Chemical Engineering Science 61 (2006) 6454 – 6467

www.elsevier.com/locate/ces

Removal of chlorinated volatile organic contaminants from water by

pervaporation using a novel polyurethane urea–poly (methyl methacrylate)
interpenetrating network membrane
Swatilekha Das, A.K. Banthia, Basudam Adhikari ∗
Materials Science Centre, Indian Institute of Technology, Kharagpur 721302, India

Received 3 April 2006; received in revised form 26 May 2006; accepted 9 June 2006
Available online 14 June 2006

Abstract
Polymer membranes are potentially selective for separation of organic compounds from a mixture by pervaporation. A novel crosslinked hy-
droxyterminated polybutadiene based (HTPB) polyurethane urea (PUU)–poly (methyl methacrylate) (PMMA) interpenetrating network (IPN)
membrane has been developed for the selective removal of chlorinated volatile organic compounds (VOCs) such as 1, 1, 2, 2-tetrachloroethane,
chloroform, carbon tetrachloride, trichloroethylene present in water in very low concentration by pervaporation. IPNs of different PMMA
content and also different crosslink density were used. Since the selective permeation and diffusion of the VOCs through the membrane
are dependent on their interaction with the membrane material, their sorption and diffusion behaviors through the membrane were also in-
vestigated by swelling the membrane in pure VOCs. The sorption and diffusion behaviors were explained with the help of their solubility
parameter data and calculated interaction parameter data of the membrane polymers with the VOCs. From the swelling kinetics data, diffu-
sion coefficients of the VOCs through the membrane were calculated. Diffusion coefficients increased with the increase in crosslink density
and PMMA content in the membrane. In pervaporation experiment, concentrations of chlorinated organic compounds in feed were varied
from 100 ppm (0.01%) to 1000 ppm (0.1%). All the three IPN membranes showed excellent separation performances of the chlorinated VOCs
from water. One IPN containing 26% PMMA (PUU–PMMA-3) produced 88.7% trichloroethylene in permeate, 0.2 kg/m2 h trichloroethy-
lene flux and a separation factor of 7842 from a 0.1% aqueous feed after a pervaporation run of 3 h at 30 ◦ C. All the three IPN mem-
branes of different compositions have shown the separation performances, viz., flux and separation factor for all the VOCs in the order
1, 1, 2, 2-tetrachloroethane < carbon tetrachloride < chloroform < trichloroethylene.
䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Polymers; Membranes; Separations; Pervaporation; Selectivity; Diffusion

1. Introduction organics from their aqueous solutions at very low concentra-

tion (< 1000 ppm), pervaporation offers excellent possibilities
Chlorinated volatile organic compounds (VOCs) such as to compete with alternative techniques like adsorption onto
chloroethanes, chloromethanes, chloroethylenes, carbon tetra- activated carbon, air stripping and biological treatment (Blume
chloride, etc. frequently contaminate ground water and soil. et al., 1990; Feng et al., 1994; Yang et al., 1995; Lau et al.,
These VOCs, released as wastewater from various industries, 1997). Being slow, biological treatment is not always a very
are potential carcinogens and are a threat to living beings. effective process. Although air stripping and adsorption are
So the industrial wastewater needs to be treated to remove established processes but these suffer from the disadvantage of
VOCs prior to discharge (Long, 1995; Caetano et al., 1995; pollutant transfer to the second phase. The expensive air strip-
Osada and Nakagawa, 1992). For specific removal of volatile ping process is applied to compounds having significant higher
partition coefficient to air over water. Activated carbon adsorp-
∗ Corresponding author. Tel.: +91 3222 283966; fax: +91 3222 255303. tion is not effective economically as the spent carbon has to be
E-mail address: ba@matsc.iitkgp.ernet.in (B. Adhikari). regenerated time to time or disposed off and disposing of spent

0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.06.014
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6455

carbon should be done in environmentally accepted manner. SBR and nitrile rubber for separation of both chlorinated and
The attractiveness of pervaporation, on the other hand, lies in non-chlorinated aliphatic as well as aromatic hydrocarbons
the fact that the polluting compounds are selectively removed for a wide range of their concentrations in feed. It appears
from the feed in almost pure form. from the chemical nature of chlorinated VOCs that a mem-
The removal of chlorinated VOCs using various permselec- brane with both flexible non-polar and rigid polar organic do-
tive membranes by pervaporation, for example, silicone rubber mains would be more suitable for their separation. Segmented
(Gales et al., 2000), polyether block polyamide (PEBA) (Meckl polyurethanes with elastomeric soft domain and rigid urethane
and Lichtenthaler, 1996), crosslinked poly (acrylate-co-acrylic as well as urea domain can be projected as an ideal material of
acid) (Hoshi et al., 1998, 1999) were investigated. Silica such type. Although segmented polyurethane membranes have
filled silicone rubber, PEBA and crosslinked poly (acrylate- been used for separation of aromatic compounds and other
co-acrylic acid) membranes were employed to separate ethyl VOCs but there are no reports of separation of chlorinated
butanoate, methanol, acetone, chloroform, trichloroethylene VOCs using hydroxy terminated polybutadiene (HTPB)-based
(TCE), trichloroethane, tetrachloroethylene and carbon tetra- polyurethane urea (PUU)–polymethyl methacrylate (PMMA)
chloride from water (Gales et al., 2002; Sohn et al., 2000; interpenetrating network (IPN) membranes.
Meckl and Lichtenthaler, 1996; Hoshi et al., 1998, 1999). The main objective of this investigation is the development
Baker et al. (1997) used silicone rubber and EPDM mem- of novel crosslinked HTPB-based PUU–PMMA IPN mem-
branes in spiral-wound modules to separate toluene/water and branes for the selective removal of chlorinated VOCs such as
TCE water mixtures. They got maximum toluene fluxes of 1, 1, 2, 2-tetrachloroethane, chloroform, carbon tetrachloride,
0.049 and 0.043 kg/m2 h by using EPDM and silicone rubber TCE present in water in very low concentration by pervapora-
membrane, respectively, from a feed concentration of 140 ppm tion. Crosslinked IPNs of PUU–PMMA of different composi-
toluene in water, and obtained a maximum TCE flux of about tions were prepared and used for separation of these VOCs by
0.006 kg/m2 h from a 100 ppm feed using silicone rubber pervaporation.
spiral wound module. Lau et al. (1997) separated chloroform The sorption and diffusion behaviors of these IPN mem-
from water using novel silicone rubber membrane prepared branes in pure VOCs are also reported. The sorption and dif-
by crosslinking silylstyrene oligomer and reported a chloro- fusion behaviors were interpreted by solubility parameter and
form flux of 0.021 kg/m2 h and separation factor of 807 from interaction parameter data of the membrane polymers with the
a 500 ppm chloroform in water. Ji et al. (1994) separated VOCs. Diffusion coefficients of the VOCs through the mem-
trichloroethane from water by using polydimethylsiloxane brane were also calculated.
(PDMS) and PEBA membrane and got 0.013 (from 146 ppm
feed) and 0.011 kg/m2 h (from 300 ppm feed) fluxes and sepa-
ration factors of 2040 and 450 using PDMS and PEBA mem- 2. Experimental
branes, respectively. Nijhuis et al. (1991) and Dutta and Sikdar
(1999) got TCE fluxes of 0.018 (from 250 ppm feed) and 2.1. Materials
0.013 kg/m2 h (from 100 ppm feed) using PDMS and styrene
butadiene membrane, respectively. Brun et al. (1985) separated HTPB (functionality 2.4 (mixture of bi and tri functional
chloroform from water (from feed concentration 250 ppm) and molecules), hydroxyl value 43.2 mg KOH/g) of number average
got separation factors of 21,000 and 27,000 and chloroform molecular weight 2580 was received from VSSC, India; 2, 4
fluxes of 0.09 and0.047 kg/m2 h using acrylonitrile butadiene toluene diisocyanate (TDI, E. Merck); catalyst dibutyltindi-
copolymer and styrene butadiene membranes, respectively. laurate (DBTDL, Fluka AG); 4, 4 -diaminodiphenylether
Enneking et al. (1993) reported the permeability of benzene commonly known as oxydianiline (ODA, Fluka AG); methyl
and toluene by pervaporation using segmented polyurethane methacrylate (MMA, Burgoyne Barbidges & Co.); ethylene
membranes. Ponangi and Pintauro (1996) investigated vapor- glycol dimethacrylate (EGDMA, E. Merck); azobisisobuty-
phase separation of different VOCs, viz., trichloroethylene, ronitrile (AIBN, E. Merck); tetrahydrofuran (THF, E. Merck);
TCE, carbon tetrachloride, benzene, toluene, p-xylene, hexane, 1, 1, 2, 2-tetrachloroethane (E. Merck); chloroform (E. Merck);
and benzene/toluene/xylene from nitrogen using polyurethane carbon tetrachloride (E. Merck) and TCE (E. Merck) were
membranes having polyether or polyester soft segments. Using used as received.
polyurethane/polyadipate and polyimide/polyadipate copoly-
mer membranes Ho et al. (1996) also separated aromatic and 2.2. Synthesis of polyurethane prepolymer
aliphatic compounds by pervaporation, where polyurethane or
polyimide hard segment provided thermal stability and solvent Prepolyurethane was prepared by reacting HTPB (2.48 g)
resistance, while the polyadipate soft segment governed se- with TDI in dry THF (50 ml) in presence of DBTDL cata-
lectivity and flux. In a recent review, Peng et al. (2003) have lyst (0.01 wt% based on HTPB), using varying mole ratios of
nicely discussed the separations of a wide range of different NCO:OH such as 1.2:1, 1.5:1 and 2.0:1. The polyurethane for-
VOCs from their aqueous solutions of different feed concentra- mation reaction was continued at 30 ◦ C for 60 min with care-
tions. From this review it is seen that people have made major ful and controlled stirring. At the end of this period a viscous
use of both homo and copoloymers of PDMS, PEBA, PVDF solution of prepolyurethane in THF was obtained. The pre-
membranes compared to other membranes, viz., PE, EPDM, polyurethane synthesis reaction is shown in Scheme 1.
6456 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

OCN O NCO
O

CH3 NH C O O C HN CH3

O NCO
HO OH +
OCN O C HN CH3
Bifucntional HTPB DBTDL OCN O
+ CH3 NCO
OH NH C O OH
CH3
HO OH
Trifucntional HTPB
CH3
NCO

+
NH

C O

O
OCN O O NCO

NH C O O C HN CH3
CH3

NCO terminated prepolyurethane

Scheme 1. Synthesis of prepolyurethane.

2.3. Synthesis of PUU–PMMA interpenetrating polymer 65 ◦ C), being highly volatile, slowly evaporate with simulta-
networks neous crosslinking of PUU. Then the membrane was heated
in an oven at 80 ◦ C for 5 h for thermal curing and in this
The required quantities of prepolyurethane (1.0 g), MMA conditions remaining MMA and EGDMA, if any, underwent
monomer (10–30 wt% of prepolyurethane), EGDMA (cross- thermal polymerization and crosslinking. In order to know
linking agent) (1 wt% based on the MMA used), ODA the composition of this IPN membrane the percent conver-
(polyurethane chain extender) (10 mol% based on HTPB), sion of MMA-EGDMA-AIBN to crosslinked PMMA within
AIBN initiator (0.5% based on MMA used) were placed in a the PUU–PMMA IPN was obtained by subtracting the to-
round bottom flask fitted with a magnetic stirrer. The content tal mass of HTPB, TDI and ODA used for the synthesis of
was stirred for 30 min at 60 ◦ C to form a uniform mixture PUU from the total mass of dry and cured PUU–PMMA IPN
during which time the prepolyurethane reacted with diamine membrane.
to form PUU with simultaneous formation of crosslinked
PMMA from MMA, EGDMA and AIBN within the PUU
matrix. This entire reaction was carried out under dry oxy- 2.5. FTIR analysis of membrane
gen free nitrogen blanket. The end product was obtained as
a viscous mass of PUU–PMMA IPN in THF (Schemes 2 A FTIR spectrophotometer (Thermo Nicolet, Nexus 870, us-
and 3). ing a zinc selenide crystal and OMNIC software) was used for
characterization of the prepared IPN membrane.
2.4. Membrane casting
2.6. Tensile property measurement
The solution of PUU–PMMA IPN in THF was subjected
to vacuum to remove trapped nitrogen gas and excess solvent Tensile strength and elongation at break of PUU–PMMA
present in it. Then the highly viscous mass of PUU–PMMA IPN membranes were measured using Hounsfield H10KS
in THF was cast on a flat-base glass petridish and allowed Universal Testing Machine (UTM). According to ASTM
overnight for moisture curing at room temperature (30 ◦ C) and specifications, rectangular strips of 6 mm width were cut
laboratory humid condition (72% RH). During this period of out from the polymer membrane. The strips were well
exposure in ambient conditions of temperature and humid- gripped using thick paper during the measurement of tensile
ity MMA (b.p.: 92 ◦ C), EGDMA (b.p.: 89 ◦ C) and THF (b.p.: strength.
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6457

O O
OCN NCO
HN NH C NH O NH C

NCO n

+
OCN NCO
O O
NCO terminated prepolyurethane C O NH
NH NH C

O C
+
NH
O O

HN NH C NH O NH C
m
H2N O NH2

Polyurethane urea

Scheme 2. Synthesis of polyurethane urea (PUU).

O O
HN NH C NH O NH C
m
+
O O
+ MMA + EGDMA
NH C NH O NH C
O C

NH O O

HN NH C NH O NH C
n

Polyurethane urea

AIBN

IPN of polyurethane urea and PMMA

Scheme 3. Synthesis of PUU and PMMA IPN polymer.

2.7. Pervaporation setup tioned for 24 h by immersing in the feed solution prior to perva-
poration run to attain equilibrium swelling in the feed solution.
Pervaporation of chlorinated VOC–water mixture was car- The feed temperature was maintained by circulating hot water
ried out in a pervaporation cell. It was assembled from two through the cell jacket. For all measurements, the downstream
cylindrical half-cells made of stainless steel fastened together pressure was maintained at 666.61 Pa (5 mmHg) by applying
by nuts and bolts. The membrane was supported on a sintered vacuum. The permeate vapor was collected in a glass condenser
(perforated) stainless steel plate placed at the joint of two cells. suspended inside a cryogenic trap maintained at −40 ◦ C. The
The membrane area was 2.9 × 10−3 m2 and the volume of the experiment was run for 3 h with no change in flux with time.
feed given in a batch was 300 ml. The membrane was condi- All the pervaporation runs were repeated twice for each of the
6458 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

feed compositions studied with 0.5–1.0% variations in flux data Volume fraction of polymer in swollen state was then calcu-
and the average results are reported. lated as
1
2.8. Flux Vp = , (5)
Q
where Q is the degree of volume swelling at equilibrium and
The flux can be calculated from the weight of the permeate
Vp is the volume fraction of polymer in swollen state.
collected after pervaporation run from the following equation:
In the swelling kinetics study, circular samples of diameter
Flux, J = Q/(At), (1) 1.5 cm of definite thickness were used for sorption of pure
VOCs. After taking the dry weight the samples were placed in
where Q is the quantity of permeates collected in time t and A
four different chlorinated VOCs kept in weighing bottle with
is effective area of membrane.
standard joint stopper at 30 ◦ C. Specimens were taken out at
regular intervals of time and liquid adhered at the surface was
2.9. Separation selectivity wiped off, weighed immediately and replaced in the VOCs.
This procedure was continued till equilibrium. The sorption
The concentration of VOC in permeate was estimated by UV of the VOCs (Mt ) at time t into the polymer is expressed by
absorption measurement. The separation selectivity of perme- (Mathew et al., 1995)
ation is expressed as
mc /mr

p(VOC/water) = (CVOC
2 2
/Cwater 1
)/(CVOC 1
/Cwater ), (2) Mt = × 100, (6)
mi
where C represents concentration term and superscripts 1 and where mc is the mass of VOC taken up at time t, mr is the
2 represent feed and permeate, respectively. molecular mass of VOC and mi is the dry weight of membrane
sample. At equilibrium swelling Mt was considered as M∝ .
2.10. Swelling study In order to realize the mechanism of sorption, the values of
Mt and M∝ were substituted in the following general equation
Small pieces of weighed PUU–PMMA IPN membranes (Tetsuya et al., 1995):
were kept immersed in pure chlorinated VOCs separately at Mt
room temperature (30 ◦ C). Since the membranes were found = kt n , (7)
M∞
to achieve equilibrium swelling within 48 h, after 48 h of im-
mersion the membranes were taken out and their weights were where k is a constant, which depends on the structural charac-
measured immediately after wiping out the surface liquid by teristics of polymer and its interaction with VOCs. The value
soft tissue paper. The degree of swelling was calculated as of exponent n governs the mode of transport, when n = 0.5,
follows: diffusion obeys Fick’s law, when n = 1, the diffusion is said
to be non-Fickian. In the present system, the values of n were
Ww − Wd
Degree of swelling = , (3) obtained from the linear plot of log (Mt /M∝ ) versus log t.
Wd The transport of penetrant molecules (VOCs) through poly-
where Wd is the initial dry weight of membrane and Ww is mer membranes is also quantified by other terms such as diffu-
the weight of the membrane after 48 h swelling (at equilibrium sion coefficient (D) and sorption coefficient (S). The diffusion
sorption). coefficient (Eq. (8)) (Ajithkumar et al., 2000), which is a mea-
The solubility parameter () is square root of cohesive energy sure of the ability of the penetrant molecules to move through
density for simple liquids, which is readily calculated from the the polymer matrix, was obtained from the slope of a plot of
molar enthalpy of vaporization and the liquid density. For poly- Mt versus t 1/2 (Eq. (9)). The sorption coefficient S, which gives
mers, it is dependent on the atomic constitution of polymers an idea about the equilibrium sorption, was calculated from
and can be determined experimentally by measuring the sorp- Eq. (10) (Erred, 1986)
tion of a series of liquids of known  and observing which of  
 hM t 2
the liquid swells the polymer to a greater extent. Since for poly- D= , (8)
mers of known structure it can be easily calculated by the use t 4M∞
of molar-attraction constants E (Hoy, 1970) following Eq. (4) 
Mt 4 Dt
(Billmeyer, 1994), the  values of the PUU–PMMA IPN mem- = 1/2 , (9)
M∞  h2
branes were calculated using the molar attraction constants for
contribution of different groups available in standard literature m∞
S= , (10)
(Burrel, 1975), mp


 E where h is the thickness of the sample, m∝ and mp represent the
= , (4) mass of VOC taken up at equilibrium and the initial mass of the
M
membrane, respectively. The permeability coefficient P, which
where  is the density, M is the molecular weight of repeat unit
gives a combined effect of both D and S was also calculated as
of polymer and E is the sum total of molar attraction constants
of different groups present in the polymer repeat unit. P = D × S. (11)
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6459

The average molecular weight of the polymer chain segments selectively permeated component (Semenova et al., 1997). The
between two crosslinks (Mc ), which is related to the crosslink separation performance of VOCs depends upon the distribution
density, was measured from the well-known Flory–Rehner of soft/hard segments as well as that of hydrophobic and hy-
equation (Flory and Rehner, 1943), drophilic domains. Based on this concept we dispersed some
1/3
polar domains (formed by urea and urethane groups of PUU
−V1 (Vp − 21 Vp ) and PMMA) as active centers in the non-polar matrix (HTPB)
Mc = , (12)
ln(1 − Vp ) + Vp + 12 Vp2 to increase the permselectivity of the membrane towards chlori-
nated VOCs. The permselectivity to a specific component by a
where Vp is the volume fraction of the polymer in the swollen membrane depends on factors like chemical nature of permeants
membrane, V1 is the molar volume of solvent (VOC),  is the and membrane, steric interaction, available free volume within
density of the polymer network, 12 is the polymer solvent the membrane matrix and membrane stability in the environ-
interaction parameter, which is calculated as (Xiao et al., 1990) ment of feed to be separated (Okumus et al., 2003). Therefore,
B + V1 (p − s )2 the main purpose behind the development of IPN membrane is
12 = , (13) the incorporation of polar domains (urea and urethane groups
RT of PUU and PMMA) dispersed in non-polar matrix (HTPB) for
where p and s are the solubility parameters of the polymer the separation of chlorinated hydrocarbons. Urethane groups
and the solvent (VOC), respectively, and B, which is the lattice formed by the reaction of isocyanate groups of TDI and hy-
constant is taken as 0.34. droxyl groups of HTPB and urea groups formed by the reaction
The average degree of crosslinking () and the total number of isocyanate groups and amine groups of the chain extender
of chain segments between two crosslinks per unit volume (N) (ODA) form the hard segment in the membrane. HTPB con-
were also calculated for all the samples using the following tributes to the soft segment. In order to vary the hard segment
equations (Saikumar and Rajadurai, 1987): concentration, the NCO/OH ratio was varied in all the mem-
branes prepared. Moreover, VOC permeation rate is expected
1
= , (14) to vary with crosslink density of PUU–PMMA membrane in
2Mc a diffusion-controlled pervaporation process. So three types of
 membranes were prepared by changing the amounts of PMMA
N= , (15)
Mc and within each type hard segment concentration was varied by
varying the NCO/OH ratio. The membrane designations, com-
where  is the density of the polymer network.
positions and characteristics are shown in Table 1.
3. Results and discussion
3.2. FTIR analysis of membrane
3.1. Synthesis of membrane
The PUU membrane was prepared from HTPB, TDI and
IPNs are the materials containing two or more polymers in ODA. The PUU was further interpenetrated with PMMA by
a network form in which at least one of the polymers is syn- polymerizing MMA in the PUU matrix. That this membrane
thesized or crosslinked in the immediate presence of the other. contains urethane, urea linkages and PMMA segments was as-
They differ in their swelling behavior from other crosslinked certained by FTIR spectroscopic analysis. In FTIR spectra of
polymers as they consist of two components, one rubbery and the three different PUU–PMMA membranes (Fig. 1) a strong
the other glassy. Selective sorption from a feed mixture can characteristic N–H stretching absorption peak at 3290 cm−1
be governed by the presence of active centers in the polymer indicates the presence of hydrogen bonded urethane linkage.
network, which are capable of specific interactions with the The shift of the N–H stretching band towards lower values is

Table 1
Compositions and physical characteristics of different PUU–PMMA IPN membranes

Membrane (%) NCO/OH Specific Tensile strength Elongation

designation PMMA (mol/mol) gravity (MPa) at break (%)

PUU–PMMA-1 8.51 2.0/1 1.69 61.5 12.4

PUU– PMMA-1 8.51 1.5/1 1.67 55.7 13.7
PUU– PMMA-1 8.51 1.2/1 1.64 52.3 17.3
PUU–PMMA-2 16.99 2.0/1 1.74 63.7 16.0
PUU–PMMA-2 16.99 1.5/1 1.71 61.9 21.7
PUU– PMMA-2 16.99 1.2/1 1.69 60.4 26.7
PUU–PMMA-3 26.62 2.0/1 1.77 65.5 24.8
PUU– PMMA-3 26.62 1.5/1 1.76 64.6 27.4
PUU– PMMA-3 26.62 1.2/1 1.74 61.7 29.9
6460 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

0 0
PUU-PMMA-1 PUU-PMMA-2

50
50
% Absorbance

% Absorbance
100
100

150
150

200
200
4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000
-1 (cm-1
Wavenumber (cm ) Wavenumber )

0
PUU-PMMA-3

50
% Absorbance

100

150

200

4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm-1)

Fig 1. FTIR spectra of PUU–PMMA IPN membranes.

attributed to the occurrence of hydrogen bonding. There is a of PMMA content but it decreased with the decrease of hard
strong absorption at 1743 cm−1 due to free carbonyl group and segment content with a reverse trend in elongation at break.
at 1703 cm−1 due to hydrogen-bonded carbonyl of ester group
of PMMA. Another peak observed at 1642 cm−1 is due to hy-
3.4. Membrane swelling in VOCs and evaluation of diffusion
drogen bonded urea carbonyl of PUU indicating the presence
parameters
of urea linkage. Therefore, the FTIR absorption bands indi-
cate the presence of both the PUU and PMMA in this IPN
The selective permeation of a solvent molecule through a
membrane.
polymer membrane depends on the solubility parameters of
the diffusing species and the polymer. Swelling behavior of
3.3. Tensile property the membrane in a pure solvent is also governed by their
solubility parameter values. Therefore, before subjecting the
In order to judge the ability of the prepared membrane to PUU–PMMA IPN membranes to pervaporation separation of
withstand mechanical stress during the pervaporation operation chlorinated VOCs, their swelling performances were assessed
the tensile property of the prepared membranes was measured. by immersing the membranes in pure VOCs. The degree of
The mechanical properties of the synthesized PUU–PMMA swelling of the membranes in pure 1, 1, 2, 2-tetrachloroethane,
IPNs such as tensile strength and elongation at break were carbon tetrachloride, chloroform, TCE is shown in Table 2. It
measured and the results are shown in Table 1. It is seen from is seen that the degree of swelling correlates well with the sol-
the data that with the increase in soft segment in the membrane ubility parameter values of membrane polymers and the VOCs.
tensile strength decreases but elongation at break increases. The It is also interesting to see from Table 2 that degree of swelling
tensile strength of the membranes increased with the increase in all VOCs increases with the increase in PMMA content
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6461

Table 2
Solubility parameters of chlorinated VOCs and different PUU–PMMA IPN membranes and degree of swelling of the membranes in the VOCs

Membrane NCO/OH Solubility Degree of swelling in

designation (mol/mol) Parameter 1∗ 2∗ 3∗ 4∗

(MPa)1/2 (18.9) (18.8) (17.7) (17.5)

PUU–PMMA-1 2.0/1 14.11 1.87 2.10 2.23 2.48

PUU– PMMA-1 1.5/1 14.19 1.88 2.13 2.28 2.53
PUU– PMMA-1 1.2/1 15.06 1.91 2.17 2.33 2.57
PUU–PMMA-2 2.0/1 15.13 2.11 2.36 2.55 2.87
PUU– PMMA-2 1.5/1 15.18 2.15 2.41 2.61 2.96
PUU– PMMA-2 1.2/1 15.21 2.20 2.46 2.67 3.11
PUU–PMMA-3 2.0/1 16.36 2.29 2.64 2.89 3.26
PUU– PMMA-3 1.5/1 16.38 2.34 2.69 2.97 3.35
PUU– PMMA-3 1.2/1 16.42 2.39 2.75 3.05 3.48

Data in the parenthesis designate solubility parameters (in (MPa)1/2 ) of corresponding VOCs. (1∗ ) 1, 1, 2, 2-Tetrachloroethane, (2∗ ) carbon tetrachloride, (3∗ )
chloroform, and (4∗ ) trichloroethylene.

Table 3
Values of chlorinated VOCs uptake (mol%) at equilibrium (M∞ ) and n for the PUU–PMMA IPN membranes studied at 30 ◦ C

Polymer NCO/OH M∞ (mol%) n

(mol/mol) 1∗ 2∗ 3∗ 4∗ 1∗ 2∗ 3∗ 4∗

PUU–PMMA-1 2.0/1 1.61 1.73 1.84 1.95 0.51 0.54 0.58 0.59
PUU– PMMA-1 1.5/1 1.78 1.88 1.98 2.06 0.54 0.59 0.63 0.64
PUU– PMMA-1 1.2/1 1.96 2.01 2.17 2.28 0.58 0.61 0.66 0.70
PUU–PMMA-2 2.0/1 1.79 1.86 1.95 2.02 0.54 0.56 0.57 0.62
PUU– PMMA-2 1.5/1 1.92 1.99 2.12 2.19 0.56 0.58 0.61 0.64
PUU– PMMA-2 1.2/1 2.11 2.18 2.26 2.34 0.61 0.59 0.64 0.68
PUU–PMMA-3 2.0/1 1.88 2.18 2.24 2.31 0.56 0.55 0.59 0.62
PUU– PMMA-3 1.5/1 2.09 2.23 2.34 2.42 0.57 0.57 0.60 0.64
PUU– PMMA-3 1.2/1 2.32 2.39 2.45 2.52 0.59 0.60 0.63 0.69

(1∗ ) 1, 1, 2, 2-Tetrachloroethane, (2∗ ) carbon tetrachloride, (3∗ ) chloroform, and (4∗ ) trichloroethylene.

(PUU–PMMA-1 to PUU–PMMA-3) as well as with the de- swelling (Table 2) within each level of PMMA content. From
crease in hard segment content (from NCO/OH ratio 2.0/1 to the curves it is clear that for all the membranes TCE has
1.2/1). The degree of swelling of all the membranes is highest shown maximum values of Mt . Again with the increase in
in TCE. The contribution of PMMA to the increase in degree PMMA content and decrease in NCO/OH ratio the VOC sorp-
of swelling is due to the increase of polar PMMA content in tion increases, which is evident from M∞ values (Table 3).
the membrane. On the other hand, since less NCO content in This behavior can be explained on the basis of crosslink den-
the membrane decreases crosslink density it is also an addi- sity and composition of membrane network. As NCO/OH
tional cause of increasing the degree of swelling. So the degree ratio decreases, crosslink density decreases and the hard seg-
of swelling of the membranes in pure chlorinated VOCs indi- ments become less rigid and less dense. Hence the ability of
cates the permselective behavior of these membranes, which polymer chains to accommodate VOC molecules increases. At
are expected to yield higher concentration of the VOCs in the NCO/OH ratio of 1.2/1, the hard segments of the membrane
permeate after pervaporation separation. assume maximum flexibility due to less crosslink points and
To know the nature of diffusion (i.e., Fickian/non-Fickian) of thus the sorption capacity becomes maximum (Velankar and
VOCs occurring through the membranes, evaluation of diffu- Cooper, 1998). The contribution of increased PMMA level to
sion constant is necessary, which in turn can help to understand the increase in VOC sorption is attributed to the incorporation
the separation performances of the VOCs by pervaporation as of more ester groups of PMMA with attendant increase in
well as the suitability of the membrane used for the purpose. polarity and interaction with VOCs (Uragami et al., 2001).
The extent of sorption of pure VOCs by the membranes at As mentioned in Section 2.10 the nature of diffusion
equilibrium (M∝ ) and n values (of Eq. (7)) are included in (Fickian/non-Fickian) can be understood from the value of ex-
Table 3. The diffusion coefficients of VOCs were obtained ponent n of Eq. (7). The calculated values of n shown in Table
from the slopes of plots of Mt versus t 1/2 (Fig. 2) follow- 3 lie in the ranges 0.51–0.61 for 1, 1, 2, 2 tetrachloroethane,
ing Eqs. (8) and (9) for the three representative membranes 0.54–0.61 for carbon tetrachloride, 0.57–0.66 for chloroform
PUU– PMMA-1 , PUU– PMMA-2 and PUU– PMMA-3 and 0.59–0.70 for TCE, which indicate that 1, 1, 2, 2 tetra-
(NCO/OH = 1.2/1), which have shown maximum degree of chloroethane and carbon tetrachloride follow normal Fickian
6462 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

2.5 2.5
PUU-PMMA-1" PUU-PMMA-2"

2.0 2.0
Mt (%)

1.5

Mt (%)
1.5

1.0 1.0
1,1,2,2-Tetrachloroethane 1,1,2,2-Tetrachloroethane
Carbon tetrachloride Carbon tetrachloride
Chloroform Chloroform
0.5 0.5
Trichloroethylene Trichloroethylene

0.0 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
(a) 1/2 1/2
Time (min) (b) Time (min)

3.0

PUU-PMMA-3"
2.5

2.0
Mt (%)

1.5

1.0 1,1,2,2-Tetrachloroethane
Carbon tetrachloride
Chloroform
0.5 Trichloroethylene

0.0
0 5 10 15 20 25 30
(c) Time 1/2 (min)

Fig 2. The sorption curves for the uptake of chlorinated VOCs (in mol%) by PUU–PMMA IPN membranes: (a) PUU– PMMA-1 ; (b) PUU– PMMA-2 ;
(c) PUU– PMMA-3 .

Table 4
Values of diffusion coefficient (D), sorption coefficient (S) and permeability coefficient (P) of VOCs through all PUU–PMMA IPN membranes at 30 ◦ C

Polymer NCO/OH D × 1010 (m2 /s) S P (m2 /s)

(mol/mol) 1∗ 2∗ 3∗ 4∗ 1∗ 2∗ 3∗ 4∗ 1∗ 2∗ 3∗ 4∗

PUU–PMMA-1 2.0/1 4.49 4.75 5.41 6.58 1.87 1.98 2.08 2.17 8.39 9.40 11.25 14.27
PUU– PMMA-1 1.5/1 4.56 4.87 5.56 6.71 1.99 2.04 2.17 2.23 9.07 9.93 12.06 14.96
PUU– PMMA-1 1.2/1 4.61 4.98 5.67 6.88 2.13 2.19 2.26 2.35 9.82 10.90 12.81 16.16
PUU–PMMA-2 2.0/1 4.62 5.02 5.74 6.92 2.05 2.16 2.29 2.37 9.47 11.49 13.14 16.40
PUU– PMMA-2 1.5/1 4.68 5.14 5.87 7.01 2.11 2.28 2.38 2.46 9.87 11.72 13.97 17.24
PUU– PMMA-2 1.2/1 4.73 5.20 5.98 7.12 2.24 2.38 2.44 2.56 10.59 12.38 14.59 18.22
PUU–PMMA-3 2.0/1 4.69 5.18 5.94 7.21 2.18 2.25 2.39 2.46 10.22 11.65 14.19 17.73
PUU– PMMA-3 1.5/1 4.75 5.24 6.03 7.24 2.26 2.34 2.45 2.53 10.73 12.26 14.77 18.32
PUU– PMMA-3 1.2/1 4.78 5.36 6.11 7.29 2.32 2.42 2.54 2.61 11.08 12.97 15.51 19.02

(1∗ ) 1, 1, 2, 2-Tetrachloroethane, (2∗ ) carbon tetrachloride, (3∗ ) chloroform, and (4∗ ) trichloroethylene.

diffusion but chloroform and TCE deviate slightly from normal tent of the membrane (Table 4). This signifies more affinity of
Fickian diffusion. VOC molecules to the PMMA moiety, as also evident from
For a given NCO/OH ratio, the diffusion coefficient and sorp- their M∞ value. All the IPN membranes have shown highest
tion coefficient increases with an increase in the PMMA con- sorption and diffusion of TCE. This is due to the solubility
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6463

Table 5
Values of volume fraction (Vp ), number of chains per unit volume (N), and degree of crosslinking () for the PUU–PMMA IPNs studied

Polymer NCO/OH Vp N × 10−3  × 104

1∗ 2∗ 3∗ 4∗ (kmol/m3 ) (kmol/kg)

PUU–PMMA-1 2.0/1 0.436 0.378 0.346 0.306 1.83 5.37

PUU– PMMA-1 1.5/1 0.428 0.359 0.327 0.295 1.73 5.13
PUU– PMMA-1 1.2/1 0.412 0.345 0.312 0.284 1.65 4.96
PUU–PMMA-2 2.0/1 0.474 0.424 0.392 0.348 1.94 5.68
PUU– PMMA-2 1.5/1 0.461 0.409 0.382 0.339 1.85 5.48
PUU– PMMA-2 1.2/1 0.442 0.391 0.361 0.324 1.74 5.23
PUU–PMMA-3 2.0/1 0.535 0.476 0.448 0.403 2.31 6.77
PUU– PMMA-3 1.5/1 0.520 0.457 0.431 0.383 2.12 6.29
PUU– PMMA-3 1.2/1 0.498 0.434 0.412 0.369 1.99 5.98

(1∗ ) 1, 1, 2, 2-Tetrachloroethane, (2∗ ) carbon tetrachloride, (3∗ ) chloroform, and (4∗ ) trichloroethylene.

160
180
1,1,2,2-Tetrachloroethane flux (kgxm-2xh-1)X103

Carbon tetrachloride flux (kgxm-2xh-1)X103

PUU-PMMA-1'' PUU-PMMA-1''
150 170
PUU-PMMA-2'' PUU-PMMA-2''
PUU-PMMA-3'' PUU-PMMA-3''
140 160

150
130
140
120
130
110 120

100 110

100
90
90
80
80
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
(a) 1,1,2,2-Tetrachloroethane in feed (%) (b) Carbon tetrachloride in feed (%)

200

PUU-PMMA-1'' 200 PUU-PMMA-1''

Trichloroethylene flux (kgxm-2xh-1)X103

180 PUU-PMMA-2'' PUU-PMMA-2''

Chloroform flux (kgxm-2xh-1)X103

PUU-PMMA-3'' PUU-PMMA-3''
180
160

160
140
140
120
120
100
100

80
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
(c) Chloroform in feed (%) (d) Trichloroethylene in feed (%)

Fig 3. Variation of pervaporation fluxes of chlorinated VOCs as functions of their concentrations in feed for different membranes at 30 ◦ C: (a) 1, 1, 2, 2-
tetrachloroethane; (b) carbon tetrachloride; (c) chloroform; (d) trichloroethylene.
6464 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

parameter () matching of respective polymers and the VOCs

(Table 2). It is also observed that the sorption and diffusion co- 200

Chlorinated VOC flux (Kg m-2 h-1)X103)

efficients decrease with an increase in the NCO/OH ratio for a
given composition. 180
The values of volume fraction of polymer in the swollen
membrane (Vp ), degree of crosslinking () and the number 160
of polymer chains per unit volume (N ) were calculated using
Eqs. (7), (12), (14) and (15) and the results are given in Table
140
5. It is relevant to point out here that the parameters Mc , 
and N were obtained for a system of two crosslinked polymers
PUU and PMMA interpenetrated in each other. The polymer 120
1,1,2,2-Tetrachloroethane
chain segment between two crosslink points can be either the Carbon tetrachloride
contribution from a single polymer or from the both of the IPN 100 Chloroform
Trichloroethylene
system. Due to crosslinked network system identity of chemical
composition of the chain segment between the crosslink points
is, therefore, difficult to judge. So the calculated values of N 0.00 0.02 0.04 0.06 0.08 0.10
(total number of chain segments between two crosslinks) and Chlorinated VOCs in feed (%)
 both are assumed to be average contributions from the two Fig 4. Comparison of pervaporation fluxes of chlorinated VOCs with their
interpenetrated polymers in the membrane. From the data in concentrations in feed for PUU– PMMA-3 membrane at 30 ◦ C.
Table 5 it is seen that all membranes have shown high crosslink
density. For a fixed NCO/OH ratio Vp increases from 1, 1, 2, 2
tetrachloroethane to TCE, which is also evident from solubility brane. This comparative flux picture seems to be better than
parameter matching of VOCs and polymers. As the NCO/OH the reported flux results (0.011–0.09 kg/m2 h) of TCE, chloro-
ratio increases, the number of crosslink points increases with form, trichloroethane for PDMS, PEBA, SBR, nitrile rubber,
low values of Mc . Also, it is observed that with increase in etc. membranes for a 100–1000 ppm range of feed concentra-
PMMA proportion in the membrane crosslink density increases tions (Ji et al., 1994; Nijhuis et al., 1991; Dutta and Sikdar,
remarkably with simultaneous increase in VOC sorption. It is 1999; Brun et al., 1985; Schnabel et al., 1998). Again with
due to the increase in polarity of the membrane when more decrease in NCO/OH ratio as the membrane flexibility in-
PMMA is present. creases flux of chlorinated VOCs is increased (Fig. 5). All
the membranes have shown highest flux for TCE. From the
results it is observed that the flux for VOCs varied in the order
3.5. Flux 1, 1, 2, 2-tetrachloroethane<carbon tetrachloride<chloroform
< TCE. This data also supports the selectiveness of the mem-
The effect of feed concentration on the permeation flux of brane towards the VOC separated. Incorporation of PMMA in
1, 1, 2, 2-tetrachloroethane, chloroform, carbon tetrachloride the membrane increases the separation efficiency.
and TCE through PUU–PMMA membranes was investigated
and the results are given in Fig. 3. Feed concentration of 3.6. Separation factor
the chlorinated organic compounds was varied from 100 ppm
(0.01%) to 1000 ppm (0.1%). With increase in the feed con- In Fig. 6 the variation of separation factor of VOCs for
centration flux of chlorinated organic compounds increases. As PUU– PMMA-1 , PUU– PMMA-2 , PUU– PMMA-3 mem-
the VOC concentration in the feed is increased, the membrane branes are shown. The separation factor of PUU– PMMA-3
is more swollen due to polymer chain flexibility and increased membrane is higher for all four chlorinated organic compounds
interaction with PMMA component. McBride et al. (1979) re- than the other membranes due to the presence of more amount
ported that transport of small molecules such as acetone, chlo- of PMMA and higher amount of soft segment, which is also
roform vapors occurs through an elastomeric phase formed by evident from Fig. 5. The separation factor results as shown in
soft segment in segmented polyurethanes. However, hard do- Fig. 6 for PUU–PMMA IPN membranes are found to be supe-
mains, which serve as virtual crosslinks by providing junction rior at least in respect of TCE (30,000–42,000 for 100 ppm feed
points for the soft segments and as reinforcing filler can influ- concentration) and chloroform (2500–6000 for 1000 ppm feed
ence the permeation process either by suppressing membrane concentration) in comparison to reported results of separation
swelling or by altering the path of the permeating molecules. factors for TCE (5600 for 100 ppm feed concentration) using
As a result, the energy required for diffusive transport of VOCs styrene–butadiene–styrene block copolymer (Dutta and Sikdar,
through membrane decreased. A comparative flux picture of 1999) and that for chloroform (1670 for 1000 ppm feed concen-
all the VOCs through PUU– PMMA-3 membrane is shown in tration) using PDMS hollow fiber membrane (Schnabel et al.,
Fig. 4. From Fig. 4 it is seen that from 100 ppm feed concentra- 1998). On the basis of this result, it can be said that the intro-
tion 0.14, 0.125, 0.115 and 0.092 kg/m2 h fluxes were obtained duction of PMMA in the PUU has become an effective way to
for TCE, chloroform, carbon tetra chloride and 1, 1, 2, 2- provide improved membrane performance. PMMA in the PUU
tetrachloroethane, respectively, using PUU– PMMA-3 mem- membrane increases the interaction with chlorinated organic
 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467 6465

220 9000
Chlorinated VOC flux (Kg m-2 h-1)X 103

Chlorinated VOC separation factor

PUU-PMMA-3 PUU-PMMA-3
210 8000
PUU-PMMA-3' PUU-PMMA-3'
PUU-PMMA-3"
PUU-PMMA-3"
200
7000
190
6000
180
5000
170
4000
160
3000
150
1 2 3 4 1 2 3 4
(a) Chlorinated VOCs (b) Chlorinated VOCs

Fig 5. Change of pervaporation flux and separation factor of chlorinated VOCs for a constant feed concentration (0.1%) with increasing soft segment in the
PUU–PMMA IPN membranes at 30 ◦ C (The numerals on the X-axis stands for VOCs such as (1) 1, 1, 2, 2-tetrachloroethane, (2) carbon tetrachloride, (3)
chloroform, and (4) trichloroethylene.).

27000
21000
PUU-PMMA-1''
1,1,2,2-Tetrachloroethane separation factor

PUU-PMMA-1''
24000
Carbon tetrachloride separation factor

PUU-PMMA-2''
18000 PUU-PMMA-2''
PUU-PMMA-3''
PUU-PMMA-3'' 21000
15000
18000

12000 15000

9000 12000

9000
6000

6000
3000
3000
0
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10

(a) 1,1,2,2-Tetrachloroethane in feed (%) (b) Carbon tetrachloride in feed (%)

35000 45000

40000
30000 PUU-PMMA-1'' PUU-PMMA-1''
Trichloroethylene separation factor

PUU-PMMA-2'' PUU-PMMA-2''
35000
Chloroform separation factor

25000 PUU-PMMA-3'' PUU-PMMA-3''

30000
20000
25000

15000 20000

10000 15000

10000
5000

5000
0
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
(c) Chloroform in feed (%) (d) Trichloroethylene in feed (%)

Fig 6. Variation of pervaporation separation factor of chlorinated VOCs with their concentrations in feed for different PUU–PMMA IPN membranes at 30 ◦ C:
(a) 1, 1, 2, 2-tetrachloroethane; (b) carbon tetrachloride; (c) chloroform; (d) trichloroethylene.
6466 S. Das et al. / Chemical Engineering Science 61 (2006) 6454 – 6467

compounds. This behavior was also supported from solubility PUU polyurethane urea
parameter data and swelling of PUU–PMMA membranes and Q degree of volume swelling at equilibrium
VOCs. Q quantity of permeate, kg
S sorption coefficient
TDI 2, 4 toluene diisocyanate
4. Conclusion THF tetrahydrofuran
V1 molar volume of VOC, m3 /kmol
The IPN membranes of HTPB-based PUU and PMMA Vp volume fraction of polymer in swollen state
showed high crosslink density and high sorption values for VOC volatile organic compound
1, 1, 2, 2-tetrachloroethane, carbon tetrachloride, chloroform, Wd initial dry weight of membrane, kg
and TCE. Again the sorption increases with increase in the Ww weight of the membrane after 48 h swelling, kg
PMMA content in the membrane and with decrease in the
NCO/OH ratio i.e., with decrease in crosslink density. The Greek letters
diffusion study also supports this behavior of the membranes.
Therefore, it can be concluded that the prepared membranes
p(VOC/water) separation selectivity of permeation of VOC
have a strong affinity towards the solvents such as 1, 1, 2, 2-  solubility parameter, MPa1/2
tetrachloroethane, carbon tetrachloride, chloroform, and TCE. p solubility parameters of the polymer, MPa1/2
These VOCs can easily permeate through the membranes and s solubility parameters of solvent (VOC), MPa1/2
it has good separation ability of chlorinated VOCs from their  degree of crosslinking, kmol/kg
dilute aqueous solution by pervaporation, which is evident  density of the polymer network, kg/m3
from high flux and separation factor values. It was found that 12 polymer VOC interaction parameter
membranes with higher amount of soft segment and PMMA
content provided good separation performances. Hence, the
VOC selectivity and flux can be tailored with the variation of Acknowledgments
NCO/OH ratio and PMMA proportion in the IPN membranes.
The authors are grateful to CSIR, India for granting research
fund to carry out the present investigation.
Notation
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