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1.
In the current study, we report on the dielectric behavior of colossal-dielectric-constant Na1/2La1/2Cu3Ti4O12 (NLCTO) ceramics prepared by mechanochemical synthesis and spark plasma sintering (SPS) at 850 °C, 900 °C, and 925 °C for 10 min. X-ray powder diffraction analysis showed that all the ceramics have a cubic phase. Scanning electron microscope observations revealed an increase in the average grain size from 175 to 300 nm with an increase in the sintering temperature. SPS NLCTO ceramics showed a room-temperature colossal dielectric constant (>103) and a comparatively high dielectric loss (>0.1) over most of the studied frequency range (1 Hz–40 MHz). Two relaxation peaks were observed in the spectra of the electrical modulus and attributed to the response of grain and grain boundary. According to the Nyquist plots of complex impedance, the SPS NLCTO ceramics have semiconductor grains surrounded by electrically resistive grain boundaries. The colossal dielectric constant of SPS NLCTO ceramics was attributed to the internal barrier layer capacitance (IBLC) effect. The high dielectric loss is thought to be due to the low resistivity of the grain boundary of SPS NLCTO.  相似文献   

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Bi2Al4O9 ceramics are difficult to sinter to greater than 80% theoretical density due to peritectic decomposition at 1,070 °C. A novel processing method is discussed where a high-bismuth oxide-based liquid is used as a sintering aid. After sintering, the high bismuth oxide phase is removed by leaching with 40% acetic acid. The resulting samples are phase pure and ∼91% dense. The grain size varies in a wide range with the average grain size of ∼1 μm. The electrical properties of these ceramics were measured as functions of temperature (550–850 °C) and oxygen partial pressure (6×10−6–1 atm). The total conductivity was separated into electronic and ionic contributions. The low ionic conductivity indicates that the material is not an ‘intrinsically defective fast ion conductor’. The ionic conductivity is due almost exclusively to compensating oxygen vacancies related to impurities. With increasing temperature and decreasing oxygen partial pressure, the electronic conduction dominates over the ionic conduction.  相似文献   

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The Aurivillius oxides were originally of interest for their ferroelectric properties and have recently been explored in the field of oxide ion conductivity. Atomistic simulation methods have been carried out for Bi3TiNbO9, Bi4Ti3O12, BaBi4Ti4O15 and Ba2Bi4Ti5O18 doped with Pb, Al, Ga, In, Ta to determine defect energy in the materials by employing efficient energy minimization procedures. The calculations rest upon the specification of an interatomic potential model, which expresses the total energy of the system as a function of the nuclear coordinates. The Born model framework, which partitions the total energy into long‐range Coulombic interactions and a short‐range term to model the repulsions and van der Waals forces between electron charge clouds, is employed. This is embodied in the GULP simulation code. Dopant solution energy versus ion size trends are found for both isovalent and aliovalent dopant incorporation at Bi and Ta sites. Trivalent dopants (Al, Ga, In) and Pb are more favorable on the Bi site, whereas Ta dopants preferentially occupy the Ti site.  相似文献   

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The Fe3O4/TiO2/Bi2O3 composites were synthesized by a sol–gel method and used as improved photocatalysts for the degradation of methyl orange (MO) under simulated sunlight at room temperature. The as-prepared Fe3O4/TiO2/Bi2O3 composites were characterized by X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS). TEM analysis reveals that the composite has a core–shell structure and diameters of Fe3O4 core is about 200 nm. DRS results reveal that all composites showed red shift in optical absorption. TiO2, Fe3O4, and Bi2O3 exist mainly as separate phases in the Fe3O4/TiO2/Bi2O3 composites based on XPS analysis. The photocatalytic degradation of MO with the prepared photocatalysts was studied under simulated sunlight illumination. Photocatalytic reactivity test indicated that the removal efficiency of MO with the Fe3O4/TiO2/Bi2O3 photocatalyst was higher than that of pure TiO2 and Fe3O4/TiO2. Recovery rate of Fe3O4/TiO2/Bi2O3 photocatalysts achieved 80 % after five times reuse.  相似文献   

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《Solid State Sciences》2012,14(9):1378-1384
Transparent thin films were prepared by a sol–gel method starting from precursor formation in solution, subsequent spin coating followed by a heating ramp up to a maximum of 700 °C. Starting from a Bi2MoO6 synthesis route, the phase formation and thin film processing of the bismuth containing materials Bi2WO6, Bi3Ti4O12 and additionally of the tungsten–bronze structure Sr0.75Ba0.25Nb2O6 were studied. Spin coating was used to adjust the film thickness in a wide range from 6 to 200 nm. All films were obtained as multicrystalline pure phases according to X-ray diffraction analyses. Scanning electron micrographs revealed homogeneous coatings composed of nanoparticles with a crystallite size varying between 20 and 100 nm, furthermore the UV–VIS spectra demonstrated a high transparency of the films, 80–90% at 600 nm.  相似文献   

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Gan  Huihui  Liu  Jin  Zhang  Huining  Qian  Yongxing  Jin  Huixia  Zhang  Kefeng 《Research on Chemical Intermediates》2018,44(3):2123-2138
Research on Chemical Intermediates - A hybrid bismuth titanate Bi4Ti3O12/Bi2Ti2O7 obtained via a one-step annealing procedure was employed as photocatalyst to oxidize rhodamine B dyes (RhB) and...  相似文献   

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Different amounts of CuO are used to synthesize CaCu3+xTi4O12 (CCxTO, −1 ≤ x ≤ 1) powders in this work. In order to investigate the effects of Cu constituent on the componential, morphological, and dielectric properties, 975 °C is selected as the sintering temperature to prepare the ceramic pellets with different x values from −0.2 to 0.2. They basically keep the same component and morphology despite the different Cu constituents in the ceramics. Cu component has complex effects on their dielectric properties, whose changes are not linear with the Cu increase. However, the CC0.2TO ceramic sample has the most frequency-independent dielectric constant and the lowest dielectric loss.  相似文献   

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近年来,卤氧铋(BiOX,X=Cl,Br,I)作为多功能半导体光催化材料,因其具有独特的层状结构和电子结构,吸引了广泛关注.然而,相对低的导带(CB)和高的价带(VB)位置导致其氧化还原能力弱,从而限制了其实际应用.研究表明,通过富铋策略调控BiOX中元素化学计量比,可以实现对其能带结构的可控调控.尽管富铋半导体材料被视为有效的可见光光催化剂的候选材料之一,但是单一组分的富铋光催化剂不利于光生载流子的分离和迁移.具有匹配能带结构的富铋基复合光催化剂的构建已被证实可以加速光生电子-空穴对的分离和迁移.与传统的Ⅱ型异质结构相比,S型异质结既可以有效地分离光生载流子,又可以增强其氧化还原能力.如果双富铋基半导体之间能形成S型异质结,不仅可以拓展可见光响应,而且还可以增强光生电荷的氧化还原能力.基于Bi4O5I2/Bi4O5Br2的匹配能带,制备具有强氧化还原能力的S型Bi4O5I2/Bi4O5Br2异质结是可行的.除了电子结构外,表面缺陷的引入也对改善光催化性能起到了重要作用.氧空位(OVs)作为一种典型的缺陷,可以捕获电子来抑制光诱导载流子的复合,并加速这些捕获载流子向吸附剂的转移.此外,它们还可以充当有机污染物和分子氧的吸附位点,促进吸附和降解效率.目前,光催化材料中OVs的形成通常需要复杂、苛刻的条件,如高温、高压、惰性或还原气氛处理等,因此寻找简便有效的方法生成OVs仍然具有挑战性.此外,在无惰性或还原气氛下对有机前驱体进行热处理被认为是形成OVs的有效方法.鉴于此,本文通过低温煅烧二维纳米片有机前驱体BiOAc0.6Br0.2I0.2(Ac-=CH3COO-)固溶体,成功合成了表面富有氧空位的一维纳米棒状的S型Bi4O5I2/Bi4O5Br2异质结(Bi4O5I2/Bi4O5Br2-OV).X射线衍射、高分辨率透射电子显微镜电子顺磁共振以及X射线光电子能谱分析(XPS)等结果均证实了表面氧空位的存在.同时,根据吸收光谱图和肖特基曲线计算出Bi4O5I2和Bi4O5Br2的能带结构,而且通过XPS价带谱进一步证实了所计算的价带的可靠性.根据捕获剂实验、氯化硝基四氮唑蓝(NBT)转移以及对苯二甲酸荧光均证实了h+、·OH和·O2-是参与光催化降解的主要活性物种.再结合上述能带结构以及活性物种的类型推断出光生载流子的迁移方式将遵循S型机制,而不是传统的II型异质结.而且,通过光电流、阻抗和稳态荧光均证实了表面OVs和S型异质结的协同效应,有利于提高Bi4O5I2/Bi4O5Br2-OV的光生电子空穴对的分离效率,并延长其寿命,从而有效地提高其光催化性能.在可见光照射下,OVs和S型异质结的协同效应赋予Bi4O5I2/Bi4O5Br2-OV显著的可见光光催化性能,对抗生素四环素和染料罗丹明B的去除率分别高达90.2%和97.0%,均高于Bi4O5I2(56.8%和71.8%)、Bi4O5Br2(47.4%和68.4%)、固溶体BiOAc0.6Br0.2I0.2(67.0%和84.0%)以及表面具有低氧空位浓度的Bi4O5I2/Bi4O5Br2-P(30.6%和40.4%).此外,在实际废水或电解质存在下,S型Bi4O5I2/Bi4O5Br2-OV异质结仍呈现出优异的光催化性能.本文不仅为OVs修饰的富铋基异质结的设计提供了有效策略,也为界面载流子的分离和迁移提供了切实可行的途径.  相似文献   

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Barium bismuth titanate (BaBi4Ti4O15, BBT) powders were synthesized using the Pechini method, and related ceramics were prepared using a solid-state reaction method. The structure and morphology of the BBT specimens were examined by the X-ray diffraction and scanning electron microscopy. Complexation of citric acid with metallic cations was detected by Fourier-transform infrared spectroscopy. Thermal analyses of the obtained gels were performed using differential thermal gravimetry. Pure BBT powders could be obtained at a relatively low temperature of 500 °C. A broad dielectric peak around Curie temperature and significant frequency diffusion of the maximum dielectric permittivity were observed. The diffuseness parameter was 1.82, and relaxation was attributed to cationic disordering at the A-site of BBT.  相似文献   

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This study is reporting the role of embedded ferroelectric ceramics Bi4Ti3O12 (BTO = 1–5 wt%) into the polyvinylidene fluoride (PVDF) composites on its structural, bonding, surface morphology, and dielectric response. Especially lead free flexible composite electrodes have lot of attention due to its high dielectric permittivity and energy storage density. X-ray diffraction spectra confirms monophasic orthorhombic structure of composites, while Fourier transform infrared (FTIR) spectra confirms the bonding behavior. Scanning electron microscopy (SEM) images surface morphology of homogeneously distributed ceramic particles with interconnected network. Dielectric constant has been found to be improved from 9.56 to 13.73 for BTO5%PVDF95% composites at frequency of 1 kHz attributes promoted interfacial polarization of PVDF and effectively limited the charge leakage in the composites, implying promising applications in flexible electronic devices.  相似文献   

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Polyaniline–Nd2O3:Al2O3 nanocomposites were prepared by in situ oxidative polymerization method using different weight percentages of oxide powders. The prepared nanocomposites were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction for molecular and crystal structures. Scanning electron microscopy and transmission electron microscopy images show the tubular structure of polyaniline nanocomposite with embedded metal oxides. The electrical conductivity of the nanocomposites increases with increase in temperature as well as with concentration of Nd2O3:Al2O3 particles in polyaniline. This is because of the hopping of charge polarons and extended chain length of the nanocomposites as evidenced by the negative thermal coefficient (NTC) characteristic. A high NTC value of 2.67 was found in nanocomposites with 15 wt% of oxide particles. These nanocomposites show low dielectric constant and dielectric loss; the electrical conductivity is higher than 0.3 S/cm as confirmed by Cole–Cole plot that indicates a decrease in both grain resistance and bulk resistance of the nanocomposites. The current–voltage and capacitance–voltage measurements were also carried out. The carrier mobility μ values of pure polyaniline and nanocomposites were found to be 4.27 × 10?3 and 1.45 × 10–2 H.M?1, respectively. A significant enhancement in carrier mobility was observed in comparison with the literature. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

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Polycrystalline ceramic samples of Bi2Sn2?xTixO7 (x?=?0.0, 0.2, 0.4, 0.6, 0.8) have been synthesized by conventional solid-state reaction method. The effect of homovalent cation (titanium) substitution on the Sn-site on the structural, morphological, electrical and thermal properties of the pure Bi2Sn2O7 ceramics have been studied by X-ray diffraction (XRD) followed by scanning electron microscopic techniques, dc conductivity and modulated differential scanning calorimetry. The XRD analysis carried out by performing the Rietveld refinement using the space group Fd3m indicates that the increase of titanium contents do not lead to any secondary phase. The grain size distributions of all the samples were investigated by SEM. It was found that the grain sizes are strongly influenced by the addition of titanium to the system. The frequency and temperature dependent dielectric studies have been carried out. The dc conductivity measurement was carried out for all the compounds and the activation energies were calculated using the relation ???=???0 exp(?E a/kT). The modulated differential scanning calorimetry has been used to investigate the effect of substitution on the specific heat, heat flow and other thermal parameters of the compounds. The results are discussed in detail.  相似文献   

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