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.

Phase Solubility Changes during Hydration of Monocalciumaluminate and Calcite-The Influence of Alkali Accumulation.

The reaction of CA (monocalcium aluminate) with calcite was closely monitored with regard to phase development, pore water ion content and heat flow. Calcite acts as filler and reactant, finally leading to thermodynamically stable products after hydration at ambient conditions. For better understanding the mechanism taking place, a CA-cement and a commercial calcite mix were compared to a pure CA and pure calcite mix. Both reaction paths were compared. Thermodynamic modeling with PhreeqC gave insight about factors that can influence the course of the hydration reaction. Alkali ions in pore solution of the CA-cement relocate solubility curves of hydration products. Taking into account as many of the alkaline ions as possible, resulted in the closest representation of the measured phase content, confirming thermodynamic modeling. The high dynamics that develop during reaction could only be addressed if a concentration of alkalis in the pore solution at later points in time was respected, thus leading to a shift of solubility curves over time. This was not observed with the pure CA in absence of alkalis.

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.

Setting Mechanism of a CDHA Forming α-TCP Cement Modified with Sodium Phytate for Improved Injectability.

A calcium deficient hydroxyapatite (CDHA) forming cement with a bimodal grain size distribution, composed of α-TCP and fine grained CDHA at a weight ratio of 9:1, was modified by the addition of sodium phytate (IP6) in variable amounts ranging from 0.25 to 2 wt.%, related to the powder content. The injectability of the cement paste was drastically increased by the IP6 addition, independent of the amount of added IP6. Additionally, the cement paste viscosity during the first minutes decreased. These effects could be clearly related to a slightly more negative zeta potential. Furthermore, IP6 was shown to strongly retard the setting reaction, as can be seen both in the calorimetry and X-ray diffraction measurements. In addition, octacalcium phosphate (OCP) was identified as a further setting product. All measurements were performed at 23 °C and 37 °C to assess the effect of temperature on the setting reaction for both clinical handling by the surgeon and the final hardening in the bone defect.

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.

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.

Reaction kinetics of dual setting α-tricalcium phosphate cements.

Addition of ductile polymers to calcium-deficient hydroxyapatite (CDHA)-forming bone cements based on α-tricalcium phosphate (α-TCP) is a promising approach to improve the mechanical performance of α-TCP cements and extend their application to load-bearing defects, which is else impeded by the brittleness of the hardened cement. One suitable polymer is poly-(2-hydroxyethylmethacrylate) (p-HEMA), which forms during cement setting by radical polymerisation of the monomer. In this study the hydration kinetics and the mechanical performance of α-TCP cements modified with addition of different HEMA concentrations (0-50 wt% in the cement liquid) was investigated by quantitative in situ XRD and four-point bending tests. Morphology of CDHA crystals was monitored by scanning electron microscopy. The hydration of α-TCP to CDHA was increasingly impeded and the visible crystal size of CDHA increasingly reduced with increasing HEMA concentration. Modification of the cements by adding 50 wt% HEMA to the cement liquid changed the brittle performance of the hardened cement to a pseudoplastic behaviour, reduced the flexural modulus and increased the work of fracture, while lower HEMA concentrations had no significant effect on these parameters. In such a composite, the extent of CDHA formation was considerably reduced (34.0 ± 1.8 wt% CDHA with 50 % HEMA compared to 54.1 ± 2.4 wt% CDHA in the reference formed after 48 h), while the general reaction kinetics were not changed. In conclusion, while the extent of CDHA formation was decreased, the mechanical properties were noticeably improved by addition of HEMA. Hence, α-TCP/HEMA composites might be suitable for application in some load-bearing defects and have adequate properties for mechanical treatment after implantation, like insertion of screws.

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.

Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite.

Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA.