Sensors and Actuators B 120 (2007) 719–723

Fabrication of long-term hydrophilic surfaces of poly(dimethyl siloxane)

using 2-hydroxy ethyl methacrylate
Dhananjay S. Bodas, Chantal Khan-Malek ∗
FEMTO-ST/Department LPMO CNRS UMR 6174, 32 Av. de l’Observatoire, Besançon 25044, France
Received 16 January 2006; received in revised form 9 March 2006; accepted 24 March 2006
Available online 2 May 2006

Abstract
In the present work, 2-hydroxy ethyl methacrylate (HEMA) was used to modify surface of poly(dimethyl siloxane) (PDMS) elastomer. Fourier
transform infrared spectroscopy (FTIR) and wetting angle measurements were used for the analysis of modified surface and hydrophilic stability
of PDMS. Results of the surface reconstruction reveal that long-term hydrophilic surfaces of PDMS can be achieved by use of HEMA.
© 2006 Elsevier B.V. All rights reserved.

Keywords: PDMS; Surface modification; Contact angle measurements; Hydrophilicity

1. Introduction have appeared on tailor-made permanently hydrophilic surfaces

The polymer with different properties at its surface is lately
one of the most popular areas of research in polymer chemistry
[1–3]. Amongst all the techniques of surface modification, func-
tional group implantation using plasma grafting [4] has emerged
to be the most rational alternative due to many obvious advan-
tages including uniform and controlled modification. However,
it is often reported that hydrophilic functionalities generated at
the polymer interface as a result of plasma grafting are temporary
and are lost with storage time [5–7]. This phenomenon termed,
as ‘surface reconstruction’ is the major drawback associated
with this technique. Surface dynamics leading to hydrophobic
recovery depends on many factors like polymer physio-chemical
properties, temperature, storage time and is therefore, a feebly
understood complex phenomenon, which differs from one sub-
strate to another [8,9]. The hydrophobic recovery is determined
by an increase in the water contact angle, the rate of which varies
with the nature of polymer.
The loss of surface functionality with time is the major
concern of the researcher working in the area of surface modi-
fication. Although, there are a large number of reports on the
surface modification of polymers [10], only a few of them
∗ Corresponding author. Tel.: +33 381 853 999; fax: +33 381 853 998.
E-mail addresses: dhananjay.bodas@gmail.com (D.S. Bodas),
chantal.khan-malek@lpmo.edu (C. Khan-Malek).
[11–14]. The report presented here is a part of our study aimed at
fabrication of permanently hydrophilic surfaces via controlled
grafting of HEMA. It is well known that exposure of poly-
mer film to plasma conditions leads to degradation and surface
cross-linking [15,16]. Taking the advantage of the drawbacks of
cross-linked surfaces, we have accomplished deliberate cross-
linking of HEMA onto the PDMS surface.
Poly(dimethyl siloxane) (PDMS) elastomer is the most
widely and one of the most versatile material used in the con-
struction of microfluidic devices, in particular for rapid pro-
totyping. One of the reasons for the popularity of PDMS is
the particularly straightforward manufacturing methods. PDMS
has essential characteristics like, it is elastomeric, can be opti-
cally transparent, is chemically inert, is permeable to gases and
amenable to fabrication via rapid prototyping [17,18]. However,
in spite of the many advantages of PDMS, the surface of PDMS
is naturally hydrophobic and cannot be used as it is for a variety
of applications. A number of efforts have been made to mod-
ify the surface of PDMS micro channels, in order to enhance
hydrophilicity and EOF which limit its applicability for analyt-
ical devices.
In the present study, functional HEMA monomers were spin
coated onto the surface of the PDMS and exposed to the oxygen
plasma to obtain long-term hydrophilic surfaces with a cross-
linked network of grafted monomers. Surface reconstruction
was studied as a function of storage time under ambient con-
dition upon storage. All the samples are analyzed using surface

0925-4005/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.03.037
720 D.S. Bodas, C. Khan-Malek / Sensors and Actuators B 120 (2007) 719–723

sensitive technique like FTIR spectroscopy and contact angle Table 1

measurement. The results of the graft density (Gd ) and contact angle measurements (θ) of
HEMA coated on pure PDMS and pretreated PDMS sample

2. Experimental Sample Gd (mg/cm2 ) Θ (◦ )

HEMA on pure PDMS 0.123 10

A 2-component PDMS from Dow Corning (SYLGARD 184)
with a 10:1 base to curing agent mixing ratio was used. The two
components were thoroughly mixed and degassed in vacuo to
remove bubbles. The mixture was cured at a 100 ◦ C for 1 h.
The process involved a monomer HEMA, commercially
available from Aldrich Chemicals. The surface modification
was conducted in two ways. Firstly, HEMA was spin coated
on pristine PDMS at a spin speed of 1500 rpm for 15 s (thick-
ness ∼600 nm). The HEMA-coated PDMS was then treated with
oxygen plasma at a constant pressure of 100 ␮barr at an oxy-
gen flow rate of 20 sccm. RF power was maintained at 100 W
for 5 min. All plasma treatments were carried out in a Plassys
reactive ion etching (RIE) system using an RF power supply
of 13.56 MHz frequency coupled via a matching network for
the plasma excitation. A capacitive coupling was used for the
plasma excitation.
In the second process, oxygen modification of PDMS was car-
ried out at a system pressure of 100 ␮barr and flow rate 20 sccm,
and an RF power of 100 W was used for 30 s for the modifi-
cation. HEMA was then spin coated onto the oxygen modified
PDMS surface at a spin speed of 1500 rpm for 15 s (thickness
∼600 nm). The HEMA-coated PDMS was finally treated with
oxygen plasma at a constant pressure of 100 ␮barr at an oxygen
flow rate of 20 sccm. RF power was varied from 50 to100 W
with a time variation of 1–5 min.
ATR-FTIR spectra were recorded using a Nicolet 5-PC FTIR
spectrometer to assess the changes on the surface after differ-
ent modifications. The FTIR spectra were recorded within 5 min
of surface modification. Graft density (Gd ) was defined as the
difference in the film weight before and after grafting divided
by the total surface area of the film. The sample dimensions
for graft density measurements were 2.54 cm × 1 cm. All the
samples were also characterized for hydrophilic stability using
contact angle measurements. In present study, a manual con-
tact angle measurement setup was used having an error of ±2◦ .
Deionized water droplet (2 ␮L) was delivered on the PDMS
surface by a calibrated syringe. The static contact angles were
measured before and after modification, as well as a function
of time within the time interval of 0–12 h, every 5 min at the
beginning and every hour thereafter.
HEMA on pretreated PDMS 0.153 7
on pretreated PDMS generates better hydrophilicity compared
to HEMA coated on pristine PDMS (parameters used for plasma
treatment are: RF power 100 W at 5 min treatment time). This
is due to higher content of hydroxyl groups attached to the film
for HEMA coated on pretreated PDMS.
3.1. ATR-FTIR
The presence of surface anchored HEMA onto the PDMS film
for pretreated PDMS is evident from the ATR-FTIR spectrum in
Fig. 1b. Fig. 1a gives an ATR-FTIR spectrum for pristine PDMS
for comparison. Also, ATR-FTIR spectrum for HEMA coated
on pristine PDMS in Fig. 1c. These samples of HEMA coated
on pristine PDMS and HEMA coated on pretreated PDMS are
treated at plasma power of 100 W for 5 min. The presence of
hump from 3200 to 3600 cm−1 in Fig. 1b and Fig. 1c indicates
hydroxyl group of HEMA. The hump in case of Fig. 1a is of
lower intensity compared to that in Fig. 1c indicating surface
anchored HEMA. The vibrational frequencies corresponding to
1710 cm−1 (O C O) and 1163 cm−1 (1◦ alcohol) are evident
in Fig. 1b. Fig. 1c shows vibrational frequency corresponding to
O C O at 1720 cm−1 [19–23]. Peak corresponding to 1◦ alco-
hol is missing in Fig. 1c indicating that pretreatment of PDMS
facilitates bonding between two surfaces. Also a shift in peak
intensity is observed in the two spectra for HEMA coated on

3. Results

HEMA grafted onto the surface of PDMS is substantiated

by gravimetric analysis, the contact angle measurements and
ATR-FTIR. The results of the gravimetric analysis, graft den-
sity (Gd ) and contact angle measurements (θ) are compiled in
the Table 1. The gravimetric analysis reveals that the anchoring
of HEMA is more efficient when PDMS has been pre treated in
oxygen plasma. This is due to formation of silanol bonds on the
PDMS surface which facilitate attachment of HEMA. It is obvi- Fig. 1. ATR-FTIR spectra for (a) pristine PDMS, (b) HEMA coated on pretreated
ous from the contact angle measurements that the HEMA coated PDMS (c) HEMA coated on pristine PDMS.
 D.S. Bodas, C. Khan-Malek / Sensors and Actuators B 120 (2007) 719–723
pristine PDMS (1720 cm−1 ) and HEMA coated on pretreated
PDMS (1710 cm−1 ). Presence of peak at 1163 cm−1 and a shift
of peak at 1710 cm−1 from standard indicated reconstruction
in HEMA on PDMS surface. This might be thought as cross-
linking of HEMA functional monomer on the surface of PDMS.
Moreover, the pendent segments in pretreated PDMS undergo
cross-linking with HEMA under the influence of plasma, a pro-
cess similar to the vulcanization of rubber. To substantiate our
Fig. 2. Graph of water contact angle vs. aging time with plasma power and
exposure time for HEMA coated on pretreated PDMS.
721
claim we have carried out surface reconstruction of the both the
PDMS films.
3.2. Contact angle measurements
Contact angle measurements were carried out for HEMA-
coated on pretreated PDMS film with variation in oxygen plasma
parameters. Plasma power was varied from 50 to 100 W and
treatment time was varied from 1 to 5 min. Contact angles were
measured after 5 min interval for 1 h to study aging effect of
the film in clean room atmosphere. Fig. 2 shows a graph of
variation of contact angle with aging time for various treatment
parameters. It is clear from the graph that as the plasma power
or treatment time is increased lower contact angle is obtained.
Hydrophilic stability is also improved with increase in plasma
power and treatment time. Increase beyond 100 W plasma power
produced rough film surface which can be visible visually. Also
increase in treatment time beyond 5 min does not improve the
hydrophilic stability any further. Hence, plasma power of 100 W
and treatment time of 5 min was optimum parameters for treat-
ment of HEMA coated on pretreated PDMS. Fig. 3 shows a
graph of contact angle versus aging time for HEMA-coated on
pristine PDMS and HEMA-coated on pretreated PDMS sam-
ples. The oxygen plasma parameters for both the treatments are
kept same (100 W plasma power for 5 min). The contact angles
were recorded after 5 min interval initially and after every hour
later till 12 h. Similar measurements were carried out on same
film till 2 weeks. For comparison, contact angle data for pristine
PDMS and that for O2 plasma modified PDMS are given. The O2
plasma treatment has been carried out in a reactive ion etching
(RIE) system at system pressure 100 ␮barr, plasma power 150 W
for 15 min at oxygen flow rate of 20 sccm. It can be clearly seen
from the graph that HEMA-coated on pretreated PDMS sam-
ple has more hydrophilic stability than that of HEMA-coated
on pristine PDMS as well as that of O2 plasma treated sample.
Similar study has been reported by Choi and Yang [23] for Syl-
gard PDMS. They have used spin coated HEMA on pretreated
PDMS. They have carried out post baking of HEMA on a hot
plate at various temperatures. In the present study no post baking
Fig. 3. Graph of water contact angle vs. aging time for various different treat-
ments.
722 D.S. Bodas, C. Khan-Malek / Sensors and Actuators B 120 (2007) 719–723

Table 2 clean room atmosphere was monitored by the changes in water

The results contact angle measurements (θ) of HEMA coated on pure PDMS
and pretreated PDMS sample after aging
Sample
HEMA on pure PDMS (◦ )
HEMA on pretreated PDMS (◦ )
contact angle, the values of which are complied in Table 2. The
decrease in surface hydrophilicity is a common symptom if sur-
12 h 24 h 1 week 2 weeks face instability is encountered after reactive plasma treatment,
36 40 65 86 which is due to the mobility of polymer chains and dynamic
20 26 41 49 nature of the surface. This phenomenon is common in case of
elastomers on account of their exceptional flexibility, PDMS in
particular. Here, the oxygen plasma treated films demonstrate
a very high degree of hydrophobic recovery which has been
reported extensively in the literature, whereas HEMA coated
on pretreated PDMS shows little amount of reconstruction.
As reported, use of higher plasma powers hardly shows any
improvement in surface reconstruction, whereas longer expo-
sures to plasma cause surface erosion. An SEM micrograph was
recorded at a power 150 W for 10 min exposure and 100 W power
for 20 min plasma exposure (shown in Fig. 4a and b) to show
this effect.
The behavior of HEMA coated film is mainly due to the
cross-linked network at the surface, which does not permit the
orientation/free mobility of the grafted polymer chains bearing
functional groups. A very small hydrophobic recovery in HEMA
coated samples may be due to the free rotation of the functional
groups generated on the grafted polymer chains due to the reac-
tive plasma.

5. Conclusion

The surface modification of Sylgard 184 PDMS was studied

Fig. 4. SEM of HEMA coated on PDMS at (a) 150 W plasma power for 10 min
exposure and (b) 100 W plasma power for 20 min exposure to plasma.
in terms of hydrophilic stability using HEMA modification. The
study shows in particular the possibility of grafting long-term
stable hydrophilic functional groups onto PDMS using oxygen
plasma induced polymerization of HEMA. HEMA-coated on
pretreated PDMS shows excellent hydrophilic stability. Aging
for 2 weeks in clean room atmosphere shows increase in con-
tact angle from 7◦ (just after treatment) to 49◦ . HEMA-coated
on pristine PDMS recovers in 2 weeks to its original hydropho-
bicity. The contact angle value measured after 2 weeks is 86◦ .
This is due to free rotation of the functional groups generated
on the grafted polymer chains due to the reactive plasma. These
results may find use in the construction of microfluidic devices
with PDMS as it increases the time available for sealing e.g.
cover and channels, confers superior wetting properties to the
microchannels that facilitate channel filling, and may prevent
bio-fouling.

conditions are used after spin coating HEMA on pretreated or

pristine PDMS samples. Acknowledgements

4. Discussion Dr. M. Fromm (LMN, Besançon) and Dr. J. Takadoum

Attempts have been made in past to fabricate long-
term hydrophilic surfaces by covalent grafting of functional
monomers, however, uncertainty still prevails in locating the
functional groups at the interface, since they migrate below the
grafted homopolymer chains to attain a minimum free energy
state. In the present study, surface reconstruction upon aging in
(ENSMM, Besançon) are respectively thanked for the help with
recording FTIR spectra and for lending the contact angle mea-
surement apparatus.
The work was performed within the framework of the 4M
Network of Excellence “Multi Material Micro Manufacture:
Technology and applications (4M)” (EC funding FP6-500274-1;
www.4m-net.org).
 D.S. Bodas, C. Khan-Malek / Sensors and Actuators B 120 (2007) 719–723
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Biographies
Dhananjay S. Bodas is currently working as a Research Scientist in Insti-
tute of Bioengineering and Nanotechnology (IBN), Singapore. He did his
postdoc from FEMTO-ST/Department LPMO, Besançon, France. Currently
he is working on a biochip for gene synthesis using rapid prototyping tech-
niques on various polymer substrates. His interests include micro–nano-
contact printing for local surface modification, surface and interface physics
and micro–nano-fluidics for biological applications using softlithographic
techniques.
Chantal Khan-Malek, a physical chemist by training, is a senior scientist at
the National Center of Scientific Research (CNRS), France. Her research inter-
ests are in micro- and nano-materials science and engineering and her research
expertise includes micro- and nano-manufacturing technologies. After exploring
the limits of X-ray nanolithography on synchrotron radiation at Bagneux and
Orsay (France), she pioneered the manufacture of advanced optics for X-ray
and EUV, then applied X-rays to the manufacture of high-aspect-ratio microsys-
tems, in Germany (Mainz) and in US (Berkeley and Baton Rouge). Her present
focus is on the development of a polymeric platform for microfluidic-based sys-
tems, with particular emphasis on replication technologies for biocompatible
and biodegradable polymers for biological and biomedical applications at the
FEMTO-ST Institute/Department LPMO in Besançon, France. FEMTO-ST is
a new organizational entity of approximately 350 people which encompasses
already existing research labs in the Franche-Comté region in the fields of
Information Science and Technology as well as Engineering Sciences, with,
in particular, activities in the field of microsystems and micro- and nano-
technology.