Effect of co-precipitation plus spray-drying of nano-CaF₂ on mechanical and fluoride properties of nanocomposite

Objective: Fluoride (F)-releasing restoratives typically are either weak mechanically or release only low levels of F ions. The objectives of this study were to: (1) develop a novel photo-cured nanocomposite with strong mechanical properties and high levels of sustained F ion release via a two-step “co-precipitation + spray-drying” technique to synthesize CaF₂ nanoparticles (nCaF₂); and (2) investigate the effect of spray-drying treatment after co-precipitation of nCaF₂ on mechanical properties and F ion release of composite. Methods: Two types of CaF₂ particles were synthesized: A co-precipitation method yielded CaF₂cp; “co-precipitation + spray-drying” yielded nCaF₂cpsd. Composites were fabricated with fillers of: (1) 0% CaF₂ + 70% glass; (2) 10% CaF₂cp + 60% glass; (3) 15% CaF₂cp + 55% glass; (4) 20% CaF₂cp + 50% glass; (5) 10% nCaF₂cpsd + 60% glass; (6) 15% nCaF₂cpsd + 55% glass; and (7) 20% nCaF₂cpsd + 50% glass. A commercial F-releasing nanocomposite served as control. Results: The nCaF₂cpsd had much smaller particle size (median = 32 nm) and narrower distribution (22–57 nm) than CaF₂cp (median = 5.25 μm, 162 nm–67 μm). The composite containing nCaF₂cpsd had greater flowability, flexural strength, elastic modulus and hardness than CaF₂cp composite and commercial control composite. At 84-day immersion in water, the nanocomposites containing 20% nCaF₂cpsd had 65 times higher cumulative F release, and 77 times greater long-term F-release rate, than commercial control. Conclusions: A novel two-step “co-precipitation + spray-drying” technique of synthesizing nCaF₂ was developed. The photo-cured nanocomposite containing 20% nCaF₂cpsd possessed strong mechanical properties and excellent long-term F-release ability, and hence is promising for dental restoration applications to inhibit secondary caries.