Effect of experimental resin cements containing thio-urethane oligomers on the durability of ceramic-composite bonded interfaces.

Thio-urethane oligomers improve conversion and mechanical properties of resin cements. The objective of this study was to evaluate the effect of resin cements formulated with thio-urethane (TU) oligomers on microtensile bond strength (µTBS) of ceramics to composites subjected to thermal/mechanical cycling. Methods: BisGMA/UDMA/TEGDMA (50/30/20 wt%) containg 0 (control, EC) or 20 wt% aliphatic or aromatic thiourethane (HDDI and BDI, respectively) were mixed with CQ/amine (0.2/0.8 wt%) and 25 wt% 0.7um Ba glass. Rely X Ultimate (RU-3M ESPE) was used as the commercial control. The cements were sandwiched between ceramic (IPS e.max Press) and resin composite blocks (Filtek Supreme, 3 M-ESPE). Eight bonded blocks were produced per experimental group. Prior to bonding, ceramic surfaces were etched (20 s - 10% HF) and silanized. Composite surfaces were treated with Single Bond Universal (3 M ESPE). Specimens were stored for 24 h in distilled water at 37 °C, and then either tested immediately, or subjected to thermal (10,000, 5 °C and 55 °C) or mechanical cycling (300,000 cycles). Sticks (1 mm2, average of 25 sticks per block) were cut and tested for µTBS (1.0 mm/min). Data were analyzed with two-way ANOVA/Tukey's test (α = 5%). Fracture surfaces were analyzed to determine failure modes. Results: The µTBS for HDDI and RU was significantly higher than BDI and EC cements. BDI led to significantly higher µTBS than EC after 24 h, Tc and Mf. µTBS decreased significantly after thermal/mechanical cycling for all groups. Failure modes were predominantly adhesive or mixed. Significance: The use of selected thio-urethane oligomers was able to increase the µTBS of composite-cement-ceramic specimens. Tc and Mf reduced µTBS for all resins cements.

Optical properties and colorimetric evaluation of resin cements formulated with thio-urethane oligomers.

OBJECTIVE: The aim of this study was to evaluate the color parameters and optical properties of resin cements (RCs) formulated with thio-urethanes (TUs). MATERIALS AND METHODS: Six TUs were synthesized by combining thiols (pentaerythritol tetra-3-mercaptopropionate [PETMP] or trimethylol-tris-3-mercaptopropionate [TMP]) with di-functional isocyanates (1,6-Hexanediol-diissocyante [HDDI] [aliphatic-AL] or 1,3-bis(1-isocyanato-1-methylethyl) benzene [BDI] [aromatic-AR] or Dicyclohexylmethane 4,4'-Diisocyanate [HMDI] [cyclic-CC]). TUs (20 wt%) were added to a BisGMA/UDMA/TEGDMA matrix. Filler was introduced at 60 wt%. Fluorescence was evaluated through an UV-light emitting equipment. Coordinates L*, a*, and b* were obtained in the black and white reflectance to evaluate the contrast ratio (CR) and translucency parameter (TP00 ). The coordinates obtained from transmittance were used to evaluate lightness (L*), chroma (C*), color difference (ΔE00 ) after 6 month, and whiteness index for Dentistry (WID ). RESULTS: RCs formulated with TUs presented significantly higher CR, and fluorescence (with T_AR). Significantly lower C*, L*, and TP00 (except for P_AR and T_AL) were also observed in RCs containing TUs. ΔE00 were not significant among the materials. WID was not influenced. CONCLUSION: RCs composed by TU oligomers present higher CR and lower translucency. The material also present higher fluorescence depending on the oligomer used. CLINICAL SIGNIFICANCE: The use of thio-urethanes to formulate resin cements can ensure a luting material with improved potential to mask colored substrates due to the higher contrast ratio and lower translucency obtained. A final higher fluorescence of restoration is also expected with the use of specific oligomer.

Resin cements formulated with thio-urethanes can strengthen porcelain and increase bond strength to ceramics.

OBJECTIVES: The use of thio-urethane oligomers has been shown to significantly improve the mechanical properties of resin cements (RCs). The aim of this study was to use thio-urethane-modified RC to potentially reinforce the porcelain-RC structure and to improve the bond strength to zirconia and lithium disilicate. METHODS: Six oligomers were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP, P) or trimethylol-tris-3-mercaptopropionate (TMP, T) - with di-functional isocyanates - 1,6-Hexanediol-diissocyante (HDDI) (aliphatic, AL) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic, AR) or Dicyclohexylmethane 4,4'-Diisocyanate (HMDI) (cyclic, CC). Thio-urethanes (20 wt%) were added to a BisGMA/UDMA/TEGDMA organic matrix. Filler was introduced at 60 wt%. The microshear bond strength (µSBS), Weibull modulus (m), and failure pattern of RCs bonded to zirconia (ZR) and lithium disilicate (LD) ceramics was evaluated. Biaxial flexural test and fractographic analysis of porcelain discs bonded to RCs were also performed. The biaxial flexural strength (σbf) and m were calculated in the tensile surfaces of porcelain and RC structures (Z = 0 and Z = -t2, respectively). RESULTS: The µSBS was improved with RCs formulated with oligomers P_AL or T_AL bonded to LD and P_AL, P_AR or T_CC bonded to zirconia in comparison to controls. Mixed failures predominated in all groups. σbf had superior values at Z = 0 with RCs formulated with oligomers P_AL, P_AR, T_AL, or T_CC in comparison to control; σbf increased with all RCs composed by thio-urethanes at Z = -t2. Fractographic analysis revealed all fracture origins at Z = 0. CONCLUSION: The use of specific thio-urethane oligomers as components of RCs increased both the biaxial flexural strength of the porcelain-RC structure and the µSBS to LD and ZR. CLINICAL SIGNIFICANCE: The current investigation suggests that it is possible to reinforce the porcelain-RC pair and obtain higher bond strength to LD and ZR with RCs formulated with selected types of thio-urethane oligomers.

Shrinkage / stress reduction and mechanical properties improvement in restorative composites formulated with thio-urethane oligomers.

Thio-urethane oligomers (TUs) have been shown to favorably modify methacrylate networks to reduce stress and significantly increase fracture toughness. Since those are very desirable features in dental applications, the objective of this work was to characterize restorative composites formulated with the addition of TUs. TUs were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP) or trimethylol-tris-3-mercaptopropionate (TMP) - with isocyanates - 1,6-Hexanediol-diissocyante (HDDI) (aliphatic) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic) or dicyclohexylmethane 4,4'-Diisocyanate (HMDI) (cyclic), at 1:2 isocyanate:thiol, leaving pendant thiols. 20wt% TU were added to BisGMA-TEGDMA (70-30%). To this organic matrix, 70wt% silanated inorganic fillers were added. Near-IR was used to follow methacrylate conversion and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM) and toughness (T), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS) was measured with the bonded disk technique. Glass transition temperature (Tg) and heterogeneity of network were obtained with dynamic mechanical analysis. The addition of TUs led to an increase in mechanical properties (except for Tg and FS). Fracture toughness ranged from 1.6-1.94MPam1/2 for TU-modified groups, an increase of 33-61% in relation to the control (1.21 ± 0.1MPam1/2). Toughness showed a two-fold increase in relation to the control: from 0.91MPa to values ranging from 1.70-1.95MPa. Flexural modulus was statistically higher for the TU-modified groups. The Tg, as expected, decreased for all TU groups due to the greater flexibility imparted to the network (which also explains the increase in toughness and fracture toughness). Narrower tan-delta peaks suggest more homogeneous networks for the TU-modified materials, though differences were marked only for TMP_AL. Degree of conversion was not affected by the addition of TUs. VS was similar for all groups, with one exception where VS dropped (PETMP-cyclic). Finally, PS showed a reduction of 23-57% for TU-modified groups (6.7 ± 1.3 to 11.9 ± 1.0MPa) in relation to the control (15.56 ± 1.4MPa). The addition of thio-urethane oligomers was able to reduce polymerization stress by up to 57% while increasing fracture toughness by up to 61%.

Rheological and mechanical properties and interfacial stress development of composite cements modified with thio-urethane oligomers.

OBJECTIVES: Thio-urethane oligomers have been shown to reduce stress and increase toughness in highly filled composite materials. This study evaluated the influence of thio-urethane backbone structure on rheological and mechanical properties of resin cements modified with a fixed concentration of the oligomers. METHODS: Thio-urethane oligomers (TU) were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP) or trimethylol-tris-3-mercaptopropionate (TMP) - with isocyanates - 1,6-hexanediol-diissocyante (HDDI) (aliphatic) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic) or dicyclohexylmethane 4,4'-diisocyanate (HMDI) (cyclic), at 1:2 isocyanate:thiol, leaving pendant thiols. 20wt% TU were added to BisGMA-UDMA-TEGDMA (5:3:2). 60wt% silanated inorganic fillers were added. Near-IR was used to follow methacrylate conversion and rate of polymerization ( [Formula: see text] ). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). PS was measured on the Bioman. Viscosity (V) and gel-points (defined as the crossover between storage and loss shear moduli (G'/G″)) were obtained with rheometry. Glass transition temperature (Tg), cross-link density and homogeneity of the network were obtained with dynamic mechanical analysis. Film-thickness was evaluated according to ISO 4049. RESULTS: DC and mechanical properties increased and [Formula: see text] and PS decreased with the addition of TUs. Gelation (G'/G″) was delayed and DC at G'/G″ increased in TU groups. Tg and cross-link density dropped in TU groups, while oligomers let to more homogenous networks. An increase in V was observed, with no effect on film-thickness. Significant reductions in PS were achieved at the same time conversion and mechanical properties increased. SIGNIFICANCE: The addition of thio-urethane oligomers proved successful in improving several key properties of resin cements, without disrupting the procedures dentists use to polymerize the material. This approach has potential to be translated to commercial materials very readily.

Characterization of methacrylate-based composites containing thio-urethane oligomers.

OBJECTIVE: To evaluate the ability of thio-urethane oligomers to improve the properties of restorative composite resins. METHODS: Oligomers were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 0-20 wt% to BisGMA-TEGDMA (70-30 wt%). Silanated inorganic fillers were added (70 wt%). Materials were photoactivated at 800 mW/cm(2) filtered to 320-500 nm. Near-IR was used to follow degree of methacrylate conversion (DC). Mechanical properties were evaluated in three-point bending with 2 mm × 2 mm × 25 mm bars for flexural strength/modulus and toughness (FS/E, and T) according to ISO 4049, and 2 mm × 5 mm × 25 mm notched specimens for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Results were analyzed with ANOVA/Tukey's test (α=5%). RESULTS: Significant increase in DC was observed in thio-urethane-containing materials especially for the group with 20 wt% of aliphatic version. Materials composed by oligomers also promoted higher FS, E, and KIC in comparison to controls irrespective of thio-urethane type. A significant increase in toughness was detected by ANOVA, but not distinguished in the groups. The PS was significantly reduced by the presence of thio-urethane for almost all groups. CONCLUSIONS: The use of thio-urethane oligomer to compose methacrylate-based restorative composite promote increase in DC, FS, E and KIC while significant reduces PS. SIGNIFICANCE: A simple additive was shown to reduce stress while increasing convrersion and mechanical properties, mainly fracture toughness. This has he potential of increasing the service life of dental composites, without changing current operatory procedures.

Thio-urethane oligomers improve the properties of light-cured resin cements.

Thio-urethanes were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 10-30 phr to BisGMA-UDMA-TEGDMA (5:3:2, BUT). 25 wt% silanated inorganic fillers were added. Commercial cement (Relyx Veneer, 3M-ESPE) was also evaluated with 10-20 phr of aromatic oligomer. Near-IR was used to follow methacrylate conversion (DC) and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS, %) was measured with the bonded disk technique. Results were analyzed with ANOVA/Tukey's test (α=5%). In general terms, for BUT cements, conversion and mechanical properties in flexure increased for selected groups with the addition of thio-urethane oligomers. The aromatic versions resulted in greater FS/FM than aliphatic. Fracture toughness increased by two-fold in the experimental groups (from 1.17 ± 0.36 MPam(1/2) to around 3.23 ± 0.22 MPam(1/2)). Rpmax decreased with the addition of thio-urethanes, though the vitrification point was not statistically different from the control. VS and PS decreased with both oligomers. For the commercial cement, 20 phr of oligomer increased DC, vitrification, reduced Rpmax and also significantly increased KIC, and reduced PS and FM. Thio-urethane oligomers were shown to favorably modify conventional dimethacrylate networks. Significant reductions in polymerization stress were achieved at the same time conversion and fracture toughness increased.