Sintering and compensation effect of donor- and acceptor-codoped 3mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350 °C. The enhancement is accounted for by a liquid phase sintering mechanism. The addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol % at 1300–1600 °C results in the destabilization of tetragonal (t-) phase and the decrease of final density in 3 mol% Y₂O₃-TZP (tetragonal ZrO₂ polycrystals). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m-) ZrO₂ and a second phase of Ta₂Zr₆O₁₇. The decreasing in final density is attributed to the increase of m-ZrO₂ content. Complete destabilization of t-ZrO₂ to m-ZrO₂ in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor- and acceptor-codoping defect chemistry.     

Sintering and compensation effect of donor and acceptor codoped 3 mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350°C. The enhancement is accounted for by a liquid phase sintering mechanism. While the addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol% at 1300–1600°C results in the decrease of final density and in the destabilization of the tetragonal (t) phase of the 3 mol% Y₂O₃-t-ZrO₂ (TZP). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m) ZrO₂ phase and a second Ta₂Zr₆O₁₇ phase. The decrease is attributed to the increase of m-ZrO₂ content in these samples. Complete phase transformation from t-ZrO₂ to m-ZrO₂ observed in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor and acceptor codoping defect chemistry.     

Microstructure and mechanical properties of ZrO2-Gd2O3 tetragonal polycrystals

The phases, transformability, microstructure and mechanical properties of ZrO₂-Gd₂O₃ polycrystals containing 1.75–8 mol% Gd₂O₃ were studied. The samples were prepared by a coprecipitation route followed by sintering at 1400°C for 2 hours. The grain size was in the range of 0.1–0.2 m except for some large grains at high Gd₂O₃ contents. Only a tetragonal phase was observed between 2–4 mol% Gd₂O₃ and a cubic phase for compositions containing 9.6 mol% Gd₂O₃. A peak K _IC of 12 MPa m^1/2 and a strength of 800 MPa were obtained in the 2 mol% Gd₂O₃ alloy for which the t m transformation on the fracture surface was also found to be maximum. Transformation toughening is able to account for most of the toughness of the samples.     

Hot isostatic pressing of tetragonal ZrO2 solid-solution powders prepared from acetylacetonates in the system ZrO2-Y2O3-Al2O3

In compositions having ZrO₂/Y₂O₃=(74.25–71.25)/(0.75–3.75) (mol% ratio) with 25 mol% Al₂O₃, metastable t-ZrO₂ solid solutions crystallize at 780° to 860°C from amorphous materials prepared by the simultaneous hydrolysis of zirconium, yttrium and aluminium acetylacetonates. Hot isostatic pressing has been performed for 1 h at 1130 and 1230°C under 196 MPa using their powders. Two kinds of material are fabricated: (i) perfect ZrO₂ solid-solution ceramics and (ii) composites of ZrO₂ solid solution and -Al₂O₃. Their mechanical properties are examined, in connection with microstructures and t/m ZrO₂ ratios. Composites with a homogeneous dispersed -Al₂O₃ derived from solid-solution ceramics result in a remarkable increase of strength.     

Si3N4-ZrO2 composites with small Al2O3 and Y2O3 additions prepared by HIP

Si₃N₄-ZrO₂ composites have been prepared by hot isostatic pressing at 1550 and 1750 °C, using both unstabilized ZrO₂ and ZrO₂ stabilized with 3 mol% Y₂O₃. The composites were formed with a zirconia addition of 0, 5, 10, 15 and 20 wt%, with respect to the silicon nitride, together with 0–4 wt% Al₂O₃ and 0–6 wt% Y₂O₃. Composites prepared at 1550 °C contained substantial amounts of unreacted -Si₃N₄, and full density was achieved only when 1 wt% Al₂O₃ or 4 wt % Y₂O₃ had been added. These materials were generally harder and more brittle than those densified at the higher temperature. When the ZrO₂ starting powder was stabilized by Y₂O₃, fully dense Si₃N₄-ZrO₂ composites could be prepared at 1750 °C even without other oxide additives. Densification at 1750 °C resulted in the highest fracture toughness values. Several groups of materials densified at 1750 °C showed a good combination of Vickers hardness (HV10) and indentation fracture toughness; around 1450 kg mm^–2 and 4.5 MPam^1/2, respectively. Examples of such materials were either Si₃N₄ formed with an addition of 2–6 wt% Y₂O₃ or Si₃N₄-ZrO₂ composites with a simultaneous addition of 2–6 wt%Y₂O₃ and 2–4 wt% Al₂O₃.     

Phase relationships in the system Si3N4-Y2O3-SiO2

Examination of compositions in the system Si₃N₄-Y₂O₃-SiO₂ using sintered samples revealed the existence of two regions of melting and three silicon yttrium oxynitride phases. The regions of melting occur at 1600° C at high SiO₂ concentrations (13 mol% Si₃N₄ + 19 mol% Y₂O₃ + 68 mol% SiO₂) and at 1650° C at high Y₂O₃ concentrations (25 mol % Si₃N₄ + 75 mol % Y₂O₃). Two ternary phases 4Y₂O₃ ·SiO₂ ·Si₃N₄ and 10Y₂O₃ ·9SiO₂ ·Si₃N₄ and one binary phase Si₃N₄ ·Y₂O₃ were observed. The 4Y₂O₃ ·SiO₂ ·Si₃N₄ phase has a monoclinic structure (a= 11.038 Å, b=10.076 Å, c=7.552 Å, =108° 40) and appears to be isostructural with silicates of the wohlerite cuspidine series. The 10Y₂O₃ ·9SiO₂ ·Si₃N₄ phase has a hexagonal unit cell (a=7.598 Å c=4.908 Å). Features of the Si₃N₄-Y₂O₃-SiO₂ systems are discussed in terms of the role of Y₂O₃ in the hot-pressing of Si₃N₄, and it is suggested that Y₂O₃ promotes a liquid-phase sintering process which incorporates dissolution and precipitation of Si₃N₄ at the solid-liquid interface.Visiting Research Associate at Aerospace Research Laboratories, Wright-Patterson Air Force Base, Ohio 45433, under Contract No. F33615-73-C-4155 when this work was carried out.     

The high-temperature thermal expansion of BiPbSrCaCuO superconductor and the oxide components (Bi2O3, PbO,CaO, CuO)

The thermal expansion of superconducting Bi_1.6Pb_0.4Sr₂Ca₂Cu₃Ox (BiPbSrCaCuO) and its oxide components Bi₂O₃, PbO, CaO and CuO have been studied by high-temperature dilatometric measurements (30–800°C). The thermal expansion coefficient for the BiPbSrCaCuO superconductor in the range 150–830°C is =6.4×10^–6K^–1. The temperature dependences of L/L of pressed Bi₂O₃ reveals sharp changes of length on heating (T ₁=712°C), and on cooling (T ₂=637°C and T ₃=577°C), caused by the phase transition monoclinic-cubic (T ₁) and by reverse transitions via a metastable phase (T ₂ and T ₃). By thermal expansion measurements of melted Bi₂O₃ it is shown that hysteresis in the forward and the reverse phase transitions may be partly caused by grain boundary effect in pressed Bi₂O₃. The thermal expansion of red PbO reveals a sharp decrease in L/L, on heating (T ₁=490°C), related with the phase transition of tetragonal (red, a=0.3962 nm, c=0.5025 nm)-orthorhombic (yellow, a=0.5489 nm, b=0.4756 nm, c=0.5895 nm). The possible causes of irreversibility of the phase transition in PbO are discussed. In the range 50–740°C the coefficient of thermal expansion of pressed Bi₂O₃ (_m=3.6 × 10^–6 and _c=16.6×10^–6K^–1 for monoclinic and cubic Bi₂O₃ respectively), the melted Bi₂O₃ (_m=7.6×10^–6 and _c=11.5×10^–6K^–1), PbO (_t=9.4×10⁶ and _or=3.3×10^–6K^–1 for tetragonal and orthorhombic PbO respectively), CaO (=6.1×10^–6K^–1) and CuO (=4.3×10^–6K^–1) are presented.     

Preparation and study of YSTZ-Al2O3 nanocomposites

Yttria stabilized zirconia-alumina (YSTZ-Al₂O₃) nanocomposite system with various Al₂O₃ concentrations has been synthesized by sol-gel route. The experimental techniques XRD, DTA, TGA, FT-Raman, FT-IR, SEM, Vickers hardness measurements, density measurements and Impedance spectroscopy were used to characterize the synthesized specimens. DTA result shows two exothermic reactions: one around 760°C and another around 960°C. XRD results confirm that the specimen starts to crystallize on heating above 750°C. Well resolved XRD reflections corresponding to tetragonal (t) ZrO₂ were obtained after the specimens were heated at 1000°C. FT-Raman results confirmed that the crystallites developed above 750°C was t-ZrO₂. It was observed from the XRD and DTA results that the bulk and grain boundary region crystallize independently in two different temperatures with a difference in temperature of about 200°C. The crystallization temperatures increase with Al₂O₃ contents. At 1300°C, the pure YSTZ and 5 and 10 wt % Al₂O₃ added YSTZ specimens underwent structural transformation from tetragonal to monoclinic ZrO₂. But, the tetragonal symmetry remains stable at 1300°C with an addition of 15 wt % Al₂O₃. The system which retain its tetragonal symmetry at its processing temperature (1300°C) gives high hardness and maximum density values. Almost 100% theoretical density value was obtained at 1300°C with an addition of 15 wt % of Al₂O₃.     

Formation and hot isostatic pressing of ZrO2 solid solution in the system ZrO2-Al2O3

In the system of ZrO₂-Al₂O₃, cubic ZrO₂ solid solutions containing up to 40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials prepared by the simultaneous hydrolysis of zirconium and aluminium alkoxides. At higher temperatures, they transform into tetragonal solid solutions. Metastable ZrO₂ solid solution powders containing 25 mol% Al₂O₃ have been sintered at 1000–1150 °C under 196 M Pausing the hot isostatic pressing technique. The solid solution ceramics consisting of homogeneous microstructure with an average grain size of 50 nm exhibited a very high fracture toughness of 23 MN m ^–1.5. They have been characterized by X-ray diffraction and electron probe surface analyses.     

Effect of dopant concentration on electrical conductivity in the Sc2O3-ZrO2 system

Electrical conductivity measurements have been made as a function of dopant concentration (4 to 8 mol% Sc₂O₃) in the scandia-zirconia system, All the compositions studied had a tetragonal structure. The hombohedral phase was present only in samples prepared from mechanical mixtures of Sc₂O₃ and ZrO₂. In specimens prepared by coprecipitation, no phase lines were observed and the monoclinic zirconia (m-ZrO₂) phase was present for only Sc₂O₃ contents 5 mol %. The conductivity of Sc₂O₃-ZrO₂ decreased continuously with time up to 300 h anneal time between 700 and 1000° C. X-ray diffraction of coprecipated specimens of 7.8 mol % Sc₂O₃-ZrO₂ composition annealed at 1000° C (28 days), 750° C (42 days) or 460° C (189 days) did not reveal any changes to account for this. However, transmission electron microscopy showed that changes associated with the formation of very fine precipitates had occurred. The activation energy for conduction in the low-temperature region decreased monotonically with decrease in the scandia content. Jumps in the conductivity curves and hysterisis effects were observed in specimens containing m-ZrO₂.     

Sintering of 3 mol % Y2O3-TZP and its fracture after ageing treatment

TZP ceramic of 99.7% theoretical relative final density was obtained by pressureless sintering a commercial co-precipitated 3 mol % Y₂O₃-ZrO₂ powder at 1400° C for 10 h. Fracture surfaces of the aged material revealed that the fracture of TZP ceramic was typified by an intergranular mode in areas where the phase was mainly tetragonal, whereas the transgranular mode was found predominantly in the area containing more monoclinic phase. Microcracks induced by the (t) (m) transformation provided short paths for water to accelerate the property degradation of TZP upon low-temperature ageing in a humid atmosphere.     

Synthesis and characterization of rod-like Y2O3 and Y2O3:Eu3+

Y₂O₃ rods 100 to 200 nm in diameter and 10 to 20 m in length are accessible via polyol-mediated synthesis of a precursor material with similar shape. By heating of Y(CH₃COO)₃ · xH₂O and a defined amount of water at 190°C in diethylene glycol, the rod-like precursor material is formed. Infrared spectroscopy (IR), differential thermal analysis (DTA) and thermal gravimetry (TG) evidence that this precursor material still contains acetate. However, the precursor material can be transformed to Y₂O₃ by sintering at 600°C without destruction of the rod-like shape. According to X-ray powder diffraction analysis, the rods are well crystallized. They can be assumed to be with [100] orientation. By doping with Eu³⁺ (5 mol%), red emitting phosphor rods can be realized. With optical spectroscopy the typical line emission of Eu³⁺ is observed. Diffuse reflectance of Y₂O₃:Eu³⁺ rods is determined to be higher than 95% in the visible. While exciting at 254 nm (Hg-discharge), a quantum efficiency of 38.5% is proven for the prepared Y₂O₃:Eu³⁺ rods.     

Phase Relations along the Y2O3–CuWO4Join in the Y2O3–WO3–CuO System

The phase relations in the Y₂O₃–WO₃–CuO system were studied by x-ray diffraction and thermal analysis. The results were used to construct the 800°C section of the phase diagram. Based on the new and earlier data on the liquidus relations, the section through the Y₂O₃–WO₃–CuO phase diagram along the Y₂O₃–CuWO₄join was mapped out.     

Chemical and structural properties of the system Fe2O3-Cr2O3

Chemical and structural properties of the mixed metal oxides (1–x)Fe₂O₃+xCr₂O₃ were studied by different techniques. X-ray powder diffraction showed the existence of solid solutions, (Fe_1–x Cr _x )₂O₃, over the whole concentration region, 0x1. The gradual replacement of Fe³⁺ with Cr³⁺ ions in samples prepared at 900°C caused changes in unit-cell parameters; most of these changes took place in the region fromx0.3–0.9. The samples having the fraction of Cr₂O₃ in the region from 0.7–0.8, contained two closely related phases, with slightly different compositions. After an additional heat treatment at 1100°C, these samples contained only one phase.⁵⁷Fe Mössbauer spectroscopy showed a gradual decrease of hyperfine magnetic field with increasing Cr₂O₃ content. The sample having the fraction of Cr₂O₃ of 0.7, and prepared at 900°C, exhibited two separated sextets at room temperature, in comparison with other compositions showing one sextet. It was shown that Fourier transform infrared (FT-IR) spectroscopy is a powerful method for the investigation of structural changes in these solid solutions. The increase in the Cr₂O₃ content resulted in shifts of the corresponding infrared bands. In addition, a gradual transition of the spectrum typical for -Fe₂O₃ to the spectrum typical for Cr₂O₃ was shown. The transition effects observed in the FT-IR spectra were correlated with the X-ray powder diffraction and⁵⁷Fe Mössbauer spectroscopic results.     

Microstructure, electrical properties, and degradation behavior of praseodymium oxides-based zinc oxide varistors doped with Y2O3

The microstructure, electrical properties, and degradation behavior of Pr-based zinc oxide varistors, which are composed of Zn-Pr-Co-Cr-Y oxides were investigated according to Y₂O₃ additive content in the range 0.5–4.0 mol%. The majority of the Sadded Y₂O₃ were segregated at the multiple ZnO grain junctions and grain boundaries. The average grain size was markedly decreased in the range 27.3–8.6 m with increasing Y₂O₃ additive content. Y₂O₃ acted as an inhibitor of grain growth. Additions of Y₂O₃ increased the varistor voltage in the range 36.90–686.58 V/mm, increased the nonlinear exponent in the range 3.75–87.42, decreased the leakage current in the range 115.48–0.047A, increased the barrier height in the range 1.06–2.16 eV, and decreased the donor concentration in the rang 1.87 × 10¹⁸–0.19 × 10¹⁸ cm^–3. Y₂O₃ acted as an acceptor, as a result of the decrease of donor concentration. All Pr-based ZnO varistors doped with Y₂O₃ exhibited very predominant degradation characteristics, which show a nearly symmetric I-V after the stress. In particular, since 4.0 mol% Y₂O₃-added ZnO varistor has not only very excellent non-ohmicity, but also very stable degradation behavior, it is estimated to be sufficiently used to various application fields.     

A new tentative phase equilibrium diagram for the ZrO2-CeO2 system in air

The phase relationships over a wide range of temperature and compositions in the ZrO₂-CeO₂ system have been reinvestigated. From DTA results, thermal expansion measurements andK _IC determinations it was established that additions of CeO₂ to ZrO₂ decreases the monoclinic to tetragonal ZrO₂ transition temperature, from 990 ° C to 150 50 ° C, and an invariant eutectoid point at approximately 15 mol% CeO₂ exists. The extent of the different single- and two-phase fields were determined with precise lattice parameter measurements on quenched samples. Evidence for the existence of a binary compound Ce₂Zr₃O₁₀ (ø-phase) was obtained by X-ray diffraction. The ø-phase was stable below approximately 800 ° C, above which it decomposes into tetragonal zirconia + fluorite ceria solid solutions. Taking into account the polymorphic tetragonal-cubic transition and the narrowness of the two-phase tetragonal zirconia + fluorite ceria field above 2000 ° C, the existence of a new invariant eutectoid point was assumed, in which the metastable fluorite zirconia solid solution decomposes into tetragonal zirconia + fluorite ceria solid solutions. From the results obtained, the phase diagram also incorporates a eutectic point located at approximately 2300 ° C and 24 mol % CeO₂.     

Sintering process of Y2O3 and Al2O3-doped Si3N4

The sintering process of Y₂O₃- and Al₂O₃-doped Si₃N₄ has been investigated by dilatometry and microstructural observations. The densification progressed through three processes. The bulk density increased to 85% theoretical without the formation of -Si₃N₄ in the initial process. The densification once terminated after the second process. The / transformation of Si₃N₄ and the related formation of prismatic grains reduced the densification rate in the second process, although the grain size and the aspect ratio were very small. The final process was the densification of -Si₃N₄, where the fibrous grains grew remarkably. The kinetic order for the densification of -Si₃N₄ indicated a diffusion-rate controlling mechanism with the activation energy of 244 kJ mol^–1 (<1450 ° C) and 193 kJ mol^–1 (>1450 ° C). The influence of heating rate on the grain growth was characterized by a parameter derived from kinetic parameters. The relationships between grain growth and densification behaviour have also been discussed.     

Phase Composition, Electrical Conductivity, and Stability of ZrO2–Sc2O3–Cr2O3 Solid Electrolytes

The phase composition, electrical conductivity, and structural and electrical stability of ZrO₂–Sc₂O₃–Cr₂O₃ solid electrolytes prepared by solid-state reactions involving three-step firing at 1350, 1850 (vacuum), and 1300°C were studied for compositions along two lines: x(0.91ZrO₂ + 0.09Sc₂O₃)–yCr₂O₃ (I) andx(0.89ZrO₂ + 0.11Sc₂O₃)–yCr₂O₃ (II), x + y = 1, y = 0–0.04. The results indicate that the ternary solid solutions withy= 0.01–0.02 retain a cubic structure in a broad temperature range, down to room temperature. This increases the low-temperature (<600°C) conductivity of the solid electrolytes, especially in system II. In both systems, Cr₂O₃ solubility is about 3 mol %. Stability tests at 900°C for 200 h reduce the conductivity of the solid electrolytes, particularly at the lower Sc₂O₃ content and in the presence of Cr₂O₃. The reduction in conductivity is due to the decomposition of the high-temperature tetragonal phase and the formation of a tetragonal phase with a low stabilizer content.     

Composition of New Tungsten-Containing Phases in the Y2O3–BaO–WO3–CuO System

The compositions of two new phases (cubic and tetragonal) in the Y₂O₃–BaO–WO₃–CuO system were determined. The dissolution behavior of these phases was found to correlate with their composition.     

Formation of diffusionlessly transformed tetragonal phases in rapid quenching of ZrO2-Y2O3 melts

ZrO₂ polycrystals, partially stabilized by 2 to 7 mol% Y₂O₃, were arc-melted and rapidly quenched using an arc-imaging furnace with a hammer-anvil unit. Some of the specimens were further annealed at 1700° C for 3 h in air. The phases and the microstructures of these ZrO₂-Y₂O₃ polycrystals were examined through X-ray diffraction and transmission electron microscopy. Special emphasis was placed upon the examination of the microstructure of the metastable tetragonal phase (t phase) which was formed by a diffusionless transformation of the high-temperature cubic phase. It was found that the t phase exhibits a twinned and mosaic structure made of alternating layers of twin-related variants. A comparison of the present experimental results with other related works has also been made.