Inner Electrodes for Multilayer Varistors

In the present study, Pt or AgPd metal is used as the inner electrode for Bi₂O₃-doped ZnO multilayer varistors (MLV). The growth of the ZnO grains is constrained by the presence of the inner electrodes. The Pt inner electrodes are chemically inert to Bi₂O₃-doped ZnO. The Bi₂O₃ could react with Pd to form PdBi₂O₄. The Bi₂O₃-rich liquid also tends to wet the AgPd electrode. The size of ZnO grains in the MLV/AgPd specimen is larger. The ZnO grains in the MLV/AgPd specimen can even grow to a size larger than the layer thickness at the expense of electrode continuity.     

Characterization of Silver Interdiffusion into (Zn,Mg)TiO3+x:Bi:Sb Multilayer Ceramic Capacitor

In this study, (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ multilayer ceramic capacitors (MLCCs) with different proportions of a silver (Ag)–palladium (Pd) mixture acting as the inner electrode were sintered at 925°C for 2 h to evaluate the effect of the inner electrode on reliability. The main results reveal that the lifetime is inversely proportional to the Ag content in the Ag/Pd inner electrode. Ag diffusion into the (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC during cofiring at 925°C for 2 h and Ag migration at 140°C against 200 V are both responsible for the short lifetime of the (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC, particularly the latter factor. A Bi,Sb-rich secondary phase was present at the triple junction and a small amount of Ag was detected from the second phase for a (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC with a high Ag content in the inner electrode of Ag/Pd=99/01. However, this was not the case with a low Ag content in the inner electrode of Ag/Pd=90/10. This means that the Bi,Sb-rich second phase plays an important role in determining the degradation of insulation resistance due to the excessive formation of oxygen vacancies from the reaction of Ag⁺ for Bi³⁺ or Sb⁵⁺ substitution to lower the activation energy of the (Zn,Mg)TiO₃+Bi₂O₃+Sb₂O₅ dielectrics and to enhance markedly the effect of Ag migration.     

Interaction of Silver/Palladium Electrodes with Lead-and Bismuth-Based Electroceramics

In this study the phase relations between Pd or 70Ag/30Pd electrode systems with commercially important Bi-or Pb-based oxides were determined to establish the conditions under which detrimental interfacial chemical reactions may occur. For the reaction of Pd with Bi compounds, PdBi₂O₄ formation was observed if the reaction proceeded at temperatures less than 835°C. At higher temperatures a Pd (Bi) alloy formed containing the maximum solubility of the Bi, i.e., 16 at.%. For the reaction of Pd with Pb compounds, a Pd (Pb) alloy formed which in all instances exhibited the maximum solubility of the Pb, i.e., 14 at.%. These reactions had an adverse effect on the local stoichiometry and composition of the dielectric, causing depletion of Bi or Pb. Studies on commercial capacitor dielectrics from DuPont (X7R and Z5U formulations) and Pb (Mg_1/3Nb_2/3)O₃ showed that the use of Pd electrodes decreased the dielectric constant substantially, which was due to the formation of a low permittivity phase in series connectivity with the unaltered dielectric.     

Temperature/Composition Phase Diagram of the System Bi2O3-PbO

The Bi₂O₃-PbO phase diagram was determined using differential thermal analysis and both room- and high-temperature X-ray powder diffraction. The phase diagram contains a single eutectic at 73 mol% PbO and 635°C. A body-centered cubic solid solution exists above ∼600°C within a composition range of 30 to 65 mol% PbO. The compounds α-Bi₂O₃, σ5-Bi₂O₃, and γ-PbO (litharge) have wide solubility ranges. Four compounds, 6Bi₂O₃·PbO, 3Bi₂O₃·2PbO, 4Bi₂O₃,5PbO, and Bi₂O₃·3PbO, are formed in this system and the previously unreported X-ray diffraction patterns of the latter three compounds are reported. Diffraction patterns for some of these mixed oxides have been observed in ZnO-based varistors grown using Bi₂O₃ and PbO as sintering aids.     

Phase Equilibrium Studies in the System Iron Oxide-Al2O3-Cr2O3

Subsolidus phase relations in the system iron oride-Al₂O₂-Cr₂O₃ in air and at 1 atm. O₂ pressure have been studied in the. temperature interval 1250° to 1500°C. At temperatures below 1318° C. only sesquioxides with hexagonal corundum structure are present as equilibrium phases. In the temperature interval 1318° to 1410°C. in air and 1318° to 1495° C. at 1 atm. O₂, pressure the monoclinic phase Fe₂O₃. Al₂O₃ with some Cr₂O₃ in solid solution is present in the phase assemblage of certain mixtures. At temperatures above 1380°C. in air and above 1445°C. at 1 atm. O₂ pressure a complex spinel solid solution is one of the phases present in appropriate composition areas of the system. X-ray data relating d- spacing to composition of solid solution phases are given.     

Microwave Dielectric Properties of Low Firing Temperature Bi2W2O9 Ceramics

Phase stability, sinterability, and microwave dielectric properties of Bi₂W₂O₉ ceramics and their cofireability with Ag, Cu, and Au electrodes have been investigated. Single-phase Bi₂W₂O₉ powder was synthesized by solid-state reaction in air at 800°C for 3 days. X-ray powder diffraction data show Bi₂W₂O₉ to have an orthorhombic crystal structure described by the noncentrosymmetric space group Pna 2₁, with lattice parameters a =5.4401(8), b =5.4191(8), c =23.713(4) Å. Ceramics fired at temperatures up to 865°C remain single-phase but above this temperature ferroelectric Bi₂WO₆ appears as a secondary phase. The measured relative permittivity of Bi₂W₂O₉ ceramics increases continuously from 28.6 to 40.7 for compacts fired between 860° and 885°C. The bulk relative permittivity of Bi₂W₂O₉ corrected for porosity was calculated as 41.3. Bi₂W₂O₉ ceramics fired up to 875°C exhibit moderate quality factors, Q × f _r, ∼7500–7700 GHz and negative temperature coefficient of resonant frequency, ∼−54 to −63 ppm/°C. Chemical compatibility experiments show Bi₂W₂O₉ ceramics to react with both Ag and Cu electrodes, but to form good contacts with Au electrodes.     

Structural Dependence on Sintering Temperature of Lead Zirconate-Titanate Solid Solutions

Pb(Zr_0.525Ti_0.475)O₃ piezoceramics, both unmodified and doped with 2 wt% Bi₂O₃ or Nb₂O₅, were prepared by the usual techniques, using sintering temperatures from 900° to 1250°C. The microstructural data showed that the sintering temperature which produces minimum porosity is altered by the oxide additions. X-ray diffraction demonstrated the coexistence of both ferroelectric phases. The lattice parameter measurements showed that the tetragonal and rhombohedra1 unit cells of the two ferroelectric phases depend on the sintering temperature.     

Thermodynamic Modeling of Equilibrium Subsolidus Phase Relations in the Ag–Pd–O2 System

From literature values of the thermodynamic activity of Pd in Ag/Pd solid solutions and the Gibbs free energy of formation of PdO as a function of temperature, subsolidus equilibrium phase relations in the Pd–Ag–O₂ system have been calculated and compared to results from high-temperature XRD analyses. The developed model takes into account the nonideal activity of Pd in Ag/Pd solid solutions and confirms that increasing the Ag/Pd ratio or decreasing the oxygen activity decreases the temperature at which PdO reduces. It also accurately predicts that the temperature range over which the PdO reduces is broad for Ag-rich compositions, and narrow for Pd-rich compositions.     

Reactions in the System PbO-Ta2O5

Subsolidus phase relations in the binary system PbO-Ta₂O₅ were investigated by the quenching method. The following compounds were identified by X-ray diffraction patterns: PbO -2Ta2O₅, PbO Ta₂O₆, 3PbO 2Ta₂P₅, 2PbO Ta₂O₆, 5PbO -2Ta₂O₅, and 3PbOTa₂O₅ The 1:1 compound has rhombohedral symmetry when it is prepared below 1150°C. Above this temperature, it yields an orthorhombic phase. Compounds with the same ratio of lead oxide to pentoxide exist in the systems PbO-Ta₂O₆ and PbO-Nb₂O₅.     

Factors Determining Grain Orientation in Bismuth Sodium Potassium Titanate–Lead Zirconate Titanate Solid Solutions Made by the Reactive Templated Grain Growth Method

Grain-oriented Bi_0.5(Na_0.85K_0.15)_0.5TiO₃-Pb(Zr_{1− x} Ti _x )O₃ (BNKT-PZT) ceramics were prepared via the reactive templated grain growth method, using platelike Bi₄Ti₃O₁₂ particles. Factors that determine the degree of orientation were examined. Prereacted PZT gave a larger degree of orientation than PZT raw materials (PbO, ZrO₂, and TiO₂) in the 75BNKT-25PZT ( x = 0.5) system. Increases in the titanium concentration in the PZT of the 75BNKT-25PZT system and in the BNKT concentration in the y BNKT-(100 − y )PZT ( x = 0.5) system increased the degree of orientation. The direction of material transport between BNKT and PZT was important to obtain ceramics with a large degree of orientation.     

Microstructures of SrTiO3 Internal Boundary Layer Capacitors During and After Processing and Resultant Electrical Properties

The microstructure of strontium titanate internal boundary layer capacitors at various stages in their processing was studied by transmission electron microscopy of rapidly quenched and normally cooled samples. Compositions containing excess TiO₂, Al₂O₃, and SiO₂ have a completely wetting liquid phase at the sintering temperature; during cooling Ti_nO_{2 n −1}, Magneli phases precipitate at multiple grain junctions. Diffused metal oxides and flux (Bi₂O₃, PbO, CuO, and B₂O₃) rapidly penetrate as a liquid phase along boundaries in postsintering heat treatment. This liquid phase disappears during slow cooling.     

Phase Relations in the System Bi2O3-WO3

Phase relations in the system Bi₂O₃-WO₃ were studied from 500° to 1100°C. Four intermediate phases, 7Bi₂O₃· WO₃, 7Bi₂O₃· 2WO₃, Bi₂O₃· WO₃, and Bi₂O₃· 2WO₃, were found. The 7B₂O · WO₃ phase is tetragonal with a ₀= 5.52 Å and c ₀= 17.39 Å and transforms to the fcc structure at 784°C; 7Bi₂O₃· 2WO₃ has the fcc structure and forms an extensive range of solid solutions in the system. Both Bi₂O₃· WO₃ and Bi₂O₃· 2WO₃ are orthorhombic with (in Å) a ₀= 5.45, b ₀=5.46, c ₀= 16.42 and a ₀= 5.42, b ₀= 5.41, c ₀= 23.7, respectively. Two eutectic points and one peritectic exist in the system at, respectively, 905°± 3°C and 64 mol% WO₃, 907°± 3°C and 70 mol% WO₃, and 965°± 5°C and 10 mol% WO₃.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Phase Relations and Dielectric Properties in the Bi2O3–ZnO–Ta2O5 System

Dielectric properties and phase formation of Bi-based pyrochlore ceramics were evaluated for the Bi₂O₃–ZnO–Ta₂O₅ system. The compositional range r Bi₂(Zn_1/3Ta_2/3)₂O₇· (1− r )(Bi_3/2Zn_1/2)(Zn_1/2Ta_3/2)O₇ (0 ≤ r ≤ 1) in Bi₂O₃–ZnO–Ta₂O₅ was investigated to determine the relative solubility of BZT cubic (α-BZT, r = 0) and the pseudo-orthorhombic (β-BZT, r = 1) end members. It was found that extrinsic factors, such as kinetically limited phase formation and bismuth loss, contribute to apparent phase boundaries in addition to thermodynamic stability of each phase. Considering this, the locations of true phase boundaries were r < 0.30 and r ≥ 0.74 for α and β phases, respectively. Dielectric constants between 58 and 80 and low dielectric loss (tan δ < 0.003) were measured for the complete compositional range. The temperature coefficient of capacitance was controlled by composition, which was found to be <30 ppm/°C at the edge of β-phase solid solution. In addition to the excellent dielectric properties these materials can be sintered at low temperatures, which make Bi-based pyrochlores promising candidates for high-frequency electronic applications.     

The System Bi2O3-SiO2

The Bi₂O₃-rich side of the system Bi₂O₃-SiO₂ was studied with powder X-ray diffraction and differential thermal analysis. In the composition 6Bi₂O₃. x SiO₂, the metastable γ phase (bcc) was observed to exist over the range of 0 < x ≤ 1. In most of the compositions studied, metastable phases of water-quenched melts transformed into another metastable phase before reaching stable phases. A modification of the phase diagram is proposed.     

Effects of Titanium Oxide on Equilibria Among Refractory Phases in the System CaO-MgO-Iron Oxide

The role of titanium oxide in some important refractory systems was elucidated by studying selected equilibria in the system CaO-MgO-iron oxide-titanium oxide at O₂ pressures of 0.21 atm (air) and 10⁻⁹ atm and under the extreme reducing conditions imposed by the presence of metallic Ti in contact with the oxide phases. Solidus relations were determined for the system CaO-MgO-TiO₂ in air; 6 composition triangles were delineated, within each of which 3 crystalline phases coexist in equilibrium with liquid at a constant solidus temperature. The solidus temperatures range from 1407° to 1670°C. There is also a composition area within which MgO coexists with a Ca₄Ti₃O₁₀-Ca₃Ti₂O₇ solid solution, with solidus temperatures varying continuously from 1659° to 1670°C. Studies of reactions between MgO and titanium oxide in contact with metallic Ti in a closed system indicate that the mutual solubility between MgO and TiO at 1400°C is very small. Addition of 5 wt% TiO₂ to the system CaO-MgO-iron oxide at 1500°C in air and in 10⁻⁹ atm O₂ decreases the amount of iron oxide which can be absorbed by a CaO-MgO body without formation of a liquid phase; hence, titanium oxide has a strong deleterious effect on the refractoriness of such bodies.     

Reaction Pathways in the Synthesis of Photorefractive gamma-Bi12MO20 (M = Si, Ge, or Ti)

Reaction pathways in the synthesis of three photorefractive silicates—γ-Bi₁₂ SiO₂₀ (BSO), γ-Bi₁₂ GeO₂₀ (BGO), and gamma-Bi₁₂ TiO₂₀ (BTO)—were systematically investigated. The main results were as follows: (i) all the reactions of the form 6Bi₂O₃+ MO₂→> γ-Bi₁₂ MO₂₀ (SR1 for M = Si, SR2 for M = Ge, SR3 for M = Ti) in the solid state seemed to be diffusion-controlled processes and were affected by both temperature and time, where the reaction temperature increases in the order SR1 < SR2 < SR3; (ii) the metastable phases Bi₂ SiO₅ (tetragonal) in reaction SR1, Bi₂ GeO₅ (orthorhombic) in reaction SR2, Bi₄ Ti₃ O₁₂ (orthorhombic) in reaction SR3 may be formed and seemed to greatly accelerate the above-mentioned solid-state reaction processes; and (iii) for a continuous heating process, pure γ-Bi₁₂ SiO₂₀ and γ-Bi₁₂ GeO₂₀ could be produced before melting, whereas pure γ-Bi₁₂ TiO₂0 could not be produced, even if all the mixed phases had melted.     

Effects of Doping Trivalent Ions in Bismuth Borate Glasses

Bismuth borate glasses from the system: 40Bi₂O₃–59B₂O₃–1Tv₂O₃ (where Tv=Al, Y, Nd, Sm, and Eu) and three glasses of composition: 40Bi₂O₃–60B₂O₃, 37.5Bi₂O₃–62.5B₂O₃ and 38Bi₂O₃–60B₂O₃–2Al₂O₃ were prepared by melt quenching and characterized by density, UV-visible absorption spectroscopy and differential thermal analysis (DTA) studies. Bismuth borate glasses exhibit a very strong optical absorption band just below their absorption edge. Glasses were devitrified by heat treatment at temperatures above their glass transition temperatures and the crystalline phases produced in them were characterized by Fourier transform infrared (FTIR) absorption spectroscopy and X-ray diffraction (XRD). Bi₃B₅O₁₂ was found to be the most abundant phase in all devitrified samples. DTA studies on glasses and FTIR and XRD analysis on crystallized samples revealed that very small amounts of trivalent ion doping causes significant changes in the devitrification properties of bismuth borate glasses; rare-earth ions promote the formation of metastable BiBO₃–I and BiBO₃–II phases during glass crystallization.     

Kinetics of Solid-State Reaction of Bi2O3 and Fe2O3

Solid-state reactions of equimolar mixtures of Bi₂O₃ and Fe₂O₃ from 625° to 830°C and their kinetics were investigated. The reaction rates were determined from the integrated X-ray diffraction intensities of the strongest peaks of the reactants and products. The activation energy for the formation of BiFeO₃ was 96.6±9.0 kcal/mol; that for a second-phase compound, Bi₂Fe₄O₉, which formed above 675°C, was 99.4±9.0 kcal/mol. Specific rate constants for these simultaneous reactions were obtained. The preparation of single-phase BiFeO₃ from the stoichiometric mixture of Bi₂O₃ and Fe₂O₃ is discussed.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.