Problem 10.

3
If copper (which has a melting point of 1085°C)
homogeneously nucleates at 849°C, calculate the critical
radius given values of –1.77 x 109 J/m3 and 0.200 J/m2,
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 x 109
J/m3 ) and the surface free energy (0.200 J/m2). Solution to this problem
requires the utilization of Equation 10.6 as
 Problem 10.4
(a) For the solidification of iron, calculate the critical radius r* and the
activation free energy ∆G∗ if nucleation is homogeneous. Values for the
latent heat of fusion and surface free energy are –1.85 x109 J/m3 and 0.204
J/m2, respectively. Use the supercooling value found in Table 10.1.

(b) Now 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.

Table 10.1 Degree of Supercooling (∆T)

Values (Homogeneous Nucleation) for
Several Metals
 Solution
(a) This portion of the problem asks that we compute r* and ∆G* for the
homogeneous nucleation of the solidification of Fe. First of all, Equation 10.6
is used to compute the critical radius. The melting temperature for iron,
found inside the front cover is 1538°C; also values of ∆𝐻𝑓 (–1.85 x 109 J/m3)
and 𝛾 (0.204 J/m2) are given in the problem statement, and the supercooling
value found in Table 10.1 is 295°C (or 295 K). Thus, from Equation 10.6 we
have
 Solution
For computation of the activation free energy, Equation 10.7 is employed. Thus

(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 a3 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
 Solution

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
 Problem 10.5
(a) Assume for the solidification of iron (Problem 10.4) that nucleation is
homogeneous, and the number of stable nuclei is 106 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 this part of the problem we are asked to calculate the critical radius for
the solidification of iron (per Problem 10.4), for 200 K and 300 K degrees of
supercooling, and assuming that the there are 106 nuclei per meter cubed for
homogeneous nucleation. In order to calculate the critical radii, we replace the
Tm – T term in Equation 10.6 by the degree of supercooling (denoted as ∆T) cited
in the problem.

For 200 K supercooling,

 Solution
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, it is necessary to use Equation 10.8.
However, we must first determine the value of K1 in Equation 10.8, which
in turn requires that we calculate ∆G* at the homogeneous nucleation
temperature using Equation 10.7; this was done in Problem 10.4, and
yielded a value of ∆G* = 1.57 x 10-18 J. Now for the computation of K1,
using the value of n* for at the homogenous nucleation temperature (106
nuclei/m3):
 Solution

Now for 200 K supercooling, it is first necessary to recalculate the value ∆G* of
using Equation 10.7, where, again, the Tm – T term is replaced by the number of
degrees of supercooling, denoted as OT, which in this case is 200 K.
Thus
 Solution
And, from Equation 10.8, the value of n* is

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

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

(b) Relative to critical radius, r* for 300 K supercooling is slightly smaller that for
200 K (1.33 nm versus 2.00 nm). [From Problem 10.4, 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 x 10-35 stable nuclei at ∆T = 200 K, versus 2.32 x 107
stable nuclei at ∆T = 300 K!
 Problem 10.6
For some transformation having kinetics that obey the Avrami
equation (Equation 10.17), the parameter n is known to have
a value of 1.7. If, after 100 s, the reaction is 50% complete,
how long (total time) will it take the transformation to go to
99% completion?
 Solution
This problem calls for us to compute the length of time required
for a reaction to go to 99% completion. It first becomes
necessary to solve for the parameter k in Equation 10.17. In
order to do this it is best manipulate the equation such that k is
the dependent variable. We first rearrange Equation 10.17 as

and then take natural logarithms of both sides:

Now solving for k gives

 Solution
And, from the problem statement, for y = 0.50 when t = 100 s
and given that n = 1.7, the value of k is equal to

We now want to manipulate Equation 10.17 such that t is the

dependent variable. The above equation may be written in the
form:

And solving this expression for t leads to

Now, using this equation and the value of k determined
above, the time to 99% transformation completion is equal to
 Problem 10.8
It is known that the kinetics of recrystallization for some alloy obey the Avrami
equation and that the value of n in the exponential is 2.5. If, at some temperature,
the fraction recrystallized is 0.40 after 200 min, determine the rate of
recrystallization at this temperature.
 Solution
This problem gives us the value of y (0.40) at some time t (200 min), and
also the value of n (2.5) for the recrystallization of an alloy at some
temperature, and then asks that we determine the rate of recrystallization
at this same temperature. It is first necessary to calculate the value of k.
We first rearrange Equation 10.17 as

and then take natural logarithms of both sides:

Now solving for k gives

which, using the values cited above for y, n, and t yields

At this point we want to compute t0.5, the value of t for y = 0.5, which means
that it is necessary to establish a form of Equation 10.17 in which t is the
dependent variable. From one of the above equations
 Solution
And solving this expression for t leads to

For t0.5, this equation takes the form

and incorporation of the value of k determined above, as well as the value of n

cited in the problem statement (2.5), then t0.5 is equal to

Therefore, from Equation 10.18, the rate is just

 Problem 10.18
Using the isothermal transformation diagram for an iron–carbon alloy of
eutectoid composition (Figure 10.22), specify the nature of the final
microstructure (in terms of microconstituents present and approximate
percentages of each) of a small specimen that has been subjected to the
following time–temperature treatments. In each case assume that the
specimen begins at 760°C (1400°F) and that it has been held at this
temperature long enough to have achieved a complete and homogeneous
austenitic structure.

(a) Cool rapidly to 700°C (1290°F), hold for 104 s, then quench to room
temperature.
(b) Reheat the specimen in part (a) to 700°C (1290°F) for 20 h.
(c) Rapidly cool to 600°C (1110°F), hold for 4 s, rapidly cool to 450°C
(840°F), hold for 10 s, then quench to room temperature.
(d) Cool rapidly to 400°C (750°F), hold for 2 s, then quench to room
temperature.
(e) Cool rapidly to 400°C (750°F), hold for 20 s, then quench to room
temperature.
 Problem 10.18
(f) Cool rapidly to 400°C (750°F), hold for 200 s, then quench to room temperature.
(g) Rapidly cool to 575°C (1065°F), hold for 20 s, rapidly cool to 350°C (660°F),
hold for 100 s, then quench to room temperature.
(h) Rapidly cool to 250°C (480°F), hold for 100 s, then quench to room temperature
in water. Reheat to 315°C (600°F) for 1 h and slowly cool to room temperature.
 Solution
(a) Cool rapidly to 700°C (1290°F), hold for 104 s, then quench to room
temperature.

After cooling and holding at 700°C

for 104 s, approximately 50% of the
specimen has transformed to
coarse pearlite. Upon cooling to
room temperature, the remaining
50% transforms to martensite.
Hence, the final microstructure
consists of about 50% coarse
pearlite and 50% martensite.
 Solution
(b) Reheat the specimen in part (a) to 700°C (1290°F) for 20 h.

Heating to 700°C for 20 h the specimen in part (a) will transform the
coarse pearlite and martensite to spheroidite.
 Solution
(c) Rapidly cool to 600°C (1110°F), hold for 4 s, rapidly cool to 450°C (840°F),
hold for 10 s, then quench to room temperature.

After cooling to and holding at 600°C

for 4 s, approximately 50% of the
specimen has transformed to pearlite
(medium). During the rapid cooling to
450°C no transformations occur. At
450°C we start timing again at zero
time; while holding at 450°C for 10 s,
approximately 50 percent of the
remaining unreacted 50% (or 25% of
the original specimen) will transform to
bainite. And upon cooling to room
temperature, the remaining 25% of the
original specimen transforms to
martensite. Hence, the final
microstructure consists of about 50%
pearlite (medium), 25% bainite, and
25% martensite.
 Solution
(d) Cool rapidly to 400°C (750°F), hold for 2 s, then quench to room
temperature.

After cooling to and holding at

400°C for 2s, no of the
transformation begin lines have
been crossed, and therefore, the
specimen is 100% austenite. Upon
cooling rapidly to room
temperature, all of the specimen
transforms to martensite, such that
the final microstructure is 100%
martensite.
 Solution
(e) Cool rapidly to 400°C (750°F), hold for 20 s, then quench to room
temperature.

After cooling and holding at

400°C for 20s, approximately
40% of the specimen has
transformed to bainite. Upon
cooling to room temperature, the
remaining 60% transforms to
martensite. Hence, the final
microstructure consists of about
40% bainite and 60%
martensite.
 Solution
(f) Cool rapidly to 400°C (750°F), hold for 200 s, then quench to room temperature.

After cooling and holding at

400°C for 200s, the entire
specimen has transformed to
bainite. Therefore, during the
cooling to room temperature no
additional transformations will
occur. Hence, the final
microstructure consists of 100%
bainite.
 Solution
(g) Rapidly cool to 575°C (1065°F), hold for 20 s, rapidly cool to 350°C (660°F),
hold for 100 s, then quench to room temperature.

After cooling and holding at 575°C for

20 s, the entire specimen has
transformed to fine pearlite. Therefore,
during the second heat treatment at
350°C no additional transformations will
occur. Hence, the final microstructure
consists of 100% fine pearlite.
 Solution
(h) Rapidly cool to 250°C (480°F), hold for 100 s, then quench to room temperature
in water. Reheat to 315°C (600°F) for 1 h and slowly cool to room temperature.

After cooling and holding at 250°C for

100 s, no transformations will have
occurred at this point, the entire
specimen is still austenite. Upon
rapidly cooling to room temperature in
water, the specimen will completely
transform to martensite. The second
heat treatment (at 315°C for 1 h)—not
shown on the above plot—will
transform the material to tempered
martensite. Hence, the final
microstructure is 100% tempered
martensite.