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ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 324|P a g e
PIV Measurement for Electroosmotic Flow in Sio2pdms Surface
Modified Microchannel
Shrok Allami1,2
, Naif Al-Hardan2
, Qahtan Aljimily2
1
Scholar visitor, university of California, Irvine - USA.
2
Ministry of Science and Technology, Baghdad – Iraq
Abstract
Electroosmotic is a flow created under the application of electric field on the fluid. Recently, PDMS exhibits
great potential in microfluidic device for many applications. The less ability to support electroosmotic flow and
flow instability with time are the phenomena associated with the fluid flow in PDMS microchannel. To improve
fluid flow in PDMS, microchannel surface modified with SiO2, different thicknesses, by PECVD was employed.
Surface characterizations were carried out using atomic force microscope (AFM) and scanning electron
microscopy (SEM). Whereby; UV-visible spectrometer and X-ray diffraction (XRD) were employed to identify
optical properties and structural phase of the modified PDMS respectively. Particle image velocimetry (PIV)
was used to track particles in PDMS microchannel, native and modified. We demonstrated that PDMS surface
modified with SiO2 slowing down fluid flow comparing to native PDMS allowing reaction and/or measurements
taken place in microchannel. Fluid stability in PDMS, native and surface modified, were monitored via
electrical resistance – time measurements with the aid of Cd2+
aqueous solution mixed with AuNP colloidal.
SiO2 PDMS surface modified microchannel achieved stable time- fluid flow.
Keywords: PDMS surface modification, microfluidic, and Electrophoresis flow.
I. Introduction
Recently,Microfluidicdeviceshavereceivedconsiderab
leattentionduetotheirwideapplicationsinchemicalandb
iochemicalsensing.Thesedevicesoffermanyadvantage
ssuchasreducingthesamplesize, reagent
consumption,analysistime,andhigh-sensitivity [1].
Severalmaterialswereusedtofabricatethemas;siliconw
afers(Si),glasses,andpolymers.Polydimethylsiloxane(
PDMS)hasseveraladvantages,suchaselastomeric,bioc
ompatibility,gaspermeability,opticaltransparency,mol
dinginsubmicrometerfeatures,easeofbonding,relativel
ychemicalinertness,andlowcostthosemakeitthemostpo
lymersusedformicrofluidicdevice[1].Microfluidicdevi
cesweredesignedtoallowbulkfluidsandmolecularspeci
estransportationinmicrochipelectrokinetically(includi
ngbothelectro-
osmosisandelectrophoresis)upontheapplicationoftheel
ectricfield[2].Theseelectrokineticallydrivenmicrosyst
emscanbeeasilyintegratedwithavarietyofseparationan
dsampledetectiontechniques[1].Enhancingfluidssprea
dingandstayingoversurfacesforawhiletoletreactions,m
ixingorthemeasurementstakenplaceareoneofthemajor
microfluidicmaterialrequirements[3].PDMSimprove
mentwasthemaingoalforseveralresearchgroups.PDMS
surfaceoxidizingusingdifferentmethodsasUVandplas
matreatments[4].Treatmentswillcreateweakbondsbet
weenoxidizedPDMSsurfaceandwatermoleculesallowi
ngfluidspreadingoverthesurface.However,diffusionofl
owmolecularweightchainsfromthebulktosurfacearesul
tinPDMSoriginalhydrophobicityregains[5].Shankeret
alreferredthisregainsinPDMSsurfaceoxygenplasmatre
atmenttoSi-
OgroupcreationthathastheabilitychangetoSi-
OHgroupwithinthreehoursatambientair[2].Othergroup
shaveworkedonPDMSsurfacemodificationsviathinfil
mdeposition,gold[6],titaniumdioxide(TiO2)[7],andSi
O2layer[8,9].ToenhancethesustainabilityofPDMSsurf
acehydrophobicityDogheeetalhad depositedSiO2laye
rby atmospheric
pressureplasmaenhancedchemicalvapordeposition.Fir
st,hydrocarbonlayerwascoatedonPDMSsurfaceusingC
H4asthereactantgasthenahydrophilicSiOxlayerwasdep
ositedusingtetraethylorthosilicateandoxygen(TEOS-
O2[8].SiO2layerwasdepositedalsobyanothergroupviai
n-situsol-
gelmodificationtoincreaseandstabile'selectroosmoticfl
owinmicrochannel[9].
Recently,attentionhasbeenfocusedonstudyin
gandoptimizingfluid’stransportationinmicrochannelra
therthanjustimprovingitssurfacehydrophobicity[10].T
hesestudiesfocusedonelectro-
osmosisflow(EOF)andits
variableswithtimeandmeasurementcondition.
Differenttechniqueshavebeenusedtostudyele
ctro-
osmosisflow(EOF)inmicrochannel.Currentmonitoring
techniqueisanaveragevelocitymeasurementofelectro-
osmoticflow(EOF)bymonitoringtheelectriccurrentcha
ngewithtime[11].Kahsalmeasuredfluidflowinmicroch
annel,fabricatedwithself-
RESEARCH ARTICLE OPEN ACCESS
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 325|P a g e
assemblyhydrophilicparticles,usingopticalimagingin
measuringmarker'sdisplacementbetweentowbuffersol
utions[12].Particleimagetransportationwasusedtomea
surethelargeparticlesorcells'velocitiesthroughtherectif
icationofthe(AC)electro-
osmoticflowsinopenmicrochannels[13].
Microparticle'simagevelocimetry(PIV)wasal
soemployedtogetherwithacurrentmonitoringtechnique
,totrackparticlesandobtainelectrokineticallybulkfluidfl
owvelocity[1,14].Xueqindemonstratedthatinlowionic
strengthsolutionsnearneutralpH,oxidizedPDMShadfo
ur-
foldgreaterEOFmobilitycomparedtonativePDMS[2].
The aim of this work is to modify PDMS
surface by deposition hydrophilic SiO2 layer,
deposited by plasma enhances chemical vapor
deposition (PECVD) and studying its effect on
electro-osmosis flow (EOF) in microchannel, species
adsorption prevention, and elimination of PDMS
surface hydrophobicity recovery. Amorphous Si
interlayer was used to create a direct and stable bond
with free Si-O- group that creates on DPMS surface
by oxygen plasma treatment. The modified PDMS
properties were evaluated by surface morphology,
optical properties, and water contact angle
measurement. The effect of PDMS surface
modification on electrophoresis mobility was studied
by particle's image velocimetry. The effect of inert
SiO2 layer on the absorption of Cd2+ in aqueous
solution mixed with AuNP colloidal was
demonstrated through electric resistance
measurement's stability in microchannel.
II. Experimental work
2.1 PDMS Fabrication and surface modification
by SiO2
Sylgard® 184 oligomer and curing agent
were thoroughly mixed at 10:1 mass ratio degassed
for 30 min and poured over cleaned flat and patterned
Si wafer. For electrophoresis measurements,
photolithography was used to get Si wafer mold
contain single straight micro-channel, 300 µm in
width, 50 µm in depth and 4 cm in length. The
poured PDMS was cured at 65oC for 180 min. Then
master was kept overnight inside an oven maintained
at 60◦C. The cured PDMS layers were carefully
peeled off from the wafers, flat PDMS were cut into
the required dimensions. Flat and slabs with
microchannel features PDMS were cleaned
ultrasonically for 10 min with deionized water;
ethanol and deionized water subsequently then dried
using air flow.
PDMS, flat and patterned, were oxygen
plasma treated using 124 watts RF power for 3
minutes. Within 30 minutes, treated PDMS were
loaded in BMR, low temperature plasma enhance
chemical vapor deposition machine (PECVD) to
deposit 2 and 4 nm thickness amorphous silicon
layers by applying 1000 watts RF power and using
H2 and SiH4 gases with flow rates of 50 and 25
sccm(Standard Cubic Centimeters per Minute)
respectively. Hydrophilic SiO2 thin films with 10, 20,
and 30 nm thickness were deposited next step using
25, 10, and 7 sccm gas flow rates for O2, Ar, and
SiH4 respectively maintaining the chamber pressure
at 10 m Torr (milliTorr) and RF power at 1000 watt.
2.2 PDMS microchip's fabrication for
electrophoretic and electric
resistancemeasurements
For electrophoretic measurements, PDMS
layer with microchannel, native or modified, and thin
flat PDMS were sealed together to form PDMS
microchip by clamping them between two PMMA
sheets. To indicate specious absorption via electric
resistance stability a simple microchip was designed
and fabricated as shown in Fig.1. That formed from
two inlet reservoirs for Cd aqueous solution and
AuNP (gold nanoparticles) colloidal, 10 cm length
mixing microchannel perpendicular to 3 cm length
measurement microchannel Two reservoirs were used
for Cu measurement electrodes. PDMS with
microchannel features and thin flat PDMS, native or
modified, were sealed together between two PMMA
sheets. Cd2+ aqueous solution prepared from
dissolution of cadmium acetate in distill water, and
AuNP colloidal were inlets into micro-channels
under negative pressure driven at room temperature.
Figure 1.Sketch design for Microfluidic used to
detect Cd2+ in water via electric resistance
measurement.
2.3 Characterizations
Thin film crystalline structure, surface
morphology, and roughness were identified by
Rigaku Smart Lab X-ray Diffractometer, and PNI
Nano-R AFM respectively. UV-Visible spectrometer
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 326|P a g e
from Shimadzu with wavelength range 190-850 nm
was employed to investigate changes in PDMS
absorption spectrum.
It is well known hydrophilic changes determined
through water contact angle (WCA), that can be
measured by the angle formed between the solid and
tangent to the drop surface. Average values from
three measurements were considered for 10 µl
distilled water droplets volume. Water contact angles
were analyzed using Lucia software.
2.4 Electroosmotic flow measurements
Initially, 20 µm fluorescent polystyrene
latex microspheres beads (from Polysciences Inc.) in
distilled water were used to flue under driven
pressure through fabricated PDMS microchips. DC
potential values range (100-1000V) was applied on
one reservoir while keeping another reservoir
grounded. Particles velocities were measured with the
aid of imaging using an optical microscope and
fluorescence light. Electrophoresis mobility was
calculated via beads migration through microchannel
after 30 s of applying voltage. Fig. 2 illustrates beads
tracking under applied potential.
Figure 2: Image illustration for micro particles
tracking into micro-channel
III. Results and discussions
3.1 Deposition layer appearance and Optical
properties
PDMS with the SiO2 deposition layers
appeared glosser than native PDMS. SiO2 deposited
layer was flat and hard enough to resist scratching.
Unless we hold PDMS samples on PMMA substrate
during depositions and investigations, cracks were
observedin SiO2 surface layer under optical
microscope Fig.3a, and under high resolution SEM,
Fig. 3b. These cracks referred to; residual thermal
stresses, which increases with film thickness, and to
SiO2 brittleness and its adhesion problems to PDMS.
Niu referred brittle cracks in TiO2 thin film coated
PDMS samples to flexibility and bending during
handling [15], while Feng referred them to weak
adhesion between gold as coating layer and PDMS
surface [5].
The transmittance of the fabricated device is
extremely crucial in monitoring fluid flow in micro-
channels; hence the surface modification must not
have a great impact on the device original
transparency. The deposited SiO2 thin films of
different thickness had yellowish color. Fig. 4 shows
native and coated PDMS transparence spectrums.
PDMS is optically clear at a wide range of
wavelengths, amorphous SiO2 thin film absorb light
in the visible region and reduce transparency.
Figure 3: Modified PDMS surface images by a-
optical microscope b- SEM
3.2 Surface morphology
Amorphous Si interlayer, via XRD results,
affect surface morphology of the subsequent SiO2
layer. In its early stage of nucleation amorphous Si
formed islands that increased with thickness; these
plays a very important role in determining the
subsequent roughness evolution[16].Increasing Si
interlayer thickness to 4 nm would increase the roots
mean square (rms) roughness of SiO2 surface (Table
1). Fig. 5 depicts the AFM images for surface
morphology. We can indicate that SiO2 surface
morphology, with nano thickness, fellows amorphous
Si under layer morphology.
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
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Figure 4: UV-Visible spectrum for native and
modified PDMS
Table 1:Effect of the Si interlayer thickness on the
roughness of SiO2 modified PDMS surface.
Si
thickness nm
SiO2
thickness nm
rms roughness
nm
2 10 1.511
2 20 1.610
2 30 1.544
4 10 3.129
4 20 3.702
4 30 4.37
A
B
C
D
E
Figure 5: The AFM morphology images for the
modified PDMS surface samples. (a) 2Si-10SiO2 (b)
2Si-20SiO2, (c) 4Si-10 SiO2 (d) 4Si-20 SiO2 (e) 4Si-
30 SiO2
3.3 Contact Angleand XRD
Surface wettability (or hydrophilic
properties) has a great impact on fluid flow and
bubbles formation in PDMS microchannels. Fig. 6
reveals WCA changes over the PDMS samples with
time under atmospheric condition. The PDMS
samples coated with SiO2 films are more hydrophilic
than the native one in contrary; they lost their
hydrophobicity with time.
WCA of the native PDMS was 83⁰ changed
to 15-32⁰ directly after SiO2 deposition. After 3 hr.
WCA began increasing to 50-67⁰ within 7 hr and
stayed stable for several days. Those results are in
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 328|P a g e
good agreement with previous works. Maturos found
that PDMS coated with titanium dioxide thin film
before oxygen plasma treatment lost its
hydrophobicitywithin 3 hr. [7]. PDMS hydrophobic
recovery refers to the migration of uncured and
highly mobile oligomers from the bulk to the surface
changing Si-O- bond on the surface to Si-OH at room
temperature [2]. No crystalline peaks were detected
by XRD technique from SiO2 deposited layers.
Figure 6 : WCA for modified PDMS surface
3.4 Electrophoreses flow in native PDMS
microchannel
Introducing aqueous solution wasdifficult
and bubble formation appeared during negative
pressure driven flow in native PDMS microchannels.
While electro osmotic flow (EOF) had non uniform
beads velocities. This is due to poor surface charge
and nonpolar hydrophobic species absorption in the
surface [17]. Native PDMS composes of repeating
group Si-CH3, which does not expect to have a net
surface charge [2]. Negative charged SiO- groups
create at PDMS-liquid interface when PDMS be in
contact with moderate pH aqueous solution for a
while [1]. These charged silanol groups attract
cationic species from bulk liquid, repel anions and
forming electrical double layer (EDL). The potential
drop occurred across diffuse portion of EDL is
defined as the zeta potential. When an external
electric field applied parallel to EDL wall near zeta
potential portion, it will exert force on the diffuse
ions and moves them toward the cathode. While the
uncharged bulk liquid, during electroosmotic flow,
pumped by viscous interactions between EDL ions
and the liquid [1] as illustrated in Fig.7. These would
explain particles non uniformvelocities in native
PDMS microchannel with applied potential
strength.Fig.8 shows particles velocities (in
micron/sec) increasing with applied potential in
native PDMS microchannel. Increasing applied
potential subsequently will increased external electric
field applied parallel to EDL wall near zeta potential
portion,that exert large force on the diffuse ions and
increase their velocities toward the cathode.
Figure7: Sketch illustrates EOF driving force into
PDMS.
Figure8: PIV for native and modified PDMS surface
microchannel
3.5 Electrophoresis flow in modified PDMS
microchannel
Pressure driven flow in modified PDMS
microchannel was without difficulties faced
introducing aqueous solution, limitation in bubbles
formation, stable fluid flow, and uniform beads
velocities across microchannel.
The effect of PDMS surface modification on
electrophoresis mobility was studied by particle's
image velocimetry. As shown in Fig.9 microchannel
constructed from PDMS modified with SiO2 had
lower beads velocities than native PDMS
microchannel under different applied potentials
strength and with various SiO2 thicknesses used. It
could be noticed also, beads velocities decreased with
SiO2 thicknesses. As well-known SiO2is inert and
non-charged layer, soit presents a barrier prevents
specious absorption, eliminates EDL and zeta
potential formation, and enhances stable EOF with
uniform beads velocities across microchannel. Thus,
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 329|P a g e
eliminates EDL and zeta potential formation would
increase forces needed to move fluid ions and beads
in it. That does explain particles slowing down
velocities under the same applied potential condition
into modified PDMS microchannel compared to
native PDMS microchannel. In addition to that and as
explained before SiO2 on PDMS roughened
microchannel surface, that is a common cause of
premature breakdown and slowing down fluid stream
over materials surface [18]. Moreover, SiO2 surface
film had cracks, observed clearly via optical
microscope.These grooves in film surface exert as
specious capturing regions, which slowing down
them and elongate their staying time [19].
Figure9:The PIV for different SiO2 thickness
modified PDMS surface microchannel
3.6 Electric resistance of Cd+2 aqueous solutions
mixed with AuNPcolloidal in modified PDMS
surface
Cadmium acetate aqueous solution classified
as coordination polymer, featuring acetate ligands
interconnecting cadmium centers. Its aqueous
solution with AuNP colloidal mixture, prepared in
our previous work [20], can exhibit water
solubleconjugated conductive polyelectrolyte.
Conductive polyelectrolyte phenomenon refers to
carboxylate groups on AuNPs surface that bonded to
Cd+2 owing to nanoparticles aggregating and
networking [21]. This could be understood from the
electric resistance measurements at modified PDMS
microchannel that decreased with Cd ions in
polyelectrolytes as shown in Fig.10 due to
nanoparticles aggregating and networking increasing.
Fig.11 shows polyelectrolytes electrical resistance
with time in native and modified microchannel.
Stable electric resistance observed at modified
microchannel after 0.5 min compared to native
microchannel. SiO2 deposited layer gives evidence to
prevent species absorption into PDMS surface and
enhance getting stable fluid flow into microchannel
fabricated from PDMS.
Figure10: The electric resistance for Cd aqueous
solution and AuNP colloidal mixture at modified
PDMS microchannel
Figure11: The electric resistance stability with time at
native and modified PDMS microchannel.
IV. Conclusions
In summary, we report in PDMS surface
modification by deposition of SiO2in micro-channel.
SiO2 alerts the PDMS optical and surface properties.
PDMS new surface recovers part of its
hydrophobicity after 7 hours and became stable for
several days, increasing Si interlayer and SiO2
thickness found to reduce surface lost
hydrophobicity. Electrophoresis flow on modified
and native PDMS were studied using the particles
image velocimetry. Particles velocities in modified
PDMS microchannels became more stable, slowing
down to approximately it’shalve value with SiO2
thickness and electric field strength. SiO2 deposition
layer prevents species absorption into PDMS
microchannel surface and enhance the solutions
stabilities into microchannel.
V. Acknowledgment
The authors acknowledge many thanks to
CRDF global for their support. The main author
ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com
ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330
www.ijera.com 330|P a g e
ShrokAllamiwould like to express thanks to her host
G.P.Li director of California Institute for
Telecommunications and Information Technology
(Calit2), University of California Irvine, USA. Mo
Kibali, Albert Yee, Jack in INRF, Sarkis and Jason in
UCI for their great supports and advisements to
conduct this work.
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  • 1. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 324|P a g e PIV Measurement for Electroosmotic Flow in Sio2pdms Surface Modified Microchannel Shrok Allami1,2 , Naif Al-Hardan2 , Qahtan Aljimily2 1 Scholar visitor, university of California, Irvine - USA. 2 Ministry of Science and Technology, Baghdad – Iraq Abstract Electroosmotic is a flow created under the application of electric field on the fluid. Recently, PDMS exhibits great potential in microfluidic device for many applications. The less ability to support electroosmotic flow and flow instability with time are the phenomena associated with the fluid flow in PDMS microchannel. To improve fluid flow in PDMS, microchannel surface modified with SiO2, different thicknesses, by PECVD was employed. Surface characterizations were carried out using atomic force microscope (AFM) and scanning electron microscopy (SEM). Whereby; UV-visible spectrometer and X-ray diffraction (XRD) were employed to identify optical properties and structural phase of the modified PDMS respectively. Particle image velocimetry (PIV) was used to track particles in PDMS microchannel, native and modified. We demonstrated that PDMS surface modified with SiO2 slowing down fluid flow comparing to native PDMS allowing reaction and/or measurements taken place in microchannel. Fluid stability in PDMS, native and surface modified, were monitored via electrical resistance – time measurements with the aid of Cd2+ aqueous solution mixed with AuNP colloidal. SiO2 PDMS surface modified microchannel achieved stable time- fluid flow. Keywords: PDMS surface modification, microfluidic, and Electrophoresis flow. I. Introduction Recently,Microfluidicdeviceshavereceivedconsiderab leattentionduetotheirwideapplicationsinchemicalandb iochemicalsensing.Thesedevicesoffermanyadvantage ssuchasreducingthesamplesize, reagent consumption,analysistime,andhigh-sensitivity [1]. Severalmaterialswereusedtofabricatethemas;siliconw afers(Si),glasses,andpolymers.Polydimethylsiloxane( PDMS)hasseveraladvantages,suchaselastomeric,bioc ompatibility,gaspermeability,opticaltransparency,mol dinginsubmicrometerfeatures,easeofbonding,relativel ychemicalinertness,andlowcostthosemakeitthemostpo lymersusedformicrofluidicdevice[1].Microfluidicdevi cesweredesignedtoallowbulkfluidsandmolecularspeci estransportationinmicrochipelectrokinetically(includi ngbothelectro- osmosisandelectrophoresis)upontheapplicationoftheel ectricfield[2].Theseelectrokineticallydrivenmicrosyst emscanbeeasilyintegratedwithavarietyofseparationan dsampledetectiontechniques[1].Enhancingfluidssprea dingandstayingoversurfacesforawhiletoletreactions,m ixingorthemeasurementstakenplaceareoneofthemajor microfluidicmaterialrequirements[3].PDMSimprove mentwasthemaingoalforseveralresearchgroups.PDMS surfaceoxidizingusingdifferentmethodsasUVandplas matreatments[4].Treatmentswillcreateweakbondsbet weenoxidizedPDMSsurfaceandwatermoleculesallowi ngfluidspreadingoverthesurface.However,diffusionofl owmolecularweightchainsfromthebulktosurfacearesul tinPDMSoriginalhydrophobicityregains[5].Shankeret alreferredthisregainsinPDMSsurfaceoxygenplasmatre atmenttoSi- OgroupcreationthathastheabilitychangetoSi- OHgroupwithinthreehoursatambientair[2].Othergroup shaveworkedonPDMSsurfacemodificationsviathinfil mdeposition,gold[6],titaniumdioxide(TiO2)[7],andSi O2layer[8,9].ToenhancethesustainabilityofPDMSsurf acehydrophobicityDogheeetalhad depositedSiO2laye rby atmospheric pressureplasmaenhancedchemicalvapordeposition.Fir st,hydrocarbonlayerwascoatedonPDMSsurfaceusingC H4asthereactantgasthenahydrophilicSiOxlayerwasdep ositedusingtetraethylorthosilicateandoxygen(TEOS- O2[8].SiO2layerwasdepositedalsobyanothergroupviai n-situsol- gelmodificationtoincreaseandstabile'selectroosmoticfl owinmicrochannel[9]. Recently,attentionhasbeenfocusedonstudyin gandoptimizingfluid’stransportationinmicrochannelra therthanjustimprovingitssurfacehydrophobicity[10].T hesestudiesfocusedonelectro- osmosisflow(EOF)andits variableswithtimeandmeasurementcondition. Differenttechniqueshavebeenusedtostudyele ctro- osmosisflow(EOF)inmicrochannel.Currentmonitoring techniqueisanaveragevelocitymeasurementofelectro- osmoticflow(EOF)bymonitoringtheelectriccurrentcha ngewithtime[11].Kahsalmeasuredfluidflowinmicroch annel,fabricatedwithself- RESEARCH ARTICLE OPEN ACCESS
  • 2. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 325|P a g e assemblyhydrophilicparticles,usingopticalimagingin measuringmarker'sdisplacementbetweentowbuffersol utions[12].Particleimagetransportationwasusedtomea surethelargeparticlesorcells'velocitiesthroughtherectif icationofthe(AC)electro- osmoticflowsinopenmicrochannels[13]. Microparticle'simagevelocimetry(PIV)wasal soemployedtogetherwithacurrentmonitoringtechnique ,totrackparticlesandobtainelectrokineticallybulkfluidfl owvelocity[1,14].Xueqindemonstratedthatinlowionic strengthsolutionsnearneutralpH,oxidizedPDMShadfo ur- foldgreaterEOFmobilitycomparedtonativePDMS[2]. The aim of this work is to modify PDMS surface by deposition hydrophilic SiO2 layer, deposited by plasma enhances chemical vapor deposition (PECVD) and studying its effect on electro-osmosis flow (EOF) in microchannel, species adsorption prevention, and elimination of PDMS surface hydrophobicity recovery. Amorphous Si interlayer was used to create a direct and stable bond with free Si-O- group that creates on DPMS surface by oxygen plasma treatment. The modified PDMS properties were evaluated by surface morphology, optical properties, and water contact angle measurement. The effect of PDMS surface modification on electrophoresis mobility was studied by particle's image velocimetry. The effect of inert SiO2 layer on the absorption of Cd2+ in aqueous solution mixed with AuNP colloidal was demonstrated through electric resistance measurement's stability in microchannel. II. Experimental work 2.1 PDMS Fabrication and surface modification by SiO2 Sylgard® 184 oligomer and curing agent were thoroughly mixed at 10:1 mass ratio degassed for 30 min and poured over cleaned flat and patterned Si wafer. For electrophoresis measurements, photolithography was used to get Si wafer mold contain single straight micro-channel, 300 µm in width, 50 µm in depth and 4 cm in length. The poured PDMS was cured at 65oC for 180 min. Then master was kept overnight inside an oven maintained at 60◦C. The cured PDMS layers were carefully peeled off from the wafers, flat PDMS were cut into the required dimensions. Flat and slabs with microchannel features PDMS were cleaned ultrasonically for 10 min with deionized water; ethanol and deionized water subsequently then dried using air flow. PDMS, flat and patterned, were oxygen plasma treated using 124 watts RF power for 3 minutes. Within 30 minutes, treated PDMS were loaded in BMR, low temperature plasma enhance chemical vapor deposition machine (PECVD) to deposit 2 and 4 nm thickness amorphous silicon layers by applying 1000 watts RF power and using H2 and SiH4 gases with flow rates of 50 and 25 sccm(Standard Cubic Centimeters per Minute) respectively. Hydrophilic SiO2 thin films with 10, 20, and 30 nm thickness were deposited next step using 25, 10, and 7 sccm gas flow rates for O2, Ar, and SiH4 respectively maintaining the chamber pressure at 10 m Torr (milliTorr) and RF power at 1000 watt. 2.2 PDMS microchip's fabrication for electrophoretic and electric resistancemeasurements For electrophoretic measurements, PDMS layer with microchannel, native or modified, and thin flat PDMS were sealed together to form PDMS microchip by clamping them between two PMMA sheets. To indicate specious absorption via electric resistance stability a simple microchip was designed and fabricated as shown in Fig.1. That formed from two inlet reservoirs for Cd aqueous solution and AuNP (gold nanoparticles) colloidal, 10 cm length mixing microchannel perpendicular to 3 cm length measurement microchannel Two reservoirs were used for Cu measurement electrodes. PDMS with microchannel features and thin flat PDMS, native or modified, were sealed together between two PMMA sheets. Cd2+ aqueous solution prepared from dissolution of cadmium acetate in distill water, and AuNP colloidal were inlets into micro-channels under negative pressure driven at room temperature. Figure 1.Sketch design for Microfluidic used to detect Cd2+ in water via electric resistance measurement. 2.3 Characterizations Thin film crystalline structure, surface morphology, and roughness were identified by Rigaku Smart Lab X-ray Diffractometer, and PNI Nano-R AFM respectively. UV-Visible spectrometer
  • 3. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 326|P a g e from Shimadzu with wavelength range 190-850 nm was employed to investigate changes in PDMS absorption spectrum. It is well known hydrophilic changes determined through water contact angle (WCA), that can be measured by the angle formed between the solid and tangent to the drop surface. Average values from three measurements were considered for 10 µl distilled water droplets volume. Water contact angles were analyzed using Lucia software. 2.4 Electroosmotic flow measurements Initially, 20 µm fluorescent polystyrene latex microspheres beads (from Polysciences Inc.) in distilled water were used to flue under driven pressure through fabricated PDMS microchips. DC potential values range (100-1000V) was applied on one reservoir while keeping another reservoir grounded. Particles velocities were measured with the aid of imaging using an optical microscope and fluorescence light. Electrophoresis mobility was calculated via beads migration through microchannel after 30 s of applying voltage. Fig. 2 illustrates beads tracking under applied potential. Figure 2: Image illustration for micro particles tracking into micro-channel III. Results and discussions 3.1 Deposition layer appearance and Optical properties PDMS with the SiO2 deposition layers appeared glosser than native PDMS. SiO2 deposited layer was flat and hard enough to resist scratching. Unless we hold PDMS samples on PMMA substrate during depositions and investigations, cracks were observedin SiO2 surface layer under optical microscope Fig.3a, and under high resolution SEM, Fig. 3b. These cracks referred to; residual thermal stresses, which increases with film thickness, and to SiO2 brittleness and its adhesion problems to PDMS. Niu referred brittle cracks in TiO2 thin film coated PDMS samples to flexibility and bending during handling [15], while Feng referred them to weak adhesion between gold as coating layer and PDMS surface [5]. The transmittance of the fabricated device is extremely crucial in monitoring fluid flow in micro- channels; hence the surface modification must not have a great impact on the device original transparency. The deposited SiO2 thin films of different thickness had yellowish color. Fig. 4 shows native and coated PDMS transparence spectrums. PDMS is optically clear at a wide range of wavelengths, amorphous SiO2 thin film absorb light in the visible region and reduce transparency. Figure 3: Modified PDMS surface images by a- optical microscope b- SEM 3.2 Surface morphology Amorphous Si interlayer, via XRD results, affect surface morphology of the subsequent SiO2 layer. In its early stage of nucleation amorphous Si formed islands that increased with thickness; these plays a very important role in determining the subsequent roughness evolution[16].Increasing Si interlayer thickness to 4 nm would increase the roots mean square (rms) roughness of SiO2 surface (Table 1). Fig. 5 depicts the AFM images for surface morphology. We can indicate that SiO2 surface morphology, with nano thickness, fellows amorphous Si under layer morphology.
  • 4. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 327|P a g e Figure 4: UV-Visible spectrum for native and modified PDMS Table 1:Effect of the Si interlayer thickness on the roughness of SiO2 modified PDMS surface. Si thickness nm SiO2 thickness nm rms roughness nm 2 10 1.511 2 20 1.610 2 30 1.544 4 10 3.129 4 20 3.702 4 30 4.37 A B C D E Figure 5: The AFM morphology images for the modified PDMS surface samples. (a) 2Si-10SiO2 (b) 2Si-20SiO2, (c) 4Si-10 SiO2 (d) 4Si-20 SiO2 (e) 4Si- 30 SiO2 3.3 Contact Angleand XRD Surface wettability (or hydrophilic properties) has a great impact on fluid flow and bubbles formation in PDMS microchannels. Fig. 6 reveals WCA changes over the PDMS samples with time under atmospheric condition. The PDMS samples coated with SiO2 films are more hydrophilic than the native one in contrary; they lost their hydrophobicity with time. WCA of the native PDMS was 83⁰ changed to 15-32⁰ directly after SiO2 deposition. After 3 hr. WCA began increasing to 50-67⁰ within 7 hr and stayed stable for several days. Those results are in
  • 5. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 328|P a g e good agreement with previous works. Maturos found that PDMS coated with titanium dioxide thin film before oxygen plasma treatment lost its hydrophobicitywithin 3 hr. [7]. PDMS hydrophobic recovery refers to the migration of uncured and highly mobile oligomers from the bulk to the surface changing Si-O- bond on the surface to Si-OH at room temperature [2]. No crystalline peaks were detected by XRD technique from SiO2 deposited layers. Figure 6 : WCA for modified PDMS surface 3.4 Electrophoreses flow in native PDMS microchannel Introducing aqueous solution wasdifficult and bubble formation appeared during negative pressure driven flow in native PDMS microchannels. While electro osmotic flow (EOF) had non uniform beads velocities. This is due to poor surface charge and nonpolar hydrophobic species absorption in the surface [17]. Native PDMS composes of repeating group Si-CH3, which does not expect to have a net surface charge [2]. Negative charged SiO- groups create at PDMS-liquid interface when PDMS be in contact with moderate pH aqueous solution for a while [1]. These charged silanol groups attract cationic species from bulk liquid, repel anions and forming electrical double layer (EDL). The potential drop occurred across diffuse portion of EDL is defined as the zeta potential. When an external electric field applied parallel to EDL wall near zeta potential portion, it will exert force on the diffuse ions and moves them toward the cathode. While the uncharged bulk liquid, during electroosmotic flow, pumped by viscous interactions between EDL ions and the liquid [1] as illustrated in Fig.7. These would explain particles non uniformvelocities in native PDMS microchannel with applied potential strength.Fig.8 shows particles velocities (in micron/sec) increasing with applied potential in native PDMS microchannel. Increasing applied potential subsequently will increased external electric field applied parallel to EDL wall near zeta potential portion,that exert large force on the diffuse ions and increase their velocities toward the cathode. Figure7: Sketch illustrates EOF driving force into PDMS. Figure8: PIV for native and modified PDMS surface microchannel 3.5 Electrophoresis flow in modified PDMS microchannel Pressure driven flow in modified PDMS microchannel was without difficulties faced introducing aqueous solution, limitation in bubbles formation, stable fluid flow, and uniform beads velocities across microchannel. The effect of PDMS surface modification on electrophoresis mobility was studied by particle's image velocimetry. As shown in Fig.9 microchannel constructed from PDMS modified with SiO2 had lower beads velocities than native PDMS microchannel under different applied potentials strength and with various SiO2 thicknesses used. It could be noticed also, beads velocities decreased with SiO2 thicknesses. As well-known SiO2is inert and non-charged layer, soit presents a barrier prevents specious absorption, eliminates EDL and zeta potential formation, and enhances stable EOF with uniform beads velocities across microchannel. Thus,
  • 6. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 329|P a g e eliminates EDL and zeta potential formation would increase forces needed to move fluid ions and beads in it. That does explain particles slowing down velocities under the same applied potential condition into modified PDMS microchannel compared to native PDMS microchannel. In addition to that and as explained before SiO2 on PDMS roughened microchannel surface, that is a common cause of premature breakdown and slowing down fluid stream over materials surface [18]. Moreover, SiO2 surface film had cracks, observed clearly via optical microscope.These grooves in film surface exert as specious capturing regions, which slowing down them and elongate their staying time [19]. Figure9:The PIV for different SiO2 thickness modified PDMS surface microchannel 3.6 Electric resistance of Cd+2 aqueous solutions mixed with AuNPcolloidal in modified PDMS surface Cadmium acetate aqueous solution classified as coordination polymer, featuring acetate ligands interconnecting cadmium centers. Its aqueous solution with AuNP colloidal mixture, prepared in our previous work [20], can exhibit water solubleconjugated conductive polyelectrolyte. Conductive polyelectrolyte phenomenon refers to carboxylate groups on AuNPs surface that bonded to Cd+2 owing to nanoparticles aggregating and networking [21]. This could be understood from the electric resistance measurements at modified PDMS microchannel that decreased with Cd ions in polyelectrolytes as shown in Fig.10 due to nanoparticles aggregating and networking increasing. Fig.11 shows polyelectrolytes electrical resistance with time in native and modified microchannel. Stable electric resistance observed at modified microchannel after 0.5 min compared to native microchannel. SiO2 deposited layer gives evidence to prevent species absorption into PDMS surface and enhance getting stable fluid flow into microchannel fabricated from PDMS. Figure10: The electric resistance for Cd aqueous solution and AuNP colloidal mixture at modified PDMS microchannel Figure11: The electric resistance stability with time at native and modified PDMS microchannel. IV. Conclusions In summary, we report in PDMS surface modification by deposition of SiO2in micro-channel. SiO2 alerts the PDMS optical and surface properties. PDMS new surface recovers part of its hydrophobicity after 7 hours and became stable for several days, increasing Si interlayer and SiO2 thickness found to reduce surface lost hydrophobicity. Electrophoresis flow on modified and native PDMS were studied using the particles image velocimetry. Particles velocities in modified PDMS microchannels became more stable, slowing down to approximately it’shalve value with SiO2 thickness and electric field strength. SiO2 deposition layer prevents species absorption into PDMS microchannel surface and enhance the solutions stabilities into microchannel. V. Acknowledgment The authors acknowledge many thanks to CRDF global for their support. The main author
  • 7. ShrokAllami et al Int. Journal of Engineering Research and Applications www.ijera.com ISSN : 2248-9622, Vol. 4, Issue 4( Version 1), April 2014, pp.324-330 www.ijera.com 330|P a g e ShrokAllamiwould like to express thanks to her host G.P.Li director of California Institute for Telecommunications and Information Technology (Calit2), University of California Irvine, USA. Mo Kibali, Albert Yee, Jack in INRF, Sarkis and Jason in UCI for their great supports and advisements to conduct this work. References [1] Jueyu Li and Min Wang, Chemical modification on top of nanotopography to enhance surface properties of PDMS, Surface & Coatings Technology, 2012; 206; 2161–2167. [2] ShankarDevasenathipathy and Juan G. Santiago, Particle Tracking Techniques for Electrokinetic Microchannel Flows, Anal. Chem., 2002; 74; 3704-3713. [3] Xueqin Rena, Mark Bachmanb, Christopher Simsc and G.P. Li, Electroosmotic properties of microfluidic channels composed of (polydimethylsiloxane), Journal of Chromatography B, 762;2001;117–125. [4] Christine Seguin, Jessica M., McLachlan and Peter R. Norton, Surface modification of poly (dimethylsiloxane) for microfluidic assay applications, Applied Surface Science, 256;2010; 2524–2531. [5] Jinwen Zhou, Recent developments in PDMS surface modification for microfluidic devices, Electrophoresis,31;2010;2–16. [6] Jiang-Tao Feng and Ya-Pu Zhao, Influence of different amount of Au on the wetting behavior of PDMS membrane, Biomed Microdevices, 10; 2008; 65–72, DOI 10.1007/s10544-007-9110-2 [7] Seunghwan Lee, Nicholas D. Spencer, Aqueous lubrication of polymers: Influence of surface modification, Tribology International - TRIBOL INT,38; 2005;11; 922-930. [8] DongheeLeea, Sung Yanga, Surface modification of PDMS by atmospheric-pressure plasma-enhanced chemical vapor deposition and analysis of long-lasting surface hydrophilicity, Sensors and Actuators B, 162;2012;425– 434 [9] Ingrid Hoek, Andrea Bubendorfer, Tim Kemmitt, W. Mike Arnold, IN-SITU Sol-gel modification of PDMS electrophoretic analytical device, in ;The 14th International Conference on Miniaturized Systems for Chemistry and Life Sciences 3 - 7 October 2010, Groningen, The Netherlands, p.1943- 1945. [10] KyoMiyaki, Hu-Lie Zeng, TatsuroNakagama, and Katsumi Uchiyama, Steady surface modification of polydimethylsiloxane microchannel and its application in simultaneous analysis of homocysteine and glutathione in human serum, Journal of Chromatography A, 1166;2007; 201–206 [11] Walter Schrott, ZdeněkSlouka, Petr Červenka, JiříSton, Marek Nebyla, Michal Přibyl,a) and DalimilŠnita, Study on surface properties of PDMS microfluidic chips treated with albumin, Biomicrofluidics, 3, 4, 2009, 044101. [12] Wintana T. Kahsai, Uyen H. T. Pham, Jeyantt S. Sankaran, and Samir M. Iqbal, Self- assembled synthesis and characterization of microchannels in polymeric membranes, J. Appl. Phys. 112; 2012;024701. [13] Kim.M.J., Kihm, and K.D., Microscopic PIV measurements for electro-osmotic flows in PDMS microchannels, Journal of Visualization, 7; 2;2004; 111-118. [14] NingBao, Jing-Juan Xu, Qing Zhang, Ji-Liang Hang, and Hong-Yuan Chen, Electroosmotic flow in poly(dimethylsiloxane) microchannels, Journal of Chromatography A, 1099;2005;203– 206 [15] Niu, Z. Q., Gao, F., Jia, X. Y., Zhang W. P., et al, Synthesis studies of sputtering TiO2 films on poly(dimethylsiloxane) for surface modification, Colloid Surf. A Physicochem. Eng. Aspects, 272;2006; 170–175. [16] Y. A. Kryukov, N. J. Podraza, R. W. Collins, and J. G. Amar, Experimental and theoretical study of the evolution of surface roughness in amorphous silicon films grown by low- temperature plasma-enhanced chemical vapor deposition. PHYSICAL REVIEW B, 80, 085403, 2009 [17] Qin Tu , Jian-Chun Wang, Yanrong Zhang, Rui Liu, Wenming Liu, Li Ren Sh, et al, Surface modification of poly(dimethylsiloxane) and its applications in microfluidics-based biological analysis, Reviews in Analytical Chemistry, 31; 3-4, 2012; 177–192. [18] Challa S. Kumar. Microfluidic Device in Nanotechnology; John Wiley & Sons Inc.; 2010. [19] Venuanand, Siddharth Ghosh, Moumita Ghosh, G.Mohan Rao, ReemaRailkar and Rajan R Dighe, Surface modification of PDMS using atmospheric glow discharge plasma with 1,1,1.2-tetrafluoroethane for biomolecules immobilisation , App.Surf.Sci., 257;2011; 8378- 8384 [20] Shrok Al-Lami, jamal F. Hamodi, hussian Ibrahim, Aws Faisal, FaydaHamood, and Abidl Hussein Nagim, Micro-fluidic device for Cd+ detection using gold nano particles, in; The fifth scientific conference on nanotechnology, advance materials and their applications; SCNMA2013; Baghdad,Iraq. [21] Diana Vilela, María C. González, Alberto Escarpa, Sensing colorimetric approaches based on gold and silver nanoparticles aggregation: Chemical creativity behind the assay. A review, AnalyticaChimicaActa, 751; 2012; 24-43