Pressureless Sintering of Zirconium Diboride Using Boron Carbide and Carbon Additions

The synergistic roles of boron carbide and carbon additions in the enhanced densification of zirconium diboride (ZrB₂) by pressureless sintering have been studied. ZrB₂ was sintered to >99% relative density at 1900°C. The combination of 2 wt% boron carbide and 1 wt% carbon promoted densification by removing surface oxide impurities (ZrO₂ and B₂O₃) and inhibiting grain growth. Four-point bending strength (473±43 MPa), Vickers' microhardness (19.6±0.4 GPa), fracture toughness (3.5±0.6 MPa·m^1/2), and Young's modulus (507 GPa) were measured. Thermal gravimetry showed that the combination of additives did not have an adverse effect on the oxidation behavior.     

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.     

Elastic Moduli of Transparent Yttria

The elastic moduli of yttria (Y₂O₃) samples that were made from powders with various particle morphologies were studied by means of ultrasonic measurements. The soundwave velocities in the longitudinal and transverse modes were measured. The elastic moduli were calculated from the sound velocities and density. For the high-purity, high-density (>5000 kg/m³) Y₂O₃ that was prepared in the present study, the average density and elastic moduli (and their standard deviations) were as follows: density (ρ) of 5020 ± 18 kg/m³, Young's modulus ( E ) of 179.8 ± 4.8 GPa, shear modulus ( G ) of 69.2 ± 2.0 GPa, bulk modulus ( B ) of 148.9 ± 3.0 GPa, and Poisson's ratio (ν) of 0.299 ± 0.004. The average longitudinal and transverse soundwave velocities ( V _l and V _t, respectively) were 6931 ± 65 and 3712 ± 49 m/s, respectively. The elastic moduli of lanthana-strengthened yttria (LSY) were ∼6% lower than those of high-purity Y₂O₃, and the nu value for LSY was ∼0.304. It has been argued that soundwave velocity is better than density, in regard to predicting the elastic moduli of fully dense and slightly porous materials. A linear equation that describes the change of the elastic moduli with soundwave velocity alone has been suggested. This equation was applicable to a relative elastic moduli range of 0.75–1.02.     

Thermomechanical Properties of β-Sialon Synthesized from Kaolin

β-Sialon powder was synthesized by the simultaneous reduction and nitridation of Hadong kaolin at 1350°C in an N₂–H₂ atmosphere, using graphite as a reducing agent. The average particle size of β-sialon powder was about 4.5 μm. The synthesized β-sialon powder was pressureless sintered from 1450° to 1850°C under a N₂ atmosphere. The relative density, modulus of rupture, fracture toughness, and microhardness of β-sialon ceramics sintered at 1800°C for 1 h were 92%, 248 MPa, 2.8 MN/m^3/2, and 13.3 GN/m², respectively. The critical temperature difference (ΔT_c) in water-quench thermal-shock behavior was about 375°C for the synthesized β-sialon ceramics.     

Sintering Behavior of Gehlenite, Part II. Microstructure and Mechanical Properties

A self-toughened gehlenite (2CaO·Al₂O₃·SiO₂ or "C₂AS") ceramic with randomly distributed platelet grains was prepared by the organic steric entrapment (PVA) route. The gehlenite ceramic had a density of 2.698–2.875 g/cm³, corresponding to a relative density of 90%–96%. The platelet gehlenite grains had an average thickness of 3.6±0.8 μm and a width of 12.9±3.7 μm, respectively, with an average aspect ratio of 3.6. The three-point bending strength, fracture toughness, and Young's modulus attained were 142.1±12.1 MPa, 2.32±0.12 MPa·m^1/2, and 108±6.8 GPa, respectively. Fractography as well as Vickers indentation crack propagation profiles showed that crack deflection, crack blunting, and pinning effects due to the randomly distributed platelet grains were considered to be responsible for the good mechanical properties of the gehlenite ceramic.     

Microstructure and Mechanical Properties of Hot-Pressed α-Al2O3-Seeded γ-Alumina Ceramics

High-quality alumina ceramics were fabricated by a hot pressing with MgO and SiO₂ as additives using α-Al₂O₃-seeded nanocrystalline γ-Al₂O₃ powders as the raw material. Densification behavior, microstructure evolution, and mechanical properties of alumina were investigated from 1250°C to 1450°C. The seeded γ-Al₂O₃ sintered to 98% relative density at 1300°C. Obvious grain growth was observed at 1400°C and plate-like grains formed at 1450°C. For the 1350°C hot-pressed alumina ceramics, the grain boundary regions were generally clean. Spinel and mullite formed in the triple-grain junction regions. The bending strength and fracture toughness were 565 MPa and 4.5 MPa·m^1/2, respectively. For the 1300°C sintered alumina ceramics, the corresponding values were 492 MPa and 4.9 MPa·m^1/2.     

Preparation and Characterization of Samaria-Doped Ceria Electrolyte Materials for Solid Oxide Fuel Cells

The microstructure, thermal expansion, mechanical property, and ionic conductivity of samaria-doped ceria (SDC) prepared by coprecipitation were investigated in this paper. The results revealed that the average particle size ranged from 10.9±0.4 to 13.5±0.5 nm, crystallite dimension varied from 8.6±0.3 to 10.7±0.4 nm, and the specific surface area distribution ranged from 62.6±1.8 to 76.7±2.2 m²/g for SDC powders prepared by coprecipitation. The dependence of lattice parameter, a, versus dopant concentration, x , of Sm³⁺ ion shows that these solid solutions obey Vegard's rule as a ( x )=5.4089+0.10743 x for Ce_{1− x} Sm _x O_{2−1/2 x} . For SDC ceramics sintered at 1500°C for 5 h, the bulk density was over 95% of the theoretical density; the maximum ionic conductivity, σ_800°C=(22.3±1.14) × 10⁻³ S/cm with minimum activation energy, E _a=0.89±0.02 eV, was found in the Ce_0.80Sm_0.20O_1.90 ceramic. A dense Ce_0.8Sm_0.2O_1.9 ceramic with a grain size distribution of 0.5–4 μm can be obtained by controlling the soaking time at 1500°C. When the soaking time was increased, the microhardness of Ce_0.8Sm_0.2O_1.9 ceramic increased, the toughness slightly decreased, which was related to grain growth with the soaking time.     

Microstructure-Mechanical Property Relationships in Hot Isostatically Pressed Alumina and Zirconia-Toughened Alumina

The rates of densification and the mechanical properties of pure Al₂O₃ and ZrO₂-toughened Al₂O₃ (ZTA) have been investigated as a function of the temperatures and time schedules used for hot isostatic pressing (HIP) as a postsintering heat treatment for samples which had already been pressureless sintered in air at 1460°C for 45 min. ZTA hot isostatically presed at 1400°C had a finer grain size and a narrower grain size distribution than ZTA hot isostatically pressed at 1600°C. At both HIP conditions, the density which could be obtained was almost the maximum theoretical density. The amount of grinding-induced and fracture-induced monoclinic ZrO₂ formed as a result of the tetragonal → monoclinic martensitic transformation in ZTA was higher in the samples hot isostatically pressed at 1400°C. ZTA hot isostatically pressed at 1600°C and 100 MPa had fewer flaws and higher strengths than ZTA hot isostatically pressed at 1400°C for the same time, with a gradual improvement in mechanical properties with increasing HIP time at each of these two temperatures. The best mechanical properties were obtained from ZTA hot isostatically pressed at 100 MPa and 1600°C for 1 h: these specimens had a four-point bend strength of 940 ± 15 MPa at room temperature and 540 ± 15 MPa at 1000°C and an indentation fracture toughness at room temperature of 9.4 ± 0.2 MPa·m^1/2.     

Effect of Micmcracking on the Fracture Toughness and Fracture Surface Fractal Dimension of Lithia-Based Glass-Ceramics

The effect of thermally induced microcracks on the fracture toughness and fractal dimension of fully crystalline lithia disilicate glass-ceramics was studied. The fracture toughness, K _IC, for the nonmicrocracked lithia disilicate, 3.02 ± 0.12 MPa·m^1/2, was significantly greater than the value of 1.31 ± 0.05 MPa·m^1/2 for the microcracked specimens. The fractal dimensional increment, D *, was 0.24 ± 0.01 for nonmicrocracked lithia disilicate specimens compared with a value of 0.18 ± 0.01 for the microcracked specimens. The relationship between K _IC and D * implies that the two materials exhibit dissimilar fracture behavior because of microstructural differences. Estimates of the characteristic length involved in the fracture process, a ₀, indicate that the materials have an identical fracture process at the atomic level. This apparent contradiction may be explained by the scale on which the measurements were taken. It is suggested that fractal analysis at the atomic level would yield equivalent D * values for the two different microstructures.     

Pressureless Sintering of Zirconium Diboride

Zirconium diboride (ZrB₂) ceramics were sintered to a relative density of ∼98% without applied external pressure. Densification studies were performed in the temperature range of 1900°–2150°C. Examination of bulk density as a function of temperature revealed that shrinkage started at ∼2100°C, with significant densification occurring at only 2150°C. At 2150°C, isothermal holds were used to determine the effect of time on relative density and microstructure. For a hold time of 540 min at 2150°C, ZrB₂ pellets reached an average density of 6.02±0.04 g/cm³ (98% of theoretical) with an average grain size of 9.0±5.6 μm. Four-point bend strength, elastic modulus, and Vickers' hardness were measured for sintered ZrB₂ and compared with values reported for hot-pressed materials. Vickers' hardness of sintered ZrB₂ was 14.5±2.6 GPa, which was significantly lower when compared with 23 GPa for hot-pressed ZrB₂. Strength and elastic modulus of the ZrB₂ were 444±30 MPa and 454 GPa, which were comparable with values reported for hot-pressed ZrB₂. The ability to densify ZrB₂ ceramics without hot pressing should enable near-net shape processing, which would significantly reduce the cost of fabricating ZrB₂ components compared with conventional hot pressing and machining.     

Pressureless Densification of Zirconium Diboride with Boron Carbide Additions

Zirconium diboride (ZrB₂) was densified (>98% relative density) at temperatures as low as 1850°C by pressureless sintering. Sintering was activated by removing oxide impurities (B₂O₃ and ZrO₂) from particle surfaces. Boron oxide had a high vapor pressure and was removed during heating under a mild vacuum (∼150 mTorr). Zirconia was more persistent and had to be removed by chemical reaction. Both WC and B₄C were evaluated as additives to facilitate the removal of ZrO₂. Reactions were proposed based on thermodynamic analysis and then confirmed by X-ray diffraction analysis of reacted powder mixtures. After the preliminary powder studies, densification was studied using either as-received ZrB₂ (surface area ∼1 m²/g) or attrition-milled ZrB₂ (surface area ∼7.5 m²/g) with WC and/or B₄C as a sintering aid. ZrB₂ containing only WC could be sintered to ∼95% relative density in 4 h at 2050°C under vacuum. In contrast, the addition of B₄C allowed for sintering to >98% relative density in 1 h at 1850°C under vacuum.     

H2O-Catalyzed Sintering of ∼2-nm-Cross- Section Particles of MgO

MgO produced by vacuum decomposition of Mg(OH) ₂ is formed as aggregates containing both open and closed pores. The surface area and the volume of the open pores, as measured by N₂ adsorption, were found to be 300 m²/g and 0.14 cm³/g, respectively. Through calorimetric and TEM studies, reported elsewhere, the initial surface area and volume of the closed pores are shown to be 550 ± 150 m²/g and 0.19 cm³/g, respectively. The samples were sintered in the presence of water at 823 K. The elimination of the closed pores and coarsening of the open pores dominate early stage sintering under the conditions studied. From the above observations, it is argued that the sintering behavior is governed primarily, not by diffusion, but by a surface step. It is postulated that the nature of the surface step is the formation of new ion layers by random fluctuations in closed pores and in smaller open pores for which edge effects are thermodynamically favorable.     

Mode I Fracture Toughness of a Small-Grained Silicon Nitride: Orientation, Temperature, and Crack Length Effects

The Mode I fracture toughness ( K _{I C} ) of a small-grained Si₃N₄ was determined as a function of hot-pressing orientation, temperature, testing atmosphere, and crack length using the single-edge precracked beam method. The diameter of the Si₃N₄ grains was <0.4 µm, with aspect ratios of 2–8. K _{I C} at 25°C was 6.6 ± 0.2 and 5.9 ± 0.1 MPa·m^1/2 for the T–S and T–L orientations, respectively. This difference was attributed to the amount of elongated grains in the plane of crack growth. For both orientations, a continual decrease in K _IC was observed through 1200°C, to ∼4.1 MPa·m^1/2, before increasing rapidly to 7.5–8 MPa·m^1/2 at 1300°C. The decrease in K _IC through 1200°C was a result of grain-boundary glassy phase softening. At 1300°C, reorientation of elongated grains in the direction of the applied load was suggested to explain the large increase in K _IC. Crack healing was observed in specimens annealed in air. No R -curve behavior was observed for crack lengths as short as 300 µm at either 25° or 1000°C.     

Al2O3/TiC Based Metal Cutting Tools by Microwave Sintering Followed by Hot Isostatic Pressing

The feasibility of producing Al₂O₃/TiC metal cutting tools by fast microwave sintering followed by hot isostatic pressing was examined. Microwave heating profiles able to ensure near-full densification of Al₂O₃/TiC ceramic components were determined. Simple-shape specimens could be sintered to a bulk density of 97% theoretical density (TD) while in the case of tool-shaped ones maximal densification levels attained were somewhat lower, i.e., ∼95% TD. Temperature uniformization—within the heating chamber—by using a particulate SiC susceptor noticeably reduced tool cracking propensity. Densification levels in the range acceptable for commercial tool manufacturing (≥98% TD) were achieved by hot isostatic pressing of the microwave-sintered parts. The isostatically pressed parts exhibited a Vickers hardness H _v≅ 2000 kg/mm² and a fracture toughness K _IC∼ 4.3 MPa·m^1/2.     

Low-Temperature Sintering of Alumina with Liquid-Forming Additives

Simultaneous application of colloidal processing and liquid-forming additives to alumina resulted in a sintered density of >99% in 1 h at a temperature as low as 1070°C for a commercial high-purity alumina powder at a total dopant level of 2 mol%. The additives were 0.9% CuO + 0.9% TiO₂+ 0.1% B₂O₃+ 0.1% MgO. At higher temperatures or after prolonged sintering, the doped alumina ceramic developed a duplex microstructure containing large elongated grains and exhibited a relatively high fracture toughness of ∼ 3.8 MPa · m^1/2 as compared to a value of ∼ 2.6 MPa · m^1/2 for the undoped alumina.     

Grain Growth in Fe3O4

Sintering and microstructural evolution were studied in Fe₃O₄ as a model system for spinel ferrites. Fe₃O₄ powder, purified by the salt-crystallization method, was sintered to ∼99.5% density in a CO-CO₂ atmosphere. The p _O2 Of the sintering atmosphere drastically affects the microstructure (grain size) of sintered Fe₃O₄ without significantly affecting density. The measured grain-boundary mobilities, M , of Fe₃O₄ fit the equation M=M ₀( T ) p _O2^−1/2 with M ₀( T ) = 2.5×10⁵ exp[-(609kJ·mol-¹/ RT ](m/s)(N/m²)^−l. The grain-boundary migration process appeared to be pore-drag controlled, with lattice diffusion of oxygen as the most likely rate-limiting step.     

Combined Mode I–Mode II Fracture of 12-mol%-Ceria-Doped Tetragonal Zirconia Polycrystalline Ceramic

The mode I, mode II, and combined mode Imode II fracture behavior of ceria-doped tetragonal zirconia polycrystalline (Ce-TZP) ceramic was studied. The single-edge-precracked-beam (SEPB) samples were fractured using the asymmetric four-point-bend geometry. The ratio of mode I to mode II loading was varied by varying the degree of asymmetry in the four-point-bend geometry. The minimum strain energy density theory best described the mixed-mode fracture behavior of Ce-TZP with the mode I fracture toughness, K _IC= 8.2 ± 0.6 MPa·m^1/2, and the mode II fracture toughness, K_IIC= 8.6± 1.3 MPa·m^1/2.     

Subcritical Crack Growth in Lead Zirconate Titanate

Subcritical crack growth in terms of velocity–stress intensity factor ( v – K ) curves in lead zirconate titanate (PZT) were experimentally characterized on poled and unpoled compact tension specimens. The poled specimens were tested under open- and short-circuit electrical boundary conditions, which resulted in an increase in fracture toughness by 0.2 MPa·m^1/2 for the accessible velocity range ( v = 10⁻⁹ to 10⁻⁴ m/s) in the open-circuit case. Subcritical crack growth of unpoled specimens was obtained under ambient (relative humidity = 35%) and dry (relative humidity ∼ 0.02%) conditions over a regime in stress intensity factor of 0.5 MPa·m^1/2.     

Pressureless Sintering and Properties of Titanium Diboride Ceramics Containing Chromium and Iron

The simultaneous addition of 0.5 wt% Cr and Fe was found to enhance the densification of TiB₂. The densities of specimens that were sintered for 2 h at 1800° and 1900°C were 97.6% and 98.8% of the theoretical value, respectively. The mechanical properties of the specimen sintered at 1800°C, which had a strength of 506 MPa and a fracture toughness of 6.16 MPa·m^1/2, were much better than those observed in the specimen sintered at 1900°C.