Preparation and Characterization of POSS-SiO2/

Cyanate Ester Composites With High Performance

Mengmeng Zhang, Hongxia Yan, Chao Liu, Junping Zhang

Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, XiAn, Shaanxi
710129, Peoples Republic of China

In this article, a hybrid filler based on polyhedral oligomeric silsesquioxane and silica, coded as POSS-SiO2,
has been successfully synthesized. The structure of
POSS-SiO2 was studied by Fourier-transform infrared
spectra, X-ray diffraction, and scanning electron
microscopy. Then the POSS-SiO2 was compounded
with dicyclopentadiene bisphenol dicyanate ester
(DCPDCE) resin to prepare composites. The effects of
POSS-SiO2 on the curing reaction, mechanical, thermal, dielectric and tribological properties of DCPDCE
resin were investigated systematically. Results of differential scanning calorimetry show that the addition
of POSS-SiO2 can facilitate the curing reaction of
DCPDCE and decrease the curing temperature of
DCPDCE. Compared with pure DCPDCE resin, the
impact and flexural strengths of the composites materials are improved markedly with up to 72 and 52%
increasing magnitude, respectively. Meanwhile, the
POSS-SiO2/DCPDCE systems exhibit lower dielectric
constant and loss than pure DCPDCE resin over the
testing frequency from 10 to 60 MHz. In addition, the
thermal stability and tribological properties of POSSSiO2/DCPDCE composites are also superior to that of
pure DCPDCE resin. POLYM. COMPOS., 00:000000,
C 2014 Society of Plastics Engineers
2014. V

INTRODUCTION
Cyanate ester resins are important high-temperature
thermosetting resins. The cured cyanate ester resins
exhibit good mechanical properties, superior dielectric
properties, excellent adhesive properties and good moisture resistance, etc. [1, 2]. These unique properties of cyanate resins make them excellent candidates for many
cutting-edge applications such as high-frequency numeric
printed circuit board, aerospace structures, adhesives and
functional materials [35]. It is well known that cyanate
ester monomers can be polymerized to form threedimensional networks of oxygen-linked triazine ring
through the cyclotrimerization reaction of three cyanate

Correspondence to: H.X. Yan; e-mail: hongxiayan@nwpu.edu.cn

DOI 10.1002/pc.23091
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2014 Society of Plastics Engineers
V

POLYMER COMPOSITES2014

ester groups. However, the cured cyanate ester resin consists of stiff network of triazine groups with highly crosslinking density, resulting in its brittleness that restricts its
further prosperity into the advanced industrial applications. Therefore, it has been a hot topic during the last
decade to modify and toughen cyanate ester resins. In
recent years, many researches have focused on improving
their performance by introducing different types of fillers,
such as nanoclays [6, 7], carbon nanotubes [8, 9], carbon
fibers [10, 11], and polyhedral oligomeric silsesquioxanes
[1214].
Polyhedral oligomeric silsesquioxanes (POSS) are a
family of nanoscale chemical structures that contain a
silicon-oxygen core based on (SiO1.5)n and have each
apex (silicon atom) connected to some organic groups
[15]. It is this combination of an inorganic core covered
with an organic shell at the molecular level that has led
POSS structures to being labeled as organicinorganic
hybrid materials. POSS are attracting increased attention
due to their unique cage-like molecular structures and
interesting physicochemical properties. In addition, POSS
possess not only good compatibility but also reactivity
with many thermosetting polymers. They have been used
to modify various thermosetting resins such as epoxy
[16], polyimide [17], phenolic resin [18], cyanate ester
resin [19], etc., and the results prove that they can be
used as effective fillers for the improvement in mechanical, dielectric, thermal, and other physical properties.
As we all know, POSS are hard to process and very
expensive material. A composites that using only POSS
as a single filler is actually not relevant for certain industrial purpose. This is where the idea of combination
POSS with other type of filler seems practical. Silica
(SiO2) is highly stable, chemically inert, shows high
mechanical strength and high susceptibility to modifications [20], and offers the possibility to improve properties
like mechanical [21, 22], thermal [23], and tribological
properties [24, 25]. In addition, it is much cheaper than
POSS, showing a great attraction for actual applications;
It is believed that by reducing the usage of POSS and
replaces it with SiO2, which is much cheaper as hybrid
fillers in composites will reduce the production cost

reagents were all commercial products with analysis

grades.
Sample Preparation
SCH. 1. The structure of DCPDCE.

without compromising the mechanical properties of those

particular composites too much. However, SiO2 has a
strong tendency of particles to agglomerate because of its
high surface energy. The solgel process is one of the
techniques used to improve the dispersion of fillers in and
adhesion to a hydrophobic polymer matrix [26]. Therefore, in order to develop POSS-based cyanate ester composites with high performance and lower cost, the
combination of POSS and SiO2 through solgel process
can be a useful method for achieving homogeneous dispersion of fillers in cyanate ester matrix.
To our best knowledge, reports on the modification of
cyanate esters are mostly focused on bisphenol A dicyanate ester resins. However, comparing to bisphenol A
dicyanate ester, dicyclopendiene bisphenol dicyanate
esters (DCPDCE) have the advantages of higher glass
transformation temperature, better dielectric properties,
lower water absorption and more balanced mechanical
properties. Unfortunately, few works have been reported
on the studies of DCPDCE. Therefore, in this article, a
new hybrid filler based on POSS and SiO2, coded as
POSS-SiO2 was synthesized through sol mixing method
and used as a modifier to improve the properties of
DCPDCE resin. A series of POSS-SiO2/DCPDCE composites containing different contents of POSS-SiO2 were
developed by melt casting and then curing. The effects of
POSS-SiO2 on the mechanical, thermal, dielectric and tribological properties of DCPDCE resin were investigated
to develop high performance materials.
EXPERIMENTAL
Materials
Dicyclopentadiene bisphenol diyanate ester (DCPDCE)
was purchased from Yangzhou Jiangdu Wuqiao Resin
Plant (Jiangsu, China), the structure of DCPDCE was
shown in Scheme 1. Chloropropyl POSS was synthesized
according to the literature [27]. Tetraethylorthosilicate
was purchased from Tianjin Fuchen Chemical Reagents
Factory (Tianjin, China). Ethanol was purchased from
Tianjin Tianli Chemical Reagents Co. Hydrochloric acid
was purchased from Beijing Chemical Works (Beijing,
China). Methanol was purchased from Tianjin Fuyu Fine
Chemical Co. (Tianjin, China). Dimethyl sulfoxide was
purchased from Guangdong Guanghua Sci-Tech Co.
(Guangdong, China). Sodium hydroxide was purchased
from Tianjin Jinbei Fine Chemical Co. (Tianjin, China).
Distilled water was produced from our laboratory. Other
2 POLYMER COMPOSITES2014

Preparation of POSS-OH. In a 250-ml four-mouth

flask holding a nitrogen inlet, mechanical stirrer, refluxcondenser, constant-pressure funnel and thermometer,
optimum dimethyl sulfoxide (50 ml), and chloropropyl
POSS (2.0 g) were added. At 30 C, sodium hydroxide
solution (0.1 mol/l, 50 ml) was slowly added into the
flask through the constant-pressure funnel. Then, the reaction mass was slowly heated to 80 C at which the reaction continued for 56 h. After that, the pH value of the
solution was adjusted to 7 using deionized water. Then
the water was removed from the product through a separatory funnel. After separation, the obtained product was
dried at 60 C in a vacuum oven for about 7 h to vaporize
the solvent. Finally, a white gel was obtained, which is
hydroxyl POSS, coded as POSS-OH.
Preparation of SiO2 sol. The SiO2 was prepared by a
solgel technique using tetraethylorthosilicate as precursor. In detail, tetraethylorthosilicate (25 ml) and ethanol
(25 ml) were charged into a glass beaker equipped with a
magnetic stirrer, then a mixture of distilled water (35 ml),
ethanol (25 ml), and hydrochloric acid (10 ml) was
slowly added into the breaker. And the reaction mass was
stirred at room temperature for 810 h. The obtained
SiO2 sol was kept still for further use.
Preparation of POSS-SiO2. POSS-OH (50 ml) and
SiO2 sol (50 ml) were combined in a 500-ml conical flask
equipped with a magnetic stirrer. Ethanol (50 ml) was
subsequently added into the conical flask to dilute the sol
mixture. Then the reaction mixture was stirred for 12 h at
room temperature. The synthesis route of POSS-SiO2 was
shown in Scheme 2. The obtained POSS-SiO2 sol was
kept still for another 24 h, and then the ethanol was
vaporized.
Preparation of POSS-SiO2/DCPDCE Composites.
The DCPDCE was heated to 100 C in a glass beaker and
kept at this constant temperature until melting. The appropriate amount of POSS-SiO2 was then carefully mixed
with the melted DCPDCE using a mechanical high shear
dispersion process. The mixture, consisting of prepolymer
and POSS-SiO2, was heated to 140 C in an oil bath and
kept at this temperature for 1520 min with stirring. Then
the mixture was put into a preheated mold with release
agent followed by degassing at 140 C for 1 h in a vacuum oven. After that the mixture was cured and postcured via the procedures of 160 C/1 h 1 180 C/1
h 1 200 C/2 h 1 220 C/2 h and 240 C/2 h, respectively.
Finally, the mold was cooled to room temperature and
demolded to get the samples of POSS-SiO2/DCPDCE
system.
DOI 10.1002/pc

SCH. 2. The synthesis route of POSS-SiO2.

The samples of pure DCPDCE resin were prepared in

the same manner as above. All samples were dried at
120 C under vacuum for 6 h and kept in a dry environment prior to testing.

Measurements
Fourier Transform Infrared (FTIR) spectrum was
recorded between 400 and 4,000 cm21 with a resolution
of 2 cm21 on a Nicolet FTIR 5700 spectrometer. The
POSS-OH or POSS-SiO2 powder was mixed with potassium bromide (KBr) powder, to form the homogeneous
mixture using a grinder, and then the mixture was compression molded at 10 bar pressure to make a thin disc
for the test.
X-ray diffraction (XRD) investigation was carried out
using a XPert Pro MPD diffractometer with Cu Ka radiation (k 5 0.154178 nm). The tube voltage was 36 kV,
and the current was 20 mA. Scans were taken over the 2h
range of 585 with the scanning rate of 0.02 /s.
Gel time was determined with a standard hot-plate
with a temperature controller. The resin (3.0 g) was
spread on the surface of the hot-plate preheated to a certain temperature. And the resin was stirred by a glass rod.
The time required for the resin to stop legging is called
the gel time. For each condition, three samples were
tested, and the data were averaged. Differential scanning
calorimetry (DSC, MDSC2910, TA Instruments) experiments were performed at a heating rate of 10 C/min in a
nitrogen atmosphere.
Impact strength was determined according to GB/
T2571-1995. Samples were cut into strips of (50 6 0.02)
3 (7 6 0.02) 3 (4 6 0.02) mm3 by a cutting machine.
The impact strength tests were performed using a Charpy
impact machine tester (XCJ-L, China). Five samples were
DOI 10.1002/pc

tested for each composition, and the results are presented

as an average for tested samples.
Flexural strength was measured according to GB/
T2570-1995. Samples were cut into strips of (80 6 0.02)
3 (10 6 0.02) 3 (4 6 0.02) mm3. The flexural tests were
performed using an electronic universal testing machine
(RIGER-20, China) at a crosshead speed of 2 mm min21.
Five samples were tested for each composition, and the
results are presented as an average for tested samples.
Scanning electron micrographs (SEM) were performed
on a HITACHIS-570 instrument. For SEM samples preparation, the specimens was sputtered with a thin layer
(about 10 nm) of gold by vapor deposition on a stainless
steel stub using a vacuum sputter coater.
Thermal gravimetrical analysis (TGA) tests were performed by using Perkin Elmer TGA-7 at a heating rate of
5 C/min in a nitrogen atmosphere from 50 to 800 C.
The dielectric constant and loss factor were measured
by a high frequency QBG-3 Gauger and a S914 dielectric
loss test set (China) at the frequency between 10 and 50
MHz. The sample dimension was (25 6 0.02) 3
(25 6 0.02) 3 (3 6 0.02) mm3. For each condition, five
samples were tested the data were averaged.
The tribological properties tests were measured according to GB3960-83. The sample dimension was
(35 6 0.02) 3 (7 6 0.02) 3 (4 6 0.02) mm3. The tribological properties performed using a friction and wear testing
machine (MM-200). Before each test, the counterpart
steel ring and samples were abraded with No. 900 waterabrasive paper. Then the steel ring and samples were
cleaned by acetone. All the friction and wear experiments
were conducted at room temperature. Friction coefficient
was measured under a load of 196 N and test duration of
120 min. The wear rate was measured using equation.
Wear rate 5 Dm/q. Where Dm is the weight loss of the
sample and q is the density of samples in g/cm3.
POLYMER COMPOSITES2014 3

FIG. 1. FTIR spectra of POSS-OH (a) and POSS-SiO2 (b). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

RESULTS AND DISCUSSION

Characteristics of POSS-SiO2
The structure of POSS-SiO2 was characterized by various
spectroscopic measurements, including FTIR spectroscopy,
XRD, and SEM. Figure 1 shows FTIR spectra for the POSSOH and POSS-SiO2 hybrid. As expected, the FTIR spectrum
of POSS-OH shows the presence of hydroxyl groups
(3,409 cm21), CH (2,954 cm21), CSi (1,272 cm21), and
SiOSi (1,108 cm21). In the case of POSS-SiO2, as shown
in Fig. 1b, the peaks at around 3,410, 2,941, and 1,272 cm21,
which are assigned to OH, CH, and CSi, respectively,
continue to be observed. The broad band is found at around
1,090 cm21 corresponding to SiOSi and SiOC, and the
absorption peaks of SiOC are overlaid by the intense
absorption peaks of SiOSi. These observations suggest that
the SiO2 has been chemically grafted onto POSS-OH.
Further evidence on the successful grafting of the SiO2 onto
the POSS-OH can be demonstrated by XRD spectra, as shown
in Fig. 2. It can be seen that POSS-OH shows amorphous
bands over 2h  2022 in the XRD profile, and there still
exists some small sharp diffraction peaks, which indicates a
largely disordered structure with a low crystallinity. Although
SiO2 is crystalline, the XRD results of POSS-SiO2 show that
POSS-SiO2 is amorphous and displays a broad peak at 2h 
22 , which is a typical feature peak of amorphous silica [28,
29]. This is because that SiO2 is chemically incorporated into
the POSS-OH and forms chemical bonds between POSS-OH
and SiO2, which destroyed the crystalline of SiO2.
SEM is used to investigate the morphology of POSSOH and POSS-SiO2 particles. Figure 3a represents the
micrograph of POSS-OH, it is found that the particles
size of POSS-OH is not uniform and there exists some
large aggregates. POSS-OH contains large amount of
reactive hydroxyl groups, so it is very easy for POSS-OH
molecules to copolymerize to form crosslinked network,
resulting in bigger molecular structures. In contrast, as
4 POLYMER COMPOSITES2014

FIG. 2. XRD spectra of POSS-OH (a) and POSS-SiO2 (b). [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

shown in Fig. 3b, the size of POSS-SiO2 particles is

much smaller. Because of the new chemical bonds forming between POSS-OH and SiO2, the number of hydroxy
groups on the surface of POSS-OH is decreased and the
POSS-OH molecular aggregation is effectively prevented.
As a result, the particle size of POSS-SiO2 is decreased.
Curing behavior of POSS-SiO2/DCPDCE Composites
Gel time is generally used to evaluate the curing behavior of a resin, a shorter gel time indicates a bigger curing
activity. Figure 4 depicts the gel time of DCPDCE resin
and POSS-SiO2/DCPDCE composites at different temperatures, it can be observed that the addition of POSS-SiO2
can effectively decrease the gel time of DCPDCE, indicting
that the addition of POSS-SiO2 can catalyze the gelation of
DCPDCE. This phenomenon is mainly contributed to the
intensive promotion of the curing reaction of DCPDCE by
OH groups in the molecule of POSS-SiO2 [12].
In order to further confirm the role of POSS-SiO2 on the
curing reaction of DCPDCE prepolymer, comparative DSC
analyses of DCPDCE resin and 1.0 wt% POSS-SiO2/
DCPDCE system at the heating rate of 10 C/min were carried out, and the corresponding curves are depicted in Fig.
5. Comparing with DCPDCE, the maximum curing temperature of POSS-SiO2/DCPDCE shifts to lower temperature
with a gap of about 10 C, demonstrating that the curing
process of DCPDCE can be accelerated by a small amount
of POSS-SiO2 loading. The decreased curing and postcuring temperature is beneficial to manufacture cyanate
ester-based composites for industrial application.

Mechanical Properties of POSS-SiO2/DCPDCE

Composites
Figure 6 shows the impact strengths of DCPDCE resin
and POSS-SiO2/DCPDCE systems. It is observed that all
DOI 10.1002/pc

FIG. 3. SEM photographs of POSS-OH and POSS-SiO2 particles (a: POSS-OH; b: POSS-SiO2).

the POSS-SiO2/DCPDCE composites exhibit higher

impact strengths than pure DCPDCE resin, and 1.0 wt%
POSS-SiO2/DCPDCE system has the maximum impact
strength (16.3 kJ/m2), which is increased by 72% compared with that of pure DCPDCE, indicating that the
addition of POSS-SiO2 can significantly improve the
toughness of DCPDCE resin. Figure 7 shows the flexural
strengths of DCPDCE resin and POSS-SiO2/DCPDCE
systems, and a similar trend can be observed. The 1.0
wt% POSS-SiO2/DCPDCE system has the maximum flexural strength (140.1 MPa), which is increased by 52%
compared with that of pure DCPDCE resin. Therefore, it
can be concluded that the addition of POSS-SiO2 can efficiently improve the mechanical properties of DCPDCE
resin. The toughening and reinforcing effects of POSSSiO2 loading can be contributed to the two facts. First,
the POSS-SiO2 particles inherently posses excellent
mechanical properties, which can bring obviously tough-

ening and reinforcing effects on the molecular chains. On

one hand, they can efficiently distribute the stresses concentrated on the tip of the cracks. On the other hand, they
can exist in the way of cracks to prevent their development [30]. Second, the OH groups in the molecule of
POSS-SiO2 can react with NCO in DCPDCE, leading to
improved interfacial bonding strength between fillers and
matrix. For the POSS-SiO2/DCPDCE system, the probability of forming a strong combination will be enhanced.
Therefore, the mechanical properties of POSS-SiO2/
DCPDCE system are increased as the contents of POSSSiO2 from 0.0 to 1.0 wt%. However, when the fillers content is high enough (>1.0 wt%), the mechanical properties of the composites decrease with the increasing
concentration of fillers. When the content of fillers is too
large, the concentration of POSS-SiO2 is big enough to
form aggregates, and thus reducing the mechanical

FIG. 4. Dependence of gel time on temperature for DCPDCE and

POSS-SiO2/DCPDCE systems. [Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]

FIG. 5. DSC curves of DCPDCE and 1.0 wt% POSS-SiO2/DCPDCE

system. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

DOI 10.1002/pc

POLYMER COMPOSITES2014 5

Thermal Properties of POSS-SiO2/DCPDCE Composites

FIG. 6. Impact strengths of DCPDCE resin and POSS-SiO2/DCPDCE

systems.

properties. But the 1.5 wt% POSS-SO2/DCPDCE system

still possesses better mechanical properties than neat
resin.
In order to further confirm the effect of POSS-SiO2 on
the toughness of DCPDCE resin, SEM images of the fracture surfaces of samples after impact tests are taken and
shown in Fig. 8, it can be observed that pure DCPDCE
resin has smooth and river like surface, exhibiting a typical brittle feature (Fig. 8a). While with the incorporation
of POSS-SiO2 into DCPDCE resin, the fracture surface
becomes much rougher, and there exist large amount of
ductile sunken areas, exhibiting a typical rough feature
(Fig. 8b). It is also noted that there exists no obvious
aggregates on the fracture surface of POSS-SiO2/
DCPDCE system, which suggests that appropriate amount
of POSS-SiO2 particles can be dispersed in the DCPDCE
matrix homogeneously.

FIG. 7. Flexural strengths of DCPDCE resin and POSS-SiO2/DCPDCE

systems.

6 POLYMER COMPOSITES2014

Figure 9 displays TGA and corresponding differential

thermogravimetric (DTG) thermograms for pure DCPDCE
and 1.0 wt% POSS-SiO2/DCPDCE system. Compared to
that of pure DCPDCE, the TGA curve of the POSS-SiO2/
DCPDCE system shifts toward higher temperature and
the onset temperature of thermal degradation for the
POSS-SiO2/DCPDCE system is increased from 390 C for
pure DCPDCE to 408 C. The peak decomposition temperature of the DTG curve represents the temperature at
which the maximum weight loss rate is reached. The
peak decomposition temperature of the POSS-SiO2/
DCPDCE system appears at about 433 C and is increased
by about 10 C compared to that of pure DCPDCE. These
results indicate that the addition of POSS-SiO2 improves
the thermal stability of DCPDCE resin, which can be
attributed to the following reasons. Firstly, POSS-SiO2
introduces a large amount of SiO and SiC bonds, which
possess large bonding energies. This is favorable for
increasing the thermal stability of the composites. Secondly, the POSS-SiO2 particles dispersed in the resin act
as physical interlock points in the cured resin, which can
provide a sterically hindered environment and restrain the
mobility of polymer chains [31]. Thirdly, the good interfacial adhesion between POSS-SiO2 and DCPDCE resin
also provides contribution to the increase in thermal stability. Specifically, a strong interfacial adhesion is beneficial in restricting the segmental motions and thus
increasing the energy consumption of polymer chains
degradation.

Dielectric Properties of POSS-SiO2/DCPDCE Composites

Figure 10 shows overlay plots of dependence of dielectric constant on frequency for pure DCPDCE resin and
modified systems. It can be seen that the dielectric constants of POSS-SiO2/DCPDCE systems are lower than
those of DCPDCE resin, and the higher the POSS-SiO2
concentration is, the lower the dielectric constant. Meanwhile, the dielectric constant and loss of POSS-SiO2/
DCPDCE system remain stable over the testing frequency
band from 10 to 60 MHz. The decrease in dielectric constant may be explained by the following reasons. First,
POSS-SiO2 possesses many unoccupied spaces. Incorporation of POSS-SiO2 into DCPDCE resin is like introducing air bubbles into the matrix, while the dielectric
constant of air is very low (about 1), so the addition of
POSS-SiO2 will inevitably reduce the dielectric constant
of DCPDCE matrix. Second, the addition of POSS-SiO2
into DCPDCE resin promotes the self-polymerization of
NCO groups, which increases the productivity of symmetrical triazine rings (or decreases the polarization of the
resultant structure), and the modified DCPDCE system
tends to form networks with greater symmetry and larger
space hinder, which is beneficial for decreasing the
dielectric constant [32]. In addition, small amount of
DOI 10.1002/pc

FIG. 8. SEM photographs of fracture surfaces for pure DCPDCE and POSS-SiO2/DCPDCE system (a: pure
DCPDCE; b: 1.0 wt% POSS-SiO2/DCPDCE system).

POSS-SiO2 can fill the space between polymeric chains

of DCPDCE. The regularity of the POSS-SiO2/DCPDCE
system will be enhanced, decreasing the number of polarized groups in the resin [33]. This is also one reason that
POSS-SiO2/DCPDCE systems have lower dielectric constants than DCPDCE resin.
Dielectric loss is mainly dependent on the polarity of
polymeric molecules and the density of polar groups. The
higher the polarity of molecules and the density of polar
groups, the higher the dielectric loss will be. Figure 11
displays the effect of POSS-SiO2 on the dielectric loss of
POSS-SiO2/DCPDCE systems. The change in dielectric
loss versus content of POSS-SiO2 is similar to that of
dielectric constant. As discussed earlier, the incorporation
of POSS-SiO2 can increase the symmetry and space
hinder of cured network, and the network will become
more insensitive to polarize relaxation. Moreover, with
POSS-SiO2 filling the molecular space between polymer
chains, the molecular space is smaller compared with the
original DCPDCE, and the mobility of chain segments

FIG. 9. Overlay TGA and DTG curves of DCPDCE resin and 1.0 wt%
POSS-SiO2/DCPDCE system. [Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]

DOI 10.1002/pc

will be restricted, thus reducing the relaxation loss of conductive dipole segment. As a result, the dielectric loss
factors of POSS-SiO2/DCPDCE systems are decreased
compared with pure DCPDCE resin.

Tribological Properties of POSS-SiO2/DCPDCE

Composites
The curves of variation in friction coefficient with sliding time for the composites with various POSS-SiO2 contents are shown in Fig. 12. It can be seen that the friction
coefficient starts with a running-in period followed by a
steady state period. This is mainly due to the formation
of wear debris between the friction surfaces during the
running-in period. This wear debris is compacted and
back transfers onto the friction surface, lowering the friction coefficient in the steady state period [34]. In addition, it is found that the friction coefficient decreases

FIG. 10. Dielectric constants of DCPDCE resin and POSS-SiO2/

DCPDCE systems versus frequency. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]

POLYMER COMPOSITES2014 7

FIG. 11. Dielectric loss factors of DCPDCE resin and POSS-SiO2/

DCPDCE systems versus frequency. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]

from 0.38 to 0.32 with the small addition (0.5 wt%) of

POSS-SiO2 into DCPDCE resin, and which continually
decreases with the continuous increase in POSS-SiO2
content in POSS-SiO2/DCPDCE systems. In case of 1.5
wt% POSS-SiO2/DCPDCE system, its friction coefficient
is 0.26, which is much lower than that of pure DCPDCE
resin.
Figure 13 shows the wear rates of the composites with
various POSS-SiO2 contents. It is observed that the addition of POSS-SiO2 also results in a decrease in the wear
rate, and the 1.0 wt% POSS-SiO2/DCPDCE system has
the minimum value of 1.7 3 106 mm3/Nm, which is
deceased by 65% compared with pure DCPDCE resin.
These results indicate that the incorporation of POSSSiO2 can improve the tribological properties of DCPDCE
resin. The improvement in tribological properties may be
attributed to the following facts. First, the rigid and hard

FIG. 13. Wear rates of DCPDCE resin and POSS-SiO2/DCPDCE

systems.

POSS-SiO2 particles in matrix can efficiently distribute

the stresses during constant sliding, and hence reduce friction and wear. Second, the interface adhesion between the
fillers and matrix is good, which is also favorable for
improving the tribological properties of DCPDCE resin.
Another assumption is a rolling effect of particles. In
some researches with various material pairs [35, 36], a
rolling effect of the nano- or microscale particles could
be expected under certain wear conditions, e.g., surface
roughness and hardness of the material pairs and particles
etc. This effect could reduce both the friction coefficient
and the wear rate.

CONCLUSIONS
A novel kind of high-performance composite has been
prepared by a melting mixing method with POSS-SiO2 as
filler and DCPDCE as matrix. The incorporation of
POSS-SiO2 can catalyze and accelerate the reaction of
DCPDCE resin. Meanwhile, the appropriate content of
POSS-SiO2 can significantly enhance the mechanical
properties including flexural and impact strengths of
DCPDCE resin. Moreover, the POSS-SiO2/DCPDCE systems exhibit better thermal stability, dielectric and tribological properties than pure DCPDCE resin. Especially,
when the concentration of POSS-SiO2 is 1.0 wt%, the
best overall performance of POSS-SiO2/DCPDCE composites can be achieved. The attractive features suggest that
POSS-SiO2/DCPDCE composites have great potential in
the fabrication of high-performance materials such as
adhesives, coating, electronic packaging, etc., for cuttingedge industries.
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FIG. 12. Variation curves of friction coefficient with sliding time for
DCPDCE resin and POSS-SiO2/DCPDCE systems. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.
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8 POLYMER COMPOSITES2014

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