Journal of Membrane Science 520 (2016) 779789

Contents lists available at ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Plasma modication of substrate with poly(methylhydrosiloxane) for

enhancing the interfacial stability of PDMS/PAN composite membrane
Hui Zhou a,b, Yi Su a, Xiangrong Chen a, Jianquan Luo a,b, Sheng Tan a,b, Yinhua Wan a,b,n
a
b

State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
University of Chinese Academy of Sciences, Beijing 100049, PR China

art ic l e i nf o

a b s t r a c t

Article history:
Received 18 April 2016
Received in revised form
24 July 2016
Accepted 22 August 2016
Available online 24 August 2016

This paper described a facile approach to improve the interfacial stability of poly(dimethylsiloxane)/
polyacrylonitrile (PDMS/PAN) composite membranes mediated by poly(methylhydrosiloxane) (PMHS).
The surface of PAN substrates was modied with PMHS by plasma treatment. The chemical structure and
surface morphology of modied PAN substrates were characterized by ATR-IR, XPS, SEM, AFM and CA.
The interfacial stability of composite membranes was estimated using the crosshatch tape adhesion test
and the swelling experiment. The results showed that the composite membranes supported by modied
PAN substrates exhibited high interfacial adhesion and the corresponding PDMS separation layer displayed quite low swelling degrees in toluene and n-heptane, due to the enhanced interfacial interaction.
Such enhancement was produced by the stronger mechanical interlocking (increased surface roughness
of substrate) and the presence of chemical bonding between PDMS layer and modied PAN substrate.
Furthermore, these composite membranes showed good pervaporation performance with a separation
factor about 4.2 and a high ux above 9.5 kg m 2 h 1 in the separation of azeotropic methanol/toluene
mixture at 30 C. This work demonstrated that plasma-induced immobilization of PMHS on PAN substrate was an efcient way to improve the interfacial stability of PDMS/PAN composite membrane
without sacrice of its pervaporation performance.
& 2016 Elsevier B.V. All rights reserved.

Keywords:
Poly(dimethylsiloxane)
Composite membrane
Interfacial stability
Plasma
Pervaporation

1. Introduction
Pervaporation is a promising technique in dehydration of organic solvents, removal of trace organics from water, and separation of azeotropic organic mixtures [1]. Recently, the application of
pervaporation in liquid separation has been developed rapidly
with the advantages of being economical, safe and ecofriendly
[2,3]. In the process of pervaporation, membrane is the key factor
that affects its feasibility and economical efciency [4]. Composite
membrane which comprises a thin separation layer (0.120 mm)
and a porous substrate, has the greater potential to offer higher
separation performance and mechanical stability, and thus is
competitive for industrial applications [5]. The thin separation
layer generally determines the pervaporation performance, while
the substrate endows the composite membrane necessary mechanical strength [6]. The commonly used methods to fabricate
composite membranes include interfacial polymerization, plasma
polymerization and direct coating [79]. As to composite membranes fabricated by direct coating, the structure stability was of
n

Corresponding author.
E-mail address: yhwan@home.ipe.ac.cn (Y. Wan).

http://dx.doi.org/10.1016/j.memsci.2016.08.039
0376-7388/& 2016 Elsevier B.V. All rights reserved.

great concern, because of the different swelling behaviors or poor

interfacial compatibility between separation layer and substrate
[1012]. It has been reported that with the increase of operation
time, this type of composite membranes was prone to delaminate
at the interface between the separation layer and substrate [10,13].
In order to improve the structure stability of composite membranes fabricated by coating, great efforts have been devoted to
enhance the interfacial interaction between separation layer and
substrate. Zhao et al. [12] reported that the structure stability of
chitosan (CS)/polyacrylonitrile (PAN) composite membrane was
improved by introducing a transition layer of polycarbophil calcium (PCP). The interfacial adhesion strength of the composite
membrane was enhanced due to the ionic bonds between carboxy
groups of PCP and amino groups of CS. Liu et al. [14] found that the
structure stability between CS layer and polysulfone substrate
(PSf) increased after grafting poly(styrene sulfonic acid) (PSSA) on
PSf substrates, because sulfonic acid groups of PSSA reacted with
amino groups of CS and thus chemically bonded the two layers.
Guo et al. [15] enhanced the structure stability of poly(vinyl alcohol) (PVA)/polyethersulfone (PES) composite membrane by hydrophilic modication of PES substrate. In addition to these hydrophilic polymer-based composite membranes, the structure
stability of hydrophobic polymer-based composite membranes

780

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

had aroused extensive concern due to the chemical inertness of

hydrophobic polymers. Wei et al. [16] investigated the effect of the
surface roughness of substrates on the interfacial adhesion between PDMS layer and ceramic substrate. A signicant increase in
the interfacial adhesion was observed when the surface roughness
of ceramic substrate increased from 0.440 to 1.510 mm. Such an
increase was caused by the stronger mechanical interlocking. Wu
et al. [10] introduced aminopropyl groups in PDMS layer to enhance the interfacial stability of PDMS/PES composite membrane
by forming hydrogen bonds between sulfone of PES and amino in
PDMS. Nevertheless, to the best of our knowledge, few attempt
was dedicated to strengthen the interfacial stability of PDMSbased composite membrane by covalent bond. The probable reason could be the absence of active groups on the surface for many
commonly used polymeric substrates, such as PAN, polyethylene
(PE) and poly(vinlidene uoride) (PVDF).
Plasma is an efcient technique to initiate chemical reactions at
the surface of polymer substrates [17]. The accelerated electrons
from the plasma have sufcient energy to induce cleavage of the
chemical bonds in polymer structure and to form macromolecule
radicals, which subsequently initiate grafting reaction [18]. This
treatment gives rise to an increase of reaction activity for substrates. On the one hand, plasma graft polymerization of monomers could be used to fabricate separation layers that are covalently anchored on substrates [19,20]. These plasma-polymerized
layers had unique structures and showed quite different pervaporation performance from traditional polymer layers [21]. On the
other hand, plasma treatment combined with pre-adsorption of
liquid macromolecules, allows the covalent immobilization of
functional species on substrates as well as the preservation of
important properties of macromolecules (e.g. chain mobility and
functional groups) [22]. This method has been successfully used to
immobilize poly(ethylene glycol) or poly(N-vinyl-2-pyrrolidone)
on the surface of microporous membrane to increase its antifouling property [2325]. Using this plasma process, it is speculated
that poly(methylhydrosiloxane) (PMHS) macromolecule, which is
the crosslinking agent in hydrosilylation of vinyl terminated poly
(dimethylsiloxane), could be chemically attached to the surface of
polymeric substrates, with the retention of functional chemistry
available for further reactions in cure of PDMS.
The objective of this study was to examine the feasibility of
enhancing the interfacial stability of PDMS/PAN composite membrane by plasma-induced immobilization of PMHS on PAN substrates. The PAN substrates were rstly pretreated with PMHS/nheptane solution and then followed by Ar plasma treatment. The
chemical composition and surface morphology of modied PAN
substrates were characterized by ATR-IR, XPS, SEM and AFM. The
interfacial stability of PDMS/PAN composite membranes was assessed by the crosshatch tape adhesion test and the swelling experiment. Furthermore, the PDMS composite membranes were
applied in separation of azeotropic methanol/toluene mixture.

2. Experimental
2.1. Materials
The asymmetric microporous PAN substrate with a molecular
weight cut-off of 20 kDa was purchased from Sepro Co., USA.
PMHS (Mn 17003200 ) was obtained from J&K Scientic Co., Ltd.,
China. Vinyl terminated poly(dimethylsiloxane) was purchased
from GE Toshiba Silicones Co., Ltd., Japan. Platinum(0)-1,3-divinyl1,1,3,3-tetramethyl-disiloxane complex solution was purchased
from SigmaAldrich Co., Ltd., USA. Argon (Ar, 99.99%) gas was
provided by Beijing Qianxi Gas Co., Ltd., China. n-heptane, toluene,
ethyl acetate and methanol of analytical grade were obtained from

Fig. 1. ATR-IR spectra of pristine PAN, PAN pre-adsorbed with PMHS (PAN-1), ultrasonically washed PAN-1 without plasma treatment (PAN-2), and modied PAN
substrates. PAN-120 W-10 s refers to modied PAN substrate with plasma treatment conditions of 120 W and 10 s.

Fig. 2. XPS spectra of pristine and modied PAN substrates. PAN-120 W-10 s refers
to modied PAN substrate with plasma treatment conditions of 120 W and 10 s.

Beijing Chemical Plant, China. All the materials were used as received without any further purication.
2.2. Modication of PAN substrates
Pristine PAN substrate was dipped into 2 wt% PMHS solution
dissolved in n-heptane for 1 h. Then, it was taken out and dried at
room temperature for the following plasma treatment. Plasma
treatment was performed on a YZD08-2C plasma generator made
by Scie-lab (Beijing) Tech. Co., Ltd., China. The pretreated PAN
substrate was placed on the ground electrode in plasma chamber.
The glow discharge was generated between two electrodes with
an Ar ow into the chamber. The plasma exposure time varied
from 10 s to 120 s and the radio-frequency (RF) power changed
from 60 W to 150 W. After that, the substrate was taken out from
the chamber, and washed ultrasonically in n-heptane for 60 min to
remove physically adsorbed PMHS. Finally, the modied PAN
substrates were dried in a vacuum oven at 40 C for further
characterization and use.
2.3. Preparation of PDMS/PAN composite membranes
The composite membranes were prepared by conventional

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

781

Table 1
Surface elemental composition and chemical state of silicon for pristine and modied PAN substrates.
Membranes

PAN
PAN-120 W-10 sa
PAN-90 W-60 s
PAN-120 W-60 s
PAN-120 W-120 s
a

Elemental composition (%)

Chemical state of silicon (%)

Si

M (101.4 eV)

D (102.1 eV)

T (102.8 eV)

Q (103.6 eV)

74.94
41.84
26.30
25.05
16.84

23.06
2.91
1.94
1.88
1.41

2.00
35.02
48.12
48.49
54.95

20.23
23.64
24.58
26.80

6.43
0.16
0.00
0.00

36.37
15.83
14.99
5.75

43.14
48.72
49.07
37.02

14.06
35.30
35.93
57.24

PAN-120 W-10 s refers to modied PAN substrate with plasma treatment conditions of 120 W and 10 s.

Fig. 3. Curve-tting of Si 2p core level for modied PAN substrates: (a) PAN-120 W-10 s; (b) PAN-90 W-60 s; (c) PAN-120 W-60 s; (d) PAN-120 W-120 s. M: [(CH3)3SiO1/2]; D:
[(CH3)2SiO2/2]; T: [(CH3)SiO3/2]; Q: [SiO4/2].

coating method. Vinyl terminated poly(dimethylsiloxane) and

PMHS were dissolved in n-heptane. The mixed solution was agitated vigorously for 10 min as the platinum catalyst was added.
Prior to coating, pristine or modied PAN substrate was immersed
in distilled water at room temperature for 5 h. Residual water at
the substrate surface was quickly wiped off with a lter paper
when the substrate was removed from water. Then, the coating
solution was poured and spread over the substrate surface using a
coating knife. The as-cast membrane was left for 30 min at room
temperature and subsequently transferred to a vacuum oven at
90 C overnight for complete curing.

2.4. Characterization of PAN substrates

The ATR-IR spectra of PAN substrates were determined by a
Nicolet iS50 Spectrometer (Thermo Fisher Scientic Co, USA) over
a scanning range of 4004000 cm 1. XPS analysis was performed
on a Thermo Escalab 250Xi (Thermo Fisher Scientic Co, USA)
equipped with a monochromatic Al K radiation source
(1486.6 eV) to detect the surface chemical compositions of PAN
substrates. Survey spectra over a range of 01350 eV and a highresolution spectrum of Si 2p were collected. The surface morphology of PAN substrates was inspected by a JSM 6700F Scanning

782

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

Fig. 4. Surface images of pristine and modied PAN substrates: (a) pristine PAN; (b) PAN-120 W-10 s; (c) PAN-120 W-60 s; (d) PAN-120 W-120 s.

Electron Microscope (SEM, JEOL Ltd., Japan). The samples were

sputtered with a thin gold layer at 20 mA for 120 s. The surface
roughness of PAN substrates was measured by a Bioscope Catalyst
Atomic Force Microscope (AFM, Bruker, German). The samples
were xed on a double-sided tape and scanned by semi-contact
mode in the air. Five different locations were tested, and the
average value of roughness was reported. Contact angle of PAN
substrates was measured by a Dataphysics OCA 20 Optical Contact
Angle Measuring Device (Dataphysics Co, Germany) at room
temperature. The average value of six different locations for a
sample was taken as its water contact angle.
2.5. Characterization of PDMS/PAN composite membranes
The cross-section morphology of composite membranes was
inspected by SEM. The composite membranes were fractured in
liquid nitrogen and then sputtered with a thin gold layer at 20 mA
for 120 s.
The interfacial adhesion of composite membranes was estimated using the crosshatch tape adhesion test according to ASTM
D3359-B [26]. The test was carried out using an eleven-blade
scribe which made 11 parallel cuts spaced 1 mm apart. Cuts in a
crosshatch pattern were made in the composite membranes using
the metal scriber and then a piece of tape was placed over the
crosshatch region. After 90 s, the tape was removed back upon
itself at an angle of 180. The crosshatch region was inspected by
an optical microscope to determine how much of the PDMS layer
has been removed from the PAN substrate. The adhesion is rated
on a scale of 5B to 0B (best to worst). 5B represents perfect

adhesion without delamination; 4B indicates less than 5% delamination; 3B refers to a delaminated area of 515%, 2B denotes a
delaminated area of 1535%, 1B stands for a delaminated area of
3565% and 0B represents larger than 65% delamination of the
lm. The measurement of each membrane was performed on
three different locations. Optical microscopic images of the
crosshatch tests were captured using an optical microscope
equipped with a Nikon camera.
The swelling behavior of PDMS separation layer was evaluated
by immersing membranes in toluene, n-heptane and ethyl acetate
at 40 C, respectively. The dry PDMS/PAN composite membranes
and PAN substrates without PDMS layer were weighed before
being immersed. After four days, the swollen samples were taken
out from the solvents, wiped with tissue paper to remove the
surface liquid and then weighed again. The swelling degree (DS, %)
was calculated by:

DS( %) =

WsWd
100
Wd

(1)

where Wd and Ws are the weights of the dried and swollen

samples, respectively. Then, the swelling degree of PDMS separation layer can be calculated by:

DSPDMS =

DScomposite DSPAN (1 )

(2)

where DScomposite and DSPAN are the swelling degrees of PDMS/PAN

composite membrane and the PAN substrate without PDMS layer,
respectively; is the weight fraction of PDMS layer to the total

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

783

Fig. 5. Two- and three-dimensional AMF images of substrates surface over a scans size of 10 mm  10 mm: (a), (a') pristine PAN substrate and (b), (b') modied PAN substrate
(plasma treatment conditions of 120 W and 60 s).

Table 2
Surface roughness of pristine and modied PAN substrates measured by AFM (Rq:
the root mean square roughness, Ra: the average roughness).
Substrates PAN

Modied PAN
PAN-120
W-10 sa

Rq (nm)
Ra (nm)

12.12 22.97
8.65 15.69

PAN-90
W-60 s

PAN-120
W-60 s

PAN-120
W-120 s

19.76
15.03

19.09
14.59

19.61
14.56

a
PAN-120 W-10 s refers to modied PAN substrate with plasma treatment
conditions of 120 W and 10 s.

composite membrane.
2.6. Pervaporation experiments
Pervaporation experiments were carried out on a home-made
apparatus as described elsewhere [27]. A at composite membrane with an effective membrane area of 18.86 cm2 was placed in
a pervaporation test cell. The feed solution was 32% toluene/methanol mixture and maintained at 30 C in water bath. A peristaltic
pump was used to recirculate the feed solution from feed tank to
the pervaporation cell with a ow rate of 700 mL/min. During the
experiment, the downstream pressure was kept below 500 Pa by a
vacuum pump. The permeate vapor was condensed in a cold trap
which was cooled with liquid nitrogen. Samples of both retentate
and permeate were collected and their compositions were

Fig. 6. Water contact angles of pristine PAN substrate and modied PAN substrates
with plasma RF power of 120 W.

determined by an Agilent 7890 Gas Chromatography (Agilent Co,

USA). The pervaporation performance of the membrane was
evaluated in terms of the permeate ux and separation factor. The
permeate ux was determined by weighing the permeate collected in cold trap for a given time. To eliminate the effect of PDMS
thickness on ux, the normalized ux (J, normalized to 10 mm) was
used, as calculated by the following equation:

784

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

Fig. 7. Cross-section morphologies of PDMS composite membranes supported by (a), (a') pristine PAN substrate and (b), (b') modied PAN substrate (plasma treatment
conditions: 120 W and 60 s).

J=

Wd
10At

(3)

where W (g) is the weight of liquid collected in the traps during an

experiment time interval t (h). A (m2) is the effective area of the
composite membrane. d (mm) is the thickness of PDMS separation
layer.
The separation factor () was calculated as:

T / M =

YT /YM
XT /XM

(4)

where X and Y are the weight fractions of substances in the feed

and permeate, respectively, while subscripts T and M denote
toluene and methanol, respectively.

3. Results and discussion

3.1. Characterization of PAN substrates
Plasma is an efcient technique for covalent immobilization of
functional species on the surface of membranes [2225]. In this
study, plasma was used to immobilize PMHS chains on the surface
of PAN substrates. Fig. 1 shows the ATR-IR spectra of pristine and
modied PAN substrates. The pristine PAN substrate showed two
strong adsorption peaks at 2245 and 1452 cm 1 belonging to CN
and CH2, respectively. After physical adsorption of PMHS, the
ATR-IR spectrum of substrate (PAN-1) presented the characteristic
peaks of PMHS. While such physically adsorbed PMHS could be

removed by ultrasonic washing, as the ATR-IR spectra of pristine

PAN and PAN-2 were almost the same. The ATR-IR spectra for
modied PAN substrates which were treated by plasma and then
ultrasonically washed, exhibited the characteristic peaks of PMHS.
Those peaks are 2170 and 901 cm 1 for SiH group, 1260 and
770 cm 1 for SiCH3 group, 1050 cm 1 for SiOSi group and
847 cm 1 for Si(CH3)3 group, respectively. It conrms that PMHS
precursor was successfully immobilized on the surface of PAN
substrate by plasma. However, the ratio of peak intensity of SiO
Si to that of Si(CH3)x (or SiH) was much high for modied PAN
substrates compared with PAN-1. The ATR-IR spectrum of PAN-1
substrate was believed to be the simple combination of PMHS and
PAN substrate, and the ratio (SiOSi/Si(CH3)x) was equal to the
nascent PMHS precursor. The high ratio of modied PAN substrates indicates that SiC or SiH bonds were broken while SiO
bonds formed during the plasma process [28,29]. Overall, parts of
SiH groups were still preserved on the PMHS chains after plasma
treatment for 120 s. These SiH groups would participate in the
curing reaction of PDMS layer during the preparation of composite
membranes and hence formed chemical bond between PAN substrates and PDMS layer.
XPS for pristine and modied PAN substrates were taken to
further determine the chemical changes undergoing on the substrate surface (Fig. 2). Two strong peaks assigned to C 1s and N 1s
were observed in the spectrum of pristine PAN substrate. After
immobilization of PMHS, the two peaks decreased greatly. New
peaks belonging to Si 2p, Si 2s and O 1s emerged in the spectra of
modied PAN substrates. The elemental compositions determined
by XPS are presented in Table 1. The small amount of oxygen in

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

785

Fig. 8. Light microscopic images of composite membranes supported by (a), (a') pristine PAN substrate and (b), (b') modied PAN substrate (plasma treatment conditions:
120 W and 60 s) after crosshatch tape adhesion test.

Table 3
Interfacial adhesion classication of PDMS composite membranes supported by
pristine and modied PAN substrates.
Substrates

Tape test rank

(ASTM)

Table 4
Solubility parameters and difference in solubility parameters between polymer and
solvent.

PAN Modied PAN

0B

PAN120 W-10 sa

PAN90 W-60 s

PAN120 W-60 s

PAN-120 W120 s

5B

5B

5B

5B

a
PAN-120 W-10 s refers to modied PAN substrate with plasma treatment
conditions of 120 W and 10 s.

Fig. 9. Swelling degrees of PDMS separation layer supported on pristine PAN

substrate and modied PAN substrate (plasma treatment conditions of 120 W and
60 s), in toluene, n-heptane and ethyl acetate at 40 C for four days.

pristine PAN was attributed to the additives in the commercial

PAN substrate [30]. For modied PAN substrates, the silicon concentration increased with the increase of plasma exposure time

Toluene [37]
n-heptane [37]
Ethyl acetate [37]
PDMS [38]
PAN [39]
a

d (MPa1/2)

p (MPa1/2) h (MPa1/2)

PDMS,ja

PAN,ja

18.0
15.3
15.8
15.9
13.8

1.4
0.0
5.3
0.1
16.2

3.66
4.74
5.77

18.47

19.21
21.14
12.75
18.47

2.0
0.0
7.2
4.7
13.5

i,j is calculated by the equation: i, j = (d, i d, j )2 + (p, i p, j )2 + (h, i h, j )2 .

and RF power, implying that more PMHS precursor was immobilized on the surface of PAN substrate. As the exposure time or
RF power increased, more reactive species (radicals, ions, molecular excited states, etc.) were created both on the substrates
surface and the physically adsorbed PMHS precursor, and hence
promoted the immobilization process of PMHS on PAN substrates
[25,31]. The oxygen concentration also increased after immobilization of PMHS on PAN substrates. From the theoretical
composition of PMHS precursor, it is expected that the concentration of silicon and oxygen should be equal. However, the
results in Table 1 reveal that the oxygen concentration was higher
than that of silicon. This high amount of oxygen was mainly because of the increased oxidation states of silicon for immobilized
PMHS chains. As shown in Fig. 3, the amount of silicon in M
([(CH3)3SiO1/2]) and D ([(CH3)2SiO2/2]) states decreased with the
increase of exposure time, while the amount of silicon in T ([(CH3)
SiO3/2]) and Q ([SiO4/2]) states increased. It seems that plasma
converted the silicon from M and D types to T and Q types, as the
same as reported by O'Neill et al. [29]. After exposure above 60 s,
the majority of the silicon atoms were bonded to three or four
oxygen atoms. Those trends indicate that the PMHS precursor
immobilized on PAN surface was highly crosslinked [28].

786

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

Fig. 10. Effects of RF power (a) and exposure time (b) on pervaporation performance for PDMS/PAN composite membranes. Feed concentration: 32 wt% toluene
at 30 C.

power had the same effect on surface pores. But such effect was
not signicant as that of exposure time, because the amount of
immobilized PMHS increased much faster with the exposure time
than that of RF power (Table 1). When exposure time was above
120 s, the immobilized PMHS precursor melted together leading to
complete blockage of surface pores, and the PAN surface became
almost nonporous. The surface morphology of substrate was reported to have great inuence on pervaporation performance for
composite membranes [5,33]. It could be anticipated that the
permeate ux of composite membranes supported on the modied PAN substrates would decrease with an excessive immobilization of PMHS.
It is well known that the surface roughness of substrates has a
signicant inuence on the interfacial adhesion of composite
membranes [16,34]. Herein, AFM was used to evaluate the surface
roughness of PAN substrates. Fig. 5 presents the two- and threedimensional AFM images of the pristine and modied PAN substrates. Compared with pristine PAN substrate, some bulges were
observed on the surface of modied PAN substrate. These bulges
might be the aggregates of PMHS precursor on PAN surface. The
roughness parameters of each AFM image were determined using
the NanoScope Analysis software and the values are summarized
in Table 2. The root mean square roughness (Rq) for pristine PAN
substrate was 12.12 nm, which increased to 19.0922.97 nm after
immobilization of PMHS precursor. The arithmetical average
roughness (Ra) also increased from 8.65 nm for pristine PAN to
14.5615.69 nm for modied PAN substrates. Those results indicate that the plasma-induced immobilization of PMHS led to an
increased surface roughness for PAN substrates. Such increment in
surface roughness provided more contact area between PDMS
separation layer and PAN substrate, and hence gave rise to higher
interfacial interaction for composite membrane [16].
The water contact angles of PAN substrates before and after
modication are shown in Fig. 6. The surface of pristine PAN
substrate was highly hydrophilic with a contact angle of 46.9.
After immobilization of PMHS, the water contact angle increased
to around 100, indicating that the surface of modied PAN substrates became hydrophobic. This transformation was attributed to
the instinct hydrophobicity of PMHS precursor and the increased
surface roughness (Table 2). Nguyen et al. [28] reported that the
water contact angles of ethylene propylene diene elastomeric
terpolymer (EPDM) substrate increased from 82 to 120 after
deposition of tetramethyldisiloxane. The approximate hydrophobicity between the surface of modied PAN substrates and
PDMS (contact angle 114) might be helpful to improve the interfacial compatibility for PDMS/PAN composite membranes [35].
3.2. Characterization of PDMS/PAN composite membranes

Fig. 11. Effect of immersion time on the pervaporation performance of composite

membrane supported by pristine PAN substrate and modied PAN substrate
(plasma treatment condition: 120 W and 60 s).

The surface morphology of the pristine and modied PAN

substrates was characterized by SEM (Fig. 4). The pristine PAN
substrate had a well-dened pore size of about 20 nm, but after
modication, both the surface pore size and porosity expectedly
decreased. This phenomenon was owing to the coverage of the
immobilized PMHS precursor on the substrates surface [32].
Moreover, with the increase of exposure time, both the surface
pore size and porosity were decreasing because more PMHS precursors were immobilized on the PAN surface. The increase in RF

3.2.1. Cross-section morphology of PDMS/PAN composite membranes

The cross-section morphology of PDMS composite membranes
supported by pristine and modied PAN substrates were examined
by SEM. As can be seen from Fig. 7(a) and (b), the PDMS separation
layer with a thickness of 1016 mm was properly cast on the top of
PAN substrate, and no split at the interface was observed for both
composite membranes. Such integrated structure was attributed
to the penetration of PDMS solution into PAN substrates during
coating process, as show in Fig. 7(a') and (b'). This phenomenon
was also reported by Vankelecom et al. [36] with PDMS/PVDF
composite membranes. After cured at high temperature, the penetrated PDMS was mechanically interlocked in the PAN substrates, which contributed to the interfacial adhesion for composite membranes [16]. More importantly, compared with membrane supported by pristine PAN substrate, the interface of composite membrane supported by modied PAN substrate appeared
to be a little more integrated (Fig. 7(a) and (b)), which was resulted

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

from the favorable compatibility and the chemical bonding between PDMS separation layer and modied PAN substrate.
3.2.2. Interfacial adhesion of PDMS/PAN composite membranes
The interfacial adhesion of PDMS/PAN composite membranes
was estimated using the crosshatch tape adhesion test. Fig. 8
shows the optical microscopic images of composite membranes
after crosshatch tape adhesion test. The rough regions in the microscopic images were surface of PAN substrate with detached
PDMS, whereas the smooth regions were surface of the retained
PDMS layer. Clearly, either the at regions or the edges of the
crosshatch for PDMS composite membrane supported by pristine
PAN substrate were destroyed in the crosshatch test (Fig. 8(a) and
(a')). The PDMS layer could be easily peeled from the pristine PAN
substrate by tape. The adhesion classication was ranked as ASTM0B, indicating that PDMS exhibited poor adhesion to pristine PAN
substrate. In contrast, the adhesion of PDMS layer to the modied
PAN substrate was quite good. The microscopic images showed no
delamination (Fig. 8(b) and (b')) and it was hard to peel the PDMS
layer from the modied PAN substrate by tape. The adhesion
classication of PDMS layer to the modied PAN substrates with
different plasma treatment conditions is summarized in Table 3.
Obviously, the surface modication of PAN substrates remarkably
improved the interfacial adhesion of PDMS/PAN composite membranes, while the plasma treatment conditions showed little effect
on the interfacial adhesion under the experimental conditions
examined.
For the composite membrane supported by pristine PAN substrate, the mechanical interlocking was the dominant factor for
adhesion as no chemical reaction was involved, while it could not
protect composite membrane from detaching under an external
force. As to composite membranes supported by the modied PAN
substrates, both the mechanical interlocking and the chemical
reaction contributed to the interfacial adhesion. In detail, rstly,
the increased surface roughness of modied PAN substrates
mentioned above, strengthened the mechanical interlocking and
provided more contact area for chemical reaction [16]. Secondly,
some SiH groups on modied PAN substrate surface participated
in the curing reaction of PDMS separation layer and hence improved the interfacial adhesion obviously. The resulting high interfacial adhesion could avoid delamination of composite membrane under the abrasion and friction forces that may occur in
practical application.
3.2.3. Swelling behavior of PDMS/PAN composite membranes
The swelling behaviors of membranes were tested by pure toluene, n-heptane and ethyl acetate at 40 C. Fig. 9 shows the
swelling degrees of PDMS separation layer for composite membranes. It can be seen that the swelling degree of PDMS separation
layer in different solvents followed this order: toluene4 nheptane4ethyl acetate. The swelling behavior of PDMS depends
on its afnity to solvent and can be estimated by solubility parameters. Table 4 presents the Hansen solubility parameters of
polymers and solvents, as well as the difference in the solubility
parameter between two components (i,j) [3739]. The smaller
i,j results in higher swelling degree of polymer i in solvent j
[40]. Obviously, the values PDMS,j was in good agreement with
the swelling behaviors of PDMS layer in different solvents. Compared with PDMS,j, the values PAN,j was larger implying that
the PAN substrate would have much lower swelling degree in the
three solvents.
Fig. 9 shows that the PDMS layer supported on modied PAN
substrate had much lower swelling degrees than that on pristine
PAN substrate. This was attributed to the different interfacial interactions between PDMS layer and substrates. For PDMS layer
supported on pristine PAN substrate, the interfacial interaction

787

mainly referred to the mechanical interlocking. But under the big

shear stress caused by different swelling behaviors between PDMS
layer and PAN substrate [41], this interaction was not strong enough to conne the PDMS chains around the surface of PAN substrate, and the PDMS layer swelled extensively. However, for PDMS
layer supported on modied PAN substrate, the interfacial interaction included enhanced mechanical interlocking and chemical
bonding. This strong interfacial interaction could overcome the big
shear stress and conned the PDMS polymer chains around the
surface of PAN substrate. Thus, the swelling of PDMS layer was
suppressed by the low-swelling PAN substrate. It was expected
that this kind of PDMS composite membranes could maintain an
integrated structure and had a longer lifetime in separation of
organics mixtures.
3.3. Pervaporation performance of PDMS/PAN composite membranes
One of the promising applications of pervaporation is separation of azeotropic organic mixtures [2]. The toluene/methanol
mixture, which is commonly found in the petrochemical and
pharmaceutical industries, form an azeotropic solution with a
composition of 32 wt% toluene at a constant pressure of 101.3 kPa
[42,43]. Herein, the PDMS composite membranes prepared in this
work were employed for the separation of azeotropic toluene/
methanol mixture at 30 C.
Fig. 10 shows the pervaporation performance of PDMS/PAN
composite membranes. The separation factor for all composite
membranes was around 4.2, indicating that the effect of surface
modication of PAN substrates on selectivity was negligible. The
total ux for composite membranes supported by the modied
PAN substrates was lower than that of the membrane supported
by pristine PAN substrate (i.e. the points at RF power of zero in
Fig. 10(a)). This ux drop might be attributed to the additional
mass transfer resistance of immobilized PMHS on substrate
surface.
With the increase of plasma RF power and exposure time, more
PMHS precursor were immobilized on the modied PAN surface
and the total ux kept on decreasing. Nevertheless, the composite
membrane still displayed a high ux above 9.5 kg m 2 h 1 when
the plasma exposure time was less than or equal to 60 s (Fig. 10
(b)). Further increasing exposure time would lead to a signicant
decrease of total ux, because the surface of PAN substrates was
almost covered with the immobilized PMHS precursor. As shown
in Fig. 4(d), the PAN substrate became nearly nonporous after
exposure for 120 s. Such nonporous surface of substrate brought
great mass transfer resistance and had a negative effect on ux.
These results indicate that with a suitable immobilization of PMHS
on PAN substrate surface, the PDMS/PAN composite membrane
could maintain its good separation factor and high ux.
To evaluate the operation stability of membrane, PDMS composite membranes supported by pristine PAN and modied PAN
substrates were immersed in model permeate with a concentration of 67 wt% toluene for a certain period, and then tested by
pervaporation experiment. As can be seen from Fig. 11, the total
ux increased and the separation factor slightly decreased after
long-term immersion for both composite membranes. Similar
phenomenon was also reported by Wu et al. [10]. The total ux
increased nearly by 100% for the membrane supported by pristine
PAN substrate, while only by 18% for the membrane supported by
modied PAN substrate. This was attributed to the different
swelling degrees of PDMS separation layers for two composite
membranes. For the membrane supported by pristine PAN substrate, the higher swelling degree of PDMS separation layer resulted in a larger free volume for the diffusion of organics, and
thus a greater increment in total ux. However, this membrane
showed delamination on the edge after immersion for 15 days. The

788

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

delamination was aggravated by the subsequently repeating immersion and pervaporation experiments. Finally, this composite
membrane collapsed after 30-days' test and could not be used for
pervaporation any more. On the contrary, the composite membrane supported by modied PAN substrate maintained an integrated structure and a stable pervaporation performance even
after immersion for 40 days. This states that modication of PAN
substrate effectively improved the solvent-resistant property of
the PDMS/PAN composite membrane. Therefore, it can be expected that composite membrane supported by modied PAN
substrate could maintain its structure stability in long-time running, and could be highly promising in separation of organic
mixtures.

4. Conclusion
A facile approach for fabricating PDMS/PAN composite membranes with improved interfacial stability was developed. The
surface of PAN substrates was modied with PMHS by plasma
treatment. This modication not only enhanced the surface
roughness of PAN substrates which strengthened the mechanical
interlocking, but also endowed chemical binding between PDMS
separation layer and PAN substrates. As a result, the interfacial
adhesion of PDMS/PAN composite membranes was improved remarkably from ASTM-0B to ASTM-5B after the modication of PAN
substrates. Meanwhile, the swelling of PDMS separation layer for
this new composite membrane was largely suppressed, especially
in toluene and n-heptane solvents, due to the strong conning
effect of improved interfacial interaction.
In the separation of azeotropic methanol/toluene mixtures, the
pervaporation performance of this composite membrane did not
change obviously with suitable modication of PAN substrate,
displaying a separation factor about 4.2 and a high ux above
9.5 kg m 2 h 1. Moreover, even after immersion in 67 wt% toluene/methanol mixture above 900 h, the composite membranes
supported by the modied PAN substrate still maintained its integrated structure and kept a stable separation performance. This
study demonstrates that plasma-induced immobilization of functional chains on substrates could be an efcient way to improve
the interfacial stability of composite membranes combined with
excellent separation performance.

Acknowledgments
This work was supported by the National High Technology
Research and Development Program of China (Grant NoS.
2012AA021202, 2013AA065803), the National Natural Science
Foundation of China, China (Grant No. 21176239) and the Chinese
Academy of Sciences' Key Deployment Project (Grant No. KSZDEW-2-017-3).

References
[1] X. Feng, R.Y.M. Huang, Liquid separation by membrane pervaporation: a review, Ind.
Eng. Chem. Res. 36 (1997) 10481066.
[2] B. Smitha, D. Suhanya, S. Sridhar, M. Ramakrishna, Separation of organic-organic
mixtures by pervaporation-a review, J. Membr. Sci. 241 (2004) 121.
[3] J. Kujawski, A. Rozicka, M. Bryjak, W. Kujawski, Pervaporative removal of acetone,
butanol and ethanol from binary and multicomponent aqueous mixtures, Sep. Purif.
Technol. 132 (2014) 422429.
[4] H. Zhou, Y. Su, X. Chen, S. Yi, Y. Wan, Modication of silicalite-1 by vinyltrimethoxysilane (VTMS) and preparation of silicalite-1 lled polydimethylsiloxane
(PDMS) hybrid pervaporation membranes, Sep. Purif. Technol. 75 (2010) 286294.
[5] R.D. Offeman, C.N. Ludvik, A novel method to fabricate high permeance, high selectivity thin-lm composite membranes, J. Membr. Sci. 380 (2011) 163170.
[6] J.M.S. Henis, M.K. Tripodi, Composite hollow ber membranes for gas separation:

the resistance model approach, J. Membr. Sci. 8 (1981) 233246.

[7] Y.K. Ong, G.M. Shi, N.L. Le, Y.P. Tang, J. Zuo, S.P. Nunes, T.-S. Chung, Recent membrane
development for pervaporation processes, Prog. Polym. Sci. 57 (2016) 131.
[8] W.J. Lau, A.F. Ismail, N. Misdan, M.A. Kassim, A recent progress in thin lm composite membrane: a review, Desalination 287 (2012) 190199.
[9] S. Hermans, H. Marin, C.V. Goethem, I.F. Vankelecom, Recent developments in thin
lm (nano) composite membranes for solvent resistant nanoltration, Curr. Opin.
Chem. Eng. 8 (2015) 4554.
[10] H. Wu, X. Zhang, D. Xu, B. Li, Z. Jiang, Enhancing the interfacial stability and solventresistant property of PDMS/PES composite membrane by introducing a bifunctional
aminosilane, J. Membr. Sci. 337 (2009) 6169.
[11] J. Chen, X. Chen, X. Yin, J. Ma, Z. Jiang, Bioinspired fabrication of composite pervaporation membranes with high permeation ux and structural stability, J. Membr.
Sci. 344 (2009) 136143.
[12] C. Zhao, H. Wu, X. Li, F. Pan, Y. Li, J. Zhao, Z. Jiang, P. Zhang, X. Cao, B. Wang, High
performance composite membranes with a polycarbophil calcium transition layer
for pervaporation dehydration of ethanol, J. Membr. Sci. 429 (2013) 409417.
[13] W. Wei, S. Xia, G. Liu, X. Dong, W. Jin, N. Xu, Effects of polydimethylsiloxane (PDMS)
molecular weight on performance of PDMS/ceramic composite membranes, J.
Membr. Sci. 375 (2011) 334344.
[14] Y.L. Liu, C.H. Yu, L.C. Ma, G.C. Lin, H.A. Tsai, J.Y. Lai, The effects of surface modications on preparation and pervaporation dehydration performance of chitosan/
polysulfone composite hollow-ber membranes, J. Membr. Sci. 311 (2008) 243250.
[15] R. Guo, X. Fang, H. Wu, Z. Jiang, Preparation and pervaporation performance of
surface crosslinked PVA/PES composite membrane, J. Membr. Sci. 322 (2008) 3238.
[16] W. Wei, S. Xia, G. Liu, X. Gu, W. Jin, N. Xu, Interfacial adhesion between polymer
separation layer and ceramic support for composite membrane, AIChE J. 56 (2009)
15841592.
[17] N. Nady, M.C.R. Franssen, H. Zuilhof, M.S.M. Eldin, R. Boom, K. Schron, Modication
methods for poly(arylsulfone) membranes: a mini-review focusing on surface
modication, Desalination 275 (2011) 19.
[18] A. Bhattacharyaa, B.N. Misra, Grafting: a versatile means to modify polymers techniques, factors and applications, Prog. Polym. Sci. 29 (2004) 767814.
[19] Z. Li, B. Zhang, L. Qu, J. Ren, Y. Li, A novel atmospheric dielectric barrier discharge
(DBD) plasma graft-lling technique to fabricate the composite membranes for
pervaporation of aromatic/aliphatic hydrocarbons, J. Membr. Sci. 371 (2011)
163170.
[20] T. Yamaguchi, S. Nakao, S. Kimura, Plasma-graft lling polymerization: preparation
of a new type of pervaporation membrane for organic liquid mixtures, Macromolecules 24 (1991) 55225527.
[21] S. Roualdes, J. Durand, R.W. Field, Comparative performance of various plasma
polysiloxane lms for the pervaporative recovery of organics from aqueous streams,
J. Membr. Sci. 211 (2003) 113126.
[22] M. Nitschke, S. Zschoche, A. Baier, F. Simon, C. Werner, Low pressure plasma immobilization of thin hydrogel lms on polymer surfaces, Surf. Coat. Technol. 185
(2004) 120125.
[23] J. Ju, T. Wang, Q. Wang, Superhydrophilic and underwater superoleophobic PVDF
membranes via plasma-induced surface PEGDA for effective separation of oil-inwater emulsions, Colloid Surf. A 481 (2015) 151157.
[24] P. Wang, K.L. Tan, E.T. Kang, K.G. Neoh, Plasma-induced immobilization of poly
(ethylene glycol) onto poly(vinylidene uoride) microporous membrane, J. Membr.
Sci. 195 (2002) 103114.
[25] Z.M. Liu, Z.K. Xu, L.S. Wan, J. Wu, M. Ulbricht, Surface modication of polypropylene
microltration membranes by the immobilization of poly(N-vinyl-2-pyrrolidone): a
facile plasma approach, J. Membr. Sci. 249 (2005) 2131.
[26] ASTM D3359-08, Standard Test Methods for Measuring Adhesion by Tape Test,
United States, 2008.
[27] X. Zhuang, X. Chen, Y. Su, J. Luo, S. Feng, H. Zhou, Y. Wan, Surface modication of
silicalite-1 with alkoxysilanes to improve the performance of PDMS/silicalite-1
pervaporation membranes: preparation, characterization and modeling, J. Membr.
Sci. 499 (2016) 386395.
[28] N.D. Tran, N.R. Choudhury, N.K. Dutta, Surface tailoring of an ethylene propylene
diene elastomeric terpolymer via plasma-polymerized coating of tetramethyldisiloxane, Polym. Int. 54 (2005) 513525.
[29] L. O'Neill, N. Shephard, S.R. Leadley, L.A. O'Hare, Atmospheric pressure plasma
polymerised primer to promote adhesion of silicones, J. Adhes. 84 (2008) 562577.
[30] Z.P. Zhao, J. Li, J. Chen, C.X. Chen, Nanoltration membrane prepared from polyacrylonitrile ultraltration membrane by low-temperature plasma: 2. Grafting of
styrene in vapor phase, J. Membr. Sci. 251 (2005) 239245.
[31] Z.P. Zhao, N. Li, M.S. Li, Y. Zhang, Controllable modication of polymer membranes
by long-distance and dynamic low-temperature plasma ow: long-distance and
dynamic characteristics, Plasma Chem. Plasma P. 32 (2012) 12431258.
[32] S. Belfer, A. Bottino, G. Capannelli, Preparation and characterization of layered
membranes constructed by sequential redox-initiated grafting onto polyacrylonitrile ultraltration membranes, J. Appl. Polym. Sci. 98 (2005) 509520.
[33] J.G. Wijmans, P. Hao, Inuence of the porous support on diffusion in composite
membranes, J. Membr. Sci. 494 (2015) 7885.
[34] D.E. Packham, Surface energy, surface topography and adhesion, Int. J. Adhes. Adhes.
23 (2003) 437448.
[35] G. Liu, F. Xiangli, W. Wei, S. Liu, W. Jin, Improved performance of PDMS/ceramic
composite pervaporation membranes by ZSM-5 homogeneously dispersed in PDMS
via a surface graft/coating approach, Chem. Eng. J. 174 (2011) 495503.
[36] I.F.J. Vankelecom, B. Moermans, G. Verschueren, P.A. Jacobs, Intrusion of PDMS top
layers in porous supports, J. Membr. Sci. 158 (1999) 289297.
[37] A.F. Barton, Solubility parameters, Chem. Rev. 75 (1975) 731753.
[38] J. Niemist, W. Kujawski, R.L. Keiski, Pervaporation performance of composite poly
(dimethyl siloxane) membrane for butanol recovery from model solutions, J.
Membr. Sci. 434 (2013) 5564.
[39] S. Mandal, V.G. Pangarkar, Development of co-polymer membranes for pervaporative separation of methanol from methanol/benzene mixture-a solubility

H. Zhou et al. / Journal of Membrane Science 520 (2016) 779789

parameter approach, Sep. Purif. Technol. 30 (2003) 147168.

[40] K. Hendrix, G. Koeckelberghs, I.F.J. Vankelecom, Study of phase inversion parameters for PEEK-based nanoltration membranes, J. Membr. Sci. 452 (2014)
241252.
[41] P. Shao, R. Huang, X. Feng, W. Anderson, R. Pal, C. Burns, Composite membranes
with an integrated skin layer: preparation, structural characteristics and pervaporation performance, J. Membr. Sci. 254 (2005) 111.

789

[42] P. Garg, R.P. Singh, V. Choudhary, Selective polydimethylsiloxane/polyimide blended

IPN pervaporation membrane for methanol/toluene azeotrope separation, Sep.
Purif. Technol. 76 (2011) 407418.
[43] S.J. Lue, J.S. Ou, C.H. Kuo, H.Y. Chen, T.H. Yang, Pervaporative separation of azeotropic
methanol/toluene mixtures in polyurethanepoly(dimethylsiloxane) (PUPDMS)
blend membranes: correlation with sorption and diffusion behaviors in a binary
solution system, J. Membr. Sci. 347 (2010) 108115.