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International Journal of Polymeric Materials and

Polymeric Biomaterials

ISSN: 0091-4037 (Print) 1563-535X (Online) Journal homepage: https://www.tandfonline.com/loi/gpom20

Production of PDMS microparticles by


emulsification of two phases and their potential
biological application

Yo Han Choi, Kwang Hyo Chung, Hyo Bong Hong & Woon Seob Lee

To cite this article: Yo Han Choi, Kwang Hyo Chung, Hyo Bong Hong & Woon Seob Lee (2018)
Production of PDMS microparticles by emulsification of two phases and their potential biological
application, International Journal of Polymeric Materials and Polymeric Biomaterials, 67:11,
686-692, DOI: 10.1080/00914037.2017.1375494

To link to this article: https://doi.org/10.1080/00914037.2017.1375494

View supplementary material Published online: 28 Sep 2017.

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INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS AND POLYMERIC BIOMATERIALS
2018, VOL. 67, NO. 11, 686–692
https://doi.org/10.1080/00914037.2017.1375494

none defined

Production of PDMS microparticles by emulsification of two phases and


their potential biological application
Yo Han Choia, Kwang Hyo Chunga, Hyo Bong Honga and Woon Seob Leeb
a
Electronics and Telecommunications Research Institute, Daejeon, Republic of Korea; bMemory Manufacturing Operation Center,
Samsung Electronics, Suwon, Republic of Korea

ABSTRACT ARTICLE HISTORY


Poly(dimethylsiloxane) (PDMS) has been widely used for prototyping of chips. Among many kinds of Received 4 May 2017
microstructures, it is almost impossible to make few micron-sized PDMS particles through microfluidic Accepted 19 August 2017
focusing methods because of the highly viscous property of uncured PDMS. Vigorous mixing of PDMS KEYWORDS
with water resulted in small, spherical particles was found. Furthermore, a simple and easy method was Emulsion; gene delivery;
devised to assure an emulsion state. The PDMS–water emulsion was made using two syringes connected particle; PDMS
by a needle. This emulsion was rapidly heated to cure the PDMS within the emulsion. The resultant
PDMS was examined using spectroscopic methods to determine the particulate morphology and size
distribution. PDMS particles of which the size was around 1 µm with a narrow size distribution was
produced. DNA delivery into cultured animal cells through these PDMS microparticles was also
demonstrated as an illustrative application. These biologically inert microparticles will find many more
practical applications with additional fine-tuning modifications based on discussed considerations.
GRAPHICAL ABSTRACT

1. Introduction serial synthesis [13]. Moreover, the high viscosity of PDMS


is another serious obstacle to the microfluidic focusing meth-
Particles 1 µm or less in diameter have been widely used based
ods. Production of PDMS particles by physical emulsification
on their outstanding merits, which include their relatively
was also reported, but only to harvest particles with irregular
high surface-to-volume ratio. Polystyrene, for example,
sizes [14,15]. There was a report showing the synthesis of
because of properties such as biocompatibility, nontoxicity,
monodisperse PDMS particles with diameter of 1.5–2.5 µm;
strong adsorption ability, and chemical inertness, has been
however, it took 12–24 h to complete the synthesis, and also
the choice for the particles used in academic and practical
required vigorous shaking and chemical reactions [16].
fields [1–4]. Another currently used polymer, poly(dimethlysi-
Poly(dimethylsiloxane) is very elastic and gas permeable,
loxane) (PDMS), which has been used as electric insulation,
unlike other solid polymers for microparticles [17]. Therefore,
has more recently been actively adopted in microchip
mass production of PDMS microparticles will open a new era
fabrication fields for use in prototyping microstructures
of microparticle applications. For example, a gas sensor of
[5–8] and soft lithography [9,10]. Microbeads of PDMS were
PDMS particles made use of their gas permeability [11]. In
also reported, which were made by combining microfluidic
addition, the hydrophobicity of PDMS could be beneficial if
control and instantaneous heat curing [11]. There have been
a hydrophobic drug is the target of delivery [18]. A primitive
many trials performing microfluidic droplet formation and
trial of PDMS particles’ production was previously reported
describing relevant applications [12,13]. In spite of the
[19]. In this report, a systematic approach is described for
advantage of creating monodisperse particles of adjustable
producing PDMS microparticles, and analytical data are
sizes, however, these microfluidic-dependent methods are
presented. The practical potential of PDMS microparticles is
not amenable to mass production because of their mode of

CONTACT Yo Han Choi tabby@etri.re.kr Electronics and Telecommunications Research Institute, 161 Gajeong-dong, Yuseong-gu, Daejeon,
Republic of Korea.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpom.
Supplemental data for this article can be accessed on the publisher’s website.
© 2017 Taylor & Francis
INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS AND POLYMERIC BIOMATERIALS 687

also demonstrated by their use in gene deliveries, one of the cuvette (Sigma). The particle size distribution was measured
most popular biological applications. using a Zetasizer Nano ZS90 (Malvern) according to the
manual of manufacturer instructions. Zetasizer Software 7.03
2. Experimental was used for the analysis and data acquisition.

2.1. Preparation of reagents


2.6. Cell culture
Poly(dimethylsiloxane) (Sylgard 184) was purchased from
COS-7, a monkey kidney cell line, was a kind gift from
Dow Corning. The silicone elastomer was mixed with 1/10
Dr Jeong Won Park at ETRI in South Korea. Cells were grown
volume of curing agent. The mixture was gently stirred for
at 37°C in a humidified incubator supplied with 5% CO2.
more than 5 min, and the uncured PDMS mixture was used
Dulbecco’s modified Eagle’s medium, supplemented with fetal
within an hour. Plasmid DNAs, pEF1a-AcGFP1-C1, which
bovine serum and gentamicin (10% and 0.05 mg/mL, respect-
expresses GFP (green fluorescent protein); and pCMV-TET3G
ively), was used for the maintenance of cells. All cell culture
with pTRES3G-BI-Luc control, which expresses luciferase
reagents were purchased from Welgene. The GFP expression
inductively, were purchased from Clontech and amplified
was observed with a light microscope (Eclipse TE2000-U,
through Escherichia coli using conventional methods [20].
Nikon) equipped with a CCD camera and an ultraviolet light
Plasmids were purified using a commercial product, Plasmid
source. Micro-Manager 1.4 (Micro-Manager) with ImageJ
Plus Giga Kit (Qiagen).
1.48 v was used for operation of microscope and acquisition
of image data.
2.2. Vortex mixing of two phases
A portion (0.5 mL) of PDMS was mixed with triple the volume 2.7. Surface coating of PDMS particles with
of distilled water in a 50-mL conical tube. These two immis- plasmid DNA
cible phases were mixed using a vortex mixer (Vortex Genie
2, Scientific Industries) at its maximum output for 10 min. Just Poly(dimethylsiloxane) particles were coated with plasmid
after the end of vortex mixing, the mixture was directly poured DNA according to the procedures in a previous report,
into 200 mL of boiling water for instantaneous curing. The with some modifications [21]. Chitosan (MW 200 kDa, Sigma)
PDMS particles in the water were harvested by centrifugation was dissolved in 0.4% (w/w) of acetic acid to make 0.5% (w/v)
for 5 min at 1500�g at room temperature. stock solution. This stock was diluted with distilled water to
0.05% (w/v) working solution. The solvent of the plasmid
DNA was substituted with 10 mM 2-(N-morpholino)ethane-
2.3. Emulsification by Luer lock syringes sulfonic acid (MES, Sigma) buffer. PDMS particles were
The uncured PDMS mixture was mixed with distilled water poured into a 0.05% (w/v) chitosan solution and incubated
using two Luer lock syringes. Two Luer lock syringes for 30 min at ambient room temperature. The particles were
(Norm-Ject) were connected through a Luer lock metal needle then washed with distilled water by centrifugation at
of gauge number 18, 20, or 25 (Cadence Science). Each barrel 20,000�g for 20 min at 4°C. PDMS particles were resuspended
of the syringes was moved to-and-fro 10 times to achieve with 0.5 mg/mL of DNA solution and incubated further for 2 h
emulsification. The emulsified mixture was directly poured at 4°C. Finally, unbound DNA was washed out with MES
into 50 mL of boiling water, and the mixture was centrifuged buffer.
for 5 min at 1,500�g to remove large particles. The super-
natant was centrifuged again for 5 min at 8,000�g to harvest 2.8. Scrape loading of PDMS particles into cultured
the PDMS particles. mammalian cells
Poly(dimethylsiloxane) particles were introduced into cultured
2.4. Microscopic examination of PDMS particles
cells by scrape loading as previously described with some
The morphologies of the produced PDMS particles were modifications [22,23]. 5 � 104 COS-7 cells were plated in each
observed with a surgical endoscopy system (Camscope DCS- well of a 6-well plate on the day before usage. About 2 � 1010
pro, Sometech) or with a light microscope (Eclipse TE2000- PDMS particles coated with or without plasmid DNA in
U, Nikon) equipped with a CCD camera. The detailed 0.5 mL of PBS were poured on COS-7 cells of which the media
morphologies were also examined using a scanning electron had been removed and washed once with PBS. The cells were
microscope (SEM). Briefly, the PDMS particles were placed then scraped from the culture surface with a rubber policeman
on a piece of silicon wafer and allowed to dry at room tem- (Nunc). After being harvested by centrifugation at 1000�g for
perature before being sputter coated with Au for the SEM 2 min, the cells were plated again in their previous wells with
inspections. The prepared specimens were examined with a new culture media.
SEM (Sirion, FEI Company) operated at an accelerating
voltage of 10 keV, with a 10-mm working distance. 2.9. Luciferase assay
A luciferase assay was performed according to the manufac-
2.5. Size analyses of PDMS particles
turer’s instructions. COS-7 cells were scape-loaded with about
The produced PDMS particles were suspended in 1 mL of 2 � 1010 PDMS particles that had been coated with pCMV-
distilled water and poured into a transparent polystyrene TET3G and pTRES3G-BI-Luc control. After 4 h of scrape
688 Y. H. CHOI ET AL.

loading, cells were stimulated with doxycycline (300 ng/mL). parts of immunization protocols [24]. An emulsion of PDMS
Cells were then harvested and washed with PBS for 24 h after and several times volume of distilled water were created using
scape loading. Next, 20 µL of cell lysate was mixed with 100 µL this needle and the syringes by directing the liquid back and
of Luciferase Assay Reagent (Promega) in a Corning 96-well forth 10 times with to-and-fro manual movements, which took
white plate. The luminescence was measured using a Spectra- only tens of seconds (Figure 2). The optimal volume ratio was
Max L (molecular devices). pretested for two perspectives, particles size and manual
feasibility. Emulsions with different five volume ratios of
PDMS to distilled water (1:1, 1:2, 1:3, 1:4, 1:5, and 1:10) were
3. Results
tested. Using more distilled water made emulsification easier
Because of the immiscibility of PDMS with water, distilled but lowered the yield. There was no detectable difference
water was selected as the emulsion partner of PDMS. A portion among harvested particles from emulsions of different mixing
(0.5 mL) of PDMS with curing agent was mixed with 1.5 mL of ratios, except for 1:1 and 1:2, which mostly produced lumps of
distilled water. After vigorous vortex mixing for 10 min, the PDMS (data not shown). Therefore, the 1:5 ratio for this work
mixture was poured into boiling water. This preliminary was chosen.
experiment resulted in primitive but promising products. As the two immiscible phases are mixed, the emulsifying
Figure 1 shows the particles obtained after drying of the to-and-fro movements become harder to perform by hand.
water. The diameter of particles varied from several tens of It was reported that the addition of surfactant(s) promoted
micrometer to several millimeter with extreme heterogeneity. emulsification by reducing the surface tension existing at the
Most of the particles, however, were perfectly spherical. interface of two immiscible materials [25]. Moreover, adequate
Therefore, it is able to produce smaller spherical PDMS amount of sodium dodecyl sulfate (SDS), one of the anionic
particles by introducing harsher shearing conditions is surfactants, is known to increase emulsion stability when used
speculated, and that the harsher condition would possibly with proteins [26]. Therefore, SDS at 1, 5, and 10% (w/v) was
improve heterogeneity by narrowing the available range of prepared in distilled water, and PDMS was mixed with these
physical dimensions of particles. SDS solutions at a ratio of 1:5 (PDMS:SDS solution). The
As a matter of fact, PDMS particles had previously been resistance to the back-and-forth movements was greatly
produced through emulsification using a commercially reduced when SDS solution replaced the distilled water.
available stirrer [14–16]. However, those methods required However, the presence of SDS did not make notable
spending from several hours to a day. A pressure-drop differences in the size distribution. There was no detectable
phenomenon using conventional syringes for fast, easy, and concentration-dependent pattern, either. Furthermore, emul-
simple emulsification was adopted. Two Luer-lock-type sions with 5 and 10% of SDS did not show any clear particle
syringes connected with a needle have been used routinely structures when SDS was not washed out before SEM imaging
for emulsification of oily adjuvant, Freund’s adjuvant, with (data not shown). In fact, the deleterious effect of excess SDS
aqueous antigen solution, which is one of the most common on the emulsion stability was also discussed at the same
report [26]. Addition of SDS was inevitable only for the
emulsification using 25 gauge needle.
Figure 3 shows SEM images of representative particles
made using this method. Particles harvested just before
centrifugation at 1,500�g showed great variation in size
(Figure 3a). After centrifugation, most of the larger particles
had been removed, leaving particles of about 1 µm sizes
(Figures 3b and 3c). Even so, some variations could be
detected when diluted particles were imaged (Figure 3d).
Smaller particles seemed to be buried within larger ones in

Figure 2. Emulsification of PDMS with distilled water using two connected


syringes. Each syringe with PDMS or with distilled water was connected through
a needle (top). One piston was pushed into its barrel to inject the contained
Figure 1. Macroscopic PDMS particles of diverse sizes. Uncured PDMS was mixed material into the other connected syringe (middle). The mixture, alternately,
by vortexing with triple volumes of distilled water; then instantaneously cured in was injected into the opposite syringe again (bottom). This to-and-fro movement
hot water. The diameter of the obtained PDMS particles varies from several tens of cycle was performed 10 times to achieve emulsification. Note: PDMS, poly
micrometer to several millimeter. Note: PDMS, poly(dimethlysiloxane). (dimethlysiloxane).
INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS AND POLYMERIC BIOMATERIALS 689

Figure 3. SEM images of the produced PDMS particles. Particles showed heterogeneous sizes just after curing (a). Brief centrifugation removed the larger ones,
leaving the relatively regular ones (b), mainly around 1 µm (c). Several hundreds of nanometer variation could be detected when diluted particles were examined
(d). Smaller particles seemed to be buried within larger ones in dense samples (c). Note: SEM, scanning electron microscope; PDMS, poly(dimethlysiloxane).

dense samples. It was apparent in the visuals that PDMS par- volume would be 0.523 µm3, 100 mg of PDMS should make
ticles have spherical morphology, and that direct contact about 2 � 1011 particles.
between particles seemed to have resulted in squashing of The PDMS particles were analyzed to measure the details of
the contact areas (Figure 3d). Because simple dilution of the their size distribution. As shown in Figure 4, the size of most
particles could make the particles separate, the contact among particles was around 1 µm. Actually, there was some shift of
particles may not be an irreversible phenomenon. If the the size of most frequently observed peaks among the different
squashing of particles after contact had been irreversible, productions. However, the peak was always around 1 µm,
essentially no particle could have retained their spherical mor- within more or less a couple of 100 nm and the shapes of
phology. The separated spherical morphology was very stable the peaks were always similar. In the example in Figure 4,
in water as already found no morphological alteration through the most frequently observed size was 989.8 nm and the stan-
SEM even 6 months after the original production and storage dard deviation was �217.8 nm. Several other size distributions
in water at room temperature. The number of PDMS particles are summarized in Table 1 with numerical data, and each
could be approximated from each fractional mass. Large graphical result is depicted in Supplemental Figures.
particles precipitated by centrifugation at 1,500�g weighed It was reported that DNA was directly delivered into cells
about 100 mg when 200 mg of uncured PDMS was used for through several micron-sized alginate particles using poly-
the initial emulsification. If the average diameter of the rest ethylene glycol [27,28]. As an illustrative example of practical
is assumed to be 1 µm (see below, Figure 4), of which the application, PDMS particles could be delivered into cells

Table 1. Additional measurements of different lots of PDMS microparticles.


Sizes of main peaks, percentages of those peaks, and standard deviations are
noted.
Size (nm) Intensity (%) St. dev. (nm)
a 754.9 100.0 108.5
b 765.6 100.0 105.4
c 798.4 100.0 171.4
d 952.7 100.0 210.7
ea 989.8 100.0 217.8
f 1267 100.0 247.8
Figure 4. The size distribution of the PDMS particles was optically analyzed. The g 1269 100.0 228.8
size of the main peak is 989.8 nm with standard deviation of 217.8 nm. There h 1302 100.0 259.4
were some detectable but not drastic shifts of main peaks among the different i 1327 100.0 284.4
lots of PDMS particles, and more analyses are shown in Table 1. Note: PDMS, PDMS, poly(dimethlysiloxane).
a
poly(dimethlysiloxane). This is the same one in Fig. 4.
690 Y. H. CHOI ET AL.

Gene delivery was also demonstrated using a luciferase


assay. PDMS particles coated with plasmids of a luciferase
gene and additional plasmids of an inductive gene were
scrape-loaded into COS-7 cells, as indicated above. The
luciferase activity was apparently detected by these COS-7
cells, as shown in Figure 6. As compared with cells that had
been loaded with mock DNA-coated PDMS particles, cells that
had been loaded with luciferase DNA-coated ones showed
luciferase activity that was about 1,000 times greater. Taken
with the detection of GFP, this result clearly demonstrates that
the PDMS microparticles were able to be delivered into cells
with exogenous materials. The successful delivery of DNA
through PDMS particles must have been achieved mainly by
its small size. By the way, if the size uniformity is not good,
larger ones will not contribute to the gene delivery, but just
exhaust DNA. Therefore, uniform size may be very important
also for the efficient delivery only if the size is adequately
small.

Figure 5. GFP expression by the plasmids delivered through PDMS particles.


COS-7 cells were scrape-loaded with PDMS particles that had been coated with
4. Discussion
plasmids of the GFP gene. After 24 h of scrape loading, cells were detected under
a fluorescence microscope. Scale bars ¼ 50 µm. Note: GFP, green fluorescent The flow in the device was theoretically analyzed using a flow
protein; PDMS, poly(dimethlysiloxane). model shown in Figure 7. Three circular channels of different
diameters [D1, D2, and D3 for Channel 1, 2, and 3, respectively.
accompanying DNA as a reporter was demonstrated. Scrape D1 (¼D3) > D2] were connected longitudinally. The flow is
loading is a transfection method based on mechanical stress. constricted and expanded from Channel 1 to Channel 3 with
It is expected that the PDMS particles could be delivered into a constant flow rate Q. For the laminar Hagen–Poiseuille flow,
cells because of their small sizes, although scape loading was the pressure drop (DP) and the wall shear stress (τw) in the
generally used with DNA and proteins. The PDMS particles circular channel of length L and of diameter D are expressed
were coated with plasmids of the GFP gene with the aid of as Eqs. 1 and 2, respectively [29].
chitosan. COS-7 cells were scrape loaded with these particles, 128lLQ
and the expression of GFP was detected confirming the DP ¼ ð1Þ
pD4
delivery of PDMS particles. As shown in Figure 5, clear fluor- dv 32lQ
escence was detected after 24 h of scrape loading. Although the sw ¼ l ¼ ð2Þ
dr pD3
overall transfection efficiency was low, maybe less than 1%,
fluorescence was clearly detected in the repeated verifying The pressure drop is proportional to the length of each
experiments. channel and inversely proportional to the biquadrate of the
diameter. Moreover, the wall shear stress of each channel is
inversely proportional to the cube of the diameter and inde-
pendent of the length of channel. From Eqs. 1 and 2, the ratio
of pressure drops and the ratio of the wall shear stresses
between wide and narrow channels can be described by
� �
DP2 L2 D1 4
¼ ð3Þ
DP1 L1 D2
� �3
sw;2 D1
¼ ð4Þ
sw;1 D2

Figure 6. Luciferase activities in COS-7 cells were measured. The cell extract of
COS-7 cells that had been scrape-loaded with PDMS particles coated with
plasmids of the GFP gene was harvested, and a luciferase assay was performed
using a commercial kit. Luciferase activity, which indicates a successful gene
delivery, was apparently detected (right column) as compared with the control Figure 7. Schematic flow model. Each barrel of two syringes and connecting
(left column). Note: PDMS, poly(dimethlysiloxane); GFP, green fluorescent protein. needle are depicted as Channel 1, Channel 3, and Channel 2, respectively.
INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS AND POLYMERIC BIOMATERIALS 691

Thus, the pressure drop mainly occurs in the narrow channel applied at the syringe plunge is 13 N. When the gauge of the
when the diameter ratio (D1/D2) is very high, as it is in the device connecting needle (Channel 2) is changed to gauge 25 (D2 ¼
(D1 ¼ 11.73 mm, D2 ¼ 0.584 mm for the 20 gauge needle). Simi- 0.241 mm), the pressure drop and shear stress are changed
larly, the shear rate, which is proportional to the shear stress for to DP2 ¼ 4.15 � 105 Pa, τw,2 ¼ 1.25 � 104 Pa and the shear rate
a Newtonian fluid, becomes relatively very high in the narrow of 1.45 � 106 1/s. Also, the driving force applied at the syringe
channel. This means that the ultrahigh shear deformation plunge is 449 N. This results means that the pressure drop,
(∼8,000 times greater) occurs within the needle of the device. shear rate, and force dramatically vary at the gauge range
In addition, the real values of the pressure drop, shear between 20 and 25. If it is to use the smaller needles at the con-
stress, and total force for dimensions and flow conditions of necting channel (gauge number above 25), the device is to be
the device (D1 ¼ 11.73 mm, D2 ¼ 0.584 mm, D3 ¼ 11.73 mm, modified to endure the extremely high pressure and shear.
L1 ¼ 20.0 mm, L2 ¼ 20.0 mm, L3 ¼ 20.0 mm, and Q ¼ 2 mL/s) Meanwhile, although the shear rate (∼1.02 � 105 and
were calculated. The viscosity of PDMS–water emulsion is 1.45 � 106 1/s for 20 gauge and 25 gauge needles, respectively)
constant regardless of the shear rate [actually, PDMS shows and the average velocity (∼7.47 and 43.8 m/s for 20 gauge and
shear thinning behavior at high shear rates (>10,000 1/s) 25 gauge needles, respectively) are very high in the connecting
and high viscosity (>5,000 cSt)] [30] was assumed and calcu- needle, the flow is still under a laminar flow regime. The flow
lated it using the Refutas equation [31]. This is a useful becomes laminar when the Reynolds number [29], which is
method for estimating the viscosity of a blend of multiple defined in Eq. 8, is below 2,300. The Reynolds number is 97
liquids. The calculation of viscosity of the PDMS–water blend and 234 for the needles of 20 gauge and 25 gauge, respectively.
is performed in three steps, as follows. The smaller diameter of the channel and the high viscosity of
1. Calculate the viscosity blending number (VBN) of the water the fluid in the device cause the flow to remain laminar. This
and PDMS: makes the diameter of the PDMS particles nearly constant and
reproducible under the designed experimental conditions.
VBN ¼ 14:534 � ln½lnðv þ 0:8Þ� þ 10:975 ð5Þ
where ν is the kinematic viscosity in centistokes (cSt). �
qVD
2. Calculate the VBN of the blend: Re ¼ ð8Þ
l
VBNBlend ¼ ½xwater � VBNwater � þ ½xPDMS � VBNPDMS � ð6Þ
The use of a needle with a larger gauge number (smaller
where x is the mass fraction of each component of the diameter) generated few differences. Smaller and a little bit
blend. more even particles could be harvested in addition to the
3. Determine the kinematic viscosity of the blend by solving decreased initial large particles using a 25 gauge needle rather
Eq. 5 for ν: than 18 or 20 gauge needles. The pressure drop is directly
� � �� related to shear stress, which exerts an effect on the formation
VBNBlend 10:975
v ¼ exp exp 0:8 ð7Þ of emulsion. Therefore, the thinner the needle, the harsher will
14:534
be the emulsifying condition. However, each flow within 20
The viscosity of water is 1 cSt, and that of PDMS is 5,000 and 25 gauge needles was calculated to be still under a laminar
cSt. The viscosity values of the PDMS–water blend for several flow regime, which might have caused few differences among
mass ratios using Eqs. 5–7 were obtained, and the results are particles from different needles. Keeping laminar flow also
shown in Figure 8. For the blend liquid of the mass fraction seems to have contributed the relatively regular particles
0.5, the viscosity is about 8.6 cSt assuming its density is (detailed theoretical analyses of the emulsifying flow are dis-
1,000 kg/m3. For the values above, it is obtained: DP1 ¼ DP3 ¼ cussed in the Supplementary Data). Using needles thinner
0.74 Pa, DP2 ¼ 1.2 � 105 Pa, τw,1 ¼ τw,3 ¼ 0.109 Pa, τw,2 ¼ than 25 gauge, in addition, seems to require modification of
879 Pa, and a shear rate of 1.02 � 105 1/s. The driving force the methods because of the extremely high pressure and shear
force within the syringes. As a matter of fact, it was almost
impossible to perform the manual to-and-fro movements
using a 25 gauge needle if there was no SDS.
The major shortcoming of this method is the lack of fine
control for particle size. However, considering that the smal-
lest organic particles that are commercially available, such as
polystyrene, have sizes around 1 µm, the method will be very
useful for mass producing particles of sizes that are in frequent
demand. In addition, although it is failed in making smaller
PDMS particles by addition of a diluent, hexane, intending
to lower the viscosity of uncured PDMS (data not shown),
future developments for modulation of the viscosity should
present chances to control the size of PDMS particles down
to several tens of nanometers. Changing the materials would
open additional value of this method. Currently, it is success-
Figure 8. Variation of viscosity of PDMS–water emulsion for several mass ratios fully applied to another less viscous material to make
obtained by the Refutas equations. Note: PDMS, poly(dimethlysiloxane). 300–500 nm-sized particles [32]. In this primitive study, sol
692 Y. H. CHOI ET AL.

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