Improvements to light transmittance in light-cured composite resins by the utilisation of low refractive index dimethacrylates

In an effort to improve the light transmittance of light-cured composite resins while avoiding degradation of their physical properties, 4 dimethacrylates having low refractive indices and a bulky backbones such as alicyclic or fluorine-substituted bisphenol groups were synthesized. The depths of cure and physical properties of 6 experimental composite resins containing these new monomers were, then, examined and compared to those of 3 control composite resins containing UDMA, BisMEPP, or BisGMA. The depths of cure of the experimental group containing the synthesized monomers were greater than those of the control group with the exception of the composite containing UDMA. The depth of cure increased as the difference between the refractive indices of the matrix monomer and silica filler decreased. The physical properties of 2 composites in the experimental group were comparable to those of the control group. The matrix monomers of these 2 composites were a mixture of 4,8-dimethacryloxymethylene tricyclo [5.2.1.0] decane or 2,2-bis (4-methacryloxyethoxy phenyl) hexafluoropropane and TEGDMA in a molar ratio of 1/1.     

Evaluation of two Bis-GMA analogues as potential monomer diluents to improve the mechanical properties of light-cured composite resins.

OBJECTIVES: The aim of this study was to investigate the influence of new diluent agents, diluent ratio and filler content, on relevant mechanical properties of several novel composite resins containing Bis-GMA as resin matrices, and to compare these with the properties of composites based on TEGDMA, a conventionally used diluent. METHODS: Two Bis-GMA analogues were synthesized and 20 experimental composite resins were prepared combining three monomer mixtures (Bis-GMA/TEGDMA, Bis-GMA/CH3 Bis-GMA and Bis-GMA/CF3 Bis-GMA), at three dilution rates (85/15, 10/90, 0/100) and three levels of hybrid filler content (barium aluminosilicate glass): 0, 10 and 35%. Flexural strength (FS), modulus of elasticity (ME) and microhardness (VHN) of the composites were evaluated. Five specimens of each material were prepared for each mechanical test, light-cured over 120 s and stored in water at 37 degrees C for 1 week. Three-point bending test was used for FS measurement and VHN was quantified by using a Vickers microindentor. Data were analyzed by ANOVA and Student-Newman-Keuls tests (P<0.05). RESULTS: Materials with CH3 Bis-GMA showed an enhanced VHN. Mean FS was higher for matrices containing TEGDMA. Overall, dilution favored FS and VHN but not ME. Filler loading specially improved ME and VHN. SIGNIFICANCE: Results correlate with an increase in the extent of polymerization due to the higher flexibility of the less viscous comonomer starting system and the hydrophobic character of the Bis-GMA analogues.     

Novel light-cured resins and composites with improved physicochemical properties.

OBJECTIVES: The aim of this study was to determine the effect of two new diluent agents (Bis-GMA analogues), at different dilution levels and filler contents on relevant physicochemical properties of several novel resins and composites containing Bis-GMA as matrix. Composites using TEGDMA as diluent were used as control. METHODS: Twenty formulations were prepared combining three monomer mixtures (Bis-GMA/TEGDMA, Bis-GMA/CH(3) Bis-GMA and Bis-GMA/CF(3) Bis-GMA), at three dilution levels (85/15, 10/90, 0/100) and two percentages of filler loading (silanated barium aluminosilicate glass): 0%, 10%, 35%. Preliminary rheological testing was performed in order to obtain the viscosity of the resin samples. Resins and composites were then inserted into molds and light-cured (500mW/cm(2)). The properties evaluated were: (1) homogeneity of curing (HC), using FTIR or Vickers microindentor, (2) microhardness, by a Vickers microindentor, (3) depths of cure and oxygen inhibitor effect (OIE), quantified by scraping, (4) water contact angle on the materials surface, (5) water sorption and solubility, performed by the Oysaed-Ruyter method and (6) scanning electron microscopy analysis of the specimens surfaces. Data were analyzed by ANOVA and Student-Newman-Keuls tests (p<0.05). RESULTS: Materials with CH(3) Bis-GMA and CF(3) Bis-GMA exhibited less hydrophilicity, water sorption and solubility. Bis-GMA dilution induced an increase in depth of cure and promoted a higher OIE, particularly when the diluent was TEGDMA. Filler loading reduced the OIE and increased hydrophobicity of the resins. SIGNIFICANCE: CH(3) Bis-GMA may be considered as good candidate to be used as diluent because when replacing TEGDMA-induced lower hydrolytic degradation and increase in HC.     

Dimethacrylate monomers with varied fluorine contents and distributions.

OBJECTIVES: There are many unique properties associated with fluorinated polymers that make these materials attractive for use in the challenging oral environment. This study was devised to better define the influence of fluorine content and its structural distribution on properties of fluorinated resins and composites, especially with regard to their water-related and mechanical properties. METHODS: A series of fluorinated dimethacrylate monomers was prepared by reaction of aromatic diepoxides with fluoroalcohols and subsequent conversion of the resulting diols to the methacrylates. Composites based on monomer systems comprised of the fluorinated monomers with 1,10-decamethylene dimethacrylate and reinforced with silanized quartz filler were evaluated for conversion, water contact angle, water sorption and diametral tensile strength. RESULTS: By selection of reactants, fluorine was introduced as trifluoromethyl groups, extended fluoroalkyl pendant chains, or combinations of the two. Photopolymerization conversion among the experimental composites was generally equal to or greater than that of a conventional Bis-GMA/TEGDMA composite. While the water contact angles generally increased with fluorine content, no correlation was obtained between fluorine content and water sorption of the composites. The mechanical strength of the fluorinated composites showed a general decline with increasing fluorine content and consistent variations due to specific structural features. SIGNIFICANCE: A versatile route to fluorinated dimethacrylates with diverse structural and fluorine distribution patterns is presented. Composites from these monomers are very hydrophobic but have relatively low mechanical strength. The monomers described can be considered as useful additives to moderate the water sorption of conventional resins. However, the results of this study point to specific fluorinated resin structures that are expected to provide a more optimal balance between hydrophobicity and mechanical strength that will improve the long-term performance of dental composites.     

Physical and mechanical properties of an experimental dental composite based on a new monomer.

OBJECTIVE: The purpose of this study was to investigate the physical and mechanical properties of a dental composite based on BTDMA, a new dimethacrylate monomer based on BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), and to compare these with the properties of a composite based on commonly used Bis-GMA monomer. METHODS: Experimental composites were prepared by mixing the silane-treated filler with the monomers. The prepared pastes were inserted into the test molds and heat-cured. Light-cured composites were also prepared using camphorquinone and amine as photoinitiator system. Degree of conversion of the light-cured and heat-cured composites was measured using FTIR spectroscopy. The flexural strength, flexural modulus, diametral tensile strength (DTS), water sorption, water contact angle, microhardness and thermal expansion coefficient of the prepared composites were measured and compared. Water uptake of the monomers was also measured. RESULTS: The results showed that the mechanical properties of the new composite are comparable with the properties of the Bis-GMA-based composite but its water sorption is higher. BTDMA as a monomer containing aromatic rings and carboxylic acid groups in its structure gives a composite with good mechanical properties. There is a close relation between the contact angle, water sorption of the cured composite and water uptake of their monomers. SIGNIFICANCE: Finding new monomers as alternatives for Bis-GMA have been a challenge in the field of dental materials and any investigation into the properties of new composites would be beneficial in the development of dental materials.     

Hydrolytic stability of experimental hydroxyapatite-filled dental composite materials.

OBJECTIVES: The purpose of this study was to analyze the behavior in water, related to mechanical properties, of experimental composites for dental restoration. METHODS: The studied materials were composed of a visible-light-curing monomer mixture (Bis-GMA and TEGDMA or HEMA) and micrometric, nanometric or a mixture of both sizes hydroxyapatite particles as a reinforcing filler. Filler particles were modified with a coupling agent (citric, hydrosuccinic, acrylic or methacrylic acid or silane). The hydrolytic stability of the evaluated materials was studied through total elution and water-uptake tests. Percent net-mass variation was daily monitored and analyzed as a function of time. Mechanical performance was examined through flexural properties and Vickers hardness. Morphological surface changes were observed with scanning electron microscopy. ANOVA statistical analysis was performed (P<0.05). RESULTS: In general, the use of HEMA instead of TEGDMA did not substantially worsen the composite quality. Dental composites containing only nanometric particles of hydroxyapatite as a filler are unsuitable for clinical performance. Midway-filled composite resins loaded with micro-HAP particles, coated with citric, acrylic or methacrylic acid displayed low percent elution and water-uptake values. Mechanical properties were similar or even superior to those measured for silane treated particles. SIGNIFICANCE: More research is needed to further improve the interaction of nano-HAP particles with the polymeric matrix, either as a single filler or, preferentially, mixed with micro-HAP, that will allow to increase the total loading of reinforcing filler and, hence, to improve the mechanical properties.     

Effect of filler system on the mechanical properties of light-cured composite resins. I. Effect of various types of silica fillers on the mechanical properties of the composite resins

To investigate the effect of silica fillers on the mechanical properties of visible light-cured composite resins, Bis-GMA-based composites with four types of silica fillers were prepared. The mechanical properties of the composites with splinter-shaped silica fillers increased with increasing the filler fraction. Although the spherical silica filler could be filled more with resin monomer than the splinter-shaped silica filler, the mechanical properties of spherical silica-filled composite were relatively lower than those of the composite with splinter-shaped silica fillers. The micro particle silica-filled composite showed no obvious increase in the mechanical properties in either the dry or wet conditions. SEM observations of the fractured resin surface revealed that fracture occurred through the resin matrix as well as the resin/filler interface and the mechanical properties of each composite resin were correlated with the nature of crack propagation.     

Mechanical properties and cure depth of UDMA-based composite resins

Mechanical properties and cure depth of visible light-cured composite resins based on six types of UDMA (IP-HEMA, IP-HPMA, XY-HPMA, MC-HPMA, UEDMA and UPDMA) monomers were investigated. Under wet conditions, the mechanical properties of the composite resins based on aliphatic UDMA (UEDMA and UPDMA) monomers were inferior to those based on the other UDMA monomers containing aromatic or cyclohexane rings in their chemical structures. The cure depth for these UDMA-based composite resins increased with increasing irradiation time. The composite resin based on the XY-HPMA monomer showed a cure depth and transmission coefficient superior to the other composite resins.     

Heat curing behavior of light-cured composite resins investigated by dynamic differential scanning calorimetry

The heat curing behavior of light-cured restorative composite resins, light-cured crown and bridge veneering resins, pure dimethacrylate monomers, Bis-GMA monomers containing various initiators, and monomer mixtures were investigated by slow heating at a constant rate with differential scanning calorimetry (DSC) without any light irradiation--the so-called dynamic DSC measurement. Some of the light-cured restorative composite resins and the light-cured crown and bridge veneering resins showed a sharp exothermic peak due to heat curing. Pure TEDMA also showed a sharp exothermic peak, whereas the Bis-GMA monomers containing catalysts for light curing showed no exothermic peak. It seems that heat curing behavior of light-cured composite resins depends not on the decomposition of camphorquinone, but on that of the monomer itself.     

Effect of monomer structure on the mechanical properties of light-cured composite resins

The effects of monomer structure on the mechanical properties of visible light-cured composite resins based on the seven types of aromatic dimethacrylates were investigated. The results of this study suggested that the mechanical properties of the composite resins were dependent upon the chemical structure of the dimethacrylate monomers employed. The composites based on dimethacrylates with hydroxy groups showed a relatively significant decrease in flexural strength, elastic modulus, and compressive proportional limit under wet conditions. The segmental mobility of dimethacrylate monomers considerably influenced the nature of cured composites. Bis-GMA-F-based composite showed superior mechanical properties to a conventional Bis-GMA-based material. The SEM observation of fractured surfaces revealed that failure mainly occurred through the resin matrix of the composite resins.     

Development of dental composite resin utilizing low-shrinking and low-viscous monomers

To lower the viscosity of composite resins, experimental composite resins were produced using low-viscosity monomer mixtures of newly developed polyfunctional acrylates, and the mechanical and physical properties of the hardened composites were investigated. Mechanical (i.e., compressive, diametral tensile, and bending) strength of a polymer obtained from one new monomer mixture without fillers was similar to that of a bis-GMA/TEGDMA (2/1 weight ratio) based polymer. As for the hardened composites, the mechanical strength of composites produced using the new monomer mixtures showed a different tendency from that of bis-GMA based composites. Further, even the viscosity of composite pastes with high filler content was markedly lower than that of bis-GMA based composites. In terms of setting shrinkage, the composites consisting of new monomer mixtures exhibited significantly smaller shrinkage than the bis-GMA based composites, and decreased with increase in filler content.     

Durability of commercial composite resin. Chronological change in transverse strength and transverse elastic modulus of composite resin immersed in MeOH

The durability of visible light-cured composite resin was examined. Five kinds of commercial redox type composite resin and 7 kinds of visible light-cured composite resin were used and their base monomers were analyzed by HPLC. After the set products were immersed in MeOH, transverse strength and transverse elastic modulus were measured. Furthermore, the MeOH sorption, solubility in MeOH and main soluble component were examined. The main component of the base monomer in all 5 kinds of redox type was Bis-GMA. Seven kinds of visible light-cured composite resin consisted of 4 kinds of Bis-GMA (including BMPEPP) and 3 kinds of UDMA. Both cases of redox type and visible light-cured type of composite resin, when they were immersed in MeOH, transverse strength and transverse elastic modulus decreased. In the case of redox type (Clearfil posterior new bond), the decrease of transverse strength and transverse elastic modulus was small, that is, its base monomer was Bis-GMA, and large quantities of hybrid type filler were mixed. In the case of redox type, transverse strength and transverse elastic modulus showed a tendency to decrease with the increase of MeOH sorption. Solubility of 12 kinds of these composite resins was 0.25-4.78% and its main component in Pyrofil light bond A was BMPEPP, the residual were coincident with the main component of base monomer.     

Polymer properties on resins composed of UDMA and methacrylates with the carboxyl group.

The properties of dental matrix resins have been improved by synthesis of new monomers. However, except for improvements in water-resistance, monomers with better mechanical properties than Bis-GMA and UDMA could not being synthesized. Changing the point of emphasis, we tried to improve the mechanical properties controlling the matrix resin higher structure using noncovalent bonds. We prepared a matrix resin structured by UDMA, which is a high viscosity base monomer with imino groups, and by a low viscosity acidic monomer with carboxyl groups, which permits noncovalent bonds such as hydrogen bonds or electrostatic interaction with imino groups. The maximal mechanical strength for matrix resins structured by UDMA and an acidic monomer was obtained with a composition of imino groups and carboxyl groups at a ratio of 1:1. This mechanical strength value was higher than those obtained with UDMA resin or with a Bis-GMA/TEGDMA/UDMA resin with typical composition. The improvement in mechanical properties may be due to the complex based on noncovalent bonds, between the imino groups of UDMA and the carboxyl groups of the acidic monomers.     

Refractive index mismatch and monomer reactivity influence composite curing depth

Limited cure depth is a drawback of light-activated composites. We hypothesize that curing light transmission and cure depth are influenced by monomer reactivity and filler/resin refractive index mismatch. Light transmission throughout cure was recorded for composites based on strontium (refractive index 1.51) or barium (refractive index 1.53) glass fillers. Fillers were mixed (70 wt%) with 4 bisphenol-A diglycidyl-ether-dimethacrylate (bis-GMA):triethylene glycol dimethacrylate (TEGDMA) formulations with refractive indices ranging from 1.4703 to 1.5370. Following polymerization, cure depth and pre- and post-cure translucency parameters were determined. Transmission changes and cure depths related to monomer reactivity and filler/resin refractive index mismatch with significant interaction. Composites became more opaque or translucent on curing. Optimizing filler/resin refractive index mismatch provides increased curing depth and assists shade-matching.     

Fabrication and evaluation of Bis-GMA/TEGDMA dental resins/composites containing nano fibrillar silicate.

OBJECTIVE: To investigate the reinforcement of Bis-GMA/TEGDMA dental resins (without conventional glass filler) and composites (with conventional glass filler) with various mass fractions of nano fibrillar silicate (FS). METHODS: Three dispersion methods were studied to separate the silanized FS as nano-scaled single crystals and uniformly distribute them into dental matrices. The photo-curing behaviors of the Bis-GMA/TEGDMA/FS resins were monitored in situ by RT-NIR to study the photopolymerization rate and the vinyl double bond conversion. Mechanical properties (flexural strength, elastic modulus and work-of-fracture) of the nano FS reinforced resins/composites were tested, and analysis of variance (ANOVA) was used for the statistical analysis of the acquired data. The morphology of nano FS and the representative fracture surfaces of its reinforced resins/composites were examined by SEM/TEM. RESULTS: Impregnation of small mass fractions (1% and 2.5%) of nano FS into Bis-GMA/TEGDMA (50/50 mass ratio) dental resins/composites improved the mechanical properties substantially. Larger mass fraction of impregnation (7.5%), however, did not further improve the mechanical properties (one way ANOVA, P>0.05) and may even reduce the mechanical properties. The high degree of separation and uniform distribution of nano FS into dental resins/composites was a challenge. Impregnation of nano FS into dental resins/composites could result in two opposite effects: a reinforcing effect due to the highly separated and uniformly distributed nano FS single crystals, or a weakening effect due to the formation of FS agglomerates/particles. SIGNIFICANCE: Uniform distribution of highly separated nano FS single crystals into dental resins/composites could significantly improve the mechanical properties of the resins/composites.     

Transmittance of light-cured composite resins. 1. Measurement of transmittance with time

The factors that influence the change of the transmittance of light-cured composite resins during polymerization were examined. Six experimental composite resins such as used organic composite filler and fourteen commercial composite resins were investigated using the experimental device for measurement of the transmittance. The transmittance of the experimental composite resins were from 25 to 73%. The transmittance of the experimental composite resins changed with time; a group with increasing transmittance (G1), a group giving a maximum transmittance (G2), and a group with decreasing transmittance (G3). These changes of transmittance were influenced by the difference in the refractive indices between matrix resin and filler, but the refractive index that indicated a maximum transmittance of matrix resin during polymerization could not be observed when the refractive index of the matrix resin and filler was same. The light transmitted through the commercial composite resins was less than half of the irradiation light. This change of transmittance could also be classified into the three groups mentioned above. The commercial composite resins belonged to the group with increasing transmittance (G1).     

Bending strength and depth of cure of light-cured composite resins irradiated using filters that simulate enamel

This study evaluates the light-attenuating effects of enamel on the properties of light-cured restorative resins using simple experimental filters. Three filters were designed to replicate the light transmittance characteristics of 0.5, 1.0 and 1.5 mm thick human enamel. The bending strength, depth of cure, and levels of residual monomer for 12 shades of three commercial light-cured composite resins were examined. These resins were cured either using direct irradiation from a light source or irradiation through one of the filters. For all materials, the bending strength and depth of cure of specimens irradiated through a filter were lower and the levels of residual monomer were higher than those found in specimens irradiated directly. The results indicate that the light-attenuating effect of enamel reduces the polymerization efficiency, resulting in poorer mechanical properties of light-cured composite resins.     

Evaluation of methylene lactone monomers in dental resins.

alpha-Methylene-gamma-butyrolactone (MBL), which can be described as the cyclic analog of methyl methacrylate, exhibits greater reactivity in free radical polymerizations than conventional methacrylate monomers. Unfilled resin formulations composed of Bis-GMA/MBL or Bis-GMA/TEGDMA/MBL were light-cured. The effect of the more reactive methylene lactone monomer on mechanical properties and the degree of conversion of the polymers was examined. The infrared absorption bands for the carbon-carbon double bonds of MBL and the methacrylate monomers are well resolved and allow the conversion of each component to be calculated individually. The incorporation of a small amount of MBL (5 w/o) to Bis-GMA significantly increased the conversion; however, additional MBL (10 to 30 w/o) did not further increase the Bis-GMA conversion level. This appears to indicate an incompatibility between MBL and the bulky Bis-GMA monomer. Addition of 10 w/o MBL to Bis-GMA/TEGDMA (7:3) resulted in a cured resin with 71% methacrylate and 75% overall conversion efficiencies compared with the 57% conversion of the control formulation. The diametral tensile and the transverse strengths were approximately 10% greater for the MBL resin compared with the Bis-GMA/TEGDMA control; however, these differences were not statistically significant. The synthesis and polymerization of several substituted methylene lactones was also studied.     

Dimethacrylate based on cycloaliphatic epoxide for dental composite.

OBJECTIVES: The aim of this study was to investigate the kinetics and mechanical properties of dimethacrylate monomer based on cycloaliphatic epoxide for dental restorative composite. METHODS: Dimethacrylate based on cycloaliphatic epoxide (EPCDMA) was copolymeirzed with TEGDMA by varying the curing conditions: monomer composition and light intensity. A real-time near FTIR technique was employed to monitor the double bond conversion and the rate of polymerization. Dynamic mechanical analysis was performed on a dynamic mechanical analyzer, and volume shrinkage of the cured samples was determined by pycnometric method. RESULTS: The results of kinetics showed that, two peaks of maximum rate of polymerization (Rpmax) occurred when the amount of TEGDMA was more than 30wt%. Increasing the amount of TEGDMA, the final double bond conversion and polymerization shrinkage both increased, while the glass transition temperature (Tg) decreased. All EPCDMA/TEGDMA mixtures had slightly higher storage modulus at body temperature (37 degrees C). When compared with Bis-GMA/TEGDMA (70/30), the EPCDMA/TEGDMA (70/30) system assumed similar reactivity and volume shrinkage but higher Tg. SIGNIFICANCE: EPCDMA had comparable mechanical properties to those of Bis-GMA.     

The effect of resin matrix composition on the polymerization shrinkage and rheological properties of experimental dental composites.

OBJECTIVES: This study was undertaken to evaluate the effect of the resin matrix composition of experimental composites on their polymerization shrinkage and rheological properties. METHODS: Six experimental composites consisting of varying ratios of Bis-GMA, TEGDMA, and UDMA were made. All composites had the same amount of filler (barium-aluminum-silicate glass, 76.5 wt.%) and initiator concentrations (camphorquinone, 1.7 wt.%). To investigate the effects of different resin matrices on the polymerization shrinkage, a newly developed measurement method was used. Using a rotational rheometer, a dynamic oscillatory shear test was undertaken to evaluate the rheological properties, including the storage shear modulus (G'), loss shear modulus (G'), loss tangent (tandelta), phase angle (delta), and complex viscosity (eta*) of the experimental composites as a function of frequency (0.1-10Hz). RESULTS: The polymerization shrinkage and complex viscosity of the experimental composites ranged from 2.61 to 3.88 vol.% and from 3.8 to 181.4Pas, respectively. The experimental composite composed of 17.5% Bis-GMA and 4.4% TEGDMA showed the lowest shrinkage and highest viscosity. The composite composed of 8.7% Bis-GMA and 13.1% TEGDMA showed the highest shrinkage and lowest viscosity. With increasing TEGDMA content, the polymerization shrinkage increased but the viscosity decreased. The substitution of UDMA for TEGDMA reduced the shrinkage level but increased viscosity. There was an inverse relationship between the polymerization shrinkage and complex viscosity. All experimental composites exhibited pseudoplasticity. SIGNIFICANCE: Within the limitations of this study, resin matrix composition significantly affected the volumetric shrinkage and rheological properties of the experimental composites.