Received: 9 October 2020 Revised: 7 December 2020 Accepted: 10 December 2020

DOI: 10.1002/pc.25924

RESEARCH ARTICLE

Coaxial electrospinning process toward optimal

nanoparticle dispersion in polymeric matrix

Francisco Sebastian Navarro Oliva1 | Léo Picart1 |

Christopher Y. Leon-Valdivieso1 | Ahmed Benalla1 | Luc Lenglet2 |
Alejandro Ospina1 | Jacques Jestin3 | Fahmi Bedoui1

1
Roberval Laboratory, FRE UTC-CNRS
2012, Sorbonne Universités, Université de
Technologie de Compiègne, Compiègne,
France
2
NORMAFIN, LEVALLOIS-PERRET,
France
3
DPT, Institut Laue-Langevin, 71 avenue
des Martyrs, Grenoble, France
Correspondence
Fahmi Bedoui, Roberval Laboratory, FRE
UTC-CNRS 2012, Sorbonne Universités,
Université de Technologie de Compiègne,
Compiègne, France.
Email: fahmi.bedoui@utc.fr
Abstract
Nanoreinforced polymers have gained popularity in the last decades since
they exhibit enhanced properties (compared to pristine polymers) that are
useful in a wide range of applications. Unfortunately, dispersion of
nanoparticles (NPs) into polymeric matrices is a major problem since they
tend to form agglomerates, limiting the improvement of properties and
further applications. In this work, we propose the use of coaxial
electrospinning as one-step method to disperse NPs in a polymeric matrix.
Particularly, iron oxide (Fe3O4) NP with a monomodal and bimodal size dis-
tributions were dispersed in polyvinylidene fluoride (PVDF), a material that
is well known for its improved piezoelectric properties when it is processed
via electrospinning. The results indicate that the incorporation of NP modi-
fied the polymeric fiber depending on their surface-to-volume ratio (smaller
NP promoted smaller fiber size). Moreover, transmission electron micros-
copy revealed a good NP dispersion in the polymer, especially for the
smallest NP size (monomodal). Finally, each NP size distributions were
well preserved in the electrospun mats compared to the initial NP solutions,
demonstrating the suitability of this technique for the fabrication of
nanoreinforced PVDF structures with tailored NP size. Overall, this method
could represent a facile and practical alternative to fabricate materials with
piezoelectric/super-paramagnetic properties.

KEYWORDS
coaxial electrospinning, nanofibers, nanoparticle dispersion

1 | INTRODUCTION kinds of metallic or ceramic materials for different applica-

The use of nanoparticle (NP) reinforced polymers has
received the attention of materials scientists in the last
decades, since they provide with a facile/versatile alterna-
tive to enhance the thermal, mechanical,[1] magnetic,[2]
electrical,[3] and energy storage[4] properties of unmodified
polymers, having also the potential to substitute different
tions.[5] Improvements of these properties can be achieved
with NP volume fractions as low as 3%–10% (wt/wt).[6–8]
However, one of their major drawbacks is the lack of com-
patibility between the inorganic NPs and the polymeric
matrix, leading to poor dispersion and formation of aggre-
gates, limiting their applicability and even displaying nega-
tive effects on their performance.[9]

Polymer Composites. 2021;42:1565–1573. wileyonlinelibrary.com/journal/pc © 2021 Society of Plastics Engineers 1565

1566
Diverse methods have been explored to increase the
dispersion of NP into polymeric matrices: shear mixing
and sonication, sol-gel process and chemical modification
of either components.[10] Although these strategies
generally render good NP dispersion in the composites,
they also present some specific drawbacks: dispersion
promoted by physical forces (shear mixing-sonication)
could be reversed because of the hydrophilic nature of
NP's cover and therefore dispersing agents are neces-
sary[11,12]; composites developed through sol-gel tech-
nique in some cases present weak bonding and hard
porosity control, in addition to time-consuming aging/
drying processes[13]; finally, NP surface modification
(polymer-grafting onto the hydroxyl groups included)
is perhaps the most common method to prepare
homogenous NP/polymer composites although it nor-
mally comprises two or more synthetic steps.[9] For
instance, in a recent approach, Ding et al. prepared
polymer nanocomposites using anionic and cationic
ligands as NP dispersant, emulsifier, and comonomer
(i.e., the ligands copolymerized with the polymer
matrix).[14] Despite the qualitatively-enhanced NP dis-
persion, increased tensile strength (77% higher com-
pared to nonmodified polymer) and improved thermal
stability (24 C higher than control), this method impli-
cated multiple (preparative) steps, which turns it rather
unpractical.
The preparation of polymeric composites via
electrospinning has gained attention lately,[15–18] not only
because NP reinforce the fibrillar structure of electrospun
mats, but also the fiber networks could protect NP from
environmental processes such as corrosion and oxida-
tion.[19] However, this process still relies on the mixing of
the components (polymer + NP) in the syringe prior to
the electrospinning of the solution; this condition can
result in the formation of aggregates (depending on the
flow rate) that will not only be incorporated onto the
fibers but could also provoke nozzle clogging and affect
the fabrication process.
Coaxial electrospinning has emerged as a straightfor-
ward alternative to conventional electrospinning for pro-
ducing well-dispersed nanoreinforced polymers by
injecting the components in a core-shell fashion.[20–23]
Moreover, this technique has been useful in the produc-
tion of NP/polymer mats with improved properties such
as thermal stability, photodegradation performance and
superparamagnetic properties.[2,24,25]
In this work, we employed coaxial electrospinning
as a one-step alternative to fabricate nanoreinforced
polyvinylidene fluoride (PVDF) featuring the disper-
sion of iron oxide (Fe3O4) NP with different size distri-
butions (monomodal or bimodal) within the polymeric
NAVARRO OLIVA ET AL.
fibers. Our main goal is to reach a good qualitative NP
dispersion within the fibrillar network for each NP size
distribution. Here, PVDF was chosen since it is well
known that electrospinning promotes the appearance
of its β-phase, one of its five crystal polymorphs which
presents a highly polar organization,[26] making it a
potential candidate for the development of materials
with ferroelectric/piezoelectric properties. Further,
PVDF is a highly tunable material when used in
nanocomposites; improvements on its mechanical,
thermal, electrical, and electromagnetic properties
have been already reported.[8,27,28] Additionally, we
aim the incorporation of Fe3O4 NP into the PVDF net-
work since they can provide with super-paramagnetic
properties to the final electrospun composite, making
it relevant for energy harvesting or biomedical
applications.
2 | MATERIALS AND METHODS
2.1 | Coaxial electrospinning of polymer
and NPs
The representation of the coaxial electrospinning set-
up used in this study is shown in Figure 1. In brief,
1.876 g of polyvinylidene fluoride (PVDF, ref:
FV306300, Goodfellow, Ltd, Cambridge, UK) were
dissolved in 10 ml of a dimethylformamide (DMF)-
acetone mix (40/60 vol/vol) and stirred (400 rpm) at
70  C during 1 h. The PVDF solution (18% wt/wt) was
then left to cool down for another 15 min before load-
ing it into the shell syringe. The core syringe was
loaded with a 5 mg/ml solution of iron oxide (Fe 3 O 4 )
NPs with oleic acid as a surface ligand in toluene
(CytoDiagnostics, Inc., Burlinton, Canada), which
was used without further purification. Four NP sizes
were used in this study: 5 nm (batch n :
O0124817E3127), 10 nm (batch n  : O0228119F31380),
20 nm (batch n  : O0328119F31381) and a mix of
10 and 20 nm (batch n  : O317217F29229), which are
here referred as NP5, NP10, NP20, and NP10-20, cor-
respondingly. Both core and shell syringes were
loaded onto separate automatic KDS-100 pumps
(Kd Scientific) whose flow rates were set at 0.005 and
0.020 ml/min, respectively, and their content injected
through silicone tubings into a coaxial needle system
(Spraybase, Maynooth, Ireland). A distance of 18 cm
was kept between the coaxial needle and a flat collec-
tor while a voltage of 17.5 kV was imposed between
them throughout the whole process. The total
electrospinning time per sample was 20 min.
NAVARRO OLIVA ET AL. 1567

FIGURE 1 Schematic representation of the electrospinning process [Color figure can be viewed at wileyonlinelibrary.com]

T A B L E 1 Parameters used for the fabrication of Fe3O4

NP/PVDF composites via coaxial electrospinning 2.2 | Scanning electron microscopy
Parameters Samples were cut in squares (approximately 5 × 5 mm2) out
CNP 0.005 g/ml of the electrospun film, mounted on carbon discs, metal-
CPVDF 0.170 g/ml coated with gold (5 nm) and observed using a Quanta FEG
QNP 0.005 ml/min 250 from FEI Environmental Scanning Electron Microscope
QPVDF 0.020 ml/min
(SEM). The fiber size distribution was manually measured
using the software Ellix (by Microvision) and ImageJ
ρNP 5.17 g/ml
(by National Institutes of Health) on the acquired SEM
ρPVDF 1.78 g/ml
images, considering at least 120 measures per sample (n = 3).
fm/fv (th) 0.73%/0.25%

Abbreviations: NP, nanoparticle; PVDF, polyvinylidene fluoride.

In this study, a theoretical volume ratio of NP in the
composite (fv) = 0.25% was chosen. The NP and PVDF
solution flow rates (ml/min; QNP and QPVDF) were set
according to the following equation:
C NP × QNP
fv =
C NP × QNP + ρρNP × CPVDF × QPVDF
PVDF
where CNP and CPVDF are the concentrations (g/ml) of
NP and PVDF in solution, respectively, and ρNP and
ρPVDF their corresponding densities (g/ml). The final
parameters are given in Table 1.
2.3 | Transmission electron microscopy
The size distribution of Fe3O4 NP was determined with a
2100F (JEOL, Ltd) Transmission Electron Microscope
(TEM) by applying an acceleration voltage of 200 kV.
Carbon-coated mesh grids were used to collect the samples
to be analyzed: for the pure Fe3O4 NP, a single drop of the
NP solution was placed on the grid, leaving the solvent to
evaporate at room temperature; for the NP-containing
PVDF matrices, the grid was placed on the electrospinning
collector to allow fibers deposition during 15 s. The NP
diameter distribution was manually quantified from the
acquired TEM images using the software Ellix (v. 10.4.3)
and ImageJ on at least 300 measures per sample (n = 3).
1568 NAVARRO OLIVA ET AL.

F I G U R E 2 Transmission electron
microscopy images of nanoparticle
(NP) solutions and size distribution
for NP5 (A), NP10 (B), NP20 (C), and
NP10-20 (D)

3 | R ESULTS A NS DISCUSSION of each type of NP was investigated. Figure 2 shows that

NP5, NP10, NP20, and NP10-20 suspensions exhibit a
The main goal in this study is to achieve a homogeneous good dispersion without the presence of aggregates or
NP distribution in the PVDF matrix. First, the initial state clusters (surfactant-driven behavior). NP5, NP10, and
NAVARRO OLIVA ET AL. 1569

F I G U R E 3 Scanning electron microscopy images of electrospun polymeric matrices (polyvinylidene fluoride [PVDF], PVDF + NP5,
PVDF + NP10, PVDF + NP20, and PVDF + NP10-20) and their corresponding fiber size distribution. Insets: zoom-in to the fibers in the
composite images. Scale bar = 1 μm

TABLE 2 NP size and the resulting polymeric matrix fiber size

Fiber
NP size (nm) size (nm)
Pure PVDF — 250.5 ± 66.7
PVDF + NP5 5.95 ± 0.98 153.6 ± 36.6
PVDF + NP10 9.28 ± 1.15 189.4 ± 42.1
PVDF + NP20 17.30 ± 2.25 215.1 ± 42.7
PVDF + NP10- 16.56 ± 1.41, 10.57 ± 1.61 214.1 ± 42.4
20

Abbreviations: NP, nanoparticle; PVDF, polyvinylidene fluoride.

Coaxial electrospinning was used to fabricate the

F I G U R E 4 Fiber size distribution of electrospun polymeric
matrices (polyvinylidene fluoride [PVDF], PVDF + NP5, PVDF
+ NP10, PVDF + NP20, and PVDF + NP10-20) [Color figure can
be viewed at wileyonlinelibrary.com]
NP20 displayed a monomodal distribution, whereas
NP10-20 was bimodal, being relevant since it could pro-
vide with a model to fabricate bimodal-sized NP compos-
ites. Reinforced matrices with bimodal particle
distribution have been reported to improve mechanical
properties such as bending and compressive
strengths[29,30] when compared to the monomodal distri-
bution version.
Fe3O4/PVDF composites by fine-tuning the process
parameters (see 2.1 for final parameters used) until the
electrospun film presented a “consistent appearance”
(i.e., color uniformity would imply a good mac-
rodispersion of NP across the entire mat). The flow rates
(QNP and QPVDF) were cautiously controlled throughout
the whole process to ensure the reproducibility of the
chosen theoretical NP/PVDF volume ratio, by cleaning
the coaxial system and syringes thoroughly after the con-
tinuous production of two mats to avoid nozzle clogging
(caused either by the polymer or NP) and consequent
changes in flow rates.
The nanostructure of the resulting matrix was analyzed
via SEM (Figure 3). Micrographs show that the
1570 NAVARRO OLIVA ET AL.

F I G U R E 5 Schematic representation of coaxial electrospinning comparing two different size distributions. The main difference is based
on the nanoparticle (NP) surface-to-volume ratio: for a given fraction volume the total amount of NP is different because of their size
distribution, exhibiting a higher negatively-charged surface area for NP5 (1), increasing the electrostatic attraction and thus stretching the
fibers to a higher extent compared to NP20 (2). This stretching effect results in reduced fiber diameter in polyvinylidene fluoride [PVDF]
+ NP5 matrices compared to PVDF + NP20 [Color figure can be viewed at wileyonlinelibrary.com]

F I G U R E 6 Transmission
electron microscopy images of pure
only polyvinylidene fluoride
[PVDF], PVDF + NP5, PVDF
+ NP10, PVDF + NP20, and PVDF
+ NP10-20 matrices. Insets: zoom-in
to individual fibers. White arrows
indicate the location of NP on the
edges of the fibers
NAVARRO OLIVA ET AL.
F I G U R E 7 Size distribution of nanoparticle (NP) in their solvent and in the composite for NP5 (A), NP10 (B), NP20 (C), and NP10-20
(D) [Color figure can be viewed at wileyonlinelibrary.com]
incorporation of either iron oxide NPs into the polymeric
network caused a qualitative change in the roughness com-
pared to only-PVDF matrices (more grooved surfaces can
be observed). Moreover, there is an apparent decrease in
the fiber size distribution of the composites compared to
the pristine matrices (only-PVDF = 250.5 ± 66.7 nm;
PVDF+NP5 = 153.6 ± 36.6 nm; PVDF+NP10 =
189.4 ± 42.1 nm; PVDF+NP20 = 215.1 ± 42.7 nm; PVDF
+NP10-20 = 214.1 ± 42.4), which can be ascribed to an
increased polarization (due to the presence of negatively
charged NP) in the electrospinning jet, stretching the
fibers to a longer extent and reducing, thus, their diam-
eter[31] (graph in Figure 3, Figure 4, Table 2). This
effect is more pronounced in the samples where NP5
(smallest NP) are present, which we assumed it is
unequivocally related to the increased surface-to-
volume ratio provoking a fiber size reduction
(Figure 5).
Our results are in accordance with Li et al: they found
that (core-shell structured) nanoreinforced composites
exhibited a reduction in average fiber diameter compared
to their only-polymer versions. Moreover, this size decre-
ment was accentuated with increasing concentrations of
1571
cellulose-nanocrystals in the composite fibers, which con-
firms the role of conductivity and viscosity of the spin-
ning solutions not only in the final diameter of the fibers,
but also in their smoothness (or roughness) and general
structure.[2] Importantly, none of our samples presented
the formation of visible bead structures in the fibers,
which indicates that our coaxial electrospinning parame-
ters are adequate.
Samples were observed on the TEM to corroborate
the presence of NP in the PVDF matrix (Figure 6): the
inclusion of each NP distribution can be observed as well
as a good dispersion within the fiber, with negligible for-
mation of agglomerates in both types of composites.
Interestingly, some of the reinforced fibers showed the
presence of NP located on their edges rather than the
core (especially in the PVDF + NP10-20 composites).
This phenomenon, along with other factors such as
(inner) flow and jet bending instabilities[32,33] could
account for the appearance of the grooved morphologies
seen by SEM.
Further evaluation of NP size revealed that the diam-
eter distribution was well preserved in the final material
(Figure 7) compared to the initial NP solutions (ie,
1572
NP5: 5.48 ± 0.81 nm vs. 5.95 ± 0.95 nm; NP10:
9.19 ± 1.15 nm vs. 9.28 ± 1.15 nm; NP20: 17.51 ± 2.50 nm
vs. 17.30 ± 2.25 nm; NP10-20:10.91 ± 1.99 nm vs.
10.57 ± 1.61 nm [peak 1] and 17.01 ± 1.71 nm vs.
16.56 ± 1.41 nm [peak 2]); showing that this processing
method ensures the integrity of NP on the final reinforced
PVDF matrix.
4 | C ON C L U S I ON S
In this study, we showed the feasibility of coaxial
electrospinning to prepare NP-reinforced composites
(PVDF + Fe3O4), particularly for monomodal and
bimodal NP size distributions. The addition of NP
affected the fiber's morphology (decreased diameter)
by, presumably, increasing the electrostatic forces
between the electrospinning solution and the collector,
accelerating the jet and stretching to a higher degree
the negatively charged fibers. The incorporation of
NP5 in the PVDF matrix resulted in a stretching effect
due to the increased surface-to-volume ratio. The dis-
persion of NP in the fibers (as seen by TEM) was nota-
bly better in PVDF + NP5 composites compared to
PVDF + NP-20; the latter presented the formation of
clusters on the edges of the fiber, therefore optimiza-
tion of the process for this size distribution would be
required. Finally, the size distribution of the particles
is well preserved from the initial solution to the final
composite material. This fabrication process could be
used as a model to prepare Fe3O4 NP-containing mate-
rials for energy harvesting applications, therefore the
study of their magnetic properties needs to be further
studied.
CONFLICT OF INTEREST
The authors declare no potential conflict of interest.
ORCID
Fahmi Bedoui https://orcid.org/0000-0002-2607-5209
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