New Uniformly Porous CaZrO3/MgO Composites with Three-Dimensional Network Structure from Natural Dolomite

Porous CaZrO₃/MgO composites with a uniform three-dimensional (3-D) network structure have been successfully synthesized using reactive sintering of highly pure mixtures of natural dolomite (CaMg(CO₃)₂) and synthesized zirconia powders with LiF additive. Equimolar dolomite and zirconia powders doped with 0.5 wt% LiF were cold isostatically pressed at 200 MPa and sintered at 1100–1400°C for 2 h in air. Through the liquid formation via LiF doping, strong necks were formed between constituent particles before completion of the pyrolysis of dolomite, resulting in the formation of a 3-D network structure. During and after the formation of the network structure, CO₂ was given off to form a homogeneous open-pore structure. The pore-size distribution was very narrow (with pore size ∼ 1 μm), and the porosity was controllable (e.g., ∼30%–50%) by changing the sintering temperature. The porous composites can be applied as filter materials with good structural stability at high temperatures.     

Formation and Sintering Characteristics of Aluminum Borate Whiskers

A boric acid-stabilized aluminum acetate powder was decomposed to aluminum borate (Al₁₈B₄O₃₃) by calcining at 1000°C. The powder was then ball-milled, compacted, and fired to temperatures of 1500°, 1600°, and 1700°C for a period of 1 h. The resulting aluminum borate ceramic had a whiskerlike grain morphology, with the whisker length approaching 20 μm and a diameter of 2–3 μm. The sintered compact showed no shrinkage upon firing, had a porosity of ∼50%, a narrow pore size distribution, and an average pore size of 1–3 μm.     

Low-Temperature Fine-Grained Alumina–Aluminum Titanate Composites Produced from a Titania-Coated Alumina Precursor

A method for the preparation of alumina–aluminum titanate (AT) composites, which can be sintered to high density with a fine-grained microstructure at <1450°C, is reported. The composite precursor is alumina particles coated by sol–gel-derived titania, which reacts during sintering to form AT in situ at temperature as low as 1300°C. The composite can be sintered at 1350°C to 98% density with 1.5–2.0 μm grain size. Other composites containing 5–50 wt% AT are also investigated.     

Influence of Sintering Temperature on Grain Growth and Phase Structure of Compositionally Optimized High-Performance Li/Ta-Modified (Na,K)NbO3 Ceramics

Microstructure characteristics, phase transition, and electrical properties of (Na_0.535K_0.485)_0.926Li_0.074(Nb_0.942Ta_0.058)O₃ (NKN-LT) lead-free piezoelectric ceramics prepared by normal sintering are investigated with an emphasis on the influence of sintering temperature. Some abnormal coarse grains of 20–30 μm in diameter are formed in a matrix consisting of about 2 μm fine grains when the sintering temperature was relatively low (980°C). However, only normally grown grains were observed when the sintering temperature was increased to 1020°C. On the other hand, orthorhombic and tetragonal phases coexisted in the ceramics sintered at 980°–1000°C, whereas the tetragonal phase becomes dominant when sintered above 1020°C. For the ceramics sintered at 1000°C, the piezoelectric constant d ₃₃ is enhanced to 276 pC/N, which is a high value for the Li- and Ta-modified (Na,K)NbO₃ ceramics system. The other piezoelectric and ferroelectric properties are as follows: planar electromechanical coupling factor k _p=46.2%, thickness electromechanical coupling factor k _t=36%, mechanical quality factor Q _m=18, remnant polarization P _r=21.1 μC/cm², and coercive field E _c=1.85 kV/mm.     

Fabrication of Transparent Hydroxyapatite Sintered Body with High Crystal Orientation by Pulse Electric Current Sintering

Transparent hydroxyapatite (HAp) sintered body with a high crystal orientation and a relative density of 99.7% was fabricated by the pulse electric current sintering method; the c -axis of HAp crystals with a hexagonal column morphology and ca. 200 μm × 25 μm in size was oriented perpendicular to the pressure direction. The sintered temperature increased to 1200°C at a heating rate of 50°C/min for 10 min and a pressure of 50 MPa was applied. The orientation indexes were calculated from X-ray diffraction patterns of the planes perpendicular and parallel to the pressure direction. The optical transmittance was greater than 70% over the wavelength of 700 nm.     

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.     

Molten-Salt Synthesis of Ba1–xPbxTiO3 in the System BaTiO3–PbCl2

Ba_{1– x} Pb _x TiO₃ powder with a fixed composition was prepared by the reaction of BaTiO₃ powders with molten PbCl₂at various PbCl₂/BaTiO₃ molar ratios at 600° and 800°C in a nitrogen atmosphere. When 0.1 μm powder was used, the reaction was finished when x = 0.9. Two phases of BaTiO₃and a solid solution of Ba_{1– x} Pb _x TiO₃ coexisted, but the final phase gave a solid solution of Ba_{1– x} Pb _x TiO₃ at 800°C. When 0.5 μm powder was used, the two phases coexisted in the products at 600°C at PbCl₂/BaTiO₃= 1.0. A sintered compact of Ba_{1– x} Pb _x TiO₃ powders solid solution was prepared by hot isostatic pressing, and its dielectric constant was measured in the temperature range 20°–550°C.     

Reactive Synthesis of a Porous Calcium Zirconate/Spinel Composite with Idiomorphic Spinel Grains

Porous CaZrO₃/MgAl₂O₄ composites were synthesized in air by pressureless reactive sintering of an equimolar mixture of dolomite (CaMg(CO₃)₂), monoclinic zirconia ( m -ZrO₂), and α-alumina powders, with a 0.5 wt% lithium fluoride additive. The reaction behavior of the mixed powders (with/without LiF additive) was studied using high-temperature X-ray diffraction. A bulk porous composite resulted from sintering at 1300°C for 2 h (in a nearly closed container, so as to increase the LiF-doping effect), which consisted of fine grains (CaZrO₃ and MgAl₂O₄, ∼0.5–1 μm) and well-grown idiomorphic ones (MgAl₂O₄ octahedra ∼ 2–4 μm). The idiomorphic spinel grains were located around the inner walls of relatively large pores. The composite showed appreciably high bending strength (σ_f= 110 ± 8 MPa for a porosity of 31%). The porous CaZrO₃/MgAl₂O₄ composites can be applied as high-temperature filters and lightweight structural components.     

Sintering and Characterization of Polycrystalline Monoclinic, Tetragonal, and Cubic Zirconia

Polycrystalline monoclinic ( m ), tetragonal ( t ), and cubic ( c ) ZrO₂, sintered at 1500°C, were annealed in the cubic stability field and rapidly cooled to permit the displacive c → t ' transformation to occur in compositions containing 0–6 mol% Y₂O₃. The bulk fracture toughness of coarse-grained (> 25 μm) m , t ', and c zirconias were compared with conventionally sintered, fine-grained (typically less than 1 μm) materials. The ferroelastic monoclinic and tetragonal zirconias were more than twice as tough as paraelastic cubic zirconia.     

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.     

Synthesis of Dense Lead Titanate Ceramics with Submicrometer Grains by Spark Plasma Sintering

Dense PbTiO₃ ceramics consisting of submicrometer-sized grains were prepared using the spark-plasma-sintering (SPS) method. Hydrothermally prepared PbTiO₃ (0.1 μm) was used as a starting powder. The powder was densified to ≳98% of the theoretical X-ray density by the SPS process. The average grain size of the spark-plasma-sintered ceramics (SPS ceramics) was ≲1 μm, even after sintering at 900°–1100°C, because of the short sintering period (1–3 min). The measured permittivity of the SPS ceramics showed almost no frequency dependence over the range 10¹–10⁶ Hz, mainly because pores were absent from the ceramics. The coercive field of the SPS ceramics was somewhat higher than that of conventionally sintered ceramics, which could be attributed to the small-grained microstructures of the SPS ceramics.     

Electrophoretic Deposition of Ferroelectric Barium Titanate Thick Films and Their Dielectric Properties

Barium titanate thick films 10–70 μm thick were obtained using a unique electrophoretic deposition technique, which utilizes a mixed ethanol–acetylacetone suspension as the dispersive medium. The capacitance of the BaTiO₃ films was measured as 25–70 nF, at temperatures of up to 200°C, giving a dielectric constant of 4000–12000 and dielectric loss (tan δ) of 0.13–0.51. In the sintered films thus deposited, (111) orientation was observed, and the degree of orientation was found to increase with decrease of the thickness of the films. In so-oriented films, the Curie point was confirmed to be near 120°C.     

Effect of Heat Treatment on Grain Size, Phase Assemblage, and Mechanical Properties of 3 mol% Y-TZP

The effect of heat treatment on the grain size, phase assemblage, and mechanical properties of a 3 mol% Y-TZP ceramic was investigated. Specimens were initially sintered for 2 h at 1450°C to near theoretical density; some specimens were then heat-treated at 1550°, 1650°, 1750°, or 1850°C to coarsen the microstructure. The average grain size increased with heat treatment from <0.5 to ∼10 μ-m. Phase analyses revealed predominantly tetragonal and cubic phases below 1750°C, with a significant decrease in tetragonal content and increase in monoclinic content for temperatures >1750°C. The maximum fraction of tetragonal phase that transformed during fracture corresponded with the largest tetragonal grain size of ∼5–6 μm. Strength was on the order of 1 GPa, and was surprisingly insensitive to heat-treatment temperature and grain size, contrary to previous studies. The fracture toughness increased from 4 to 10 MPa.m^1/2 with increasing grain size, owing to an increasing transformation zone size. Grain sizes larger than 5–6 μm spontaneously transformed to monoclinic phase during cooling. Such critical grain sizes are much larger than those found in past investigations, and may be due to the greater fraction of cubic phase present which decreases the strain energy arising from crystallographic thermal expansion anisotropy of the tetragonal phase.     

Synthesis and Densification of Transparent Magnesium Aluminate Spinel by SPS Processing

Mixtures of elementary oxides, MgO–Al₂O₃, were used to fabricate transparent polycrystalline magnesium aluminate spinel specimens by means of the spark plasma sintering technique. A sintering aid, 1 wt% of LiF, was added to the mixed powder. The presence of the additive promotes the synthesis of spinel that starts at 900°C and is completed at 1100°C. The LiF additive wets spinel on its melting and promotes densification, which is completed at 1600°C. LiF vapor plays a cardinal role in eliminating residual carbon contamination and in the fully dense state, allows attaining a 78% level of optical transmittance. The optimal conditions for achieving adequate transparency were determined and the role of the LiF addition in the various stages of the process is discussed.     

B6O–c-BN Composites Prepared by High-Pressure Sintering

High-pressure sintering behavior in the B₆O– c -BN system was investigated using in-laboratory-synthesized B₆O and commercially available c -BN powders (with an average grain size of 0.5, 3, or 6 μm). No reaction occurred between the two components under the high-pressure (4–6 GPa) and high-temperature (1500°–1800°C) conditions that have been investigated. Well-dispersed, sintered B₆O– x ( c -BN) composites (where x = 0–60 vol%) of almost-full density were prepared by sintering at a pressure of 6 GPa and temperature of 1800°C for 20 min. The maximum Vickers microhardness (46 GPa) of these composites was attained by adding 40 vol% c -BN with an average grain size of 0.5 μm. The fracture toughness of these composites increased as the c -BN content increased; the maximum fracture toughness (1.5–1.8 MPa^.m^1/2) was observed for x = 40–60 vol%. Crack deflection along the B₆O– c -BN grain boundary contributed to increasing the fracture toughness.     

Spark Plasma Sintering of Nano-Sized TiN Prepared from TiO2 by Controlled Hydrolysis of TiCl4 and Ti(O-i-C3H7)4 Solution

Nano-sized TiO₂ powders were prepared by controlled hydrolysis of TiCl₄ and Ti(O-i-C₃H₇)₄ solutions and nitrided in flowing NH₃ gas at 700°–1000°C to form TiN. Nano-sized TiN was densified by spark plasma sintering at 1300°–1600°C to produce TiN ceramics with a relative density of 98% at 1600°C. The microstructure of the etched ceramic surface was observed by SEM, which revealed the formation of uniformly sized 1–2 μm grains in the TiCl₄-derived product and 10–20 μm in the Ti(O-i-C₃H₇)₄-derived TiN. The electric resisitivity and Vickers micro-hardness of the TiN ceramics was also measured.     

Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Effect of Microstructure on the Tribological and Mechanical Properties of CuO-Doped 3Y-TZP Ceramics

Dense 8 mol% CuO-doped 3Y-TZP ceramics were prepared by pressureless sintering for 8 h at 1500° and 1550°C, respectively. Transmission electron spectroscopy revealed that the ceramic sintered at 1500°C exhibits grain boundaries free of any amorphous phase, while crystalline copper-oxide grains were found in the zirconia matrix, whereas the sample sintered at 1550°C contains a Cu-rich amorphous grain boundary layer. The tribological behavior of these materials was tested under dry-sliding conditions using a pin-on-disk tribometer. The material sintered at 1500°C showed self-lubrication resulting in a low coefficient of friction ( f ) of 0.2–0.3 and a low specific wear rate ( k ) ≪ 10⁻⁶ mm³·(N·m)⁻¹. In contrast, the material sintered at 1550°C showed poor tribological behavior ( f =0.8–0.9; k ≫ 10⁻⁶ mm³·(N·m)⁻¹ under the same conditions. The difference in the tribological behavior of these two materials was interpreted on the basis of mechanical properties and microstructural characteristics.     

Spin Coating of a Ca(Ti,Fe)O3 Dense Film on a Porous Substrate for Electrochemical Permeation of Oxygen

A dense Ca(Ti_0.75Fe_0.25)O_3−α (Ca(Ti,Fe)O₃) film, which is a mixed conductor of oxide ions and electrons/holes, was prepared on a porous CaTiO₃ substrate by a spin-coating method. The calcined Ca(Ti,Fe)O₃ powder with 2–3 μm grain sizes was mixed with a dispersant in ethanol to form the slurry for spin coating. A uniform Ca(Ti,Fe)O₃ green film was obtained at 1000–1500 rpm on the rotating porous CaTiO₃ substrate, which had an average pore diameter of a few micrometers. The optimum sintering conditions for the spin-coated films were a soaking temperature of 1235°C and a holding time of 2 h, in air. A dense, sintered Ca(Ti,Fe)O₃ film }20–50 μm thick was prepared by repeating the coatingsintering process. The gas-tight film prepared on the porous substrate exhibited higher electrochemical permeation of oxygen at an operating temperature of 1000°C compared with that of thicker, sintered Ca(Ti,Fe)O₃ disks.     

High-Density Pressureless-Sintered HfC-Based Composites

Hafnium carbide (HfC)-(5, 10, and 20 vol%) MoSi₂ ceramics were pressureless sintered at 1950°C in an argon flux. The materials had nearly full density (96%–98%), with mean grain sizes in the range of 3–4 μm. Depending on the MoSi₂ amount (5–20 vol%), the mechanical properties were in the following ranges: hardness 16–15 GPa, Young's modulus 434–385 GPa, fracture toughness 3.6–3.4 MPa·m^1/2, and room-temperature 4-point flexural strength 465–383 MPa.