Ind. Eng. Chem. Res.

1996, 35, 3179-3185 3179

Hydrodynamic Permeability of Hydrogels Stabilized within Porous

Membranes
Vivek Kapur,† John C. Charkoudian,‡ Stephen B. Kessler,§ and John L. Anderson*,|
Colloids, Polymers and Surfaces Program, Department of Chemical Engineering, Carnegie Mellon University,
Pittsburgh, Pennsylvania 15213, Millipore Corporation, 80 Ashby Road, Bedford, Massachusetts 01730, and
HemaSure Inc., 140 Locke Drive, Marlborough, Massachusetts 01752

The purpose of this work was to demonstrate that cross-linked polymer gels can be stabilized
against mechanical and osmotic forces by confining them in a microporous support. The
hydrodynamic (Darcy) permeability was measured for neutral and charged polyacrylamide (PA)
gels synthesized in semirigid membranes having a hydraulic mean pore diameter of 0.5 µm and
a porosity of 67%. The permeability was determined by measuring the flow rate of aqueous
solutions as a function of pressure drop across the membranes. The membrane-supported gels
were stable and yielded a constant permeability when the pressure drop was increased to 300
bar/cm. No swelling/deswelling was observed with the charged gels (0.3-0.4 equiv/L) when the
ionic strength was varied between 0.01 and 1.0 M, and the permeability was essentially
independent of ionic strength. The permeability of the neutral gel varied as φ-3.3 where φ is the
polymer volume fraction, whereas literature data for bulk PA gels shows the dependence to be
φ-1.4. The permeability of the membrane-supported neutral PA gel was greater than the
literature values for the bulk gel at low φ but comparable to the bulk gels when φ > 0.08.

Introduction where v is the superficial solvent velocity through the

The promise of gels as viable separation devices for
large-scale processes rests on the ability to stabilize
them in configurations that take advantage of their
space-filling capacity yet maintain their integrity. Poly-
meric gels can be selective media based on molecular
size (Gehrke and Cussler, 1986; Tong and Anderson,
1996) and ion exchange (Boschetti et al., 1995; Gehrke
et al., 1989). The basic engineering problem is to protect
gels against mechanical and osmotic forces. An example
of this challenge is chromatography. Highly cross-
linked gels have been used for the packing of chromato-
graphic columns; however, the large pressure gradients
required to achieve flows through beds of particles less
than 0.05 mm diameter can cause deformation and
collapse of the gel particles.
An approach to overcome the stability problem is to
fabricate gels within pores of a rigid matrix such as
silica particles (Boschetti, 1994) or a rigid polymer
membrane. If the pores are much larger than the
effective mesh dimension of the gel, then the gel will
control molecular and viscous transport within the pores
(Kim and Anderson, 1991). Such “gel in a shell”
composite structures offer mechanical strength without
sacrificing the functionality of the gel (Boschetti et al.,
1995); that is, the gel network can be optimized with
respect to chemistry, charge, and cross-linking.
An important property of gels is their hydrodynamic
(Darcy) permeability, k, which is defined by Darcy’s law:
k amide (PA) and derivatized (charged) PA gels that were
v)- ∇P (1)
η
* Author to whom correspondence should be addressed:
Phone: (412)268-6986. Fax: (412)268-7139. E-mail: jlacheme
+@andrew.cmu.edu.
† Present address: E. I. duPont de Nemours and Co.,
Experimental Station, Wilmington, DE 19880.
‡ Millipore Corporation.
§ HemaSure Inc.
| Carnegie Mellon University.
S0888-5885(96)00015-2 CCC: $12.00
gel, η is the solvent viscosity, and P is the pressure. The
above equation assumes the gel is isotropic. The
hydrodynamic screening length, xk, is a measure of the
mean spacing between the fibers (polymer chains)
forming the gel network. Darcy’s law is valid at
distances greater than xk from boundaries where a no-
slip velocity condition is imposed; within distances of
about xk, Brinkman’s equation (Brinkman, 1947; How-
ells, 1974) describes the velocity field.
Measurements of k for gels are valuable for two
reasons. First, k depends on the the microstructure of
the gel, and hence its measurement gives insight into
the microstructure; and second, k along with solute
diffusion coefficients must be known to model molecular
transport within gels (Johnson et al., 1996; Tong and
Anderson, 1996). However, experimental determination
of k for bulk gels is difficult because of their compress-
ibility. Often a plot of superficial velocity versus applied
pressure across a thin film of gel is nonlinear because
the gel compresses and k decreases as pressure in-
creases.
There are two objectives of this work: first, to
demonstrate that a cross-linked gel can be stabilized
with respect to mechanical (pressure) and osmotic forces
by synthesizing it in a porous membrane; second, to
compare the hydrodynamic permeability of membrane-
supported gels with bulk gels. We report experimental
results for the permeability of cross-linked polyacryl-
formed within the pores of poly(vinylidene fluoride)
membranes. The data are broken into two sets, one for
the neutral gels and the other for the charged gels. With
the neutral gels, we are interested in the variation of
permeability with polymer volume fraction of the gel
and how our results compare with literature data for
the permeability of bulk gels (Tokita, 1993; White, 1960)
as well as the stability (i.e., the constancy of the
permeability) at large pressure gradients. With the
charged gels, our focus is on the ability of the porous
© 1996 American Chemical Society
3180 Ind. Eng. Chem. Res., Vol. 35, No. 9, 1996

membrane to stabilize the gel when the ionic strength

of the solution changes.

Experimental Section
A summary of materials and methods is given below.
More details are available elsewhere (Kapur, 1995).
Synthesis of Gel-Pore Composite Membranes.
The neutral PA gel membranes were made at the
Millipore Corporation (Bedford, MA). A poly(vinylidene
fluoride) (PVDF) membrane (Durapore, Millipore Corp.)
of nominal pore diameter 0.22 µm was used as the
support. These membranes can be obtained in two Figure 1. Apparatus for measuring Darcy permeability of the
forms: with a thin polyacrylate coating to make them membrane: km ) ηvm/(-∆P/L) where L is the membrane thickness
hydrophilic (Steuck, 1986) or without any coating (0.125 mm), η is the viscosity of the aqueous solution, and vm )
(hydrophobic). The hydrophilic membranes were used Q/Am.
for synthesis of the neutral PA gels. The membrane was
first soaked for 2 min in a degassed aqueous solution of vp(wm+g - wm)
φ) (2)
acrylamide monomer plus the cross-linking agent (N,N- πRm2L
methylenebisacrylamide) and photo-initiator (trade-
name Darocur 2959 ) 4-(2-hydroxyethoxy)phenyl-(2-
where Rm is the radius (2.35 cm), L the thickness (0.125
propyl) ketone, Ciba Geigy, Inc.). The membrane was
mm),  the porosity of the membrane (0.67), and vp the
then removed from the solution and placed between two
partial specific volume of PA (0.7 cm3/gm (Munk et al.,
thin polyethylene sheets. Excess solution was removed
1980)). The second method was based on determination
by gentle application of a rubberized roll bar. Polym-
of the nitrogen content of the membrane (Desert Ana-
erization was accomplished by transporting the sand-
lytics, Tucson, AZ). The nitrogen determination was
wich through a Fusion Systems UV (H bulb) unit at 12
converted into PA content per unit volume of membrane,
ft/min. After UV curing, the membrane was immersed
from which φ was calculated (Kapur, 1995). The values
in deionized/filtered water (MilliQ purified). The mem-
of φ by these two methods were in good agreement in
branes were stored in buffered solutions at pH 5.9 or
all cases. The nitrogen-based analysis was probably
pH 8.5. The cross-link density (CL), which is defined
more accurate, so its result was used for φ except for
as the ratio of (mass of bisacrylamide)/(mass of acryl-
the two lowest values of φ for which the nitrogen
amide), was 6% for all the data reported here. The UV
analysis was not available.
energy was too low to expect any significant covalent
The polymer volume fraction of the charged PA gels
binding of the PA to either the PVDF surface or the thin
was determined by the gravimetric method only. Equa-
polyacrylate coating.
tion 2 was used, and the specific volume was assumed
The charged membrane-supported gels were made at
to be the value for PA (0.7 gm/cm3). From representa-
BioSepra Inc. (Marlborough, MA). Hydrophobic Du-
tive samples of the membrane-supported gels, we found
rapore membranes (i.e., no coating on the PVDF) of 0.22
that φ ) 0.12 ( 0.01 for the Q form and φ ) 0.16 ( 0.01
µm nominal pore diameter were used as the support.
for the S form.
Gels based on monomers carrying either positive (Q,
Measurement of Hydrodynamic Permeability.
quaternary amine) or negative (S, sulfonate) groups
The membrane hydraulic permeability (km) is defined
were synthesized using methods similar to those de-
by
scribed by Girot and Boschetti (1993, 1995), which result
in substantially homogeneous, clear gels of low CL. The
two referenced patents pertain to the formation of such
ηvm
km ) (3)
gels within porous mineral oxide particles. To form the (-∆P/L)
same gels within microporous PVDF membranes, the
following procedure was used. The internal surfaces of where vm is the water flow rate (Q) divided by the
the membranes were treated using methods similar to available membrane area (Am ) 5.07 cm2). The ap-
those described in the above referenced patents. Work- paratus is sketched in Figure 1. The membrane was
ing inside a nitrogen-purged glovebag, each membrane mounted on a porous stainless steel screen that provided
sample was placed inside an individual polyethylene negligible resistance to flow. The low-pressure reservoir
pouch. Solution containing monomers, cross-linkers, was a block of Plexiglas with holes drilled at a converg-
and polymerization catalyst was applied to each mem- ing angle. The total volume of the low-pressure reser-
brane using a microliter syringe. Each pouch was then voir was 0.35 cm3.
sealed, and the glovebag was heated to 85 °C for 1.5 h Pressurized nitrogen was used to force water through
to effect polymerization. The resulting gel-filled mem- the membrane. The water was obtained from a MilliQ2
branes were washed in deionized water and stored in system. Buffer solutions of sodium dihydrogen phos-
appropriate buffers. The charge density based on the phate/sodium hydroxide and sodium chloride (pH ) 5.9)
pore volume was 0.4 mequiv/cm3 for the Q form and 0.3 or sodium borate/hydrochloric acid and sodium chloride
mequiv/cm3 for the S form. (pH ) 8.5) were prefiltered in-line with 0.2 and 0.1 µm
The volume fraction (φ) of polymer (monomer plus pore size polyester Nuclepore membranes. Pressure
cross-linking agent) in the neutral PA gel membranes was measured with Validyne DP-15 transducers. The
was determined in two ways. The first method was solvent flow rate was measured by following the move-
based on the weight of the dry membrane before ment of a bubble in a precision-bore capillary (radius )
synthesis of the gel (wm) and the weight of the dry 0.275 mm) connected to the low-pressure side of the
membrane after the gel was formed (wm+g). The gel Plexiglas cell. The hydrodynamic resistance of the
volume fraction was computed from membrane without gel in the pores was more than 100

Figure 2. Sample data for three gel-filled membranes (neutral
PA) with different polymer volume fractions (φ) in the pores. km
is the slope of the straight lines.
times the sum of the resistances of all other components
in the system. The membrane permeability was deter-
mined by measuring Q versus ∆P, correcting η for the
temperature during the experiment (20-25, ( 0.5 °C
during an experiment), and then using eq 3 to compute
km. Sample data for three gel-filled membranes are
plotted in Figure 2.
With some of the gel-filled membranes at low φ there
was a very slight curvature to the plot of vm versus ∆P.
The values of km reported here are the extrapolations
to zero pressure. The reduction in km in going from the
lowest to the highest pressure (-∆Pmax ≈ 3 bar) was
always less than 7% of the extrapolated zero-pressure
value of km.
Since cross-linked gels are elastic media, it is impor-
tant to recognize elastic relaxation in making pressure-
flow measurements. Scherer (1989) modeled the time
course of compression of a elastic thin film that is
supported by a plane on the low-pressure side. If time
zero is defined when the pressure drop is first impressed
across the film, then the time required before the stress
in the film becomes essentially linear is given by
L2η
τe )
Mk
where M is the uniaxial elastic modulus of the film. For
polymeric gels with φ ) 0.1, the osmotic modulus is of
order 1 bar and increases as φ2.3 (Sellen, 1987). Taking
this value for the elastic modulus, a bulk gel film of
thickness comparable to our membranes (≈0.1 mm)
would have τe ≈ 100 s; steady-state flow would only be
expected for times longer than this. The times for a flow
measurement at one pressure were about 103 s. The
system was allowed to equilibrate for 10-60 min before
the flow rate was recorded. Moreover, two repeatable
measurments were taken for each increment in pres-
sure.
Characterization of Bare Durapore Membranes.
The Durapore membranes had a nominal pore diameter
of 0.22 µm. We measured the porosity of sample
membranes by gravimetric methods and found  ) 0.67
( 0.02. The nominal thickness of the membranes was
0.125 mm; this value was confirmed by our measure-
ments. These characterizations were done with hydro-
philic membranes.
Ind. Eng. Chem. Res., Vol. 35, No. 9, 1996 3181
Pore volume and pore-size distribution of sample
hydrophobic membranes were determined by mercury
porosimetry (Micrometrics Corporation, Norcross, GA).
From these data we found that  ) 0.67 and the mean
pore diameter equaled 0.4 µm.  was calculated from
the measured specific pore volume (mL/g of solid) and
the density of PDVF (1.77 gm/mL). The mean pore
diameter was defined as the diameter at 50% volume
intrusion.
The Darcy permeability of the bare membranes (kmo)
was about 2-3 × 10-11 cm2. The Kozeny equation
(Happel and Brenner, 1973) relates the permeability to
the hydraulic radius (rh ) pore volume/surface area) and
porosity () of the porous medium:
rh2
kmo ) (5)
K*
where K* is the Kozeny constant, which equals 2 for
parallel capillary-type pores of circular cross section and
25/6 for consolidated structures (for example, packed
beds) with  less than 0.5. The value of K* increases
as  increases and is about 5 for  ≈ 2/3. Taking the
equivalent pore diameter to be 4rh and using the value
2 × 10-11 cm2 for the Darcy permeability, we estimate
the hydraulic mean pore diameter to be 0.5 µm, which
falls between the values obtained by electron microscopy
(0.6 µm) (Allegrezza and Kazan, 1993) and the poro-
simetry data (0.4 µm).
Conversion of measurements of km to the permeability
of the gel itself (k) requires knowledge of /τ where τ is
the “tortuosity factor”:
(τ)
-1
k) km (6)
The ratio /τ can be experimentally determined by
measuring the diffusion rate (M) of a solute through a
bare Durapore membrane as a function of concentration
difference:
M ) kD(-∆C) (7a)
 DoAo
kD0 ) lim kD ) (7b)
ωf∞ τ L
where Do is the diffusion coefficient of the solute, Ao is
(4) the membrane area for these diffusion experiments (2.9
cm2), and ω is the rotation rate (rad/s) of the stirring
bars. A diaphragm diffusion cell with rotating stirring
bars oriented parallel to the membrane surface on both
sides was used. Extrapolation of the experimental kD
to infinite stirring speed, as shown in Figure 3, allows
the determination of the intrinsic membrane coefficient
kDo (Malone and Anderson, 1977). The two solutes were
ribonuclease A and bovine serum albumin. Because
both solutes are 2 orders of magnitude smaller than the
mean pore size of the membrane, Do essentially equals
the diffusion coefficient in solution.
The mean value of /τ for the two solutes is 0.29.
Given that the porosity of the bare membranes was 0.67,
we have τ ) 2.3, which is consistent with the value
derived from the Kozeny constant (K*/2 ) 2.5).
If Darcy’s law (eq 1) is valid in the gel phase of the
membrane, then the pressure obeys Laplace’s equation
in the gel-filled pore spaces because ∇‚v ) 0. Note that
the solute (protein) concentration within the gel-free
pore spaces of the bare membrane also obeys Laplace’s
equation during diffusion. The mathematical analogy
3182 Ind. Eng. Chem. Res., Vol. 35, No. 9, 1996
Figure 3. Diffusion of proteins across a bare (no gel) membrane
to determine /τ. kD is the overall mass transfer coefficient (cm3/s)
defined by eq 7a, where kDo is mass transfer coefficient for
Durapore membrane (ω f ∞) defined by eq 7b, ω is the angular
velocity (rad/s) of the stirrers in the diffusion cell, and Do is the
diffusion coefficient (19 °C) of the protein in solution (cm2/s). /τ
is computed from the intercept of the best-fit straight lines and
eq 7b. The values are 0.31 for ribonuclease A and 0.26 for bovine
serum albumin; error estimates on each determination are ( 0.03.
between pressure in the pressure-flow experiments with
gel-filled membranes and protein concentration within
the bare membrane in the diffusion experiments means
that the tortuosity factor is the same for both processes.
Thus, the hydrodynamic permeability of the gel itself
(k) is related to the hydrodynamic permeability mea-
sured for the membrane (km) by eq 6 with /τ ) 0.29.
Results
Neutral PA Gels. The experimental values of k for
neutral PA gels are plotted against polymer volume
fraction of the gel in Figure 4. There was no measurable
effect of ionic strength (0.001 f 1.0 M) or pH (3.0 f
9.0) (Kapur, 1995). The straight line is a power law fit
to these data, neglecting the values for φ < 0.04:
k ) 4.35 × 10-18φ-3.34 (cm2) (8)
The exponent on φ is larger than the value 1.5 derived
from the theory of deGennes (1979) for entangled
polymer networks. Data for the sedimentation of linear
polymers in solution above the semidilute concentration
yield an exponent near 1.5 (Mijnlieff and Jaspers, 1971;
Nystrom and Roots, 1980; Ethier, 1986).
Tokita (Tokita, 1993; Tokita and Tanaka, 1991)
measured the Darcy permeability of bulk, neutral PA
gels that were synthesized as films 1 mm thick. Tokita’s
data for 2.2% cross-linked gels are represented by the
following empirical expression (Tong, 1995):
k ) 2.64 × 10-16φ-1.42 (CL ) 2.2%) (9a)
Tokita also measured the effect of cross-link density at
φ ≈ 0.035. The following empirical expression fits his
data over the range 0.7-24.0% cross-link density (Tong,
1995):
k ) 2.48 × 10-14CL0.295 (φ ≈ 0.035) (9b)
where CL ) % cross-link density (100 × mass of cross-
linker/monomer). The increase in permeability with
Figure 4. Hydrodynamic permeability (k) versus total polymer
volume fraction (φ) for PA gels. The symbols are from our
experiments (6% CL) with k determined from km using eq 7 and
/τ ) 0.29. Literature data for bulk PA gels are represented by
the lines: Tokita (1993), eq 9; White (1960), eq 10.
increasing CL implies that more cross-linking causes
greater microscopic heterogeneity of the gel structure,
as suggested by Weiss et al. (1981). This hypothesis is
also consistent with the measured increase in the
partitioning of macromolecules with increasing CL
(Tong, 1995).
White (1960) also measured the permeability of bulk
PA gels. At CL ) 5%, he obtained data that are fit by
the following empirical expression over the range 0.04
< φ < 0.11:
k ) 1.015 × 10-16φ-1.083 (cm2) (10)
These permeabilities are an order of magnitude lower
than those measured by Tokita. A possible explanation
is that the hydraulic permeability of bulk gels is difficult
to measure accurately due to their compressibility.
Since White’s measurements were performed at 20-fold
higher pressures than Tokita’s, greater compression of
the gel is to be expected, which would result in lower
apparent permeabilities. It is our opinion that Tokita’s
results are the most representative of bulk, neutral PA
gels.
In Figure 4, we compare our data for the membrane-
supported gels (CL ) 6%) with the data of Tokita (1993)
and White (1960). It appears that the membrane-
supported gels were more permeable than the bulk gels
at low φ, but the differences were small when φ g 0.08.
In general though, the differences between Tokita’s data
and ours are less than the differences in permeability
cited for bulk PA gels by different research groups.
Charged PA Gels. Figures 5 and 6 display data for
the charged gels. Table 1 summarizes the results. The
reproducibility between membranes with the same
nominal gel composition is excellent; the standard
deviation of the measurements is less than 10% of the

Figure 5. Flowrate data for membranes filled with charged PA
gels at 0.05 M ionic strength. The symbols represent different
membranes. The straight lines are linear best fits of all the data
to eq 3. (a) Q gel: km ) 0.122 × 10-14 cm2; (b) S gel: km ) 0.0435
× 10-14 cm2.
Table 1. Results for Hydrodynamic Permeability of
Membrane-Supported, Charged PA-Based Gelsa
gel type IS (M) k × 1014 (cm2)
Q 0.05 0.420 ( 0.035b
Q 0.01 0.342
0.10 0.452
1.00 0.679
S 0.05 0.150 ( 0.013c
S 0.01 0.152
1.00 0.169
a Q form: quaternary amine, pH ) 8.5, charge density ) 0.4
mequiv/cm3 gel, φ ) 0.12 ( 0.01. S form: sulfonate, pH ) 5.9,
charge density ) 0.3 mequiv/cm3 gel, φ ) 0.16 ( 0.01. IS means
ionic strength of the buffered solution, defined as 1/2∑izi2Ci where
zi and Ci are the equivalent valence and concentration of ions of
type i. b Six different membranes prepared in the same manner.
The ( value is the standard deviation of the data. c Four different
membranes prepared in the same manner. The ( value is the
standard deviation of the data.
mean for both positive (Q) and negative (S) gels. No
hysteresis in the pressure-flowrate measurements was
observed when the pressure was first increased and
then decreased. The mean values of permeabilty for the
Q and S gels at 1.0 M ionic strength are plotted in
Ind. Eng. Chem. Res., Vol. 35, No. 9, 1996 3183
Figure 6. Flow versus solution ionic strength (M ) molarity) of
charged PA gels. The order of the experiments is given by the order
of the symbols in the legend (top ) first). The ionic strength was
computed using the standard formula 1/2∑izi2Ci where zi and Ci
are the equivalent valence and concentration of ions of type i.
Increases in ionic strength were achieved by adding sodium
chloride to the buffered solution.
Figure 4 for comparison with the neutral gels. The
permeability of the charged gels was approximately the
same as the neutral gels for the given values of φ.
Figure 6 is interesting in that there is only a small
effect of ionic strength on the permeability. The small
increase in k in going from 0.01 to 1.0 M can be
explained in two ways. First, electroviscous effects that
retard flow are damped by increasing the ionic strength.
Second, the effective solvent quality for a charged
polymer decreases at higher ionic strength; a decrease
in solvent quality can result in an increase in the
permeability of entangled polymer chains (Mijnlieff and
Jaspers, 1971). At higher ionic strengths the charged
groups on the PA chains are less repelled so that
Brownian fluctuations in local gel volume fraction are
greater, leading to a higher permeability.
Figure 6 shows that the charged gels in the pores
were stable with respect to large osmotic stresses. We
found that bulk samples of these gels collapsed to less
than 20% of their total volume (φ increased by a factor
of 5 or more) when the ionic strength was increased from
0.01 to 1.0 M. It appears that confining the gel in a
3184 Ind. Eng. Chem. Res., Vol. 35, No. 9, 1996
porous matrix minimized such osmotic swelling/deswell-
ing. Furthermore, the recovery of the same value of k
when the ionic strength was first increased from 0.01
to 1.0 M and then reduced to 0.01 M (Figure 6a)
demonstrates the stability of this system.
Discussion
Hydrodynamic Theories of Permeability. Be-
cause polymeric gels have a chain-like structure, they
are often modeled as a network of straight cylinders of
radius af. The Darcy permeability is expressed in
general as a function of the volume fraction of chains
(φ):
k ) af2f(φ) (11)
where f(φ) depends on the spatial arrangement of the
chains. Several models are based on a regular periodic
array of cylinders. Sangani and Acrivos (1982) consid-
ered a regular square array of cylinders with flow
oriented perpendicular to the axes of the cylinders at
an angle of 45° with respect to the alignment of the
array. They numerically solved the Stokes equations
for this alignment and computed the drag on each
cylinder. Tsay and Weinbaum (1991) converted the
drag per cylinder to a Darcy permeability and obtained
the following empirical expression from the calculations
of Sangani and Acrivos:
[x ]
2.377
π branes that were studied here, when taken together
f(φ) ) 0.0572 -2 (12a)
φ
Drummond and Tahir (1984) also solved the Stokes
equations for flow past regular arrays of parallel
cylinders. Their results are represented by the following
equation:
1 at low φ is that the method of synthesis was different.
f(φ) ) [-ln φ - 1.476 + 2φ - 1.774φ2 + 4.076φ3]
8φ
(12b)
The difference between the above two expressions is 6%
or less for 0.01 < φ < 0.15. Durlofsky and Brady (1987)
and Phillips et al. (1989,1990) numerically solved the
Stokes equations for flow through networks of chains
of spheres (af ) sphere radius) arranged in periodic
configurations. Their calculated permeabilities are
comparable to those predicted from eq 12.
Jackson and James (1986) reviewed experimental
data for flow through fibrous media over a large varia-
tion of af and found that the following expression, which
is semi-empirical in nature, fits much of the data:
3 membrane-supported charged gels were resistant to
f(φ) ) - [ln(φ) + 0.931] (13)
20φ
Spielman and Goren (1968) modeled a network of
straight cylinders by considering it a Brinkman fluid.
The result for a random orientation of the cylinders is
[ ]
x2 5x K1(x)
x2 ) 4φ (14)
3 6 K0(x)
+
where x ) af/xk and Kn is the modified Bessel function
of the second kind. Values of k computed from eq 14
are about 25% higher than from eq 13 over the range
0.01 < φ < 0.15. Note that the algebraic form of eq 14
is less convenient than eq 11. A least-squares fit of eq
13 to the data of Tokita (1993) at 2.2% CL (see eq 9a)
gives af ) 5.7 Å, which is comparable to the value (6.5
Å) determined from measurements of the partitioning
of globular proteins in bulk gels (Tong and Anderson,
1995). Theoretical models for hydrodynamic perme-
ability do not explicitly account for cross-link density.
Tokita’s data (see eq 9b) show an increase in k as CL
increases. This trend has also been noted by Weiss et
al. (1981). The random network models represented by
eq 11 would require af to increase as CL increases if it
is applied to gels at different cross-link density. A
physical interpretation of this increase in af can be
constructed by imagining that an increased cross-link
density results in “bundling” of the polymer chains, that
is, microsegregation of the polymer.
Bulk versus Membrane-Supported Gels. Because
the pore size (≈0.5 µm) of our membranes was much
greater than the hydrodynamic screening length of the
gel (xk < 4 nm), the microstructure of the gel should
be the same in the pores as in a bulk gel. Figure 4
suggests that there might be a difference between
membrane-supported neutral gels and bulk gels at low
φ; however, Tokita’s data could be in error at low φ
because of some compression of the bulk gel when
subjected to pressure.
One might speculate that there were defects in the
low φ gels synthesized in the porous membranes, which
would explain the higher permeabilities. We believe
this was not the case. Measurements of diffusion and
filtration of proteins through the same gel-filled mem-
with the hydrodynamic permeability data, show con-
clusively that the gel substantially filled the porous
membranes (Kapur, 1995; Kapur et al., 1996). In
aggregate, these experimental results prove that the
membrane-supported gels were essentially defect free.
One possible explanation for the different permeabili-
ties for the bulk and membrane-supported neutral gels
In the membrane-supported neutral gels, the polymer-
ization was photo-initiated whereas the bulk gels stud-
ied by Tokita (1993) were chemically initiated. Righetti
et al. (1981) have found that gels synthesized with
different initiators and promoters can have different
properties.
Summary
The hydrodynamic permeability of the membrane-
supported gels was reproducible between membranes
for a given cross-link density and polymer volume
fraction. Compression of the gel, which would have
been indicated by a lack of proportionality between
water flow rate and applied pressure, was negligible up
to pressure gradients as great as 300 bar/cm. The
osmotic deswelling/swelling, and their permeability
varied little when the ionic strength was changed from
0.01 to 1.0 M. The permeabilities of the positive (Q)
and negative (S) gels were the same as for the neutral
gels at the same polymer volume fraction.
The important result is that our experiments dem-
onstrate that stable, essentially defect-free and non-
compressible gels can be fabricated within microporous
supports.
Acknowledgment
This research was supported by NSF Grant CTS-
9122573 and by BioSepra, Inc. We greatly appreciate
the assistance of Dr. J. Y. Koo of BioSepra, Inc., who

synthesized the membrane-supported charged gels.
J.L.A. wishes to express his gratitude to Eli Ruckenstein
for his encouragement, advice, and friendship over the
years.
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Received for review January 17, 1996
Revised manuscript received June 18, 1996
Accepted June 22, 1996X
IE960015Z
X Abstract published in Advance ACS Abstracts, August 15,
1996.