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.

Clinical applications of glass-ceramics in dentistry.

Glass-ceramics featuring special properties can be used as a basis to develop biomaterials. It is generally differentiated between highly durable biomaterials for restorative dental applications and bioactive glass-ceramics for medical use, for example, bone replacements. In detail, this paper presents one biomaterial from each of these two groups of materials. In respect to the restorative dental biomaterials, the authors give an overview of the most important glass-ceramics for clinical applications. Leucite, leucite-apatite, lithium disilicate and apatite containing glass-ceramics represent biomaterials for these applications. In detail, the authors report on nucleation and crystallization mechanisms and properties of leucite-apatite glass-ceramics. The mechanism of apatite nucleation is characterized by a heterogeneous process. Primary crystal phases of alpha - and beta -NaCaPO4 were determined. Rhenanite glass-ceramics represent biomaterials with high surface reactivity in simulated body fluid, SBF, and exhibit reactive behaviour in tests with bone cells. Cell adhesion phenomena and cell growth were observed. Suitable colonization and proliferation and differentiation of cells as a preliminary stage in the development of a material for bone regeneration applications was established. The authors conclude that the processes of heterogeneous nucleation and crystallization are important for controlling the required reactions in both biomaterial groups.