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1.
The ionic conductivity of cubic solid solutions in the system CaO -Y2 O3 -ZrO2 was examined. Particular Y2 O3 -ZrO2 binary compositions were more conductive at elevated temperatures (>600°C) than either CaO-ZrO2 binary or CaO-Y2 O3 -ZrO2 ternary compositions. The higher ionic conductivity appears to be related to a lower activation energy rather than to the number of oxygen vacancies dictated by composition. Those compositions of highest conductivity lie close to the cubic-monoclinic solid-solution phase boundary. Conductivity-temperature data are presented that indicate a reversible order-disorder transition for Y2 O3 -ZrO2 cubic solid solutions containing 20 and 25 mole % Y2 O3 . The transference number for the oxygen ion at 1000°C for Y2 O2 -ZrO2 cubic solid solutions is greater than 0.99. 相似文献
2.
The phase relations for the Sc2 O3 -Ta2 O5 system in the composition range of 50-100 mol% Sc2 O3 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 Sc5.5 Ta1.5 O12 phase, defect-fluorite-type cubic phase (F-phase, space group Fm 3 m ), ScTaO4 , and Sc2 O3 were found in the system. The Sc5.5 Ta1.5 O12 phase formed in 78 mol% Sc2 O3 at <1700°C and seemed to melt incongruently. The F-phase formed in ∼75 mol% Sc2 O3 and decomposed to Sc5.5 Ta1.5 O12 and ScTaO4 at <1700°C. The F-phase melted congruently at 2344°± 2°C in 80 mol% Sc2 O3 . The eutectic point seemed to exist at ∼2300°C in 90 mol% Sc2 O3 . 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. 相似文献
3.
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
4.
The electrical conductivity of M2 O3 -ZrO2 compositions containing 6 to 24 mole % M2 O3 , where M represents La, Sm, Y, Yb, or Sc, was examined. Only Sm2 O3 , Y2 O3 , and Yb2 O3 formed cubic solid solutions with ZrO2 over most of this substitutional range. Scandia forms a wide cubic solid solution region with ZrO2 at temperatures above 130°C whereas the cubic solid solution region at room temperature is narrow (6 to 8 mole % Sc2 O3 ). Lanthana additions to ZrO2 produced no fluorite-type cubic solid solutions within the compositional range investigated. Generally, the electrical conductivity of these cubic solid solutions increased as the size of the substituted cation decreased and the electrical conductivity for each binary system attained a maximum at about 10 to 12 mole % M2 O3 . 相似文献
5.
Yoshiyuki Yokogawa Nobuo Ishizawa Shigeyuki Smiya Masahiro Yoshimura 《Journal of the American Ceramic Society》1991,74(9):2073-2076
The Phase relations of the system Gd2 O3 -Ta2 O5 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 Gd3 TaO7 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 Gd2 O3–Ta2O5 in the Gd2 O3 –rich portion 相似文献
6.
The phase relations for the system y2 o3 –Ta2 o5 in the composition range 50 to 100 mol% Y2 O3 have been studied by solid-state reactions at 1350°, 1500°, or 17000C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phases (W2 phase, space group C2221 ), fluorite-type cubic phases (F phase, space group Fm3m )and another orthorhombic phase (O phase, space group Cmmm )are found in the system. The W2 phase forms in 75 mol% Y2 O3 under 17000C and O phase in 70 mol% Y2 O3 up to 1700°C These phases seem to melt incongruently. The F phase forms in about 80 mol% Y2 O3 and melts congruently at 2454° 3°C. Two eutectic points seem to exist at about 2220°C 90 mol% Y2 O3 , and at about 1990°C, 62 mol% Y2 O3 . A Phase diagram including the above three phases were not identified with each other. 相似文献
7.
The subsolidus phase relations in the entire system ZrO2 -Y2 O3 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% Y2 O3 and ∼490°C, ( b ) cubic zirconia solid solutiow→δ-phase Y4 Zr3 O12 +hexagonalphase Y6 ZrO11 at 45 mol% Y2 O3 and ∼1325°±25°C, and ( c ) yttria C -type solid solution→wcubic zirconia solid solution+ hexagonal phase Y6 ZrO11 at ∼72 mol% Y2 O3 and 1650°±50°C. Two ordered phases were also found in the system, one at 40 mol% Y2 O3 with ideal formula Y4 Zr3 O12 , and another, a new hexagonal phase, at 75 mol% Y2 O3 with formula Y6 ZrO11 . 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 -Y2 O3 . 相似文献
8.
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
9.
Doreen D. Edwards Pollyanna E. Folkins Thomas O. Mason 《Journal of the American Ceramic Society》1997,80(1):253-257
Subsolidus phase relationships in the Ga2 O3 –In2 O3 system were studied by X-ray diffraction and electron probe microanalysis (EPMA) for the temperature range of 800°–1400°C. The solubility limit of In2 O3 in the β-gallia structure decreases with increasing temperature from 44.1 ± 0.5 mol% at 1000°C to 41.4 ± 0.5 mol% at 1400°C. The solubility limit of Ga2 O3 in cubic In2 O3 increases with temperature from 4.X ± 0.5 mol% at 1000°C to 10.0 ± 0.5 mol% at 1400°C. The previously reported transparent conducting oxide phase in the Ga-In-O system cannot be GaInO3 , which is not stable, but is likely the In-doped β-Ga2 O3 solid solution. 相似文献
10.
On the basis of 190 runs made up to 1860°C in sealed noble-metal containers the following revisions have been made in the equilibrium diagram for the system A12 O3 –SiO2 . Mullite melts congruently at 1850°C. The extent of equilibrium solid solution in mullite at solidus temperature is from approximately 60 mole % Al2 O3 (3/2 ratio) to 63 mole % A12 O3 . Metastable solid solutions can be prepared up to about 67 mole % Al2 O3 . There is no evidence for stable solubility of excess SiO2 beyond the 3/2 composition at pressures below 3 kbars. Refractive indices are presented for glasses containing up to 60 mole % Al2 O3 and from them the composition of the eutectic is confirmed at 5 mole % SiO2 . The variation in lattice constants of the mullite solid solution is not an unequivocal guide to composition since mullites at one composition produced at different temperatures show differences in spacing, no doubt reflecting Al-Si ordering phenomena. The possibility of quartz and corundum being the stable assemblage at some low temperatures and pressures cannot be ruled out. A new anhydrous phase in the system is described, which was previously thought to be synthetic andalusite; it is probably a new polymorph of the Al2 SiO5 composition with ortho-rhombic unit-cell dimensions a =7.55 A, b =8.27 A, and c = 5.66 A. 相似文献
11.
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
12.
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
13.
ROBERT RUH K. S. MAZDIYASNI P. G. VALENTINE H. O. BIELSTEIN 《Journal of the American Ceramic Society》1984,67(9):190-C
Subsolidus phase relations in the low-Y2 O3 portion of the system ZrO2- Y2 O3 were studied using DTA with fired samples and X-ray phase identification and lattice parameter techniques with quenched samples. Approximately 1.5% Y2 O3 is soluble in monoclinic ZrO2 , a two-phase monoclinic solid solution plus cubic solid solution region exists to ∼7.5% Y2 O3 below ∼500°C, and a two-phase tetragonal solid solution plus cubic solid solution exists from ∼1.5 to 7.5% Y2 O3 from ∼500° to ∼1600°C. At higher Y2 O3 compositions, cubic ZrO2 solid solution occurs. 相似文献
14.
MADELEINE H. WARZEE MARCEL MAURICE FRANZ HALLA WALTER R. RUSTON 《Journal of the American Ceramic Society》1965,48(1):15-17
In the binary system PbO–Laz O3 only one compound, 4PbO.La2 O3 , 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 La2 O3 , corresponding to half the a parameter of the C form of La2 O3 . The solid solutions existing between the compositions La2 O3 –2Pb0 and pure La2 O3 have a cubic face–centered lattice and obey Vegard's rule. The systems of PbO with Sm2 O3 and Gd2 O8 are quite similar to that with La2 O3 . The compound Sm2 O3 .4Pb0 decomposes at 1000°C with evaporation of PbO; Sm2 O3 remains in the B modification. 相似文献
15.
Jin-Ho Lee Masatomo Yashima Masato Kakihana Masahiro Yoshimura 《Journal of the American Ceramic Society》1998,81(4):894-900
The phase equilibria in the Y2 O3 -Nb2 O5 system have been studied at temperatures of 1500° and 1700°C in the compositional region of 0-50 mol% Nb2 O5 . The solubility limits of the C-type Y2 O3 cubic phase and the YNbO4 monoclinic phase are 2.5 (±1.0) mol% Nb2 O5 and 0.2 (±0.4) mol% Y2 O3 , respectively, at 1700°C. The fluorite (F) single phase exists in the region of 20.1-27.7 mol% Nb2 O5 at 1700°C, and in the region of 21.1-27.0 mol% Nb2 O5 at 1500°C, respectively. Conductivity of the Y2 O3 - x mol% Nb2 O5 system increases as the value of x increases, to a maximum at x = 20 in the compositional region of 0 ≤ x ≤ 20, as a result of the increase in the fraction of F phase. In the F single-phase region, the conductivity decreases in the region of 20-25 mol% Nb2 O5 , because of the decrease in the content of oxygen vacancies, whereas the conductivity at x = 27 is larger than that at x = 25. The conductivity decreases as the value of x increases in the region of 27.5 ≤ x ≤ 50, because of the decrease in the fraction of F. The 20 mol% Nb2 O5 sample exhibits the highest conductivity and a very wide range of ionic domain, at least up to log p O 2 =−20 (where p O 2 is given in units of atm), which indicates practical usefulness as an ionic conductor. 相似文献
16.
VICTOR J. TENNERY KENNETH W. HANG RICHARD E. NOVAK 《Journal of the American Ceramic Society》1968,51(12):671-674
Extensive solid solution was observed in the system Pb(Sc1/2 /,Nb1/2 ,)1-x ,Tix ,O3 . In the range 0 ≤ x ≤ 0.425 a rhombohedral ferroelectric phase was stable at 25° C. In the range 0.45 ≤ x ≤ 1.00 a tetragonal ferroelectric phase was stable at this temperature. The phase diagram of the system below 500° C strongly resembles that of PbZrO3 −PbTiO3 . The compound Pb(Sc1/2 Nb1/2 )O3 exhibited rhombohedral perovskite cell symmetry below the ferroelectric ↔ paraelectric transition temperature, and the angle a was acute. The radial coupling coefficient was 0.46 for the composition Sc1/2 Nb1/2 )0.575 Ti0.4250 O3 . At 25°C this composition consisted primarily of the rhombohedral phase with a small amount of the tetragonal phase present. The ferroelectric ↔ paraelectric transition occurred over a temperature range in the rhombohedral phase field. The spontaneous polarization was finite at temperatures considerably above the temperature of the permittivity maximum for a given rhombohedral solid solution. 相似文献
17.
The Bi2 O3 -PbO phase diagram was determined using differential thermal analysis and both room- and high-temperature X-ray powder diffraction. The phase diagram contains a single eutectic at 73 mol% PbO and 635°C. A body-centered cubic solid solution exists above ∼600°C within a composition range of 30 to 65 mol% PbO. The compounds α-Bi2 O3 , σ5-Bi2 O3 , and γ-PbO (litharge) have wide solubility ranges. Four compounds, 6Bi2 O3 ·PbO, 3Bi2 O3 ·2PbO, 4Bi2 O3 ,5PbO, and Bi2 O3 ·3PbO, are formed in this system and the previously unreported X-ray diffraction patterns of the latter three compounds are reported. Diffraction patterns for some of these mixed oxides have been observed in ZnO-based varistors grown using Bi2 O3 and PbO as sintering aids. 相似文献
18.
Measurements were made of temperature and ternary composition for coexisting liquid and crystalline phases on the air isobar in the system Fe2 O3 -Fe3 O4 -YFeO3 with particular regard to the stability range and compositional limits of yttrium iron garnet. Phase equilibrium relations were determined by conventional quenching techniques combined with measurements of loss in weight at the reaction temperature to locate true ternary compositions. The intersection of the air isobar with the ternary univariant boundary curve for coexisting magnetite, garnet, and liquid phases results in a eutectic-type situation at the composition Y0.27 Fe1.73 O2.87 and 1469°± 2°C. A similar intersection of the isobar with the boundary curve for coexisting garnet, orthoferrite, and liquid phases gives rise to a peritectic-type reaction at 1555° 3°C. and Y0.44 Fe1.56 O2.89 The yttrium iron garnet crystallizing from liquids within these temperature and composition limits contains up to 0.5 mole % iron oxide in excess of the stoichiometric formula in terms of the starting composition 37.5 mole % Y2 O3 , 62.5 mole % Fe2 O3 . At 1470° C. the garnet phase in equilibrium with oxide liquid contains 2 mole % FeO in solid solution. The small solubility of excess of iron oxide and partial reduction of the garnet phase in air are unavoidable during equilibrium growth from the melt. 相似文献
19.
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
20.
The phase relations in the systems MgO-Y2 O3 -ZrO2 and CaO-MgO-ZrO2 were established at 1220° and 1420°C. The system MgO-Y2 O3 -ZrO2 possesses a much-larger cubic ZrO2 solid solution phase field than the system CaO-MgO-ZrO2 at both temperatures. The ordered δ phase (Zr3 Y4 O12 ) was found to be stable in the system ZrO2 -Y2 O3 at 1220°C. Two ordered phases φ1 (CaZr4 O9 ) and φ2 (Ca6 Zr19 O44 ) were stable at 1220°C in the system ZrO2 -CaO. At 1420°C no ordered phase appears in either system, in agreement with the previously determined temperature limits of the stability for the δ, φ1 , and φ2 phases. The existence of the compound Mg3 Yz O6 could not be confirmed. 相似文献