Microstructures and electrical responses of pure and chromium-doped CaCu3Ti4O12 ceramics

Pure and chromium-doped CCTO (CaCu₃Ti₄O₁₂) ceramics were prepared by a conventional solid-state reaction method, and the effects of chromium doping on the microstructures and electrical properties of these ceramics were investigated. Efficient crystalline phase formation accompanied by dopant-induced lattice constant expansion was confirmed through X-ray diffraction studies. Scanning electron microscopy (SEM) results show that doping effectively enhanced grain growth or densification, which should increase the complex permittivity. The dielectric constant reached a value as high as 20,000 (at 1 kHz) at a chromium-doping concentration of 3%. The electrical relaxation and dc conductivity of the pure and chromium-doped CCTO ceramics were measured in the 300-500 K temperature range, and the electrical data were analyzed in the framework of the dielectric as well as the electric modulus formalisms. The obtained activation energy associated with the electrical relaxation, determined from the electric modulus spectra, was 0.50-0.60 eV, which was very close to the value of the activation energy for dc conductivity (0.50 ± 0.05 eV). These results suggest that the movement of oxygen vacancies at the grain boundaries is responsible for both the conduction and relaxation processes. The short-range hopping of oxygen vacancies as “polarons” is similar to the reorientation of the dipole and leads to dielectric relaxation. The proposed explanation of the electric properties of pure and chromium-doped CCTO ceramics is supported by the data from the impedance spectrum.     

CaCu_3Ti_4O_(12)陶瓷的巨介电响应机理

针对CaCu3Ti4O12(CCTO)陶瓷的巨介电性起源存在较大争议的情况,以少量MnO2取代CCTO中CuO或TiO2、采用固相反应法烧结制备名义成分为CaCu3-xMnxTi4O12(x=0~0.3)和CaCu3Ti4-yMnyO12(y=0~0.1)的陶瓷。通过微结构和电性能的演变讨论CCTO陶瓷的巨介电响应机理。结果表明:加入少量MnO2后,所有陶瓷均为体心立方(BCC)类钙钛矿结构的CCTO单相;但是,CCTO陶瓷显微结构从异常长大的晶粒转变成均匀的细小晶粒;同时,CCTO陶瓷的电阻率从107-.cm显著提高到109-.cm;介电常数从104显著下降到102;介电损耗从10-1急剧降低到10-3;CCTO陶瓷的巨介电响应是由半导体化的晶界/亚晶界和相对绝缘的晶粒/亚晶粒组成的内部阻挡层电容器(IBLC)所致。在较低温度下(<1 100℃)烧结获得高介电常数、低损耗和温度稳定的CCTO基陶瓷,找到一种降低CCTO陶瓷介电损耗的有效方法。     

Al_2O_3/(Ag_(72)Cu_(28))_(97)Ti_3/Ti-6Al-4V界面结构及性能研究

在1．8ks,1073K－1173K条件下对Al2O3/(Ag72Cu28)97Ti3/Ti-6Al-4V进行了钎焊试验。通过扫描电镜、波谱、能谱、X射线衍射界面结构进行了分析。小于1123K的界面结构为Al2O3/Cu2Ti4O/Cu4Ti3/Ag-Cu共晶＋富Ag相＋Ti固溶体;1173K的界面结构为Al2O3/Cu3TiO5 CuAl2O4/Cu4Ti3/富Ag相。采用拉剪试验测试了接头剪切强度。在1．8ks,1123K时剪切强度最高达到189MPa,大于或小于1123K接头强度呈下降趋势。     

Al_2O_3/(Ag_(72)Cu_(28))_(97)Ti_3/Ti-6Al-4V界面结构及性能研究

在 1.8 ks,10 73 K～ 1173 K条件下对 Al2 O3/ ( Ag72 Cu2 8) 97Ti3/ Ti- 6Al- 4 V进行了钎焊试验。通过扫描电镜、波谱、能谱、X射线衍射对界面结构进行了分析。小于 112 3 K的界面结构为 Al2 O3/ Cu2 Ti4 O/ Cu4 Ti3/ Ag- Cu共晶 +富 Ag相 + Ti固溶体 ;1173 K的界面结构为 Al2 O3/ Cu3Ti O5+ Cu Al2 O4 / Cu4 Ti3/富 Ag相。采用拉剪试验测试了接头剪切强度。在 1.8ks,112 3 K时剪切强度最高达到 189MPa,大于或小于 112 3 K接头强度呈下降趋势。     

铈掺杂对钙铋钛铁电陶瓷取向及性能的影响

用固相烧结工艺,制备了不同Ce掺量CaBi_(4-x)CexTi_4O_(15)的陶瓷样品.用X射线衍射对其显微结构进行了分析,并测试了样品的介电、铁电性能,研究了烧结温度对样品晶粒取向和铁电性能的影响.结果发现Ce掺杂未改变CaBi_(4-x)CexTi_4O_(15)的晶体结构,1150 ℃烧结所得样品中a轴取向晶粒较多,有利于样品的铁电性能;x=0.2为最佳掺量,样品剩余极化强度最大,2P_r=18.4 mC/cm~2 ,对应的矫顽场强度2E_c=99 kV/cm,相对介电常数ε_r=165,介电损耗tanδ=2×10~(-3).     

溶胶—凝胶法制备CaCu3Ti4O12-MgTiO3复合陶瓷的介电性能与IV特性

通过溶胶凝胶方法制备得到CaCu3Ti4O12-MgTiO3复合陶瓷粉料,并在1000,1050和1100℃3个温度点烧结成瓷。采用XRD、SEM等对得到的样品成分、结构进行了分析,发现材料为CCTO-MgTiO3/MgTi2O4复相体系。在此基础上,对材料的介电性能、IV非线性特性做了相关测试。复合陶瓷在1100℃下烧结后,其介电常数比纯的CCTO要提高3到4倍。对材料的IV测试发现,复合陶瓷的IV非线性系数可以通过复合体系的线性法则拟合得到,材料的非线性系数约为4.56。     

烧结温度对Sr_2Bi_4Ti_5O_(18)铁电陶瓷性能的影响

用固相合成方法制备了Sr_2Bi_4Ti_5O_(18)铁电陶瓷,研究了烧结温度对Sr_2Bi_4Ti_5O_(18)铁电陶瓷相结构、显微结构、铁电性能和介电性能的影响,分析了相关机理.结果表明,在1150C℃进行烧结,样品晶粒发育完全,晶粒α轴择优取向,铁电性能优良,剩余极化强度2P,达到15.3μC/cm2、矫顽场强2E_c为103kV/cm;在100kHz～1MHz频率范围内,介电常数为176～168,介电损耗为0.027～0.025,具有较好的频率稳定性.     

低温烧结Bi_6Ti_5TeO_(22)和Bi_2Ti_3TeO_(12)陶瓷及其微波介电性能

采用固相烧结法,研究了不同温度和配方Bi_2O_3-TiO_2-TeO_2体系陶瓷的低温烧结情况,研究了产物物相、微观结构和微波介电性能.研究表明,配方A(Bi_2O_3:TiO_2:TeO_2=1:3:1)在800 ℃以上煅烧可制备出较纯净的Bi_6Ti_5TeO_(22),配方B (Bi_2O_3:TiO_2:TeO_2=1.025:3:1)在700℃以上煅烧可制备纯净的Bi_2Ti_3TeO_(12)粉末.所得Bi_6Ti_5TeO_(22)和Bi_2Ti_3TeO_(12)粉末都能在750～900 ℃度实现低温烧结.配方B在750℃烧结的介电性能较好,ε_r=32.5,介电损失为0.20%(100 MHz).     

添加玻璃料对BaSm_2Ti_4O_(12)微波介质陶瓷烧结行为和介电性能的影响

利用固相法制备BaSm_2Ti_4O_(12)(BST)微波介质陶瓷.研究了复合添加Li_2CO_3-B_2O_3-SiO_2-CaO-Al_2O_3(LBSCA)和BaO-B_2O_3-SiO_2(BBS) 玻璃料对BaSm_2Ti_4O_(12)微波介质陶瓷的烧结性能、介电性能、相组成和微观结构的影响.研究表明:复合掺杂10% LBSCA和2%～5% BBS可使烧结温度降至900 ℃.XRD分析表明复合掺杂两种玻璃料的BST陶瓷主晶相为BaSm_2Ti_4O_(12)相,玻璃料以玻璃相的形式存在陶瓷晶粒间.复合掺杂10% LBSCA+3%BBS玻璃料的BST陶瓷可在900 ℃、保温2 h条件下烧结致密,微波介电性能为:ε_r =55.63,Q_f = 4266 GHz,τ_f= -13.5×10~(-6)℃~(-1),这种陶瓷材料有望与纯Ag电极共烧,制作各种多层微波频率元器件.     

Dielectric relaxation behaviors of pure and Pr6O11-doped CaCu3Ti4O12 ceramics in high temperature range

Pure and Pr₆O₁₁-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were prepared by conventional solid-state reaction method. The compositions and structures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influences of Pr-ion concentration on dielectric properties of CCTO were measured in the ranges of 60 Hz-3 MHz and 290-490 K. The third phase of Ca₂CuO₃ was observed from the XRD of CCTO ceramics. From SEM, the grain size was decreased obviously with high valence Pr-ion (mixing valence of Pr³⁺ and Pr⁴⁺) substituting Ca²⁺. The room temperature dielectric constant of Pr-doped CCTO ceramics, sintered at 1323 K, was an order of magnitude lower than the pure CCTO ceramics due to the grain size decreasing and Schottky potential increasing. The dielectric spectra of Pr-doped CCTO were flatter than that of pure CCTO. The loss tangent of Pr-doped CCTO ceramics was less than 0.20 in 2 × 10²-10⁵ Hz region below 440 K. The complex impedance spectra of pure and Pr-doped CCTOs were fitted by ZView. From low to high frequency, three semicircles were observed corresponding to three different conducting regions: electrode interface, grain boundary and grain. By fitting the resistors R and capacitors C, the activation energies of grain boundary and electrode contact were calculated. All doped CCTOs showed higher activation energies of grain boundary and electrode than those of pure CCTO ceramics, which were concordant with the decreasing of dielectric constant after Pr₆O₁₁ doping.     

Influence of CaF2 on the structure and dielectric properties of Ag（Nb0.8Ta0.2）O3 ceramics

Ag(Nb0.8Ta0.2)O3 ceramics were prepared by the traditional solid-state reaction method. The effect of CaF2 addition on the structure and di-electric properties of Ag(Nb0.8Ta0.2)O3 ceramics was investigated. The addition of CaF2 led the ceramics to a larger grain size and distortion of lattice. With the addition of 4.5 wt.% CaF2, the permittivity of the ceramics increased from 442 to 1028, the dielectric loss decreased sharply from 6.12 × 10-3 to 8.6 × 10-4, and the temperature coefficient of capacitance decreased from 1834 ppm/°C to-50 ppm/°C (at 1 MHz). These results indicated that the high permittivity was related with a large grain size, a low grain boundary density, and the weak Ta-O or Nb-O bond strength caused by the addition of CaF2.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Influence of sintering schedule on the electrical properties of Mn（NO3）2-doped Ba0.92Ca0.08TiO3 PTCR ceramics

The relationship of electrical properties of Mn-doped Ba0.92Ca0.08TiO3 PTCR (positive temperature coefficient resistance) ceramics with two sintering schedules was discussed. Using TEM (transmission electron microscope) combined with EDS (energy dispersive X-ray spectrometer), the Mn ions distributed at grain boundaries were analyzed. The results show that the PTCR effect of Mn-doped PTCR ceramics is more dependent on the sintering schedule than those of Mn free. The phenomenon may be caused by the valence states variance of Mn ions segregated at the grain boundaries.     

Ti基非晶及准纳米晶材料制备技术研究

用Al、B取代Ti50Ni15Cu25Sn3Be7中有毒的Be元素,采用真空甩带及铜模吸铸法制备名义成分为Ti50Ni15Cu25-Sn3Al6.9B0.1的非晶合金。对制得的合金经热处理制备准纳米晶体。采用SEM观察组织及晶粒大小。XRD分析结果表明,铜模吸铸法所制得的合金为晶态加少量非晶。DTA分析表明,合金存在三个相变转变点,转变温度分别为Te1=350℃、Te2=430℃和Te3=510℃。合金经800℃油淬10min、350℃回火12h后晶粒细化,晶粒尺寸在1μm以下,其中析出相的晶粒尺寸已是准纳米级或纳米级尺度。回火24h后晶粒明显长大,晶粒平均尺寸在10μm左右。     

Preparation and Dielectric Properties of CaCu3Ti4O12 Ceramics with Different Additives

Li₂CO₃, MgCO₃, BaCO₃, and Bi₂O₃ dopants were introduced into CaCu₃Ti₄O₁₂ (CCTO) ceramics in order to improve the dielectric properties. The CCTO ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure, and dielectric behavior were carefully investigated. The pure structure without any impurity phases can be confirmed by the x-ray diffraction patterns. Scanning Electron Microscopy (SEM) analysis illuminated that the grains of Ca_0.90Li_0.20Cu₃Ti₄O₁₂ ceramics were greater than that of pure CCTO. It was important for the properties of the CCTO ceramics to study the additives in complex impedance spectroscopy. It was found that the Ca_0.90Li_0.20Cu₃Ti₄O₁₂ ceramics had the higher permittivity (>45000), the lower dielectric loss (<0.025) than those of CCTO at 1 kHz at room temperature and good temperature stability from ?30 to 75 °C.     

溶胶-凝胶法制备Ni掺杂CaCu3Ti4O12陶瓷的显微组织及电性能（英文）

采用溶胶凝胶法制备掺杂不同含量NiO(CaCu3NixTi4O12+x,x=0, 0.1, 0.2, 0.3)的CCTO陶瓷,通过扫描电镜和 X 射线衍射对其显微组织和相成分进行了分析,并研究了NiO掺杂对CCTO介电和压敏性能的影响。研究结果表明:Ni对CCTO陶瓷的相位成分没有影响,与用传统固相法制得的样品相比,用溶胶-凝胶法制成的样品具有更小的晶粒尺寸。从介电测量结果来看,当 x=0.2 时,样品具有最高的介电常数和最低的介电损耗。当x=0.3时,得到最低的漏电流,最小值为 0.295,同时,具有最高的阀值电压与非线性系数,最大值分别为1326V/mm和3.1。     

CaCu3Ti4O12 ceramics from basic co-precipitation (BCP) method: Fabrication and properties

High dielectric CaCu₃Ti₄O₁₂ (CCTO) ceramics have been successfully prepared by a novel basic co-precipitation (BCP) method. Compared with the conventional solid-state and/or soft chemistry methods, the BCP method has many advantages such as relatively lower sintering temperature, shorter sintering time and lower costs. The XRD patterns confirm the formation of CCTO crystal phase in the as-prepared samples. Influences of initial ingredients and sintering condition on phase composition, microstructure and dielectric property have been investigated through series of trials. The correlation between the process of the grain growth and dielectric properties of final products has been explored. The final products exhibit the dielectric constants higher than 10,000 and the dielectric losses lower than 0.15 at 1 KHz.     

ACu3Ti4O12(A=Ca, Sr, Ba)的介电性能

利用传统固相反应法制备理想摩尔配比的CaCu3Ti4O12(CCTO)、SrCu3Ti4O12(SCTO)和BaCu3Ti4O12(BCTO)陶瓷样品,测量它们在不同频率下的介电常数和介电损耗随温度的变化关系.结果发现,CaCu3Ti4O12的介电性能基本上属于德拜弛豫,而造成SCTO和BCTO与CCTO介电性能差异巨大的原因是结构的畸变和杂相的出现.     

活性元素Y和Ce对Fe—25Cr—40Ni合金高温氧化的影响

用离子背散射和慢正电子束研究了活性元素Y和Ce对Fe-25Cr—40Ni合金在高温初期氧化动力学、氧化膜表层成份和微观缺陷结构的影响,实验结果表明了微量活性元素(≥0.05%)在高温氧化初期显著减少了合金的氧化速率,有效地促进了Cr_2O_3的生长,抑制了Fe和Ni氧化物的形成,改善了氧化膜的微观结构,活性元素结合进入氧化膜并在外层膜中(约几十nm)富集,活性元素Ce抗氧化机理不同于Y,Ce使合金氧化膜的空位缺陷显著降低,主要控制了阳离子沿晶格空位向外扩散,而含Y合金由氧化初期主要控制阳离子沿晶格扩散转变为主要控制阳离子沿晶界向外扩散。     

Preparation and characterization of Mg-doped CaCu3Ti4O12 thin films

Mg-doped CaCu_3?xMg_xTi₄O₁₂ (x=0, 0.05, 0.1, 0.15, 0.2, at.%) thin films were prepared by a modified sol?gel method. A comparative study on the microstructure and electrical properties of Mg-doped CaCu₃Ti₄O₁₂ (CCTO) thin films was carried out. The grain sizes of the Mg-doped CCTO thin films were smaller in comparison to the undoped CCTO films. Furthermore, compared to undoped CCTO films, Mg-doped CCTO thin films obtained higher dielectric constant as well as excellent frequency stability. Meanwhile, Mg doping could reduce the dielectric loss of CCTO thin films in the frequency range of 10⁴?10⁶ Hz. The results showed that the Mg-doped CCTO thin films had the better electrical characteristics compared with the undoped CCTO films. The nonlinear coefficient of Mg-doped CCTO thin films at x=0.15 and x=0.1 was improved to 7.4 and 6.0, respectively.