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1.
The sintering behavior of gadolinia-doped ceria powders was studied by the master sintering curve (MSC). Dilatometric analyses of powders produced by a soft chemical method were performed to provide the experimental data set for the construction of the MSC. The assumed model provided good fittings of the MSC and the activation energy for the sintering of Ce1−x Gd x O3−δ, with x = 0, 0.05, 0.1, and 0.2 were found to be in the 218–325 KJ/mol range, depending on the dopant content. The results supported that both the nanometric size of the particles and the difference in ionic radii between Gd3+ and Ce4+ affects the sintering of Gd-doped CeO2.  相似文献   

2.
Ca3Co4O9 powder was prepared by a polyacrylamide gel route in this paper. The effect of the processing on microstructure and thermoelectric properties of Ca3Co4O9 ceramics via spark plasma sintering were investigated. Electrical measurement shows that the Seebeck coefficient and conductivity are 170 μV/K and 128 S/cm, respectively, at 700 °C, yielding a power factor value of 3.70 × 10−4 W m−1 K−2 at 700 °C, which is larger than that of Ca3Co4O9 ceramics via solid-state reaction processing. The polyacrylamide gel processing is a fast, cheap, reproducible and easily scaled up chemical route to improve the thermoelectric properties of Ca3Co4O9 ceramics by preparing the homogeneous and pure Ca3Co4O9 phase.  相似文献   

3.
(Pb1−xSrx)Nb1.96Ti0.05O6 with 2 wt% excess PbO (x = 0, 0.02, 0.04, 0.06, 0.08) piezoelectric ceramics with high Curie temperature were fabricated via the conventional solid state reaction method. Effects of Sr2+ amount on crystallite structure, microstructure, dielectric and piezoelectric properties were studied. The substitution of Sr2+ ions for Pb2+ ions is effective to lower sintering temperatures. X-ray diffraction patterns indicate that all ceramics form the single orthorhombic ferroelectric phase. The doping of Sr2+ ions facilitates improving densification of the ceramics. Grain size and lattice parameters of the ceramics vary with the change of the Sr2+ contents. Both Curie temperature and maximum dielectric constant change with increasing the Sr2+ amounts. The dielectric constant data were also studied using the Curie–Weiss law and modified Curie–Weiss law. The ceramic with x = 0.04 possesses excellent piezoelectric and dielectric properties, presenting a high potential to be used in high-temperature applications as piezoelectric transducers.  相似文献   

4.
The production of bulk high T c superconducting phase (2223) by EDTA-gel (ethylenediaminetetraacetic acid) techniques has been investigated. It is shown that close control of pH is necessary for the production of a well-complexed precursor which allows subsequent decomposition in two stages at 300 and 800°C. The problem of carbonate formation was investigated experimentally and solved. Precursors are characterised by Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) and the sintering behaviour was monitored by dilatometry. At least three different phases Bi2Sr2Cax−1CuxO8+y (BSCCO); where x=1, 2, 3 were identified within superconducting pellets using XRD, named as Bi2Sr2CuO7 (2201), Bi2Sr2CaCu2O9 (2212) and Bi2Sr2Ca3O10 (2223). The superconducting properties of the sintered samples were studied by vibrating sample magnetometer (VSM). Transition to a superconducting state around 80 K appeared in samples (sintered at 845°C) containing the Bi2Sr2Ca1Cu2Oy (2212) phase. Liquid phase sintering of the samples aided the formation of Bi2Sr2Ca2Cu3Ox (2223) phase at high temperature (860°C), which showed a superconducting transition temperature of 108 K.  相似文献   

5.
Deficiency in the A sublattice of perovskite-type Sr1– y Fe0.8Ti0.2O3–δ (y=0–0.06) leads to suppression of oxygen-vacancy ordering and to increasing oxygen ionic conductivity, unit cell volume, thermal expansion, and stability in CO2-containing atmospheres. The total electrical conductivity, predominantly p-type electronic in air, decreases with increasing A-site deficiency at 300–700 K and is essentially independent of the cation vacancy concentration at higher temperatures. Oxygen ion transference numbers for Sr1– y Fe0.8Ti0.2O3–δ in air, estimated from the faradaic efficiency and oxygen permeation data, vary in the range from 0.002 to 0.015 at 1073–1223 K, increasing with temperature. The maximum ionic conductivity was observed for Sr0.97Fe0.8Ti0.2O3–δ ceramics. In the system Sr0.97Fe1– x Ti x O3–δ (x=0.1–0.6), thermal expansion and electron-hole conductivity both decrease with x. Moderate additions of titanium (up to 20%) in Sr0.97(Fe,Ti)O3–δ result in higher ionic conductivity and lower activation energy for ionic transport, owing to disordering in the oxygen sublattice; further doping decreases the ionic conduction. It was shown that time degradation of the oxygen permeability, characteristic of Sr(Fe,Ti)O3–δ membranes and resulting from partial ordering processes, can be reduced by cycling of the oxygen pressure at the membrane permeate side. Thermal expansion coefficients of Sr1– y Ti1– x Fe x O3–δ (x=0.10–0.60, y=0–0.06) in air are in the range (11.7–16.5)×10–6 K–1 at 350–750 K and (16.6–31.1)×10–6 K–1 at 750–1050 K. Electronic Publication  相似文献   

6.
Tysonite solid solutions Bi1−x Ba x O y F3−x−2y in the BiF3-BiOF-BaF2 system were obtained by solid-phase synthesis in sealed copper tubes in an argon atmosphere at 873 K with subsequent quenching. The solid solutions were studied by X-ray diffraction, electron diffraction, and impedance spectroscopy. On the basis of X-ray powder diffraction data, the homogeneity ranges of the tysonite solid solutions were determined and the scheme of their location in the BiF3-BiOF-BaF2 system at 873 K was suggested. Aliovalent substitutions in both the cation and anion sublattices Ba2+ → Bi3+ and O2− → F made it possible to vary the concentration of anion vacancies. It was found that, at a high concentration of anion defects at 873 K, the hexagonal tysonite modification with space group P63/mmc is stable. With a decrease in the defect concentration, the trigonal tysonite modification with space group $ P\bar 3c1 $ P\bar 3c1 becomes stable. An ordered monoclinic tysonite-type modification BiO y F3 − 2y (0.13 < y < 0.23) was revealed. For the homogeneity ranges of all tysonite phases, dependences of the unit cell parameters and conductivity on the composition along the sections with a constant barium or oxygen content were reported. The most probable location of oxygen anions and anion vacancies in the tysonite structure is discussed.  相似文献   

7.
The area of existence of Gd2Sr1−x Ca x Al2O7 solid solutions at x ≤ 0.5 was determined by the X-ray phase analysis. It was found by full-profile X-ray structural analysis that, in contrast to La2Sr1−x Ca x Al2O7 solid solutions, the Ca2+ cations occupy not only AO9 nine-vertex fragments, but also AO12 oxygen cubooctahedra. Full ordering of Sr2+ cations in the perovskite layer is observed at the calcium content x 0.5. Original Russian Text ? I.A. Zvereva, A.G. Cherepova, Yu.E. Smirnov, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 4, pp. 557–563. For communication XI, see [1].  相似文献   

8.
Ba1−x Sr x TiO3(x = 0–0.5, BST) nanofibers with diameters of 150–210 nm were prepared by using electrospun BST/polyvinylpyrrolidone (PVP) composite fibers by calcination for 2 h at temperatures in the range of 650–800 °C in air. The morphology and crystal structure of calcined BST/PVP nanofibers were characterized as functions of calcination temperature and Sr content with an aid of XRD, FT-IR, and TEM. Although several unknown XRD peaks were detected when the fibers were calcined at temperatures less than 750 °C, they disappeared with increasing the temperature (above 750 °C) due to its thermal decomposition and complete reaction in the formation of BST. In addition, the FT-IR studies of BST/PVP fibers revealed that the intensities of the O–H stretching vibration bands (at 3430 and 1425 cm−1) became weaker with increasing the calcination temperature and a broad band at 540 cm−1, Ti–O vibration, appeared sharper and narrower after calcination above 750 °C due to the formation of metal oxide bonds. However, no effect of Sr content on the crystal structure of the composites was detected.  相似文献   

9.
New environmentally inorganic pigments based on Bi2O3 doped by metal ions, such as Zr4+ and Dy3+ have been developed and characterized using the methods thermal analysis, X-ray powder diffraction, and spectral reflectance data. The compounds having formula Bi2−x Dy x/2Zr3x/8O3 (x = 0.2, 0.6, 1.0, and 1.2) were prepared by the solid state reaction. Methods of thermal analysis were used for determination of the temperature region of the pigment formation and thermal stability of compounds. The incorporation of doped ions in Bi2O3 changes the color from yellow to orange and also contributes to a growth of their thermal stability. This property gives a direction for coloring ceramic glazes.  相似文献   

10.
Ca0.6La0.267TiO3 nanocrystalline powders were successfully synthesized by the sol–gel method using PEG1000 as a dispersant in this study. The sinterability of the powders and the microwave dielectric properties of the ceramics were also investigated. The XRD diffraction result showed that pure Ca0.6La0.267TiO3 powder with orthorhombic perovskite structure could be synthesized at 600 °C for 2 h without any detectable intermediate phase. The average grain size of the as-synthesized powder was as low as 35 nm. Compared with Ca0.6La0.267TiO3 ceramics fabricated by conventional solid-state process, the bulk materials prepared by sintering as-prepared nanopowders performed better in densification and microwave dielectric properties. The ceramics sintered at 1,300 °C exhibited a higher relative density of 98.3% combined with a dielectric constant (ε r ) of 120.3, a quality factor (Q × f) of 23,550 GHz and a temperature coefficient of resonant frequency (τ f ) of +220.7 ppm/°C, respectively.  相似文献   

11.
Electrical conductivity, dielectric permittivity and mechanical hardness of the polycrystalline CeO2 + xSm2O3 (x = 0, 10.9–15.9 mol %) films prepared by Electron Beam Physical Vapour Deposition (EB-PVD) and Ionic Beam Assisted Deposition, (IBAD), techniques were investigated in dependence on their structure and microstructure influenced by the deposition conditions, namely composition, deposition temperature and Ar+ ion bombardment. The electrical conductivity of doped ceria prepared without Ar+ ion bombardment and investigated by the impedance spectroscopy, IS, was found to be predominantly ionic one under the oxidizing atmosphere/low-temperature conditions and the higher amounts of Sm2O3 (>10 mol %) used. The bulk conductivity as a part of total measured conductivity was a subject of interest because the grain boundary conductivity was found to be ∼3 orders of magnitude lower than the corresponding bulk conductivity. Ar+ ion bombardment acted as a reducer (Ce4+ → Ce3+) resulting in the development of electronic conductivity. Dielectric permittivity determined from the bulk parallel capacitance measured at room temperature and the frequency of 1 MHz, similarly as the mechanical hardness measured by indentation (classical Vickers and Depth Sensing Indentation-DSI) techniques were also found to be dependent on the deposition conditions. The approximative value of hardness for the investigated films deposited on the substrate was estimated using a simple phenomenological model described by the power function HV = HV 0 + aP b and compared with the so-called apparent hardness (substrate + investigated film) determined by the classical Vickers formula. Results obtained are analyzed and discussed.  相似文献   

12.
Sr0.8La0.2Zn0.2Fe11.8O19/poly(vinyl pyrrolidone) (PVP) composite fiber precursors were prepared by the sol–gel assisted electrospinning. Subsequently, the M-type ferrite Sr0.8La0.2Zn0.2Fe11.8O19 nanofibers with diameters about 120 nm were obtained by calcination of these precursors at different heat treatment conditions. The precursor and resultant Sr0.8La0.2Zn0.2Fe11.8O19 nanofibers were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectrometer and vibrating sample magnetometer. With the calcination temperature increased up to 1,000 °C for 2 h or the holding time prolonged to 12 h at 900 °C, the Sr0.8La0.2Zn0.2Fe11.8O19 particles gradually grow into a hexagonal elongated plate-like morphology due to the dimensional control along the nanofiber length. These elongated plate-like particles will be linked one by one to form the nanofiber with a necklace-like morphology. The magnetic properties of the Sr0.8La0.2Zn0.2Fe11.8O19 nanofibers are closely related to grain sizes, impurities and defects in the ferrite, which are influenced by the calcination temperature, holding time and heating rate. After calcined at 900 °C for 12 h with a heating rate of 3 °C/min, the optimized magnetic properties are achieved with the specific saturation magnetization 75.0 A m2 kg−1 and coercivity 426.3 kA m−1 for the Sr0.8La0.2Zn0.2Fe11.8O19 nanofibers.  相似文献   

13.
YBaCo4O7 compound is capable to intake and release a large amount of oxygen in the temperature range of 200–400°C. In the present study, the effect of Zn, Ga and Fe substitution for Co on the oxygen adsorption/desorption properties of YBaCo4O7 were investigated by thermogravimetry (TG) method. Due to fixed oxidation state of Zn2+ ions, the substitution of Zn2+ for Co2+ suppresses the oxygen adsorption of YBaCo4−xZnxO7. The substitution of Ga3+ for Co3+ also decreases the oxygen absorption capacity of YBaCo4−xGaxO7. This can be explained by the strong affinity of Ga3+ ions towards the GaO4 tetrahedron. Compared with Zn- and Ga-substituted samples, the drop of oxygen adsorption capacity is smallest for Fe-substituted samples because of the similar changeability of oxidation states of Co and Fe ions.  相似文献   

14.
The magnetic, electronic, and structural properties of the solid solutions LaxSr1−xRuO3 and LaxCa1−xRuO3 have been studied by 99Ru Mössbauer spectroscopy and other techniques. The LaxCa1−xRuO3 phases are reported for the first time and have been shown by powder X-ray diffraction measurements to be orthorhombically distorted perovskites. Electrical resistivity measurements on compacted powders show that all the phases are metallic with p 10−3, ohm-cm. Progressive substitution of Sr2+ by La3+ in ferromagnetic SrRuO3 leads to a rapid collapse of the magnetic hyper-fine splitting at 4.2°K. For x = 0.25 some ruthenium ions still experience a magnetic field but for 0.4 x 0.75 only single, narrow resonance lines are observed, consistent both with the complete removal of the ferromagnetism and with the presence of an averaged ruthenium oxidation state in each phase, i.e., Lax3+Sr1−x2+Ru(4−x)+O3 rather than Lax3+Sr1−x2+Rux3+Ru1−x4+O3. LaRuO3 and CaRuO3 both give essentially single-line spectra at 4.2°K, indicating that the ruthenium ions in these oxides are not involved in long-range antiferromagnetic order but are paramagnetic. The solid solutions LaxCa1−xRuO3 (0 < x 0.6) give sharp symmetrical singlets with chemical isomer shifts (relative to the Ru metal) which move progressively from the value characteristic of Ru4+ (−0.303 mm sec−1) toward the value for Ru3+ (−0.557 mm sec−1), consistent with the presence of intermediate ruthenium oxidation states in these phases also.  相似文献   

15.
One of the most important challenges with solid oxide fuel cells (SOFC) is to find cathode materials with high enough catalytic activity for the dissociation of the molecular oxygen. Oxide mixed conductors with the perovskite structure (ABO3) and high Co content in the B site have been extensively studied to be used as cathode in SOFC. This is the second part of a review of high temperature properties of two mixed conductors systems. The first part was focused on the n = 2 Sr3FeMO6+δ (M = Fe, Co, Ni) Rudlesdden Popper phases, while in this paper we discuss the thermodynamic and transport properties of the perovskite solid solution Sr1−x La x Fe0.2Co0.8O3−δ (0 ≤ x ≤ 0.4) in the temperature range 773 ≤ T ≤ 1173 K. In particular, the interest has been focused on the x = 0 sample, which exhibits large ionic conductivity values (σi ~1 S cm−1), but suffers a structural transformation from cubic to orthorhombic symmetry because the ordering of the oxygen vacancies when the oxygen partial pressure decreases. Measurements of the oxygen chemical potential ( m\textO2 \mu_{{{\text{O}}_{2} }} ) as function of oxygen content and temperature, coupled with high temperature X-ray diffraction data, permitted us to broaden the knowledge of the T–δ–p(O2) phase diagram for the x = 0 sample. In addition, we have investigated the effects of the La incorporation on the stability range of the cubic phases of the Sr1−x La x Fe0.2Co0.8O3−δ solid solution.  相似文献   

16.
From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ca2+ (aq)+1·Sr2+ (nb) ⇆ 1·Ca2+ (nb) + Sr2+ (aq) taking place in the two-phase water-nitrobenzene system (1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K ex (Ca2+, 1·Sr2+) = 2.4±0.1. Further, the stability constant of the valinomycin-calcium complex (abbrev. 1·Ca2+) in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β nb (1·Ca2+) = 8.3±0.1. By using quantum mechanical DFT calculations, the most probable structure of the 1·Ca2+·2H2O complex species was predicted. In this complex, the “central” Ca2+ cation is bound by strong bonds to two oxygen atoms of the respective water molecules and to four ester carbonyl oxygens of the parent valinomycin ligand 1. Finally, the calculated binding energy of the considered complex 1·Ca2+·2H2O is −319.2 kcal/mol, which confirms the relatively high stability of this cationic complex species.  相似文献   

17.
A new oxide phase La1.5Sr1.5 Mn1.25Ni0.75O6.67 ± 0.05, a member of the An + 1 BnO3n+1(n=2) Rad-dlesden—Popper homologue series, was synthesized, and its structure and magnetic properties characterized. Magnetic anomalies associated with the competition between antiferromagnetic and ferromagnetic orders are observed in the range of the temperatures studied (2-400 K). The ESR spectra of the compound feature the constriction of a magnetic signal and a shift toward g(Mn4+).  相似文献   

18.
Dielectric and Raman scattering experiments were performed on polycrystalline Pb1−x−yCaxSryTiO3 thin films as a function of temperature. Temperature-dependent dielectric measurements revealed a decreasing ferroelectric-to-paraelectric phase transition temperature and peak dielectric permittivity showed a broad phase transition near room temperature with increasing levels of CaO12 and SrO12 clusters. Therefore, for higher levels of substitution, the possible random position of the CaO12 and SrO12 clusters leads to a diffuse state. At 100 kHz, the ferroelectric-to-paraelectric phase transition temperatures were 633, 495 and 206 K for PCST90 (Pb0.90Ca0.05Sr0.05TiO3), PCST70 (Pb0.70Ca0.15Sr0.15TiO3) and PCST30 (Pb0.30Ca0.35Sr0.35TiO3) thin films, respectively. The evolution of the Raman spectra was also studied as a function of temperature. The temperature dependence of the E(1TO) soft mode frequencies was used to characterize the phase transition. Raman peaks were observed above the ferroelectric-to-paraelectric phase transition temperature, although all optical modes should be inactive in Raman scattering. The origin of these modes was interpreted as a breakdown of the local cubic symmetry by the random distribution of CaO12 and SrO12 clusters.  相似文献   

19.
Ferroelectric thin films of Nd and Mn co-doped bismuth titanate, Bi3.15Nd0.85Ti3−x Mn x O12 (BNTM) (x = 0–0.1), were fabricated on Pt/TiO2/SiO2/Si(100) substrates by a sol–gel technique. The BNTM films had a polycrystalline perovskite structure and uniform and dense surface morphologies. A lattice distortion was observed in the BNTM films due to Mn ion doping. The ferroelectric measurement of the films indicated that the values of coercive field (E c ) decreased gradually with the increase of the Mn content (x), however, the remanent polarization (P r ) increase firstly and then decrease with the increase of x. The sample with x = 0.05 had optimum electrical properties and a maximum 2P r value. The 2P r and 2E c values of the film at a maximum applied electric field of 400 kV/cm were 38.3 μC/cm2 and 180 kV/cm, respectively. Moreover, this BNTM capacitors did not show fatigue behaviors after 1.0 × 1010 switching cycles at a frequency of 1 MHz, suggesting a fatigue-free character. The main reason for the increase of the 2P r and the decrease of the 2E c might be attributed to the lattice distortion in BNTM films due to Mn ion doping.  相似文献   

20.
Nano-composites of SnO(V2O3) x (x = 0, 0.25, and 0.5) and SnO(VO)0.5 are prepared from SnO and V2O3/VO by high-energy ball milling (HEB) and are characterized by X-ray diffraction (XRD), scanning electron microscopy, and high-resolution transmission electron microscopy techniques. Interestingly, SnO and SnO(VO)0.5 are unstable to HEB and disproportionate to Sn and SnO2, whereas HEB of SnO(V2O3) x gives rise to SnO2.VO x . Galvanostatic cycling of the phases is carried out at 60 mA g−1 (0.12 C) in the voltage range 0.005–0.8 V vs. Li. The nano-SnO(V2O3)0.5 showed a first-charge capacity of 435 (±5) mAh g−1 which stabilized to 380 (±5) mAh g−1 with no noticeable fading in the range of 10–60 cycles. Under similar cycling conditions, nano-SnO (x = 0), nano-SnO(V2O3)0.25, and nano-SnO(VO)0.5 showed initial reversible capacities between 630 and 390 (±5) mAh g−1. Between 10 and 50 cycles, nano-SnO showed a capacity fade as high as 59%, whereas the above two VO x -containing composites showed capacity fade ranging from 10% to 28%. In all the nano-composites, the average discharge potential is 0.2–0.3 V and average charge potential is 0.5–0.6 V vs. Li, and the coulombic efficiency is 96–98% after 10 cycles. The observed galvanostatic cycling, cyclic voltammetry, and ex situ XRD data are interpreted in terms of the alloying–de-alloying reaction of Sn in the nano-composite “Sn-VO x -Li2O” with VO x acting as an electronically conducting matrix.  相似文献   

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