Oxide-solution interfaces, theoretical model

Numerous studies have attempted to elucidate the role of Mo in the passivity of stainless steel. It has been proposed from XPS studies that Mo forms a solid solution with CrOOH with the result tiiat Mo is inhibited from dissolving trans-passively [9]. Others have proposed that active sites are rapidly covered with molybdenum oxyhydroxide or molybdate salts, thereby inhibiting localized corrosion [10]. Yet another study proposed that molybdate is formed by oxidation of an Mo dissolution product [11]. The oxyanion is then precipitated preferentially at active sites, where repassivation follows. It has also been proposed that in an oxide lattice dominated by three-valent species of Cr and Fe, ferrous ions will be accompanied by point defects. These defects are conjectured to be canceled by the presence of four- and six-valent Mo species [1]. Hence, the more defect-free film will be less able to be penetrated by aggressive anions. A theoretical study proposed a solute vacancy interaction model in which Mo " is assumed to interact electrostatically with oppositely charged cation vacancies [ 12]. As a consequence, the cation vacancy flux is gradually reduced in the passive film from the solution side to the metal-film interface, thus hindering vacancy condensation at the metal-oxide interface, which the authors postulate acts as a precursor for localized film breakdown [12]. 

Polymers can adsorb spontaneously from solution on to surfaces if the interaction between the polymer and the surface is more favorable than that of the solvent with the surface. For example, a polymer like poly(ethylene oxide) (PEO) is soluble in water but will adsorb on various hydrophobic surfaces and on the water/air interface. This is the case of equilibrium adsorption where the concentration of the polymer monomers increases close to the surface with respect to their concentration in the bulk solution. We discuss this phenomenon at length both on the level of a single polymer chain (valid only for extremely dilute polymer solutions), see Section II, and for polymers adsorbing from (semidilute) solutions, see Section III. In Fig. 2a we schematically show the volume fraction profile (p(z) of monomers as a function of the distance z from the adsorbing substrate. In the bulk, i.e., far away from the substrate surface, the volume fraction of the monomers is (p], whereas, at the surface, the corresponding value is (p > (p]. The theoretical models address questions in relation to the polymer conformations at the interface, the local concentration of polymer in the vicinity of the surface, and the total amount of adsorbing polymer chains. In turn, the knowledge of the polymer interfacial behavior is used to calcu-... 

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