Alternative monomer for BisGMA-free resin composites formulations

ObjectiveWater sorption, high volumetric shrinkage, polymerization stress, and potential estrogenic effects triggered by leached compounds are some of the major concerns related to BisGMA-TEGDMA co-monomer systems used in dental composites. These deficiencies call for the development of alternative organic matrices in order to maximize the clinical lifespan of resin composite dental restorations. This study proposes BisGMA-free systems based on the combination of UDMA and a newly synthesized diurethane dimethacrylate, and evaluates key mechanical and physical properties of the resulting materials.Methods2EMATE-BDI (2-hydroxy-1-ethyl methacrylate) was synthesized by the reaction between 2-hydroxy-1-ethyl methacrylate with a difunctional isocyanate (1.3-bis (1- isocyanato-1-methylethylbenzene) – BDI). The compound was copolymerized with UDMA (urethane dimethacrylate) at 40 and 60 wt%. UDMA copolymerizations with 40 and 60 wt% TEGDMA (triethylene glycol dimethacrylate) were tested as controls, as well as a formulation based in BisGMA (bisphenol A-glycidyl methacrylate)-TEGDMA 60:40% (BT). The organic matrices were made polymerizable by the addition of DMPA (2.2-dimethoxyphenoxy acetophenone) and DPI-PF6 (diphenyliodonium hexafluorophosphate) at 0.2 and 0.4 wt%, respectively. Formulations were tested as composite with the addition of 70 wt% inorganic content consisting of barium borosilicate glass (0.7 μm) and fumed silica mixed in 95 and 5 wt%, respectively. All photocuring procedures were carried out by a mercury arc lamp filtered to 320–500 nm at 800 mW/cm². The experimental resin composites were tested for kinetics of polymerization and polymerization stress in real time. Flexural strength, elastic modulus, water sorption, and solubility were assessed according to ISO 4049. Biofilm formation was analyzed after 24 h by luciferase assay. Data were statistically analyzed by one-way ANOVA and Tukey's test (α ≤ 0.05).ResultsIn general, the addition of 2EMATE-BDI into the formulations decreased the maximum rate of polymerization (RP_MAX), the degree of conversion at RP_MAX (DC at RP_MAX), and the final degree of conversion (final DC). However, these reductions did not compromise mechanical properties, which were comparable to the BT controls, especially after 7-day water incubation. The incorporation of 60 wt% 2EMATE-BDI reduced water sorption of the composite. 2EMATE-BDI containing formulations showed reduction in polymerization stress of 30% and 50% in comparison to BT control and TEGDMA copolymerizations, respectively. Biofilm formation was similar among the tested groups.SignificanceThe use of the newly synthesized diurethane dimethacrylate as co-monomer in dental resin composite formulations seems to be a promising option to develop polymers with low-shrinkage and potentially decreased water degradation.     

Influence of various irradiation processes on the mechanical properties and polymerisation kinetics of bulk-fill resin based composites

ObjectivesTo assess the effect of irradiation time and distance of the light tip on the micro-mechanical properties and polymerisation kinetics of two bulk-fill resin-based composites at simulated clinically relevant filling depth.MethodsMicro-mechanical properties (Vickers hardness (HV), depth of cure (DOC) and indentation modulus (E)) and polymerisation kinetics (real-time increase of degree of cure (DC)) of two bulk-fill resin-based composites (Tetric EvoCeram^® Bulk Fill, Ivoclar Vivadent and x-tra base, Voco) were assessed at varying depth (0.1–6 mm in 100 μm steps for E and HV and 0.1, 2, 4 and 6 mm for DC), irradiation time (10, 20 or 40 s, Elipar Freelight2) and distances from the light tip (0 and 7 mm). Curing unit's irradiance was monitored in 1 mm steps at distances up to 10 mm away from the light tip on a laboratory-grade spectrometer.ResultsMultivariate analysis (α = 0.05), Student's t-test and Pearson correlation analysis were considered. The influence of material on the measured mechanical properties was significant (η² = 0.080 for E and 0.256 for HV), while the parameters irradiation time, distance from the light tip and depth emphasise a stronger influence on Tetric EvoCeram^® Bulk Fill. The polymerisation kinetics could be described by an exponential sum function, distinguishing between the gel and the glass phase. The above mentioned parameters strongly influenced the start of polymerisation (gel phase), and were of less importance for the glass phase.ConclusionsBoth materials enable at least 4 mm thick increments to be cured in one step under clinically relevant curing conditions.Clinical significanceThe susceptibility to variation in irradiance was material dependent, thus properties measured under clinically simulated curing conditions might vary to a different extent from those measured under ideal curing conditions.     

Determination of the optimal photoinitiator concentration in dental composites based on essential material properties

ObjectivesThe aim of this study was to determine the concentrations of the photosensitizer (camphoroquinone, CQ) and coinitiator (ethyl-4-dimethylaminobenzoate, EDMAB) that resulted in maximum conversion but generated minimum contraction stress in experimental composites.MethodsExperimental composites were prepared with an identical resin formulation [TEGDMA:UDMA:bis-GMA of 30.25:33.65:33.65]. Five groups of resin were prepared at varied CQ concentrations (0.1, 0.2, 0.4, 0.8 and 1.6 wt% of the resin). Five subgroups of resin were prepared at each level of CQ concentration, by adding EDMAB at 0.05, 0.1, 0.2, 0.4 and 0.8 wt% of the resin, resulting in 25 experimental resins. Finally, strontium glass (～3 μm) and silica (0.04 μm) were added at 71.5 and 12.6 wt% of the composite, respectively. Samples (n = 3) were then evaluated for Knoop hardness (KHN), degree of conversion (DC), depth of cure (DoC) and contraction stress (CS).ResultsThere was an optimal CQ and EDMAB concentration that resulted in maximum DC and KHN, beyond which increased concentration resulted in a decline in those properties. KHN testing identified two regions of maxima with best overlaps occurring at CQ:EDMAB ratio of 1.44:0.42 and 1.05:1.65 mol%. DC evaluation showed one region of maximum, the best overlap occurring at CQ:EDMAB ratio of 2.40:0.83 mol%. DoC was 4 mm. Overall, maximum CS was attained before the system reached the maximum possible conversion and hardness.Significance(1) Selection of optimal photoinitiator/amine concentration is critical to materials’ formulation, for excessive amounts can compromise materials’ properties. (2) There was no sufficient evidence to suggest that contraction stress can be reduced by lowering CQ/EDMAB concentration without compromising DC and KHN.     

Influence of curing modes on the degree of conversion and mechanical parameters of dual-cured luting agents

PurposeTo investigate the effects of different curing modes, including tack cure, on the degree of conversion (DC) and mechanical parameters of dual-cured luting agents for all-ceramic restorations.MethodsImmediate light curing, intermittent light curing (2-s tack cure and a 1-min interval before the main cure), delayed light cuing (2-min delay) and chemical or no light curing were used to cure two dual-cured luting agents, RelyX Unicem and PermaCem 2.0, through a 1.5-mm thick lithium disilicate ceramic slide. DC (n = 3), micro-hardness (n = 5), shrinkage strain (n = 4) and shrinkage stress (n = 3) were measured under the aforementioned curing modes. The data were analyzed using two-way ANOVA and post-hoc Tukey HSD test, with the level of significance set at α = 0.05.ResultsFor both luting agents, all the light-curing modes produced similar final DC, but using chemical cure only could significantly reduce the DC. The mechanical parameters followed a similar pattern. There were positive but nonlinear correlations between DC and the other mechanical parameters, with the increase in these parameters with DC being slower initially.ConclusionsProvided adequate light curing is applied to a dual-cured luting agent, delaying the light curing or using a tack cure first to facilitate seating of a restoration may not have a significant impact on the luting agent’s final degree of conversion. However, using chemical cure only may result in inadequate cure of the luting agent and is recommended only for highly opaque restorations.     

Color matching ability of resin composites incorporating supra-nano spherical filler producing structural color

ObjectiveThe aim of this study was to evaluate the optical properties of supra-nano spherical fillers with different diameters and the color matching ability of resin composites (RC) incorporating these fillers.MethodsTwo types of SiO₂–ZrO₂ nano fillers with different diameters (150 nm and 260 nm) were used. The size distribution of each filler was measured and filler morphology was observed. The colors and spectral reflection spectra were measured by a spectral reflectometer. Experimental RCs incorporating ?150-nm/?260-nm filler (D150RC/D260RC) were prepared. For the base dentin part, disc specimens (Estelite Astelia: A1B, A2B, A3B, A3.5B, or A4B) were prepared with a cylindrical cavity. Estelite Astelia with NE shade was layered on top as the enamel layer. Disk specimens with different cavity depths were prepared using A3B shade. Experimental RC was used to fill the cavity, and spectral reflection spectrums were obtained and analyzed. Filtek Supreme Ultra (FSU) with A3B shade was used (n = 10) as a control.ResultsBoth ?150-nm and ?260-nm nano fillers showed uniform spherical shape and exhibited no aggregation. The maximum peaks of the spectral reflection spectra of the ?150-nm and ?260-nm nano fillers were 380 nm and 580 nm, producing structural colors close to blue and yellow, respectively. The spectral reflection spectrum of FSU had a broad peak at 540 nm, and D150RC had a significant peak at 420 nm. The D260RC specimen had a broad peak at 680 nm. The peaks of D150RC and D260RC significantly decreased in accordance with the shift in base RC shade from A1B to A4B. There was no significant difference in the peak of the reflection spectral spectra among different cavity depths of D260RC. These results suggest that the experimental RC could reflect base RC colors via the matrix resin, and the amount of transmitted light from the base RC was not much different with cavity depth.SignificanceD260RC producing structural color demonstrated a broad spectrum and reduction in brightness and chromatic value by adapting to surrounding restorative materials, suggesting its ability to enhance the chameleon (blending) effects to improve color matching. D260RC showed better color matching ability than resin composite containing uniformly sized ?150-nm SiO₂–ZrO₂ supra-nano spherical filler.     

Evaluation of the filler packing structures in dental resin composites: From theory to practice

Objectives

The aim of this study is to evaluate the packing properties of uniform silica particles and their mixture with secondary particles yielding maximally loaded dental composites. We intend to verify the difference between the idealized models (the close-packed structures and the random-packed structures) and the actual experimental results, in order to provide guidance for the preparation of dental composites. The influence of secondary particle size and the resin composition on the physical–mechanical properties and the rheological properties of the experimental dental composites was also investigated.

Niobium containing bioactive glasses as remineralizing filler for adhesive resins

ObjectiveThe aim of this study was to incorporate sol–gel-derived bioactive glass as filler into experimental adhesive resins and evaluate the influence of glass composition on the physicochemical and biological properties of the developed adhesives.Materials and methodsSol–gel particles were produced with or without the addition of niobium (BAGNb or BAG, respectively). The produced particles were incorporated (2 wt%) into experimental adhesive resins formulated with 66 wt% bisphenol A-glycidyl methacrylate and 33 wt% hydroxyethyl methacrylate. Ethyl dimethyl-4-aminobenzoate and camphorquinone were used as photoinitiator system. Two experimental groups were produced: A_BAGNb and A_BAG. The adhesive without particles was used as control (A_CG). The materials were tested for their degree of conversion, softening in solvent, and cytotoxicity. The mineral deposition was analyzed by Raman spectroscopy. Flexural strength and immediate and 1-year microtensile bond strength were evaluated.ResultsNo statistical difference was found in degree of conversion. A_BAGNb showed reduced softening and higher mineral deposition than A_CG and A_BAG after 28 days. A_BAG and A_BAGNb resulted in higher cell viability and lower flexural strength when compared to A_CG. After 1-year, A_BAGNb and A_BAG presented statistically significant lower μTBS values.SignificanceSol–gel-derived bioactive glasses promoted increased mineral deposition and cell viability for experimental adhesives with increased phosphate content and longitudinal μTBS values for the A_BAGNb group. These results suggest the potential of the studied particles to be applied as bioactive fillers for dental adhesives. Reductions in longitudinal μTBS and flexural strength, however, were observed for both glasses compositions and must be considered.     

Fabrication and characterization of remineralizing dental composites containing calcium type pre-reacted glass-ionomer (PRG-Ca) fillers

ObjectiveTo fabricate and characterize dental composites with calcium type pre-reacted glass-ionomer (PRG-Ca) fillers.MethodsPRG-Ca fillers were prepared by the reaction of calcium fluoroaluminosilicate glass with polyacrylic acid. Seven dental composites were produced from the same organic matrix (70/30 wt% Bis-GMA/TEGDMA), with partial replacement of barium borosilicate (BaBSi) fillers (60 wt%) by PRG-Ca fillers (wt%): E0 (0) – control, E1 (10), E2 (20), E3 (30), E4 (40), E5 (50) and E6 (60). Enamel remineralization was evaluated in caries-like enamel lesions induced by S. mutans biofilm using micro-CT. The following properties were characterized: degree of conversion (DC%), roughness (Ra), Knoop hardness (KHN), flexural strength (FS), flexural modulus (FM), water sorption (W_sp), water solubility (W_sl), and translucency (TP). Data were analyzed to one-way ANOVA and Tukey’s HSD test (α = 0.05).ResultsAll composites with PRG-Ca induced enamel remineralization. E0 and E1 presented similar and highest DC% than E2 = E3 = E4 = E5 = E6. Ra and KHN were not influenced by PRG-Ca fillers (p < 0.05). The higher the content of PRG-Ca, the lower FS, FM and TP (p < 0.05). W_sp increased linearly with the content of PRG-Ca fillers (p < 0.05). E6 presented the highest W_sl (p < 0.05), while the W_sl of the other composites were not different from each other (p > 0.05).SignificanceIncorporation of 10–40 wt.% of PRG-Ca fillers endowed remineralizing potential to dental composites without jeopardizing the overall behavior of their physicochemical properties. Dental composites with PRG-Ca fillers seems to be a good alternative for reinforcing the enamel against caries development.     

Resin viscosity determines the condition for a valid exposure reciprocity law in dental composites

ObjectiveTo provide conditions for the validity of the exposure reciprocity law as it pertains to the photopolymerization of dimethacrylate-based dental composites.MethodsComposites made from different mass ratios of resin blends (Bis-GMA/TEGDMA and UDMA/TEGDMA) and silanized micro-sized glass fillers were used. All the composites used camphorquinone and ethyl 4-dimethylaminobenzoate as the photo initiator system. A cantilever beam-based instrument (NIST SRI 6005) coupled with NIR spectroscopy and a microprobe thermocouple was used to simultaneously measure the degree of conversion (DC), the polymerization stress (PS) due to the shrinkage, and the temperature change (TC) in real time during the photocuring process. The instrument has an integrated LED light curing unit providing irradiances ranging from 0.01 W/cm² to 4 W/cm² at a peak wavelength of 460 nm (blue light). Vickers hardness of the composites was also measured.ResultsFor every dental composite there exists a minimum radiant exposure required for an adequate polymerization (i.e., insignificant increase in polymerization with any further increase in the radiant exposure). This minimum predominantly depends on the resin viscosity of composite and can be predicted using an empirical equation established based on the test results. If the radiant exposure is above this minimum, the exposure reciprocity law is valid with respect to DC for high-fill composites (filler contents >50% by mass) while invalid for low-fill composites (that are clinically irrelevant).SignificanceThe study promotes better understanding on the applicability of the exposure reciprocity law for dental composites. It also provides a guidance for altering the radiant exposure, with the clinically available curing light unit, needed to adequately cure the dental composite in question.     

Bis-GMA co-polymerizations: Influence on conversion,flexural properties,fracture toughness and susceptibility to ethanol degradation of experimental composites

ObjectivesThe aim of this study was to evaluate the influence of monomer content on fracture toughness (K_Ic) before and after ethanol solution storage, flexural properties and degree of conversion (DC) of bisphenol A glycidyl methacrylate (Bis-GMA) co-polymers.MethodsFive formulations were tested, containing Bis-GMA (B) combined with TEGDMA (T), UDMA (U) or Bis-EMA (E), as follows (in mol%): 30B:70T; 30B:35T:35U; 30B:70U; 30B:35T:35E; 30B:70E. Bimodal filler was introduced at 80 wt%. Single-edge notched beams for fracture toughness (FT, 25 mm × 5 mm × 2.5 mm, a/w = 0.5, n = 20) and 10 mm × 2 mm × 1 mm beams for flexural strength (FS) and modulus (FM) determination (10 mm × 2 mm × 1 mm, n = 10) were built and then stored in distilled water for 24 h at 37 °C. All FS/FM beams and half of the FT specimens were immediately submitted to three-point bending test. The remaining FT specimens were stored in a 75%ethanol/25%water (v/v) solution for 3 months prior to testing. DC was determined with FT-Raman spectroscopy in fragments of both FT and FS/FM specimens at 24 h. Data were submitted to one-way ANOVA/Tukey test (α = 5%).ResultsThe 30B:70T composite presented the highest K_Ic value (in MPa m^1/2) at 24 h (1.3 ± 0.4), statistically similar to 30B:35T:35U and 30B:70U, while 30B:70E presented the lowest value (0.5 ± 0.1). After ethanol storage, reductions in K_Ic ranged from 33 to 72%. The 30B:70E material presented the lowest reduction in FT and 30B:70U, the highest. DC was similar among groups (69–73%), except for 30B:70U (52 ± 4%, p < 0.001). 30B:70U and 30B:35T:35U presented the highest FS (125 ± 21 and 122 ± 14 MPa, respectively), statistically different from 30B:70T or 30B:70E (92 ± 20 and 94 ± 16 MPa, respectively). Composites containing UDMA or Bis-EMA associated with Bis-GMA presented similar FM, statistically lower than 30B:35T:35U.SignificanceComposites formulated with Bis-GMA:TEGDMA:UDMA presented the best compromise between conversion and mechanical properties.     

The effect of excitation laser power in Raman spectroscopic measurements of the degree of conversion of resin composites

ObjectivesTo evaluate the effect of excitation laser power in Raman spectrometry by comparing the spectra and the degree of conversion (DC) values obtained using excitation powers between 300 and 1000 mW.MethodsFive commercial and three experimental resin composites were light cured at 1200 mW/cm² for 10–20 s from a commercial blue-violet LED dental curing unit. Raman spectra were collected from composite specimens within 9 min after light-curing. The excitation laser (1064 nm) was focused on the spot of 0.4 mm in diameter. The following powers were used for specimen excitation (mW): 300, 400, 600, 800, and 1000. From Raman spectra, the DC values were calculated and compared among different laser powers. Also, vector-normalized Raman spectra collected using the lowest excitation power (300 mW) were compared to those collected using the maximum excitation power (1000 mW).ResultsVarying the excitation laser power between 300 and 1000 mW resulted in statistically significant differences in both the DC values and the intensity of particular spectral features. The effect of varying laser power on Raman spectra and obtained DC values was material-dependent. The DC values measured within an individual material using different laser powers varied between 3.2 and 7.2% (absolute DC difference). The spectral bands affected by variations in laser power were assigned to symmetric and asymmetric stretching of −CH₂ (2900-3100 cm⁻¹), symmetric stretching of aliphatic CC (1640 cm⁻¹) and scissoring of C–H (1458 cm⁻¹).SignificanceThe DC can be artificially elevated through increasing excitation laser power. This effect should be considered in Raman spectroscopic evaluations of DC in specimens during ongoing post-cure polymerization.     

Reinforcement of experimental composite materials based on amorphous calcium phosphate with inert fillers

ObjectivesThe aim of this study was to examine the influence of the addition of glass fillers with different sizes and degrees of silanization percentages to remineralizing composite materials based on amorphous calcium phosphate (ACP).MethodsFour different materials were tested in this study. Three ACP based materials: 0-ACP (40 wt% ACP, 60 wt% resin), Ba-ACP (40 wt% ACP, 50 wt% resin, 10 wt% barium-glass) and Sr-ACP (40 wt% ACP, 50 wt% resin, 10 wt% strontium-glass) were compared to the control material, resin modified glass ionomer (Fuji II LC capsule, GC, Japan). The fillers and composites were characterized using scanning electron microscopy. Flexural strength and modulus were determined using a three-point bending test. Calcium and phosphate ion release from ACP based composites was measured using inductively coupled plasma atomic emission spectroscopy.ResultsThe addition of barium-glass fillers (35.4 (29.1–42.1) MPa) (median (25–75%)) had improved the flexural strength in comparison to the 0-ACP (24.8 (20.8–36.9) MPa) and glass ionomer control (33.1 (29.7–36.2) MPa). The admixture of strontium-glass (20.3 (19.5–22.2) MPa) did not have any effect on flexural strength, but significantly improved its flexural modulus (6.4 (4.8–6.9) GPa) in comparison to 0-ACP (3.9 (3.4–4.1) GPa) and Ba-ACP (4.6 (4.2–6.9) GPa). Ion release kinetics was not affected by the addition of inert fillers to the ACP composites.SignificanceIncorporation of barium-glass fillers to the composition of ACP composites contributed to the improvement of flexural strength and modulus, with no adverse influence on ion release profiles.     

Improvement on properties of experimental resin cements containing an iodonium salt cured under challenging polymerization conditions

ObjectiveThe use of resin cements in clinical practice entails photopolymerization through prosthetic devices, which precludes light penetration. The objective of this study was to modify experimental resin cements (ERCs) with diphenyliodonium hexafluorophosphate (DPI) in an attempt to improve chemical and mechanical properties of materials cured with reduced irradiance and final radiant exposure.MethodsA co-monomer base containing a 1:1 mass ratio of 2.2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (bis-GMA) and triethyleneglycol dimethacrylate (TEGDMA) was prepared, with 1 mol% of camphorquinone and 2 mol% of ethyl 4-(dimethylamino)benzoate as initiator system. The resin was divided into 4 fractions according to the DPI concentrations (0, 0.5, 1 and 2 mol%). The challenging polymerization condition was simulated performing the light activation (12, 23 and 46 s) through a ceramic block (3 mm thick). The irradiance was assessed with a calibrated spectrometer (1320 mW/cm²), resulting in three levels of radiant exposure (0.58, 1.1 and 2.2 J/cm²). The polymerization kinetics was evaluated in real-time using a spectrometer (Near-IR). Water sorption and solubility was analyzed and the cohesive strength of resins obtained through the microtensile test. Polymerization stress was assessed by Bioman method.ResultsResins containing DPI had higher degree of conversion and rate of polymerization than the control (without DPI). The use of DPI reduced water sorption and solubility, and led to higher cohesive strength compared to resins without the iodonium salt. However, the stress of polymerization was higher for experimental resins with DPI.SignificanceEven under remarkably reduced irradiance, cements containing a ternary initiating system with an iodonium salt can present an optimal degree of conversion and chemical/mechanical properties.     

The effect of resin composite pre-heating on monomer conversion and polymerization shrinkage

ObjectivesTo determine monomer conversion and polymerization shrinkage of a resin composite after different pre-heating procedures and storage intervals.MethodsFor a commercial resin-based composite the immediate (5 min) and final (24 h) degree of conversion was measured on top and bottom surfaces utilizing FTIR spectroscopy. Composite pre-heating temperatures were selected between 10 and 68 °C. Polymerization shrinkage was measured according to Archimedes’ principles of buoyancy after 5 min at respective pre-heating temperatures and after 24 h dark and wet storage at 37 °C. Intra-cavity temperature development was monitored using a K-type thermocouple.ResultsNo significant increase in immediate as well as in final degree of conversion were measured from composite pre-heating at 68 °C compared to 54 and 39 °C. Linear correlations were detected immediately after photo-polymerization and on the top surface after 24 h storage. Polymerization shrinkage as a function of pre-heating temperatures exhibited a linear correlation after 5 min, but no statistically different behavior after 24 h.SignificancePre-heating of resin composites does not increase degree of conversion over time. It can be clinically beneficial, due to a superior marginal adaptation. This advantageous effect of reduced material paste viscosity has to be clinically addressed, since temperature rapidly drops to the physiological level upon removal from the pre-heating device.     

Effect of the amount of 3-methacyloxypropyltrimethoxysilane coupling agent on physical properties of dental resin nanocomposites

ObjectivesThe purpose of this study was to evaluate the effect of the amount of 3-methacryloxypropyl-trimethoxysilane (γ-MPS) coupling agent on some physical–mechanical properties of an experimental resin composite for understanding the optimum amount of silanization.MethodsSilica nanoparticles (Aerosil OX 50) used as filler were silanized with 5 different amounts of γ-MPS 1.0, 2.5, 5.0, 7.5 and 10 wt% relative to silica. The silanizated silica nanoparticles were identified by FT-IR spectroscopy and thermogravimetric analysis (TGA). Then the silanized nanoparticles (60 wt%) were mixed with a Bis-GMA/TEGDMA (50/50 wt/wt) matrix. Degree of conversion of light cured composites was determined by FT-IR analysis. The static flexural strength and flexural modulus were measured using a three-point bending set up. The dynamic thermomechanical properties were determined by DMA analyzer. Sorption, solubility and volumetric change were determined after storage of composites in water or ethanol/water solution. Thermogravimetric analysis was performed in air and in nitrogen atmosphere from 50 to 800 °C.ResultsAt lower silane amounts used (1.0, 2.5 wt%) the silane molecules must have a parallel orientation relative to the silica surface. At higher silane amounts (>2.5 wt%) silane molecules form a layer around the filler particles which now have to occupy a random, parallel and perpendicularly orientation relative to the silica surface. No significant statistic difference was found to exist between the flexural strength and flexural modulus values of composites with different silane contents. Dynamic elastic modulus E′ showed a maximum value for the composite contained 5 wt% silane. The composites with the higher amounts of silane showed the lower values for the tan δ at the T_g revealing that these composites have better interfacial adhesion between filler and matrix.SignificanceThe amount of silane used for the silanization of silica particles affect the orientation of the silane molecules relative to the silica surface. This seems to affect the dynamic mechanical properties of composites.     

Curing efficiency of four self-etching,self-adhesive resin cements

ObjectivesTo evaluate the degree of cure (%DC) of four self-etching, self-adhesive resin cements, and one conventional resin cement, in their self- and dual-curing mode.MethodsThe self-etching, self-adhesive resin cements studied were RelyX? Unicem (3M? ESPE? AG), Maxcem? (Kerr Corporation), Biscem? (Bisco, Inc.) and Multilink^® Sprint (Ivoclar Vivadent^® AG) and the classic resin cement was Multilink^® Automix (Ivoclar Vivadent^® AG). Twelve specimens of each material (1.8 mm × 4 mm × 4 mm) were prepared in room temperature (23 ± 1) °C following the manufacturers’ instructions. Six of them were treated as dual-cured, thus irradiated for 20 s with a halogen light curing unit and left undisturbed for 5 min. The other six were treated as self-cured and were not irradiated, but left in dark and dry conditions for 10 min. The assessment of the %DC was made using micro-ATR FTIR spectrometry.ResultsThe %DC in their self-curing mode was very low (10.82–24.93%), with Multilink Sprint exhibiting the highest values among the five. In the dual-curing mode the values obtained were also low (26.40–41.52%), with the exception of Multilink Automix (61.36%). Maxcem was found to have the lowest DC.SignificanceThe low %DC found raises questions as to whether these materials can be successfully used in clinical applications, where light attenuation takes place. Increased irradiation times could potentially lead to higher %DC, in applications where light is not completely blocked by the overlying restoration.     

Effect of proanthocyanidins and photo-initiators on photo-polymerization of a dental adhesive

ObjectivesTo evaluate the effects of proanthocyanidins (PA) and photoinitiator type on the degree of conversion (DC) and polymerization rate (PR) of a model dental adhesive.MethodsThree types of photo-initiation systems were introduced into the Bis-GMA/HEMA co-monomer mixture, resulting in four resin formulations including CQ/A (0.5 wt% CQ and EDMAB), CQ/A/I-1 (0.5 wt% CQ, EDMAB and DPIHP), CQ/A/I-2 (1.0 wt% CQ, EDMAB and DPIHP), and TPO (2.1 wt% TPO). For each resin formulation, adhesives containing 0%, 2.5%, 5% and 10% of PA with respect to the weight of resin were produced after mixing the resin with various amount of PA/ethanol solution. When light-cured, the RP and DC of each adhesive was determined using ATR-FTIR spectroscopy.ResultsAcross and within the initiator groups, the DC followed the general trend of CQ/A < CQ/A/I-1 < CQ/A/I-2 < TPO and 0-PA > 2.5-PA > 5-PA > 10-PA, respectively. The change of PR with respect to photo-initiation systems and PA content was in a similar but less pronounced pattern.ConclusionPA hampered the polymerization of all adhesives regardless of photoinitiators used. The initiator formulations CQ/A/I-2 and TPO are better fit for PA-containing adhesives, both leading to >65% DC in the presence of 5% PA.Clinical significanceThe inclusion of PA in dental adhesives has been limited by its interference with the light-curing of adhesive resins. This study found photo-initiation formulations that could maintain a satisfactory degree of monomer conversion while a significant amount of PA is incorporated.     

Conversion kinetics of rapid photo-polymerized resin composites

ObjectiveTo measure the degrees of conversion (DC), conversion kinetics, and the effect of post-irradiation time on rapid photo-polymerized bulk-fill resin composites under conditions equivalent to clinical depths of 1 and 4 mm.Methods36 specimens (n = 3), based on two resin composites incorporating PowerCure rapid-polymerization technology in two consistencies (PFill; PFlow) and two comparators with matching consistencies (Eceram; EFlow), were investigated from the same manufacturer (Ivoclar AG, Liechtenstein). Specimens were prepared within 4 mm diameter cylindrical molds, of either 1 mm or 4 mm depths respectively, to simulate near-surface and deep locations in a bulk-fill restoration. The independent variables in this study were: materials, thickness and time. Two high irradiance polymerization protocols were utilized for PowerCure materials: 2000 and 3050 mW/cm² for 5 and 3 s, respectively. A standard (1200 mW/cm²) polymerization protocol was used with control materials. FTIR was utilized to measure DC in real-time for 24 h post-irradiation. The data were analyzed using Welch’s-ANOVA, Games-Howell post-hoc test, kinetic dual-exponential sum function and independent sample t-tests (p = 0.05).ResultsThe DC of the materials ranged between 44.7–59.0 % after 5 min, which increased after 24 h reaching 55.7–71.0 % (p < 0.05). Specimen thickness did not influence the overall DC. At 5 min, the highest DC was shown in EFlow. But PFlow, irradiated for 3 s and 5 s exhibited comparable results (p > 0.05). PFill composite irradiated with the 3 s and 5 s protocols did not differ from ECeram (p > 0.05). Specimen thickness and material viscosity affected polymerization kinetics and rate of polymerization (RP_max). Faster polymerization occurred in 1 mm specimens (except PFill-5 s and ECeram). PFill and PFlow exhibited faster conversion than the controls. RP_max varied across the specimen groups between 4.3–8.8 %/s with corresponding DC _RPmax between 22.2–45.3 %.SignificancePolymerization kinetics and RP_max were influenced by specimen thickness and material viscosity. PFill and PFlow materials produced an overall comparable conversion at 5 min and 24 h post-irradiation, despite the ultra-short irradiation times, throughout the 4 mm specimen thickness.     

Effects of monomer ratios and highly radiopaque fillers on degree of conversion and shrinkage-strain of dental resin composites

ObjectivesThe degree of conversion (DC) and polymerization shrinkage of resin composites are closely related manifestations of the same process. Ideal dental composite would show an optimal degree of conversion and minimal polymerization shrinkage. These seem to be antagonistic goals, as an increase in monomer conversion leads to a high polymerization shrinkage. This paper aims to determine the effect of opaque mineral fillers and monomer ratios on the DC and the shrinkage-strain of experimental composites based on (BisGMA/TEGDMA) monomers (traditionally used monomers). A relationship between the shrinkage-strain and the degree of conversion values was also investigated. The radiopacity of these experimental composites has been investigated in a previous paper.MethodsExperimental resin composites were prepared by mixing different monomer ratios of (BisGMA/TEGDMA) with Camphoroquinone and dimethyl aminoethyl methacrylate (DMAEMA) as photo-initiator system. Five different radiopacifying filler agents: La₂O₃, BaO, BaSO₄, SrO and ZrO₂ at various volume fractions ranging from 0 to 80 wt.% were added to the mixture. The degree of conversion of experimental composites containing different opaque fillers contents was measured using FTIR/ATR spectroscopy. The shrinkage-strain of specimens, photopolymerized at circa 500 mW/cm², was measured using the bonded-disk technique at room temperature with respect to time.ResultsThe result revealed that the DC and the shrinkage-strain decrease slightly with the increasing of opaque fillers loadings, but this decrease is not significant. However, these two properties are closely related to the monomer concentration of the organic matrix. The results have also showed a linear correlation between the shrinkage-strain and DC of experimental composites investigated.SignificanceThe nature and the volume effects of the opaque fillers on the DC and shrinkage of the experimental composites investigated were not significant. However, this study has confirmed the importance of viscosity in the system and shrinkage behavior of dimethacrylate monomers studied. Then we confirmed that direct relationships linked the shrinkage and the DC of filled dental resin composites.     

Evaluation of physical properties of fiber-reinforced composite resin

ObjectivesThis study aimed to investigate physical properties of a fiber-reinforced CAD/CAM resin disc, which included woven layers of multi-directional glass fibers.MethodsFiber orientations of CAD/CAM specimens (TRINIA, SHOFU) were specified as longitudinal (L), longitudinal-rotated (LR), and anti-longitudinal (AL). A fiber-reinforced composite (everX posterior, GC (E)) and a conventional composite (Beauti core flow paste, SHOFU (B)) were also tested.A three-point bending test and a tensile test with notchless prism-shaped specimens were conducted using a universal testing machine (AUTOGRAPH AG-IS, Shimadzu). A water absorption test was also carried out after the specimens were stored in water for 24 h or 1 week. Flexural strength and fracture toughness were obtained by conducting a three-point bending test.ResultsTRINIA L and LR groups showed significantly high flexural strength (254.2 ± 22.3 and 248.8 ± 16.7 MPa, respectively). Those were approximately 2.5 times higher than those in AL, E, and B groups (96.8–98.0 MPa) (p < 0.05, ANOVA and Tukey HSD test). No significant difference was shown in flexural modulus among the experimental groups. The fracture toughness in L group (9.1 ± 0.4 MPa/m^1/2) was found to be significantly higher than those in other groups (1.9–3.0 MPa/m^1/2; p < 0.05). TRINIA group demonstrated significantly lower water absorption (4.7 ± 1.9 μg/mm³) than did E (16.1 ± 3.1 μg/mm³) and B (17.3 ± 3.7 μg/mm³) groups (p < 0.05).SignificanceTRINIA demonstrated distinct anisotropy. TRINIA can be used as a superior restorative material when specifying directions of its fiber mesh layers.