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DIFFUSION
PROBLEM SOLUTIONS
5.1 Self-diffusion is atomic migration in pure metals--i.e., when all atoms exchanging positions are of the
same type. Interdiffusion is diffusion of atoms of one metal into another metal.
5.2 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.
5.3 (a) With vacancy diffusion, atomic motion is from one lattice site to an adjacent vacancy. Selfdiffusion 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.
5.4 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 species--i.e.,
the diffusion flux is independent of time.
5.5 (a) The driving force is that which compels a reaction to occur.
(b) The driving force for steady-state diffusion is the concentration gradient.
5.6 This problem calls for the mass of hydrogen, per hour, that diffuses through a Pd sheet. It first
becomes necessary to employ both Equations (5.1a) and (5.3). Combining these expressions and
solving for the mass yields
M = JAt =
85
= 2.6 x 10
-3
kg/h
3
5.7 We are asked to determine the position at which the nitrogen concentration is 2 kg/m . This problem
is solved by using Equation (5.3) in the form
J =
3
If we take C to be the point at which the concentration of nitrogen is 4 kg/m , then it becomes
A
necessary to solve for x , as
B
C
xB = x A + D A
Assume x
xB = 0 + 6 x 10 -11 m2 /s
-3
= 1 x 10 m = 1 mm
5.8 This problem calls for computation of the diffusion coefficient for a steady-state diffusion situation.
3
Let us first convert the carbon concentrations from wt% to kg C/m using Equation (4.9a). For 0.012
wt% C
''
CC
=
CC
0.012
CC
0.012
2.25 g / cm3
86
0.944 kg C/m
CC'' =
0.0075
0.0075
2.25 g / cm3
= 0.590 kg C/m
D =
= 3.95 x 10
-11
2
m /s
5.9 This problems asks for us to compute the diffusion flux of hydrogen gas through a 1-mm thick plate of
iron at 250C when the pressures on the two sides are 0.15 and 7.5 MPa. Ultimately we will employ
Equation (5.3) to solve this problem.
concentration of hydrogen at each face using Equation (5.11). At the low pressure (or B) side
CH(B) = 1.34 x 10 -2
-6
9.93 x 10 wt%
Whereas, for the high pressure (or A) side
CH(A) = 1.34 x 10 -2
87
-5
7.02 x 10 wt%
We now convert concentrations in weight percent to mass of hydrogen per unit volume of solid. At
-6
-9
face B there are 9.93 x 10 g (or 9.93 x 10 kg) of hydrogen in 100 g of Fe, which is virtually pure
3
iron. From the density of iron (7.87 g/cm ), the volume iron in 100 g (V ) is just
B
VB =
100 g
7.87 g / cm 3
= 12.7 cm
= 1.27 x 10
-5
Therefore, the concentration of hydrogen at the B face in kilograms of H per cubic meter of alloy [
''
CH(B)
] is just
''
CH(B)
=
9.93 x 10
CH(B)
VB
-5
''
CH(A)
=
7.02 x 10
3
m , and
CH(A )
VA
Thus, the concentration gradient is just the difference between these concentrations of hydrogen
divided by the thickness of the iron membrane; that is
''
''
CH(B)
CH(A)
C
=
x
xB xA
7.82 x 10
88
At this time it becomes necessary to calculate the value of the diffusion coefficient at 250C using
Equation (5.8). Thus,
D = D o exp
= 1.4 x 10
= 6.41 x 10
-9
2
m /s
And, finally, the diffusion flux is computed using Equation (5.3) by taking the negative product of this
diffusion coefficient and the concentration gradient, as
J =
=
Cx =
B
exp
Dt
is a solution to
C
2C
= D
t
x 2
simply by taking appropriate derivatives of the C expression. When this is carried out,
x
2
C
C
B
= D
=
2
1/
t
x
2 D 2t 3 / 2
5.11
x2
2 Dt 1
exp
x2
4Dt
We are asked to compute the diffusion time required for a specific nonsteady-state diffusion
situation. It is first necessary to use Equation (5.5).
89
C x
-3
m. Thus,
or
x
erf
2 Dt
erf(z)
0.85
0.7707
0.7727
0.90
0.7970
From which
z = 0.854 =
x
2 Dt
D = 2.3 x 10 -5 m2 /s
= 1.93 x 10
Thus,
90
-11
2
m /s
2 x 10
0.854 =
Thus,
x
erf
2 Dt
erf (z)
0.40
0.4284
0.4545
0.45
0.4755
And,
z = 0.4277
Which means that
x
2 Dt
= 0.4277
And, finally
91
x = 2(0.4277)
4.3 x 10
Dt = (0.8554)
= 1.06 x 10
-3
m = 1.06 mm
5.13 This problem asks us to compute the nitrogen concentration (C ) at the 1 mm position after a 10 h
x
diffusion time, when diffusion is nonsteady- state. From Equation (5.5)
C x
= 1
= 1 - erf (0.527)
Using data in Table 5.1 and linear interpolation
z
erf (z)
0.500
0.5205
0.527
0.550
0.5633
0.527
from which
y = erf (0.527) = 0.5436
Thus,
Cx
92
C = 0.046 wt% N
x
5.14 (a) The solution to Fick's second law for a diffusion couple composed of two semi-infinite solids of
the same material is as follows:
C1
C x =
for the boundary conditions
C = C for x < 0, and t = 0
1
(b) For this particular silver-gold diffusion couple for which C = 5 wt% Au and C = 2 wt% Au, we
1
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, the equation in part (a) takes the form
5
2.5 =
It now becomes necessary to compute the diffusion coefficient at 750C (1023 K) given that D = 8.5
o
-5 2
x 10 m /s and Q = 202,100 J/mol. From Equation (5.8) we have
d
D = D oexp
= 8.5 x 10
-5
2
m /s
= 4.03 x 10
-15
2
m /s
93
5
2.5 =
erf (z)
0.650
0.6420
0.6667
0.700
0.6778
from which
y = 0.6844 =
393.8
x2
x2
1 = 2
t1
t2
Thus,
(2.5 mm)
10 h
(5.0 mm)
t2
from which
t = 40 h
2
5.16 We are asked to compute the diffusion coefficients of C in both and iron at 900C. Using the
data in Table 5.2,
= 1.69 x 10
-10
2
m /s
= 5.86 x 10
-12
2
m /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 0.74); 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.
5.17 This problem asks us to compute the magnitude of D for the diffusion of Zn in Cu at 650C (923 K).
From Table 5.2
D = 2.4 x 10-5 m2 /s
95
= 4.8 x 10
-16
2
m /s
5.18 We are asked to calculate the temperature at which the diffusion coefficient for the diffusion of Cu in
-17 2
Ni has a value of 6.5 x 10
m /s. Solving for T from Equation (5.9a)
T =
and using the data from Table 5.2 for the diffusion of Cu in Ni
T =
= 1152 K = 879C
5.19 For this problem we are given D and Q for the diffusion of Cr in Ni, and asked to compute the
o
d
-14 2
temperature at which D = 1.2 x 10
m /s. Solving for T from Equation (5.9a) yields
T =
Qd
R ln D o
(8.31 J/mol - K) ln 1.1 x 10 -4
= 1427 K = 1154C
5.20 In this problem we are given Q
Q
Do = D exp d
RT
96
-14
2
m /s. It first becomes
= 1.0 x 10
-14
2
m /s
= 1.22 x 10
-4
2
m /s
D = 1.22 x 10
-4
2
m /s
= 4.8 x 10
-13
2
m /s
5.21 (a) Using Equation (5.9a), we set up two simultaneous equations with Q and D as unknowns.
d
o
-16
Solving for Q in terms of temperatures T and T (1273 K and 1473 K) and D and D (9.4 x 10
d
1
2
1
2
-14 2
and 2.4 x 10
m /s), we get
Q d =
= 252,400 J/mol
Now, solving for D from Equation (5.8)
o
Q
d
Do = D1exp
RT
= 9.4 x 10
-16
2
m /s
97
= 2.2 x 10
-5
2
m /s
D = 2.2 x 10
-5
2
m /s
= 5.4 x 10
-15
2
m /s
5.22 (a) Using Equation (5.9a), we set up two simultaneous equations with Q and D as unknowns.
d
o
Solving for Q in terms of temperatures T and T (873 K [600C] and 973 K [700C]) and D and
d
1
2
1
-14
-13 2
D (5.5 x 10
and 3.9 x 10
m /s), we get
2
Q d =
= 138,300 J/mol
Now, solving for D from Equation (5.8)
o
Q
d
Do = D1exp
RT
= 5.5 x 10
-14
2
m /s
= 1.05 x 10
98
-5
2
m /s
D = 1.05 x 10
-5
2
m /s
= 3.8 x 10
-12
2
m /s
5.23 This problem asks us to determine the values of Q and D for the diffusion of Au in Ag from the
d
o
plot of log D versus 1/T. According to Equation (5.9b) the slope of this plot is equal to - Q /2.3R
d
(rather than - Q /R since we are using log D rather than ln D) and the intercept at 1/T = 0 gives the
d
value of log D . The slope is equal to
o
slope =
-3
-3 -1
Taking 1/T and 1/T as 1.0 x 10 and 0.90 x 10 K , respectively, then the values of log D and
1
2
1
log D are 14.68 and 13.57, respectively. Therefore,
2
Q d =
= 212,200 J/mol
Rather than trying to make a graphical extrapolation to determine D , a more accurate value is
o
obtained analytically using Equation (5.9b) taking a specific value of both D and T (from 1/T) from the
-14 2
-3
plot given in the problem; for example, D = 1.0 x 10
m /s at T = 1064 K (1/T = 0.94 x 10 ).
Therefore
99
Q d
Do = D exp
RT
= 1.0 x 10
-14
2
m /s
= 2.65 x 10
5.24
-4
2
m /s
This problem asks that we compute the temperature at which the diffusion flux is 6.3 x 10
2
kg/m -s. Combining Equations (5.3) and (5.8) yields
J =
-10
T = d
R
80, 000 J / mol
=
8.31 J / mol - K
= 900 K = 627C
5.25 In order to solve this problem, we must first compute the value of D from the data given at 1200C
o
(1473 K); this requires the combining of both Equations (5.3) and (5.8). Solving for D from these
o
expressions gives
Do =
100
= 2.18 x 10
-5
2
m /s
The value of the diffusion flux at 1273 K may be computed using these same two equations as
follows:
J =
= 1.21 x 10
-8
2
kg/m -s
5.26 To solve this problem it is necessary to employ Equation (5.7) which takes on the form
D900t 900 = DT t T
At 900C, and using the data from Table 5.2
D900 = 2.3 x 10
-5
2
m /s
= 5.9 x 10
Thus,
5.9 x 10
-12
-12
2
m /s
m /s
And
D = 4.43 x 10
-11
2
m /s
101
= 1353 K = 1080C
5.27 (a) We are asked to calculate the diffusion coefficient for Cu in Al at 500C. Using the data in Table
5.2
D = D o exp
= 6.5 x 10
-5
2
m /s
= 4.15 x 10
-14
2
m /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 (5.7) is employed as
D500t 500 = D600t600
D600 = 6.5 x 10
-5
2
m /s
= 4.69 x 10
Thus,
t 600 =
-13
2
m /s
D500 t500
D600
4.15 x 10
102
5.28 In order to determine the temperature to which the diffusion couple must be heated so as to produce
a concentration of 3.0 wt% Ni at the 2-mm position, we must first utilize Equation (5.6b) with time t
being a constant. That is
2
x
= constant
D
Or
x2
1000
D1000
x2
T
DT
DT =
2
x
(2 mm) 2 2.7
x 10
= 2.21 x 10
-13
2
m /s
We now need to find the T at which D has this value. This is accomplished by rearranging Equation
(5.9a) and solving for T as
T =
Qd
R ln D
o
= 1357 K = 1084C
5.29 In order to determine the position within the diffusion couple at which the concentration of A in B is
2.5 wt%, we must employ Equation (5.6b) with t constant. That is
103
x
= constant
D
Or
x2800
D800
800
and D
1000
2
x1000
D1000
D800 = 1.5 x 10 -4 m2 /s
= 1.22 x 10
-10
2
m /s
D1000 = 1.5 x 10 -4 m2 /s
= 1.11 x 10
Now, solving for x
1000
-9
2
m /s
yields
x1000 = x 800
= (5 mm)
D 1000
D
800
1.11 x 10
= 15.1 mm
5.30 In order to compute the diffusion time at 900C to produce a carbon concentration of 0.75 wt% at a
position 0.5 mm below the surface we must employ Equation (5.6b) with position constant; that is
Dt = constant
Or
104
and D
600
900
D600 = 6.2 x 10
-7
-7
900
-11
2
m /s
2
m /s
= 1.69 x 10
Now, solving for t
2
m /s. Therefore,
2
m /s
= 1.01 x 10
D900 = 6.2 x 10
-7
-10
2
m /s
gives
t 900 =
D600 t 600
D900
1.01 x 10
= 5.98 min
5.31 This problem asks us to compute the temperature at which a nonsteady-state 48 h diffusion anneal
was carried out in order to give a carbon concentration of 0.30 wt% C in FCC Fe at a position 3.5
mm below the surface. From Equation (5.5)
C x
Or
x
erf
2 Dt
105
Now it becomes necessary to, using the data in Table 5.1 and linear interpolation, to determine the
x
value of 2 Dt .
z
erf (z)
0.90
0.7970
0.8000
0.95
0.8209
From which
y = 0.9063
Thus,
x
2 Dt
= 0.9063
D =
(4t)(0.9063 )2
3.5 x 10
Now, in order to solve for the temperature at which D has the above value, we must employ Equation
(5.9a); solving for T yields
T =
Qd
R ln Do
From Table 5.2, D and Q for the diffusion of C in FCC Fe are 2.3 x 10
o
d
respectively. Therefore
106
-5
2
m /s and 148,000 J/mol,
T =
= 1283 K = 1010C
Design Problems
5.D1 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 an iron
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 (5.3). 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 five times that of nitrogen, and concentrations are proportional to the square root of
the partial pressure, the diffusion flux of hydrogen J is the square root of 5 times the diffusion flux of
H
nitrogen J --i.e.
N
JH
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
J
2.5 x 10
1
x
x
5 JN
5
x
x
3
2.75 x 10
107
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 = 3467 K
which value is extremely high (surely above the vaporization point of iron). Thus, such a diffusion
process is not possible.
5.D2 This problem calls for us to ascertain whether or not an A -B gas mixture may be enriched with
2
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 (5.3). Inasmuch as the partial pressures on the highpressure side of the sheet are the same, and the pressure of A on the low pressure side is 2.5 times
2
that of B , and concentrations are proportional to the square root of the partial pressure, the diffusion
2
flux of A, J , is the square root of 2.5 times the diffusion flux of nitrogen J --i.e.
A
JA =
2.5 JB
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
J
=
3
1.5 x 10
2.5 JB
2.5
108
2.0 x 10
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 = 568 K (295C)
5.D3 This is a nonsteady-state diffusion situation; thus, it is necessary to employ Equation (5.5), utilizing
the following values for the concentration parameters:
C = 0.0025 wt% N
o
C = 0.45 wt% N
s
C = 0.12 wt% N
x
Therefore
C x
= 0.2626 = 1
And thus
1
erf (z)
0.7500
0.7112
0.7374
0.8000
0.7421
109
0.7374
From which
y =
x
2 Dt
= 0.7924
-4
m. Therefore
4.5 x 10
Which leads to
Dt = 8.06 x 10
-8
2
m
Furthermore, the diffusion coefficient depends on temperature according to Equation (5.8); and, as
-7 2
stipulated in the problem, D = 3 x 10 m /s and Q = 76,150 J/mol. Hence
o
d
Dt = Doexp
3.0 x 10
-7
m /s
t (in s) =
0.269
exp
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.
_________________________________
Temperature
Time
110
(C)
_________________________________
500
37,900
10.5
550
18,400
5.1
600
9,700
2.7
__________________________________
5.D4 This is a nonsteady-state diffusion situation; thus, it is necessary to employ Equation (5.5), utilizing
the following values for the following parameters:
C = 0.15 wt% C
o
1.2 wt% C C 1.4 wt% C
s
C = 0.75 wt% C
x
x = 0.65 mm
Let us begin by assuming a specific value for the surface concentration within the specified range
say 1.2 wt% C. Therefore
C x
= 0.5714 = 1
And thus
1
erf (z)
0.4000
0.4284
0.4286
0.4500
0.4755
111
0.4286
From which
y =
x
2 Dt
= 0.4002
-4
m. Therefore
6.5 x 10
Which leads to
Dt = 6.59 x 10
-7
2
m
Furthermore, the diffusion coefficient depends on temperature according to Equation (5.8); and, as
-5 2
noted in Design Example 5.1, D = 2.3 x 10 m /s and Q = 148,000 J/mol. Hence
o
d
Dt = Doexp
2.3 x 10
-5
m /s
t (in s) =
2.86 x 10
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.
_________________________________
112
Temperature
(C)
Time
s
_________________________________
1000
34,100
9.5
1100
12,300
3.4
1200
5,100
1.4
__________________________________
Now, let us repeat the above procedure for two other values of the surface concentration, say 1.3 wt
% C and 1.4 wt% C. Below is a tabulation of the results, again using temperatures of 1000 C,
1100C, and 1200C.
C
s
(wt% C)
1.3
1.4
Temperature
Time
(C)
1000
26,700
7.4
1100
9,600
2.7
1200
4,000
1.1
1000
21,100
6.1
1100
7,900
2.2
1200
1,500
0.9
113