MM 677: Diffusion and Kinetics

Assignment 4: Atomic models of diffusion and

diffusivity evaluation

1. Consider an atom making random jumps in 1-D – either to the right

or to the left. If it makes N - random jumps, how much does it get
displaced from its initial position? Write an Octave script to carry out
this simulation; run this simulation starting with five different random
seeds and report the average as the result. Extend the script to do the
simulation in 2-D. What is the result? Consider the ratio of the net
displacement to the total distance travelled by the atom in 1- and 2-D.
What do you see? What can you conclude from these numbers?

2. In the derivation of diffusivity as a function of atomic jumps in the case

of interstitial diffusion, we have used n1 − n2 = −α2 ∂C B
∂x
. Derive this
expression.

3. Show that the vacancy

concentration XV at any temperature T is given
∆GV
by XV = exp − RT .

4. Consider the data shown in Table 1. Plot the diffusivity at the melt-
ing temperature, D(Tm ), as a function of normalised activation energy,
namely, RTQm . What do you observe? How will you explain your obser-
vations?

5. Show that in the case of self-diffusivity, the diffusivity of the tracer is

orders of magnitude smaller than the diffusivity of the vacancy.
Hint: Instead of considering the jump of the tracer atom, consider the
movement of vacancy; when an atom jumps into the vacant site, we
can consider the vacancy to have made an opposite jump. In such a
scenario, there is complete analogy with interstitial diffusion because a
vacant site is always surrounded by atoms and hence has equal proba-
bility to jump to any of the neighbouring sites. So, DV = 16 ΓV α2 and
hence DB = XV DV .

6. In the substitutional solid, show that the atomic flux defined including
the lattice movement (as in Eq.1) leads to the flux of B atoms to be

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 Element Tm (in K) D0 (mm2 s−1 ) Q (kJ mol−1 )

Fe (α) 1811 200 239.7

Fe (γ) 1805 49 284.1
Cr 2130 20 308.6
V 2163 28.8 309.2
Nb 2741 1240 439.6
Mo 2890 180 460.6
Ta 3269 124 413.3
Al 933 170 142
Ag 1234 40 184.6
Au 1336 10.7 176.9
Cu 1356 31 200.3
Ni 1726 190 279.7
Pt 2046 22 278.4

Table 1: The data of different elements, their melting point, and the diffu-
sivity (D0 and activation energy).

equal and opposite that of A atoms.

∂CA
JA = −DA + vCA (1)
∂x
7. Consider a diffusion couple made up of pure A and pure B. Plot the
composition profiles, the fluxes of A, B and vacancies, and the rate of
change of vacancies, schematically. State your assumptions clearly.
8. Consider the interdiffusion coefficient in a very dilute solution. What
do you observe? Why?
Hint: Dilute solution implies XB → 0. The diffusivity in such a
scenario is also called the impurity diffusion.
9. Often, DB in a dilute solution of B in A (the impurity diffusion) is
found to be greater than intrinsic diffusivity of the host DA . What
could be the reason?

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10. Laser flash method
Let us consider the working principle of laser flash method for deter-
mining the thermal diffusivity of a solid. In this method, we flash a
laser on the surface of a material and instantaneously raise its temper-
ature to T0 over a shallow region – that is, a region whose depth is very
small compared to the size of the sample. Then, we can obtain the
thermal diffusivity of the sample by monitoring the temperature at the
other end as a function of time – specifically, from the time required
for half of the maximum value to be reached.
As we have shown the Fick’s second law and the law of heat conduction
are mathematically identical. Hence, we can use the series solution that
we derived using the variable separable method and analyse the laser
flash method results.
This problem is based on Parker et al, Journal of Applied Physics,
Vol. 32, No. 9, pp. 1679-1684 (1961). Of course, there are important
corrections to be made relaxing some of the assumptions. But those
are outside the scope of this course.

• Let T (x, 0) be the initial temperature profile within a thermally

insulated solid of thickness L. Then, using the appropriate initial
and boundary conditions and using the variable seperable tech-
nique, it can be shown that the temperature distribution at time
t is given by

Z L
1
T (x, t) = T (x, 0)dx (2)
L 0
∞  2 2  h nπx i Z L
2 X −n π αt h nπx i
+ exp cos T (x, 0) cos dx
L n=1 L2 L 0 L

where α is the thermal diffusivity (in m2 /sec).

Let Q (in J/m2 ) be the laser energy absorbed, instantaneously at
a depth of d from the surface x = 0; let us assume the solid to be
thermally insulated and be of uniform thickness L (in m). Thus,

Q
T (x, 0) = for 0 < x < d (3)
ρcd

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 and
T (x, 0) = 0 for d < x < L (4)
where ρ is the density (in kg/m3 ) and c is the heat capacity (in
J/kgK).
Substituting these conditions in Eq. 2, to obtain
D
T (x, t) = (5)
ρcL
" ∞ #
−n2 π 2 αt
X h nπx i sin [nπd/L] 
+ 1+2 cos exp
n=1
L nπd/L L2

• Assuming the material to be opaque, and since d/L ≪ 1, we

can replace sin [nπd/L] by nπd/L. So, that x = L, with this
approximation, we find
" ∞  2 2 #
D X −n π αt
T (L, t) = 1+2 (−1)n exp 2
(6)
ρcL n=1
L

Let Tmax be the maximum temperature at x = L; let T ′ be the

normalised temperature at the rear x = L; that is T ′ = TT(L,t)
max
.
2
Further, using ω 2 = πLαt
2 , we obtain

∞
X
′
T =1+2 (−1)n exp (−n2 ω 2 ) (7)
n=1

Using Octave, plot Eq. 7.

• When does the temperature becomes half the maximum value?
How can we obtain α from t 1 ?
2

11. Tracer diffusion: diffusivity

The thin film solution is typically used to obtain the tracer diffusion
coefficient. Typically a thin film of radioactive tracer is plated on a
cylinder and the diffusion is allowed to take place for a set amount of
time. Then, by sectioning the sample and measuring the radioactivity,
and comparing the results with thin film solution, one can obtain the
diffusivity of tracer in the given material.

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 Distance (in cm) Normalised fraction of iostopes

0.0002122 0.015616
0.0004751 0.015085
0.0007642 0.014471
0.0010528 0.01353
0.0014736 0.012754
0.0018941 0.011814
0.0022095 0.011119
0.0025514 0.010465
0.0029723 0.00977
0.0033933 0.009117
0.0037616 0.008463
0.004209 0.00781
0.0045509 0.007197
0.0049194 0.006666
0.005367 0.006136
0.0058674 0.005606
0.0063939 0.004912
0.0070523 0.004219
0.0078163 0.003567
0.008633 0.002875
0.0093183 0.002469
0.0102673 0.001982
0.0111371 0.001454
0.0119809 0.001131
0.0133787 0.00077
0.0148294 0.000491
0.0164914 0.000336
0.0185227 0.000183
0.0203169 0.000152
0.0218472 0.00016

Table 2: The tabulated values of distance versus isotope concentration. See

R A De Souza and M Martin, phys. stat. sol. (c) 4, No. 6, 1785–1801 (2007)
(DOI 10.1002/pssc.200675227)

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 In an experiment on oxygen tracer diffusion in Fe-doped SrTiO3 , a sam-
ple annealed at 973 K for 86300 seconds, the depth and the normalised
oxygen isotope fraction are as given in Table 2.
This data given in the table is also available as an csv file named Trac-
erDiffusionData.csv
Using this data, evaluate the diffusivity by fitting a straight line to the
logarithm of concentration and square of distance. Specifically,

• Read the data and plot it.

• Consider the thin-film source solution:
M x2
c(x, t) = √ exp − (8)
4πDt 4Dt

Fit the given data to this expression and hence evaluate D.

• Plot the residuals of the the fit. What can you say about the fit?
• Read the paper of De Souza and Martin? What is their comment
about the fit? ]bf Hint: Check their explanation about tracer
surface exchange coefficient.

12. Boltzmann-Matano analysis

Let us consider the data on Cu-Zn diffusion couple from the work of
Hozha, Oettel and Heger (Hoxha A, Oettel H, Heger D. Calculation
of the interdiffusion coefficient in the Cu-Zn diffusion couple. In AIP
Conference Proceedings 2010 Jan 21 (Vol. 1203, No. 1, pp. 591-595).
American Institute of Physics.) I have digitised the data from the figure
2 of the paper. The data corresponds to one hour of diffusion at 653 K
and is shown in Table 3.
This data is also saved as a csv file called CuZnDiffusionProfile.csv.

• Using Octave, plot the data.

• Identify the Matano interface;
Hint: In order to identify the Matano interface, fit the given data
to a tanh profile (an S curve). Since tanh goes from -1 to +1 as x
goes from -∞ to ∞, you have to fit the function c2m (1 + tanh(ax −
b)) where cm is the maximum value of the composition and a and

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 Distance (in µm) Concentration of Zn (in wt.%)

75.2 0.9
80.0 3.6
80.1 14.5
82.0 29.9
82.0 43.2
83.6 49.3
84.4 53.9
85.2 58.8
87.6 62.0
89.0 64.0
92.1 65.6
98.2 67.0
118.1 67.7
142.7 67.9
166.0 69.0

Table 3: The tabulated values of distance versus Zn concentration in a Cu-

Zn diffusion couple. See Hoxha A, Oettel H, Heger D. Calculation of the
interdiffusion coefficient in the Cu-Zn diffusion couple. In AIP Conference
Proceedings 2010 Jan 21 (Vol. 1203, No. 1, pp. 591-595). American Institute
of Physics.

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 b are the parameters to be determined. You may use non-linear
least squares for the fitting exercise.
and,
• Evaluate the diffusivity as a function of composition D(c) across
the diffusion couple.
Hint: Once the Matano interface (or, the reference x = 0) is
identified, the diffusivity at any concentration c can be obtained
using the formula
R c′
1 xdc
D(c′ ) = − 0 
 dc (9)
2t0 dx c=c′

For example, show that the diffusivity at c = 20 wt.% Zn is 2.2 ×

10−14 m2 /sec (at 653 K).

13. Consider a diffusion couple experiment in Cu-Zn system with inert

markers. It is given that the composition at the inert marker is XZn =
0.22 and the composition gradient at the inert marker is ∂X∂xZn = 0.09mm−1 .
Further, if the velocity of the inert marker is known to be 2.52 ×10−8
mm2 s−1 , and that the interdiffusion coefficient at the marker is 2.816
×10−13 m2 s−1 , calculate the diffusivities of Zn and Cu.

14. Consider a metallic system with a very high dislocation density of the
order of 1015 m−2 . Let the pipe radius be 1.27 nm (which is approx-
imately 5b, where b is the magnitude of the Burger’s vector in this
system). What is the total area of the pipe per unit area of the ma-
trix? At a temperature where the ratio of the pipe diffusivity to the
bulk diffusivity is 0.9, what is the ratio of the apparent diffusivity to
the bulk diffusivity? Suppose if the temperature is reduced such that
the ratio of the pipe diffusivity to the bulk diffusivity is 100, what is
the ratio of the apparent diffusivity to the bulk diffusivity?