New evidence for an oxycarbonate phase as an intermediate step in BaTiO3 preparation

A newly developed method of spray hydrolysis of a barium-titanium double alkoxide will be described as an efficient synthetic route for the preparation of a stoichiometric BaTiO₃ powder. During the thermal treatment of the corresponding precursor a barium-titanium oxycarbonate appears as an intermediate. High resolution electron microscopy (HREM) and electron energy loss spectroscopy (EELS) at ionization edges (ELNES), along with X-ray powder diffractometry (XRD), Fourier-transformed infrared spectroscopy (FTIR), and thermoanalytical measurements provide evidence of the existence of such an oxycarbonate phase. The comparison of the measured EEL spectra with quantum-mechanical calculations using density functional theory (DFT) reveals that this intermediate phase is characterized by an electronic C-Ti interaction in the crystal lattice and a specific modification of the carbonate bond.     

纳米钛酸钡中钡和钛含量的快速测定

本文介绍快速测定纳米BaTiO3,中钡和钛含量的一种测定方法.用浓盐酸溶样,EDTA掩蔽钛,硫酸铵作为沉淀剂测定钡含量;用硫酸、硫酸铵溶样,金属铝还原二氧化钛,硫氰酸铵作指示剂,硫酸铁铵作标准滴定溶液测定钛含量.本法可以为研制和生产纳米钛酸钡提供一个快速、准确的钡钛含量分析测试方法.     

BaTiO_3粉体中Ti/Ba比分析方法的比较

提出了用ＫＯＨ熔融分解ＢａＴｉＯ３粉体〔１〕，再用浓ＨＣｌ酸化后，用感应耦合等离子体发射光谱法（ＩＣＰ—ＡＥＳ法）测定试样中的Ｔｉ／Ｂａ比，并与化学分析法的结果作了比较，显示出ＩＣＰ—ＡＥＳ法简便，快速，结果更好。     

钡钛比对钛酸钡陶瓷PTCR性能的影响

钡钛比是影响钛酸钡陶瓷PTCR性能的重要因素，采用固相反应法制备了不同钡钛比的样品，研究了钡钛比对钛酸钡陶瓷的显微结构和性能的影响。实验表明，轻微钛过量的系统具有较好的PTCR特性和较低的室温电阻率，与此相反，过量钡的存在将对烧结和半导化产生不利影响。并且钛过量的系统中过量的钛应该在一次配料中加入，否则由于钛在晶界上过量的偏析将导致难于烧结和过高的电阻。在实验的基础上对钛酸钡基PTCR陶瓷表面态的本质进行了讨论，认为受主表面态是VBa”和吸附O^2-共同作用的结果。     

Phase transformation in the synthesis of Ba(Ti1-xMx)O3-based PTCR ceramic

Systems based on BaTiO₃ with aliovalent substitutions of titanium by niobium, tantalum, molybdenum and tungsten have been investigated. The effect of substitution on the microstructure and electrophysical properties of ceramic is shown. Novel compounds with perovskite structure have been synthesized.     

Diffuse phase transition and ferroelectric study of (Ba,Bi)(Ti,Cr)O3 ceramics

Lead-free perovskite type (Ba_0.94Bi_0.06)(Ti_0.94Cr_0.06)O₃ (BBTC) ceramics have been prepared by the conventional mixed oxide method. The XRD results showed that BBTC ceramics have single phase tetragonal symmetry with space group P4mm. Dielectric studies exhibited a diffuse phase transition characterized by a strong temperature and frequency dispersion of permittivity. The quantitative characterization based on empirical parameters (ΔT_m, γ, ΔT_relax, and ΔT_dif) confirmed its relaxor nature. The origin of relax ferroelectric behavior is caused by the polar nanoclusters, which were arose due to the heterovalent substitutions of Bi³⁺ and Cr³⁺ at Ba²⁺ and Ti⁴⁺ sites. The P–E loops obtained at the temperature quite above T_m supported the diffuse phase transition behavior of the samples.     

Creating adjoining polymorphic phase transition (PPT) regions in ferroelectric (Ba,Sr)(Zr,Ti)O3 ceramics

In this work, we report the polymorphic phase transitions(PPT) in ferroelectric Ba_0.95Sr_0.05Zr_xTi_(1-x)O₃ (BSZT, x = 0.01–0.10) ceramics synthesized by using a solid-state reaction method. The doping elements and composition ratios were selected to create adjoining PPT phase boundaries near room temperature, hence to achieve a broadened peak of piezoelectric performance with respect to composition. The temperature-composition phase diagram was constructed and the effects of PPT on the electromechanical and ferroelectric properties of the ceramics were investigated. It was revealed that the two adjacent PPT regions at room temperature showed different characteristics in property enhancement. However, due to the proximity of the phase boundaries, Ba_0.95Sr_0.05Zr_xTi_(1-x)O₃ ceramics in a fairly broad range of compositions (0.02 ≤ x ≤ 0.07) showed excellent piezoelectric properties, including a large piezoelectric constant (312 pC/N ≤ d₃₃ ≤ 365 pC/N) and a high electromechanical coupling coefficient k_p (0.42 ≤ k_p ≤ 0.49).     

Phenomenological modeling of phase transitions and electrocaloric effect in Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3

Ba(Zr_0.2Ti_0.8)O₃-x(Ba_0.7Ca_0.3)TiO₃ (BZT-xBCT) is a promising lead-free ferroelectric system. In this paper, we present two sets of free energy coefficients and carry out phenomenological modeling to study the phase transition and electrocaloric effect. The calculated phase diagram is in excellent quantitative agreement with experiments. Furthermore, we propose a new method based on effective internal electric field to simulate polarization in the macroscopic paraelectric state of ferroelectric relaxor. The computed composition and temperature-dependent entropy and temperature change induced by electrocaloric effect are in good agreement with the measured data available for single crystal.     

Electrocaloric Effect in Ba(Zr,Ti)O3–(Ba,Ca)TiO3 Ceramics Measured Directly

In this paper, we report on studies of the electrocaloric (EC) effect in lead‐free (1?x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ ceramics with compositions range between 0.32 ≤ x ≤ 0.45. The EC effect was measured directly using a modified differential scanning calorimeter. The maximum EC temperature change, ΔT_direct = 0.33 K under an electric field of 2 kV/mm, was observed for the composition with x = 0.32 at ~63°C. We found that the EC effect peaks not only around the Curie temperature but also at the transition between the ferroelectric phases with different symmetries. A strong discrepancy observed between the results of the direct measurements and indirect estimations points out that using Maxwell's equations is invalid for the thermodynamic nonequilibrium conditions that accompany only partial (incomplete) poling of ceramics. We also observe a nonlinearity of the EC effect above the Curie temperature and in the temperature range corresponding to the tetragonal ferroelectric phase.     

Dielectric and Structural Studies in the Systems Ba(Ti, Nb)O3 and Ba(Ti, Ta)O3

The dielectric properties, lattice parameters, and X-ray and neutron diffraction intensities of solid solutions of BaTiO₃ containing Nb or Ta were studied. These solid solutions have a perovskite-type structure with part of the Ti⁴⁺ ions replaced by Nb⁵⁺ or Ta⁶⁺ ions and with some cation vacancies. These solid solutions exhibit a remarkable lowering of the Curie point, but the tetragonal-orthorhombic and the orthorhombic-rhombohedral transition points are raised.     

A facile pot synthesis of (Ti3AlC2) MAX phase and its derived MXene (Ti3C2Tx)

Various processing techniques reported in the literature for synthesizing the Ti₃AlC₂ MAX phase involve high calcination temperature, expensive equipment, and inert environmental requirement. Here, we report a cost-effective, solid-state, single-step synthesis route of the Ti₃AlC₂ MAX phase. Optimizing the stoichiometry of the precursors and controlling the thermal treatment, the desired MAX phase has been attained, as confirmed by XRD analysis. Further, Ti₃C₂T_x (where, T_x: O, OH, F functional groups) MXene was prepared from this one-pot synthesized MAX phase. FESEM, TEM, and Raman spectroscopy were used to ensure that the hexagonal structure of the MAX phase was retained in as-synthesized MXene. Further, XPS was employed to detect the presence of surface functional groups (-O, –OH, and –F) on the MXene surface. UV–vis spectroscopy shows a strong absorption peak in the NIR region.     

Local structure study of phase transition behavior in Ba(Ti,Sn)O3 perovskite by X-ray absorption fine structure

In this work, BaTi_1−xSn_xO₃ (BST) powders (x=0–0.95) were synthesized by a conventional mixed-oxide method. The phase information was investigated by a combination of X-ray diffraction and X-ray absorption spectroscopy techniques. The XRD measurements indicated the global phase transition from tetragonal to cubic perovskite structure. From the synchrotron X-ray Absorption Near-Edge Structure (XANES) measurements at the Ti K-edge and Sn L₃-edge, it was seen that an increase of Sn content in BaTiO₃ affected the phase transition behavior and local structure of BST. In addition, the local structure of Ba(Ti,Sn)O₃ materials were experimentally determined and compared with that obtained from the simulation. The local structure obtained from the XANES technique provided additional structural information unavailable from XRD investigation. Finally, the phase transition behavior from relaxor ferroelectric to polar cluster in BST system was discussed and attributed mainly to the change in the local structure.     

High piezoelectricity in CuO-modified Ba(Ti0.90Sn0.10)O3 lead-free ceramics with modulated phase structure

High piezoelectricity was achieved in Ba(Ti_0.90Sn_0.10)O₃ lead-free ceramics by optimizing CuO addition and sintering temperature. The phase structure of 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramic is coexisting rhombohedral and tetragonal phases as sintered at 1300 °C. The coexistence of rhombohedral, tetragonal and orthorhombic phases appears in 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramics as sintered at 1350–1450 °C, which leads to highly enhanced d₃₃ up to 650pC/N. This work demonstrates that high piezoelectric property (d₃₃ = 650pC/N) can be obtained in BaTiO₃-based lead-free piezoceramics with a simple composition modification by modulating phase structures, which also indicates that Ba(Ti,Sn)O₃ is a promising candidate to replace the lead-based piezoceramics.     

On the origin of grain size effects in Ba(Ti0.96Sn0.04)O3 perovskite ceramics

Over the last 50 years, the study of grain size effects in ferroelectric ceramics has attracted great research interest. Although different theoretical models have been proposed to account for the variation in structure and properties of ferroelectrics with respect to the size of structural grains, the underlying mechanisms are still under debate. Here, we report the results of a study on the influence of grain size on the structural and physical properties of Ba(Ti_0.96Sn_0.04)O₃ (BTS), a ferroelectric compound that represents a model perovskite system, where the effects of point defects, stoichiometry imbalance and phase transitions are minimized by chemical substitution. It was found that different microscopic mechanisms are responsible for the different grain size dependences observed in BTS. High permittivity is achieved in fine-grained BTS ceramics due to high domain wall density and polar nanoregions; high d₃₃ is obtained in coarse-grained ceramics due to a high degree of domain alignment during poling; large electric field-induced strain in intermediate-grained ceramics is an outcome of a favorable interplay between constraints from grain boundaries and reversible reorientation of non-180° domains and polar nanoregions. These paradigms can be regarded as general guidelines for the optimization of specific properties of ferroelectric ceramics through grain size control.     

Enhanced thermal stability of piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O3 systems through tailoring phase transition behavior

Good thermal stability in lead-free BaTiO₃ ceramics is important for their applications above room temperature. In this study, thermal stable piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O₃ ceramics was enhanced by tailoring their phase transition behaviors. Comparison between (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ and (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ revealed that latter system at y?=?0.80 had much better thermal stable piezoelectric coefficient than the former at x?=?0.45. Both systems crystalized in tetragonal to orthorhombic phase boundary at room temperature. The phase transition temperature and degree of diffusion were adjusted by Ca and Zr ions contents and demonstrated great influence on temperature dependent dielectric permittivity, hysteresis loops, and in-situ domain structures. The improved thermal stability of (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ prepared at y?=?0.80 was linked to its higher paraelectric to ferroelectric phase transition temperature (T_m?=?115.7?°C) and less degree of diffusion (degree of diffusion constant γ?=?1.35). By comparison, (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ prepared at x?=?0.45 revealed T_m?=?81.3?°C and γ?=?1.65. Overall, these findings look promising for future stimulation of phase transition behaviors and design of piezoelectric materials with good thermal stabilities.     

Green synthesis,formation mechanism and oxidation of Ti3SiC2 powder from bamboo charcoal,Ti and Si

Using low-cost and highly reactive bamboo charcoal, Ti and Si elemental powders as starting materials, Ti₃SiC₂ powder was synthesized via a simple and cost-efficient pressureless sintering technique in argon atmosphere. The influences of synthesis temperature, holding time and Si content on the Ti₃SiC₂ content of the synthesized products were investigated, and the analysis indicated that the relative content of Ti₃SiC₂ reached 98.9 wt% with a molar ratio of 3Ti/1.2Si/2.2C at 1400 °C for 1.5 h. The Ti₃SiC₂ with good crystallinity and homogeneous nanolayered structure was synthesized at lower temperatures due to the high reactivity and high specific surface area of bamboo charcoal. The non-isothermal oxidation behavior showed that Ti₃SiC₂ powder was stable in air below 540 °C. With the temperature increasing up to 1300 °C, continuous and dense TiO₂ and SiO₂ oxidation layers were formed on the surface of Ti₃SiC₂ particles, which conferred good oxidation resistance to Ti₃SiC₂ powder.     

Effect of compositional variations on phase transition and electric field-induced strain of (Pb,Ba) (Nb,Zr, Sn,Ti)O3 ceramics

(Pb_0.97Ba_0.02)Nb_0.02(Zr_0.55Sn_0.45?xTi_x)_0.98O₃ (PBNZST, 0.03≤x≤0.06) ceramics were prepared by conventional solid state synthesis and their crystal structure, ferroelectric, dielectric, and electric field-induced strain properties were systemically investigated. A transformation from antiferroelectric (AFE) phase to ferroelectric (FE) phase was observed at 0.05<x<0.06. Besides, with the increase of Ti content, the electric field-induced strain decreased, due to the larger strain of AFE ceramics compared to FE ceramics. Further, when the measuring frequency decreased, the strain improved, because the electric field at low frequency allows a more efficient switching of domains, resulting in larger strain. The maximum strain of 0.55% was obtained in (Pb_0.97Ba_0.02)Nb_0.02(Zr_0.55Sn_0.45?xTi_x)_0.98O₃ antiferroelectric ceramics with x=0.03 at 2 Hz.     

Ferroelectric,dielectric, and impedance properties of Sm-modified Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 ceramics

To investigate the effect of Sm doping on the electrical properties of Ba(Zr_0.2Ti_0.8)O₃-x(Ba_0.7Ca_0.3)TiO₃ (BZT-xBCT) (x = 40, 50, 60) ceramics, three Sm-modified ceramics were prepared using the conventional solid-state reaction method. Related electrical measurements, including ferroelectric and dielectric investigations and impedance spectroscopy, were recorded for these ceramics. It was found that a tilted morphotropic phase boundary resulted from the addition of Sm, which induced the best piezoelectric properties and insulating behaviour in the Sm-BZT-60BCT sample. An abnormal P-E loop shrinkage appeared in the Sm-BZT-50BCT sample but not in the other two samples. This could be attributable to the different electronegativities between Ca²⁺ and Ba²⁺ and between Zr⁴⁺ and Ti⁴⁺, whose contents are different in varied samples and have an effect on defect-dipole alignment as well as spontaneous polarization. The activation energies for the bulk conductivity in the three composites were calculated to be 0.28 ± 0.01, 0.08 ± 0.01, and 0.36 ± 0.01 eV, confirming the existence of oxygen vacancies in our samples. The Sm dopant is responsible for the oxygen vacancies. This also leads to an increased Curie temperature in the three composites.     

Hydrothermal synthesis of Ba(Ti, Sn)O3 fine powders and dielectric properties of the corresponding ceramics

Fine powders of submicron-sized crystallites of BaTiO₃ were prepared at 85–130°C by the hydrothermal method, starting from TiO₂.ξH₂O gel and Ba(OH)₂ solution. The products obtained below 110°C incorporated considerable amounts of H₂O and OH⁻ in the lattice. As-prepared BaTiO₃ is cubic and converts to the tetragonal phase after heat treatment at 1200°C, accompanied by the loss of residual OH⁻ ions. Hydrothermal reaction of SnO₂.ξH₂O gel with Ba(OH)₂ at 150–260°C gives rise to the hydrated phase, BaSn(OH)₆.3H₂O, due to the amphoteric nature of SnO₂.ξH₂O which stabilises Sn(OH)₆²⁻ anions in basic media. On heating in air or releasing the pressure in situ at 260°C, BaSn(OH)₆.3H₂O converts to BaSnO₃ through an intermediate, BaSnO(OH)₄. Solid solutions of Ba(Ti,Sn)O₃ are directly formed from (TiO₂ + SnO₂)..ξH₂O gel up to 35 mol% SnO₂. At higher Sn contents, the hydrothermal products are mixtures of BaSn(OH)₆.3H₂O and BaTiO₃, which on annealing at 1000°C result in monophasic Ba(Ti,Sn)O₃. The sintering characteristics and the dielectric properties of the ceramics prepared out of these fine powders are presented. The dielectric properties of fine-grained Ba(Ti,Sn)O₃ ceramics are explained on the basis of the prevailing diffuse phase transition behaviour.     

Influence of [Ba + Ca]/[Ti + Zr] Ratio on the Interfacial Property of (Ba,Ca)(Ti,Zr)O3 (BCTZ) Powders in an Aqueous Medium

We report findings on the electrokinetic and solubility behaviors of (Ba,Ca)(Ti,Zr)O₃ (BCTZ) powders having three different [Ba + Ca]/[Ti + Zr] ratios: 0.995, 1.000, and 1.005. Electrokinetic and solubility properties of BCTZ powders in aqueous media are phenomenologically similar to BaTiO₃. Ba and Ca ions, occupying primarily A-sites on the perovskite lattice, dissolve during acid titration, which results in surface depletion of A-site cations in the surface region of BCTZ particles. The electrokinetics of colloidal BCTZ powders reflects changes in the surface chemistry that occur as a result of dissolution and adsorption/reprecipitation of surface ions. An increase in [Ba + Ca]/[Ti + Zr] ratio results in an increase in the dynamic mobility at all pH values, an increase in the titration hysteresis, and an increase in the isoelectric pH. Each of these effects can be attributed to Ba and Ca in the near-surface region of BCTZ.