Fabrication and Sintering of Fine Yttria-Doped Ceria Powder

Yttria–doped ceria powder was prepared from oxalate precursors. The oxalate coprecipitation bath parameters were closely monitored and found to influence the sintering behavior of the subsequently obtained oxide powders strongly. The use of concentrated (Ce,Y) metal nitrate solutions and dilute neutralized oxalic acid for coprecipitation were identified as the most–important parameters. Following calcination at 700°C, compacts of such powders were sintered to high density (98%) at 1400°C (4 h). Ball milling of the powder further reduced the sintering temperature. Dry milling, for tape–casting applications of the powder in particular, was more effective than wet milling. Tape–cast membranes were fired at 1400°C (2 h), with resulting densities of 98%.     

Diffusion Sintering: II, Initial Sintering Kinetics of Alumina

The initial sintering kinetics of alumina have been studied by measuring the isothermal shrinkage of compacts of several alumina powders in air. The shrinkage of these compacts can best be described by a grain-boundary vacancy diffusion model for the temperature range 1200° to 1600°C. The behavior of the compacts is consistent with the model after an initial shrinkage has occurred. The magnitude of this initial shrinkage is constant for identical specimens and is independent of the sintering temperature.     

Electrochemical Synthesis and Sintering of Nanocrystalline Cerium(IV) Oxide Powders

Nanocrystalline CeO₂ powders were prepared electrochemically by the cathodic electrogeneration of base, and their sintering behavior was investigated. X-ray diffraction and transmission electron microscopy revealed that the as-prepared powders were crystalline cerium(IV) oxide with the cubic fluorite structure. The lattice parameter of the electrogenerated material was 0.5419 nm. The powders consisted of nonaggregated, faceted particles. The average crystallite size was a function of the solution temperature. It increased from 10 nm at 29°C to 14 nm at 80°C. Consolidated powders were sintered in air at both a constant heating rate of 10°C/min and under isothermal conditions. The temperature at which sintering started (750°C) for nanocrystalline CeO₂ powders was only about 100°C lower than that of coarser-grained powders (850°C). However, the sintering rate was enhanced. The temperature at which shrinkage stopped was 200°-300°C lower with the nanoscale powder than with micrometer-sized powders. A sintered specimen with 99.8% of theoretical density and a grain size of about 350 nm was obtained by sintering at 1300°C for 2 h.     

Fabrication of Transparent Yttria Ceramics by the Low-Temperature Synthesis of Yttrium Hydroxide

Thin flakes of yttrium hydroxide agglomerated in a manner resembling houses of cards with aging at 10°C. The agglomerate then dissociated into fine yttria particles with calcination at >800°C. The particle size of the calcined powder increased appreciably as the calcination temperature increased. The shrinkage curve indicated similar densification behavior among undoped yttria powders calcined at 800°–1000°C, despite considerable particle growth as the calcination temperature increased. Increasing the calcination temperature to >1000°C shifted the shrinkage curve appreciably to the high-temperature region. Sulfate-ion-doped yttria particles had round edges, irrespective of calcination temperature, in contrast to the sharp edges of the undoped yttria particles. A calcination temperature of <1000°C resulted in skeleton yttria particles, which exhibited poor sinterability. At a calcination temperature >1000°C, the skeleton particles dissociated into monodispersed particles that densified easily. When the calcination temperature was >1000°C and the average particle sizes were similar, the undoped and sulfate-ion-doped yttria showed similar densification rates. The transparency of the sintered yttria ceramics was dependent on both the calcination temperature and sulfate-ion doping: that is, sulfate-ion doping and calcining at 1100°C were both necessary conditions for the fabrication of a transparent body.     

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.     

Calcination and Sintering Study of Thoria

Data on the effect of calcination temperature on surface area, apparent crystallite size, compactibility, sintered density, and volume shrinkage are presented for thoria prepared from the oxy-carbonate, chloride, nitrate, and oxalate. Surface area and volume shrinkage decreased with rising calcination temperature. Thoria obtained from the oxycarbonate exhibited the greatest sinterability; material derived from the nitrate showed the least. Maximum bulk densities were achieved using material resulting from the calcination of the oxycarbonate between 600° and 100°C. Densities of 95 to 98% of the theoretical value of thoria were attained by compacting these powders at pressures above 20 tsi and firing at 1500°C for 24 hours. Urania-thoria solid solutions incorporating thoria obtained by calcination of the chloride exhibited the highest fired densities.     

Strengthening of Porous Mullite and Zirconia CMC Matrices by Evaporation/Condensation

A processing method using evaporation/condensation sintering in an HCl atmosphere was developed for strengthening porous materials without shrinkage. Strengthening without shrinkage is useful in preventing voids and cracks that might be formed during constrained densification, e.g., a porous matrix in a continuous fiber reinforced ceramic composite. Mixtures of mullite and zirconia (monoclinic, tetragonal (3 mol% Y₂O₃), and cubic (8 mol% Y₂O₃)) were studied and exposed to HCl vapor at temperatures up to 1300°C. It was observed that the evaporation–condensation mass transport process produced a porous material with minimal shrinkage. As the crystal structure of the starting tetragonal and cubic zirconia powders did not change after extensive coarsening, it appeared that zirconium and yttrium were transported in the same proportion via evaporation/condensation. The process produced significant coarsening of the zirconia grains, which made the material resistant to densification when heated to 1200°C in air. Because the sintering produced coarsening without shrinkage, the pores also coarsened and a porous microstructure was retained. Mixtures of mullite and zirconia were used because mullite does not densify under the processing conditions used here, namely, heat treatments up to 1300°C. The mullite particles acted as a non-densifying second phase to further inhibit shrinkage when the mullite/zirconia composite was heated up to 1200°C in air. The coarsened cubic zirconia plus mullite mixture had the least densification after heat treatments in air of 100 h at 1200°C.     

High-Temperature Proton-Conducting LaNbO4-Based Materials: Powder Synthesis by Spray Pyrolysis

Submicrometer lanthanum ortho-niobate (LaNbO₄ (LN))-based powders have been prepared by spray pyrolysis of an aqueous solution containing stable La–EDTA and Nb–malic acid complexes. The powders had a particle size of ∼0.1 μm, a narrow particle size distribution, and high purity after calcination above 800°C. The powders possessed excellent sintering properties resulting in >98% dense materials at 1200°C. The present route is shown to be excellent for the large-scale preparation of high-quality LaNbO₄-based powders.     

Hot-Pressing of β-SiC Powder with Al-B-C Additives

The sintering behavior of β-SiC powders with additions of Al, B, and C was studied at 1600° to 1800°C with applied pressures of 20 to 60 MPa. Ceramics with densities of ∼3.08 g/cm³ were obtained by hot-pressing at 1650°C and 50 MPa. The bending strength did not degrade up to 1200°C. A large amount of a second phase, which was apparently Al₈B₄C₇, was observed as streaks in the microstructure. It is suggested that a liquid phase, which coexisted with this compound, enhanced densification.     

Sintering Behavior of In Situ Cobalt Oxide-Doped Cerium–Gadolinium Oxide Prepared by Flame Spray Pyrolysis

Ce_0.9Gd_0.1O_1.95 (CGO10) and in situ cobalt oxide-doped CGO10 were prepared by pilot-scale flame spray synthesis, yielding powders with an average particle size of 40 nm. Cobalt oxide was shown to be a very effective sintering aid for CGO10 and lowered the maximum sintering temperature from 1450° to about 1200°C. Sintering studies revealed that in situ cobalt oxide-doped CGO10 exhibited a temperature of maximum shrinkage rate of 880°C for a dopant concentration of 1 mol% CoO_{1− x} , whereas for conventionally cobalt oxide-doped CGO10, this temperature was 914°C. This decrease is believed to be a result of a more homogeneous dopant distribution of the in situ cobalt oxide-doped CGO nanopowders as compared with the powders in which the doping was introduced as nitrates.     

Effect of Silicon Substitution on the Sintering and Microstructure of Hydroxyapatite

The substitution of between 0 and 1.6 wt% silicon (Si-HA) in hydroxyapatite (HA) inhibited densification at low temperatures (1000°–1150°C), with these effects being more significant as the level of silicon substitution was increased. For higher sintering temperatures (1200°–1300°C), the sintered densities of HA and Si-HA compositions were comparable. Examination of the ceramic microstructures by scanning electron microscopy (SEM) showed that silicon substitution also inhibited grain growth at higher sintering temperatures (1200°–1300°C). The negative effect of silicon substitution on the sintering of HA at low temperatures (1000°–1150°C) was reflected in the hardness values of the ceramics. However, for higher sintering temperatures, e.g., 1300°C, where sintered densities were comparable, the hardness values of Si-HA compositions were equal to or greater than that of HA, reflecting the smaller grain sizes observed for the former.     

High-Performance Multilayer Capacitor Dielectrics from Chemically Prepared Powders

Advantages of chemically prepared powders for electronic ceramics have been demonstrated for a number of multilayer capacitor (MLC) dielectrics. A cost-efficient precipitation process was developed to produce undoped or doped crystalline barium titanate powder with a narrow particle size distribution close to 0.5 μm. More complex compositions, e.g., barium-neodymium titanate, were amorphous as precipitated but could be crystallized by calcination below 1000°C. Additional compositional modifications, to adjust electrical properties or to lower sintering temperature, were accomplished by doping the surface of the powder particles using a solution coating process. Exceptional fired densities and electrical performance were obtained.     

Effects of Calcination on the Microstructures and Photocatalytic Properties of Nanosized Titanium Dioxide Powders Prepared by Vapor Hydrolysis

Ultrafine titanium dioxide powders are produced in an aerosol reactor using vapor hydrolysis of titanium tetraisopropoxide (TTIP) at 260°C and higher temperatures (600°, 700°, 800°, and 900°C). The effect of calcination on the microstructure characteristics and the photoactivity is studied. The powders are characterized using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), and transmission electron microscopy (TEM) analyses. The photocatalytic activity of the powders is also studied using degradation of phenol in water as a test reaction. The powder produced at 260°C is calcined at 500° to 900°C while those produced at higher temperatures are calcined at 600°C for 3 h. Raw powder produced at 260°C is amorphous but becomes crystalline after calcination. As the calcination temperature increases, the surface area decreases but the rutile-to-anatase ratio and the anatase and rutile crystallite sizes increase. The photoactivity increases as calcination temperature increases to 900°C, when the powder becomes densified and the surface area drops significantly because of sintering. Powders produced at higher temperatures are predominantly anatase and are generally more photoactive. Calcination of the powders at 600°C for 3 h results in little loss of surface areas and enhances the photoactivity. Among the factors examined, large surface area and good dispersion of the powders in the reaction mixture are favorable to photoactivity. Conversely, prolonged calcination at high temperatures is detrimental to photoactivity. However, surface area, crystallite size, anatase-to-rutile ratio, and dispersity of the powders alone cannot account for the observed trend of photoactivity. The role of crystallinity needs to be investigated.     

Effect of Co-Precipitation on the Low-Temperature Sintering of Biphasic Calcium Phosphate

Three types of biphasic calcium phosphate (BCP) powders were prepared and their sintering behavior was investigated. The specific surface area and HA/TCP ratio were similar in all three specimens. Most of the densification in the co-precipitated s-BCP occurred before the β- to α-TCP phase transformation, and a maximum density of ∼95% was obtained at 1100°C. The mixture of separately precipitated and calcined hydroxyapatite (HA) and tricalcium phosphate (TCP) (m-BCP) showed a poor sintering behavior, and the apparent density was below 70% at temperatures up to 1200°C. In the commercial HA and TCP mixture (c-BCP), the low temperature sintering was poor, but densification continued without the phase transformation due to the presence of MgO, achieving almost full densification at 1200°C.     

Influence of Calcination Temperature on the Microstructure and Mechanical Properties of a Gel-Derived and Sintered 3 mol% Y-TZP Material

A pure coprecipitated 3 mol% Y-TZP powder was subjected to two calcination temperatures, 600° and 1000°C, prior to compaction and sintering. Significant differences in the initial sintering behavior were observed. The lower temperature calcined powder exhibited abnormal grain growth. The resultant mechanical properties mirrored the microstructure with the lower temperature calcined material having lower flexural strength. Hardness measurements of the two sintered bodies revealed significant differences in the two phases of the lower temperature calcined material. Differences in reactivity of the two powders after calcination are suggested as the basis for the difference in microstructure and resultant mechanical properties.     

Microstructural evolution during sintering in MgO powders precipitated from sea water under induced agglomeration conditions

Green compacts pressed by means of uniaxial compaction with Magnesia (MgO) powders precipitated from sea water and calcined at different temperatures were sintered under H₂ atmosphere at 1700 °C. The calcination, carried out between 900 and 1200 °C had a great influence in the final density and the microstructure. The densification of MgO agglomerated powders seems to be predictably related to grain growth and thus coarsening kinetics. At calcination temperatures higher than 900 °C, the volume of large pores was increased notably suggesting that the inhibited grain growth adversely affected the thermodynamics of pore sintering. Relative densities between 74 and 98% of theoretical density were reached in compacts obtained at different compaction pressures. The microstructural differences were examined by Scanning Electron Microscopy (SEM).     

Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering

Hafnium diboride (HfB₂)- and hafnium carbide (HfC)-based materials containing MoSi₂ as sintering aid in the volumetric range 1%–9% were densified by spark plasma sintering at temperatures between 1750° and 1950°C. Fully dense samples were obtained with an initial MoSi₂ content of 3 and 9 vol% at 1750°–1800°C. When the doping level was reduced, it was necessary to raise the sintering temperature in order to obtain samples with densities higher than 97%. Undoped powders had to be sintered at 2100°–2200°C. For doped materials, fine microstructures were obtained when the thermal treatment was lower than 1850°C. Silicon carbide formation was observed in both carbide- and boride-based materials. Nanoindentation hardness values were in the range of 25–28 GPa and were independent of the starting composition. The nanoindentation Young's modulus and the fracture toughness of the HfB₂-based materials were higher than those of the HfC-based materials. The flexural strength of the HfB₂-based material with 9 vol% of MoSi₂ was higher at 1500°C than at room temperature.     

High-Temperature Proton-Conducting Lanthanum Ortho-Niobate-Based Materials. Part II: Sintering Properties and Solubility of Alkaline Earth Oxides

The sintering properties and microstructure of La_{1− x} A _x NbO₄ powders ( x =0, 0.005, and 0.02 and A=Ca, Sr, and Ba), prepared by spray pyrolysis have been investigated. Dense materials (>97%) were obtained by conventional sintering at 1200°C and by hot pressing (25 MPa) at 1050°C, respectively. Homogeneous materials were obtained and the average grain size obtained by the two densification methods was ∼2.0 and ∼0.4 μm, respectively, for the 2% doped materials. Pure lanthanum ortho-niobate (LaNbO₄) showed a higher degree of grain growth. In the acceptor-doped materials, secondary phases were observed to inhibit grain growth at 1200°C. At 1400°C or higher, molten secondary phases in the Ba-doped materials resulted in severe grain growth, causing microcracking during cooling due to crystallographic anisotropy. A low solubility of AO (A=Ca, Sr, and Ba) in LaNbO₄ is inferred from the presence of secondary phases, and 1 mol% solubility of SrO in LaNbO₄ was found by electron microprobe analysis. The electrical conductivity in wet hydrogen of the materials demonstrated that the main charge carrier was protons up to 1000°C and reached a maximum value of ∼8·10⁻⁴ S/cm at 900°C.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Solid-State Reactive Sintering of Transparent Polycrystalline Nd:YAG Ceramics

Transparent polycrystalline Nd:YAG ceramics were fabricated by solid-state reactive sintering a mixture of commercial Al₂O₃, Y₂O₃, and Nd₂O₃ powders. The powders were mixed in methanol and doped with 0.5 wt% tetraethoxysilane (TEOS), dried, and pressed. Pressed samples were sintered from 1700° to 1850°C in vacuum without calcination. Transparent fully dense samples with average grain sizes of ∼50 μm were obtained at 1800°C for all Nd₂O₃ levels studied (0, 1, 3, and 5 at.%). The sintering temperature was little affected by Nd concentration, but SiO₂ doping lowered the sintering temperature by ∼100°C. Abnormal grain growth was frequently observed in samples sintered at 1850°C. The Nd concentration was determined by energy-dispersive spectroscopy to be uniform throughout the samples. The in-line transmittance was >80% in the 350–900 nm range regardless of the Nd concentration. The best 1 at.% Nd:YAG ceramics (2 mm thick) achieved 84% transmittance, which is equivalent to 0.9 at.% Nd:YAG single crystals grown by the Czochralski method.