Preparation and microstructural characterization of (Nd1−xGdx)2(Ce1−xZrx)2O7 solid solutions

(Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ (0 ≤ x ≤ 1.0) powders with an average particle size of 100 nm were synthesized with chemical-coprecipitation and calcination method, and were characterized by X-ray diffractometry and scanning electron microscopy. The sintering behaviour of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ powders was studied by pressureless sintering at 1600–1700 °C for 10 h in air. The relative densities of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions increase with increasing the sintering temperature, and gradually decrease with increasing the content of neodymium and cerium at identical temperature levels. (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions have a single phase of defect fluorite-type structure among all the composition combinations studied. The lattice parameters of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions agree well with the Vegard's rule.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanorods prepared by the solvothermal annealing method

Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods have been prepared by the thermal decomposition of the corresponding oxalate precursor, which was synthesized by the template-, surfactant-free solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM). The obtained Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods were built by many nanoparticles with average sizes around 20 nm to form one-dimensional arrays. Vibrating sample magnetometry measurements show that the coercivity of the ferrite nanorods decreases with increasing Zn content, whereas the specific saturation magnetization initially increases and then decreases with the increase of Zn content. The maximum saturation magnetization value of the as-prepared sample (Co_0.5Zn_0.5Fe₂O₄) reaches 43.0 emu g⁻¹.     

Structural,magnetic and dielectric behavior of Mg1−xCaxNiyFe2−yO4 nano-ferrites synthesized by the micro-emulsion method

Ca–Ni co-substituted samples of nanocrystalline spinel ferrites with chemical formula Mg_1−xCa_xNi_yFe_2−y O₄ (x=0.0–0.6, y=0.0–1.2) were synthesized by the micro-emulsion method and were annealed at 700 °C for 7 h. The synthesized samples were characterized by x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometry (VSM) and dielectric measurements. The XRD and FTIR analysis reveals that single phase samples can be achieved by substituting Ca and Ni ions at Mg and Fe sites respectively in cubic spinel nano-ferrites. The crystallite size of the synthesized samples was found in the range 29–45 nm. The saturation magnetization (M_s) increases from 9.84 to 24.99 emu/g up to x=0.2, y=0.4 and then decreases, while the coercivity (H_c) increases continuously from 94 to 153 Oe with the increase in dopants concentration. The dielectric properties of these nano materials were also studied at room temperature in the frequency range 100 MHz to 3 GHz. The dielectric parameters were found to decrease with the increased Ca–Ni concentration. Further the peaking behavior was observed beyond 1.5 GHz. The frequency dependent dielectric properties of all the samples have been explained qualitatively on the basis of the Maxwell–Wagner two-layer model according to Koop's phenomenological theory. The enhanced magnetic parameters and reduced dielectric properties make the synthesized materials suitable for switching and high frequency applications, respectively.     

Zr-doped Li[Ni0.5−xMn0.5−xZr2x]O2 (x = 0, 0.025) as cathode material for lithium ion batteries

Layered Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) have been prepared by the mixed hydroxide and molten-salt synthesis method. The individual particles of synthesized materials have a sub-microsize range of 200-500 nm, and LiNi_0.475Mn_0.475Zr_0.05O₂ has a rougher surface than that of LiNi_0.5Mn_0.5O₂. The Li/Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) electrodes were cycled between 4.5 and 2.0 V at a current density of 15 mA/g, the discharge capacity of both cells increased during the first ten cycles. The discharge capacity of the Li/LiNi_0.475Mn_0.475Zr_0.05O₂ cell increased from 150 to 220 mAh/g, which is 50 mAh/g larger than that of the Li/LiNi_0.5Mn_0.5O₂ cell. We found that the oxidation of oxygen and the Mn³⁺ ion concerned this phenomenon from the cyclic voltammetry (CV). Thermal stability of the charged Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) cathode was improved by Zr doping.     

Microstructural and electrical behavior of Bi4V2−xCuxO11−δ (0 ≤ x ≤ 0.4)

Cation substituted bismuth vanadate possesses high oxygen ion conductivity at lower temperatures. The ionic conductivity of this material at 300 °C is 50–100 times more than any other solid electrolyte. Three phases (α, β, γ) are observed in the substituted compound; α and γ are low and high conducting phase, respectively. Samples of Bi₄V_2−xCu_xO_11−δ (x = 0–0.4) were prepared by solid-state reaction technique. Impedance spectroscopy measurements were carried out in the frequency range of 100 Hz to 100 kHz using gold sputtered cylindrical shaped pellets to obtain bulk ionic conductivities as a function of the substitution and temperature. The change of slopes observed in the Arrhenius plots is in agreement with the phase transitions for all the compositions. The highest ionic conductivity of the Cu-substituted compound was observed in Bi₄V_1.8Cu_0.2O_11−δ which is attributed to its lower activation energy. Microstructural studies indicated the stabilization of high temperature γ-phase at low temperature in those samples whose ionic conductivity observed was higher.     

Structure,magnetic and electrical transport properties of the perovskites Sm1−xCaxFe1−xMnxO3

The structure of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.0 ≤ x ≤ 1.0) compounds was investigated. The lattice parameters increase with coupled substitution Sm³⁺ by Ca²⁺ and Mn⁴⁺ for Fe³⁺. The variation of parameter, c, is larger than that of a and b, respectivly. The detailed analysis of magnetic properties of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.1 ≤ x ≤ 0.9) shows that local magnetic interaction between Fe³⁺ and Fe³⁺ and Mn⁴⁺ and Mn⁴⁺ at below magnetic transition temperature is antiferromagnetic. Above magnetic transition temperature the presence of large magnetic cluster is proposed and the sizes of magnetic clusters decrease with Mn⁴⁺. The electrical transport behaviors related with small polaron hopping and variable range hopping models.     

Synthesis and negative thermal expansion property of Y2−xLaxW3O12 (0≤x≤2)

Y_2−xLa_xW₃O₁₂ solid solutions were successfully synthesized by the solid state reaction method. The microstructure, hygroscopicity and thermal expansion property of the resulting samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and thermal mechanical analysis (TMA). Results indicate that the structural phase transition of the Y_2−xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phase can form for 0≤x≤0.4 with orthorhombic structure and for 1.5≤x≤2 with monoclinic one. High lanthanum content leads to a low relative density of Y_2−xLa_xW₃O₁₂ ceramic. Thermal expansion coefficients of the Y_2−xLa_xW₃O₁₂ (0≤x≤2) ceramics also vary from −9.59×10⁻⁶ K⁻¹ to 2.06×10⁻⁶ K⁻¹ with increasing substituted content of lanthanum. The obtained Y_0.25La_1.75W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.66×10⁻⁶ K⁻¹ from 103 °C to 700 °C.     

Characterization of Mg1−xNixAl2O4 solid solutions prepared by combustion synthesis

Mg_1−xNi_xAl₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) solid solutions have been prepared by combustion synthesis. After annealing the combustion synthesized powders at 1000 °C for 3 h single-phase Mg_1−xNi_xAl₂O₄ was obtained over the entire range of compositions. The lattice parameter of Mg_1−xNi_xAl₂O₄ gradually increased from 8.049 Å (NiAl₂O₄) to 8.085 Å (MgAl₂O₄), which certified the formation of the spinel solid solutions. All samples prepared by combustion synthesis had blue color shades, denoting the inclusion of Ni²⁺ in the spinel structure in octahedral and tetrahedral configuration. The crystallite size of Mg_1−xNi_xAl₂O₄ was in the range of 35-39 nm and the specific surface area varied between 5.8 and 7.0 m²/g.     

Structure,dielectric and optical properties of Bi1.5+xZnNb1.5O7+1.5x pyrochlores

Non-stoichiometric pyrochlore ceramics with formula Bi_1.5+xZnNb_1.5O_7+1.5x were systematically investigated. Crystal structures of the compounds were studied by X-ray diffraction (XRD) technique. The structures were identified as pure cubic pyrochlores when |x| < 0.1. Dielectric and optical properties of the compositions when x = −0.1, 0 and 0.1 were studied. All samples have high resistivities and low dielectric loss. With increasing x in Bi_1.5+xZnNb_1.5O_7+1.5x, the lattice constant, permittivity, temperature coefficient of permittivity and thermal expansion coefficient increased, while dielectric loss decreased. Raman spectra indicated that the intensity of Bi–O stretching become stronger with increasing x. A vibration mode emerging at 861 cm⁻¹ when x = −0.1 means that the B–O coordination environment is significantly more disordered. Absorption spectra suggested that the bandgap energy become lower from 2.86 to 2.70 eV as lattice constants increased. Strong absorption occurs at wavelengths from 433 to 459 nm, shows that samples have the ability to respond to wavelengths in the visible light region.     

Parallel oxygen and chlorine evolution on Ru1−xNixO2−y nanostructured electrodes

Nanocrystalline materials with chemical composition corresponding to formula Ru_1−xNi_xO_2−y (0.02 < x < 0.30) were prepared by sol-gel approach. Substitution of Ru by Ni has a minor effect on the structural characteristics extractable from X-ray diffraction patterns. The electrocatalytic behavior of Ru_1−xNi_xO_2−y with respect to parallel oxygen (oxygen evolution reaction, OER) and chlorine (chlorine evolution reaction, CER) evolution in acidic media was studied by voltammetry combined with differential electrochemical mass spectrometry (DEMS). The DEMS data indicate a significant decrease of the over-voltage for chlorine evolution with respect to that of pure RuO₂. The oxygen evolution is slightly hindered. The increasing Ni content affects the electrode material activity and selectivity. The overall material's activity increases with increasing Ni content. The activity of the Ru-Ni-O oxides towards Cl₂ evolution shows a distinguished maximum for material containing 10% of Ni. Further increase of Ni content results in suppression of Cl₂ evolution in favor of O₂ evolution. A model reflecting the cation-cation interactions resulting from Ni-doping is proposed to explain the observed trends in electrocatalytic behavior.     

Phase transition and negative thermal expansion properties of Sc2−xCrxMo3O12

The crystal structure, phase transition and thermal expansion behaviors of solid solutions Sc_2−xCr_xMo₃O₁₂ (0≤x≤2) were investigated using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). At room temperature, samples with x≤0.7 and x≥0.8 crystallize in orthorhombic and monoclinic structures, respectively. DSC result indicates that the phase transition of Sc_0.5Cr_1.5Mo₃O₁₂ from monoclinic to orthorhombic structure occurs at 203.66 °C. The linear thermal expansion coefficient of orthorhombic phases varies from −2.334×10⁻⁶ °C⁻¹ to 0.993×10⁻⁶ °C⁻¹ when x increases from 0.0 to 1.5. The near-zero linear thermal expansion coefficients of −0.512×10⁻⁶ °C⁻¹ and −0.466×10⁻⁶ °C⁻¹ are observed for compounds with x=0.5 and 0.7, respectively.     

Structural and magnetic properties of NiFe2−xBixO4 (x = 0, 0.1, 0.15) nanoparticles prepared via sol-gel method

NiFe_2−xBi_xO₄ (x = 0, 0.1, 0.15) nanopowders were synthesized via sol-gel method. The precursor gels were calcined at 773 K in air for 1 h to obtain the pure nanostructured NiFe_2−xBi_xO₄ spinel phase. The crystal structure and magnetic properties of the substituted spinel series of NiFe_2−xBi_xO₄ have been investigated by means of ⁵⁷Fe Mössbauer spectroscopy, transmission electron microscopy and alternating gradient force magnetometry. Mössbauer spectroscopic measurements revealed that Bi³⁺ cations tend to occupy octahedral positions in the structure of the substituted ferrite, i.e., the crystal-chemical formula of the as-prepared nanoparticles may be written as: (Fe)[NiFe_1−xBi_x]O₄ (x = 0, 0.1, 0.15), where parentheses and square brackets enclose cations on sites of tetrahedral and octahedral coordination, respectively. Selective area electron diffraction studies provided evidence that the samples of the NiFe_2−xBi_xO₄ series, independently of x, exhibit the cubic spinel structure. The values of the saturation magnetization and the coercive field of NiFe_2−xBi_xO₄ nanoparticles were found to decrease with increasing degree of bismuth substitution.     

Synthesis of negative thermal expansion materials ZrW2−xMoxO8 (0 ≤ x ≤ 2) using hydrothermal method

Negative thermal expansion materials ZrW_2−xMo_xO₈ (0 ≤ x ≤ 2) have been successfully synthesized by the reaction of a mixture of ammonium tungstate and ammonium molybdate with zirconium oxynitrate using a hydrothermal method. Effect of substituted ion Mo on the microstructure, α-to-β and cubic to trigonal phase transition in resulting ZrW_2−xMo_xO₈ powders was examined by the XRD experiments. It was found that the structural phase transition temperature decreased slightly with increasing substituted content. The cubic to trigonal phase transition was also influenced by substituted content. The resulting products decomposed to WO₃/MoO₃ and ZrO₂ as temperature increasing when x ≤ 0.5 and while x > 0.5, the cubic phase transited to trigonal phase. The effect of substituted Mo on the morphology of resulting products was also investigated by SEM experiments.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Synthesis and tunable thermal expansion properties of Sc2−xYxW3O12 solid solutions

A new series of rare earth solid solutions Sc_2−xY_xW₃O₁₂ was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc_2−xY_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc_2−xY_xW₃O₁₂ samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc₂W₃O₁₂-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y₂W₃O₁₂·nH₂O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc_2−xY_xW₃O₁₂. Thus it is proposed that thermal expansion properties of Sc_2−xY_xW₃O₁₂ can be adjusted by the employment of Y dopant; the obtained Sc_1.5Y_0.5W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10⁻⁶ °C⁻¹ in the 25–250 °C range.     

Sintering behavior and microwave dielectric properties of a new low-permittivity ceramic system Ca(Mg1−xAlx)(Si1−x/2Alx/2)2O6

The diopside ceramics with a formula of Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆ (x=0.01–0.3) were synthesized via a traditional solid-state reaction method, and their solid solubility, sintering behavior and microwave dielectric properties were investigated. The results revealed that the solubility limit of Al₂O₃ in Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆, which is defined as x, was between 0.15 and 0.2, and a second phase of CaAl₂SiO₆ presented when the x value reached 0.2. Appropriate Al³⁺ substitution for Mg²⁺ and Si⁴⁺ could promote the sintering process and lower the densification temperature, and a broadened densification temperature range of 1250–1300 °C was obtained for the compositions of x=0.08–0.15. With the increase of the x value, the dielectric constant (ε_r) increased roughly linearly, and the temperature coefficient of frequency (τ_f) showed a rising trend. The Q×f values increased from 57,322 GHz to 59,772 GHz as the x value increased from 0.01 to 0.08, and then they were saturated in the range of x=0.08–0.2. Further increase of the x value (x≥0.25) deteriorated the microwave dielectric properties. Good microwave dielectric properties of ε_r=7.89, Q×f=59,772 GHz and τ_f=−42.12 ppm/°C were obtained for the ceramics with the composition of x=0.08 sintered at 1275 °C.     

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

LiNi_1−xCo_xO₂ (x = 0, 0.1, 0.2) cathode materials were successfully synthesized by a rheological phase reaction method with calcination time of 0.5 h at 800 °C. All obtained powders are pure phase with α-NaFeO₂ structure (R-3m space group). The samples deliver an initial discharge capacity of 182, 199 and 189 mAh g⁻¹ (25 mA g⁻¹, 4.35-3.0 V), respectively. The reaction mechanism was also discussed, which consists of a series of defect reactions. As a result of these defect reactions, the reaction of forming LiNi_1−xCo_xO₂ takes place in high speed.     

Structure,dielectric and piezoelectric properties of Ba0.90Ca0.10Ti1−xSnxO3 lead-free ceramics

Lead-free piezoelectric ceramics Ba_0.90Ca_0.10Ti_1−xSn_xO₃ have been prepared by a conventional ceramic fabrication technique and the effects of Sn⁴⁺ on the structure, dielectric and piezoelectric properties of the ceramics have been investigated. All the ceramics exhibit a pure perovskite structure. After the substitution of Sn⁴⁺, the crystal structure of ceramics is transformed gradually from a tetragonal to an orthorhombic phase, and becomes a pseudo-cubic phase at x≥0.14. The substitution also decreases the Curie temperature greatly from 138 °C at x=0 to 33 °C at x=0.12, and shifts the orthorhombic–tetragonal phase transition to higher temperatures. Coexistence of the orthorhombic and tetragonal phases is formed in the ceramic at x=0.10, leading to significant improvements in the piezoelectric properties: d₃₃=521 pC/N and k_p=45.5%. Our results also reveal that the ceramics sintered at higher temperatures contain larger grains, and thus exhibit more noticeable tetragonal–orthorhombic phase transition and enhanced ferroelectric and piezoelectric properties.     

Solubility limits and microwave dielectric properties of Ba6−3xSm8+2xTi18O54 solid solution

Upper and lower solubility limits in Ba_6−3xSm_8+2xTi₁₈O₅₄ tungsten bronze ceramics were determined by Rietveld refinement of XRD data combined with backscattered electron images, and the variation tendency of microwave dielectric characteristics was also investigated. The upper solubility limit was confirmed as x = 2/3, while the lower solubility limit was determined as 1/4 instead of the previously reported one x = 3/10. The dielectric constant of Ba_6−3xSm_8+2xTi₁₈O₅₄ ceramics decreases monotonically with increasing x, while the small temperature coefficient of resonant frequency with complex variation tendency is observed for the compositions 1/2 ≤ x ≤ 4/5. The Qf value increases at first, reaches the maximum around x = 2/3, and turns to decrease for x > 7/10.     

MnxCu1−xCo2O4 used as bifunctional electrocatalyst in alkaline medium

Composite film electrodes containing mechanically mixed Mn_xCu_1−xCo₂O₄ (0 ≤ x ≤ 1) particles, carbon black Vulcan XC72R and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) were formed on the glassy carbon disk surface of a rotating ring-disk electrode (RRDE) and studied for the oxygen reduction and evolution reactions (ORR and OER, respectively) in 1 M KOH solution. The electrocatalytic activities for both reactions were observed to depend strongly on the Mn content in CuCo₂O₄. An opposite trend was observed for the apparent and intrinsic electrocatalytic activities for the ORR; the simultaneous presence of Cu and Mn was found to be detrimental to the intrinsic charge density, but beneficial to the geometric charge density with a maximum for Mn_0.6Cu_0.4Co₂O₄. The latter was characterized by the highest total number of electrons exchanged per O₂ molecule, n, close to 4, greater k₁ (4e⁻ process)/k₂ (2e⁻ process) ratios, and by a unique and low Tafel slope (−41 mV dec⁻¹). The results obtained for the OER showed that the intrinsic electrocatalytic activity is determined by the number of active sites (Co⁴⁺) electrochemically formed at the oxide surface prior to the OER, from Co³⁺ cations. The partial substitution of Cu by Mn in CuCo₂O₄ was found to decrease the OER activity.