Y2O3 doped Ba0.9Ca0.1Ti0.9Sn0.1O3 ceramics with improved piezoelectric properties

Lead-free Ba_0.90Ca_0.10Ti_0.90Sn_0.10O₃-xY₂O₃ (BCTSY, x = 0–0.09) ceramics were prepared by traditional solid-state sintering method. All the BCTSY samples showed pure perovskite structures without detectable impurity. Orthorhombic/tetragonal phase coexisted in the sample of x = 0.03 to 0.07. Remarkable enhancement of the electric properties were achieved at x = 0.03 with d₃₃ of 650 pC/N, K_p of 59.6%, and the remnant polarization P_r of 10.2 μC/cm². The strengthened temperature stability of piezoelectricity is beneficial to the application of the piezoceramics.     

Effects of ZrSiO4 content on properties of SiO2-based ceramics prepared by digital light processing

SiO₂-based ceramic cores are widely used in the preparation of gas turbine engine hollow blades due to their excellent chemical stability and easy removal after casting. In this paper, ZrSiO₄ reinforced SiO₂-based ceramics were fabricated using digital light processing (DLP) technology. The results showed that the addition of ZrSiO₄ reduced the cure depth due to its high UV light absorptivity and refractive index. When the content of ZrSiO₄ increased to 15 wt%, the cristobalite content reached the maximum, and radial shrinkage reached the minimum of 1.4%. ZrSiO₄ grains could hinder the propagation of cracks, enhancing the room-temperature flexural strength. At 1550 °C, fracturing across SiO₂ grains in SiO₂-based ceramics led to the great improvement of high-temperature flexural strength. When the content of ZrSiO₄ reached 15 wt%, the flexural strength at room temperature and high temperature was 11.5 MPa and 36.7 MPa, respectively. Therefore, the SiO₂-based ceramics prepared using DLP technology have good room temperature and high temperature properties, and are expected to be used for hollow blade casting.     

Effect of organic fibers addition on digital light processing for Al2O3 porous ceramics

Porous ceramics based on additive manufacturing have great application potential in many industries, including filtration, catalysis, and heat insulation. In this research, we propose a method for manufacturing porous ceramics with connected channels structure through ceramic digital light processing (DLP) and organic fiber decomposition. The crossed fibers in the green body, working as a pore-forming agent, were decomposed and removed to form connected channels in ceramic. It was confirmed that ball milling changed the fiber morphology during slurry preparation, which was beneficial to promote fibers crossing. Besides, we focused on the influence of the “Sponge Compression effect” during the DLP process, which affected the fibers distribution. The existence of fibers in the green body resulted in uneven pressure distribution during the debinding process, providing a potential source of cracks. Results show that this method can produce channels with a diameter of 100 μm and high connectivity, providing great potential in fabricating high connectivity porous ceramics with complex shapes and structures.     

High permittivity and low dielectric loss of the (Ca0.9Sr0.1)1-xLa2x/3Cu3Ti4O12 ceramics

In this work, we have systematically studied the effects of La³⁺/Sr²⁺ dopants on the crystal structure, microstructure, dielectric response and electrical properties of (Ca_0.9Sr_0.1)_1-xLa_2x/3Cu₃Ti₄O₁₂ (x = 0, 0.025, 0.05 and 0.075) ceramics. XRD results show that the lattice parameter increases with the increase in the La³⁺ content. SEM micrographs illustrate that a small amount added of La³⁺ can reduce the grain size of CCTO during sintering. With increasing La³⁺ content, the grains grow larger. Dielectric measurements indicated that all doped samples synthesized by the solid-state reaction exhibit giant dielectric constants ε'>10⁴ over a large frequency range (10 Hz to 1 MHz) and at any temperature below 600 K. In particular, the ceramic with x = 0.05 exhibits a colossal dielectric permittivity ～5.49 × 10⁴; which increases by about 50% compared to that of the undoped ceramic. In addition, the doped ceramic also presents a low dielectric loss ～ 0.08 at 20 °C and 0.6 kHz. The giant dielectric properties of these samples can be explained by the (IBLC) model.     

Influence of the processing way for La3+-doping on crystal structure,microstructure, and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3 ceramics

Perovskite ceramics with a formula of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) were produced through a conventional solid-state reaction procedure following three different La³⁺-doping methods using powders of La₂O₃, or La₂O₃/Al₂O₃ powder mixture, or LaAlO₃. La³⁺ doping favored grain growth and densification, affected the grain size distribution, and improved the dielectric properties of the produced sintered CTLA ceramics. The doping methods had a strong influence on these properties. More specifically, doping with La₂O₃ and La₂O₃/Al₂O₃ resulted in formation of solid solution, while a secondary phase formed in the CTLA ceramics doped with LaAlO₃, which caused a coarsening of the microstructure and lowered the La³⁺ doping effects on the dielectric properties. The experimental results suggest that La³⁺ doping improves the dielectric properties of the sintered CTLA perovskite ceramics, which are further enhanced by doping with Al³⁺ ions in small amounts. However, further increase of Al³⁺ ions content jeopardizes them.     

Y-TZP,Ce-TZP and as-synthesized Ce-TZP/Al2O3 materials in the development of high loading rate digital light processing formulations

Y-TZP, Ce-TZP and Ce-TZP/Al₂O₃ materials are widely investigated in dentistry. Digital Light Processing (DLP) is considered as a breakthrough technology for the dental field to fine print Y-TZP green parts. High loading photocurable formulations (>45 vol%) with Y-TZP, Ce-TZP commercial powders and Ce-TZP/30 vol% Al₂O₃ as-synthesized powder suitable to DLP printing were achieved in this study. A low specific surface area (5–13 m²/g) of particles without any pores and 1 wt% to 2 wt% of steric dispersant are required to obtain high loading formulations. The as-synthesized composites provide these properties by increasing the calcination temperature from 800 °C to 1200 °C. The as-prepared ceramic formulations based on the same photocurable resin exhibit a curing behavior suitable to DLP process for Y-TZP formulations (thickness > 50 μm in few seconds with a high conversion rate) in comparison with ceria ceramic. The ceria is a strongly UV absorbing material and a specific formulation is developed to obtain 80% of conversion and a cured thickness of 75 μm in 0.5 s.     

Enhanced dielectric breakdown strength in Ni2O3 modified Al2O3-SiO2-TiO2 based dielectric ceramics

Dielectric ceramics have raised particular interest since they enable pulsed-power systems to achieve high voltage gradient and compact miniaturization. In this work, x wt%Ni₂O₃ doped Al₂O₃-SiO₂-TiO₂ based dielectric ceramics were prepared using conventional solid-state reaction and the effects of Ni₂O₃ on the crystal structure, dielectric properties and dielectric breakdown strength were investigated. It was found that with the doping of Ni₂O₃, the Al₂O₃-SiO₂-TiO₂ based dielectric ceramics became denser and the distribution of each phase was more uniform. For the composition of x?=?2.0, the dielectric breakdown strength was increased into 82.1?kV/mm, more than twice compared with that of the undoped one. In addition, the relationship between the dielectric breakdown strength and the resistance of Al₂O₃-SiO₂-TiO₂ based dielectric ceramics was discussed. The results show that the doping of Ni₂O₃ is a very feasible way to improve the dielectric breakdown strength and optimize the dielectric properties for the Al₂O₃-SiO₂-TiO₂ based dielectric ceramics.     

Preparation and microwave dielectric properties of low-loss MgZrNb2O8 ceramics

A novel low-loss microwave dielectric material MgZrNb₂O₈ was reported for the first time. Single-phase MgZrNb₂O₈ was prepared by a conventional mixed-oxide route and sintered in the temperature range of 1280–1360 °C. The microstructure and microwave dielectric properties were investigated systematically. The X-ray diffraction results showed that all samples exhibit a single wolframite structure. When the sintering temperature was lower than 1340 °C, the Q×f value mainly depended on the relative density. However, when the sintering temperature was above 1340 °C, the Q×f value mainly relied on the grain morphology in addition to the density. The MgZrNb₂O₈ ceramic sintered at 1340 °C for 4 h exhibited excellent microwave dielectric of ε_r=26, Q×f=120,816 GHz (where f=6.85 GHz), and τ_f=?50.2 ppm/°C. These results demonstrate that MgZrNb₂O₈ could be a promising candidate material for the application of highly selective microwave ceramic resonators and filters.     

Microwave sintering of dense and lattice 3Y-TZP samples shaped by digital light processing

Nowadays it is possible to produce ceramic parts with solid and complex shapes with rapid and efficient shaping and sintering techniques. In this paper, 3mol% yttria stabilized zirconia (3Y-TZP) dense and lattice parts were shaped by Digital light processing method (DLP) and densified by conventional (CV) and microwave (MW) sintering. 3Y-TZP samples were MW sintered up to 1550 °C with different heating rates (10, 30, and 50 °C/min) for the dense samples and 30 °C/min for the lattice samples. Controlled thermal cycles with a homogenous heating and no thermal runaway was reached. CV sintering was carried out at 10 °C/min up to 1550 °C. No inter-layer delamination was detected after sintering by the two methods. Both dense and lattice MW-sintered samples reached high final densities (equivalent to obtained values with CV-sintered samples, i.e., ≥98% T.D.), but exhibited a lower average grain size than CV-sintered materials. The different architectures between dense and lattice samples resulted in a different specific absorbed power: the power absorbed by the dense sample is lower than that absorbed by the lattice one meaning that this sample architecture heats up easily.     

Rutile TiO2 microwave dielectric ceramics prepared via cold sintering assisted two step sintering

In this work, a sintering route named cold sintering assisted two step sintering process (CSP-TS) is presented to prepare rutile TiO₂ ceramics with submicron grain sizes. Cold sintering process at 300 °C with tetrabutyl titanate and water as the liquid phase yields a ‘green body’ with a relatively high density of ～80 %, and finally dense (98.5–99.8 %) rutile TiO₂ ceramics with grain sizes of ～600 nm can be obtained in the second sintering process at 950?1000 °C. The microstructural analysis with SEM and TEM indicates that the CSP-TS samples sintered at 950 °C have an obvious phenomenon of recrystallization, accompanying by a decrease of amorphous phases and a formation of clear grain boundaries. Besides, the rutile TiO₂ ceramics prepared by CSP-TS possess excellent microwave dielectric properties with relative permittivity of 92.0–98.4 and Q × f values of 27,800?31,900 GHz. Therefore, it is feasible to utilize CSP-TS to prepare ceramics with small grain sizes at low sintering temperatures.     

Vinyl polysilazane based photo-curable resin derived ceramics manufactured by digital light processing with Al flake as the active filler

Al flake was used as the filler to optimize the properties of vinyl-polysilazane based photo-curable resin derived ceramics (P-PDCs) manufactured by digital light processing. Al flake addition showed a significant inhibitory effect on the macroscopic cracking and the micrometer voids of the P-PDCs. With the Al flake content of 0.6 wt%, P-PDCs pyrolysed at 1300 °C exhibited a maximum Vickers hardness and bending strength of 9.47 GPa and 89.39 MPa, respectively. The Nano-indentation measurements showed an improvement of the elastic modulus from 74.56 GPa to 85.62 GPa, and the indentation hardness from 7.12 GPa to 12.47 GPa as the increase of the Al flake. During pyrolyzing, the pristine Al flake reacted with the pyrolysed by-product obtained hollow lamellar Al₂O₃ phase of varying aspect ratios in the forming matrix, which acted not only as a strengthening phase on the mechanical properties but also as a channel for the release of gaseous.     

Effect of CuO/MnO additives on microstructure and microwave dielectric properties of 3ZrO2-3TiO2-ZnNb2O6 ceramics

The effect of CuO/MnO additives on phase composition, microstructures, sintering behavior, and microwave dielectric properties of 3ZrO₂-3TiO₂-ZnNb₂O₆ (3Z-3T-ZN) ceramics prepared by conventional solid-state route were systematically investigated. CuO/MnO doped ceramics exhibited a main phase of α-PbO₂-structured ZrTi₂O₆ and a secondary phase of rutile TiO₂. SEM results showed that the grain size of MnO doped ceramics became larger with increasing amount of dopants. The presence of CuO/MnO additives effectively reduced the sintering temperature of 3Z-3T-ZN ceramics to 1220 °C. MnO doped into ceramics could enhance the Q×f values significantly. The 0.5 wt% CuO doped 3Z-3T-ZN ceramics with 0.5 wt% of MnO, sintered at 1220 °C for 4 h, was measured to show superior microwave dielectric properties, with an ε_r of 41.02, a Q×f value of 44,230 GHz (at 5.2 GHz), and τ_f value of +2.32 ppm/°C.     

Microstructural and microwave dielectric properties of LZT (Li2ZnTi3O8) ceramics sintered in presence of bismuth borate glass for LTCC applications

In the present research, the Li₂ZnTi₃O₈(LZT) ceramics were synthesized throughout solid-state ceramic processing, then mixed with bismuth borate (BiBO) glass prepared based on conventional melt quenching method. Wetting behavior of BiBO glass on the LZT ceramic substrate was monitored by hot stage microscopy. Afterward, dielectric LZT ceramics containing different amounts of BiBO glass (0.25–6 wt%) were sintered at various temperatures. X-ray diffraction and electron back scatter diffraction examinations revealed the presence of two crystalline phases of Li₂ZnTi₃O₈ and Bi₂Ti₂O₇. The maximum value of relative density (above 95%) was obtained in the case of specimens contained more than 5 wt% glass. The microwave dielectric properties of the finally sintered BiBO glass containing LZT ceramics were as follows: dielectric constant (ε_r) = 21.44–25.09, quality factor (Q × f) = 10839–54708 GHz and temperature coefficient of resonant frequency (τ_f) = (? 15.58) ? (? 12.86)ppm/°C.     

Silicon carbide whiskers reinforced SiOC ceramics through digital light processing 3D printing technology

Polymer derived silicon oxycarbide ceramic materials and silicon carbide whiskers reinforced ceramic composite are prepared through digital light processing (DLP) 3D printing technology in the present work. A new type of UV-curable preceramic polymer is firstly synthesized and then two types of photopolymer resins with and without SiC whiskers as reinforcement are prepared. Due to the high curing rate and good fluidity of the resins, they are applied in DLP 3D printing and various 3D objects with complicated structures and high printing resolution have been printed. The derived ceramic materials show amorphous microstructure and there is no apparent porosity and cracking throughout the whole sample surface of the ceramic materials and the SiC whiskers are uniformly embedded in the ceramic matrix and remain intact and unaffected during the pyrolysis process. The SiC whiskers reduced the shrinkage and mass loss. More importantly, it significantly improves the mechanical performance of the derived ceramic materials in which the compressive strength increases from 77.5 ± 10.2 MPa to 98.4 ± 12.3 MPa. Benefiting from the easiness of the fabrication, high printing resolution and excellent mechanical performance, the derived ceramic materials have great potential applications in various areas.     

Improved non-ohmic and dielectric properties of Cr3+ doped CaCu3Ti4O12 ceramics prepared by a polymer pyrolysis solution route

CaCu_3-xCr_xTi₄O₁₂ (x?=?0.00–0.20) ceramics were prepared via a polymer pyrolysis solution route. Their dielectric properties were improved by Cr³⁺ doping resulting in an optimal dielectric constant value of 7156 and a low tanδ?value of 0.092 in a sample with x?=?0.08. This might have resulted from a decrease in oxygen vacancies at grain boundaries. XANES spectra confirmed the presence of Cu⁺ ions in all ceramic samples with a decreasing Cu⁺/Cu²⁺ ratio due to an increased content of Cr³⁺ ions. All CaCu_3-xCr_xTi₄O₁₂ ceramics showed nonlinear characteristic with improvement in both the breakdown field (E_b) and its nonlinear coefficient (α). Interestingly, the highest values of α, ～ 114.4, and that of E_b, ～8455.0?±?123.6?V?cm^?1, were obtained in a CaCu_3-xCr_xTi₄O₁₂ sample with x?=?0.08. The improvement of dielectric and nonlinear properties suggests that they originate from a reduction of oxygen vacancies at grain boundaries.     

Nb-doped BaTiO3-(Bi0.5Na0.5)TiO3 ceramics with core-shell structure for high-temperature dielectric applications

Nb-doped 0.90BaTiO₃-0.10(Bi_0.5Na_0.5)TiO₃ temperature-insensitive ceramics with novel core-shell structure were sintered at low temperature by the conventional solid-state reaction method. The beneficial role of Nb in facilitating the formation of core-shell structure because of chemical inhomogeneity is verified, which is responsible for the weak temperature dependence of dielectric properties. Temperature dependence of permittivity measured at different frequencies shows high frequency dispersion at low temperature, while without relaxor characteristic at high temperature. The Vogel–Fulcher model was adopted to study the relaxor behaviour of Nb-doped 0.90BaTiO₃-0.10(Bi_0.5Na_0.5)TiO₃ ceramics at low temperature. The samples with an addition of 1.5?mol% Nb₂O₅ provide a temperature coefficient of capacitance meeting the requirements of the X9R characteristic, and result exhibits an optimum dielectric behaviour of ε_r ～1900, tanδ ～1.8% at room temperature, making the material a promising candidate for high temperature applications.     

Enhanced dielectric,ferroelectric and magnetic properties of Ba4Sm2Fe2Nb8O30 RT multiferroics prepared by microwave sintering

High density Ba₄Sm₂Fe₂Nb₈O₃₀ (BSFN) multiferroics ceramics with tetragonal tungsten bronze structure had been prepared by microwave sintering (MS) for 30min and conventional sintering (CS) methods for 4 h at 1275 °C. Single tungsten bronze phase and equiaxial grains are obtained for the MS BSFN ceramics, while a small amount secondary phase of SmNbO₄ is observed in the CS BSFN ceramics with columnar grains. Compared to Ba₄Sm₂Fe₂Nb₈O₃₀ ceramics prepared by CS method, enhanced dielectric, ferroelectric and magnetic properties are achieved for the MS BSFN ceramics. The values of electric polarization Pr and coercive electric field Ec are 2.11 μC/cm² and 7.14 kV/cm for the MS BSFN ceramics, respectively. Meantime, the magnetic polarization Mr of 0.410emu/g and coercive magnetic field Hc of 2930Oe are also obtained for the MS BSFN ceramics. Based on the density, crystal structure, point defect and grain, the reasons of enhanced dielectric, ferroelectric and magnetic properties are discussed for the MS BSFN ceramics It is indicated that Ba₄Sm₂Fe₂Nb₈O₃₀ is an intrinsic room temperature multiferroic materials.     

Microstructure and dielectric characteristics of Nb2O5 doped BaTiO3-Bi(Znl/2Til/2)O3 ceramics for capacitor applications

The effects of Nb₂O₅ addition on the dielectric properties and phase formation of 0.8BaTiO₃-0.2Bi(Zn_l/2Ti_l/2)O₃ (0.8BT-0.2BZT) ceramics were investigated. The desired perovskite phase was achieved with Nb₂O₅ doping levels being in the range of 0.5 wt.%–3.0 wt.%. The 0.8BT-0.2BZT ceramics doped with 1.5 wt.% Nb₂O₅ was found to possess a moderate dielectric constant (ε = 1170) and low dielectric loss (tanδ = 1%) at room temperature and 1 kHz frequency, showing a flat dielectric behavior over the temperature range of −55 °C–200 °C. Based on this composition, the X9R-MLCC (multilayer ceramic capacitor) with Ag0.7-Pd0.3 electrode was sintered at 1060 °C. The optimized capacitance of the MLCC is 26.5 nF, with dielectric loss tanδ of 0.9% and electrical resistance of 4.50 × 10¹¹ Ω at room temperature, leading to a high time constant of 11,900 s, decreasing to 175 s at 200 °C, being one order higher than those of commercial X7R MLCC. In addition, the equivalent series resistance (ESR) was found to be on the order of 0.2 mΩ at 2 MHz, much lower than that of the DC Bus Capacitor Bank for the automotive inverters (where the desired characteristic is <3 mΩ). All these characteristics of the newly developed MLCC will benefit the high temperature and high power capacitor applications.     

Effect of closed pores on dielectric properties of 0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3 porous ceramics

Porous 0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃ ceramics are fabricated via the pore-forming agent method with polymethyl methacrylate (PMMA) and stearic acid (SA) as pore forming agents, and microstructure observations demonstrate that the porosity, pore shape, and pore sizes can be controlled by the synthesis technology. The dielectric properties of porous ceramics are found not only correlated to the pore-matrix composite model, but also have a significant grain-size effect. Based on the Zener Theory, pining forces exerted by pores on the grain boundary are calculated, to explain the shape effect of pores on grain boundary migration. A phase-field simulation is carried out to investigate pore shape effect on the grain size regulation in porous polycrystalline, and simulation results are in good agreements with experiential results as well as theoretical calculations. Thus, a modified equation is proposed to predict the effective permittivity of the porous piezoelectric ceramics by considering effects of porosity, pore shape and grain size.     

Composite bioceramic scaffolds with controllable photothermal performance fabricated by digital light processing and vacuum infiltration

Photothermal scaffolds can help clear bone tumor cells after resection. In this work, hydroxyapatite-akermanite-Fe₃O₄ (HA-AK-FE) bioceramic scaffolds were fabricated by infiltrating digital light processing (DLP)-printed HA-AK scaffolds in nano-Fe₃O₄ solution. The prepared HA-AK-FE samples exhibited excellent and controllable photothermal performance under the irradiation of 808 nm near-infrared light. By controlling nano-Fe₃O₄ concentration, irradiation power and infiltration time, temperature of HA-AK-FE samples could be regulated in a wide range from room temperature to 150 °C within 15 s. Photothermal temperature remained stable after 4 times repeated irradiations. In SBF solution and under subcutaneous tissue, the heating rate and photothermal temperature decreased obviously compared with in air, but they could still meet the needs of killing tumors (41–48 °C). The Fe release concentration of wafers after immersing in SBF for 1 day was 0.037 mg/L and non-venomous. These results confirm the feasibility and controllability of fabricating photothermal scaffolds by coating nano-Fe₃O₄ with vacuum infiltration, and the prepared HA-AK-FE scaffolds are hopeful to be used in photothermal therapy of bone tumors.