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Preparation and characterization of a BisGMA-resin dental restorative composites with glass, silica and titania ﬁllers
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: email@example.com
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 (25°C) 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 ﬁllers, Dynamic mechanical analysis, Nanoindentation, Elastic modulus
The ﬁeld 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 ﬂowable 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 ﬁller-matrix bonding agent, and within this limitation we studied the effect of different ﬁller particle materials on the respective elastic properties. Three different types of ﬁllers 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 ﬁller 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 bioﬁlm 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 ﬂexural strength and fracture toughness. However, indentation only reports about the response to compressive stress, whereas ﬂexural 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 ﬁgures 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
Germany). as to the sufﬁcient optical density required for a good statistical analysis. The irradiance of this lamp was evaluated in comparison with other light sources used in both literature and recent clinical practice10-12). The third type of ﬁllers used was ball-milled glass. after drying the IPA suspension of ball-milled glass the ﬁller particles were measured again in DLS upon mixing them into the resin. we selected a X-Cite 120 lamp (EXFO. ﬁlled with 100 g of glass and zirconia balls. The suspension was then poured into a previously weighted glass beaker. The overall system was blended again by spatulation for additional 3 min. Also. for each suspension 3 series of 3 measurements each were repeated and averaged. consisting in camphorquinone (CQ) as a photoinitiator and dimethyl amino ethyl methacrylate (DMAEMA) as an amine reducing agent.3 mm3. We used 30 balls of 5 mm diameter together with 60 balls of 3 mm diameter. The ball-miller used was a PM100 (Retsch. 31(4): 635–644 sticking to the jar bottom. and are crystalline in character (anatase). the particle size of each ﬁller material was ﬁrst measured by dynamic light scattering (DLS) in IPA suspensions. The former is the traditional resin monomer used in dental restorative composites since more than half a century9). and then moved on to a more diluted suspension of the same material. The latter is one among several monomers usually mixed with BisGMA to make the paste more ﬂuid and handy during manipulation (viscosity decreasing co-monomer)1). Since the mixtures had to be manipulated in the light for several minutes. which was placed at a distance of ~3 cm from the specimens to be cured. USA). and ‘as collected’ material from the ball-milled glass). with ~95% transmittance at a 455– 490 nm wavelength pass band. similarly to the commercial particles. and are amorphous in character. 718483 and 232033. The system was carefully blended by spatulation for 3 min. CQ and DMAEMA were added in 1:1 weight ratio. After drying. As a result of this step. which were applied starting from the central region ﬁrst and moving to the two side regions later on. After milling. microscopic imaging was also used to further assess the size of bare primary particles and particle aggregates. The missing CQ-DMAEMA part should not affect signiﬁcantly the rheology of the system. Filler materials Two of the three types of ﬁllers used were commercial materials. optical microscopy specimen coverslips were used (Menzel-Gläser. for a total milling time of 5 h. For the source. for these measurements we used BisGMA and TEGDMA only without photopolymerizing system (CQ-DMAEMA). on which MATERIALS AND METHODS Resin matrix 2. these slides are so thin that it was possible to load them directly into the ball-miller jar without preliminary fragmentation. These coverslips are made of borosilicate glass (D 263 M type. Since CQ has a peak of light absorbance at 470 nm wavelength. and placed in a bell rest chamber pumped to low vacuum (~100 mbar) to remove air bubbles formed during spatulation. The paste was then poured into a clean antisticking mold of Teﬂon. The titania particles are described as ‘powder’ without any size speciﬁcation. the hot jar (~80°C) was let to cool down to room temperature (RT) in place. This lamp is a high output power white light source with a broad smooth spectrum. namely silica and titania particles (Sigma-Aldrich products no. Italy). but these could be easily broken down into ﬁne powder by simply touching them with steel tweezers. Finally. In case of ﬁller loading. and the system was spatulated again for up to additional 15 min for the highest loading cases.5% wt of the total co-monomer. the respective particles were added in 10 or 50% wt proportion of the overall organic matrix paste. We went on with dilution until the measurement quality resulting from the instrument report remained acceptable. polystyrene cuvettes were used in a Nano-ZS setup (Malvern Instruments.5 wt% of the co-monomer). a ﬁlter was taken from a ﬂuorescence cube GFP (Semrock. due to the low percentage (0. the intensity of various light sources available in our laboratory was preliminary measured with a power meter Nova II (Ophir. The milling was carried out in 20 mL isopropanol (IPA. respectively). Germany). For selection of the most appropriate photo-curing lamp. In addition to DLS measurements in IPA. Photo-curing conditions The elongated beam shape of the specimens (see Dyamic mechanical analysis for the size) required three irradiation cycles for each specimen. the glass appeared to be agglomerated in large plates . The silica particles are described as ‘nanopowder’ with average diameter of 12 nm. normally used for optical microscopy imaging of specimens stained with ﬂuorescent dyes. All products were supplied by Sigma-Aldrich (Milan.636 Dent Mater J 2012. which efﬁciently starts the polymerization reaction after ampliﬁcation by the electrons extracted from DMAEMA. and was let to dry in an oven at 90°C for 4 h. Sigma-Aldrich) at a rotating speed of 450 RPM. To this goal.2′-bis[4-3-(methacryloxy-2-hydroxy-propoxy)-phenyl]propane (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) were mixed in 7:3 ratio by weight. Germany). decreasing the concentration to 50% at each step. Schott AG. To this goal. we measured both the full spectrum power (‘white light’) and the power at a selected blue region window only (‘blue light’). We started from concentrated IPA suspensions (~5 g/L for the commercial powders. USA). Despite the large planar dimensions. such that their total amount was 0. before opening it. In order to compare the commercial nanosilica and titania powders with the glass ball-milled in IPA. UK). operated with a 50 mL zirconia jar. Canada). It was thus possible to mix this powder thoroughly with the resin paste. of size 20×20×0. The co-monomer mixture was further added with the photopolymerization system. with alternating cycles of 1 min clockwise and 1 min counterclockwise rotation without resting time.
made each of a cantilever with nominal spring constant and resonance frequency of ~60 N/m and ~450 kHz.g.000 cm–1. both offsets of indentation and force were let to ﬁt automatically by the AFM software within a broad range of forces. and of a terminal transverse pyramidal tip with apex diameter and full aperture angle of ~20 nm and ~22°. tip elastic modulus. actual contact point (δ. For optimal signal-to-noise ratio. which showed evidence of the presence of ﬁllers in the composites. the same values of the remaining working parameters were used later also for the composites. Temperature sweeps at strain frequency of 1 Hz were carried out. in a range of +2 to +62°C (with 5°C steps. After acquisition. In particular. Clearly. 50 scans were averaged per sample spectrum. In Fig.874 cm–1 (symmetric stretching of CH3) and 1. During the temperature scans both the storage modulus E′ and the loss modulus E″ were recorded. AFM nanoindentation The same samples as prepared for the DMA were used. low enough to minimize viscous drag effects. respectively. when ingesting from hot food to icy drinks.350–3.550 cm–1 band (OH stretching) is slightly depressed. with 30 μm scan size and 2562 pixels). with an aperture diameter of 3 mm and a spectral resolution of 4 cm–1. respectively. We performed nanoindentation by means of an AFM used in so-called ‘force spectroscopy’ mode. RESULTS Resin curing evaluation In Fig. such that they could be properly investigated by nanoindentation at the considered low indentations δ (up to limited maximum values of δmax~100 nm only). with spatial map sampling of 302 pixels. All the spectra were baseline-corrected by third order polynomial and were normalized thereafter.126 cm–1 (symmetric vibration of -C-O-C-) of TEGDMA increasing the adjacent shoulders of BisGMA. 0)). The 3.024 datapoints. USA). In fact. F)=(0. (data not shown). occasionally AFM imaging was carried out with the same probe (in Tapping mode. all the composite samples were still ﬂat and smooth enough at the surface. with some features. under strain control in the materials linear regime. since it should represent well the limit values occurring in human mouth in normal operating conditions. The FTIR spectra were acquired by a Vertex 70 spectrometer (Bruker. The interferograms were corrected using a zero-ﬁlling factor of 2. Given the high number of parameters in the Hertz model. the indentation was calculated from the z movement of the actuator ∆z and from the change in cantilever deﬂection ∆D (partially compensating the former) as δ=∆z–∆D. representing the in-phase (real) and out-of-phase (imaginary) parts of a complex modulus E*=E′+iE″. the force-distance curves were acquired in water to remove the effect of aspeciﬁc tip-surface adhesion due to ambient moisture. such that for this the compression modulus EAFM resulting from nanoindentation was equal to the respective ﬂexural modulus E′ resulting from the DMA experiments. as determined by a prior calibration in static loading mode. both soon after pouring the paste into the Teﬂon molds and after its irradiation. We carried out DMA measurements in single-cantilever mode. Fourier transformed infrared spectroscopy In order to verify the conversion of the co-monomer paste into a polymerized resin. both individually and blended in the resulting mixture (red line). occurring due to the stress lagging behind the applied strain with some phase angle delay. The force-indentation data were ﬁnally ﬁt to the Hertz model of elastic contact.771 cm–1 (N(CH3)2 band) and of CQ at 1.5 Hz frequency. sample and tip materials Poisson’s ratios. We used a MFP-3D AFM (Asylum Research. with z actuation loops of 1 μm range and 0. Fourier transformed infrared spectroscopy (FTIR) was carried out for all the specimens at RT in ambient air. which methods were both tested for curing the bare resin. Additionally. the peaks at 2.000). such as to minimize the deviations between ﬁtting curve and data-points (reduced χ2≤1. respectively. in the range of 400–4. The maximum applied strain was ±35 μm.Dent Mater J 2012. BisGMA and TEGDMA dominate the spectrum of the mixture. such as e. 25%–75% of Fmax. The curves had 1. The samples were analyzed in attenuated total reﬂection conﬁguration. Russia). For reaching the lowest temperatures in this range. The peaks of DMAEMA at 2.637 and 1. collecting force-distance curves on given specimen sites. USA). and apodized by applying the Blackman-Harris 3-term correction function for the Fourier transformation.580 cm–1 is observed. and again in de-ionized water for determination of the appropriate optical lever sensitivity.747 cm–1 (C=O vibration) do not appear in the mixture. USA) equipped with gold coated silicon probes NSG20 (NT-MDT. Dynamic mechanical analysis All the materials were shaped with the Teﬂon mold to be rectangular beams of 13×35×2 mm3 in size. the effect of photo-curing is reported. 1a) the FTIR spectra of the uncured components of the organic paste are presented.e. as compared to the bare resin surface (data not shown). 31(4): 635–644 basis we decided to set our irradiation time to 105 and 210 min for ‘white’ and ‘blue’ light. 5°C/min rate). due to the low relative contribution of the respective components. After this initial setup. The AFM probe was calibrated in 637 air for determination of the cantilever spring constant. respectively. with . 1b). However. i. liquid nitrogen was used as a coolant. using the unload part of the force loop to ﬁnd the elastic modulus values EAFM. The typical lateral scan size was 5 μm. with instrument compliance of less than 0. before carrying out the respective tests. the remaining parameters were adjusted on the bare resin reference material. Preliminary to the AFM nanoindentation experiments. On these samples we performed dynamic mechanical analysis (DMA) by means of a Q800 setup (TA Instruments. (indenting tip size and shape. a signiﬁcant change in the bands centered around 1.2 μm/N.
which also showed the highest time-delayed increased one week later (black curve in Fig. 2a)–c). red) and after irradiation. according to a peak intensity method14): DC = 100 [ 1 (I1637 / I1580) pol (I1637 / I1580) mon ] (1) time scale. This condition (gray curve in Fig. 4). 1 applied to the spectra in Fig. 4). a relative increase of the second one.e. In fact. corresponding to the stretching of the aliphatic and aromatic (i.638 Dent Mater J 2012. no further change was observed. according to different conditions. +11%. CQ and DMAEMA.e. which was ﬁrst applied on suspensions of the respective powder in IPA. for all materials the apparent average particle size had decreased. as well as of the (uncured) mixture of the same compounds (red line). The adopted method of progressively more diluted suspension should minimize the effect of agglomeration. The ﬁnal distributions of particles size in IPA are shown in red in Fig. it turns out that the highest conversion is found for ‘white’ light curing (see Fig. 1 a) FTIR spectra of individual BisGMA. In fact. b) FTIR spectra of the resin mixture before (uncured. after 3 to 5 dilution steps. TEGDMA. spectral measurement repeated on ‘white’ light exposed resin after one week of storage in ambient light at RT showed still signiﬁcant ongoing conversion on that . reaching either a more stable value or the limit of lowest acceptable measurement quality mentioned above. and also showed lesser improvement at one week time (~63%. only reached ~57% soon after curing (Fig. The apparent mean particle size in IPA is ~650 nm for glass (Fig. respectively. (+25% in DC). 1b). and the subscripts outside the parentheses refer to the spectra before (‘mon’) and after (‘pol’) photo-curing. 1b)). 4). Filler size characterization The apparent size of the ﬁller particles was determined by means of DLS. 1b)) provided a DC of ~75% soon after cure. 31(4): 635–644 Fig. allowing for a determination of particle size as close as possible to the primary particles. respectively. when repeated again after one month since irradiation. 2b) red bars). respectively. From eq. i. reaching ~94% (see Fig. as a measure of photo-polymerization. 2a) red bars) and ~950 nm for titania (Fig. curve not shown). the degree of conversion (DC) of the monomer mixture into the polymer (photo-cured mixture) can be evaluated from the following equation. 1b). The ‘blue’ exposed resin. However. Thus. For silica where I1637 and I1580 are the peak intensities of the bands at the respective wavenumber positions. showing no effect of possible absorbance of moisture or other ambient contaminants. on the contrary (blue curve in Fig. ring) C=C bonds.
additional determination of particle size was also carried out by microscopy. (Fig.2d)). Indeed. for the glass the presence of mostly submicrometer sized particles is also accompanied by some larger ones (up to 2÷3 μm in at least one direction). The titania particles distribution in the resin (Fig.2b) green bars) still showed a single population peak same as in IPA. centered around ~200 nm. and two more peaks on both the small and large size sides. the silica particles distribution (Fig. centered around ~180 and ~610 nm size.2a) green bars) showed three peaks. (see Fig. and the surfaces were imaged. Similarly. with size population distributions in green color. Samples mechanical properties We ﬁrst carried out DMA on the bare resin samples. We ﬁrst tried AFM.2c) green bars) is again partly overlapped with the IPA one.2b). we also carried out DLS of the ﬁller particles dispersed in the resin. two peaks at ~9 and ~24 nm appear.2e)). the image of the titania particles shows a primary particle size of 210±60 nm (mean±standard deviation). titania and glass.2a)–c). and c) silica. and e) SEM of titania particles. To this goal. showing overall good consistency with the nominal mean particle size of 12 nm. 2c) red bars) two populations showed up. yet signiﬁcantly shifted to lower size. b) titania. Finally.Dent Mater J 2012. These results are also included in Fig. The respective . Therefore for titania we used SEM. The images showed a general agreement with DLS results in the resin. probably due to particle aggregates loosely bound to the substrates and swept during the scan. the same IPA solutions used for DLS were drop-cast onto glass slides. we restricted our measurements to the 10 wt% samples. to assess the mechanical properties resulting from the different curing conditions. Since the 50 wt% ﬁller loaded mixtures were too viscous to be properly poured into the DLS cuvettes. in agreement with the green distribution in Fig. 2 a)–c): distributions of particle size (populations by particle number) obtained in IPA (red bars) and in resin co-monomer (green bars). i. with the intermediate one (~700 nm) well overlapped with the distribution in IPA (red bars). centered at ~240 and ~2000 nm. In fact. In particular.e. In order to characterize a system closer to the ﬁnal samples. whereas for the titania particles it turned out into unstable images. respectively. The glass particles distribution in the resin (Fig. for those ﬁllers without any nominal reference value for the primary particles size. for the particles of: a) glass. 31(4): 635–644 639 Fig. which worked for the relatively larger and more irregular glass particles (see Fig. respectively. after 5 nm platinum coating. d)–e): images of ﬁller particles drop-cast onto glass slides from IPA: d) AFM of glass particles. but with the middle shifted towards smaller size.
Actually. 3b) we decided to plot the damping factor tanδ=E″/E′ rather than the loss modulus E″ or the total complex modulus |E*|=√(E′ 2+E″ 2). respectively. in the absence of a solvent or any particle bonding agent coating. yet with void and ﬁlled symbol for the lower and higher loading. It was unfortunately not possible to measure the 50%wt loading sample of silica particles. 4. the E′ values at RT have been extracted from Fig. From Fig. tanδ=E″/E′ can better account for the shift of behavior from elastic to viscous of the material at the different temperatures. it was not possible to mix them properly with the resin paste at the considered high loading limit. In Fig. In Fig. In fact. only one out of the three mentioned parameters is independent in addition to E′. but also the slowest decrease slope than the other curves. 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. However. In Fig. 3b).640 Dent Mater J 2012. E′ and damping factor tanδ are plotted for the successful composites. storage modulus Fig. such that each choice is allowed. as from manufacturer data sheet) that. Data points of composites with the same ﬁller type but different loading have been plotted with same color and symbol shape. On the contrary. the curve of 10%wt silica sample shows . as expected due to the increased ﬂuidity of the resin at higher temperatures. measurements are presented in Fig. 3a) the storage modulus E′ decreases monotonously in all cases. these nanoparticles had such a high speciﬁc surface area (~200 m2/g. 5. 3. opposite than expected. In fact. even if of limited extent (approximately +10% over all the temperature range). 3 (‘blue’ light curing curve). as done sometimes in the literature15). whereas for the ‘blue’ cured resin (blue line) only a weak maximum seems to appear close to the upper temperature limit. 31(4): 635–644 Fig. For an easier comparison with DC. 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. The ‘white’ cured storage modulus curve shows not only the highest values at all temperatures. In Fig. stressing the possible correlation between the two quantities. We then carried out DMA on the composites. In Fig. clearly no maximum appears for the ‘white’ light cured resin (black line). Also. 5a). 3 a) Storage modulus E′ and b) damping factor tanδ=E″/E′ of bare resin samples cured in different conditions. the titania composites show a marked decrease in modulus on increasing loading. 4 Comparison between DC from the FTIR spectra and storage modulus E′ at RT from the 1 Hz DMA frequency scan in Fig. it is clear that the titania composites exhibit overall lower elasticity than the glass composites. 3a) and plotted again along with the respective DC values in Fig. 5a). for the glass composites an increase in modulus is observed on increasing loading.
this control information shows again. whereas in DMA at RT the 10%wt silica composite scores the same as the two glass composites. and not signiﬁcantly different between them. as its curve is the most ﬂat. where the relative error with respect to the mean is increased from ~32% to ~42%. 5b). from left to right: bare resin. respectively. due to the higher sensitivity of H to the uncertainty in contact area with respect to E. Additionally. The hardness from the nanoindentation experiments (blue bars) is also plotted. Also in this parameter. Finally. describing the amount of viscous character of the material. the lowest decreasing slope with increasing temperature. in nanoindentation it is signiﬁcantly higher. Additionally. 6 is in good qualitative agreement with DMA results. Indeed. Again. this curves starts at the lowest temperatures with E′ values only lower than for the glass composites. In fact. a larger deviation is expected for the low (10%wt) loading composites. For the damping factor plotted in Fig. and ends at the highest temperatures with higher E′ than those samples. 5a)). 31(4): 635–644 641 Fig. showing high thermal stability in the operating temperature range. that no glass transition occurs in the considered temperature range. Overall. The cross-point is approximately placed between the RT and the body temperature values. for all the composites. the lowest moduli from nanoindentation come from the titania composites. the relative error on HAFM is higher than that on EAFM. does the silica composite perform better than the others. the elastic modulus reported in Fig. whereas for the bad cured 50%wt titania composite DMA . when available. 3b)). the results of the nanoindentation analysis are summarized in Fig. and composites with glass. 6 bars for the measured hardness H have also been plot. for the 50%wt and the 10%wt composites. Fig.Dent Mater J 2012. Also similarly to DMA. 6. 6 Flexural (red bars) and compression modulus (green bars) of cured specimens of all considered materials. However. 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. 5 a) Storage modulus E′ and b) damping factor tanδ=E″/E′ of resin composites with different ﬁller materials and loading. an even higher error is found for both HAFM and EAFM for the low loading composites. and clearly the stiffest composite of all. in both techniques the glass composites show values signiﬁcantly higher than the bare resin. In general. 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. where the values of EAFM modulus are compared with the E′ modulus from DMA. similarly to the bare resin case (Fig. for the two different loadings considered. These error bars are approximately ~24% and ~33% of the respective mean values. the glass composites with different loading are very close to each other (even more than for E′ in Fig. titania and silica ﬁllers. which is an additional information obtained from the Hertz ﬁts. In fact.
but we suspected that the pulsed irradiation regime could modify the photo-curing process dynamics or chemistry. polymer cross-linking is not the only mechanism showed a modulus even lower than the bare resin. 1 and the respective DC calculated and plotted in Fig. Actually. respectively. in Fig. and a simple exposure reciprocity law between incident irradiance at specimen pinc and exposure time t. with a=1. we stuck to our continuous light source and rather extended the irradiation times. the ball-milled glass particles stay below that limit. borrowed from a spectroscopy laboratory close by. for maximum 2 mm thick restorations. resulting in the presence of some primary and some very large particles. the decrease in DC resulting from the DMA thermal scan did not correspond to a decreased modulus but rather increased it. in high loading composites the light could even not reach at all the deepest matrix levels. the heating cycle decreased the DC to ~26% (Fig. which is also reduced in quantity. for the only particles of known size. the silica nanoparticles. this can have two counteracting effects. pinca t=constant. One possible reason for this effect could be the partial vaporization of water molecules trapped inside the resin. This lamp was the most powerful continuous wave source of blue light available in our laboratory. instead. such as to follow more closely the conventional photo-curing adopted in normal dental practice. we could use pulsed lasers with high peak power. for compressive nanoindentation test the presence of ﬁllers makes the resulting modulus higher than the resin even in that negative case. Therefore. Concerning the direct microscopic imaging of the ﬁllers. 4). 4). Similarly. which is in agreement with the highest DC value observed (Fig. Therefore. 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. at the speciﬁed distance. Clearly. for the curing of the composites we decided to adopt the ‘blue’ light exposure. we assumed a general compensation of these effects on the considered specimens (thickness ~2 mm). The lamps are usually placed close to contact (~2 mm) with the dental composite restoration. On the other hand. DISCUSSION Current commercial dentist lamps are based on LEDs which present a typical emission light power of ~1. some light exits the specimen and is lost. 3a) present an inversion of ranking when compared with the respective DC (Fig. However.000 mW/ cm2 with a total delivered dose surface density of ~280 J/ cm2 can be estimated. 31(4): 635–644 polymerization. in turn. In particular on the long time side of this law. the ‘white’ cured sample was the one with the best polymerized resin. Therefore.e. 3a). the glass particles were less free to move. Independent on the highest DC obtained with the ‘white’ light exposure.000 mW in the spectral region of 460–480 nm wavelength. low loading composites should be cured even faster than bare resin specimens. Overall. thermal effects also applied in the FTIR measurement repeated after DMA study (magenta curve in Fig. In particular. were chosen to reach the same dose surface density of the dentists lamp. and applied to the composites the same ‘blue’ irradiation procedure used for the bare resin specimens. the two curves of the ‘blue’ cured resin in Fig. We assumed 100% absorption of the delivered dose. by eventually modifying the reaction path and the resulting material properties. In fact. and the resulting size can be supposed to be the real primary particle size. 1b)). clearly aggregation was less effective in the resin. which hinders chain propagation during the . Indeed. The selected times of 105 and 210 min for ‘white’ and ‘blue’ light. However. when exposed to the white light the resin was locally heated above 80°C. In fact.642 Dent Mater J 2012. In common practice two 10 s irradiation cycles of these lamps are used. 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. 2d)–e) we have shown images of bare stand-alone particles only. some degree of aggregation in suspension is present in IPA at least for silica. it can still be considered valid in a ﬁrst approximation. which has typical diameter of 3 mm and is completely covered by a light spot of approximately the same size. appearing even smaller than the titania particles. the apparent size in IPA is much larger than the nominal value. Whereas this assumption can have limited validity in some cases also depending on parameters such as photoinitiator system. Regarding the ﬁller particle size from Fig. and a lower degree of both aggregation and sedimentation appears. after heating effects. and not of particles embedded inside the cured composites. 4). On the other hand. 4. In fact. one more problem appears in the composites due to the ﬁllers scattering the light off its original straight path through the organic phase. due to the higher viscosity as compared to solvent. When discussing the FTIR spectra in Fig. Alternatively. a used irradiance of ~14. rather than as reinforcing agents16). In this case. it has been shown that there is no minimum irradiance under which no photopolymerization starts13). i. Obviously. In Fig. and desired depth of cure. respectively. most light incoming on the ﬁllers is not absorbed by them but rather redirected to the locally surrounding matrix. In fact. it should be kept in mind that it is not totally clear to what extent thermal effects played a role in the curing. 2 it clearly appears that all the average particles in IPA are at maximum of micrometer size. For the titania particles. obviously. ﬁller loading. When repeating the DLS measurements of the ﬁller particles in the resin medium. also given the probably slow reaction rate following the low used irradiance. it is known that for tensile measurement the presence of non-bonded ﬁllers can even act as detrimental defect sites. On one hand.
which is less by volume. the respective transition.4 and 2. However. In Fig. Obviously.7% for glass. reporting DMA measurements of the composites. These are normally considered to allow for a better distribution of stress. However. as low as ~10%. where one side of the specimen is under compression as well whereas the opposite side is on the contrary under tension. the rate of applied load is such that the maximum load Fmax is reached in half the time period of the force-distance loop. From the nanoindentation results. 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 g/cm3 for bare resin and glass. In fact.18). this weak maximum disappears (magenta curve).Dent Mater J 2012. it can already be considered a good result for the relatively low loading achieved (10%wt. ﬁllers of glass or other milled material have relatively large size population.e. one could expect a higher modulus for the titania ones. Actually. the strain rate is such that a cycle with amplitude of 35 μm is performed with a frequency of 1 Hz. In Fig.7. 10%wt corresponds to volume loadings of 4. 4. 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 makes the respective dental restorative materials belong to the class of ‘hybrids’.9 g/cm3 for titania. similar to the titania ﬁllers (in the 10%wt sample) exhibit higher plasticizing effect on the resin. The ﬁnal maximum appearing for the 50%wt titania sample is probably associated with secondary effects such as the incomplete curing in case of this sample. which showed much lower DC. making the AFM moduli always higher than the DMA ones. at the 10% loading the mostly probed character of the composite is still assigned to the resin matrix more than the ﬁller particles. Finally. On the other hand. uniform composites) even at the low loading of 10%wt. Whereas this value is still far from the minimum requirement for dental restorative composite of posterior teeth. the latter effect can be the reason of a higher modulus found in compressive mode of nanoindentation with respect to ﬂexural mode of DMA. 5a). in our case the ball-milling provided rather narrow particle size distribution (±31% of the mean. the glass ﬁllers. and thus only specimens processed in exactly the same way should be compared in expected mechanical properties with respect to their DC. overall the compressive modulus EAFM is approximately twice as much as the ﬂexural modulus E′. In Fig. all higher than bare resin (~57% with ‘blue’ light). Being the frequency 0. 5. in the present experiment. 31(4): 635–644 accounting for the increase in the mechanical properties of the polymer. as from Fig. obviously. on repeating the temperature scan. with a highest value of ~5. due to the crystalline phase of the particles. perhaps due to more difﬁcult diffusion of the latter after the higher size. When discussing the results in Fig. at 50% the titania sample could not be properly cured. The apparent glass transition is probably due only to a higher ﬂuidity of the not polymerized material. probably due to some higher ﬂow of the titania particles in the resin with respect to the glass ones. in our nanoindentation. due to the higher strain rate applied17. it should be considered that additional effects also arise from the different effective values of loading by volume. In fact.1 g/cm3 and 2. the crystalline titania composite with 50%wt loading as measured by DMA showed elastic modulus even lower than the bare resin. However. when comparing composites of different ﬁller materials as in the present case. On the contrary. In fact. In fact. silica and titania. as determined by us by weighting and differential volumetric measurements of water in graduated cylinders. Between the composites with silica and titania ﬁllers. which is well known for its use as a white pigment in paints. and 1. due to the ﬁller being heavier than the 643 resin). the other composites were properly hardened and had DC values between 60 and 75%. as the ﬁller is maintaining the modulus at relatively high levels during all the thermal cycle. Finally. is less pronounced.3 GPa for the nanosilica composite. 4. 2a)). Indeed. Indeed. respectively. which provided better dispersion and higher uniformity of the composite. Usually. the 50%wt titania sample also showed direct evidence of incomplete curing as its surface was still gelly and sticky after curing. more than one order of magnitude faster than during indentation. it should be mentioned that the respective DC values were similar for all samples but for the 50%wt titania sample. despite its high DC (~75% vs 60% and 70% of the glass samples) also shows high viscosity. due to the high reﬂectance of the titania. and increase strength and toughness and eventually elastic modulus1). it is known that dynamic test mode should result in a higher value of the measured modulus. In DMA. previous investigations of titania ﬁlled composites used thermal curing instead of photo-curing19). was related to orientation of some side groups of the polymer or localized backbone motions (beta transition). which can set to ~10 GPa. the 10%wt titania sample. on the other hand. 3b). if any. 5b). as mentioned above. This was also indirectly conﬁrmed by the AFM nanoindentation measurements. a peculiarity of the resin matrix. the densities of the various ﬁller materials are rather different: 2. we conclude that no glass transition occurs for the resin in the considered temperature range.1–10 μm). resulting in less regions of resin only domains. in the absence of a bonding agent. which means 140 μm/s. which found monomodal distributions of material stiffness (i.5 Hz and the overall z sweep 1 μm. Therefore. obviously the effect due to the different type of loading scheme dominates. probably due to the larger primary particle size. whereas 50%wt corresponds . as expected due to the dominating effect of less resin quantity to be cured in the composite for the same dose delivered. this corresponds to 2 μ/s. according to the manufacturers’ data sheets. On the contrary. spanning at least one order of magnitude (1–10 μm and often 0. the decrease in modulus.6 g/ cm3 for silica and 3. In this way. However.
and Mao SS. even if in 10%wt loading only. Barone A. Stieg AZ. 14) Rueggeberg FA. showing good stability at operating conditions. Lambrechts P. Thin Solid Films 2010. Pacheco MTT. 46: 5044-5049. 518: 4425-4431. Static and dynamic moduli of composite restorative materials. Hardness evaluation of a dental composite polymerized with experimental LED-based devices. and applications. CONCLUSION After identifying the most appropriate conditions for light curing our resin matrix. 19: 531-541. 32: 525-535. Nanocharacterization in Dentistry. J Mater Sci 2011. 7) Chen X. Tuboy AM. Calibration of FTIR conversion analysis of contemporary dental resin composites. 29 and 20% for the same sequence of materials. Additionally. 19) Yoshida K. 6) Salerno M. modiﬁcations. Int J Mol Sci 2010. 6: 241-249. 17: 309-315. Tay FR. Chem Rev 2007. 17) Braem M. In ﬂexural tests the elastic modulus was always lower than the compression test values. Thorat S. Javadpour J. Barbosa Pinheiro AL. Taira Y. Investigation of mechanical properties of experimental Bis-GMA/TEGDMA dental composite resins containing various mass fractions of silica nanoparticles. However. 90: 1122-1128. 9) Bowen RL. Darr AH. J Oral Rehabil 1997. probably around 20% already for the 10%wt sample and above 90% for the 50%wt sample. Properties of opaque resin composite containing coated and silanized Titanium dioxide. Sawston. Additionally. Derchi G. Arola AA. Salerno M. Vicker’s hardness and Raman spectroscopy evaluation of a dental composite cured by an argon laser and a halogen lamp. Pucci CR. Use of epoxy resins in restorative materials. J Dent Res 2011. editor. Diaspro A. no thermal transitions were observed at the investigated temperatures for any material. Niu L-N. and compared it to static nanoindentation carried out by AFM. 3) Sharma S. 8) Pignatelli F. Dai L. Fukushima M.4%vol. Effect of biomimetic remineralization on the dynamic nanomechanical properties of dentin hybrid layers. Cross SE. .6 GPa was found. Titanium dioxide nanomaterials: synthesis. Directional enhancement of refractive index and tunable wettability of polymeric coatings due to preferential dispersion of colloidal TiO2 nanorods towards their surface. the highest modulus was observed for the nanosilica ﬁller. Dental Mater 2001. This calculation is made according to nominal densities of bulk materials. In compression. the volume loading of our nanosilica was obviously much higher. Nanotechnology in dental sciences: moving towards a ﬁner way of doing dentistry. 4) Wahl MJ. Titania ﬁllers could be of interest in future applications where their photocatalytic effect could be useful to promote local antibacterial or remineralization reactions. 2) Uskoković V. Carzino R. J Prosthod 2010. 18) Jacobsen PH. regarding the solvent effects20). corresponding in turn to ~4. in glass composite no increase in elastic modulus was observed on increase of loading from 10 to 50%wt. 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