Enhancement of grain growth and electrical conductivity of La0.8Sr0.2MnO3 ceramics by microwave irradiation

We studied crystallization, grain growth and electric properties of La_0.8Sr_0.2MnO₃ (LSM) ceramics which were produced using the microwave-treatment. While co-precipitated nanoparticles remain mainly amorphous, the microwave irradiated particles are crystallized into LSM and La₂Mn₂O₇ at 550 °C, due to higher dielectric polarizability of La. This, in turn, decreases the amount of the second phase La₂O₃ in calcined powder and promotes the growth of perovskite grains during sintering at 1400 °C. Larger grains of LSM ceramics lower the activation energy of small polaron hopping from 0.35 eV to 0.24 eV and increases high-temperature electric conductivity. In addition, high crystallinity of LSM ceramics from the microwave-treatment suppresses a chemical reaction with ZrO₂ and NiO in a temperature range of 900 – 1100 °C under oxidizing and reducing ambiances. These results show that LSM ceramics from the microwave-assisted reaction meet requirements for an interconnect layer for solid oxide electrolysis cells.     

Enhanced high temperature dielectric polarization of barium titanate/magnesium aluminum spinel composites and their potential in microwave absorption

Antioxidant materials with high permittivity are highly desirable for thin, microwave-absorbing materials at high temperature (MAMHT) due to their great impedance matching. In this work, composite ceramics composed of BaTiO₃ and MgAl₂O₄ (BTMAS) synthesized by a traditional solid-state sintering method have been studied for their high temperature microwave dielectric properties. When the temperature rose between 473 K–573 K, the real part of permittivity (ε’) of BTMAS increased significantly relative to room temperature. As the temperature increased further to 873 K, ε’ gradually fell. Based on the collection of permittivities obtained by the inverse resolution of specific reflectivity, BT36 (36 mol % BaTiO₃) was suitable for 1.1 mm thick microwave-absorbing materials from 300 K – 873 K. The envisaged material had an absorption bandwidth of 2 GHz (RL<-5 dB) which could move between microwave X-band as the temperature changed. Therefore, there is great potential for BTMAS in reducing the thickness of MAMHT.     

A novel high-entropy perovskite ceramics Sr0.9La0.1(Zr0.25Sn0.25Ti0.25Hf0.25)O3 with low thermal conductivity and high Seebeck coefficient

In this work, a novel high-entropy n-type thermoelectric material Sr_0.9La_0.1(Zr_0.25Sn_0.25Ti_0.25Hf_0.25)O₃ with pure perovskite phase was prepared using a conventional solid state processing route. The results of TEM and XPS show that various types of crystal defects and lattice distortions, such as oxygen vacancies, edge dislocations, in-phase rotations of octahedron and antiparallel cation displacements coexist in this high-entropy ceramic. At 873 K, the high-entropy ceramics showed both a low thermal conductivity (1.89 W/m/K) and a high Seebeck coefficient (393 μV/K). This work highlights a way to obtain high-performance perovskite-type oxide thermoelectric materials through high-entropy composition design.     

Suppressed temperature dependence of the resonant frequency of a AgNb0.5Ta0.5O3 composite vs. single-phase ceramics

AgNb_0.5Ta_0.5O₃ ceramics were synthesized and analyzed, with respect to their dielectric properties, in the radio- and microwave-frequency ranges. The influences of different synthesis conditions were investigated and correlated with the difficulties in preparing single-phase ceramics, as a consequence of the inhomogeneous distribution of Nb and Ta ions and the decomposition of the matrix phase. The results revealed that with the simple mixing of all three oxides and subsequent firing in air, it is possible to prepare composite material that is attractive for microwave applications due to inhomogeneity of the B-site cation distribution – a well-known issue that was in our case shown to be an advantage for decreasing the temperature dependence of the resonant frequency over a broad temperature range. On the other hand, we also succeeded in fabricating single-phase ceramics with a very high density through the initial formation of a precursor and sintering in an overpressure of oxygen.     

Phase evolution and microstructure of new Sr0.5Zr2(PO4)3-NdPO4 composite ceramics prepared by one-step microwave sintering

Sodium Zirconium Phosphate (NaZr₂(PO₄)₃, hereinafter NZP) and monazite are both potential materials for immobilization of nuclear waste. In this work, novel (1-x)Sr_0.5Zr₂(PO₄)₃-xNdPO₄ composite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) for simultaneously immobilizing the simulated fission product (FP) Sr and trivalent minor actinide (MA) Nd were prepared by one-step microwave sintering technique, in which Sr and Nd were immobilized into NZP and monazite type structures, respectively. The phase evolution and microstructure of the samples were investigated by X-ray diffraction (XRD), Raman, and backscattering scanning electron microscopy (BSE). The results showed that the expected composite ceramics were successfully obtained by one-step microwave sintering at 1050 °C for 2 h. The as-prepared samples consisted of Sr_0.5Zr₂(PO₄)₃ and NdPO₄ phases, and the content of the two phases varied regularly as x changed, generally conforming to the designed nominal chemical composition. Importantly, the composite ceramics presented the homogenous and dense microstructure. The relative density of the composite ceramics was more than 95%, meanwhile, the Vickers-hardness of the samples was higher than 600 MPa. It was indicated that NZP-monazite type composite ceramics could be a potential matrix for the simultaneous immobilization of actinide and fission product.     

MgO-Y2O3:Eu composite ceramics with high quantum yield and excellent thermal performance

MgO-Y₂O₃:Eu composite ceramics with high quantum yield and excellent thermal performance were successfully synthesized by vacuum sintering. All samples exhibited uniform composite microstructures and pure binary phase. Eu³⁺ ions were completely incorporated into Y₂O₃ phase, and the optimal Eu concentration is 15 at%. Sintered at 1800 °C, the fluorescent properties of MgO- z vol% Y₂O₃: Eu (z = 30, 40, 50, 60, 70, 100) composites proved to be independent on component proportion, including the similar fluorescence lifetimes (953–983 μs), quantum yield (70%−80%), and activation energy (ΔE) of thermal quenching (0.163 eV). Significantly, thermal conductivity of composites with 30 vol%, 50 vol% and 70 vol% MgO attained 11.58, 17.45, and 29.65 W/(m∙K) at room temperature, which are nearly 2, 3, and 5 times as high as that of 15 at% Eu:Y₂O₃ ceramic (5.90 W/(m∙K)), respectively, demonstrating their potential for application in high-power-density display and lighting technology.     

Co2O3 substitution effects on the structure and microwave dielectric properties of low-firing (Zn0.9Mg0.1)TiO3 ceramics

Low-firing (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ (x = 0.02–0.10) (ZMC_xT) microwave dielectric ceramics with high temperature stability were synthesized via conventional solid-state reaction. The influences of Co₂O₃ substitution on the phase composition, microstructure and microwave dielectric properties of ZMC_xT ceramics were discussed. Rietveld refinement results show the coexistence of ZnTiO₃ and ZnB₂O₄ phases at x = 0.02–0.10. (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ ceramic with x = 0.06 (ZMC_0.06T) obtains the best combination microwave dielectric properties of: ε_r = 21.58, Q × f = 53,948 GHz, τ_f = ? 54.38 ppm/°C. For expanding its application in LTCC field, 3 wt% ZnO-B₂O₃-SiO₂ (ZBS) and 9 wt% TiO₂ was added into ZMC_0.06T ceramic, great microwave dielectric properties were achieved at 900 °C for 4 h: ε_r = 26.03, Q × f = 34,830 GHz, τ_f = ? 4 ppm/°C, making the composite ceramic a promising candidate for LTCC industry.     

(Ce,Gd):YAG-Al2O3 composite ceramics for high-brightness yellow light-emitting diode applications

(Ce,Gd):YAG-Al₂O₃ composite ceramics were prepared for high-brightness yellow LED (565?590 nm) applications. Phase fraction, microstructure, thermal quenching effect, and luminescent properties of composite ceramics with varying compositions were studied in detail. Collaborating composite ceramics with InGaN blue chips, the relationship between thermal conductivity, temperature rise during LED-driven phosphor conversion, and steady-state luminous efficiency were elucidated. As the proportion of Al₂O₃ increases from 0 to 40 wt%, the steady-state luminous efficiency of yellow LED is enhanced from 100.88–109.49 lm W^?1, benefiting from the increased thermal stability and reduced operating temperature of ceramics (from 141.1–132.2 °C). Additionally, scattering behavior and extraction efficiency of composite ceramics with different thicknesses were investigated.     

Dielectric,ferroelectric and magnetoelectric properties of in-situ synthesized CoFe2O4/BaTiO3 composite ceramics

Magnetoelectric composite materials have attracted more and more attention because of their coupling of ferroelectricity and ferromagnetism. It is a hotspot to realize the combination of ferromagnetic phase and ferroelectric phase. In this work, we used a new strategy to prepare CoFe₂O₄/BaTiO₃ composite ceramics: firstly, porous ferromagnetic CoFe₂O₄ phase was prepared by annealing of MOFs (metal organic frameworks) precursor Fe₃[Co(CN)₆]₂. And then, the ferroelectric BaTiO₃ phase in-situ grew in the pores of CoFe₂O₄ by a hydrothermal method. In the end, the CoFe₂O₄/BaTiO₃ composite ceramics sintered at different temperatures have been synthesized. The effects of sintering temperature on the structure, dielectric and ferroelectric properties have also been studied. Because the crystallinity and density increase with the increase of sintering temperature, the composite ceramic sintered at 1200 °C shows the best dielectric properties. It is found that sintering temperature has little effect on the ferroelectric and magnetic properties of ceramics. Taking the CoFe₂O₄/BaTiO₃ composite ceramic sintered at 1200 °C as an example, derived from the interaction between the ferromagnetic CoFe₂O₄ phase and ferroelectric BaTiO₃ phase, the applied magnetic field lead to the reduction of P_r and E_c.     

Effect of Li nonstoichiometry and TiO2 addition on the microwave dielectric properties of Li3PO4 ceramics

Li₃PO₄ ceramic is a promising microwave ceramic material with low dielectric constant. The effect of Li nonstoichiometry on phase compositions, microstructures, and microwave dielectric characteristics of Li₃PO₄ ceramics, on the other hand, has been examined infrequently. Therefore, in the first part of this study, the stoichiometry and Li nonstoichiometry compositions based on Li_3+xPO₄(x = 0, 0.03, 0.06, 0.09, 0.12 and 0.15) were prepared by conventional solid-phase method. The results show that a few nonstoichiometric lithium ions enter the lattice of Li_3+xPO₄. Compared with the chemical content of Li₃PO₄, the sintering characteristics, relative dielectric constants and quality factors of Li_3+xPO₄ ceramics can be improved by slightly excessive Li ions, while the properties of Li₃PO₄ ceramics can be deteriorated by excessive Li ions. Li_3.12PO₄ ceramics sintered at 975 °C for 2 h have good dielectric properties (ε_r = 5.89, Q×f = 44,000 GHz, τ_f = ?206 ppm/^°C). In order to improve its large negative temperature coefficient of resonant frequency, in the following study, rutile nano TiO₂ particles were added as τ_f compensator. Adding TiO₂ powders not only effectively improve the temperature stabilities of the multiphase ceramics, but also make the grain growth more uniform. With the increase of TiO₂ content from 0.40 to 0.60, τ_f increases from ?73.5 ppm/^°C to +42.3 ppm/^°C. The best dielectric property of 0.45Li_3.12PO₄-0.55TiO₂ composite ceramic is ε_r = 13.29, Q×f = 40,700 GHz, τ_f = +8.8 ppm/^°C.     

Grain orientation evolution and multi-scale interfaces enhanced thermoelectric properties of textured Sr0.9La0.1TiO3 based ceramics

Sr_0.9La_0.1TiO₃ based textured ceramics (SLTT-S3T) with a texture fraction of 0.81 are successfully fabricated by the reactive template grain growth method, in which Sr_0.9La_0.1TiO₃/20 wt%Ti was used as matrix and 10 wt% plate-like Sr₃Ti₂O₇ template seeds were used as templates. The phase transition, microstructure evolution, and the anisotropic thermoelectric properties of SLTT-S3T ceramics were investigated. The results show that the ceramics are mainly composed of Sr_0.9La_0.1TiO₃ and rutile TiO₂ phases. Grains grow with a preferred orientation along (h00). A maximum ZT of 0.26 at 1073 K was achieved in the direction perpendicular to the tape casting direction. The low lattice thermal conductivity of 1.9 W/(m K) at 1073 K was obtained decreased by 34%, 40%, and 38% compared with non-textured, SrTiO₃ and Sr_0.9La_0.1TiO₃ ceramics prepared by the same process, can be attributed to the enhanced phonon scattering by the complex multi-scale boundaries and interfaces. This work provides a strategy of microstructural design for thermoelectric oxides to decrease intrinsic lattice thermal conductivity and further regulate thermoelectric properties via texture engineering.     

烧结气氛对合成MgAl2O4-Ti(C,N)复合陶瓷的影响

以金属铝粉、钛白粉和轻烧MgO细粉为原料,通过设计100%焦炭粒(简称C气氛),10%钛白粉 90%焦炭粒(简称TC气氛),以及10%硅微粉 90%焦炭粒(简称SC气氛)3种埋粉条件下的高温烧结还原性气氛,采用X射线衍射仪(XRD)、扫描电镜(SEM)和微区电子探针分析(EPMA)等手段,研究了铝热还原氮化法(1600℃3h)制备MgAl2O4-Ti(C,N)复合陶瓷在不同烧结气氛下的相组成和显微结构的变化。结果表明在不同气氛下,烧后试样的主要物相均为MgAl2O4和Ti(C,N),Ti(C,N)可能会固溶氧,气氛对Ti(C,N)的影响较大。和单纯埋炭气氛下相比,在TC气氛下有助于Ti(C,N)的生成,但晶粒细小;在SC气氛下不利于Ti(C,N)的生成,且有玻璃相存在。     

Effects of non-stoichiometric defects on the dielectric properties of (Ba0.5Sr0.5)xTiO3-ZnGa2O4 composite ceramics

In order to explore the effects of non-stoichiometric defects on the dielectric properties of composite ceramics, 70 wt% (Ba_0.5Sr_0.5)_xTiO₃-30 wt%ZnGa₂O₄ ((BS)_xT50-ZG, x = (Ba + Sr)/Ti = 0.99, 1.00, 1.01 and 1.05) composite ceramics were fabricated by the traditional sintering technique. The association between structure and dielectric properties has been studied. The results show that the distortion of the crystal lattice brought by the partial Schottky defects, namely [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^×, induces a decrease in the Curie temperature of (BS)_xT50-ZG composite ceramics. The orientation of the elastic dipoles brought by oxygen vacancies causes the pinning of the domain walls, which reduces the dielectric loss at low frequencies. Tunability is related to the dipole polarization caused by [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^× defect complexes. In addition, compared with the composite ceramic with x = 1, the Q values of the composite ceramics with x < 1 and x > 1 decreases due to the deterioration of the microstructure homogeneity and the enhancement of the disorder of the B-site cations in (BS)_xT50.     

Enhanced multiferroic properties of Bi4Ti3-xCoxO12/La0.67Sr0.33MnO3 layered composite thin films

In this work, Bi₄Ti_3-xCo_xO₁₂/La_0.67Sr_0.33MnO₃ (BITC_x/LSMO, x = 0.025, 0.05, 0.10 and 0.15) layered magnetoelectric (ME) composite thin films were successfully synthesized by chemical solution deposition, and the effect of Co²⁺ doping content on the microstructure, leakage, dielectric property, ferroelectricity, ferromagnetism and ME coupling performance of BITC_x/LSMO composite thin films was investigated. Co²⁺ doping induces improved ferroelectricity and weak ferromagnetism for the BITC_x phase. Especially, the single-phase BITC_0.05 film exhibits a maximum ME voltage coefficient (α_E) of 0.445 mV/cm·Oe at room temperature, suggesting excellent single-phase multiferroic properties. The BITC_0.05/LSMO composite thin film possesses the lowest leakage current density, maximum ?_r, minimum tanδ, highest remnant polarization of 24.2 μC/cm², lowest coercive field of 137 kV/cm and improved saturation magnetization along with a maximum a_E value of 27.3 V/cm·Oe. Based on these findings, Co²⁺-doped Bi₄Ti₃O₁₂ has excellent single-phase multiferroic properties, and the incorporation of magnetic ion-doped Bi₄Ti₃O₁₂ with ferromagnetic oxides benefits the improvement of ME composite thin films.     

(Cu1/3Nb2/3)4+ ionic substituting effects,low-temperature sintering behaviors,and improved temperature stability of Ba3Nb4Ti4O21 microwave dielectric ceramics

In this study, (Cu_1/3Nb_2/3)⁴⁺ complex cation and BaO–ZnO–B₂O₃ glass frit were adopted to solve the high sintering temperature and poor temperature stability of Ba₃Nb₄Ti₄O₂₁ ceramics. It is shown that pure Ba₃Nb₄Ti₄O₂₁ phase was formed when Ti site was partially replaced by (Cu_1/3Nb_2/3)⁴⁺ cation. The increasing number of dopants decreases the dielectric polarizability, correspondingly, the dielectric constant and temperature coefficient of the resonance frequency values are reduced consistently. The variation of the Q × f value is determined by internal ionic packing fraction and external sintering densification. The (Cu_1/3Nb_2/3)⁴⁺ cation effectively decreases the suitable sintering temperature from 1200 to 1050 °C while greatly improving the temperature stability. BaO–ZnO–B₂O₃ glass was used to further improve the low-temperature sintering characteristics of Ba₃Nb₄Ti₄O₂₁ ceramics. It is proven that the addition of glass frits effectively decreases the temperature to 925 °C with combinational excellent microwave dielectric properties: ε_r ～55.6, Q × f ～5700 GHz, τ_f ～3 ppm/^°C, making the Ba₃Nb₄Ti₄O₂₁ ceramics promising in the applications of low-temperature cofired ceramic technology.     

Thermal properties of La2O3-doped ZrB2- and HfB2-based ultra-high temperature ceramics

Thermal properties of La₂O₃-doped ZrB₂- and HfB₂-based ultra high temperature ceramics (UHTCs) have been measured at temperatures from room temperature to 2000 °C and compared with SiC-doped ZrB₂- and HfB₂-based UHTCs and monolithic ZrB₂ and HfB₂. Thermal conductivities of La₂O₃-doped UHTCs remain constant around 55–60 W/mK from 1500 °C to 1900 °C while SiC-doped UHTCs showed a trend to decreasing values over this range.     

A novel Sn0.9Ni0.1P2O7/KPO3 composite electrolyte with improved electrical properties for intermediate temperature fuel cells

In this study, a novel Sn_0.9Ni_0.1P₂O₇/KPO₃ composite electrolyte was prepared by a mechanical mixing method. The Raman spectrum and X-ray diffraction of Sn_0.9Ni_0.1P₂O₇/KPO₃ indicated that the main microstructure is pyrophosphate phase and KPO₃ mainly exists in amorphous state in the composite. The intermediate temperature (400–700 °C) electrical properties of Sn_0.9Ni_0.1P₂O₇/KPO₃ were studied by means of electrochemical impedance spectroscopy. The maximum conductivity of Sn_0.9Ni_0.1P₂O₇/KPO₃ was 6.1 × 10⁻² S cm⁻¹ in a dry nitrogen atmosphere at 700 °C. The log σ ～ log (pO₂) results showed that Sn_0.9Ni_0.1P₂O₇/KPO₃ is a pure ionic conductor in an oxidizing atmosphere and a hybrid conductor of proton and electron hole under a reductive atmosphere. The maximum power density of Sn_0.9Ni_0.1P₂O₇/KPO₃ (thickness: 1.2 mm) was 434 mW cm⁻² at 700 °C.     

Improved microstructure and high quality factor of Li2Ti0.9(Zn1/3Ta2/3)0.1O3 microwave ceramics with LiF additive for LTCC applications

In this study, LiF was utilized to decrease sintering temperature, improve microstructure, enhance Q×f, and regulate τ_f of Li₂Ti_0.9(Zn_1/3Ta_2/3)_0.1O₃ (abbreviated as LTZT) ceramics. A complete solid solution together with a phase transition from monoclinic to cubic rock salt structure occurred. The cell volume of LTZT ceramics decreased as the LiF content increased. Relatively dense and uniform microstructures were observed for the ceramics as the LiF content was not less than 2 wt%. The dielectric constant of LTZT ceramics initially increased and then decreased with the increasing LiF content. The FWHM of the Raman band at about 808 cm^?1 was closely related to the Q×f value. Notably, the samples with 3 wt% LiF exhibited the highest relative density of 97.4 % and satisfactory microwave dielectric properties of ε_r = 23.14 ± 0.16, Q×f = 110,090 ± 1100 GHz, and τ_f = +3.25 ± 1.45 ppm/°C when sintered at 950 °C. Good chemical compatibility with silver indicated the ceramic is a promising candidate in LTCC applications.     

Effects of ZrO2 on the photoluminescence of 0.5 at% Eu:(Y0.9La0.1)2O3 transparent ceramics

Zr-codoped 0.5 at% Eu: (Y_0.9La_0.1)₂O₃ ceramics sintered in H₂-reducing atomsphere, together with the ceramics with annealing treatment, were fabricated by solid-state reactions and the effects of Zr codoping on these materials’ photoluminescence examined. The obtained emission spectra showed that Zr codoping adjust the materials’ photoluminescence with UV excitation and a logical explanation was proposed. The results suggested that an Eu-doped, yttrium-lanthanum oxide transparent ceramic with Zr in low concentration appeared to have promising potential in modern lighting applications.