Scaffolding, ladders, chains, and rare ferrimagnetism in intermetallic borides: electronic structure calculations and magnetic ordering

The electronic structures of "Ti(9-n)Fe(2+n)Ru(18)B(8)" (n=0, 0.5, 1, 2, 3), in connection to the recently synthesized Ti(9-n)Fe(2+n)Ru(18)B(8) (n=1, 2), have been investigated and analyzed using LSDA tight-binding calculations to elucidate the distribution of Fe and Ti, to determine the maximum Fe content, and to explore possible magnetic structures to interpret experimental magnetization results. Through a combination of calculations on specific models and using the rigid band approximation, which is validated by the DOS curves for "Ti(9-n)Fe(2+n)Ru(18)B(8)" (n=0, 0.5, 1, 2, 3), mixing of Fe and Ti is anticipated at both the 2b- and 4h-chain sites. The model "Ti(8.5)Fe(2.5)Ru(18)B(8)" (n=0.5) revealed that both Brewer-type Ti-Ru interactions as well as ligand field splitting of the Fe 3d orbitals regulated the observed valence electron counts between 220 and 228 electrons/formula unit. Finally, models of magnetic structures were created using "Ti(6)Fe(5)Ru(18)B(8)" (n=3). A rigid band analysis of the LSDA DOS curves concluded preferred ferromagnetic ordering at low Fe content (n≤0.75) and ferrimagnetic ordering at higher Fe content (n>0.75). Ferrimagnetism arises from antiferromagnetic exchange coupling in the scaffold of Fe1-ladder and 4h-chain sites.     

Scaffolding, ladders, chains, and rare ferrimagnetism in intermetallic borides: synthesis, crystal chemistry and magnetism

Single-phase polycrystalline samples and single crystals of the complex boride phases Ti(8)Fe(3)Ru(18)B(8) and Ti(7)Fe(4)Ru(18)B(8) have been synthesized by arc melting the elements. The phases were characterized by powder and single-crystal X-ray diffraction as well as energy-dispersive X-ray analysis. They are new substitutional variants of the Zn(11)Rh(18)B(8) structure type, space group P4/mbm (no. 127). The particularity of their crystal structure lies in the simultaneous presence of dumbbells which form ladders of magnetically active iron atoms along the [001] direction and two additional mixed iron/titanium chains occupying Wyckoff sites 4h and 2b. The ladder substructure is ca. 3.0 ? from the two chains at the 4h, which creates the sequence chain-ladder-chain, establishing a new structural and magnetic motif, the scaffold. The other chain (at 2b) is separated by at least 6.5 ? from this scaffold. According to magnetization measurements, Ti(8)Fe(3)Ru(18)B(8) and Ti(7)Fe(4)Ru(18)B(8) order ferrimagnetically below 210 and 220 K, respectively, with the latter having much higher magnetic moments than the former. However, the magnetic moment observed for Ti(8)Fe(3)Ru(18)B(8) is unexpectedly smaller than the recently reported Ti(9)Fe(2)Ru(18)B(8) ferromagnet. The variation of the magnetic moments observed in these new phases can be adequately understood by assuming a ferrimagnetic ordering involving the three different iron sites. Furthermore, the recorded hysteresis loops indicate a semihard magnetic behavior for the two phases. The highest H(c) value (28.6 kA/m), measured for Ti(7)Fe(4)Ru(18)B(8), lies just at the border of those of hard magnetic materials.     

Effect of Residual Stresses on Delamination Cracks in Fiber Reinforced Composites

In the processing of cross-ply fiber reinforced materials, residual stresses, as well as possible transverse cracking may arise. These affect the stress field about a delamination between two layers. In this investigation, the effect of residual stresses resulting from curing and transverse cracks is examined. A 0°/90°/0° ply system is considered with a delamination assumed between one of the 0° and 90° layers. The residual stresses along the interface without the delamination are calculated. First, this analysis is done neglecting the transverse cracks in the 90° layer. Then, the transverse cracks are included and several methods are employed to calculate the residual stresses. These include the shear lag method, a semi-analytic method and the finite element method. It is seen that the latter two methods produce similar results. By means of the superposition principle, the stress intensity factors resulting from the residual stresses are obtained for the delamination. Use is made of the conservative M-integral with tractions along the crack faces.     

Optimization of microvia-technology using excimer laser for build-up layer application in microelectronics

In interconnection microelectronics microvias play a key role in the manufacture of high-density circuitry for use in electronic systems such as portable, smart sensors and computing applications. In the current work an excimer laser is used and microvias in the dielectric of the build-up layer are generated with the mask imaging method. Different laser parameters (demagnification factor, energy transmission percentage, fluence) are optimised in order to obtain microvias with different diameters, taper angle and aspect ratio. With electrochemical Cu-deposition interconnections between the upper and the underlying circuitry are realised. A nearly uniform thickness of the plated copper is obtained, and quality of the plating is assessed by means of the degree of delamination of the electrochemically deposited copper.     

An all-speed relaxation scheme for interface flows with surface tension

We consider interface flows where compressibility and capillary forces (surface tension) are significant. These flows are described by a non-conservative, unconditionally hyperbolic multiphase model. The numerical approximation is based on finite-volume method for unstructured grids. At the discrete level, the surface tension is approximated by a volume force (CSF formulation). The interface physical properties are recovered by designing an appropriate linearized Riemann solver (Relaxation scheme) that prevents spurious oscillations near material interfaces. For low-speed flows, a preconditioning linearization is proposed and the low Mach asymptotic is formally recovered. Numerical computations, for a bubble equilibrium, converge to the required Laplace law and the dynamic of a drop, falling under gravity, is in agreement with experimental observations.     

Orbites hétérocliniques au voisinage d'une bifurcation de Poincaré dégénérée pour les champs de vecteurs de ℝ2

We consider a ²-ordinary differential equation, where the fixed point (0, 0) presents a degenerate Poincaré-bifurcation of resonancek(=2k) and dominanced(=k–1). We prove the existence of a 2-dimensional linear manifoldV in the parameter space. , on which the perturbed dominant differential system (SD) possesses heteroclinic orbits between fixed points. The numerical continuation of the local stable or unstable manifolds of the saddle fixed points shows that for any neighborhood, in , of a point ofV corresponding to a saddle heteroclinic orbit, there exists only one stable (resp. unstable) periodic orbit close to the stable — in the Andronov sense [1]-(resp. unstable) heteroclinic orbit. Applications are given fork=4 andk=6.     

Electrocatalytic activity of carbon-supported metallophthalocyanine catalysts toward oxygen reduction reaction in alkaline solution

Carbon-supported metallophthalocyanine catalysts, composed of a transition central metal M (M = Co, Mn, Ni, Fe) in the phthalocyanine ring, were synthesized in this work. As cathodic reaction in a fuel cell, the oxygen reduction reaction (ORR) was investigated in alkaline medium with linear scanning voltammetry at the surface of these electrocatalysts deposited onto a rotating disk electrode (RDE). It was found that the number of electrons transferred depended on the nature of the metallic cation in the catalyst. Evidences provided with Koutecky-Levich approach showed that iron phthalocyanine (FePc) exhibited the better electrocatalytic ability toward the ORR with four electrons exchanged and low activation overpotential. Among these different as-prepared materials, MnPc and FePc led to a four-electron pathway, while CoPc and NiPc proceeded by a two-electron route. The latter reaction process was also determined with a rotating ring-disk electrode (RRDE), which allowed the determination of hydrogen peroxide formed as O₂ reduction intermediate in a small amount, i.e., less than 1.2 %.