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1.
Dense symmetric membranes of CaTi0.85?xFe0.15MnxO3?δ (x = 0.1, 0.15, 0.25, 0.4) are investigated in order to determine the optimal Mn dopant content with respect to highest O2 flux. O2 permeation measurements are performed as function of temperature between 700°C–1000°C and as function of the feed side ranging between 0.01 and 1 bar. X‐ray photoelectron spectroscopy is utilized to elucidate the charge state of Mn, and synchrotron radiation X‐ray powder diffraction (SR‐XPD) is employed to investigate the structure symmetry and cell volume of the perovskite phase at temperatures up to 800°C. The highest O2 permeability is found for x = 0.25 over the whole temperature and ranges, followed by x = 0.4 above 850°C. The O2 permeability for x = 0.25 reaches 0.01 mL(STP) min?1 cm?1 at 925°C with 0.21 bar feed side and Ar sweep gas. X‐ray photoelectron spectroscopy indicates that the charge state of Mn changes from approx. +3 to +4 when x > 0.1, which implies that Mn mainly improves electronic conductivity for x > 0.1. The cell volume is found to decrease linearly with Mn content, which coincides with an increase in the activation energy of O2 permeability. These results are consistent with the interpretation of the temperature and dependency of O2 permeation. The sintering behavior and thermal expansion properties are investigated by dilatometry, which show improved sinterability with increasing Mn content and that the thermal expansion coefficient decreases from 12.4 to 11.9 × 10?6 K?1 for x = 0 and x = 0.25, respectively.  相似文献   

2.
Phase equilibria were experimentally investigated in the MgO–MnOx and the ZrO2–MgO–MnOx systems for different oxygen partial pressures by powder X‐ray diffractometry, scanning electron microscopy, and differential thermal analysis. The formation of two compositionally and structurally different β‐spinel solid solutions was observed in the MgO–MnOx system in air in the temperature interval 1473–1713 K. Isothermal sections of the ZrO2–MgO–MnOx phase diagram were constructed for air conditions ( = 0.21 bar) at 1913, 1813, 1713, 1613, and 1523 K. In addition, isothermal sections at 1913 and 1523 K were constructed for = 10?4 bar. The β‐spinel and halite phases of the MgO–MnOx system were found to dissolve up to 2 and 5 mol% ZrO2. A continuous c‐ZrO2 solid solution forms between the boundary ZrO2–MnOx and ZrO2–MgO systems. It stabilizes in the ZrO2–MgO–MnOx system down to at least 1613 K in air and down to 1506 K at = 10?4 bar.  相似文献   

3.
High‐resolution synchrotron powder X‐ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (Tc). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson‐Mehl‐Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T≥1240°C the mullitization had the same kinetics. The activation energy E at T≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol?1. In analysis using a time‐temperature‐transformation diagram for mullitization, a mullitization curve of ζ=1% can be described as where t is time, n is a reaction‐mechanism‐dependent parameter determined as 0.324 by JMA‐analysis, k0 is the frequency factor, EA is the activation energy for atomic diffusion, and represents the activation energy for nucleation. The results of fitting the data to this equation were Tc=1199°C, A=3.9×106 kJ mol?1 K?2, EA=605 kJ mol?1, and k0=3.65×1015. We conclude that the boundary between sillimanite and mullite+SiO2 in the phase diagram is ~1200°C.  相似文献   

4.
Lead‐free MnO‐doped 0.955K0.5Na0.5NbO3‐0.045Bi0.5Na0.5ZrO3 (Abbreviated as KNN‐0.045BNZ) ceramics have been prepared by the conventional solid‐state sintering method in reducing atmosphere ( = 1 × 10?10 atm) and air. For ceramics sintered in reducing atmosphere, only Mn2+ ions exist in ceramics who preferentially occupy the cation vacancies in A‐site at = 0.2‐0.4, whereas Mn2+ ions substitute for Zr4+ ions in B‐site to form defects () at > 0.4. For ceramics sintered in air, mixed Mn2+, Mn3+, and Mn4+ ions coexist here. The Mn2+ ions preferentially occupy the cation vacancies in A‐site at = 0.2‐0.4 and then Mn2+ ions substitute for Zr4+ ions in B‐site at > 0.4. Meanwhile, the Mn3+ ions and Mn4+ ions substitute for Nb5+ ions in B‐site to form defects () at = 0.2‐0.8. The (, , and ) dipolar defects show a positive dipolar defect contribution (DDC) to the , whereas the dipolar defects () show a negative DDC to the . The dipolar defects ( ‐ and ) can help improve the temperature stability of . The 0.4% MnO‐doped KNN‐0.045BNZ ceramics sintered in reducing atmosphere show excellent piezoelectric constant d33 = 300 pC/N and 0.2% MnO‐doped KNN‐0.045BNZ ceramics sintered in air possess optimal piezoelectric constant d33 = 290 pC/N.  相似文献   

5.
A luminescent Eu, Dy: SrAl2O4 glass‐ceramics with high transparency in the visible region was successfully synthesized using the frozen sorbet technique with the control of O2 partial pressure () for the oxidation of Eu2+ ions. The glass‐ceramics include Eu2+, Eu3+, and Dy3+ ions, and thus exhibits three characteristic types of emission bands, 4f–5d at around 520 nm (Eu2+ ions), 4f–4f at 610 nm (Eu3+ ions), and 480 nm (Dy3+ ions). The Eu, Dy: SrAl2O4 glass‐ceramics provide remarkable long‐persistent luminescence under dark condition. The glass‐ceramics also exhibits color‐changing luminescence in the visible region based on their remarkable light storage properties. The luminescent Eu, Dy: SrAl2O4 glass‐ceramics using the frozen sorbet technique with control of are promising materials for application in novel photonic and light storage materials.  相似文献   

6.
Containerless levitation technique, where the undercooling can be treated as one of the major thermodynamic parameters, was used to study the influence of oxygen partial pressure () on the microstructure and physical properties of rare‐earth orthoferrites RFeO3 (where R = Rare‐earth element) in the ranges from 105 to 10?1 Pa. The microstructure of the as‐solidified samples changed into orthorhombic RFeO3 (o‐RFeO3), metastable hexagonal RFeO3 (h‐RFeO3), and Fe2+‐containing RFe2O4 and a new metastable R3Fe2O7 phases with decreasing . The effect of on the magnetic properties was indicated as that the saturation magnetization gradually increased for R = La to Yb and decreased for R = Lu with decreasing due to the formation of metastable and magnetic phases such as Fe3O4 and Fe.  相似文献   

7.
The hosts with low maximum phonon energy (MPE) are preferred since the nonradiative consumption of the luminescence centers in them are low. Among the low MPE hosts, the oxide ones are more favored owing to their excellent stability and easy synthesis. In this work, the optical and spectroscopic properties of BaGd2O4:Er3+ phosphor were studied. The MPE of BaGd2O4 host was observed from Eu3+ phonon sideband (PSB) spectrum and Raman spectrum to be 477 cm−1 which does not second to the fluoride hosts. The refractive index, which is indispensable for Judd–Ofelt calculation, was confirmed from the both approaches of the Eu3+-probe and the band gap energy, and the similar refractive indices were confirmed, therefore the average refractive index 2.01 was used in the Judd–Ofelt calculation. The Judd–Ofelt parameters of Er3+ in BaGd2O4 host was confirmed to be = 7.91 × 10−21 cm2, = 2.36 × 10−21 cm2, and = 9.00 × 10−22 cm2. Furthermore, the internal quantum efficiencies for 4F9/2 and 4IJ (J = 9/2, 11/2, and 13/2) levels were determined. Finally, the optical temperature sensing properties were studied in detail, and the temperature calibration curve was experimentally derived, meanwhile the maximum absolute sensitivity was confirmed to be 0.0028 K−1.  相似文献   

8.
In this work, the nonstoichiometric 0.99Bi0.505(Na0.8K0.2)0.5‐xTiO3‐0.01SrTiO3 (BNKST(0.5‐x)) ceramics with x=0‐0.03 were synthesized by conventional solid‐state reaction method. The composition‐induced structural transitions were investigated by Raman spectra, dielectric analyses, and electrical measurements. It is found that the relaxor phase can be induced through the modulation of the (Na, K) content. The (Na, K) deficiency in BNKST(0.5‐x) ceramics favors a more disordered local structure and can result in the loss of long‐range ferroelectricity. The x=0.015 critical composition possesses relatively high positive strain Spos of 0.42% and large signal piezoelectric constant d33* of 479 pm V?1 at 6 kV mm?1, along with the good temperature (25‐120°C) and frequency (1‐20 Hz) stability. The recoverable large strain responses in nonstoichiometric ceramics can be attributed to the reversible relaxor‐ferroelectric phase transition, which is closely related to the complex defects (, , and ) and the local random fields. This work may be helpful for the exploration of high‐performance NBT‐based lead‐free materials by means of A‐site compositional modification.  相似文献   

9.
Lead‐free MnO‐doped 0.955K0.5Na0.5NbO3‐0.045Bi0.5Na0.5ZrO3 (abbreviate as KNN‐0.045BNZ) ceramics have been prepared by a conventional solid‐state sintering method in reducing atmosphere. The MnO addition can suppress the emergence of the liquid phase and improve the homogenization of grain size. All ceramics sintered in reducing atmosphere show a two‐phase coexistence zone composed of rhombohedral (R) and tetragonal (T) phase. MnO dopant results in the content increase in R phase and slight increase in Curie temperature TC. For KNN‐0.045BNZ ceramics, Mn2+ ions preferentially occupy the cation vacancies in A‐site to decrease oxygen vacancy concentration for 0.2%‐0.4% MnO content, whereas Mn2+ ions substitute for Zr4+ ions in B‐site to form oxygen vacancies at  0.5. The defect dipole is formed at the moderate concentration from 0.5 to 0.6, which can provide a preserve force to improve the temperature stability of piezoelectric properties for kp and . The Mn0.4 ceramics show excellent electrical properties with quasistatic piezoelectric constant d33 = 300 pC/N, electromechanical coupling coefficient kp = 51.2%, high field piezoelectric constant  = 430 pm/V (at Emax = 25 kV/cm) and TC = ~345°C, insulation resistivity ρ  =  6.13 × 1011 Ωcm.  相似文献   

10.
A system for mass relaxation studies based on a gallium phosphate piezocrystal microbalance has been developed, built, and successfully used to characterize a representative mixed ionic and electronic conducting material. The apparatus is constructed to achieve reactor gas exchange times as short as 2 seconds and temporal resolution in mass measurement of 0.1 seconds. These characteristics enabled evaluation of mass relaxations that occurred on the 6 seconds time scale. Proof of concept for materials characterization capabilities of the system was carried out using 10% praseodymium‐doped cerium oxide (PCO), a material that undergoes, at selected temperatures and oxygen partial pressures, changes in mass but not in conductivity. Thin films were deposited on the piezocrystals via pulsed laser deposition (PLD). Mass relaxation curves were collected at 700°C upon application of a small step change in oxygen partial pressure, . Using two different films, the surface reaction constant, kS, was obtained over the range from 10?4 to 0.1 atm. Its value is found to vary between 9.7 × 10?6 and 1.7 × 10?4 cm/s, displaying a power law dependence on , with a law exponent of 0.67 ± 0.02, as averaged over the two sets of results. This steep dependence of kS on is surprisingly independent of a change in dominant defect type within the range of measurement.  相似文献   

11.
The ion valence state, phase composition, microstructure, and microwave dielectric properties of Sr(1?1.5x)CexTiO3 (x = 0.1–0.67, SCT) ceramics were systematically investigated. Sr(1?1.5x)CexTiO3 ceramics were produced with gradual structural evolution from a cubic to a tetragonal and turned to an orthorhombic structure in the range of 0.1 ≤ x ≤ 0.67. Above a critical Ce proportion (x = 0.4), microstructural changes and normal grain growth initially occurred. On the basis of chemical analysis results, the reduction of Ti4+ ions was hastened by tetravalent ions (Ce4+). By contrast, this reduction was inhibited by trivalent ions (Ce3+). The observed dielectric behavior was strongly influenced by phase composition, oxygen vacancies (), and defect dipoles, namely, () and (). Temperature stable ceramics sintered at 1350°C for 3 h in air yielded an intermediate value of dielectric constant (εr = 40), with the smallest reported value of temperature coefficient of resonant frequency (τf = +0.9 ppm/°C), and quality factor (Q × f = 5699 GHz) at x = 0.6.  相似文献   

12.
The combined additions of Ca2+ and to the SiO2–ZrO2 system were attempted through in situ sol–gel technique. Six different combinations were synthesized and the results were compared with pure SiO2–ZrO2 system. The synthesized materials were subjected to accelerated leaching tests to evaluate their phase degradation behavior, nanoindentation for mechanical analysis, and immersion tests in simulated body fluids (SBF) to test their apatite forming ability. The results confirmed the phase stability of t‐ZrO2 till 1100°C and the presence of SiO2, Ca2+, and in t‐ZrO2 matrix exhibited good apatite forming ability during SBF immersion and their reluctance in phase degradation during accelerated leaching tests. However, the values of hardness and Young's modulus were found inferior in comparison with the commercial t‐ZrO2 products.  相似文献   

13.
We report the pulsed-laser deposition of epitaxial double-perovskite Bi2FeCrO6 (BFCO) films on the (001)-, (110), and (111)-oriented single-crystal SrTiO3 substrates. All of the BFCO films with various orientations show the and superlattice-diffraction peaks. The intensity ratios between the -superlattice and the main 111-diffraction peak can be tailored by simply adjusting the laser repetition rate and substrate temperature, reaching up to 4.4%. However, both optical absorption spectra and magnetic measurements evidence that the strong superlattice peaks are not correlated with the B-site Fe3+/Cr3+ cation ordering. Instead, the epitaxial (111)-oriented Bi2FeCrO6 films show an enhanced remanent polarization of 92 μC/cm2 at 10 K, much larger than the predicted values by density-functional theory calculations. Positive-up-negative-down (PUND) measurements with a time interval of 10 μs further support these observations. Therefore, our experimental results reveal that the strong superlattice peaks may come from A- or B-site cation shifts along the pseudo-cubic [111] direction, which further enhance the ferroelectric polarization of the BFCO thin films.  相似文献   

14.
Lead‐free Ba0.7Ca0.3Ti1?xSnxO3 (x=0.00, 0.025, 0.050, 0.075, and 0.1, abbreviated as BCST) electroceramic system was prepared by the solid‐state reaction method and its ferroelectric, piezoelectric, and electrostrictive properties were investigated. X‐ray diffraction shows that the compositions with x≤0.05 exhibit a tetragonal crystal structure having P4mm symmetry; while the compositions x=0.075 and 0.1 exhibit a mixed P4mm+Amm2 phase coexistence of tetragonal and orthorhombic and P4mm+Pmm pseudo‐cubic lattice symmetries, respectively, at room temperature. The dense microstructure having relative density ~90%‐92% and average grain size in the range ~2.36 μm to 8.56 μm was observed for BCST ceramics. Temperature‐dependent dielectric measurements support the presence of phase coexistence and show the decrease in Curie temperature (TC) with Sn4+ substitution. The dielectric loss (tan δ) values in the temperature range (?100°C to 150°C) was observed to be <4%, for all BCST ceramics. The BCST compositions exhibit typical polarization‐electric field (P‐E) hysteresis and electric field induced strain (S‐E) butterfly loop, which confirms the ferroelectric and piezoelectric character. The compositions x=0.025, 0.05 and 0.075 show the peaking behavior of displacement current density () to an applied electric field () (J‐E) which implies the saturation state of polarization. The maximum electrostrictive coefficient (Q33) value of 0.0667 m4/C2 was observed for x=0.075 and it is higher than some of the significant lead‐based electrostrictive materials. The compositions x=0.05 and 0.075 exhibit the notable electrostrictive properties that may be useful for piezoelectric Ac device applications. The observed results are discussed and correlated with the structure‐property‐composition.  相似文献   

15.
This article considers the diverse substitutional effects of the Sn cations in the BaTiO3 lattice and its impact on the electrical conduction as a function of A/B stoichiometry, oxygen partial pressure, and temperature. High‐density specimens were fabricated in the different oxygen partial pressures to control the valence state of Sn ion. Specifically, the nonstoichiometric materials were sintered in a low pO2 atmosphere (10?14 atm at 1320°C) and in a high pO2 atmosphere (10?0.21 atm at 1320°C), respectively. It is found that Sn occupying the Ti‐site acts as an acceptor dopant, and the electronic conductivity varies from a n‐type to p‐type transition, with increasing oxygen activity as mostly expected. However, there is an unusual case noted with Sn doping the A‐site where the conductivity, σ, is invariant at high pO2's, i.e., σ ~  with m ≈ 0 in the high pO2 regime. The variation of the conductivity is explained by a valence changing of Sn ion from +2 to +3 to +4 with increasing oxygen partial pressure, and we model this data across all conditions within a self‐consistent defect chemistry model.  相似文献   

16.
By conventional ceramics sintering technique, the lead‐free 0.85Bi0.5Na0.5(1?x)Li0.5xTiO3‐0.11Bi0.5K0.5TiO3‐0.04BaTiO3 (x =0–0.15) piezoelectric ceramics were obtained and the effects of Li dopant on the piezoelectric, dielectric, and ferroelectric properties were studied. With increasing Li addition, the temperature‐dependent permittivity exhibited the normal ferroelectric‐to‐ergodic relaxor (FE‐to‐ER) transition temperature (TFEER, abbreviated as TF‐R) decreasing down to room temperature. The increasing Li content also enhanced the diffuseness of the FE‐to‐ER transition behavior. For composition with x = 0.15, a large unipolar strain of 0.37% ( = Smax/Emax = 570 pm/V) was achieved under 6.5 kV/mm applied electric field at room temperature. Both unipolar and bipolar strain curves related to the temperature closely, and when the temperature reached the TF‐R, the normalized strain achieved a maximum value (e.g., for x = 0.10, = 755 pm/V) owing to the electric‐field‐induced ER‐to‐FE state transition.  相似文献   

17.
The pervoskite‐type oxides have received attention due to their potential applications in catalysis, solid oxide fuel cells, gas sensors, and gas separable membranes. In view of their importance in oxygen separation from air, BaxSr1?xFeO3?δ (0≤x≤1.0) samples have been synthesized by sol‐gel process and investigated with regard to phase(s), oxygen permeation, and electrical conductivity. These compounds possess at room temperature, a perovskite‐type cubic, mixture of rhombohedral and hexagonal, and hexagonal phase(s) depending upon the composition 0≤x≤0.94, x=0.96‐0.98, and x=1.0, respectively. The barium incorporation causes initially enhancement but decrease in electrical conductivity above x=0.94. Above 800°C, all the compositions exhibit a stable cubic phase. The compacts made in the form of discs serve as stable oxygen permeable membranes displaying flux density () of ~2.45‐3.58 mL/cm2.min at 1000°C. A good correlation has been demonstrated between the oxygen permeation and the electrical conductivity data. The maximum values of and conductivity correspond to BaxSr1?xFeO3?δ (x=0.94) with a perovskite‐type cubic structure. Hence, this membrane is quite suitable for oxygen separation technology.  相似文献   

18.
The oxygen nonstoichiometry of large oxygen‐deficient Ruddlesden–Popper oxides LaxSr3?xFe2O7?δ (LSFO7‐x) (x = 0, 0.25, 0.5) was measured by the high‐temperature gravimetry and the coulometric titration. In the composition series, the P(O2) dependencies exhibited typical plateaus at δ = (2?[])/2. Meanwhile, La0.5Sr2.5Fe2O7?δ showed the smallest oxygen nonstoichiometry and was the most thermochemically stable compound against P(O2), temperature, and the La content. Based on the defect equilibrium model and the statistical thermodynamic calculation derived oxygen nonstoichiometric data, the substitution of La for Sr‐site can promote the forward reaction of oxygen incorporation, the backward reaction of the disproportionation of the charge carriers, and oxygen redistribution between the O1 and O3 sites, resulting in the reduction of oxygen‐deficient and the lower decomposition P(O2). The obtained thermodynamic quantities of the partial molar enthalpy of oxygen, , and the partial molar entropy of oxygen, , calculated from the statistical thermodynamic calculation are in good agreement with those using the Gibbs–Helmholtz equation.  相似文献   

19.
When incorporating actinides into zirconolite for high-level radioactive waste immobilization, Al3+ and Fe3+ ions generally act as charge compensators. In this study, we rationally designed a series of (Ln = La, Nd, Gd, Ho, Yb) to unravel the dopant solubility and evolutions of the crystalline phase and local environment of cations through synchrotron X-ray methods. It was found that single zirconolite phase is difficult to obtain and the fraction of perovskite have an increase with x from 0.1 to 0.9 in . Formation of both zirconolite-2M and zirconolite-3O phases was observed in and . Phase transformation from zirconolite-2M to 3O occurs at x = 0.7 for while x = 0.9 for . The solubility of and to form single zirconolite-2M can reach to 0.9 f.u. and 0.7 f.u., respectively. The evolution of lattice parameters of zirconolite in is greatly related to the ionic radii of cations and substitution mechanism among the cations. X-ray absorption near edge spectroscopy revealed that Fe3+ ions replace both five- and six-coordinated Ti sites and the ratio of TiO5 to TiO6 decreases when increasing dopant concentration in the . For the local environment of Zr4+, the major form is ZrO7 with a trace of ZrO8.  相似文献   

20.
A series of Ba1.5Sr1.5Co2+xZrxFe24-2xO41 hexaferrites (x = 0.00, 0.01, 0.03, 0.05, 0.07, and 0.09) were successfully prepared by the conventional solid-state reaction method. It was found that as the Co2+ and Zr4+ ions entered the hexaferrite structure, the lattice parameters increased, whereas the relative density increased when x = 0.00-0.03 and then decreased. A suitable amount of substitution increased the DC resistivity, reduced the magnetic and dielectric losses, and made the μ $\mu ^{\prime}$ and ε $\varepsilon ^{\prime}$ closer to each other. At x = 0.03, the relative density and DC resistivity of the samples reached their maxim. Besides, both the magnetic and dielectric losses were lowest within the frequency range of 10 MHz-1 GHz. Meanwhile, the hexaferrite was impedance matched to free space, and the miniaturization factor was about 15. Therefore, this low-loss ferrite with almost equal permeability and permittivity could be meaningful for antenna miniaturization and high-frequency applications.  相似文献   

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