折叠结构的PVDF/BTO复合薄膜压电纳米发电机的制备及性能研究

为提高聚偏氟乙烯(PVDF)的压电输出性能,将钛酸钡(BTO)纳米颗粒引入到PVDF溶液中,使用流延法制备PVDF/BTO复合压电薄膜,采用高温拉伸与电极化工艺处理复合薄膜。使用扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、差示扫描量热仪和准静态压电常数测试仪对复合薄膜的形貌和压电性能进行表征,探究BTO含量对PVDF/BTO复合薄膜的影响,研究BTO诱导PVDF链条偶极子重新排列形成β晶型的机理。结果表明,当BTO含量为10%(质量分数)时,PVDF/BTO复合薄膜的晶体结构中β晶型的含量最多,压电性能最强。最后设计了不同层数的折叠结构并组装制成压电纳米发电机(PENG),发现折叠层数越多,PENG的最大输出电压越高。

Effect of solvents on the morphology and structure of barium titanate synthesized by a one-step hydrothermal method

Tetragonal barium titanate was synthesized from barium hydroxide octahydrate and titanium tetrachloride through a simple one-step hydrothermal method.The effect of different solvents on the crystal structure and morphology of barium titanate nanoparticles during the hy-drothermal process was investigated.Except for ethylene glycol/water solvent,impurity-free barium titanate was synthesized in pure water,methanol/water,ethanol/water,and isopropyl alcohol/water mixed solvents.Compared with other alcohols,ethanol promotes the formation of a tetragonal structure.In addition,characterization studies confirm that particles synthesized in methanol/water,ethanol/water,and isopropyl al-cohol/water mixed solvents are smaller in size than those synthesized in pure water.In the case of alcohol-containing solvents,the particle size decreases in the order of isopropanol,ethanol,and methanol.Among all the media used in this study,ethanol/water is considered the optimum reaction media for barium titanate with high tetragonality(defined as the ratio of two lattice parameters c and a,c/a=1.0088)and small aver-age particle size(82 nm),which indicates its great application potential in multilayer ceramic capacitors.

表面负载Fe_(3)O_(4)对BT@PANI/PVDF复合材料介电性能的影响

通过氧化沉淀法制备出钛酸钡@聚苯胺-四氧化三铁(BT@PANI-Fe_(3)O_(4))核壳粒子,并以此为填料制备了聚偏氟乙烯(PVDF)介电复合材料,研究了硫酸亚铁铵(FAS)与BT@PANI核壳粒子的质量比对复合材料介电性能的影响。结果表明:在测试频率范围,复合材料的介电常数随着FAS与BT@PANI质量比的增加而增大,当FAS与BT@PANI核壳粒子的质量比为1∶1时,BT@PANI-Fe_(3)O_(4)/PVDF复合材料的介电常数可达14(100 Hz),与BT@PANI/PVDF(12,100 Hz)复合材料相比,介电常数得到提高,介电损耗保持在0.1左右,在高频时,BT@PANI-Fe_(3)O_(4)/PVDF介电损耗(0.03,104 Hz)小于BT@PANI/PVDF(0.09,104 Hz)复合材料,满足实际应用。报道的多壳层策略可以扩展到各种无机杂化物,以开发新型介电纳米复合材料。

Dopant Behaviours of Sm_2O_3 on Microstructure and Properties of Barium Zirconium Titanate Ceramics

The effect of Sm 2O 3 dopant on the sintering characteristics and dielectric properties of barium zirconium titanate ceramics (BaZr x Ti 1- x O 3) was investigated. It is shown that trace amount of Sm 2O 3 can greatly affect the grain growth and densification of barium zirconium titanate ceramics during sintering. At the same time, the dielectric peak at high temperature shifts to lower temperature and that at low temperature shifts to higher temperature. The two dielectric peaks overlap with each other when the Sm 2O 3 dopant content varies from 0 25% to 1%, and the maximum relative dielectric constant is greatly enhanced. These effects may be attributed to the substitution actions of the rare earth element in perovskite lattice. At the doping content of 0 75%, the dielectric constant maximum of 23570 can be obtained. By adopting some proper additives, an excellent Y5V dielective material is obtained, and the room temperature properties are as follows: relative dielectric constant ε RT ≥23,000, dielectric loss tgδ≤0 0075 and the breakdown strength under alternating field E b≥5 kV·mm -1 .

Optimized growth and dielectric properties of barium titanate thin films on polycrystalline Ni foils

Barium titanate（BTO） thin films were deposited on polycrystalline Ni foils by using the polymer assisted deposition（PAD） technique.The growth conditions including ambient and annealing temperatures were carefully optimized based on thermal dynamic analysis to control the oxidation processing and interdiffusion.Crystal structures,surface morphologies,and dielectric performance were examined and compared for BTO thin films annealed under different temperatures.Correlations between the fabrication conditions,microstructures,and dielectric properties were discussed.BTO thin films fabricated under the optimized conditions show good crystalline structure and promising dielectric properties with εr～ 400 and tan δ 〈 0.025 at 100 kHz.The data demonstrate that BTO films grown on polycrystalline Ni substrates by PAD are promising in device applications.

Effects of Dysprosium Oxide Doping on Microstructure and Properties of Barium Titanate Ceramic

Different amounts of dysprosium oxide were incorporated into barium titanate powders synthesized by hydrothermal method. Relations of substitution behaviors and lattice parameters with solid-solubility were studied. Furthermore, the influences of dysprosium oxide doping fraction on grain size and dielectric properties of barium titanate ceramic, including dielectric constant and breakdown electric field strength , were investigated via scanning electron microscope, X-ray diffraction and electric property tester. The results show that dysprosium oxide can restrain abnormal grain growth during sintering and that fine-grained and high density of barium titanate ceramic can result in excellent dielectric properties. As mass fraction of dysprosium oxide is 0.6%, the lattice parameters of grain increase to the maximum because of the lowest vacancy concentration. The electric property parameters are cited as following： dielectric constant （25 ℃ ） reaches 4100, the change in relative dielectric constant with temperature is - 10% to 10% within the range of - 15 - 100 ℃, breakdown electric field strength （alternating current） achieves 3.2 kV·mm^-1, which can be used in manufacturing high voltage ceramic capacitors

PREPARATION OF HIGH-PURITY AND NANOMETER-SCALE BARIUM TITANATE POWDERS

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Barium titanate ceramic inks for continuous ink-jet printing synthesized by mechanical mixing and sol-gel methods

Ink-jet printing of ceramic thick films is one of low cost on-site ceramic pattern fabrication methods.It is necessary to investigate the rheological behaviour of ceramic inks and drying behaviour of droplets.Two kinds of BaTiO3 ceramic inks were prepared by mechanical mixing and sol-gel methods,respectively.The effect of preparation parameters,such as quantity of polyacrylic acid(PAA)and solid content,on physicochemical and rheologic properties of the ceramic inks was investigated.The results show that they satisfy the requirements of continuous ink-jet printing.The appearances of printed dots and single printed layers were observed by SEM.The SEM images indicate that dots printed with mixing method ink are in ring shape,and dots printed with sol-gel method ink are in pancake shape,so the printed layer surface with the latter ink is smoother.The causes of these phenomena were discussed.

Modulating the Selectivity of Photocatalytic CO_(2)Reduction in Barium Titanate by Introducing Oxygen Vacancies

Artifi cial photosynthetic reduction of CO_(2) into valuable chemicals is one of the most promising approaches to solve the energy crisis and decreasing atmospheric CO_(2) emissions.However,the poor selectivity accompanied by the low activity of photocatalysts limits the development of photocatalytic CO_(2) reduction.Herein,inspired by the use of oxygen vacancy engi-neering to promote the adsorption and activation of CO_(2) molecules,we introduced oxygen vacancies in the representative barium titanate(BaTiO 3)photocatalyst for photocatalytic CO_(2) reduction.We found that oxygen vacancies brought signifi cant diff erences in the CO_(2) photoreduction activity and selectivity of BaTiO 3.The intrinsic BaTiO 3 showed a low photocatalytic activity with the dominant product of CO,whereas BaTiO 3 with oxygen vacancies exhibited a tenfold improvement in photocatalytic activity,with a high selectivity of~90%to CH 4.We propose that the presence of oxygen vacancies promotes CO_(2) and H 2 O adsorption onto the BaTiO 3 surface and also improves the separation and transfer of photogenerated carriers,thereby boosting the photocatalytic CO_(2) reduction to CH 4.This work highlights the essential role of oxygen vacancies in tuning the selectivity of photocatalytic reduction of CO_(2) into valuable chemicals.

Low Temperature One-Step Synthesis of Barium Titanate:Thermodynamic Modeling and Experimental Synthesis

A thermodynamic model has been developed to determine the reaction conditions favoring low temperature direct synthesis of barium titanate (BaTiO3). The method utilizes standard-state thermodynamic data for solid and aqueous species and a Debye-Hǔckel coefficients model to represent solution nonideality. The method has been used to generate phase stability diagrams that indicate the ranges of pH and reagent concentrations, for which various species predominate in the system at a given temperature. Also, yield diagrams have been constructed that indicate the concentration, pH and temperature conditions for which different yields of crystalline BaTiO3 can be obtained. The stability and yield diagrams have been used to predict the optimum synthesis conditions (e.g.,reagent concentrations, pH and temperature). Subsequently, these predictions have been experimentally verified.As a result, phase-pure perovskite BaTiO3 has been obtained at temperature ranging from 55 to 85℃ using BaCl2,TiCl4 as a source for Ba and Ti. and NaOH as a orecioitator.

Low Temperature One Step Synthesis of Barium Titanate: Particle Formation Mechanism and Large-scale Synthesis

The formation of BaTiO3 nanoparticles via the reaction of BaCl2, TiCl4 and NaOH in aqueous solution has been systematically studied. The formation of BaTiO3 from the ionic precursors has been elucidated to be a very rapid process, occurring at temperature higher than 60℃. Furthermore, the particle size could be controlled by the proper selection of the synthesis conditions (e.g. reactant concentration of 0.5—1.0mol·L-1, temperature of 80— 95℃ and pH≥13). A two-step precipitation mechanism was proposed. The first stage of the synthesis involved the formation of amorphous Ti-rich gel phase. The second stage of the synthesis was the reaction between the amor-phous phase and the solution-based Ba2+ ions, which led to the crystallization of BaTiO3. Based on the particle for-mation mechanism, a novel method, high gravity reactive precipitation, was proposed and used to mass production of BaTiO3 of average particle size of about 60 nm and with narrow particle size distribution. Because it could break up the amorphous Ti-rich gel into small pieces, intensify mass transfer, promote the reaction rate of amorphous Ti-rich gel with Ba2+ ions.

Electro-rheological Effect of Barium Titanate Particles Coated with Urea and Suspended in Methyl Silicone Oil

Barium titanate nano-powders were synthesized under defined conditions. The surface of these particles was successfully modified by coating with urea. The characteristics of these composite particles were studied by X-ray diffraction,transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. The electro-rheological (ER) effects of these particles suspended in methyl-silicone oil were measured. The particle,methyl-silicon oil ratio was 30%-35% weight percent. The experimental results indicate that these ER particles exhibit a remarkable ER effect. The ER fluid shows Bingham characteristics and the static shearing stress increases with an increase of the electric field strength. The highest static shearing stress under a 4 MV/m electric field is 13.2 kPa at room temperature,an increase of about 8.7 kPa compared to untreated BaTiO(C2O4)2 powders.

基于改性BT提高PVDF复合材料介电性能的研究

以酒石酸为螯合剂对钛酸钡(BT)进行表面改性,制备改性BT/聚偏二氟乙烯(PVDF)两相复合材料,并对制备的复合材料做介电性能分析。结果表明:改性后的BT能显著地提高复合材料的介电性能,且随着改性BT体积分数的增加介电常数逐渐增大;当改性BT体积分数增加到70%时,复合材料的介电常数在100Hz处为174,达到了最大值,与此同时系列改性BT复合材料的介电损耗能保持在较低水平,在100Hz处均为0.05左右。通过Lichtenecker对数方程对复合材料介电性能增强机制分析发现,酒石酸在BT表面的改性显著地改善了BT与PVDF基体的相容性,在BT表面形成了高介电性的界面弛豫区域,从而迅速提高了聚合物的介电性能。

Properties of composition sinter prepared from fibrous barium titanate and nanometer zirconia

Fibrous Batium Titanate particles, 30 50 μm long, prepared by a hydrothermal reaction, and the monoclinic phase and nanometer Zirconia, 11.6 nm long were prepared by citric acid reaction respectively. Then, the two were composite sintered to produce a new functional material by making full use of crystal axis orientation of fibers and the activity of nanometer powder. The analydid of composition and microstructure of the new material in terms of XRD and SEM. shows that the solid solution was formed between fibers and nanometer powder, and the distance between lattice (d value) of Barium Titanate changed. But the crystal axis orientations of fibers remain unchanged.

Preparation and characterization of barium strontium titanate/silicon nanoporous pillar array composite thin films by a sol-gel method

Barium strontium titanate （Ba0.5Sr0.5TiO3, BST）/silicon nanoporous pillar array （Si-NPA） thin films were prepared by a spin-coating/annealing technique based on Si-NPA with micro/nano-structure. Both the isomer conversion of acetylacetone and the network structure combined by enol and Ti-alkoxide facilitate the formation of the BST sol and the subsequent crystallization. Before the perovskite BST begins to form, the intermediate phase （Ba, Sr）Ti2OsCO3 is found. The boundary between BST and Si-NPA is of clarity and little interface diffusion, disclosing that Si-NPA is an ideal template substrate in the preparation of multifunctional composite films.

HYBRID AND CHARACTERISTIC OF POLYANILINEBARIUM TITANATE NANOCOMPOSITE PARTICLES

Polyaniline-barium titanate (PAn-Ba-TiO3) ultrafine composite particles were prepared by the oxidative polymerization of aniline with H2O2 while barium titanate nanoparticles were synthesized with a sol-gel method. The infrared spectrogram shows that the polymerization of PAn in the hybrid process of PAn-BaTiO3 is similar with the polymeric process of pure aniline, and there is interaction of PAn and BaTiO3 in the PAn-Ba-TiO3. SEM and TEM results show that the average diameter of the composite particles is 1.50μm and the diameters of BaTiO3 nanoparticles are 5 - 15 nm in the composite particle. The electrical conductivity of the ultrafine com-posite particles is transformable from 10°to 10-11S/cm by equilibrium doping or dedoping method using various concentration of HCl or NaOH solutions.

Characterization and growth dynamics of barium titanate crystallite on nanometer scale

Barium titanate powder on nanometer scale was synthesized by means of co-precipitation. The thermal mass loss, crystal grain growth and phase transition of the barium titanate nanometer powder were investigated by TG (Thermogravimetric)-DTA (Differential scanning calorimetric) and XRD (X-ray powder diffractometer) at different heat treatment temperatures. The results show that amorphous barium titanate powder can transfer into tetragonal symmetry structure after heat treatment. When the heat treatment temperature is below 900℃, the grains grow rapidly because the activation energy at low temperature is greatly less than that at high temperature. By controlling the heat treatment temperature, the optimization of the barium titanate crystallite size and formation of tetragonal phase can be realized.

Performance Evaluation of Rectangular Microstrip Patch Antennas Loaded with Plastic and Barium-Titanate Substrates at GSM 1800 MHz Band

In this paper, the resonance and radiation characteristics of patch antennas fabricated with two different types of dielectric substrates have been investigated and compared at GSM 1800 MHz band. At first, the above-stated characteristics of a patch antenna loaded with conventional plastic substrate have been investigated. Later a high permittivity dielectric material (barium titanate) has been used as the antenna substrate. The main goal here is to reduce the antenna size with a high permittivity dielectric material and then to compare its resonance and radiation performance with the earlier low permittivity substrate loaded prototype. It is found that with the use of high permittivity substrate the antenna volume gets smaller (about 6% of the plastic substrate prototype) although the gain decreases by around 2.5 dB.

BTO NWs/PVDF柔性复合薄膜的制备及其压电性能研究

该文通过两步水热法制备了钛酸钡纳米线(BTO NWs),采用旋涂法与聚偏氟乙烯(PVDF)复合制备BTO NWs/PVDF复合薄膜。系统地研究了水热反应中不同NaOH浓度、不同反应时间及不同BTO NWs掺杂量对BTO NWs/PVDF复合薄膜压电输出性能的影响,并与商用钛酸钡纳米球(BTO NPs)制备的BTO NPs/PVDF复合薄膜进行了压电性能对比。结果表明,当NaOH浓度为10 mol/L,反应时间为10 h时,BTO NWs/PVDF复合薄膜开路电压和短路电流分别可达5.42 V和1.81μA。当BTO NWs掺杂量(质量分数)为20%时,复合压电薄膜的开路电压可达9.34 V,短路电流可达2.15μA,分别是BTO NPs/PVDF复合薄膜输出电压和电流的1.92倍和1.49倍。当负载电阻值为5 MΩ时,BTO NWs/PVDF复合薄膜输出功率可达1.44μW。经过4000次循环敲击测试,BTO NWs/PVDF复合薄膜表现出良好的机械稳定性,其有望在自供电器件、柔性可穿戴电子设备等领域得到广泛应用。

Structural and Dielectric Properties of Sn Doped Barium Magnesuim Zirconium Titanate Perovskite Ceramics

Perovskite type ceramics (Ba0.9Mg0.1)(SnxZr0.4-xTi0.6)O3 (with x = 0.01, 0.02, 0.03 and 0.04) relaxor composition prepared through solid state reaction route and calcinated at temperature is 1150°C for 5 hrs with intermediate mixing. The room temperature XRD study suggests that all the samples have the single phase cubic symmetry with space group pm 3 m. The pellets were sintered at 1500°C for 4 hrs. Scanning Electron Microscope (SEM) observations revealed enhanced micro structural uniformity and retarded grain growth with decreasing Sn content. The dielectric measurements at constant frequency show that dielectric constant increases with Sn content. Loss factor and dielectric constant decreased with increasing frequency but at very high frequencies it was independent.