Electric-field effect on crystal growth in the Li<Subscript>3</Subscript>PO<Subscript>4</Subscript>-Li<Subscript>4</Subscript>GeO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-LiF system

We have studied the electric-field effect on crystallization processes in the Li₃PO₄-Li₄GeO₄-Li₂MoO₄-LiF system. In zero field, Li_3+x P_1?x Ge _x O₄ (x = 0.31) crystals were grown on the cathode under the conditions of this study. At low applied voltages (≤ 0.5 V), we obtained Li₂MoO₄, Li₂GeO₃, and Li_1.3Mo₃O₈. In the range V = 0.5–1 V, crystals of Li_3+x P_1?x Ge _x O₄ solid solutions with x = 0.17, 0.25, 0.28, 0.29, and 0.36 were obtained. An applied electric field was shown to reduce the melting temperature of the starting mixtures and the crystallization onset temperature.     

Effect of Al Substitution in Structural and Magnetic Properties of MnCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single-phase samples of Mn(Cr_1?x Al _x )₂O₄ (x = 0 – 0.30) with cubic spinel structure were prepared and the lattice constant is found to decrease from a = 8.4396 Å for x = 0 to a = 8.3801 Å for x = 0.30. The substitution of Al at Cr site is confirmed from the blue shift of Raman modes. Magnetization measurements and analysis show all the prepared samples exhibit ferrimagnetic transition with transition temperature in the range of 46 K for x = 0 to 33 K for x = 0.30. The saturation magnetization (M _s ) and the estimated anisotropy constant (K) show an anomalous behavior up to x = 0.10 and beyond that they decrease monotonously. They are explained by considering different site preferences of Al ³⁺ ions as the doping concentration is increased. The theoretical and experimental effective magnetic moment of the samples is found to be comparable and it decreases with increase in Al concentration.     

The magnetic properties of BiY<Subscript>2</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles doped with Cr ions

BiY₂Cr _x Fe_5?x O₁₂ (x = 0, 0.05, 0.1, 0.2, 0.3) nanocrystals were synthesized by using a sol-gel method. Samples were characterized by the powder X-ray diffraction (XRD), the thermal gravity analysis (TGA) and the differential thermal analysis (DTA), the vibrating sample magnetometer(VSM) and Mössbauer spectrums. The average sizes of the particles were determined by the Scherrer’s formula. The special Ms and Mössbauer spectra of BiY₂Cr _x Fe_5?x O₁₂ nanocrystals are researched at room temperature. It is seen that the special Mss of samples are initially increased with increasing Cr³⁺ content (x < 0.1), and decreased with increasing content of Cr³⁺ ions (x > 0.1).     

Study of Magnetic Entropy Change in Nd<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> by Means of Theoretical Models

Magnetic entropy change (?ΔS _M ) of Nd_0.67 Ba_0.33Mn_0.98Fe_0.02O₃ perovskite have been analyzed by means of theoretical models. An excellent agreement has been found between the (ΔS_M) values estimated by Landau theory and those obtained using the classical Maxwell relation. In order to estimate the spontaneous magnetization M _{s pont}(T), we used the mean-field theory to analyses the (ΔS_M) vs. M ² data. The obtained M _{s pont}(T) values are in good agreement with those found from the classical extrapolation from the Arrott plots(H/M vs. M ²), confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in our system. At a relatively low magnetic field, a phenomenological model has been used to estimate the values of the magnetic entropy change. The results are in good agreement with those obtained from the experimental data using Maxwell relation.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.     

Growth and properties of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript>-NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

Platelike Li_{1 ? x} Na _x Cu₂O₂ single crystals up to 2 × 10 × 10 mm in dimensions have been grown by slowly cooling (1 ? x)Li₂CO₃·xNa₂O₂·4CuO melts in alundum crucibles in air. Li_{1 ? x} Na _x Cu₂O₂ solid solutions in the LiCu₂O₂-NaCu₂O₂ system have been shown to exist in the composition range 0.78 < x < 1. The temperature stability ranges of NaCu₂O₂ and LiCu₂O₂ are 780–930 and 890–1050°C, respectively. The Mössbauer spectra and electrical conductivity of the crystals have been measured.     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

Effect of Ni Doping at Pd Site in Nb<Subscript>2</Subscript>PdS<Subscript>5</Subscript> Superconductor

The superconducting properties of Nb₂PdS₅ superconductor have been investigated with Ni doping at Pd site All the bulk polycrystalline Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.10) samples are crystallized in singlephase monoclinic structure. The electrical resistivity and magnetic measurements of Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.15) were carried out to study the variation of superconducting critical parameters with Ni doping. Superconductivity in Nb₂PdS₅ sample completely disappears for x ≥ 0.15. We observed that the ratio of upper critical field to transition temperature decreases with increasing Ni concentration. Also, the magnetization study of Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.15) samples shows similar superconducting behaviour. In summary, the superconductivity in Nb₂PdS₅ sample is slightly varying with partial doping of Ni at Pd site in Nb₂PdS₅ superconductor.     

Synthesis,structure, and magnetic properties of rare-earth-doped Ni<Subscript>0.75</Subscript>Zn<Subscript>0.25</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nickel zinc ferrite

We have developed processes for the synthesis of Ni_0.75Zn_0.25Fe_2–xLn_xO₄ ferrite solid solutions with the spinel structure and investigated the effect of the rare-earth elements Nd, Gd, Yb, and Lu on the chemical composition, extent, lattice parameters, and magnetic properties of the solid solutions. The results demonstrate that rare-earth solubility in the parent spinel reaches ≈2.5 at %, which leads to changes in the magnetic characteristics of the material, in particular in its saturation magnetization M_s, T_C, and coercive force H_c.     

Phase Diagrams of the Systems CuBiS<Subscript>2</Subscript>-LnBiS<Subscript>3</Subscript> (Ln = La,Nd)

Phase relations in the CuBiS₂-LaBiS₃ and CuBiS₂-NdBiS₃ systems were studied for the first time using physicochemical analysis, and the T-x phase diagrams of these systems were constructed. Both systems contain quaternary compounds with the Cu₂LnBi₃S₇ stoichiometry, which melt incongruently at 815 and 910 K, respectively. Cu₂LaBi₃S₇ and Cu₂NdBi₃S₇ are isostructural with one another and crystallize in orthorhombic symmetry. The lattice parameters of Cu₂LaBi₃S₇ are a = 14.66 Å, b = 21.60 Å, and c = 4.12 Å, and those of Cu₂NdBi₃S₇ are a = 14.60 Å, b = 21.56 Å, and c = 4.10 Å.     

Crystallization from high-temperature solutions in the K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied general trends of crystallization from high-temperature solutions in the K₂O-P₂O₅-V₂O₅-Bi₂O₃ system at P/V = 0.5?2.0, K/(P + V) = 0.7?1.4, and Bi₂O₃ contents from 25 to 50 wt % and identified the stability regions of BiPO₄, K₃Bi₅(PO₄)₆, K₂Bi₃O(PO₄)₃, and K₃Bi₂(PO₄)_{3 ? x} (VO₄) _x (x = 0?3) solid solutions. The synthesized compounds have been characterized by X-ray powder diffraction and IR spectroscopy, and the structure of two solid solutions has been determined by single-crystal X-ray diffraction (sp. gr. C ₂/c): K₃Bi₂(PO₄)₂(VO₄), a = 13.8857(8), b = 13.5432(5), c = 6.8679(4) Å, β = 114.031(7)°; K₃Bi₂(PO₄)_1.25(VO₄)_1.75, a = 13.907(4), b = 13.615(2), c = 6.956(2) Å, β = 113.52(4)°.     

A catalyst-free new polyol method synthesized hot-pressed Cu-doped Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanorods and their thermoelectric properties

This is the first report on the thermoelectric properties of a catalyst-free polyol method used to prepare stoichiometric Bi_2?x Cu _x S₃ samples, x = 0.1, 0.2, 0.3, 0.4, via hot pressing. Various systematic approaches to arrive at in their stoichiometric compositions are explored precisely with introduction of excess precursor of S. X-ray diffraction data analysis using Rietveld refinement confirms a polyhedral orthorhombic crystal structure with a space group Pnma, in contrast to Pbnm reported earlier. Raman data further substantiates this. X-ray photoelectron spectroscopy confirms the valence states of the constituent elements (Bi³⁺, Cu²⁺, and S^2?) and energy dispersive X-ray analysis corroborates their compositions. The particle sizes of the pure Bi₂S₃ nanoparticles were 20, 35, and 82 nm as determined from the Scherrer formula, atomic force microscopy, and dynamic light scattering, respectively. Their transmission electron microscopy image shows rod-like nanostructures elongated in the 〈010〉 direction with an average diameter of 23 nm and a length of several hundreds of nanometers. A 34% improvement in the thermoelectric figure of merit is observed for Bi_1.6Cu_0.4S₃ as compared to pure Bi₂S₃ at 300 K.

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Solid-state reactions in the system Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

The formation mechanisms of Li _x Na_{1 ?x} Ta _y Nb_{1 ? y} O₃ perovskite solid solutions in the Li₂CO₃-Na₂CO₃-Nb₂O₅-Ta₂O₅ system have been studied by x-ray diffraction, differential thermal analysis, thermogravimetry, IR spectroscopy, and mass spectrometry at temperatures from 300 to 1100°C. The results indicate that the synthesis of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions involves a complex sequence of consecutive and parallel solid-state reactions. An optimized synthesis procedure for Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions is proposed.     

Giant Magnetoresistance in Topological Insulator Bi<Subscript>1.98</Subscript>Nd<Subscript>0.02</Subscript>Se<Subscript>3</Subscript> Single Crystal

Doped topological insulators (TI) Bi_2?x Nd _x Se₃ single crystals were prepared by the self-flux method. The phase structure, magnetic properties, and electrical transport properties of the samples were studied. The X-ray diffraction (XRD) patterns of the sample indicate an incorporation of Nd into the Bi₂Se₃, and the crystal can be easily cleaved with silvery surface. The Bi_2?x Nd _x Se₃ sample shows a giant magnetoresistance (MR) with different magnetic field. The positive magnetoresistance (MR) can reach 190 % at the field of 9 Tesla when the field is perpendicular to ab-plane of the crystal. In addition, at low magnetic fields, the MR exhibits a weak antilocalization (WAL) cusp.     

Growth and magnetic properties of spin coated Co<Subscript>0.6</Subscript>Zn<Subscript>0.4</Subscript>Mn<Subscript>0.3</Subscript>Fe<Subscript>1.7</Subscript>O<Subscript>4</Subscript> ultrathin films on silicon (100), (110) and (111) substrates

This paper reports growth of Co_0.6Zn_0.4Mn_0.3Fe_1.7O₄ (CZFMO) ultrathin films (thickness: 23–30 nm) by spin coating technique on silicon (100), (110) and (111) substrates. The deposited films were annealed at 700 °C for 1 h in the oxygen environment. All the films were found to be polycrystalline in nature. The CZFMO films were found to have minimal residual stress (13–50 MPa), which could be an encouraging feature for novel microwave miniaturized device applications. Room temperature magnetic measurements demonstrated completely saturated hysteresis loop with the highest squareness ratio (M _R /M _S )?~?60% for the film grown on Si (110) substrate. On the other hand CZFMO films on Si (100) and Si (111) substrates showed unsaturated hysteresis loops with M _R /M _S ~ 10 and 5%, respectively. The reason for the better magnetic properties of the ultrathin CZFMO film on Si (110) substrate seems to be its better crystalline quality and larger grain size compared to those of other films.     

Effect of Zr Addition on Bi<Subscript>1.8</Subscript>Pb<Subscript>0.4</Subscript>Sr<Subscript>2.0</Subscript>Ca<Subscript>1.1</Subscript>Cu<Subscript>2.1</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Superconductor

The polycrystalline Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1 M_xO _y , with M = Zr (x = 0.0, 0.02, 0.04), were synthesized by solid-state reaction method and studied by X-ray diffraction analysis (XRD), scanning electron microscopy equipped with energy dispersive of X-ray analysis (SEM/EDX) and resistivity versus temperature measurements. The influence of the Zr addition on the Tc and microstructure properties of the superconducting compounds has been studied. SEM observations show whiskers grains randomly distributed and microstructural change due to the addition of Zr. The ZrO₂ was incorporated into the crystalline structure of BSCCO system in all samples. The crystallographic structure remains in a tetragonal form where a= b≠c. Generally, all samples exhibit semiconductor behaviour above \(T_{\mathrm {c}}^{\text {onset}}\). The onset critical temperature \(T_{\mathrm {c}}^{\text {onset}}\) increases up to 86 with x = 0.02. There is an enhancement in the critical temperature for doped samples as compared with pure Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1O _y .Changes in superconducting properties of ZrO₂ nanoparticle added Bi-2212 system were discussed.     

Comparative Magnetic and Structural Properties Study of Micro- and Nanopowders of Nd<Subscript>2</Subscript>Fe<Subscript>14</Subscript>B Doped with Ni

Micropowders of melted and heat-treated Nd₁₆(Fe_76?x Ni _x )B₈ alloys system, with x = 0, 10, 20, and 25 (size distribution under 20 μm), were studied and compared with the study of nanopowders obtained, from the previous ones, by surfactant-assisted ball-milling process during 2 h. By XRD, a majority of Nd₂Fe₁₄B hard phase and a minority of α-Fe, Nd_1.1Fe₄B₄ and NdNi₂ phases were detected. The last one increases with Ni content. The crystallite size of the hard phase, in both types of samples, is not affected by the Ni content; however, the grains in micropowders are oblate, with a mean size of 37 nm, while those of the nanopowders are symmetric, with a mean size of 35 nm. Mössbauer spectra were fitted with seven sextets, which correspond to the six ferromagnetic sites of the hard phase and that of the α-Fe, and a doublet corresponding to the paramagnetic Nd_1.1Fe₄B₄ phase. The mean hyperfine magnetic field, for both types of samples, decreases with Ni content. The hysteresis loops of both types of samples show a hard magnetic character, however, the coercive field and the M _r/M _s values for nanopowders are greater than those obtained for micropowders for all the Ni contents. Values of H _c = 2 kOe and M _r/ M _s = 0.54 were obtained for nanopowders with 10 at.% Ni. From the hysteresis loops, which include the initial magnetization curve, Henkel plots for all the samples were obtained. These plots show that for micropowders, the predominant magnetic interaction is of dipolar type, while for nanopowders, the ferromagnetic exchange is the predominant one, which favored the magnetization.     

Magnetic properties of LaInO<Subscript>3</Subscript>-based perovskite-structure photoluminescent materials doped with Nd<Superscript>3+</Superscript>, Cr<Superscript>3+</Superscript>, and Mn<Superscript>3+</Superscript> ions

Single-phase ceramic samples of La_1–xNd_xInO₃ (0.007 ≤ x ≤ 0.05), LaIn_0.99M_0.01O₃, and La_0.95Nd_0.05In_0.995M_0.005O₃ (M = Cr³⁺ and Mn³⁺) solid solutions have been prepared by solid-state reactions, and their crystal structure, magnetic field dependences of their specific magnetization at 5 and 300 K, and temperature dependences of their molar magnetic susceptibility have been studied. It has been shown that the 300-K specific magnetization of the La_1–xNd_xInO₃ (x = 0.02, 0.05), La_0.95Nd_0.05In_0.995M_0.005O₃ (M = Cr³⁺ and Mn³⁺), and LaIn_0.99Mn_0.01O₃ solid solutions increases linearly with increasing magnetic field strength up to 14 T and that the magnitude of the 300-K specific magnetization of the La_0.993Nd_0.007InO₃ and LaIn_0.99Cr_0.01O₃ solid solutions increases linearly, but they have diamagnetic magnetization. At a temperature of 5 K, the magnetization of all the indates studied here increases nonlinearly with increasing magnetic field strength, gradually approaching magnetic saturation, without, however, reaching it in a magnetic field of 14 T. In the temperature range where the Curie–Weiss law is obeyed (5–30 K), the effective magnetic moments obtained for the Nd³⁺ ion (\({\mu _{effN{d^{3 + }}}}\)) in the La_1–xNd_xInO₃ solid solutions with x = 0.007, 0.02, and 0.05 are 2.95μ_B, 3.09μ_B, and 2.75μ_B, respectively, which is well below the theoretical value \({\mu _{effN{d^{3 + }}}}\)= 3.62μ_B. The effective magnetic moments of the Cr³⁺ and Mn³⁺ ions in the LaIn_0.99Cr_0.01O₃ and LaIn_0.99Mn_0.01O₃ solid solutions are 3.87μ^B and 5.11μ^B, respectively, and differ only slightly from the theoretical values \({\mu _{effC{r^{3 + }}}}\)= 3.87μ^B and \({\mu _{effM{n^{3 + }}}}\)= 4.9μ^B.     

Tuning of Dielectric Parameters of (NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/CuTl-1223 Nano-superconductor Composites by Temperature and Frequency

Nickel ferrite (NiFe₂O₄) nanoparticles and Cu_0.5Tl_0.5Ba₂Ca₂Cu₃O_10?δ (CuTl-1223) superconductor were prepared separately and then mixed in an appropriate ratios at the final stage to obtain (NiFe₂O₄) _x /CuTl-1223 (x = 0, 0.5, and 1.0 wt%) nano-superconductor composites. There was no significant change observed in crystal structure of the host CuTl-1223 superconducting matrix after the addition of NiFe₂O₄ nanoparticles. The value of zero-resistivity critical temperature { T _{c(R = 0)} (K)} was decreased with increasing content of these nanoparticles in these composites. Maximum values of dielectric loss tangent (tanδ) at lowest possible frequency of 40 Hz were increased with the increase of operating temperature, while its values were decreased and become almost zero at higher frequencies for all these samples at all operating temperatures. A peak in dielectric loss tangent was shifted towards lower frequency values with the addition of these nanoparticles in CuTl-1223 superconducting matrix. The dielectric loss tangent peak was also shifted towards lower frequency values in all these samples with increasing operating temperature, which shows the relaxator-like behavior in these samples. The dielectric parameters of these composites can be tuned by frequency, operating temperatures, and nature and content of these nanoparticles.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.