Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Microwave dielectric properties of Ca[(Li1/3Nb2/3)1−x Tix]O3−δ ceramics with glass

The effect of the addition of glass on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−x Ti_x]O_3−δ(CLNT) was investigated. Addition of glass (B₂O₃-ZnO-SiO₂-PbO system) improved the densification and reduced the sintering temperature from 1150^∘C to 900^∘C of Ca[(Li_1/3Nb_2/3)_1−x -Ti_x]O_3−δ microwave dielectric ceramics. As increasing glass contents from 10 wt% to 15 wt%, the dielectric constants (ε_r) and bulk density were increased. The quality factor (Q⋅f₀), however, was decreased slightly. The temperature coefficients of the resonant frequency (τ_f) shifted positive value as increasing glass contents over Ti content is 0.2 mol. The dielectric properties of Ca[(Li_1/3Nb_2/3)_0.75Ti_0.25]O_3−δ with 10 wt% glass sintered at 900^∘C for 3 h were ε_r = 40 Q·f₀ = 11500 GHz, τ_f = 8, ppm/°C. The relationship between the microstructure and dielectric properties of ceramics was studied by X-ray diffraction (XRD), and scanning electron microscope (SEM).     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ε _r ), high quality factor (Q × f), and small temperature coefficient of resonant frequency (TCF) are required for the application of chip passive components in wireless communication low temperature co-fired ceramics (LTCC). In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₅Nb₆O₂₈ ceramics were investigated as a function of B₂O₃-CuO content. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250^∘C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ε _r of 37, TCF of −12 ppm/^∘C. The addition of B₂O₃-CuO was revealed to lower the sintering temperature of Ba₃Ti₅Nb₆O₂₈, 900^∘C and to enhance the microwave dielectric properties: Q × f of 32,500 GHz, ε _r of 40, TCF of 9 ppm/^∘C. From the X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Control of Microwave Dielectric Properties in the System BaO ⋅ Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>—BaO ⋅ Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>

BaO ⋅ Nd₂O₃ ⋅ 4TiO₂—based ceramics were prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1200–1450^∘C. Microstructures were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM); microwave dielectric properties were determined at 3 GHz by the Hakki and Coleman method. Product densities were at least 95% theoretical. The addition of up to 1 wt% Al₂O₃ to the starting mixtures reduced the sintering temperatures by at least 100^∘C. Incorporation of small levels of Al into the structure (initially Ti sites) led to an increase in Q × f values, from 6200 to 7000 GHz, a decrease in relative permittivity (ε_r) from 88 to 78, and moved the temperature coefficient of resonant frequency (τ_f) towards zero. The addition of 0.5 wt% Al₂O₃ with 8 wt% Bi₂O₃ improved densification, increased both ε_r (to 88) and Q× f (to 8000 GHz) and moved τ_f closer to zero. Ceramics in the system (1 − x)BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + xBaO ⋅ Al₂O₃ ⋅ 4TiO₂ exhibited very limited solid solubility. The end member BaO ⋅ Al₂O₃ ⋅ 4TiO₂ was tetragonal in structure with the following dielectric properties: ε_r = 35; Q× f = 5000 GHz; τ_f = −15ppm/^∘C. Microstructures of the mixed Nd-Al compositions contained two distinct phases, Nd-rich needle-like grains and large Al-rich, lath-shaped grains. Products with near zero τ_f were achieved at compositions of approximately 0.14BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + 0.86BaO ⋅ Al₂O₃ ⋅ 4TiO₂, where Q× f = 8200 GHz and ε_r = 71.     

Influence of sintering temperatures on the electrical property of bismuth sodium titanate based piezoelectric ceramics

A systematic investigation of cerium and stannum doped 0.94(Bi_0.5Na_0.5)TiO₃−0.06BaTiO₃ (Sn&Ce-BNT6BT) based lead-free piezoelectric ceramics is undertaken to understand the influence of sintering temperature on electrical properties. The X-ray diffraction patterns showed that all of the Sn&Ce-BNT6BT ceramics exhibited a single perovskite structure with the co-existence of the rhombohedral and tetragonal phase. The smaller grain size of Sn&Ce-BNT6BT ceramics was obtained at lower sintering temperature, and more cubical grains of Sn&Ce-BNT6BT ceramics were obtained at higher sintering temperature. The temperature dependence of dielectric permittivity of the compositions exhibited strong dispersion with the increasing temperature, and the dielectric loss tangent increased dramatically while the temperature over 225^∘C. The depolarization temperature T _d of Sn&Ce-BNT6BT ceramics sintered at 1160^∘C was 92.6^∘C. The remnant polarizations P _r for Sn&Ce-BNT6BT ceramics sintered at 1120 and 1200^∘C were found to be 28.8 and 33.4 μC/cm² at room temperature, respectively.     

Low Temperature Sintering of BaTi<Subscript>4</Subscript>O<Subscript>9</Subscript>-Based Middle-<Emphasis Type="Italic">k</Emphasis> Dielectric Composition for LTCC Applications

Effect of glass addition on the low-temperature sintering and microwave dielectric properties of BaTi₄O₉-based ceramics were studied to develop the middle-k dielectric composition for the functional substrate of low-temperature co-fired ceramics. When 10 wt% of glass was added, sufficient densification was obtained and the relative density more than 98% was reached at the sintering temperature of 875C. The microwave dielectric properties were k = 32, Q × f = 9000 GHz, and t_cf = 10 ppm/C. As the added amount of glass frit with base dielectric composition, phase changes from BaTi₄O₉ to BaTi₅O₁₁ and Ba₄Ti₁₃O₃₀ was observed, which result in the modification of microwave dielectric properties.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

Dielectric properties of nanocrystalline TiO2 prepared using spark plasma sintering

Ultra fine rutile powders (below 50 nm) were prepared via the sol-gel process and bulk type TiO₂ specimens were fabricated using spark plasma sintering (SPS). The TiO₂ specimen sintered at a low temperature (720^∘C) exhibited a highly relative density (97%) and a nano-sized grain structure (200 nm). Dielectric properties of spark plasma sintered TiO₂ specimens including dielectric constants (k) and losses (tan δ) were measured. The TiO₂ specimen, obtained by SPS, showed a high dielectric constant (∼780) and a low tan δ (∼0.005), and a relaxation behavior at 1 MHz. After the subsequent annealing process of the TiO₂ specimen in O₂ flow, the dielectric constants remarkably decreased (k = 100s). These dielectric properties of nanocrystalline TiO₂ specimens prepared by SPS were discussed in terms of space charges produced by the reduction of Ti⁴⁺ ions and crystallographic orientations of grains.     

Effects of structural characteristics on microwave dielectric properties of (1−x)CaWO4 –xLaNbO4 ceramics

Dependences of microwave dielectric properties on the structural characteristics of (1−x)CaWO₄–xLaNbO₄ ceramics were investigated as a function of LaNbO₄ content (0.0 ≤ x ≤ 0.5). A single phase with tetragonal scheelite structure was obtained up to x = 0.35, and then the mixture phases with scheelite and fergusonite structure were detected. With the increase of LaNbO₄, the deviation of the observed dielectric polarizabilities calculated by the Clausius-Mosotti equation from the theoretical values calculated by the additivity rule of dielectric polarizability, was decreased due to the decrease of oxygen bond valence in ABO₄ scheelite structure. Dielectric constant (K) and temperature coefficient of resonant frequency (TCF) were increased with LaNbO₄ content due to the decrease of oxygen bond valence. Q ⋅ fvalue was dependent on the atomic packing fraction of unit cell as well as the grain size. Typically, K = 13.3, Qf = 50,000 GHz and TCF = −8.7 ppm/^oC were obtained for the specimens with 0.3 mol of LaNbO₄ sintered at 1150^oC for 3 h.     

Synthesis of Pb(Ni1/3Nb2/3)0.72Ti0.28O3 perovskite ceramics by a reaction-sintering process

Pb(Ni_1/3Nb_2/3)_0.72Ti_0.28O₃ (PNNT) perovskite ceramics produced by a reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂, Nb₂O₅ and TiO₂ was pressed and sintered directly into PNNT ceramics. PNNT ceramics of 100% perovskite phase were obtained. For PNNT sintered for 2 h in PbO compensated atmosphere, maximum density reaches a value 8.49 g/cm³ (99.8% of the theoretical value) at 1250^∘C. A maximum dielectric constant 20600 occurred around 37^∘C at 1 kHz in PNNT sintered at 1250^∘C for 2 h.     

Synthesis and sintering properties of (La0.8Ca0.2−x Sr x )CrO3 perovskite materials for SOFC interconnect

Synthesis and sintering properties of the (La_0.8Ca_0.2−x Sr _x )CrO₃ samples doped by two alkaline earth metals in comparison to the doped only by one alkaline earth metal were evaluated by phase analysis, sintering properties, thermal expansion behaviors, and electrical conductivity. The sintered (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) and (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0.2) were found to have orthorhombic and rhombohedral symmetries, respectively. Relative density of the (La_0.8Sr_0.2)CrO₃ sample sintered at 1500^∘C for 5 h was lower than that of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) sample. TECs of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, 0.1, and 0.2) in air were 11 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, and 11.3 × 10⁻⁶/^∘C, respectively. The electric conductivity of the (La_0.8Ca_0.2−x Sr _x )CrO₃ sample was determined.     

Control of 0.2CaTiO3-0.8Li0.5Nd0.5TiO3 microwave dielectric ceramics by additions of Bi2Ti2O7

Ceramics of 0.2CaTiO₃-0.8Li_0.5Nd_0.5TiO₃) have been prepared by the mixed oxide route using additions of Bi₂O₃-2TiO₂ (up to 15 wt%). Powders were calcined 1100^∘C; cylindrical specimens were fired at temperatures in the range 1250–1325^∘C. Sintered products were typically 95% dense. The microstructures were dominated by angular grains 1–2 μm in size. With increasing levels of Bi₂O₃-2TiO₂ additions, needle and lath shaped second phases developed. For Bi₂Ti₂O₇ additions up to 5 wt%, the relative permittivity increased from 95 to 131, the product of dielectric Q value and measurement frequency increased from 2150 to 2450 GHz and the temperature coefficient of resonant frequency (τ _f ) increased from −28pp/^∘C to +22pp/^∘C. A product with temperature stable τ _f could be obtained at ∼2 wt% Bi₂Ti₂O₇ additions. For high levels of additives, there is minimal change in relative permittivity, the Qxf values degrade and τ _f becomes increasingly negative.     

Sintering and dielectric properties of Al2O3 ceramics doped by TiO2 and CuO

The effects of CuO and TiO₂ additives on the microstructure and microwave dielectric properties of Al₂O₃ ceramics were investigated. Al₂O₃ ceramics with CuO and TiO₂ additions can be well sintered to achieve 93∼98% theoretical densities below 1,360 °C due to Ti₄Cu₂O liquid phase sintering effect. The Qf values decreased with increasing CuO and TiO₂ content, due to the formation of the second phase Ti₄Cu₂O. However, the varying behaviors of the dielectric constant (ɛ _r ) and temperature coefficients (τ _f ) were associated with phase constitutions, as a result of the change of CuO and TiO₂content. The τ _f can be shifted close to 0 ppm/°C by controlling the content of CuO and TiO₂. The specimens with 0.5 wt.% CuO and 7 wt.% TiO₂ sintered at 1,360 °C for 4 h showed ɛ _r of 11.8, Qf value of 30,000 GHz, and τ _f of −7 ppm/°C.     

Microwave Dielectric Properties of CuO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript> Ceramics with Low Sintering Temperature

Microwave dielectric properties of low temperature sintering ZnNb₂O₆ ceramics doped with CuO-V₂O₅-Bi₂O₃ additions were investigated systematically. The co-doping of CuO, V₂O₅ and Bi₂O₃ can significantly lower the sintering temperature of ZnNb₂O₆ ceramics from 1150 to 870C. The secondary phase containing Cu, V, Bi and Zn was observed at grain boundary junctions, and the amount of secondary phase increased with increasing CuO-V₂O₅-Bi₂O₃ content. The dielectric properties at microwave frequencies (7–9 GHz) in this system exhibited a significant dependence on the relative density, content of additives and microstructure of the ceramics. The dielectric constant ( _r) of ZnNb₂O₆ ceramics increased from 21.95 to 24.18 with increasing CuO-V₂O₅-Bi₂O₃ additions from 1.5 to 4.0 wt%. The quality factors (Q× f) of this system decreased with increasing CuO-V₂O₅-Bi₂O₃ content and ranged from 36118 to 67100 GHz for sintered ceramics, furthermore, all Q× f values of samples with CuO-V₂O₅-Bi₂O₃ additions are lower than that of un-doped ZnNb₂O₆ ceramics sintered at 1150C for 2 h. The temperature coefficient of resonant frequency ( _f) changed from –33.16 to –25.96 ppm/C with increasing CuO-V₂O₅-Bi₂O₃ from 1.5 to 4.0 wt%     

Ferroelectricity in Aurivillius-Type Structure Ceramics with n = 2 and (SrBi2Nb2O9)0.35(Bi3TiNbO9)0.65 Composition

Aurivillius-type structure compounds are good candidates for their use as high temperature piezoelectrics, due to their high ferro-paraelectric phase transition temperature. However, this characteristic correlates with a high coercive field that makes difficult the poling process, necessary to have piezoelectric activity. The electric properties, specially conductivity, limit the maximum poling field. On the other hand, piezoelectric properties are directly related to the ferroelectric remanent polarization. Thus, the study of both characteristics is towards improving the piezoelectric properties of these materials. In this work, ceramics with nominal composition (SrBi₂Nb₂O₉)_0.35(Bi₃TiNbO₉)_0.65 (T_C∼ 760^∘C), prepared by hot pressing of mechanically activated precursors, have been studied. The electrical properties (permittivity, dielectric loss factor and d.c. conductivity) as a function of frequency and temperature have been measured, up to temperatures higher than the ferro-paraelectric phase transition, and their anisotropy explained in terms of the ceramic texture. Well-saturated ferroelectric hysteresis loops at 250^∘C have been obtained, with values of P_r = 21.4 μ C/cm² and E_c = 70.4 kV/cm.     

Synthesis of nanocomposites of PMN-PT-BT with metal oxides via surface modification

Low-temperature-sinterable PMN-PT-BT [0.96 (0.91Pb(Mg_1/3Nb_2/3)O₃-0.09PbTiO₃)-0.04BaTiO₃] powder was first prepared by the modified mixed oxide method and then metal (M = Cu, Mg, Ag) oxides were introduced as their nitrate salts. Precalcined PMN-PT-BT/MO composite powders were surface modified with the magnesia sol to suppress diffusion of Ag or metal oxides. Such prepared composite powders were sintered > 98% T.D. at 850–900^∘C and showed homogeneous microstructures with <100 nm Ag or metal oxide particles. Nanoparticles were located mostly in grains and some on grain boundaries. Grain growth was substantially inhibited and resulted in grain size of ∼2 μm. The nanocomposites of PBT/Ag and PBT/MgO showed substantially improved sintered densities and dielectric properties at sintering temperature below 1000^∘C, but the PBT/CuO composite was hardly affected. The PBT/Ag composites treated with the MgO sol showed good handling strength of MOR > 120 MPa. The proper amount of the magnesia sol for surface modification seemed to be 0.5–1.0 wt.     

Dielectric and mechanical properties of hot-pressed SiCN/Si3N4composites

A series of high temperature radar wave-absorbing materials, SiCN/Si₃N₄ceramics, were prepared by hot-pressing. The nanometer SiCN powder, used as an absorber in the SiCN/Si₃N₄ceramic, was synthesized through laser pyrolysis of ((CH₃)₃Si)₂NH) and NH₃. The dielectric and mechanical properties of the prepared ceramics were investigated. XRD and SAED were conducted to study the growth of crystals in the ceramics. The results showed that the transformation of Si₃N₄from α to β was inhibited. The growth of the rod-like β -Si₃N₄grains in SiCN/Si₃N₄ceramics was retarded during hot-pressing process due to the existence of the nanometer SiCN particles. The relative density and the strength of the composites both decreased with the increase of the SiCN content in the composites. The dielectric properties of the ceramics prepared at different temperatures were very different. For the samples sintered at 1600^∘C and 1700^∘C, both the real and imaginary parts of the complex permittivity of them increased as the content of SCN powder in the sample obviously. For the sample with same concentration of SCN, the real and imaginary parts of them varied with the sintering temperature. SAED pattern revealed that structure of the SiCN in SiCN/Si₃N₄sintered at 1800^∘C tended to crystallize fully. Its real, imaginary parts and dissipation factor were much lower than those sintered at 1600^∘C and 1700^∘C greatly. Supported by national natural science foundation of China (No. 50572090)     

Effect of SnO2 on improvement on the microwave dielectric properties of Ba2Ti9O20

Effect of SnO₂ addition on the crystal structure/microstructure and the related microwave dielectric properties of the Ba₂Ti₉O₂₀ were systematically investigated. Incorporation of SnO₂ markedly stabilized the phase constituent and microstructure for the Ba₂Ti₉O₂₀ such that high quality materials can be obtained in a much wider processing window. The sintered density of the Ba₂Ti₉O₂₀ increased linearly, but the microwave dielectric constant (K) decreased monotonically, with the SnO₂ doping concentration. The quality factor (Qxf) of the materials increased firstly due to the addition of SnO₂, but decreased slightly with further increase in SnO₂ content. The best microwave dielectric properties obtained are K = 38.5 and Qxf = 31,500 GHz, which occurs for the 0.055 mol SnO₂-doped and 1350 °C/4 h sintered samples. These properties are markedly better than those for undoped materials (K = 38.8 and Qxf = 26,500 GHz).     

Microstructural and piezoelectric properties of PZN substituted PMN-PZT ceramics for multilayer piezoelectric transformer

In this paper, in order to develop the low temperature sintering ceramics for multilayer piezoelectric transformers, Pb[(Mn_1/3,Nb_2/3)_0.07(Zn_1/3Nb_2/3)_a (Zr_0.48Ti_0.52)_1-0.07-aO₃] ceramics were prepared with the variations of PZN from 2 to 14 mol% and their dielectric and piezoelectric properties were investigated. Sintering temperature was varied from 940 to 1000^∘C. At 8 mol% PZN substituted specimen sintered at 970^∘C, electromechanical coupling factor(kp), mechanical quality factor(Qm), dielectric constant and peizoelectric constant(d₃₃) showed the optimal values of 0.536, 1803, 1551 and 328[pC/N], respectively, for multilayer piezoelectric transformer application.