Stereolithographical fabrication of dense Si3N4 ceramics by slurry optimization and pressure sintering

Photocurable gray-colored Si₃N₄ ceramic slurry with high solid loading, suitable viscosity and high curing depth is critical to fabricate dense ceramic parts with complex shape and high surface precision by stereolithography technology. In the present study, Si₃N₄ ceramic slurry with suitable viscosity, high solid loading (45 vol %) and curing depth of 50 μm was prepared successfully when surface modifier KH560 (1 wt%) and dispersant Darvan (1 wt%) were used. The slurry exhibits the shear thinning behavior. Based on the Beer-Lambert formula, D_p (the attenuation length) and E_c (the critical energy dose) of Si₃N₄ ceramic slurry with solid loading of 45 vol % were derived as 0.032 mm and 0.177 mJ/mm², respectively. Si₃N₄ ceramic green parts with complex shape and high surface precision were successfully fabricated by stereolithography technology. After optimizing the debinding and sintering process for green parts, dense Si₃N₄ ceramics with 3.28 g/cm³ sintering density were fabricated. The microhardness and fracture toughness of as-sintered Si₃N₄ ceramics are ~14.63 GPa and ~5.82 MPa m^1/2, respectively, which are comparable to those of the samples by traditional dry-pressed and pressureless sintering technology. These results show that ceramic stereolithography technology could be promising to fabricate high performance ceramics, especially for gray-colored monolithic Si₃N₄ ceramics.     

Influence of the content of polymethyl methacrylate on the properties of porous Si3N4 ceramics fabricated by digital light processing

Porous Si₃N₄ ceramics are highly regarded as ideal materials for radomes due to their unique characteristics. However, the slurry used for the preparation of porous Si₃N₄ ceramics suffers from a low cure depth, making it challenging to fabricate ceramic components using DLP technology. In this study, porous Si₃N₄ ceramics were prepared by combining DLP technology with pore-forming agent method. The addition of polymethyl methacrylate (PMMA) powders with lower refractive index than that of Si₃N₄ powders can improve the penetration depth of ultraviolet light in the Si₃N₄ slurry. A systematic study was conducted to investigate the influence of the addition of PMMA powders on the properties of Si₃N₄ slurries and porous Si₃N₄ ceramics. When PMMA powders were added at 10 wt%, the slurry with a lowest viscosity of 0.13 Pa s (the shear rate is 30 s⁻¹) and cure depth of 40.0 μm (the exposure energy is 600 mJ/cm²) was obtained. With the increase of PMMA content, porous Si₃N₄ ceramics experienced a gradual decrease in both the flexural strength and bulk density, while the porosity increased from 14.41% to 27.62%. Specifically, when 20 wt% PMMA was added, the resulting porous Si₃N₄ ceramics had a lowest bulk density (2.41 g/cm³), a maximum porosity (27.62%), and a flexural strength (435.87 MPa). The study is of great significance in establishing an experimental foundation for fabricating porous Si₃N₄ ceramics by using DLP technology.     

Effect of polystyrene addition on properties of porous Si3N4 ceramics fabricated by digital light processing

Porous Si₃N₄ ceramics with high strength and high transmittance have been widely used in the field of defense and military. Additive manufacturing (AM) technology is one of the effective means to fabricate porous Si₃N₄ ceramics. Nevertheless, it is difficult to prepare porous Si₃N₄ ceramics by using digital light processing (DLP) because of the large refractive index difference between Si₃N₄ powders and photosensitive resin. In this study, the effects of the amount of polystyrene (PS) powders on the properties of Si₃N₄ ceramic slurries and sintered ceramics were systematically discussed. The addition of PS reduced the overall refractive index of powders and increased the average particle size of powders, thus improving the cure depth of Si₃N₄ ceramic slurries from 11.0 ± 2.0 μm to 55.7 ± 1.8 μm. With the increase of PS content, the shrinkage and porosity of Si₃N₄ ceramics gradually increased, and the bulk density and flexural strength showed the opposite trend. The slurry with low viscosity (2.38 Pa٠s at a shear rate of 30 s⁻¹) and high cure depth (51.2 ± 4.6 μm) was obtained when the content of PS was 15 wt%, which met the thickness requirements for printing. The total porosity of Si₃N₄ ceramics reached the maximum values at 28.21 ± 2.58%. The addition of PS solved the problem of low cure depth of slurries, and PS as a pore-forming agent could help Si₃N₄ ceramics form porous structure. This research provides valuable insights into the fabrication of non-oxide ceramics with high refractive index using DLP technology.     

Improving cure performance of Si3N4 suspension with a high refractive index resin for stereolithography-based additive manufacturing

Silicon nitride (Si₃N₄) slurries with high solid loading, low viscosity and good stability is difficulty prepared, due to low intrinsic surface charge and a large refractive index (RI) difference between Si₃N₄ powder and resin. In this paper, the curing behavior of Si₃N₄ slurry with different functional group and RI of resin monomer were systematically researched, and then the kind and optimum content of dispersant were investigated. Subsequently, a high solid loading Si₃N₄ slurry (44 vol%) with good curing behavior, low viscosity and favorable stability was successfully prepared. Lastly, the dense Si₃N₄ ceramic parts were fabricated by the suitable Si₃N₄ slurry (44 vol%) via stereolithography. After debinding and sintering process, the relative density and flexural strength of Si₃N₄ ceramic were 98.28% and 800 ± 27.28 Mpa, respectively.     

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.     

Mechanical and dielectric properties of Si3N4-SiO2 ceramics prepared by digital light processing based 3D printing and oxidation sintering

Si₃N₄-SiO₂ ceramics are considered as the preferred high-performance wave-transmitting material in the aerospace field. However, traditional fabrication methods for Si₃N₄-SiO₂ ceramics have the disadvantages of high cost and complicated fabrication process. In this paper, Si₃N₄-SiO₂ ceramics with excellent mechanical and dielectric properties were fabricated by digital light processing-based 3D printing combined with oxidation sintering. Firstly, the curing thickness and viscosity of slurries with different solid loadings for vat photopolymerization-based 3D printing were studied. Then, the effects of the sintering temperature on the linear shrinkage, phase composition, microstructure, flexural strength, and dielectric properties of Si₃N₄-SiO₂ ceramics, and the influences of solid loading on them were explored. The curing thickness and viscosity of the slurry with a solid loading of 55 vol% were 30 μm and ∼1.5 Pa‧s, respectively. The open porosity and the flexural strength of Si₃N₄-SiO₂ ceramic with a solid loading of 55 vol% were 4.3 ± 0.61% and 76 ± 5.6 MPa, respectively. In the electromagnetic wave band of 8–18 GHz, the dielectric constant of Si₃N₄-SiO₂ ceramics was within the range of less than 4, and the dielectric loss remained below 0.09. The method of digital light processing-based 3D printing combined with oxidation sintering can be further extended in the preparation of Si₃N₄-based structure-function integrated ceramics.     

Fabrication of Si3N4 ceramics substrates with high thermal conductivity by tape casting and gas pressure sintering

In this paper, high thermal conductivity Si₃N₄ ceramics were successfully fabricated through exploring and optimizing the tape casting process. The impact of various organic additives on the rheological characteristics of Si₃N₄ slurry was explored, and the pore size distribution and microstructure of the green tapes at different solid loadings were investigated, as well as the microstructure of Si₃N₄ ceramics. Green tapes with a narrow pore size distribution, a small average pore size, and a high density of 1.88 g cm⁻³ were prepared by the investigation and optimization of the Si₃N₄ slurry formulation. After gas pressure sintering, Si₃N₄ ceramics with a density of 3.23 g cm⁻³, dimensions of 78 mm × 78 mm, and a thickness of 0.55 mm were obtained. The microstructure of the Si₃N₄ ceramics showed a bimodal distribution and a low content of glassy phases. The thermal conductivity of the Si₃N₄ ceramics was 100.5 W m⁻¹ K⁻¹, the flexural strength was 735 ± 24 MPa, and the fracture toughness was 7.17 MPa m^1/2.     

In-situ reaction synthesis of porous Si2N2O-Si3N4 multiphase ceramics with low dielectric constant via silica poly-hollow microspheres

In the present work, a novel and facile process has been proposed to fabricate porous Si₂N₂O-Si₃N₄ multiphase ceramics with low dielectric constant (ε_r＜4.0). Since silica poly-hollow microspheres could serve as the source of SiO₂ and the pore-forming agent, they have been introduced into Si₃N₄ slurry through the gelcasting technique. This process is benefited from the liquid phase sintering reaction between SiO₂ and Si₃N₄ with the aid of sintering additives, leading to in-situ synthesis of Si₂N₂O phase and porous structure. The content of silica poly-hollow microspheres has great influence on the properties of the final products. It indicates that Si₂N₂O phase would become the major phase when the content of silica poly-hollow microspheres was above 25 wt%. Furthermore, the micromorphology results reveal that the content of pores with many smaller aggregate microspheres increases as microspheres amount rises. As a result, along with the addition of silica poly-hollow microspheres, the bulk density decreases to 1.32±0.01 g/cm³, and open porosity ranges from 28.4±0.4% to 52.0±0.5%. Porous Si₂N₂O-Si₃N₄ multiphase ceramics prepared with 25 wt% silica poly-hollow microspheres addition possess flexural strength of 42.3±3.8 MPa, low dielectric constant of 3.31 and loss tangent of 1.93×10⁻³. It turns out to be an effective method to fabricate porous Si₂N₂O-Si₃N₄ composites with excellent mechanical and dielectric properties, which could be applied to radome materials.     

Effects of surfactant and particle size on the microstructure and strength of Si3N4 foams with high porosity

The highly porous Si₃N₄ ceramic foams were prepared by direct foaming with mixed surfactants. The surface tension and viscosity of slurries were tailored by different carbon chain length of surfactants and different mean Si₃N₄ particle size to achieve the pore size controlling. The nearly linear relationship between the pore size and the ratio of surface tension to viscosity was observed, which indicates that the pore size could be precisely tailored by the slurry properties. Si₃N₄ ceramic foams with porosity of nearly 94%, mean pore size of 110–230 µm, and compressive strength of 1.24–3.51 MPa were obtained.     

High-purity stoichiometric Si3N4 ceramics through trimethylsilyl-substituted polysilazanes

Trimethylsilyl-substituted polysilazanes were designed and successfully synthesized. They were used to fabricate high-purity stoichiometric Si₃N₄ ceramics through pyrolysis process. Trimethylsilyl groups improved the stability of polysilazanes and easily escaped during pyrolysis, which effectively reduced oxygen and carbon content in the final polymer-derived Si₃N₄. The C content of Si₃N₄ ceramic was below 0.06 wt%, and the O content was below 1.2 wt%. The Si₃N₄ ceramics remained amorphous up to 1400°C, yet they were completely transformed into α-Si₃N₄ at 1500°C. Synergistic effect from low oxygen and carbon content contributed to highly stable amorphous state of Si₃N₄ till high temperatures. This amorphous Si₃N₄ ceramics could be used in cutting-edge technology where high purity is compulsory.     

Fabrication and properties of Si2N2O-Si3N4 ceramics via direct ink writing and low-temperature sintering

Direct ink writing (DIW) and low-temperature sintering methods were applied to prepare Si₂N₂O-Si₃N₄ ceramics for radome materials. Lattices of Si-SiO₂ green body were printed by DIW with 78 wt % solid portion of water-based Si-SiO₂ slurry, in which silicon particles and silica fume were used as the solid portion and Methylcellulose (HPMC) was used as the dispersant. Effects of HPMC addition on stability and silica fume content on rheological properties of the slurry were studied, respectively. The pseudoplastic mechanism of the slurry was analyzed. The Si-SiO₂ green bodies were sintered at 1250 °C–1400 °C in nitrogen. The effect of temperature on phase composition, microstructure, mechanical and dielectric properties of samples was investigated. With the HPMC addition of 0.12 wt% and the silica fume proportion of 30 wt% in solid portion, a stable and pseudoplastic slurry with the yield stress of 110.9 Pa was obtained, which is suitable for DIW. With the decrease of initial holding temperature, more N₂ enters the sample and reacts with silicon and silica fume, promoting the generation of Si₂N₂O and Si₃N₄. The optimal condition yields Si₂N₂O-Si₃N₄ ceramics with apparent porosity of 42.73%, compressive strength of 24.7 MPa, dielectric constant of 4.89 and loss tangent of 0.0054. It is found that columnar Si₃N₄ comes from a direct reaction between silicon and N₂, and fibrous Si₂N₂O is mainly generated by the reaction between silicon, SiO(g), and N₂ through the chemical vapor deposition mechanism. Good dielectric properties are achieved due to high porosity, high proportion of Si₂N₂O phase and no residual silicon.     

Fabrication strategy of complicated Al2O3-Si3N4 functionally graded materials by stereolithography 3D printing

For multi-ceramic materials based on the stereolithography (SL) principle, a 3D printing strategy was developed, and then an Al₂O₃-Si₃N₄ functionally graded material (FGM) ceramic part was fabricated using this strategy. Six groups of mixtures, with a Si₃N₄ content gradient of 20 vol% and a certain bimodal particle size distribution, were prepared using UV-curable pastes. A modified formula was proposed to evaluate the relationship between the actual minimum voidage of mixtures and the viscosities of their corresponding pastes. The viscosity of each paste was controlled using the prediction formula and optimization of dispersants. To design theprinting layer thickness, a mathematical relationship was established between Si₃N₄ content and curing depth of paste. The Al₂O₃-Si₃N₄ green body without deformation was printed using optimized parameters such as a layer thickness of 40 μm and a paste viscosity of ∼13,000 mPa·s. Finally, using debinding and sintering, denseparts having a complicated shape were obtained.     

Processing of hydroxyapatite and its composites using ceramic fused filament fabrication (CF3)

In this article, we report the fabrication of hydroxyapatite (HAp) and its composites with 7.75 vol% Si₃N₄ (HAp10SN) using ceramic fused filament fabrication (CF³). Homogeneous feedstock with 40 vol% ceramic powder was prepared and used to extrude filaments for further printing using a desktop printer. Our results showed that the addition of Si₃N₄ to HAp increases the feedstock viscosity. However, the filaments and CF³ parts made using HAp and HAp10SN feedstocks exhibited comparable densities without gross defects. We have obtained relatively smoother CF³ parts with HAp10SN than pure HAp, which is attributed to their high feedstock viscosity and formation of liquid phase during sintering. Sintering at 1250 °C for 4 h in air, after thermal debinding, resulted in a relative density of ~85% with HAp and tricalcium phosphate (TCP) as major constituents. Sintered HAp10SN samples also revealed almost 70% reduction in the grain size and 4-fold increase in the hardness compared to pure HAp. Our results indicate that the CF³ processed HAp10SN samples containing ~15% porosity, Si₃N₄ particles and Si-substituted HAp/TCP have strong potential as bone replacements.     

Robust super-hydrophobic inorganic nanoparticles modified layered structure Si2N2O membrane for membrane distillation

Robust super-hydrophobic ceramic membranes consisting of layered structure Si₂N₂O grains and organosilane-derived inorganic nanoparticles were successfully fabricated and employed for membrane distillation. First, phase inversion and sintering method were used to prepare porous Si₂N₂O membranes. The slurry composition and sintering temperature were optimized to obtain a pure phase Si₂N₂O membrane with high bending strength, tailored average pore size, and high permeability. Then, the Si₂N₂O membranes were modified with organosilane-derived inorganic nanoparticles through ammonolysis and pyrolysis reactions. Due to the micro and nano-hierarchical rough structures and the presence of -Si-CH₃ groups, the membranes showed super-hydrophobicity with a water contact angle of 152 ± 1°. Finally, the membranes were applied to desalinate seawater by sweeping gas membrane distillation. A stable water flux of 76 ± 0.9 L/(m² day) with a salt rejection of > 99% was recorded during 30 h distillation test at 75 °C, demonstrating the stability and durability of the membranes.     

Application of polypropylene carbonate for the tape casting of silicon nitride ceramics

QPAC40 (polypropylene carbonate), with a little decomposition residue, is commonly used as a binder in aluminum nitride (AlN) tape casting. In this paper, we tried to explore its application in silicon nitride (Si₃N₄) tape casting. By studying the influence of dispersant, binder, plasticizer/binder ratio, and solid loading on slurry and green tape properties, the optimum formulation of the tape casting of Si₃N₄ slurry was determined, and the green tape with a uniform structure and relative density up to 63.16% was prepared. Si₃N₄ ceramics were obtained by debinding at 600°C for 1 h in vacuum and gas-pressure sintering at 1830°C for 2 h in N₂. The thermal conductivity and flexural strength of Si₃N₄ ceramics were 56.28 ± 1.21 W/(m·K) and 1130.67 ± 23.58 MPa, respectively. These results indicated that QPAC40 can be used to prepare Si₃N₄ sheets through tape casting.     

Microstructure,high-temperature mechanical and dielectric properties of novel Si3N4 f/SiNO wave-transparent composites

Continuous Si₃N₄ fiber reinforced SiNO matrix composites (Si₃N_4 f/SiNO composites) were innovatively prepared for long-time high-temperature resistant wave-transparent materials of hypersonic aircraft. The microstructure, high-temperature mechanical and dielectric properties of Si₃N_4 f/SiNO composites were investigated in detail. The as-fabricated Si₃N_4 f/SiNO composites have homogeneous SiNO matrix distribution for the special winding process, which is beneficial for the mechanical strength and wave-transparent properties. The average tensile strength and flexural strength at room temperature is 87.8 MPa and 171.2 MPa respectively, which suggests Si₃N_4 f/SiNO composites have excellent mechanical strength. The tensile strength value decreases to 54.6 MPa after heat-treated at 1000 ℃ for the surface reactions between the SiNO matrix and Si₃N₄ fibers. After heat-treated at 1550 ℃, the composites have the tensile strength value of 24.2 MPa for the high strength retention rate of Si₃N₄ fibers at this temperature. Si₃N_4 f/SiNO composites have excellent room temperature dielectric properties and excellent dielectric stability in different frequency bands (7–18 GHz). The dielectric constant values vary from 3.69 to 3.75 while the dielectric loss attains the order of 10^?3. The dielectric constants and dielectric loss of Si₃N_4 f/SiNO composites are relatively stable from RT to 800 ℃. The as-fabricated Si₃N_4 f/SiNO composites that have excellent high temperature resistance and dielectric properties are the ideal high temperature wave-transparent composites.     

Effects of AlN inorganic binder on the properties of porous Si3N4 ceramics prepared by selective laser sintering

Porous Si₃N₄ ceramics are widely used in the aerospace field due to its lightweight, high-strength, and high wave transmission. Traditional manufacturing methods are difficult to fabricate complex structural and functional ceramic parts. In this paper, selective laser sintering (SLS) technology was applied to prepare porous Si₃N₄ ceramics using AlN as an inorganic binder. And the effects of AlN content on the properties of the obtained ceramic samples were explored. As the AlN content increased, nano-Al₂O₃ and nano-SiO₂ formed the eutectic liquid phase, enhancing the sintering densification and phase transformation of Si₃N₄ poly-hollow microspheres (PHMs). The island-like partial densification structures in Si₃N₄ green bodies increased. During the high-temperature sintering, the eutectic liquid phase partially transformed into the mullite phase or reacted with AlN and Si₃N₄ to form the Sialon phase. With the increase of AlN content, the fracture mode of Si₃N₄ ceramics changed from fracturing along PHMs to fracturing across PHMs. The bonding depth between PHMs increased and the connection between the grains was tighter, so the Si₃N₄ ceramics became denser. With the increase of AlN addition, the total porosity of the porous Si₃N₄ ceramics tended to decrease and the flexural strength gradually increased. When AlN content was 20 wt%, the total porosity and the flexural strength were 33.6% and 23.9 MPa, respectively. The addition of AlN inorganic binder was carried out to develop a novel way to prepare high-performance porous Si₃N₄ ceramics by SLS.     

3D printing of honeycomb Si3N4 ceramic

In this paper, a honeycomb Si₃N₄ ceramic was fabricated by 3D printing with a well-preserved structure. The effects of Si₃N₄ content on the rheological properties of Si₃N₄/sol–silica ink and the printing resolution of products were investigated. The microstructure, phase composition, liner shrinkage rate, and fracture behavior of printed samples before and after sintering were systematically characterized in detail. The results showed that the modified inks had the optimized rheological properties, and the stress–shear rate curves corresponding to each slurry could be well described by Bingham and Herschel–Bulkley fluid models. The corresponding slump rates of the printed samples with different Si₃N₄ to sol–silica mass ratios were all lower than 4%, and the linear shrinkage rate of all of the samples after sintering was below 20%. The fracture behavior under compressive loading of the honeycomb Si₃N₄ ceramics tended to be non-catastrophic fractures both before and after sintering. The compressive strengths of all of the printed samples decreased with the increase of the Si₃N₄ content, and the highest compressive strength of the honeycomb ceramics could reach 131.2 MPa after sintering at 1600°C, which was about 366.9% higher than that of the samples in green state prior to the sintering.     

Fabrication and characterization of Si3N4 whisker-reinforced SiO2 ceramic for radome materials

Fused silica ceramic has become one of the most widely used radome materials in the world since the 1970s. But its poor mechanical properties restricted its application to some extent. To improve the mechanical properties of the fused silica ceramic and keep its characteristic for radome materials, silicon nitride (Si₃N₄) whisker-reinforced fused silica ceramics were prepared by a slip-casting method in the work. The influence of Si₃N₄ whisker contents on the properties of the slurry was studied, indicating that the preferable pH values of the slurry were 4–6 and whisker contents were 10 wt.%. The flexural strength of as-prepared Si₃N_4w/SiO₂ ceramic was about 74.35 MPa, exhibiting an increase of 7.75% over that of the pure silica sample. Its dielectric constant in the range from 8 to 12 GHz and tanδ under 10 GHz were, respectively, 3.37 and .0011. It is of great interest to find that Si₃N_4w/SiO₂ has excellent oxidization resistance and its mass maintains even at 1270°C.     

Effect of Si addition on the mechanical and thermal properties of sintered reaction bonded silicon nitride

Advanced silicon nitride (Si₃N₄) ceramics were fabricated using a mixture of Si₃N₄ and silicon (Si) powders via conventional processing and sintering method. These Si₃N₄ ceramics with sintering additives of ZrO₂ + Gd₂O₃ + MgO were sintered at 1800 °C and 0.1 MPa in N₂ atmosphere for 2 h. The effects of added Si content on density, phases, microstructure, flexural strength, and thermal conductivity of the sintered Si₃N₄ samples were investigated in this study. The results showed that with the increase of Si content added, the density of the samples decreased from 3.39 g/cm³ to 2.92 g/cm³ except for the sample without initial Si₃N₄ powder addition, while the thermal diffusivity of the samples decreased slightly. This study suggested that addition of Si powder, which varied from 0 to 100%, in the starting materials might provide a promising route to fabricate cost-effective Si₃N₄ ceramics with a good combination of mechanical and thermal properties.