L.C.C. Boaro

Monomers used in resin composites: degree of conversion, mechanical properties and water sorption/solubility

The organic phase of resin composites is constituted by dimethacrylate resins, the most common monomers being the bisphenol A diglycidildimethacrylate (BisGMA), its ethoxylated version (BisEMA), triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA). This study compared the homopolymers formed from the monomers used in restorative dental composites in terms of their degree of conversion (DC) and reaction kinetics (by near infra-red spectroscopy, n=3), mechanical properties (flexural modulus and strength in three point-bending, FM and FS, respectively, n=15), water sorption and solubility (WS and SL, respectively - ISO 4049, n=5). Materials were made photopolymerizable by the addition of camphoroquinone/dimethylamine ethyl methacrylate. TEGDMA showed the highest DC, followed by BisEMA, UDMA and BisGMA, both at 10 min and at 24h (p<0.001). UDMA showed the highest rate of polymerization, followed by TEGDMA, BisEMA and BisGMA (H(0)=13.254, p<0.001). UDMA and TEGDMA presented similar FM, significantly higher (p<0.001) than BisEMA and BisGMA, which in turn present statistically similar values (p>0.001). For FS, UDMA presented the highest value (p<0.001), followed by TEGDMA, then by BisEMA and BisGMA, which were statistically similar (p>0.001). BisGMA showed the highest WS, and TEGDMA and BisEMA the lowest. UDMA was statistically similar to all (H(0)=16.074, p<0.001). TEGDMA presented the highest SL, followed by UDMA, BisGMA and BisEMA (p<0.001). The tested homopolymers presented different behaviors in terms of polymerization kinetics, flexural properties, water sorption and solubility. Therefore, the use of copolymers is justified in order to obtain high DC and mechanical properties, as well as good resistance to water degradation.

Influence of the bonding substrate in dental composite polymerization stress testing

Our objective was to compare the polymerization stress (sigma(pol)) of a series of composites obtained using poly(methyl methacrylate) (PMMA) or glass as bonding substrates, and to compare the results with those from in vitro microleakage of composite restorations. The tested hypothesis was that stress values obtained in a less rigid testing system (i.e. using PMMA) would show a better relationship with microleakage data. Five dental composites were tested: Filtek Z250 (FZ), Z100 (Z1), Concept (CO), Durafill (DU) and Heliomolar (HM). sigma(pol) was determined in 1mm high specimens inserted between two rods (Ø=5mm) of either PMMA or glass. The composite elastic modulus (E) was obtained by three-point bending. sigma(pol) and E data were submitted to a one-way analysis of variance/Tukey test (alpha=0.05). For the microleakage test (MI), bovine incisors received cylindrical cavities (Ø=5mm, h=2mm), which were restored in bulk. After storage for 24h in water, specimens were subjected to dye penetration using AgNO(3) as tracer. Specimens were sectioned twice, perpendicularly, and microleakage was measured (in millimeters) under 20x magnification. Data from MI were submitted to the Kruskal-Wallis test. Means (SD) of sigma(pol) (MPa) using glass/PMMA were FZ: 7.5(1.8)(A)/2.5(0.2)(bc); Z1: 7.3(0.5)(A)/2.8(0.3)(ab); CO: 6.8(1.1)(A)/3.2(0.5)(a); DU: 4.5(0.7)(B)/2.0(0.2)(bc); HM: 3.5(0.2)(B)/2.3(0.3)(c). sigma(pol) obtained using PMMA rods were 34-67% lower than with glass. Means (SD) for tooth average/tooth maximum microleakage were FZ: 0.92(0.19)(B)/1.53(0.30)(a); Z1: 1.19(0.21)(A)/1.75(0.20)(a); CO: 1.26(0.25)(A)/1.78(0.24)(a); DU: 0.83(0.30)(B)/1.68(0.46)(a); HM: 0.81(0.27)(B)/1.64(0.54)(a). The tested hypothesis was confirmed, as the composites showed the same ordering both in the polymerization stress test using PMMA rods and in the microleakage test.

Effect of Immediate or Delayed Light Activation on Curing Kinetics and Shrinkage Stress of Dual-Cure Resin Cements

OBJECTIVES This study evaluated the effect of light activation (absence, immediate, or delayed) on conversion kinetics and polymerization stress of three commercial dual-cured resin cements (Enforce, RelyX ARC, and Panavia F). METHODS Degree of conversion (DC) was monitored for 30 minutes using real-time near–Fourier transform infrared spectroscopy. The cement was mixed, placed on the spectrometer sample holder, and light activated either immediately or after five minutes (delayed light activation). When no light activation was performed, the materials were protected from light exposure (control). DC was evaluated at five and 30 minutes postmixture. Maximum rates of polymerization (Rp(max)) were obtained from the first derivative of the DC vs time curve. Polymerization stress was monitored for 30 minutes in 1-mm-thick specimens inserted between two cylinders attached to a universal testing machine. Data were submitted to analysis of variance/Tukey tests (α=0.05). RESULTS Immediate light activation promoted the highest DC at five minutes. At 30 minutes, only RelyX ARC did not present a significant difference in DC between activation modes. Enforce and Panavia F presented higher Rp(max) for immediate and delayed light-activation, respectively. RelyX ARC showed similar Rp(max) for all activation modes. The absence of light activation resulted in the lowest stress followed by delayed light activation, while immediate light activation led to the highest values. RelyX ARC showed higher stress than Enforce, while the stress of Panavia F was similar to that of the others. CONCLUSION Delayed light activation reduced the polymerization stress of the resin cements tested without jeopardizing DC.

A comparative study between crack analysis and a mechanical test for assessing the polymerization stress of restorative composites

OBJECTIVES To verify the hypothesis that crack analysis and a mechanical test would rank a series of composites in a similar order with respect to polymerization stress. Also, both tests would show similar relationships between stress and composite elastic modulus and/or shrinkage. METHODS Soda-lime glass discs (2-mm thick) with a central perforation (3.5-mm diameter) received four Vickers indentations 500 μm from the cavity margin. The indent cracks were measured (500×) prior and 10 min after the cavity was restored with one of six materials (Kalore/KL, Gradia/GR, Ice/IC, Wave/WV, Majesty Flow/MF, and Majesty Posterior/MP). Stresses at the indent site were calculated based on glass fracture toughness and increase in crack length. Stress at the bonded interface was calculated using the equation for an internally pressurized cylinder. The mechanical test used a universal testing machine and glass rods (5-mm diameter) as substrate. An extensometer monitored specimen height (2mm). Nominal stress was calculated dividing the maximum shrinkage force by the specimen cross-sectional area. Composite elastic modulus was determined by nanoindentation and post-gel shrinkage was measured using strain gages. Data were subjected to one-way ANOVA/Tukey or Kruskal-Wallis/Mann-Whitney tests (alpha: 5%). RESULTS Both tests grouped the composites in three statistical subsets, with small differences in overlapping between the intermediate subset (MF, WV) and the highest (MP, IC) or the lowest stress materials (KL, GR). Higher stresses were developed by composites with high modulus and/or high shrinkage. SIGNIFICANCE Crack analysis demonstrated to be as effective as the mechanical test to rank composites regarding polymerization stress.

Experimental and FE displacement and polymerization stress of bonded restorations as a function of the C-Factor, volume and substrate stiffness

OBJECTIVES To determine the free surface displacement of resin-composite restorations as a function of the C-Factor, volume and substrate stiffness, and to compare the results with interfacial stress values evaluated by finite element analysis (FEA). METHODS Surface displacement was determined by an extensometer using restorations with 4 or 6mm diameter and 1 or 2mm depth, prepared in either bovine teeth or glass. The maximum displacement of the free surface was monitored for 5 min from the start of photoactivation, at an acquisition rate of 1s(-1). Axisymmetric cavity models were performed by FEA. Structural stiffness and maximum stresses were investigated. RESULTS For glass, displacement showed a stronger correlation with volume (r=0.771) than with C-Factor (r=0.395, p<0.001 for both). For teeth, a stronger correlation was found with C-Factor (r=0.709; p<0.001) than with volume (r=0.546, p<0.001). For similar dimensions, stress and displacement were defined by stiffness. Simultaneous increases in volume and C-Factor led to increases in stress and surface displacement. Maximum stresses were located at the cavosurface angle, internal angle (glass) and at the dentine-enamel junction (teeth). The displacement of the restorations free surface was related to interfacial stress development. CONCLUSIONS Structural stiffness seems to affect the shrinkage stress at the tooth/resin-composite interface in bonded restorations. Deep restorations are always problematic because they showed high shear stress, regardless of their width. FEA is the only tool capable of detecting shear stress due to polymerization as there is still no reliable experimental alternative.

Influence of polymeric matrix on the physical and chemical properties of experimental composites

Nowadays, the main reasons for replacement of resin-based composite restorations are fracture or problems with the integrity of their interface, such as marginal staining, microleakage, or secondary caries. The aim of the present study was to evaluate the influence of the organic matrix on polymerization stress (PS), degree of conversion (DC), elastic modulus (E), flexural strength (FS), Knoop hardness (KHN), sorption (SP), and solubility (SL). In order to obtain a material which combines better mechanical properties with lower PS, seven experimental composites were prepared using BisGMA to TEGDMA molar ratios of 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 and 8:2 and 40% of silica. PS was obtained in a universal testing machine, using acrylic as bonding substrate. DC was determined using Fourier Transform Raman spectroscopy. E and FS were obtained by the three-point bending test. KHN was measured by a microindentation test using a load of 25 g for 30 s. SP and SL were assessed according to ISO 4049. The data were submitted to one-way ANOVA. The increase in BisGMA concentration resulted in the decrease of PS, DC, E, FS and KHN. However, it did not change the SP and SL values. FS, E and KHN showed a strong and direct relationship with the DC of the materials. The composite material with a BisGMA to TEGDMA molar ratio of 1:1 was the one with better mechanical properties and lower PS.

Evaluation of flexural modulus, flexural strength and degree of conversion in BISGMA/TEGDMA resin filled with montmorillonite nanoparticles

This study had as its main objective to evaluate the flexural properties (strength and modulus) and degree of conversion of a dimethacrylate resin containing different amounts of nanoparticulated clay Montomorillonite (MMT) as filler. A series of composites containing similar amounts (in volume) of barium glass particles was also tested as control data. Eight formulations with polymeric matrix-based BisGMA/TEGDMA (Bisphenol A Bis(2-hydroxy-3 methacryloxypropyl)Ether/Triethyleneglycol Dimethacrylate), four added with MMT and four added with barium glass in the volume concentration of 20, 30, 40 and 50 vol% were studied. The degree of conversion was determined using near-IR spectroscopy. Elastic modulus and flexural strength were determined by the three-point bending test. The dispersion of MMT nanoparticles was determined by means of X-ray diffraction and transmission electron microscopy analysis. The fillers montomorillonite and barium glass interacted with polymer matrix-based BisGMA/TEGDMA in a distinct manner. Although the addition of montomorillonite nanoparticles resulted in similar degree of conversion and higher elastic modulus values at all concentrations tested, only at the 20 vol% the flexural strength was statistically higher, compared to the control groups filled with barium glass. This could be related to the need of concentration optimization of montomorillonite for each type of polymer matrix in order to adjust or improve mechanical properties. The addition of low concentrations (<l 20% vol) of montomorillonite nanoparticles in dental composites resins – such as additive or hybrid filler – should be studied, aiming to the reduction of polymerization shrinkage, better mechanical properties and improvement of a new technology for future applications.

Combination of Bioactive Polymeric Membranes and Stem Cells for Periodontal Regeneration: In Vitro and In Vivo Analyses.

Regeneration of periodontal tissues requires a concerted effort to obtain consistent and predictable results in vivo. The aim of the present study was to test a new family of bioactive polymeric membranes in combination with stem cell therapy for periodontal regeneration. In particular, the novel polyester poly(isosorbide succinate-co-L-lactide) (PisPLLA) was compared with poly(L-lactide) (PLLA). Both polymers were combined with collagen (COL), hydroxyapatite (HA) and the growth factor bone morphogenetic protein-7 (BMP7), and their osteoinductive capacity was evaluated via in vitro and in vivo experiments. Membranes composed of PLLA/COL/HA or PisPLLA/COL/HA were able to promote periodontal regeneration and new bone formation in fenestration defects in rat jaws. According to quantitative real-time polymerase chain reaction (qRT-PCR) and Alizarin Red assays, better osteoconductive capacity and increased extracellular mineralization were observed for PLLA/COL/HA, whereas better osteoinductive properties were associated with PisPLLA/COL/HA. We concluded that membranes composed of either PisPLLA/COL/HA or PLLA/COL/HA present promising results in vitro as well as in vivo and that these materials could be potentially applied in periodontal regeneration.

Mechanical characterization and ion release of bioactive dental composites containing calcium phosphate particles

OBJECTIVE to verify the effect of the addition of dicalcium phosphate dihydrate (DCPD) particles functionalized with di- or triethylene glycol dimethacrylate (DEGDMA or TEGDMA) on the degree of conversion (DC), post-gel shrinkage (PS), mechanical properties, and ion release of experimental composites. METHODS Four composites were prepared containing a BisGMA/TEGDMA matrix and 60 vol% of fillers. The positive control contained only barium glass fillers, while in the other composites 15 vol% of the barium was replaced by DCPD. Besides the functionalized particles, non-functionalized DCPD was also tested. DC after 24 h (n = 3) was determined by FTIR spectroscopy. The strain gage method was used to obtain PS 5 min after photoactivation (n = 5). Flexural strength and modulus (n = 10) were calculated based on the biaxial flexural test results, after specimen storage for 24 h or 60 days in water. The same storage times were used for fracture toughness testing (FT, n = 10). Calcium and phosphate release up to 60 days was quantified by ICP-OES (n = 3). Data were analyzed by ANOVA/Tukey test (alpha: 5%). RESULTS Composites containing functionalized DCPD presented higher DC than the control (p < 0.001). The material containing DEGDMA-functionalized particles showed higher PS than the other composites (p < 0.001). After 60 days, only the composite with DEGDMA-functionalized DCPD presented fracture strength similar to the control, while for flexural modulus only the composite with TEGDMA-functionalized particles was lower than the control (p < 0.001). FT of all composites containing DCPD was higher than the control after 60 days (p < 0.005). Calcium release was higher for the composite with non-functionalized DCPD at 15 days and no significant reductions were observed for composites with functionalized DCPD during the observation period (p < 0.001). For all the tested composites, phosphate release was higher at 15 days than in the subsequent periods, and no difference among them was recorded at 45 and 60 days (p < 0.001). CONCLUSIONS DCPD functionalization affected all the studied variables. The composite with DEGDMA-functionalized particles was the only material with strength similar to the control after 60 days in water; however, it also presented the highest shrinkage. The presence of DCPD improved FT, regardless of functionalization. DCPD functionalization reduced ion release only during the first 15 days.

Influence of pH cycling and mechanical loading on the resin-dentin microtensile bond strength

Abstract The durability of adhesive interfaces is still a problem in adhesive restorations in dentistry. Laboratorial ageing methods have been proposed to predict the performance of materials, but they still require standardization. The objective of this study was to evaluate the resin-dentin microtensile bond strength of composite restorations subjected to pH cycling and different levels of mechanical loading. Resin blocks were built over a flat superficial dentin of bovine incisors (n = 40), using a three-step adhesive system. Half of the specimens were submitted to 10 cycles of pH cycling, followed by mechanical loading (0, 500,000; 1,000,000; 2,000,000 cycles – 98 N, 4 Hz). The other half was directly subjected to mechanical loading. After ageing, all groups were subjected to a microtensile bond test. Data were analyzed using two-way ANOVA and Tukey’s test (α = 0.05). The frequency of the early de-bonding was compared using the Chi-square test (α = 0.05). The statistical analysis revealed that the cross-product interaction ‘pH cycling’ vs. ‘number of mechanical loading cycles’ (p = 0.72) as well as the main factor ‘pH cycling’ (p = 0.49) was not statistically significant, and they were not able to reduce the resin–dentin bond strength values. Regarding the number of mechanical loading cycles, the groups subjected to 2,000,000 cycles showed lower bond strength values than the others (p = 0.003). The frequency of debonded specimens increased with mechanical loading. Therefore, it can be concluded that in this restorative model, at least 2,000,000 mechanical cycles are need to decrease the microtensile strength and simulate the ageing of the interface.