abstract: The passivity of metals is a phenomenon of vast importance as it prevents many materials in important applications from rapid deterioration by corrosion. Alloying with a sufficient quantity of passivating elements (Cr, Al, Si), typically in the range of 10% - 20%, is commonly employed to improve the corrosion resistance of elemental metals. However, the compositional criteria for enhanced corrosion resistance have been a long-standing unanswered question for alloys design. With the emerging interest in multi-principal element alloy design, a percolation model is developed herein for the initial stage of passive film formation, termed primary passivation. The successful validation of the assumptions and predictions of the model in three corrosion-resistant binary alloys, Fe-Cr, Ni-Cr, and Cu-Rh supports that the model which can be used to provide a quantitative design strategy for designing corrosion-resistant alloys. To date, this is the only model that can provide such criteria for alloy design.The model relates alloy passivation to site percolation of the passivating elements in the alloy matrix. In the initial passivation stage, Fe (Ni in Ni-Cr or Cu in Cu-Rh) is selectively dissolved, destroying the passive network built up by Cr (or Rh) oxides and undercutting isolated incipient Cr (Rh) oxide nuclei. The only way to prevent undercutting and form a stable protective passive film is if the concentration of Cr (Rh) is high enough to realize site percolation within the thickness of the passive film or the dissolution depth. This 2D-3D percolation cross-over transition explains the compositional dependent passivation of these alloys. The theoretical description of the transition and its assumptions is examined via experiments and kinetic Monte Carlo simulations. The initial passivation scenario of the dissolution selectivity is validated by the inductively coupled plasma mass spectrum (ICP-MS). The electronic effect not considered in the kinetic Monte Carlo simulations is addressed by density functional theory (DFT). Additionally, the impact of the atomic configuration parameter on alloy passivation is experimentally measured, which turns out to agree well with the model predictions developed using Monte Carlo renormalization group (MC-RNG) methods. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020