Mechanisms of enhanced heterogeneous nucleation during solidification in binary Al-Mg alloys

This is the post-print version of the Article. The official published version can be accessed from the link below - Copyright @ 2012 ElsevierThe mechanisms involved in the grain refinement of Al–Mg alloys through varying the Mg content and applying intensive melt shearing were investigated. It was found that the oxide formed in Al–Mg alloys under normal melting conditions is MgAl2O4, which displays an equiaxed and faceted morphology with {1 1 1} planes exposed as its natural surfaces. Depending on the Mg content, MgAl2O4 particles exist either as oxide films in dilute Al–Mg alloys (Mg 1 wt.%). Such MgAl2O4 particles can act as potent sites for nucleation of α-Al grains, which is evidenced by the well-defined cube-on-cube orientation relationship between MgAl2O4 and α-Al. Enhanced heterogeneous nucleation in Al–Mg alloys can be attributed to the high potency of MgAl2O4 particles with a lattice misfit of 1.4% and the increased number density of MgAl2O4 particles due to either natural dispersion by the increased Mg content or forced dispersion through intensive melt shearing. It was also found that intensive melt shearing leads to significant grain refinement of dilute Al–Mg alloys by effective dispersion of the MgAl2O4 particles entrapped in oxide films, but it has marginal effect on the grain refinement of concentrated Al–Mg alloys, where MgAl2O4 particles have been naturally dispersed into individual particles by the increased Mg content.This study is funded from the EPSRC Grant EP/H026177/1

A first-principles study of tunneling magnetoresistance in Fe/MgAl2O4/Fe(001) magnetic tunnel junctions

We investigated the spin-dependent transport properties of Fe/MgAl2O4/Fe(001) magnetic tunneling junctions (MTJs) on the basis of first-principles calculations of the electronic structures and the ballistic conductance. The calculated tunneling magnetoresistance (TMR) ratio of a Fe/MgAl2O4/Fe(001) MTJ was about 160%, which was much smaller than that of a Fe/MgO/Fe(001) MTJ (1600%) for the same barrier thickness. However, there was an evanescent state with delta 1 symmetry in the energy gap around the Fermi level of normal spinel MgAl2O4, indicating the possibility of a large TMR in Fe/MgAl2O4/Fe(001) MTJs. The small TMR ratio of the Fe/MgAl2O4/Fe(001) MTJ was due to new conductive channels in the minority spin states resulting from a band-folding effect in the two-dimensional (2-D) Brillouin zone of the in-plane wave vector (k//) of the Fe electrode. Since the in-plane cell size of MgAl2O4 is twice that of the primitive in-plane cell size of bcc Fe, the bands in the boundary edges are folded, and minority-spin states coupled with the delta 1 evanescent state in the MgAl2O4 barrier appear at k//=0, which reduces the TMR ratio of the MTJs significantly.Comment: 5 pages, 6 figures, 1 tabl

Structural relaxation around substitutional Cr3+ in MgAl2O4

The structural environment of substitutional Cr3+ ion in MgAl2O4 spinel has been investigated by Cr K-edge Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopies. First-principles computations of the structural relaxation and of the XANES spectrum have been performed, with a good agreement to the experiment. The Cr-O distance is close to that in MgCr2O4, indicating a full relaxation of the first neighbors, and the second shell of Al atoms relaxes partially. These observations demonstrate that Vegard's law is not obeyed in the MgAl2O4-MgCr2O4 solid solution. Despite some angular site distortion, the local D3d symmetry of the B-site of the spinel structure is retained during the substitution of Cr for Al. Here, we show that the relaxation is accomodated by strain-induced bond buckling, with angular tilts of the Mg-centred tetrahedra around the Cr-centred octahedron. By contrast, there is no significant alteration of the angles between the edge-sharing octahedra, which build chains aligned along the three four-fold axes of the cubic structure.Comment: 7 pages, 4 figure

Synthesis of a Structured Material Based on Compact Spheres Coated with Zn or Mg Spinel

In this work, a synthesis method of coating with thin layers of MgAl2O4 or ZnAl2O4 over alpha-Al2O3 spheres were developed.The method consisted in the deposition of a primer of bohemite on the spheres, followed by the impregnation with a solution of Mg or Zn nitrates, and further thermal treatments in order to obtain MAl2O4 (M: Mg or Zn). This method was modified to improve the thickness and purity of the layer material. With this method, layers of uniform and adequate thickness and good adhesion were achieved. Pt catalysts prepared with these materials as supports displayed good catalytic performances in the n-butanedehydrogenation reaction, especially those obtained with purified supports.Fil: Bocanegra, Sonia Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Ballarini, Adriana Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Fe/Co Alloys for the Catalytic Chemical Vapor Deposition Synthesis of Single- and Double-Walled Carbon Nanotubes (CNTs). 2. The CNT−Fe/Co−MgAl2O4 System

A detailed 57Fe Mössbauer study of the Mg(0.8)Fe(0.2-y)Co(y)Al2O4 (y = 0, 0.05, 0.1, 0.15, 0.2) solid solutions and of the CNT-Fe/Co-MgAl2O4 nanocomposite powders prepared by reduction in H2-CH4 has allowed characterization of the different iron phases involved in the catalytic process of carbon nanotube (CNT) formation and to correlate these results with the carbon and CNT contents. The oxide precursors consist of defective spinels of general formulas (Mg(1-x-y)(2+)Fe(x-3alpha)(2+)Fe(2alpha)(3+)[symbol: see text](alpha)Co(y)(2+)Al2(3+))O4(2-) . The metallic phase in the CNT-Fe/Co-MgAl2O4 nanocomposite powders is mostly in the form of the ferromagnetic alpha-Fe/Co alloy with the desired composition. For high iron initial proportions, the additional formation of Fe3C and gamma-Fe-C is observed while for high cobalt initial proportions, the additional formation of a gamma-Fe/Co-C phase is favored. The higher yield of CNTs is observed for postreaction alpha-Fe(0.50)Co(0.50) catalytic particles, which form no carbide and have a narrow size distribution. Alloying is beneficial for this system with respect to the formation of CNTs

Hydrogen production by methanol steam reforming on NiSn/MgO-Al 2O3 catalysts: The role of MgO addition

The effect of the magnesia loading on the surface structure and catalytic properties of NiSn/MgO-Al2O3 catalysts for hydrogen production by methanol steam reforming has been investigated. The catalysts have been obtained by impregnation of γ-Al2O3 by the incipient wetness method, with variation of the MgO content. X-ray diffraction (XRD), BET surface area and H2-temperature programmed reduction (TPR) have been used to characterise the prepared catalysts. From this, it has been concluded that the incorporation of MgO results in the formation of MgAl 2O4 spinel, which modifies the acid-base properties of the catalysts. The formation of Ni-Sn alloys after the reductive pre-treatment has also been evidenced. The influence of the temperature of reaction and of the MgO loading on the hydrogen production by reforming of methanol has been established. Moreover, tests of catalytic stability have been carried out for more than 20 h. The carbonaceous deposits have been examined by temperature-programmed oxidation (TPO). The analysis of the catalysts after reaction has confirmed the low level of carbon formation on these catalysts. In no case, carbon nanotubes have been detected on the solids.Junta de Andalucía TEP106Ministerio de Ciencia e Innovación ENE2009-14522-C05-0