Amorphous CaCO3: Influence of the Formation Time on Its Degree of Hydration and Stability

Calcium carbonate (CaCO3) is one of the most abundant biominerals that is prevalent in rocks and often used as a structural material in marine animals. Many of these natural CaCO3-based materials display excellent mechanical properties that are difficult to reproduce by man-made counterparts. This difficulty arises from the incomplete understanding of the influence of processing conditions on the structure and composition of CaCO3. To gain a better understanding of the evolution of the structure and composition of amorphous CaCO3 (ACC) particles during early stages, we introduce a new, organic solvent-free method that quenches this process with a high temporal resolution. We produce ACC particles inside small airborne drops that are formed with a microfluidic spray-dryer. These drops dry within 100 ms to 10 s and thereby arrest the formation of CaCO3 particles on that time scale. Using the microfluidic spray-dryer, we demonstrate that the amount of mobile water contained in ACC particles increases with increasing formation time and hence with increasing particle size. As a result of the higher concentration of mobile water, larger particles are less stable against temperature-induced solid-state crystallization and electron beam-induced decomposition than smaller counterparts. The amount of mobile water contained in ACC can be substantially reduced, and hence their kinetic stability against solid-state transformations increased, if certain organic additives, such as poly(acrylic acid) (PAA), are incorporated. These insights might open up new opportunities to fabricate biomimetic CaCO3-based materials with tunable structures and hence with properties that can be adapted to the needs of specific applications.