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.

Cold-Sprayed Composite Metal-Fluoropolymer Coatings for Alloy Protection against Corrosion and Wear.

Results of studying the properties of composite fluoropolymer-containing coatings formed by the cold spray (CS) method on the surface of constructional steel are presented. Different ways of protective coating formation are proposed. The composition of coatings was studied using SEM/EDX analysis. The incorporation of super-dispersed polytetrafluoroethylene (SPTFE) into the coating increases the corrosion resistance of the copper-zinc-based cold-sprayed coating. Analysis of the electrochemical properties obtained using EIS (electrochemical impedance spectroscopy) and PDP (potentiodynamic polarization) indicates that samples treated with SPTFE on a base copper-zinc coating showed lower corrosion current density and higher impedance modulus (jc = 8.5 × 10-7 A cm-2, |Z|f=0.1 Hz = 5.3 × 104 Ω∙cm2) than the specimen with cold-sprayed SPTFE (jc = 6.1 × 10-6 A cm-2, |Z|f=0.1 Hz = 8.1 × 103 Ω∙cm2). The best anticorrosion properties were revealed for the sample with a cold-sprayed base Cu-Zn layer annealed at 500 °C for 1 h, followed by SPTFE friction treatment and re-annealed at 350 °C for 1 h. The corrosion current density jc of such a coating is 25 times lower than that for the base Cu-Zn coating. The antifriction properties and hydrophobicity of the formed layers are described. Obtained results indicate that cold-sprayed polymer-containing coatings effectively improve the corrosion and wear resistivity of the treated material.

Composite Coatings of AMg3 Alloy Formed by a Combination of Plasma Electrolytic Oxidation and Fluoropolymer Spraying.

This paper presents the results of an investigation of the changes in the corrosion, wear resistance, and wettability of composite coatings formed on the AMg3 alloy through plasma electrolytic oxidation (PEO) and subsequent spraying with an organofluorine polymer. The evaluation of the electrochemical properties of the composite layers revealed a decrease in the corrosion current density compared with the PEO coating (from 3.8 × 10-8 to 3.1 × 10-11 A/cm2). The analysis of the wear resistance of composite coatings established that the application of this type of coating reduced the wear of the samples by two orders of magnitude when compared with the PEO layer. Using the contact-angle measurement, it was found that with an increase in the number of polymer spray applications, the wettability of coatings decreased, so the contact angle for the composite coating with triple fluoropolymer application increased by 134.3° compared to the base PEO coating.

Surface Modification of Additively Fabricated Titanium-Based Implants by Means of Bioactive Micro-Arc Oxidation Coatings for Bone Replacement.

In this work, the micro-arc oxidation method is used to fabricate surface-modified complex-structured titanium implant coatings to improve biocompatibility. Depending on the utilized electrolyte solution and micro-arc oxidation process parameters, three different types of coatings (one of them-oxide, another two-calcium phosphates) were obtained, differing in their coating thickness, crystallite phase composition and, thus, with a significantly different biocompatibility. An analytical approach based on X-ray computed tomography utilizing software-aided coating recognition is employed in this work to reveal their structural uniformity. Electrochemical studies prove that the coatings exhibit varying levels of corrosion protection. In vitro and in vivo experiments of the three different micro-arc oxidation coatings prove high biocompatibility towards adult stem cells (investigation of cell adhesion, proliferation and osteogenic differentiation), as well as in vivo biocompatibility (including histological analysis). These results demonstrate superior biological properties compared to unmodified titanium surfaces. The ratio of calcium and phosphorus in coatings, as well as their phase composition, have a great influence on the biological response of the coatings.

Moss-like Hierarchical Architecture Self-Assembled by Ultrathin Na2Ti3O7 Nanotubes: Synthesis, Electrical Conductivity, and Electrochemical Performance in Sodium-Ion Batteries.

Nanocrystalline layer-structured monoclinic Na2Ti3O7 is currently under consideration for usage in solid state electrolyte applications or electrochemical devices, including sodium-ion batteries, fuel cells, and sensors. Herein, a facile one-pot hydrothermal synthetic procedure is developed to prepare self-assembled moss-like hierarchical porous structure constructed by ultrathin Na2Ti3O7 nanotubes with an outer diameter of 6-9 nm, a wall thickness of 2-3 nm, and a length of several hundred nanometers. The phase and chemical transformations, optoelectronic, conductive, and electrochemical properties of as-prepared hierarchically-organized Na2Ti3O7 nanotubes have been studied. It is established that the obtained substance possesses an electrical conductivity of 3.34 × 10-4 S/cm at room temperature allowing faster motion of charge carriers. Besides, the unique hierarchical Na2Ti3O7 architecture exhibits promising cycling and rate performance as an anode material for sodium-ion batteries. In particular, after 50 charge/discharge cycles at the current loads of 50, 150, 350, and 800 mA/g, the reversible capacities of about 145, 120, 100, and 80 mA∙h/g, respectively, were achieved. Upon prolonged cycling at 350 mA/g, the capacity of approximately 95 mA∙h/g at the 200th cycle was observed with a Coulombic efficiency of almost 100% showing the retention as high as 95.0% initial storage. At last, it is found that residual water in the un-annealed nanotubular Na2Ti3O7 affects its electrochemical properties.

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.

Enhancing Lithium and Sodium Storage Properties of TiO2(B) Nanobelts by Doping with Nickel and Zinc.

Nickel- and zinc-doped TiO2(B) nanobelts were synthesized using a hydrothermal technique. It was found that the incorporation of 5 at.% Ni into bronze TiO2 expanded the unit cell by 4%. Furthermore, Ni dopant induced the 3d energy levels within TiO2(B) band structure and oxygen defects, narrowing the band gap from 3.28 eV (undoped) to 2.70 eV. Oppositely, Zn entered restrictedly into TiO2(B), but nonetheless, improves its electronic properties (Eg is narrowed to 3.21 eV). The conductivity of nickel- (2.24 × 10-8 S·cm-1) and zinc-containing (3.29 × 10-9 S·cm-1) TiO2(B) exceeds that of unmodified TiO2(B) (1.05 × 10-10 S·cm-1). When tested for electrochemical storage, nickel-doped mesoporous TiO2(B) nanobelts exhibited improved electrochemical performance. For lithium batteries, a reversible capacity of 173 mAh·g-1 was reached after 100 cycles at the current load of 50 mA·g-1, whereas, for unmodified and Zn-doped samples, around 140 and 151 mAh·g-1 was obtained. Moreover, Ni doping enhanced the rate capability of TiO2(B) nanobelts (104 mAh·g-1 at a current density of 1.8 A·g-1). In terms of sodium storage, nickel-doped TiO2(B) nanobelts exhibited improved cycling with a stabilized reversible capacity of 97 mAh·g-1 over 50 cycles at the current load of 35 mA·g-1.

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.

Atmospheric and Marine Corrosion of PEO and Composite Coatings Obtained on Al-Cu-Mg Aluminum Alloy.

Wrought Al-Cu-Mg aluminum alloy (D16) was treated by bipolar plasma electrolytic oxidation to create a base plasma electrolytic oxidation (PEO)-coating with corrosion protection and mechanical properties superior to bare alloy's natural oxide layer. Additional protection was provided by the application of polymer, thus creating a composite coating. Electrochemical and scratch tests, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction studies were performed. Degradation of coatings in the marine atmosphere and seawater was evaluated. The composite polymer-containing coating provided better corrosion protection of aluminum alloy compared to the PEO-coating, although seawater affected both. During the atmospheric exposure, the PEO-coating provided reasonably good protection, and the composite coating showed excellent performance.

Effect of Microstructure on the Corrosion Resistance of TIG Welded 1579 Alloy.

The paper studies microstructure, chemical composition and corrosion activity of the tungsten inert gas welded joint of the Al-Mg-Sc alloy. An intensive corrosion attack of the heat affected zone (HAZ) was found due to precipitation of secondary phases at recrystallized grain boundaries. The ccorrosion process initiated along the boundary of α-Al grains, where a high concentration of anodic (Mg2Si and Mg2Al3) and cathodic phases ((MnFe)Al6) was observed. Increased temperatures during welding led to coalescence of the anodic phases in HAZ. Additionally, HAZ was found to be enriched with hard intermetallic compounds (Mg2Si and (MnFe)Al6). This area had a higher microhardness (930 MPa) compared to base metal (BM, 895 MPa) and fusion zone (FZ, 810 MPa). The volume fraction of secondary phases was 26% in BM, 28% in FZ and 38% in HAZ. The average grain size increased in the following order: (9 ± 3) µm (BM) < (16 ± 3) µm (HAZ) < (21 ± 5) µm (FZ). A plasma electrolytic oxidation (PEO) coating of aluminum-based material was applied to protect the weld from oxidation. The PEO-coating provided a high corrosion protection in the aggressive Cl--containing environment.

Corrosion of the Welded Aluminium Alloy in 0.5 M NaCl Solution. Part 2: Coating Protection.

The high electrochemical activity of the aircraft 1579 aluminium alloy with a welded joint and the necessity of the coating formation to protect this material against corrosion as well as to increase the stability of the weld interface in the corrosive medium has been previously established. In this work, two suggested methods of protective coating formation based on plasma electrolytic oxidation (PEO) in tartrate-fluoride electrolyte significantly increased the protective properties of the welded joint area of the 1579 Al alloy. The electrochemical properties of the formed surface layers have been investigated using SVET (scanning vibrating electrode technique) and SIET (scanning ion-selective electrode technique), EIS (electrochemical impedance spectroscopy), OCP (open circuit potential), and PDP (potentiodynamic polarization) in 0.5 M NaCl. The less expressed character of the local electrochemical processes on the welded 1579 Al alloy with the composite coating in comparison with the base PEO-layer has been established. Polymer-containing coatings obtained using superdispersed polytetrafluoroethylene (SPTFE) treatment are characterized by the best possible protective properties and prevent the material from corrosion destruction. Single SPTFE treatment enables one to increase PEO-layer protection by 5.5 times. The results of this study indicate that SVET and SIET are promising to characterize and to compare corrosion behaviour of coated and uncoated samples with a welded joint in chloride-containing media.

Corrosion of the Welded Aluminium Alloy in 0.5 M NaCl Solution. Part 1: Specificity of Development.

This work consists of two parts. In the first part, the kinetics and mechanism of corrosion on the surface of the welded joint area of the aircraft 1579 aluminium alloy have been studied using SVET (scanning vibrating electrode technique) and SIET (scanning ion-selective electrode technique) in 0.5 M NaCl. The results have revealed the corrosion process development within the weld interface due to the presence of microdefects in the morphological structure. Features of the 1579 Al alloy corrosion have also been investigated through immersion experiments, quantitative analysis of dissolved alloying elements by means of atomic absorption spectroscopy, and corrosion products characterization using XRD (X-ray diffraction) analysis. The presence of Mg as an alloying element in the 1579 Al alloy sufficiently increases the bulk pH values as a result of the intensive dissolution of Mg. These factors accelerate the corrosion activity of the studied material in the 0.5 M NaCl solution. Corrosion evolution analysis of the 1579 Al alloy sample showed the importance of the coating formation to protect this alloy against corrosion and to increase the stability of this system in the corrosive media.

Effect of Hf-doping on electrochemical performance of anatase TiO2 as an anode material for lithium storage.

Hafnium-doped titania (Hf/Ti = 0.01; 0.03; 0.05) had been facilely synthesized via a template sol-gel method on carbon fibre. Physico-chemical properties of the as-synthesized materials were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetry analysis and Brunauer-Emmett-Teller measurements. It was confirmed that Hf4+ substitute in the Ti4+ sites, forming Ti1-x Hf x O2 (x = 0.01; 0.03; 0.05) solid solutions with an anatase crystal structure. The Ti1-x Hf x O2 materials are hollow microtubes (length of 10-100 µm, outer diameter of 1-5 µm) composed of nanoparticles (average size of 15-20 nm) with a surface area of 80-90 m2 g-1 and pore volume of 0.294-0.372 cm3 g-1. The effect of Hf ion incorporation on the electrochemical behaviour of anatase TiO2 in the Li-ion battery anode was investigated by galvanostatic charge/discharge and electrochemical impedance spectroscopy. It was established that Ti0.95Hf0.05O2 shows significantly higher reversibility (154.2 mAh g-1) after 35-fold cycling at a C/10 rate in comparison with undoped titania (55.9 mAh g-1). The better performance offered by Hf4+ substitution of the Ti4+ into anatase TiO2 mainly results from a more open crystal structure, which has been achieved via the difference in ionic radius values of Ti4+ (0.604 Å) and Hf4+ (0.71 Å). The obtained results are in good accord with those for anatase TiO2 doped with Zr4+ (0.72 Å), published earlier. Furthermore, improved electrical conductivity of Hf-doped anatase TiO2 materials owing to charge redistribution in the lattice and enhanced interfacial lithium storage owing to increased surface area directly depending on the Hf/Ti atomic ratio have a beneficial effect on electrochemical properties.

In vivo study of osteogenerating properties of calcium-phosphate coating on titanium alloy Ti-6Al-4V.

The method of formation of bioactive calcium-phosphate coating on medical titanium alloy Ti-6Al-4V (3.5-5.3% V; 5.3-6.8% Al; balance -Ti) by plasma electrolytic oxidation (PEO) has been developed. Evaluation of osteogenerating properties of the coating at fractures of the shaft of the femur on Wistar line laboratory rats has been performed. It has been established that the calcium-phosphate PEO coating accelerates osteogenesis and promotes the formation of a pronounced periosteal callus in the fracture area. The presence of calcium phosphates in the PEO coating surface layer significantly accelerates the growth of bone tissue on the titanium surface.