Microstructural and magnetic characterization of Nd2Fe17 ball milled alloys

Microstructural and magnetic changes induced by ball milling in Nd₂Fe₁₇ alloy have been investigated. X-ray and neutron powder diffraction studies have shown that the main crystalline phase present in the as-cast Nd₂Fe₁₇ compound is the rhombohedral Th₂Zn₁₇-type crystal structure. Contrary to other materials, the crystal structure does not change after milling, and the crystal lattice parameters slightly increases while the induced strain is less than 0.1%. It has been observed from SEM and TEM images that the microstructure consists of agglomerates of nanoparticles with a mean size around 20 nm, and from magnetic measurements a broadening of the temperature range in which ferromagnetic to paramagnetic transition takes place.     

N‐σ versus π configuration in mono‐ and bis‐pyrrole and imidazole derivatives of alkaline earth metals

A theoretical study of the preferred N‐σ or π configuration of the mono‐ and bis‐pyrrole and imidazole derivatives of alkaline earth metals has been carried by means of DFT and ab initio methods, up to G2 computational level. The energetic results show that the beryllium derivatives prefer the N‐σ configuration while the calcium ones prefer the π one. In the case of magnesium, both configurations present similar stability. The calculated dissociation enthalpies correspond to the fact that the metallic atom is strongly bonded to the azoles in both configurations. The NBO analysis shows that the systems can be considered as formed by the azolates interacting with the charged metallic atom and thus the Natural Energy Decomposition Analysis (NEDA) indicates that the main attractive force is the electrostatic. Copyright © 2009 John Wiley & Sons, Ltd.     

Control of spontaneous emission by complex nanostructures

Spontaneous emission in the presence of complex nanostructures is discussed by use of a calculational scheme that permits us to deal with interfaces of arbitrary shape. Control over the field associated with the emission is shown to be attainable. In particular, decay rates are offered for geometries that lead to focusing and collimation of near- and far-field distributions. Emission from axially symmetric gratings is shown to lead to narrow angular distributions of emission, and focusing at the foci of dielectric ellipsoids is achieved for dimensions comparable with the wavelength. In the latter case the total emission rate for two atoms in an ellipsoidal cavity is shown to be enhanced in a way that deviates from the predictions of the Dicke effect by means of intermediate- and far-field contributions.     

Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Control of crystalline phases in magnetic Fe nanoparticles inserted inside a matrix of porous carbon

Two magnetic composites made up of Fe nanoparticles (Fe-NPs) embedded in a porous amorphous carbon matrix are presented. One of the samples, Fe-S-AC, was obtained with the aid of sucrose and the other, Fe-AC, in the absence of this substance. The XRD patterns show Bragg diffraction peaks associated with α-Fe and γ-Fe crystalline phases in the Fe-AC sample, while only peaks corresponding to the α-Fe phase are observed for Fe-S-AC powders. The Fe-NPs exhibit broad particle-size distributions for both samples, 5–50 nm for Fe-AC, whereas two populations (2–8 and 10–70 nm) for the Fe-S-AC composite are found. This fact gives rise to poorly defined blocking temperatures, as it can be deduced from the broad maxima observed in M_ZFC(T) variations. In addition, M(H) curves for both Fe-AC and Fe-S-AC samples reveal the existence of exchange-bias effect for T<60 K, probably due to a magnetic coupling within a core/shell structure of the Fe-NPs, although this effect was observed to be less significant for Fe-S-AC.     

Magneto-volume effects in Fe–Cu solid solutions

The magnetic properties of Fe–Cu metastable solid solutions have been investigated by means of neutron diffraction and magnetisation measurements. These compounds exhibit ferromagnetic order with Curie temperatures above room temperature for concentrations beyond 40 at% in Fe. The magnetic moment at 5 K can reach values over 2 μ_B, while the high field susceptibility is similar to that found in FCC–FeNi Invar alloys. These features together with the low values for the linear coefficient for thermal expansion in the ferromagnetic region suggest that magneto-volume anomalies, including Invar behaviour, play a major role in the magnetic properties of this system when the crystal structure is face centred cubic. Such behaviour could be explained using theoretical total-band energy calculations.     

Ionic mobility and ionic association of singly charged ions in glycerol

Experimental molar conductivity data for KCl, NaCl and LiCl in glycerol at 298.15?K were analysed by least-square fitting in the concentration range 0.5–100?mol?m^?3in order to compute the values of the molar conductivity at infinite dilution Λ⁰and the Onsager constant S. Using previously measured transference numbers and assuming the Kohlrausch infinite dilution law, the limiting ionic mobilities were deduced. The results obtained show that the transport mechanisms in this solvent and other similar hydrogen-bonded solvents such as water and ethylene glycol are the same. The data were also interpreted in terms of ion–ion and ion–solvent interactions using the Fuoss paired ion model in the concentration range 0.5–100?mol?m^?3. The fitting of Fuoss’ equation of 1978 to these data led us to an estimate of the ionic association by computing the conductimetric pairing constants. The latter were further analysed by Gilkerson's equation to yield the difference between the solvation energy of the free ions and the ion pairs. The computed values allow an estimation of whether the electrolyte is a structure maker or a structure breaker.     

The Blume-Emery-Griffiths neural network with synchronous updating and variable dilution

The thermodynamic and retrieval properties of the Blume-Emery-Griffiths neural network with synchronous updating and variable dilution are studied using replica mean-field theory. Several forms of dilution are allowed by pruning the different types of couplings present in the Hamiltonian. The appearance and properties of two-cycles are discussed. Capacity-temperature phase diagrams are derived for several values of the pattern activity. The results are compared with those for sequential updating. The effect of self-coupling is studied. Furthermore, the optimal combination of dilution parameters giving the largest critical capacity is obtained.     

Observation of resonant behavior in the energy velocity of diffused light

In this Letter we demonstrate Mie resonances mediated transport of light in randomly arranged, monodisperse dielectric spheres packed at high filling fractions. By means of both static and dynamic optical experiments we show resonant behavior in the key transport parameters and, in particular, we find that the energy transport velocity, which is lower than the group velocity, also displays a resonant behavior.