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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

at Middle East Technical Univ on June 11, 2015hip.sagepub.comDownloaded from

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.

Zhang et al 469


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.

470 High Performance Polymers 23(6)


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.

Zhang et al 471


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.



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.

Zhang et al 473


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.



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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