Preparation,structure and electrical conductivity of pyrochlore-type samarium–lanthanum zirconate ceramics

A series of zirconate compounds with the general formula Sm_2–xLa_xZr₂O₇ (0 ? x ? 1.0) were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, structure and electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics were investigated by the Archimedes method, X-ray diffraction and impedance spectroscopy measurements. Sm_2–xLa_xZr₂O₇ (0 ? x ? 1.0) ceramics exhibit a pyrochlore-type structure. The measured electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics obeys the Arrhenius relation and gradually increases with increasing temperature from 673 to 1173 K. Sm_2–xLa_xZr₂O₇ ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10^?4 to 1.0 atm at all test temperature levels. The electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics decreases with increasing lanthanum content at identical temperature levels.     

Electrical conductivity of LaxSr2−xFe1−yRuyO4±δ

Materials of the K₂NiF₄ structure type have been prepared and the electrical conductivity in air determined for a number of compositions in the La_xSr_2−xFe_1−yRu_yO_4±δ solid solution series including three with Ru substituted for Fe on the B site: La_0.2Sr_1.8Fe_0.6Ru_0.4O_4±δ, La_0.4Sr_1.6Fe_0.7Ru_0.3O_4±δ, and La_0.6Sr_1.4Fe_0.8Ru_0.2O_4±δ. Overall the total conductivity values measured were lower than expected for the Ru-doped materials, with a peak conductivity of ≈2 S cm⁻¹ at 700 °C. In the undoped La_xSr_2−xFeO_4±δ materials, a significant jump in conductivity was observed between the x = 0.7 and 0.8 compositions and was related to the bonding in the materials and the Fe³⁺/Fe⁴⁺ redox behaviour. In all materials, the conduction behaviour was found to follow a semi-conducting trend.     

Electrochemical performance of (La,Sr)(Co,Fe)O3−δ–(Ce,Sm)O2−θ–CuO composite cathodes for intermediate temperature solid oxide fuel cells

La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Sm_0.2O_2?θ–CuO composite cathodes were studied for the potential application in intermediate temperature solid oxide fuel cells. Ce_0.8Sm_0.2O_2?θ electrolyte with porous Ce_0.8Sm_0.2O_2?θ interlayer was successfully prepared by one-step sintering process. The effect of interlayer between cathode and electrolyte and CuO on the electrochemical performance of the composite cathodes was investigated by AC impedance spectroscopy. The application of interlayer decreased the area specific resistance of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Sm_0.2O_2?θ cathode. The addition of CuO to La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ reduced the phase formation temperature of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ by 150 °C and the addition of CuO to La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Sm_0.2O_2?θ cathode reduced the optimal calcination temperature of the cathode to 800 °C. The composite cathode with 2 mol% CuO calcined at 800 °C exhibited the lowest area specific resistance of 0.05 Ω cm² at 700 °C in air, which was reduced by 67% compared with that of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Sm_0.2O_2?θ cathode. The studies of the corresponding single cell performance, thermal expansion and thermal cycling behaviors further indicated that the composite cathode with 2 mol% CuO could be a promising cathode material.     

Fabrication and electrical properties of Si-based La10−xBix(SiO4)6O3 apatite ionic conductor

In this paper we report an investigation about the relationship between Bi content and conductivity for the La_10?xBi_x(SiO₄)₆O₃ (x = 0.5–2) specimens. Increasing Bi content in apatite-type La_10?xBi_x(SiO₄)₆O₃ specimen leads to increasing the average grain size and sinterability because some Bi ion deposited at grain boundaries which promotes grain growth. The relative sintered density of the La₈Bi₂(SiO₄)₆O₃ specimen is 98%. There is a small shift in diffraction angle of XRD peaks, complicated lattice distortion was observed in the X-ray pattern with increasing content of Bi. Electrical conductivity of La_10?xBi_x(SiO₄)₆O₃ specimen increased with increasing Bi contents and the value of the La₈Bi₂(SiO₄)₆O₃ specimen is 2.4 × 10^?4 S cm^?1 at 700 °C.     

Synthesis of Mg1−xCoxAl2O4 blue pigments via combustion route

MgAl₂O₄ was successfully used as crystalline host network for the synthesis of cobalt-based blue ceramic pigments. Different compositions of Mg_1?xCo_xAl₂O₄ (x = 0.1–0.3) powders have been prepared by the combustion reaction of corresponding metal nitrates with mixtures of urea and β-alanine. The resultant powders were characterized by means of XRD, TG-DTA, EDAX, SEM, BET surface area, diffuse reflectance spectrometry and CIEL1a1b1 color measurement. For x = 0.2, thermal analysis investigations evidenced that combustion reaction occurs at 276 °C. XRD analysis certified the formation of the designed solid solution, no additional thermal treatment being required. EDAX elemental analysis confirmed the purity of the as-prepared compound. The resulted powders had large surface areas, which varied from 8.7 to 62.6 m²/g. The crystallite size of Mg_1?xCo_xAl₂O₄ powders was less than 15 nm. Experimental results evidenced that as the proportion of Co²⁺ increased, the crystallite size decreased and the specific surface area increased. The diffuse reflectance spectra of the Mg_1?xCo_xAl₂O₄ pigments confirmed the presence of tetrahedrally coordinated Co²⁺. CIEL1a1b1 chromatic coordinates indicated that the bluest color was obtained for x = 0.2.     

Synthesis of hexagonal lanthanum germanate apatites through site selective isovalent doping with yttrium

Apatite-type lanthanum silicates/germanates have been attracting considerable interest as a new class of oxide ion conductors, whose conductivity is mediated by oxide ion interstitials. For the germanates, it has been shown that, depending on composition, the cell can be either hexagonal or triclinic, with evidence for reduced low-temperature conductivities for the latter, attributed to increased defect trapping in this lower symmetry cell. In this paper we show that site selective doping of Y into the triclinic apatite-type oxide ion conductors, La_9.33+z(GeO₄)₆O_2+3z/2 (0.33 ≤ z ≤ 0.67) results in a hexagonal lattice for the complete series with correspondingly enhanced low-temperature conductivity.     

Microwave-polyol controlled synthesis and magnetic properties of monodisperse CoxNi1−xFe2O4/MWCNT nanocomposites

Monodisperse Co_xNi_1−xFe₂O₄ nanoparticles (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1) with controllable composition attached on the multi-walled carbon nanotubes (MWCNTs) were prepared by microwave-polyol method. The composition of Co_xNi_1−xFe₂O₄ nanoparticles can be controlled through adjusting the atomic ratios of cobalt and nickel nitrate in the mixed solution. The influence of the microwave power and microwave irradiation time on the monodispersion of nanoparticles was also investigated. The results show quasi-spherical Co_xNi_1−xFe₂O₄ nanoparticles with the face-centered cubic structure and average crystallite size (6 nm) are uniformly dispersed on MWCNTs. The saturation magnetization of Co_xNi_1−xFe₂O₄/MWCNT nanocomposites increases gradually from 12.90 to 20.03 emu/g with increasing Co²⁺ concentration. The coercivity is almost zero at room temperature, which indicates the superparamagnetic behavior.     

Synthesis of nanosized (Zn1−xCox)Al2O4 spinels: New pink ceramic pigments

The Zn_1?xCo_xAl₂O₄ system has been reported to show a blue color with particles sizes that range from 36 nm to 30 μm. However, we have observed a pink color in this system with nanoparticles of an average size of 10 nm.Such differences in the optical properties of this nanosystem are related to the distribution of the cobalt cations in octahedral sites rather than in tetrahedral sites as in standard cobaltite spinels.The solid solution Zn_1?xCo_xAl₂O₄ (x = 0.2, 0.4, 0.6, 0.8 and 1) was synthesized by a co-precipitation reaction from the metallic salts and subsequent calcinations.The color properties and the high thermal stability (1400 °C) of these nanostructures suggest that they have the potential to be applied as satisfactory ceramic pigments.     

Synthesis and characterization of Gd3+ and Nd3+ co-doped ceria by using citric acid–nitrate combustion method

A series of Ce_0.8Gd_0.2?xNd_xO_2?δ (x = 0–0.20) compositions have been synthesized by citric acid–nitrate combustion method. XRD measurements indicate that all the obtained materials crystallized in cubic fluorite-type structure. Lattice parameters were calculated by Rietveld method and the parameter a values in Ce_0.8Gd_0.2?xNd_xO_2?δ system obey Vegard's law, a (Å) = 5.4224 + 0.1208x. The obtained powders have good sinterability and the relative density could reach above 95% after being sintered at 1400 °C. Impedance spectroscopy measurements indicated that the conductivity of Ce_0.8Gd_0.2?xNd_xO_2?δ first increased and then decreased with Nd dopant content x. The maximum conductivity, σ_700 °C = 6.26 × 10^?2 S/cm, was found in Ce_0.8Gd_0.12Nd_0.08O_1.9 when sintered at 1300 °C. The corresponding activation energies of conduction had a minimum value E_a = 0.676 eV. The results tested experimentally the validity of the effective atomic number concept of recent density functional theory, which had suggested that co-dopant with effective atomic number between 61 (Pm) and 62 (Sm) was the ideal dopant exhibiting high ionic conductivity and low activation energy.     

Cation distribution in the Bi4 − xRExTi3O12 (RE = La,Nd) solid solution and Curie temperature dependence

Bi_4 ? xRE_xTi₃O₁₂ (RE = La, Nd) ferroelectric powders were prepared by a co-precipitation route. Raman spectroscopy and X-ray diffraction were employed to determine the crystal site of La³⁺ and Nd³⁺ as well as the effect of their addition on the crystal structure. It was found that La atoms were not only placed preferentially in pseudo-perovskite A sites for concentrations x ≤ 1.2 but also substituted for Bi³⁺ in (Bi₂O₂)^2 + layers for greater concentrations. A similar behavior was observed with the limit value x = 0.8 in case of Nd³⁺. In solid solution La or Nd³⁺ ions diminish the distortions in the octahedron formed by oxygen atoms, so there is a tendency to undergo a transition in crystal symmetry from orthorhombic to tetragonal. Finally differential scanning calorimetry (DSC) shows a linear dependence of the Curie temperature (T_c) when the amount of La³⁺ or Nd³⁺ was increased.     

Thermoelectric and magnetic properties of Ca3Co4–xCuxO9 + δ with x = 0.00, 0.05, 0.07, 0.10 and 0.15

Ca₃Co_4–xCu_xO_9 + δ (x = 0.00, 0.05, 0.07, 0.10 and 0.15) samples were prepared by conventional solid-state synthesis and their thermoelectric properties were systematically investigated. The thermopower of all the samples was positive, indicating that the predominant carriers are holes over the entire temperature range. Ca₃Co_3.85Cu_0.15O_9 + δ had the highest power factor of 2.17 μW cm⁻¹ K⁻² at 141 K, representing an improvement of about 64.4% compared to undoped Ca₃Co₄O_9 + δ. Magnetization measurements indicated that all the samples exhibit a low-spin state of cobalt ions. The observed effective magnetic moments decreased with increasing copper content.     

High permittivity and low dielectric loss of Na0.5Bi0.5−xLaxCu3Ti4O12 ceramics

The phase structure, microstructure and dielectric properties of Na_0.5Bi_0.5?xLa_xCu₃Ti₄O₁₂ (NBLCTO) ceramics were investigated. La³⁺ substitution had a great influence on the phase structure and dielectric properties. The results showed that the pure phase could be more easily obtained when substituting La³⁺ for Bi³⁺. Under the same processing condition (970 °C for 7.5 h) and measuring condition (10 kHz around room temperature), NBLCTO ceramics with x = 0.10 possessed the highest permittivity (1.02 × 10⁴) and lowest dielectric loss (0.022). The obtained NBLCTO ceramics with x = 0.10 also had good frequency stability and good temperature stability (?1.87% to +3.27%) from ?60 °C to 120 °C at both 1 and 10 kHz. Complex impedance results revealed that the grain resistance R_g was 7.18 Ω cm and the grain boundary resistance R_gb was 1.19 × 10⁶ Ω cm.     

Structure,chemical stability and electrical conductivity of perovskite La0.6Sr0.4M0.3Fe0.7O3−δ (M = Co,Ti) oxides

The perovskite La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) powders have been synthesized by the citrate gel method. The structural and chemical stability of the La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) oxides were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. The electrical conductivities of the sintered La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) ceramics were measured. The results demonstrate the chemical stability in H₂/helium (He) atmosphere of the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3?δ oxide is improved significantly compared to that of the La_0.6Sr_0.4Co_0.3Fe_0.7O_3?δ oxide. The incorporation of Ti^3+/4+ ions in the perovskite structure can significantly stabilize the neighboring oxygen octahedral due to the stronger bonding strength, leading to the enhanced structural and chemical stability of the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3?δ. In addition, the perovskite La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) oxides possess much higher chemical stability in CO₂/He atmosphere than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ oxide, in which the perovskite structure is destroyed completely in a flowing CO₂-containing atmosphere.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

Facile synthesis of cubic fluorite nano-Ce1−xZrxO2 via hydrothermal crystallization method

Nano-Ce_1?xZr_xO₂ (x = 0.15, 0.25, 0.5) were synthesized via co-precipitation using NH₄OH as precipitant and hydrothermal crystallization. The XRD results confirmed that the cubic fluorite nano-Ce_1?xZr_xO₂ can form in NH₄OH solution (pH > 10) at 150 °C for 12 h, and well crystallized 20–50 nm nano-Ce_1?xZr_xO₂ were obtained at 200 °C for 22 h. The crystal growth of Ce_1?xZr_xO₂ was suppressed under higher OH^? concentration and crystallite size decreased with increasing concentration of NH₄OH. Ce3d XP spectra showed that the main valence state of the cerium on Ce_1?xZr_xO₂ surface is +4, and substituting Ce⁴⁺ with Zr⁴⁺ has no obvious influence on Ce³⁺/Ce⁴⁺ ratio.     

Effects of interstitial Li+ ions on the properties of novel Li4.08Zn0.04Si0.96O4 ceramic electrolyte

The aim of this work was to investigate the effects of interstitial ions in the novel Li_4 + 2xZn_xSi_1 − xO₄ (x = 0.04) compound prepared via sol gel method. The compound was indexed to the monoclinic unit cell in the space group P2_1/m and the chemical composition of the compound was very close to the designed composition. The introduction of two interstitial Li⁺ ions increased charge carrier concentration in the doped system resulting in an enhancement of conductivity by an order of magnitude as compared to that of the parent compound, Li₄SiO₄. The compound of Li_4.08Zn_0.04Si_0.96O₄ exhibited total conductivity values of 2.51 × 10^− 5 S cm^− 1 at ambient temperature and 3.01 × 10^− 3 S cm^− 1 at 500 °C. Ionic transference number corresponding to Li⁺ ion transport was also found to be higher than the value obtained for the parent compound. This proved that interstitial Li⁺ ions contributed to the total conductivity in the sample. Linear sweep voltammetry result showed that the Li_4.08Zn_0.04Si_0.96O₄ ceramic electrolyte was electrochemically stable up to 5.80 V versus a Li/Li⁺ reference electrode.     

Structure,nonstoichiometry, sintering and oxygen permeability of perovskite SrCo1−2x(Fe,Nb)xO3−δ (x = 0.05, 0.10) oxides

The novel Fe/Nb co-substituted SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.05, 0.10) oxides have been synthesized and characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetry (TG), and scanning electron microscopy (SEM). The XRD and DSC results demonstrate that the structural stability of the Fe/Nb co-substituted samples x = 0.05, 0.10 is improved greatly compared to the sample x = 0.00. The Fe/Nb co-doping in the SrCoO_3?δ oxide results in the improved structural stability of the SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.05, 0.10) oxides. The nonstoichiometric and sintering properties were investigated by TG and SEM, and the oxygen permeation fluxes were measured at 800–950 °C for the sample x = 0.10. The improved oxygen permeability of the ceramic SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.10) membrane compared to the (Ba_0.5Sr_0.5)(Co_0.8Fe_0.2)O_3?δ and SrCo_0.8Fe_0.2O_3–δ membranes, was observed under an air/He oxygen partial pressure gradient at 800–950 °C.     

Controlled synthesis and magnetic properties of Co1−xNix/MWCNT nanocomposites by microwave irradiation

Co_1?xNi_x alloy nanoparticles (x = 0.2, 0.5, 0.6, and 0.8) with the diameter 15–28 nm attached on the surface of multi-walled carbon nanotubes (MWCNTs) were prepared to form Co_1?xNi_x/MWCNT nanocomposites by microwave irradiation. Experimental results demonstrated that Co_1?xNi_x alloy nanoparticles with quasi-spherical and face-centered cubic structure had been attached on the MWCNTs, the composition and size of Co_1?xNi_x alloy nanoparticles could be controlled through adjusting the atomic ratios of metal Co to Ni in the mixed acetate solution, the microwave power and microwave irradiation time, respectively. Both the coercivity and the saturation magnetization of Co_1?xNi_x alloy nanoparticles increased with increasing Co concentration from x = 0.8 to 0.5, and decreased when Co concentration was increased from x = 0.5 to 0.2. These confirm that microwave synthesis is promising for fabricating alloy nanoparticles attached on MWCNTs for magnetic storage and ultra high-density magnetic recording applications.     

Synthesis,structural and electrical properties of triethylene glycol (TREG) stabilized Mn0.2Co0.8Fe2O4 NPs

Triethylene glycol (TREG) stabilized Mn_0.2Co_0.8Fe₂O₄ NPs was synthesized by a glycothermal reaction. XRD analysis identified the product as Mn_0.2Co_0.8Fe₂O₄ with a high phase purity. Nano-sized particles with an average size of about 6–8 nm were obtained with nearly single crystalline nature with TEM analysis. Superparamagnetic-like behavior of TREG stabilized Mn_0.2Co_0.8Fe₂O₄ NPs was observed by VSM. The binding between TREG and Mn_0.2Co_0.8Fe₂O₄ NPs was investigated with FT-IR and found to be via O on the TREG and NP surface. TG analysis indicated that the Mn_0.2Co_0.8Fe₂O₄ NP content was about 40%, with a TREG-shell content to be around 60%. Overall conductivity of the nanocomposite is in the range of 10^?10 to 10^?7 S cm^?1 with a strong dependence on temperature and frequency, indicating ionic conductivity. The nanocomposite exhibited lower ?’ and ?″ compared to TREG stabilized Mn_0.2Co_0.8Fe₂O₄ NPs due to the doping of co-doping of manganese and cobalt.     

Synthesis and electrical conductivity of La0.6Sr0.4Ru1−xMgxO3−δ (x = 0–0.6) perovskite solid solution

Sr and Mg were doped at La- and Ru-sites of perovskite oxide LaRuO₃, respectively, to enhance electrical conductivity and catalytic property as a cathode material for a low temperature solid oxide fuel cell. Crystal structure and particle morphology of La_0.6Sr_0.4Ru_1?xMg_xO_3?δ powders (shorten as LSRM) and electrical conductivity of sintered LSRM were studied. LSRM powders (x = 0–0.6) were prepared by co-precipitation method using metal nitrate solutions and ammonium carbonate solution. The freeze-dried powders were heated at 1273 K in air to form LSRM solid solution of orthorhombic structure. The true densities and particle sizes of LSRM solid solution, where valence of Ru was estimated to be 3+, decreased with increasing Mg content. The electrical conductivity of LSRM at x = 0–0.3 was almost independent of temperature and was in a range of 19–360 S cm^?1 at 1073 K. Hole conduction contributed to the high electrical conductivities. LSRM at x = 0.4 and 0.5 was a mixed conductor of oxide ions and holes, and showed a conductivity of 11 S cm^?1 at 1073 K in air. This conductivity decreased at a lower oxygen pressure and reached a constant value below 10 Pa of oxygen pressure.