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Photo curing of low-cytotoxic alkyne carbonate/thiol formulations leads to tough polymers with adjustable degradation behavior for 3D printing of biomedical devices.

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Bioactive glasses and glass ceramics like the 45S5 formulation have been studied toward biocompatibility and biodegradability for years. Nevertheless, clinical applications as bone substitute or scaffold material are highly limited because of the often poor mechanical behavior of bioactive glasses. In this study, we are able to provide a new production alternative for 45S5 bioactive glass structures resulting in parts with high density and strength. Using the stereolithographic ceramic manufacturing (SLCM) process, it is possible to additively produce solid bulk glass ceramics as well as delicate scaffold structures. Recent developments in SLCM slurry preparation together with an appropriate selection of raw materials led to 3D parts with a very homogeneous microstructure and a density of about 2.7 g/cm³. Due to the low number and small size of defects, a high biaxial bending strength of 124 MPa was achieved. Weibull distribution also underlines good process control showing a Weibull modulus of 8.6 and a characteristic strength of 131 MPa for the samples tested here. By reaching bending strength values of natural cortical bone, bioactive glasses processed with SLCM could eventually advance to be an interesting bone substitute material even in load‐bearing applications, valuing the huge efforts undertaken to understand their bioactive behavior.

Within the large variety of different additive manufacturing technologies stereolithography excels in high precision and surface quality. Using the Digital Light Processing (DLP) Technology a stereolithography-based system was developed, which is specifically designed for the processing of highly filled photopolymers.The powder-filled suspension enables the 3D-fabrication of a so called ceramic green part. In order to get a dense ceramic structure, subsequent thermal processing steps after the 3D-printing process are necessary. First, the polymer-ceramic composites heated up to 400°C. During this processing step, called debinding, the organic components are burned out. The resulting part, consisting of powder particles stabilized by physical interactions, is further heated to sinter the particles together, and the final, fully dense ceramic part is obtained.The debinding step is the most critical process. The used components have different evaporation or decomposition temperatures and behaviors. Thereby a reduction in weight and also in dimension occurs, which depends on the portion and composition of the organic components and especially on the temperature cycle. Furthermore, the physical characteristics of the ceramic powder, such as the particle size and the size distribution influence the debinding behavior. To measure the changes in weight and dimension a thermo-gravimetric (TGA) and a thermo-mechanical analysis (TMA) can be used. To avoid too high internal gas pressures inside the green parts a preferably constant gas evolution rate is seeked. Also the ‘surface-to-volume ratio’ affects the debinding characteristics. Therefore, optimized debinding cycles for specific geometries allow the crack-free debinding of parts with a wall thickness up to 20 mm.