Composition- and temperature-dependent liquid structures in Al-Cu alloys: an ab initio molecular dynamics and x-ray...

The composition- and temperature-dependent liquid structures in eight Al_rich-Cu binary alloys (from hypoeutectic Al₉₃Cu₇ to hypereutectic Al₇₀Cu₃₀) have been experimentally and computationally studied by x-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. The remarkable agreements of structure factors for all liquid Al_rich-Cu alloys obtained from high-temperature high-energy XRD measurements and AIMD simulations have been achieved, which consolidates the analyses of structural evolutions in Al_rich-Cu liquids during the cooling processing by AIMD simulations. The heat capacity of liquid Al_rich-Cu alloys continuously increases and presents no abnormal peak when reducing the temperature, which differs from the reported prediction for 55-atom Al_rich-Cu nanoliquids. The diffusivities of Al and Cu undergo an increasing deviation from Arrhenius behavior by tuning Cu concentration from 7 to 30 atomic percentages, correlated to the local ordering in these liquids by means of coordination number, bond-angle distribution, Honeycutt-Andersen index, bond-orientational order and Voronoi tessellation analyses. Upon cooling, the microstructure of the liquid Al_rich-Cu alloys inclines to form Al₂Cu crystal-like local atomic ordering, especially in the hypereutectic liquids. The favorable short-range ordering between Cu and Al atoms could cause the non-Arrhenius diffusion behavior.