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Electronic mail: ghf@engineering.ucsb.edu The disk radius to thickness aspect ratio is denoted by
1
D i /D 0 5 . ~5!
11 ma 2 f 2
A second, widely used ~and misused!! expression for D i
was presented in an earlier study by Nielsen10 of the perme-
ability of filled polymer systems. His expression can be writ-
ten ~in the present notation as!
1
D i /D 0 5 . ~6!
11 af
Clearly, Eqs. ~5! and ~6! make quite different predictions
in the dilute ~af !1! and semidilute ~a f @1! regimes.
Equation ~5! was derived by Cussler et al. with a picture
similar to Fig. 2~b! in mind, so we might expect it to be most
relevant in the semidilute regime, where it reduces to
D i /D 0 '1/( ma 2 f 2 );1/(nR 3 ) 2 . On the other hand, Eq. ~6!
was deduced with arguments most applicable in the dilute
regime, where it suggests D i /D 0 '12 af . The lack of a
‘‘geometric factor’’ in this expression, however, appears sus-
picious.
In the present paper we attempt to reconcile these two
formulas and, indeed, argue that Eq. ~5! is appropriate in the
semidilute regime and that a suitably modified version of Eq.
~6! is appropriate for dilute dispersions. Moreover, we ex-
plicitly estimate the geometric factor m for randomly posi-
tioned disk particles of uniform size and shape and provide a
FIG. 3. The diagrammatic expansion of the self-energy function S(q) de-
crossover formula to interpolate between the asymptotic di- fined in Eq. ~9!. The graphical series includes all topologically allowed
lute and semidilute regimes. Orientational disorder and poly- diagrams ~according to the rules for constructing diagrams outlined in the
dispersity effects are briefly discussed. text! that have no nodes ~are one-particle irreducible!.
wave vector k8 is given a value of the ‘‘T matrix’’ T(k8 ,k,û) although we believe that this agreement breaks down at the
discussed below. The assignment of wave vectors must en- next order, i.e., O @ ( af ) 3 # .
sure that momentum is conserved at each circle ~i.e., the The role of orientational imperfection is relatively easy
directed sum of all wave vectors entering and leaving the to address in the dilute regime. In particular, if we assume
circle is zero! but not necessarily at each vertex. Finally, that the disks in a composite have independently distributed
there is an implied integration, (2 p ) 23 * dk, over each inter- orientations, then the rules for constructing diagrams are un-
nal wave vector k. changed and the rules for evaluating diagrams are simply
The T matrix, or scattering matrix, can be extracted from modified as follows. In place of a simple factor of n for a
the Green’s function solution to the diffusion equation in a composite with perfect orientational alignment, each circle
matrix containing a single impermeable disk that is oriented ~e.g., the ith circle! in a composite with orientationally dis-
along the direction û. In Appendix A, we calculate the T ordered disks contributes a factor of n P u (ûi ), where P u (û)
matrix to leading order in slenderness, i.e., e 5a/R→0. We is the orientational distribution function characteristic of
obtain each disk and ûi is the orientation of the ith disk ~circle!.
Moreover, any vertex appearing in the ith circle contributes a
p 2D 0R 3 factor of T(k8 ,k,ûi ), where k8 and k reflect the outgoing and
T ~ q,k,û! 5 q k F ~ u q' 2k' u R ! , ~10!
ln~ R/a ! i i incoming wave vectors, respectively. Finally, an integration
over the orientations of all circles that appear in a diagram is
where F(x) is simply related to a Bessel function: F(x)
implied.
[2J 1 (x)/x. We denote a wave vector in the direction of û
With these slight rule changes, it is straightforward to
by q i 5q–û and in the plane transverse to û by q' 5( d
investigate the effect of orientational disorder on the barrier
2ûû)–q.
properties of dilute disk composites. To order af, we simply
According to the diagram rules, the number of powers of
orientation average the T matrix, weighted by the distribution
n is equal to the number of circles appearing in a diagram.
function P u (û). To bound the magnitude of the effect, we
As there is only a single diagram with one circle @Fig. 3~a!#
explicitly examine the case of an isotropic distribution of
this diagram should give the leading asymptotic behavior of
disk orientations P u (û)51/(4 p ). Such a composite of ran-
S~q! at a low density of disks. To first order in n, we thus
domly oriented disks is macroscopically isotropic and is
have16
characterized by a single diffusion coefficient D. Orientation-
p D 0 af 2 ally averaging T(q,q,ûi ) in this case leads to
S ~ q! 5nT ~ q,q,û! 1O ~ n 2 ! 5 q i 1O ~ n 2 ! , ~11!
ln a p af
D/D 0 512 1O @~ af ! 2 # . ~15!
which leads to 3 ln a
D i /D 0 512 k ~ af ! 1 k 2 ~ af ! 2 1O @~ af ! 3 # , ~13!
III. ANALYSIS OF THE SEMIDILUTE REGIME
where k[p/ln a is the geometric factor encountered above.
Thus, to second order in af, the dilute series is indistin- In the semidilute regime of disk concentration, af @1
guishable from the ‘‘modified Nielsen’’ formula and f!1, penetrant diffusion parallel to û becomes ex-
tremely tortuous, as the barriers to diffusion are highly over-
1 lapping @see Fig. 2~b!#. Cussler et al.1,2 have put forth ana-
D i /D 0 5 ~14!
11 kaf lytical arguments, simulation data, and experimental data to
J. Chem. Phys., Vol. 110, No. 4, 22 January 1999 G. H. Fredrickson and J. Bicerano 2185
S D
to the slits present distinct barriers that can be quantified.1,2 2
In disordered composites such as the present disk system, 1 1 1
F 2~ x ! 5 1 , ~20!
these barriers are less well defined and geometrically more 4 11a 1 x 11a 2 x
complex. From a computational point of view, however, this where a 1 5(22 A2)/4'0.146 447 and a 2 5(21 A2)/4
does not present added difficulties once the statistics of par- '0.853 553.
ticle placement have been specified ~e.g., random, uncorre- For x@1, these formulas reduce to F 1 (x);4/x 2 and
lated disk positions!. Nevertheless, the correlated wave vec- F 2 (x);16/x 2 , so the rate of convergence of this sequence of
tor integrals in the multiple scattering diagrams of Appendix approximants is not rapid. Nevertheless, Eq. ~20! encapsu-
B do indirectly reflect the geometrical complexity of a dis- lates all our knowledge about the problem, including reduc-
ordered disk composite. tion to the Cussler–Aris expression D i /D 0 ;1/( ma 2 f 2 ) for
A convenient functional form that is consistent with af @1, but with a geometric factor
these limiting results for both af !1 and af @1 is
m 5 p 2 / ~ 16 ln2 a ! ~21!
D i /D 0 'F m ~ kaf ! , ~17!
that depends logarithmically on the disk aspect ratio. Clearly,
where ~as above! k5p/ln a and F m (x) is the function
the numerical prefactor in this expression is subject to some
F m~ x ! 5S1
m
m
(
j51
1
11a j x D 2
. ~18!
uncertainty as it has been obtained by extending a series
beyond its domain of asymptotic utility.
In Fig. 4, the function F 2 (x) is plotted against the
The constant coefficients, a 1 ,...,a m , appearing in F m (x) are ‘‘modified Nielsen’’ formula, F N (x)51/(11x), and the
determined by comparing the expansion of this function in ‘‘modified Cussler–Aris’’ formula given by Eq. ~5! with m
powers of x with a dilute expansion of D i /D 0 carried out to chosen according to Eq. ~21!. Our expression for F 2 (x)
O @ ( af ) m # . While not a unique extension of the series, it should evidently be used in place of the modified Nielson
2186 J. Chem. Phys., Vol. 110, No. 4, 22 January 1999 G. H. Fredrickson and J. Bicerano
formula whenever kaf *3, while the modified Cussler–Aris obtain an asymptotic expression for the T matrix, valid to
formula asymptotes to F 2 (x) only for ka f *12. leading order in slenderness, i.e., e 5a/R→0.
A convenient route to slender body theory for a compos-
IV. DISCUSSION ite with an impermeable disk is to impose vanishing diffu-
sivity in the disk interior and then extract the limiting behav-
In the present paper we have analyzed the barrier prop-
ior for e→0. To this end, we wish to solve the point source
erties of composites that contain oriented, regularly sized,
equation
impermeable disks of large aspect ratio. Assuming randomly
distributed disk centers-of-mass with no spatial correlations, “• @ D ~ r! “G ~ r!# 52 d ~ r! , ~A1!
we have developed expressions for the diffusion coefficient
where D(r) is a diffusion coefficient that is defined to vanish
D i that characterize mass transport in the direction normal to
inside the particle and is equal to D 0 in the matrix outside of
the flat faces of the disks. In the dilute regime, where the
the particle. By introducing a function z~r!, which is unity
product of the disk aspect ratio a and disk volume fraction f
inside the particle and zero in the matrix, this can be ex-
is small compared with unity, Eq. ~13! is a useful asymptotic
pressed as
expansion in which each term has been evaluated to leading
order in disk slenderness ~1/a !1!. Alternatively, the ‘‘modi- D ~ r! 5D 0 2D 0 z ~ r! . ~A2!
fied Nielsen’’ formula @Eq. ~14!# can be used. In the semidi-
lute regime, where af @1, but the disk volume fraction f is Our next step is to introduce spatial Fourier transforms,
still small compared with unity, we find that the Cussler– defined, e.g., for the Green’s function according to
Aris formula @Eq. ~5!# is appropriate, but with a value of the
‘‘geometric factor’’ m given by Eq. ~21! that can be signifi- G ~ q! 5 E dr exp~ 2iq–r! G ~ r! . ~A3!
cantly smaller than unity.
The finding that m!1 for slender disks may explain the Transformation of Eq. ~A1! leads to the following integral
discrepency noted by Cussler et al.1 that aspect ratios de- equation:
duced from application of Eq. ~5! with m51 to diffusion data
were significantly smaller than aspect ratios deduced from
direct measurements of the flake-like filler particles. Use of
G ~ q! 5G 0 ~ q ! 1U 0 G 0 ~ q ! E k
exp@ 2i ~ q2k! –R1 #
our formula for m increases the predictions for a based on 3V ~ q,k! G ~ k! . ~A4!
their data by a factor of roughly 6, which is in much better
agreement with the directly measured aspect ratios. Here, * k[ * dk/(2 p ) 3 , where R1 denotes the position of the
While the formulas presented here were derived for center-of-mass of the disk, and U 0 is a bare scattering vertex
highly idealized situations of regularly shaped, sized, and strength defined by
distributed particles, the formalism on which they are based U 0 52 p aR 2 D 0 . ~A5!
is quite versatile and can be easily extended to more realistic
situations. For example, we briefly discussed the effects of The bare Green’s function, which describes diffusive propa-
orientational disorder and size polydispersity on the barrier gation in the matrix without particles, is given by
properties of dilute disk composites in Sec. II. The real chal- G 0 ~ q ! 51/~ D 0 q 2 ! , ~A6!
lenge from the standpoint of ‘‘first-principles’’ prediction of
barrier properties, however, is in gathering enough informa- and V(q,k) is a bare scattering vertex that reflects the form
tion about particle geometry, size, and shape dispersion, and factor of the particle:
spatial and orientational distribution of particles so that an V ~ q,k! 5q–kF ~ u q' 2k' u R ! j 0 @~ q i 2k i ! a # . ~A7!
accurate microstructural model of the composite can be con-
structed. Only with such a detailed model can one hope to In this expression, F(x)[2J 1 (x)/x, where J 1 (x) is the fa-
circumvent experimentation in this challenging area of re- miliar Bessel function of degree 1, and j 0 (x)[sin(x)/x is the
search. spherical Bessel function of order zero. We denote a wave
vector component in the direction parallel to the disk orien-
ACKNOWLEDGMENT tation û by q i 5q–û and define a transverse ~perpendicular!
wave vector by q' 5( d2ûû)•q.
This work was supported by the National Science Foun- The T matrix T(q,k) is defined by the relation
dation under Award Number DMR-9870785 ~G.H.F.!.
Our next step is to scale all parallel wave vectors by 1/a, all
perpendicular wave vectors by 1/R, and introduce a dimen- E dz j 0 ~ x2z ! j 0 ~ z2y ! 5 p j 0 ~ x2y ! , ~A17!
sionless T matrix defined by S(q,k)5T(q,k)a 2 /U 0 . This
leads to the following dimensionless integral equation:
S ~ q,k! 5 ~ q i k i 1 e 2 q' •k' ! F ~ u q' 2k' u ! j 0 ~ q i 2k i !
E dz F ~ u x2zu ! F ~ u z2yu ! 54 p F ~ u x2yu ! . ~A18!
ES D
The amplitude A is obtained via a solvability condition
q i p i 1 e 2 q' •p' on the next order equation in the hierarchy. In particular, at
12 p
p p 2i 1 e 2 p'2 O( e 0 ) we have
3F ~ u q' 2p' u ! j 0 ~ q i 2p i ! S ~ p,k! .
Of key interest is the asymptotic behavior of the solution
~A10!
M 1 ~ q,k! 5
1
4p2
E E dpi dp'
to Eq. ~A10! in the limit of large aspect ratio, i.e., e→0. To 3F ~ u q' 2p' u ! j 0 ~ q i 2 p i ! M 1 ~ p,k! 1Q ~ q,k! ,
facilitate the asymptotic analysis, we note that the terms pro-
~A19!
portional to e 2 q' in Eq. ~A10! yield contributions at higher
order in e than the remaining terms in the equation; hence, where Q(q,k) is the following inhomogeneous term:
we consider them no further. The term 1/(p 2i 1 e 2 p'2 ) in the
Q ~ q,k! 5F ~ u q' 2k' u ! j 0 ~ q i 2k i !
integrand, however, must be treated more carefully to effect
the asymptotic analysis. To this end, we reexpress this factor
as 2
2pe
ln~ 1/e !
ES
p
p'2
p i 1 e 2 p'2
2 D
1 1 e 2 p'2
5 3F ~ u q' 2p' u ! j 0 ~ q i 2 p i ! M 0 ~ p,k! . ~A20!
22 ~A11!
p 2i 1 e 2 p'2 pi p 2i ~ p 2i 1 e 2 p'2 !
The second term in this expression proves to be O(1) on
and replace S(q,k) in favor of a new scattering matrix subsequent asymptotic analysis for e→0. Equation ~A19! is
M (q,k) according to an inhomogeneous Fredholm equation ~second kind! for the
unknown function M 1 . However, because the constant mul-
S ~ q,k! [q i k i M ~ q,k! . ~A12!
tiplying the integral operator on the right hand side of this
These steps lead to the following equation: expression corresponds to an exact eigenvalue, a solution for
M 1 exists only if the projection of the inhomogeneous term
M ~ q,k! 5F ~ u q' 2k' u ! j 0 ~ q i 2k i ! Q onto the eigenfunction, Eq. ~A16!, exactly vanishes. This
12 p Ep
F ~ u q' 2p' u ! j 0 ~ q i 2p i ! M ~ p,k!
criterion provides a solvability condition that determines the
amplitude A. We find
22 p e 2 ES p'2
D A 21 5
e
p ln~ 1/e !
E E
0
`
dx
`
0
dy
y 3 F 2 ~ y ! j 20 ~ x !
x 21 e 2y 2
, ~A21!
p p i 1 e p'
2 2 2
M 0 ~ q,k! 5
1
4p2
E E dp i dp' E ce
`
dx x 21 j 20 ~ x ! ;ln~ 1/e ! ~A23!
3F ~ u q' 2p' u ! j 0 ~ q i 2p i ! M 0 ~ p,k! . ~A15! for any O(1) constant cutoff c, we obtain
This is an eigenvalue equation and, indeed, 1/(4 p ) coin- 2
A5 p /2. ~A24!
cides with an exact eigenvalue of the integral operator. The
Combining the above results, we thus arrive at the fol-
corresponding eigenfunction is given by
lowing leading order asymptotic approximation for the T ma-
M 0 ~ q,k! 5AF ~ u q' 2k' u ! j 0 ~ q i 2k i ! , ~A16! trix:
21
dx exp~ 2ik i x ! , ~B7!
calculation of the T matrix in Appendix A, we are concerned
only with computing this sum, S 2 (q) to leading order in disk
slenderness e. F ~ k' ! 5
1
p
E dx exp~ 2ik' •x! , ~B8!
We begin by evaluating Diag ~3b!. Applying the dia-
where the integral in the latter expression is over a two-
gram rules outlined in Sec. II, we obtain
dimensional disk of unit radius. To summarize our results,
Diag~3b)5
n 2 q 2i T 30
D 20
E k 4i
k~ k i 1k' !
2 2 2
we find that the diagram with two circles: m internal solid
arrows and m11 vertices has a value
n 2 q 2i T m11 1
3F 2 ~ u q' 2k' u R ! j 20 @~ q i 2k i ! a # , ~B1! 0
. ~B9!
Dm
0 ~ 2 p aR 2 ! m21
where the ‘‘amplitude’’ of the T matrix has been denoted as
The sum of two-body diagrams is thus a geometric series
p 2D 0R 3 that can be evaluated in closed form. The a→0 limit of this
T 0[ ~B2!
ln~ R/a ! sum is
and we employ the same shorthand as in Appendix A: * k S 2 ~ q ! 52q 2i n 2 T 20 /D 0 . ~B10!
[(2 p ) 23 * dk. Rescaling k i by 1/a and k' by 1/R in the
Thus, while the individual diagrams in the two-body series
integrals appearing in Eq. ~B1! leads to
are singular in the limit of vanishing disk thickness a→0,
Diag~3b)5
n 2 q 2i T 30
D 20 ~ 2 p ! 3 aR 2
E E`
2`
dx dy
the overall sum is finite ~apart from the logarithmic factor in
T 0 ). Combining this result with Eq. ~9! reproduces the
O @ ( af ) 2 # term given in Eq. ~13!.
x 4 F 2 ~ u q' R2yu ! j 20 ~ q i a2x !
3 ~B3!
1
. E. L. Cussler, S. E. Hughes, W. J. Ward III, and R. Aris, J. Membr. Sci.
~ x 21 e 2y 2 !2 38, 161 ~1988!.
2
D. M. Eitzman, R. R. Melkote, and E. L. Cussler, AIChE. J. 42, 2 ~1996!.
Asymptotic evaluation of the integrals for e→0 is readily 3
T. Lan, P. D. Kaviratna, and T. J. Pinnavaia, Chem. Mater. 6, 573 ~1994!.
carried out by noting the convolution properties of j 0 and F 4
P. B. Messersmith and E. P. Giannelis, J. Polym. Sci., Part A: Polym.
given in Eqs. ~A17! and ~A18!. This leads to Chem. 33, 1047 ~1995!.
5
K. Yano, A. Usuki, and A. Okada, J. Polym. Sci., Part A: Polym. Chem.
n 2 q 2i T 30 1 35, 2289 ~1997!.
Diag~3b)5 . ~B4! 6
P. M. Subramanian, Polym. Eng. Sci. 25, 483 ~1985!.
D 20 2 p aR 2 7
P. G. de Gennes and J. Prost, The Physics of Liquid Crystals ~Oxford,
New York, 1993!.
Next, we turn to the evaluation of Diag ~3c!. Applying 8
R. Aris, Arch. Ration. Mech. Anal. 95, 83 ~1986!.
the diagram rules, we find 9
W. T. Brydges, S. T. Gulati, and G. Baum, J. Mater. Sci. 10, 2044 ~1975!.
10
L. E. Nielsen, J. Macromol. Sci. ~Chem.! A1, 929 ~1967!.
Diag~3c)5
n 2 q 2i T 40
D 30
EE
k p
k 2i p 2i ~ q i 1p i 2k i ! 2
k 2 p 2 u q1p2ku 2
11
12
13
M. Lax, Rev. Mod. Phys. 23, 287 ~1951!.
M. Bixon and R. Zwanzig, J. Chem. Phys. 75, 2354 ~1981!.
T. R. Kirkpatrick, J. Chem. Phys. 76, 4255 ~1982!.
14
G. H. Fredrickson and E. S. G. Shaqfeh, Phys. Fluids A 1, 3 ~1989!.
3F 2 ~ u q' 2k' u R ! F 2 ~ u k' 2p' u R ! 15
The condition that the self-energy diagrams have no nodes is equivalent to
one-particle irreducibility in the language of field theory.
3 j 20 @~ q i 2k i ! a # j 20 @~ k i 2p i ! a # . ~B5! 16
Note that ln(R/a)5ln(2a);ln a for a→` ~i.e., e→0!.
We again scale the internal parallel wave vectors p i and k i
17
Note that af 5 p nR 3 provides the R dependence in this expression.
18
Note that in the two-dimensional problem of periodically placed line ob-
by 1/a and the internal perpendicular wave vectors p' and stacles, a finite value for m is obtained for infinitely thin plates (a→0).
k' by 1/R. Asymptotic analysis for e→0 and application of 19
H. Risken, The Fokker-Planck Equation, 2nd ed. ~Springer, New York,
Eqs. ~A17! and ~A18! leads to 1989!.