掺镧钛酸钡陶瓷晶界的再氧化

掺La的BaTiO3陶瓷在H2和Ar（体积比1：99）的还原气氛下烧结后,在氧分压p（CO2）-260Pa的气氛（Ar和O2的混合气体）下进行氧化,测量了吸氧量不同时的复阻抗图谱,研究了再氧化过程中晶粒和晶界的吸附氧对电阻率的影响。结果表明：在还原气氛下烧结可以扩展有效施主掺杂浓度的范围,通过晶粒的异常生长．制备出高施主掺杂量（10％,摩尔分数）的半导性BaTiO3陶瓷。再氧化过程中,随氧化温度的升高（1017～1380℃）,晶界吸附氧的量增大,晶界处的晶界势垒包括两部分：外部晶界吸收氧原子充当表面受主态;内部晶界在氧化过程中被氧化形成正离子空位（Ti空位）充当受主态．从而提高了受主态密度,导致样品的正温度系数电阻效应增强。     

BaTiO3基PTCR中晶界氧元素的作用分析

采用柠檬酸盐溶胶-凝胶法制备出复合掺杂的BaTiO3粉体,然后成型烧结制备了PTCR试片.首先通过氩气气氛热处理试验,验证了氧能够有效地提高PTC效应,进而利用透射电镜对典型试片的晶界区和晶粒内部的元素成分进行能谱定量分析,表明晶界区的氧含量明显高于晶粒内部,甚至超过了施、受主含量的总和.分析了氧对晶界势垒的影响,用晶界层状氧吸附模型进行了解释.     

涂覆扩散型SrTiO3基陶瓷晶界叠加势垒模型

根据涂覆扩散型ＳｒＴｉＯ３基陶瓷的晶界结构特点，势扩散分布与压敏电压的关系，提出了两晶粒之间的ｎ－ｎ‘－ｉ－ｎ’－ｎ的物理模型以及晶界叠加势垒模型。以此模型推导晶势垒高度与扩散层深度的公式，对实验数据，晶界势垒高度及其在晶界的分布进行了模拟，其结果明确地说明了摭用层浓度增加，晶界势垒高度提高从而ＶｌｍＡ提高、并证明了叠加势垒模型比Ｓｃｈｏｔｔｋｙ势垒模型更加合理。     

SrTiO3复合功能陶瓷的AC阻抗谱研究

本文采用一次烧成法制备出SrTiO3电容-压敏复合功能陶瓷,测试了样品的交流阻抗谱,确定了样品的等效电路,分析了不同氧化热处理条件下的晶粒和晶界电学特性.结果表明,SrTiO3复合功能陶瓷晶界存在多种受主态形态,氧化热处理过程中晶粒保持其半导体特性,晶界绝缘程度显著提高.     

n—型SrTiO_3半导瓷的压敏特性

采用一次烧成法研制成了具有压敏特性的n—型SrTiO_3晶界层电容器。n—型SrTiO_3半导瓷的压敏特性起因于氧化保温阶段晶粒表面的吸附氧、锶空位V_(sr)”(或V_(sr)')及掺杂的受主体Cu~+对Sr~(2+)位的不等价取代所组成的晶界内过剩负电荷。讨论了La_2O_3/CuO在0.5～2.5、氧化保温时间τO_2在10至25分钟时对SrTiO_3半导瓷的非线性系数a和V_(1mA/mm)的影响。     

ZnO压敏陶瓷的晶界行为

晶界的结构、组成、性能以及相之间的界面与氧化锌压敏陶瓷的非线性、电性能、老化、化学性能方面有着重要联系。本文就ZnO压敏陶瓷的晶界行为以及工艺技术对晶界的影响因素进行了讨论 ,分析了关于ZnO压敏陶瓷导电、老化的晶界机理 ,大量研究表明 ,其多种特性均为晶界现象。     

SrTiO3陶瓷晶界层电容器材料的晶界研究Ⅰ.晶界结构

利用高分辨电镜研究了低温一次烧结SrTiO_3陶瓷晶界层电容器材料的晶界结构,发现在西晶粒间存在着4种典型的晶界类型。通过构筑晶界形成的结构模型,揭示了两晶粒间晶界形成的特征,认为两晶粒间晶界相的形成既与两晶粒间的液相成份和杂质组成有关,亦与两晶粒的相对取向有关。此外,还与两次烧结SrTiO_3陶瓷晶界层电容器材料的晶界结构作了比较。     

La掺杂对(In0.5Nb0.5)0.10Ti0.90O2陶瓷微观结构和介电性能的影响

In和Nb共掺杂TiO₂(INTO)陶瓷在100 kHz以下的巨大介电常数源于内部势垒层电容效应。根据这种电容效应,通过增加晶界对介电性能的贡献来降低其低频介电损耗。因此,将La掺杂到INTO陶瓷中,通过细化晶粒并增加晶界数量来降低陶瓷制备过程中的能耗。结果表明,La掺杂减小了INTO陶瓷的晶粒尺寸,增加了陶瓷中晶界的数量,并且陶瓷中析出LaNbTiO₆二次相,在陶瓷晶粒之间形成高阻态的相界,降低陶瓷的低频介电损耗,优化了陶瓷介电常数的频率稳定性。     

掺杂TiO_2制备低压ZnO压敏陶瓷

主要研究了晶粒助长剂TiO2、烧成条件等对ZnO低压压敏陶瓷电性能的影响。结果表明:TiO2的掺入能显著促进晶粒生长,降低压敏电压V1mA,但掺入量超过一定值后一方面会生成阻止晶粒继续生长的晶界反应层,促使压敏电压又有所升高,另一方面会生成钛酸铋立方相而引起富铋晶界相含量的减少,导致非线性特性下降。提高烧成温度可以促进晶粒生长,降低压敏电压,但温度过高时由于铋的挥发加剧,利用提高烧成温度降低压敏电压会引起非线性特性和漏流等性能的劣化。     

稀土Pr(OH)_3和Eu(OH)_3与单晶氧化铝界面的反应

本实验观察研究了稀土Pr(OH)3和Eu(OH)3在氧化铝单晶表面的行为,分别采用扫描电镜和能谱仪对截面进行形貌和成分分析。研究表明,在高温作用下,由于Al3+的扩散速率高于稀土离子,Al3+会扩散到稀土层中与稀土发生反应生成稀土和氧化铝的复合氧化物,而由于这种复合氧化物和氧化铝的晶粒高温下热膨胀各向异性的影响,导致两者发生剥离,也就是说在稀土添加的氧化铝陶瓷中,晶界上第二相的存在会弱化晶界结合强度。本实验旨在为稀土对氧化铝陶瓷性能的影响提供一定的指导意义。     

Varistor Performance of ZnO-Based Ceramics Related to Their Densification and Structural Development

Electrical potential barriers are often observed in ZnO-based ceramics. Earlier studies on ZnO photoconduction have shown that the narrow regions, where the sintered grains have grown together, control the resistance of the entire sample. In those regions, the surface/volume ratio is sufficiently high for the acceptor concentration (which occurs because of adsorbed oxygen) to exceed the donor concentration inside the ZnO grains. More recent works have shown that Schottky barriers result from interface states because of the chemisorbed oxygen ion at the ZnO-ceramic grain boundaries. The work reported in this paper involves the relationship between the densification of the microstructure and the varistor performance of ZnO ceramics. The emphasis of densification percentage as an indicator of the degree of sintering shows the desirability of continuity across ZnO grain boundaries, without the presence of voids or films of second phases, in optimizing varistor behavior. The effect of oxygen partial pressure on the development of varistor microstructure and electrical properties, as well the kinetics of grain growth, during the sintering process have been determined and are discussed.     

Electrical Nonuniformity of Grain Boundaries within ZnO Varistors

ZnO varistors with and without ZnO crystalline seeds have been prepared through conventional ceramic processing. Their electrical nonuniformity has been carefully examined using microcontact measurements of single grain boundaries, current-voltage ( I-V ) characteristics, and dielectric temperature spectra of bulk samples. Three types of grain boundaries with barrier heights of 0.2, 0.5, and 0.6 eV are identified in a ZnO varistor with the seeds, while only one with 0.4 eV barrier height has been found in a varistor without the seeds. Using a computerized electric circuit simulation, the influence of boundary thickness and grain size on I-V characteristics of varistor is investigated extensively. The simulated results show that currents passing across various grain boundaries are quite different. For a model varistor (1 × 1 × 1 mm³) with different grain size, a good agreement between measured data and simulated curves can be achieved.     

氧化锌压敏电阻的烧结行为

为了研究ZnO压敏电阻组成中非化学配比氧化物对ZnO压敏电阻导电性能的影响,采用在不同氧分压条件下烧结样品以研究其烧结行为。结果表明：ZnO晶粒的电导率对数与氧分压对数成线性关系;斜率为-1/4;间隙Zn原子以一价电离Zni形式存在。由于CoO,MnO和NiO阳离子空位氧化物多偏析于晶界,晶界处氧的增加有利于降低压敏电阻漏电流,烧结时间从2h延长到8h,漏电流从5μA/cm^2降到3.6μA/cm^2。波谱分析表明：掺杂氧化物在晶界处都有偏析,ZnO晶粒中掺杂原子混溶比例不完全与掺杂阳离子半径相关。     

Micro four-point probe investigation of individual ZnO grain boundaries in a varistor ceramic

The varistor effect in ZnO ceramics is triggered by the behavior of the grain boundaries. To understand this effect in detail we have electrically characterized individual grain boundaries. Here, we apply the micro four-point probe method to measure the electrical properties of individual grain boundaries in a polycrystalline ZnO varistor ceramic with a mean grain size of 10 μm. The investigation revealed a wide spread in electrical properties, like nonlinearty exponents from 10 to 150 and switching voltages from 2.3 V to 3.6 V.     

Fe_2O_3掺杂对ZnO-Pr_6O_(11)系压敏电阻材料电学性能的影响

通过烧结法制备了Fe2O3掺杂的ZnO–Pr6O11压敏电阻材料,研究了Fe2O3掺杂量对ZnO–Pr6O11系压敏电阻材料电学性能的影响。实验表明:当Fe2O3掺杂量小于0.005%(摩尔分数,下同)时,ZnO–Pr6O11系压敏电阻材料的非线性系数和压敏电压随Fe2O3掺杂量增大而逐渐提高。当Fe2O3掺杂量为0.005%时,压敏电压达到最大值571V/mm,非线性系数达到最大值26。当Fe2O3掺杂量大于0.005%时,非线性系数和压敏电压均急剧下降。过量Fe2O3使ZnO压敏电阻材料非线性下降的主要原因是:Fe元素偏析在晶界处,提供额外载流子降低了晶界电阻率,同时晶界处PrFeO3相的堆积会破坏晶界结构,从而影响压敏电阻材料的电学性能。     

Varistor and Magnetic Properties of Nickel Copper Zinc Niobium Ferrite Doped with Bi2O3

Bi₂O₃ was added into nickel copper zinc niobium ferrite and treated with different thermal processes to change the grain‐boundary chemical composition. The relationship between the grain‐boundary composition and varistor properties were investigated using scanning electron microscopy, transmission electron microscopy, energy dispersion spectroscopy, and X‐ray photoelectric spectroscopy. The experimental results show that Bi₂O₃ reacts and diffuses into the spinel ferrite grain, forming bismuth iron compounds, causing the spinel ferrite chemical composition near grain boundary becomes iron deficient. The Fe deficiency spinel ferrite near the grain boundary then changes into p‐type conduction. The annealing process after sintering improves the bismuth oxide diffusion and chemical reaction near the grain boundary, which can increase the grain‐boundary resistivity. The n‐type semiconductive grain interior and p‐type spinel ferrite near the grain‐boundary combination can form a double Schottky barrier, leading the specimen to exhibit varistor properties. A multifunctional varistor‐magnetic material with a nonlinear coefficient of 10 and initial permeability of about 225 at 10 MHz can be successfully fabricated by sinteringNi_0.2881Cu_0.1825Zn_0.4802Nb_0.0096Fe_2.0168O₄ ferrites added with 5 mol% Bi₂O₃ sintered at 950°C, then annealed at 650°C for 1 h.     

Electrical and hydrogen reduction enhances kinetics in doped zirconia and ceria: I. grain growth study

The kinetics of mass transport is central to ceramic processing and device stability. In this work, the effect of electrical and hydrogen reduction on the grain growth behavior of doped zirconia and ceria has been investigated. Faster grain growth has been observed under reducing conditions in all cases. The results firmly establish that a depressed local oxygen potential can enhance cation kinetics in fluorite‐structured oxide ceramics. Meanwhile, a large electrical current can generate a sharp, spatially varied oxygen potential profile, creating a graded microstructure with a dramatic grain size transition across the length of the sample.     

添加Nd2O3对氧化锌压敏阀片电性能与显微组织的影响

研究了微量Nd2O3添加剂对氧化锌压敏阀片的压敏电位梯度、漏电流和压比的影响,并对其显微组织进行了分析研究,从理论上探讨了Nd2O3对氧化锌压敏阀片电性能与组织的作用机理。研究结果表明:当Nd2O3的摩尔分数为0.04％时,氧化锌压敏阀片的压敏电位梯度最高,漏电流最小,压比最低,具有优良的综合电性能。其原因是Nd2O3加入到氧化锌压敏阀片中,使晶粒尺寸减小所致。     

Electric force microscopy investigations of barrier formations in ZnO-based varistors

The well known metal-oxide varistors (MOVs) are polycrystalline electronic ceramic materials whose electrical behavior is dominated by their grain boundaries. ZnO-based varistors are MOVs whose nonlinear properties are characterized by an electrical resistance that decreases as the applied voltage field increases. The objective of this work was to image the Schottky barriers in ZnO doped with 0.5 mol.% Cu and x wt.% G (G is a frit and x = 0, 1 and 5%). The frit is used to form a glassy insulating layer around grain boundaries. Samples were sintered at 850 °C and the microstructures were analyzed by atomic force microscopy (Nanoscope IIIa, VEECO Instruments). Electric force microscopy (EFM) experiments were conducted to map the electric field distribution on the surface of CuO–ZnO-based varistors. The formation of Schottky barriers was observed and their width measured.     

Origin of the High Permittivity and Varistor Behavior in SnO2–Zn2SnO4 Composite Ceramics

SnO₂–Zn₂SnO₄ composite ceramics with a colossal dielectric permittivity and varistor behavior are prepared by traditional ceramic processing. By increasing bias voltage from 0 to 10 V at a low frequency (~10³ Hz) and at room temperature, the relative permittivity decreased rapidly from about 20 000 to several thousand, whereas the radius of the semicircle in the complex impedance decreased and the tail gradually disappeared. However, the peak height and the position of the imaginary part of the complex modulus in the spectra were independent of the applied DC voltage. The slope deduced from the bias voltage‐dependent straight lines of the double‐logarithmic imaginary permittivity spectra were constant with a value of ?0.63 at high frequencies and they decreased to ?1 at low frequencies. The results strongly indicate that a number of weekly trapped charges existed in the ceramic bulk. From the temperature‐dependent dielectric and electric modulus spectra, the trapped charge activation energy was about 0.32 eV, which may be associated with the oxygen vacancies. Based on the results, a modified equivalent circuit related to the colossal dielectric permittivity and varistor properties was proposed, in which a Warburg impedance was added in parallel with the resistance and capacitance.