MSE 408: Phase Transformations

Homework Assignment 4: Nucleation

Due by 5 pm on Monday, March 3
Reading: Lecture notes from class, my notes posted on blackboard and Hoyt, Chapter 3
should contain most of the information and ideas you need to do this assignment.
1. For nucleation of solid Cu from the melt, assume that the solid-liquid interfacial free
energy is =0.140 J/m2, the latent heat of fusion is L=13.26 kJ/mole, the melting
temperature is TM=1357 K, and the solid molar volume is Vm=7.589 cm3/mole. Assume
that the free-energy difference between solid and liquid bulk phases is given by the
relation G=LT/Tm, where T is the undercooling (T =T-TM).
a. Compute the critical radius of a spherical crystal nucleus for undercoolings of T=10,
100 and 300 and 600 K. For which of these temperatures might you suspect that the
continuum-thermodynamics analysis that we have used in class might be inaccurate?
Explain your answer.
b. Assuming that the liquid density is 0.126 mole/cm3, what is the average number of
critical nuclei in a 1 m3 volume at these four temperatures under steady-state nucleation
conditions. (Hint: Youll need to use the answer to problem 6.)
c. Derive the following expression for the Zeldovich factor:

where Na is Avogadros number. Use this expression to derive the values for Z for each of
the values of T given in part (a).
2. Consider further the nucleation of solid Cu from its melt. Use the properties given in
problem (2), and assume that the activation energy for liquid diffusion is Ga=0.3 eV
(and is relatively temperature-independent), and the jump distance is =2 Angstroms.
a. For nucleation of a crystalline solid from a liquid phase, the following expression can
be used for (g*):
( g*) n1s1 ( g*) 2 / 3

kT
exp Ga / kT
h

where s1 is the surface area of the monomer, h is Plancks constant, Ga is the activation
energy, and is the jump distance. Calculate and plot the steady-state nucleation rate (Jss)
as a function of undercooling from T=0 to T=600 K (note: it will be helpful to make
use of a semi-log plot, i.e., plotting log(Jss) versus T).
b. Based on the results of part (a), how long would you have to wait for one nucleus to
form in a 1 cm3 volume at undercoolings of T=50, 100 and 200 K? Note the extreme
sensitivity of the nucleation rate to relatively small changes in the undercooling.

c. Change the surface energy from is =0.140 J/m2 to =0.240 J/m2. Repeat the
calculation of part b. Given that the interfacial energy is very difficult to measure, what
does this imply about the challenge of predicting nucleation rates in materials?
c. In part (a) you should find that the nucleation rate continues to increase with increasing
T. Would you expect this trend to continue indefinitely? Explain your answer (hint:
think about the glass transition).
d. Compute incubation times over the same range of temperatures as in part (a).
The following problems 4 and 5 are based on the following paper: R. W. Hyland, Jr., Met.
Trans. A, vol. 23A, pg. 1947 (1992). I will post a pdf of this article on Blackboard, of you
can make your own copy from the library. For the problems below, most of the
information that is needed can be found in the manuscript. For example, you can read the
values for the free-energy driving force and the elastic energy from Figs. 8 and 9. You
will need in addition the following information:
Lattice constant of product phase (Al3Sc): 4.10 .
Volume per atom in the matrix (Al): 16.6 3/atom.
For D in Equations 7-9 of the paper, use the value for the solute (Sc):
D=DSc=D0 exp(-Q / RT)
where D0=3560 m2/s and Q=283 kJ/mol. This is valid since the solution is dilute.
For the interfacial free energy use =95 mJ/m2.
Note that in Fig. 9, the figure caption and the vertical axis of the plot are not
consistent. I believe that the figure caption is incorrect.
3. Complete parts (a)-(d) below.
a. Calculate and plot the steady-state nucleation rate of Al3Sc precipitates in an Al-0.11 at.
% Sc alloy at the following temperatures: 700 K, 650 K, 600 K, 550 K and 500 K.
b. Compute the incubation times () for the same temperatures as in part (a).
c. Summarize in a paragraph the experimental approach used to measure the
homogeneous nucleation rate and identify some of the key challenges associated with
these measurements. List one or two other experimental methods that could be used to
measure the nucleation rate.
4. For the same temperatures considered in 4 (a), calculate the ratio of the heterogeneous
nucleation rate relative to the homogeneous nucleation rate for the case of heterogeneous
nucleation on a grain-boundary plane for grain sizes of (i) 1 mm, (ii) 10 m, and (ii) 10
nm. Assume the grain-boundary energy is equal to 100 mJ/m2, and that the effective
grain-boundary width is 5
5. Using the same approach that we used in class to derive JSS, derive the following
approximate expression (Hint: Expand W(g) in a Taylor series about g*):
f (g)
n( g )

What is the value of f(g*)?

1
erfc Z ( g g *)
2