Exercícios Callister

CHAPTER 6
DIFFUSION
PROBLEM SOLUTIONS
Introduction
6.1 Briefly explain the difference between self-diffusion and interdiffusion.
Solution
Self-diffusion is atomic migration in pure metalsi.e., when all atoms exchanging positions are of the
same type. Interdiffusion is diffusion of atoms of one metal into another metal.
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6.2 Self-diffusion involves the motion of atoms that are all of the same type; therefore, it is not subject to
observation by compositional changes, as with interdiffusion. Suggest one way in which self-diffusion may be
monitored.
Solution
Self-diffusion may be monitored by using radioactive isotopes of the metal being studied. The motion of
these isotopic atoms may be monitored by measurement of radioactivity level.
Diffusion Mechanisms
6.3 (a) Compare interstitial and vacancy atomic mechanisms for diffusion.
(b) Cite two reasons why interstitial diffusion is normally more rapid than vacancy diffusion.
Solution
(a) With vacancy diffusion, atomic motion is from one lattice site to an adjacent vacancy. Self-diffusion
and the diffusion of substitutional impurities proceed via this mechanism. On the other hand, atomic motion is from
interstitial site to adjacent interstitial site for the interstitial diffusion mechanism.
(b) Interstitial diffusion is normally more rapid than vacancy diffusion because: (1) interstitial atoms,
being smaller, are more mobile; and (2) the probability of an empty adjacent interstitial site is greater than for a
vacancy adjacent to a host (or substitutional impurity) atom.
Steady-State Diffusion
6.4 Briefly explain the concept of steady state as it applies to diffusion.
Solution
Steady-state diffusion is the situation wherein the rate of diffusion into a given system is just equal to the
rate of diffusion out, such that there is no net accumulation or depletion of diffusing speciesi.e., the diffusion flux
is independent of time.
6.5 (a) Briefly explain the concept of a driving force.

(b) What is the driving force for steady-state diffusion?
Solution
(a) The driving force is that which compels a reaction to occur.
(b) The driving force for steady-state diffusion is the concentration gradient.
6.6 The purification of hydrogen gas by diffusion through a palladium sheet was discussed in Section 6.3.
Compute the number of kilograms of hydrogen that pass per hour through a 5-mm-thick sheet of palladium having
an area of 0.20 m2 at 500C. Assume a diffusion coefficient of 1.0 10-8 m2/s, that the respective concentrations at
the high- and low-pressure sides of the plate are 2.4 and 0.6 kg of hydrogen per cubic meter of palladium, and that
steady-state conditions have been attained.
Solution
This problem calls for the mass of hydrogen, per hour, that diffuses through a Pd sheet. It first becomes
necessary to employ both Equations 6.1a and 6.3. Combining these expressions and solving for the mass yields
M = JAt = ! DAt
"C
"x
# 0.6 ! 2.4 kg / m3 &

= ! (1.0 " 10 -8 m2 /s)(0.20 m2 ) (3600 s/h) %
(
$ 5 " 10!3 m '
= 2.6 10-3 kg/h
6.7 A sheet of steel 1.5 mm thick has nitrogen atmospheres on both sides at 1200C and is permitted to
achieve a steady-state diffusion condition. The diffusion coefficient for nitrogen in steel at this temperature is 6
10-11 m2/s, and the diffusion flux is found to be 1.2 10-7 kg/m2-s. Also, it is known that the concentration of
nitrogen in the steel at the high-pressure surface is 4 kg/m3. How far into the sheet from this high-pressure side will
the concentration be 2.0 kg/m3? Assume a linear concentration profile.
Solution
This problem is solved by using Equation 6.3 in the form
C ! CB
J = ! D A
xA ! xB
If we take CA to be the point at which the concentration of nitrogen is 4 kg/m3, then it becomes necessary to solve
for xB, as
" C ! CB %
xB = xA + D $ A
'
J
#
&
Assume xA is zero at the surface, in which case
# 4 kg / m3 " 2 kg / m3 &
xB = 0 + (6 ! 10 -11 m2 /s) %
(
$ 1.2 ! 10"7 kg / m2 - s '
= 1 10-3 m = 1 mm
6.8 A sheet of BCC iron 1 mm thick was exposed to a carburizing gas atmosphere on one side and a
decarburizing atmosphere on the other side at 725C. After having reached steady state, the iron was quickly
cooled to room temperature. The carbon concentrations at the two surfaces of the sheet were determined to be
0.012 and 0.0075 wt%, respectively. Compute the diffusion coefficient if the diffusion flux is 1.4 10-8 kg/m2-s.
Hint: Use Equation 5.12 to convert the concentrations from weight percent to kilograms of carbon per cubic meter
of iron.
Solution
Let us first convert the carbon concentrations from weight percent to kilograms carbon per meter cubed
using Equation 5.12a. For 0.012 wt% C
CC" =
CC
!C
CC
+
C Fe
" 10 3
! Fe
0.012
! 10 3
0.012
99.988
+
2.25 g/cm3
7.87 g/cm3
0.944 kg C/m3
Similarly, for 0.0075 wt% C
CC" =
0.0075
! 10 3
0.0075
99.9925
+
2.25 g/cm3
7.87 g/cm3
= 0.590 kg C/m3
Now, using a rearranged form of Equation 6.3
"x ! x %
B'
D = ! J$ A
$# C A ! C B '&
#
&
! 10!3 m
= ! (1.40 " 10 -8 kg/m2 - s)%
(
3
3
$ 0.944 kg/m ! 0.590 kg/m '
= 3.95 10-11 m2/s
6.9 When -iron is subjected to an atmosphere of hydrogen gas, the concentration of hydrogen in the iron,
CH (in weight percent), is a function of hydrogen pressure, pH 2 (in MPa), and absolute temperature (T) according
to
# 27.2 kJ / mol &

CH = 1.34 ! 10"2 pH 2 exp%"
(
$
'
RT
(6.16)
Furthermore, the values of D0 and Qd for this diffusion system are 1.4 10-7 m2/s and 13,400 J/mol, respectively.
Consider a thin iron membrane 1 mm thick that is at 250C. Compute the diffusion flux through this membrane if
the hydrogen pressure on one side of the membrane is 0.15 MPa (1.48 atm) and that on the other side is 7.5 MPa
(74 atm).
Solution
Ultimately we will employ Equation 6.3 to solve this problem. However, it first becomes necessary to
determine the concentration of hydrogen at each face using Equation 6.16. At the low pressure (or B) side
#
&
27, 200 J/mol
CH(B) = (1.34 ! 10 -2 ) 0.15 MPa exp %"
(
$ (8.31 J/mol - K)(250 + 273 K) '
9.93 10-6 wt%
Whereas, for the high pressure (or A) side
#
&
27, 200 J/mol
CH(A) = (1.34 ! 10 -2 ) 7.5 MPa exp %"
(
$ (8.31 J/mol - K)(250 + 273 K) '
7.02 10-5 wt%
We now convert concentrations in weight percent to mass of nitrogen per unit volume of solid. At face B there are
9.93 10-6 g (or 9.93 10-9 kg) of hydrogen in 100 g of Fe, which is virtually pure iron. From the density of iron
(7.87 g/cm3), the volume iron in 100 g (V ) is just
B
VB =
100 g
= 12.7 cm 3 = 1.27 ! 10-5 m 3
3
7.87 g/cm
Therefore, the concentration of hydrogen at the B face in kilograms of H per cubic meter of alloy [ C H(B)
] is just
''
CH(B)
=
CH(B)
VB
9.93 ! 10"9 kg
= 7.82 ! 10 -4 kg/m3
1.27 ! 10"5 m3
At the A face the volume of iron in 100 g (VA) will also be 1.27 10-5 m3, and
''
CH(A)
=
CH(A)
VA
7.02 ! 10"8 kg
= 5.53 ! 10 -3 kg/m3
1.27 ! 10"5 m3
Thus, the concentration gradient is just the difference between these concentrations of nitrogen divided by the
thickness of the iron membrane; that is
''
''
CH(B)
" CH(A)
!C
=
!x
xB " xA
7.82 ! 10"4 kg / m3 " 5.53 ! 10"3 kg / m3

= " 4.75 kg/m4
10"3 m
At this time it becomes necessary to calculate the value of the diffusion coefficient at 250C using Equation 6.8.
Thus,
" Q %
D = D0 exp $! d '
# RT &
#
&
13,400 J/mol
= (1.4 ! 10"7 m2 /s) exp %"
(
$ (8.31 J/mol " K)(250 + 273 K) '
= 6.41 10-9 m2/s
And, finally, the diffusion flux is computed using Equation 6.3 by taking the negative product of this diffusion
coefficient and the concentration gradient, as
J =!D
"C
"x
= ! (6.41 " 10-9 m 2 /s)(! 4.75 kg/m 4 ) = 3.05 " 10-8 kg/m 2 -s
Nonsteady-State Diffusion
6.10 Show that
Cx =
" x2 %
B
exp $!
'
Dt
# 4 Dt &
is also a solution to Equation 6.4b. The parameter B is a constant, being independent of both x and t.
Solution
It can be shown that
Cx =
" x2 %
B
exp $!
'
Dt
# 4 Dt &
is a solution to
!C
!2C
= D
!t
!x 2
simply by taking appropriate derivatives of the Cx expression. When this is carried out,
# x2
&
# x2 &
!C
!2 C
B
= D 2 =
"
1
exp
%
(
% " 4 Dt (
!t
!x
2 D1/2t 3/2 $ 2 Dt
'
$
'
6.11 Determine the carburizing time necessary to achieve a carbon concentration of 0.45 wt% at a
position 2 mm into an ironcarbon alloy that initially contains 0.20 wt% C. The surface concentration is to be
maintained at 1.30 wt% C, and the treatment is to be conducted at 1000C. Use the diffusion data for -Fe in Table
6.2.
Solution
In order to solve this problem it is first necessary to use Equation 6.5:
C x ! C0
" x %
= 1 ! erf $
'
# 2 Dt &
Cs ! C0
wherein, Cx = 0.45, C0 = 0.20, Cs = 1.30, and x = 2 mm = 2 10-3 m. Thus,
Cx ! C0 0.45 ! 0.20
" x %
=
= 0.2273 = 1 ! erf $
# 2 Dt '&
Cs ! C0 1.30 ! 0.20
or
! x $
erf #
& = 1 ' 0.2273 = 0.7727
" 2 Dt %
By linear interpolation using data from Table 6.1
erf(z)
0.85
0.7707
0.7727
0.90
0.7970
z ! 0.850
0.7727 ! 0.7707
=
0.900 ! 0.850 0.7970 ! 0.7707
From which
z = 0.854 =
x
2 Dt
Now, from Table 6.2, at 1000C (1273 K)
#
&
148,000 J/mol
D = (2.3 ! 10-5 m 2 /s) exp % "
(
(8.31
J/mol-K)(1273
K)
$
'
= 1.93 10-11 m2/s
Thus,
0.854 =
2 ! 10"3 m
(2) (1.93 ! 10"11 m2 /s) (t)
Solving for t yields

t = 7.1 104 s = 19.7 h
6.12 An FCC iron-carbon alloy initially containing 0.35 wt% C is exposed to an oxygen-rich and virtually
carbon-free atmosphere at 1400 K (1127C). Under these circumstances the carbon diffuses from the alloy and
reacts at the surface with the oxygen in the atmosphere; that is, the carbon concentration at the surface position is
maintained essentially at 0 wt% C. (This process of carbon depletion is termed decarburization.) At what position
will the carbon concentration be 0.15 wt% after a 10-h treatment? The value of D at 1400 K is 6.9 10-11 m2/s.
Solution
This problem asks that we determine the position at which the carbon concentration is 0.15 wt% after a 10h heat treatment at 1325 K when C0 = 0.35 wt% C. From Equation 6.5
Cx ! C0
0.15 ! 0.35
" x %
=
= 0.5714 = 1 ! erf $
# 2 Dt '&
Cs ! C0
0 ! 0.35
Thus,
! x $
erf #
& = 0.4286
" 2 Dt %
Using data in Table 6.1 and linear interpolation
erf (z)
0.40
0.4284
0.4286
0.45
0.4755
z ! 0.40
0.4286 ! 0.4284
=
0.45 ! 0.40 0.4755 ! 0.4284
And
z = 0.4002
Which means that
x
= 0.4002
2 Dt
And finally
x = 2(0.4002) Dt = (0.8004)
(6.9 ! 10"11 m2 /s)( 3.6 ! 10 4 s)
= 1.26 10-3 m = 1.26 mm

Note: this problem may also be solved using the Diffusion module in the VMSE software. Open the Diffusion
module, click on the Diffusion Design submodule, and then do the following:
1. Enter the given data in left-hand window that appears. In the window below the label D Value enter
the value of the diffusion coefficientviz. 6.9e-11.
2. In the window just below the label Initial, C0 enter the initial concentrationviz. 0.35.
3. In the window the lies below Surface, Cs enter the surface concentrationviz. 0.
4. Then in the Diffusion Time t window enter the time in seconds; in 10 h there are (60 s/min)(60
min/h)(10 h) = 36,000 sso enter the value 3.6e4.
5. Next, at the bottom of this window click on the button labeled Add curve.
6. On the right portion of the screen will appear a concentration profile for this particular diffusion
situation. A diamond-shaped cursor will appear at the upper left-hand corner of the resulting curve. Click and drag
this cursor down the curve to the point at which the number below Concentration: reads 0.15 wt%. Then read
the value under the Distance:. For this problem, this value (the solution to the problem) ranges between 1.24 and
1.30 mm.
6.13 Nitrogen from a gaseous phase is to be diffused into pure iron at 700C. If the surface concentration
is maintained at 0.1 wt% N, what will be the concentration 1 mm from the surface after 10 h? The diffusion
coefficient for nitrogen in iron at 700C is 2.5 10-11 m2/s.
Solution
This problem asks us to compute the nitrogen concentration (Cx) at the 1 mm position after a 10 h diffusion
time, when diffusion is nonsteady-state. From Equation 6.5
Cx ! C0
C ! 0
" x %
= x
= 1 ! erf $
# 2 Dt '&
Cs ! C0
0.1 ! 0
#
&
10 !3 m
(
= 1 ! erf %
% (2) (2.5 " 10 !11 m 2 /s) (10 h)(3600 s/h) (
$
'
= 1 erf (0.527)
Using data in Table 6.1 and linear interpolation
erf (z)
0.500
0.5205
0.527
0.550
0.5633
0.527 ! 0.500
y ! 0.5205
=
0.550 ! 0.500
0.5633 ! 0.5205
from which
y = erf (0.527) = 0.5436
Thus,
Cx ! 0
= 1.0 ! 0.5436
0.1 ! 0
This expression gives

Cx = 0.046 wt% N
module, click on the Diffusion Design submodule, and then do the following:
1. Enter the given data in left-hand window that appears. In the window below the label D Value enter
the value of the diffusion coefficientviz. 2.5e-11.
2. In the window just below the label Initial, C0 enter the initial concentrationviz. 0.
3. In the window the lies below Surface, Cs enter the surface concentrationviz. 0.1.
4. Then in the Diffusion Time t window enter the time in seconds; in 10 h there are (60 s/min)(60
min/h)(10 h) = 36,000 sso enter the value 3.6e4.
5. Next, at the bottom of this window click on the button labeled Add curve.
6. On the right portion of the screen will appear a concentration profile for this particular diffusion
situation. A diamond-shaped cursor will appear at the upper left-hand corner of the resulting curve. Click and drag
this cursor down the curve to the point at which the number below Distance: reads 1.00 mm. Then read the
value under the Concentration:. For this problem, this value (the solution to the problem) is 0.05 wt%.
6.14 Consider a diffusion couple composed of two semi-infinite solids of the same metal and that each side
of the diffusion couple has a different concentration of the same elemental impurity; furthermore, assume each
impurity level is constant throughout its side of the diffusion couple. For this situation, the solution to Ficks second
law (assuming that the diffusion coefficient for the impurity is independent of concentration), is as follows:
! C + C2 $
! C1 ' C2 $ ! x $
Cx = # 1
&% ' #"
&% erf #"
&
"
2
2
2 Dt %
(6.17)
In this expression, when the x = 0 position is taken as the initial diffusion couple interface, then C1 is the impurity
concentration for x < 0, and C2 is the impurity content for x > 0.
A diffusion couple composed of two silver-gold alloys is formed; these alloys have compositions of 98 wt%
Ag2 wt% Au and 95 wt% Ag5 wt% Au. Determine the time for which this diffusion couple must be heated at
750C (1023 K) in order for the composition to be 2.5 wt% Au at the 50-mm position into the 2 wt% Au side of the
diffusion couple. Preexponential and activation energy values for Au diffusion in Ag are 8.5 105 m2/s and
202,100 J/mol, respectively.
Solution
For this platinum-gold diffusion couple for which C1 = 5 wt% Au and C2 = 2 wt% Au, we are asked to
determine the diffusion time at 750C that will give a composition of 2.5 wt% Au at the 50 m position. Thus, for
this problem, Equation 6.17 takes the form
! 5 + 2$
! 5 ' 2 $ ! 50 ( 10 '6 m $
2.5 = #
' #
erf
" 2 &%
" 2 &% #" 2 Dt &%
It now becomes necessary to compute the diffusion coefficient at 750C (1023 K) given that D0 = 8.5 10-5 m2/s
and Qd = 202,100 J/mol. From Equation 6.8 we have
" Q %
D = D0 exp $! d '
# RT &
#
&
202,100 J/mol
= (8.5 ! 10 -5 m2 /s) exp %"
(
$ (8.31 J/mol " K)(1023 K) '
= 4.03 10-15 m2/s
Substitution of this value into the above equation leads to
)
,
50 ( 10 '6 m
! 5 + 2$ ! 5 ' 2$
.
2.5 = #
' #
erf +
&
&
" 2 % " 2 %
+ 2 (4.03 ( 10 '15 m 2 /s) (t) .
*
-
This expression reduces to the following form:
! 393.8 s $
0.6667 = erf #
&
t %
"
Using data in Table 6.1, it is necessary to determine the value of z for which the error function is 0.6667 We use
linear interpolation as follows:
erf (z)
0.650
0.6420
0.6667
0.700
0.6778
y ! 0.650
0.6667 ! 0.6420
=
0.700 ! 0.650
0.6778 ! 0.6420
from which
y = 0.6844 =
393.8 s
t
And solving for t gives

t = 3.31 105 s = 92 h
6.15 For a steel alloy it has been determined that a carburizing heat treatment of 10-h duration will raise
the carbon concentration to 0.45 wt% at a point 2.5 mm from the surface. Estimate the time necessary to achieve
the same concentration at a 5.0-mm position for an identical steel and at the same carburizing temperature.
Solution
This problem calls for an estimate of the time necessary to achieve a carbon concentration of 0.45 wt% at a
point 5.0 mm from the surface. From Equation 6.6b,
x2
= constant
Dt
But since the temperature is constant, so also is D constant, and
x2
= constant
t
or
x12
t1
x22
t2
Thus,
(2.5 mm) 2
(5.0 mm) 2
=
10 h
t2
from which
t2 = 40 h
Factors That Influence Diffusion

6.16 Cite the values of the diffusion coefficients for the interdiffusion of carbon in both -iron (BCC) and
-iron (FCC) at 900C. Which is larger? Explain why this is the case.
Solution
We are asked to compute the diffusion coefficients of C in both and iron at 900C. Using the data in
Table 6.2,
80,000 J/mol
$
'
D! = (6.2 " 10-7 m 2 /s) exp & #
)
(8.31
J/mol-K)(1173
K)
%
(
= 1.69 10-10 m2/s
148,000 J/mol
$
'
D! = (2.3 " 10-5 m 2 /s) exp & #
)
% (8.31 J/mol-K)(1173 K) (
= 5.86 10-12 m2/s

The D for diffusion of C in BCC iron is larger, the reason being that the atomic packing factor is smaller
than for FCC iron (0.68 versus 0.74Section 3.4); this means that there is slightly more interstitial void space in
the BCC Fe, and, therefore, the motion of the interstitial carbon atoms occurs more easily.
6.17 Using the data in Table 6.2, compute the value of D for the diffusion of zinc in copper at 650C.
Solution
Incorporating the appropriate data from Table 6.2 into Equation 6.8 leads to
189,000 J/mol
#
&
D = (2.4 ! 10-5 m 2 /s) exp % "
(
(8.31
J/mol-K)(650
+
273
K)
$
'
= 4.8 10-16 m2/s

module, click on the D vs 1/T Plot submodule, and then do the following:
1. In the left-hand window that appears, click on the Zn-Cu pair under the Diffusing Species-Host
Metal headings.
2. Next, at the bottom of this window, click the Add Curve button.
3. A log D versus 1/T plot then appears, with a line for the temperature dependence of the diffusion
coefficient for Zn in Cu. Now under Temp Range in the boxes appearing below T Max change the temperature
to either 650 C or 923 K. At the top of this curve is a diamond-shaped cursor. Click-and-drag this cursor down
the line to the point at which the entry under the Temperature (T): label reads 923 K (inasmuch as this is the
Kelvin equivalent of 650C). Finally, the diffusion coefficient value at this temperature is given under the label
Diff Coeff (D):. For this problem, the value is 4.7 10-16 m2/s.
6.18 At what temperature will the diffusion coefficient for the diffusion of copper in nickel have a value of
6.5 10
-17
m2/s? Use the diffusion data in Table 6.2.

Solution
Solving for T from Equation 6.9a
T = !
Qd
R (ln D ! ln D0 )
and using the data from Table 6.2 for the diffusion of Cu in Ni (i.e., D0 = 2.7 10-5 m2/s and Qd = 256,000 J/mol) ,
we get
T = !
256,000 J/mol
#
(8.31 J/mol-K) $ ln (6.5 " 10-17 m 2 /s) ! ln (2.7 " 10 -5 m 2 /s) %&
= 1152 K = 879C
1. In the left-hand window that appears, there is a preset set of data for several diffusion systems. Click on
the box for which Cu is the diffusing species and Ni is the host metal. Next, at the bottom of this window, click the
Add Curve button.
coefficient for Cu in Ni. At the top of this curve is a diamond-shaped cursor. Click-and-drag this cursor down the
line to the point at which the entry under the Diff Coeff (D): label reads 6.5 10-17 m2/s. The temperature at
which the diffusion coefficient has this value is given under the label Temperature (T):. For this problem, the
value is 1153 K.
6.19 The preexponential and activation energy for the diffusion of iron in cobalt are 1.1 10-5 m2/s and
253,300 J/mol, respectively. At what temperature will the diffusion coefficient have a value of 2.1 10-14 m2/s?
Solution
For this problem we are given D0 (1.1 10-5) and Qd (253,300 J/mol) for the diffusion of Fe in Co, and
asked to compute the temperature at which D = 2.1 10-14 m2/s. Solving for T from Equation 6.9a yields
T =
Qd
R (ln D0 ! ln D)
253,300 J/mol
#
(8.31 J/mol-K) $ ln (1.1 ! 10-5 m 2 /s) " ln (2.1 ! 10-14 m 2 /s)%&
= 1518 K = 1245C
1. In the left-hand window that appears, click on the Custom1 box.
2. In the column on the right-hand side of this window enter the data for this problem. In the window
under D0 enter preexponential valueviz. 1.1e-5. Next just below the Qd window enter the activation
energy valueviz. 253.3. It is next necessary to specify a temperature range over which the data is to be plotted.
The temperature at which D has the stipulated value is probably between 1000C and 1500C, so enter 1000 in the
T Min box that is beside C; and similarly for the maximum temperatureenter 1500 in the box below T
Max.
3. Next, at the bottom of this window, click the Add Curve button.
coefficient for Fe in Co. At the top of this curve is a diamond-shaped cursor. Click-and-drag this cursor down the
line to the point at which the entry under the Diff Coeff (D): label reads 2.1 10-14 m2/s. The temperature at
which the diffusion coefficient has this value is given under the label Temperature (T):. For this problem, the
value is 1519 K.
6.20 The activation energy for the diffusion of carbon in chromium is 111,000 J/mol. Calculate the
diffusion coefficient at 1100 K (827C), given that D at 1400 K (1127C) is 6.25 10-11 m2/s.
Solution
To solve this problem it first becomes necessary to solve for D0 from Equation 6.8 as
!Q $
D0 = D exp # d &
" RT %
"
%
111, 000 J / mol
= (6.25 ! 10 -11 m2 /s) exp $
'
# (8.31 J/mol - K)(1400 K) &
= 8.7 10-7 m2/s
Now, solving for D at 1100 K (again using Equation 6.8) gives
111,000 J/mol
#
&
D = (8.7 ! 10-7 m 2 /s) exp % "
(
$ (8.31 J/mol-K)(1100 K) '
= 4.6 10-12 m2/s
6.21 The diffusion coefficients for iron in nickel are given at two temperatures:
T (K)
D (m2/s)
1273
9.4 1016
1473
2.4 1014
(a) Determine the values of D0 and the activation energy Qd.

(b) What is the magnitude of D at 1100C (1373 K)?
Solution
(a) Using Equation 6.9a, we set up two simultaneous equations with Qd and D0 as unknowns as follows:
ln D1 = lnD0 !
Qd " 1 %
$ '
R $# T1 '&
ln D2 = lnD0 !
Qd " 1 %
$ '
R $# T2 '&
Now, solving for Qd in terms of temperatures T1 and T2 (1273 K and 1473 K) and D1 and D2 (9.4 10-16 and 2.4
10-14 m2/s), we get
Qd = ! R
ln D1 ! ln D2
1
1
!
T1 T2
# ln (9.4 " 10 -16 ) ! ln (2.4 " 10 -14 )%

&
= ! (8.31 J/mol-K) $
1
1
!
1273 K
1473 K
= 252,400 J/mol
Now, solving for D0 from Equation 6.8 (and using the 1273 K value of D)
!Q $
D0 = D1 exp ## d &&
" RT1 %
"
%
252, 400 J/mol
= (9.4 ! 10 -16 m2 /s) exp $
'
# (8.31 J/mol - K)(1273 K) &
= 2.2 10-5 m2/s
(b) Using these values of D0 and Qd, D at 1373 K is just
#
&
252, 400 J/mol
D = (2.2 ! 10 -5 m2 /s) exp %"
(
$ (8.31 J/mol - K)(1373 K) '
= 5.4 10-15 m2/s
module, click on the D0 and Qd from Experimental Data submodule, and then do the following:
1. In the left-hand window that appears, enter the two temperatures from the table in the book (viz. 1273
and 1473, in the first two boxes under the column labeled T (K). Next, enter the corresponding diffusion
coefficient values (viz. 9.4e-16 and 2.4e-14).
3. Next, at the bottom of this window, click the Plot data button.
4. A log D versus 1/T plot then appears, with a line for the temperature dependence for this diffusion
system. At the top of this window are given values for D0 and Qd; for this specific problem these values are 2.17
10-5 m2/s and 252 kJ/mol, respectively
5. To solve the (b) part of the problem we utilize the diamond-shaped cursor that is located at the top of the
line on this plot. Click-and-drag this cursor down the line to the point at which the entry under the Temperature
(T): label reads 1373. The value of the diffusion coefficient at this temperature is given under the label Diff
Coeff (D):. For our problem, this value is 5.4 10-15 m2/s.
6.22 The diffusion coefficients for silver in copper are given at two temperatures:
T (C)
D (m2/s)
650
5.5 1016
900
1.3 1013
(a) Determine the values of D0 and Qd.

(b) What is the magnitude of D at 875C?
Solution
(a) Using Equation 6.9a, we set up two simultaneous equations with Qd and D0 as unknowns as follows:
ln D1 = lnD0 !
Qd " 1 %
$ '
R $# T1 '&
ln D2 = lnD0 !
Qd " 1 %
$ '
R $# T2 '&
Solving for Qd in terms of temperatures T1 and T2 (923 K [650C] and 1173 K [900C]) and D1 and D2 (5.5 10-16
and 1.3 10-13 m2/s), we get
Qd = ! R
= !
ln D1 ! ln D2
1
1
!
T1 T2
(8.31 J/mol-K) #$ ln (5.5 " 10 -16 ) ! ln (1.3 " 10 -13 )%&

1
1
!
923 K
1173 K
= 196,700 J/mol
Now, solving for D0 from Equation 6.8 (and using the 650C value of D)
!Q $
D0 = D1 exp ## d &&
" RT1 %
"
%
196, 700 J/mol
= (5.5 ! 10 -16 m2 /s) exp $
'
# (8.31 J/mol - K)(923 K) &
= 7.5 10-5 m2/s
(b) Using these values of D0 and Qd, D at 1148 K (875C) is just
#
&
196, 700 J/mol
D = (7.5 ! 10 -5 m2 /s) exp %"
(
$ (8.31 J/mol - K)(1148 K) '
= 8.3 10-14 m2/s
module, click on the D0 and Qd from Experimental Data submodule, and then do the following:
1. In the left-hand window that appears, enter the two temperatures from the table in the book (converted
from degrees Celsius to Kelvins) (viz. 923 (650C) and 1173 (900C), in the first two boxes under the column
labeled T (K). Next, enter the corresponding diffusion coefficient values (viz. 5.5e-16 and 1.3e-13).
3. Next, at the bottom of this window, click the Plot data button.
4. A log D versus 1/T plot then appears, with a line for the temperature dependence for this diffusion
system. At the top of this window are given values for D0 and Qd; for this specific problem these values are 7.55
10-5 m2/s and 196 kJ/mol, respectively
5. To solve the (b) part of the problem we utilize the diamond-shaped cursor that is located at the top of the
line on this plot. Click-and-drag this cursor down the line to the point at which the entry under the Temperature
(T): label reads 1148 (i.e., 875C). The value of the diffusion coefficient at this temperature is given under the
label Diff Coeff (D):. For our problem, this value is 8.9 10-14 m2/s.
6.23 The accompanying figure shows a plot of the logarithm (to the base 10) of the diffusion coefficient
versus reciprocal of the absolute temperature for the diffusion of iron in chromium. Determine values for the
activation energy and preexponential.
Solution
This problem asks us to determine the values of Qd and D0 for the diffusion of Fe in Cr from the plot of log
Q
(rather than ! d since we are
2.3 R
R
using log D rather than ln D) and the intercept at 1/T = 0 gives the value of log D0. The slope is equal to
D versus 1/T. According to Equation 6.9b the slope of this plot is equal to !
slope =
Qd
! (log D) log D1 ( log D2

=
1
1
" 1%
(
!$ '
#T&
T1
T2
Taking 1/T1 and 1/T2 as 0.65 10-3 and 0.60 10-3 K-1, respectively, then the corresponding values of D1 and D2
are 2.51 10-16 and 1.82 10-15, as noted in the figure below.
The values of log D1 and log D2 are 15.60 and 14.74, and therefore,
Qd = ! 2.3 R (slope)
Qd = ! 2.3 R
log D1 ! log D2
1
1
!
T1
T2
#
&
!15.60 ! (!14.74)
= ! (2.3)(8.31 J/mol - K) %
(
$ (0.65 " 10!3 ! 0.60 " 10!3 ) K!1 '
= 329,000 J/mol
Rather than trying to make a graphical extrapolation to determine D0, a more accurate value is obtained
analytically using Equation 6.9b taking a specific value of both D and T (from 1/T) from the plot given in the
problem; for example, D = 1.0 10-15 m2/s at T = 1626 K (1/T = 0.615 10-3 K-1). Therefore
!Q $
D0 = D exp # d &
" RT %
329,000 J/mol
"
%
= (1.0 ! 10-15 m 2 /s) exp $
'
# (8.31 J/mol-K)(1626 K) &
= 3.75 10-5 m2/s
6.24 Carbon is allowed to diffuse through a steel plate 15 mm thick. The concentrations of carbon at the
two faces are 0.65 and 0.30 kg C/m3 Fe, which are maintained constant. If the preexponential and activation energy
are 6.2 10-7 m2/s and 80,000 J/mol, respectively, compute the temperature at which the diffusion flux is 1.43 10-9
kg/m2-s.
Solution
Combining Equations 6.3 and 6.8 yields
J = !D
= ! D0
"C
"x
"C
# Q &
exp % ! d (
$ RT '
"x
Solving for T from this expression leads to
!Q $
T = # d&
" R%
1
! D0 (C $
ln # '
" J (x &%
And incorporation of values provided in the problem statement yields
! 80,000 J/mol $
=#
" 8.31 J/mol-K &%
1
' 10 (7 m 2 /s
) (6.2
)(0.65 kg/m 3 ( 0.30 kg/m 3 ) ,
ln +
(1.43 ' 10 (9 kg/m 2 -s)(15 ' 10 (3 m ) .*
= 1044 K = 771C
6.25 The steady-state diffusion flux through a metal plate is 5.4 10-10 kg/m2-s at a temperature of 727C
(1000 K) and when the concentration gradient is -350 kg/m4. Calculate the diffusion flux at 1027C (1300 K) for
the same concentration gradient and assuming an activation energy for diffusion of 125,000 J/mol.
Solution
In order to solve this problem, we must first compute the value of D0 from the data given at 727C (1000
K); this requires the combining of both Equations 6.3 and 6.8 as
J = !D
"C
"x
# Q &
"C
= ! D0
exp %! d (
"x
$ RT '
Solving for D0 from the above expression gives
D0 = !
#Q &
J
exp % d (
"C
$ RT '
"x
# 5.4 " 10 !10 kg/m 2 -s &

125,000 J/mol
)
,
= !%
( exp + (8.31 J/mol-K)(1000 K) .
4
! 350 kg / m
$
'
*
= 5.26 10-6 m2/s
The value of the diffusion flux at 1300 K may be computed using these same two equations as follows:
# "C &
# Q &
J = ! D0 %
exp % ! d (
(
$ RT '
$ "x '
125,000 J/mol
#
&
= ! (5.26 " 10-6 m 2 /s)(!350 kg/m 4 ) exp % !
(
$ (8.31 J/mol-K)(1300 K) '
= 1.74 10-8 kg/m2-s
6.26 At approximately what temperature would a specimen of -iron have to be carburized for 2 h to
produce the same diffusion result as carburization at 900C for 15 h?
Solution
To solve this problem it is necessary to employ Equation 6.7
Dt = constant
Which, for this problem, takes the form
D900 t900 = DT t T
At 900C, and using the data from Table 6.2, for the diffusion of carbon in -ironi.e.,
D0 = 2.3 10-5 m2/s
Qd = 148,000 J/mol
the diffusion coefficient is equal to
#
&
148,000 J/mol
D900 = (2.3 ! 10-5 m 2 /s) exp % "
(
$ (8.31 J/mol-K)(900 + 273 K ) '
= 5.9 10-12 m2/s
Thus, from the above equation
(5.9
! 10 -12 m2 /s) (15 h) = DT (2 h)
And solving for DT
DT =
(5.9 ! 10 -12
m2 /s)(15 h)
= 4.43 ! 10 -11 m2 /s
2h
Now, solving for T from Equation 6.9a gives
T =!
Qd
R (ln DT ! ln D0 )
= !
148,000 J/mol
(8.31 J/mol-K) #$ ln (4.43 " 10-11 m 2 /s) ! ln (2.3 " 10-5 m 2 /s)%&
= 1353 K = 1080C
6.27 (a) Calculate the diffusion coefficient for copper in aluminum at 500C.
(b) What time will be required at 600C to produce the same diffusion result (in terms of concentration at a
specific point) as for 10 h at 500C?
Solution
(a) We are asked to calculate the diffusion coefficient for Cu in Al at 500C. Using the data in Table 6.2
and Equation 6.8
" Q %
D = D0 exp $! d '
# RT &
#
&
136,000 J / mol
= (6.5 ! 10 -5 m2 /s) exp %"
(
$ (8.31 J/mol - K)(500 + 273 K) '
= 4.15 10-14 m2/s
(b) This portion of the problem calls for the time required at 600C to produce the same diffusion result as
for 10 h at 500C. Equation 6.7 is employed as
D500 t500 = D600 t 600

Now, from Equation 6.8 the value of the diffusion coefficient at 600C is calculated as
#
&
136,000 J/mol
D600 = (6.5 ! 10 -5 m2 /s) exp %"
(
$ (8.31 J/mol - K)(600 + 273 K) '
= 4.69 10-13 m2/s
Thus,
t600 =
D500 t 500
D600
(4.15 ! 10"14 m2 /s) (10 h) =

(4.69 ! 10"13 m2 /s)
0.88 h
6.28 A diffusion couple similar to that shown in Figure 6.1a is fashioned of two hypothetical A and B
metals. After a 30-min heat treatment at 1500 K, the concentration of metal A in B is 84 wt% A at the 6-mm position
in metal B. At what temperature must this diffusion couple be heated to produce this same concentration (i.e., 84
wt% A) at a 4-mm position after 30 min? For the diffusion coefficient of metal A in metal B, assume preexponential
and activation energy values of 1.0 10-4 m2/s and 75,000 J/mol, respectively.
Solution
In order to determine the temperature to which the diffusion couple must be heated so as to produce a
concentration of 84 wt% A at the 4.0-mm position, we must first utilize Equation 6.6b with time t being a constant.
That is
x2
= constant
D
Or
2
x1500
x2
= T
D1500 DT
Now, solving for DT from this equation, yields
DT =
xT2 D1500
2
x1500
and incorporating the temperature dependence of D1500 utilizing Equation 6.8, realizing that for the diffusion of A
in B
D0 = 1.0 10-4 m2/s
Qd = 75,000 J/mol
then
DT =
xT2 D1500
2
x1500
( xT2 ) (*) D0 exp "$# ! QRTd %'& +-,

2
x1500
(4 mm)2 +(1.0 ! 10"4 m 2 /s)exp % "

=
+*
&,
75,000 J/mol
(.
(8.31 J/mol-K)(1500 K) ' .-
(6 mm)2
= 1.08 10-7 m2/s

We now need to find the T at which D has this value. This is accomplished by rearranging Equation 6.9a and
solving for T as
T =
Qd
R (lnD0 ! lnD)
75,000 J/mol
(8.31 J/mol-K) #$ ln (1.0 ! 10-4 m 2 /s) " ln (1.08 ! 10-7 m 2 /s)%&
= 1321 K = 1048C
6.29 A diffusion couple similar to that shown in Figure 6.1a is prepared using two hypothetical metals A
and B. After a 30-h heat treatment at 1000 K (and subsequently cooling to room temperature) the concentration of
A in B is 3.2 wt% at the 15.5-mm position within metal B. If another heat treatment is conducted on an identical
diffusion couple, but at 800 K for 30 h, at what position will the composition be 3.2 wt% A? Assume that the
preexponential and activation energy for the diffusion coefficient are 1.8 10-5 m2/s and 152,000 J/mol,
respectively.
Solution
In order to determine the position within the diffusion couple at which the concentration of A in B is 3.2
wt%, we must employ Equation 6.6b with t constant. That is
x2
= constant
D
Or
2
x800
D800
2
x1000
D1000
It is first necessary to compute values for both D800 and D1000; this is accomplished using Equation 6.8 as follows:
#
&
152,000 J/mol
D800 = (1.8 ! 10-5 m 2 /s) exp % "
(
(8.31
J/mol-K)(800
K)
$
'
= 2.12 10-15 m2/s
152,000 J/mol
#
&
D1000 = (1.8 ! 10-5 m 2 /s) exp % "
(
(8.31
J/mol-K)(1000
K)
$
'
= 2.05 10-13 m2/s

Now, solving the above expression for x800 yields
x800 = x1000
D800
D1000
= (15.5 mm)
2.12 ! 10 "15 m 2 /s
2.05 ! 10 "13 m 2 /s
= 1.6 mm
6.30 The outer surface of a steel gear is to be hardened by increasing its carbon content. The carbon is to
be supplied from an external carbon-rich atmosphere that is maintained at an elevated temperature. A diffusion
heat treatment at 850C (1123 K) for 10 min increases the carbon concentration to 0.90 wt% at a position 1.0 mm
below the surface. Estimate the diffusion time required at 650C (923 K) to achieve this same concentration also at
a 1.0-mm position.
Assume that the surface carbon content is the same for both heat treatments, which is
maintained constant. Use the diffusion data in Table 6.2 for C diffusion in -Fe.
Solution
In order to compute the diffusion time at 650C to produce a carbon concentration of 0.90 wt% at a
position 1.0 mm below the surface we must employ Equation 6.6b with position (x) constant; that is
Dt = constant
Or
D850 t850 = D650 t 650

In addition, it is necessary to compute values for both D850 and D650 using Equation 6.8. From Table 6.2, for the
diffusion of C in -Fe, Qd = 80,000 J/mol and D0 = 6.2 10-7 m2/s. Therefore,
#
&
80,000 J/mol
D850 = (6.2 ! 10-7 m 2 /s) exp % "
(
$ (8.31 J/mol-K)(850 + 273 K) '
= 1.17 10-10 m2/s
#
&
80,000 J/mol
D650 = (6.2 ! 10-7 m 2 /s) exp % "
(
$ (8.31 J/mol-K)(650 + 273 K) '
= 1.83 10-11 m2/s
Now, solving the original equation for t650 gives
t650 =
D850 t 850
D650
(1.17
! 10"10 m2 /s) (10 min)

1.83 ! 10"11 m2 /s
= 63.9 min
6.31 An FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated temperature
and in an atmosphere in which the surface carbon concentration is maintained at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the surface, determine the temperature at which the
treatment was carried out.
Solution
This problem asks us to compute the temperature at which a nonsteady-state 49.5 h diffusion anneal was
carried out in order to give a carbon concentration of 0.35 wt% C in FCC Fe at a position 4.0 mm below the surface.
From Equation 6.5
" x %
Cx ! C0
0.35 ! 0.20
=
= 0.1875 = 1 ! erf $
'
Cs ! C0
1.0 ! 0.20
# 2 Dt &
Or
! x $
erf #
& = 0.8125
" 2 Dt %
Now it becomes necessary, using the data in Table 6.1 and linear interpolation, to determine the value of
x
.
2 Dt
Thus
erf (z)
0.90
0.7970
0.8125
0.95
0.8209
y ! 0.90
0.8125 ! 0.7970
=
0.95 ! 0.90
0.8209 ! 0.7970
From which
y = 0.9324
Thus,
x
= 0.9324
2 Dt
-3
And since t = 49.5 h (178,200 s) and x = 4.0 mm (4.0 10 m), solving for D from the above equation yields
D =
x2
(4t)(0.9324 ) 2
(4.0 ! 10"3 m)2

(4)(178, 200 s)(0.869 )
= 2.58 ! 10 -11 m2 /s
Now, in order to determine the temperature at which D has the above value, we must employ Equation 6.9a; solving
this equation for T yields
T =
Qd
R (lnD0 ! lnD)
From Table 6.2, D0 and Qd for the diffusion of C in FCC Fe are 2.3 10
-5
m /s and 148,000 J/mol, respectively.
Therefore
T =
148,000 J/mol
#
(8.31 J/mol-K) $ ln (2.3 ! 10-5 m 2 /s) " ln (2.58 ! 10-11 m 2 /s)%&
= 1300 K = 1027C
Diffusion in Semiconducting Materials

6.32 Phosphorus atoms are to be diffused into a silicon wafer using both predeposition and drive-in heat
treatments; the background concentration of P in this silicon material is known to be 5 1019 atoms/m3. The
predeposition treatment is to be conducted at 950C for 45 minutes; the surface concentration of P is to be
maintained at a constant level of 1.5 1026 atoms/m3. Drive-in diffusion will be carried out at 1200C for a period
of 2.5 h. For the diffusion of P in Si, values of Qd and D0 are 3.40 eV and 1.1 10-4 m2/s, respectively.
(a) Calculate the value of Q0.
(b) Determine the value of xj for the drive-in diffusion treatment.
(c) Also for the drive-in treatment, compute the position x at which the concentration of P atoms is 1024 m-3.
Solution
(a) For this portion of the problem we are asked to determine the value of Q0. This is possible using
Equation 6.12. However, it is first necessary to determine the value of D for the predeposition treatment [Dp at Tp =
950C (1223 K)] using Equation 6.8. Thus
" Q %
D p = D0 exp $ ! d '
# kT p &
3.40 eV
#
&
= (1.1 ! 10 "4 m 2 /s)exp % "
(
"5
(8.62
!
10
eV/atom-K)(1223
K)
$
'
= 1.08 ! 10"18 m2 /s
The value of Q0 may be determined as follows:
Q0 = 2C s
= (2)(1.5 ! 10 26 atoms / m3)
D pt p
!
(1.08 ! 10"18 m2 /s)(45 min)(60 s / min)

#
= 9.14 ! 1018 atoms / m2
(b) Computation of the junction depth requires that we use Equation 6.13. However, before this is possible
it is necessary to calculate D at the temperature of the drive-in treatment [Dd at 1200C (1473 K)]. Thus,
#
&
3.40 eV
Dd = (1.1 ! 10 "4 m 2 /s)exp % "
(
"5
$ (8.62 ! 10 eV/atom-K)(1473 K ) '
= 2.58 ! 10"16 m2 /s
Now from Equation 6.13
(
"
Q0
x j = * (4Dd t d ) ln$$
*)
# C B !Dd t d
1/ 2
%+
''&,
1/2
*,
$
' .,
9.14 ! 1018 atoms/m 2
= +(4)(2.58 ! 10 "16 m 2 /s)(9000 s) ln &
)/
&% (5 ! 1019 atoms/m 3 ) (# )(2.58 ! 10 "16 m 2 /s)(9000 s) )( 0,
-,
= 1.21 ! 10"5 m = 12.1 m

(c) For a concentration of 1024 P atoms/m3 for the drive-in treatment, we compute the value of x using
Equation 6.11. However, it is first necessary to manipulate Equation 6.11 so that x is the dependent variable.
Taking natural logarithms of both sides leads to
" Q0 %
x2
ln C(x,t) = ln $
'(
# ! Dd t d & 4Dd t d
Now, rearranging and solving for x leads to
(*
"
Q0
x = )(4Dd t d ) ln $
C(x,t)
! Dd t d
$#
+*
1/2
% ,*
''& .*
Now, incorporating values for Q0 and Dd determined above and taking C(x,t) = 1024 P atoms/m3 yields
1/2
*
$
' .,
9.14 ! 1018
,
)/
x = +(4)(2.58 ! 10 "16 )(9000) ln &
24 ) (# )(2.58 ! 10 "16 )(9000) )
&
(10
%
( 0,
-,
= 3.36 ! 10 "6 m = 3.36 m
6.33 Aluminum atoms are to be diffused into a silicon wafer using both predeposition and drive-in heat
treatments; the background concentration of Al in this silicon material is known to be 3 1019 atoms/m3. The drivein diffusion treatment is to be carried out at 1050C for a period of 4.0 h, which gives a junction depth xj of 3.0 m.
Compute the predeposition diffusion time at 950C if the surface concentration is maintained at a constant level of 2
1025 atoms/m3. For the diffusion of Al in Si, values of Qd and D0 are 3.41 eV and 1.38 10-4 m2/s, respectively.
Solution
This problem asks that we compute the time for the predeposition heat treatment for the diffusion of Al in
Si. In order to do this it is necessary to determine the value of Q0 from Equation 6.13. However, before doing this
we must first calculate Dd, using Equation 6.8. Therefore
" Q %
Dd = D0 exp $ ! d '
# kTd &
#
&
3.41 eV
= (1.38 ! 10 "4 m 2 /s) exp % "
(
"5
(8.62
!
10
eV/atom-K)(1050C
+
273
K)
$
'
= 1.43 ! 10 "17 m 2 /s
Now, solving for Q0 in Equation 6.13 leads to
" x 2j %
Q0 = C B ! Dd t d exp $
'
# 4Dd t d &
In the problem statement we are given the following values:

CB = 3 1019 atoms/m3
td = 4 h (14,400 s)
xj = 3.0 m = 3.0 10-6 m
Therefore, incorporating these values into the above equation yields
$
&
(3.0 ! 10 #6 m)2
Q0 = $(3 ! 1019 atoms/m 3 ) (" )(1.43 ! 10 #17 m 2 /s)(14, 400 s) & exp (
)
#17
2
%
'
% (4)(1.43 ! 10 m /s)(14, 400 s) '
= 1.34 ! 1018 atoms/m 2

We may now compute the value of tp using Equation 6.12. However, before this is possible it is necessary to
determine Dp (at 950C) using Equation 6.8. Thus
#
&
3.41 eV
D p = (1.38 ! 10 "4 m 2 /s) exp % "
(
"5
$ (8.62 ! 10 eV/atom-K)(950C + 273 K) '
= 1.24 ! 10 "18 m 2 /s
Now, solving for tp in Equation 6.12 we get
tp =
!Q02
4C s2 D p
And incorporating the value of Cs provided in the problem statement (2 1025 atoms/m3) as well as values for Q0
and Dp determined above, leads to
tp =
! (1.34 " 1018 atoms/m)2

(4)(2 " 10 25 atoms/m 3 )2 (1.24 " 10 #18 m 2 /s)
= 2.84 ! 10 3 s = 47.4 min
Diffusion in Polymeric Materials

6.34 Consider the diffusion of water vapor through a polypropylene (PP) sheet 2 mm thick. The pressures
of H2O at the two faces are 1 kPa and 10 kPa, which are maintained constant. Assuming conditions of steady state,
what is the diffusion flux in [(cm3 STP)/cm2-s] at 298 K?
Solution
This is a permeability problem in which we are asked to compute the diffusion flux of water vapor through
a 2-mm thick sheet of polypropylene. In order to solve this problem it is necessary to employ Equation 6.14. The
permeability coefficient of H2O through PP is given in Table 6.4 as 38 10-13 (cm3 STP)-cm/cm2-s-Pa. Thus, from
Equation 6.14
J = PM
!P
P " P1
= PM 2
!x
!x
and taking P1 = 1 kPa (1,000 Pa) and P2 = 10 kPa (10,000 Pa) we get
"
(cm 3 STP)(cm) % ) 10,000 Pa ( 1,000 Pa ,
= $ 38 ! 10-13
' +
.0.2 cm
cm 2 -s-Pa & *
#
= 1.71 ! 10-7
(cm 3 STP)
cm 2 -s
6.35 Argon diffuses through a high-density polyethylene (HDPE) sheet 40 mm thick at a rate of 4.0 107
(cm3 STP)/cm2-s at 325 K. The pressures of argon at the two faces are 5000 kPa and 1500 kPa, which are
maintained constant. Assuming conditions of steady state, what is the permeability coefficient at 325 K?
Solution
This problem asks us to compute the permeability coefficient for argon through high density polyethylene
at 325 K given a steady-state permeability situation. It is necessary for us to Equation 6.14 in order to solve this
problem. Rearranging this expression and solving for the permeability coefficient gives
PM =
J !x
J !x
=
!P
P2 " P1
Taking P1 = 1500 kPa (1,500,000 Pa) and P2 = 5000 kPa (5,000,000 Pa), the permeability coefficient of Ar through
HDPE is equal to
3
"
-7 (cm STP) % (4 cm)
$ 4.0 ! 10
'
cm 2 -s &
PM = #
(5,000,000 Pa ( 1,500,000 Pa)
= 4.57 ! 10-13
(cm 3 STP)(cm)
cm 2 -s-Pa
6.36 The permeability coefficient of a type of small gas molecule in a polymer is dependent on absolute
temperature according to the following equation:
" Qp %
PM = PM 0 exp $ !
# RT '&
where PM 0 and Qp are constants for a given gas-polymer pair. Consider the diffusion of hydrogen through a
poly(dimethyl siloxane) (PDMSO) sheet 20 mm thick. The hydrogen pressures at the two faces are 10 kPa and 1
kPa, which are maintained constant. Compute the diffusion flux [in (cm3 STP)/cm2 s] at 350 K. For this diffusion
system
PM 0 = 1.45 ! 10 "8 (cm 3 STP)(cm)/cm 2 - s - Pa

Qp = 13.7 kJ/mol
Assume a condition of steady state diffusion.
Solution
This problem asks that we compute the diffusion flux at 350 K for hydrogen in poly(dimethyl siloxane)
(PDMSO). It is first necessary to compute the value of the permeability coefficient at 350 K. The temperature
dependence of PM is given in the problem statement, as follows:
" Q %
p
'
PM = PM exp $$!
'
0
RT
#
&
And incorporating values provided for the constants PM and Qp, we get
0
"
"
%
(cm 3 STP)(cm) %
13, 700 J/mol
PM = $1.45 ! 10-8
' exp $ (
'
2 -s-Pa
(8.31
J/mol
-K)(350
K)
cm
#
&
#
&
= 1.31 ! 10 "10
(cm 3 STP)(cm)
cm 2 -s-Pa
And using Equation 6.14, the diffusion flux is equal to
J = PM
= 1.31 ! 10-10
!P
P " P1
= PM 2
!x
!x
(cm 3 STP)(cm) # 10,000 Pa " 1,000 Pa &

%$
('
2.0 cm
cm 2 -s-Pa
= 5.90 ! 10-7
(cm 3 STP)
cm 2 -s
DESIGN PROBLEMS
Steady-State Diffusion
6.D1 It is desired to enrich the partial pressure of hydrogen in a hydrogen-nitrogen gas mixture for which
the partial pressures of both gases are 0.1013 MPa (1 atm). It has been proposed to accomplish this by passing
both gases through a thin sheet of some metal at an elevated temperature; inasmuch as hydrogen diffuses through
the plate at a higher rate than does nitrogen, the partial pressure of hydrogen will be higher on the exit side of the
sheet. The design calls for partial pressures of 0.0709 MPa (0.7 atm) and 0.02026 MPa (0.2 atm), respectively, for
hydrogen and nitrogen. The concentrations of hydrogen and nitrogen (CH and CN, in mol/m3) in this metal are
functions of gas partial pressures (pH and pN , in MPa) and absolute temperature and are given by the following
2
2
expressions:
# 27.8 kJ/mol &

CH = 2.5 ! 10 3 pH 2 exp %"
(
$
'
RT
(6.18a)
# 37.6 kJ/mol &

CN = 2.75 ! 10"3 pN 2 exp %"
(
$
'
RT
(6.18b)
Furthermore, the diffusion coefficients for the diffusion of these gases in this metal are functions of the absolute
temperature as follows:
# 13.4 kJ/mol &

DH (m 2 /s) = 1.4 ! 10 "7 exp % "
('
$
RT
(6.19a)
# 76.15 kJ/mol &

DN (m 2 /s) = 3.0 ! 10 "7 exp % "
('
$
RT
(6.19b)
Is it possible to purify hydrogen gas in this manner? If so, specify a temperature at which the process may be
carried out, and also the thickness of metal sheet that would be required. If this procedure is not possible, then state
the reason(s) why.
Solution
This problem calls for us to ascertain whether or not a hydrogen-nitrogen gas mixture may be enriched with
respect to hydrogen partial pressure by allowing the gases to diffuse through a metal sheet at an elevated
temperature. If this is possible, the temperature and sheet thickness are to be specified; if such is not possible, then
we are to state the reasons why. Since this situation involves steady-state diffusion, we employ Fick's first law,
Equation 6.3. Inasmuch as the partial pressures on the high-pressure side of the sheet are the same, and the pressure
of hydrogen on the low pressure side is 3.5 times that of nitrogen, and concentrations are proportional to the square
root of the partial pressure, the diffusion flux of hydrogen JH is the square root of 3.5 times the diffusion flux of
nitrogen JNi.e.
JH =
3.5 J N
Thus, equating the Fick's law expressions incorporating the given equations for the diffusion coefficients and
concentrations in terms of partial pressures leads to the following
JH =
(2.5 ! 10 3 )(
(2.75 ! 10 3 )(
0.1013 MPa "
0.1013 MPa "
1
"
!x
# 27.8 kJ &
#
&
0.0709 MPa exp % "
(1.4 ! 10 "7 m 2 /s) exp % " 13.4 kJ (
(
RT '
RT '
$
$
3.5 J N
3.5
"
!x
# 37.6 kJ &
#
&
0.02026 MPa exp % "
(3.0 ! 10 "7 m 2 /s) exp % " 76.15 kJ (
(
RT '
RT '
$
$
The x's cancel out, which means that the process is independent of sheet thickness. Now solving the above
expression for the absolute temperature T gives
T = 3237 K
which value is extremely high (surely above the melting point of the metal). Thus, such a diffusion process is not
possible.
6.D2 A gas mixture is found to contain two diatomic A and B species, the partial pressures of which for
both are 0.05065 MPa (0.5 atm). This mixture is to be enriched in the partial pressure of the A species by passing
both gases through a thin sheet of some metal at an elevated temperature. The resulting enriched mixture is to have
a partial pressure of 0.02026 MPa (0.2 atm) for gas A and 0.01013 MPa (0.1 atm) for gas B. The concentrations of
A and B (CA and CB, in mol/m3) are functions of gas partial pressures (pA and pB , in MPa) and absolute
2
temperature according to the following expressions:
" 25.0 kJ/mol %

C A = 200 pA 2 exp $!
'
#
&
RT
(6.20a)
# 30.0 kJ/mol &

CB = 1.0 ! 10"3 pB 2 exp %"
(
$
'
RT
(6.20b)
Furthermore, the diffusion coefficients for the diffusion of these gases in the metal are functions of the absolute
temperature as follows:
# 15.0 kJ/mol &

DA (m 2 /s) = 4.0 ! 10 "7 exp % "
('
$
RT
(6.21a)
# 24.0 kJ/mol &

DB (m 2 /s) = 2.5 ! 10 "6 exp % "
('
$
RT
(6.21b)
Is it possible to purify the A gas in this manner? If so, specify a temperature at which the process may be carried
out, and also the thickness of metal sheet that would be required. If this procedure is not possible, then state the
reason(s) why.
Solution
This problem calls for us to ascertain whether or not an A2-B2 gas mixture may be enriched with respect to
the A partial pressure by allowing the gases to diffuse through a metal sheet at an elevated temperature. If this is
possible, the temperature and sheet thickness are to be specified; if such is not possible, then we are to state the
reasons why.
Since this situation involves steady-state diffusion, we employ Fick's first law, Equation 6.3.
Inasmuch as the partial pressures on the high-pressure side of the sheet are the same, and the pressure of A2 on the
low pressure side is 2.0 times that of B2, and concentrations are proportional to the square root of the partial
pressure, the diffusion flux of A, JA, is the square root of 2.0 times the diffusion flux of nitrogen JBi.e.
JA =
2.0 J B
Thus, equating the Fick's law expressions incorporating the given equations for the diffusion coefficients and
concentrations in terms of partial pressures leads to the following
JA =
(200)(
(1.0
0.05065 MPa !
! 10 3 )
1
"
!x
" 25.0 kJ %
"
%
0.02026 MPa exp $ !
(4.0 ( 10 !7 m 2 /s) exp $ ! 15.0 kJ '
RT '&
RT &
#
#
0.05065 MPa "
2.0 J B
2.0
"
!x
# 30.0 kJ &
# 24.0 kJ &
"6 2
0.01013 MPa exp % "
( (2.5 ! 10 m /s) exp %$ "
(
$
RT '
RT '
The x's cancel out, which means that the process is independent of sheet thickness. Now solving the above
expression for the absolute temperature T gives
T = 401 K (128C)
Thus, it is possible to carry out this procedure at 401 K or 128C.
Nonsteady-State Diffusion
6.D3 The wear resistance of a steel shaft is to be improved by hardening its surface. This is to be
accomplished by increasing the nitrogen content within an outer surface layer as a result of nitrogen diffusion into
the steel. The nitrogen is to be supplied from an external nitrogen-rich gas at an elevated and constant temperature.
The initial nitrogen content of the steel is 0.002 wt%, whereas the surface concentration is to be maintained at 0.50
wt%. For this treatment to be effective, a nitrogen content of 0.10 wt% must be established at a position 0.40 mm
below the surface. Specify appropriate heat treatments in terms of temperature and time for temperatures between
475C and 625C. The preexponential and activation energy for the diffusion of nitrogen in iron are 3 10-7 m2/s
and 76,150 J/mol, respectively, over this temperature range.
Solution
This is a nonsteady-state diffusion situation; thus, it is necessary to employ Equation 6.5, utilizing the
following values for the concentration parameters:
C0 = 0.002 wt% N
Cs = 0.50 wt% N
Cx = 0.10 wt% N
Therefore
Cx ! C0 0.10 ! 0.002
=
Cs ! C0 0.50 ! 0.002
" x %
= 0.1968 = 1 ! erf $
# 2 Dt '&
And thus
" x %
1 ! 0.1968 = 0.8032 = erf $
# 2 Dt '&
Using linear interpolation and the data presented in Table 6.1
erf (z)
0.9000
0.7970
0.8032
0.9500
0.8209
0.8032 ! 0.7970
y ! 0.9000
=
0.8209 ! 0.7970
0.9500 ! 0.9000
From which
y =
x
= 0.9130
2 Dt
The problem stipulates that x = 0.40 mm = 4.0 10-4 m. Therefore
4.0 ! 10"4 m
= 0.9130
2 Dt
Which leads to
Dt = 4.80 10-8 m2
Furthermore, the diffusion coefficient depends on temperature according to Equation 6.8; and as stipulated in the
problem statement, D0 = 3 10-7 m2/s and Qd = 76,150 J/mol. Hence
" Q %
Dt = D0 exp $ ! d ' (t) = 4.80 ( 10-8 m 2
# RT &
(3.0
76,150 J/mol &

#
"8
2
! 10-7 m 2 /s) exp % "
( (t) = 4.80 ! 10 m
$ (8.31 J/mol-K)(T ) '
And solving for the time t
t (in s) =
0.160
" 9163.7 %
exp $ !
'
#
T &
Thus, the required diffusion time may be computed for some specified temperature (in K). Below are tabulated t
values for three different temperatures that lie within the range stipulated in the problem statement.
Temperature
(C)
Time
h
500
22,500
6.3
550
11,000
3.1
600
5800
1.6
Diffusion in Semiconducting Materials

6.D4 One integrated circuit design calls for the diffusion of arsenic into silicon wafers; the background
concentration of As in Si is 2.5 1020 atoms/m3. The predeposition heat treatment is to be conducted at 1000C for
45 min, with a constant surface concentration of 8 1026 As atoms/m3. At a drive-in treatment temperature of
1100C, determine the diffusion time required for a junction depth of 1.2 m. For this system, values of Qd and D0
are 4.10 eV and 2.29 10-3 m2/s, respectively.
Solution
This problem asks that we compute the drive-in diffusion time for arsenic diffusion in silicon. It is first
necessary to determine the value of Q0 using Equation 6.12. But before this is possible, the value of Dp at 1000C
must be computed with the aid of Equation 6.8. Thus,
" Q %
D p = D0 exp $ ! d '
# kT p &
#
&
4.10 eV
= (2.29 ! 10 "3 m 2 /s)exp % "
"5 eV/atom-K)(1000C + 273 K) (
(8.62
!
10
$
'
= 1.36 ! 10"19 m2 /s
Now for the computation of Q0 using Equation 6.12:
Q0 = 2C s
= (2)(8 ! 10 26 atoms/m 3 )
D pt p
!
(1.36 ! 10 "19 m 2 /s)(45 min)(60 s/min)

#
= 1.73 ! 1019 atoms/m2

We now desire to calculate td in Equation 6.13. Algebraic manipulation and rearrangement of this expression leads
to
! x 2j $
Q0
exp #
& =
C B ' Dd t d
" 4Dd t d %
At this point it is necessary to determine the value of Dd (at 1100C). Thus
#
&
4.10 eV
Dd = (2.29 ! 10 "3 m 2 /s)exp % "
(
"5
$ (8.62 ! 10 eV/atom-K)(1100C + 273 K) '
= 2.06 ! 10"18 m2 /s
And incorporation of values of all parameters except td in the above expression yields
#
&
(1.2 ! 10 "6 m)2
1.73 ! 1019 atoms/m 2
exp %
=
(
"18 m 2 /s)t
(2.5 ! 10 20 atoms/m 3 ) () )(2.06 ! 10 "18 m 2 /s)t d
d'
$ (4)(2.06 ! 10
which expression reduces to
" 1.75 ! 10 5 s %
2.72 ! 10 7 s1/2
exp $
=
'
td
td
#
&
Solving for td is not a simple matter. One possibility is to use a graphing technique. Let us take the logarithm of
both sides of the above equation, which gives
" 2.72 ! 10 7 s1/2 %

1.75 ! 10 5 s
= ln $
'
td
td
#
&
Now if we plot the terms on both left and right hand sides of this equation versus td, the value of td at the point of
intersection of the two resulting curves is correct answer. Below is such a plot:
As noted, the two curves intersect at about 13,900 s, which corresponds to td = 3.86 h.
Fundamentals of Engineering Questions and Problems

6.1FE Atoms of which of the following elements diffuse most rapidly in iron?
(A) Mo
(B) C
(C) Cr
(D) W
Solution
The correct answer is B. Carbon atoms diffuse most rapidly because they are smaller than atoms of Mo,
Cr, and W. Furthermore, diffusion of C in Fe is via an interstitial mechanism, whereas for Mo, Cr, and W the
mechanism is vacancy diffusion.
6.2FE Calculate the diffusion coefficient for copper in aluminum at 600C. Preexponential and activation
-5
energy values for this system are 6.5 10 m /s and 136,000 J/mol, respectively.
(A) 5.7 10-2 m2/s
(B) 9.4 10-17 m2/s
(C) 4.7 10-13 m2/s
(D) 3.9 10-2 m2/s
Solution
We are asked to calculate the diffusion coefficient for Cu in Al at 600C, given values for D0 and Qd. This
determination is possible using Equation 6.8 as follows:
" Q %
D = D0 exp $ ! d '
# RT &
#
&
136,000 J/mol
= (6.5 ! 10-5 m 2 /s)exp % "
(
$ (8.31 J/mol-K)(600 + 273 K) '
= 4.7 10-13 m2/s
Therefore, the correct answer is C.

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CHAPTER 6

6.5 (a) Briefly explain the concept of a driving force.

# 0.6 ! 2.4 kg / m3 &

Similarly, for 0.0075 wt% C

= 3.95 10-11 m2/s

# 27.2 kJ / mol &

7.82 ! 10"4 kg / m3 " 5.53 ! 10"3 kg / m3

It can be shown that

wherein, Cx = 0.45, C0 = 0.20, Cs = 1.30, and x = 2 mm = 2 10-3 m. Thus,

By linear interpolation using data from Table 6.1

Now, from Table 6.2, at 1000C (1273 K)

Solving for t yields

Using data in Table 6.1 and linear interpolation

Which means that

(6.9 ! 10"11 m2 /s)( 3.6 ! 10 4 s)

= 1.26 10-3 m = 1.26 mm

Using data in Table 6.1 and linear interpolation

This expression gives

This expression reduces to the following form:

And solving for t gives

Factors That Influence Diffusion

= 1.69 10-10 m2/s

= 5.86 10-12 m2/s

= 4.8 10-16 m2/s

m2/s? Use the diffusion data in Table 6.2.

Solving for T from Equation 6.9a

= 4.6 10-12 m2/s

(a) Determine the values of D0 and the activation energy Qd.

# ln (9.4 " 10 -16 ) ! ln (2.4 " 10 -14 )%

(a) Determine the values of D0 and Qd.

(8.31 J/mol-K) #$ ln (5.5 " 10 -16 ) ! ln (1.3 " 10 -13 )%&

! (log D) log D1 ( log D2

Solving for T from this expression leads to

And incorporation of values provided in the problem statement yields

# 5.4 " 10 !10 kg/m 2 -s &

= 1.74 10-8 kg/m2-s

! 10 -12 m2 /s) (15 h) = DT (2 h)

And solving for DT

Now, solving for T from Equation 6.9a gives

D500 t500 = D600 t 600

(4.15 ! 10"14 m2 /s) (10 h) =

Now, solving for DT from this equation, yields

( xT2 ) (*) D0 exp "$# ! QRTd %'& +-,

(4 mm)2 +(1.0 ! 10"4 m 2 /s)exp % "

= 1.08 10-7 m2/s

= 2.05 10-13 m2/s

D850 t850 = D650 t 650

! 10"10 m2 /s) (10 min)

(4.0 ! 10"3 m)2

m /s and 148,000 J/mol, respectively.

Diffusion in Semiconducting Materials

(1.08 ! 10"18 m2 /s)(45 min)(60 s / min)

= 9.14 ! 1018 atoms / m2

= 1.21 ! 10"5 m = 12.1 m

Now, rearranging and solving for x leads to

= 3.36 ! 10 "6 m = 3.36 m

In the problem statement we are given the following values:

= 1.34 ! 1018 atoms/m 2

! (1.34 " 1018 atoms/m)2

= 2.84 ! 10 3 s = 47.4 min