Surface treatments for controlling corrosion rate of biodegradable Mg and Mg-based alloy implants

Abstract

Due to their excellent biodegradability characteristics, Mg and Mg-based alloys have become an emerging material in biomedical implants, notably for repair of bone as well as coronary arterial stents. However, the main problem with Mg-based alloys is their rapid corrosion in aggressive environments such as human bodily fluids. Previously, many approaches such as control of alloying materials, composition and surface treatments, have been attempted to regulate the corrosion rate. This article presents a comprehensive review of recent research focusing on surface treatment techniques utilised to control the corrosion rate and surface integrity of Mg-based alloys in both in vitro and in vivo environments. Surface treatments generally involve the controlled deposition of thin film coatings using various coating processes, and mechanical surfacing such as machining, deep rolling or low plasticity burnishing. The aim is to either make a protective thin layer of a material or to change the micro-structure and mechanical properties at the surface and sub-surface levels, which will prevent rapid corrosion and thus delay the degradation of the alloys. We have organised the review of past works on coatings by categorising the coatings into two classes—conversion and deposition coatings—while works on mechanical treatments are reviewed based on the tool-based processes which affect the sub-surface microstructure and mechanical properties of the material. Various types of coatings and their processing techniques under two classes of coating and mechanical treatment approaches have been analysed and discussed to investigate their impact on the corrosion performance, biomechanical integrity, biocompatibility and cell viability. Potential challenges and future directions in designing and developing the improved biodegradable Mg/Mg-based alloy implants were addressed and discussed. The literature reveals that no solutions are yet complete and hence new and innovative approaches are required to leverage the benefit of Mg-based alloys. Hybrid treatments combining innovative biomimetic coating and mechanical processing would be regarded as a potentially promising way to tackle the corrosion problem. Synergetic cutting-burnishing integrated with cryogenic cooling may be another encouraging approach in this regard. More studies focusing on rigorous testing, evaluation and characterisation are needed to assess the efficacy of the methods.     

The effect of selected alloying element additions on properties of Mg-based alloy as bioimplants: A literature review

This review investigates the current application limitations of Mg and Mg alloys. The key issues hindering the application of biodegradable Mg alloys as implants are their fast degradation rate and biological consideration. We have discussed the effect of some selected alloying element additions on the properties of the Mg-based alloy, especially the nutrient elements in human (Zn, Mn, Ca, Sr). Different grain sizes, phase constituents and distributions consequently influence the mechanical properties of the Mg alloys. Solution strengthening and precipitation strengthening are enhanced by the addition of alloying elements, generally improving the mechanical properties. Besides, the hot working process can also improve the mechanical properties. Combination of different processing steps is suggested to be adopted in the fabrication of Mg-based alloys. Corrosion properties of these Mg-based alloys have been measured in vitro and in vivo. The degradation mechanism is also discussed in terms of corrosion types, rates, by-products and response of the surrounding tissues. Moreover, the clinical response and requirements of degradable implants are presented, especially for the nutrient elements (Ca, Mn, Zn, Sr). This review provides information related to different Mg alloying elements and presents the promising candidates for an ideal implant.     

Surface Modification on Biodegradable Magnesium Alloys as Orthopedic Implant Materials to Improve the Bio-adaptability:A Review

Magnesium(Mg) and its alloys as a novel kind of biodegradable material have attracted much fundamental research and valuable exploration to develop its clinical application. Mg alloys degrade too fast at the early stage after implantation, thus commonly leading to some problems such as osteolysis, early fast mechanical loss, hydric bubble aggregation, gap formation between the implants and the tissue. Surface modification is one of the effective methods to control the degradation property of Mg alloys to adapt to the need of organism. Some coatings with bioactive elements have been developed, especially for the micro-arc oxidation coating, which has high adhesion strength and can be added with Ca, P, and Sr elements. Chemical deposition coating including bio-mimetic deposition coating, electro-deposition coating and chemical conversion coating can provide good anticorrosion property as well as better bioactivity with higher Ca and P content in the coating. From the biodegradation study, it can be seen that surface coating protected the Mg alloys at the early stage providing the Mg alloy substrate with lower degradation rate. The biocompatibility study showed that the surface modification could provide the cell and tissue stable and weak alkaline surface micro-environment adapting to the cell adhesion and tissue growth.The surface modification also decreased the mechanical loss at the early stage adapting to the loadbearing requirement at this stage. From the interface strength between Mg alloys implants and the surrounding tissue study, it can be seen that the surface modification improved the bio-adhesion of Mg alloys with the surrounding tissue, which is believed to be contributed to the tissue adaptability of the surface modification. Therefore, the surface modification adapts the biodegradable magnesium alloys to the need of biodegradation, biocompatibility and mechanical loss property. For the different clinical application, different surface modification methods can be provided to adapt to the clinical requirements for the Mg alloy implants.     

Challenges and Solutions for the Additive Manufacturing of Biodegradable Magnesium Implants

Due to their capability of fabricating geometrically complex structures, additive manufacturing (AM) techniques have provided unprecedented opportunities to produce biodegradable metallic implants—especially using Mg alloys, which exhibit appropriate mechanical properties and outstanding biocompatibility. However, many challenges hinder the fabrication of AM-processed biodegradable Mg-based implants, such as the difficulty of Mg powder preparation, powder splash, and crack formation during the AM process. In the present work, the challenges of AM-processed Mg components are analyzed and solutions to these challenges are proposed. A novel Mg-based alloy (Mg–Nd–Zn–Zr alloy, JDBM) powder with a smooth surface and good roundness was first synthesized successfully, and the AM parameters for Mg-based alloys were optimized. Based on the optimized parameters, porous JDBM scaffolds with three different architectures (biomimetic, diamond, and gyroid) were then fabricated by selective laser melting (SLM), and their mechanical properties and degradation behavior were evaluated. Finally, the gyroid scaffolds with the best performance were selected for dicalcium phosphate dihydrate (DCPD) coating treatment, which greatly suppressed the degradation rate and increased the cytocompatibility, indicating a promising prospect for clinical application as bone tissue engineering scaffolds.     

Blood compatibility of zinc–calcium phosphate conversion coating on Mg–1.33Li–0.6Ca alloy

Magnesium alloys as a new class of biomaterials possess biodegradability and biocompatibility in comparison with currently used metal implants. However, their rapid corrosion rates are necessary to be manipulated by appropriate coatings. In this paper, a new attempt was used to develop a zinc-calcium phosphate (Zn-Ca-P) conversion coating on Mg-1.33Li-0.6Ca alloys to increase the biocompatibility and improve the corrosion resistance. In vitro blood biocompatibility of the alloy with and without the Zn-Ca-P coating was investigated to determine its suitability as a degradable medical biomaterial. Blood biocompatibility was assessed from the hemolysis test, the dynamic cruor time test, blood cell count and SEM observation of the platelet adhesion to membrane surface. The results showed that the Zn-Ca-P coating on Mg-1.33Li-0.6Ca alloys had good blood compatibility, which is in accordance with the requirements for medical biomaterials.     

Surface Refinement of Metal Foams

Aluminium foams produced via the PM‐process are characterized by a moderate specific strength, a high surface roughness, and a poor wear behavior; to increase their mechanical properties and to improve the surface finish, wear and corrosion resistance; thermally sprayed coatings can be applied. The quality of the coating depends on the coating material, the chosen process, the preparation of the surface and spraying parameters. Aluminium alloys and iron based alloys for abrasive applications were deposited via electric arc spraying, ceramic coatings against wear were deposited by means of plasma spraying. Hard metallic coatings for severe abrasive applications were applied by high‐velocity‐oxyfuel spraying (HVOF). The results proved the suitability of this technique to significantly enhance the mechanical properties and the surface finish of metal foams. The specific strength and stiffness of the new composite materials outperform pure metal foams. The corrosion behavior was tested performing a salt spray test.     

镁及其合金表面防护性涂层国外研究进展

综述了近年来国外镁及其合金表面防护性涂层的研究进展,其中包括化学转化涂层、阳极氧化膜层、镀层(电镀、化学镀)、扩散膜层、激光表面合金改性层、气相沉积层及有机涂层等在镁合金基体上的应用情况,分析了其各自的利弊,并对镁合金表面防护技术的发展方向进行了展望.     

Design and characterizations of novel biodegradable ternary Zn-based alloys with IIA nutrient alloying elements Mg,Ca and Sr

Apart from the industrial and automotive applications, Zn and Zn-based alloys are considered as a new kind of potential biodegradable material quite recently. However, one drawback of pure Zn as potential biodegradable metal lies in that pure Zn has quite low strength and plasticity. In the present study, three important IIA essential nutrient elements Mg, Ca and Sr and hot-rolling and hot-extrusion thermal deformations have been applied to overcome the drawback of pure Zn and benefit the biocompatibility of Zn-based potential implants. The microstructure, mechanical properties, corrosion behavior, hemocompatibility, in vitro cytocompatibility were studied systematically to investigate their feasibility as bioabsorbable implants. The results showed that the mechanical properties of the ternary Zn–1Mg–1Ca, Zn–1Mg–1Sr and Zn–1Ca–1Sr alloys are much higher than that of pure Zn, owing to both the alloying effects and thermal deformation effects. In vitro hemolytic rate test and cell viability test indicated that the addition of the IIA nutrient alloying elements Mg, Ca and Sr into Zn can benefit their hemocompatibility and cytocompatibility, which would further guarantee the biosafety of these new kind of biodegradable Zn-based implants for future clinical applications.     

镁合金预处理对其表面有机涂层耐蚀性的影响

镁合金压铸件上涂覆有机涂层后的耐蚀性能与其涂装前的表面处理状态有着密切关系.采用中性盐雾试验和盐水浸渍法对经喷砂、打磨、无铬化学转化、微弧氧化4种不同表面预处理后的丙烯酸树脂涂层进行了耐蚀性测试.结果表明:采用合适的预处理能显著提高涂层的耐蚀性能,其中微弧氧化涂层耐蚀性最佳,在盐雾和盐水浸渍试验中失效时间分别达96 h和168 h;预处理后基材表面光滑的涂层失效形式以起泡为主,而具有微孔或粗糙表面的涂层则以点蚀为主.     

镁合金表面水滑石膜耐蚀性研究进展

镁合金由于具有优异的性能受到研究者的关注和重视,但易腐蚀的特性严重制约了其工程应用,故需采取合适的手段增强其耐蚀性。水滑石膜具有良好的离子交换性及物理屏障作用,近年来在镁合金表面改性方面逐步得到发展。介绍了多种镁合金表面水滑石膜层的制备工艺及其成膜原理,初步探讨了其在腐蚀环境下的耐蚀机制,并详述了几种进一步提高水滑石膜质量的改性方法及原理,展望了未来研究的工作重点和发展方向。     

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.     

Improvement of <Emphasis Type="Italic">in vitro</Emphasis> behavior of an Mg alloy using a nanostructured composite bioceramic coating

Magnesium (Mg) alloys as a new group of biodegradable metal implants are being extensively investigated as a promising selection for biomaterials applications due to their apt mechanical and biological performance. However, as a foremost drawback of Mg alloys, the high degradation in body fluid prevents its clinical applications. In this work, a bioceramic composite coating is developed composed of diopside, bredigite, and fluoridated hydroxyapatite on the AZ91 Mg alloy in order to moderate the degradation rate, while improving its bioactivity, cell compatibility, and mechanical integrity. Microstructural studies were performed using a transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD) analysis, and energy dispersive spectroscopy (EDS). The degradation properties of samples were carried out under two steps, including electrochemical corrosion test and immersion test in simulated body fluid (SBF). Additionally, compression test was performed to evaluate the mechanical integrity of the specimens. L-929 fibroblast cells were cultured on the samples to determine the cell compatibility of the samples, including the cell viability and attachment. The degradation results suggest that the composite coating decreases the degradation and improves the bioactivity of AZ91 Mg alloy substrate. No considerable deterioration in the compression strength was observed for the coated samples compared to the uncoated sample after 4 weeks immersion. Cytotoxicity test indicated that the coatings improve the cell compatibility of AZ91 alloy for L-929 cells.     

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.     

Coatings on Mg alloys and their mechanical properties: A review

Poor corrosion resistance is a serious drawback of Mg alloys, restricting their practical applications. Coating is one of the effective techniques for improvement in the poor corrosion resistance. In this paper, the coating processes for Mg alloys so far developed are reviewed. Among several processes, the coating processes based on mechanical energy, including metal forming, are attractive because the corrosion resistance and formability of Mg alloys are simultaneously improved.     

Cerium-based coating for enhancing the corrosion resistance of bio-degradable Mg implants

Recently there has been interest in employing degradable metallic implants for internal fixation in bone fracture healing. The major purpose of using degradable implants is to avoid a second surgery for implant removal when bone healing has completed. However, the corrosion rate of Mg in vivo is too high. Thus increasing the corrosion resistance of Mg is the key problem to address in the development of degradable Mg implants. One possible route is by way of surface treatment, which would lower the corrosion rate at the initial phase of bone healing, the period during which the implant provides mechanical support for the broken bone. In the present study cerium oxide coating was prepared on pure Mg by cathodic deposition in cerium nitrate solution followed by hydrothermal treatment. The coated samples were characterized by SEM, EDS and XRD. The corrosion resistance in Hanks’ solution (a simulated body fluid) was studied using polarization method and electrochemical impedance spectroscopy (EIS). The corrosion resistance of cerium oxide coated Mg in Hanks’ solution at 37 °C and pH 7.4 was higher than that of bare Mg by about two orders of magnitude.     

Bio-corrosion characterization of Mg–Zn–X (X = Ca, Mn, Si) alloys for biomedical applications

The successful applications of magnesium-based alloys as biodegradable orthopedic implants are mainly inhibited due to their high degradation rates in physiological environment. This study examines the bio-corrosion behaviour of Mg–2Zn–0.2X (X = Ca, Mn, Si) alloys in Ringer’s physiological solution that simulates bodily fluids, and compares it with that of AZ91 magnesium alloy. Potentiodynamic polarization and electrochemical impedance spectroscopy results showed a better corrosion behaviour of AZ91 alloy with respect to Mg–2Zn–0.2Ca and Mg–2Zn–0.2Si alloys. On the contrary, enhanced corrosion resistance was observed for Mg–2Zn–0.2Mn alloy compared to the AZ91 one: Mg–2Zn–0.2Mn alloy exhibited a four-fold increase in the polarization resistance than AZ91 alloy after 168 h exposure to the Ringer’s physiological solution. The improved corrosion behaviour of the Mg–2Zn–0.2Mn alloy with respect to the AZ91 one can be ascribed to enhanced protective properties of the Mg(OH)₂ surface layer. The present study suggests the Mg–2Zn–0.2Mn alloy as a promising candidate for its applications in degradable orthopedic implants, and is worthwhile to further investigate the in vivo corrosion behaviour as well as assessed the mechanical properties of this alloy.     

Mechanical and bio-corrosion properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys

Binary Mg–xCa alloys and the quaternary Mg–Ca–Mn–xZn were studied to investigate their bio-corrosion and mechanical properties. The surface morphology of specimens was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results of mechanical properties show that the yield strength (YS), ultimate tensile strength (UTS) and elongation of quaternary alloy increased significantly with the addition of zinc (Zn) up to 4 wt.%. However, further addition of Zn content beyond 4 wt.% did not improve yield strength and ultimate tensile strength. In contrast, increasing calcium (Ca) content has a deleterious effect on binary Mg–Ca alloys. Compression tests of the magnesium (Mg) alloys revealed that the compression strength of quaternary alloy was higher than that of binary alloy. However, binary Mg–Ca alloy showed higher reduction in compression strength after immersion in simulated body fluid. The bio-corrosion behaviour of the binary and quaternary Mg alloys were investigated using immersion tests and electrochemical tests. Electrochemical tests shows that the corrosion potential (E_corr) of binary Mg–2Ca significantly shifted toward nobeler direction from −1996.8 to −1616.6 mV_SCE with the addition of 0.5 wt.% manganese (Mn) and 2 wt.% Zn content. However, further addition of Zn to 7 wt.% into quaternary alloy has the reverse effect. Immersion tests show that the quaternary alloy accompanied by two secondary phases presented higher corrosion resistance compared to binary alloys with single secondary phase. The degradation behaviour demonstrates that Mg–2Ca–0.5Mn–2Zn alloy had the lowest degradation rate among quaternary alloys. In contrast, the binary Mg–2Ca alloy demonstrated higher corrosion rates, with Mg–4Ca alloy having the highest rating. Our analysis showed the Mg–2Ca–0.5Mn–2Zn alloy with suitable mechanical properties and excellent corrosion resistance can be used as biodegradable implants.     

Influence of coatings and hot corrosion on the fatigue behaviour of nickel-based superalloys

The fatigue behaviour of materials and components is strongly affected by the surface conditions, i.e. the surface finish and the materials properties in the near- surface region. Therefore any change in these conditions during fabrication or service may change the fatigue properties.It is common practice to coat turbine blades with materials that are resistant to hot corrosion. However, this treatment involves chemical and mechanical changes in the materials surface properties which could also change the fatigue properties of these components. The recommended heat treatment for the coating normally differs from that which produces the best mechanical or creep properties of the base metal and hence may cause additional changes in the fatigue properties. Chemical and mechanical changes in the surface conditions of an uncoated component may also take place during operation. Additionally, a large amount of notching may occur since oxidation and hot corrosion are not homogeneously distributed but take place preferentially at sites such as grain boundaries.In this work we investigate the effect of Pt-Al coatings on the high cycle fatigue (HCF) behaviour of the cast nickel-based alloys IN 738LC and IN 939 which are commonly used in large industrial gas turbines. A reduction in the fatigue life due to the coating was observed. However, the simultaneous occurence of hot corrosion attack and cyclic loading was much more detrimental. Fractographic and metallographic investigations showed that, in the as-coated condition, the crack initiation sites in the Pt-Al-coated alloys were internal pores situated just below the surface of the substrate. After aging or hot corrosion cracks initiate at the surface probably as a result of notch development by the attack. When HCF and hot corrosion are acting concurrently the coatings are expected to give a beneficial effect by protecting the surface from accelerated crack initiation.     

Corrosion studies of modified organosilane coated magnesium–yttrium alloy in different environments

Magnesium (Mg) and its alloys have numerous potential applications as biodegradable implants, but the fast degradation rate of Mg alloys at the initial implanted stage could be a problem. This paper describes the modification of the water-based bis-[triethoxysilyl] ethane (BTSE) silane applied to the surface of magnesium–yttrium (Mg–4Y) to increase its corrosion resistance. Surface characterization by SEM, FTIR, and EDX showed that the hydrolysis and condensation of the silane resulted in a covalent bonding to the Mg–4Y surface. Corrosion behavior of the uncoated and coated Mg–4Y alloy was evaluated in different environments by using a novel self-developed corrosion probe. Based on the electrochemical results of DC polarization and electrochemical impedance spectroscopy (EIS), we conclude that the epoxy-modified BTSE silane coating successfully increases the corrosion resistance at the initial stage of implantation. The corrosion rates in the flesh of dead mice environments such as body cavity and subcutaneous tissue of the mice were lower than the corrosion rates in in vitro environments.