Studies on structural and thermal expansion properties of Ho2−xLnxMo4O15 (Ln = Er, Sm and Ce) solid solutions

Three new series of Ho_2−xEr_xMo₄O₁₅ (x = 0.0–2.0), Ho_2−xSm_xMo₄O₁₅ (x = 0.0–0.6) and Ho_2−xCe_xMo₄O₁₅ (x = 0.0–0.25) solid solutions have been prepared successfully by solid-state reaction and studied by powder X-ray diffraction. All the XRD patterns of these molybdates can be indexed in monoclinic space group P2₁/c. Lattice parameters a, b and c of Ho_2−xLn_xMo₄O₁₅ decrease linearly with increasing erbium content and increase with increasing samarium or cerium content. Thermal expansion behaviors of Ho_2−xLn_xMo₄O₁₅ have been investigated in the 25–500 °C temperature range with high-temperature X-ray diffraction. The temperature dependence of Mo(2)–O14 interaction looks like to be responsible for their thermal expansion behaviors.     

New dielectric material system of La(Mg1/2Ti1/2)O3–Ca0.6La0.8/3TiO3 for microwave applications

The microstructure and microwave dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics system with ZnO additions (0.5 wt.%) investigated by the conventional solid-state route have been studied. Doping with ZnO (0.5 wt.%) can effectively promote the densification and the dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. 0.6La(Mg_1/2Ti_1/2)O₃–0.4Ca_0.6La_0.8/3TiO₃ ceramics with 0.5 wt.% ZnO addition possess a dielectric constant (_r) of 43.6, a Q × f value of 48,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −1 ppm/°C sintering at 1475 °C. As the content of La(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 62,900 (GHz) for x = 0.8 is achieved at the sintering temperature 1475 °C. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Influence of B site substituent Ti on the structure and thermophysical properties of A2B2O7-type pyrochlore Gd2Zr2O7

Since the structural integrity of A₂B₂O₇-type pyrochlores relies mostly on the interconnecting BO₆ octahedra, Ti⁴⁺ was selected to partially substitute Zr⁴⁺ in Gd₂Zr₂O₇ in order to distort the pyrochlore structure in order to improve the material’s thermophysical properties for potential use as high-temperature thermal insulation. As evidenced by X-ray diffraction and Raman spectroscopy studies, incorporation of Ti⁴⁺ simultaneously leads to long-range ordering of the pyrochlore structure as well as local lattice distortion. These two effects have been shown to be competitive in determining the crystal energy of the Gd₂(Zr_1−xTi_x)₂O₇ series and result in a minimum value of the Young’s modulus at x = 0.3 and a maximum value of the coefficient of thermal expansion at x = 0.2. At lower temperatures, the thermal conductivity of Gd₂Zr₂O₇ was significantly reduced by Ti⁴⁺ doping, and its composition dependence was accurately modeled by taking into account the phonon scattering by mass and strain fluctuations at the B site.     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

Structural, magnetic and electrical transport properties for a series of La1−xSrxFe1−xMnxO3 (0.3 ≤ x ≤ 0.7) compounds

The structural, electrical transport and magnetic properties have been studied for compounds: La_1−xSr_xFe_1−xMn_xO₃ (0.3 ≤ x ≤ 0.7). The lattice parameter, a, first decreases with x, and followed by an increase when Sr²⁺ and Mn⁴⁺ was continuously doped. The cell parameters, b and c, slightly decrease with coupled substitution of Sr²⁺ for La³⁺ and Mn⁴⁺ for Fe³⁺. In the paramagnetic temperature range, formation of magnetic clusters is suggested; the sizes of clusters decrease with x up to 0.5, following that they increase sharply with continuing doping. The electrical behaviors of all specimens demonstrate insulators and the electrical resistivity increases with content of Mn⁴⁺ and Sr²⁺ ions doped. A variable range hopping model is suitable to describe electrical transport process for the compounds at low temperature. At high temperature the electrical transport process can be described by bipolaron model for all compounds.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Studies on structural and electrical properties of Co1−xNixFe1.9Mn0.1O4 ferrite

Nickel-doped iron-deficient cobalt ferrite with small amount of manganese having the chemical composition Co_1−xNi_xFe_1.9Mn_0.1O₄, with x = 0.2, 0.4, 0.6 and 0.8, were prepared by standard double sintering ceramic method. The spinel phase formation was confirmed by X-ray diffraction (XRD). The DC resistivity measurements with temperature indicate a semiconducting behavior showing a linear decrease with increasing temperature and the doping of Ni enhances the resistivity. Maximum resistivity of the order of 10⁹ Ω cm was found for composition x = 0.8. Room temperature dielectric constant measurements with frequency (100 Hz to 1 MHz), show usual dielectric dispersion. Also, the variation of room temperature AC conductivity as a function of frequency were studied and explained by using Maxwell–Wagner two-layer model. The studies on dielectric constant (′), loss tangent (tan δ) and AC conductivity (σ_AC), at four different frequencies (viz., 1, 10, 100 kHz and 1 MHz), with temperature were made.     

Subsolidus phase relations of the SrO–Ta2O5–CuO system at 900 °C in air

The subsolidus phase relations of the SrO–Ta₂O₅–CuO system were investigated in air. The samples were equilibrated at 900 °C. The ternary oxide Sr₃Ta₂CuO₉ compound is stable under these conditions. This phase presents a solid solution range, its actual composition being Sr₃Ta_2−xCu_1+xO_9+δ with 0.0 ≤ x ≤ 0.2. Up to about 5 at.% Cu can be incorporated in the Sr_3−xTa_1+xO_5.5+δ phase. Similarities with the SrO–Nb₂O₅–CuO system are discussed.     

Study of the electrical conduction behaviour of the Ba1−xLaxTi1−xNixO3 (x 0.10) system

The electrical conduction behaviour of the Ba_1−xLa_xTi_1−xNi_xO₃ (x 0.10) system has been studied by complex plane impedance analysis and measurements of a.c. conductivity in the temperature range 400–575 K. The values of the bulk resistance for these samples are obtained from a circular arc passing through the origin in their impedance plots. A.c. conductivity obeys the relation σ_a.c.αω⁸ in the temperature range of measurements. These results indicate that conduction occurs in this system because of hopping of charge carriers between localized nickel sites.     

Thermoelectric properties of Sn1−x−yTiySbxO2 ceramics

Thermoelectric properties of Sn_1−x−yTi_y Sb_xO₂ ceramics were investigated in detail. The addition of Sb into SnO₂ matrix increased the electric conductivity, σ. The increase in the σ value should be caused by the increase in the carrier concentration. The Seebeck coefficients of all the samples were negative, which means that these samples have n-type conduction. The samples of this study have porous structure. The maximum Z value of all the samples measured in this study was 2.4 × 10⁻⁵ K⁻¹.     

Formation and properties of BaxFe3−xO4 with spinel structure by mechanochemical reaction of α-Fe2O3 and BaCO3

Magnetic Ba_xFe_3−xO₄ (x  0.23) with spinel structure was fabricated by ball milling of mixture of BaCO₃ and nonmagnetic α-Fe₂O₃ powders, and the molar ratio of BaCO₃ and α-Fe₂O₃ is 1:6. In the milling process, a mechanochemical reaction took place between BaCO₃ and α-Fe₂O₃, and Ba cation incorporated into α-Fe₂O₃ with rhombohedral structure to form a α-(Fe,Ba)₂O₃ solid solution. The Ba content in the α-(Fe,Ba)₂O₃ increased with increasing milling time, when the Ba content exceeded a limited solubility, the α-(Fe,Ba)₂O₃ transformed into a phase of Ba_xFe_3−xO₄ with spinel structure, where the Ba cation occupied an octahedral site or tetrahedral site. The product obtained in the balling process was different from that prepared in the annealing process at atmospheric pressure, which was BaFe₂O₄ with orthorhombic structure. Accompanying the crystal structure transition from α-(Fe,Ba)₂O₃ to Ba_xFe_3−xO₄, the magnetic properties also changed from nonmagnetism into ferromagnetism. The saturation magnetization was 53.3 emu/g and coercivity was 113.7 Oe. The mechanism of transitions of the crystal structure was discussed in the present work.     

Fabrication and performance of La0.8Sr0.2MnO3/YSZ graded composite cathodes for SOFC

The performance of multi-layer (1 − x) La_0.8Sr_0.2MnO₃/x YSZ graded composite cathodes was studied as electrode materials for intermediate solid oxide fuel cells (SOFC). The thermal expansion coefficient, electrical conductivity, and electrochemical performance of multi-layer composite cathodes were investigated. The thermal expansion coefficient and electrical conductivity decreased with the increase in YSZ content. The (1 -x)La_0.8Sr_0.2MnO₃/x YSZ composite cathode greatly increased the length of the active triple phase boundary line (TPBL) among electrode, electrolyte, and gas phase, leading to a decrease in polarization resistance and an increase in polarization current density. The polarization current density of the triple-layer graded composite cathode (0.77 A/cm²) was the highest and that of the monolayer cathode (0.13 A/cm²) was the lowest. The polarization resistance (R_p) of the triple-layer graded composite cathode was only 0.182 ω·cm² and that of the monolayer composite cathode was 0.323 ω·cm². The power density of the triple-layer graded composite cathode was the highest and that of the monolayer composite cathode was the lowest. The triple-layer graded composite cathode had superior performance.     

The influence of gallium on the magnetocaloric properties of Gd5Si2Ge2

Gd₅Si₂Ge₂ was alloyed with varying amounts of Ga to study its influence on the giant magnetocaloric effect. Investigations on Gd₅(Si_2−xGe_2−x)Ga_2x with 2x = 0.03, 0.05 and 0.13 were carried out using X-ray powder diffraction, temperature and magnetic field dependent magnetization measurements, and differential scanning calorimetry. We observe that as the Ga content increases, the temperature stability range of the monoclinic phase narrows, and the orthorhombic structure gains stability. This is expected to be related to the decrease in the (Si/Ge)(Si/Ge) bond distance in the monoclinic phase. The maximum entropy change for the parent compound at 270 K was found to be 9.8 J kg⁻¹ K⁻¹ in an applied field of 5 T. For 2x = 0.03, this value reduces to 8.5 J kg⁻¹ K⁻¹, and the temperature corresponding to the maximum entropy change shifts marginally to 278 K. For other 2x values, the maximum entropy change further decreases.     

Study of ac impedance spectroscopy of Al doped MnFe2−2xAl2xO4

We have reported electrical properties of Al doped MnFe₂O₄ ferrite using ac impedance spectroscopy as a function of frequency (42 Hz to 5 MHz) at different temperatures (300–473 K). XRD analysis shows that all the compositions are single phase cubic spinel in structure. The complex impedance analysis has been used to separate the grain and grain boundary resistance of MnFe_2−2xAl_2xO₄. From the analysis of impedance spectra it is found that the real (Z′), and imaginary (Z″) part of the impedance decrease with increasing frequency and both are found to decrease with Al doping up to 20%, and thereafter, these increase with further increasing the Al concentration. Experimental results have been fitted with two parallel RC equivalent circuits in series.     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Effect of potassium doping on the structural, magnetic and magnetocaloric properties of La0.7Sr0.3−xKxMnO3 perovskite manganites

We investigate the effect of potassium doping on the structural, magnetic and magnetocaloric properties of La_0.7Sr_0.3−xK_xMnO₃ (x = 0.05, 0.1, 0.15 and 0.2) powder samples. Our polycrystalline compounds were synthesized using the solid-state reaction at high temperature. X-ray diffraction characterizations showed that all our studied samples crystallize in the distorted rhombohedral system with space group. With increasing potassium content, the unit cell volume exhibits a broad maximum around x = 0.15. Magnetization measurements versus temperature showed that all our samples exhibit a paramagnetic to ferromagnetic transition with decreasing temperature. The Curie temperature T_C is found to decrease from 365 K for x = 0 to 328 K for x = 0.2 as well as the saturated magnetization M_sp which shifts from 3.68 μ_B/Mn for x = 0 to 3.05 μ_B/Mn for x = 0.2. The critical exponent γ defined as M_sp (T) = M_sp(0)[1−(T/T_C)]^γ is found to remain almost constant and equal to 0.33 for all our samples. The maximum of magnetic entropy changes |ΔS_max| of La_0.7Sr_0.3−xK_xMnO₃ for x = 0.05 and 0.15 is found to be respectively, 1.37 and 1.2 J kg⁻¹ K⁻¹ under a magnetic field change of 1 T.     

Structural, magnetic and magnetotransport properties of La0.8Sr0.2MnO3/xLaMnO3 composites

The effect of LMO doping on the structure, magnetic and magnetotransport properties of La_0.8Sr_0.2MnO₃ (LSMO)/xLaMnO₃ (LMO) has been investigated. Two types of LSMO/xLMO composites, named as SL_x (low temperature sintered samples) and SH_x (high temperature sintered samples) samples, were prepared by different sintering temperature and solid-state reaction method. The presence of LMO at the grain boundaries increases the disordered states at the surface of the grains and therefore the magnetization and transition temperature decrease by increasing the amount of LMO doping level. Results show that the rate of decreasing of transition temperature is much more for high temperaure sintered samples. Also the resistivity of samples increases by the increase of LMO doping level. Results also show that the LMO doping has an effect on a low field magnetoresistance (LFMR). The value of LFMR increases for low doping level of 0 ≤ x ≤ 15, for SL_x samples and 0 ≤ x ≤ 10 for SH_x samples. Also LFMR decreases at high doping level. The spin dependent tunneling and scattering at the interfaces of the grain boundaries are responsible for the increase of LFMR at low doping level, while reduction of LFMR at high doping level may result from the grain boundary becoming too thick for electron tunneling.     

Self-propagating high-temperature synthesis with post-heat treatment of La1−xSrxFeO3 (x = 0–1) perovskite as catalyst for soot combustion

La_1−xSr_xFeO₃ (x = 0–1) perovskite, Sr-substituted LaFeO₃, was prepared by Self-propagating high-temperature synthesis (SHS) and its catalytic activity for soot combustion was experimentally examined in comparison with that of a conventional Pt/Al₂O₃ catalyst. The products were also characterized by XRD, FE-SEM, and BET specific surface area. The XRD analysis revealed that all the products had a perovskite phase as the major compound, together with intermediate phases with higher x values (x = 0.7–1). The BET specific surface area of the products increased with x. Moreover, the catalytic activity for soot combustion also increased with x, wherein the BET specific surface area appeared an appropriate index for explaining the observed activity. The sample with x = 0.8 exhibited the highest activity for soot combustion among all the SHS products. The soot combustion temperature of this product was as much as 100 °C lower than that of non-catalytic soot combustion. In other words, it had the same activity as that at only 20 °C higher, in comparison to conventional Pt/Al₂O₃ catalyst. More significantly, average apparent activation energy of sample with x = 0.8 calculated by Friedman method using TG/DTA was approximately 15 kJ/mol lower than that of Pt/Al₂O₃ catalyst. This result suggested that La_1−xSr_xFeO₃ has the possibility to be an alternative catalyst to Pt/Al₂O₃ catalyst.     

Investigation of the dependency of the upper critical magnetic field on the content x in Y1−xYbx/2Gdx/2Ba2Cu3O7−y superconducting structures

The Y_1−xYb_x/2Gd_x/2Ba₂Cu₃O_7−y superconducting samples for x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 were prepared by using the solid-state reaction technique. Resistivity measurements of the samples were performed in QD–PPMS system under different magnetic fields up to 5 T in zero fields cooling regime. Using the resistivity data, the upper critical magnetic field H_c2(0) at T = 0 K for 50% of R_n was calculated by the extrapolation H_c2(T) to the temperature T = 0 K. The coherence length in T = 0 K were calculated from H_c2(0) and the effects of x in the composition on both the coherence length and the upper critical magnetic field were examined. The results showed that H_c2(0) varied from 84.05 to 122.26 T with the content x. The upper critical magnetic field in the temperature T = 0 K slightly decreased with increasing the content x. Using the content x, the upper critical magnetic field can be controlled and this can be used in the superconductivity applications.     

A novel proton conducting Ba0.95K0.05Ce0.6Zr0.2Gd0.16Zn0.04O3−δ for SOFC

A new proton conducting Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte membrane was prepared on NiO-based anode support by suspension spray followed by a co-sintering at 1400 °C for 4 h. Chemical stability test shows that this new proton conductor displays adequate chemical stability against CO₂ at intermediate temperatures. The conductivity of Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ in humidified H₂ is about 50% higher than that of BaCe_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ from 500 to 800 °C. With La_0.8Sr_0.2MnO_3−δ cathode, fuel cell with Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte shows 1.02 V of OCV and 354 mW/cm² of maximum power density at 700 °C, respectively. And the cell performance did not degrade after running at least for 10 h.