Dental Materials Journal 2012; 31(4): 635644

Preparation and characterization of a BisGMA-resin dental restorative composites with glass, silica and titania llers
Sanjay THORAT 1,2, Niranjan PATRA 1, Roberta RUFFILLI 3, Alberto DIASPRO 1 and Marco SALERNO 1
University of Genova, viale Causa 13, I-16145 Genova, Italy Istituto Italiano di Tecnologia, Department of Nanophysics, via Morego 30, I-16163 Genova, Italy 3 Istituto Italiano di Tecnologia, Department of Nanochemistry, via Morego 30, I-16163 Genova, Italy Corresponding author, Marco SALERNO; E-mail: marco.salerno@iit.it
1 2

A photo-polymerizable Bisphenol-A diglycidylether methacrylate resin was characterized by Fourier transform infrared spectroscopy after its irradiation under different conditions to identify the best curing. Bonding-agent free composites with particles of ball-milled glass, silica and titania at loading of 10 and 50%wt were prepared, and their viscoelastic properties investigated by dynamic mechanical analysis, in experimental conditions close to the working environment in the mouth. All composites showed good stability at the considered conditions. The stiffest composite was the silica one, which was based on the smallest primary particles. The storage moduli close to room temperature (25C) and mastication frequency (1 Hz) were extracted as reference bending moduli for the materials, and compared to static compressive moduli measured by nanoindentation performed by atomic force microscopy. Nanoindentation showed qualitative results in agreement with dynamic mechanical analysis as to the ranking of different materials, while resulting in approximately two-fold elastic modulus. Keywords: Dental restorative composites, Inorganic llers, Dynamic mechanical analysis, Nanoindentation, Elastic modulus

INTRODUCTION
The eld of dental restorative resin composites is still open for improvement and thus a much active area of research1). In fact, despite the recent advancements both in chemistry of the resins and in development of novel nanoparticles and related technologies2,3), many combinations thereof have to be explored and the respective recipes have to be optimized yet. The main issue with the dental resin composites is that still their mechanical properties can only barely approach those of dental amalgam4). Unfortunately, the industrial manufacturers of dental composites, which have the resources in both man-power and accessible instrumental techniques, on the one hand are forced to focus on the health issues of the novel materials, and on the other hand are pushed to deliver new products on the market as soon as possible to win the race with their competitors. As a result, materials that are poorly characterized in physical and mechanical properties are sometimes released and promoted beyond their real performances, as it has been the case in the last decade for several owable composites5,6). In this scenario, a deeper understanding of the combined effects of the various parameters of composite materials is to be attained, by preliminary investigations carried out in the laboratory. In this work we investigated simple composite systems without ller-matrix bonding agent, and within this limitation we studied the effect of different ller particle materials on the respective elastic properties. Three different types of llers were selected, namely ball-milled

glass, and commercial particles of titania and silica. The ball-milled glass was chosen for the potential control of the particle size in our laboratory in view of future developments, and the commercial silica particles were chosen as the standard counterpart for comparisons. Titania has been chosen additionally as a novel ller material, thanks to its mechanical stiffness due to the crystalline particles nature, and to the interesting possible photo-activity. In fact, it is known that titania is a good absorber of UV light potentially driving chemical reactions (photocatalytic effect7)), which could be used to trigger e.g. periodic biolm removal and/or changing its surface wettability to superhydrophobic character8). In most existing literature the mechanical properties of dental composites are investigated by means of static loading methods, such as nanoindentation to measure elastic modulus and hardness, or universal tester to measure exural strength and fracture toughness. However, indentation only reports about the response to compressive stress, whereas exural stress loading is also important in restorations, which exhibit interfaces bonded to the native tooth cavity. On the other hand, strength and toughness tests are destructive, making it impossible to repeat testing of the same specimens over the time. Furthermore, both methods are static and can only partially account for the viscoelastic nature intrinsic in the polymeric matrix phase of the dental restorative composites. Therefore, we decided to use dynamic mechanical testing as the main experimental technique, to provide a more realistic characterization of the materials considered.

Color gures can be viewed in the online issue, which is available at J-STAGE. Received Dec 12, 2011: Accepted Apr 2, 2012 doi:10.4012/dmj.2011-251 JOI JST.JSTAGE/dmj/2011-251

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sticking to the jar bottom, but these could be easily broken down into ne powder by simply touching them with steel tweezers. It was thus possible to mix this powder thoroughly with the resin paste, similarly to the commercial particles. In order to compare the commercial nanosilica and titania powders with the glass ball-milled in IPA, the particle size of each ller material was rst measured by dynamic light scattering (DLS) in IPA suspensions. To this goal, polystyrene cuvettes were used in a Nano-ZS setup (Malvern Instruments, UK). We started from concentrated IPA suspensions (~5 g/L for the commercial powders, and as collected material from the ball-milled glass), and then moved on to a more diluted suspension of the same material, decreasing the concentration to 50% at each step. We went on with dilution until the measurement quality resulting from the instrument report remained acceptable, as to the sufcient optical density required for a good statistical analysis. Also, for each suspension 3 series of 3 measurements each were repeated and averaged. In addition to DLS measurements in IPA, after drying the IPA suspension of ball-milled glass the ller particles were measured again in DLS upon mixing them into the resin. Since the mixtures had to be manipulated in the light for several minutes, for these measurements we used BisGMA and TEGDMA only without photopolymerizing system (CQ-DMAEMA). The missing CQ-DMAEMA part should not affect signicantly the rheology of the system, due to the low percentage (0.5 wt% of the co-monomer). Finally, microscopic imaging was also used to further assess the size of bare primary particles and particle aggregates. Photo-curing conditions The elongated beam shape of the specimens (see Dyamic mechanical analysis for the size) required three irradiation cycles for each specimen, which were applied starting from the central region rst and moving to the two side regions later on. For selection of the most appropriate photo-curing lamp, the intensity of various light sources available in our laboratory was preliminary measured with a power meter Nova II (Ophir, USA). Since CQ has a peak of light absorbance at 470 nm wavelength, which efciently starts the polymerization reaction after amplication by the electrons extracted from DMAEMA, we measured both the full spectrum power (white light) and the power at a selected blue region window only (blue light). To this goal, a lter was taken from a uorescence cube GFP (Semrock, USA), with ~95% transmittance at a 455 490 nm wavelength pass band. As a result of this step, we selected a X-Cite 120 lamp (EXFO, Canada), which was placed at a distance of ~3 cm from the specimens to be cured. This lamp is a high output power white light source with a broad smooth spectrum, normally used for optical microscopy imaging of specimens stained with uorescent dyes. The irradiance of this lamp was evaluated in comparison with other light sources used in both literature and recent clinical practice10-12), on which

MATERIALS AND METHODS

Resin matrix 2,2-bis[4-3-(methacryloxy-2-hydroxy-propoxy)-phenyl]propane (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) were mixed in 7:3 ratio by weight. The former is the traditional resin monomer used in dental restorative composites since more than half a century9). The latter is one among several monomers usually mixed with BisGMA to make the paste more uid and handy during manipulation (viscosity decreasing co-monomer)1). The system was carefully blended by spatulation for 3 min. The co-monomer mixture was further added with the photopolymerization system, consisting in camphorquinone (CQ) as a photoinitiator and dimethyl amino ethyl methacrylate (DMAEMA) as an amine reducing agent. CQ and DMAEMA were added in 1:1 weight ratio, such that their total amount was 0.5% wt of the total co-monomer. All products were supplied by Sigma-Aldrich (Milan, Italy). The overall system was blended again by spatulation for additional 3 min. In case of ller loading, the respective particles were added in 10 or 50% wt proportion of the overall organic matrix paste, and the system was spatulated again for up to additional 15 min for the highest loading cases. The paste was then poured into a clean antisticking mold of Teon, and placed in a bell rest chamber pumped to low vacuum (~100 mbar) to remove air bubbles formed during spatulation. Filler materials Two of the three types of llers used were commercial materials, namely silica and titania particles (Sigma-Aldrich products no. 718483 and 232033, respectively). The silica particles are described as nanopowder with average diameter of 12 nm, and are amorphous in character. The titania particles are described as powder without any size specication, and are crystalline in character (anatase). The third type of llers used was ball-milled glass. For the source, optical microscopy specimen coverslips were used (Menzel-Glser, Germany), of size 20200.3 mm3. These coverslips are made of borosilicate glass (D 263 M type, Schott AG, Germany). Despite the large planar dimensions, these slides are so thin that it was possible to load them directly into the ball-miller jar without preliminary fragmentation. The ball-miller used was a PM100 (Retsch, Germany), operated with a 50 mL zirconia jar, lled with 100 g of glass and zirconia balls. We used 30 balls of 5 mm diameter together with 60 balls of 3 mm diameter. The milling was carried out in 20 mL isopropanol (IPA, Sigma-Aldrich) at a rotating speed of 450 RPM, with alternating cycles of 1 min clockwise and 1 min counterclockwise rotation without resting time, for a total milling time of 5 h. After milling, the hot jar (~80C) was let to cool down to room temperature (RT) in place, before opening it. The suspension was then poured into a previously weighted glass beaker, and was let to dry in an oven at 90C for 4 h. After drying, the glass appeared to be agglomerated in large plates

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basis we decided to set our irradiation time to 105 and 210 min for white and blue light, respectively, which methods were both tested for curing the bare resin. Fourier transformed infrared spectroscopy In order to verify the conversion of the co-monomer paste into a polymerized resin, Fourier transformed infrared spectroscopy (FTIR) was carried out for all the specimens at RT in ambient air, both soon after pouring the paste into the Teon molds and after its irradiation. The FTIR spectra were acquired by a Vertex 70 spectrometer (Bruker, USA), in the range of 4004,000 cm1. The samples were analyzed in attenuated total reection conguration, with an aperture diameter of 3 mm and a spectral resolution of 4 cm1. For optimal signal-to-noise ratio, 50 scans were averaged per sample spectrum, and apodized by applying the Blackman-Harris 3-term correction function for the Fourier transformation. The interferograms were corrected using a zero-lling factor of 2. All the spectra were baseline-corrected by third order polynomial and were normalized thereafter. Dynamic mechanical analysis All the materials were shaped with the Teon mold to be rectangular beams of 13352 mm3 in size. On these samples we performed dynamic mechanical analysis (DMA) by means of a Q800 setup (TA Instruments, USA), with instrument compliance of less than 0.2 m/N, as determined by a prior calibration in static loading mode. We carried out DMA measurements in single-cantilever mode, under strain control in the materials linear regime. The maximum applied strain was 35 m. Temperature sweeps at strain frequency of 1 Hz were carried out, in a range of +2 to +62C (with 5C steps, 5C/min rate), since it should represent well the limit values occurring in human mouth in normal operating conditions, when ingesting from hot food to icy drinks. For reaching the lowest temperatures in this range, liquid nitrogen was used as a coolant. During the temperature scans both the storage modulus E and the loss modulus E were recorded, representing the in-phase (real) and out-of-phase (imaginary) parts of a complex modulus E*=E+iE, respectively, occurring due to the stress lagging behind the applied strain with some phase angle delay. AFM nanoindentation The same samples as prepared for the DMA were used, before carrying out the respective tests. We performed nanoindentation by means of an AFM used in so-called force spectroscopy mode, i.e. collecting force-distance curves on given specimen sites. We used a MFP-3D AFM (Asylum Research, USA) equipped with gold coated silicon probes NSG20 (NT-MDT, Russia), made each of a cantilever with nominal spring constant and resonance frequency of ~60 N/m and ~450 kHz, respectively, and of a terminal transverse pyramidal tip with apex diameter and full aperture angle of ~20 nm and ~22, respectively. The typical lateral scan size was 5 m, with spatial map sampling of 302 pixels. The AFM probe was calibrated in

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air for determination of the cantilever spring constant, and again in de-ionized water for determination of the appropriate optical lever sensitivity. In fact, the force-distance curves were acquired in water to remove the effect of aspecic tip-surface adhesion due to ambient moisture. The curves had 1,024 datapoints, with z actuation loops of 1 m range and 0.5 Hz frequency, low enough to minimize viscous drag effects, (data not shown). Preliminary to the AFM nanoindentation experiments, occasionally AFM imaging was carried out with the same probe (in Tapping mode, with 30 m scan size and 2562 pixels), which showed evidence of the presence of llers in the composites, as compared to the bare resin surface (data not shown). However, all the composite samples were still at and smooth enough at the surface, such that they could be properly investigated by nanoindentation at the considered low indentations (up to limited maximum values of max~100 nm only). After acquisition, the indentation was calculated from the z movement of the actuator z and from the change in cantilever deection D (partially compensating the former) as =zD. The force-indentation data were nally t to the Hertz model of elastic contact, using the unload part of the force loop to nd the elastic modulus values EAFM. Given the high number of parameters in the Hertz model, (indenting tip size and shape, sample and tip materials Poissons ratios, tip elastic modulus, actual contact point (, F)=(0, 0)), both offsets of indentation and force were let to t automatically by the AFM software within a broad range of forces, 25%75% of Fmax, such as to minimize the deviations between tting curve and data-points (reduced 21,000). Additionally, the remaining parameters were adjusted on the bare resin reference material, such that for this the compression modulus EAFM resulting from nanoindentation was equal to the respective exural modulus E resulting from the DMA experiments. After this initial setup, the same values of the remaining working parameters were used later also for the composites.

RESULTS
Resin curing evaluation In Fig. 1a) the FTIR spectra of the uncured components of the organic paste are presented, both individually and blended in the resulting mixture (red line). Clearly, BisGMA and TEGDMA dominate the spectrum of the mixture, with some features, such as e.g. the peaks at 2,874 cm1 (symmetric stretching of CH3) and 1,126 cm1 (symmetric vibration of -C-O-C-) of TEGDMA increasing the adjacent shoulders of BisGMA. The peaks of DMAEMA at 2,771 cm1 (N(CH3)2 band) and of CQ at 1,747 cm1 (C=O vibration) do not appear in the mixture, due to the low relative contribution of the respective components. The 3,3503,550 cm1 band (OH stretching) is slightly depressed. In Fig. 1b), the effect of photo-curing is reported. In particular, a signicant change in the bands centered around 1,637 and 1,580 cm1 is observed, with

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Fig. 1

a) FTIR spectra of individual BisGMA, TEGDMA, CQ and DMAEMA, as well as of the (uncured) mixture of the same compounds (red line). b) FTIR spectra of the resin mixture before (uncured, red) and after irradiation, according to different conditions.

a relative increase of the second one, corresponding to the stretching of the aliphatic and aromatic (i.e. ring) C=C bonds, respectively. In fact, as a measure of photo-polymerization, the degree of conversion (DC) of the monomer mixture into the polymer (photo-cured mixture) can be evaluated from the following equation, according to a peak intensity method14): DC = 100 [ 1 (I1637 / I1580) pol (I1637 / I1580) mon ] (1)

time scale, (+25% in DC). However, when repeated again after one month since irradiation, no further change was observed, showing no effect of possible absorbance of moisture or other ambient contaminants. The blue exposed resin, on the contrary (blue curve in Fig. 1b)), only reached ~57% soon after curing (Fig. 4), and also showed lesser improvement at one week time (~63%, i.e. +11%, curve not shown). Filler size characterization The apparent size of the ller particles was determined by means of DLS, which was rst applied on suspensions of the respective powder in IPA. The adopted method of progressively more diluted suspension should minimize the effect of agglomeration, allowing for a determination of particle size as close as possible to the primary particles. In fact, after 3 to 5 dilution steps, for all materials the apparent average particle size had decreased, reaching either a more stable value or the limit of lowest acceptable measurement quality mentioned above. The nal distributions of particles size in IPA are shown in red in Fig. 2a)c). The apparent mean particle size in IPA is ~650 nm for glass (Fig. 2a) red bars) and ~950 nm for titania (Fig. 2b) red bars), respectively. For silica

where I1637 and I1580 are the peak intensities of the bands at the respective wavenumber positions, and the subscripts outside the parentheses refer to the spectra before (mon) and after (pol) photo-curing, respectively. From eq. 1 applied to the spectra in Fig. 1b), it turns out that the highest conversion is found for white light curing (see Fig. 4). This condition (gray curve in Fig. 1b)) provided a DC of ~75% soon after cure, which also showed the highest time-delayed increased one week later (black curve in Fig. 1b), reaching ~94% (see Fig. 4). Thus, spectral measurement repeated on white light exposed resin after one week of storage in ambient light at RT showed still signicant ongoing conversion on that

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Fig. 2

a)c): distributions of particle size (populations by particle number) obtained in IPA (red bars) and in resin co-monomer (green bars), for the particles of: a) glass, b) titania, and c) silica. d)e): images of ller particles drop-cast onto glass slides from IPA: d) AFM of glass particles, and e) SEM of titania particles.

(Fig. 2c) red bars) two populations showed up, centered around ~180 and ~610 nm size, respectively. In order to characterize a system closer to the nal samples, we also carried out DLS of the ller particles dispersed in the resin. Since the 50 wt% ller loaded mixtures were too viscous to be properly poured into the DLS cuvettes, we restricted our measurements to the 10 wt% samples. These results are also included in Fig.2a)c), with size population distributions in green color. The glass particles distribution in the resin (Fig.2a) green bars) showed three peaks, with the intermediate one (~700 nm) well overlapped with the distribution in IPA (red bars), and two more peaks on both the small and large size sides, centered at ~240 and ~2000 nm, respectively. The titania particles distribution in the resin (Fig.2b) green bars) still showed a single population peak same as in IPA, yet signicantly shifted to lower size, centered around ~200 nm. Finally, the silica particles distribution (Fig.2c) green bars) is again partly overlapped with the IPA one, but with the middle shifted towards smaller size. In particular, two peaks at ~9 and ~24 nm appear, showing overall good consistency with the nominal mean particle size of 12 nm. In fact, for those llers without any nominal

reference value for the primary particles size, i.e. titania and glass, additional determination of particle size was also carried out by microscopy. To this goal, the same IPA solutions used for DLS were drop-cast onto glass slides, and the surfaces were imaged. We rst tried AFM, which worked for the relatively larger and more irregular glass particles (see Fig.2d)), whereas for the titania particles it turned out into unstable images, probably due to particle aggregates loosely bound to the substrates and swept during the scan. Therefore for titania we used SEM, after 5 nm platinum coating, (see Fig.2e)). The images showed a general agreement with DLS results in the resin. Indeed, for the glass the presence of mostly submicrometer sized particles is also accompanied by some larger ones (up to 23 m in at least one direction). Similarly, the image of the titania particles shows a primary particle size of 21060 nm (meanstandard deviation), in agreement with the green distribution in Fig.2b). Samples mechanical properties We rst carried out DMA on the bare resin samples, to assess the mechanical properties resulting from the different curing conditions. The respective

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Fig. 3

a) Storage modulus E and b) damping factor tan=E/E of bare resin samples cured in different conditions.

measurements are presented in Fig. 3. In Fig. 3a) the storage modulus E decreases monotonously in all cases, as expected due to the increased uidity of the resin at higher temperatures. The white cured storage modulus curve shows not only the highest values at all temperatures, but also the slowest decrease slope than the other curves. For an easier comparison with DC, the E values at RT have been extracted from Fig. 3a) and plotted again along with the respective DC values in Fig. 4. In Fig. 3b) we decided to plot the damping factor tan=E/E rather than the loss modulus E or the total complex modulus |E*|=(E 2+E 2), as done sometimes in the literature15). In fact, only one out of the three mentioned parameters is independent in addition to E, such that each choice is allowed. However, whereas |E*| is usually quite close to E (being E<<E) and E alone shows maxima that can barely be associated to physical effects in the material, tan=E/E can better account for the shift of behavior from elastic to viscous of the material at the different temperatures. Actually, the maxima observed in the plots of this parameter can be assumed to represent the position of the glass transition temperature Tg for the respective polymer. In Fig. 3b), clearly no maximum appears for the white light cured resin (black line), whereas for the blue cured resin (blue line) only a weak maximum seems to appear close to the upper temperature limit. We then carried out DMA on the composites. It was unfortunately not possible to measure the 50%wt loading sample of silica particles. In fact, these nanoparticles had such a high specic surface area (~200 m2/g, as from manufacturer data sheet) that, in the absence of a solvent or any particle bonding agent coating, it was not possible to mix them properly with the resin paste at the considered high loading limit. In Fig. 5, storage modulus

Fig. 4

Comparison between DC from the FTIR spectra and storage modulus E at RT from the 1 Hz DMA frequency scan in Fig. 3 (blue light curing curve), stressing the possible correlation between the two quantities.

E and damping factor tan are plotted for the successful composites. Data points of composites with the same ller type but different loading have been plotted with same color and symbol shape, yet with void and lled symbol for the lower and higher loading, respectively. From Fig. 5a), it is clear that the titania composites exhibit overall lower elasticity than the glass composites. Also, for the glass composites an increase in modulus is observed on increasing loading, even if of limited extent (approximately +10% over all the temperature range). On the contrary, the titania composites show a marked decrease in modulus on increasing loading, opposite than expected. In Fig. 5a), the curve of 10%wt silica sample shows

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Fig. 5

a) Storage modulus E and b) damping factor tan=E/E of resin composites with different ller materials and loading, when available.

Fig. 6

Flexural (red bars) and compression modulus (green bars) of cured specimens of all considered materials, from left to right: bare resin, and composites with glass, titania and silica llers. The hardness from the nanoindentation experiments (blue bars) is also plotted.

the lowest decreasing slope with increasing temperature. In fact, this curves starts at the lowest temperatures with E values only lower than for the glass composites, and ends at the highest temperatures with higher E than those samples. The cross-point is approximately placed between the RT and the body temperature values. For the damping factor plotted in Fig. 5b), this control information shows again, similarly to the bare resin case (Fig. 3b)), that no glass transition occurs in the considered temperature range. Also in this parameter, describing the amount of viscous character of the material, does the silica composite perform better than the others, as its curve is the most at, showing high thermal stability in the operating temperature range. Again, the glass

composites with different loading are very close to each other (even more than for E in Fig. 5a)). Finally, the results of the nanoindentation analysis are summarized in Fig. 6, where the values of EAFM modulus are compared with the E modulus from DMA, for all the composites. The error bars of the AFM quantities represent one standard deviations of the populations of 302 data-points from the maps of force-distance curves on the respective samples. These error bars are approximately ~24% and ~33% of the respective mean values, for the 50%wt and the 10%wt composites, respectively. In fact, a larger deviation is expected for the low (10%wt) loading composites, where regions of dominating bare resin stiffness effect can be found on the surface more likely than in the average high loading (50%wt) composites. In Fig. 6 bars for the measured hardness H have also been plot, which is an additional information obtained from the Hertz ts. In general, the relative error on HAFM is higher than that on EAFM, due to the higher sensitivity of H to the uncertainty in contact area with respect to E. Additionally, an even higher error is found for both HAFM and EAFM for the low loading composites, where the relative error with respect to the mean is increased from ~32% to ~42%. Overall, the elastic modulus reported in Fig. 6 is in good qualitative agreement with DMA results. Indeed, in both techniques the glass composites show values signicantly higher than the bare resin, and not signicantly different between them, for the two different loadings considered. Also similarly to DMA, the lowest moduli from nanoindentation come from the titania composites. However, whereas in DMA at RT the 10%wt silica composite scores the same as the two glass composites, in nanoindentation it is signicantly higher, and clearly the stiffest composite of all. Additionally, whereas for the bad cured 50%wt titania composite DMA

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polymerization. Independent on the highest DC obtained with the white light exposure, for the curing of the composites we decided to adopt the blue light exposure, such as to follow more closely the conventional photo-curing adopted in normal dental practice. In fact, one more problem appears in the composites due to the llers scattering the light off its original straight path through the organic phase. Actually, this can have two counteracting effects. On one hand, some light exits the specimen and is lost. On the other hand, most light incoming on the llers is not absorbed by them but rather redirected to the locally surrounding matrix, which is also reduced in quantity. Therefore, low loading composites should be cured even faster than bare resin specimens. However, in high loading composites the light could even not reach at all the deepest matrix levels. Overall, we assumed a general compensation of these effects on the considered specimens (thickness ~2 mm), and applied to the composites the same blue irradiation procedure used for the bare resin specimens. Regarding the ller particle size from Fig. 2 it clearly appears that all the average particles in IPA are at maximum of micrometer size. In particular, the ball-milled glass particles stay below that limit, appearing even smaller than the titania particles. On the other hand, for the only particles of known size, i.e. the silica nanoparticles, the apparent size in IPA is much larger than the nominal value. Clearly, some degree of aggregation in suspension is present in IPA at least for silica. When repeating the DLS measurements of the ller particles in the resin medium, obviously, due to the higher viscosity as compared to solvent, the glass particles were less free to move, and a lower degree of both aggregation and sedimentation appears, resulting in the presence of some primary and some very large particles, respectively. For the titania particles, in turn, clearly aggregation was less effective in the resin, and the resulting size can be supposed to be the real primary particle size. Concerning the direct microscopic imaging of the llers, in Fig. 2d)e) we have shown images of bare stand-alone particles only, and not of particles embedded inside the cured composites. However, also given the probably slow reaction rate following the low used irradiance, there is no particular reason why the size of either the primary particles or the particle aggregates should undergo major changes during photocuring with respect to the size found in the DLS measurements in the resin. In Fig. 3a), the white cured sample was the one with the best polymerized resin, which is in agreement with the highest DC value observed (Fig. 4). In fact, the two curves of the blue cured resin in Fig. 3a) present an inversion of ranking when compared with the respective DC (Fig. 4). Indeed, the decrease in DC resulting from the DMA thermal scan did not correspond to a decreased modulus but rather increased it, instead. Obviously, polymer cross-linking is not the only mechanism

showed a modulus even lower than the bare resin, for compressive nanoindentation test the presence of llers makes the resulting modulus higher than the resin even in that negative case. In fact, it is known that for tensile measurement the presence of non-bonded llers can even act as detrimental defect sites, rather than as reinforcing agents16).

DISCUSSION
Current commercial dentist lamps are based on LEDs which present a typical emission light power of ~1,000 mW in the spectral region of 460480 nm wavelength. In common practice two 10 s irradiation cycles of these lamps are used, for maximum 2 mm thick restorations. The lamps are usually placed close to contact (~2 mm) with the dental composite restoration, which has typical diameter of 3 mm and is completely covered by a light spot of approximately the same size, at the specied distance. Therefore, a used irradiance of ~14,000 mW/ cm2 with a total delivered dose surface density of ~280 J/ cm2 can be estimated. The lamp used by us had a power measured in the blue region of ~60 mW at 3 cm distance from the sensor on a circular area of 13 mm diameter. This lamp was the most powerful continuous wave source of blue light available in our laboratory. Alternatively, we could use pulsed lasers with high peak power, borrowed from a spectroscopy laboratory close by, but we suspected that the pulsed irradiation regime could modify the photo-curing process dynamics or chemistry, after heating effects. Therefore, we stuck to our continuous light source and rather extended the irradiation times. The selected times of 105 and 210 min for white and blue light, respectively, were chosen to reach the same dose surface density of the dentists lamp. We assumed 100% absorption of the delivered dose, and a simple exposure reciprocity law between incident irradiance at specimen pinc and exposure time t, pinca t=constant, with a=1. Whereas this assumption can have limited validity in some cases also depending on parameters such as photoinitiator system, ller loading, and desired depth of cure, it can still be considered valid in a rst approximation. In particular on the long time side of this law, it has been shown that there is no minimum irradiance under which no photopolymerization starts13). When discussing the FTIR spectra in Fig. 1 and the respective DC calculated and plotted in Fig. 4, it should be kept in mind that it is not totally clear to what extent thermal effects played a role in the curing, by eventually modifying the reaction path and the resulting material properties. In fact, when exposed to the white light the resin was locally heated above 80C. Similarly, thermal effects also applied in the FTIR measurement repeated after DMA study (magenta curve in Fig. 1b)). In this case, the heating cycle decreased the DC to ~26% (Fig. 4). One possible reason for this effect could be the partial vaporization of water molecules trapped inside the resin, which hinders chain propagation during the

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accounting for the increase in the mechanical properties of the polymer, and thus only specimens processed in exactly the same way should be compared in expected mechanical properties with respect to their DC. In Fig. 3b), the observed minor transition (curve peak) for the blue cured resin (blue line) can partly account for the inversion of E ranking with respect to DC observed in Fig. 4. However, on repeating the temperature scan, this weak maximum disappears (magenta curve). Obviously, the respective transition, if any, was related to orientation of some side groups of the polymer or localized backbone motions (beta transition). Finally, we conclude that no glass transition occurs for the resin in the considered temperature range. When discussing the results in Fig. 5, reporting DMA measurements of the composites, it should be mentioned that the respective DC values were similar for all samples but for the 50%wt titania sample, which showed much lower DC, as low as ~10%. In fact, the 50%wt titania sample also showed direct evidence of incomplete curing as its surface was still gelly and sticky after curing. On the contrary, the other composites were properly hardened and had DC values between 60 and 75%, all higher than bare resin (~57% with blue light), as expected due to the dominating effect of less resin quantity to be cured in the composite for the same dose delivered. In Fig. 5a), the more limited decrease in storage modulus with increasing temperature for the silica samples than for all the other samples may be due to the smallest particle size, which provided better dispersion and higher uniformity of the composite, resulting in less regions of resin only domains. In this way, the decrease in modulus, a peculiarity of the resin matrix, is less pronounced, as the ller is maintaining the modulus at relatively high levels during all the thermal cycle. On the contrary, the glass llers, similar to the titania llers (in the 10%wt sample) exhibit higher plasticizing effect on the resin, probably due to the larger primary particle size. In Fig. 5b), the 10%wt titania sample, despite its high DC (~75% vs 60% and 70% of the glass samples) also shows high viscosity, probably due to some higher ow of the titania particles in the resin with respect to the glass ones, perhaps due to more difcult diffusion of the latter after the higher size. The nal maximum appearing for the 50%wt titania sample is probably associated with secondary effects such as the incomplete curing in case of this sample, as mentioned above. The apparent glass transition is probably due only to a higher uidity of the not polymerized material. From the nanoindentation results, overall the compressive modulus EAFM is approximately twice as much as the exural modulus E, with a highest value of ~5.3 GPa for the nanosilica composite. Whereas this value is still far from the minimum requirement for dental restorative composite of posterior teeth, which can set to ~10 GPa, it can already be considered a good result for the relatively low loading achieved (10%wt, which is less by volume, due to the ller being heavier than the

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resin), in the absence of a bonding agent. In fact, the latter effect can be the reason of a higher modulus found in compressive mode of nanoindentation with respect to exural mode of DMA, where one side of the specimen is under compression as well whereas the opposite side is on the contrary under tension. Actually, it is known that dynamic test mode should result in a higher value of the measured modulus, due to the higher strain rate applied17,18). Indeed, in our nanoindentation, the rate of applied load is such that the maximum load Fmax is reached in half the time period of the force-distance loop. Being the frequency 0.5 Hz and the overall z sweep 1 m, this corresponds to 2 /s. In DMA, on the other hand, the strain rate is such that a cycle with amplitude of 35 m is performed with a frequency of 1 Hz, which means 140 m/s, more than one order of magnitude faster than during indentation. However, in the present experiment, obviously the effect due to the different type of loading scheme dominates, making the AFM moduli always higher than the DMA ones. Usually, llers of glass or other milled material have relatively large size population, spanning at least one order of magnitude (110 m and often 0.110 m), which makes the respective dental restorative materials belong to the class of hybrids. These are normally considered to allow for a better distribution of stress, and increase strength and toughness and eventually elastic modulus1). However, in our case the ball-milling provided rather narrow particle size distribution (31% of the mean, as from Fig. 2a)). This was also indirectly conrmed by the AFM nanoindentation measurements, which found monomodal distributions of material stiffness (i.e. uniform composites) even at the low loading of 10%wt. Between the composites with silica and titania llers, one could expect a higher modulus for the titania ones, due to the crystalline phase of the particles. However, obviously, at the 10% loading the mostly probed character of the composite is still assigned to the resin matrix more than the ller particles. On the other hand, at 50% the titania sample could not be properly cured, due to the high reectance of the titania, which is well known for its use as a white pigment in paints. In fact, previous investigations of titania lled composites used thermal curing instead of photo-curing19). Indeed, the crystalline titania composite with 50%wt loading as measured by DMA showed elastic modulus even lower than the bare resin. Finally, when comparing composites of different ller materials as in the present case, it should be considered that additional effects also arise from the different effective values of loading by volume. In fact, the densities of the various ller materials are rather different: 2.6 g/ cm3 for silica and 3.9 g/cm3 for titania, according to the manufacturers data sheets, and 1.1 g/cm3 and 2.4 g/cm3 for bare resin and glass, as determined by us by weighting and differential volumetric measurements of water in graduated cylinders. Therefore, 10%wt corresponds to volume loadings of 4.7, 4.4 and 2.7% for glass, silica and titania, respectively, whereas 50%wt corresponds

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5) Han L, Ishizaki H, Fukushima M, Okiji T. Morphological analysis of owable resins after long-term storage or surface polishing with a mini-brush. Dent Mater J 2009; 28: 277284. 6) Salerno M, Derchi G, Thorat S, Ceseracciu L, Ruflli R, Barone A. Surface morphology and mechanical properties of new-generation owable resin composites for dental restoration. Dent Mater 2011; 27: 1221-1228. 7) Chen X, and Mao SS. Titanium dioxide nanomaterials: synthesis, properties, modications, and applications. Chem Rev 2007; 107: 2891-2959. 8) Pignatelli F, Carzino R, Salerno M, Scotto M, Canale C, Distaso M, Rizzi F, Caputo G, Cozzoli PD, Cingolani R, Athanassiou A. Directional enhancement of refractive index and tunable wettability of polymeric coatings due to preferential dispersion of colloidal TiO2 nanorods towards their surface. Thin Solid Films 2010; 518: 4425-4431. 9) Bowen RL. Use of epoxy resins in restorative materials. J Dent Res 1956; 35: 360-369. 10) Kurachi C, Tuboy AM, Magalhaes DV, Bagnato VS. Hardness evaluation of a dental composite polymerized with experimental LED-based devices. Dental Mater 2001; 17: 309-315. 11) Silva Soares LE, Martin AA, Barbosa Pinheiro AL, Pacheco MTT. Vickers hardness and Raman spectroscopy evaluation of a dental composite cured by an argon laser and a halogen lamp. J Biomed Opt 2004; 9: 601-608. 12) Hosseinalipour M, Javadpour J, Rezaie H, Dadras T, Hayati AN. Investigation of mechanical properties of experimental Bis-GMA/TEGDMA dental composite resins containing various mass fractions of silica nanoparticles. J Prosthod 2010; 19:112-117. 13) Musanje L, Darvell BW. Polymerization of resin composite restorative materials: exposure reciprocity. Dent Mater 2003; 19: 531-541. 14) Rueggeberg FA, Hashinger DT, Fairhurst CW. Calibration of FTIR conversion analysis of contemporary dental resin composites. Dent Mater 1990; 6: 241-249. 15) Ryou H, Niu L-N, Dai L, Pucci CR, Arola AA, Pashley DH, Tay FR. Effect of biomimetic remineralization on the dynamic nanomechanical properties of dentin hybrid layers. J Dent Res 2011; 90: 1122-1128. 16) Darvell BW. In: Darvell BW, editor. Materials science for dentistry. 9th ed. Sawston, Cambridge: Woodhead Publishing Limited; 2011. 17) Braem M, Davidson CL, Vanherle G, Van Doren V, Lambrechts P. The relationship between test methodology and elastic behavior of composites. J Dent Res 1986; 66: 1036-1039. 18) Jacobsen PH, Darr AH. Static and dynamic moduli of composite restorative materials. J Oral Rehabil 1997; 24: 265-273. 19) Yoshida K, Taira Y, Atsuta M. Properties of opaque resin composite containing coated and silanized Titanium dioxide. J Dent Res 2001; 80: 864-868. 20) Patra N, Salerno M, Diaspro A, Athanassiou A. Effect of solvents on the dynamic viscoelastic behavior of poly(methyl methacrylate) lm prepared by solvent casting. J Mater Sci 2011; 46: 5044-5049.

to 31, 29 and 20% for the same sequence of materials. This calculation is made according to nominal densities of bulk materials. However, the volume loading of our nanosilica was obviously much higher, due to its uffy form, probably around 20% already for the 10%wt sample and above 90% for the 50%wt sample, which could not be made at all. One way to overcome this problem could be using surfactant coated nanosilica, or suspend it in a solvent also good for the resin phase, before mixing everything together. However, this method will probably raise other questions, regarding the solvent effects20).

CONCLUSION
After identifying the most appropriate conditions for light curing our resin matrix, we carried out DMA characterization of bonding-agent free composites with different ller materials under exural stress, and compared it to static nanoindentation carried out by AFM. The elastic modulus of the composites was always improved or at least remained the same as the bare resin in all compression tests. In exural tests the elastic modulus was always lower than the compression test values, and even decreased with respect to bare resin in the 50%wt titania sample. Additionally, in glass composite no increase in elastic modulus was observed on increase of loading from 10 to 50%wt. In compression, which is in many cases the most important loading mode of dental restoration materials, the highest modulus was observed for the nanosilica ller, even if in 10%wt loading only, corresponding in turn to ~4.4%vol. In this case, an elastic modulus as high as 5.31.6 GPa was found. Additionally, no thermal transitions were observed at the investigated temperatures for any material, showing good stability at operating conditions. Titania llers could be of interest in future applications where their photocatalytic effect could be useful to promote local antibacterial or remineralization reactions.

REFERENCES
1) Chen M-H. Update on Dental Nanocomposites. J Dent Res 2010; 89; 549-560. 2) Uskokovi V, Bertassoni LE. Nanotechnology in dental sciences: moving towards a ner way of doing dentistry. Materials 2010; 3: 1674-1691. 3) Sharma S, Cross SE, Hsueh C, Wali RP, Stieg AZ, Gimzewski JK. Nanocharacterization in Dentistry. Int J Mol Sci 2010; 11: 2523-2545. 4) Wahl MJ. AmalgamResurrection and redemption. Part 1: the clinical and legal mythology of anti-amalgam. Quintessence Int 2001; 32: 525-535.