7 Design of Advanced Membranes

and Substrates for Water

Purification and Desalination
James Economy, Jinwen Wang, and Chaoyi B a
Center of Advanced Materials for the Purification of Water with Systems,
Department of hlaterials Science and Engineering,
University of Illinois at Urtmna-Champaign, Urbana, I L , U S A

7.1 Overview 96
7.2 Novel Method to Make a Continuous Micro-Mesopore
Membrane with Tailored Surface Chemistry for Use
in Nanofiltration 97
7.3 Deposition of Polyelectrolyte Complex Films under
Pressure and from Organic Solvents 99
7.4 Solvent Resistant Hydrolyzed Polyacrylonitrile
Membranes 100
7.5 Polyimides Membranes for Nanofiltration 101
7.6 Conclusions 104

Abstract
To be useful in a desalination process, membranes must exhibit a number of
characteristics such as high water flux, high salt rejection, mechanical stability,
resistance to fouling, and low cost. A number of polymer materials such as
cellulose acetates, thin film composite (TFC) polyamides, cross-linked poly
(furfuryl alcohol) and sulfonated polyethersulforie have been investigated for
desalination. Of these, cellulose acetates and TFC polyamides have been the
most successful. However, cellulose acetate membranes slowly hydrolyze over
time, are easily attacked by bacteria, and generally are not used above 35°C.
Aromatic polyamides, although without those problems, have low resistance to
fouling, as well as a low chlorine tolerance due to the existence of secondary
amides and electron-rich aromatic rings. The currently available substrates
used for the preparation of TFC membranes include polysulfone and
polyethersulfone. Most of these membrane substrates, however, have relatively
poor chemical and thermal stabilities, and for ultrafiltration (UF) are susceptible
to performance degradation caused by fouling. Therefore, the development of

Savagc ct al. (cds.), Nmotechnoloyy Applications for Clean Wuter, 95-105,

0 2009 William Andrew Inc.
96 DRINK
I N G WATER

more thermally and chemically resistant selective top layers and substrates is
critically rcquired for water purification. We have demonstratcd a new method
to conveniently make nanofiltration membranes with tailored surface chemistry
from U F membrancs.

7.1 Overview
Since the introduction of Loeb-Sourirajan membranes in the early 1960s,
membrane processes have received widespread applications due to their low
energy demand. The Loeb -Sourirajan membranes arc formcd by the immersion
of a casting solution into water. These membranes, sometimes named as phase
separation membranes, are asymmetric porous membranes [ 13. By using these
porous membranes as mechanical supports, John Cadotte deposited a thin
selective layer to make a thin film composite (TFC) membrane [2]. Most
pressure-driven membranes are in these two categories, that is, phase separation
membranes and TFC membranes. According to pore diameters, there are four
categories of pressure-driven membranes-these include microfiltration (MF),
ultrafiltration (UF), nanofiltration ( N F ) , and reverse osmosis (RO) membranes.
Nanofiltratiori, defined by many “as a process between Ultrafiltration (UF)
and Reverse Osmosis (RO),” is a rclatively recent technology, largely developed
over the past decade. Typically, N F membranes have sodium chloride rejections
between 20 and 80 percent and molecular weight cutoffs for dissolved organic
solutes of 200-1000 Dalton. Their low-pressure operation (4-14 bars) provides
increased energy savings with significantly lower installation and operating
costs. A number of polymer materials have been investigated for N F
applications [3,4]. Cellulose acetate (CA) membrane and polyamide TFC
membrane have been the most successful:

1. Cellulose acetate membranes. Cellulose is a linear, rod-like

material that renders nienibranes mechanically robust. Cellulose
acetate was the first high-performance NF/RO membrane material
discovered. Today, CA membranes still maintain a small fraction
of the market because they are easy to make, mechanically tough,
and resistant to degradation by chlorine up to 1 ppm. However,
CA membranes slowly hydrolyze over time and are stable only
in the pH range of 4-6. Salt rejection decreases as temperature
increases and therefore CA membranes are generally not used
above 35°C. In addition, they are easily attacked by bacteria.
2. Polyamide TFC membranes. A more successful, commercially
availablc NF/RO membrane is the TFC aromatic polyamide
membrane. This type of membrane has higher salt rejections
and fluxes than CA membranes. On the other hand, aromatic
polyamides, have several disadvantages including:
a. Low resistance to fouling. Membrane fouling (scale, silt,
biofouling, organic fouling, etc.) is the main came of permeate
7: DESIGN MEMBRANES
OF ADVANCED AND SUBSTRATES, ECONOMY
El' AL. 97

flux decline and loss of water quality. Fouling can decrease

total throughput more than 30 percent, and further increase
capital costs by 15 percent resulting from membrane cleaning.
b. Limited oxidant tolerance due to the existence of secondary
amides and electron-rich aromatic rings [5].Selectivity is rapidly
and permanently lost once exposed to feed water containing
more than a few ppb levels of chlorine or hypochlorite
disinfectants. It creates major problems in designing for
effective pretreatment of chlorine to destroy microorganisms.
c. Chemical and thermal instabilities. The substrate layer of TFC
membranes, usually polysulfone, is attacked by many solvents,
which limits deposition of a permselective, ultrathin membrane
from solvent systems [such as Dimethylformamide (DMF),
and N-methyl-pyrrolidone (NMP)]. Most TFC membranes
can only lie used below 30-50°C because of limitations of
the polysulfone. On the other hand, hot wastewater from
the food, chemical, and petroleum processing industries are
discharged directly and the energy lost is estimated at one to
two percent of the total energy consumption in United States
annually. Developing chemically stable substrates, which
operate at higher temperatures, will result in substantial
energy savings. Therefore, the development of more thermally
and chemically resistant selective top layers and substrates is
critically required for water purification.

In this chapter we describe the development of four new systems that address
these problems: (i) Novel method to make a continuous micro-mesopore
membrane with tailored surface chemistry for use in nanofiltration; (ii) Deposition
of polyelectrolyte complex films under pressure and from organic solvents; (iii)
Solvent resistant hydrolyzed polyacrylonitrile (PAN) membranes; (iv) Polyimides
(PIS) membranes for nanofiltration.

7.2 Novel Method t o Make a Continuous

Micro-Mesopore Membrane with Tailored
Surface Chemistry for Use in Nanofiltration
We have demonstrated a new method to conveniently make N F membranes
with tailored surface chemistry from U F membranes. Because of the large pore
size in the U F membrane it is easier to modify the pore surface chemistry.
After the introduction of functional groups, meso-macropores in U F membranes
were shrunk into micro-mesopores by surface tension forces at the vapor-liquid
interface within the capillary pores during heat treatment. On the other
hand, with use of specific reagents such as Lewis acids, which can act as both
attracting centers and fillings, micro-mesopores will be kept open and lead to
98 D R IN KINNTATER
G

denser concentrations of functional groups on the wall. Due to both interactions,

N F membranes with controlled highly dense pore surfaco functional groups
were prepared directly from U F membranes during heat treatment. Cationic
arid anionic exchange N F PAN mcmbranes were easily prepared from UF
membranes by the aforementioned method in the presence of ZnC1,. By the
reaction between riitrile groups and NaOH or 3-(dimethy1arnino)propyl arnine,
negative or positive functional groups were introduced into the meso-macropores
of PAN U F membranes. These meso-macropores were then reduced into the
range of micro-mesopores by taking advantage of surface tension forces within
the capillary pores during heat treatment in the presence of ZnC1,. A typical
procedure of this method is illustrated in Fig. 7.1 [6,7].
This method could be extended to other polymer systems such as polystyrene
or poly (styrene-co-acrylonitrile). In these systems, UF membranes could be
precipitated from non-solvents besides water by the phase separation technique.
These non-solvents can cause functional groups of the polymers to migrate
onto the meso-macro continuous pore surface as in the case of water and nitrile
groups of PAN. Also, the large pore size in the U F membrane allows easier
modification of the pore surface chemistry. With the help of templates that
interact with the functional groups on the meso-macro pore surface, as in the

Phase Separation Technique

w
CN CN CN CN
Water as a Non-solvent

Figure 7.1 Preparation of cationic exchange polyacrylonitrile nanofiltration membranes.

DMF: Dimethylformamide; NF: Nanofiltration; PAN: polyacrylonitrile; PVP:
Polyvinylpyrrolidone; UF: Ultrafiltration.
7: D E 5 l C N OF MEMERANES
ADVANCED AND SUBSTRATES, ECON(IMY
ET AL. 99

case of ZnC1, with nitrile groups, continuous rriicropores with highly dense
pore surface functional groups could be formed during the heating and
evaporation of the solvent of the template, for example, water and ZnCl,, once
the surface tension force excceds the modulus of the polymers.

7.3 Deposition of Polyelectrolyte Complex Films

under Pressure and from Organic Solvents
The alternating physisorption of oppositely charged polyelectroytes on
porous supports is a relatively new technique that provides a simple way to
create ultrathin polyelectrolyte multilayers (PEM) [8,9]. There are many
advantages of PEM films for N F membranes [lo]. This “layer-by-layer” or
“electrostatic self-assembly” (ESA) method affords control over thickness,
charge density, and composition of the selective skin layer in NF membranes.
Moreover, a wide range of polyelectrolytes is available to form PEM films.
Therefore, flux, selectivity, and possibly fouling rates of N F membranes could
be tailored by judicious selection of constituent polyelectrolytes. Despite the
versatility of PEM films, studies for N F application thus far primarily focused
on poly (styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH) [ll],
PSS/Chitosan [ 121,PSS/poly(diallyldimethylammoniumchloride)(PDADMAC)
[12], hyaluronic acid (HA)/Chitosan [12], and poly (vinyl amine)/poly (vinyl
sulfate) [13]. Bruening et al. [11,12] reported that the PSS/PDADMAC films
showed limited salt rejection of up to 40 percent for a feed concentration of
0.01M NaC1. The PEM membranes using Chitosan as polycation showed even
lower solute rejections probably because Chitosan has lower charge density
than PDADMAC and thus fewer ionic cross-links could be formed in the films.
Although Tieke et al. [13] achieved 84 percent rejection for 0.01M NaC1, the
flux was relatively low (approximately 0.013 m’ m day at 5 bars) since he
deposited 60-bilayer poly (vinyl amine)/poly (vinyl sulfate) films on PAN/
poly(ethy1ene terephthalate (PET) supporting membranes. In addition, all
these PEM films were prcpared in water. The formation of PEM films in
organic solvents for N F application has received much less attention.
We have demonstrated the preparation of PEM films having a high salt
rejection (up to 80 percent) with only several bilayers (below five bilayers) of
sulfonated poly (ether ether ketone) (sPEEK) and branched polyethylenimine
(PEI). It was found that the salt rejection was increased two or three times by
pressing water through the membrane during the film deposition as shown in
Fig. 7.2. One possible explanation of this effect might be the survival of the
fittest. When the film was formed, there were some weaker regions in every
single layer. These regions could not withstand the pressure applied. Whereas
in the next deposition cycle, stronger layers might form on these damaged
regions. Therefore, membranes suitablc for the corresponding pressure survived.
The final membrane is more compact than those prepared without pressure.
We also deposited PEM consisting of sPEEK and PEI from organic solvents,
100 DRINKING
WATER

2 - 80

1.6
-
ZI
- 60
rn
1.2

- 20
0.4

0 0 0
0 5 10 15 20 25 30
P r e s s u r e (bars)

Figure 7.2 Performance of polyelectrolyte multilayers prepared at different pressures.

for example, methanol. The salt rejection can be up to 80 percent for 2g/L
NaCl solution. This PEM is expected to be more stable in aqueous environments
since the sPEEK we used is insoluble in water [14].

7.4 Solvent Resistant Hydrolyzed

Polyacrylonitrile Membranes
Although polymeric membranes are primarily used with aqueous systems,
nunierous separation technologies for solutions polluted by organic solvents
could be optimized by the application of solvent resistant polymeric membranes.
Thc rapidly expanding interest in the separation of low niolecular weight
substances from nonaqueous solutions by membrane technologies also demands
solvent-stable membranes. It should be rioted that the substrate layer of TFC
membranes, usually polysulfone, is attacked by many solvents. This limits
deposition of a permselective, ultrathin membrane from solvent systems (such
as DMF, NMP) and limits the developmcnt of new RO/NF membranes.
Several approaches have been reported to develop PAN membranes with
improved chemical stability not only to common solvents but also to polar
aprotic solvcnts such as DMF, N,N-dimethylacetamide (DMAc), and NMP.
Thcse approaches used systems such as PAN/metal ethoxides [15], PAN/
sodiuni hydroxide and heating [16,17], poly(acrylonitri1e-co-vinylacetate)/
hydroxylamine/sodium carbonate/cyanuric chloride [ 181,and poly( acrylonitrile-
co-glycidylmethacrylate) or poly(acrylonitri1e-co-viriylbenzylchloride)/
multifunctional amines [19-21] to form cross-linked networks. However, we
have found that PAN membranes become resistant to all solvents just after
treatment with NaOH. By this simple method we can develop N F / U F
7: DESIGN M E ~ I B H A NAND
OF ADVANCED ES SUBSTRATEb, ECONOMY
C I AL. 101

membranes or substrates with excellent solvent resistance for TFC RO/NF

membranes. The degree of swelling of hydrolyzed PAN membranes in DMF is
shown in Fig. 7.3, where (a) is the degree of swelling of membranes with the
polyester support. In general, the swelling ratio in length decreases with the
hydrolysis. As expected, the degree of swelling in length is very small, even
zero, due to the limitation from the polyester support. In the direction of
thickness, the membrane swells and the swell ratio is almost stable between 21
and 33 hours of hydrolysis. Interestedly, after about 40 hours of hydrolysis,
there are negative swelling ratios, that is, membranes shrink. Figure 7.3(b)
shows the degree of swelling of membranes without the polyester support.
Again, the swelling ratio in length decreases with the hydrolysis. In the direction
of thickness, the swell ratio is close to a constant for membranes hydrolyzed
between 24 and 33 hours. After 40 hours of hydrolysis, membranes shrink in
both directions. The phenomena discussed earlier indicate that the cross-
linking degree increases as the hydrolysis progresses [22].

7.5 Polyimides Membranes for Nanofiltration

Currently, it is still a challenge to develop chemically and thermally stable
polymeric membranes that can withstand harsh environments such as pH
extremes, Cl,, organic solvents, and very low or high temperatures, and so on,
while maintaining the separation ability of the commercial TFC membranes [23].
Some high-performance polymers such as PIS, PEI, polybenzimidazole (PBI) ,
and so on have been considered for developing a new generation of membranes
for water purification and desalination. For example, PBI has been fabricated
into hollow-fiber nanofiltration membranes for separation of multivalent ions,
chromate, and cephalexin [24-261.

(b) 80

60 --
A

8
1
40 .-
0
.-
2- 20-
-
a,
3 0-
cn
10 0
-20 --
10 20 30 40 0
40- -40
Hydrolyzed Time with 1M NaOH (Hours) Hydrolyzed Time with 1M NaOH (Hours)

Figure 7.3 Effects of hydrolysis time on the length swell ( 0 ) and thickness swell (M)
of polyacrylonitrile ultrafltration membranes in DMF for 72 hours with (a) and without
(b) nonwoven polyester support.
102 DRINKING
WATER

Due to their unique properties, PIS have hecn developed into membrane for
separation of gases, vapors, and liquids [27]. Polyimide membranes exhibit
excellent resistance to almost all chemical agents. Their thermal resistance
allows separations to be performed for a long time at elevated temperatures.
Specifically, poly(pyromel1itic dianhydride-co-4,4'-oxydianiline)(PhIDA/ODA
PI) has a vcry high glass transition temperature of approximately 400°Carid
excellent resistance to most nonoxidizing acids at room temperature and
almost all organic solvents [as].However, because the PMDA/ODA PI is both
insoluble and infusible, any products, including membranes, can only be
processed from its precursor, polyamic acid (PAA), which requires an additional
step to transform the PAA into PI by either thermal or chemical treatments.
So far, studies have focused on its fabrication into asymmetric membranes for
separation of gases and organics [29-33]. A dense symmetric membrane has
also been prepared from PAA solution via solvent evaporation followed by
chemical imidization. The fully imidized membrane showed very high salt
rejection but low water flux [34].
Neutralization of the acid groups prior to imidization would improve the
hydrolytic stability and physical properties of the PAA. The neutralizers can
be tertiary aniines [35] or metal ions [36,37].However, the PAA amine salt
polymers are soluble in water and thus may not be suitable for developing
asymmetric membranes by phase inversion method. On the other hand, the
metal ions, such its Zn", Co2+,Ni2', Cu2+,can strongly coordinate with the
carboxylic groups, which would increase the PAA's mechanical properties and
the solution viscosity. In our research, zinc chloride was added to the PAA/
NMP solution to prepare a casting solution for developing a PI membrane. It
has been shown that by adding the ZnCl,, viscosity of the casting solution
increased, probably because of the complex formation between PAA and Zn2+
as shown in Fig. 7.4.
The increase of viscosity of the casting solution had strong influence on
membrane morphology and permeability. Our preliminary data showcd that
with ZnC1, additive, macrovoids in the membranes were depressed and water
permeability was improved. The resultant membranes developed under
optimized conditions can he used for a substrate to prepare thermally stable
composite membranes for NF/RO application [38].
A unique feature of PIS is their chemical reaction with amines, which results
in the opening of some of the imide functions to form ortho-diamide functions.
This reaction can be used to introduce functional groups onto the P I membrane
surface by choosing suitable amines. In particular, by reacting with
multifunctional amines (di- or higher functional), PIS can be cross-linked so
that the P I membranes would show improved separation efficiency and solvent
resistance. For example, W. Albrecht et al. studied the surface furictionalization
of poly(ether imide) membranes by di- arid multivalent arnines. It was shown
that when using high molecular weight PEI as modifying agent, the poly(ether
imide) membranes became insoluble even in the polar aprotic solvents, such as
DMAc, and high contents of amine groups were detected [39]. These amine
7: DESIGNOF ADVANCED A N D SUBSTRATES,
MEMBRANES E C O N O ~ETI YAL. 103

-HN

0 0-
Figure 7.4 Interaction between Zn2+ and polyamic acid.

groups made the membrane more hydrophilic and positively charged as shown
by contact angle and streaming potential studies [39,40].
Lenzirig P84 is a soluble co-polyimide of 3, 3', 4, 4'-benzophenone
tetracarboxylic dianhydride with 80 percent toluenediisocynate and 20 percent
methylphenylenediisocyanate (BTDA-TDI/MDI) with a Tg of 315°C. Chemical
modification of the P84 membranes has been performed by treatment with
diamines for use either for pervaporation dehydration of isopropariol [41] or
for nanofiltration in polar aprotic solvents, such as DMF, NMP [42]. The
diamine-modified P84 membranes were good for separation of organics because
of the improved organic resistance. For electrolyte removal, however, membrane
charge would play an important role because of the Donnan exclusion effect.
For example, the commercial membranes are generally negatively charged [43]
and multivalent anions, like sulfate and phosphatc, are rejected more
effectively [44].
In our work [45], by modifying the P84 membranes using PEI, positively
charged nanofiltratiori membranes were obtained, which showed 50.9 k 5.1 percent
rejection to 2.0 g/L NaCl solution with a flux of 1.2 f 0.1 m3 m day when
tested at 13.8 bar and room temperature. After modification, the membranes
were cross-linked by the PEI and showed good resistance to organic solvents.
Development of the PEI-modified P84 membranes not only provides a
solvent resistant and positively charged NF membrane for removal of heavy
metal ions (> 98 percent rejection t o Zn2+,CiiZf,or Fe"+) but also affords the
design of a completely new type of anti-fouling membrane consisting of an
erasable polyelectrolyte protective coating. This area appears to be of great
commercial value.

7.6 Conclusions
The functionalities on the pore wall surface are very important to facilitate
the flow of water and inhibit transport of salt for N F applications. We developed
several ways to design and prepare a microporous polymeric membrane with a
high density of functional groups.
104 WATER
DRINKING

One approach we considered involved the use of surface tension forces within
the capillary pores during heat treatment in the presence of Lewis acids (e.g.,
ZnC1,). Asymmetric PAN N F membranes with tailored surface chemistry were
conveniently prepared from PAN UF membranes by this new technique. In
addition, the solvent resistance of hydrolyzed PAN membranes was studied.
The other approach we developed involved the use of pressure during the
alternating physisorption of oppositely charged polyelectrolytes on porous
supports. For example, new PEMs as selective skins in composite membranes
for N F were prepared by alternating layer-by-layer deposition of sulfonated
sPEEK and PEI. During this electrostatic stlf-assembly deposition, it was
demonstrated that thc use of pressure could increase the salt rejection of the
PEMs by one to two times.
Finally, PMDA/ODA P I membrane was developed from its precursor, PAA,
using ZnC1, as additive. It was found that ZnC1, could improve membrane’s
hydrolytic stability, mechanical strength, and permeability. In addition, NF
membranes were developed by chemical modification of P84 copolyimide using
PEI. This membrane showed good desalination performance and solvent
stability.

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