Volume 2 Number 43 21 November 2014 Pages 18151–18698

Journal of
Materials Chemistry A
Materials for energy and sustainability
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ISSN 2050-7488

PAPER
Pengli Zhu, Daoqiang (Daniel) Lu, Rong Sun et al.
Core–shell SiO2@RGO hybrids for epoxy composites with low percolation
threshold and enhanced thermo-mechanical properties
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Materials Chemistry A
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Core–shell SiO2@RGO hybrids for epoxy

composites with low percolation threshold and
Cite this: J. Mater. Chem. A, 2014, 2,
18246 enhanced thermo-mechanical properties†
Liang Huang,ab Pengli Zhu,*a Gang Li,a Daoqiang (Daniel) Lu,*a Rong Sun*a
and Chingping Wongcd

Reduced graphene oxide (RGO)-encapsulated SiO2 hybrids (SiO2@RGO) were fabricated from the thermal
reduction of electrostatically assembled SiO2@GO hybrids. Then, epoxy composites, filled with SiO2,
SiO2@GO and SiO2@RGO hybrids, were prepared by a solvent-free curing process, and their thermal,
dielectric and thermo-mechanical properties were investigated and compared. In the SiO2@RGO/epoxy
composites, the mono-dispersed SiO2 nanoparticles are firmly embedded in the thin layer of RGO
nanosheets, forming unique core–shell nanostructures that effectively prevent the aggregation of RGO
nanosheets in the polymer matrix, construct conductive pathways at the particle–polymer interface and
afford the epoxy composites with outstanding thermo-mechanical properties. The dielectric properties of
the SiO2@RGO/epoxy composites exhibit a typical percolation transition near 0.174 vol% for RGO (20 wt%
of SiO2@RGO hybrids), where the dielectric constant could reach 77.23 at 1 kHz, which is 22 times that of
the neat epoxy resin. Upon further increase of the loading content, the gradual contact of the filler
particles leads to the formation of interfacial continuous conductive networks, and both the thermal
conductivity and dielectric constant of the composites show a dramatic increase. With a filler loading of
40 wt% SiO2@RGO (0.373 vol% for RGO), a thermal conductivity of 0.452 W m
1 K
1 is obtained, which is
two times larger than that of neat epoxy. In addition, SiO2@RGO/epoxy composites reveal significantly
Received 18th July 2014
Accepted 19th August 2014
decreased coefficient of thermal expansion (CTE) and increased glass transition temperature (Tg). We
believe this special core–shell SiO2@RGO structure, with its inner mechanically enhanced inorganic
DOI: 10.1039/c4ta03702b
particles and outer interfacial conductive phase, could make full use of the enhancement effect of
www.rsc.org/MaterialsA different components and thus endow the polymer composites with outstanding properties overall.

enhancement of diverse properties. For example, polymers could

1 Introduction be endowed with improved thermal conductivity and mechanical
Signicant attention has been devoted to the development and properties by introducing h-BN nanosheets.1 The dielectric prop-
investigation of polymer-based nanocomposites in recent years, erties might be signicantly improved by incorporating conductive
with the object of obtaining high-performance materials. Polymers carbon nanotubes in the percolative composites.2
have been modied by incorporating various inorganic llers to Graphene, a monolayer of carbon atoms arranged into a two-
achieve tunable physical properties, such as mechanical, magnetic, dimensional honeycomb lattice, has aroused tremendous
optical, and electrical properties. Different ller types lead to the scientic and industrial interest owing to its electrical, optical,
thermal and mechanical properties.3–5 For instance, its high
thermal conductivity (5000 W m
1 K
1) and high electrical
conductivity (6000 S cm
1) enable it to be an excellent ller for
a
Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen,
China. E-mail: [email protected]
b
thermal and electrical enhancement in polymer materials.6
Shenzhen College of Advanced Technology, University of Chinese Academy of Sciences,
Numerous reports have focused on the preparation and struc-
Shenzhen, China
c
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta,
tural property investigation of graphene/polymer composites in
USA the past few years.7–9 However, the development of high-perfor-
d
Department of Electronic Engineering, The Chinese University of Hong Kong, Hong mance graphene-based composites is still very difficult, since the
Kong, China dispersion state of graphene in polymer composites signicantly
† Electronic supplementary information (ESI) available: Images of GO and SiO2@ inuences the properties of the composites.10–12 The aggregation
GO hybrids with different assembly mass ratios; photograph of the preparation
of graphene is always inevitable in polymer composites, due to
process; TGA curves of GO, RGO, SiO2, SiO2–NH2, SiO2@GO and SiO2@RGO;
summary of the reported percolation threshold and dielectric properties of the
the p–p stacking in layers and weak interactions with solvents or
graphene/polymer composites. See DOI: 10.1039/c4ta03702b most of the polymer matrixes. As a result, reports on the physical

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properties of graphene-based composites are signicantly Co., Ltd. The epoxy resin used was mixture of epoxy-828 (from
compromised or even unavailable.13 Shell Chemicals) and epoxy-4221 (from Synasia Inc.) with a
Considering the above reasons, in developing polymer-based mass ratio of 1 : 1. This mixture was used in combination with
composites with multiple functions, graphene is usually co-lled commercial methylhexahydrophthalic anhydride (MHHPA,
with other inorganic components to obtain multifunctional Polynt Chemical Co., Ltd.) as curing agent and 1-cyanoethyl-2-
polymer composites or enhance a specic physical property with ethyl-4-methylimidazole (2E4MZ-CN, Shikoku Chemicals Co.,
only a small amount of graphene loading. For instance, Wang Ltd.) as curing accelerator. All other chemicals were of analytical
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et al.14 fabricated surface-functionalized graphene nanosheets grade and used without further purication.
and BaTiO3 nanoparticles co-lled with PVDF composites, which
show a much higher permittivity and a lower dielectric loss than
the binary nanocomposites over the frequency range of 102 to 106 2.2 Preparation of SiO2@RGO hybrid particles
Hz. Anchoring functional inorganic particles on the surface of Mono-dispersed SiO2 nanoparticles were prepared according to
graphene sheets is another type of hybrid ller structure, which the well-known Stöber process.26 GO was prepared by the
always appear as separated graphene@particle sheets.7,15 Qian Hummers method.27 Preparation of the SiO2@RGO hybrid
et al.16 successfully prepared alumina-coated graphene sheet particles could be simply divided into three steps: (1) surface
hybrids/PVDF composites which possess not only high thermal modication of SiO2 with APTES coupling agent to get the
conductivity, but also are electrically insulating. In addition, positively charged SiO2–NH2 particles; (2) electrostatic assembly
owing to their excellent exibility, ultrathin graphene sheets are of negative exfoliated GO sheets with the SiO2–NH2 particles;
able to coat onto the surfaces of inorganic particles.17,18 Zhang and (3) thermal reduction of SiO2@GO hybrid particles to
et al.11 synthesized a core–shell CuS@RGO hybrid by using an in SiO2@RGO. The process is illustrated graphically in Fig. 1.
situ growth approach in the presence of CTAB under wet-chem- The surface modication of SiO2 with APTES coupling agent
ical conduction (140  C), and its PVDF composites possessed was carried out in liquid environment. In a typical process, SiO2
excellent dielectric and absorption properties. Overall, the powder (5 g) was rst dispersed in a mixed solution of ethanol
potential usage of graphene–inorganic particle-based functional (95 mL) and H2O (5 mL) by ultrasonication. Then, the pH of the
polymer composites has attracted more and more attention. suspension solution was adjusted to a range of 4–5 with formic
Among the diverse inorganic particles, SiO2 has been widely acid to promote the hydrolysis of APTES, followed by adding 0.5
used as a functional inorganic ller to fabricate electronics g APTES coupling agent. The mixture was stirred and reuxed at
packaging materials with improved thermo-mechanical prop- 95  C for 24 h to complete the coupling reaction. The obtained
erties in the microelectronics industries.19–21 Thermo-mechan- SiO2–NH2 particles were centrifuged, washed three times with
ical properties, including glass transition temperature (Tg), ethanol and deionized water, and dried under vacuum.
coefficient of thermal expansion (CTE), as well as storage The SiO2@GO hybrid particles were fabricated by simply
modulus are critical evaluating parameters of the polymer mixing the SiO2–NH2 aqueous suspension and the GO solution.
composites.22–24 Considering that the polymer composites oen At rst, well-dispersed GO aqueous solution was fabricated by
perform crucial functions in electrical applications and are the exfoliating of GO in water with an ultrasonic cell disruptor.
subjected to rigorous thermal cycling, achieving more excellent Then, 500 mL SiO2–NH2 aqueous suspension (10 mg mL
1) was
thermo-mechanical properties could effectively improve the added into the well-dispersed 500 mL GO solution (0.2 mg
thermal stability and enhance device lifetime.25 mL
1) under mild stirring for 1 h. When stirring was stopped,
In this work, SiO2@RGO hybrids were prepared by thermal SiO2@GO hybrid particles were quickly precipitated at the
reduction of the electrostatically assembled SiO2@GO hybrids bottom of the beaker, leaving the upper transparent aqueous
and, their epoxy composites were fabricated by a solvent-free solution. The SiO2@GO hybrids were collected, washed with
curing method. The SiO2@RGO/epoxy exhibited enhanced deionized water to remove the excessive GO nanosheets, and
thermal conductivity, dielectric and thermo-mechanical prop- then freeze-dried under vacuum. Finally, the resulting
erties; particularly when only 0.174 vol% of RGO was used, the SiO2@GO hybrids were thermally reduced at 600  C under
dielectric constant of the composites shows 22-fold increase as nitrogen atmosphere, resulting in the SiO2@RGO hybrid
compared with the neat epoxy. These excellent comprehensive particles.
properties are attributed to the typical ultrathin RGO nano-
sheet-wrapped SiO2 structures, which is efficient in building the
thermal or electrical conductivity paths in the ller–matrix 2.3 Preparation of epoxy-based composites
interface, and also, the inner rigid SiO2 particles could help the To avoid the negative effects of the residual solvent, the epoxy-
uniform dispersion of RGO in the epoxy matrix and afford based composites were fabricated by a solvent-free method. In a
improved thermo-mechanical properties. typical process, the specied quantity of epoxy resin, hardener
and llers were premixed by a high speed mixer. Aer that, a
2 Experimental stoichiometric amount of catalyst was added to the mixture and
mixed with a high-speed mixer under vacuum. Finally, the
2.1 Materials uniform nanocomposite suspensions were gently poured into
Graphite powder (8000 mesh, 99.95%) and (3-aminopropyl) the silicone mold, cured at 150  C for 2 h, and then heated at
triethoxysilane (APTES) were purchased from Aladdin Industrial 180  C for further 2 h. Neat epoxy resin and all epoxy composites

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Fig. 1 The overall fabrication procedure for electrostatic self-assembly of SiO2@RGO: (1) surface modification, (2) electrostatic assembly and (3)
thermal reduction.

with different kinds of llers (SiO2, SiO2@GO and SiO2@RGO) of 1 Hz, temperature range from 50 to 250  C and a ramp rate of
were prepared by the same procedure. 3  C min
1, under single cantilever mode. Coefficient of
thermal expansion (CTE) was measured on a thermo-mechan-
2.4 Characterization ical analyzer (TMA, NETZSCH Instruments, Model 402Fl) with a
heating rate of 3  C min
1 from 50 to 300  C. Several cycling
Morphology observation of the llers and composites were tests were necessary to erase previous thermal history.
obtained using eld-emission scanning electron microscope
(FE-SEM, FEI Nova Nano SEM 450) and transmission electron
microscopy (TEM, FEI Tecnai G2F20 S-TWIN). Fourier trans- 3 Results and discussion
form infrared spectra (FT-IR) were recorded using a VERTEX 70 3.1 Characterization of SiO2@RGO hybrids
spectrometer between 400 and 4000 cm
1. Raman character-
ization was conducted on a Raman spectroscopy (Renishaw SiO2@RGO hybrids were prepared from the thermal reduction
inVia). Thermo-gravimetric analysis (TGA) was performed using of the electrostatically assembled SiO2@GO hybrids. Amination
TA Q600 Thermo-gravimetric analyzer at a heating rate of 10  C of SiO2 particles led to the switch of their surface charge state
min
1 in nitrogen and air. X-ray photoelectron spectroscopy from negative to positive and thus have the ability to assemble
(XPS) spectra were recorded on a PHI-5702 multifunctional with negative GO sheets in water.29 Owing to the hydrophilic
spectrometer using an Al Ka X-ray excitation source. groups (e.g., carboxyl, carbonyl, hydroxyl for GO; amidogen and
Thermal conductivity was measured with a LW-9389 TIM hydroxyl for SiO2), both of the GO and SiO2 particles disperse
resistance and conductivity measurement (Long Win Science & well in water. However, it was observed that the assembled
Technology, Taiwan), which was designed according to the SiO2@GO hybrid particles quickly settle down to the bottom,
standard of ASTM D-5470-06. The thermal conductivity was and the spherical SiO2 particles turn from white to brown as the
calculated from thermal diffusivity according to eqn (1): solution progressively becomes transparent during the
assembly process (Fig. 1). This is a clear indication of the
QL
l¼
(1) assembly between GO and SiO2 nanoparticles. The mass ratio of
ADT 1 : 50 (GO : SiO2) is the most suitable value to achieve saturated
where l is the apparent thermal conductivity (W m
1 K
1), Q is assembly (Fig. S1†). This assembly process is so easy that the
heat ux (W or J s
1), and L and A are the thickness (m) and area uniform core–shell SiO2@GO and SiO2@RGO hybrids can be
(m2) of a specimen, respectively. DT is the temperature differ- fabricated on a large scale (Fig. S2†).
ence between temperature sensors of the hot meter bar (K).28 Further, SEM and TEM measurements were employed to
The test was conducted at 80  C. identify the morphology of the SiO2@GO and SiO2@RGO
The dielectric properties, including effective dielectric hybrids (Fig. 2). Compared with the bare SiO2 particles
constant (3eff) and dielectric loss (tan d), were measured using (400 nm) with visibly spherical morphology and smooth
an impedance analyzer (Agilent 4294 A) in the frequency range surface (Fig. 2a), aer electrostatic assembly, the SiO2 nano-
of 100 Hz to 10 MHz. The storage modulus and glass transition particles are intimately encapsulated by ultrathin GO nano-
temperature (Tg) were measured using a Q800 dynamic sheets, which show clear creases and rough textures on the
mechanical analyzer (DMA, TA Instruments, USA) at a frequency particle surface (Fig. 2b). Aer further reduction under high

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Fig. 2 SEM images of the (a) raw SiO2, (b) SiO2@GO hybrids and (c)
SiO2@RGO hybrids; TEM images of encapsulated structure (d)
SiO2@GO hybrids and (e) SiO2@RGO hybrids.

temperature, a tighter, wizened morphology can be observed in

the SiO2@RGO spheres (Fig. 2c) compared with SiO2@GO
particles (Fig. 2b). The tighter wrapping morphology of gra-
phene on the SiO2 surface means a release of absorbed water
and air in the interface area, which is considered to benet the Fig. 3 (a) FT-IR spectra of SiO2, SiO2–NH2, SiO2@GO, SiO2@RGO and
GO; (b) Raman spectra of GO, SiO2@GO and SiO2@RGO; (c) XPS
composites' performance. The wrinkles of GO on the SiO2
survey spectra of the as-prepared SiO2, SiO2@GO and SiO2@RGO and
surface are further marked in the TEM image of SiO2@GO C 1s XPS spectra of (d) SiO2@GO and (e) SiO2@RGO; (f) TGA curves of
hybrids by arrows (Fig. 2d), conrming that the exible and SiO2@RGO under N2 and air.
ultrathin GO sheets have indeed successfully encapsulated the
modied SiO2 particles. However, for the SiO2@RGO hybrids
(Fig. 2e), only few wrinkles could be found, and the graphene
nanosheets anchored tightly on the SiO2 surface with a thick- shows Raman spectra of GO, SiO2@GO and SiO2@RGO,
ness of less than 5 nm (marked in the inset Fig. 2e). respectively. The Raman spectrum of GO exhibits typical D and
FT-IR spectra were employed to conrm the covalent G bands at 1352 and 1589 cm
1. The spectra of SiO2@GO and
attachment of the APTES coupling agent. As Fig. 3a shows, the SiO2@RGO hybrids show two strong, sharp peaks at 1352/1593
main peaks of the SiO2 spectra at 1111, 802 and 478 cm
1 are and 1341/1591 cm
1, respectively, which are attributed to the D
attributed to Si–O–Si stretching and bending vibrations; the and G bands of GO or RGO, indicating the presence of GO/RGO
band at 953 cm
1 to the Si–OH stretching vibration, which sheets in the hybrids. In addition, a small increase of the ID/IG
disappears from the spectra curve of SiO2@RGO aer high- ratio for SiO2@RGO (0.89) compared with that of GO (0.82) and
temperature reduction; and the band at 1645 cm
1 to the O–H SiO2@GO (0.84) appears, suggesting the decrease of the sp2 in-
bending vibration of the adsorbed water molecules.30 Aer the plane domain induced by the introduction of defects and
amination reaction, several minor bands at around 2982 cm
1, disorder of the sp2 domains.35
corresponding to the C–H stretching vibration of the hydro- The XPS spectra of SiO2, SiO2@GO and SiO2@RGO are
carbon chains of the graing APTES, are observed.29 For GO, the shown in Fig. 3c–e. The C 1s, O 1s, Si 2s and Si 2p peaks can be
peak at 3412 cm
1 is attributed to –OH stretching vibrations of distinctly observed in the survey XPS spectra of SiO2@GO and
the adsorbed water molecules and structural –OH groups.16 SiO2@RGO (shown in Fig. 3c). In addition, the intensity ratios of
Peaks at 1728, 1624, 1400 and 1094 cm
1 are assigned to the the C 1s peak to the Si 2s and Si 2p peaks of SiO2@GO and
C]O stretching, H–O–H bending, ]C–H vibration and C–O SiO2@RGO, compared with the raw SiO2, are much higher due
stretching, respectively.31 Due to the ultralow content of GO and to the addition of GO or RGO sheets. The ne spectra of C 1s of
RGO in the core–shell hybrids, the peaks of GO or RGO are a SiO2@GO and SiO2@RGO are shown in Fig. 3d and e, respec-
little weak in the SiO2@GO and SiO2@RGO spectra curve. tively. The C 1s peak can be further divided into four peaks,
The presence of the surface coating GO/RGO was further which can be attributed to carbon atoms with different func-
conrmed by Raman spectroscopy, which has been utilized as a tional groups, including the C]C (284.7 eV), C–O (285.6 eV),
powerful tool for the characterization of graphene and its C–O–C (286.9 eV) and O]C–O (288.5 eV) bonds, respectively.34
derivatives. The Raman spectrum of graphene is characterized Compared to the C]C peak, the peaks of the oxidized groups
by two main features, the G mode arising from the rst-order were much weaker aer thermal reduction, revealing that the
scattering of the E2g phonon of C sp2 atoms (usually observed at GO has been successfully reduced. However, some residual
1575 cm
1) and the D mode arising from a breathing mode of oxygen groups still exist in the SiO2@RGO hybrids, which is
k-point photons of A1g symmetry (1350 cm
1).32–34 Fig. 3b inevitable and in agreement with the previous report.36,37

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The TGA curves of GO, RGO, SiO2, SiO2–NH2, SiO2@GO, and state (Fig. 5d) and even tortuous ribbons (Fig. 5b, c, e and f).
SiO2@RGO were tested and are shown in Fig. S3.† They indicate These rough fractographs originate from the pulling-out of the
the thermal stability of different samples and the successful epoxy composites, indicating the inhibition ability of the
step-by-step surface coating of the SiO2 nanoparticles. Further, llers on the propagation and advancing of cracks in the
the weight loss of the SiO2@RGO hybrids in N2 and air was composite interface. In addition, it should be noted that
investigated to calculate the mass fraction of surface-coated aggregation appears in SiO2/epoxy composites (marked circle
RGO sheets in the hybrids (Fig. 3f). When thermally treated in Fig. 5b), indicating a relatively weak interfacial compati-
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under N2 atmosphere, the SiO2@RGO hybrids exhibited 1.42 bility between ller particles and the epoxy matrix. However,
wt% loss at 800  C, which may result from the residual or because of the abundant functional groups of GO, surface
adsorbed impurities. However, when the same SiO2@RGO wrapping of GO could improve the dispersion of the SiO2
samples were treated in air, a total weight loss of 2.89 wt% was particles effectively. The high-magnication fracture image of
observed in the curve. In addition, it is obviously seen that the SiO2@GO/epoxy composites (inset of Fig. 5c) implies that the
TGA curve has two degradation stages, which belong to the loss particles are almost uniformly embedded in the epoxy resin,
of residual impurities and decomposition of RGO sheets, with strong interface interaction.
respectively. Therefore, by subtracting the weight loss of The SEM images of SiO2@RGO/epoxy composites with
SiO2@RGO hybrids in N2 from the total loss in air, the quality of different loading levels are shown in Fig. 5d–f. For low-lling
the surface-coated RGO sheets could be calculated to be SiO2@RGO/epoxy composites (20 wt%), some small SiO2@RGO
1.47 wt% (the theory content of GO in the SiO2@GO hybrids is clusters are found (Fig. 5d) because of the encapsulation of a
1.96 wt%). single graphene sheet on several SiO2 nanoparticles (Fig. 2c).
Based on the TGA results, we could calculate the volume When the ller content is increased to 30 wt%, the SiO2@RGO
ratio of RGO in SiO2@RGO/epoxy composites by eqn (2): particles gradually contact with each other, and the cluster
rcomposite boundaries become unapparent. For instance, a few scattered
RGOðvol%Þ ¼ RGOðwt%Þ  (2) smooth areas of epoxy, made up by the cluster boundaries, can
rRGO
be found in the composites with 30 wt% SiO2@RGO hybrid
where rcomposite and rRGO are the density of the epoxy compos- loading; an initial conducting pathway appeared in the epoxy
ites and RGO, respectively. The density of RGO is widely matrix. When the particle content was further increased to
accepted as 2.2 g cm
3.14 Additionally, the density of the 40 wt%, the cluster boundaries became difficult to nd, and the
prepared SiO2@RGO/epoxy composites can be obtained by particles interconnected together, leading to the contacting of
density balance. Densities of the composites and the calculated interfacial RGO sheets, indicating the further completion of the
RGO volume fractions in the composites are proled in Fig. 4. conducting networks.

3.2 Morphology of the epoxy-based composites

3.3 Thermal conductivity of the composites
The fracture morphology, exhibiting the dispersion and
compatibility of SiO2, SiO2@GO and SiO2@RGO in the epoxy The thermal conductivities of the neat epoxy, SiO2/epoxy,
matrix, are shown in Fig. 5. The fractured surface of the neat SiO2@GO/epoxy and SiO2@RGO/epoxy composites were
epoxy shows a smooth and featureless morphology with a investigated and compared, as shown in Fig. 6a. It should be
typical brittle fracture process (Fig. 5a), revealing its nature of noted that the thermal conductivity of the epoxy composites
weak resistance to crack initiation and propagation.38 In the increases in the order of neat epoxy < SiO2/epoxy < SiO2@GO/
case of composites with llers, the fracture surface exhibits epoxy < SiO2@RGO/epoxy (same ller loading of 30 wt%). Two
rougher morphology with river-like structures in low lling

Fig. 5SEM images of the fractured morphology of (a) neat epoxy, (b)
30 wt% SiO2/epoxy, (c) 30 wt% SiO2@GO/epoxy, (d) 20 wt% SiO2@
Fig. 4 Densities of the SiO2@RGO/epoxy composites and the calcu- RGO/epoxy, (e) 30 wt% SiO2@RGO/epoxy, (f) 40 wt% SiO2@RGO/
lated volume fractions of RGO in the composites. epoxy composites.

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major factors can explain the enhancement of thermal little increment in the dielectric permittivity occurred for
conductivity. Considering the existing defects in SiO2/epoxy SiO2@GO, when comparing with the same 30 wt% SiO2/epoxy
composites, one factor is that the GO and RGO wrapping can composites (about 2 times at 1 kHz). However, for SiO2@RGO/
improve the dispersion state of the ller particles in epoxy epoxy composites, even at a low lling content of 10 wt%, a
matrix to avoid the formation of agglomeration and voids. On substantial increase in dielectric permittivity can be observed,
the other hand, it is clear that the thermal conductivity of the i.e., from 3 (0 wt%) to 21 (10 wt%), which is 2.8 times larger
composite is deeply affected by the intrinsic thermal than that of 30 wt% SiO2@GO/epoxy composites. The large
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conductivity of llers in the polymer matrix.39 Hence, the difference could be ascribed to the much lower intrinsic
other factor is that the intrinsic thermal conductivity of RGO conductivity of GO, which agrees with its performance on the
is much higher than that of GO and SiO2, therefore leading to thermal conductivity.
a higher thermal conductivity for SiO2@RGO-lled epoxy Fig. 7b and c show the frequency dependence of the
composites. dielectric permittivity and loss for neat epoxy and SiO2@RGO/
Fig. 6b shows the thermal conductivity of SiO2@RGO/epoxy epoxy composites. In the case of fSiO2@RGO # 20 wt%, namely
composites with different ller loading. It is clear that the for 0 wt%, 10 wt% and 20 wt% ller loading, the permittivity of
formation of thermal conducting pathways in the epoxy matrix composites shows good frequency stability. The dielectric
can effectively improve the thermal conductivity. For compos- constant of 20 wt% SiO2@RGO/epoxy composites is 77 at
ites lled with llers below 20 wt%, most SiO2@RGO clusters 1 kHz, which is 22 times that of the neat epoxy resin (3 ¼ 3).
are separated from each other in the matrix, which makes However, when fSiO2@RGO > 20 wt%, the dielectric constant of
inefficient the transport of thermal energy from one high the composites decreases substantially with the increase of
thermal conductivity phase to another. Hence, there is only a frequency. When fSiO2@RGO ¼ 30 wt%, the measured value of
small increase of the thermal conductivity from 10 wt% to the effective dielectric constant of the percolative composites
20 wt%. At 30 wt% lling content, initial thermal conducting at 1 kHz can reach as high as 3  106, which is much higher
pathways are formed, which also could be seen in Fig. 5e, than that of the epoxy matrix. Meanwhile, owing to the
leading to a signicantly increased thermal conductivity, by outstanding conductivity of RGO and the formation of elec-
136% from 0.287 W m
1 K
1 (20 wt%) to 0.391 W m
1 K
1. trical paths in the epoxy matrix, the dielectric loss also
When ller content was further increased to 40 wt%, the increases near the percolation threshold. The dielectric loss of
thermal conductivity networks are further completed through SiO2@RGO/epoxy composites at 1 kHz is 0.24 at fSiO2@RGO ¼
the interface area by RGO sheets. Hence, a higher thermal 10 wt% and 0.60 when fSiO2@RGO ¼ 20 wt%. Moreover, a
conductivity is obtained at 40 wt% (0.373 vol% RGO) with a dramatic increase of dielectric constant for 30 wt% SiO2@
value of 0.452 W m
1 K
1, which is about 200% of the thermal RGO/epoxy composites appears with a high dielectric loss of
conductivity of neat epoxy. The interfacial thermal conducting 60, which is the inevitable consequence of the formation of the
pathway constructed by the RGO sheets is also illustrated in conductive network constructed by a certain content of
Fig. 6c. conductive llers; this would cause signicant leakage
current, and thus result in high dielectric loss.12 The variation
3.4 Dielectric properties of the composites of the dielectric constant and dielectric loss of SiO2@RGO/
epoxy composites as a function of SiO2@RGO mass fraction
The permittivity of the composites lled with different llers (fSiO2@RGO) at 1 kHz are also shown in Fig. 7d. It could be
was studied and is shown in Fig. 7a. It can be found that only a observed that a limited increment in the dielectric permittivity
occurred when fSiO2@RGO # 20 wt%, and a sudden large
increase appeared in the dielectric permittivity when fSiO2@RGO
> 20 wt%. Percolation theory, which is considered as a typical
theory in polymer composites with conductive llers, can be
employed to explain this phenomenon.2,40,41 The dielectric
permittivity of SiO2@RGO/epoxy composites near the
percolation threshold can be described by eqn (3) as follows:42

3eff f 3epoxy (fc
f)
s for f < fc (3)

where 3epoxy and 3eff represent the dielectric permittivity of the

matrix and the composites, f is the volume fraction of the ller,
fc is the percolation threshold and s is the critical exponent. As
expected, the dielectric properties of the SiO2@RGO/epoxy
composites show a typical percolation transition behaviour as
the mass fraction of SiO2@RGO in the insulating epoxy matrix
Fig. 6 (a) Thermal conductivity of epoxy composites with different increases. The approximate percolation threshold for the
filler types, (b) SiO2@RGO/epoxy composites with different mass
SiO2@RGO/epoxy composites is near 20 wt%, at which the
fractions and (c) schematic of the interfacial conductive pathways in
the SiO2@RGO/epoxy composites. content of RGO in the composites is only 0.174 vol%.

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Fig. 7 (a) Dielectric permittivity of epoxy composites with different filler types. (b) and (c) are dependence of the dielectric permittivity and loss of
SiO2@RGO/epoxy composites on the frequency, respectively. (d) Dielectric permittivity and dielectric loss of SiO2@RGO/epoxy composites as a
function of fSiO2@RGO at 1 kHz.

The conductivity data were used to further verify the the inner rigid SiO2 plays a supporting role that promotes the
formation of conductive pathways in the SiO2@RGO/epoxy uniform dispersion of ultrathin RGO in the epoxy matrix; under
composites. Fig. 8a and b display the conductivity of SiO2@ this situation, only a small amount of RGO achieves great
RGO/epoxy composites as a function of fSiO2@RGO at 1 kHz and enhancement of the thermal and electrical properties.
frequency, respectively. For the composites with low lling
content (fSiO2@RGO # 20 wt%), the conductivity increases slightly
from 5.72  10
5 S m
1 for 10 wt% to 6.69  10
5 S m
1 for
20 wt% at 1 kHz, because the llers could not effectively contact
with one another to form conductive pathways. Due to their
insulating nature, the conductivity curves show a strong
dependence on the frequency. However, as fSiO2@RGO increased
to 30 wt%, the conductivity further increases to 2.56  10
2
S m
1, and an insulator–semiconductor transition is clearly
observed, which is caused by the formation of effective physical
electrical pathways in the composites. At this ller loading
content, the composites exhibit a conducting feature that is
nearly frequency-independent. The results are in good agree-
ment with the variations of former thermal and dielectric
properties of SiO2@RGO/epoxy composites.
From the above dielectric and conductivity properties of the
SiO2@RGO/epoxy composites, it is known that the dielectric
constant, dielectric loss and conductivity of the composites
exhibit a remarkable change between the loading weight frac-
tions of 20 wt% and 30 wt%. At these two loading levels of epoxy
composites, the corresponding RGO volume fractions are 0.174
vol% and 0.271 vol%, respectively. These values are much lower Fig. 8 (a) Conductivity of the SiO2@RGO/epoxy composites with
than those that have been reported for graphene-lled different mass fractions at 1 kHz and (b) as a function of frequency at
composites (Table S1†).14,15,43 We think the main reason is that room temperature.

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Paper Journal of Materials Chemistry A

3.5 Thermo-mechanical properties of the composites modulus falls by a few orders of magnitude, and the
composites undergo the transition from glassy to rubbery
Thermo-mechanical properties of the epoxy composites were
state. These glass transition peaks can be seen in damping
evaluated using DMA and TMA at various temperatures. The
spectra (tan d) (Fig. 9b), and the temperature at the peak is
results are shown in Fig. 9. One can recognize that the
called the glass transition temperature (Tg). The changes in Tg
incorporation of different llers leads to the increase of
in epoxy composites not only yield insights into the funda-
storage modulus in both glassy and rubbery regions,
mental changes in polymer chain dynamics, but also relate to
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compared to that of neat epoxy (Fig. 9a). This can be well

explained by the increase stiffness resulting from the rein- the enhancement of thermal stability critical for their appli-
forcement effect of the nanollers. In the initial glassy state, cations.44 It can be found that the Tg values of neat epoxy
increase aer lling with different llers. For example, the Tg
the epoxy lled by SiO2 nanoparticles exhibited an enhanced
of the 30 wt% SiO2/epoxy composites is 168.6  C, increasing by
storage modulus compared to pure epoxy, and the SiO2@RGO/
about 15  C compared to the neat epoxy (Table 1). However,
epoxy composites showed the most effective reinforcement of
aer surface coating by GO, Tg of composites decreased to
storage modulus. With increasing temperature, the storage
161.2  C. The reason could be that the extra functional groups
of GO in epoxy composites decrease the degree of cross-link-
ing by partial absorption of, or reaction with, the curing
agent.45,46 Another article also reported similar results.29 When
the surface functional groups of GO were eliminated by
thermal reduction, the Tg of SiO2@RGO/epoxy composites
increased to 167.9  C, which is almost equal to the value of
SiO2-only lled epoxy composites (168.6  C), increasing by
about 14.3  C compared to the neat epoxy.
The effect of SiO2@RGO hybrids particle loading on the
thermal expansion of the epoxy matrix is shown in Fig. 9c. All
specimens exhibit a gradual change in the slope of thermal
strain with temperature increase, which represents the transi-
tion from a glassy region to a rubbery region. The CTE value of
the glassy region and rubbery region, which are marked as CTE1
and CTE2, was determined by the slope of linear regression at a
temperature interval of 50–100  C and 200–250  C, respectively,
based on eqn (4),
L dL
a¼ (4)
L0 dT
where L0 is the initial length of the sample, and L is the length at
temperature T.24 Fig. 9d shows the CTE1 and CTE2 values of the
SiO2@RGO/epoxy composites as a function of different loading
contents. Both CTE1 and CTE2 gradually decrease as the ller
loading increases, because of the increasing lling of the low-
CTE SiO2 particles. For the 40 wt% lling SiO2@RGO/epoxy
composites, CTE1 and CTE2 are 46.0 and 138.4 ppm  C
1,
which decrease by about 16.5 and 55.8 ppm  C
1 compared with
neat epoxy. Consequently, lling of SiO2@RGO particles
improved the dimensional stability of the epoxy resin with
temperature changes.

Table 1 Dynamic mechanical properties of neat epoxy and 30 wt%

filled epoxy composites

Storage modulus
Samples (GPa at 50  C) Tg ( C)

Fig. 9 Plots of dynamic mechanical curves for neat epoxy and Neat epoxy 2.62 153.6
30 wt% filling epoxy composites with different fillers: (a) storage SiO2/epoxy 3.24 168.6
modulus, (b) damping spectra (tan d), and (c) thermal strain curves; SiO2@GO/epoxy 3.23 161.2
(d) CTE values of SiO2@RGO/epoxy composites in the glassy region SiO2@RGO/epoxy 3.56 167.9
and rubbery region.

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10 H. C. Schniepp, J. L. Li, M. J. McAllister, H. Sai, M. H. Alonso,

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