Shift of the Curie Point of Barium Titanate Ceramics with Sintering Temperature

Definite increases in the Curie point (T_C) of undoped and lanthanum- (La-) doped (<0.5 at.%) barium titanate (BaTiO₃) ceramics sintered at elevated temperatures in the range of 1300°-1450°C were observed. Both undoped and 0.3 at.% La-doped BaTiO₃ (chosen as a typical doping concentration to yield semiconducting materials) ceramics showed almost the same T_C behavior; their T_C values increased by ∼3.5°C as the sintering temperature was increased from 1300° to 1450°C. Semiconducting 0.3 at.% La-doped materials increased in room-temperature bulk resistivity and TC with increased sintering temperature. The bulk resistivity of the La-doped materials, which was obtained from complex impedance analysis, increased from ∼2 omega cm for the material sintered at 1350°C to ∼6 ω cm at 1450°C. The phenomenon of bulk resistivity increase with sintering temperature was observed in the materials with a doping concentration of ≥ 0.2 at.% La, but was not observed in those doped with <0.2 at.% La. The mechanisms of TC and the bulk resistivity increase observed in the present materials with increased sintering temperature are discussed based on various models found in the literature, particularly in terms of the defect chemistry in semiconducting BaTiO₃ ceramics and the influence of liquid phases present during sintering.     

Spark Plasma Sintering of Nanocrystalline Niobium Nitride Powders

Nanocrystalline niobium nitride (NbN) powders were sintered by spark plasma sintering under a nitrogen atmosphere at temperatures from 1040° to 1230°C. Fully dense bulk NbN ceramic with grain sizes of 0.5–1.0 μm was obtained at 1130°C. The effects of sintering temperature on the density, phase content, electrical conductivity, Vickers hardness, and microstructure of the NbN ceramic were discussed.     

α-β Sialon Ceramics Made from Different Silicon Nitride Powders

The present work is concerned with the sintering of an α-β sialon ceramic using five different silicon nitride powders from a single source. The parameters varied in the silicon nitride were the amount of "free' silicon, iron content, α:β ratio, and grain size as measured by BET surface. The sintering atmosphere was varied by use of protective powder beds with passive (boron nitride) and active (SiO-generating) properties. Five sintering temperatures between 1600° and 1800°C were used. Microstructural characterization as well as density, hardness, and fracture toughness measurements were carried out. The sintering conditions were found to be critical for obtaining fully dense materials and low weight change. The optimum sintering temperature was 1750°C. The silicon nitride powder with a high content of free silicon resulted in a material which was more susceptible to the sintering atmosphere conditions. An α-β sialon made from a silicon nitride powder with a high β-α phase ratio resulted in a higher β-α ratio in the sintered material.     

Experimental determination of ultrasonic wave velocities in plastics as functions of temperature. III. Rigid epoxy foam

The velocity and attenuation of longitudinal bulk waves in a solid epoxy foam were measured by an acoustic pulse technique in the frequency range of 0.667–4.0 Mc./sec. and in the temperature range from ambient to 150°C. The measurements are reported with the density of the solid epoxy and with aluminum impurity loading as parameters. Over the indicated temperature and frequency ranges, complete attenuation and velocity measurements are reported for one foam corresponding to a density of 0.325 g./cc. In the density range of 0.088–0.325 g./cc. for the unloaded foams, attenuation is reported at room temperature. It is observed that the longitudinal velocities for all the densities decrease with temperature by about 40% in a span of 100°C. and that an approximately linear relation exists with temperature. The velocities in the foams loaded with small percentages of aluminum and heat-treated at 250°C. exhibit temperature behavior which is dependent upon the combined effects of loading, density change, and epoxy properties. For the loaded foam with the highest density (1.068 g./cc.), velocity is reported to a temperature of about 250°C. The velocities of all the various density samples with the exception of the loaded foams exhibit inflections at a temperature of about 110°C. The attenuation–temperature measurements on the 0.325 g./cc. sample show similar behavior at this temperature except that the effect is much more pronounced than the velocity inflection, hence a better indication of the transition. The precision of the measurement is about 2% for the relative longitudinal velocities and about 20% for the attenuation.     

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.     

Hot Pressing of Tantalum Carbide With and Without Sintering Additives

Densification of tantalum carbide (TaC) was studied by hot pressing at temperatures ranging from 1900° to 2400°C with and without sintering additives. Without sintering additives, the relative density increased from 75% at 1900°C to 96% at 2400°C. A microstructural examination showed no observable grain growth up to 2300°C. Densification was enhanced with carbon (C) and/or B₄C additions. TaC with a 0.78 wt% C addition achieved a relative density of 97% at 2300°C. Additions of 0.36 wt% B₄C or 0.43 wt% B₄C and 0.13 wt% C increased the relative density to 98% at 2200°C, accompanied by rapid grain growth at 2100°C and higher temperatures.     

Densification of Si3N4 with LiYO2 Additive

This paper deals with the densification and phase transformation during pressureless sintering of Si₃N₄ with LiYO₂ as the sintering additive. The dilatometric shrinkage data show that the first Li₂O- rich liquid forms as low as 1250°C, resulting in a significant reduction of sintering temperature. On sintering at 1500°C the bulk density increases to more than 90% of the theoretical density with only minor phase transformation from α-Si₃N₄ to β-Si₃N₄ taking place. At 1600°C the secondary phase has been completely converted into a glassy phase and total conversion of α-Si₃N₄ to β-Si₃N₄ takes place. The grain growth is anisotropic, leading to a microstructure which has potential for enhanced fracture toughness. Li₂O evaporates during sintering. Thus, the liquid phase is transient and the final material might have promising mechanical properties as well as promising high-temperature properties despite the low sintering temperature. The results show that the Li₂O−Y₂O₃ system can provide very effective low-temperature sintering additives for silicon nitride.     

Thermal Shock Damage Assessment in Ceramics Using Ultrasonic Waves

Structural ceramics are susceptible to microcrack damage by thermal shock. There is a critical temperature for thermal shock damage initiation with damage severity increasing at greater shock temperatures. In this work the applicability of an ultrasonic method to determine the critical temperature and the accumulated damage is demonstrated in alumina. Information is obtained via velocity and attenuation measurements using surface and obliquely incident bulk ultrasonic waves. The elastic anisotropy effect due to preferred crack orientation has been estimated. The critical temperature for the alumina is about 200°C. The damage increases steeply from 200° to 400°C and grows significantly above 400°C. Changes of up to 17% from the original values in the effective shear moduli and up to 45% in the longitudinal effective modulus in the direction transverse to crack orientation are measured at high thermal shock temperatures.     

Correlations between Strength and Acoustic Properties in Yttria-Stabilized Zirconia Polycrystals

The strength, bulk density, and acoustic properties of nine Y₂O₃-stabilized ZrO₂ polycrystals (Y-TZPs) were evaluated in the present study. The samples showed a strong correlation between strength and acoustic properties, a phenomenon that reflects the internal bulk structure, especially the Pore size distribution. Strength increased with a decrease in the attenuation coefficient and with an increase in the transverse wave velocity of the samples. On the other hand, the bulk density of the samples showed no clear relationship with strength. Bulk density reflects only the amount of pore volume in the test piece, whereas the acoustic properties are sensitive to defects or inhomogeneities in the microstructure. The attenuation coefficient and transverse wave velocity thus seem to be good parameters for estimating the strength of Y-TZPs.     

Sintering and Characterization of Nanophase Zinc Oxide

Nanocrystalline, single-phase undoped ZnO was sintered to 95%–98% of theoretical density at 650°–700°C, using pressureless isothermal sintering. The density increased very rapidly at 500°–600°C, remained constant with sintering temperature until ∼900°C, and then decreased slightly. The estimated activation energy for densification at 600°–700°C (275 kJ/mol) was comparable to grain-growth activation energies previously reported for microcrystalline ZnO but much greater than the grain-growth activation energy measured in the present work. A bimodal microstructure, consisting of nanocrystalline grains within larger ensembles ("supergrains"), was observed, and both modes grew as the sintering temperature increased. The grain-growth activation energy for the nanocrystalline grains was extremely low, ∼20 kJ/mol. The activation energy for the growth of the supergrains depended strongly on temperature but was ∼54 kJ/mol at >500°C. The important mechanisms probably are rearrangement of the nanoparticle grains, with simultaneous surface and boundary diffusion, and vapor transport above 900°C.     

Electrical Properties of High-Density Iron-Deficient Nickel-Zinc Ferrites

The dc resistivity of nickel-zinc ferrite was studied as a function of nickel/zinc ratio, apparent density, temperature, and grain size. Resistivities of Ni_0.40Zn_0.51Fe_1.90O₄– and Ni_0.35Zn_0.65-Fe_1.90O₄– are similar. Evaluation of samples sintered between 1100° and 1220°C showed that densification proceeds rapidly for sintering temperatures 1170°C; for these specimens the room temperature resistivity increases to an equilibrium value with sintering time. Samples sintered to 99+% of theoretical density at lower temperatures densify slowly; the resistivity is invariant with sintering time. The Seebeck coefficient for the p -type ferrites is 550 μV/°C from 200° to 700°C; the dielectric constant varies from 17.3 at 0.5 MHz to 16.4 at 15 MHz.     

Density and Permeability of Sintered Slip-Cast Magnesia

Fused magnesia was ball-milled in ethanol for 14, 30, 48, and 100 hours, and particle-size distributions were determined. Specimens were slip-cast from the suspensions and were fired in air at 1300°, 1400°, and 1470°C, for times up to 8 hours, and gas-permeability and bulk density determinations were performed on the fired pieces. For all specimens the gas flow was essentially of the Knudsen type. The maximum bulk density, 96.7% of theoretical, was obtained by sintering a specimen, cast from the magnesia ball-milled for 100 hours, at 1470° for 3 hours. At this density the permeability was zero. The relation between permeability and porosity could be represented by the equation K _M = 6.9 ° 10⁻¹⁰( P_F )^2.54, where P_F is 100( d ₀ - d/do ). Here d is the bulk density and d ₀ is a constant representing the bulk density at which the permeability becomes zero. The foregoing equation fits the data for all specimens if it is assumed that do is a function of the particle-size distribution in the slip, varying from 3.36 g per cm³ for the magnesia ball-milled for 100 hours to 3.58 g per cm ³ for the magnesia ball-milled for 14 hours.     

Critical Current Densities in Thin Ceramic Tapes of Superconducting Ba2YCu3O7

Tape-cast slurries of Ba₂YCu₃O₇ powders offer a convenient means of preparing sintered ceramic samples for critical current density (J_c) measurements where the transport cross section is small and the current electrode areas are large. Samples were sintered from 900° to 1000°C and characterized for bulk density, grain size, phase composition, T_c, and J_c. Bulk density and grain size both increase with sintering temperature while all samples were single-phase perovskite except for those sintered at 900°C. The onset temperature for superconductivity is constant at about 93 K while the transition sharpens to R=0 at about 92 K for the densest samples. J_c rises with sintering temperature to a maximum of ∼10³ A/cm². A linear relationship between J_c and bulk density is predicted from microstructural considerations.     

Characteristics of Si3N4-SiO2-Ce2O3 Compositions Sintered in High-pressure Nitrogen

Full-density Si₃N₄-SiO₂-Ce₂O₃ compositions were prepared by sintering with 2.5 MPa nitrogen pressure at temperatures of 1900° and 2090°C. Room-temperature flexural strengths near 700 MPa for sintered material compared favorably with the strength of hot-pressed material. At 1370°C, where flexural strengths as high as 363 MPa were obtained, it was observed that the coarsest structure was the strongest and the finest structure was the weakest. One of the compositions tested, Si₃N₄-8.7 wt% SiO₂-8.3 wt%-Ce₂O₃, was found to have excellent 200-h oxidation resistance at 700°, 1000°, and 1370°C, without incidence of 700° to 1000°C phase instability and cracking.     

Two-Stage Sintering of Alumina with Submicrometer Grain Size

This work verifies the applicability of two-stage sintering as a means of suppressing the final stage grain growth of submicrometer alumina. The first heating step should be short at a relatively high-temperature (1400°–1450°C) in order to close porosity without significant grain growth. The second step at temperatures around 1150°C facilitates further densification with limited grain growth. Fine-grained alumina with a relative density of 98.8% and a grain size of 0.9 μm was prepared by two-stage sintering. A standard sintering process resulted in ceramics with identical relative density and a grain size of 1.6 μm.     

Processing of a Silicon-Carbide-Whisker-Reinforced Glass-Ceramic Composite by Microwave Heating

A calcium magnesium aluminosilicate-based glass that contained 10 wt% of silicon carbide whiskers (SiC _w ) as reinforcement was prepared by tape casting, followed by sintering either in a conventional furnace or in a microwave oven. The results were consistent with retardation of glass sintering through whisker bridging. The glass, by itself, was sintered to almost-full density at 750°C for 4 h by conventional furnace sintering; the best sintered composite, with an estimated density of ∼90%, was obtained at 800°C with a dwell time of 4 h. Sintering at a temperature of >800°C did not improve the densification but rather resulted in severe whisker oxidation. A reduced densification rate was observed for the samples that were sintered in nitrogen. By contrast, in the microwave oven, almost-full density for the glass and ∼95% of the theoretical density for the composite were obtainable at 850°C for 15 min, which represented a reduction of ∼10 h of the total processing time and a reduced SiC _w oxidation.     

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.     

Sintering of Alumina at Temperatures of 1400°C. and Below

Previous investigators have indicated that both small particles and the addition of certain oxides promote the sintering of alumina at temperatures below 1700°C. By utilizing combinations of oxides and small particle size, the sintering temperature of 96% alumina bodies was reduced in this investigation to the 1300° to 1400°C. range. It is proposed that this low-temperature sintering is aided by the formation of a liquid phase. Thin sections of the alumina sintered at low temperatures revealed bodies with small grain size whose bulk densities were above 3.80 gm. per cc.     

Sintering of Nanophase γ-Al2O3 Powder

The sintering of ultrafine γ-Al₂O₃ powder (particle size ∼10–20 nm) prepared by an inert gas condensation technique was investigated in air at a constant heating rate of 10°C/min. Qualitatively, the kinetics followed those of transition aluminas prepared by other methods. Measurable shrinkage commenced at ∼ 1000°C and showed a region of rapid sintering between ∼1125° and 1175°C followed by a transition to a much reduced sintering rate at higher temperatures. Starting from an initial density of ∼0.60 relative to the theoretical value, the powder compact reached a relative density of 0.82 after sintering to 1350°C. Compared to compacts prepared from the as-received powder, dispersion of the powder in water prior to compaction produced a drastic change in the microstructural evolution and a significant reduction in the densification rate during sintering. The incorporation of a step involving the rapid heating of the loose powder to ∼1300°C prior to compaction (which resulted in the transformation to α-Al₂O₃) provided a method for significantly increasing the density during sintering.     

Agglomerate and Particle Size Effects on Sintering Yttria-Stabilized Zirconia

The initial-, intermediate-, and final-stage sintering of fine crystallite yttria-stabilized zirconia was studied. Experiments were conducted on powder lots of differing agglomerate size and one specially prepared agglomerate-free powder. Initial-stage sintering kinetics were compared with a sintering study on larger crystallite size calcia-stabilized zirconia to access the Herring scaling law. It was found that agglomerates limit attainable green density, interfere with the development of microstructure, impede initial-stage sintering kinetics, and limit the potential benefit of fine crystallites on final-stage sintering. An gglomerate free powder centrifuge-cast to 74% green density was sintered to 99.5% of theoretical density in a 1 h 1100°C cycle, which is ∼300°C lower than necessary for an agglomerated but equal crystallite size powder.