New Insights Into Application Relevant Properties of Cu2+-Doped Brushite Cements.

Doping of brushite cements with metal ions can entail many positive effects on biological and physicochemical properties. Cu2+ ions are known to exhibit antibacterial properties and can additionally have different positive effects on cells as trace elements, whereas high Cu2+ concentrations are cytotoxic. For therapeutical applications of bone cement, a combination of good biocompatibility and sufficient mechanical properties is required. Therefore, the aim of this study was to investigate different physicochemical and biological aspects, relevant for application, of a brushite cement with Cu2+-doped ß-tricalcium phosphate, monocalcium phosphate monohydrate and phytic acid as setting retarder. Additionally, the ion release was compared with a cement with citric acid as setting retarder. The investigated cements showed good injectability coefficients, as well as compressive strength values sufficient for application. Furthermore, no antibacterial effects were detected irrespective of the Cu2+ concentration or the bacterial strain. The cell experiments with eluate samples showed that the viability of MC3T3-E1 cells tended to decrease with increasing Cu2+ concentration in the cement. It is suggested that these biological responses are caused by the difference in the Cu2+ release from the hardened cement depending on the solvent medium. Furthermore, the cements showed a steady release of Cu2+ ions to a lesser extent in comparison with a cement with citric acid as setting retarder, where a burst release of Cu2+ was observed. In conclusion, despite the anticipated antibacterial effect of Cu2+-doped cements was lacking and mammalian cell viability was slightly affected, Cu2+-concentrations maintained the physicochemical properties as well as the compressive strength of cements and the slow ion release from cements produced with phytic acid is considered advantageous compared to citric acid-based formulations.

Fatigue strength of bilayer yttria-stabilized zirconia after low-temperature degradation.

This study examined the impact of interfacial interactions on bilayer yttria-stabilized zirconia (YSZ) used in dental restorations. In-house bilayer structures of 3YSZ and 5YSZ composition underwent hydrothermal degradation to compare the properties of control and low-temperature degradation (LTD) treated groups. Biaxial flexural strength via piston-on-three-balls, staircase fatigue strength over 106 cycles at 15 Hz, phase characterization and quantification through XRD and Rietveld refinement, and fractography were conducted. Weibull analysis was employed to determine the Weibull modulus and characteristic strength. Results demonstrated an enhancement in the mechanical performance of 3YSZ composition after LTD treatment, whereas the mechanical properties of 5YSZ remained largely unaffected post-degradation. Fractographic analysis revealed that failure originated at the surface tensile location across all specimen groups. These findings offer insights into the mechanical behavior of bilayer zirconia structures and reinforce the significance of hydrothermal treatment in enhancing their performance, particularly in the case of 3Y compositions.

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.

On the assignment of quartz-like LiAlSi2O6 - SiO2 solid solutions in dental lithium silicate glass-ceramics: Virgilite, high quartz, low quartz or stuffed quartz derivatives?

OBJECTIVES: Here we aim to provide a background on X-Ray Diffraction analysis of quartz-like crystal structures with varying amounts of Al3+ and Li+ substitution, existing confusions on their nomenclature and its implications for novel lithium silicate glass-ceramics. METHODS: We reviewed the literature dealing with modifications of the quartz crystal structure and their stuffed LiAlSi2O6 derivates, LiAlSi2O6 - SiO2 solid solutions, the terminology of such phases and criteria used to define the structure known as virgilite. Based on this information, we attempted to allocate the quartz-like phases found in CEREC TesseraTM, InitialTM LiSi Block and Amber® Mill in the range of LiAlO2 - SiO2 solid solutions. For this purpose, their lattice parameters obtained from Rietveld refinement were compared with the lattice parameters of members of the corresponding solid solutions with defined SiO2 molar fraction found in the literature. RESULTS: Based on the lattice parameters available for low quartz, high quartz and its stuffed derivatives, including LiAlSi2O6 and the mineral virgilite, a plot of the a- and c-parameters vs. the mol% SiO2 related to LiAlO2 was constructed with the literature data and the data found for the three dental lithium silicates. As per the definitions of virgilite as either LixAlxSi3-xO6, with 0.5 < x < 1 or especially as members of the LiAlSi2O6 - SiO2 solid-solution series with more than 50 mol% LiAlSi2O6, the crystal structures in CEREC TesseraTM, InitialTM LiSi Block and Amber® Mill failed to fall within the ranges of mol% SiO2 confined for virgilite. SIGNIFICANCE: Based on available literature and definitions, the quartz-like phases found in the three dental lithium silicates should be addressed as stuffed (probably low) quartz solid solutions instead of "virgilite". However determined by mineralogical practices, the term "virgilite" for parts of the LiAlSi2O6 - SiO2 solid solution is ambiguous and can be considered as arbitrary.

Grasping the Lithium hype: Insights into modern dental Lithium Silicate glass-ceramics.

OBJECTIVES: Lithium-based glass-ceramics are currently dominating the landscape of dental restorative ceramic materials, with new products taking the market by storm in the last years. Though, the difference among all these new and old products is not readily accessible for the practitioner, who faces the dilemma of reaching a blind choice or trusting manufacturers' marketing brochures. To add confusion, new compositions tend to wear material terminologies inherited from vanguard dental lithium disilicates, disregarding accuracy. Here we aim to characterize such materials for their microstructure, crystalline fraction, glass chemistry and mechanical properties. METHODS: Eleven commercial dental lithium-based glass ceramics were evaluated: IPS e.max® CAD, IPS e.max® Press, Celtra® Duo, Suprinity® PC, Initial™ LiSi Press, Initial™ LiSi Block, Amber® Mill, Amber® Press, N!CE®, Obsidian® and CEREC Tessera™. The chemical composition of their base glasses was measured by X-Ray Fluorescence Spectroscopy (XRF) and Inductive Coupled Plasma Optical Emission Spectroscopy (ICP-OES), as well as the composition of their residual glass by subtracting the oxides bound in the crystallized fraction, characterized by X-Ray Diffraction (XRD) and Rietveld refinement, and quantified accurately using the G-factor method (QXRD). The crystallization behavior is revealed by differential scanning calorimetry (DSC) curves. Elastic constants are provided from Resonant Ultrasound Spectroscopy (RUS) and the fracture toughness measured by the Ball-on-Three-Balls method (B3B- K Ic). The microstructure is revealed by field-emission scanning electron microscopy (FE-SEM). RESULTS: The base glasses showed a wide range of SiO2 /Li2O ratios, from 1.5 to 3.0, with the degree of depolymerization dropping from ½ to 2/3 of the initial connectivity. Materials contained Li2SiO3+Li3PO4, Li2SiO3+Li3PO4+Li2Si2O5, Li2Si2O5+Li3PO4+ Cristobalite and/or Quartz and Li2Si2O5+Li3 PO4+LiAlSi2O6, in crystallinity degrees from 45 to 80 vol%. Crystalline phases could be traced to their crystallization peaks on the DSC curves. Pressable materials and IPS e.max® CAD were the only material showing micrometric phases, with N!CE® and Initial™ LiSi Block showing solely nanometric crystals, with the rest presenting a mixture of submicrometric and nanometric particles. Fracture toughness from 1.45 to 2.30 MPa√m were measured, with the linear correlation to crystalline fraction breaking down for submicrometric and nanometric crystal phases. SIGNIFICANCE: Dental lithium-based silicate glass-ceramics cannot be all put in the same bag, as differences exist in chemical composition, microstructure, crystallinity and mechanical properties. Pressable materials still perform better mechanically than CAM/CAM blocks, which loose resistance to fracture when crystal phases enter the submicrometric and nanometric range.

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.

Crack-healing during two-stage crystallization of biomedical lithium (di)silicate glass-ceramics.

OBJECTIVE: The study is aimed to evaluate the two single commercially available two-step lithium-(di)silicate systems by analyzing their parent glass composition and studying the quantitative crystalline and glass phase evolution during the second stage heat-treatment. The mechanical repercussions of the crystallization firing were evaluated using strength and fracture toughness tests. METHODS: XRF and ICP-OES were used to determine the oxide composition of the parent glasses in Suprinity PC (Vita Zahnfabrik) and IPS e.max CAD (Ivoclar-Vivadent). The crystalline phase of both materials was determined by quantitative XRD and the G-factor method in the partially and post-crystallization states. The oxide composition of the residual glass phase was derived by subtracting the chemistry of the crystalline phase fractions from the parent glass composition. Mechanical testing of biaxial flexural strength and fracture toughness were used to demonstrate how crack-like defects behave during crystallization. RESULTS: The two tested lithium (di)silicate systems showed strong differences in oxide composition of the parent glass. This showed to influence the transformation of lithium metasilicate in lithium disilicate, with the former remaining in high vol.% fraction in the post-crystallization Suprinity PC. In IPS e.max CAD cristobalite precipitated at the surface during the second-heat treatment. Strength and fracture toughness tests revealed that crack in both materials, whether introduced by grinding or indentation, heal during the crystallization firing. Cristobalite seemed to have contributed to a surface strengthening effect in IPS e.max CAD. SIGNIFICANCE: Accurate crystalline phase quantification aids in the determination of the residual glass composition in dental glass-ceramics. For both systems crystallization firing induced healing of cracks generated by CAM grinding.

Effect of sintering parameters on phase evolution and strength of dental lithium silicate glass-ceramics.

OBJECTIVE: With the establishment of CAD/CAM technology, competing lithium silicate based formulations have been introduced for clinical use, but little is known about their phase composition. Here we investigate a commercially available SiO2-Al2O3-K2O-Li2O-P2O5-ZrO2 system to evaluate the crystal phase evolution during the second heat treatment by changing the main crystallization parameters. METHODS: With a focus on the final stage of crystallization, we characterized the dimensional changes in the crystallographic structure of the residual Li2SiO3 and the lithium orthophosphate (Li3PO4) phases with variations in crystallization parameters, i.e. time, temperature and cooling rate over the range of the glass transition temperature Tg. The phase fractions (crystalline and glass) and the sizes of coherent scattering domains (CSDs) were resolved by means of quantitative X-Ray Diffraction using Rietveld refinement combined with an external standard method (G-factor). Biaxial flexure testing was conducted to evaluate the influence of crystallization parameters on the characteristic strength and natural defect distribution. RESULTS: An increase in crystallization temperature from 840 to 880°C resulted in a significant reduction of the Li2Si2O5 content, which indicated a reversion of the Li2SiO3 to Li2Si2O5 phase transformation. Reduction to 800°C had no significant effect. Furthermore, the CSD sizes of Li2SiO3 and Li3PO4 continuously increased with increasing temperature, which was accompanied by an increase in strength parameters. Reducing the cooling rate over the range of Tg resulted in an increased strength at low failure probabilities. SIGNIFICANCE: These findings help to establish recommendations for adjustment of the crystallization protocol, which has potential to increase the clinical reliability of the material investigated.

Hydration mechanism of a calcium phosphate cement modified with phytic acid.

Calcium phosphate cements composed of ß-tricalcium phosphate (ß-TCP) and phosphoric acid were modified by addition of 5, 10, 12.5, 15 and 20 wt% phytic acid (IP6) related to the ß-TCP content and compared to a reference containing 0.5 M citric acid monohydrate solution as setting regulator. The hydration reaction of these cements was investigated by isothermal calorimetry and in-situ X-ray diffraction at 23 °C and 37 °C. The cements were further characterized with respect to their injectability, rheology, zeta potential and time-resolved compressive strength development. Injectability was strongly improved by IP6 addition, while the maximum effect was already reached by the addition of 5 wt% IP6. This could be clearly related to an increase of the negative zeta potential leading to a mutual repulsion of cement particles. A further increase of the IP6 content had a detrimental effect on initial paste viscosity and shifted the gelation point to earlier time points. IP6 was further proven to act as a retarder for the cement setting reaction, whereas the effect was stronger for higher IP6 concentrations. Additionally, IP6 favoured the formation of monetite instead of brushite and a better mechanical performance compared to the IP6 free reference cement. STATEMENT OF SIGNIFICANCE: Calcium phosphate cements (CPCs) are clinically applied for bone repair due to their excellent biocompatibility and bone regeneration capacity. A deep understanding of the setting mechanism is the prerequisite for the targeted fabrication and application of such bone cements, whereas setting characteristics are usually adjusted by additives. Here, novel injectable CPC formulations were developed by modifying a cement composed of ß-tricalcium phosphate and phosphoric acid with phytic acid (IP6). A detailed investigation of the setting mechanism of the IP6 modified CPCs is provided, which demonstrated the effectiveness of IP6 as setting regulator to adjust the reaction time and kind of setting product. Additionally, the high surface charge of cement particles after IP6 addition was effective in dispersing cement particles leading to low viscous cement pastes, which can be directly applied through a syringe for minimal invasive surgery.

Hydration mechanism of partially amorphized ß-tricalcium phosphate.

Calcium phosphate cements (CPCs) are applied as bone cements due to their excellent biocompatibility. In the present study, the quantitative phase content development during hydration of partially amorphized ß-tricalcium phosphate (ß-TCP) within the first 24h was investigated by in-situ X-ray diffraction (XRD) combined with the G-factor method, an external standard method. The quantity of amorphous phase (ATCP) in the powders was determined by the G-factor method. The hydration model established for partially amorphized ß-TCP indicates that ATCP reacted first, followed by the hydration of a small fraction of crystalline ß-TCP starting after some h. Consequently, hydration resulted in biphasic samples composed of calcium deficient hydroxyapatite (CDHA) and crystalline ß-TCP. The ratio wt%(CDHA)/wt%(ß-TCP) after 24h hydration was adjustable by the initial ATCP content. The crystallinity of CDHA was nearly independent of the ATCP content. Since the biological degradability of CDHA and ß-TCP differ, the degradation performance of the set cements is expected to be adjustable by varying the ATCP content. The present study provided a basic understanding of the hydration mechanism of partially amorphized ß-TCP, which is the prerequisite for the development of applicable CPC formulations. STATEMENT OF SIGNIFICANCE: Calcium phosphate cements (CPCs) are medically applied for bone repair due to their excellent biocompatibility. ß-Tricalcium phosphate (ß-TCP), which is hardly reactive in water in its crystalline state, was previously shown to be activatable by partial amorphization. This provides potential for the development of new CPCs setting to biphasic samples composed of ß-TCP and calcium deficient hydroxyapatite (CDHA). The degradation performance of these cements is expected to be adjustable by varying the ratio of CDHA to ß-TCP. In the present study, the so far unknown setting mechanism of partially amorphized ß-TCP was investigated in detail. The results contribute to the basic understanding of the hydration of partially amorphized ß-TCP, which is important for the targeted development of new cement formulations.

Calorimetry investigations of milled α-tricalcium phosphate (α-TCP) powders to determine the formation enthalpies of α-TCP and X-ray amorphous tricalcium phosphate.

One α-tricalcium phosphate (α-TCP) powder was either calcined at 500°C to obtain fully crystalline α-TCP or milled for different durations to obtain α-TCP powders containing various amounts of X-ray amorphous tricalcium phosphate (ATCP). These powders containing between 0 and 71wt.% ATCP and up to 2.0±0.1wt.% ß-TCP as minor phase were then hydrated in 0.1M Na2HPO4 aqueous solution and the resulting heat flows were measured by isothermal calorimetry. Additionally, the evolution of the phase composition during hydration was determined by in situ XRD combined with the G-factor method, an external standard method which facilitates the indirect quantification of amorphous phases. Maximum ATCP hydration was reached after about 1h, while that of crystalline α-TCP hydration occurred between 4 and 11h, depending on the ATCP content. An enthalpy of formation of -4065±6kJ/mol (T=23°C) was calculated for ATCP (Ca3(PO4)2), while for crystalline α-TCP (α-Ca3(PO4)2) a value of -4113±6kJ/mol (T=23°C) was determined.