ANALYTICAL SOLUTION OF FICK’S SECOND LAW WHEN THE

DIFFUSION COEFFICIENT VARIES DIRECTLY AS CONCENTRATION*

A. D. PELTONf and T. H. ETSELL$

9 simple analytical solution of Fick’s second law for linear diffusion has been obtained for the case
in which the interdiffusion coefficient varies directly with concentration. D = Do. c/co, for initial
conditions c = co for 2: < 0, and c = 0 for r > 0 in a semi-infinite medium both for the oase of a
stationary and a moving boundary and also in an infinite medium. The solution is applied to calculate
kinetic paramet,ers for the growth of some spinels according to A0 + B,O, = AB,O,.

SOLUTION ANALYTIQUE DE LA DEUXIEME LO1 DE FICK QUAND LE COEFFICIENT DE

DIFFUSION VARIE DANS LE MEME SENS QUE LA CONCENTRATION
me solution analytique simple de la deuxi&ne loi de Fick pour la diffusion Ii&aim a BtB obtenue
pour le cas ob le coefficient d’interdiffusion varie dam le m&me sens que la concentration, D = Do c/co,
les conditions initiales &ant c = co pour z < 0, et c = 0 pour z > 0 dam un milieu semi-infini ZLla
fois pour une le cas d’une front&-e stationmire et celui d’une for&&e en mouvement, et Bgalement
dam un milieu infini. La solution est appliquCe au calcul des param&res cinbtiques de croissance de
certains spinelles obCissant B la relation A0 + B,O, = AB,O,.

EINE ANALYTISCHE LOSUNG DES ZWEITEN FICKSCHEN GESETZES BE1 LINEARER

ABH.%NGIGKEIT DES DIFFUSIONSKOEFFIZIENTEN VON DER KONZENTRATION
Eine einfache analytische L&ung des zweiten Fickschen Gesetzes fiir lineare Diffusion wurde gefunden
fiir den Fall eines linearen Zusammenhangs zwischen Diffusionskoeffizient und Konzentration
(D = Do c/c”), sowie fiir die Anfangsbedingungen: Halbraum mit c = co fiir z < 0 und c = 0 fiir
z :> 0. Die L~sung gilt sowohl fiir eine stationtire als such fiir eine bewegende Grenzfliiche; sie gilt
ebenfalls im unendlich ausgedehnten Medium. Mit Hilfe der gefundenen LGsung werden Wachstu-
msparameter einigrr Spinelle (A0 + B,O, = AB,O,) berechnet.

INTRODUCTION This problem has been treated numerically by

Fick’s second law for linear diffusion Wagner.“) A typical concentration profile at some
time after t = 0 is shown in Fig. l(a).
ac a ac
z=z (Da.x
1 (1)

F
9

where c = concentration, t = time, x = distance,

D = interdiffusion coefficient, has been solved to
give simple analytical solutions of the form c =
c(x, t) only for cases in which D is independent of
concentration. For certain other functions D(c),
numerical solutions have been obtained, and a few
complex formal and approximate analytical solutions
are also available.(1-5) Most of this work is discussed
by Crank.(‘j)
It is the purpose of the present paper to develop
a simple analytical solution of equation (1) when

D = Do ’ c/c” (2)

where Do and co are constants. The first case to be FIG. 1. Profile of concentration c vs. distance z or of
considered will be diffusion in a semi-infinite medium y vs. y when D = Do . c/co.

with conditions
The problem stated with equations (14) is of
c: = 0 when t = 0,x > 0 (3) importance in the study of several solid state reac-
c = CO when t> 0,x=0 tions. An example is the formation of spinels. For
(4)
instance, if NiO and CrsO, are brought into contact
at elevated temperatures, a spine1 product phase
* Received March 29, 1972.
t Institut for theoretishe Hiittenkunde der technischen NiCrsO, grows between the two original phases.
UniversitBt, Clausthal, West Germany. Present address: At the same time, since Cr,O, is soluble in NiO at
Dept. of Metallurgy and Materials Science, Massachusetts
Institute of Technology. Cambridge, Mass. 02 139, USA. these temperatures, there will also be transport of
f Max-Planck-Institut fiir Chemie, Maim, West Germany. Cr,O, into the NiO phase. If the spinel-NiO boundary
Present address: Dept. of Metallurgy and Materials Science,
University of Toronto, Toronto, 5, Ontario, Canada. is at x = 0 in Fig. l(a), with NiO on the right, then
ACTA METALLURGICA, VOL. 20, NOVEMBER 1972 1269
1270 ACTA METALLURGICA, VOL. 20, 1972

the concentration profile of CrsO, in the NiO is as Physically meaningful solutions for the stationary
in Fig. l(a), with co the saturation concentration. boundary ease exist only over the interval 0 < z < 1.
~resko~ch(s) has shown experimentally that in this A power series solution of the form
ease the interdiffusion coefficient in the NiO phase co
follows equation (2) very closely. This can be y = 2 a,x”
interpreted by assuming cation diffusion via cation n=l

vacancies, the concentrations of which are given by may be sought, where the series starts with the n = 1
the local amount of chromium ions substituted on term because of boundary condition (11). A similar
nickel lattice sites, Cr&, since two Cr& ions form one series can be written for $:
doubly ionized cation vacancy, V&, to maintain
electroneutrality, and the thermal intrinsic disorder
n=l
is low. A similar concentration dependence of D
By substituting equations (13) and (14) into equation
for the diffusion of CrsO, into MgO@) and of A&O,
(9) and equating coefficients of zn, the following
into MgO(rO) during the formation of the corre-
relationship between the ~~~cients a, and 6, is
sponding spinels has also been found. Equation (2)
obtained
is also closely obeyed for the diffusion of S&l, into
KCl,d*) of PbCI,- into AgCl(‘Jr) and undoubtedly n- 1
b, = 2~+~ (&,--a- It 1 w
for many other cases of aliovalent doping in which n
the concentration of mobile majority lattice defects
Equations (13)-(15) may now be substituted into
varies as the concentration of dopant, and the~al
equation (10) and eoe~~ients of z” equated to give
intrinsic disorder can be neglected.
the following expressions for the coef6cients a, :
Of particular importance in Fig. I(a) is the fact
that, as pointed out by Wagner,(‘) there will be an a, = 2y+s (16)
advancing plane at x+ such that c = 0 for x > x+. as = -a,/4 (17)
This results from the fact that D = 0 when c = 0.
l---n
DIFFUSION IN A SEMI-INFINITE MEDIUM a, = -
ns
a,_1 - - ’ t1 ma,a,,+,[n = 3,4, .. I
‘

nal m=2
Fick’s equation (1) may be transformed by mesns (18)
of the usual substitution By setting
Y = 2/(4DOt)1’a (5) aj = YjLzl WV
(where the factor Do is introduced solely for mathe- in equation (lS), a recursion relationship for Y$
matical convenience) and with the further substitution in terms of only vs, vs, . . . , Y+~ may be obtained,
thus indicating that each coefficient aj can, in fact,
y = c/co (6)
be written as in equation (19), where vi is a simple
to give an ordinary differential equation in only numerical factor.
y and Y, The first few terms in equation (13) have been
calculated to give
2Y(~~~~Y)= -~(~2~~~Y2) - (~~~~Y)Z
so that y is a function only of Y as shown in Fig. 1(b)
(7)
1 ( 1
Y = 2Y+2 z--4t+$2d+576z4
1
There will be a value Y+ = ~+/(4DOt)l/~ such t#hat
y=Ofory> y.+.
11 1
The further substitution 86400
+ -25-P 115200 2s + . .> @.v
z = 1 - y/y+ (3) Substitution of boundary condition (12) into equation
is now made to give Fiok’s equation (1) in the following (20) gives (to 6 terms)
form
y+ = 0.8081 (21)
d#dy = 2Y+2(1 - z) (9)
where and thus, the final solution of the original problem is
4 = ~(~~~~~) (19)
~-;f~+-&~+~ti
The boundary conditions are now simply 576
y = 0 at x = O(y = Y+) (11) 11 1
+ -~5_--.- 2.6+.,. (2%
y=l at z = l(y = 0) (12) 86400 115200
 PELTON AND ETSELL: ANALYTICAL SOLUTION OF FICK’S SECOND LAW 1271

The very rapid apparent convergence of the series tion (20), but with the following boundary condition
may be noted. Since 0 < z < 1, then, the cubic and replacing the condition of equation (12)
higher terms are virtually negligible. A plot of y
y=l at z = zl(y = yr) (24)
vs. y is shown in Fig. l(b). This curve is nearly
where
coincident with that calculated numerically by
yi = x1/(4DOt)l’” (25)
Wa,gner.(‘) The value of y+ = 0.8081 may be com-
pared with Wagner’s value of 0.81. Near y = y+ 21 = 1 - YJY+ (26)
(2 = 0), the curve is nearly linear, and only near y = 0
Substitution into equation (20) gives
(z = 1) does the quadratic 22 term become noticeable.
A linear join has been made in Fig. l(b) to show clearly -1

the overall departure from linearity.

MOVING BOUNDARY
2y+2 =
( z1 - ; z12 + ; 213+ . .
1 (27)

If values of ;i are chosen, values of y+ may be calcu-

During the course of many solid state reactions,
lated from equation (2i), and then equation (26) can
the product phase A$, spatially separates the react-
be used to find the corresponding value of yi. A
ants A and B from each other, so that the reaction
plot of y+ vs. yi is given in Fig. 3. If only the first
proceeds only through diffusion
in the solid A,B,.
two terms in equation (27) are used, the following
In Fig. 2, the reactants
A and B were originally in
approximation results :
contact at x = 0 at t = 0. The product phase, of
width Ax, grows by counterdiffusion of A and B.
y = ~1 + (4~1’+ 6P2
If, at the same time, there is a significant mutual f (28)
3
solubility of A and B, then transport of B into A
and of A into B will occur. A typical concentration This gives y+ accurate to better than 1 per cent for
profile, cR, of component B for this case is shown in yi > 0, and is also quite a good approximation for
Fig. 2. - small negative values of yi.
If yi is linown, y+ can be obtained from Fig. 3
B Av BP A
[equation (27)], or from equation (28). Substitution
I
into equation (20) then gives the final solution of the
I
I diffusion equation. Some solutions for various
I
I
I

/c:
\
ca=c 7-x
0 I

AX -

FIG. 2. Concentration profile cs of component B in

reaot,ant phases A and B and in product phase AVB,
during a solid state rea+on. Original A-B boundary
was at z = 0.

It may easily be shown(12) that the phase boundary

1 in Fig. 2 advances following a parabolic growth law.
That is:
x1 cc t1’2 (23)
For the specific case in which the interdiffusion co-
I I .

10

efficient in phase A is given by equation (2) (where

c = cfi, co := cRO at boundary I), the solution of the
FIG. 3. y+ vs. y1 [from equation (27)] andf, vs. 11, [from
diffusion equation in phase A is again given by aqua- equation (35)].
1272 ACTA METALLURQICA, VOL. 20, 1972

equation (20) using a computer, the radius of con-

vergence appears to be about 4.5. The sum increases
slowly as z increases and becomes virtually constant
from z = 3.9 to 4.5. Values of zr in this range give
a profile (Fig. 5) in agreement with ‘that calculated
numeri~aily for the case of an infinite medium. As
z is increased further beyond 4.5, the sum exhibits
a rapid decrease towards - co.
Also, for large values of n, the absolute values of
the coeffcients very closely obey the relationship

Y (32)
Fm. 4. Solutions of F&k’s equation with a moving
boundary for vrtrious values of y1 when I) = Do . c/c*.
values of TJ~
are shown in Fig. 4. For g1 > 0 (advanc-
ing boundary), the higher terms in the power series
become less and less important, and the profiIes
become more and more nearly linear. For y1 < 0
(receding boundary), z becomes greater than unity
near y = 2/r, and so higher terms become more
important and significant departures from linearity
are observed.
DIFFUSION IN AN INFINITE
MEDIUM
Diffusion in an infinite medium (over the interval
-oo<z< co) subject, at t = 0, to the initial
where K is 8 constant. Values of K calculated from
equation (32) for 27 < n, < 200 all lie in the range
4.57 < K Q 4.90. If this relationship continues to be
obeyed 8s n approaches infinity, then, again, a value
of K w 4.5 would be a lower estimate of the radius
of convergence of the series in equation (20).
As may be appreciated from Fig. 5 or Fig. 3, 8
radius of convergence of 4.5 (yr = -2.2) is certainly
sufficient for any practical calculations (as,for that
matter, is the value 3.1 (yr = -1.26) which has been,
rigorously proven in the Appendix to be a minimum
possible value of the radius of convergence).
I 1

conditions
c = co if 2<0 (29)
c=o if x>O (30)
mtly also be treated. This case is equivalent to the
moving boundary case just discussed with yr = - co,
so that boundary condition (24) simply becomes:
Y = 1 when x = -ce(t > 0). From Fig. 3 it can
be seen that y+ rapidly approaches a limiting value
as yi becomes more and more negative. Calculations
show
y+ = 0.620 (31)
constant to three decimal places for y1 < -1.8 Y
(zr > 3.9). Substitution of equation (31) into equa- Fro. 5. Solution of Fiok’ls equation when D = Do * c/co
tion (20) then gives the final solution of the problem. for an infmite medium with initial conditions c = 8,
2 < 0; 0 = 0, r > 0.
A plot of y vs. y is shown in Fig. 5. It may be noted
that y = 0.588 at y = 0. This problem also has been NUMERICAL EXAMPLES
treated numerically by Wagnert71 who obtained & A general solution of the kinetic problem illustrated
value of y = 0.59 at y = 0. in Fig. 2 has been obtained. (i2) A growth rate constant
Mfor the product layer is defined as follows
CONVERGENCE OF THE SERIES
Ax = UP (33)
In the Appendix it is proven that the power series
in equation (20) converges at least for all values of z Another growth rate constant /l may be defined as
less than 3 I1. that’which results when phases A and l3 presaturated
Based on a calculation of the coeflleients a, to with each other are used- as reactants. (That is, in
n = 200 and the sum of the brackets terms in this case, c, = cBo for all x 2 x1 in phase A.) The
 I’ELTON AND ETSELL: ANALYTICAL SOLUTION OF FICK’S SECOND LAW 1273

TABLE 1. Calculated kinetic parameters for formation of A&,0, spinels

R -
using BP DC+
linear (when &a+ > i&z+ > &-) (when oas+ >+ nc$+ ;% %z-)
R = LX//~ approximationclzl (om2/sec . 10’0) (cm2/sec. 1010)
.40 (a,) fl
NiO 1580 0.862 0.80 0.75 10.8 2.4
Xi0 1450 0.907 0.87 0.83 1.57 0.35
Xi0 1383 0.909 0.87 0.84 0.63 0.14
NiO 1330 0.898 0.86 0.83 0.20 0.044
MgO 1640 1.13 0.94 0.93 11.2 2.48
MgO 1340 1.71 0.992 0.992 0.25 0.055

parameters cc and ,!? are called rate constants of the the plot given previously (Fig. 2 of R’ef. 12). It may
first and second kind, respectively. It is of importance also be easily shown that for small values of y1 in the
to be able to calculate ,8, which is of more fundamental approximate range -0.15 < y1 < 0.30, fi is approxi-
interest, from measured values of a, or alternatively, mated by
in practical applications, to be able to estimate the fi = 0.8875 + 1.25oy, (36)
ratio R = a//?,which is the ratio of the actual product
t’hickness to the thickness obtained if no transport For y1 > 0.30, the following approximation may be
in phases A and B occurred. The ratio R has been used :
related’12) to the various elementary parameters 4~1 + (4~1~ + W”
fl = (371
(diffusion coefficients, solubilities, etc.) for the general 3
case, for any given concentration dependence of
Values of fi and of R = MI/?calculated for the forma-
D(c) in phases A and B, through use of a function
tion of NiCr,O, and MgCr,O, spinels at various
f,which is given by
temperatures are shown in Table 1. The values of R
(34) are compared in Table 1 to those calculated pre
(where y = cB/cBo in phase A), and by the use of a viously(l2) using the linear approximation to the
similar function fi to account for the transport of concentration profile. From the values of R = u//?
A into the B phase. Examples were given(12) for the and from the measured values of the reaction rate
formation of NiCr,O, and MgCrzO, product spine1 constants of the first kind, ~1, rate constants of the
phases, where phase A is NO or MgO and phase B second kind, B, may be calculated. These values have
is CrO,,, (so written for notational consistency). In then been used along with values of the free energies
t’hese systems there is negligible solubility of A in of formation of the spinels, as discussed previously,(12)
phase B, but there is appreciable solubility of CrO,,, to calculate average diffusion coefficients in the spine1
in NiO or MgO and, as discussed previously, equation phases for two limiting cases :
(2) holds in phase A where c = cCro3,2, and co = (i) Ni2+ or Mg2+ is the rate-determining diffusing
&o3,2 at boundary 1. Solubilities and values of Do ion, in which case l&+ or DMgz+ in the spine1 phase
and CIhave been measured for these systems.@*g) is calculated;
In order to calculate fi, an approximate solution of (ii) C!?+ is the rate-determining species, in which
t,he moving boundary case due to Wagner (see Ref. 9) case DC++ in the spine1 phase is calculated. Results
was used,‘12) in which a linear profile of y vs. y was are listed in Table 1.
assumed. In view of the present analytical solution,
ACKNOWLEDGMENTS
however, it can be shown that this approximation was
not very exact. and so the calculations will now be The authors wish to thank Professor H. Schmalzried
redone. for comments on the manuscript and Mr. L. SchBfer
Substituting equations (8) and (20) into equation for his valuable help regarding the Appendix.
(34) and performing the differentiation, one obtains Financial assistance from the National Research
Council of Canada is also gratefully acknowledged.
fi = zy, 1 - f Z1 + ; Q + k6 213 + . . .) (35) REFERENCES
(
1. H. FUJITA, Textile Res. J. 22, 757, 823 (1952); 24, 234
where y+ is given by equation (27) (Fig. 3) or, approxi- (1954); J. CoZZoid Sci. 9, 269 (1954).
2. L. J. GOSTING and H. FUJITA, J. Am. &em. SIX. 79,
mately, by equation (28). Values of fi may thus be 1359 (1957).
easily calculated for various values of yl. A plot 3. J. GILLIS and 0. KEDEM, J. Polymer A%. 11, 545 (1953).
4. D. M. CLARKE, J. chem. Phy.s. 27, 29 (1957).
of fi vs. y1 is also given in Fig. 3. This supercedes 5. J. R. PHILIP, Amt. J. Ph.ys. 13, I (1960).
3
1274 ACTA METALLURCICA, VOL. 20, 1972

6. J. CRANK, The Mathematics of Difftmim. Oxford where the first and third summations in (A.2) have
University Press (1957).
7. C. WAGNER, J. them. Phys. 18,1227 (1960). been combined by replacing the index m with
8. C. GRESKOVICH, J. Am. Ceram.Soc. 58,498 (1970). (n-m+l)inthethirdsum.
9. C. GRESEOVICH and V. S. STUBICAN, J. Phys. Chem.
Solids 30,909 (1969); J. Am. Get-am. Sot. 53, 251 (1970). It will now be shown that the final summation in
IO. W.P. WHITNEY, II and V. S. STXBICAN, J. Am.Ceram. (A.3) becomes negligibly small for large values of
Sot. 54,349 (1971); d. Phgc Chem. ~oZ~e 33,305 (1971).
Il. H. SCHMALZRIED andH. WEFIN~,~h~~~~, 485 (1969). j and n. [What this means is that for large values
12. A. D. PELTON,H.SCHMALZRIED~~~C.GRESKOVICH,B~~. of n in equation {18), only the lower and higher terms
Bunseng. Phys. Chem. 76, 543 (1972).
in the summation are significant. The middle terms
APPENDIX are negligible.] The proof will be made by replacing
An inductive proof will be made. Let j and n the final summation in (A.3) by an integral :
be two positive integers, wit,h n > 2j - 1, such that
the relationship
1

II%7&
-
"1
G pm2

holds for j < m < n - 1 where R is some positive

(A.11
X
[w(n -
W

w + 1)]2dw (A'*)

number. A similar proof to the following could be

The limits of integration have been extended by 1
made with m* replacing the factor m2 in (A.l), where
at each end to ensure the validity of inequality
E > 1. The choice of E = 2 has been chosen for the
(A.4). Replacing (n + 1) by 2k, and letting (w - k) =
sake of simplicity. For a given value of R, inequality
u, the integral may be evaluated :
(A.l) must be demonstr&ted by actual ~lculations
of ana in the interval. It must now be proven that B+k
(Al) is also true for m = n. The maximum value of (k2 - u2Jadu = R(n; 1)
R for which this proof can be made is a lower estimate
of the radius of convergence of the series. From 1 1
X --
equation (18) it is seen that j-l n-j+2
j-l

-I- 2n
-Q + lj2
ln n ;t; 2 (A.51

’ RGnL+l(n - m + 1)s When j is large the integral becomes negligibly small

and, in this limit, inequality (A.3) is given by

Rn--n2+1(n- m + 1)2

x I%-&11E2 1 (A-2)
By computer calculations it has been shown that
inequality (A.1) is true for0 < R < 4.0 for 21 < m <
where the sum in equation (18) has been split into
200. Values of j = 50 and n = 201 are sufficient to
three sums. From inequality (A.2) the reason for the
ensure that the approximation of large j can be made,
inequality n > 2j - 1 given above can be seen.
and that n > 2j - 1. A lower estimate of the radius
Rearrangement of (A.2) gives
of convergence is then given as the maximum value
of R for which
j-l

R m-l mz, la,l R"-lg 1 (A-7)

x bmi
(n - m + 1)2+ ii
This has been found by trial and error to be given by
n-j+1 m R = 3.1. [Terms in the sum in (A-7) for m > 9 were
XI: (A.3)
m=j [m(n - m + 1)12
I found to be negligible.]