Electrochemical Synthesis of Small SrTiO3 Particles

Small strontium titanate (SrTiO₃) particles with an average particle size of about 100 nm have been successfully synthesized by a simple and fast electrochemical route, in which Ti metal plates are used as electrodes and an aqueous solution of KOH and Sr(OH)₂ as an electrolyte. Anodic sparks played a key role, and KOH concentration was one of the most significant factors that affected the appearance of anodic sparks in this method. XRD patterns indicated that the powders obtained in our study were a pure perovskite phase SrTiO₃ with a cubic structure, whose size and morphology were subsequently studied by transmission electron microscopy. UV-VIS result showed that the products had better UV absorption and visible light response than TiO₂-P25.     

Homogeneous ZrO2–Al2O3 Composite Prepared by Nano-ZrO2 Particle Multilayer-Coated Al2O3 Particles

ZrO₂–Al₂O₃ nanocomposite particles were synthesized by coating nano-ZrO₂ particles on the surface of Al₂O₃ particles via the layer-by-layer (LBL) method. Polyacrylic acid (PAA) adsorption successfully modified the Al₂O₃ surface charge. Multilayer coating was successfully implemented, which was characterized by ξ potential, particle size. X-ray diffraction patterns showed that the content of ZrO₂ in the final powders could be well controlled by the LBL method. The powders coated with three layers of nano-ZrO₂ particles, which contained about 12 wt% ZrO₂, were compacted by dry press and cold isostatically pressed methods. After sintering the compact at 1450°C for 2 h under atmosphere, a sintered body with a low pore microstructure was obtained. Scanning electron microscopy micrographs of the sintered body indicated that ZrO₂ was well dispersed in the Al₂O₃ matrix.     

Microwave Plasma Synthesis of Nanostructured γ-Al2O3 Powders

Nanostructured Al₂O₃ powders have been synthesized by combustion of aluminum powder in a microwave oxygen plasma, and characterized by X-ray diffraction and electron microscopy. The main phase is γ-Al₂O₃, with a small amount of δ-Al₂O₃. The particles are truncated octahedral in shape, with mean particle sizes of 21–24 nm. The effect of reaction chamber pressure on the phase composition and the particle size was studied. The γ-alumina content increases and the mean particle size decreases with decreasing pressure. No α-Al₂O₃ appears in the final particles. Electron microscopy studies find that a particle may contain more than one phase.     

Formation of SiO2, Al2O3, and 3Al2O3. 2SiO2 Particles in a Counterflow Diffusion Flame

SiO₂, Al₂O₃, and 3Al₂O₃.2SiO₂ powders were synthesized by combustion of SiCl₄ or/and AlCl₃ using a counterflow diffusion flame. The SiO₂ and Al₂O₃ powders produced under various operation conditions were all amorphous and the particles were in the form of agglomerates of small particles (mostly 20 to 30 nm in diameter). The 3Al₂O₃.2SiO₂ powder produced with a low-temperature flame was also amorphous and had a similar morphology. However, those produced with high-temperature flames had poorly crystallized mullite and spinel structure, and the particles, in addition to agglomerates of small particles (20 to 30 nm in diameter), contained larger, spherical particles 150 to 130 nm in diameter). Laser light scattering and extinction measurements of the particle size and number density distributions in the flame suggested that rapid fusion leading to the formation of the larger, spherical particles occurred in a specific region of the flame.     

Sintering of Partially Stabilized Zirconia by Microwave Heating Using ZnO–MnO2–Al2O3 Plates in a Domestic Microwave Oven

Partially stabilized zirconia (PSZ) powders were fully densified by microwave heating using a domestic microwave oven. Pressed powder compacts of PSZ were sandwiched between two ZnO–MnO₂–Al₂O₃ ceramic plates and put into the microwave oven. In the first step, PSZ green pellets were heated by self-heating of ZnO–MnO₂–Al₂O₃ ceramics (1000°C). In the second step, the heated PSZ pellets absorbed microwave energy and self-heated up to a higher temperature (1250°C), leading to densification. The density of PSZ obtained by heating in the microwave oven for 16 min was 5.7 g/cm³, which was approximately equal to the density of bodies sintered at 1300°C for 4 h or 1400°C for 16 min by the conventional method. The average grain size of the sample obtained by this method was larger than the average grain size of samples sintered by the conventional method with a similar heating process.     

Synthesis of NiO-Deposited YSZ Composite Powders by Urea Hydrolysis

The urea hydrolysis method was used to prepare NiO-deposited YSZ composite powders. First, micrometer-sized YSZ particles were fabricated, and then the nanosized NiO particles were deposited on the surface of the YSZ particles. The microstructure of composite powders and the sintered bulk were further characterized with the aid of XRD, SEM, and TEM. The results indicated that the mesoporous and microsheet-like Ni(OH)₂· x H₂O ( x =0–1) crystals were deposited on the surface of YSZ particles. As the concentration of Ni²⁺ ion in the stock solution increased, the deposited NiO content and thickness of NiO layer on the YSZ particle surface also increased. In addition, the YSZ particle size showed significant influence on the microstructure and conductivity of Ni/YSZ cermet anode produced by NiO-deposited YSZ composite powders. Such NiO-deposited YSZ composite powders can be easily sintered to form a continuous NiO network.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

Metal Propionate Synthesis of Magnetoresistive La1−x(Ca,Sr)xMnO3 Thin Films

A flexible chemical solution deposition (CSD) method for the preparation of magnetoresistive La_1−x (Ca,Sr)x MnO₃thin films based completely on metal propionates is pre-sented.A number of polycrystalline thin films with varying stoichiometries were deposited on different substrate ma-terials at temperatures between 550° and 850°C. The crys-tallization behavior on selected substrates was found to de-pend on the thin film stoichiometry. Magnetoresistivity and magnetization were measured as a function of temperature. For the selected samples, a magnetic Curie temperature TC, a metal–semiconductor transition, and magnetoresistive behavior were observed. These measurements demon-strated that La_1−x(Ca,Sr)x MnO₃ thin films with properties well known from films deposited by PLD or sputtering can be prepared by a simple, propionate-based CSD method.     

Effect of Processing Parameters on the Morphology of Hydrothermally Derived PbTiO3 Powders

The influence of processing parameters on the growth and morphology of hydrothermally derived lead titanate (PbTiO₃) powders was investigated. PbTiO₃ powder was synthesized by suspending nanocrystalline powders of TiO₂ in aqueous solutions of KOH and Pb(CH₃COO)₂·3H₂O at temperatures ranging from 120° to 200°C. PbTiO₃ growth initiated in the <100> exposing the (001) surfaces and resulting in a faceted platelet morphology. Particle growth proceeded by further nucleation and growth on existing (001) surfaces. Through repeated dissolution and precipitation, the platelet clusters coarsened into larger cuboidal particles. PbTiO₃ particle size was controlled by either inhibiting or promoting dissolution-precipitation. Dissolution-precipitation was inhibited by lowering the KOH concentration or the reaction temperature, or maintaining an excess of lead ions in solution, while it was promoted by increasing the KOH concentration and temperature. Coarsening of PbTiO₃ particles coincided with decreases in the X-ray diffraction (XRD) peak breadth, the asymmetry of l component XRD reflections, and the c -axis length.     

Synthesis of Nano-sized BaTiO3 Powders by the Rotary-Hydrothermal Process

Nano-sized BaTiO₃ powders with narrow size distribution and high tetragonality were attempted to be synthesized by the rotary-hydrothermal process in a water system as a novel technique, using a mixture of anatase-type TiO₂ and Ba(OH)₂ as starting material. The rotary-hydrothermal syntheses were performed under conditions with a rotary-speed of 20 revolutions per minute at 423–523 K for 3–96 h. Highly- and mono-dispersed BaTiO₃ powders mainly composed of coarse-faceted particles with the tetragonal phase were successfully synthesized by controlling the conditions for rotary-hydrothermal treatments. TEM and TG results revealed that these coarse-faceted BaTiO₃ particles contained very few structural defects such as hydroxyl content. Thus, the rotary-hydrothermal process was a useful method to synthesize very high-quality BaTiO₃ particles, and the further control of various conditions of the rotary-hydrothermal treatment is expected to control the crystalline phase and microstructures of final BaTiO₃ powders.     

Effect of MnO2 Addition on the Structure and Electrical Properties of Pb(Zn1/3Nb2/3)0.20(Zr0.50Ti0.50)0.80O3 Ceramics

Pb(Zn_1/3Nb_2/3)_0.20(Zr_0.50Ti_0.50)_0.80O₃ ceramics of pure perovskite structure were prepared by the two-stage method with the addition of 0–3.0 wt% MnO₂ and their piezoelectric properties were investigated systematically. The MnO₂ addition influences in a pronounced way both the crystal structure and the microstructure of the materials. The materials are transformed from the tetragonal to the rhombohedral structure, and the grain size is enhanced when manganese cations are added. The distortion of crystal structure for samples with MnO₂ addition can be explained by the Jahn–Teller effect. The values of electromechanical coupling factor ( k _p) and dielectric loss (tan δ) are optimized for 0.5-wt%-MnO₂-doped samples ( k _p= 0.60, tan δ= 0.2%) and the mechanical quality factor ( Q _m) is maximized for 1.0-wt%-MnO₂-doped samples ( Q _m= 1041), which suggests that oxygen vacancies formed by substituting Mn³⁺ and Mn²⁺ ions for B-site ions (e.g., Ti⁴⁺ and Zr⁴⁺ ions) in the perovskite structure partially inhibited polarization reversal in the ferroelectrics. The ceramics with 0.50–1.0 wt% MnO₂ addition show great promise as practical materials for piezoelectric applications.     

Characteristics and Formation Mechanism of BaTiO3 Powders Prepared by Twin-Fluid and Ultrasonic Spray-Pyrolysis Methods

Spherical fine (micrometer and submicrometer in size) homogeneous BaTiO₃ powders were synthesized from ethanol: water solutions of BaCl₂ and TiCl₄ using the spray-pyrolysis technique. Two different atomizers—twin-fluid and ultrasonic, with a resonant frequency of 2.5 × 10⁶ Hz—were used for mist generation. Hollow spherical particles containing a certain amount of unreacted BaCl₂ phase and having a mean particle diameter of 2.5 μm were obtained at 1173 K using a twin-fluid atomizing system. Decomposition of precursors and their transition to the cubic BaTiO₃ phase occurred, even at 973 K in the case of the ultrasonic atomizing system. For the initial droplet size of 2.2 μm and residence time of ∼60 s, spherical BaTiO₃ particles with the mean particle diameter of 0.53 μm were obtained. A BaTiO₃ formation mechanism has been proposed as a reaction between TiO₂ and BaCl₂ rather than a reaction of oxides.     

Effects of Composition on the Reaction Kinetics of Hydrothermally Derived Barium Strontium Titanate

Barium strontium titanate (BST, Ba _x Sr_{1− x} TiO₃) powders were fabricated by reacting nanocrystalline TiO₂ with aqueous alkaline solutions containing Ba and Sr at 80°C. Measurements of reaction kinetics showed that Ba-rich BST compositions exhibited more rapid reaction rates compared with Sr-rich BST compositions, and the reaction rate increased monotonically with increasing Ba content. The average particle size also increased with increasing Ba content, with the particle growth rate of BaTiO₃ being approximately a factor of 10 greater than SrTiO₃. The increase in growth rate from Sr-rich to Ba-rich BST corresponded to a morphological transition from 20 to 30 nm cuboidal particles to 80 nm raspberry-like particles, respectively.     

Effect of Particle Size on the Room-Temperature Crystal Structure of Barium Titanate

The room-temperature tetragonal-to-cubic transformation in BaTiO₃ powders with decreasing particle size has been carefully studied, using materials prepared mainly by hydrothermal methods. Hydrothermal BaTiO₃ powders exhibited a more uniform particle size distribution than oxalate-route powders, with X-ray diffraction and electron microscopy indicating that powders 0.19 μm in size were fully cubic while powders 0.27 μ were completely tetragonal (within a 5% detection limit for cubic material) at room temperature. The tetragonal-to-cubic transformation temperature was also found to lie in the range of 121°± 3°C for BaTiO₃ powders with room-temperature ( c/a ) values > 1.008. No transformation could be detected using differential scanning calorimetry for BaTiO₃ particles with a ( c/a ) > 1.008 at room temperature. BaTiO₃ powder with a particle size just too small (0.19 μm) to be tetragonal at room temperature remained cubic down to 80 K. Different models for the cubic-to-tetragonal room-temperature transformation are discussed. Hydroxyl ions do not appear to greatly affect the cubic-to-tetragonal transformation, which appears to be essentially dependent on particle size. It is concluded that a model based on surface free energy, as previously discussed for the monoclinic-to-tetragonal transformation at room temperature of fine ZrO₂ particles, is consistent with the experimental data.     

Synthesis of Monodispersed Fine Hafnium Diboride Powders Using Carbo/Borothermal Reduction of Hafnium Dioxide

Fine hafnium diboride (HfB₂) powders have been prepared by modified carbothermal/borothermal reduction of hafnium dioxide (HfO₂) at relatively low temperatures (1500°–1600°C) for 1–2 h. The XRD patterns could be indexed as hexagonal HfB₂ and no evidence of HfC, HfO₂, or other impurities was observed. Glow discharge mass spectrometer analysis indicates that the synthesized HfB₂ powders had high purity. The synthesized HfB₂ powders had small average crystallite size (around 1 μm) and low oxygen content (<0.30 wt%). Scanning electron microscopy observation of the as-prepared powders demonstrated quasi-column morphology and laser particle size analysis showed monodispersity (polydispersity 0.005).     

Inclusions of Nanometer-Sized Al2O3 Particles in a Crystalline (Sc,Lu)2(WO4)3 Matrix

Nanometer-sized Al₂O₃ particles were successfully synthesized as crystalline inclusions by mixing both components to form the nanometer-sized particles and the (Sc,Lu)₂(WO₄)₃ matrices in a crystal lattice by preparing a solid solution of (Sc,Lu)₂(WO₄)₃ and Al₂(MoO₄)₃ and then decomposing the solid solution. The particles were dispersed uniformly and without agglomeration, which is commonly observed with conventional preparation techniques. The average particle size of the Al₂O₃ was 3.5 nm, and the standard deviation was estimated to be 1.1 nm.     

Piezoelectric Properties of Pb(Mg1/3Nb2/3)O3 PbTiO3 -PbZrO3 Ceramics Modified with Certain Additives

Effects of additives on the piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-PbZrO₃ ceramics in a perovskite-type structure are described. The tetragonality of Pb(Mg_1/3Nb_2/3)_0.375-Ti_0.375Zr_0.25O₃ ceramics increased with the addition of NiO, Cr₂O₃, or Fe₂O₃ but decreased with the addition of MnO₂ or CoO. The dielectric and piezoelectric properties of the base composition were improved markedly through selection of additives in proper amounts. Addition of NiO yielded a high dielectric constant and planar coupling coefficient for compositions at the morphotropic transition boundary. High mechanical Q -factors and low electrical dissipation factors were obtained by addition of MnO₂. Addition of both NiO and MnO₂ produced a mechanical Q -factor of 2051 and a planar coupling coefficient of 0.553. The resonant frequency of Pb(Mg_1/2Nb_2/3)_0.4375Ti_0.4375 zr_0.125O₃ containing MnO₂ had very low temperature and time dependence. The microstructure indicated that ceramics with a high mechanical Q -factor had a fine, uniform grain structure. Addition of Cr₂O₃ retarded grain growth and addition of MnO₂, NiO, CoO, or Fe₂O₃ promoted grain growth in the ternary system.     

Improvement in the Microstructures and Dielectric Properties of Barium Strontium Titanate Glass–Ceramics by AlF3/MnO2 Addition

The microstructures and dielectric properties of barium strontium titanate glass–ceramics are closely related to the AlF₃ and MnO₂ additions. The grain morphology was changed by adding AlF₃, while the dielectric loss was decreased significantly by adding MnO₂. At the same time the breakdown strength (BDS) was improved by doping 4 mol% AlF₃ and 1 mol% MnO₂ with the glass–ceramics. The present investigation resulted in the development of glass–ceramic compositions with high dielectric BDS and low dielectric loss for high energy density capacitor applications.     

Mechanochemical Synthesis and Electrochemical Properties of LiMn2O4

Spinel LiMn₂O₄ as a cathode material for lithium secondary batteries has been synthesized by a mechanochemical process, and its electrochemical properties have been characterized. Highly disordered nanocrystalline LiMn₂O₄ powders have been prepared by the mechanochemical processing of Li₂O and MnO₂ powder mixtures for 24 h. Electrochemical characterization of mechanochemically processed powder has shown that the intercalation of Li⁺ takes place with an initial capacity of 167 mA·h/g in the 2.5–4.3 V range and has better capacity retention as compared to the well-ordered crystalline LiMn₂O₄ powders. The better capacity retention of the mechanochemically processed LiMn₂O₄ powder may be attributed to the highly disordered structure that could accommodate the Jahn–Teller distortion of the spinel structure during Li⁺ intercalation around the 3 V region.     

Single-Source Sol-Gel Synthesis of Nanocrystalline ZnAl2O4: Structural and Optical Properties

Nanometer-sized zinc aluminate (ZnAl₂O₄) particles were synthesized from heterometal alkoxides, [ZnAl₂(OR)₈], possessing an ideal cation stoichiometry for the ZnAl₂O₄ spinel. ZnAl₂O₄ is formed at 400°C, which is the lowest temperature reported for the formation of monophasic ZnAl₂O₄. ²⁷Al magic-angle spinning nuclear magnetic resonance spectroscopy revealed that ZnAl₂O₄ possesses an inverse structure at <900°C, while the normal spinel phase is observed at higher temperatures. The homogeneity of the in-depth composition and Zn:Al stoichiometry (1:2) was confirmed by electron spectroscopy for chemical analysis. Evaluation of the valence-band spectra of ZnAl₂O₄ and ZnS suggested that the hybridization of O 2 p and Zn 3 d orbitals is responsible for lowering the bandgap in the latter. The average crystallite size showed an exponential relationship to the calcination temperature (X-ray diffractometry and transmission electron microscopy data). The optical spectra of different spinel powders (average particle sizes, 20–250 nm) showed that the absorption edge exhibits a blue shift as particle size decreases.