Preparation by sol–gel and solid state reaction methods and properties investigation of double perovskite Sr2FeMoO6

Double perovskite Sr₂FeMoO₆ was prepared by two ways consisting in sol–gel technique and solid-state reaction method. The resulting powders from gel and mixed oxides precursors showed microstructures consisting of very fine grains (0.5–0.8 μm) and a crystalline perovskite structure. The structural and microstructural properties of the double perovskite Sr₂FeMoO₆ powders as-prepared and ceramics were compared. Tetragonal Sr₂FeMoO₆ pellets were prepared from the two powders by spark plasma sintering at: 1000, 1100 and 1200 °C and then annealing at 1200 °C, 2 h in 5%H₂/Ar. The pellets presented different magnetic characteristics. The saturation magnetization of the samples prepared by sol–gel is close to those prepared by conventional synthesis method.     

Room-temperature large magnetocaloric effect and critical behavior in La0.6Dy0.1Sr0.3MnO3

The effect of dysprosium incorporation in La_0.7Sr_0.3MnO₃ perovskite manganite on its magnetic properties, magnetocaloric effect and critical behavior was investigated. The temperature dependent magnetization data exhibit a sharp paramagnetic–ferromagnetic transition at T_C=307 K, which nature has been identified to be a second-order transition by the scaling laws for magnetocaloric effect. The maximum magnetic entropy change and the relative cooling power are found to be, respectively, 8.314 J/kg K and 187 J/kg for a 5 T magnetic field change without a hysteresis loss, making this material a promising candidate for magnetic refrigeration at room temperature. To study the critical behavior of the paramagnetic–ferromagnetic transition, some related critical exponents (β, γ, and δ) have been also calculated. The values of critical exponents indicate that the present phase transition does not belong to the common transition classes but shows some abnormal variation. We suggest that the induced lattice disordering and magnetic disordering due to Dysprosium incorporation are essential reasons for the presence of a large magnetocaloric effect and of an anomalous ferromagnetic phase transition in the present material     

The role of the synthesis route to obtain densified TiO2-doped alumina ceramics

Alumina specimens doped with 1 wt.% of titanium oxide were successfully prepared by three different synthesis routes: Pechini method, coprecipitation and sol–gel processes. This paper describes the phase sequence in each synthesis process and its effect on the final particle size and shape, as well as, on the microstructure of the calcined powders and the sintering behaviour. The intermediate phases to obtain α-alumina were κ-Al₂O₃, θ-Al₂O₃ and γ-Al₂O₃for the Pechini, coprecipitation and sol–gel processes, respectively, as could be detected by FT-IR and XRD. Secondly, the calcined powders were isopressed and sintered at 1625 °C for 4 h. Density measurements, and microstructure were investigated by Archimedes method and TEM/SEM, respectively. The sintering behaviour of the materials is discussed on the basis of the characteristic of the metastable phases obtained by each route. Coprecipitation yielded rounded particles with the smallest size. Sol–gel process produced larger grains with vermicular shapes and Pechini method led to hexagonal corundum crystals.     

Low-temperature synthesis and microwave dielectric properties of trirutile-structure MgTa2O6 ceramics by aqueous sol–gel process

Trirutile-structure MgTa₂O₆ ceramics were prepared by aqueous sol–gel method and microwave dielectric properties were investigated. Highly reactive nanosized MgTa₂O₆ powders were successfully synthesized at 500 °C in oxygen atmosphere with particle sizes of 20–40 nm. The evolution of phase formation was detected by DTA–TG and XRD. Sintering characteristic and microwave dielectric properties of MgTa₂O₆ ceramics were studied at different temperatures ranging from 1100 to 1300 °C. With the increase of sintering temperature, density, ?_r and Q · f values increased and saturated at 1200 °C with excellent microwave properties of ?_r ～ 30.1, Q · f ～ 57,300 GHz and τ_f ～ 29 ppm/°C. The sintering temperature of MgTa₂O₆ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state method.     

Polarization-induced electro resistance and magneto resistance in La0.67Ca0.33MnO3/BaTiO3 composite film

La_0.67Ca_0.33MnO₃/BaTiO₃ composite films have been grown on Nb-doped SrTiO₃ substrates by the sol–gel method. The magnetic and ferroelectric properties in the composite films are investigated. A three-state memory is formed by applying a vertical electric field across the La_0.67Ca_0.33MnO₃/BaTiO₃ heterostructure, this behavior is attributed to the polarization-mediated resistive switching effect. In addition, the transport properties of La_0.67Ca_0.33MnO₃ thin film can be modulated by an external magnetic field, a 10.3 K shift of the metal insulator transition temperature is obtained with the change of applied magnetic field from 0 T to 6 T. Consequently, in La_0.67Ca_0.33MnO₃/BaTiO₃ heterostructure, the resistance behavior can be modulated by piezoelectric effect, ferroelectric polarization and magnetic field simultaneously.     

SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating

A technique for densifying ultra high temperature ceramic composites while minimising grain growth is reported. As-purchased ZrB₂ powder was treated with a zirconia-carbon sol–gel coating. Carbothermal reduction at 1450 °C produced 100–200 nm crystalline ZrC particles attached on the surface of ZrB₂ powders. The densification behaviour of the sol–gel coated powder was compared with both the as-purchased ZrB₂ and a compositionally similar ZrB₂–ZrC mixture. All three samples were densified by spark plasma sintering (SPS). The ZrB₂ reference sample was slow to densify until 1800 °C and was not fully dense even at 2000 °C, while the sol–gel modified ZrB₂ powder completed densification by 1800 °C. The process was studied by ram displacement data, gas evolution, SEM, and XRD. The sol–gel coated nanoparticles on the ZrB₂ powder played a number of important roles in sintering, facilitating superior densification by carbothermal reduction, nanoparticle coalescence and solid-state diffusion, and controlling grain growth and pore removal by Zener pinning. The sol–gel surface modification is a promising technique to develop ultra-high temperature ceramic composites with high density and minimum grain growth.     

Structural,magnetic and magnetocaloric study of La0.7−xEuxSr0.3MnO3 (x=0.1, 0.2 and 0.3) manganites

This paper reports the structural, magnetic and magnetocaloric properties of La_0.7−xEu_xSr_0.3MnO₃ (x=0.1, 0.2 and 0.3) polycrystalline manganites elaborated using the solid-state reaction at high temperatures. The X-ray powder diffraction shows that all the prepared compounds are single phase. La_0.6Eu_0.1Sr_0.3MnO₃ is crystallized in the rhombohedral symmetry, whereas a structural transition towards orthorhombic system is observed for x≥0.2. Eu doping was found to induce a decrease of the Curie temperature T_C from 343 K (x=0.1) to 272 K (x=0.3). All compounds undergo a large magnetocaloric effect and have consequently potential applications in magnetic refrigeration domain around room temperature.     

Synthesis and microwave dielectric properties of pseudobrookite-type structure Mg5Nb4O15 ceramics by aqueous sol–gel technique

Pseudobrookite-type Mg₅Nb₄O₁₅ ceramics were prepared by aqueous sol–gel process and microwave dielectric properties were investigated. Highly reactive nanosized Mg₅Nb₄O₁₅ powders were successfully synthesized at 600 °C in oxygen atmosphere with particle sizes of 20–40 nm firstly and then phase evolution was detected by DTA-TG and XRD. Sintering characteristics and microwave dielectric properties of Mg₅Nb₄O₁₅ ceramics were studied at different temperatures ranging from 1200 °C to 1400 °C. With the increase of sintering temperature, density, ?_r and Q·f values increased, and then saturated at 1300 °C. Excellent microwave properties of ?_r ～11.3, Q·f ～43,300 GHz and τ_f ～?58 ppm/°C, were obtained finally. The sintering temperature of Mg₅Nb₄O₁₅ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state methods.     

The effect of Co doping on the magnetic and magnetocaloric properties of Pr0.7Ca0.3Mn1−xCoxO3 manganites

In this work, we report the effect of low amount of cobalt doping at the Mn-site on the magnetic and magnetocaloric properties of Pr_0.7Ca_0.3Mn_1−xCo_xO₃ (0≤x≤0.1) powder samples. Our samples, elaborated using the solid–solid reaction method at high temperature, are single phase and crystallize in the orthorhombic system with Pnma space group. While the parent compound Pr_0.7Ca_0.3MnO₃ exhibits a charge order state at low temperature, the substituted samples with low amount of cobalt exhibit a paramagnetic to ferromagnetic transition with decreasing temperature. The Curie temperature T_C increases with Co content from 105 K for x=0 to 116 K for x=0.1. The maximum values of the magnetic entropy change $\left|\mathrm{\Delta }{S}_{\mathrm{M}}^{\max }\right|$ are found to be 0.8 J/kg K, 2.2 J/kg K, 3.1 J/kg K and 3.2 J/kg K in a magnetic field change of 5 T for x=0, 0.02, 0.05 and 0.1 respectively. The maximum value of the relative cooling power RCP is found to be 378.2 J/kg in the Pr_0.7Ca_0.3Mn_0.95Co_0.05O₃ at 5 T. This value of RCP is about 92% of that obtained in gadolinium metal, known as one of the most important materials for magnetic refrigeration, at the same magnetic field change of 5 T.     

Effect of MnO2 addition on microstructure and electrical properties of ZnO–V2O5-based varistor ceramics

The microstructure and electrical properties of ternary system ZnO–0.5 mol% V₂O₅–MnO₂ ceramics sintered were investigated in accordance with MnO₂ content by sintering at 900 °C. For all samples, the microstructure of the ternary system ZnO–V₂O₅–MnO₂ ceramics consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the binary system ZnO–V₂O₅ ceramics was found to restrict the abnormal grain growth of ZnO. The breakdown field in the E–J characteristics increased from 175 to 992 V/cm with the increase of MnO₂ content. The incorporation of MnO₂ improved non-ohmic properties by increasing non-ohmic coefficient. The highest non-ohmic coefficient (27.2) in the ternary system ZnO–0.5 mol% V₂O₅–MnO₂ was obtained for MnO₂ content of 2.0 mol%.     

Structural,dielectric, and piezoelectric properties of fine-grained NBT–BT0.11 ceramic derived from gel precursor

(Na_1/2Bi_1/2)TiO₃ doped in situ with 11 mol% BaTiO₃ (NBT–BT_0.11) powders were synthesized by a sol–gel method, and the electrical properties of the resulting ceramics were investigated. The powders consisting of uniform and fine preliminary particles of about 50 nm were prepared by calcining the gel precursor at 700 °C. (Na_1/2Bi_1/2)_0.89Ba_0.11TiO₃ ceramics, sintered at temperatures up to 1150 °C have a rhombohedral symmetry, while the ceramic sintered at 1200 °C exhibits a tetragonal crystalline structure. The ceramics show high dielectric constant (?_r ～ 5456), dielectric loss of 0.02, depolarization temperature T_d ～ 110 °C and temperature corresponding to the maximum value of dielectric constant T_m ～ 262 °C. The dielectric constant (?₃₃) and the piezoelectric constant (d₃₃) attain the maximum values of 924 and 13 pC/N, respectively, while the electromechanical coupling factor (k_p) value is 0.035. The NBT–BT_0.11 ceramics derived from sol–gel present high mechanical quality factor (Q_m ～ 860). The dielectric and piezoelectric properties values of NBT–BT_0.11 ceramics derived from sol–gel are smaller than those of samples produced by the conventional solid state reaction method, due to the grains size and oxygen vacancies that generate dipolar defects.     

Influence of Ce addition on the structural,magnetic, and magnetocaloric properties in La0.7−xCexSr0.3MnO3 (0≤x≤0.3) ceramic compound

We report improvement in the magnetocaloric properties of Ce-doped lanthanum manganites. Polycrystalline La_0.7−xCe_xSr_0.30MnO₃ (0≤x≥0.3) samples were prepared using the conventional solid-state reaction method with phase purity and structure confirmed using X-ray diffraction. Temperature dependent magnetization measurements and Arrott analysis reveal second order ferromagnetic transition in parent sample and as well as in doped sample with Curie temperature decreasing progressively with increasing Ce-concentration from ~370 K for x=0.0 to 310 K for x=0.30. Magnetic entropy change (ΔS_M) was calculated by applying the thermodynamic Maxwell equation to a series of isothermal field dependent magnetization curves. A large ΔS_M associated with the ferromagnetic–paramagnetic transition in La_0.7−xCe_xSr_0.30MnO₃ samples has been observed. The value of ΔS_M was found to increase with Ce-doping up to x=0.15 and the highest value of 2.12 J kg⁻¹ K⁻¹ (at ΔH=2 T) was observed for La_0.55Ce_0.15Sr_0.30MnO₃ sample near the Curie temperature of 356 K. Also, improved relative cooling power of ~122 J kg⁻¹ was observed for the same sample. Due to the large magnetic entropy change and high Curie temperature, the La_0.55Ce_0.15Sr_0.30MnO₃ sample is suggested to be used as potential magnetic refrigerants for magnetic refrigeration technology above room temperature.     

Highly stable and selective ethanol sensor based on α-Fe2O3 nanoparticles prepared by Pechini sol–gel method

In the present work, α-Fe₂O₃ nanoparticles were successfully synthesized by Pechini sol–gel (PSG) method following annealing at 550 °C. The morphology and microstructure of the prepared α-Fe₂O₃ nanoparticles were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis. The electrical and sensing properties were also investigated. The α-Fe₂O₃ based sensor showed good sensitivity and selectivity towards ethanol at the optimal temperature of 225 °C. Moreover, the sensor displayed good electrical and sensing stability. These results suggest the potential applications of α-Fe₂O₃ synthesized by Pechini sol–gel method as a sensor material for ethanol detection.     

Effect of Pb excess in sol–gel process on phase composition in PFN ceramics

Lead iron niobate Pb(Fe_0.5Nb_0.5)O₃ (PFN) precursors were prepared using sol–gel synthesis by mixing acetates Pb and Fe with Nb-ethylene glycol–tartarate (Pechini) complex at 80 °C and calcination of gels at 600 °C. Single pyrochlore phase with structure close to Pb₃Nb₄O₁₃ was formed in stoichiometric precursor and Pb₃Nb₄O₁₃ with small amount of perovskite phase Pb(Fe_0.5Nb_0.5)O₃ in nonstoichiometric precursor prepared with the excess of Pb in molar ratio (Pb:Fe:Nb = 1.2:0.5:0.5). Average particle sizes of PFN calcined powders were ～120 nm. The metastable pyrochlore phase was partially decomposed to perovskite phase at sintering temperature of 1150 °C for 2, 4 and 6 h. Excess of Pb caused increasing of the density (7.4 g/cm³) and content of the perovskite phase (～53 vol.%) in ceramics sintered for 4 h. In microstructures of PFN ceramics sintered at 1150 °C for different times, the bimodal grain size distribution was observed with small spherical grains of perovskite phase and larger octahedral grains, which represent the pyrochlore phase. Results of EDX analysis confirm that complex types of pyrochlore phases that differ in iron content were present in ceramics.     

Large relative cooling power of Bi-doped La0.8−xBixSr0.08(Ca0.55Ba0.45)0.12MnO3 (x=0.0, 0.1 and 0.3) perovskites: Magnetic and magnetocaloric properties

We report magnetic and magnetocaloric properties of La_0.8−xBi_xSr_0.08(Ca_0.55Ba_0.45)_0.12MnO₃ (x=0.0, 0.1 and 0.3) perovskite manganites. Polycrystalline samples have been synthesized in air by the sol gel method at a sintering temperature of 1150 °C. Powder X-ray diffraction data show that samples are phase pure and their cell parameters slightly decrease with increase in Bi content. Scanning electron micrographs show that the average particle size increases with increase in Bi content. The temperature dependent magnetization measurements show that the Curie temperatures decrease from 315 K (x=0.0) to 140 K (x=0.3) with increase in Bi content. The isothermal magnetization data is used to estimate the magnetic entropy changes (−$\Delta S_M$) and their calculated values are 1.12 J kg⁻¹ K⁻¹, 1.96 J kg⁻¹ K⁻¹ and 1.62 J kg⁻¹ K⁻¹ for x=0.0, 0.1 and 0.3 samples respectively under an applied magnetic field of 2.0 T. The corresponding values of relative cooling power (RCP) are 90 J kg⁻¹, 180 J kg⁻¹, 136 J kg⁻¹ for x=0.0, 0.1 and 0.3 samples respectively. These results of magnetocaloric effect in our samples suggest that they are promising materials for the magnetic refrigeration applications.     

Large magnetocaloric effect of La0.67Pb0.33Mn1−xCoxO3 in small magnetic field variation

In this work, we studied in detail the magnetocaloric properties of La_0.67Pb_0.33MnO₃ according to the phenomenological model. Based on this model, a large magnetic entropy change has been discovered in La_0.67Pb_0.33MnO₃ when subjected to low magnetic field variation of 0.05 T. Furthermore, the results of Co doping clearly indicate that the magnetocaloric effect in this system is tunable. Therefore, this tuning makes this ceramic series potentially practical for the improvement of multimaterial layered magnetocaloric regenerators.     

Enhanced piezoelectric properties of Aurivillius-type sodium lanthanum bismuth titanate (Na0.5La0.5Bi4Ti4O15) by B-site manganese modification

The Aurivillius-type bismuth layer-structured ferroelectrics (BLSFs) sodium lanthanum bismuth titanate (Na_0.5La_0.5Bi₄Ti₄O₁₅, NLBT) polycrystalline ceramics with 0.0–0.4 wt% MnO₂ were synthesized using conventional solid-state processing. Phase analyses were performed by X-ray powder diffraction (XRPD), and the microstructural morphology was assessed by scanning electron microscopy (SEM). The dielectric and piezoelectric properties of the manganese-modified NLBT ceramics were investigated in detail. The results show that manganese is very effective in promoting the piezoelectric activities of NLBT ceramics, and the reasons for piezoelectric activities enhancement by manganese modification are explained. The NLBT ceramics modified with 0.2 wt% MnO₂ (NLBT-Mn2) possess good piezoelectric properties, with a piezoelectric coefficient d₃₃ of 28 pC/N. This value is the highest value among the modified NLBT-based piezoelectric ceramics examined. The temperature-dependent dielectric spectra show that the Curie temperature T_c of the manganese-modified NLBT ceramics is slightly higher than that of the pure NLBT ceramics. Thermal annealing analysis revealed that the manganese-modified NLBT ceramics possess good thermal stabilities up to 500 °C. These results demonstrate that the manganese-modified NLBT ceramics are promising materials for high temperature piezoelectric applications.     

Microwave dielectric properties of low-fired Li2MnO3 ceramics co-doped with LiF–TiO2

Li₂MnO₃ ceramics co-doped with 2 wt% LiF and x wt% TiO₂ (x=0, 3, 5, 7, 10) were prepared by solid-state reaction for low-temperature co-fired ceramics (LTCC) applications. The sintering temperatures of Li₂MnO₃ ceramics were successfully lowered to 925°C due to the formation of a LiF liquid phase. Their temperature stability was improved by doping with TiO₂. A typical Li₂MnO₃-2 wt% LiF-5 wt% TiO₂ sample with well-densified microstructures displayed optimum dielectric properties (ε_r=13.8, Q×f= 23,270 GHz, τ_f=1.2 ppm/°C). Such sample was compatible with Ag electrodes, which suggests suitability of the developed material for LTCC applications in wireless communication systems.     

Sol–emulsion–gel synthesis of cordierite ceramics for high-frequency multilayer chip inductors

Nano-Cordierite powders used for high frequency chip inductors (MLCIs) were prepared by sol–emulsion–gel method. Effects of precursor concentration and [H₂O]/[Si] molar ratio on this material were studied. The sol–emulsion–gel processing of Mg₂Al₄Si₅O₁₈ as well as its dielectric property were investigated. Owing to the better packing efficiency and therefore higher surface energy of the freestanding nano-powder, the pressed pellets made by cordierite powder showed 98.6% theoretical density at 900 °C for 2 h. The additive Bi₂O₃ was utilized to promote the crystallization or transformation to α-cordierite and sintering. The sol–emulsion–gel-derived cordierite ceramics have low dielectric constant (ε=3.0～4.0; 18 GHz) and low dielectric loss (tgδ<0.001; 18 GHz) and can be co-fired with high conductivity metals such as Au, Ag/Pd internal electrode at low temperature (900 °C), suggesting that it was an ideal dielectric material for high-frequency multilayer chip inductors.     

Synthesis and characterization of electrospun aluminum doped Li1.6Mn1.6O4 spinel

Three dimensional porous Li_1.6Al_0.6MnO₄ (LAMO) nanofibers were successfully prepared for the first time, via a facile electrospinning homogenous solution of lithium acetate, manganese nitrate and aluminum nitrate in polyvinyl alcohol and polyvinylpyrolidone solution followed by calcination of the as-spun nanofibers at 500, 700 and 900 °C. The processing parameters were; voltage 25 kV, flow rate 0.7 ml/h, the distance between the needle and collector 10 cm and the inner diameter of the needle 0.499 mm. X-ray diffraction of the samples prepared by using electrospinning and sol–gel revealed that Li_1.6Al_0.6MnO₄ phase was formed at; 500 °C and 700 °C, respectively. Field Emission Scanning Electron Microscopy revealed that the electrospun nanofibers at 700 °C were fabricated with diameter 250 nm, and the single fiber composed of 30 nm LAMO grains. On the other hand, samples calcined at 700 °C, prepared by sol–gel, show coalescence of the fine grains of LAMO in the form of microspheres with an average diameter of 1 µm and each microsphere is composed of fine crystals of LAMO. The characteristics of the prepared spinel make them promising for use in lithium adsorption from polluted effluents.