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.

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

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.

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.

Enhancing energy storage density of poly(arylene ether nitrile)via incorporating modified barium titanate nanorods and hotstretching

Dielectric energy storage materials that are extensively employed in capacitors and other electronic devices have attracted increasing attentions amid the rapid progress of electronic technology.However,the commercialized polymeric and ceramic dielectric materials characterized by low energy storage density face numerous limitations in practical applications.In this study,we report the simultaneous enhancement of dielectric properties of poly(arylene ether nitrile)(PEN)through the incorporating of sulfonated PEN(SPEN)modified barium titanate nanorods(BTNR)(SPEN@BTNR)and hot-stretching.BTNR is synthesized using a two-step hydrothermal method,aminated with KH550,and then reacted with SPEN to form the cladding-modified SPEN@BTNR.Due to the intrinsic high permittivity of barium titanate(BT)and enhanced compatibility between SPEN@BTNR and PEN stemming from the cladding of SPEN,the dielectric constant and breakdown strength of SPEN@BTNR/PEN composite are as high as 14.0 at 103 Hz and 198.1 kV/mm at the doping amount of 15 wt.%,respectively.As a result,the energy storage density of SPEN@BTNR/PEN is increased to 2.43 J/cm^(3),compared with that of 0.82 J/cm^(3)for PEN.In addition,derived from the rearrangement of SPEN@BTNR and orientation of PEN after hot-stretching,the dielectric constant and breakdown strength of SPEN@BTNR/PEN with 15 wt.%fillers are further enhanced to 17.1 and 204.8 kV/mm,respectively,resulting in an energy storage density of 3.36 J/cm^(3).The boosting of energy storage density up to 310%provides a new idea for improving the performances of dielectric energy storage materials.

Ultrasmall barium titanate nanoparticles modulated stretchable dielectric elastomer sensors with large deformability and high sensitivity

Large deformability and high sensitivity is difficult to be realized simultaneously in flexible sensors.Herein,taking advantage of the high permittivity and highly active surfaces of the ultrasmall barium titanate nanoparticles(BT NPs)and the high stretchability of the p(BA-GMA)elastomer matrix,we propose a high-performance soft stretchable sensor.The addition of the ultrasmall BT NPs can not only increase the permittivity and capacitance of polyacrylate-matrix composite dielectric material to obtain a high sensitivity,but also basically maintains the excellent mechanical properties of the polymer matrix.The dielectric constants of the composite films increase from 5.68 to 13.13 at 10 kHz with the increase of BT NPs content from 0 to 15 vol.%,which results in a high capacitance of 236.16 pF for 15 vol.%BT/p(BA-GMA)sensor.Combining the high permittivity and the large deformability(a maximal deformation of 87.2%),the 15 vol.%BT/p(BA-GMA)sensor has high sensitivity and shows high linearity and stable output even if under dynamic measurement.The dual-mode sensor that utilizes the orthogonality of capacitance-resistance is designed,which shows excellent performance in monitoring human body movements and noncontact measurement.The results present that the BT/p(BA-GMA)-based sensor has high stability and reliability not exceed 65C,which can meet the application requirements in dynamic monitoring.

Electroactive barium titanate coated titanium scaffold improves osteogenesis and osseointegration with low-intensity pulsed ultrasound for large segmental bone defects

For large segmental bone defects,porous titanium scaffolds have some advantages,however,they lack electrical activity which hinders their further use.In this study,a barium titanate(BaTiO3)piezoelectric ceramic was used to modify the surface of a porous Ti6Al4V scaffold(pTi),which was characterized by scanning electron microscopy,energy dispersive spectroscopy,X-ray photoelectron spectroscopy,and roughness and water contact angle analyses.Low intensity pulsed ultrasound(LIPUS)was applied in vitro and in vivo study.The activity of bone marrow mesenchymal stem cells,including adhesion,proliferation,and gene expression,was significantly superior in the BaTiO3/pTi,pTi+LIPUS,and BaTiO3/pTi+LIPUS groups than in the pTi group.The activity was also higher in the BaTiO3/pTi+LIPUS group than in the BaTiO3/pTi and pTi+LIPUS groups.Additionally,micro-computed tomography,the mineral apposition rate,histomorphology,and the peak pull-out load showed that these scaffold conditions significantly enhanced osteogenesis and osseointegration 6 and 12 weeks after implantation in large segmental bone defects in the radius of rabbits compared with those resulting from the pTi condition.Consequently,the improved osteogenesis and osseointegration make the BaTiO3/pTi+LIPUS a promising method to promote bone regeneration in large segmental bone defects for clinical application.

Preparation of Oriented Barium Titanate Thin Films by Combination of Electrophoretic Deposition with Hydrothermal Treatment

Highly oriented barium titanate （BaTiO 3） thin films on Pt substrate were fabricated by combination of electrophoretic deposition with hydrothermal treatment.The structure and morphology of thin films were characterized by X-ray diffraction and field-emission scanning electron microscopy.It is found that the titania precursor film,Ba（OH）2 concentration and hydrothermal temperature play crucial roles in the film morphology and orientation.The BaTiO3 thin films with highly （110） preferred orientation can be formed on polycrystalline Pt substrate by appropriate adjustment of the reaction conditions.The orientation parameter f of highly oriented BaTiO3 films was up to 1.00.The films exhibited a smooth and crack-free surface and remained in the layered structure.In situ topotactic transformation and dissolution-crystallization mechanisms were proposed to explain the morphology and orientation of BaTiO3 films during hydrothermal treatment.

Enhanced energy storage properties of barium titanate ceramics made from surface modified particles

Surface modification of barium titanate particles has been carried out using a wet chemical method.The microstructural and dielectric properties of the ceramics made from surface modified particles were extensively investigated by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,and dielectric properties measurements.The breakdown strength increased by 69%and 117%for the Al_(2)O_(3) and B_(2)O_(3)–SiO_(2) modified ceramics,respectively.An energy storage density of up to 3.2 J/cm^(3) has been obtained.The suppression of grain boundary electron transport and reduction in pore defects lead to the energy storage properties enhancement of the modified ceramics.These results indicated that surface modification of ceramic particles is a promising approach to obtain dielectric ceramics with high energy storage density.

Preparation of optical active single-handed helical barium titanate nanotubes and characterization of dielectric properties

Left and right-handed helical barium titanate nanotubes are prepared with the impregnation of Ba（OH）2 into single-handed helical titania nanotubes.Wide angle X-ray diffraction pattern and transmission electron microscopy image indicate that they are constructed by nanoparticles with a partially crystalline structure.The diffuse reflertance circular dichroism spectra indicate that they exhibit optical activity which was proposed to originate from chiral defects on the inner surfaces of the nanotubes.Both the dielectric constant and tanδ decrease with increasing the frequency.At 10 and 100 Hz,one dielectric constant peak at 9.6℃ and one tanδ peak at 5.0℃ are observed at -120℃ to 180℃.

Dielectric property of polyimide/barium titanate composites and its influence factors (Ⅱ)

Using poly(amic acid)(PAA)as a precursor followed by thermal imidization,the polyimide/barium titanate composite films were successfully prepared by a direct mixing method and in situ process.The influence of processing factors,such as particle size,distribution mode and polymerization method on dielectric prop-erties was studied.Results revealed that the dielectric constant(ε)of the composite film increased by using bigger fillers or employing in situ polymerization and bimodal distribution.When the composite film contain-ing 50 Vol-%of BaTiO3 with size in 100 nm was pre-pared via in situ process,its dielectric constant reached 45 at 10 kHz.

Atomic-resolution characterization on the structure of strontium doped barium titanate nanoparticles

Ferroelectric barium titanate nanoparticles(BTO NPs)may play critical roles in miniaturized passive electronic devices such as multi-layered ceramic capacitors.While increasing experimental and theoretical understandings on the structure of BTO and doped BTO have been developed over the past decade,the majority of the investigation was carried out in thin-film materials;therefore,the doping effect on nanoparticles remains unclear.Especially,doping-induced local composition and structure fluctuation across single nanoparticles have yet to be unveiled.In this work,we use electron microscopy-based techniques including high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM),integrated differential phase contrast(iDPC)-STEM,and energy dispersive X-ray spectroscopy(EDX)mapping to reveal atomically resolved chemical and crystal structure of BTO and strontium doped BTO nanoparticles.Powder X-ray diffraction(PXRD)results indicate that the increasing strontium doping causes a structural transition from tetragonal to cubic phase,but the microscopic data validate substantial compositional and microstructural inhomogeneities in strontium doped BTO nanoparticles.Our work provides new insights into the structure of doped BTO NPs and will facilitate the materials design for next-generation high-density nano-dielectric devices.

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 .

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.

Photocatalytic Degradation of Oxytetracycline Dihydrate from Aqueous Solution Using Nano ZnO and ZnO.xBaTiO3 (x = 3%, 18%, 33% and 48%)

Traditional wastewater mostly contains pharmaceutical ingredients. Therefore, the wastewater must be completely free from antibiotics before its release into the environment. In the present study, photocatalytic degradation was done to investigate the removal efficiency of Oxytetracycline Dihydrate (OTC) using ZnO, ZnO/3%BaTiO3 (3 BZ), ZnO/18%BaTiO3 (18 BZ), ZnO/ 33%BaTiO3 (33 BZ) and ZnO/48%BaTiO3 (48 BZ) under UV light. After the exposure time of 420 min, about 99.57% and 97.87% of OTC was degraded using ZnO and 3 BZ respectively. Further, increasing the amount of BaTiO3 in ZnO prolongs the degradation time. Therefore, faster efficiency was found using ZnO nanoparticles. The observed reaction rate constant using ZnO was 0.00933 min-1 which decreased to 0.00532 min-1 using 48 BZ, indicating the decrease of reaction rate for increasing the amount of BaTiO3. Hence, the use of ZnO photocatalyst is anticipated to be a promising technique for the photocatalytic degradation of contaminated wastewater with oxytetracycline antibiotics using UV light.

Effects of Cerium Doping at Ti Sites and Europium Doping at Ba Sites on Dielectric Properties of BaTiO_3 Ceramics

Two special rare earth elements cerium and europium were chosen to conduct chemical modification of the BaTiO3 structure. The cold-pressing ceramic processing technique was used to prepare barium titanate ceramics doped with Ce at Ti sites and with Eu at Ba sites on the base of formulas Ba （ Ti1 -x Cex ） O3 （x = 0. 05, 0. 10 ） （CBT） and （ Ba1-y Euy ） Ti1-x/8O3 （ y = 0. 05, 0. 10） （EBT）. Associated with structures and microstructures, the effects of cerium and europium doping on dielectric properties of BaTiO3 ceramics were discussed. The CBT ceramics exhibit a pseudocubic perovskite structure, while the EBT ceramics exhibit a tetragonal perovskite structure with the exception of the existence of a small percentage of the Eu2Ti2O7 phase. The Curie peak of BaTiO3 shifts towards room temperature at rates of 3 ℃/mol Ce atoms and 10 ℃/mol Eu atoms（ Eu≤5% ）, respectively. Compared with the CBT ceramics, the EBT ceramics show significant advantages, such as a narrow fine grain size distribution（ 1 μm）, a lower porosity and a higher density（5.85 g/cm^3）, more stable dielectric-temperature dependence（ ε′= 1600-1800 at t 〈 50℃ ） and a lower dissipation factor（ 〈 0. 05 ）. The stability of dielectric constant with frequency in BaTiO3 can extend to 107 Hz due to Ce and Eu doping.

Effect of milling process on the core-shell structures and dielectric properties of fine-grained BaTiO_3-based X7R ceramic materials

Fine-grained BaTiO3-based X7R ceramic materials were prepared and the effects of milling process on the core-shell structures and dielectric properties were investigated using scanning electron microscope, transmission electron microscope, and energy dispersive spectroscopy （EDS）. As the milling time extends, the dielectric constant of the ceramics increases, whereas the temperature coefficient of capacitance at 125℃ drops quickly. The changes in dielectric properties are considered relevant to the microstructure evolution caused by the milling process. Defects on the surface of BaTiO3 particles increase because of the effects of milling process, which will make it easier for additives to diffuse into the interior grains. As the milling time increases, the shell region gets thicker and the core region gets smaller; however, EDS results show that the chemical inhomogeneity between grain core and grain shell becomes weaker.

Fabrication of BaTiO_3 Inverse Opal Photonic Crystal

The colloidal crystal template or opal with a closed-packed face centered cubic (fcc) lattice, was prepared from monodisperse polystyrene (PS) spheres by gravity sedimentation. The template was used for the generation of photonic crystal. The template provided void space for infiltration of liquid precursor composed of titanium butyloxide, barium acetate, ethanol, and acetic acid. The opal composite was hydrolyzed, dried, sintered by heating for completely removing PS spheres to form BaTiO3 photonic crystals with inverse opal structure. The PS spheres were replaced by air spheres, which interconnected each other through the windows on the BaTiO3 wall. So both the BaTiO3 wall and air void constitute continuous phases.