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aCII!NCI!@OIAeCT-

ELSEVIER

MEMBRANE
SCIENCE

Journal of M embrane Science 270 (2006) 101 - 107


www.elsevier.com/locatelmemsci

Surface modification of mesoporous membranes by fluoro-silane


coupling reagent for CO2 separation
N. Abidi a, A. Sivade a, D. Bourret a .*, A. Larbot a , B. Boutevin b ,
F. Guida-Pietrasanta b, A. Ratsimihety b
b

Instilut Europeen des Membranes, UMR 5635, IEMICNRS /9/9, Route de Mende. 34293 MOnIpellier Cedex 5, France
Lahora/oire de Chimie Ma cromo/ecu/aire. UPRESA 5076 CNRS, NSCM, 8 Rue de f'Eeole lIonna/e, 34296 Motllp ellier Cedex. France

Received 8 March 2004; accepted 6 June 2005


Available online 17 October 2005

Abstract

The potentia1 of hybrid organic- inorganic membranes for separaling organic molecules from air, based on solubility selective mechanism,
was evaluated. Alumina and titan a membranes with average pore size near 4 nm were surface modified using trimethoxysilane fluorinated
coupling reagent. The penneabilities to helium. nitrogen. methane. ethane. propane. butane and carbon dioxide were evaluated at feed

pressures lying between (1.5 x 10' and 3.5 x 10' Pal 1.5 and 3.5 bar and permeate outlet near I x 10' Pa (I bar). The permeabilities of the
grafted membranes generally decreased by about two to three orders of magnitude compared with the untreated membranes. The C0 21N 2
permselectivity increased significantly in the case of the Ti02 gmfted membrane. The membranes performances were compared and the
Ti02 grafteu. membrane exhibits highcr permselectivity and permeability, so that. it is a good candidate for CO2 to N l separation and CO2 to
hydrocarbon separation.

2005 Elsevier B. V. All rights reserved.


Keywords: Surface modification; F1uorosilane: Ceramic membrane: Gas permeation; Grafted membranes

1. Introduction

During the few last years, special attention has been paid
to ceramic membranes for gas separation because of their
thermal and chemical stabilities compared to those of polymeric membranes [1.2]. Interesting application may include
the separation of C02 from gas mixtures. which is of particular interest for environmental protection. Unfortunately.
the mechanism for gas transport in commercially available
porous ceramic membranes with pores < I 0 nm is Knudsen
diffusion. Therefore. the separation efficiency between gases
having a small difference in molecular weights. such as C02
and N2. is quite low. Thus, many researchers have tried to
modify the surface of ceramic membranes in order to enhance
the C02/N2 separation factor by gas transport mechanisms
other than Knudsen diffusion [3-12].
Corresponding author.
E-mail addrn f>: bourret @criLuniv-montp2.fr ( D. Bo urret).
03767388/$ - see front matter () 2005 Elsevier B. V. All rights reserved.
doi: I 0.1OI6lj.memsci .2005.06.054

For membranes with pores <lOnm, surface modification


by covalently bonded molecular mono-layer is one of the
more convenient ways to alter membrane performance. Such
modification can increase the performances of the membrane
by, on one hand, reducing the mean pore size, and on the other
hand. by promoting an eventual specific interaction between
the surface of the membrane and the permeating molecules
to enhance penneation.
Miller and Koros [13] modified commercially available
Membralox mesoporous alumina membranes with an average pore size of 4 nm. A vapour-phase deposition was used to
link trichlorosilane coupling reagent to the alumina surface.
Paterson and coworkers [14-16J perfonned such surface modification using wet chemistry routes rather than
vapour-phase in order to link the coupling reagent. With
octadecyltrichlorosilane [14]. the C02/N2 permselectivity
(i.e .. the ratio of single gas permeabilities) obtained was
only 1.05. a little higher than the Knudsen ideal separation
factor. 0.8. Similar behaviour than for permeation through

102

N. Abidi et al. / Journal of Membrane Science 270 (2006) 101-107

low-density polyethylene membranes was obtained by Randon and Paterson [15] using n-dodecylphosphate as coupling
reagent (C021N2 permselectivity of 4.5 for the modified
membrane compare to 2.5 or 12.6 for, respectively, high and
low-density polyethylene). The best C021N2 permselectivity
(10.2) was obtained [16] for a modified ,,{-A}z03 membrane
with a monolayer of polydimethylsilane on its surface. In
this case the transfer mechanism through the PDMS-aIumina
membrane was a solubility/diffusion one.
The coupling reagent used by Hyun et aI. [17] was phenyltriethoxysilane having a special functional group (phenyl
radical) with a high affinity for C02. The C021N2 permselectivity was 2.15 and a mixed Knudsen/surface diffusion
was deduced for C02 transfer mechanism through the modified membrane.
Mejean et al. [18] performed surface modification of
commercially available ,,{-Al203 membrane (mean pore
size 5 nm) with fluorinated triethoxysilane and dodecyltriethoxysilane. The C021N2 permselectivity were 4.0 for fluorinated triethoxysilane and 5.3 for dodecyltriethoxysilane.
A mixed Knudsen/surface diffusion was deduced for C02
transfer mechanism through the modified membranes.
More recently, Javaid et al. [19] modified commercially
available Membralox mesoporous alumina membranes
with an average pore size of 5 and 12 nm using solutions
of alkyl trichlorosilanes in toluene. Their approach seems to
be ideal for creating solubility-selective membranes because
of the ability to deliver a large number of desired chemical
groups while still remaining a relatively high free volume.
The main objective of this work was to synthesize
organic-inorganic hybrid membranes comprised of fluorinated triethoxysilane grafted to the surface of commercially
available mesoporous membranes, and evaluate their performance for C021N2 separation. Fluorinated coupling reagents
were preferred to alkyl ones because in each case C02 has a
high solubility, but alkanes have poor solubility in fluorinated
compounds [18]. Thus, for separation of a mixture .of C02,
alkanes and N2, ceramic membranes modified by fluorinated
coupling reagent will be more efficient due to large C021N2
and low C02/alkanes permselectivities. However, some large
C02/alkanes permselectivities were obtained due to the fact
that a multilayer surface diffusion can occurs for butane in
the case of ,,{-A}z03 modified membrane.
In this paper, commercially available mesoporous Ti02
and ,,{-Al203 membranes were surface-modified with fluorinated coupling reagent. The fluorinated-coupling reagent,
CsF 17C2~Si(OCH3h, was delivered in chloroform and .
grafted to the surface via SiOH groups formed by hydrolysis
of triethoxy groups with surface water. The membrane was
tested for permeance to methane, ethane, propane, butane,
carbon dioxide, helium and nitrogen. Helium was used in
order to test Knudsen flow for the membrane. Methane,
ethane, propane, butane and carbon dioxide were used to evaluate C021N2 and C02/alkanes permselectivities. Section 2
provides the details of the fluorinated coupling reagent synthesis, membrane elaboration and permeation testing. The

results are presented in Section 3, with additional discussion.


Section 4 contains our conclusions.

2. Experimental

2.1. Fluorinated coupling reagent synthesis


The fluorinated-coupling reagent used in this work was
(3,3,4,4,5,5,6,6,7,7,S,8,9,9,10,10,10-heptadecafluorodecy1)trimethoxysilane, CsF17C214Si(OCH3h. It was synthesized
in two steps by the following reactions [2S]:
(i) Hydrosilysation of CgF 17CH2=CH2
CSF17CH=CH2 + HSiCl3 --+ CgF17C2H4SiCb
(ii) Methoxylation of trichlorosilane
CgF17C2H4SiCI3 + CH30H --+ CgF17C2H4Si(OCH3)3

2.2. Membrane synthesis procedure


The mesoporous Ti02 membrane used in this study was
provided by "Cerasiv" (France). The membrane had a 1.1 J.Lm
thick active layer as measured by SEM. An average pore
size of 4 nm was deduced from BET. The active layer was
deposited on the inner surface of a Zr02-aA1203 multi-layer
support, which had a much larger pore size (200 nm for the
intermediate layer and SOO nm for the supporting one as given
by SEM analysis). Thus, this macroporous support had no
significant resistance to gas permeation compare to the active
layer.
The "{-Ah03 membrane was purchased to the "ExekiaPall" (France). The membrane had a 3 /-Lm thick active layer
with a porosity of 40%. An average pore size of 4 nm was
measured for this active layer by BET. The outer support was
made with ex-alumina with much larger pore size (200 nm for
the intermediate layer and 800 nm for the supporting one as
given by SEM analysis) and had no significant effect on gas
permeation compare to the active layer.
In both cases, the tubes bad an outer diameter of 1.0 cm
and an inner diameter of 0.7 cm. For our experiments, we cut
the tubes into 15 cm long pieces using a diamonded saw.
After cutting, the membranes were soaked in ethanol for
1 h and then, in bi-distilled water for 1 h at ambient temperature (ethanol was obtained from Merck with purity >99%).
The membranes were, then, dried in an oven at 120C during 1 day in order to leave only surface hydroxyl groups and
part of the first hydration layer. After the heat treatment, the
membranes were stored in a glove box.
Solution (10- 3 moll-I) of the fluorinated-coupling
reagent in anhydrous chloroform (Aldrich) was prepared in
a glove box. The tubular membrane was filled with the solution and hermetically closed. At that point, it was remove
from the glove box and the solvent was allowed to evaporate
though the membrane at 20C. During this evaporation, the

N. Abidi et al. / Joumal of Membrane Science 270 (2006) 101- /07

103

membrane was manually turned over and over each 5 min.


After complete evaporation of the solvent (i.e., all the solvent
was removed from the membrane), the membrane was soaked
in pure solvent for I h, this treatment was repeated three
times in order to remove all the remaining free (physisorbed)
fluorinated-coupling reagent.

constant, T the absolute temperature and P mea, is the mean


pressure in the membrane. When the mean free path of the
gas molecules is much larger than the pore diameter Knudsen
diffusion occurs:

2.3. Procedure for gas permeation

where Tk is the tonuosity factor for Knudsen flow and v is


the gas mean molecular velocity given by:

Only pure gas permeation measurements were run in this


study. The tubular membrane was held in a cylindrical housing with feed and retentate openings at either end of the tube
and a penneate opening on the housing side. At each ends,
rubber gaskets were held tight on the tube side by screw
caps to insure sealing. Before each measurement the retentate exit was dead-ended and primary vacuum was held in the
cylindrical housing for 10 min. Then, gas was introduced in
the cylindrical housing through feed and retentate openings.
This washing operation was made three times before measurements. During an experiment, gas was provided to the
feed inlet and the retentate exit was held in the dead-ended
position. Thus, all of the gas was forced to flow across the
membrane and through the penneate outlet. The penneate
outlet was connected to a bubble flow meter that exhaust in
an extractor hood, so that the penneate pressure was always
atmospheric. The pressure of the feed was adjusted with a
pressure reducer and measured with a pressure gauge. The
pennselectivities were deduced from the ratio of single gas
penneabilities.
The gases used were helium, nitrogen, carbon dioxide,
methane, ethane, propane and butane (purity of, at least,
99.9%) supplied by Air Liquide (France). Volumetric flow
measurements were perfonned at feed pressures ranging
between (1.5 x lOS and 3.5 x lOs Pal (1.5 and 3.5 bar) by
0.5 x lOs Pa (0.5 bar) step. The values of ambient temperature and pressure measured during experiments were used
to conven volumetric flow rate to molecular flow assuming
ideal gas behaviour. For each mean pressure, the permeance
was calculated by dividing the molar flow rate by the membrane flow area and the difference between feed and ambient
(permeate) pressures. The penneability was, then, deduced
by multiplying the penneance by the active layer thickness.

(2)

V=

(:~r2

(3)

where M is the gas molecular weight.


In ceramic membranes with pore diameters between 3 and
30 nm Knudsen diffusion is the "nonnal" mechanism and the
separation is proponional to the inverse square root of the
molecular weights. Nevenheless, since porous membranes
have a pore-size distribution, gas transpon may simultaneously occur by both viscous and Knudsen flow mechanisms
leading to:
(4)

so that, CI and C2 can be deduced from the Fo =f{Pmea,) plot.


Surface flow is always added and can be considered,
in a first approximation, as the flow of a two-dimensional
adsorbed gas, which runs parallel and independent of the gas
flow. The ratio of the flux through the gas phase with respect
to the surface flux can reach values of three or more but, in
general, is smaller than one. Several models have been developed to describe surface flow [22]:
(i) The hydrodynamic model (GiUiland) where the
adsorbed gas is considered as a liquid film which glides
across the surface under the pressure gradient.
(ii) The hopping model where molecules hop over the surface from site to site.
(iii) The random walk hopping model which is the most frequently used. It is based on a two-dimensional Fick's
law and leads to:

Fo = C3D,

(~;) rpl

(5)

where D, is the diffusion coefficient and x, is the fractional


I
surface occupation of the mobile specimen. The term
expresses the increase of internal surface when decreasing
rp, specific interactions are lumped in C3.
Multilayer adsorption occurs when the relative pressure
PIP, (P, is the condensation pressure) is increased so thai a
species is adsorbed in several layers. This is an extension of
the monolayer adsorption and surface diffusion models can
be extended to include the multilayer diffusion [23J. Due to
monolayer and subsequently multilayer diffusion. the permeability will increase until a maximum is reached. This
maximum occurs as capillary condensation slans and a liquid meniscus is formed. After this point, the permeability

"p

3. Transport mechanisms
The transpon of gas through a porous membrane can occur
by several mechanisms [20). When the mean free path of the
gas molecules is much smaller than the pore diameter, viscous
flow occurs and the penneability, Fo , is given by [21]:
(I)

where e is the porosity, q the gas viscosity, Tv the tonuosity factor for the viscous flow, rp the pore radius, R the gas

N. Abidi el al. / Journal of Membrane Science 270 (2006) 101-107

104

decreases due to the liquid transport contribution (the permeability for vapour flow is much higher than for liquid flow).
This qualitative picture was illustrated by Lee and Wang using
six possible modes for a cylindrical capillary in case of multilayer diffusion and capillary condensation [241
If the pore size is decreased (rp < 3 nm), the contribution
of the surface flow increases while the gas phase diffusion
contribution decreases. There will be a gradual change to
solution-diffusion type of transport as present in most of the
non-porous polymer membranes or to mechanisms like those
in microporous membranes where adsorption plays an important role [25,261.

Picture I. SEM surface analysis of the TiOz membrane (the straig hlline is

4. Results and discussion

300 nm long).

4.1 . Original membranes

All the measurements were run at pressure difference lying


from 0.1 x 105 to 0.5 x I Pa (0.1 to 0.5 bar). The plots of
the molar fluxes against the pressure difference were always
observed to be linear for both Ti02 and jI-A1203 membranes.
Thus, the permeabilities were obtained from linear regression
of these data and were constant in the pressure range f>Pequal
to (0.1-0.5) x I Pa. These permeabilities plotted against
the reciprocal of the square root of the molecular weights
of the gases are linear and so the mechanism for the gas
permeation is simple Knudsen flow (Fig. I).
At 20 C, the nitrogen permeability of the unmodified jI-AI20) membrane was constant at 13.4 x 10- 12
mols- I m- I Pa- I, this value is rather smaller than those of
Randon and Paterson [15] and lavaid et al. [19] for commercially available 5 nm jI-alumina membranes (i.e., respectively. 24 x 10- 12 and 41.6x 10- 12 mo l s - 1 m- Ipa- I ).
Such differences are related to the pore size difference and
the tortuosity factor, T, which is linked to the pores distribution and shape factor. For the Ti02 membrane, the nitrogen
permeability at 20 C was 25.5 x 10- 12 mol s-I m- I Pa- I,
thus its value of iT is higher than that of the jI-A1203
membrane. Thi s is confirmed by SEM analysis of the active

as

as

..

'a,

'II! 6
.~

'0

..4

layers were one can see larger voids in the Ti02 membrane
(Picture I) than in the jI-AIz03 membrane (Picture 2). These
voids are not linked together so that, the overall permeability
is increased but the flow remains a Knudsen one (i.e., only
the tortuosity factor, T, decreases).

4.2. Grafted membranes


4.2.1. TiOz membrane
Fig. 2 shows the permeabilities of the different gases as a
function of the mean pressure in lhe membrane. For all gases

the permeability is higher than that of Helium. This result


suggests that, even if some Knudsen flow still remains, other
mechanisms, certainly related to the surface modification,
occur for these gases.
Furthermore, the permeability of butane increases from
4 x 10- 14 to 14 X 10- 14 mol m- I s-I Pa- I when Pmc." is
equal to 0.85 x 105 and 1.1 x 105 Pa, respectively. This fast
increase is characteristic of a multilayer surface diffusion.
Thus, for P mc." <0.85 x 105 Pa monolayer surface diffusion is the main mechanism for butane transport and for
Pmc," > 0.85 x 105 Pa a multilayer surface diffusion occurs.

He(AI, O,)
N2(AI, O,)
x C02(AI,O,)
t,. C3H8(AI,O,)

<> He(TiOJ

o N2(TIO,'

+ C02(TiO,)

o C3H8(TiO~)

Fig. I. Penneabilities to He. N2. C02. C3Hg against Win (M: molec ular
weigh!) for TiOl and Al20 3 bare membranes.

Picture 2. SEM surface analysis of the A1203 membrane (the straight line
is 300 nm long).

N. Abidi el 01. / Journal o/Membrane Science 270 (2(X)6) 101- 107


:I: He
ON2
OCH4
I>C2H6
DC3H8
-C4Hl0
.C02

surface and the gas molecules, but also by the condensabiljty of the gas. Here, only C4H to is to be considered.
(iv) FOp forthe gas transport through the pore necks and at tbe
surface ofTi02 grajns. This mechanism depends greatly
on the solubility of the gas in the fluorinated chain, so
that FOp(COz)>> FOp(alkanes) > FOp (N 2) > FOp(He). On
the other hand, the diffusion step of this mechanism
is improved by the higher mobility of the fluorinated
chains.

t05

Me.n Pressurexl0-5 (Pa)


Fig . 2. Penneabilities to He. N2, C02, CH4 . C2H6 . C]Hs. C4HlO gases for
the Ti02 grafted membrane.

Methane, ethane and propane have approximately the same


permeability than butane at Pme n <0.85 x 105 Paand exhibit
a slight increase until P mean = 2.25 x 105 Pa. So, it can be concluded that a monolayer surface diffusion is also the main
mechanism for these gases. These results suggest that the
Knudsen diffusion pan of the permeability still remains but
decreases greatly due to lower value of (elrk) rp geometric
factor and that this reduction is not balanced by the surface
flow enhancement.
However, the only surface flow is not sufficient to explain
the high C02 permeability and it is necessary to also consider
the gas transport by a solubilisation-diffusion mechanism as
in dense polymer membranes. Effectively, after surface grafting most of the pore the CSFI7C2l4Si= chains can block
necks. In this situation, the gas transport through the pore
necks and at the surface of Ti02 grains is controlled by
a solubilisation-diffusion mechanism as in dense polymer
membranes. Thus, the overall permeability is the sum of various contributions:
(i) FOk for Knudsen diffusion trough the empty voids
which remains connected. Nevertheless, few empty
pores still remain in the membrane so that the tortuosity is drastically increased and the (irk) rp
geometric factor lowered. This contribution depends
on the square root of the molecular weight so that
FOk(He)> FOk(CH4) > FOk(N2) > FOk(C2H6) > FQk(C02)
= FOk(C3HS) > FQk(C4 H 10)
(ii) Fom for a monolayer surface diffusion, which is affected
by specific interactions between the fluorinated surface and the gas molecules, such interactions, are
lumped in the constant C3 of Eq. (5). This contribution will increase when the solubility of the gas
molecules in the fluorinated chain increases that is
to say, when the interactions between the fluorinated
surface and the gas molecules increase. C02 is very
soluble in fluorinated compounds, alkanes are slightly
soluble, Nz and He very slightly soluble 118] so that
FOm(C02) >> Fom(alkanes) > Fom(Nz) > FOm(He).
(iii) FOnlUt for a multilayer surface diffusion, which is
affected by specific interactions between the fluorinated

For each gas the permeability is the sum of these individual


contributions, but some of them are jnsignificant for some
gases.

4.2.2. AlzOj membrane


Butane has too low gas flow to be measured with our
experimental device (minimum permeability detectable for
butane: I x 10- 16 mol m- 1 s- 1 Pa- I) and so we can suggest
that capillary condensation occurs in this case. This is only
possible if the connected pores are smaller than those in the
TiOz membrane.
Fig. 3 shows the permeabilities of the different gases as a
function of the mean pressure in the membrane. Nitrogen,
methane and propane exhibit the same permeabiliy lying
between 0.2 x 10- 14 and 0.28 x 10- 14 mol m- I s - t Pa- I
when Pme.n is equal to 0 .75 x 105 and 2.25 x lOS Pa, respectively. These values are lower than that of helium but are
not in the Knudsen ratio, so we can deduce that the monolayer surface diffusion is smaller in the Al203 grafted membrane than in the TiOz one. This situation can be explained
by a diminution of the number of " partially filled pores".
Such hypothesis also explajns that the permeabilities are
lower in the AI20 3 grafted membrane than in the Ti02
one.
For ethane, due to the typical fast rise of the gas flow, we
must suppose that the surface flow is important and so that
we are just at the beginning of a multilayer surface diffusion.
To explain the high COz permeability it is necessary to
consider, as for Ti02 membrane, not only the monolayer surface diffusion but also a solubilisation-djffusion mechanism
as in dense polymer membranes.

..

":

10
o ClHI
b.C2H6

"e;
(;

S-

'b

..
~
:;;
....
E
..

f(;N2

";'''!

@!i"F@

xH.

1l!:tA#

oc ...

;t( )( )( )( ;t( :I:


)(

;t(;t(;t(;t(;t(

hM~~M 1:lCCC

0
0

Q.

Mean Pressurexl0' (Pa)


Fig. 3. Pemleabilities to He. N2. C0 2. C ~ . C2H6. C J Hs. C" H to gase'\ fo r
the A1 zO] grafted membrane.

N. I&bidi et al. / JoumaJ of Membrane Science 270 (2006) 101-107

106

l:

12
10

> 8

..

a; 8

E4

:.

15

.6"""" .....

._.-

-L.toger ..... ~)t' ..

+u,..- ..... fC,.II'~

14

13

(11]

X,. ....Mt27!
1Ill.........."'11

fj.

selective membranes for separation of C02 from mixtures


with N2 and alkanes. This property is essentially due to the
solubility differences of these different gases in fluorinated
compounds.
Furthermore, the Ti~ grafted membrane exhibits a multilayer diffusion with butane. So that, with the same alkane
chain were butane is more soluble than in our fluorinated
chain, one can expect higher butaneIN2 separation efficiency.

DIff....... [17]

Oflrl6l_1NJOlI

0:.:

O'* __ (lI:)2)

14

12

11

10

References

log(Pennoabilily (mol..".m' .Pa'n


Fig. 4. Pennstlectivities Fo(COz)IFo(N2) against the

C~

permeability,

Fo(COz) compared 10 the literature data.

{I] R.R. Shave (Ed.), Inorganic Membranes: Synthesis, Characteristics

and Applications, Van Nostrand Reinhold, New York.. 1991, pp.


1()"{;3.

4.3. Comparison WiTh previous works

In Fig. 4. the permselectivities FO(C02)IFo(N2) against


fortwo polymers and several grafted membranes reported in the literature.
Compared to polyethylene membrane, our grafted Ti02
membrane exhibits a significantly higher permitivity for the
same permselectivity; on the other hand. the Al203 grafted
membrane has higher permitivity but less permselectivity.
With polydimethyl-siloxane (PDMS), which is one of the
best polymers currently used for solubility-based membrane
separation [27], the AI20J grafted membrane exhibits a significantly lesser permselectivity for about the same selectivity
and permeability. Unlike. the Ti02 grafted membrane has
higher pennselectivity but lesser permeability than PDMS
membrane, so that, these membranes exhibit rather similar
performances.
The comparison of our Ah03 grafted membrane with
others studies also on grafted Ah03 membranes [l4, 16, 17]
shows that these grafted membranes exhibit rather similar
performances. Unlike. ourTi02 grafted membrane has higher
permselectivity and permeability, so that. this membrane is
the best candidate for C021N2 separation.
These results show that the Ti02 grafted membrane is a
good candidate for C02 to N2 separation . Furthermore. this
membrane allows a good separation of C02 from alkanes,
so that it will be more efficient than PDMS for separation of
CO2 from mixtures with N2 and alkanes.
Fo(C~) are given

5. Conclusions
In previous work in the literature, the surface of inorganic
mesoporous membranes were chemically modified using different chains oftrichlorosilanes.ln this work. we have shown
that modifications of the same kind can be achieved using
trimethoxy fluoro silanes. We further demonstrated that the
gas permeation properties of such membranes can be controlled through the nature of the substrate and oligomer
choice. This approach seems ideal for creating solubility

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