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Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents. Nevertheless, the steps for preparing composite coatings are usually complicated and time-consuming. Herein, a novel composite coating, composed of bioactive magnesium thioctic acid (MTA) layer formed by deposition and corrosion-resistant magnesium hydroxide (Mg(OH)2) layer grown in situ, is simply fabricated on ZE21B alloys via one-step electrodeposition. Scanning electron microscopy (SEM) shows that the electrodeposited coating has a compact and uniform structure. And the high adhesion of the MTA/Mg(OH)2 hybrid coating is also confirmed by the micro-scratch test. Electrochemical test, scanning kelvin probe (SKP), and hydrogen evolution measurement indicate that the hybrid coating effectively reduces the degradation rate of Mg substrates. Haemocompatibility experiment and cell culture trial detect that the composite coating is of fine biocompatibility. Finally, the preparation mechanism of MTA/Mg(OH)2 hybrid coatings is discussed and proposed. This coating shows a great potential application for cardiovascular stents.

Smart micro-arc oxidation (MAO)/epoxy resin (EP) composite coatings were formed on AZ31 magnesium (Mg) alloy. Mesoporous silica nanocontainers (MSN) encapsulated with sodium benzoate (SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena: (1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value (∼ 5.18 × 10−8 Ω−1), and thus exhibiting significant corrosion inhibition and self-healing function; and (2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion (1.13 × 1010 Ω cm2). However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance, and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

In this study, the effects of intermetallic compounds (Mg17Al12 and Al8Mn5) on the Mg-Al layered double hydroxide (LDH) formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)2 steam coatings on AZ80 Mg alloy were investigated. Citric acid (CA) was used to activate the alloy surface during the pretreatment process. The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)2 steam coating. The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated. The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM, EDS, XRD and FT-IR. The corrosion resistance of the coated samples was evaluated using different techniques, i.e., potentiodynamic polarization (PDP), electrochemical impedance spectrum (EIS) and hydrogen evolution test. The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds. The surface area fraction of Mg17Al12 and Al8Mn5 phases on the surface of the alloy was significantly higher after the CA pretreatment, and thus promoted the growth of the subsequent Mg-Al-LDH coatings. The CA pretreatment for 30 s resulted in a denser and thicker LDH coating. Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy. The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.

Mg-1 wt.% Li-1 wt.% Ca (LX11) and Mg-4 wt.% Li-1 wt.% Ca (LX41) alloys share the same hexagonal closed-packed crystalline structure. However, the differences in microstructure, mechanical properties, and degradation rates between the two alloys are not well understood. Hereby, the above three aspects of LX11 and LX41 alloys were studied via optical microscopy, tensile tests, and electrochemical polarization and electrochemical impedance spectroscopy, together with hydrogen evolution. The concentration of the released Mg2+, Ca2+, and Li+ ions was analyzed using a flame atomic absorption spectrophotometer. Results demonstrated that the LX11 alloy was composed of finer α-Mg grains, fewer twins, and smaller volume fractions of the intermetallic phases Mg2Ca than the LX41 alloy. The increasing Li concentration generated a weak decrease in the yield strength of the Mg–Li–Ca alloys, a remarkable increase in elongation to failure, and a stable ultimate tensile strength. The LX11 alloy had better corrosion resistance than the LX41 alloy. The release rate of the cations (Mg2+, Ca2+, and Li+) varied significantly with time. The release rate of metallic ions in Hank's solution cannot reflect the true corrosion rate of Mg–Li–Ca alloys due to the formation of the precipitated corrosion products and their difference in solubility. The dealloying corrosion mechanism of the Mg2Ca phase in Mg–Li–Ca alloys was proposed.

Layered double hydroxide (LDH) coatings on magnesium (Mg) alloys shine brightly in the field of corrosion protection because of their special ion-exchange function. State-of-the-art steam coating as a type of LDH film preparation technique has emerged in recent years because only pure water is required as the steam source and its environmentally friendly LDH coating fits the current need for green development. Moreover, this coating can effectively inhibit the corrosion of the Mg alloy substrate due to the chemical bonding between the coating and the Mg alloy substrate. This review systematically explains cutting-edge advancements in the growth mechanism and corrosion behavior of LDH steam coatings, and analyzes the advantages and limitations of the steam-coating method. The influencing factors including pressure, CO2/CO32−, aluminum content of the substrate alloy, solution type, and acid-pickling pretreatment, as well as the post-treatment of steam-coating defects, are comprehensively elucidated, providing new insights into the development of the in situ steam-coating technique. Finally, existing issues and future prospects are discussed to further accelerate the widespread application of Mg alloys.

Surgical failures, caused by postoperative infections of bone implants, are commonly met, which cannot be treated precisely with intravenous antibiotics. Photothermal therapy (PTT) and photodynamic therapy (PDT) have attracted widespread attention due to their non-invasive antibacterial effects on tissues and no bacterial resistance, which may be an excellent approach to solve infections related to bone implants for biodegradable magnesium alloys. Herein, a sodium copper chlorophyllin (SCC) with a porphyrin ring induced Ca–P coating was prepared on AZ31 magnesium alloy via layer-by-layer (LbL) assembly. The morphology and composition of the samples were characterized through field emission scanning electron microscope (FE-SEM) with affiliated energy dispersive spectrometer (EDS), X-ray diffractometer (XRD), and Fourier infrared spectrometer (FTIR) and X-ray photoelectron spectrometer (XPS) as well. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and hydrogen evolution experiments were employed to evaluate the corrosion behavior of the samples. Atomic absorption spectrophotometer was used to measure Cu elemental content of different immersion periods. Cytocompatibility and antibacterial performance of the coatings were probed using in vitro cytotoxicity tests (MTT assay), live/dead cell staining and plate counting method. The results showed that the obtained (Ca–P/SCC)10 coating exhibited good corrosion resistance, antimicrobial activity (especially under 808 nm irradiation) and biocompatibility. The antibacterial rates for E. coli and S. aureus were 99.9% and 99.8%, respectively; and the photothermal conversion efficiency was as high as 42.1%. Triple antibacterial mechanisms including photodynamic, photothermal reactions and copper-ions release were proposed. This coating exhibited a promising application for biodegradable magnesium alloys.

Magnesium is a candidate metal for biodegradable implant applications for its biodegradation tendency and excellent biocompatibility. Unfortunately, the high degradation rate of magnesium and also its localized degradation in physiological conditions are the main issues for its successful implant applications. The degradation rate of magnesium has been reduced to some degree via alloying, but the localized degradation susceptibility is a great concern. For many years, hydroxyapatite (HAp), a biocompatible ceramic material, has been extensively used for bio-implant applications. Recently, a substantial amount of research has been carried out on coating HAp on magnesium-based materials for improved degradation resistance in particular and also to enhance the biocompatibility. This review article focuses on the different methods of HAp coating on magnesium-based materials and also the recent cutting-edge advancements made in the coating process for improved degradation resistance and biocompatibility. The mechanical stability of the HAp coated magnesium-based materials is also discussed.

Mg alloys possess biodegradability, suitable mechanical properties, and biocompatibility, which make them possible to be used as biodegradable implants. However, the uncontrollable degradation of Mg alloys limits their general applications. In addition to the factors from the metallic materials themselves, like alloy compositions, heat treatment process and microstructure, some external factors, relating to the test/service environment, also affect the degradation rate of Mg alloys, such as inorganic salts, bioorganic small molecules, bioorganic macromolecules. The influence of bioorganic molecules on Mg corrosion and its protection has attracted more and more attentions. In this work, the cutting-edge advances in the influence of bioorganic molecules (i.e., protein, glucose, amino acids, vitamins and polypeptide) and their coupling effect on Mg degradation and the formation of protection coatings were reviewed. The research orientations of biomedical Mg alloys in exploring degradation mechanisms in vitro were proposed, and the impact of bioorganic molecules on the protective approaches were also explored.

Superhydrophobic coatings have been considerably used in corrosion and its protection of metallic Mg. And the comprehensive performance (hydrophobicity, bonding strength, and corrosion resistance, etc.) of the top coating may be highly dependent on the physical and chemical properties of the primer or under coat. Herein, an integrated superhydrophobic polypropylene (PP) coating was fabricated on the micro-arc oxidized Mg substrate via one-step dipping. Surface morphologies and chemical compositions of the composite coating were examined through Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM) together with X-ray photoelectron spectroscopy (XPS). The surface wettability of the coating was determined by contact angle and sliding angle. The corrosion-resistant performance was evaluated via electrochemical and immersion measurements. The results showed that the hybrid coating possessed micron-scaled granular structure on the surface with a high water contact angle of 167.2 ± 0.8° and a low water sliding angle of 2.7 ± 0.5°. The corrosion resistance of superhydrophobic coating was obviously enhanced with a low corrosion current density of 8.76 × 10−9 A/cm2, and the coating still maintained integrity after 248 h of immersion in 3.5 wt% NaCl aqueous solution. The MAO coating provides better adhesion of PP to the surface. Hence, the superhydrophobic coating exhibited superior bonding strength, corrosion resistance and durability.

Biodegradable magnesium alloys are challenging to be implanted in patients with hyperglycemia and diabetes. A hypothesis is suggested that glucose accelerates microbial ingress and in vitro degradation of Mg–Li–Ca implants. Corrosion resistance and mechanical properties was demonstrated using electrochemical, hydrogen evolution and tensile tests. The bacteria from Hank's solution were isolated via 16S rRNA gene analysis. The results revealed that Mg–1Li–1Ca alloy exhibited different responses to Hank's solution with and without glucose. The solution acidity was ascribed to Microbacterium hominis and Enterobacter xiangfangensis, indicating that glucose promoted microbial activity and degradation and deterioration in mechanical property of Mg–1Li–1Ca alloy.

Protein exerts a critical influence on the degradation behavior of absorbable magnesium (Mg)-based implants. However, the interaction mechanism between protein and a micro-arc oxidation (MAO) coating on Mg alloys remains unclear. Hereby, a MAO coating was fabricated on AZ31 Mg alloy. And its degradation behavior in phosphate buffer saline (PBS) containing bovine serum albumin (BSA) was investigated and compared with that of the uncoated alloy. Surface morphologies and chemical compositions were studied using Field-emission scanning electron microscope (FE-SEM), Fourier transform infrared spectrophotometer (FT-IR) and X-ray diffraction (XRD). The degradation behavior of the bare Mg alloy and its MAO coating was studied through electrochemical and hydrogen evolution tests. Cytotoxicity assay was applied to evaluate the biocompatibility of Mg alloy substrate and MAO coating. Results indicated that the presence of BSA decreased the degradation rate of Mg alloy substrate because BSA (RCH(NH2)COO‾) molecules combined with Mg2+ ions to form (RCH(NH2)COO)2Mg and thus inhibited the dissolution of Mg(OH)2 by impeding the attack of Cl‾ ions. In the case of MAO coated Mg alloy, the adsorption of BSA on MAO coating and the formation of (RCH(NH2)COO)2Mg exhibited a synergistic effect and enhanced the corrosion resistance of the coated alloy significantly. Furthermore, cell bioactive assay suggested that the MAO coating had good viability for MG63 cells due to its high surface area.

Basically, Mg–Al layered double hydroxide (LDH) coatings are prepared on the surface of micro-arc oxidation (MAO) coated magnesium (Mg) alloys at a high temperature or a low pH value. This scenario leads to the growth rate of LDH coating inferior to the dissolution rate of the MAO coating. This in turn results in limited corrosion resistance of the composite coating. In this study, a Mg–Al LDH coating on MAO-coated Mg alloy AZ31 is prepared through a water bath with a higher pH (13.76) at a lower temperature (60 °C). FE-SEM, EDS, XRD, XPS, and FT-IR are applied to analyze the surface morphology, chemical compositions, and growth process. Electrochemical polarization, electrochemical impedance spectroscopy (EIS) and hydrogen evolution tests are employed to evaluate the corrosion resistance of the samples. The results disclose that the MAO coating is completely covered by the nanosheet-structured LDH coating with a thickness of approximately 3.8 μm. The corrosion current density of the MAO-LDH composite coating is decreased four orders of magnitude in comparison to its substrate; the presence of a wide passivation region in anodic polarization branch demonstrates its strong self-healing ability, indicating the hybrid coating possesses excellent corrosion resistance. The formation mechanism of the LDH coating on the MAO-coated Mg alloy is proposed. Furthermore, the cytocompatibility is assessed via an indirect extraction test for MC3T3-E1 pre-osteoblasts, which indicates an acceptable cytocompatibility of osteoblasts for the composite coating.

The biocorrosion of magnesium in the external physiological environment is still difficult to accurately evaluate the degradation behavior in vivo, particularly, in the microenvironment of the patients with hyperglycemia or diabetes. Thus, we explored the synergistic effects of glucose and protein on the biodegradation of pure magnesium, so as to have a deeper understanding the mechanism of the degradation in vivo. The surface morphology and corrosion product composition of pure magnesium were investigated using SEM, EDS, FTIR, XRD and XPS. The effect of glucose and albumin on the degradation rate of pure magnesium was investigated via electrochemical and immersion tests. The adsorption of glucose and albumin on the sample surface was observed using fluorescence microscopy. The results showed that the presence of 2 g/L glucose changed the micromorphology of corrosion products on the magnesium surface by reacting with metal cations, thus inhibiting the corrosion of pure magnesium. Protein formed a barrier layer to protect the magnesium at early stage of immersion. The chelation reaction between protein and magnesium surface might accelerate the degradation at later stage. There may be a critical glucose (albumin) content. Biodegradation of pure magnesium was inhibited at low concentrations and promoted at high concentrations. The synergistic effect of glucose and protein restrained the adsorption of aggressive chloride ions to a certain extent, and thus inhibited the degradation of pure magnesium considerably. Moreover, XPS results indicated that glucose promoted the adsorption of protein on the sample surface.

Micro-arc oxidation (MAO) coating with outstanding adhesion strength to Mg alloys has attracted more and more attention. However, owing to the porous structure, aggressive ions easily invaded the MAO/substrate interface through the through pores, limiting long-term corrosion resistance. Therefore, a dense and biocompatible tantalum oxide (Ta2O5) nanofilm was deposited on MAO coated Mg alloy AZ31 through atomic layer deposition (ALD) technique to seal the micropores and regulate the degradation rate. Surface micrography, chemical compositions and crystallographic structure were characterized using FE-SEM, EDS, XPS and XRD. The corrosion resistance of all samples was evaluated through electrochemical and hydrogen evolution tests. Results revealed that the Ta2O5 film mainly existed in the form of amorphousness. Moreover, uniform deposition of Ta2O5 film and effective sealing of micropores and microcracks in MAO coating were achieved. The current density (icorr) of the composite coating decreased three orders of magnitude than that of the substrate and MAO coating, improving corrosion resistance. Besides, the formation and corrosion resistance mechanisms of the composite coating were proposed. Keywords: Magnesium alloys, Micro-arc oxidation, Atomic layer deposition, Coatings

The clinic applications of bioabsorbable magnesium (Mg) and its alloys have been significantly restricted owing to their poor corrosion resistance. Besides elemental alloying, surface modification and functionality is a major approach to increasing corrosion resistance for magnesium alloys. This article reviews the cutting-edge advances and progress of biodegradable surface coatings upon Mg alloys over the last decades, aims to build up a knowledge framework of surface modification on biodegradable Mg alloys. A considerable number of conversion, deposition, mechanical and functional coatings and their preparation methods are discussed. The emphasis has been placed on the composition of chemical conversion and deposited coatings to overcome the disadvantages of adhesion, corrosion resistance and biocompatibility of a single coating for biomedical materials. The issues have been addressed on the integration of the structural and functional factors of the composite coatings. Keywords: Magnesium alloy, Biomaterial, Corrosion resistance, Coating, Biodegradability

Bioinspired coatings with decreased corrosion rate and enhanced bond strength are at the core of future clinic applications on degradable magnesium (Mg)-based implants. The hybrid of organic and inorganic compounds offers a strategy to fabricate biodegradable, biocompatible and compact coatings on biomedical Mg alloys. Hereby, a comparison with and without DNA addition was made on the corrosion resistance and adhesion strength of Ca–P coatings fabricated on AZ31 alloy via hydrothermal deposition. The morphology, chemical composition, and crystallographic structure of the coatings were investigated by means of SEM, EDS and FTIR as well as XRD before and after corrosion tests. Corrosion resistance was evaluated via potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS) and hydrogen evolution tests in Hank's solution. Results show that the coatings are mainly characterized by tricalcium phosphate (TCP), dicalcium phosphate anhydrous (DCPA) and calcium-deficient hydroxyapatite (CDHA). The presence of DNA leads to the formation of Ca–P coating with improved corrosion resistance and adhesion strength. Additionally, the formation mechanism for DNA-induced Ca–P coating is proposed. The DNA-induced Ca–P coating exhibits a promising future for controlling the corrosion rate of biodegradable Mg alloys. Keywords: DNA, Corrosion resistance, Biodegradability, Magnesium alloys, Coatings

A SnO2-doped dicalcium phosphate coating was prepared on AZ31 alloy by means of hydrothermal deposition. The results showed that the coating possessed a globular morphology with a long lamellar crystalline structure and a thickness of approximately 40 μm. The surface of the coating became smooth with an increase additive amount of the SnO2 nanoparticles. The corrosion current density and hydrogen evolution rate of the coating prepared in presence of SnO2 were reduced compared to the coating without SnO2 and the bare AZ31 substrate, indicating an improvement in the corrosion resistance of the SnO2-doped coating. Keywords: Phosphate coating, Biomaterials, Magnesium alloys, Corrosion, Stannic oxide