Structural,thermal and mechanical properties of aluminum nitride ceramics with CeO2 as a sintering aid

AlN ceramics have been prepared with CeO₂ as a sintering aid at a sintering temperature of 1900 °C. The effect of CeO₂ contents on the microstructure, density, thermal conductivity and hardness was investigated. Addition of CeO₂ exerted a significant effect on the densification of AlN ceramics and hence on the microstructure. Thermal conductivity of AlN ceramics increased with CeO₂ content and was greater than that of Y₂O₃-doped AlN ceramics at a similar sintering temperature. The resulting AlN ceramics with 1.50 wt% of CeO₂ had the highest relative density of 99.94%, thermal conductivity of 156 W m⁻¹ K⁻¹ and hardness of 72.46 kg/mm².     

Novel two-step sintering and in situ bonding method for fabrication of ZrP2O7 ceramics

Sintering performance at high temperatures is a serious issue for tetravalent metal pyrophosphate MP₂O₇ ceramics (M = Ti, Zr, Hf, Ge, Sn, etc.). Herein, we investigated the influence of high synthesis temperatures and amounts of ZrP₂O₇ precursors on the properties of ZrP₂O₇ ceramics. A ZrP₂O₇ powder was first synthesised via a solid-state reaction; this powder was used in the fabrication of the ZrP₂O₇ ceramic using a combination of two-step sintering and in situ bonding using MgO as the sintering aid. The phase composition and microstructure of the ZrP₂O₇ powder as well as the ZrP₂O₇ ceramic were studied by X-ray diffraction and scanning electron microscopy. The physical properties and room-temperature thermal conductivity of the ZrP₂O₇ ceramic were investigated. The ceramic exhibited high thermal stability at 1350 °C. This study indicates that the mechanical properties of the ZrP₂O₇ ceramic can be enhanced while maintaining their low thermal conductivity by sintering it at 1300 °C with the addition of an appropriate amount of the ZrP₂O₇ precursors to the ZrP₂O₇ powder.     

Ab initio computations of electronic,mechanical, lattice dynamical and thermal properties of ZrP2O7

A systematical ab initio analysis of ZrP₂O₇ is presented in this work. Density functional theory (DFT) computations were performed for the electronic, mechanical, lattice dynamical and thermal properties of ZrP₂O₇. The lattice constants determined from the theoretical calculation are consistent with the experimental results. Based on the analyses on the electronic density of states, charge density and electron localization function of ZrP₂O₇, heterogeneous bonding nature is revealed and confirmed by the phonon density of states. We also reported the second-order elastic constants and polycrystalline mechanical properties of ZrP₂O₇ for the first time. According to the calculated polycrystalline moduli, the minimum thermal conductivity of ZrP₂O₇ is estimated to be 1.15 W m⁻¹ K⁻¹. Our theoretical results illustrate that ZrP₂O₇ is a promising candidate as thermal barrier coating and high temperature binding material.     

On the potential of porous ZrP2O7 ceramics for thermal insulating and wave-transmitting applications at high temperatures

Sintering at high temperature is a serious problem for porous thermal insulating ceramics. To search for sintering-resistant ceramics, ZrP₂O₇ is selected as the backbone material and porous ZrP₂O₇ ceramics with 40−60 vol% porosities and strength of 3−14 MPa are fabricated. The volume shrinkage of the 60 vol% porosity ZrP₂O₇ is only 1.4 % when heated at 1773 K for 6 h and the thermal conductivity, which is as low as 0.18 W m^-1 K^-1, keeps almost unchanged. The dielectric constants are stable in the frequency range of 7−19 GHz when the temperature increases from 298 K to 1273 K. As the porosity increases from 44 % to 60 %, the dielectric constant at 19 GHz and 1273 K decreases from 3.4 to 2.5. Good sintering-resistance, ultra-low thermal conductivity and low dielectric constant at high temperatures make porous ZrP₂O₇ suitable for applications as thermal insulating and wave-transmitting materials at high temperatures.     

Ionic conductivity and mechanical properties of Y2O3-doped CeO2 ceramics synthesis by microwave-induced combustion

We developed a new method, i.e. microwave-induced combustion synthesis to produce highly sinterable Y₂O₃-doped CeO₂ nanopowders. The process took only 15 min to yield Y₂O₃-doped CeO₂ powders. We also investigated the conductivity of Y₂O₃-doped CeO₂ ceramics. It was found Y₂O₃ concentration to have a large effect on the morphology, activation energy, ionic conductivity, and mechanical properties of Y₂O₃-doped CeO₂ ceramics. The results revealed that the bulk densities of Y₂O₃-doped CeO₂ ceramics sintered at 1420 °C for 5 h were all higher than 92% of the theoretical densities, and the maximum ionic conductivity, σ_800 °C = 0.023 S/cm at 800 °C, the minimum activation energy, E_a = 0.954 eV determined in the temperature of 300–800 °C and the maximum fracture toughness, K_IC = 1.825 ± 0.188 MPa m^1/2 were found for 9 mol.% Y₂O₃-doped CeO₂ specimen. The grain size of CeO₂ decreases with increasing Y₂O₃ concentration. The fracture toughness was found to increase at increased Y₂O₃ concentration, because of the decrease of CeO₂ grain size.     

Novel ZrP2O7 ceramic foams with controllable structures and ultra-low thermal conductivity

This study demonstrated the synthesis of novel zirconium pyrophosphate (ZrP₂O₇) ceramic foams via a two-step method using a foam casting technique. The synthesised foams functioned as thermal insulators with a highly controllable performance. We investigated the effects of the addition of foaming and thickening agents as well as the solid content of the slurries on the slurry, mechanical properties, thermal conductivities, and microstructure of ZrP₂O₇ ceramic foams. The ZrP₂O₇ ceramic foams synthesised at 1473 K exhibited a porosity, compressive strength, and thermal conductivity of 75.2–89.1 %, 1.95–0.02 MPa, and 0.144–0.057 W/(m K) (298–573 K), respectively. The increase in the porosity to >60 % will facilitate applications based on the low thermal conductivities of the foams.     

Microstructural evolution and dielectric properties of SiO2-doped CaCu3Ti4O12 ceramics

The abnormal grain growth (AGG) behavior of undoped and SiO₂-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. With the addition of 2 wt.% SiO₂, the AGG-triggering temperature decreased from 1100 to 1060 °C, and the temperature for obtaining a uniform and coarse microstructure decreased from 1140 to 1100 °C. The lowering of the AGG temperature by SiO₂ addition was attributed to the formation of a CuO-SiO₂-rich intergranular phase at lower temperature. The apparent dielectric permittivity of coarse SiO₂-doped CCTO ceramics was ∼10 times higher than that of fine SiO₂-doped CCTO ceramics at the frequency of 10³–10⁵ Hz. The doping of SiO₂ to CCTO ceramics provides an efficient route of improving the dielectric properties via grain coarsening. The correlation between the microstructure and apparent permittivity suggests the presence of a barrier layer near the grain boundary.     

Synthesis,characterization, and electrical conduction of 10 mol% Dy2O3-doped CeO2 ceramics

Well-densified 10 mol% Dy₂O₃-doped CeO₂ (20DDC) ceramics with average grain sizes of ∼0.12–1.5 μm were fabricated by pressureless sintering at 950–1550 °C using a reactive powder thermally decomposed from a carbonate precursor, which was synthesized via a carbonate coprecipitation method employing nitrates as the starting salts and ammonium carbonate as the precipitant. Electrical conductivity of the ceramics, measured by the dc three-point impedance method, shows a V-shape curve against the average grain size. The sample with the smallest grain size of 0.12 μm exhibits a high conductivity of ∼10^−1.74 S/cm at the measurement temperature of 700 °C, which is about the same conduction level of the micro-grained 10 mol% Sm₂O₃- or Gd₂O₃-doped CeO₂, two leading electrolyte materials.     

Crystal structure,infrared-reflectivity spectra,and microwave dielectric properties of novel Ce2(MoO4)2(Mo2O7) ceramics

Novel Ce₂(MoO₄)₂(Mo₂O₇) (CMO) ceramics were prepared by a conventional solid-state method, and the microwave dielectric properties were investigated. X-ray diffraction results illustrated that pure Ce₂(MoO₄)₂(Mo₂O₇) structure formed upon sintering at 600 °C-725 °C. [CeO₇], [CeO₈], [MoO₄], and [MoO₆] polyhedra were connected to form a three-dimensional structure of CMO ceramics. Analysis based on chemical bond theory indicated that the Mo–O bond critically affected the ceramics’ performance. Furthermore, infrared-reflectivity spectra analysis revealed that the primary polarisation contribution was from ionic polarisation. Notably, the optimum microwave dielectric properties of ε_r = 10.69, Q·f = 49,440 GHz (@ 9.29 GHz), and τ_f = −30.4 ppm/°C were obtained in CMO ceramics sintered at 700 °C.     

The effect of rare earth oxides on the pressureless liquid phase sintering of α-SiC

Silicon carbide (SiC) ceramics have been fabricated by pressureless liquid phase sintering with Al₂O₃ and rare-earth oxides (Lu₂O₃, Er₂O₃ and CeO₂) as sintering additives. The effect was investigated of the different types of rare earth oxides on the mechanical property, thermal conductivity and microstructure of pressureless liquid phase sintered SiC ceramics. The room temperature mechanical properties of the ceramics were affected by the type of rare earth oxides. The high temperature performances of the ceramics were influenced by the triple junction grain boundary phases. With well crystallized triple junction grain boundary phase, the SiC ceramic with Al₂O₃–Lu₂O₃ as sintering additive showed good high temperature (1300 °C) performance. With clean SiC grain boundary, the SiC ceramic with Al₂O₃–CeO₂ as sintering additive showed good room temperature thermal conductivity. By using appropriate rare earth oxide, targeted tailoring of the demanding properties of pressureless liquid phase sintered SiC ceramics can be achieved.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

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.     

Structure,thermal properties and hot corrosion behaviors of Gd2Hf2O7 as a potential thermal barrier coating material

In this work, Gd₂Hf₂O₇ ceramics were synthesized and investigated as a potential thermal barrier coating (TBC) material. The phase composition, microstructure and associated thermal properties of Gd₂Hf₂O₇ ceramics were characterized systematically. Results show that the thermal conductivity of Gd₂Hf₂O₇ ceramics is 1.40 Wm⁻¹K⁻¹ at 1200 °C, ~25% lower than that of 8 wt% yttria partially stabilized zirconia (8YSZ). Gd₂Hf₂O₇ ceramics also present large thermal expansion coefficients, which decrease from 12.0 × 10⁻⁶ K⁻¹ to 11.3 × 10⁻⁶ K⁻¹ (300–1200 °C). Besides, the hot corrosion behaviors of Gd₂Hf₂O₇ ceramics exposed to V₂O₅ and Na₂SO₄ + V₂O₅ salts at temperatures of 900–1200 °C were discussed in great detail. We pay much attention on the corrosion process, corrosion mechanism and corrosion damage of Gd₂Hf₂O₇ ceramics subjected to molten V₂O₅ and Na₂SO₄ + V₂O₅ salts at different temperatures.     

Effect of hot-pressing sintering on thermal and electrical properties of AlN ceramics with impedance spectroscopy and dielectric relaxations analysis

The effects of hot-pressing sintering on the phase composition, microstructure, thermal and electrical properties of AlN ceramics with CeO₂–CeF₃ additives were studied. During hot-pressing sintering, high pressure reduced the grain boundary phase CeAlO₃ and decreased the concentration of oxygen in AlN ceramics. The hot-pressing sintered AlN samples had a much higher thermal conductivity of 191.9 W/m·K than pressureless sintered ones because of the great reduction of grain boundary phases and oxygen impurities in AlN ceramic. As the carbon content in hot-pressing sintered sample was very high, carbon contamination led to the decrease in electrical resistivity and changes in polarization mechanisms for AlN ceramics. The relaxation peak in the dielectric temperature spectrum with an activation energy of 0.64 eV for hot-pressing sintered samples was caused by electrons from free carbon at low temperature. Overall, hot-pressing sintering can effectively increase the thermal conductivity and change the electrical properties of AlN ceramics.     

Low-temperature firing and microwave dielectric properties of 16CaO–9Li2O–12Sm2O3–63TiO2 ceramics with V2O5 addition

The sintering behaviors and microwave dielectric properties of the 16CaO–9Li₂O–12Sm₂O₃–63TiO₂ (abbreviated CLST) ceramics with different amounts of V₂O₅ addition had been investigated in this paper. The sintering temperature of the CLST ceramic had been efficiently decreased by nearly 100 °C. No secondary phase was observed in the CLST ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLST ceramics with small amounts of V₂O₅ addition could be well sintered at 1200 °C for 3 h without much degradation in the microwave dielectric properties. Especially, the 0.75 wt.% V₂O₅-doped ceramics sintered at 1200 °C for 3 h have optimum microwave dielectric properties of Kr = 100.4, Q × f = 5600 GHz, and TCF = 7 ppm/°C. Obviously, V₂O₅ could be a suitable sintering aid that improves densification and microwave dielectric properties of the CLST ceramics.     

Preparation and properties of MgAl2O4 spinel ceramics by double-doped CeO2 and La2O3

Magnesium aluminate spinel (MgAl₂O₄) ceramics are high-performance and carbon-free materials widely used in both military and civilian fields. However, it is usually challenging to densify during the solid-state sintering process. The excellent properties of some rare earth oxides have been proved to promote the densification of MgAl₂O₄ spinel ceramics. But the mechanism of promoting sintering is not clear. In the present work, MgAl₂O₄ spinel ceramics have been successfully fabricated by co-doping CeO₂ and La₂O₃ via a single-stage solid-state reaction sintering. The effects of addition amounts of CeO₂ and La₂O₃ on phase compositions, microstructures, sintering characteristics, cold compressive strength, and thermal shock resistance of as-prepared MgAl₂O₄ spinel ceramics were systematically investigated. The results show that by co-doping CeO₂ and La₂O₃ can increase the defect concentration due to the lattice distortion. This could promote the movement of Al³⁺ and Mg²⁺ at high temperature, which is beneficial to the formation of more secondary MgAl₂O₄ spinel. t-ZrO₂ with more Ce⁴⁺ filling between spinel grains could prevent the growth of grains and promote the densification, besides the new-formed LaAlO₃ that was mainly distributed along the grain boundary of the MgAl₂O₄ phase, both of which were favorable for the formation of dense microstructure of MgAl₂O₄ spinel materials. At the same time, the formation of more secondary MgAl₂O₄ spinel and sintering densification also improve the mechanical properties of spinel ceramics. La³⁺ will segregate to the spinel grain boundary, preventing grain boundary movement and absorbing the main crack's fracture energy. With 3 wt% CeO₂ and 3 wt% La₂O₃ co-doping, the bulk density of the sample increased from 3.02 g∙cm⁻³ to 3.55 g∙cm⁻³; the apparent porosity decreased from 12.21% to 9.97%; the cold compressive strength increased from 172.88 MPa to 189.54 MPa; and the residual strength retention ratio after thermal shock increased from 84.92% to 89.15%.     

Structure refinement,defects evolution and calcium doping of Sr2CeO4 microwave dielectric ceramics with high quality factor

Sr_2-2xCa_2xCeO₄ (x = 0, 0.025, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8) ceramics were synthesized through cold isostatic pressing and solid-state reaction. The microstructure, defects, microwave dielectric properties, and the effect of Ca²⁺ doping of Sr₂CeO₄ ceramics were systematically investigated. As the sintering temperature increased, the densities of Sr₂CeO₄ ceramics rose, the content of oxygen vacancies increased, and Ce⁴⁺ reduction would be enhanced. In addition, the Sr₂CeO₄ structure had poor compatibility with Ca²⁺. The major phase could be kept unchanged only when x ≤ 0.1. The reason was that the doping of Ca²⁺ intensified the distortion of the CeO₆ octahedron and induced the structural transformation of the common edges (Sr₂CeO₄) to the common angles (SrCeO₃). With the increase of dopant, the densities of Sr_2-2xCa_2xCeO₄ ceramics increased significantly, while the content of oxygen vacancies also increased. The microwave dielectric properties were mainly influenced by the density, structural symmetry, defects, and the second phase SrCeO₃. The dielectric permittivity (ε_r) of 13.4–15, the quality factor (Qf) of 118,580–52,170 GHz, and the temperature coefficient of resonant frequency (τ_f) of ?58.3 ～ ?47.5 ppm/°C were obtained for Sr_2-2xCa_2xCeO₄ ceramics When x ≤ 0.1. This work has provided a foundation for further research on cerate microwave dielectric ceramics.     

Sintering behavior and microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics modified by B2O3–Li2O–Al2O3 and CeO2

A low temperature sintering method was used to avoid the relatively high sintering temperatures typically required to prepare 0.67CaTiO₃–0.33LaAlO₃ (CTLA) ceramics. Additionally, CeO₂ was introduced into the CTLA ceramics as an oxygen-storage material to improve their microwave dielectric properties. 0.67CaTiO₃–0.33LaAlO₃ ceramics co-doped with B₂O₃–Li₂O–Al₂O₃ and CeO₂ were prepared by a conventional two-step solid-state reaction process. The sintering behavior, crystal structure, surface morphology, and microwave dielectric proprieties of the prepared ceramic samples were studied, and the reaction mechanism of CeO₂ was elucidated. CTLA+0.05 wt% BLA+3 wt% CeO₂ ceramics sintered at 1360 °C for 4 h exhibited the optimal microwave dielectric properties: dielectric constant (ε_r)=45.02, quality factor (Q×f)=43102 GHz, and temperature coefficient of resonant frequency (τ_f)=2.1 ppm/°C. The successful preparation of high-performance microwave dielectric ceramics provides a direction for the future development and commercialization of CTLA ceramics.     

Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics

Porous mullite ceramics are potential advanced thermal insulating materials. Pore structure and purity are the main factors that affect properties of these ceramics. In this study, high performance porous mullite ceramics were prepared via aqueous gel-casting using mullite fibers and kaolin as the raw materials and ρ-Al₂O₃ as the gelling agent. Effects of addition of mullite fibers on the pore structure and properties were examined. The results indicated that mullite phase in situ formed by kaolin, and ρ-Al₂O₃ ensured the purity of mullite samples and mullite fibers bonded together to form a nest-like structure, greatly improving the properties of ceramic samples. In particular, the apparent porosity of mullite samples reached 73.6%. In the presence of 75% of mullite fibers, the thermal conductivity was only 0.289 W/m K at room temperature. Moreover, the mullite samples possessed relatively high cold compressive strength in the range of 4.9–9.6 MPa. Therefore, porous mullite ceramics prepared via aqueous gel-casting could be used for wide applications in thermal insulation materials, attributing to the excellent properties such as high cold compressive strength and low thermal conductivity.     

Effects of CeO2 addition on the properties of cordierite-bonded porous SiC ceramics

Cordierite-bonded porous SiC ceramics were fabricated with and without CeO₂ addition in air by an in situ reaction bonding technique. The effects of CeO₂ addition on the phase composition, microstructure and properties of porous SiC ceramics were investigated. It was found that the CeO₂ addition strongly promotes the phase transformation towards cordierite while inhibits the formation of spinel. With CeO₂ addition, the neck growth was enhanced, and the mechanical properties of porous SiC ceramics were improved. When 2.0 wt.% CeO₂ was added, a flexural strength of 35.3 MPa was achieved at an open porosity of 42.1%. Pore size distribution characterization by mercury porosimetry indicated that 2.0 wt.% CeO₂ addition enlarged the average pore size of porous SiC ceramics and introduced a bigger homogeneity in pore size. In addition, it was found that higher permeability was obtained after adding 2.0 wt.% CeO₂. Moreover, the thermal shock resistance of cordierite-bonded porous SiC ceramics was also improved by the addition of CeO₂.