Magnetic properties of Nd-Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles

Nb³⁺-substituted garnet nanoparticles Y_3−xNd_xFe₅O₁₂ (x = 0.0, 0.5, 1.0, 1.5, and 2.0) were fabricated by a sol-gel method and their crystalline structures and magnetic properties were investigated by using X-ray diffraction (XRD), thermal analysis (DTA/TG), and vibrating sample magnetometer (VSM). The XRD patterns of Y_3−xNd_xFe₅O₁₂ have only peaks of the garnet structure and the sizes of particles range from 34 to 70 nm. From the results of VSM, it is shown that when the Nd concentration x ( 1.0, the saturation magnetization of Y_3−xNd_xFe₅O₁₂ increases as the Nd concentration (x) is increased, and gets its maximum at x = 1.0, but when x ( 1.0, the saturation magnetization decreases with increasing the Nd concentration (x), this may be due to the distortion of the microstructure of Y_3−xNd_xFe₅O₁₂, which leads to the decrease of the effective moment formed by Fe³⁺. Meanwhile, it is observed that with the enhancement of the surface spin effects, the saturation magnetization rises as the particle size is increased.     

The synthesis and the magnetic properties of Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BiY<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>5</Subscript>O<Subscript>12 </Subscript>nanoparticles

Sm _x BiY_2–x Fe₅O₁₂ (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8) nanocrystals were fabricated by sol–gel method. Samples were characterized by powder X-ray diffraction (XRD), thermal gravity analysis (TGA) and differential thermal analysis (DTA), transmission electron microscopy (TEM), vibrating sample magnetometer(VSM). The samples were calcined at 850 °C and 1000 °C and the average size of the particles were determined by Scherrer’s formula . In this paper, we discussed the effect of Sm³⁺ substitution for Y³⁺ on magnetic properties of BiY₂Fe₅O₁₂. The magnetic properties of Sm _x BiY_2−x Fe₅O₁₂ are decreased with increasing content of Sm ion.     

Unusual magnetic and transport properties of the CMR Pr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3−<Emphasis Type="Italic">y</Emphasis></Subscript> system

The substituted nonstoichiometric perovskite Pr_1−x Ca _x MnO_3−y compounds have been synthesized by a standard combustion technique, which show uniphase solid solutions. The all samples of the Pr_1−x Ca _x MnO_3−y system show an orthorhombic crystal system and the cell volumes are decreased with increasing the larger amounts of substituted atoms or the increasing x values. The mixed valence of Mn ions is identified by the XAS (XANES/EXAFS) spectroscopy and the amounts of Mn⁴⁺ ions are determined by an iodometric titration method. Nonstoichiometric chemical formulas of the Pr_1−x Ca _x Mn_1−τ³⁺Mn_τ⁴⁺O_3−y compounds have been obviously formulated. Magnetic properties are investigated by SQUID and thus the Pr_1−x Ca _x MnO_3−y (x = 0.4, 0.6, and 0.8) compounds show the transition from antiferromagnetic state to paramagnetic state. The Pr_1−x Ca _x MnO_3−y (x = 0.0, 0.2, and 1.0) compounds show the transition from ferromagnetic state to paramagnetic state. The facts that Mn⁴⁺ contents play important roles in the magnetic ordering have been found out. The transport properties have been studied by the DC electrical conductivity measurement under magnetic fields of 0 G and 3 kG. Maximum and minimum MR ratios are 1016% of the Pr_0.6Ca_0.4MnO_2.846, and −77.5% of the PrMnO_3.021 compound, respectively.     

Study of structure and properties of ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the ternary system ZnO–Bi₂O₃–P₂O₅ were prepared and studied in two compositional series 50ZnO–xBi₂O₃–(50 − x)P₂O₅ and (50 − y)ZnO–yBi₂O₃–50P₂O₅. Two distinct glass-forming regions were found in the 50ZnO–xBi₂O₃–(50 − x)P₂O₅ glass series with x = 0–10 and 20–35 mol.% Bi₂O₃. All prepared Bi₂O₃-containing glasses reveal a high chemical durability. Small additions of Bi₂O₃ (∼5 mol.%) improve thermal stability of glasses. All glasses crystallize on heating within the temperature range of 505–583 °C. Structural studies by Raman and ³¹P MAS NMR spectroscopies showed the rapid depolymerisation of phosphate chains within the first region with x = 0–15 and the presence of isolated Q⁰ phosphate units within the second region with x = 20–35. Raman studies showed that bismuth is incorporated in the glass structure in BiO₆ units and their vibrational bands were observed within the spectral region of 350–700 cm⁻¹. The evolution of properties and the spectroscopic data are both in accordance with a network former effect of Bi₂O₃.     

Electrical properties of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses exhibiting majority charge carrier reversal

The thermoelectric power and d.c electrical conductivity of x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses were measured. The Seebeck coefficient (Q) varied from +88 μ V K⁻¹ to −93 μV K⁻¹ as a function of V₂O₅ mol%. Glasses with 10 and 15 mol% V₂O₅ exhibited p-type conduction and glasses with 25 and 30 mol% V₂O₅ exhibited n-type conduction. The majority charge carrier reversal occurred at x = 20 mol% V₂O₅. The variation of Q was interpreted in terms of the variation in vanadium ion ratio (V^{5 +}/V^{4 +}). d.c electrical conduction in x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses was studied in the temperature range of 150 to 480 K. All the glass compositions exhibited a cross over from small polaron hopping (SPH) to variable range hopping (VRH) conduction mechanism. Mott parameter analysis of the low temperature data gave values for the density of states at Fermi level N (E_F) between 1.7 × 10²⁶ and 3.9 × 10²⁶ m⁻³ eV⁻¹ at 230 K and hopping distance for VRH (R_VRH) between 3.8 × 10⁻⁹m to 3.4 × 10⁻⁹ m. The disorder energy was found to vary between 0.02 and 0.03 eV. N (E_F) and R_VRH exhibit an interesting composition dependence.     

Magnetic and Superconducting Properties of Doped and Undoped Double Perovskite Sr<Subscript>2</Subscript>YRuO<Subscript>6</Subscript>

We report here SQUID (magnetization) measurements, along with supporting specific heat, Raman, SEM (scanning electron microscope), EDX (energy dispersive X-ray) and XRD (X-ray diffraction) measurements, on Cu-doped and undoped double perovskite Sr₂²⁺Y³⁺Ru⁵⁺O₆^2-\mathrm{Sr}_{2}^{2+}\mathrm{Y}^{3+}\mathrm{Ru}^{5+}\mathrm{O}_{6}^{2-} (abbreviated as SrY2116) system grown as single crystal using high-temperature solution growth technique. These measurements show the undoped system to be a nonmetallic (insulating) spin glass (SG) and the ∼5–30% Cu-doped (i.e. Cu-concentration/(Cu + Ru-concentration) ∼5–30%) system to be a spin glass superconductor (SGSC) with T _c (critical temperature) ∼28–31 K and superconducting volume fraction, f _sc∼2.2–9%. To mention, similar measurements done on undoped and Cu-doped BaY2116 and BaPr2116 systems show for them the same (SG, SGSC) behaviors. However they show a decrease in T _c and f _sc when diamagnetic Y³⁺ ions are replaced by Pr³⁺ spins, presumably due to enhanced internal pair breaking, and also decreased Cu–O–Cu overlap, owing to Pr³⁺ presence; these phenomena are known to exist in the Pr123 compound, PrBa₂Cu₃O_7−δ (δ∼0), due to ∼10% of Pr³⁺ ions having tendency to occupy Ba²⁺ sites. Measurements done on undoped and Cu-doped SrHo2116 show similar SG and SGSC properties. Further, the undoped and Cu-doped SrY2116 crystals grown by hydrothermal growth technique (i.e., grown using lower temperature and high pressure) show same behaviors. From these investigations it can be said that the undoped Ru-double perovskites (A₂BB′O₆, B′=Ru) are SG systems and that Cu-doped Ru-double perovskites (A₂BB′O _δ , δ∼6, B′=Ru_1−x Cu _x , 0<x≲0.3) are SG superconductors (SGSCs). Results are discussed.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

A study on electrodeposited Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

Zn_1−x Fe _x alloys were electrochemically deposited on AISI 4140 steel substrates from sulfate bath. The bath was consisted of 40 g dm⁻³ ZnSO₄·7H₂O, 20–40 g dm⁻³ FeSO₄·7H₂O_, 25 g dm⁻³ Na₃C₆H₅O₇, and 16 g dm⁻³ H₃BO_3. The effect of bath composition on the electrical resistivity, the phase structure, and the corrosion behavior were investigated by the current–voltage measurements versus temperature, the X-ray diffraction (XRD) analysis, the atomic absorption spectrometry analysis, and the polarization measurements, respectively. Iron content was shown to strongly affect the structure, the electrical resistivity and the corrosion stability of Zn–Fe alloys.     

Sol–gel synthesis of Ce-substituted BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>

Ce-substituted BaFe₁₂O₁₉ (BaCe _x Fe_12−x O₁₉, x = 0, 0.01, 0.03, 0.05) was prepared by citrate sol–gel method. The thermal decomposition process of precursor was investigated by TG-DSC. The phase composition of the BaCe _x Fe_12−x O₁₉ was characterized by X-ray powder diffraction analysis (XRD) which reveals that the BaCe _x Fe_12−x O₁₉ crystallizes in a hexagonal structure. The lattice parameter of BaCe _x Fe_12−x O₁₉ increases slightly when Ce was substituted into BaFe₁₂O₁₉. The average crystallite size calculated from the XRD line broadening is about 30–33 nm and no intermediate phases are detected in the XRD patterns. The transmission electron microscope (TEM) analysis indicates that the particles of samples obtained are the rod-like morphology.     

Structural changes induced by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> addition in strontium-borate glass matrix

Glasses of the xFe₂O₃·(100−x)[B₂O₃·SrO] system, with 0 ≤ x ≤ 30 mol% were studied by X-ray diffraction, density, optical microscopy and FT-IR spectroscopy measurements. The X-ray patterns for the prepared system show that vitreous phase is present only in the sample with x < 40 mol%. For x ≥ 40 mol% in the studied samples is evidenced crystalline phase of Fe₂O₃. SEM measurements for the sample with x = 40 mol% shows that there are formed Fe₂O₃ microcrystallites with 10–20 μm dimension. FT-IR spectroscopy measurements shown that BO₃ and BO₄ are the main structural units of the glass system and the iron ions are located in the glass network.     

Synthesis and photoluminescence properties of LiEu(W,Mo)<Subscript>2</Subscript>O<Subscript>8</Subscript>:Bi<Superscript>3+</Superscript> red-emitting phosphor for white-LEDs

LiEu_1−x (W_2−y Mo _y )O₈:xBi³⁺ series red-emitting phosphors were synthesized by solid state reaction. The structure, morphology, and photoluminescent properties of phosphors were studied by X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectrum, respectively. X-ray powder diffraction analysis showed that the as-obtained phosphors belong to the scheelite structure. The average particle size of the investigated phosphor was about 8 μm. The excitation spectrum exhibits a charge-transfer broad band along with some sharp peaks from the typical 4f–4f transitions of Eu³⁺. Under excitation of UV, near-UV, or blue light, these phosphors showed strong red emission at 615 nm due to ⁵D₀–⁷F₂ transition of Eu³⁺. The incorporation of Mo⁶⁺ into LiEuW₂O₈:Bi³⁺ could induce red-shift of the charge-transfer broad band and a remarkable increase of photoluminescence. The highest red-emission intensity was observed with LiEu_0.80Mo₂O₈:0.20Bi³⁺. Compared with the commercial red-emitting phosphor, Y₂O₂S:Eu³⁺, the emission intensity of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor is much stronger than that of Y₂O₂S:Eu³⁺ and its chromaticity coordinates are closer to the standard values than that of the commercial phosphor. The optical properties of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor make it attractive for the application in white-light-emitting diodes (LEDs), in particular for near-UV InGaN-based white-LEDs.     

Electrical properties of perovskite-like compounds in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> system

The electrical properties of layered perovskite-like compounds with the general formula Bi _{m + 1}Fe _{m − 3}Ti₃O_{3m + 3} have been studied in relation to their physicochemical properties and structure.     

Properties of Mg(Fe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>O<Subscript>4 + δ</Subscript> solid solutions in stable and metastable states

Using pyrohydrolytic synthesis, we have obtained a continuous series of Mg(Fe_{1 − x} Ga _x )₂O_{4 + δ} solid solutions, as checked by X-ray diffraction. The magnetization and coercivity of the samples have been determined from field dependences in applied magnetic fields of ±5 T, and their conductivity has been assessed using current-voltage measurements at 300 K in electric fields from −200 to +200 V. The effective band gap of the solid solutions has been evaluated from their absorption spectra obtained by diffuse reflectance measurements. The optimal composition for spintronic applications is Mg(Fe_0.8Ga_0.2)₂O_{4 + δ}.     

Effect of secondary heat treatment on the spectroscopic properties of Na<Subscript>2</Subscript>O-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

We have studied the optical absorption and luminescence spectra of 45Na₂O · xNb₂O₅ · (55 − x)P₂O₅ glasses containing 5, 10, 20, 25, 30, and 35 mol % Nb₂O₅. The results indicate that the absorption band around 26000 cm⁻¹, responsible for the yellow color of the glasses, is due to the [Nb^(5+)--O⁻] center and disappears upon secondary heat treatment. Heat treatment of europium-doped glasses increases the concentration of Eu³⁺ centers in an asymmetric environment, which is accompanied by an increase in luminescence efficiency. The reason for this is that the Eu³⁺ ions are located outside the niobate subsystem of the glass matrix. The europium in the glasses studied acts as a protector ion.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Effect of combined doping (y<Superscript>3 +</Superscript> + fe<Superscript>3 +</Superscript>) on structural features of nanodispersed zirconium oxide

Fully stabilized zirconium dioxide is widely used. One of the basic requirements to this material is the thermal stability of the structure. The most effective stabilizer for zirconium oxide is yttrium oxide. However, the structure of Y-ZrO₂ degraded at low temperature. Partial substitution of Fe^{3 +} for Y³⁺ decreases both the crystallization and sintering temperature of zirconia ceramic. The aim of present work is the investigation of structural peculiarities of zirconium oxide stabilized by combined dopant depending on chemical composition, synthesis conditions and heat treatment. The polymorphic composition of a ZrO₂-based materials has been determined in series of samples that correspond to the formula [1−(x+y)]ZrO₂⋅xY₂O₃⋅yFe₂O₃ in the temperature range 620–1570 K. It has been found that at the same molar ratio ZrO₂ : doping oxides, the degree of ZrO₂ stabilization increases, and the low-temperature degradation process is retarded by the partial substitution of Fe^{3 +} for Y³⁺. Nonequivalent sites of Fe^{3 +} ions have been identified: two with octahedral coordination for CPH and three with octa-, penta- and tetrahedral coordination for SPH. The possibility of cluster distribution of Fe³⁺ ions and the dependence of the number of vacancies on synthesis conditions have been shown.     

Spectroscopic studies of TeO<Subscript>2</Subscript>–ZnO–Er<Subscript>2</Subscript>O<Subscript>3</Subscript> glass system

Series of glass based on the (80 − x)TeO₂–20ZnO–(x)Er₂O₃ system (0.5 mol% ≤ x ≤ 2.5 mol%) has successfully been made by melt quenching technique. The optical properties of glass have been investigated by means of IR and Raman spectroscopy. It is observed that as the Er₂O₃ content is being increased, the sharp IR absorption peaks are consistently shifted from 650 to 672 cm⁻¹ while the Raman shift intensity around 640–670 cm⁻¹ is decreases but increases around 720–740 cm⁻¹. It is found out that both phenomenons are related to the structural changes between the stretching vibration mode of TeO₄ tbp and TeO₃ tp, and bending vibration mode of Te–O bonds in the glass linkages.     

Nano-domain structure of Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript> spinel

XRD-pure Li₄Mn₅O₁₂ spinels are obtained below 600 °C from oxalate and acetate precursors. The morphology consists of nanometric particles (about 25 nm) with a narrow particle size distribution. HRTEM and electron paramagnetic resonance (EPR) spectroscopy of Mn⁴⁺ are employed for local structure analysis. The HRTEM images recorded on nano-domains in Li₄Mn₅O₁₂ reveal its complex structure. HRTEM shows one-dimensional structure images, which are compatible with the (111) plane of the cubic spinel structure and the (001) plane of monoclinic Li₂MnO₃. For Li₄Mn₅O₁₂ compositions annealed between 400 and 800 °C, EPR spectroscopy shows the appearance of two types of Mn⁴⁺ ions having different metal environments: (i) Mn⁴⁺ ions surrounded by Li⁺ and Mn⁴⁺ and (ii) Mn⁴⁺ ions in Mn⁴⁺-rich environment. The composition of the Li⁺, Mn⁴⁺-shell around Mn⁴⁺ mimics the local environment of Mn⁴⁺ in monoclinic Li₂MnO₃, while the Mn⁴⁺-rich environment is related with that of the spinel phase. The structure of XRD-pure Li₄Mn₅O₁₂ comprises nano-domains with a Li₂MnO₃-like and a Li_4/3−x Mn_5/3+x O₄ composition rather than a single spinel phase with Li in tetrahedral and Li_1/3Mn_5/3 in octahedral spinel sites. The annealing of Li₄Mn₅O₁₂ at temperature higher than 600 °C leads to its decomposition into monoclinic Li₂MnO₃ and spinel Li_4/3−x Mn_5/3+x O₄.     

Modifying the oxygen adsorption properties of YBaCo<Subscript>4</Subscript>O<Subscript>7</Subscript> by Ca,Al, and Fe doping

The doping effect of Ca, Al, and Fe on the oxygen adsorption properties of YBaCo₄O₇ was investigated by thermogravimetry (TG) method. It was found that the original YBaCo₄O₇ oxygen adsorption properties can be modified greatly by Ca, Al, and Fe doping. Ca doping in Y sites eliminates the oxygen adsorption at low temperature (~300 °C) but the oxygen adsorption properties at high temperature is almost unchanged. Minor Al doping in Co sites eliminates the oxygen adsorption hump at high temperature, but the hump at low temperature is preserved. Fe appearance in YBaCo₃Al_1−x Fe _x O₇ seems to weaken the effect of Al doping, so the oxygen hump at high temperature emerges again. The doping effect was discussed based on elements valence, binding energy between cations and oxygen ions, and distortion of crystal structure.     

Synthesis and structural studies of Na<Subscript>2</Subscript>O-ZnO-ZnF<Subscript>2</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> oxyfluoride glasses

This paper describes the synthesis and spectroscopic studies of the glass system, 20Na₂O-(20-x) ZnO-xZnF₂-60B₂O₃(x = 0, 5, 10, 15, 20), prepared by melt quenching method. The analyses of DSC and XRD did not show the crystallinity of the glass sample. ¹¹B MAS-NMR shows the presence of sharp peak around −14 ppm. From the IR studies, the broadening of the peak around 1200–1400 and 800–1100 cm⁻¹ shows the presence of mixed linkages like B-O-B, B-O-Zn in the network.