5.

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.
5.6 The purification of hydrogen gas by diffusion through a palladium sheet was discussed in Section 5.3.
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 500°C. Assume a diffusion coefficient of 1.0 × 10-8 m2/s, that the
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 5.1a and 5.3. Combining these expressions and solving for
the mass yields

"C
M = JAt = ! DAt
"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

5.7 A sheet of steel 1.5 mm thick has nitrogen atmospheres on both sides at 1200°C 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 5.3 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
5.12 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 (1127°C). 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 10-h heat treatment at 1325 K when C0 = 0.35 wt% C. From Equation 5.5

Cx ! C0 0.15 ! 0.35 " x %

= = 0.5714 = 1 ! erf $ '
Cs ! C0 0 ! 0.35 # 2 Dt &

Thus,

! x $
erf # & = 0.4286
" 2 Dt %

Using data in Table 5.1 and linear interpolation

z erf (z)
0.40 0.4284
z 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 coefficient—viz. “6.9e-11”.

2. In the window just below the label “Initial, C0” enter the initial concentration—viz. “0.35”.

3. In the window the lies below “Surface, Cs” enter the surface concentration—viz. “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 s—so 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) is ranges between 1.24 and 1.30 mm.

5.21 The diffusion coefficients for iron in nickel are given at two temperatures:

T (K) D (m2/s)
1273 9.4 × 10–16
1473 2.4 × 10–14

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

(b) What is the magnitude of D at 1100ºC (1373 K)?

Solution

(a) Using Equation 5.9a, we set up two simultaneous equations with Qd and D0 as unknowns as

follows:

Qd " 1 %
ln D1 = lnD0 ! $ '
R $# T1 '&

Qd " 1 %
ln D2 = lnD0 ! $ '
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

ln D1 ! ln D2
Qd = ! R
1 1
!
T1 T2

= ! (8.31 J/mol - K)
[ln (9.4 " 10 -16) ! ]
ln (2.4 " 10 -14 )
1 1
!
1273 K 1473 K

= 252,400 J/mol

Now, solving for D0 from Equation 5.8 (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

Note: this problem may also be solved using the “Diffusion” module in the VMSE software. Open the

“Diffusion” 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 give 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.
5.32 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 950°C 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
1200°C 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
24 -3
10 m .

Solution

(a) For this portion of the problem we are asked to determine the value of Q0. This is possible

using Equation 5.12. However, it is first necessary to determine the value of D for the predeposition
treatment [Dp at Tp = 950°C (1223 K)] using Equation 5.8. Thus

" Q %
D p = D0 exp$$! d ''
# kT p &

# 3.40 eV &
= (1.1 ! 10"4 m2 /s) exp%" (
$ (8.62 ! 10"5 eV / atom " K)(1223 K) '

= 1.08 ! 10"18 m2 /s

The value of Q0 may be determined as follows:

D pt p
Q0 = 2C s
!

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

= (2)(1.5 ! 10 26 atoms / m3)
#
= 9.14 ! 1018 atoms / m2

(b) Computation of the junction depth requires that we use Equation 5.13. However, before this
is possible it is necessary to calculate D at the temperature of the drive-in treatment [Dd at 1200°C (1473

K)]. Thus,
 # 3.40 eV &
Dd = (1.1 ! 10"4 m2 /s) exp%" "5 (
$ (8.62 ! 10 eV / atom " K)(1473 K) '

= 2.58 ! 10"16 m2 /s

Now from Equation 5.13

1/ 2
( " Q0 %+
x j = * (4Dd t d ) ln$$ '-
'-
*) # C B !Dd t d &,

1/ 2
*, $ '.,
"16 9.14 ! 1018 atoms / m2
= + (4)(2.58 ! 10 m /s)(9000 s) ln&
2 )/
,- &% (5 ! 1019 atoms / m3 ) (#)(2.58 ! 10"16 m2 /s)(9000 s) )(,0

= 1.21 ! 10"5 m = 12.1 µm

(c) For a concentration of 1024 P atoms/m3 for the drive-in treatment, we compute the value of x
using Equation 5.11. However, it is first necessary to manipulate Equation 5.11 so that x is the dependent
variable. Taking natural logarithms of both sides leads to

" Q % x2
lnC (x, t) = ln$$ 0 '(
' 4D t
# !Dd t d & d d

Now, rearranging and solving for x leads to

1/ 2
(* " Q0 %,*
x = ) (4Dd t d ) ln$ '-
*+ $# C (x, t) !Dd t d '&*.

Now, incorporating values for Q0 and Dd determined above and taking C(x,t) = 1024 P atoms/m3 yields

1/ 2
*, $ '.,
9.14 ! 10 18
x = + (4)(2.58 ! 10"16 )(9000) ln& )/
,- &% (10 24 ) (#)(2.58 ! 10"16 )(9000) )(,0
= 3.36 ! 10"6 m = 3.36 µm