共查询到20条相似文献,搜索用时 31 毫秒
1.
A microprobe study of interdiffusion between 1033° and 1238°C in the system SrF2 -BaF2 was conducted using single crystals. The interdiffusion coefficient, D , generally decreased with increasing SrF2 concentration, but the composition dependence of D decreased with decreasing temperature. Extrapolation of D values to infinite dilution allowed the impurity cation self- diffusion coefficients:
The values for DSr in BaF2 are in excellent agreement with tracer results. An analysis of the activation energies for cations diffusing in alkaline-earth fluorides shows a direct correlation between constriction ratio and migration energy for a single ion diffusing in different fluorides. An apparent anomaly arises when attempting to correlate migration energy with structural information for different cations diffusing in the same fluoride. 相似文献
The values for D
2.
WILLIAM C. HAGEL 《Journal of the American Ceramic Society》1965,48(2):70-75
Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a Pt10Rh chamber, and spheres of α-Cr2 O3 containing three or less grains was determined from 1100° to 1450°C. Isotope equilibrium on crystal surfaces appears to be quickly established, and the rate-determining factor is self-diffusion conforming to the relation D = 15.9 exp(-101,000/ RT) cm2 sec−1 . Changing sphere diameters caused no detectable variation in diffusion coefficients. Anions are the much slower diffusing species in this oxide. 相似文献
3.
The composition of the diffusing unit for silicon was determined for the system Na2 O-CaO-SiO2 at 1200°C from an analysis of the concentration distributions in interdiffusion using a multiatomic ion model described in terms of self-diffusion coefficients of constituent elements. The results indicated that silicon diffuses in a 7-membered ring form and that the number of Si atoms in the silicate ion is not less than 35. 相似文献
4.
Samples of 65 μm-grain-size AL2 O3 containing 0.05 wt% Mg and 40 μm-grain-size AL2 O3 containing 0.13 wt% Mg, both MgO-saturated, undergo compressive deformation in the range 1580° to 1800°C with results interpreted as diffusional creep rate-limited by grain-boundary diffusion with the Coble boundary-diffusion model giving
A lower deformation rate for an unsaturated composition indicates that MgO additions enhance grain-boundary diffusion. 相似文献
A lower deformation rate for an unsaturated composition indicates that MgO additions enhance grain-boundary diffusion. 相似文献
5.
Ken Ando Yasumichi Oishi Hiroyuki Hase Koichi Kitazawa 《Journal of the American Ceramic Society》1983,66(12):222-C
Self-diffusion coefficients of the oxygen ion in single-crystal Y2 O3 were determined by the gas-solid isotope exchange technique. The results in the range 1100° to 1500°C are described by D=7.3 X 10-6 exp [-19l(kJ/mol)/RT] cm2 /s. Comparison of the results with those for oxides with the fluorite-type structure indicates that the regularly arranged vacant anion sites in the C-type structure do not contribute eflectively to oxygen ion diffusion . 相似文献
6.
High-temperature diffusion kinetics and phase relations between couples of fused SiO2 or cristobalite and sapphire or mullite were investigated in air and in helium. Subsolidus liquid formation between sapphire and cristobalite indicates the existence of a metastable system without mullite. A liquid phase is considered to be essential for the nucleation of mullite. The growth rate of mullite exceeded its dissolution rate in semi-infinite fused-SiO2 -sapphire couples above 1634°C. The inter-facial liquid compositions provided data for a minor revision of the mullite liquidus curve. Diffusion coefficients calculated from the Al profiles vary greatly with concentration and temperature, resulting in a large range of values for apparent activation energy, which decreases with increasing Al2 O3 content (∼310 to ∼60 kcal/mol for ∼4 to ∼22 wt% Al2 O3 ). The diffusion process in the liquid is considered to be cooperative movement of oxygen-containing Al and Si complexes whose nature changes with composition and temperature; this change in the diffusing species contributes to the range in the values of experimental apparent activation energies. 相似文献
7.
Surface, grain-boundary, and volume inter diffusion coefficients for the NiO-Al2 O3 system were measured concurrently by using a diffusion couple consisting of an A12 O3 bicrystal and an NiO single crystal. The A12 O3 bicrystals having various tilt angles were fabricated by firing 2 single crystals to be joined in an H2 atmosphere at 1800°C for 30 h. Diffusion profiles over the surface, along the grain boundary, and in the bulk of the bicrystal were determined with an electron probe microanalyzer. Mathematical analysis of the diffusion profiles gives D s = 7.41×10-2 exp (-35,200/ RT ), D gb = 2.14×10-1 exp (-63,100/ RT ) (tilt angle =30°), and D v = 1.26×104 exp (-104,000/ RT ). The grain-boundary diffusion coefficient increases with the mismatch at the boundary. 相似文献
8.
Chemical diffusion coefficients for Si were measured in potassium silicate compositions containing from 64 to 85 wt% SiO2 ; unidirectional diffusion couples were heated for 0.1 to 720 h at 600° to 1400°C. The diffusion coefficients, which were calculated by the Boltzmann-Matano method, are described for a silicate containing 70 wt% SiO2 by:
The diffusion coefficients decreased with increasing O2 pressure. Below 800°C, the coefficients decreased with increasing SiO2 concentration; above 800°C, their dependence on SiO2 concentration was too weak to detect by the methods used. On the basis of a simple structural model for the glass, it was possible, from a phenomenological analysis of the diffusion, to establish a relation between the oxygen self-diffusion coefficient and the chemical diffusion coefficient for a given composition. 相似文献
The diffusion coefficients decreased with increasing O
9.
Activities of NiO were measured in the oxide and spinel solutions of the system MnO–NiO–Al2 O3 at 1300° and 1400° C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity–composition relations in spinel solid solutions at 1300° and 1400°C. The MnAl2 O4 –NiAl2 O4 solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl2 O4 from its oxide components (MnO + Al2 O3 ) at 1300° and 1400°C is calculated to be −24.97 and −26.56 kJ. mol−1 , respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models. 相似文献
10.
Equilibrium phase diagrams for the systems MgCl2 -MgF2 , CaCl2 -MgF2 and NaCl-MgF2 were determined by differential thermal analysis, thermal analysis, and temperature-composition equilibrium techniques. Simple eutectics were observed at 78.0±0.5 mol% MgCl2 and 628°±2°C in the MgCl2 -MgF2 system, at 87.5±0.5 mol% CaCl2 and 694°±2°C in the CaCl2 -MgF2 system, and at 95.5±0.5 mol% NaCl and 786°±3°C in the NaCl-MgF2 system. The phase diagrams determined for these systems were compared with phase diagrams that were computed using Temkin's model. The phase diagrams of the CaCl2 -MgF2 and NaCl-MgF2 systems were also compared with diagrams that were computed using the expression suggested by Flood et al. for reciprocal systems. The experimentally determined and computed phase diagrams agreed for the MgCl2 -MgF2 system but not for the CaCl2 -MgF2 and NaCl-MgF2 systems. 相似文献
11.
Phase equilibria in the system MnO–CoO–Cr2 O3 were investigated at 1300°C under controlled oxygen partial pressures by using the gas equilibration technique. The CoO activities in various phase assemblages of the system were measured by determining the partial pressures of oxygen in the gas phase for coexistence with metallic cobalt. The activity data revealed that at 1300°C, MnO–CoO and MnCr2 O4 –CoCr2 O4 solid solutions exhibit mild positive departures from ideal behavior. The activities in the stoichiometric spinel solutions were found to be in good agreement with those predicted from a model based on cation distribution equilibria. The standard free energy of formation of the compound CoCr2 O4 from its oxide components at 1300°C was determined as −37 636 J/mol, while that for MnCr2 O4 was found as −44 316 J/mol. 相似文献
12.
Stoichiometric NiAl2 O4 , CuAl2 O4 , and ZnAl2 O4 spinels were prepared and equilibrated at temperatures from 600° to 1400°C. The parameters u and x , denoting the oxygen position and fraction of divalent cations on tetrahedral sites, respectively, were determined from a detailed X-ray diffraction analysis. In NiAl2 O4 , x increased from 0.07 at 595° to 0.26 at 1391°C; in CuAl2 O4 , x decreased from 0.68 at 613° to 0.64 at 1195°C; and in ZnAl2 O4 , x decreased from 0.96 at 905° to 0.94 at 1197°C. The form of the temperature dependence of x could not be described using theoretically based equations advanced in the literature. A more general equation which allows for a non-distributional contribution to the configurational entropy was derived and observed to properly describe the temperature dependence; the results indicate that short-range order is of definite significance in these intermediate aluminate spinels. 相似文献
13.
R. J. BRATTON 《Journal of the American Ceramic Society》1971,54(3):141-143
The sintering and grain-growth kinetics of finely divided MgAl2 O4 were determined from 1300° to 1600°C for densities up to 96% of theoretical. These results show that sintering is governed by volume diffusion and that the temperature dependence of the diffusivities is 157 exp [(-118 kcal/mol)/ RT ] cm2 /s. Grain growth follows the expression ( G 2 - G 0 2 )= Kt , where K =51.3 exp [(-110 kcal/mol)/ RT ] cm2 /s. 相似文献
14.
Studies of the oxidation of Gd and Dy at P O2 's from 10−0.3 to 10−14.5 atm and temperatures from 727° to 1327°C indicate both semiconducting and ionic-conducting domains in the sesquioxides formed. At higher temperatures, where dense coarsegrained oxide layers developed, the rate of oxidation in the high- P 02 semiconducting domain yielded oxygen diffusion coefficients in Dy2 O3 in excellent agreement with literature values derived from oxidation of partially reduced oxide single crystals. Under the same conditions, the oxidation of Gd yielded oxygen diffusion coefficients in cubic Gd2 O3 which are considerably below literature values for monoclinic single-crystal Gd2 O3 . At lower temperatures, porous scales were formed, and apparent diffusion coefficients derived from oxidation rates show a smaller temperature dependence than the high-temperature data. At low P O2 , the oxides behave as ionic conductors, and metal oxidation rates result in estimates of the electronic contribution to the electrical conductivity of the order of 10−6 to 10−7 Ω−1 cm−1 . 相似文献
15.
The subsolidus miscibility gap for the TiO2 -SnO2 system was redetermined. The critical temperature, 1430°C, is intermediate between that determined by Padurow, 1330°C, and that determined by Garcia and Speidel, 1475°C. Although the phase boundary is slightly asymmetric (the critical composition occurs at 47 mol% TiO2 ), it fits the regular-solution model down to 1200°C. Calculations of the coherent spinodal using the regular-solution model indicated depression of the spinodal below Tc , by 105°, 310°, and 387° for composition fluctuations along the [001], <101>, and <100> directions, respectively. These depressions of the spinodal are much greater than those calculated by Stubican and Schultz; this discrepancy is believed to result from an error in the latter workers' calculations. During the present work, positive deviations from Vegard's law were found in this system. Both the magnitude and the sign of the deviation can be predicted using a theory based on nonlinear second-order elasticity. 相似文献
16.
Stephan Senz reas Graff Werner Blum Dietrich Hesse Hans-Peter Abicht 《Journal of the American Ceramic Society》1998,81(5):1317-1321
Fresnoite grows at 700° and 800°C, and Ba6 Ti7 O40 grows at 1200°C with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured fresnoite is formed at higher temperatures. The SiO2 films react with the BaTiO3 crystals, forming the phases Ba2 TiSi2 O8 (fresnoite) and Ba6 Ti17 O40 . At 700° and 800°C, both phases grow with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured polycrystalline phases are formed at higher temperatures. 相似文献
17.
R. J. Cava Eva M. Vogel David W. Johnson Jr. 《Journal of the American Ceramic Society》1982,65(9):c157-c159
The reported activation volume for sodium ion transport in the fast-ion conductor Na3 Zr2 Si2 PO12 is surprisingly large. Therefore, attempts were made to alter the size of the diffusion channels through partial substitution of As, Ge, Ti, Th, and Hffor the framework cations to decrease geometric structural hinderance of the diffusion process. Sodium ion conductivity is improved at temperatures below 200°C far the Hf substitutions. The existence and electrical properties of the apparently isostructural Na3 Hf2 Si2 PO12 , which has a room-temperature conductivity of 1.0Ω10−3 Ω cm−1 , are reported. 相似文献
18.
Yoshio Sakka Yasumichi Oishi Ken Ando Yoji Ikeda 《Journal of the American Ceramic Society》1993,76(5):1381-1383
Zr–Hf interdiffusion was studied in the temperature range of 1650° to 1850°C in air for polycrystalline fluorite-cubic systems of 90CeO2 ·10(Zr1- x Hf x )O2 and 60CeO2 ·40(Zr1- x Hf x )O2 . Lattice and grain-boundary diffusion parameters were calculated from the Zr–Hf concentration distributions by using the grain-boundary diffusion equation of Oishi and Ichimura. The cation iattice diffusivity was close to that in the fluorite-cubic Y2 O2 -ZrO2 solid solution. 相似文献
19.
Elena R. Andrievskaya Lidiya M. Lopato 《Journal of the American Ceramic Society》1992,75(11):3026-3032
Phase equilibria in the system HfO2 –Y2 O3 –CaO were studied in the temperature range 1250° to 2850°C by both experimental methods (X-ray phase analysis at 20° to 2000°C, petrography, annealing and quenching, differential thermal analysis in He at temperatures to 2500°C, thermal analysis in air using a solar furnace at temperatures to 3000°C, and electron microprobe X-ray analysis) and theoretical means (development of a mathematical model for the liquidus surface by means of the reduced polynomial method). Phase equilibria were determined by the structure of the restricting binary systems. No ternary compounds were found. The liquidus was characterized by the presence of six four-phase, invariant equilibria. Solid solutions were based on monoclinic (M), tetragonal (T), and cubic (F) modifications of HfO2 ; C and H forms of Y2 O3 ; CaO; and CaHfO3 that crystallized in two polymorphous modifications, namely, the cubic and rhombic perovskite-type structure. 相似文献
20.
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