Stability properties and microstructure properties of microwave-sintered CeO2 doped zirconia ceramics

Nanosized CeO₂–ZrO₂ powders prepared by atmospheric pressure pyrolysis were used as raw materials to prepare CeO₂–ZrO₂ ceramics using microwave sintering. The samples were characterised using bulk density measurements, X-ray diffraction (XRD), Fourier Transform Infrared Spectrometer (FT-IR), Raman, and scanning electron microscopy (SEM). The purpose was to determine the optimised microwave sintering process for CeO₂–ZrO₂ ceramics and reveal the corresponding mechanism. The results show that with a CeO₂ addition content above 5 mol%, the tetragonal phase peak appeared obviously in the sample. The results show that the tetragonal phase peak appears when the CeO₂ content is more than 5 mol%. The dopants, namely CeO₂, have reduced the solid solution's phase transformation temperature with the assistance of microwave heating. Additionally, the grain size of the CeO₂–ZrO₂ ceramics has shown a negative relationship with Ce content at a temperature of 900 °C. The reason is that the rapid sintering due to microwave sintering and the oxygen vacancies generated by CeO₂ can effectively inhibit grain growth. The regulation mechanism on microwave sintering of CeO₂–ZrO₂ ceramic was clarified, and the technical prototype of controlled prepared CeO₂–ZrO₂ ceramics by microwave sintering was constructed.     

Effect of oxide nanofillers on fabrication,structure, and properties of zirconia-based composites

We have studied the effect of NiO on the sintering of yttria-stabilized zirconia at temperatures ranging from 1300 °C to 1500 °C in air and argon environments. It was found that the addition of NiO stabilized the cubic phase of ZrO₂ independently from the sintering atmosphere. The monoclinic phase of ZrO₂ formed only during sintering within the air environment at temperatures higher than 1450 °C. The transformation of NiO to Ni by reversible decomposition depends on the sintering atmosphere, and this can lead to variations in the nature of inclusions and in changes of the structure and properties of nanocomposite materials in the system ZrO₂–NiO(Ni). NiO and Ni inclusions can increase the indentation fracture toughness of zirconia–nickel oxide composite material more than 50%, which can be compared with zirconia ceramics during sintering in a neutral atmosphere alone.     

Ball milling assisted preparation of nano La–Y/ZrO2 powder ternary oxide system: Influence of doping amounts

Zirconia powder with good dispersion, fine particle size, and stability is used as high-quality raw material in many fields, such as ceramic materials and refractories. In this paper, the influence of lanthanum oxide (La₂O₃) and yttrium oxide (Y₂O₃) co-doped zirconia (ZrO₂) on its phase transformation behavior, phase stability, and microstructure were investigated. The ball milling method is applied to fabricate different amounts of La₂O₃-doped yttrium oxide stabilized zirconia oxide. Then, the powder obtained from ball milling was roasted using the microwave sintering method. The samples were characterized using XRD, FT-IR, Raman, SEM and BET to determine the optimal conditions for La₂O₃–Y₂O₃ co-doped ZrO₂ powder. The results showed that replacing part of Y₂O₃ with La₂O₃ increases zirconia powder's tetragonal and cubic phase, enhancing the fracture strength of the subsequent synthesized materials. At the same time, the stability of zirconia stabilized with La₂O₃ doping is significantly improved compared to that of Y₂O₃ alone. According to all analysis methods, when the doping amount is 2.8Y0.2La, the powder's phase composition, stability, particle size distribution, and dispersion degree are the best compared with other doping amounts in our study. The obtained powder has a smaller specific surface area, a lower surface energy, a smaller porosity, and a higher density. The samples under this condition can be better used in subsequent materials. The enhancement of various properties of zirconia can significantly prolong the service life of materials in practical applications.     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Controlled sintering and phase transformation of yttria-doped tetragonal zirconia polycrystal material

In this paper, 3 mol% yttria-doped tetragonal zirconia polycrystal material (3 mol% Y₂O₃–ZrO₂) was prepared using an optimised pressureless sintering process. The phase change and particle size distribution of Y₂O₃–ZrO₂ during sintering were studied, and the effect of sintering temperature on the properties of Y₂O₃–ZrO₂ was analysed. The raw materials and prepared samples were analysed using XRD, Raman spectroscopy, SEM, and Gaussian mathematical fitting. The results show that sintering encourages the transformation of the monoclinic phase into the tetragonal phase, thus improving the crystallinity of the sample. The relative content of the tetragonal phase in the sample increased from 57.43% to 99.80% after sintering at 1200 °C for 1 h. In the range of sintering temperatures studied in this paper (800–1200 °C), the zirconia material sintered at 1000 °C presented the lowest porosity and the best density.     

Study on drying kinetics of calcium oxide doped zirconia by microwave-assisted drying

Ca–ZrO₂ is an essential structural and functional material, which is commonly used in refractories, electronic ceramics, and functional ceramics. The properties of Ca–ZrO₂ materials are depending on the quality of Ca–ZrO₂ powders. The main factors affecting the quality of powder are sintering temperature and the drying effect. This paper applied modern microwave drying technology to dry Ca–ZrO₂ powder. The impact of initial mass, microwave heating power, and initial moisture content on the drying of Ca–ZrO₂ were explored. The results showed that the average drying rate increased with the rise of initial mass, microwave heating power, and initial moisture content. Wang and Singh, Page, and Quadratic Model were applied to fit Ca–ZrO₂ with an initial moisture content of 5.6%, mass of 30 g, and microwave output power of 400 W. The results displayed that the Page model had a better fitting effect. It was also applicable to other different initial moisture content, original mass, and microwave heating power. The diffusion coefficient calculated by Fick's second law displayed that with the increase of initial mass, initial moisture content, and microwave heating power of Ca–ZrO₂, the effective diffusion coefficient increased first and then declined. When the Ca–ZrO₂ of microwave heating power was 640 W, mass was 30 g, and the moisture content was 5.65%, the effective diffusion coefficients of zirconia were 1.42533 × 10^?13, 2.91806 × 10^?13, 5.652.2471 × 10^?13 m²/s, respectively. To determine the activation energy of microwave dried zirconia, using the relationship between microwave power and activation energy, the activation energy of microwave dried zirconia was calculated to be ?23.39 g/W. This paper aims to rich experimental data for the industrial application of microwaves to strengthen dried zirconia and propose a theoretical basis.     

A structural study of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-partially stabilized zirconia ceramics

Partially stabilized zirconia ceramics ZrO₂ (Y₂O₃) of different structures and phase compositions are tested for thermal stability and thermal shock. The ceramics can be used as solid electrolytes in oxygen activity sensors for fluid heat transfer agents (lead).__________Translated from Novye Ogneupory, No. 10, pp. 56 – 59, October, 2004.     

Terahertz probing of low-temperature degradation in zirconia bioceramics

ZrO₂-based ceramics are widely used in biomedical applications due to its color, biocompatibility, and excellent mechanical properties. However, low-temperature degradation (LTD) introduces a potential risk for long-term reliability of these materials. The development of innovative nondestructive techniques, which can explore LTD in zirconia-derived compounds, is strongly required. Yttria stabilized zirconia, 3Y-TZP, is one of the well-developed ZrO₂-based ceramics with improved resistance to LTD for dental crown and implant applications. Here, 3Y-TZP ceramic powders were pressed and sintered to study the LTD phenomenon by phase transition behavior. The LTD-driven tetragonal-to-monoclinic phase transition was confirmed by XRD. XPS analysis demonstrated that induced LTD reduced the oxygen vacancies which supports these findings. It is proved that after the degradation, the 3Y-TZP ceramics show the decreased dielectric permittivity at terahertz frequencies due to the crystallographic phase transformation. Terahertz nondestructive probe is a promising method to investigate LTD in zirconia ceramics.     

Phases in La2O3 and NiO doped (Zr,Sn)TiO4 microwave dielectric ceramics

Dielectric ceramics with composition in the ZrO₂–SnO₂–TiO₂ system containing La₂O₃ and NiO as sintering aids were prepared and investigated by XRD, XPS, SEM, EDS, and microwave dielectric measurements. Ceramics prepared with defloculed slurry using a Dyno-Mill^®, and sintered at 1370°C exhibit very good microwave dielectric characteristics: ε=37 and QF up to 62 000 at 4 GHz. We have observed a matrix phase with at least two or three different secondary phases in function of the employed grinding media (balls of zircon or magnesium stabilised zirconia). So, we have synthesised and characterised these phases.     

Effect of sintering time on the microstructure and stability of Al2O3–ZrO2 composite powders under microwave-assisted sintering

The function of ceramic coating is closely related to the construction technology and the quality of ceramic powders. Generally, Al₂O₃–ZrO₂ powders are rapidly sprayed on the material surface at high temperatures to obtain better performance. Improving the quality of Al₂O₃–ZrO₂ powders can make them more widely used in ceramic coating. In this paper, microwave sintering was used to enhance the sintering process of the powders, and the effect of sintering time on the microstructure, properties, and stability of Al₂O₃–ZrO₂ powders was investigated. The results proved that microwave heating could improve the crystallinity and stability of the samples. At 900 °C, the tetragonal phase content in samples with different sintering times were 63.05%, 63.25%, 62.39%, and 63.22%, respectively. The average particle sizes obtained by Gaussian fitting are 1.04 μm, 0.83 μm, 0.88 μm, 0.86 μm, respectively. The Gaussian fitting particle size data was consistent with the normal distribution. Compared with the particle size of raw material (1.10 μm), the particles were refined, and the dispersion effect was noticeable. Therefore, the best sintering time for microwave sintering Al₂O₃ stabilized zirconia was 2 h. This paper aims to provide reasonable data support for improving the preparation of high-quality Al₂O₃-PSZ ceramic powders and to guide the industrial production of Al₂O₃-PSZ powders.     

Microwave hybrid sintering of Al2O3 and Al2O3–ZrO2 composites,and effects of ZrO2 crystal structure on mechanical properties,thermal properties,and sintering kinetics

Structural ceramics such as Al₂O₃ and Al₂O₃–ZrO₂ composites are widely used in harsh environment applications. The conventional sintering process for fabrication of these ceramics is time-consuming method that requires large amount of energy. Microwave sintering is a novel way to resolve this problem. However, to date, very limited research has been carried out to study the effects of different ZrO₂ crystal structures on Al₂O₃–ZrO₂ composites, especially on the sintering kinetics, when fabricated by microwave sintering.The microwave hybrid sintering of Al₂O₃ and Al₂O₃–ZrO₂ composites was performed in this study. Tetragonal zirconia and cubic zirconia were used as two different reinforcements for an α–alumina matrix, and the mechanical and thermal properties were studied. It was found that Al₂O₃ experienced a remarkable increase in fracture toughness of up to 42% when t-ZrO₂ was added. Al₂O₃–c-ZrO₂ also showed increased fracture toughness. The sintering kinetics were also thoroughly investigated, and the average activation energy values for the intermediate stage of sintering were estimated to be 246 ± 11 kJ/mol for pure Al₂O₃, 319 ± 71 kJ/mol for Al₂O₃–c-ZrO₂, and 342 ± 77 kJ/mol for Al₂O₃–t-ZrO₂. These values indicated that the activation energy was increased by the addition of either type of ZrO₂, with the highest value shown by Al₂O₃–t-ZrO₂.     

Sintering behaviour and properties of zirconia ceramics prepared by pressureless sintering

Improvements in the sintering process and powder quality can lead to wider application of zirconia in ceramics. In this study, the effects of different temperatures on the stability, relative content of the tetragonal phase, and composition of Al₂O₃–ZrO₂ ceramic powders were explored using pressureless-assisted sintering. The crystallinity of the sintered Al₂O₃–ZrO₂ samples was significantly improved. The content of the tetragonal-phase ZrO₂ in sintered ceramic powders was 52.07%, 52.46%, 56.16%, 63.99%, and 64.90%, respectively, which was significantly higher than those of the raw materials. The average particle size of the sintered samples decreased from 1.07 μm to 0.17 μm with an increase in temperature, indicating that the ceramic powder particles were refined. The sample that was subjected to pressureless-assisted sintering at 1200 °C and held for 1 h exhibited the best stability and more uniform particle distribution compared to other samples. The particle size distribution data were closer to the standard line, satisfying the requirements of the normal distribution law. The results revealed that a high temperature was more favourable to the solid solution, and the formation of an Al₂O₃–ZrO₂ solid solution can diminish the influence of the volume expansion of ceramic powders on the sample properties during sintering. Therefore, the addition of the sintering aid Al₂O₃ significantly promotes the densification of the powders, and the pressureless sintering technique reduces the sintering temperature of the solid solution, thus imparting a crystalline structure and excellent mechanical properties to the material.     

Broad sintering temperature range and stable microwave dielectric properties of Mg2TiO4–CeO2 composite ceramics

There has been extensive research on microwave dielectric materials considering their application in 5G and 6G communication technologies. In this study, the sintering temperature range of Mg₂TiO₄–CeO₂ (MT-C) ceramics was broadened using a composite of CeO₂ and Mg₂TiO₄ ceramics, and their microwave dielectric performance was stabilized. Low-loss MT-C composite ceramics were prepared using the solid-phase reaction method, and their microwave dielectric properties, microscopic morphologies, and phase structures were investigated. The proposed MT-C ceramics contained Mg₂TiO₄ and CeO₂ phases; their average grain size was maintained at 2–4 μm in the sintering temperature range of 1275–1425 °C, and the samples were uniformly dense without porosity. The cross-distribution of Mg₂TiO₄ and CeO₂ grains in the samples inhibited the growth of ceramic grains, providing uniform and dense surfaces. The dielectric loss of MT-C ceramics remained constant in the temperature range of 1300–1425 °C at 9 × 10^?4 (8.45 ≤ f ≤ 8.75 GHz). As opposed to the base material, MT-C ceramics are advantageous owing to their wide sintering temperature range and the stable microwave dielectric properties, and there are suitable substrate materials for further industrial applications.     

Fabrication and characterization of bioactive zirconia-based nanocrystalline glass-ceramics for dental abutment

Zirconia-based ceramics are becoming a popular biomaterial in dental implantology due to their natural silver-white color, excellent mechanical properties, and good biocompatibility. However, zirconia-based ceramics are biologically inert, which limits their ability to integrate with the surrounding human tissues. To solve this problem, the bioactive elements of calcium (Ca) and phosphorus (P) were doped in high-strength ZrO₂–SiO₂ nanocrystalline glass-ceramics (NCGCs) to overcome the biological inertness of ZrO₂-based ceramics. XRD results showed that tetragonal zirconia (t-ZrO₂) and monoclinic zirconia (m-ZrO₂) were the only two crystalline phases after spark plasma sintering. Ca and P dopants acted as destabilizer of t-ZrO₂, enhancing its transformability to m-ZrO₂ during sintering. The amount of t-ZrO₂ exerted significant effects on the average flexural strength of the NCGCs. The NCGC with 45 mol% ZrO₂ were composed of 64.5 vol% t-ZrO₂ and 35.5 vol% m-ZrO₂ after sintering at 1230 °C. And, the average flexural strength and Vickers hardness of the NCGC was 615 MPa and 1049 HV, respectively. In comparison, the NCGC with 65 mol% ZrO₂ were composed of 12.6 vol% t-ZrO₂ and 87.4 vol% m-ZrO₂ after sintering at 1150 °C. The average flexural strength and Vickers hardness of the NCGC was 293 MPa and 839 HV, respectively. Interestingly, the NCGCs exhibited a plastic deformation behavior during flexural strength test, which was different from traditional brittle ceramics. The ion release results demonstrated that Ca²⁺ and Si⁴⁺ ions kept on releasing from the surface of the material. The formation of hydroxyapatite in the in-vitro apatite formation test indicated that the NCGCs had good biological activity. The doped ZrO₂-based NCGCs combined moderate strength and good bioactivity. Hence, the NCGCs show promising potential to be used in sub-gingival regions, such as dental abutments.     

Synthesis,Microstructure, and Microwave Dielectric Properties of Spinel ZnGa2O4 Ceramics

Spinel ZnGa₂O₄ ceramics were synthesized by conventional solid‐state method and their microwave dielectric properties were investigated. The phase evolution and microstructures of specimens were studied by XRD and SEM. The textured surface microstructures of ZnGa₂O₄ ceramics formed at high sintering temperatures. The spinel‐structured ZnGa₂O₄ ceramics sintered at 1385°C exhibited excellent microwave dielectric properties: a dielectric constant (ε_r) of 10.4, a quality factor (Q × f) of 94.600 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?27 ppm/°C. ZnGa₂O₄ ceramics have a low sintering temperature, a wide temperature region, and a small negative τ_f value. They are promising candidate materials for millimeter‐wave devices.     

Properties of porous zirconia ceramics fabricated by using various pore-forming agents

The present work proposes a new method for fabrication partially stabilized porous zirconia ceramics using monoclinic zirconia as raw material, yttrium nitrate and magnesium compounds as pore-forming agents and stabilizers. Effects of different pore-forming agents, firing temperatures and firing time on properties of samples were investigated. Thermal decomposition of yttrium nitrate and magnesium compounds creates a large number of pores, and thus porous zirconia ceramics were fabricated. ZrO₂ can be partially stabilized by Y₂O₃ and MgO derived from the precursors. The porous ZrO₂ ceramics obtained by using Y(NO₃)₃·6H₂O and 4MgCO₃·Mg(OH)₂·6H₂O as pore-forming agents had relatively high stabilization ratio, uniform pores and high strength. The optimum firing temperature and firing time are 1400 °C and 3 h, and the samples have the stabilization ratio of 45.7%, high cold crushing strength (26 MPa), uniform pores, and apparent porosity is about 40%.     

Microstructure and phase transformation behavior of Al2O3–ZrO2 under microwave sintering

Zirconia is an inorganic, nonmetallic material with excellent properties. However, the brittleness of the zirconia, resulting from the thermal performance during the heating and cooling process, seriously limits the application of zirconia in the metallurgical, military, and aerospace industries. Al₂O₃ doped ZrO₂ was developed to improve the potential material's toughness. This paper studied the evolution of the surface functional groups, phase composition, toughening mechanism, and particle morphology of Al₂O₃ doped ZrO₂ during the heating process. Especially microwave heating was selected as the heating method during the experiments to save energy consumption. The results showed that the phase transition temperature was reduced by the microwave sintering technique, which also promoted the transformation between the m-ZrO₂ and t-ZrO₂, advancing the crystallinity and structural properties of the samples. The specific surface area shows a positive relationship with the microwave heating temperature, while the particle size of the powder decreased with the temperature increase. The optimized sintering effect appears at 1000 °C in the studied roasting temperature range (800 °C–1200 °C) for Al₂O₃–ZrO₂ powders. With the optimized sintering temperature, the void of the granular zirconia material was controlled, and the best micromorphology was obtained. In practical production, the application of microwave sintering and alumina doping is beneficial to saving costs and protecting the environment.     

Li2ZrO3 based Li-ion conductors doped with halide ions & sintered in oxygen-deficient atmosphere

All-solid-state batteries have recently attracted much attention for their high energy density and safety. Li₂ZrO₃-based Li-ion conductors with high electrochemical stability have potential applications for electrolytes in all-solid-state batteries. In this work, comparative investigations of Li₂ZrO₃ and halogen doped Li₂ZrO₃ ceramics were conducted by sintering at 700 °C in air or in oxygen-deficient atmosphere which was induced by a simple setup covering with corundum crucible. The analysis of phase composition reveals that the undoped Li₂ZrO₃ ceramic sintered in air contains pure monoclinic phase, while halogen-doped Li₂ZrO₃ sintered in air and all ceramics sintered in oxygen-deficient atmosphere are simultaneously composed of monoclinic and tetragonal phases. Li₂ZrO₃ ceramic with tetragonal phases has higher conductivity (0.28 mS cm⁻¹ for undoped Li₂ZrO₃) than the pure monoclinic Li₂ZrO₃ (0.07 mS cm⁻¹), and halogen doping can further enhance the conductivity of Li₂ZrO₃ ceramics higher than 0.5 mS cm⁻¹ at room temperature.     

Reaction and phases from monoclinic zirconia and calcium aluminate cement at high temperatures

Solid state reaction using m-ZrO₂ and high alumina cement as starting materials was studied. Various compositions containing different proportions of calcium aluminate cement (5–50 mol% CaO in ZrO₂) were reaction sintered at 1300–1500 °C. Crystalline phase formation and densification of Ca stabilized ZrO₂ composites was investigated by X-ray diffraction analysis, density and shrinkage measurements. Scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy was used to examine the microstructure. The main crystalline phases formed are related to the expected with the equilibrium phase diagram of the ZrO₂–CaO–Al₂O₃ system. Stabilized c-ZrO₂ is formed with the composition of Ca_0.15Zr_0.85O_1.85. The sintering of the mixtures leads to porous composites materials. Textural properties were analyzed considering the initial composition and the present crystalline phases.     

Effect of waste-derived MA spinel on sintering and stabilization behavior of partially stabilized double phase zirconia

Cubic-stabilized zirconia ceramic composites have been synthesized by conventional sintering, starting from commercial m-ZrO₂, Y₂O₃, and waste-derived magnesium aluminate spinel (MA) powders. In this work, the effect of sintering temperature and MA content on stabilization and densification properties of YSZ have been duly considered. MA-free YSZ0 composite sintered at 1600°C-1700°C revealed m- and t-ZrO₂ dual-phase structure where its m-ZrO₂ was partially stabilized upon temperature rising into tetragonal phase by Y³⁺ diffusion inside zirconia structure. YSZ10-50 composites containing 10-50 wt% MA demonstrated dissimilar behavior where their m-ZrO₂ was transformed and stabilized into a cubic form by diffusion of Y³⁺, Mg⁺², and Al⁺³ inside zirconia lattice. Furthermore, densification of YSZ10-50 powder mixtures by conventional sintering at 1600°C for 2 hours resulted in fully dense compacts with micrometer-sized grains. The outcomes indicate that MA has a significant effect on m-ZrO₂ stabilization into the cubic phase structure at room temperature. In this respect, this study offers huge potentials for developing fully stabilized c-ZrO₂ ceramics that could be possibly used as industrial ceramics for structural applications of harsh chemical and thermal environmental conditions.