Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Solid-State Synthesis of Ultrafine BaTiO3 Powders from Nanocrystalline BaCO3 and TiO2

Barium titanate has been prepared by solid-state reaction of nanocrystalline TiO₂ (70 nm) with BaCO₃ of different particle size (650, 140, and 50 nm). The results give evidence of a strong effect of the size of BaCO₃ in the solid-state synthesis of barium titanate. The use of nanocrystalline BaCO₃ already leads to formation of the single-phase BaTiO₃ after calcination for 8 h at 800°C. The final powder consists of primary particles of ≈100 nm, has a narrow particle size distribution with d ₅₀=270 nm, and no agglomerates larger than 800 nm. For the coarser carbonate, 4 h calcination at 1000°C are required and the final powder is much coarser. Solid-state reaction of nanocrystalline BaCO₃ and TiO₂ represents an alternative to chemical preparation routes for the production of barium titanate ultrafine powders.     

YBCO Oxalate Coprecipitation in Alcoholic Solutions

A process for synthesis of ultrafine YBa₂Cu₃O_7–x powder by oxalate coprecipitation from nearly saturated solutions of the metal acetates and a 2-propanol solution of oxalic acid was developed. The coprecipitation was complete within 5 min in an ice bath at 0–2°C. The final stoichiometry was Y:Ba:Cu = 1:1.994:2.991, while the particle size and surface area in the homogeneous coprecipitated powder were 0.1–0.2 pm and 24.9 m².g⁻¹, respectively. Because of the uniformity and particle size of the coprecipitated material, reactive YBCO powder with a surface area of 1.7 m².g⁻¹ can be obtained at 780°C in about 12 h.     

Preparation of BaTi4O9 from Oxalates

A barium titanate precursor with a barium:titanium ratio of 1:4 was prepared by controlled coprecipitation of mixed barium and titanium species with an ammonium oxalate aqueous solution at pH 7. The results of thermal analysis and IR measurement show that the obtained precursor is a mixture of BaC₂O₄·0.5H₂O and TiO(OH)₂·1.5H₂O in a molar ratio of 1:4. Crystallized BaTi₄O₉ was obtained by the thermal decomposition of a precipitate precursor at 1300°C for 2 h in air. The dimensions of the powder calcined at 1000°C are between 100 and 300 nm. The grain dimensions of the sintered sample for 2 h at 1300°C are of the order of 10 to 30 μm. Dielectric properties of disk-shaped sintered specimens in the microwave frequency region were measured using the TE₀₁₁ mode. Excellent microwave characteristics for BaTi₄O₉—ɛ= 38 ± 0.5, Q = 3800–4000 at 6–7 GHz and τ _f = 11 ± 0.7 ppm/°C—were found.     

Processing and Characterization of Microemulsion-Derived Lead Magnesium Niobate

Lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), with 3 wt% excess PbO content has been successfully prepared via a microemulsion processing technique. By stepwise hydrolysis using aqueous ammonia as the precipitant, hydroxide precursor was obtained from nitrate solutions dispersed in the nanosized aqueous domains of a microemulsion consisting of cyclohexane, mixed poly(oxyethylene)₅ nonyl phenol ether (NP5) and poly(oxyethylene)₉ nonyl phenol ether (NP9), and an aqueous phase. Upon calcination of the microemulsion-derived precursor at 780°C, an ultrafine perovskite PMN powder with less than 5% pyrochlore phase was obtained. The percentage of perovskite phase increases with increasing calcination temperature, reaching ∼98% at 900°C. The resulting PMN powder exhibits a near-spherical particle morphology although particle agglomerates of ∼0.3 µm in average diameter occur when they are calcined at 850°C. When sintered at 1150°C, the microemulsion-derived PMN showed a maximum relative density of ∼95.6% theoretical density, which gives a maximum dielectric constant of ∼11 000 at 1 kHz and a Curie temperature of -6°C.     

Alkoxide-Hydroxide Route to Syntheltize BaTiO3-Based Powders

When preparing homogeneous, fine barium titanate powders, the major difficulty is to avoid the spontaneous self-condensation between the Ti-OH groups. In the usual way of preparing fine barium titanate powders, chelating agents (citrate, oxalate) or simply unidentate ligands (alkoxy or carboxyl groups) are used to complex titanium atoms. Another way is to mix barium and titanium precursors in a strongly basic medium. The condensation between the Ti(OH)^2-₆Ba²⁺ species directly gives the perovskite compound. Using an alkoxide-hydroxide route, a homogeneous Ba-Ti solution was prepared that completely advanced by condensation between the Ti(OH)^2-₆Ba²⁺ species and led to a controlled-stoichiometry powder. Concerning pure barium titanate, dried powders exhibited the cubic perovskite structure, and a direct sintering at 1150°C, without calcination, led to highly dense BaTiO₃ bodies with fine-grained uniform microstructure (1 μm) that exhibited a high permittivity value at room temperature ( K = 5400). The alkoxide-hydroxide method was also used to prepare dense alkaline-earth perovskite ceramics with complex compositions.     

Alternative Route for Synthesis of Barium Titanyl Oxalate: Molecular Precursor for Macrocrystalline Barium Titanate Powders

An important molecular precursor to barium titanate, namely, barium titanyl oxalate [BaTiO(C₂O₄)₂.4H₂O], has been synthesized by an alternative route. An alcoholic solution containing 1 mol of butyl titanate monomer [(C₄H₉O)₄Ti] is reacted with alcoholic solution containing 2 mol of oxalic acid (H₂C₂O₄:2H₂O) to form an intermediate soluble oxalotitanic acid [H₂TiO(C₂O₄)₂.nH₂O]. The oxalotitanic acid in alcoholic medium is subjected to cation exchange reaction with aqueous solution containing equimolar barium acetate to form an insoluble barium titanyl oxalate (BTO) in yields of 80–85% at room temperature. The pyrolysis of BTO in air at T .750°C/5 h produced barium titanate (BT) powders.     

Peroxo-oxalate Preparation of Doped Barium Titanate

The peroxo-oxalate complexation method is a method that can be used for the preparation of doped barium titanate. In this paper we focus on BaTi_0.91Zr_0.09O₃, which can be used for discharge capacitors in lamp starters. The preparation method described here is based on the complexation and subsequent precipitation in basic environment of Ba, Ti, and Zr ions with hydrogen peroxide and oxalate. The influence of several process parameters, like precipitation temperature and pH, on powder properties is described. A single-phase perovskite crystal structure is obtained after calcination starting from a chloride precursor solution using a precipitation temperature of 40°C and a pH of 9. Because the peroxo-oxalate process starts with inexpensive chlorides and is performed in air, the peroxo-oxalate process is suitable for the commercial production of doped barium titanate.     

Ferroelectrics of Ultrafine Particle Size: I, Synthesis of Titanate Powders of Ultrafine Particle Size

Two methods used to synthesize high-purity ferroelectric titanate powders in controlled, narrow size distributions, with average particle diameters <1000 A, were: (1) isothermal pyrolysis of barium titanyl oxalate or mixed calcium-barium titanyl oxalates as low as 550° and 825°C, respectively, average particle sizes depending strongly on the pyrolysis temperature; and (2) hydrolysis of titanate esters in barium hydroxide. Using solvent media of controlled polarity, high-purity stoichiometric BaTiO₃ was obtained with average sizes as small as 100 A. Factors affecting stoichiometry and particle size are discussed in terms of assumed reaction mechanisms.     

Coprecipitation and Hydrothermal Synthesis of Ultrafine 5.5 mol% CeO2-2 mol% YO1.5ZrO2 Powders

Ultrafine 5.5 mol% CeO₂—2 mol% YO_1.5ZrO₂ powders with controllable crystallite size were synthesized by two kinds of coprecipitation methods and subsequent crystallization treatment. The amorphous gel produced by ammonia coprecipitation and hydrothermal treatment at 200°C for 3.5 h results in an ultrafine powder with a surface area of 206 m²/g and a crystallite size of 4.8 nm. The powder produced by urea hydrolysis and calcination exhibits a purely tetragonal phase. In addition, the powders crystallized by hydrothermal treatment exhibit high packing density and can be sintered at lower temperature (,1400°C) with nearly 100% tetragonal phase achieved.     

Low-Temperature Fabrication of Transparent Yttrium Aluminum Garnet (YAG) Ceramics without Additives

A carbonate precursor of yttrium aluminum garnet (YAG) with an approximate composition of NH₄AlY_0.6(CO₃)_1.9(OH)₂·0.9H₂O was synthesized via a coprecipitation method from a mixed solution of ammonium aluminum sulfate and yttrium nitrate, using ammonium hydrogen carbonate as the precipitant. The precursor precipitate was characterized using chemical analysis, differential thermal analysis/thermogravimetry, X-ray diffractometry, and scanning electron microscopy. The sinterability of the YAG powders was evaluated by sintering at a constant rate of heating in air and vacuum sintering. The results showed that the precursor completely transforms to YAG at ∼1000°C via the formation of a yttrium aluminate perovskite (YAP) phase. YAG powders obtained by calcining the precursor at temperatures of ≤1200°C were highly sinterable and could be densified to transparency under vacuum at 1700°C in 1 h without additives.     

Bismuth Titanate from Mechanical Activation of a Chemically Coprecipitated Precursor

Most of the chemistry-based preparation routes for bismuth titanate (BIT) involve calcination at elevated temperatures in order to realize precursor-to-ceramic conversion. In a completely different approach using an amorphous BIT hydroxide precursor, nanocrystalline particles of layered perovskite BIT are synthesized by mechanical activation, skipping the detrimental crystallite coarsening and particle aggregation encountered at high temperatures. Mechanical activation leads to nucleation and steady growth of BIT crystallites in the amorphous precursor matrix, while Bi₂O₃ is involved as an intermediate transitional phase. The activation-derived BIT particles demonstrate a rounded morphology of ∼50 nm in size. This is in contrast to the BIT derived from calcination of the coprecipitated precursor at 600°C that is dominated by coarsened platelike particles. The former is sintered to a density of >95% theoretical at 875°C for 2 h, leading to a dielectric constant of ∼1260 when measured at 1 MHz and the Curie temperature of 646°C.     

State of Magnesia in Magnesia (10.4 mol%)-Doped Zirconia Powder Prepared from Coprecipitation

MgO (10.4 mol%)-doped ZrO₂ powder, which was prepared by coprecipitation and calcination at 750°C, was leached and milled, respectively. The powders were characterized by Auger electron scanning microprobe and XRD technologies. Only the 2.3 mol% MgO was soluble in ZrO₂; it stabilized ZrO₂ as the metastable tetragonal phase (crystallite size ∼45 nm) at room temperature. The rest of the MgO (8.1 mol%) existed on the surface of the ZrO₂ grains in the prepared powder.     

Nano α-Al2O3 Powder Preparation by Calcining an Emulsion Precursor

An experimental study has been conducted to evaluate the formation of nano α-Al₂O₃ under various conditions, such as different calcining temperatures and emulsion ratios of aqueous aluminum nitrate solutions and oleic acid with a high-speed stirring mixer. Four batches of the precursor powders were calcined at three different temperatures of 1000°, 1050°, and 1100°C for 2 h and a terminal product of nano α-Al₂O₃ powders was obtained. The products have been identified by X-ray diffraction (XRD), specific surface area measurement scanning electron microscope, and transmission electron microscope (TEM). The XRD results show that the phase of powders is determined to be α-Al₂O₃, indicating that the overall process has been effective. The optimum calcination temperature of the precursor powder for crystallization of nano α-Al₂O₃ was found to be 1000°C for 2 h. The TEM image indicates that the particle grains have a sub-spherical shape with a mean size of 50–100 nm.     

Fabrication of Transparent, Sintered Sc2O3 Ceramics

We report here the fabrication of transparent Sc₂O₃ ceramics via vacuum sintering. The starting Sc₂O₃ powders are pyrolyzed from a basic sulfate precursor (Sc(OH)_2.6(SO₄)_0.2·H₂O) precipitated from scandium sulfate solution with hexamethylenetetramine as the precipitant. Thermal decomposition behavior of the precursor is studied via differential thermal analysis/thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffractometry, and elemental analysis. Sinterability of the Sc₂O₃ powders is studied via dilatometry. Microstructure evolution of the ceramic during sintering is investigated via field emission scanning electron microscopy. The best calcination temperature for the precursor is 1100°C, at which the resultant Sc₂O₃ powder is ultrafine (∼85 nm), well dispersed, and almost free from residual sulfur contamination. With this reactive powder, transparent Sc₂O₃ ceramics having an average grain size of ∼9 μm and showing a visible wavelength transmittance of ∼60–62% (∼76% of that of Sc₂O₃ single crystal) have been fabricated via vacuum sintering at a relatively low temperature of 1700°C for 4 h.     

Properties of the Solid Electrolyte Gadolinia-Doped Ceria Prepared by Thermal Decomposition of Mixed Cerium-Gadolinium Oxalate

Fine-grained powder of the mixed oxide (CeO₂)_0.9(Gd₂O₃)_0.1, which is an ionic conductor for oxygen ions, was prepared by coprecipitation of the corresponding oxalates followed by calcination. The powder was used to prepare pellets sintered at a relatively low temperature of 1000°C compared with the usual sintering temperature of 1700° to 1800°C. The size of the powder grains was determined from BET surface area (S_BET) measurements. The effect of precipitation conditions and calcination temperature on S_bet was examined. The largest surface area measured was 88 m²/g. Decomposition of the oxalate powder was followed using an optical dilatometer. The decomposition was indicated by a large shrinkage and it was completed below 300°C (for a heating rate of 3.3°C/min). The formation of the oxide was verified by X–ray diffraction analysis. It shows that the product of decomposition is the oxide and that decomposition can be carried to completion at 250°C if the heating lasts for 1 h. The pellets had a density of 83% of theoretical, small grains (0.5 μm), and a conductivity which, at 900°C, is two–thirds of the conductivity of dense samples obtained from the same raw material, but calcined and fired at much higher temperatures.     

Hydrothermal Synthesis for Large Barium Titanate Powders at a Low Temperature: Effect of Titania Aging in an Alkaline Solution

Monodisperse and spherical barium titanate (BaTiO₃) powders with diameters of 200–470 nm were directly prepared by a low-temperature hydrothermal method at 90°C. Spherical titania (TiO₂) powders, ranging in size from 150 to 420 nm, were initially prepared by a controlled hydrolysis and condensation reaction, aged in a highly alkaline solution for 12 h, and then hydrothermally reacted with barium hydroxide to be converted to BaTiO₃ without a morphological change. The aging step of the TiO₂, where the surface of TiO₂ was highly densified through elimination of the pores, was indispensable to retain the sizes and shapes of TiO₂ in the resulting BaTiO₃. This was due to the fact that the formation of BaTiO₃ proceeded by an in situ reaction mechanism. The resulting BaTiO₃ powders exhibited dense and nonporous structures even after calcination at 1000°C.     

Nanosized PbZrO3 Powder from Oxalate Precursor: Microwave-Aided Synthesis and Thermal Characterization

Nanosized lead zirconate (PbZrO₃) powder was synthesized from its oxalate precursor, namely lead zirconyl oxalate (LZO). LZO heated in a microwave heating system for 1 h yielded the PbZrO₃ at 600°C. The same precursor (LZO), when heated in a resistance-heated furnace at 850°C for 3 h, does not give a pure product. Thermogravimetry, differential thermal analysis, and X-ray diffraction techniques were used to characterize the precursor and optimize the conditions for microwave processing. The particle size of PbZrO₃ powder prepared at 600°C using microwave heating was measured using transmission electron microscopy (TEM). The TEM images show that the particles of PbZrO₃ are spherical in shape and that the particle size varies between 20 and 22 nm.     

Fine Strontium Ferrite Powders from an Ethanol-Based Microemulsion

A fine strontium ferrite powder with high coercivity was successfully prepared by forming hydroxide precursor particles in the continuous ethanol-based phase of a microemulsion consisting of iso-octane, NP9, and an ethanol solution containing Sr²⁺ and Fe³⁺ cations at a molar ratio of 1:12. The microemulsion-derived hydroxide precursor was calcined at various temperatures, ranging from 600° to 1100°C, to develop the hexagonal strontium ferrite phase. X-ray diffractometry and infrared characterizations revealed that the formation mechanisms of strontium ferrite in the microemulsion-derived precursor differed from those of the precursor derived by conventional coprecipitation. The microemulsion resulted in a strontium ferrite of finer particle size and better magnetic properties than those of the conventionally coprecipitated strontium ferrite. The microemulsion-derived strontium ferrite exhibited an intrinsic coercivity of 6195 Oe and a saturation magnetization of 58.28 emu/g when calcined at 900^oC. The saturation magnetization increased further, to 69.75 emu/g, when the microemulsion-derived precursor was calcined at 1100^oC.     

Reactive Ceria Nanopowders via Carbonate Precipitation

Nanocrystalline CeO₂ powders have been successfully synthesized via a carbonate precipitation method, using ammonium carbonate (AC) as the precipitant and cerium nitrate hexahydrate as the cerium source. The AC/Ce³⁺ molar ratio ( R ) affects significantly precursor properties, and spherical nanoparticles can be produced only in a narrow range of 2 < R ≤ 3. The precursor, having an approximate composition of Ce(OH)CO₃·2.5H₂O, decomposes to CeO₂ at temperatures ≥300°C. The CeO₂ powder calcined at 700°C exhibits high reactivity and can be densified to >99% of theoretical at 1000°C.