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1.
The phase diagram for the system Bi2O3-B2O3 has been determined experimentally. The melting point of Bi2O3 has been redetermined as 825° C with an estimated overall uncertainty of about ±3°C, and the molal heat of fusion of Bi2O3, calculated from the slope of the liquidus curve, is 2050 cal per mole. The system contains a body-centered cubic phase of approximate composition 12Bi2O3·B2O3, which melts incongruently at 632°C. Four congruently melting compounds exist in the system: 2Bi2O3· B2O3·5B2O3, Bi2O3·3B2O3, and Bi2O3·4B2O3, with melting points, respectively, of 675°, 722°, 708°, and 715°C. The Bi2O3·4B2O3 compound exhibits a sluggish transformation at 696°C. Compositions containing up to 97.5 wt% (85 mole %) Bi2O3 can be partly or totally quenched to glass. Indices of the quenched glasses are greater than 1.74. A region of liquid immiscibility extends at 709°C from almost pure B2O3 to 19.0 mole % Bi2O3. The extent of immiscibility theoretically calculated agrees with the experimentally determined value when 1.20 A is used for the ionic radius of Bi3+.  相似文献   

2.
B. Nayak  D.K. Sahu 《Electrochimica acta》1983,28(10):1335-1338
The emf of cells (A) Pt, H2|HCl(m)|Hg2Cl2, Hg and (C). AgAgCl|HCl(m)|Hg2Cl2, Hg have been measured at intervals of 5°C over the temperature range 5–55°C (278.15–328.15 K) using formamide as the solvent. The molal standard potentials of Hg, Hg2Cl2 electrode, determined on the basis of emf data of cell (A), agree well with those derived from the emf of cell (C) using known values of E0Ag-AgCl reported earlier. Based on emf data of these cells, the standard thermodynamic changes ΔG0, ΔH0 and ΔS0 for the cell reactions as well as the mean molal activity coefficients of HCl at rounded molalities have been determined.  相似文献   

3.
Ceramics with temperature-stable dielectric characteristics have been developed in the system: 0.6[0.85Na0.5Bi0.5TiO3-(0.15-x)Ba0.8Ca0.2TiO3-xBi(Mg0.5Ti0.5)O3]?0.4NaNbO3, x ≤ 0.15. Dielectric measurements exhibited relaxor ferroelectric characteristics with temperature-stable relative permittivity from εr~1330 ± 15% in the temperature range from ?70?°C to 215?°C and tanδ ≤ 0.02 from ?20?°C to 380?°C for x = 0 compositions. For the Bi(Mg0.5Ti0.5)O3 modified compositions the temperature range of stable relative permittivity extended from ?70?°C to 400?°C, with εr ~ 950 ± 15% and tanδ ≤ 0.02 from ?70?°C to 260?°C. Values of dc resistivity were ~ 108 Ω?m at a temperature of 300?°C and the corresponding RC constant values were in the range from 0.40 ? 0.78?s at 300?°C. All ceramic samples exhibited a linear polarisation-electric field response at maximum applied electric field of 5?kV/cm (1?kHz).  相似文献   

4.
Phase relations for the systems ZrO2–WO2–WO3 and HfO2–WO2–WO3 from 1000° to 1700° C were determined by the quenching technique using sealed sample containers. In the system ZrO2–WO3, 1:2 compound, ZrW2O8 forms, having a cubic structure with a= 9.159 A. The ZrW2O8 melts incongruently at 1257°± 3°C to ZrO2 and liquid and has a lower limit of stability at 1105°C, below which ZrO2 and WO3 coexist in equilibrium. One eutectic and one peritectic were established: at 1231°± 3°C and 74 mole % WO3, and at 1257°± 3°C and 71 mole % WO3, respectively. Along the join ZrO2–WO2, no compound formed. Two invariant points were determined: ZrO2, WO2, W, and liquid are in equilibrium at 1430°± 5°C and 76 mole % WO2, whereas WO2, W18O49, W, and liquid coexist at 1530°± 5°C and 89 mole % WO2- Equilibrium relations in the system ZrO2–WO2–WO3 were investigated at four temperatures. At 1200°C, a cubic phase with composition near W20O58 was found; it exists in equilibrium with ZrO2, W18O49, W20O58, and WO3. As the temperature increases, the liquid formed along the ZrO2–WO3 join extends into the ternary system, crosses the join ZrO2–W20O58 at 1300°C, and crosses the join ZrO2–W18O49 at 1400°C. The cubic phase can take more zirconium into its solid solution at 1300° than at 1200°C. At 1500°C, the system can no longer be treated as a simple ternary oxide system because of the presence of metallic tungsten, and equilibrium relations are presented on the basis of the system ZrO2–W–WO3. Phase equilibrium relations in the systems HfO2–WO3, HfO2–WO2, and HfO2–WO2–WO3 in the temperature ranges studied are much like those in the corresponding zirconium system.  相似文献   

5.
The influence of CaF2 on the kinetics of the reaction C+C2S → C3S in five-component diffusion sandwiches (CaOSiO2Al2O3Fe2O3MgO) was determined in the temperature interval 1350°C to 1500°C. With the addition of 0.5% CaF2 to the reacting system the rate of reaction increased by a factor of 2.4 at a reaction temperature of 1350°C, and a factor of 1.2 at 1500°C. Addition of 1% CaF2 raised the reaction rate 2.8 times at 1350°C and 1.7 times at 1500°C. The effect of CaF2 on the rate of C3S formation may be attributed to the fact that the C3S primary field is much wider in the CSCaF2 system than in the CSAF system.  相似文献   

6.
Multiple ion substitutions to Na0.5Bi0.5TiO3 give rise to favourable dielectric properties over the technologically important temperature range ?55?°C to 300?°C. A relative permittivity, εr,?=?1300?±?15% was recorded, with low loss tangent, tanδ?≤?0.025, for temperatures from 310?°C to 0?°C, tanδ increasing to 0.05 at ?55?°C (1?kHz) in the targeted solid solution (1–x)[0.85Na0.5Bi0.5TiO3–0.15Ba0.8Ca0.2Ti1-yZryO3]–xNaNbO3: x?=?0.3, y?=?0.2. The εr-T plots for NaNbO3 contents x?<?0.2 exhibited a frequency-dependent inflection below the temperature of a broad dielectric peak. Higher levels of niobate substitution resulted in a single peak with frequency dispersion, typical of a normal relaxor ferroelectric. Experimental trends in properties suggest that the dielectric inflection is the true relaxor dielectric peak and appears as an inflection due to overlap with an independent broad dielectric peak. Process-related cation and oxygen vacancies and their possible contributions to dielectric properties are discussed.  相似文献   

7.
Li3/8Sr7/16-3x/2LaxZr1/4Nb3/4O3 (x = 0, 0.05, 0.10, 0.15, 0.20) were synthesized using the conventional solid-state reaction method. In order to increase the vacancy concentration, La3+ was doped on the Sr2+ site. Crystal structures of doped samples were characterized by X-ray diffraction. Except, perovskite-type Li3/8Sr7/16-3x/2LaxZr1/4Nb3/4O3 (x = 0, 0.05, 0.10, 0.15) samples were fabricated by heat treatment at 1250 °C, 1275 °C, 1275 °C and 1275 °C, respectively, for 15 h. Lattice sizes decreased with the increase of doping amounts because of the smaller ion radius of La3+ compared to that of Sr2+. Ionic conductivities of the samples were measured by AC impedance spectroscopy. The results showed that the ionic conductivity increases at first and then decreases with raising doping amounts and sintering temperatures. So the optimized composition Li3/8Sr7/16-3x/2LaxZr1/4Nb3/4O3 (x = 0.05) sintered at 1275 °C was selected with the highest total conductivity of 3.33 × 10?5 S cm?1at 30 °C and an activation energy of 0.27 eV. Additionally, potentiostatic polarization test was used to evaluate the electronic conductivity. The optimal composition Li3/8Sr7/16-3x/2LaxZr1/4Nb3/4O3 (x = 0.05) as a possible Li-ion conducting solid electrolyte has an electronic conductivity of only 8.39 × 10?9 S cm?1.  相似文献   

8.
Phase relationships in the system Li2O, B2O3-B2O3 were studied by the quenching method using twenty compositions. The crystalline phases encountered were (a) Li2O, B2O3, which melts congruently at 849°± 2°C., (b) Li2O.-2B2O3, which melts congruently at 917°± 2°C., (c) a new compound, 2Li2O-5B2O3, which melts incongruently at 856°± 2°C. and dissociates below 696°± 4°C., (d) Li2O.3B2O3, which melts incongruently at 834°± 4°C. and dissociates below 595°± 20°C., and (e) probably Li2O.4B2O3, which melts incongruently at 635°± 10°C. Reactions were sluggish at temperatures near 600°C., resulting in metastable relations. Hence phase equilibrium data relating to the lower stability limit of Li2O.3B2O3 and to the upper stability limit of Li2O.4B2O3 are considered to be tentative. Properties of the glasses and crystalline phases were studied. The refractive index of the glasses increased with the addition of Li2O up to 22%, but further additions up to 40% had no substantial effect. Glasses containing less than 30% Li2O were water soluble. Limited data on the density and thermal expansion of the glasses are presented. Li2OB2O3 was euhedral, lath-shaped, length-fast, biaxial negative (2V = 27°), with nα= 1.540, nβ= 1.612, nγ= 1.616. Li2O.2B2O3 was uniaxial negative, with ne= 1.560, nw= 1.605. Li2O.3B2O3 was biaxial negative (2V = 75° to 80°), with nα= 1.576, nβ= 1.602, nγ= 1.605. X-ray powder diffraction data for the five crystalline compounds are presented. Thermal expansion data for Li2O-B2O3 and Li2O.2B2O3 and limited data on the fluorescent properties of the compounds are given. X-ray diffraction data are also presented for Li2O.B2O3.4H2O and Li2O.-5B2O3. 10H2O. Li2O B2O3 was obtained by heating the first hydrate at 450° to 680° C. X-ray diffraction showed Li2O.4B2O3 and Li2O-3B2O3 to be the crystalline products obtained during heating the decahydrate at 500°C. and 600°C., respectively.  相似文献   

9.
The influences of Li2O-B2O3-SiO2 glass (LBS) on the activation energy, phase composition, the stability of the structure and microwave dielectric properties of Zn0.15Nb0.3Ti0.55O2 ceramics have been systematically investigated. LBS glass acted as flux former and contributed to the reactive liquid-phase sintering mechanism, which remarkably lowed the sintering temperature from 1150?°C to 900?°C and enhanced the shrinkage and densification of ceramic at the low sintering temperatures. The ceramics with 1.5?wt% LBS glass sintered at 900?°C for 3?h show great properties: εr = 73.59, Q × f = 8024?GHz, τf = 270.54?ppm/°C.  相似文献   

10.
The electrochemical response of infiltrated La0.5Ba0.5CoO3-δ (LBC) in porous La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) has been investigated. The thermal expansion coefficient (TEC) of the resulting electrode was measured, obtaining α?=?12.5?×?10?6 K?1, a value similar to that of LSGM. The polarization resistance (Rp) and the processes involved in the oxygen reduction reaction (ORR) for the new electrode were studied and analyzed through complex impedance spectroscopy measurements as a function of temperature and oxygen partial pressure (pO2), using a symmetrical cell. The value of Rp for the infiltrated LBC turned out to be lower than that measured for an electrode prepared with a composite LBC-LSGM (1:1?wt%) by an order of magnitude, for the temperature range 750?°C ≤ T?≤?900?°C, and about 5 times lower for the temperature range 450?°C≤ T?≤?650?°C. At 600?°C, the LBC infiltrated cathode exhibits a polarization resistance Rp =?0.22?Ω?cm2, in air. The complex impedance spectra show two processes, one identified as low frequency (LF),with a characteristic frequency of 10?Hz, and the other as intermediate frequency (IF), with a range between 0.05 and 2000?Hz. The LF process could be associated to the diffusion of oxygen in the gas phase through the pores of the electrode. Its resistance, RLF =?0.01?Ωc?m2, was found to be independent of the temperature and half of that obtained for the LBC composite cathode. On the other hand, the IF process is related to charge transfer at the electrode surface and the electrode-electrolyte interface. The LBC cobaltite infiltrated in the LSGM scaffolds offers an adequate thermal expansion coefficient and good electrocatalytic activity for the ORR.  相似文献   

11.
The electrocaloric effect (ECE) of Mn doped Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT:Mn) single crystals with particular emphasis on the impact of crystallographic orientations and phase transitions were investigated systematically. Orientation-dependent phase transitions have been demonstrated by the dielectric and strain behaviors. Intriguingly, the negative ECE of 0.02?°C and 0.002?°C were obtained firstly in [001]-oriented PIN-PMN-PT:Mn crystals near the rhombohedral→tetragonal phase transformation and in [011]-oriented crystals near the rhombohedral→orthorhombic phase transformation, respectively. However, only the positive ECE was found in [111]-oriented crystals near the tetragonal→rhombohedral phase transition. Additionally, the maximum ECE temperature changes calculated in [001]-, [011]- and [111]-oriented crystals were 0.33?°C, 0.46?°C and 0.38?°C, respectively. Our results suggest that the negative ECE is attributed to electric field-induced phase transitions, whose critical field decreases with the increase of temperature. The phase transition-mediated coexistence of positive and negative effects in the relaxor-ferroelectric single crystals is beneficial to enhance the efficiency of the solid-state cooling devices.  相似文献   

12.
Emf measurements of cells of the type Pt, H2 (g, 1 atm) |HCl (m), 1-PrOH (X), H2O (Y)| AgCl/Ag at 5–45°C and m 0·005–0·15 mol/kg have been used to derive the standard potentials of the cells by a theoretically justified polynomial curve-fitting technique, the mean activity coefficient of HCl (molal scale), the medium effect, the relative partial molal heat content and the thermodynamic function (mol-fraction scale) for the transfer of HCl from water to the respective 1-PrOH-H2O media. Em° is expressed as a function of temperature. The electrostatic part of the thermodynamic functions was computed according to Born's model and hence the chemical effect of the solvents on the transfer process has been evaluated. The significance of the results discussed with regard to the acid-base properties and the structural effects of the solvents with further additions of 1-PrOH.  相似文献   

13.
A dense γ-Y2Si2O7/B2O3-Al2O3-SiO2 glass coating was fabricated by slurry spraying method on porous Si3N4 ceramic for water resistance. Thermal shock failure was recognized as one of the key failure modes for porous Si3N4 radome materials. In this paper, thermal shock resistance of the coated porous Si3N4 ceramics were investigated through rapid quenching thermal shock experiments and transient finite element analysis. Thermal shock resistance of the coating was tested at 700 °C, 800 °C, 900 °C and 1000 °C. Results showed that the cracks initiated within the coating after thermal shock from 800 °C to room temperature, thus leading to the reduction of the water resistance. Based on the finite element simulation results, thermal shock failure tended to occur in the coating layer with increasing temperature gradient, and the critical thermal shock failure temperature was measured as 872.24 °C. The results obtained from finite element analysis agree well with that from the thermal shock tests, indicating accuracy and feasibility of this numerical simulation method. Effects of thermo-physical properties for the coating material on its thermal shock resistance were also discussed. Thermal expansion coefficient of the coating material played a more decisive role in decreasing the tangent tensile stress.  相似文献   

14.
In this work, ultra-low loss Li2MgTi0.7(Mg1/3Nb2/3)0.3O4 ceramics were successfully prepared via the conventional solid-state method. X-ray photoelectron spectroscopy (XPS), thermally stimulated depolarization current (TSDC) and bond energy were used to determine the distinction between intrinsic and extrinsic dielectric loss in (Mg1/3Nb2/3)4+ ions substituted ceramics. The addition of (Mg1/3Nb2/3)4+ ions enhances the bond energy in unit cell without changing the crystal structure of Li2MgTiO4, which results in high Q·f value as an intrinsic factor. The extrinsic factors such as porosity and grain size influence the dielectric loss at lower sintering temperature, while the oxygen vacancies play dominant role when the ceramics densified at 1400?°C. The Li2MgTi0.7(Mg1/3Nb2/3)0.3O4 ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: εr =?16.19, Q·f?=?160,000?GHz and τf =??3.14?ppm/°C. In addition, a certain amount of LiF can effectively lower the sintering temperature of the matrix, and the Li2MgTi0.7(Mg1/3Nb2/3)0.3O4-3?wt% LiF ceramics sintered at 1100?°C possess balanced properties with εr?=?16.32, Q·f?=?145,384?GHz and τf =??16.33?ppm/°C.  相似文献   

15.
Layered perovskite oxides with and without Ca-doped NdBa0.5Sr0.25Ca0.25Co2O5+δ (NBSCaCO) and NdBa0.5Sr0.5Co2O5+δ (NBSCO) are studied to investigate the effects of Ca doping on the crystal structure, thermal behavior, electrical and electrochemical properties. Both NBSCO and NBSCaCO are tetragonal structure with P4/mmm space group. The average thermal expansion coefficient (TEC) value is reduced from 23.3?×?10?6 K?1 to 19.8?×?10?6 K?1 during 30–800?°C. The electrical conductivities are increased by Ca doping. Both electrical conductivities of NBSCO and NBSCaCO are higher than 600?S·cm?1 over 30–800?°C. Substitution of Sr with Ca can effectively improve the electrochemical properties of NBSCaCO. From 650?°C to 800?°C, the area specific resistance (ASR) of NBSCaCO are decreased from 0.62 to 0.062?Ω?cm2 and the corresponding output power density are increased from 258 to 812?mW?cm?2. On the basis of these results, Ca doped layered perovskite NBSCaCO can be a good cathode candidate material for SOFC application.  相似文献   

16.
A new dinitrogen species is found by ir absorption at 1935 cm?1 (Type B) when a dinitrogen species at 2020 cm?1 (Type A) prepared from N2 on RuAl2O3K is treated with H2 above 170 °C or with NH3 at 25 °C, or when H2-treated catalyst is treated with N2 at 250 °C. The Type B species is more reactive to H2 or O2 than the Type A species. Another ir band is found at around 1870 cm?1 (Type C) when Type B species is evacuated at 200 °C. Both species, B and C, are likely located on the surface, while the Type A species is in an absorbed state. The Type C species is removed rapidly on introduction of H2 or NH3 at 25 °C, probably by displacement. The very low wavenumber, the high sensitivity to gases, and the high stability to evacuation disclose the unique character of the Type C species.  相似文献   

17.
In the present work, Al2O3-SiO2-B2O3 composite nanofibers with mullite-type structure were prepared using electrospinning technique. The microstructure and elastic modulus of the composite nanofibers obtained at elevated temperatures were studied. The results showed that Al4B2O9 phase formed at 900 °C and then transformed to Al18B4O33 at 1100 °C. Mullite was also detected in the nanofibers prepared at 1100 °C. Amorphous SiO2 existed in all samples even the calcination temperature reached up to 1400 °C. The continuous and uniform structure of the composite nanofibers was kept after calcining at different temperatures, while rougher surface was evident due to the growth of the grain caused by the elevated temperature. An increase of elastic modulus of the samples from 9.47 ± 1.91 GPa to 27.30 ± 2.61 GPa was observed when calcination temperatures increased from 800 °C to 1400 °C.  相似文献   

18.
Standard lead—lead sulphate electrode potential was determined over the temperature range 20–240°C from emf measurements of the Pb, PbSO4H2SO4 (0.05M)K2SO4KClHCl(0.1M)/AgCl, Ag and Pb, PbSO4H2SO4(m)K2SO4H2SO4(0.05M)PbSO4, Pb cells where m = 0.005, 0.01, 0.1 and 0.5 M. To this effect lead—lead sulphate electrode potential was calculated using the temperature relationship of the standard silver—silver chloride electrode potential and activity coefficients of hydrochloric acid determined by Greeley et al. at temperatures up to 260°C. Diffusion potentials occurring at the phase boundaries in the cells under investigation were calculated using the Henderson's equation. Values of the standard lead—lead sulphate electrode potential were determined by extrapolation of the E°′ function to the zero ionic strength which was calculated using the second sulphuric acid dissociation constant determined by Lietzke et al. at temperatures up to 300°C. The standard electrode potential was described in the temperature range 20–240°C by the following relationship: E°Pb, PbSO4/SO2?4(V) = 0.040-0.00126T. A change in entropy ΔS° of the electrode reaction Pb + SO2?4 = PbSO4 + 2e? is constant in this temperature range and is ?243 JK?1 mol?1 (?1018 cal K?1 mol?1).  相似文献   

19.
0.82[0.94Bi0.5Na0.5TiO3-0.06BaTiO3]-0.18CaZrO3:xZnO (BNT-BT-CZ:xZnO, x = 0–0.40 with interval of 0.10) high temperature dielectric composites were prepared and the structural and electrical properties were investigated. Significantly improved temperature-insensitive permittivity spectra have been observed in the composites: the temperature range for low variance in permittivity (Δεrr,150?°C < 10%) is 70–190?°C for x?=?0, whereas it is extended at least to 30–250?°C for the optimal x?=?0.10 at 1?kHz. Especially, for this optimal composite, the variance of permittivity is less than 4.0% in the temperature range of 30–400?°C with the suitable permittivity value of ~ 600 at 10?kHz. By comparatively investigating the properties of unpoled and poled samples, the improved temperature-insensitive permittivity is rationalized by the ZnO-induced local electric field that can suppress the evolution of polar nanoregions and thus enhance the temperature-insensitivity of permittivity.  相似文献   

20.
In the present work, we report a method of fabrication of dense 10 mol% Mg2+-doped cerium pyrophosphate-phosphate (Ce0.9Mg0.1P2O7-PmOn; CMP-P) composites by microwave heat-treatment of the preformed Ce0.9Mg0.1P2O7 substrates in the presence of phosphoric acid. The composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The microwave heating at 375 °C for 5 min resulted in the formation of dense CMP-P composites which retained most of the pyrophosphate phase. The electrical conductivity was extracted from the EIS data and for the CMP-P composite prepared by H3PO4 loading for 10 h and microwave heat-treatment for 5 min it was found to be >10?2 S m?1 in 100–250 °C range with a maximum of 0.062 S cm?1 at 190 °C, which was significant for its application as electrolyte in intermediate temperature fuel cells.  相似文献   

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