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Microwave Absorption Properties of BiFeO3-based Solid Solution Powders
Journal of Ceramics 2025, 46(5): 1018-1026
Published: 01 October 2025
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Background and purposes

With the rapid development of radar and semiconductor technologies, intelligent electronic devices are widely used in autonomous vehicles, 5G base stations and unmanned aerial systems. The electromagnetic radiation pollution not only disrupts the function of nearby electronic equipment but also compromises information security. The most efficacious approach to address this issue is to develop advanced electromagnetic wave absorbers with strong absorption, thin thickness and wide absorption bandwidth. Bismuth ferrite (BiFeO3) exhibits magnetoelectric coupling effects at room temperature, holding promise for applications as microwave absorbing materials. However, its inherent weak magnetism and insufficient impedance matching restrict its development as an absorbing material. In this study, BiFeO3, Bi0.9La0.1FeO3, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 powders were synthesized by using chemical co-precipitation method. The effects of rare-earth element on phase composition, microstructure, elemental distribution, oxygen vacancy concentration, electromagnetic parameters, and microwave absorption properties of the BiFeO3-based solid solution materials were systematically studied. With increasing content of rare-earth element, BiFeO3 gradually transitioned from a rhombohedral structure to an orthorhombic structure, while the Bi2O3 impurity phase in the obtained materials gradually disappeared and the oxygen vacancy concentration increased. Excessively high oxygen vacancy concentration tended to weaken the microwave absorption performance of the materials. Bi0.9La0.1FeO3 exhibited a moderate oxygen vacancy concentration, achieving a minimum reflection loss (RLmin) of - 42.62 dB at a thickness of 2.36 mm and a maximum effective absorption bandwidth (EABmax) of 1.38 GHz, demonstrating the optimal microwave absorption performance among the synthesized BiFeO3-based solid solutions. The results provided guiding significance for the solid solution composition design and performance regulation of novel microwave absorbing materials.

Methods

A series of BiFeO3-based powders, including BiFeO3, Bi0.9La0.1FeO3, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3, were synthesized by using a chemical co-precipitation method. Stoichiometric amounts of metal nitrates (Bi, La, Nd, Sm, Fe)were dissolved in deionized water, followed by a series of processes, including ammonia precipitation, centrifugation and drying. The precursors were calcined at 600-1000 ℃ for 2 h to obtain phase-pure powders. Phase composition of the as-synthesized particles was characterized by using X-ray diffraction analyzer (XRD, D8 Advance, Bruker). Particle sizes of the synthesized powders were measured by using a laser particle size analysis (Litersizer500, Anton Paar, Austria). Microstructure and element distribution were analyzed by using field emission scanning electron microscope (SEM, SU8010, Hitachi, Japan) equipped with an energy dispersive X-ray spectrometer (EDS, SU8220, Hitachi, Japan). Chemical composition and electronic states of the synthesized powders were examined by using X-ray photoelectron spectroscopy (XPS, Escalab 250Xi). Electromagnetic parameters, namely complex permittivity and permeability, were measured with a vector network analyzer in the 2-18 GHz frequency range. Microwave absorption properties, including reflection loss (RL) and effective absorption bandwidth (EAB), were calculated according to transmission line theory.

Results

XRD results revealed that 20 at.% La solid solution induced a rhombohedral-to-orthorhombic phase transition in BiFeO3. Further multi-element solid solutions (Bi0.33La0.33Nd0.33FeO3) stabilized the single orthorhombic perovskite phase(PDF#86-1518). The average particle size of BiFeO3 is~713 nm. The particle size of 10 at.% La solid solution decreased to~201 nm, whereas those of Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 increased to~824 nm and~2.23 μm, respectively. EDS results confirmed uniform element distribution without segregation. XPS results showed that the multi-element solid solutions significantly had increased oxygen vacancy concentrations. Among the synthesized powders, Bi0.9La0.1FeO3 exhibited optimal microwave absorption performance, achieving a minimum reflection loss (RLmin) of - 42.62 dB at 12.4 GHz (2.36 mm thickness) and an EABmax of 1.38 GHz (5 mm thickness). In contrast, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 showed degraded microwave absorption performance, with RLmin of - 16.35 dB and - 24.79 dB, respectively, due to excessive oxygen vacancies, which weakened the unevenness of charge distribution, thereby leading to a reduction in polarization effects and consequently disrupted impedance matching and weakened polarization relaxation.

Conclusions

BiFeO3 powder and Bi0.9La0.1FeO3, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 solid solution powders were synthesized by using a chemical co-precipitation method, to study the effects of rare-earth element at the Bi-site on phase composition, microstructure, oxygen vacancy concentration, electromagnetic parameters and microwave absorption properties of BiFeO3. The main conclusions are as follows.

(1) Rare-earth element doping at the Bi-site altered the crystal structure of BiFeO3 and inhibited the presence of Bi2O3 n the final products. The as-synthesized pure BiFeO3 exhibited a rhombohedral structure with a certain amount of Bi2O3. When the La content increased from 10 at.% to 20 at.%, phase transition occurred from rhombohedral to orthorhombic structure, while the content of Bi2O3 impurity phase significantly reduced. Further increasing the doping content and types of rare-earth elements resulted in Bi0.33La0.33Nd0.33FeO3 with single orthorhombic perovskite structure without the presence of Bi2O3.

(2) Rare-earth element doping at the Bi-site varied the oxygen vacancy concentration in BiFeO3, thereby regulating the microwave absorption performance of the materials. The oxygen vacancy concentrations of pure BiFeO3 powder and Bi0.9La0.1FeO3, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 solid solution powders increased with increasing content of the rare-earth element. Bi0.9La0.1FeO3 exhibited a moderate oxygen vacancy concentration and the optimal microwave absorption performance, achieving a minimum reflection loss (RLmin) of - 42.62 dB at a thickness of 2.36 mm at 12.4 GHz, with a maximum effective absorption bandwidth (EABmax) extended to 1.38 GHz (at 5 mm thickness). Its excellent performance originated from the significant increase in dielectric loss and ideal impedance matching, enabling efficient electromagnetic wave absorption and dissipation near 12 GHz. In contrast, Bi0.8La0.2FeO3 and Bi0.33La0.33Nd0.33FeO3 had excessively high oxygen vacancy concentrations, which weakened the uneven charge distribution and thus reduced the polarization effect, leading to reduction in microwave absorption performance.

Open Access Issue
The Indentation Load Effect of Hardness of Non-Stoichiometric High-Entropy Carbides (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C1-x
Advanced Ceramics 2024, 45(1-2): 169-176
Published: 01 April 2024
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This paper studied the indentation size effect (ISE) of non-stoichiometric high-entropy carbide ceramics (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C1-x (HEC1-x, x=0-0.5) with different carbon vacancy concentration. The experimental results showed that the indentation size increased and the hardness decreased rapidly as the load increased from 0.05 kgf to 1 kgf. Moreover, the proportional specimen resistance (PSR) model can describe the indentation size effect of high-entropy carbides in this study. The hardness decreased gradually with the load rised, but the degree of change decreased first and then increased with the increase of carbon vacancy concentration, which revealed that the ISE in HEC1-x system had the same trend of variation with the increase of carbon vacancy concentration. The hardness of HEC0.8 had the smallest change with the increase of load, indicating it had the weakest ISE. According to the fited polynomial curves of load-indentation size relationship, the true hardness of ceramics increased first and then decreased with the increase of carbon vacancy concentration, and the maximum value was 22.2 GPa at HEC0.9.

Open Access Issue
The Effect of SiC on The Laser Ablation Resistance of High-Entropy Diboride Ceramics
Advanced Ceramics 2024, 45(5): 417-433
Published: 01 October 2024
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ablation resistance is a key property of ultra-high temperature ceramics (UHTCs) for application in aviation and aerospace. The laser ablation test is one of the effective methods to evaluate the ablation resistance of UHTCs. High-entropy diboride ceramics is a new member of the family of UHTCs, and it is of great significance to understand its laser ablation resistance and related mechanisms for the development of new high-performance UHTCs. However, the laser ablation resistance of highentropy diboride ceramics is not known clearly till now. In response to this problem, the laser ablation resistance of high-entropy diboride (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 (HEB) ceramics and (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2-20 vol % SiC (HEB-20SiC) composite ceramics have been investigated using a CO2 laser with wavelength of 10.6 μm and spot diameter of 2 mm to heat the surface of the samples upto ultra-high temperatures in this work. The effect of the SiC secondary phase on the hightemperature oxidation and ablation behavior of HEB ceramics has been studied. It is found that the highest surface temperature, the linear ablation rate and the mass ablation rate of HEB composite ceramics after the laser powder density reached 57.3 MW/m2 and dwelled 300 s are 2256 ℃, 0.12 μm/s and -0.014 mg/s, respectively. In contrast, under the same laser ablation test condition, the highest surface temperature, the linear ablation rate and the mass ablation rate of HEB-20SiC composite ceramics are 2168 ℃, 0.08 μm/s and -0.007 mg/s, respectively, which are lower than those of HEB ceramics by ~100 ℃, 33.3 % and 50 %. HEB-20SiC ceramics have higher thermal conductivity than HEB ceramics, and the SiO2 phase produced by the oxidation of the SiC phase melts and evaporates at high temperatures, which takes away part of the heat and consequently effectively reduces the ablation temperature on the surface of the samples so that HEB-20SiC ceramics show better laser ablation resistance than HEB ceramics

Open Access Issue
Oxidation Resistance of Equimolar Multicomponent Transition Metal Carbide Solid Solution
Advanced Ceramics 2024, 45(6): 541-557
Published: 01 December 2024
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transition metal carbides and their solid solutions have high melting points and excellent mechanical properties, which have broad application prospects in the machining and aerospace industries. However, their low oxidation resistance at high temperatures limits further development and applications. In this work, using ZrC as the basic group component, by introducing IVB and VB group transition metal elements Ti, Hf, Nb and Ta, the binary, ternary, quaternary and quinary equimolar transition metal carbide solid solution powders are synthesized by carbothermal reduction process and their dense ceramics with compositions of (Ti1/2Zr1/2)C、(Ti1/3Zr1/3Hf1/3)C、(Ti1/4Zr1/4Hf1/4Nb1/4)C、(Ti1/4Zr1/4Hf1/4Ta1/4)C、(Ti1/4Zr1/4Nb1/4Ta1/4)C、(Zr1/4Hf1/4Nb1/4Ta1/4)C、(Ti1/5Zr1/5Hf1/5Nb1/5Ta1/5)C are prepared by spark plasma sintering. The oxidation resistance of the ceramics at 1200℃ in flowing air is evaluated. The effects of the component number and the transition metal elements on the materials' oxidation behavior are analyzed. The results show that all the samples are single-phase solid solutions with NaCl-type cubic crystal structure. As the component number increases, the mixing entropy of the materials increases, and the thickness of the oxide layer and the oxidation weight gain rate of the materials after the oxidation test becomes smaller. Among the four quaternary carbide solid solution ceramics with the same mixing entropy, the carbide solid solution ceramics containing Nb elements showed better oxidation resistance. After oxidized at 1200 ℃ for 10 min in flowing air, five-component transition metal carbide solid solution (Ti1/5Zr1/5Hf1/5Nb1/5Ta1/5)C ceramics with the largest mixing entropy and containing Nb elements shows an oxide layer thickness 21.5 μm and a mass gain per unit surface area of 1.62 mg/cm2, respectively, which were significantly lower than those of other binary, ternary, and quaternary equimolar carbide solid solution ceramics. The results reveal increased mixing entropy of the multicomponent transition metal carbides solid solution improved their thermodynamic stability. Meanwhile, the low-melting-point oxidation products, such as Nb2O5 and Zr6Nb2O17, promoted the densification of the surface oxide layer. These two factors synergistically improve the oxidation resistance of the prepared ceramics. The study can provide a reference for the new compositional design of antioxidant transition metal carbide ceramics.

Issue
Structure and Mechanical Properties of ZrN1-x Ceramics Prepared with Reactive Spark Plasma Sintering
Journal of Ceramics 2022, 43(4): 629-636
Published: 01 August 2022
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ZrN1−x (x = 0–0.3) ceramics with different nitrogen vacancy concentrations were prepared by using reactive spark plasma sintering, with ZrN and ZrH2 powders as raw materials. With increasing concentration of nitrogen vacancy from 0 to 0.3, relative density of the samples sintered at 1600 ℃ increased from 90.5% to 99.6%, while the second phase of ZrO2 gradually dissolved into the matrix, the oxygen content of the matrix phase increased from 0.03 at.% to 10.04 at.%, the average grain size increased from 3.12 μm to 33.13 μm and the lattice constant first increased and then decreased. The lattice constants of ZrN1.0, ZrN0.9, ZrN0.8 and ZrN0.7 are 4.5769 Å, 4.5806 Å, 4.5834 Å and 4.5799 Å, respectively. The Young's modulus of ZrN1−x decreased gradually with increasing concentration of nitrogen vacancy, while the Young's modulus of ZrN1.0-1700 and ZrN0.7-1600 with similar relative density were 365 GPa and 300 GPa, respectively. The experimental lattice constant and Young's modulus are consistent with the first-principles calculations results.

Open Access Research Article Issue
Dual-phase medium-entropy diboride–carbide ceramics with metal element exchange during sintering
Journal of Advanced Ceramics 2025, 14(1): 9221007
Published: 13 January 2025
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Multiphase composition design is a strategy for optimizing the microstructures and properties of ceramic materials through mutual inhibition of grain growth, complementary property improvement, or even mutually reinforcing effects. More interesting phenomena can be expected if chemical interactions between the constituent phases exist. In this study, spark plasma sintering was used to prepare fully dense dual-phase (Zr,Hf,Ta)B2–(Zr,Hf,Ta)C ceramics from self-synthesized equimolar medium-entropy diboride and carbide powders. The obtained ceramics were composed of two distinct solid solution phases, the Zr-rich diboride phase and the Ta-rich carbide phase, indicating that metal element exchange occurred between the starting equimolar medium-entropy diboride and carbide phases during sintering. Owing to the mutual grain-boundary pinning effect, fine-grained dual-phase ceramics were obtained. The chemical driving force originating from metal element exchange during the sintering process is considered to promote the densification process of the ceramics. The metal element exchange between the medium-entropy diboride and carbide phases significantly increased the Young’s modulus of the dual-phase ceramics. The dual-phase medium-entropy 50 vol% (Zr,Hf,Ta)B2–50 vol% (Zr,Hf,Ta)C ceramics with the smallest grain size exhibited the highest hardness of 22.4±0.2 GPa. It is inferred that optimized comprehensive properties or performance of dual-phase high-entropy or medium-entropy ceramics of diborides and carbides can be achieved by adjusting both the volume content and the metal element composition of the corresponding starting powders of diborides and carbides.

Open Access Review Issue
Emerging high-entropy strategy: A booster to the development of cathode materials for power batteries
Journal of Advanced Ceramics 2024, 13(8): 1093-1118
Published: 30 August 2024
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The coordinated development of new energy vehicles and the energy storage industry has become essential for reducing carbon emissions. The cathode material is the key material that determines the energy density and cost of a power battery, but currently developed and applied cathode materials cannot meet the requirements for high specific capacity, low cost, safety, and good stability. High-entropy materials (HEMs) are a new type of single-phase material composed of multiple principal elements in equimolar or near-equimolar ratios. The interaction between multiple elements can play an important role in improving the comprehensive properties of the material, which is expected to solve the limitations of battery materials in practical applications. Therefore, this review provides a comprehensive overview of the current development status and modification strategies of power batteries (lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs)), proposes a high-entropy design strategy, and analyses the structure–activity relationship between the high-entropy effects and battery performance. Finally, future research topics related to high-entropy cathode materials, including computational guide design, specific synthesis methods, high-entropy electrochemistry, and high-throughput databases, are proposed. This review aims to provide practical guidance for the development of high-entropy cathode materials for next-generation power batteries.

Open Access Research Article Issue
Synergistic effects of high-entropy engineering and particulate toughening on the properties of rare-earth aluminate-based ceramic composites
Journal of Advanced Ceramics 2023, 12(4): 861-872
Published: 14 March 2023
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Rare-earth aluminates (REAlO3) are potential thermal barrier coating (TBC) materials, but the relatively high thermal conductivity (k0, ~13.6 W·m−1·K−1) and low fracture toughness (KIC, ~1.9 MPa·m1/2) limit their application. This work proposed a strategy to improve their properties through the synergistic effects of high-entropy engineering and particulate toughening. High-entropy (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)AlO3 (HEAO)-based particulate composites with different contents of high-entropy (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 (HEZO) were designed and successfully prepared by solid-state sintering. The high-entropy feature of both the matrix and secondary phases causes the strong phonon scattering and the incorporation of the HEZO secondary phase, remarkedly inhibiting the grain growth of the HEAO phase. As a result, HEAO–xHEZO (x = 0, 5%, 10%, 25%, and 50% in volume) ceramic composites show low thermal conductivity and high fracture toughness. Compared to the most commonly applied TBC material—yttria stabilized-zirconia (YSZ), the HEAO–25%HEZO particulate composite has a lower thermal conductivity of 0.96–1.17 W·m−1·K−1 (298–1273 K), enhanced fracture toughness of 3.94±0.35 MPa·m1/2, and comparable linear coefficient of thermal expansion (CTE) of 10.5×10−6 K−1. It is believed that the proposed strategy should be revelatory for the design of new coating materials including TBCs and environmental barrier coatings (EBCs).

Open Access Research Article Issue
Fast grain growth phenomenon in high-entropy ceramics: A case study in rare-earth hexaaluminates
Journal of Advanced Ceramics 2023, 12(1): 111-121
Published: 23 December 2022
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It is generally reported that the grain growth in high-entropy ceramics at high temperatures is relatively slower than that in the corresponding single-component ceramics owing to the so-called sluggish diffusion effect. In this study, we report a fast grain growth phenomenon in the high-entropy ceramics (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)MgAl11O19 (HEMA) prepared by a conventional solid-state reaction method. The results demonstrate that the grain sizes of the as-sintered HEMA ceramics are larger than those of the corresponding five single-component ceramics prepared by the same pressureless sintering process, and the grain growth rate of HEMA ceramics is obviously higher than those of the five single-component ceramics during the subsequent heat treatment. Such fast grain growth phenomenon indicates that the sluggish diffusion effect cannot dominate the grain growth behavior of the current high-entropy ceramics. The X-ray photoelectron spectroscopy (XPS) analysis reveals that there are more oxygen vacancies (OV) in the high-entropy ceramics than those in the single-component ceramics owing to the variable valance states of Eu ion. The high-temperature electrical conductivities of the HEMA ceramics support this analysis. It is considered that the high concentration of OV and its high mobility in HEMA ceramics contribute to the accelerated migration and diffusion of cations and consequently increase the grain growth rate. Based on this study, it is believed that multiple intrinsic factors for the high-entropy ceramic system will simultaneously determine the grain growth behavior at high temperatures.

Open Access Research Article Issue
Equiatomic 9-cation high-entropy carbide ceramics of the IVB, VB, and VIB groups and thermodynamic analysis of the sintering process
Journal of Advanced Ceramics 2022, 11(7): 1082-1092
Published: 02 July 2022
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The preparation of high-entropy (HE) ceramics with designed composition is essential for verifying the formability models and evaluating the properties of the ceramics. However, inevitable oxygen contamination in non-oxide ceramics will result in the formation of metal oxide impurity phases remaining in the specimen or even escaping from the specimen during the sintering process, making the elemental compositions of the HE phase deviated from the designed ones. In this work, the preparation and thermodynamic analysis during the processing of equiatomic 9-cation HE carbide (HEC9) ceramics of the IVB, VB, and VIB groups were studied focusing on the removing of the inevitable oxygen impurity existed in the starting carbide powders and the oxygen contamination during the powder mixing processing. The results demonstrate that densification by spark plasma sintering (SPS) by directly using the mixed powders of the corresponding single-component carbides will inhibit the oxygen-removing carbothermal reduction reactions, and most of the oxide impurities will remain in the sample as (Zr,Hf)O2 phase. Pretreatment of the mixed powders at high temperatures in vacuum will remove most part of the oxygen impurity but result in a remarkable escape of gaseous Cr owing to the oxygen-removing reaction between Cr3C2 and various oxide impurities. It is found that graphite addition enhances the oxygen-removing effect and simultaneously prevents the escape of gaseous Cr. On the other hand, although WC, VC, and Mo2C can also act as oxygen-removing agents, there is no metal-containing gaseous substance formation in the temperature range of this study. By using the heat-treated powders with added graphite, equiatomic HEC9 ceramics were successfully prepared by SPS.

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