Synthesis of Nanocrystalline Lanthanum Strontium Manganite Powder by the Urea–Formaldehyde Polymer Gel Combustion Route

Nanocrystalline lanthanum strontium manganite (LSM) powder has been synthesized by combustion of a transparent gel obtained by the polymerization of methylol urea and urea in a solution containing La³⁺, Sr²⁺, and Mn²⁺ (LSM ions). Chemistry of the transparent urea–formaldehyde (UF) polymer gel formation and structure of the gel have been proposed such that the LSM ions act in between the growing UF polymer chains by interacting through NH, OH, and CO groups by co-ordination and prevent polymer self-assembly through inter-chain hydrogen bonding as evidenced from infrared spectrum. Thermally stable structures formed by the decomposition of UF polymer below 300°C undergo combustion in the presence of nitrate oxidant in a temperature range from 350°–450°C. A perovskite LSM phase has been formed by self-sustained combustion of the dried gel initiated with little kerosene. The powder obtained after deagglomeration and calcination at 600°C for 2 h has a D ₅₀ value of 0.19 μm, and the particles are aggregates of crystallites 10–25 nm in size.     

Hydroxyapatite Coating on Thermally Oxidized Titanium Substrates

Titanium substrates were oxidized in oxygen or air at temperatures of 600°–800°C, then immersed in solutions of 2.0m M – 20.7m M CaCl₂ and 1.2m M –12.4m M KH₂PO₄ for aging periods of 0.5–10 d. The titanium surface was successfully coated with hydroxyapatite (HAP) when the substrates were oxidized in oxygen gas at 610°C for 1 h and then aged in a solution of 2.00m M Ca²⁺ and 1.20m M PO₄³⁻. The Ca/P ratio of the surface coating increased toward its stoichiometric HAP value (return 10/6) as the aging time increased; the Ca/P ratio attained a value of 1.66 after 10 d.     

Transparent Hydroxyapatite Ceramics through Gelcasting and Low-Temperature Sintering

Transparent hydroxyapatite (HAP) was prepared by sintering gel-cast powder compacts at 1000°C for 2 h; the resultant HAP material was studied using X-ray diffractometry, transmission electron microscopy, scanning electron microscopy, and microhardness measurement. Nanoscale HAP crystallites were prepared using a precipitation method that involved calcium nitrate and ammonium dihydrogen orthophosphate solutions; the preparation was conducted at a temperature of 0°C. The precipitate was gel-cast and sintered at 1000°C in the form of a transparent ceramic that had a uniform grain size of 250 μm. The maximum Vickers microhardness obtained for a sample sintered at 1000°C was 6.57 GPa. The sintering behavior of gel-cast samples prepared from high-temperature-precipitated HAP was compared with that of material prepared at 0°C.     

Methanol–Water System for Solvothermal Synthesis of YVO4:Eu with High Photoluminescent Intensity

A methanol–water mixed solvent was used as a reaction medium for the preparation of Eu³⁺-doped YVO₄ phosphor materials. These were synthesized by a solvothermal method at 150°–300°C using a 10 vol% solution of water in methanol as the reaction medium followed by calcination at 1000°–1200°C. The phase composition and optical properties of the products were characterized by X-ray diffraction, scanning electron microscope, and photoluminescence spectroscopy. The powders obtained were composed of spherical particles ∼0.5 μm in size, with an internal structure that was different for samples prepared under subcritical and supercritical conditions of methanol. After the calcination, the powders obtained at 240°–300°C retained the initial raspberry-like morphology, whereas the morphology of samples prepared at 150°–210°C changed significantly due to noticeable sintering. The fluorescence intensity exhibited by the prepared samples was higher than the fluorescence intensity shown by one of the best commercial YVO₄:Eu phosphors having a large particle size.     

Conversion of Tetranary Borate Glasses to Phosphate Compounds in Aqueous Phosphate Solution

In our earlier work, it was found that particles of a ternary alkali-borate glass, containing either CaO or BaO, converted completely to a crystalline phosphate of calcium or barium when reacted in an aqueous phosphate solution at 37°C. The present work is an extension of our earlier work to investigate the conversion of tetranary borate glass with the composition 10Li₂O·10CaO·10(AeO or T₂O₃)·60B₂O₃ (weight percent), where Ae is the alkai-earth metal Mg or Ba, and T is the transition metal La, Sm, or Dy. In the experiments, particles of each glass (150–300 μm) were reacted in 0.25 M K₂HPO₄ solution with a starting pH of ∼9.0 at 37°C. Weight loss and pH measurements indicated that the reaction was complete after 30–50 h, yielding an amorphous product. X-ray fluorescence showed that the as-formed product consisted of a calcium phosphate phase that contained the alkali-earth metal or transition metal present in the starting glass. Heating the as-formed material for 8 h at 600°–700°C produced a mixture of two crystalline phosphates: calcium phosphate and an alkali-earth or transition metal phosphate. The kinetics and mechanism of converting tetranary borate glass to phosphate materials are discussed and compared with data from earlier work for the conversion of ternary borate glass.     

Young's Modulus, Flexural Strength, and Fracture of Yttria-Stabilized Zirconia versus Temperature

The flexural strength and elastic modulus of cubic zirconia that was stabilized with 6.5 mol% yttria was determined in the temperature range of 25°–1500°C in air. Specimens were diamond machined from both hot-pressed and sintered billets that were prepared from alkoxy-derived powders. The flexural strength of the hot-pressed material decreased, from }300 MPa at 25°C to 50 MPa at 1000°C, and then increased slightly as the temperature increased to 1500°C. The flexural strength of the sintered material decreased, from 150 MPa at 25°C to 25 MPa at 750°C, and then appeared to increase slightly to }1500°C. Flexural strengths were comparable to other fully stabilized zirconia materials. The overall fracture mode was transgranular at low temperatures, mixed mode at }500°–1000°C, and intergranular at higher temperatures. Pores or pore agglomerates along grain boundaries and at triple points were fracture origins. The value of the porosity-corrected Youngs moduli was 222 GPa at 25°C, decreased to }180 GPa at 400°C, and then was relatively constant with increasing temperature to 1350°C.     

Electrical Properties of Manganese-Doped Titanium Dioxide

The electrical conductivity and Seebeck coefficient for TiO₂ doped with varying amounts of MnO₂ have been measured over the temperature range of 900°–1100°C. The Hall coefficient was also measured over the temperature range of 300°–500°C. The electrical conductivity and carrier density were found to decrease initially, go through a minimum at approximately x = 0.0001–0.001, and then increase with increasing content of MnO. For dopant levels above 0.01 at.%, p -type electrical conduction behavior was observed.     

Sol–Gel Synthesis of Silica-Based Oxyfluoride Glass-Ceramic Thin Films: Incorporation of Eu3+ Activators into Crystallites

Transparent oxyfluoride glass-ceramic thin films were prepared using a sol–gel method starting from rare-earth trifluoroacetate/silicon alkoxide solutions. SiO₂–LaF₃ and SiO₂–LaOF glass-ceramics were formed by heating at temperatures of 300°–500°C and 600°–900°C, respectively. Eu³⁺ activators were successfully incorporated into oxyfluoride crystals, as evidenced by their luminescent properties, such as capability of a charge-transfer (O^2––Eu³⁺) excitation, suppression of a multiphonon relaxation, and occurrence of a cross-relaxation at low Eu³⁺ concentrations. As a result, the films exhibited strong red emission by ultraviolet excitation. The incorporation supposedly originated from decomposition of the (La,Eu)-trifluoroacetates in the silica-gel matrix.     

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.     

Thermal Evolution and Sintering Behavior of a 2:1 Mullite Gel

The thermal evolution of a mullite gel of composition 2Al₂O₃·SiO₂ has been investigated. The gel crystallized at 1300°C into an alumina-rich mullite and corundum, instead of single-phase 2Al₂O₃·SiO₂ mullite. The amount of Al₂O₃ that dissolved in the mullite structure has been determined in the 1300–1780°C temperature range by measuring the mullite lattice parameters. A maximum limit for the amount of Al₂O₃ in solid solution has been observed. Densification of the gel powders has been analyzed up to temperatures of 1780°C. The microstructure of dense materials always showed the presence of residual Al₂O₃ particles.     

Nanocrystalline Mullite Synthesis at a Low Temperature: Effect of Copper Ions

Nanocrystalline mullite with grain sizes in the range of 13–30 nm has been prepared by the sol–gel route at a temperature as low as 600°C with the incorporation of copper ions as copper sulfate. Characterization of the copper-doped mullite was performed by DTA–TG, X-ray diffraction (XRD), FESEM, and FTIR spectroscopy.     

Direct Formation of Mg–Al-Layered Double-Hydroxide Films on Glass Substrate by the Sol–Gel Method With Hot Water Treatment

Amorphous Al₂O₃–MgO thin films with an Mg/Al ratio of unity were prepared on glass substrates by the sol–gel method with a heat treatment at 300°C for 30 min. By immersing the films in water containing sodium hydroxide (pH 10–13) at 100°C, nano-crystals of Mg–Al-layered double hydroxide (LDH) with a hexagonal structure, which is called hydrotalcite and the most basic composition of LDH, were precipitated on the amorphous Al₂O₃–MgO films. The maximum amount of Mg–Al nanocrystals was obtained when the film was immersed in basic solution of pH 12.     

Novel Mullite Synthesis Based on Alumina Nanoparticles and a Preceramic Polymer

Heating in air of a selected mixture of a silicone resin and alumina nanoparticles in the temperature range 1200°–1500°C yielded dense, crack-free mullite samples. Al₂O₃, due to its nanometric size, proved to be very reactive toward silica, deriving from the ceramization of the preceramic polymer, leading to the formation of a large volume fraction of mullite crystals even at low firing temperatures (1250°C). Because of the homogeneity of the distribution of alumina nanoparticles in the starting system, the ceramized samples exhibited a very fine microstructure consisting of crystals with an average dimension in the range of 50–300 nm.     

Nanostructured Dense ZrO2 Thin Films from Nanoparticles Obtained by Emulsion Precipitation

Nonagglomerated spherical ZrO₂ particles of 5–8 nm size were made by emulsion precipitation. Their crystallization and film-forming characteristics were investigated and compared with nanosized ZrO₂ powders obtained by sol–gel precipitation. High-temperature X-ray diffraction indicated that the emulsion-derived particles are amorphous and crystallize at 500°C into tetragonal zirconia, which is stable up to 1000°C. Crystallite growth from 5–20 nm occurred between 500°–900°C. Films of 6–75 nm thickness were made by spreading, spin coating, and controlled deposition techniques and annealed at 500°–600°C. The occurrence of t -ZrO₂ in the emulsion-precipitated powder is explained by the low degree of agglomeration and the corresponding low coarsening on heating to 500°–800°C, whereas the agglomerated state of the sol–gel precipitate powder favors the occurrence of the monoclinic form of zirconia under similar conditions.     

Sol-Gel Synthesis of a New Oxide-Ion Conductor Sr- and Mg-Doped LaGaO3 Perovskite

Sr- and Mg-doped LaGaO₃ powders were prepared from a salt acetate solution. The stable solution was peptized by reacting ammonium hydroxide with the precursor solution. Thermal analysis (DTA/TGA) was used to characterize first the dehydration and then the thermal decomposition of the organic ligands of the dried gel. The transformation from amorphous powders into a crystallized, homogeneous oxide phase corresponds to two endothermic peaks in the DTA curve; the first one at 150°C is related to the removal of water and is followed by a shoulder at 250°C. The second peak at 300°C corresponds to a superposition of two decomposition reactions: acetate salt into its oxycarbonate and this oxycarbonate into its oxide. Two subsequent exothermic peaks correspond to oxidation of evolved gases such as methane, hydrogen, and carbon monoxide. TEM observations show an average 10 nm particle size of the LaGaO₃powder after annealing at 600°C. X-ray diffraction patterns indicate a pure primitive-cubic phase is formed by 1300°C without formation of any SrLaGaO₃ impurity. The impedance spectroscopy on a 93%-dense sample exhibits no grain-boundary contribution and an ac conductivity σ= 0.11 Ω⁻¹·cm⁻¹ at 800°C.     

Low-Temperature Synthesis of Calcium Hexa-Aluminate

Calcium hexa-aluminate (CaO·6Al₂O₃) has been prepared from calcium nitrate and aluminum sulfate solutions in the temperature range of 1000°–1400°C. A 0.3 mol/L solution of aluminum sulfate was prepared, and calcium nitrate was dissolved in it in a ratio that produced 6 mol of Al₂(SO₄)₃·16H₂O for each mole of Ca(NO₃)₂·4H₂O. It was dried over a hot magnetic stirrer at ∼70°C and fired at 1000°–1400°C for 30–360 min. The phases formed were determined by XRD. It was observed that CaO·Al₂O₃ and CaO·2Al₂O₃ were also formed as reaction intermediates in the reaction mix of CaO·6Al₂O₃. The kinetics of the formation of CaO·6Al₂O₃ have been studied using the phase-boundary-controlled equation 1 − (1 − x )^1/3= K log t and the Arrhenius plot. The activation energy for the low-temperature synthesis of CaO·6Al₂O₃ was 40 kJ/mol.     

Preparation of Titanium Nitride Films from Amide Precursors Synthesized by Electrolysis

A TiN precursor solution was synthesized by galvanostatic electrolysis of Ti metal and isopropylamine at a current density of 50 mA·cm⁻² at room temperature. TiN films were prepared by dip-coating of the precursor solution on a Si wafer, followed by two-stage heat treatment at 400°C and a fixed temperature of 800–1200°C in flowing N₂, N₂/NH₃, or NH₃ gas. The TiN films were characterized by XRD, chemical analysis, XPS, and electrical resistivity measurements. The TiN films were composed of uniform grains 20 to 200 nm in size with thicknesses ranging from 300 to 400 nm at temperatures of 800–1200°C. The effect of the heat treatment atmosphere (N₂ and NH₃) on the impurity content, crystallinity, particle size, and electrical resistivity is discussed.     

Synthesis of BaTiO3 Particles with Tailored Size by Precipitation from Aqueous Solutions

Well-defined and stoichiometric spherical particles of BaTiO₃ of narrow size distribution were produced at 82° and 92°3C by precipitation from chloride solutions in a strong alkaline environment. The size of the particles can be tailored in the range from ≅10³ to 70–80 nm by increasing the barium concentration from ≅0.07 to 0.7 mol/L. The particles are composed of tight aggregates resulting from the assembly of several nanocrystals. The size of the nanocrystals decreases from 200–300 to 30–40 nm by increasing reactant concentration. At low barium concentration (≤0.07 mol/L at 82°3C, ≤0.06 mol/L at 92°3C), formation of BaTiO₃ is strongly slowed down and nonstoichiometric, Ti-rich powders are produced. Under these conditions, the particles have the tendency to develop a dendritic-like morphology.     

Porous, Biphasic CaCO3-Calcium Phosphate Biomedical Cement Scaffolds from Calcite (CaCO3) Powder

Calcite (CaCO₃) is a geologically abundant material, which can be used as a starting material in producing biomedical scaffolds for clinical dental and orthopedic applications. Bone-filling applications require porous, biocompatible, and resorbable materials. Commercially available CaCO₃ powders were physically mixed, for 80–90 s, with an orthophosphoric acid (H₃PO₄) solution, which was partially neutralized to pH 3.2 by adding NaOH, to form biphasic, micro-, and macroporous calcite-apatitic calcium phosphate (Ap-CaP) cement scaffolds of low strength. The resultant carbonated and Na-doped Ap-CaP phase in these scaffolds crystallographically and spectroscopically resembled calcium hydroxyapatite. Upon mixing CaCO₃ powders and the setting solution, carbon dioxide gas was in situ generated and formed the pores. Thus formed scaffolds contained pores over the range of 20–750 μm. Scaffolds were also converted to single-phase Ap-CaP, without altering their porosity, by soaking them in 0.5  M phosphate buffer solutions at 80°C for 36 h in glass bottles. Soerensen's buffer solution was also shown to be able to convert the calcite powders into single-phase Ap-CaP powders upon soaking at 60–80°C. This robust procedure of synthesizing Ap-CaP bioceramics is simple and economical.     

Electrospinning Zirconia Fiber From a Suspension

A zirconia suspension containing 5–10 nm size zirconia particles was modified by adding different amounts of polymer solution to enable electrospinning of zirconia fibers from a range of compositions. The electrospun fibers were heat treated at 600° and 1200°C, and analysis of size distribution reveals that zirconia fibers down to about 200 nm in diameter can be prepared in this way, in contrast to other spinning processes, which are able to produce zirconia fibers having diameters ≥3000 nm.