Cockle shells are a natural reservoir of calcium carbonate (CaCO3), which is widely used in bone repair, tissue scaffolds, and the development of advanced drug delivery systems. Although many studies report on the preparation of CaCO3, the development of a nanosized spherical CaCO3 precursor for calcium oxide (CaO) that is suitable to be incorporated in dental material was scarce. Therefore, this study aimed to synthesize a nanosized spherical CaCO3 precursor for CaO derived from cockle shells using a sol–gel method. Cockle shells were crushed to powder form and mixed with hydrochloric acid, forming calcium chloride (CaCl2). Potassium carbonate (K2CO3) was then fed to the diluted CaCl2 to obtain CaCO3. The effect of experimental parameters on the morphology of CaCO3, such as volume of water, type of solvents, feeding rate of K2CO3, and drying method, were investigated using field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry (XRD), Brunauer–Emmett–Teller surface area analysis, and thermogravimetric analysis. Optimized CaCO3 was then calcined to form CaO. XRD analysis of CaCO3 nanoparticles was indicative of the formation of a calcite phase. The well-structured spherical shape of CaCO3 was obtained by the optimum condition of the addition of 50 mL of water into CaCl2 in ethanolic solution with a 1 h feeding rate of K2CO3. Less agglomeration of CaCO3 was obtained using a freeze-drying technique with the surface area of 26 m2/g and average particle size of 39 nm. Spherical shaped nanosized CaO (22–70 nm) was also synthesized. The reproducibility, low cost, and simplicity of the method suggest its potential applications in the large-scale synthesis of the nanoparticles, with spherical morphology in an industrial setting.
Various oxides are used to stabilize zirconium oxide (ZrO2), but their superior hardness causes wear of the machining tool. Calcia-doped zirconia has been studied but reports on properties suitable for dental application are lacking. Therefore, this study aimed to fabricate and characterize zirconia stabilized by calcium oxide (CaO) derived from cockle shells and compare it with zirconia stabilized by commercial CaO, sintered at different temperatures. In this study, 176 pressed pellets of zirconia mixed with CaO either derived from cockle shells or commercial CaO were sintered between 1200 and 1500 °C to produce calcia-doped zirconia. Characterizations were made with SEM and XRD. Specimens were subjected to density, compressive and flexural strength, and Vickers hardness testing. Data were analyzed using the independent t-test and one-way ANOVA. XRD revealed the zirconia was stabilized into tetragonal and cubic phases (Ca-SZ). Ca-SZ cockle shells (CS) and Ca-SZ commercial (CC) have average particle sizes of 267 nm and 272 nm, respectively, with similar surface roughness. At 1400 °C sintering temperature, flexural strengths were 1165 and 1152 MPa, compressive strengths were 4914 and 4913 MPa, and Vickers hardness were 977 and 960 MPa for Ca-SZ(CS) and Ca-SZ(CC), respectively. Both Ca-SZ materials showed no significant difference in most properties (p < 0.05) when sintered at different temperatures. The fully sintered Ca-SZ is less hard compared to the ceria-stabilized tetragonal zirconia polycrystal (Ce-TZP) available on the market. Thus, Ca-SZ may be used as an alternative to the current zirconia available on the market for dental application.
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