Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Effect of SiO2@polydopamine core/shell nanoparticles as multifunctional

filler for an aeronautical epoxy resin
Aldobenedetto Zotti 1, Simona Zuppolini 1, Anna Borriello ⇑, Mauro Zarrelli
Institute for Polymers, Composites and Biomaterials, National Research Council of Italy, 80055 Portici, Naples, Italy

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

Article history: Polydopamine (PDA) coated SiO2 nanoparticles (SiO2@PDA) were considered as filler for an aeronautical
Received 7 October 2019 graded epoxy matrix. The nanoparticles (NPs) were synthesized by a modified one-step procedure, based
Received in revised form 20 January 2020 on the nucleation and growth of SiO2 NPs followed by the growth of a thin PDA layer on the silica surface.
Accepted 23 January 2020
TEM observations have revealed that Core/Shell Nanoparticles (CSNPs) are characterized by a core with
Available online xxxx
a diameter of 250 nm and a 15 nm thick PDA shell. Nanocomposites with different filler concentrations
(0.1, 1 and 5 wt%) were manufactured. Preliminary fracture toughness results show an increase of both
Keywords:
KIC and GIC with addition of 1 wt% of CSNPs. Further samples will be tested by thermal and mechanical
Epoxy resin
Core/shell nanoparticles (CSNPs)
techniques, with particular attention to the thermal stability and fracture toughness properties.
Polydopamine (PDA) Ó 2020 Elsevier Ltd. All rights reserved.
Thermosetting resin Selection and peer-review under responsibility of the scientific committee of the 12th International
Fracture tougheness Conference on Composite Science and Technology.

1. Introduction of POSS as inner core, b) soft-ductile segments of rubber as a mid-

Thanks to their outstanding mechanical, thermal and electrical
properties epoxy resins have gained an increasing interest in a
wide spectrum of commercial fields such as high-performances
adhesives, coatings and matrix in composites [1]. Nevertheless,
the low thermal stability and the intrinsic brittleness limit the
employment of epoxy resins for extreme applications. In the last
decades many fillers, different in terms of chemical nature, shape
and size, were employed as modifier of epoxy resins: thermoplastic
nanoparticles (NPs) [2], inorganic NPs [3] and core/shell NPs [4] are
just a few examples.
Core/shell nanoparticles (CSNPs) have attracted the interest of
the scientific community because, considering low CSNPs contents,
it is possible to provide new interesting features to the hosting
matrix or improve its intrinsic properties [4,5]. Liu et al. [4] have
demonstrated an improvement of the Young’s modulus, tensile
strength, impact strength and fracture toughness of the epoxy
matrix with the addition of a small amount of nanoparticles (up
to 2 wt%). CSNPs are designed in order to take advantage of the sin-
gle phases properties constituting them. For example, Thitsartarn
et al. [5] have synthesized nanoparticles consisting of a) a rigid part
⇑ Corresponding author.
E-mail address: borriell@unina.it (A. Borriello).
1
Authors contributed equally to the paper.
dle layer and terminated with (c) the active functional groups, able
to strongly bind to the hosting matrix. Results have shown the syn-
ergetic effect of each layer to enhance both strength and toughness
of the nanocomposite. Zotti et al. [6] have induced ferro-magnetic
properties into an epoxy matrix adding Fe@C CSNPs: in fact, the
coercitivity increase up to 623 Oe with only 1 wt% of CSNPs. It is
noteworthy that CSNPs can be designed with tailored physical
properties, and this offers the possibility to manufacture nanocom-
posites with novel properties. Li et al. [7] have developed highly
transparent polymer nanocomposites using CSNPs consisting of a
silica core (low refractive index) and a titanium oxide shell (high
refractive index). Authors have tuned the shell thickness in order
to obtain NPs with the same refractive index of the hosting matrix,
nullifying the particles light scattering that causes the opacity of
the polymer.
In this work, silica@polydopamine NPs (SiO2@PDA) were
employed as filler in an aeronautical grade epoxy matrix. The
CSNPs were synthesized by a modified one-step procedure [8],
based on the nucleation and growth of SiO2 NPs followed by the
growth of a thin PDA layer on the silica surface. Nanocomposites
with different SiO2@PDA contents (0.1, 1 and 5 wt%) were manu-
factured and these samples will be thermally and mechanically
characterized, with particular attention to the thermal stability
and fracture toughness properties.

https://doi.org/10.1016/j.matpr.2020.01.407
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 12th International Conference on Composite Science and Technology.

Please cite this article as: A. Zotti, S. Zuppolini, A. Borriello et al., Effect of SiO2@polydopamine core/shell nanoparticles as multifunctional filler for an aero-
nautical epoxy resin, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.407
2 A. Zotti et al. / Materials Today: Proceedings xxx (xxxx) xxx

2. Materials and methods nominal dimensions of 3  6  27 mm. The specimen was loaded
in a 3-point bending configuration using an Instron 4301 equipped
Tetraethyl orthosilicate (TEOS), (3-aminopropyl)triethoxysilane with a 250 N load cell at a displacement rate of 1 mm/min.
(APTES), dopamine hydrochloride (DA, 98%), ammonium hydrox-
ide (NH4OH, 25%), ethanol and tetrahydrofuran (THF) were pur-
chased from Sigma-Aldrich. All the chemicals were used as 3. Results and discussions
received without further treatment.
The used resin system was RTM6 epoxy supplied by Hexcel Fig. 1 reports the FTIR spectra of pristine SiO2 NPs (a), pure DA
Composites (Duxford, UK); this is a pre-mixed epoxy-amine sys- (b) and synthesized SiO2@PDA NPs (c). In the DA spectrum the
tem developed for liquid infusion processes as characterized by a characteristic primary amine bending and stretching modes, cen-
very low viscosity (50 mPa s at 120 °C). tered at 1615 cm 1, 1580 cm 1 and 3346 cm 1, are clearly visible,
The synthesis procedure of SiO2@PDA CSNPs is reported in as well as the band at 3100 cm 1 corresponding to catechol –OH
Scheme 1. In a 500 mL three necked round bottom flask were stretching. In SiO2 NPs spectrum the peaks at 787 and 1038 cm 1
mixed ethanol (50 mL), distilled water (18 mL) and NH4OH correspond to the stretching of the Si-O and Si-OH bonds, respec-
(6.3 mL). The solution was mixed for 10 min, and then a mixture tively. In the SiO2@PDA NPs spectrum (c) the combined presence
of TEOS (14.7 mL) and APTES (5.2 mL) (75:25 molar ratio) was of both silica and DA peaks can be observed. In particular, the shifts
added dropwise. The system was refluxed at 78 °C and stirring undergone by the DA peaks associated to the amine vibrations
for 90 min. Then the silica suspension was cooled to room temper- (1615 and 1580 cm 1) toward higher wavenumber is indicative
ature. Successively, 6 mL of NH4OH and 400 mg of DA (4.0 g L 1) of indole and indoline structures formation. The low relative inten-
were added and the reaction was maintained in stirring at 25 °C sity of the polymeric shell characteristic peaks compared to the sil-
for 24 h. The synthesized SiO2@PDA NPs were collected by cen- ica core ones could be attributable to the formation of SiO2@PDA
trifugation (5000 rpm for 10 min) and washed in ethanol three NPs with a low shell/core ratio.
times. CSNPs were finally dried in oven at 50 °C for 48 h. That hypothesis is verified by TEM observations reported in
The appropriate amount of synthesized CSNPs (0.1, 1 or 5 wt%) Fig. 2: a thin shell (15 nm thick) grown around the silica core
was dispersed in 10 mL of THF at 60 °C for 30 min, in order to
increase the filler dispersion in the epoxy matrix. The suspension
was mixed with the epoxy resin (30 g) in a round-bottom flask
and the solvent was removed by rotavapor (at 90 °C, under vac-
uum). The solvent-free mixture was mechanically mixed by using
a Dispersing System ULTRA-TURRAXÒ T 25 digital at 90 °C for
30 min, and then degassed in oven under vacuum at 90 °C for
1 h. After degasing, the SiO2@PDA/RTM6 mixture was poured in a
stainless steel mould, previously coated with a release agent (FRE-
KOTE 70), and cured: the employed curing profile was 90 min at
160 °C, followed by 120 min at 180 °C.
SiO2@PDA NPs were analysed by using Fourier Transform Infra-
red (FTIR) analysis in the 4000–400 cm 1 region. The Transmission
Electron Microscopy (TEM) observations were performed to esti-
mate the polymeric shell thickness. Thermogravimetrical Analysis
(TGA) on the synthesized CSNPs was carried out by using a Q500
system by TA Instruments: tests were performed in nitrogen atmo-
sphere with 10 °C/min heating ramp.
Preliminary fracture toughness tests were performed on the
CSNPs/RTM6 systems according ASTM D5045 standard. The chosen
Fig. 1. FTIR spectra of a) pristine SiO2, b) pure DA and c) SiO2@PDA NPs.
sample geometry is the Single Edge Notched Beam (SENB) with

Scheme 1. SiO2@PDA synthesis.

Please cite this article as: A. Zotti, S. Zuppolini, A. Borriello et al., Effect of SiO2@polydopamine core/shell nanoparticles as multifunctional filler for an aero-
nautical epoxy resin, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.407
 A. Zotti et al. / Materials Today: Proceedings xxx (xxxx) xxx 3

Fig. 2. TEM observations of SiO2@PDA NPs: a) low and b) high magnification.

content the nanocomposites colour changes from transparent-

Fig. 3. TGA thermograms (in nitrogen) of SiO2 NPs (red curve) and SiO2@PDA NPs
(blue curve). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
of about 230–240 nm is observable. The presence of a thin shell
around SiO2 core is also confirmed by the TGA results, reported
in Fig. 3. In fact, the small weight residual difference (DW  16%)
between bare SiO2 NPs and SiO2@PDA NPs is indicative of a low
organic content in the synthesized filler.
Employing the synthesized CSNPs, nanocomposites with 3 dif-
ferent filler contents have been prepared. In Fig. 4 are reported
the manufactured plates, and it is evident that increasing the filler
yellow to opaque-brown. The change in colour is associated to
the PDA shell colour, which results dark brown, while the change
in transparency is due to the silica core, which acts as scattering
site for the incident light preventing its transmission.
Preliminary fracture toughness results (see Fig. 5) have shown
an increase of both KIC and GIC for the samples loaded with 1 wt%
of CSNPs. KIC is the critical stress intensity factor and represents
the critical stress amplification factor near the edge of a crack.
GIC is the critical strain energy release rate and represents the
energy needed to create two surfaces during crack propagation.
The magnitude of KIC and GIC improvement compared to the neat
resin is equal to 23% and 48%, respectively.
In order to explain the remarkable improvement of fracture
toughness properties it is necessary to investigate both filler dis-
persion and fracture morphology. Fig. 6 shows the fracture surface
of the nanocomposite loaded with 1 wt% of CSNPs, obtained after a
fracture toughness test. The filler is homogeneously distributed in
the hosting matrix. The formation of small CSNPs clusters, with an
average dimension of about 5–10 lm, is highlighted by further
zooming. Finally, the highest zoom in Fig. 6 allows to observe the
effects of the two mechanisms involved during the crack propaga-
tion: the crack pinning and the plastic deformation phenomenons.
The first is attributable to the presence of the hard silica shell, and
is recognizable by the typical tails behind particles or clusters. The
second phenomenon is instead associated to the presence of the
polymeric shell, and is highlighted by the stretched matrix seg-
ment around the particles.

Fig. 4. SiO2@PDA NPs filling epoxy resin. From left to the right; respectively 0.1 wt%, 1 wt% and 5 wt% NPs.

Please cite this article as: A. Zotti, S. Zuppolini, A. Borriello et al., Effect of SiO2@polydopamine core/shell nanoparticles as multifunctional filler for an aero-
nautical epoxy resin, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.407
4 A. Zotti et al. / Materials Today: Proceedings xxx (xxxx) xxx

Fig. 5. a) KIC and b) GIC results relative to the system loaded with 1 wt% of SiO2@PDA.

Fig. 6. Fracture surface of the system loaded with 1 wt% of SiO2@PDA NPs.

The manufactured plates will be cut according the chosen tests
standards, with particular attention towards thermomechanical
and thermal properties, and further fracture toughness tests will
be performed.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This study was financially supported from European Project:
EXTREME dynamic loading-pushing the boundaries of aerospace
composite material structures-Grant Agreement ID 636549. The
authors would like to thank Ms Cristina Del Barone for the techni-
cal support in the use of TEM equipment.
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Please cite this article as: A. Zotti, S. Zuppolini, A. Borriello et al., Effect of SiO2@polydopamine core/shell nanoparticles as multifunctional filler for an aero-
nautical epoxy resin, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.407