Tin(IV) Oxide Coating of Aluminum Borate Whiskers and Alumina Particles by Chemical Vapor Deposition

Aluminum borate whiskers of 0.5–1.0 μ diameter and alumina particles of 10–20 μ diameter were coated with SnO₂ by the reaction of SnCl₄–H₂O–N₂ gas mixtures in a rotary kiln reactor. Prior to coating, the whiskers were slightly etched to ensure adhesion between the SnO₂ layer and the whisker surface. The whiskers were coated at 100°C for 1 h, and then at 300°C for 2 h. This procedure was effective for covering the entire whisker surface with a uniform SnO₂ layer. Precoating was not necessary for the alumina particles. A compressed disk of the coated whiskers had an electrical conductivity of 30–40 S/m.     

Suppression of Grain Growth in Sol–Gel-Derived Tin Dioxide Ultrathin Films

Tin dioxide thin films of various thicknesses up to 150 nm were prepared on quartz glass substrates from a sol solution of SnO₂ (particle size 3 nm) by a spin-coating method and subjected to calcination at different temperatures up to 800°C for 30 min. The grain size of SnO₂ was found to be far smaller than those obtained from the SnO₂ sol-derived powder under the same calcination conditions. The suppression of grain growth of SnO₂ was more conspicuous as the film thickness decreased so that in the thinnest film (20 nm thick) the SnO₂ grain size remained as small as 6 nm after calcination at 800°C. It is suggested that the SnO₂ grains in the ultrathin film deposited on the substrate are restrained from moving and coalescing with each other, resulting in the suppression of grain growth.     

Hot Isostatic Pressing of Reactive SnO2 Powder

Tin(IV) oxide (SnO₂) crystallizes at room temperature by adding hydrazine monohydrate ((NH₂)₂· H₂O) to a hydrochloric acid solution of tin, followed by washing and drying. Well-densified SnO₂ ceramics (99.8% of theoretical) with an average grain size of 0.9 μm have been fabricated by hot isostatic pressing for 2 h at 900°C and 196 MPa. Their Vickers hardness and bending strength are 14.4 GPa and 200 MPa, respectively. They exhibit an electrical conductivity of 2 × 10⁻³−9 × 10⁻³ S·cm⁻¹ at room temperature.     

Synthesis of Ruthenium Dioxide Thin Films by a Solution Chemistry Technique

Smooth, fine-grained RuO₂ thin films have been synthesized and deposited onto 〈100〉 silicon substrates via a solution chemistry technique. Ruthenium(III) chloride n-hydrate dissolved in ethanol was used as the precursor solution. Thin films from a 0. 38M solution were spun at 4000 rpm for 20 s onto the substrates and fired at temperatures between 400° and 800°C. XRD analysis shows that RuO₂ forms over this entire temperature range. Using an appropriate firing schedule, the grain growth can be controlled and reproduced to provide for a uniform grain size distribution consisting of equiaxed, submicrometer diameter grains. The electrical resistance of the films has been measured at 300 K using the conventional four-point probe technique. The resistivity values range from 1. 8 μΩ·m for the films with an average grain size of 250 nm to 3.1 μΩ·m for the films with 30 nm grains. The presence of residual carbon and hydrogen is not believed to have a significant effect on the resistivity.     

Synthesis and Stability of Nanocrystalline Lead Stannate

Nano-crystalline PbSnO₃ was synthesized by a sol–gel route. It was an anion-deficient pyrochlore ( a = b = c = 1.0677 nm) with space group Fd3m. TEM images confirmed the nano-size of particles as ∼10 nm, aggregated into larger clusters up to 1 μm. DSC-TGA investigation revealed that the PbSnO₃ was unstable >800°C with 2.95% weight loss. The products of the reactions, Pb₂SnO₄ and SnO₂, were identified by in situ high-temperature XRD. The complex decomposition reactions were deduced as (2 + x )PbSnO₃= Pb₂SnO₄+ (1 + x )SnO₂+ x PbO ( x = 0.104). The lattice parameters of PbSnO₃ were determined by high-temperature XRD. The cell volume of PbSnO₃ increased with increasing temperatures. The average volumetric thermal expansion of PbSnO₃ was calculated as (β= 3.35 × 10⁻⁵/°C).     

(Pr, Co, Nb)-Doped SnO2 Varistor Ceramics

The effect on microstructure and electrical properties of (Co, Nb)-doped SnO₂ varistors upon the addition of Pr₂O₃ was investigated by scanning electron microscopy and by determining I – V , ɛ– f , and R – f relations. The threshold electric field of the SnO₂-based varistors increased significantly from 850 to 2280 V/mm, and the relative dielectric constants of the SnO₂-based varistors decreased greatly from 784 to 280 as Pr₂O₃ concentration was increased up to 0.3 mol%. The significant decrease of the SnO₂ grain size, from 4.50 to 1.76 μm with increasing Pr₂O₃ concentration over the range of 0–0.3 mol%, is the origin for the increase in the threshold voltage and decrease of the dielectric constants. The grain size reduction is attributed to the segregation of Pr₂O₃ at grain boundaries hindering the SnO₂ grains from conglomerating into large particles. Varistors were found to have a superhigh threshold voltage and a comparatively large nonlinear coefficient α. For 0.15 mol% Pr₂O₃-doped sample, threshold electric field and nonlinear coefficient α were measured to be 1540 V/mm and 61, and for 0.3 mol% Pr₂O₃-doped sample, V and α were 2150 V/mm and 42, respectively. Superhigh threshold voltage and large nonlinear coefficient α qualify the Pr-doped SnO₂ varistor as an excellent candidate for a high voltage protection system.     

Electrical Conductivity of Heat-Treated SnO2 Films

Variations in electrical conduction which were caused by heat treatment of SnO₂ films vapor-deposited on glass were studied. In the range 20° to 230°C, the relative importance of semiconduction processes attributed to 3 types of donors (probably O vacancies, interstitial Sn ions, and Cl ions) was determined as a function of heat treatment. A decrease in conductivity at constant temperature above 230°C was ascribed to grain growth of the SnO₂ crystals deposited initially.     

Microstructure of Nanocrystalline Yttria-Doped Zirconia Thin Films Obtained by Sol–Gel Processing

Nano- and microcrystalline yttria-stabilized zirconia (YSZ) thin films with a dopant concentration of 8.3±0.3 mol% Y₂O₃ were prepared with a variation in grain size by two orders of magnitude. A sol–gel-based method with consecutive rapid thermal annealing was applied to fabricate YSZ films, resulting in about 400 nm YSZ on sapphire substrates. The average grain sizes were varied between 5 nm and 0.5 μm by heat treatment in the temperature range of 650°–1350°C for 24 h. High-resolution (HRTEM) and conventional transmission electron microscopy analyses confirmed specimens—irrespective of the thermal treatment—consisting of cubic ( c -)ZrO₂ grains with nanoscaled tetragonal precipitates coherently embedded in the cubic matrix. Energy-dispersive X-ray spectroscopy and HRTEM on a large number of specimens yielded a homogeneous yttria concentration within the grains and at the grain boundaries with the absence of impurities, i.e. silica at the grain boundaries.     

Mechanical Properties of CoAl Materials with the Combined Additions of ZrO2(3Y) and Al2O3

Intermetallic CoAl powder has been prepared via self-propagating high-temperature synthesis (SHS). Dense CoAl materials (99.6% of theoretical) with the combined additions of ZrO₂(3Y) and Al₂O₃ have been fabricated via spark plasma sintering (SPS) for 10 min at 1300°C and 30 MPa. The microstructures are such that tetragonal ZrO₂ (0.3 μm) and Al₂O₃ (0.5 μm) particles are located at the grain boundaries of the CoAl (8.5 μm) matrix. Improved mechanical properties are obtained; especially the fracture toughness and the bending strength of the materials with ZrO₂(3Y)/Al₂O₃= 16/4 mol% are 3.87 MPa·m^1/2 and 1080 MPa, respectively, and high strength (>600 MPa) can be retained up to 1000°C.     

Low-Temperature Preparation and Magnetic Properties of V-Doped SnO2 Nanoparticles

A solid solution of vanadium (V)-doped tin oxide (SnO₂) particles of average diameter 2 nm and V content of 19 at.% was prepared at normal pressure and low temperature (100°C) by mixing wet SnO₂ gel SnO₂· x H₂O with a boiling solution of vanadium oxide (V₂O₅). Experimental characterizations using X-ray, electron diffraction, and transmission electron microscope show evidence of a pure single phase. The nanoparticles exhibit a mixed magnetic behavior, namely paramagnetic and ferromagnetic. Their thermal stability is also investigated. At higher temperature, 850°C, some amount of Fe precipitates from the solid solution.     

Thermal Softening Behavior and Application to Transparent Thick Films of Poly(benzylsilsesquioxane) Particles Prepared by the Sol–Gel Process

Thick films of poly(benzylsilsesquioxane) (BnSiO_3/2) particles, prepared by the sol–gel process, were deposited onto indium-tin-oxide-coated glass substrates by electrophoresis for the application to the micropatterning of the films. BnSiO_3/2 particles were thermally softened and sintered at ∼50°C, which was above the glass transition temperature of the particles. The films prepared by the electrophoretic sol–gel deposition consisted of aggregates of particles with diameters of 0.2–1 μm and were opaque. The film shrank from 2.5 μm to 1.4 μm in thickness and became transparent upon sintering of the particles during heat treatment at temperatures >100°C.     

Sol–Gel Processing and Characterization of Pure and Metal-Doped SnO2 Thin Films

A chloride-based inorganic sol–gel route was used for preparing pure and metal (osmium, nickel, palladium, platinum)-doped SnO₂ sol. SnCl₄ was first reacted with propanol, then the resulting compound was hydrolyzed and subsequently mixed with solutions of the metal dopants. The obtained sols were used for depositing thin films by spin coating or for preparing powders by solvent evaporation at 110°C. FTIR spectroscopy and thermal analysis of the powders revealed that chlorine still bound to tin stabilized the sol against gelation by hindering the condensation reactions. Film characterizations showed that platinum and palladium, unlike nickel and osmium, were likely to form nanoparticles in the SnO₂ lattice. This result was discussed with regard to the different ways that platinum and palladium, on one hand, and nickel and osmium, on the other, modified the growth of SnO₂ grains and the film roughness and morphology. Dopants that formed nanoparticles (platinum, palladium) resulted in the roughest film, while dopants that did not form particles (nickel, osmium) resulted in SnO₂ grain size very close to that of pure SnO₂.     

Microindentation-Induced Transformation in 3.5-mol%-Yttria-Partially-Stabilized Zirconia Single Crystals

The temperature dependence of the Vickers microhardness was studied in 3.4-mol%-Y₂O₃-partially-stabilized ZrO₂ (Y-PSZ) single crystals up to 1000°C; the samples had previously been annealed at 1600°C for 150 h to develop "colony" precipitates of tetragonal ZrO₂ in the cubic ZrO₂ matrix. Indentation caused extensive stress-induced martensitic transformation of the colony precipitates to monoclinic symmetry in zones which extended in extreme cases up to several hundred micrometers from the indent. For indents made at 500°C and above, the M _d and M _f temperatures are 450° and 310°C, respectively; A _s is ∼600°C ( M _d is the temperature of initial transformation (the "martensite start temperature") in deformed samples; M _f is the temperature at which the final transformation occurs; A _s is the temperature at which the reverse (monoclinic → tetragonal) transformation begins). However, extensive transformation zones are also found for indents made at 200°, 300°, and 400°C. The dislocation density introduced during indentation is responsible for nucleating the transformation in a zone adjacent to the indent. However, the transformation zone extends further than the plastic zone around the indent, indicating extensive autocatalytic transformation. Transformation within the zone appeared to occur in individual plates with {110} habit planes. The plate dimensions (∼100 μm ×∼175 μm ×∼10 μm) are large compared to the size of the colony precipitates (∼2 μm in maximum dimension).     

Effects of Zirconia on Microstructure and Dielectric Properties of Barium Titanate Ceramics

Dielectric properties and structural characteristics of BaTiO₃ ceramics are significantly influenced by small addition (2 wt%) of ZrO₂. SEM and TEM observations revealed enhanced microstructural uniformity and retarded grain growth depending on sintering temperature. Above 1320°C, Zr diffusion into the BaTiO₃ lattice resulted in a chemical modification of the tetragonal structure and the development of core–shell grains. Below 1320°C, TEM analysis showed ZrO₂ at the grain boundaries as discrete particles (∼0.03μm). X-ray diffraction analysis revealed a decrease in the axial (c/a) ratio with decreasing grain size. A corresponding decrease in the spontaneous polarization, and twinned domain structures, were also observed in the fine-grained ceramics. These samples also showed a flattened permittivity response with temperature and significantly lower losses.     

Effects of a Conducting LaNiO3 Thick Film as a Buffer Layer of a Pb(Zr,Ti)O3 Film on Titanium Substrates

A conducting 8-μm-thick LaNiO₃ (LNO) film was deposited on a Ti substrate by aerosol deposition for use as a diffusion barrier between a lead zirconate titanate (PZT) and a Ti substrate during postannealing. The deposited 20-μm-thick PZT films were annealed at 800°C. The PZT film deposited without LNO was cracked and partially detached from the substrate after postannealing, presumably due to a severe reaction with the Ti substrate, while no significant reactions were observed when the LNO buffer layer was used. The remnant polarization and relative dielectric constant of the 20-μm-thick annealed PZT films deposited on the LNO-buffered Ti substrate were 43 μC/cm² and 1010, respectively.     

Sintering Temperature Dependence of Grain Boundary Resistivity in a Rare-Earth-Doped ZnO Varistor

We present a rare-earth-doped ZnO ceramic with nonohmic electrical properties. Analysis of the microstructure and composition indicates that the ceramic is composed of the main phase of ZnO and the second phase of rare-earth oxides (e.g., Dy₂O₃, Pr₆O₁₁, Pr₂O₃). The average grain size is markedly increased from 3 to 18 μm, with an increase in the sintering temperature from 1150° to 1350°C. The corresponding varistor voltage and nonlinear coefficient decrease from 1014 to 578 V/mm, and from 15.8 to 6.8, respectively. The resistivity of grain and grain boundary evaluated by the complex impedance spectrum indicates that the resistivity of the grain is approximately constant (∼10³Ω), and the resistivity of the grain boundary decreases. The relative dielectric permittivity of the sintered ceramic samples is much larger than that of pure ZnO ceramic, which should be ascribed to the internal boundary layer capacitance effect.     

Resistance of Titanium Diboride to High-Temperature Plastic Yielding

Polycrystalline TiB₂ specimens of 3 μm average grain size but free of lamellar precipitates were compression-tested to 1900°C and 500 MPa. No plastic yielding was detected. Under such conditions, most other structural ceramics do exhibit yield behavior. The results suggest the existence of a high Peierls stress, presumably related to Ti—B bonding. This finding contrasts with a report on ZrB₂ in which resistance to yielding was attributed to lamellar precipitates.     

Processing and Mechanical Behavior of CrN/ZrO2(2Y) Composites

CrN powder consisting of granular particles of ∼3 μm has been prepared by self-propagating high-temperature synthesis under a nitrogen pressure of 12 MPa using Cr metal. Dense pure CrN ceramics and CrN/ZrO₂(2Y) composites in the CrN-rich region have been fabricated by hot isostatic pressing for 2 h at 1300°C and 196 MPa. The former ceramics have a fracture toughness ( K _IC) of 3.3 MPa ·m^1/2 and a bending strength (σ_b) of 400 MPa. In the latter materials almost all of the ZrO₂(2Y) grains (0.36–0.41 μm) are located in the grain boundaries of CrN (∼4.6 μm). The values of K _IC (6.1 MPa · m^1/2) and σ_b (1070 MPa) are obtained in the composites containing 50 vol% ZrO₂(2Y).     

Dielectric Properties of Fluxed Barium Titanate Ceramics with Zirconia Additions

BaTiO₃ compacts, when fluxed with <2 vol% of a complex borate glass phase, were sintered to near theoretical density at temperatures <1175°C in 2 h. Microstructural analysis showed a uniform grain size <1.0 μm with 0.75 wt% ZrO₂ added to the flux phase as a grain growth inhibitor. TEM analysis revealed a microcrystalline grain-boundary phase with the ZrO₂ resident along the grain boundaries. These samples displayed an essentially flat dielectric profile, low dissipation factors (<2%) over the range 25° to 125°C, a near linear dependence (≅±15%) between 25° and −55°C, and significantly increased voltage stability. X-ray diffraction analyss of these small-grained materials indicated a suppression of the tetragonal structure toward a more cubic modification.     

Characterization and Electrophoretic Deposition of Poly(Phenylsilsesquioxane)–Titania Hybrid Particles Prepared by the Sol–Gel Method

Poly(phenylsilsesquioxane)–titania (PhSiO_3/2–TiO₂) hybrid particles were prepared from phenyltriethoxysilane and titanium tetra- n -butoxide by the sol–gel method. Fourier transform infrared spectra showed that PhSiO_3/2 and the TiO₂ components were hybridized through Si–O–Ti bonds. The refractive index of the particles was monotonically increased from 1.57 to 1.62 with an increase in the TiO₂ content. The PhSiO_3/2–TiO₂ particles were electrophoretically deposited on indium tin oxide (ITO)-coated glass substrates to form opaque, thick films about 3 μm in thickness. When the mole ratio x in (1− x )PhSiO_3/2· x TiO₂ was equal to or less than 0.05, the deposited PhSiO_3/2–TiO₂ films became transparent with a heat treatment at 400°C because of the thermal sintering of the particles.