Laser additive manufacturing of biodegradable Mg-based alloys for biomedical applications: A review

Metallic implants are widely used in internal fixation of bone fracture in surgical treatment.They are mainly used for providing mechanical support and stability during bone reunion,which usually takes a few months to complete.Conventional implants made of stainless steels,Ti-based alloys and CoCrMo alloys have been widely used for orthopedic reconstruction due to their high strength and high corrosion resistance.Such metallic implants will remain permanently inside the body after implantation,and a second surgery after bone healing is needed because the long-term presence of implant will lead to various problems.An implant removal surgery not only incurs expenditure,but also risk and psychological burden.As a consequence,studies on the development of biodegradable implants,which would degrade and disappear in vivo after bone reunion is completed,have drawn researchers’attention.In this connection,Mg-based alloys have shown great potentials as promising implant materials mainly due to their low density,inherent biocompatibility,biodegradability and mechanical properties close to those of bone.However,the high degradation rate of Mg-based implants in vivo is the biggest hurdle to overcome.Apart from materials selection,a fixation implant is ideally tailor-made in size and shape for an individual case,for best surgical outcomes.Therefore,laser additive manufacturing(LAM),with the advent of sophisticated laser systems and software,is an ideal process to solve these problems.In this paper,we reviewed the progress in LAM of biodegradable Mg-based alloys for biomedical applications.The effect of powder properties and laser processing parameter on the formability and quality was thoroughly discussed.The microstructure,phase constituents and metallurgical defects formed in the LAMed samples were delineated.The mechanical properties,corrosion resistance,biocompatibility and antibacterial properties of the LAMed samples were summarized and compared with samples fabricated by traditional processes.In addition,we have made some suggestions for advancing the knowledge in the LAM of Mg-based alloys for biomedical implants.

A homogenous microstructural Mg-based matrix model for orthopedic application with generating uniform and smooth corrosion product layer in Ringer’s solution:Study on biodegradable behavior of Mg-Zn alloys prepared by powder metallurgy as a case

For high corrosion resistance and extensively modified biodegradable Mg-based alloys and composites for bone implants,a new Mgbased matrix model prepared by powder metallurgy is discussed and developed.In this research,Mg-5 wt.%Zn alloys were selected as a case.And they were impacted by hot extrusion and aging treatments to construct microstructure with different characteristics.Their selfforming corrosion product layer in Ringer’s solution,biodegradable behavior and corrosion mechanism were minutely investigated by in vitro degradation,electrochemical corrosion and cytocompatibility.The results demonstrated the extruded Mg-5 wt.%Zn alloy aged for 96 h showed high corrosion resistance,good biocompatibility for L929 and excellent ability of maintaining sample integrity during the immersion.Significantly,the alloy showed fine-grain microstructure and uniform distributed hundred nano-sized second phases,which promoted the formation of the uniform and smooth corrosion product layer at the beginning of immersion.The corrosion product layer was more stable in chloride containing aqueous solution and could be directly formed and repaired quickly,which effectively protected the matrix from further corrosion.In addition,an ideal model of Mg-based matrix for bone tissue engineering was tried to presume and propose by discussing the causal relationship between microstructure and bio-corrosion process.

Progress and prospects of Mg-based amorphous alloys in azo dye wastewater treatment

Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problems like difficulty in preparation and poor cycling stability need to be solved.At present,Mg-based amorphous alloys applied in wastewater degradation are available in powder and ribbon.The amorphous alloy powder fabricated by ball milling has a high specific surface area,and its reactivity is thousands of times better than that of gas atomized alloy powder.But the development is limited due to the high energy consumption,difficult and costly process of powder recycling.The single roller melt-spinning method is a new manufacturing process of amorphous alloy ribbon.Compared to amorphous powder,the specific surface area of amorphous ribbon is relatively lower,therefore,it is necessary to carry out surface modification to enhance it.Dealloying is a way that can form a pore structure on the surface of the amorphous alloys,increasing the specific surface area and providing more reactive sites,which all contribute to the catalytic performance.Exploring the optimal conditions for Mg-based amorphous alloys in wastewater degradation by adjusting amorphous alloy composition,choosing suitable method to preparation and surface modification,reducing cost,expanding the pH range will advance the steps to put Mg-based amorphous alloys in industrial environments into practice.

A multi-functional MgF_(2)/polydopamine/hyaluronan-astaxanthin coating on the biodegradable ZE21B alloy with better corrosion resistance and biocompatibility for cardiovascular application

The cardiovascular diseases(CVD)continue to be the major threat to global public health over the years,while one of the effective methods to treat CVD is stent intervention.Biomedical magnesium(Mg)alloys have great potential applications in cardiovascular stents benefit from their excellent biodegradability and absorbability.However,excessive degradation rate and the delayed surface endothelialization still limit their further application.In this study,we modified a Mg-Zn-Y-Nd alloy(ZE21B)by preparing MgF_(2) as the corrosion resistance layer,the dopamine polymer film(PDA)as the bonding layer,and hyaluronic acid(HA)loaded astaxanthin(ASTA)as an important layer to directing the cardiovascular cells fate.The electrochemical test results showed that the MgF_(2)/PDA/HA-ASTA coating improved the corrosion resistance of ZE21B.The cytocompatibility experiments also demonstrated that this novel composite coating also selectively promoted endothelial cells proliferation,inhibited hyperproliferation of smooth muscle cells and adhesion of macrophages.Compared with the HAloaded rapamycin(RAPA)coating,our MgF_(2)/PDA/HA-ASTA coating showed better blood compatibility and cytocompatibility,indicating stronger multi-functions for the ZE21B alloy on cardiovascular application.

Improving corrosion resistance of additively manufactured WE43 magnesium alloy by high temperature oxidation for biodegradable applications

Laser powder bed fusion(L-PBF)has been employed to additively manufacture WE43 magnesium(Mg)alloy biodegradable implants,but WE43 L-PBF samples exhibit excessively rapid corrosion.In this work,dense WE43 L-PBF samples were built with the relativity density reaching 99.9%.High temperature oxidation was performed on the L-PBF samples in circulating air via various heating temperatures and holding durations.The oxidation and diffusion at the elevated temperature generated a gradient structure composed of an oxide layer at the surface,a transition layer in the middle and the matrix.The oxide layer consisted of rare earth(RE)oxides,and became dense and thick with increasing the holding duration.The matrix was composed ofα-Mg,RE oxides and Mg_(24)RE_(5) precipitates.The precipitates almost disappeared in the transition layer.Enhanced passivation effect was observed in the samples treated by a suitable high temperature oxidation.The original L-PBF samples lost 40%weight after 3-day immersion in Hank’s solution,and broke into fragments after 7-day immersion.The casted and solution treated samples lost roughly half of the weight after 28-day immersion.The high temperature oxidation samples,which were heated at 525℃ for 8 h,kept the structural integrity,and lost only 6.88%weight after 28-day immersion.The substantially improved corrosion resistance was contributed to the gradient structure at the surface.On one hand,the outmost dense layer of RE oxides isolated the corrosive medium;on the other hand,the transition layer considerably inhibited the corrosion owing to the lack of precipitates.Overall,high temperature oxidation provides an efficient,economic and safe approach to inhibit the corrosion of WE43 L-PBF samples,and has promising prospects for future clinical applications.

Degradation Rate Assessment of Biodegradable Magnesium Alloys

Biodegradable magnesium alloys have been widely used in medical implants. But safety concerns were put forward for the high degradation rate of biodegradable magnesium alloy. The optimal biodegradable magnesium alloys that give rise to the desired degradation rate hasn’t yet to be defined. Assessing the degradation rate of biodegradable magnesium alloys involves in vitro testing, in vivo testing, numerical modeling, understanding the factors influencing their degradation in physiological environments, biocompatibility testing, and clinical studies. It is important to standardize analytical tools aimed at assessing the degradation rate of biodegradable magnesium alloys. It is advisable to identify the threshold for safe degradation rate of biodegradable magnesium alloys in biomedical applications.

Advances in coatings on biodegradable magnesium alloys

The clinic applications of bioabsorbable magnesium(Mg)and its alloys have been significantly restricted owing to their poor corrosion resistance.Besides elemental alloying,surface modification and functionality is a major approach to increasing corrosion resistance for magnesium alloys.This article reviews the cutting-edge advances and progress of biodegradable surface coatings upon Mg alloys over the last decades,aims to build up a knowledge framework of surface modification on biodegradable Mg alloys.A considerable number of conversion,deposition,mechanical and functional coatings and their preparation methods are discussed.The emphasis has been placed on the composition of chemical conversion and deposited coatings to overcome the disadvantages of adhesion,corrosion resistance and biocompatibility of a single coating for biomedical materials.The issues have been addressed on the integration of the structural and functional factors of the composite coatings.

Structural and corrosion characterization of biodegradable Mg-RE (RE=Gd, Y, Nd) alloys

Binary Mg-Gd （up to 5% Gd in mass fraction）, Mg-Nd （up to 9% Nd in mass fraction） and ternary Mg-Gd-Y （up to 5% Gd, 1% Y） alloys with precisely determined contents of cathodic impurities （Fe, Ni, Cu, Co） were studied. The alloys were studied in the as-cast state （cooling rate of 500 K/min） and after solution heat treatment （T4）. Structures were investigated by optical and scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction and glow discharge spectrometry. Structural investigation was completed by Vickers hardness measurements. Corrosion behavior in the simulated physiological solution （9 g/L NaCl） was assessed by immersion tests and potentiodynamic measurements. It was found that the structures of the as-cast alloys were dominated by fine a-Mg dendrites and eutectic Mg-RE phases. The dendrites exhibited RE-concentration gradients which were most pronounced in the Mg-Gd alloys. For this reason, the T4 heat treatment of the Mg-Gd alloy led to the formation of a new cuboidal Mg5Gd phase. The corrosion resistance was significantly improved by Gd. The effect of Nd was weak and the addition of Y to Mg-Gd alloys had harmful effect on the corrosion resistance. The T4 heat treatment strongly accelerated the corrosion of Mg-Gd alloys. Its effect on the corrosion of Mg-Nd alloys was not significant. The observed corrosion behavior of the alloys was discussed in relation to their structural states and contents of cathodic impurities.

Biodegradable Mg alloys for orthopedic implants——A review

The last decade has seen a significant growth in the market for alloys used for implants,especially for those intended for orthopedic implants.Research into biodegradable magnesium-based alloys has made great strides in this period,so huge progress has been made in their use in the medical industry.The important factors that led to the intensification of research in this regard,were social but also economic,wanting to improve the quality of life,by reducing the use of conventionally permanent metallic implants(stainless steel,cobalt-based alloys,and titanium alloys)which involve the second implant removal surgery and other undesirable effects(stress shielding and metal ion releases),with a negative impact on the emotional and physical condition of patients,and by significantly reducing the costs for both the patient and the health system in the field of orthopedics.This paper refers to the impact and importance of biodegradable Mg alloys,reviewing the beginning of their development,the significant characteristics that make them so desirable for such applications(orthopedic implants)but also the characteristics that must be modulated(corrosion rate and mechanical properties)to arrive at the ideal product for the targeted application.It highlights,in detail,the mechanism and aspects related to the corrosion behaviour of Mg alloys,electrochemical characterization techniques/methods,as well as strategies to improve the corrosion behaviour and mechanical properties of these types of biodegradable alloys.The means of optimization,the category and the effect of the alloying elements,the design criteria,the requirements that the implants of biodegradable alloys Mg-based must meet and the aspects related to their efficiency are also presented.Finally,the potential applications in the specialized clinics,as well as the final products currently used and made by important prestigious companies in the world are approached.

Corrosion resistance of bioinspired DNA-induced Ca-P coating on biodegradable magnesium alloy

Bioinspired coatings with decreased corrosion rate and enhanced bond strength are at the core of future clinic applications on degradable magnesium(Mg)-based implants.The hybrid of organic and inorganic compounds offers a strategy to fabricate biodegradable,biocompatible and compact coatings on biomedical Mg alloys.Hereby,a comparison with and without DNA addition was made on the corrosion resistance and adhesion strength of Ca-P coatings fabricated on AZ31 alloy via hydrothermal deposition.The morphology,chemical composition,and crystallographic structure of the coatings were investigated by means of SEM,EDS and FTIR as well as XRD before and after corrosion tests.Corrosion resistance was evaluated via potentiodynamic polarization curves,electrochemical impedance spectroscopy(EIS)and hydrogen evolution tests in Hank’s solution.Results show that the coatings are mainly characterized by tricalcium phosphate(TCP),dicalcium phosphate anhydrous(DCPA)and calcium-deficient hydroxyapatite(CDHA).The presence of DNA leads to the formation of Ca-P coating with improved corrosion resistance and adhesion strength.Additionally,the formation mechanism for DNA-induced Ca-P coating is proposed.The DNA-induced Ca-P coating exhibits a promising future for controlling the corrosion rate of biodegradable Mg alloys.©2019 Published by Elsevier B.V.on behalf of Chongqing University.

A comprehensive review on biocompatible Mg-based alloys as temporary orthopaedic implants:Current status,challenges,and future prospects

Mg and its alloys are drawing huge attention since the last two decades as a viable option for temporary implants applications.A commendable progress has already been made in the development of these alloys.The biodegradable nature of Mg,appreciable biocompatibility of elemental Mg,and its close resemblance to natural bone in terms of density and elastic modulus make them highly preferable option amongst other available alternatives in this field.This review article presents an overview covering the recent advancements made in the field of Mg-based biodegradable implants for orthopaedic implant applications.The paper focuses on alloy development and fabrication techniques,the state of the art of important Mg-based alloy systems in terms of their mechanical properties,in-vitro and in-vivo degradation behaviour and cytotoxicity.Further,the paper reviews the current progress achieved in the clinical transition of Mg-based alloys for orthopaedic fixtures.The review also includes the degradation mechanisms of the alloys in physiological environment and highlights the mismatch existing between the rate of bone healing and alloy degradation due to rapid corrosion of the alloys in such environment,which has still restricted their widespread application.Finally,the surface coating techniques available for the alloys as an effective way to reduce the degradation rate are reviewed,followed by a discussion on the future research prospects.

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed . The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

Open cellular magnesium alloys for biodegradable orthopaedic implants

Replication processing using NaCl spaceholders offers the possibility to produce cellular structures for a range of Mg alloys. Four Mg alloys (AZ63, M2, ZM21 and MZX211) were processed into open cellular structures with a pore size near 500 μm and a porosity of 75% using an optimized NaCl leaching procedure. The production method was found to be robust and yielded samples of acceptable strength and stiffness. Their dissolution rate (by H2 release in simulated body fluid) and mechanical properties (by cyclic compression) were measured. For all 4 alloys the initial mechanical properties mimic those of cancellous bone;however, the dissolution rate is too high for direct use in the human body, leading to excessive hydrogen evolution and overly rapid degradation of mechanical properties. Further post-processing of the material is thus required.

Influence of bimodal grain size distribution on the corrosion behavior of friction stir processed biodegradable AZ31 magnesium alloy

In the present study,AZ31 magnesium alloy sheets were processed by friction stir processing(FSP)to investigate the effect of the grain refinement and grain size distribution on the corrosion behavior.Grain refinement from a starting size of 16.4±6.8µm to 3.2±1.2µm was attained after FSP.Remarkably,bimodal grain size distribution was observed in the nugget zone with a combination of coarse(11.62±8.4µm)and fine grains(3.2±1.2µm).Due to the grain refinement,a slight improvement in the hardness was found in the nugget zone of FSPed AZ31.The bimodal grain size distribution in the stir zone showed pronounced influence on the corrosion rate of FSPed AZ31 as observed from the immersion and electrochemical tests.From the X-ray diffraction analysis,more amount of Mg(OH)_(2) was observed on FSPed AZ31 compared with the unprocessed AZ31.Polarization measurements demonstrated the higher corrosion current density for FSPed AZ31(8.92×10^(−5)A/cm^(2))compared with the unprocessed condition(2.90×10^(−5)A/cm^(2))that can be attributed to the texture effect and large variations in the grain size which led to non-uniform galvanic intensities.

Effect of solution treatment on corrosion characteristics of biodegradable Mg-6Zn alloy

A binary Mg-6Zn biodegradable alloy was solution treated to evaluate the effects of resulting microstructure changes on the alloy＇s degradation rate and mechanisms in-vitro. The treatment was conducted at 350 °C for 6-48 h. Optical and scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction were used to analyze the as-cast and treated samples. Immersion and electrochemical tests were performed in simulated body fluid at 37 °C to assess the samples corrosion resistance. To confirm the results of the corrosion tests, p H measurement was carried out. It is found that over 24 h solution treatment dissolves intermetallic phases in matrix and produces an almost single phase microstructure. Decreasing the intermetallic phases results in lower cathode/anode region ratios and lowers corrosion rates. The results of the electrochemical and mass loss tests reveal that extended solution treatment improves the corrosion resistance of the alloy. The results also show that solution at 350 °C for 24 h enhances the corrosion resistance of the as-cast alloy more than 60%. In addition, decreasing intermetallic phases in the microstructure accompanied a lower p H rise reduced corrosion rate. Solution treatment is suggested as a corrosion improving process for the application of Mg-Zn alloys as biodegradable implant materials.

Effects of alloying elements and thermomechanical process on the mechanical and corrosion properties of biodegradable Mg alloys

In this study,four different Mg-Zn-Ca-Mn alloys were produced using gravity die casting method.Mn content was kept constant in all alloys,while Zn and Ca were added in two different ratios.Homogenization heat treatment was applied to all cast alloys and a specimen from each homogenized alloy was hot rolled.Microstructure,mechanical properties,and corrosion behavior of the homogenized and hot rolled alloys were investigated as comparatively.Following results were obtained;grain size decreased significantly with increasing Zn content,Zn promoted Ca 2 Mg 6 Zn 3 phase formation,corrosion resistance increased with increasing Zn/Ca atomic ratio,hot rolling resulted in much higher tensile strength but much lower ductility and toughness.Among the homogenized and hot rolled alloys,ZXM300-h alloy(hot rolled ZXM300 alloy)with its 146±2.5 MPa yield strength,229±3.7 MPa tensile strength,%1.6±0.1 elongation and 0.029 mm/yr.immersion corrosion rate exhibited the best mechanical properties and corrosion resistance to be used as a biodegradable alloy such as fracture bone plate material.

Hydrogen storage behavior of Mg-based alloy catalyzed by carbon-cobalt composites

The composites comprised of Co nanoparticle and C nanosheet were prepared though a high-temperature carbonization reaction.The catalysis of Co@C composites on the hydrogen storage behavior of Mg_(90)Ce_(5)Y_(5)alloy was investigated in detail by XRD,SEM,TEM,PCI,and DSC method.Because of the synergistic catalytic function of C and Co in C@Co nanocomposites,the Mg_(90)Ce_(5)Y_(5)alloy with 10 wt.%C@Co shows the excellent hydrogen absorption and desorption performances.Time for releasing hydrogen reduces from 150 min to 11 min with the addition of the C@Co composites at the temperature of 300℃.Meanwhile,the dehydrogenation activation energy also declines from 130.3 to 81.9 kJ mol^(-1)H_(2)after the addition of the C@Co composites.This positive effect attributes to the C layer with the high defect density and the Co nanoparticles,which reduces the energy barriers for the nucleation of Mg/MgH_(2)phase and the recombination of hydrogen molecule.Besides,the C@Co composites also improve the activation property of the Mg_(90)Ce_(5)Y_(5)alloy which was folly activated in the first cycle.Moreover,the temperature for initial dehydrogenation and the endothermic peak of the alloy hydride were also decreased.Although the addition of the C@Co composites increases the plateau pressures and decreases the value of the decomposition enthalpy,these differences are so small that the improvement on thermodynamics can hardly be seen.

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1). after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).

Effect of extrusion process on microstructure and mechanical and corrosion properties of biodegradable Mg-5Zn-1.5Y magnesium alloy

The effect of extrusion temperature and ratio on the microstructure, hardness, compression, and corrosion behavior of Mg-5Zn-1.5Y alloy were analyzed in this study. The microstructural observations revealed that the cast alloy consists of α-Mg grains, and Mg3Zn6Y and Mg3Zn3Y2 intermetallic compounds, mostly located on the α-Mg grain boundaries. Extruded alloy at higher temperatures showed coarser grain microstructures, whereas those extruded at higher ratios contained finer ones, although more dynamic recrystalized grains with lower intermetallics were measured at both conditions. Combined conditions of the lower temperature (340°C) and higher ratio (1:11.5) provided higher compressive strengths. However, no significant hardness improvement was achieved. The extrusion process could decrease the corrosion rate of the cast alloy in simulated body fluid for over 80% due to primarily the refined microstructure. The extrusion temperature showed a more pronounced effect on corrosion resistance compared to the extrusion ratio, and the higher the extrusion temperature, the higher the corrosion resistance.

Microstructure and mechanical and corrosion properties of hot-extruded Mg–Zn–Ca–(Mn)biodegradable alloys

Biodegradable Mg-based implants are widely used in clinical applications because they exhibit mechanical properties comparable to those of human bone and require no revision surgery for their removal.Among Mg-based alloys,Mg–Zn–Ca–(Mn)alloys have been extensively investigated for medical applications because the constituent elements of these alloys,Mg,Zn,Ca,and Mn,are present in human tissues as nutrient elements.In this study,we investigated the effect of the hot extrusion temperature on the microstructure,mechanical properties,and biodegradation rate of Mg–Zn–Ca–(Mn)alloys.The results showed that the addition of Mn and a decrease in the extrusion temperature resulted in grain refinement followed by an increase in the strength and a decrease in the elongation at fracture of the alloys.The alloys showed different mechanical properties along the directions parallel and perpendicular to the extrusion direction.The corrosion test of the alloys in the Hanks’solution revealed that the addition of Mn significantly reduced the corrosion rate of the alloys.The Mg–2 wt%Zn–0.7 wt%Ca–1 wt%Mn alloy hot-extruded at 300℃ with an ultimate tensile strength of 278MPa,an yield strength of 229MPa,an elongation at fracture of 10%,and a corrosion rate of 0.3 mm/year was found to be suitable for orthopedic implants.