Otto van den Berg

A Shape-Recovery Polymer Coating for the Corrosion Protection of Metallic Surfaces

Self-healing polymer coatings are a type of smart material aimed for advanced corrosion protection of metals. This paper presents the synthesis and characterization of two new UV-cure self-healing coatings based on acrylated polycaprolactone polyurethanes. On a macroscopic scale, the cured films all show outstanding mechanical properties, combining relatively high Youngs modulus of up to 270 MPa with a strain at break above 350%. After thermal activation the strained films recover up to 97% of their original length. Optical and electron microscopy reveals the self-healing properties of these coatings on hot dip galvanized steel with scratches and microindentations. The temperature-induced closing of such defects restores the corrosion protection and barrier properties of the coating as shown by electrochemical impedance spectroscopy and scanning vibrating electrode technique. Therefore, such coatings are a complementary option for encapsulation-based autonomous corrosion protection systems.

100% thiol-functionalized ethylene PMOs prepared by “thiol acid–ene” chemistry

A novel thiol functionalized bis-silane PMO precursor was synthesized by highly efficient thiol acid-ene chemistry between the double bonds of 1,2-(E)-bis(triethoxysilyl)ethene and thioacetic acid. After aminolysis the self-assembly process of the formed SH-precursor with Pluronic P123 under acidic conditions yields the first 100% thiol-PMO material with good structural ordering.

Efficient microencapsulation of a liquid isocyanate with in situ shell functionalization

We report on a one-pot, facile approach for the encapsulation of the liquid hexamethylene diisocyanate isocyanurate trimer in polyurea microcapsules formed via the oil-in-water interfacial reaction of an uretonimine-modified diphenyl methane diisocyanate trimer with triaminopyrimidine, with in situ shell functionalization/modification using different types of hydrophobic agents. Remarkably, the use of hexamethylenedisilazane resulted in microcapsules of about 70 μm in diameter, with a smooth outer surface and a high isocyanate core content up to 85 wt% as determined by quantitative online FT-IR analysis of the extracted core. On the other hand, the use of an alkylamine, fluorinated aromatic amine and/or perfluoride amine provided microcapsules of approximately 100 to 150 μm in diameter containing around 65–75 wt% of the isocyanate core content, with the outer shell surface bearing pendant hydrophobic groups as confirmed by SEM-EDX. The effects of the functionalizing compound on the microcapsule properties such as shell morphology, size distribution and stability were assessed. After one day immersion in water, the initial isocyanate content of the microcapsules with a non-functionalized shell dropped rapidly from 49 to 15 wt%, whereas the ones with the modified shell structure maintained their core content, suggesting a significantly enhanced microcapsule stability.

A Multiple-Action Self-Healing Coating

This paper describes a self-healing coating for corrosion protection of metals which combines two different types of self-healing mechanisms in one coating with multiple-healing functionality. 2-Mercaptobenzothiazole (MBT) was loaded into layered double hydroxide (LDH) carriers which were mixed into an acrylated polycaprolactone polyurethane based shape recovery coating and applied on Hot Dip Galvanized steel (HDG). The effect of triggered release of MBT on the protection of HDG became visible when samples with manually applied defects in the coating were immersed in 0.05 M NaCl solution (first, autonomous healing mechanism). The shape recovery (second, non-autonomous healing mechanism) was triggered by heating the samples for 2 minutes to 60°C. SEM-EDX and Raman Spectroscopy proved the presence of MBT in the LDH, in the MBT-loaded LDH in the coating and the released MBT on the HDG surface in the damaged area after being in contact with a solution containing corrosive ions. Electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) demonstrate the corrosion protection effect of MBT in the coating with a defect and the restoration of the barrier properties of the coating after defect closure. This way, the independent mechanisms of this multi-action self-healing coating could be demonstrated.