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1.
Lanthanum-doped bismuth titanate (Bi3.25La0.75Ti3O12 or BLT) is important ferroelectric materials for FeRAMS, which need further improved by substituting isovalent cations to assist the elimination of defects such as oxygen vacancy. In this work, fabrication and investigation of substituting Mn4+ for Ti4+ ion on B-site of Bi3.25La0.75Ti3O12 ceramics were carried out. X-ray diffraction patterns of BLTMn ceramics indicated orthorhombic structure with lattice distortion, especially for samples with higher concentration of MnO2 dopant. Microstructural investigation showed that all ceramics composed mainly of plate-like grains. An increase in MnO2 doping content increased diameter and thickness of grains but reduced density of the ceramics. Electrical conductivity was found to decrease while dielectric constant increased with Mn4+ doping concentration.  相似文献   

2.
Pure and lanthanum doped barium bismuth titanate BaBi4−xLaxTi4O15 (BBLT, x=0, 0.05, 0.15, 0.30) ceramics were prepared utilizing solid state method. The X-ray diffraction (XRD) data confirmed formation of single-phase Aurivillius compounds while SEM micrographs did not show evident grain size change of doped ceramics. Dielectric properties were investigated in 1.21 kHz to 1 MHz frequency range and in the temperature range of 20 to 727 °C. When Bi3+ is substituted with La3+, a significant disorder was induced and the material exhibited broadening of the phase transition. Impedance analysis confirmed the presence of two semicircular arcs in doped samples suggesting the existence of grain and grain-boundary conduction. The dc-conductivity and activation energies were evaluated for all compositions.  相似文献   

3.
Nano-size Ca1−χLa2χ/3Cu3Ti4O12 (χ = 0.00, 0.05, 0.10, 0.15 and 0.20) precursor powders were prepared via the sol–gel method and the citrate auto-ignition route and then processed into micro-crystal Ca1−χLa2χ/3Cu3Ti4O12 ceramics under heat treatment. Characterization of the as-obtained ceramics with XRD and SEM showed an average grain sizes of ∼1–2 μm, indicating La3+ amount to have little impact on grain size. The room-temperature dielectric constant of the Ca1−χLa2χ/3Cu3Ti4O12 ceramics sintered at 1000 °C was of the order of 103–104 despite the variation of χ values. Compared with CaCu3Ti4O12, La3+-doped CaCu3Ti4O12 showed a flatter dielectric constant curve related to frequency. It was found that the loss tangent of the Ca1−χLa2χ/3Cu3Ti4O12 ceramics was less than 0.20 in ∼600–105 Hz region, which rapidly decreased to a minimum value of 0.03 by La3+doping with χ = 0.05. Our measurement of the ceramics conductivities (σ) also indicated that the appropriate introduction of La3+ into CaCu3Ti4O12 would distinctly result in its dielectric properties.  相似文献   

4.
The bismuth layer-structured Na0.5Bi4.5-xPrxTi4O15 (x?=?0, 0.1, 0.2, 0.3, 0.4, and 0.5) (NBT-xPr3+) ceramics were fabricated using the traditional solid reaction process. The effect of different Pr3+ contents on dielectric, ferroelectric and piezoelectric properties of Na0.5Bi4.5Ti4O15 ceramics were investigated. The grain size of Pr3+-doping ceramics was found to be smaller than that of pure one, the maximum dielectric constant and Curie temperature Tc gradually decreased with increasing Pr3+ contents, and the dielectric loss decreased at high temperature by Pr3+-doping. Moreover, the activation energy (Ea), resistivity (Z’), remanent polarization (2Pr) and piezoelectric constant (d33) increased by Pr3+-doping. The NBT-xPr3+ ceramics with x?=?0.3 achieved the optimal properties with the maximum dielectric constant of 1109.18, minimum loss of 0.00822 (250?kHz), Ea of 1.122?eV, Z’ of 7.9?kΩ?cm (725 ºC), d33 of 18 pC/N, 2Pr of 12.04 μC/cm2. The enhancement was due to the addition of Pr3+ which suppressed the decreasing of resistivity at high temperature and made it possible for NBT-xPr3+ ceramics to be poled in perpendicular direction, implying that it is a great improvement for Na0.5Bi4.5Ti4O15 ceramics in electrical properties.  相似文献   

5.
Red-light-emitting phosphors of La2Mo2O9:Pr3+ and S-doped La2Mo2O9:Pr3+ were prepared by high temperature solid state reaction. Under the excitation of 450 nm blue light, all samples produced a red emission peak at 650 nm corresponding to the characteristic transition of Pr3+ (3P03F2). The dependence of Pr3+ doping content (x) on the luminescent intensity was analyzed, and the optimal doping content of Pr3+ was x=0.07. After a small quantity of sulfur was introduced into the system, the luminescence intensity of phosphors was obviously enhanced. The reasons for the enhancement of luminescence are due to improved crystallization after S doping and the relatively large electronegativity difference between S and Mo. Additionally, the coincidence of the excitation wavelength with the emission of GaN chips may recommend this phosphor system as a potential candidate for use in white light-emitting diodes.  相似文献   

6.
New ferroelectric ceramics Bi-BZT of ABO3 perovskite type were synthesized in the (Ba1−3x/2Bix)(ZryTi1−y)O3 system by solid state reaction route. The effect of the substitution of barium by bismuth in the A cationic site on structural and dielectric properties was investigated. The dielectric constant was studied in the temperature range from 20 K to 320 K at frequencies ranging from 0.2 to 100 kHz. A clear relaxor behavior was observed for samples with x ≥ 0.075 and y = 0.1. In this case the value of the relaxation parameter γ ≈ 2 estimated from the linear fit of the modified Curie–Weiss law, indicates the relaxor nature of the Bi-BZT ceramics. The dielectric relaxation rate follows Vogel–Fulcher relation with an activation energy of 0.26 eV and 0.27 eV, an attempt frequency f0 = 3.4 × 1012 Hz and 5.7 × 1012 Hz and a static freezing temperature TVF = 98 K and 94 K respectively for x = 0.075 and x = 0.1.  相似文献   

7.
In this work, [(Bi1-xLax)0.5Na0.5]0.94Ba0.06(Ti1-5y/4Nby)O3 ceramics have been developed by the dual-substitution of La3+ for Bi3+ and Nb5+ for Ti4+ and prepared by an ordinary sintering technique. All ceramics can be well-sintered at 1200 °C. The addition of La3+ and Nb5+ reduces the grain size and improve the dielectric breakdown strength of the ceramics; moreover, after the introduction of La3+ and Nb5+, the remanent polarization of the ceramics is significantly reduced, while the maximum polarization remains the same large value as that of the ceramic without the doping of La3+ and Nb5+. As a result, high energy storage density and discharge efficiency are achieved at x/y = 0.07/0.02, giving the large storage density of 1.83 J/cm3 and high discharging efficiency of 70%. The present work presents a feasible strategy to develop energy storage materials based on perovskite ferroelectrics by the partial substitutions in the A and B sites.  相似文献   

8.
Ca0.9La0.067TiO3 (abbreviated as CLT) ceramics doped with different amount of Al2O3 were prepared via the solid state reaction method. The anti-reduction mechanism of Ti4+ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al2O3. The results showed that Al3+ substituted for Ti4+ to form solid solution and the solid solubility limit of Al3+ is near 1.11 mol%. Furthermore, the reduction of Ti4+ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al2O3 exhibited good microwave dielectric properties: εr = 141, Q × f = 6848 GHz, τf = 576 ppm/°C.  相似文献   

9.
The synthesis of intercluster porous nanocomposites obtained from polyoxometallate compounds such as the [AlO4Al12(OH)24(H2O)12]7+ cation (named Al13) and the Anderson-type [Al1−x Cr x Mo6O24H6]3− anion (named Al1−x Cr x Mo6) has been performed in order to study the interaction between the two cluster ions, the stability of the XMo6 planar configuration, the products obtained after thermal treatment, the structure and the local symmetry of the Cr3+ species. Chemical, thermal, structural and spectroscopic characterizations of the original and thermally treated phases have been followed by different techniques such as TG-DTA, XRD, SEM-EDAX, and mainly by EPR. All the results have shown that the structure of the intercluster nanocomposites (Al13)(Al1−x Cr x Mo6)2 precursors is similar to that reported by Son et al. for the chromium-free (Al13)(AlMo6)2 intercluster nanocomposite [Son et al., J. Am. Chem. Soc. 122 (2000) 7432]. After thermal treatment in air at several temperatures of the (Al13)(Al1−x Cr x Mo6)2 nanocomposites the following phases have been observed and characterised: (i) at 400 °C an amorphous phase containing dispersed Cr3+ ions; (ii) at 700 °C a crystalline phase corresponding to Cr2(MoO4)3/Al2(MoO4)3 solid solutions; (iii) at 950 °C α-Al2O3/Cr2O3 solid solutions with a random dispersion of the Cr3+ ions.  相似文献   

10.
We report on the structure, dielectric, ferroelectric, and photoluminescent properties of Sm3+-doped Bi4Ti3O12 thin films which were prepared on fused silica and Pt/Ti/SiO2/Si substrates by sol-gel method. The X-ray diffraction analysis confirmed that the Bi4-xSmxTi3O12 (BSmT) thin films were well crystallized in layered perovskite structure without any secondary phase. Raman spectra indicated that the structure of BSmT thin films was significantly distorted because of the Sm3+ doping. An appropriate doping amount of Sm3+ ions leads to obvious enhancement in ferroelectric and dielectric properties of BSmT thin films due to structure distortion and reduction in defects. In addition, the BSmT thin films also show orange-red color emission at 601?nm and long florescence lifetime (> 0.6?ms). This study indicated that lead-free BSmT thin films, which are featuring good electrical and photoluminescent properties, may have potential applications in integrated optoelectronic devices.  相似文献   

11.
Mesoporous BixTi1−xO2 spheres with core–shell chamber were prepared by alcoholysis under solvothermal conditions. The cross-condensation between Ti–OH and Bi–OH ensured complete incorporation of Bi-dopants into TiO2 lattice, though Bi atom is much bigger than Ti. Meanwhile, the aggregation of titania building clusters into spheres and their subsequent reactions including dissolution and re-deposition processes lead to the hollow spheres with tunable interior structure. The Bi-doping induced strong spectral response in visible region owing to the formation of narrow intermediate energy band gaps. Meanwhile, multiple reflections within the sphere interior voids promoted the light absorbance. As a result, the as-prepared BixTi1−xO2 spheres exhibited much higher activity than the undoped TiO2, the Bi2O3/TiO2 obtained by impregnating the TiO2 with Bi(NO3)3 solution, and the BixTi1−xO2 after being ground during photodegradation of p-chlorophenol under visible light irradiation. Meanwhile, the BixTi1−xO2 could be used repetitively for 10 times owing to the high hydrothermal stability and the absence of Bi-leaching.  相似文献   

12.
Bi4?xLaxTi3O12 (BLT) ceramics were prepared and studied in this work in terms of La3+-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (xL) of La3+ into the Bi4Ti3O12 (BIT) matrix was here found to locate slightly above x = 1.5. Further, La3+ had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric–paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La3+ content.  相似文献   

13.
Polycrystalline Ni doped Na.5Bi0.5TiO3 samples (Na0.5Bi0.5)Ti1-xNixO3, (x?=?0.5, 0.10, 0.15) have been prepared by solid state reaction. The appearance of the additional peak in X-ray diffraction pattern indicates the ordering of Ti4+ and Ni2+ ions. Polygonal grains are converted into flakes with an increase of Ni concentration. Replacement of Ti4+ by Ni2+ strongly modifies the relative contribution of two peaks in the Raman bands within 200–400?cm?1. Oxygen vacancy is observed in X-ray photoelectron spectrum to maintain charge neutrality due to aliovalent doping. Broad diffuse phase transition centered at the dielectric constant maximum indicates relaxor behaviour. Comparison between impedance and electric modulus spectrum suggests non-Debye relaxation. The ac conductivity follows the power law with the frequency exponent lies 0.52???0.72. The generation of holes by divalent Ni dopant at tetravalent Ti sites enhances optical band gap.  相似文献   

14.
Lanthanum molybdate, La2Mo2O9, has been attracted considerable attention owing to its high concentration of intrinsic oxygen vacancies, which could be reflected by enhanced phonon scattering and low thermal conductivity. A new series of La2Mo2O9‐based oxides of the general formula La2?xSmxMo2?xWxO9, where x ≤ 0.2, were synthesized by citric acid sol–gel process. The variation in thermal conductivity with Sm3+and W6+ fractions was analyzed based on structure information provided by X‐ray diffraction and Raman spectroscopy. The fully dense La2?xSmxMo2?xWxO9 ceramics showed a minimum thermal conductivity value [κ = 0.84 W·(m·K)?1,T = 1073 K] at the composition of La1.8Sm0.2Mo1.8W0.2O9, which stems from the multiple enhanced phonon scatterings due to mass and strain fluctuations at the La3+ and Mo6+ sites as well as the high concentration of intrinsic oxygen vacancies embedded in the crystal lattice. The thermal conductivities present an abrupt decrease at the structural transition, which is due to the phase transformation from a low‐temperature ordered form (monoclinic α‐La2Mo2O9) to a high‐temperature disordered form (cubic β‐La2Mo2O9).  相似文献   

15.
In this study, Sm3+ doped Na0.5La0.5Bi8-xSmxTi7O27 (NBT-BITL-xSm, x = 0, 0.01, 0.015, 0.02, and 0.03) ceramics were synthesized via a conventional solid-state reaction process. The structural, electrical, and photoluminescence properties of NBT-BITL-xSm ceramics were systematically investigated. The crystal structure of NBT-BITL-xSm was refined using XRD Rietveld refinement and found to possess a single orthorhombic structure at room temperature. Raman spectroscopy revealed that Sm3+ ions preferred to substitute for Bi3+ located in the A-sites of pseudo-perovskite layers, inducing a slight decrease in orthorhombic distortion. Strong characteristic emission peaks of Sm3+ ions were observed in orange-red regions under a 407 nm laser source, and the sample with x = 0.015 achieved the optimal photoluminescent property. Dielectric measurements showed double anomaly permittivity peaks at the temperature of 589 and 600°C (Tm and Tc, respectively). The complex impedance spectrum indicated that the electrical conductivities mainly originated from crystal grains at high temperature. The activation energy was calculated to be 1.37–1.44 eV from Arrhenius fitting results. After Sm3+ substitution, the activation energy for conductivity was increased as a result of reduced oxygen vacancies.  相似文献   

16.
Pb0.325Sr0.675Ti1-xMnxO3 ceramics (x?=?0, 0.001, 0.005, 0.01, and 0.05) were successfully prepared by traditional solid-state reaction method. It was found that the lattice constant calculated through Rietveld refinement initially increased and then decreased with increasing Mn content, which was attributed to the variation in valence state of Mn and Ti ions. The microstructure gradually varied from the coexistence of large grains and fine grains for x?=?0 to the uniform grain for x?=?0.05 by increasing the doping Mn ions. With increasing Mn content from x?=?0 to x?=?0.05, the Curie temperature (Tc) dramatically decreased from 25?°C to ??40?°C and dielectric maximum decreased from 27,100 to 13,200. Pb0.325Sr0.675Ti1-xMnxO3 ceramics with x?=?0.001 showed the lowest dielectric loss of 0.006 with a relatively high dielectric peak value of ~ 21,000. The grain boundaries resistance obtained from the complex impedance decreased with the increase of Mn content. The decrease in resistance was ascribed to oxygen vacancies and electronics produced by the change of ionic valence state. X-ray photoemission spectroscopy revealed that Ti ions were Ti4+ and the valences of Mn ions were deduced to be mainly in the form of Mn2+ and/or Mn3+ for ceramics with low content of Mn, while the Ti ions were in the form of Ti3+ and Ti4+ and Mn ions were diverse valence states with the coexistence of Mn2+, Mn3+, and Mn4+ for ceramics with x?=?0.01 and 0.05.  相似文献   

17.
Y2−xLaxMo3O12 (x=0, 0.5, 2) ceramics were successfully synthesized by the solid state reaction method. The microstructure, composition and thermal expansion property of the resulting samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and dilatometry. Results indicate that the Y1.5La0.5Mo3O12 crystallizes in monoclinic Tb2Mo3O12-type structure and it is non-hygroscopic. The Y1.5La0.5Mo3O12 ceramic is denser than the Y2Mo3O12 and La2Mo3O12 ceramics, and its relative density can reach 94.12% of the theoretical value. Most importantly, it shows almost zero thermal expansion and its thermal coefficient is 0.87×10−6 K−1 from 178 °C to 600 °C. Y2Mo3O12 ceramic shows negative thermal expansion whereas La2Mo3O12 ceramic shows positive thermal expansion, their thermal expansion coefficients being−12.06×10−6 K−1 and 8.88×10−6×10−6 K−1, respectively.  相似文献   

18.
In this study, densification, microstructural evolution and microwave dielectric properties of (1 − x)BiSbO4xBi2Mo2O9 ceramics (x = 0–0.25) were investigated. Bi2Mo2O9 was selected as the sintering aid as well as the modifier of the dielectric properties for BiSbO4 ceramic. In comparison with pure BiSbO4 densified at 1100 °C, the 0.75BiSbO4–0.25Bi2Mo2O9 composites emerged to reach maximum sintering density at 775 °C. No other second phase was detected while the microstructure exhibited a bimodal grain size distribution as both 1–2 μm large grains of Bi2Mo2O9 and 0.2–0.5 μm fine grains of BiSbO4 were observed. The ceramic with the best performance in terms of microwave dielectric properties in this system is found to be the 0.82BiSbO4–0.18Bi2Mo2O9 composite, which reports a ?r of 24.3, a Q × f of 24,019 GHz, and a τf of −4 ppm/°C when sintered at 825 °C.  相似文献   

19.
《Ceramics International》2020,46(2):1334-1342
The electrical properties of La2Ti2O7 (LTO) ceramics have been enhanced through the substitution of La3+ ions by Pr3+ ions. Almost all doped Pr3+ ions will get at A - site without causing a change on monoclinic phase of LTO. The average grain size is 17.8 μm for La1.9Pr0.1Ti2O7 ceramics. The relaxation activation energy which is contributed by defect dipoles that are formed from TiO6 oxygen octahedrons’ distortions in grains is 1.6 eV for La1.8Pr0.2Ti2O7 ceramics. This kind of defects will be activated from 520 °C and completely be activated until 650 °C. The piezoelectric coefficient d33 = 3.0 pC/N of La2-xPrxTi2O7 ceramics maintains stable when the Pr3+ doping content x ranging from 0.1 to 0.3.  相似文献   

20.
The microwave dielectric properties of Sm(Mg0.5Ti0.5)O3 incorporated with various amount of Bi2O3 and B2O3 additives have been investigated systematically. In this study, both Bi2O3 and B2O3 additives acting as a sintering aid can effectively lower the sintering temperature from 1550 °C to 1300 °C. The ionic radius of Bi3+ for a coordination number of 6 is 0.103 nm, whereas the ionic radius of B3+ is 0.027 nm. Clearly, the ionic radius of Bi3+ is greatly larger than one of B3+, which resulted in the specimens incorporated with Bi2O3 having larger lattice parameters and cell volume than those incorporated with B2O3. The experimental results show that no second phase was observed throughout the entire experiments. Depending on the interfacial tension, the liquid phase may penetrate the grain boundaries completely, in which case the grains will be separated from one another by a thin layer as shown in Sm(Mg0.5Ti0.5)O3 ceramics incorporated with Bi2O3. Whereas, in Sm(Mg0.5Ti0.5)O3 ceramics incorporated with B2O3, the volume fraction of liquid is high, the grains may dissolve into the liquid phase, and rapidly rearrange, in which case contact points between agglomerates will be dissolved due to their higher solubility in the liquid, leading plate-like shape microstructure.A dielectric constant (?r) of 29.3, a high Q × f value of 26,335 GHz (at 8.84 GHz), and a τf of −32.5 ppm/°C can be obtained for Sm(Mg0.5Ti0.5)O3 ceramics incorporated with 10 mol% Bi2O3 sintered at 1300 °C. While Sm(Mg0.5Ti0.5)O3 ceramics incorporated with 5 mol% B2O3 can effectively lower temperature coefficient of resonant frequency, which value is −21.6 ppm/°C. The Sm(Mg0.5Ti0.5)O3 ceramic incorporated with heavily Bi2O3 and B2O3 additives exhibits a substantial reduction in temperature (∼250 °C) and compatible dielectric properties in comparison with that of an un-doped one. This implied that this ceramic is suitable for miniaturization in the application of dielectric resonators and filters by being appropriately incorporated with a sintering aid.  相似文献   

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