Frederick A. Rueggeberg

The Effect of Oxygen Inhibition on an Unfilled/Filled Composite System

Oxygen is known to inhibit vinyl polymerization in resins used for restorative dentistry. This research examined the effects of unfilled resin being blown into a thin layer on etched bovine enamel in atmospheres of room air, argon, or a combination of the two. Onto this thin, cured resin surface, filled resin was added and cured under atmospheric conditions similar to those of the initial polymerization of the unfilled resin. Comparison of the effects of the different testing atmospheres was made by measurement of the shear bond strength of the resin/composite disc to the etched bovine enamel. Monomer conversion values of the unfilled resin were calculated from the infrared spectra of the simulated tooth/disc assembly. Blowing unfilled resin with compressed room air prior to curing caused poor monomer conversion values and resulted in low shear bond strength to etched enamel. Both high monomer conversion and shear strength values resulted when specimens were cured under all-argon conditions. A clinically practical method of maintenance of the tooth under a continuous stream of argon while being cured in room air was shown to provide greater monomer conversion than curing under room-air conditions alone. SEM evaluation showed that the inhibited layer present in room-air curing was both physically displaced by and absorbed into the overlying filled composite. Specimens cured in argon showed an intact, uniformly thick layer of bonding resin next to the etched enamel, with no displacement by or absorption into the composite addition. Unfilled resin cured in room air had a significantly greater thickness of polymerization-inhibited material than did resin cured in an argon atmosphere.

Effect of water content on the physical properties of model dentine primer and bonding resins

OBJECTIVE Primers and adhesives containing hydroxyethyl methacrylate (HEMA) are placed on moist dentine even though several studies indicate that water may interfere with the polymerization reaction. The purpose of this study was to evaluate the influence of increasing amounts of water on the physical properties of a model dentine primer resin (HEMA) and model dentine bonding resin (a mixture of HEMA and Bis-GMA). METHODS Miniature (ca 10 x 0.5 mm (long x thick) hour-glass shaped and parallel-sided specimens were created by casting the monomer or comonomer mixtures into appropriately shaped moulds. The water content was either 0, 5, 9, 17 or 29 vol%. One hour after polymerization, half the specimens were subjected to physical testing under dry conditions. The other half were immersed in water for 24 h and then tested while wet. The ultimate tensile strength (UTS), modulus of elasticity (E), percent elongation at failure, and toughness were calculated. RESULTS The properties of the dry-stored primer and bonding resins were not altered by water incorporation up to 9 vol%. Higher water content lowered the physical properties (P < 0.05). Immersion of primers polymers in water for 24 h significantly decreased their properties. Water immersion of the bonding resins was unaffected only for specimens containing 0 or 5 vol% water. CONCLUSIONS The plasticizing effects of extrinsic water are far more important than the effects of intrinsic water in poly-HEMA resin. Hybrid layers composed primarily of poly-HEMA would be expected to be more elastic than those made with bifunctional, cross-linked polymer chains.

Effects of HEMA on water evaporation from water-HEMA mixtures.

OBJECTIVES The aims of this research were: (1) to determine the relative rates of evaporation of water and HEMA, and (2) to determine the effects of increasing concentrations of HEMA on the rate of evaporation of water from water and HEMA mixtures. METHODS Ten microliters of each solution (100% H2O, 75% H2O-25% HEMA, 50% H2O-50% HEMA, 25% HEMA, 100% HEMA) were placed on the pan of a thermogravimetric analysis instrument held at 37 degrees C. The rate of spontaneous weight loss was measured as a function of time and relative humidity (RH) and compared statistically using ANOVA and Scheffé F test. RESULTS The rate of evaporation of pure water was 32-fold higher than that of 100% HEMA. Addition of HEMA to water lowered the rate of evaporation of water from the water-HEMA mixtures in a manner that was proportional to its effect on lowering the vapor pressure of water (p < 0.05 comparing 50% HEMA with 75% HEMA). The rate of evaporation of water from water-HEMA mixtures was higher (p < 0.05) when the ambient gas was at 0% RH than when it was at 51% RH. SIGNIFICANCE The results indicate that as water evaporates from water-HEMA mixtures, the concentration of HEMA rises because it is relatively non-volatile. This rise in HEMA concentration lowers the vapor pressure of water making it more difficult to remove the last amounts of water. This residual water may interfere with polymerization of adhesive monomers, thereby lowering the quality of the hybrid layer.

Correlation of cytotoxicity, filler loading and curing time of dental composites.

Previous studies have shown that dental resin composites tested in cell culture produce cytotoxic effects on human gingival tissues. In this study, the cytotoxic potential of resin composites on primary human gingival fibroblast cultures was evaluated, based on inhibition of cellular protein synthesis measured by [35S] methionine incorporation. Both resin content and percentage of monomer conversion were considered as potential causes of cytotoxicity. Three resin composites were selected to provide a range of filler content from 45 to 86 wt%. Duplicate sample discs (1 mm thick x 10 mm diameter) of each composite were polymerized for 15, 30 and 60 s, followed by heat (110 degrees C, 10 min), and the degree of monomer conversion for each sample group was measured using Fourier transform infrared spectrophotometry. Identically fabricated discs were placed into 35 mm culture dishes with gingival fibroblasts and incubated for 24 h at 37 degrees C. The cell monolayers then were labelled at 24 h with [35S] methionine, washed and solubilized; then incorporated radioactivity was quantitated by liquid scintillation spectrometry. For each composite, as the percentage of monomer conversion increased, cellular toxicity decreased. In comparing different composites having similar monomer conversions, it was found that the filler/resin ratio was not the only factor determining the composites relative toxicity.

State-of-the-art: Dental photocuring - A review

Light curing in dentistry has truly revolutionized the practice of this art and science. With the exception bonding to tooth structure, there is perhaps no single advancement that has promoted the ease, efficiency, productivity, and success of performing dentistry. Like most every major advancements in this profession, the technology underlying the successful application of light curing in dentistry did not arise from within the profession, but instead was the result of innovative adaptations in applying new advances to clinical treatment. One cannot appreciate the current status of dental photocuring without first appreciating the history and innovations of the science and industry underlying the advances from which it developed. This review will place the current status of the art within the context of its historical progression, enabling a better appreciation for the benefits and remaining issues that photocuring has brought us. Lastly, the manuscript will present thoughts for future considerations in the field, offering suggestions as to how current advances in light-generating science might yet be adapted for dental use.

Polymerization Kinetics of Pre-heated Composite

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 (R p max), time to achieve R p max, and conversion at R p max were calculated from infrared spectra. Composite pre-warming enhanced maximal polymerization rate and overall monomer conversion (top significantly greater than 2 mm). Time when R p max occurred did not change with temperature, but occurred sooner at the top than at 2-mm depth. Conversion at R p max increased with temperature, allowing more of the reaction to occur prior to vitrification than at room temperature.

Solvent-induced dimensional changes in EDTA-demineralized dentin matrix

The purpose of this study was to test the null hypothesis that the re-expansion of dried matrix and the shrinkage of moist, demineralized dentin is not influenced by polar solvents. Dentin disks were prepared from midcoronal dentin of extracted human third molars. After complete demineralization in 0.5M of EDTA (pH 7), the specimens were placed in the well of a device that measures changes in matrix height in real time. Dry, collapsed matrices were created by blowing dry N(2) on the specimens until they shrank to a stable plateau. Polar solvents [water, methanol, ethanol, n-propanol, n-butanol, formamide, ethylene glycol, hydroxyethyl methacrylate (HEMA), or mixtures of water-HEMA] as model primers then were added and the degree of re-expansion measured. These same solvents also were applied to moist, expanded matrices and the solvent-induced shrinkages measured. Regression analysis was used to test the correlations between matrix height and Hansens dispersive, polar, hydrogen bonding, and total solubility parameters (delta(d), delta(p), delta(h), delta(t)). The results indicate that water-free polar solvents of low hydrogen bonding (H-bond) ability (e.g., neat HEMA) do not re-expand dried matrices and that they shrink moist matrices. When HEMA was mixed with progressively higher water concentrations, the model water-HEMA primers expanded the dried matrix in proportion to their water concentrations and they produced less shrinkage of moist matrices. Solvents with higher H-bonding capacities (methanol, ethanol, ethylene glycol, formamide, and water) re-expanded the dried matrix in proportion to their solubility parameters for H-bonding (delta(h)). They also induced small transient shrinkages of moist matrices, which slowly re-expanded. The results require rejection of the null hypothesis.

Effect of curing mode on the polymerization characteristics of dual-cured resin cement systems

OBJECTIVES To evaluate the effects of different curing conditions on the degree of conversion (DC) of dual-cured cementing systems [combination of bonding agent (BA) and resin cement (RC)] using infrared spectroscopy. METHODS Four fourth generation products [Scotchbond Multipurpose Plus/RelyX (3M ESPE), Optibond/Nexus 2 (Kerr), All Bond2/Duolink (Bisco), and Bond-It!/Lute-It! (Pentron)], and three fifth generation materials [Bond1/Lute-It! (Pentron), Prime&Bond NT Dual-Cure/Calibra (Dentsply), and Optibond Solo Dual Cure/Nexus 2 (Kerr)] were applied to the surface of a horizontal attenuated-total-reflectance unit, and were polymerized using one of four conditions: self-cure (SC), direct light exposure through glass slide (DLE, XL3000/3M ESPE) or through pre-cured resin discs (shades A2;A4/2mm thick/Z250/3M ESPE). Infrared spectra of the uncured cementing systems were recorded immediately after application to the ATR, after the system was light-cured or left to self-cure, and spectra were obtained 5 and 10 min later. DC was calculated using standard techniques of observing changes in aliphatic-to-aromatic peak ratios pre- and post-curing. Data (n=5) were analyzed by two-way repeated measures ANOVA and Tukeys test (p=0.05). RESULTS Changes in aliphatic-to-aromatic peak ratios before and after placing RC onto the BA demonstrated that a combined layer was created. All groups exhibited higher DC after 10 min than after 5 min, except the DLE group of Bond-it!/Lute-it!. No significant differences in DC were observed among light-activated groups regardless of the resin disc shade in three of the four fourth generation cementing systems. The SC groups exhibited lower DC than the DLE groups for both fourth and fifth generation products either after 5 or 10 min. CONCLUSION The chemistry of the bonding interface changed when RCs were applied to uncured BAs. The presence of an indirect restoration can decrease the DC of some cementing systems and the self-curing mode leads to lower DC than the light-activating one.

Effect of Heating Delay on Conversion and Strength of a Post-cured Resin Composite

Physical property enhancement in light-cured resin composites from post-cure heating is attributed to free radicals created during initial photocuring, the number of which decreases following initial light-curing. Clinically, it is important to know when the number of remaining free radicals is too low to provide for additional conversion of monomer in post-cure-heated specimens. The hypothesis tested is that the potential for additional conversion in post-cure-heated resin composite restorations is dependent upon the time after initial light-curing at which the specimen is exposed to heat treatment. This research examined the effect of delay in post-cure heating after initial photo-activation on strength and monomer conversion of a commercial resin composite material. Discs (10 x 1 mm) of Herculite XRV (Kerr/Sybron, Orange, CA) were photocured at standardized conditions. One group was left unheated, and another was subjected to post-cure heating (Brilliant DI-500, Coltene AG, Altstatten, Switzerland) at the following times after being light-cured : 5 and 30 min, and 6, 24, 48, 72, 96, and 120 hrs. After the appropriate delay time, unheated and heated specimens (n = 10) were tested for biaxial flexural strength at a constant stressing rate. Recovered, fractured strength specimens (n = 10) were analyzed for cure by means of IR spectroscopy. Post-cure heating increased strength over that of the unheated specimens only for the shortest delay times: 5 or 30 min. Thereafter, strength values were statistically equivalent (p < 0.05). Delay in heating did not significantly enhance strength of post-cure-heated specimens, but delay in time did improve strength of the unheated groups. The greatest monomer conversion was obtained when post-cure heating was applied within 6 hrs following light-curing. The difference in cure between unheated and heated specimens remained significant up to 96 hrs of delay. Flexural strength of post-cure-heated specimens remained unchanged with time delay for heating specimens. Maximal monomer conversion of post-cured specimens is obtained only within 6 hrs of light-curing. The potential for additional conversion arising from post-cure heat treatment is dependent upon the time following initial curing at which heat is applied following initial light-curing. However, delay in heat application has no influence on flexural strength.

Effects of residual ethanol on the rate and degree of conversion of five experimental resins

OBJECTIVES This study examined the extent of ethanol retention in five comonomer blends of experimental methacrylate-based dental adhesives, containing (10, 20, or 30 wt.%) ethanol, after solvent evaporation, as well as observing the effect of residual ethanol and exposure duration on degree of conversion (DC). The null hypothesis that was tested was that residual, unevaporated ethanol has no effect on the rate or extent of DC of polymerized adhesive resins. METHODS A known mass of each mixture was placed in glass wells and evaporated for 60s. The mass of the mixtures before and after evaporation was measured, allowing calculation of the gravimetric ethanol loss/retention. RESULTS The concentration of retained ethanol increased significantly with ethanol concentration (p<0.01): 1.1-1.9 mole/L for 10% ethanol/90% comonomers, 2.2-3.5 mole/L for 20% ethanol, and 2.6-3.7 mole/L for 30% ethanol/70% comonomers. As ethanol is evaporated from solvated comonomer mixtures, the molar concentration of comonomers increases, reducing the vapor pressure of the remaining ethanol. Thus, the fractional loss of ethanol solvent decreases as the comonomer concentration increases. The DC of 10, 20, and 30 wt.% ethanol blends increased with ethanol concentration in four of the five experimental resins (p<0.05), increasing by 30-45% when 10 or 20 wt.% ethanol was added to neat resins, regardless of exposure duration. Depending on the resin system, inclusion of 30% ethanol lowered DC at 20s but increased DC after 40-60s of light exposure. SIGNIFICANCE Since 10 and 20 wt.% ethanol-resin blends increased the DC of solvated resins by 30-45% over neat resins, the test null hypothesis is rejected. Even with prolonged evaporation, 4-9% residual ethanol concentration can remain in 90/10 (wt./wt.) comonomer-ethanol mixtures. This is thought to be because comonomers lower the vapor pressure of ethanol. This amount of residual ethanol facilitates DC but lowers the rate of polymerization.