Stability-limited ion-exchange of calcium with zinc in biomimetic hydroxyapatite
Mark M. J. van Rijt, Sjoerd W. Nooteboom, Arno van der Weijden, Willem L. Noorduin, Gijsbertus de With
Abstract
The exchange of Ca2+ ions in hydroxyapatite (HAp) with Zn2+ ions into Zn-HAp is of interest for applications ranging from bone tissue engineering to the use as a precursor in subsequent ion-exchange reactions. Previous studies, using direct synthesis, showed that ~ 20 mol% Zn2+ ions can be incorporated into HAp, before byproducts are observed. However, this is realized at the cost of a loss in crystallinity and control over crystal size and shape with increasing amounts of Zn2+ ion incorporation. In this work a simple post-synthetic ion-exchange strategy for the formation of Zn-HAp has been investigated. By merely exposing HAp to high concentrations of zinc nitrate in water, up to 22 mol% of the Ca2+ ions can displaced by Zn2+ ions without any measured loss in crystallinity and preservation of crystallite size and shape. It was found that the incorporation of Zn2+ ions destabilizes the HAp crystals resulting in their gradual dissolution and reprecipitation. Consequently, promoting the exchange of Ca2+ with Zn2+ions using increased reaction times, sonication and increased temperature results in an increased dissolution of HAp and precipitation of hopeite crystals, thereby preventing the formation of more zinc rich Zn-HAp.