Advances in coatings on Mg alloys and their anti-microbial activity for implant applications

Magnesium matrix composites reinforced by calcium phosphate could not show the desired effect on the magnesium breakdown rate. Rapid disintegration rate limited the magnesium alloys used as biodegradable implant material. The rate of degradation can be minimized and biological activity can be improved in the magnesium alloy by Hydroxyapatite (HA) coating with the improvement of bone induction and conduction abilities. Various alkali post-treatment and conversion coating methods are applied to deposit HA coatings and biocompatible dicalcium phosphate dihydrate (DCPD) on magnesium alloy so that corrosion resistance and surface biocompatibility can be improved to be used in bone tissue engineering applications. Magnesium's corrosion resistance will weaken its antibacterial properties, which are linked to and proportional to the alkaline pH at the time of breakdown. The goal of this study is to bring together and compare contemporary research on different coatings on magnesium and related alloys in relation to antibacterial functionalized activities. A though review has been performed on in vivo and in vitro cytocompatibility, material property, corrosion resistance, and antibacterial properties of the coatings. Increased degradation behavior, biocompatibility, and bioactivity have been achieved following multiple procedures such as alkali treatment with HA electrochemical deposition on magnesium alloy. Multifunctional coatings can make safe and bioactive magnesium alloy surfaces for biodegradable implant applications.     

Surface synthesization of magnesium alloys for improving corrosion resistance and implant applications

In the field of biodegradable material, a new research area has emerged for magnesium (Mg) and its alloys because of its high biocompatibility and biomechanical compatibility. This review summarizes many important types of research that have been done on degradable coatings on magnesium and its alloys for various implant applications. When magnesium alloys come into contact with other metals, they have a low open circuit potential and are consequently prone to galvanic corrosion. When exposed to air or a humid environment, magnesium may rapidly oxidize and generate a thin layer of loose MgO. Its applications were limited due to these drawbacks. Different types of corrosion have been studied in relation to magnesium and its alloys. Several coating methods are described, split into conversion and deposition coatings based on the individual processing procedures employed. This paper covers the most recent advancements in the development of biodegradable Mg alloy coatings over the last decade, revealing that the corrosion resistance of Mg and its alloys increases in most of circumstances due to coatings. Corrosion rate, coating morphology, adhesion, and surface chemistry were identified and explored as significant elements affecting coating performance. Calcium phosphate coatings made by deposition or conversion processes established for orthopedic purposes are the focus of many investigations according to a review of the literature. More research is needed on organic-based biodegradable coatings to improve corrosion resistance. Improved mechanical qualities are also crucial for coating materials. Developing adequate methodologies for studying the corrosion process in depth and over time is still a hot topic of research.     

Electrochemical Behavior of Dental Ni‐Cr Wirolloy Coated with Eco‐friendly Films in Artificial Saliva

The electrochemical corrosion behavior of the non‐precious Ni‐Cr Wirolloy, being used in dentistry, was investigated before and after applying of two types of eco‐friendly coatings, polyvinyl silsesquioxane (PVS) and nano‐hydroxyapatite (nHAP) separately in artificial saliva solution at 37 °C for 14 d of immersion. The study aimed to investigate the effectiveness of the introduced coating films in enhancing the corrosion resistance of the alloy, and in decreasing the leaching of the toxic Ni ions from the alloy into the environment. The electrochemical corrosion investigation methods used are; open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The evaluated results revealed that the electrochemically coated alloy with PVS. prepared at cathodic potential showed higher corrosion resistance and more stable film compared to that prepared by conventional dip‐coating method. At the same time, the nHAP electrochemically coated film provided the best anti‐corrosion properties over all examined time intervals. The obtained results were confirmed via surface analysis, which assured the formation of the prepared coatings on the alloy surface. Chemical analysis of the corrosion product/solutions showed that the effect of electrochemically deposited nHAP and PVS. polymer films in suppression of Ni ions leaching is similar and slightly higher than that of the chemically coated PVS. one; however, all of them are efficient in decreasing the leaching of the risky Ni ions into the solution.     

Characterization and cytocompatibility of polydopamine on MAO‐HA coating supported on Mg‐Zn‐Ca alloy

Magnesium has been suggested as a potential biodegradable metal for the usage as orthopaedic implants. However, high degradation rate in physiological environment remains the biggest challenge, impeding wide clinical application of magnesium‐based biomaterials. In order to reduce its degradation rate and improve the biocompatibility, micro‐arc oxidation coating doped with HA particles (MAO‐HA) was applied as the inner coating, and polydopamine (PDA) film was synthesized by dopamine self‐polymerization as the outer coating. The microstructure evolution of the coating was characterized using scanning electron microscopy (SEM), atomic force microscope (AFM), X‐ray diffraction analyses (XRD), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results showed that PDA film had covered the entire surface of MAO‐HA coating and the pore size of MAO‐HA coating decreased. The root mean square (RMS) roughness of PDA/MAO‐HA coatings was approximately 106.46 nm, which was closer to the optimum surface roughness for cellular attachment as compared with MAO‐HA coatings. Contact angle measurement indicated that the surface wettability had been transformed from hydrophobic to hydrophilic due to the introduction of PDA. The PDA/MAO‐HA coatings exhibited better corrosion resistance in vitro, with the self‐corrosion potential increasing by 150 mV and the corrosion current density decreasing from 2.09 × 10^?5 A/cm ² to 1.46 × 10^?6 A/cm ² . In hydrogen evolution tests, the corrosion rates of the samples coated with PDA/MAO‐HA and MAO‐HA were 4.40 and 5.95 mm/y, respectively. MTS assay test and cell‐surface interactions experiment demonstrated that PDA/MAO‐HA coatings exhibited good cellular compatibility and could promote the adhesion and proliferation of MC3T3‐E1 cells.     

Electrochemical Sensing of Dissolved Hydrogen in Aqueous Solutions as a Tool to Monitor Magnesium Alloy Corrosion

Magnesium and its alloys have been the focus of the development of biodegradable metallic implant materials for years. Since water is reduced to form hydrogen gas during their corrosion, the amount and rate of hydrogen evolution, and therefore the dissolved hydrogen, could be used as an indicator to monitor and compare the corrosion. Here we report on a commercially available Clark‐Type amperometric microsensor and a simple potentiometric sensor for hydrogen to monitor the corrosion of a magnesium alloy in aqueous solutions. The sensors were compared using rare‐earth containing Mg alloy discs (Mg with 4 % Y, 2 % Nd, 0.5 % Ga, 0.5 % Dy) immersed in phosphate buffered saline (pH 7.4) and 3.5 % NaCl.     

Effect of SiC/nano‐CeO2 on wear resistance and microstructures of Ti3Al/γ‐Ni matrix laser‐cladded composite coating on Ti–6Al–4V alloy

The Ti–6Al–4V alloy is an important aviation material, but has a poor resistance to slide wear. Laser cladding of the Al₃Ti + Ni/Cr/C + TiB₂/Al₂O₃ + SiC/nano‐CeO₂ preplaced powders on the Ti–6Al–4V alloy can form the Ti₃Al/γ‐Ni matrix composite coating, which improves the wear resistance of the substrate. In this study, the Al₃Ti + Ni/Cr/C + TiB₂/Al₂O₃ + SiC/nano‐CeO₂ laser‐cladded coating was researched by means of X‐ray diffraction, scanning electron microscopy, and energy dispersive spectrometry. The experimental results indicate that under the action of SiC/nano‐CeO₂, this composite coating exhibited a fine microstructure. Furthermore, the proper content of nano‐CeO₂ decreased the crack tendency. The results above indicated that, it is feasible to improve the tribological property of the Al₃Ti + Ni/Cr/C + TiB₂/Al₂O₃ laser‐cladded coating by adding of SiC/nano‐CeO₂. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization and corrosion properties of Ti‐O/HA composite coatings on Mg‐Zn alloy

Biodegradable magnesium alloys have been widely investigated in the field of biomaterials because they can be gradually dissolved and absorbed by the human body without long‐term existence. However, it was found that bare magnesium implants suffered from rapid corrosion. Surface modification is applied to improve the corrosion resistance and biocompatibility of magnesium implants. In this study, Ti‐O/HA composite coatings including typical flakes and nanofibers were fabricated on the Mg‐Zn alloy. The Ti‐O films were deposited on the magnesium alloy by direct current magnetron sputtering, and subsequently coated with HA flakes and nanofibers by electrochemical deposition, respectively. The obtained coatings were investigated by X‐ray diffraction, Fourier Transform Infrared spectroscopy and scanning electron microscopy. The corrosion resistance was evaluated by potentiodynamic polarization and hydrogen evolution tests in simulated body fluid at 37 °C. The results show that the compact Ti‐O films are composed of particles within the size of 100 nm, the outermost HA coatings are predominantly composed of HA and doped with Na⁺, Mg²⁺ ions and functional groups. The stronger diffraction and broader peak in nanofibers than typical flakes around 25.8° are ascribed to the preferential growth in orientation (002). The morphology of HA coatings changed from typical flakes into nanofibers with the addition of NaF, the mechanism to explain the difference is also discussed. The corrosion resistance was improved significantly by the coatings, the corrosion rates in the 10 days were 4.13, 1.77, 0.96 and 0.85 mm/y, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Corrosion behaviour of mechanically polished AA7075‐T6 aluminium alloy

In the present study, the effects of mechanical polishing on the microstructure and corrosion behaviour of AA7075 aluminium alloy are investigated. It was found that a nano‐grained, near‐surface deformed layer, up to 400 nm thickness, is developed due to significant surface shear stress during mechanically polishing. Within the near‐surface deformed layer, the alloying elements have been redistributed and the microstructure of the alloy is modified; in particular, the normal MgZn₂ particles for T6 are absent. However, segregation bands, approximately 10‐nm thick, containing mainly zinc, are found at the grain boundaries within the near‐surface deformed layer. The presence of such segregation bands promoted localised corrosion along the grain boundaries within the near‐surface deformed layer due to microgalvanic action. During anodic polarisation of mechanically polished alloy in sodium chloride solution, two breakdown potentials were observed at ?750 mV and ?700 mV, respectively. The first breakdown potential is associated with an increased electrochemical activity of the near‐surface deformed layer, and the second breakdown potential is associated with typical pitting of the bulk alloy. Copyright © 2009 John Wiley & Sons, Ltd.     

添加氧化铈对AZ91D镁合金表面富镁涂层的保护作用

通过Machu测试、电化学交流阻抗(EIS)和扫描电子显微镜(SEM)等方法研究了添加氧化铈对AZ91D镁合金表面富镁涂层防护性能的影响.氧化铈添加量较少(0.1%,w)时,对涂层耐蚀性无影响;添加量过多(3%)时,涂层耐蚀性降低;添加氧化铈颗粒为0.5%时,涂层的阻抗增大,涂层电容降低,对AZ91D镁合金基体的保护性能明显提高.尽管添加氧化铈不改变富镁涂层对AZ91D镁合金的保护机制,但可显著延长涂层的服役寿命.氧化铈能够降低纯镁颗粒的电化学反应活性,使镁粉腐蚀速率降低,阴极保护时间延长.添加一定量氧化铈后,也有利于涂层屏蔽性能提高,氧化铈能降低AZ91D镁合金表面阳极腐蚀电流密度,提高镁合金腐蚀电位,从而有利于富镁涂层发挥对镁合金基体的阴极保护作用.     

Corrosion resistance and cytotoxicity of a MgF2 coating on biomedical Mg–1Ca alloy via vacuum evaporation deposition method

To reduce the biocorrosion rate and enhance the biocompatibility by surface modification, MgF₂ coatings were prepared on Mg–1Ca alloy using vacuum evaporation deposition method. The average thickness of the coating was about 0.95 µm. The results of immersion test and electrochemical test indicated that the corrosion rate of Mg–1Ca alloy was effectively decreased after coating with MgF₂. The MgF₂ coating induced calcium phosphate deposition on Mg–1Ca alloy. After 72 h culture, MG63 cells and MC3T3‐E1 cells were well spread on the surface of the MgF₂‐coated Mg–1Ca alloy, while few cells were observed on uncoated Mg–1Ca alloy samples. In summary, MgF₂ coating showed beneficial effects on the corrosion resistance and thus improved cell response of the Mg–1Ca alloy effectively and should be a good surface modification method for other biomedical magnesium alloys. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization and corrosion resistance of pure Mg modified by micro‐arc oxidation using phosphate electrolyte with/without NaOH

Magnesium and its alloys have been suggested as potential absorbable implant materials due to their excellent biodegradability and biocompatibility. Current researchers focus on reducing the rapid corrosion rate of Mg and its alloys by alloying and surface modification. To improve the corrosion resistance, pure Mg is modified by micro‐arc oxidation (MAO) in phosphate electrolyte containing sodium hydroxide and its properties are compared with those formed using only phosphate or sodium hydroxide as electrolytes. A uniform and stable coating layer is formed on Mg after MAO treatment in phosphate electrolyte containing sodium hydroxide. The corrosion resistance of MAO‐coated Mg is evaluated by potentiodynamic polarization study and immersion test. The results reveal that MAO coating enables a good improvement in corrosion resistance, and among them, coatings treated using phosphate electrolyte containing sodium hydroxide offer the best performance. Copyright © 2013 John Wiley & Sons, Ltd.     

Corrosion behavior of electroless Ni–P/TiO2 nanocomposite coatings

Composite Ni–P/nano‐TiO₂ coatings were prepared by simultaneous electroless deposition of Ni–P and nano‐TiO₂ on a low carbon steel substrate. The deposition was carried out from stirred solutions containing suspended nano‐TiO₂ particles. The Ni–P and Ni–P/nano‐TiO₂ coatings before and after heat treatment were characterized by X‐ray diffraction, scanning electron microscopy and energy dispersive X‐ray spectroscopy. The micro‐structural morphologies of the coatings significantly varied with the nano‐TiO₂ content. The corrosion resistance of as‐plated and heat‐treated Ni–P and Ni–P/nano‐TiO₂ coatings was investigated by anodic polarization, Tafel plots and electrochemical impedance spectroscopic (EIS) studies in 3.5% NaCl solution. Ni–P/nano‐TiO₂ coating exhibited superior corrosion resistance over Ni–P coating. Copyright © 2015 John Wiley & Sons, Ltd.     

Biocorrosion and osteoconductivity of PCL/nHAp composite porous film-based coating of magnesium alloy

The present study was aimed at designing a novel porous hydroxyapatite/poly(ε-caprolactone) (nHAp/PCL) hybrid nanocomposite matrix on a magnesium substrate with high and low porosity. The coated samples were prepared using a dip-coating technique in order to enhance the bioactivity and biocompatibility of the implant and to control the degradation rate of magnesium alloys. The mechanical and biocompatible properties of the coated and uncoated samples were investigated and an in vitro test for corrosion was conducted by electrochemical polarization and measurement of weight loss. The corrosion test results demonstrated that both the pristine PCL and nHAp/PCL composites showed good corrosion resistance in SBF. However, during the extended incubation time, the composite coatings exhibited more uniform and superior resistance to corrosion attack than pristine PCL, and were able to survive severe localized corrosion in physiological solution. Furthermore, the bioactivity of the composite film was determined by the rapid formation of uniform CaP nanoparticles on the sample surfaces during immersion in SBF. The mechanical integrity of the composite coatings displayed better performance (∼34% higher) than the uncoated samples. Finally, our results suggest that the nHAp incorporated with novel PCL composite membranes on magnesium substrates may serve as an excellent 3-D platform for cell attachment, proliferation, migration, and growth in bone tissue. This novel as-synthesized nHAp/PCL membrane on magnesium implants could be used as a potential material for orthopedic applications in the future.     

Strontium-doped hardystonite plasma sprayed coatings with robust antimicrobial activity

A strontium-doped hardystonite (Sr-HT) bioceramic, in bulk form, demonstrates excellent bioactivity for bone regeneration with high fracture toughness and compressive strength. This work examines the antibacterial and mechanical properties of Sr-HT coatings on an alpha-beta titanium alloy with a high specific strength and excellent corrosion resistance (Ti-6Al-4V) produced by atmospheric plasma spray (APS) as the deposition coating technique. A hydroxyapatite (HAp) APS coating, a commercial bioceramic coating, is chosen as the control. The in-situ observation showed that Sr-HT powders experience temperatures during plasma processing that exceeded their melting point to form a coating well adhered to the substrate. It was demonstrated that the Sr-HT coating possessed superior antibacterial properties against Gram-positive methicillin-resistant Staphylococcus aureus (MRSA) and Gram-negative Pseudomonas aeruginosa. In addition, the Sr-HT coating exhibits a uniform distribution of hardness and elastic moduli, higher nanohardness and elastic moduli compared to the equivalent properties of the HAp coating. Moreover, the Sr-HT coating outperforms the HAp coating regarding scratch and wear resistance. The bonding and shear strength of the Sr-HT coating are higher than the values required for orthopedic implant coatings. The Sr-HT coating also allows efficient zinc, silicon and strontium ions release when immersed in cell culture media. In summary, the antibacterial capabilities and the mechanical properties of the Sr-HT APS coating exceed those of the commercial HAp APS coating. Therefore, Sr-HT APS coatings are candidates for bioceramic coating applications in orthopedic implants.     

Ca-P Conversion Coating on AZ60 Magnesium Alloy for Biomedical Application

To improve the anti-corrosion behaviors of magnesium alloy in the inner environment of human body,a bioactive Ca-P coating was deposited on the AZ60 magnesium alloy by a novel simple method.The morphologies of the Ca-P coatings formed under different treatment time were studied by scanning electron microscopy（SEM）.The corrosion behaviors of Ca-P coating were investigated by electrochemical polarization test and electrochemical impedance spectroscopy in both 3％（mass fraction） NaCl solution and simulated body fluid（SBF）.Immersion test in SBF was performed to evaluate the corrosion rate of Ca-P coated magnesium alloy.X-Ray diffraction（XRD） analysis result shows that the coating mentioned above mainly consists of dicalcium phosphate dehydrate（CaHPO4·2H2O,DCPD） and β-tricalcium phosphate dehydrate[β-TCP,Ca3（PO4）2],which exhibits good corrosion resistance.After magnesium alloy was immersed in 1 mol/L NaOH solution at 80 ℃ for 2 h,hydroxyapatite [Ca10（PO4）6（OH）2,HA]appeared on the magnesium alloy substrate,which can further decrease the corrosion rate of AZ60 magnesium alloy in SBF.     

hytic Acid Conversion Coatings of Magnesium

A chrome‐free conversion coating treatment for magnesium by phytic acid solution was developed. The immersion experiments were used for evaluating the effects of the processing parameters (such as conversion temperature and time, concentration and pH value of phytic acid solution) on the corrosion resistance of the phytic acid conversion coating. The morphologies and compositions of the coatings were determined by SEM and EDS respectively. The experimental results indicated that the corrosion resistance of the conversion coating formed in the solution containing 0.5% phytic acid at 25°C and pH=4 for 30 min was higher than that of natural oxide, and the conversion coating formed on the surface of magnesium was of multilayer mainly consisting of Mg, C, O and P. The thicknesses of the conversion coatings were approximately 1.0–15 µm and the conversion coatings presented obvious network‐like cracks. The electrochemical potentiodynamic polarization experiment indicated that the free corrosion potential of the magnesium with phytic acid conversion coating was increased, and its corrosion current and corrosion rate declined in 3.5% NaCl solution. Phytic acid conversion coating could improve the electrochemical property of magnesium and provide effective protection, which can improve the corrosion resistance of magnesium.     

Cross‐linked waterborne alkyd hybrid resin coatings modified by fluorinated acrylate‐siloxane with high waterproof and anticorrosive performance

Waterborne alkyd resin coatings are ideal for use as corrosion protection coatings because of its high cost‐effective and environmental advantages. However, their uses are restricted to general applications due to their poor acid, water, and alkali resistance. In this work, waterborne alkyd hybrid resins modified with fluorinated acrylate‐siloxane were synthesized via a surfactant‐free miniemulsion polymerization process using maleic anhydride and silicon modified alkyd resin, dodecafluoroheptyl methacrylate, methyl methacrylate, and butyl acrylate as monomers. And then, crosslinking alkyd resin films were prepared at room temperature using trimethylolpropane‐tris‐(β‐N‐azir‐idinyl) propionate (XR‐100) as the crosslinking agent. The acquired films had lower water absorption and higher water contact angles and had better mechanical/thermal properties, as well as good waterproof property. Most importantly, the electrochemical corrosion studies revealed that the cross‐linked coating exhibited superior corrosion resistance performance with an inhibition efficiency of 99.95% and a corrosion rate of 6.95 × 10^?3 mm per year.     

超音速火焰喷涂含铝或锌中间层的YSZ热障涂层

在镁合金基底表面直接制备热障涂层,涂层的耐蚀性较差。采用超音速火焰喷涂法在镁合金基底和热障涂层之间分别制备了Al涂层和Zn涂层。通过XRD,SEM和EDS对涂层进行物相、微观结构和点扫描元素分析,采用电化学工作站对Al涂层试样和Zn涂层试样进行耐腐蚀性分析,同时研究了含Al中间层和含Zn中间层的热障涂层的抗热震性能。结果表明:Al涂层表面粗糙度(10.237±0.527μm)大于Zn涂层表面粗糙度(7.171±0.488μm),且喷涂过程中仅有轻微氧化。Al涂层试样的耐腐蚀性优于Zn涂层试样。含Zn中间层的热障涂层具有更好的抗热震性能。     

AZ91镁合金表面稀土转化膜的制备及耐蚀性能研究

采用在镁合金表面形成无毒、无污染的稀土铈转化膜的方法解决AZ91镁合金表面的腐蚀问题。确定了最佳成膜工艺参数，讨论了处理液的浓度、成膜温度和成膜时间等因素对转化膜耐蚀性的影响。利用湿热实验、阳极极化曲线的测定等实验方法评价了转化膜对镁合金表面的防护作用。结果表明，在潮湿温热条件下稀土铈转化膜试样仍能保持膜层的完整性并具有较高的覆盖度，腐蚀现象不明显。腐蚀电势升高，出现钝化现象，腐蚀电流密度下降，稀土铈转化膜可以提高AZ91镁合金的耐蚀性能。用扫描电镜观察了膜的微观形貌，稀土铈转化膜是由基膜和附着的细小颗粒组成，最佳工艺形成的铈转化膜无破碎现象，对AZ91镁合金表面的腐蚀过程的发生有明显的抑制作用。     

非晶态Ni-W-B合金的电沉积及其热处理前后的性能

To strengthen the properties of Ni-W alloy, dimethylamine borane （DMAB） was added to an alloy Ni-W electrolyte solution and a ternary Ni-W-B alloy was electrodeposited. The electrodeposition, crystallographic structure, surface morphology, heat treatment and corrosion resistance, of the alloy were studied by DSC, XRD, SEM and electrochemical techniques. The results showed that the structure of the alloy was greatly affected by the cooperation of boron compound. DSC experiment combined with X-ray diffractometry indicated that the obtained Ni-W-B alloy was still in amorphous structure although W content in the alloy was decreased by the addition of DMAB. After heat treatment at 400 ℃ for 1 h, the microhardness was increased from 612 to 947 kg.mm^-2 that was com- parative to Cr coating. The appearance of the as-plated coating was in f＇me and slice grains and kept almost no change after heat treatment. In w=0.03 NaC1 solution the as-plated coating presented very good corrosion resistance. After the coating was heat-treated its corrosion resistance was enhanced.