Pressureless Sintering of Dense Si3N4 and Si3N4/SiC Composites with Nitrate Additives

The effect of aluminum and yttrium nitrate additives on the densification of monolithic Si₃N₄ and a Si₃N₄/SiC composite by pressureless sintering was compared with that of oxide additives. The surfaces of Si₃N₄ particles milled with aluminum and yttrium nitrates, which were added as methanol solutions, were coated with a different layer containing Al and Y from that of Si₃N₄ particles milled with oxide additives. Monolithic Si₃N₄ could be sintered to 94% of theoretical density (TD) at 1500°C with nitrate additives. The sintering temperature was about 100°C lower than the case with oxide additives. After pressureless sintering at 1750°C for 2 h in N₂, the bulk density of a Si₃N₄/20 wt% SiC composite reached 95% TD with nitrate additives.     

Fabrication of NiO Nanoparticle-Coated Lead Zirconate Titanate Powders by the Heterogeneous Precipitation Method

NiO nanoparticle-coated lead zirconate titanate (PZT) powders are successfully fabricated by the heterogeneous precipitation method using PZT, Ni(NO₃)₂·6H₂O, and NH₄HCO₃ as the starting materials. The amorphous NiCO₃·2Ni(OH)₂·2H₂O are uniformly coated on the surface of PZT particles. XRD analysis and the selected-area diffraction (SAD) pattern indicate that the amorphous coating layer is crystallized to NiO after being calcined at 400°C for 2 h. TEM images show that the NiO particles of ∼8 nm are spherical and weakly agglomerated. The thickness of the nanocrystalline NiO coating layer on the surface of PZT particle is ∼30 nm.     

Nanosized Zinc-Oxide Particles Derived from Mechanical Activation of Zn5(NO3)2(OH)8·2H2O in Sodium Chloride

Nanosized ZnO particles are successfully synthesized via mechanical activation of a zinc nitrate hydroxide hydrate (Zn₅(NO₃)₂(OH)₈·2H₂O) precursor in NaCl matrix for 15 h. The ZnO particles obtained are in the nanosize range of ∼20 nm, with a well-established hexagonal morphology. They compare favorably with those derived from conventional calcination of the precursor. The decomposition of Zn₅(NO₃)₂(OH)₈·2H₂O precursor and formation of nanocrystalline ZnO cannot be completed by mechanical activation in the absence of NaCl, which acts as both an effective dispersing matrix and drying agent although it remains chemically inert during mechanical activation. The powder derived from calcination at 400°C does not possess powder characteristics comparable to that of the powder derived from the mechanical activation in NaCl, because of the extensive particle coarsening and aggregation at the calcination temperature.     

Water-Based Gelcasting of Surface-Coated Silicon Nitride Powder

A layer of Y₂O₃–Al₂O₃, used as a sintering aid, was coated onto the surface of Si₃N₄ particles by the precipitation of inorganic salts from a water-based solution containing Al(NO₃)₃, Y(NO₃)₃, and urea. The electrokinetic and colloidal characteristics of the Si₃N₄ powder were changed significantly by the coating layer. As a result, dispersion of the Y₂O₃–Al₂O₃-coated Si₃N₄ powder was significantly greater than that of the original powder. Furthermore, the Y₂O₃–Al₂O₃ coating layer prevented the hydrogen-gas-discharging problem that occurred during gelcasting of the original Si₃N₄ powder because of reaction between the uncoated powder and the basic aqueous solution in suspension. Surface coating, as well as the gelcasting process, significantly improved the microstructure, room-temperature bending strength, and Weibull modulus of the resulting ceramic bodies.     

A Novel Way to Synthesize Yttrium Aluminum Garnet from Metal–Inorganic Precursors

Yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) was synthesized by sol–gel processing from the stoichiometric amounts of aluminum pellets, Y(NO₃)₃·6H₂O, and Al(NO₃)₃·9H₂O or AlCl₃·6H₂O, with suitable kinds of acid (citric acid, acetic acid, etc.) as catalysts. Polycrystalline YAG powder was obtained by drying the YAG precursor followed by calcination at temperatures above 900°C. Thermogravimetry/differential thermal analysis and Fourier transform infrared specotrscopic analyses in air showed an exothermic peak at ∼900°C, attributed to the formation of a polycrystalline YAG phase and weight loss of 60% at 1000°C, caused by the decomposition of hydroxyl and NO₃⁻, etc. X-ray diffraction analysis showed that YAG can be formed at 900°C, and no other intermediate was observed. In particular, the YAG sol can be used for dry-spinning fibers with the aid of some organic polymer.     

Effect of Some Additives on the Specific Surface of Alumina Obtained from Aluminum-Ammonium Alum

The effect of Al(NO₃)₃·9H₂O, AlCl₃·6H₂O, Al(CH₃COO)₃, and NH₄F on the specific surface of Al₂O₃ obtained from aluminum-ammonium alum by calcining was studied. It was found that the use of these additives makes it possible to obtain Al₂O₃ with specific surface varying from 1 to 135 m²/g after thermal treatment in the interval from 1273 to 1423 K. The changes in the morphology and structure of powederd Al₂O₃ obtained from alum containing these additives were studied by electron microscope observations.     

Preparation of Composite Particles by Pulsed Nd-YAG Laser Decomposition of [(CH3)2N]4Ti to TiN-Coat TiO2, Al2O3, or Si3N4 Powders

Irradiation of Ti[N(CH₃)₂]₄ by the 1.064-μm line of a pulsed Nd: YAG laser in the presence of TiO₂, Al₂O₃, or Si₃N₄ particles has been found to form amorphous deposits on the oxide particles. The resulting materials can be processed into TiN/TiO₂, TiN/Al₂O₃, or TiN/Si₃N₄ composites with the TiN component on the surface of the particles. The powders have been characterized by Raman spectroscopy and X-ray powder diffraction studies. The surface analysis of the composites by X-ray photoelectron spectroscopy and high-resolution electron microscopy is presented.     

Fabrication of Translucent Magnesium Aluminum Spinel Ceramics

A precursor for magnesium aluminum spinel powder, composed of crystalline ammonium dawsonite hydrate (NH₄Al(OH)₂CO₃·H₂O) and hydrotalcite (Mg₆Al₂(CO₃)(OH)₁₆·4H₂O) phases, was synthesized via precipitation, using ammonium bicarbonate as the precipitant. The precursor was characterized by differential thermal analysis/thermogravimetry, X-ray diffractometry, and scanning electron microscopy. Reactive spinel powder, which could be densified to translucency under vacuum at 1750°C in 2 h without additives, was obtained by calcining the precursor at 1100°C for 2 h.     

Effects of Seed Layer Characteristics on the Synthesis of ZnO Nanowires

Single crystalline zinc oxide (ZnO) nanowires were synthesized on sputter-deposited ZnO seed layers via hydrothermal reactions in an equimolar (20 mM) aqueous solutions of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ at 90°C. The sputter-deposited ZnO seed layers were prepared to exhibit different crystalline structures in order to examine their effects on the growth of ZnO nanowires. It was found that the nanowire diameter depends on the size of the (002) grains of the seed layer. This is attributed to the epitaxially growth of the nanowires from the columnar grains of the seed layer which is shown by the TEM analysis.     

Solid-State Synthesis of LaCoO3 Perovskite Nanocrystals

A solid-state reaction process has been developed to synthesize perovskite-type LaCoO₃ nanocrystals with grain diameters of 15–40 nm. In the first step of the preparation, ∼5 nm composite hydroxide nanoparticles are synthesized by the solid-state reaction of La(NO₃)₃· n H₂O and Co(NO₃)₂·6H₂O with KOH at ambient temperature. A perovskite-type rhombohedral LaCoO₃ phase appears at 550°C, after the hydroxide has been calcined at various temperatures. The phase transformation process is complete at ∼800°C, yielding a single-phase binary oxide. The results indicate that the new process is convenient, inexpensive, and effective for obtaining LaCoO₃ nanocrystals with high yield.     

Synthesis and Characterization of Amorphous Si2N2O

Amorphous silicon oxynitride powder was synthesized by nitridation of high-purity silica in ammonia at 1120°C. The resulting material was X-ray amorphous, and its chemical characteristics were determined by X-ray photoelectron spectroscopy (XPS) and ²⁹Si nuclear magnetic resonance (NMR). The XPS analysis showed a shift to lower binding energies for the Si₂ p peak with increasing nitrogen content. Upon initial nitridation, the full width at half maximum (FWHM) of the Si₂ p peak increased, but decreased again at higher nitrogen contents, thus showing the formation of a silicon oxynitride phase with a single or small range of composition. The ²⁹Si NMR analysis showed the formation of (amorphous) Si₃N₄ (Si–N₄) and possibly two oxynitride phases (Si–N₃O, Si–N₂O₂). It is concluded that while XPS, FT-IR, and nitrogen analysis may show the formation of an homogeneous, amorphous silicon oxynitride (Si₂N₂O) phase, the formation of phase–pure, amorphous Si₂N₂O is extremely difficult via this route.     

Silicon Nitride Joining

Hot-pressed Si₃N₄ was joined using an Mgo-A1₂O₃-SiO₂ glass composition chosen to approximate the oxide portion of the grain-boundary phase in the ceramic. After it has been heated at 1550° to 1650°, the interface of the joined ceramic is an interlocking mixture of Si₂N₂O, β-Si₃N₄, and a residual oxy-nitride glass. The kinetics of reactions between Si₃N₄ and the molten joining composition were studied by X-ray diffraction analysis of the phases present in Si₃N4 powder-glass mixtures quenched after varied heat treatments. Analytical transmission electron microscopy of the composition and micro-structure of the reaction zone in joined specimens, together with the X-ray diffraction results, suggests that the driving force for joining is the lowering of the Si₃N₄ interfacial energy when it is wet by the molten silicate, augmented by the negative Gibbs energy for the reaction SiO₂( l ) + Si₃N₄= 2Si₂N₂O.     

Electroceramics from Source Materials via Molecular Intermediates: PbTiO3 from TiO2 via [Ti(catecholate)3]2-

The precursor [NH₄]₂[Ti(catecholate)₃] · 2H₂O is known to react with Ba(OH)₂· 8H₂O in an acid/base process that generates Ba[Ti(catecholate)₃] · 3H₂O, a compound which undergoes low-temperatue calcination to produce BaTiO₃ powder. Attempts to develop similar routes to PbTiO₃ have been frustrated, since lead(II) hydroxide does not exist. The amphoteric yellow PbO and the basic oxide, Pb₆O(OH)₆⁴⁺, are both insufficiently basic to react with [NH₄]₂[Ti(catecholate)₃] · 2H₂O. Based on the large sizes of both the [Ti(catecholate)₃]^2- anion and the Pb²⁺ cation, a precipitation method has been developed in which lead nitrate and [NH₄]₂[Ti(catecholate)₃] · 2H₂O are added together in an aqueous medium causing precipitation and leaving only NH₄NO₃ in solution. The lead-titanium-catecholate complex that forms in this manner undergoes low-temperature pyrolysis to produce PbTiO₃. SEM indicates a submicrometer ultimate crystallite size.     

Preparation of Fine, Spherical Yttria-Stabilized Zirconia by the Spray-Pyrolysis Method

Fine yttria-stabilized zirconia powders were prepared by the spray pyrolysis of aqueous solutions of ZrOCl₂·8H₂O and Y(NO₃)₃·5H₂O (3 mol%). An appropriate thermal treatment resulted in slightly porous spherical particles with a narrow size distribution. The sintering ability of these powders was evaluated.     

Nanometer-Sized ZrO2 Particles Prepared by a Sol–Emulsion–Gel Method

ZrO₂ powder was prepared by a sol–emulsion–gel method at temperatures below 140°C from ZrO(NO₃)₂· n H₂O. The asprepared powder was amorphous, but crystallized into the tetragonal structure by 600°C. The metastable tetragonal powder (600°C) was comprised of ultrafine 4- to 6-nm size particles. On heat treatment, the tetragonal form completely transformed into the monoclinic state at 1100°C. Preliminary studies indicate good sinterability with densities greater than 94% at 1100°C and with a grain size of 0.25 μ.     

Synthesis and Characterization of (Ce0.67Tb0.33)MnxMg1−xAl11O19 Phosphors Derived by Sol–Gel Processing

A (Ce_0.67Tb_0.33)Mn _x Mg_{1− x} Al₁₁O₁₉ phosphor powder was synthesized, using a simple sol–gel process, by mixing citric acid with CeO₂, Tb₄O₇, Al(NO₃)₃·9H₂O, Mg(OH)₂·4MgCO₃·6H₂O, and Mn(CH₃COO)₂. The phosphor crystallized completely at 1200°C, and the phosphor particle size was between 1 and 5 μm. The excitation spectrum was characteristic of Ce³⁺, while the emission spectrum was composed of lines from Tb³⁺ and Mn²⁺. The Mn²⁺ gave a green fluorescence band, and concentration quenching occurred when x > 0.10. The luminescent properties of the phosphor were explained by a configurational coordinate model.     

Role of Si2N2O in the Passive Oxidation of Chemically-Vapor-Deposited Si3N4

The results of two-step oxidation experiments on chemically-vapor-deposited Si₃N₄ and SiC at 1350°C show that a correlation exists between the presence of a Si₂N₂O interphase and the strong oxidation resistance of Si₃N₄. During normal oxidation, k _p for SiC was 15 times higher than that for Si₃N₄, and the oxide scale on Si₃N₄ was found by SEM and TEM to contain a prominent Si₂N₂O inner layer. However, when oxidized samples are annealed in Ar for 1.5 h at 1500°C and reoxidized at 1350°C as before, three things happen: the oxidation k _p increases over 55-fold for Si₃N₄, and 3.5-fold for SiC; the Si₃N₄ and SiC oxidize with nearly equal k _p's; and, most significant, the oxide scale on Si₃N₄ is found to be lacking an inner Si₂N₂O layer. The implications of this correlation for the competing models of Si₃N₄ oxidation are discussed.     

Reduction and Sintering of a Nickel–Dispersed-Alumina Composite and Its Properties

High-density nickel–dispersed-alumina (Al₂O₃/nickel) composites with superior mechanical properties were obtained by the hydrogen reduction and the hot pressing of alumina–nickel oxide (Al₂O₃/NiO) mixed powders. The mixtures were prepared by using NiO or nickel nitrate (Ni(NO₃)₂· n H₂O) as a dispersion source of nickel metal. Microstructural investigations of the composite fabricated using nitrate powder revealed that fine nickel particles, } 100 nm in diameter, dispersed homogeneously at the matrix grain boundaries, forming the intergranular nanocomposite. High strength (.1 GPa) and high-temperature hardness were registered for the composite that contained a small amount of nickel dispersion. The ferromagnetic properties of nickel, such as high coercive force, were observed, because of the fine magnetic dispersions, which indicates a functional value of structural composites.     

Synthesis of Nanosized Spherical Rhabdophane Particles

Spherical 10 nm rhabdophane (LaPO₄·H₂O) particles were made by controlled precipitation in water using lanthanum citrate chelate and phosphoric acid (La-Cit⁺/H₃PO₄) at a temperature of 30°C. Rod-shaped 10 nm × 100 nm rhabdophane particles were made by direct precipitation from lanthanum nitrate and phosphoric acid (La(NO₃)₃/H₃PO₄). The lanthanum nitrate to phosphoric acid molar ratios (La:P) were fixed at 1:1 and 1:5 for both methods to study their effect on particle size and shape. The particles were characterized with DTA/TGA, XRD, TEM, SEM, Fourier Transform infrared spectroscopy, and ζ potential measurements. The spherical particle surfaces had absorbed citric acid. The point of zero charge of the rod-shaped and spherical particles was pH 5.4 and 4.3, respectively. Formation mechanisms for the spherical particles are discussed.     

Oxidation of CVD Si3N4 at 1550° to 1650°C

A thermo gravimetric study of the oxidation behavior of chemically vapor-deposited amorphous and crystalline Si₃N₄ (CVD Si₃N₄) was made in dry oxygen (0.1 MPa) at 1550° to 1650°C. The specimens were prepared under various deposition conditions using a mixture of SiCl₄, NH₃, and H₂ gases. The crystalline CVD Si₃N₄ indicated a parabolic oxidation kinetics over the whole temperature range, whereas the amorphous CVD Si₃N₄ changed from a parabolic to a linear law with increased temperature. The oxidation mechanism is discussed in terms of the activation energy for the oxidation and the microstructure of the formed oxide films.