Hierarchically porous 3D-printed akermanite scaffolds from silicones and engineered fillers

The present investigation is dedicated to the manufacturing of reticulated three-dimensional akermanite scaffolds, developed by direct reaction between silica, from the oxidation of a commercial silicone resin and oxide fillers, forming pastes for direct ink writing. Crack-free scaffolds, with dense and regular struts, were due to the use of CaCO₃ (micro) and MgO nano-particles as reactive fillers. An excellent phase purity was obtained, with the help of the liquid phase provided by anhydrous sodium borate (Na₂B₄O₇), upon firing. The structure of the scaffolds, finally, was successfully modified by using Mg(OH)₂ and hydrated sodium borate: besides macro-porosity from direct ink writing, the new scaffolds exhibited homogenous ‘spongy’ struts (owing to water vapor release in the heating step), with no crack. Both types of scaffolds (with dense or porous struts) exhibited remarkable strength-to-density ratios.     

Novel glass-ceramic SOFC sealants from glass powders and a reactive silicone binder

The processing of sintered ceramics is often conditioned by the debinding step. The binders may determine some defects in the final product directly, by causing some gas evolution even at an advanced state of densification, due to incomplete decomposition at low temperature, or indirectly, by offering poor adhesion between particles, so that ‘green’ compacts may be easily damaged. The present investigation is aimed at exploring a novel concept for sintered glass-ceramics, based on the adoption of a silicone polymer as reacting binder, providing an abundant ceramic residue after firing. A glass belonging to the CaO-MgO-Al₂O₃-SiO₂ system, already studied as a sealant in solid oxide fuel cell (SOFC) planar stack design, was reproduced in form of ‘silica-defective’ variants, featuring a SiO₂ content, in the overall formulation, reduced up to 15?wt%. The overall silica content was recovered by mixing powders of the new glasses with the silicone: upon firing in air, the interaction between glass powders and polymer-derived silica led to glass-ceramics with the same phase assemblage than that formed by the reference glass and with a CTE of 9.5?×?10^?6 K^-1. The new approach has been successfully applied to the manufacturing of glass-ceramic seals as joining materials for solid oxide cells.     

Additive manufacturing and direct synthesis of sphene ceramic scaffolds from a silicone resin and reactive fillers

Sphene (CaTiSiO₅, i.e. CaO·TiO₂·SiO₂) ceramics were successfully developed via the polymer derived ceramics route, starting from a commercial silicone containing specific oxide fillers. The approach allowed the combination of synthesis, in conditions of high phase purity, and advanced manufacturing. In particular, the adopted starting materials enabled an easy preparation of pastes, to be used for direct ink writing (DIW) of three-dimensional reticulated scaffolds. Sphene scaffolds, after firing at 1300 °C, were always regular and crack-free, despite changes in the line spacing, resulting in variable porosity (from ≈ 59 to 74 %), and exhibited a compressive strength from 3.9 to 12.7 MPa. The porosity was actually hierarchical, considering the formation of ‘spongy’ struts. In vitro tests, with increasing immersion time in SBF solution, confirmed the bioactivity, combined with a quite slow ion release, useful to maintain the pH value at nearly physiological values. Additional biological tests, consisting of the seeding of scaffold with normal human adult dermal fibroblasts, showed adequate cell viability and no toxicity effect.     

B-doped hardystonite bioceramics from preceramic polymers and fillers: Synthesis and application to foams and 3D-printed scaffolds

Highly porous hardystonite-based bioceramics, in the form of foams and 3D scaffolds, were obtained by the thermal treatment, in air, of silicone resins and engineered micro-sized oxide fillers. Besides CaO and ZnO precursors (CaCO₃ and ZnO powders), calcium borate, in both hydrated and anhydrous form (Ca₂B₆O₁₁·5H₂O and Ca₂B₆O₁₁, respectively), was added to commercial silicone resins, with a significant impact on the microstructural evolution. In hydrated form, calcium borate led to a substantial foaming of silicone-based mixtures, at low temperature (420 °C); after dehydration, upon firing, the salt provided a liquid phase, favouring ionic interdiffusion, with the development of novel B-contaning hardystonite-based solid solutions (Ca₂Zn_1-xB_2xSi_2-xO₇). Although fired at lower temperature than previously developed silicone-derived hardystonite cellular ceramics (950 °C, instead of 1200 °C), the newly obtained foams and scaffold exhibit substantial improvements in the mechanical properties.     

Direct ink writing additive manufacturing of porous alumina-based ceramic cores modified with nanosized MgO

Alumina-based ceramic cores, widely applied to cast alloy, have been restricted by the increased complexity of castings, the resultant complex equipment and cost. In this research, to address the aforesaid disadvantages, direct ink writing, a green additive manufacturing method, is utilized to directly fabricate a new kind of nanosized MgO strengthened alumina-based ceramic cores. Slurries with various compositions exhibits ideal shear-thinning behaviors, owing to the hydrogen bond formed between polyvinylpyrrolidone and kaolin molecules. We notice that introducing nanosized MgO reduces drying shrinkage of green specimens and greatly promotes liquid-phase sintering, leading to rather more densified samples. Overall, it is anticipated that the current approach is effective in rapidly manufacturing alumina-based ceramics and some other ceramics with high strength, low shrinkage and high quality.     

The fabrication and characterization of bioactive Akermanite/Octacalcium phosphate glass-ceramic scaffolds produced via PDC method

In the present study, a bioactive silicate-phosphate glass-ceramic scaffold was fabricated via the polymer-derived ceramics (PDC) method. K₂HPO₄ phosphate salt was used as the P₂O₅ precursor in this method. The effect of K₂HPO₄ wt% and heat treatment temperatures (900–1100 °C) was evaluated. It was observed that although increasing the wt% of K₂HPO₄ led to the formation of scaffolds with higher densities and strengths, it could also increase the formation of the calcium phase, which could result in improper release behavior of scaffolds. On the other hand, higher heat treatment temperatures enhanced the strength of the scaffolds but eliminated the bioactive octacalcium phosphate (OCP) phase. X-ray diffraction (XRD) analysis showed that the dissolution of the OCP phase in simulated body fluid (SBF) resulted in precipitation of hydroxyapatite (HA) on the scaffold surface which enhanced the bioactivity. Furthermore, based on microstructural studies by Scanning Electron Microscopy (SEM), the fabricated scaffold possessed a wide range of pore sizes, appropriate for osteointegration and bone formation. The optimum wt% of phosphate salt was less than 6 wt% and the optimum heat treatment temperature was 1000 °C. After the optimization of compositions and processing, Alamar Blue Assay was used to evaluate HOb cell cultures, showing a continuous proliferation for the optimized samples.     

Direct ink writing of chopped carbon fibers reinforced polymer-derived SiC composites with low shrinkage and high strength

The chopped carbon fiber reinforced SiC (C_f/SiC) composite has been regarded as one of the excellent high-temperature structural materials for applications in aerospace and military fields. This paper presented a novel printing strategy using direct ink writing (DIW) of chopped fibers reinforced polymer-derived ceramics (PDCs) with polymer infiltration and pyrolysis (PIP) process for the fabrication of C_f/SiC composites with high strength and low shrinkage. Five types of PDCs printing inks with different C_f contents were prepared, their rheological properties and alignment of carbon fiber in the printing filament were studied. The 3D scaffold structures and bending test samples of C_f/SiC composites were fabricated with different C_f contents. The results found that the C_f/SiC composite with 30 wt% C_f content has high bending strength (～ 7.09 MPa) and negligible linear shrinkage (～ 0.48%). After the PIP process, the defects on the C_f/SiC composite structures were sufficiently filled, and the bending strength of C_f/SiC composite can reach up to about 100 MPa, which was about 30 times greater than that of the pure SiC matrix without C_f. This work demonstrated that the printed C_f/SiC composites by using this method is beneficial to the development of the precision and complex high-temperature structural members.     

Direct ink writing of geopolymeric inks

The development of geopolymeric inks with optimized rheological properties for DIW is presented; several inks with different water content and additives were compared to determine which parameters enable extrusion as well as shape retention. It is a challenging task, because the inks are subjected to ongoing poly-condensation reactions which continuously modify their rheological properties over time.Highly porous ceramic lattices (porosity up to ∼71 vol%) were fabricated with ∼0.8 mm struts and unsupported features with very limited sagging. Their physical and mechanical properties were characterized and correlated. Our approach can be successfully extended to other formulations.Geopolymeric foams have recently been proven as suitable for water filtration; the use of precisely designed, non stochastic printed structures could enhance the mechanical properties of the porous components, provide a better control of pressure drop and fluid dynamics inside the part and improve their performances consistently.     

Engineering of silicone-based mixtures for the digital light processing of Åkermanite scaffolds

Silicones mixed with oxide fillers are interesting precursors for several bioactive glass-ceramics. A key point is represented by the coupling of synthesis and shaping, since highly porous bodies, in form of foams or scaffolds, are first manufactured with silicones in the polymeric state, at low temperature, and later subjected to ceramic transformation. After successful application of direct ink writing, the present study illustrates the tuning of silicone-based mixtures in order to form åkermanite (Ca₂MgSi₂O₇) reticulated scaffolds by digital light processing. This implied the selection of commercial silicones, producing stable and homogeneous blends with a photocurable resin and enabling the manufacturing of defect-free printed scaffolds, before and after firing, without fillers. The blends were further refined with the introduction of fillers, followed by firing at 1100 °C, in air. Optimized samples (from H44 resin) and reactive fillers (including up to 4.5 wt.% borax additive), led to crack-free and phase-pure scaffolds with microporous struts.     

Direct ink writing of wollastonite-diopside glass-ceramic scaffolds from a silicone resin and engineered fillers

Wollastonite-diopside scaffolds have been successfully developed by direct ink writing of an ink made of silicone polymer and inorganic fillers. The main reason for using a silicone in the ink formulation consisted in its double effect, in controlling the ink rheology and in developing of wollastonite and diopside crystalline phases upon heat treatment. The obtained 3D wollastonite-diopside scaffolds featured regular geometries, and a high compressive strength (3.9–4.9 MPa) when considering the large amount of porosity (68–76 vol.%). A glass with the same oxide composition as the silicone-based ink and crystallizing into wollastonite and diopside, was produced and used as additional filler. This addition enabled the fabrication of even stronger 3D printed scaffolds (∼8 MPa for a porosity of 67 vol%), owing to the enhanced viscous flow upon firing which reduced the micro-cracks in the scaffold struts generated by the preceramic polymer decomposition. The obtained highly porous wollastonite-diopside glass-ceramic scaffolds are suitable candidates for bone tissue engineering.     

Fabrication of forsterite scaffolds with photothermal-induced antibacterial activity by 3D printing and polymer-derived ceramics strategy

Bacterial infection of the implanting materials is one of the greatest challenges in bone tissue engineering. In this study, porous forsterite scaffolds with antibacterial activity have been fabricated by combining 3D printing and polymer-derived ceramics (PDCs) strategy, which effectively avoided the generation of MgSiO₃ and MgO impurities. Forsterite scaffolds sintered in an argon atmosphere can generate free carbon in the scaffolds, which exhibited excellent photothermal effect and could inhibit the growth of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) in vitro. In addition, forsterite scaffolds have uniform macroporous structure, high compressive strength (>30 MPa) and low degradation rate. Hence, forsterite scaffolds fabricated by combining 3D printing and PDCs strategy would be a promising candidate for bone tissue engineering.     

Additive manufacturing of Csf/SiC composites with high fiber content by direct ink writing and liquid silicon infiltration

Direct ink writing (DIW) provides a new route to produce SiC-based composites with complex structure. In this study, we additive manufactured short carbon fiber reinforced SiC ceramic matrix composites (Csf/SiC composites) with different short carbon fiber content through direct ink writing combined with liquid silicon infiltration (LSI). The effects of short carbon fiber content on the microstructure and mechanical properties of the DIW green parts and the final Csf/SiC composites were investigated. The results showed that the Csf content played an important role in maintaining the structure of the green parts. As the Csf content increases, the dimension deviation ratio of the sample decreased at all stages. With the Csf content of 40 vol%, the final Csf/SiC composite had low free Si content and high β-SiC content. The maximum density, tensile strength and bending strength of the Csf/SiC composites were 2.88 ± 0.06 g/cm³, 53.68 MPa and 253.63 MPa respectively. It is believed that this study can give some understanding for the additive manufacturing of fiber reinforced ceramic matrix composites.     

3D printing of fine alumina powders by binder jetting

Additive manufacturing of ceramics is still at an early-development stage; however, the huge interest in custom production of these materials has led to the development of different techniques that could provide highly performing devices. In this work, alumina (α-Al₂O₃) components were produced by binder jetting 3D printing (BJ), a powder-based technique that enables the ex-situ thermal treatment of the printed parts. The employment of fine particles has led to high green relative density values (>60 %), as predicted by Lubachevsky-Stillinger algorithm and DEM modelling. Then, extended sintering has been observed on samples treated at 1750 °C that have reached a final density of 75.4 %. Finally, the mechanical properties of the sintered material have been assessed through bending test for flexural resistance and micro-indentation for Vickers hardness evaluation.     

A deep insight into the preparation of ceramic bone scaffolds utilizing robocasting technique

From long ago, orthopedists and physicians are trying to deal with bone diseases and disorders, while today, in the regenerative medicine field, bone scaffolds are being in attendance. Although there were common methods for fabricating bone scaffolds, such as foam casting and gas foaming, additive manufacturing (AM) techniques have been considered for producing bone scaffolds due to some appealing features such as creating a hierarchical structure, regular and controlled porosity, and designing of the complicated structures.AM techniques are divided into three categories, including extrusion-based, powder-based, and vat polymerization (light-based) techniques. Among the AM methods, the robocasting technique as an extrusion-based method is highly regarded for designing high-strength scaffolds for bone tissue regeneration owing to special features, for instance, a low-volume binder and the ability to print all types of ceramic materials as well as metals and polymers.This study discusses the robocasting method, as well as the essential parameters that are involved in 3D printing of the ideal scaffold with this method, such as the material, the structure of the robotic device, the printing parameters, the properties of the ideal paste or ink, the role of binder and its types in robocasting, and the rheological properties required in robocasting method. Also, future prospects and clinical applications of this technique were reviewed.     

Digital light processing additive manufacturing of in situ mullite-zirconia composites

Digital light processing (DLP) can produce small series ceramic parts with complex geometries and tiny structures without the high cost of molds usually associated with traditional ceramic processing. However, the availability of feedstock of different ceramics for the technique is still limited. Mullite-zirconia composites are refractory materials with diverse applications, nevertheless, their 3D printing has never been reported. In this work, alumina and zircon were used as raw materials for additive manufacturing by DLP followed by in situ mullite and zirconia formation. Thus, coarse zircon powder was milled to submicrometric size, alumina-zircon photosensitive slurries were prepared and characterized, parts were manufactured in a commercial DLP 3D printer, debound, and sintered at different temperatures. The printed parts sintered at 1600 °C completed the reaction sintering and reached a flexural strength of 84 ± 13 MPa. The process proved capable of producing detailed parts that would be unfeasible by other manufacturing methods.     

Vat photopolymerization-based additive manufacturing of high-strength RB-SiC ceramics by introducing quasi-spherical diamond

Silicon carbide is one of the most important high-performance engineering ceramics. However, SiC ceramics with complex structure and high mechanical performance are difficult to shape, sinter, and process. Additive manufacturing is expected to solve the above problems, but the photosensitive slurry with low solid content leads to high residual Si content and low strength of final components. Here, we presented one novel strategy to prepare high-strength SiC components with complex structure by introducing quasi-spherical diamond powder as the high-density carbon source through vat photopolymerization 3D printing technology and reactive melt infiltration process. The final RB–SiC ceramics exhibited a specific flexural strength of 312.45 ± 18.75 MPa and elastic modulus of 359.16 ± 4.57 GPa, demonstrating one of the highest flexural strength and elastic modules among those reported for 3D-printed SiC composites. Owing to the high mechanical performance and simple fabrication process, this strategy has significant advantages in the manufacturing of structural SiC ceramics.     

UV-assisted direct ink writing of Si3N4/SiC preceramic polymer suspensions

Direct ink writing (DIW) offers a flexible and readily available processing route for achieving ceramic components with complex shapes and geometries. The successful printing of ceramic green bodies using DIW typically requires the formulation of particle-loaded inks having a narrow window of rheological properties that enable both flow through the nozzle and support the weight of additional layers. Herein, we present a method for DIW that employs UV-curing to enable printing of otherwise unprintable inks. The inks used in this study are suspensions consisting of a commercially available polycarbosilane precursor and silicon nitride, Si₃N₄, powders. A diacrylate cross-linker and photointiator were employed to enable UV-curing. The effect of cross-linker content on UV-rheology and cure depth as they pertain to printing, and slump in self-supported lattice structures, are discussed. UV-assisted DIW produced components of a high degree of complexity, capable of supporting over-hanging structures, low shrinkage, and relatively high degree of ceramic conversion     

Additive manufacturing of SiSiC by layerwise slurry deposition and binder jetting (LSD-print)

The current work presents for the first time results on the Additive Manufacturing of SiSiC complex parts based on the Layerwise Slurry Deposition (LSD) process. This technology allows to deposit highly packed powder layers by spreading a ceramic slurry and drying. The capillary forces acting during the process are responsible for the dense powder packing and the good joining between layers. The LSD process can be combined with binder jetting to print 2D cross-sections of an object in each successive layer, thus forming a 3D part. This process is named LSD-print.By LSD-print and silicon infiltration, SiSiC parts with complex geometries and features down to 1 mm and an aspect ratio up to 4:1 could be demonstrated.The density and morphology were investigated for a large number of samples. Furthermore, the density and the mechanical properties, measured by ball-on-three-balls method, were in all three building directions close to isostatic pressed references.     

3D printing Si3N4-bonded SiC refractories fabricated using colloidal films-containing slurries based on non-spherical SiC and Si powders

Stable slurries for Si₃N₄-bonded SiC refractories for direct ink writing (DIW) were successfully prepared from a mixture of non-spherical silicon carbide (SiC) and silicon (Si) powders with an average particle size of D₅₀ = 41.98 μm. The rheological properties and printability of slurries prepared using polyvinyl alcohol (PVA; 4–16 wt %) or hydroxypropyl methylcellulose (HPMC, 0.5–2 wt.%) were investigated with the effect of sintering temperature on the mechanical performance, phase, and microstructure of Si₃N₄-bonded SiC refractory products. The results indicated that slurries prepared with the HPMC solution showed better printability than those prepared with the PVA solution because colloidal films formed by HPMC in slurries play a role in encasing particles, preventing solid−liquid separation and contributing to plasticity and lubrication, which guarantees the smooth extrusion and homogeneity of slurries. The successful printing of SiC–Si slurries is not only related to proper viscosity, yield value, and shear thinning characteristics but it is also crucial for maintaining the homogeneity of slurries under extrusion pressure. Optimal SiC–Si slurries containing 52 vol % SiC–Si and 1.5 wt% HPMC exhibited proper viscosity, shear thinning, and homogeneity characteristics during printing. The obtained specimens achieved the best printing performance with height and section retention rates of 98.7% and 97.6%, respectively. When sintered at 1450 °C, Si₃N₄ fibres grow further and reach a diameter of 342.5 nm, the nitriding rate is 92.43%, the fibres tend to form a full network structure, and the mechanical properties of Si₃N₄-bonded SiC products are the best.     

Facilitation mechanisms of ceramic additive manufacturing: Acceleration and phase transition

Ceramic additive manufacturing has been drawn massive attention as a novel processing for directly fabricating complex ceramic architectures. However, the uncured monomer causes defects in producing green body, debinding and sintering process in case of stereolithography. Therefore, high conversion of cured layer is required for the reliability and stability. Here, we report facilitation mechanisms of ceramic particles with acceleration and phase transition occuring in on-propagating matrix in suspension; scattering, free volume and micro-gel.. Scattering, lengthening the path of UV light, demonstrates higher efficiency of initiation confirmed with 1.6 times increased initial slope of heat flow. The free volume, securing the volumetric reaction site even in solidifying resin, indicates 0.45 times faster rate and two times rapider acceleration, respectively. Finally, micro-gel, generated as a result of steric hindrance between ceramic particles and glassified matrix with a prolonged diffusion, exhibits increase up to 26% in two phases systems.