Surface & Coatings Technology 202 (2008) 5663–5667

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Formation of super-hydrophobic and water-repellency surface with

hexamethyldisiloxane (HMDSO) coating on polyethyleneteraphtalate
fiber by atmosperic pressure plasma polymerization
Young-Yeon Ji a,c, Yong-Cheol Hong b,c, Suck-Hyun Lee c, Sung-Dae Kim a, Sang-Sik Kim a,⁎
a
Center for Plasma Technology, Institute for Advanced Engineering, 633-2, Goan-ri, Baegam-Myeon, Cheoin-Gu, Yongin-Si 449-863, Republic of Korea
b
Plasma Laboratory, Odeur System Korea Co. Ltd., Shinyoung Royal Palace, 249-6, Nonhyun-Dong, Kangnam-Gu, Seoul 135-832, Republic of Korea
c
Department of Molecular Science and Technology, Ajou University, San 5, Wonchon-Dong, Youngtong-Gu, Suwon 443-749, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Available online 21 June 2008 It has been reported that plasma treatments are to modify surface properties of polymers such as adhesivity,
hydrophliicity and hydrophobicity. The plasma interaction with the surface produces modification of its
Keywords: chemical structure and morphology.
Coating
In this study, surface modification of polyester fiber with high water-repellency and super-hydrophobic was
Hexamethyldisiloxane (HMDSO)
carried out plasma polymerization coating. Polyester fiber with water-repellency was treated with
Polyethyleneteraphtalate fiber
atmospheric pressure middle frequency (MF) and radio frequency (RF) plasma system using Ar and
hexamethyldisiloxane (HMDSO). The Ar gas has been used as carrier gas. The plasma coated PET fiber of
HMDSO with water-repellency of 90 rating showed higher water-repellency than untreated PET fiber with
water-repellency of 0 rating.
The surface morphologies of plasma treated fiber were characterized by scanning electron microscopy (SEM).
The Fourier transform infrared (FT-IR) spectrometry analyzed the chemical composition of the polymer
surface.
© 2008 Published by Elsevier B.V.

1. Introduction and water-repellency coating [4,5]. Hence, an additional surface

modification is required to achieve the desired properties, while
The use of plasmas for surface modification and polymerization to maintaining the characteristics of the volume [6,7]. Especially,
deposit thin films are very attractive due to control over surface hydrophobic and water-repellency surface treatments of various
chemistry. The films deposited by plasma polymerization have a good substances are of great interest in recent years [8–10]. Among many
adhesion to the substrate, are pinhole free, and have mechanical and techniques that can be utilized for super-hydrophobic and water-
chemical stabilities. The plasma polymerization technique has also repellency treatment, plasma based processes have been widely
been employed conventionally to fabricate thin functional films that studied and developed [11–13]. To improve the super-hydrophobic
facilitate surface modification of materials [1–3]. When polymeric and water-repellency, coating material must be added to amplify the
materials are exposed to plasma, radicals are created in the polymeric hydrophobicity. It is known that chemical modification of artificial
chain. These radicals can initiate polymerization reaction when they materials using fluoropolymeric [14,15] coating induced wastewater
are in contact with monomers in a liquid or gaseous phase. Electrons and dioxin. However plasma polymerization of silicon compound is an
in plasma with a polymer surface generate radicals at the surface of environmentally friendly technology of surface modification for
the polymer through excitation of the polymer molecules. super-hydrophobic material.
As a result, a grafting polymer is formed on the surface of the In this study, the silicon compounds such as hexamethyldisiloxane
polymeric material. The produced film has ample range of prospective (HMDSO) and inactive gas argon (Ar) are used. The Ar gas is used as
applications in anticorrosive surfaces, electrical resistors, scratch the carrier gas of the monomer. Hexamethyldisiloxane (HMDSO) is
resistance coating, optical filters, properties, chemical barrier coatings one of the most common materials used for coating. This paper
demonstrates a manufacturable method for formation of super-
hydrophobic and water-repellency coating on a polyester fiber. The
water-repellency coating was produced by an in-line atmospheric
⁎ Corresponding author. Tel.: +82 31 330 7540; fax: +82 31 330 7113. middle frequency (MF) and radio frequency (RF) plasmas process
E-mail address: [email protected] (S.-S. Kim). using mixture of Ar gas and HMDSO liquid. The system does not

0257-8972/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.surfcoat.2008.06.151
5664 Y.-Y. Ji et al. / Surface & Coatings Technology 202 (2008) 5663–5667

Fig. 1. Schematic diagram of plasma coating system apparatus.

require any vacuum line and is operated in an in-line mode, not in a HMDSO was injected at approximately 0.017 lpm. In the atmospheric
batch mode. So it can be easily scaled up for application to large HMDSO–Ar plasma treatment for high water-repellency coating, two
substrate surfaces or continuous processing [16,17]. important parameters were the speed at which the sample was moved
under the plasma head and the treatment times. When the plasma
2. Experimental treatment speed was increased by more than 20 mm/s, we needed
more cycles of plasma treatments to get the water-repellency.
2.1. Plasma treatment But treated surface became like white layer when treatment time
increases above 30 times.
A schematic presentation of the plasma polymerization system is
shown in Fig. 1. The power electrode in Fig. 1 was connected to a 2.2. Material
13.56 MHz RF supply through an L-C matching unit (or a 25 kHz MF
supply) and was covered with a quartz tube as a dielectric. The 16 cm In this work, hexamethyldisiloxane (HMDSO) of Fig. 2 was
long and 1 cm wide slit in the ground electrode was machined for obtained from Aldrich (98% pure) and used as received. Pointfours
plasma evolution downstream. The gap between the quartz tube and Corporation provided the sample of polyester fiber (polyester 92%,
the ground electrode was 1 mm. The distance between the plasma spandex 8%). Argon was used as carrier gas (500 sccm) and a HMDSO
device and the sample was 2 mm. The atmospheric MF glow- (10 ml/h) was used as a reactive material.
discharge plasma system was connected to plasma generator (SOFTAL,
Germany) 25 kHz with a maximum power of 4 kW and atmospheric 2.3. Characterization methods
RF glow-discharge plasma system was connected to plasma generator
13.56 MHz with a maximum power of 1 kW. All of the samples in this The chemical composition of the PET fiber was characterized by
work were treated at the plasma power of 100–300 W, especially fourier transform infrared (FT-IR) spectroscopy (Nicolet Avatar 370)
200 W and at a speed of 20 mm/s. The plasma was generated in which is suitable for the collection of spectra in the range between 650
ambient air with argon gas supplied through a gas hole array. and 4000 cm− 1.
Introduction of argon gas flow was very important for uniform and Each spectrum with a resolution of 4 cm− 1 was recorded by 32
stable plasma generation within the capability of the RF power supply scans. The morphology of the surface was observed with scanning
used for the experiment. The central electrode was powered by a electron microscope (SEM, Philips XL-30 CP). The thermal character-
25 KHz MF source (4000 W maximum power). The MF and RF power ization of the plasma treated PET fiber was carried out by thermo-
source used to check a change of the inherent property such as gravimetric analysis (TGA) in nitrogen at a heating rate 10 °C/min with
damage of PET fiber after the plasma treatment. a TGA 2050 (TA instruments). The flow rate was maintained at 10 and
In this test, 1 liter per minute (lpm) argon was introduced for stable 90 cc/min for the balance part and the furnace area, respectively. In
discharge. Since the plasma was operated in a glow-discharge mode, it this case, the sample weighed about 100 mg.
could be directly applied to metallic substrates, in addition to non-
conducting substrates without arc or streamer. HMDSO (98%, Aldrich)
was maintained at 100 °C and was bubbled by 0.1 lpm argon. And then
Table 1
Water-repellency standard chart

Rating Evaluation
100 No sticking or wetting of upper surface
90 Slight random sticking or wetting of upper surface
80 Wetting of upper surface at spray points
70 Partial wetting of whole of upper surface
50 Complete wetting of whole of upper surface
0 Complete setting of whole upper and lower surfaces
Fig. 2. Chemical structure of hexamethyldisiloxane.
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Fig. 3. Water-repellency test of (1) raw polyester, (a) HMDSO MF plasma coated polyester for (2) 10 times, (3) 15 times, (4) 20 times and (b) HMDSO RF plasma coated polyester for (2)
10 times, (3) 15 times, (4) 20 times.

2.4. Water-repellency test treatment passes increased, on the other hand, the ratings increased
from 50 to 90.
To measure the water-repellency of plasma coating, test was The water-repellency test presented in Fig. 3(b) shows differences
performed according to American Association of Textile Chemists and of plasma treated fiber and untreated fiber. Untreated polyester fiber
Colorists (AATCC). Generally, the AATCC spray test uses a set small expressed water-repellency test of 0 rating. In contrast, plasma coated
quantity of water placed about four inches over a fabric. The fabric is polyester fiber improved water-repellency class from 0 to 90 rating
set at a 45° angle to the stream of the liquid. The liquid is then allowed follow to AATCC 22 standard test. The reason of this result is that
to gravity feed through a standardizer spreader nozzle. The duration super-hydrophobic surface was formed by silicon compounds with
of exposure is about 30 s at a glancing angle 45° to the fabric. A visual HMDSO plasma treatment. The silicon compounds coated PET fiber
rating of how well the water beads up, based on a scale of 100 points, showed the water-repellency property.
is given to the fabric. Evaluation is accomplished by comparing the The FT-IR spectra of HMDSO-coated PET fiber are shown in Fig. 4.
wetted pattern with a standard chart of Table 1 [18]. The peak attributed to Si–O–Si bonds appeared at around 1080 cm− 1.
The peaks around 1030 cm− 1 are attributed to Si–O–C. The Si–(CH3)2
3. Results and discussion and Si–C was assigned at 790 cm− 1 and 851 cm− 1, respectively [19].
It can be noticed that, increasing the time of exposure in plasma,
The water-repellency on PET fabrics was obtained from the MF and there is an increase of Si–O–Si, Si–(CH3)2 and Si–C bonds relatively to
RF HMDSO plasma coated fibers treated for 20 passes. untreated PET fiber. The contents of silicon compounds were
The case of the MF plasma in Fig. 3, before the plasma treatment, increased by plasma treatment time of long term. But fiber surface
water-repellency test on PET fiber was less than 50 rating. The water- was covered with white powder when plasma treatment was done
repellency did not change noticeably for samples treated with one more than 30 times. Also, inherent peak of PET fiber was decreased by
pass. Sample treated 15 times with the plasma started showing HMDSO plasma. The peak of aromatic C–H (730 cm− 1), O–CfO
water-repellency test of 70 rating and treated over 20 times with (1250 cm− 1) and ester CfO (1750 cm− 1) little decrease and the peak at
water-repellency test of 90 rating. As shown in Fig. 3(a), the PET fiber 1350 cm− 1 and 1410 cm− 1 sign to the aliphatic C–H substantially
without plasma completely absorbed sprayed-water. As the plasma decreased relatively to untreated PET. We postulated on the basis of
FT-IR results that fragmentation mechanism of HMDSO and reaction
mechanism between PET and HMDSO by plasma. From generated

Fig. 4. FT-IR spectra of HMDSO-coated polyester fiber (a) raw material, plasma coated
fiber of HMDSO for (b) 15 times and (c) 20 times. Fig. 5. Fragmentation mechanism of the HMDSO.
5666 Y.-Y. Ji et al. / Surface & Coatings Technology 202 (2008) 5663–5667

Fig. 6. Reaction mechanism between PET and HMDSO by plasma.

electron by plasma process, fragmentation of the monomer was

suggested by M. Goujon [20]. The Si–O bond (8.3 eV) is broken by
high-energy electron collisions. Also, Si–C (4.5 eV) and C–H (3.5 eV)
bonds are broken by lower energy electrons (Fig. 5).
The C–H radical groups were generated by plasma at fiber surface,
because chain scission of PET took place [21] through in order from
low dissociation energy to high dissociation energy (C–H (3.5 eV), C–O
(3.7 eV), C = O (7.6 eV)). Consequently, the radical groups bonded to the
activated specious of HMDSO (Fig. 6).
The change of the PET surface morphology is mainly caused by the
bonding of activated species and depends on the plasma condition in
coated processes using HMDSO. Plasma coated fiber showed white
layer such as silicon compound in Fig. 7. And these white layers were Fig. 8. EDS analysis of (a) non-coated polyester, (b) plasma coated polyester of HMDSO
analyzed by EDX to confirm whether these are silicon compounds or for 20 times.
other compounds. The EDS results of Fig. 8, the Si content of plasma
coated PET fiber were 20% higher than that of untreated PET fiber temperature for 10% mass loss through TGA analysis of Fig. 9. These
(Table 2). In the SEM image of Fig. 7, we confirmed white layer such as data were compared with those for raw PET. Raw PET fiber and RF
silicon compounds. The inherent property of PET fiber investigated plasma treated PET fiber showed temperature for 10% mass loss in the

Fig. 7. SEM image of (a) non-coated polyester, (b) plasma coated polyester of HMDSO for 20 times.
 Y.-Y. Ji et al. / Surface & Coatings Technology 202 (2008) 5663–5667 5667

Table 2
EDS results of HMDSO plasma coated PET

Atom Untreated PET (wt.%) Plasma coated PET (wt.%)

Si 4.05 24.18
Au 95.95 75.82

TGA curve at about 378 °C, but MF plasma treated PET fiber caused to
temperature for 10% mass loss in the TGA curve at about 363 °C, which
the RF plasma do not change the inherent property of the fiber as
compared with the MF plasma. A much-increased amount of non-
volatile residue was observed at 700 °C for the MF and RF HMDSO
plasma coated fiber, compared with the untreated PET fiber. We
postulated that the increase in the non-volatile residue of HMDSO-
coated PET fiber from the interaction of HMDSO with PET. That is, Si
compounds were coated by HMDSO plasma treatment on PET fiber.

4. Conclusions Fig. 9. TGA thermograms scanned at a heating rate of 10 °C/min under nitrogen; (a) raw
polyester, (b) MF plasma treated polyester of HMDSO for 20 times and (c) RF plasma
treated polyester of HMDSO for 20 times.
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atmospheric MF and RF plasma of HMDSO. Such improvement was
attributed to the introduced silicon atoms on the fiber surface or a
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