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.     

Properties regulation of SiC ceramics prepared via stereolithography combined with reactive melt infiltration techniques

Stereolithography(SLA) combined with reactive melt infiltration (RMI) is an effective way to fabricate silicon carbide(SiC) ceramic components with complex shapes and high precision. The purpose of this paper is to increase the content of SiC in the sintered body and improve the properties of SiC ceramics prepared by SLA/RMI technologies by the impregnation of the precursor of carbon source after debinding. The effects of the concentration of phenolic resin solution on the strength of sintered body were studied. The results show that this method can reduce the coefficient of thermal expansion and improve the thermal conductivity of the final body. At the same time, when the concentration of phenolic resin solution is 40 wt%, the final body obtained the best comprehensive properties. The value of bulk density, flexural strength and elastic modulus were 2.89 g/cm³, 244.17 ± 5.13 MPa and 402.39 GPa, respectively. This strategy provides a promising prospect for the preparation of space optical mirrors with complex shapes and high strength by the SLA/RMI method.     

Stereolithography 3D printing of SiC ceramic with potential for lightweight optical mirror

Silicon carbide (SiC) ceramic is the most prospective candidate material for space-based lightweight optical mirror. Stereolithography 3D printing has been reported to fabricate many kinds of ceramics, showing great potential for fabricating lightweight SiC ceramic optical mirror. In this paper, SiC ceramic was fabricated using stereolithography 3D printing combined with polymer burn-out, pre-sintering, and precursor infiltration and pyrolysis (PIP). The relative density, flexural strength, and microstructure during each step were investigated. The as-prepared lightweight SiC ceramic optical mirror exhibited high accuracy and high quality. Finally, it was proved that stereolithography 3D printing has a great potential for lightweight SiC ceramic optical mirror fabrication.     

Effects of CVI SiC amount and deposition rates on properties of SiCf/SiC composites fabricated by hybrid chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) routes

The SiC_f/SiC composites have been manufactured by a hybrid route combining chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) techniques. A relatively low deposition rate of CVI SiC matrix is favored ascribing to that its rapid deposition tends to cause a ‘surface sealing’ effect, which generates plenty of closed pores and severely damages the microstructural homogeneity of final composites. For a given fiber preform, there exists an optimized value of CVI SiC matrix to be introduced, at which the flexural strength of resultant composites reaches a peak value, which is almost twice of that for composites manufactured from the single PIP or CVI route. Further, this optimized CVI SiC amount is unveiled to be determined by a critical thickness t₀, which relates to the average fiber distance in fiber preforms. While the deposited SiC thickness on fibers exceeds t₀, closed pores will be generated, hence damaging the microstructural homogeneity of final composites. By applying an optimized CVI SiC deposition rate and amount, the prepared SiC_f/SiC composites exhibit increased densities, reduced porosity, superior mechanical properties, increased microstructural homogeneity and thus reduced mechanical property deviations, suggesting a hybrid CVI and PIP route is a promising technique to manufacture SiC_f/SiC composites for industrial applications.     

Comparative ablation behaviors of C/SiC-HfC composites prepared by reactive melt infiltration and precursor infiltration and pyrolysis routes

Carbon fiber reinforced silicon carbide-hafnium carbide (C/SiC-HfC) composites were prepared by reactive melt infiltration (RMI) and precursor infiltration and pyrolysis (PIP) routes. The ablation behaviors of the two composites were investigated and compared under an oxyacetylene torch flame. The C/SiC-HfC composites prepared by PIP showed a better ablation resistance than those synthetized by RMI. Microstructural observations revealed an island distribution of HfC for the sample prepared by RMI, which resulted in SiC being directly oxidized during the ablation process. In contrast, the PIP-prepared sample showed a uniform distribution of HfC, which resulted in SiC being oxidized via the Knudsen diffusion mechanism under ablation. The Knudsen diffusion of oxidants retarded the oxidation process, thereby increasing the ablation resistance of the C/SiC-HfC composites prepared by PIP.     

SiC and SiOC ceramic articles produced by stereolithography of acrylate modified polycarbosilane systems

3D printed ceramic articles are receiving increased interest recently. Stereolithography (STL) is the method of choice where surface quality, high resolution and high aspect ratio architectures are concerned. Recently, we have developed a UV curable system consisting of allylhydridopolycarbosilane (AHPCS) and multifunctional acrylates. In our present work we investigate the photo-crosslinking mechanism and use selected formulations for the 3D printing of SiC rich ceramic articles using a desktop STL device. High resolution and complex shape articles are demonstrated. The versatile curing method can be used for the STL of practically most other vinyl/allyl modified preceramic polymers. The nano-porosity as well as SiOxCy composition can be tailored in a wide range for specific applications by the ratio of acrylate to AHPCS and by the type of acrylate and AHPCS used.     

Fabrication of dense polymer‐derived silicon carbonitride ceramic bulks by precursor infiltration and pyrolysis processes without losing piezoresistivity

Dense polymer‐derived silicon carbonitride (SiCN) ceramic bulks were fabricated by powder consolidation following precursor infiltration and pyrolysis (PIP) densification. The density and open porosity of the ceramics varied from 1.42 g/cm³ and 32.75% before the PIP to 2.29 g/cm³ and 3.64% after the PIP, respectively. The electrical conductivity of the ceramics sharply increased from 6.26 × 10^?10 S/cm before the PIP process to 3.20 × 10^?7 S/cm after the 1st cycle of PIP and then gradually increased to 6.89 × 10^?6 S/cm after four cycles of PIP. However, the piezoresistive coefficient did not change with the PIP. The Raman and electron paramagnetic resonance results show that the graphitization level of free carbon in ceramics derived from PIP was higher than the ceramics derived from powder consolidation. The high graphitization level of free carbon leads to a high conductivity, and thus the conductivity of ceramics increased significantly after the PIP process. The carbon cluster size, which is related to the gauge factor of piezoresistivity, did not change significantly after the PIP process; thus, the gauge factor did not change significantly. Dense, large‐scale polymer‐derived ceramics were fabricated by combined conventional powder consolidation and PIP without the loss of piezoresistivity. These ceramics have potential application as both structural and functional components that can bear loads as well as monitor variations in external stress.     

Effects of fine grains and sintering additives on stereolithography additive manufactured Al2O3 ceramic

Al₂O₃ ceramics are fabricated by stereolithography based additive manufacturing in present reports. To improve the densification and performance of Al₂O₃ ceramic, the introduction of fine grains or sintering additives has been studied by traditional fabrication techniques. However, no research has focused on the effects of adding fine grains and sintering additives on the stereolithography additive manufactured Al₂O₃ ceramic. In this study, both fine grains and sintering additives were added firstly, and then the effects of fine grains and sintering additives on the relative density, microstructure, mechanical properties, and physical properties of the stereolithography additive manufactured Al₂O₃ ceramics were investigated. Finally, defect-free Al₂O₃ ceramic lattice structures with high precise and high compressive strength were manufactured.     

High-temperature properties and interface evolution of C/SiBCN composites prepared by precursor infiltration and pyrolysis

C/SiBCN composites with a density of 1.64 g/cm³ were prepared via precursor infiltration and pyrolysis and the bending strength and modulus at room temperature was 305 MPa and 53.5 GPa. The precursor derived SiBCN ceramics showed good thermal stability at 1600 °C and the SiC and Si₃N₄ crystals appeared above 1700 °C. The bending strength of the composites was 180 MPa after heat treatment at 1500 °C, and maintained at 40 MPa-50 MPa after heat treatment for 2 h at 1600 °C–1900 °C. In C/SiBCN composites, SiBCN matrix could retain amorphous up to 1500 °C and SiC grains appeared at 1600 °C but without Si₃N₄. The reason for no detection of Si₃N₄ was that the carbon fiber reacted with Si₃N₄ to form an interface layer (composed of SiC and unreacted C) and a polycrystalline transition layer (composed of B and C elements), leading to the degradation of the mechanical properties.     

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.     

Development of a numerical simulation model for predicting the curing of ceramic systems in the stereolithography process

The control of ceramic green parts dimensions produced by stereolithography is a central concern of the ceramic additive manufacturing industry. The presence of ceramic particles within the photopolymerizable system induces UV-laser beam scattering phenomenon, disrupting the polymerization process. This study focuses on the development of a numerical simulation model of the curing process, considering the scattering phenomenon. This paper presents each stages of the development of the numerical simulation model, supported and finally validated by experimentation on a commercial photopolymerizable alumina paste. Firstly, the numerical simulation model is presented. Then, a Greco-Latin square design of experiments is conducted to reduce the number of experiments. Subsequently, material-dependent parameters are identified through simulations and experimental measurements, and a scattering law is proposed. Finally, the simulation model enables to simulate easily and with accuracy the cure widths and the cure depth. It also provides visualization of the exposure distribution and the scattering phenomenon.     

Development of a silicon carbide ceramic based counter-flow heat exchanger by binder jetting and liquid silicon infiltration for concentrating solar power

A silicon carbide ceramic counter-flow heat exchanger with integrated headers was printed by binder jetting additive manufacturing process. Multiple phenolic binder infiltration cycles (3 or 5) followed by pyrolysis were conducted to increase the net carbon content of the printed SiC specimens. Subsequently, to attain full densification, silicon melt infiltration was used. The microstructure and mechanical properties were comprehensively characterized on the densified material. The chemical compositions and visual distribution of the various regions in the specimens were determined via scanning electron microscopy, while X-ray diffraction and synchrotron μ-computed tomography were used to provide a quantitative assessment of the volume fractions of the identified phase regions. Microhardness measurements showed dependence on the local microstructure. The fracture strength of the material was correlated with the specimen density and agreed with the reported values in the literature. High-temperature exposure at 750 °C for up to 200 h did not degrade the strength for the specimens with three phenolic-binder infiltrations; however, the strengths degraded for ones with five phenolic-binder infiltrations. The associated fracture toughnesses of the specimens were ～3.4 MPam^1/2 at room temperature and 750 °C, and the thermal conductivities varied from >150 W/mK at room temperature to ～45 W/mK at 750 °C. Hence, this study validated the use of the binder-jetting printed SiC ceramic materials for high-temperature heat exchanges. Finally, we also present in this work the first successful fabrication of a binder-jetting printed one-piece dense SiC ceramic heat exchanger body with unblocked channels that can be used for the flow of heat transfer fluids.     

Additive manufacturing of silicon carbide by selective laser sintering of PA12 powders and polymer infiltration and pyrolysis

In this work, we propose a novel hybrid additive manufacturing technique, which combines selective laser sintering (SLS) of polyamide powders and subsequent preceramic polymer infiltration and pyrolysis to manufacture Silicon Carbide components for complex architectures. By controlling the porosity of the sintered polymeric preform we are able to control the shrinkage upon the first infiltration and pyrolysis. This enabled the manufacturing of smaller features than those achievable with other manufacturing techniques. The mechanical strength of the resulting ceramic increased with the number of reinfiltration cycles up to 24 MPa, inversely the residual porosity decreased to 10 vol%. The microstructure showed two distinct phases of SiOC and SiC. The first was attributed to the interaction between the porous polyamide and the ceramic precursor during the first infiltration. SiC derived from the pyrolysis of the preceramic precursor alone.     

Microstructure and ablation properties of La2O3 modified C/C-SiC composites prepared via precursor infiltration pyrolysis

Effects of La₂O₃ modification on the microstructure, mechanical and ablation properties of C/C-SiC composites were investigated. Experimental results show that a new La₁₀(SiO₄)₆O₃ phase was generated during heat treatment process. The presence of the La-compounds, namely La₂O₃ and La₁₀(SiO₄)₆O₃, had an important impact on the structure of reinforced skeleton and the molten oxide film, and thus strongly affected the mechanical and ablation properties of the composites. Excessive La addition induced the structural damage of the reinforced skeleton, resulting in weakened mechanical and ablation properties. The C/C-SiC composites with 25.65 wt.% La₂O₃ addition displayed better mechanical properties and the best ablation resistance. The La₁₀(SiO₄)₆O₃ phase could react with molten silica to form a viscous glass during ablation. The transformation of La-compounds into La₂Si₂O₇ can reduce the ablation of SiO₂ and enhance the glass film, so as to protect the composites from further ablation.     

Preparation of Si3N4 ceramic based on digital light processing 3D printing and precursor infiltration and pyrolysis

The emergence of digital light processing (DLP) 3D printing technology creates favorable conditions for the preparation of complex structure silicon nitride (Si₃N₄) ceramics. However, the introduction of photosensitive resin also makes the Si₃N₄ ceramics prepared by 3D printing have low density and poor mechanical properties. In this study, high-density Si₃N₄ ceramics were prepared at low temperatures by combining DLP 3D printing with precursor infiltration and pyrolysis (PIP). The Si₃N₄ photocurable slurry with high solid content and high stability was prepared based on the optimal design of slurry components. Si₃N₄ green parts were successfully printed and formed by setting appropriate printing parameters. The debinding process of printed green parts was further studied, and the results showed that samples without defects and obvious deformation can be obtained by setting the heating rate at .1°C/min. The effect of the PIP cycle on the microstructure and mechanical properties of the Si₃N₄ ceramics was studied. The experimental results showed that the mass change and open porosity of the samples tended to be stable after eight PIP cycles, and the open porosity, density, and bending strength of the Si₃N₄ ceramics were 1.30% (reduced by 97%), 2.64 g/cm³ (increased by 43.5%), and 162.35 MPa.     

Investigation of oleic acid as a dispersant for hydroxyapatite powders for use in ceramic filled photo-curable resins for stereolithography

Stereolithography allows production of porous hydroxyapatite scaffolds for bone regeneration but is limited by the challenging rheology of ceramic filled resins. Oleic acid, a natural fatty acid, was applied in concentrations of 0.0–0.3 wt% to improve the rheological properties of HAp resins for the fabrication of solid cylinders and scaffolds by digital light processing (DLP) printing in a wiperless system. Bonding by chemisorption was confirmed by FTIR analysis. The powders were then incorporated into a photo-curable resin of 1–6 hexanediol diacrylate at 18–30 vol%. The shear viscosity and sedimentation rates of photocurable resins containing HAp powder decreased with increasing concentration of oleic acid. The curing depth and width of resins containing the HAp were unchanged as a result of the presence of oleic acid. Oleic acid improved the printing behaviour of the resins allowing the fabrication of scaffolds with continuous macro-porosity on a wiperless DLP system.     

Significance of modification of slurry infiltration process for the precursor impregnation and pyrolysis process of SiCf/SiC composites

Several intermediate steps were applied before the precursor infiltration and pyrolysis process to improve the infiltration of SiC slurry for promoting the infiltration of SiC slurry into fiber voids. These steps include sonication, popping, electrophoretic deposition, vacuum infiltration and cold isostatic pressing (CIP). The intermediate processes, especially popping and CIP, had a beneficial effect on green density enhancement and improving the homogeneous infiltration of the slurry into fiber fabrics. The density of the SiC_fiber/SiC_filler green body was 2.20 g/cm³, which corresponded to 68 % of relative density. The SiC_f/SiC composite has a high density of 2.65 g/cm³ after seven PIP cycles.     

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.     

Selective laser reaction synthesis of SiC,Si3N4 and HfC/SiC composites for additive manufacturing

Selective laser reaction sintering techniques (SLRS) techniques were investigated for the production of near net-shape non-oxide ceramics including SiC, Si₃N₄, and HfC/SiC composites that might be compatible with prevailing powder bed fusion additive manufacturing processes. Reaction bonded layers of covalent ceramics were produced using in-situ reactions that occur during selective laser processing and layer formation. During SLRS, precursor materials composed of metal and/or metal oxide powders were fashioned into powder beds for conversion to non-oxide ceramic layers. Laser-processing was used to initiate simultaneous chemical conversion and local interparticle bonding of precursor particles in 100 vol% CH₄ or NH₃ gases. Several factors related to the reaction synthesis process—precursor chemistry, gas-solid and gas-liquid synthesis mechanisms, precursor vapor pressures—were investigated in relation to resulting microstructures and non-oxide yields. Results indicated that the volumetric changes which occurred during in-situ conversion of single component precursors negatively impacted the surface layer microstructure. To circumvent the internal stresses and cracking that accompanied the conversion of Si or Hf (that expands upon conversion) or SiO_x (that contracts during conversion), optimized ratios of the precursor constituents were used to produce near isovolumetric conversion to the product phase. Phase characterization indicated that precipitation of SiC from the Si/SiO₂ melt formed continuous, crack-free, and dense layers of 93.7 wt% SiC that were approximately 35 µm thick_, while sintered HfC/SiC composites (84.2 wt% yield) were produced from the laser-processing of Hf/SiO₂ in CH₄. By contrast, the SLRS of Si/SiO_x precursor materials used to produce Si₃N₄ resulted in whisker formation and materials vaporization due to the high temperatures required for conversion. The results demonstrate that under appropriate processing conditions and precursor selection, the formation of near net-shape SiC and SiC composites might be achieved through single-step AM-compatible techniques.     

Thermal properties of Cf/HfC and Cf/HfC-SiC composites prepared by precursor infiltration and pyrolysis

Ultra-high temperature ceramic infiltrated carbon-fibre composites were prepared by precursor infiltration and pyrolysis (PIP) using a laboratory synthesized precursor. Microstructures and thermal properties including thermal expansion, thermal diffusivity, specific heat capacity and oxidative stability are correlated. XRD reveals the presence of C_f-HfC and C_f-HfC-SiC phases without formation of oxides. The CTE observed at 1200?°C is slightly higher for C_f-HfC (3.36?×?10^?6?K^?1) compared to C_f-HfC-SiC (2.95?×?10^?6?K^?1) composites. Lower thermal diffusivity of the C_f-HfC-SiC compared to C_f-HfC composites is attributed to a thermal barrier effect and cracks in the composites which formed due to the CTE mismatch between carbon fibre and the matrix as well as CO generated during graphitization. The thermal conductivity of C_f-HfC (4.18?±?0.14?Wm^?1?K^?1) is higher than that of C_f-HfC-SiC composite (3.33?±?0.42?Wm^?1?K^?1). Composites microstructures were coarse with some protruding particles (5?μm) with a homogeneous dense (～70%) matrix (HfC and HfC-SiC) for both composites.