Adv Funct Materials - 2009 - Kim - Solvent Resistant PDMS Microfluidic Devices With Hybrid Inorganic Organic Polymer

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Solvent-Resistant PDMS Microfluidic Devices with

Hybrid Inorganic/Organic Polymer Coatings
By Bo-Yeol Kim, Lan-Young Hong, Young-Min Chung, Dong-Pyo Kim,* and
Chang-Soo Lee*
using conventional microfabrication techni-

This study presents a method for the fabrication of solvent-resistant ques, such as photolithography, etching, and
micromachining.[1,3] However, these techni-
poly(dimethylsiloxane) (PDMS) microfluidic devices by coating the
ques are expensive and require clean rooms,
microfluidic channel with a hybrid inorganic/organic polymer (HR4). This intensive labor, and complicated procedures.
modification dramatically increases the resistance of PDMS microfluidic Alternatively, soft lithography has been
channels to various solvents, because it leads to a significant reduction in the proposed to solve those issues because soft
rate of solvent absorption and consequent swelling. The compatibility of materials can provide easy fabrication, cost-
modified PDMS with a wide range of solvents is investigated by evaluating the effective processing, and rapid manufactur-
ing of actuators containing valves, pumps, or
swelling ratio measured through weight changes in a standard block. The
mixers.[4,5] Among several soft materials,
HR4-modified PDMS microfluidic device can be applied to the formation of poly(dimethylsiloxane) (PDMS) is one of the
water-in-oil (W/O) and oil-in-water (O/W) emulsions. The generation of most useful materials for a wide range
organic solvent droplets with high monodispersity in the microfluidic device of applications including microfluidic
without swelling problems is demonstrated. The advantage of this proposed devices, biosensors, and unconventional
lithography. It has several advantages,
method is that it can be used to rapidly fabricate microfluidic devices using
such as chemical stability, porous structure,
the bulk properties of PDMS, while also increasing their resistance to various transparency, easy fabrication, low
organic solvents. This high compatibility with a variety of solvents of cost, and commercial availability.[5] However,
HR4-modified PDMS can expand the application of microfluidic systems to PDMS poses a critical problem of swelling
many research fields. in common organic solvents.[6] This
induces deformation, distortion, or even
collapse of the microfluidic channels,
and thus leaching of uncured monomers and oligomers
and leakage from the microfluidic channels may occur.[7–9]
Therefore, it is difficult to perform many organic reactions and/
or solvent- based material syntheses in PDMS-based microfluidic
1. Introduction systems.
To solve these problems, there are several reports on the
There has been a rapid expansion of microfluidic systems since fabrication of solvent-compatible microfluidic devices.[7–13] Those
the first miniaturized gas chromatography equipment was methods are classified using two main approaches. One is the use
developed around 1975.[1,2] Early generations of microfluidic of new solvent-resistant materials.[9–12] For example, microfluidic
devices were fabricated mainly from silicon, glass, and quartz devices can be made from photocurable teflon, thiolene, or
preceramic polymers. The other approach involves the use of
[*] Prof. C. S. Lee, B. Y. Kim surface modification of the PDMS microfluidic channels with
Department of Chemical Engineering solvent-retarding and solvent-resistant materials such as teflon,
Chungnam National University poly(urethaneacrylate), or silane compounds.[7,8,13–15] Although
Daejeon 305-764 (Korea) the modification of PDMS with a thin teflon film to provide easy
E-mail: rhadum@cnu.ac.kr
handling has been reported, teflon does not adhere well to the
Prof. D. P. Kim, Dr. L. Y. Hong
Department of Applied Chemistry PDMS layer because of its very low surface energy, therefore such
Chungnam National University surfaces have a difficulty in bonding when the modified substrate
Daejeon 305-764 (Korea) is used to make microfluidic devices.[13] It is also difficult to obtain
E-mail: dpkim@cnu.ac.kr a good resistance against strongly hydrophobic organic solvents
Dr. Y. M. Chung through the modification of PDMS with poly(urethaneacrylate),
SK Energy
Daejeon 305-712 (Korea)
because polyurethane can easily swell in a number of organic
solvents.[8] With regards to applying a silane coating to the PDMS
DOI: 10.1002/adfm.200901024 microchannel,[7] a limited control existed over the thickness of the
3796 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2009, 19, 3796–3803
16163028, 2009, 23, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.200901024 by Technion-Israel Institution Of Technology, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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silane compounds after polymerization, and the channel shape 2. Results and Discussion
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was changed from rectangular to round because the sealed
microchannel was purged with air to remove unreacted 2.1. Surface Modification of PDMS
compounds. Moreover, the fabrication of extended microchannel
lengths with complicated designs, such as channels that are several
tens of centimeters long, was difficult to achieve because of the We used HR4 for the stable surface modification of PDMS because
required pressure resistance. Abate et al.[7] utilized a preconverted it is a promising hybrid material that is capable of rapid
gel that contained a relatively low amount of water (molar ratio of polymerization using photocuring or thermal curing. Moreover,
[H2O]/([TEOS] þ [MTES], TEOS ¼ tetraethylorthosilicate, METS ¼ it is optically transparent, formed by simple covalent bonding with
methyl triethoxysilane) around 5.0). This low water addition, a silanol group, liquid at room temperature, and thermally stable.
compared to the 10 to 20 times molar excess of water for general Surface modification of PDMS involves oxygen-plasma treatment,
sol–gel silica reactions, might produce insufficiently condensed bonding of HR4 onto the treated PDMS surface under UV
silicate network structures. Moreover, the coating films generally irradiation, followed by full polymerization of the coated HR4
are further condensed by the long-term exposure to moisture in using thermal curing (Fig. 1A,B). Chemical modification of the
the ambient air, which results in low durability because of PDMS surface involves linking of the silanol groups in HR4 with
shrinkage, crack formation, or delamination. In particular, those the silanol groups on the PDMS surface under UV irradiation.
problems are more apparent in the case of thick sol–gel derived To confirm our modification of the PDMS surface, both pristine
silica films. In addition, although the method is performed using and modified PDMS samples were investigated by contact-angle
rectangular microchannels, it always produces more circular measurements, Fourier transform infrared (FT-IR), and scanning
cross sections within the microchannels, because the silane electron microscopy (SEM). Contact-angle measurements were
compounds are filled into the corners during polymerization. used to compare the surface property of the modified PDMS with
Surface modification of PDMS, however, remains a promising the surface characteristics of the original PDMS and of HR4 on
technique if we could retain the desired bulk properties of PDMS glass. The measured contact angles are shown in Table 1. The
for mass-processing purposes.[7,8,13] In addition, little actual contact angle of PDMS modified with HR4 (65.1 0.88) lies
experimental data can be found that deals with solvent between that of an unmodified PDMS surface (106.9 0.4) and
resistance, although two main approaches have been well that of an HR4 surface on glass (42.4 0.58) and indicates a weak
established. Droplet-based microfluidic systems and digital hydrophilicity. PDMS microfluidic devices with strong hydro-
microfluidic systems as upcoming areas of microfluidic phobicity tend to trap air bubbles easily when filled with water as a
applications are attractive because they provide discrete and carrier fluid and these are difficult to eliminate from the
distinct volumes of fluids in the continuous phase of an microchannels.[6] Thus, in the case of PDMS microfluidic
immiscible liquid.[2,16] Unlike continuous microfluidic channels modified with HR4, the problem of air trapping is
systems, each droplet can be controlled independently by alleviated because the modified PDMS demonstrates a weakly
transportation, mixing, merging, reaction, and analysis.[2,10,17] hydrophilicity. Although hydrophilic PDMS surfaces have been
Also, these systems can be used as discrete microreactors for obtained before by simple plasma pretreatment, this hydrophi-
performing various chemical reactions such as micro/nano- licity disappears within a few hours. However, a stable coating of
particle synthesis, bromination, hydrolysis, and precipita- HR4 onto PDMS preserves the modified surface properties
tion.[18] In addition, multiparallel processing and integration without any deterioration for six months even if the modified
are both possible because multiple identical and homogeneous PDMS blocks are stored under ambient environmental
droplets are formed in a short time to increase throughput conditions.
and efficiency.[19,20] Thus, the fabrication of solvent-resistant Figure 2 shows FT-IR spectra of a PDMS, inherent HR4, and a
microfluidic devices is a prerequisite for the formation of modified PDMS sample. The pristine PDMS shows characteristic
organic droplets if we are to realize droplet-based chemical peaks of symmetric stretching, asymmetric stretching, and
reactions.[7,9] deformation vibrations of the methyl groups at 2963, 2906, and
We present here a simple and easy method for the stable surface 1258 cm1, respectively. Typically, methyl rocking and SiC
modification of PDMS using a solvent-resistant organic/inorganic vibrations appear at around 800 cm1, while asymmetric stretch-
hybrid material (HR4) to provide solvent compatibility, while the ing vibrations of SiOSi emerge between 930 and 1200 cm1.[22]
inherent bulk properties of PDMS are retained for the rapid In the case of HR4, the FT-IR spectrum shows a distinctive peak at
prototyping of microfluidic devices.[21] First, the PDMS surface 950 cm1 corresponding to the SiOTi stretching vibration,
was treated with oxygen plasma to produce a silicate layer and which indicates the generation of a hybrid phase (SiOTi) with a
then it was reacted with HR4 using covalent siloxane coupling. direct bond between two metalloxanes during the synthesis of
Thermal polymerization of HR4 was then performed to improve HR4 resins.[23] In addition, the absorption peak at 1100 cm1
its rigidity. The proposed method provided a material with two corresponding to the SiOSi linkage caused by the condensa-
distinctive properties: a great reduction in swelling in response to tion of TEOS–3-mercapto-propyl-trimethoxy silane (MPTMS) is
solvents and a capacity for rapid generation of organic phase also detected.[24] By contrast, for the HR4-coated PDMS surface,
droplets in water-in-oil (W/O) and oil-in-water O/W emulsions. the overlapping SiOSi and SiOTi linkages produce a broad
Furthermore, we thoroughly investigated the solvent compatibility peak in the range of 880–1200 cm1. The characteristic peak of the
of the modified PDMS substrates with the measurement of vinyl group at 1560 cm1 in the HR4 solution disappears in the FT-
absorption rates and swelling properties against several organic IR spectrum of the HR4-coated PDMS surface. In addition, the
solvents. broad peak between 3050 cm1 and 3700 cm1 (OH stretching)
Adv. Funct. Mater. 2009, 19, 3796–3803 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3797
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results from combined OH stretching, including the

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SiOH stretching in the silica unit, the COH

stretching in the polyethyleneglycol (PEG) unit, and
the SOH stretching in the catechol salt (4,5-
dihydroxy-m-benzenedisulfonic acid, Tiron) in the
HR4 resin, and the SiOH stretching of PDMS after
treatment with oxygen plasma. These SiOH groups
between PDMS and HR4 play a role in binding of the
active sites and increasing the strength of adhesion
between PDMS and HR4. These results prove that the
HR4 hybrid materials are polymerized and covalently
bound to the PDMS surface successfully.
Finally, to confirm the surface coating with HR4
directly, SEM analysis was carried out on both
unmodified and modified PDMS surfaces. Figure 3
shows the SEM images of cross sections of unmodified
PDMS and HR4-treated PDMS. As expected, the HR4,
being a hybrid material, does not infiltrate into the
PDMS but binds onto the PDMS surface. The
thickness of the coated HR4 layer is about 1.5 mm.
Additionally, in contrast to the PDMS material, the
HR4 coating shows inherent strength and hardness,
as it is composed mainly of inorganic materials.
We found, however, that cracking of the HR4 layer on
the PDMS substrate occasionally occurred when the
thickness of the HR4 layer exceeded 10 mm. For thin
films of HR4, under 10 mm in thickness, we did not
observe cracking under our experimental conditions.
The phenomenon of cracking might be attributed to
residual stress between the soft PDMS and hard HR4
materials, because the magnitudes of strain in the two
substances are quite different. As with glass, HR4 has a
higher level of residual stress associated with the
inherent properties of inorganic materials. The main
substrate for the microfluidic device, however, consists
of flexible PDMS polymers exhibiting lower residual
stress; consequently, the possibility of cracks in the
HR4 film on a compliant PDMS substrate is much
higher than that of a stiffer substrate because of this
imbalance of residual stress levels.
2.2. Absorption Rates of Various Organic Solvents
The collapse and blockage of microfluidic channels are

related to the swelling of PDMS when organic solvents
are loaded. To clarify the effect of HR4 coating on
PDMS, we investigated the rate of absorption with
several kinds of organic solvents. Changes in PDMS
sample weights were measured sequentially with
Figure 1. A) Schematic diagram of the microfabrication of a microfluidic device. The solvents placed on unmodified and modified PDMS
surface modification sequentially consists of oxygen-plasma treatment for the increase of
for one hour, with both surfaces having identical
HR4 adhesion, spin-coating of HR4, selective removal of HR4 onto the bonding region
exposed surface areas. The initial absorption rates (a)
with wiping off along the microchannel, and oxygen-plasma treatment for bonding
between the PDMS region and glass substrate. B) PDMS surface modification with HR4 were calculated within 10 min because the absorption
for the investigation of solvent resistance. First, the PDMS surface was activated by rate of HR4-modified PDMS began to level off after
oxygen-plasma treatment. The HR4 was then spin-coated and linked with PDMS under 10 min, eventually reaching a plateau. Therefore,
UV irradiation, after which full thermal polymerization of the coated HR4 was performed. we need only consider initial absorption rates for the
C) SEM image of a cross section of the finished microfluidic channel. linear region to compare their solvent resistances
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Table 1. Comparison of water contact angle of PDMS and HR4-modified
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PDMS.
Sample Water contact angle [8]
PDMS 106.9 0.4

HR4 on glass 42.4 0.5
HR4-modified PDMS 65.1 0.8
between the PDMS and HR4-modified PDMS. The initial

absorption rate of the solvent can be calculated from zeroth-order
kinetics: [14,25]
@M
¼a (1)
@t
where M is the weight of the solvent absorbed by a given substrate

and a is the rate constant of absorption. The weight gain of PDMS
in toluene is shown in Figure 4 as an example, since toluene is
widely used in chemical synthesis and causes significant swelling
of PDMS. Toluene is absorbed more slowly by the HR4-coated
PDMS than by the unmodified PDMS substrate (Fig. 4). The
surface modification of PDMS with HR4 results in a clear
decrease of solvent absorption for all tested materials (Table 2).
Thus, the HR4-modified PDMS surface has the potential to
alleviate the swelling problems of microchannels caused by
solvent absorption.
To confirm the stability of these microfluidic channels, we
examined the swelling properties of the microfluidic channels with
and without HR4 surface modification. Because solvent resistance
can be easily confirmed by the swelling or deformation of the
PDMS microfluidic channels, we introduced a toluene solution
into both the unmodified and modified PDMS microfluidic
devices and analyzed time-lapse images of the shape of the
microfluidic channels for one hour. We observed narrowing of the
unmodified PDMS microfluidic channels, even when they had
Figure 3. SEM images of cross sections of A) a PDMS and B) an HR4-
coated PDMS microfluidic channel. The initial microchannel is about
200 mm (width) 100 mm (height). After being coated with HR4, the
microchannel is about 197 mm 98.5 mm, because the thickness of the
HR4 thin layer deposited onto the PDMS microfluidic channel is about
1.5 mm. The scale bar indicates 1 mm.
only been in contact with the solvent for 10 min (Fig. 5A). This can
be related to the swelling of the PDMS microfluidic channel, which
is driven by the absorption of solvent. The change in width of the
modified PDMS microfluidic channel during the same experi-
ment, however, is not as dramatic. This observation clearly
demonstrates the stable modification of PDMS with the HR4
hybrid materials resulting in solvent resistance. Also, in order to
determine the degree of chemical resistance of the HR4 surface
modification of PDMS, we investigated the diffusion of a solute
from an aqueous solution into the PDMS polymer. For a clear view
of the experiment, a rhodamine fluorescence dye was used as the
probing molecule of chemical resistance.[7] First, unmodified and
Figure 2. Fourier-transform infrared (FT-IR) absorbance spectra of PDMS, modified microchannels were loaded with a 50 mM aqueous
HR4, and HR4-coated PDMS. solution of rhodamine B. The microchannels were then stored in a
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2.3. Solvent Stability

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Investigating the solvent stability of the HR4-modified PDMS was

important to evaluate our proposed approach because the
stability of microfluidic devices and reproducibility of organic-
based droplet formation depend on the solvent resistance of
the materials used in fabricating microfluidic channels. When
investigating the relationship between the thickness of HR4
and solvent resistance, our preliminary study found that HR4
coatings on PDMS substrates that exceed 1.5 mm in thickness
showed a similar solvent resistance to that of plain HR4. Therefore,
we started by examining the solvent resistance of HR4 films of
1.5 mm in thickness.
To examine the effect of the solvent on the modified PDMS
surface, pristine PDMS and modified PDMS blocks were
investigated by measuring the swelling ratio over 12 h. To
minimize experimental errors, we measured the swelling ratios
of three different samples for each solvent. The average swelling
ratio determined for each solvent is given in Table 2, with an error
Figure 4. Measurement of the absorption of toluene by PDMS and HR4- of 3%.
coated PDMS. The inset graph shows the initial absorption rate within Solvents that penetrate polymers cause them to swell. As
10 min, indicating that the absorption rate of HR4-modified PDMS shows shown in Table 2, the PDMS substrate modified with HR4
good linearity.
shows a significant resistance against strongly absorbing
solvents including benzene, cyclohexene, THF, heptane, hexane,
toluene, triethylamine, pentane, chloroform, and trichloroethy-
dark room for 72 h and the water was allowed to evaporate. In the lene. In addition, these solvents do not induce cracking or
case of an unmodified PDMS microchannel, rhodamine B peeling of the HR4 coating layer. In polar solvents, including
diffused into the walls of the PDMS. Thus, the fluorescence water, methanol, dimethylsulfoxide (DMSO), ethanol, acetonitrile,
signal was detected only at the wall of the PDMS microchannel dimethylformamide (DMF), and acetone, pristine PDMS is
(Fig. 5B). In contrast, there was no diffusion into the walls of the found to be relatively compatible with all except acetone. The
modified microchannels. The fluorescence molecules remained modified PDMS surfaces are even more compatible with polar
on the surface of the microchannels, which clearly indicates that solvents as they cause little to no swelling. When PDMS
modification of the PDMS microchannels prevented the diffusion microchannels come into contact with a solvent that causes
of molecules (Fig. 5B). swelling, the solvent may extract non-crosslinked oligomers
Table 2. Swelling ratios of PDMS and HR4-modified PDMS in various solvents.
Solvents Absorption rate (a) Degree of swelling
PDMS [105; g s1] HR4–PDMS [105; g s1] PDMS [a] (D D01) PDMS [%] HR4–PDMS [%]
Water 0.00 0.00 1.00 0.00 0.00

Ethanol 0.25 0.24 1.04 1.50 1.70
DMSO 0.31 0.26 1.00 2.91 2.18
Methanol 0.35 0.11 1.02 2.30 0.77
Acetonitrile 0.46 0.79 1.01 5.04 3.45
DMF 0.93 0.68 1.02 6.18 4.73
Acetone 2.23 0.90 1.06 13.53 7.40
Benzene 6.64 2.35 1.28 43.62 15.42
Cyclohexene 7.18 2.44 1.33 46.80 15.69
THF 13.43 4.40 1.38 95.91 22.30
Heptane 13.73 5.97 1.34 101.33 37.61
Hexane 15.00 2.62 1.35 112.07 14.65
Toluene 15.68 2.55 1.31 114.96 9.76
Triethylamine 16.75 4.47 1.58 118.30 37.60
Pentane 16.61 5.70 1.44 123.73 34.29
Chloroform 18.67 4.22 1.39 127.52 33.10
Trichloroethylene 25.96 4.84 1.34 173.67 27.55
[a] Reference values of swelling ratio (D D01) of PDMS are as reported [12]. We calculated the swelling ratio of PDMS (%) using [(W–W0)/W0] 100 after
the loading of various solvents for 12 h. The sequence of solvents is arranged in order of the swelling ratio of PDMS for various solvents.
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2.4. Generation of Emulsion Droplets in
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Modified PDMS Microchannels
To demonstrate the feasibility of solvent-based

emulsion applications, we tested HR4-mod-
ified microfluidic devices for droplet genera-
tion in oil-in-water (O/W) and water-in-oil (W/
O) systems. The HR4-coated PDMS was shown
to be weakly hydrophilic (see before) because
the contact angle was about 65.1 0.88
(Table 1), which is suitable for the formation
of W/O emulsions. We easily produced emul-
sions using water as the dispersed phase and
toluene as the continuous phase in our
modified microfluidic device. Figure 6A indi-
cates that droplets of water in toluene are
generated successfully in our modified micro-
fluidic device. For an O/W emulsion, the
microfluidic device was used to generate
droplets of toluene in a continuous phase of
water. Because the HR4-modified surface is
weakly hydrophilic, we added sodium dodecyl
sulfate (SDS) into the continuous water
solution to stabilize interfacial tensions among
the microfluidic wall and the water and toluene
interface.[14,26] The toluene fluid was intro-
duced from the central microchannel to meet
the water fluid containing the SDS surfactant
that had been injected from both side channels.
Shear forces caused droplets to form and to
pinch off at the junction. Thus, droplets of
toluene in water can also be successfully
Figure 5. A) Comparison of the resistance of PDMS and HR4-coated PDMS to the flowing of
toluene in microfluidic channels. Images a and e show the unmodified and modified empty generated in our HR4-modified microfluidic
microchannels at the start (t ¼ 0). B) Comparison of the diffusion of rhodamine B molecules in device (Fig. 6B). There is no coalescence of
the tested microfluidic channels: rhodamine B diffused into the walls of the unmodified PDMS droplets in the microchannel because the O/W
microchannel, whereas in the case of the modified PDMS channel, the diffusion of rhodamine B emulsion system is stable. Furthermore, the
has been prevented and the molecules stay on the surface of the HR4-coated PDMS. resistant microfluidic device consistently pro-
duced O/W and W/O emulsions during the
continuous introduction of solvents for
6 months. In addition, the droplets produced
had a very narrow size distribution (Fig. 6C),
from the bulk PDMS, whereby the extracted oligomers can then indicating that the PDMS microfluidic device modified with HR4
contaminate the sample or reaction system. In the case of modified was able to produce stable microdroplet emulsions (O/W, W/O)
PDMS, however, we find no detectable amounts of extracted with high monodispersity.
oligomers in any of the solvents. Because our investigations
focused on determining the solvent stability of HR4 over a period
of twelve hours, this study deals with relatively short-term
preliminary results. We realize that further study is needed to
address issues dealing with the long-term solvent stability of the
3. Conclusions
HR4 film. We have created a simple method for the fabrication of solvent-
A dramatic reduction in the swelling ratio was obtained by the resistant microfluidic devices using a coating of a hybrid
surface modification of PDMS. The compatibility of HR4- inorganic/organic polymer, which results in the rapid fabrication
modified PDMS with several kinds of solvents is an interesting of microfluidic devices and increases solvent compatibility. The
result for the application of microfluidic systems in solvent-based proposed method, a simple coating of HR4 on PDMS, allows for
reactions. Furthermore, modifying the PDMS substrate avoids the rapid prototyping of microfluidic devices including multiple
problems with contamination of the samples or reaction systems cycles of design, microfabrication, and rapid evaluation of
caused by the extraction of non-crosslinked oligomers. Thus, our performance while retaining solvent resistance. Detailed informa-
proposed method is useful for the fabrication of microfluidic tion on the compatibility of various solvents was investigated
devices without swelling problems. by measuring the swelling of PDMS against each solvent.
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4. Experimental
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Synthesis of the Organic/Inorganic Hybrid

Prepolymer (HR4): HR4 prepolymers were prepared
by consecutive sol–gel reactions. At first, tetraethyl
orthosilicate (TEOS; 1 mol) was hydrolyzed in
aqueous ethanol solution (ethanol/H2O ¼ 8:12,
20 mol, pH 3.0) at 60 8C. Pluronic P123 (HOEO20-
PO70EO20H; BASF, NJ, USA) was dissolved in
ethanol. Then, the Pluronic 123 solution was added
into the prehydrolyzed TEOS sol as structure-
directing agent. Simultaneously, a titanium tetra-
chloride (TiCl4 in 20% aqueous ethanol) solution
was also prepared at room temperature. A typical
SiO2TiO2 mesoporous composite sol containing
Tiron ((OH)2C6H2(SO3Na)2H2O) was made with an
optimized ratio (TEOS/TiCl4/Tiron ¼ 1:0.1:0.025).
To make the HR4-coating solution, the composite
sols were mixed with equivalent amounts of
3-methacryloxypropyltrimethoxysilane (MEMO) as
a silane coupling agent and polyethylene glycol
dimethacrylate (PEGDMA) as a hydrophilic organic
component. Finally, the composition of the hydro-
philic HR4 prepolymer was adjusted to TEOS/TiCl4/
MEMO/PEGDMA ¼ 1:0.1:0.88:0.416.
Surface Modification of PDMS with HR4: A
mixture of PDMS prepolymer and curing agent
(10:1) (Sylgard 184, Dow Corning, MI, USA) was
stirred and degassed using a vacuum pump. The
mixture was poured over a master mold, then cured
at 65 8C for 4 h and peeled off. The PDMS replicas
were then treated by oxygen plasma (high power RF,
20 s, 0.2 Torr, 60 sccm of O2) (PDC-002, Harrick
Plasma, NY, USA) to form a silicate layer with
hydroxyl groups (OH) on the surface. These
groups not only provide a hydrophilic surface but
also allow further chemical reactions with HR4. The
HR4 prepolymer was then spin-coated at 3000 rpm
for 20 s onto the surface of the oxidized PDMS
replica. We controlled the thickness of the HR4
coating from 500 nm to 20 mm using various
combinations of HR4 concentrations, along with
the speed and time of the spin-coating procedure. An
increase of thickness of HR4, however, resulted in an
increase of surface roughness. In addition, if the HR4
film coating exceeded 10 mm in thickness occasion-
Figure 6. The formation of organic and aqueous droplets in an HR4-modified PDMS flow- ally cracking occurred after deposition on a PDMS
focusing microfluidic device. A) Oil-in-water (O/W) emulsions were obtained from 10 mL min1 of block. After 1 min exposure to UV light (l ¼ 250–
continuous phase (SDS solution: 1% w/v) and 7 mL min1 of disperse phase (toluene). B) Water- 400 nm) for chemical activation of the HR4, the
in-oil (W/O) emulsions were obtained from 10 mL min1 of continuous phase (toluene) and 7 mL modified PDMS blocks were baked at 65 8C for 1 h.
min1 of disperse phase (water). A toluene solution with dissolved fluorescent dye and water were To further stabilize the interface between HR4 and
used as the organic and aqueous phases, respectively. The fluorescent dye 4-diphenylamino- plasma-treated PDMS blocks, they were heated at
benzaldehyde was used as it is only soluble in hydrophobic organic solvents. In the case of O/W 150 8C for more than 4 h (Fig. 1A).
emulsions, we added sodium dodecyl sulfate (SDS; surfactant) into the continuous aqueous Fabrication of Microfluidic Devices: Microfluidic
phase. C) Size distribution of emulsions both of O/W and W/O; the average droplet sizes are devices were fabricated after surface modification of
116.1 2.1 mm and 162.4 4.2 mm, respectively. PDMS with HR4, before baking (Fig. 1B). After
coating the PDMS, all excess HR4 on the bonding
region (both sides of the microfluidic channel) was
removed by brushing with a soft PDMS slab blade.
Furthermore, the proposed method shows strong potential for After selective removal of the excess HR4 solution (the region for bonding
expanding the application of PDMS-based microfluidic systems the PDMS to a glass substrate), the device was cured for the stable
into other fields, such as organic synthesis, microchemical anchoring and polymerization of the HR4 prepolymer selectively onto the
reactors, organic solvent-based droplet formation, and micro- microfluidic channel. After complete thermal curing, the modified PDMS
microfluidic device could be bonded easily with glass using oxygen-plasma
molds or nanomolds in unconventional patterning. This method treatment (20 s). The microchannel of the assembled device had three
can be used to replace glass, metal, or silicon-based devices for HR4-modified regions and a glass region at the bottom. An SEM image of a
organic-phase systems, but it also enables many water-based cross section of the assembled microfluidic device is shown before
experiments currently being carried out in PDMS devices. (Fig. 1C).
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Measurements of Swelling Ratio and Absorption Rate: To measure the Received: June 9, 2009
FULL PAPER
solvent resistance and absorption rate, pristine PDMS and HR4-modified Revised: August 28, 2009
PDMS blocks were prepared as 20 mm square blocks, 1.5 mm deep. For Published online: November 9, 2009
measuring the absorption rate, we calculated the amount of absorption of
the solvent into the PDMS blocks while the PDMS blocks were contacted
with various solvents for 1h. In order to calculate the degree of swelling,
several kinds of solvents were loaded onto the PDMS blocks for 12 h and [1] J. West, M. Becker, S. Tombrink, A. Manz, Anal Chem. 2008, 80, 4403.
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benzene, cyclohexane, chloroform, hexane, and toluene [12]. Therefore,
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microfluidic device to assess its solvent resistance and compatibility. The Y. M. Chung, C. S. Lee, Lab Chip 2008, 8, 1544. c) N. Prasad, J. Perumal,
flow focusing design provided a high shear force at the interface junction C. H. Choi, C. S. Lee, D. P. Kim, Adv. Funct. Mater. 2009, 19, 1656.
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Acknowledgements [21] a) D. P. Kim, L. Y. Hong, J. H. Won, Y. S. Park, C. K. Shin, world patent WO
This study was supported by a grant from the Korea Health 21 R&D Project, 07/069867 A1, (2007). b) L. Y. Hong, D. H. Lee, D. P. Kim, J. Phys. Chem.
Ministry of Health and Welfare (Project No: A062254), Korea Research Solids 2008, 69, 1436.
Foundation grant (KRF-2008-331-D00131), and the Korea Science and [22] I. J. Chen, E. Lindner, Langmuir 2007, 23, 3118.
Engineering Foundation grant (KOSEF) (MEST No. R01-2008-000–11260- [23] K. S. Guan, B. J. Lu, Y. S. Yin, Surf. Coat. Technol. 2003, 173, 219.
0). This work was also funded by the 2008 Creative Research Initiative [24] L. Y. Hong, Y. S. Cho, D. P. Kim, J. Ind. Eng. Chem. 2005, 11, 275.
Program [R16-2008-138-01000-0]. We appreciate Anderson Shum (Harvard [25] Y. S. Kim, J. Park, H. H. Lee, Appl. Phys. Lett. 2002, 81, 1011.
University) for his helpful discussions. Supporting information is available [26] J. H. Xu, S. W. Li, J. Tan, Y. J. Wang, G. S. Luo, Langmuir 2006, 22,
online at Wiley InterScience or from the authors. 7943.

Adv Funct Materials - 2009 - Kim - Solvent Resistant PDMS Microfluidic Devices With Hybrid Inorganic Organic Polymer

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Solvent-Resistant PDMS Microfluidic Devices with

using conventional microfabrication techni-

results from combined OH stretching, including the

SiOH stretching in the silica unit, the COH

2.2. Absorption Rates of Various Organic Solvents

The collapse and blockage of microfluidic channels are

Table 1. Comparison of water contact angle of PDMS and HR4-modified

Sample Water contact angle [8]

PDMS 106.9 0.4

between the PDMS and HR4-modified PDMS. The initial

where M is the weight of the solvent absorbed by a given substrate

2.3. Solvent Stability

Investigating the solvent stability of the HR4-modified PDMS was

Table 2. Swelling ratios of PDMS and HR4-modified PDMS in various solvents.

Solvents Absorption rate (a) Degree of swelling

Water 0.00 0.00 1.00 0.00 0.00

2.4. Generation of Emulsion Droplets in

To demonstrate the feasibility of solvent-based

Synthesis of the Organic/Inorganic Hybrid

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