4.

3 Calculate the activation energy for vacancy formation in aluminum, given that the equilibrium
number of vacancies at 500C (773 K) is 7.57 10
23
m
-3
. The atomic weight and density (at 500C)
for aluminum are, respectively, 26.98 g/mol and 2.62 g/cm
3
.

Solution
Upon examination of Equation 4.1, all parameters besides Q
v
are given except N, the total number
of atomic sites. However, N is related to the density, (
Al
), Avogadro's number (N
A
), and the atomic
weight (A
Al
) according to Equation 4.2 as



N =
N
A

Al
A
Al



=
(6.022 10
23
atoms/ mol)(2.62 g/ cm
3
)
26.98 g/ mol


= 5.85 10
22
atoms/cm
3
= 5.85 10
28
atoms/m
3


Now, taking natural logarithms of both sides of Equation 4.1,



ln N
v
= ln N
Q
v
kT


and, after some algebraic manipulation



Q
v
= kT ln
N
v
N
|
\

|
.
|



= (8.62 10
-5
eV/atom- K)(500C + 273 K) ln
7.57 10
23
m
3
5.85 10
28
m
3



(

(

= 0.75 eV/atom
4.6 Derive the following equations:
(a) Equation 4.7a
(b) Equation 4.9a
(c) Equation 4.10a
(d) Equation 4.11b

Solution
(a) This problem asks that we derive Equation 4.7a. To begin, C
1
is defined according to
Equation 4.3 as



C
1
=
m
1
m
1
+ m
2
100

or, equivalently



C
1
=
m
1
'
m
1
'
+ m
2
'
100

where the primed m's indicate masses in grams. From Equation 4.4 we may write



m
1
'

= n
m1
A
1



m
2
'

= n
m2
A
2


And, substitution into the C
1
expression above



C
1
=
n
m1
A
1
n
m1
A
1
+ n
m2
A
2
100

From Equation 4.5 it is the case that



n
m1
=
C
1
'
(n
m1
+ n
m2
)
100




n
m2
=
C
2
'
(n
m1
+ n
m2
)
100


And substitution of these expressions into the above equation leads to



C
1
=
C
1
'
A
1
C
1
'
A
1
+ C
2
'
A
2
100

which is just Equation 4.7a.

(b) This problem asks that we derive Equation 4.9a. To begin,


C
1
"
is defined as the mass of
component 1 per unit volume of alloy, or



C
1
"

=
m
1
V


If we assume that the total alloy volume V is equal to the sum of the volumes of the two
constituents--i.e., V = V
1
+ V
2
--then



C
1
"
=
m
1
V
1
+ V
2


Furthermore, the volume of each constituent is related to its density and mass as



V
1
=
m
1

1




V
2
=
m
2

2


This leads to



C
1
"
=
m
1
m
1

1
+
m
2

2


From Equation 4.3, m
1
and m
2
may be expressed as follows:



m
1
=
C
1
(m
1
+ m
2
)
100




m
2
=
C
2
(m
1
+ m
2
)
100


Substitution of these equations into the preceding expression yields



C
1
"
=
C
1
(m
1
+ m
2
)
100
C
1
(m
1
+ m
2
)
100

1
+
C
2
(m
1
+ m
2
)
100

2




=
C
1
C
1

1
+
C
2

2


If the densities
1
and
2
are given in units of g/cm
3
, then conversion to units of kg/m
3
requires that we
multiply this equation by 10
3
, inasmuch as

1 g/cm
3
= 10
3
kg/m
3


Therefore, the previous equation takes the form



C
1
"
=
C
1
C
1

1
+
C
2

2
10
3


which is the desired expression.


(c) Now we are asked to derive Equation 4.10a. The density of an alloy
ave
is just the total
alloy mass M divided by its volume V

ave
=
M
V


Or, in terms of the component elements 1 and 2

ave
=
m
1
+ m
2
V
1
+ V
2


[Note: here it is assumed that the total alloy volume is equal to the separate volumes of the individual
components, which is only an approximation; normally V will not be exactly equal to (V
1

+ V
2
)].
Each of V
1
and V
2
may be expressed in terms of its mass and density as,



V
1
=
m
1

1




V
2
=
m
2

2


When these expressions are substituted into the above equation, we get

ave
=
m
1
+ m
2
m
1

1
+
m
2

2


Furthermore, from Equation 4.3



m
1
=
C
1
(m
1
+ m
2
)
100




m
2
=
C
2
(m
1
+ m
2
)
100


Which, when substituted into the above
ave
expression yields

ave
=
m
1
+ m
2
C
1
(m
1
+ m
2
)
100

1
+
C
2
(m
1
+ m
2
)
100

2


And, finally, this equation reduces to



=
100
C
1

1
+
C
2

2


(d) And, finally, the derivation of Equation 4.11b for A
ave
is requested. The alloy average
molecular weight is just the ratio of total alloy mass in grams M and the total number of moles in the
alloy N
m
. That is



A
ave
=
M
N
m
=
m
1
'

+ m
2
'
n
m1
+ n
m2


But using Equation 4.4 we may write



m
1
'
= n
m1
A
1




m
2
'
= n
m2
A
2


Which, when substituted into the above A
ave
expression yields



A
ave
=
M'
N
m
=
n
m1
A
1
+ n
m2
A
2
n
m1
+ n
m2


Furthermore, from Equation 4.5



n
m1
=
C
1
'
(n
m1
+ n
m2
)
100




n
m2
=
C
2
'
(n
m1
+ n
m2
)
100


Thus, substitution of these expressions into the above equation for A
ave
yields



A
ave
=
C
1
'
A
1
(n
m1
+ n
m2
)
100
+
C
2
'
A
2
(n
m1
+ n
m2
)
100
n
m1
+ n
m2





=
C
1
'
A
1
+ C
2
'
A
2
100


which is the desired result.
4.10 What is the composition, in atom percent, of an alloy that contains 98 g tin and 65 g of lead?

Solution
The concentration of an element in an alloy, in atom percent, may be computed using Equation
4.5. However, it first becomes necessary to compute the number of moles of both Sn and Pb, using
Equation 4.4. Thus, the number of moles of Sn is just



n
m
Sn
=
m
Sn
'
A
Sn
=
98 g
118.71 g / mol
= 0.826 mol

Likewise, for Pb



n
m
Pb
=
65 g
207.2 g/ mol
= 0.314 mol

Now, use of Equation 4.5 yields



C
Sn
'
=
n
m
Sn
n
m
Sn
+ n
m
Pb
100


=
0.826 mol
0.826 mol + 0.314 mol
100 = 72.5 at%

Also,



C
Pb
'
= =
0.314 mol
0.826 mol + 0.314 mol
100 = 27.5 at%
4.13 Convert the atom percent composition in Problem 4.11 to weight percent.

Solution
The composition in atom percent for Problem 4.11 is 50.0 at% Cu, 49.7 at% Zn, and 0.3 at% Pb.
Modification of Equation 4.7 to take into account a three-component alloy leads to the following



C
Cu
=
C
Cu
'
A
Cu
C
Cu
'
A
Cu
+ C
Zn
'
A
Zn
+ C
Pb
'
A
Pb
100


=
(50.0) (63.55 g/ mol)
(50.0) (63.55 g / mol) + (49.7) (65.41 g / mol) + (0.3) (207.2 g/ mol)
100

= 49.0 wt%




C
Zn
=
C
Zn
'
A
Zn
C
Cu
'
A
Cu
+ C
Zn
'
A
Zn
+ C
Pb
'
A
Pb
100


=
(49.7) (65.41 g/ mol)
(50.0) (63.55 g / mol) + (49.7) (65.41 g / mol) + (0.3) (207.2 g/ mol)
100

= 50.1 wt%




C
Pb
=
C
Pb
'
A
Pb
C
Cu
'
A
Cu
+ C
Zn
'
A
Zn
+ C
Pb
'
A
Pb
100


=
(0.3) (207.2 g/ mol)
(50.0) (63.55 g / mol) + (49.7) (65.41 g / mol) + (0.3) (207.2 g/ mol)
100

= 1.0 wt%
4.17 Calculate the unit cell edge length for an 85 wt% Fe-15 wt% V alloy. All of the vanadium is in
solid solution, and, at room temperature the crystal structure for this alloy is BCC.

Solution
In order to solve this problem it is necessary to employ Equation 3.5; in this expression density
and atomic weight will be averages for the alloythat is

ave
=
nA
ave
V
C
N
A


Inasmuch as the unit cell is cubic, then V
C
= a
3
, then

ave
=
nA
ave
a
3
N
A



And solving this equation for the unit cell edge length, leads to



a =
nA
ave

ave
N
A
|
\


|
.
|
|
1/ 3


Expressions for A
ave
and
ave
are found in Equations 4.11a and 4.10a, respectively, which, when
incorporated into the above expression yields



a =
n
100
C
Fe
A
Fe
+
C
V
A
V
|
\




|
.
|
|
|
|
100
C
Fe

Fe
+
C
V

V
|
\




|
.
|
|
|
|
N
A











(

(
(
(
(
(
(
(
(
(
1/ 3


Since the crystal structure is BCC, the value of n in the above expression is 2 atoms per unit cell.
The atomic weights for Fe and V are 55.85 and 50.94 g/mol, respectively (Figure 2.6), whereas the
densities for the Fe and V are 7.87 g/cm
3
and 6.10 g/cm
3
(from inside the front cover). Substitution
of these, as well as the concentration values stipulated in the problem statement, into the above
equation gives



a =
(2 atoms/unit cell)
100
85 wt%
55.85 g/mol
+
15 wt%
50.94 g/mol
|
\




|
.
|
|
|
|
100
85 wt%
7.87 g/cm
3
+
15 wt%
6.10 g/cm
3
|
\




|
.
|
|
|
|
6.022 10
23
atoms/mol
( )











(

(
(
(
(
(
(
(
(
(
1/ 3



= 2.89 10
-8
cm = 0.289 nm
4.32 (a) Using the intercept method, determine the average grain size, in millimeters, of the specimen
whose microstructure is shown in Figure 4.14(b); use at least seven straight-line segments.
(b) Estimate the ASTM grain size number for this material.

Solution
(a) Below is shown the photomicrograph of Figure 4.14(b), on which seven straight line segments,
each of which is 60 mm long has been constructed; these lines are labeled 1 through 7.



In order to determine the average grain diameter, it is necessary to count the number of grains
intersected by each of these line segments. These data are tabulated below.

Line Number No. Grains Intersected
1 11
2 10
3 9
4 8.5
5 7
6 10
7 8

The average number of grain boundary intersections for these lines was 9.1. Therefore, the average
line length intersected is just


60 mm
9.1
= 6.59 mm

Hence, the average grain diameter, d, is



d =
ave. line length intersected
magnification
=
6.59 mm
100
= 6.59 10
2
mm

(b) This portion of the problem calls for us to estimate the ASTM grain size number for this
same material. The average grain size number, n, is related to the number of grains per square inch,
N, at a magnification of 100 according to Equation 4.16. Inasmuch as the magnification is 100, the
value of N is measured directly from the micrograph. The photomicrograph on which has been
constructed a square 1 in. on a side is shown below.



The total number of complete grains within this square is approximately 10 (taking into account grain
fractions). Now, in order to solve for n in Equation 4.16, it is first necessary to take logarithms as



log N = (n 1) log 2

From which n equals



n =
log N
log 2
+ 1


=
log 10
log 2
+ 1 = 4.3