Influence of 4ZnO–B2O3 Addition on Dielectric Properties and Microstructures of Barium Strontium Titanate

This study investigates the effect of 4ZnO–B₂O₃ on the sintering behavior, dielectric properties, and microstructures of Ba_0.6Sr_0.4TiO₃ (BST) ceramics. These ceramics were sintered in air at temperatures ranging from 900°C to 1080°C. BST ceramics with 4ZnO–B₂O₃ addition can be sintered to a theoretical density higher than 95% at 1050°C. A secondary phase (Ba₂ZnTi₅O₁₃) is produced in the BST ceramics during 4ZnO–B₂O₃ addition. Compositional analysis using TEM-EDX of the BST ceramics with 3 wt% 4ZnO–B₂O₃ revealed that the Zn ion is generally located at the triple points. This result indicates that BaO, TiO₂, and ZnO form a liquid phase that acts as a secondary phase at the lower sintering temperatures. The amount of secondary phase was observed to increase as the amount of 4ZnO–B₂O₃ additives increased. In addition, the original Ba_0.6Sr_0.4TiO₃ phase was shifted to the Ba_0.5Sr_0.5TiO₃ phase by the addition of 3 wt% 4ZnO–B₂O₃ at 1050°C. The Ba_0.6Sr_0.4TiO₃ ceramic with 2 wt% 4ZnO–B₂O₃ sintered at 1050°C in air for 2 h exhibited dielectric properties of ɛ_r=1883 and dissipation loss=0.36%. Moreover, BST with 1 wt% 4ZnO–B₂O₃ addition sintered at 1080°C exhibits dielectric properties of ɛ_r=2330, dissipation loss=0.29%, and bulk density >95% of theoretical density.     

Influences of B2O3/CuO additions on the sintering behavior,microstructure and microwave dielectric properties of 6Nd[(Zn0.7Co0.3)0.5Ti0.5]O3–4(Na0.5Nd0.5)TiO3 ceramics

B₂O₃ and CuO were codoped into 6Nd[(Zn_0.7Co_0.3)_0.5Ti_0.5]O₃–4(Na_0.5Nd_0.5)TiO₃ (abbreviated as 6NZCT–4NNT) ceramics as sintering aids. The influences of the sintering aids on the sintering characteristics, microstructure and microwave dielectric properties of the 6NZCT–4NNT ceramics were systematically investigated as a function of the proportion of B₂O₃ and CuO. Codoping could greatly reduce the sintering temperature from 1410 °C to 1150 °C, indicating that B₂O₃/CuO are good sintering aids for 6NZCT–4NNT ceramics. The B₂O₃/CuO sintering aids had no significant impact on the phase purity of the investigated ceramics, even though a solid solution was formed due to Cu²⁺ ion substitution. However, they had evident influences on the surface morphology and grain size. The average grain size was enlarged with increasing amounts of CuO in the B₂O₃/CuO sintering aids. Remarkable deterioration of the microwave dielectric properties for 6NZCT-4NNT ceramics was not observed when codoping an appropriate amount of B₂O₃ and CuO. The 6NZCT–4NNT ceramics codoped with 2.0 mol% B₂O₃ and 2.0 mol% CuO sintered at 1150 °C for 3 h exhibited a homogeneous microstructure and promising microwave dielectric properties: an appropriate dielectric constant (ε_r = 49.37), a high quality factor (QF = 47,295 GHz), and a near-zero temperature coefficient of resonant frequency (TCF = +0.9 ppm/^°C).     

Microstructures and dielectric properties of spark plasma sintered Ba0.4Sr0.6TiO3/CaCu3Ti4O12 composite ceramics

(1 − x)Ba_0.4Sr_0.6TiO₃/xCaCu₃Ti₄O₁₂ composite ceramics were prepared by spark plasma sintering. Sintering behavior, microstructures and dielectric properties of the composite ceramics were investigated by XRD, SEM, EDS and dielectric spectrometer. Dense composite ceramics consisting of Ba_0.4Sr_0.6TiO₃ phase and CaCu₃Ti₄O₁₂ phase were prepared at 800 °C for 0 min. The dielectric loss of the composite ceramic decreased with increasing amount of Ba_0.4Sr_0.6TiO₃, and the high dielectric constant were retained. Moreover, the better temperature stability of dielectric constant was obtained. These improvements of dielectric characteristics have great scientific significance for potential application.     

Low temperature sintering of the Ba2Ti9O20 ceramics using B2O3/CuO and BaCu(B2O5) additives

The effects of B₂O₃/CuO and BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of Ba₂Ti₉O₂₀ ceramics were investigated. The B₂O₃ added Ba₂Ti₉O₂₀ ceramics were not able to be sintered below 1000 °C. However, when both CuO and B₂O₃ were added, they were sintered below 900 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the Ba₂Ti₉O₂₀ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the Ba₂Ti₉O₂₀ ceramics. Good microwave dielectric properties of Qxf = 16,000 GHz, ɛ_r = 36.0 and τ_f = 9.11 ppm/°C were obtained for the Ba₂Ti₉O₂₀ ceramics containing 10.0 mol% BaCu(B₂O₅) sintered at 875 °C for 2 h.     

Effects of adding B2O3 on microwave dielectric properties of 0.9625MgTiO3-0.0375(Ca0.5Sr0.5)TiO3 composite ceramics

A series of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics added with different amounts of B₂O₃ (1-5 wt%) were prepared via the solid state sintering method using the pre-synthesized raw MgTiO₃ and (Ca_0.5Sr_0.5)TiO₃ powders by molten-salt reaction. The sintering temperature of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics can be reduced from 1275°C to 1175°C due to the liquid phase sintering effect of B₂O₃. When the adding amount of B₂O₃ was more than 2 wt%, a new phase MgTi₂O₅ could be detected by X-ray diffraction, which would substantially degrade the dielectric properties of the obtained ceramics. Resultantly, the quality factor (Q·f) and dielectric constant (ε_r) of the samples increase first and decrease later with increasing addition amount of B₂O₃. In addition, the temperature coefficient of resonant frequency (τ_f) progressively increases with increasing content of B₂O₃. By sintering at 1175°C for 4 hours, the obtained 0.9625MgTiO₃-0.0375Ca_0.5Sr_0.5TiO₃ composite ceramics with 2 wt% B₂O₃ possess the optimal microwave dielectric properties of ε_r = 18.9, Q·f = 57 000 GHz and τ_f = −1.2 ppm/°C.     

Colossal dielectric permittivity in (Al+Nb) co-doped Ba0.4Sr0.6TiO3 ceramics

Stimulated by the outstanding colossal permittivity behavior achieved in trivalent and pentavalent cations co-doped rutile TiO₂ ceramics, the co-doping effects on the dielectric behavior of Ba_0.4Sr_0.6TiO₃ ceramics were further explored. In this work, (Al + Nb) co-doped Ba_0.4Sr_0.6TiO₃ ceramics were synthesized via a standard solid state ceramic route. The structural evolution was analyzed using X-ray diffraction patterns and Raman spectra. Dense microstructures with no apparent change of grain morphology were observed from the scanning electron microscopy. A huge enhancement of dielectric permittivity was obtained with 1 mol% (Al + Nb) doping and excellent dielectric performances (ε_r ∼ 20,000, tanδ ∼ 0.06 at 1 kHz) were achieved after further heat treatment. The formation of electron pinned defect dipoles localized in grains may account for the optimization of dielectric behaviors and the corresponding chemical valence states were confirmed from the XPS results.     

Microwave dielectric properties and low-temperature sintering of Ba3Ti4Nb4O21 ceramics with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ɛ_r), high quality factor (Q × f) and small temperature coefficient of resonant frequency (τ_f) are required for the application of chip passive components in the wireless communication technologies. In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₄Nb₄O₂₁ ceramics were investigated as a function of B₂O₃–CuO content. Ba₃Ti₄Nb₄O₂₁ ceramics with B₂O₃ or CuO addition could be sintered above 1100 °C. However, the additions of both B₂O₃ and CuO successfully reduced the sintering temperature of Ba₃Ti₄Nb₄O₂₁ ceramics from 1350 to 900 °C without detriment to the microwave dielectric properties. From the X-ray diffraction (XRD) studies, the sintering behaviors and the microwave dielectric properties of low-fired Ba₃Ti₄Nb₄O₂₁ ceramics were examined and discussed in the formation of the secondary phases. The Ba₃Ti₄Nb₄O₂₁ sample with 1 wt% B₂O₃ and 3 wt% CuO addition, sintered at 900 °C for 2 h, had the good dielectric properties: ɛ_r = 65, Q × f = 16,000 GHz and τ_f = 101 ppm/°C.     

Grain-size-insensitive dielectric properties of Sr0.6Ba0.4Nb2O6 relaxor ferroelectric ceramics with tetragonal tungsten bronze structure

The influence of grain size on the dielectric properties of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) ceramics with a tetragonal tungsten bronze structure was examined. The conventional and two-step sintering procedures were used to fabricate dense and phase-pure SBN60 ceramics with grain sizes ranging from 2.2 μm to 17.3 μm. In the temperature dependence of the dielectric permittivity, all samples showed a relaxor-like broad dielectric peak with a maximum at around 60 °C. The maximum dielectric permittivity and dielectric maximum temperature of the SBN ceramics were found to be less dependent on the grain size. The reason for the grain-size-insensitive dielectric properties of the SBN60 ceramics is discussed based on the analysis of the dielectric properties and Raman spectra.     

Microstructure and Dielectric Properties of Nickel‐Doped Ba0.7Sr0.3TiO3 Ceramics Fabricated by Solgel Method

A study of phase transition, microstructure, and dielectric properties of Ba_0.7Sr_0.3Ti_1–xNi_xO₃ (BSTN) ceramics prepared by slow‐injection solgel technique with x ranging from 0 to 1 mol% is reported in this article. The as‐prepared BSTN material was calcined at 800 and 1000°C and subsequently sintered at 1100 and 1200°C, respectively. The optimized condition was found to be Ba_0.7Sr_0.3TiO₃ doped with 1 mol% nickel calcined at 1000°C and sintered at 1200°C having the lowest dielectric loss of 0.02 with a dielectric constant of 1603 which was measured at a frequency of 1 kHz at room temperature.     

The structures and dielectric properties of Ba0.80Sr0.20TiO3/Pb0.82La0.18TiO3 composite thick films with addition of PbO–B2O3 glass

Sol–gel derived Ba_0.80Sr_0.20TiO₃ (BST) and Pb_0.82La_0.18TiO₃ (PLT) powders and a low-melting PbO–B₂O₃ glass powder were mixed to prepare paste. The composite thick films (∼40 μm) were fabricated by screen-printing the paste onto the Al₂O₃ substrates with screen-printed silver bottom electrode and then sintered at the low temperature 650–800 °C, respectively. X-ray diffraction (XRD), transmission microscope (TEM), scanning electron microscope (SEM) and an impedance analyzer were used to analyze the structures, microstructures and dielectric properties of the powders and the composite thick films. The results show that the composite thick films containing sol–gel derived Ba_0.80Sr_0.20TiO₃ and Pb_0.82La_0.18TiO₃ perovskite phases have been fabricated by using the PbO–B₂O₃ glass as a sintering aid. Compared to conventional sintering at ≥1200 °C, high densification of the composite thick films is achieved at temperature as low as 800 °C by the “wetting” and “infiltration” of the liquid phase on the particles. The homogenization of the BST and PLT perovskite phase in the composite thick films is evitable by controlling the sintering temperature and time. The formation of the small amount of pyrochlore phase in composite thick films sintered at 800 °C is resulted from both the volatilization of PbO and the interaction between the PLT and PbO–B₂O₃ glass. The relative dielectric properties of the composite thick films exhibit good temperature-stable behavior, and the variation of the relative dielectric constant is less than 10% in the temperature range 0–300 °C.     

Improvement of dielectric loss of (Ba,Sr)(Ti,Zr)O3 ferroelectrics for tunable devices

(Ba_0.6Sr_0.4)(Ti_1−xZr_x)O₃ (0.05 ≤ x ≤ 0.3) ferroelectric materials have cubic perovskite structure and show paraelectric properties at room temperature. Curie point shifted to a negative value as increasing Zr content in (Ba_0.6Sr_0.4)(Ti_1−xZr_x)O₃ system. When Zr substituted 0.1 mol, the dielectric constant, dielectric loss, tunability, Curie point and FOM were 4500, 0.0005, 63%, −1.6 °C and 1260, respectively. This composition shows excellent microwave dielectric properties than those of (Ba_0.6Sr_0.4)TiO₃ ferroelectrics, which are limelight materials for tunable devices such as varactors, phase shifters and frequency agile filters, etc.     

Effects of MnO2 and WO3 co-doping and sintering temperature on microstructure,microwave dielectric properties of Ba2Ti9O20 microwave ceramics

Ba₂Ti₉O₂₀ (short for B2T9) ceramics doped with 0.9 mol% MnO₂ and y mol% WO₃ were prepared by solid-state reaction. The influence of sintering temperature, content of WO₃ dopant and the molar ratio x of TiO₂: BaCO₃ on crystal structure, microstructures as well as microwave dielectric properties of B2T9 ceramics was systematically investigated. The major phase of all samples is B2T9, and the minor phase is BaWO₄, respectively. The content of impurity TiO₂ alternates with the variation of compositions and sintering temperature, which also leads to different microwave dielectric properties. With the continuous increase of the sintering temperature, the B2T9 phase grains gradually grow larger and transform from rod grains to plate-like grains. The enlargement and flattening of grains also result in the decrease of compactness and deterioration of microwave dielectric properties. It is found that B2T9 ceramics possess better performance when the sintering temperature is 1340°C, which is related to lower TiO₂ content, BaWO₄, B2T9 grain size, aspect ratio of B2T9 phase and high compactness. When x = 4 and y = 0.2, the relative dielectric constant, quality factor and the temperature coefficient of resonant frequency are 38, 23758 and 7 ppm/°C, respectively.     

Property optimization of Ba0.4Sr0.6TiO3–BaMoO4 composite ceramics for tunable microwave applications

(1 ? x)Ba_0.4Sr_0.6TiO₃–xBaMoO₄ ceramics with x = 5, 10, 20, 30, 40 and 60 wt% were prepared by traditional solid-state reaction method. Two crystalline phases, a cubic perovskite structure Ba_0.4Sr_0.6TiO₃ (BST) and a tetragonal scheelite structure BaMoO₄ (BM) were obtained by XRD analysis. The microwave dielectric properties of Ba_0.4Sr_0.6TiO₃–BaMoO₄ composite ceramics were investigated systematically. The results show that the composite ceramics exhibited promising microwave properties. The dielectric constant can be adjusted in the range from 900 to 78, while maintaining relatively high tunability from 27.3% to 12.8% under a direct current electric field of 60 kV/cm and Q values from 619 to 67 in the gigahertz frequency region.     

Improved dielectric properties of Ba0.5Sr0.5TiO3–ZnAl2O4 composite ceramics using double sintering

Ba_0.5Sr_0.5TiO₃–ZnAl₂O₄ composite ceramics were prepared by double sintering and conventional sintering. The results show that the double sintering can effectively reduce the ion diffusion between Ba_0.5Sr_0.5TiO₃ and ZnAl₂O₄ phases. The double sintered samples exhibit higher density and more uniform grain size distribution than the conventional sintered samples. The dielectric permittivity of double sintered samples is lower than that of conventional sintered samples. Impedance spectrum analysis shows that the oxygen vacancy content and grain boundary resistance of the double sintered samples is lower than that of the conventional sintered samples, which indicates that the Q value of the double sintered samples is higher than that of the conventional sintered samples. The optimum dielectric tunability and Q value of double sintered 60 wt%Ba_0.5Sr_0.5TiO₃-40 wt%ZnAl₂O₄ sample are 23.4% at 30 kV/cm and 276 at 2.257 GHz, respectively. Therefore, double sintering is a strategy that can effectively adjust the dielectric tunability and Q value of BST-ZA composite ceramics.     

A Novel Magnetodielectric Solid Solution Ceramic 0.4LiFe5O8–0.6Li2MgTi3O8 with Excellent Microwave Dielectric Properties

In this study, a novel spinel solid solution ceramic of 0.4LiFe₅O₈–0.6Li₂MgTi₃O₈ (0.4LFO–0.6LMT) has been developed and investigated. It is found that the 40 mol% LiFe₅O₈ and 60 mol% Li₂MgTi₃O₈ are fully soluble in each other and a disordered spinel phase is formed. The ceramic sample sintered at 1050°C/2 h exhibits both good magnetic and dielectric properties in the frequency range 1–10 MHz, with a permeability between 29.9~14.1 and magnetic loss tangent between 0.12~0.67, permittivity between 16.92~16.94 and dielectric loss tangent between 5.9 × 10^?3–2.3 × 10^?2. The sample also has good microwave dielectric properties with a relative permittivity of 16.1, a high quality factor (Q × f) ~28 500 GHz (at 7.8 GHz). Furthermore, 3 wt% H₃BO₃–CuO (BCu) addition can effectively lower the sintering temperature to 925°C and does not degrade the magnetodielectric properties. The chemical compatibility with silver electrode indicates that this kind of ceramics is a good candidate for the low‐temperature cofired ceramic (LTCC) application.     

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.     

Effect of V2O5 on sintering behaviour,microstructure and dielectric properties of textured Sr0.4Ba0.6Nb2O6 ceramics

The acicular Sr_0.39Ba_0.48K_0.32Nb₂O₆ single crystal particles were first prepared by the reaction of SrCO₃, BaCO₃ and Nb₂O₅ in molten K₂SO₄ at 1300 °C for 3 h. By using these single crystal particles as seeds and V₂O₅ as additives, textured Sr_0.4Ba_0.6Nb₂O₆ (SBN40) ceramics were obtained. The effect of V₂O₅ on sintering behaviour, microstructure and dielectric properties of textured SBN40 ceramics was investigated. The experimental results show that the addition of V₂O₅ can accelerate the densification rate of the material and encourage the texture of SBN40 ceramics, which further improves the anisotropy in dielectric properties between different directions of textured SBN40 ceramics.     

Grain size-driven effect on the functional properties in Ba0.6Sr0.4TiO3 ceramics consolidated by spark plasma sintering

Dense fine-grained Ba_0.6Sr_0.4TiO₃ ceramics with submicronic grains sizes (GS) have been prepared using nanopowders synthesized via sol-gel route and consolidated by Spark Plasma Sintering (SPS). By changing SPS parameters, the GS was reduced from 214 nm to 74 nm. Diffuse ferroelectric-paraelectric phase transitions and low values of dielectric permittivity (<1000) at the Curie temperature (T_C ∼280 K) were revealed by Impedance Spectroscopy in all sintered ceramics. The GS reduction from submicron to nanoscale range reflects in a gradually diminishment of dielectric constant, tunability, polarisation and storage energy properties. Raman spectroscopy investigations pointed out the presence of polar nanoclusters above the T_C. The short-range polar order is affected by the GS decrease, but becomes more thermally stable. The observed properties of Ba_0.6Sr_0.4TiO₃ nanostructured ceramics are interpreted by considering the interplay between the GS reduction, the role of low-permittivity grain boundaries and the diffuse character of the ferroelectric-to-paraelectric transformation.     

Dielectric relaxation behavior and energy storage properties in Ba0.4Sr0.6Zr0.15Ti0.85O3 ceramics with glass additives

Ba_0.4Sr_0.6Zr_0.15Ti_0.85O₃ ceramics with SrO–B₂O₃–SiO₂ glass additives were prepared via the solid state reaction route. The effects of glass contents on the sintering behavior, dielectric properties, microstructures, and energy storage properties of BSZT ceramics were investigated. Dielectric breakdown strength of 22.4 kV/mm was achieved for BSZT ceramics with 20 wt% glass addition. Dielectric relaxation behavior was observed in dielectric loss versus temperature plots. In order to investigate the mechanism of dielectric breakdown performance, the relationship between dielectric breakdown strength and grain boundary barrier was studied by the measurements of breakdown strength and activation energy. A discharged energy density of 0.45 J/cm³ with an energy efficiency of 88.2% was achieved for BSZT ceramics with 5 wt% glass addition.     

Effect of CuO/MnO additives on microstructure and microwave dielectric properties of 3ZrO2-3TiO2-ZnNb2O6 ceramics

The effect of CuO/MnO additives on phase composition, microstructures, sintering behavior, and microwave dielectric properties of 3ZrO₂-3TiO₂-ZnNb₂O₆ (3Z-3T-ZN) ceramics prepared by conventional solid-state route were systematically investigated. CuO/MnO doped ceramics exhibited a main phase of α-PbO₂-structured ZrTi₂O₆ and a secondary phase of rutile TiO₂. SEM results showed that the grain size of MnO doped ceramics became larger with increasing amount of dopants. The presence of CuO/MnO additives effectively reduced the sintering temperature of 3Z-3T-ZN ceramics to 1220 °C. MnO doped into ceramics could enhance the Q×f values significantly. The 0.5 wt% CuO doped 3Z-3T-ZN ceramics with 0.5 wt% of MnO, sintered at 1220 °C for 4 h, was measured to show superior microwave dielectric properties, with an ε_r of 41.02, a Q×f value of 44,230 GHz (at 5.2 GHz), and τ_f value of +2.32 ppm/°C.