Corrosion resistance of in-situ growth of nano-sized Mg(OH)2 on micro-arc oxidized magnesium alloy AZ31—Influence of EDTA

One of the major obstacles for the clinical use of biodegradable magnesium (Mg)-based materials is their high corrosion rate. Micro-arc oxidation (MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)₂ film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium (EDTA-2Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)₂ hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)₂ coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating. The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)₂ film. The current density of Mg(OH)₂-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)₂-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.     

Surface Engineering of Biodegradable Magnesium Alloys for Enhanced Orthopedic Implants

Magnesium (Mg) alloys have been promised for biomedical implants in orthopedic field, however, the fast corrosion rate and mode challenge their clinical application. To push Mg alloys materials into practice, a composite coating with biodegradable and high compatible components to improve anticorrosion property of an Mg alloy (i.e., AZ31) is designed and fabricated. The inner layer is micro‐nano structured Mg(OH)₂ through hydrothermal treatment. Then stearic acid (SA) is introduced to modify Mg(OH)₂ for better reducing the gap below a surface‐degradation polymer layer of poly(1,3‐trimethylene carbonate). Benefited by the SA modification effect, this sandwiched coating avoids corrosive medium penetration via enhancing the adhesion strength at the interface between outer and inner layers. Both in vitro and in vivo tests indicate that the composite coating modified AZ31 perform a better anticorrosion behavior and biocompatibility compared to bare AZ31. Strikingly, a 1.7‐fold improvement in volume of newly formed bone is observed surrounding the composite coating modified implant after 12 week implantation. The sandwiched biocompatible coating strategy paves a hopeful way for future translational application of Mg alloys orthopedic materials in clinics.     

MAO-DCPD composite coating on Mg alloy for degradable implant applications

Magnesium (Mg) is a promising metallic material for use as degradable orthopedic implants. The density and Young's modulus of Mg are close to those of human bone, and it is non-toxic and degradable in body fluids. However, the realization of Mg as an implant material is hampered by its high corrosion rate. The present article aims at improving the corrosion resistance and bioactivity of a Mg alloy AZ80 via surface treatment. AZ80 was coated with a composite coating consisting of an oxide layer formed by micro-arc oxidation (MAO) and a top layer of dicalcium phosphate dihydrate (DCPD, CaHPO₄·2H₂O) fabricated by electrodeposition. The corrosion behavior and apatite-forming ability in simulated body fluids (SBFs) were studied using hydrogen evolution measurements and SEM. The results show that the MAO-DCPD composite coating significantly reduces the corrosion rate of AZ80 and at the same time enhances the deposition of apatite on the coating.     

Preliminary study of biodegradation of AZ31B magnesium alloy

Magnesium alloys are potential to be developed as a new type of biodegradable implant material by use of their active corrosion behavior. Both in vitro and in vivo biodegradation properties of an AZ31B magnesium alloy were investigated in this work. The results showed that AZ31B alloy has a proper degradation rate and much lower hydrogen release in Hank’s solution, with a degradation rate of about 0.3 mm/year and hydrogen release below 0.15 mL/cm². The animal implantation test showed that the AZ31B alloy could slowly biodegrade in femur of the rabbit and form calcium phosphate around the alloy sample, with the Ca/P ratio close to the natural bone.     

Micromorphological effect of calcium phosphate coating on compatibility of magnesium alloy with osteoblast

Abstract

Octacalcium phosphate (OCP) and hydroxyapatite (HAp) coatings were developed to control the degradation speed and to improve the biocompatibility of biodegradable magnesium alloys. Osteoblast MG-63 was cultured directly on OCP- and HAp-coated Mg-3Al-1Zn (wt%, AZ31) alloy (OCP- and HAp-AZ31) to evaluate cell compatibility. Cell proliferation was remarkably improved with OCP and HAp coatings which reduced the corrosion and prevented the H₂O₂ generation on Mg alloy substrate. OCP-AZ31 showed sparse distribution of living cell colonies and dead cells. HAp-AZ31 showed dense and homogeneous distribution of living cells, with dead cells localized over and around corrosion pits, some of which were formed underneath the coating. These results demonstrated that cells were dead due to changes in the local environment, and it is necessary to evaluate the local biocompatibility of magnesium alloys. Cell density on HAp-AZ31 was higher than that on OCP-AZ31 although there was not a significant difference in the amount of Mg ions released in medium between OCP- and HAp-AZ31. The outer layer of OCP and HAp coatings consisted of plate-like crystal with a thickness of around 0.1 μm and rod-like crystals with a diameter of around 0.1 μm, respectively, which grew from a continuous inner layer. Osteoblasts formed focal contacts on the tips of plate-like OCP and rod-like HAp crystals, with heights of 2–5 μm. The spacing between OCP tips of 0.8–1.1 μm was wider than that between HAp tips of 0.2–0.3 μm. These results demonstrated that cell proliferation depended on the micromorphology of the coatings which governed spacing of focal contacts. Consequently, HAp coating is suitable for improving cell compatibility and bone-forming ability of the Mg alloy.     

Corrosion resistance of biodegradable polymeric layer-by-layer coatings on magnesium alloy AZ31

Biocompatible polyelectrolyte multilayers (PEMs) and polysiloxane hybrid coatings were prepared to improve the corrosion resistance of biodegradable Mg alloy AZ31. The PEMs, which contained alternating poly(sodium 4-styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH), were first self-assembled on the surface of the AZ31 alloy substrate via electrostatic interactions, designated as (PAH/PSS)₅/AZ31. Then, the (PAH/PSS)₅/AZ31 samples were dipped into a methyltrimethoxysilane (MTMS) solution to fabricate the PMTMS films, designated as PMTMS/(PAH/PSS)₅/AZ31. The surface morphologies, microstructures and chemical compositions of the films were investigated by FE-SEM, FTIR, XRD and XPS. Potentiodynamic polarization, electrochemical impedance spectroscopy and hydrogen evolution measurements demonstrated that the PMTMS/(PAH/PSS)₅/AZ31 composite film significantly enhanced the corrosion resistance of the AZ31 alloy in Hank’s balanced salt solution (HBSS). The PAH and PSS films effectively improved the deposition of Ca-P compounds including Ca₃(PO₄)₂ and hydroxyapatite (HA). Moreover, the corrosion mechanism of the composite coating was discussed. These coatings could be an alternative candidate coating for biodegradable Mg alloys.     

Effect of surface coating on antibacterial behavior of magnesium based metals

Antibacterial behaviors of magnesium (Mg) based metal, pure Mg and AZ31 alloy, with and without surface coatings were studied. The results indicated that both pure Mg and AZ31 alloy had strong antibacterial effect against Escherichia coli and Staphylococcus aureus with rapid increases of pH values of the bacterial suspensions. Pure Mg with porous silicon-contained (Si) coating by micro-arc oxidation still maintained its antibacterial ability while with a mild increase of the pH value. However, pure Mg and AZ31 alloy with fluorine-contained (F) and Si coatings by chemical conversion, respectively, lost their antibacterial abilities with nearly no change of the pH values, owing to the much dense coatings on surfaces.     

Enhanced corrosion resistance and cytocompatibility of biomimetic hyaluronic acid functionalised silane coating on AZ31 Mg alloy for orthopaedic applications

This paper reports the corrosion resistant and cytocompatible properties of the hyaluronic acid-silane coating on AZ31 Mg alloy. In this study, the osteoinductive properties of high molecular weight hyaluronic acid (HA, 1–4?MDa) and the corrosion protection of silane coatings were incorporated as a composite coating on biodegradable AZ31 Mg alloy for orthopaedic applications. The multi-step fabrication of coatings first involved dip coating of a passivated AZ31 Mg alloy with a methyltriethoxysilane-tetraethoxysilane sol-gel to deposit a dense, cross-linked and corrosion resistant silane coating (AZ31-MT). The second step was to create an amine-functionalised surface by treating coated alloy with 3-aminopropyl-triethoxy silane (AZ31-MT-A) which facilitated the immobilisation of HA via EDC-NHS coupling reactions at two different concentrations i.e 1?mg.ml^?1 (AZ31-MT-A-HA1) and 2?mg.ml^?1 (AZ31-MT-A-HA2). These coatings were characterised by Fourier transform infrared spectroscopy, atomic force microscopy and static contact angle measurements which confirmed the successful assembly of the full coatings onto AZ31 Mg alloy. The influence of HA-silane coating on the corrosion of Mg alloy was investigated by electrical impedance spectroscopy and long-term immersion studies measurements in HEPES buffered DMEM. The results showed an enhanced corrosion resistance of HA functionalised silane coated AZ31 substrate over the uncoated equivalent alloy. Furthermore, the cytocompatibility of MC3T3-E1 osteoblasts was evaluated on HA-coated AZ31-MT-A substrates by live-dead staining, quantification of total cellular DNA content, scanning electron microscope and alkaline phosphatase activity. The results showed HA concentration-dependent improvement of osteoblast cellular response in terms of enhanced cell adhesion, proliferation and differentiation. These findings hold great promise in employing such biomimetic multifunctional coatings to improve the corrosion resistance and cytocompatibility of biodegradable Mg-based alloy for orthopaedic applications.

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Self-catalytic degradation of iron-bearing chemical conversion coating on magnesium alloys ---- Influence of Fe content

A number of industrial and biomedical fields, such as hydraulic fracturing balls for gas and petroleum exploitation and implant materials, require Mg alloys with rapid dissolution. An iron-bearing phosphate chemical conversion (PCC) coating with self-catalytic degradation function was fabricated on the Mg alloy AZ31. Surface morphologies, chemical compositions and degradation behaviors of the PCC coating were investigated through FE-SEM, XPS, XRD, FTIR, electrochemical and hydrogen evolution tests. Results indicated that the PCC coating was characterized by iron, its phosphates and hydroxides, amorphous Mg(OH)₂ and Mg_3−n(H_nPO₄)₂. The self-catalytic degradation effects were predominately concerned with the Fe concentration, chemical composition and microstructure of the PCC coating, which were ascribed to the galvanic corrosion between Fe in the PCC coating and the Mg substrate. The coating with higher Fe content and porous microstructure exhibited a higher degradation rate than that of the AZ31 substrate, while the coating with a trace of Fe and compact surface disclosed a slightly enhanced corrosion resistance for the AZ31 substrate.     

Biodegradable poly(lactide-co-glycolide) coatings on magnesium alloys for orthopedic applications

Polymeric film coatings were applied by dip coating on two magnesium alloy systems, AZ31 and Mg4Y, in an attempt to slow the degradation of these alloys under in vitro conditions. Poly(lactic-co-glycolic acid) polymer in solution was explored at various concentrations, yielding coatings of varying thicknesses on the alloy substrates. Electrochemical corrosion studies indicate that the coatings initially provide some corrosion protection. Degradation studies showed reduced degradation over 3 days, but beyond this time point however, do not maintain a reduction in corrosion rate. Scanning electron microscopy indicates inhomogeneous coating durability, with gas pocket formation in the polymer coating, resulting in eventual detachment from the alloy surface. In vitro studies of cell viability utilizing mouse osteoblast cells showed improved biocompatibility of polymer coated substrates over the bare AZ31 and Mg4Y substrates. Results demonstrate that while challenges remain for long term degradation control, the developed polymeric coatings nevertheless provide short term corrosion protection and improved biocompatibility of magnesium alloys for possible use in orthopedic applications.     

Improved corrosion resistance of Mg alloy AZ31B induced by selective evaporation of Mg using large pulsed electron beam irradiation

Large pulsed electron beam (LPEB) irradiation was employed as a surface treatment of magnesium (Mg) alloy AZ31B to enhance its corrosion and wear resistance. Selective evaporation of Mg induced by LPEB irradiation at an energy density of 5 J/cm² for 40 cycles has led to the formation of an Al-enriched re-solidified layer with nano-grained structure consisting of Mg_3.1Al_0.9 metastable phase. The formation of such a re-solidified layer after LPEB irradiation has enabled a decrease in corrosion rate of Mg alloy AZ31B in 3.5% NaCl solution. Different equivalent electrical circuit models were proposed to account for the corrosion behavior of untreated Mg alloy AZ31B and those subjected to LPEB irradiation. A decrease in wear depth when compared to that of the untreated alloy suggests an increase in wear resistance of LPEB-irradiated Mg alloy AZ31B. Adhesive wear is the predominant mechanism of untreated Mg alloy AZ31B while abrasive wear mechanism dominates for LPEB-irradiated Mg alloy AZ31B.     

Fluoride treatment and in vitro corrosion behavior of an AZ31B magnesium alloy

As a new class of biodegradable material, magnesium alloys have attracted much attention in recent years. In order to improve the corrosion resistance, a fluoride coating was prepared on the surface of AZ31B magnesium alloy. The surface characterization analysis showed a dense coating with some irregular pores was formed. The TF-XRD analysis indicated that the coating was mainly composed of MgO and MgF₂. Electrochemical and immersion tests proved that the fluoride conversion coating significantly improved the corrosion resistance of AZ31B. Three-point bending test revealed that the degradation behavior of the fluoride treated AZ31B could meet the requirement as a biodegradable material.     

Electrochemical characteristics of calcium-phosphatized AZ31 magnesium alloy in 0.9 % NaCl solution

Magnesium alloys suffer from their high reactivity in common environments. Protective layers are widely created on the surface of magnesium alloys to improve their corrosion resistance. This article evaluates the influence of a calcium-phosphate layer on the electrochemical characteristics of AZ31 magnesium alloy in 0.9 % NaCl solution. The calcium phosphate (CaP) layer was electrochemically deposited in a solution containing 0.1 M Ca(NO₃)₂, 0.06 M NH₄H₂PO₄ and 10 ml l^?1 of H₂O₂. The formed surface layer was composed mainly of brushite [(dicalcium phosphate dihidrate (DCPD)] as proved by energy-dispersive X-ray analysis. The surface morphology was observed by scanning electron microscopy. Immersion test was performed in order to observe degradation of the calcium phosphatized surfaces. The influence of the phosphate layer on the electrochemical characteristics of AZ31, in 0.9 % NaCl solution, was evaluated by potentiodynamic measurements and electrochemical impedance spectroscopy. The obtained results were analysed by the Tafel-extrapolation method and equivalent circuits method. The results showed that the polarization resistance of the DCPD-coated surface is about 25 times higher than that of non-coated surface. The CaP electro-deposition process increased the activation energy of corrosion process.     

Effect of Fe ions on the thermal and optical properties of the ceramic coating grown in-situ on AZ31 Mg Alloy

This research investigates the effect of Fe₂(SO₄)₃ on the thermal and optical properties of the ceramic coatings formed on AZ31 Mg alloy. The different ceramic coatings were obtained by plasma electrolytic oxidation (PEO) in electrolytes that contain varied concentrations of Fe₂(SO₄)₃. The microstructure, element distribution, composition as well as the thermal and optical properties of the coatings were studied with scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray Diffraction (XRD), UV–VIS–NIR spectrophotometer and infrared reflectometer. The results show that all of the coatings prepared were mainly composed with MgO, with trace-amount of Fe₃O₄ presents and Fe seems entered into the MgO crystal structure. With the increasing of the concentration of Fe₂(SO₄)₃, the solar absorptance and infrared emittance increased initially but then remain stable. We found that at the concentrations 8 g L⁻¹, the coating has the highest solar absorptance (0.94) and infrared emittance (0.83). Our results show that coatings formed with this method could be useful as a thermal control coating in a variety of applications, such as in the spacecraft.     

In vitro corrosion resistance and antibacterial performance of novel tin dioxide-doped calcium phosphate coating on degradable Mg-1Li-1Ca alloy

A SnO_2-doped calcium phosphate(Ca-P-Sn) coating was constructed on Mg-1 Li-1 Ca alloy by a hydrothermal process. The fabricated functional coatings were investigated using scanning electron microscopy(SEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FT-IR). A triple-layered structure, which is composed of Ca_3(PO_4)_2,(Ca, Mg)_3(PO_4)_2, SnO_2, and MgHPO_4·3 H_2O, is evident and leads to the formation of Ca_(10)(PO_4)_6(OH)_2 in Hank's solution. Electrochemical measurements, hydrogen evolution tests and plating counts reveal that the corrosion resistance and antibacterial activity were improved through the coating treatment. The embedded SnO_2 nanoparticles enhanced crystallisation of the coating.The formation and degradation mechanisms of the coating were discussed.     

An electrodeposition method of calcium phosphate coatings on titanium alloy

Calcium phosphates coatings were deposited onto titanium alloy discs via en electrodeposition method. Titanium alloy discs were blasted with calcium phosphate particles, then etched in a mixture of nitric and fluoric acids and rinsed in demineralized water. The titanium alloy disc (cathode) and platinum mesh (anode) were immersed in a supersaturated calcium phosphate electrolyte buffered at pH 7.4 and connected to a current generator. The microstructure, chemical composition and crystallinity of the electrodeposited coatings were studied as function of time 10–120 min, temperature 25–80°C, current density 8–120 mA/cm², magnesium and hydrogen carbonate amounts (0.1–1 mM). Uniform calcium phosphate coatings were obtained in 30 min but coating thickness increased with deposition time. Raising the temperature of electrolyte resulted in more uniform coatings as ionic mobility increased. Low current density was preferable due to hydrogen gas evolving at the cathode, which disturbed the deposition of calcium phosphate crystals on titanium. The amounts of magnesium and hydrogen carbonate ions affected both the homogeneity and morphology of the coatings. This study showed that the electrodeposition method is efficient for coating titanium with osteoconductive calcium phosphate layers.     

Enhanced biocorrosion resistance and biocompatibility of degradable Mg–Nd–Zn–Zr alloy by brushite coating

To further improve the corrosion resistance and biocompatibility of Mg–Nd–Zn–Zr alloy (JDBM), a biodegradable calcium phosphate coating (Ca–P coating) with high bonding strength was developed using a novel chemical deposition method. The main composition of the Ca–P coating was brushite (CaHPO₄·2H₂O). The bonding strength between the coating and the JDBM substrate was measured to be over 10 MPa, and the thickness of the coating layer was about 10–30 μm. The in vitro corrosion tests indicated that the Ca–P treatment improved the corrosion resistance of JDBM alloy in Hank's solution. Ca–P treatment significantly reduced the hemolysis rate of JDBM alloy from 48% to 0.68%, and induced no toxicity to MC3T3-E1 cells. The in vivo implantation experiment in New Zealand's rabbit tibia showed that the degradation rate was reduced obviously by the Ca–P treatment and less gas was produced from Ca–P treated JDBM bone plates and screws in early stage of the implantation, and at least 10 weeks degradation time can be prolonged by the present coating techniques. Both Ca–P treated and untreated JDBM Mg alloy induced bone growth. The primary results indicate that the present Ca–P treatment is a promising technique for the degradable Mg-based biomaterials for orthopedic applications.     

Aqueous deposition of calcium phosphates and silicate substituted calcium phosphates on magnesium alloys

Attempts were made to deposit homogeneous films of calcium phosphates (CaPs) on two magnesium alloy systems, AZ31 and Mg-4Y, through an aqueous phosphating bath method. The deposition of silicate substituted CaPs by this aqueous method was also explored as silicate substitution is believed to increase the bioactivity of CaPs. The effect of doped and undoped coatings on the in vitro degradation and bioactivity of both alloy systems was studied. FTIR and EDX confirmed the deposition of Ca, P, and Si on both alloys and the coatings appeared to consist primarily biphasic mixtures of hydroxyapatite and β-TCP. These largely inhomogeneous coatings, as observed by SEM, were not shown to have any significant effect on maintaining the physiological pH of the culture medium in comparison to the uncoated samples, as the pH remained approximately in the 8.4-8.7 range. Interestingly, despite similar pH profiles between the coated and uncoated samples, CaP coatings affected the degradation of both alloys. These doped and undoped calcium phosphate coatings were observed to decrease the degradation of AZ31 whereas they increased the degradation of Mg-4Y. In vitro studies on cell attachment using MC3T3-E1 mouse osteoblasts showed that between the uncoated alloys, Mg-4Y appeared to be the more biocompatible of the two. Silicate substituted CaP coatings were observed to increase the cell attachment on AZ31 compared to bare and undoped CaPs coated samples, but did not have as great of an effect on increasing cell attachment on Mg-4Y.     

Corrosion and wear resistance of AZ91D magnesium alloy with and without microarc oxidation coating in Hank’s solution

Immersion test, electrochemistry test and block-on-cylinder type wear test have been applied to study the corrosion and wear resistance of AZ91D Mg alloy with and without microarc oxidation (MAO) treatment in Hank’s solution. Through MAO, a ceramic coating is directly formed on the surface of AZ91D Mg alloy, by which its corrosion and wear resistances are greatly improved. The immersion test results show the mass loss of untreated AZ91D Mg is 15 times of that of MAO ones after 21 days immersion test. The electrochemical corrosion experiments show that the corrosion potential of Mg alloy is improved from −1.5786 V to −0.43019 V through MAO surface treatment, the corrosion current is reduced from 0.028703 A/cm² to 2.0456 × 10⁻⁷ A/cm², and the polarization resistance is improved from 1.2753 × 10⁻⁵ Ω/cm² to 0.90886 Ω/cm². The lubricate sliding wear test results show the mass loss of untreated AZ91D Mg is 1.5 times of that of MAO ones.     

Influence of dicalcium phosphate dihydrate coating on the in vitro degradation of Mg-Zn alloy

To reduce the degradation rate and further to improve the biocompatibility of magnesium alloy, dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) has been fabricated on a kind of magnesium-zinc alloy by way of electrodeposition method. The experimental results of XRD, SEM and EDS showed that the electrodeposited coating on the Mg-Zn alloy mainly contains the flake-like DCPD, along with some octacalcium phosphate (Ca₈(HPO₄)₂(PO₄)₄·4H₂O, OCP). After the in vitro degradation of the coated alloy in modified-simulated body fluid (m-SBF), it was proved that the coating could reduce the degradation rate effectively, and the samples were covered by calcium phosphate salts with a higher Ca/P ratio. Therefore, it indicates that compared with the bare alloy, the DCPD coating rendered a more biocompatible surface, and is a promising coating candidate for biomedical magnesium materials.