Phase formation, grain growth and magnetic properties of NiCuZn ferrites

We studied the effects of iron-deficient, stoichiometric and iron-excessive compositions on the phase formation, crystal structure, grain growth and magnetic property of NiCuZn ferrites. As the Fe₂O₃ ratio increased from iron-deficiency 47.0 mol% to iron-excess 54.0 mol%, the X-ray diffraction peaks initially shifted towards lower angle and then moved to higher angle. Correspondingly, an initial increase in lattice parameter followed by a subsequent decrease was observed. The lattice parameter showed a maximum 8.396 Å when the Fe₂O₃ ratio was 49.0 mol%. When the system was iron-deficient, ZnO phase was detected in addition to the spinel phase. However, equimolar and iron-excessive compositions exhibited a single spinel phase. As the content of Fe₂O₃ increased, the grain size, density, saturation induction and initial permeability first increased and then decreased. Core losses at 50 kHz and 150 mT, however, changed in the opposite way. Finally, NiCuZn ferrite with an equimolar composition (50.0 mol%) showed the highest initial permeability (1467), highest saturation induction (361 mT) and lowest core losses (234 kW/m³).     

Upconversion luminescence of colloidal solution of Y2O3 nano-particles doped with trivalent rare-earth ions

We have studied upconversion luminescence of colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺. Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ show sintering and agglomeration, because they are synthesized by firing a hydroxy carbonate precursor. Colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ is prepared through two-step dispersion process and the average diameter of the primary nano-particles is about 50 nm. Under excitation with 980-nm laser diode, upconversion luminescence of colloidal solution of the primary Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ in methyl isobuthyl ketone strongly appeared near 660 nm and weakly near 550 nm.     

Low temperature sintering of sub-stoichiometric Ni-Cu-Zn ferrites: Shrinkage, microstructure and permeability

We have studied sub-stoichiometric Ni-Cu-Zn ferrites with iron deficiency (i.e., <50mol% Fe₂O₃) of composition Ni_0.20Cu_0.20Zn_0.60+zFe_2−zO_4−(z/2) with 0≤z≤0.06. The temperature of maximum shrinkage rate is shifted from T=1000 °C for z=0 towards lower temperatures down to T=900 °C for a sub-stoichiometric ferrite with z=0.02. Dense samples are obtained after firing at 900 °C for z>0 only. Sub-stoichiometric compositions (z>0) do not form single-phase spinel ferrites after sintering at 900 °C, but rather represent mixtures of CuO and a stoichiometric ferrite with slightly modified composition. The formation of small amounts of CuO at grain boundaries is demonstrated by XRD and SEM. The permeability is increased from μ=80 for stoichiometric ferrites (z=0) to μ=660 for z=0.02. The formation of CuO during sintering of sub-stoichiometric ferrites supports densification and is a prerequisite for low temperature firing of multilayer inductors. Addition of 1 wt% Bi₂O₃ as liquid phase sintering aid is required to provide sufficient densification of the stoichiometric ferrite (z=0) at 900 °C. Addition of 0.37 wt% Bi₂O₃ to a sub-stoichiometric ferrite (z=0.02) results in dense samples after firing at 900 °C; however, the microstructure formation is dominated by heterogeneous grain growth.     

Dielectric dispersion in PbO-Sb2O3-As2O3:V2O5 glasses

Dielectric properties, viz. dielectric constant ε′, loss tan δ and a.c conductivity σ_ac (over a wide range of frequency and temperature) and dielectric breakdown strength of PbO-Sb₂O₃-As₂O₃ glasses doped with V₂O₅ (ranging from 0 to 0.5 mol%) are studied. Analysis of these results, based on optical absorption and ESR spectra, indicates that the insulating strength of the glasses is comparatively high when the concentration of V₂O₅ is about 0.3 mol% in the glass matrix.     

Photoelectron spectroscopic investigation of transformation of trifluoroacetate precursors into superconducting YBa2Cu3O7−δ films

X-ray photoelectron spectroscopy (XPS) has been used to investigate the evolution of surface chemistry of YBa₂Cu₃O_7−δ (Y123) films prepared by the metalorganic deposition (MOD) process using trifluoroacetate (TFA) precursors. Detailed XPS core-level spectra obtained from the samples quenched from various points during the calcining and firing stages have been reported for the first time and are used to identify surface species. The XPS data show evidence of formation of intermediate phases such as Y-O-F, BaF₂, and CuO during the calcining process, which are the decomposition products of yttrium, barium, and copper trifluoroacetates, respectively. The TFA precursors are completely decomposed at the end of calcination. The change of binding energies for Y 3d_5/2, Ba 3d_5/2, and O 1s during the firing process indicates that Y123 starts to form at 800 °C after 0.5 h firing. Based on the experimental results, an alternative mechanism of the chemical evolution from precursor to final film in the TFA-MOD process is proposed.     

Magnetic studies of Li-Zn ferrites prepared by citrate precursor method

Ferrites having the general formula Li_0.5−0.5xZn_xFe_2.5−0.5xO₄ where 0≤x≤0.6 in steps of 0.2 were prepared by the citrate precursor method. The Curie temperature measured shows a decrease with increasing Zn concentration. Experimental results show that the room temperature initial permeability increases with the increase in the concentration of zinc. The initial permeability has also been studied as a function of frequency in the range of 100 Hz-1 MHz. The real part of initial permeability referred as initial permeability and the imaginary part of initial permeability better known as permeability loss show dispersion with frequency. Possible mechanism contributing to the above processes is discussed.     

Improvement in electrical and magnetic properties of mixed Mg-Al-Mn ferrite system synthesized by citrate precursor technique

In the present work, mixed magnesium-manganese ferrites of composition Mg_0.9Mn_0.1Al_0.3Co_zFe_1.7−zO₄ where z=0.3, 0.5 and 0.7 have been synthesized by the citrate precursor technique. X-ray diffraction patterns of the samples confirmed the formation of single-phase spinel structure. The ferrites have been investigated for their electric and magnetic properties such as dc resistivity, Curie temperature, saturation magnetization, initial permeability and relative loss factor (RLF). Fairly constant value of initial permeability over a wide frequency range (0.1-20 MHz) and low values of the relative loss factor of the order of 10⁻⁴-10⁻⁵, in the frequency range 0.1-30 MHz, are the cardinal achievements of the present investigation. In addition to this, initial permeability was found to increase with an increase in temperature while RLF was observed to be low at these temperatures. The dc resistivity and Curie temperature were found to increase with an increase in cobalt content. The mechanisms contributing to these results are discussed in detail in this paper.     

Effect of sintering temperature on structural and magnetic properties of NiCuZn and MgCuZn ferrites

The low temperature microwave sintered NiCuZn and MgCuZn ferrites with compositions Ni_0.35Cu_0.05Zn_0.60Fe₂O₄ and Mg_0.35Cu_0.05Zn_0.60Fe₂O₄ were synthesized by conventional mixed oxide method. NiCuZn and MgCuZn ferrite samples obtained showed better sintered densities at 950 and 900 °C, respectively. The scanning electron micrographs of both the ferrite samples appear to be very much similar. The magnitude of initial permeability of MgCuZn ferrite samples is found to be obviously higher than those of NiCuZn ferrite samples at all sintering temperatures. This is mainly due to the fact that MgCuZn ferrite has smaller magnetocrystalline anisotropy constant and magnetostrictive constant. NiCuZn ferrites have higher saturation magnetization than MgCuZn ferrites, which is due to the higher magnetic moment of NiCuZn ferrites. Our results indicate that the microwave sintering method seems to be a potential technique in the MLCI technology.     

Physical studies on composites Ag7I4VO4-Al2O3

The electrical properties of the solid electrolytes Ag₇I₄VO₄-Al₂O₃ (0-40 mol% Al₂O₃) are investigated. The electrical conductivity, dielectric constant and dielectric loss are increased by increasing the concentration of Al₂O₃; showing a maximum at 30 mol% Al₂O₃. The conductivity is found to be increased by decreasing the particle size of Al₂O₃. The results are explained using the random resistor network model (RRN). This is due to the formation of a highly conducting interface layer along the matrix-particle interface. This layer is destroyed at concentrations higher than 30 mol% Al₂O₃.     

Al Kα and Cu Kα1 excited XPS of vanadium oxide and VF3 powders: Measurement of the V 1s – KLL Auger parameters

Al Kα (hν = 1486.6 eV) excited XPS shows that powder samples of V₂O₃, V₂O₅ and VF₃ are surface contaminated and that the V₂O₃ can be cleaned by heating in vacuum at 400 °C. The greater sampling depth of Cu Kα₁ (hν = 8047.8 eV) excited XPS allows measurement of the bulk V 1s – KL₂L₃ Auger parameters (APs) for these materials. The APs of VF₃ and V₂O₅, relative to V metal, fall into the range of values expected for metal fluorides and oxides with non-local final state core-hole screening, whereas the AP of V₂O₃ is significantly closer to that of V metal. We ascribe this to a greater final state valence orbital occupation following photionisation in V₂O₃, part of which results from metal-like screening.     

Magnetic and structural properties of CaO–SiO2–P2O5–Na2O–Fe2O3 glass ceramics

Magnetic properties of glass ceramics derived from glasses with composition 41CaO·(52−x)SiO₂·4P₂O₅·xFe₂O₃·3Na₂O (2?x?10 mol% iron oxide (Fe₂O₃)) are reported. Structural investigation revealed the presence of nanocrystalline magnetite phase in the heat-treated samples containing x?2 mol% Fe₂O₃. Magnetic hysteresis cycles of the glass-ceramic samples were obtained with a maximum applied field of ±20 kOe as well as a low field of ±500 Oe, in order to evaluate the potential of these glass ceramics for hyperthermia treatment of cancer. Samples with x>2 mol% of iron oxide exhibited magnetic behavior similar to soft magnetic materials with low coercivity. The evolution of magnetic properties in these samples as a function of iron oxide molar concentration is correlated with the amount and crystallite size of magnetite phase present in them.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

Structural, electrical and magnetic characterizations of Ni-Cu-Zn ferrite synthesized by citrate precursor method

Fine powders of NiCuZn ferrite with composition Ni_(0.7−x)Cu_xZn_0.3Fe₂O₄ (where x=0, 0.2, 0.4 and 0.6) were prepared by the citrate precursor method. X-ray diffraction measurements confirm the formation of single-phase cubic spinel structure. The grain size was estimated by SEM micrograph which increases with Cu content. Dielectric constant (?) and loss tangent (tan δ) were measured as a function of frequency. The ? and tan δ show a decreasing trend with increase of frequency for all the samples. The DC resistivity was measured as a function of temperature. The temperature-dependent DC resistivity measurements show that the room-temperature DC resistivity of NiCuZn ferrite with x=0.2 is of the order of 10⁹ Ω cm. The AC conductivity (σ_AC) was studied as a function of frequency. The hysteresis data indicate that the maximum saturation magnetization of 38.66 emu/g is obtained for the composition with x=0.2.     

Enhancement of initial permeability due to Mn substitution in polycrystalline Ni0.50−xMnxZn0.50Fe2O4

The structural and magnetic properties of Mn substituted Ni_0.50−xMn_xZn_0.50Fe₂O₄ (where x=0.00, 0.10 and 0.20) sintered at various temperatures have been investigated thoroughly. The lattice parameter, average grain size and initial permeability increase with Mn substitution. Both bulk density and initial permeability increase with increasing sintering temperature from 1250 to 1300 °C and above 1300 °C they decrease. The Ni_0.30Mn_0.20Zn_0.50Fe₂O₄ sintered at 1300 °C shows the highest relative quality factor and highest initial permeability among the studied samples. The initial permeability strongly depends on average grain size and intragranular porosity. From the magnetization as a function of applied magnetic field, M(H), it is clear that at room temperature all samples are in ferrimagnetic state. The number of Bohr magneton, n(μ_B), and Neel temperature, T_N, decrease with increasing Mn substitution. It is found that Mn substitution in Ni_0.50−xMn_xZn_0.50Fe₂O₄ (where x=0.20) decreases the Neel temperature by 25% but increases the initial permeability by 76%. Possible explanation for the observed characteristics of microstructure, initial permeability, DC magnetization and Neel temperature of the studied samples are discussed.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

Effect of Bi2O3 on EPR, optical transmission and DC conductivity of vanadyl doped alkali bismuth borate glasses

Glasses with composition xBi₂O₃·(30−x)M₂O·70B₂O₃ (M=Li, Na) containing 2 mol% V₂O₅ have been prepared over the range 0≤x≤15 (x is in mol%). The electron paramagnetic resonance spectra of VO²⁺ of these glasses have been recorded in the X-band (≈9.3 GHz) at room temperature (RT≈300 K). Spin Hamiltonian parameters, g_∥, g_⊥, A_∥, A_⊥, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. The molecular orbital coefficients, α² and γ², have been calculated by recording the optical transmission spectra. In xBi₂O₃·(30−x)Li₂O·70B₂O₃ glasses there is decrease in the tetragonality of the V⁴⁺O₆ complex for x up to 6 mol% whereas for x≥6 mol%, tetragonality increases. In xBi₂O₃·(30−x)Na₂O·70B₂O₃ glasses there is increase in the tetragonality of the V⁴⁺O₆ complex with increasing x. The 3d_xy orbit expands with increase in Bi₂O₃:M₂O ratio. Values of the theoretical optical basicity, Λ_th, have also been reported. The DC conductivity increases with increase in temperature. The order of conductivity is 10⁻⁵ ohm⁻¹ m⁻¹ at low temperature and 10⁻³ ohm⁻¹ m⁻¹ at high temperature. The DC conductivity decreases and the activation energy increases with increase in Bi₂O₃:M₂O ratio.     

Effect of Li2O and CoO-doping of CuO/Fe2O3 system on its surface and catalytic properties

Physicochemical, surface and catalytic properties of pure and doped CuO/Fe₂O₃ system were investigated using X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), nitrogen adsorption at −196 °C and CO-oxidation by O₂ at 80-220 °C using a static method. The dopants were Li₂O (2.5 mol%) and CoO (2.5 and 5 mol%). The results revealed that the increase in precalcination temperature from 400 to 600 °C and Li₂O-doping of CuO/Fe₂O₃ system enhanced CuFe₂O₄ formation. However, heating both pure and doped solids at 600 °C did not lead to complete conversion of reacting oxides into CuFe₂O₄. The promotion effect of Li₂O dopant was attributed to dissolution of some of dopant ions in the lattices of CuO and Fe₂O₃ with subsequent increase in the mobility of reacting cations. CoO-doping led also to the formation of mixed ferrite Co_xCu_1−xFe₂O₄. The doping process of the system investigated decreased to a large extent the crystallite size of unreacted portion of Fe₂O₃ in mixed solids calcined at 600 °C. This process led to a significant increase in the S_BET of the treated solids. Doping CuO/Fe₂O₃ system with either Li₂O or CoO, followed by calcination at 400 and 600 °C decreased its catalytic activity in CO-oxidation by O₂. However, the activation energy of the catalyzed reaction was not much affected by doping.     

Effect of size and synthesis route on the magnetic properties of chemically prepared nanosize ZnFe2O4

Magnetization of the ZnFe₂O₄ sample of average size 4 nm measured with SQUID in the temperature range 5–300 K shows anomalous behaviour in field cooled (FC) and zero-field-cooled (ZFC) conditions. The FC and ZFC curves measured in 50 Oe field cross each other a little before the peaks. No such anomaly is observed with samples of 6 nm particle size made with the same procedure. The characteristics of the FC and ZFC curves are very different in ZnFe₂O₄ samples of the same size (6 nm) made via two different chemical routes. The genesis of these differences are suggested to be in cationic configuration and spin disorder. Fe-extended X-ray absorption fine structure (EXAFS) studies show that there is around 80% inversion in case of zinc ferrite (ZnFe₂O₄) with the particle size 4 nm, whereas ZnFe₂O₄ of size 6 nm shows 40% inversion. The samples with an average particle size of 7 nm and more show negligible inversion. Theoretical simulations suggest that the electrostatic energy of the system plays a crucial role in deciding the cationic configuration of spinel ferrites.     

Elastic properties of lead-phosphate glasses doped with samarium trioxide

A series of ternary lead-phosphate glasses doped with samarium trioxide, xSm₂O₃-(40−x)PbO-60 P₂O₅ (where x=0.1 to 0.5 mol%) have been prepared by using conventional melt quenching method and their elastic properties have been studied at room temperature. Results from the studies show that both longitudinal and transverse sound velocities decrease by increasing the Sm₂O₃ content. Elastic moduli, Poisson's ratios decrease with increase of Sm₂O₃ composition up to 0.3 mol% and then there is a slight increasing trend observed at 0.4 mol%. The densities of these glasses have been measured by using displacement method. The variations of these parameters have been discussed with respect to samarium trioxide concentration.     

VPO catalysts synthesized on substrates with modified activated carbons

VPO catalysts were prepared on oxidized and unoxidized activated carbons differing in initial porous structure. Carbons were oxidized under relatively soft (30% H₂O₂, 200 °C) and hard (50% H₂O₂, 350 °C) conditions. Carbon modification was carried out hydrothermally in a traditional autoclave (HTT) or a microwave reactor (MWT). The synthesis was also carried out under hydrothermal (HTS or MWS) conditions. V₂O₅ and NH₄VO₃ were used as precursors. The samples are characterized by diversified porous structure at S_BET = 732-1617 m²/g and V_por = 0.44-0.90 cm³/g, as well as various degree of VPO crystallinity. Possibility of preparation of the VPO catalysts under ecologically appropriate conditions, i.e. in aqueous solutions, was shown.