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1.
Phase equilibria of the La2 O3 –SrO–CuO system have been determined at 950°C at 30 kbar (3 GPa). Stable phases at the apexes of the ternary phase diagram are CuO, La2 O3 , and SrO. Stable intermediate phases are La2 , CuO4 and La2 Cu2 O5 in the LaO1.5 –CuO binary and Sr2 CuO3 , SrCuO2 , and Sr14 Cu24 O41 in the CuO–SrO binary. The La2– x Sr x -CuO4–δ solid solution is stable for 0.00 is ≤ x ≤ 1.29, the La2– x Sr1+ x Cu2 O6+δ solid solution is stable for 0.03 ≤ x ≤0.20, the La2– x Sr x Cu2 O5–δ solid solution is stable for 0.00 ≤ x ≤1.08, and the La x Sr14– x Cu24 O41 solid solution is stable for 0.00 ≤ x ≤ 6.15. The 30 kbar phase diagram differs from the 1 atm (0.1 MPa) and 10 kbar (1 GPa) results principally in the absence of La1– x Sr2+ x Cu2 O5.5+δ as a stable phase and the extended range of the La2– x Sr x Cu2 O5–δ solid solution at 30 kbar. 相似文献
2.
Subsolidus phase relations in the La2 O3 –BaO–CuO system were studied at 950°C. Three previously reported binary compounds exist (La2 CuO4 , BaLa2 O4 , and BaCuO2 ) and five previously reported ternary phases occur (La2-x Bax CuO4-(x/2)+δ , La4-2x Ba2+2x Cu2-x O10-2x , La2-x Ba1+x Cu2 O6-(x-2) , La3-x Ba3+x Cu6 O14±δ , and La4 BaCu5 O13+δ ). Of the seven phases in the diagram, all but BaLa2 O4 , BaCuO2 , and La4 BaCu5 O13+δ were shown to exhibit significant ranges of solubility. The diagram is important in that both >30 K (La2-x Bax CuO4-(x/2)+δ ) and >90 K (La3-x Ba3+x Cu6 O14+δ , x=1) superconductors occur. 相似文献
3.
The phase diagram for the CuO-rich part of the La2 O3 ─CuO join was redetermined. La2 Cu2 O5 was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu7 O19 had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La2 O3 ─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La1.9 Ca1.1 Cu2 O5.9 and LaCa2 Cu3 O8.6 , were stable at these temperatures, with three binary phases, Ca2 CuO3 , CaCu2 O3 , and La2 CuO4 . La2 Cu2 O5 and La8 Cu7 O19 were stable only at 1020°C, and did not support solid-solution formation. 相似文献
4.
Anita Fossdal Mari-Ann Einarsrud Tor Grande 《Journal of the American Ceramic Society》2005,88(7):1988-1991
The phase relations in the pseudo-ternary system La2 O3 –SrO–Fe2 O3 have been investigated in air. Isothermal sections at 1100° and 1300°C are presented based on X-ray diffraction and thermal analysis of annealed samples. Extended solid solubility was observed for the compounds Sr n +1− v La v Fe n O3 n +1−δ ( n =1, 2, 3, and ∞) and Sr1− x La x Fe12 O19 , while only limited solubility of La in Sr4− z La z Fe6 O13±δ was observed. At high Fe2 O3 content, a liquid with low La2 O3 content was stable at 1300°C. 相似文献
5.
P. K. GALLAGHER D. W. JOHNSON JR. E. M. VOGEL 《Journal of the American Ceramic Society》1977,60(1-2):28-31
Samples of LaMn1-x Cux O3-y in the range 0≤x≤0.8 were prepared from freeze-dried solutions of the nitrates. Samples with x≤0.6 were single-phase perovskites. At higher values of x , the samples contained La2 CuO4 and CuO as well as the perovskite phase. Samples of LaMn1−x ,Cux ,O3−y supported on ceramic monoliths or when mixed with powdered A12 O3 exhibit catalytic activity for the oxidation of CO. Greatest activity is shown for 0.4≤x≤0.7. Although the catalysts are severely poisoned by SO2 , 2% H2 O in the gas stream causes only slight deactivation. Activities of other oxide catalysts were also measured and compared. Rate constants per unit surface area at 200° to 400°C follow the order Co3 O4 >Pt>LaMn1−x Cux O3−y (0.4≤x≤0.7)>copper chromite>La1−x Srx ,MnO3 ≤ other substituted LaMnO3 materials, CuO, or La2 CuO4 . The perovskite catalyst is more stable than Co3 O4 or copper chromite when heated in 10% H2 + 90% N2 . 相似文献
6.
Winnie Wong-Ng Lawrence P. Cook Boris Paretzkin Michael D. Hill Judith K. Stalick 《Journal of the American Ceramic Society》1994,77(9):2354-2362
Crystal chemistry and subsolidus phase equilibrium studies of the Ba-Nd-Cu-O system near the CuO and Nd2 O3 corners have been carried cut at 950°C in air. Two solid-solution series have been identified in the Ba-Nd-Cu-O system. The first series involves the high- T c superconductor phase, and has the formula Ba2–x Nd1+x Cu3 O6+z , where × < ≅ 0.7. At the ideal compound stoichiometry of Ba2 NdCu3 O6+z , the transformation from the high- T c orthorhombic to tetragonal phase occurs at 550°–575°C in air. This temperature varies as a function of composition, and at x ≅ 0.2 to 0.3 it occurs at 950°C. The second solid solution is the non-superconducting "brown phase" represented by Ba2+2x -Nd4–2x Cu2–x O10–2z 0 ≤ x ≤ 0.1. Preliminary phase diagrams of the BaO–Nd2 O3 and Nd2 O3 –CuOx systems are also presented. Standard X-ray diffraction patterns of BaNd2 –CuO5 and (Nd1.9 Ca0.1 )CuO4–z are provided. 相似文献
7.
C. N. Pleczulewski J. E. McAdams T. O. Mason 《Journal of the American Ceramic Society》1990,73(10):3088-3090
Phase composition and compatibilites at 930° to 950°C were determined for the system Eu2 O3 –BaO–CuO in air. The binary compound Eu2 CuO4 dissolves Ba to the extent 0 x 0.02 in Eu2-x Bax CuO4 , whereas the other binary compounds, Eu2 BaO4 and BaCuO2 , do not exhibit solid solubility. Three ternary compounds were obtained, Eu2 BaCuO5 and two solid solution phases. The first contains the 90 K '123' superconductor and has solubility limits represented by Eu1+x Ba2-x Cu3 O7±y , where 0 x 0.5. The second has a solubility limit represented as Eu1+x Ba8-x Cu4 Oy , where 0 x 0.44. The limited solid solution range of this phase provides insight concerning the probable solid solution range of the analogous phase in the Y2 O3 -BaO-CuO system. 相似文献
8.
Anurag Dwivedi Mark A. Rodriguez Alastair N. Cormack 《Journal of the American Ceramic Society》1992,75(7):1993-1996
Compositions of La1- x Ba x CuO3 , where x ranges from 0.0 to 0.5, were fired in air, oxygen-enriched air, and oxygen. Studies show that BaO cannot make a solid solution with LaCuO3 without changing the basic structure. The resulting phases, in all attempts, were the binary compounds La2 CuO4 , La1- x Ba x CuO3-δ ( x = 0.2 to 0.5), or their mixtures. All samples showed metallic conductivity. Extra oxygen in the reaction atmosphere appeared to encourage the formation of the LaCuO3 -based phases of La1- x Ba x CuO3-δ ( x = 0.2 or 0.5). We provide a defect-chemical and thermodynamical explanation for this observation. 相似文献
9.
Chemical Compatibility between Strontium-Doped Lanthanum Manganite and Yttria-Stabilized Zirconia 总被引:1,自引:0,他引:1
Guido Stochniol Emmanuel Syskakis Aristides Naoumidis 《Journal of the American Ceramic Society》1995,78(4):929-932
Equimolar powder mixtures and multilayer pellets of single-phase Sr-doped lanthanum manganite perovskite materials Lay-x Srx MnO3 with La content y = 1 and 0.95 and Sr content 0 ≤ x ≤ 0.5 were annealed in air with 8 mol% Y2 O3 -ZrO2 at 1470 K, up to 400 h and at 1670 K. up to 200 h. X-ray diffraction and electron probe microanalysis confirmed the formation of La2 Zr2 O7 or SrZrO3 depending on the composition of the perovskites. No reaction products could be detected for La0.95-x Sr x MnO3 with 0.2 ≤ x ≤ 0.4 after annealing for 400 h at 1470 K, and for the perovskite La0.65 Sr0.3 MnO3 even after annealing for 200 h at 1670 K. The results demonstrate the improved chemical compatibility of La-deficient perovskites against reaction with zirconia and can provide a basis for the selection of a sufficiently chemically stable material for the air electrode of solid oxide fuel cells. 相似文献
10.
Bryan C. Hendrix Teruyoshi Abe Janine C. Borofka Pin-Chin Wang John K. Tien 《Journal of the American Ceramic Society》1993,76(4):1008-1010
The response of ceramic superconductors and ceramic composites to compressive stresses at high temperatures has been examined. Monolithic YBa2 Cu3 O7-δ and composite YBa2 Cu3 O7 -δ6 /Ag were tested at constant true strain rates from 10-6 to 10-3 s-1 at temperatures from 800° to 950°C. Fine-grained monolithic YBa2 Cu3 O7-δ appears to have a regime of superplastic deformation between temperatures of 850° and 950°C at strain rates from 10-6 to 10-4 S-1 . The addition of 20 vol% Ag to a coarser-grained material enhances the ductility of the ceramic and lowers the flow stress by a factor of 3 to 10. However, there is no evidence of superplasticity in the composite material in the range of temperature and strain rate where it was tested. 相似文献
11.
Chung-Yi Tsai Anthony G. Dixon Yi Hua Ma William R. Moser Marina R. Pascucci 《Journal of the American Ceramic Society》1998,81(6):1437-1444
La1- x A' x Fe0.8 Co0.2 O3-δ (A'= Ca, Sr, Ba) perovskite powders were synthesized to attain the desired properties of high O2 flux and stability under reducing conditions. Steady-state oxygen permeation rates for La1- x A' x Fe0.8 -Co0.2 O3-δ perovskite membranes in nonreacting experiments with air on one side and helium on the other side of the membrane were in the order A' x = Ba0.8 > Ba0.6 > Ca0.6 > Sr0.6 . Partial oxidation of methane to syngas (CO + H2 ) was performed in a dense La0.2 Ba0.8 Fe0.8 Co0.2 O3-δ membrane reactor at 850°C in which oxygen was separated from air and simultaneously fed into the methane stream. The reducing atmosphere affected the membrane reaction-side surface while barium enrichment occurred on the air-side surface. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h. 相似文献
12.
Michael Rozumek Peter Majewski Heike Schluckwerder Fritz Aldinger Klaus Künstler Gerhard Tomandl 《Journal of the American Ceramic Society》2004,87(9):1795-1798
Ceramics of the melilite-type compound La1+ x Sr1− x Ga3 O7−δ were prepared by conventional ceramic processing. Samples prepared represented the entire homogeneity region of the phase (i.e., x =−0.15 to 0.60). Electrochemical characterization under variable temperature and atmospheric conditions in the vicinity of air entailed four-point direct-current conductivity measurements and electromotive force measurements. La1+ x Sr1− x Ga3 O7−δ samples exhibited a p -type behavior with generally increased conductivity with increased substitution of lanthanum for strontium, which reached a saturation value of ∼10−1 S·cm−1 at 950°C. 相似文献
13.
David H. Chmielewski Kenneth H. Sandhage 《Journal of the American Ceramic Society》1995,78(9):2504-2512
Bi2 Sr2 Ca2 Cu2 O8±δ -type compound thick films were exposed to oxygen-argon-gas mixtures (1% to 20% oxygen gas) at elevated pressures (up to 207 MPa) and temperatures (500° to 940°C) for times ranging from 5 to 96 h. At a sufficiently high oxygen fugacity and temperature, Bi2 Sr2 Ca1 Cu2 O8±δ decomposed via a solid-state reaction. Room-temperature X-ray diffractometry and electron probe microanalysis of decomposed films revealed the presence of Bi2 (Sr,Ca)2 -Cu1 O6±θ ro-type compound, Bi2 Sr2 ,Ca1 O8±δ -type compound, and CuO. Bi2 Sr2 Ca1 Cu2 O8±δ decomposition was accompanied by a modest weight gain, which was consistent with an oxidation reaction. The solid-state decomposition reaction could be reversed by heat treatment of decomposed films at 860°C in pure, flowing oxygen at ambient pressure. 相似文献
14.
JUNICHIRO MIZUSAKI TADASHI SASAMOTO† W. ROGER CANNON‡ H. KENT BOWEN 《Journal of the American Ceramic Society》1983,66(4):247-252
The electrical conductivity and Seebeck coefficients of La1-x Sr x FeO3 ( x =0.1, 0.25) were measured as a function of oxygen partial pressure, PO2 , at T =900° to 1300°C. The electrical conduction was p type in the higher PO2 range, and n type in the lower P O2 range. The Seebeck coefficient indicated that the conduction was due to electron hopping between Fe× Fe and FeFe , in the higher PO2 range and electron hopping between Fe'Fe and Fe× Fe in the lower range. The carrier concentrations were calculated from the values of electrical conductivity and Seebeck coefficient. From the P O2 dependences of the carrier concentrations, the defect structure of La1-x Sr x FeO3 was determined. It was found that the electrical properties can be described by considering the imperfections SrLa , Vo , FeFe , and Fe'Fe . 相似文献
15.
The stability of the (Bi,Pb)2 Sr2 Ca2 Cu3 O10±δ -type compound has been evaluated under conditions of elevated temperature (500°-860°C) and elevated oxygen fugacity (i.e., in O2 /Ar gas mixtures containing ≤120% O2 , at total pressures of 5207 MPa). At sufficiently high oxygen fugacities and temperatures, the (Bi,Pb)2 Sr2 Ca2 Cu3 O10±δ -type compound transformed into a mixture of a strontium-rich (Bi,Pb)1 -(Sr,Ca,Cu)2 Oy -type compound, a calcium-rich (Bi,Pb)2 -(Sr,Ca,Cu)2 Oy -type compound, CuO, and a small amount of (Sr,Ca)O. The decomposition of the (Bi,Pb)2 Sr2 Ca2 -Cu3 O10±δ -type compound was accompanied by a 2%-3% weight gain, which was consistent with an oxidation reaction. The conditions of oxygen fugacity and temperature leading to decomposition, and the resulting decomposition products, are compared for the (Bi,Pb)2 Sr2 Ca2 Cu2 O10±δ -type and Bi2 Sr2 Ca1 Cu2 O8±Ψ -type compounds. 相似文献
16.
Carlos E. Bamberger Tamara J. Havedock Otto C. Kopp† 《Journal of the American Ceramic Society》1994,77(6):1659-1661
The ternary system SrO-CeO2 -TiO2 was investigated using X-ray diffractometry. The formation of a new compound, Sr2 Ce2 Ti5 O16 , was established, and its compatibilities with SrO, SrCeO3 , and SrTiO3 were studied. The results revealed the existence of a series of compounds Sr6–12x Ce6x Ti5 O16 and solid solutions Sr2+n Ce2 Ti5+n O16+3n ( n ≤ 6). 相似文献
17.
Steven P. Simner Michael D. Anderson Jeffry W. Stevenson 《Journal of the American Ceramic Society》2004,87(8):1471-1476
(La0.8 Sr0.2 )0.98 Fe0.98 Cu0.02 O3−δ can be sintered directly onto YSZ (without the need for a protective ceria interlayer). Though subject to an extended "burn-in" period (∼200 h), anode-supported YSZ cells using the Cu-doped LSF achieve power densities ranging from 1.3 to 1.7 W/cm2 at 750°C and 0.7 V. These cells have also demonstrated 500 h of stable performance. The results are somewhat surprising given that XRD indicates an interaction between (La0.8 Sr0.2 )0.98 Fe0.98 -Cu0.02 O3−δ and YSZ resulting in the formation of strontium zirconate and/or monoclinic zirconia. The amount and type of reaction product was found to be dependent on cathode and electrolyte powder precalcination temperatures. 相似文献
18.
The influence of Nd2 O3 doping on the reaction process and sintering behavior of BaCeO3 is investigated. Formation of BaCeO3 is initiated at 800°C and completed at 1000°C. When Nd2 O3 is added to the starting materials, the formation of BaCe1–x Ndx O3–δ is delayed and the temperature for complete reaction is increased to 1100°C. Only a BaCe1-x Ndx O3–δ solid solution with an orthorhombic crystal structure is present in the specimens for x ≤ 0.1. A secondary phase rich in Ce and Nd is formed within grains and at grain boundaries, when the Nd2 O3 content is greater than the solubility limit (x ≥ 0.2). Pure BaCeO3 is difficult to sinter, even at 1500°C, and only a porous microstructure could be obtained. However, doping BaCeO3 with Nd2 O3 markedly enhances its sinterability. The enhancement of the sinterability of Nd2 O3 -doped specimens at x ≤ 0.1 is attributed to the increase in the concentration of oxygen ion vacancies, which increases the diffusion rate. At x ≥ 0.2, the grain size is abnormally coarsened, which is caused by the formation of a liquid phase. While this liquid phase accelerates sintering, its beneficial effect on densification is counteracted by the segregation of the secondary grain-boundary phase which inhibits sintering. 相似文献
19.
Sara Bals Jo Verbeeck Gustaaf Van Tendeloo Yi-Lin Liu Jean-Claude Grivel 《Journal of the American Ceramic Society》2005,88(2):431-436
The microstructural and compositional evolution during initial annealing of a superconducting (Bi,Pb)2 Sr2 Ca2 Cu3 O10+δ /Ag tape is studied using quantitative transmission electron microscopy. Special attention is devoted to the occurrence of Pb-rich liquids, which are crucial for the Bi2 Sr2 CaCu2 O8+δ to (Bi,Pb)2 Sr2 Ca2 Cu3 O10+δ transformation. Ca and/or Pb-rich (Bi,Pb)2 Sr2 CaCu2 O8+δ grains dissolve into a liquid, which reacts with Ca-rich phases to increase the liquid's Ca-content. This leads to (Bi,Pb)2 Sr2 Ca2 Cu3 O10+δ formation. Apparently, a Ca/Sr ratio of around 1 is sufficient to keep (Bi,Pb)2 Sr2 Ca2 Cu3 O10+δ nucleation going. It is confirmed that Ag particles are transported from the Ag-sheath into the oxide core by the liquid and not by mechanical treatment of the tape. 相似文献
20.
Danjela Kuer Darko Hanel Janez Holc Marko Hrovat Drago Kolar 《Journal of the American Ceramic Society》2001,84(5):1148-1154
La1− y Sr y Fe1− x Al x O3−δ perovskites were studied as potential materials for solid-oxide fuel cell (SOFC) cathodes. The phase relations in the LaFeO3 –SrFeO3−δ –LaAlO3 system were investigated by X-ray powder diffraction analysis. The defect structure of the La1− y Sr y Fe1− x Al x O3−δ perovskites was investigated by Mössbauer spectroscopy and weight-loss analysis. Relations between the nonstoichiometry and the conductivity of the La1− y Sr y Fe1− x Al x O3−δ perovskites were investigated. The incorporation of aluminum ( x ) into LaFe1− x Alx O3 was found to have no influence on the defect structure but to decrease the conductivity. The incorporation of strontium ( y ) into La1− y Sr y Fe1− x Al x O3−δ promotes the formation of anion vacancies and Fe4+ that lead to higher conductivity. 相似文献