钛酸锶钡陶瓷材料的掺杂改性

钛酸锶钡(BST)是一种重要的具有钙钛矿结构的铁电材料。顺电态下,其介电损耗较小,结构稳定。因此对顺电态下的BST进行掺杂改性是近年来铁电材料的研究热点之一。本文简要介绍了目前国内外科研工作者利用稀土、碱土氧化物进行掺杂时对BST的微观结构、介电损耗、介电常数以及可调率方面的影响。     

Ag~+掺杂钛酸锶钡基玻璃陶瓷的显微结构和介电性能

采用熔融法制备了钛酸锶钡（barium strontium titanate,BST）基玻璃,然后将此玻璃样品在不同的温度下进行热处理得到BST基玻璃陶瓷,采用差热分析研究了BST基玻璃陶瓷析晶过程中的热力学特征,用扫描电子显微镜和X射线衍射分别分析了玻璃陶瓷的显微结构和相结构,并且系统研究了该玻璃陶瓷的介电特性以及耐击穿电场强度。结果表明：0.3%（质量分数）Ag＋掺杂时,BST基玻璃中BST相的析晶温度从885℃下降到840℃,有利于玻璃体中BST晶体的析出。另外,Ag＋的掺杂有利于提高BST基玻璃陶瓷的介电常数,同时能维持较低的介电损耗。此外,Ag＋掺杂能够提高BST基玻璃的耐击穿电场强度,其在800℃热处理后,可达96.3 kV/mm,高于未掺杂Ag＋的BST基玻璃的52.5kV/mm。     

二氧化硅掺杂钛酸锶钡陶瓷的介电性能与电卡效应

采用传统的固相反应法制备二氧化硅（SiO₂）掺杂钛酸锶钡（Ba_0.65Sr_0.35TiO₃,BST）陶瓷（BST+x%SiO₂）,研究了掺杂二氧化硅对BST陶瓷的物相、微观形貌、介电性能及电卡效应的影响。结果表明：掺杂二氧化硅并未改变BST陶瓷的晶型结构,但有助于提升晶粒的均匀性和材料介电性能频率的稳定性。随着二氧化硅掺杂量增加,BST陶瓷的介电常数呈现单调递减趋势,介电弥散特性逐渐增强。二氧化硅的掺杂有利于提升BST陶瓷的电卡性能,其中BST+3%SiO₂陶瓷具有最优的电卡效应,在30 ℃下可获得最大电卡绝热温变（ΔT_max）,ΔT_max和ΔT_max/ΔE分别为1.6 ℃、8.00×10 ^-7 ℃·m/V,电卡效应半峰宽（T_span）为10 ℃左右。     

钛酸锶钡铁电陶瓷材料掺杂改性研究进展

综述了最近几年国内外专家对钛酸锶钡(BST)铁电陶瓷材料的掺杂改性方面的研究情况,介绍了不同掺杂物对BST材料性能的影响,简述了BST陶瓷材料的应用趋势。论述了掺杂物掺杂改性材料的组成、结构和性能之间的关系,提出了研究中需要解决的一些问题,展望了钛酸锶钡电介质材料掺杂改性的发展方向。     

掺杂氧化铌对钛酸锶钡铁电陶瓷材料显微结构和介电性能的影响

钛酸锶钡(barium strontium titanate,BST)铁电陶瓷材料的介电常数(ε)随外加直流电场的变化呈现非线性特性.纯BST材料由于较高的ε和较大的介电损耗(tanδ)不能满足移相器介质材料的要求.通过在BST中添加氧化铌(Nb2O5)来改善BST铁电陶瓷材料的介电性能.结果表明:在BST体系中微量掺杂Nb2O5,Nb5 以取代Ti4 的方式存在于钙钛矿的晶格中,形成均匀的固溶体Ba0.5Sr0.5Ti1-xNbxO3.随Nb5 添加量的增加,Curie峰逐渐变宽,峰高逐渐降低,相变弥散效应增强.Nb5 的掺杂能显著降低并稳定BST陶瓷的tanδ,改善BST体系的介电性能.     

Crystal Structure and Dielectric Properites of Bao.6Sr0.4TiO3/MgO Ceramics Doped with ZrO2 and MnO2

通过固相反应法制备Mn、Zr共掺杂钛酸锶钡／氧化镁陶瓷粉体,经干压成型后在空气气氛中于l450℃烧结4h,通过扫描电子显微镜和X射线衍射研究了ZrO2和MnO2共掺杂的Bao6Sro4TiO3／MgO复合陶瓷材料的微结构和介电性能。结果表明：Zr02可以显著降低材料的介电常数和介电损耗,有效提高了陶瓷材料的温度稳定性;随ZrO2添加量的增加,体系的晶胞参数略有增加,MgO在钛酸锶钡中以独立相的形式存在：制备出的BST铁电陶瓷材料的25℃相对介电常数较低（＆〈110）,介质损耗小于1．0×10^-3（在频率为10kHz时）,温度系数小于6．012×10^-3,可调性大于20％（8．0kV／mm）,适用于制作移相器。     

微量Ce3+、Nb5+、Zn2+对钛酸锶钡基陶瓷介电性能的影响

通过研究Ce³⁺、Nb⁵⁺、Zn²⁺对钛酸锶钡基陶瓷介电性能的影响,结果发现Ce³⁺、Nb⁵⁺、Zn²⁺各离子单一掺杂提高其介电性能是有限的,而充分运用各微量离子作用机理,控制钛酸锶钡的Ce³⁺、Nb⁵⁺、Zn²⁺引入量,能综合提高钛酸锶钡基陶瓷的介电性能。     

改性钛酸锶/PVDF复合材料介电性能研究

采用具有强络合能力的酒石酸在碱性溶液中对SrTiO3陶瓷颗粒进行表面改性,将改性后的SrTiO3颗粒与聚偏二氟乙烯(PVDF)经热压共混成型,制备出系列陶瓷/聚合物基复合材料,对改性SrTiO3/PVDF复合材料进行了介电性能分析。结果表明:添加了改性SrTiO3的复合材料比未改性SrTiO3复合材料的介电常数增加值达34%以上,同时,改性复合材料的介电损耗仍保持较低水平;随着改性SrTiO3在复合材料中含量的增加,介电常数也随之增加,介电损耗仍保持不变,改性后的陶瓷/聚合物复合材料表现出优异的综合介电性能。     

B2O3-Li2O掺杂低温烧结Ba0.6Sr0.4TiO3陶瓷的介电性能

采用传统陶瓷制备工艺,通过B2O3-Li2O的有效掺杂,低温液相烧结制备了Ba0.6Sr0.4TiO3(BST)陶瓷,并对其介电性能进行了研究.X射线衍射分析和介电性能测试结果表明:适量B2O3-Li2O掺杂的BST陶瓷,经97S℃烧结4h,所得样品的主晶相为钙钛矿结构,未出现明显的杂相;随B2O3-Li2O掺杂量的增加,BST陶瓷材料的介电常数减小,Curie峰变得弥散宽化,介电损耗则与未掺杂BST陶瓷的保持一致,即在0.003以下:适量B2O3-Li2O的掺杂对BST陶瓷材料的Curie温度和介电调制性能影响不大.     

Microstructure and dielectric properties of Ba0.6Sr0.4TiO3-MgAl2O4 composite ceramics

(1 − x)Ba_0.6Sr_0.4TiO₃-xMgAl₂O₄(x = 25, 30, 35 and 40 wt%) composite ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and tunability of the composites have been investigated. The XRD patterns analysis reveals two crystalline phases, a cubic perovskite structure Ba_0.6Sr_0.4TiO₃ (BST) and a spinel structure MgAl₂O₄ (MA). SEM observations show that the BST grains slightly dwindle and agglomerate with increasing amounts of MA. A dielectric peak with very strong frequency dispersion is observed at higher MA content, and the Curie temperature shifts to a higher temperature with increasing MA content. The ceramic sample with 30 wt% MA has the optimized properties: the dielectric constant is 1503, the dielectric loss is 0.003 at 10 kHz and 25 °C, the tunability is 23.63% under a dc electric field of 1.0 kV/mm, which is suitable for ferroelectric phase shifter.     

Effect of MgO Doping on the Phase Transformations of BaTiO3

The successive phase transformations in MgO-doped BaTiO₃ were studied. Upon MgO doping, dielectric anomalies corresponding to lower phase transformations were broadened and depressed, while an anomaly for a cubic–tetragonal transformation remained and shifted to a lower temperature. XRD peak splitting upon tetragonality of BaTiO₃ was decreased, and the peaks exhibited abnormally broadened profiles which are different from the one for cubic BaTiO₃ above T _c. Raman spectroscopy revealed the existence of orthorhombic phase at room temperature for the solid solution with 0.5 mol% or more MgO. The temperature dependence of the Raman spectrum showed that orthorhombic and rhombohedral phases in MgO-doped BaTiO₃ were stabilized at higher temperatures than pure BaTiO₃.     

Roles of Ba/Ti Ratios in the Dielectric Properties of BaTiO3 Ceramics

The effect of the Ba/Ti ratio on microstructure, dielectric/ferroelectric properties, and domain width was studied using optical microscopy, ɛ( T ) curves, D – E hysteresis, and transmission electron microscopy. Although Ti-excess samples showed abnormal grain growth and a decrease of room-temperature permittivity due to a liquid phase at grain boundaries, its ferroelectric properties were similar to those of stoichiometric BaTiO₃ ceramics. However, in Ba-excess samples, an increase of permittivity and ferroelectric properties different from those of stoichiometry were found. Changes in domain width and ferroelectric transition behavior indicated that the variation of dielectric properties was related to the internal stress. It is proposed that this internal stress originated from differences in the thermal expansion coefficient between the matrix and the second phase.     

热处理对 Ba0.6Sr0.4TiO3 厚膜介电性能的影响

采用柠檬酸盐法制备了Ba_(0.6)Sr_(0.4)TiO_3粉体,通过丝网印刷法制备了Ba_(0.6)Sr_(0.4)TiO_3厚膜,研究了在空气气氛中进行热处理前后厚膜样品的介电性能。研究结果表明,在空气气氛中进行热处理可以有效地提高厚膜样品的介电性能。经过1000°C热处理,厚膜样品在10 kH z下的介电损耗由1.7%降为1.1%,其优质系数由33提高到55。     

Electrical Properties of Sr0.7Ba0.3TiO3 Ceramics Doped with Nb2O5, 3Li2O · 2SiO2, and Bi2O3

The electrical properties of Sr_0.5Ba_0.3TiO₃ in the presence of Nb₂O₅ as a donor, 3Li₂O · 2SiO₂ as a sintering agent, and Bi₂O₃ as a dopant have been studied. When the compositions of the ceramics were 1 mol Sr_0.7Ba_0.3TiO₃+ 0.5 mol% Nb₂O₅+ 2 mol% 3Li₂O · 2SiO₂+ 0.2 mol% Bi₂O₃, the ceramics were sintered at 1100°C and exhibited the following characteristics: apparent dielectric constant ɛ, 25000; loss factor tan δ, 2%; insulating resistivity ρ_j, 10¹⁰Ω· cm; variation of dielectric constant with temperature Δɛ/ɛ (−25° to +85°C), +10%, −14%. ɛ and tan δ show only small changes with frequency. The study shows this ceramic can be used in multilayer technology.     

MgSiO_3掺杂Ba_（0.4）Sr_（0.6）TiO_3陶瓷的介电调谐特性及微波性能（英文）

MgSiO3掺杂 Ba0.4Sr0.6TiO3陶瓷具有 Ba1-xSrxTiO3、（Ba,Sr）2TiSi2O8、Ba4MgTi11O27和 Mg2TiO4多相结构。MgSiO3低掺量（质量分数≤10%）陶瓷样品具有条形晶粒和细晶粒组成的微结构;随着 MgSiO3掺量增加,陶瓷样品形成晶粒细小、均匀的微结构;当 MgS...     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Influence of Stress and Chemical Homogeneity on Dielectric Properties of BaTi0.9Zr0.1O3

The influence of mechanical stress and chemical homogeneity on the permittivity of BaTi_0.9Zr_0.1O₃ ceramics prepared from mixed-oxide and hydrothermal powders was studied. To reduce stress, liquid-phase sintering was applied in conjunction with a low heating rate to stimulate the formation of large grains. The influence of chemical homogeneity was studied by variations in sintering temperatures and times. For both types of ceramics, the dielectric constant at the Curie temperature was influenced by both factors, but to a different extent. In the mixed oxide ceramic, chemical homogeneity played a more prominent role, while internal stress appeared to exert a larger influence in the hydrothermal ceramics. The dielectric constant at the Curie temperature could be increased by 5%–10% by an annealing treatment at 200°C, followed by slow cooling.     

PbO-SiO2玻璃对Ba0.4Sr0.6TiO3陶瓷致密度和介电性能的影响

为了制备耐高压、高储能密度陶瓷电容器,研究了不同PbO-SiO2(PS)玻璃添加量对Ba0.4Sr0.6TiO3陶瓷致密度和介电性能的影响。结果表明:PS玻璃能有效降低Ba0.4Sr0.6TiO3陶瓷的烧结温度,细化晶粒,提高样品的致密度。添加适量PS玻璃改善了Ba0.4Sr0.6TiO3陶瓷的介电性能。添加质量分数为1%PS玻璃的Ba0.4Sr0.6TiO3陶瓷在1100℃烧结致密,相对密度达到98.3%,平均击穿场强达到15.4kV/mm,相对于纯Ba0.4Sr0.6TiO3陶瓷的提高了1.5倍,1kHz的室温相对介电常数达到1179,介电损耗为6×10-4。