Hybrid Coatings for Active Protection against Corrosion of Mg and Its Alloys.

A novel approach to surface modification was developed to improve the corrosion performance of biodegradable magnesium alloys. Additively manufactured magnesium samples and Mg-Mn-based magnesium alloys were used in this study. This method involves the combination of plasma electrolytic oxidation to create a porous ceramic-like matrix, followed by treatment with protective biocompatible agents. The most efficient method for the PEO-layer impregnation using sodium oleate and polycaprolactone was selected and optimized. The correlation between the structure, composition, and protective properties of the hybrid coatings was established. The composition of the formed polymer-containing layers was established using XPS and Raman microspectroscopy. The presence of sodium oleate and its distribution across the coating surface was confirmed at the microscale. The corrosion-protection level of the hybrid layers was assessed using potentiodynamic polarization measurements, electrochemical impedance spectroscopy, hydrogen evolution testing, and gravimetry (mass-loss tests) in vitro. The oleate-containing polycaprolactone layers (HC-SO 0.1-2) demonstrated stable corrosion behavior even after 7 days of immersion in Hank's balanced salt solution. The corrosion-current density and impedance modulus measured at a frequency of 0.1 Hz for the samples with hybrid coating after 7 days of exposure were equal to 5.68 × 10-8 A∙cm-2 and 2.03 × 106 Ω∙cm2, respectively. The developed method of surface modification demonstrates the coating's self-healing properties. The effectiveness of employing hybrid anticorrosive bioactive PEO coatings for biomedical products made from magnesium and its alloys was demonstrated.

A Superior Corrosion Protection of Mg Alloy via Smart Nontoxic Hybrid Inhibitor-Containing Coatings.

The increase of corrosion resistance of magnesium and its alloys by forming the smart self-healing hybrid coatings was achieved in this work in two steps. In the first step, using the plasma electrolytic oxidation (PEO) treatment, a ceramic-like bioactive coating was synthesized on the surface of biodegradable MA8 magnesium alloy. During the second step, the formed porous PEO layer was impregnated with a corrosion inhibitor 8-hydroxyquinoline (8-HQ) and bioresorbable polymer polycaprolactone (PCL) in different variations to enhance the protective properties of the coating. The composition, anticorrosion, and antifriction properties of the formed coatings were studied. 8-HQ allows controlling the rate of material degradation due to the self-healing effect of the smart coating. PCL treatment of the inhibitor-containing layer significantly improves the corrosion and wear resistance and retains an inhibitor in the pores of the PEO layer. It was revealed that the corrosion inhibitor incorporation method (including the number of steps, impregnation, and the type of solvent) significantly matters to the self-healing mechanism. The hybrid coatings obtained by a 1-step treatment in a dichloromethane solution containing 6 wt.% polycaprolactone and 15 g/L of 8-HQ are characterized by the best corrosion resistance. This coating demonstrates the lowest value of corrosion current density (3.02 × 10-7 A cm-2). The formation of the hybrid coating results in the corrosion rate decrease by 18 times (0.007 mm year-1) as compared to the blank PEO layer (0.128 mm year-1). An inhibitor efficiency was established to be 83.9%. The mechanism of corrosion protection of Mg alloy via smart hybrid coating was revealed.

The Effect of Smart PEO-Coatings Impregnated with Corrosion Inhibitors on the Protective Properties of AlMg3 Aluminum Alloy.

The protective coating with a self-organized microtubular structure was formed using plasma electrolytic oxidation (PEO) on AlMg3 aluminum alloy in the tartrate-fluoride electrolyte. This protective layer was further modified using corrosion inhibitors of the azole group (1,2,4-triazole, benzotriazole) and polymer material (polyvinilidene fluoride, PVDF). X-ray diffraction analysis and scanning electron microscopy with energy dispersive spectroscopy were used to study the morphology and composition of the obtained oxide coatings. The presence of the inhibitor in the PEO-layer was confirmed using micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The level of corrosion protection of formed coatings as well as the effect of loaded inhibitors on the anticorrosion efficiency was evaluated using electrochemical impedance spectroscopy (EIS) and localized scanning techniques (SVET/SIET). The coating impregnation with corrosion inhibitors of the azole group significantly improves the corrosion characteristics of the material. Impregnation of the base PEO-layer with 1,2,4-triazole during 24 h results in a 36 times increase in the impedance modulus measured at the lowest frequency (|Z|f=0.1Hz). Additional sealing of impregnated coating with polymer improves the corrosion stability of the treated material. On the base of the obtained data, the optimal way of protective inhibitor- and polymer-containing formation using surface treatment was suggested. The best barrier properties were established for hybrid coatings obtained by the immersion of a PEO-coated sample in 1,2,4-triazole solution for 24 h and following spraying the PVDF solution. The value of |Z|f=0.1Hz for this protective layer increased by more than two orders of magnitude in comparison with the base PEO-layer. The three-stage mechanism of corrosion inhibition of the sample with smart inhibitor-containing coating was established.

New Polycaprolactone-Containing Self-Healing Coating Design for Enhance Corrosion Resistance of the Magnesium and Its Alloys.

The method of hybrid coating formation on the surface of a bioresorbable wrought magnesium alloy and magnesium obtained by additive technology was proposed. Plasma electrolytic oxidation (PEO) with subsequent treatment of the material using an organic biocompatible corrosion inhibitor and a bioresorbable polymer material was used to obtain the protective layers. The optimal method of surface treatment was suggested. Using SEM/EDX analysis, XRD, XPS, and confocal Raman microspectroscopy, the composition of the formed surface layers was determined. The corrosion protection performance of the formed coatings was studied by potentiodynamic polarization and electrochemical impedance spectroscopy techniques in 0.9 wt.% NaCl and HBSS. Hydrogen evolution and mass loss tests were performed to study the corrosion rate of samples with different types of protective coatings. Sealing the pores of PEO coating with a polymeric material contributes to a significant reduction in the amount of the inhibitor diffusing into a corrosive medium. The best barrier properties were established for the hybrid coating formed with a one-stage application of benzotriazole and polycaprolactone. Such layers reduce the rate of alloy degradation due to active protection.

Icephobic Performance of Combined Fluorine-Containing Composite Layers on Al-Mg-Mn-Si Alloy Surface.

This paper presents the results of an evaluation of anti-icing properties of samples obtained by plasma electrolytic oxidation (PEO) with a subsequent application of superdispersed polytetrafluoroethylene (SPTFE) and polyvinylidenefluoride (PVDF). A combined treatment of the samples with SPTFE and PVDF is also presented. It is revealed that impregnation of a PEO layer with fluoropolymer materials leads to a significant increase in surface relief uniformity. Combined PVDF-SPFTE layers with a ratio of PVDF to SPTFE of 1:4 reveal the best electrochemical characteristics, hydrophobicity and icephobic properties among all of the studied samples. It is shown that the decrease in corrosion current density Ic for PVDF-SPFTE coatings is higher by more than five orders of magnitude in comparison with uncoated aluminum alloy. The contact angle for PVDF-SPFTE coatings attain 160.5°, which allows us to classify the coating as superhydrophobic with promising anti-icing performance. A treatment of a PEO layer with PVDF-SPFTE leads to a decrease in ice adhesion strength by 22.1 times compared to an untreated PEO coating.

Bioactive Coatings Formed on Titanium by Plasma Electrolytic Oxidation: Composition and Properties.

Bioactive coatings on VT1-0 commercially pure titanium were formed by the plasma electrolytic oxidation (PEO). A study of the morphological features of coatings was carried out using scanning electron microscopy. A composition of formed coatings was investigated using energy-dispersive spectroscopy and X-ray diffractometry analysis. It was shown that PEO-coatings have calcium phosphate in their composition, which increases the bioactivity of the surface layer. Electrochemical properties of the samples were studied by potentiondynamic polarization and electrochemical impedance spectroscopy in different physiological media: simulated body fluid and minimum essential medium. The data of electrochemical studies indicate more than 15 times decrease in the corrosion current density for the sample with coating (5.0 × 10-9 A/cm2) as compared to the bare titanium (7.7 × 10-8 A/cm2). The formed PEO-layers have elastoplastic properties close to human bone (12-30 GPa) and a lower friction coefficient in comparison with bare metal. The wettability of PEO-layers increased. The contact angle for formed coatings reduced by more than 60° in comparison with bare metal (from 73° for titanium to 8° for PEO-coating). Such an increase in surface hydrophilicity contributes to the greater biocompatibility of the formed coating in comparison with commercially pure titanium. PEO can be prospective as a method for improving titanium surface bioactivity.