Surface Precipitation Route for the Development of Cordierite-Zirconia Composites

Based on the interfacial electrochemical properties of aqueous cordierite dispersion, a novel interfacial scheme for fabricating cordierite-ZrO₂ composite with a dense and homogeneous microstructure was proposed and tested. In the present processing route, cordierite particles were first uniformly coated with a thin layer (∼40 nm) of aluminum hydroxide by an in situ surface-induced coating. Then, a controlled surface precipitation of ultrafine zirconium hydroxide precursor onto the coated cordierite particles was performed to obtain a composite with a uniform spatial distribution of the dispersed ZrO₂ particles throughout the matrix. The coated layer acted to suppress the formation of zircon phase during sintering. The enhanced fracture toughness observed in the presence of ZrO₂ was partly attributed to the t → m transformation toughening of the dispersed tetragonal ZrO₂ particles.     

Y2O2S:Eu Red Phosphor Powders Coated with Silica

Y₂O₂S:Eu red phosphor powders were coated with silica (SiO₂), using sol–gel and heterocoagulation techniques. Phosphor powders were dispersed in ethanol with tetraethyl orthosilicate and water. Hydrochloric acid was used to catalyze the sol–gel reaction, and an amorphous film 10–20 nm thick was observed via transmission electron microscopy (TEM). Colloidal SiO₂ powders 10–70 nm in size were used, and the SiO₂ powder coating was made by controlling pH values in the range of 4.5–8, in which a negatively charged surface of SiO₂ powder and a positively charged surface of red phosphor powder were formed. Then, SiO₂ powders were adsorbed electrically onto the phosphor powder surface, as evidenced by TEM, dissolution, and zeta potential measurements. Chemical bonding in the coating was studied using electron spectroscopy for chemical analysis and Fourier transform infrared spectroscopy.     

Carbothermal Synthesis of Boron Nitride Coatings on Silicon Carbide

Pure BN coatings have been synthesized on the surface of SiC powders and fibers by a novel carbothermal nitridation method. Three stages are involved in the process: first, formation of a carbon layer on the SiC by the extraction of Si with chlorine; second, infiltration of the resulting nanoporous carbide-derived carbon (CDC) coating by a saturated boric acid solution; and finally, nitridation in ammonia at atmospheric pressure to produce the pure BN coating. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS) were used to characterize the phase, elemental composition, and surface morphology of the coatings. The intermediate carbon layer acts as a template for BN growth, facilitates the formation of BN, and prevents the degradation of SiC fibers during nitridation. The whole process is simple, cost-effective, and less toxic due to the use of H₃BO₃ and NH₃ as precursors at atmospheric pressure compared with most commonly used chemical vapor deposition (CVD) methods. Uniform BN coatings obtained by this method prevent the bridging of fibers in the tow. The coating of powders is possible, which cannot be achieved by conventional CVD methods.     

Surface Modification of Si3N4 Powders by Coprecipitation of Sintering Aids

Two commercial Si₃N₄ powders were coated with sintering aids by coprecipitation. Lanthanum and yttrium nitrates were used as sintering aid precursors. Electrokinetic sonic amplitude measurements and X-ray photoemission spectroscopy analysis were used to investigate electrokinetic behavior and surface properties, respectively. Coprecipitation produced different effects on the composition of the coating layer depending on the actual features of the starting Si₃N₄ powders. The electrokinetic behavior of aqueous suspensions with coated powders depended strongly on the additives, their solubility, and the rate of oxidation of the coated layer. The coprecipitation conditions had to be carefully controlled to obtain reproducible composition and morphology of the coating layers. Treatments of the starting powder, pH, and washing volumes were optimized to tailor the coating layer and improve the coprecipitation yield.     

Microstructure of Varistors Prepared with Zinc Oxide Nanoparticles Coated with Bi2O3

Zinc oxide (ZnO) nanoparticles coated with 1–5 wt% Bi₂O₃ were prepared by precipitating a Bi(NO₃)₃ solution onto a ZnO precursor. Transmission electron microscopy showed that a homogeneous Bi₂O₃ layer coated the surface of the ZnO nanoparticles and that the ZnO particle size was ∼30–50 nm. Scanning electron microscopy showed that ZnO grains sintered at 1150°C were homogeneous in size and surrounded by a uniform Bi₂O₃ layer. When the ZnO grains were surrounded fully by Bi₂O₃ liquid phases, further increases in the ZnO grain size were not affected by the Bi₂O₃ content. This predesigned ZnO nanoparticle structure was shown to promote homogeneous ZnO grains with perfect crystal growth.     

Microstructure and Thermal Shock Resistance of Molten Glass-Coated Carbon Materials Fabricated by Interfacial Control

Carbon substrates were coated completely with a molten silicate glass, where the wettability of carbon to glass was improved by infiltration and pyrolysis of perhydropolysilazane. Microstructures of the carbon–glass interface were dependent on P n ₂ during coating. Coating at lower P n ₂ induced the formation of cristobalite at the carbon–glass interface. When the coating was performed at higher P n ₂, the glass and carbon were strongly adhered, without the formation of cristobalite. Coating at higher P n ₂ improved the thermal shock resistance of the glass layer, because crack initiation was not induced by the phase transformation of cristobalite during the cooling process. In the case of coating at higher P n ₂, an oxynitride glass layer was formed at the glass subsurface by dissolution of N₂. A porous glass subsurface layer with uniform spherical micro-pores could be produced by soaking near the glass transition temperature in a steam environment. The porous layer with fine and homogeneous microstructure acts as a thermal shock absorbing layer, so that glass-coated carbon with a porous glass layer has excellent thermal shock resistance in addition to steam oxidation resistance.     

Reactive Hot Pressing of SiC/MoSi2 Nanocomposites

Dense SiC/MoSi₂ nanocomposites were fabricated by reactive hot pressing the mixed powders of Mo, Si, and nano-SiC particles coated homogeneously on the surface of Si powder by polymer processing. Phase composition and microstructure were determined by methods of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive spectrometry. The nanocomposites obtained consisted of MoSi₂, β-SiC, less Mo₅Si₃, and SiO₂. A uniform dispersion of nano-SiC particles was obtained in the MoSi₂ matrix. The relative densities of the monolithic material and nanocomposite were above 98%. The room-temperature flexural strength of 15 vol% SiC/MoSi₂ nanocomposite was 610 MPa, which increased 141% compared with that of the monolithic MoSi₂. The fracture toughness of the nanocomposite exceeded that of pure MoSi₂, and the 1200°C yield strength measured for the nanocomposite reached 720 MPa.     

Effect of Powder Coating on Stabilizer Distribution in CeO2-Stabilized ZrO2 Ceramics

The phase and microstructure relationship of 12 mol% CeO₂-stabilized ZrO₂ ceramics prepared from coated powder was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersed X-ray spectroscopy (EDS). As compared with the sample prepared with co-precipitated method, which exhibited a similar grain size distribution, the EDS analysis revealed that the powder coating induced a wide distribution of CeO₂ solubility, which decreases monotonically with the increase of grain size. This variation of stabilizer content from grain to grain rendered many large grains in the monoclinic phase. Stronger cerium segregation to grain boundaries was observed between large grains, which often form thin amorphous films there. The inhomogeneous CeO₂ distribution keeps more tetragonal ZrO₂ grains close to the phase boundary to facilitate the transforming toughness. Addition of an Al₂O₃ precursor in coated powders effectively raises the overall CeO₂ stabilizer content in the grains and preserves more transformable tetragonal phase in the microstructure, which further enhanced the fracture toughness. The dependence of CeO₂ solubility on grain size may be explained in a simple coating-controlled diffusion and growth process that deserves further investigation.     

Fabrication of Machinable Silicon Carbide-Boron Nitride Ceramic Nanocomposites

SiC/BN nanocomposite powders with the microstructure of micrometer-sized SiC particles coated with nanometer-sized BN particles were prepared via a chemical reaction, which used a mixture of boric acid (H₃BO₃) and urea (CO(NH₂)₂) as reactants coated on the surface of the SiC particles to react under a nitrogen-gas atmosphere. The results of XRD, TEM, and SAED studies showed that the coating layer (BN) was composed mostly of amorphous and nanometer-sized BN particles at the reaction temperature of 850°C. When the nanocomposite powders were hot-pressed at 1850°C, machinable SiC/BN ceramic nanocomposites with fine grain size and homogeneous microstructure were fabricated. The composite that contained 20 wt% BN exhibited high strength (the three-point bending strength was 588.4 ± 26.8 MPa) and excellent machinability.     

Effects of Copper Coating on the Crystalline Structure of Fine Barium Titanate Particles

We have investigated the effect of a metal coating—copper—on the tetragonal structure of fine barium titanate (BaTiO₃) particles. The BaTiO₃ particles were synthesized by a sol-gel method and heat treated at temperatures >900°C for various amounts of time before coating. The copper coating was achieved by an electroless coating technique. The transmission electron microscopy micrographs revealed that the coated powder contained fine BaTiO₃ particles that were embedded in copper patches. The X-ray diffractometry patterns showed that the copper coating increased the c/a ratio of the fine BaTiO₃ particles. For powders that were heat treated at 900°C for 10 h and were initially cubic, the copper coating changed the c/a ratio, from 1 to 1.0034. For powders that were calcined at 900°C for 20 h and were initially tetragonal, the copper coating further enhanced the c/a ratio, from 1.0028 to 1.0043. When the copper-coated BaTiO₃ particles were oxidized, the c/a ratio was reduced to a value that was approximately equal to or below that of the uncoated powders. A conductive coating can eliminate the depolarization energy of an insulating polar particle. The fact that the copper coating promoted the polar tetragonal phase but the nonconductive copper-oxide coating did not was consistent with the interpretation that the presence of the cubic phase (nonpolar) in small BaTiO₃ particles was caused by the depolarization effect.     

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.     

High-Temperature Oxidation Behavior of Solution Precursor Plasma Sprayed Nanoceria Coating on Martensitic Steels

Solution precursor plasma spray (SPPS) is used to deposit nanoceria coating on a 410 martensitic stainless steel. The process of pyrolysis in converting the cerium nitrate solution to cerium oxide, the microstructure and the surface chemistry is confirmed by thermodynamic calculations, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. Subsequent exposure of the coated steel in atmospheric air to cyclic oxidation at 1000°C revealed excellent corrosion resistance of the steel in presence of the SPPS-processed nanoceria coating. The formation of the nanostructured (10–100 nm) ceria coating is studied using transmission electron microscopy. Relative Ce⁴⁺ and Ce³⁺ concentration in the coating was determined from XPS high-resolution spectrum. Cross-section scanning electron microscopy showed the presence of an impervious nature of the protective layer with reduced scale thickness in the coated-oxidized sample. After a pre-oxidation treatment at 1273 K of the coated specimen, the oxidation kinetics showed a significant decrease as compared with the uncoated martensitic steel.     

Two Phase Monazite/Xenotime 30LaPO4–70YPO4 Coating of Ceramic Fiber Tows

Equiaxed yttrium–lanthanum phosphate nanoparticles (Y_0.7,La_0.3)PO₄·0.7H₂O were made and used to continuously coat Nextel^™ 720 fiber tows. The particles were precipitated from a mixture of yttrium and lanthanum citrate chelate and phosphoric acid (H₃PO₄), and characterized with differential thermal analysis and thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The coated fibers were heat treated at 1000°–1300°C for 1, 10, and 100 h. Coating grain growth kinetics and coated fiber strengths were determined and compared with equiaxed La-monazite coatings. The relationships between coating porosity, coating hermeticity, and coated fiber strength are discussed.     

Precipitation Coating of Monazite on Woven Ceramic Fibers: II. Effect of Processing Conditions on Coating Morphology and Strength Retention of Nextel™ 610 and 720 Fibers

Woven cloths of Nextel^™ 610 and 720 fibers were coated with monazite by precipitation. The cloths were first saturated with concentrated precursor solutions, and then submerged in warm water to initiate precipitation onto the fiber surfaces. Coatings were characterized by scanning electron microscopy, and transmission electron microscopy; thermogravimetric analysis was performed on LaPO₄ owders precipitated in solution under the same conditions as the coatings were deposited. Coating thickness distributions were measured and analyzed. Coated fiber strength was measured following heat treatment for 2 h at 1200°C. Processing conditions which retain a substantial fraction of the uncoated fiber strength are identified, and are discussed in the context of current understanding of strength degradation in coated fibers. Strength retention of coated Nextel^™ 610 fibers following heat treatment was broadly insensitive to precursor solution chemistry and was more strongly affected by intercoat firings which govern the final coating microstructure. For fixed processing conditions, more strength degradation was observed in Nextel^™ 720 due to higher residual stresses in the fiber.     

TEM Investigation of Impurity Phases and the Penetration of Liquid Aluminum in Hot Isostatically Pressed TiB2 Compacts

The microstructure of materials compacted from commercially produced TiB₂ powders was investigated using transmission electron microscopy. A number of impurity phases that are introduced during the various processing stages were identified. After exposure to liquid aluminum, grain boundaries and triple junctions of TiB₂ were found to be penetrated by aluminum. In the penetrated regions pure aluminum, two aluminum oxides, and an (Al₂OC)₁- _x (AlN) _x . phase were identified. A SiO₂ glass phase, introduced during hot isostatic pressing, is believed to be responsible for the formation of alumina. None of the other impurity phases were found to react with aluminum.     

Preparation of Lead Zirconate Titanate (Pb(Zr0.52Ti0.48)O3) by Homogeneous Precipitation and Calcination

Preparation of phase-pure PZT (Pb(Zr_0.52Ti_0.48)O₃) powders was achieved, in the presence of urea (CH₄N₂O), by homogeneous precipitation. Aqueous solutions of PbCl₂, ZrOCl₂·8H₂O, and TiCl₄ were used as the starting materials in the synthesis of phase-pure PZT powders. Phase evolution behavior of precursor powders was studied by powder X-ray diffraction (XRD) in air, over the temperature range of 90° to 750°C. The morphology of the formed powders was studied by scanning electron microscopy (SEM). Semiquantitative chemical analyses of the samples were performed by energy-dispersive X-ray spectroscopy (EDXS).     

Spherical Rhabdophane Sols. II: Fiber Coating

A rhabdophane (LaPO₄·nH₂O) sol with fine spherical particles was used to coat Nextel™ 720 fiber tows continuously with monazite (LaPO₄). The coatings are compared with those made previously from rod-shaped particles. The coated fibers were heat-treated at 1000°–1300°C for 1, 10, and 100 h. The effect of heat treatment temperature and time on coating microstructure was characterized by scanning electron microscopy and transmission electron microscopy, and the strengths of the coated fibers were measured after coating and heat treatment. Grain shapes and grain growth rates were measured. Coating thickness uniformity was quantified by a fit to a truncated extreme-value distribution. Coating hermeticity was evaluated by analysis of grain growth rates. The spherical particles promote more rapid coating densification and local hermeticity, but introduce problems with sintering shrinkage cracking that are not present in coatings derived from rod-shaped particles.     

Low-Temperature Synthesis of Nanocrystalline Zinc Titanate Materials with High Specific Surface Area

Nanocrystalline zinc titanate (ZnTiO₃) was synthesized at low temperatures through the combination of a sol–gel processing and a polymer binder method. ZnTiO₃ powders of ∼5 nm in size were obtained by heating pastes, which were composed of a Zn-Ti methanolic solution containing acetylacetone and an organic polymer binder, at 500°C in air. Thermal decomposition behavior of the pastes was analyzed by thermogravimetry-differential thermal analysis. Crystallinity of ZnTiO₃ was examined by transmission electron microscopy. The BET measurement revealed that the powders had a relatively high specific surface area of 106 m²/g.     

Scanning Force Microscopy Study of Ceramic Fibers for Advanced Composites

The surface roughness and topography of three different Al₂O₃ fibers were evaluated using atomic force microscopy (AFM). The fibers used were as-received, refractory-metal coated, and Y₂O₃/refractory-metal duplex-layer coated. The refractory-metal coating and Y₂O₃ coating on the Al₂O₃ fibers increased the average surface roughness from 13.3 to 17.1 and 18.8 nm, respectively. The topographic image of the fibers evaluated by AFM was compared to that obtained by scanning electron microscopy. Lateral force microscopy (LFM) was used to measure the distribution of the friction force on the refractory-metal-coated Al₂O₃ surfaces, with friction coefficients ranging from 0.2 to 0.8; the average friction coefficient was 0.38. Tailoring the mechanical properties at fiber/matrix interfaces by surface modification of Al₂O₃ fibers to improve the overall mechanical properties of the composites also was proposed.     

Sintering of Monosized, Spherical Yttria Powders

Monosized, spherical Y₂O₃ was processed from raw commercial Y₂O₃ by homogeneous precipitation in aqueous solution via urea decomposition. Dry-pressed pellets of the synthesized and raw powders were sintered to 1500°, 1600°, and 1700°C for 7 to 720 min. Microstructural development was followed with scanning electron microscopy. The differences between sintering behavior of the two powders are discussed.