The aim of this study is to develop polymeric thin films for corrosion protection of magnesium alloy AZ31. As polymer matrix, poly(4-vinyl pyridine) (P4VP) is selected due to its semiconducting properties and protonic conductivity. Polyacrylic acid is tested as crosslinking layers to improve interfacial adhesion. The macroscopic corrosion properties of the multilayer coatings are investigated by means of electrochemical methods, such as linear sweep voltammetry and electrochemical impedance spectroscopy (EIS), in corrosive media simulating technical and biomedical applications. It is demonstrated that thin multilayer coatings can suppress the corrosion rates of magnesium alloys. To our best knowledge, this is the first demonstration of the use of P4VP as a conducting polymer film with protonic conductivity for corrosion protection of magnesium alloys.
Water-stable metal−organic frameworks (MOFs) with proton-conducting behavior have attracted great attention as promising materials for proton-exchange membrane fuel cells. Herein, we report the mechanochemical gram-scale synthesis of three new mixed-ligand phosphonate-based MOFs, {Co(H2PhDPA)(4,4′-bipy)H2O)·2H2O}n (BAM-1), {Fe(H2PhDPA)(4,4′-bipy) (H2O)·2H2O}n (BAM-2), and {Cu(H2PhDPA)(dpe)2(H2O)2·2H2O}n (BAM-3) [where H2PhDPA = phenylene diphosphonate, 4,4′-bipy = 4,4′-bipyridine, and dpe = 1,2-di(4-pyridyl)ethylene]. Single-crystal X-ray diffraction measurements revealed that BAM-1 and BAM-2 are isostructural and possess a three-dimensional (3D) network structure comprising one-dimensional (1D) channels filled with guest water molecules. Instead, BAM-3 displays a 1D network structure extended into a 3D supramolecular structure through hydrogenbonding and π−π interactions. In all three structures, guest water molecules are interconnected with the uncoordinated acidic hydroxyl groups of the phosphonate moieties and coordinated water molecules by means of extended hydrogen-bonding interactions. BAM-1 and BAM-2 showed a gradual increase in proton conductivity with increasing temperature and reached 4.9 × 10−5 and 4.4 × 10−5 S cm−1 at 90 °C and 98% relative humidity (RH). The highest proton conductivity recorded for BAM-3 was 1.4 × 10−5 S cm−1 at 50 °C and 98% RH. Upon further heating, BAM-3 undergoes dehydration followed by a phase transition to another crystalline form which largely affects its performance. All compounds exhibited a proton hopping (Grotthuss model) mechanism, as suggested by their low activation energy.
Mg is a very promising material for lightweight construction and biomedical applications. However, the applicability of Mg and its alloys is hindered by its high corrosion susceptibility. Moreover, due to the toxicity of most inorganic conversion coating systems, the development of novel pre-treatment strategies for technical alloys are of vital importance. The aim of this study is to develop polymeric bilayer thin films for corrosion protection of Mg-alloys. As polymer matrix, poly(4-vinyl pyridine) (P4VP) was selected due to its semiconducting properties and protonic conductivity. In contrast to ICPs with electronic conductivity, the pH-dependant, reversible protonation/de-protonation capability of the P4VP has been utilized to synthesize environment-responsive coatings. Polyacrylicacid (PAA) was tested as crosslinking layers to improve interfacial interactions between the polymeric layers. The macroscopic corrosion properties of the bilayer coatings were investigated by means of electrochemical methods such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) in corrosive media simulating technical and biomedical applications. The presentation summarizes our recent results on the synthesis and characterization of this novel coating system with a special focus on their interfacial stability and corrosion protection properties.
Mg is a very promising material for lightweight construction and biomedical applications. However, the applicability of Mg and its alloys is hindered by its high corrosion susceptibility. Moreover, due to the toxicity of most inorganic conversion coating systems, the development of novel pre-treatment strategies for technical alloys are of vital importance. Recently, the application of intrinsically conducting polymers (ICPs) have been introduced as an alternative approach for corrosion protection of Mg alloys. ICPs with electronic conductivity are known to be able to passivate small defects, however they fail in the presence of large defects due to fast coating reduction and increased cation transport if macroscopically extended percolation networks exist.
The aim of this study is to develop graphene-polymer nanocomposite thin films for corrosion protection of Mg-alloys. As polymer matrix, poly(4-vinyl pyridine) (P4VP) was selected due to its semiconducting properties and protonic conductivity. In contrast to ICPs with electronic conductivity, the pH-dependant, reversible protonation/de-protonation capability of the P4VP has been utilized to synthesize environment-responsive coatings. The presentation summarizes our recent results on the synthesis and characterization of this novel coating system with a special focus on their interfacial stability and corrosion protection properties.
Crystalline porous materials are recognized as promising proton conductors for the proton exchange membrane (PEM) in fuel cell technology owing to their tunable framework structure. However, it is still a challenging bulk synthesis for real-world applications of these materials. Herein, we report the mechanochemical gram-scale synthesis of two isostructural metal hydrogen-bonded organic frameworks (MHOFs) of Co(II) and Ni(II) based on 1-hydroxyethylidenediphosphonic acid (HEDPH4) with 2,2′-bipyridine (2,2′-bipy): Co(HEDPH3)2(2,2′-bipy)·H2O (1) and Ni(HEDPH3)2(2,2′-bipy)·H2O (2). In situ monitoring of the mechanochemical synthesis using different synchrotron-based techniques revealed a one-step mechanism – the starting materials are directly converted to the product. With the existence of extensive hydrogen bonds with amphiprotic uncoordinated phosphonate hydroxyl and oxygen atoms, both frameworks exhibited proton conduction in the range of 10–4 S cm–1 at room temperature under humid conditions. This study demonstrates the potential of green mechanosynthesis for bulk material preparation of framework-based solid-state proton conductors.