Preceramic polymers, i.e., polymers that are converted into ceramics upon heat treatment, have been successfully used for almost 40 years to give advanced ceramics, especially belonging to the ternary SiCO and SiCN systems or to the quaternary SiBCN system. One of their main advantages is the possibility of combining the shaping and synthesis of ceramics: components can be shaped at the precursor stage by conventional plastic-forming techniques, such as spinning, blowing, injection molding, warm pressing and resin transfer molding, and then converted into ceramics by treatments typically above 800 °C. The extension of the approach to a wider range of ceramic compositions and applications, both structural and thermo-structural (refractory components, thermal barrier coatings) or functional (bioactive ceramics, luminescent materials), mainly relies on modifications of the polymers at the nano-scale, i.e., on the introduction of nano-sized fillers and/or chemical additives, leading to nano-structured ceramic components upon thermal conversion. Fillers and additives may react with the main ceramic residue of the polymer, leading to ceramics of significant engineering interest (such as silicates and SiAlONs), or cause the formation of secondary phases, significantly affecting the functionalities of the polymer-derived matrix.

1Magnesium is a trace element in the human body, known to have important effects on cell 2 differentiation and the mineralisation of calcified tissues. This study aimed to synthesise

Wollastonite (CaSiO3) and diopside (CaMgSi2O6) silicate ceramics have been widely investigated as highly bioactive materials, suitable for bone tissue engineering applications. In the present paper, highly porous glass-ceramic foams, with both wollastonite and diopside as crystal phases, were developed from the thermal treatment of silicone polymers filled with CaO and MgO precursors, in the form of micro-sized particles. The foaming was due to water release, at low temperature, in the polymeric matrix before ceramic conversion, mainly operated by hydrated sodium phosphate, used as a secondary filler. This additive proved to be “multifunctional”, since it additionally favored the phase development, by the formation of a liquid phase upon firing, in turn promoting the ionic interdiffusion. The liquid phase was promoted also by the incorporation of powders of a glass crystallizing itself in wollastonite and diopside, with significant improvements in both structural integrity and crushing strength. The biological characterization of polymer-derived wollastonite-diopside foams, to assess the bioactivity of the samples, was performed by means of a cell culture test. The MTT assay and LDH activity tests gave positive results in terms of cell viability.

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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 SiO/CaCO 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.

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.

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