Phase transition and piezoelectric properties of lead-free (Bi1/2Na1/2)TiO3–BaTiO3 ceramics

(1−x)(Bi_0.5Na_0.5)TiO₃–xBaTiO₃ ceramics (x=0.03, 0.06, 0.08, 0.12, 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, and 0.90) were fabricated by a conventional solid-state reaction and their phase transitions and piezoelectric properties were investigated using XRD analyses, Curie temperature, the frequency dependance of dielectric constant, and P–E curves. A complete solid solution with a perovskite structure was formed in the whole composition range of BNT–BT and more than two phase transitions arising from a compositional change were found. With increasing BaTiO₃ content, the sequence of phase transitions from a rhombohedral structure to unknown tetragonal structures and finally a tetragonal structure with the space group P4mm has been established. While the rhombohedral–tetragonal phase transition led to superior piezoelectric properties in BNT–BT ceramics, other phase transitions between tetragonal structures had a little effect on piezoelectric properties. The d₃₃, ε_r, k_p, k_t, and Q_m and values lied in ranges of 40–130 pC/N, 400–900, 10–30%, 15–30%, and 50–250, respectively.     

Bi(Zn1/2Ti1/2)O3 modified BiFeO3–BaTiO3 lead-free piezoelectric ceramics with high temperature stability

Lead-free high-temperature ceramics with compositions of 0.71BiFe_1−x(Zn_1/2Ti_1/2)_xO₃–0.29BaTiO₃ (BFZTx–BT, x=0–0.05 mol fraction) were fabricated by a conventional solid state reaction method. The effect of Bi(Zn_1/2Ti_1/2)O₃ (BZT) addition on the microstructure, electrical properties, relaxor behavior, and temperature stability has been studied. XRD patterns revealed that all compositions formed a single perovskite phase of pseudo-cubic crystal structure. The grain size was slightly affected by BZT addition. The diffuse phase transition and strong frequency dispersion of dielectric permittivity are observed for BZT modified ceramics. The addition of BZT into BFZTx–BT was also found to affect the piezoelectric properties and temperature stability of the ceramics with maximum values observed for x=0.5% and 1% BFZTx–BT compositions, respectively. The optimum piezoelectric properties with d₃₃=163 pC/N, together with high-temperature stability with a depolarization temperature T_d∼380 °C, reveal the BFZTx–BT ceramics to be promising high-temperature Pb-free piezoelectric materials.     

Stress-dependent ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramic systems

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN systems were investigated. (1 − x)Pb(Zr_1/2Ti_1/2)O₃(xPb(Zn_1/3Nb_2/3)O₃ or (1 − x)PZT–(x)PZN (x = 0.1–0.5) ceramics were prepared by a conventional mixed-oxide method. The ferroelectric properties under compressive stress of the PZT–PZN ceramics were observed at stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remanent polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelectric domain switching processes.     

Composite wasteform based on SiO2–PbO–CaO–ZrO2–TiO2–(B2O3–K2O) parent glass with zircon as the second component

Many different types of glass and ceramic wasteforms have been investigated for nuclear waste immobilization. This study deals with synthesizing composite wasteforms based on a parent glass belonging to the SiO₂–PbO–CaO–ZrO₂–TiO₂–(B₂O₃–K₂O) system with the use of zircon as a second component. The fabrication involves powder mixing, pressing and pressureless sintering. The processing conditions were investigated so as to achieve the highest density and the best sintering temperature for different amounts of zircon, i.e. 5, 10 and 15 wt%. The sintered products were studied by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM); as well as ICP-MAS for leaching experiments. The most promising composite containing zirkelite and titanite crystals in a lead-rich glassy matrix was obtained at 700 °C for 10 wt% zircon.     

Piezoelectric and dielectric properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Ba(Zr0.04Ti0.96)O3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–xBa(Zr_0.04Ti_0.96)O₃ (abbreviated as BNBT–BZT100x, wherein x from 0 to 10 mol%) were fabricated. We have studied effects of amount of BZT content on the electrical properties and microstructures. X-ray diffraction analysis indicates that a solid solution is formed when BZT diffuses into the BNBT lattice, and further the crystal structure of sintered hybrid changes from rhombohedral to tetragonal symmetry along with increasing BZT content. Piezoelectric property measurements reveal that the BNBT–BZT4 ceramics has the highest piezoelectric performance, for example, the piezoelectric constant d₃₃ reaches to 167 pC/N and planar electromechanical coupling factor k_p is up to 0.27. In addition, the effect of Bi₂O₃ on the electrical properties and microstructure of the BNBT–BZT4 ceramics have also been studied, and found that the doping of Bi enhances the piezoelectric properties of ceramics.     

Bi2O3对K2O–B2O3–SrO–Al2O3–Nb2O5–SiO2玻璃陶瓷介电储能性能的影响

随着电力电子系统的不断发展,高功率脉冲电容器的需求增多。电介质电容器因具有放电功率大、充放电速度快及性能稳定等优点,在电力系统、电子器件、脉冲电源等方面发挥着重要作用,广泛应用于民用领域及军事领域。通过熔融压延制备玻璃基体,采用可控结晶工艺研究了不同含量的Bi₂O₃ (x=0.0%、1.0%、2.0%、4.0%,摩尔分数)对K₂O–B₂O₃–Sr O–Al₂O₃–Nb₂O₅–SiO₂玻璃陶瓷物相演化、微观结构、介电和储能性能的影响。在该玻璃陶瓷中,KSr₂Nb₅O₁₅为主要析出晶相,当Bi₂O₃的加入量为x=2.0%(摩尔分数)时,热处理温度为950℃时,玻璃陶瓷样品的储能密度最大可达到1.27 J/cm³,室温下介电常数可达342,是热处...     

Microstructure and electrical properties of (Na0.5K0.5)1−2xMgxNbO3–Bi0.5Na0.5TiO3 lead-free piezoelectric ceramics

0.975[(Na_0.5K_0.5)_1−2xMg_xNbO₃]–0.025(Bi_0.5Na_0.5TiO₃) (KNMN–BNT, x=0, 0.01, 0.02, 0.03, 0.04 and 0.05) lead-free piezoelectric ceramics were fabricated by the conventional solid-state sintering method. The dependence of Mg content on the microstructure and electrical properties of the ceramics is investigated. The X-ray diffraction (XRD) analysis revealed that an appropriate amount of Mg diffused into the KNN–BNT lattice to form a stable solid solution, the ceramics possessed a pure perovskite structure, and a morphotropic phase boundary (MPB) between the orthorhombic and tetragonal phases was observed with the composition of 0.02≤x≤0.05. The orthorhombic–tetragonal transition temperature (T_O–T) is less than 95 °C and the Curie temperature (T_c) is almost unchanged (~360 °C) with the increase of MgO content. The ceramics with x=0.02 showed enhanced piezoelectric and ferroelectric properties because of close proximity to the MPB, i.e., d₃₃~210 pC/N, k_p~0.41, 2E_c~22.4 kV/cm and 2P_r~39.2 μC/cm². Moreover, the dielectric properties exhibited optimal effects with x=0.02, that is ε_r~637 and tan δ~0.09. These results indicate that the introduction of MgO is an effective method to improve the density as well as the electrical properties and the temperature stability of the KNN–BNT ceramics. As a result, the KNMN–BNT ceramic is a promising candidate for lead-free piezoelectric materials.     

Mechanosynthesis of nanocomposites in TiO2–B2O3–Mg–Al quaternary system

The mechanochemical behavior of TiO₂–B₂O₃–Mg–Al quaternary system to synthesize various composite nanopowders was studied. A mixture of boron oxide and titanium dioxide powders along with different amounts of magnesium and aluminum was milled using a high-energy planetary ball mill to persuade necessary conditions for the occurrence of a mechanically induced self-sustaining reaction (MSR). Results showed that the formation of composite nanopowders was influenced strongly by the reducing agents content. In the absence of Al (100 wt% Mg), TiB₂ nanopowder was formed after 34 min of milling. In the presence of x wt% Mg–y wt% Al (x=40 and 70; y=100−x), mechanical activation was completed after 37–40 min which caused the formation of TiB₂–MgFe_0.6Al_1.4O₄ composite nanopowders. In the case of 10 wt% Mg–90 wt% Al, a ternary nanocomposite (TiB₂–MgAl₂O₄–Al₂O₃) was produced after 43 min of milling. Besides, Al₂O₃–TiB₂ nanocomposite was formed after 90 min of milling in the absence of Mg (100 wt% Al). From the SEM images, mechanochemical process reached a steady state after short milling times where the particles have become homogenized in size and shape. The reaction mechanism steps were proposed to clarify the reactions occurring during mechanochemical process.     

n(Bi2O3)/n(SiO2)对Bi2O3-B2O3-SiO2系光伏玻璃背板油墨微观结构和反射率的影响

随着光伏发射极和背面钝化电池双面双玻组件产业的兴起,光伏玻璃背板用光伏油墨的需求量逐年递增。光伏油墨制备成涂层后,其致密程度将直接影响自身的反射率,进而对光伏电池的光电转化效率产生影响。本文通过改变n(Bi₂O₃)/n(SiO₂),探究玻璃熔剂析晶和其对Bi₂O₃-B₂O₃-SiO₂系玻璃熔剂所制备光伏油墨的影响。采用DSC和Raman对玻璃熔剂的特征行为进行了表征,采用XRD、SEM、色度仪对不同光伏油墨涂层的微观结构和反射率进行了研究,并提出了光伏油墨涂层的光反射增强机制。研究表明,n(Bi₂O₃)/n(SiO₂)的升高会使[BiO₃]和[BiO₆]基团含量增多,破坏[SiO₄]玻璃网络的能力增强,玻璃熔剂的转变温度和析晶峰温度逐渐降低,玻璃熔剂的析晶能力逐渐增大。在短时间内烤制...     

(1-x)Li0.05(K0.5Na0.5)0.95NbO3-x(Bi0.5Na0.5)TiO3无铅压电陶瓷的结构与电性能研究

采用固相反应法制备了(1-x)Li0.05(K0.5Na0.5)0.95NbO3-x(Bi0.5Na0.5)TiO3(LKNN-BNT)无铅压电陶瓷,研究了BNT的添加量x(0,0.005,0.01,0.02)对LKNN-BNT陶瓷的结构与电性能影响。X射线衍射(XRD)分析结果表明当x≤0.005时,陶瓷为正交钙钛矿结构,而当x≥0.01时,陶瓷则转变为四方钙钛矿结构,说明该陶瓷的多型相转变(PPT)区域为0.005相似文献   

Temperature-independent and enhanced dielectric properties for two-layer structure capacitors with 0.8Pb(Fe2/3W1/3)O3–0.2PbTiO3–MnO and 0.7Pb(Fe2/3W1/3)O3–0.3PbTiO3–MnO ceramics

This study fabricates capacitors with two-layer structure and different compositions, 0.8Pb(Fe_2/3W_1/3)O₃–0.2PbTiO₃–MnO and 0.7Pb(Fe_2/3W_1/3)O₃–0.3PbTiO₃–MnO, by using the conventional solid state oxide reaction method. By using the temperature compensation effect and adjusting the thickness ratio of the two layers with different compositions, the temperature–dielectric peak is enhanced and smoothed. The dielectric loss, space charge polarization and dc conduction are suppressed at the highest temperature region. Furthermore, the Maxwell–Wagner model is used to fit and explain the dielectric behaviors. This study also provides suggestions and discussion related to the effect of the interfacial region based on the experimental data and fitting results.     

Influence of the synthesis route on sol–gel SiO2–TiO2 (1:1) xerogels and powders

Five different sol–gel routes are used in order to synthesize mixed SiO₂–TiO₂ materials. Simple mixing of the Ti and Si precursors, pre-hydrolyzing of TEOS, modification of the Ti alkoxide with acetic acid, isoamyl alcohol and acetylacetone lead to translucent gels with different time of gelation. Different techniques such as TGA, DTA, XRD and IR spectroscopy are used to characterize each material. IR spectroscopy revealed the presence of Si–O–Ti and Si–O–Si bonds for all the xerogels letting suppose a composite microstructure of the gels. Pre-hydrolyzing of TEOS and modification of Ti alkoxide with isoamyl alcohol are the most appropriate routes to retain the anatase phase up to 1100 °C.     

Bi2O3/Bi2S3二元异质结光催化剂的合成与制备

半导体光催化技术是解决能源危机和环境污染的有效手段。本文采用水热法制备了Bi₂O₃、Bi₂S₃及Bi₂O₃/Bi₂S₃复合物。以SEM、XRD等表征方法对样品进行分析,以染料为目标污染物考察了催化剂的光催化性能,并以染料的pH值和催化剂的用量以及催化剂的配比三个因素进行光催化实验,通过实验可知在催化剂对染料MB降解时,染料溶液p H值为3、催化剂为10 mg时为最优的降解效果,最大降解率可以达到96%,并提出了复合催化剂在光催化反应中的可能机理。     

The influence of In2O3 on electrical characteristics of iron mixed Li2O–PbO–B2O3–SiO2–Bi2O3 multi-component glass system

Glasses of the composition 19Li₂O–20PbO–20B₂O₃–30SiO₂–(10−x) Bi₂O₃–1Fe₂O₃: xIn₂O₃ with six values of x (0 to 5.0) were synthesized. Dielectric properties viz., dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, electric modulus, M(ω) over wide ranges of frequency and temperature and also dielectric break down strength have been studied as a function of In₂O₃ concentration. The temperature dispersion of real part of dielectric constant, ε′(ω) has been analyzed using space charge polarization model. The dielectric loss (and also the electric moduli) variation with frequency and temperature exhibited relaxation effects and these effects were attributed to the divalent iron ion complexes. The ac conductivity exhibited maximal effect, whereas the activation energy for the conductivity demonstrated minimal magnitude at about 1.0 mol% of In₂O₃. The conductivity mechanism is understood due to the polaronic transfer between Fe²⁺ and Fe³⁺ ions. The low temperature ac conductivity mechanism is explained following the quantum mechanical tunneling model. Spectroscopic studies viz., optical absorption and ESR spectra have revealed that the redox ratio (Fe²⁺/Fe³⁺) is maximal when the concentration of In₂O₃ is ~1.0 mol%. The higher values of dielectric parameters observed at 1.0 mol% of In₂O₃ are attributed to the presence of iron ions largely in divalent state and act as modifiers. The analysis of these results together with spectroscopic studies has indicated that when In₂O₃ is present in the glass matrix in higher concentrations (more than 1.0 mol%) iron ions predominantly exist in trivalent state, occupy substitutional positions and make the glass more rigid. Such enhanced rigidity of the network is causing the decrease of dielectric parameters with the concentration of In₂O₃. Finally it is concluded that In₂O₃ mostly participate in the glass network in octahedral positions and make act as reducing agent (for iron ions) in the studied glass matrix when its concentration is ≤1.0 mol%.     

The effect of pre-milling/pre-synthesis process and excess Ba on the microstructure and dielectric/piezoelectric properties of nano-sized 0.94[(Bi0.5Na0.5)TiO3]–0.06[Ba(1+x)TiO3]

Lead-free piezoelectric ceramic specimens of 0.94[(Bi_0.5Na_0.5)TiO₃]–0.06[Ba_(1+x)TiO₃] (where 0 ≤ x ≤ 0.03) (abbreviated as nano-sized BNBT6(x)) compositions containing excess Ba were synthesized by a modified mixed oxide method. In this modified process (Bi_0.5Na_0.5)TiO₃ and Ba_(1+x)TiO₃ were separately prepared by pre-milling the starting powders in high energy mill (HEM) in order to obtain nano-particle size. BNBT6(x) specimens were also prepared by the conventional process to be compared with the former one. The pre-milling of the raw materials lowered the calcination temperatures of (Bi_0.5Na_0.5)TiO₃ and Ba_(1+x)TiO₃ by 110 and 200 °C, respectively, as compared with the conventional process. High energy milling improved the reaction activity and homogeneity of the materials used throughout the process, enhanced the sintering density and grain uniformity, and decreased the grain size. The effects of excess Ba on the characteristic of nano-sized BNBT6(x) specimens were systematically investigated. The piezoelectric and dielectric properties of BNBT6(x) specimens containing various amounts of excess Ba show maximum values of the planar electromechanical coupling factor (k_p) of 38% and the piezoelectric constant (d₃₃) of 198 pC/N with Ba excess amount of 0.02 mol [BNBT6(0.02)]. The d₃₃ then decreases with increasing excess Ba content to 0.03 mol, whereas the relative dielectric permittivity (K^T₃₃) steadily increases with increasing excess Ba and reaches the maximum value of 785 for this composition. Besides, the depolarization temperature (T_d) slightly decreased within the range of x = 0–0.01 mol and then tends to rapidly decrease with the excess Ba of 0.02 mol. In addition to this, the T_d remains unchanged with the higher excess Ba of 0.03 mol. The modified mixing and milling method were considered to be a new and promising process for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties.     

In vitro bioactivity of glass–ceramics of the CaMgSi2O6–CaSiO3–Ca5(PO4)3F–Na2SiO3 system with TiO2 or ZnO additives

Glass–ceramic materials based on diopside [CaMgSi₂O₆]–wollastonite [CaSiO₃]–fluoroapatite [Ca₅(PO₄)₃F]–sodium silicate [Na₂SiO₃] system with TiO₂ or ZnO additives were successfully prepared and examined in vitro, by using a simulated body fluid (SBF) solution, to be suitable for restorative dental and bone implant materials. In vitro bioactivity of the glass–ceramics was examined by using scanning electron microscopy equipped with energy dispersive X-ray detectors (EDAX–SEM) and inductive coupled plasma emission spectroscopy (ICP).     

Emission analysis of CdO–Bi2O3–B2O3 glasses doped with Eu and Tb

This article reports on the emission properties of cadmium bismuth borate (CdBiB) glasses as a function of doping concentrations of Eu³⁺ and Tb³⁺ ions. The functional groups present in the glasses have been identified by analyzing FT-IR spectra. The emission spectra of Eu³⁺ and Tb³⁺:CdBiB glasses have shown reddish green emissions at 616 nm (⁵D₀→⁷F₂) under the excitation at 465 nm and at 547 nm (⁵D₄→⁷F₅) under the excitation at 485 nm, respectively. The Judd–Ofelt (J–O) theory was applied to evaluate the J–O intensity parameters from the absorption and the emission spectra; by using the J–O intensity (Ω_λ) parameters, spontaneous emission transition probability (A), total radiative transition rate (A_T), radiative lifetime (τ_R) and branching ratios (β) of the various emission transitions have been computed for both Eu³⁺ and Tb³⁺:CdBiB glasses. The quenching behavior in the emission intensity with increased concentration of Eu³⁺ and Tb³⁺ was observed, which could be useful for optimizing the compositions toward practical applications.     

TiO2–g-C3N4/BMMS光催化氧化脱硫催化剂

为了提高TiO₂的光催化氧化脱硫(PODS)活性,利用负载和复合的协同作用,将TiO₂与g-C₃N₄复合,并负载于双介孔二氧化硅(BMMS)上,制备了TiO₂–g-C₃N₄/BMMS。以含二苯并噻吩(DBT)的十二烷溶液为模拟油,评价了催化剂的催化性能;优化了反应条件并提出了催化反应机理。结果表明:TiO₂–g-C₃N₄/BMMS具有明显的双介孔结构,TiO₂与g-C₃N₄已实现复合并负载于BMMS上,TiO₂–g-C₃N₄活性组分在载体上分散良好,与单一TiO₂相比对光的吸收能力增强,催化活性有明显提高,优化后的反应条件为,催化剂用量3%(质量分数),O/S摩尔比为10:1,萃取剂与模拟油体积比为1:1,此时脱硫率可达96.6%,且重复使用8次后脱硫率仍保持85%以上,PODS过程中的主要活性中间物种是·O₂^–和h⁺。     

Bi2O3-ZnO-Nb2O3(BZN)系复相陶瓷的相转变

重新讨论了BZN系(α+β)复相陶瓷中α相与β相之间的相转变. 研究表明BZN系α相与β相是有一定固溶范围的三元化合物,α相的固溶范围受温度的影响较大,β相的固溶范围受温度的影响较小. 复相(α+β)的相组成因此受温度的影响,随温度升高,α相的固溶范围变大,对β相的固溶度增加,复相中β相减少,α相增加. 随温度降低,α相的固溶范围变小,对β相的固溶度减小,β相从α相中脱溶,复相中α相减少,β相增加.     

Internal bias field relaxation in poled Mn-doped Pb(Mn1/3Sb2/3)O3–Pb(Zr,Ti)O3 ceramics

The frequency, electric field cycling and temperature dependences of the polarization–electric field (P–E), strain–electric field (S–E) loops in poled Mn-doped 0.05Pb(Mn_1/3Sb_2/3)O₃–0.50PbZrO₃–0.45PbTiO₃ ceramics have been investigated. The P–E and S–E loops are strongly asymmetric corresponding to the presence of an internal bias field E_i after poling and aging, indicating that the domain walls are strongly pinned by preferentially oriented defect dipoles formed by the acceptor dopant ions (Mn²⁺/Mn³⁺) and O²⁻ vacancies. Whereas, the loops exhibit a tendency of changing from asymmetric shapes to normal symmetric ones with increasing electric field amplitude or decreasing frequency. Repeated electric field cycling as well as high temperature results in a similar effect. Meanwhile, the E_i reduces consequently, providing evidence of domain depinning or internal bias field relaxation. It is suggested that the reorientation of the defect dipoles and depinning of domain walls arising from high temperature or electric field cycling are responsible for this extrinsic internal bias field relaxation process.