Arabian Journal of Chemistry (2019) 12, 5162–5172

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Preparation of various nanofiber layers using wire

electrospinning system
Fatma Yalcinkaya

Centre for Nanomaterials, Advanced Technology and Innovation, Technical University of Liberec, Studentska 2, 46117
Liberec, Czech Republic

Received 7 September 2016; accepted 16 December 2016

Available online 26 December 2016

KEYWORDS Abstract This study focuses on the preparation of various polymeric nanofibers using new indus-
Nanofiber; trial production equipment – a wire electrospinning system. The disadvantages of each polymeric
Mass production; nanofiber were improved by mixing suitable polymer/polymer-solvent/solvent systems. A total of
Nanospider; 9 types of polymers (polyamide, polyvinylidene fluoride, polyacrylonitrile, polyurethane, polysul-
Chitosan; fone, chitosan, cellulose acetate, polyvinyl butyral, and polycaprolactone) and their mixtures were
Cellulose acetate electrospun using a wire electrospinning system. The resultant fiber surface morphology showed
that the wire electrospinning method is suitable for the production of various polymers on an indus-
trial scale. Moreover, polymer mixtures changed the adhesion properties, increased productivity
and reduced the fiber diameter of nanofibers.
Ó 2016 The Author. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

The application area of polymeric nanofibers has been increased since

the late 20th century due to their highly porous structure and high
aspect ratio and the new design of materials. The nanofibers can be
Abbreviations: CA, cellulose acetate; PCL, polycaprolactone; CH, produced easily using needle and needleless electrospinning, force spin-
chitosan; PA6, polyamide 6; PSU, polysulfone; PVDF, polyvinylidene ning, melt-blown, island-in-the-sea, drawing, etc. (Torobin and
fluoride; PU, polyurethane; PAN, polyacrylonitrile; AA, acetic acid; Findlow, 2001; Huang et al., 2012; Fabbricante et al., 2000; Huang,
DAA, diluted acetic acid; FA, formic acid; DMF, dimethylformamide; 2009; Nain et al., 2006; Jirsak et al., 2004). The biggest challenges
DMAC, dimethylacetamide; SEM, scanning electron microscope; Aw, for creating nanofibers are mass production and complicated struc-
area weight of nanofiber; G, weight of nanofiber at given area in gram; tures from multiple-fluid spinning processes (Wen et al., 2016; Yang
A, measured area of the web in square meter; HOB, human et al., 2016a; Yu et al., 2016). Among the various techniques reported
osteoblastic in the literature, the free surface electrospinning system using Nanospi-
E-mail address: [email protected] der electrospinning technology is one of the most demanded technolo-
gies for the continuous and mass production of nanofiber layers. The
Peer review under responsibility of King Saud University.
Nanospider technology was firstly developed by Jirsak et al. (2004),
and then the new models were improved by Elmarco (Petras et al.,
2010, 2009a, 2009b). The principle of the Nanospider equipment is
based on a rotating electrode immersed into a polymer bath. The role
Production and hosting by Elsevier
of the rotating roller electrode is to feed the solution on the surface of
http://dx.doi.org/10.1016/j.arabjc.2016.12.012
1878-5352 Ó 2016 The Author. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Preparation of various nanofiber layers 5163

Table 1 Polymer and polymer mixture solutions.

Polymers Polymer ratio (% wt.) Solvent ratio (% wt.) Total concentration of polymer in solution (% wt.)
PA6 AA:FA (2:1) 8
PVB AA 11
PCL AA:FA (2:1) 12
CH DAA 8
CA AA 9
PSU DMAC 10
PVDF DMAC 13
PAN DMAC 8
PU DMF 13
CA:PVB 1:1 AA 10
CA:PA6 1:1 AA:FA 8.5
PA6:CH 1:1 AA:FA:DAA 8
PA6:PCL 1:1 AA:FA 10
PA6:PVB 1:1 AA:FA 9.5
PCL:PVB 1:1 AA:FA 11.5
CH:PVB 1:1 AA:DAA 9.5
PCL:CH 1:1 AA:FA:DAA 10
PU:PSU 1:1 DMF:DMAC 11.5
PVDF:PAN 1:1 DMAC 10.5

Table 2 Spinning conditions of solution on wire electrospinning system.

Solution Applied voltage/ Relative humidity- Wide of Speed of substrate Diameter of
distance (kV/cm) Temperature (%-°C) substrate (cm) (mm/min) wire (mm)
PA6, CA:PA6, PA6:PCL 3.28 30–22.5 40 13 0.2
PVB, CA:PVB, PA6: 3.28 30–22.5 40 13 0.2
PVB, PCL:PVB
PCL 3.28 30–22.5 40 13 0.2
CH, PA6:CH, PCL:CH 3.28 30–22.5 40 13 0.2
CA 3.28 30–22.5 40 13 0.2
PSU, PU:PSU 3.88 26–22.0 40 13 0.2
PVDF, PVDF:PAN 3.80 33–22.5 40 13 0.2
PAN 3.80 33–22.5 40 13 0.2
PU 3.88 26–22.0 40 13 0.2

Table 3 Spinning performance of nanofiber webs.

Polymers Aw (g/m2)
PA6 0.800
PVB 3.53
PCL 5.00
CH Not spinnable
CA 3.50
PSU 8.20
PVDF 6.80
PAN 3.50
PU 5.40
CA:PVB 3.62
CA:PA6 3.83
PA6:CH 0.40
PA6:PCL 1.70
PA6:PVB 8.20
PCL:PVB 7.10
Figure 1 Schematic illustration of a Nanospider new generation
CH:PVB Solution precipitate
electrospinning device, (A) a solution tank feeds the solution PCL:CH Droplets, no fiber
toward the wire, (B) wire electrode, (C) spinning area, (D) take-up PU:PSU 13.80
cylinder connected to backing material, and (E) high voltage PVDF:PAN 6.98
supply.
5164 F. Yalcinkaya

Figure 2 Preparation of nanofiber webs to calculate Aw.

Figure 3 SEM images of the PA6/CH mixture electrospun nanofiber.

the roller. The biggest difference between the first (roller electrospin- spinnability of various polymeric solutions. Moreover, the closed feed-
ning) and the new generation Nanospider (wire electrospinning) is ing system makes it possible to keep solution viscosity stable over time.
the type of electrode and feeding unit. In new generation technology, On the open surface, some hygroscopic polymer solutions can easily
there is a conveyor wire electrode and a close bath unit conveyed on absorb the humidity and change the viscosity and properties of the
the wire for the feeding of the solution. The effective electrostatic field solution over time. Using a wire electrode the Nanospider equipment
on a thin wire is higher than roller surface which might affect the prevents the undesirable variations in the polymer solution during
Preparation of various nanofiber layers 5165

long-term usage. The use of the conveyor wire can easily remove the the solution’s viscosity stable over time. In the force spinning method,
ex-solution, and the new fresh solution is always supplied to the productivity is very high but the controlling of the fiber diameter and
electrode. diameter distribution is not easy. In melt electrospinning, productivity
The wire electrospinning system has great advantages compared to is high but the fiber diameter and diameter distribution are wide. The
many mass production methods. Roller, disk or spring electrospinning drawing method has very low productivity rates while the fiber diam-
systems have high productivity rates, with the fiber diameters varying eter is high. In the island-in-the-sea method, the fibers are produced in
between 80 and 700 nm with a standard deviation of ±50 nm. How- entanglement form and the fiber diameter varies between 800 and
ever, the solution is on an open surface and it is difficult to maintain 2500 nm with a standard deviation of ±200 nm.

Figure 4 SEM images of (A) CA, (B) CA + PVB, (C) CA + PA6.

5166 F. Yalcinkaya

The advantage of using the wire electrode Nanospider equipment is information about the production of nanofibers using wire electrospin-
the easy formation of nanofibers on a thin wire (
0.2 mm). The pro- ning in the literature. Herein, a wide range of polymer and polymer
ductivity rate is very high; the fibers are thin (80–700 nm) and have mixtures were fabricated and the disadvantages of each polymer were
a narrow standard deviation (±30 nm). eliminated and new features added by using polymer mixtures. The
In this study, various electrospun polymeric nanofibers were fabri- improvement of the various nanofiber webs’ disadvantages was studied
cated using wire electrospinning. Unlike in the case of roller electrode for the first time.
Nanospider electrospinning (Yalcinkaya et al., 2014, 2016a, 2016b, The fiber diameter of nanofibers can be changed through electro-
2015; Yener et al., 2013; Yener and Jirsak, 2012; Cengiz et al., 2010; spinning parameters. However, controlling the fiber diameter is not
Sasithorn and Martinova, 2014; Jirsak et al., 2010), there is not enough an easy process. Changing the spinning parameters (applied voltage,

Figure 5 SEM images of (A) PVB, (B) PA6, (C) PA6 + PVB nanofibers.
Preparation of various nanofiber layers 5167

distance between electrodes, solution properties and speed of carriage) The diversity of spinnable polymers showed that the use of the wire
can make changes on the fiber diameter but parameters alone are not electrode Nanospider equipment had big advantages for the continu-
sufficient to obtain nanofibers without beads. Herein, some of the ous mass production of nanofibers. The resulting nanofibers are suit-
polymer mixtures were used to change the surface morphology of able for application in air filtration, water filtration, ion-battery
the nanofiber layers. separation, bio-medical application, cosmetics, etc. (Bella, 2015;

Figure 6 SEM images of (A) PCL, (B) PCL + PA6, (C) PCL + PVB nanofibers.
5168 F. Yalcinkaya

Figure 7 SEM images of (A) PSU, (B) PU, (C) PVDF, (D) PAN nanofibers.

Bella et al., 2015; Yalcin Enis and Gok Sadikoglu, 2016; Yalcinkaya centages of the prepared solutions and mixtures are shown in
et al., 2016a, 2016b; Yang et al., 2016b). The aim of the preparation Table 1. For the solution mixtures, first the single polymer
of mixture fibers was to eliminate disadvantages such as weakness, solution was prepared, and then the polymer blends were pre-
abrasion, hydrophilicity/hydrophobicity, and oleophilicity/oleopho- pared at a given weight ratio according to Table 1 and mixed
bicity and improve and combine the advantages of polymers. The
overnight. The concentration ratio was determined according
blended nanofibers are more advantageous compared to single electro-
spun nanofibers for improving the mechanical, structural, antibacte- to our previous experiments and known-how.
rial, biocompatible and engineered properties of materials. The spinning conditions kept stable during process are
shown in Table 2. The schematic figure of the new generation
Nanospider equipment is shown in Fig. 1.
2. Experimental The solution is placed into a feed unit (A, B). The wire is
placed in the middle of the solution tank. The feed unit is mov-
50.000 g/mol cellulose acetate (CA) and 45.000 g/mol poly- ing back and forth and the solution is feeding on the wire. The
caprolactone (PCL) were purchased from Sigma–Aldrich; veg- upward part has a second wire electrode, which generally has
etal chitosan (CH) was purchased from KitoZyme; the opposite charge to the downward wire electrode or is
60.000 g/mol polyvinyl butyral was purchased from Mowital; grounded. If the electrical field between the electrodes over-
ultra-aramid B24 polyamide 6 and Ultrason E600P polysul- comes the surface tension of the polymer solution, fibers are
fone (PSU) were purchased from BASF; Polyvinylidene fluo- formed (C). A conveyer backing/supporting material is placed
ride (PVDF) was donated by Kynar 761A; polyurethane was in between the two electrodes to collect the fibers, moving at a
purchased from Larithane LS 1086; 150.000 g/mol polyacry- desired speed using take-up cylinders (D).
lonitrile (PAN) was purchased from Dimachema Pigment Cor- The nanofibers were analyzed using a scanning electron
poration. The solvents, %99 acetic acid (AA) and %56 diluted microscope (SEM, Tescan Vega3 SB). All samples were gold-
acetic acid (DAA), formic acid (FA), dimethylformamide coated for 60 s and 7 nm thickness before SEM imaging to
(DMF), and dimethylacetamide (DMAC) were purchased reduce the effect of charging. The Image-J software was used
from Penta s.r.o. The polymers were dissolved in the solvent to measure the average fiber diameter from more than 50 dif-
for 30 h and mixed to form a homogenous solution. The per- ferent randomly selected fibers.
Preparation of various nanofiber layers 5169

Figure 7 (continued)

The productivity of the nanofiber webs can be compared good candidate for biomedical application and adsorbent
calculating the area weight (basis weight) of the samples. materials to remove dyes from industrial wastewater (Iqbal
Table 3 shows the area weight of each polymeric nanofiber et al., 2011; Sobahi et al., 2014; Kenawy et al., 2015). The idea
web. The area weight of the nanofibers was calculated accord- of mixing chitosan with other polymers is to improve
ing to Eq. (1): spinnability and mechanical and biocompatible properties.
G The results showed that only the mixture of a chitosan and
Aw ¼ g=m2 ð1Þ polyamide 6 solution forms nanofiber structures with a low
A
area weight and fiber diameter.
where Aw is the area weight of the nanofiber web, G is the The results of chitosan and polyamide 6 mixture nanofibers
weight of nanofibers at a given area (gram), and A is the mea- are given in Fig. 3.
sured area of the web (m2). The samples were cut into sheets of Fig. 3 shows that there are two types of fiber in polymer
10  10 cm2 (3 for each sample), separated and weighted as mixture nanofibers. It can be observed that the average fiber
shown in Fig. 2. diameter is less than 100 nm. Moreover, some fibers have bro-
ken ends. The reason can be explained as follows: chitosan has
3. Result and discussion low concentration (8%) with very high viscosity, which pre-
vents the continuous fiber forming, with the drops breaking
The results showed that some of the polymers and their mix- following fiber formation. The entanglement between the chi-
tures did not form fibers as shown in Table 3. Each polymer tosan macromolecules is not strong enough to produce contin-
solution showed different spinnability and spinning perfor- uous nanofibers. Chitosan has an effective volume fraction
mance. Spinning performance is an important parameter for that is much greater than its actual volume fraction, which
the productivity. means physical properties equivalent to higher concentrations
The spinning of a pristine chitosan polymer solution is of less complex molecules (LeCorre-Bordes et al., 2016). It can
quite difficult due to high viscosity. Gel-like networks prevent be suggested that chitosan nanofibers can be produced with a
the formation of electrospun fibers. Chitosan nanofiber is a mixture of PA6 for possible application of microfiltration,
5170 F. Yalcinkaya

Figure 8 SEM images of (A) PSU + PU and (B) PVDF + PAN.

enzyme immobilization (Li et al., 2014; Maryskova et al., an additional polymer has a huge effect on the final polymer
2016) or human osteoblastic (HOB) cell culture applications diameter and the bead structure as well. The mixture of CA
(Nirmala et al., 2011). with PA6 or PVB did not change the spinning performance
Cellulose acetate nanofibers are biocompatible and have of pristine CA nanofibers. Among all CA and mixtures, CA
high hydrophilicity, which make them a good candidate for + PA6 nanofibers are an excellent candidate for air
water treatment. It has been mentioned that spinning of CA (Matulevicius et al., 2016; Nicosia et al., 2016) and water filtra-
solutions is not easy to control (Liu et al., 2016). Despite tion (Carpenter et al., 2015; Zhou et al., 2016).
changing process parameters, beads form easily. As shown in It was observed that during spinning PVB nanofibers have
Fig. 4(A), we also observed many beads on the surface of the ability to stick to all the surfaces of the spinning unit, take-
the web. The easy way to eliminate the bead structure is mixing up cylinders and the feed tank, which leads to difficulty in
with other polymer. In this way, not only are the beads elimi- keeping nanofibers on the surface of backing materials. The
nated, but it is also possible to enhance the advantages of mixing of PVB with PA6 nanofibers has the advantage of
nanofibers. decreasing the average fiber diameter and leads to narrower
The idea of mixing CA with PA6 or PVB polymers is to fiber diameter distribution. Moreover, the adhesion problem
reduce the bead structure and improve surface morphology of the PVB nanofibers was eliminated and the area weight
(Fig. 4). CA + PVB nanofibers have almost 5 times higher was increased almost 2.3 times, which translates into lower
fiber diameters than pristine CA nanofibers, while CA energy costs.
+ PA6 nanofiber diameters are almost equal to pristine CA. Polycaprolactone is a low-cost, biodegradable polyester.
The PVB nanofibers have an average nanofiber diameter of Studies showed that the biocompatibility of PCL nanofibers
around 350–370 nm, PA6 of around 40–60 nm (Fig. 5), and has a promising future in biomedical applications (Mahjour
their mixture of around 180–200 nm. The results indicate that et al., 2016; Venugopal et al. (2005); Thorvaldsson et al.,
Preparation of various nanofiber layers 5171

2008; Pajoumshariati et al., 2016). It was found that the adhe- bers have a small fiber diameter of around 60 nm, which sug-
sion property of PCL nanofibers is much lower than that of gests a potential application area for high-efficiency air
protein nanofibers, which might be a disadvantage for the lam- filtration.
ination process (Baker et al., 2016). To improve the adhesion The PA6 and PVB nanofibers were electrospun with aver-
properties of PCL nanofibers, the mixture of PCL + PA6 age fiber diameters of around 50 and 400 nm respectively.
and PCL + PVB was prepared. PVB has excellent adhesion PVB is quite a cheap polymer compared to other polymers
properties and is very cheap compared to PCL and PA6. and is easy to process and handle. There are not many studies
The results of SEM are shown in Fig. 6. about the application of PVB nanofibers. Based on the appli-
Fig. 6 shows that the mixture of PCL and PA6 solutions cation area, the fiber diameter of PVB nanofibers can be
increases the bead structure of nanofibers while the spinning reduced and the spinning performance can be increased by
performance decreases dramatically. On the other hand, mix- mixing with PA6.
ing PVB with PCL decreases the formation of beads on the PCL was mixed with PA6 and PVB. The resulting electro-
surface of the layer but increases the average fiber diameter 3 spun fibers showed that a mixture of PCL + PA6 creates
times. The area weight of PCL was increased by adding beads on the surface of the nanofiber. On the other hand, a
PVB. If the adhesion properties of PVB nanofibers are consid- mixture of PCL + PVB nanofibers has good surface morphol-
ered, it can be concluded that nanofibers from the mixture of ogy and very high productivity. Using the adhesion properties
PCL with PVB would have increased adhesion properties of PVB, the adhesion properties of PCL nanofibers can be
and also a decreased bead structure of nanofiber layers. improved.
Polysulfone, polyurethane, polyvinylidene fluoride and PSU, PU, PVDF and PAN all have special properties for
polyacrylonitrile are good candidates for wastewater filtration, various application areas. The mechanical properties and the
reverse and forward osmosis and membrane distillation. All area weight of PSU and PAN nanofibers were improved by
the polymers were easily electrospun into nanofibers using mixing with PU and PVDF respectively.
the wire electrospinning system. The SEM results of the vari-
ous polymers are shown in Fig. 7.
In our previous experiments, we found that PSU nanofibers
are not good in terms of their mechanical and abrasion prop-
erties. PSU nanofibers are damaged and removed from the
backing material very easily under slight tension. PU nanofi-
bers have good tensile properties and elasticity, and are insol-
uble in water. A mixture of PU with PSU improved the
mechanical and abrasion properties of nanofibers. When exter-
nal tension was applied, the PU/PSU nanofibers were not
damaged or removed from the backing material (Fig. 8).
PAN has highly polar groups in the backbone that improve
the hydrophilicity of the materials and are advantageous for
wastewater treatment as they decreased the fouling effect.
PVDF nanofibers are quite strong but highly hydrophobic.
Combining PVDF with PAN can improve the hydrophilicity
and mechanical properties of nanofibers. The mixture of nano-
fiber layers is shown in Fig. 8.
Pristine PU and PVDF nanofibers have a larger fiber diam-
eter and diameter distribution in comparison with PSU and
PAN. Both PSU and PAN nanofibers have a diameter of less
than 100 nm, which is promising for air and water filtration.
On the other hand, the mechanical properties and hydropho-
bicity of PSU and PVDF are disadvantages and can be easily
eliminated by mixing with PU and PAN respectively. The mix-
ture of PSU + PU nanofibers has an average fiber diameter of
around 120–140 nm while that of the PAN + PVDF mixture
is around 120 nm. Both results of the mixture showed signifi-
cant surface morphology and small fiber diameters, which
make them a good candidate for water and air filtration. The
mixing of PSU/PU increased the area weight of PSU and
PU 1.68 and 2.5 times respectively, while the mixture of
PAN/PVDF increased PAN and PVDF to 1.99 and 1.02
respectively.
The main results of the work can be summarized as follows:
Mixing a chitosan polymer with PA6 can form nanofibers
while a mixture of CH + PVB and CH + PCL did not form
nanofibers.
Bead-free cellulose acetate nanofibers were produced by Figure 9 Comparison of various nanofiber webs according to
mixing with PA6 and PVB polymers. The CA + PA6 nanofi- their (A) fiber diameter and (B) area weight.
5172 F. Yalcinkaya

Hereby, Fig. 9 shows the area weight and the fiber diameter LeCorre-Bordes, D., Tucker, N., Huber, T., Buunk, N., Staiger, M.P.,
of all polymers and polymer mixtures. The idea of mixing 2016. J. Mater. Sci. 51 (14), 6686.
polymers mainly showed advantages with respect to fiber Li, C.J., Zhang, S.S., Wang, J.N., Liu, T.Y., 2014. Catal. Today 224,
diameter, diameter distribution and area weight. 94.
Liu, C., Li, X., Liu, T., Liu, Z., Li, N., Zhang, Y., Xiao, C., Feng, X.,
2016. J. Membrane Sci. 512, 1.
4. Conclusion Mahjour, S.B., Sefat, F., Polunin, Y., Wang, L., Wang, H., 2016. J.
Biomed. Mater. Res. A. 104, 1479.
The production of nanofibers using wire electrospinning has not been Maryskova, M., Ardao, I., Garcia-Gonzalez, C.A., Martinova, L.,
yet investigated in detail, although this technology has been utilized on Rotkova, J., Sevcu, A., 2016. Enzyme Microb. Tech. 89, 31.
an industrial scale. Wire electrospinning systems are superior to many Matulevicius, J., Kliucininkas, L., Prasauskas, T., Buivydiene, D.,
production methods in the market due to their high productivity and Martuzevicius, D., 2016. J. Aerosol. Sci. 92, 27.
ease of setting up and cleaning. Almost all polymers that form nanofi- Nain, A.S., Wong, J.C., Amon, C., Sitti, M., 2006. Appl. Phys. Lett. 89
bers in the needle electrospinning system can be electrospun using (18), 183105.
needle-free wire electrospinning at higher production efficiency rates. Nicosia, A., Keppler, T., Müller, F.A., Vazquez, B., Ravegnani, F.,
It can be concluded that most common polymers in the market Monticelli, P., Belosi, F., 2016. Chem. Eng. Sci. 153, 284.
could be easily electrospun to produce nanofibers using the wire elec- Nirmala, R., Navamathavan, R., Kang, H.S., El-Newehy, M.H., Kim,
trospinning system. The results of this work provide an insight into the H.Y., 2011. Colloid. Surface. B 83, 173.
industrial application of nanofibers. The optimization of nanofiber lay- Pajoumshariati, S., Yavari, S.K., Shokrgozar, M.A., 2016. Ann.
ers is time consuming and costly. The optimization process was almost Biomed. Eng. 44, 1808.
completed by mixing of various spinnable polymers and the disadvan- Petras, D., Maly, M., Kovac, M., Stromsky, V., Pozner, J., Trdlicka,
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Acknowledgment 2007137530.
Petras, D., Maly, M., Pozner, J., Trdlicka, J., Kovac, M., 2010. US
The results of this project LO1201 were obtained through the Patents, 20100034914.
financial support of the Ministry of Education, Youth and Sasithorn, N., Martinova, L., 2014. J. Nanomater., 9 Article ID
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‘‘National Programme for Sustainability I”. Special thanks 7 (5), 741.
to Ms. Tamara Pavlovova and Mr. Jerome Chauveau, Kynar Thorvaldsson, A., Stenhamre, H., Gatenholm, P., Walkenström, P.,
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