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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 456462

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Development of novel dental nanocomposites reinforced with polyhedral oligomeric silsesquioxane (POSS)
Xiaorong Wu a, , Yi Sun a , Weili Xie b , Yanju Liu a , Xueyu Song a
a b

Department of Astronautic Science and Mechanics, Harbin Institute of Technology, China Department of Stomatology, Harbin Medical University, China

a r t i c l e
Article history:

i n f o

a b s t r a c t
Objectives. It has been the focus to develop low shrinkage dental composite resins in recent ten years. A major difculty in developing low shrinkage dental materials is that their deciency in mechanical properties cannot satisfy the clinical purpose. The aim of this study is to develop novel dental nanocomposites incorporated with polyhedral oligomeric silsesquioxane (POSS). It is especially interesting to evaluate the volumetric shrinkage and mechanical properties, improve the shrinkage, working performances and service life of dental composite resins.

Received 14 April 2009 Received in revised form 18 July 2009 Accepted 16 November 2009

Keywords: Dental composite resins Nanocomposites Shrinkage Polyhedral oligomeric silsesquioxane (POSS) Mechanical properties

Methods. The effect of added POSS on the composites mechanical properties has been evaluated. The weight percentages of added POSS are 0, 2, 5, 10 and 15 wt% respectively. Fourier-transform infra-red spectroscopy and X-ray diffraction were used to characterize their microstructures. Physico-mechanical properties that were investigated included volumetric shrinkage, exural strength, exural modulus, compressive strength, compressive modulus, Vikers hardness and fracture energy. Furthermore, the possible reinforced mechanism has been discussed. Results. The shrinkage of novel nanocomposites decreased from 3.53% to 2.18%. The nanocomposites incorporated with POSS showed greatly improved mechanical properties, for example, with only 2 wt% POSS added, the nanocompsites exural strength increased 15%, compressive strength increased 12%, hardness increased 15% and uncommonly, even the toughness of resins was obviously increased. With 5 wt% POSS polymerized, compressive strength increased from 192 MPa to 251 MPa and compressive modulus increased from 3.93 GPa to 6.62 GPa, but exure strength began to decline from 87 MPa to 75 MPa. This nding indicated that the reinforcing mechanism of exure state maybe different from that of compressive state. Conclusions. The mechanical properties and volumetric shrinkage of dental composite resins polymerized with POSS can be improved signicantly. In current study, the nanocomposite with 2 wt% POSS incorporated is observed to achieve the best improved effects. 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +86 0451 86414825. E-mail addresses: wuxr2230@163.com, atanackovic@uns.ns.ac.yu (X. Wu). 0109-5641/$ see front matter 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.dental.2009.11.161

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1.

Introduction

The development of dental restorative materials, in particular direct resin-based lling composites, has revolutionized the eld of dentistry over the past 30 years. This development has been achieved mainly through organic monomer discovery, modications in formulation, the use of new tailor-made llers (e.g. nanollers or clusters for the composite) or advances in light curing equipment and efcient photo initiators [1]. Despite these developmental advances, some problems still limit the use of composites in dental restoration. Most improvements are focused on the reduction of polymerization shrinkage [25], as well as the improvement of wear resistance [68], mechanical properties [912], biocompatibility [1315], and processing properties [16,17]. Polyhedral oligomeric silsesquixanes (POSS) is one typical organicinorganic hybrid nanocomposite, which has been developed since the end of last century. POSS is really a nanostructural chemical whose molecule is 1.5 nm isotropic in structure. POSS monomer is represented by the empirical formula (RSiO1.5)n with an inorganic silica-like core (SiO1.5 ) surrounded by organic corner groups R. It has been revealed that the performances of POSSmodied polymers are usually attractive. They not only have the organic characters such as good processability, toughness and low cost, but also hold excellent inorganic performances in mechanics, thermodynamics, anti-oxidation, etc. [1820]. At present, it is a very important way to get functional and good performance materials modied by POSS. Sellinger and Laine [21] rst mentioned the possibility of POSS being used in dental restorative materials. In a latter study, the research group of Culbertson and co-workers [22] evaluated the systems of POSS incorporated with neat resins (without ller). The results showed that miscibility between the POSS component and the matrix, especially the diluents, played a very important role in improving the properties of the formulated thermosets. Based on the research of Culbertson and co-workers group [22], Fong et al.s team [23] explored novel polymeric dental restorative composites, in which POSS-MA was used to partially (or completely) replace Bis-GMA. The results showed that only a small percentage of POSS-MA substitution of Bis-GMA in the resin systems could improve the mechanical properties of the composites. However, it was a pity that there was no distinct improvement in such important properties as compressive strength, hardness and toughness. Dodiuk-Kenig et al. [24] believed that the type of the grafted functional group of the caged silica was the dominant factor in nanotailoring of improved dental composites and adhesives. It showed that the mechanical properties of dental composites and adhesives were improved by acrylated POSS but deteriorated by octaphenyl grafted POSS. Many other research works [2527] have been done on the structural design of the POSS molecule, synthesizing the process of modied resins, as well as properties characterization. But we have to admit that considerably complicated techniques of synthesis and rigorous conditions of reaction are needed for most new POSS monomers. Therefore, this seri-

Fig. 1 Molecular anatomy of multifunctional methacryl POSS.

ously limits the development and application of POSS in dental restorations. In this paper, multifunctional methacryl POSS cage mixture (n = 8, 10, 12) (from Hybrid Plastics) was explored to be added into dental composite resins to develop novel dental nanocomposites with improved properties. Multifunctional methacryl POSS molecules anatomy (showed by Fig. 1) consists of an inorganic cage built with silicon and oxygen, and each Si is attached by a methacrylate functional group. Additionally, the methacryl POSS is soluble in the composite resins. The aim of the study was to develop novel dental nanocomposites with POSS incorporated, evaluate their polymerization shrinkage, mechanical properties, and improve working performances and service life.

2.
2.1.

Materials and methods


Formulation of nanocomposites

Methacryl POSS was obtained from Hybrid Plastics (Fountain Valley, CA). Bis-GMA (Bisphenol A glycerolate dimethacrylate) and TEGDMA (Tri(ethylenglycol) dimethacrylate, TEGDMA, 98%) were from Aldrich Chemical Co. (shown in Fig. 2). All monomers were used as received without further purication.

Fig. 2 Molecular structures of the monomers and photo-initiation system.

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Table 1 Weight percentage of the components used in dental nanocomposites (wt%). Composites code Resin matrix wt% POSS wt% BG wt%
P00 P02 P05 P10 P15 40 38 35 30 25 0 2 5 10 15 60 60 60 60 60

metric shrinkage was calculated using the formula: Shrinkage V % = 1


uncured cured

100%

(1)

The commonly used visible light photo-initiator CQ (camphorquinone, 97%) and co-initiator (2-(dimethylamino) ethyl methacrylate, DMAEMA, 98%) were selected for this research. Both CQ and DMAEMA were also from Aldrich Chemical Co. The ller used in this study was nely milled silanized barium oxide glass powder (BG) with an average particle size of 0.8 m, provided by the materials laboratory of the School of Stomatology at Peking University.

The samples involved in this part of the study were prepared under a two-step photo-initiated curing process. First, the samples were exposed to visible light and cured for 60 s, then the visible light switched off, 60 min later, the second photo-initiated curing began and lasted for another 30 s.

2.6.

Flexural strength and exural modulus

2.2.

Synthesis of materials

A solution containing 49.5 wt% Bis-GMA, 49.5 wt% TEGDMA, 0.5 wt% CQ and 0.5 wt% DMAEMA was prepared by mixing sufciently in a container kept away from light. Then multifunctional methacryl POSS was proportionately added to the solution of neat resins as Table 1 and magnetically blended uniformly. Finally, BG was slowly put into the mixture and stirred in the vacuum mixer allowing for the escape of air bubbles. In this study the curing time of each sample was 40 s at room temperature, except special explanation. Five specimens were prepared for each type of material and immersed in distilled water at 37 C for 24 h after taking out of the stainless steel molds, followed by a careful polish in a longitudinal direction under water with 2400 grit silicon carbide paper. The nal dimensions of the specimens were then measured accurately and recorded immediately before testing.

The specimens were prepared in stainless steel molds with a dimension of 2 mm in width by 2 mm in depth by 25 mm in length. Flexural strength (FS) and exural elastic modulus (Ef ) were obtained by three-point exure testing (according to ISO4049: 2000) at a crosshead speed 0.5 mm/min. The test was performed on a T1-FR010TH A50 (ZWICK Materials Testing Machine, Germany). Calculations were made using formulas as follows: FS = 3PL 2WT 2 P d L3 4WT 3 (2)

Ef =

(3)

where P is the load at fracture, L is the distance between two supports (which was set to be 20 mm), W is the width of the specimen, T is the thickness of the specimen and d is the deection at load P.

2.7.

Compressive strength and compressive modulus

2.3.

FTIR characterization

Fourier-transform infra-red spectroscopy (FTIR) was utilized to evaluate the degree of conversion. The mid-IR spectra were collected with an AVATAR360 (Nicolet, USA) instrument equipped with 4000400 cm1 wave speed. A blank KBr pellet was used for the collection of the background spectrum. The samples involved in this part of the study were neat resins without ller.

Compressive strength (CS) and compressive elastic modulus (EC ) were measured by compressive testing at a crosshead speed of 10 mm/min with cylindrical samples with the dimensions 3 mm in diameter by 7 mm in length. The test was performed on a T1-FR010TH A50 (ZWICK Materials Testing Machine, Germany). Calculations were made using formulas as follows: CS = 4P D2 4L0 (FH FL ) D2 (LH LL ) (4)

EC =

(5)

2.4.

X-ray characterization
where D is the diameter of the specimen, L0 is the length of the specimen, FH (FL ) and LH (LL ) is the end(start) of the corresponding load and distortion of the specimen in the elastic phase of loaddistortion curve.

Wide-angle X-ray diffraction (WAXD) was performed using a D/max-B rotational anode X-ray diffractometer (Japan) with Cu Ka irradiation (wavelength of 1.54 ) using a nickel lter. The X-rays were collimated with a pinhole collimator. Data points were collected over the 2 range of 1090 at 0.02 intervals. The samples involved in this part of the study were neat resins without ller.

2.8.

Hardness

2.5.

Shrinkage

According to ISO3521, a pycnometer was used to measure the density ( ) of uncured and cured resin specimens. The volu-

Vickers hardness (HV) was determined using a depth-sensing microindentation technique on BZ2.5/TSIS (Universal Hardness Testing Instrument, Germany). The specimens were indented with a Vickers indenter, whose diamond press head was in right square pyramid shape with 136 relatively angle. Vickers hardness (HV) data was obtained by dividing the peak

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Fig. 3 FTIR spectra of the resins irradiated for 40 s. (a) P00 (Wposs = 0 wt%) and (b) P02 (Wposs = 2 wt%).

load (Pmax ) over the maximum projected contact area (Amax ) as follows: HV = Pmax Pmax = 1.8544 Amax d2 (6)

where d is the average length of two indented diagonals.

2.9.

Fracture energy

P00 and Fig. 3(b) P02, it could be seen that the weakened degree of C C absorption of P02 was greater than that of P00. It accounted for why the degree of conversion of P02 was greater than that of P00. The methacrylate double bond conversion is one of the important properties in dental composite resins. Generally, the mechanical property of resins can be improved with an increase in conversion. It was also proved later in this paper.

Fracture energy (Nmm) is the dissipative outside energy during fracture, which can be calculated by the enclosed area of stressstrain fracture curve obtained from three-point exure test. In the physics, the square of toughness is namely the energy release rate. Therefore, fracture energy can be the measurement of the toughness of the materials, and usually, the greater the fracture energy, the tougher the material.

3.2.

WAXD

3.

Results and discussion

In this paper, 40/60 (wt%) was chosen as the ratio of resin matrix/inorganic ller. The composite resins with such ratio not only had proper viscosity to keep the ller from depositing, but also had sufcient uidity to make resins easy to be processed. In this paper, the effects of dental nanocomposites with different weight percentage (015 wt%) POSS on the polymerization shrinkage and mechanical properties were investigated.

Wide angle X-ray diffraction was employed to investigate whether POSS crystal peaks appear in the nanocomposites of the WAXD proles. In this study, wide-angle X-ray diffraction data (Fig. 4) indicated that all POSS nanocomposites were amorphous, even when the mass fraction of the methacryl POSS monomers in the resin mixture was as high as 15%, no POSS crystal peaks could be identied, which conrmed that the multifunctional POSS had polymerized within the resin matrix.

3.1.

Degree of conversion

The FTIR spectra shown in Fig. 3 were the mid-IR measurements of the C C absorption at 1635 cm1 . Uncured and cured resins were evaluated, which deadline stood for uncured samples and dashed stood for cured ones. From FTIR spectra (Fig. 3) it can be seen that the intensity of C C absorption at 1635 cm1 was obviously weaker after curing. It proved that the methacrylate double bonds had partly conversed and the resins had polymerized during curing. Compared with Fig. 3(a)

Fig. 4 WAXD proles of the nanocomposites.

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3.3.

Shrinkage

Most dental composite resins are free-radical initiation photopolymers, and volumetric shrinkage during polymerization is usually high. Volumetric shrinkage causes microleakage, a well-known effect of contraction gaps at the interface between resin and tooth. Saliva, uid, food residue and microorganisms trapped in the gaps lead to decayed teeth and damaged enamel, which is a major problem in current restorative and esthetic dentistry. The change in the distances among atoms caused by polymerization is probably the major reason for the shrinkage. Van der Waals forces acting on molecules of the monomers turn into covalent bonds and the distances among atoms become shorter from 0.3 to 0.5 nm to 0.154 nm. Therefore, the compact arrangements make the volume shrink during polymerization. Another possible reason of the shrinkage is the change in the free volume which exists owing to molecules in the polymer not being fully compacted. The free volume of molecules with liquid state before curing is greater than their loose state. After curing, monomers polymerize with matrix to form a cross-linked net framework [28] and the movement of chains is limited by plenty of cross-linked points. Therefore, the free volume becomes smaller and causes remarkable shrinkage. In this paper, the volumetric shrinkage of novel systems with POSS was evaluated. The results of the shrinkage of composite resins synthesized are shown in Fig. 5. Shrinkage was from 3.53% to 3.10% when only 2 wt% POSS was incorporated, and it reduced from 3.53% to 2.18% when 15 wt% POSS was used. The results proved that multifunctional methacryl POSS can effectively reduce the shrinkage of resins and that shrinkage is reduced with the increasing percentage of POSS. The possible reason is that the special nanocubic structure of POSS may limit the change of the resins free volume after a crosslinked net framework is formed. Therefore, the shrinkage of resins with POSS incorporated was decreased.

Fig. 6. With only 2 wt% POSS added, the nanocompsites exural strength increased 15%, compressive strength increased 12%, compressive modulus increased 4% and exural modulus showed no change. With 5 wt% POSS polymerized, compressive strength increased from 192 MPa to 251 MPa and compressive modulus increased from 3.93 GPa to 6.62 GPa, but exural strength began to decline from 87 MPa to 75 MPa. This nding indicated that the reinforcing mechanism of the exure state maybe different from that of the compressive state. Flexural strength, a very important property for dental restorations, can reect the ability that the materials to withstand complex stress. In current research, it was found that with only 2 wt%, POSS copolymerized in resins, exural strength increased 15% and compressive strength increased 12% (see Fig. 6). This result accorded with the above part of degree of conversion. A lot of researches [3032] indicated that the dispersion of nanoparticles was the key factor for improving the mechanical properties of the matrix. Libor et al. [28] proved that POSS monomer did not simply mix physically with resins but polymerize with matrix to form a cross-linked net framework. That makes POSS disperse uniformly in the matrix and is less aggregated, which was also proved by the abovementioned wide-angle X-ray diffraction data. It can probably explain the results that exural strength and compressive strength of nanocomposites were improved by introducing POSS. When the weight percentage of POSS was more than 10 wt%, it was found that the mechanical properties of nanocomposites decreased sharply (Fig. 6). The reason may that be the formation of a cross-linked polymeric network with more POSS was so rapid, that it limited the speed of the mobility of reactive species. And more POSS monomers could not be polymerized and then congregated. Therefore, the mechanical properties of nanocomposites deteriorated seriously.

3.5. 3.4. Mechanical properties

Hardness

The nanocomposites incorporated with POSS showed greatly improved mechanical properties. The test results are shown in

While strength itself is of great importance in determining a materials service performance, bulk properties are only part of the story. The surface behavior of a restoration, such as hardness, is another important mechanical property. Hardness can reect the ability of resisting plastic distortion and may scale with wear for certain materials. The hardness of materials should be as close as possible to that of the natural tooth. In this study, the hardness of novel nanocomposites was increased from 349 MPa to 400 MPa (Fig. 7), and consequently closer to the hardness of dentin (570600 MPa). It is probably because the special rigid cubic structure of POSS improved the hardness of the matrix.

3.6.

Fracture energy

Fig. 5 Shrinkage of the nanocomposites with different weight percentage of POSS.

It was found that with only 2 wt% POSS, fracture energy increased 56% (Fig. 8), which can be a measurement of the toughness of the materials. Traditionally, with increasing strength and stiffness of reinforced polymers, the toughness of the materials usually declined. Uncommonly, in this study, POSS monomer was also found to be obviously helpful in increasing the toughness of resins. This is an important nd-

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Fig. 6 Mechanical properties of the nanocomposites with different weight percentage of POSS.

ing for the clinical perspective because, in some structures of dentures, toughness of material is a desired property. The improvement may be down to the methacrylate functional groups attached in POSS molecules. Their exible long chain structures may provide better toughness for the resin matrix. In addition, interface action between nano-POSS particles and matrix would be stronger for their formed cross-linked networks. It needs to absorb more energy during fracture. This is another possible reason why POSS increases the toughness of the matrix.

Fig. 8 Fracture energy of the dental nanocomposites.

4.

Conclusion

Fig. 7 Hardness of the dental nanocomposites.

The authors synthesized POSS-modied dental composite resins. The mechanical behavior and volumetric shrinkage of the composite resins copolymerized with multifunctional methacryl POSS were examined for their dependence on the weight fraction of POSS monomer (015 wt%). In this study, the nanocomposite with 2 wt% POSS incorporated was observed to achieve all-around improved effects, whose exural strength increased 15%, compressive strength increased 12%, compres-

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sive modulus increased 4%, hardness increased 15%, fracture energy increased 56% and volumetric shrinkage decreased from 3.53 to 3.10. The dental composite resins polymerized with POSS can improve their mechanical properties and volumetric shrinkage; increase the dental nanocomposites working performances and service life.

[14]

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Acknowledgements
This work was supported by the National Natural Science Foundation of China (10472028), the Doctoral Program Foundation of Ministry of Education of China (20070213054), the Natural Science Foundation of Heilongjiang Province (D0329) and the Excellent Youth Foundation of Heilongjiang Province. We thank the help of Dr. Daming Gu, Department of Applied Chemistry, Harbin Institute of Technology, for supplying the laboratory.

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