SiC-Whisker-Reinforced Al2O3 Composites by Free Sintering of Coated Powders

SiC whiskers were coated with a thick cladding of finegrained Al₂O₃ powder by controlled heterogeneous precipitation in a concentrated suspension of whiskers. After calcination, the coated whiskers were compacted by cold isostatic pressing and sintered at a constant heating rate of 5°C/min in a helium atmosphere. The parameters which control the coating process and the sintering characteristics of the consolidated powders are reported. Starting with an initial matrix density of 40–45% of the theoretical, composites containing up to ≅20 vol% whiskers (aspect ratio ≅15) were sintered freely to nearly theoretical density below 1800°C. By comparison, a similar composite formed by mechanical mixing of the whiskers and the precipitated Al₂O₃ powder reached a density of only 68% of the theoretical after sintering under identical conditions. For a fixed whisker content, the sinterability of the composites formed from the coated whiskers shows a fairly strong dependence on the whisker aspect ratio.     

Flexure Strength, Fracture Toughness, and Slow Crack Growth of YSZ/Alumina Composites at High Temperatures

Flexure strength and fracture toughness of zirconia–alumina composites, fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with 0–30 mol% alumina particulates or platelets, were determined as a function of alumina content at 1000°C in air. Both strength and fracture toughness of the two composite systems increased with increasing alumina content. For a given alumina content, flexure strength of the particulate composites was greater than that of the platelet composites at higher alumina contents (≥20 mol%); whereas, fracture toughness of the platelet composites was greater than that of the particulate counterparts, regardless of the alumina content. The susceptibility to slow crack growth (SCG), determined at 1000°C via constant stress-rate testing, was greatest for 30 mol% particulate composite with SCG parameter n =5–8 and was least for 30 mol% platelet composite with n =33. Elastic modulus of both composite systems decreased below 400°C and then remained almost unchanged up to 1000°C, forming a unique transition around 400°C, irrespective of alumina content.     

Finite Size Effect on the Sinterability and Dielectric Properties of ZnNb2O6–ZBS Glass Composites

ZnNb₂O₆ (ZN) is a columbite-structured niobate compound showing excellent dielectric properties and comparatively low sintering temperatures (∼1200°C). Hence it is a good candidate for possible low-temperature cofired ceramics (LTCC) applications. In the present investigation, ZnNb₂O₆ was synthesized in the form of micrometer-sized powder using a conventional solid-state ceramic synthesis route as well as in the form of nanosized powder by a polymer complex method. The finite size effect of ZN particles on sinterability and microwave dielectric properties of sintered pellets was evaluated. The phase formation was confirmed from the X-ray diffraction (XRD) analysis. The particle size distribution of the nanoparticles was found to be of the order of 18–20 nm by using high-resolution transmission electron microscopy analysis and 30 nm by analyzing the XRD patterns using Debye Scherrer's formula, after correcting for the instrument broadening effects. A ZN–60ZnO–30B₂O₃–10SiO₂ (ZBS) composite was made by adding predetermined amounts of glasses. The microstructures of the sintered pellets of ZN and ZN–ZBS composites were examined using scanning electron microscopy and analyzed using image analysis. The nano-ZN–ZBS composites were sintered to 93% of the reported density at 925°C/2 h, with microwave dielectric properties of ɛ_r=22.5, Q × f ∼12 800 GHz, and τ_f=−69.6 ppm/°C, emerging as a potential material for possible LTCC applications.     

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.     

Preparation of Mullite Cordierite Composite Powders by the Sol-Gel Method: Its Characteristics and Sintering

Mullite/cordierite composite powders containing different proportions of cordierite were prepared by the sol-gel method using boehmite, colloidal silica, and Mg(NO₃)₂·6H₂O. Mullite and cordierite sols were prepared separately and mixed to form the composite sol. Mullitization temperature depends on the cordierite content in the composite. Also, α-cordierite crystallizes at a lower temperature in a mullite-rich (MC20) composite. The XRD patterns of the powders calcined at 1450°C for 12 h showed that mullite and cordierite exist as two different phases, and no additional phases were observed. The IR absorbance spectra of composites showed characteristic peak corresponding to both mullite and cordierite. The sintered density of the powders increases with temperature up to 1450°C and decreases beyound the melting point of cordierite (1455°C). The microstructure of MC30 sintered at 1440°C for 3 h consisted of acicular grains, whereas in MC40 and MC50 equiaxed grain morphology was observed under similar sintering conditions. The flexural strength and Vickers hardness decreases with the increase of cordierite content in the composite. Dielectric constant and thermal expansion showed a similar behavior.     

Novel Composites Constituted from Hafnia and a Polymer-Derived Ceramic as an Interface: Phase for Severe Ultrahigh Temperature Applications

HfO₂–SiCN (polymer-derived silicon carbonitride) composites were prepared by two methods. In one case, equal volume fractions of HfO₂ and pyrolyzed powders of SiCN were co-sintered, to create a particulate composite . The second type, called interface composites , were prepared by coating HfO₂ particles with a thin film of the polymer precursor, followed by sintering so that densification and pyrolysis of the precursor occurred simultaneously; this process results in a ∼5-nm-thick grain boundary film constituted from Hf, O, and Si. The fracture properties and environmental degradation (in a humid environment at a velocity of 17.6–35.0 cm/s at 1300°C) of these two composites were measured. They were compared with the properties of a reference material made by sintering HfO₂ powders without any additives, under similar conditions (1450°C for 2 h in air). The interface composite yielded the highest sintered density (0.90), exhibited negligible grain growth, and possessed the highest fracture strength (110 MPa). The strength remained immune to hydrothermal oxidation for several hundred hours. In contrast, the particulate composite suffered severe degradation in strength after hydrothermal exposure. The interface composites, with their highly refractory grain boundaries, represent a new class of ceramics for structural applications in harsh environments and at ultrahigh temperatures.     

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.     

In Situ Synthesis of Ultrafine ZrB2–SiC Composite Powders and the Pressureless Sintering Behaviors

Ultrafine ZrB₂–SiC composite powders have been synthesized in situ using carbothermal reduction reactions via the sol–gel method at 1500°C for 1 h. The powders synthesized had a relatively smaller average crystallite size (<200 nm), a larger specific surface area (∼20 m²/g), and a lower oxygen content (∼1.0 wt %). Composites of ZrB₂+20 wt% SiC were pressureless sintered to ∼96.6% theoretical density at 2250°C for 2 h under an argon atmosphere using B₄C and Mo as sintering aids. Vickers hardness and flexural strength of the sintered ceramic composites were 13.9±0.3 GPa and 294±14 MPa, respectively. The microstructure of the composites revealed that elongated SiC grain dispersed uniformly in the ZrB₂ matrix. Oxidation from 1100° to 1600°C for 30 min showed no decrease in strength below 1400°C but considerable decrease in strength with a rapid weight increment was observed above 1500°C. The formation of a protective borosilicate glassy coating appeared at 1400°C and was gradually destroyed in the form of bubble at higher temperatures.     

Microstructural and Mechanical Properties of Hydroxyapatite–Zirconia Composites

This work focuses on the improvement of the mechanical properties of hydroxyapatite (HA) through the addition of 3 mol% yttria partially stabilized zirconia (PSZ). Enamel-derived HA (EHA) from freshly extracted human teeth and commercial HA (CHA) were chosen as the matrix. The effects of addition up to 10 wt% of PSZ and of sintering temperature (1000°–1300°C) on the density, microhardness, and compression strength were evaluated. For EHA–PSZ composites, the density and mechanical properties were generally enhanced by adding 5 wt% PSZ, especially after sintering at 1200°C, whereas CHA–PSZ composites showed lower strength values at sintering temperatures of 1200° and 1300°C with respect to EHA–PSZ composites. This may be due to the lower stability of CHA–PSZ composites with higher amounts of calcium zirconate formed over 1100°C when compared with EHA–PSZ composites.     

Modeling and Fabrication of Fine-Grain Alumina-Zirconia Composites Produced from Nanocrystalline Precursors

Fully dense fine-grained 32.6-vol%-zirconia-toughened alumina composites have been fabricated from nanocrystalline rapidly solidified material. A model considering the thermodynamics of the constrained t -ZrO₂ m -ZrO₂ phase transformation was developed for this percolated two-phase material. This analysis indicated that the grain size at which this phase transformation is thermodynamically favorable was 1.26 µm in a composite that contained 32.6 vol% ZrO₂ and was stabilized with 1.50 mol% Y₂O₃. These results of the model compared favorably with experimental results, showing that grains of this size could be retained after heating to temperatures of as high as 1600°C. The rapidly solidified precursor was ball-milled into submicrometer powder and centrifugally cast into green specimens that were pressureless sintered to full density at temperatures as low as 1500°C. A composite containing nearly 100% t -ZrO₂ was produced by pressureless sintering at 1500°C and a composite containing 45 vol% t -ZrO₂/55 vol% m -ZrO₂ was obtained by sintering at 1600°C. The resulting two-phase microstructures contained uniformly distributed, micrometer-size grains whose sizes are consistent with the facilitation of transformation and microcrack toughening.     

Densification and Phase Transformation of β-SiAlON–Cubic Boron Nitride Composites Prepared by Spark Plasma Sintering

β-SiAlON–cubic boron nitride (cBN) composites were prepared from β-SiAlON and cBN powders at 1600°–1900°C under a pressure of 100 MPa by spark plasma sintering. The effects of cBN content and sintering temperature on densification and phase transformation of the β-SiAlON–cBN composites were studied. When 10–30 vol% cBN was added to β-SiAlON, the shrinkage rate of the compacts increased. The compacts of β-SiAlON–BN composites originally containing 10–30 vol% cBN ceased to shrink at a temperature lower than that of β-SiAlON and the density of the composites increased. The densification of β-SiAlON–BN composites originally containing >40 vol% cBN was suppressed. The phase transformation of cBN to hexagonal BN in the β-SiAlON–BN composite was inhibited to a greater degree than that in the cBN body.     

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.     

Dispersion and Slip Casting of Hydroxyapatite

The dispersibility in deionized water of hydroxyapatite (HA) synthesized by a high-temperature (1000°C) solid-state reaction between tricalcium phosphate and calcium hydroxide was investigated as a function of the pH of the medium and the quantity of two dispersing agents (A = inorganic, B = organic) added to the slips. Although pH modification had a negligible effect on dispersibility, both of the dispersing agents produced a good dispersion at considerably higher concentrations (>2 wt% of HA). At optimum amounts (2–4 wt%) of the dispersing agents, the slips showed near-Newtonian flow behavior up to 45 wt% solids loading and non-Newtonian behavior at >50 wt%. By the optimal addition of dispersing agents and conditioning by ball milling, 60–67 wt% (32–39 vol%) solids-loaded HA slips could be cast into plaster molds to produce 50%–58% dense green bodies, which, in turn, sintered to 90%–94% density in the temperature range 1300°–1400°C. The sintered HA exhibited a three-point flexural strength of 40–60 MPa and a homogeneous microstructure, with interspersed microporosities.     

Mg–Cu–Zn Ferrites for Multilayer Inductors

Mg–Cu–Zn ferrites can be sintered at T ≤950°C to sufficient density and display adequate permeability profiles for application in multilayer ferrite inductors. The permeability and Curie temperature have to be optimized by proper selection of composition. Ferrites with <50 mol% Fe₂O₃ reveal enhanced densification behavior. Submicrometer powders prepared by fine milling show good sintering activity and density after firing at 900°C. Nano-size ferrite powders prepared by coprecipitation or flame synthesis lead to high density; maximum shrinkage already occurs at T <800°C. The use of Bi₂O₃ as a sintering additive further improves the densification, but also affects the microstructure and, hence, the permeability. A maximum permeability of μ_i=450–500 is obtained.     

SiC/ZTM Nanocomposite with Needlelike Mullite Grains and Enhanced Mechanical Properties

Zirconia-toughened mullite (SiC/ZTM) nanocomposites were prepared by a chemical precipitation method. The samples showed good sinterability and could be densified to >98.7% of the theoretical density at 1350°–1550°C. Because of the addition of mullite seeds in the starting powder and the pinning effects of ZrO₂ and SiC particles on mullite grain growth, a fine-grained microstructure formed. Mullite grains were generally equiaxed for the sample sintered at 1400°C; whereas, for the sample sintered at 1550°C, most mullite grains took a needlelike morphology, and SiC particles were primarily located within mullite grains. The strength and toughness increased with the increasing sintering temperature, and reached their respective maximum of 780 MPa and 3.7 MPa·m^1/2 for the sample sintered at 1550°C.     

Enhancing Electrical Properties in NBT–KBT Lead-Free Piezoelectric Ceramics by Optimizing Sintering Temperature

Conventional sintering of (Na_{1− x} K _x )_0.5Bi_0.5TiO₃ (abbreviated as NKBT x , x =18–22 mol%) lead-free piezoelectric ceramics was investigated to clarify the optimal sintering temperature for densification and electrical properties. Both sintered density and electrical properties were sensitive to sintering temperature; particularly, the piezoelectric properties deteriorated when the ceramics were sintered above the optimum temperature. The NKBT20 and NKBT22 ceramics synthesized at 1110°–1170°C showed a phase transition from tetragonal to rhombohedral symmetry, which was similar to the morphotropic phase boundary (MPB). Because of such MPB-like behavior, the highest piezoelectric constant ( d ₃₃) of about 192 pC/N with a high electromechanical coupling factor ( k _p) of about 32% were obtained in the NKBT22 ceramics sintered at 1150°C.     

Flexure Strength of Melt-Infiltration-Processed Titanium Carbide/Nickel Aluminide Composites

TiC/Ni₃Al composites were prepared using a simple melt-infiltration process, performed at either 1300° or 1400°C, with the Ni₃Al content varied over the range of 8–25 vol%. Densities >96% of theoretical were obtained for all composites. Four-point flexure strengths at 22°C increased as the Ni₃Al content increased (i.e., ∼1100 MPa at 20 vol% Ni₃Al), with the highest strengths being observed for composites processed at 1300°C, because of reduced TiC grain size. Strengths at elevated temperatures increased with test temperature, up to ∼1000°C. As with the yielding behavior of the Ni₃Al alloy used, a maximum in composite strength (∼1350 MPa) versus temperature was observed; this occurred at 950°C, which is ∼300°C above the yield maximum for the alloy. Extensive plastic strain was achieved in the composites even at high loading rates at 1135°C, and the yield stress was dependent on the applied loading rate.     

High-Temperature Mechanical Properties of SiC–Mo5(Si,Al)3C Composites

SiC–Mo₅(Si,Al)₃C composites were fabricated by the melt infiltration process, and the infiltration characteristics were studied in detail. Fracture strength and toughness were measured up to 1600°C using a three-point bending test and indentation strength method, respectively. Both fracture strength and toughness significantly increased at 1400°C with respect to the values at room temperature. These increases were mainly attributed to plastic deformation of the infiltrated Mo₅(Si,Al)₃C phases at elevated temperatures, which acted as ductile toughening inclusions. Compressive creep tests were used to study the creep behavior of the composite in the range of 1550°–1650°C and 150–200 MPa. The stress exponent and activation energy were 1.3 and 277 kJ/mol, respectively. Preliminary oxidation tests showed that the composites exhibited good oxidation resistance at 1500°C because of the formation of a dense oxide scale.     

Pressureless Sintering of High-Density ZrB2–SiC Ceramic Composites

Ultra-high-temperature ceramic composites of ZrB₂ 20 wt%SiC were pressureless sintered under an argon atmosphere. The starting ZrB₂ powder was synthesized via the sol–gel method with a small crystallite size and a large specific surface area. Dry-pressed compacts using 4 wt% Mo as a sintering aid can be pressureless sintered to ∼97.7% theoretical density at 2250°C for 2 h. Vickers hardness and fracture toughness of the sintered ceramic composites were 14.82±0.25 GPa and 5.39±0.13 MPa·m^1/2, respectively. In addition to the good sinterability of the ZrB₂ powders, X-ray diffraction and scanning electron microscopy results showed that Mo formed a solid solution with ZrB₂, which was believed to be beneficial for the densification process.     

Synthesis, Properties, and Oxidation of Alumina-Titanium Nitride Composites

Al₂O₃-TiN composites varying from 60 to 66.6 mol% TiN were prepared by an in situ reaction between TiO₂ and AlN. N₂ or O₂ evolution takes place, depending on the composition selected. A pseudobrookite (PB) phase appears in the reaction product, the amount decreasing as the TiO₂:AlN ratio becomes poor in AlN. The in situ reaction product can be pressureless sintered to 94% to 97% theoretical density at 1600°C in N₂. The four-point flexural strength varies from 280 to 430 MPa at room temperature. The fracture toughness is 3 to 4.7 MPa.m^1/2. Oxidation of a 94% dense TiN-Al₂O₃ composite in the temperature range 710° to 1050°C was also studied. A layer of TiO₂ (rutile) protects the composite at 710°C from further oxidation with a weight gain of 0.08 mg/cm² in 90 min. In the temperature range 820° to 1050°C, the initial oxidation kinetics are parabolic, with an activation energy of 216.5 kJ/mol. Linear oxidation kinetics with an activation energy of 113.7 kJ/mol pertain at longer times.