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Comment on “diffusion of iron, cobalt and nickel in silver”
ACTA
328
METALLURGICA,
VOL.
12, 1964
Comment
on “Diffusion of iron, cobalt and nickel in silver”*
Results the
in the recent work by Hirano
diffusion
crystalline previous.
of
iron,
and
silver differ markedly works
Hirone
cobalt
and
of Mullen,(2)
Yamamoto.c4J
these differences,
from
Hirone The
et uZ.(~) on
nickel
aZ.,t3)
and
cited(l)
for
et
reason
which are, for example,
orders of magnitude
in poly-
those in the
about three
for the diffusion
coefficient
of
iron in silver, was that previous investigators(2-4) used the wrong solution experimental
to Pick’s second law for the
conditions
of the present
encountered.
note is to examine
and to propose a more reasonable FIG. 3. The y-plot constructed by integrating the graphs
of Fig. 2.
The iron y-plot may be summarised Yflll) ~ =
1.028 f
0.008,
Y*
YWm, 1.045 & 0.009,
Mykura.(l)
Simple
than at (100) for section
theory
for Ni obtained
predicts
for
clean
by f.c.c-
et aZ.(s)) a deeper cusp at (111)
and also predicts C.
a steeper
This difference
found that surface diffusion
gradient
may
be due to
possibly
on these specimens
Values
of D may
They
No faceting with
range
also derived;
106O”C, compares
and our y-plot
The twin boundary
the result,
exp
is con-
energy
was
yr/y,,.
= 0.014 & 0.004 at with the value of 0.017 f 0.006
be calculated
by fitting
straight
from
0.73 x lo-l3
to
1.85 x lo-l3
This is of the same order as the value of 2.60 x lo-l3 cm2/sec
determined
“correct”
by
Hirano
et al.(l)
using
the
solution to the diffusion equation,
C _ =
c,
also due to such impurity
was observed this.
solution of the diffusion
cm2/sec for the initial and final values respectively.
was
adsorption. sistent
of Hirano
lines through the first three and the last three points.
impurity adsorption near { 1001; Blakely and Mykuraf3) slower near {loo},
data
of Co60 in silver at 788°C
yields a plot of In (A) vs. X2 which is a smooth curve.
A in Fig. 2, where we find the steepest
slope in section
for their
1.044 < ~‘@!!! < 1.068.
to the results
(Mackenzie
of the penetration
A = &
in y at (100) with a shallower cusp at
is similar
surfaces
0.012
Y(loo,
The minimum
argument
equation,
Yt100,
Y%” __ = Y(loo,
(111)
Examination
by means of the “incorrect”
= 1.058 f
The purpose
these differences
existence. et uZ.fl) for the diffusion
as:
had
erf
1 _
(Y-5 275 1-
Therefore
the differences
magnitude
cannot be explained
of about
three
On the other hand, if it is recognized of Hirano sectioning
et al.(l) were technique
orders
of
by this argument.
obtained
by
that the data a very
and that the anomalous,
thin near-
obtained by Blakely and Mykura from a much smaller
surface
number of twins.
in such data, the differences can be readily resolved. For example, in the work of Pawel and Lundy”) on
M. M. acknowledges
the receipt
of a maintenance
diffusion
effect(s-9)
plays
grantfromD.S.I.R.,andwethanktheB.I.andS.R.A.
the diffusion
of Nbss in tantalum
for providing
the diffusion
coefficient
the specimen
material.
Department of Natural Philosophy University of Glasgow Glasgow, W.2 References. 1. H. MYEURA, Acta Met. 9, 570 (1961).
August
28, 1963.
role
it was shown that
at 1250°C as calculated
from
M. MCLEAN
data near the surface was 1.7 x 10Ws cm2/sec, while
H. MYKURA
deeper into the same specimen a value of 1.5 x lo-l3 We simply suggest that cm2/sec was obtained. Hirano et uZ.fl) were studying this anomalous near-
2. W. M. ROBERTSON and P. G. SHEWMON, Trans. Amer. Inst. Min. (Met&.) Engrs. 224, 804 (1962). 3. J. M. BLAEELY and H. MYKURA,Acta Met. 11, 399 (1963). 4. H. MYKURA, Bull. Inst. Metals 4, 102 (1958). 5. J. M. MACKENIE, A. J. W. MOORE and J. F. NICHOLAS, J. Phys. Chem. Solids 23, 185 (1962). * Received
an important
surface effect, continued,
and that if their sectioning
the calculated
have approached
diffusion
had been
coefficients
those of other investigators.
would The
same suggestion probably applies to the earlier study of impurity diffusion in aluminum by Hirano et &.(lO,
LETTERS
The fact
that
more
penetration
exists
ported
1958
in
for by
than
one zone
diffusion
or region
specimens
Williams
and
TO THE
of
was re-
Slifkinol)
for
EDITOR
329
small, being of the order of lop4 cm. prevailed
This situation
because the time of diffusion was restricted
to maintain
a constant
interface
concentration,
C,,
Under these conditions,
the
diffusion of gold in silver. Subsequent works by Kosenko(5) in 1961 and Ignatkov and Kosenko(Q in
during the diffusion run.
1963 quantitatively
the correct one, and a good fit was observed
between
this
distance
penetration
plots
germanium Lundy(‘)
Williams
have
penetration
diffusion
further
theoretical
of impurities
The works of Styris and demonstrated
and
pointed
carefully
anomalous
out
and experimental
a need
for
evaluation
of
Until this is done and the anomalous
behavior
is understood,
reports
mental work in the field of isotope distinguish
near-surface
in
and Slifkin(s) and, Pawel and
behavior
such behavior.
two and three zones in
for the diffusion
single crystals.
Tomizuka,(*)
careful
described
between
measurements
effect and of bulk diffusion.
that the anomalous
of experi-
diffusion
diffusion
behavior
solution of the diffusion equation used in our paper is solution
and
the
concentration
measurements.
When the diffusion time was increased
to
penetration
extend
the
discontinuous found,
neither
by the discussers
centration
vs. distance measurements.
to establish suitable boundary
of the
limited. Although
for the case
were necessarily
we believe that the very low diffusivities
are
effect, and are thus consistent
determined.
to the conThus, in order
reported in our paper are valid, it is possible that they
law for calculating
are still to be
nor the one
conditions
distances
expected
at C, was not
conformed
things as proper choice of a solution to Pick’s second diffusion coefficients
the
our solution
suggested
at hand, the penetration
has on such
distance,
change in concentration
and then
should
The effects
vs.
representative
of
the
cited by the discussers.
anomalous
near-surface
with the other findings
Evidently,
this phenomenon
W. BIERMANN
is not confined to systems with very small solubilities.
Metals and Ceramics Division
F. R. WINSLOW
However,
the origin of the near-surface
effect remains
Oak Ridge National Laboratory
T. S. LUNDY
obscure.
The fact that the interface
concentration
Oak Ridge, Tennessee
stayed fixed during our diffusion the interface
References 1. K. HIRANO, M. COHEN md B. L. AVERBACH, Acta Met. 11, 463 (1963). 2. J. G. MULLEN, Phys.Rev. 121, 1649 (1961). 3. T. HIRONE, S. MIURA and T. SUZUOKA, J. Phya. Sot. Japan 16, 2456 (1961). 4. T. HIRONE and H. YAMAMOTO. J. Phwa. Sot. Japan 16. 455 (1961). 5. V. E. KOSENKO, Fiz. Tverd. Tela 3, 2102 (1961). 6. V. D. IONATKOV and V. E. KOSENKO, Fiz. Tverd. Tela 4, 1627 (1962). I. R. E. PAWEL and T. S. LUNDY, ORNL-TM-575, May 1963. 8. D. L. STYRIS and C. T. TOMIZUKA, J. Appl. Phya. 34, 1001 (1963). 9. G. P. WILLIAMS, JR. and L. SLIFKIN, Acta Met. 11, 319 (1963).
10. K. HIRANO, R. P. AGARWALA and M. COHEN, Acta Met. 10, 857 (1962). 11. G. P. WILLIAMS, JR. and L. SLIFKIN, Phya. Rev. Letters 1, 243 (1958). * Received
Reply
August
In addition, the diffusivities activation
energy
characteristic
was
surface effective
effect
and
on nickel
that
barrier.
were low even though the
lattice
words, the low diffusivities small D, values.
as a diffusion
only
of regular
about
one-half
diffusion;
stemmed
that
in other
from extremely
These results suggest that the near-
might
concentration
be caused
by an unduly
of vacancies
low
in the diffusion
zone. Department of Metallurgy
KEN-ICHI
HIRANO
Massachusetts Institute
MORRIS COHEN
of Technology,
B. L. AVERBACH
Cambridge
Massachusetts
12, 1963.
to comment cobalt
was not acting
runs indicates
Reference
“Diffusion
of
iron,
in silver”*
Biermann et aZ.(l) have rightly pointed out that the diffusion penetrations studied in our paper were quite
1. W. BERMAN, F. R. WINSLOW and T. S. LUNDY, this issue p. 328 * Received
October
23. 1963.
Ada Me!.,
328
METALLURGICA,
VOL.
12, 1964
Comment
on “Diffusion of iron, cobalt and nickel in silver”*
Results the
in the recent work by Hirano
diffusion
crystalline previous.
of
iron,
and
silver differ markedly works
Hirone
cobalt
and
of Mullen,(2)
Yamamoto.c4J
these differences,
from
Hirone The
et uZ.(~) on
nickel
aZ.,t3)
and
cited(l)
for
et
reason
which are, for example,
orders of magnitude
in poly-
those in the
about three
for the diffusion
coefficient
of
iron in silver, was that previous investigators(2-4) used the wrong solution experimental
to Pick’s second law for the
conditions
of the present
encountered.
note is to examine
and to propose a more reasonable FIG. 3. The y-plot constructed by integrating the graphs
of Fig. 2.
The iron y-plot may be summarised Yflll) ~ =
1.028 f
0.008,
Y*
YWm, 1.045 & 0.009,
Mykura.(l)
Simple
than at (100) for section
theory
for Ni obtained
predicts
for
clean
by f.c.c-
et aZ.(s)) a deeper cusp at (111)
and also predicts C.
a steeper
This difference
found that surface diffusion
gradient
may
be due to
possibly
on these specimens
Values
of D may
They
No faceting with
range
also derived;
106O”C, compares
and our y-plot
The twin boundary
the result,
exp
is con-
energy
was
yr/y,,.
= 0.014 & 0.004 at with the value of 0.017 f 0.006
be calculated
by fitting
straight
from
0.73 x lo-l3
to
1.85 x lo-l3
This is of the same order as the value of 2.60 x lo-l3 cm2/sec
determined
“correct”
by
Hirano
et al.(l)
using
the
solution to the diffusion equation,
C _ =
c,
also due to such impurity
was observed this.
solution of the diffusion
cm2/sec for the initial and final values respectively.
was
adsorption. sistent
of Hirano
lines through the first three and the last three points.
impurity adsorption near { 1001; Blakely and Mykuraf3) slower near {loo},
data
of Co60 in silver at 788°C
yields a plot of In (A) vs. X2 which is a smooth curve.
A in Fig. 2, where we find the steepest
slope in section
for their
1.044 < ~‘@!!! < 1.068.
to the results
(Mackenzie
of the penetration
A = &
in y at (100) with a shallower cusp at
is similar
surfaces
0.012
Y(loo,
The minimum
argument
equation,
Yt100,
Y%” __ = Y(loo,
(111)
Examination
by means of the “incorrect”
= 1.058 f
The purpose
these differences
existence. et uZ.fl) for the diffusion
as:
had
erf
1 _
(Y-5 275 1-
Therefore
the differences
magnitude
cannot be explained
of about
three
On the other hand, if it is recognized of Hirano sectioning
et al.(l) were technique
orders
of
by this argument.
obtained
by
that the data a very
and that the anomalous,
thin near-
obtained by Blakely and Mykura from a much smaller
surface
number of twins.
in such data, the differences can be readily resolved. For example, in the work of Pawel and Lundy”) on
M. M. acknowledges
the receipt
of a maintenance
diffusion
effect(s-9)
plays
grantfromD.S.I.R.,andwethanktheB.I.andS.R.A.
the diffusion
of Nbss in tantalum
for providing
the diffusion
coefficient
the specimen
material.
Department of Natural Philosophy University of Glasgow Glasgow, W.2 References. 1. H. MYEURA, Acta Met. 9, 570 (1961).
August
28, 1963.
role
it was shown that
at 1250°C as calculated
from
M. MCLEAN
data near the surface was 1.7 x 10Ws cm2/sec, while
H. MYKURA
deeper into the same specimen a value of 1.5 x lo-l3 We simply suggest that cm2/sec was obtained. Hirano et uZ.fl) were studying this anomalous near-
2. W. M. ROBERTSON and P. G. SHEWMON, Trans. Amer. Inst. Min. (Met&.) Engrs. 224, 804 (1962). 3. J. M. BLAEELY and H. MYKURA,Acta Met. 11, 399 (1963). 4. H. MYKURA, Bull. Inst. Metals 4, 102 (1958). 5. J. M. MACKENIE, A. J. W. MOORE and J. F. NICHOLAS, J. Phys. Chem. Solids 23, 185 (1962). * Received
an important
surface effect, continued,
and that if their sectioning
the calculated
have approached
diffusion
had been
coefficients
those of other investigators.
would The
same suggestion probably applies to the earlier study of impurity diffusion in aluminum by Hirano et &.(lO,
LETTERS
The fact
that
more
penetration
exists
ported
1958
in
for by
than
one zone
diffusion
or region
specimens
Williams
and
TO THE
of
was re-
Slifkinol)
for
EDITOR
329
small, being of the order of lop4 cm. prevailed
This situation
because the time of diffusion was restricted
to maintain
a constant
interface
concentration,
C,,
Under these conditions,
the
diffusion of gold in silver. Subsequent works by Kosenko(5) in 1961 and Ignatkov and Kosenko(Q in
during the diffusion run.
1963 quantitatively
the correct one, and a good fit was observed
between
this
distance
penetration
plots
germanium Lundy(‘)
Williams
have
penetration
diffusion
further
theoretical
of impurities
The works of Styris and demonstrated
and
pointed
carefully
anomalous
out
and experimental
a need
for
evaluation
of
Until this is done and the anomalous
behavior
is understood,
reports
mental work in the field of isotope distinguish
near-surface
in
and Slifkin(s) and, Pawel and
behavior
such behavior.
two and three zones in
for the diffusion
single crystals.
Tomizuka,(*)
careful
described
between
measurements
effect and of bulk diffusion.
that the anomalous
of experi-
diffusion
diffusion
behavior
solution of the diffusion equation used in our paper is solution
and
the
concentration
measurements.
When the diffusion time was increased
to
penetration
extend
the
discontinuous found,
neither
by the discussers
centration
vs. distance measurements.
to establish suitable boundary
of the
limited. Although
for the case
were necessarily
we believe that the very low diffusivities
are
effect, and are thus consistent
determined.
to the conThus, in order
reported in our paper are valid, it is possible that they
law for calculating
are still to be
nor the one
conditions
distances
expected
at C, was not
conformed
things as proper choice of a solution to Pick’s second diffusion coefficients
the
our solution
suggested
at hand, the penetration
has on such
distance,
change in concentration
and then
should
The effects
vs.
representative
of
the
cited by the discussers.
anomalous
near-surface
with the other findings
Evidently,
this phenomenon
W. BIERMANN
is not confined to systems with very small solubilities.
Metals and Ceramics Division
F. R. WINSLOW
However,
the origin of the near-surface
effect remains
Oak Ridge National Laboratory
T. S. LUNDY
obscure.
The fact that the interface
concentration
Oak Ridge, Tennessee
stayed fixed during our diffusion the interface
References 1. K. HIRANO, M. COHEN md B. L. AVERBACH, Acta Met. 11, 463 (1963). 2. J. G. MULLEN, Phys.Rev. 121, 1649 (1961). 3. T. HIRONE, S. MIURA and T. SUZUOKA, J. Phya. Sot. Japan 16, 2456 (1961). 4. T. HIRONE and H. YAMAMOTO. J. Phwa. Sot. Japan 16. 455 (1961). 5. V. E. KOSENKO, Fiz. Tverd. Tela 3, 2102 (1961). 6. V. D. IONATKOV and V. E. KOSENKO, Fiz. Tverd. Tela 4, 1627 (1962). I. R. E. PAWEL and T. S. LUNDY, ORNL-TM-575, May 1963. 8. D. L. STYRIS and C. T. TOMIZUKA, J. Appl. Phya. 34, 1001 (1963). 9. G. P. WILLIAMS, JR. and L. SLIFKIN, Acta Met. 11, 319 (1963).
10. K. HIRANO, R. P. AGARWALA and M. COHEN, Acta Met. 10, 857 (1962). 11. G. P. WILLIAMS, JR. and L. SLIFKIN, Phya. Rev. Letters 1, 243 (1958). * Received
Reply
August
In addition, the diffusivities activation
energy
characteristic
was
surface effective
effect
and
on nickel
that
barrier.
were low even though the
lattice
words, the low diffusivities small D, values.
as a diffusion
only
of regular
about
one-half
diffusion;
stemmed
that
in other
from extremely
These results suggest that the near-
might
concentration
be caused
by an unduly
of vacancies
low
in the diffusion
zone. Department of Metallurgy
KEN-ICHI
HIRANO
Massachusetts Institute
MORRIS COHEN
of Technology,
B. L. AVERBACH
Cambridge
Massachusetts
12, 1963.
to comment cobalt
was not acting
runs indicates
Reference
“Diffusion
of
iron,
in silver”*
Biermann et aZ.(l) have rightly pointed out that the diffusion penetrations studied in our paper were quite
1. W. BERMAN, F. R. WINSLOW and T. S. LUNDY, this issue p. 328 * Received
October
23. 1963.
Ada Me!.,