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.     

Anisotropy management on microstructure and mechanical property in 3D printing of silica-based ceramic cores

Ceramic core is an essential component in the precise casting of hollow turbine blades, and the investigation on 3D printing of silica-based ceramic cores is crucial to the development of aviation industry; however, they are suffered from difficulty in high-temperature strength and structural anisotropy. In present work, silica-based ceramic cores were prepared via DLP stereolithography 3D printing, and the anisotropy management on microstructures and properties were explored based on the particle size of fused silica powders. In 3D printed ceramic cores with coarse powders, significant anisotropy was displayed exhibiting multilayer structure with large gaps in horizontal printing and uniform porous microstructure in the vertical direction, which was further explained by the particle deposition in printing. With finer silica powders, the uniformity in the microstructures was highly improved, attributed to the enhanced particle dispersion in ceramic slurries and promoted interlayer particle rearrangement during sintering. To evaluate the anisotropy in mechanical property, the ratio of vertical strength to horizontal strength (σ_V/σ_H) was proposed, which rose from 0.48 to 0.86 as the particle size decreased from 35 µm to 5 µm, suggesting enhanced mechanical uniformity. While the average particle size of silica powders was 5 µm, the flexure strengths of ceramic cores in different directions were up to 18.5 MPa and 16.3 MPa at 1540 °C with σ_V/σ_H ratio of 0.88, which well satisfied the demands for the casting of turbine blades. This work inspires new guidance on the anisotropy management in ceramic cores prepared by 3D printing, and provides new technology for fabrication of silica-based ceramic cores with superior high temperature mechanical properties.     

Relaxor Ferroelectric BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for Energy Storage Application

Perovskite solid solution ceramics of (1 ? x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (BT–BMN) (x = 0.05–0.2) were synthesized by solid‐state reaction technique. The results show that the BMN addition could lower the sintering temperature of BT‐based ceramics. X‐ray diffraction results reveal a pure perovskite structure for all studied samples. Dielectric measurements exhibit a relaxor‐like characteristic for the BT–BMN ceramics, where broadened phase transition peaks change to a temperature‐stable permittivity plateau (from ?50°C to 300°C) with increasing the BMN content (x = 0.2), and slim polarization–electric field hysteresis loops were observed in samples with x ≥ 0.1. The dielectric breakdown strength and electrical resistivity of BT–BMN ceramics show their maxima of 287.7 kV/cm and 1.53 × 10¹³ Ω cm at x = 0.15, and an energy density of about 1.13 J/cm³ is achieved in the sample of x = 0.1.     

Dielectric,Ferroelectric, and Piezoelectric Properties of BiFeO3–BaTiO3 Ceramics

Perovskite solid solution ceramics of (1 ? x)BiFeO₃–xBaTiO₃ (1 ? x)BF–xBT, 0.2 ≤ x ≤ 0.45) with high electrical resistivity were prepared by solid‐state reaction method. Actual ferroelectric hysteresis loops and temperature dependence of dielectric constant of the ceramics were obtained. Ceramics of 0.7BF–0.3BT with small rhombohedral distortion show highest remnant polarization (P_r = 26.0 μC/cm²) and piezoelectric coefficient (d₃₃ = 134 pC/N). Compositions with pseudo‐cubic symmetry (intermediate phases) show relaxor‐like dielectric anomaly. The values of P_r and d₃₃ decrease with increasing BT content, from 24.8 μC/cm² and 104 pC/N for 0.65BF–0.35BT to 8.2 μC/cm² and 5 pC/N for 0.55BF–0.45BT.     

Chemical stability of KNbO3, NaNbO3, and K0.5Na0.5NbO3 in aqueous medium

In recent years, potassium sodium niobate (K_0.5Na_0.5NbO₃, KNN) has become popular and promising among perovskite lead‐free piezoceramic systems. In this study, the chemical stability of KNN powders in aqueous medium was investigated as a function of pH, time, and powder surface area. To better understand the dissolution behavior of the complex KNN stoichiometry, subconstituents such as potassium niobate (KNbO₃, KN) and sodium niobate (NaNbO₃, NN) were investigated separately first. Results showed that all of the cations in the structure underwent dissolution in different values. Indicating that KNN undergoes incongruent dissolution in aqueous medium, the dissolution of A site cations was higher at lower pH while the dissolution of B site cations increased at higher initial pH. The order of released cation concentrations (C_A1 = K > C_{A2 = Na} > C_B = Nb) fits with inverse relationship of cation field strength (FS) order, B = Nb⁵⁺_FS > A₂ = Na⁺_FS>A₁ = K⁺_FS, at pH 4, 7 and 10 for NN, KN, and KNN. Calculated diffuse layer thickness from the ICP data confirmed to outer amorphous layer in TEM image. Also, the ratio of normalized cation concentration versus surface area of powders showed that incongruent dissolution kinetic was driven by the diffusion step.     

Piezoelectric properties of [001]-textured high-power PMnN-PZT piezoceramics sintered at a low temperature

The 1.0 mol% CuO-added 0.14Pb(Mn1/3Nb2/3)O₃-0.86Pb(Zr_0.55Ti_0.45)O₃ (CPMnN-PZT) piezoceramics were synthesized at low temperatures (≤ 950 °C) by the columbite method to remove the pyrochlore phase. It exhibited a high Q_m of 3016 and a high T_C of 309 °C. However, it showed small d₃₃ and k_p values of 143 pC/N and 0.43, respectively. The CPMnN-PZT piezoceramic was textured along the [001] direction using BaTiO₃ (BT) templates to enhance its soft piezoelectric properties. The [001]-textured CPMnN-PZT + y vol% BT piezoceramics (1.0 ≤ y ≤ 5.0) were densified at a low temperature of 950 °C with a high Lotgering factor (≥ 92%). The textured sample (y = 1.0) showed a high Q_m of 1400 with increased d₃₃ and k_p values of 278 pC/N and 0.58, respectively, and its piezoelectricity showed excellent temperature stability up to 225 °C. Therefore, the textured CPMnN-PZT sample can be used for developing high-power piezoelectric devices.     

Influence of bimodal particle distribution on material properties of BaTiO3 fabricated by paste extrusion 3D printing

Barium titanate (BaTiO₃) is a lead-free piezoelectric ceramic widely used in sensors and actuators applications. However, there are many manufacturing challenges to process BaTiO₃ due to the brittle nature of ceramics. Most current sensors based on piezoelectricity are limited to mold shapes or flat 2D structures, which narrow their applications. Paste extrusion (PE) 3D printing technique allows the fabrication of complex geometry ceramics with less design limitations. However, the piezoelectric property of 3D printed ceramics is typically lower than those fabricated using traditional means due to lower density. Herein, a study to evaluate the influence of bimodal particle distribution on improving density and piezoelectricity of BaTiO₃ ceramics fabricated using PE 3D printing is presented. 3D printed and compression pressed samples under the same mixing ratios were compared. The highest packing density was obtained using 50-50% vol. fraction of bimodal particles for both types of samples. A predictive model for packing density was validated by experimental results. The highest piezoelectric coefficient of 350 pC/N was obtained using 50-50% vol. bimodal particle distribution. This piezoelectric coefficient is 40% higher than the monodispersed sample using 100 nm particles with a piezoelectric coefficient of 250 pC/N.     

Effect of Na0.5Bi0.5TiO3 on dielectric properties of BaTiO3 based ceramics

In this work, Na_0.5Bi_0.5TiO₃ (NBT) was used to improve the high temperature dielectric properties of Nb, Co-doped BaTiO₃ (BT). Different x was selected (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4) to optimize the ratio of BT to NBT in (1 ? x) BT–xNBT solid solution. The dielectric constant of the original X7R material is about 4900 at room temperature, decreasing to 2500 with NBT addition (x = 0.2). Of important is that the temperature stability was improved with dielectric constant variation being less than ±15% up to 160 °C.     

Controllable preparation of two-dimensional oriented BaTiO3 polycrystals from K0.8Ti1.73Li0.27O4 crystals by a one-step solvothermal process

Titanate precursors play an important role in obtaining oriented titanate materials via topochemical conversion. In this study, a two-dimensional (2D) K_0.8Ti_1.73Li_0.27O₄ (KTLO) crystal was successfully prepared by a one-step solvothermal process using TiO₂, LiOH?H₂O, and KOH as raw materials in ethanol/water mixed solvent for the first time. Meanwhile, the conditions and influencing factors for the solvothermal preparation of KTLO were investigated and analysed. With a ratio of ethanol/water of 20:5, better 2D KTLO can be obtained by reacting at 150 °C for 24 h. On this basis, KTLO was used directly to perform solvothermal treatment with Ba(OH)₂, and 2D BaTiO₃ (BT) was easily prepared by adjusting the reaction conditions (concentration, temperature, and time). When the solvothermal treatment was carried out in 0.5 mol/L Ba(OH)₂ solution at 80 °C for 1.5 h, 2D BT crystals could be easily obtained through the topochemical reaction mechanism. This strategy not only develops new methods for preparing precursors but also greatly simplifies the preparation process of BT and provides new research ideas for the preparation of functional materials.     

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.     

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.     

High-performance and high-precision Al2O3 architectures enabled by high-solid-loading,graphene-containing slurries for top-down DLP 3D printing

To date, obtaining the high-solid-loading Al₂O₃ slurry and overcoming the trade-off between high solid loading and printing accuracy and strength of printed green bodies to achieve high-performance and precision Al₂O₃ ceramic parts by DLP 3D printing remain challenging. In this study, an Al₂O₃ slurry with high solid loading of 60 vol% was developed through dispersant optimisation for top-down DLP 3D printing. Graphene was innovatively introduced during slurry fabrication to decouple the printing accuracy and strength of green bodies from such high solid loading. Simultaneously, graphene addition could considerably reduce slurry fluidity, thereby facilitating its coordination with top-down DLP. With 0.07 wt% graphene addition, the dimension deviations of printed green bodies improved from 90 to 880 µm to ≤ 70 µm, and the bending strength increased by 17.75%. High-performance and precise Al₂O₃ ceramic components with low sintering shrinkages were prepared. The density and microhardness were 99.7% and 18.61 GPa, respectively.     

Structural and piezoelectric properties of textured NLKNS-CZ thick films and their application in planar piezoactuator

0.97(Na_0.5-xLi_xK_0.5)(Nb_0.89Sb_0.11)O₃-0.03CaZrO₃ [(N_0.5-xL_xK)(NS)-CZ] piezoceramic (x = 0.325) has a pseudocubic-tetragonal-orthorhombic (PC-T-O) multi-structure. The PC structure formed in this piezoceramic was identified as the R3m rhombohedral structure. This piezoceramic showed the large piezoelectric charge constant (d₃₃) of 515 pC/N due to the PC-T-O multi-structure. The NaNbO₃ (NN) templates were used to texture the (N_0.5-xL_xK)(NS)-CZ thick films along the (001) direction, and the textured thick film (x = 0.0375) had a large Lotgering factor of 95.6%. The PC-T-O multi-structure was observed in this thick film (x = 0.0375), but the thick film (x = 0.0325) showed a PC-O structure owing to the diffusion of the NN templates into the thick film. The textured thick film (x = 0.0375) exhibited an increased d₃₃ of 625 pC/N because of the PC-T-O multi-structure and the lineup of grains along the [001] direction. A textured thick film (x = 0.0375) was used to fabricate a planar-type actuator to confirm its applicability to electrical devices. This actuator exhibits large acceleration (580.3 G) and displacement (150 μm) at a low electric field of 0.2 kV/mm with a short response time of 3.0 ms. Therefore, the (N_0.5-xL_xK)(NS)-CZ thick films are excellent lead-free piezoceramics.     

Remarkably High‐Temperature Stability of Bi(Fe1−xAlx)O3–BaTiO3 Solid Solution with Near‐Zero Temperature Coefficient of Piezoelectric Properties

The 0.72Bi(Fe_1?xAl_x)O₃–0.28BaTiO₃ (x = 0, 0.01, 0.03, 0.05, and 0.07, abbreviated as BFAx–BT) lead‐free high‐temperature ceramics were prepared by the conventional ceramic processing. Systematic investigation on the microstructures, crystalline structures, dielectric and piezoelectric properties, and high‐temperature stability of piezoelectric properties was carried out. The crystalline structures of BFAx–BT ceramics evolve from rhombohedral structure with x < 0.01 to the coexistence of rhombohedral structure and pseudocubic phases with x ≈ 0.01, finally to pseudocubic phases when x > 0.03. Remarkably high‐temperature stability with near‐zero temperature coefficient of piezoelectric properties (TCk_p), together with improved piezoelectric properties has been achieved for x = 0.01 BFAx–BT ceramics. The BFAx–BT(x = 0.01) ceramics simultaneously show the excellent piezoelectric properties of d₃₃ = 151 pC/N, k_p = 0.31 and super‐high‐temperature stability of T_d = 420°C, TCk_p = 1 × 10^?4. It is considered that the observed strong piezoelectricity and remarkably high‐temperature stability should be ascribed to the phase coexistence of rhombohedral and pseudocubic phases. The rhombohedral phases have a positive TCk_p value and the pseudocubic phases possess a negative TCk_p value. Thus, the TCk_p value of BFAx–BT ceramics can be tuned by composition of x.     

Microstructure and electrical properties of Er-doped 0.67 Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 ceramics with BaTiO3 templates

In this study, [001]-oriented Er-doped 0.67 Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (0.67PMN-0.33 PT) textured ceramics with different BaTiO₃ (BT) template concentrations were explored. The samples were prepared by tape-casting. Er³⁺ was added to modify the electrical properties of the polycrystalline ceramics, and the BT template was used to improve the texture of polycrystalline ceramics. The 0.67PMN-0.33 PT textured ceramics contained coexisting rhombohedral and tetragonal phases. The ceramics became increasingly textured as the sintering temperature increased up to 1250 °C. The piezoelectric coefficient of 0.67PMN-0.33 PT with 5 wt% BT was 634 pC/N, which is 1.2 times than that of randomly oriented 0.67PMN-0.33 PT. The strain of the ceramic with 5 wt% BT increased by 12.5% relative to a random control specimen. Analysis of the electrical properties and microstructure suggested that the enhancement of the piezoelectric coefficient and strain may be caused by the addition of Er³⁺ and the BT template. First, the directional growth of grains along the template affected the change-of-phase distribution of the system and formed a more adaptive phase. Second, Er³⁺ was substitutionally doped on the A-site of the perovskite to form local heterostructures. Finally, the relaxation components of the templates and Er³⁺ changed in the solid solution with the matrix. The solid solution of the BT templates and Er-doped-matrix powder changed the relaxation degree, which affected the interactions at the polar nanoregions and increased the piezoelectric coefficient of the ceramics.     

Dielectric properties and impedance analysis of BaTiO3-based ceramics with core-shell structure

In this paper, a core-shell structure, where the BaTiO₃ (BT) particles were coated with 0.25Bi(Zn_1/2Ti_1/2)O₃-0.75BaTiO₃ [BT@x(0.25BZT-0.75BT)] by sol-gel method, was fabricated and confirmed by transmission electron microscopy (TEM). The impedance data of BT, 0.25BZT-0.75BT and BT@x(0.25BZT-0.75BT) (x=0.5–1.0) ceramics was collected and fitted by different equivalent circuits. The core and shell regions of BT@x(0.25BZT-0.75BT) (x=0.5–1.0) ceramics can be separated in complex impedance plots (fitted by a 4RC equivalent circuit), according to the activation energies of BT and 0.25BZT-0.75BT. The calculated activation energy of the core part in BT@x(0.25BZT-0.75BT) ceramics is relatively stable, being closer to the activation energy (0.86 eV) of BT, while the activation energy of the shell was found to increase from 0.28 eV to 0.53 eV with increasing the shell thickness. The average core/shell ratio (d_gc/d_gs) for BT@0.8(0.25BZT-0.75BT) ceramics was found to be on the order of 7.26, calculated by a modified two-layer dielectric model. In addition, Lichtenecker formula was used to simulate the dielectric constant of BT@0.8(0.25BZT-0.75BT) ceramics at room temperature and the simulated results are in agreement with the measured values.     

Enhanced resistivity and strain stability of BiFeO3–BaTiO3 ceramics by hot-press sintering in oxygen atmosphere

Even though BiFeO₃–BaTiO₃ (BF–BT) with high Curie temperature and excellent piezoelectric properties is very suitable for high-temperature applications, its rapid reduction in resistivity with temperature limits its further application. So far, there is no effective method to improve the resistivity of BF–BT at a high-temperature state. In this work, hot-press sintering combined with an oxygen atmosphere was used to prepare (1 − x)BF–xBT (x = 0.2–0.33) ceramics for the first time, which reduced the sintering temperature from 1000 to 920°C. The controllable grain size can be achieved by adjusting the sintering temperature and the applied pressure. The X-ray photoelectron spectroscopy results confirmed that using hot-press sintering effectively avoided the generation of heterovalent Fe ions, and the resistivity of BF–BT ceramics at the high-temperature stage was improved by two orders of magnitude. It was found that hot-press sintering can cause the oriented growth of the sample along the (1 1 0) direction, and further refined X-ray diffraction was used to accurately analyze the changes in the lattice structure. The hot-press sintered samples obtained larger polarization strength, especially the electro-induced strain showed excellent temperature stability in the wide temperature range of 30–170°C. Hot-pressing sintering combined with an oxygen atmosphere is more suitable for preparing high insulation and electrical breakdown resistance ceramics.     

Controlled anisotropy in 3D printing of silica-based ceramic cores through oxidization reaction of aluminum powders

Ceramic cores are key components to form inner hollow structures in aero-engine blades, and 3D printing is an ideal molding technology for ceramic cores. In this work, silica-based ceramic cores are fabricate via 3D printing of digital light processing (DLP) stereolithography, and the anisotropy in microstructure and property are controlled by aluminum powders. The ceramic cores without aluminum powders exhibit anisotropic microstructure with interlayer gaps, which get narrower and disappear with doping of 7.5–10 wt% of aluminum powders, due to the volume expansion during oxidization reaction of aluminum powders filling the interlayer gaps. The anisotropy in mechanical property is rely on the printing direction, and the ratio of strength in different directions (σ_V/σ_H) is put forward to value the mechanical anisotropy; the ratios rise from 0.40 to 0.92 at room temperature and 0.51 to 0.97 at 1540 °C, as 7.5 wt% of aluminum is doped, and the optimized ceramic cores show high-temperature strengths of 16.6 MPa and 16.1 MPa in different printing directions. Even though ceramic cores with 10 wt% of aluminum show uniform microstructure and higher σ_V/σ_H ratio, the weak particle bonding within printing layers limits their mechanical property, and the strengths decrease to 13.8 MPa and 13.4 MPa at 1540 °C. This work inspires a new technique to excellent high-temperature mechanical properties with anisotropy control in 3D printing of ceramic cores.     

Orientation dependence of electric field induced phase transitions in lead-free (Na0.5Bi0.5)TiO3-based single crystals

The orientation dependence of the electric field induced strain and phase transitions in 0.92(Na_0.5Bi_0.5)TiO₃–0.06BaTiO₃–0.02(K_0.5Na_0.5)NbO₃ (NBT–6BT–2KNN) single crystals has been investigated. The evolution of Raman spectra with electric field reveals that a tetragonal ferroelectric phase is initially induced at E = 14 kV/cm and completed above E = 25 kV/cm for [001] oriented single crystals. When the electric field is applied along [111] direction, a partial phase transition from pseudocubic to rhombohedral structure is triggered at E = 19 kV/cm, which is higher than that for inducing tetragonal ferroelectric phase along [001] direction. Both field-induced phase structures and stability of NBT–6BT–2KNN single crystal are strongly associated with the crystallographic orientations. These results provide a better understanding to the field-induced macroscopic strain in lead-free NBT-based ferroelectrics.     

Enhanced mechanical properties of 3D printed alumina ceramics by using sintering aids

Stereolithography based 3D printing provides an efficient pathway to fabricate alumina ceramics, and the exploration on the mechanical properties of 3D printed alumina ceramics is crucial to the development of 3D printing ceramic technology. However, alumina ceramics are difficult to sinter due to their high melting point. In this work, alumina ceramics were prepared via stereolithography based 3D printing technology, and the improvement in the mechanical properties was investigated based on the content, the type and the particle size of sintering aids (TiO₂, CaCO₃, and MgO). The flexural strength of the sintered ceramics increased greatly (from 139.2 MPa to 216.7 MPa) with the increase in TiO₂ content (from 0.5 wt% to 1.5 wt%), while significant anisotropy in mechanical properties (216.7 MPa in X-Z plane and 121.0 MPa in X–Y plane) was observed for the ceramics with the addition of 1.5 wt TiO₂. The shrinkage and flexural strength of the ceramics decreased with the increase in CaCO₃ content due to the formation of elongated grains, which led to the formation of large-sized residual pores in the ceramics. The addition of MgO help decrease the anisotropic differences in shrinkage and flexural strength of the sintered ceramics due to the formation of regularly shaped grains. This work provides guidance on the adjustment in flexural strength, shrinkage, and anisotropic behavior of 3D printed alumina ceramics, and provides new methods for the fabrication of 3D printed alumina ceramics with superior mechanical properties.