Phase evolution in lithium disilicate glass-ceramics based on non-stoichiometric compositions of a multi-component system: structural studies by 29Si single and double resonance solid state NMR.

The crystallization mechanism of a high-strength lithium disilicate glass-ceramic in the SiO(2)-Li(2)O-P(2)O(5)-Al(2)O(3)-K(2)O-(ZrO(2)) system, used as restorative dentistry material, has been examined on the basis of quantitative (29)Si magic angle spinning (MAS) and (29)Si{(7)Li} rotational echo double resonance (REDOR) NMR spectroscopy. Crystallization occurs in two stages: near 650 °C a significant fraction of the Q(3) units disproportionates into crystalline Li(2)SiO(3) and Q(4) units. Upon further annealing of this glass-ceramic to 850 °C the crystalline Li(2)SiO(3) phase reacts with the Q(4) units of the softened residual glass matrix, resulting in the crystallization of Li(2)Si(2)O(5). The NMR experiments provide detailed insight into the spatial distribution of the lithium ions suggesting the absence of lithium ion clustering in the residual glassy component of the final glass-ceramic. (31)P MAS-NMR spectra indicate that phosphate acts as a lithium ion scavenger, resulting in the predominant formation of orthophosphate (P(0)) and some pyrophosphate (P(1)) groups. Crystallization of Li(2)SiO(3) occurs concomitantly with the formation of a highly disordered Li(3)PO(4) phase as evidenced from strong linebroadening effects in the (31)P MAS-NMR spectra. Well-crystallized Li(3)PO(4) is only formed at annealing conditions resulting in the formation of crystalline lithium disilicate. These results argue against an epitaxial nucleation process previously proposed in the literature and rather suggest that the nucleation of both lithium metasilicate and lithium disilicate starts at the phase boundary between the disordered lithium phosphate phase and the glass matrix.

Synthesis of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide - a tailor-made photoinitiator for dental adhesives.

Because of the poor solubility of the commercially available bisacylphosphine oxides in dental acidic aqueous primer formulations, bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide (WBAPO) was synthesized starting from 3-(chloromethyl)-2,4,6-trimethylbenzoic acid by the dichlorophosphine route. The substituent was introduced by etherification with 2-(allyloxy)ethanol. In the second step, 3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoic acid was chlorinated. The formed acid chloride showed an unexpected low thermal stability. Its thermal rearrangement at 180 ° C resulted in a fast formation of 3-(chloromethyl)-2,4,6-trimethylbenzoic acid 2-(allyloxy)ethyl ester. In the third step, the acid chloride was reacted with phenylphosphine dilithium with the formation of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine, which was oxidized to WBAPO. The structure of WBAPO was confirmed by ¹H NMR, ¹³C NMR, ³¹P NMR, and IR spectroscopy, as well as elemental analysis. WBAPO, a yellow liquid, possesses improved solubility in polar solvents and shows UV-vis absorption, and a high photoreactivity comparable with the commercially available bisacylphosphine oxides. A sufficient storage stability was found in dental acidic aqueous primer formulations.

Benzoyl germanium derivatives as novel visible light photoinitiators for dental materials.

OBJECTIVES: The objective of this study was to investigate the use of benzoyl germanium derivatives as a novel visible light photoinitiator of resin-based dental composites. Selected mechanical properties, such as flexural strength and flexural modulus, setting time, storage stability, and UV light stability, of the composites based on the novel photoinitiators benzoyltrimethylgermane (BTMGe) or dibenzoyldiethylgermane (DBDEGe) were investigated and compared to the properties of materials that are cured with a mixture of camphorquinone (CQ) and ethyl 4-(N,N-dimethylamino)benzoate (EMBO). METHODS: The flexural strength and flexural modulus of elasticity were determined according to ISO 4049. For this purpose, test specimens (2 mm x 2 mm x 25 mm) of the composites investigated were prepared in stainless steel moulds and light-cured (150 mW/cm2, 2 s x 180 s). The flexural strength and flexural modulus of elasticity were measured after immersing the cured specimens in water for 24h at 37 degrees C and in certain cases, after they had been boiled for 24h in water. In addition, the setting time, curing depth, storage and UV stability of selected composites were determined. RESULTS: The novel photoinitiators BTMGe or DBDEGe can be used to substitute the binary photoinitiator CQ/EMBO in visible light-cured restorative composites. Especially, DBDEGe showed a significantly higher photocuring activity in composites with a filler load of about 60 wt. % in comparison to that of CQ/EMBO. In addition, composites based on BTMGe or DBDEGe showed an improved UV stability and a storage stability comparable to that of CQ/EMBO-based composites.

Sol-gel materials 2. Light-curing dental composites based on ormocers of cross-linking alkoxysilane methacrylates and further nano-components.

OBJECTIVES: The objective of this study was to investigate the use of ormocers, which were synthesized from amine or amide dimethacrylate trialkoxysilanes. Ormocers showed improved biocompatibility in dimethacrylate-diluent-free composite restoratives. Selected mechanical properties, such as flexural strength and flexural modulus of experimental composites containing ormocers were investigated. In addition, the influence of methacrylate-substituted ZrO2 clusters and SiO2 organosols on the mechanical properties of composites was studied. METHODS: The flexural strength and flexural modulus of elasticity were determined according to ISO 4049: 2000. For this purpose, test specimens (2mmx2mmx25mm) of the composites investigated were prepared in stainless steel moulds and light-cured (150mW/cm2, 2x180s). The flexural strength and flexural modulus of elasticity were measured after the samples had been stored in water for 24h at 37 degrees C. RESULTS: While visible light-cured dimethacrylate-diluent-free composite restoratives based on the investigated ormocers showed a similar flexural strength and flexural modulus of elasticity compared to composites that contain only dimethacrylates, their double bond conversion was considerable lower. The simultaneous addition of methacrylate-substituted ZrO2 clusters and SiO2 organosols to the ormocer composite improved the mechanical properties of the composites. SIGNIFICANCE: Ormocers of amine or amide dimethacrylate trialkoxysilanes enabled the preparation of dimethacrylate-diluent-free composite restoratives. Based on the lower cytotoxicity of the ormocers, the prepared restorative composites should show improved biocompatibility. With the addition of nanoparticles, such as methacrylate-substituted ZrO2 clusters or SiO2 organosols, the mechanical properties of composites can be improved.

A partially aromatic urethane dimethacrylate as a new substitute for Bis-GMA in restorative composites.

OBJECTIVES: The objective of this study was to investigate the use of a new, partially aromatic urethane dimethacrylate in visible-light cured resin-based composite restoratives. Selected mechanical properties, such as flexural strength and flexural modulus of elasticity, of model monomer mixtures and composites containing the new urethane dimethacrylate were investigated and compared to the properties of materials that are based on Bis-GMA, at present the most frequently used cross-linker in restorative composites. In addition, the polymerization shrinkage and the water sorption of selected composites were determined. METHODS: The flexural strength, flexural modulus of elasticity, and the water sorption were determined according to ISO 4049:2000. Test specimens (rods: 2 mmx2 mmx25 mm; discs: d=15 mm and h=1 mm) of the investigated composites were prepared in stainless steel molds and light-cured (150 mW/cm2, 2x180 s). The flexural strength and flexural modulus of rods were measured after the samples had been stored under dry conditions or in water for 24 h at 37 degrees C as well as after they had been stored in water for 7 days at 37 degrees C. The water sorption was determined with discs. The polymerization shrinkage was calculated from the densities of the uncured composite pastes and cured composites. RESULTS: Visible light cured mixtures of dimethacrylate diluents with the new urethane dimethacrylate and composites based on these mixtures show a reactivity, flexural strength, flexural modulus of elasticity, polymerization shrinkage and water sorption similar to those of materials that are based on Bis-GMA. The composites did not show any strong deterioration of the mechanical properties after water storage.

Clinical applications of glass-ceramics in dentistry.

Glass-ceramics featuring special properties can be used as a basis to develop biomaterials. It is generally differentiated between highly durable biomaterials for restorative dental applications and bioactive glass-ceramics for medical use, for example, bone replacements. In detail, this paper presents one biomaterial from each of these two groups of materials. In respect to the restorative dental biomaterials, the authors give an overview of the most important glass-ceramics for clinical applications. Leucite, leucite-apatite, lithium disilicate and apatite containing glass-ceramics represent biomaterials for these applications. In detail, the authors report on nucleation and crystallization mechanisms and properties of leucite-apatite glass-ceramics. The mechanism of apatite nucleation is characterized by a heterogeneous process. Primary crystal phases of alpha - and beta -NaCaPO4 were determined. Rhenanite glass-ceramics represent biomaterials with high surface reactivity in simulated body fluid, SBF, and exhibit reactive behaviour in tests with bone cells. Cell adhesion phenomena and cell growth were observed. Suitable colonization and proliferation and differentiation of cells as a preliminary stage in the development of a material for bone regeneration applications was established. The authors conclude that the processes of heterogeneous nucleation and crystallization are important for controlling the required reactions in both biomaterial groups.

Bis-(acrylamide)s as new cross-linkers for resin-based composite restoratives.

OBJECTIVES: The objective of this study was to investigate the use of three new bis-(acrylamide)s as cross-linker in resin-based composite restoratives. Selected mechanical properties such as flexural strength and flexural modulus of model composites containing bis-(acrylamide)s were investigated and compared to the properties of composites that are based on only conventional dimethacrylates. In addition, the hydrolytic stability of composites containing an acidic monomer was examined. METHODS: The flexural strength and flexural modulus of elasticity were determined according to ISO 4049:2000. For this purpose, test specimens (2 mm x 2 mm x 25 mm) of the composites investigated were prepared in stainless steel moulds and light-cured (150 mW/cm2, 2 x 180 s). The flexural strength and flexural modulus were measured after the samples had been stored in dry conditions or in water for 24 h at 37 degrees C as well as after they had been stored in water for 7 days at 37 degrees C, and in certain cases, after they had been boiled for 24 h in water. RESULTS: Visible light cured mixtures of dimethacrylates with bis-(acrylamide)s and composites based on these mixtures show a similar reactivity, flexural strength and flexural modulus of elasticity compared to materials that contain only dimethacrylate. The composites did not show any deterioration of the mechanical properties after water storage. Only when strongly acidic monomers were added to the composites containing dimethacrylates or bis-(acrylamide)s did the flexural strength and flexural modulus of the samples decrease after they were stored in water. SIGNIFICANCE: Bis-(acrylamide)s were similarly reactive than dimethacrylates and therefore can be used as diluents to substitute dimethacrylate diluents in composites. Although the bis-(acrylamide)s are entirely soluble in water, non-ionic materials based on bis-(acrylamide)s did not strongly change their mechanical properties during storage in water.