The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions.

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The adsorption of poly(vinylformamide) (PVFA) and its derivative statistical copolymer poly(vinyl-formamide-co-vinylamine) (PVFA-co-PVAm) on metallic copper and copper oxide particles as well as planar copper surfaces was studied as a function of the degree of hydrolysis of PVFA, the pH, and the polymer concentration in solution. The chemical composition and molecular structure of the PVFA-co-PVAm layers were investigated by surface-sensitive spectroscopic methods such as XPS, DRIFT spectroscopy, and ellipsometry. The findings allowed us to explain the adsorption mechanisms and the forces driving the PVFA-co-PVAm adsorption. It was shown that PVFA-co-PVAm layers thicker than 30 nm are able to protect the planar copper surface against corrosive attack.

Poly(vinyl amine) (PVAm) reacts with acetone in aqueous solution. It generates imine and aminal moieties along the PVAm backbone. The molecular structure of acetone‐modified PVAm is confirmed by liquid 1H and 13C as well as solid state 13C NMR and ATR‐FTIR spectroscopies. Model compounds produced from 1,3‐diaminopropane with acetone in chloroform are used to assign the solid state 13C NMR signals of the modified polymer. Quantitative elemental analysis of acetone‐modified PVAm samples supports the analytical results. The mechanism of the imine and aminal formation is discussed with regard to the anomeric stabilization of the incipient hemiaminal intermediate. The rapid and unexpectedly favorable formation of PVAm acetone hemiaminal, acetone imine, and aminal formation has implications for the conduct of PVAm research and even the interpretation of prior published results. As acetone was often used in the past to precipitate waterborne PVAm derivatives, this finding has a severe impact on the interpretation of research results. The consequences and the revised interpretation of selected publications are discussed.