Structure Property Relationship in BaTiO3–Na0.5Bi0.5TiO3–Nb2O5–NiO X8R System

A novel BaTiO₃–Na_0.5Bi_0.5TiO₃–Nb₂O₅–NiO (BT‐NBT‐Nb‐Ni) system that meets the X8R specification (?55°C–150°C, ΔC/C≤±15%) of multilayer ceramic capacitors (MLCCs) was fabricated, with a maximum dielectric constant of 2350 at room temperature (25°C). Core–shell microstructure was observed by transmission electron microscopy (TEM), accounting for the good dielectric temperature stability. The role of Ni on the formation of core–shell structure and phase structure, and the subsequent relationship between structure and dielectric/ionic conduction properties were investigated. It was observed that the addition of Ni could adjust the ratio of core/shell, and significantly reduces the dielectric loss over the studied temperature range. A new Ba₁₁(Ni, Ti)₂₈O_66+x phase with a 10‐layer close‐packed structure was identified by X‐ray diffraction (XRD), serving as a source of oxygen vacancies for ionic conduction in addition to Ba(Ni,Ti)O₃. Furthermore, the impedance spectroscopy measurements demonstrated the remarkable impact of these Ni‐induced oxygen vacancies on both the grain and grain‐boundary conductivities.     

High‐Temperature Multilayer Ceramic Capacitors Based on 100−x(94Bi1/2Na1/2TiO3–6BaTiO3)–xK0.5Na0.5NbO3

The potential high‐temperature dielectric materials 100?x(94Bi_1/2Na_1/2TiO₃–6BaTiO₃)–xK_0.5Na_0.5NbO₃ with x = 12, 18, and 24 were processed as bulk samples in order to examine the reduction of sintering temperature by means of CuO as sintering aid. Due to the successful reduction of sintering temperature, low cost Ag:Pd could be used as a co‐fired electrode material for multilayer ceramic capacitors (MLCCs). Fabrication of 8 μm thick, dense MLCCs with self‐contained, nonreactive electrodes is reported for a wide range of compositions of Bi_1/2Na_1/2TiO₃–BaTiO₃–K_0.5Na_0.5NbO₃. Among the manufactured MLCCs, those with compositions x = 24 showed the most promising dielectric properties for applications where high operating temperatures are needed. The temperature‐dependence of permittivity was quite low, revealing a change of less than ±10% compared to its 150°C‐value in the range of 40°C–225°C. For samples sintered at 1000°C, an RC constant of about 300 s was obtained at 150°C. Furthermore, these x = 24 MLCCs exhibited the finest microstructures among the compositions examined; making it a suitable candidate for further miniaturization of layer thickness as required for state‐of‐the art devices.     

Flexible /PET/batio3/ layer–layer composite film with enhanced dielectric properties fabricated by highly loaded /batio3/ coating with acrylic resin as binder

Flexible layer–layer poly(ethylene phthalate) (PET)/BaTiO₃ composite films with enhanced dielectric permittivity were fabricated by spin coating method, consisting of PET substrate film layer and modified BaTiO₃/acrylic resin hybrid coating layer. The thickness of coating layer was less than 3 μm (about 2% of PET film thickness), and therefore, the PET/barium titanate (BT) composite films remained flexible even at high volume fraction of BaTiO₃ fillers. The volume contents of BaTiO₃ were varied from 0 to 80%, and the solid contents of BaTiO₃/acrylic resin were in the range of 51.8–72.9%. Scanning electron microscopy showed strong interaction of finely dispersed BaTiO₃ particles with acrylic resin. Morphological profile also displayed uniform coating layer of modified BaTiO₃/acrylic resin and its strong adhesion with PET film. The dielectric constant of the PET/BaTiO₃ composite films increased by about 26% at 60 vol % BaTiO₃ loading when compared with the pristine PET film, whereas the dielectric loss decreased slightly. In addition, PET‐grafted poly(hydroxylethyl methacrylate) brushes were used as substrate to introduce covalent bonding with the coating layer. Further enhancement of dielectric constant and reduction of dielectric loss were realized when compared with the composite films with bare PET substrate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42508.     

Core–Shell Structure and Dielectric Properties of Ba0.991Bi0.006TiO3@Nb2O5–Co3O4 Ceramics

To meet the needs of future multilayer ceramic capacitors (MLCCs), thinner dielectric layers are necessary. To achieve this goal, the grain size and uniformity of the particles must be effectively controlled. In this study, we confirmed a core–shell particle structure by means of X‐ray diffraction, scanning electron microscopy, and energy‐dispersive spectroscopy. The dielectric properties of the ceramics were measured using an LCR meter. We found Ba_0.991Bi_0.006TiO₃ particles form a core that was coated with a homogeneous Nb₂O₅–Co₃O₄ layer (~9 nm). The relationship between core–shell structure and ε_r‐T curves of the Ba_0.991Bi_0.006TiO₃@Nb₂O₅–Co₃O₄ ceramics by different sintering temperature has been investigated. Dense, fine‐grained Ba_0.991Bi_0.006TiO@Nb₂O₅–Co₃O₄ ceramics were obtained by sintering at 1160°C. The ceramics met the X8R requirements, with a maximum dielectric constant of 2795, and a low dielectric loss at room temperature of 0.89%.     

Evaluation of Rare‐Earth Modified ZrB2–SiC Ablation Resistance Using an Oxyacetylene Torch

Rare‐earth modified ZrB₂–SiC coatings were prepared via mechanical mixing Sm₂O₃ or Tm₂O₃ powders with spray‐dried ZrB₂, or by chemically doping samarium ions into spray‐dried ZrB₂. In either approach, SiC powders were also added and coatings were fabricated via shrouded air plasma spray. An oxyacetylene torch was utilized to evaluate the coatings under high heat flux conditions for hold times of 30 and 60 s. The resulting phases and microstructures were evaluated as a function of rare‐earth type, modification approach, and ablation time. A brittle m‐ZrO₂ scale was observed in the ZrB₂/SiC‐only coating after ablative tests; during cooling this scale detached from the unreacted coating. In contrast, rare‐earth modified coatings formed a protective oxide scale consisting primarily of either Sm_0.2Zr_0.8O_1.9 or Tm_0.2Zr_0.8O_1.9, along with small amount of m‐ZrO₂. These rare‐earth oxide scales displayed high thermal stability and remained adhered to the unreacted coating during heating and cooling, offering additional oxidation protection.     

Polar Nanoregions and Dielectric Properties of BaTiO3‐Based Y5V Multilayer Ceramic Capacitors

Commercial EIA‐Y5V base‐metal‐electrode multilayer ceramic capacitors (BME‐MLCCs) made of (CaO+ZrO₂)‐doped BaTiO₃ are analyzed for the microstructure and investigated for its relation to dielectric properties. The characteristic diffuse scattering (DS) intensities observed in BaTiO₃ ceramics and the featureless “solid‐solution” grains in Y5V capacitor chips are originated from multiple Ti sites in the dynamic BaTiO₃ structure. The pseudo‐cubic (PC)‐grains retaining the overall cubic (C‐) symmetry metastably at room temperature are embedded with polar nanoregions (PNRs) in the ferroelectric (FE) tetragonal (T‐), and rhombohedral (R‐) phases, as revealed by high‐resolution transmission electron microscopy (HRTEM). The presence of PNRs contributes effectively to large relative permittivity ε_r ≈ 13 200 at 25°C. The FE T‐domains grow from within PC‐grains at the expense of embedded PNRs after prolonged annealing by extending “oxidizing firing” at 950°C in pO₂ = 10^?7 atm. These domains contain less Zr with otherwise homogeneously distributed solutes in PNR‐dispersed PC‐grains. Although preserving the relaxors characteristics, ε_r is reduced to ~11 000 after 12 h, and then to ~9000 after 24 h annealing. The reduction in ε_r is attributed to the annealing‐induced FE T‐domains grown at the expense of PNRs in PC‐grains. The Vögel–Fulcher analysis indicates that Y5V ceramics are in the relaxor FE category, containing PNRs derived from polarization frustration.     

Improved Energy Storage Properties of Fine‐Crystalline BaTiO3 Ceramics by Coating Powders with Al2O3 and SiO2

The multilayer structure of capacitor demands for fine grain size of dielectric ceramics in devices, because the thinner layer which needs ceramics with fine grain size is helpful in enlarging the capacitance. In this paper, the aqueous chemical coating method was utilized to modify the BaTiO₃ particles. The fine‐crystalline BaTiO₃ ceramics with an average grain size below 200 nm without abnormal grain growth by co‐coating Al₂O₃ and SiO₂ has been prepared. The phase composition, microstructures of coated particles and ceramics, and dielectric properties were investigated. For samples containing 3 wt% of Al₂O₃ and 1 wt% of SiO₂, the energy storage density is 0.725 J/cm³ and the efficiency of the ceramic samples can keep above 80%. The breakdown strength was improved to about 190 kV/cm.     

Catalytic Combustion‐Type Hydrogen Sensor Using BaTiO3‐based PTC Thermistor

A catalytic combustion‐type gas sensor using a positive temperature coefficient (PTC) thermistor, which shows a sharp resistance change around Curie temperature, was developed for the detection of hydrogen. La‐doped BaTiO₃ (Ba_0.998 La_0.002 TiO₃) was prepared through a solid‐state method and an oxalic acid method. La‐doped BaTiO₃ obtained by the oxalic acid method showed improved PTC properties, due to the formation of fine particles, as compared to that prepared with the solid‐state method. The resulting sensor device showed a fairly high H₂ sensitivity in the range of 100–1000 ppm. In addition, the H₂ sensitivity and response speed were improved by coating a Pt/SiO₂ catalyst on the sensor device because the catalytic combustion efficiency of H₂ was improved by the catalyst coating.     

Enhancement on electric responses of BaTiO3 particles with polymer‐coating

To enhance electric response by polymer coating, BaTiO₃/polymer shell–core composite particles were prepared by emulsion polymerization with polyimide, chitosan, polystyrene, polyacrylic acid, and polyacrylamide. Their micro structure was characterized by transmission electron microscopy, Fourier transform infrared, and automatic X‐ray diffraction, their properties were investigated using optical contact angle and dielectric constant, and their electric responses were studied indirectly by dynamic viscoelasticity analyzer. The results showed that BaTiO₃ cores remained in cubic, the surface hydrophilic of the particles changed as follows: BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS, and the dielectric constants of the particles varied with the order of that BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS. Eventually, the particles' electric response activities exhibited the order of BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS > BaTiO₃. Furthermore, the electric response of the particles showed a chief dependence on polymer‐coating, surface hydrophilic, and dielectric constant. As a result, BaTiO₃ particles' electric response was much enhanced by polymer‐coating, and their compatibility to aqueous continuous phase was ameliorated. For the BaTiO₃/polymer particles, fine surface hydrophile and high dielectric constant dominated the strong response to electric field. Ultimately, BaTiO₃/PI and BaTiO₃/PAM particles possessed the strongest electric response in the five composite particles. The conclusion suggests an effective approach to prepare excellent hydrous electrorheological elastomers. POLYM. COMPOS., 34:897–903, 2013. © 2013 Society of Plastics Engineers     

X9R BaTiO3‐Based Dielectric Ceramics with Multilayer Core–Shell Structure Produced by Polymer‐Network Gel Coating Method

The modified polymer‐network gel route has been developed to prepare a multilayer core –shell structure of BaTiO ₃‐ based dielectric ceramics. The core of particle was BaTiO₃, whereas 0.7BaTiO₃–0.3Bi(Zn_1/2Ti_1/2)O₃ (0.7BT–0.3BZT) and Nb oxides were coated as the multilayer shell compositions, which were confirmed by energy dispersive spectroscopy testing. The dielectric properties of BaTiO₃‐based samples with multilayer core–shell structure were found to meet the X9R specification. The dielectric constant was 1190 and the dielectric loss was 1.3% at room temperature.     

Dy3+‐Doped Selenide Chalcogenide Glasses: Influence of Dy3+ Dopant‐Additive and Containment

This work reports on process‐induced impurities in rare‐earth ion: Dy³⁺‐doped selenide chalcogenide glasses, which are significant materials for active photonic devices in the mid‐infrared region. In particular, the effect of contamination from the silica glass ampoule containment used in chalcogenide glass synthesis is studied. Heat‐treating Dy‐foil‐only, and DyCl₃‐only, separately, within evacuated silica glass ampoules gives direct evidence of silica ampoule corrosion by the rare‐earth additives. The presence of [Ga₂Se₃] associated with [Dy] on the silica glass ampoule that has been contact with the chalcogenide glass during glass melting, is reported for the first time. Studies of 0–3000 ppmw Dy³⁺‐doped Ge_16.5As₉Ga₁₀Se_64.5 glasses show that Dy‐foil is better than DyCl₃ as the Dy³⁺ additive in Ge‐As‐Ga‐Se glass in aspects of avoiding bulk crystallization, improving glass surface quality and lowering optical loss. However, some limited Dy/Si/O related contamination is observed on the surfaces of Dy‐foil‐doped chalcogenide glasses, as found for DyCl₃‐doped chalcogenide glasses, reported in our previous work. The surface contamination indicates the production of Dy₂O₃ and/or [≡Si‐O‐Dy=]‐containing particles during chalcogenide glass melting, which are potential light‐scattering centers in chalcogenide bulk glass and heterogeneous nucleation agents for α‐Ga₂Se₃ crystals.     

Effect of BaTiO3 on the microwave absorbing properties of Co‐doped Ni‐Zn ferrite nanocomposites

Coprecipitation and hydrothermal method were utilized for the synthesis of Co‐doped Ni‐Zn ferrite and barium titanate nanoparticles. The microwave absorption properties of Co‐doped Ni‐Zn ferrite/barium titanate nanocomposites with single layer structure were studied in the frequency range of 8.2–12.4 GHz.The spectroscopic characterizations of the nanocomposites were examined using X‐ ray diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering measurement. Thermogravimetric analysis indicated the high thermal stabilities of the composites. The composite materials showed brilliant microwave absorbing properties in a wide range of frequency in the X‐band region with the minimum return loss of ?42.53 dB at 11.81 GHz when sample thickness was 2 mm and the mechanisms of microwave absorption are happening mainly due to the dielectric loss. Compared with pure Co‐doped Ni‐Zn ferrite, Co‐doped Ni‐Zn ferrite/BaTiO₃ composites exhibited enhanced absorbing properties. The microwave absorbing properties can be modulated by controlling the BaTiO₃ content of the absorbers and also by changing the sample thicknesses. Therefore, these composites can be used as lightweight and highly effective microwave absorbers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39926.     

Reduction of Ti4+ to Ti3+ in Boron‐Doped BaTiO3 at Very Low Temperature

Reduction of Ti⁴⁺ to Ti³⁺ was found in boron‐doped BaTiO₃ ceramics when we sintered the samples at very low temperature (>850°C) in 5%H₂/Ar. Such reduction did not occur in pristine BaTiO₃ ceramic. The methods such as UV–vis spectroscopy, luminescence spectroscopy, and X‐ray photoelectron spectroscopy confirmed the reduction by showing the presence of Ti³⁺. The results of Ti–K‐edge X‐ray absorption near‐edge structure measurement (XANES) indicated that boron doping changed the geometry of Ti‐oxygen in BaTiO₃ to some extent. It was likely that some boron ions stayed at interstitial sites of BaTiO₃ lattice and acted as donors, which might trigger the reduction. The reduced boron‐doped BaTiO₃ were semiconducting and had very low room‐temperature resistivity (<100 Ω m). However, different from the n‐type rare‐earth‐doped BaTiO₃ ceramics, they did not display positive temperature coefficient resistance (PTCR) behavior.     

Gasphasensynthese von Kern/Mantel‐Partikeln am Beispiel von TiO2‐Nanopartikeln mit elektrisch leitendem Mantel

An advanced process enables synthesis and coating of individual TiO₂‐core particles with a shell of transparent conducting oxide (TCO) from the gas phase in one reactor. TiO₂ particles were coated with fluorine‐doped tin oxide (SnO₂:F) or antimony‐doped tin oxide (SnO₂:Sb). Specific electrical conductivity of the core/shell particles was up to 8 · 10^–3 S cm^–1. Variation of process parameters allows modifying dopant level and conductivity in an easy way.     

Processing of 0.7BaTiO3–0.3BiScO3 Solid‐Solution Coatings

Coatings with the 0.7BaTiO₃–0.3BiScO₃ solid‐solution composition were formed on palladium and single‐crystal (001) SrTiO₃ substrates using a polymeric metal citrate precursor. Solutions of TiOCl₂, Ba(NO₃)₂, Sc(NO₃)₃, and Bi(NO₃)₃ were mixed with citric acid and polymerized with ethylene glycol. Stable mixed‐metal citrate solutions were formed at pH > 9 and used for coatings. The phase and composition of powders and coatings were characterized using DTA, TGA, SEM, TEM, and X‐ray diffraction. Single‐phase cubic 0.7BaTiO₃–0.3BiScO₃ solid solutions formed at 600°C. Coatings on Pd using precursors doped with 5 wt% lithium nitrate were dense after sintering at 950°C/1 h. Coatings without lithium nitrate required 1050°C/50 h to densify. Coatings on SrTiO₃ heat‐treated at 1150°C were dense but formed a (Sc,Ti)‐rich second phase.     

Effects of promoters on catalytic activity and carbon deposition of Ni/γ‐Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed‐bed reactor using unpromoted and promoted Ni/γ‐Al₂O₃ catalysts. The effects of promoters, such as alkali metal oxide (Na₂O), alkaline‐earth metal oxides (MgO, CaO) and rare‐earth metal oxides (La₂O₃, CeO₂), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO‐, La₂O₃‐ and CeO₂‐promoted Ni/γ‐Al₂O₃ catalysts exhibited higher stability whereas MgO‐ and Na₂O‐promoted catalysts demonstrated lower activity and significant deactivation. Metal‐oxide promoters (Na₂O, MgO, La₂O₃, and CeO₂) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. © 2000 Society of Chemical Industry     

Current Understanding of Structure–Processing–Property Relationships in BaTiO3–Bi(M)O3 Dielectrics

As part of a continued push for high permittivity dielectrics suitable for use at elevated operating temperatures and/or large electric fields, modifications of BaTiO₃ with Bi(M)O₃, where M represents a net‐trivalent B‐site occupied by one or more species, have received a great deal of recent attention. Materials in this composition family exhibit weakly coupled relaxor behavior that is not only remarkably stable at high temperatures and under large electric fields, but is also quite similar across various identities of M. Moderate levels of Bi content (as much as 50 mol%) appear to be crucial to the stability of the dielectric response. In addition, the presence of significant Bi reduces the processing temperatures required for densification and increases the required oxygen content in processing atmospheres relative to traditional X7R‐type BaTiO₃‐based dielectrics. Although detailed understanding of the structure–processing–property relationships in this class of materials is still in its infancy, this article reviews the current state of understanding of the mechanisms underlying the high and stable values of both relative permittivity and resistivity that are characteristic of BaTiO₃‐Bi(M)O₃ dielectrics as well as the processing challenges and opportunities associated with these materials.     

Flexible 0–3 Ceramic‐Polymer Composites of Barium Titanate and Epoxidized Natural Rubber

Flexible composites with a high electrical permittivity are pursued in materials research, due to their potential applications in electrical devices. We synthesized such ceramic‐polymer composites from BaTiO₃ and epoxidized natural rubber. The influence of BaTiO₃ concentration on cure characteristics, mechanical (static & dynamic), dielectric, and morphological properties of the composites was investigated. The tensile strength and elongation at break decreased with BaTiO₃ loading, while the storage modulus and permittivity of composites increased. As for dynamic electrical properties, the dielectric loss factor and tan δ of the composites showed a maximum peak within the frequency range extending up to 10⁵ Hz, reflecting the relaxation process of the polymer matrix. All of the composites showed two peaks in the frequency dependence of electric modulus, due to conductivity and molecular relaxation. Scanning electron microscopy micrographs confirmed the 0–3 structure of composites, with isolated BaTiO₃ particles.     

X‐ray Absorption Spectroscopy Studies of the Room‐Temperature Ferromagnetic Fe‐Doped 6H–BaTiO3

We investigated the effect of annealing temperature on magnetic properties of 2% and 10% Fe‐doped BaTiO₃. To understand the possible structural differences between samples treated at different annealing temperatures, and to correlate them with the magnetic properties, several characterization techniques, such as X‐ray diffraction and X‐ray absorption spectroscopic methods (XANES and EXAFS) were employed. We found that the 2% Fe‐doped BaTiO₃ pseudocubic perovskite is paramagnetic regardless of the heat‐treatment conditions. Initially paramagnetic 10% Fe‐doped 6H–BaTiO₃, treated at 1250°C, became ferromagnetic after additional annealing at higher temperature. We have crystalographically characterized the cation ordering processes in the 6H–BaTiO₃ that occurred during the high‐temperature annealing. The ferromagnetism that is induced in this stage is most probably associated with the observed diffusion processes but it extrinsic character still cannot be fully disregarded.     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.