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Article
Study on morphology and mechanicalproperties of PMMA-basednanocomposites containingPOSS molecules or functionalizedSiO2 particles
Chunling Zhang1, Xuetao Bai1, Xiaoli Lian2,Yanli Dou1 and Hong Liu2
AbstractNanocomposites of octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) and functionalized SiO2 were investigatedin order to determine the effect of particles on the morphology and mechanical properties of PMMA. The outcome of thestudy suggested that functionalized SiO2 and octavinylPOSS molecule had different morphology. As proved by X-ray dif-fraction and transmission electron microscopy analysis, the crystal structure of OVPOSS molecule was significantly differ-ent from amorphous aggregates of functionalized SiO2. With the additional particles in the nanocomposites, the sizes ofoctavinylPOSS and functionalized SiO2 began to reduce. This illustrated that the separation of aggregates led to the for-mation of irregular POSS molecules and amorphous SiO2 particles varied. Differential scanning calorimetry analysis indi-cated that PMMA-POSS nanocomposites had a homogeneous system. However, there was a significant phase separationat 3 wt.% SiO2. PMMA-SiO2 nanocomposites displayed lower reinforcing effects than expected, based on the mechanicalproperties of nanocomposites containing OVPOSS molecules.
KeywordsOctavinyl polyhedral oligomeric silsesquioxane, functionalized SiO2, nanocomposites, morphology, mechanical properties
Introduction
Nowadays, self-curing polymethyl methacrylate (PMMA)
resins are widely used in construction of a fractured denture
base because of their easier operability in comparison with
heat-curing resins.13 However, some problems, such as
lower hardness, lower strength, poor wear resistance, etc.
have been identified. Based on the property required, dif-
ferent types of materials have been produced. Fibers, metal
wires and nanoparticles are important materials which have
been reported recently. However, on the one hand, there is
inadequate adhesion of fibers or metal with polymethyl
methacrylate and on the other hand, silica nanoparticles are
easy to aggregate in the polymer matrix owing to high sur-
face area and surface energy.47 The properties of nano-
composite can be improved significantly because of the
modification of the structure and dynamics of a polymer
near the functionalized SiO2 particle surface.8,9
Polyhedral oligomeric silsesquioxane (POSS) has a cage-
like structure composed of a siliconoxygen framework, in
which a Si atom is connected to an organic group. The unique
hybrid organicinorganic structure and size ( 1.5 nm dia-meter and molecular weights 1 kg mol1) make POSSthe smallest possible particles of silica with applications in
synthetic templates for nanostructured materials.1012
Kopesky found that the addition of cyclohexyl-POSS and
methacryl-POSS to PMMA resin provided the highest tough-
ness values.13,14 Xu also found that a stronger dipoledipole
interaction might play the main role between the POSS and
1 Key Laboratory of Automobile Materials of Ministry of Education, College
of Materials Science and Engineering, Jilin University, Changchun, PR China2Comprehensive Department, College of Stomatology, Jilin University,
Changchun, PR China
Corresponding Author:
Chunling Zhang, Key Laboratory of Automobile Materials of Ministry of
Education, College of Materials Science and Engineering, Jilin University,
Changchun, 130025, PR China
Email: [email protected]
High Performance Polymers23(6) 468476 The Author(s) 2011Reprints and permission:sagepub.co.uk/journalsPermissions.navDOI: 10.1177/0954008311417023hip.sagepub.com
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the carbonyl of PMMA blends.15 Some studies have indi-
cated that the physical and mechanical properties of nano-
composites can be significantly improved when filled with
POSS nanoparticles.1618
In the present study, octavinylPOSS (OVPOSS) and
functionalized SiO2, which have similar SiO bonds and
different molecular structure, were selected and a series
of nanocomposites were prepared. Fourier transform
infrared (FT-IR) spectra, X-ray diffraction (XRD) patterns,
thermogravimetric analysis (TGA), scanning electron
microscopy (SEM) and transmission electron microscopy
(TEM) photographs were used to explain the morphology
of OVPOSS and functionalized SiO2. Differential
scanning calorimetry (DSC) analysis revealed the thermal
properties of the nanocomposites. The influence of
the mechanical properties of nanocomposites were also
investigated.
Experimental
Starting materials
Methyl methacrylate (MMA) and self-curing polymethyl-
methacrylate resin (PMMA) were supplied by Shanghai
New Century Dental Materials Co., Ltd. The g-methacrylox-ypropyltrimethoxysilane (MPS) and vinyltrimethoxysilane
were bought from Nanjing Shuguang Chemical Group Co.,
Ltd of China. SiO2 was obtained from Degussa. Ethanol,
methanol, toluene, cyclohexane and tetrahydrofuran were
provided by Beijing Chemical Works and Tianjin Tiantai
Fine Chemistry Reagent Company of China.
Synthesis of functionalized SiO2
Hydroxyl groups spread over the surface of SiO2, so
SiO2 particles cannot be dispersed directly in resins. Func-
tionalized SiO2 was synthesized followed published proce-
dures.19 Dried SiO2 (5 g, 0.83 mol) and toluene (100 mL,
0.94 mol) were stirred for 2 h at room temperature, and then
the mixture was mixed with g-methacryloxypropyltri-methoxysilane (MPS) (2.5 mL, 0.01 mol) at 110 C for12 h with constant stirring. The mixture was centrifugally
separated and the product was washed several times with
toluene to remove any impurities and unreacted monomers.
Finally, the white product was dried under vacuum at
120 C for 2 h.
Synthesis of OVPOSS
OVPOSS was synthesized by following the published
procedures.20 Ethanol (200 mL, 3.54 mol) and vinyltri-
methoxysilane (100 mL, 0.65 mol) were added to the
flask, which was equipped with a stirrer. The concen-
trated hydrochloric acid (2 mL, 0.065 mol) and distilled
water (15 mL, 0.83 mol) were added dropwise into the
reaction mixture. A white powder was obtained after stir-
ring and refluxing at 60 C for 40 h. The samples werethen washed several times with cyclohexane. Finally, the
recrystallization of OVPOSS by tetrahydrofuran and
methanol was dried at 60 C in a vacuum drying oven.1H-NMR: (CDCl3, ppm) 6.0 (2H, CHCH2); 29Si-NMR (ppm, solid state): 80.0 (SiO); FT-IR (cm1)with KBr powder: 1600 (CHCH), 1410, 1280 (CH),1110 (SiOSi) (Scheme 1).
Scheme 1. Synthesis of functionalized SiO2 and OctavinylPOSS.
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Preparation of nanocomposites
MMA solutions containing 0.5 1, 1.5, 2, 2.5, and 3 wt.%POSS were prepared in a container. The solutions were dis-
persed uniformly by ultrasonic shaking (frequency: 28 kHz,
applied power: 250 W) for 5 min. Then, self-curing poly-
methylmethacrylate resin was proportionately added to the
mixed solution. The mixture was transferred quickly into
molds after the samples had been mixed homogenously.
Finally, the nanocomposites were cured in a standard mold
at room temperature. The nanocomposites containing SiO2were prepared by the same method. In the present study
each sample was prepared at 25 C for 2 h after being takenout of the stainless steel molds and these samples were then
dried completely in a vacuum oven at 40 C.
Characterization
The IR spectra were recorded using a Nexus 670 intelligent
Fourier transform infrared (FT-IR) spectrometer and the
KBr pellet technique. 1H-, 29Si-NMR spectra were
recorded using CDCl3, as a solvent and TMS as an internal
standard on AVANCE500MHz. The microstructures of the
films were analyzed by XRD measurements. The grafting
percentages of functionalized SiO2 were determined by
TGA on a Perkin Elmer Pryis I instrument with a heating
rate of 10 C min1 from 30 to 600 C. The diffractogramswere obtained from a Japan D/max 2500PC XRD at 5*40
scan area. The dispersion state of the OVPOSS and functio-
nalized SiO2 were observed by using TEM (JEM-2010;
Japan). The bulk morphology of the nanocomposites was
analyzed by SEM using a JSM-6700F Microscope (Japan)
at an operating voltage of 15 kV. The nanocomposites were
cut into pieces and the SEM pictures were taken on the flat
surfaces. Samples were sputter-coated with a 10-nm-thick
layer of palladium prior to imaging. Hardness was
determined using a plastic ball indentation hardness tester
(QYS-96, China). The specimens were indented using a
Rockwell indenter having a 5 mm diamond press head. The
friction coefficient tests were carried out using a high-
temperature friction and wear tester (MG-2000, China).
The tribological performance of specimens was evaluated
using a metal-disk test, which was carried out under a
10 N load for up to 1000 rotations at ambient temperature
and humidity. Impact notched specimens (length: 100 mm,
width: 4 mm, and thickness: 1 mm) were tested on an
instrumented memory-type cantilever beam impact testing
machine (JJ-20, China).
Results and discussion
Synthesis and structural characterization
Figure 1(a), (b) and (c) present the FT-IR spectra of pure
SiO2, functionalized SiO2 and PMMA-SiO2, respectively.
As seen in Figure 1(a), strong absorption peaks appeared at
3440 cm1 (SiOH), 1090 cm1 (SiOSi) and 810 cm1
(SiO) in the FT-IR spectrum of SiO2. Furthermore,
Figure 1(b) shows that new absorption peaks appeared in the
spectrum of functionalized SiO2 at 1700 cm1 (CO) and
2940 cm1 (CH2), respectively, indicating that the functiona-lized SiO2 contains the acrylate group. Comparing
Figure 1(b) with Figure 1(c), it was found that the absorption
peaks in the spectrum of PMMA-SiO2 that occur at
1730 cm1 (CO) and 2950 cm1 (CH2) become corre-spondingly stronger than those in the spectrum of functiona-
lized SiO2.19,21
Figure 2 presents the TGA curves of pure SiO2 and func-
tionalized SiO2 under a nitrogen atmosphere. All the sam-
ples were washed for several times, allowing free MPS to
be completely removed. As shown in Figure 2, the functio-
nalized SiO2 was 16.3%. According to Equation (1), the
Figure 1. FT-IR spectra of (a) pure SiO2; (b) functionalized SiO2;(c) PMMA-SiO2.
Figure 2. TGA curves of (a) pure SiO2; (b) functionalized SiO2,SiO2 wt.% 5 g; MPS wt.% 2.5 mL.
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Figure 3. (a) X- ray diffraction spectra of functionalized SiO2 and PMMA-SiO2 nanocomposites; (b) X-ray diffraction spectra ofOVPOSS and PMMA-POSS nanocomposites.
Figure 4. (a) and (b) TEM images of octavinylPOSS; (c) and (d) TEM images of SiO2 particles.
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individual grafting percentage of functionalized SiO2 is
17.2%.22 Thus the TGA results were in good agreementwith the FT-IR spectra results, showing that MPS chains
had been successfully grafted onto the surface of SiO2.19
Percentage of grafting % Polymer grafted gSilica used g 100%
1The XRD for functionalized SiO2, pure OVPOSS and
nanocomposites is shown in Figure 3. According to Figure
3, the functionalized SiO2 is totally amorphous in nature at
2y 14 and does not show any sharp diffraction peaks.The XRD patterns of PMMASiO2 nanocomposites show
broad peaks at 2y 14, which correspond to the PMMApeak, but the SiO2 characteristic peaks at 2y 24have dis-appeared in the PMMASiO2 nanocomposites. As the con-
tent of SiO2 increased, the amorphous peak at 2y 24didnot shift obviously. As the addition of SiO2 did not induce
any crystallinity in these polymers, the result indicated that
the nanocomposites had a homogeneous system.23
Figure 3(b) presents a comparison of the X-ray diffrac-
tion patterns for PMMA, PMMA-POSS, and pure
OVPOSS. Among a variety of bands, the pure POSS profile
shows six distinct diffraction peaks at 2y 9.703,13.102, 19.669, 20.998, 22.914 and 23.683, corre-sponding to d-spacings of 8.99, 6.75, 4.51, 4.23, 3.88 and
3.75 nm, respectively.24,25 The first peak, corresponding
to a d-spacing of 8.99 nm, reflects the size of POSS mole-
cules and the remaining peaks are due to their rhombohe-
dral crystal structure.2427 The X-ray diffraction peaks of
nanocomposites showed a different diffraction pattern
including a sharp peak of nanocomposites at 2y 9.743and an amorphous peak at 2y 13.4. The amorphous peakwas found to shift as the 2y orientation reduced as the con-tent of POSS increased. It indicates that the distance
between the polymer chains had increased due to the
OVPOSS particles.
Figure 5. (a) SEM image of PMMA-2 wt.% POSS nanocomposites. (b) SEM image of PMMA-3 wt.% POSS nanocomposites. (c) SEMimage of PMMA-2 wt.%SiO2 nanocomposites. (d) SEM image of PMMA-3 wt.%SiO2 nanocomposites.
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Morphology analysis
More information regarding the microstructure in OVPOSS
and SiO2 was obtained by direct morphological examina-
tion using TEM. Figure 4 shows the micrograph of
OVPOSS molecules and SiO2 particles. It can be seen that
the morphology of OVPOSS was an irregular cube. The
size of the OVPOSS molecules was found to vary from
680 to 920 nm, and the average size of molecule was
780 nm. Another study reported that the aggregation of
cyclohexyl-POSS molecules led to the formation of short
cylinders, and the average length and diameter of POSS-
rich cylinders were approximately 62.5 and 12 nm.28 It
demonstrated that the morphology of OVPOSS molecules
led to the formation of aggregation. XRD analysis also
showed the size of POSS to be 354 to 740 nm. This result
was the same as the conclusion coming from the TEM
image analysis. The particle size distribution of SiO2 was
found to vary from 106 to 554 nm. A large amount of SiO2particles had aggregated although MPS had been tethered
onto the surface of SiO2.
The significant differences in the dispersion processes
for the two nanocomposites are reflected in the final
morphologies observed by SEM. Figure 5 shows a group
of SEM images of the samples with 2, 3 wt.% POSS and2, 3 wt.% SiO2. Clearly, the surface of the sample with2 wt.% POSS was uniformly distributed. However, theimage of the sample with 2 wt.% SiO2 implied aggregateparticles on their surfaces. Figure 6 shows the particle size
distribution, corresponding to the nanocomposites of Figure
5, respectively. The OVPOSS size of the nanocomposites
varied from 68 to 113 nm, and the average size of molecules
was 89 nm. The SiO2 size of nanocomposites varied from 66
to 194 nm, and the average size of particles was 112 nm. In
comparison with the TEM analysis, the average size of
OVPOSS molecules had reduced from 680 to 89 nm. This
Figure 6. Particle size of nanocomposites.
Figure 7. (a) DSC curves of PMMA-POSS nanocomposites; (b) DSC curves of PMMA-SiO2 nanocomposites.
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illustrates that the OVPOSS crystal aggregate separation led
to the formation of irregular cube variation.
Thermal properties of nanocomposites
The DSC technique was used to investigate glass transi-
tion temperature of PMMA-POSS and PMMA-SiO2
nanocomposites. Each nanocomposite has a single Tg in
Figure 7(a). With the increasing content of POSS, Tgslightly decreased. It was also found that methacryl-POSS
could disperse in PMMA at a low content before significant
phase separation.18 It indicates that PMMA-POSS has a
homogeneous system at a low content. In Figure 7(b) DSC
curves are presented for the PMMA-SiO2 nanocomposites.
Loadings up to 3 wt.% led to a decrease in the glass transi-tion temperature Tg. In the 3 wt.% nanocomposites, a secondglass transition event has appeared and this indicates signif-
icant phase separation at this loading.
Mechanical properties analysis
Figure 8(a) shows the hardness of the nanocomposites at
different content. The PMMA-POSS exhibited a hardness
value of 152 MPa, which is obviously higher than that of
PMMA-SiO2 (120 MPa). PMMA-POSS nanocomposites
have higher hardness than that of the nanocomposites. The
friction coefficient of PMMA-SiO2 increased rapidly with
increasing SiO2 content from 0 to 2 wt.% but this trenddecreased when the SiO2 content exceeded 2 wt.%, andthe PMMA-SiO2 has a minimum value in Figure 8(b).
Figure 8(c) shows the impact strength of the nanocompo-
sites as a function of particle loading. It was found that the
impact strength increased from 1.3 to 2.5 kJ m2 for nano-composite of PMMAwith 2wt.% SiO2. However, the impactstrength at breakdecreased, respectively, for the same loading
of particles. These results indicate that the mechanical prop-
erties of the nanocomposites containing POSS were much
better than that of PMMA-SiO2 nanocomposites.
Figure 8. (a) Hardness of nanocomposites; (b) friction coefficient of nanocomposites; (c) impact strength of nanocomposites.
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Conclusions
Nanocomposites of PMMA with OVPOSS and func-
tionalized SiO2 were analyzed to determine the effect of
particles on the morphology and mechanical properties
of PMMA. XRD, SEM, and TEM were employed for all
nanocomposites in order to confirm the morphology and
showed that the reduction in aggregate size with increas-
ing particles. DSC showed that phase separation became
apparent in the nanocomposites containing functionalized
SiO2 in comparison with PMMA-POSS nanocomposites
at the same loading (f 3 wt.%). The mechanical prop-erties of PMMA-POSS nanocomposites were higher than
those of the nanocomposites containing functionalized
SiO2 at the same content.
Acknowledgements
The financial support provided by the Development Project of
Jilin Province Science and Technology of China (No.
20100544) and the Innovation Project of Jilin University (No.
200903012) is gratefully acknowledged.
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