Grain-Boundary Cavitation and Bloating of Isostatically Hot-Pressed Magnesia-Partially-Stabilized Zirconia on Air Annealing

Commercially sintered magnesia-partially-stabilized zirconia was densified to near theoretical density by isostatic hot-pressing at 200 MPa and 1700°C in argon. Subsequent air annealing above 1100°C resulted in bloating of the material due to grain-boundary cavitation. Mass spectrometry of crushed samples detected the evolution of CO₂ and possibly CO on annealing; the hot-pressed material showed a sudden gas evolution above 1400°C. Preliminary Auger and ESCA analysis identified the presence of carbon as graphite and an undefined carbide in both the sintered and the hot-pressed material.     

2223 Phase Formation in Bi(Pb)─Sr─C─a─Cu─O: II, The Role of Temperature—Reaction Mechanism

The formation mechanism, the temperature range for the growth, and the thermal stability of the 2223 phase in Bi(Pb)─Sr─Ca─Cu─O have been investigated using DTA/TG, XRD, SEM/EDAX, TEM, EPMA, four-probe resistance and acsusceptibility measurement. The formation of the 2223 phase was found to follow a dissolution–precipitation process. A 2212 phase first reacts with the liquid phase formed via an incongruent melting of the Ca₂PbO₄ phase, and a dissolution of CaO and CuO takes place. The 2201 phase, which has the largest negative free energy, is then precipitated from the melt; the nucleation and growth of the 2223 phase are subsequently developed by the reaction between the 2201 phase precipitates and ions of Ca²⁺ and Cu²⁺ present in the liquid phase. The 2223 phase is formed at temperatures in the range 827°C T < 856°C. The optimum temperature T _f for the formation of 2223 phase is 845°± 5°C. The 2223 phase is thermodynamically unstable at temperatures above 856°C.     

2223 Phase Formation in Bi(Pb)─Sr─Ca─Cu─O: III, The Role of Atmosphere

The formation of second phases during the preparation of the 2223 phase and their stability in the Bi system under various annealing temperatures and atmospheres have been studied. The 2201 precipitates developed at ∼830°C, and their conversion to the 2223 phase can be completed in the temperature range 810°C ≤ T < 830°C. A Ca₂PbO₄-like phase can precipitate from the liquid phase at ∼830°C during cooling. A (Sr,Ca)₁₄Cu₂₄O₄₁ phase is usually found accompanying the synthesis of the 2223 phase. This secondary phase is stable in an oxidizing atmosphere but can be eliminated by annealing under a low oxygen atmosphere or by choosing a suitable starting composition and set of sintering conditions. The precipitation of Ca₂PbO₄-like phase can be avoided by using a relatively fast cooling rate. Unlike the YBa₂Cu₃O _x superconductor, the 2223 phase can be stable under a wide range of atmospheres, such as argon, air, and oxygen.     

Superconducting Characteristics of Polycrystalline Magnesium Diboride Ceramics Fabricated by a Spark Plasma Sintering Technique

Highly densified MgB₂ superconductors were successfully fabricated using a spark plasma sintering (SPS) technique, and their superconductivity with respect to microstructural evolution was evaluated. Full densification with final density close to the theoretical density was achieved at a temperature of 1000°C within a total SPS processing time of 40 min. Both an MgB₂ specimen sintered at 1000°C for 30 min and one sintered at 1050°C for 10 min exhibited a high critical transition temperature ( T _c) similar to that of an MgB₂ single crystal (39 K), and a very sharp superconducting transition width (Δ T ) less than 0.5 K. In addition, high critical current densities ( J _c) of 7.7 × 10⁵ A/cm² in a field of 0.6 T at 5 K and of 8.3 × 10⁴ A/cm² in a field of 0.09 T at 35 K were obtained. These excellent superconducting characteristics of the SPS-processed MgB₂ are attributed to uniformly distributed secondary MgO phase nanoparticles and well-developed dislocations in the microstructure that may act effectively as extrinsic flux pinning sites, resulting in the strong pinning force showing a high J _c of 8.7 × 10⁴ A/cm² even in the condition of a field of 4 T at 5 K.     

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.     

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.     

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.     

Effect of Hot-Pressing Temperature on Densification and Mechanical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid

The effect of hot-pressing temperature on the densification behavior and mechanical properties of titanium diboride (TiB₂) was investigated. TiB₂ specimens were hot-pressed for 1 h at temperatures in the range of 1500°–1800°C, with an addition of 2.5 wt% of silicon nitride (Si₃N₄) as a sintering aid. The density increased markedly at temperatures in the range of 1500°–1600°C and remained constant thereafter. The formation of a eutectic liquid at 1550°C was attributed to the steep increase in density. The hot-pressing temperature also improved the mechanical properties, such as the flexural strength, Vickers hardness, and fracture toughness of the specimens. Similar to the density, the mechanical properties improved remarkably at ∼1550°C, so that optimum properties were obtainable at temperatures as low as 1600°C.     

High/Low Modulus Si3N4-BN Composite for Improved Electrical and Thermal Shock Behavior

High-density Si₃N₄+6% CeO₂ composites with 5 to 50% BN were fabricated by hot-pressing. BN remained as a discrete phase. Dielectric constants were 4 to 8 and loss tangents were 0.0008 to 0.06 for the room temperature to 1100°C range for compositions with 10 to 50% BN. Thermal-expansion values perpendicular to the hot-pressing direction were somewhat less than those of hot-pressed Si₃N₄+6% CeO₂. Flexure strengths at room temperature were considerably lower than those of hot-pressed Si₃N₄+6% CeO₂ but values at 1000°, 1250°, and 1400°C in air were only slightly lower. Young's modulus values were found to decrease with increasing BN content at all temperatures. Better thermal shock resistance was found than for commercial hot-pressed Si₃N₄.     

Effect of Grain Size on the Thermal Conductivity of Si3N4

Polycrystalline Si₃N₄ samples with different grain-size distributions and a nearly constant volume content of grain-boundary phase (6.3 vol%) were fabricated by hot-pressing at 1800°C and subsequent HIP sintering at 2400°C. The HIP treatment of hot-pressed Si₃N₄ resulted in the formation of a large amount of ß-Si₃N₄ grains ∼10 µm in diameter and ∼50 µm long, and the elimination of smaller matrix grains. The room-temperature thermal conductivities of the HIPed Si₃N₄ materials were 80 and 102 Wm⁻¹K⁻¹, respectively, in the directions parallel and perpendicular to the hot-pressing axis. These values are slightly higher than those obtained for hot-pressed samples (78 and 93 Wm⁻¹K⁻¹). The calculated phonon mean free path of sintered Si₃N₄ was ∼20 nm at room temperature, which is very small as compared to the grain size. Experimental observations and theoretical calculations showed that the thermal conductivity of Si₃N₄ at room temperature is independent of grain size, but is controlled by the internal defect structure of the grains such as point defects and dislocations.     

Thermal Shock Resistance and Fracture Behavior of ZrB2–Based Fibrous Monolith Ceramics

The thermal shock resistance and fracture behavior of zirconium diboride (ZrB₂)-based fibrous monoliths (FM) were studied. FMs containing cells of ZrB₂–30 vol% SiC with cell boundaries composed of graphite–15 vol% ZrB₂ were hot pressed at 1900°C. The average flexure strength of the FMs was 375 MPa, less than half of the strength of hot-pressed ZrB₂–30 vol% SiC. Flexure specimens failed noncatastrophically and retained 50%–85% of their original strength after the first fracture event. A critical thermal shock temperature (Δ T _c) of 1400°C was measured by water quench thermal shock testing, a 250% improvement over the previously reported Δ T _c values for ZrB₂ and ZrB₂–30 vol% SiC of similar dimensions (4 mm × 3 mm × 45 mm). The flexure strength was maintained with Δ T _c values of 1350°C and below. As Δ T _c increased, the stiffness of the flexure specimen decreased linearly. The lower stiffness and improvement in thermal shock resistance is attributed to crack propagation in the cell boundary and crack deflection around the load-bearing cells. The critical thermal shock was attributed to the fracture of the ZrB₂–30% SiC cell material.     

Phase Relations in the Ternary Systems Nd─B─N, Sm─B─N, and Gd─B─N

Phase relations and phase stabilities have been derived for the ternary systems RE─B─N (RE = Nd, Sm, or Gd) at elevated temperatures (1400°C and above) by means of X-ray powder analysis. Under the experimental conditions selected, various ternary compounds are found to be stable: Nd₃B₂N₄ with the Ce₃B₂N₄ type and (Nd,Sm,Gd)BN₂ with the PrBN₂ type. Phase equilibria at 1400°C and under 10⁵ Pa of argon are mainly characterized by the incompatibility of the RE metals Nd, Sm, and Gd with BN due to the competing equilibria between the RE tetraborides and the RE mononitrides. Each of the ternary compounds, however, is found to be in a two-phase equilibrium with hex -BN. Because of the different thermodynamic stabilities within the various structure series of ternary rare-earth boron nitrides RE₃B₂N₄ and REBN₂, the compound Nd₃B₂N₄ is observed only at temperatures below 1800°C and under 10⁵ Pa of Ar, whereas GdBN₂ is found to be stable only at temperatures above 1400°C under a partial pressure of 10⁵ Pa of N₂.     

Processing Dependence of Texture, and Critical Properties of YBa2Cu3O7−δ Films on RABiTS Substrates by a Non-Fluorine MOD Method

YBa₂Cu₃O_{7− δ} (YBCO or Y123) films on rolling-assisted biaxially textured substrates (RABiTS) were prepared via a fluorine-free metallorganic deposition (MOD) through spin coating, burnout, and high temperature anneal. The effects of substrate texture and surface energy of the CeO₂ cap layer were investigated. Except for the commonly accepted key factors, such as the textures of substrate and buffer layers, we found some other factors, for example, the deposition temperature of the cap layer, are also critical to the epitaxial growth of Y123 phase. With the CeO₂ cap layer deposited at relative high temperature of 700°C, a critical current density, J _c, over 1 MA/cm² has been demonstrated for the first time on Ni-RABiTS by a fluorine-free MOD method. Whereas for samples with CeO₂ cap layers deposited at a lower temperature of 600°C, even though XRD data showed a better texture on these buffer layers, texture degradations of YBCO grains under the optimized processing conditions were observed and a lower oxygen partial pressure around 40 ppm was necessary for the epitaxial growth of Y123 phase. As a result, J _c fell to 0.45 MA/cm² at 77 K. The observed phenomena points to the change of surface energy and reactivity of the CeO₂ cap layer with respect to the CeO₂ deposition temperature. In this paper, the YBCO phase diagram was also summarized.     

Microstructural Observations on Hot-Pressed Si3N4

The development of microstructure in hot-pressed Si_aN₄ was studiehd for a typical Si₃N₄ powder with and without BeSiN₂ as a densification aid. The effect of hot-pressing temperature on density, α- to β-Si₃N₄ conversion and specific surface area showed that BeSiN₂ appears to increase the mobility of the system by enhancing densification, α- to β-Si₃N₄ transformation, and grain growth at temperatures between 1450° and 1800°. These processes appear to occur in the presence of a liquid phase.     

Rapid Hot-Pressing of Ultrafine PSZ Powders

The process of compaction and densification of ultrafine (40- to 60-nm grain size) powder of partially stabilized zirconia with 3 mol% of Y₂O₃ (Y3-PSZ) during rapid hot-pressing was investigated. A special apparatus was designed to allow rapid application of 1.6 GPa of quasi-isostatic pressure at temperatures of 1100° to 1300°C to powder compacts encapsulated in glass under vacuum. Pressure was applied for 10 s, then the samples were rapidly cooled to room temperature, removed from the encapsulating glass, and characterized using SEM, TEM, and X-ray diffraction. Density and mechanical properties of the prepared materials were measured and compared with those of similar materials fabricated using conventional hot-pressing. SEM and TEM observations revealed that the ultrafine grains of the starting powder coarsened rapidly during the initial heating, and the compacts developed large (> 10 μm) and small (< 1 μm) pores. The process of densification under pressure consisted of closing of the large pores, whereas the small pores were relatively unaffected by the application of pressure at all investigated temperatures. The major mechanism of densification during the rapid pressing appears to be rearrangement and sliding of grains around the large pores. The material prepared by rapid pressing at 1300°C had higher hardness ( H _v= 1400 versus 1300 kg/mm²) but somewhat lower fracture toughness ( K _{I C} = 5.5 versus 6.0 MPa · m^1/2) compared with the conventionally hot-pressed Y3-PSZ. Density of the material pressed at 1300°C was 97% of theoretical density.     

Al2O3─SiC Composites from Aluminosilicate Precursors

Al₂O₃ and SiC composite materials have been produced from mixtures of aluminosilicates (both natural minerals and synthetic) and carbon as precursor materials. These composites are produced by heating a mixture of kaolinite (or synthetic aluminosilicates) and carbon in stoichiometric proportion above 1550°C, so that only Al₂O₃ and SiC remain as the major phases. A similar process has also been used for synthesizing other composite powders having mixtures of Al₂O₃, SiC, TiC, and ZrO₂ in different proportions (all compounds together or selective mixtures of some of them), as desired. The microstructure of hot-pressed dense compacts, produced from these powders, revealed that the SiC phase is distributed very homogeneously, even occasionally within Al₂O₃ grains on a nanosize scale. The homogeneous distribution of SiC particles within the system produced high fracture toughness of the hot-pressed material (K_IC∼ 7.0 MPa · m^1/2) and having Vicker's hardness values greater than 2000 kgf/mm².     

Phase Transformation and Processing of Poly crystalline Gadolinium Selenide, GdSei.1.49

Polymorphic phase transformation in a thermoelectric material, GdSe_1.49, from cubic to orthorhombic symmetry at temperatures from 800° to 1000°C causes a 1% volume expansion, which generates microcracks. Sintered polycrystalline cubic GdSe_1.49 preforms with at least 97% densities were vacuum annealed at 900°C for 300 h to fully convert to the orthorhombic lattice, encapsulated in nickel containers, and then isostatically hot-pressed. Hot-pressing at or below 1000°C resulted in 96%-dense orthorhombic GdSe_1.49 polycrystals containing large pores, whereas hot-pressing above 1200°C produced fully dense cubic polycrystals with a duplex microstructure. The electrical resistivity of the orthorhombic GdSe_1.49 (hot-pressed below 1000°C) was about 5 times that of the as-sintered cubic GdSe_1.49; the increase appears to be related to the presence of the orthorhombic phase, micro-cracks, large pores, and a Se-rich grain-boundary phase in the hot-pressed orthorhombic GdSei_1.49.     

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.     

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.     

Densification, Sintering Reactions, and Properties of Titanium Diboride With Titanium Disilicide as a Sintering Aid

In the present investigation, we explore the feasibility of using TiSi₂ as a sintering aid to densify titanium diboride (TiB₂) at a lower sintering temperature (<1700°C). The hot-pressing experiments were conducted in the temperature range of 1400°–1650°C for 1 h in an argon atmosphere and TiSi₂ addition to TiB₂ was restricted up to 10 wt%, with an overall objective to densify the materials with a fine microstructure as well as to assess the feasibility of enhancing the mechanical and electrical properties. When all the materials were hot pressed at 1650°C, the hot-pressed TiB₂– X % TiSi₂ ( X =0, 2.5, 5, 10 wt%) composites were found to be densified to more than 98%ρ_th (theoretical density), except monolithic TiB₂ (∼94%ρ_th). An interesting observation is the formation of a Ti₅Si₃ phase and this phase formation is described by thermodynamically feasible sintering reactions. Our experimental results suggest that the optimal TiB₂–5 wt% TiSi₂ composite can exhibit an excellent combination of properties, including a high hardness of 25 GPa, an elastic modulus of 518 GPa, an indentation toughness of ∼6 MPa·m^1/2, a four-point flexural strength of more than 400 MPa, and an electrical resistivity of 10 μΩ·cm.