Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.     

Characterization of ceramic components fabricated using binder jetting additive manufacturing technology

Binder jetting additive manufacturing is an emerging technology with capability of processing a wide range of commercial materials, including metals and ceramics (316 SS, 420 SS, Inconel 625, Iron, Silica). In this project, aluminum oxide (Al₂O₃) powder was used for part fabrication. Various build parameters (e.g. layer thickness, saturation, particle size) were modified and different sintering profiles were investigated to achieve nearly full-density parts (~96%). The material's microstructure and physical properties were characterized. Full XRD, compression testing, and dielectric testing were conducted on all parts. Sintered alumina parts were achieved with an average compressive strength of 131.86 MPa (16 h sintering profile) and a dielectric constant of 9.47–5.65 for a frequency range of 20 Hz to 1 MHz. The complexity offered by additive processing aluminum oxide can be extended to the manufacturing of high value energy and environmental components for environmental systems (e.g. filters and membranes) or biomedical implants with integrated reticulated structures for improved osseointegration.     

Additive manufacturing of lead-free KNN by binder jetting

Additive manufacturing of lead-free piezoceramics is of great interest, given the large request of application-oriented designs with optimal performances and reduced material consumption. Binder Jetting (BJ) is an additive manufacturing technique potentially suited to the production of ceramic components, however the number of feasibility studies on BJ of piezoceramics is extremely limited and totally lacking in the case of sodium-potassium niobate (KNN). In this work, as-synthesised powders are employed in the BJ 3D printing process. Microstructural properties, such as porosity, grain size distributions, and phase composition are studied by SEM, XRD and MIP (Mercury Intrusion Porosimetry) and compared to die-pressed pellets. Analyses reveal considerable residual porosity (~40%) regardless of the printing parameters, with a weak preferential orientation parallel to the printing plane. The piezoelectric characterization demonstrates an outstanding d₃₃ value of 80–90 pC N^?1. Finally, Figures of Merits for the employment as porous piezoceramics in the direct mode are presented.     

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.     

Concurrent reaction-bonded joining and densification of additively manufactured silicon carbide by liquid silicon infiltration

In this study, additive-manufactured silicon carbide preforms were joined and densified by reaction bonding via liquid silicon infiltration. The silicon carbide preforms were first printed by binder jetting additive manufacturing. To demonstrate concurrent joining and densification, two preforms with carbon or parchment papers at the interface were concurrently joined and infiltrated by liquid silicon. Results showed a robust interface with thicknesses ranging from 150 to 500 µm, depending on the paper type and the number of paper layers. High-energy synchrotron X-ray revealed that β-phase silicon carbide was formed inside the interface. Finally, two additively manufactured samples with complicated channel geometry were successfully joined. Energy dispersive spectroscopy of the interface of the channeled samples showed a consistent and robust joining. This concurrent approach of joining and densification enables efficiency improvement of fabricating silicon carbide parts with complicated geometries and widens geometry freedom for additive manufacturing of silicon carbide.     

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.     

Additive manufacturing of zirconia ceramics by material jetting

The possibility of additive manufacturing of ceramics has been reported widely in scientific literature. This study investigates the potential of direct inkjet printing or material jetting of 3Y-TZP ceramics by assessing the microstructure and mechanical properties of the sintered printed parts. The technique allows to print in layers of 10.5 μm, with an as-printed green density of 58 % and nearly fully sintered density of 6.03 ± 0.1 g/cm³ (99.7 % TD). The dimensions of the green and sintered parts were highly accurate but showed an anisotropic roughness in function of the building direction, mainly due to the support structures. The biaxial bending and 4-point bending strength of the sintered material was found to be substantially higher in the XY direction than in the building (Z) direction. SEM and X-Ray computed tomography revealed the presence of delamination cracks, agglomerates and spherical pores, which were identified as fracture origins on fractured surfaces.     

Binder jetting additive manufacturing of silicon carbide ceramics: Development of bimodal powder feedstocks by modeling and experimental methods

A limitation of binder jetting additive manufacturing is the low density of fabricated parts. Mixing powders with different sizes is a promising approach to increase powder bed packing density and, hence, printed part density. However, in previous studies mixed powder feedstock was prepared by trial and error method. In this research, both modeling and experimental methods were used to prepare the bimodal powder feedstocks. Analytical packing model was introduced for irregular powders. A bimodal powder was prepared by mixing two different-sized silicon carbide powders (i.e. coarse and fine) using ball mill, and their tap densities were measured. Silicon carbide plates were printed using the coarse and bimodal powders by a commercial binder jetting system. Results showed that the modeling method could predict the tap density of bimodal powders with high accuracy. The printed parts from bimodal powder achieved higher green densities than those from the unimodal powder.     

Post-infiltration to improve the density of binder jetting ceramic parts

Infiltration of printed bodies with a ceramic suspension is a relevant approach to enhance density and properties of the porous binder-jetted parts. In the present work, significant improvements of alumina parts processed through this combination printing-infiltration was reported. The density of non-infiltrated (but sintered) samples only reached 55.3 ± 1.1% of the theoretical density while it raised up to 87.9 ± 0.5% after infiltration of a pre-consolidated body followed by sintering. Influence of multi-infiltration operations, pre-consolidation temperature, solids loading of suspensions and duration of infiltration on the final part density were discussed. Infiltration mechanism and porosity distribution have been carefully investigated. It was demonstrated that the ceramic suspension infiltrated the pre-consolidated ceramic skeleton mostly under the effect of gravity which may result in density heterogeneities of the infiltrated parts. The reported processing route can be straightforwardly applied to other ceramic systems and is particularly inexpensive, and it is believed to have industrial relevance.     

Effect of binder system on the thermophysical properties of 3D-printed zirconia ceramics

Fabrication of 3D-printed ceramic parts with high complexity and high spatial resolution often demands low wall thickness as well as high stiffness at the green state, whereas printing simpler geometries may tolerate thicker, more compliant walls with the advantage of a rapid binder-burn-out and sintering process. In this work, the influence of the binder system on the thermophysical properties of 3D-printed stabilized zirconia ceramics was investigated. Samples were fabricated with the lithography-based ceramic manufacturing (LCM) technology using two different photosensitive ceramic suspensions (LithaCon 3Y230 and LithaCon 3Y210), with the same ZrO₂ powder. A significant difference in stiffness in the green state (~3 MPa vs. ~32 MPa for LithaCon 3Y230 and LithaCon 3Y210, respectively) was measured, associated with a rather loose or a linked network formed in the binder due to photopolymerization. Both materials reached high relative densities, that is, >99%, exhibiting a homogeneous fine-grained microstructure. No significant differences on the coefficient of thermal expansion (11.18 ppm/K vs. 11.17 ppm/K) or Young's modulus (207 GPa vs. 205 GPa) were measured, thus demonstrating the potential of tailoring binder systems to achieve the required accuracy in 3D-printed parts, without detrimental effects on material's microstructure and thermophysical properties at the sintered state.     

Synthesis and properties of macroporous SiC ceramics synthesized by 3D printing and chemical vapor infiltration/deposition

Open porosity cellular SiC-based ceramics have a great potential for energy conversion, e.g. as solar receivers. In spite of their tolerance to damage, structural applications at high temperature remain limited due to high production costs or inappropriate properties. The objective of this work was to investigate an original route for the manufacturing of porous SiC ceramics based on 3D printing and chemical vapor infiltration/deposition (CVI/CVD). After binder jetting 3D-printing, the green α-SiC porous structures were reinforced by CVI/CVD of SiC using CH₃SiCl₃/H₂. The multiscale structure of the SiC porous specimens was carefully examined as well as the elemental and phase content at the microscale. The oxidation and thermal shock resistance of the porous SiC structures and model specimens were also studied, as well as the thermal and mechanical properties. The pure and dense CVI/CVD-SiC coating considerably improves the mechanical strength, oxidation resistance and thermal diffusivity of the material.     

The effect of particle size distribution on the microstructure and properties of Al2O3 ceramics formed by stereolithography

Stereolithography (SL) shows advantages for preparing alumina-based ceramics with complex structures. The effects of the particle size distribution, which strongly influence the sintering properties in ceramic SL, have not been systematically explored until now. Herein, the influence of the particle size distribution on SL-manufactured alumina ceramics was investigated, including bending strength at room temperature, post-sintering shrinkage, porosity, and microstructural morphology. Seven particle size distributions of alumina ceramics were studied (in μm/μm: 30/5, 20/3, 10/2, 5/2, 5/0.8, 3/0.5, and 2/0.3); a coarse:fine particle ratio of 6:4 was maintained. At the same sintering temperature, the degree of sintering was greater for finer particle sizes. The particle size distribution had a larger influence on flexural strength, porosity and shrinkage than sintering temperature when the particle size distribution difference reached 10-fold but was weaker for 10 μm/2 μm, 5 μm/2 μm and 5 μm/0.8 μm. The sintering shrinkage characteristics of cuboid samples with different particle sizes were studied. The use of coarse particles influenced the accuracy of small-scale samples. When the particle size was comparable to the sample width, such as 30 μm/5 μm and 5 mm, the width shrinkage was consistent with the height shrinkage. When the particle size was much smaller than the sample width, such as 2 μm/0.3 μm and 5 mm, the width shrinkage was consistent with the length shrinkage. The results of this study provide meaningful guidance for future research on applications of SL and precise control of alumina ceramics through particle gradation.     

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.     

Binder jetting additive manufacturing of aluminum nitride components

In this work, we report on the novel fabrication of aluminum nitride (AlN) components using Binder Jetting (BJT) additive manufacturing (AM). The AlN constructs were subjected to post-fabrication thermal treatment by hot isostatic pressing (HIPing) for 8 hours at a pressure of 206 MPa and temperature of 1900 °C. This treatment resulted in a 60.1% relative density maximum densification for AlN. The BJT printed AlN specimens were analyzed using various characterization techniques. The purity, microstructure, and polycrystallinity of the AlN phase formed were confirmed by techniques that included x-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM). Second harmonic generation (SHG) microscopy showed polarization dependence and second harmonic signal at 470 nm, indicating the potential to produce thermal and optical-mechanical devices. Mechanical properties obtained by nanoindentation resulted in an elastic modulus of ~251 GPa when measured in fully dense, contiguous crystalline regions, corresponding to an apparent, porous bulk stiffness of ~90 GPa for the final, 60.1 % dense products. Finally, the laser flash method (LFM) was used to measure the thermal conductivity of the material as a function of temperature resulting in values from 4.82 W/mK to 3.17 W/mK for the temperature range from 23 °C to 500 °C, respectively.     

3D printing of porcelain by layerwise slurry deposition

The Layerwise Slurry Deposition is a technology for the deposition of highly packed powder layers. A powder bed is achieved by depositing and drying layers of a ceramic suspension by means of a doctor blade. This deposition technique was combined with the binder jetting technology to develop a novel Additive Manufacturing technology, named LSD-print. The LSD-print was applied to a porcelain ceramic. It is shown that it was possible to produce parts with high definition, good surface finish and at the same time having physical and mechanical properties close to those of traditionally processed porcelain, e.g. by slip casting.This technology shows high future potential for being integrated alongside traditional production of porcelain, as it is easily scalable to large areas while maintaining a good definition. Both the Layerwise Slurry Deposition method and the binder jetting technologies are readily scalable to areas as large as >1?m².     

Preparation of a hydrophobic cerium oxide nanoparticle coating with polymer binder via a facile solution route

In this work, cerium oxide (CeO₂) nanoparticles (NPs) were synthesized using a facile, low temperature solution process and coated using spin coating and spray coating approaches, for the fabrication of a hydrophobic surface coating. Silicon wafer (Si) substrates coated with CeO₂ NPs exhibited excellent hydrophobic behavior, but poor adhesion of the NPs to the substrate was observed - likely due to the low surface polarity of CeO₂ NPs. Polyacrylic acid (PAA) was introduced as an adhesion promoter to improve NP surface characteristics and obtain an adherent and cohesive coating. Slight polarity tuning and binder inclusion significantly enhanced the binding capability of the NPs as determined by peel-off measurements. The superior mechanical properties of NP coatings were attributed to the incorporation of PAA in the polymeric network. It improves inter-particle and particle-substrate secondary interactions, ultimately aiding NP cohesion and adhesion when deposited onto the Si substrate. The adhesive and hydrophobic properties of CeO₂ NP coatings were maintained upon exposure to high temperatures, and the coatings are transparent as well, making them suitable for various applications, such as cookware, glass coating and technology components.     

Effect of silica sol on performance and surface precision of alumina ceramic shell prepared by binder jetting

Using 3D printing technology to prepare ceramic shell used for precision investment casting can realize short process and efficient preparation of the ceramic shell, which has a great application potential in the casting field. However, the 3D printed ceramic shells often have the problems of low strength and accuracy. In this paper, a silica sol room temperature dip coating treatment combined with high temperature sintering method was proposed to improve the strength and surface precision of the ceramic shell prepared by the binder jetting. The effects of silica sol concentration and dip coating time on performance and surface precision of the alumina ceramic shell were studied. The mechanical properties and surface precision of the alumina ceramic shell prepared by the binder jetting were improved significantly with the increases of the sol concentration and dip coating time. With the dip coating time of 90 s and sol concentration of 30%, the maximum bending strength of the alumina ceramic reached 44.8 MPa, which was 18.9 times higher than that of the untreated alumina ceramic. The top surface roughness and side roughness of the alumina ceramic decreased from 6.87 μm to 5.70 μm and 7.55 μm–6.46 μm, respectively, compared to those of the untreated alumina ceramic.     

Additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites via paper laminating,direct slurry writing,and precursor infiltration and pyrolysis

In this study, continuous carbon reinforced C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C–SiC high entropy ceramic matrix composites were additively manufactured through paper laminating (PL), direct slurry writing (DSW), and precursor infiltration and pyrolysis (PIP). (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C high entropy ceramic (HEC) powders were synthesized by pressureless sintering and ball milling. A certain proportion of HEC powder, SiC powder, water, binder, and dispersant were mixed to prepare the HEC-SiC slurry. Meanwhile, BN coating was prepared on the 2D fiber cloth surface by the boric acid-urea method and then the cloth was cut into required shape. Additive manufacturing were conducted subsequently. Firstly, one piece of the as-treated carbon fiber cloth was auto-placed on the workbench by paper laminating (PL). Then, the HEC-SiC slurry was extruded onto the surface of the cloth by direct slurry writing (DSW). PL and DSW process were repeated, and a C_f/HEC-SiC preform was obtained after 3 cycles. At last, the preform was densified by precursor infiltration and pyrolysis (PIP) and the final C_f/HEC-SiC composite was prepared. The open porosity of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 7.7, 10.6, and 11.3%, respectively. And the density of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 2.9, 2.7 and 2.3 g/cm³, respectively. The mechanical properties of the C_f/HEC-SiC composites increased firstly and then decreased with the HEC content increase, reaching the maximum value when the HEC volume fraction was 30%. The mechanical properties of the C_f/HEC-SiC composites containing 45, 30 and 15% HEC were as follows: flexural strength (180.4 ± 14 MPa, 183.7 ± 4 MPa, and 173.9 ± 4 MPa), fracture toughness (11.9 ± 0.17 MPa m^1/2, 14.6 ± 2.89 MPa m^1/2, and 11.3 ± 1.88 MPa m^1/2), and tensile strength (71.5 ± 4.9 MPa, 98.4 ± 12.2 MPa, and 73.4 ± 8.5 MPa). From this study, the additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites was achieved, opening a new insight into the manufacturing of ceramic matrix composites.     

Additive manufacturing of zirconia parts by indirect selective laser sintering

Thermally induced phase separation (TIPS) was used to produce spherical polypropylene–zirconia composite powder for selective laser sintering (SLS). The influence of the composition of the composite starting powder and the SLS parameters on the density and strength of the composite SLS parts was investigated, allowing realizing SLS parts with a relative density of 36%. Pressure infiltration (PI) and warm isostatic pressing (WIPing) were applied to increase the green density of the ZrO₂–PP SLSed parts. Infiltrating the SLS parts with an aqueous 30 vol.% ZrO₂ suspension allowed to increase the sintered density from 32 to 54%. WIPing (135 °C and 64 MPa) of the SLS and SLS/infiltrated complex shape green polymer–ceramic composite parts prior to debinding and sintering allowed raising the sintered density of the 3 mol Y₂O₃ stabilized ZrO₂ parts to 92 and 85%, respectively.     

Enhanced electromagnetic microwave absorption properties of SiCN(Fe) ceramics produced by additive manufacturing via in-situ reaction of ferrocene

SiCN(Fe) ceramics with excellent electromagnetic wave (EMW) absorption performance were successfully prepared from a preceramic polymer doped with ferrocene. Additive manufacturing (Digital Light Processing), providing enhanced structural design ability, was employed to fabricate samples with complex architectures. During pyrolysis, ferrocene catalyzed the in-situ formation of a large amount of turbostratic carbon, graphite and SiC nanosized phases, which formed carrier channels in the electromagnetic field and increased the conductivity loss. Meanwhile, it also increased the dipole polarization, interface polarization and the dielectric properties of the material, which finally enhanced the EMW absorption capacity of SiCN(Fe) ceramics. When containing 0.5 wt% ferrocene, the material showed good performance with EAB 4.57 GHz at 1.30 mm, and RL_min −61.34 dB at 2.22 mm. The RL_min of 3D-SiCN-0.5 ceramics was −6 dB, and the RL of the X-band was lower than −4 dB at 2 mm.