Synthesis and characterization of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>–Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> magnetoelectric composites with dielectric and magnetic properties

Composite structures consisting of (001)-oriented SrTiO₃ (STO)/La_0.7Sr_0.3MnO₃ (LSMO) films of 30 nm thickness, grown on an (001) Pb(Mg_1/3Nb_2/3)TiO₃– 28 mol.% PbTiO₃ piezoelectric relaxor-ferroelectric single-crystalline wafer were investigated by means of Wide-Angle X-ray Diffraction (WAXRD) in situ under influence of a d.c. electric field with strength E up to ±18 kV/cm. The WAXRD measurements of the films and substrate reflection profiles resulted in a determination of the strain s in the films and the substrate separately. The strained state of the STO/LSMO films is effectively controlled by a huge converse piezoelectric effect of the PMN-PT substrate. The coefficients of coupling between electric-field-induced out-of-plane strain in the films and in the substrate for the composite system STO/LSMO/PMN-PT are obtained.     

First principles study on electronic and optical properties of Al<Subscript>x</Subscript>Ga<Subscript>1−x</Subscript>N and In<Subscript>y</Subscript>Ga<Subscript>1−y</Subscript>N

The band structure, density of states of Al_xGa_1?xN and In_yGa_1?yN was performed by the first-principles method within the local density approximation. The calculated energy gaps of the AlN, Al_0.5Ga_0.5N, GaN, In_0.5Ga_0.5N and InN were 5.48, 4.23, 3.137, 1.274 and 0.504 eV, which were in agreement with the experimental result. The dielectric functions, absorption coefficient and loss function were calculated based on Kramers–Kronig relations. Further more, the relationships between electronic structure and optical properties were investigated theoretically. For Al_xGa_1?xN and In_yGa_1?yN materials, the micromechanism of the optical properties were explained.     

Internal friction and magnetoelectric response in two-layer composites Tb<Subscript>0.12</Subscript>Dy<Subscript>0.2</Subscript>Fe<Subscript>0.68</Subscript>–PbZr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>O<Subscript>3</Subscript>

The inverse magnetoelectric effect and internal friction in two-layer composites based on ferromagnetic Tb_0.12Dy_0.2Fe_0.68 and piezoelectric PbZr_0.53Ti_0.47O₃ are studied in an ac electrical field in the frequency range of 52–213 kHz at temperatures of 293 to 400 K. A correlation is found between the internal friction and the efficiency of the inverse magnetoelectric transformation at resonant frequencies.     

μSR study of Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

A comparative μSR study of ceramic samples of the EuMn₂O₅ and Eu_0.8Ce_0.2Mn₂O₅ multiferroics is performed in the temperature range from 15 to 300 K. It is found that the Ce doping of the EuMn₂O₅ sample slightly reduces the temperature of the magnetic phase transition from T _N = 45 K for the EuMn₂O₅ sample to T _N = 42.5 K for the Eu_0.8Ce_0.2Mn₂O₅ sample. Below the temperature T _N for both samples, there are two types of localization of a thermalized muon with different temperature dependences of the precession frequency of the magnetic moment of the muon in an internal magnetic field. The higher frequency in both samples refers to the initial antiferromagnetic matrix. The behavior of this frequency in Eu_0.8Ce_0.2Mn₂O₅ follows the Curie–Weiss law with the exponent β = 0.29 ± 0.02, which differs from the value β = 0.39 standard for 3D Heisenberg magnetics and is observed in EuMn₂O₅, because of the strong frustration of the doped sample. The temperature-independent low frequency is due to the presence of Mn³⁺–Mn⁴⁺ ferromagnetic pairs located along the b axis of the antiferromagnetic matrix and in the regions of phase separation, which contain such ion pairs and e _g electrons recharging them. In both samples, polarization losses are the same (about 20%) and are associated with the formation of Mn⁴⁺–Mn⁴⁺ + Mu complexes near Mn³⁺–Mn⁴⁺ ferromagnetic pairs. In the temperature interval from 25 to 45 K, the separation of the Eu_0.8Ce_0.2Mn₂O₅ structure into two fractions where the relaxation rates of polarization of muons differ by an order of magnitude is revealed. This effect is due to a change in the state of regions of phase separation (1D superlattices) at the indicated temperatures. Such effect in EuMn₂O₅ is significantly weaker.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Cluster spin glass and superparamagnetism in RuSr<Subscript>2</Subscript>Eu<Subscript>1.5</Subscript>Ce<Subscript>0.5</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10-</Subscript><Subscript>δ</Subscript>

We investigate in detail the dc magnetization and nonlinear ac susceptibility behavior of the superconducting ferromagnet RuSr₂Eu_1.5Ce_0.5Cu₂O_{10- δ} (Ru1222) to develop a comprehensive understanding of the spin glass and superparamagnetism in this material. The structural properties of the system result in the formation of magnetic (ferromagnetic) clusters of different sizes, shapes and properties. The magnetic clustering of the system leads to observation of various features in dc magnetization and ac susceptibility consistent with superparamagnetism and cluster spin glass states, which can coexist or stand alone, depending on the temperature range considered. Experimental results of magnetic measurements in combination with their analysis have enabled us to explain and distinguish these phenomena, as well as to propose a temperature dependent scenario of the system behavior.     

Electrical switching in the MoO<Subscript>3</Subscript>–WO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> and MoO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

High field electrical switching on blown films of MoO₃(60%)–P₂O₅(40%), MoO₃(50%)–WO₃(10%)–P₂O₅(40%), and MoO₃(45%)–WO₃(15%)–P₂O₅(40%) having different thicknesses was studied and compared. Switching was observed using two terminal samples. S-type current–voltage characteristic (current-controlled negative resistance—CCNR) with memory was observed in molybdenum–phosphate glasses, but N-type characteristic (voltage-controlled negative resistance—VCNR) with threshold in tungsten–molybdenum–phosphate glasses was observed. The important observation was that with the addition of WO₃ to binary MoO₃–P₂O5 led to a change of I–V characteristic from CCNR with memory to VCNR with threshold. The measurements of density and molar volume showed linear relation between MoO₃ content and density which decreased with the increase of MoO₃ content. The samples’ thickness had no significant effect on threshold voltage. The attained results also indicated that the electrode material had no effect on switching property of devices. The switching behavior of the devices did not show any dependence on the polarity of the applied voltage. In terms of the effect of heat on the switching behavior of molybdenum–phosphate glasses, it was found that threshold voltage decreases with increasing of temperature. Finally, the switching phenomenon was explained by thermal (formation of crystalline filaments) and electronic models.     

Investigation of quasicrystalline Al<Subscript>62.5</Subscript>Cu<Subscript>25</Subscript>Fe<Subscript>12.5</Subscript> and crystalline β-Al<Subscript>50</Subscript>Cu<Subscript>33</Subscript>Fe<Subscript>17</Subscript> alloys by X-ray photoelectron spectroscopy

The electronic spectra of the valence band and core levels of the surface of polygrain alloys with the icosahedral structure and the β-(CsCl)-type solid solution of Al₅₀Cu₃₃Fe₁₇ were investigated by X-ray photoelectron spectroscopy (XPS). The obtained XPS spectra of the Al_62.5Cu₂₅Fe_12.5 alloy, in comparison with those of the crystalline Al₅₀Cu₃₃Fe₁₇ alloy demonstrate narrowing and a decrease in asymmetry of the Fe2p core level and a decrease in the electron state density N(E _F ) near the Fermi level, features expected for the poorly conducting icosahedral phase. The XPS data are compared with the estimates of N(E _F ) based on the low-temperature specific heat measurements.     

Preparation,structure and properties of La<Subscript>0.67</Subscript>Pb<Subscript>0.33</Subscript>(Mn<Subscript>1-x</Subscript>Co<Subscript>x</Subscript>)O<Subscript>3-δ</Subscript>

La_0.67Pb_0.33(Mn_1-xCo_x)O_3-δ ceramics with x=0, 0.01, 0.03, 0.06, 0.1 and 0.15 have been prepared in a two-step procedure. Precursor gels were made by the wet chemical malic acid method. The gels were calcined and then converted into ceramics by heat treatment at 950 °C and 1000 °C in air. X-ray diffraction showed that the compounds were phase pure. The crystal structure symmetry of the compounds was confirmed to be rhombohedral (space group R3̄c) for the whole investigated range of x. All compounds undergo a paramagnetic–ferromagnetic phase transition between 335 K and 225 K. The basic magnetic characteristics such as the Curie temperature , the paramagnetic Curie temperature θ, the effective magnetic moment and the saturated magnetization decrease with increasing Co doping. The ferromagnetic transition is accompanied by an anomaly in the electrical resistance for all compounds. The high-temperature insulator–metal transitions () do not coincide with the relevant . A large magnetoresistance peak of about 15% was observed for all compounds at . PACS 72.80.Ga; 75.47.Lx; 75.60.Ej     

Synthesis and characterization of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>·LiMn<Subscript>0.33</Subscript>Fe<Subscript>0.67</Subscript>PO<Subscript>4</Subscript>/C cathode materials

A new polyanionic cathode material, Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C for lithium-ion batteries, was synthesized using a sol-gel method and with N,N-dimethyl formamide as a dispersion agent. The analysis of electron transmission spectroscopy and X-ray diffraction revealed that the composite contained two phases. The material has high crystallinity with a grain size of 20–50 nm. The valence states of Mn, V, and Fe in the composite were analyzed by X-ray photoelectron spectroscopy. The electrochemical kinetics in Li₃V₂(PO₄)₃ is effectively enhanced by the incorporation of LiMnPO₄ and LiFePO₄, via structure modification and reduced Li diffusion length. The Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C materials displayed high rate capacity and steady cycle performance with discharge capacity remained 148 mAh g^?1 after 50 cycles at the rate of 0.2C. In particular, the composite exhibited excellent reversible capacities, with the values of 157, 134, 120, 102, and 94 mAh g^?1 at charge/discharge 0.2, 0.5, 1, 2, and 5C rates, respectively.     

Subsolidus phase relation and crystal structure in the Pr<Subscript>1+x-y</Subscript>Ba<Subscript>2-x-z</Subscript>Ca<Subscript>y+z</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7±δ</Subscript> system

The Pr_1+xBa_2-xCu₃O_7± solid solution was investigated by means of X-ray powder diffraction combined with Rietveld analysis. A Pr123 single phase could be synthesized under Pr-rich conditions by sintering at 950 °C in air. The solubility range of Pr_1+xBa_2-xCu₃O_7± solid solution is 0.08x0.80. The structure of Pr_1+xBa_2-xCu₃O_7± for 0.08x<0.30 is orthorhombic. The structure transforms into tetragonal for 0.30x0.80. To form the Pr123 single phase, the Ba sites in the Pr123 structure must have partial Pr ions, and the least amount is x=0.08. Ba ions cannot occupy the sites of Pr ions. In the Pr123 structure, Ca ions can replace Pr ions; the highest value is x=0.4 in the PrBa_2-xCa_xCu₃O_7± system under our experimental conditions. However, Ca ions cannot replace Ba ions. The ionic radius plays a more important role than the chemical properties in the substitution between Pr, Ba and Ca ions in the Pr123 structure. PACS 61.50.Ah; 64.70.Kb; 61.72.Ff     

Maxwell–Wagner relaxation and magnetodielectric properties of Bi<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> ceramics

The complex permittivity ε = ε′–iε″ of manganite bismuth–lanthanum Bi_0.5La_0.5MnO₃ ceramics has been measured at temperature T = 78 K in the frequency range f = 200–10⁵ Hz and in the magnetic induction range B = 0–5 T. Dielectric relaxation and the pronounced magnetodielectric effect have been detected. The explanation based on the superposition of Maxwell–Wagner relaxation and the magnetoresistance effect has been proposed.     

Sol–gel synthesis and characterization of Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite solid electrolytes

Composite solid electrolytes in the system (1???x)Li₂CO₃–xAl₂O₃, with x?=?0.0–0.5 (mole), were synthesized by a sol–gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy-dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed an amorphous feature of Li₂CO₃ and traces of α-LiAlO₂, γ-LiAlO₂ and LiAl₅O₈. The prepared composite samples possess high ionic conductivities at 130–180 °C on account of the presence of lithium aluminates as well as the formation of a high concentration of an amorphous phase of Li₂CO₃ via this sol–gel preparative technique.     

The role of structural and nonstructural water in oxyfluoride K<Subscript>2</Subscript>WO<Subscript>2</Subscript>F<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

X-ray structural and polarization optical investigations have been performed, and birefringence and rotation angles of the optical indicatrix φ _b and φ _c of the K₂WO₂F₄ · H₂O crystal have been measured in the temperature range of 100–600 K. The structure and symmetry of compounds at room temperature have been refined. It has been established that the layered crystal K₂WO₂F₄ · H₂O can exist in two states (A and B) depending on the atmospheric humidity and undergoes the sequence of reversible and irreversible phase transformations G ₃ ↔ G ₂ → G ₁ → G ₀. The sequences of changes in the phase symmetry P [`1]\bar 1 ↔ C2/m → P4/nmm for samples A and m ↔ C2/m → P4/nmm for samples B have been found. The second-order proper ferroelastic phase transition (P [`1]\bar 1 ↔ C2/m) at T ₀₃ = 270–290 K (G ₃ ↔ G ₂) is accompanied by twinning and appearance of the shift deformation x ₆. The crystal system of the substance for the B crystals remains invariable after the second-order phase transition G ₃ ↔ G ₂. The irreversible first-order phase transition G ₂ → G ₁ occurs in a temperature range T ₀₂ ≈ 350–380 K; it is accompanied by the loss of the crystallization water, which then is reduced easily from the atmosphere for a day. The substance decomposes at T ₀₁ ≈ 510 K (G ₁ → G ₀). The distinction between the A and B crystals has been explained by the presence or absence of free water in interlayer spacings.     

Sm valence states and magnetic properties in SmBe<Subscript>13</Subscript> and SmTi<Subscript>2</Subscript>Al<Subscript>20</Subscript> investigated by Sm synchrotron-radiation-based Mössbauer spectroscopy

Synchrotron-Radiation-based \(^{\mathrm {149}}\)Sm Mössbauer spectroscopy was applied to Sm intermetallics, SmBe₁₃ and SmTi₂Al₂₀. Temperature dependence of the Mössbauer parameters in SmBe₁₃ indicate the Sm valence state is purely trivalent. SmBe₁₃ also showed second-order Doppler shift in synchrotron-radiation-based \(^{\mathrm {149}}\)Sm Mössbauer spectroscopy. The Mössbauer parameters obtained in SmTi₂Al₂₀ suggest that the Sm valence is fluctuating and the magnitude of the magnetic moment is reduced by hybridization between 4f and conduction electrons and/or effect of crystal electric field.     

Mössbauer and magnetic studies of the phase state of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/La<Subscript>0.9</Subscript>Ca<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> composites

The formation of an intermediate phase in SrFe₁₂O₁₉/La_0.9Ca_0.1MnO₃ composites was demonstrated for the first time using only Mössbauer spectroscopy. The SrFe₁₂O₁₉/La_0.9Ca_0.1MnO₃ composite was prepared by the two-stage (sol–gel and hydrothermal) synthesis with varying initial conditions. The X-ray diffraction studies showed that the composite consisted of two phases: well-formed structures of manganite La_0.9Ca_0.1MnO₃ and hexagonal ferrite SrFe₁₂O₁₉. It was found that nanocrystalline La_0.9Ca_0.1MnO₃ particles with size d ? 150 nm formed in the composites at the surface of plate-like SrFe₁₂O₁₉ crystallites. The Mössbauer studies showed that the composite contained additional (intermediate) phase La_0.9Ca_0.1Mn(Fe)O₃ that formed at the interface between SrFe12O19 and La_0.9Ca_0.1MnO₃ phases. The intermediate phase concentration increased with the molar content of La_0.9Ca_0.1MnO₃; in this case, the fraction of the surface of SrFe₁₂O₁₉ crystallites coated with La_0.9Ca_0.1MnO₃ increased, which led to the increase in the total area of the interface surface and the intermediate phase concentration.     

Preparation and characterization of organic–inorganic hybrid compound [N(C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Cl<Subscript>6</Subscript>

Organic–inorganic hybrid sample [N(C₄H₉)₄]₂Cu₂Cl₆ was prepared via the reaction between copper chloride and tetrabutylammonium chloride. The compound was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC), DTA-TGA analysis and electrical impedance spectroscopy. DSC studies indicate a presence of one-phase transition at 343 K. The complex impedance of compound [N(C₄H₉)₄]₂Cu₂Cl₆ have been investigated in temperature and frequency ranges 300–380 K and 200 Hz–5 MHz, respectively. The Z′ and Z″ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The frequency dependence of the conductivity is interpreted in term of Jonscher's law: s(w) = s_dc + Awⁿ \sigma (\omega ){ } = {\sigma_{\rm{dc}}} + { }A{\omega^n} . The conductivity follows the Arrhenius relation. The variation of the value of these elements with temperatures confirmed the availability of the phase transition at 343 K detected by DSC and electrical measurements.     

Preparation and characterization of LiNi<Subscript>0.495</Subscript>M<Subscript>0.01</Subscript>Mn<Subscript>0.495</Subscript>O<Subscript>2</Subscript> (M = Zn,Co, and Y) for lithium ion batteries

Layered structured LiNi_0.5Mn_0.5O₂ and LiNi_0.495M_0.01Mn_0.495O₂ (M = Zn, Co, and Y) compounds were prepared by PVP (poly(vinyl pyrrolidone))-assisted sol-gel method, and their structural, morphological, vibrational, transport, and electrochemical properties were characterized by XRD, SEM, FTIR, Raman, AC impedance, and galvanostatic charge and discharge analysis. XRD patterns reveal that doping does not change the crystal structure of the LiNi_0.5Mn_0.5O₂ compound. SEM images show that the average size of the particle is in sub-micron ranges. The AC impedance studies shows an electrical conductivity of ～2.5 × 10^?7 S/cm for the parent compound. The introduction of Zn/Co/Y at equivalent sites increased the electrical conductivity by one order ～10^?6 S/cm. The compound LiNi_0.495Co_0.01Mn_0.495O₂ shows the highest electrical conductivity of 2.85 × 10^?6 S/cm and delivers a specific discharge capacity of 110 mAh/g at the end of the 25th cycle in the voltage window of 2.5–4.4 V for a current density of 30 mA/g.     

Controlled flame synthesis of αFe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: effect of flame configuration,flame temperature,and additive loading

Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe₂O₃ and magnetite Fe₃O₄. We found that the synthesized nanoparticles were smaller (6–12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50–60 nm) when CH₄, O₂, Ar, and N₂ gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH₄, O₂, Ar gas flow rates were kept constant, and N₂ gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N₂ cooling demonstrated that particles no larger than 50–60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the outer annulus along with the CH₄ in the inverse diffusion flame configuration. When particles were synthesized in the presence of the TTIP additive, larger monodispersed individual particles (50–90 nm) were synthesized as observed by TEM. In this article, we show that iron oxide nanoparticles of varied morphology, composition, and size can be synthesized and controlled by varying flame configuration, flame temperature, and additive loading.