Corrosion Behaviors of Long‐Period Stacking Ordered Structure in Mg Alloys Used in Biomaterials: A Review

The long‐period stacking ordered (LPSO) phases have distinctive microstructures and significant effect on the promotion of mechanical properties of Mg alloys, which have received considerable attention not only as industrial materials but also as biodegradable implant materials recently. By now, numerous researchers devote to study the effects of the microstructures of LPSO phases on the mechanical properties of Mg alloys. But a few of them reveal the relationship between LPSO phases and corrosion behaviors of Mg alloys. Therefore, the knowledge of characteristics of LPSO phases and their effects on biocorrosion behaviors is essential. In this review, the current understanding about the structure, growth, transformation, and deformation of LPSO phases in Mg alloys are summarized. The recent developments of biocorrosion behaviors of Mg alloys are reviewed. The information on the immersion and corrosion mechanisms of Mg alloys are provided. The role of LPSO structures on corrosion behaviors of Mg alloys is intensively analyzed. Based on the current understandings, some problems are pointed out and suggestions for further research of Mg alloys with LPSO structures using as biomedical materials are provided.

     

Magnesium based degradable biomaterials: A review

Magnesium has been suggested as a revolutionary biodegradable metal for biomedical applications. The corrosion of magnesium, however, is too rapid to match the rates of tissue healing and, additionally, exhibits the localized corrosion mechanism. Thus it is necessary to control the corrosion behaviors of magnesium for their practical use. This paper comprehensively reviews the research progress on the development of representative magnesium based alloys, including Mg-Ca, Mg-Sr, Mg-Zn and Mg-REE alloy systems as well as the bulk metallic glass. The influence of alloying element on their microstructures, mechanical properties and corrosion behaviors is summarized. The mechanical and corrosion properties of wrought magnesium alloys are also discussed in comparison with those of cast alloys. Furthermore, this review also covers research carried out in the field of the degradable coatings on magnesium alloys for biomedical applications. Calcium phosphate and biodegradable polymer coatings are discussed based on different preparation techniques used. We also compare the effect of different coatings on the corrosion behaviors of magnesium alloys substrate.     

生物可降解镁合金的发展现状与展望

镁合金作为新型可降解医用金属材料,近年来成为生物材料领域的研究热点,并越来越受到生物、材料和医学界的关注和重视.从工程用镁合金、新型医用镁合金、表面改性镁合金和新颖结构镁合金4个方面综述了国际和国内生物可降解镁合金方面的研究现状,系统地介绍和总结了目前生物可降解镁合金材料的合金设计、力学性能、体液腐蚀特性、细胞毒性和动物体内植入实验的相关结果,展望了未来生物可降解镁合金亟待解决的科学问题和应用前景.     

可生物降解镁合金血管支架管坯的材料制备及成形研究进展

对可生物降解镁合金血管支架的研究现状进行了综述。镁合金作为新型可降解物材料成为了研究热点,其中血管支架是其最有前景的应用方向之一。镁合金微细管材成形困难及镁合金血管支架腐蚀速率过快,是制约其大规模临床应用的2个主要因素。作者介绍了近期国内外的相关研究,包括改善镁合金力学性能,以及为提高成形极限采取的新成形方法,为提高镁合金耐腐蚀性而采取的各种处理方法等。     

Recent advances in biodegradation controls over Mg alloys for bone fracture management: A review

Magnesium (Mg) alloys possess comparable physical and mechanical properties to bone, making them an outstanding candidate of implant materials for bone fracture treatment. In addition to the excellent biocompatibility, and bioactivity, the engagement of Mg alloys is key for a number of biological functionalities in the human body. The unique biodegradation nature of Mg alloy implants implies that it may not require a secondary removal procedure when the expected supporting tasks accomplish, as they may simply and safely “disappear” over time. Nonetheless, the demonstrated drawback of potentially rapid degradation, is an issue that must be addressed appropriately for Mg implants and is consequently given unique attention in this review article. Herein, the critical criteria and the state-of-the-art strategies for controlling the degradation process of Mg alloys are reported. Furthermore, future developments of biodegradable Mg and its alloys systems with satisfactory specifications for clinical trials and deployment, are discussed. This review aims to provide information to materials scientists and clinical practitioners in the context of developing practical biodegradable Mg alloys.     

A preliminary study for novel use of two Mg alloys (WE43 and Mg3Gd)

In this study, two types of magnesium alloys (WE43 and Mg3Gd) were compared with Heal-All membrane (a biodegradable membrane used in guided bone regeneration) in vitro to determine whether the alloys could be used as biodegradable membranes. Degradation behavior was assessed using immersion testing with simulated body fluid (SBF). Microstructural characteristics before and after immersion were evaluated through scanning electron microscopy, and degradation products were analyzed with energy dispersive spectrometry (EDS). To evaluate the biocompatibility of the three types of materials, we performed cytotoxicity, adhesion, and mineralization tests using human osteoblast-like MG63 cells. Immersion testing results showed no significant difference in degradation rate between WE43 and Mg3Gd alloys. However, both Mg alloys corroded faster than the Heal-All membrane, with pitting corrosion as the main corrosion mode for the alloys. Degradation products mainly included P- and Ca-containing apatites on the surface of WE43 and Mg3Gd, whereas these apatites were rarely detected on the surface of the Heal-All membrane. All three type of materials exhibited good biocompatibility. In the mineralization experiment, the alkaline phosphatase (ALP) activity of 10 % Mg3Gd extract was significantly higher than the extracts of the two other materials and the negative control. This study highlighted the potential of these Mg-REE alloys for uses in bone regeneration and further studies and refinements are obviously required.     

Effects of Li addition on the corrosion behaviour and biocompatibility of Mg(Li)–Zn–Ca metallic glasses

Magnesium alloys with suitable corrosion behaviour and good mechanical properties are desired for biodegradable materials. In the current study, novel Mg–Li-based metallic glasses (MGs) demonstrate potential clinical applications as implantable biodegradable materials. The amorphous structure of MGs provides suitable elastic modulus with human bone. The enhanced corrosion resistance of MGs realises a uniform corrosion process, as well as maintains a stable acid-based environment, and increases cell proliferation. A schematic model is proposed to illustrate the corrosion mechanisms of MGs. Adding Li significantly improves the corrosion resistance of MGs. Both the indirect cytotoxicity and direct cell culture assays are conducted using transfected osteoblasts (hFOB) cells. Results show that the novel Mg–Li–Zn–Ca MGs have good biocompatibility.     

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.     

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

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.     

In Vivo and In Vitro Degradation Behavior of Magnesium Alloys as Biomaterials

The corrosion behavior of pure Mg,AZ31,and AZ91D were evaluated in various in vitro and in vivo environments to investigate the potential application of these metals as biodegradable implant materials.DC polarization tests and immersion tests were performed in different simulated body solutions,such as distilled(DI) water,simulated body fluid(SBF) and phosphate buffered solution(PBS).Mg/Mg alloys were also implanted in different places in a mouse for in vivo weight loss and biocompatibility investigations.The in vivo subcutis bio-corrosion rate was lower than the corrosion rate for all of the in vitro simulated corrosive environments.The Mg/Mg alloys were biocompatible based on histology results for the liver,heart,kidney,skin and lung of the mouse during the two months implantation.Optical microscopy and scanning electron microscopy were carried out to investigate the morphology and topography of Mg/Mg alloys after immersion testing and implantation to understand the corrosion mechanisms.     

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.     

Recent Research and Development Activities on Mg Alloys at CAAM

A brief review of recent research and development activities on light weight Mg alloys at the Center for Advanced Aerospace Materials (CAAM) is reported. Current research projects include various fields such as: (i) development of high strength/ductility Mg alloys; (ii) improvement in corrosion resistant of Mg alloys; (iii) semisolid state processing of Mg alloys and (iv) development of ultralight Mg alloys. For commercial utilization of Mg alloy parts, several problems, such as melting/casting, corrosion and recycling, have to be tackled. This review also contains a brief summary of the development project of Mg alloy parts for commercial application, mainly for automobile parts.     

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.     

Atomic-scale analysis of light alloys using atom probe tomography

The present paper reviews recent progress in atomic-scale characterisation of composition and nanostructure of light alloy materials using the technique of atom probe tomography. In particular, the present review will highlight atom-by-atom analysis of solid solution architecture, including solute clustering and short-range order, with reference to current limitations of spatial resolution and detector efficiency of atom probe tomography and methods to address these limitations. This leads to discussion of prediction of mechanical properties by simulation and modelling of the strengthening effect exerted by solute clusters and the role of experimental atom probe data to assist in this process. The unique contribution of atom probe tomography to the study of corrosion and hydrogen embrittlement of light alloys will also be discussed as well as a brief insight into its potential application for the investigation of solute strengthening of twinning in Mg alloys.     

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.     

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.     

生物医用可降解锌基合金的研究进展

锌基合金是近几年新兴的一种医用可降解材料,有望应用于心血管支架及骨植入等医疗器械。锌是人体必需的营养元素,具有良好的生物相容性及适宜的体内降解速率,作为可降解合金的基体有很广的应用前景。然而,生物可降解锌基合金的设计、加工、强化及降解机理等研究尚处于起步阶段,还需要做大量的基础研究工作。本文以最终医疗器械产品的理想标准要求为切入点,从生物相容性、力学性能及抗腐蚀性能等方面对近几年医用锌基合金的研究成果进行了综述分析,并展望了其未来的发展方向。     

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.     

可生物降解镁合金微细管的加工成形:坯料超细晶化、工艺参数优化、新技术开发及应用

镁合金作为新型可生物降解材料在血管支架等植介入产品领域具有广阔的应用前景,然而镁合金微细管材的精密加工特别是冷成形十分困难,这是制约其大规模临床推广应用的主要因素之一。全面综述了近期关于可生物降解镁合金微细管加工成形的研究进展,重点介绍了镁合金坯料显微组织的调控,镁合金微细管精密加工参数的优化和新型加工技术的开发及应用。最后,指出了可生物降解镁合金微细管加工成形的研究方向。