J. Mater. Sci. Technol. ›› 2020, Vol. 36: 27-36.DOI: 10.1016/j.jmst.2019.04.038
• Research Article • Previous Articles Next Articles
Wei Cuiab, Qibin Songc, Huhu Suab, Zhiqing Yangab, Rui Yangab, Na Lia*(), Xing Zhangab*()
Received:
2019-01-19
Revised:
2019-03-06
Accepted:
2019-04-25
Published:
2020-01-01
Online:
2020-02-11
Contact:
Li Na,Zhang Xing
About author:
1 These two authors contributed equally to this work.
Wei Cui, Qibin Song, Huhu Su, Zhiqing Yang, Rui Yang, Na Li, Xing Zhang. Synergistic effects of Mg-substitution and particle size of chicken eggshells on hydrothermal synthesis of biphasic calcium phosphate nanocrystals[J]. J. Mater. Sci. Technol., 2020, 36: 27-36.
Fig. 1. XRD patterns of seashell (0% Mg), eggshell (2% Mg) and sea urchin spine (11.5% Mg) samples before (a, b) and after (c, d) hydrothermal reactions at 200 °C for 24 h. With the increase of Mg content, the diffraction peaks of calcite (104) and β-TCP (0210) shifted to the large angles (b, d). XRD patterns (e) and FTIR spectra (f) of products by hydrothermal reactions of eggshell samples (~150-840 μm) at 200 °C for 2, 4, 8 and 24 h. C was abbreviation for calcite. T was abbreviation for β-TCP. H was abbreviation for hydroxyapatite.
Mg content (mol.%) | #1 | #2 | #3 | Ave. | Std. |
---|---|---|---|---|---|
Seashell | 0 | 0 | 0 | 0 | 0 |
Eggshell | 3.3% | 2.0% | 0.8% | 2.0% | 1.0% |
Sea urchin spine | 10.8% | 11.4% | 12.4% | 11.5% | 0.7% |
Table 1 ICP results for Mg contents (Mg/(Mg + Ca)) from seashell, eggshell and sea urchin spine samples.
Mg content (mol.%) | #1 | #2 | #3 | Ave. | Std. |
---|---|---|---|---|---|
Seashell | 0 | 0 | 0 | 0 | 0 |
Eggshell | 3.3% | 2.0% | 0.8% | 2.0% | 1.0% |
Sea urchin spine | 10.8% | 11.4% | 12.4% | 11.5% | 0.7% |
Fig. 2. SEM images of an eggshell section (a) composed of the inner mammillary knob layer (b), the middle palisade layer (c), and the outer cuticle layer (d). Micro- and sub-micron pore structures were found inside of eggshells (d-f). A TEM bright field image of the palisade layer of an eggshell sample showed the dense structure with sub-micron pores (g), and the corresponding electron diffraction confirmed the crystal lattices of calcite (h). A high-resolution TEM image indicated nano grains of calcite in the eggshell sample after exposure to electron beams (i).
Fig. 3. SEM images of HA nanoparticles on the surfaces of eggshell samples (~150-840 μm) after hydrothermal reactions at 200 °C for 2 h (a), 4 h (b) and 24 h (c). TEM bright field images (d, e) and electron diffraction pattern (f) of HA nanoparticles on the internal surfaces of micro-pores after hydrothermal reactions at 200 °C for 24 h. The high-magnification image (e) was from the selected area of the yellow dashed square in (d). The yellow dashed circle in (e) indicated the HA granules on the internal surface consisted of nano-size particles.
Fig. 4. SEM figures of the interior of an eggshell sample (~150-840 μm) after hydrothermal reactions at 200 °C for 2 h (a), 4 h (b) and 24 h (c). TEM bright field images (d, e) of β-TCP particles after hydrothermal conversion of the eggshell sample for 24 h, and corresponding electron diffraction pattern (f). The yellow dashed square in (d) indicated the initial split from a pore caused by the lattice volume shrinkage from Mg-calcite to β-TCP. Beta-TCP particles consisted of nano grains of ~3-20 nm with the same orientation (e, f).
Fig. 5. XRD patterns of BCP products through hydrothermal reactions of eggshell samples with different sizes at 200 °C for 24 h (a). Diffraction peaks of HA (202) and β-TCP (220) overlapped in the XRD patterns, highlighted with yellow color (a). Fitting of the XRD pattern for peak area measurement (b). The linear relationship of Aβ-TCP/(Aβ-TCP+AHA) and Wβ-TCP/(Wβ-TCP+WHA) based on ten samples with different β-TCP contents (c). Calculated β-TCP contents (wt.%) in BCP products (d) from eggshell samples with different sizes based on the linear relationship in (c).
Fig. 6. Schematic diagrams for hydrothermal reactions of eggshell samples: ion-exchange reactions for β-TCP nanocrystals formation in the interior of the sample, CO32- ions in Mg-calcite lattices were substituted by PO43- ions, resulting in the formation of Mg-TCP (a), dissolution-reprecipitation reactions for HA nanocrystals formation on the outer surface of the sample (b) and on the internal surface of a micro-size pore (c) from saturated Ca2+, PO43- and OH- ions in the solution.
Fig. 7. OD values from cell culture media with/without BCP extracts using different particle sizes after culture with MC3T3-E1 cells for 24 and 72 h using the CCK8 assay (a). Fluorescence staining of cells cultured for 24 h with BCP extracts using different particle sizes: < 45 μm (b), 45-75 μm (c), 150-840 μm (d), and the control group (without BCP extracts) (e). The cell nuclei and smooth muscle alpha-actin were stained with DAPI (blue) and FITC-phalloidin (green), respectively. SEM images showed cell spreading with a large number of filopodia when cultured atop of a BCP sample for 24 h (f, g).
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