Separation and Purification Technology 51 (2006) 352–358

Pervaporative removal of benzene from aqueous solution through

supramolecule calixarene filled PDMS composite membranes
Hong Wu a , Liang Liu a , Fusheng Pan a , Changlai Hu a , Zhongyi Jiang a,b,∗
a Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b State Key Laboratory of Functional Polymer Materials for Adsorption and Separation, Nankai University, Tianjin 300071, PR China

Received 17 December 2005; received in revised form 24 February 2006; accepted 24 February 2006

Abstract
A novel composite membrane using supramolecule calix[4]arene filled polydimethylsiloxane (PDMS) as the top active layer and non-woven
fabric as the support layer was developed for the pervaporative removal of benzene from water. Compared to unfilled PDMS homogenous
membrane, the composite membrane exhibits both higher separation factor and higher benzene flux by 1.8- and 3.2-folds, respectively. Effects of
pervaporation operating parameters such as feed Reynolds number, benzene concentration in feed, downstream pressure and operating temperature
on the permeation flux and separation factor had been investigated. The benzene permeation flux was proportional to both the benzene concentration
in feed and the downstream vacuum. From the temperature dependent permeation flux values, Arrhenius activation energies for permeation of
benzene and water were estimated.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pervaporation; Calix[4]arene; Polydimethylsiloxane (PDMS); Composite membrane; Benzene

1. Introduction tion temperature (Tg about 150 K). As a result, PDMS-based

membranes usually have a relatively higher flux for organics
Pervaporation as a membrane separation process has unique than glass-state membranes. In order to further improve the
advantages and potential applications in the dehydration of membrane selectivity for organic compounds, several kinds of
water–organic mixtures [1,2], removal of volatile organic com- fillers such as active carbon and carbon molecular sieve have
ponents (VOCs) from dilute aqueous wastes [3] and separation been added into PDMS matrix due to their absorptive ability for
of close boiling point mixtures or azeotropes [4]. Among these organics [7–12].
applications, the removal of trace VOCs from wastewater or Calixarenes with supramolecular structures have received
groundwater by pervaporation has been much attractive due to much attention recently due to their use in biological and
an increasing demand for environmental protection [5]. Com- synthetic receptor models as well as easy single-step prepara-
pared with such traditional methods that generally used for tion. The flexible calixarene framework requires small energy
VOCs removal such as gas distillation and adsorption, pervapo- changes to accommodate guest molecules, which makes them
ration is less energy consuming and complex. Since the VOCs exceptionally resourceful host molecules. It is well known that
concentration in aqueous solution is usually very low, organic- the ␲-rich cavity in calixarene is suitable for the inclusion of
permselective membranes are obviously much more favorable neutral guest of complementary size such as aromatic com-
than water-permselective membranes. pounds, hydrocarbons and chlorohydrocarbons. It can be imag-
Polydimethylsiloxane (PDMS), as a typical organic- ined that the moderate supramolecular interaction which lies
permselective membrane material, has been widely used in between the physical adsorption and chemical adsorption, may
pervaporative membrane development [6]. Its flexible chains improve the pervaporation performance of PDMS membrane
give PDMS a rubber character with a rather low glass transi- to some extent [13,14]. Uragami has investigated the effect of
the addition of tert-butylcalix[4]arene (CA) to PMMA-b-PDMS
membrane for the removal of benzene from dilute aqueous solu-
∗ Corresponding author. Tel.: +86 22 27892143; fax: +86 22 27892143. tion [15,16]. The experimental results indicated that addition
E-mail address: [email protected] (Z. Jiang). of CA to PMMA-b-PDMS membrane increased the separation

1383-5866/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.02.017
 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358 353

factor from 1800 to 2300. Our previous work also confirmed remove PEG, dried in vacuum for 24 h to remove the water and
that the addition of CA to PDMS membrane could improve swelled in the feed solutions before being evaluated.
the separation performance, for example, after 3 wt% of CA
was incorporated into PDMS, the membrane separation factor 2.2.4. PDMS composite membrane
increased from 3302 to 5604 while the benzene flux decreased Unfilled PDMS composite membrane was also prepared for
only slightly [17]. the purpose of comparison. The preparation procedure was just
In this paper, a novel composite membrane using CA filled the same as the above filled PDMS composite membranes (Sec-
PDMS as the thin active layer and non-woven fabric as the sup- tion 2.2.3) except that casting solution A was used here instead
port layer was developed in expectation of achieving both high of B.
separation factor and high permeation flux in the pervaporation
process of removing benzene from aqueous solution. The effects 2.3. Scanning electron microscopic (SEM) studies
of operating conditions including feed flow rate (Reynolds num-
ber), benzene concentration in feed, downstream pressure and The membrane samples were fractured in liquid nitrogen and
temperature on the separation performance of the filled compos- coated with gold to observe the cross section morphologies by
ite membrane were examined. scanning electron microscopy (XL30ESEM, Philips).

2. Experimental 2.4. Pervaporation experiment

2.1. Materials A schematic diagram of the pervaporation test unit is shown

in Fig. 1. The membranes were fixed into a plate and frame
Polydimethylsiloxane prepolymer was purchased from Bei- pervaporation test cell. An aqueous solution of benzene flowed
jing Huaer Co. Ltd. CA was purchased from Nankai University. from the feed tank by the circulation pump and passed through
Non-woven fabric was purchased from Deepak fertilizers & the pervaporation cell continuously. The feed Reynolds num-
Petrochemical Co. Ltd. All the other solvents and reagents were ber was varied by changing the feed flow rate. Permeate was
of analytical grade and used as received. collected alternatively by two cold traps immersed in liquid
nitrogen. The effective membrane area was 25.6 × 10−4 m2 . The
2.2. Membrane preparation concentrations of the feed and permeate were analyzed by gas
chromatograph (Hewlett–Packard 6890) using diethyl amine as
2.2.1. PDMS membrane an internal standard compound.
For the preparation of unfilled PDMS homogenous mem- The separation factor of benzene/water mixture was
brane, PDMS prepolymer, solvent (toluene), crosslinking agent expressed as Eq. (1):
(tretraethylorthosilicate, TEOS) and catalyst (dibutyltin dilau-
cbP /cw
P
rate) were mixed with a 1:1:0.1:0.02 of weight ratio to form α= (1)
the casting solution (designated as casting solution A). Then, cbF /cw
F

the casting solution was poured onto an organic glass plate and
where cbP and cwP represent the benzene and water concentra-
cast with a casting knife to form a film. After being left at room
tions in the permeate, respectively (wt%), cbF and cw F represent
temperature for 24 h, crosslinked solid membranes were formed
the benzene and water concentrations in the feed, respectively
as toluene evaporated eventually. The membranes were further
(wt%).
dried in vacuum for another 24 h and swelled sufficiently in the
The permeation flux (J) of benzene and water at steady state
feed solutions before being evaluated.
was determined as follows: first, the total permeate weight within
2.2.2. CA-f-PDMS membrane
For the preparation of the CA-filled PDMS homogenous
membrane, 3 wt% CA (related to the weight of PDMS) was
added into the casting solution A under stirring for 10 min to
form casting solution B. The rest preparation processes were
just as same as the above procedure (Section 2.2.1).

2.2.3. CA-f-PDMS composite membrane

For the preparation of the CA-filled PDMS composite mem-
branes, the non-woven fabric was first immersed in a 20 wt%
PEG-10,000 solution for 24 h [18]. Then, the casting solution
B was poured onto the fabric surface and the fabric was hung
vertically. By this way, the excess solution flowed down from
the hemline and, as toluene evaporated completely, a thin active Fig. 1. Schematic diagram of the pervaporation apparatus 1: heater, 2: thermo-
layer was formed on the non-woven fabric surface. The com- couple, 3: feed container, 4: circulation pump, 5: flowmeter, 6: membrane cell,
posite membranes were immersed in distilled water for 24 h to 7: cold trap, 8: liquid nitrogen, 9: desiccator, 10: buffer, 11: vacuum pump.
354 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358

a certain period of time (t) was measured, and the amount of where t is the experimental time interval for the pervaporation
benzene and water (W) was calculated by multiplying the total and A is the effective membrane area.
weight by, respectively, the benzene and water concentration in
the permeate. The flux was calculated by Eq. (2):

W 3. Results and discussion

J= (2)
At
3.1. SEM micrographs of composite membranes

The cross section structures of the CA-f-PDMS membrane,

CA-f-PDMS composite membrane and the non-woven fabric
substrate are shown in Fig. 2(a–c), respectively. The existence
of CA in CA-f-PDMS membrane and in the active layer of
CA-f-PDMS composite membrane can be observed clearly. The
thickness of the CA-f-PDMS membrane was about 150 ␮m and
that of the pure PDMS membrane was about 200 ␮m (not shown
in the figure). The CA-f-PDMS top layer of about 50 ␮m thick-
ness was tightly adhered on the surface of the non-woven fabric
substrate and the total thickness of the CA-f-PDMS composite
membrane is about 150 ␮m.

Fig. 3. Effect of feed Reynolds numbers on benzene flux (a) and water
flux (b): PDMS membrane(
); CA-f-PDMS membrane(); PDMS composite
membrane(); CA-f-PDMS composite membrane(×). Benzene concentration
Fig. 2. Cross sections of CA-f-PDMS membrane (a), CA-f-PDMS composite in feed solution: 1.39 kg m−3 ; operating temperature: 333 K, downstream pres-
membrane (b), and non-woven fabric (c). sure: 1 kPa.
 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358 355

3.2. Effects of feed Reynolds numbers on benzene and

water fluxes

The effects of feed Reynolds numbers on the benzene flux and

water flux of PDMS membrane, CA-f-PDMS membrane, PDMS
composite membrane, CA-f-PDMS composite membrane are

Fig. 4. Effect of benzene concentration in feed on benzene flux: PDMS mem-

brane (
); CA-f-PDMS membrane(); PDMS composite membrane(); CA-f-
PDMS composite membrane(×). Operating temperature: 333 K, feed Reynolds
number: 20,800, downstream pressure: 1 kPa.

Fig. 5. Effect of downstream pressure on benzene flux (a) and separation fac- Fig. 6. Effect of operating temperature on benzene flux (a), water flux (b)
tor (b): PDMS membrane(
); CA-f-PDMS membrane(); PDMS composite and separation factor (c): PDMS membrane(
); CA-f-PDMS membrane ();
membrane();CA-f-PDMS composite membrane(×). Benzene concentration in PDMS composite membrane(); CA-f-PDMS composite membrane(×). Ben-
feed solution: 1.39 kg m−3 , operating temperature: 333 K, feed Reynolds num- zene concentration in feed solution: 1.39 kg m−3 , feed Reynolds number: 20,800,
ber: 20,800. downstream pressure: 1 kPa.
356 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358

shown in Fig. 3(a) and (b). The PDMS composite membrane

and CA-f-PDMS composite membrane exhibited both much
higher benzene flux and water flux than PDMS membrane
and CA-f-PDMS membrane in the whole range of Reynolds
number tested due to the decrease of thickness of membrane
active layer. The addition of CA lowered the water flux of the
membranes (CA-f-PDMS membrane and CA-f-PDMS compos-
ite membrane) compared with pure PDMS homogenous and
composite membranes, but has little influence on the benzene
flux. While the benzene fluxes of the two types of compos-
ite membranes (PDMS composite membrane and CA-f-PDMS
composite membrane) increased with the enhancement of feed
Reynolds number, those of the two homogeneous membranes
(PDMS membrane and CA-f-PDMS membrane) seemed to be
little influenced by feed Reynolds number. The total permeation
resistance is composed of boundary resistance and membrane
resistance. With the increase of Reynolds number, the thick-
ness of the boundary layer decreased and so did the boundary
resistance. For homogeneous membrane, membrane resistance
contributed more than the boundary resistance especially in the
pervaporation of dilute benzene aqueous solution. For composite
membrane whose active layer was much thinner, the influence
of boundary resistance became relatively greater to some extent
compared to the decreased membrane resistance. Therefore, the
benzene and water flux of composite membranes increased more
obviously than that of homogeneous membranes with Reynolds
number increasing.

3.3. Effect of feed concentration on benzene flux

Fig. 4 shows the effect of benzene concentration in feed

on benzene flux. Linear relationships between benzene con-
centration in feed and benzene flux were obtained for all the Fig. 7. Arrhenius relationship between benzene flux (a), water flux (b) and
membranes in the range of feed benzene concentration from operating temperature: PDMS membrane (
); CA-f-PDMS membrane ();
0.3 to 1.4 kg m−3 . With the increase of benzene in feed, the PDMS composite membrane(); CA-f-PDMS composite membrane(×). Oper-
ating conditions are the same as Fig. 6(a).
amount of benzene dissolved on the membrane upstream sur-
face increased, resulting in an increased concentration difference
between the upstream side and downstream side. The benzene benzene flux of CA-f-PDMS composite membrane decreased
flux was increased due to the increased diffusion driving force from about 400 to 300 g m−2 h−1 and the separation factor
caused by the concentration difference. This result was in con- increased from 5913 to 7550. Lower vacuums reduced the driv-
sistence with that obtained by other researchers [19–21]. ing force for diffusion through the membrane, leading to a lower
flux. On the contrary for the pervaporative removal of volatile
3.4. Effects of downstream pressure on benzene flux and benzene from aqueous solution, since benzene is much more
separation factor volatile than water, in general, the desorption of benzene at the
permeate–membrane interface is much easier than that of the
The effects of downstream pressure (1–12 kPa) on benzene water, indicating that desorption of water is more significantly
flux and separation factor are shown in Fig. 5(a) and (b). influenced by the downstream pressure. Therefore, the separa-
As the downstream pressure increased from 1 to 10 kPa, the tion factor increased with increase of downstream pressure.

Table 1
The activation energy values for permeation of benzene and water
Membranes PDMS CA-f-PDMS PDMS composite CA-f-PDMS
membrane membrane membrane composite membrane

Ea,p for benzene (kJ mol−1 ) 6.40 ± 0.07 9.66 ± 0.08 6.10 ± 0.07 16.52 ± 0.02
Ea,p for water (kJ mol−1 ) 16.52 ± 0.02 44.26 ± 0.24 58.16 ± 0.16 23.04 ± 0.01
 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358 357

3.5. Effect of operating temperature on the permeate flux

and separation factor

The effects of operating temperature on the benzene flux,

water flux and separation factor are shown in Fig. 6(a–c), respec-
tively. It is observed that for all the membranes both the benzene
and water flux increased monotonically with the increase of
temperature while the separation factor decreased. When the
operating temperature increased from 309 to 333 K, the ben-
zene flux of CA-f-PDMS composite membrane increased from
254 to 407 g m−2 h−1 . Pervious sorption experiment results (not
shown in this manuscript) indicated that the sorption of benzene
and water was little influenced by the increase of tempera-
ture (309–333 K). Therefore, according to the solution-diffusion
mechanism, the diffusion process was the governing factor in the
permeation. As indicated by the free-volume theory [22], when
the temperature increases, both the frequency and amplitude of
the chain jumping increase and thus, the free-volume becomes
larger. Therefore, permeation of the diffusing molecules through
the membranes becomes easier, resulting in an increase of flux.
In addition, the mobility of the diffusing molecules is also
enhanced by the increase of temperature.
When the relationship between the benzene flux or the water
flux and the operating temperature was expressed in the form
of ln(Jb ) ∼1/T or ln(Jw ) ∼1/T, as shown in Fig. 7(a) and (b),
it could be seen that the relationship obeys the Arrhenius-type
relationship. The activation energy for permeation can be then
calculated from the following Arrhenius-type expression:


Ea,p
J = B exp − (3)
RT
where B is a constant, T is the operating temperature, Ea,p is the Fig. 8. (a) Comparison of separation factor (a) and benzene flux (b) of the mem-
branes: PDMS membrane (1); CA-f-PDMS membrane (2); PDMS composite
activation energy for permeation, and R is the gas constant. The membrane (3); CA-f-PDMS composite membrane (4). Benzene concentration
activation energy values for permeation of benzene and water in feed solution: 1.39 kg m−3 , feed Reynolds number: 20,800, operating tem-
were estimated and presented in Table 1. Activation energy perature: 333 K, downstream pressure: 1 kPa.
of permeation shows the degree of temperature dependency
of component flux. As the temperature increases, water flux
increases more rapidly than benzene flux due to its higher acti-
vation energy and thus, causes the decrease of separation factor.
Table 2
Comparison of pervaporation performances
Membrane material Temperature (◦ C) Benzene Benzene flux Separation References
concentration (wt%) (g m−2 h−1 ) factor

PVDF 25 0.08 43 250 [21]

PDMSDVS 40 0.05 70.9 2886 [13]
PDMSDMMA 40 0.05 51.4 1853 [13]
PDMSDVB 40 0.05 45.5 3099 [13]
PDMSEGDM 40 0.05 49.6 2011 [13]
PFA-g-PDMS 40 0.05 21.6 4600 [23]
PMMA-g-PDMS 40 0.05 12 3700 [23]
PEMA-g-PDMS 40 0.05 9.3 2400 [14]
CA filled PDMS-g-PMMA 40 0.05 23 1800 [16]
CA filled PDMS-b-PMMA 40 0.05 43 2300 [15]
Silicone rubber composite membrane 40 0.13 75 629 [3]
PDMS membrane 60 0.14 126 3302 This study
CA-f-PDMS membrane 60 0.14 116 5604 This study
PDMS composite membrane 60 0.14 365 4600 This study
CA-f-PDMS composite membrane 60 0.14 407 5913 This study
358 H. Wu et al. / Separation and Purification Technology 51 (2006) 352–358

Besides, it also could be observed from Fig. 7(a) that as the [2] M.D. Kurkuri, U.S. Toti, T.M. Aminabhavi, Syntheses and characterization
temperature increased, the benzene flux of CA-f-PDMS mem- of blend membranes of sodium alginate and poly(vinyl alcohol) for the
brane and CA-f-PDMS composite membrane increased more pervaporation separation of water + isopropanol mixtures, J. Appl. Polym.
Sci. 86 (2002) 3642–3651.
rapidly than those of PDMS membrane and PDMS composite [3] R.W. Baker, J.G. Wijmans, Process for recovering organic components
membrane. This phenomenon indicates that the permeability of from liquid streams, United States Patent 5,169,533 (1992).
benzene in CA filled PDMS membrane was more sensitive to [4] B. Smitha, D. Suhanya, S. Sridhar, M. Ramakrishna, Separation of
the temperature than that in CA-free PDMS membrane. organic–organic mixtures by pervaporation—a review, J. Membr. Sci. 241
(2004) 1–21.
[5] M. Peng, L.M. Vane, S.X. Liu, Recent advances in VOCs removal from
3.6. Summary and comparison of pervaporation water by pervaporation, J. Hazard. Mater. 98 (2003) 69–90.
performances [6] J.E. Mark, Some interesting things about polysiloxanes, Acc. Chem. Res.
37 (2004) 946–953.
The separation factor and benzene flux of the four kinds of [7] J.-M. Duval, B. Folkers, M.H.V. Mulder, G. Desgrandchamps, C.A. Smol-
membranes are summarized in Fig. 8(a) and (b). Separation fac- ders, Separation of a toluene/ethanol mixture by pervaporation using active
carbon-filled polymeric membranes, Sep. Sci. Technol. 29 (1994) 357–
tor was increased by the addition of CA without reduction of 373.
benzene flux. In comparison, CA-f-PDMS composite membrane [8] W. Ji, S.K. Sikdar, S.-T. Hwang, Sorption, diffusion and permeation of
showed both the highest benzene flux and the highest separation 1,1,1-trichloroethane through adsorbent-filled polymeric membranes, J.
factor among the four kinds of membranes. Membr. Sci. 103 (1995) 243–255.
A comparison between the pervaporation results in this study [9] L. Li, Z. Xiao, Z. Zhang, S. Tan, Pervaporation of acetic acid/water mixtures
through carbon molecular sieve-filled PDMS membranes, Chem. Eng. J.
and those reported in some literature work is made and listed in 97 (2004) 83–86.
Table 2. As can be seen, the CA-f-PDMS composite membrane [10] S.-Y. Lu, C.-P. Chiu, H.-Y. Huang, Pervaporation of acetic/water mixtures
prepared in this research showed better performance than those through silicalite filled polydimethylsiloxane membranes, J. Membr. Sci.
membranes presented in other reports for pervaporative removal 176 (2000) 159–167.
of benzene from dilute aqueous solution. [11] S.K. Ganguly, A.N. Goswami, Surface diffusion kinetics in the adsorption
of acetic acid on activated carbon, Sep. Sci. Technol. 31 (1996) 1267–
1278.
4. Conclusions [12] F. Peng, Z. Jiang, C. Hu, Y. Wang, H. Xu, J. Liu, Removing benzene from
aqueous solution using CMS-filled PDMS pervaporation membranes, Sep.
The pervaporation properties of CA filled PDMS composite Purif. Technol. 48 (2006) 229–234.
membranes for benzene removal from aqueous solution were [13] A.T. Macias, J.E. Norton, J.D. Evanseck, Impact of multiple cation-␲ inter-
action upon Calix[4]arene substrate binding and specificity, J. Am. Chem.
investigated. Due to the special structure and moderate inter-
Soc. 125 (2003) 2351–2360.
action towards benzene of CA, the incorporation of CA into [14] A. Dominik, H.J. Roth, K.D. Schierbaum, W. Gopel, Supramolecular com-
PDMS matrix improved the permselectivity of the PDMS mem- plexes based on calixarenes: force field calculations and applications for
brane significantly with little decreasing of benzene flux. By the chemical sensors, Supramolecular Sci. 1 (1994) 11–19.
combination of filling and composite preparation technique, a [15] T. Uragami, T. Meotoiwa, T. Miyata, Effects of morphology of multicompo-
nent polymer membranes containing calixarene on permselective removal
new type composite membrane using CA filled PDMS as the
of benzene from a dilute aqueous solution of benzene, Macromolecules 36
thin active layer and non-woven fabric as the support layer was (6) (2003) 2041–2048.
developed. The benzene flux showed linear increasing relation- [16] T. Uragami, T. Meotoiwa, T. Miyata, Effects of the addition of Calixarene
ship with the benzene concentration in feed and the downstream to microphase-separated membranes for the removal of volatile organic
vacuum. The Arrhenius correlation between the benzene flux compounds from dilute aqueous solutions, Macromolecules 34 (19) (2001)
6806–6811.
and the feed temperature was obtained. Compared to the unfilled
[17] L. Liu, Researches on the preparation and the separation properties of novel
PDMS homogenous membrane, the separation factor increased PDMS pervaporation membranes, M.S. dissertation, Tianjin University,
from 3302 to 5913 and the benzene flux increased from 126 to 2005.
407 g m−2 h−1 ), better than those membranes reported in other [18] H.J. Kim, S.S. Nah, B.R. Min, A new technique for preparation of PDMS
current literatures. pervaporation membrane for VOC removal, Adv. Environ. Res. 6 (2002)
255–264.
[19] J.D. Li, C.X. Chen, B.B. Han, Y. Peng, J. Zou, W.J. Jiang, Laboratory and
Acknowledgements pilot-scale study on dehydration of benzene by pervaporation, J. Membr.
Sci. 203 (2002) 127–136.
The financial support from the Cross-Century Talent Rais- [20] K. Jian, P.N. Pintauro, R. Ponangi, Separation of dilute organic/water mix-
ing Program of Ministry of Education of China, the Sinopec tures with asymmetric poly(vinylidene fluoride) membranes, J. Membr.
Research Program (NO. X500003), the key project of Ministry Sci. 117 (1996) 117–133.
[21] K. Jian, P.N. Pintauro, Asymmetric PVDF hollow-fiber membranes for
of Education of China are greatly appreciated. organic/water pervaporation separations, J. Membr. Sci. 135 (1997) 41–53.
[22] R.C. Binning, R.J. Lee, J.F. Jennings, E.C. Martin, Separation of liquid
References mixtures by permeation, Ind. Eng. Chem. 53 (1961) 45–50.
[23] T. Miyata, H. Yamada, T. Uragami, Surface modification of microphase-
[1] J.M. Haack, W. Lenk, D. Lehmann, K. Lunkwitz, Pervaporation separation separated membranes by fluorine-containing polymer additive and removal
of water/alcohol mixtures using composite membranes based on polyelec- of dilute benzene in water through these membranes, Macromolecules 34
trolyte multiplayer assemblies, J. Membr. Sci. 184 (2001) 233–243. (23) (2001) 8026–8033.