High-Performance HVOF-Sprayed Fe-Based Amorphous Coating on LA141 Magnesium Alloy via Optimizing Oxygen Flow and Kerosene Flow

To solve the problem of poor corrosion and wear resistance of Mg-Li alloys, Fe-based amorphous coatings were prepared by high velocity oxygen-fuel spraying technology (HVOF) on the LA141 magnesium alloy substrate with a Ni60 intermediate layer. The microstructure and performance of Fe-based amorphous coatings with different oxygen flow and kerosene flow were characterized and analyzed. The results demonstrate that there is an optimal oxygen/kerosene ratio where the porosity of Fe-based amorphous coating is the lowest. Moreover, the amorphous content increases with the decrease in the oxygen/kerosene ratio. In particular, when the oxygen flow is 53.8 m³/h and the kerosene flow is 26.5 L/h, the Fe-based amorphous coating possesses the lowest porosity (0.87%), the highest hardness (801 HV₀.₁), the highest bonding strength (56.9 MPa), and an excellent corrosion and wear resistance. Additionally, it can be seen that the Fe-based amorphous coating is composed of amorphous splats and amorphous oxides, but the Ni60 intermediate layer exhibits an amorphous and crystalline multi-phase structure. The high bonding strength of the coating is attributed to the low porosity of Fe-based amorphous coating and the localized metallurgical bonding between different layers. Finally, the mechanisms on corrosion and wear of Fe-based amorphous coatings are also discussed.     

Review of the Effect of Surface Coating Modification on Magnesium Alloy Biocompatibility

Magnesium alloy, as an absorbable and implantable biomaterial, has been greatly developed in the application field of biomaterials in recent years due to its excellent biocompatibility and biomechanics. However, due to the poor corrosion resistance of magnesium alloy in the physiological environment, the degradation rate will be unbalanced, which seriously affects the clinical use. There are two main ways to improve the corrosion resistance of magnesium alloy: one is by adding alloying elements, the other is by surface modification technology. Compared with adding alloy elements, the surface coating modification has the following advantages: (1) The surface coating modification is carried out without changing the matrix elements of magnesium alloy, avoiding the introduction of other elements; (2) The corrosion resistance of magnesium alloy can be improved by relatively simple physical, chemical, or electrochemical improvement. From the perspective of corrosion resistance and biocompatibility of biomedical magnesium alloy materials, this paper summarizes the application and characteristics of six different surface coating modifications in the biomedical magnesium alloy field, including chemical conversion method, micro-arc oxidation method, sol-gel method, electrophoretic deposition, hydrothermal method, and thermal spraying method. In the last section, it looks forward to the development prospect of surface coating modification and points out that preparing modified coatings on the implant surface combined with various modification post-treatment technologies is the main direction to improve biocompatibility and realize clinical functionalization.     

Effect of Pre-Oxidation Treatment on Corrosion Resistance of FeCoSiBPC Amorphous Alloy

In this paper, the corrosion resistance of FeCoSiBPC amorphous alloy after pre-oxidation and non-oxidation heat treatment is investigated. The corrosion behaviors of Fe₈₀Co₃Si₃B₁₀P₁C₃ amorphous alloys in 1 mol/L NaCl solution were investigated by the electrochemical workstation. The pre-oxidation heat treatment can improve the corrosion resistance of FeCoSiBPC amorphous alloy through an increase in the Ecorr value from −0.736 to −0.668 V, which makes it easy to reach a passive state. The corroded morphology and products of amorphous alloys were tested by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The SEM/TEM analysis showed that, after pre-oxidation treatment, the oxide layer was divided into two layers: the inner layer was amorphous, the outer layer appeared crystalline, and the main oxide was Fe₂O₃. During the oxidation process, Co and P elements diffused from the inner layer to the outer layer, forming phosphorus and cobalt oxides with high corrosion resistance on the surface of the ribbon, thereby improving the corrosion resistance of the ribbon.     

Microstructure and Wear Resistance of Laser Cladding of Fe-Based Alloy Coatings in Different Areas of Cladding Layer

In this study, laser cladding technology was used to prepare Fe-based alloy coating on a 27SiMn hydraulic support, and a turning treatment was used to obtain samples of the upper and middle regions of the cladding layer. The influence of microstructure, phase composition, hardness, and wear resistance in different areas of the cladding layer was studied through scanning electron microscopy (SEM), X-ray diffractometry (XRD), friction and wear tests, and microhardness. The results show that the bcc phase content in the upper region of the cladding layer is less than that in the middle region of the cladding layer, and the upper region of the cladding layer contains more metal compounds. The hardness of the middle region of the cladding layer is higher than that of the upper region of the cladding layer. At the same time, the main wear mechanism of the upper region of the cladding layer is adhesive wear and abrasive wear. The wear mechanism of the middle region of the cladding layer is mainly abrasive wear, with better wear resistance than the upper region of the cladding layer.     

The Effect of Heat Treatment on the Corrosion Resistance of Fe-Based Amorphous Alloy Coating Prepared by High Velocity Oxygen Fuel Method

In this study, Fe₄₀Cr₁₉Mo₁₈C₁₅B₈ amorphous coatings were prepared using high velocity oxygen fuel (HVOF) technology. Different temperatures were used in the heat treatment (600 °C, 650 °C, and 700 °C) and the annealed coatings were analyzed by DSC, SEM, TEM, and XRD. XRD and DSC results showed that the coating started to form a crystalline structure after annealing at 650 °C. From the SEM observation, it can be found that when the annealing temperature of the Fe-based amorphous alloy coating reached 700 °C, the surface morphology of the coating became relatively flat. TEM observation showed that when the annealing temperature of the Fe-based amorphous alloy coating was 700 °C, crystal grains in the coating recrystallized with a grain size of 5–20 nm. SAED analysis showed that the precipitated carbide phase was M₂₃C₆ phase with different crystal orientations (M = Fe, Cr, Mo). Finally, the corrosion polarization curve showed that the corrosion current density of the coating after annealing only increased by 9.13 μA/cm², which indicated that the coating after annealing treatment still had excellent corrosion resistance. It also proved that the Fe-based amorphous alloy coating can be used in high-temperature environments. XPS analysis showed that after annealing FeO and Fe₂O₃ oxide components increased, and the formation of a large number of crystals in the coating resulted in a decrease in corrosion resistance.     

Properties of Microplasma Coating on AZ91 Magnesium Alloy Prepared from Electrolyte with and without the Borax Addition

Magnesium alloys, due to their unique properties, low density and high strength properties, are becoming more frequently used in industrial applications. However, a limitation of their use may be the need to ensure high abrasive wear resistance and corrosion resistance. Therefore, magnesium alloys are often protected by applying protective coatings. The paper presents the influence of the modification of the electrolyte composition, with or without the addition of borax, on the morphology (observed by SEM method) and phase composition (analyzed by EDS and XRD) of the formed layers on the AZ91 magnesium alloy, and their abrasive wear (determined with Ball-on-Disc method) and corrosion resistance (evaluated using the immersion method and by electrochemical tests), especially in chloride solutions. It has been clearly demonstrated that the modification of the electrolyte composition significantly impacts the final properties of the protective coatings on the AZ91 alloy formed by the plasma electrolytic oxidation (PEO) process. On the basis of the results, it was found that the new type of PEO coatings with the borax addition, compared to base PEO coatings, showed significantly higher abrasion resistance and an order of magnitude lower corrosion rate.     

Microstructure and Corrosion Resistance of AZ91 Magnesium Alloy after Surface Remelting Treatment

The effect of surface remelting treatment on the microstructure and corrosion resistance of the AZ91 magnesium alloy was studied. The surface layer was remelted by GTAW (gas tungsten arc welding). An original two-burner system with welding torches operating in a tandem configuration was used, allowing the combination of cleaning the surface from oxides with the remelting process. The studies of the corrosion resistance of the alloy included electrochemical tests and measurements of the rate of hydrogen evolution. The results showed that surface remelting treatment leads to favorable microstructural changes, manifested in strong grain refinement and a more uniform arrangement of the β-Mg₁₇Al₁₂ phase. The changes in the microstructure caused by remelting and the accompanying fast crystallization contributed to an increase in the corrosion resistance of the remelted samples in comparison to their non-remelted equivalents. The results obtained on the basis of the polarization curves showed three-fold lower values of the corrosion current density in the case of the remelted material than the value of the corrosion current density determined for the starting material. In turn, in the case of measurements of the electrochemical noise and corrosion rate determined by the method of measuring the rate of hydrogen evolution, this value for the remelted alloy was two times lower. The research also showed that GTAW technology is highly effective and can be a valuable alternative to laser techniques. The complete experimental details, obtained results and their analyses are presented in this paper.     

Effect of SiC Nanoparticles on AZ31 Magnesium Alloy

Magnesium alloys are attractive for the production of lightweight parts in modern automobile and aerospace industries due to their advanced properties. Their mechanical properties are usually enhanced by the incorporation with reinforcement particles. In the current study, reinforced AZ31 magnesium alloy was fabricated through the addition of bulk Al and the incorporation of SiC nanoparticles using a stir casting process to obtain AZ31-SiC nanocomposites. Scanning electron microscope (SEM) investigations revealed the formation of Mg₁₇Al₁₂ lamellar intermetallic structures and SiC clusters in the nanocomposites. Energy dispersive spectroscopy (EDS) detected the uniform distribution of SiC nanoparticles in the AZ31-SiC nanocomposites. Enhancements in hardness and yield strength (YS) were detected in the fabricated nanocomposites. This behavior was referred to a joint strengthening mechanisms which showed matrix-reinforcement coefficient of thermal expansion (CTE) and elastic modulus mismatches, Orowan strengthening, and load transfer mechanism. The mechanical properties and wear resistance were gradually increased with an increase in SiC content in the nanocomposite. The maximum values were obtained from nanocomposites containing 1 wt% of SiC (AZ31-1SiC). AZ31-1SiC nanocomposite YS and hardness were improved by 27% and 30%, respectively, compared to AZ31 alloy. This nanocomposite also exhibited the highest wear resistance; its wear mass loss and depth of the worn surface decreased by 26% and 15%, respectively, compared to AZ31 alloy.     

A Comparative Study of Aluminium and Titanium Warm Sprayed Coatings on AZ91E Magnesium Alloy

Aluminium (Al) and titanium (Ti) coatings were applied on AZ91E magnesium alloy using a low-pressure warm spray (WS) method. The deposition was completed using three different nitrogen flow rates (NFR) for both coatings. NFR effects on coating microstructure and other physical properties were systematically studied. Microstructural characterization was performed using scanning electron microscopy (SEM), and the porosity was estimated using two methods—image analysis and X-ray microtomography. The coating adhesion strength, wear resistance, and hardness were examined. The protective properties of the coatings were verified via a salt spray test. Decreasing NFR during coating deposition produced more dense and compact coatings. However, these conditions increased the oxidation of the powder. Al coatings showed lower hardness and wear resistance than Ti coatings, although they are more suitable for corrosion protection due to their low porosity and high compactness.     

Preparation and Characterization of Hydroxyapatite Coating on AZ31 Magnesium Alloy Induced by Carboxymethyl Cellulose-Dopamine

Magnesium and its alloys have become potential implant materials in the future because of light weight, mechanical properties similar to natural bone, good biocompatibility, and degradability in physiological environment. However, due to the rapid corrosion and degradation of magnesium alloys in vivo, especially in the environment containing chloride ions, the application of magnesium alloys as implant materials has been limited. Therefore, improving the corrosion resistance of magnesium alloy and ensuring good biocompatibility is the main focus of the current research. In this study, hydroxyapatite coating was prepared on magnesium alloy surface using carboxymethyl cellulose-dopamine hydrogel as inducer to improve corrosion resistance and biocompatibility. Surface characterization techniques (scanning electron microscopy, Fourier-transformed infrared spectroscopy, energy dispersive X-ray spectroscopy- and X-ray diffraction) confirmed the formation of hydroxyapatite on the surface of AZ31 alloy. Corrosion resistance tests have proved the protective effect of Carboxymethyl cellulose-Dopamine/hydroxyapatite (CMC-DA/HA) coating on the surface of AZ31 alloy. According to MC3T3-E1 cell viability and Live/Dead staining, the coating also showed good biocompatibility. The results will provide new ideas for the biological application of magnesium alloys.     

Recent Progress in Functionalized Coatings for Corrosion Protection of Magnesium Alloys—A Review

Magnesium (Mg) and its alloys, which have good mechanical properties and damping capacities, are considered as potential candidate materials in the industrial field. Nevertheless, fast corrosion is the main obstacle that seriously hinders its wide applications. Surface modification is an available method to avoid the contact between corrosive media and Mg substrates, thus extending the service life of Mg-based materials. Generally, manufacturing a dense and stable coating as physical barriers can effectively inhibit the corrosion of Mg substrates; however, in some complex service environments, physical barrier coating only may not satisfy the long-term service of Mg alloys. In this case, it is very important to endow the coating with suitable functional characteristics, such as superhydrophobic and self-healing properties. In this review, the various surface treatments reported are presented first, followed by the methods employed for developing superhydrophobic surfaces with micro/nanostructuring, and an overview of the various advanced self-healing coatings, devolved on Mg alloys in the past decade, is further summarized. The corresponding preparation strategies and protection mechanisms of functional coatings are further discussed. A potential research direction is also briefly proposed to help guide functional strategies and inspire further innovations. It is hoped that the summary of this paper will be helpful to the surface modification of Mg alloys and promote the further development of this emerging research field.     

Influence of Sulfate-Reducing Bacteria on the Corrosion Residual Strength of an AZ91D Magnesium Alloy

In this paper, the corrosion residual strength of the AZ91D magnesium alloy in the presence of sulfate-reducing bacteria is studied. In the experiments, the chemical composition of corrosion film was analyzed by a scanning electron microscope with energy dispersive X-ray spectroscopy. In addition, a series of instruments, such as scanning electronic microscope, pH-meter and an AG-10TA materials test machine, were applied to test and record the morphology of the corrosion product, fracture texture and mechanical properties of the AZ91D magnesium alloy. The experiments show that the sulfate-reducing bacteria (SRB) play an important role in the corrosion process of the AZ91D magnesium alloy. Pitting corrosion was enhanced by sulfate-reducing bacteria. Corrosion pits are important defects that could lead to a significant stress concentration in the tensile process. As a result, sulfate-reducing bacteria influence the corrosion residual strength of the AZ91D magnesium alloy by accelerating pitting corrosion.     

Comparison of Different Cermet Coatings Sprayed on Magnesium Alloy by HVOF

In the present study, two different cermet coatings, WC–CrC–Ni and Cr₃C₂–NiCr, manufactured by the high-velocity oxy-fuel (HVOF) method were studied. They are labeled as follows: WC–CrC–Ni coating—WC and Cr₃C₂–NiCr coating—CrC. These coatings were deposited onto a magnesium alloy (AZ31) substrate. The goal of the study was to compare these two types of cermet coating, which were investigated in terms of microstructure features and selected mechanical properties, such as hardness, instrumented indentation, fracture toughness, and wear resistance. The results reveal that the WC content influenced the hardness and Young’s modulus. The most noticeable effect of WC addition was observed for the wear resistance. WC coatings had a wear intensity value that was almost two times lower, equal to 6.5·10⁻⁶ mm³/N·m, whereas for CrC ones it was equal to 12.6·10⁻⁶ mm³/N·m. On the other hand, the WC coating exhibited a lower value of fracture toughness.     

On the Corrosion Fatigue of Magnesium Alloys Aimed at Biomedical Applications: New Insights from the Influence of Testing Frequency and Surface Modification of the Alloy ZK60

Magnesium alloys are contemporary candidates for many structural applications of which medical applications, such as bioresorbable implants, are of significant interest to the community and a challenge to materials scientists. The generally poor resistance of magnesium alloys to environmentally assisted fracture, resulting, in particular, in faster-than-desired bio-corrosion degradation in body fluids, strongly impedes their broad uptake in clinical practice. Since temporary structures implanted to support osteosynthesis or healing tissues may experience variable loading, the resistance to bio-corrosion fatigue is a critical issue that has yet to be understood in order to maintain the structural integrity and to prevent the premature failure of implants. In the present communication, we address several aspects of the corrosion fatigue behaviour of magnesium alloys, using the popular commercial ZK60 Mg-Zn-Zr alloy as a representative example. Specifically, the effects of the testing frequency, surface roughness and metallic coatings are discussed in conjunction with the fatigue fractography after the testing of miniature specimens in air and simulated body fluid. It is demonstrated that accelerated environmentally assisted degradation under cyclic loading occurs due to a complicated interplay between corrosion damage, stress corrosion cracking and cyclic loads. The occurrence of corrosion fatigue in Mg alloys is exaggerated by the significant sensitivity to the testing frequency. The fatigue life or strength reduced remarkably with a decrease in the test frequency.     

Influence of Zeolite Coating on the Corrosion Resistance of AZ91D Magnesium Alloy

The protective performance of zeolite coating on AZ91D magnesium alloy was evaluated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in 0.1 M sodium chloride solution (NaCl). Electrical equivalent circuit (EEC) was developed based upon hypothetical corrosion mechanisms and simulated to correspond to the experimental data. The morphology and the chemical nature of the coating were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. Post corrosion morphologies of the zeolite coated and the uncoated AZ91D alloy were investigated using SEM. The corrosion resistance of the zeolite coated specimen was at least one order of magnitude higher than the uncoated specimen.     

Morphology and Anti-Corrosive Performance of Cr(III) Passivated Zn–Fe Alloy Coating on NdFeB Substrate

In this study, low-iron Zn–Fe alloy coatings and pure Zn coatings, with or without trivalent chromium passivation treatment, were electrodeposited onto a sintered NdFeB magnet from a weak acid chloride bath. The surface morphology and structure of the coatings were then examined using the X-ray diffraction, a scanning electron microscope and 3D white-light interfering surface analysis. Meanwhile, the electrodeposition behavior and anti-corrosive properties of the coatings were investigated using cyclic voltammetry, potentiodynamic polarization, electrochemical impedance spectroscopy, and natural salt spray tests. The results indicate that a passivated Zn–Fe alloy coating with a 0.9 wt.% Fe content provided much better corrosion resistance than a pure Zn coating and could provide both anodic protection and physical barrier function in the NdFeB substrates. The Fe element in Zn–Fe alloy coating was predominantly in solid solution in η-phase and small amounts in elemental form, which was beneficial to acquire a compact coating and passivation film. Finally, the passivated Zn–Fe alloy coating withstood 210 h against a neutral 3.5 wt.% NaCl salt spray without any white rust, which was 3–4 times longer than the pure Zn coating.     

Effect of Parylene C on the Corrosion Resistance of Bioresorbable Cardiovascular Stents Made of Magnesium Alloy ‘Original ZM10’

Magnesium (Mg) alloy has attracted significant attention as a bioresorbable scaffold for use as a next-generation stent because of its mechanical properties and biocompatibility. However, Mg alloy quickly degrades in the physiological environment. In this study, we investigated whether applying a parylene C coating can improve the corrosion resistance of a Mg alloy stent, which is made of ‘Original ZM10’, free of aluminum and rare earth elements. The coating exhibited a smooth surface with no large cracks, even after balloon expansion of the stent, and improved the corrosion resistance of the stent in cell culture medium. In particular, the parylene C coating of a hydrofluoric acid-treated Mg alloy stent led to excellent corrosion resistance. In addition, the parylene C coating did not affect a polymer layer consisting of poly(ε-caprolactone) and poly(D,L-lactic acid) applied as an additional coating for the drug release to suppress restenosis. Parylene C is a promising surface coating for bioresorbable Mg alloy stents for clinical applications.     

The Effect of Solidification Rate on the Corrosion Resistance of Die-Cast AZ91 Magnesium Alloy

To increase the utilization of die-cast Mg alloys with various shapes in a variety of environments, the corrosion behaviors of commercial die-cast Mg alloys with different thicknesses were investigated in neutral and alkali solutions at ambient temperature. A decrease in the thickness of a specimen leads to an increase in cooling and solidification rates, which, in turn, decreases the size of the eutectic β phases and the interphase distance, thus improving the hardness of the specimen. Specimens with relatively large β phases were more corroded under neutral conditions due to severe galvanic corrosion at the interface between α-Mg and the β phases, whereas they were protected by passivation films formed on the substrate in the alkaline solution. However, in the case of the alloy with thin thickness and high solidification rate, the fine β phases improved corrosion resistance by forming a net structure that acted as a barrier to corrosion propagation of the α matrix. These results suggest that the size and distribution of the eutectic phases should be appropriately controlled, depending on the environment.     

Improving the Properties of Composite Titanium Nitride Layers on the AZ91D Magnesium Alloy Using Hydrothermal Treatment

Coating magnesium alloys with nitride surface layers is a prospective way of improving their intrinsically poor surface properties; in particular, their tribological and corrosion resistance. These layers are usually produced using PVD methods using magnetron sputtering or arc evaporation. Even though the thus-produced layers significantly increase the wear resistance of the alloys, their effects on corrosion resistance are unsatisfactory because of the poor tightness, characteristic of PVD-produced products. Tightness acquires crucial significance when the substrate is a highly-active magnesium alloy, hence our idea to tighten the layers by subjecting them to a post-deposition chemical-hydrothermal-type treatment. This paper presents the results of our experiments with a new hybrid surface engineering method, using a final tightening pressure hydrothermal gas treatment in overheated steam of the composite titanium nitride layers PVD, produced on AZ91D magnesium alloy. The proposed method resulted in an outstanding improvement of the performance properties, in particular resistance to corrosion and wear, yielding values that exceed those exhibited by commercially anodized alloys and austenitic stainless 316L steel. The developed hybrid method produces new, high-performance corrosion and wear resistant, lightweight magnesium base materials, suitable for heavy duty applications.     

Recent Advances on Development of Hydroxyapatite Coating on Biodegradable Magnesium Alloys: A Review

The wide application of magnesium alloys as biodegradable implant materials is limited because of their fast degradation rate. Hydroxyapatite (HA) coating can reduce the degradation rate of Mg alloys and improve the biological activity of Mg alloys, and has the ability of bone induction and bone conduction. The preparation of HA coating on the surface of degradable Mg alloys can improve the existing problems, to a certain extent. This paper reviewed different preparation methods of HA coatings on biodegradable Mg alloys, and their effects on magnesium alloys’ degradation, biocompatibility, and osteogenic properties. However, no coating prepared can meet the above requirements. There was a lack of systematic research on the degradation of coating samples in vivo, and the osteogenic performance. Therefore, future research can focus on combining existing coating preparation technology and complementary advantages to develop new coating preparation techniques, to obtain more balanced coatings. Second, further study on the metabolic mechanism of HA-coated Mg alloys in vivo can help to predict its degradation behavior, and finally achieve controllable degradation, and further promote the study of the osteogenic effect of HA-coated Mg alloys in vivo.