Domain structure of Bi4Ti3O12 ceramics revealed by chemical etching

Chemical etching of bismuth titanate (Bi₄Ti₃O₁₂) ceramics was developed using a mixture of different agents based on HF, NH₄F and H₂O. Thermal etching modifies the surface morphology and this give place to rounded plate-like grains. Suitable etching of Bi₄Ti₃O₁₂ samples could be however achieved with chemical agents, because it preserves the original shape of the platelets. Furthermore with this kind of etching two relevant features of the microstructure arise in scanning electron microscopy (SEM) micrographs: the domain structure of the etched grains and the presence of square-shaped holes inside the platelets.     

Shock-sintering of low-voltage ZnO-based varistor ceramics with Bi4Ti3O12 additions

Microstructure development in ZnO ceramics with Bi₄Ti₃O₁₂ (BIT) additions was studied in dependence of sintering temperature, inversion boundary (IBs) nucleation, heating rate and doping with transition metal oxides (NiO, MnO₂ and Co₃O₄). We demonstrated that one of the essential conditions for homogeneous microstructure development in this system is rapid release and efficient distribution of TiO₂, necessary for the formation of Ti-rich (tail-to-tail) IBs in ZnO grains. This can be achieved via the so-called shock-sintering procedure described in this article. Immediate decomposition of BIT to TiO₂-rich Bi₂O₃ liquid phase above 1200 °C leads to nucleation of ZnO grains with IBs. Exploiting the growth of ZnO grains with IBs, microstructure development can be easily controlled via the IB-induced grain growth mechanism, previously described in SnO₂-doped and Sb₂O₃-doped ZnO. In contrast to conventional sintering, where erratic nucleation of IBs leads to bimodal grain size distribution, shock-sintering sintering regime produces microstructures with uniform coarse-grain sizes, required for low-voltage varistor ceramics.     

MgTiO3-Bi4Ti3O12微波介质陶瓷的制备及性能研究

采用传统固相法制备了Bi4Ti3O12掺杂的MgTiO3陶瓷,研究了其对MgTiO3陶瓷烧结特性及微波介电性能的影响。通过测试分析发现,Bi4Ti3O12不仅可以显著降低陶瓷的烧结温度,同时还可以大大提高其介电常数,当Bi4Ti3O12/MgTiO3摩尔比为0.02时,MgTiO3-0.02Bi4Ti3O12陶瓷的最佳烧结温度为1 150℃,介电常数为31.99。     

Enhanced pyroelectric and piezoelectric responses in W/Mn-codoped Bi4Ti3O12 Aurivillius ceramics

The pyroelectric and piezoelectric properties of 4 at% Mn-doped Bi₄Ti_2.9W_0.1O₁₂ (BiTW-Mn) Aurivillius ceramic were investigated and compared to Bi₄Ti_2.9W_0.1O₁₂ (BiTW) counterpart, which were fabricated using a conventional solid state reaction method. High resistivities of 4.9?×?10¹² and 2.5?×?10¹¹ Ω?cm at 100?°C were obtained in the W-doped and W/Mn-codoped BiT ceramics, respectively. They showed similar activation energies and ionic-p-type mixed conduction mechanisms. Higher pyroelectric coefficients of 57.1?μC/m²K and piezoelectric coefficients of 21 pC/N, as well as much lower dielectric loss of 0.003 were achieved in W/Mn-codoped ceramics. These property changes were mainly induced by $\text{M}{\text{n}}_{\text{Ti}}^{}?{\text{V}}_{\text{o}}^{}$ defect dipoles. The effect of acceptor doping was evidenced by an internal bias field, shown by a horizontal offset in the polarization-field behavior. The improved properties together with high thermal stability indicate that BiTW-Mn may be a promising candidate for pyroelectric and piezoelectric devices at elevated temperatures.     

Colossal dielectric permittivity and relevant mechanism of Bi2/3Cu3Ti4O12 ceramics

Bi_2/3Cu₃Ti₄O₁₂ (BCTO) ceramics with pure perovskite phase were successfully prepared by traditional solid-state reaction technique. Uniformly distributed and dense grains with the grain size of 2–3 μm were observed by SEM. A giant low-frequency dielectric permittivity of ~3.3×10⁵ was obtained. The analysis of complex impedance revealed that Bi_2/3Cu₃Ti₄O₁₂ ceramics are electrically heterogeneous. There are three kinds of dielectric response detected in Bi_2/3Cu₃Ti₄O₁₂ ceramics, which existed in the low-frequency range, middle-frequency range, and high-frequency range, respectively. Through the study of dielectric spectrum at different temperatures, the relatively low activation energy of 0.30 eV for middle-frequency dielectric response was calculated, which suggested that this Middle-frequency dielectric response can be ascribed to grain boundaries response. In view of the analysis of dielectric spectrum at low temperatures, the activation energy of 0.07 eV for high frequency dielectric response was found. This value illustrated that dielectric response at high frequencies was associated with grains polarization effect. The comparison of dielectric spectra of Bi_2/3Cu₃Ti₄O₁₂ ceramics with different types of electrodes revealed that giant low-frequency dielectric constant was attributed to the electrode polarization effect.     

片状Bi4Ti3O12的合成及表征

采用熔盐法制备了Bi4Ti3O12粉体,研究了煅烧温度和盐的加入量对粉体显微形貌的影响.结果表明:Bi4Ti3O12晶粒呈较规则的薄片状四边形;烧温度的升高,晶粒尺寸显著增大,a-b面取向生长明显;盐与反应原料的质量比为1:1时,晶粒尺寸分布均匀,为6～8μm;晶粒生长遵循Ostwald熟化机理.     

Bi4Ti3O12 nanoparticles prepared by hydrothermal synthesis

The influence of hydrothermal conditions (including starting materials, reaction temperature and time) on the crystal structure and the morphology of Bi₄Ti₃O₁₂ particles are discussed in this paper. Bi₄Ti₃O₁₂ nanocrystalline particles were hydrothermally synthesized at temperatures in the range of 180–230 °C for 4–12 h, from Bi(NO₃)₃·5H₂O, TiCl₄ and NaOH solution. The XRD results revealed that a typical bismuth layered perovskite structure Bi₄Ti₃O₁₂ was obtained. The TEM showed that the Bi₄Ti₃O₁₂ nanoparticles are tabular, and the sizes are about 200 nm.     

Microstructural,structural and electrical properties of La3+-modified Bi4Ti3O12 ferroelectric ceramics

Bi_4?xLa_xTi₃O₁₂ (BLT) ceramics were prepared and studied in this work in terms of La³⁺-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (x_L) of La³⁺ into the Bi₄Ti₃O₁₂ (BIT) matrix was here found to locate slightly above x = 1.5. Further, La³⁺ had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric–paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La³⁺ content.     

Dielectric properties of Sm-doped CaCu3Ti4O12 ceramics

The effects of Sm substitution on structure, dielectric properties and conductivity of CaCu₃Ti₄O₁₂ ceramics were investigated. Ca_1?xSm_xCu₃Ti₄O₁₂ (x=0.0%, 0.5%, 1.0%) ceramics were synthesized by the solid-state reaction method. Single phase crystal of the ceramics with space group Im3 was obtained. With increasing Sm content, the dielectric loss of Ca_1?xSm_xCu₃Ti₄O₁₂ ceramics improved but the dielectric constant also decreased significantly, with both the low- and high-temperature dielectric relaxations suppressed.     

Dielectric and ferroelectric properties of Ta-modified Bi3.25La0.75Ti3O12 ceramics

B-site modified Bi_3.25La_0.75Ti_3-xTa_xO₁₂ ceramics were prepared by the conventional solid-state reaction method. The influence of Ta₂O₅ on microstructure and electric properties of the ceramics was investigated. The results demonstrated that Ta⁵⁺ ions were dissolved into the perovskite lattice and homogeneously distributed in the matrix without forming any minority phase. The conduction mechanism and dielectric response behavior were transformed with Ta substation, which is triggered by varied structural distortion characteristics and defect diploes. The Curie temperature decreased gradually with increasing Ta content and a relaxor-like behavior was observed for x = 0.09 sample. The internal bias field is decreased with Ta doping, because the substitution of Ta⁵⁺ at B-site contributes to release the involved oxygen vacancies in defect diploes. Moreover, further increasing Ta content causes a reduction in the oxygen vacancies located at lattice misfits, resulting in a decrease of coercive fields. An improved ferroelectric properties were obtained for x = 0.09 sample with a relatively lower coercive field and a larger spontaneous polarization.     

Dielectric properties of CaCu3Ti4O12 based multiphased ceramics

A “soft chemistry” method, the coprecipitation, has been used to synthesize the perovskite CaCu₃Ti₄O₁₂ (CCT). Three main types of materials were obtained for both powders and sintered ceramics: a monophased consisting of the pure CCT phase, a biphased (CCT + CaTiO₃), and a three-phased (CCT + CaTiO₃ + copper oxide (CuO or Cu₂O)). These ceramics, sintered at low temperature, 1050 °C, present original dielectric properties. The relative permittivity determined in the temperature range (−150 < T < 250 °C) is significantly higher than the one reported in the literature. Internal barrier layer capacitor is the probable mechanism to explain the particular behaviour. Moreover, the presence of a copper oxide phase beside the perovksite CCT plays an important role for enhancing the dielectric properties.     

Synthesis and dielectric anomalies of CdCu3Ti4O12 ceramics

CdCu₃Ti₄O₁₂ ceramics were successfully synthetized by the conventional solid-state reaction method. The influences of sintering parameters on phase structure, microstructure and dielectric properties were investigated systematically. CdCu₃Ti₄O₁₂ ceramics sintered at 1020 °C for 15 h exhibited high temperature stability and outstanding dielectric properties, evidenced by the △C_T/C_25 °C ranges from −14.8% to 12.1% measured from −55 to 125 °C at 1 kHz, and the giant dielectric constant ε′=2.4×10⁴ as well as dielectric loss tanδ=0.072. Four dielectric anomalies were evidenced in dielectric temperature spectra and the related physical mechanisms were discussed in detail. The oxygen vacancies play an important role in dielectric anomalies in the high temperature range.     

Enhanced electrical behavior in Ca1-xSrxCu3Ti4O12 ceramics

Polycrystalline Ca_1-xSr_xCu₃Ti₄O₁₂ ceramics were studied as a function of the strontium content in order to understand its effects on the structure, microstructure and electrical characteristics of these compounds. Our results showed that the Sr²⁺ cationic substitution into the A sites of the initial CaCu₃Ti₄O₁₂ (CCTO) phase leads to crystalline phases with specific stoichiometry. Although the same space group is observed, the cationic substitution induces larger lattice parameter, phase density, and chemical bonding length when compared to the initial CCTO phase. Microstructure results indicated that the strontium content has a significant influence on sample sinterability leading to changes in grain growth and densification process. The non-ohmic characterization showed that the Ca_0.5Sr_0.5Cu₃Ti₄O₁₂ phase exhibits improved breakdown electric field (32 kV/cm), non-linear coefficient (269) and lower leakage current (26 μA), while the SrCu₃Ti₄O₁₂ phase presents permittivity of about 5000 at 1 kHz.     

Effect of magnetic CoFe2O4 component on sintering densification process of Bi3.15Nd0.85Ti3O12 ceramics

Sintering densification processes of the composite ceramics (Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT)/CoFe₂O₄ (CFO)) have been investigated using dilatometric experiments combining with the TG-DTA, density measurements and microstructure studies. Microstructures analyses and quantitative calculations show that the composite ceramics achieve densification at low temperatures (<1150 °C). The formation of coherent-lattice interfaces between (200)/(020)_BNdT and (310)_CFO are considered to play an important role on such densification. The intrinsic preferred orientation of BNdT grains is suppressed by CFO phase because of this coherent relationship. Although the sintering activation energies of 0.8BNdT-0.2CFO are about 2.7 times larger than those of pure BNdT due to the pinning effect, the composite ceramic could still be densified, indicating the formation energy of coherent-lattices provided the extra sintering force. The even coercive electric fields of the resulting pure BNdT and 0.8BNdT-0.2CFO ceramic are approximately 89 and 97 kV/cm, respectively, at 250 kV/cm. The polarization of 0.8BNdT-0.2CFO reaches saturation around 430 kV/cm.     

水热法制备钛酸铋粉体的研究

以TiCl4乙醇溶液和Bi（NO3）3·5H2O为原料．NaOH为矿化剂，其摩尔配比的关系为TiCl：Bi（NO3）3·5H2O：NaOH=0．1：0．75：1．5．用水热法合成钙钛矿结构的钛酸铋粉体。讨论了水热合成条件（前驱物和粉体处理、晶化时间、填充率）对钛酸铋粉体结构和形貌的影响。XRD、SEM分析表明，在240℃，晶化时间16h，填充比为60％的条件下，可制备平均晶粒粒径为9～12nm，团聚较轻，颗粒边界明显．球形的钛酸铋粉体。     

钛酸铋纳米粉体的水热合成及表征

采用分析纯Bi(NO3)3·5H2O和TiO2为原料,以NaOH 为矿化剂,用水热法合成了钛酸铋纳米粉体.讨论了水热反应温度和晶化时间对钛酸铋粉体结构和形貌的影响.研究结果表明,随着水热温度的提高及晶化时间的延长,晶体结晶程度提高;在140～180 ℃和30～72 h的水热条件下,合成了纯的Bi4Ti3O12粉体,其主要由方形片状的纳米晶组成,为典型的钙钛矿结构.并结合实验结果探讨了钛酸铋的水热合成机理.     

钛酸铋陶瓷靶材的热压烧结

纯相、高致密度、结晶良好的陶瓷靶材是物理气相沉积薄膜的前提.采用热压烧结方法制备钛酸铋(Bi4Ti3O12)陶瓷靶材,重点研究了制备工艺对靶材的物相、微观结构和致密度的影响.以Bi2O3和TiO2微粉为原料,采用固相反应法,在800℃合成出纯相的Bi4Ti3O12粉体;加入过量3wt%的Bi2O3,可以有效防止烧结过程中因Bi挥发所产生的杂相,得到纯相的Bi4Ti3O12陶瓷;采用热压烧结方法,进一步实现了Bi4Ti3O12粉体的致密烧结,确定了适宜的制备条件为850℃,30MPa,2b,在该条件下制备的Bi4Ti3O12陶瓷致密度达到99%,晶粒呈片层状,大小约2-4μm,可满足靶材制备薄膜的需求.     

Preparation of Bi4Ti3O12 particles by crystallization from glass

Glass from the Bi₂O₃–TiO₂–B₂O₃ system was formed by rapid quenching of the melt. After annealing at 500 °C, the glass crystallized in the form of plate-like particles. The particles thus formed were separated through an acid treatment. Field emission scanning electron microscopy showed a layered structure for the particles. XRD observations revealed that the crystalline form was Bi₄Ti₃O₁₂, a useful material in the electronics industry.     

Relaxor‐like behaviors in Na1/2Bi1/2Cu3Ti4O12 ceramics

Dielectric properties of Na_1/2Bi_1/2Cu₃Ti₄O₁₂ ceramics were evaluated over the temperature range 300‐720 K. Two relaxor‐like dielectric anomalies were found. The low‐temperature anomaly was confirmed to be an oxygen‐vacancy‐related relaxation process. It is a pseudo‐relaxor behavior caused by a bulk relaxation and a Maxwell‐Wagner relaxation. The high‐temperature one was evidenced to be an electric ferroelectric phase‐transition process resulting from the oxygen‐vacancy ordering.     

Enhancement of giant dielectric response in Ga-doped CaCu3Ti4O12 ceramics

The influences of Ga³⁺ doping ions on the microstructure, dielectric and electrical properties of CaCu₃Ti₄O₁₂ ceramics were investigated systematically. Addition of Ga³⁺ ions can cause a great increase in the mean grain size of CaCu₃Ti₄O₁₂ ceramics. This is ascribed to the ability of Ga³⁺ doping to enhance grain boundary mobility. Doping CaCu₃Ti₄O₁₂ with 0.25 mol% of Ga³⁺ caused a large increase in its dielectric constant from 5439 to 31,331. The loss tangent decreased from 0.153 to 0.044. The giant dielectric response and dielectric relaxation behavior can be well described by the internal barrier layer capacitor model based on Maxwell?Wagner polarization at grain boundaries. The nonlinear coefficient, breakdown field, and electrostatic potential barrier at grain boundaries decreased with increasing Ga³⁺ content. Our results demonstrated the importance of ceramic microstructure and electrical responses of grain and grain boundaries in controlling the giant dielectric response and dielectric relaxation behavior of CaCu₃Ti₄O₁₂ ceramics.