A novel approach to heal the sol-gel coating system on magnesium alloy for corrosion protection

Sol-gel-based coatings exhibit high potentiality to be as an alternative to toxic chromate coatings for surface pre-treatment of metals and alloys. However, as soon as even small defects appear in the coating, the coating cannot stop the development of corrosion process. Present work demonstrates the possibility to use zinc nitrate as healing agent to repair the organic silane coatings in NaCl solution. The zinc nitrate was added to the 0.005 M NaCl solution where AZ91D magnesium alloy coated with organic silane coating was immersed. The healing process and the healing mechanism were investigated by electrochemical measurements and scanning electron microcopy coupled with energy dispersive spectroscopy. The results demonstrated the introduction of zinc nitrate to the electrolyte could stop the development of corrosion process of the coating system and a remarkable recovery on corrosion resistance could be obtained. This effect may be attributed to the formation of zinc oxide/hydroxide on the defective areas, hindering the corrosion activities.     

Complex anticorrosion coating for ZK30 magnesium alloy

This work aims at developing a new complex anticorrosion protection system for ZK30 magnesium alloy. This protective coating is based on an anodic oxide layer loaded with corrosion inhibitors in its pores, which is then sealed with a sol–gel hybrid polymer. The porous oxide layer is produced by spark anodizing. The sol–gel film shows good adhesion to the oxide layer as it penetrates through the pores of the anodized layer forming an additional transient oxide–sol–gel interlayer.The thickness of this complex protective coating is about 3.7–7.0 μm. A blank oxide–sol–gel coating system or one doped with Ce³⁺ ions proved to be effective corrosion protection for the magnesium alloy preventing corrosion attack after exposure for a relatively long duration in an aggressive NaCl solution.The structure and the thickness of the anodized layer and the sol–gel film were characterized by scanning electron microscopy (SEM). The corrosion behaviour of the ZK30 substrates pre-treated with the complex coating was tested by electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET), and scanning ion-selective electrode techniques (SIET).     

Bioactive HA/TiO2 coating on magnesium alloy for biomedical applications

Magnesium alloys are new class of biodegradable alloys having many favourable properties to overcome the limitations of currently used biomedical alloys. Recently, several coatings have been developed to overcome their higher degradation rate. In this regard, a new attempt has been made to develop Hydroxyapatite and Hydroxyapatite/TiO₂ coatings on magnesium alloys to increase the biocompatibility and reduce the corrosion rate. The coated surfaces were characterized by Fourier-Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction Analysis (XRD), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) Spectroscopy, Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM). Contact angle measurements proved higher hydrophilic nature of HA/TiO₂ coating compared to HA coating. In-vitro studies showed that HA–TiO₂ coated alloy exhibited higher osteoinduction compared to HA coated alloy. Hydrogen evolution studies and corrosion studies confirmed greater reduction in degradation rate of HA/TiO₂ coated alloy. Vickers microhardness test also showed enhancement in mechanical strength of the composite coated alloy compared to HA coated alloy. Three point bend test depicted better adherence of the HA/TiO₂ coating compared to HA coating on the substrate. Cell culture studies proved higher cell attachment and proliferation on composite coated alloy by controlling the release of magnesium ions into the surrounding body tissue.     

A calcium phosphate coating improving corrosion resistance of the biodegradable magnesium alloy with graphene oxide modifying the deposition

Biodegradable magnesium alloy is an ideal material for medical implant applications, but its application is limited by its rapid degradation. Therefore, it becomes the main goal to improve corrosion resistance. In this study, a calcium phosphate dihydrate/graphene oxide composite coating was designed on the AZ60 alloy for medical applications. A calcium phosphate dihydrate coating was first prepared by biomimetic deposition on the alkali pretreated magnesium alloy, and graphene oxide was dispersed in the solution to modify the deposition. The results showed that graphene oxide could not only alter the loose striped calcium phosphate coating to the compact flaked composite coating, but also enhance the corrosion resistance with a reduced corrosion current density by 2 orders of magnitude, an increased impedance by 3 orders of magnitude and a corrosion rate down to 7/20. The in vitro biocompatibility of the composite coating was also demonstrated by a series cell experiments, with a cell viability of 120%. The composite coating provides a feasible method to enhance the corrosion resistance and biocompatibility of magnesium alloys.     

Fault-tolerant hybrid epoxy-silane coating for corrosion protection of magnesium alloy AZ31

In this work, a hybrid epoxy-silane coating was developed for corrosion protection of magnesium alloy AZ31. The average thickness of the film produced by dip-coating procedure was 14 μm. The adhesion strength of the epoxy-silane coating to the Mg substrate was evaluated by pull-off tests and was found to be higher than 16 MPa both in dry and wet conditions. The hybrid epoxy-silane coating showed high corrosion resistance both when intact and when punched through by a needle. The low frequency impedance of intact coating was higher than 1 GΩ cm² after one month of immersion in 3.5% NaCl solution. Both, artificially induced defects and corrosion sites that appeared on the metal surface did not propagate. Their passivation behavior, that we call fault-tolerance, was observed by EIS, SVET-SIET and SEM-EDS. It was ascribed to the good adhesion, high coating integrity and corrosion inhibiting effect provided by diethylenetriamine used as epoxy hardener.     

Preparation and corrosion resistance studies of zirconia coating on fluorinated AZ91D magnesium alloy

Novel anti-corrosion zirconia coating was prepared via the sol–gel method for AZ91D magnesium alloy using zirconium nitrate hydrate as a precursor modified with acetylacetone (AcAc). Magnesium alloy substrates were first fluorinated in 20% HF aqueous solution at room temperature for 20 h, then, the zirconia coating was deposited on the fluorinated sample by dip coating. Basing on the sol–gel process, a chelate complex from the reaction of zirconium coordinating AcAc was formed which was supported by UV–vis spectrum analysis. The result showed that the absorption peak could be seen for the sol at 308 nm, which was red-shifted by 36 nm from that of methanol form of AcAc (272 nm). Moreover, Fourier transform infrared (FT-IR) spectrum analysis was performed to examine the structural differences between the gel and AcAc. The results indicated that the chelate complex with a bidentante structure was formed through the interaction chemically between zirconium nitrate and AcAc. The surface morphology of the zirconia coating was characterized by scanning electron microscope (SEM), an uniform coating can be obtained on the fluorinated sample. The corrosion resistance of the substrate, the fluorinated with and without the zirconia coating in the 3.5 wt.% NaCl solution was studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests, respectively. The results demonstrated that the zirconia coating could greatly improve the corrosion resistance of the AZ91D magnesium alloy. Furthermore, the effect of the different heat-treatment temperatures for the zirconia coating on corrosion resistance was also discussed.     

氧化石墨烯/羟基磷灰石涂层对镁合金耐腐蚀性的影响

采用仿生法在改性模拟体液中于镁合金表面制备了羟基磷灰石(HA)涂层和氧化石墨烯/羟基磷灰石(GO/HA)复合涂层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)对两种涂层进行了形貌和结构表征,通过析氢量测量、极化曲线和交流阻抗等方法分别研究了裸镁合金、含HA涂层及GO/HA涂层镁合金在pH为7.4的模拟体液(SBF)和3.5%NaCl溶液中的腐蚀行为。结果表明,氧化石墨烯增加了羟基磷灰石涂层的致密性,含GO/HA复合涂层的AZ91镁合金耐腐蚀性能最好,相对于裸镁合金,其腐蚀电流密度降低了一个数量级,析氢量降低了52%。     

镁合金表面防护涂层的研究进展

镁合金以其高比强度、比模量和优异的力学性能,已在众多领域受到广泛关注。但是,化学活性高、耐蚀性能差的缺陷制约了其应用范围。寻找一种合适的表面处理方法已成为必然。本文概述了国内外关于镁合金表面防护涂层的研究现状,主要有化学转化膜、阳极氧化膜、金属涂(镀)层、激光表面合金改性层、气相沉积层和溶胶-凝胶涂层等。展望了镁合金表面防护涂层的发展趋势。     

Microstructure and properties of Nb2O5/Mg gradient coating on AZ31 magnesium alloy by magnetron sputtering

A Nb₂O₅/Mg gradient coating was synthesized on AZ31 magnesium alloy through the magnetron sputtering technique. The microstructure and properties of the coating were investigated by SEM, AFM, EDS and XPS, scratch tester, nanoindenter, friction tester, and electrochemical workstation, with a Nb₂O₅ monolayer coating as a control. The results show that all the as-disposed films have an amorphous columnar structure, and can improve the mechanical, anti-wear and anti-corrosion properties of AZ31 magnesium alloy. The Nb₂O₅/Mg gradient coating shows a gradual change in chemical composition through its depth, decreasing the residual stress of the coating/substrate system, thus reducing the risk of film cracking, and increasing compactness of the coating. Compared with a Nb₂O₅ single-layer film of the same thickness, the gradient coating exhibits increased adhesion, H/E and H³/E² increased by about 16 times, 7.8% and 100% respectively, and a wear rate reduced by more than an order of magnitude. In addition, the gradient coating has better corrosion resistance, having a two orders of magnitude lower current density and one order of magnitude higher polarization resistance. This study provides a workable strategy for improving the performance of ceramic coatings on magnesium alloy, for medical applications.     

AZ31镁合金稀土转化成膜工艺研究

本文对AZ31镁合金表面稀土转化成膜工艺进行了研究。分析了不同的成膜工艺参数丽土盐溶液组成、转化成膜时间）对稀土转化膜的形貌及耐蚀性能的影响。扫描电镜分析了不同成膜工艺形成的稀土转化膜的表面形貌;极化曲线研究了转化膜的电化学腐蚀行为。结果表明：当转化液中硝酸铈浓度为4．3423g·L^-1和硝酸镧浓度为4．3302g·L^-1时,转化膜的耐蚀性能最好;成膜时间对膜的耐蚀性也有不同程度的影响。     

Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy

This work aims to develop and study new anticorrosion films for AZ31B magnesium alloy based on the sol-gel coating approach.Hybrid organic-inorganic sols were synthesized by copolymerization of epoxy-siloxane and titanium or zirconium alkoxides. Tris(trimethylsilyl) phosphate was also used as additive to confer additional corrosion protection to magnesium-based alloy. A sol-gel coating, about 5-μm thick, shows good adhesion to the metal substrate and prevents corrosion attack in 0.005 M NaCl solution for 2 weeks. The sol-gel coating system doped with tris(trimethylsilyl)-phosphate revealed improved corrosion protection of the magnesium alloy due to formation of hydrolytically stable Mg-O-P chemical bonds.The structure and the thickness of the sol-gel film were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The corrosion behaviour of AZ31B substrates pre-treated with the sol-gel derived hybrid coatings was tested by electrochemical impedance spectroscopy (EIS). The chemical composition of the silylphosphate-containing sol-gel film at different depths was investigated by X-ray photoelectron spectroscopy (XPS) with depth profiling.     

Novel copper immersion coating on magnesium alloy AZ91D in an alkaline bath

Copper immersion coating of magnesium alloys has, to date, been conducted only in acidic baths. This article describes a novel alkaline bath for copper immersion coating on AZ91D magnesium alloy. Prior to the coating process, a chemical etching process of the magnesium substrate was optimized using orthogonal experimental methodology. The copper immersion coating was then investigated with regard to the effect of pH and fluoride content in the deposition bath. It was revealed during the coating process that an increase of pH and fluoride content led to a surface film formation on the magnesium substrate. The surface film formation occurred simultaneously with copper reduction, rendering a controlled magnesium dissolution, thereby a controlled copper deposition. With optimized conditions of chemical etching and immersion coating processes, uniform copper deposits were achieved.     

Electrophoretic deposition of bioactive glass nanopowders on magnesium based alloy for biomedical applications

To slow down the initial biodegradation rate of magnesium (Mg) alloy, crystalline nano-sized bioactive glass coating was used to deposit on micro-arc oxidized AZ91 samples via electrophoretic deposition (EPD). Zeta potential and conductivity of the bioactive glass suspension were characterized at various pH values to identify the most stable dispersion conditions. The bone-bonding properties of bioactive glass coated samples were evaluated in terms of apatite-forming ability during the immersion in simulated body fluid (SBF) solution. Results revealed that the ability to form a bioactive glass coating via EPD was influenced by the degree of its crystalline phase composition. Moreover, the potentiodynamic polarization tests recorded significant drops in corrosion current density and corrosion rate of the coated samples which implies a good level of corrosion protective behavior. These preliminary results show that this process will enable the development of Mg implants in the later stage of bone healing.     

Preparation and characterization of a double-layer coating on magnesium alloy AZ91D

A double-layer coating was prepared on AZ91D alloy by plasma electrolytic oxidation (PEO) plus electroless plating (EP). The plasma eletrolytic oxidation film was prepared in a silicate bath as an inner layer of the coating. Electroless plated Ni-P layer grew from the pores of the PEO film in a nickelous acetate bath and formed as the outer layer of the coating. The microstructure and crystallographic structure was observed with FESEM and XRD. The corrosion resistance of the double-layer coating was evaluated by means of chronopotentiometric (E-t), potentiodynamic polarization (E-i), neutral salt spray test and electrochemical impedance spectroscopy (EIS) test. Compared with the data of as-cast AZ91D magnesium, the open circuit potential of the double-layer coated AZ91D alloy increased by 1.1815 V, while the self-corrosion current density decreased by two orders of magnitude. E-i, EIS result showed that the corrosion resistance of magnesium alloy AZ91D was improved by the double-layer coating. The salt spray test and polarization test results show that the pitting corrosion resistance of AZ91D alloy was improved greatly. An equivalent circuit was proposed to fit the impedance diagrams of AZ91D alloy with the coating.     

医用镍钛合金表面微弧氧化膜层的显微结构及耐蚀性

采用由NaAlO2和NaH2PO2组成的电解液,以微弧氧化技术在医用镍钛合金表面制备Al2O3陶瓷膜层,以减少合金表面Ni含量,并进一步提高其耐腐蚀性能,使其具有良好的生物相容性.随微弧氧化过程中处理时间的延长,试样表面的游动火花由白色逐渐向橙色转变,火花数减少但尺寸增大.所得陶瓷膜层由γ-Al2O3晶相组成,随着处理...     

封闭处理对镁合金磷酸钡转化膜的影响

在Na2SiO3和NaOH溶液中,研究了封闭处理对AZ91D镁合金磷酸钡转化膜的影响,采用扫描电镜(SEM)和X射线衍射谱(XRD)研究了封闭前后磷酸钡转化膜的表面形貌及其相组成,采用全浸蚀试验和电化学方法检测了膜层的抗腐蚀性能。结果表明,封闭后的磷酸盐转化膜更加平整、致密。与封闭前的转化膜相比,封闭后的转化膜新增了C、Si元素和一些晶态物质,如SiO2、BaSi4O9、Na2SiO3和MgF2。封闭处理可以明显提高镁合金磷酸钡转化膜的抗腐蚀性能。     

抗水化镁钙质涂料的研制与应用

采用石灰石(或方解石)、消石灰制取镁钙质涂料,材料具有抗水化、耐侵蚀、净化钢水的特点。     

Preparation and corrosion resistance of a self-sealing hydroxyapatite- MgO coating on magnesium alloy by microarc oxidation

An ideal self-sealing hydroxyapatite (HA)-MgO coating was designed on an AZ31 Mg alloy by one-step microarc oxidation (MAO) with the addition of HA nanoparticles into a base electrolyte. The formation mechanism of the self-sealing HA-MAO coating was discussed. The effect of the nano-HA addition on the corrosion resistance of the MAO coating was evaluated by corrosion tests in Hank's solution. The results show that HA nanoparticles inertly incorporated into the MAO coating during the process of coating growth. HA and MgO were the main constituents of the HA-MAO coating. The HA nanoparticles were absent in the inner barrier layer but concentrated in the outer porous layer. In addition, HA nanoparticles accumulated much more inside coating defects than in the other zones, which resulted in the nearly ideal sealing of micropores on the coating surface. By forming a denser and more stable outer layer, the incorporation of HA nanoparticles greatly enhanced the anti-corrosion properties of the MAO coating.     

Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.     

Corrosion protection behavior of AZ31 magnesium alloy with cathodic electrophoretic coating pretreated by silane

As an alternative process to phosphate and chromate conversion coatings, silane pretreatment was used to improve the performance of cathodic electrophoretic coating (E-coat) on AZ31 Mg alloy in this study. The galvanic corrosion behavior of AZ31 Mg alloy with E-coat coupled with Q235 steel was investigated. Compared to bare Mg alloy and Mg alloy with conventional painting, the corrosion properties of the AZ31 Mg alloy pretreated with silane and subsequently E-coated were studied during salt solution immersion and salt spray testing. The surface morphologies of the Mg alloy were examined in detail after immersion in NaCl solution for different times using digital photography and scanning electron microscopy (SEM). The corrosion current density of the specimens was characterized by DC polarization tests. It was found that silane pretreatment of AZ31 Mg alloy followed by subsequent E-coat led to much better corrosion protection than that without silane treatment. The silane pretreatment and E-coat delayed the galvanic corrosion of Mg alloy coupled with 235 steel bolts.