Fabrication of Fe/Fe<Subscript>3</Subscript>C-functionalized carbon nanotubes and their electromagnetic and microwave absorbing properties

Fe/Fe₃C-functionalized carbon nanotubes (CNTs) have been prepared by the floating catalyst chemical vapor-deposition method. It is demonstrated that the Fe and Fe₃C nanostructures are both encapsulated in the CNTs or decorated on the surface of CNTs. The Fe/Fe₃C content in the composites can easily be adjusted by changing the ferrocene concentration in the preparation. The electromagnetic properties of the CNTs have been evaluated in the frequency range of 2–18 GHz, and the nanocomposites exhibit excellent microwave absorbing performance. The CNT composites with higher Fe/Fe₃C content show enhanced microwave reflection losses. The significant influence of the Fe/Fe₃C nanostructures on the microwave absorption is realized by tuning the characteristic impedance of the nanocomposites. With increasing thickness, the maximum reflection loss peak shifts to lower frequency. The microwave absorbing performance of the composites is mainly caused by dielectric loss, resulting from the continuous CNT networks with excellent electrical conductivity.     

Structural and electrical properties of BiFeO<Subscript>3</Subscript>-Pb(ZrTi)O<Subscript>3</Subscript> composites

The polycrystalline (Bi_1-xPb_x)(Fe_1-xZr_0.6xTi_0.4x)O₃ (x=0.15, 0.25, 0.40, 0.50) (BPFZT) nanoceramic composites were synthesized using mechanical activation and solid-state reaction techniques. The formation of single-phase compounds with 100% solubility of BiFeO₃ and Pb(Zr_0.6Ti_0.4)O₃ was confirmed by an X-ray diffraction (XRD) technique. Detailed structural analysis of the fabricated BPFZT composites suggests the formation of tetragonal structure (i.e., distorted perovskite) for all composition. The dielectric constant and loss-tangent of the BPFZT composites decrease on increasing frequency and temperature. It has also been observed that the leakage current and loss-tangent are reduced by increasing the contents of PZT in the BPFZT composites, and hence they may be considered useful for some applications. The values of activation energies and the nature of variation of conductivity with temperature and frequencies suggest that the space charge and oxygen ion vacancies play a significant role in the conduction process. PACS 61.10.Nz; 77.22.Ch; 77.84.Lf; 81.20.Ev     

Effect of KNbO<Subscript>3</Subscript> modification on structural,electrical and magnetic properties of BiFeO<Subscript>3</Subscript>

The polycrystalline samples of (Bi_1?x K _x ) (Fe_1?x Nb _x ) O₃ (BKFN) for x = 0.0, 0.1, 0.2 and 0.3 were synthesized by a solid-state reaction method. The X-ray diffraction patterns of BKFN exhibit that the addition of KNbO₃ in BiFeO₃ gradually changes its structure from rhombohedral to pseudocubic. The analysis of scanning electron micrograph clearly showed that the sintered samples have well-defined and uniformly distributed grains. Addition of KNbO₃ to BiFeO₃ enhances the dielectric, ferroelectric and ferromagnetic properties of BiFeO₃. Detailed studies of impedance and related parameters of BKFN using the complex impedance spectroscopic technique exhibit the significant contributions of grain and grain boundaries in the resistive and transport properties of the materials. Some oxygen vacancies created in the ceramic samples during high-temperature processing play an important role in the conduction mechanism. The leakage current or tangent loss of BiFeO₃ is greatly reduced on addition of KNbO₃ to the parent compound BiFeO₃. Preliminary studies of ferroelectric and magnetic characteristics of the samples reveal the existence of ferroelectric, and weak ferromagnetic ordered ceramics.     

Preparation and electrochemical properties of LiFePO<Subscript>4</Subscript>/graphene composites from tailoring graphene oxides

LiFePO₄/graphene composites have been prepared by using tailoring graphene oxide (GO) nanosheets as precursors. The structure and electrochemical properties of the composites were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), Raman microscopy, and a variety of electrochemical testing techniques. The decrease in graphene size reduces the contact resistance between activated materials, and enhances the lithium-ion transport in LiFePO₄/graphene composites. With low weight fractions of small-size graphene sheets, the composites show better electrochemical performance than those with large size graphene sheets.     

Contactless density measurement of high-temperature BiFeO<Subscript>3</Subscript> and BaTiO<Subscript>3</Subscript>

The density of liquid and undercooled BiFeO₃ and high-temperature solid, liquid, and undercooled BaTiO₃ was measured with an electrostatic levitation furnace. The density was obtained with an ultraviolet-based imaging technique that allowed excellent sample contrast throughout all phases of processing, including at elevated temperatures. Over the 1250- to 1490-K temperature range, the density of liquid BiFeO₃ can be expressed as _L(T)=6.70×10³–1.31(T-T_m)(kgm^-3) (±2 per cent) with T_m=1423 K, yielding a volume coefficient of thermal expansion _L(T)=1.9×10^-4 K^-1. For BaTiO₃, the density of the solid can be expressed as _S(T)=5.04×10³–0.21(T-T_m) (T_m=1893 K) over the 1220- to 1893-K range, yielding a volume coefficient of thermal expansion _S(T)=4.2×10^-5 K^-1, whereas that of the liquid can be expressed as _L(T)=4.04×10³-0.34(T-T_m) over the 1300- to 2025-K range with _L(T)=8.4×10^-5 K^-1. PACS 77.84.-s; 81.05.Je; 81.20.n     

Effect of heat treatment on the structure and properties of a BiFeO<Subscript>3</Subscript> nanopowder

This paper presents the results of an investigation of changes in the structure, magnetic, electrical, and thermal properties of a nanostructured bismuth ferrite powder prepared by the combustion of nitrateorganic precursors before and after heat treatment at temperatures of 500, 600, 700, and 800°C. It has been shown that there is a dependence of the magnetic properties on the dispersion of the particles. The specific features of the temperature and frequency dependences of the dielectric properties over wide ranges of frequencies and temperatures, as well as near the Néel temperature, have been considered.     

Weak ferromagnetism in BiFeO<Subscript>3</Subscript>-based multiferroics

The magnetic properties of the Bi_{1 ? x} Ln _x FeO₃ (Ln is a rare-earth ion), Bi_{1 ? x} A _x FeO_{3 ? x/2} (A is an alkali earth ion), and BiFe_{1 ? x} Ti _x O_{3 + δ} solid solutions in magnetic fields up to 14 T have been studied. The concentration ranges of the existence of the ferroelectric phase described by the space group R3c have been determined. It is shown that the substitution of the rare-earth ions for the Bi³⁺ ions leads to a sharp decrease in the critical fields inducing the metamagnetic transition from a modulated antiferromagnetic state to a weakly ferromagnetic one; however, the modulated structure in the concentration range of the R3c phase is mainly retained. The substitution of the alkali earth ions (x ～ 0.1) for the bismuth ions leads to the total destruction of the modulated structure and to the implementation of the weakly ferromagnetic state within the R3c phase. A homogeneous weakly ferromagnetic state has been revealed when the Ti⁴⁺ ions (x = 0.1) are substituted for the Fe³⁺ ions in the ferroelectric R3c phase.     

Specific features of structural states in the BiFeO<Subscript>3</Subscript>-YMnO<Subscript>3</Subscript> solid solutions

The (1 − x)BiFeO_3−x YMnO₃ solid solutions have been found to undergo the following sequence of phase transformations with increasing x: R3c → Pbnm → C2 → Pnma → P6₃ cm. It has been established that the Pbnm and Pnma phases have different orientations of atomic displacements and can exhibit antiferroelectric properties.     

Thermal stability and electrical conductivity of multiferroics BiFeO<Subscript>3</Subscript>/REEs

Ceramic samples of bismuth ferrite and solid solutions of Bi_{1 − x} A _x FeO₃ type (where A = Lu, Yb, Tm, Er, Ho, Dy, Tb, Gb, Eu, Sm, Nd, Pr, La; 0.05 ≤ x ≤ 0.20; Δx = 0.05) were prepared. Spectra of the real part of electrical conductivity were studied within the range 10⁻⁴–10⁻⁶ Hz. The dependence of the samples’ thermal stability and electrical conductivity on the size of the substituting ions was established.     

Specific features of the thermal,magnetic, and dielectric properties of multiferroics BiFeO<Subscript>3</Subscript> and Bi<Subscript>0.95</Subscript>La<Subscript>0.05</Subscript>FeO<Subscript>3</Subscript>

Thermophysical, magnetic, and dielectric properties of multiferroic BiFeO₃ and Bi_0.95La_0.05FeO₃ ceramic compounds were comprehensively studied. Anomalies of the permittivity near an antiferromagnetic phase transition related to the structural variations were detected. The temperature T _N was determined from the temperature dependences of the thermal expansion coefficient, heat capacity, and differential susceptibility. It is shown that the transition point is shifted to higher temperatures as the rare-earth La ion substitutes for Bi. It is established that an insignificant substitution of lanthanum for bismuth enhances the magnetic properties of bismuth ferrite and the magnetodielectric effect.     

Effects of BaTiO<Subscript>3</Subscript> and SrTiO<Subscript>3</Subscript> as the buffer layers of epitaxial BiFeO<Subscript>3</Subscript> thin films

BiFeO₃ (BFO) thin films with BaTiO₃ (BTO) or SrTiO₃ (STO) as buffer layer were epitaxially grown on SrRuO₃-covered SrTiO₃ substrates. X-ray diffraction measurements show that the BTO buffer causes tensile strain in the BFO films, whereas the STO buffer causes compressive strain. Different ferroelectric domain structures caused by these two strain statuses are revealed by piezoelectric force microscopy. Electrical and magnetical measurements show that the tensile-strained BFO/BTO samples have reduced leakage current and large ferroelectric polarization and magnetization, compared with compressively strained BFO/STO. These results demonstrate that the electrical and magnetical properties of BFO thin films can be artificially modified by using a buffer layer.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Lattice dynamics of BiFeO<Subscript>3</Subscript> under hydrostatic pressure

The vibrational frequencies of the BiFeO₃ crystal lattice in the cubic phase (Pm3m) and the rhombohedral paraelectric phase (R3c) are calculated in terms of the ab initio model of an ionic crystal with the inclusion of the dipole and quadrupole polarizabilities. In the ferroelectric phase with the symmetry R3c, the calculated spontaneous polarization of 136 μC cm^?2 agrees well with the experimental data. The dependences of the unit cell volume, the elastic modulus, and the vibrational frequencies on the pressure are calculated. It is found that the frequency of an unstable ferroelectric mode in both the cubic (Pm3m) and rhombohedral (R3c) phases are almost independent of the applied pressure, in contrast to classical ferroelectrics with a perovskite structure, where the ferroelectric instability is very sensitive to a variation in the pressure.     

Phase states in solid solutions based on BiFeO<Subscript>3</Subscript>

Concentration and temperature regions of the existence of different phases (R3c, Pbnm, P4mm, Amm2, Pbcm, and Pm3m) in solid solutions of BiFeO₃-BiMnO₃, BiFeO₃-KNbO₃, and BiFeO₃-NaNbO₃ are determined.     

<Superscript>57</Superscript>Fe NMR study of multiferroic BiFeO<Subscript>3</Subscript>

The effects of the ⁵⁷Fe isotope content and high-frequency magnetic field amplitude h ₁ on the shape of the NMR spectrum of multiferroic BiFeO₃ at T = 4.2 K are studied by pulsed nuclear magnetic resonance. The NMR spectrum shape and transverse relaxation time T ₂ are found to depend strongly on the ⁵⁷Fe isotope content and h ₁ in multiferroic BiFeO₃ in the presence of a spatial spin-modulated structure of a cycloid type. In a sample with a high ⁵⁷Fe isotope content, the Suhl-Nakamura interaction contributes substantially to T ₂. When these dynamic effects are taken into account for analysis of the NMR spectrum shape, an undisturbed (without an anharmonicity effect) spatial spin-modulated structure of a cycloid type is shown to exist in BiFeO₃.     

On the room temperature multiferroic BiFeO<Subscript>3</Subscript>: magnetic,dielectric and thermal properties

Magnetic dc susceptibility between 1.5 and 800 K, ac susceptibility and magnetization, thermodynamic properties, temperature dependence of radio and audio-wave dielectric constants and conductivity, contact-free dielectric constants at mm-wavelengths, as well as ferroelectric polarization are reported for single crystalline BiFeO₃. A well developed anomaly in the magnetic susceptibility signals the onset of antiferromagnetic order close to 635 K. Beside this anomaly no further indications of phase or glass transitions are indicated in the magnetic dc and ac susceptibilities down to the lowest temperatures. The heat capacity has been measured from 2 K up to room temperature and significant contributions from magnon excitations have been detected. From the low-temperature heat capacity an anisotropy gap of the magnon modes of the order of 6 meV has been determined. The dielectric constants measured in standard two-point configuration are dominated by Maxwell-Wagner like effects for temperatures T > 300 K and frequencies below 1 MHz. At lower temperatures the temperature dependence of the dielectric constant and loss reveals no anomalies outside the experimental errors, indicating neither phase transitions nor strong spin phonon coupling. The temperature dependence of the dielectric constant was measured contact free at microwave frequencies. At room temperature the dielectric constant has an intrinsic value of 53. The loss is substantial and strongly frequency dependent indicating the predominance of hopping conductivity. Finally, in small thin samples we were able to measure the ferroelectric polarization between 10 and 200 K. The saturation polarization is of the order of 40 μC/cm², comparable to reports in literature.     

Infrared optical properties of BiFeO<Subscript>3</Subscript> thin films prepared by chemical solution deposition

We report the electrical and optical properties of P-doped epitaxial ZnO thin films grown heteroepitaxially on sapphire substrates or homoepitaxially on ZnO wafers grown by the hydrothermal method, respectively. As-grown heteroepitaxial thin films exhibit semi-insulating to strongly n-conducting behavior depending on the P-content and the oxygen partial pressure applied during deposition. New features are observed in the recombination spectra compared to nominally undoped ZnO thin films. The spectral position of these new features also depends on the growth conditions making a clear correlation between P-incorporation and particular spectral features feasible. For the homoepitaxially grown thin films lateral scanning capacitance microscopy measurements revealed areas of both n- and p-type majority carriers.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Toroidal moments as indicator for magneto-electric coupling: the case of BiFeO<Subscript>3</Subscript> versus FeTiO<Subscript>3</Subscript>

In this paper we present an analysis of the magnetic toroidal moment and its relation to the various structural modes in R3c-distorted perovskites with magnetic cations on either the perovskite A or B site. We evaluate the toroidal moment in the limit of localized magnetic moments and show that the full magnetic symmetry can be taken into account by considering small induced magnetic moments on the oxygen sites. Our results give a transparent picture of the possible coupling between magnetization, electric polarization, and toroidal moment, thereby highlighting the different roles played by the various structural distortions in multiferroic BiFeO₃ and in the recently discussed isostructural material FeTiO₃, which has been predicted to exhibit electric field-induced magnetization switching.     

Dielectric relaxation in magnetoelectric composite 0.85BiFeO<Subscript>3</Subscript>–0.15MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>

Dielectric properties of 0.85BiFeO₃–0.15MgFe₂O₄ composite fabricated with conventional ceramic technology are studied in the temperature interval of 20–250°C at frequencies of 25 Hz to 1 MHz. Dielectric relaxation is observed, the nature of which is discussed in the context of a mechanism of interaction between ferroelectric domain boundaries and point defects.