The coloring process of monolithic dental zirconia caused considerable debate on the possible effects of different coloring methods. The main objective of this study was to investigate the influence of pigments in 3 multilayer 5-mol% yttria partially stabilized zirconia (5Y-PSZ) disks (Lava Esthetic A2 [Zr-AGG_A2] and Bleach [Zr-AGG_BL], both 3M Oral Care, and Katana STML A2 [Zr-NoAGG], Kuraray Noritake). The influence of pigment addition on the translucency parameter (TP00), fracture toughness, Vickers hardness, biaxial strength, and hydrothermal stability was assessed and correlated with the microstructure and phase composition. The pigment composition and distribution were evaluated by light and fluorescence microscopy, electron probe microanalysis, and nano–scanning electron microscopy. The chemical and phase composition and aging behavior were assessed using X-ray fluorescence and X-ray diffraction, respectively, while the aging sensitivity of the pigments was evaluated using micro-Raman spectroscopy. In contrast to Zr-NoAGG, possessing a typical 5Y-PSZ microstructure, the pigment additions in both Zr-AGG_A2/BL zirconia resulted in large yellow and blue fluorescent Er-, Hf-, and Al-containing agglomerates composed of small grains (0.57 µm and 0.38 µm, respectively, vs. 0.92 µm for the surrounding grains) with lower Y2O3 content. Zr-AGG_A2 had the lowest aging resistance, with transformation degradation occurring exclusively within the pigment agglomerates. All zirconia grades had a high Y2O3 content (4.2%–5.7 mol%) tetragonal ZrO2 phase and a high (42%–55 wt%) cubic ZrO2 phase content. Although no statistical differences were measured for hardness and toughness, Zr-NoAGG had a significantly higher TP00, higher flexural strength, and lower mechanical reliability compared to both Zr-AGG_A2/BL zirconia. The rare-earth oxide-containing zirconia agglomerates that were added as pigments to the multilayered monolithic Zr-AGG_A2/BL zirconia are the cause for their lower optical and mechanical properties and reduced aging resistance.
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