Rutile TiO 2 was formulated into polyurethane/polysiloxane hybrid coatings in order to investigate the influence of pigmentation on the inorganic phase of the hybrid coatings. Two urethanes were prepared from the isocyanurate of hexane diisocyanate (HDI), alkoxysilane modified HDI, and tetraethyl orthosilicate (TEOS) oligomers, with oligoesters derived from either cyclohexane diacids (CHDA) and 2-butyl-2-ethyl-1,3-propanediol (BEPD) or adipic acid (AA), isophthalic acid (IPA), 1,6-hexanediol (HD), and trimethylol propane (TMP). The oligoesters were spectroscopically characterized using GPC, FT-IR, and NMR. Chemical interaction between the TiO 2 and the sol-gel precursor was investigated using solid-state 29 Si NMR and XPS. The morphology, mechanical, viscoelastic, thermal properties of the pigmented coatings are evaluated as a function of pigmentation volume concentration (PVC). Using AFM and SEM, the pigment was observed to be well dispersed in the polymer binder. The thermal stability, the tensile modulus, and strength of the coatings were enhanced with increasing PVC, whereas the pull-off adhesion and flexibility (elongation-at-break) were reduced with increasing PVC. Finally, the pigmented coatings were evaluated by electrochemical impedance spectroscopy (EIS) and the results showed that 10 wt % of the pigment improved the corrosion resistance of the entire coating system.
We investigate the transpassivity of superaustenitic stainless steel UNS N08367 in 2.5 M LiCl solution by using cyclic potentiodynamic polarization (CPP), electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). The CPP curve exhibits negative hysteresis, which indicates a transpassive dissolution process instead of pitting corrosion. The transition from the passive region to the transpassive region is characterized by EIS and equivalent circuit analysis. During the transpassive dissolution of the N08367 alloy, two reactions of adsorbed intermediates are dominant, as indicated by the two inductive loops at the transpassive region. The first inductive loop is associated with the faster reaction, i.e., the adsorption of Fe intermediates. This fast reaction is significantly influenced by the preferential dissolution of Fe during the transpassive dissolution. The second inductive loop is correlated with the adsorption of the Cr intermediate. In contrast to Fe, the Cr content on the surface increases in the transpassive region compared with the content in the passive region. The XPS spectra support the time and frequency domain approach for the preferential dissolution, and the dominant species resulted from the interfacial processes at the transpassive region.
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