Effect of Concentrationdependent Diffusion Coefficients On Precipitate Growth Kinetics

Effect of concentrationdependent diffusion coefficients on precipitate
growth kinetics
L. C. Brown

Citation: J. Appl. Phys. 43, 4443 (1972); doi: 10.1063/1.1660941
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Effect of concentration-dependent diffusion coefficients on precipitate
growth kinetics
L. C. Brown'
Department of Metallurgy, University of British Columbia, Vancouver, Canada
(Received 14 February 1971; in final form 3 July 1972)
A theoretical analysis is presented for the growth kinetics of a phase precipitated from supersaturated solid solution in a
system with concentration-dependent diffusion coefficients. It is shown that at high supersaturations and for all
precipitate shapes the graphs relating growth rate to supersaturation for constant diffusion coefficients can be used,
provided the diffusion coefficient is taken as i5, the weighted average coefficient. For low supersaturations, the same
graphs can be used the diffusion coefficient is taken as i5 for spherical precipitates and]j for planar
precipitates, where 15 is very close to the first moment of the diffusion coefficient about the interface composition. At
other supersaturations the diffusion coefficient to be used lies intermediate between D and D for all precipitate
shapes, the actual value depending on the shape of the D-vs-concentration curve. For cylindrical precipitates, the
.growth rate always lies exactly halfway between the growth rates for planar precipitates and spherical precipitates. The
procedure outlined here should give growth rates accurate to within 1.5% of the difference between growth rates
calculated for diffusion coefficients at the phase-boundary composition and well away from the phase boundary. For
many purposes it is sufficient to use one diffusion coefficient covering all precipitate shapes and all supersaturations.
This is best taken as D and will give maximum errors of 6% for spherical precipitates and 15% for planar precipitates.
I. INTRODUCTION
Precipitation of the equilibrium phase from a super-
saturated solid solution generally occurs by a diffusion-
controlled reaction with the precipitates being in the
form of Widmanstatten sideplates or grain-boundary
allotriomorphs. The composition profile across a typi-
cal growing precipitate before impingement of the dif-
fusion fields is shown in Fig. 1. The growth of the a
phase is dependent on the diffusion of atoms down the
composition gradient in the i3 phase away from the
interface.
When the diffusion coefficient is a constant, solutions
for the growth rate of the new phase are well known for
planar, cylindrical, spherical, and spheroidal precipi-
tates. 1-4 In every case, parabolic growth is obtained,
with the dimensions of the precipitate increasing ac-
cording to the law
(1 )
The growth rate depends on D, the diffusion coefficient
in the supersaturated phase, and on a which as shown
in Fig. 1 is a function of the fractional supersaturation,
defined in this work as
1== 0
1
- coo, 0 < 1<1.
c
1
-co
(2)
The problem of determining growth kinetics is much
more complex when the diffusion coefficient is a func-
tion of compOSition. Growth is still parabolic with time,
but the rate parameter is difficult to determine. An
analytical solution for the growth of planar precipitates
has been developed by Atkinson. 5 This is exact but
applicable only to limited ranges of variation of diffu-
sion coefficient with concentration. Atkinson has also
developed numerical solutions applicable to many shapes
of precipitate. 6.7 Basically the technique involves carry-
ing out a large number of Boltzmann-Matano analyses
on elements in which it can be assumed that D is equal
to a constant. This procedure is the most general one
available but requires a computer for reasonable ac-
curacy. A modification of Atkinson's procedure is used
extensively in the present paper as an independent
method of calculating growth rates in order to compare
with the results of the theory developed here.
The procedure established in the present work is to
make use of the same graphs for growth rate versus
supersaturation as for constant values of the diffusion
coefficient (Fig. 1) and to replace D in Eq. (1) by an
effective diffusion coefficient De which represents some
average value taken from the graph of D vs c. The val-
ue of De to be chosen will depend on the degree of super-
saturation and on the shape of the precipitate.
II. HIGH SUPERSATURATIONS
The growth rate for planar, cylindrical, and spherical
precipitates becomes infinite as j-1. This requires
the composition gradient in the matrix to be large in
order to have a large flux of atoms away from the phase
boundary, and leads to the width of the diffusion field
being much smaller than at low supersaturations. The
precipitate size is also very large and so curvatures on
the cylindrical and spherical precipitates are quite
small. Both these factors-short diffusion distances and
small curvatures-minimize the point effect of diffu-
Sion, and in the limit as 1-1 the diffusion fields around
the three precipitate shapes will be similar. Hence, if
25

(3--

-J----.
FIG. 1. The growth rate (X2 = 0'2 Dt) of planar, cylindrical, and
spherical preCipitates from supersaturated solid solution as a
function of the supersaturation, /= (C
l
- C..) I(C
I
- CO),
4443 J. Appl. Phys .. Vol. 43. No. 11. November 1972
4444
L.C. BROWN
c,
c
FIG. 2. Growth of precipitates at high supersaturation.
a value for De can be found for one precipitate shape,
this will be true for all precipitate shapes. For sim-
plicity, planar precipitates will be considered.
The procedure involves solving the diffusion equation
ac _ ac
at - ax ax'
(3)
with the boundary conditions c=c
I
and D==D
I
at x=X,
the phase boundary; and C = Coo and D = Doo at x = 00. Sub-
stituting A = x/fl and integrating gives the Boltzmann-
Matano equation
(4)
2 shows the composition profile for a precipitate
at high supersaturation drawn in A space. The phase
boundary is at a position
L=x/fl.
The composition range Coo to c
i
is divided into n ele-
ments each of magnitude oc. At some intermediate
composition, cr=coo +roc with A=Ar' and area under
the curve measured from A=O is given approximately
by (c, - c.,)L =rocL. As 1-1 and L - 00 this will be-
come exactly true. Substituting in Eq. (3) gives OAr
=2D/rL, and the area of the shaded strip
IiA = (2D/L)oc.
Summing for all strips from c == Coo to c = c
i
and letting
OC - 0 leads to
A=(2/L)l
c
I Ddc . (5)
Coo
The solute in area A must have come from solute re-
moved from the region now occupied by the new phase.
i. e. ,
A = (coo - co)L.
The supersaturation I is thus given by
1= L(c! - coo)
L(c
l
- c.,} +A
(6)
Hence for a particular supersaturation I, range of
matrix composition (cl-Coo), and variation of D with c,
there is a particular growth parameter L. What is now
required is the constant value for D, De' which for the
same supersaturation and matrix composition range will
have the same growth rate L. This requires that the
area under the curve for De measured from A = L equals
area A, i. e. , the area under the curve for D(e), since
1. Appl. Phys., Vol. 43, No. II, November 1972
c,
i
Z 075
o
i=

a:
f..
Z
W
U
Z
o
r 025

FIG. 3. Composition profile in the matrix at high supersatura-
tion for D proportional to concentration, with D
t
(the diffusion
coefficient at C
I
) equal to one and Doo (the diffusion coefficient
at cj equal to zero. The profile for LJ= 0.5, a constant, is
also shown.
in Eq. (6) every other parameter is the same:
:. A = lCI Dedc = lCI D(c)de,
C, Coo
or
- ( )-llC! - -
De- c1-coo Ddc-D.
Coo
(7)
The composition profile for a linear variation of diffu-
sion coefficient is shown in Fig. 3, and clearly indicates
that the area under the 15 curve is the same as that
under the D(c) curve. It also shows that at e = c, the
gradients of the two curves are equal, since in Eq. (4)
the areas under the curves are essentially the same and
the diffusion coefficients are equal.
III. LOW SUPERSATURATIONS
A. Spherical precipitates
In this case the diffusion equation is written in the form
ae == ..!.. (r2D ae) .
at r2 ar or
(8)
Substituting A = r/fl gives the Boltzmann-Matano equa-
tion applicable to spherical precipitates
de _ A
3
de
dA - - 2A
2
D(c) .
(9)
i
c,
z
0 075
i=

a:

050
z
w
U
z
0 025
u
I
C'"
02 0'4 06
Co IT
L

FIG. 4. Composition profile for a spherical precipitate with
D= 1, a constant, and a supersaturation, f= 5. 7 X10-
5

CONCENTRATION-DE PENDENT DIFFUSION
4445
c,
r
z
0

a:

z
UJ
u
z
0
u
I
02
c.
o 05 10 25
A
,.
FIG. 5. Composition profile at low supersaturation for D
proportional to concentration, with D
j
1 and O. The
profile for O. 5 is also shown.
At low supersaturations the movement of the phase
boundary is small, so that L ==Rlfi, the position of the
phase boundary in A space, tends to zero. When this is
the case, dcldA-oo at .\==L, and the integral in (9) is
defined almost entirely by the profile at concentrations
near This is shown clearly for D equal to a constant
in Fig. 4 for an extremely low supersaturation. Thus in
the limit as L-O, Eq. (9) can be rewritten as
dc kl
dA = - 2A2D(c) ,
where kl is a constant for all values of c.
It is interesting to note that a similar expression for
dcl d.\ is obtained if LaPlace's equation
- Dr2- =0
o oc)
or or '
(10)
corresponding to steady-state diffusion, is solved rather
than the diffusion equation. The constant ki in (10) now
corresponds to the constant of integration. The use of
LaPlace's equation to represent growth of spherical
precipitates has been discussed in detail by Aaron et
al.
B
for the case of D equal to a constant.
i 100
z
o 075
i=

1%
050
UJ
u
z
8 025
I
..
FIG. 6. Composition profiles calculated at low supersaturation
for D proportional to concentration, i. e. , D C, and for D D,
assuming that the area under the curve is a constant indepen-
dent of concentration.

0'8
04 0'6 0'8 (,0
-- CONCENTRATlON __
FIG. 7. Curves showing an exponential variation of diffusion
coefficient with concentration. Numbers on the curves give D
at the midpoint concentration, C 0.5 and the corresponding
value of a in the expression (D - D.) /(Dj - D.) (&" - 1) /(e" -1).
Integrating (10) from c=c
1
to gives
2 lCI
kl = L Coo Ddc,
and substituting this in (9) at A=L leads to
C
dC) 1 I
C
I
d.\ == LD Ddc.
L 1 Ceo
(11)
The movement of the phase is controlled by the flux of
atoms down the composition gradient. In .\ space this
can be written
== (c1 - co).
(12)
It should be noted that this formula is true also for
planar and cylindrical precipitates. Substituting (11) in
(12) leads to
(13)
which gives the growth rate L as a function of the super-
saturation (c
i
- co) and the variation of D with c. Again
we wish to compare this with the constant value for D,
De' which has the same growth rate L at the same super-
saturation (c
1
- co), From (13), this requires
)
l
CI -
De=(ci-COO -1 Ddc=D.
Coo
I
o

FIG. 8. Some theoretical graphs of diffusion coefficient vs
concentration.
J. Appl. Phys., Vol. 43, No. II, November 1972
4446
L. C. BROWN
TABLE 1. Values for R = (De - D.,) I(D
j
- D.,) at low supersaturation calculated for different forms of variation of diffusion
coefficient with concentration.
Form of variation of R obtained by numerical analysis R calculated from theory using:
D with c Dj/Doo = 0 Dj/Doo-l D/Doo- 00 De from De from ]) from
Eq. (12) Eq. (13) Eq. (10)
Exponential a = - 9.190 0.973 0.956 0.952 0.976 0.937 0.891
a=-5.889 0.940 0.919 0.913 0.946 0.908 0.833
(see Fig. 8)a=-2.773 0.843 0.821 0.811 0.855 0.821 0.706
a=-1. 508 0.767 0.748 0.734 0.782 0.751 0.621
a= 0.001 0.648 0.632 0.616 0.666 0.639 0.500
a= 1. 508 0.524 0.510 0.487 0.540 0.518 0.379
a= 2.773 0.428 0.418 0.392 0.443 0.425 0.294
a= 5.889 0.269 0.263 0.236 0.280 0.269 0.167
a= 9. 190 O. 185 0.182 0.157 0.194 0.186 0.109
Fig. 9 (b) 0.753 0.704 0.658 0.755 0.725 0.505
Fig. 9 (c)a 0.911 0.881 0.873 0.901 0.865 0.800
Fig. 9 (d) O. 806 0.779 0.764 0.816 0.783 0.629
Fig. 9 (e) 0.911 0.906 0.901 0.920 0.883 0.843
aD
I
is taken as the diffusion coefficient between c = 0.147 and c = 0.347.
Hence for spherical precipitates at both low and high
supersaturation, the effective diffusion coefficient is
given by i5. It might be thought that this would be true
also for intermediate supersaturations. However, this
is not the case and, as will be discussed shortly, at
intermediate supersaturations De deviates from i5 in the
direction of D
I

B. Planar precipitates
For planar growth at low supersaturations, De is not
given by 15 but rather by a value closer to D
1
The rea-
son for this can be explained most clearly by comparing
composition profiles at high and low supersaturation.
Profiles for D proportional to concentration and for D
= 15 are shown in Figs. 3 and 5. As already discussed,
the gradients of the D = D(c) and D = i5 curves at c = C
are equal at high supersaturation. This will also be
essentially true at low supersaturation assuming a neg-
ligible change in shapes of the curves relative to one
another. The diffusion coefficient values are also equal
at c and so from (4) the areas under the curves at c
must be equal. Considering the total area (AI) under
the curves, it is clear that the area under the D=D(c)
curve exceeds that under the 15 curve by an amount A2 .
At low supersaturation the growth rate for a planar
precipitate is given by
L=AJ,
(14)
and so at a particular supersaturation the growth rate
corresponding to the profile for D is less than that for
D=D(c), and De will therefore be larger than D and has
deviated from 15 in the direction of D
1

There is no exact expression for De at low supersatura-
tion. A reasonably accurate value for De can be ob-
tained using the same concept as for spherical precipi-
tates, assuming that in Eq. (4) the integral is a con-
stant independent of concentration. This is saying that
the area under the composition profile is a constant k2
as c varies from Coo to c
p
and as can be seen in Fig. 5,
this is not accurate. However, the procedure gives a
simple value for De and is justified by the reasonable
accuracy of the results obtained. As with spherical
precipitates it is equivalent to solving LaPlace's equa-
tion rather than the diffusion equation.
Rewriting (4) and integrating gives the area under the
curve
(15)
where, for convenience, the following boundary condi-
tions are used
c =0 at A= 00,
c= 1 at A=Ci,
c = X for A < Ci .
Equation (14) shows that the profile for D=De should
have the same area Al as given by (15) and thus
(16)
De=2 fa1 Dcdc. (17)
Hence this model predicts that De at low supersatura-
tion is given by the first moment of the diffusion coef-
ficient about the interface concentration.
The model predicts that for D equal to a constant, the
profiles are straight lines rather than error functions
as they should truly be. The compOSition profile for the
0785
1'0
075

08
r
i
070
A4
06
K(J>
065
K'
I
0'4
I
060
055
02
0'500
0 02 0'4 0'6 0'8 10

FIG. 9. Graph of Kif) =A3/A4 and K', the normalized form of
K, plotted as a function of supersaturation!, for a constant
value of the diffusion coefficient D.
CONCENTRATION-DEPENDENT DIFFUSION
4447
10
i
0'8
z
Q
06
I-
oe(
a:
I-
z
04
UJ
u
Z
0
u 0'2
I
0
1'5
xU
FIG. 10. Composition profile for an exponential variation of the
diffusion coefficient with a = 9.190, DI = 1, D .. = 0 (see Fig. 8) at
a supersaturation f= 0.200. The composition profile for De =
0.144 is also shown. Lines defining various areas referred to
in the text are also marked.
case D = c is shown in Fig. 6. The profile for D = 15 lies
wholly within the profile for D = c, whereas, as shown
in Fig. 5, the two curves should intersect at c = 0 .15.
Hence the model gives somewhat too high an area under
the D = c curve and so overestimates the De value. As
will be seen shortly, however, the overestimate is
small and De calculated from (17) need only be reduced
by 4% to give good agreement with values calculated by
numerical analysis. Other methods for finding De have
been developed. However, the procedure outlined above
appears the best as it is fairly simple and gives good
agreement with values calculated by numerical analysis.
In order to see the agreement between the values of De
calculated from Eq. (17) and those obtained from nu-
merical analysis, it is necessary to select a wide range
of values for Dl and D .. and a wide range of curve shapes
for D vs c. Most diffusion coefficients are found ex-
perimentally to vary either linearly or exponentially
with composition, and so a series of D-vs-c profiles
given by
D-D.. e
c
-1
Dl -D", = e -1
(18)
was used. As a - 0, the profile tends to a straight line.
Figure 7 shows the profiles that were selected for eval-
uation of De' Values of De were found for these composi-
tion profiles at several values of the ratio D/D .. vary-
ing from 0 to 00. As shown in Table I, it was found that
the ratio
R=De-D ..
Dl - D ..
is almost independent of the range of diffusion coeffi-
cients Dl/D .. for any particular value of a. This means
that at any concentration the distance between the pro-
files for D=D(c) and D .. relative to the distance be-
tween the profiles for Dl and D", at the same concentra-
tion is always the same, independent of the range of
diffusion coefficients involved.
Values of the ratio R calculated using De obtained from
Eq. (17) are also shown in Table 1. In general, these
values are slightly too high, as expected. However, if
R is decreased by 4% the theoretical values all lie with-
in three percentage points of the values found by nu-
merical analysis. Values of D were also used for cal-
culating R in Table I and these all give values that are
Significantly too low.
It is thus found that for linear and exponential variations
of D with c, De should be given by
D=1.92 f/Dcdc +0.04D.,. (19)
In general, provided the D-vs-c curve does not deviate
too far from a straight line and provided D1/D., lies in
the range 0.2-5, Eq. (19) should give De values ac-
curate to within 1 .5o/c of the difference between Dl and
D.,.
Figure 8 shows some other variations of D with c.
These in general do not bear much relationship to ex-
perimental curves of D with c. However, as seen in
Table I, values of De calculated from (19) normally
agree well with the values obtained by numerical anal-
ysis, thus confirming the general applicability of the
theory developed here.
IV. INTERMEDIATE SUPERSATURATIONS
A. Planar precipitates
Values for De have been found at both f = 0 and f = 1, and
it is now necessary to find De at intermediate
supersaturations.
As discussed in Sec. ill B, composition profiles at high
and low supersaturation are quite different, even for the
case of a constant diffusion coefficient. This is not just
due to the fact that the area under the curve (A
4
, see
Fig. 9) decreases to zero as f - 1 but also that the ac-
tual shape of the curve changes. This change in shape
is best represented by the ratio K(f) = Ai A
4
, where As
is the area under the tangent to the composition profile
at c = 1 (Fig. 9) and is related to the supersaturation f
5
0'8
Q=- 9'190
i
06
De
0
1
I
Oct>
O 0 0 I

0'2 I
0 06 I
0'2

I 06
+
I 0'2
x I 0
Do
02 0'4 06 0-8 10
- - r ~
FIG. 11. Plot of the ratio S= (De - D) fro -D) vs supersaturation
for linear (a = o. 001) and exponential (a = 9. 190) variations of
the diffusion coefficient, where 15 is the effective diffusion
coefficient at f= 0 and D is the effective diffusion coefficient at
f= 1. For a = 0.001, results for several values of Dl and Doc
are plotted.
4448
L. C. BROWN
K)
i
0-8
z
0
06
l-
e:(
a:
I-
z
UJ
u
z
0
u
I
0
x
FIG. 12. Composition profile for an exponential variation of
the diffusion coefficient with a = - 9.190, D
j
= 0, 1 (see Fig.
8) at a supersaturationj=0.200. The approximate equivalent
profile C = O. 25 erfdX and the profile for De = O. 0298 are also
plotted. Lines defining areas referred to in the text are also
marked.
by the equation
A
3
=D//L.
It can be shown that
K{f) =.L .erfd
a
2 a lerfc ta
(20)
(21)
where a =L/fi5. This varies from t1T at/=O to tat
/ = 1 (Fig. 9), indicating the large change in the shape
of the composition profile.
Consider now a composition profile for D = D(c) which
does not change shape with increasing supersaturation
(Fig. 10). The significance of this will be discussed
shortly. At any supersaturation, a line AB can be drawn
from e = 1 generating a triangle having an area As equal
to that under the actual composition profile. De will be
the diffusion coefficient which at the particular super-
saturation will have the same area As under its com-
position profile. Drawing the tangent to this curve at
e = 1 gives an area As with
As =KAs = (D/DA)A
s
'
or (22)
De=KDA'
where DA is the diffusion coefficient associated with the
profile which has AB as its tangent. Knowing that De
equals 15 and 15 at / = 1 and / = 0, respectively, gives
D-15
DA = K(O) -K(l)
where K(O) and K(l) are values of Kat /=0 and /= 1,
respectively. Substituting in (22), followed by some
algebra, leads to
De=I5+Kl(fJ-I5), (23)
where K 1 is the normalized form of K and is plotted as
a function of / in Fig. 9. Thus if 15 and 15 are known , De
can be found at any intermediate supersaturation.
J. Appl. Phys., Vol. 43, No. 11, November 1972
It is now necessary to discuss which curves for D vs e
agree well with the above theory.
In the calculations for De at low supersaturation it was
found that for a particular shape of the D-vs-e curve,
the ratio

was almost independent of the range of diffusion coef-
ficients. This is also true at other supersaturations. In
Fig. 11 values of the ratio
S=(D -15)/(D-D)
e
are plotted as a function of / for a linear variation of
diffusion coefficient with concentration, the values for
De being obtained by numerical analysis. The curve is
independent of the ratio despite a range of values
of from 0 to 00. The reason for this is that, just
as for /=0, the curve for D=D(e) at any supersatura-
tion always has the same intermediate position between
the curves for D = 15 and D == i5, independent of the ratio
It is thus only necessary to consider one value
of this ratio for any particular shape of D-vs-e plot.
Figures 10 and 12 show composition profiles corre-
sponding to two extreme variations of the D-vs-e curve:
a == + 9 .190 and a == - 9 . 190. As seen in Fig. 7, the curve
for a = + 9 .190 lies close to D for most of the composi-
tion range, changing quickly to Dl as e -1. The corre-
sponding composition profile, Fig. 10, has an almost
rectangular form. This profile will change shape very
little with increasing supersaturation. At all / values,
the area under the curve will be essentially propor-
tional to concentration and so the integral in the Boltz-
mann-Matano equation [Eq. (4)1 is given by
fc/ Ade=k
3
e,
where k3 increases progressively with increasing super-
saturation. Supstituting in (4) and integrating gives the
composition profile as
A= (2/k) f (D/e) de. (24)
Only the constant k3 changes with supersaturation, in-
dicating that the shape of the profile does not change.
08
i
0-6
De
I
0'4
Curve from
Fig.10
02
0'2 0'4 06 0'8 1'0
-- -----'"
FIG. 13.1'1ot of De vs supersaturation for various values of
the ratio 15/]): Curves are calculated for D= 1, 0 < C < Cj and
D=O, Cj<c<1.
CONCE NTRATION -DE PE NDE NT DIFF USION
4449
D ? S ~ ~ - - - - - - - - - - - - - - - - - - ~
t 06
I 0'6
De
I
0'4
02
D vS.c Curve
in Fig.9
0 a

b
+
c
x d
0 e
02 04 06 0'8
- - ~ - ~
'0
FIG. 14. Plot of De vs supersaturation for the D-vs-c curves
shown in Fig. 8. The curves in Fig. 8 all have the same ratio
of DjD= 0.50.
Hence D-vs-c curves which change rapidly only close to
c = 1 agree very well with the theory given above which
assumes little change in shape of the composition pro-
file with changing supersaturation.
The composition profile in Fig. 12 for a = - 9 .190 shows
a maximum shape change with increasing supersatura-
tion. At low f, the integral in the Boltzmann-Matano
equation can be taken as almost constant, independent of
c, and the composition profile is
(25)
At sufficiently high supersaturation, however, the in-
tegral in Eq. (4) becomes proportional to c and the
profile is given by Eq. (24). Thus this profile changes
shape markedly with increasing supersaturation and
agrees poorly with the theory outlined above.
The variation of De with f for this type of D-vs-c curve
is found most easily by approximating profiles such as
shown in Fig. 12 by the simple function
, erfc(A!2v'D:')
c = c erfc(L/2-1n:J .
Evaluating areas under the composition profile atf=O
andf=l gives
c'=D/D
with D =..f15 in this special case.
Initially, attention will be focused on compositions up to
c' with an apparent supersaturation f' defined as
f'=Lc'/(Lc' +A
7
),
(26)
where A7 is the area under the composition profile mea-
sured from A = L. The tangent at c' generates an area
As, with As=c'f'/L from Eq. (20). ButA
s
=K{f')A
7
,
where K{f') is found from Fig. 9, and so
A
7
=c'f'/K{f')L.
(27)
ConSidering now the complete composition range from
c = 0 to c = 1, the actual supersaturation f is given by
f=L/(L +A
7
)
The profile for De is such that the area under it equals
A
7
, and again from (20)
A7=Def/K{f)L. (28)
Equating (27) and (28) leads to
, f' K{J)
De=c fK{J')'
(29)
giving De=D atf=O and De=D atf=l as required.
Plots of De vs supersaturation are given in Fig. 13 for
various values of c'=D/15. When c' approaches unity,
the curve for De vs ftends to that given by Eq. (23),
which is based on the theory that the shape of the com-
position profile does not change with supersaturation.
This follows directly from the fact that the ratio S is
independent of D/D
w
at any supersaturation, and since
the profile for D = 0, 0 < c < c 1; D = 1, c 1 < C < 1 has
essentially a rectangular form and does not change
shape with increasing supersaturation. In Eq. (29) the
change in the ratio!' / f with increasing f is much great-
er than the change in K{f)/K{f'). When c is small,
f f' in Eq. (28) and De deviates very little from its
value at f = 0 even when f is quite large. Only when f
approaches unity does Eq. (29) start to change and then
De changes rapidly to D. This effect becomes progres-
sivly more marked as c' - O.
The analysis presented here has been developed for a
step variation of diffusion coefficient with concentra-
tion. This in general bears little relationship to the ex-
perimentally observed linear and exponential variations
of diffusion coefficient. Only for the case of an exponen-
tial variation, with a in Eq. (18) equal to a large positive
or negative number, is the analYSis applicable. It does,
however, show that it is the ratio D/D or, more
generally,
D-Dl
T=-_--, O<T<l
D-D
1
(30)
that controls the shape of the De -vs -f curve. When T is
small, it means that the diffusion coefficient varies
rapidly close to c = 0 and the plot of De vs f changes
rapidly close to f = 1. When T is large, the D-vs-c
curve changes rapidly near c = 1 and the plot of De vs f
D
i
80
:: r
I-
60
z
UJ
De
v
a:
0'41
III 40
Q.
I
20
02
0'2 0'4 06 08
--1 >
FIG. 15. Diagram illustrating the theory for De in spherical
preCipitates. The percent contribution from planar growth
together with the corresponding values for De are shown, as
well as the values for De for spherical growth calculated from
these.
J. Appl. Phys., Vol. 43, No. 11, November 1972
4450 L. C. BROWN
0
0, 0 ..
0 0 I
0-8

0'2 I
i
0 0-6 I

I 06
0'6
+
I 0'2
x I 0
De
I

FIG. 16. Variation of De vs supersaturation for spherical
precipitates obtained by numerical analysis. Results for a
linear and exponential variation of D vs c are plotted.
is much more nearly linear. The ratio T thus com-
pletely defines the variation of De vs j and this is true
for any curve of diffusion coefficient versus concentra-
tion. A severe test of this is given by taking the com-
position profiles shown in Fig. 8. These have com-
pletely different shapes but the same value of T, and
when De is plotted vs j, the curves essentially coincide
(Fig. 14).
B. Spherical precipitates
It has been shown that at both high and low supersatura-
tions, De for spherical growth is given by D. At inter-
mediate supersaturations, however, De deviates !.rom
this and has a value intermediate between D and D. A
simple analysis to explain this variation will be
presented.
Figure 1 shows that when the diffusion coefficient is a
constant, the growth rate (Q'2D) for a spherical precipi-
tate at high supersaturation is three times that for a
planar precipitate. This factor of 3 represents the dif-
ference between the three-dimensional growth of a
sphere and the one -dimensional growth of a plane. At
all supersaturations less than unity, however, the
growth rate for spherical preCipitates is always greater
than three times that for planar ones. This difference is
due to the point effect of diffuSion, i. e., the contribu-
tion to the growth rate from the divergence of the diffu-
sion flux. Thus at any supersaturation the growth rate
of a spherical precipitate is made up partly of that
characteristic of a planar precipitate plus an
extra contribution caused by the divergence of the
diffusion flux, i. e. ,
(31)
The contribution from the planar term varies progres-
sively from 0% atj=O to 100% atj==1 and is shown in
Fig. 15.
When the diffusion coefficient is concentration depen-
dent, approximately the same contributions to the
growth rate will occur from the planar and divergent
terms. Equation (31) will still hold except that the dif-
J. Appl. Phys., VoL 43, No. 11, November 1972
fusion coefficients used in the three terms will be dif-
ferent. For the planar contribution, the diffusion coef-
ficient to be D
p
, will be given from Fig. 13 and
will vary from D to I5 with increasing supersatiration.
The contribution from the divergence term will have a
diffusion coefficient equal to 15, since this is the idffu-
sion coefficient at j == 0 where the contribution from the
divergence term is 100%. Thus for concentration-de-
pendent diffusion coefficients, Eq. (31) should be re-
written as
(32)
and would be expected to be exact as Dl approaches D",
in value.
Values of De calculated from Eq. (32) are plotted in
Fig. 15 for two values of the ratio T. The curves have
a simple convex shape with the maximum increasing in
value as T increases. The curves depend only on the
shape of the D-vs-c plot, and not on the range of diffu-
sion coefficient values, since the De-vs-j curves for
planar precipitates do not depend on this. Figure 16
shows values for De obtained by numerical analysis.
The agreement with the calculated curves in Fig. 15 is
moderate, and the curves are almost independent of the
range of diffusion coefficient values. The magnitude of
the maximum deviation from D increases with increas-
ing T although not as much as predicted by Eq. (32).
Over all, the simple theory developed here gives the
general form of the De -vs -j variation but not its exact
shape. Figure 17 gives the best average curves for De
vs j plotted as a function of the ratio T, the curves for
spherical precipitates being obtained from the best fit
to data obtained by numerical analysis for various
curves of D vs c. The maximum error in De obtained
from these curves should always be less than 7% of the
difference CD - D) and less than 1 % of the difference
(D
1
-D",).
V. CYLINDRICAL PRECIPITATES
Figure 1 shows that for a constant value of the diffusion
coefficient, the growth rate (2) for a cylindrical pre-
08
C5 0 02 0-4 oe
--f-
FIG. 17. Average values for De vs supersaturation for planar
and spherical growth. Numbers on the curves refer to
different values of the ratio T.
CONCE NTRATION -DE PE NDENT DIFFUSION
4451
TABLE II. Growth of 0' from supersaturated y in
Fe-I. 4-at. % C alloys.
Temperature De L from theory L from numeri-
(C) cal analysis
(x10
8
cm
2
/sed (Xl0
4
cm/sec
1
/
2
) (x10
4
cm/sec
1
/
2
)
Planar precipitates
740 10.558 3.113 3. 124
720 9.359 3.839 3.836
700 8.238 4.452 4.439
675 7.093 5.095 5.074
Spherical precipitates
740 10.316 7.191 7.221
720 8.970 8.242 8.253
700 7.831 9.105 9.111
675 6.677 9.979 10.007
cipitate is exactly midway between the rates for spheri-
cal and planar precipitates at the same supersaturation.
This is due to the fact that on one plane the diffusion
field around a cylindrical precipitate resembles that for
a plane, while on the plane at right angles the diffusion
field resembles that for a sphere. This will also be true
when the diffusion coefficient is concentration depen-
dent, with the growth rate of a cylinder being given by
L2 == .!.(L2 + L2)
a 2 P s'
(33)
where L; and are the growth rates for a plane and a
sphere at the same supersaturation. This is an exact
procedure, and it was indeed found that values for La
obtained by numerical analysis were in very close
agreement with those obtained from Eq. (33).
VI. DISCUSSION
The work presented in this paper has shown that growth
rates for precipitates in systems with varying diffusion
coefficients can be determined in the same way as with
constant diffusion coefficients provided an effective dif-
fusion coefficient (De) determined from the graph of D
vs c is used. For high and low supersaturations De is
found using Eqs. (7) and (19). Note that in Eq. (19) it is
necessary to specify that c = 1 at the phase interface and
c = 0 well away from the interface. At intermediate
supersaturations it is necessary to determine the shape
factor T [Eq. (30)1 for the experimental diffusion coef-
ficient variation and to use the appropriate curve in Fig.
17 to determine De' The procedure should always give
growth rates within 1.5% of the true value and does not
require a computer.
For many problems, high degrees of accuracy are not
required, and it is perfectly adequate to represent De
by jj over the complete range of supersaturation. Using
15 will give higher accuracy in determining growth rates
than will either Dl or D"" and in general the maximum
error in De will be less than 15% of the difference be-
tween Dl and D",. For planar precipitates the maximum
error will occur at low supersaturations, while for
spherical precipitates the maximum error will occur at
/-0.35 and will be less than 6%.
One of the most important phase transformations in-
volving concentration-dependent diffusion coefficients is
the preCipitation of O! from supersaturated yin Fe-C
alloys. The diffusion coefficient in austenite varies as
D = 0.5 exp(- 30C
o
) exp(- Qo/RT),
with
Q
o
==38 300 -1. 9X 10
5
C
o
+5. 5
Co being given in atom fraction. 9
For an alloy with l.4-at. % C transformed at 700C, the
diffusion coefficient varies by a factor of 3.3. Values of
the growth rate obtained from the present theory and by
numerical analysis are given in Table II. The agree-
ment between the two sets is better than 0.5%, indicat-
ing the correctness of the procedure used here.
VII. CONCLUSIONS
(1) The growth rate of precipitates forming from super-
saturated solid solution in a system with concentration-
dependent diffusion coefficients can be found using the
graphs and equations relating supersaturation to growth
rate for systems with constant diffusion coefficients
(Fig. 1), provided an effective diffusion coefficient (De)
is obtained from the graph of D vs concentration.
(ii) At high supersaturations for all shapes of precipi-
tate, De is given by 15, Eq. (7). For spherical precipi-
tates at low supersaturation, De is also given by 15. For
planar precipitates at low supersaturation, De deviates
from 15 in the direction of D
1
, the diffusion coefficient
at the interface composition, and De equals D, given by
Eq. (19) to an accuracy of 1. 5%.
(iii) At other supersaturations, De lies intermediate be-
tween 15 and D for both planar and spherical precipi-
tates. The actual value of De at a given supersaturation
is a function of the ratio T [Eq. (30) 1 which depends on
the shape of the D-vs-concentration curve. Values of
De for different T and / values are given in Fig. 17 for
planar and spherical precipitates.
(iv) The procedure should give growth rates accurate to
within 1.5% of the difference between growth rates cal-
culated for D = Dl and D == D",.
(v) Cylindrical precipitates have growth rates exactly
intermediate between the corresponding rates for planar
and spherical precipitates at the same supersaturation.
(vi) For many purposes it is sufficient to define one ef-
fective diffusion coefficient covering all precipitate
shapes and supersaturations. The simplest value is 15,
and this will give a maximum error of 6% for spherical
precipitates and 15% for planar precipitates, the error
being greatest at / "'" 0.35 for spherical precipitates and
/ == 0 for planar ones. The error here is defined as the
percentage of the difference between the growth rates
calculated for Dl and D",. It is not in general satisfac-
tory to use Dl or D", for the effective diffusion coeffi-
cient, although if a choice has to be made, Dl is slightly
better than D",.
ACKNOWLEDGMENTS
The author wishes to thank Professor M. E. Hargreaves
of the Department of Metallurgy, University of Mel-
4452
L.C. BROWN
bourne for provision of facilities. This work was par-
tially financed by the National Research Council under
Grant No. A-2549.
'Currently Visiting Professor, Department of Metallurgy, University of
Melbourne, Victoria, Australia.
'e. Zener, J. Appl. Phys. 20,950 (1949).
'F. e. Frank, Proc. R. Soc. A 201, 586 (1950).
3F. S. Ham, Q. Appl. Math. 17, 137 (1959).
'G. Horvay and J. W. Cahn, Acta Met. 9, 695 (1961).
'e. Atkinson, Acta Met. 15, 1207 (1967).
6c. Atkinson, Acta Met. 16,950 (1968).
'C. Atkinson, Trans. AIME 245, 801 (1969).
'H. B. Aaron, D. Fainstein, and G. R. Kotler, J. Appl. Phys. 41, 4404 (1970).
'L. Kaufman, S. V. Radcliffe, and M. Cohen, in Decomposition of Austenite by
Diffusional Processes, edited by Zackay and Aaronson (Interscience, New
York, 1962), p. 313.
Evolution of pulses in parametric wave interactions utilized in the initial-value
mode
Edwards S. Cassedy
Department of Electrical Engineering and Electrophysics, Polytechnic Institute of Brooklyn, Brooklyn, New York 11201
Charles R. Evans
Department of Electrical Engineering, University of Singapore, Singapore
(Received 23 August 1971)
Traveling-wave parametric devices operating in the initial-value mode are modeled and analyzed. In the initial-value
mode of operation, a signal pulse is injected into a nonlinear medium and allowed to propagate into the medium before
the parametric pump is turned on. Examples of such operation have been based on magnetoelasticity and on
photoe!asticity with microwave sources and lasers, respectively, as the pump, and elastic wave pulses as the signal. Such
devices are characterized here by a generic model of coupled transmission lines, with time-space periodic (parametric)
coupling. Rigorous (Floquet-mode) solutions of the periodic model are utilized for initial values of small-signal
perturbances having pulse envelopes. Unstable responses to the initial excitation are calculated and shown to be
predicted on the basis of the technique of asymptotic response previously used in the theory of plasma instabilities. The
Fourier-La Place representation is evaluated here using the (w-first) order of integration best suited to the asymptotic
response, in which the instability characteristics can be displayed directly in terms of saddle-point location and
branch-point separation of the instability dispersion function in k space. Characteristics such as thresholds of convective
and absolute instabilities are found in terms of pump amplitude and losses. Growth rates-temporal or spatial as
appropriate-and instability (crest) velocities are found in terms of the transmission line parameters. Finally, as a
practical matter, it is noted that these unstable "natural responses" of the pumped medium introduce a distortion of the
initial pulse envelope which would be unwanted in applications for delay lines and echo memories.
INTRODUCTION
Traveling-wave parametric amplifiers have usually
been enviSioned as bounded one-dimensional nonlinear
wave interaction systems, in which the pump wave is
always present, undepleted, and is very large. The
system is modeled as a bounded time-space periodic
medium, in which the time-space periodicity is always
"on". A steady single-frequency signal inserted at one
end emerges amplified at the other end in accordance
with a factor exp [1m (k)L], where Im(k) is the appro-
priate imaginary part of k for purely real w as re-
quired by a dispersion relation ~ ( w , k) = 0, and where
L is the length of the bounded system. A rigorous for-
mulation of the model of such a problem has been given
by Peng and Cassedyl and Peng.
2
Recently, a different mode of operation of traveling-
wave devices has been used. 3,4 In this mode of opera-
tion, a signal pulse is injected into the nonlinear me-
dium before the pump wave is "turned on",
This mode of operation of parametric traveling-wave
devices will be called the initial-value mode and will be
modeled by a homogeneous infinite one-dimensional
time-space periodic medium in which the time-space
periodicity exists at time t=O everywhere in space,
and for which there are at time t= 0 initial values of the
small-signal variables. These initial values of small
signal represent those in the physical system which
were injected before the pump wave was actually turned
on. The model appears to be a reasonable model for a
bounded medium for which neither the small-signal
J. App\. Phys., Vol. 43, No. II, November 1972
waves nor any waves coupled to them by the pump wave
reach a boundary of the real system in the duration of
the pumping, so that the medium may be regarded as
infinite.
The initial-value mode of operation described here has
been used experimentally in two traveling-wave sys-
tems: one based on magnetoelasticity3 and the other on
photo elasticity . 4
In the magnetoelastic system, the pumping wave is es-
sentially a wave on the upper branch of the extra-
ordinary electromagnetic-wave dispersion curve and is
very much faster than the other waves involved (spin
and acoustic waves cross coupled to form magneto-
elastic waves). In the experiments, a spin wave is in-
serted into the medium and allowed to propagate to a
region of the inhomogeneous medium where it assumes
the magnetoacoustic character, at which time a pump
pulse is applied. Experimental results are described in
the literature. 3,5 Pulse distortion is observed as are
differences between the amplification observed with
continuous pumping and with pulsed pumping. Although
the inhomogeneous aspects of the magnetoelastic me-
dium have not been modeled here, the model used does
indicate that pulse distortion is an inherent aspect of
the use of parametriC interactions in the initial-value
mode of operation.
The photoelastic experimental results are also de-
scribed in the literature. 4 In the photoelastic experi-
ments, an acoustic pulse is inj ected into the photo-
elastic medium and a laser pumping pulse applied later.

Effect of Concentrationdependent Diffusion Coefficients On Precipitate Growth Kinetics

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