David C. Watts

Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function

The empirical dielectric decay function γ(t)= exp –(t/τ0)β may be transformed analytically to give the frequency dependent complex dielectric constant if β is chosen to be 0.50. The resulting dielectric constant and dielectric loss curves are non-symmetrical about the logarithm of the frequency of maximum loss, and are intermediate between the Cole-Cole and Davidson-Cole empirical relations. Using a short extrapolation procedure, good agreement is obtained between the empirical representation and the experimental curves for the α relaxation in polyethyl acrylate. It is suggested that the present representation would have a general application to the α relaxations in other polymers. The Hamon approximation, with a small applied correction, is valid for the present function with β= 0.50 in the range log(ωτ0) > –0.5, but cannot be used at lower frequencies.

Determination of polymerization shrinkage kinetics in visible-light-cured materials: methods development

An instrument for the reproducible measurement of polymerization shrinkage kinetics is described, constructed around a disc-shaped specimen sandwiched between two glass plates. Test specimens of light-sensitive dental restorative materials were irradiated through the lower, rigid plate. The upper, non-rigid plate was readily deflected by an increase of the adhesive stress from the polymerizing and shrinking sample. Deflection was measured by an LVDT transducer and computer-recorded. Dimensional changes were confined to the specimen disc-thickness dimension, such that the fractional linear shrinkage approximated the volumetric shrinkage. Shrinkage data are reported for representative materials: unfilled and resin composites, base-lining materials, and an impression material. Equilibrium shrinkage magnitudes ranged from 0.65%, for the impression material, to 7.9% for the unfilled resin. The kinetic behavior was approximately characterized by an overall time constant, ranging from 12.5 to 280 s, associated with an exponential growth curve, although the initial shrinkage was near-linear in time, for many materials, due to non-steady-state concentrations of polymer free-radicals. The test-specimen geometry facilitates rapid and essentially uniform cure and hence the determination of minimum possible time-constants at each ambient temperature and incident light-intensity. Study of hybrid glass-ionomer materials, without spurious dehydration effects, was also achieved.

Further considerations of non symmetrical dielectric relaxation behaviour arising from a simple empirical decay function

The empirical dielectric decay function ϕ(t)= exp –(t/τ0)β, 0 0, but significant corrections may have to be applied for β >0.5 and log ωτ0 < 0.

Photo-polymerization shrinkage-stress kinetics in resin-composites: methods development

OBJECTIVES Studies of free shrinkage-strain kinetics on restoratives have begun to multiply. However, there have been fewer investigations of the more difficult problem of concurrent stress-kinetic measurements. The aim was to outline design parameters for a new methodology for this problem, amenable especially to light-cured materials, and to present illustrative results for a range of restorative composites. METHODS Absolute values of stress measurable for a given material and geometry are dependent upon the stiffness of the measurement system. In an infinitely stiff system, the measured stress would also tend towards infinity. Real teeth and their cavities are not infinitely stiff; they have elastic and visco-elastic compliance. Consequently, it is important that some minimal, but essentially constant compliance be allowed, whatever the final or time-dependent modulus of the material may be. This goal has been realised by measurement of the time-development, for a disk-geometry specimen (phi=10, h approximately 1.0 mm) of stress (S(r)), with a calibrated cantilever beam-geometry load cell. A novel specimen-holder design was used for this purpose, held in a rigid base assembly. Specimen thicknesses (or gap-widths) of 0.8 and 1.2 mm were specifically investigated on four representative resin-composites. Concurrent measurements were made of the end-displacement of the cantilever load cell, relative to a lower glass plate retaining the specimen. RESULTS Load-calibration of the cantilever load cell gave an end-displacement per unit stress of circa 6 microm/MPa. This compares with literature values for cuspal compliance or displacement of circa 20 microm. Re-normalisation of the stress-data was implemented. This was accomplished assuming Hookes law behavior at each instant and equivalent to a stiffer system, with a correction (multiplier) factor of 4 on the raw-stress values. For the materials examined, resultant maximum-stress levels determined were circa 5-8 MPa Stress-levels obtained at 1.2mm thickness were slightly higher (11-15%) than the level of stress obtained at 0.8 mm thickness. This is attributable to the greater mass of material undergoing shrinkage at 1.2 mm, offset slightly by the different C-factors. SIGNIFICANCE The new device is a practical and self-contained system for rapid and accurate measurement of stress-kinetics in photo-polymerising and also self-cure materials.

Resin composite monomers alter MTT and LDH activity of human gingival fibroblasts in vitro.

OBJECTIVES Substances such as monomers may be released from composite resin systems and may induce adverse effects in biological tissues. The aim of this study is to investigate the cytotoxic concentrations of resin composite monomers on cultures of human gingival fibroblasts. METHODS A range of dilutions of five resin composite monomers (HEMA, HPMA, DMAEMA, TEGDMA, and Bis-GMA) were added to the culture medium of human gingival fibroblasts for 24 h. Their cytotoxic effects were measured by using two colorimetric functional assays, mitochondrial dehydrogenase activity (MTT) and lactate dehydrogenase activity (LDH) assay. The logP values (water/octanol partition) of test monomers were also calculated computationally. RESULTS Mitochondrial reducing activity assessed with the MTT test was inhibited by all monomers and all the monomers increased the LDH release in a reproducible dose dependent manner. A wide range of TC 50 values (concentrations altering MTT and LDH activity by 50%) (0.32-5.8 mM by MTT assay and 0.36-6.7 mM by LDH assay) was observed. Ranking of composite resin monomer cytotoxicities (TC 50) were similar for both the MTT and LDH assays, (Bis-GMA>TEGDMA>DMAEMA>HPMA >HEMA). However, the MTT assay was found to be more sensitive than the LDH assay, particularly when lower doses of the tested monomers were determined. The ranking of TC 50 concentrations correlated with the calculated logP values. SIGNIFICANCE Monomers used in dental restorative materials show a variety of toxic effects on gingival fibroblasts. A combination approach using MTT and LDH assays provides valuable information about their toxic effects.

Fracture toughness of human dentin.

Plane strain fracture toughness (KIC) was determined for coronal dentin using compact tension test-pieces obtained from recently extracted permanent lower molar teeth. Specimens were prepared and tested such that the moving crack front was aligned parallel to the tubule orientation. The fracture toughness (K IC) was temperature-invariant in the range 0-60°C, and the mean value obtained was 3.08 MN.(m)-1.5 (SD: 0.33). The critical strain energy release rate (GIC) of dentin was also calculated utilizing modulus data and was found to increase slightly with temperature, possibly as a consequence of significant temperature-dependence of the modulus: The fracture toughness of dentin is midway in the range (0.23- 6.56) observed for cortical bone and is a factor of two greater than that exhibited by most current restorative materials.

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

OBJECTIVES The 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. METHODS Experimental 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/cm(2), was measured using the bonded-disk technique at room temperature with respect to time. RESULTS The 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. SIGNIFICANCE The 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.

Performance of two blue light-emitting-diode dental light curing units with distance and irradiation-time.

OBJECTIVES To assess the performance of two blue light-emitting-diode (LED) curing units, in terms of their spectral output and irradiance and the depth of cure (dcure) produced in standard hybrid and modified composites, compared with a conventional quartz tungsten halogen (QTH) light curing unit. METHODS The following light curing units (LCUs) were studied: Elipar-Freelight-1 LED (LED-1) 3 M-ESPE, Ultralume-2 LED (LED-2) Optident, and the Optilux-500 QTH (QTH-1) Sybron-Kerr. For each LCU, using a UV-visible spectrophotometer, the output spectrum was measured and the irradiance of emitted light as a function of source-detector distance. Three composites were studied of similar formulation but differing in their initiator concentrations and/or opacity. These were: Tetric Ceram (A3), Tetric Ceram HB containing an additional photoinitiator responding to approximately 435 nm (A3) and Tetric Ceram Bleach (L). dcure was measured using a calibrated digital needle-penetrometer, as a function of source-specimen distance and for irradiance periods of 10, 20 and 40 s. RESULTS Each unit delivered a single peak in the blue region of the visible spectrum. The wavelength maxima for LED-1, LED-2 and QTH-1 were 486.4, 458.2 and 495.2 nm, respectively. Cure-depth (dcure) values varied significantly (p<0.001) with irradiance times and source-specimen distance for both LED and QTH sources. The percentage reduction in dcure values resulting from LED versus QTH irradiance increased with source-specimen distance. SIGNIFICANCE The LED-LCUs had an energy-efficient spectral output for conventional composite curing but had a lower irradiance compared with the QTH-LCU, leading to reduced performance in depths of cure. Design improvements to provide greater irradiance from the LED-1 and to a lesser extent LED-2, should result in increased performance.

Marginal gap formation of light-activated restorative materials : effects of immediate setting shrinkage and bond strength

OBJECTIVES The purpose of this study was to explore multiple correlations between shrinkage, bonding and marginal gap parameters, immediately after light-activation, for three classes of restorative materials. The correlations of interest were between: (a) their marginal gap formation in tooth cavities, (b) their free setting shrinkage-strain determined by two different measurement methods ((i) the marginal gap-width in a non-bonding Teflon cavity and (ii) a linear (diametral) measure of shrinkage-strain), and (c) their shear bond strengths to enamel and to dentin. METHODS The maximum marginal gap width and the opposing width (if any) in the tooth cavity were measured immediately (3 min) after light-activation. Two factors for the setting shrinkage-strain and the shear bond strength to enamel and to dentin were measured concomitantly. RESULTS Out of the set of restorative materials investigated, those that produced a smaller marginal gap in the tooth cavity had a smaller marginal gap in the Teflon cavity. There was a highly significant correlation between the two parameters (r=0.914, p<0.001). However, no relationship was observed between the marginal gap in the tooth cavity and the immediate diametral shrinkage-strain (p>0.05). Thus the restorative materials that produced a smaller marginal gap in the tooth cavity did not generally have a smaller diametral setting shrinkage-strain. Furthermore, no relationship was observed between the marginal gap in the tooth cavity and the shear bond strength to enamel or to dentin (p>0.50). SIGNIFICANCE For light-activated restorative materials during the early stage of setting (<5 min), the free shrinkage-strain, measured by marginal-gaps in Teflon cavities, had a greater correlation with immediate marginal-gaps in tooth cavities than either the immediate diametral shrinkage-strain or the bond strengths to the tooth structure.

Hygroscopic dimensional changes of self-adhering and new resin-matrix composites during water sorption/desorption cycles.

OBJECTIVES To study hygroscopic dimensional changes in new resin-matrix composites during water sorption/desorption cycles. METHODS Five materials were examined: a self-adhering flowable composite: Vertise® Flow (VF), a universal composite: GC Kalore (GCK), two micro-fine hybrid composites: GC Gradia Direct Anterior (GDA) and GC Gradia Direct Posterior (GDP), and a posterior restorative composite: Filtek® Silorane (FS). Five disk-shaped specimens of each material were prepared (15 mm diameter × 2 mm thickness) according to ISO 4049. The mean diameter of each specimen was measured by a custom-built laser micrometer (to a resolution of 200 nm) periodically over 150d water immersion and 40d recondition periods at (37 ± 1)°C. Perspex controls were used. Data analysis was performed by repeated measures ANOVA, one-way ANOVA and Tukeys post hoc test (p<0.05). RESULTS Differences in hygroscopic expansion were found for all test materials during sorption, ranging from 0.74% (± 0.05) for FS to 4.82% (± 0.13) for VF. The differences were significant for all materials (p<0.001), except between GCK and GDA. The mathematical relationship between diametral expansion and square root of time was non-linear. VF exhibited significant dehydration shrinkage. SIGNIFICANCE The silorane composite FS had the lowest hygroscopic expansion. The extent of compensation of polymerization shrinkage by hygroscopic expansion depends on materials, specimen dimensions and time-scale. So the clinical situation must be taken into consideration in the application of these findings.