Giant piezoelectricity,rhombohedral-orthorhombic-tetragonal phase coexistence and domain configurations of (K,Na)(Nb,Sb)O3–BiFeO3–(Bi,Na)ZrO3 ceramics

Research on lead-free piezoelectric ceramics has been an important subject in recent years due to increasingly strong environmental concerns. In this paper, we report the piezoelectric performance, phase transitions and domain structure for a series of dense (0.994-x)(K_0.40Na_0.60)(Nb_0.955Sb_0.045)O₃–0.006BiFeO₃–x(Bi_0.50Na_0.50)ZrO₃ ceramics prepared by two step-sintering through solid-state reaction. Among these ceramics, the one with x = 0.03 shows a giant piezoelectricity with remarkably high piezoelectric coefficient d₃₃ of 550 pC/N at room temperature. Concurrent measurements of ε′ and ε′′ vs. temperature dependences and X-ray diffraction analysis showed that ceramics with x ≤ 0.04 are in rhombohedral-orthorhombic-tetragonal (R-O-T) phase coexistence at room temperature. More intriguingly, the rhombohedral-orthorhombic phase transition temperature, T_R-O, is almost independent of the (Bi_0.50Na_0.50)ZrO₃ content, while orthorhombic-tetragonal phase transition temperature, T _O-T, decreases largely with increasing the (Bi_0.50Na_0.50)ZrO₃ content. Domain configurations of the ceramic with x = 0.03 were investigated by acid-etching. Complicated domain patterns consisting of watermark-shaped domains of long parallel stripes separated by irregularly shaped boundaries are seen before poling. In contrast, relatively simple domain patterns of long parallel stripes with some nanodomains appearing in a part of broad stripes are observed after poling. The obtained excellent piezoelectric properties are ascribed to the R-O-T phase coexistence and the corresponding characteristic domain structure.     

Universal Brønsted-Evans-Polanyi Relations for C–C,C–O,C–N,N–O,N–N,and O–O Dissociation Reactions

Abstract  

It is shown that for all the essential bond forming and bond breaking reactions on metal surfaces, the reactivity of the metal surface correlates linearly with the reaction energy in a single universal relation. Such correlations provide an easy way of establishing trends in reactivity among the different transition metals.     

Microstructure and electrical properties of ZnO–ZrO2–Bi2O3–M3O4 (MCo,Mn) varistors

Phase evolution, microstructure and the electrical properties of ZrO₂-added pyrochlore-free ZnO–Bi₂O₃–M₃O₄ (MCo, Mn) varistors have been studied as functions of ZrO₂ content up to 10 vol% and the sintering temperature between 900 and 1300 °C. Zirconia remained as intergranular second phase particles up to 1100 °C, which retarded densification and inhibited the grain growth of ZnO. At higher temperatures, on the contrary, ZrO₂ particles began to be entrapped in ZnO grains and irreversibly transform from monoclinic to stable cubic phase dissolving transition metal ions. The grain size of ZnO decreased with increasing ZrO₂ content, and increased with the increase of the sintering temperature. Accordingly breakdown voltage changed with both ZrO₂ content and the sintering temperature as was expected. Nonlinear coefficient (α) depended primarily on the sintering temperature: it increased to >40 up to 1000 °C, and significantly decreased to <30 at higher temperatures probably due to the volatilization of Bi₂O₃. While the specimens sintered at 1200 °C or above had relatively high leakage current (I_L) and large clamping ratio (C_R), those with ZrO₂ content of 0.5–5.0 vol% and sintered below 1200 °C revealed low I_L of ⩽20 μA/cm² and C_R well below 2.0. In spite that varistor characteristics of ZrO₂-added system could not match those of commercial ZnO varistors, its low temperature sinterability and ease of breakdown voltage control via ZrO₂ content without a serious loss of its figures of merit are worth noticing, particularly for multi-layered chip varistor (MLV) application.     

Electrochemical properties of Pb–Sb, Pb–Ca–Sn and Pb–Co3O4 anodes in copper electrowinning

Three types of anode, Pb–Sb, Pb–Ca–Sn and Pb–Co₃O₄, for copper electrowinning were investigated. The corrosion resistance, as evaluated by cyclic voltammetric (CV) measurements was higher for Pb–Co₃O₄ than for Pb–Sb and Pb–Ca–Sn. During prolonged electrowinning under galvanostatic conditions, the anodic reaction on the Pb–Co₃O₄ anode was depolarized by 0.053 V as compared to Pb–Sb, and by 0.106 V with respect to Pb–Ca–Sn. The composition and structure of the anodic layer were determined by XPS, X-ray and SEM analyses. The surface layer on the three anodes examined was composed mainly of PbSO₄, -PbO₂ and -PbO₂. Different structure of the surface layer was observed: loose and highly spread coral-like structure in the case of Pb–Sb; fibrous structure in the case of Pb–Ca–Sn and dense, fine-grained structure in the case of Pb–Co₃O₄.     

Energy storage performance of BiFeO3–SrTiO3–BaTiO3 relaxor ferroelectric ceramics

Dielectric capacitors reveal great potential in the application of high power and/or pulsed power electronic devices owing to their ultrafast charge–discharge rate and ultrahigh power density. Among various dielectric capacitors, the environment-friendly lead-free dielectric ceramics have drawn extensive investigations in recent years. Nevertheless, the relatively small recoverable energy storage density (W_rec) is still an obstacle for their application. Herein, the (0.55−x)BiFeO₃–0.45SrTiO₃–xBaTiO₃ ternary ceramics with 0.1 wt% MnO₂ were prepared by the solid-state reaction, and achieved enhanced relaxor behavior as well as breakdown strength E_b. As a result, the x = 0.12 ceramic exhibited superior comprehensive energy storage performance of large E_b (50.4 kV/mm), ultrahigh W_rec (7.3 J/cm³), high efficiency η (86.3%), relatively fast charge–discharge speed (t_0.9 = 6.1 μs) and outstanding reliability under different frequency, fatigue, and temperature, indicating that the BiFeO₃-based relaxor ferroelectric ceramics are prospective alternatives for electrostatic energy storage.     

Synthesis,structure and dielectric properties of (1−x)[0.9BiFeO3–0.1DyFeO3]–xPbTiO3 pseudo-binary ceramics

In order to develop multiferroics with large magnetization and polarization, we have prepared a series of (1?x)[0.9BiFeO₃–0.1DyFeO₃]–xPbTiO₃ [BDF–xPT] solid solution ceramics by solid state reaction. X-ray diffraction reveals that, with the increase of PbTiO₃ concentration, the solid solution transforms from a rhombohedral to a tetragonal phase with the presence of a morphotropic phase boundary (MPB) region located at 0.28≤x≤0.40 at room temperature, in which the rhombohedral, tetragonal and orthorhombic phases coexist. The temperature dependence of the dielectric permittivity indicates that the Curie temperature decreases with the increasing amount of PbTiO₃. Based upon the structural analysis and dielectric characterization, a preliminary phase diagram for the BDF?xPT pseudo-binary system has been proposed. It is found that the ceramics of compositions around the MPB exhibits much better dielectric properties with dielectric constant of the BDF–0.37PT ceramics reaching 459 at 1 kHz, confirming the beneficial effects of the MPB on the dielectric performance.     

Phase compositions and equilibria in the CaO–Al2O3–Fe2O3–SO3 system,for assemblages containing ye'elimite and ferrite Ca2(Al,Fe)O5

Phase equilibria in the CaO–Al₂O₃–Fe₂O₃–SO₃ system have been studied, mainly at 1325 °C. In particular the solid solution compositions of ye'elimite Ca₄(Al₆O₁₂)SO₄ and brownmillerite (C₂(A,F)) phases have been analysed and used to estimate the composition boundaries of these phases in their co-existence with liquid at 1325 °C. Sulfate and iron oxide facilitate the formation of a liquid phase, whose amount increases with overall Fe₂O₃ content. However, the solubility of sulfate in this liquid phase is very low and liquid formation tends to lead to the volatilisation of sulfate in unsealed samples.     

CaO–Al–Al_2O_3–CaCO_3–O_2体系燃烧合成铝酸钙热力学研究

计算了CaO–Al–Al_2O_3–CaCO_3–O_2体系燃烧合成铝酸钙的绝热温度,运用物质自由能函数理论,对主要反应进行了热力学计算,分析了燃烧合成铝酸钙的物相生成过程。结果表明:体系绝热温度随产物中CA_2含量的增加而降低,但均大于1800K,说明反应可自持;在反应初期,C_(12)A7的生成驱动力最大,其次是CA、CA_2的生成驱动力,C_(12)A_7为主要生成物相;随着反应的进行,铝酸钙不同物相间会发生转化,C_(12)A_7转化CA_2的驱动力最大,其次是C_(12)A_7转化为CA;C_(12)A_7和CA2共同转化成CA的驱动力最小,因此形成以CA、CA_2为主要物相的产物,且CA的含量大于CA_2的含量。燃波前端C_(12)A_7特征峰强度最大;反应区C_(12)A_7的特征峰强度减小,而CA、CA_2的特征峰强度增加;产物区C_(12)A_7特征峰强度消失,且CA的特征峰强度大于CA2的特征峰强度,表明产物中CA的含量大于CA2的,与热力学分析结果一致。在反应区有片状CA和颗粒状CA_2生成;在产物区CA_2弥散在CA中。     

Bimetallic Au–Cu, Ag–Cu/CrAl3O6 Catalysts for Methanol Synthesis

The influence of silver and gold addition on the activity and physicochemical properties of supported Cu/CrAl₃O₆ catalysts was the aim of this work. The reduction of CrAl₃O₆ support shows only one reduction stage attributed to Cr (VI) species reduction originating from previously oxidized binary oxide. Supported copper catalysts reduce in one or two stages depending on copper concentration representing the reduction of copper oxide—CuO, copper oxide chemically combined with Cr(III) oxide as copper chromite—CuCr₂O₄ and Cr(VI) species originating from surface chromate ions CrO₄ ^2?. Additionally, the introduction of silver into supported copper catalysts Cu/CrAl₃O₆ can led to the appearance of silver chromate phase. XRD investigations of support CrAl₃O₆ alone, supported copper and gold and silver promoted copper supported catalysts calcined at 400, 700 and 900 °C indicated the presence of highly amorphous alumina γ-Al₂O₃ like structure network in which some of cationic locations of aluminum were occupied by chromium atoms and small quantities of α-Cr₂O₃ phase. Additionally, for copper, silver–copper, and gold–copper supported catalysts the following oxide phases were distinguished: monometallic oxides CuO, Ag₂O, binary oxides CuAl₂O₄, Ag₂CrO₄, CuCr₂O₄ and even ternary oxide CuAlCrO₄. In the case of gold promoted copper supported catalysts metallic gold phase was detected. Activity tests carried out for these catalysts show that the most active was 20 wt.% Cu/CrAl₃O₆ catalyst. Promotion of copper catalysts by silver improves the activity in methanol synthesis, what can be assigned to silver chromate formation. The analogical gold chromate like formation was not confirmed.     

New catalytic functions of Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys in the conversions of methanol

Pd and Pt supported on ZnO, Ga₂O₃ and In₂O₃ exhibit high catalytic performance for the steam reforming of methanol, CH₃OH+H₂OCO₂+3HH₂, and the dehydrogenation of methanol to HCOOCH₃, 2CH₃OHHCOOCH₃+2HH₂. Combined results with temperature-programmed reduction (TPR) and XRD method revealed that Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys were produced upon reduction. Over the catalysts having the alloy phase, the reactions proceeded selectively, whereas the catalysts having metallic phase exhibited poor selectivities.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

High-temperature BiFeO3–PbTiO3-Ba(Zr,Ti)O3 ternary ceramics with excellent piezoelectricity

Ternary ceramics of (0.87−x)BiFeO₃–xPbTiO₃–0.13Ba(Zr_0.5Ti_0.5)O₃ (BF–xPT–0.13BZT, 0.27 ≤ x ≤ 0.37) were prepared by the traditional solid state reaction methods. X-ray diffraction results display that BF-xPT-0.13BZT ternary ceramics of x ≥ 0.29 exhibit the perovskite structure with dominant tetragonal (T) phases mixed with a small amount of rhombohedral (R) phases. Scanning electron microscopy (SEM) images reveal that the average grain size of BF-xPT-0.13BZT ternary ceramics is in a range of 10–11 μm, increasing first and then decreasing with the increase of PbTiO₃ (PT) content. The low tanδ of about 0.015 and high Curie temperature T_c of above 450°C were obtained for BF-xPT-0.13BZT ternary ceramics. Moreover, the fluctuation of piezoelectric coefficient d₃₃ is less than ±10% over a broad temperature range of 30°C–400°C. BF-xPT-0.13BZT ternary ceramics for x = 0.33 possess the maximum T_c and d₃₃ of 470°C and 320 pC/N respectively, with the room temperature resistivity of about 10¹¹ Ω·cm. These results indicate that BF-xPT-0.13BZT ternary ceramics for x = 0.33 with both excellent piezoelectric properties and high Curie temperature have promising applications in high-temperature piezoelectric devices.     

Fabrication,tunable fluorescence emission and energy transfer of Tm3+-Dy3+ co-activated P2O5–B2O3–SrO–K2O glasses

A growing demand for white light-emitting diodes (W-LEDs) gives rise to continuous exploration of functional fluorescence glasses. In this paper, Tm³⁺/Dy³⁺ single- and co-doped glasses with composition (in mol%) of 30P₂O₅–10B₂O₃–23SrO–37K₂O were synthesized using the melt-quenching method in air. The physical properties, glass structure, luminescence characteristics and energy transfer mechanism of the glasses were systematically studied. As glass network modifiers, Tm³⁺ and Dy³⁺ ions can densify the glass structure. Excitation wavelength and doping concentration of Tm³⁺/Dy³⁺ ions have a direct impact on the emission intensities of blue and orange light as well as the color coordinate of the as-prepared glasses. A white light very close to standard white light can be obtained under 354 nm excitation when the content of Tm³⁺ and Dy³⁺ is 0.2 mol% and 1.0 mol%, respectively. The results of the emission spectra and decay curves reveal the existence of energy transfer from Tm³⁺ to Dy³⁺. The analytic results based on the Inokuti-Hirayama model indicate that the electrical dipole-dipole interaction may be the main mechanism of energy transfer. Moreover, Tm³⁺/Dy³⁺ co-activated glass phosphor has good thermal stability and chrominance stability and it is a promising candidate for white LEDs and display device.     

H3BO3–NaCl–MgCl2–H2O体系相平衡及工艺分析

测定了25, 100℃下H3BO3–NaCl–MgCl2–H2O体系的溶解度数据，并依据绘制的相图对我国西藏含钠镁的硼矿资源采用盐酸分解法制备硼酸的生产工艺进行了讨论.     

1–(3–硝基–2–吡啶)–1H–苯并三唑的合成与表征

以苯并三氮唑和2–氯–3–硝基–吡啶为原料,合成出1–(3–硝基–2–吡啶)–1H–苯并三唑。采用元素分析、核磁共振光谱等手段鉴定了目标产物结构,并用DSC测定了产物的熔点。考察了反应溶剂、溶剂用量、缚酸剂种类、缚酸剂用量对该反应收率和产品纯度的影响。确定的最佳工艺条件为:以工业乙醇为反应溶剂,溶剂与反应物的原料比为200 mL∶0.1 mol,Na2CO3为反应缚酸剂,缚酸剂与苯并三氮唑的摩尔比为1∶1,反应时间为12 h。     

Optical properties of novel oxyfluoride glasses on the systems of LaF3–LaO3/2–NbO5/2 and LaF3–LaO3/2–NbO5/2–AlO3/2

Oxyfluoride glasses of xLaF₃–(60 − x)LaO_3/2–40NbO_5/2 (x = 0, 5, 10, 35) and xLaF₃–(60 − x)LaO_3/2–30NbO_5/2–10AlO_3/2 (x = 0, 10, 20, 30) were prepared using a levitation technique. Both the glass-transition temperature, T_g, and onset crystallization temperature, T_c, were lowered by substituting a part of the oxygen with fluorine in the glasses. An appropriate amount of fluorine maximized the difference between the temperatures, ΔT (= T_c − T_g), indicating the improvement in the glass-forming ability. The atomic packing densities of the glasses were approximately 60%, which gradually increased with the fluorine content. The absorption edge of the glasses shifted toward the shorter wavelength region in the ultraviolet spectra and toward the longer region in the infrared spectra by fluorine substitution. In addition, in one of the oxyfluoride glasses, a wide transparency from 307 nm to 9.2 µm was realized. Furthermore, the glass exhibited superior optical properties, with a combination of a high refractive index, n_d, of 2.020 and low wavelength dispersion, v_d, of 30.1. The effect of fluorine substitution on the n_d and its v_d was analyzed using the Lorentz–Lorenz dispersion formula.     

Liquid-phase sintering of Pb(Zr,Ti)O3 using PbO–WO3 additive

The objective of this work was to lower the sintering temperature of lead zirconate titanate (PZT) without reducing the piezoelectric performance. PZT was sintered using PbO–WO₃ additive of eutectic composition, which assists the densification process by liquid-phase formation. Sintering was carried out from 1075 to 1125 °C between 1 and 4 h. Density, dielectric properties and piezoelectric properties were measured. Microstructure and fracture mechanism have been studied by SEM. At the mildest sintering conditions, the additive has a positive effect on dielectric and piezoelectric properties. The liquid-phase sintering leads to a denser material without additional grain growth. PZT with PbO–WO₃ additive is mechanically weaker than pure PZT. The liquid phase leads to weaker grain boundaries and the material cracks in intergranular fracture, whereas pure PZT has a mixture of intergranular and transgranular fracture, and PZT sintered conventionally at 1260 °C has transgranular fracture.