nucleation is homogeneous, and the number of stable nuclei is 10 6 nuclei per cubic meter. Calculate the critical radius and the number of stable nuclei that exist at the following degrees of supercooling: 200 K and 300 K.

(b) What is significant about the magnitudes of these critical radii and the numbers of stable nuclei?

Solution: (a) For 200 K supercooling,

And, for 300 K supercooling,

In order to compute the number of stable nuclei that exist at 200 K and 300 K degrees of supercooling. we must first determine the value of K 1 , which in turn requires that we calculate ΔG* at the homogeneous nucleation temperature; this was done in (Problem 2), and yielded a value of ΔG* = 1.57 × 10 -18 J. Now for

the computation of K 1 , using the value of n* for at the homogenous nucleation temperature (10 6 nuclei/m 3 ):

Now for 200 K supercooling, it is first necessary to recalculate the value of ΔG*

Thus:

And the value of n* is

Now, for 300 K supercooling the value of ΔG* is equal to

from which we compute the number of stable nuclei at 300 K of supercooling as

Solution: (b) Relative to critical radius, r* for 300 K supercooling is slightly smaller than that for 200 K (1.33 nm versus 2.00 nm). [From Problem 2, the value of r* at the homogeneous nucleation temperature (295 K) was 1.35 nm.]

More significant, however, are the values of n* at these two degrees of supercooling, which are dramatically different; 3.5×10 -35 stable nuclei at ΔT = 200 K, versus 2.32×10 7 stable nuclei at ΔT = 300 K !!!

Question (4): Use Equations

and

to estimate the number of crystal-like clusters in 1 mm3 of copper at its melting point for spherical clusters containing (a) 10 atoms, (b) 60 atoms. What volume of liquid copper is likely to contain one cluster of 100 atoms? The atomic volume of liquid copper is 1.6×10 29 m 3 , γ SL is 0.177 J.m 2 , k = 1.38×10 23 J.K 1 , T m = 1356 K. For 1 mm 3 of liquid copper, n 0 = 6.25×10 19 atoms.

Solution: at the equilibrium melting temperature T m .

At the equilibrium melting temperature ΔG V = 0, so that

For a cluster containing n c atoms with an atomic volume Ω we have

Therefore the expression for ΔG r becomes

For 1 mm 3 of liquid copper, n 0 = 6.25×10 19 atoms. Therefore, when n c = 10 atoms, n r = 9×10 13 clusters mm 3 ; when n c = 60 atoms, n r = 3 clusters mm 3 ; when n c = 100 atoms, n r = 4×10 8 clusters mm 3 ; or, alternatively, 1 cluster in 2.5×10 7 mm 3 .