The effect of cure rate on the mechanical properties of dental resins.

The potential for maximizing conversion of room-temperature, photoactivated resin composite in the oral environment is limited. Pre-heating composite prior to light-curing is hypothesized to increase monomer conversion and reduce the duration of light exposure. Composite temperature was controlled at between 3°C and 60°C prior to exposure with a conventional quartz-tungsten-halogen curing unit: 5, 10, 20, or 40 sec. Monomer conversion was calculated from infrared spectra at 0 mm (top) and 2-mm-deep surfaces 5 min after light initiation. A strong, positive correlation existed between temperature and monomer conversion: top r2 = 0.999, 2 mm r2 = 0.998. Conversion ranged from 31.6% (3°C) to 67.3% (60°C). The duration of light exposure, reduced by 50 to 75% with pre-heated composite, yielded the same or significantly higher conversion (p = 0.001) than with control (22°C, 20 sec). Both hypotheses were accepted: Pre-heating composite prior to photoactivation provides greater conversion requiring reduced light e...

Monomer Conversion of Pre-heated Composite

Use of near-IR to monitor the influence of external heating on dental composite photopolymerization.

Temperature affects the polymerization behavior of dimethacrylate-based materials. This study describes the influence of pre-polymerization temperature and exposure duration on polymerization kinetics of a commercial dental photo-activated composite at the top and at 2-mm depth. We used the temperature-controlled stage of a diamond-attenuated-total-reflectance unit to pre-set composite temperature between 3° and 60°C. Composite was light-exposed by a conventional quartz-tungsten-halogen curing unit for 5, 10, 20, or 40 sec. Real-time conversion, maximum conversion rate (Rpmax), time to achieve Rpmax, and conversion at Rpmax were calculated from infrared spectra. Composite pre-warming enhanced maximal polymerization rate and overall monomer conversion (top significantly greater than 2 mm). Time when Rpmax occurred did not change with temperature, but occurred sooner at the top than at 2-mm depth. Conversion at Rpmax increased with temperature, allowing more of the reaction to occur prior to vitrification t...

Polymerization Kinetics of Pre-heated Composite

The ratio of the double-bond content of monomer to polymer, i.e. degree of conversion (DC) has been used frequently as a convenient means of comparing the behavior and properties of dental composites and adhesives. The purpose of this investigation was to study the relationship of photopolymerization processes, bulk properties, and structure using model dentin adhesives cured in the presence of different ethanol content as an example. There was little difference in the DC of model BisGMA-based adhesives cured in the presence of ethanol concentrations ranging from 0 to 40 wt %, but there were substantial differences in the mechanical properties. Ultimate tensile strength (UTS) and modulus of elasticity decreased with an increase in ethanol content. Polymer structure was revealed by thermal behavior in the glass transition temperature (Tg) region; these measurements were obtained by modulated temperature differential scanning calorimetry (MTDSC) technology, which removes the competing irreversible effects associated with release of volatiles and residual curing. Glass transition temperature of model adhesives decreased substantially with an increase in ethanol content. The DC based on the quantity of remaining double bond has been used extensively to characterize and provide a relative assessment of the quality of dentin adhesives and dental composites. Since polymers differing in linearity, and therefore crosslink density, may have a similar degree of conversion, the measurement of monomer/polymer conversion does not necessarily provide complete representation of the quality or durability of the polymer structure.

Relationship of solvent to the photopolymerization process, properties, and structure in model dentin adhesives

The curing kinetics of dimethacrylate-based vinyl ester resins were studied by scanning and isothermal DSC, gel time studies, and by DMTA. The rate of polymerization was raised by increased methyl ethyl ketone peroxide (MEKP) concentration but the cocatalyst, cobalt octoate, retarded the reaction rate, except at very low concentrations. By contrast, the gel time was reduced for all increases in either peroxide or cobalt concentration. This contradictory behavior was explained by a kinetic scheme in which the cobalt species play a dual role of catalyzing the formation of radicals from MEKP and of destroying the primary and polymeric radicals. The scanning DSC curves exhibited multiple peaks as observed by other workers, but in the present work, these peaks were attributed to the individual influence of temperature on each of fundamental reaction steps in the free radical polymerization. Physical aging appeared to occur during the isothermal polymerization of samples cured below the “fully cured” glass transition temperature (Tg). For these undercured materials, the difference between the DSC Tg and the isothermal curing temperature was approximately 11°C. Dynamic mechanical analysis of a partially cured sample exhibited anomalous behavior caused by the reinitiation of cure of the sample during the DMTA experiment. For partially cured resins, the DSC Tg increased monotonically with the degree of cure, and this dependence was fitted to an equation related to the Couchman and DiBenedetto equations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 769–781, 1997

Peter J. Burchill

Papers

Curing Kinetics and Thermal Properties of Vinyl Ester Resins