Materials and Design 114 (2017) 303–311

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Highly porous fibers prepared by centrifugal spinning

Teng Hou, Xianglong Li, Yishen Lu, Bin Yang ⁎
National Engineering Lab for Textile Fiber Materials and Processing Technology, College of Materials and Textiles, Zhejiang Sci-Tech University, 310018, China.

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Porous EC/PVP fibers were fabricated by

centrifugal spinning while nonporous fi-
bers were obtained in electrospinning.
• The porous EC/PVP fibers showed great
high specific surface area and contact
angle.
• The mechanism was established to clar-
ify the morphology change between
centrifugal-spun fibers and electrospun
fibers.
• The centrifugal spinning is meaningful
for the rapid and large-scale fabrication
of porous fibers.

a r t i c l e i n f o a b s t r a c t

Article history: Ethyl cellulose (EC)/polyvinyl pyrrolidone (PVP) fibers with micro- and nano-porous throughout structures are
Received 14 September 2016 fabricated by centrifugal spinning a binary solvent system of ethanol and water. A combination of different pa-
Received in revised form 3 November 2016 rameters including EC/PVP ratios, ethanol/water ratios and rheological properties are investigated to demon-
Accepted 4 November 2016
strate pore formation. The specific surface area of EC/PVP fibers increases more than 11 times when the binary
Available online 9 November 2016
solvent contains 30% water. However, fibers with porous structure cannot be obtained in electrospinning process
Keywords:
under the same solution and ambient conditions. The result indicates that the spinning method greatly influences
Throughout porous structure the diameter and solvent evaporation of the jets, and as a consequence, fiber morphology varies in the two spin-
EC/PVP fibers ning processes.
Centrifugal spinning © 2016 Elsevier Ltd. All rights reserved.
Pore formation

1. Introduction
Due to the large specific surface area, micro- and nano-porous fibers
have multiple applications in biomaterials [1–4], energy [5] and filtra-
tion [6]. Among these, biomaterials have attracted great scientific and
technological interests. As one of the most commonly used cellulose de-
rivatives, EC has been widely employed in drug release [7–10] and pack-
aging [11] for the biocompatible, nonbiodegradable and eco-friendly
properties. Besides, EC exhibits excellent plasticity, good solubility in or-
ganic solvents, high mechanical intensity, good heat-resistance, cold-
⁎ Corresponding author.
E-mail address: yangbin665959@gmail.com (B. Yang).
resistance and stability [12,13]. However, EC fibers with micro- and
nano- porous structures, which could have potential applications,
have been hardly ever reported. Researchers have reported several
methods to fabricate porous fibers by using self-assembly [14], phase
separation [15] and electrospinning [16]. Among these techniques,
electrospinning is the most popular method. According to some reports,
EC fibers fabricated in electrospinning process are mostly of smooth
surface morphology [17–19]. Park et al. [20] reported porous EC fi-
bers fabricated with electrospinning, though only a few of pores on
the surface. Besides, high voltage, sensitive to dielectric constant,
and low fiber yield limit the application of electrospinning [21].
Thus, methods for rapid manufacturing micro- and nano-porous EC
fibers are of great interest.

http://dx.doi.org/10.1016/j.matdes.2016.11.019
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
304 T. Hou et al. / Materials and Design 114 (2017) 303–311
In recent years, centrifugal spinning, a novel technique for gener-
ating micro- to nano-fibers, has successfully overcome the obstacles
that electrospinning encounters [22–25]. This method utilizes cen-
trifugal force to draw polymer jets into fibers instead of electrostatic
force, so that both nonconductive and conductive polymers can be
spun in solutions or in melts [26]. One of the important features of
centrifugal spinning process is its high production rate. With two
nozzles, the average production rate of a simple centrifugal spinning
instrument is around 50 g/h, which is at least two orders of magni-
tude higher than a lab-scale electrospinning process(0.1–1.0 g/h)
[24,27–29]. Although the production rate of melt blown is higher
than centrifugal spinning [30], the melt blown has limited material
choices and the materials must be spun in melts.
In 1991, a patent disclosed a rotating spinning centrifuge that can
fabricate polymer fibers in molten or liquid state [31]. After that, some re-
search groups attempted to employ different spinneret shape to improve
the quality of the spun fibers, while the fiber diameter produced by this
method was still much thicker than that produced by electrospinning
[32,33]. In 2010, Oya et al. [34] used a centrifugal spinning to produce car-
bon nanomaterials, and then centrifugal spinning has drawn wide atten-
tion again. Lozano et al. [25] well developed this technology and named it
Forcespinning, which means materials that are hard to fabricate by
electrospinning or other methods can be successfully forcespun into
micro- to nanometer range fibers. By now, the centrifugal spinning has
been successfully used to fabricate micro- and nano-fibers of polymers
[26,35–38], ceramics [39–42] and protein [43]. Besides, centrifugal spin-
ning develops some special superiorities in manufacturing amylose rich
starch-based fibers compared with electrospinning [44]. In addition, the
centrifugal-spun material is more suitable for tissue engineering applica-
tions, for the 3D fluffy structure [45].
The parameters of centrifugal spinning process greatly influence
fiber morphology and diameter such as rotational speed, concentration,
evaporation rate (for solutions), temperature (for melts), and collection
distance. For solution spinning, concentration and rotational speed are
considered as the main factors among the aforementioned parameters.
The lower the concentration, the thinner the fibers and the narrower
the fiber diameter distribution, while the rotational speed has a subtle
effect on fiber diameter [46]. However, nozzles of the spinneret are eas-
ily clogged up due to the high viscosity or the small needle size. Chen et
al. [47] reported a nozzle-less centrifugal spinning method which solved
the problem and also improved the production rate. Compared with
electrospun fibers, the larger fiber diameter and fiber diameter distribu-
tion of centrifugal-spun fibers have limited its development in fine
chemicals, but the feature combined with 3D fluffy fiber assembly ap-
peals to biomaterials [48]. Therefore, centrifugal spinning have great ad-
vantages in generating micro- and nano-fibers. So far, there is few
reports on the micro- and nano-porous fibers fabricated by centrifugal
spinning without further treatments. Although Ren et al. [37] reported
the porous PLLA fibers fabricated by centrifugal spinning, the porous
structure was developed after surface etching treatment.
In this study, the throughout porous EC/PVP fibers are prepared by
centrifugal spinning a binary solvent system without further treat-
ments. Structure and characterizations are investigated by changing
polymer and solvent ratios and controlling processing parameters. The
morphology, viscosity, specific surface area and contact angle (CA) are
measured. Meanwhile, the formation mechanism for different struc-
tures between centrifugal-spun fibers and electrospun fibers which
are fabricated under the same solution and ambient conditions is
discussed.
2. Materials and methods
2.1. Materials
Ethyl cellulose (EC, 18–22 mPa·s) and Polyvinyl pyrrolidone (PVP,
MW = 1,300,000) purchased from Aladdin (Shanghai, China) were
used without further purification. Ethanol (Aladdin, China) and water
were selected as the solvent to dissolve EC and PVP polymers [18,49,50].
2.2. Synthesis of EC/PVP solutions
EC and PVP were dissolved in ethanol and water for 10 h to pre-
pare a mass-volume concentration of 15% uniform polymer solution
for centrifugal spinning. A range of EC/PVP polymer mass ratios was
studied, which included 10%/90%, 30%/70%, 50%/50%, 70%/30%, and
90%/10%, and the ethanol/water were varied at 70%/30%, 80%/20%
and 90%/10% volume ratio. To get a full spectrum of solution proper-
ties which helped the study of inducing porous fibers, the viscosity of
the solution mixture was measured at room temperature after the
degassing procedure.
2.3. Centrifugal spinning process
The centrifugal spinning setup is shown in Fig. 1, including motor,
spinneret and collector. The spinneret is fixed on a shaft which is con-
trolled by the motor. In this study, the rotational speed of the spinneret
was controlled at 3500 rpm. The distance between the spinneret orifice
and the rod collector was 12 cm.
2.4. Electrospinning process
The schematic diagram of electrospinning system is shown in Fig. 2,
including high voltage power supply, needle (25 G), syringe (1 mL), and
collector with aluminum foil. The tip-to-collector distance was set at
12 cm. The high voltage provided by the power supply was adjusted
at 7 kV.
2.5. Fibers characterization
The morphology of fibers was characterized by FE-SEM and TEM.
The centrifugal-spun fibers and electrospun fibers were examined on
a ZEISS type-ULTRA55 scanning electron microscope and a JEM-2100
transmission electron microscope. Image Pro Plus 6.0 was used to mea-
sure the diameters of the fibers. The average fiber diameter and distri-
butions were determined from 100 random fibers.
Physica MCR 301 rheometer was used to obtain the rheological
properties of the solution. The used geometry was cone-plate (50 mm
diameter; 0.341 mm gap). Viscosity data were collected at the shear
rate ranging from 0.1 to 100 s−1 at 20 °C.
Micromeritics ASAP 2020HD88 was used to analyze the specific sur-
face area of the samples. The samples were degassed at 80 °C for 24 h
prior to the measurement in order to remove adsorbed impurities and
moisture.
Fig. 1. Centrifugal spinning system.
 T. Hou et al. / Materials and Design 114 (2017) 303–311
Fig. 2. Schematic diagram of electrospinning.
The CA measurement was performed with a DSA20 Kruss Goniome-
ter. Water droplet was dropped onto a levelled fibers membrane surface
and the images of the water drop on the fibers membrane surface were
captured by an optical system to calculate the CA. Each sample was test-
ed at least three times.
3. Results and discussion
3.1. Surface morphology
The SEM images of centrifugal-spun EC/PVP fibers are shown in
Fig. 3. It can be seen from Fig. 3 that the smooth surfaces are replaced
by the rough morphologies with the increasing of water and EC contents
and fiber diameters are all in micrometer range. With the increase of
water in mixed solvent, there appear cracks on fiber surfaces (Fig. 3a, f
and k). With increased EC content in the solution, there appear grooves
on the fiber surfaces (Fig. 3a, b, c, d and e). Fig. 4 shows a change of fiber
diameters with different water and EC contents, and the average fiber
diameter is about 2–4 μm. As shown in Fig. 4a, when keeping the
same mass ratio of EC, the average diameter of fibers increases with
Fig. 3. SEM images of EC/PVP fibers formed at different EC/PVP and ethanol/water ratios, (a) 10%/90%; 90%/10%, (b) 30%/70%; 90%/10%, (c) 50%/50%; 90%/10%, (d) 70%/30%; 90%/10%, (e)
90%/10%; 90%/10%, (f) 10%/90%; 80%/20%, (g) 30%/70%; 80%/20%, (h) 50%/50%; 80%/20%, (i) 70%/30%; 80%/20%, (j) 90%/10%; 80%/20%, (k) 10%/90%; 70%/30%, (l) 30%/70%; 70%/30%, (m)
50%/50%; 70%/30%, (n) 70%/30%; 70%/30%, (o) 90%/10%; 70%/30%.
305
the increase of water content in the solvent mixture. Fig. 4b shows
that the fiber diameter distributions are affected by both water and EC.
It is interesting to note that there is a morphology mutation in
Fig. 3o. The fibers with porous interior and surface were fabricated at
a specific situation (EC/PVP = 90%/10%; ethanol/water = 70%/30%).
The resultant average fiber diameter is 6.73 μm, which is 2 times than
that of the other ratios. More experiments had been done to make
sure the ratios of EC/PVP and ethanol/water that generated fibers with
porous structure. Fig. 5 shows a series of SEM images for different EC
contents and fixed ethanol/water ratio of 70%/30%. These indicate that
when EC contains over 85%, porous structure comes into being with it.
However, only few fibers will be found when the content of EC exceeds
95%. Obviously, PVP can improve the spinnability [51]. At certain EC/PVP
ratio of 90%/10%, Fig. 6 shows a change in fiber morphology with water
contents of 20%, 25%, 30%, 35% and 40%, respectively. At the same EC/
PVP ratio, with the increase of water in mixed solvent, there appears
grooved fibers, and at 30% water content, the porous structure of resul-
tant fibers grows accordingly (Fig. 6C and c). With further increased
water in the solvent mixture, there appears cakes on the aluminum
foil collector. As a non-solvent for EC, when water contained over 35%
of the solvent, a mass of EC deposited in 5 min still standing in the
experiment. In this case, fibers with porous structure produce in the
range from 25% to 35% of water in the solvent. The result shows that
when the water ranges in content from 25% to 35%, and the content
of EC is between 85% and 95%, the highly porous fibers will be
manufactured.
The above results imply that the emerging tendency of the porous
structure of fibers increases with reducing the ratio of ethanol/water
and increasing the ratio of EC/PVP. Furthermore, the formation of
pores on the jets would waste a large amount of energy which, oth-
erwise, could be used to further stretch the jets into even smaller fi-
bers [52]. As shown in Fig. 3o, with further increased water in the
solvent mixture, there appears evident pores and ever-increasing
fiber diameters.
3.2. Rheological properties
In order to quantify the critical polymer viscosity for generating po-
rous fibers under different EC/PVP and ethanol/water ratios, we studied
306 T. Hou et al. / Materials and Design 114 (2017) 303–311
Fig. 4. Plots for average fiber diameter and distributions of different water concentration and EC content.
the rheological properties of the solution with water containing from
10% to 30% as shown in Fig. 7 in which each symbol represents a certain
EC/PVP ratio. In the studied water range, the variation of slope can be
clearly observed. The shape of the viscosity curves shows decreasing
viscosity values with increasing shear rate, indicating that all solutions
behave as non-Newtonian, shear-thinning fluids. The viscosity curves
are almost identical Fig. 7a and b, but a mutation occurs in Fig. 7c with
EC/PVP = 90%/10%, the curve of it overpasses others at lower shear
rate, the result agrees very well with the change in fiber morphology.
To further elucidate on the viscosity mutation of solution mixed with
EC contenting around 90%, more experiments had been done with EC
content varying at 85%, 90%, 95% and 100%, respectively, and 100%
PVP dissolved in a certain ratio solvent (ethanol/water = 70%/30%),
the resultant graph is Fig. 7d. When EC contains over 80% in the blends,
shear thinning behavior could be obviously observed at very low shear
rates. Notable change in fiber morphology could be found when EC con-
tains over 85% in the solute. These results correspond with the SEM
study, indicating the morphology of spun fibers with porous structure
impacted by rheological properties. The results agree very well with
previous reports that the rheological properties of a polymer solution
greatly influence jet formation and stability as well as nanofiber mor-
phology [53,54].
3.3. Specific surface area
The results depicted in Table 1 show changes of BET surface areas of
fibers under different conditions. For the centrifugal-spun fibers, the
Fig. 5. SEM images of EC/PVP fibers formed at certain ratio of ethanol/water = 70%/30%, (A; a) 100% EC, (B; b) 95% EC, (C; c) 90% EC, (D; d) 85% EC, (E; e) 100% PVP.
BET surface area is 12.86 m2 g−1 after adding 30% (v/v) water in the sol-
vent, which increases more than 11 times compared with centrifugal-
spun fibers developed from 100% ethanol solvent and 4 times that of
electrospun fibers under the same conditions (EC/PVP = 90%/10%; eth-
anol/water = 70%/30%), suggesting that water plays a pivotal role in po-
rous structure formation and spinning method as well. These results are
consistent with the corresponding morphologies indicated in the SEM
images discussed above. Therefore, it is anticipated that centrifugal-
spun EC/PVP fibers with high surface area and porous structure can
stimulate the fibroblast action and proliferation in order to repair in-
jured tissues. According to the previous reports, high surface area of
5–100 m2 g−1 is extremely efficient for fluid absorption and dermal de-
livery. Since the surface area of EC/PVP porous fibers in this paper is in
that range, they have potential for cell attachment and proliferation in
wound healing [55].
3.4. Hydrophobicity of centrifugal-spun fibers
Many investigations proved that besides chemical nature of the sur-
faces, the roughness of surfaces is also a fundamental feature for the cre-
ation of a hydrophobic surface [56,57]. Hydrophobicity was evaluated
by measuring the CA formed between water drop and the surface of
samples in this paper. Results are mean value of three measurements
on different parts of the sample. The results of the CA measurements
are presented in Figs. 8 and 9. As shown in Fig. 8a, the CA of EC/PVP fi-
bers was measured to be 73.21°, after improving the water content
and increasing the content of EC, the CA of EC/PVP fibers increased to
 T. Hou et al. / Materials and Design 114 (2017) 303–311 307

Fig. 6. SEM images of EC/PVP fibers formed at certain ratio of EC/PVP = 90%/10%, (A; a) 20% water, (B; b) 25% water, (C; c) 30% water, (D; d) 35% water, (E; e) 40% water.

148.59° (Fig. 8o). The increased roughness of EC/PVP fibers and the hy-
drophobicity offered by EC plays an important role in improving the hy-
drophobicity of centrifugal-spun fibers.
Obviously, the higher surface area and roughness are provided by
the throughout porous structure. The result demonstrates that water
plays an important role in establishing high surface area and even po-
rous structure when EC contains more than 85% of the solute [58].
Moreover, it is worth noting that compared with pure EC fibers and
pure PVP fibers, the presence of pores in the EC/PVP fibers greatly
increases further benefiting applications where large surface area is
required.
3.5. Mechanism of porous fibers formation
As stated earlier, porous fibers can hardly be prepared by
electrospinning with EC as the raw or principal ingredient. To further
elucidate the changes between centrifugal- spun fibers and electrospun
fibers, experiments had been done at the same solution parameters and

Fig. 7. Plots of apparent viscosity versus shear rate for different water concentration and varied EC/PVP ratios, (a) 10%water, (b) 20%water, (c; d) 30%water.
308 T. Hou et al. / Materials and Design 114 (2017) 303–311

Table 1
SEM and surface area data of different nanofibers.

Sample BET surface area m2 g−1 SEM

EC/PVP = 90%/10% 12.86

ethanol/water = 70%/30%
centrifugal spinning

EC/PVP = 90%/10% 3.38

Ethanol/water = 70%/30%
Electrospinning

EC/PVP = 90%/10% 1.08

Ethanol/water = 100%/0%
Centrifugal spinning

Fig. 9. Plots for contact angle of different water concentration.

ambient environment, the properties of the electrospun fibers were an-
alyzed by SEM, TEM and CA measurements, and the results are shown in
Fig. 10b. Because porous fibers can be obtained in electrospinning if the
applied voltage is lower enough [49], the applied voltage was set at 7 kV
which is a critical value that can produce jets in the electrospinning
process.
As can be seen from Fig. 10, there is a clear difference between the
centrifugal-spun fibers and the electrospun fibers. Throughout porous
fibers were successfully fabricated by centrifugal spinning while nonpo-
rous fibers were obtained in electrospinning process with the identical
solution and ambient conditions. Meanwhile, the CA results for the pre-
pared porous centrifugal-spun fibers showed high CA values (CA =
148.59°). However, the electrospun fibers had considerably lower CA
(CA = 102.65°). This can be explained by the change of the roughness
of the fiber surfaces, thus, it can be speculated that the spinning method
is also a pivotal factor which could change fiber morphology.
To demonstrate how the spinning method (centrifugal spinning
and electrospinning) influencing pore formation, a schematic dia-
gram was brought up as shown in Fig. 11. Before discussing the dif-
ference between centrifugal spinning and electrospinning, it is
important to figure out the reasons for pore formation in centrifugal
spinning. This phenomenon can occur for some reasons. Firstly, due
to the difference in vapor pressure between ethanol and water. In
the process, a cylindrical polymer fluid jet initially consists of poly-
mer chains and solvent molecules. Since the vapor pressure of etha-
nol is very high compared to water, it is expected to evaporate
quickly during the process leaving behind water. Another possible
mechanism for the phenomenon is due to the phase separation. As
the non-solvent of EC, water molecules reunited into groups and
led to water-rich regions and solute-rich regions during the process.

Fig. 8. Images of contact angle at different EC/PVP and ethanol/water ratios, (a) 10%/90%; 90%/10%, (b) 30%/70%; 90%/10%, (c) 50%/50%; 90%/10%, (d) 70%/30%; 90%/10%, (e) 90%/10%; 90%/
10%, (f) 10%/90%; 80%/20%, (g) 30%/70%; 80%/20%, (h) 50%/50%; 80%/20%, (i) 70%/30%; 80%/20%, (j) 90%/10%; 80%/20%, (k) 10%/90%; 70%/30%, (l) 30%/70%; 70%/30%, (m) 50%/50%; 70%/
30%, (n) 70%/30%; 70%/30%, (o) 90%/10%; 70%/30%.
 T. Hou et al. / Materials and Design 114 (2017) 303–311 309

Fig. 10. (a) Centrifugal-spun fibers, (b) Electrospun fibers, i and ii are images of TEM.

Eventually, water-rich regions turned into pores throughout the fi-
bers with the continued evaporation of solvent [59].
Nonetheless, the reasons mentioned above for pore formation is not
suitable for electrospinning process. From the SEM and TEM images
showed in Fig. 10b, we noticed that only grooved surfaces and lumens
could be found in the fibers. As we know, ‘the jet splitting instability’
in the electrospinning process, which lead to rapid solvent evaporation
at a time scale down to the millisecond range, so most of polymer lean
nuclei to grow ripe pore induced by the rapid phase separation, and hol-
low structures show up with further evaporation of the remainder inner
the fiber [60]. It is noteworthy that the average diameter of fibers fabri-
cated in electrospinning process is less than 1 μm while that of fibers
manufactured by centrifugal spinning is about 7 μm, which means the
solution jets produced by centrifugal spinning are several times more
than that of electrospinning, that is, the water molecules get more
chances to reunite during the solidification process and fibers with
throughout pore structure were manufactured eventually in centrifugal
spinning process. In addition, the TEM results revealed that there maybe
two or more lumens in the electrospun fiber at the same time and the
hollow structure is distributed randomly in the fiber.
In order to make it clear that whether the electrostatic force could
influence the pore formation, the high voltage was imparted on the cen-
trifugal spinning instrument and the results are shown in Fig. 12. From
the result, we have made a conclusion that the porous structures will be
reduced with the increase of voltage while fiber diameters decreases
slightly. During the spinning process, the electrostatic force existed all
the time, the EC/PVP chains were stretched and aligned along the elec-
tric field direction. To some extent, the aggregation effect of solvent
weakened, thus, long and narrow lumens appeared in electrospun fi-
bers (Fig. 10b).
In summary, this study underlines the importance of the centrifugal
spinning method in porous fibers generation. As different applications
require different levels of fiber diameters and porosity, this simplistic
approach will provide a comprehensive platform for a broad variety of
applications.
4. Conclusions
The EC/PVP fibers with throughout porous structures are successful-
ly fabricated with centrifugal spinning process. Experiments reveal that
solution properties and spinning method are key factors to determine
fiber structure. By means of controlling EC mass ratios and water vol-
ume ratios at 85%–95% and 25%–35%, respectively, the porous structure
comes into beings in centrifugal spinning process. The CA measure-
ments confirm that the centrifugal-spun porous fibers exhibit a rougher
surface with greater hydrophobicity.
However, nonporous fibers are obtained in electrospinning process
under the identical solution and ambient conditions. Obviously, the
spinning method greatly influences the diameter and solvent evapo-
ration of the jets, thus, fiber structure varies in different spinning

Fig. 11. Mechanism of fiber formation.

310 T. Hou et al. / Materials and Design 114 (2017) 303–311
Fig. 12. SEM images of electro-centrifugal-spun fibers, (a) 2500 rpm; 0 kV, (b) 2500 rpm; 4 kV, (c) 2500 rpm; 6 kV. The spinning solution concentration is 15% (w/v) with EC/PVP =
90%/10% and ethanol/water = 70%/30%.
processes. The introduced centrifugal spinning is meaningful for the
rapid and large-scale fabrication of porous fibers in many applica-
tions, such as tissue engineering, filtration, electrode and drug-
release.
Acknowledgements
This work was supported by the Natural Science Foundation of Zhe-
jiang Province of China (No. LY17E030009).
References
[1] D. Salamon, S. Teixeira, S.M. Dutczak, D.F. Stamatialis, Facile method of building hy-
droxyapatite 3D scaffolds assembled from porous hollow fibers enabling nutrient
delivery, Ceram. Int. 40 (2014) 14793–14799.
[2] M.M. Asli, B. Pourdeyhimi, E.G. Loboa, Release profiles of tricalcium phosphate nano-
particles from poly(L-lactic acid) electrospun scaffolds with single component, core–
sheath, or porous fiber morphologies: effects on hASC viability and osteogenic dif-
ferentiation, Macromol. Biosci. 12 (2012) 893–900.
[3] H.R. Pant, M.P. Neupane, B. Pant, G. Panthi, H.J. Oh, M.H. Lee, H.Y. Kim, Fabrication of
highly porous poly(ɛ-caprolactone) fibers for novel tissue scaffold via water-bath
electrospinning, Colloid Surface B 88 (2011) 587–592.
[4] D.E. Mogosanu, R. Verplancke, P. Dubruel, J. Vanfleteren, Fabrication of 3-dimension-
al biodegradable microfluidic environments for tissue engineering applications,
Mater. Des. 89 (2016) 1315–1324.
[5] B. Wang, J.L. Cheng, Y.P. Wu, D. Wang, D.N. He, Porous NiO fibers prepared by
electrospinning as high performance anode materials for lithium ion batteries,
Electrochem. Commun. 23 (2012) 5–8.
[6] H.Q. Wu, J.H. Kong, X.Y. Yao, C.Y. Zhao, Y.L. Dong, X.H. Lu, Polydopamine-assisted at-
tachment of β-cyclodextrin on porous electrospun fibers for water purification
under highly basic condition, Chem. Eng. J. 270 (2015) 101–109.
[7] L.Y. Huang, C.B. White, X.X. Shen, D.G. Yu, L.M. Zhu, Time-engineeringed biphasic
drug release by electrospun nanofiber meshes, Int. J. Pharm. 436 (2012) 88–96.
[8] L. Bruno, S. Kasapis, P.W.S. Heng, Effect of polymer molecular weight on the struc-
tural properties of nonaqueous ethyl cellulose gels intended for topical drug deliv-
ery, Carbohydr. Polym. 88 (2012) 382–388.
[9] D.G. Yu, X. Wang, X.Y. Li, W. Chian, Y. Li, Y.Z. Liao, Electrospun biphasic drug release
polyvinylpyrrolidone/ethyl cellulose core/sheath nanofibers, Acta Biomater. 9
(2013) 5665–5672.
[10] C. Jian, C. Gong, S.Q. Wang, S.F. Wang, X.M. Xie, Y. Wei, J.Y. Yuan, Multifunctional
comb copolymer ethyl cellulose-g-poly(ɛ-caprolactone)-rhodamine B/folate: syn-
thesis, characterization and targeted bonding application, Eur. Polym. J. 55 (2014)
235–244.
[11] H.M.N. Iqbal, G. Kyazze, T. Tron, T. Keshavarz, A preliminary study on the develop-
ment and characterisation of enzymatically grafted P(3HB)-ethyl cellulose based
novel composites, Cellulose 21 (2014) 3613–3621.
[12] W.Z. Yuan, J.Y. Yuan, F.B. Zhang, X.M. Xie, Syntheses, characterization, and in vitro
degradation of ethyl cellulose-graft-poly(ɛ-caprolactone)-block-poly(L-lactide) co-
polymers by sequential ring-opening polymerization, Biomacromolecules 8
(2007) 1101–1108.
[13] J. Zhu, X.T. Dong, X.L. Wang, Y.Z. Wang, Preparation and properties of a novel biode-
gradable ethyl cellulose grafting copolymer with poly(p-dioxanone) side-chains,
Carbohydr. Polym. 80 (2010) 350–359.
[14] S.G. Zhang, Fabrication of novel biomaterials through molecular self-assembly, Nat.
Biotechnol. 21 (2003) 1171–1178.
[15] H. Lo, M.S. Ponticiello, K.W. Leong, Fabrication of controlled release biodegradable
foams by phase separation, Tissue Eng. 1 (2007) 15–28.
[16] P. Dayal, J. Liu, S. Kumar, T. Kyu, Experimental and theoretical investigations of po-
rous structure formation in electrospun fibers, Macromolecules 40 (2007)
7689–7694.
[17] X.H. Wu, L.G. Wang, H. Yu, Y. Huang, Effect of solvent on morphology of
electrospinning ethyl cellulose fibers, J. Appl. Polym. Sci. 97 (2005) 1292–1297.
[18] B. Ahmad, S. Stoyanov, E. Pelan, E. Stride, M. Edirisinghe, Electrospinning of ethyl
cellulose fibres with glass and steel needle configurations, Food Res. Int. 54
(2013) 1761–1772.
[19] S.U. Zahra, X.X. Shen, H.Y. Li, L.M. Zhu, Study of sustained release drug-loaded nano-
fibers of cellulose acetate and ethyl cellulose polymer blends prepared by
electrospinning and their in-vitro drug release profiles, J. Polym. Res. 21 (2014) 602.
[20] J.Y. Park, S.W. Han, I.H. Lee, Preparation of electrospun porous ethyl cellulose fiber
by THF/DMAc binary solvent system, J. Ind. Eng. Chem. 13 (2007) 1002–1008.
[21] A. Baji, Y.W. Mai, S.C. Wong, M. Abtahi, P. Chen, Electrospinning of polymer nanofi-
bers: effects on oriented morphology, structures and tensile properties, Compos. Sci.
Technol. 70 (2010) 703–718.
[22] M.R. Badrossamay, H.A. Mcllwee, J.A. Goss, K.K. Parker, Nanofiber assembly by rotary
jet-spinning, Nano Lett. 10 (2010) 2257–2261.
[23] L.A. Mary, T. Senthilram, S. Suganya, L. Nagarajan, J. Venugopal, S. Ramakrishna,
V.R.G. Dev, Centrifugal spun ultrafine fibrous web as a potential drug delivery vehi-
cle, Express Polym Lett 7 (2013) 238–248.
[24] S. Padron, A. Fuentes, D. Caruntu, K. Lozano, Experimental study of nanofiber pro-
duction through forcespinning, J. Appl. Phys. 113 (2013) 024318.
[25] K. Sarkar, C. Gomez, S. Zambrano, M. Ramirez, E. Hoyos, H. Vasquez, K. Lozano,
Electrospinning to Forcespinning™, Mater. Today 13 (2010) 12–14.
[26] Z. McEachin, K. Lozano, Production and characterization of polycaprolactone nano-
fibers via Forcespinning™ technology, J. Appl. Polym. Sci. 126 (2012) 473–479.
[27] S. Zhang, W.S. Shim, J. Kim, Design of ultra-fine nonwovens via electrospinning of
Nylon 6: spinning parameters and filtration efficiency, Mater. Des. 30 (2009)
3659–3666.
[28] X.W. Zhang, Y. Lu, Centrifugal spinning: an alternative approach to fabricate nanofi-
bers at high speed and low cost, Polym. Rev. 54 (2014) 677–701.
[29] L.Y. Ji, Z. Lin, Y. Li, Y.Z. Liang, O. Toprakci, Q. Shi, X.W. Zhang, Formation and charac-
terization of core-sheath nanofibers through electrospinning and surface-initiated
polymerization, Polymer 51 (2010) 4368–4374.
[30] F. Zuo, D.H. Tan, Z.F. Wang, S. Jeung, C.W. Macosko, F.S. Bates, Nanofibers from melt
blown fiber-in-fiber polymer blends, ACS Macro Lett. 2 (2013) 301–305.
[31] L. Erich, U.S. Patent 5,075,063, December 24, 1991.
[32] H. Voelker, H.D. Zettler, W. Fath, H. Berbner, U.S. Patent 5,494,616, February 27,
1996.
[33] M. Luo, A.N. Neogi, U.S. Patent 6,221,487, April 24, 2001.
[34] A. Oya, T. Sando, U.S. Patent 7,763,228 B2, July 27, 2010.
[35] B. Vazquez, H. Vasquez, K. Lozano, Preparation and characterization of
polyvinylidene fluoride nanofibrous membranes by Forcespinning™, Polym. Eng.
Sci. 52 (2012) 2260–2265.
[36] Y. Lu, Y. Li, S. Zhang, G.J. Xu, F. Fu, H. Lee, X.W. Zhang, Parameter study and charac-
terization for polyacrylonitrile nanofibers fabricated via centrifugal spinning pro-
cess, Eur. Polym. J. 49 (2013) 3834–3845.
[37] L.Y. Ren, V. Pandit, J. Elkin, T. Denman, J.A. Cooper, S.P. Kotha, Large-scale and
highly efficient synthesis of micro- and nano-fibers with controlled fiber mor-
phology by centrifugal jet spinning for tissue regeneration, Nanoscale 5 (2013)
2337–2345.
[38] B.C. Weng, F.H. Xu, M. Alcoutlabi, Y.B. Mao, K. Lozano, Fibrous cellulose membrane
mass produced via forcespinning® for lithium-ion battery separators, Cellulose 22
(2015) 1311–1320.
[39] N. Bao, Z.T. Wei, Z.H. Ma, F. Liu, G.B. Yin, Si-doped mesoporous TiO2 continuous fi-
bers: preparation by centrifugal spinning and photocatalytic properties, J. Hazard.
Mater. 174 (2010) 129–136.
[40] H.Y. Liu, Y. Chen, G.S. Liu, S.G. Pei, J.Q. Liu, H. Ji, R.D. Wang, Preparation of high-qual-
ity zirconia fibers by super-high rotational centrifugal spinning of inorganic sol,
Mater. Manuf. Process. 28 (2013) 133–138.
[41] Q. Zhang, X. Wu, H.H. Chen, B. Yang, Preparation and photoelectric properties of in-
dium tin oxide depositional optical fiber by centrifugal spinning, J. Mater. Sci. Mater.
Electron. 26 (2015) 9031–9036.
[42] L. Xia, J.G. Ju, W. Xu, C.K. Ding, B.W. Cheng, Preparation and characterization of
hollow Fe 2O 3 ultra-fine fibers by centrifugal spinning, Mater. Des. 96 (2016)
439–445.
 T. Hou et al. / Materials and Design 114 (2017) 303–311
[43] C. Liu, J.Q. Sun, M. Shao, B. Yang, A comparison of centrifugally-spun and electrospun
regenerated silk fibroin nanofiber structures and properties, RSC Adv. 5 (2015)
98553–98558.
[44] X.L. Li, H.H. Chen, B. Yang, Centrifugally spun starch-based fibers from amylopectin
rich starches, Carbohydr. Polym. 137 (2016) 459–465.
[45] A.M. Loordhuswamy, V.R. Krishnaswamy, P.S. Korrapati, S. Thinakaran, G.D.V.
Rengaswami, Fabrication of highly aligned fibrous scaffolds for tissue regeneration
by centrifugal spinning technology, Mater. Sci. Eng. C 42 (2014) 799–807.
[46] H.Z. Xu, H.H. Chen, X.L. Li, C. Liu, B. Yang, A comparative study of jet formation in
nozzle- and nozzle-less centrifugal spinning systems, J. Polym. Sci. Polym. Phys. 52
(2014) 1547–1559.
[47] H.H. Chen, H.Z. Xu, J.Q. Sun, C. Liu, B. Yang, Effective method for high-throughput
manufacturing of ultrafine fibres via needleless centrifugal spinning, Micro Nano
Lett. 10 (2015) 81–84.
[48] L. Wang, J. Shi, L. Liu, E. Secret, Y. Chen, Fabrication of polymer fiber scaffolds by cen-
trifugal spinning for cell culture studies, Microelectron. Eng. 88 (2011) 1718–1721.
[49] Z.H. Qi, H. Yu, Y.M. Chen, M.F. Zhu, Highly porous fibers prepared by electrospinning
a ternary system of nonsolvent/solvent/poly(L-lactic acid), Mater. Lett. 63 (2009)
415–418.
[50] J. Hjärtstam, T. Hjertber, Studies of the water permeability and mechanical proper-
ties of a film made of an ethyl cellulose-ethanol-water ternary mixture, J. Appl.
Polym. Sci. 74 (1999) 2056–2062.
[51] R. Jayakumar, M. Prabaharan, S.V. Nair, H. Tamura, Novel chitin and chitosan nano-
fibers in biomedical applications, Biotechnol. Adv. 28 (2010) 142–150.
311
[52] L. Xu, N. Si, E.W.M. Lee, Effect of humidity on surface morphology of charged jet,
Heat Transf. Res. 44 (2013) 441–445.
[53] R. Rošic, J. Pelipenko, P. Kocbek, S. Baumgartner, M. Bešter-Rogač, J. Kristl, The role of
rheology of polymer solutions in predicting nanofiber formation by electrospinning,
Eur. Polym. J. 48 (2012) 1374–1384.
[54] A. Abbasi, M.M. Nasef, M. Takeshi, R. Faridi-Majidi, Electrospinning of nylon-6,6 so-
lutions into nanofibers: rheology and morphology relationships, Chin. J. Polym. Sci.
32 (2014) 793–804.
[55] Z.M. Huang, Y.Z. Zhang, M. Kotaki, S. Ramakrishna, A review on polymer nanofibers
by electrospinning and their applications in nanocomposites, Compos. Sci. Technol.
63 (2003) 2223–2253.
[56] D. Quéré, Wetting and roughness, Annu. Rev. Mater. Res. 38 (2008) 71–99.
[57] A.B.D. Cassie, S. Baxter, Wettability of porous surfaces, Trans. Faraday Soc. 40 (1944)
546–551.
[58] X.L. Yu, H.F. Xiang, Y.H. Long, N. Zhao, X.L. Zhang, J. Xu, Preparation of porous poly-
acrylonitrile fibers by electrospinning a ternary system of PAN/DMF/H2O, Mater.
Lett. 64 (2010) 2407–2409.
[59] E.S. Medeiros, L.H.C. Mattoso, R.D. Offeman, D.F. Wood, W.J. Orts, Effect of relative
humidity on the morphology of electrospun polymer fibers, Can. J. Chem. 86
(2008) 590–599.
[60] D.H. Reneker, A.L. Yarin, Electrospinning jets and polymer nanofibers, Polymer 49
(2008) 2387–2425.