Monomer conversion of composite dental resins photoactivated by a halogen lamp and a LED: a FT-Raman spectroscopy study

Eighteen circular blocks of resins cured either by a LED or a halogen lamp (20, 40 and 60 s), had their top (T) and bottom (B) surfaces studied using a FT-Raman spectrometer. Systematic changes in the intensity of the methacrylate C=C stretching mode at 1638 cm-1 as a function of exposure duration were observed. The calculated degree of conversion (DC) ranged from 45.0% (B) to 52.0% (T) and from 49.0% (B) to 55.0% (T) for the LED and halogen lamp, respectively. LED and halogen light produced similar DC values with 40 and 60 s of irradiation.

Effect of Pre-Heating Resin Composite and Light-Curing Units on Monomer Conversion

The purpose of this study was to evaluate the effect of pre-heating resin composite photo-cured with light-curing units (LCU) by FT-IR. Twenty specimens were made in a metallic mold (4 mm diameter x 2 mm thick) from composite resin-Tetric Ceram (R) (Ivoclar/Vivadent) at room temperature (25 degrees C) and pre heated to 37, 54, and 60 degrees C. The specimens were cured with halogen curing light (QTH) and light emitted by diodes (LED) during 40 s. Then, the specimens were pulverized, pressed with KBr and analyzed with FT-IR. The data were submitted to statistical analysis of variance and Kruskal-Wallis test. Study data showed no statistically significant difference to the degree of conversion for the different light curing units (QTH and LED) (p > 0.05). With the increase of temperature there was significant increase in the degree of conversion (p < 0.05). In this study were not found evidence that the light curing unit and temperature influenced the degree of conversion.

Effect of pre-heating resin composite and light-curing units on monomer conversion

The purpose of this study was to evaluate the effect of pre-heating resin composite photo-cured with light-curing units (LCU) by FT-IR. Twenty specimens were made in a metallic mold (4 mm diameter × 2 mm thick) from composite resin-Tetric Ceram® (Ivoclar/Vivadent) at room temperature (25°C) and pre-heated to 37, 54, and 60°C. The specimens were cured with halogen curing light (QTH) and light emitted by diodes (LED) during 40 s. Then, the specimens were pulverized, pressed with KBr and analyzed with FT-IR. The data were submitted to statistical analysis of variance and Kruskal-Wallis test. Study data showed no statistically significant difference to the degree of conversion for the different light curing units (QTH and LED) (p > 0.05). With the increase of temperature there was significant increase in the degree of conversion (p < 0.05). In this study were not found evidence that the light curing unit and temperature influenced the degree of conversion. © 2010 Pleiades Publishing, Ltd.

Long-term surface hardness and monomer conversion of a nonofilled and a microhybrid composite resin

Objective: This study aims to evaluate the degree of conversion (DC) and hydrolytic degradation through the Vickers hardness test (HV) of a nanofilled (Filtek™ Z-250, 3M) and a microhybrid (Filtek™Supreme-XT, 3M) composite resin. Materials and methods: Eight disk-shaped specimens (4 mm diameter × 2 mm thick, ISO 4049) of each material were prepared for each test. Composites were inserted into single increment in a metallic matrix and light-cured for 40 seconds. VH readings were performed for each specimen at predetermined intervals: immediately after polymerization (control), 1, 2, 3, 7, 14, 21, 30 and 180 days. After curing, initial hardness measurements were performed and the specimens were immersed in artificial saliva at 37°C. For DC (%), specimens were ground, pressed with KBr and analyzed by FT-IR spectrophotometer. Results: Student t-test showed that there was no difference between the resins for DC (p = 0.252). ANOVA analysis revealed that Z-250 VH means were all greater than S-XT, for both top and bottom surfaces, whatever the storage-period in artificial saliva (p < 0.001). After 180 days of storage, the hardness obtained for S-XT was similar with that at the baseline, for both top and bottom surfaces. While for Z-250 hardness was not significantly different from baseline only for top surface, but there was a significant decrease observed in hardness for bottom surface. Conclusion: The materials tested showed no evidence of hydrolytic degradation in a significant way, in a 6-month storagetime in artificial saliva. Nanofilled resin presents a monomer conversion comparable to the conventional microhybrid.

The effect of polymerization mode on monomer conversion, free radical entrapment, and interaction with hydroxyapatite of commercial self-adhesive cements

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Composite pre-heating: Effects on marginal adaptation, degree of conversion and mechanical properties

Objectives. This study evaluated the effect of composite pre-polymerization temperature and energy density on the marginal adaptation (MA), degree of conversion (DC), flexural strength (FS), and polymer cross-linking (PCL) of a resin composite (Filtek Z350, 3M/ESPE). Methods. For MA, class V cavities (4mmx2mmx2mm) were prepared in 40 bovine incisors. The adhesive system Adper Single Bond 2 (3M/ESPE) was applied. Before being placed in the cavities, the resin composite was either kept at room-temperature (25 degrees C) or previously pre-heated to 68 degrees C in the Calset (TM) device (AdDent Inc., Danbury, CT, USA). The composite was then light polymerized for 20 or 40s at 600mW/cm(2) (12 or 24 J/cm(2), respectively). The percentage of gaps was analyzed by scanning electron microscopy, after sectioning the restorations and preparing epoxy resin replicas. DC (n = 3) was obtained by FT-Raman spectroscopy on irradiated and non-irradiated composite surfaces. FS (n = 10) was measured by the three-point-bending test. KHN (n = 6) was measured after 24h dry storage and again after immersion in 100% ethanol solution for 24 h, to calculate PCL density. Data were analyzed by appropriate statistical analyses. Results. The pre-heated composite showed better MA than the room-temperature groups. A higher number of gaps were observed in the room-temperature groups, irrespective of the energy density, mainly in the axial wall (p < 0.05). Composite pre-heating and energy density did not affect the DC, FS and PCL (p > 0.05). Significance. Pre-heating the composite prior to light polymerization similar in a clinical situation did not alter the mechanical properties and monomer conversion of the composite, but provided enhanced composite adaptation to cavity walls. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.

Continuous and gradual photo-activation methods: influence on degree of conversion and crosslink density of composite resins

Thermal properties and degree of conversion (DC%) of two composite resins (microhybrid and nanocomposite) and two photo-activation methods (continuous and gradual) displayed by the light-emitting diode (LED) light-curing units (LCUs) were investigated in this study. Differential scanning calorimetry (DSC) thermal analysis technique was used to investigate the glass transition temperature (T(g)) and degradation temperature. The DC% was determined by Fourier transform infrared spectroscopy (FT-IR). The results showed that the microhybrid composite resin presented the highest T(g) and degradation temperature values, i.e., the best thermal stability. Gradual photo-activation methods showed higher or similar T(g) and degradation temperature values when compared to continuous method. The Elipar Freelight 2 (TM) LCU showed the lowest T(g) values. With respect to the DC%, the photo-activation method did not influence the final conversion of composite resins. However, Elipar Freelight 2 (TM) LCU and microhybrid resin showed the lowest DC% values. Thus, the presented results suggest that gradual method photo-activation with LED LCUs provides adequate degree of conversion without promoting changes in the polymer chain of composite resins. However, the thermal properties and final conversion of composite resins can be influenced by the kind of composite resin and LCU.

Effect of ceramic shade on the degree of conversion of a dual-cure resin cement analyzed by FTIR

Objectives: The aim of this research was to evaluate the degree of monomer conversion of different resin cement shades when photocured under different feldspathic ceramic shades. The photocuring time was also evaluated as well as the translucency of each ceramic shade. Methods: Three VITA VM7 ceramic shades (Base Dentin 0M1, Base Dentin 2M2 and Base Dentin 5M3) were used to determine the translucency percentage. A spectrophotometer MiniScan was used to measure the opacity percentage of each specimen (2-mm-thick) and then the translucency was calculated. To measure the degree of conversion (DC), the resin cement (Variolink II; A3 Yellow and transparent) specimens (thickness: 100 μm) were photocured under a ceramic block (2-mm-thick) for 20 or 40 s. Specimens photocured without the ceramic block were used as control. Sixteen groups (n = 3) were evaluated. Micro-ATR/FTIR spectrometry was used to evaluate the extent of polymerization of all specimens after 24 h. The %DC was calculated of experimentally polymerized versus maximally polymerized composite. Results: The translucency percentages of 0M1, 2M2 and 5M3 ceramics were 12.41 (1.02)%, 5.75 (1.91)% and 1.07 (0.03)%, respectively. The %DC of both resin cement shades cured under ceramic 5M3 was significantly lower than the other groups (p < 0.05). The %DC of 0M1 groups exhibited no significant difference from 2M2 groups (p > 0.05), with the exception of the transparent cement photocured for 40 s. Conclusion: Photocuring under 2 mm ceramic showed that the increase in chroma saturation significantly decreased Variolink II resin cement %DC (100-μm-thick). © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of Temperature on the Degree of Conversion and Working Time of Dual-Cured Resin Cements Exposed to Different Curing Conditions

Objectives: This study evaluated the degree of conversion (DC) and working time (WT) of two commercial, dual-cured resin cements polymerized at varying temperatures and under different curing-light accessible conditions, using Fourier transformed infrared analysis (FTIR). Materials and Methods: Calibra (Cal; Dentsply Caulk) and Variolink II (Ivoclar Vivadent) were tested at 25 degrees C or preheated to 37 degrees C or 50 degrees C and applied to a similar-temperature surface of a horizontal attenuated-total-reflectance unit (ATR) attached to an infrared spectrometer. The products were polymerized using one of four conditions: direct light exposure only (600 mW/cm(2)) through a glass slide or through a 1.5- or 3.0-mm-thick ceramic disc (A2 shade, IPS e.max, Ivoclar Vivadent) or allowed to self-cure in the absence of light curing. FTIR spectra were recorded for 20 min (1 spectrum/s, 16 scans/spectrum, resolution 4 cm(-1)) immediately after application to the ATR. DC was calculated using standard techniques of observing changes in aliphatic-to-aromatic peak ratios precuring and 20-min postcuring as well as during each 1-second interval. Time-based monomer conversion analysis was used to determine WT at each temperature. DC and WT data (n=6) were analyzed by two-way analysis of variance and Tukey post hoc test (p=0.05). Results: Higher temperatures increased DC regardless of curing mode and product. For Calibra, only the 3-mm-thick ceramic group showed lower DC than the other groups at 25 degrees C (p=0.01830), while no significant difference was observed among groups at 37 degrees C and 50 degrees C. For Variolink, the 3-mm-thick ceramic group showed lower DC than the 1-mm-thick group only at 25 degrees C, while the self-cure group showed lower DC than the others at all temperatures (p=0.00001). WT decreased with increasing temperature: at 37 degrees C near 70% reduction and at 50 degrees C near 90% for both products, with WT reduction reaching clinically inappropriate times in some cases (p=0.00001). Conclusion: Elevated temperature during polymerization of dual-cured cements increased DC. WT was reduced with elevated temperature, but the extent of reduction might not be clinically acceptable.

Development of a Continuous Emulsion Copolymerization Process in a Tubular Reactor

This contribution describes the development of a continuous emulsion copolymerization processs for vinyl acetate and n-butyl acrylate in a tubular reactor. Special features of this reactor include the use of oscillatory (pulsed) flow and internals (sieve plates) to prevent polymer fouling and promote good radial mixing, along with a controlled amount of axial mixing. The copolymer system studied (vinyl acetate and butyl acrylate) is strongly prone to composition drift due to very different reactivity ratios. An axially dispersed plug flow model, based on classical free radical copolymerization kinetics, was developed for this process and used successfully to optimize the lateral feeding profile to reduce compositional drift. An energy balance was included in the model equations to predict the effect of temperature variations on the process. The model predictions were validated with experimental data for monomer conversion, copolymer composition, average particle size, and temperature measured along the reactor length.

Modeling Vinyl Acetate and n-Butyl Acrylate Emulsion Copolymerization Process

This work presents a mathematical model for the vinyl acetate and n-butyl acrylate emulsion copolymerization process in batch reactors. The model is able to explain the effects of simultaneous changes in emulsifier concentration, initiator concentration, monomer-to-water ratio, and monomer feed composition on monomer conversion, copolymer composition and, to lesser extent, average particle size evolution histories. The main features of the system, such as the increase in the rate of polymerization as temperature, emulsifier, and initiator concentrations increase are correctly represented by the model. The model accounts for the basic features of the process and may be useful for practical applications, despite its simplicity and a reduced number of adjustable parameters.

Effects of adhesive temperature on the early and 6-month dentin bonding

Objectives: The aim of this study was to test the effect of adhesive temperature on the bond strength to dentin (mu TBS) and silver nitrate uptake (SNU) of an ethanol/water (Adper Single Bond 2 [SB]) and an acetone-based (Prime&Bond 2.1 [PB]) etch-and-rinse adhesive system. Methods: The bottles of each adhesive were kept in various temperatures (5 degrees C, 20 degrees C, 37 degrees C and 50 degrees C) for 1 h previously to its application in the occlusal demineralized dentin of 40 molars. Bonded sticks (0.8 mm(2)) were tested in tension (0.5 mm/min) immediately (IM) or after 6 months (6 M) of water storage. Two bonded sticks from each hemi-tooth were immersed in silver nitrate and analyzed by SEM. Data were analyzed by two-way repeated measures ANOVA and Tukey`s test (alpha = 0.05). Results: No significant difference in mu TBS was detected for both adhesives at 5 degrees C and 20 degrees C. The highest bond strength for PB was observed in the 37 degrees C group while for SB it was in the 50 degrees C. Significant reductions of bond strengths were observed for PB at 37 degrees C and SB at 50 degrees C after 6 M of water storage. Silver nitrate deposition was seen in all hybrid layers, irrespective of the group. Lower silver nitrate deposition (water trees) in the adhesive layer was seen for PB and SB at higher temperatures. Conclusions: The heating or refrigeration of the adhesives did not improve their resin-dentin bond resistance to water degradation over time. (C) 2009 Elsevier Ltd. All rights reserved.

Characterization of dimethacrylate polymeric networks: A study of the crosslinked structure formed by monomers used in dental composites

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. (C) 2010 Elsevier Ltd. All rights reserved.

Adhesive Temperature: Effects on Adhesive Properties and Resin-Dentin Bond Strength

Objectives: To evaluate the effect of adhesive temperature on the resin-dentin bond strength (mu TBS), nanoleakage (NL), adhesive layer thickness (AL), and degree of conversion (DC) of ethanol/water- (SB) and acetone-based (PB) etch-and-rinse adhesive systems. Methods: The bottles of the two adhesives were kept at each temperature (5 degrees C, 20 degrees C, 37 degrees C, and 50 degrees C) for 2 hours before application to demineralized dentin surfaces of 40 molars. Specimens were prepared for mu TBS testing. Bonded sticks (0.8 mm(2)) were tested under tension (0.5 mm/min). Three bonded sticks from each tooth were immersed in silver nitrate and analyzed by scanning electron microscopy. The DC of the adhesives was evaluated by Fourier transformed infrared spectroscopy. Results: Lower mu TBS was observed for PB at 50 degrees C. For SB, the mu TBS values were similar for all temperatures. DC was higher at 50 degrees C for PB. Higher NL and thicker AL were observed for both adhesives in the 5 degrees C and 20 degrees C groups compared to the 37 degrees C and 50 degrees C groups. The higher temperatures (37 degrees C or 50 degrees C) reduced the number of pores within the adhesive layer of both adhesive systems. Conclusions: It could be useful to use an ethanol/water-based adhesive at 37 degrees C or 50 degrees C and an acetone-based adhesive at 37 degrees C to improve adhesive performance.