The role of plasticizer in optimizing the rheological behavior of ceramic pastes intended for stereolithography-based additive manufacturing

Adding plasticizer is an efficient way to regulate the rheological behavior of ceramic paste and quality of green body in stereolithography-based additive manufacturing. The type and content of plasticizers (polyethylene glycol (PEG) and dibutyl phthalate (DBP)) had substantial effects on the rheological behavior and solid loading of ceramic paste, leading to varied macro / micro structure and strength of the green and sintered parts. DBP significantly reduced the viscosity and increased solid loading, and could adjust the flexibility of the green body by reducing the crosslinking density of UV curing system. PEG could inhibit crack initiation to some extent, but it was less effective for preventing cracking than DBP on ceramic parts with large-sized cross sections. It was concluded that DBP was more suitable as a plasticizer in alumina paste for SL additive manufacturing to form dense parts without defects.     

Digital light processing of ceramic components from polysiloxanes

Additive manufacturing using photocurable polymers is one method to answer the increased demand of ceramic structures with complicated morphology by fabricating ceramic parts with high resolution and good surface quality. We introduce here a new method to fabricate SiOC ceramic structures by utilizing a simple physical blend between two different preceramic polysiloxanes, one providing photosensitive acrylate groups while the other one a high ceramic yield. Different blend ratios have been realized and respectively optimized concerning the printing additives and setting times to fabricate exact replications of highly complex polysiloxane structures by Digital Light Processing. After pyrolysis, a uniform, homogenous shrinkage was observed yielding dense, pore- as well as crack-free SiOC ceramics. By adjusting the ratio between the different polysiloxanes, parameters such as the ceramic yield, shrinkage, chemical composition and resolution after pyrolysis could be tailored in a wide range of values.     

Controlling properties of ceramic formulations for porcelain robocasting

Porcelain pastes (PlotPastes) were formulated to be used on an additive manufacturing (AM) process (material extrusion) process, primarily robocasting (R3D) technique. The material morphological and thermal characteristics were evaluated by scanning electron microscopy (SEM), differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The rheology and the electrical potential of the ceramic particles were also studied to select and adequate the porcelain paste properties to the R3D AM technique. It was found that shifting the pH values to acidic, the surface charge of the particles changes and increases the pastes viscosity due to agglomeration effects. This behaviour was exploited to optimize the paste rheological behaviour which resulted in the optimum pH at 1.94 (PlotPaste 5). This paste was used in the study of R3D operating parameters. It was found that small variations in pressure and speed affects the dimensional accuracy of the printed models. The results showed the disruptive potential of porcelain R3D in the production of customized ceramic products.     

Influence of irradiation parameters on the polymerization of ceramic reactive suspensions for stereolithography

Stereolithography is an additive manufacturing process which makes it possible to fabricate useful complex 3D ceramic parts, with a high dimensional resolution and a good surface finish. Stereolithography is based on the selective UV polymerization of a reactive system consisting in a dispersion of ceramic particles in a curable monomer/oligomer resin. In order to reach a homogeneous polymerization in the green part, and to limit the risk of cracking and/or deformation during subsequent stages of debinding and sintering due to internal stresses, the influence of various fabrication parameters (laser power, scanning speed, number of irradiations) on the degree of polymerization was investigated. In addition, the impact of the irradiation of the subsequent upper layers onto the previously deposited and irradiated layers was evaluated. The degree of conversion was determined by Fourier Transform Infrared Spectroscopy (FTIR). Raman spectroscopy was also used and a brief comparison between these two methods is given.     

DLP 3D printing of scandia-stabilized zirconia ceramics

The present article aims to explore the printability of scandia-stabilized zirconia ceramic parts using desktop and low-cost DLP 3D printer. The acrylate-based homogeneous slurries with zirconia powder stabilized by 6 mol.% of Sc₂O₃ (6ScSZ) and 10 mol.% of Sc₂O₃ and 1 mol.% of Y₂O₃ (10Sc1YSZ) were prepared with appropriate rheological and UV-curing properties. In comparison with yttria-stabilized zirconia, slurries filled with 6ScSZ and 10Sc1YSZ powders reviled lower viscosity at the same solid content. The cure depth of the suspensions was suitable to print the objects with 50 μm of layer thickness, good interlayers connection, and surface finishing. No critical defects in ceramics such as cracks or delamination were observed. Both ceramics have the Vickers microhardness value of 11 GPa and the high ionic conductivity up to 0.2 S/сm at 900 °C demonstrating that the DLP is a promising method of fabricating scandia-stabilized zirconia parts as electrolyte material for SOFC application.     

陶瓷增材制造

陶瓷的脆性和高硬度使得传统陶瓷成型工艺不易制备具有复杂形状和结构的陶瓷制件。本文总结了目前发展较快的激光选区熔融、激光选区烧结、三维打印、立体光固化、自由挤出成型等增材制造工艺在陶瓷领域的研究进展。面向复杂结构和高性能陶瓷制品的定制化快速制造需求,陶瓷增材制造技术展现出极大优势,在传统陶瓷行业、生物医疗等领域得到了应用。但是,陶瓷增材制造仍面临着打印材料及大尺寸、高致密度复杂结构陶瓷零件制造等难题,这些也将是增材制造技术未来发展的重要研究方向。     

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.     

Additive manufacturing of electrofused mullite slurry by digital light processing

Mullite, one of the main refractory materials, has several applications that may demand tiny structures with complex geometries, and digital light processing (DLP) can produce such parts with outstanding dimensional precision and surface quality. In this work, electrofused mullite powder was used as a raw material for additive manufacturing by DLP. Photosensitive mullite suspensions were developed and their rheological behavior, stability, and thermal decomposition were investigated. Mullite parts were printed from suspensions with different ceramic loadings, debound, and sintered at different temperatures (from 1500 to 1650 °C). Density and strength increased with an increase in both solid loading and sintering temperature. Printed parts from slurry with 50 vol% of solid loading sintered at 1650 °C reached a relative density of 97.7 ± 0.3 % and flexural strength of 95.2 ± 5.0 MPa.     

Compressive strength of β-TCP scaffolds fabricated via lithography-based manufacturing for bone tissue engineering

Bone is a vital organ that is responsible for the support and movement of body as well as the storage and transportation of cells and nutrients. Disease, along with traumatic events, can leave regions of bone with large voids and/or defects. Related surgical procedures, such as allografts, autografts, and arthroplasty, are reported to amount to roughly €9.6bn annually, emphasising the need for bone repair/replacement globally. Tricalcium phosphate (TCP) is a bioactive ceramic that has been identified as a suitable material for bone tissue engineering applications due to its excellent bioresorbability and overall biocompatibility. Through lithography-based ceramic manufacturing (LCM), β -TCP scaffolds were fabricated across nine different designs in this work. Pore size, unit cell size, and unit cell geometry were altered to vary the porosity of these scaffolds. Following fabrication, the material composition, topography, macrostructure, and microstructure of the β-TCP scaffolds were characterised. The effects of porosity and unit cell geometry on the compressive strengths of β -TCP scaffolds were analysed in detail. Compressive strengths of the scaffolds were measured between 1.4 ± 0.5 MPa and 67.6 ± 13.3 MPa across a porosity range of 5.58 ± 0.09% to 59.36 ± 0.18%. The strength of these scaffolds was considerably lower than that of the compressive strength of cortical bone (100–200 MPa), but mimic the compressive strength of cancellous bone well (0.1–16 MPa). While scaffolds of β-TCP alone may not be suitable for load-bearing applications, they demonstrate enough mechanical stability for bone regeneration/tissue engineering applications. They hold more potential in the regeneration of small bone defects/voids or in composite materials.     

Digital light processing of wollastonite-diopside glass-ceramic complex structures

In this work, the possibility of shaping a glass-filled photosensitive polymer resin with Digital Light Processing (DLP) into a complex 3D structure and transforming it subsequently into a bioactive glass-ceramic scaffold was investigated. The influence of the printing conditions and the heat-treatment was studied using a 41?vol% glass-filled acrylated polymer resin. Scaffolds with designed architecture were turned into a wollastonite-diopside glass-ceramic at 1100?°C. They completely maintained their shape, exhibited no viscous flow and showed a homogenous linear shrinkage of around 25%. At 83?vol% porosity structures with Kelvin cell design exhibited a compressive strength exceeding 3?MPa, demonstrating that the material is suitable for the fabrication of bioceramic scaffolds for bone tissue engineering applications.     

Complex mullite structures fabricated via digital light processing of a preceramic polysiloxane with active alumina fillers

By taking advantage of the multi-functional properties of preceramic polymers, their transformation into ceramic material at low sintering temperatures and the processing capabilities of polymer manufacturing processes, mullite components were fabricated by additive manufacturing. A photocurable silicone preceramic polymer resin containing alumina particles was shaped into complex structures via Digital Light Processing. Dense and crack-free, highly complex porous mullite ceramics were produced by firing a mixture of a commercially available photosensitive polysiloxane as the silica source, containing alumina powder as active filler, in air at a low sintering temperature (1300 °C). In particular, the developed formulations, coupled with the additive manufacturing approach, allow for precise control of the architecture of the porous ceramic components, providing better properties compared to parts with stochastic porosity.     

Rheology of organics-free aqueous ceramic suspensions for additive manufacturing of dense silicon nitride ceramics

A dense structure of silicon nitride ceramic was fabricated by direct ink writing using aqueous suspensions. The rheology of the suspensions was carefully tailored by the particle chemical state and the ion concentrations, without the use of any organics. The surface chemical states of the Si₃N₄ powder were modified by calcination at 600 °C at various times. The minimum absolute value of zeta potential, calculated by the DLVO theory, was 19 mV at which the interaction was attractive interaction. Suspensions with solid volume fraction of 25–40 vol% exhibited pseudoplastic behavior with yield stresses ≥55 Pa and equilibrium storage moduli ≥ 10⁴ Pa. These enabled suspensions to flow through the nozzle and retain the shape of the printed parts. The flexural strength of Si₃N₄ ceramics produced using a 40 vol% suspension was 348 MPa. This strategy provides a simple process for fabricating high-performance ceramics based on the DIW.     

Digital light processing stereolithography of zirconia ceramics: Slurry elaboration and orientation-reliant mechanical properties

Digital Light Processing (DLP) is a promising technique for the preparation of ceramic parts with complex shapes and high accuracy. In this study, 3 mol% yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) UV-curable slurries were prepared and printed via DLP. Two different solid loadings (40.5 and 43.6 vol%, respectively) and printing directions were investigated to assess the influence of these parameters on physical and mechanical properties of the sintered parts. Zirconia samples were sintered at 1550 °C for 1 h, achieving a very high relative density (99.2%TD), regardless of solid loading and printing direction. FE-SEM micrographs shown a homogeneous and defect-free cross section with an average grains size of 0.56 ± 0.19 µm. Finally, mechanical properties were influenced by printing direction and zirconia vol%. Indeed, the composition with the higher solid loading (i.e. 43.6 vol%) had the highest three-point flexural strength (751 ± 83 MPa) when tested perpendicular to the printing plane.     

The preparation of SiC ceramic photosensitive slurry for rapid stereolithography

Stereolithography is one of the most widely used additive manufacturing techniques for preparing high precision and complex ceramic components. Due to the high optical absorbance and refractive index of SiC powder, the rapid stereolithography of SiC ceramics components has become a key challenge. Here, we innovatively use graded silica to improve the curing thickness, rheological and settling performance of the slurry. And we presented a preparation method of SiC ceramic slurry for stereolithography with high solid content, low viscosity, low sedimentation rate and high curing thickness. The printable precision of the slurry is more than 75 μm, the dynamic viscosity is less than 2 Pa·s, and the 24 h sedimentation height is less than 5%. This strategy demonstrates a tantalizing possibility and promising prospect to rapid stereolithography of large size SiC ceramic green body.     

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.     

Additive manufacturing of ceramics: Advances,challenges, and outlook

Additive manufacturing (AM) of ceramics is relatively more challenging with respect to polymers and metals, owing to their high melting temperatures and inherent brittleness. Thus, this review aims to provide a comprehensive survey of recent AM technologies successfully employed to produce net shape ceramic components. In recent years, several techniques have been developed and the latest progress in this field are highlighted, as well as the current challenges in the complex shaped ceramic parts production via AM technologies. The state of the art concerning the various 3D printing processes applied to the fabrication of ceramic components is discussed with, for each method, the presentation of its advantages, disadvantages, and possible applications. The potential of AM for producing complex shape ceramic components and the challenges to overcome are discussed as well.     

Fused deposition modeling of Si3N4 ceramics: A cost-effective 3D-printing route for dense and high performance non-oxide ceramic materials

Dense Si₃N₄ ceramics were prepared by fused deposition molding method accompanied by gas pressure sintering. In this study, the surface steps, inter layer bonding and microstructure evolution were characterized and dense Si₃N₄ ceramics without obvious defects were obtained. It was verified that layer thickness and nozzle diameter have little impact on the density and flexural strength of both green and sintered parts. As to the filling strategy, contour offset path was more effective to obtain sintered part with higher flexural strength than parallel lines and grid path, which was due to the possible voids appeared at the intersection of print paths with different directions. The highest flexure strength 824.74 ± 85 MPa was obtained with layer thickness 0.15 mm, nozzle size 0.6 mm and contour offset path. The reliability of the obtained Si₃N₄ ceramics was also investigated and complex shaped Si₃N₄ ceramic parts with good shape keeping was prepared successfully.     

Dispersion and stability of SiC ceramic slurry for stereolithography

Stereolithography based additive manufacturing provides an effective method to fabricate complex-shaped SiC ceramic components. The dispersion and stability of the ceramic slurry are very important for stereolithography. In this study, the dispersion and stability of SiC ceramic slurries were investigated systematically. The effects of resin monomers, dispersants, particle size, solid loading and ball milling time on the dispersion, rheological behavior and stability of SiC ceramic slurries were studied in detail. Finally, an optimal SiC ceramic slurry for stereolithography based additive manufacturing was obtained, and complex-shaped SiC ceramic architectures were fabricated.     

Preparation and characterization of Ce-ZrO2/Al2O3 composites by DLP-based stereolithography

This work investigates the printability of Ce-ZrO₂/Al₂O₃ composites through a Digital Light Processing (DLP) technology. Commercially available 10 mol% CeO₂ and 12 mol% CeO₂-stabilized zirconia were mixed with alumina powders, to provide 11 mol% CeO₂-stabilized ZrO₂/16 vol% Al₂O₃ (Ce-ZA₁₆) composite materials. The powders were dispersed under wet conditions, and the homogeneous nanometric dispersion was maintained once added into the liquid monomer. Slurries at several solid loadings were explored, with and without dispersant addition. First, the key role of the dispersant to significantly enhance the solid loading and thus the sintered density was demonstrated. Second, among different dispersant-added slurries at various solid loadings, ranging from 65 to 80 wt%, the best compromise between rheological behavior and curing depth was established. The best formulations, comprised between 70 and 80 wt%, successfully provided fully dense and completely homogeneous composites.