We
demonstrate the growth of dendritic magnesium deposits with
fractal morphologies exhibiting shear moduli in excess of values for
polymeric separators upon the galvanostatic electrodeposition of metallic
Mg from Grignard reagents in symmetric Mg–Mg cells. Dendritic
growth is understood on the basis of the competing influences of reaction
rate, electrolyte transport rate, and self-diffusion barrier.
Galvanostatic electrodeposition from Grignard reagents in symmetric Mg–Mg cells is used to map Mg morphologies from fractal aggregates of 2D nanoplatelets to highly anisotropic dendrites with singular growth fronts and entangled nanowire mats.
The tight atomic packing generally exhibited by alloys and intermetallics can create the impression of their being composed of hard spheres arranged to maximize their density. As such, the atomic size factor has historically been central to explanations of the structural chemistry of these systems. However, the role atomic size plays structurally has traditionally been inferred from empirical considerations. The recently developed DFT-Chemical Pressure (CP) analysis has opened a path to investigating these effects with theory. In this article, we provide a step-by-step tutorial on the DFT-CP method for non-specialists, along with advances in the approach that broaden its applicability. A new version of the CP software package is introduced, which features an interactive system that guides the user in preparing the necessary electronic structure data and generating the CP scheme, with the results being readily visualized with a web browser (and easily incorporated into websites). For demonstration purposes, we investigate the origins of the crystal structure of K3Au5Tl, which represents an intergrowth of Laves and Zintl phase domains. Here, CP analysis reveals that the intergrowth is supported by complementary CP features of NaTl-type KTl and MgCu2-type KAu2 phases. In this way, K3Au5Tl exemplifies how CP effects can drive the merging for geometrical motifs derived from different families of intermetallics through a mechanism referred to as epitaxial stabilization.
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