Ab initio molecular dynamics study of interactions between isolated polyhedral oligomeric silsesquioxane trisilanols and aluminum

Trisilanol polyhedral oligomeric silsesquioxane (POSS) are a category of inorganic–organic material that comprise an inorganic open cage silica structure, organic attachments, and silanol (SiOH) groups. Recently, trisilanol POSS was added to Al-based alloys, and found to promote substantial microstructural refinement, and improved mechanical strength and fatigue life compared to conventional compositions. Such microstructural modifications and property enhancements are usually attributed to silanolAl bonds that formed within the liquid-state, prior to solidification. However, details of such high-temperature chemical interactions remain unclear. Here, we performed ab initio molecular dynamics simulations at 1500 K, to probe the chemical interactions between isolated trisilanol POSS molecule and discreet Al atoms. Al atoms modified the silanol groups to form, two energetically favorable coordinate complexes: monodentate SiOAl and bidentate (SiO)2Al. Such complexes were formed by Al atoms attracting electrons towards themselves from the POSS molecule. Crucially, this bonding mechanism allowed trisilanol POSS to organize the neighboring Al atoms into geometric motifs that can potentially serve as nucleation sites within liquid-Al, and facilitate microstructural refinement.