Effect of High‐Temperature Aging on the Fracture Toughness of 40 mol% Ceria‐Stabilized Zirconia

The 40 mol% CeO₂‐stabilized ZrO₂ ceramic was synthesized by the sol‐spray pyrolysis method and aged at 1400°C–1600°C. The effects of high‐temperature aging on its fracture toughness were investigated after heat treatments at 1500°C for 6–150 h in air. Characterization results indicated that the activation energy for grain growth of 40 mol% CeO₂‐stabilized ZrO₂ was 593 ± 47 kJ/mol. The average grain size of this ceramic varied from 1.4 to 5.6 μm within the aging condition of 1500°C for 6–150 h. The Ce‐lean tetragonal phase has a constant tetragonality (ratio of the c‐axis to a‐axis of the crystal lattice) of 1.0178 during the aging process. It was found that the fracture toughness of 40 mol% CeO₂‐stabilized ZrO₂ was determined to be 2.0 ± 0.1 MPa·m^1/2, which did not vary significantly with prolonging aging time. Since no monoclinic zirconia was detected in the regions around the indentation crack‐middle and crack‐tip, the high fracture toughness maintained after high‐temperature aging can be attributed to the remarkable stability of the tetragonal phase in 40 mol% CeO₂‐stabilized ZrO₂ composition.     

Phase‐dependent radiation‐resistant behavior of BaTiO3: An in situ X‐ray diffraction study

The radiation‐resistant response of BaTiO₃ in the tetragonal and rhombohedral phases on exposure to 100 MeV Ag⁷⁺ ion irradiation was investigated by in situ X‐ray diffraction (XRD) at room temperature (300 K) and low temperature (25 K), respectively. This study revealed that the BaTiO₃ in rhombohedral phase retained crystallinity up to an ion fluence of 1×10¹⁴ ions/cm², whereas tetragonal phase amorphized at much lower fluence viz. 1×10¹³ ions/cm². The in situ XRD along with Raman spectroscopy studies revealed that BaTiO₃ in rhombohedral phase is more radiation resistant than that of tetragonal phase. The density functional theory (DFT) calculations confirmed higher bond strength of rhombohedral phase as compared to tetragonal phase, which supported the experimental result of higher radiation stability of rhombohedral phase. The theoretical predictions on high‐temperature phase will be of relevance to the nuclear waste applications.     

Structural,dielectric, and piezoelectric properties of Ce-doped Bi7Ti4.2Ta0.3W0.5O21 intergrowth ferroelectric ceramics

The Bi_7-xCe_xTi_4.2Ta_0.3W_0.5O₂₁ (BTTW-BITT-xCe, x = 0.05, 0.10, 0.15, 0.20) ceramics were studied as potential materials for high-temperature applications. The microstructure, dielectric, piezoelectric and ferroelectric properties of Ce doped BTTW-BITT samples were analyzed in detail. The results indicated that an appropriate amount of Ce ion doping could inhibit the growth of grains, suppress the relaxation peak, reduce high-temperature dielectric losses, and greatly improve the piezoelectric activities. The optimal ceramics was obtained at x = 0.15, which possessed a maximum piezoelectric constant of d₃₃ = 23.4 pC/N, a high Curie temperature of 713 °C, a loss value of 6% at 500 °C, and a favorable thermal stability of d₃₃ = 21.1 pC/N (90% of the initial value) at 500 °C. This result indicates that BTTW-BITT-0.15Ce has great potential for applications in the high temperature fields. In addition, XPS results showed that there were two Ce valences states, Ce³⁺ and Ce⁴⁺present in the BTTW-BITT-xCe ceramics.     

Microwave Dielectric Properties of Novel Glass‐Free Low‐Firing Li2CeO3 Ceramics

Novel glass–free low temperature firing microwave dielectric ceramics Li₂CeO₃ with high Q prepared through a conventional solid‐state reaction method had been investigated. All the specimens in this paper have sintering temperature lower than 750°C. XRD studies revealed single cubic phase. The microwave dielectric properties were correlated with the sintering conditions. At 720°C/4 h, Li₂CeO₃ ceramics possessed the excellent microwave dielectric properties of ε_r = 15.8, Q × f = 143 700 (GHz), and τ_f  = ?123 ppm/°C. Li₂CeO₃ ceramics could be excellent candidates for glass‐free low‐temperature co‐fired ceramics substrates.     

Experimental Phase Diagram Determination and Thermodynamic Assessment of the CeO2‐Gd2O3‐CoO System

New phase diagram data and a thermodynamic assessment of the CeO‐Gd₂O₃‐CoO system using the CALPHAD approach are presented. This information is needed to understand the surprisingly low sintering temperature (950°C–1050°C) of CeO₂‐based materials doped with small amounts of transition metal oxide (e.g., CoO). Experimental phase equilibria between 1100°C and 1300°C are reported based on the analysis of annealed and molten samples. No isolated compound exists in the ternary. At 1300°C the Co solubility in the ternary compounds Ce_1?x?yGd_xCo_yO_2?x/2?y (fluorite) is 2.7 mol% and is less than 1 mol% in the Gd_2?xCe_xO_3+x/2 (bixbyite). The Ce solubility in the perovskite GdCoO_3?δ was found to be 1 mol%. The lowest temperature eutectic melt in the ternary has a composition of 57.2 mol% Co and 41.1 mol% Gd melting at an onset temperature of 1303 ± 5°C, which is close to the binary eutectic in the Gd₂O₃‐CoO system at 60 ± 2 mol% Co and 1348 ± 1°C.     

Zr‐ and Tb‐doped barium cerate‐based cermet membrane for hydrogen separation application

Ba_0.8Ce_0.35Zr_0.5Tb_0.15O_3‐δ (BCZT) perovskite has been synthesized by glycine‐assisted solution combustion method. The Ni‐Ba_0.8Ce_0.35Zr_0.5Tb_0.15O_3‐δ‐based cermet membrane is obtained by cosintering NiO and BCZT powder mixture at 1550°C in reducing atmosphere. The X‐ray diffraction pattern of sintered pellet shows the characteristic peaks of both Ni and BCZT phases. FESEM image and elemental mapping confirm the presence of randomly distributed metallic nickel in the BCZT matrix. An electrical conductivity of ~14 S/cm at 700°C is achieved in Ni‐BCZT membrane, which reduced further with increase in temperature (>700°C). The cermet membrane (1.5 mm thick) shows a highest hydrogen permeation flux of ~0.07 mL/min/cm² at 900°C. Chemical stability of Ni‐BCZT membrane has also been examined under humid and carbon dioxide containing atmosphere. The membrane shows good structural stability without any significant change in hydrogen permeation flux.     

Superior temperature‐stable dielectrics for MLCCs based on Bi0.5Na0.5TiO3‐NaNbO3 system modified by CaZrO3

An ultra‐wide temperature stable ceramic system based on (1?x) [0.94(0.75Bi_0.5Na_0.5TiO₃?0.25NaNbO₃)?0.06BaTiO₃]?xCaZrO₃ (CZ100x) is developed for capacitor application in this study. All samples exhibit characteristics of pseudocubic structures in XRD patterns. With CaZrO₃ addition, the coupling effect of polar nanoregions (PNRs) is weakening, leading to greatly improved temperature stability of dielectric properties. Among all samples, the most attractive properties are obtained in the composition of CZ10 at <15% variation in dielectric permittivity spanning from ?55°C to 400°C and lower than 0.02 of dielectric loss of between ?60°C and 300°C, accompanied by high DC resistivity (10⁷ Ω m at 300°C, calculated by fitting Jonscher's power law). Furthermore, tentative multilayer ceramic capacitors (MLCCs) composed of CZ10 dielectric and Ag:Pd (70:30) internal electrode layers were fabricated by tape casting and cofiring processes. Temperature‐stable dielectric property in formation of MLCC was successfully realized, with small ΔC/C_25°C (<15%) and loss factor (≤ 0.02) between ?55°C and 340°C. Meanwhile, CZ10‐based MLCC showed temperature‐insensitive energy storage density of 0.31?0.35 J/cm³ and high‐energy efficiency of above 77% at 120 kV/cm in the range of ?55 to 175°C. All of these exhibit wonderful temperature‐stable dielectric properties and indicate the promising future of CZ10 dielectric as high‐temperature ceramic capacitors.     

Determinations of Ce solid solution mechanism and limit thermal conductivity of YTaO4 ceramics

x mol% CeO₂-YTaO₄ (x = 0, 3, 6, 9, 12) ceramics have been synthesized by the spark plasma sintering (SPS) technique. We focus on the changes in lattice distortion, bonding length, thermal conductivity, thermal expansion, and phase stability of the prepared samples. XRD, Raman, and XPS are used to determine the chemical valence and solid solution mechanism of Ce in the lattice of YTaO₄, while its effects on thermal/mechanical properties are elucidated from microstructures. Y³⁺ is substituted via Ce³⁺, and all samples maintain a monoclinic phase. The limit thermal conductivity (1.2 W?m^?1?K^?1, 900 °C) is realized in 9 mol% CeO₂-YTaO₄, and the thermal expansion coefficients are increased to 10.2 × 10^?6 K^?1 at 1200 °C. Furthermore, the exceptional phase stability and mechanical properties of all samples indicate that they can provide good thermal insulation at high temperatures, and have higher working temperatures than the current YSZ thermal barrier coatings.     

Novel BiFeO3–BaTiO3–Ba(Mg1/3Nb2/3)O3 Lead‐Free Relaxor Ferroelectric Ceramics for Energy‐Storage Capacitors

A novel lead‐free relaxor ferroelectric ceramic of (0.67?x)BiFeO₃–0.33BaTiO₃–xBa(Mg_1/3Nb_2/3)O₃ [(0.67?x)BF–0.33BT–xBMN, x = 0–0.1] was prepared by a solid‐state reaction method. A relatively high maximum polarization P_max of 38 μC/cm² and a low remanent polarization P_r of 5.7 μC/cm² were attained under 12.5 kV/mm in the x = 0.06 sample, leading to an excellent energy‐storage density of W ~1.56 J/cm³ and a moderate energy‐storage efficiency of η ~75%. Moreover, a good temperature stability of the energy storage was obtained in the x = 0.06 sample from 25°C to 190°C. The achievement of these characteristics was basically attributed to an electric field induced reversible ergodic to ferroelectric phase transition owing to similar free energies near a critical freezing temperature. The results indicate that the (0.67?x)BF–0.33BT–xBMN lead‐free realxor ferroelectric ceramic could be a promising dielectric material for energy‐storage capacitors.     

Significant Enhancement of the Dielectric Constant through the Doping of CeO2 into HfO2 by Atomic Layer Deposition

Films of CeO₂ were deposited by atomic layer deposition (ALD) using a Ce(mmp)₄ [mmp = 1‐methoxy‐2‐methyl‐2‐propanolate] precursor and H₂O reactant. The growth characteristics and film properties of ALD CeO₂ were investigated. The ALD CeO₂ process produced highly pure, stoichiometric films with polycrystalline cubic phases. Using the ALD CeO₂ process, the effects of Ce doping into an HfO₂ gate dielectric were systematically investigated. Regardless of Ce/(Ce + Hf) composition, all ALD Ce_xHf_1?xO₂ films exhibited constant growth rates of approximately 1.3 Å/cycle, which is essentially identical to the ALD HfO₂ growth rates. After high‐temperature vacuum annealing at 900°C, it was verified, based on X‐ray diffraction and high‐resolution cross‐sectional transmission electron microscopy results, that all samples with various Ce/(Ce + Hf) compositions were transformed from nanocrystalline to stabilized cubic or tetragonal HfO₂ phases. In addition, the dielectric constant of the Ce_xHf_1?xO₂ films significantly increased, depending on the Ce doping content. The maximum dielectric constant value was found to be nearly 39 for the Ce/(Ce + Hf) concentration of ~11%.     

Low‐Temperature Sintering and Electric Properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 Ferroelectric Ceramics with CuO Additive

The low‐temperature sintering and electric properties of Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ (PZTN 95/5) ferroelectric ceramics with CuO addition was investigated. The CuO addition significantly promoted the densification and reduced the sintering temperature of PZTN 95/5 ceramics by more than 200°C. The 0.2 wt% CuO‐added sample sintered at 1150°C exhibited the optimum relative density of 96.7% and excellent electric properties with values of P_r = 37.80 μC/cm², T_C = 223°C, ε_r = 329, and tan δ = 0.016, which were superior to that of PZTN 95/5 ceramics sintered at 1350°C.     

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

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

Large electric‐field‐induced strain and enhanced piezoelectric constant in CuO‐modified BiFeO3‐BaTiO3 ceramics

In this work, we fabricated the (1‐x)BiFeO₃‐xBaTiO₃+y‰ mol CuO ceramics by the modified thermal quenching technique. The pure perovskite phase was formed and a morphotropic phase boundary (MPB) was observed in the ceramics with x = 0.30‐0.33. The addition of CuO can significantly enhance the density of the BiFeO₃‐BaTiO₃ material. Importantly, an enhanced piezoelectric constant (d₃₃=165 pC/N), a large electric‐field‐induced strain (?S = 0.54%: peak to peak strain) and a large piezoelectric actuator constant (d₃₃*=449 pm/V) together with a high Curie temperature (T_C) of 503°C were observed in the ceramics with x = 0.30 and y = 5. As a result, the enhanced piezoelectricity and large electric‐field‐induced strain could significantly stimulate further researches in BFO‐based ceramics.     

Bio-template synthesis of CeO2 ultrathin nanosheets for highly selective and sensitive detection of ppb-level p-xylene vapor

Highly selective of carcinogenic and flammable p-xylene vapor and its sensing detection through metal oxides-based sensors has recently attracted much attention. In this work, mesoporous CeO₂ nanosheets were synthesized by simple cerium nitrate impregnation and air calcination using rose petals as bio-template. The effect of calcination temperature on its microstructure, Ce³⁺/Ce⁴⁺ mole ratio, as well as sensing performance was investigated. The CeO₂-650 ultrathin nanosheets calcined at 650 °C are assembled by cross-linking nanoparticles with small size, which possess homogeneous mesoporous distribution and relatively large specific surface area. At 217 °C, the sensor fabricated from CeO₂-650 ultrathin nanosheets shows short response time (T_res = 5 s), high selectivity and response (S = 22.1) towards 100 ppm p-xylene vapor, and its limit of detection (30 ppb) is the lowest among reported sensors based on pure metal oxides. The good sensing performance mainly originate from the synergistic effect of intrinsic features of mesoporous CeO₂-650 ultrathin nanosheets, surface adsorbed oxygen control, oxygen vacancy defects induced by Ce³⁺ and biotemplate imprinting. Therefore, mesoporous CeO₂-650 ultrathin nanosheets could be utilized as candidate for the detection of trace p-xylene vapor.     

Ce3+ doped Lu3Al5O12 ceramics prepared by spark plasma sintering technology using micrometre powders: Microstructure,luminescence, and scintillation properties

Ce³⁺ doped Lu₃Al₅O₁₂ (Ce:LuAG) ceramics were fabricated by the solid-state reaction method through spark plasma sintering (SPS) from 1350 °C to 1700 °C for 5 min at a pressure of 50 MPa using micro powders. The average grain size of the SPSed ceramics gradually grew from 0.42 µm (1400 °C) to 1.55 µm (1700 °C), which is nearly one order of magnitude lower than that of vacuum sintered (VSed) Ce:LuAG ceramics (~24.6 µm). Characteristic Ce³⁺ emission peaking at around 510 nm appeared and 92% photoluminescence intensity of room temperature can be reserved at 200 °C revealing excellent thermal stability. The maximum radioluminescence intensity reached around 3 times of VSed Ce:LuAG ceramics and 7.8 times of BGO crystals. The maximum scintillation light yield under γ-ray (¹³⁷Cs) excitation reached 9634 pho/MeV @ 2 μs. It is concluded that SPS technology is a feasible way to develop Ce:LuAG ceramics and further optical enhancement can be expected.     

Lattice Defects Induce Multiferroic Responses in Ce,La‐Substituted BaFe0.01Ti0.99O3 Nanostructures

Single‐phase multiferroic Ba(Fe_0.67Ce_0.33)_0.01Ti_0.99O₃ (BFTO:Ce) and Ba(Fe_0.67La_0.33)_0.01Ti_0.99O₃ (BFTO:La) nanostructures were synthesized by a hydrothermal method (180°C/48 h). Rietveld refinement of X‐ray diffraction could confirm crystalline phase and lattice deformation by Ce, La into BFTO. The Ce and La doping induce nanoaggregation‐type BFTO nanostructural product due to their ionic size effect and chemical behavior with OH^? ions. Raman active modes show tetragonal phase and defects due to vacancies in the BFTO lattice. Photoluminescence spectrum involves multiple visible emissions due to defects/vacancies. The observed ferroelectric polarization is enhanced due to shape/size effect of nanoparticles, lattice distortion, and filling of d orbital in the perovskite BaTiO₃. The room‐temperature magnetic behavior is described due to antiferromagnetic interactions that strengthen by Ce and La doping. The zero‐field cooling and field cooling magnetic measurement at 500 Oe indicates antiferromagnetic to ferromagnetic transition. Dynamic magnetoelectric coupling was investigated, and maximum longitudinal magnetoelectric coefficient is 62.65 and 49.79 mV/cmOe, respectively, measured for BFTO:Ce and BFTO:La. The magnetocapacitance measurements induce negative values that described in terms of magnetoresistance and magnetic phase transition effects. The influence of oxygen vacancy on multiferroicity is evaluated by valance states of O ions.     

Temperature‐Stable Relative Permittivity from −70°C to 500°C in (Ba0.8Ca0.2)TiO3–Bi(Mg0.5Ti0.5)O3–NaNbO3 Ceramics

Temperature‐stable relaxor dielectrics have been developed in the solid solution system: 0.45Ba_0.8Ca_0.2TiO₃–(0.55 ? x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃. Ceramics of composition x = 0 have a relative permittivity ?_r = 950 ± 15% over a wide temperature range from +70°C to 600°C. Modification with NaNbO₃ at x = 0.2 decreases the lower limiting temperature to ?70°C, but also decreases relative permittivity such that ?_r ~ 600 ± 15% over the temperature range ?70°C to 500°C. For composition x = 0.3, the low‐temperature dispersion in loss tangent, tan δ, (at 1 kHz) shifts to lower temperature, giving tan δ values ≤0.02 across the temperature range ?60°C to 300°C in combination with ?_r ~ 550 ± 15%. Values of dc resistivity for all samples are of the order of 10¹⁰ Ω m at 250°C and 10⁷ Ω m at 400°C.     

Microstructure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of Sc‐Modified BiFeO3–BaTiO3 Multiferroic Ceramics with MnO2 Addition

0.725BiFe_1?xSc_xO₃–0.275BaTiO₃ + y mol% MnO₂ multiferroic ceramics were fabricated by a conventional ceramic technique and the effects of Sc doping and sintering temperature on microstructure, multiferroic, and piezoelectric properties of the ceramics were studied. The ceramics can be well sintered at the wide low sintering temperature range 930°C–990°C and possess a pure perovskite structure. The ceramics with x/y = 0.01–0.02/1.0 sintered at 960°C possess high resistivity (~2 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 19.1–20.4 μm/cm²), good piezoelectric properties (d₃₃ = 127–128 pC/N, k_p = 36.6%–36.9%), and very high Curie temperature (618°C–636°C). The increase in sintering temperature improves the densification, electric insulation, ferroelectric, and piezoelectric properties of the ceramics. A small amount of Sc doping (x ≤ 0.04) and the increase in the sintering temperature significantly enhance the ferromagnetic properties of the ceramics. Improved ferromagnetism with remnant magnetization M_r of 0.059 and 0.10 emu/g and coercive field H_c of 2.51 and 2.76 kOe are obtained in the ceramics with x/y = 0.04/1.0 (sintered at 960°C) and 0.02/1.0 (sintered at 1050°C), respectively. Because of the high T_C (636°C), the ceramic with x/y = 0.02/1.0 shows good temperature stability of piezoelectric properties. Our results also show that the addition of MnO₂ is essential to obtain the ceramics with good electrical properties and electric insulation.     

Effects of cerium on structures and electrical properties of (Nb,Ta) modified Bi4Ti3O12 piezoelectric ceramics

Bi₄Ti₃O₁₂ high-temperature piezoelectric ceramics composed of 0.03 mol (Nb, Ta)⁵⁺ substituting B site and x mol CeO₂ (x = 0–0.05, abbreviated as BCTNT100x) substituting A site were synthesized by the conventional solid-state reaction method. The effects of Ce additive on the structures and electrical properties of resulting Bi₄Ti₃O₁₂-based ceramics were systematically investigated. In-situ temperature-dependent X-ray diffraction (XRD) confirmed that the phase structure of BCTNT100x ceramics change from orthorhombic structure to tetragonal structure as temperature increased. The ceramics at Ce content x = 0.03 illustrated optimal performances with superior piezoelectric constant (d₃₃ = 36.5 pC/N), high Curie temperature (T_C = 649 °C), and large remanent polarization (2P_r = 21.6 μC/cm²). BCTNT3 ceramics also possessed high d₃₃ of 32.5 pC/N at an annealing temperature of 600°C, with electrical resistivity preserved at 10⁶ Ω cm at 500 °C. These results demonstrate that BCTNT100x ceramics can be used as high-temperature piezoelectric devices.