Origin of Microwave Dielectric Loss in ZnNb2O6-TiO2

(1− x )ZnNb₂O₆· x TiO₂ ceramics were prepared using both anatase and rutile forms of TiO₂. At a composition of x = 0.58, a mixture region of ixiolite (ZnTiNb₂O₈) and rutile was observed and the temperature coefficient of resonant frequency (τ_f) was ∼0 ppm/°C. We found that although ɛ_r and τ_f were comparable, the quality factor ( Q × f , Q ≈ 1/ tan δ, f = resonant frequency) of 0.42ZnNb₂O₆·0.58TiO₂ prepared from anatase and rutile was 6000 and 29 000, respectively. The origin of the difference in Q × f of both samples was investigated by measuring electrical conductivity and by analysis of the anatase–rutile phase transition. The anatase-derived sample had higher conductivity, which was related to the reduction of Ti⁴⁺. It is suggested that the increase of dielectric loss originates from an increase in Ti³⁺ and oxygen vacancies due to an anatase–rutile phase transition.     

Microwave Dielectric Properties of Low-Fired ZnNb2O6 Ceramics with BiVO4 Addition

The BiVO₄ additive was found effective for low-temperature firing of ZnNb₂O₆ polycrystalline ceramics below 950°C in air without a serious degradation in their microwave dielectric properties. Dense BiVO₄-doped ZnNb₂O₆ samples of a relative sintered density over 95% could be prepared even at 925°C. An optimally processed specimen exhibited excellent microwave dielectric properties of Q · f = 55000 GHz, ɛ_r= 26, and τ_f=−57 ppm/°C. With increasing BiVO₄ addition up to 20 mol% relative to ZnNb₂O₆, while the quality factor Q · f was gradually decreased, the relative dielectric constant, ɛ_r, was linearly increased and the temperature coefficient of resonant frequency, τ_f, was slightly increased. The variations in Q · f and ɛ_r are surely attributable to the residual BiVO₄ in the ZnNb₂O₆ matrix. An unexpected slight increase in τ_f is probably due to the formation of the Bi(V,Nb)O₄-type solid solution.     

Atmospheric Dependence on Dielectric Loss of 1/6Ba5Nb4O15· 5/6BaNb2O6 Ceramics

Samples of 1/6Ba₅Nb₄O₁₅·5/6BaNb₂O₆ along with the pure end members, Ba₅Nb₄O₁₅ and BaNb₂O₆, were sintered under low oxygen partial pressure. The degradation mechanisms of dielectric loss in this reducing atmosphere have been studied. We found that the degradation occurred primarily due to the formation of oxygen vacancies caused by the reduction of Nb⁵⁺. This was determined by measuring the electrical conductivity, and through X-ray photoelectron spectroscopy. More importantly, the dielectric loss of 1/6Ba₅Nb₄O₁₅·5/6BaNb₂O₆ samples with higher temperature stability was further decreased on sintering in a reducing atmosphere. This observation has been explained by considering the increased porosity and formation of a reduced second phase, Ba_0.65NbO₃.     

Characterization and Microwave Dielectric Properties of M2+Nb2O6 Ceramics

This paper details the investigation of the quality factor ( Q ), dielectric permittivity (ɛ_r) and temperature coefficient of resonant frequency (τ_f) of the TE_01δ mode of the columbite binary niobate ceramics, with the formula MNb₂O₆ where M=²⁺ cation, in relation to their degree of sintering, microstructure and phase composition. The ceramics were made from a mixed oxide preparative route and fired over a range of temperatures from 800° to 1400°C, and most formed the columbite structure. A comprehensive study was made of the niobates containing the transition metal cations M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺, and the group II metal cations M=Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺. All columbite niobates were found to have ɛ_r between 17 and 22 and negative τ_f values between –45 and –76 ppm/°C, and ZnNb₂O₆, MgNb₂O₆, CaNb₂O₆, and CoNb₂O₆ had high Q f values of 84 500, 79 600, 49 600, and 41 700 GHz, respectively. The Q f of MgNb₂O₆ was found to rise to over 95 000 GHz when heated at 1300°C for 50 h.     

Grain-Oriented PbNb2O6 Ceramics

Grain-oriented ceramics of ferroelectric lead metaniobate have been prepared by molten salt synthesis of anisotropic crystallites followed by doctor blade casting. The sintered ceramics have an orthorhombic texture with elongated c axis grains parallel to the casting direction. This allows efficient poling in directions perpendicular to the tape.     

Microwave Dielectric Properties of 5Li2O–0.583Nb2O5–3.248TiO2 Ceramics with V2O5

The effects of V₂O₅ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O–0.583Nb₂O₅–3.248TiO₂ (LNT) ceramics have been investigated. With addition of low-level doping of V₂O₅ (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V₂O₅ addition. The addition of V₂O₅ does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the excellent microwave dielectric properties of ɛ_r=21.5, Q × f =32 938 GHz, and τ_f=6.1 ppm/°C could be obtained for the 1 wt% V₂O₅-doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.     

Tailoring the Microwave Dielectric Properties of MgNb2O6 and Mg4Nb2O9 Ceramics

The columbites MgNb₂O₆, MgTa₂O₆, and corundum-type Mg₄Nb₂O₉ ceramics were prepared by the conventional solid-state ceramic route. The structure and microstructure of the sintered samples were investigated by X-ray diffraction and scanning electron microscopic techniques. The microwave dielectric properties of the samples were measured by the resonance method in the frequency range 4–6 GHz. The dielectric properties have been tailored by forming a solid solution between MgNb₂O₆ and MgTa₂O₆ and by the substitution of TiO₂ for Nb₂O₅ in both MgNb₂O₆ and Mg₄Nb₂O₉ ceramics. The Mg(Nb_0.7Ta_1.3)O₆ has ɛ_r=29, Q _u× f =67 800 GHz, and τ_f=0.8 ppm/°C and the MgO–(0.4)Nb₂O₅–(1.5)TiO₂ composition has ɛ_r=34.5, Q _u× f =81 300 GHz, and τ_f=−2 ppm/°C.     

Microwave Dielectric Properties and Chemical Resistance of Low-Temperature-Sintered CaZrB2O6 Ceramics

Dolomite-type borate ceramics consisting of CaZrB₂O₆ were synthesized via a conventional solid-state reaction route; low-temperature sintering was explored using Bi₂O₃–CuO additives of 1–7 wt% for low-temperature co-fired ceramics applications. For several sintering temperatures, the microwave dielectric properties and chemical resistance of the ceramics were investigated. The CaZrB₂O₆ ceramics with 3 wt% Bi₂O₃–CuO addition could be sintered below 925°C, and the microwave dielectric properties of the low-temperature samples were ɛ_r=10.55, Q × f =87,350 GHz, and τ_f=+2 ppm/°C. The chemical resistance test result showed that both CaZrB₂O₆- and Bi₂O₃–CuO-added CaZrB₂O₆ ceramics were durable in basic solution but were degraded in acid solution.     

Phase Structure and Dielectric Properties of Bi2O3-ZnO-Nb2O5-Based Dielectric Ceramics

Phase structures and dielectric properties of the compounds with formulas BixZn_2/3Nb_4/3O_4+3x/2 (group M), Bi_xZn_8/3-x Nb_4/3O_6+x/2 (group V), and Bi_xZn_2-2x/3Nb_2-x/3O₇ (group W) have been investigated. Initial results indicate that a cubic pyrochlore structure is the predominant phase of these compound. Most of the measured ceramic specimens exhibit dielectric properties suitable as temperatures-stable and temperature-compensating dielectrics in the capacitor industry. The values of the dielectric constant K are 80-160, while those of the temperature coefficient are–500 to + 160 ppm/°C. The composition limits of the single pyrochlore phase are determined mainly by Bi₂O₃ additives.     

Modification of MgAl2O4 Microwave Dielectric Ceramics by Zn Substitution

MgAl₂O₄ microwave dielectric ceramics were modified by Zn substitution for Mg, and their dielectric characteristics were evaluated, along with their structures. Dense (Mg_{1− x} Zn _x )Al₂O₄ ceramics were obtained by sintering at 1550°–1650°C in air for 3 h, and the (Mg_{1− x} Zn _x )Al₂O₄ solid solution was determined in the entire composition range. With Zn substitution for Mg, the dielectric constant ɛ of MgAl₂O₄ just varied from 7.90 to 8.56, while the Q × f value had significantly improved up to a maximal value of 106 000 GHz at x =1.0. Moreover, the τ_f of MgAl₂O₄ ceramics had declined from −73 to −63 ppm/°C.     

Melting Properties of Bi2O3-ZnO-Nb2O5-Based Dielectric Ceramics

Cubic-pyrochlore-structure α-phase and low-symmetry-structure ß-phase are the basic phases of dielectric ceramics that are based on Bi₂O₃-ZnO-Nb₂O₅ (BZN). In this paper, the melting behaviors of the α-phase and the ß-phase have been explored using differential thermal analysis and X-ray diffractometry. The results show that BZN-based α-phase is a congruent compound; its congruent melting point is 1190°C. BZN-based ß-phase is an incongruent compound that dissociates to form α-phase and a liquid phase, with an absorption of heat, at its incongruent melting point (peritectic temperature) of 1100°C. Upon cooling, the α-phase reacts with the liquid phase to form the ß-phase via peritectic reaction. Upon quenching, the BZN-based cubic-fluorite phase precipitates from the liquid phase.     

Influence of V2O5 Additions to 5Li2O–1Nb2O5–5TiO2 Ceramics on Sintering Temperature and Microwave Dielectric Properties

The effects of the addition of V₂O₅ on the sintering behavior, microstructure, and microwave dielectric properties of 5Li₂O–1Nb₂O₅–5TiO₂ (LNT) ceramics have been investigated. With low-level doping of V₂O₅ (≤3 wt%), the microstructure of the LNT ceramic changed from a special two-level intergrowth structure into a two-phase composite structure with separate grains. And the sintering temperature of the LNT ceramics could be lowered to around 900°C by adding a small amount of V₂O₅ without much degradation in microwave dielectric properties. Typically, better microwave dielectric properties of ɛ_r=41.7, Q × f =7820 GHz, and τ _f =45 ppm/°C could be obtained for the 1 wt% V₂O₅-doped ceramics sintered at 900°C.     

Dielectric Studies in the System CdO-Nb2O5

Results of studies on the effect of compositional changes and impurities on the electrical characteristics of single-crystal, hot-pressed, and dry-pressed and fired cadmium niobate are presented. Specimens of compositions from CdNb₂O₆ to Cd_2.1Nb₂O_7.1 were studied optically, electrically, and by X-ray diffraction. Cadmium metaniobate remains paraelectric from –180° to +400°C. and acts primarily as a diluent to the ferroelectric properties of cadmium niobate. The Curie point of cadmium niobate occurs at approximately –85°C. with a dielectric constant peak of 6600 for a [110] crystal cut. Indications of antiferroelectricity are discussed. Room-temperature measurements in the paraelectric phase at 21 kilomegacycles indicate a dielectric constant of 150 with a dissipation factor of less than 0.002 as compared with the high losses of BaTiO₃ in this frequency range.     

Effects of Sm2O3 and Gd2O3+ Nd2O3 on Electromechanical Properties of PbTiO3 Ceramics

The electromechanical properties of PbTiO₃ ceramics, modified by substitution of Sm or Gd + Nd (same average atomic radius as Sm) for Pb, were studied in the range of 6% to 14% substitution. The modified PbTiO₃ ceramics were stable, and the Curie temperature decreased linearly over this composition range. The 10% Sm composition had a large anisotropy in the coupling factor ratio, k _t / k _p , and a similar, but weaker, effect developed for 12% (1/2 Gd + 1/2 Nd). This indicates that other than average ion size may influence the electromechanical coupling factor ratio.     

New Yellow Ceramic Pigment Based on Codoping Pyrochlore-type Y2Ti2O7 with V5+ and Ca2+

A new yellow pigment with the pyrochlore structure Ca_xY_{2− x} V _x Ti_{2− x} O₇ was prepared as a substitute for the decreasing variety of available yellow ceramic pigments due to the severe regulation of toxic lead and cadmium. The solubility limit of vanadium in this pigment was found to be 1.5 wt% as V₂O₅ or 0.13 as x in the above formula expression. Characterization of vanadium in the vanadium pyrochlore yellow pigment by electron spectroscopy for chemical analysis and electron spin resonance showed that the oxidation state of vanadium was V⁵⁺ and its yellow color mostly originated from V⁵⁺ substituted for Ti⁴⁺. Comparison of color characteristics of Ca_xY_{2− x} V _x Ti_{2− x} O₇ with those of commercial V–SnO₂ and V–ZrO₂ revealed that Ca _x Y_{2− x} V _x Ti₂₋O₇ had better color strength and brightness than the commercial pigments.     

The Li2O–Nb2O5–TiO2 Composite Microwave Dielectric Ceramics with Adjustable Permittivities

A group of new y M-phase/(1− y ) Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ composite ceramics with adjustable permittivities for low-temperature co-fired ceramic applications was initially investigated in the study. The 0.5 M-phase/0.5 Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ ( x =0.01, 0.02, 0.04, 0.06, 0.081) composite ceramics were first investigated to find the appropriate "Li₂TiO₃ss" composition ( x value). The best dielectric properties of ɛ_r=40.1, Q × f values up to 9318 GHz, τ_f=25 ppm/°C, were obtained for the ceramics composites at x =0.02. Based on the good dielectric properties, the suitable "Li₂TiO₃ss" composition with x =0.02 was mixed with the Li_1.0Nb_0.6Ti_0.5O₃ powder as the ratio of y "M-phase"/(1− y ) "Li₂TiO₃ss" ( y =0.2, 0.4, 0.5, 0.6, 0.8). By adjusting the y values, the group of composite ceramics could exhibit largely are adjustable permittivities varying from ∼20 to ∼60, while Q × f and τ_f values relatively good. Nevertheless, in this study, because there are interactions between the M-phase and Li₂TiO₃ss during sintering process, their microwave dielectric properties could not be predicted precisely by the empirical model.     

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.     

Finite Size Effect on the Sinterability and Dielectric Properties of ZnNb2O6–ZBS Glass Composites

ZnNb₂O₆ (ZN) is a columbite-structured niobate compound showing excellent dielectric properties and comparatively low sintering temperatures (∼1200°C). Hence it is a good candidate for possible low-temperature cofired ceramics (LTCC) applications. In the present investigation, ZnNb₂O₆ was synthesized in the form of micrometer-sized powder using a conventional solid-state ceramic synthesis route as well as in the form of nanosized powder by a polymer complex method. The finite size effect of ZN particles on sinterability and microwave dielectric properties of sintered pellets was evaluated. The phase formation was confirmed from the X-ray diffraction (XRD) analysis. The particle size distribution of the nanoparticles was found to be of the order of 18–20 nm by using high-resolution transmission electron microscopy analysis and 30 nm by analyzing the XRD patterns using Debye Scherrer's formula, after correcting for the instrument broadening effects. A ZN–60ZnO–30B₂O₃–10SiO₂ (ZBS) composite was made by adding predetermined amounts of glasses. The microstructures of the sintered pellets of ZN and ZN–ZBS composites were examined using scanning electron microscopy and analyzed using image analysis. The nano-ZN–ZBS composites were sintered to 93% of the reported density at 925°C/2 h, with microwave dielectric properties of ɛ_r=22.5, Q × f ∼12 800 GHz, and τ_f=−69.6 ppm/°C, emerging as a potential material for possible LTCC applications.