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The roles of growth direction and Si content on the columnar/equiaxed transition and on dendritic spacings of Al–Cu–Si alloys still remain as an open field to be studied. In the present investigation, Al–6 wt-Cu–4 wt-Si and Al–6 wt-Cu alloys were directionally solidified upwards and horizontally under transient heat flow conditions. The experimental results include tip growth rate and cooling rates, optical microscopy, scanning electron microscopy energy dispersive spectrometry and dendrite arm spacings. It was found that silicon alloying contributes to significant refinement of primary/secondary dendritic spacings for the upward configuration as compared with corresponding results of the horizontal growth. Experimental growth laws are proposed, and the effects of the presence/absence of solutal convection in both growth directions are discussed.

In this work, we measured the metal-binding sites of natural and synthetic dihydroxyindole (DHI) melanins and their respective interactions with Fe(III) ions. Besides the two acid groups detected for the DHI system: catechol (Cat) and quinone-imine (QI), acetate groups were detected in the natural oligomer by potentiometric titrations. At acidic pH values, Fe(III) complexation with synthetic melanin was detected in an Fe(OH)(CatH2Cat) interaction. With an increase of pH, three new interactions occurred: dihydroxide diprotonated catechol, Fe(OH)2(CatH2Cat)−, dihydroxide monoprotonated catechol, [Fe(OH)2(CatHCat)]2−, and an interaction resulting from the association of one quinone-imine and a catechol group, [Fe(OH)2(Qi−)(CatHCat)]3−. In the natural melanin system, we detected the same interactions involving catechol and quinone-imine groups but also the metal interacts with acetate group at pH values lower than 4.0. Furthermore, interactions in the synthetic system were also characterized by infrared spectroscopy by using the characteristic vibrations of catechol and quinone-imine groups. Finally, scanning electronic microscopy (SEM) and energy-dispersive X-ray (EDS) analysis were used to examine the differences in morphology of these two systems in the absence and presence of Fe(III) ions. The mole ratio of metal and donor atoms was obtained by the EDS analysis.

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