粒度对纳米掺杂BaTiO3陶瓷结构和性能的影响

制备了纳米掺杂BaTiO3陶瓷,研究了纳米掺杂剂和BaTiO3的粒度对BaTiO3陶瓷的微观结构和介电性能的影响．结果表明,小粒度、高分散的纳米掺杂剂更易对BaTiO3颗粒实现均匀包裹,有效地抑制晶粒生长并形成更多的壳-芯晶粒,大比表面积使更多高活性的表面原子与BaTiO3发生原子输运形成传质,导致晶粒壳／芯比增大,从而提高其介电性能．纳米掺杂陶瓷的平均晶粒尺寸和四方率与BaTiO3粒度几乎成正比．随着BaTiO3粒度的减小,立方晶粒壳增大而四方晶粒芯减小,陶瓷由四方晶相向赝立方晶相转变,居里峰被显著压制,从而改善介电温度特性．同时,晶粒的壳与芯之间失配产生的内应力随之增加,使居里点向高温方向移动．     

The influence of firing profile and additives on the PTCR effect and microstructure of BaTiO3 ceramics

Nonstoichiometric BaTiO₃ PTCR type materials are investigated with various amounts of MnO₂, Sb₂O₃ and MgO dopants. Specimens fired with a nonisothermal rate-controlled sintering profile exhibit a rather fine and uniform microstructure as compared to those processed by conventional sintering techniques. The temperature at which the resistivity anomaly begins is observed to decrease with Sb₂O₃ and MgO contents. The Curie point of BaTiO₃-based ceramics can be altered by addition of Sb₂O₃, and the dielectric peak is maintained by the presence of MgO additive. Magnesium ions act as acceptors in the BaTiO₂ lattice, while antimony ions as donors. The presence of magnesium compensates some of the antimony, hence the doped-BaTiO₃ seminonductive region is pushed to higher contents.     

Effects of BiNbO4 on the microstructure and dielectric properties of BaTiO3-based ceramics

The microstructure and dielectric properties of ternary system BaTiO₃ (BT)–Bi_0.5Na_0.5TiO₃ (BNT)–BiNbO₄ were investigated. In the case of 1 mol% BNT addition, the Curie point (T _c) of BaTiO₃ was increased from 130 to 140 °C. The dielectric constant peak at T _c was markedly depressed with the addition of BiNbO₄, whereas an enhancement in the dielectric constant at lower temperature was observed. The addition of BiNbO₄ improved the temperature dependence of the dielectric constants of BaTiO₃-BNT system ceramics and the temperature coefficient of capacitance curves satisfied the EIA X8R specification with 3–4 mol% BiNbO₄. The dielectric constant peak at T _c was suppressed evidently due to over high-sintering temperature. As the BiNbO₄ content was increased, the Curie point progressively moved to lower temperatures. SEM indicated that fine and homogeneous grains were observed with 1 mol% BiNbO₄ addition. However, secondary phase grains appeared with increasing the BiNbO₄ content, which were identified as Ba₂TiO₄, NaBiTi₂O₆, and BaTiNb₄O₁₃ by XRD. Moreover, the proportion of the secondary phase grains increased as the BiNbO₄ content increased.     

纳米BaTiO3基PTCR瓷粉的制备及其性能

本文以TiCl4为原料,将其水解生成的H2TiO3与化学计量比的Ba(OH)2·8H2O及Ca,Sr,Y,Mn的醋酸盐在室温下混合研磨后,于100℃烘干,再经800℃热处理,得到了一系列掺杂Ba0.85-xYx Sr0.07Ca0.08 MnyTi1-yO3纳米固溶体粉末.经XRD物相分析证明,产品为立方晶系的完全互溶取代固溶体.TEM电镜形貌分析,粒子分布较均匀,基本呈规则球形,粒径大约50 nm.通过制陶实验,研究了材料的PTC效应,当施主Y和受主Mn的掺杂量分别为1mol%和0.04mol%时,得到了室温电阻13Ω左右,升阻比达到106,电阻温度系数α为21.9%/℃的性质优良的PTC陶瓷材料.     

Effects of BaNb2O6 addition on microstructure and dielectric properties of BaTiO3 ceramics

(1 ? x)BaTiO₃–xBaNb₂O₆ [(1 ? x)BT–xBN] ceramics with x = 0, 0.005, 0.008, 0.01, 0.02, 0.03 were prepared by a conventional solid-state reaction route. The effect of BN addition on phase composition, microstructure and dielectric properties of BT-based ceramics were investigated by X-ray diffraction, scanning electron microscope and impedance spectroscopy. The results showed that a systematic structure change from the ferroelectric tetragonal phase to pseudo-cubic phase was observed near x = 0.01 at room temperature. It resulted in a considerable change of density, grain size and dielectric properties of the samples when BN was introduced. Meanwhile, it also lowered the sintering temperature of the ceramics. The dielectric constant peak and the variation rate of capacitance at Curie temperature are markedly depressed and broaden with increasing BN content. Especially, the ceramics with x = 0.008 and x = 0.01 showed good dielectric properties over the measured temperature range. Optimal dielectric properties of ε = 3,851, tanδ = 0.7 % at room temperature and Δε/ε₂₅ ≤ ±6.8 % (?55 to 125 °C) were obtained for the BT-based ceramics doped with 0.8 mol% BN, which was obviously superior to BaTiO₃ and BaNb₂O₆ ceramic, and it met the requirements of EIA X7R specifications.     

Effect of MgO addition on the electrical transport properties of highly Sb-doped BaTiO3 ceramics

BaTiO3 ceramics doped with Sb donors and Mg acceptors have been fabricated. The lattice constant ratio c/a and the Curie point Tc decrease with increasing Sb concentration. The minimum room temperature resistivity min of the codoped BaTiO3 occurs at a composition of 0.9 mole% Sb2O3-1 mole% MgO as compared to the literature reported min at 0.3 mole% antimony for the Sb2O3-doped BaTiO3. The Mg2+ ion acts as an acceptor in the BaTiO3 ceramics, which compensates the donor contribution from Sb3+ and shifts the doped-BaTiO3 semiconducting region to higher antimony content. The calculated donor concentration confirms the compensation effect of Mg acceptors over Sb donors. The temperature dependence of both barrier height and dielectric constant of specimens is discussed. © 1998 Chapman & Hall     

The microstructure developments and electrical properties of calcium-modified barium titanate ceramics

The microstructure and electrical behaviour of calcium-modified BaTiO₃ ceramics of compositions (a) (Ba_1-x Ca _x )TiO₃, (b) Ba(Ti_1-x Ca _x )O_3-x and (c) (Ba_1-x/2Ca _x/2) (Ti_1-x/2Ca _x/2) O3_3-x/2 have been investigated. These characteristics are observed to vary systematically with the cationic ratio, = (Ba + Ca)/Ti, rather than the amount (x-value) and sites that Ca²⁺ ions are supposed to occupy. A large uniform grain microstructure and normal dielectric behaviour are obtained for 1.01 samples (groups I and II), whereas an ultra-fine grain microstructure and diffuse phase transformation (DPT) characteristics are observed for 1.08 samples (groups III). The latter is proposed to be the suppression of tetragonal to cubic transformation due to the formation of second phase. When the sintering atmosphere is changed from air to H₂/N₂ mixture, the electrical resistivity decreases and dielectric loss increases tremendously for = 0.99 samples (groups I), whereas the high electrical resistivity and low dielectric loss characteristics are preserved for 1.01 samples (groups II and III). The mechanism by which the cationic ratio improves the resistance of the materials to a reducing atmosphere is proposed to be the formation of hexagonal BaTiO_3- phase which consumes the oxygen vacancies generated.     

Sr掺杂对WO3陶瓷电学性质及微观结构的影响

利用传统的陶瓷制备工艺制备了Sr掺杂的WO3陶瓷样品,测量了样品的显微结构和电学性质.结果表明,对于Sr掺杂来说,浓度为2 mol%是一个临界点,在这一点处电学性质和微观结构都将发生显著的变化.掺杂浓度为0.2 mol%的样品表现出较高的非线性系数8.7.实验中发现部分样品表现出电学的不稳定性,我们认为这种不稳定性与相共存以及由此导致的极化有关.     

The influence of the distribution of Cu-rich phase on the micromorphology and dielectric properties of BaTiO3 ceramics

Journal of Materials Science: Materials in Electronics - The (1-x)BaTiO3-xCuO ceramics (x?=?0, 0.5, 1.0, 1.5 and 2.0 wt%) were prepared by the traditional solid-state reaction...     

La改性 BaTiO3陶瓷的结构与电性能

采用气相扩渗和液相掺杂两种方法制备了 La改性的 BaTiO3陶瓷,并对其组成、结构、形貌以 及电性能的变化进行了研究. La的液相掺杂可使纯 BaTiO3陶瓷的电阻率从 4.0× 1012Ω· m下降 为 3.0× 106Ω· m; 而 La的气相扩渗使其电阻率下降更为明显, 变为 8.2× 104Ω· m. La掺杂 BaTiO3陶瓷的晶粒电阻随温度的变化,呈现出明显的 NTC效应,而晶界电阻则呈现 PTC效应. La 扩渗 BaTiO3陶瓷的晶粒电阻随温度的变化,呈现出明显的 PTC效应;晶界电阻随着温度的升高急 剧连续降低 ,样品总电阻的 PTC效应已不存在. XRD分析表明, La掺杂的 BaTiO3陶瓷并没有形成 新相,而扩渗的 La元素已经与陶瓷组元发生了复杂反应,生成了 La2C2O2 、 Ba5La4Ti8O27一些新的 化合物,从而导致了导电性的显著变化. SEM分析表明, La扩渗的 BaTiO3陶瓷,因形成新相,从而 使形核数量增多,形成了均匀、细小、弥散的形貌特征.     

The effect of aluminium on the electrical and mechanical properties of BaTiO3 ceramics as a function of sintering temperature

The effect of aluminium additions on the mechanical behaviour of BaTiO₃ positive temperature coefficient of resistance ceramics sintered in air at temperatures ranging between 1220 and 1400° C has been investigated. Tensile strength has been measured indirectly by the diametral compression of lapped discs using concave loading anvils. Values of ∼ 85 and ∼ 110 MPa for samples fired near their optimum sintering temperature were determined for two batches of material, the latter of which contained additions of Al₂O₃ (0.55 mol%). Strength did not vary systematically with grain size and appeared to be controlled by near surface defects. The size of these cavities, which were generally crescent shaped, was consistent with the material having a bulk fracture toughness of ∼1.3 MPam^1/2. The higher mechanical strength of samples which contained Al₂O₃ additions was attributed to the enhanced “healing up” of these cavities by the liquid phase giving a smaller inherent critical defect size rather than by increasing the bulk toughness of the ceramic.     

Effect of sintering atmospheres on the microstructure and dielectric properties of Yb/Mg co-doped BaTiO3 ceramics

The effect of Yb/Mg co-doping on the microstructure and electrical properties of BaTiO₃ ceramics sintered under oxidizing, reducing and annealed conditions was investigated. XRD analyses indicated the suppression of the solubilities of the acceptor ions in BaTiO₃ under the reducing and annealed conditions_. DSC measurements indicated that addition of too much Yb would cause the collapse of the core-shell structure in the BaTiO₃ ceramics. The effect of sintering atmospheres on the microstructure and dielectric properties was attributed to the change of the solubilities of the acceptor ions in this core-shell-structured material.     

Effect of sintering temperature on microstructure and electrical properties of ZVMCDN ceramics

The microstructure and electrical properties of ZnO-V₂O₅-MnO₂-Co₃O₄-Dy₂O₃-Nb₂O₅ (ZVMCDN) ceramics were investigated in accordance with sintering temperature (850-950 °C). The microstructure of the samples consisted of mainly ZnO grain as a main phase, and Zn₃(VO₄)₂, ZnV₂O₄, and DyVO₄ as the minor secondary phases. The sintered density decreased from 5.69 to 5.52 g/cm³ due to the volatility of V₂O₅ in accordance with increasing sintering temperature. The maximum nonlinear coefficient (57) was obtained at 925 °C. The donor concentration increased from 1.15 × 10¹⁸/cm³ to 11.1 × 10¹⁸/cm³ in accordance with increasing sintering temperature and the barrier height exhibited the maximum value (1.03 eV) at 925 °C.     

Effect of Sm2O3 dopant on microstructure and electrical properties of ZnO-based varistor ceramics

ZnO-based varistor ceramics doped with fixed Y₂O₃ and different Sm₂O₃ have been prepared by the conventional solid-state reaction route, and the phase composition, microstructure and electrical properties have been investigated by XRD, SEM and a V–I source/measure unit. The XRD analyses show the presence of primary phase ZnO and some minor secondary phases. Doping appropriate contents of Sm₂O₃ decrease the leakage current and enhance nonlinearity characteristics of ZnO-based varistor ceramics markedly. The varistor ceramics with 0.25 mol% Sm₂O₃ sintered at 1,125 °C for 1 h exhibit reasonable electrical properties with the breakdown field of 446.4 V/mm, the nonlinear coefficient of 65.8 and the leakage current of 2.36 μA/cm². The results illustrate that doping Y₂O₃ and Sm₂O₃ may be a promising route for the production of ZnO-based varistor ceramics with good electrical properties.     

Influence of sintering atmosphere on the microstructure and electrical properties of BaTiO3-based X8R materials

The effect of sintering atmosphere on the microstructure and capacity-temperature characteristics (TCC) of Yb-Mg and Yb-Mn substituted BaTiO₃ was investigated. The XRD and SEM results indicated the suppression of the solubilities of the acceptor ions when firing under reducing conditions. Mn was confirmed to promote the grain growth of Yb₂Ti₂O₇ while Mg could suppress the grain growth of this second phase. The X8R specification (−55 to 150°C, ΔC/C=±15% or less) could be satisfied by firing under proper conditions for the two compositions. It is suggested that the change of the solubilities of the acceptor ions, as well as the valence states of the Mn ions would affect the TCC behavior of the core-shell-structured BaTiO₃ materials.