Synthesis,characterization, and microwave dielectric properties of ZnTiTa2O8 ceramics with ixiolite structure obtained through the aqueous sol–gel process

Nano-sized ZnTiTa₂O₈ powders with ixiolite structure, with particle sizes ranging from 10 nm to 30 nm, were synthesized by thermal decomposition at 950 °C. The precursors were obtained by aqueous sol–gel and the compacted and sintered ceramics with nearly full density were obtained through subsequent heat treatment. The microstructure and electrical performance were characterized by field emission scanning electron microscopy, x-ray diffraction, and microwave dielectric measurements. All the samples prepared in the range 950–1150 °C exhibit single ixiolite phase and relative density between ~87% and ~94%. The variation of permittivity and Q·ƒ value agreed with that of the relative density. Pure ZnTiTa₂O₈ ceramic sintered at 1050 °C for 4 h exhibited good microwave dielectric properties with a permittivity of 35.7, Q·ƒ value of 57,550 GHz, and the temperature coefficient of resonant frequency of about −24.7 ppm/°C. The relatively low sintering temperature and excellent dielectric properties in the microwave range would make these ceramics promising for applications in electronics.     

Temperature-independent permittivity of xBaTiO3–(1−x)(0.5Bi(Mg1/2Ti1/2)O3–0.5BiScO3) ceramics

xBaTiO₃–(1−x)(0.5Bi(Mg_1/2Ti_1/2)O₃-0.5BiScO₃) or xBT–(1−x)(0.5BMT–0.5BS) (x=0.45–0.60) ceramics were prepared by using the conventional mixed oxide method. Perovskite structure with pseudo-cubic symmetry was observed in all the compositions. Dielectric measurement results indicated that all the samples showed dielectric relaxation behavior. As the content BaTiO₃ was decreased from 0.60 to 0.45, temperature coefficient of permittivity (TCε) in the range of 200–400 °C was improved from −706 to −152 ppm/°C, while the permittivity at 400 °C was increased from 1208 to 1613. The temperature stability of permittivity was further improved by using 2 mol% Ba-deficiency. It was found that lattice parameter and grain size of the 2 mol% Ba-deficient ceramics were smaller than those of their corresponding stoichiometric (S) counterparts, with TCε in the range of 200–400 °C to be improved noticeably. For example, TCε of the Ba-deficiency sample with x=0.45 was −75 ppm/°C in the temperature range of 200–400 °C and the permittivity was 1567 at 400 °C. The results obtained in this work indicated that xBT–(1−x)(0.5BMT–0.5BS) ceramics are very promising candidates for high temperature capacitor applications.     

In situ preparation of CoFe2O4–Pb(ZrTi)O3 multiferroic composites by gel-combustion technique

Diphase magnetoelectric composites of CoFe₂O₄–Pb(ZrTi)O₃ were prepared by citrate–nitrate combustion technique by using Pb(Zr,Ti)O₃ template powders obtained by the mixed oxide method. Pure diphase powder composites with a good crystallinity were obtained after calcination. The composition and purity were maintained after sintering at temperature of 1100 °C/2 h, which ensured limited reactions at interfaces, while by sintering at 1250 °C/2 h, some small amounts of secondary phases identified as nonstoichiometric ZrO_2?x resulted. The method allowed to produce diphase ceramics with homogeneous microstructures and a very good mixing of the two phases. The dielectric and magnetic investigation at room temperature confirmed the formation of composite ceramics with both dielectric and magnetic properties at room temperature, with permittivity and magnetization resulted as sum properties from the parent Pb(Zr,Ti)O₃ and ferrite phases.     

Dielectric behaviors of Nb2O5–Co2O3 doped BaTiO3–Bi(Mg1/2Ti1/2)O3 ceramics

Nb₂O₅ and Nb–Co doped 0.85BaTiO₃–0.15Bi(Mg_1/2Ti_1/2)O₃ (0.85BT–0.15BMT) ceramics were investigated. From XRD patterns, undesired phase was observed when the (Nb₂O₅/Nb-Co) doping levels exceed 3 wt.%/2 wt.%, giving rise to the deteriorate dielectric constant. The 0.85BT–0.15BMT ceramics doped with 2 wt.%Nb₂O₅ was found to possess a moderate dielectric constant (? ～ 1000) and low dielectric loss (tan δ = 0.9%) at room temperature and 1 kHz, showing flat dielectric behavior over the temperature range from ?55 to 155 °C. It was found that the formation of core–shell structure in the BT based ceramics is controlled by the doping sequence of Nb- and Bi-oxides.     

Low temperature firing of BiSbO4 microwave dielectric ceramic with B2O3–CuO addition

The influence of B₂O₃–CuO addition on the sintering behavior, phase composition, microstructure and microwave dielectric properties of BiSbO₄ ceramic have been investigated. The BiSbO₄ ceramics can be well densified to approach above 95% theoretical density in the sintering temperature range from 840 to 960 °C as the addition amount of B₂O₃–CuO increases from 0.6 to 1.2 wt.%. Sintered ceramic samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The microwave permittivity ?_r saturated at 19–20 and Qf values varied between 33,000 and 46,000 GHz while temperature coefficient of resonant frequency shifting between ?70 and ?60 ppm/°C at sintering temperature around 930 °C. Lowering sintering temperature of BiSbO₄ ceramics makes it possible for application in low temperature co-fired ceramic technology.     

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.     

Influence of MnO2 and Co3O4 dopants on dielectric properties of Pb(Fe2/3W1/3)O3 ceramics

Dielectric properties of Pb(Fe_2/3W_1/3)O₃ ceramic doped with 0.05–1 mol% of MnO₂ or Co₃O₄ were investigated in a wide temperature range from −160 to 450 °C at frequencies 10 Hz–1 MHz. Besides the maxima corresponding to the ferroelectric–paraelectric transition, at higher temperatures other peaks in temperature dependencies of relative electrical permittivity and dissipation factor were observed, attributed to dielectric relaxation. The location and height of these peaks are strongly related to frequency and the dopant level. Both MnO₂ and Co₃O₄ addition caused a significant increase in the resistivity of PFW ceramic—from 10⁶ Ω cm for undoped samples to 10¹¹ Ω cm for those with 1 mol% of a dopant. The activation energies of relaxation calculated on the basis of dielectric measurements are very close to the conduction activation energies determined in similar temperature range.     

Low sintering temperature of (Zn0.65Mg0.35)TiO3–xCaTiO3-based dielectric with controlled temperature coefficient

(Zn_0.65Mg_0.35)TiO₃–xCaTiO₃-based dielectric ceramics sintered at low temperature thanks to ZnO–B₂O₃ glass phase addition are investigated. The effects of such additions on the dilatometric curves, the microstructure, the phase composition and the dielectric properties have been carefully examined. It is shown that the sintering temperature is significantly lowered to 930 °C by the addition of 2 wt.% of ZnO–B₂O₃ glass phase. The temperature coefficient of permittivity (τ_?) could be controlled by varying the CaTiO₃ content and lead to near zero τ_? value. As an optimal composition, (Zn_0.65Mg_0.35)TiO₃ + 7%CaTiO₃, co-sinterable with silver electrodes at 930 °C, exhibits at 1 MHz, a relative permittivity of ?_r = 21, a temperature coefficient of the permittivity τ_? of ?4 ppm/°C and low dielectric losses (tan(δ) < 10^?3). These interesting properties make this system promising to manufacture Ag-based electrodes multilayer dielectric devices.     

The dielectric properties for (Nb,In,B) co-doped rutile TiO2 ceramics

Recently, colossal permittivities (~10⁵) and low loss factors (<0.1) were reported in (Nb+In) co-doped rutile TiO₂ ceramics, which have attracted considerable attention. In this work, (Nb,In,B) co-doped rutile TiO₂ ceramics were investigated for achieving temperature- and frequency- stable dielectric properties in TiO₂ based colossal dielectric ceramics. The (Nb,In,B) co-doped rutile TiO₂ ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and complex impedance of 1 mol.% (Nb+In) co-doped rutile TiO₂ (TINO) and xwt% B₂O₃ (x=0.5, 1, 2 and 4) doped TINO were systematically investigated and compared. It was found that by doping B₂O₃ the sintering temperature of TINO ceramics can be reduced by 100 °C. Meanwhile, the dielectric loss of TINO ceramics was decreased by doping B₂O₃. In the ₂wt% B₂O₃ doped TINO ceramics, the dielectric permittivity kept a high value of >2.0×10⁵ and the dielectric loss was lower than 0.1 in a frequency range of 10²−10⁵ Hz and a temperature range of 25–200 °C.     

Low-temperature synthesis and microwave dielectric properties of trirutile-structure MgTa2O6 ceramics by aqueous sol–gel process

Trirutile-structure MgTa₂O₆ ceramics were prepared by aqueous sol–gel method and microwave dielectric properties were investigated. Highly reactive nanosized MgTa₂O₆ powders were successfully synthesized at 500 °C in oxygen atmosphere with particle sizes of 20–40 nm. The evolution of phase formation was detected by DTA–TG and XRD. Sintering characteristic and microwave dielectric properties of MgTa₂O₆ ceramics were studied at different temperatures ranging from 1100 to 1300 °C. With the increase of sintering temperature, density, ?_r and Q · f values increased and saturated at 1200 °C with excellent microwave properties of ?_r ～ 30.1, Q · f ～ 57,300 GHz and τ_f ～ 29 ppm/°C. The sintering temperature of MgTa₂O₆ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state method.     

Grain size effect on electromechanical properties and non-linear response of dense nano and microstructured PIN–PT ceramics

Nanopowders of 0.63Pb(In_1/2Nb_1/2)O₃–0.37PbTiO₃ were synthesized by solid state reaction using the continuous attrition milling followed by high-energy ball milling techniques in air at room temperature. After milling for 8 h nanopowders of 20–30 nm grain size are obtained. Sintering by hot pressing of PIN–37PT green pellets leads to dense ceramics with average grain size varying from 100 nm to 1 μm. The dielectric and piezoelectric properties of PIN–37PT nanostructured ceramics with grain size bigger than about 160 nm remain roughly unchanged and comparable to those of microstructured ceramics. In addition, the stability of the permittivity and dielectric losses under high ac electric field grows when the grain size decreases. The material becomes less non-linear with decreasing grain size. This result is attractive for acoustic transducer applications.     

High-temperature dielectrics in CaZrO3-modified Bi1/2Na1/2TiO3-based lead-free ceramics

Materials in two composition regimes, Bi_1/2Na_1/2TiO₃–BaTiO₃–CaZrO₃ (BNT–BT–CZ) and Bi_1/2Na_1/2TiO₃–BaTiO₃–K_0.5Na_0.5NbO₃–CaZrO₃ (BNT–BT–KNN–CZ), were synthesized via the mixed oxide route and their structural, dielectric and electrical properties were investigated. CZ was identified to render the two local maxima in permittivity more diffused. This resulted in temperature-insensitive relative permittivity spectra with average values from ～470 up to ～2300 and operational windows of at least ～400 °C with less than 15% of variation in the temperature range from ?100 up to above 500 °C. Moreover, loss factors are below ～10% and RC constants range from ～0.03 s up to ～4 s at 300 °C. The materials of current investigation are highly attractive for developing capacitors of wide temperature usage.     

Origin of giant dielectric response in LiCuNb3O9 distorted perovskite ceramics

LiCuNb₃O₉ ceramics with the distorted cubic perovskite structure were prepared by a solid-state reaction method. The ceramic exhibited a very large value of permittivity (∼4.4 × 10⁴ at 100 kHz) at room temperature (∼300 K) and a low-temperature dielectric relaxation behaviour following the Arrhenius law. The origin of the giant dielectric response of the LiCuNb₃O₉ ceramics was correlated with the structure of the ceramics. The barrier layers in the grain boundaries and the mixed-valent structure of Cu⁺/Cu²⁺ were found to contribute to the giant permittivity of the ceramics and confirmed by X-ray spectroscopy and complex impedance spectroscopy analyses.     

The structure and properties of 0.95MgTiO3–0.05CaTiO3 ceramics co-doped with ZnO–ZrO2

The (Mg_0.93Ca_0.05Zn_0.02)(Ti_1?xZr_x)O₃ ceramics were prepared by conventional solid-state route. The dielectric properties and structure of (Mg_0.93Ca_0.05Zn_0.02)(Ti_1?xZr_x)O₃ ceramics were investigated. It has been found that MgTiO₃ and CaTiO₃ are the main phases and a second phase CaZrTi₂O₇ appeared in 95MCT ceramics co-doped with Zn–Zr. With Zn–Zr additive, the sintering temperature of 95MCT ceramics can be reduced to 1300 °C, and adjust the temperature coefficient of dielectric constant. With the increasing of Zr content, dielectric constant ?_r decrease from 22.6 to 19.91 and the temperature coefficient of dielectric constant α_c from 5.93 to 2.52 ppm/°C when x = 0.01, 0.02, 0.03 and 0.04 mol respectively. The 95MCT ceramics with x = 0.02 has a dielectric constant ?_r of 22.02, a dielectric loss of 2.78 × 10^?4 and a temperature coefficient of dielectric constant α_c value of 2.98 ppm/°C.     

Colossal permittivity and impedance analysis of tantalum and samarium co-doped TiO2 ceramics

In this study, (Ta_0.5Sm_0.5)_xTi_1−xO₂ (x = 0, 0.02, 0.06, 0.15) ceramics (referred to as TSTO) were fabricated by a standard solid-state reaction. As revealed by the X-ray diffraction (XRD) spectra, the TSTOs exhibit a tetragonal rutile TiO₂ structure. All the TSTO ceramics display colossal permittivity (~ 10²–10⁵). Moreover, the optimal ceramic, (Ta_0.5Sm_0.5)_0.02Ti_0.98O₂, exhibits high performance over a wide temperature range from 20 °C to 160 °C. At 1 kHz, the dielectric constant and dielectric loss are 2.30 × 10⁴ and 0.11 at 20 °C; they are 3.85 × 10⁴ and 0.64 at 160 °C. Dielectric and impedance spectra analyses for the TSTO ceramics indicate that the CP behavior over a broad temperature range in (Ta+Sm) co-doped TiO₂ could be explained by the internal barrier layer capacitance (IBLC) model, which consists of semiconducting grains and insulating grain boundaries.     

BiFeO3 ceramics synthesized by spark plasma sintering

Phase-pure BiFeO₃ particles were synthesized by an improved solid state technique. High density BiFeO₃ ceramics were prepared using these particles by spark plasma sintering (SPS). The dielectric permittivity and loss of SPS samples were measured as functions of sintering temperature, frequency, and annealing conditions. Dielectric spectra of the ceramics annealed at 650 °C were characterized in a broad range of temperature (300–725 K) and frequency (100 Hz to 20 MHz). Two kinds of dielectric relaxation following the Arrhenius law were detected in low and high temperature ranges, respectively. The low temperature dielectric relaxation could be almost completely removed by annealing in vacuum and it should be assigned to be a valence fluctuation of Fe ions, while the high temperature dielectric relaxation was proposed to stem from the short-range motion of oxygen vacancies.     

Microwave dielectric properties of Bi-substituted La(Mg1/2Ti1/2)O3

The system La(Mg_1/2Ti_1/2)O₃–Bi(Mg_1/2Ti_1/2)O₃ (LMT–BMT) was investigated in respect to formation of perovskite solid solutions based on lanthanum magnesium titanate. Single-phase perovskite (1 − x)LMT–xBMT ceramics (0 ≤ x ≤ 0.3) were prepared and their crystal structure and dielectric properties were studied. It has been found that within the solubility range the crystal structure of Bi-substituted LMT remains monoclinic, P2₁/n. Unit cell volume was evaluated to be almost independent on x, varying within the experimental error. Relative permittivity of the ceramics increases by almost a factor of 3 in the range 0 ≤ x ≤ 0.3 and its value is 40–45 at the compositional region where temperature coefficient of the resonant frequency passes a zero-value. Compositional and temperature variations of the dielectric parameters for LMT–BMT estimated at different frequency ranges are considered in comparison with those observed in other Bi-substituted ceramics based on LMT.     

Low-temperature sintering and microwave dielectric properties of Nd(Co1/2Ti1/2)O3 ceramics using glass addition of oxides

The microstructures and microwave dielectric characteristics of complex perovskite Nd(Co_1/2Ti_1/2)O₃ ceramics with 60P₂O₅–15ZnO–5La₂O₃–5Al₂O₃–5Na₂O–5MgO–5Yb₂O₃ (PZLANMY) additions (1–4 wt%) prepared through the conventional solid-state route were investigated. It was found that Nd(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1210 °C owing to the sintering aid of PZLANMY-glass addition. At 1300 °C, Nd(Co_1/2Ti_1/2)O₃ ceramics with 1 wt% of PZLANMY-glass addition possess a dielectric constant (ε_r) of 27, a Q×f value of 64,000 GHz and a temperature coefficient of resonant frequency (τ_f) of ?29 ppm/°C. The PZLANMY-glass doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices that require low sintering temperature.     

Low-temperature microwave and THz dielectric response in novel microwave ceramics

Low-temperature dielectric properties of BaZn_1/3Nb_2/3O₃-based ceramics, CeO₂-based ceramics and Ruddlesden–Popper Sr_n+1Ti_nO_3n+1 (n = 1–4) ceramics has been studied in microwave, THz and infrared frequency range down to 10 K. Extrinsic dielectric losses originating probably from diffusion of charged defects are observed in two families of compounds by a minimum in the temperature dependence of microwave quality Q. The rise of microwave permittivity and dielectric losses at low temperatures in Sr_n+1Ti_nO_3n+1 (n = 2–4) ceramics was explained by softening of an optical polar mode in SrTiO₃, which is in the Sr_n+1Ti_nO_3n+1 (n = 3, 4) ceramics contained as a second phase.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.