Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.     

Structure and magnetic properties of perovskite Sr2CuNbO6−δ

Single phase perovskite Sr₂CuNbO_6−δ with a high proportion of Cu¹⁺ ions and oxygen vacancies was synthesized by solid-state reaction. The structure was determined by Rietveld method with space group Pm3m. Isotropic g value was evaluated from electron spin resonance (ESR) measurements. The ESR result is consistent with that of magnetic susceptibility.     

Local order and structural transitions in the molecule-based layer ferrimagnet (n-C4H9)4N FeFe(C2O4)3

Local structural order and temperature-dependent structural variation have been studied in the molecular-based layer ferrimagnet (n-C₄H₉)₄N Fe^IIFe^III(C₂O₄)₃ by EXAFS and high resolution X-ray powder diffraction. The EXAFS spectra measured at the Fe K-edge are successfully modelled by successive O, C, O and metal shells, showing that even when there is extensive structural disorder due to stacking faults, the local structural order in this class of ferrimagnets is fully retained. In this salt, which shows remarkable negative magnetisation at low temperature (Néel class Q), the EXAFS Debye-Waller factor has a discontinuity at 40 K, corresponding to one found in the magnetisation. At the same temperature there is also a change in the expansion of the lattice as evidenced by the high resolution X-ray powder diffraction.     

Features of the electrochemical lithium insertion into monophosphate tungsten bronzes (PO2)4(WO3)2m (m=9 and 10)

Electrochemical lithium insertion into (PO₂)₄(WO₃)_2m, where m=9 and 10, has allowed the determination of several phases Li_x(PO₂)₄(WO₃)_2m between 3.4 and 0.01 V vs Li⁺/Li⁰. After the first cycle the electrochemical system was unable to maintain the high specific capacity of the cells (540 Ah/kg) due to irreversible processes. Nevertheless at high voltage values, above 1.4 V vs Li⁺/Li⁰, the lithium insertion proceeded through a reversible mechanism. By means of X-ray diffraction experiments we have detected the nature of different phases Li_x(PO₂)₄(WO₃)_2m formed and we have established a correlation with the reversible/irreversible processes detected during the electrochemical insertion.     

Synthesis, structure and magnetic properties in the Nd2O3-Gd2O3 mixed system synthesized at 1200 °C

Phase relation studies in the Gd₂O₃-Nd₂O₃ system have been performed on (Gd_1−xNd_x)₂O₃ samples (0?x?1) with the purpose of performing a systematic study of the composition effects on their structural and magnetic properties. All the samples were synthesized by calcination of the related oxalates at 1200 °C in order to ensure the complete decomposition of the oxalates. Five phase regions, namely an A-type hexagonal, a B-type monoclinic, a C-type cubic solid solution and two biphasic mixtures of the former three phase fields were detected in this system. The magnetic susceptibility measurements showed the presence of antiferromagnetic interactions in all samples. The Curie-Weiss temperature shows a nonlinear dependence on concentration. Deduced effective magnetic moments are close to the free ion values.     

Effects of Na2CO3 flux addition on the structure and photoluminescence properties for Eu-doped YVO4 phosphor

The luminescence properties of (Y_0.9Eu_0.1)VO₄ phosphor with Na₂CO₃ flux prepared using the solid-state reaction were investigated. The XRD patterns show that all of the peaks are attributed to the YVO₄ phase. The best crystallinity was obtained with 2 wt% Na₂CO₃ flux addition. The surface morphology of (Y_0.9Eu_0.1)VO₄ phosphor changed from fluffy to a bar shape structure after Na₂CO₃ flux addition due to the tetragonal crystal system of YVO₄. The calcined powders emit bright red luminescence centered at 618 nm due to the ⁵D₀→⁷F₂ electric dipole transition under an excitation wavelength of 318 nm; its intensity was increased about 15% with 2 wt% Na₂CO₃ flux addition. Red shift behavior was observed for the charge transfer state (CTS) absorption, which was due to the grain size of (Y_0.9Eu_0.1)VO₄ phosphor increasing with increasing flux content. For 2 wt% Na₂CO₃ flux addition, the red emission of the (Y_0.9Eu_0.1)VO₄ phosphor had CIE chromaticity coordinates of (0.66, 0.34), which are very close to the NTSC system standard red chromaticity coordinates of (0.67, 0.33).     

Synthesis and characterization of room-temperature ferromagnetism in Fe- and Ni-co-doped In2O3

Observation of room-temperature ferromagnetism in Fe- and Ni-co-doped In₂O₃ samples (In_0.9Fe_0.1−xNi_x)₂O₃ (0?x?0.1) prepared by citric acid sol-gel auto-igniting method is reported. All of the samples with intermediate x values are ferromagnetic at room-temperature. The highest saturation magnetization (0.453 μ_B/Fe+Ni ions) moment is reached in the sample with x=0.04. The highest solubility of Fe and Ni ions in the In₂O₃ lattice is around 10 and 4 at%, respectively. The 10 at% Fe-doped sample is found to be weakly ferromagnetic, while the 10 at% Ni-doped sample is paramagnetic. Extensive structure including Extended X-ray absorption fine structure (EXAFS), magnetic and magneto-transport including Hall effects studies on the samples indicate the observed ferromagnetism is intrinsic rather than from the secondary impurity phases.     

Preparation of LiCoO2 nanofibers by electrospinning technique

Using a sol-gel processing and electrospinning technique, extrathin fibers of PVA (polyvinyl alcohol)/lithium chloride/cobalt acetate composite were prepared. After calcinations of the above precursor fibers at 600°C, LiCoO₂ nanofibers with a diameter of 100-150 nm, were successfully obtained. Measurements of TG/DTA, IR, XRD, Raman, SEM, EDS, respectively, were performed to characterize the properties of the as-prepared materials. We observed a strong correlation between crystalline phase and morphology of the fibers and calcinations temperature.     

Interaction of copper and NO2: Effect of joint presence of SO2, relative humidity and temperature

This paper reports laboratory tests involving the dry deposition on copper surfaces of NO₂, alone and in combination with SO₂, at different concentrations (200 and 800 μg m⁻³), temperatures (15, 25 and 35 °C) and relative humidities (50%, 70% and 90%). Gravimetric results and characterisation of the corrosion products by optical microscopy, scanning electron microscopy (SEM/EDX), grazing incidence X-ray diffraction (GIXD) and X-ray photoelectron spectroscopy (XPS) show that the corrosive effect of NO₂ acting alone depends greatly on the RH. At 90% RH copper behaves in the same way as in unpolluted atmospheres, while at lower RH localised attack is detected. Analysis reveals the presence of basic copper nitrate (gerhardtite, Cu₂(OH)₃NO₃). However, in SO₂-polluted atmospheres no differential behaviour with RH or temperature is observed. In these atmospheres copper corrosion is similar to that obtained in unpolluted or in NO₂-polluted atmospheres at high RH, although GIXD detects basic copper sulphate (posnjakite, Cu₄(OH)₆SO₄·2H₂O). In the case of mixed atmospheres (SO₂+NO₂) a significant accelerating effect is observed when [NO₂]>[SO₂]. Otherwise an inhibitive effect is detected. At high RH in the presence of SO₂, NO₂ favours SO₂ oxidation and finally sulphuric acid formation, which attacks the cuprite layer. S-containing compounds, especially basic copper sulphate, are easily detected by GIXD and XPS in the outermost corrosion product layer. However, at low RH, NO₂ reacts preferentially with adsorbed water to produce nitrous and nitric acids that attack the cuprite layer. In this case, an outer corrosion product layer containing copper nitrite (soluble) and basic copper nitrate is formed over an intermediate layer that contains significant amounts of basic copper sulphate from the previous interaction of sulphuric acid and cuprite.     

Growth and characterization of new transparent conductive oxides single crystals β-Ga2O3: Sn

Tin oxide doped β-Ga₂O₃ single crystals are recognized as transparent conductive oxides (TCOs) materials. They have a larger band gap (4.8 eV) than any other TCOs, thus can be transparent in UV region. This property shows that they have the potential to make the optoelectronic device used in even shorter wavelength than usual TCOs. β-Ga₂O₃ single crystals doped with different Sn⁴⁺ concentrations were grown by the floating zone technique. Their optical properties and electrical conductivities were systematically studied. It has been found that their conductivities and optical properties were influenced by the Sn⁴⁺ concentrations and annealing.     

Observation of ordered orbital of YTIO3 by the X-ray magnetic diffraction experiments

X-ray magnetic diffraction (XMD) experiments of ferromagnetic YTiO₃ were performed. The orbital-magnetic form factor (L) and the spin-magnetic form factor (S) were individually measured by utilizing the LS separation method of the XMD. The experiments consisted of two parts. The first was the measurement of the orbital-magnetic form factor to examine whether the orbital moment of this compound was quenched or not. The second was the measurement of the spin-magnetic form factor to examine whether the ordered orbital of Ti-3d electrons was observed by the XMD. The result of the first experiment suggested quenching of the orbital moment. In the second experiment, the spin-magnetic form factor was observed for the total 22 reciprocal-lattice points. Calculated spin-magnetic form factor with a model wave function of the ordered orbital reproduced the observed one well. This result shows that the ordered orbital of Ti-3d electrons can be observed by the XMD.     

Orientation-dependent dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films prepared by sol-gel method

The orientation-dependent dielectric properties of barium stannate titanate (Ba(Sn_0.15Ti_0.85)O₃, BTS) thin films grown on (1 0 0) LaAlO₃ single-crystal substrates through sol-gel process were investigated. The nonlinear dielectric properties of the BTS films were measured using an inter-digital capacitor (IDC). The results show that the in-plane dielectric properties of BTS films exhibited a strong sensitivity to orientation. The upward shift of Curie temperature (T_c) of the highly (1 0 0)-oriented BTS thin films is believed to be attributing to a tensile stress along the in-plane direction inside the film. A high tunability of 47.03% was obtained for the highly (1 0 0)-oriented BTS films, which is about three times larger than that of the BTS films with random orientation, measured at a frequency of 1 MHz and an applied electric field of 80 kV/cm. This work clearly reveals the highly promising potential of BTS films for application in tunable microwave devices.     

Influence of Co, Ni and Zn substitution for Cu on the structural and superconducting properties of (Hg0.7Cr0.3)Sr2CuO4+δ

The effect of Co, Ni and Zn substitutions for Cu on the phase stability and superconducting properties of (Hg_0.7Cr_0.3)Sr₂CuO_4+δ was investigated. X-ray diffraction (XRD) revealed that both Co and Zn are soluble in the (Hg_0.7Cr_0.3)Sr₂CuO_4+δ material up to about 5% of the Cu content, whereas the solubility of Ni is extended up to 10%. Electrical resistivity and magnetic susceptibility measurements show that the value of the superconducting critical temperature T_c decreases linearly with the impurity content. The depression of T_c indicates that the suppression of the superconductivity in Co- and Ni-substituted samples is much stronger than that in Zn-substituted ones. The residual resistivity scales linearly with the doping level as expected from the impurity scattering due to disorder. Some possible explanations for the stronger suppression of T_c by the Co and Ni substitution than by Zn substitution are provided.     

Microwave absorption properties of Sr2FeMoO6 nanoparticles

The microwave absorption properties of nanosized double perovskite Sr₂FeMoO₆ and epoxy resin composites were investigated in the frequency range of 2-18 GHz using the coaxial method. The Sr₂FeMoO₆ composites with an optimal 20 wt% epoxy resin showed a strong electromagnetic attenuation of −49.3 dB at 8.58 GHz with a matching thickness of 2.15 mm. Moreover the optimum absorption frequency at which the reflection loss is less than −20 dB, which corresponds to 99% reflection loss of the incident microwave, is from 5.7 to 13.2 GHz with the matching thickness ranging from 3.0 to 1.5 mm. The excellent microwave-absorption properties are a consequence of a proper electromagnetic match due to the existence of the insulating matrix of anti-site defects and anti-phase domains, which not only contribute to the dielectric loss but also to the reduced eddy current loss.     

Spin glass like behavior in Cd0.42Mn0.58In2S4

The magnetic behavior of the diluted magnetic semiconductor Cd_0.42Mn_0.58In₂S₄ has been study by dc magnetization and ac susceptibility experiments. Zero field cooled and field cooled measurements reveal irreversibility below T_irr=2.60±0.15 K. Ac susceptibility data, performed as a function of the temperature and the frequency, confirm the spin-glass like behavior of the material with T_f=2.75±0.15 K. High temperature susceptibility data follow a typical Curie-Weiss law with θ=−74±1 K which suggests predominant antiferromagnetic interactions. The randomness of the magnetic ions, necessary to explain the magnetic behavior of the material, has been determined by X-ray powder diffraction experiments.     

Structural and luminescence characterization of synthetic Cr-doped Ni3(PO4)2

Ni_3–xCr_2x/3(PO₄)₂ (x=0 and 0.02) microcrystalline powders were obtained as single phases via a modified sol–gel Pechini-type in situ polymerizable complex method. The samples were characterized using scanning electron microscopy, X-ray diffraction, cathodoluminescence (CL), and thermoluminescence (TL) techniques. We found that Cr³⁺ doping modified the average particle and distribution. The mean particle size was 0.441 μm for Ni₃(PO₄)₂ and 0.267 μm for Ni_2.98Cr_0.013(PO₄)₂. The results also reveal that Cr³⁺ doping notably enhanced the CL and TL UV-blue emission.     

Structural and magnetic ordering in the VxNb1+yS2 system

The influence of composition on the structural ordering and magnetism in the V_xNb_1+yS₂ system has been investigated by X-ray diffraction and magnetic measurements. Stoichiometric V_1/3NbS₂ did not exhibit the structural ordering of vanadium between the NbS₂ layers. In the ordered structure, the vanadium composition deviated from the ideal value of to both higher and lower values, while the niobium composition was in the range of 0.05?y?0.18. Excess niobium, y>0, is thought to play an essential role in the structural ordering in this system. For samples with excess niobium and ordered structures, a magnetic transition was observed at 20-50 K, depending on the composition. The spontaneous magnetization of 3-5×10⁻³ μ_B/V atom is thought to be intrinsic to this system. The magnetization curves consisted of a constant and a proportional parts of the magnetic field, which correspond to the spontaneous magnetization and high-field susceptibility, respectively. The magnetization curves and the temperature dependencies of the high-field susceptibility were quite similar to those of the canted antiferromagnetic NiS₂. A correlation between the structural and magnetic ordering is suggested.     

Thermal stability of A-site ordered PrBaMn2O6 manganites

The crystal structure and electromagnetic properties as well as thermal stability of the A-site ordered PrBaMn₂O₆ manganites have been investigated. These samples have been prepared by using ‘two-steps’ synthesis mode. They have tetragonal structure with no tilt of MnO₆ octahedra and show ferromagnetic metal to paramagnetic semiconductor transition. The most significant structural feature of the A-site ordered manganites is that the MnO₂ sublattice is sandwiched by two types of rock-salt layers PrO and BaO. The different degree of Pr and Ba ions in the A-sublattice is revealed. The A-site ordered PrBaMn₂O₆ sample with maximum degree of the A-site order demonstrates ferromagnetic metallic to paramagnetic insulating transition with the Curie point ∼320 K. The A-site disordered Pr_0.50Ba_0.50MnO₃ sample is ferromagnetic metal below T_C≈140 K. The cation order in these compounds is stable in air up to 1300 °C. For the partly A-site ordered samples the magnetic and electronic phase separation is observed. The magnetotransport properties of the A-site ordered manganites treated under different conditions are discussed in terms of the superexchange interactions and A-site order degree.     

Magnetotransport coefficients of Sm0.55Sr0.45MnO3

Measurements of resistivity, magnetization, Seebeck coefficient in 0 and 1.5 T and Nernst coeffecient in 0.3, 0.9 and 1.8 T as a function of temperature on a polycrystalline sample Sm_0.55Sr_0.45MnO₃ are presented. The data demonstrate that an increase in both the carrier density and the mobility of the charge carriers is responsible for the observed colossal magnetoresistance in this compound.     

Magnetic and dielectric properties of Ni0.8Co0.1Cu0.1Fe2O4+PZT composites

Magnetoelectric composites of Ni_0.8Co_0.1Cu_0.1Fe₂O₄ and Lead Zirconate Titanate (PZT) were prepared by using conventional ceramic method. The measured values of saturation magnetization (M_s) and magnetic moments (μ_B) are in accordance with the volume fraction of ferrite content in the composite. The dielectric constant of the composites decreases with frequency. The plots of dielectric constant () against temperature (T) show a peak at their respective transition temperatures. The ME output was measured by varying dc bias magnetic field. A large ME output signal of 776 mV/cm was observed for 35% ferrite +65% ferroelectric composite. The magnetoelectric (ME) response is found to be dependent on the content of ferrite phase.