Christian Ritzberger

Properties and Clinical Application of Three Types of Dental Glass-Ceramics and Ceramics for CAD-CAM Technologies

The main properties (mechanical, thermal and chemical) and clinical application for dental restoration are demonstrated for three types of glass-ceramics and sintered polycrystalline ceramic produced by Ivoclar Vivadent AG. Two types of glass-ceramics are derived from the leucite-type and the lithium disilicate-type. The third type of dental materials represents a ZrO2 ceramic. CAD/CAM technology is a procedure to manufacture dental ceramic restoration. Leucite-type glass-ceramics demonstrate high translucency, preferable optical/mechanical properties and an application as dental inlays, onlays and crowns. Based on an improvement of the mechanical parameters, specially the strength and toughness, the lithium disilicate glass-ceramics are used as crowns; applying a procedure to machine an intermediate product and producing the final glass-ceramic by an additional heat treatment. Small dental bridges of lithium disilicate glass-ceramic were fabricated using a molding technology. ZrO2 ceramics show high toughness and strength and were veneered with fluoroapatite glass-ceramic. Machining is possible with a porous intermediate product.

Formation and crystal growth of needle-like fluoroapatite in functional glass-ceramics

The objective of the study is to analyze the solid state reactions leading to the precipitation of fluoroapatite, Ca5(PO4)3F, in two different functional glass-ceramic systems (labeled A and B) of interest for restorative dentistry. Combined X-ray diffraction (XRD), electron microscopy (SEM and TEM) and solid state nuclear magnetic resonance (NMR) are used to characterize the solid state reactions, leading to the formation of primary and secondary crystalline phases, as well as the structural changes occurring in the residual glass matrix during this process. The results indicate that, depending on the composition of the ceramic, fluoroapatite crystallization can proceed by different mechanisms: (1) precipitation in a parallel process accompanying the formation of rhenanite (NaCaPO4) primary crystals (glass-ceramic A), and (2) formation from amorphous and/or disordered crystalline precursor phases that are already segregated within a phase separated glass matrix (glass-ceramic B). In the latter case, this disordered phase transforms by solid state reaction into fluoroapatite at high temperatures of heat treatment of the glass-ceramic. The needle-like morphology of fluoroapatite in glass-ceramics mimics the morphology of hydroxyl-carbonato apatite in human teeth.

Radiopaque Strontium Fluoroapatite Glass-Ceramics.

The controlled precipitation of strontium fluoroapatite crystals was studied in four base glass compositions derived from the SiO2–Al2O3–Y2O3–SrO–Na2O–K2O/Rb2O/Cs2O–P2O5–F system. The crystal phase formation of these glasses and the main properties of the glass-ceramics, such as thermal and optical properties and radiopacity were compared with a fifth, a reference glass-ceramic. The reference glass-ceramic was characterized as Ca-fluoroapatite glass-ceramic. The four strontium fluoroapatite glass-ceramics showed the following crystal phases: (a) Sr5(PO4)3F – leucite, KAlSi2O6, (b) Sr5(PO4)3F – leucite, KAlSi2O6, and nano-sized NaSrPO4, (c) Sr5(PO4)3F – pollucite, CsAlSi2O6, and nano-sized NaSrPO4, and (d) Sr5(PO4)3F – Rb-leucite, RbAlSi2O6, and nano-sized NaSrPO4. The proof of crystal phase formation was possible by X-ray diffraction. The microstructures, which were studied using scanning electron microscopy, demonstrated a uniform distribution of the crystals in the glass matrix. The Sr-fluoroapatites were precipitated based on an internal crystallization process, and the crystals demonstrated a needle-like morphology. The study of the crystal growth of needle-like Sr-fluoroapatites gave a clear evidence of an Ostwald ripening mechanism. The formation of leucite, pollucite, and Rb-leucite was based on a surface crystallization mechanism. Therefore, a twofold crystallization mechanism was successfully applied to develop these types of glass-ceramics. The main focus of this study was the controlled development of glass-ceramics exhibiting high radiopacity in comparison to the reference glass-ceramic. This goal could be achieved with all four glass-ceramics with the preferred development of the Sr-fluoroapatite – pollucite-type glass-ceramic. In addition to this main development, it was possible to control the thermal properties. Especially the Rb-leucite containing glass-ceramic showed the highest coefficient of thermal expansion (CTE). These glass-ceramics allow optical properties, especially the translucency and color, to be tailored to the needs of biomaterials for dental applications. The authors conclude that it is possible to use twofold crystallization processes to develop glass-ceramic biomaterials featuring different properties, such as specific radiopacity values, CTEs, and optical characteristics.

Properties and Crystallization Phenomena in Li2Si2O5–Ca5(PO4)3F and Li2Si2O5–Sr5(PO4)3F Glass–Ceramics Via Twofold Internal Crystallization

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass–ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass–ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F− were prepared within the glasses of the SiO2–Li2O–K2O–CaO/SrO–Al2O3–P2O5–F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass–ceramics was established. The microstructures of the glass–ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass–ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass–ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass–ceramics. The authors conclude that the twofold crystallization of Li2Si2O5–Ca5(PO4)3F or Li2Si2O5–Sr5(PO4)3F glass–ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass–ceramics and, hence, displays new potential for dental applications.

Controlled Parallel Crystallization of Lithium Disilicate and Diopside Using a Combination of Internal and Surface Nucleation

In the mid-19th century, Dr. Donald Stookey identified the importance and usability of nucleating agents and mechanisms for the development of glass-ceramic materials. Today, a number of various internal and surface mechanisms as well as combinations thereof have been established in the production of glass-ceramic materials. In order to create new innovative material properties the present study focuses on the precipitation of CaMgSiO6 as a minor phase in Li2Si2O5 based glass-ceramics. In the base glass of the SiO2-Li2O-P2O5-Al2O3-K2O-MgO-CaO system P2O5 serves as nucleating agent for the internal precipitation of Li2Si2O5 crystals while a mechanical activation of the glass surface by means of ball milling is necessary to nucleate the minor CaMgSi2O6 crystal phase. For a successful precipitation of CaMgSi2O6 a minimum ratio of MgO and CaO in the range between 1.4 mol% and 2.9 mol% in the base glasses was determined. The nucleation and crystallization of both crystal phases takes place during sintering a powder compact. Dependent on the quality of the sintering process the dense Li2Si2O5-CaMgSi2O6 glass-ceramics show a mean biaxial strength of up to 392 ± 98 MPa. The microstructure of the glass-ceramics is formed by large (5-10 µm) bar like CaMgSi2O6 crystals randomly embedded in a matrix of small (≤ 0.5 µm) plate like Li2Si2O5 crystals arranged in an interlocking manner. While there is no significant influence of the minor CaMgSi2O6 phase on the strength of the material, the translucency of the material decreases upon precipitation of the minor phase.