Three-Dimensional-Printed Molds from Water-Soluble Sulfate Ceramics for Biocomposite Formation through Low-Pressure Injection Molding.

Powder mixtures of MgSO4 with 5-20 mol.% Na2SO4 or K2SO4 were used as precursors for making water-soluble ceramic molds to create thermoplastic polymer/calcium phosphate composites by low pressure injection molding. To increase the strength of the ceramic molds, 5 wt.% of tetragonal ZrO2 (Y2O3-stabilized) was added to the precursor powders. A uniform distribution of ZrO2 particles was obtained. The average grain size for Na-containing ceramics ranged from 3.5 ± 0.8 µm for MgSO4/Na2SO4 = 91/9% to 4.8 ± 1.1 µm for MgSO4/Na2SO4 = 83/17%. For K-containing ceramics, the values were 3.5 ± 0.8 µm for all of the samples. The addition of ZrO2 made a significant contribution to the strength of ceramics: for the MgSO4/Na2SO4 = 83/17% sample, the compressive strength increased by 49% (up to 6.7 ± 1.3 MPa), and for the stronger MgSO4/K2SO4 = 83/17% by 39% (up to 8.4 ± 0.6 MPa). The average dissolution time of the ceramic molds in water did not exceed 25 min.

Stereolithographic fabrication of three-dimensional permeable scaffolds from CaP/PEGDA hydrogel biocomposites for use as bone grafts.

Polyethylene glycol diacrylate-based hydrogels filled with calcium phosphates (CaP, Ca/P < 1.5) were stereolithographically fabricated as three-dimensional permeable biocomposites for bone tissue regeneration, probed by several instrumental techniques (including scanning electron microscopy, infrared and UV-vis spectroscopy), and subjected to rheological/mechanical property analysis. As the CaP content increased from 0 to 10 wt%, Young's modulus and mechanical strength increased from 4 to 11 kPa and from 34 to 167 kPa, respectively. Moreover, the enhanced elastic properties and tuneable swelling behaviour of the fabricated composites made them well suited for bone defect filling.

The Interplay of manganese and nitrate in hydroxyapatite nanoparticles as revealed by pulsed EPR and DFT.

The interplay of oppositely charged substitutions in the structure of hydroxyapatite (HAp) nanopowders is investigated on the atomic level by pulsed electron paramagnetic resonance (EPR) technique and ab initio density functional theory calculations. Benefits of EPR to determine Mn(2+) ions in nano-HAp samples are demonstrated. A simple approach based on the measurements of electron spin relaxation times allowed observing the strong influence of fast-relaxing Mn(2+) ions on the relaxation characteristics of the nitrate ions (NO3(-)/NO3(2-)) incorporated in trace amounts. Based on the results of ab initio calculations, we show the propensity of Mn(2+) and NO3(-)/NO3(2-) to associate within the HAp crystal lattice. This could have a direct impact on the functional properties of the material especially to resorption and ion exchange. Furthermore, such an effect can increase a propensity of undesired impurities to incorporate into the doped nanocrystals.

Combination of EPR measurements and DFT calculations to study nitrate impurities in the carbonated nanohydroxyapatite.

We demonstrate the application of the combined experimental-computational approach for studying the anionic impurities in hydroxyapatite (HAp). Influence of the carbonation level (x) on the concentration of the NO3(2-) radicals in the HAp nanocrystals of Ca10-xNax(PO4)6-x(CO3)x(OH)2 with x in the range 0 < x < 2 and average sizes of 30 nm is investigated by different analytical methods including electron paramagnetic resonance (EPR). Stable NO3(2-) radicals are formed under X-ray irradiation of nano-HAp samples from NO3(-) ions incorporated in trace amounts during the wet synthesis process. Density functional theory (DFT) based calculations show energetic preference for the PO4 group substitution by NO3(-) ions. Comparison of the calculated and experimental spectroscopic parameters (g and hyperfine tensors) reveals that EPR detects the NO3(2-) radicals located in the positions of the PO4 group only. It is shown that with the increase in x, the carbonate ions substitute the NO3(2-)/NO3(-) ions. DFT calculations confirm that carbonate incorporation in HAp structure is energetically more favorable than the formation of the nitrate defect.