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1.
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
2.
The dissolution rate of sapphire into CaO-MgO-Al2 O3 -SiO2 (CMAS) melts was investigated at 1450° and 1550°C. The effects of immersion time, specimen rotation rate, and magnesia concentration in the bulk melt on the sapphire dissolution rate and on the growth rate of magnesium aluminate spinel at the sapphire/melt interface were determined. The processes of direct and indirect sapphire dissolution into CMAS melts are discussed, with the support of kinetic and microprobe data.1 A model of indirect sapphire dissolution1,2 is used along with the equations of Tedmon3 to describe the kinetics of indirect dissolution and spinel layer growth during forced-convective and static sapphire dissolution. 相似文献
3.
Federica Bondioli Anna Maria Ferrari Cristina Leonelli Tiziano Manfredini Laura Linati Piercarlo Mustarelli 《Journal of the American Ceramic Society》2000,83(8):2036-2040
The aim of this work is to study the structural characteristics and properties of the solid solution (Al,Cr)2 O3 . XRD analysis, 27 Al MAS-NMR measurements, and microstructural characterization were used to determine the relationship between color and crystallochemical properties of the compounds formed. In particular, to determine more accurately the mechanism of solid solution formation above the miscibility gap of the system, the marker technique was used. In order to define the behavior of the system for temperatures below the miscibility gap at 1 bar pressure, the composition Al2 O3 :Cr2 O3 1:1 was studied with high-temperature XRD. 相似文献
4.
Liquidus equilibrium relations for the air isobaric section of the system Y2 O3 –Fe2 O3 –FeO–Al2 O3 are presented. A Complete solid-solution series is found between yttrium iron garnet and yttrium aluminum garnet as well as extensive solid solutions in the spinel, hematite, orthoferrite, and corundum phases. Minimum melting temperatures are raised progressively with the addition of alumina from 1469°C in the system Y–Fe–O to a quaternary isobaric peritectic at 1547°C and composition Y 0.22 Fe 1.08 Al 0.70 O 2.83 * Liquidus temperatures increase rapidly with alumina substitutions beyond this point. The thermal stability of the garnet phase is increased with alumina substitution to the extent that above composition Y 0.75 Fe 0.65 Al 0.60 O 3 garnet melts directly to oxide liquid without the intrusion of the orthoferrite phase. Garnet solid solutions between Y 0.75 Fe 1.25 O 3 and Y 0.75 Fe 0.32- Al 0.93 O 3 can be crystallized from oxide liquids at minimum temperatures ranging from 1469° to 1547°C, respectively. During equilibrium crystallization of the garnet phase, large changes in composition occur through reaction with the liquid. Unless care is taken to minimize temperature fluctuations and unless growth proceeds very slowly, the crystals may show extensive compositional variation from core to exterior. 相似文献
5.
Phase relations in air at 1300°C were determined for the system MgO-Cr2 O3 −Fe2 O3 by conventional quenching techniques. Details of the phase equilibria were established for: (1) the sesquioxide solid solution between Cr2 O3 and Fe2 O3 , (2) the spinel solid solution field between MgCr2 O4 and MgFe2 O4 , and (3) the periclase solid solution field for MgO. Selected tie lines connecting coexisting compositions were established with X-ray diffractometer data. Diffuse reflectance spectra, diffractometer intensity ratios, and lattice parameter measurements were obtained for quenched samples to study the structural inversion in the spinel series MgCr2 O4-MgFe2 O4 . 相似文献
6.
Thermal and X-ray studies show that there is complete solid solution between MgO.Cr2 O3 and MgO.Al2 O3 and that the spinel solid solutions are stable with no exsolution down to temperatures as low as 510°C. There is no solid solution of excess Cr2 O3 in MgO.Cr2 O3 nor of MgO.Cr2 O3 in Cr2 O3 . The join MgO.Cr2 O3 –Al2 O3 is found to be nonbinary; compositions along that join yield mixtures of a chromium oxide-alumina solid solution and a spinel solid solution on firing to temperatures high enough to promote solid-state reaction. Chromium oxide loss by volatilization increases at higher temperature. At a given temperature, chromium oxide loss is found to vary directly with the partial pressure of oxygen in the furnace atmosphere and with the ratio of MgO to SiO2 in the charges heated. 相似文献
7.
Activity–composition relations of FeCr2 O4 –FeAl2 O4 and MnCr2 O4 –MnAl2 O4 solid solutions were derived from activity–composition relations of Cr2 O3 –Al2 O3 solid solutions and directions of conjugation lines between coexisting spinel and sesquioxide phases in the systems FeO–Cr2 O3 –Al2 O3 and MnO–Cr2 O3 –Al2 O3 . Moderate positive deviations from ideality were observed. 相似文献
8.
JONG-HEE PARK WAYNE E. KING STEVEN J. ROTHMAN 《Journal of the American Ceramic Society》1987,70(12):880-885
The cation diffusivities in the lattice and along dislocations and grain boundaries have been measured on sintered polycrysals of Cr2 O3 ; and Cr2 Cr2 O3 -0.09 wt% Y2 O3 at1100°C and at the pO2 corresponding to that of Cr/Cr2 O3 equilibrium at that temperature. Results for lattice and dislocation diffusivities in pure Cr2 O3 are in good agreement with previous work. The present results indicate that yttrium additions have negligible effect on lattice and dislocation diffusion. However, grain-boundary diffusion in pure Cr2 O3 is significantly slower than grain-boundary diffusion in Cr2 O3 -0.09 wt% Y2 O3 . The results are discussed in terms of their implications for the reactive-element effect in high-temperature oxidation of chromium-containing alloys. 相似文献
9.
SiO2 -Al2 O3 melts containing 42 and 60 wt% A12 O3 were homogenized at 2090°C (∼10°) and crystallized by various heat treatment schedules in sealed molybdenum crucibles. Mullite containing ∼78 wt% A12 O3 precipitated from the 60 wt% A12 O3 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 A12 O3 in the mullite decreased with a corresponding increase in the Al2 O3 content of the glass. A similar decrease of Al2 O3 in mullite was observed when crystallized melts were reheated at 1725°± 10°C; the lowest A12 O3 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. 相似文献
10.
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
11.
The quenching method has been used to determine approximate phase relations in the system iron oxide-Cr2 O3 in air. Only two crystalline phases, a sesquioxide solid solution (Fe2 O3 –Cr2 O3 ) with corundum structure and a spinel solid solution (approximately FeO ·Fe2 O3 –FeO – Cr2 O3 ), occur in this system at conditions of temperature and O2 partial pressure (0.21 atm.) used in this investigation. Liquidus temperatures increase rapidly as Cr2 O3 is added to iron oxide, from 1591°C. for the pure iron oxide end member to a maximum of approximately 2265°C. for Cr2 O3 . Spinel(ss) is the primary crystalline phase in iron oxide-rich mixtures and sesquioxide (ss) in Cr2 O3 –rich mixtures. These two crystalline phases are present together in equilibrium with a liquid and gas (po2 = 0.21 atm.) at approximately 2075°C. 相似文献
12.
The phase diagrams in the Al2 O3 –Cr2 O3 and V2 O3 –Cr2 O3 systems have been assessed by thermodynamic modeling with existing data from the literature. While the regular and subregular solution models were used in the Al2 O3 –Cr2 O3 system to represent the Gibbs free energies of the liquid and solid phases, respectively, the regular solution model was applied to both phases in the V2 O3 –Cr2 O3 system. By using the liquidus, solidus, and/or miscibility gap data, the interaction parameters of the liquid and solid phases were optimized through a multiple linear regression method. The phase diagrams calculated from these models are in good agreement with experimental data. Also, the solid miscibility gap and chemical spinodal in the V2 O3 –Cr2 O3 system were estimated. 相似文献
13.
JUN'ICHI NAKANO TOMOAKI YAMADA SHINTARO MIYAZAWA 《Journal of the American Ceramic Society》1979,62(9-10):465-467
In the ternary system Li2 O-Nd2 O3 -P2 05 , part of the phase diagram relevant to the growth of single LindP4 O12 (LNP) crystals was examined. LNP melts incongruently and decomposes into NdP3 O9 and liquid at the peritectic temperature of 970°C. For the crystal growth, an Li2 O-P2 O5 mixture should be used as a flux. The melt compositions from which LNP nucleates were clarified. 相似文献
14.
The dc electrical conductivity of MgO-doped Cr2 O3 and the defect models with the defect structure of a sesquioxide were investigated as a function of oxygen partial pressure, temperature, and dopant content. The electrical conductivity of MgO-doped Cr2 O3 is increased with oxygen partial pressure and temperature. The electrical conductivity of MgO-doped Cr2 O3 within the solubility limit is increased with MgO content because of the creation of holes and the annihilation of chromium vacancies. Above the solubility limit, however, it is decreased with increasing MgO content owing to the formation of the spinel phase (MgCr2 O4 ). 相似文献
15.
Shingo Hirano Masaru Yoshinaka Ken Hirota Osamu Yamaguchi 《Journal of the American Ceramic Society》1996,79(1):171-176
In the ZrO2 -Cr2 O3 system, metastable t -ZrO2 solid solutions containing up to 11 mol% Cr2 O3 crystallize at low temperatures from amorphous materials prepared by the hydrazine method. The lattice parameter c decreases linearly from 0.5149 to 0.5077 nm with increased Cr2 O3 content, whereas the lattice parameter a is a constant value ( a = 0.5077 nm) regardless of the starting composition. At higher temperatures, transformation (decomposition) of the solid solutions proceeds in the following way: t (ss)→ t (ss) + m + Cr2 O3 → m + Cr2 O3 . Above 11 mol% Cr2 O3 addition, c-ZrO2 phases are formed in the presence of Cr2 O3 . The t -ZrO2 solid solution powders have been characterized for particle size, shape, and surface area. They consist of very fine particles (15–30 nm) showing thin platelike morphology. Dense ZrO2 (3Y)-Cr2 O3 composite ceramics (∼99.7% of theoretical) with an average grain size of 0.3 μm have been fabricated by hot isostatic pressing for 2 h at 1400°C and 196 MPa. Their fracture toughness increases with increased Cr2 O3 content. The highest K Ic value of 9.5 MPa·;m1/2 is achieved in the composite ceramics containing 10 mol% Cr2 O3 . 相似文献
16.
A study of the solid solution of TiO2 , Fe2 O3 , and Cr2 03 in mullite was made by measuring the changes in lattice parameters and unit-cell volume. Synthetic mullite (3O3 -2SiO2 ) was reacted with up to 12 weight % of the oxides at temperatures ranging from 1000° to 17000C. The approximate minimum temperature required for the formation of solid solution was 12000C. for Fe2 03 and 1400°C. for Cr2 O3 and TiO3 . The maximum amount of solid solution found was 2 to 4% TiO2 at 1600°C., 10 to 12% Fe2 Os at 1300°C., and 8 to 10% CrZ O3 at 1600OC. Lattice parameters and unit-cell volumes for each solid solution series increased with increasing amounts of foreign oxide. There was good agreement between the calculated and observed increase in cell dimensions for the iron oxide series. Except in the case of titania, there was good agreement between X-ray data and petrographic observations. 相似文献
17.
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
18.
Arno Kaiser Burkhard Sommer Eduard Woermann 《Journal of the American Ceramic Society》1992,75(6):1463-1471
The system CaO–chromium oxide in air is reinvestigated and the existence of intermediate phases with chromium in oxidation states >3+ (Ca5 Cr3 O12 , Ca3 (CrO4 )2 , and Ca5 (CrO4 )3 ) confirmed. Under reducing conditions these phases are unstable. A metastable, polymorphic form of calcium chromite, δ -CaCr2 O4 , is observed. In the CaO-rich section of the CaO–Al2 O3 –Cr2 O3 system a ternary intermediate phase, chrome-haüyne, Ca4 [(Al,Cr3+ )6 O12 ](Cr6+ O4 ), coexists with calcium chromate and calcium aluminate phases. In air, low melting temperatures are preserved in all assemblages containing calcium chromate phases. Under reducing conditions a new ternary phase, Ca6 Al4 Cr2 O15 , coexists with CaO, CaCr2 O4 , chrome-haüyne, and calcium aluminate phases. The influence of chromium oxide additions on the solidus temperatures of the CaO–Al2 O3 system is insignificant. 相似文献
19.
The quenching technique has been used to determine equilibrium relations in the system manganese oxide-Cr2 O3 in air in the temperature range 600° to 1980°C. The following isobaric invariant situations have been determined: At 910°± 5°C tetragonal Mn3 O4 solid solution, cubic Mn3 O4 solid solution (=spinel), Mn2 O3 solid solution, and gas coexist in equilibrium. Cubic Mn3 O4 solid solution, Cr2 O3 solid solution, liquid, and gas are present together in equilibrium at 1970°± 20°C. The invariant situation at which cubic Mn3 O4 solid solution, Mn2 O3 solid solution, Cr2 O3 solid solution, and gas exist together in equilibrium is below 600°C. 相似文献
20.
The weight loss of Cr2 O3 in oxidizing environments (Po2 = 1 to 10−3 atm) at 1200°C was measured. Both hot-pressed and sintered Cr2 O3 pellets were investigated in O2 /Ar gas mixtures, and the dependence of the weight loss on the O2 partial pressure, the gas flow rate, and the total pressure was determined independently. The experimentally determined O2 partial pressure dependence (rate ∝ PO2 3/4 ) corresponds to that expected for the reaction Cr2 O3 (s)+3/2O2 ⇌2CrO3 (g). The flow rate and total pressure dependencies show that mass transport through a gaseous boundary layer is the rate-controlling step in the oxidation/vaporization of Cr2 O3 . Evaporation coefficients for the loss of CrO3 (g) under the experimental conditions were <0.01. 相似文献