Ivo Carlos Correa

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

OBJECTIVES The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. METHODS A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R(p)(max)) profile of the model resin. RESULTS In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ+EDAB exhibited higher DC and R(p)(max) values. In formulations that contained ternary initiator systems, the group CQ+QTX+EDAB was the only one of the investigated experimental groups that exhibited an R(p)(max) value greater than that of CQ+EDAB. The groups QTX+EDAB+DPIHFP and QTX+DPIHFP+SULF exhibited values similar to those of CQ+EDAB with respect to the final DC; however, they also exhibited lower reactivity. SIGNIFICANCE Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations.

The effect of combining photoinitiator systems on the color and curing profile of resin-based composites

OBJECTIVE To evaluate the effect of combining camphorquinone (CQ) and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) on the color and curing profile of resin-based composites. METHODS Experimental composites were produced with different CQ and TPO molar concentrations: CQ-only, 3CQ:1TPO, 1CQ:1TPO, 1CQ:3TPO, and TPO-only. Polywave LED was characterized using a beam profiler. Block-shaped samples (5mm×5mm×3mm depth) were cured in a custom-designed mold with a polywave LED positioned to compare the regions exposed to the 420-495nm and 380-420nm LED emittances. To map the cure profile, degree of conversion (DC) of longitudinal cross-sections from each block were evaluated by FT-NIR. Color, light-transmittance and light-absorption during curing were evaluated on specimens 1-3mm thick. Data were analyzed using ANOVA/Tukeys test (α=0.05; β=0.2). RESULTS Though the polywave LED beam profile was non-uniform, up to a depth of 2mm no differences in DC were found among the composites containing CQ with TPO added up to 50%, regardless of the position under the curing tip. Composites with higher TPO concentration showed a decrease in DC beginning with a depth of 1mm, while composites with higher or similar CQ concentrations did not show decreased DC until a depth of 3mm. Higher TPO concentration reduced initial yellowness and color change after curing; and lower CQ concentration decreased light-absorption at greater depths. SIGNIFICANCE The combination of CQ with TPO added up to 50% reduced the yellowness and color change of composites after curing without affecting cure efficiency up to a depth of 2mm.

The effect of using mixed initiator systems on the efficiency of photopolymerization of dental resins

A study was performed in order to determine the efficiency of the simultaneous use of the photoinitiators phenylpropanedione (PPD) and camphorquinone (CQ) in the polymerization of acrylic polymers and evaluate possible mechanisms leading to synergism or antagonism. It was found that efficiencies of both initiators taken individually are higher than that of their mixture, indicating that when both dyes are used simultaneously there will be an energy transfer from the more efficient initiator (CQ) to the less efficient one (PPD). Also, there was no proof of any reaction between the amine present in the CQ formulation and the PPD excited state.

Effect of the loading of organomodified clays on the thermal and mechanical properties of a model dental resin

Experimental dental resins composed of triethyleneglycol dimethacrylate, urethane dimethacrylate, ethoxylated bisphenol-A-dimethacrylate and bisphenol A glycidyl methacrylate containing an organoclay as filler were prepared by photopolymerization. The addition of organoclay fillers results in slower polymerization rates (0.59 and 0.24 mol L-1 min-1, for the formulations without and with 15% of organoclay, respectively) and lower degrees of conversion (0.50 and 0.35 for the formulations without and with 15% of organoclay), as determined by photocalorimetry. The influence of the organoclay on the thermal and mechanical properties of the resins was evaluated using thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) techniques. The (tan δ) and E´ curves indicate the formation of more rigid materials and the damping curve data indicates more homogeneous materials. An increase of storage modulus, E’, was observed for composites with the higher organoclay filler contents. These effects are due to the higher viscosity of the systems with organoclay, resulting in a lower mobility of the radicals during the propagation step of polymerization, as well as to the scattering of the incident photopolymerizing radiation, which lowers the amount of initiation centres.

Light-emitting Diode Beam Profile and Spectral Output Influence on the Degree of Conversion of Bulk Fill Composites

OBJECTIVES To evaluate the beam profile and the spectral output of monowave and polywave light-emitting diodes (LEDs) and their influence on the degree of conversion (DC) of bulk fill composites. METHODS A monowave LED (Smartlite Focus, Dentsply) and a polywave LED (Valo Cordless, Ultradent) were characterized using a resin calibrator and a laser beam profile analyzer. Two bulk fill composites, Sonic Fill 2 (SF) containing camphorquinone (CQ) and Tetric EvoCeram Bulk Fill (TEB) containing CQ associated with alternative photoinitiators, were placed in custom-designed molds (n=3) and photoactivated by the monowave or polywave LED with 20 J/cm2. To map the DC, longitudinal cross sections (0.5 mm thick) from the center of the restoration were evaluated using FT-NIR microscopy. SF and TEB light transmittances (n=3) through 4-mm-thick specimens were evaluated during curing. Data were analyzed using a split-plot analysis of variance and Tukey test (α=0.05; β=0.2). RESULTS The monowave LED had a radiant emittance of 20 ± 0.5 J/cm2 over 420-495 nm, and the polywave LED had an emittance of 15.5 ± 0.4 J/cm2 over 420-495 nm and of 4.5 ± 0.2 J/cm2 over 380-420 nm. The total radiant exposure at the bottom of TEB was 2.2 ± 0.2 J/cm2 with the monowave LED and 1.6 ± 0.3 J/cm2 with the polywave LED, and for SF it was 0.4 ± 0.1 J/cm2 for both LEDs. There were no differences in the curing profiles produced either by the monowave or the polywave LED (p=0.9), according to the regions under influence of blue and/or violet emission at the same depth. There was no statistical difference in the DC for SF using the monowave or polywave LED at any depth (p=0.29). TEB had a higher DC at up to 2 mm in depth when the polywave LED was used (p<0.004), but no differences were found when starting at 2.5 mm. CONCLUSIONS Monowave and polywave LEDs emitted nonhomogeneous light beams, but this did not affect the DC homogeneity of bulk fill composites. For composites containing CQ associated with alternative photoinitiators, polywave LEDs had a higher DC, but only at the top part of the restoration; lower wavelength absorption photoinitiators were ineffective in deeper areas.