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.     

Surface modification of α-Al2O3 with dicarboxylic acids for the preparation of UV-curable ceramic suspensions

Stereolithography of UV-curable ceramic suspensions can benefit from the preparation of stable, low viscosity and high solid loading ceramic suspensions without yield stress. Appropriately adding dispersants could optimize the rheological behavior to meet the requirements of stereolithography. In this work, short-chain dicarboxylic acids were utilized to modify the alumina particles and achieve well dispersed ceramic suspensions. The maximum adsorption capacities of dicarboxylic acids were determined by the method of High Performance Liquid Chromatography and the mechanism of surface modification and dispersion was also discussed. Dicarboxylic acids’ influence on the rheology behavior was systematically studied. When doses of dicarboxylic acids reach their maximum adsorption capacities, the alumina suspensions would achieve their lowest viscosities and yield stresses. 45 vol% alumina suspension with a viscosity ˂2 Pa s at shear rate 30 s⁻¹ was successfully formulated. A sintering density of 96.5% can be achieved for the sebacic acid-modified alumina UV-curable suspension.     

Digital light processing of Si-based composite ceramics and bulk silica ceramics from a high solid loading polysiloxane/SiO2 slurry

Nowadays, 3D polymer-derived silicon oxycarbide ceramics (SiOC) can be fabricated by the stereolithography method successfully. However, due to their intrinsically poor ceramic content and the large thermal shrinkage during the pyrolysis, it is difficult for the bulk 3D polysiloxane precursors to be pyrolyzed into dense 3D-ceramics. Herein, the ceramic content of the photocurable polysiloxane precursors was increased by adding a large amount of SiO₂ powders into the low solid content epoxy-acrylic siloxane. After being added with proper dispersant, the viscosity of the high solid loading polysiloxane/SiO₂ slurry can reach a proper level. Bulk 3D-silica ceramics with the wall-thickness around 8 mm can be conveniently fabricated from the polysiloxane/SiO₂ slurry by stereolithography and a two-step sintering process. The addition of a proper sintering aid NaF can promote the 3D-PSO/SiO₂ precursor to be converted into dense and crack-free 3D-silica ceramics with good mechanical proprieties.     

Rheological behavior and curing deformation of paste containing 85 wt% Al2O3 ceramic during SLA-3D printing

The preparation of high solids loading Al₂O₃ paste is of great significance for improving the properties of ceramics formed by UV-curing. However, the solid contents of alumina slurry used by digital light processing (DLP) and traditional alumina paste for stereolithography (SLA) are both less than 80 wt%. With increase in solid content, the viscosity of paste increases sharply, and rheological property deteriorates. In this study, ceramic paste containing 85 wt% (62 vol%) Al₂O₃ was prepared for SLA-3D printing of ceramics, and more than 85 wt% solid content was achieved by dispersant and other additives. Effects of different dispersants on rheological and curing properties of Al₂O₃ ceramic paste were studied. At room temperature, the viscosity of 85 wt% Al₂O₃ ceramic paste was 51733 mPa s at shear rate of 30 s^?1. A novel method was proposed to control curing deformation of parts during printing. As-manufactured ceramic did not show any cracks by naked eye and exhibited excellent mechanical properties, with three-point bending strength of 540 MPa, fracture toughness of 4.19 MPa m^1/2, Vickers hardness of 16 GPa, surface roughness of 0.463 μm, and density of 3.86 g/cm³.     

Fabrication of bulk piezoelectric and dielectric BaTiO3 ceramics using paste extrusion 3D printing technique

A simple and facile method was developed to fabricate functional bulk barium titanate (BaTiO₃, BT) ceramics using the paste extrusion 3D printing technique. The BT ceramic is a lead-free ferroelectric material widely used for various applications in sensors, energy storage, and harvesting. There are several traditional methods (eg, tape casting) to process bulk BT ceramics but they have disadvantages such as difficult handing without shape deformation, demolding, complex geometric shapes, expansive molds, etc. In this research, we utilized the paste extrusion 3D printing technique to overcome the traditional issues and developed printable ceramic suspensions containing BT ceramic powder, polyvinylidene fluoride (PVDF), N,N-dimethylformamide (DMF) through simple mixing method and chemical formulation. This PVDF solution erformed multiple roles of binder, plasticizer, and dispersant for excellent manufacturability while providing high volume percent and density of the final bulk ceramic. Based on empirical data, it was found that the maximum binder ratio with good viscosity and retention for desired geometry is 1:8.8, while the maximum BT content is 35.45 vol% (77.01 wt%) in order to achieve maximum density of 3.93 g/cm³ (65.3%) for 3D printed BT ceramic. Among different sintering temperatures, it was observed that the sintered BT ceramic at 1400°C had highest grain growth and tetragonality which affected high performing piezoelectric and dielectric properties, 200 pC/N and 4730 at 10³ Hz respectively. This paste extrusion 3D printing technique and simple synthesis method for ceramic suspensions are expected to enable rapid massive production, customization, design flexibility of the bulk piezoelectric and dielectric devices for next generation technology.     

Development and evaluation of Al2O3–ZrO2 composite processed by digital light 3D printing

Digital Light Processing (DLP) is a promising approach to fabricate delicate ceramic components with high-fidelity structural features. In this work, the alumina and zirconia/alumina ceramic suspensions with low viscosity and high solid loading (40 vol%) were prepared specifically for DLP 3D printing. After debinding and sintering, the final parts were obtained without any defects. The surface morphologies and mechanical properties of alumina (Al₂O₃) and zirconia toughened alumina (ZTA) composites were investigated and the results showed that the final parts exhibited high relative densities and good interlayer combination at the sintering temperature of 1600 °C. Comparing with the Al₂O₃, the ZTA composites exhibited significantly enhanced density (99.4%), bending strength (516.7 MPa) and indentation fracture toughness (7.76 MPa m^1/2).     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂ reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thanks to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂-reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thank to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

3D printing ceramic cores for investment casting of turbine blades,using LCD screen printers: The mixture design and characterisation

The primary objective of this study is to demonstrate the possibility of developing silica, alumina, and zircon-based photocurable ceramic suspensions that can be used for visible light photopolymerization (> 450 nm) and to optimise the binder formulations for the purpose of LCD-based ceramic 3D printing applications. Reference ceramic components for this work are ceramic cores employed in the investment casting of high-pressure turbine blades and vanes. Arguably, one of the most critical steps in photoinduced ceramic 3D printing is developing suitable ceramic suspensions, having high ceramic loading, low viscosity, and short curing times. Ceramic suspensions with four different novel binder formulations and commercial ceramic powders used in core manufacturing (SiO₂, Al₂O₃ and ZrSiO₄) were investigated to achieve the best trade-off between: (1) their curing performance (cure depth and curing speed), (2) rheological properties of the binder mixtures at the solid loadings of 60 vol.% for SiO₂, 55 vol.% for ZrSiO₄, and 45 vol.% for Al₂O₃; and (3) the green body mechanical properties of the mixtures after printing. The effect of ceramic particles on the selected binders was examined individually, and the correlation between cure depth (C_d), volumetric loading, and curing speed are evaluated. The results show all binders designed in this study provide an adequate cure depth, even at high ceramic loadings. When the curing behaviour of all unloaded binder mixtures from the previous study [1] compared with the 10 vol.% SiO₂ loaded mixtures, the cure depth of all formulated binder mixtures increased 50–55 % and the curing thickness of 60 vol.% SiO₂ loaded suspensions were still slightly higher than their unloaded counterparts. The rheology outcomes indicate that lower viscosity binders always result in lower viscosity of the ceramic loaded inks, even without taking the effect of dispersants into account. Besides, the addition of N-Vinyl-2-Pyrrolidone (NVP) monofunctional monomer to the binder mixtures significantly reduces the viscosity and changes the normally linear relationship of the mix viscosity and its silica loading content. Among the binder formulations loaded with 60 vol.% of SiO₂, the formulation providing the lowest viscosity and highest mechanical property consists of 5 wt.% of NVP, 45 wt.% of HDDA and 50 wt.% of Photocentric 34 resin. Although this binder mixture showed the highest green flexural strength when loaded by 55 vol.% ZrSiO₄, all other mixtures loaded with zircon flour also demonstrated a near-fluid behaviour, below 200 s^?1. In Al₂O₃ loaded mixtures, the HDDA di-functional binder formulations present lowest viscosity and the di- and multifunctional monomer blends (HDDA-Photocentric27) showed the highest mechanical properties when used in a 50/50 ratio. This work summarises the best binder choices for silica, alumina and zircon based ceramic suspensions used in core printing for investment casting applications through LCD screen printing.     

Fractions design of irregular particles in suspensions for the fabrication of multiscale ceramic components by gelcasting

A new approach for the preparation of suspensions with a high solid loading and low viscosity by using irregular particles was proposed. These suspensions were prepared for the fabrication of multiscale ceramic components by gelcasting. Based on the Funk-Dinger function and fractal theory, the closest packing theory was applied to optimize the volume fractions of different particles. The maximum solid loading of slurries prepared for gelcasting was 62 vol%, and the viscosity at a shear rate of 100 s^?1 was only 0.29 Pa s. By as-prepared suspensions, a decimeter-scale ceramic part with submillimeter features was fabricated successfully by gelcasting, which verify the feasibility of the proposed method.     

High solid loading,low viscosity photosensitive Al2O3 slurry for stereolithography based additive manufacturing

Photosensitive Al₂O₃-resin slurries with high solid loading, low viscosity used for stereolithography based additive manufacturing were prepared in this paper. The dispersion behavior and rheological behavior of the Al₂O₃-resin slurries were studied by rheology observation and sedimentation tests. The dispersant type, concentration and solid loading had significant effects on the rheological behavior and stability of the photosensitive Al₂O₃-resin slurries. A long term stability and homogeneity slurry was obtained when the dispersant and concentration were KOS110 and 5?wt%, respectively. The Al₂O₃ slurry prepared with a high solid loading up to 60?vol%, low viscosity of 15.4?Pa?s at 200?s^?1 was chosen for stereolithography based additive manufacturing.     

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.     

The effect of the surfactants on the formulation of UV-curable SLA alumina suspension

Stereolithography (SLA) has been regarded as the most promising rapid prototype (RP) production method for ceramic parts recently because of its better precision in size and site control. The rheological behavior and curing behavior of suspensions are controlling factors for ceramic stereolithography. In this work, oleic acid (OA), stearic acid (SA) and Poly(Acrylate Ammonium) (PAA-NH₄) were studied as the surfactant for HDDA-based suspension formulation. Modified alumina particles exhibit different wettability with HDDA monomer and thus the different rheology behavior and stability between the formulated suspensions. OA shows the best performance among all three dispersants. 40 vol% alumina suspensions with a viscosity ˂3 Pa s at 30 s⁻¹ shear rate were successfully formulated with OA and SA. A sintering density of 95% can be reached for the OA- and SA-modified alumina UV-curable resins.     

3D printing orientation controlled PMN-PT piezoelectric ceramics

Piezoelectric textured ceramics have drawn increasing research and industry interests by balancing the production cost and material performances. A new approach to realize the texture in piezoelectric ceramics is developed based on 3D printing stereolithography (SL) technique and successfully applied in the preparation of < 001 > -textured 0.71(Sm_0.01Pb_0.985)(Mg_1/3Nb_2/3)O₃-0.29(Sm_0.01Pb_0.985)TiO₃ (1 %Sm-PMN-29PT) ceramics in this work. As a critical process in texture ceramic fabrication, the alignment of BaTiO₃ templates along the horizontal direction is achieved by the shear force produced from the relative motion between the resin container and the blade during SL. The textured ceramics with obvious grain orientation features are successfully obtained. The enhanced piezoelectric properties of d₃₃ ≈ 652 pC N^?1 and d₃₃* ≈ 800 pm V^?1 are achieved in the 3D printed textured ceramic, which are about 60 % and 40 %, respectively, higher than their non-textured counterparts. Moreover, the textured sample shows a significant improvement on thermal stability of d₃₃*_T, which varies by less than ± 6 % from RT to 110 °C. Furthermore, the introduction of 3D printing into the synthesis of textured piezoelectric ceramics shows great advantages over the traditional tape-casting method. This work is expected to provide a promising way for the future design of textured piezoelectric functional materials.     

Development of a high solid loading β-TCP suspension with a low refractive index contrast for DLP -based ceramic stereolithography

Digital light processing (DLP)-based ceramic stereolithography has recently been regarded as a promising method to produce bioceramic scaffolds because of its high processing accuracy. However, this process suffers from light scattering that can reduce its resolution. This study shows that a reactive monomer OPPEA (2-([1,1′-biphenyl]-2-yloxy) can weaken the light scattering in β-tricalcium phosphate (β-TCP) suspensions and increase the broadening depth by decreasing the refractive index contrast. Moreover, a β-TCP suspension with a low viscosity (5.76 Pa·s at 100 s^?1), high solid loading (52 vol%) and high cure depth (>200 μm) without any broadening was developed by investigating the rheological behavior and cure behavior of the β-TCP suspensions. β-TCP scaffolds with a triply periodic minimal surface structure were also fabricated and exhibited a submicron-scale structure and low shrinkage rate (8%) after sintering. This suspension holds great promise for fabricating controllable β-TCP scaffold structures for bone tissue engineering by ceramic stereolithography.     

Strengthening three-dimensional printed ultra-light ceramic lattices

Ceramic is a typical brittle-essence material, which makes the low strength a fatal problem for ultra-light ceramic lattices with ultra-high porosity. In this study, ultra-light ceramic lattices with calculated density of ca. 0.8 g/cm³ and porosity up to ca. 80% reaching maximum compressive strength of 107 MPa were successfully printed by a three-dimensional (3D) printing technology stereolithography. Ultra-high-specific strength of the printed ceramic lattices (32 N·m/g) was even much higher than that of the steel lattices (2 N·m/g) (Int J Mach Tool Manuf, 62, 2012, 32). Short-cut quartz fibers and in situ growing Si₃N₄ whiskers were introduced as reinforcements to improve the strength of the printed lattices. Compressive strengths of the ceramic lattices improved by 2.8 and 3.6 times stronger than the originals, respectively. Significantly, energy absorption of the ceramic lattices under compression reached over 10 times larger than before. In comparison with the originals, micronano reinforcements significantly improved the compressive properties of the lattices with microsupporting structures and network formed in internal pores while maintaining the ultra-light structure.     

A review on the rheological behavior and formulations of ceramic suspensions for vat photopolymerization

Vat photopolymerization is an additive manufacturing process that produces high-performance ceramic parts. A critical step in the process is the preparation of a suspension that meets the requirements of high ceramic loading and proper rheological behavior, since an increase in solid loading might compromise the suspension rheology, resulting in non-uniform layer recoating. This review examines the rheological behavior of ceramic suspensions for vat photopolymerization, discussing the influence of the suspension formulation (solid loading, ceramic particle size and size distribution, monomers, diluents, and dispersants) on rheological aspects such as viscosity, shear-thinning/thickening behavior, critical shear rate, yield stress, and thixotropy. It provides a summary of the best formulations, which achieved low viscosity (<3 Pa.s) and high solid loading (>40 vol%), and reports the main trends and challenges of ceramic vat photopolymerization, suggesting general guidelines for the preparation of highly loaded photocurable ceramic suspensions with low viscosity.     

Comparison of dispersants performance on the suspension Lu2O3:Eu stability and high-density compacts on their basis

The conditions for obtaining a stable Lu₂O₃:Eu³⁺ suspension of spherical particles with a diameter of 100 nm using three dispersants possessing an electrosteric stabilizing effect (Dolapix CE 64, Darvan 821 A, Darvan C-N) have been studied. It has been shown that in colloidal processing of ceramics the packing density and microstructure of green bodies can be controlled by regulating the interactions between ceramic particles in the suspension. The influence of the molecular weight and concentration of the dispersant on the stability of Lu₂O₃:Eu³⁺ suspensions containing 5-10 vol.% of the solid loading has been considered. It has been determined that use of Dolapix CE 64 with a concentration of 1 mass.% in the alkaline pH range allows to obtain suspensions with high stability and low viscosity (∼1.7 сP). Such suspensions were used to produce compacts with a maximum relative density of ∼52% and uniform density distribution by the pressure slip casting method. The obtained compacts were densified into translucent Lu₂O₃:Eu³⁺ ceramics by the vacuum sintering method.     

Direct ink writing of 3D piezoelectric ceramics with complex unsupported structures

Piezoelectric ceramic, as a typical smart material, shows great potential in applications of sensing & actuation, smart structure and energy harvesting. However, the use of traditional methods to fabricate complex and high-precision piezoelectric ceramic devices faces huge technical difficulties and high molding costs. Direct ink writing is a typical additive manufacturing technology, but has limited capabilities when preparing ceramic products with complex unsupported structures. In this work, a combined process of direct ink writing (DIW) and secondary shaping of flexible ceramic green body has been developed and proved to produce complex piezoelectric ceramics. The PZT ink shows shear thinning behavior and appropriate viscoelasticity such as moderate viscosity and high storage modulus. The printed green body can be flexibly deformed and the samples after polarization show good piezoelectric properties, with an average d₃₃ up to 265 pC/N. This work demonstrates an attractive method for geometrically complex piezoceramic with unique macro structure due to its simplicity and low cost, and provides a solution to the key problems in the existing manufacturing technology of 3D ceramics.     

A new empirical viscosity model for ceramic suspensions

This paper presents a new predictive viscosity model for ceramic suspensions. Starting from Einstein's model (1906), various theoretical, empirical, and phenomenological models have been proposed for different suspension systems. However, there is still a lack of reliable model for ceramic suspensions used in colloidal ceramic shape-forming methods. Here, the rheological properties of ceramic suspensions comprising NiO/YSZ (nickel oxide/yttria stabilized zirconia) as the ceramic powder, and furfuryl alcohol as the suspending media were measured over a range of shear-rates (between 1 and 1000 s⁻¹) and different solid volume fractions from 0 to 0.4010. An empirical equation was then developed for the ceramic suspensions using the mobility parameter (?/(?_m−?)), which links Einstein's model with the more recent relative viscosity models. The proposed model was used to predict the relative viscosity data, showing excellent agreement to the experimental data from this study and with reported data in literature for other ceramic systems. The model was also used to estimate the maximum solid volume fraction for the ceramic suspensions (?_m=0.571), with better accuracy than those estimated by existing models.