Elke Apel

Phenomena and mechanisms of crack propagation in glass-ceramics

Lithium disilicate, leucite and apatite glass-ceramics have become state-of-the-art framework materials in the fabrication of all-ceramic dental restorative materials. The goal of this study was to examine the crack propagation behaviour of these three known glass-ceramic materials after they have been subjected to Vickers indentation and to characterize their crack opening profiles (delta(meas) vs. (a-r)). For this purpose, various methods of optical examination were employed. Optical microscopy investigations were performed to examine the crack phenomena at a macroscopic level, while high-resolution techniques, such as scanning electron microscopy (SEM) and atomic force microscopy (AFM), were employed to investigate the crack phenomena at a microscopic level. The crack patterns of the three glass-ceramics vary from fairly straightforward to more complex, depending on the amount of residual glass matrix present in the material. The high-strength lithium disilicate crystals feature a high degree of crosslinking, thereby preventing crack propagation. In this material, the crack propagates only through the residual glass phase, which constitutes 30%-40% by volume. Having a high glass content of more than 65% by volume, the leucite and apatite glass-ceramics show far more complex crack patterns. Cracks in the leucite glass-ceramic propagate through both the glass and crystal phase. The apatite glass-ceramic shows a similar crack behaviour as an inorganic-organic composite material containing nanoscale fillers, which are pulled out in the surroundings of the crack tip. The observed crack behaviour and the calculated K(tip) values of the three types of glass-ceramics were compared to the K(IC) values determined according to the SEVNB method.

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.

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.