The functional requirements for synthetic tissue substitutes appear deceptively simple: they should provide a porous matrix with interconnecting porosity and surface properties that promote rapid tissue ingrowth; at the same time, they should possess sufficient stiffness, strength and toughness to prevent crushing under physiological loads until full integration and healing are reached. Despite extensive efforts and first encouraging results, current biomaterials for tissue regeneration tend to suffer common limitations: insufficient tissue-material interaction and an inherent lack of strength and toughness associated with porosity. The challenge persists to synthesize materials that mimic both structure and mechanical performance of the natural tissue and permit strong tissue-implant interfaces to be formed. In the case of bone substitute materials, for example, the goal is to engineer high-performance composites with effective properties that, similar to natural mineralized tissue, exceed by orders of magnitude the properties of its constituents. It is still difficult with current technology to emulate in synthetic biomaterials multi-level hierarchical composite structures that are thought to be the origin of the observed mechanical property amplification in biological materials. Freeze casting permits to manufacture such complex, hybrid materials through excellent control of structural and mechanical properties. As a processing technique for the manufacture of biomaterials, freeze casting therefore has great promise.
The development of materials to support bone regeneration requires flexible fabrication technologies able to tailor chemistry and architecture for specific applications. In this work, we describe the preparation of ceramic-based inks for robotic-assisted deposition (robocasting) using Pluronic® F-127 solutions. This approach allows the preparation of pseudoplastic inks with solid contents ranging between 30–50 vol% enabling them to flow through a narrow printing nozzle while supporting the weight of the printed structure. Ink formulation does not require the manipulation of the pH or the use of highly volatile organic components. Therefore, the approach can be used to prepare materials with a wide range of compositions, and here we use it to build hydroxyapatite (HA), β-tricalcium phosphate (β-TCP), and biphasic (HA/β-TCP) structures. The flow of the inks is controlled by the Pluronic® content and the particle-size distribution of the ceramic powders. The use of wide size distributions favors flow through the narrow printing nozzles, and we have been able to use printing nozzles as narrow as 100 μm in diameter, applying relatively low printing pressures. The microporosity of the printed lines increases with increasing Pluronic® contents and lower sintering temperatures. Microporosity can play a key role in determining the biological response to the materials, but it also affects the strength of the structure.
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