Nanocrystallite interface effect and exchange bias phenomenology in Cr2O3 and NiO nanoparticles

Nanocrystalline Cr₂O₃ and NiO are prepared using high-energy ball milling. Average sizes of the particles obtained from Scanning Electron Microscopy and crystallite sizes obtained from X-ray diffraction are larger for Cr₂O₃ than NiO particles. At low temperature, large high-field magnetization and small coercivity lead to a weak exchange bias for Cr₂O₃, whereas small high-field magnetization and large coercivity lead to a considerable exchange bias for NiO. The training effect is observed for NiO at 4 K which could be described with a recursive formula constructed in the framework of the spin configurational relaxation model. The results suggest that the pinning mechanism at the interface between the antiferromagnetic and the weak ferromagnetic component ascribed to uncompensated spins leads to the exchange bias effect.     

The formation model of Ni-Cr oxides on NiCoCrAlY-sprayed coating

The atomic arrangement and distribution of oxides (Cr₂O₃, NiCr₂O₄ and NiO) on the sprayed-NiCoCrAlY coating after oxidation are analyzed. The formation and the growth model of Ni-Cr oxide phases are discussed according to the matching relationship between atoms. The outline character and a scale of spinel NiCr₂O₄ are discussed. The results show that Cr atoms can form two close-packed arrangements in the crystal plane of Cr₂O₃ perpendicular to 〈0 0 1〉 orientation. The atomic spacing in the first arrangement corresponds to double that of Ni/Ni₃Al in {1 1 1} crystal face. This suggests that Ni/Ni₃Al is the substrate for Cr₂O₃ to grow along 〈0 0 1〉 direction. The lattice mismatch between Cr₂O₃ and Ni/Ni₃Al is less than that of Al₂O₃, which indicates that Cr₂O₃ is easier to form than Al₂O₃ during the oxidation process. The atomic spacing in another close-packed arrangement of Cr₂O₃ perpendicular to 〈0 0 1〉 orientation is approximately equal to that of Ni or Cr in the plane of NiCr₂O₄ and NiO perpendicular to 〈1 1 1〉 orientation. So Cr₂O₃ can be the substrate for NiCr₂O₄ and NiO to grow in the 〈0 0 1〉 direction. NiCr₂O₄ and NiO can grow directly along the 〈1 1 1〉 orientation on each other. NiCr₂O₄ can grow outward in the planes of Cr₂O₃ perpendicular to 〈0 0 1〉 and grow inward along 〈1 1 1〉 orientation of NiO.     

Effect of some additions on the sinterability and magnetic properties of barium hexaferrite

The effect of additions on the densification of previously prepared stoichiometric barium hexaferrite, during the initial and intermediate stages of sintering, as well as on the coercivity and remanence were studied. The effect of non-stoichiometry, SiO₂, Al₂O₃, Cr₂O₃, TiO₂, SnO₂, MnO₂, MgO, NiO and Bi₂O₃ is included.While SiO₂ and Bi₂O₃ form liquid phases that increase the density, Al₂O₃, Cr₂O₃ and MnO₂ form a limited solid solution and are generally beneficial when added in the proper amounts. At 1300 SiO₂ up to 0.55% and Al₂O₃ up to 1% gave better magnetic properties. On the other hand addition of TiO₂, MgO, NiO or SnO₂ has a deleterious effect.     

Effect of CaO-B2O3-SiO2 glass on the magnetic and dielectric properties of NiCuZn ferrites

NiCuZn ferrites with different contents of CaO-B₂O₃-SiO₂ glasses were synthesized by a conventional ceramic technology and sintered at 1050 °C. It was found that the addition of CaO-B₂O₃-SiO₂ influenced the magnetic and dielectric properties of the ferrites. The saturation magnetization increased at first and reached its maximum with the sample of 2 wt% CaO-B₂O₃-SiO₂, and then decreased. The initial permeability decreased with the content of CaO-B₂O₃-SiO₂ but the cut-off frequency increased. The quality factor decreased first and then increased; the maximum quality factor was obtained in the sample with 3 wt% CaO-B₂O₃-SiO₂. With increasing content of CaO-B₂O₃-SiO₂, the permittivity increased sharply. The possible reasons responsible for these changes are explained.     

Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.     

Redox equilibrium of samarium ions doped in Al2O3-SiO2 glasses

Redox reaction of samarium ions doped in Al₂O₃-SiO₂ glasses, prepared by a rapid cooling technique of the melts, was examined by the measurement of the optical absorption and fluorescence properties. It was found that the doped samarium ions are easily reduced and oxidized by heating in H₂ and O₂ gases, respectively. The redox kinetics of samarium in the H₂ and O₂ atmospheres obey good first-order kinetics. The activation energy for the Sm³⁺ reduction in the 10Al₂O₃90SiO₂ glass was estimated to be ∼70 kJ/mol, which decreased with the increasing Al₂O₃ content. On the other hand, the activation energies for the oxidation were ∼90 kJ/mol, which only slightly depends on the glass composition. In these glasses, the samarium ions are preferentially surrounded by the Al-O polyhedra, where the oxygen ions are easily removed to form defect centers. It was concluded that the movement of the oxygen ions in the Al-O polyhedra determine the redox equilibrium of the samarium ions.     

AgI(Cr2O3)混合离子导体改性的机理研究

本文研究了Agl(Cr₂O₃)混合离子导体的红外吸收光谱、近紫外、可见反射光谱,透射电子显微镜的显微形貌及成份分析,发现混合离子导体的微观结构与纯Agl,Cr₂O₃不同。由透射电子显微镜的显微形貌得出不同于他人的介质模型。提出电介质引起的变形极化,导致了微观精细结构改变的观点。并对其物性改变的机理给予了讨论。 关键词：     

Complex impedance spectroscopy studies of (La0.70−xNdx)Sr0.30Mn0.70Cr0.30O3 (x≤0.30) perovskite compounds

The transport properties of Nd-doped perovskite materials (La_0.7−xNd_x)Sr_0.3Mn_0.7Cr_0.3O₃ (x≤0.30) were investigated using impedance spectroscopy techniques over a wide range of temperatures and frequencies. AC conductance analyses indicate that the conduction mechanism is strongly dependent on temperature and frequency. The DC conductance plots can be described using the small polaron hopping (SPH) model, with an apparent reduction of the polaron activation energy below the Curie temperature T_C. Complex impedance plots exhibit semicircular arcs described by an electrical equivalent circuit. Off-centered semicircular impedance plots show that the Nd-doped compounds obey to a non-Debye relaxation process. The conductivity of grains and grain-boundaries has been estimated. The activation energies calculated from the conductance and from time relaxation analyses are comparable. This indicates that the same type of charge carriers is responsible for both the electrical conduction and relaxation phenomena.     

Low-temperature electronic and magnetic transitions in the antiferromagnetic semiconductor Cr0.5Mn0.5S

Experimental-theoretical studies were carried out of the electrical and magnetic properties of the antiferromagnetic semiconductor Cr_0.5Mn_0.5S in the temperature range 4.2–300 K. A magnetic antiferromagnetic-ferrimagnetic phase transition was observed along with a semimetalsemiconductor electronic transition. Monte Carlo calculations indicate that the changes in the type of magnetic ordering and conductivity are due to the cooperative Jahn-Teller effect caused by the Cr₂₊ ions. Fiz. Tverd. Tela (St. Petersburg) 41, 1660–1664 (September 1999)     

Multiplet splitting patterns exhibited by the first row transition metal oxides in X-ray photoelectron spectroscopy

High resolution photoelectron spectra from transition metal ions in TiO₂, V₂O₅, VO₂, V₂O₃, MnO, Mn₂O₃, MnO₂, Cr₂O₃, FeO, CoO, NiO, CuO, Cu₂O, FeSrO₃, and Cu doped CaTiO₃ were re-examined using a constrained curve fitting approach. Effective fits of the multiplet splitting present could be attained for the oxides with unfilled 3d bands if multiple final states were assumed. The type of transitions implied, also suggest the classification of these oxides during core level photoelectron emission as either; Mott–Hubbard (V₂O₅, VO₂, V₂O₃, Cr₂O₃, and FeO), intermediate (MnO, Mn₂O₃, and MnO₂) or charge transfer type compounds (FeSrO₃, CoO, NiO, CuO and Cu doped CaTiO₃). These transitions along with relationships defining the splitting energy with respect to the total spin and binding energy are discussed.     

Thermochemical and electrochemical study of sodium and zinc insertion into α-UO3 − y and α-U3O8

New sodium and zinc insertion compounds of the uranium oxides UO_2.95(α-UO₃) and UO_2.67(α-U₃O₈), were synthesized at ambient temperature. Enthalpies of formation were measured calorimetrically and corresponding free energies of formation were determined electrochemically. Electronic changes on insertion were monitored by measurements of magnetic susceptibilities.     

On the use of NiO as sintering additive for BaCe0,9Y0,1O3 − α

The effect of nickel oxide addition on the densification behaviour and electrical conductivity of BaCe_0.9Y_0.1O_3 ? α (BCY10) is investigated. Small addition (4 mol%) of this sintering aid reduces the sintering temperature by 200 °C and promotes the densification. 95% of the theoretical density was reached after sintering at 1250 °C for 10 h in air. Addition of NiO has no detrimental effect on the total conductivity of BCY10 in wet hydrogen. Nevertheless, the activation energy of the recorded blocking effect is higher than that of the bulk contribution, indicating different electrical properties between grains and internal interfaces in pure and NiO doped BCY10.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Horizontally networked carbon nanotubes grown on Au–Fe catalyst nanoparticles

Undoped and doped indium tin oxide (ITO) with different concentrations (2, 4, and 6 mol%) of different dopants (CuO, Cr₂O₃, and ZrO₂) were prepared in the nano-size scale (19–33 nm) using Pechini method. The thermal decomposition of the precursors was studied. The electrical properties of all the prepared samples were investigated. All the investigated systems have higher conductivity than that of ITO. For ITO doped with CuO, as the concentration of CuO increases, the conductivity increases. The highest conductivity was obtained for ITO doped with 6 mol% of CuO. For ITO doped with Cr₂O₃, as the concentration of Cr₂O₃ increases the conductivity increases and above 4 mol% Cr₂O₃ the conductivity decreases. For ITO doped with ZrO₂, as the ZrO₂ concentration increases, the conductivity increases up to 4 mol% of ZrO₂ and then decreases. The band gap was detected for all the investigated systems.     

Hydrogen-Water Deuterium Exchange Reaction Over Mixed Oxide Supported Nickel Catalysts

Three series of catalysts, Ni/Al₂O₃-SiO₂, Ni/Al₂O₃-Cr₂O₃ and Ni/SiO₂-Cr₂O₃, were prepared by co-precipitation. In all samples the nickel content was kept constant at 70 at.% Ni, while the support composition was varied. The nickel surface areas, which are required to measure the specific catalytic activities, were determined by hydrogen chemisorption. In the case of the single oxide supported nickel catalysts, the order of the specific catalytic activity values was: Ni/Cr₂O₃<Ni/Al₂O₃<Ni/SiO₂. The specific catalytic activity of the Ni/Al₂O₃-SiO₂ samples, as a function of the support composition, follows approximately the weighted sum of the specific activities of the single oxide supported nickel catalysts. The specific catalytic activity value of the Ni/Al₂O₃-Cr₂O₃ and Ni/SiO₂-Cr₂O₃ samples more closely resembled that of Ni/Cr₂O₃ catalyst. The presence on chromia surface of the chromic anhydride and its tendency to spread onto are supposed to be the cause of this behaviour. Due to their enhanced activity, the Ni/Al₂O₃-Cr₂O₃ catalysts can be used for the production and detritiation of heavy water.     

Thermodynamic test of defect formation energies calculated by simulation techniques for nonstoichiometric oxides. application to CeO2−x, UO2 ± x, TiO2−x, Mn1−xO,Fe1−xO

A relation has been derived between (i) ΔH(O₂), the partial molar enthalpy of mixing of oxygen in a nonstoichiometric oxide, which may be directly measured by high temperature microcalorimetry, and (ii) the defect formation energies which may be calculated by simulation techniques. This relation permits the testing of the consistency between the experimental ΔH(O₂) and the theoretical defect formation energies. This thermodynamic test, though necessary, is not sufficient since it does not take entropy terms into account. As yet this test can be rigorously applied only for small deviations from stoichiometry, but may be however very useful for large deviations. Applications have been developed for the oxides UO_2+x, UO_2?x, TiO_2?x, Mn_1?xO, Fe_1?xO and CeO_2?x. For the first five oxides, it concluded that the theoretical formation energies for the majority defects derived from simulation calculations are not compatible with experimental ΔH(O₂). A good agreement is found for CeO_2?x.     

Electrical conduction in Fe2O3 and Cr2O3

The influence of some impurities on the conduction properties of Cr₂O₃ and Fe₂O₃ are examined and contrasted. A mechanism is proposed to account for the effect of Ti in Cr₂O₃.     

Transport properties of lead phosphate glass doped by cobalt,vanadium and chromium oxides

The electrical transport properties were investigated of a glass system of basic composition 50?mol. % Pb₃O₄–50?mol. % P₂O₅ containing CoO, Cr₂O₃ or V₂O₅ dopanys. The ac conductivity and the thermoelectric power were measured as a function of temperature. Properties such as dielectric constant, loss factor tangent and electrical conductivity are reported in the frequency range 200?Hz–100?kHz and temperature range 300–450?K. The variation in electrical conductivity with temperature was found to depend on the types of transition metal ions involved. The temperature dependence of the frequency exponent, s, was analyzed using different theoretical models. The variation of the thermoelectric power with temperature indicated the presence of more than one conduction mechanism for the investigated samples. This result was confirmed with the results of the dielectric properties at different frequencies. The introduction of cobalt ions in glass formers improves the electrical properties of non-crystalline ionic conductors.     

An ultrasonic characterization of ferrofluid

Nanoparticles of Cr₂O₃ are prepared through hydrothermal synthesis process using CrO₃/PVA in aqueous solution using sucrose as a reducing agent. The calcination temperature is taken 300 and 350 °C. XRD and SEM of the powdered Cr₂O₃ particles are done for the characterization. The average particle size is found 30–80 nm. It is found that average particle size increases with calcination temperature. The UV–visible absorption spectra are taken for the study of photo-physical properties of ferrofluids. Ultrasonic velocity and absorption measurements are performed in Cr₂O₃ ferrofluid using variable path interferometer and pulse-echo techniques, respectively. The achieved results are discussed in correlation with the magnetic and other physical properties of Cr₂O₃.     

Electronic excitations on clean and adsorbate-covered oxide surfaces

We have studied electronic excitations at the surfaces of NiO (100), Cr₂O₃(111), and Al₂O₃(111) thin films with Electron Energy Loss Spectroscopy (EELS). On NiO (100) we observe surface electronic excitations in the energy range of the band gap which shift upon adsorption of NO. Ab initio cluster calculations show that these excitations occur within the Ni ions at the oxide surface. The (111) surface of Cr₂O₃ is characterized by distinct excitations which are also strongly influenced by the interaction with adsorbates. Temperature-dependent measurements show that two different states of the surface exist which are separated by an activation energy of about 10 meV. For Al₂O₃(111) we present data for a CO adsorbate. The oxide is quite inert with respect to CO adsorption as indicated by desorption temperatures between 38 K and 67 K. Due to the weak interaction with the substrate the a³II valence excitation of CO shows a clearly detectable vibrational splitting which has not been observed previously for a CO adsorbate in the (sub)monolayer coverage range. For several different adsorption state the lifetimes of the a³II state could be estimated from the halfwidths of the loss peaks, yielding values between 10^–15 s for the most strongly bound species and 10^–14 s for the CO multilayer.