Structure and microwave dielectric properties of La(2−x)/3Nax(Mg1/2W1/2)O3

The structure evolution, sintering behavior and microwave dielectric properties of La_(2−x)/3Na_x(Mg_1/2W_1/2)O₃ (x = 0–0.5) were investigated in this paper. The X-ray diffraction (XRD) results show that all samples exhibit single phase, and the structure changed from orthorhombic when 0 ≤ x < 0.3 to monoclinic phase when 0.3 ≤ x ≤ 0.5. The size and ordering degree of A/B-site domains decrease with the increase in x value. The sintering temperature of the Na-doped samples increased compared to the pure La_2/3(Mg_1/2W_1/2)O₃ (LMW) due to the estimated decrease in the concentration of A-site vacancies. The addition of Na⁺ ion does not affect the dielectric permittivity greatly. The Q × f value decreases with the increase in x value, although the estimated concentration of A-site vacancies decreases with increasing x, which may be ascribed to the decrease of A/B-site ordering and domain size with the increase in x. The temperature coefficient of resonant frequency changed from negative values into positive values with the increase in x value.     

Preparation and characterisation of LaNixCo1−xO3 thin films on polycrystalline Al2O3-substrates

The perovskite LaNi_xCo_1−xO₃ exhibits metallic conductivity with a change from p- to n-type conduction around x=0·5, thus being a candidate for electrodes or buffer layers in thin film technology. Thin films of LaNi_xCo_1−xO₃ have been grown onto polycrystalline Al₂O₃ substrates by Chemical Solution Deposition (CSD) of nitrate solutions in ethanol/butylacetate. The solutions were applied by dip-coating. After pyrolysis the compounds are formed in air at temperatures between 600°C and 750°C. Formation of the perovskite phase was confirmed by grazing angle X-ray diffraction. Electron micrographs revealed that the obtained films were smooth and crack-free and consisted of nanocrystalline LaNi_xCo_1−xO₃ particles. The thickness of the films was between 200 nm and 400 nm, depending on the conditions of the dipcoating procedure. Specific conductivities of the film were measured using the van der Pauw-method and were found to be around 400 S/cm for LaNiO₃ and around 1 S/cm for LaCoO₃ at room temperature.     

Lanthanum nickelate thin films deposited by spray pyrolysis: Crystallization,microstructure and electrochemical properties

Thin films from the La_n+1Ni_nO_3n+1 system exhibit favorable dielectric and electrochemical properties that may prove useful for a variety of devices ranging from ferroelectrics to low-temperature solid oxide fuel cells. The present work covers the compositional, microstructural and electrochemical characterization of thin lanthanum nickelate films deposited by spray pyrolysis. In accordance with the phase diagram, LaNiO_3?δ or La₄Ni₃O_10?δ films were obtained during annealing of spray deposited films at temperatures between 540 °C and 1100 °C. Whereas LaNiO_3?δ films exhibited a high metallic conductivity, La₄Ni₃O_10?δ films were semiconducting. Electrochemical impedance spectroscopy indicated an increase of the area specific oxygen reduction resistance with the annealing temperature. The study highlights how the phase and microstructure of thin films from the La_n+1Ni_nO_3n+1 system can be tailored by annealing of initially amorphous films. LaNiO_3?δ films have a high potential for application in electrochemical devices operating at low temperatures where high electrical conductivity is required.     

Catalytic activity of nanometer La1−xSrxCoO3 (x = 0, 0.2) perovskites towards VOCs combustion

Combustive oxidation of volatile organic compounds (VOCs), such as propyl alcohol, toluene and cyclohexane, were studied. The combustion was catalyzed by nanoparticles of La_1−xSr_xCoO₃ (x = 0, 0.2) perovskites prepared by a co-precipitation method. The results showed high activities of the perovskite catalysts. Compared to LaCoO₃, in particular, La_0.8Sr_0.2CoO₃ was much higher in catalytic ability. The total oxidation of VOCs followed the increasing order: cyclohexane < toluene < propyl alcohol. The T_99% of cyclohexane was 40 °C lower than that of toluene, which appeared to be determined by the bond strengths of the weakest C–H and C–C bonds. The 100-h stability experiments showed that La_1−xSr_xCoO₃ (x = 0, 0.2) perovskite was highly stable.     

X-ray diffraction and infrared spectra studies of FexMn2.34−xNi0.66O4 (0 < x < 1) NTC ceramics

Series of Fe_xMn_2.34−xNi_0.66O₄ (0 < x < 1) NTC ceramics were prepared by the Pechini method. Resistivity, thermal constant (B) and aging values were measured. It was found that the resistivity increased with increasing iron content x. The B value however first decreased with increasing x in the range of x < 0.6 and then increased with further increase in x. Aging reached a maximum in the middle range (x = 0.4–0.6) of iron content. X-ray diffraction (XRD) and infrared analysis were used to determine the distribution of Fe³⁺ ions. The Fe³⁺ ions were found to occupy both A- and B-site when x < 0.6 and then go to B-site when x > 0.6. An redistribution of the Fe³⁺ ions between A- and B-site was related to the aging of the NTC thermistor.     

Effect of La-Ni substitution on structural,magnetic and microwave absorption properties of barium ferrite

In this paper, La-Ni substituted barium ferrite nanoparticles were prepared by a co-precipitation method. The morphology, structure, magnetic and microwave absorption properties of samples were accomplished by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), vibrating sample magnetometer (VSM) and vector network analysis. From the results evaluation, it can be seen that the magnetoplumbite structure for all of the samples have been formed and the average crystallite sizes of Ba_1−xLa_xFe_12−xNi_xO₁₉ nanoparticles within in the range of 50.9–65.5 nm. Ba_0.9La_0.1Fe_11.9Ni_0.1O₁₉ exhibits a remarkable reflection loss of −13.5 dB at 13.05 GHz with a matching thickness of 1.5 mm. The reflection loss results indicate that Ba_0.9La_0.1Fe_11.9Ni_0.1O₁₉ nanoparticles may be used as a potential for thin microwave absorbers.     

Lattice oxygen of La1−xSrxMO3 (M = Mn,Ni) and LaMnO3−αFβ perovskite oxides for the partial oxidation of methane to synthesis gas

The partial oxidation of methane to synthesis gas by using the lattice oxygen of La_1−xSr_xMO₃ (M = Mn, Ni; x = 0–0.4) and LaMnO_3−αF_β (β/(3 − α) = 0.1) perovskite oxides was explored. Approximately 75% CO selectivity at 16% CH₄ conversion with H₂/CO molar ratio of ca. 2.5 can be achieved at 800 °C. The stability of the perovskite structure and the reactivity/selectivity of lattice oxygen are found to be dependent on (i) B-site element, (ii) degree of substitution of La with Sr, and (iii) fluorination of the perovskite oxide.     

Effect of site occupancies of rare earth ions on electrical properties in Ni-MLCC based on BaTiO3

The site occupancies of rare earth ions for Ba-site to Ti-site were quantitatively estimated in (Ba_1−x,R_x)(Ti_1−x,R_x)O₃ (R = Eu, Ho), (Ba_1−3xEu_2x)TiO₃, and Ba(Ti_1−2xEu_2x)O_3−x systems by applying the Rietveld refinement to the data obtained from the synchrotron radiation powder diffraction measurement. The occupational ratio of Ba-site to Ti-site for the larger rare earth ion (Eu) was 49/51 (x = 0.10), whereas for the smaller ion (Ho) was 9/91 (x = 0.01) in (Ba_1−x,R_x)(Ti_1−x,R_x)O₃ system. Furthermore, the occupational ratio was greatly dependent on the Ba/Ti ratio, in (Ba_1−3xEu_2x)TiO₃ system it was 92/8 (x = 0.03), whereas that in Ba(Ti_1−2xEu_2x)O_3−x system was 20/80 (x = 0.01). The Curie point shifted to lower temperature effectively with increasing in the occupational ratio of rare earth ion into Ba-site.     

Ordering structure of barium magnesium niobate ceramic with A-site substitution

The ordering behaviour of Ba(Mg_1/3Nb_2/3)O₃ ceramics (BMN) substituted by La³⁺, Na⁺, K⁺ was investigated using X-ray powder diffraction and transmission electron microscopy. The 1:2 ordered structure of BMN can be transformed to 1:1 ordered structure by substituting a small amount of La cation ion into the A-site. Moreover, the degree of ordering was increased with La content in the compound, and reached almost unity at [La] = 50 mol%. When the La ion in (Ba_1−xLa_x)(Mg_(1+x)/3Nb_(2−x)/3)O₃ (BLMN) was substituted by Na or K ions, the 1:1 ordered structure of BLMN was transformed into the 1:2 ordered structure. The degree of 1:2 ordering was influenced by the sintering temperature and the size difference between the A and B site ions.     

Influence of A- and B-site doping on the properties of the system La2CoO4±δ

In the present paper the compounds LaSrCo_0.5M_0.5O_4±δ (M = Co, Fe, Mn, Ni) and La_1.4Sr_0.6Co_0.5M_0.5O_4±δ (M = Co, Ni) were prepared and characterised in order to elucidate the influence of strontium doping on A-site as well as doping with transition metals on B-site of the mixed conductor La₂CoO_4±δ. All the prepared oxides of this paper possessed the K₂NiF₄ structure, exhibited high electrical conductivity (>100 S/cm) and adequately low linear thermal expansion coefficient. Therefore, they are very promising materials for high temperature electrochemical applications.     

Fabrication and phase transition of La2−xLuxZr2O7 transparent ceramics

A series of transparent ceramics with the composition of La_2−xLu_xZr₂O₇ (x = 0−2.0) were prepared by solid-state reactive sintering in vacuum. With the increase of Lu content (x), phase transition from pyrochlore to defective fluorite occurred and a two-phase region existed in the range of x = 0.6−1.2. Grain sizes of the pyrochlore phase dominated samples (x < 0.5) were 11−14 μm, and that of the defective fluorite phase dominated samples were larger than 60 μm. However, grain sizes of the samples in the two-phase region were smaller than 3 μm. The La_0.8Lu_1.2Zr₂O₇ ceramic with the smallest grain size (∼2.5 μm) reached a highest in-line transmittance of 72.4% at 1100 nm among all the samples.     

Phase relationships and transport in Ti-, Ce- and Zr-substituted lanthanum silicate systems

The solubility of Ti⁴⁺ in the lattice of apatite-type La_9.83Si_6−xTi_xO_26.75 corresponds to approximately 28% of the Si-site density. The conductivity of La_9.83Si_6−xTi_xO_26.75 (x = 1–2) is predominantly oxygen-ionic and independent of the oxygen partial pressure in the p(O₂) range from 10⁻²⁰ to 0.3 atm. The electron transference numbers determined by the modified faradaic efficiency technique are lower than 0.006 at 900–950 °C in air. The open-circuit voltage of oxygen concentration cells with Ti-doped silicate electrolytes is close to the theoretical Nernst value both under oxygen/air and air/10%H₂–90%N₂ gradients at 700–950 °C, suggesting the stabilization of Ti⁴⁺ in the apatite structure. Titanium addition in La_9.83Si_6−xTi_xO_26.75 (x = 1–2) leads to decreasing ionic conductivity and increasing activation energies from 93 to 137 kJ/mol, and enhanced degradation in reducing atmospheres due to SiO volatilization. At p(O₂) = 10⁻²⁰ atm and 1223 K, the conductivity decrease after 100 h was about 5% for x = 1 and 17% for x = 2. The solubility of Zr⁴⁺ in the La_9.83Si_6−xZr_xO_26.75 system was found to be negligible, while the maximum concentration of Ce⁴⁺ in La_9.4−xCe_xSi₆O_27−δ is approximately 5% with respect to the number of lanthanum sites.     

Microwave dielectric properties of BaxLa4Ti3 + xO12 + 3x (x = 0.0–1.0) ceramics

In the BaO–La₂O₃–TiO₂ system, the Ba_nLa₄Ti_3 + nO_12 + 3n homologous compounds exist on the tie line BaTiO₃–La₄Ti₃O₁₂ besides tungstenbronze-type like Ba_6 − 3xR_8 + 2xTi₁₈O₅₄ (R = rare earth) solid solutions. There are four kinds of compounds in the homologous series: n = 0, La₄Ti₃O₁₂; n = 1, BaLa₄Ti₄O₁₅; n = 2, Ba₂La₄Ti₅O₁₈; n = 4, Ba₄La₄Ti₇O₂₄. These compounds have the layered hexagonal perovskite-like structure, which has a common sub-structure in the crystal structure. These compounds have been investigated in our previous studies. In this study, we have investigated the phase relation and the microwave dielectric properties of Ba_xLa₄Ti_3 + xO_12 + 3x ceramics in the range of x between 0.2 and 1.0. With the increase in x, the dielectric constant ɛ_r locates around 45, the quality factor Q × f shows over 80,000 GHz at x = 0.2 and the minimum value of 30,000 GHz at x = 0.9, and the temperature coefficients of resonant frequency τ_f is improved from −17 to −12 ppm/°C. At x = 0.2, the ceramic composition obtained has dielectric constant ɛ_r = 42, the temperature coefficient of the resonant frequency τ_f  = −17 ppm/°C and a high Q × f of 86,000 GHz.     

Influence of Al-substitution on structures,resistivity and magnetic properties of LaxSr(2−x)Fe(1+y)Mo(1−y)O6 (x=3y,y=0.05, 0.1, 0.15, 0.2)

Two series of single-phased La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ and La_xSr_(2−x)Fe_(1+0.5y)Al_0.5yMo_(1−y)O₆ (x=3y, y=0.05, 0.1, 0.15 and 0.2) double perovskites were prepared by solid-state reaction. The effects of Al-substitution on the structures, resistivity and magnetic properties of La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ were investigated. Although Al-replacement exhibits a negligible influence of on the B-site ordering degree, it results in the suppression of magnetisation caused by non-magnetic Al³⁺ ions. Reduction of grain sizes leads to increased resistivity, thus an optimised magnetoresistance (MR) behaviour is observed. The greatest MR extent improvement can be obtained when y is 0.15 and the MR% of the Al-doped ceramics reaches −10.5% (10 K, 1 T), which is 2 times greater than that of the undoped ceramics (−4.6%, 10 K, 1 T). Interestingly, the Curie temperature (Tc) of both Al-doped and undoped samples maintained relatively constant values of approximately 420 K and 405 K, respectively, which were different results from the data obtained for similar electron-doping systems in the literature.     

Electrical properties of (La0.9Ca0.1)(Co1−xNix)O3−δ cathode materials for SOFCs

Modified perovskite ceramics (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ (x = 0–0.3) cathodes for solid oxide fuel cells (SOFCs) were synthesized by solid state reaction. The lattice parameters, electrical conductivity, activation energy, and microstructures of these specimens were investigated systematically in this study. The results exhibited that all specimens are rhombohedron structures and their tolerance factors were greater than 0.97, indicating that the perovskite was not distorted by Ni²⁺ cation substitution for the B site of (La_0.9Ca_0.1)CoO_3?δ. The microstructures of the (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ specimens showed good densification, and were well-sintered, with few pores. The electrical conductivity behavior conformed to the nature of a semiconductor, for all specimens. As x = 0.1, the electrical conductivity reached the maximum value of 750.3 S/cm at 800 °C, and the activation energy calculated from the Arrhenius plot of the electrical conductivity versus the reciprocal of temperature is 7.1 kJ/mol.The novelty of this study is its introduction of the concept of defect chemistry to explain the relationship between compensation mechanisms and electrical conductivity. The information gleaned regarding charge compensation mechanisms and defect formation may be valuable for a better understanding of the cathode of (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ ceramics used for SOFCs. Moreover, the information about oxygen content versus temperature is useful for expressing the relationship between electrical conductivity and composition. Therefore, we also used thermogravimetric analysis combined with the room-temperature oxygen content which was determined by iodometric titration to investigate the oxygen content from room temperature to high temperature, in air. Based on the experimental results, the (La_0.9Ca_0.1)(Co_0.9Ni_0.1)O_3?δ specimen shows high electrical conductivity. Consequently, it is identified as a promising candidate for cathode SOFC applications.     

Magnetic properties of Cu1+xMn2−xO4 and Ni1+xMn2−xO4 solid solutions

Magnetic properties of two spinel oxides solid solutions, Cu_1+xMn_2−xO₄ and Ni_1+xMn_2−xO₄, are reported. These series are characterized by two magnetic transitions: the upper one, of ferrimagnetic type, occurs at about 85 K (for copper-based) and at 105–110 K (for nickel-based spinels), independently of the x-content; the lower transition may be related to a Néel-type collinear ordering and takes place at 30 and 45 K, respectively. Application of moderate fields (H > 250 Oe) make both transitions to merge into one broad maximum in the magnetization, which takes place at lower temperature when applying larger fields. Magnetization cycles with temperature (ZFC/FC) or field (loops) allowed us to well characterize the ordered state. The effective moment follows the expected behavior when manganese ions are being substituted by ions of lower magnetic moment (Ni²⁺ and Cu²⁺).     

Catalytic removal of diesel soot particulates over K and Mg substituted La1 − xKxCo1 − yMgyO3 perovskite oxides

K and Mg substituted perovskite catalysts La_1 − xK_xCo_1 − yMg_yO₃ (x = 0–0.4, y = 0–0.2) for soot combustion were prepared by citric acid complexation and characterized by XRD, FT-IR, SEM, TEM, EDS, H₂-TPR, XPS and TG. Soot combustion was remarkably accelerated when K was introduced into LaCoO₃. Then Mg was doped into the K substituted LaCoO₃, soot combustion was further improved for the restrained growth of Co₃O₄ phase. K/Mg substitutions were responsible for enhancing activity of catalysts by improving reducibility as suggested by H₂-TPR studies. Among all the catalysts, La_0.6K_0.4Co_0.9Mg_0.1O₃ exhibited the highest activity.     

Dry reforming of methane over LaNi1−yByO3±δ (B = Mg,Co) perovskites used as catalyst precursor

Perovskites LaNiO₃, LaNi_1−xMg_xO_3−δ and LaNi_1−xCo_xO_3−δ were synthesized by auto combustion method. TPR analysis reveled that Mg or Co substituted perovskites were more difficult to reduce. The perovskites were evaluated as catalyst precursors in the dry reforming of methane. Catalysts obtained by reduction of LaNiO₃ and LaNi_1−xMg_xO_3−δ perovskite had the highest catalytic activity for CO₂ reforming of CH₄ at 700 °C using drastic reaction conditions (10 mg of catalyst, a mixture of CH₄/CO₂ without dilution gas). Methane and carbon dioxide conversions were 57% and 67%, respectively, with a H₂/CO ratio equal to 0.47.The presence of cobalt leads to a decrease of the catalytic activity. This decreasing of activity may be attributed to the Co–Ni alloy formation. Computational calculations revealed that Ni atom cleaves the C–H atom while Co is not able to activate the CH₄ molecule. The interaction energy of CH₄ with the Ni and CO atom was 18 kcal/mol and 0.7 kcal/mol, respectively.The catalysts were characterized by TPR, TEM and in situ XRD.     

Synthesis,structure and oxygen thermally programmed desorption spectra of La1−xCaxAlyFe1−yO3−δ perovskites

Perovskites La_1−xCa_xAl_yFe_1−yO_3−δ (x, y = 0 to 1) were prepared by high-temperature solid-state synthesis based on mixtures of oxides produced by colloidal milling. The XRD analysis showed that perovskites La_0.5Ca_0.5Al_yFe_1−yO_3−δ with a high Fe content (1 − y = 0.8–1.0) were of orthorhombic structure, perovskites with a medium Fe content (1 − y = 0.8–0.5) were of rhombohedral structure, and perovskite with the lowest Fe content (1 − y = 0.2) were of cubic structure. Thermally programmed desorption (TPD) of oxygen revealed that chemical desorption of oxygen in the temperature range from 200 to 1000 °C had proceeded in the two desorption peaks. The low-temperature α-peak (in the 200–550 °C temperature range) was brought about by oxygen liberated from oxygen vacancies; the high-temperature β-peak (in the 550–1000 °C temperature range) corresponded to the reduction of Fe⁴⁺ to Fe³⁺. The chemidesorption oxygen capacity increased with increasing Ca content and decreased with increasing Al content in the perovskites. The Al³⁺ ions restricted, probably for kinetic reasons, the reduction of Fe⁴⁺ and the high-temperature oxygen desorption associated with it.     

Structural and electrical properties of MgO-doped Mn1.4Ni1.2Co0.4−xMgxO4 (0 ≤ x ≤ 0.25) NTC thermistors

We have prepared polycrystalline Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ (0 ≤ x ≤ 0.25) samples using a solid-state reaction process and investigated the MgO doping effect on the microstructure and the electrical properties. It was found that, as the amount of Mg content in the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples increased, both the grain size and density decreased. The as-sintered Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples contained Mn- and Ni-rich phases with cubic spinel structure. The MgO-doped Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ negative temperature coefficient (NTC) thermistors provided various electrical properties, depending on Mg content. The electrical resistivity, B_25/85 constant, and activation energy of the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ NTC thermistors increased with increasing Mg content. The values of ρ₂₅, B_25/85 constant, and activation energy of the NTC thermistors were 11,185–20,016 Ω cm, 3635–4032 K, and 0.313–0.348 eV, respectively.