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1.
Neodymium silicate apatites are promising intermediate temperature (500°C–700°C) electrolytes for solid oxide fuel cells. The introduction of Al promotes isotropic percolation of O2?, and at low levels (0.83–2.0 wt% Al) enhances bulk conductivity. To better understand the effect of Al‐doping on intrinsic conductivity, and the impact of grain boundaries on the transport, dense Nd9.33+x/3AlxSi6?xO26 (0 ≤ x ≤ 2) pellets were prepared by spark plasma sintering. Phase purity of the products was established by powder X‐ray diffraction and the microstructure examined by scanning electron microscopy. The ionic conductivity measured by AC impedance spectroscopy for the spark plasma sintered ceramics were compared with transport in single crystals of similar composition. Intermediate Al‐doping (0.5 ≤ x ≤ 1.5) delivered superior overall conductivity for both the polycrystalline and single crystal specimens.  相似文献   

2.
In this study, the nickel doped apatite-type lanthanum silicate La9.33Si6-xNixO26-x (= 0, .5, 1.0, 1.5, 2.0) (LSNO) electrolyte powders were successfully generated by using the urea nitrate combustion method at 600°C and 6–8 min. The optimal sintering temperature was determined to be 1500°C on the basis of the linear shrinkage, relative density as a function of temperature, and microcosmic analysis. It was observed that Ni2+ successfully replaced Si4+ in [SiO4] to form the [Si(Ni)O4] tetrahedra. LSNO had a typical p63/m apatite structure of high purity. A significant change in the cell volume of the doped samples was observed, and the cell volume increased with the doped nickel content. The conductivity reached the peak value at = 1.0 (1.21 × 10−3 S·cm−1, 700°C). Nickel doping introduced the oxygen vacancies and expanded the channels for interstitial oxygen conduction. Further, it also directly reduced the amount of interstitial oxygen in the LSO structure. This led to an enhancement in the conductivity of La9.33Si6-xNixO26-x, followed by a decrease on increasing the doped nickel content. The conductivity enhancement in the Ni-doped LSO resulted from the combination of two mechanisms, namely, the oxygen vacancy defect and lattice volume enhancement mechanism.  相似文献   

3.
The magnetic properties and magnetocaloric effect for EuTi1-xFexO3 (= 0.05, 0.1) compounds are investigated. When a part of Ti4+ions were substituted by Fe ions, the AFM ordering can be significantly changed to be FM. The EuTi1-xFexO3 (= 0.05, 0.1) compounds exhibit a PM to FM transition with decreasing temperature and the Curie temperature is 6 K. Under the field changes of 1 T, and RC are valued to be 10.1 J/kg K and 50.2 J/kg for EuTi0.95Fe0.05O3; 9.6 J/kg K and 47.7 J/kg for EuTi0.9Fe0.1O3, without magnetic and thermal hysteresis. RC is almost twice as much as EuTiO3 (27 J/kg) as substitution of Fe3+ ions for Ti4+ions, which may be attributed to the magnetic transition (AFM to FM). Therefore, the giant and large RC suggest the EuTi1-xFexO3 compounds are good materials for magnetic refrigerant.  相似文献   

4.
5.
Ca3SnSi2-xGexO9 (0 ≤ x ≤ 0.8) and (1–y) Ca3SnSi1.6Ge0.4O9 – y CaSnSiO5 – 2 wt% LiF (y = 0.4 and 0.5) microwave dielectric ceramics were prepared by traditional solid-state reaction through sintering at 1250°C–1425°C for 5 h and at 875°C for 2 h, respectively. Ge4+ replaced Si4+, and Ca3SnSi2-xGexO9 (0 ≤ x ≤ 0.4) solid solutions were obtained. At 0.1 ≤ x ≤ 0.4, the Ge4+ substitution for Si4+ decreased the sintering temperature of Ca3SnSi2-xGexO9 from 1425 to 1300°C, the SnO6 octahedral distortions, and the average CaO7 decahedral distortions, which affected the τf value. The large average decahedral distortions corresponded with nearer-zero τf values at Ca3SnSi2-xGexO9 (0.1 ≤ x ≤ 0.4) ceramics. The τf value and sintering temperature of Ca3SnSi2-xGexO9 (x = 0.4) ceramic were adjusted to near-zero by CaSnSiO5 and decreased to 875°C upon the addition of 2 wt% LiF. The (1 – y) Ca3SnSi1.6Ge0.4O9 – y CaSnSiO5 – 2 wt% LiF (y = 0.5) ceramic sintered at 875°C for 2 h exhibited good microwave dielectric properties: εr = 10.3, Q × = 14 300 GHz (at 12.2 GHz), and τf = ‒5.8 ppm/°C.  相似文献   

6.
Preparation of sodium zirconium silicate phosphate (NaSICon), Na1+xZr2SixP3?xO12 (0.25 ≤ ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an = 0.25 composition at 2.3 × 10?5 S/cm. The decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.  相似文献   

7.
《Ceramics International》2022,48(6):7652-7662
Ca-doped perovskite oxides PrBa1-xCaxCoCuO5+δ (PBCCCO, x = 0–0.2) were prepared and investigated as SOFC cathode materials. PBCCCO samples are single perovskite structure with P4/mmm space group. Pr, Cu and Co ions in PBCCCO samples exist in the form of Pr3+/Pr4+, Cu2+/Cu+ and Co3+/Co4+ multi-valence states. The average TECs of PBCCCO samples were reduced from 17.4 × 10?6 K?1 (x = 0) to 16.7 × 10?6 (x = 0.1) and 16.1 × 10?6 K?1 (x = 0.2) whin RT-900°С. The electrical conductivity and electrochemical catalytic activity of PBCCCO perovskites was enhanced obviously by Ca doping. The ASR values decreased by 60.1% (@650 °C), 68.9% (@700 °C), 71.0% (@750 °C) and 72.8% (@800 °C) respectively when Ca doping content increased from x = 0 to 0.2. These results suggest PBCCCO sample with Ca doing content x = 0.2 can be a promising cathode for IT-SOFC.  相似文献   

8.
Polycrystalline Cd1?xBaxO (0 ≤ x ≤ 0.08) ceramics were synthesized via conventional solid‐state reaction method, and the effect of Ba2+ doping on the microstructure as well as the thermoelectric transport properties of the samples were investigated. It was found that doping of Ba2+ can inhibit the grain growth of CdO, resulting in a considerable reduction in grain size. Moreover, with the increase in Ba2+ doping content, both the electrical conductivity and the thermal conductivity of Cd1?xBaxO decreased, whereas the Seebeck coefficient increased. A high ZT value of 0.47 was achieved for Cd0.99Ba0.01O at 1000 K, 38% higher than the undoped CdO, mostly due to reduction of the thermal conductivity.  相似文献   

9.
《Ceramics International》2023,49(4):5884-5892
A series of novel negative temperature coefficient (NTC) thermistor materials based on La1-xCexAlO3 (0 ≤ x ≤ 0.2) ceramics were synthesized via the solid-state route. X-ray diffraction results confirmed the successful doping of Ce in the La1-xCexAlO3 crystal and the formation of a good solid solution. Scanning electron microscopy results indicated that Ce doping is beneficial for grain growth and reduces the porosity of the samples. With the increase in the Ce doping amount, the average grain size increased from 2.1793 to 10.7344 μm, and densities of the ceramics increased from 93.15% to 99.26%. The temperature vs resistance curve indicated that Ce doping reduces the resistivity of LaAlO3 materials, while reducing the B200/1400 value of the LaAlO3 ceramic. For a doping amount of 0.2, the B200/1400 value of the LaAlO3 ceramic decreased from 18175.1 to 4897.7K, and the resistivity at 1000 °C decreased from 68971.87 to 1105.15 Ω cm. In addition, the La1-xCexAlO3 (0 ≤ x ≤ 0.2) series materials exhibited good linear NTC characteristics. X-ray photoelectron spectroscopy results revealed that the resistivity of the LaAlO3 materials decreased after Ce doping owing to the transformation between the Ce4+ and Ce3+ valence states,and the concentration of Ce3+ increased with the increase in the Ce doping amount. Ce3+ increases the concentration of oxygen vacancies, decreasing the resistance. Impedance analysis findings suggested that the resistance of the La1-xCexAlO3 (0 < x ≤ 0.2) material mainly originates from the grain. These results indicate that Ce doping is an effective method to reduce the resistivity of LaAlO3. Consequently, La1-xCexAlO3 (0 ≤ x ≤ 0.2) is a promising material for NTC applications.  相似文献   

10.
The (1?x)Mg2Al4Si5O18xTiO2 |(1?x)MAS‐xT| (0 ≤ x ≤ 0.35) cordierite ceramics are fabricated by solid‐state reaction method for obtaining near‐zero temperature coefficient of resonant frequency (τf). The XRD and SEM results show that (1?x)MAS‐xT (0 ≤ x ≤ 0.10) ceramics exhibit single cordierite solid solution, whereas as 0.15 ≤ x ≤ 0.35, present composite phases of Mg2Al4Si5O18 solution and TiO2. Rietveld refinements of XRD data suggest that the [(Si4Al2)O18] hexagonal shape in cordierite structure happens to alternate change from nonsymmetrical hexagonal rings to almost centrosymmetrical equilateral rings as x increases to 0.10 comparing to that of x = 0. As Ti4+ ions squeeze into the [(Si4Al2)O18] rings structure, the orientation and shapes of the rings begin to rotate and expand from initial state of [1–20] (x = 0) to near [210] direction (x = 0.10), and then continue to expand toward close to [110] direction (x = 0.25). Due to centrosymmetry adjustment of [(Si4Al2)O18] hexagonal rings and of other microstructure factors improvement, the (1?x)MAS‐xT (x = 0.10) cordierite solution achieves optimum quality factor Qf: εr = 6.3, Qf = 55 400 GHz (17.6 GHz), τf = ?21 ppm/°C. The (1?x)MAS‐xT (x = 0.25) composites obtain a near‐zero temperature coefficient of resonance frequency: εr = 6.8, Qf = 37 800 GHz (18.4 GHz), τf = ?0.2 ppm/°C.  相似文献   

11.
In this study, the binary system of (ZrO2)1-x(Er2O3)x was investigated in the doping range of x; 0.02 ≤ x ≤ 0.12 by the Pechini method. According to X-ray diffraction (XRD) measurement results, Er2O3 doping face-centered cubic (fcc) ZrO2-based solid solution was stabilized in the doping range of 0.08 ≤ x ≤ 0.12 at 1200°C for 12 hours. Thick films of fcc-ZrO2 type powders were produced using ethyl cellulose organic binder mixture and spin-coating method. The crystallographic, microstructural, and electrical conductivity properties of the thick films were characterized via XRD, SEM, and a.c. impedance measurements, respectively. 8-ESZ ((ZrO2)1-x(Er2O3)x, x = 0.08) thick film electrolyte showed the highest electrical conduction level which is 2.51 × 10−2 ohm−1 cm−1 at 850°C under 150 mL min−1 O2 volumetric flow rate. All thick film properties of fcc-ESZ materials were optimized and improved experimentally for using as a solid electrolyte component in solid oxide fuel cell (SOFC) systems. A pre-treatment of 8-ESZ and the cathode-supported type electrochemical cell were primarily fabricated. The power density measurements of 40-LNF (LaNi1-xFexO3, x = 0.4) Cathode|Cathode Active (50:50 wt % 40-LNF:8-ESZ)| 8-ESZ Electrolyte|Anode Active (60:40 wt % NiO:8-ESZ)|NiO Anode Electrode cell stack suggest that the produced electrolytes had the usefully properties for SOFC applications.  相似文献   

12.
The structure stabilities of double perovskite ceramics‐ (1 ? x) Ba(Mg1/2W1/2)O3 + xBa(Y2/3W1/3)O3 (0.01 ≤ x ≤ 0.4) have been studied by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), and Raman spectrometry in this study. The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 8–11 GHz. The results showed that all the compounds exhibited face‐centered cubic perovskite structure. Part of Y3+ and W6+ cations occupied 4a‐site and the remaining Y3+ and Mg2+ distributed over 4b‐site, respectively, and kept the B‐site ratio 1:1 ordered. Local ordering of Y3+/Mg2+ on 4b‐site and Y3+/W6+ cations on 4a‐site within the short‐range scale could be observed with increasing Y‐doping content. The decomposition of the double perovskite compound at high temperature was successfully suppressed by doping with Y on B‐site. However, Ba2Y0.667WO6 impurity phase appeared when x > 0.1. The optimized dielectric permittivity increased with the increase in Y doping. The optimized Q × f value was remarkably improved with small amount of Y doping (x ≤ 0.02) and reached a maximum value of about 160 000 GHz at x = 0.02 composition. Further increasing in Y doping led to the decrease in Q × f value. All compositions exhibited negative τf values. The absolute value of τf decreased with increasing Y‐doping content. Excellent combined microwave dielectric properties with εr = 20, Q × = 160 000 GHz, and τf = ?21 ppm/°C could be obtained for x = 0.02 composition.  相似文献   

13.
The Ca(1+x)/2Sr(1+x)/2Zr4P6-2xSi2xO24 (CSZP6-2xS2x, 0 ≤ x ≤ 0.3) ceramics were prepared using powders synthesized by co-precipitation method, and the effects of Si4+ substitution on the structure, mechanical, and thermal expansion properties were investigated. The optimum sintering time was 4 hours, which greatly shortened the sintering process. By controlling the appropriate composition and sintering temperature, a single phase with the typical NaZr2P3O12 structure was obtained. As a function of x increasing, the parameter a increased and then decreased, while the parameter c and unit cell volume both increased. The mechanical property of CSZP6-2xS2x ceramics was affected with increasing amount of Si4+ content. The Si4+ substitution could increase the thermal expansion anisotropy and lead to the generation of microcracks, which are responsible for the increase in the amount of hysteresis between heating and cooling curves. The thermal expansion decreased progressively from 1.8 to 0.8 × 10−6/°C. The investigations indicate that the CSZP6-2xS2x ceramics are potential materials in high temperature applications  相似文献   

14.
Poly(N‐methylaniline) (PNMA) is one of the polyaniline derivatives with N‐substituted position. Polyaniline derivatives have attracted attention due to their higher solubility in common solvents than pristine polyaniline, but they still possess lower electrical conductivity. In this work, PNMA was synthesized via chemical oxidative polymerization in an ethanol–water system. The effect of surfactant type, namely anionic sodium dodecylbenzenesulfonate (SDBS), cationic cetyltrimethylammonium bromide and non‐ionic Tween20, on the electrical conductivity, doping level and morphology was investigated. PNMA prepared with the SDBS system possessed the highest electrical conductivity among the obtained PNMAs with and without surfactants. The effect of N HClO 4 /NNMA dopant mole ratios on the re‐doping, crystallinity, morphology and particle size was also examined. Using an N HClO 4 /NNMA mole ratio of 10:1 in the re‐doping process provided the highest electrical conductivity of 15.53 ± 2.5 S cm?1, a doping level of 55.59%, along with hollow spherical particles with the thinnest membrane. Electron microscopy images revealed that the morphology of PNMA particles depended mainly on the surfactant type but not the N HClO 4 /NNMA mole ratio. © 2019 Society of Chemical Industry  相似文献   

15.
《Ceramics International》2022,48(3):3592-3599
Novel BaZr(Si1-xGex)3O9 (0 ≤ x ≤ 1.0) microwave dielectric ceramics were prepared by solid-state reaction sintering at 1200–1450 °C for 5 h Ge4+ ions occupied the Si4+ positions, and BaZr(Si1-xGex)3O9 solid solutions were obtained. The BaZr(Si1-xGex)3O9 (0 ≤ x ≤ 1.0) ceramics exhibited hexagonal structures with P-6c2 space groups and octahedral layers and [Si/Ge3O9]6- rings. Owing to these structural characteristics, the ceramics exhibited low permittivity. With an increase in x, the relative permittivity (εr) values of the BaZr(Si1-xGex)3O9 (0 ≤ x ≤ 1.0) ceramics increased from 7.68 (x = 0) to 9.45 (x = 1.0), while their quality factor (Q × f) values first increased and then decreased. The Q × f value (10,300 GHz at 13.43 GHz) of the BaZrSi3O9 (x = 0) ceramic improved with the substitution of Si4+ by Ge4+. A high Q × f value (36,100 GHz at 13.81 GHz) was obtained for the BaZr(Si1-xGex)3O9 (x = 0.2) ceramic, and the Q × f values of the BaZr(Si1-xGex)3O9 ceramics could be controlled by varying the Si/Ge-site bond valence. The temperature coefficient of resonance frequency (τf) values of the BaZr(Si1-xGex)3O9 ceramics were mainly affected by the O2-site bond valence, and the optimum τf value (?22.8 ppm/°C) was achieved for the BaZrSi3O9 ceramic. The BaZr(Si1-xGex)3O9 (x = 0.2) ceramic showed the optimum microwave dielectric properties (εr = 8.36, Q × f = 36,100 GHz at 13.81 GHz, and τf = ?34.5 ppm/°C).  相似文献   

16.
AgPb2B2V3O12 (B = Mg, Zn) ceramics with low sintering temperature were synthesized via the conventional solid-state reaction route. Rietveld refinements of the X-ray diffraction patterns confirm cubic symmetry with space group . The number of observed vibrational modes and those predicted by group theoretical calculations also confirm the space group. At the optimum sintering temperature of 750°C/4 hours, AgPb2Mg2V3O12 has a relative permittivity of 23.3 ± 0.2, unloaded quality factor () of 26 900 ± 500 GHz (), and temperature coefficient of resonant frequency of 19.3 ± 1 ppm/°C, while AgPb2Zn2V3O12 has the corresponding values of 26.4 ± 0.2, 28 400 ± 500 GHz () and –18.4 ± 1 ppm/°C at 590°C/4 hours. Microwave dielectric properties of a few reported garnets and Pb2AgB2V3O12 (B = Mg, Zn) ceramics were correlated with their intrinsic characteristics such as the Raman shifts as well as width of A1g Raman bands. Higher quality factor was obtained for lower full width at half-maxima (FWHMs) values of A1g modes. The increase in B-site bond valence contributes to high and low |τf| with the substitution of Zn2+ by Mg2+. Furthermore, the high ionic polarizability and unit cell volume with Zn2+substitution contribute to increased relative permittivity.  相似文献   

17.
The BaBixNb5O15±δ (BBxN, 0.98 ≤ x ≤ 1.02) ceramics were synthesized via solid-state reaction to investigate the effect of Bi3+ nonstoichiometry on their microstructure and electrical conduction behavior. The study of the relationship between structure and conductive behavior revealed two main conclusions: (1) as the concentration of Bi3+ content increased, from deficiency to excess, the oxygen vacancies decreased, and the lattice unit volume V gradually increased; (2) there was a low-frequency Warburg electrode response besides the medium-frequency grain boundary response and high-frequency grain response, and the Bi3+ introduction could reduce conductivity. In addition, the dielectric anomalies indicated by the T1 peak and the T2 peak at 300 °C and 500 °C are related to the Warburg electrode response and to the Bi vacancy and oxygen vacancy defects, respectively.  相似文献   

18.
Single phase ceramics of composition Sr(Ti1–xMgx)O3–x: 0 ≤ x ≤ 0.01 were prepared by sol–gel synthesis and characterized by X‐ray diffraction, scanning electron microscopy, impedance spectroscopy, and current–voltage measurements. The bulk and grain‐boundary conductivities increase on application of a small dc bias voltage in the range 3–200 V/cm and at temperatures in the range 150°C–800°C. A qualitatively similar increase in conductivity occurs on increasing in the surrounding atmosphere, which shows that conduction is p type. The conductivity increase is reversible on removal of the dc bias or on reducing and is not observed in undoped SrTiO3. It is an intrinsic property of the bulk material, differs from the voltage‐dependent effects observed with varistors and is attributed to changes in redox equilibria between oxygen species at the surface which cause changes in carrier concentration in the interior. A capacitive model of this low‐field dc bias effect is presented and compared with a memristive model of high field resistance degradation.  相似文献   

19.
Ba4(Sm0.15Nd0.85)9.33Ti18-zAl3z/4O54 (BSNT-zAl, 0.0 ≤ z ≤ 2.5) ceramics were prepared via a solid-state reaction, and the effects of Al doping on the microwave dielectric properties and defect behavior of the title compound were studied. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) photographs suggested that Al ions successfully entered the lattice to form tungsten-bronze-like solid solutions. With a small amount of Al substitution, the relative dielectric constant (εr), and the temperature coefficient of resonant frequency (τf) values decreased, whereas the quality factor (Q × f) substantially increased by approximately 50%. The defect-related extrinsic dielectric loss was clarified via the thermally stimulated depolarization current (TSDC) technique. With Al doping, the TSDC relaxation of across-grain-boundary oxygen vacancies () vanished, whereas that of defect dipoles () appeared at relatively low temperatures. Therefore, in the BSNT-zAl ceramics, oxygen vacancies were more inclined to interconnect with to form defect dipoles. This could reduce the activity of and account for the notable improvement in the Q × f values. In particular, the excellent characteristics of εr = 67.33, Q × f = 16 530 GHz, and τf = +0.87 ppm/°C were achieved in the specimens with z = 1.5 sintered at 1350°C for 4 hours.  相似文献   

20.
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   

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