Leading role of grain boundaries in colossal permittivity of doped and undoped CCTO

The role of grain boundaries in the colossal permittivity ɛ of doped and undoped calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO), is illustrated by a first correlation – over four orders of magnitude – between ɛ and the capacity of grain boundaries, not that of grains, deduced from the analysis of impedance measurements. The DC resistance of the CCTO sample which is essential to make efficient capacitors for technological applications, as well as the loss factor tan(δ), are found to be correlated with the resistance of the grain boundaries rather than that of the grains. The correlation extends over almost seven orders of magnitude. These findings, consistent with the internal barrier layer capacitance (IBLC) model, indicate the leading role of grain boundaries in the origin of the capacitance of CCTO samples.     

The effect of titanium excess and deficiency on the microstructure and dielectric properties of lanthanum doped Ba0.55Sr0.45TiO3 with colossal permittivity

The temperature dependent dielectric properties of (Ba_0.54875Sr_0.44875La_0.0025)Ti_(1+x)O₃ with both an excess and a deficiency of 0.25 mol.% TiO₂ were investigated. The samples were prepared by the mixed oxide method and sintered in a conventional oven at temperatures ranging from 1400 °C to 1475 °C. The cubic perovskite structure was confirmed with XRD at room temperature. The sample with an excess of 0.25 mol.% Ti exhibited reduced grain growth while abnormal grain growth was observed for samples without Ti modification. Samples exhibited colossal permittivity for all modified compositions. With a 0.25 mol.% deficiency of Ti a permittivity over 65,000 and a tan δ under 0.05 were measured over a temperature range of ?68 °C to 150 °C and a frequency range between 50 kHz and 1 MHz. This paper shows that by fine tuning the composition, materials with new, exciting and widely adjustable dielectric properties can be achieved.     

Disappearance and recovery of colossal permittivity in (Nb+Mn) co-doped TiO2

We investigate the effects of doping and annealing on the dielectric properties of metal ions doped TiO₂ ceramics. Colossal permittivity (CP) above 10⁴ was observed in single Nb ion doped TiO₂, which was dominated by electron transport related interfacial polarization. Moreover, the CP can be dropped to 120 when simultaneously introducing Mn ion into the sample. The disappearance of CP behaviors maybe due to the multivalence of Mn which would inhibit the reduction of Ti⁴⁺ to Ti³⁺, and thus reduce delocalized electrons. Interestingly, the CP was recovered for the (Nb+Mn) co-doped TiO₂ after post-sintering heat treatment in N₂ atmosphere. The recovery of CP in the sample after annealing can be ascribed to the semiconducting grain and the insulating grain boundary, according to impedance spectroscopy. We therefore believe that this work can help us understand the mechanism of CP from a new perspective.     

Ionic conduction,colossal permittivity and dielectric relaxation behavior of solid electrolyte Li3xLa2/3-xTiO3 ceramics

Perovskite-type solid electrolyte lanthanum lithium titanate (LLTO), exhibiting high intrinsic ionic conductivity, has been attracting interests because of its potential use in all solid-state lithium-ion batteries. In this work, we prepared LLTO ceramics by solid state reaction method and studied their conductivity and dielectric properties systematically. It is found that the bulk conductivity of LLTO is several orders of magnitude higher than the grain boundary conductivity. In addition, colossal permittivity was observed in LLTO ceramics in wide frequency/temperature ranges. Two non-Debye type relaxation peaks were observed in the imaginary part of permittivity, resulting from Li⁺ ions motion and accumulation near interfaces of grains/grain boundaries/electrodes. It is suggested that colossal permittivity may originate from the lithium ion dipoles inside the samples and the interfacial polarization of lithium ion accumulation near the grain boundaries. These results clarify the relations among colossal permittivity, relaxation behavior and ionic conduction in solid ion conductor ceramics.     

A-site Ca2+ substitution induced polyvalent Cu cations and correlated polaron relaxations in colossal permittivity Li1-xCaxCuNb3O9

LiCuNb₃O₉ has been reported newly a colossal permittivity (CP) perovskite, in which the B-site NbO₆ octahedra play a bridging role in the polaron hopping. However, how the A-site modification affects the origin of the polarons and further the CP behaviours remains unexplored. To this end, A-site Ca²⁺ was incorporated to form Li_1-xCa_xCuNb₃O₉, and the local states, dielectric relaxations and conduction behaviours were comprehensively studied. The substitution induces the polyvalent Cu cations, i.e. Cu⁺/Cu²⁺/Cu³⁺. Bond valence sum calculations imply that Cu²⁺ and Cu³⁺ are underbonded, and Cu⁺ is overbonded, while B-site Nb⁵⁺ shows slightly different with theoretical pentavalence. All the compositions exhibit a similarly room-temperature CP response, but present two dielectric relaxations, i.e. T_R1:170–300 K and T_R2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the T_R1 follows the variable-range-hopping where the electron hopping between the mixed Cu⁺/Cu²⁺, while T_R2 contributes from the Cu³⁺ nearest neighbor hopping.     

Ge4+ doped CaCu2.95Zn0.05Ti4O12 ceramics: Two-step reduction of loss tangent

CaCu₃Ti₄O₁₂ ceramics have been extensively studied for their potential applications as capacitors in recent years; however, these materials exhibit very large dielectric losses. A novel approach to reducing the dielectric loss tangent in two steps, while increasing the dielectric permittivity, is presented herein. Doping CaCu₃Ti₄O₁₂ with a Zn dopant reduces the loss tangent of the ceramic material from 0.227 to 0.074, which is due to the increase in grain boundary (GB) resistance by an order of magnitude (from 6.3× 10³ to 3.93 × 10⁴ Ω cm). Zn-doping slightly changes the microstructure and dielectric permittivity of the CaCu₃Ti₄O₁₂ ceramic, which reveals that the primary role of the Zn dopant is to tune the intrinsic properties of the GBs. Surprisingly, the addition of the Ge⁴⁺ dopant into the Zn²⁺-doped CaCu₃Ti₄O₁₂ ceramic sample led to a further decrease in the loss tangent from 0.074 to 0.014, due to enhanced GB resistance (3.1 × 10⁵ Ω cm). The grain size increased remarkably from 2–3 μm to 85–90 μm, corresponding to a significant increase in the dielectric permittivity (~1–4 × 10⁴). The large increase in GB resistance is due to the intrinsic potential barrier height at the GBs and the segregation of the Cu-rich phase in the GB region. First-principles calculations revealed that Zn and Ge are preferentially located at the Cu sites in the CaCu₃Ti₄O₁₂ structure. The substitution of the Ge dopant does not hinder the role of the Zn dopant in terms of improving the electrical properties at the GBs. These phenomena are effectively explained by the internal barrier layer capacitor model. This study provides a way of improving the dielectric properties of ceramics for their practical use as capacitors.     

Optimize the dielectric properties of CaCu3Ti4O12 ceramics by adjusting the conductivities of grains and grain boundaries

Reduction of dielectric loss for CCTO ceramics is a prerequisite for their applications. Considering internal barrier layer capacitance effect, improving the capacitance and grain boundary resistance is an effective way to reduce dielectric loss. Therefore, more conductive Ti³⁺ and Cu⁺ ions were introduced to grains by adding carbon to ceramic bodies, improving the permittivity of CCTO ceramics. Annealing was performed to increase the grain boundary resistance. The dielectric loss of the CCTO ceramics thus prepared, which maintain a giant permittivity, is significantly reduced. Specifically, the CCTO ceramic with carbon addition, which was sintered at 1080 °C for 8 h and air annealed at 950 °C for 2 h, exhibits a giant permittivity of about 2.50(5)×10⁴ and a low dielectric loss of less than 0.050(2) from below 20 Hz to 50 kHz at room temperature. Meanwhile, its dielectric loss at 1–10 kHz is less than 0.050(2) from below room temperature to about 100 °C.     

Colossal permittivity in BaTiO3-0.5wt%Na0.5Ba0.5TiO3 ceramics with high insulation resistivity induced by reducing atmosphere

The donor-acceptor co-doping grain-fine BaTiO₃-0.5wt%Na_0.5Ba_0.5TiO₃ (BT-0.5wt%NBT) ceramics are obtained by conventional solid-state reaction method and sintered in different atmospheres. The dielectric properties are sensitively influenced by the sintering atmosphere, which the colossal permittivity can be activated and increased by enhanced atmospheric reducibility with the increase of H₂ content. However, the excessive H₂ content can make a significant deterioration in dielectric loss and insulation resistivity. The impedance spectra, XPS and EPR measurements indicate that sintering atmosphere can effectively regulate the concentration and distribution of charge carriers (delocalized electrons, oxygen vacancies and defects), which induce the interfacial polarization and hopping polarization. When sintered in 0.1% H₂/N₂, the sample possesses a relatively good comprehensive performance with colossal permittivity (ε_γ>4×10⁴), ultra-low dielectric loss (tanδ=0.0218) and high insulation resistivity (ρ_v>10¹¹Ω·cm), which related to the moderate values of resistance and conduction activation energy for the grain boundaries.     

Colossal permittivity in TiO2 co‐doped by donor Nb and isovalent Zr

Effect of isovalent Zr dopant on the colossal permittivity (CP) properties was investigated in (Zr + Nb) co‐doped rutile TiO₂ ceramics, i.e., Nb_0.5%Zr_xTi_1?xO₂. Compared with those of single Nb‐doped TiO₂, the CP properties of co‐doped samples showed better frequency‐stability with lower dielectric losses. Especially, a CP up to 6.4 × 10⁴ and a relatively low dielectric loss (0.029) of x = 2% sample were obtained at 1 kHz and room temperature. Moreover, both dielectric permittivity and loss were nearly independent of direct current bias, and measuring temperature from room temperature to around 100°C. Based on X‐ray photoelectron spectroscopy, the formation of oxygen vacancies was suppressed due to the incorporation of Zrions. Furthermore, it induced the enhancement of the conduction activation energy according to the impedance spectroscopy. The results will provide a new routine to achieve a low dielectric loss in the CP materials.     

采用核/壳技术制备P(VAc—BA)乳液的研究

采用核/壳技术制备了P(VAc—BA)系乳液,探讨了核/壳组成变化对乳液性能的影响。研究表明,核/壳比相同时,壳中丙烯酸丁酯(BA)含量对乳液T_g值、成膜性能及膜的力学性能均有影响;当核层和壳层中单体组成相同时,壳层的厚度越大,MFT值则越低;在总组成和核/壳比一定时,只改变核层和壳层单体的组成,也可以在一定范围内使乳液的特性发生变化。     

Influence of grain boundary sliding on diffusion in yttria doped zirconia

Grain boundary sliding during high temperature deformation can lead to stress concentrations and an enhancement of diffusion in mobile boundaries. Experiments were conducted on a fine grained 3 mol% yttria stabilized tetragonal zirconia, under conditions associated with superplastic flow involving grain boundary sliding. Tracer diffusion studies under creep conditions and without load indicate that there is no enhancement in either the lattice or grain boundary diffusivities. The experimental creep data are consistent with an interface controlled diffusion creep mechanism.     

Influence of CaF2 and AlF3 on the kinetics and mechanism of the Al electrode reaction in cryolite melts with various alumina contents

Electrochemical techniques were used to study the kinetics and mechanism of the aluminium electrode reaction in two cryolite-based melts containing cryolite with either 11 wt % AlF₃ or 5 wt % CaF₂ additions and variable alumina contents at 1000 °C. A three step electrode process was observed in both melts, comprising a preceding chemical reaction followed by two charge transfer steps. The exchange current density of the cathodic reaction was found to be dependent on the concentration of aluminium fluoride. By a combination of electrochemical impedance spectroscopy (EIS) and galvanostatic relaxation methods (GRM), the exchange current density of the first (slower) charge transfer step, the Warburg diffusion impedance, the double layer capacitance of the aluminium electrode and the rate of the preceding chemical step, were evaluated in the range of 2–8 wt % alumina. The role of the two additives, AlF₃ and CaF₂, was evaluated.     

Preparation of PBAS core-shell structured polymer by seeded emulsion polymerization and investigation in AS resin toughness

The preparation of poly(n-butyl acrylate)/poly(acrylonitrile-co-styrene), i.e., poly(BA)/poly(AN-co-St) (PBAS) core-shell structured modifier with controlled particle size was reported, and the mechanical properties of AS/PBAS blends were investigated. The modifier was prepared at a solid content of 50 wt % by a two-stage sequential emulsion polymerization. Dynamic light scattering (DLS) was used to monitor the particle diameters and showed that the particles grew without significant secondary nucleation occurring. The morphology was confirmed by means of transmission electron microscopy (TEM). According to the research on mechanical properties of the AS/PBAS blends, a remarkable toughening effect of PBAS on AS resin was found. By means of scanning electron microscopy (SEM) observation, the toughening mechanism was proposed to be crazing caused by rubber particles and shear yielding of AS matrix. Uniform dispersion of rubber particles in AS matrix was attributed to the good compatibility between AS and PBAS modifier. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of divalent cation addition on structure,conductivity and grain boundary properties in La doped ceria oxygen ion conductors

The aim of this work is to investigate the effect of divalent cations on the structure and electrical properties of Ce_0.85La_0.1D_0.05O_2-δ (D = Ca, Sr and Ba) oxygen ion conductors. The X-Ray structural analysis confirms the presence of CeDO₃ minor phase in addition to cubic fluorite phase of ceria in Sr²⁺ and Ba²⁺ added compositions. The lattice parameter of the compositions significantly depends on the ionic radius of dopants and the presence of D²⁺ ions in ceria lattice. The Ca²⁺ added composition shows the highest free oxygen vacancy concentration due to its lowest association energy and complete dissolution of Ca²⁺ ions into ceria lattice. The dopant-vacancy association energy and grain interior conductivity changes with the ionic radii of the divalent dopants. The grain boundary capacitance depends on dielectric constant, grain size and grain boundary thickness. The grain boundary conductivity shows 46% over total conductivity for Sr²⁺ added composition. The presence of CeDO₃ phase and space charge layer promotes the grain boundary resistances and affects the ion dynamics. Schematic models are proposed to understand the ion migration in grain boundaries. The scavenging effect is found to be highest in Sr²⁺ ions added composition. The defect structures, the presence of CeDO3 phase and electrical properties are correlated with each other.     

原子层沉积技术在钛改性多孔氧化铝上的应用

采用原子层沉积技术进行Al₂O₃表面钛改性,利用N2吸附-脱附、X射线衍射、X射线荧光分析、透射电镜和热重-微分热重-差示扫描量热等表征手段对改性前后的Al₂O₃载体进行表征。结果表明,钛分散到Al₂O₃表面,Al₂O₃载体表面氧化钛为锐钛矿结构,改性后的载体具有良好的热稳定性。钛分散性与Al₂O₃表面化学环境有关,钛对多孔Al₂O₃表面改性可以通过原子层沉积技术实现。     

Control of abnormal grain inclusions in the nanocrystalline diamond film deposited by hot filament CVD

Formation of abnormal grain inclusions in nanocrystalline diamond films deposited by hot filament CVD (HFCVD) was investigated. The phenomenon was attributed to two different origins: an intrinsic and an extrinsic one. The inclusions due to the intrinsic origin could be either avoided or weakened by controlling chamber pressure, CH₄/N₂ concentrations in H₂, and by positive substrate bias. The extrinsic origin for the abnormal grains was found to be the contamination from the alumina insulation tubes for the thermocouple placed near the substrate, which were degraded by the extended exposure to the high temperature and strongly reducing atmosphere.     

Control of transport phenomena in the interior of the reforming catalyst grain: A new approach to the optimisation of the reforming process

The aim of the study was to provide favourable conditions for the transport of the reagents by modifying the porous structure and shape of the reforming catalyst grain. The study entailed the analysis of the transport phenomena and reactions that occur in spherical, cylindrical and slab-shaped catalyst grains. To upgrade the efficiency of the catalyst, use was made of analytical equations that describe the changes in the concentrations of the reagents in the catalyst grain. The equations were derived from the mass balances and the kinetic scheme assumed for the reforming process. By virtue of the coefficients of reagent diffusion, the equations are a function of the porous structure parameters and can therefore define a more or less advantageous profile of concentrations. The modification of the profile by minimising the objective function proposed in the paper leads to the reduction in the influence of diffusion resistance on the course of the reforming process. The study demonstrates that after the porous structure of the experimental catalyst had been changed, it was possible to increase its specific surface area and mechanical strength and, at the same time, noticeably improve the conditions for the transport of reagents.