Shuo-Qi Li

Corrosion of molybdate intercalated hydrotalcite coating on AZ31 Mg alloy

A molybdate intercalated hydrotalcite (HT-MoO42−) coating with a nanosized lamellar structure was synthesized on AZ31 Mg alloy by a combination of the co-precipitation and hydrothermal processes. The characteristics of the coatings were investigated by SEM, EPMA, XRD, EDS and FT-IR. The corrosion resistance of the coatings was assessed by potentiodynamic polarization, electrochemical impedance spectrum, and hydrogen evolution. The results indicated that the HT-MoO42− coating, characterized by interlocking plate-like nanostructures, ion-exchange and self-healing ability, has a potential to be a “smart” coating capable of responding to stimuli from the environment.

In vitro degradation of pure Mg in response to glucose

Magnesium and its alloys are promising biodegradable biomaterials but are still challenging to be used in person with high levels of blood glucose or diabetes. To date, the influence of glucose on magnesium degradation has not yet been elucidated, this issue requires more attention. Herein, we present pure Mg exhibiting different corrosion responses to saline and Hank’s solutions with different glucose contents, and the degradation mechanism of pure Mg in the saline solution with glucose in comparison with mannitol as a control. On one hand, the corrosion rate of pure Mg increases with the glucose concentration in saline solutions. Glucose rapidly transforms into gluconic acid, which attacks the oxides of the metal and decreases the pH of the solution; it also promotes the absorption of chloride ions on the Mg surface and consequently accelerates corrosion. On the other hand, better corrosion resistance is obtained with increasing glucose content in Hank’s solution due to the fact that glucose coordinates Ca2+ ions in Hank’s solution and thus improves the formation of Ca-P compounds on the pure Mg surface. This finding will open up new avenues for research on the biodegradation of bio-Mg materials in general, which could yield many new and interesting results.

Corrosion resistance of layer-by-layer assembled polyvinylpyrrolidone/polyacrylic acid and amorphous silica films on AZ31 magnesium alloys

A layer-by-layer (LbL)-assembled composite coating containing SiO2 and a biocompatible polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) multi-layer, designated as SiO2/(PVP/PAA)5, was prepared on AZ31 Mg alloy via dip-coating. The surface morphology, microstructure and chemical composition of the coating were investigated using FE-SEM, FT-IR, XRD and XPS. The physical properties of the coating were characterized by scratch testing. The results demonstrated that the coating was amorphous and remarkably soft. PVP and PAA promoted the formation of Ca–P precipitates, and the amorphous silica film further enhanced corrosion resistance. The SiO2/(PVP/PAA)5 coating may be a promising surface modification for degradable Mg cardiovascular stents.

Corrosion resistance of Zn–Al layered double hydroxide/ poly(lactic acid) composite coating on magnesium alloy AZ31

A Zn–Al layered double hydroxide (ZnAl-LDH) coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly(lactic acid) (PLA) coating was sealed on the top layer of the ZnAl-LDH coating using vacuum freeze-drying. The characteristics of the ZnAl-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the ZnAl-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAl-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.

Self-assembled silane film and silver nanoparticles coating on magnesium alloys for corrosion resistance and antibacterial applications

Contamination resulting from microbial adhesion on magnesium alloys is very common in many applications. Self-assembly technology was employed to prepare an antibacterial composite coating by fixing silver nanoparticles (AgNPs) onto the surface of magnesium alloys. The AgNPs were immobilized on the surface of 3-aminopropyltrimethoxysilane (APTMS)-modified magnesium alloy AZ31 (APTMS/Mg) through electrostatic inter-attraction between partially protonated amino groups and negatively charged citrate-capped AgNPs, resulting in the AgNPs attached APTMS/Mg (AgNPs/APTMS/Mg) substrate. The prepared Ag colloid and functionalized AZ31 alloy were characterized by ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and electrochemical methods. Finally, the bactericidal activity of AgNPs/APTMS/Mg substrate against Escherichia coli was assessed by the inhibition zone. The results demonstrated that Si-O-Si covalent bonds existed on the substrate with the formation of inorganic Si-O-Mg bonds. AgNPs were immobilized and well-dispersed, forming a uniform submonolayer on the silane film in two dimensions. The AgNPs/APTMS-pretreated AZ31 alloys exhibited better corrosion resistance and excellent antibacterial performance.

Corrosion Resistance of Silane-Modified Hydroxyapatite Films on Degradable Magnesium Alloys

A polymethyltrimethoxysilane (PMTMS)/hydroxyapatite (HA) hybrid coating was successfully fabricated on a magnesium alloy by hydrothermal treatment and immersion method. The microstructure and composition of the coating were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. The physical properties were investigated using scratch testing. At the same time, the corrosion resistance was evaluated via electrochemical and immersion tests. The results demonstrated that the corrosion resistance of the silane hybrid coating was significantly enhanced compared with the naked magnesium alloy. Especially, the corrosion current density of the PMTMS/HA magnesium alloy was three orders of magnitude lower than that of the bare material.

In Vitro Degradation of Pure Magnesium―The Effects of Glucose and/or Amino Acid

The influences of glucose and amino acid (L-cysteine) on the degradation of pure magnesium have been investigated using SEM, XRD, Fourier transformed infrared (FTIR), X-ray photoelectron spectroscopy (XPS), polarization and electrochemical impedance spectroscopy and immersion tests. The results demonstrate that both amino acid and glucose inhibit the corrosion of pure magnesium in saline solution, whereas the presence of both amino acid and glucose accelerates the corrosion rate of pure magnesium. This may be due to the formation of -C=N- bonding (a functional group of Schiff bases) between amino acid and glucose, which restricts the formation of the protective Mg(OH)2 precipitates.

Corrosion resistance and antibacterial properties of polysiloxane modified layer-by-layer assembled self-healing coating on magnesium alloy

Magnesium (Mg) alloys have shown great potential in biomedical materials due to their biocompatibility and biodegradability. However, rapid corrosion rate, which is an inevitable obstacle, hinders their clinical applications. Besides, it is necessary to endow Mg alloys with antibacterial properties, which are crucial for temporary implants. In this study, silver nanoparticles (AgNPs) and polymethyltrimethoxysilane (PMTMS) were introduced into AZ31 Mg alloys via layer-by-layer (LbL) assembly and siloxane self-condensation reaction. The characteristics of the composite films were investigated by SEM, UV-vis, FT-IR, and XRD measurements. Corrosion resistance of the samples was measured by electrochemical and hydrogen evolution tests. Antibacterial activities of the films against Staphylococcus aureus were evaluated by plate-counting method. The results demonstrated that the composite film with smooth and uniform morphologies could enhance the corrosion resistance of Mg alloys owing to the physical barrier and the self-healing functionality of polysiloxane. Moreover, the composite coating possessed antibacterial properties and could prolong the release of assembled silver ions.

In vitro corrosion of pure magnesium and AZ91 alloy-the influence of thin electrolyte layer thickness.

In vivo degradation predication faces a huge challenge via in vitro corrosion test due to the difficulty for mimicking the complicated microenvironment with various influencing factors. A thin electrolyte layer (TEL) cell for in vitro corrosion of pure magnesium and AZ91 alloy was presented to stimulate the in vivo corrosion in the micro-environment built by the interface of the implant and its neighboring tissue. The results demonstrated that the in vivo corrosion of pure Mg and the AZ91 alloy was suppressed under TEL condition. The AZ91 alloy was more sensitive than pure Mg to the inhibition of corrosion under a TEL thickness of less than 200 µm. The TEL thickness limited the distribution of current, and thus localized corrosion was more preferred to occur under TEL condition than in bulk solution. The TEL cell might be an appropriate approach to simulating the in vivo degradation of magnesium and its alloys.

A comparison of corrosion inhibition of magnesium aluminum and zinc aluminum vanadate intercalated layered double hydroxides on magnesium alloys

The magnesium aluminum and zinc aluminum layered double hydroxides intercalated with NO3- (MgAl-NO3-LDH and ZnAl-NO3-LDH) were prepared by the coprecipitation method, and the magnesium aluminum and the zinc aluminum layered double hydroxides intercalated with VOx- (MgAl-VOx-LDH and ZnAl-VOx-LDH) were prepared by the anion-exchange method. Morphologies, microstructures and chemical compositions of LDHs were investigated by SEM, EDS, XRD, FTIR, Raman and TG analyses. The immersion tests were carried to determine the corrosion inhibition properties of MgAl-VOx-LDH and ZnAl-VOx-LDH on AZ31 Mg alloys. The results showed that ZnAl-VOx-LDH possesses the best anion-exchange and inhibition abilities. The influence of treatment parameters on microstructures of LDHs were discussed. Additionally, an inhibition mechanism for ZnAl-VOx-LDH on the AZ31 magnesium alloy was proposed and discussed.