Glass science behind lithium silicate glass-ceramics.

OBJECTIVES: Lithium silicate-based glass ceramics have evolved as a paramount restorative material in restorative and prosthetic dentistry, exhibiting outstanding esthetic and mechanical performance. Along with subtractive machining techniques, this material class has conquered the market and satisfied the patients' needs for a long-lasting, excellent, and metal-free alternative for single tooth replacements and even smaller bridgework. Despite the popularity, not much is known about the material chemistry, microstructure and terminal behaviour. METHODS: This article combines a set of own experimental data with extensive review of data from literature and other resources. Starting at manufacturer claims on unique selling propositions, properties, and microstructural features, the aim is to validate those claims, based on glass science. Deep knowledge is mandatory for understanding the microstructure evolution during the glass ceramic process. RESULTS: Fundamental glass characteristics have been addressed, leading to formation of time-temperature-transformation (TTT) diagrams, which are the basis for kinetic description of the glass ceramic process. Nucleation and crystallization kinetics are outlined in this contribution as well as analytical methods to describe the crystalline fraction and composition qualitatively and quantitatively. In relation to microstructure, the mechanical performance of lithium silicate-based glass ceramics has been investigated with focus on fracture strength versus fracture toughness as relevant clinical predictors. CONCLUSION: Fracture toughness has been found to be a stronger link to initially outlined manufacturer claims, and to more precisely match ISO recommendations for clinical indications.

Toughening by revitrification of Li2SiO3 crystals in Obsidian® dental glass-ceramic.

As a predominantly lithium-metasilicate-containing glass-ceramic, Obsidian® (Glidewell Laboratories, USA) has a peculiar composition and microstructure among other dental lithium silicates, warranting an evaluation of the crystallization process to establish relationships between microstructural evolution and mechanical properties. Blocks of the pre-crystallized material were processed into slices measuring 12 × 12 × 1.5 mm3 and subjected to the mandatory crystallization firing by interruption the heating ramp at temperatures between 700 °C and 820 °C (dwell time between 0 min and 10 min). The crystallization peaks of the base and the pre-crystallized glass were obtained by differential scanning calorimetry (DSC). The coefficient of thermal expansion and the glass transition temperature were derived from differential thermal analysis (DTA). X-ray diffraction (XRD) was performed to quantify and characterize the crystal phase fraction, whose microstructural changes were visualised using FE-SEM. The ball-on-three-balls surface crack in flexure method was used to track the evolution of fracture toughness. The microstructural evolution during crystallization firing was characterized by two regimes of growth: (i) the progressive revitrification (dissolution) of the 5 µm-sized Li2SiO3 polycrystals manifested at the boundaries of nanometric single coherent scattering domains (CSDs); (ii) the non-isothermal period is marked by an Ostwald ripening process characterized by the growth of the single crystalline structures into 0.5 µm polycrystals. The decrease in the crystal fraction of Li2SiO3 crystals from 41 vol.% to 37 vol.% is accompanied by the formation of a small amount of Li3PO4 (6 vol.%), maintaining the total crystal phase fraction mostly constant. The KIc accompanied the reverse trend of crystallinity, departing from 1.63 ± 0.02 MPa√m at the pre-crystallized stage to 1.84 ± 0.06 MPa√m after 10 min at 820 °C in a linear trend. Toughening appeared counter-intuitive in view of the decreasing crystal fraction and size, to rather relate to the relaxation of the residual stresses in the interstitial glass due to the spheroidization of the initially anisotropic, elongated Li2SiO3 crystals into round, nearly equiaxed particles, as let suggest from the disappearance of the extensive microcracking.

Thermal Evolutions to Glass-Ceramics Bearing Calcium Tungstate Crystals in Borate Glasses Doped with Photoluminescent Eu3+ Ions.

Thermal evolutions of calcium-tungstate-borate glasses were investigated for the development of luminescent glass-ceramics by using Eu3+ dopant in a borate glass matrix with calcium tungstate, which was expected to have a combined character of glass and ceramics. This study revealed that single-phase precipitation of CaWO4 crystals in borate glass matrix was possible by heat-treatment at a temperature higher than glass transition temperature Tg for (100-x) (33CaO-67B2O3)-xCa3WO6 (x = 8-15 mol%). Additionally, the crystallization of CaWO4 was found by Raman spectroscopy due to the formation of W=O double bondings of WO4 tetrahedra in the pristine glass despite starting with the higher calcium content of Ca3WO6. Eu3+ ions were excluded from the CaWO4 crystals and positioned in the borate glass phase as a stable site for them, which provided local environments in higher symmetry around Eu3+ ions.

Low-temperature degradation increases the cyclic fatigue resistance of 3Y-TZP in bending.

OBJECTIVE: Due to past failures of orthopedic 3Y-TZP femoral implants linked to accelerated tetragonal-to-monoclinic phase transformation (t → m), the susceptibility to 'low-temperature degradation' or 'ageing' of 3Y-TZP has been advertised as detrimental to its long-term structural stability. However, no systematic mechanistic experiments on the fatigue resistance of aged 3Y-TZP under cyclic loading can support such statement. In this study, we aim to clarify this issue. METHODS: Here we evaluate the subcritical crack growth behavior of 3Y-TZP under cyclic loading after 0-50 h of accelerated ageing in an autoclave at 134 °C. The same 3Y-TZP sintered at two different temperatures (1450 °C or 1650 °C) allows for the comparison of materials containing grains with different susceptibilities to transformation. The volume fraction of surface transformed grains was measured using Raman spectroscopy, and the depth of the transformed surface layer from trenches milled with a Focus-Ion Beam. The fracture toughness before and after ageing was determined using the Chevron-notch Beam method. The quasi-static flexural strength was measured in dry conditions and the cyclic lifetime in water at 10 Hz and R-ratio = 0.3 in 4-point-bending at different applied stresses. The fatigue parameter n was derived from 3 different methods, namely SN curves, crack velocity plots and Weibull distributions. RESULTS: The progression of transformation showed linear kinetics with higher rates for the 3Y-TZP sintered at 1650 °C. Accelerated transformation induced severe crack formation within the transformed layer with parallel orientation to the surface plane, which supposedly behaved as the critical crack size population governing fracture. The stress intensity factor within the transformed layer was increased due to compressive stresses. Consequently, the fatigue parameter n increased consistently from 5 to 50 h of ageing, regardless of the derivation method, suggesting an increased resistance against crack growth during cyclic loading in bending. SIGNIFICANCE: Our results do not support the long suggested negative clinical implications of LTD regarding mechanical performance, to the contrary, LTD seems to increase the resistance against subcritical crack growth in a humid environment in bending.

Chairside CAD/CAM materials. Part 1: Measurement of elastic constants and microstructural characterization.

OBJECTIVE: A deeper understanding of the mechanical behavior of dental restorative materials requires an insight into the materials elastic constants and microstructure. Here we aim to use complementary methodologies to thoroughly characterize chairside CAD/CAM materials and discuss the benefits and limitations of different analytical strategies. METHODS: Eight commercial CAM/CAM materials, ranging from polycrystalline zirconia (e.max ZirCAD, Ivoclar-Vivadent), reinforced glasses (Vitablocs Mark II, VITA; Empress CAD, Ivoclar-Vivadent) and glass-ceramics (e.max CAD, Ivoclar-Vivadent; Suprinity, VITA; Celtra Duo, Dentsply) to hybrid materials (Enamic, VITA; Lava Ultimate, 3M ESPE) have been selected. Elastic constants were evaluated using three methods: Resonant Ultrasound Spectroscopy (RUS), Resonant Beam Technique (RBT) and Ultrasonic Pulse-Echo (PE). The microstructures were characterized using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Raman Spectroscopy and X-ray Diffraction (XRD). RESULTS: Young's modulus (E), Shear modulus (G), Bulk modulus (B) and Poisson's ratio (ν) were obtained for each material. E and ν reached values ranging from 10.9 (Lava Ultimate) to 201.4 (e.max ZirCAD) and 0.173 (Empress CAD) to 0.47 (Lava Ultimate), respectively. RUS showed to be the most complex and reliable method, while the PE method the easiest to perform but most unreliable. All dynamic methods have shown limitations in measuring the elastic constants of materials showing high damping behavior (hybrid materials). SEM images, Raman spectra and XRD patterns were made available for each material, showing to be complementary tools in the characterization of their crystal phases. SIGNIFICANCE: Here different methodologies are compared for the measurement of elastic constants and microstructural characterization of CAD/CAM restorative materials. The elastic properties and crystal phases of eight materials are herein fully characterized.

Dioxygen oxidation Cu(II) → Cu(III) in the copper complex of cyclo(Lys-dHis-ßAla-His): a case study by EXAFS and XANES approach.

A former spectroscopic study of Cu(II) coordination by the 13-membered ring cyclic tetrapeptide c(Lys-dHis-ßAla-His) (DK13), revealed the presence, at alkaline pH, of a stable peptide/Cu(III) complex formed in solution by atmospheric dioxygen oxidation. To understand the nature of this coordination compound and to investigate the role of the His residues in the Cu(III) species formation, Cu K-edge XANES, and EXAFS spectra have been collected for DK13 and two other 13-membered cyclo-peptides: the diastereoisomer c(Lys-His-ßAla-His) (LK13), and c(Gly-ßAla-Gly-Lys) (GK13), devoid of His residues. Comparison of pre-edge peak features with those of Cu model compounds, allowed us to get information on copper oxidation state in two of the three peptides, DK13 and GK13: DK13 contains only Cu(III) ions in the experimental conditions, while GK13 binds only with Cu(II). For LK13/Cu complex, EXAFS spectrum suggested and UV-vis analysis confirmed the presence of a mixture of Cu(II) and Cu(III) coordinated species. Theoretical XANES spectra have been calculated by means of the MXAN code. The good agreement between theoretical and experimental XANES data collected for DK13, suggests that the refined structure, at least in the first coordination shell around Cu, is a good approximation of the DK13/Cu(III) coordination species present at strongly alkaline pH. All the data are consistent with a slightly distorted pyramidal CuN(4) unit, coming from the peptide bonds. Surprisingly, the His side-chains seemed not involved in the final, stable, Cu(III) scaffold.