Magnesium-based metals are considered as promising biodegradable orthopedic implant materials due to their potentials of enhancing bone healing and reconstruction, and in vivo absorbable characteristic without second operation for removal. However, the rapid corrosion has limited their clinical applications. Ca-P coating by electrodeposition has been supposed to be effective to control the degradation rate and enhance the bioactivity. In this work, a brushite coating was fabricated on the Mg-Sr alloy by pulse electrodeposition (PED) to evaluate its efficacy for orthopedic application. Interestingly, an inner corrosion layer was observed between the PED coating and the alloy substrate. Meanwhile the results of in vitro immersion and electrochemical tests showed that the corrosion resistance of the coated alloy was undermined in comparison with the uncoated alloy. It was deduced that the existence of this corrosion layer was attributed to the worse corrosion performance of the alloy. The mechanism on formation of the inner corrosion layer and its influence on consequent degradation were analyzed. It can be concluded that the electrodeposition coating should be not suitable for those magnesium alloys with poor corrosion resistance such as the Mg-Sr alloy. More importantly, it should be noted that the process of coating formation combined with the nature of substrate alloy is important to evaluate the efficacy of coating for biodegradable Mg-based implants application.

Considering the compatibility between degradation and bioactivity of magnesium-based implants for bone repair, micro-arc oxidation is used to modify the magnesium alloy surface in aqueous electrolytes, allowing strontium, calcium, and phosphorus to be incorporated into the coating. The thickness, composition, morphology and phase of this Sr–Ca–P containing coating are characterized by scanning electron microscopy equipped with energy dispersive X-ray spectrometer and X-ray diffraction. The in vitro and in vivo degradation of the coating is evaluated by immersion test, electrochemical test and implantation test. Moreover, the cytocompatibility is tested with osteoblast cell according to ISO 10993. The results show that Sr, Ca and P elements are incorporated into the oxide coating, and a refined structure with tiny discharging micro-pores is observed on the surface of the coating. The Sr–Ca–P coating possesses a better corrosion resistance in vitro and retards the degradation in vivo. Such coating is expected to have significant medical applications on orthopedic implants and bone repair materials.

•Three different statuses of Mg–Sr alloys are used to compare the efficacy for bone graft application.•The rapid degradation is due to intergranular distribution of Mg17Sr2 and galvanic corrosion.•The as-cast alloy with MAO coating exhibited tailored degradation and good biocompatibility.•The in vivo compatible degradation with bone healing is observed for the as-cast alloy with coating.Bone defects are very challenging in orthopedic practice. There are many practical and clinical shortcomings in the repair of the defect by using autografts, allografts or xenografts, which continue to motivate the search for better alternatives. The ideal bone grafts should provide mechanical support, fill osseous voids and enhance the bone healing. Biodegradable magnesium–strontium (Mg–Sr) alloys demonstrate good biocompatibility and osteoconductive properties, which are promising biomaterials for bone substitutes. The aim of this study was to evaluate and pair the degradation of Mg–Sr alloys for grafting with their clinical demands. The microstructure and performance of Mg–Sr alloys, in vitro degradation and biological properties including in vitro cytocompatibility and in vivo implantation were investigated. The results showed that the as-cast Mg–Sr alloy exhibited a rapid degradation rate compared with the as-extruded alloy due to the intergranular distribution of the second phase and micro-galvanic corrosion. However, the initial degradation could be tailored by the coating protection, which was proved to be cytocompatible and also suitable for bone repair observed by in vivo implantation. The integrated fracture calluses were formed and bridged the fracture gap without gas bubble accumulation, meanwhile the substitutes simultaneously degraded. In conclusion, the as-cast Mg–Sr alloy with coating is potential to be used for bone substitute alternative.

•A non-toxic Mg-based alloy system with nutrient elements Si, Sr, Ca is proposed.•Properties improved due to morphology of coarse Mg2Si change into small polygon.•Fewer, finer and homogenized Mg2Si particles are obtained after anneal-treated.•Cytocompatibility results indicate a potential application in orthopedic.Magnesium has been widely studied as a biodegradable material, where its mechanical property and biocompatibility make it preferred candidate for orthopedic implant. Proper alloying can further improve the properties of Mg. First and foremost, to guarantee the biosafety for biomedical application, the alloying element should be toxic free. To address this point, nutrient elements including Si, Sr and Ca were selected due to their biological functions in human body, especially in bone regeneration and repair. In this study, 0.5–1.0 wt% Sr and Ca were used to refine and modify the morphology of coarse Mg2Si in Mg-1.38wt% Si to obtain an uniform microstructure. Microstructure, mechanical and degradation properties of as-cast and homogenizing-annealed quaternary Mg-1.38Si-xSr-yCa (x, y = 0.5–1 wt%) alloys were investigated by optical microscopy, scanning electronic microscopy, X-ray diffraction, tensile and electrochemical measurement. Addition of Sr and Ca element cause a morphological change in Mg2Si particles from coarse Chinese script shape to small polygonal type. The presences of intermetallic phases, such as Mg2Si, CaMgSi and Mg17Sr2, were confirmed in quaternary alloys, of which content was applied to interpret the results for the quaternary system. Compared with the as-cast state, fewer, finer and homogenized microstructure were observed after an anneal heat treatment under 500 °C. The mechanical properties were improved with increase of Ca and Sr additions, which was related to the evolution of the microstructure and second phases, however, also causing an increase of corrosion rate due to the galvanic-corrosion at the same time. The cytocompatibility results revealed that the Mg-Si-Sr-Ca alloys promote the proliferation of preosteoblasts and exhibit cytotoxicity of Grade 0–1, indicating their acceptable biosafety and potential for the orthopedic applications.

•The MAO, PED and Sr-P coating were fabricated on Mg-Sr alloy to evaluate the degradation.•The MAO coating showed the greatest degradation performance among these three coatings.•The PED coating exhibited worse corrosion resistance even than Mg-Sr substrate.•The value of cell proliferation and ALP activity were ranked in the following order: MAO > Sr-P > PED.To solve the problem of rapid degradation for magnesium-based implants, surface modification especially coating method is widely studied and showed the great potential for clinical application. However, as concerned to the further application and medical translation for biodegradable magnesium alloys, there are still lack of data and comparisons among different coatings on their degradation and biological properties. This work studied three commonly used coatings on Mg-Sr alloy, including micro-arc oxidation coating, electrodeposition coating and chemical conversion coating, and compared these coatings for requirements of favorable degradation and biological performances, how each of these coating systems has performed. Finally the mechanism for the discrepancy between these coatings is proposed. The results indicate that the micro-arc oxidation coating on Mg-Sr alloy exhibited the best corrosion resistance and cell response among these coatings, and is proved to be more suitable for the orthopedic application.

Controlling the corrosion rate of magnesium alloys in vivo to match the bone repair is crucially important for application as biodegradable orthopedic implants. To solve this challenge, a Si-doped Ca–P coating with a novel dual-layer structure was deposited on AZ31 alloy substrate by pulse electrodeposition. The morphology, composition and formation of dual-layer coating were believed to be determined by pulse electrodeposition parameters, thus the deposition time, temperature, duty cycle, pH value of the electrolyte and the standing duration of mixed electrolyte were regulated to seek possible influences and mechanism on the coating formation. Weight gain and pH monitoring tests were also used to evaluate the performance of coating under the varied parameters. The results indicated that deposition temperature and time remarkably influenced the morphology, homogeneity and crystallinity of Ca–P coating. A uniform and compact coating with better degradation performance was obtained at 60 °C with deposition time of 40 min. The shorter standing duration of the electrolyte lead to an incomplete coating and uneven distribution of Si contents. The two coupled deposition models contributed to this dual-layer structure of Si-doped Ca–P coating and possible formation mechanism was proposed.

Polymers, such as poly-l-lactide (PLLA) were the first materials to be used as commercial biodegradable and bioresorbable implant materials. However, the limitations were focused on low mechanical properties and acid degradation by-products which were concerned as the source of inflammation. In this work, hybrid composites incorporated PLLA with 3–7 wt% magnesium and magnesium fluoride particles were developed to overcome drawbacks mentioned above as novel bioresorbable orthopedic implants. The morphology, mechanical and thermal properties, in vitro degradation and cytotoxicity assessment were analyzed by SEM, DSC, UTM, pH value monitoring and MTT. It was found that the tensile strength was slightly decreased with addition of Mg particles. The tensile fracture morphologies indicated that the interface adhesion between Mg particles and PLLA matrix could be contributed to the influence on mechanism property. The addition of Mg and MgF2 into PLLA was effective in neutralizing the acid environment caused by degradation by-products, which was reflected by a close pH value to body fluid. Moreover, cell viability showed better cytocompatibility of composites with the beneficial Mg ions release. Therefore, PLLA/magnesium and PLLA/magnesium fluoride hybrid composites had a promising potential for orthopedic implant application.

•A Si-doped calcium phosphate coating was achieved via pulse ED on AZ31 alloy.•The coating was composed of a porous lamellar-like layer and outer block-like apatite.•The coating showed slow degradation rate and better biomineralization property.•The coating improved cell proliferation and activity of osteogenic marker ALP.A silicon doped calcium phosphate coating was obtained successfully on AZ31 alloy substrate via pulse electrodeposition. A novel dual-layer structure was observed with a porous lamellar-like and outer block-like apatite layer. In vitro immersion tests were adopted in simulated body fluid within 28 days of immersion. Slow degradation rate obtained from weight loss was observed for the Si-doped Ca–P coating, which was also consistent with the results of electrochemical experiments showing an enhanced corrosion resistance for the coating. Further formation of an apatite-like layer on the surface after immersion proved better integrity and biomineralization performance of the coating. Biological characterization was carried out for viability, proliferation and differentiation of MG63 osteoblast-like cells. The coating showed a good cell growth and an enhanced cell proliferation. Moreover, an increased activity of osteogenic marker ALP was found. All the results demonstrated that the Si-doped calcium phosphate was perspective to be used as a coating for magnesium alloy implants to control the degradation rate and enhance the bioactivity, which would facilitate the rapidity of bone tissue repair.

•We fabricated a super-hydrophobic surface on AZ31 magnesium alloy.•The surface is covered by nubby clusters which exhibited an interesting structure with nanoscale protuberances.•The corrosion of AZ31 substrate was inhibited because of the water repellent property of super-hydrophobic surface.•Nearly no platelet adhesion was observed on the super-hydrophobic surface and the hemolysis rate was significantly reduced.Micro-nanometer scale structure of nubby clusters overlay was constructed on the surface of an AZ31 magnesium alloy by a wet chemical method. The super-hydrophobicity was achieved with a water contact angle of 142° and a sliding angle of about 5°. The microstructure and composition of the super-hydrophobic surface were characterized by SEM and FTIR. Potentiodynamic polarization and electrochemical impedance spectroscopy were used to evaluate the corrosion behavior, and the hemocompatibility of the super-hydrophobic surface was investigated by means of hemolytic and platelet adhesion tests. Results showed that the super-hydrophobic treatment could improve the corrosion resistance of magnesium alloys in PBS and inhibit blood platelet adhesion on the surface, which implied excellent hemocompatibility with controlled degradation.

Degradable or corrosive biometal is an attractive research and development (R&D) area in clinical orthopaedics. This study was designed to investigate biomechanical and biological properties of magnesium (Mg) and strontium (Sr) with a focus on Mg-based metals, including pure Mg and Mg–xwt% Sr (x = 0.25, x = 1.0, x = 1.5, x = 2.5) alloys, as potential bone graft substitutes in respect to their mechanical strength, corrosion resistance, and cytocompatibility for further optimization and establishing indications for relevant in vivo applications. Our data showed that the tensile and compressive strength increased with addition of Sr because of the Mg17Sr2 precipitation strengthen. Compared with commercially used bone graft substitutes, the mechanical properties of Mg–Sr alloys were close to those of cortical bone, and the compressive strength could reach 300 MPa, suggesting its potential application for load-bearing bone as bone defect filler. The corrosion rates of Mg–xwt% Sr alloys were controlled in the range of 0.05–0.07 mm/y, indicating feasibility of bone grafting and the in situ bone repair process. Moreover, Mg–Sr alloys also exhibit good cytocompatibility and antibacterial properties. Our innovation presented in this work supported in vivo clinical indication-based assessment of biodegradable Mg-based metals that could be potential candidates for bone graft substitutes for future orthopaedic applications.

•Novel biodegradable MgSr bone substitutes with the hollow and marginal design was fabricated•The MgSr substitutes exhibited excellent cyto-compatibility and osteo-inductivity effects•The osteo-inductivity mechanism was significant up-regulation of the typical osteogenesis-related factorsRegeneration of bone defects is a clinical challenge that usually necessitates bone grafting materials. Limited bone supply and donor site morbidity limited the application of autografting, and improved biomaterials are needed to match the performance of autografts. Osteoinductive materials would be the perfect candidates for achieving this task. Strontium (Sr) is known to encourage bone formation and also prevent osteoporosis. Such twin requirements have motivated researchers to develop Sr-substituted biomaterials for orthopedic applications. The present study demonstrated a new concept of developing biodegradable and hollow three-dimensional magnesium-strontium (MgSr) devices for grafting with their clinical demands. The microstructure and performance of MgSr devices, in vitro degradation and biological properties including in vitro cytocompatibility and osteoinductivity were investigated. The results showed that our MgSr devices exhibited good cytocompatibility and osteogenic effect. To further investigate the underlying mechanisms, RT-PCR and Western Blotting assays were taken to analyze the expression level of osteogenesis-related genes and proteins, respectively. The results showed that our MgSr devices could both up-regulate the genes and proteins expression of the transcription factors of Runt-related transcription factor 2 (RUNX2) and Osterix (OSX), as well as alkaline phosphatase (ALP), Osteopontin (OPN), Collagen I (COL I) and Osteocalcin (OCN) significantly. Taken together, our innovation presented in this work demonstrated that the hollow three-dimensional MgSr substitutes had excellent biocompatibility and osteogenesis and could be potential candidates for bone grafting for future orthopedic applications.