Siam Physics Congress SPC2012

Past, Present and Future of Physics 9-12 May 2012

The Effects of Argon and Oxygen Plasmas on the Surface Morphology of Polysulfone Membrane
Chalad Yuenyao1,3*, Thawat Chittrakarn1, Yutthana Tirawanichakul1, Prajak Saeung1, Wirach
Taweepreda2
1

Department of Physics, Faculty of Science, Prince of Songkla University, Hatyai, Songkhla90112,

Thailand
2
Membrane Science and Technology Research Center, Department of Physics, Faculty of Science,
Prince of Songkla University, Hatyai, Songkhla 90112, Thailand
3
ThEPCenter, CHE, 328 Si Ayutthaya Rd., Bangkok 10400, Thailand
*Corresponding author. E-mail: chunsupa@hotmail.com
Abstract

Polysulfone membrane films with dimension of 7x14 square centimeter surface has been
modified by the DC glow discharge plasmas where an argon and oxygen used as an ionized gas. The
argon and oxygen discharge plasmas were operated under the pressure conditions of 5.010-4 and 5.6
10-2 mbar, respectively. The discharge period for treatment of membrane film was varied between 5 to
30 minutes with an increment of 5 min/step, respectively. The treated polysulfone membrane films
were characterized by FTIR-ATR, SEM and water contact angle compared to the control sample which
is not modified by plasma discharges whilst the physical property in terms of storage modulus was also
evaluated by DMTA technique. The results showed that the argon and oxygen glow discharge plasmas
are feasible to modify the surface membrane sheet significantly, especially on their physical properties.
Keywords: Polysulfone membrane, Plasma, Surface morphology, Degradation, Permeation
Introduction
Polysulfone (PSF) both in the hollow fiber
and flat sheet membranes are widely used in the
separation process due to its chemical, thermal
and mechanical high resistance, easier for filmfabricated, as well as its hydrophilicity already
improved in several investigations through the
application of plasma treatment and others[1,7].
Plasma which is partially or fully ionized gas is
composed of highly excited atoms, neutral
molecules, electrons, ions, and free radical
species as well as photons of UV and visible
lights[2,3]. To modify the PSF polymeric
membrane surface in several applications,
especially on the separation process, it is
necessarily to understand that what process will
occur when the membrane was exposed to the
plasma. Many of processes are took place on the
surface of polymeric membranes during its
exposure to the plasma. Normally, etching or
degradation processes will take place when the
non-polymerizing gas such as O2, Ar, N2, or CO2
is used. On the other hand, when the
polymerizing gas (e.g. vapor of acrylic acid, nbutylamine and allylamine etc.,) is used, the
plasma polymer creation will occur. In order to

control the process, many parameters are

adjusted such as exposure time, working gas,

pressure or gas flow rate, as well as the

power of plasma, depending on the aim of
work. A glow discharge generated by the
electrical potential of 400 V and low
pressure of 0.2 mbar can be incorporated the
functional groups onto the surface of
polyethylene terephthalate (PET) film. As
well as the roughness and crystallinity of the
PET film surfaces were also increased[1]. In
addition to this the low pressure O2 plasma
treatment can be created the polar groups of
carbonyl, carboxyl and hydroxyl on the
surface of low density polyethylene (LDPE)
film. The appearance of these polar groups
contributes
to
increasing
of
the
hydrophilicity of the LDPE film[2].
Furthermore, the N2 and O2 plasmas can
increase the hydrophilicity of PSF membrane
as well. This phenomena will help to
decrease the fouling while increasing the
waste gases flux treatment of PSF membrane
[4,6]. The contact angle of modified polymer
films will decrease or increase depends on
the type of working gas and plasma
treatment conditions[5]. Moreover, the
permeability of nitrogen (N2) gas through the
PSF membranes was affected by plasma
treatment in which ammonia (NH3) and
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Siam Physics Congress SPC2012

Past, Present and Future of Physics 9-12 May 2012

Materials and Methods

Two types of PSF polymerfrom the different
vendor were used in this work. The first one is
commercial PSF in the flat sheet membrane
(UltrasonS3010 NAT) was supplied
from
BASF, German and the second one is pellet of
PSF (UdelP-3500 LCD MB) from Solvay,
China.In the preparation of PSF flat sheet
membrane, pellet of PSF was dried at the
temperature of 95oC for 24 h. After that it was
dissolved in dimethylacetamide (DMAc) at the
temperature of about 60 oC for 20 h. The
resulting viscous solutions were casted on the
clean glass plate, exposure to the ambient air and
coagulated in the tap water for 12 h, respectively.
The samples with dimension of 714 square
centimeter were prepared for the plasma
treatment and then samples of different sizes
were cut for different testing.
The dc glow discharge plasmas were
generated in the vacuum chamber made of
stainless steel of internal diameter 25.4 cm and
length 38.1cm. Before generating the plasma, the
chamber was evacuated to a pressure of about
5.010-4 mbar. After that Ar and O2 gases were
fed through a needle valve untilpressure
reachedabout 3.510-1 mbar. Samples of PSF
membrane were placed in between parallel
electrodes as shown in Fig.1.The exposure time
was varies from 30 s and 5 to 30 min. The power
of plasma was controlled at about 15 W by
adjustment of electric potential. After plasma
treatment, the samples were suddenly weighed to
measure the etching effects on the surface of PSF
membranes. The plasma etching or degradation
can be evaluated from the weight loss which is
calculated by the following equation [1,3]:

(1)

where
and
are the weight of untreated
and treated samples, respectively.

DC Power supply

treated with 5 W of CF4 plasma for 15 minutes.

Afterward, the N2 permeation was increased[8].
These results were reflected to the competition
between pore size reduction and degradation
mechanisms due to the plasma [9].
The aim of this study is to demonstrate how
argon (Ar) and oxygen (O2) plasma treatments
alter the surface properties; morphology,
hydrophilicity, storage modulus and the
permeability of PSF membranes. Special
attention was paid for establishing the effects of
Ar and O2 plasmas to different type of PSF films.

( )

Vacuum chamber

carbontetrafluoride (CF4) are used as the

working gases. The permeation of N2 gas
was reduced when the PSF membranes is

Cathode

Membrane
samples
Anode

Rotary pump

Figure 1. The positioning of membrane sample in

DC plasma system
The water contact angle was measured using
the sessile drop method to estimate the
hydrophilicity of PSF membrane surface before
and after treatment. The surface energy of
untreated and treated membranes was calculated
by using the equation appeared in [1] through the
obtained contact angle of distill water and
diethylene glycol (DEG, surface tension 44.8
mN/m at 25 oC). The FTIR-ATR was used to
measure the creation of some functional group
on the sample surface. The morphology of PSF
films surface was disclosed by the SEM and
mechanical property changing of the samples
were measured by using the DMTA technique. In
addition, Nitrogen gas (N2) was used to evaluate
the permeability of the sample using permeation
test system. The permeability of the films was
calculated by the expression in [5]. Finally, the
samples of PSF films from the different sources
both in untreated and treated with plasma were
compared. The brief procedure of this work was
shown in the Fig. 2.
Sample of
PSF
membranes

Weighing

Expose to Ar and O2
discharge

Water
contact
angle

FTIR

DMTA

SEM

Gas
permeation

Figure 2.The brief procedure of this work.

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Siam Physics Congress SPC2012

Past, Present and Future of Physics 9-12 May 2012

Weight loss (%)

20.0
Oxygen
Argon

15.0

120
5 minutes
10 minutes
15 minutes

100
80
60
40

20

10.0

5.0
0.0
0.5

1.0 5.0 10.0 15.0 20.0 25.0

Treatment time (min)

Figure 3. The comparison of percent weight loss

of PSF membranes treated by O2 and Ar-plasma
vary with time.
120

Contact angle (o)

surface as a function of discharge power and

treatment time was increased. For the plasma
treatment of different PSF film from different
manufacturer as shown in Fig. 4, the total effect
of Ar-discharge on the surface of the film is not
difference.

Contact angle (o)

Results and Discussion

Figure 3 shows the changes in percent
weight loss obtained from equation (1) of plasma
treated PSF membranes. It was shown that the
weight loss is increased with the increasing of
treatment time. The percent weight loss of
membrane samples treated by O2-plasma is much
higher than Ar-plasma with the same treatment
conditions for both discharge power and
treatment time. This may due to the O2 is a
higher reactive molecule more than Argon gas.

Udel P3500 LCD MB

Ultrason S3010 NAT

100
80
60
40
0

10

15

20

25

30

Treatment time (min)

35

Figure 4. The variation of contact angle for PSF

film treated between 0 to 30 mins by15W of Ardischarge.
Fig. 4 and Fig. 5 show the variation of
water contact angle of PSF films for the different
treatment times and different power of
discharges. The contact angle was sharply
reduced from 100.89 for the virgin PSF to 56.05
degree for plasma treated film in the first short
treatment time. The alteration of PSF membrane
surface for a long plasma treatment time was
highly dispersed due to the competition between
pore size reduction and degradation mechanisms.
Normally, the surface energy of polymer film is
inversely proportional to the contact angle
[1,2,4]. Therefore, the surface energy from the
measured contact angle on the PSF membrane

10

20

Power of discharge (W)

30

Figure 5.The variation of contact angle of PSF

film treated with the power of 0 to 25 w of Ardischarge for 5, 10 and 15 minutes, respectively.
To investigate the effect of plasma to the
mechanical properties of polymer film, the film
sample both before and after plasma treatment
was tested with DMTA method. The DMTA is
one of the techniques that provided an
information about the changes occurring in the
polymer when its dynamic loading in the broad
range of temperature[10]. The results of DMTA
investigations of PSF film as shown in Fig. 6
shows that the storage modulus of plasma treated
membrane is decreased.
For the morphology of the untreated and
plasma treated PSF film as shown in Fig. 7, it
was found that the plasma take effect to the film
surface. The skin surface of non-porous film
(Ultrason S3010 NAT) was cracked after treated
with plasma, indicating the beginning of the
surface degradation. For the same discharge
power, some more crack were occurred when the
film is treated with O2-plasma according to the
result of the percent weight loss. Additionally,
the number of pore and pore size were reduced
for the porous PSF film (Udel P3500 LCD MB)
as shown in Fig.7(b). This is lead to the
reduction of gas permeation through the film for
the first short period of plasma treatment time.
Generally, the ability to separate some gas of
polymer membrane will increase if the
permeability is decreased. Therefore, the
separation value should be raised for the porous
PSF film treated with plasma in short time
period.

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Siam Physics Congress SPC2012

Past, Present and Future of Physics 9-12 May 2012

Acknowledgments
Financial supported from Thailand Center
of Excellence in Physics (ThEP) through the
Fellowship program to C. Yuenyao and T.
Chittrakarn is acknowledged. The authors wish
to thank the Department of Physics, Membrane
Science and Technology Research Center and
Prince of Songkla University for providing all
the infrastructure and facilities needed in this
experiment.

Figure 6. The courses of changes storage

modulus (SM) and loss tangent (LT) vs
temperature for PSF films.

(a) Ultrason S3010 NAT (from BASF, German)

(b) Udel P3500 LCD MB (from Solvay, China)

Figure 7. The comparison of SEM micrograph of
untreated (left) and treated (right) PSF film from
different commercial company
Moreover, the creation of functional
group on the membrane surface was measures by
FTIR technique. The comparison of spectrum
from virgin and plasma treated membrane
indicated that may have some functional group is
created on the membrane surface. However, it is
necessary to perform more experiment to identify
the type of functional group that is occurred on
the porous PSF film surface.
Conclusions
The results showed that the argon and
oxygen glow discharge plasmas are feasible to
modify the surface membrane sheet significantly,
especially on their physical properties.

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Past, Present and Future of Physics 9-12 May 2012

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