Synthesis and characterization of nanocrystalline SrBi2Nb2O9 ferroelectric ceramics using TEA as the polymeric matrix

The processing conditions, reaction mechanism, fine structure of the powders, microstructure, and dielectric properties of SrBiNb₂O₉ (SBN) were systematically studied. A relative density of >80% was obtained using a two-step sintering process at moderate pressure. XRD showed that a single phase with the layered perovskite structure of SrBi₂Nb₂O₉ (SBN) was formed after calcining at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The crystallite size (D) and the effective strain (η) were found to be 38.8 nm and 0.01475, respectively, while the particle size obtained from TEM was laid between 25 and 36 nm. SEM revealed that the average grain size after sintering at 900 °C for 4 h was 0.67 μm. Dielectric constant and corresponding tangent loss were measured in the frequency range from 1 kHz to 1 MHz from which the Curie temperature (T_c) was found to be at 450 °C.     

Dielectric behaviors of (Nb2O5)(1-x)xTiO2 ceramics

The dielectric constants (K) of ceramics composition (Nb₂O₅)(_1-x): xTiO₂, (x = 0.05, 0.08, 0.11) have been measured over the temperature range from -180 °C to 180 °C in the frequency range 100 Hz-IMHz. For all three samples, the temperature dependence of the dielectric constants at various frequencies shows the dielectric dispersion and the frequency dependent dielectric losses are observed, suggesting the several relaxation phenomena. Dielectric loss data are analyzed by Arrhenius formalism indicating the presence of relaxation type dielectric mechanisms in (Nb₂O₅)(_1-x): xTiO₂ ceramics.     

PREPARATION OF PEROVSKITE 0.75Pb(Ni1/3Nb2/3)O3-0.25PbTiO3 CERAMICS USING SEMICHEMICAL METHODS AND RELATED REACTION MECHANISMS

This article discusses a mechanism for preparing perovskite powders, 0.75Pb(Ni_1/3Nb_2/3)O₃-0.25PbTiO₃ (PNN-PT), using a semichemical method (SCM).Precursors were prepared by adding aqueous Ni(Ac)₂ solutions to an alcohol slurry of PbO, Nb₂O₅, and TiO₂. The TG-DTG and DSC analysis of the precursors and XRD analysis of the powders at different thermal treatment temperatures showed that the reaction mechanisms in this method differ from those in the conventional mixed-oxide method. The aqueous Ni(Ac)₂ solution reacted with PbO to form Pb(Ac)₂ · Pb(OH)₂ · H₂O and Ni(OH)₂, which decomposed to form nascent PbO and NiO, thereby improving the reactivity and distribution of PbO and NiO. Pb₃Nb₂O₈ and NiNb₂O₆ formed and were easily converted into the perovskite phase during the thermal treatment process. At a thermal treatment temperature of 850°C, the content of the perovskite phase reached 98%. Pyrochlore-free PNN-PT ceramic was obtained after 2 h of sintering at 1100°C, and its dielectric properties were found to be excellent at temperatures ranging between -55 and 120°C.     

Electric properties of polycrystalline PbCd1/3Nb2/3O3

Temperature dependence of dielectric permittivity and electric conductivity of polycrystalline PbCd_1/3Nb_2/3O₃ in the region of phase transition have been presented. Electric properties of polycrystalline PbCd_1/3Nb_2/3O₃ depend on frequency of the measuring field. In the region of para-ferroelectric phase transition a change of electric properties takes place.     

Effects of the sintering atmosphere on Nb-based dielectrics

The effects of a forming atmosphere on the stability, the sintering and the dielectric properties of Ba₅Nb₄O₁₅, BaNb₂O₆, ZnNb₂O₆ and Zn₃Nb₂O₈ ceramics were investigated, because of the primary importance of the sintering atmosphere in relation to copper sintering. These Nb-based materials were sintered in air and in Ar/H₂10%. Zn-containing samples are very sensitive to the reductive atmosphere. ZnO volatilises at 800–850 °C and the resulting compound does not exhibit the expected properties. BaNb₂O₆ and Ba₅Nb₄O₁₅ are more stable in term of relative weight loss. Nevertheless, the phase analysis reveals a modification of the BaNb₂O₆ phase, what induces the degradation of the dielectric property stability versus temperature. The properties of Ba₅Nb₄O₁₅ are not modified by a sintering in reductive atmosphere. A relative permittivity of 38.8, a permittivity temperature coefficient of −150 ppm °C⁻¹ and an insulating resistivity of 10^10.9 Ω cm were obtained for this latter.     

Unusual ferroelastic behavior in ferroelectric lead bismuth nioebte (PbBi2Nb2O9)

X-ray and optical measurements are used to show that the spontaneous strain (b/a-1) and optical birefringence Δn_ab in single crystals of ferroelectric PbBi₂Nb₂O₉ are a function of the state of electrical poling, going to a zero in the unpoled state. In poled crystals all spontaneous strain is lost at a temperature ≃200°C below the dielectric Curie temperature in a manner reminiscent of the behavior of the perovskite relaxor ferroelectrics which have diffuse phase transitions.     

Piezoelectric properties of Pb(Mn1/3Nb2/3)O3–PbZrO3–PbTiO3 ceramics with sintering aid of 2CaO–Fe2O3 compound

Since the electromechanical devices move towards enhanced power density, high mechanical quality factor (Q_m) and electromechanical coupling factor (k_p) are commonly needed for the high powered piezoelectric transformer with Q_m≥2000 and k_p=0.60. Although Pb(Mn_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMnN–PZ–PT) ceramic system has potential for piezoelectric transformer application, further improvements of Q_m and k_p are needed. Addition of 2CaO–Fe₂O₃ has been proved to have many beneficial effects on Pb(Zr,Ti)O₃ ceramics. Therefore, 2CaO–Fe₂O₃ is used as additive in order to improve the piezoelectric properties in this study. The piezoelectric properties, density and microstructures of 0.07Pb(Mn_1/3Nb_2/3)O₃–0.468PbZrO₃–0.462PbTiO₃ (PMnN–PZ–PT) piezoelectric ceramics with 2CaO–Fe₂O₃ additive sintered at 1100 and 1250 °C have been studied. When sintering temperature is 1250 °C, Q_m has the maximum 2150 with 0.3 wt.% 2CaO–Fe₂O₃ addition. The k_p more than 0.6 is observed for samples sintered at 1100 °C. The addition of 2CaO–Fe₂O₃ can significantly enhance the densification of PMnN–PZ–PT ceramics when the sintering temperature is 1250 °C. The grain growth occurred with the amount of 2CaO–Fe₂O₃ at both sintering temperatures.     

Effect of sintering and poling conditions on the properties of 0·125Pb (Mg1/3Nb2/3)O3−0.875Pb(Zr0·5Ti0·5)O3 ceramics doped with 4PbO. B2O3

The influence of sintering and poling conditions on dielectric properties and microstructures of the system 0·125Pb(Mg_1/3Nb_2/3)O₃−0·875Pb (Zr_0·5Ti_0·5)O₃ was investigated. Specimens were prepared by the conventional mixed-oxide technique. On account of eliminating the pyrochlore phase and lowering the sintering temperature, the calcined 0·125PZT−0·875PMN ceramic was doped with 4PbO.B₂O₃ glass powder. The 4PbO.B₂O₃ glass frit not only has a low flow temperature, but also a high polarizability. Additions of 4PbO.B₂O₃ to the perovskite 0·125PMN–0·875PZT solid solution will form a liquid phase, which served as a densification aid for the ceramics. With additions of 0·2 wt% glass frit, densities in excess of 98% of theoretical were obtained after sintering at 115°C. By variation of the fabrication processes, the influence of sintering and poling conditions on the properties of the ceramics was studied.     

Piezoelectric properties of low temperature sintering in Pb(Zr,Ti)O3–Pb(Zn,Ni)1/3Nb2/3O3 ceramics for piezoelectric transformer applications

In this study, in order to develop low-temperature sintering ceramics for a multilayer piezoelectric transformer application, we explored CuO and Bi₂O₃ as sintering aids at low temperature (900 °C) sintering condition for Sb, Li and Mn-substituted 0.8Pb(Zr_0.48Ti_0.52)O₃–0.16Pb(Zn_1/3Nb_2/3)O₃–0.04Pb(Ni_1/3Nb_2/3)O₃ ceramics. These substituted ceramics have excellent piezoelectric and dielectric properties such as d₃₃  347 pC/N, k_p  0.57 and Q_m  1469 when sintered at 1200 °C. The addition of CuO decreased the sintering temperature through the formation of a liquid phase. However, the piezoelectric properties of the CuO-added ceramics sintered below 900 °C were lower than the desired values. The additional Bi₂O₃ resulted in a significant improvement in the piezoelectric properties. The composition Sb, Li and Mn-substituted 0.8Pb(Zr_0.48Ti_0.52)O₃–0.16Pb(Zn_1/3Nb_2/3)O₃–0.04Pb(Ni_1/3Nb_2/3)O₃ + 0.5 wt% CuO + 0.5 wt% Bi₂O₃ showed the value of k_p = 0.56, Q_m = 1042 (planar mode), d₃₃ = 350 pC/N, when it was sintered at 900 °C for 2 h. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric transformer application.     

Yb2O3 and Y2O3 co-doped zirconia ceramics

A suspension stabilizer-coating technique was employed to prepare x mol% Yb₂O₃ (x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y₂O₃ co-doped ZrO₂ powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb₂O₃ and Y₂O₃ co-doped zirconia ceramics. Fully dense ZrO₂ ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb₂O₃ content and the sintering parameters. Polycrystalline tetragonal ZrO₂ (TZP) and fully stabilised cubic ZrO₂ (FSZ) were achieved in the 1.0 mol% Y₂O₃ stabilised ceramic, co-doped with 1.0 mol% Yb₂O₃ and 4.0 mol% Yb₂O₃, respectively. The amount of stabilizer needed to form cubic ZrO₂ phase in the Yb₂O₃ and Y₂O₃ co-doped ZrO₂ ceramics was lower than that of single phase Y₂O₃-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m^1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb₂O₃ and 1.0 mol% Y₂O₃ ceramic at 1450 °C for 1 h.     

Investigation of some niobate-based dielectrics in view of base metal co-sintering

Bearing in mind the excellent dielectric properties at high frequency of some niobates like ZnNb₂O₆, Zn₃Nb₂O₈, BaNb₂O₆, Ba₅Nb₄O₁₅ (_r 20–45, tan δ < 10 × 10⁻⁴ and ρ_i > 10¹⁰ Ω cm), synthesis, sintering and properties of these oxides are reported. The lowering of their sintering temperature has been investigated for these four ceramics using sintering aids. Using appropriate additive, it is possible to densify these ceramics at a temperature for which base metal electrodes, e.g. Cu and Ag can be employed. Two formulations were found to be sinterable at 1000 °C (lower than the copper melting point) whereas a third formulation is co-sinterable with silver electrodes. For this later, the dielectric properties are globally maintained in comparison with the pure compound sintered at 1200 °C. This result makes this formulation suitable for silver based passive components devices manufacturing.     

Sintering and dielectric properties of Cu2Ta4O12 ceramics

In this work, Cu₂Ta₄O₁₂ ceramic was investigated as a promising, lead-free, nonferroelectric material with high dielectric permittivity. The results of impedance spectroscopy studies carried out at frequencies 10 Hz to 2 MHz over a wide temperature range from −55 to 700 °C were analyzed in the impedance, dielectric permittivity and electric modulus formalisms. In complex impedance plots two distinct arcs were distinguished, ascribed to the semiconducting grains and to the insulating grain boundaries. Cu₂Ta₄O₁₂ ceramic was found to exhibit a high dielectric permittivity exceeding 10,000 at low frequencies in the temperature range 150–740 °C. High permittivity of this material was attributed to the formation of internal (grain boundary) barrier layer capacitors. The influence of sintering conditions on microstructure, composition and dielectric properties of Cu₂Ta₄O₁₂ ceramics was also studied.     

Sintering behavior and microwave dielectric properties of Bi2O3–ZnO–Nb2O5-based ceramics sintered under air and N2 atmosphere

The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) and Bi₂(Zn_1/3Nb_2/3−xV_x)₂O₇ (BZNV, x = 0.001) sintered under air and N₂ atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V₂O₅ and N₂ atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N₂ atmosphere with _r = 76.1, Q = 850 and Q_f = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with _r = 76.7, Q = 890 and Q_f = 3580 GHz. The temperature coefficient of resonant frequency τ_f was not obviously influenced by the different atmospheres. For BZN ceramics the τ_f was −79.8 ppm/°C while τ_f is −87.5 ppm/°C for BZNV ceramics.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Dieletric and relaxation behaviors of (PbMg1/3Nb2/3O3)0.67(PbTiO3)0.33 single crystal

Dielectric permittivity along the [111] direction has been measured as a function of temperature for a relaxor ferroelectric single crystal (PbMg_1/3Nb_2/3O₃)_0.67(PbTiO₃)_0.33 (PMN-33%PT). A sharp ferroelectric phase transition was observed near 425 K and 429 K for cooling and heating processes, respectively. As temperature decreases, a diffuse phase transition (which begins near 330 K upon cooling) was detected. In addition, the nature of the thermal hysteresis for the dielectric permittivity confirms that these transitions (near 330 and 425 K upon cooling) are diffuse first-order and first-order, respectively. The frequency-dependent dielectric data ε'₁₁₁ (ƒ, T) prove the existence of an electric dipolar relaxation process between 350 and 400 K. The activation energy, the Vogel-Fulcher temperature and attempt frequency corresponding to this relaxation process are also calculated.     

Fabrication of PMN and PFN ceramics by a two-stage sintering technique

Relaxor perovskite ceramics of lead magnesium niobate (PMN) and lead iron niobate (PFN) have been prepared by employing a two-step mixed oxide synthetic route, followed by the application of a two-stage sintering method. The effect of the latter on phase formation, densification behaviour, microstructure and dielectric properties of both relaxor systems is examined. Two types of pyrochlore phase are found to co-exist with the major phase in the PMN system, i.e. Pb₃Nb₄O₁₃ and Pb_1·83Nb_1·71Mg_0·29O_6·39 with an MgO inclusion. By comparison, a PbFe₈O₁₃ pyrochlore phase with an Fe₂O₃ inclusion is observed in the PFN system. The types and concentrations of phases present are found to depend upon sintering conditions. In connection with dielectric properties, a substantial dependence of the maximum values of both relative permittivity (′_r,max) and dissipation factor (tanδ_max) on sintering regime is observed. By employing optimised two-stage sintering conditions, high density ceramics with low firing temperatures and reasonable relative permittivities can be achieved in both systems.     

Phase diagram of the system: Al2O3–ZrO2

The system Al₂O₃–ZrO₂ was studied by differential thermal analysis in inert atmosphere and in vacuum. The eutectic was located at 1866°C and 40% mass of ZrO₂. Zirconia solid solution at the eutectic temperature is up to 1.1±0.3% mass of Al₂O₃. Enthalpy of melting of this eutectic is 1080±90 J/g. Pure ZrO₂ transforms from monoclinic to tetragonal at 1162±7°C, but the saturated solid solution of ZrO₂, with 0.7±0.2% mass Al₂O₃ at this temperature, transforms at 1085±5°C. Inverse transitions occur with hysteresis correspondingly at 1055±5 and 995±5°C. Enthalpy of transformation of pure ZrO₂ from monoclinic to tetragonal phase is 42±5 J/g (5.2±0.6 J/mol) but only 30±5 J/g for a ZrO₂ saturated solid solution.     

Physicochemical surface and catalytic properties of CuO–ZnO/Al2O3 system

A series of CuO–ZnO/Al₂O₃ solids were prepared by wet impregnation using Al(OH)₃ solid and zinc and copper nitrate solutions. The amounts of copper and zinc oxides were varied between 10.3 and 16.0 wt% CuO and between 0.83 and 7.71 wt% ZnO. The prepared solids were subjected to thermal treatment at 400–1000°C. The solid–solid interactions between the different constituents of the prepared solids were studied using XRD analysis of different calcined solids. The surface characteristics of various calcined adsorbents were investigated using nitrogen adsorption at −196°C and their catalytic activities were determined using CO-oxidation by O₂ at temperatures ranged between 125°C and 200°C.

The results showed that CuO interacts with Al₂O₃ to produce copper aluminate at ≥600°C and the completion of this reaction requires heating at 1000°C. ZnO hinders the formation of CuAl₂O₄ at 600°C while stimulates its production at 800°C. The treatment of CuO/Al₂O₃ solids with different amounts of ZnO increases their specific surface area and total pore volume and hinders their sintering (the activation energy of sintering increases from 30 to 58 kJ mol⁻¹ in presence of 7.71 wt% ZnO). This treatment resulted in a progressive decrease in the catalytic activities of the investigated solids but increased their catalytic durability. Zinc and copper oxides present did not modify the mechanism of the catalyzed reaction but changed the concentration of catalytically active constituents (surface CuO crystallites) without changing their energetic nature.     

The reaction sequence and dielectric properties of BaSm2Ti4O12 ceramics

To establish the correct reaction sequence of BaO–Sm₂O₃–4TiO₂, phases present in different calcining temperatures are identified by X-ray diffraction patterns. When different calcining temperatures are used, the source phase BaO (BaCO₃) consumes below 850°C, the source phases TiO₂ and Sm₂O₃ consume at 1000 and 1150°C; the intermediate phases BaTiO₃, BaTi₄O₉, and Sm₂Ti₂O₇ consume at 1050, 1200, and 1250°C, respectively. The BaSm₂Ti₄O₁₂ phase starts to reveal at the 1100°C-calcined powder. The integrating intensity of BaSm₂Ti₄O₁₂ phase increases with the raising of calcining temperatures, accompanying with the decrease of integrating intensities of the source and intermediate phases. As the sintering temperature increases, the densities, quality values, and dielectric constants of BaSm₂Ti₄O₁₂ ceramics increase and saturate at 1325^oC. The BaSm₂Ti₄O₁₂ ceramics sintered at 1325°C have the properties of Q^*f=5180,_r=81.8, and τ_f=−19.2 ppm/°C.     

Al2O3含量对PbO-CaO-B2O3-SiO2系玻璃析晶行为与烧结性能的影响

PbO-CaO-B₂O₃-SiO₂系玻璃粉体是耐高过载低温共烧陶瓷(LTCC)生瓷带的主要组成部分。玻璃粉体的析晶行为影响烧结性能,进而决定基板的使用性能。本文研究了Al₂O₃含量对PbO-CaO-B₂O₃-SiO₂系玻璃析晶行为与烧结性能的影响。结果表明:向PbO-CaO-B₂O₃-SiO₂系玻璃中引入Al₂O₃可抑制玻璃析晶,防止高膨胀晶相的析出,并提高玻璃烧结密度;不含Al₂O₃的PbO-CaO-B₂O₃-SiO₂玻璃粉体析晶峰温度为862 ℃,烧结过程中析出方石英晶相,20~200 ℃的平均线膨胀系数高达260.8×10^-7 ℃^-1;引入2.1%(质量分数)Al₂O₃可显著抑制玻璃析晶,700 ℃烧结后膨胀系数降低至72.9×10^-7 ℃^-1,介电常数显著增大,由6.30提高至7.02。