Sol-gel processed barium titanate thin films

Ferroelectric barium titanate (BaTiO₃) thin films have been prepared by sol-gel technique from barium acetate [Ba(CH₃COO)₂] and titanium (IV) isopropoxied [Ti(CH₃)₂CHO)₄] precursors. The as-grown films were found to be amorphous which crystallized to tetragonal phase after annealing at 700°C for one hour in air. The room temperautre dielectric constant (ε) and loss tangent (tanδ) of the films were found to be 370 and 0.02 respectively. The values of the spontaneous polarization (P_s), remanent polarization (P_r) and coercive field (E_c) of the films determined from the polarization-field (P-E) hysteresis were found to be 14.0, 3.2μC-cm^-2 and 53KV-cm^-1 respectively. The coercive field of the film determined from the capacitance-voltage (C-V) characteristics is slightly lower than that determined from the P-E hysteresis loop.     

Phase transition in Sol-Gel processed barium titanate ceramics

Ferroelectric barium titanate (BaTiO₃) ceramics have been prepared from barium acetate [Ba(CH₃COO)₂] and titanium isopropoxide [Ti(CH₃)₂CHO)₄] precursors by sol-gel technique The as-grown powder was found to be amorphous which crystallized to tetragonal phase after annealing at 700°C in air for one hour. The ceramics showed well saturated polarization-field (P-E) hysteresis loops at room temperature. The values of spontaneous polarization(P_s), remanent polarization (P_r) and coercive field (E_c) of the ceramics were found to be19.0, 12.66μC-cm^-2 and 30KVcm^-1 respectively. The room temperature dielectric constant (ε) and loss tangent (tanδ) of the ceramics were found to be 1135 and 0.012 respectively. The dielectric constant and tanδ showed anomaly peaks at 125°C showing ferroelectric to paraelectric phase transition. The polarization parameters also vanish at 125°C confirming the phase transition.     

Double Precursor Solution Coating Approach for Low-Temperature Sintering of [Pb(Mg1/3Nb2/3)O3]0.63[PbTiO3]0.37 Solids

Lead-based piezoelectric ceramics typically require sintering temperatures higher than 1000°C at which significant lead loss can occur. Here, we report a double precursor solution coating (PSC) method for fabricating low-temperature sinterable polycrystalline [Pb(Mg_1/3Nb_2/3)O₃]_0.63-[PbTiO₃]_0.37 (PMN–PT) ceramics. In this method, submicrometer crystalline PMN powder was first obtained by dispersing Mg(OH)₂-coated Nb₂O₅ particles in a lead acetate/ethylene glycol solution (first PSC), followed by calcination at 800°C. The crystalline PMN powder was subsequently suspended in a PT precursor solution containing lead acetate and titanium isopropoxide in ethylene glycol to form the PMN–PT precursor powder (second PSC) that could be sintered at a temperature as low as 900°C. The resultant d ₃₃ for samples sintered at 900°, 1000°, and 1100°C for 2 h were 600, 620, and 700 pm/V, respectively, comparable with the known value. We attributed the low sintering temperature to the reactive sintering nature of the present PMN–PT precursor powder. The reaction between the nanosize PT and the submicrometer-size PMN occurred roughly in the same temperature range as the densification, 850°–900°C, thereby significantly accelerating the sintering process. The present PSC technique is very general and should be readily applicable to other multicomponent systems.     

Hydrothermal Synthesis of Bismuth Titanate Powders

Bismuth titanate was synthesized under hydrothermal conditions from an amorphous bismuth–titanium precursor gel. The gel was formed by mixing a bismuth acetate complex with titanium butoxide and then adding the solution dropwise into 6 M NaOH. The resulting gel suspension was reacted under hydrothermal conditions at temperatures ranging from 160° to 200°C to form crystalline bismuth titanate. The gel crystallization kinetics increased with temperature, which resulted in 100% crystalline bismuth titanate in 5 h at 200°C. Wavelength-dispersive spectroscopy data indicated that sodium was incorporated into bismuth titanate during processing, and X-ray diffractometry suggested that the powder was composed of the Bi₅Ti₄O₁₅ phase. Transmission electron microscopy micrographs showed that the gel particles decomposed to 100–200 nm crystalline bismuth titanate particles during hydrothermal processing.     

不同水解抑制剂下Sr2+掺杂改性纳米TiO2的制备及可见光响应行为

采用溶胶-凝胶法,以钛酸丁酯为钛源,分别以三乙醇胺和亚氨基二乙酸为水解抑制剂,制备掺杂不同含量Sr²⁺的纳米TiO₂,并对其在可见光范围内对孔雀石绿的光催化降解活性进行评价。结果表明,Sr²⁺掺杂能够有效提高纳米TiO₂的光催化性能,并确定不同条件下合成的纳米TiO₂的最佳掺杂量和反应条件。对掺杂的TiO₂进行紫外可见漫反射光谱、X射线衍射、傅里叶变换红外光谱以及氮物理等温吸附等表征,揭示了表面性能、电子结构、脱水性能、吸附性能、结晶程度和晶相结构等多方面协同作用是Sr²⁺掺杂的TiO₂具有最高光催化活性的原因。这种新型光催化剂可能在环境净化和水处理方面具有一定的应用价值。     

Sol-gel synthesis of BaTiO3 and Ba1−x−yCaySrx(ZryTi1−y)O3 perovskite powders

A BaTiO₃ powder has been prepared by the sol-gel process from the hydrolysis of a solution of barium acetate and titanium ethylate in the presence of acetic acid as a catalyst. Supplementary constituents in the form of Ca(CH₃COO)₂, Zr(OC₃H₇)₄, Sr(NO₃)₂ also can be used. Intermediate phases of barium acetate and barium carbonate have been identified by differential thermal analysis, X-ray diffraction, infra-red and scanning electron microscopy. BaTiO₃ with perovskite structure synthesizes in the temperature range from 600 to 1000°C.     

Synthesis of Strontium Titanate Nanometer Crystallites Using a Peroxide-Based Route

Nanocrystalline strontium titanate (SrTiO₃) particles were prepared using a peroxide-based route. The reaction between hydrogen peroxide and β-titanic acid yielded a peroxytitanic solution. An amorphous precipitate containing strontium and titanium was formed when a solution of strontium nitrate was added at pH 9. The precipitate was filtered, washed, and calcined. The precipitate was characterized by thermogravimetry, infrared spectroscopy, and X-ray diffraction. Powder calcined at temperatures of about 750°C within 1 h showed a well-crystallized cubic SrTiO₃ perovskite phase. Applying this synthesis procedure for SrTiO₃ nanoparticles yields powders with a grain size of nearly 50 nm.     

Structural and Optical Properties of Barium Strontium Titanate (Ba0.5Sr0.5TiO3) Thin Films

Ferroelectric Barium Strontium Titanate (Ba_0.5Sr_0.5TiO₃) or BST thin films on quartz substrates have been prepared by using a modified sol gel processing technique. The starting materials are Barium 2-ethylhexanoate Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]_2, Strontium 2-ethylhexanoate Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂ and Titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄. The precursors except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on quartz substrates by spin coating. The as-fired films were found to be amorphous, which crystallized to cubic phase after annealing at 550°C in air for 1 hr. In this paper we report the structural and optical properties of BST films prepared by the modified sol-gel process.

Communicated by Prof. E. C. Subbarao     

Multi-metal cyanide catalysts for ring-opening polymerization of propylene oxide

Polymerizations of propylene oxide (PO) have been carried out by using a series of multi-metal metal cyanide (MMC) catalysts prepared by reacting ZnCl₂ and K₃[Co(CN)₆]₂, K₄Fe(CN)₆, K₃Fe(CN)₆ and/or K₂Ni(CN)₄ in the presence of tert-butyl alcohol and polytetramethylene ether glycol as complexing agents. The resulting MMC catalysts are characterized by elemental analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and X-ray powder diffraction. The structure of MMC catalysts with broadened X-ray diffraction peaks is different from that of highly crystalline Prussian blue analogues of microporous crystalline materials due to the coordination of complexing agents. The PO polymerization behavior was tunable by changing with various metal cyanide salts after fixing a main catalyst component as ZnCl₂. Even if the basic structure of the MMC complexes is different each other, i.e. orthorhombic for Zn₂[Fe(CN)₆] and monoclinic for Zn₃[Fe(CN)₆]₂ and Zn₃[Co(CN)₆]₂, the chemical formulations become more complicated by forming MMC complexes through cyano bridges and complexing agents’ coordination and the structure more distorted from the defined crystal structures. All catalysts prepared by using K₃[Co(CN)₆]₂ showed very high activity once they were activated. Simply changing catalyst formulation by choosing different metal cyanide salts, catalytic activity, induction period, polymer molecular weight and its distribution and polymer viscosity could be tuned.     

1,2-Diolates of titanium as suitable precursors for the preparation of photoactive high surface titania

1,2-Diolates of titanium of stoichiometric formula [Ti(OCHRCH₂O)₂] (R = −H, −CH₃, −CH₂CH₃) were prepared by reacting a titanium source (titanium(IV) isopropoxide (TIP) or titanium(IV) chloride) with an excess of the respective 1,2-diol. The diol was employed in a great excess; no other solvent was present in the synthesis procedure. The titanium diolates obtained have a white powder appearance and show a high degree of crystallinity as deduced from powder X-ray diffraction. It has been observed that their stability towards moisture is determined by the R group (R = −H, −CH₃, −CH₂CH₃).

Abstract

Hydrolysis of these titanium 1,2-diolates in water was a simple way to produce high surface porous titania with BET surface area up to 300 m² g⁻¹. These as-synthesised titania contain anatase crystallites and show photocatalytic activity versus formaldehyde degradation prior to calcination. Nevertheless, the decomposition rate of formaldehyde increased notably when titania samples were annealed at 773 K. This thermal treatment increases their crystallinity at the expense of a BET surface area decrease down to 75 m² g⁻¹ or less. The photocatalytic performance of the annealed samples is superior than that of commercial TiO₂ (Degussa P-25, Hombikat UV-100).     

Low-Temperature Synthesis of Fully Crystallized Spherical BaTiO3 Particles by the Gel–Sol Method

The synthesis of spherical BaTiO₃ particles was attempted by a new technique, the "gel–sol method," at 45°C. The (Ba–Ti) gel used as a starting material was prepared by aging mixtures of titanyl acylate with a barium acetate aqueous solution ([glacial acetic acid (AcOH)]/[titanium isopropoxide (TIP)] = 4, [barium acetate]/[TIP] = 1) at 45°C for 48 h. Potassium hydroxide (KOH) was used as a catalyst for the formation of BaTiO₃. Powder X-ray diffractometry (XRD) results and Fourier-transform infrared (FT-IR) measurements for the (Ba–Ti) gel showed that the gel was amorphous, but the spatial arrangement of barium and titanium in the (Ba–Ti) gel is similar to that in crystalline BaTiO₃ particles. Fully crystallized spherical BaTiO₃ powder with a particle size of 40–250 nm formed at the very low reaction temperature of 45°C. Scanning electron microscopy images showed that the final particles formed via aggregation of the fine particles that seem to be the primary particles of bulk (Ba–Ti) gel. From the XRD, FT-IR, and Raman spectroscopy analysis, it was found that the crystal structure of the as-prepared particles continuously transformed from cubic to tetragonal as the calcination temperature increased, and high crystalline tetragonal BaTiO₃ phase was obtained at 1000°C after 1 h of heat treatment.     

Preparation of Hollow BaTiO3 and Anatase Spheres by the Layer-by-Layer Colloidal Templating Method

Hollow BaTiO₃ and anatase spheres were prepared from multilayered colloidal titanate particles. An inorganic precursor, titanium (IV) bis(ammonium lactate) dihydroxide (TALH) (chemical formula: [CH₃CH(O–)CO₂–NH₄]₂Ti(OH)₂) was used. First, a layer-by-layer (LBL) colloid-templating method was employed using TALH to generate monodispersed hollow titanate spheres. These spheres were then treated in a Ba(OH)₂ solution or distilled water under hydrothermal conditions to transform them into hollow BaTiO₃ or anatase spheres, respectively.     

Solvothermal syntheses of semiconductor photocatalysts of ultra-high activities

Thermal treatment of titanium(IV) butoxide dissolved in 2-butanol at 573 K under autogenous pressure (alcohothermal treatment) yielded microcrystalline anatase-type titanium(IV) oxide (TiO₂). Thermal treatment of oxobis(2,4-pentanedionato-O,O′)titanium (TiO(acac)₂) in ethylene glycol (EG) in the presence of sodium acetate and a small amount of water at 573 K yielded microcrystalline brookite-type TiO₂. Tungsten(VI) oxide (WO₃) powders of monoclinic crystal structure with high crystallinity were synthesized by hydrothermal treatment (HTT), at 523 or 573 K, of aqueous tungstic acid (H₂WO₄) solutions prepared from sodium tungstate by ion-exchange (IE) with a proton-type resin. Anatase and brookite TiO₂ products were calcined at various temperatures and then used for photocatalytic mineralization of acetic acid in aqueous solutions under aerated conditions and dehydrogenation of 2-propanol under deaerated conditions. Almost all the anatase-type TiO₂ samples showed the activities more than twice higher than those of representative active photocatalysts, Degussa P-25 and Ishihara ST-01 in both reactions. A brookite sample with improved crystallinity and sufficient surface area obtained by calcination at 973 K exhibited the hydrogen evolution rate almost equal to P-25. HTT WO₃ powders with various physical properties were used as photocatalyst for evolution of oxygen (O₂) from an aqueous silver sulfate solution. WO₃ powder of high crystallinity, e.g., IE-HTT-WO₃ synthesized at 573 K, gave much higher O₂ yield than commercially available WO₃ samples.     

Preparation and Characterization of BaxSr1-x, TiO3 Thin Films by a Sol-Gel Technique

Barium strontium titanate, (Ba_x,Sr_1-x TiO₃, thin films of various compositions were prepared by a sol-gel method. Solutions consisting of acetate powders and titanium IV isopropoxide in a mixture of acetic acid and ethylene glycol were spin-coated onto silicon and platinum-coated silicon substrates. Processing parameters were optimized to develop stable solutions which yielded films with relatively low crystallization temperatures. It was determined that ethylene glycol was a necessary component of the solution to increase stability to precipitation and to decrease the crystallization temperature of the films. The grain size of the films varied with annealing temperature and atmosphere and directly affected the dielectric properties. A dielectric constant of 400 and a dissipation factor of 0.04 were measured at 1 kHz for (Ba_0.8,Sr_0.2) TiO₃ films heated to 700°C for 1 h with a thickness of approximately 400 nm. Films of this composition maintained low leakage current densities for extended time periods when measured at an applied field of 75 kV/cm.     

Hydrolytic Condensation of Tin(IV) Alkoxide Compounds to Form Particles with Well-Defined Morphology

The sol-gel-type condensation of tin(IV) ethoxide [Sn(OEt)₄] n (where OEt is ethoxide) under basic conditions produced spherical, submicrometer-sized tin(IV) oxide (cassiterite) particles. Transmission electron microscopy and powder X-ray diffraction data indicated that the grain size was approximately 20 to 30 Å (2 to 3 nm). The mixed-metal alkoxide compound [ZnSn(OEt)₆] was hydrolyzed under analogous conditions to give either spherical or octahedral submicrometer-sized crystalline particles of ZnSn(OH)₆ depending on the solvents used. These data demonstrated that the stoichiometry of the mixed-metal alkoxide precursor was retained during condensation. Thermal treatment of ZnSn(OH)₆ resulted in crystallization of ZnSnO₃ at approximately 676°C. At neutral pH, hydrolysis of [ZnSn(OEt)₆] resulted in formation of a high surface area (261 m²/g) amorphous powder.     

Chemical Solution Deposition of (Pb1−xCax)TiO3 Thin Films with x∼0.5 as New Dielectrics for Tunable Components and Dynamic Random Access Memories

Calcium lead titanate ((Pb,Ca)TiO₃) thin films, with calcium contents of ∼50 at.%, have been prepared by chemical solution deposition (CSD). Different synthetic sol–gel methods have been used for the preparation of the precursor solutions. 1,3-propanediol, OH(CH₂)₃OH, and water, H₂O, were used as solvents. Lead (II) acetate trihydrate, Pb(OCOCH₃)₂·3H₂O, and titanium di-isopropoxide bis(acetylacetonate), Ti(OC₃H₇)₂(CH₃COCHCOCH₃)₂, were used as reagents of lead and titanium, respectively. Calcium was incorporated into the solutions as calcium acetate hydrate, Ca(OCOCH₃)₂· x H₂O, or as calcium acetylacetonate hydrate, Ca(CH₃COCHCOCH₃)₂· x H₂O. Only the use of calcium acetate led to precipitate-free solutions. Pb(II)–Ti(IV)–Ca(II) sols were obtained when calcium acetate was refluxed with the lead and titanium reagents in a diol–water solvent. These sols led to films with a homogeneous compositional profile. Solutions obtained by mixing a water solution of calcium acetate with a Pb(II)–Ti(IV) sol led to films with a heterogeneous compositional profile in which an interface between the film and the Pt bottom electrode is formed. The films derived from the Pb(II)–Ti(IV)–Ca(II) sols have values of dielectric constant at room temperature of ∼500, which, together with their low leakage currents, low dielectric losses, and tunability, make these films promising for dynamic random access memories and tunable devices.     

铋及钴掺杂TiO2陶瓷负载膜的制备及光催化性能

以钛酸四丁酯为钛源,Bi(NO₃)₃·5H₂O为铋源,Co(NO₃)₂·6H₂O为钴源,采用溶胶-凝胶法在陶瓷基片上分别制备了应用于固定式光催化反应器的Bi-TiO₂复合膜及Co-TiO₂复合膜。研究了涂膜方式及煅烧升温速率对膜表面形态的影响,并以甲基橙溶液为目标降解物,对比了旋涂法及浸渍提拉法制备的薄膜在不同升温速率下的光催化活性。通过热分析仪(TG-DSC)、X射线衍射仪(XRD)和扫描电镜(SEM)等测试手段分析了掺杂薄膜的结构。结果表明,采用旋涂法制备的薄膜与陶瓷基体结合较为紧密,而浸渍提拉法制备的薄膜催化活性较高。当煅烧温度为500 ℃,升温速率为10 ℃/min时,其对甲基橙的降解率较高。当摩尔比为0.010时Bi-TiO₂复合膜的催化活性较佳,100 min光降解甲基橙比率达到8.10%。钴或铋掺杂TiO₂均可提高TiO₂催化剂的光催化活性,Bi-TiO₂膜的催化活性优于Co-TiO₂膜。     

KBaB5O9的两步法制备及其过程动力学研究

本文利用溶液法制备了K₂Ba[B₄O₅(OH)₄]₂·8H₂O,并将其进行热处理制备得到了KBaB₅O₉,利用XRD、FT-IR、TG-DTA-DTG对样品进行了表征。分析研究了由K₂Ba[B₄O₅(OH)₄]₂·8H₂O热处理制备KBaB₅O₉过程中的物相变化过程,其物相变化经历脱结晶水、脱羟基、重结晶、再分解、熔融再结晶5个阶段,其中结晶水的脱失分两步进行。运用Kissinger法、Flynn-Wall-Ozawa法、Šatava-Šesták法对K₂Ba[B₄O₅(OH)₄]₂·8H₂O结晶水第二步脱失过程的动力学参数进行了计算,可知K₂Ba[B₄O₅(OH)₄]₂·8H₂O结晶水第二步脱失过程的活化能E_s为151.94 kJ/mol,指前因子的对数值lg A_s为21.25 min^-1,机理函数G(α)=(1-2α/3)-(1-α)^2/3(其中α为转化率)。     

Preparation and microstructure analysis of Fe-doped PbTiO ceramic

Fe-doped PbTiO₃ (PT) powder and bulk materials were prepared successfully by sol-gel technique and a subsequent sintering process using Fe (C₅H₅)₂ as a dopant agent. The effects of pH and temperature on the Fe-doped PT system were investigated. Thermogravimetry/differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to analyze the composition and the microstructure of the PT ceramics. The results indicated that the thermal decomposition of xerogel included three stages: volatilization of adsorption water and organic composition, oxygenolysis of n-butyl and acetate, and transformation of the crystalline phase. Well-stabilized collosol and gel could be obtained at 60°C and pH = 4.5. It was found that PbTiO₃, PbFe₂O₄, and TiO₂ crystalline appeared in the Fe-doped PT system when the mass fraction of the dopant Fe was 0.03%. Furthermore, from STM analysis, it could be seen that the grain size of doped PT ceramics was homogeneous and about 1–2 ?m, and the pore of the PT ceramic was small. As a result, the PT ceramic had high tightness.     

Synthesis of Lead Titanate: Thermodynamic Modeling and Experimental Verification

A comprehensive thermodynamic model has been developed to determine the reaction conditions favoring hydro-thermal synthesis of lead titanate (PbTiO₃). The model combines standard-state thermodynamic data for solid and aqueous species and an excess Gibbs energy model to account for the nonideality of the solution. 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 and pressure. Also, yield diagrams have been constructed that indicate the concentration, pH, and temperature conditions for which different yields of crystalline PbTiO₃ 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 PbTiO₃ has been obtained at temperatures ranging from 413 to 433 K using lead acetate or lead nitrate and commercial TiO₂ powder. Also, PbTiO₃ has been synthesized at lower temperatures (353 T 363 K) by using lead acetate and hydrous (reactive) TiO₂ and calcining the obtained amorphous product.