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1.
Ho-Yong Lee Young-Woo Rhee Suk-Joong L. Kang 《Journal of the American Ceramic Society》1996,79(6):1659-1663
When sintered 95Al2 O3 -5Fe2 O3 (wt%) specimens constituting corundum grains and iron aluminate spinel precipitates were annealed under high oxygen partial pressure (Po 2 ) where only a corundum phase is stable, fast dissolution of particulate spinel precipitates occurred, together with the migration of corundum grain boundaries. Behind the migrating boundaries, a corundum solid solution enriched with Fe2 O3 formed. Discontinuous dissolution (DD) of particulate spinel precipitates thus occurred by Po 2 increase. In contrast, when 95Al2 O3 -5Fe2 O3 specimens constituting only corundum grains were annealed under low Po 2 where both corundum and spinel phases are stable, grain boundaries migrated without spinel precipitation, leaving behind a corundum phase depleted of Fe2 O3 , similar to chemically induced grain-boundary migration (CIGM) observed during solute depletion. The volatilization of Fe2 O3 appeared to cause the boundary migration without precipitation. The observed CIGM and DD would suggest various possibilities of microstructure control in other oxide systems through oxygen partial pressure change. 相似文献
2.
An isothermal section of the ternary system MgO–Al2 O3 -Cr2 O3 was determined at 1700°± 15°C to delineate the stability field for spinel crystalline solutions (cs). Crystalline solutions were found between the pseudobinary joins MgAl2 O4 –Cr2 O3 and MgCr2 O4 -Al2 O3 , and the binary join MgAl2 O4 -MgO. The first two crystalline solutions exhibit cation vacancy models while the latter can probably be designated as a cation interstitial model. Precipitation from spinel cs may proceed directly to an equilibrium phase, (Al1-x Crx )2 O3 , with the corundum structure or through a metastable phase of the probable composition Mg(Al1-x Cr )26 O40 . The composition and temperature limits were defined where the precipitation occurs via metastable monoclinic phases. The coherency of the metastable monoclinic phase with the spinel cs matrix can be understood by considering volume changes with equivalent numbers of oxygens and known crystallographic orientation relations. Electron probe and metallographic microscope investigations showed no preferential grain boundary precipitation. 相似文献
3.
The dissolution of (Al, Cr)2 O3 into CaO—MgO—Al2 O3 —SiO2 melts, under static and forced-convective conditions was investigated at 1550°C in air. With sufficient MgO in the melt, or sufficient Cr2 O3 in (Al, Cr)2 O3 , a layer consisting of a spinel solid solution, Mg(Al, Cr)2 O4 , formed at the (Al, Cr)2 O3 /melt interface. The dissolution kinetics of 1.5 and 10 wt% Cr2 O3 specimens were determined as a function of immersion time, specimen rotation rate, and magnesia content of the melt. Electron microprobe analysis was used to characterize concentration gradients in the (Al, Cr)2 O3 sample, the Mg(Al, Cr)2 O4 spinel, or in the melt after immersion of specimens containing 1.5 to 78 mol% Cr2 O3 . The dissolution kinetics and microprobe analyses indicated that a steady-state condition was reached during forced-convective, indirect (Al, Cr)2 O3 dissolution such that spinel layer formation was rate limited by solid-state diffusion through the spinel layer and/or through the specimen, and spinel layer dissolution was rate limited by liquid-phase diffusion through a boundary layer in the melt. This is consistent with a model previously developed for the indirect dissolution of sapphire in CMAS melts. 相似文献
4.
Grain growth of ZnO during liquid-phase sintering of a ZnO-6 wt% Bi2 O3 ceramic was investigated for A12 O3 additions from 0.10 to 0.80 wt%. Sintering in air for 0.5 to 4 h at 900° to 1400°C was studied. The AI2 O3 reacted with the ZnO to form ZnAl2 O4 spinel, which reduced the rate of ZnO grain growth. The ZnO grain-growth exponent was determined to be 4 and the activation energy for ZnO grain growth was estimated to be 400 kJ/mol. These values were compared with the activation parameters for ZnO grain growth in other ceramic systems. It was confirmed that the reduced ZnO grain growth was a result of ZnAl2 O4 spinel particles pinning the ZnO grain boundaries and reducing their mobility, which explained the grain-growth exponent of 4. It was concluded that the 400 kJ/mol activation energy was related to the transport of the ZnAl2 O4 spinel particles, most probably controlled by the diffusion of O2- in the ZnAl2 O4 spinel structure. 相似文献
5.
V. S. STUBICAN C. GRESKOVICH H. A. McKINSTRY 《Journal of the American Ceramic Society》1969,52(4):174-177
A quantitative X-ray technique for measuring precipitation strains has not been previously applied in metallic or oxide systems. The Warren-Averbach analysis of strain was used to determine the buildup of elastic strain energy in the spinel crystalline solution matrix (gross composition = 60 mol% MgAl2 O2 + 40 mol% Cr2 O3 ) during the isothermal (1135°C) precipitation of a metastable (coherent) monoclinic phase. The elastic strain energy of the spinel crystalline solution matrix increased to a maximum of about 3.1 × 107 ergs/cm3 for a reaction time of 8 h. There was a marked decrease in the elastic strain energy during the initial precipitation of the equilibrium corundum crystalline solution with the composition (Al3+ 0.72 Cr3+ 0.25 )O3 . An overall diffusion activation energy for precipitation of the mono-clinic phase was approximately 86 kcal/mol. 相似文献
6.
Subsolidus phase relations in the system iron oride-Al2 O2 -Cr2 O3 in air and at 1 atm. O2 pressure have been studied in the. temperature interval 1250° to 1500°C. At temperatures below 1318° C. only sesquioxides with hexagonal corundum structure are present as equilibrium phases. In the temperature interval 1318° to 1410°C. in air and 1318° to 1495° C. at 1 atm. O2 , pressure the monoclinic phase Fe2 O3 . Al2 O3 with some Cr2 O3 in solid solution is present in the phase assemblage of certain mixtures. At temperatures above 1380°C. in air and above 1445°C. at 1 atm. O2 pressure a complex spinel solid solution is one of the phases present in appropriate composition areas of the system. X-ray data relating d- spacing to composition of solid solution phases are given. 相似文献
7.
R. R. DAYAL R. E. JOHNSON† ARNULF MUAN‡ 《Journal of the American Ceramic Society》1967,50(10):537-540
The free energy of reaction for the formation of mullite from its oxide components was derived from equilibrium studies in the system CoO-Al2 O3 -SiO2 . Within this system there appears, at solidus temperature in a certain composition area, the phase assemblage mullite + silica + spinel (= cobalt aluminate) + liquid. Determination of the oxygen pressure of a gas phase at which metallic cobalt precipitates from this phase assemblage and from the phase assemblage spinel (= cobalt aluminate) + corundum in the system CoO-Al2 O3 permits calculation of ΔG° for the reaction 3Al2 O3 + 2SiO2 = Al6 Si2 O13 . The value obtained at 1422°C is -5.8 kcal. 相似文献
8.
P. L. ROEDER F. P. GLASSER† E. F. OSBORN 《Journal of the American Ceramic Society》1968,51(10):585-593
Liquidus phase equilibrium data are presented for the system Al2 O3 -Cr2 O3 -SiO2 . The liquidus diagram is dominated by a large, high-temperature, two-liquid region overlying the primary phase field of corundum solid solution. Other important features are a narrow field for mullite solid solution, a very small cristobalite field, and a ternary eutectic at 1580°C. The eutectic liquid (6Al2 O3 -ICr2 O3 -93SiO2 ) coexists with a mullite solid solution (61Al2 O3 -10Cr2 O3 -29SiO2 ), a corundum solid solution (19Al2 O3 -81Cr2 O3 ), and cristobalite (SO2 ). Diagrams are presented to show courses of fractional crystallization, courses of equilibrium crystallization, and phase relations on isothermal planes at 1800°, 1700°, and 1575°C. Tie lines were sketched to indicate the composition of coexisting mullite and corundum solid solution phases. 相似文献
9.
G. Bhattacharya S. Zhang D. D. Jayaseelan W. E. Lee 《Journal of the American Ceramic Society》2007,90(1):97-106
Lithium borate (Li2 B4 O7 ) and sodium borate (Na2 B4 O7 ) mineralize spinel formation from stoichiometric MgO and Al2 O3 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. Na2 B4 O7 -mineralized compositions show predominantly templated grain growth at 1000°C, which changes to dissolution–precipitation at 1100°C, whereas Li2 B4 O7 -mineralized compositions show dissolution–precipitation from 1000°C. Li2 B4 O7 is a stronger mineralizer as spinel formation is complete with 3 wt% Li2 B4 O7 at 1000°C and with ≥1.5 wt% addition at 1100°C, whereas Na2 B4 O7 -mineralized compositions are found to retain some unreacted corundum even at 1100°C. 相似文献
10.
Koji Morita Keijiro Hiraga Yoshio Sakka 《Journal of the American Ceramic Society》2002,85(7):1900-1902
High-strain-rate superplasticity is attained in a 3-mol%-Y2 O3 -stabilized tetragonal ZrO2 polycrystal (3Y-TZP) dispersed with 30 vol% MgAl2 O4 spinel: tensile elongation at 1823 K reached >300% at strain rates of 1.7 × 10−2 – 3.3 × 10−1 s−1 . The flow behavior and the microstructure of this material indicate that the MgAl2 O4 dispersion should enhance accommodation processes necessary for grain boundary sliding. Such an effect is assumed to arise from an enhancement of the cation diffusion by the dissolution of Al and Mg ions into the ZrO2 matrix and from stress relaxation due to the dispersed MgAl2 O4 grains. 相似文献
11.
The subsolidus phase equilibrium diagram for the pseudobinary join MgAl2 O4 -Ga2 O3 was determined. The shape of the exsolution boundary was obtained by heat-treating samples pre- equilibrated at 1600°C. Crystalline solubility of Ga2 O3 in MgAl2 O4 decreased from 73 mole % at 1600°C to 55 mole % at 1200°C. The crystalline solution was formed by the replacement of Mg2+ ions by Ga3+ ions to produce a cation defect spinel. The phase precipitated was the mono-clinic δ-Ga2 O3 (=δ-Al2 O3 structure). Changes in the ratios of relative X-ray diffraction intensities indicated that the crystalline solutions also disorder with temperature. 相似文献
12.
ZrO2 -2 mol% Y2 O3 crystals with average grain sizes from 0.51 to 0.96 µm were prepared by sintering in air at 1400°C for 2 to 100 h. The tetragonal-to-monoclinic phase transformation associated with the low-temperature degradation was investigated to clarify how the presence of water directly affects the influence of grain size on transformation. The specimens were exposed to water at 80–120°C, a temperature range in which transformation by thermal activation is difficult in the absence of water. Contrary to expectations, this type of low-temperature transformation did not accelerate monotonously with increasing grain size. Instead, the amount of phase transformation first decreased, reaching a constant value, and then increased with increasing grain size. Such interesting results can be explained satisfactorily by the combined influences of grain size on the nucleation process, because of preferential dissolution of yttrium at the grain boundaries, and the intrinsic transformability of Y2 O3 -doped tetragonal ZrO2 grains. 相似文献
13.
Akshoy Kumar Chakravorty Dilip Kumar Ghosh 《Journal of the American Ceramic Society》1987,70(3):46-C-
The independent crystallization sequence of an Al2 O3 component is modified in the presence of SiO2 and vice versa. Mixed SiO2 -Al2 O3 , gel (28 wt% SiO2 and 72 wt% Al2 O3 ) forms neither cristobalite nor γ-Al2 O3 and corundum at 1000°C but forms Si-Al spinel; an amorphous aluminosilicate phase invariably also forms after the gel is heated. However, the composition of this amorphous aluminosilicate phase is not as yet known. 相似文献
14.
Kuan Zong Fung Anil V. Virkar David L. Drobeck 《Journal of the American Ceramic Society》1994,77(6):1638-1648
Cubic solid solutions in the Y2 O3 -Bi2 O3 system with ∼25% Y2 O3 undergo a transformation to a rhombohedral phase when annealed at temperatures ≤ 700°C. This transformation is composition-invariant and is thermally activated, and the product phase can propagate across matrix grain boundaries, indicating that there is no special crystallo-graphic orientation relationship between the product and the parent phases. Based on these observations, it is proposed that cubic → rhombohedral phase transformation in the Y2 O3 -Bi2 O3 system is a massive transformation. Samples of composition 25% Y2 O3 -75% Bi2 O3 with and without aliovalent dopants were annealed at temperatures ≤ 700°C for up to 10000 h. ZrO2 as a dopant suppressed while CaO and SrO as dopants enhanced the kinetics of phase transformation. The rate of cubic/rhombohedra1 interface migration (growth rate or interface velocity) was also similarly affected by the additions of dopants; ZrO2 suppressed while CaO enhanced the growth rate. Diffusion studies further showed that ZrO2 suppressed while CaO enhanced cation interdiffusion coefficient. These observations are rationalized on the premise that cation interstitials are more mobile compared to cation vacancies in cubic bismuth oxide. The maximum growth rate measured was ∼10−10 m/s, which is orders of magnitude smaller than typical growth rates measured in metallic alloys. This difference is explained in terms of substantially lower diffusion coefficients in these oxide systems compared to metallic alloys. 相似文献
15.
Mari Lou Balmer Fred F. Lange Vikram Jayaram Carlos G. Levi 《Journal of the American Ceramic Society》1995,78(6):1489-1494
Aqueous mixtures of zirconium acetate and aluminum nitrate were pyrolyzed and crystallized to form a metastable solid solution, Zr1- x Al x O2− x /2 ( x < 0.57). The initial, metastable phase partitions at higher temperatures to form two metastable phases, viz., t −ZrO2 +γ-Al2 O3 with a nano-scale microstructure. The microstructural observations associated with the γ- →α-Al2 O3 phase transformation in the t -ZrO2 matrix are reported for compositions containing 10, 20, and 40 mol% A12 O3 . During this phase transformation, the α-Al2 O3 grains take the form of a colony of irregular, platelike grains, all with a common crystallographic orientation. The plates contain ZrO2 inclusions and are separated by ZrO2 grains. The volume fraction of A12 O3 and the heat treatment conditions influence the final microstructure. At lower volume fractions of A12 O3 , the colonies coarsen to single, irregular plates, surrounded by polycrystalline ZrO2 . Interpenetrating microstructures produced at high volume fractions of A12 O3 exhibit very little grain growth for periods up to 24 h at 1400°C. 相似文献
16.
The preparation of near stoichiometric spinel and alumina-rich spinel composites from Al2 O3 and MgO powders with the addition of Na3 AlF6 up to 4 wt% in the temperature range 700°–1600°C was studied; 98 wt% spinel containing 72 wt% Al2 O3 can be produced from the mixture of 72 wt% (50 at.%) Al2 O3 + 28 wt% (50 at.%) MgO powders with the addition of 1 wt% Na3 AlF6 fired at 1300°C for 1 h. Spinels containing 81–85 wt% Al2 O3 can be produced from either the mixture of 90 wt% (78 at.%) Al2 O3 + 10 wt% (22 at.%) MgO or the mixture of 95 wt% (88 at.%) Al2 O3 + 5 wt% (12 at.%) MgO powders with the addition of 4 wt% Na3 AlF6 in 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% Al2 O3 . 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. 相似文献
17.
The phase equilibrium relations in the systems Y2 O3 -Al2 O3 and Gd2 O3 -Fe2 O3 were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd2 O3 -Fe2 O3 but only metastable in the system Y2 O3 -AI2 O3 . This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O3 . A new 2:1 molar ratio cubic phase has been found in the system Y2 O3 -A12 O3 . Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination. 相似文献
18.
Pomin Su Anil V. Virkar Camden R. Hubbard O. Burl Cavin Wallace D. Porter 《Journal of the American Ceramic Society》1993,76(10):2513-2520
Gd2 O3 -doped Bi2 O3 polycrystalline ceramics containing between 2 and 7 mol% Gd2 O3 were fabricated by pressureless sintering powder compacts. The as-sintered samples were tetragonal at room temperature. Hightemperature X-ray diffraction (XRD) traces showed that the samples were cubic at elevated temperatures and transformed into the tetragonal polymorph during cooling. On the basis of conductivity measurements as a function of temperature and differential scanning calorimetry (DSC), the cubic → tetragonal as well as tetragonal → cubic → teansition temperatures were determined as a function of Gd2 O3 concentration. The cubic → tetragonal transformation appears to be a displacive transformation. It was observed that additions of ZrO2 as a dopant, which is known to suppress cation interdiffusion in rare-earth oxide–Bi2 O3 systems, did not suppress the transition, consistent with it being a displacive transition. Annealing of samples at temperatures 660°C for several hundred hours led to decomposition into a mixture of monoclinic and rhombohedral phases. This shows that the tetragonal polymorph is a metastable phase. 相似文献
19.
Annealing of ZrO2 -toughened Al2 O3 (ZTA) at elevated temperatures causes growth of both the intergranular ZrO2 particles and the Al2 O3 "matrix" grains. Exaggerated ("breakaway") grain growth occurs in some, but not all, specimens. Analytical electron microscopy of two ZTA's, both of which contained a continuous amorphous (glassy) grain-boundary phase, but only one of which showed breakaway grain growth, revealed that the occurrence of breakaway grain growth could be correlated with the chemistry of the ubiquitous glassy grain-boundary phase. 相似文献
20.
Mullite transformation kinetics of sol-gel-derived diphasic mullite gels doped with P2 O5 , TiO2 , and B2 O3 were studied using quantitative X-ray diffraction and differential thermal analysis (DTA). The mullite transformation temperature initially increased with P2 O5 doping because of phase separation and formation of α-alumina and cristobalite. In TiO2 -doped samples, the mullite transformation temperature decreased with TiO2 doping, and the transformation rate increased with decreasing TiO2 particle size. Kinetic studies showed that titania reduced the activation energy for both nucleation and growth relative to pure diphasic mullite gels by lowering the glass viscosity and/or enhancing the solid-state mass transport through lattice defects. B2 O3 doping decreased the mullite transformation temperature and lowered the activation energy for both nucleation and growth but especially affected the mullite nucleation process, as indicated by the much smaller grain size. 相似文献