Crystalline Phase Change in Yttria-Partially-Stabilized Zirconia by Low-Temperature Annealing

Changes in the phase composition and microstructure of yttria-partially-stabilized zirconia by low-temperature annealing were investigated at 100° to 500°C using bodies sintered from coprecipitated fine ZrO₂-Y₂O₃ powders at varied temperatures. Tetragonal zirconia on the surfaces of bodies sintered at <1500°C transformed to the monoclinic phase at 100° to 400°C. Transformation behavior was strongly affected by grain size.     

Mullite Crystallization from SiO2-Al2O3 Melts

SiO₂-Al₂O₃ melts containing 42 and 60 wt% A1₂O₃ were homogenized at 2090°C (∼10°) and crystallized by various heat treatment schedules in sealed molybdenum crucibles. Mullite containing ∼78 wt% A1₂O₃ precipitated from the 60 wt% A1₂O₃ melts at ∼1325°± 20°C, which is the boundary of a previously calculated liquid miscibility gap. When the homogenized melts were heat-treated within this gap, the A1₂O₃ in the mullite decreased with a corresponding increase in the Al₂O₃ content of the glass. A similar decrease of Al₂O₃ in mullite was observed when crystallized melts were reheated at 1725°± 10°C; the lowest A1₂O₃ content (∼73.5 wt%) was in melts that were reheated for 110 h. All melts indicated that the composition of the precipitating mullite was sensitive to the heat treatment of the melts.     

Effects of Samarium Oxide Addition on the Phase Composition, Microstructure, and Electrical Resistivity of Aluminum Nitride Ceramics

The phase composition, microstructure, and electrical resistivity of hot-pressed AlN ceramics with 0–4.8 wt% Sm₂O₃ additive were investigated. The phase composition was approximately consistent with that estimated from the Sm₂O₃–Al₂O₃ phase diagram using the amount of added Sm₂O₃ and oxygen content of the AlN raw material. When sintered at more than 1800°C, the AlN ceramics with 1.0–2.9 wt% Sm₂O₃ additive contained an Sm-β-alumina phase wetting the grain boundaries, and their electrical resistivity considerably decreased to 10¹⁰–10¹²Ω·cm. This resistivity decrease was caused by the continuity of the Sm-β-alumina phase with a resistivity lower than that of bulk AlN.     

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.     

Microstructure and Bending Strength of 3Y-TZP/12Ce-TZP Ceramics Fabricated by Liquid-Phase Sintering at Low Temperature

With the addition of 1 wt% of MgO–Al₂O₃–SiO₂ glass as a sintering aid, 3Y-TZP/12Ce-TZP ceramics (composed from a mixture of 3Y-TZP and 12Ce-TZP powder) have been fabricated via liquid-phase sintering at 1250°–1400°C. In the sintered bodies, the grain growth of Y-TZP is almost unaffected, whereas that of Ce-TZP is inhibited. MgO·Al₂O₃ spinel and an amorphous phase that contains Al₂O₃ and SiO₂ (from the sintering aid) fully fill the grain junctions. The bending strength of 3Y-TZP/12Ce-TZP, when sintered at 1250°–1300°C, is ∼800–900 MPa, which is greater than that of 3Y-TZP ceramics without Ce-TZP particles. Ce-TZP grains and MgO·Al₂O₃ spinel in 3Y-TZP/12Ce-TZP ceramics may impede crack growth, and the bending strength is enhanced.     

Reactions and Microstructure Development in Mullite Fibers

Microstructural and compositional changes during heat treatment of sol–gel-derived mullite fibers with additions of 2 wt% B₂O₃, 2 wt% P₂O₅, 2 wt% Cr₂O₃, and (1 wt% P₂O₅+ 1 wt% Cr₂O₃) were compared with those of undoped mullite fibers. For all compositions the sequence of phase development was the crystallization of a spinel phase (†-Al₂O₃ or Al–Si spinel) from amorphous material, followed by the formation of mullite at higher temperatures. Differential thermal analysis showed that additions of B₂O₃ and P₂O₅ increased the temperature of spinel formation and that B₂O₃ significantly decreased the temperature of mullite formation. After 1 h at 1200°C, the size of mullite grains in fibers that contained B₂O₃ was less than 1000 Å the grains in fibers of other compositions were 6000 to 12000 Å. After 60 h at 1400°C, fibers modified with B₂O₃ had a grain size less than 2000 to 3000 Å the grains in fibers of other compositions were 6000 to 12000 Å. B₂O₃ was the most volatile additive.     

Effects of Additives on the Pressure-Assisted Densification and Properties of Silicon Carbide

The densification of silicon carbide (SiC) was studied using a variety of additives (Al, AlN, Al₂O₃, B₄C, C, Si₃N₄, and Y₂O₃). The onset of densification of SiC with small amounts of additives occurred at temperatures between 1500° and 1900°C with 28 MPa applied pressure. Al, B₄C, and C promoted densification, while N (added as AlN or Si₃N₄) retarded sintering. A 96.75 wt% SiC–2 wt% Al–1 wt% C–0.25 wt% B₄C starting composition yielded the same percent of theoretical density (in the range of 70%–90% theoretical density) 400°C lower than a 95 wt% SiC–5 wt% AlN material. Yttria additions promoted intergranular fracture, which increased the single-edged precracked beam fracture toughness. The appropriate selection and amount of additives allowed for the tailoring of grain size and intergranular fracture, thus controlling the mechanical properties. While oxygen was present in all materials containing aluminum, the incorporation of additional oxygen as alumina resulted in reduced sintering activity compared with Al metal. Corrosion resistance decreased in both HF and NaOH solutions at 80°C for materials containing a grain boundary phase.     

Mineralizing Effect of Li2B4O7 and Na2B4O7 on Magnesium Aluminate Spinel Formation

Lithium borate (Li₂B₄O₇) and sodium borate (Na₂B₄O₇) mineralize spinel formation from stoichiometric MgO and Al₂O₃ between 1000° and 1100°C. Mineralization with both compounds is shown to be mediated by B-containing liquids which form glass on cooling. However, the liquid compositions depend on the type of mineralizer and temperature, suggesting that templated grain growth or dissolution–precipitation mechanisms are operating, one dominating over the other under certain conditions. Na₂B₄O₇-mineralized compositions show predominantly templated grain growth at 1000°C, which changes to dissolution–precipitation at 1100°C, whereas Li₂B₄O₇-mineralized compositions show dissolution–precipitation from 1000°C. Li₂B₄O₇ is a stronger mineralizer as spinel formation is complete with 3 wt% Li₂B₄O₇ at 1000°C and with ≥1.5 wt% addition at 1100°C, whereas Na₂B₄O₇-mineralized compositions are found to retain some unreacted corundum even at 1100°C.     

Tensile Ductility in Zirconia-Dispersed Alumina at High Temperatures

High-temperature plastic flow in Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) has been examined at temperatures between 1400° and 1500°C. Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) exhibits much higher flow stress and smaller tensile elongation below about 1450°C than 0.1 wt% MgO-doped single-phase Al₂O₃. The suppression of grain growth with ZrO₂ dispersion into Al₂O₃ is not effective for improving the tensile ductility. The limited ductility in Al₂O₃-10 wt% ZrO₂ (2.5 mol% Y₂O₃) is associated with the increment of flow stress caused by ZrO₂. The ZrO₂ dispersion or segregation in Al₂O₃/Al₂O₃ boundaries suppresses the grain boundary sliding and hence results in the increased flow stress at high temperatures.     

Nd2O3-Doped Sialons with ZrO2/ZrN Additions Formed by Sintering and Hot Isostatic Pressing

β-sialon and Nd₂O₃-doped α-sialon materials of varying composition were prepared by sintering at 1775° and 1825°C and by glass-encapsulated hot isostatic pressing at 1700°C. Composites were also prepared by adding 2–20 wt% ZrO₂ (3 mol% Nd₂O₃) or 2–20 wt% ZrN to the β-sialon and α-sialon matrix, respectively. Neodymium was found to be a fairly poor α-sialon stabilizer even within the α-phase solid solution area, and addition of ZrN further inhibited the formation of the α-sialon phase. A decrease in Vickers hardness and an increase in toughness with increasing content of ZrO₂(Nd₂O₃) or ZrN were seen in both the HIPed β-sialon/ZrO₂(Nd₂O₃) composites and the HIPed Nd₂O₃-stabiIized α-sialons with ZrN additions.     

Temperature-Dependent Iron Solubility in Mullite

Sample disks prepared from Al₂O₃ (61 wt%), SiO₂ (28 wt%), and Fe₂O₃(II wt%) powders were sintered at 1270° and 1440°C and then annealed between 1300° and 1670°C. The annealed samples consisted of mullite as the main compound with minor amounts of glass and sometimes magnetite. The iron content of the mullites decreases strongly from ∼ 10.5 wt% Fe₂O₃ at 1300°C to ∼ 2.5 wt% Fe₂O₃ at 1670°C. A complex temperature-controlled exsolution mechanism of iron from mullite is considered.     

Reducing the Sintering Temperature for MgO–Al2O3Mixtures by Addition of Cryolite (Na3AlF6)

The preparation of near stoichiometric spinel and alumina-rich spinel composites from Al₂O₃and MgO powders with the addition of Na₃AlF₆up to 4 wt% in the temperature range 700°–1600°C was studied; 98 wt% spinel containing 72 wt% Al₂O₃can be produced from the mixture of 72 wt% (50 at.%) Al₂O₃+ 28 wt% (50 at.%) MgO powders with the addition of 1 wt% Na₃AlF₆fired at 1300°C for 1 h. Spinels containing 81–85 wt% Al₂O₃can be produced from either the mixture of 90 wt% (78 at.%) Al₂O₃+ 10 wt% (22 at.%) MgO or the mixture of 95 wt% (88 at.%) Al₂O₃+ 5 wt% (12 at.%) MgO powders with the addition of 4 wt% Na₃AlF₆in the temperature range 1300°–1600°C by using a torch-flame firing for 3 min, followed by quenching in water, while the same system under slow cooling in a furnace results in spinel containing 74–76 wt% Al₂O₃. Microscopic studies indicate that the alumina-rich spinel composites consist of a continuous majority spinel phase and an isolated minority corundum phase, regardless of slow cooling in a furnace or quenching in water.     

Use of Mixed-Rare-Earth Oxide in the Preparation of Reaction-Bonded Mullite at ≤1300°C

A process for production of near-net-shape mullite-matrix ceramic composites at ≤1300°C has been achieved by reaction-bonding Al₂O₃, silicon, mullite seeds, and eutectics of Al₂O₃–SiO₂–mixed-rare-earth oxide. The fusion temperature of the eutectic composition utilized is 1175°C. This liquid phase facilitates silicon oxidation, mullitization, and sintering. Mullite phase develops with low residual Al₂O₃ when 7.5 wt% mixed-rare-earth oxide and 5 wt% mullite seeds are used. The final sinter is >90% of theoretical density, >90% mullite (by quantitative XRD), and suffers 2.2% sintering shrinkage.     

Microstructure and Grain-Boundary Composition of Hot-Pressed Silicon Nitride With Yttria and Alumina

The microstructure of two hot-pressed silicon nitrides containing Y₂O₃ and Al₂O₃ was examined by electron microscopy, electron diffraction, and quantitative, energy-dispersive X-ray microanalysis. A crystalline second phase was identified in the material with additives of 5 wt% Y₂O₃+2 wt% Al₂O₃, as a solid solution of nitrogen mellilite and alumina. An amorphous third phase as narrow as 2 nm is discerned at all grain boundaries of this material by high-resolution dark-field and lattice imaging. The second phase in a material with additives of S wt% Y₂O₃+5 wt% Al₂O₃ was found to be amorphous. Some of the additional alumina additive appears in solid solution with silicon nitride. In situ hot-stage experiments in a high-voltage electron microscope show that the amorphous phase volatilizes above 1200°C, leaving a skeleton of Si₃N₄ grains linked by the mellilite crystals at triple points. The results show that intergranular glassy phases cannot be eliminated by the Y₂O₃/Al₂O₃ fluxing.     

Phase Transformation in EB-PVD Yttria Partially Stabilized Zirconia Thermal Barrier Coatings during Annealing

Electron-beam physical-vapor-deposited thermal barrier coatings consisting of ZrO₂ stabilized by 7 wt% Y₂O₃ were investigated in regard to phase transformation after annealing. Free-standing ceramic layers were heat-treated in air, for up to 200 h, in the temperature range 1200°—1400°C and then analyzed by X-ray diffractometry. Based on information obtained from the {111} and {400} peaks, the phase composition and the Y₂O₃ content in the phases were calculated. At the start of transformation, small grains of a low-Y₂O₃ t phase and a c phase formed. After >30 h at 1300°C and at 1400°C, a mixture of a t phase deficient in Y₂O₃, an m phase, and a c phase formed after cooling, with the Y₂O₃ contents in the phases roughly predicted by the phase diagrams. The results of the present study are discussed here in detail and compared with data for plasma-sprayed coatings.     

Effect of the Amount of Additives and Post-Heat Treatment on the Microstructure and Mechanical Properties of Yttrium–α-Sialon Ceramics

The yttrium–sialon ceramics with the composition of Y_0.333Si₁₀Al₂ON₁₅ and an excess addition of Y₂O₃ (2 or 5 wt%) were fabricated by hot isostatic press (HIP) sintering at 1800°C for 1 h. The resulting materials were subsequently heat-treated in the temperature range 1300–1900°C to investigate its effect on the α→β-sialon phase transformation, the morphology of α-sialon grains, and mechanical properties. The results show that α-sialons stabilized by yttrium have high thermal stability. An adjustment of the α-sialon phase composition is the dominating reaction in the investigated Y–α-sialon ceramics during low-temperature annealing. Incorporation of excess Y₂O₃ could effectively promote the formation of elongated α-sialon grains during post-heat-treating at relatively higher temperature (1700° and 1900°C) and hence resulted in a high fracture toughness ( K _IC= 6.3 MPa·m^1/2) via grain debonding and pullout effects. Although the addition of 5 wt% Y₂O₃ could promote the growth of elongated α grains with a higher aspect ratio, the higher liquid-phase content increased the interfacial bonding strength and therefore hindered interface debonding and crack deflection. The heat treatment at 1500°C significantly changed the morphology of α-sialon grains from elongated to equiaxed and hence decreased its toughness.     

High-Temperature Phase Relations in the Sc2O3-Ta2O5 System

The phase relations for the Sc₂O₃-Ta₂O₅ system in the composition range of 50-100 mol% Sc₂O₃ have been studied by using solid-state reactions at 1350°, 1500°, or 1700°C and by using thermal analyses up to the melting temperatures. The Sc_5.5Ta_1.5O₁₂ phase, defect-fluorite-type cubic phase (F-phase, space group Fm 3 m ), ScTaO₄, and Sc₂O₃ were found in the system. The Sc_5.5Ta_1.5O₁₂ phase formed in 78 mol% Sc₂O₃ at <1700°C and seemed to melt incongruently. The F-phase formed in ∼75 mol% Sc₂O₃ and decomposed to Sc_5.5Ta_1.5O₁₂ and ScTaO₄ at <1700°C. The F-phase melted congruently at 2344°± 2°C in 80 mol% Sc₂O₃. The eutectic point seemed to exist at ∼2300°C in 90 mol% Sc₂O₃. A phase diagram that includes the four above-described phases has been proposed, instead of the previous diagram in which those phases were not identified.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

Properties of Isostatically Hot-Pressed Silicon Nitride

Hot isostatic pressing was studied for densification of reaction-bonded Si₃N₄ containing various levels of Y₂O₃. Near-theoretical density was achieved for com positions containing 3 to 7 wt% Y₂O₃. An Si₃N₄-5 wt% Y₂O₃ composition had a 4-point flexural strength at 1375°C of 628 MPa and survived 117 h of stress rupture testing at 1400°C and 345 MPa .     

High-Temperature Phase Relations in the System Gd2O3-Ta2O5

The Phase relations of the system Gd₂O₃-Ta₂O₅ in the composition range 50 to100 mol% Gd2O3 was studied by solidstate reactions at 1350°, 1500°, or 1700°C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phase (W2 phase, space group C2221) with the composition of Gd3 TaO7 seems to melt incongruently; at about 2040°C, although this Gd₃TaO₇ Phase was previously reported to melt congruently. A new fluorite-type cubic phase (F phase, space group Fm3m ) was found for the first time above 1500°C in the system. It melts congruently with the composition of about 80mol% Gd2O3at 2318° 3°C. A phase diagram was proposed for the system Gd₂O3–Ta2O₅ in the Gd₂O₃–rich portion