Tasheva Tina, Yoleva Albena, Mateeva Janna, Georgiev Hristo
Department of Silicate Technology, University of Chemical Technology and Metallurgy, 8 Kliment Ohridski blvd, 1797 Sofia, Bulgaria.
Department of Industrial Safety, University of Chemical Technology and Metallurgy, 8 Kliment Ohridski blvd, 1797 Sofia, Bulgaria.
Materials (Basel). 2025 Jun 27;18(13):3059. doi: 10.3390/ma18133059.
A novel bioactive glass-ceramic was developed using biogenic hydroxyapatite (BHA) synthesized from (Black Sea) shells and monocalcium phosphate monohydrate [Ca(HPO)·HO] via solid-state synthesis. The prepared batches were obtained by combining BHA with SiO, BO, and NaO, melted at 1200 °C and melt-quenched in water to form glass-ceramic materials. Dense biogenic hydroxyapatite-based ceramics were successfully sintered at 1200 °C (2 h hold) using a 25 mass % sintering additive composed of 35 mass % BO, 45 mass % SiO, 10 mass % AlO, and 10 mass % NaO. Structural characterization was carried out using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The resulting materials consisted of a well-defined crystalline hydroxyapatite phase [Ca(PO)(OH)] alongside an amorphous phase. In samples with increased SiO and reduced BO content (composition 3), a finely dispersed NaCa(PO) crystalline phase appeared, with a reduced presence of hydroxyapatite. Bioactivity was assessed in simulated body fluid (SBF) after 10 and 20 days of immersion, confirming the material's ability to support apatite layer formation. The main structural units SiO, PO, and BO are interconnected through Si-O-Si, B-O-B, P-O-P, and mixed Si-O-Al linkages, contributing to both structural stability and bioactivity.
利用从（黑海）贝壳中合成的生物源羟基磷灰石（BHA）和一水磷酸二氢钙[Ca(H₂PO₄)₂·H₂O]，通过固态合成法开发了一种新型生物活性玻璃陶瓷。将BHA与SiO₂、B₂O₃和Na₂O混合，在1200℃下熔融并在水中进行熔体淬火，以制备玻璃陶瓷材料。使用由35质量%B₂O₃、45质量%SiO₂、10质量%Al₂O₃和10质量%Na₂O组成的25质量%烧结添加剂，在1200℃（保温2小时）成功烧结出致密的生物源羟基磷灰石基陶瓷。使用X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）和扫描电子显微镜（SEM）进行结构表征。所得材料由明确的结晶羟基磷灰石相[Ca₁₀(PO₄)₆(OH)₂]和非晶相组成。在SiO₂含量增加而B₂O₃含量降低的样品（组成3）中，出现了细分散的NaCaPO₄结晶相，羟基磷灰石的存在减少。在模拟体液（SBF）中浸泡10天和20天后评估生物活性，证实了该材料支持磷灰石层形成的能力。主要结构单元SiO₂、PO₄³⁻和B₂O₃通过Si-O-Si、B-O-B、P-O-P和混合的Si-O-Al键相互连接，有助于结构稳定性和生物活性。
