Modification of Iron with Degradable Silver Phases Processed via Laser Beam Melting for Implants with Adapted Degradation Rate

In medical technology, implants are used to improve the quality of patients’ lives. The development of materials with adapted properties can further increase the benefit of implants. If implants are only needed temporarily, biodegradable materials are beneficial. In this context, iron-based materials are promising due to their biocompatibility and mechanical properties, but the degradation rate needs to be accelerated. Apart from alloying, the creation of noble phases to cause anodic dissolution of the iron-based matrix is promising. Due to its high electrochemical potential, immiscibility with iron, biocompatibility, and antibacterial properties, silver is suited for the creation of such phases. A suitable technology for processing immiscible material combinations is powder-bed-based procedure like laser beam melting. This procedure offers short exposure times to high temperatures and therefore a limited time for diffusion of alloying elements. As the silver phases remain after the dissolution of the iron matrix, a modification is needed to ensure their degradability. Following this strategy, pure iron with 5 wt% of a degradable silver–calcium–lanthanum alloy is processed via laser beam melting. Investigation of the microstructure yields achievement of the intended microstructure and long-term degradation tests indicates an impact on the degradation, but no increased degradation rate.     

In vivo behavior of biodegradable Mg-Nd-Y-Zr-Ca alloy

The aim of the this study is to evaluate the in vivo behavior of Mg–1.5%Nd–0.5%Y–0.5%Zr implants with and without 0.4%Ca in comparison with inert Ti-6Al-4V reference implants. This was carried out by implanting cylindrical disks at the back midline of Wister male rats within the subcutaneous layer of the skin for up to 12 weeks. The degradation of magnesium-based implants in terms of hydrogen gas bubble formation was evaluated by radiography assessment; corrosion rate was analyzed by visual examination and weight loss measurements. The physiological response of the rats post-implantation was obtained by evaluating their wellbeing behavior and blood biochemical analysis including serum Mg, blood urea nitrogen, and serum creatinine. In addition, histological analyses of the soft tissue around the implants were carried out to assess local lesions relating to the implants such as inflammation, tissue necrosis, granulation, mineralization, and tumor development. The results obtained clearly indicate that apart from the normal degradation characteristics and subsequent formation of hydrogen gas bubbles, the in vivo behavior of Mg implants was adequate and comparable to that of Ti-6Al-4V reference alloy. In addition, it was evident that the corrosion degradation of the magnesium alloys was strongly related to the location of the implant within the animal’s body. The addition of 0.4%Ca improves the biodegradation corrosion resistance of the tested magnesium implants.     

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.     

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。     

In vitro degradation behavior of M1A magnesium alloy in protein-containing simulated body fluid

Magnesium alloys possess unique advantages to be used as biodegradable implants for clinical applications. In this study, in vitro cells responses and degradation behaviors of magnesium alloy M1A in simulated body fluid (SBF) and albumin-containing SBF (A-SBF) were systematically investigated. Cell responses, in terms of Cell morphology and cell proliferation, imply that M1A possesses good viability for MG63 cells. The corrosion behaviors of M1A are strongly affected by the addition of albumin through the combined effects of adsorption and chelation. Electrochemical testing indicates that such an absorbed albumin layer makes M1A to be more noble with a smaller corrosion current. Corrosion rate monitored by hydrogen evolution rate suggests that the quickly adsorbed albumin serves as an effective protective layer, resulting in a much slower hydrogen release rate at initial stage. With increasing immersion time, a higher corrosion rate is observed since the chelation effect exerts more significant acceleration effects on the removal of the passivation layer. The corrosion mode evaluated by surface morphology of the samples changes from a nonuniform-anisotropic mode for M1A in SBF to a uniform-isotropic mode for M1A in A-SBF.     

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.     

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.     

Predicting the degradation behavior of magnesium alloys with a diffusion-based theoretical model and in vitro corrosion testing

Magnesium alloys have shown great potential for their use in the medical device field, due to the promising biodegradability. However, it remains a challenge to characterize the degradation behavior of the Mg alloys in a quantitative manner. As such, controlling the degradation rate of the Mg alloys as per our needs is still hard, which greatly limits the practical application of the Mg alloys as a degradable biomaterial. This paper discussed a numerical model developed based on the diffusion theory, which can capture the experimental degradation behavior of the Mg alloys precisely. The numerical model is then implemented into a finite element scheme, where the model is calibrated with the data from our previous studies on the corrosion of the as-cast Mg-1Ca and the as-rolled Mg-3Ge binary alloys. The degradation behavior of a pin implant is predicted using the calibrated model to demonstrate the model’s capability. A standard flow is provided in a practical framework for obtaining the degradation behavior of any biomedical Mg alloys. This methodology was further verified via the comparison with enormous available experimental results. Lastly, the material parameters defined in this model were provided as a new kind of material property.     

In vitro corrosion of magnesium alloy AZ31 --- a synergetic influence of glucose and Tris

Biodegradable Mg alloys have generated great interest for biomedical applications. Accurate predictions of in vivo degradation of Mg alloys through cost-effective in vitro evaluations require the latter to be conducted in an environment close to that of physiological scenarios. However, the roles of glucose and buffering agents in regulating the in vitro degradation performance of Mg alloys has not been elucidated. Herein, degradation behavior of AZ31 alloy is investigated by hydrogen evolution measurements, pH monitoring and electrochemical tests. Results indicate that glucose plays a content-dependent role in degradation of AZ31 alloy in buffer-free saline solution. The presence of a low concentration of glucose, i.e. 1.0 g/L, decreases the corrosion rate of Mg alloy AZ31, whereas the presence of 2.0 and 3.0 g/L glucose accelerates the corrosion rate during long term immersion in saline solution. In terms of Tris-buffered saline solution, the addition of glucose increases pH value and promotes pitting corrosion or general corrosion of AZ31 alloy. This study provides a novel perspective to understand the bio-corrosion of Mg alloys in buffering agents and glucose containing solutions.     

Synergism between effects of velocity,temperature, and alloy corrosion resistance in laboratory simulated fluidised bed environments

Abstract

In studies of the erosion of alloys at elevated temperature, the combined effects of velocity, temperature, and alloy corrosion resistance are not well understood. Wide variations in the effects of velocity have been observed for alloys of different corrosion resistance in various erosion–corrosion environments. There is also some evidence that temperature can affect this relationship. The object of the present work was to undertake a systematic study of the effects of erodent velocity for two alloys, mild steel and 310 stainless steel, at elevated temperatures (300 and 600°C). The velocity was controlled at values between 1·5 and 4·5 m S^?l. Weight change data and analytical scanning electron microscopy were used to characterise the degradation in the various conditions. The results showed that the ranking order of the erosion–corrosion rates of the two different alloys varied as a function of velocity. The velocity at which the ranking of the two alloys reversed increased with increasing temperature. The reasons for such behaviour are discussed in terms of the dependence of the erosion–corrosion rate on the velocity in the various erosion–corrosion regimes.

MST/3188     

Comparison of the Corrosion Behavior of Coated and Uncoated Magnesium Alloys in an In Vitro Corrosion Environment

The in vitro degradation of magnesium alloys with various alloying elements, the effect of coatings, and the impact of an altered experimental environment are investigated. LANd442 and Nd2 alloys are subjected to a continuously moving environment during an immersion test allowing flowing SBF. Applying an MgF₂ coating to the alloys increases the corrosion resistance of LANd442 but has no effect on the corrosion rate of Nd2 within the period of investigation. It leads to a more‐even degradation with less pitting corrosion in the early stages of corrosion. A bioglass coating on Nd2 increases the corrosion rate. The mass loss, volume loss, and loss in maximum force all show the same trends as the specimens degrade over time.     

A high strength,wear and corrosion-resistant,antibacterial and biocompatible Nb-5 at.％ Ag alloy for dental and orthopedic implants

Refractory metal niobium (Nb) incorporated with a small amount of silver (Ag),the resulting Nb-Ag two-phase alloys,were fabricated by mechanical alloying and spark plasma sintering.The microstructure,mechanical properties,wear resistance,corrosion behavior,in vitro and in vivo antibacterial properties and biocompatibility of the Nb-Ag alloys were systematically investigated.The results show that the mechanical properties,wear resistance,corrosion resistance and antibacterial ability were significantly enhanced after addition of 5 at.％ Ag.The fabricated Nb-5 at.％ Ag alloy demonstrates high yield strength of up to ～ 1486 MPa and fracture strain of ～ 35 ％.The precipitated Ag particles could reduce friction and wear.The enhanced corrosion resistance was attributed to the higher relative density of the sintered alloys and the formation of a stable and dense passive film of niobium and silver oxides.In vitro and in vivo evaluations show that the Nb-5 at.％ Ag alloy also has strong antibacterial activity and good biocompati-bility and osteointegration ability.These results demonstrate great potential of the nanostructured Nb-Ag alloys for dental and orthopedic implants.     

Effect of minor content of Gd on the mechanical and degradable properties of as-cast Mg-2Zn-xGd-0.5Zr alloys

RE-containing Mg alloys used as biodegradable medical implants exhibit good promising application due to their good mechanical properties and degradation resistance. In this work, effect of Gd on the microstructure, mechanical properties and biodegradation of as-cast Mg-2Zn-xGd-0.5Zr alloys was investigated. The results showed that there were mainly α-Mg, I-phase, W-phase and MgZn2 phase in Mg-Zn-Gd-Zr alloys. With increase of the Gd content, the strength of the alloys was enhanced due to the second phase strengthening and grain refinement. The degradation resistance of Mg-2Zn-0.5Zr alloy was increased by adding 0.5%–1% Gd due to the uniformly distributed second phases which acted as a barrier to prevent the pitting corrosion. However, increasing Gd content to 2% reduced the degradation resistance of the alloy due to the galvanic corrosion between the matrix and the second phases.The good degradation resistance and mechanical properties of as-cast Mg-2Zn-1Gd-0.5Zr alloy makes it outstanding for biomaterial application.     

<Emphasis Type="Italic">In vitro</Emphasis> corrosion of magnesium alloy AZ31 — a synergetic influence of glucose and Tris

Biodegradable Mg alloys have generated great interest for biomedical applications. Accurate predictions of in vivo degradation of Mg alloys through cost-effective in vivo evaluations require the latter to be conducted in an environment close to that of physiological scenarios. However, the roles of glucose and buffering agents in regulating the in vivo degradation performance of Mg alloys has not been elucidated. Herein, degradation behavior of AZ31 alloy is investigated by hydrogen evolution measurements, pH monitoring and electrochemical tests. Results indicate that glucose plays a content-dependent role in degradation of AZ31 alloy in buffer-free saline solution. The presence of a low concentration of glucose, i.e. 1.0 g/L, decreases the corrosion rate of Mg alloy AZ31, whereas the presence of 2.0 and 3.0 g/L glucose accelerates the corrosion rate during long term immersion in saline solution. In terms of Tris-buffered saline solution, the addition of glucose increases pH value and promotes pitting corrosion or general corrosion of AZ31 alloy. This study provides a novel perspective to understand the bio-corrosion of Mg alloys in buffering agents and glucose containing solutions.     

Advanced Stellite alloys with improved metal-on-metal bearing for hip implants

Stellite 21 is a low-carbon Co–Cr–Mo alloy that has been used for hip implants for decades. The Stellite 21 implants can fail when the femoral head and the acetabular cup loosen because of limited metal-on-metal bearing. Two modified Stellite 21 alloys with better bearing capacities are proposed as replacements in this study: Cr-modified Stellite 21 with additional 10 wt.% Cr, and N-modified Stellite 21 with addition of 0.5 wt.% CrN. The wear and corrosion resistances of these alloys were investigated in simulated conditions experienced by hip implants in human bodies. The experimental results show that the proposed alloys all exhibit better wear resistance than the conventional hip implant material, but only Cr-modified Stellite 21 displays better corrosion resistance, thus this alloy should be considered for use in future hip implants.     

Microstructure, cytotoxicity and corrosion of powder-metallurgical iron alloys for biodegradable bone replacement materials

Up to now biodegradable bone implants with the ability of bearing high loads for the temporary replacement of bones or as osteosynthesis material are not available. Iron and iron based alloys have been identified as appropriate materials, since they combine high strength at medium corrosion rates. Thus, the aim of the present study is the development of a degradable iron based alloy with the perspective of using them as matrix material of cellular structures with biomechanical tailored properties. A powder metallurgical approach has been used to manufacture Fe-C, Fe-0.6P, Fe-1.6P, Fe-B and Fe-Ag samples, which have been tested with respect to their microstructure, their cytotoxicity, and their degradation rate. In order to determine the cytotoxicity of the material a monolayer culture of fibroblast and a perfusion chamber system has been chosen, which was recommended by the ISO 10993-5:1999 for biological testing of medical devices. It has been found, that in particular phosphorus features beneficial properties, since density and thus the strength of the material are increased. No corrosion inhibiting effects of phosphorus on the degradation rate have been found.     

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.     

New insights into the effect of Tris-HCl and Tris on corrosion of magnesium alloy in presence of bicarbonate,sulfate,hydrogen phosphate and dihydrogen phosphate ions

In vitro degradation is an important approach to screening appropriate biomedical magnesium(Mg) alloys at low cost. However, corrosion products deposited on Mg alloys exert a critical impact on corrosion resistance. There are no acceptable criteria on the evaluation on degradation rate of Mg alloys. Understanding the degradation behavior of Mg alloys in presence of Tris buffer is necessary. An investigation was made to compare the influence of Tris-HCl and Tris on the corrosion behavior of Mg alloy AZ31 in the presence of various anions of simulated body fluids via hydrogen evolution, p H value and electrochemical tests.The results demonstrated that the Tris-HCl buffer resulted in general corrosion due to the inhibition of the formation of corrosion products and thus increased the corrosion rate of the AZ31 alloy. Whereas Tris gave rise to pitting corrosion or general corrosion due to the fact that the hydrolysis of the amino-group of Tris led to an increase in solution p H value, and promoted the formation of corrosion products and thus a significant reduction in corrosion rate. In addition, the corrosion mechanisms in the presence of Tris-HCl and Tris were proposed. Tris-HCl as a buffer prevented the formation of precipitates of HCO_3~-, SO_4~(2-),HPO_4~(2-) and H_2PO_4~- ions during the corrosion of the AZ31 alloy due to its lower buffering p H value(x.x).Thus, both the hydrogen evolution rate and corrosion current density of the alloy were approximately one order of magnitude higher in presence of Tris-HCl than Tris and Tris-free saline solutions.     

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.