Improvement of Mechanical Properties and Corrosion Resistance of Porous β-SiAlON Ceramics by Low Y2O3 Additions

Addition of Y₂O₃ as a sintering additive to porous β-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0.5) ceramics has been investigated for improved mechanical properties. Porous SiAlON ceramics with 0.05–0.15 wt% (500–1500 wppm) Y₂O₃ were fabricated by pressureless sintering at temperatures of 1700°, 1800°, and 1850°C. The densification, microstructure, and mechanical properties were compared with those of Y₂O₃-free ceramics of the same chemical composition. Although this level of Y₂O₃ addition did not change the phase formation and grain size, the grain bonding appeared to be promoted, and the densification to be enhanced. There was a significant increase in the flexural strength of the SiAlON ceramics relative to the Y₂O₃-free counterpart. After exposure in 1 M hydrochloric acid solution at 70°C for 120 h, no remarkable weight loss and degradation of the mechanical properties (flexural and compression strength) was observed, which was attributed to the limited grain boundary phase, and with the minor Y₂O₃ addition the supposed formation of Y-α-SiAlON.     

Sintering of Si3N4 with the Addition of Rare-Earth Oxides

The effect of rare-earth oxide additives on the densification of silicon nitride by pressureless sintering at 1600° to 1700°C and by gas pressure sintering under 10 MPa of N₂ at 1800° to 2000°C was studied. When a single-component oxide, such as CeO₂, Nd₂O₃, La₂O₃, Sm₂O₃, or Y₂O₃, was used as an additive, the sintering temperature required to reach approximate theoretical density became higher as the melting temperature of the oxide increased. When a mixed oxide additive, such as Y₂O₃–Ln₂O₃ (Ln=Ce, Nd, La, Sm), was used, higher densification was achieved below 2000°C because of a lower liquid formation temperature. The sinterability of silicon nitride ceramics with the addition of rare-earth oxides is discussed in relation to the additive compositions.     

High-Temperature Strength of Liquid-Phase-Sintered SiC with AlN and Re2O3 (RE = Y, Yb)

Using AlN and RE₂O₃ (RE = Y, Yb) as sintering additives, two different SiC ceramics with high strength at 1500°C were fabricated by hot-pressing and subsequent annealing under pressure. The ceramics had a self-reinforced microstructure consisting of elongated α-SiC grains and a grain-boundary glassy phase. High-temperature strength up to 1600°C was measured and compared with that of the SiC ceramics fabricated with AlN and Er₂O₃. SiC ceramics with AlN and Y₂O₃ showed the best strength (∼630 MPa) at 1500°C, while SiC ceramics with AlN and Er₂O₃ the best strength (∼550 MPa) at 1600°C.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Effects of La2O3/ZnO Additives on Microstructure And Microwave Dielectric Properties of Zr0.8Sn0.2TiO4 Ceramics

Dielectric ceramics of Zr_0.8Sn_0.2TiO₄ containing La₂O₃ and ZnO as sintering aids were prepared and investigated for microstructure and microwave dielectric properties. Low-level doping with La₂O₃ and ZnO (up to 0.30 wt%) is good for densification and dielectric properties. These additives do not affect the dielectric constant and the temperature coefficient. Dielectric losses increase significantly at additive levels higher than 0.15 wt%. The combined additives La₂O₃ and ZnO act as grain growth enhancers. With 0.15 wt% additives, a ceramic having a dielectric constant, a quality factor, and a temperature coefficient of frequency at 4.2 GHz of 37.6, 12 800, and –2.9 ppm/°C, respectively, was obtained. The quality factor was considerably improved by prolonged sintering.     

Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

Low-Temperature High-Pressure Consolidation of Amorphous Al2O3–15 mol% Y2O3

This study examined pressure consolidation of amorphous Al₂O₃–15 mol% Y₂O₃ powders prepared by co-precipitation and spray pyrolysis. The two amorphous powders had similar true densities and crystallization sequences. Uniaxial hot pressing was carried out at 450°–600°C with a moderate pressure of 750 MPa. The co-precipitated powder could be hot pressed to a maximum relative density of 98% and remained amorphous. Pressure adversely affected the densification of the spray-pyrolyzed powder by favoring an early crystallization of γ-Al₂O₃ phase at 580°C. Plastic deformation of the amorphous phase is believed to be responsible for the large densification of the amorphous powders.     

Reactive Hot-Pressed Alumina–Boron Nitride Composites with Y2O3 Sintering Additive

The effect of Y₂O₃ addition (0–5 wt%) on the densification and properties of reactive hot-pressed alumina (Al₂O₃)–boron nitride composites based on the reaction between aluminum borate (2Al₂O₃·B₂O₃) and aluminum nitride (AlN) was investigated. The densification process was very sensitive to the amount of Y₂O₃. Compared with a low relative density of 79.3 theoretical density (TD)% for material with no Y₂O₃ addition, the material density reached 98.6 TD% with 0.25% Y₂O₃ addition. High Y₂O₃ additions resulted in the formation of a new phase Al₅Y₃O₁₂. The grain growth of the Al₂O₃ matrix was promoted by the Y₂O₃ addition. Owing to the high density and the small Al₂O₃ particle size the sample with 0.25% Y₂O₃ addition demonstrated the highest bending strength of 540 MPa.     

Field-Assisted Densification of Superhard B6O Materials with Y2O3/Al2O3 Addition

B₆O is a possible candidate of superhard materials with a hardness of 45 GPa measured on single crystals. Up to now, densification of these materials was only possible at high pressure. However, recently it was found that Al₂O₃ can be utilized as an effective sintering additive, similar to the addition of Y₂O₃/Al₂O₃ that was used in this work. The densification behavior of the material as a function of applied pressure, its microstructure evolution, and the resulting mechanical properties were investigated. A strong dependence of the densification with increasing pressure was found. The material revealed characteristic triple junctions filled with amorphous residue composed of B₂O₃, Al₂O₃, and Y₂O₃, while no amorphous grain-boundary films were observed along internal interfaces. Mechanical testing revealed on average a hardness of 33 GPa, a fracture toughness of 4 MPa·m^1/2, and a strength value of 520 MPa.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Analytical Microscopy Study of Phases and Fracture in Y2O3-La2O3 Alloys

Transmission electron microscopic analyses defined the structures and compositions in single-phase and two-phase La₂O₃-doped Y₂O₃ materials fabricated by the transient solid second-phase sintering. The composition in single-phase, 10-mol%-La₂O₃-doped, sintered and annealed samples was found to be uniform, indicating that diffusivity was sufficiently high for homogenization in the single-phase field. Two-phase, 16-mol%-La₂O₃-doped, sintered and annealed samples showed two morphologies: (1) intragranular, lath-like, monoclinic second-phase particles (twinned and untwinned) and (2) equiaxed cubic matrix. The second-phase particles were identified as the monoclinic phase derived from the high-temperature hexagonal phase through a rapid phase transition. A short, high-temperature anneal (2200°C for 1 min) of 9 mol% La₂O₃-Y₂O₃ composition was found to retain the hexagonal phase. Microchemical analyses of the phases suggested adjustments to the Y₂O₃-La₂O₃ phase diagram. Observation of the interactions of the intragranular second-phase particles with crack propagation indicated crack deflection as one of the mechanisms responsible for toughening (1.5 vs 0.9 MPa · m^1/2).     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

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.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Phases in the Binary Systems PbO—La2O3, Gd2O3, and Sm2O3

In the binary system PbO–La_zO₃ only one compound, 4PbO.La₂O₃, exists; it is flanked by two eutectics. The structure of the compound, although of lower symmetry, is intimately related to the C modification of the rare earths. Below 800° to 1000°C, metastable solid solutions are formed from oxide mixtures coprecipitated from mixed solutions of the nitrates, the cubic parameter a = 5.66 A, if extrapolated to pure La₂O₃, corresponding to half the a parameter of the C form of La₂O₃. The solid solutions existing between the compositions La₂O₃–2Pb0 and pure La₂O₃ have a cubic face–centered lattice and obey Vegard's rule. The systems of PbO with Sm₂O₃ and Gd₂O₈ are quite similar to that with La₂O₃. The compound Sm₂O₃.4Pb0 decomposes at 1000°C with evaporation of PbO; Sm₂O₃ remains in the B modification.     

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.     

Pulse Electric Current Sintering of Al2O3/3 vol% ZrO2 with Constrained Grains and High Strength

The pulse electric current sintering technique (PECS) was demonstrated to be effective in rapid densification of fine-grained Al₂O₃/3Y-ZrO₂ using available commercial powders. The composites attained full densification (>99% of TD) at 1450°C in less than 5 min. The composites sintered at a high heating rate had a fine microstructure. The incorporation of 3 vol% 3Y-ZrO₂ substantially increased the average fracture strength and the toughness of alumina to as high as 827 MPa and 6.1 MPa·m^1/2, respectively. A variation in the heating rate during the PECS process influenced grain size, microstructure, and strength, though there was little or no variation in the fracture toughness.     

Subsolidus Phase Equilibria and Ordering in the System ZrO2-Y2O3

The subsolidus phase relations in the entire system ZrO₂-Y₂O₃ were established using DTA, expansion measurements, and room- and high-temperature X-ray diffraction. Three eutectoid reactions were found in the system: ( a ) tetragonal zirconia solid solution→monoclinic zirconia solid solution+cubic zirconia solid solution at 4.5 mol% Y₂O₃ and ∼490°C, ( b ) cubic zirconia solid solutiow→δ-phase Y₄Zr₃O₁₂+hexagonalphase Y₆ZrO₁₁ at 45 mol% Y₂O₃ and ∼1325°±25°C, and ( c ) yttria C -type solid solution→wcubic zirconia solid solution+ hexagonal phase Y₆ZrO₁₁ at ∼72 mol% Y₂O₃ and 1650°±50°C. Two ordered phases were also found in the system, one at 40 mol% Y₂O₃ with ideal formula Y₄Zr₃O₁₂, and another, a new hexagonal phase, at 75 mol% Y₂O₃ with formula Y₆ZrO₁₁. They decompose at 1375° and >1750°C into cubic zirconia solid solution and yttria C -type solid solution, respectively. The extent of the cubic zirconia and yttria C -type solid solution fields was also redetermined. By incorporating the known tetragonal-cubic zirconia transition temperature and the liquidus temperatures in the system, a new tentative phase diagram is given for the system ZrO₂-Y₂O₃.     

Sintering of LaFeO3 Ceramics

The sintering of LaFeO₃ has been studied in the temperature interval 1100–1600°C in air. The effect of cation nonstoichiometry on densification, microstructure, and phase composition is emphasized. La₂O₃ was observed to inhibit both sintering and grain growth. In Fe-excess materials, exaggerated grain growth occurred, particularly above 1430°C, where a liquid phase was formed. Postsintering swelling was observed in Fe-excess materials above 1430°C. The swelling mechanism is related to phase equilibria, which are reductive in nature and lead to the evolution of oxygen gas. The density in La-excess materials remains high up to 1600°C, but the ceramics might disintegrate in air.     

Hot-Pressed MoSi2-Particulate-Reinforced α-SiAlON Composites

MoSi₂-particulate-reinforced α-SiAlON ceramic composites containing 10, 20, 25, and 30 vol% were prepared by hot pressing at 1750°-1800°C. The α-SiAlON matrix was of the composition (Y_0.48Si_10.00A1_2.30O_1.17N_15.29). The hardness for the fully dense samples changed from HV10 = 22.5 to 15.3 GPa and the toughness from 3.2 to around 5.2 MPa^.m^1/2 when up to 30 vol% MoSi₂ was present. Two interesting microstructural features have been found. First, with an increasing amount of MoSi₂ a pronounced coalescence of MoSi₂ particles formed a "dual phase" material. The second effect was the growth of elongated α-SiAlON grains in the matrix with 10 vol% MoSi₂ added. The oxidation resistance has been determined to be unaffected by the addition of 2hd vol % MoSi₂ at 1250°C in oxygen gas of l atm pressure.