Influence of ZnO/MgO substitution on sintering, crystallisation, and bio-activity of alkali-free glass-ceramics

• The addition of zinc to glasses decreased Tg and promoted crystallisation.
• Zinc enhanced the sintering ability and increased mechanical strength by 36%.
• The apatite formation ability decreased with increasing Zn contents.
• Zinc stimulated mesenchymal stem cell proliferation in a dose dependent manner.

The present study reports on the influence of partial replacement of MgO by ZnO on the structure, crystallisation behaviour and bioactivity of alkali-free bioactive glass-ceramics (GCs). A series of glass compositions (mol%): 36.07 CaO–(19.24 − x) MgO–x ZnO–5.61 P2O5–38.49 SiO2–0.59 CaF2 (x = 2–10) have been synthesised by melt–quench technique. The structural changes were investigated by solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray diffraction and differential thermal analysis. The sintering and crystallisation behaviours of glass powders were studied by hot-stage microscopy and differential thermal analysis, respectively. All the glass compositions exhibited good densification ability resulting in well sintered and mechanically strong GCs. The crystallisation and mechanical behaviour were studied under non-isothermal heating conditions at 850 °C for 1 h. Diopside was the primary crystalline phase in all the GCs followed by fluorapatite and rankinite as secondary phases. Another phase named petedunnite was identified in GCs with ZnO content > 4 mol. The proliferation of mesenchymal stem cells (MSCs) and their alkaline phosphatase activity (ALP) on GCs was revealed to be Zn-dose dependent with the highest performance being observed for 4 mol% ZnO.