Magnetic properties of Nd0.9Dy0.1Fe3(BO3)4

The magnetic properties of trigonal Nd_0.9Dy_0.1Fe₃(BO₃)₄ substituted compound with the competitive Nd-Fe and Dy-Fe exchange interactions have been investigated. It has been shown that in Nd_0.9Dy_0.1Fe₃(BO₃)₄ a spontaneous spin-reorientation transition from an ease-axis state to an easy-plane occurs near 8 K. Anomalies of the magnetization curves are observed in a spin-flop transition induced by the magnetic field B‖c. The calculations were performed using a molecular-field approximation and a crystal-field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of Nd_0.9Dy_0.1Fe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Vacuum ultraviolet luminescence from a micro-pulling-down method grown Nd:(La0.9,Ba0.1)F2.9

Vacuum ultraviolet (VUV) luminescence from a Nd³⁺:(La_1−x,Ba_x)F_3−x (x=0.1) and a Nd³⁺:LaF₃ single crystal grown by the micro-pulling-down method modified for fluoride crystal growth is discussed. Emission resulting from excitation with 157 nm pulses of a F₂ laser and by 290 nm femtosecond pulses of a Ti:sapphire laser show that the luminescence spectral and temporal characteristics are similar for both excitation cases and that they have good prospects as a VUV laser material.     

Influence of boron on the giant magnetocaloric effect of La(Fe0.9Si0.1)13

The influences of boron addition on the phase formation, Curie temperature and magnetic entropy change of the NaZn₁₃-type La(Fe_0.9Si_0.1)₁₃ compound have been investigated. Eight boron containing La(Fe_0.9Si_0.1)₁₃B_x samples were prepared with x=0, 0.03, 0.06, 0.1, 0.2, 0.3, 0.5 and 0.6, respectively. Experimental results show that a small amount of B addition in La(Fe_0.9Si_0.1)₁₃ forms the solid solution NaZn₁₃-type structure phase by substituting B for Si or doping B into interstitial position of the lattice, preserves its giant magnetocaloric effects due to their first-order structural/magnetic transition, as well as increase its Curie temperature T_c slightly. The maximum magnetic entropy changes in the magnetic field change of 0–1.6 T are around 20 J kg^–1 K^–1 for the samples with Boron addition less than 0.3, while improving the Curie temperatures by 2 K.     

Oxygen non-stoichiometry and defect thermodynamics in La2Ni0.9Fe0.1O4+δ

The oxygen hyperstoichiometry of K₂NiF₄-type La₂Ni_0.9Fe_0.1O_4+δ, studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10⁻⁵-0.7 atm at 923-1223 K, is considerably higher than that of undoped lanthanum nickelate. The p(O₂)-T-δ diagram of iron-doped lanthanum nickelate can be adequately described by introducing point-defect interaction energy in the concentration-dependent part of defect chemical potentials and accounting for the site-exclusion effects. The critical factors affecting the equilibrium oxygen incorporation process include coulombic repulsion of interstitial anions, trapping of the p-type electronic charge carriers by iron, and interaction between Fe³⁺ and holes localized on nickel cations. Due to low chemical expansion of La₂Ni_0.9Fe_0.1O_4+δ lattice, the thermodynamic functions governing oxygen intercalation, site-blocking factors and hole mobility are all independent of the defect concentrations. The predominant 3+ state of iron cations under oxidizing conditions was confirmed by the Mössbauer spectroscopy. The stability of La₂NiO₄-based phase in reducing atmospheres is essentially unaffected by doping.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.     

High-throughput characterization of local conductivity of Nd0.9Ca0.1Ba2Cu3O7−δ thin film by the low-temperature scanning microwave microscope

We developed a scanning microwave microscope (SμM) designed for high-throughput electric-property screening as well as for rapid construction of electronic phase diagrams at low temperatures. As a sensor probe, we used a high-Qλ/4 coaxial cavity resonator to which a thin needle with ball-tip end was attached. The sensor module was mounted on the low-temperature XYZ stage, which allowed us to map out the change of resonance frequency and quality factor due to the local tip-sample interaction at low temperatures. From the measurements of combinatorial thin films, such as Ti_1−xCo_xO_2−δ and Nd_0.9Ca_0.1Ba₂Cu₃O_7−δ (NCBCO), it was demonstrated that this SμM system has enough performance for the high-throughput characterization of sample conductance under variable temperature conditions.     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Enhanced hydrogen production by doping Pr into Ce0.9Hf0.1O2 for thermochemical two-step water-splitting cycle

We synthesized (Ce_0.9Hf_0.1)_1−xPr_xO_2−δ (x=0, 0.05 and 0.1) using the polymerized complex method. The synthesized samples, as well as the samples after thermochemical two-step water-splitting cycles have a fluorite structure and Pr exists in the solid solutions with both trivalent and tetravalent states, as suggested by powder X-ray Diffraction (XRD) Patterns. The reduction fraction of Ce⁴⁺ in redox cycles (oxidation step in air) and two-step water-splitting cycles (oxidation step in steam) indicates that the addition of Pr into Ce–Hf oxide solid solution cannot improve the reduction fraction of Ce⁴⁺ during the redox cycles but both the reduction fraction of Ce⁴⁺ and H₂ yield are significantly enhanced during two-step water-splitting cycles. The chemical composition of 10 mol% Pr doped Ce_0.9Hf_0.1O₂ exhibits the highest reactivity for hydrogen production in H₂-generation step by yielding an average amount of 5.72 ml g⁻¹ hydrogen gas, which is much higher than that evolved by Ce_0.9Hf_0.1O₂ (4.50 ml g⁻¹). The enhancement effect of doping Pr on the performance during two-step water-splitting cycles is because of the multivalent properties of Pr, which can: (1) reduce the amount of Ce³⁺ oxidized by contamination air (contamination air eliminated by partial oxidation of Pr³⁺ to Pr⁴⁺) in H₂-generation step; (2) enhance the reaction rate in H₂-generation step by improving the ionic conductivity (extrinsic oxygen vacancies created by the substitution of Ce⁴⁺ by Pr³⁺).     

Spectral properties of Nd-doped Sr3Ga2Ge4O14 crystal

Neodymium doped strontium gallogermanate crystals were grown successfully by the Bridgman technique. The linear thermal expansion coefficients for the c- and a-axes were measured as 5.8 × 10⁻⁶ °C⁻¹ and 6.5 × 10⁻⁶ °C⁻¹. Absorption spectra, and fluorescence spectra, as well as fluorescence decay curves of Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal, have been recorded at room temperature and used to calculate the absorption and stimulated emission cross-sections. Based on the Judd-Ofelt theory, three intensity parameters were obtained. The luminescent quantum efficiency of the ⁴F_3/2 level was determined to be approximately 73.8% for this material. Compared with other Nd³⁺-doped laser crystals, Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal displays special laser properties due to its disorder structure.     

Critical behavior and magnetic entropy change in the La0.6Sr0.4Mn0.8Fe0.1Cr0.1O3 perovskite

Critical behavior in the La_0.6Sr_0.4Mn_0.8Fe_0.1Cr_0.1O₃ ceramics was studied using magnetization methods. Results show that the paramagnetic–ferromagnetic transition is of second order. Based on the critical behavior analysis using the Banerjee criterion and the Kouvel–Fisher method, we find the critical exponents: β=0.395±0.010, γ=1.402±0.010, and δ=5.208±0.007, for which the magnetic interaction is satisfied within the three-dimensional Heisenberg model. Results indicate the presence of short-range interactions. The magnetic entropy change (−ΔS_M) reached maximum values of 1.75, 1.45, 1.15, 0.8 and 0.43 J Kg⁻¹ K⁻¹ under a magnetic field variation of 5, 4, 3, 2 and 1 T, respectively. Nevertheless, these (−ΔS_M) values are much low for any potential application at this moment. The nature of this phenomenon is discussed in relation to the characteristics of the magnetic phase transition and critical exponents.     

Structure and dielectric studies of nano-composite Fe2O3: BaTiO3 prepared by sol-gel method

Nano-structure pure barium titanate (BaTiO₃) and that was doped with iron oxide (Fe₂O₃), have been prepared by sol-gel method, using barium acetate (Ba(Ac)₂) and titanium butoxide (Ti(C₄H₉O)₄), as precursors. The as-grown prepared samples by sol-gel technique were found to be amorphous, which crystallized to the tetragonal phase after synthesized at 750 °C in air for 1 h as detected from the XRD patterns. The XRD data were confirmed by transmission electron microscope (TEM). The dielectric properties namely; dielectric constant (ε′) and loss tangent (tan δ) in the frequency range between 42 Hz and 1 MHz, at range of temperature 25-250 °C were investigated. The temperature dependence of ε′ and tan δ for the undoped and doped materials, at 1 kHz, was also investigated. As a result, tan δ increased rapidly with decreasing temperature below 125 °C (Curie temperature) while above this temperature, tan δ shows temperature independent. As a result, below and above Curie temperature, ferroelectric phase and paraelectric phase of BaTiO₃ can be obtained, respectively.     

High heat generation ability in AC magnetic field for nano-sized magnetic Y3Fe5O12 powder prepared by bead milling

Nano-sized magnetic Y₃Fe₅O₁₂ ferrite having a high heat generation ability in an AC magnetic field was prepared by bead milling. A commercial powder sample (non-milled sample) of ca. 2.9 μm in particle size did not show any temperature enhancement in the AC magnetic field. The heat generation ability in the AC magnetic field improved with a decrease in the average crystallite size for the bead-milled Y₃Fe₅O₁₂ ferrites. The highest heat ability in the AC magnetic field was for the fine Y₃Fe₅O₁₂ powder with a 15-nm crystallite size (the samples were milled for 4 h using 0.1 mm? beads). The heat generation ability of the excessively milled Y₃Fe₅O₁₂ samples decreased. The main reason for the high heat generation property of the milled samples was ascribed to an increase in the Néel relaxation of the superparamagnetic material. The heat generation ability was not influenced by the concentration of the ferrite powder. For the samples milled for 4 h using 0.1 mm? beads, the heat generation ability (W g⁻¹) was estimated using a 3.58×10⁻⁴ fH² frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which is the highest reported value of superparamagnetic materials.     

Effect of Nd concentration on structural and optical properties of Nd:Y2O3 transparent ceramic

Y₂O₃ transparent ceramics with different Nd concentration (0.1-7.0at%) were fabricated using ZrO₂ as additive. All the samples exhibit high transparency over a broad spectral region. The elements (Y, O and Nd) are uniformly distributed in the ceramic body, and the average grain size increases with Nd content. Based on the absorption spectrum, the Judd-Ofelt intensity parameters are calculated (Ω₂=4.364×10⁻²⁰ cm², Ω₄=3.609×10⁻²⁰ cm² and Ω₆=2.919×10⁻²⁰ cm²). The absorption coefficients increase linearly with Nd³⁺ doping concentration. The absorption cross-section at 804 nm and stimulated emission cross-section at 1078 nm are calculated to be 1.54×10⁻²⁰ and 7.24×10⁻²⁰ cm², respectively. All the emission bands exhibit the highest emission intensities with 1.0at% Nd³⁺ ion content, while the lifetime decreases dramatically from 321.5 μs (0.1at% Nd) to 17.9 μs (7.0at% Nd). According to the emission spectra and measured lifetime, the optimum doping concentration of Nd³⁺ ion in Y₂O₃ transparent ceramic might be around 1.0at%.     

Structural characterization of La0.9Ba0.1MnO3/Y-ZrO2 film by X-ray diffraction

Perovskite manganite La_0.9Ba_0.1MnO₃(LBMO) films were deposited on (0 0 1)-oriented single crystal yttria-stabilized zirconia (YSZ) substrate by 90° off-axis radio frequency magnetron sputtering. The film thickness ranged from 10 nm to 100 nm. Grazing incidence X-ray diffraction technique and high resolution X-ray diffraction were applied to characterize the structure of LBMO films. The LBMO film mainly consisted of (0 0 1)-orientated grain as well as weakly textured (1 1 0)-orientated grain. The results indicated that an amorphous layer with thickness of about 4 nm was formed at the LBMO/YSZ interface. The strain in LBMO film was small and averaged to be about -0.14%. The strain in the film was not lattice mismatch-induced strain but residual strain due to the difference in thermal expansion coefficient between film and substrate.     

Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

The nano-structured Fe(III)-doped TiO₂ photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe_xTi_1−xO₂ (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO₂ catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe_xTi_1−xO₂, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO₂ increases. The energy band gap of Fe(III)-doped TiO₂ is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe³⁺ is in low spin state.     

Effects of doping site and pre-sintering time on microstructure and magnetic properties of Fe-doped BaTiO3 ceramics

The A-site substituted BaTiO₃ ceramics were prepared by solid-state reaction via partial substitution of Fe for Ba²⁺. By comparison with the B-site substituted sample made under similar conditions, the effect of Fe doping site on microstructure and magnetism was investigated using X-ray diffraction, Mössbauer spectroscopy and vibrating sample magnetometer. It is found that A-site substitution can be realized to a certain extent at 7 at% Fe addition, whereas impurities are observed at higher Fe concentrations. In the nominal (Ba_0.93Fe_0.07)TiO₃ sample, the Fe ions are present as Fe²⁺ and Fe³⁺, respectively, replacing A-site Ba²⁺ and octahedral B-site Ti⁴⁺ in hexagonal perovskite lattice. The double-exchange Fe²⁺-O²⁻-Fe³⁺ interactions produce ferromagnetism well above room temperature, but the saturation magnetization and the Curie temperature are both obviously lower than those for B-site substitution due to different magnetic exchange mechanisms. In the B-site substituted sample Ba(Ti_0.93Fe_0.07)O₃, the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti⁴⁺ sites are responsible for ferromagnetism. These results mean that B-site substitution is a better way for Fe-doped BaTiO₃ system to obtain high-Curie-temperature ferromagnetism. Moreover, increasing pre-sintering time can further improve the magnetism of B-site substituted samples, through which the saturation magnetization for Ba(Ti_0.93Fe_0.07)O₃ is enhanced ∼6 times.     

Structural and magnetic properties of Sc1.1Fe3.9Al8 alloy

The crystallochemical and magnetic nature of ternary Sc_1+δFe_4−δAl₈ intermetallic with a small Sc excess δ=0.1 was investigated by scanning electron microscope, X-ray powder diffraction, neutron diffraction, Mössbauer effect and superconducting quantum interference device techniques. The sample crystallizes in a tetragonal ThMn₁₂ type structure. The excess of Sc atoms substitute Fe at the (8f) positions and have a pronounced effect on the magnetic properties. The experiments carried out in temperature range 4-320 K show that below 120 K the magnetic structure of the alloy forms a double cycloid with magnetic moments rotating according to the incommensurate in-plane wave vector, which is temperature independent up to 160 K. The value of Fe magnetic moment is close to 0.9 μ_B atom⁻¹ at 4 K. Temperature dependence of unit cell dimensions can be explained within the Debye-Grüneisen approximation.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Thermal, electrical, and electrochemical properties of Lanthanum-doped Ba0.5Sr0.5 Co0.8Fe0.2O3-δ

Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba_0.5Sr_0.5)_1-xLa_xCo_0.8Fe_0.2O_3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba_0.5Sr_0.5 Co_0.8Fe_0.2O_3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm⁻¹ at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm², which was only 46% of BSCF.