Dielectric behaviour of α-cyclodextrin,heptakis (2,3,6-tri-Omethyl)-β-cyclodextrin,randomly methylated β-cyclodextrin and low frequency Raman spectra of α- and β-cyclodextrins

The frequency and temperature dependence of the real (?′) and imaginary (?″)parts of the dielectric constant of α-cyclodrextrin (form 1; α-CD. 5.9H₂O) and α-cyclodextrin (form III; α-CD.7.6H₂O) and of the corresponding dried forms (α-CD.1.1H₂O, α-CD.2.9H₂O, respectively) has been investigated over the frequency range 0–100 k Hz and temperature range 130–350 K. In addition the dielectric behaviour has been investigated of heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (β-CD.TRIME. 0.3H₂O) and randomly methylated β-cyclodextrin (β-CD.RAME.0.8H₂O). The dielectric behaviour is described well by Debyetype relaxation (α-disperson). All α-CD systems exhibit an additional ω-dispersion at low frequencies, which is attributed to proton transport. The fact that the ?′ values of α-CD form III are larger than those of α-CD form I is attributed to the different numbers and different strengths of the intramolecular hydrogen bonds. Form III has a stable conformation which is shown by the constant values of ?′ in the temperature range 125–250 K. By contrast, in form I the ?′ values increased linearly with temperature, indicating that the system passed through succesive conformations. The temperature dependence of ?″ and phase shift ∞ in all the specimens of α-CD (forms I, III) and fully methylated β-CD do not reveal any orderdisorder transition, because the developed hydrogen bonds ae not of the flip-flop type according to their crystal structures. The partially methylated β-CD reveals the characteristics of the order-disorder transition, which was observed before in the systems dried β-CD.2H₂O and non-dried β-CD.9.8H₂O. There is a direct relation between the hydroxyl groups of β-CD and the order-disorder transition. The order-disorder transition could also be shown in dried β-CD.2.4H₂O and non-dried β-CD.9.8H₂O samples but not in dried α-CD.1.1H₂O and non-dried a-CD.5.9H₂O samples, by low frequency Raman spectroscopy (< 180 cm^?1). The step-like temperature dependence of the band at 33.7cm^?1 reveals a transition at about 223K for both β-CD samples. In the case of α-CD samples the almost linear temperature dependence of the band at 49.1 cm^?1 does not reveal any transition.     

Phase composition and magnetic characteristics of Fe-filled multi-walled carbon nanotubes

The work addresses the correlation between the phase composition and the magnetic characteristics of aligned Fe-filled multi-walled carbon nanotubes (Fe-MWCNTs) grown by pyrolysis of ferrocene on oxidized Si substrates. In a combinatorial approach we exploited the extremely high gradients of the technological parameters temperature and ferrocene flow across the surface of a substrate positioned close to the reactor wall to obtain a large variation in the structural and magnetic properties of the Fe-MWCNTs. In this way, we established several clear correlations between the Fe-filling phase composition and the overall magnetic characteristics of the aligned Fe-MWCNTs. The α-Fe rich samples, which possess a more ordered graphitic sheet structure, a higher degree of preferred crystalline orientation of the metal filling and much larger metal crystallites in comparison with the carbide-rich samples, show a much stronger magnetic anisotropy with easy axis perpendicular to the substrate and unusually high values of the coercive field H_c and the saturation field H_s. The changes in the measured saturation magnetisation M_s and the H_c values correlate well with the variation of the α-Fe content and the filling crystallinity. A special annealing treatment of the samples causes a distinct increase of the α-Fe quantity and an increase of the measured average grain size. The respective magnetic characteristics show a significant increase of the overall magnetic moment and decrease of the coercive field. The correlation between the structural and the magnetic characteristics of the annealed samples matches quite well the respective correlations in the case of as-deposited samples.     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Frequency response of polycrystalline samples of α-Zr(HPO4)2·H2O with different relative densities

Polycrystalline samples of α-Zr(HPO₄)₂·H₂O with different relative densities were investigated by ac admittance measurements at 20°C and 75% relative humidity. The analysis of the frequency response allowed an equivalent circuit to be derived whose parameters were calculated by complex non-linear regression. It was found that the response of the polycrystalline samples was accurately modelled by a parallel combination of a resistance and a constant phase-angle element, both strongly dependent on relative density. The results are discussed on the basis of the present knowledge of the electrical properties of α-Zr(HPO₄)₂·H₂O.     

Hyperfine interactions in iron — Yttrium oxide systems

Hyperfine interactions of iron — yttrium oxide systems have been investigated by Mössbauer spectroscopy and magnetic measurements. The mixed oxides having varying ratios were prepared by heating the coprecipitated oxyhydroxides to about 1000°C in air. The room temperature Mössbauer spectra are complex in nature and some of them exhibit as may as 10 well resolved peaks consisting of two sets of magnetically split hyperfine six line patterns, indicating existence of two different environments around Fe. The values of specific magnetic susceptibility change with increasing amount of yttrium is maximum for 1:1 (Y:Fe) and then falls continuously. The observed H_n values are less than the reported values for α-Fe₂O₃. From the observed data it appears that a transition for the composition of 1:1 definitely takes place and probably two species are formed. Some of the mixed oxides behave like iron filings in a magnetic field.     

Low-field AC susceptibility study of critical current density in Eu:123 and Bi:2223 superconductors

Low-field AC susceptibility measurements have been made, at different values of AC field amplitude H_m (26–600 A/m), on Eu:123 and Bi:2223 samples. Analysis of the temperature dependence of the AC susceptibility has been done employing Beans’ critical state model. The intergranular critical current density (J_c) is calculated as a function of both H_m and temperature for both samples, respectively. It is found that J_c increases with increasing H_m for both samples and its values are generally higher in Bi sample than in Eu sample. Our results are discussed in terms of zero-temperature pinning potential βI(0) in both systems.     

Dielectric properties of α-zirconium phosphate and its organic derivatives

Dielectric properties of compact discs of α-zirconium phosphate, α-zirconium bis(hydroxymethanephosphonate), in an- hydrous and monohydrated form, and of α-zirconium bis(carboxymethanephosphonate) were investigated, as a function of the temperature, at frequencies ranging from 30 Hz to 100 kHz and, in some cases, up to 2.5 MHz. In all the compounds a low frequency dispersion has been found and ascribed to polarization phenomena due to charge transfer through the compact discs. The comparison of the ?_∞ values of α-Zr(HOOCCH₂PO₃)₂, α-Zr(HPO₄)₂· H₂O and α-Zr(HOCH₂PO₃)₂· H₂O with that of α-zirconium pyrophosphate clearly indicate that orientation polarization is not present in these compounds. The dehydration of α-Zr(HPO₄)₂·H₂O and of α-Zr(HOCH₂PO₃)₂· H₂O is associated with an increment, at low frequency, of the real component of the dielectric constant and with a high frequency dispersion, due to relaxation of orientation polarization. Dielectric properties of α-zirconium phosphate are discussed on the ground of its crystalline structure.     

A qualitative and quantitative study of the oxides of aluminum and silicon using AES and XPS

Experimental AES and XPS results from powdered α-Al₂O₃, SiO₂, Al₂Si₂O₇·2H₂O and an aluminosilicate glass are presented. The AES kinetic energy and the XPS binding energy values of core-level states and the peak shapes of X-ray induced O KLL Auger transitions are presented as qualitative reference data for the purpose of aiding in the identification of unknown aluminum oxide/silicon oxide samples. The AES peak-to-peak heights and the XPS peak areas of core-level states are presented as quantitative data and are used in the calculation of empirical relative sensitivity factor values. In addition, the sensitivity factor values are given parameters according to a single variable, f₈, defined as the ratio of the volume density of the oxygen atoms to the sum of the volume densities of the aluminum and silicon atoms.     

H+对高压处理后的β-LiIO3转变为α相的作用

室温下经过不同的高压(最高为80kbar)作用后的β-LiIO₃的X射线衍射实验表明:1)受压后的β-LiIO₃在大气中发生的β→α相转变中,高压的作用是促使α相晶核形成。成核率N与压力P的关系接近于N∝e^kp(k=26.8/bar);2)受压力处理后的β-LiIO₃中的α相量在大气中的明显增加,可归结为大气中水分子在α相晶核表面上解离产生的氢离子引起了α晶核的迅速长大,这一论断受到了H⁺注入产生类似效应的支持。 关键词：     

Hydroxyl ion conduction in ytterbium-doped strontium cerate at T<580 K in H2O/air atmosphere

Open circuit voltage (OCV) measurements in H₂O/air concentration cells at T<580 K using Yb-doped SrCeO₃ electrolyte indicate that under these conditions, protons are transported through the electrolyte as -ve ions, possibly as hydroxyl (OH⁻) ions. The H⁺ ionic transport, which is generally reported, becomes the dominant mode for H₂O/air concentration cells at temperatures greater than 750 K or when H₂O/air electrodes are replaced by H₂/Ar, and the anomalous OCV sign disappears. The combination of low temperature and the presence of hydrogen and oxygen as provided by the H₂O/air system appears to be necessary for the postulated hydroxyl ion electrode reactions to take place. In addition to OCV measurements, results from impedance spectroscopy are used to provide evidence in support of the suggested hydroxyl ion mode of protonic transport under the specified conditions. These findings are directly relevant in the development of novel humidity sensors in the temperature range 450–580K and is reported in a separate paper in this conference. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Local atomic ordering in nickel based Ir and Rh alloys

Experimental measurements of the diffuse X-ray scattering are performed on alloys of Ni with Rh and Ir. The atomic short range order (SRO) parameters α_i are calculated from the measured intensity. The existence of SRO is established in the two systems. The values of α₁ are observed to have anomalously large negative values for all the samples.The experimental data so obtained is interpreted theoretically by calculating the interaction energies on the basis of electronic theory of ordering. Theoretically calculated values of interaction energies are found to be in agreement with the experimentally determined type of order in these alloys.     

Synthesis of α-Fe2O3 nanobelts and nanoflakes by thermal oxidation and study to their magnetic properties

α-Fe₂O₃ nanobelts and nanoflakes have been successfully synthesized by oxidation of iron-coated ITO glass in air. The X-ray diffraction, Raman spectrum and scanning electron microscopy are carried out to characterize the nanobelts and nanoflakes. The formation mechanism has been presented. Significantly, the magnetic investigations show that the magnetic properties are strongly shape-dependent. The magnetization measurements of belt-like and flake-like α-Fe₂O₃ in perpendicular exhibit ferromagnetic feature with the coercivity (H_c) and saturation magnetization (M_s) of 334.5 Oe and 1.35 emu/g, 239.5 Oe and 0.12 emu/g, respectively. For the parallel, belt-like and flake-like α-Fe₂O₃ also exhibit ferromagnetic feature with the H_c and M_s of 205.5 Oe and 1.44 emu/g, 159.6 Oe and 0.15 emu/g, respectively.     

Townsend-Koeffizient α für Alkoholdämpfe,Luft und Argon

Measurements of the first Townsend coefficient for the vapours of CH₃OH, C₂H₅OH, C₃H₇OH(n), C₃H₇OH(iso) are described. The experimental arrangement is tested by measuring the known values of air and argon.     

Investigation on magnetic properties of orientated nanocomposite Pr2Fe14B/α-Fe permanent magnets by micromagnetic finite-element method

Demagnetization curves for nanocomposite Pr₂Fe₁₄B/α-Fe permanent magnets with different hard grain alignment are calculated by a micromagnetic finite-element method. The results show that both remanence and coercivity increase with improving hard grains alignment. The demagnetization curves show a single-phase demagnetization behavior for the samples with grain size d of 10 nm and two-phase behavior for the samples with d of 20 and 30 nm. H_ex (reflecting the magnetic hardening of α-Fe) and H_irr (expressing the irreversible reversal of hard phase) are both enhanced with improving the hard grain alignment. The magnetic reversal in orientated nanocomposite permanent magnets is mainly controlled by inhomogeneous pinning of the nucleated type.     

Hydrogen CARS thermometry in a high-pressure H2–air flame. Test of H2 temperature accuracy and influence of line width by comparison with N2 CARS as reference

This work describes a further step towards the determination of the temperature accuracy of H₂ Q-branch CARS (Coherent Anti-Stokes Raman Scattering) at high pressure with regard to the influence of the H₂ line widths. In laminar steady H₂/air flames in the pressure range 1–15 bar and at fuel-rich conditions with stoichiometries between two and four, quasi-simultaneous temperature measurements were performed with H₂ and N₂ CARS. The temperature values deduced from H₂ CARS are in good agreement with the reference temperature from N₂ CARS. The influence of different line-width contributions on the accuracy of H₂ Q-branch thermometry was investigated in detail. Received: 10 April 2001 / Revised version: 22 May 2001 / Published online: 18 July 2001     

Structural and magnetic features of solid-phase transformations in Mn/Bi and Bi/Mn films

Solid-phase transformations at different annealing temperatures in Mn/Bi (Mn on Bi) and Bi/Mn (Bi on Mn) films have been studied using X-ray diffraction, electron microscopy, and magnetic measurements. It has been shown that the synthesis of the α-MnBi phase in polycrystalline Mn/Bi films begins at a temperature of ~120°C and the Mn and Bi layers react completely at 300°C. The resulting α-MnBi(001) samples have a large perpendicular magnetic anisotropy (K _u ? 1.5 × 10⁷ erg/cm³) and a coercive force H > H _C ~ 3 kOe. In contrast to Mn/Bi, the ferromagnetic α-MnBi phase in Bi/Mn films is not formed even at annealing processes up to 400°C and Mn clusters are formed in a Bi melt. This asymmetry in phase transformations occurs because chemosorbed oxygen existing on the surface of the Mn film in Bi/Mn films suppresses a solid-phase reaction between Mn and Bi. The analysis of the results obtained implies the existence of new low-temperature (~120°C) structural transformation in the Mn–Bi system.     

Mössbauer kinetics of formation of goethite in the basic medium: Effect of the particle size of ferrous hydroxide

The formation of goethite in the basic medium is simulated by stirring, in the presence of air, a mixture of FeSO₄.7H₂O and NaOH in the 1∶5 ratio at different initial concentration C of ferrous ions. The initial oxidation product is ferrous hydroxide and its further oxidation leads mainly to goethite through active α′-FeOOH. The kinetics of the process is studied from Mössbauer spectra.     

自旋阀型[NiFe/Cu/Co/Cu]多层膜的磁电阻、矫顽力和稳定性研究

用电子束蒸镀工艺制备了自旋阀型［NiFe/Cu/Co/Cu］_N多层膜．研究了工艺过程及磁层、非磁层厚度和矫顽力对磁电阻的影响．还研究了磁电阻的稳定性和降低中心磁场等问题．用较优化的方法，制备了中心磁场为（10—20）（10³/4π）A/m，优值大于0.2%（（10³/4π）A/m）^-1的多层膜．实验表明，磁电阻随磁场的变化在中心区内是可逆的．经200℃退火15min，中心磁场略有减小，磁电阻稍有增加．一些样品经一年多老 关键词：     

A study of the effective line width in lithium ferrites using magneto microwave Kerr effect

A new technique to determine the effective line width ΔH_eff using the dimensional resonance phenomenon observed in magneto-microwave Kerr-effect experiment is discussed. This effect depends on the Permeability tensor components and the damping parameter α. The components of permeability tensor μ have been calculated theoritically and the damping parameter α is determined from experimental data. The measurements have been made at 24 GHz on three samples of lithium ferrite and their effective line widths have been obtained both in the partially magnetised and the saturated states of magnetisation. It has been found that ΔH_eff for two states of magnetisation are different. Further, the value of ΔH_eff obtained are higher than expected at this frequency. This suggests the possibility of additional relaxation mechanisms at dimensional resonance.