A Further Study on Calcium Phosphate Gardens Grown from the Interface of κ-Carrageenan-based Hydrogels and Counterion...

Originating from the concept of classical chemical gardens, a new field coined 'chemobrionics' has recently emerged. In the present work, two chemobrionic systems grown from a hydrogel/liquid interface at different time scales (for 1, 7, 14 or 28 days) were investigated, i. e., a calcium-based hydrogel with a phosphate counterion solution (Ca-gel) and a phosphate-based hydrogel with a calcium counterion solution (P-gel). The initial pH changes of the systems were investigated, and the obtained tubular structures were studied using optical microscopy, SEM, AFM, PXRD and TGA. One of the important findings is that the tubes obtained in the Ca-gel system were straight and long, which could be explained by the larger pH difference observed between the hydrogel and the counterion solution in this system (ΔpH∼2.1) compared to the P-gel system (ΔpH∼0). The Ca-gel structures remained overall more amorphous even though increased crystallinity was observed in both systems with increased time spent in counterion solution. Both systems contained hydroxyapatite phases, with additional calcite phases observed for the P-gel structures and traces of κ-carrageenan for the Ca-gel structures. Our study provides a promising method for controlling tubular macrostructures through adjusting the reaction conditions such as maturation time and pH.