Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO2/CaCO3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.

Biocompatibility and bioactivity of porous polymer-derived Ca-Mg silicate ceramics.

Magnesium is a trace element in the human body, known to have important effects on cell differentiation and the mineralisation of calcified tissues. This study aimed to synthesise highly porous Ca-Mg silicate foamed scaffolds from preceramic polymers, with analysis of their biological response. Akermanite (Ak) and wollastonite-diopside (WD) ceramic foams were obtained from the pyrolysis of a liquid silicone mixed with reactive fillers. The porous structure was obtained by controlled water release from selected fillers (magnesium hydroxide and borax) at 350°C. The homogeneous distribution of open pores, with interconnects of modal diameters of 160-180µm was obtained and maintained after firing at 1100°C. Foams, with porosity exceeding 80%, exhibited compressive strength values of 1-2MPa. In vitro studies were conducted by immersion in SBF for 21days, showing suitable dissolution rates, pH and ionic concentrations. Cytotoxicity analysis performed in accordance with ISO10993-5 and ISO10993-12 standards confirmed excellent biocompatibility of both Ak and WD foams. In addition, MC3T3-E1 cells cultured on the Mg-containing scaffolds demonstrated enhanced osteogenic differentiation and the expression of osteogenic markers including Collagen Type I, Osteopontin and Osteocalcin, in comparison to Mg-free counterparts. The results suggest that the addition of magnesium can further enhance the bioactivity and the potential for bone regeneration applications of Ca-silicate materials. STATEMENTS OF SIGNIFICANCE: Here, we show that the incorporation of Mg in Ca-silicates plays a significant role in the enhancement of the osteogenic differentiation and matrix formation of MC3T3-E1 cells, cultured on polymer-derived highly porous scaffolds. Reduced degradation rates and improved mechanical properties are also observed, compared to Mg-free counterparts, suggesting the great potential of Ca-Mg silicates as bone tissue engineering materials. Excellent biocompatibility of the new materials, in accordance to the ISO10993-5 and ISO10993-12 standard guidelines, confirms the preceramic polymer route as an efficient synthesis methodology for bone scaffolds. The use of hydrated fillers as porogens is an additional novelty feature presented in the manuscript.

Highly porous polymer-derived wollastonite-hydroxycarbonate apatite ceramics for bone regeneration.

A novel strategy was employed to synthesize highly porous wollastonite-hydroxycarbonate apatite ceramic scaffolds for bone regeneration. A commercial liquid preceramic polymer filled with micro-CaCO3 powders was foamed at low temperature (at 350 °C), using the decomposition of a hydrazine additive, and then converted into ceramic by a treatment at 700 °C. Hydroxycarbonate apatite was later developed by a phosphatization treatment of ceramized foams, in a P-rich solution, while wollastonite was obtained by a second firing, at 900 °C. The effectiveness of the method was proven by x-ray diffraction analysis, showing the presence of the two expected crystalline phases. Porosity, interconnect size distribution and mechanical strength were in the range that is thought to be suitable for bone regeneration in non-load bearing sites (compressive strength ≈ 3 MPa, porosity ≈ 90%, modal interconnect diameter ≈ 130-160 µm). In addition, bioactivity and ion release rate were assessed in simulated body fluid (SBF). MC3T3 osteoblast precursor cells were able to colonize the material in vitro through the pore architecture and expressed osteogenic markers.

Novel processing of bioglass ceramics from silicone resins containing micro- and nano-sized oxide particle fillers.

Highly porous scaffolds with composition similar to those of 45S5 and 58S bioglasses were successfully produced by an innovative processing method based on preceramic polymers containing micro- and nano-sized fillers. Silica from the decomposition of the silicone resins reacted with the oxides deriving from the fillers, yielding glass ceramic components after heating at 1000°C. Despite the limited mechanical strength, the obtained samples possessed suitable porous architecture and promising biocompatibility and bioactivity characteristics, as testified by preliminary in vitro tests.