Accepted Manuscript

Uniformly dispersed polymeric nanofiber composites by electrospinning: Poly(vinyl

alcohol) nanofibers/polydimethylsiloxane composites

Kentaro Watanabe, Tomoki Maeda, Atsushi Hotta

PII: S0266-3538(17)32770-7
DOI: 10.1016/j.compscitech.2018.06.007
Reference: CSTE 7263

To appear in: Composites Science and Technology

Received Date: 14 November 2017

Revised Date: 20 April 2018
Accepted Date: 7 June 2018

Please cite this article as: Watanabe K, Maeda T, Hotta A, Uniformly dispersed polymeric nanofiber
composites by electrospinning: Poly(vinyl alcohol) nanofibers/polydimethylsiloxane composites,
Composites Science and Technology (2018), doi: 10.1016/j.compscitech.2018.06.007.

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 ACCEPTED MANUSCRIPT

Uniformly dispersed polymeric nanofiber composites by electrospinning:

poly(vinyl alcohol) nanofibers/polydimethylsiloxane composites

Kentaro Watanabe, Tomoki Maeda, and Atsushi Hotta

Department of Mechanical Engineering, Keio University, 3-14-1 Hiyoshi, Kohoku-ku,

Yokohama 223-8522, Japan

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Corresponding Author: Professor Atsushi Hotta

E-mail: hotta@mech.keio.ac.jp

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Postal address: Department of Mechanical Engineering, Keio University, 3-14-1

Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan

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Abstract

A method for the fabrication of homogeneous and well-dispersed polymeric

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nanofiber composites was investigated. Nanofiber fillers can be used to produce

polymeric nanocomposites by mixing the fillers to base polymers, eventually enhancing

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the mechanical property of the matrix polymers. To produce such composites,

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nanofibers were usually sandwiched by molten matrix polymers at high temperature

before molding. The traditional so-called sandwich method, however, was found to
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produce rather biased and inhomogeneous composites due largely to the solid

entanglement of the nanofibers. In this work, unwoven polymer nanofibers were

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synthesized through electrospinning by controlling the electrostatic repulsion of the

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nanofibers. We modified the electrospinning apparatus for the direct synthesis of

homogenous composites: nanofibers were electrospun and directly ejected from the

electrospinning syringe to the matrix polymer solution (not in a solid state), where a

regular metal electrode plate was replaced by an optimized metal container containing

the base polymer solution. It was found that this new fabrication method could realize

homogeneous mixing of the nanofibers that were eventually uniformly dispersed in the

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polymer solution. Poly(vinyl alcohol) (PVA) was used for nanofibers and

polydimethylsiloxane (PDMS) was used for polymer matrix. The field emission

scanning electron microscopy (FE-SEM) revealed the homogeneous and well-dispersed

PVA nanofibers in the resulting PDMS composites. The composites also presented

higher mechanical properties as compared with the composites fabricated by the

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traditional sandwich method.

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Keywords: Fibres, Nano composites, Electro-spinning, Polymer-matrix composites

(PMCs), Mechanical properties

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1. Introduction

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Polymeric nanofiber composites were nanocomposites, possibly providing
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higher mechanical properties with superior structural characteristics including high

transparency due to their nanoscale structures, as compared with traditional fiber

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composites by carbon, glass, and Kevlar fibers [1-7]. To produce polymeric nanofibers

for composite fillers, electrospinning has been widely used and recognized as an
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efficient way [8]. Various polymers have recently been successfully electrospun into
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ultrafine fibers [9-11]. Fine fibers with a very large surface area could create unique

properties such as the flexibility in surface functionalities, the superior mechanical

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performance, and the good interfacial adhesion [12-17]. In fact, Liao et al. reported a

cellulose acetate (CA) nanofiber-reinforced epoxy composite film via electrospinning

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and solution-impregnation methods [13]. Moreover, it was found that the strong
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interfacial adhesion of the CA/epoxy composites resulted in the high mechanical

strength.

As for the fabrication methods for composites, there have been quite a few

researches on the manufacturing of nanofiber composites using electrospun nanofibers.

The composites were generally obtained by sandwiching electrospun nanofibers by base

polymer films using a hot press, and the sandwich process was carried out after the

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fabrication of nanofiber sheets by electrospinning [18-20]. For the sandwich method,

the glass-transition temperatures (Tg) and the melting points (Tm) of polymeric fibers

as well as matrix polymer are both important: a composite should be molded below Tg

or Tm of the fibers, but above Tg or Tm of the base polymer, so that the molten base

polymer could effectively penetrate and fill the voids of the nanofiber sheets when

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blended [19]. The resulting sandwiched composites were reported to present enhanced

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mechanical properties for highly functionalized polymers: controlled biodegradability

by polyvinylpyrrolidone fibers/polycaprolactone and enhanced mechanical properties

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by CA nanofibers/ poly(butylene succinate) [18, 20]. These composites made by the

hot-press method, however, were relatively anisotropic and inhomogeneous, containing

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nanofibers with insufficient dispersion in the base polymer especially in the depth
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(thickness) direction. In particular, the inhomogeneity of the nanofiber composites in the

thickness direction could become prominent as the amount of the fibers decreased,
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while the uniformity in the thickness direction of the composite could be obtained when

the concentration of the fibers reached as high as 40-70%. This was mainly due to the
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firm entanglements of the nanofibers established during the synthesis through

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electrospinning.
The main purpose of this work is to modify the existing electrospinning
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method for the direct synthesis of nanofiber composites to realize uniform nanofiber
dispersion. Our challenge in this work particularly lies in improving the inhomogeneity
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of the nanofiber composites due to the lower concentration of fibers, as well as studying
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the nano-effects of the PVA/PDMS composites at the low concentrations of the PVA

fibers (1-6 wt%). Instead of using an existing earthed metal plate, polymer solution was

used as a new earthed collector that was filled up in a newly designed grounded metal

container (Fig. 1). After crosslinking, the dispersibility of poly(vinyl alcohol) (PVA)

nanofibers was studied using the field emission scanning electron microscopy

(FE-SEM) through the ruptured composite surfaces. The mechanical properties of the

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composites were also investigated by analyzing the stress-strain curves obtained by a

tensile tester.

2. Materials and Method

2.1 Materials

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For the nanofibers, PVA was used (from Junsei Chemical Co., Ltd.), which has

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the molecular weight of Mw~66,000 measured by the gel permeation chromatography

(GPC), Tm of 228°C measured by the differential scanning calorimetry (DSC), and the

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Young’s modulus of 2.5 GPa measured by a tensile tester. Distilled water and ethanol

(both from Wako Pure Chemical Industries, Ltd.) were used to dissolve PVA. PDMS

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(SILPOT 184 from Dow Corning Toray Co., Ltd.) was used as the matrix polymer with
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the Young’s modulus of 1.4 MPa.

2.2 Modified electrospinning setting for the synthesis of the fiber composites
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A new collector for the electrospinning was designed to obtain the aimed

composites in which nanofibers were well dispersed. In an ordinary electrospinning

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apparatus, the existing metal collector (plate) was simply grounded to gather fabricated
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nanofibers as indicated in Fig. 1 (a). For the new setting, the base polymer solution was

poured into a grounded metal container instead of the ordinary metal plate. Fig. 1 (b)
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shows the new optimized setting of the electrospinning apparatus presenting a

cylindrical doughnut-shaped silicone rubber packing being laid on to an aluminum tub

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to contain liquid base polymer. The dimensions of the insulating rubber packing and the
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conducting aluminum were both pre-examined and optimized: for the rubber packing,

55 mm for the internal diameter, 92 mm for the external diameter, and 0.5 mm for the

thickness were selected and for the aluminum container, 100 mm for the external

diameter. With these optimized experimental settings, the electrospun nanofibers could

be neatly synthesized and ejected into the polymer solution.

2.3 Fabrication of well-dispersed PVA/PDMS composites (PVA/PDMS-d)

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PVA pellets were dissolved in water/ethanol (10/1) to make 8 wt% of PVA

solution. The solution was stirred at 500 rpm for 24 hrs at 90˚C for the complete

dissolution. 0.3-1.5 g of the base PDMS prepolymer solution with a crosslinking agent

(PDMS prepolymer/crosslinking agent=10/1) was prepared and installed in the collector

mentioned above. PVA nanofibers were then fabricated using an electrospinning

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apparatus (IMC-1639 from Imoto Machinery Co., Ltd.) with a 5 mL syringe (Model

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1005 LT from Hamilton Co.) and a needle of 0.53 mm in diameter, where the applied

voltage was set at 7.2 kV, the feed rate was set at 0.3 ml/hour, and the tip-target distance

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was set at 8 cm. The homogeneous nanofiber morphology of the electrospun PVA was

confirmed by the SEM micrograph as shown in Fig. S1, which should make significant

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contributions to the mechanical property of the resulting PVA/PDMS composites. After
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blending the PVA nanofibers with the PDMS prepolymer, the composites were

crosslinked at 50°C under the pressure of 1 atm for ~24 hours. For comparison, the
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traditional sandwiched PVA/PDMS composites (PVA/PDMS-s) were also made by the

conventional electrospinning method. Other electrospinning conditions for

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PVA/PDMS-s were the same as those for PVA/PDMS-d.

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The PVA concentration in the PVA/PDMS composite was calculated as

follows:
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 − 

 
   % = × 100

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where WComposite was the weight of the PVA/PDMS composite and WPDMS was the

weight of the PDMS used for the fabrication of the PVA/PDMS composite.

2.4 Dispersibility of the PVA nanofibers in the composites

To evaluate the dispersibility of the PVA nanofibers in the PDMS matrix,

microstructural observations were carried out by SEM. After the tensile test, the fracture

surface was scanned using the FE-SEM to study the fiber morphology. The composite

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specimens were coated with osmium to prevent charging during the SEM measurements.

13 pictures were taken down to the depth of 70 µm from the surface of the composites,

and the detection frequency of PVA nanofibers was set and measured over the 6 µm×

14 µm square area of the SEM micrographs.

2.5 Transparency of the PVA/PDMS composites

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The light transmittance was investigated by the spectral photometer (U2810

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from Hitachi High-Technologies Co.) from 350 nm to 750 nm in wavelength for the

measurement of the transparency of the composites.

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2.6 Young’s modulus and fracture strain measurements

Tensile testing was performed to examine the mechanical properties of

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PVA/PDMS-d and PVA/PDMS-s. A dog-bone shaped specimen of 16.5 mm × 3 mm
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was prepared and used for the mechanical testing. The appropriate tensile load was

applied to the samples with the crosshead speed of 3 mm/min using a universal testing
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machine (AG-IS, Shimadzu Co.). The gauge length, the distance between the two jaws,

was set at 22 mm, and at least 4 specimens were tested for the determination of the
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mechanical properties of each sample.

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3. Results and discussions

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3.1 Dispersibility of PVA nanofibers

As shown in Fig. 2, a partially coarse surface was observed in the fractured

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surface of PVA/PDMS-s at the PVA concentrations of 1 wt% and 4 wt%. Comparing the
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fractured surface of the PVA/PDMS-s with that of pure PDMS base polymer (Fig. S1),

the coarse parts of the PVA/PDMS-s were produced by PVA nanofibers near the surface

of the composite film. In fact, the aggregations of the PVA nanofibers with 150 nm in

diameter only existed near the surface of the composite and the nanofibers were not

found relatively deep inside the composite. The experimental results indicated that the

PVA nanofibers had already been well entangled with each fiber before mixing using

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the conventional sandwich method, where the fibers were firmly fixed and immobile

during the mixing with liquid uncrosslinked PDMS. The entangled PVA nanofibers

could never be untied and loosened and consequently, and an inhomogeneous

PVA/PDMS-s composite was obtained by the traditional sandwich method.

Fig. 3 shows the SEM micrographs of the fractured surface of PVA/PDMS-d

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fabricated by the modified ES method. In contrast to the PVA/PDMS-s, the

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PVA/PDMS-d had PVA nanofibers not only at the surface but also deep inside the

composite. It was therefore concluded that the new ES method of using liquid polymer

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as a grounded collector could readily produce a relatively homogeneous composite with

well-dispersed PVA nanofibers in PDMS.

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Fig. 4 shows the evaluation of the dispersibility of PVA nanofibers by the SEM
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micrographs regarding (a) PVA/PDMS-s and (b) PVA/PDMS-d. For the quantitative

evaluation of the dispersibility, the cross-sectional micrograph of the composites was

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divided into small rectangles of 6 µm×14 µm, as was presented in Fig. 4 from the

surface to the bottom of the composite. By counting the number of the nanofibers
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penetrating the sides of the rectangles, the dispersibility of the nanofibers could be
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analyzed by presenting the frequency of the fibers shown in Fig. 5. Y-axis shows the
frequency of the nanofibers and X-axis shows the distance from the surface (i.e. the
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depth: 0 µm for the surface and 80 µm for the bottom of the composite). As was
mentioned above, it was confirmed that PVA/PDMS-s indeed presented inhomogeneity
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exhibiting aggregations of the PVA nanofibers near the surface. In contrast, as for the
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PVA/PDMS-d, independent nanofibers were evenly scattered from the surface to the

bottom of the PVA/PDMS-d specimens. In more detail, ~95% of the nanofibers

preferably existed within the depth of 20 µm for the PVA/PDMS-s. The average

frequency for the PVA/PDMS-d specimens was about 8% almost uniformly dispersed

from 0 µm to 80 µm in depth. This is because, as was discussed, the PVA nanofibers in

the PVA/PDMS-s were already too entangled to diffuse when the PDMS prepolymer

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was added to the electrospun PVA nanofiber sheets. PVA nanofibers in the

PVA/PDMS-d on the other hand, could be widely dispersed throughout the composite,

since PVA nanofibers were electrospun and, at the same time, directly ejected into the

liquid PDMS prepolymer before the hard entanglement could be established, eventually

exhibiting higher dispersibility in the resulting composites. It was expected that the

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colloidal-dispersion effects were realized in our nanofiber composites due to the

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nanoscale size of the PVA nanofibers. Macroscopically, it could also be due to the larger

density of the PVA as compared with that of the PDMS: the density of the PVA was

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~1.3 g/cm3 and the density of the PDMS was ~0.97 g/cm3, while the thickness of the

PDMS was ~0.5 mm. Hence the settling of the PVA nanofibers and the viscous

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resistance driven by the viscous PDMS prepolymer could well balance to fabricate a
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homogeneous composite with good dispersion in our experiments.

3.2 Transparency of the composites

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It was generally known that when different types of materials were mixed

inhomogeneously, the transparency of the resulting composite may be low, becoming

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translucent or rather turbid due to the dispersibility, the filler aggregations, the
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micro-voids, and/or the difference in the refraction index between the matrix and the

fillers. Thus, the transparency of the newly synthesized well-dispersed nanofiber

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composites was investigated. Fig. 6 shows the light transmittance of the PVA/PDMS

composites measured by a UV-VIS spectral photometer. The thickness of the base film
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thickness was calculated as 0.1 mm by the Lambert-Beer law [21]. By increasing the
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PVA concentration, the average light transmittance of the PVA/PDMS-s composites

became ~28% lower than that of pure PDMS. The average light transmittance of the

PVA/PDMS-d, on the other hand, became ~15% lower than that of pure PDMS even at

the highest concentration of 4 wt%. In fact, the light transmittance of the PVA/PDMS-d

was 13% higher than that of the PVA/PDMS-s. The fact that the light transparency of

the PVA/PDMS-d film was significantly higher than that of the PVA/PDMS-s film was

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also confirmed from the macroscopic view (Fig. S2). Therefore, it was confirmed that

increasing the PVA-nanofiber concentration decreased the light transmittance of the

resulting composites, and that the composites with well-dispersed nanofibers retained

higher transparency than the composites with aggregated nanofibers synthesized by the

conventional sandwich method due to the light scattering. As compared with the

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previous methods, our newly modified method could generate highly transparent

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polymeric composites by a relatively simple system requiring neither vacuuming nor

complex process for the synthesis.

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3.3 Mechanical properties of the composites

The effects of the fiber concentrations on the mechanical properties of the

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PVA/PDMS composites were studied. Fig. 7 shows the results of the tensile testing on
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the PVA/PDMS-d films with various PVA concentrations (0 wt% (pure PDMS), 0.1

wt%, 1 wt%, 2 wt%, 4 wt%, and 6 wt%). The pure PVA-nanofiber film showed a typical
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stress-strain curve of a brittle material with a sharp inclination and the low ductility in

its stress-strain curve. The pure PDMS film presented a distinctive stress-strain curve of
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a rubber material with relatively the low gradient and the high ductility in its
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stress-strain curve. In fact, the well-dispersed isotropic PVA/PDMS-d composites

almost fully retained the highly elastic characteristics up to 10% of the PVA-fiber
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concentration. The observed changes in the stress-strain curves by varying the fiber

concentrations were more drastic than the changes observed for the PVA/PDMS-s (Fig.
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S3).
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The Young’s moduli and the fracture strains of all the composites measured by

the tensile testing were presented in Fig. 8. It was found that both the PVA/PDMS-d and

the PVA/PDMS-s films had the higher Young’s moduli than the neat PDMS film with

the Young’s modulus of 1.4 MPa. In more detail, at 6 wt% of the fiber concentration, the

Young’s modulus of the sandwiched PVA/PDMS-s composite showed approximately 6

times higher than that of the pure PDMS. The Young’s modulus of PVA/PDMS-d was

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getting much higher, reaching approximately 14 times higher than that of the pure

PDMS and even about 2.3 times higher than that of the PVA/PDMS-s film with the

same fiber concentration. The difference in the Young’s moduli between PVA/PDMS-s

and PVA/PDMS-d may highly be due to the unavoidable micro-voids and the fiber

aggregations caused by the hard fiber entanglement that was intrinsic to the sandwiched

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composites. According to Fig. 8 (b), the fracture strains of the PVA/PDMS-d were

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almost constant regardless of the fiber concentrations. It was also found that the fracture

strains of the PVA/PDMS-s were lower than those of PVA/PDMS-d.

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4. Conclusions

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A homogeneous composite with well-dispersed nanofibers was made using a
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base polymer in its liquid state, either in melt or in solution, during the electrospinning,

and the liquid base polymer was also used as an earth collector for the electrospinning.
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Without using an ordinary metal plate as an electrospinning collector, electrospun

nanofibers could be properly fabricated, simultaneously being ejected into the liquid
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polymer matrix to fabricate a homogeneous composite with well-dispersed fibers. The

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cross-sectional SEM micrographs of the composites revealed the uniformly dispersed

PVA-fiber structures in the PDMS matrix. Thus, it was concluded that PVA nanofibers
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could be well dispersed into PDMS matrix by using this new method, unlike

PVA/PDMS-s that was fabricated by the conventional method. The enhancement of the
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mechanical property was confirmed for a newly made PVA/PDMS-d composite which
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also remained highly transparent due to the nanoscale fiber dispersion. Therefore, the

suggested method in this work may provide a new way to improve the inhomogeneity

of the composite materials, simultaneously enhancing the mechanical properties of the

composite just by adding fibers at low concentrations. Further studies on the use of the

various types of polymers are expected as this method could be currently used only

when the fiber polymer is not soluble to the matrix polymer in solution or in melt.

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Acknowledgements

This work was supported in part by a Grant-in-aid for Science Research (A) and by a

Fund for the Promotion of Joint International Research (Fostering Joint International

Research) (No. 15H02298 and No. 15KK0244, respectively to A.H.) from Japan

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Society for the Promotion of Science (JSPS: “KAKENHI”). A.H. is grateful to Prof

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Glenn H. Fredrickson from the University of California, Santa Barbara for offering

stimulating suggestions and encouragements.

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Appendices A. Supplemental Information

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Supplementary data related to this chapter can be found at ---.
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Figure captions

Fig. 1. (a) A traditional way of electrospinning and (b) a modified way of

electrospinning with an assemble collector to fabricate nanofiber composites for

uniformly dispersed nanofiber composites

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Fig. 2. SEM micrographs of the fracture surfaces of PVA/PDMS-s at the fiber

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concentrations of (a) 1 wt% and (b) 4 wt% under several magnifications.

Fig. 3. SEM micrographs of the fracture surfaces of PVA/PDMS-d at the fiber

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concentrations of (a) 1 wt% and (b) 4 wt% under several magnifications.

Fig. 4. Evaluating the spatial distribution of PVA nanofibers in: (a) PVA/PDMS-s and

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(b) PVA/PDMS-d by SEM cross-sectional micrographs. To facilitate visualization,
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fibers were slightly colored brown.

Fig. 5. Frequency of PVA nanofibers against the depth of the composites.

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Fig. 6. Light transmittance of PVA/PDMS composites by the UV-VIS spectral

photometer
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Fig. 7. Tensile stress-strain curves of pure PVA nanofiber, pure PDMS, and
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PVA/PDMS-d films with various PVA fiber concentrations

Fig. 8. (a) Young’s moduli and (b) fracture strains against PVA nanofiber concentrations
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of PVA/PDMS-d and PVA/PDMS-s

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

PT
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M
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