织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究

为高效制备织构压电陶瓷,以球状Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) 为基体粉体,片状BaTiO₃ （BT）为模板粉体,采用光固化成型技术代替传统流延技术制备织构压电陶瓷。研究了粉体形貌对打印浆料流动性的影响、浆料的光敏参数以及不同BT含量织构陶瓷的晶体结构和电学性能。结果表明,球状粉体浆料具有低黏度的特性,能够有效提高打印浆料的固含量,最大固含量可达86%（质量）。此时陶瓷浆料的临界曝光量与透射深度分别为127.5 mJ/cm²和21.1 μm。打印后的PNN-PZT-BT陶瓷沿[00l]_c方向生长,BT模板粉体含量从1%增长到5%,陶瓷的织构度由42%增到92%。当BT含量为3%时,样品具有最高的压电常数d₃₃=1047 pC/N。与传统的流延法相比,SLA技术的工艺优势在于制备周期短,稳定性高,能够有效降低织构陶瓷的制备难度。     

织构PNN-PZT陶瓷的光固化成型制备及其电学性能研究

为高效制备织构压电陶瓷,以球状Pb(Ni_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ (PNN-PZT) 为基体粉体,片状BaTiO₃ （BT）为模板粉体,采用光固化成型技术代替传统流延技术制备织构压电陶瓷。研究了粉体形貌对打印浆料流动性的影响、浆料的光敏参数以及不同BT含量织构陶瓷的晶体结构和电学性能。结果表明,球状粉体浆料具有低黏度的特性,能够有效提高打印浆料的固含量,最大固含量可达86%（质量）。此时陶瓷浆料的临界曝光量与透射深度分别为127.5 mJ/cm²和21.1 μm。打印后的PNN-PZT-BT陶瓷沿[00l]_c方向生长,BT模板粉体含量从1%增长到5%,陶瓷的织构度由42%增到92%。当BT含量为3%时,样品具有最高的压电常数d₃₃=1047 pC/N。与传统的流延法相比,SLA技术的工艺优势在于制备周期短,稳定性高,能够有效降低织构陶瓷的制备难度。     

Effect of the slurry composition on the piezoelectric properties of PZT ceramics fabricated via materials extrusion 3D printing

Herein, the effect of the binder content in lead zirconate titanate (PZT) slurry has been systematically studied to improve the piezoelectric properties of PZT ceramics prepared via material extrusion 3D printing. For smooth printing, a slurry with a binder concentration ranging from 6 to 12 wt% was proposed. The porosity of the green body first decreased and then increased with an increase in the binder concentration, and the minimum porosity was obtained when the binder concentration reached 10 wt%. Samples with increased density were obtained after debinding and lead-rich atmosphere sintering. PZT piezoceramics fabricated using a binder content of 10 wt% exhibit the maximum relative density (96.9%), largest piezoelectric constant (342.6 pC/N) and dielectric constant (1621). Based on the above process, the wood pile structure and helical twentytetrahedral structural components were successfully fabricated using the material extrusion process. This research lays the foundation for the engineering application of 3D printing to fabricate high-performance piezoceramics with complex shapes.     

3D Printing of BaTiO3/PVDF Composites with Electric In Situ Poling for Pressure Sensor Applications

This paper presents 3D printing of piezoelectric sensors using BaTiO₃ (BTO) filler in a poly(vinylidene) fluoride (PVDF) matrix through electric in situ poling during the 3D printing process. Several conventional methods require complicated and time‐consuming procedures. Recently developed electric poling‐assisted additive manufacturing (EPAM) process paves the way for printing of piezoelectric filaments by incorporating polarizing processes that include mechanical stretching, heat press, and electric field poling simultaneously. However, this process is limited to fabrication of a single PVDF layer and quantitative material characterizations such as piezoelectric coefficient and β‐phase percentage are not investigated. In this paper, an enhanced EPAM process is proposed that applies a higher electric field during 3D printing. To further increase piezoelectric response, BTO ceramic filler is used in the PVDF matrix. It is found that a 55.91% PVDF β‐phase content is nucleated at 15 wt% of BTO. The output current and β‐phase content gradually increase as the BTO weight percentage increases. Scanning electron microscopy analysis demonstrates that larger agglomerates are formulated as the increase of BTO filler contents and results in increase of toughness and decrease of tensile strength. The highest fatigue strength is observed at 3 wt% BTO and the fatigue strength gradually decreases as the BTO filler contents increases.     

3D打印氧化硅陶瓷的制备及性能研究

随着陶瓷3D打印技术的发展,3D打印高性能陶瓷越来越受关注,在航空航天领域得到快速应用.通过研究分散剂、浆料pH、氧化硅粉体粒径和固相含量对浆料粘度和流动性的影响,可制备出粘度低、固相含量高、流动性好的陶瓷浆料.测试了不同固相含量对SiO2陶瓷的弯曲强度、烧成收缩率、气孔率和致密度的影响.结果表明:在68vol%的固相含量条件下,烧结后SiO2陶瓷的致密度达到74.32%,烧成收缩率为0.95%.     

SLA 3D printing of high quality spine shaped β-TCP bioceramics for the hard tissue repair applications

β-TCP has excellent biodegradability and bioabsorption properties, and is regarded as an ideal hard tissue repair material. In the present study, 3D printing β-TCP green bodies was realized using the stereo lithography apparatus (SLA) technology. The effects of the KH-560 dispersant and solid loading on the slurry properties were investigated systematically. The optimized KH-560 addition amount and the solid loading of the slurry were 2.0 wt% and 48 wt%, respectively, and the corresponding slurry for the subsequent SLA 3D printing exhibited good fluidity, uniform dispersion and good stability. The sintering schedule of the printed β-TCP green bodies was optimized by the DSC-TG analysis. By sintering the green bodies at 1050 °C for 8 h, high quality β-TCP bioceramics without crack or deformation were fabricated. It was found that increasing the solid loading of the slurry would decrease the porosity while reducing the shrinkage degree of the β-TCP ceramics. However, the slurry could hardly be printed when its solid loading was higher than 50 wt%.     

Development and analysis of a high refractive index liquid phase Si3N4 slurry for mask stereolithography

Ceramic mask stereolithography additive manufacturing technology has the abilities of fast and accurate printing complex and personalized ceramic parts. However, since the ultraviolet light is strongly blocked by the ceramic particles in the slurry during exposure, the slurry with high refractive index ceramic particles has low cure depth, and serious light scattering. This investigation developed a curable silicon nitride slurry with a high refractive index liquid phase, which significantly reduced the refractive index difference between the liquid phase and the silicon nitride ceramic particles. The high refractive index acrylate monomer and solvent were chosen to increase the cure depth while ensuring the curing accuracy. Compared with the slurry whose liquid phase was pure HDDA, the addition of OPPEA and ACMO in the liquid phase showed a better refractive index increasing effect and the strongest cure depth and dimensional accuracy improvement. POE was verified as a suitable non-reactive high refractive solvent. The composition of 20 wt% OPPEA, 10 wt% ACMO, 40 wt% HDDA, and 30 wt% POE were optimized as the high refractive index liquid phase for 40 vol% solid phase silicon nitride slurry. A finite element analysis model of silicon nitride slurry was established, and the distribution of ultraviolet light intensity in silicon nitride slurry with high refractive index liquid phase was numerically simulated.     

Influence of particle size on 3D-printed piezoelectric ceramics via digital light processing with furnace sintering

To improve the properties of BaTiO₃ piezoelectric ceramics fabricated by 3D printing, effects of particle size were investigated on the properties of ceramic slurries and the electrical properties of BaTiO₃ fabricated by Digital light processing (DLP) 3D printing method. It was found that the curing ability of the slurries decreased significantly when the particle size is close to the ultraviolet wavelength, while the viscosity kept decreasing with the increase of particle size. When the particle size in a range of submicron (d₅₀<1 μm), the grain size of sintered ceramics decreased from 13.27 to 6.84 μm as particle size increasing. Moreover, the piezoelectric constant and relative permittivity of sintered ceramics were measured, and it turns out to reach 168.1 pC/N and 1512, respectively, while using the BaTiO₃ powder with particle size of 993 nm. Finally, a cellular structural BaTiO₃ ceramics was fabricated by using optimized powder and process parameters and packaged as a piezoelectric sensor, showing a good function of force-electricity conversion. These results demonstrate the feasibility of fabricating high-quality functional ceramics with designed geometry by DLP.     

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property

Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO₃ (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 μW/cm² (49.79 μW/cm³) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.     

Preparation of photosensitive SiO2/SiC ceramic slurry with high solid content for stereolithography

Stereolithography is a popular three-dimensional (3D) printing technology, which is widely used for manufacturing ceramic components owing to its high efficiency and precision. However, it is a big challenge to prepare SiC ceramic slurry with high solid content for stereolithography due to the strong light absorption and high refractive index of dark SiC powders. Here, we propose a novel strategy to develop photosensitive SiO₂/SiC ceramic slurry with high solid content of 50–65 vol% by adding spherical silica with low light absorbance and applying a stacking flow model to improve the solid content of the slurry. The as-prepared slurry exhibits excellent stereolithography properties with a dynamic viscosity lower than 20 Pa s and curing thickness more than 120 μm. Therefore, it can be successfully applied for stereolithography-based additive manufacturing of SiC green bodies with large size (100 mm), sub-millimeter accuracy (0.2 mm), and complex structure. The stacking flow model also shows immense potential for the stereolithography of other dark-color ceramics with high solid content.     

Lattice-structured SiC ceramics obtained via 3D printing,gel casting,and gaseous silicon infiltration sintering

In view of technical difficulties in preparing ceramics with complex shapes, gel casting combined with 3D printing was here adopted to prepare silicon carbide ceramic green body, and gaseous silicon infiltration sintering was used to prepare 3D lattice-structured ceramics. The preparation of the slurry, gel curing, and ceramic molding was investigated. Results demonstrate that the ratio of components affects the fluidity and stability of slurry. However, when volume fraction of the solid phase of the slurry reaches 56%, the viscosity of slurry is only 300 mPa s, and drying shrinkage rate of green body is 6.6%; these characteristics make slurry suitable for 3D complex model injection molding. Furthermore, both the temperature and the initiator affect gel curing speed. As the temperature and initiator content increase, the induction and gel time are rapidly shortened. When demolding at 300 °C and when gaseous silicon infiltration sintering is carried out at 1550 °C, a 3D lattice-structured ceramic with relative density of 87% and average compressive strength of 433 MPa can be obtained.     

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.     

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.     

Fabrication of piezoelectric nano-ceramics via stereolithography of low viscous and non-aqueous suspensions

A high-performance piezoelectric nano-ceramic was fabricated through stereolithography of low viscosity and high solid loading ceramic/polymer composite suspensions. Through the proper fitting calculation of experimental data, the maximum theoretical solid loading, rheological and curing behaviors of the suspension system were evaluated and lucubrated. The suspensions with a 40 vol% solid loading of the BaTiO₃ nanoparticles displayed shear thinning behavior and a relatively low viscosity of 232 mPa·s at 46.5 s⁻¹ shear rate. After post-process, the 3D printed ceramic specimens showed a nanometer-level grain size with a density of 5.69 g/cm³, which corresponds to about 95% of the theoretical density. The printed ceramics exhibit a piezoelectric constant of 163 pC/N and relative permittivity of 2762 respectively. The results achieved in this research indicate that the stereolithography process is a promising 3D printing technology to fabricate piezoelectric materials with complex geometries and exquisite features for the applications of ceramic components.     

Development of a 3D model to predict curing dimensions and conversion rates of curable ceramic systems during stereolithography 3D printing process

To meet industry’s expectations for manufacturing ceramic parts by stereolithography, a better comprehension of the process, in particular laser scattering through the ceramic slurry is mandatory. This knowledge makes it possible to define adapted printing conditions to control the dimensions, homogeneity of the conversion and mechanical properties of the green parts, in order to achieve better resolutions and optimize the properties of sintered parts. This approach is focused on the development of a 3D polymerization modeling for stereolithography process able to predict curing and associated thermal phenomena. First, a design of experiments is carried out to identify material-dependent parameters, calibrate and validate the model, then able to predict monomer conversion rates and dimensions after curing depending on manufacturing parameters. Finally, temperature variation and exposure homogeneity have been evaluated. These results will allow, in future studies, to interpret the differences of deformations and mechanical properties of green parts.     

3D printing of doped barium-titanate using robocasting - Toward new generation lead-free piezoceramic transducers

Lead-free piezoelectric ceramics, most commonly prepared via conventional process based on a solid-state synthesis, can be used as acoustical transducers or sensors in many application fields. Particularly in some applications where specific geometries are desirable, the need of complex, time consuming, and costly operations could make conventional process inappropriate. This paper proposes an alternative solution based on additive manufacturing (AM), which is of great interest to control and shape the structure in an automatic manner. A formulation of ceramic slurry, consisting of 80%wt doped barium titanate (BT) and organic mixture, was investigated. The synthesized slurry is revealed to be compatible with the robocasting technique while maintaining good mechanical strength after debinding and sintering steps. Empirical measures together with microscopic analysis confirm high densities of the printed BT ceramics (∼ 95% after sintering), which is consistent to those obtained in literatures. To better assess the material and process performances, microstructural, dielectric and piezoelectric characterizations are conducted on both 3D printed and conventional BT ceramics. The results demonstrate that the printed samples give rise to excellent dielectric and piezoelectric properties (d₃₃ coefficient of 260 pC/N and dielectric constant of 1800), which are very close to the values obtained by conventional method on the same composition. As only a few and recent works have been found in the literatures on such systems, this study highlights the considerable and growing potential of robocasting techniques in the field of piezoelectric ceramics. The obtained d₃₃ coefficient is revealed as the highest value reported for printed BT doped systems.     

Effect of particle grading on the properties of photosensitive slurry and BaTiO3 piezoelectric ceramic via digital light processing 3D printing

To improve the density and piezoelectric constant of BaTiO₃ ceramics prepared by Digital Light Processing 3D printing, the properties of photosensitive slurry were investigated from the perspective of particle grading, and the nitrogen-air two-step debinding and sintering process on the relative density and electrical properties were explored. It was found that as the mass ratio of coarse particles increased, the viscosity, shear stress and cure depth of the slurry decreased. When the mass ratio of fine and coarse particles was 2:8 and sintered at 1350 °C, the ceramic had better performance, with relative density reaching 95.39 ± 0.63 %. The piezoelectric constant d₃₃ was 215 ± 13 pC/N, 29.52 % higher than the single-peak powder. The relative permittivity (ε_r) and polarization (P_r) were 978 and 16.656 μC/cm². Finally, BaTiO₃ ceramics with Triply Periodic Minimal Surface structures were prepared as piezoelectric sensors, which had the highest output voltage at the same displacement when the mass ratio was 2:8.     

Key features in the development of unimorph stainless steel cantilever with screen-printed PZT dedicated to energy harvesting applications

The design and processing of vibrational energy harvester based on screen-printed piezoelectric lead zirconate titanate (Pb(ZrxTi1-x)O3 (PZT)) are described here. Two different structures, a simple cantilever and a complex zig-zag geometry made of PZT layer sandwiched between gold electrodes and supported on a metallic stainless steel substrate have been successfully fabricated by screen printing thick film technique. Compared to bulk PZT ceramics, the main limiting features at different scales are porosity, interfaces, and bending issues. The microstructural analysis of the interfaces in the cantilever has highlighted the formation of an interface between the substrate and the bottom electrode which ensures cohesion of the structure but can limit its dynamic. Bending has shown to be dependent on the thickness of the active piezoelectric layer. Dielectric and electromechanical characterizations performed on multilayers, bulk ceramics, and free-standing screen-printed disks are compared and discussed on the basis of interface issues.     

Transparent alumina ceramics fabricated by 3D printing and vacuum sintering

Transparent alumina ceramics were fabricated using an extrusion-based 3D printer and post-processing steps including debinding, vacuum sintering, and polishing. Printable slurry recipes and 3D printing parameters were optimized to fabricate quality green bodies of varying shapes and sizes. Two-step vacuum sintering profiles were found to increase density while reducing grain size and thus improving the transparency of the sintered alumina ceramics over single-step sintering profiles. The 3D printed and two-step vacuum sintered alumina ceramics achieved greater than 99 % relative density and total transmittance values of about 70 % at 800 nm and above, which was comparable to that of conventional CIP processed alumina ceramics. This demonstrates the capability of 3D printing to compete with conventional transparent ceramic forming methods along with the additional benefit of freedom of design and production of complex shapes.     

Effect of Sm3+ doping on ferroelectric,energy storage and photoluminescence properties of BaTiO3 ceramics

Rare earth doped ferroelectric ceramics have attracted much attention due to their great potential application for novel multifunctional optical-electro devices. Herein, the x% mol Sm³⁺ doped BaTiO₃ (BTO:xSm³⁺) ceramics were fabricated by the conventional solid-state reaction method. The Sm³⁺ ions composition dependent phase structure, ferroelectric, energy storage and photoluminescence properties were systematically investigated. With the increase of Sm³⁺ ions composition, the remanent polarization decreases dramatically from 15.705 μC/cm² (BTO) to 7.132 μC/cm² (BTO:3.0%Sm³⁺), but the energy storage density and efficiency increase greatly with a relative change of 79.76% and 31.13%, respectively. Furthermore, Sm³⁺ doping causes the transformation from the tetragonal to pseudo-cubic phase for BTO ceramics at room temperature, resulting in a broader temperature transition range from the ferroelectric to paraelectric phase and a lower Curie temperature. Particularly, the pure BTO and BTO:xSm³⁺ ceramics show great thermal stability for energy storage properties. In addition, under the excitation of 408 nm near-ultraviolet light, the BTO:xSm³⁺ ceramics exhibit the strongest orange-red emission peak around 596 nm with a large relative tunability of intensity by 88.97%. The results suggest that the BTO:xSm³⁺ ceramics are suitable for the design of optoelectronic devices.