The anomalous behaviour of Gd atoms (Fe1−xMnx)2 compounds

The educed Gd atoms in the X-structure (Th₆Mn₂₃-type) of Gd(Fe_1−xMn_x)₂ were magnetically investigated by comparing with Gd₆(Fe_1−yMn_y)₂₃ whose structure is Th₆Mn₂₃-type. The magnetic properties of Gd(Fe_1−xMn_x)₂ (0.4≤x≤0.7) were observed to be quite similar to those of Gd₆(Fe_1−yMn_y)₂₃ (0.4≤y≤0.7).     

A Novel Hydrophilic Modification of PTFE Membranes Using In Situ Deposited PANI

A new kind of polyaniline/polytetrafluoroethylene (PANI/PTFE) composite membrane has been successfully prepared by in situ deposition of PANI onto PTFE membranes during the aniline's dispersion polymerization. The PTFE membrane was plasma treated before the aniline polymerization; the induced alteration of morphology and surface properties accelerated the polymerization of aniline and increased the number density of the deposited PANI onto the PTFE surface. The surface properties and morphology of the membranes were characterized. The composite PANI/PTFE membrane exhibited an enhanced flux in salt water separation, which is up to 75% higher than the pristine membrane.     

Magnetic and microstructural investigations of melt-spun Fe(NdPr)B

The magnetic behavior of rapidly solidified FePrB was investigated in the composition range Fe_77+χPr₁₅B_8−χ (0 ≤ χ ≤ 4). Furthermore, the magnetic and microstructural properties of Fe(NdPr)B were analyzed in the range Fe₇₈(Nd_χPr_1−χ)₁₅B₇ (0 ≤ χ ≤ 1). The temperature dependence of the critical field was analyzed with a modified form of Brown's expression for the nucleation field. From this analysis the values for the microstructural parameters, _K and N_eff, were determined which describe the deteriorating effects of the non-ideal microstructure on the coercivity.     

聚苯胺/碳纳米管复合体的制备及其三阶非线性光学性能研究

通过原位吸附-受限生长聚合法成功制备了聚苯胺/碳纳米管(PANI/MWCNT)复合体.红外光谱和拉曼光谱证实了在碳纳米管(MWCNT)表面的包覆层为聚苯胺(PANI).紫外—可见吸收光谱表明随着MWCNT含量的增加PANI的吸收发生红移且强度提高.扫描电子显微镜和透射电子显微镜观察发现，PANI/MWCNT复合体直径为40—70nm，其中PANI的包覆层厚度约为15—20nm.利用四波混频方法测试它们的三阶非线性光学系数，结果发现PANI/MWCNT复合体的三阶非线性光学系数比纯PANI大，这说明在MWC 关键词： 碳纳米管 聚苯胺 复合体 三阶非线性光学系数     

Phase segregation of LixMn2O4 (0.6<x<1) in non-equilibrium reduction processes

Chemical synthesis routes to Li_xMn₂O₄ (0.15≤x≤1) in non-equilibrium reduction processes were developed to carry out detailed structural analysis. Non-equilibrium Li_xMn₂O₄ (0.15≤x≤1) samples were prepared by chemical lithiation of λ-MnO₂ with LiI for 24 h; longer than 1 week was needed to reach true equilibrium at room temperature. The samples were characterized by X-ray diffraction analysis. The phase diagram was different from that in the equilibrium state; three cubic phases (phases A, B and C) were observed for Li_xMn₂O₄ (0.15≤x≤1). There were two regions of two-phase coexistence: the region of 0.25<x<0.55 (phase B+phase C) and 0.6<x<1.0 (phase A+phase B). In the compositional range of 0.6<x<1.0, the lattice constants of phases A and B change with the lithium composition, this indicates that it is a structural anomaly with a metastable two-phase character in non-equilibrium reduction processes.     

Electrical and magnetic properties of polyaniline/Fe3O4 nanostructures

We report on electrical and magnetic properties of polyaniline (PANI) nanotubes (150 nm in diameter) and PANI/Fe₃O₄ nanowires (140 nm in diameter) containing Fe₃O₄ nanoparticles with a typical size of 12 nm. These systems were prepared by a template-free method. The conductivity of the nanostructures is 10⁻¹–10⁻² S/cm; and the temperature dependent resistivity follows a ln ρT^−1/2 law. The composites (6 and 20 wt% of Fe₃O₄) show a large negative magnetoresistance compared with that of pure PANI nanotubes and a considerably lower saturated magnetization (M_s=3.45 emu/g at 300 K and 4.21 emu/g at 4 K) compared with the values measured from bulk magnetite (M_s=84 emu/g) and pure Fe₃O₄ nanoparticles (M_s=65 emu/g). AC magnetic susceptibility was also measured. It is found that the peak position of the AC susceptibility of the nanocomposites shifts to a higher temperature (>245 K) compared with that of pure Fe₃O₄ nanoparticles (190–200 K). These results suggest that interactions between the polymer matrix and nanoparticles take place in these nanocomposites.     

Disruption of antiferromagnetic order in Zn-doped La2CuO4

The magnetic phase diagram of La₂(Cu_1−xZn_x)O₄ has been determined from zero-field muon-spin-rotation (ZF-μSR) data taken at LAMPF for 0 ≤ x ≤ 0.10. Antiferromagnetic onset temperatures follow T_N(x) from susceptibility measurements on the same samples. However, the order becomes long range, as evidenced by a well-defined internal magnetic field, only at temperatures well below T_N. Extrapolation of our results yields T_N → 0 K at x = 0.11 for a single (Cu_1−xZn_x)O₂ plane, and comparison with YBa₂(Cu_1−xZn_x)₃O₆ implies identical disruption of magnetism by Zn doping in the single- and double-plane systems.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Normal-state transport properties of Ba1−xKxBiO3 crystals

The normal-state transport properties of Ba_1−xK_xBiO₃ crystals with a wide range of potassium compositions (0≤x≤0.62) were studied. Although the host material BaBiO₃ has a monoclinic structure, the system changes from a monoclinic to an orthorhombic structure with a small doping of potassium (0≤x<0.35) and behaves similar to a doped semiconductor, without exhibiting superconductivity. In the composition range, holes are majority carriers in the transport phenomena. When x exceeds a critical value (0.35), the system goes into a cubic superconducting phase with a single metallic band. The vicinity of the critical composition transport phenomena is easy to understand assuming the existence of two conducting channels that are made up of metallic and semiconducting phases. Maximum T_c exceeding 30 K was observed at x0.4, where carrier density was at its maximum. Overdoping with potassium suppresses superconductivity. In the metallic composition of x>0.45, transport seems to correlate with the phonon mode with an energy distribution of 15–43 meV.     

Chemical diffusivity of BaTiO3−δ: I. Experimental determination

The chemical diffusivity of ‘undoped' polycrystalline BaTiO_3−δ was determined via a conductivity relaxation technique, at elevated temperatures (800≤T/°C≤1100) as a function of the ambient oxygen partial pressure in the range of 10⁻¹⁶≤P_O2/atm≤1 including an n- to p-type transition regime. Mathematical formulation was developed to convert conductivity relaxation to the corresponding nonstoichiometry (δ) relaxation in the transition regime. It has been found that the chemical diffusivity appears to exhibit a maximum at the n-to-p transition point where the electronic minimum conductivity falls, and that surface reaction becomes more rate-determining than diffusion as the transition point is approached from both n-type and p-type branches. Experimental details are given and the results are exhaustively compared with those reported up to date on the ‘undoped' BaTiO₃.     

Sonochemical synthesis of polyaniline nanofibers

Conventionally, micro-sized irregular polyaniline (PANI) particles were synthesized by dropwise addition of the ammonium persulfate (APS) solution into the aniline (ANI) solution with mechanical stirring. By replacing the mechanical stirring with an ultrasonic irradiation, PANI nanofibers in diameters of approximately 50 nm and lengths of 200 nm to several micrometers were prepared. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that at the early stage of polymerization, the polymers formed in both the mechanical stirred and ultrasonicated systems are in the form of nanofiber. However, with continuing of the reaction, these primary nanofibers grow and agglomerate into irregular shaped PANI particles in the mechanical stirred system, while in the case of the ultrasonic irradiation, the growth and agglomeration are effectively prevented, preserving thus the PANI nanofibers in the final product. By increasing the APS/ANI molar ratio from 0.5 to 2.5, the aspect ratios of the PANI nanofibers decreased. The PANI nanofibers exhibit higher solubility than the irregular shaped PANI particles. Although the yield, as well as the conductivity of the ultrasonic synthesized PANI nanofibers, was slightly lower than the irregular shaped PANI particles, the ultrasonic synthesis approach is one of the facile and scalable approaches in synthesizing PANI nanofibers in comparison with other ones without use of templates (e.g., the interfacial polymerization and rapid mixing polymerization). UV-Vis and Fourier transformed infrared (FTIR) spectra indicated ultrasound had no significant effect on the chemical structure of the PANI.     

Synthesis and Characterization of Conductive Polyaniline Nanoparticles Through Ultrasonic Assisted Inverse Microemulsion Polymerization

Polyaniline (PANI) nanoparticles were prepared through ultrasonic assisted inverse microemulsion polymerization method. Polymerization of aniline was confined to a nanoreactor named water pool surrounded by surfactant molecules in the apolar continuous phase. The size of the PANI nanoparticles decreases with the decrease of the value. The spherical nanoparticles (10–50 nm) can further form the uniform submicrometer aggregates with a size of 200 400 nm induced by ethanol, and the size of the aggregate decreases with the decrease of the value. The morphology of aggregates as well as aggregation behavior of PANI nanoparticles were characterized by TEM. The polymerization rate, UV–vis absorption spectra, FTIR spectra, XRD, as well as the conductivity were examined at different [water]/[surfactant] molar ratio, i.e. value. Ultrasound enhances the polymerization rate of aniline that is usually very slow under conventional stirring in inverse microemulsion and contributes to produce spherical nanoparticles. Also, ultrasound irradiation promotes the diffusion of HCl molecules and improves the degree of doping. Polymerization of aniline occurred in the confined nanoreactor in microemulsion and strengthens the hydrogen-bonding of amine and imine of PANI molecular chains, which improves the degree of crystallinity. The conductivity of obtained PANI is in the magnitude of 10^-1 S cm^-1, and is changed with value.     

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

Electrocatalytic oxidation of formaldehyde on platinum well-dispersed into single-wall carbon nanotube/polyaniline composite film

Single-walled carbon nanotubes (SWNTs)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The composite films were dispersed Pt by electrodeposition technique. The presence of SWNTs and platinum in the composite film was confirmed by XRD analysis and scanning electron microscopy (SEM). Four-point probe investigation and electrochemical impedance spectroscopy (EIS) revealed that the well arrangement of PANI coated SWNTs in these films enhanced electric conductivity and facilitated the charge-transfer of the composite films. Cyclic voltammogram (CV) and chronoamperogram showed that Pt-modified SWNT/PANI composite film performs higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formaldehyde oxidation. The results imply that the SWNT/PANI composite film as a promising support material improves the electrocatalytic activity for formaldehyde oxidation greatly.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

Magnetic properties and composition range of non-stoichiometric m-type hexagonal ferrites prepared by ion exchange

Single crystals of Ba, Sr M-type hexagonal ferrites were prepared by ion exchange in Ba, Sr containing molten salts from single crystals of β″ -ferrites. A fast diffusion of the divalent Ba²⁺, Sr²⁺ is observed leading to a non-stoichiometric M-type ferrite with chemical formula: Ba_1+xFe_10.5Co_0.25O_17+x (0 ≤ x ≤ 0.25). x depending on the exchange reaction time. Saturation magnetization ranges from 19 to 64 emu/g depending on exchange conditions. The Curie temperature is (470 ± 5)°C. An easy axis direction (M_s c) has been determined in all cases. The observed anisotropy is considerably lower than that of M ferrite. The calculated anisotropy constants are, in 10⁶ erg/cm³, K₁ = 0.8 and K₂ = 1.0 at room temperature.     

Lithium insertion to ReO3-type metastable phase in the Nb2O5–WO3 system

Lithium insertion to distorted ReO₃-type metastable solid solution Nb_xW_1−xO_3−x/2 (0≤x<0.25) has been studied by chemical and electrochemical methods. In the course of lithium insertion into tetragonal compounds, transition to a cubic phase was found to occur in the region where values of y (in Li_yNb_xW_1−xO_3−x/2) fall between 0.2 and 0.3, and the phase transition was found to depend on the conditions of the reaction. Changes in OCV and lattice parameters in tetragonal region (y<0.2) were discussed from the viewpoint of the ordering of lithium ions. Also, the component diffusion coefficient of lithium in tetragonal compounds Li_0.1Nb_xW_1−xO_3−x/2 (0≤x≤0.23) was found to increase with niobium content when x≤0.10, and to saturate at 4×10⁻⁹ cm²/s.     

Improvement of the adhesion between polyaniline and commercial carbon paper by acid treatment and its application in supercapacitor electrodes

Commercial carbon paper was coated with polyaniline (PANI) using in situ polymerization of aniline. Prior to the PANI coating, acid treatment was performed to carboxylate the surface of the carbon paper for enhancing PANI adhesion by sonication of the carbon paper in a mixture of concentrated sulfuric and nitric acids. The loading mass density of PANI on the acid-treated carbon paper increased more than three times compared to that on the carbon paper without acid treatment. The specific capacitance also increased from 112 to 174 F/g in a two-electrode system (calculated using a total mass of carbon paper and PANI) due to better PANI coating on the acid-treated carbon paper. The simple acid treatment provides good adhesion of PANI to the commercial carbon paper and can be applied to prepare supercapacitor electrodes.