Structural,Raman, and Dielectric Studies on Multiferroic Mn‐doped Bi1−xLaxFeO3 Ceramics

Multiferroic Bi_1?xLa_xFeO₃ [BLFO (x)] ceramics with x = 0.10–0.50 and Mn‐doped BLFO (x = 0.30) ceramics with different doping contents (0.1–1.0 mol%) were prepared by solid‐state reaction method. They were crystallized in a perovskite phase with rhombohedral symmetry. In the BLFO (x) system, a composition (x)‐driven structural transformation (R3c→C222) was observed at x = 0.30. The formation of Bi₂Fe₄O₉ impure phase was effectively suppressed with increasing the x value, and the rhombohedral distortion in the BLFO ceramics was decreased, leading to some Raman active modes disappeared. A significant red frequency shift (~13 cm^?1) of the Raman mode of 232 cm^?1 in the BLFO ceramics was observed, which strongly perceived a significant destabilization in the octahedral oxygen chains, and in turn affected the local FeO₆ octahedral environment. In the Mn‐doped BLFO (x = 0.30) ceramics, the intensity of the Raman mode near 628 cm^?1 was increased with increasing the Mn‐doping content, which was resulted from an enhanced local Jahn–Teller distortions of the (Mn,Fe)O₆ octahedra. Electron microscopy images revealed some changes in the ceramic grain sizes and their morphologies in the Mn‐doped samples at different contents. Wedge‐shaped 71° ferroelectric domains with domain walls lying on the {110} planes were observed in the BLFO (x = 0.30) ceramics, whereas in the 1.0 mol% Mn‐doped BLFO (x = 0.30) samples, 71° ferroelectric domains exhibited a parallel band‐shaped morphology with average domain width of 95 nm. Dielectric studies revealed that high dielectric loss of the BLFO (x = 0.30) ceramics was drastically reduced from 0.8 to 0.01 (measured @ 10⁴ Hz) via 1.0 mol% Mn‐doping. The underlying mechanisms can be understood by a charge disproportion between the Mn⁴⁺ and Fe²⁺ in the Mn‐doped samples, where a reaction of Mn⁴⁺ + Fe²⁺→Mn³⁺ + Fe³⁺ is taken place, resulting in the reduction in the oxygen vacancies and a suppression of the electron hopping from Fe³⁺ to Fe²⁺ ions effectively.     

Effect of BBS‐Based Frit on the Low Temperature Sintering and Electrical Properties of KNN Lead‐Free Piezoceramics

Using BaO–B₂O₃–SiO₂ (BBS)‐based frit as sintering aid, the K_0.49Na_0.51NbO₃ (KNN) + x wt% BBS (x = 1.0, 1.5, 2.0 and 2.5) lead‐free piezoelectric ceramics were successfully fabricated by solid‐state reaction method under low‐sintering temperature of 1000°C. The effect of BBS frit doping amount on the structure and electrical properties of the ceramics was investigated. The KNN ceramics with 1.5 wt% BBS frit showed optimal properties as follows: piezoelectric constant d₃₃ = 108 pC/N, planar electromechanical coupling coefficient k_p = 41%, mechanical quality factor Q_m = 225, relative dielectric constant ε_r = 410, dielectric loss tanδ = 0.57% and Curie temperature T_c = 400°C. This ceramic sample should be a good lead‐free candidate for actuators or high temperature sensors application due to its ultra‐low tanδ, relatively high Q_m and T_c.     

Highly Dense,Transparent α‐Al2O3 Ceramics From Ultrafine Nanoparticles Via a Standard SPS Sintering

Using discrete, ultrafine alumina, highly dense transparent (71% real in‐line transmission, RIT, λ = 640 nm) ceramics were achieved with grain size as small as 260 nm using standard SPS sintering. We show that use of La³⁺ as a dopant greatly reduces sensitivity to the sintering temperatures. Transparent alumina were achieved in a large range of sintering temperatures, 1140°C < T < 1200°C, thus providing better reliability and flexibility into the fabrication of large sintered transparent ceramic bodies.     

Fabrication and characterization of IR-transparent Fe2+ doped MgAl2O4 ceramics

Initial investigations on the preparation of highly transparent Fe²⁺:MgAl₂O₄ ceramics using nanopowders synthesized in a laser plume were carried out. For the first time, dense Fe²⁺:MgAl₂O₄ ceramics with high transmission in the mid-IR range were fabricated at a temperature as low as 1300°C and with a short sintering time (1 hour). The obtained Fe²⁺:MgAl₂O₄ ceramics contain a secondary (MgO)_0.91(FeO)_0.09 phase with a low wt% content, causing a substantial decrease in transmittance in the visible range. The transmittance increases with an increase in wavelength due to a decrease in Rayleigh scattering and reaches 85.6% at λ = 4 μm, which is close to the theoretical value. The absorption cross section of divalent iron ions was estimated to be σ = (1.66 ± 0.14) × 10⁻²⁰ cm².     

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.     

Low Temperature Sintering and Enhanced Piezoelectricity of Lead‐Free (Na0.52K0.4425Li0.0375)(Nb0.86Ta0.06Sb0.08)O3 Ceramics Prepared from Nano‐Powders

(Na_0.52K_0.4425Li_0.0375)(Nb_0.86Ta_0.06Sb_0.08)O₃ powders were synthesized via sol–gel and solid‐state reaction methods as a raw material for the preparation of the ceramics. Dependence of piezoelectric properties and microstructure on sintering temperatures was investigated in this study. Sol–gel‐derived nano‐powders could be densified at a lower temperature of 940°C and exhibited excellent electrical properties after sintering at 1020°C (d₃₃ = 424 pC/N, d₃₃^* = 780 pm/V, k_p = 52.1%, and T_c = 265°C). The enhanced electric properties were most likely due to the coexistence of orthorhombic and tetragonal phase in the samples at room temperature, homogenous microstructure with fine grain and high density.     

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.     

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.     

Low‐firing and temperature stable microwave dielectric ceramics: Ba2LnV3O11 (Ln = Nd,Sm)

Low‐firing and temperature stable microwave dielectric ceramics of Ba₂LnV₃O₁₁ (Ln = Nd, Sm) were prepared by solid‐state reaction. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the phase purity, crystal structure, sintering behavior, and microstructure. The XRD patterns indicated that Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics belong to monoclinic crystal system with P2₁/c space group in the whole sintering temperature range (800°C ‐900°C). Both ceramics could be well densified at 880°C for 4 hours with relative densities higher than 96%. The Ba₂LnV₃O₁₁ (Ln = Nd, Sm) samples sintered at 880°C for 4 hours exhibited excellent microwave dielectric properties: ε_r = 12.05, Q × f = 23 010 GHz, τ_f = ?7.7 ppm/°C, and ε_r = 12.19, Q × f = 27 120 GHz, τ_f = ?16.2 ppm/°C, respectively. Besides, Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics could be well co‐fired with the silver electrode at 880°C.     

Low‐Temperature‐Fired ReVO4 (Re = La,Ce) Microwave Dielectric Ceramics

We report a series of ReVO₄ (Re = La, Ce) microwave dielectric ceramics fabricated by a standard solid‐state reaction method. X‐ray diffraction and scanning electron microscopy measurements were performed to explore the phase purity, sintering behavior, and microstructure. The analysis revealed that pure and dense monoclinic LaVO₄ ceramics with a monazite structure and tetragonal CeVO₄ ceramics with a zircon structure could be obtained in their respective sintering temperature range. Furthermore, LaVO₄ and CeVO₄ ceramics sintered at 850°C and 950°C for 4 h possessed out‐bound microwave dielectric properties: ε_r = 14.2, Q × f = 48197 GHz, τ_f = ?37.9 ppm/°C, and ε_r = 12.3, Q × f = 41 460 GHz, τ_f = ?34.4 ppm/°C, respectively. The overall results suggest that the ReVO₄ ceramics could be promising materials for low‐temperature‐cofired ceramic technology.     

Phase Evolution,Magnetic, Optical,and Dielectric Properties of Zr‐Substituted Bi0.9Gd0.1FeO3 Multiferroics

Polycrystalline BiFeO₃ (BFO) and Bi_0.90Gd_0.10Fe_1?xZr_xO₃ (x = 0.0–0.10; BGFZ_x) ceramics were synthesized by solid‐state reaction method. Rietveld analysis of X‐ray diffraction patterns showed that BFO and BGFZ_x = 0.0 samples are stabilized in rhombohedral structure (space group R3c), whereas a small fraction of orthorhombic phase (space group Pn2₁a) is observed for BGFZ_{x = 0.03–0.10} samples. Suppression and disappearance of some Raman modes indicated a structural phase transition with addition of Zr dopant at Fe site. Magnetic measurements exhibited weak ferromagnetic behavior of BGFZ_x samples with increasing Zr⁺⁴ concentrations. The insertion of Gd⁺³ ions at Bi⁺³ sites and nonmagnetic Zr⁺⁴ ions at Fe⁺³ sites in Fe–O–Fe network suppressed the spin cycloid structure of BFO which in turn enhanced the magnetization of these ceramics. Electron spin resonance spectra revealed the breaking of spin cycloid of BFO due to the development of free spins with addition of Zr⁺⁴ dopants at Fe sites. UV–Visible diffuse reflectance spectra showed one d–d crystal field transition and two charge‐transfer (C–T) transitions along with a sharp absorption of light in visible region for all samples. Almost frequency‐independent dielectric constant and dielectric loss along with very low values of dielectric loss indicated greatly improved dielectric properties for BGFZ_{x = 0.03–0.10} samples.     

Dy3+/Ce3+ Codoped YAG Transparent Ceramics for Single‐Composition Tunable White‐Light Phosphor

Superior optical, thermal, and mechanical properties of transparent ceramics are very important in the applications of solid lasers, solid‐state lighting, and transparent armors. Herein, a series of (Dy_0.03Ce_xY_0.97?x)₃Al₅O₁₂ transparent ceramics were fabricated using vacuum reactive sintering method. Importantly, these Dy³⁺/Ce³⁺ codoped yttrium aluminum garnet (YAG) transparent ceramics served as single‐composition tunable white‐light phosphors for UV‐LEDs is developed for the first time. By combining with commercially available UV‐LEDs directly, the optimal chromaticity coordinates and correlated color temperature (CCT) are (x = 0.33, y = 0.35) and 5609 K, respectively. Notably, the codoping of Ce³⁺ enhances the luminescent intensity of Dy³⁺ ions while excited at 327 nm. The emission color of YAG transparent ceramics can be tuned from white to yellow through energy transfer between Dy³⁺ and Ce³⁺. These new phosphors, possessing of pure CIE chromaticity and environmentally friendly nature, are promising for applications in white UV‐LEDs.     

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.     

Effect of Gd Content on Luminescence Properties of Eu3+‐Doped La2−xGdxZr2O7 Transparent Ceramics

3 at.% Eu³⁺‐doped La_2?xGd_xZr₂O₇ (x = 0–2.0) transparent ceramics were fabricated by vacuum sintering. The effect of Gd content on crystal structure, in‐line transmittance, and luminescence property of the ceramics were investigated. The ceramics are all cubic pyrochlore structure with high transparency. The cut‐off edge of the transmittance curve of the ceramics varied with Gd content and was also affected by the annealing process. The luminescence intensity became stronger for the ceramics annealed in air. As Gd content increased, the energy band structure as well as the luminescence behavior of the ceramics was changed; in addition, the symmetry of the crystal lattice reduced, resulting in the shift of the strongest luminescence peak from 585 nm to around 630 nm.     

Enhanced insulating and piezoelectric properties of BiFeO3-BaTiO3-Bi0.5Na0.5TiO3 ceramics with high Curie temperature

BiFeO₃-BaTiO₃ ceramics are promising lead-free piezoelectric ceramics due to their high piezoelectric properties and high Curie temperature, but their high leakage current density makes the poling difficult. In this study, a decreased leakage current density by three orders of magnitude was obtained in Bi_0.5Na_0.5TiO₃ (BNT) added 0.67BiFeO₃-0.33BaTiO₃ (BF-BT) ceramics. It was found that the largely improved insulating properties benefit from the reduced oxygen vacancies and weak reduction of Fe³⁺ to Fe²⁺ as confirmed by photoluminescence and X-ray photoelectron spectroscopy measurements, thereby contributing to high-temperature and high-field poling. In addition, the introduction of BNT leaded to increased grain size. Due to the grown grains as well as reduced oxygen vacancies and Fe²⁺, enhanced insulating and optimal piezoelectric properties with P_r = 24.2 µC/cm², d₃₃ = 183 pC/N, k_p = 0.28, and T_C = 467°C were achieved in BF-BT-0.05BNT ceramics.     

Ni-Cu-Zn ferrites with high Curie temperature for multilayer inductors with increased operating temperatures

We studied the sintering behavior and magnetic properties of Ni_0.60-yCu_yZn_0.42Fe_1.98O_3.99 ferrites. The shrinkage is shifted toward lower temperature with increasing Cu content y. The addition of Bi₂O₃ sintering aid induces enhanced shrinkage at T < 900°C and dense ceramics are obtained after sintering at 900°C. Such ferrites exhibit a permeability of µ = 135-250 depending on the composition, sintering temperature and concentration of sintering additive. Ferrites with y = 0.20 show a high Curie temperature of T_c = 307°C. Multilayer inductors were fabricated and cofired at 900°C using ferrite tapes without and with 0.75 wt% Bi₂O₃. The compatibility of ferrite tapes with different metal pastes (Ag, AgPd, and Au) was evaluated. Ferrite tapes were also integrated between layers of low-k dielectric CT708 tapes and successfully cofired at 900°C. Preliminary tests indicate that the multilayer inductors can be operated up to temperatures of 250°C. This demonstrates that high-T_c Ni-Cu-Zn ferrites are promising magnetic materials for inductive components for high operating temperatures.     

Phase,domain, and microstructures in Sr2+ substituted low-temperature sintering PZT-based relaxor ferroelectrics

The Ag-Pd internal electrode of multilayer piezoelectric ceramics needs to be sintered below 1000°C, and lead wires and components need to be welded with lead-free solder at 260°C. PNN–PMW–PZT–xSr piezoelectric ceramics with high Curie temperature (T_c > 260°C) were synthesized at a low sintering temperature (960°C) to meet the requirements of multilayer piezoelectric devices. The relationship between structures (phase, domain, and microstructures) and electrical properties (piezo/ferroelectric properties, and dielectric relaxation) in the Sr²⁺ substituted ceramics was investigated. Rietveld refinement and Raman spectra show that Sr²⁺ substitution can cause the phase change and increase the force constant of [BO₆] octahedron. The piezoelectric response increases with increasing the content of the tetragonal phase (CTP) in the rhombohedral-tetragonal (R-T) coexisted ceramics. The ceramics with 0.6 mol% Sr²⁺ substitution have minimum activation energy for domain wall movement (E_a) of 0.0362 eV which favors the formation of nanometer-sized domains, and possess excellent electrical properties (d₃₃ = 623 pC/N, d₃₃^* =783 pm/V, T_c =295°C). The higher the CTP, the lower the E_a. The lower E_a favors the rotation of polarization direction and extension, and is beneficial to the generation of the nanometer-size domains, resulting in high piezoelectric properties.     

Properties and structures of nonstoichiometric (K,Na)NbO3‐based lead‐free ceramics

The 0.968[(K_0.48Na_0.52)]Nb_0.95+xSb_0.05O₃–0.032(Bi_0.5Na_0.5)ZrO₃ [KNN_xS–BNZ] lead‐free ceramics with nonstoichiometric niobium ion were fabricated via conventional solid‐state sintering technique and their piezoelectric, dielectric and ferroelectric properties were investigated. When x = 0.010, enhanced piezoelectric properties (d₃₃ ≈ 421 pC/N and k_p ≈ 0.47) were obtained due to the construction of rhombohendral—tetragonal phase boundary near room temperature. The KNN_xS–BNZ ceramics possesses enhanced Curie temperature (T_c) with improved piezoelectric constant. A large d₃₃ of ~421 pC/N and a high T_c ~256°C can be simultaneously induced in the ceramics with x = 0.010. Especially, good thermal stability was observed in a broad temperature range. The results indicated that our work could benefit development of KNN‐based ceramics and widen their application range.     

Enhancement of piezoelectric properties of BF–BT ceramics by using ZrO2 powder bed during the sintering process

ZrO₂ powders of various particle sizes (0.15, 0.7, 500 µm) were used to simulate loose powder bed sintering to prepare BF–BT piezoelectric ceramics. The phase structure, dielectric properties, ferroelectric properties, and piezoelectric properties were compared with the samples sintered by the conventional powder bed method (i.e., powder of the same composition as the sample). Results showed that the use of loose ZrO₂ powder bed could improve the heat conduction rate and the sintering quality of bulk BF–BT piezoelectric ceramics. The XPS results showed that the samples sintered with 500 µm ZrO₂ powder beds had the lowest concentration of Fe²⁺, exhibited the largest piezoelectric coefficients (d₃₃ = 201 pC/N). In contrast, the sample sintered with a conventional powder bed under the same sintering conditions had a piezoelectric coefficient d₃₃ of 156 pC/N.     

Thermal stability and electric‐field‐induced strain behaviors for PIN‐PSN‐PT piezoelectric ceramics

Pb (In_1/2Nb_1/2) O₃‐Pb (Sc_1/2Nb_1/2) O₃‐PbTiO₃ (PIN‐PSN‐PT) ternary ceramics with compositions near morphotropic phase boundary (MPB) were fabricated by solid‐state‐sintering process. Dielectric and piezoelectric properties of xPIN‐yPSN‐zPT (x = 0.19, 0.23 and z = 0.365, 0.385) ceramics were investigated as a function of temperature, showing high T_r‐t and T_c on the order of 160 ~ 200°C and 280 ~ 290°C, respectively. The xPIN‐yPSN‐0.365PT (x = 0.19 and 0.23) ceramics do not depolarize at the temperature up to 200°C, showing a better thermal stability when compared to the state‐of‐the‐art relaxor‐PbTiO₃ systems. A slight variation (<9%) of k_p, k_t, and k₃₃ was observed in the temperature range of 25°C‐160°C for xPIN‐yPSN‐0.385PT (x = 0.19 and 0.23) ceramics. Rayleigh analysis was employed to quantify the contribution of domain wall motion to piezoelectric response, where the domain wall contribution was found to increase with composition approaching MPB for PIN‐PSN‐PT system.